Abteilung Verfahrenstechnik

Publikationen Verfahrenstechnik

Peer Reviewed Publikationen

Akert, F., Aebischer, P., Udert, K. M., & Reidy, B. (2024). Aurin, ein Dünger aus menschlichem Urin im Praxistest auf Sportrasen. Rasen: Turf: Gazon: European Journal of Turfgrass Science, 55(1), 16-21. , Institutional Repository

Um Nährstoffkreisläufe möglichst zu schließen und Nährstoffe effizient zu nutzen, wurde ein aus menschlichem Urin produzierter Dünger (Aurin) auf einem für Fußball genutzten Sportrasen getestet. Dabei wurde die Rasenfläche in drei Teilflächen unterteilt und von April bis Oktober mit herkömmlichem Handelsdünger (HD), Aurin (A) und Aurin mit Ergänzungsdüngung von Kalium, Phosphor und Magnesium (A+) gedüngt. Die Teilflächen wurden zwischen April und November regelmäßig bonitiert und mittels Multispektralbildanalyse untersucht. Im April, September und Oktober wurden Bodenproben entnommen, um den Nmin Gehalt im Boden zu bestimmen. Aus den Ergebnissen der Untersuchungen zeigten sich nur bei der Rasenfarbe und beim Nmin Gehalt des Bodens geringe Unterschiede. Dabei schien die Nährstoffergänzung von Aurin einen positiven Effekt auf die Stickstoffaufnahme in die Pflanze zu haben. Dies wirkte sich vor allem während Trockenperioden positiv auf die Rasenfarbe aus. Praktische Beobachtungen durch die Pflegeverantwortlichen zeigten, dass ein höheres Ausbringungsintervall mit geringeren Aurin-Mengen sinnvoll war. So konnten die Vernässung der Fläche und die kurzzeitige Verätzung des Rasens verhindert werden. Auch das Stoßwachstum in den Tagen nach der Düngung konnte so gebremst werden. Dieser Praxistest zeigt auf, dass Dünger aus menschlichem Urin eine interessante Option für eine kreislauffähige Bewirtschaftung von Sportrasen oder andere Kulturen mit hohem Stickstoffbedarf darstellen kann. Dies ist allerdings mit einem höheren Arbeitsaufwand in der Bewirtschaftung verbunden.
Bosshard, J., Eugster, F., Gulde, R., & Singer, H. (2024). Abwasser aus der Formulierung von Arzneimitteln. Wirkstoffeinträge in Schweizer Gewässer. Aqua & Gas, 104(3), 50-57. , Institutional Repository

Wirkstoffeinträge von formulierenden Pharmabetrieben führen häufig zu Spitzenkonzentrationen in kommunalen Abwasserreinigungsanlagen. Schweizweite Untersuchungen in Zusammenarbeit mit neun Betrieben zeigen das Ausmass der Einträge für unterschiedliche Abwasservorbehandlungen. Die Studie schliesst wichtige Kenntnislücken bezüglich der Abwasserbelastung von formulierenden Pharmabetrieben und zeigt Handlungsoptionen für die Unternehmen auf.
Bou-Sarkis, A., Paul, E., Bessiere, Y., Derlon, N., & Girbal-Neuhauser, E. (2024). Impact of biochemical properties on the gelation of EPS extracted from aerobic granules. Journal of Environmental Chemical Engineering, 12(5), 113648 (10 pp.). doi:10.1016/j.jece.2024.113648, Institutional Repository

Extracellular Polymeric Substances (EPS) extracted from aerobic granular sludge are a promising source of gel-forming biopolymers. Gaining insights on the charge distribution of these polymers was performed through a fractionation using anionic chromatography. A gelling factor (GF) based on the apparent gel volume and the reactivity of polymers to calcium was attributed to each eluted fraction. The GF values of the eluted anionic EPS correlated with their negative charge. A GF of 0.04 ± 0.03 is measured for molecules eluted at NaCl 0.25 M and a GF of 0.32 ± 0.02 for the molecules eluted at NaCl 0.75 M. However, upon reaching a very high negative charge (elution at NaCl 1 M), the gelation capacity decreases. The size distribution of gelling molecules was analyzed by Size Exclusion Chromatography. High Molecular Weight (MW) molecules are predominantly involved in gelation (between 65 % and 100 % of the high molecular weight fraction from each sample) while low MW molecules participation is relatively limited (lower than 40 % of the low molecular weight fraction from each sample). Moreover, infra-red spectroscopy analysis of the molecules before and after calcium addition showed that mostly proteins and polysaccharides contribute to the hydrogel formation. Colorimetric methods showed that around 60 % of the uronic acids present in the samples could form hydrogels whereas proteins’ participation varied between 0 % and 100 % depending on the fraction. Thus, modulating EPS extraction and purification methods to ensure the preservation of their molecular weight and the selection of appropriate negative charge could be a strategy for EPS valorization.
Brander, A., Wunderlin, P., Gulde, R., & Böhler, M. (2024). MV-Stufen Stabil Betreiben. Hilfreiche Betriebsparameter. Aqua & Gas, 104(1), 54-61. , Institutional Repository

Der Reinigungseffekt für Mikroverunreinigungen wird von ARA über periodische Messungen der Leitsubstanzen bestimmt. Für den täglichen Betrieb lassen sich zusätzlich anhand von UV-Messungen sowie anhand der dosierten Mengen an Ozon oder Aktivkohle zeitnahe Aussagen zur Reinigungsleistung machen.
Endres, L. S., Jacquin, C., González-Lemos, S., Rodríguez-Rodríguez, L., Sliwinski, J., Kaushal, N., … Stoll, H. M. (2024). Climatic and cave settings influence on drip water fluorescent organic matter with implications for fluorescent laminations in stalagmites. Quaternary Research, 118, 41-61. doi:10.1017/qua.2023.41, Institutional Repository

Speleothem fluorescence can provide insights into past vegetation dynamics and stalagmite chronology. However, its origin and especially the formation of fluorescent laminations in stalagmites are poorly understood. We conducted a year-long monthly monitoring of drip water fluorescence in La Vallina Cave (northern Iberian Peninsula) and compared the results to drip water chemistry and active speleothems from the same sites. Drip waters were analyzed using fluorescence spectroscopy and parallel factor analysis (PARAFAC). The resulting five-component model indicates contributions from vegetation, microbial activity, and bedrock. Intra-site fluorescence variability is mainly influenced by changes in overlying vegetation, water reservoir time, and respiration rates. Contrary to prevailing views, we find no systematic increase in drip water fluorescence during rainy conditions across drip sites and seasonal variations in drip water fluorescence are absent at a location where present-day speleothem layers form. Our findings challenge the notion of a higher abundance of humic-like fluorescence during the rainy season as the primary cause for layer formation and suggest additional controls on drip water fluorescence, such as bedrock interaction and microbial reprocessing. We also propose that growth rate may control the dilation of the fluorescence signal in stalagmites, indicating other potential mechanisms for fluorescent layer formation.
Faust, V., Markus, P., Schielke-Jenni, S., Timmer, M. J., De Paepe, J., Ganigué, R., … Udert, K. M. (2024). Conditions for successful nitrogen removal from source-separated urine by partial nitritation/anammox. PLoS Water, 3(5), e0000235 (23 pp.). doi:10.1371/journal.pwat.0000235, Institutional Repository

Partial nitritation/anammox (PN/A) of source-separated urine is less energy-intensive and potentially cheaper and more environmentally friendly than conventional nitrogen removal from mixed sewage. However, PN/A of undiluted source-separated urine has not yet been established. In this study, the feasibility of PN/A for source-separated urine (total nitrogen 2 to 3 g-N L-1). To evaluate the influence of different factors, one- and two-stage configurations were operated using different influents, i.e. source-separated urine, synthetic urine, and urine with additional divalent cations. While partial nitritation was successfully achieved in both configurations with digester supernatant and urine, anammox activity was lost shortly after switching from digester supernatant to the urine influents. Toxic organic compounds or pharmaceuticals and the high monovalent to divalent cation ratio were suspected as causes of anammox failure, but were ruled out due to the different reactor configurations and influent compositions tested. Other suspected factors such as COD/N ratio, phosphate and sulfate inhibition, nitrogen compound inhibition, metal inhibition, pH and dissolved oxygen were also systematically excluded. Instead, the high salt concentration in urine compared to the digester supernatant most likely caused the reactor to fail due to the disintegration of large flocs, and the resulting challenge of biomass retention. The shortcomings of the floccular sludge system were overcome by using biofilm carriers, resulting in successful PN/A. This hybrid system ran for 140 days with nitrogen removal rates of up to 1000 mg-N L-1 d-1 with an average of 410 ± 220 mg-N L-1 d-1, and a nitrogen removal efficiency of 93 ± 3% at 30C.
Faust, V., Vlaeminck, S. E., Ganigué, R., & Udert, K. M. (2024). Influence of pH on urine nitrification: community shifts of ammonia-oxidizing bacteria and inhibition of nitrite-oxidizing bacteria. ACS ES&T Engineering, 4(2), 342-353. doi:10.1021/acsestengg.3c00320, Institutional Repository

Urine nitrification is pH-sensitive due to limited alkalinity and high residual ammonium concentrations. This study aimed to investigate how the pH affects nitrogen conversion and the microbial community of urine nitrification with a pH-based feeding strategy. First, kinetic parameters for NH3, HNO2, and NO2- limitation and inhibition were determined for nitrifiers from a urine nitrification reactor. The turning point for ammonia-oxidizing bacteria (AOB), i.e., the substrate concentration at which a further increase would lead to a decrease in activity due to inhibitory effects, was at an NH3 concentration of 12 mg-N L-1, which was reached only at pH values above 7. The total nitrite turning point for nitrite-oxidizing bacteria (NOB) was pH-dependent, e.g., 18 mg-N L-1 at pH 6.3. Second, four years of data from two 120 L reactors were analyzed, showing that stable nitrification with low nitrite was most likely between pH 5.8 and 6.7. And third, six 12 L urine nitrification reactors were operated at total nitrogen concentrations of 1300 and 3600 mg-N L-1 and pH values between 2.5 and 8.5. At pH 6, the AOB Nitrosomonas europaea was found, and the NOB belonged to the genus Nitrobacter. At pH 7, nitrite accumulated, and Nitrosomonas halophila was the dominant AOB. NOB were inhibited by HNO2 accumulation. At pH 8.5, the AOB Nitrosomonas stercoris became dominant, and NH3 inhibited NOB. Without influent, the pH dropped to 2.5 due to the growth of the acid-tolerant AOB “Candidatus Nitrosacidococcus urinae”. In conclusion, pH is a decisive process control parameter for urine nitrification by influencing the selection and kinetics of nitrifiers.
Frossard, E., Crain, G., Giménez de Azcárate Bordóns, I., Hirschvogel, C., Oberson, A., Paille, C., … Udert, K. M. (2024). Recycling nutrients from organic waste for growing higher plants in the Micro Ecological Life Support System Alternative (MELiSSA) loop during long-term space missions. Life Sciences in Space Research, 40, 176-185. doi:10.1016/j.lssr.2023.08.005, Institutional Repository

Space agencies are developing Bioregenerative Life Support Systems (BLSS) in view of upcoming long-term crewed space missions. Most of these BLSS plan to include various crops to produce different types of foods, clean water, and O2 while capturing CO2 from the atmosphere. However, growing these plants will require the appropriate addition of nutrients in forms that are available. As shipping fertilizers from Earth would be too costly, it will be necessary to use waste-derived nutrients. Using the example of the MELiSSA (Micro-Ecological Life Support System Alternative) loop of the European Space Agency, this paper reviews what should be considered so that nutrients recycled from waste streams could be used by plants grown in a hydroponic system. Whereas substantial research has been conducted on nitrogen and phosphorus recovery from human urine, much work remains to be done on recovering nutrients from other liquid and solid organic waste. It is essential to continue to study ways to efficiently remove sodium and chloride from urine and other organic waste to prevent the spread of these elements to the rest of the MELiSSA loop. A full nitrogen balance at habitat level will have to be achieved; on one hand, sufficient N2 will be needed to maintain atmospheric pressure at a proper level and on the other, enough mineral nitrogen will have to be provided to the plants to ensure biomass production. From a plant nutrition point of view, we will need to evaluate whether the flux of nutrients reaching the hydroponic system will enable the production of nutrient solutions able to sustain a wide variety of crops. We will also have to assess the nutrient use efficiency of these crops and how that efficiency might be increased. Techniques and sensors will have to be developed to grow the plants, considering low levels or the total absence of gravity, the limited volume available to plant growth systems, variations in plant needs, the recycling of nutrient solutions, and eventually the ultimate disposal of waste that can no longer be used.
Fumasoli, A., Probst, M., Wett, B., Derlon, N., Wenger, R., & Rérolle, M. (2024). Indense - Verfahren für Granulierten Schlamm. Erfahrungen und Erkenntnisse aus einem ein jährigen Pilotenversuch auf der ARA Gossau-Grüningen. Aqua & Gas, 104(1), 32-39. , Institutional Repository

Das inDENSE®-Verfahren wurde auf der ARA Gossau-Grüningen getestet. Nach einem Jahr wurde ein Anteil an granuliertem Schlamm von rund 50% und ein Schlammvolumenindex zwischen 40 und 70 ml/g beobachtet. DNA-Analysen zeigten, dass die bakterielle Gesamtpopulation saisonal konstanter blieb und Nitrit-oxidierende Bakterien im granulierten Schlamm akkumulierten. Durch die verbesserten Absetzeigenschaften können die Kapazität der ARA und die Stickstoffelimination signifikant gesteigert werden.
Galgani, F., Lusher, A. L., Strand, J., Haarr, M. L., Vinci, M., Molina Jack, E., … van Bavel, B. (2024). Revisiting the strategy for marine litter monitoring within the european marine strategy framework directive (MSFD). Ocean and Coastal Management, 255, 107254 (11 pp.). doi:10.1016/j.ocecoaman.2024.107254, Institutional Repository

Marine litter and non-degradable plastic pollution is of global concern. Regular monitoring programs are being established to assess and understand the scale of this pollution. In Europe, the goal of the European Marine Strategy Framework Directive (MSFD) is to assess trends in Good Environmental Status and support large-scale actions at the regional level. Marine litter monitoring requires tailored sampling strategies, protocols and indicators, that align with specific objectives and are tailored for local or regional needs. In addition, the uneven spatial and temporal distributions of marine litter present a challenge when designing a statistically powerful monitoring program. In this paper, we critically review the existing marine litter monitoring programs in Europe. We discuss the main constraints, including environmental, logistical, scientific, and ethical factors. Additionally, we outline the critical gaps and shortcomings in monitoring MSFD beaches/shorelines, floating litter, seafloor litter, microplastics, and harm. Several priorities must be established to shape the future of monitoring within the MSFD. Recent developments in analytical approaches, including optimizing protocols and sampling strategies, gaining a better understanding of the spatiotemporal heterogeneity of litter and its implications for survey design and replication, and the inclusion of newly validated methodologies that have achieved sufficient technical readiness, must be considered. Although there are well-established methods for assessing beaches, floating and seafloor litter, it will be necessary to implement monitoring schemes for microplastics in sediments and invertebrates as robust analytical methods become available for targeting smaller particle size classes. Furthermore, the inclusion of indicators for entanglement and injury to marine organisms will have to be considered in the near future. Moreover, the following actions will enhance the effectiveness of monitoring efforts: (1) creating an inventory of accumulation areas and sources of specific types of litter (e.g., fishing gear), (2) monitoring riverine inputs of litter, (3) monitoring atmospheric inputs including microplastics, (4) accidental inputs during extreme weather events, and (5) studying how species at risk may be transported by litter. We provide recommendations to support long-term, effective, and well-coordinated marine litter monitoring within the MSFD to achieve a comprehensive and accurate understanding of marine litter in EU waters. This will allow the development of measures to mitigate the impacts of marine pollution and eventually to evaluate the success of the respective measures.
Ganesanandamoorthy, P., Joss, A., Gruber, W., Bührer, T., & Thomann, M. (2024). Online-Nitritmessung. Vergleich von Online-Nitritsensoren für die Abwassereinigung. Aqua & Gas, 104(1), 26-31. , Institutional Repository

Nitrit ist eine ökotoxikologisch problematische Substanz und führt auf Kläranlagen ausserdem zur Bildung von klimaschädlichem Lachgas. In der hier vorgestellten Studie werden verschiedene Online-Sensoren verglichen und deren Messunsicherheit in Ablauf und Belebtschlamm erfasst.
Grigg, A. R. C., Notini, L., Kaegi, R., ThomasArrigo, L. K., & Kretzschmar, R. (2024). Aluminium substitution affects jarosite transformation to iron oxyhydroxides in the presence of aqueous Fe(II). Geochimica et Cosmochimica Acta, 374, 72-84. doi:10.1016/j.gca.2024.04.008, Institutional Repository

Jarosite is an abundant mineral in acidic environments, often found in acid sulfate soil (ASS) and acid-mine drainage (AMD). As a store of Fe, K, S and acidity, and a scavenger for major and trace elements, jarosite plays an important role in the biogeochemistry of acid sulfate environments. When ASS and AMD become anoxic, reducing conditions can set in, producing conditions that are outside the thermodynamic stability field of jarosite. In this study, we investigated the transformation of synthetic and natural jarosite with various degrees of Al-for-Fe substitution under circumneutral anoxic conditions in the presence of Fe(II), to understand the rates and pathways of jarosite and Al-jarosite transformation, the role of competing transformation pathways, the fate of Al during transformation and the different reactivity of natural and synthetic Al-jarosite. Synthetic jarosite (containing 0 %–7 % Al-for-Fe substitution) and a natural Al-substituted jarosite sample from an ASS in Thailand were suspended in solutions of 57Fe(II) at pH 7 for 24 h under anoxic conditions. The chosen experimental conditions mimic the Fe(II) concentrations and pH found in flooded ASS under reducing conditions. Changes in mineral composition of the suspensions were determined by Rietveld analysis of X-ray diffraction patterns at six time points. The fate of Al was determined by XRD, Raman spectroscopy and energy dispersive X-ray spectroscopy analysis of the jarosite and product minerals. Different transformation pathways that occurred simultaneously were traced by using 57Fe Mössbauer spectroscopy and aqueous Fe isotope composition. The analysis showed that 7 % Al-for-Fe substitution in jarosite more than halved the mineral transformation rate compared to unsubstituted jarosite, regardless of the Fe(II) concentrations. Indeed, 7 % Al-for-Fe substitution had a greater effect on the transformation rate than an order-of-magnitude decrease in the Fe(II) concentrations in all Al-for-Fe substitution treatments. The transformation products in all samples were goethite, lepidocrocite and ferrihydrite, with minor amounts of magnetite forming from jarosite with no or low Al-for-Fe substitution reacted with high Fe(II) concentrations. Lepidocrocite was the dominant product in reactors without aluminium, but lepidocrocite was not strongly enriched in 57Fe, suggesting that it may not have formed exclusively from Fe in solution during the Fe(II)-catalysed transformation of other minerals. In high-Al systems, lepidocrocite appeared to be a sink for Al, although its formation in Al-rich samples was suppressed. Natural jarosite reacted more than an order of magnitude more slowly than the synthetic jarosite and Al-jarosite, indicating that the properties of the synthetic jarosite do not completely account for the stability of natural jarosite under anoxic circumneutral conditions. The results provide an important baseline for understanding the drivers of jarosite transformation or stability in ASS and AMD.
Grigg, A. R. C., Notini, L., Kaegi, R., ThomasArrigo, L. K., & Kretzschmar, R. (2024). Structural effects of aluminum and iron occupancy in minerals of the jarosite-alunite solid solution. ACS Earth and Space Chemistry, 8(2), 194-206. doi:10.1021/acsearthspacechem.3c00174, Institutional Repository

The alunite supergroup of minerals contains several hydroxysulfate mineral phases that commonly occur in acidic natural and engineered environments. The main division of the mineral supergroup defines two minerals, jarosite and alunite, based on the relative structural occupancy by Al or Fe, respectively. However, intermediate members of the jarosite-alunite solid solution have not been extensively characterized, especially in the environment. Here, we link the mineral unit cell sizes measured by X-ray diffraction, peak shifts in Raman spectra, fitting parameters in Mössbauer spectroscopy, and elemental quantification by EDX spectroscopy to known amounts of Al substitution in two synthetic series of Al-substituted jarosite (up to Al-for-Fe substitution of 9.5%) and unknown Al substitution in a natural jarosite isolated from an acid sulfate soil. Strong correlations were observed between the Al substitution of the jarosite samples and unit cell size, position of several vibrational peaks in Raman spectroscopy, and the temperature of magnetic ordering. In addition, elemental mapping provided a robust way to characterize the Al content of jarosite. As the techniques were effective in quantifying the Al or Fe content of jarosite-alunite supergroup mineral samples, without the need for sample dissolution, the findings support the application of these spectroscopy techniques to characterize natural jarosite-alunite samples. Using these techniques, we demonstrate at least 5% Al-for-Fe substitution in a jarosite sample from an acid sulfate soil. Application to environmental samples is especially useful in cases where it is otherwise difficult to directly measure the Al content of a mineral sample or when Al-for-Fe substitution influences the spectral responses to substitution at other sites in the crystal structure.
Harder, R., Metson, G. S., Macura, B., Johannesdottir, S., Wielemaker, R., Seddon, D., … McConville, J. R. (2024). Egestabase - an online evidence platform to discover and explore options to recover plant nutrients from human excreta and domestic wastewater for reuse in agriculture. MethodsX, 12, 102774 (10 pp.). doi:10.1016/j.mex.2024.102774, Institutional Repository

Restoring nutrient circularity across scales is important for ecosystem integrity as well as nutrient and food security. As such, research and development of technologies to recover plant nutrients from various organic residues has intensified. Yet, this emerging field is diverse and difficult to navigate, especially for newcomers. As an increasing number of actors search for circular solutions to nutrient management, there is a need to simplify access to the latest knowledge. Since the majority of nutrients entering urban areas end up in human excreta, we have chosen to focus on human excreta and domestic wastewater. Through systematic mapping with stakeholder engagement, we compiled and consolidated available evidence from research and practice. In this paper, we present ‘Egestabase’ – a carefully curated open-access online evidence platform that presents this evidence base in a systematic and accessible manner. We hope that this online evidence platform helps a variety of actors to navigate evidence on circular nutrient solutions for human excreta and domestic wastewater with ease and keep track of new findings.
Heusser, A., Dax, A., McArdell, C. S., & Udert, K. M. (2024). Comparing the adsorption of micropollutants on activated carbon from anaerobically stored, organics-depleted, and nitrified urine. Water Research, 257, 121615 (12 pp.). doi:10.1016/j.watres.2024.121615, Institutional Repository

Separate collection and treatment of urine optimizes nutrient recovery and enhances micropollutant removal from municipal wastewater. One typical urine treatment train includes nutrient recovery in three biological processes: anaerobic storage, followed by aerobic organics degradation concurrently with nitrification. These are usually followed by activated carbon adsorption to remove micropollutants. However, removing micropollutants prior to nitrification would protect nitrifiers from potential inhibition by pharmaceuticals. In addition, combining simplified biological treatment with activated carbon adsorption could offer a cheap and robust process for removing micropollutants where nutrient recovery is not the first priority, as a partial loss of ammonia occurs without nitrification. In this study, we investigated whether activated carbon adsorption could also take place between the three biological treatment steps. We tested the effectiveness of micropollutant removal with activated carbon after each biological treatment step by conducting experiments with anaerobically stored urine, organics-depleted urine, and nitrified urine. The urine solutions were spiked with 19 pharmaceuticals: amisulpride, atenolol, atenolol acid, candesartan, carbamazepine, citalopram, clarithromycin, darunavir, diclofenac, emtricitabine, fexofenadine, hydrochlorothiazide, irbesartan, lidocaine, metoprolol, N4-acetylsulfamethoxazole, sulfamethoxazole, trimethoprim, venlafaxine, and two artificial sweeteners, acesulfame and sucralose. Batch experiments were conducted with powdered activated carbon (PAC) to determine how much activated carbon achieve which degree of micropollutant removal and how organics, pH, and speciation change from ammonium to nitrate influence adsorption. Micropollutant removal was also tested in granular activated carbon (GAC) columns, which is the preferred technology for micropollutant removal from urine. The carbon usage rates (CUR) per person were lower for all urine solutions than for municipal wastewater. The results showed that organics depletion would be needed when micropollutant removal was the sole aim of urine treatment, as the degradation of easily biodegradable organics prevented clogging of GAC columns. However, CUR did hardly improve with organics-depleted urine compared to stored urine. The lowest CUR was achieved with nitrified urine. This resulted from the additional organics removal during nitrification and not the lower pH or the partial conversion of ammonium to nitrate. In addition, we showed that the relative pharmaceutical removal in all solutions was independent of the initial pharmaceutical concentration unless the background organics matrix changed considerably. We conclude that removal of micropollutants in GAC columns from organics-depleted urine can be performed without clogging, but with the drawback of a higher carbon usage compared to removal from nitrified urine.
Heusser, A., Wackernagel, I., Reinmann, M., & Udert, K. M. (2024). Increasing urine nitrification performance with sequential membrane aerated biofilm reactors. Water Research, 261, 122019 (10 pp.). doi:10.1016/j.watres.2024.122019, Institutional Repository

This study aimed to investigate whether separating organics depletion from nitrification increases the overall performance of urine nitrification. Separate organics depletion was facilitated with membrane aerated biofilm reactors (MABRs). The high pH and ammonia concentration in stored urine inhibited nitrification in the first stage and therewith allowed the separation of organics depletion from nitrification. An organics removal of 70 % was achieved at organic loading rates in the influent of 3.7 gCOD d−1 m−2. Organics depletion in a continuous flow stirred tank reactor (CSTR) for organics depletion led to ammonia stripping through diffused aeration of up to 13 %. Using an MABR, diffusion into the lumen amounted for 4 % ammonia loss only. In the MABR, headspace volume and therefore ammonia loss through the headspace was negligible. By aerating the downstream MABR for nitrification with the off-gas of the MABR for organics depletion, 96 % of the ammonia stripped in the first stage could be recovered in the second stage, so that the overall ammonia loss was negligibly low. Nitrification of the organics-depleted urine was studied in MABRs, CSTRs, and sequencing batch reactors in fed batch mode (FBRs), the latter two operated with suspended biomass. The experiments demonstrated that upstream organics depletion can double the nitrification rate. In a laboratory-scale MABR, nitrification rates were recorded of up to 830 mgN L−1 d−1 (3.1 gN m−2 d−1) with ambient air and over 1500 mgN L−1 d−1 (6.7 gN m−2 d−1) with oxygen-enriched air. Experiments with a laboratory-scale MABR showed that increasing operational parameters such as pH, recirculation flow, scouring frequency, and oxygen content increased the nitrification rate. The nitrification in the MABR was robust even at high pH setpoints of 6.9 and was robust against process failures arising from operational mistakes. The hydraulic retention time (HRT) required for nitrification was only 1 to 2 days. With the preceding organics depletion, the HRT for our system requires 2 to 3 days in total, whereas a combined activated sludge system requires 4 to 8 days. The N2O concentration in the off-gas increases with increasing nitrification rates; however, the N2O emission factor was 2.8 % on average and independent of nitrification rates. These results indicate that the MABR technology has a high potential for efficient and robust production of ammonium nitrate from source-separated urine.
Kirchgeorg, S., Aucone, E., Wenk, F., & Mintchev, S. (2024). Design, modeling, and control of AVOCADO: a multimodal aerial-tethered robot for tree canopy exploration. IEEE Transactions on Robotics, 40, 592-605. doi:10.1109/TRO.2023.3334630, Institutional Repository

Forests provide vital resources and services for humanity, but preserving and restoring them is challenging due to the difficulty of obtaining actionable data, especially in inaccessible areas, such as forest canopies. To address this, we follow the lead of arboreal animals that exploit multiple modes of locomotion. We combine aerial and tethered movements to enable AVOCADO to navigate within a tree canopy. Starting from the top of a tree, it can descend with the tether and maneuver around obstacles with thrusters. We extend our previous work with a new mechanical design with a protective shell, increased computational power and cameras for state estimation. We introduce a dynamic model and simulation, and perform a quasistatic and dynamic validation. For autonomy, we derive a control framework in simulation to regulate tether length, tilt, and heading, before transfer to the robot. We evaluate the controllers for trajectory tracking through experiments. AVOCADO can follow trajectories around obstacles and reject disturbances on the tether. Exploiting multimodal mobility will advance the exploration of tree canopies to actively monitor the true value of our forests.
Kuehr, S., Kaegi, R., Raths, J., Sinnet, B., Kipf, M., Rehkämper, M., … Georgantzopoulou, A. (2024). Reduced bioavailability of Au and isotopically enriched 109Ag nanoparticles transformed through a pilot wastewater treatment plant in Hyalella azteca under environmentally relevant exposure scenarios. Science of the Total Environment, 949, 174768 (13 pp.). doi:10.1016/j.scitotenv.2024.174768, Institutional Repository

Wastewater Treatment Plants (WWTP) are a major repository and entrance path of nanoparticles (NP) in the environment and hence play a major role in the final NP fate and toxicity. Studies on silver nanoparticles (AgNP) transport via the WWTP system and uptake by aquatic organisms have so far been carried out using unrealistically high AgNP concentrations, unlikely to be encountered in the aquatic environment. The use of high AgNP concentrations is necessitated by both the low sensitivity of the detection methods used and the need to distinguish background Ag from spiked AgNP.
In this study, isotopically enriched 109AgNP were synthesized to overcome these shortcomings and characterized by a broad range of methods including transmission electron microscopy, dynamic and electrophoretic light scattering. 109AgNP and gold NP (AuNP) were spiked to a pilot wastewater treatment plant fed with municipal wastewater for up to 21 days. AuNP were used as chemically less reactive tracer. The uptake of the pristine and transformed NP present in the effluent was assessed using the benthic amphipod Hyalella azteca in fresh- and brackish water exposures at environmentally relevant concentrations of 30 to 500 ng Au/L and 39 to 260 ng Ag/L. The unique isotopic signature of the 109AgNP allowed to detect the material at environmentally relevant concentrations in the presence of a much higher natural Ag background. The results show that the transformations reduce the NP uptake at environmentally relevant exposure concentrations. For 109Ag, lower accumulation factors (AF) were obtained after exposure to transformed NP (250–350) compared to the AF values obtained for pristine 109AgNP (750–840). The reduced AF values observed for H. azteca exposed to effluent from the AuNP-spiked WWTP indicate that biological transformation processes (e.g. eco-corona formation) seem to be involved in addition to chemical transformation.
Meynet, P., Joss, A., Davenport, R. J., & Fenner, K. (2024). Impact of long-term temperature shifts on activated sludge microbiome dynamics and micropollutant removal. Water Research, 258, 121790 (10 pp.). doi:10.1016/j.watres.2024.121790, Institutional Repository

Micropollutants removal efficiency strongly vary across different aerobic wastewater treatment plants, resulting in their frequent detection in surface and ground waters. Seasonal temperature variation is a major factor influencing plant performance, but it is still unclear how prolonged periods of temperature change impact microbiome and micropollutant biotransformation. This work investigates the effect of long-term temperature variation on the microbial dynamics in an activated sludge system, and the impact on micropollutant biotransformation. Sequencing batch reactors were used as model system and 4–40 °C temperature range was studied. 16S rRNA amplicon sequencing showed that temperature drives microbial structure (gDNA) and activity (RNA), rather than time, and this was stronger below 15 °C and above 25 °C. The microbial community was richest and more diverse at 20 °C, while rarer and more specific taxa became predominant over time, at more extreme temperatures. This suggested that less abundant taxa might be responsible for maintaining the biotransformation capability in the activated sludge at extreme temperatures. Micropollutant biotransformation rates mostly deviated from the classic Arrhenius model below 15 °C and above 25 °C, indicating that prolonged exposure to temperature changes leads to temperature-induced taxonomic shifts, resulting in the emerging of different sets of biotransformation pathways over different temperature ranges.
Nopp-Mayr, U., Layendecker, S., Sittenthaler, M., Philipp, M., Kägi, R., & Weinberger, I. (2024). Microplastic loads in Eurasian otter (Lutra lutra) feces - targeting a standardized protocol and first results from an alpine stream, the River Inn. Environmental Monitoring and Assessment, 196(8), 707 (14 pp.). doi:10.1007/s10661-024-12791-z, Institutional Repository

Microplastics (MP) are omnipresent in a wide range of environments, constituting a potential threat for aquatic and terrestrial wildlife. Effects in consumers range from physical injuries to pathological reactions. Due to potential bioaccumulation of MP, predators are of particular concern for MP induced health effects. The Eurasian otter is an apex predator in (semi-)aquatic habitats feeding primarily on fish. Furthermore, the species is classified as “near threatened” on the IUCN Red List. Thus, the Eurasian otter is of conservation concern and may serve as a bioindicator for MP pollution. Feces can be used to detect pollutants, including MP. Initial studies confirmed the presence of MP in otter feces (= spraints). However, as specific, validated protocols targeting at an efficient and standardized extraction of MP from otter spraints are missing, experimental results reported from different groups are challenging to compare. Therefore, we (i) present steps towards a standardized protocol for the extraction of MP from otter feces, (ii) give recommendations for field sample collection of otter spraints, and (iii) provide a user-friendly step-by-step workflow for MP extraction and analysis. Applying this framework to field samples from five study sites along the River Inn (n = 50), we detected MP of different sizes and shapes (ranging from microfibers to road abrasion and tire wear) in all otter spraint samples.
Pechaud, Y., Derlon, N., Queinnec, I., Bessiere, Y., & Paul, E. (2024). Modelling biofilm development: the importance of considering the link between EPS distribution, detachment mechanisms and physical properties. Water Research, 250, 120985 (16 pp.). doi:10.1016/j.watres.2023.120985, Institutional Repository

In industry, treatments against biofilms need to be optimized and, in the wastewater treatment field, biofilm composition needs to be controlled. Therefore, describing the biochemical and physical structures of biofilms is now required to better understand the influence of operating parameters and treatment on biofilms. The present study aims to investigate how growth conditions influence EPS composition, biofilm physical properties and volume detachment using a 1D biofilm model. Two types of EPS are considered in the present model, proteins and polysaccharides. The main hypotheses are that: (i) the production of polysaccharides occurs mainly under strong nutrient limitation(s) while the production of proteins is coupled to both the substrate uptake rate and the lysis process; (ii) the local biofilm porosity depends on the local biofilm composition. Both volume and surface detachment occur in biofilms and volume detachment extent depends on the biofilm local cohesion and thus on the local composition of biofilms for a given shear stress.
The model is based on experimental trends and aims to represent these observations on the basis of biochemical and physical processes. Four case studies covering a wide range of contrasting growth conditions such as different COD/N ratios, applied SOLR and shear stresses are investigated. The model predicts how the biochemical and physical biofilm structures change as a result of contrasting growth conditions. More precisely simulation results are in good agreement with the main experimental observations reported in the literature, such as: (i) a strong nitrogen limitation of growth induces an important accumulation of polysaccharides leading to a more porous and homogenous biofilm, (ii) a high applied surface organic loading load allows to obtain a high biofilm thickness, (iii) a strong shear stress applied during the biofilm growth leads to a reduction of the biofilm thickness and to a consolidation of the biofilm structure. Overall, this model represents a relevant decision tool for the selection of appropriate enzymatic treatments in the context of negative biofilm control. From our results, it appears that protease based treatments should be more appropriate for biofilms developed under low COD/N ratios (about 20 gCOD/gN) whereas both glucosidases and proteases based treatments should be more appropriate for biofilms developed under high COD/N ratio (about 70 gCOD/gN). In addition, the model could be useful for other applications such as resource recovery in biofilms or granules, and help to better understand biological membrane fouling.
Reynaert, E., Nagappa, D., Sigrist, J. A., & Morgenroth, E. (2024). Ensuring microbial water quality for on-site water reuse: importance of online sensors for reliable operation. Water Research X, 22, 100215 (8 pp.). doi:10.1016/j.wroa.2024.100215, Institutional Repository

A growing number of cities and regions are promoting or mandating on-site treatment and reuse of wastewater, which has resulted in the implementation of several thousand on-site water reuse systems on a global scale. However, there is only limited information on the (microbial) water quality from implemented systems. The focus of this study was on two best-in-class on-site water reuse systems in Bengaluru, India, which typically met the local water quality requirements during monthly compliance testing. This study aimed to (i) assess the microbial quality of the reclaimed water at a high temporal resolution (daily or every 15 min), and (ii) explore whether measurements from commercially available sensors can be used to improve the operation of such systems. The monitoring campaign revealed high variations in microbial water quality, even in these best-in-class systems, rendering the water inadequate for the intended reuse applications (toilet flushing and landscape irrigation). These variations were attributed to two key factors: (1) the low frequency of chlorination, and (2) fluctuations of the chlorine demand of the water, in particular of ammonium concentrations. Such fluctuations are likely inherent to on-site systems, which rely on a low level of process control. The monitoring campaign showed that the microbial water quality was most closely related to oxidation–reduction potential (ORP) and free chlorine sensors. Due to its relatively low cost and low need for maintenance, the ORP emerges as a compelling candidate for automating the chlorination to effectively manage variations in chlorine demand and ensure safe water reuse. Overall, this study underscores the necessity of integrating treatment trains, operation, and monitoring for safe on-site water reuse.
Reynaert, E., Sylvestre, É., Morgenroth, E., & Julian, T. R. (2024). Greywater recycling for diverse collection scales and appliances: enteric pathogen log-removal targets and treatment trains. Water Research, 264, 122216 (13 pp.). doi:10.1016/j.watres.2024.122216, Institutional Repository

In light of increasingly diverse greywater reuse applications, this study proposes risk-based log-removal targets (LRTs) to aid the selection of treatment trains for greywater recycling at different collection scales, including appliance-scale reuse of individual greywater streams. An epidemiology-based model was used to simulate the concentrations of prevalent and treatment-resistant reference pathogens (protozoa: Giardia and Cryptosporidium spp., bacteria: Salmonella and Campylobacter spp., viruses: rotavirus, norovirus, adenovirus, and Coxsackievirus B5) in the greywater streams for collection scales of 5-, 100-, and a 1000-people. Using quantitative microbial risk assessment (QMRA), we calculated LRTs to meet a health benchmark of 10–4 infections per person per year over 10′000 Monte Carlo iterations. LRTs were highest for norovirus at the 5-people scale and for adenovirus at the 100- and 1000-people scales. Example treatment trains were designed to meet the 95 % quantiles of LRTs. Treatment trains consisted of an aerated membrane bioreactor, chlorination, and, if required, UV disinfection. In most cases, rotavirus, norovirus, adenovirus and Cryptosporidium spp. determined the overall treatment train requirements. Norovirus was most often critical to dimension the chlorination (concentration × time values) and adenovirus determined the required UV dose. Smaller collection scales did not generally allow for simpler treatment trains due to the high LRTs associated with viruses, with the exception of recirculating washing machines and handwashing stations. Similarly, treating greywater sources individually resulted in lower LRTs, but the lower required LRTs nevertheless did not generally allow for simpler treatment trains. For instance, LRTs for a recirculating washing machine were around 3-log units lower compared to LRTs for indoor reuse of combined greywater (1000-people scale), but both scenarios necessitated treatment with a membrane bioreactor, chlorination and UV disinfection. However, simpler treatment trains may be feasible for small-scale and application-scale reuse if: (i) less conservative health benchmarks are used for household-based systems, considering the reduced relative importance of treated greywater in pathogen transmission in households, and (ii) higher log-removal values (LRVs) can be validated for unit processes, enabling simpler treatment trains for a larger number of appliance-scale reuse systems.
Schwarzfischer, M., Ruoss, T. S., Niechcial, A., Lee, S. S., Wawrzyniak, M., Laimbacher, A., … Spalinger, M. R. (2024). Impact of nanoplastic particles on macrophage inflammation and intestinal health in a mouse model of inflammatory bowel disease. Nanomaterials, 14(16), 1350 (15 pp.). doi:10.3390/nano14161350, Institutional Repository

Background: The increasing presence of plastics in the human diet is raising public concern about the potential risks posed by nanoplastic (NP) particles, which can emerge from the degradation of plastic debris. NP ingestion poses particular risks to individuals with inflammatory bowel disease (IBD), as compromised epithelial barriers may facilitate NP translocation. Methods: In vitro, bone-marrow-derived macrophages (BMDMs) were exposed to 25 nm polymethacrylate (PMMA) or 50 nm polystyrene (PS) particles to assess morphological changes and alterations in pro- and anti-inflammatory gene expression. In vivo, mice received PMMA NP particles for 6 months before acute dextran sodium sulfate (DSS) colitis was induced to investigate NP impacts on intestinal health and inflammation. Results: PMMA and PS NP exposure in BMDMs induced morphological changes indicative of a proinflammatory phenotype characterized by enlarged amoeboid cell shapes. It also triggered an inflammatory response, indicated by increased expression of proinflammatory cytokines such as Tnfa and Il6. Unexpectedly, long-term PMMA NP administration did not affect the intestinal epithelial barrier or exacerbate acute DSS-induced colitis in mice. Colonoscopy and histological analysis revealed no NP-related changes, suggesting adverse effects on intestinal health or inflammation. Conclusion: Our findings from animal models offer some reassurance to IBD patients regarding the effects of NP ingestion. However, variations in lifestyle and dietary habits may lead to significantly higher plastic intake in certain individuals, raising concerns about potential long-term gastrointestinal effects of lifelong plastic consumption.
Seller-Brison, C., Brison, A., Yu, Y., Robinson, S. L., & Fenner, K. (2024). Adaptation towards catabolic biodegradation of trace organic contaminants in activated sludge. Water Research, 266, 122431 (14 pp.). doi:10.1016/j.watres.2024.122431, Institutional Repository

Trace organic contaminants (TrOCs) are omnipresent in wastewater treatment plants (WWTPs), yet, their removal during wastewater treatment is oftentimes incomplete and underlying biotransformation mechanisms are not fully understood. In this study, we elucidate how different factors, including pre-exposure levels and duration, influence microbial adaptation towards catabolic TrOC biodegradation and its potential role in biological wastewater treatment. Four sequencing batch reactors (SBRs) were operated in parallel in three succeeding phases, adding and removing a selection of 26 TrOCs at different concentration levels. After each phase of SBR operation, a series of batch experiments was conducted to monitor biotransformation kinetics of those same TrOCs across various spike concentrations. For half of our test TrOCs, we detected increased biotransformation in sludge pre-exposed to TrOC concentrations ≥5 µg L−1 over a 30-day period, with most significant differences observed for the insect repellent DEET and the artificial sweetener saccharin. Accordingly, 16S rRNA amplicon sequencing revealed enrichment of taxa that have previously been linked to catabolic biodegradation of several test TrOCs, e.g., Bosea sp. and Shinella sp. for acesulfame degradation, and Pseudomonas sp. for caffeine, cyclamate, DEET, metformin, paracetamol, and isoproturon degradation. We further conducted shotgun metagenomics to query for gene products previously reported to be involved in the TrOCs’ biodegradation pathways. In the future, directed microbial adaptation may be a solution to improve bioremediation of TrOCs in contaminated environments or in WWTPs.
Stetten, L., Kaegi, R., Hofmann, T., & von der Kammer, F. (2024). Depth-dependent transformation of ZnO and Ag nanoparticles in sulfate-reducing sediments tracked using scanning transmission electron microscopy. Environmental Science: Nano, 11(1), 136-148. doi:10.1039/d3en00550j, Institutional Repository

Studies on the transformation of engineered nanomaterials (ENMs) based on relevant environmental exposure scenarios are scarce. In this context, we investigated the use of Transmission Electron Microscopy (TEM) grids to expose minute amounts of ZnO and Ag nanoparticles (NPs) to artificial and natural aqueous media and follow their transformation using scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy. Short-term experiments conducted with inorganic sulfides confirmed the potential of using TEM grids to monitor the transformation of ENMs at the single particle level. After 30 min, Ag NPs transformed into Ag-sulfides, with Ag : S ratios ≈ 2 : 1, while ZnO NPs showed little evidence of Zn-sulfides precipitation after 6 hours. Ag NPs and ZnO NPs were also exposed to depth-dependent pore water concentration gradients in freshwater sediment columns. After three days and four weeks, all the Ag NPs observed were transformed into Ag-sulfides with various morphologies and Ag : S ratios (1 ≤ Ag/S ≤ 2), depending on the depth and duration of the exposure. Furthermore, a depth-dependent transformation was observed for ZnO NPs. At low sulfide concentration, in the first millimeters below the water-sediment interface, ZnO NPs were completely transformed into ZnS harboring empty shell structures, together with smaller particles in their vicinity. By contrast, ZnO cores persisted in the deeper layers, indicating that ZnO NPs dissolution was inhibited at high sulfide concentrations. Our results demonstrate the advantage of experimental and analytical strategies adapted to study the transformation of ENMs under environmentally relevant conditions, to unravel transformation rates and products not yet considered in risk assessment studies.
Sylvestre, É., Jahne, M. A., Reynaert, E., Morgenroth, E., & Julian, T. R. (2024). A critical evaluation of parametric models for predicting faecal indicator bacteria concentrations in greywater. Microbial Risk Analysis, 26, 100297 (8 pp.). doi:10.1016/j.mran.2024.100297, Institutional Repository

Greywater reuse is a strategy to address water scarcity, necessitating the selection of treatment processes that balance cost-efficiency and human health risks. A key aspect in evaluating these risks is understanding pathogen contamination levels in greywater, a complex task due to intermittent pathogen occurrences. To address this, faecal indicator organisms like E. coli are often monitored as proxies to evaluate faecal contamination levels and infer pathogen concentrations. However, the wide variability in faecal indicator concentrations poses challenges in their modelling for quantitative microbial risk assessment (QMRA). Our study critically assesses the adequacy of parametric models in predicting the variability in E. coli concentrations in greywater. We found that models that build on summary statistics, like medians and standard deviations, can substantially underestimate the variability in E. coli concentrations. More appropriate models may provide more accurate estimations of, and uncertainty around, peak E. coli concentrations. To demonstrate this, a Poisson lognormal distribution model is fit to a data set of E. coli concentrations measured in shower and laundry greywater sources. This model estimated arithmetic mean E. coli concentrations in laundry waters at approximately 1.0E + 06 MPN 100 mL−1. These results are around 2.0 log10 units higher than estimations from a previously used hierarchical lognormal model based on aggregated summary data from multiple studies. Such differences are considerable when assessing human health risks and setting pathogen reduction targets for greywater reuse. This research highlights the importance of making raw monitoring data available for more accurate statistical evaluations than those based on summary statistics. It also emphasizes the crucial role of model comparison, selection, and validation to inform policy-relevant outcomes.
Timmer, M. J., De Paepe, J., Van Winckel, T., Spiller, M., Spacova, I., De Paepe, K., … Vlaeminck, S. E. (2024). Resource-efficient nitrogen removal from source-separated urine with partial nitritation/anammox in a membrane-aerated biofilm reactor. ACS ES&T Engineering, 4(7), 1609-1621. doi:10.1021/acsestengg.4c00058, Institutional Repository

Source separation and decentralized urine treatment can cut costs in centralized wastewater treatment by diverting 80% of the nitrogen load in sewage. One promising approach for nitrogen removal from source-separated urine is partial nitritation/anammox (PN/A), reducing the aeration demand by 67% and organic dosage by 100% compared to nitrification/denitrification. While previous studies with suspended biomass have encountered stability issues during PN/A treatment of urine, a PN/A biofilm was hypothesized to be more resilient. Its use for urine treatment has been pioneered here for maximum rates and efficiencies in an energy-efficient membrane-aerated biofilm reactor (MABR). Nitrogen removal rates of 1.0 g N L-1 d-1 and removal efficiencies of 80-95% were achieved during a 335-day operational period at 28 °C on stabilized (pH > 11.5), diluted urine (10%). A balance between N2 and NO3- formation was observed while optimizing the supply of O2 through intermittent aeration and was rate limiting for the conversion toward N2. A short-term operation on less- and undiluted urine yielded N removal rates of 0.6-0.8 g N L-1 d-1 and removal efficiencies of 93% on 66% urine and 85% on undiluted urine. Metataxonomic analysis and fluorescence in situ hybridization confirmed the presence in the biofilm of nitrifiers (Nitrosomonas, Nitrospira) at the membrane side and anammox bacteria ("Candidatus Brocadia") at the anoxic bulk side. The findings suggest that a biofilm approach to PN/A treatment of urine overcomes stability issues and that a PN/A-MABR has significant potential for resource-efficient decentralized urine treatment. In human long-duration deep-space missions, this gravity-independent technology could produce N2 to compensate artificial atmosphere losses while facilitating water recovery from urine.
la Cecilia, D., Philipp, M., Kaegi, R., Schirmer, M., & Moeck, C. (2024). Microplastics attenuation from surface water to drinking water: impact of treatment and managed aquifer recharge – and identification uncertainties. Science of the Total Environment, 908, 168378 (12 pp.). doi:10.1016/j.scitotenv.2023.168378, Institutional Repository

River water can be used to recharge aquifers exploited for drinking water production. Several recent studies reported microplastics (MPs) in river water, and therefore, the potential contamination of groundwater by MPs is a growing concern among stakeholders and citizens. In this research, we investigate the fate of MPs (> 20 μm) along six different stages of a major Managed Aquifer Recharge (MAR)-water supply system in Switzerland. About 20 l of water were filtered using steel meshes at each location in triplicates. In the laboratory, MPs deposited on the anodisc filters were identified using Focal Plane Array (FPA) micro-Fourier-Transform-InfraRed (μFTIR) spectroscopy. The obtained hyperspectral data were processed using the imaging software Microplastics Finder for MPs identification and classification. Our results revealed a 20-fold decrease in MPs concentration from the Rhine River bed water (112 ± 27.4 MPs/l) to after the coagulation, flocculation and sedimentation (5.5 ± 2.2 MPs/l), a further 3-fold decrease to after the sand-filtration system (1.8 ± 0.9 MPs/l), corresponding to an overall removal efficiency of 98.4 %. The MPs concentrations remained low following MAR (2.7 ± 0.7 MPs/l) through a Quaternary gravel aquifer. Activated carbon filters did not substantially further reduce MPs concentrations. The percentage of fragments (≈95 %) prevailed over fibers (≈5 %) at all locations, with fibers being longer and more abundant in the river water. Overall, this study demonstrates the effectiveness of the treatment systems to remove MPs larger than 20 μm. Finally, we calculated an uncertainty in MPs concentrations of one order of magnitude depending on the user-defined parameters inside the MPs identification and classification model. The Quality Assurance/Quality Control approach followed during laboratory analysis highlighted an accumulation of surrogate particles at the edges of the disc, which would have an impact for MPs number upscaling.
Ballikaya, P., Brunner, I., Cocozza, C., Grolimund, D., Kaegi, R., Murazzi, M. E., … Cherubini, P. (2023). First evidence of nanoparticle uptake through leaves and roots in beech (Fagus sylvatica L.) and pine (Pinus sylvestris L.). Tree Physiology, 43(2), 262-276. doi:10.1093/treephys/tpac117, Institutional Repository

Trees have been used for phytoremediation and as biomonitors of air pollution. However, the mechanisms by which trees mitigate nanoparticle pollution in the environment are still unclear. We investigated whether two important tree species, European beech (Fagus sylvatica L.) and Scots pine (Pinus sylvestris L.), are able to take up and transport differently charged gold nanoparticles (Au-NPs) into their stem by comparing leaf-to-root and root-to-leaf pathways. Au-NPs were taken up by roots and leaves, and a small fraction was transported to the stem in both species. Au-NPs were transported from leaves to roots but not vice versa. Leaf Au uptake was higher in beech than in pine, probably because of the higher stomatal density and wood characteristics of beech. Confocal (3D) analysis confirmed the presence of Au-NPs in trichomes and leaf blade, about 20–30 μm below the leaf surface in beech. Most Au-NPs likely penetrated into the stomatal openings through diffusion of Au-NPs as suggested by the 3D XRF scanning analysis. However, trichomes were probably involved in the uptake and internal immobilization of NPs, besides their ability to retain them on the leaf surface. The surface charge of Au-NPs may have played a role in their adhesion and uptake, but not in their transport to different tree compartments. Stomatal conductance did not influence the uptake of Au-NPs. This is the first study that shows nanoparticle uptake and transport in beech and pine, contributing to a better understanding of the interactions of NPs with different tree species.
Bou-Sarkis, A., Paul, E., Girbal-Neuhauser, E., Derlon, N., & Bessiere, Y. (2023). Detection of gel-forming polymers via calcium crosslinking, applied to the screening of extracellular polymeric substances extracted from biological aggregates. Gels, 9(2), 157 (14 pp.). doi:10.3390/gels9020157, Institutional Repository

The valorization of biological aggregates through the extraction of hydrogel-forming polymers can enhance the economics and sustainability of various processes in which bacteria are involved in organic waste transformation, such as wastewater treatment. Achieving these goals requires the development of a method capable of detecting the presence of gel-forming polymers in complex mixtures containing biopolymers that are most often unknown and uncharacterized. A miniaturized screening method capable of detecting gelation via ionic crosslinking using only 1 to 3 mg of the tested samples (commercial molecules or extracellular polymeric substances, EPSs) is proposed. The method consists of calculating a percentage of reactivity (%R) through UV-vis spectra and determining the percentage of gel volume (%Vg) formed after the addition of calcium. Both factors were combined to give a gelling factor (GF), and the test was applied to pure commercial molecules (BSA, DNA, alginate (ALV), and a mixture of them), allowing the classification of the following solutions according to their gel-forming capacity: GF(ALV) > GF(ALV+DNA) > GF(BSA+ALV+DNA) > GF(BSA+ALV) > GF(DNA) > GF(BSA+DNA) > GF(BSA). As a relevant tool for screening hydrogel-forming solutions, the method was applied to the EPS extracted from aerobic granular sludge. The EPS (0.5% w/v) had a GF of 0.16 ± 0.03, equivalent to approximately half of the GF of ALV (0.38 ± 0.02 at 0.5% w/v). The developed test pushes the limits of the existing gel-detection techniques because it allows for quicker, less consuming, and more informative gelation detection through the use of simple methods that do not require sophisticated equipment.
Brison, A., Rossi, P., & Derlon, N. (2023). Single CSTR can be as effective as an SBR in selecting PHA-storing biomass from municipal wastewater-derived feedstock. Water Research X, 18, 100165 (13 pp.). doi:10.1016/j.wroa.2023.100165, Institutional Repository

A key step for the production of polyhydroxyalkanoates (PHAs) from organic waste streams is the selection of a biomass with a high PHA-storage capacity (selection-step), which is usually performed in sequencing batch reactors (SBR). A major advancement would be to perform such selection in continuous reactors to facilitate the full-scale implementation of PHA production from municipal wastewater (MWW)-derived feedstock. The present study therefore investigates to what extent a simple continuous-flow stirred-tank reactor (CSTR) represents a relevant alternative to anSBR. To this end, we operated two selection reactors (CSTR vs. SBR) on filtered primary sludge fermentate while performing a detailed analysis of the microbial communities, and monitoring PHA-storage over long-term (∼150 days) and during accumulation batches. Our study demonstrates that a simple CSTR is as effective as an SBR in selecting biomass with high PHA-storage capacity (up to 0.65 gPHA gVSS−1) while being 50% more efficient in terms of substrate to biomass conversion yields. We also show that such selection can occur on VFA-rich feedstock containing nitrogen (N) and phosphorus (P) in excess, whereas previously, selection of PHA-storing organisms in a single CSTR has only been studied under P limitation. We further found that microbial competition was mostly affected by nutrient availability (N and P) rather than by the reactor operation mode (CSTR vs. SBR). Similar microbial communities therefore developed in both selection reactors, while microbial communities were very different depending on N availability. Rhodobacteraceae gen. were most abundant when growth conditions were stable and N-limited, whereas dynamic N- (and P-) excess conditions favoured the selection of the known PHA-storer Comamonas, and led to the highest observed PHA-storage capacity. Overall, we demonstrate that biomass with high storage capacity can be selected in a simple CSTR on a wider range of feedstock than just P-limited ones.
Daigger, G. T., Kuo, J., Derlon, N., Houweling, D., Jimenez, J. A., Johnson, B. R., … Boltz, J. P. (2023). Biological and physical selectors for mobile biofilms, aerobic granules, and densified-biological flocs in continuously flowing wastewater treatment processes: a state-of-the-art review. Water Research, 242, 120245 (13 pp.). doi:10.1016/j.watres.2023.120245, Institutional Repository

There have been significant advances in the use of biological and physical selectors for the intensification of continuously flowing biological wastewater treatment (WWT) processes. Biological selection allows for the development of large biological aggregates (e.g., mobile biofilm, aerobic granules, and densified biological flocs). Physical selection controls the solids residence times of large biological aggregates and ordinary biological flocs, and is usually accomplished using screens or hydrocyclones. Large biological aggregates can facilitate different biological transformations in a single reactor and enhance liquid and solids separation. Continuous-flow WWT processes incorporating biological and physical selectors offer benefits that can include reduced footprint, lower costs, and improved WWT process performance. Thus, it is expected that both interest in and application of these processes will increase significantly in the future. This review provides a comprehensive summary of biological and physical selectors and their design and operation.
Faust, V., Boon, N., Ganigué, R., Vlaeminck, S. E., & Udert, K. M. (2023). Optimizing control strategies for urine nitrification: narrow pH control band enhances process stability and reduces nitrous oxide emissions. Frontiers in Environmental Science, 11, 1275152 (14 pp.). doi:10.3389/fenvs.2023.1275152, Institutional Repository

Nitrification is well-suited for urine stabilization. No base dosage is required if the pH is controlled within an appropriate operating range by urine feeding, producing an ammonium-nitrate fertilizer. However, the process is highly dependent on the selected pH set-points and is susceptible to process failures such as nitrite accumulation or the growth of acid-tolerant ammonia-oxidizing bacteria. To address the need for a robust and reliable process in decentralized applications, two different strategies were tested: operating a two-position pH controller (inflow on/off) with a narrow pH control band at 6.20/6.25 (∆pH = 0.05, narrow-pH) vs. a wider pH control band at 6.00/6.50 (∆pH = 0.50, wide-pH). These variations in pH also cause variations in the chemical speciation of ammonia and nitrite and, as shown, the microbial production of nitrite. It was hypothesized that the higher fluctuations would result in greater microbial diversity and, thus, a more robust process. The diversity of nitrifiers was higher in the wide-pH reactor, while the diversity of the entire microbiome was similar in both systems. However, the wide-pH reactor was more susceptible to tested process disturbances caused by increasing pH or temperature, decreasing dissolved oxygen, or an influent stop. In addition, with an emission factor of 0.47%, the nitrous oxide (N2O) emissions from the wide-pH reactor were twice as high as the N2O emissions from the narrow-pH reactor, most likely due to the nitrite fluctuations. Based on these results, a narrow control band is recommended for pH control in urine nitrification.
Gottschalk, F., Debray, B., Klaessig, F., Park, B., Lacome, J. M., Vignes, A., … Kaegi, R. (2023). Predicting accidental release of engineered nanomaterials to the environment. Nature Nanotechnology, 18, 412-418. doi:10.1038/s41565-022-01290-2, Institutional Repository

Challenges in distinguishing between natural and engineered nanomaterials (ENMs) and the lack of historical records on ENM accidents have hampered attempts to estimate the accidental release and associated environmental impacts of ENMs. Building on knowledge from the nuclear power industry, we provide an assessment of the likelihood of accidental release rates of ENMs within the next 10 and 30 years. We evaluate risk predictive methodology and compare the results with empirical evidence, which enables us to propose modelling approaches to estimate accidental release risk probabilities. Results from two independent modelling approaches based on either assigning 0.5% of reported accidents to ENM-releasing accidents (M1) or based on an evaluation of expert opinions (M2) correlate well and predict severe accidental release of 7% (M1) in the next 10 years and of 10% and 20% for M2 and M1, respectively, in the next 30 years. We discuss the relevance of these results in a regulatory context.
Herold, G., Rodino, F., Golparvar, A., Reynaert, E., & Carrara, S. (2023). Enhancing water safety in decentralized water reuse systems with low-cost prussian blue amperometric sensors for free chlorine monitoring. IEEE Sensors Letters, 7(9), 6005704 (4 pp.). doi:10.1109/LSENS.2023.3307084, Institutional Repository

The challenge of providing sustainable and safe water services in regions lacking centralized water infrastructure can be addressed through the utilization of on-site treatment and reuse of wastewater. However, the widespread implementation of decentralized water reuse systems is currently hindered by the considerable expenses associated with remote water quality monitoring. Specifically, when using chlorination for treatment, the fabrication and maintenance costs of free chlorine sensors pose significant drawbacks to their implementation. In this study, we present an alternative solution by mitigating the sensor cost through the utilization of electrochemical sensing coupled with a cleanroom-free sensor fabrication process. We meticulously optimized the electrodeposition process to enhance sensor stability and ensure reproducibility, achieved through precise control of reactant concentrations. Our findings demonstrate the feasibility of obtaining consistent measurements in treated greywater by employing controlled Prussian Blue electrodeposition on readily available screen-printed electrodes, resulting in variation as low as 7.44% (n = 6). Furthermore, cyclic voltammetry experiments reveal a distinct peak at -0.11 V, indicating the presence of free chlorine in treated greywater samples. This characteristic is leveraged in chronoamperometric sensing, enabling robust chemical detection with a wide dynamic linearity range (R2 = 0.9933) spanning from 0.06 to 6.28 ppm of free chlorine in treated greywater samples and a competitive sensitivity reaching 7.6 μA/cm2 per ppm.
Heusser, A., Dax, A., McArdell, C. S., & Udert, K. M. (2023). High content of low molecular weight organics does not always affect pharmaceutical adsorption on activated carbon: the case of acetate, propionate and ethanol in source-separated urine. Water Research X, 21, 100199 (10 pp.). doi:10.1016/j.wroa.2023.100199, Institutional Repository

Adsorption on activated carbon is a common process to remove pharmaceuticals in wastewater treatment. Activated carbon adsorption is usually applied to wastewater with a low content of biological degradable organics, i.e. after biological treatment. Especially low molecular weight (LMW) compounds are known to compete with pharmaceuticals for adsorption sites. The goal of this study was to test the hypothesis that biological treatment is necessary for efficient pharmaceutical removal. Source-separated urine after anaerobic storage (anaerobically stored urine) and after aerobic biological removal of organics without nitrification (organics-depleted urine) were used in this study. In anaerobically stored urine 60% of the organic compounds were LMW organics, of which about 40% were acetate and propionate. 74% of the DOC and 100% of acetate and propionate were removed during aerobic biological treatment. To investigate the effect of the organic compounds on pharmaceutical removal, sorption experiments with 19 spiked pharmaceuticals and one artificial sweetener were conducted with powdered activated carbon. Ethanol, another LMW organic, was included in the study, as it is regularly used for pharmaceutical spiking thereby strongly increasing the DOC content. The experiments showed that the adsorption of the pharmaceuticals and the sweetener were hardly affected by the easily biodegradable LMW organics or ethanol. Therefore, it was concluded that biological pre-treatment is not necessary for efficient pharmaceutical adsorption. Since acetate, propionate and ethanol contribute substantially to the DOC content but do not absorb UV light, the latter is recommended as indicator for pharmaceutical removal in solutions with high contents of biodegradable LMW organics.
Huang, K., Eschenbach, W., Wei, J., Hausherr, D., Frey, C., Kupferschmid, A., … Mohn, J. (2023). Simultaneous 15N online analysis in NH4+, NO2-, NO3-, and N2O to trace N2O production pathways in nitrogen-polluted aqueous environments. ACS ES&T Water, 3(11), 3485-3495. doi:10.1021/acsestwater.3c00216, Institutional Repository

Engineered nitrogen (N) removal processes in water treatment plants and N-transformation reactions in polluted environments represent prominent sources of the potent greenhouse gas, nitrous oxide (N2O). The relevance of microbial and abiotic formation pathways can be assessed by using 15N tracer techniques. While 15N-N2O analysis with optical analyzers is straightforward, the quantification of atom % 15N of inorganic N compounds, such as ammonium (NH4+), nitrite (NO2-), and nitrate (NO3-), requires discrete sample analyses that are time-consuming and labor-intensive. In this study, we developed an automated sample preparation unit, coupled to a membrane inlet quadrupole mass spectrometer, for the online, quasi-simultaneous analysis of atom % 15N in NH4+, NO2-, and NO3-. This technique was designed and validated for 15N-spiking applications at moderate (100-200 μmol L-1, 1 atom % 15N) to high (2-3 mmol L-1, 33 atom % 15N) dissolved inorganic N concentrations typically encountered in sewer systems or contaminated watersheds. The high potential of the developed system, in combination with 15N-N2O analysis by Fourier-transform infrared spectroscopy, to constrain N transformations and sources of N2O was demonstrated in a feasibility study, where nitrifier denitrification was identified as the primary N2O formation pathway during the partial NH4+ oxidation to NO2- in a lab-scale sequencing batch reactor.
Joëlle Kubeneck, L., ThomasArrigo, L. K., Rothwell, K. A., Kaegi, R., & Kretzschmar, R. (2023). Competitive incorporation of Mn and Mg in vivianite at varying salinity and effects on crystal structure and morphology. Geochimica et Cosmochimica Acta, 346, 231-244. doi:10.1016/j.gca.2023.01.029, Institutional Repository

Vivianite, a ferrous phosphate mineral, can be an important phosphorus (P) sink in non-sulfidic, reducing coastal sediments. The Fe in the crystal structure of vivianite can be substituted by other divalent metal cations such as Mn2+ or Mg2+. Since Mg is much more abundant in coastal porewaters than Mn, the more frequent reports of Mn substitution in vivianites of coastal sediments has been suggested to indicate a preferential incorporation of Mn over Mg into the crystal structure of vivianite. However, although both Mn and Mg substitution in vivianite are environmentally relevant, it is yet unknown whether Mn or Mg is preferentially incorporated and how these isomorphic substitutions alter the crystal structure and morphology of vivianite, parameters which may influence vivianite reactivity. Here, we studied the incorporation of Mn and/or Mg in vivianites formed by co-precipitation at pH 7 in the presence of varying dissolved Mn and/or Mg concentrations and solution salinities resembling an estuarine gradient from 0 to 9 psu. In total, 19 different vivianites were synthesized, with up to 50% of Fe substituted by Mn and Mg. Thermodynamic equilibrium calculations showed that aqueous Mg speciation was altered with increasing salinity, while Mn speciation was less affected, likely explaining the preferential incorporation of Mn in the vivianite structure at higher salinities. 57Fe-Mössbauer spectroscopy revealed that both Mn and Mg were preferentially incorporated in the double-octahedral Fe position, at which intervalence charge transfer is possible during the oxidation of vivianite. In contrast to Mg, which is redox inactive, incorporated Mn can participate in heteronuclear intervalence charge transfer with Fe. Thus, incorporation of either cation may impact the reactivity of vivianite under oxidizing conditions in element specific ways. Results of complementary analyses including X-ray diffraction, electron microscopy and Fe K-edge X-ray absorption spectroscopy further showed that incorporation of Mn and/or Mg led to smaller particle size, increased crystal roughness and thinner crystals, as well as systematic changes in unit cell parameters. These observed changes in crystal morphology might impact the reactivity of vivianite in natural environments and thus the effect of cation incorporation in vivianite should be considered when studying Fe and P cycling in coastal sediments.
Kizgin, A., Schmidt, D., Joss, A., Hollender, J., Morgenroth, E., Kienle, C., & Langer, M. (2023). Application of biological early warning systems in wastewater treatment plants: Introducing a promising approach to monitor changing wastewater composition. Journal of Environmental Management, 347, 119001 (12 pp.). doi:10.1016/j.jenvman.2023.119001, Institutional Repository

Wastewater treatment plants (WWTPs) are a major source of micropollutants to surface waters. Currently, their chemical or biological monitoring is realized by using grab or composite samples, which provides only snapshots of the current wastewater composition. Especially in WWTPs with industrial input, the wastewater composition can be highly variable and a continuous assessment would be advantageous, but very labor and cost intensive. A promising concept are automated real-time biological early warning systems (BEWS), where living organisms are constantly exposed to the water and an alarm is triggered if the organism's responses exceed a harmful threshold of acute toxicity. Currently, BEWS are established for drinking water and surface water but are seldom applied to monitor wastewater. This study demonstrates that a battery of BEWS using algae (Chlorella vulgaris in the Algae Toximeter, bbe Moldaenke), water flea (Daphnia magna in the DaphTox II, bbe Moldaenke) and gammarids (Gammarus pulex in the Sensaguard, REMONDIS Aqua) can be adapted for wastewater surveillance. For continuous low-maintenance operation, a back-washable membrane filtration system is indispensable for adequate preparation of treated wastewater. Only minor deviations in the reaction of the organisms towards treated and filtered wastewater compared to surface waters were detected. After spiking treated wastewater with two concentrations of the model compounds diuron, chlorpyrifos methyl, and sertraline, the organisms in the different BEWS showed clear responses depending on the respective compound, concentration and mode of action. Immediate effects on photosynthetic activity of algae were detected for diuron exposure, and strong behavioral changes in water flea and gammarids after exposure to chlorpyrifos methyl or sertraline were observed, which triggered automated alarms. Different types of data analysis were applied to extract more information out of the specific behavioral traits, than only provided by the vendors algorithms. To investigate, whether behavioral movement changes can be linked to impact other endpoints, the effects on feeding activity of G. pulex were evaluated and results indicated significant differences between the exposures. Overall, these findings provide an important basis indicating that BEWS have the potential to act as alarm systems for pollution events in the wastewater sector.
Kollmann, J., Nath, S., Singh, S., Balasubramanian, S., Reynaert, E., Morgenroth, E., & Contzen, N. (2023). Acceptance of on-site wastewater treatment and reuse in Bengaluru, India: the role of perceived costs, risks, and benefits. Science of the Total Environment, 895, 165042 (11 pp.). doi:10.1016/j.scitotenv.2023.165042, Institutional Repository

In dealing with water pollution and freshwater scarcity, on-site treatment and reuse of domestic wastewater has shown to be a promising solution. To increase on-site wastewater treatment and reuse, some cities, among them Bengaluru in India, have mandated the installation and use of the necessary technology in certain building types. However, even with a mandate, a successful and sustainable implementation of the technology, including reliable operation, monitoring, and maintenance, depends on the acceptance (i.e. positive valuation) of the technology and its use by the (prospective) users. Literature on technology acceptance indicates perceived costs, risks, and benefits of the respective technology as key predictors of acceptance. Therefore, the present online study assessed this relationship for on-site systems in Bengaluru. The relation was analysed separately for mandated users of on-site systems (N = 103) and current non-users (i.e. potential prospective users, should the mandate be expanded; N = 232), as the perceptions might differ between the two groups, due to the personal experience with the technology among users. The results show that for mandated users and non-users, acceptance of on-site systems is explained by perceived benefits only, namely a positive image of users, environmental benefits, and, only for non-users, also financial benefits for the city. The findings suggest that interventions aimed at promoting on-site systems should include emphasis on the benefits of on-site systems. Whenever possible, interventions should be tailored to the target group's individual cost, risk, and benefit perception.
Larivé, O., Torii, S., Derlon, N., & Kohn, T. (2023). Selective elimination of enterovirus genotypes by activated sludge and chlorination. Environmental Science: Water Research and Technology, 9(6), 1620-1633. doi:10.1039/d3ew00050h, Institutional Repository

Enteroviruses, which are commonly circulating viruses shed in the stool, are released into the sewage system and only partially removed or inactivated, resulting in the discharge of infectious enteroviruses into the environment. Activated sludge and chlorination remove or inactivate enterovirus genotypes to different extents, and thus have the potential to shape the population that will be discharged. The goal of this study was to evaluate how activated sludge and chlorination treatment shape an enterovirus population at the genotype level, using a population of eight genotypes commonly found in sewage: CVA9, CVB1, CVB2, CVB3, CVB4, CVB5, E25, E30. Our results show that the extent of inactivation varied among genotypes, but also across sludge samples. We find that the effluent of activated sludge systems will be depleted in CVA9, CVB1 and CVB2 while E25 together with CVB3, CVB4 and CVB5 will be prevalent. Furthermore, we found that microbial inactivation was the main mechanism of infectivity loss in the activated sludge, while adsorption to the sludge flocs was not significant. During effluent chlorination, we also observed that CVB5, CVB3 and to a lesser extent E25 were less susceptible to chlorination while E30 was readily inactivated, and activated sludge-derived EPS provided further protection against chlorination. This study contributes to a better understanding of the variability of sewage treatment efficacy against different enteroviruses.
Maghsoodi, M., Jacquin, C., Teychené, B., Lesage, G., & Snow, S. D. (2023). Delineating the effects of molecular and colloidal interactions of dissolved organic matter on titania photocatalysis. Langmuir, 39(10), 3752-3761. doi:10.1021/acs.langmuir.2c03487, Institutional Repository

In the face of significant challenges to practical applications of photocatalysis for water treatment, recent reports revealed a potential route to overcome a problem posed by dissolved organic matter (DOM). These studies showed that inhibition of photocatalytic processes by DOM is driven largely by competition for active surface sites on TiO2 or other catalysts, and controlling the type of DOM present in solution could significantly mitigate DOM fouling. Whether or not control of solution parameters could achieve the same preventative action is not known. Here, a series of DOM isolates, including humic acid (HA) and transphilic (TPI), hydrophobic (HPO), or colloidal fractions of organic matter from a membrane bioreactor mixed liquor supernatant, were tested for inhibitory activity under a range of pH values (3, 5, 7, and 9) and ionic compositions (NaCl, CaCl2, and Al2(SO4)3 with ionic strengths (IS) ranging from 0 to 3 M). The resulting TiO2-DOM agglomerates were monitored for size and ζ-potential. Inhibitory profiles were generated using para-chlorobenzoic acid (pCBA) as probe with varying concentrations of inhibitory DOM for each solution condition to discern the extent of surface-phase quenching of radicals. Manipulation of pH clearly impacted inhibition, and the effect varied by DOM type; for example, interference occurred at all pHs for HA, at neutral or basic pHs for TPI, and only at pH 7 for HPO. Particle sizes did not correlate with inhibitory action of DOM. Increases in ionic strength induced growth of TiO2 and TiO2-DOM agglomerates, but again, particle sizes did not correlate to inhibition by DOM. The changes to IS, regardless of ion type, were not affected by the presence of TPI or HPO. Since particle stability did not correlate directly with photocatalytic activity, we suggest that surface-based quenching reactions arise from site-specific adsorption rather than generalized particle destabilization and aggregation.
Nenonen, V. V., Kaegi, R., Hug, S. J., Göttlicher, J., Mangold, S., Winkel, L. H. E., & Voegelin, A. (2023). Formation and transformation of Fe(III)- and Ca-precipitates in aqueous solutions and effects on phosphate retention over time. Geochimica et Cosmochimica Acta, 360, 207-230. doi:10.1016/j.gca.2023.09.004, Institutional Repository

Exfiltration of anoxic phosphate-rich groundwater into surface water leads to the oxidation of dissolved Fe(II) and the formation of Fe(III)-precipitates that can retain phosphate (PO4) and thereby attenuate eutrophication. Fresh Fe(III)-precipitates transform into more stable phases over time, and retained PO4 may be released again. In parallel, CO2 outgassing can promote the formation of Ca-phosphates or -carbonates that also sequester PO4. In laboratory experiments, we studied the effects of Mg, Ca, silicate (SiO4) and PO4 on these processes. Fresh Fe(III)-precipitates were formed in bicarbonate-buffered aqueous solutions at pH ∼ 7.0 via the oxidation of 0.5 mM Fe(II) in the presence of 0.15 or 0.025 mM PO4, at Mg or Ca concentrations of 0, 0.4, 1.2 or 4 mM and in the absence or presence of 0.5 mM SiO4. After CO2 outgassing, the suspensions were allowed to age for 100 d at pH ∼ 8. Changes in the composition and structure of Fe(III)- and Ca-precipitates over time were probed with spectroscopic and microscopic techniques and were linked to variations in the retention of PO4. The oxidation of Fe(II) led to effective PO4 removal via the formation of Fe(III)-precipitates that consisted of amorphous (Ca-)Fe(III)-phosphate ((Ca)FeP), ferrihydrite (Fh) and, in SiO4-free treatments, lepidocrocite (Lp). During aging, FeP and Fh that had formed in the absence of Mg, Ca and SiO4 rapidly and nearly completely transformed into Lp. Via effects on molecular- and nanoscale precipitate structure, Mg slowed down FeP transformation into Fh, stabilized Fh, and decreased the crystallinity of Lp (in SiO4-free suspensions), Ca stabilized CaFeP against transformation into Fh, and SiO4 stabilized Fh and (Ca)FeP. Core/shell CaFeP/Fh particles formed in electrolytes that contained Ca and SiO4 hardly transformed within 100 d. Calcite only formed at low dissolved PO4 concentrations and, by incorporation of PO4, contributed to PO4 retention. Higher levels of dissolved PO4 inhibited calcite formation but could induce Ca-phosphate precipitation. Differences in precipitate formation and transformation pathways and kinetics were reflected in the extents of PO4 release over the 100-d aging period, ranging from rapid release of 77% of the total PO4 in the treatment without Mg, Ca and SiO4 at 0.15 mM total PO4 to slow release of only 0.1% of the total PO4 at initial concentrations of 4 mM Ca, 0.5 mM SiO4, and 0.025 mM PO4. In summary, this study reveals the conditions and the extents and timescales over which Fe(III)- and Ca-precipitates form and transform and how these processes affect PO4 immobilization in near-neutral natural waters. The detailed new insights into the coupling between Fe(III)- and Ca-precipitate formation and into the interdependent effects of Mg, Ca, SiO4 and PO4 are not only relevant with respect to PO4 but also with respect to the cycling of trace elements in natural and engineered systems.
Reynaert, E., Steiner, P., Yu, Q., D'Olif, L., Joller, N., Schneider, M. Y., & Morgenroth, E. (2023). Predicting microbial water quality in on-site water reuse systems with online sensors. Water Research, 240, 120075 (13 pp.). doi:10.1016/j.watres.2023.120075, Institutional Repository

Widespread implementation of on-site water reuse is hindered by the limited availability of monitoring approaches that ensure microbial quality during operation. In this study, we developed a methodology for monitoring microbial water quality in on-site water reuse systems using inexpensive and commercially available online sensors. An extensive dataset containing sensor and microbial water quality data for six of the most critical types of disruptions in membrane bioreactors with chlorination was collected. We then tested the ability of three typological machine learning algorithms - logistic regression, support-vector machine, and random forest - to predict the microbial water quality as "safe" or "unsafe" for reuse. The main criteria for model optimization was to ensure a low false positive rate (FPR) - the percentage of safe predictions when the actual condition is unsafe - which is essential to protect users health. This resulted in enforcing a fixed FPR ≤ 2%. Maximizing the true positive rate (TPR) - the percentage of safe predictions when the actual condition is safe - was given second priority. Our results show that logistic-regression-based models using only two out of the six sensors (free chlorine and oxidation-reduction potential) achieved the highest TPR. Including sensor slopes as engineered features allowed to reach similar TPRs using only one sensor instead of two. Analysis of the occurrence of false predictions showed that these were mostly early alarms, a characteristic that could be regarded as an asset in alarm management. In conclusion, the simplest algorithm in combination with only one or two sensors performed best at predicting the microbial water quality. This result provides useful insights for water quality modeling or for applications where small datasets are a common challenge and a general advantage might be gained by using simpler models that reduce the risk of overfitting, allow better interpretability, and require less computational power.
Reynaert, E., Gretener, F., Julian, T. R., & Morgenroth, E. (2023). Sensor setpoints that ensure compliance with microbial water quality targets for membrane bioreactor and chlorination treatment in on-site water reuse systems. Water Research X, 18, 100164 (13 pp.). doi:10.1016/j.wroa.2022.100164, Institutional Repository

Widespread implementation of on-site water reuse systems is hindered by the limited ability to ensure the level of treatment and protection of human health during operation. In this study, we tested the ability of five commercially available online sensors (free chlorine (FC), oxidation-reduction potential (ORP), pH, turbidity, UV absorbance at 254 nm) to predict the microbial water quality in membrane bioreactors followed by chlorination using logistic regression-based and mechanism-based models. The microbial water quality was assessed in terms of removal of enteric bacteria from the wastewater, removal of enteric viruses, and regrowth of bacteria in the treated water. We found that FC and ORP alone could predict the microbial water quality well, with ORP-based models generally performing better. We further observed that prediction accuracy did not increase when data from multiple sensors were integrated. We propose a methodology to link online sensor measurements to risk-based water quality targets, providing operation setpoints protective of human health for specific combinations of wastewaters and reuse applications. For instance, we recommend a minimum ORP of 705 mV to ensure a virus log-removal of 5, and an ORP of 765 mV for a log-removal of 6. These setpoints were selected to ensure that the percentage of events where the water is predicted to meet the quality target but it does not remains below 5%. Such a systematic approach to set sensor setpoints could be used in the development of water reuse guidelines and regulations that aim to cover a range of reuse applications with differential risks to human health.
Sam, S. B., Morgenroth, E., & Strande, L. (2023). Changes in organic fractions, cations, and stabilization from feces to fecal sludge: implications for dewatering performance and management solutions. Journal of Water Sanitation and Hygiene for Development, 13(9), 699-710. doi:10.2166/washdev.2023.086, Institutional Repository

Reliable dewatering performance remains a key challenge in fecal sludge management, and the controlling factors or mechanisms are not well understood. There remain limited studies on constituents in feces and fecal sludge and how they affect the dewaterability of fecal sludge. This study aimed at evaluating a range of constituents in feces, and to gain empirical knowledge toward a mechanistic understanding of how they influence dewaterability. In this study, cellulose reduced capillary suction time, decreased supernatant turbidity, and increased cake solids. While hemicellulose decreased supernatant turbidity, lignin increased supernatant turbidity, capillary suction time, and cake solids. Extracellular polymeric substances (EPS) increased both capillary suction time and supernatant turbidity and decreased cake solids, whereas lipids increased turbidity. Cations had no significant effect on dewatering properties. Overall, fecal sludge stored in containments had better dewatering performance than ‘fresh’ fecal sludge, which was attributed to stabilization. Field fecal sludge had a higher relative abundance of Pseudomonas, which is associated with better aggregation, and fewer small particles (<10 μm) that clog filters to reduce dewatering performance. Further understanding of stabilization and developing an agreed-upon metrics of stabilization are essential for predicting fecal sludge dewatering performance, and developing smaller footprint dewatering treatment technologies.
Sodnikar, K., Kaegi, R., Christl, I., Schroth, M. H., & Sander, M. (2023). Transport of double-stranded ribonucleic acids (dsRNA) and deoxyribonucleic acids (DNA) in sand and iron oxide-coated sand columns under varying solution chemistries. Environmental Science: Processes and Impacts, 25(12), 2067-2080. doi:10.1039/d3em00294b, Institutional Repository

Assessing ecological risks associated with the use of genetically modified RNA interference crops demands an understanding of the fate of crop-released insecticidal double-stranded RNA (dsRNA) molecules in soils. We studied the adsorption of one dsRNA and two double-stranded DNA as model nucleic acids (NAs) during transport through sand- and iron oxide-coated sand (IOCS)-filled columns over a range of solution pH and ionic compositions. Consistent with NA-sand electrostatic repulsion, we observed only slight retention of NAs in sand columns. Conversely, pronounced NA retention in IOCS columns is consistent with strong and irreversible NA adsorption involving electrostatic attraction to and inner-sphere complex formation of NAs with iron oxide coatings. Adsorption of NAs to iron oxides revealed a fast and a slow kinetic adsorption regime, possibly caused by the excluded-area effect. Adsorption of NAs to sand and IOCS increased in the presence of dissolved Mg2+ and with increasing ionic strength, reflecting cation-bridging and screening of repulsive electrostatics, respectively. The co-solute phosphate and a pre-adsorbed dissolved organic matter isolate competitively suppressed dsRNA adsorption to IOCS. Similar adsorption characteristics of dsRNA and similarly sized DNA suggest that existing information on DNA adsorption to soil particles helps in predicting adsorption and fate of dsRNA molecules in soils.
Stoffel, D., Derlon, N., Traber, J., Staaks, C., Heijnen, M., Morgenroth, E., & Jacquin, C. (2023). Gravity-driven membrane filtration with compact second-life modules daily backwashed: an alternative to conventional ultrafiltration for centralized facilities. Water Research X, 18, 100178 (12 pp.). doi:10.1016/j.wroa.2023.100178, Institutional Repository

Gravity-driven membrane (GDM) filtration is a strategic alternative to conventional ultrafiltration (UF) for the resilient production of drinking water via ultrafiltration when resources become scarce, given the low dependency on energy and chemicals, and longer membrane lifetime. Implementation at large scale requires the use of compact and low-cost membrane modules with high biopolymer removal capacity. We therefore evaluated (1) to what extent stable flux can be obtained with compact membrane modules, i.e., inside-out hollow fiber membranes, and frequent gravity-driven backwash, (2) whether we can reduce membrane expenses by effectively utilizing second-life UF modules, i.e., modules that have been discarded by treatment plant operators because they are no longer under warranty, (3) if biopolymer removal could be maintained when applying a frequent backwash and with second-life modules and (4) which GDM filtration scenarios are economically viable compared to conventional UF, when considering the influence of new or second-life modules, membrane lifetime, stable flux value and energy pricing. Our findings showed that it was possible to maintain stable fluxes around 10 L/m2/h with both new and second-life modules for 142 days, but a daily gravity-driven backwash was necessary and sufficient to compensate the continuous flux drop observed with compact modules. In addition, the backwash did not affect the biopolymer removal. Costs calculations revealed two significant findings: (1) using second-life modules made GDM filtration membrane investment less expensive than conventional UF, despite the higher module requirements for GDM filtration and (2) overall costs of GDM filtration with a gravity-driven backwash were unaffected by energy prices rise, while conventional UF costs rose significantly. The later increased the number of economically viable GDM filtration scenarios, including scenarios with new modules. In summary, we proposed an approach that could make GDM filtration in centralized facilities feasible and increase the range of UF operating conditions to better adapt to increasing environmental and societal constraints.
Sylvestre, É., Reynaert, E., & Julian, T. R. (2023). Defining risk-based monitoring frequencies to verify the performance of water treatment barriers. Environmental Science and Technology Letters, 10(4), 374-384. doi:10.1021/acs.estlett.3c00154, Institutional Repository

Preventing failures of water treatment barriers can play an important role in meeting the increasing demand for microbiologically safe water. The development and integration of failure prevention strategies into quantitative microbial risk assessment (QMRA) offer opportunities to support the design and operation of treatment trains. This study presents existing failure models and extends them to guide the development of risk-based operational monitoring strategies. For barriers with rapid performance loss, results show that a failure of 15 s should be reliably detected to verify a log reduction value (LRV) of 6.0; thus, detecting and remediating these failures may be beyond current technology. For chemical disinfection with a residual, failure durations in order of minutes should be reliably detected to verify a LRV of 6.0. Short-term failures are buffered because the disinfectant residual concentration sustains a partial reduction performance. Therefore, increasing the contact time and hydraulic mixing reduces the impact of failures. These findings demonstrate the importance of defining precise frequencies to monitor barrier performances during operation. Overall, this study highlights the utility of process-specific models for developing failure prevention strategies for water safety management.
Tamayo-Belda, M., Pérez-Olivares, A. V., Pulido-Reyes, G., Martin-Betancor, K., González-Pleiter, M., Leganés, F., … Fernández-Piñas, F. (2023). Tracking nanoplastics in freshwater microcosms and their impacts to aquatic organisms. Journal of Hazardous Materials, 445, 130625 (12 pp.). doi:10.1016/j.jhazmat.2022.130625, Institutional Repository

In this work, we used palladium-doped polystyrene NPLs (PS-NPLs with a primary size of 286 ± 4 nm) with an irregular surface morphology which allowed for particle tracking and evaluation of their toxicity on two primary producers (cyanobacterium, Anabaena sp. PCC7120 and green algae, Chlamydomonas reinhardtii) and one primary consumer (crustacean, Daphnia magna). the concentration range for Anabaena and C. reinhardtii was from 0.01 to 1000 mg/L and for D. magna, the range was from 7.5 to 120 mg/L.EC50 s ranged from 49 mg NPLs/L for D. magna (48hEC50 s) to 248 mg NPLs/L (72hEC50 s for C. reinhardtii). PS-NPLs induced dose-dependent reactive oxygen species overproduction, membrane damage and metabolic alterations. To shed light on the environmental fate of PS-NPLs, the short-term distribution of PS-NPLs under static (using lake water and sediments) and stirring (using river water and sediments) conditions was studied at laboratory scale. The results showed that most NPLs remained in the water column over the course of 48 h. The maximum percentage of settled particles (∼ 30 %) was found under stirring conditions in comparison with the ∼ 10 % observed under static ones. Natural organic matter increased the stability of the NPLs under colloidal state while organisms favored their settlement. This study expands the current knowledge of the biological effects and fate of NPLs in freshwater environments.
Ward, B. J., Nguyen, M. T., Sam, S. B., Korir, N., Niwagaba, C. B., Morgenroth, E., & Strande, L. (2023). Particle size as a driver of dewatering performance and its relationship to stabilization in fecal sludge. Journal of Environmental Management, 326, 116801 (12 pp.). doi:10.1016/j.jenvman.2022.116801, Institutional Repository

Poor and unpredictable dewatering performance of fecal sludge is a major barrier to sanitation provision in urban areas not served by sewers. Fecal sludge comprises everything that accumulates in onsite containments, and its characteristics are distinct from wastewater sludges and from feces. There is little fundamental understanding of what causes poor dewatering in fecal sludge. For the first time, we demonstrate that particle size distribution is a driver of dewatering performance in fecal sludge, and is associated with level of stabilization. Higher concentrations of small particles (<10 μm) and smaller median aggregate size (D50) corresponded to poor dewatering performance (measured by capillary suction time (CST) and supernatant turbidity) in field samples from Kenya and Uganda and in controlled laboratory anaerobic storage experiments. More stabilized fecal sludge (higher C/N, lower VSS/TSS) had better dewatering performance, corresponding to lower concentrations of small particles. Samples with the largest aggregates (D50 > 90 μm) had higher abundance of Gammaproteobacteria Pseudomonas, and samples with the smallest aggregates (D50 ≤ 50 μm) were characterized by higher abundance of Bacteroidetes Vadin HA17 and Rikenellaceae. Contrary to common perceptions, stabilization, particle size distribution, and dewatering performance were not dependent on time intervals between emptying of onsite containments or on time in controlled anaerobic storage experiments. Our results suggest that the stabilization process in onsite containments, and hence the dewaterability of sludge arriving at treatment facilities, is not dependent on time in containment but is more likely associated with specific microbial populations and the in-situ environmental conditions which promote or discourage their growth.
Wiprächtiger, M., Haupt, M., Froemelt, A., Klotz, M., Beretta, C., Osterwalder, D., … Hellweg, S. (2023). Combining industrial ecology tools to assess potential greenhouse gas reductions of a circular economy. Method development and application to Switzerland. Journal of Industrial Ecology, 27(1), 254-271. doi:10.1111/jiec.13364, Institutional Repository

Industrial ecology (IE) methodologies, such as input/output or material flow analysis and life cycle assessment (LCA), are often used for the environmental evaluation of circular economy strategies. Up to now, an approach that utilizes these methods in a systematic, integrated framework for a holistic assessment of a geographic region's sustainable circular economy potential has been lacking. The approach developed in this study (IE4CE approach) combines IE methodologies to determine the environmental impact mitigation potential of circular economy strategies for a defined geographic region. The approach foresees five steps. First, input/output analysis helps identify sectors with high environmental impacts. Second, a refined analysis is conducted using material flow and LCA. In step 3, circular strategies are used for scenario design and evaluated in step 4. In step 5, the assessment results are compiled and compared across sectors. The approach was applied to a case study of Switzerland, analyzing 8 sectors and more than 30 scenarios in depth. Carbon capture and storage (CCS) from waste incineration, biogas and cement production, food waste prevention in households, hospitality and production, and the increased recycling of plastics had the highest mitigation potential. Most of the scenarios do not influence each other. One exception is the CCS scenarios: waste avoidance scenarios decrease the reduction potential of CCS. A combination of scenarios from different sectors, including their impact on the CCS scenario potential, led to an environmental impact mitigation potential of 11.9 Mt CO2-eq for 2050, which equals 14% of Switzerland's current consumption-based impacts.
Xu, J., Chen, C., Hu, X., Chen, D., Bland, G., Wielinski, J., … Lowry, G. V. (2023). Particle-scale understanding of arsenic interactions with sulfidized nanoscale zerovalent iron and their impacts on dehalogenation reactivity. Environmental Science and Technology, 57(51), 21917-21926. doi:10.1021/acs.est.3c08635, Institutional Repository

Co-occurrence of organic contaminants and arsenic oxoanions occurs often at polluted groundwater sites, but the effect of arsenite on the reactivity of sulfidized nanoscale zerovalent iron (SNZVI) used to remediate groundwater has not been evaluated. Here, we study the interaction of arsenite [As(III)] with SNZVI at the individual-particle scale to better understand the impacts on the SNZVI properties and reactivity. Surface and intraparticle accumulation of As was observed on hydrophilic FeS-Fe0 and hydrophobic FeS2-Fe0 particles, respectively. X-ray absorption spectroscopy indicated the presence of realgar-like As-S and elemental As0 species at low and high As/Fe concentration ratios, respectively. Single-particle inductively coupled plasma time-of-flight mass spectrometry analysis identified As-containing particles both with and without Fe. The probability of finding As-containing particles without Fe increased with the S-induced hydrophobicity of SNZVI. The interactions of SNZVI materials with coexisting arsenite inhibited their reactivity with water (∼5.8-230.7-fold), trichloroethylene (∼3.6-67.5-fold), and florfenicol (∼1.1-5.9-fold). However, the overall selectivity toward trichloroethylene and florfenicol relative to water was improved (up to 9.0-fold) because the surface-associated As increased the SNZVI hydrophobicity. These results indicate that reactions of SNZVI with arsenite can remove As from groundwater and improve the properties of SNZVI for dehalogenation selectivity.
Bou-Sarkis, A., Pagliaccia, B., Ric, A., Derlon, N., Paul, E., Bessiere, Y., & Girbal-Neuhauser, E. (2022). Effects of alkaline solvents and heating temperatures on the solubilization and degradation of gel-forming Extracellular Polymeric Substances (EPS) extracted from aerobic granular sludge. Biochemical Engineering Journal, 185, 108500 (9 pp.). doi:10.1016/j.bej.2022.108500, Institutional Repository

The effects of solvents and heating temperatures on the recovery and degradation of gel-forming EPS (Extracellular Polymeric Substances) extracted from aerobic granular sludge were investigated. Sodium hydroxide has allowed a better EPS solubilization compared to sodium carbonate (711.3 ± 38 and 408.4 ± 4 mg VS /g VS respectively) but the capacity to precipitate gel-forming EPS at acidic pH was higher in sodium carbonate (22% compared to 6% in sodium hydroxide at 80 °C). Increasing the temperature from 20 °C to 80 °C during EPS solubilization has multiplied the amount of solubilized matter by 4 in sodium carbonate and 2.2 in sodium hydroxide. Similar biochemical composition but different molecular weight profiles were observed for the two solubilized EPS extracts, evidencing partial degradation of the polymers in sodium hydroxide. Furthermore, coupling molecular weight analysis and precipitation yield measurement revealed that the lower precipitation of sodium hydroxide solubilized EPS is related to the size reduction due to degradation. Altogether these results help to guide towards a unified protocol for the extraction of gel-forming EPS.
Brison, A., Rossi, P., & Derlon, N. (2022). Influent carbon to phosphorus ratio drives the selection of PHA-storing organisms in a single CSTR. Water Research X, 16, 100150 (11 pp.). doi:10.1016/j.wroa.2022.100150, Institutional Repository

Enriching a biomass with a high fraction of polyhydroxyalkanoate-storing organisms (PHA-storers) represents an essential step in the production of PHAs (bioplastics) from municipal wastewater using mixed microbial cultures. A major challenge is however to create selective growth conditions that are favourable to PHA-storers. Our study thus investigates to what extent the influent COD to phosphorus (COD:P) ratio can be used as a tool for the robust selection of PHA-storers in a single continuous-flow stirred-tank reactor (CSTR). Therefore, we operated five CSTRs in parallel, fed with synthetic wastewater (50% acetate - 50% propionate) with different COD:P ratios (200−1000 gCOD gP−1), and performed a detailed analysis of the microbial communities over long-term (30−70 solid retention times). Our study demonstrates that efficient and robust selection of PHA-storers can be achieved in a single CSTR at high influent COD:P ratios. The selective advantage for PHA-storers increases with the influent COD:P ratio, but only if growth conditions remain limited by both C-substrate and P. In contrast, selection performance deteriorates when COD:P ratios are too high and growth conditions are limited by P only. At an optimal COD:P ratio of 800 gCOD gP−1, a stable microbial community consisting of >90% PHA-storers and dominated by Pannonibacter sp. was selected in the long-term. Finally, our results suggest that high COD:P ratios provide a selective advantage to microorganisms with low cellular P requirements, explaining why different PHA-storers (i.e., Xanthobacter sp. vs. Pannonibacter sp.) were selected depending on the influent COD:P ratio (i.e., 200 vs. 800 gCOD gP−1). Overall, our results provide relevant insights for the development of a new approach for selecting PHA-storers, based on the use of a single CSTR and control of the influent COD:P ratio.
Brison, A., Rossi, P., Gelb, A., & Derlon, N. (2022). The capture technology matters: composition of municipal wastewater solids drives complexity of microbial community structure and volatile fatty acid profile during anaerobic fermentation. Science of the Total Environment, 815, 152762 (13 pp.). doi:10.1016/j.scitotenv.2021.152762, Institutional Repository

The production of volatile fatty acids (VFAs) represents a relevant option to valorize municipal wastewater (MWW). In this context, different capture technologies can be used to recover organic carbon from wastewater in form of solids, while pre-treatment of those solids has the potential to increase VFA production during subsequent fermentation. Our study investigates how VFA composition produced by fermentation is influenced (i) by the choice of the capture technology, as well as (ii) by the use of thermal alkaline pre-treatment (TAP). Therefore, the fermentation of solids originating from a primary settler, a micro-sieve, and a high-rate activated sludge (HRAS) system was investigated in continuous lab-scale fermenters, with and without TAP. Our study demonstrates that the capture technology strongly influences the composition of the produced solids, which in turn drives the complexity of the fermenter's microbial community and ultimately, of the VFA composition. Solids captured with the primary settler or micro-sieve consisted primarily of polysaccharides, and led to the establishment of a microbial community specialized in the degradation of complex carbohydrates. The produced VFA composition was relatively simple, with acetate and propionate accounting for >90% of the VFAs. In contrast, the HRAS system produced biomass-rich solids associated with higher protein contents. The microbial community which then developed in the fermenter was therefore more diversified and capable of converting a wider range of substrates (polysaccharides, proteins, amino acids). Ultimately, the produced VFA composition was more complex, with equal fractions of isoacids and propionate (both ~20%), while acetate remained the dominant acid (~50%). Finally, TAP did not significantly modify the VFA composition while increasing VFA yields on HRAS and sieved material by 35% and 20%, respectively. Overall, we demonstrated that the selection of the technology used to capture organic substrates from MWW governs the composition of the VFA cocktail, ultimately with implications for their further utilization.
Cariti, F., Tuñas Corzon, A., Fernandez-Cassi, X., Ganesanandamoorthy, P., Ort, C., Julian, T. R., & Kohn, T. (2022). Wastewater reveals the spatiotemporal spread of SARS-CoV-2 in the Canton of Ticino (Switzerland) during the onset of the COVID-19 pandemic. ACS ES&T Water, 2(11), 2194-2200. doi:10.1021/acsestwater.2c00082, Institutional Repository

Wastewater-based epidemiology (WBE) has emerged as an effective tool for monitoring SARS-CoV-2 dynamics during the COVID-19 pandemic. Here, we add a spatial component to WBE and use it to investigate SARS-CoV-2 spread in the canton of Ticino during the onset of the pandemic in Switzerland (end of February 2020 to beginning of March 2020). Ticino is located at the border to Northern Italy, where a large COVID-19 outbreak occurred in February 2020. Not surprisingly, Ticino was the site of the first clinically confirmed COVID-19 case in Switzerland. We retrospectively analyzed daily influent samples from nine wastewater treatment plants in Ticino that jointly cover an area of 20 km × 60 km and 351,000 people (>99% of the population). Our result is a fine-grained view of the spatiotemporal evolution of the COVID-19 pandemic in this canton. The wastewater analysis revealed that by February 29, 2020, SARS-CoV-2 had already spread to all catchments. At the same time, only four individual cases had been clinically confirmed across the region served by the treatment plants investigated. Our results demonstrate that WBE could serve as a versatile tool to monitor the introduction and spread of an infectious agent on a regional scale. To fully exploit its utility, WBE should be implemented in real time and become an integral part of future disease surveillance efforts.
Carles, L., Wullschleger, S., Joss, A., Eggen, R. I. L., Schirmer, K., Schuwirth, N., … Tlili, A. (2022). Wastewater microorganisms impact microbial diversity and important ecological functions of stream periphyton. Water Research, 225, 119119 (13 pp.). doi:10.1016/j.watres.2022.119119, Institutional Repository

Effluents of wastewater treatment plants can impact microbial communities in the receiving streams. However, little is known about the role of microorganisms in wastewater as opposed to other wastewater constituents, such as nutrients and micropollutants. We aimed therefore at determining the impact of wastewater microorganisms on the microbial diversity and function of periphyton, key microbial communities in streams. We used a flow-through channel system to grow periphyton upon exposure to a mixture of stream water and unfiltered or ultra-filtered wastewater. Impacts were assessed on periphyton biomass, activities and tolerance to micropollutants, as well as on microbial diversity. Our results showed that wastewater microorganisms colonized periphyton and modified its community composition, resulting for instance in an increased abundance of Chloroflexi and a decreased abundance of diatoms and green algae. This led to shifts towards heterotrophy, as suggested by the changes in nutrient stoichiometry and the increased mineralization potential of carbon substrates. An increased tolerance towards micropollutants was only found for periphyton exposed to unfiltered wastewater but not to ultra-filtered wastewater, suggesting that wastewater microorganisms were responsible for this increased tolerance. Overall, our results highlight the need to consider the role of wastewater microorganisms when studying potential impacts of wastewater on the receiving water body.
Derlon, N., Desmond, P., Rühs, P. A., & Morgenroth, E. (2022). Cross flow frequency determines the physical structure and cohesion of membrane biofilms developed during gravity-driven membrane ultrafiltration of river water: implication for hydraulic resistance. Journal of Membrane Science, 643, 120079 (10 pp.). doi:10.1016/j.memsci.2021.120079, Institutional Repository

We evaluated how intermittent shear influences the physical structure, material properties and hydraulic resistance of membrane biofilms developed during gravity-driven ultrafiltration of river water, with the ultimate goal of increasing the filtration performances. Our results indicate intermittent shear helps slowing-down the flux decline but does not help to increase the level of stabilisation of the permeate flux. After several weeks, the biofilms exposed to different shear regimes were indeed characterised by similar hydraulic resistance. But the characteristic time to achieve a stable flux increased from 7 d to 25d when increasing the shear frequency. Also, most of the hydraulic resistance (up to 95%) was governed by the base layer that remained attached after erosion tests. With increasing exposure to shear conditions, the biofilms became more cohesive and more elastic, thus resisting better to cross flow conditions. Overall, our results demonstrate that engineering membrane biofilms with a desired permeability is not feasible using intermittent shear due to significant adaptability of the biofilms to their hydraulic environment.
Derlon, N., Garcia Villodres, M., Kovács, R., Brison, A., Layer, M., Takács, I., & Morgenroth, E. (2022). Modelling of aerobic granular sludge reactors: the importance of hydrodynamic regimes, selective sludge removal and gradients. Water Science and Technology, 86(3), 410-431. doi:10.2166/wst.2022.220, Institutional Repository

Hydraulic selection is a key feature of aerobic granular sludge (AGS) systems but existing aerobic granular sludge (AGS) models neglect those mechanisms: gradients over reactor height (Hreactor), selective removal of slow settling sludge, etc. This study aimed at evaluating to what extent integration of those additional processes into AGS models is needed, i.e., at demonstrating that model predictions (biomass inventory, microbial activities and effluent quality) are affected by such additional model complexity. We therefore developed a new AGS model that includes key features of full-scale AGS systems: fill-draw operation, selective sludge removal, distinct settling models for flocs/granules. We then compared predictions of our model to those of a fully mixed AGS model. Our results demonstrate that hydraulic selection can be predicted with an assembly of four continuous stirred tank reactors in series together with a correction code for plug-flow. Concentration gradients over the reactor height during settling/plug-flow feeding strongly impact the predictions of aerobic granular sludge models in terms of microbial selection, microbial activities and ultimately effluent quality. Hydraulic selection is a key to predict selection of storing microorganisms (phosphorus-accumulating organisms (PAO) and glycogen-accumulating organisms (GAO)) and in turn effluent quality in terms of total phosphorus, and for predicting effluent solid concentration and dynamic during plug-flow feeding.
Desiante, W. L., Carles, L., Wullschleger, S., Joss, A., Stamm, C., & Fenner, K. (2022). Wastewater microorganisms impact the micropollutant biotransformation potential of natural stream biofilms. Water Research, 217, 118413 (13 pp.). doi:10.1016/j.watres.2022.118413, Institutional Repository

Biotransformation is the most important process removing manmade chemicals from the environment, yet mechanisms governing this essential ecosystem function are underexplored. To understand these mechanisms, we conducted experiments in flow-through systems, by colonizing stream biofilms under different conditions of mixing river water with treated (and ultrafiltered) wastewater. We performed biotransformation experiments with those biofilms, using a set of 75 micropollutants, and could disentangle potential mechanisms determining the biotransformation potential of stream biofilms. We showed that the increased biotransformation potential downstream of wastewater treatment plants that we observed for specific micropollutants contained in household wastewaters (downstream effect) is caused by microorganisms released with the treated effluent, rather than by the in-stream exposure to those micropollutants. Complementary data from 16S rRNA amplicon-sequencing revealed 146 amplicon sequence variants (ASVs) that followed the observed biotransformation patterns. Our results align with findings for community tolerance, and provide clear experimental evidence that microorganisms released with treated wastewater integrate into downstream biofilms and impact crucial ecosystem functions.
Desmond, P., Huisman, K. T., Sanawar, H., Farhat, N. M., Traber, J., Fridjonsson, E. O., … Vrouwenvelder, J. S. (2022). Controlling the hydraulic resistance of membrane biofilms by engineering biofilm physical structure. Water Research, 210, 118031 (14 pp.). doi:10.1016/j.watres.2021.118031, Institutional Repository

The application of membrane technology for water treatment and reuse is hampered by the development of a microbial biofilm. Biofilm growth in micro-and ultrafiltration (MF/UF) membrane modules, on both the membrane surface and feed spacer, can form a secondary membrane and exert resistance to permeation and crossflow, increasing energy demand and decreasing permeate quantity and quality. In recent years, exhaustive efforts were made to understand the chemical, structural and hydraulic characteristics of membrane biofilms. In this review, we critically assess which specific structural features of membrane biofilms exert resistance to forced water passage in MF/UF membranes systems applied to water and wastewater treatment, and how biofilm physical structure can be engineered by process operation to impose less hydraulic resistance (“below-the-pain threshold”). Counter-intuitively, biofilms with greater thickness do not always cause a higher hydraulic resistance than thinner biofilms. Dense biofilms, however, had consistently higher hydraulic resistances compared to less dense biofilms. The mechanism by which density exerts hydraulic resistance is reported in the literature to be dependant on the biofilms’ internal packing structure and EPS chemical composition (e.g., porosity, polymer concentration). Current reports of internal porosity in membrane biofilms are not supported by adequate experimental evidence or by a reliable methodology, limiting a unified understanding of biofilm internal structure. Identifying the dependency of hydraulic resistance on biofilm density invites efforts to control the hydraulic resistance of membrane biofilms by engineering internal biofilm structure. Regulation of biofilm internal structure is possible by alteration of key determinants such as feed water nutrient composition/concentration, hydraulic shear stress and resistance and can engineer biofilm structural development to decrease density and therein hydraulic resistance. Future efforts should seek to determine the extent to which the concept of “biofilm engineering” can be extended to other biofilm parameters such as mechanical stability and the implication for biofilm control/removal in engineered water systems (e.g., pipelines and/or, cooling towers) susceptible to biofouling.
Donati, F., Dente, S. M. R., Li, C., Vilaysouk, X., Froemelt, A., Nishant, R., … Hashimoto, S. (2022). The future of artificial intelligence in the context of industrial ecology. Journal of Industrial Ecology, 26(4), 1175-1181. doi:10.1111/jiec.13313, Institutional Repository

Artificial intelligence (AI) applications and digital technologies (DTs) are increasingly present in the daily lives of citizens, in cities and in industries. These developments generate large amounts of data and enhance analytical capabilities that could benefit the industrial ecology (IE) community and sustainability research in general. With this communication, we would like to address some of the opportunities, challenges, and next steps that could be undertaken by the industrial ecology community in this realm. This article is an adapted summary of the discussion held by experts in industrial ecology, AI, and sustainability during the 2021 Industrial Ecology Day conference session titled "The Future of Artificial Intelligence in the Context of Industrial Ecology." In brief, building on previous studies and communications, we advise the industrial ecology community to: (1) create internal committees and working groups to monitor and coordinate AI applications within and outside the community; (2) promote and ensure transdisciplinary efforts; (3) determine optimal infrastructure and governance of AI for IE to minimize undesired effects; and (4) act on effective representation and on reduction of digital divides.
Faust, V., van Alen, T. A., Op den Camp, H. J. M., Vlaeminck, S. E., Ganigué, R., Boon, N., & Udert, K. M. (2022). Ammonia oxidation by novel "Candidatus Nitrosacidococcus urinae" is sensitive to process disturbances at low pH and to iron limitation at neutral pH. Water Research X, 17, 100157 (11 pp.). doi:10.1016/j.wroa.2022.100157, Institutional Repository

Acid-tolerant ammonia-oxidizing bacteria (AOB) can open the door to new applications, such as partial nitritation at low pH. However, they can also be problematic because chemical nitrite oxidation occurs at low pH, leading to the release of harmful nitrogen oxide gases. In this publication, the role of acid-tolerant AOB in urine treatment was explored. On the one hand, the technical feasibility of ammonia oxidation under acidic conditions for source-separated urine with total nitrogen concentrations up to 3.5 g-N L-1 was investigated. On the other hand, the abundance and growth of acid-tolerant AOB at more neutral pH was explored. Under acidic conditions (pH of 5), ammonia oxidation rates of 500 mg-N L-1 d-1 and 10 g-N g-VSS-1 d-1 were observed, despite high concentrations of 15 mg-N L-1 of the AOB-inhibiting compound nitrous acid and low concentration of 0.04 mg-N L-1 of the substrate ammonia. However, ammonia oxidation under acidic conditions was very sensitive to process disturbances. Even short periods of less than 12 h without oxygen or without influent resulted in a complete cessation of ammonia oxidation with a recovery time of up to two months, which is a problem for low maintenance applications such as decentralized treatment. Furthermore, undesirable nitrogen losses of about 10% were observed. Under acidic conditions, a novel AOB strain was enriched with a relative abundance of up to 80%, for which the name “Candidatus (Ca.) Nitrosacidococcus urinae” is proposed. While Nitrosacidococcus members were present only to a small extent (0.004%) in urine nitrification reactors operated at pH values between 5.8 and 7, acid-tolerant AOB were always enriched during long periods without influent, resulting in an uncontrolled drop in pH to as low as 2.5. Long-term experiments at different pH values showed that the activity of “Ca. Nitrosacidococcus urinae” decreased strongly at a pH of 7, where they were also outcompeted by the acid-sensitive AOB Nitrosomonas halophila. The experiment results showed that the decreased activity of “Ca. Nitrosacidococcus urinae” correlated with the limited availability of dissolved iron at neutral pH.
Faust, V., Gruber, W., Ganigué, R., Vlaeminck, S. E., & Udert, K. M. (2022). Nitrous oxide emissions and carbon footprint of decentralized urine fertilizer production by nitrification and distillation. ACS ES&T Engineering, 2(9), 1745-1755. doi:10.1021/acsestengg.2c00082, Institutional Repository

Combining partial nitrification, granular activated carbon (GAC) filtration, and distillation is a well-studied approach to convert urine into a fertilizer. To evaluate the environmental sustainability of a technology, the operational carbon footprint and therefore nitrous oxide (N2O) emissions should be known, but N2O emissions from urine nitrification have not been assessed yet. Therefore, N2O emissions of a decentralized urine nitrification reactor were monitored for 1 month. During nitrification, 0.4-1.2% of the total nitrogen load was emitted as N2O-N with an average N2O emission factor (EFN2O) of 0.7%. Additional N2O was produced during anoxic storage between nitrification and GAC filtration with an estimated EFN2O of 0.8%, resulting in an EFN2O of 1.5% for the treatment chain. N2O emissions during nitrification can be mitigated by 60% by avoiding low dissolved oxygen or anoxic conditions and nitrite concentrations above 5 mg-N L-1. Minimizing the hydraulic retention time between nitrification and GAC filtration can reduce N2O formation during intermediate storage by 100%. Overall, the N2O emissions accounted for 45% of the operational carbon footprint of 14 kg-CO2,equiv kg-N-1 for urine fertilizer production. Using electricity from renewable sources and applying the proposed N2O mitigation strategies could potentially lower the carbon footprint by 85%.
Grigg, A. R. C., ThomasArrigo, L. K., Schulz, K., Rothwell, K. A., Kaegi, R., & Kretzschmar, R. (2022). Ferrihydrite transformations in flooded paddy soils: rates, pathways, and product spatial distributions. Environmental Science: Processes and Impacts, 24(10), 1867-1882. doi:10.1039/d2em00290f, Institutional Repository

Complex interactions between redox-driven element cycles in soils influence iron mineral transformation processes. The rates and pathways of iron mineral transformation processes have been studied intensely in model systems such as mixed suspensions, but transformation in complex heterogeneous porous media is not well understood. Here, mesh bags containing 0.5 g of ferrihydrite were incubated in five water-saturated paddy soils with contrasting microbial iron-reduction potential for up to twelve weeks. Using X-ray diffraction analysis, we show near-complete transformation of the ferrihydrite to lepidocrocite and goethite within six weeks in the soil with the highest iron(II) release, and slower transformation with higher ratios of goethite to lepidocrocite in soils with lower iron(II) release. In the least reduced soil, no mineral transformations were observed. In soils where ferrihydrite transformation occurred, the transformation rate was one to three orders of magnitude slower than transformation in comparable mixed-suspension studies. To interpret the spatial distribution of ferrihydrite and its transformation products, we developed a novel application of confocal micro-Raman spectroscopy in which we identified and mapped minerals on selected cross sections of mesh bag contents. After two weeks of flooded incubation, ferrihydrite was still abundant in the core of some mesh bags, and as a rim at the mineral–soil interface. The reacted outer core contained unevenly mixed ferrihydrite, goethite and lepidocrocite on the micrometre scale. The slower rate of transformation and uneven distribution of product minerals highlight the influence of biogeochemically complex matrices and diffusion processes on the transformation of minerals, and the importance of studying iron mineral transformation in environmental media.
Gruber, W., Magyar, P. M., Mitrovic, I., Zeyer, K., Vogel, M., von Känel, L., … Mohn, J. (2022). Tracing N2O formation in full-scale wastewater treatment with natural abundance isotopes indicates control by organic substrate and process settings. Water Research X, 15, 100130 (11 pp.). doi:10.1016/j.wroa.2022.100130, Institutional Repository

Nitrous oxide (N2O) dominates greenhouse gas emissions in wastewater treatment plants (WWTPs). Formation of N2O occurs during biological nitrogen removal, involves multiple microbial pathways, and is typically very dynamic. Consequently, N2O mitigation strategies require an improved understanding of nitrogen transformation pathways and their modulating controls. Analyses of the nitrogen (N) and oxygen (O) isotopic composition of N2O and its substrates at natural abundance have been shown to provide valuable information on formation and reduction pathways in laboratory settings, but have rarely been applied to full-scale WWTPs.
Here we show that N-species isotope ratio measurements at natural abundance level, combined with long-term N2O monitoring, allow identification of the N2O production pathways in a full-scale plug-flow WWTP (Hofen, Switzerland). Heterotrophic denitrification appears as the main N2O production pathway under all tested process conditions (0-2 mgO2/l, high and low loading conditions), while nitrifier denitrification was less important, and more variable. N2O production by hydroxylamine oxidation was not observed. Fractional N2O elimination by reduction to dinitrogen (N2) during anoxic conditions was clearly indicated by a concomitant increase in site preference, δ18O(N2O) and δ15N(N2O). N2O reduction increased with decreasing availability of dissolved inorganic N and organic substrates, which represents the link between diurnal N2O emission dynamics and organic substrate fluctuations. Consequently, dosing ammonium-rich reject water under low-organic-substrate conditions is unfavorable, as it is very likely to cause high net N2O emissions.
Our results demonstrate that monitoring of the N2O isotopic composition holds a high potential to disentangle N2O formation mechanisms in engineered systems, such as full-scale WWTP. Our study serves as a starting point for advanced campaigns in the future combining isotopic technologies in WWTP with complementary approaches, such as mathematical modeling of N2O formation or microbial assays to develop efficient N2O mitigation strategies.
Hadengue, B., Morgenroth, E., & Larsen, T. A. (2022). How to get your feet wet: Integrating urban water and building engineering for low-energy domestic hot water systems. Energy and Buildings, 271, 112318 (6 pp.). doi:10.1016/j.enbuild.2022.112318, Institutional Repository

Thanks to intense research efforts, modern low-energy buildings consume only a fraction of the space heating loads of their older counterparts. However, reducing their energy footprint further requires optimization of domestic hot water systems. This is a difficult task, because the relationship between water and energy in domestic systems is intricate and complex. In general, the intrinsic uncertainty and variability of water demand makes the planning and assessment of new technologies challenging, but also risks related for instance to water pathogens like Legionella pneumophila impose trade-offs that diminish the performance of energy-saving measures. In this short communication, we argue that truly sustainable solutions will only be found if a multi-scale, multi-disciplinary mindset is adopted by the community. We show how the collaboration and knowledge integration between experts of various fields, notably urban water specialists and building engineers, is a prerequisite to resolve some of the most pressing issues on the way to optimizing domestic hot water systems. Through concrete examples, we describe how a new, common modeling framework has already triggered the required knowledge integration, and how it could be expanded further to integrate additional disciplines.
Hadengue, B., Morgenroth, E., Larsen, T. A., & Baldini, L. (2022). Performance and dynamics of active greywater heat recovery in buildings. Applied Energy, 305, 117677 (13 pp.). doi:10.1016/j.apenergy.2021.117677, Institutional Repository

In the effort to de-carbonize the building stock, heat pumps are increasingly utilized in Switzerland, with 70% of the fast-growing heat pump market using ambient air as heat source. Inexpensive and easy to implement, these heat pumps are, however, less efficient than their ground- or water-source counterparts. In this modeling study, we aim at increasing the efficiency of air-source heat pumps using domestic greywater-contained heat. We assess the performance improvement relative to standard heat pump configurations across various climates, seasons, building envelopes, and domestic hot water consumption patterns. The results show that the annually-averaged coefficient of performance improves by 4.1% on average - ranging from 0.6% to 7.5%. This efficiency gain translates on average to 1.8 kWh/week of compressor electricity savings. Although attractive due to its simplicity, the proposed open-loop configuration - preheating of an external heat source - only leads to moderate performance improvement of air-source heat pumps. Based on these results, we extensively discuss and compare alternative system configurations and identify several fundamental differences in the heat recovery dynamics of each configuration. We show that closed-loop systems - using greywater as direct heat source - show the largest performance improvement potential, although being more expensive and complex to implement.
Hadengue, B., Morgenroth, E., & Larsen, T. A. (2022). Screening innovative technologies for energy-efficient domestic hot water systems. Journal of Environmental Management, 320, 115713 (9 pp.). doi:10.1016/j.jenvman.2022.115713, Institutional Repository

Domestic hot water systems are large energy consumers. With the aim of reducing the energy footprint of these systems, we selected and simulated five technologies across a wide range of technology readiness levels: established technologies - pipe insulation and low-flow faucets -, relatively new technologies - shower drain heat exchangers and an innovative pipe system - and a novel experimental technology - a heat exchanger connected to membrane bioreactor for on-site greywater treatment. Using the WaterHub modeling framework, we simulated the technologies alone and in combination and compared the energetic performance of fifteen scenarios with a validated reference domestic hot water system. Low-flow appliances as standalone technologies performed best with 30% less energy required for the boiler tank, but combining low-flow appliances with a membrane bioreactor heat exchanger performed best overall (50% reduction). Deep insights into the temperature dynamics at all locations in the system led to the identification of technological competition patterns to prevent and synergies to exploit. Through our results, we are able to discuss and recommend further investigations regarding critical aspects like hygiene and economic performance.
Hausherr, D., Niederdorfer, R., Bürgmann, H., Lehmann, M. F., Magyar, P., Mohn, J., … Joss, A. (2022). Successful mainstream nitritation through NOB inactivation. Science of the Total Environment, 822, 153546 (11 pp.). doi:10.1016/j.scitotenv.2022.153546, Institutional Repository

The development of new wastewater treatment processes can assist in reducing the impact of wastewater treatment on the environment. The recently developed partial nitritation anammox (PNA) process, for example, consumes less energy for aeration and reduces nitrate in the effluent without requiring additional organic carbon. However, achieving stable nitritation (ammonium oxidation; NH4+ → NO2−) at mainstream conditions (T = 10–25 °C, C:N > 10, influent ammonium < 50 mgNH4-N/L and effluent < 1 mgNH4-N/L) remains challenging. This study explores the potential and mechanism of nitrite-oxidizing bacteria (NOB) suppression in a bottom-fed sequencing batch reactor (SBR). Two bench-scale (11 L) reactors and a pilot-scale reactor (8 m3) were operated for over a year and were fed with organic substrate depleted municipal wastewater. Initially, nitratation (nitrite oxidation; NO2− → NO3−) occurred occasionally until an anaerobic phase was integrated into the operating cycle. The introduction of the anaerobic phase effectively suppressed the regrowth of NOB while nitritation was stable over 300 days, down to 8 °C and at ammonium influent concentrations < 25 mgNH4-N/L. Batch experiments and process data revealed that parameters typically affecting NOB growth (e.g., dissolved oxygen, alkalinity, trace elements, lag-phase after anoxia, free nitrous acid (FNA), free ammonia (FA), pH, sulfide, or solids retention time (SRT)) could not fully explain the suppression of nitratation. Experiments in which fresh nitrifying microbial biomass was added to the nitritation system indicated that NOB inactivation explained NOB suppression better than NOB washout at high SRT. This study concludes that bottom-fed SBRs with anaerobic phases allow for stable nitritation over a broad range of operational parameters. Coupling this type of SBR to an anammox reactor can enable efficient mainstream anammox-based wastewater treatment.
Hausherr, D., Niederdorfer, R., Bürgmann, H., Lehmann, M. F., Magyar, P., Mohn, J., … Joss, A. (2022). Successful year-round mainstream partial nitritation anammox: assessment of effluent quality, performance and N2O emissions. Water Research X, 16, 100145 (11 pp.). doi:10.1016/j.wroa.2022.100145, Institutional Repository

For two decades now, partial nitritation anammox (PNA) systems were suggested to more efficiently remove nitrogen (N) from mainstream municipal wastewater. Yet to date, only a few pilot-scale systems and even fewer full-scale implementations of this technology have been described. Process instability continues to restrict the broad application of PNA. Especially problematic are insufficient anammox biomass retention, the growth of undesired aerobic nitrite-oxidizers, and nitrous oxide (N2O) emissions. In this study, a two-stage mainstream pilot-scale PNA system, consisting of three reactors (carbon pre-treatment, nitritation, anammox - 8 m3 each), was operated over a year, treating municipal wastewater. The aim was to test whether both, robust autotrophic N removal and high effluent quality, can be achieved throughout the year. A second aim was to better understand rate limiting processes, potentially affecting the overall performance of PNA systems. In this pilot study, excellent effluent quality, in terms of inorganic nitrogen, was accomplished (average effluent concentrations: 0.4 mgNH4-N/L, 0.1 mgNO2-N/L, 0.9 mgNO3-N/L) even at wastewater temperatures previously considered problematic (as low as 8 °C). N removal was limited by nitritation rates (84 ± 43 mgNH4-N/L/d), while surplus anammox activity was observed at all times (178 ± 43 mgN/L/d). Throughout the study, nitrite-oxidation was maintained at a low level (<2.5% of ammonium consumption rate). Unfortunately, high N2O emissions from the nitritation stage (1.2% of total nitrogen in the influent) were observed, and, based on natural isotope abundance measurements, could be attributed to heterotrophic denitrification. In situ batch experiments were conducted to identify the role of dissolved oxygen (DO) and organic substrate availability in N2O emission-mitigation. The addition of organic substrate, to promote complete denitrification, was not successful in decreasing N2O emission, but increasing the DO from 0.3 to 2.9 mgO2/L decreased N2O emissions by a factor of 3.4.
Huisman, J. S., Scire, J., Caduff, L., Fernandez-Cassi, X., Ganesanandamoorthy, P., Kull, A., … Julian, T. R. (2022). Wastewater-based estimation of the effective reproductive number of SARS-CoV-2. Environmental Health Perspectives, 130(5), 057011 (12 pp.). doi:10.1289/EHP10050, Institutional Repository

BACKGROUND: The effective reproductive number, Re, is a critical indicator to monitor disease dynamics, inform regional and national policies, and estimate the effectiveness of interventions. It describes the average number of new infections caused by a single infectious person through time. To date, Re estimates are based on clinical data such as observed cases, hospitalizations, and/or deaths. These estimates are temporarily biased when clinical testing or reporting strategies change.
OBJECTIVES: We show that the dynamics of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) RNA in wastewater can be used to estimate Re in near real time, independent of clinical data and without the associated biases.
METHODS: We collected longitudinal measurements of SARS-CoV-2 RNA in wastewater in Zurich, Switzerland, and San Jose, California, USA. We combined this data with information on the temporal dynamics of shedding (the shedding load distribution) to estimate a time series proportional to the daily COVID-19 infection incidence. We estimated a wastewater-based Re from this incidence.
RESULTS: The method to estimate Re from wastewater worked robustly on data from two different countries and two wastewater matrices. The resulting estimates were as similar to the Re estimates from case report data as Re estimates based on observed cases, hospitalizations, and deaths are among each other. We further provide details on the effect of sampling frequency and the shedding load distribution on the ability to infer Re.
DISCUSSION: To our knowledge, this is the first time Re has been estimated from wastewater. This method provides a low-cost, rapid, and independent way to inform SARS-CoV-2 monitoring during the ongoing pandemic and is applicable to future wastewater-based epidemiology targeting other pathogens.
Jahn, K., Dreifuss, D., Topolsky, I., Kull, A., Ganesanandamoorthy, P., Fernandez-Cassi, X., … Beerenwinkel, N. (2022). Early detection and surveillance of SARS-CoV-2 genomic variants in wastewater using COJAC. Nature Microbiology, 7, 1151-1160. doi:10.1038/s41564-022-01185-x, Institutional Repository

The continuing emergence of SARS-CoV-2 variants of concern and variants of interest emphasizes the need for early detection and epidemiological surveillance of novel variants. We used genomic sequencing of 122 wastewater samples from three locations in Switzerland to monitor the local spread of B.1.1.7 (Alpha), B.1.351 (Beta) and P.1 (Gamma) variants of SARS-CoV-2 at a population level. We devised a bioinformatics method named COJAC (Co-Occurrence adJusted Analysis and Calling) that uses read pairs carrying multiple variant-specific signature mutations as a robust indicator of low-frequency variants. Application of COJAC revealed that a local outbreak of the Alpha variant in two Swiss cities was observable in wastewater up to 13 d before being first reported in clinical samples. We further confirmed the ability of COJAC to detect emerging variants early for the Delta variant by analysing an additional 1,339 wastewater samples. While sequencing data of single wastewater samples provide limited precision for the quantification of relative prevalence of a variant, we show that replicate and close-meshed longitudinal sequencing allow for robust estimation not only of the local prevalence but also of the transmission fitness advantage of any variant. We conclude that genomic sequencing and our computational analysis can provide population-level estimates of prevalence and fitness of emerging variants from wastewater samples earlier and on the basis of substantially fewer samples than from clinical samples. Our framework is being routinely used in large national projects in Switzerland and the UK.
Kim, A., Mutel, C. L., Froemelt, A., & Hellweg, S. (2022). Global sensitivity analysis of background life cycle inventories. Environmental Science and Technology, 56(9), 5874-5885. doi:10.1021/acs.est.1c07438, Institutional Repository

In recent years many Life Cycle Assessment (LCA) studies have been conducted to quantify the environmental performance of products and services. Some of these studies propagated numerical uncertainties in underlying data to LCA results, and several applied Global Sensitivity Analysis (GSA) to some parts of the LCA model to determine its main uncertainty drivers. However, only a few studies have tackled the GSA of complete LCA models due to the high computational cost of such analysis and the lack of appropriate methods for very high-dimensional models. This study proposes a new GSA protocol suitable for large LCA problems that, unlike existing approaches, does not make assumptions on model linearity and complexity and includes extensive validation of GSA results. We illustrate the benefits of our protocol by comparing it with an existing method in terms of filtering of noninfluential and ranking of influential uncertainty drivers and include an application example of Swiss household food consumption. We note that our protocol obtains more accurate GSA results, which leads to better understanding of LCA models, and less data collection efforts to achieve more robust estimation of environmental impacts. Implementations supporting this work are available as free and open source Python packages.
Kocic, J., Dirin, D. N., Kägi, R., Kovalenko, M. V., Günther, D., & Hattendorf, B. (2022). Direct analysis of nanoparticles in organic solvents by ICPMS with microdroplet injection. Journal of Analytical Atomic Spectrometry, 37(8), 1738-1750. doi:10.1039/d1ja00358e, Institutional Repository

In recent years, the capabilities for characterizing inorganic nanoparticles (NPs) in aqueous solvents with respect to their elemental composition, mass and particle number concentration have been expanded using single particle inductively coupled plasma mass spectrometry (sp-ICPMS). However, NPs with high monodispersity, size, shape and surface chemistry control are frequently synthesized using hot-injection methods, utilizing hydrophobic organic ligands which are only soluble in non-polar organic solvents. Due to several instrumental limitations, suspensions in organic solvents are not commonly analysed by sp-ICPMS. In this study, we investigated the direct introduction of toluene and mesitylene into an ICPMS using a microdroplet generator. With this configuration the solvent load in the ICP is substantially reduced and soot formation, causing instrumental drift, was minimized while maintaining a transport efficiency (TE) of 100%. Furthermore, the effect of different vacuum interface configurations and the addition of oxygen or nitrogen on the detection efficiency (DE) and instrumental background signals was investigated for Al, Si, Ti, Fe Cu, Ag, Cd, and Pb. The highest DE was obtained for a “Jet” interface with the addition of nitrogen at a flow rate of 10 mL min−1, resulting in an increase by a factor of 2-8 depending on the element. The lowest detectable mass, based on counting statistics, was 1.4 ag for Pb, which corresponds to a diameter of 6.1 nm of a spherical, metallic NP. The approach can not only be used for NP characterization, but also holds promise for the sensitive determination of trace elements in organic solvents.
Lamprecht, O., Wagner, B., Derlon, N., & Tlili, A. (2022). Synthetic periphyton as a model system to understand species dynamics in complex microbial freshwater communities. npj Biofilms and Microbiomes, 8, 61 (14 pp.). doi:10.1038/s41522-022-00322-y, Institutional Repository

Phototrophic biofilms, also known as periphyton, are microbial freshwater communities that drive crucial ecological processes in streams and lakes. Gaining a deep mechanistic understanding of the biological processes occurring in natural periphyton remains challenging due to the high complexity and variability of such communities. To address this challenge, we rationally developed a workflow to construct a synthetic community by co-culturing 26 phototrophic species (i.e., diatoms, green algae, and cyanobacteria) that were inoculated in a successional sequence to create a periphytic biofilm on glass slides. We show that this community is diverse, stable, and highly reproducible in terms of microbial composition, function, and 3D spatial structure of the biofilm. We also demonstrate the ability to monitor microbial dynamics at the single species level during periphyton development and how their abundances are impacted by stressors such as increased temperature and a herbicide, singly and in combination. Overall, such a synthetic periphyton, grown under controlled conditions, can be used as a model system for theory testing through targeted manipulation.
Layer, M., Brison, A., Garcia Villodres, M., Stähle, M., Házi, F., Takács, I., … Derlon, N. (2022). Microbial conversion pathways of particulate organic substrate conversion of aerobic granular sludge systems: limited anaerobic conversion and the essential role of flocs. Environmental Science: Water Research and Technology, 8(6), 1236-1251. doi:10.1039/D1EW00841B, Institutional Repository

Particulate organic substrate (XB) represents the major fraction of organic substrate in low-strength municipal wastewater (MWW) but its hydrolysis, conversion and utilisation in aerobic granular sludge (AGS) are not well understood. We systematically analysed through modelling the microbial conversion pathways of XB in AGS systems operated as sequencing batch reactors and treating municipal wastewater. Based on our current understanding of AGS systems, we developed an AGS model in Sumo® to better understand (1) during which phases of the SBR cycle (anaerobic plug-flow feeding or aerobic fully-mixed conditions), (2) by what biomass fraction (granules or flocs) and (3) via which microbial processes XB is converted into soluble organic substrate (SB) and volatile fatty acids (SVFA) and further utilised. The validity of all our results was evaluated by assessing the sensitivity of findings on the biomass distribution (floc fraction) (SCENARIO #1), SBR cycle (SCENARIO #2), and biofilm properties (SCENARIO #3). Our results indicate that only 20% of influent XB was hydrolysed and 11% of influent XB was then used for internal carbon-storage during 90 min anaerobic plug-flow feeding. The major fraction of influent XB (80%) leaked into the aerobic SBR phase, where XB was then hydrolysed and oxidised aerobically by ordinary heterotrophic organisms (OHOs). Under aerobic fully-mixed conditions, the flocs successfully competed for XB with the granules. Aerobic XB hydrolysis and its further utilisation by OHOs occurred mainly in flocs despite their minor biomass fraction (13% of total suspended solids), preventing excessive OHO growth on granules and demonstrating that flocs are beneficial for AGS systems treating MWW. Also, the model allowed us to better understand that the SBR sequence can be optimised to make better use of XB under anaerobic conditions and to reduce the leakage of XB to aerobic conditions. The introduction of a 60 min anaerobic idle phase after a 60 min plug-flow feeding phase almost doubled the anaerobic XB hydrolysis and internal carbon-storage by phosphorus and glycogen accumulating organisms (PAOs and GAOs), respectively, compared to 90 min plug-flow feeding. Nonetheless, most influent XB was still utilised by OHOs during the aerobic SBR phase.
Murazzi, M. E., Cherubini, P., Brunner, I., Kägi, R., Saurer, M., Ballikaya, P., … Gessler, A. (2022). Can forest trees take up and transport nanoplastics?. iForest, 15(2), 128-132. doi:10.3832/ifor4021-015, Institutional Repository

Plastic contamination of ecosystems has increased dramatically over the last decades, raising concerns about the negative impacts of plastic particles on aquatic and terrestrial systems. In recent years, the focus of most research has shifted from large fragments (macroplastic) to micro- (<5 mm) and more recently to nano-plastic (<1000 nm) particles as more evidence has come to light about their ubiquity in water, soils, and living systems, and their effects on ecosystem and human health. In this study, we investigate nanoplastic uptake in the roots of seedlings (1-2 years old) of three different tree species and assess their transport to different tissues. Parts of the main roots of silver birch (Betula pendula Roth), sessile oak (Quercus petraea Matt. [Liebl.]), and Norway spruce (Picea abies [L.] Karst.) were immersed for one or four days in a suspension containing 13C-labelled nano-sized polystyrene particles (13C-nPS; 99% 13C, d = 28 ± 8 (1 σ) nm). Carbon stable isotope analysis showed significant 13C enrichment (P < 0.05) in the immersed part of the root after one day of treatment in all three species, and after four days in Q. petraea alone. Signals of significant 13C enrichment were also found in the aboveground tissues of the trees. The stem of B. pendula in particular showed a significant 13C enrichment after one day of treatment (P < 0.01). This indicates that nanoplastic particles can be taken up through tree roots into the tree’s central cylinder, where they are subsequently conveyed through the tree by acropetal transport via the xylem.
Notini, L., ThomasArrigo, L. K., Kaegi, R., & Kretzschmar, R. (2022). Coexisting goethite promotes Fe(II)-catalyzed transformation of ferrihydrite to goethite. Environmental Science and Technology, 56(17), 12723-12733. doi:10.1021/acs.est.2c03925, Institutional Repository

In redox-affected soil environments, electron transfer between aqueous Fe(II) and solid-phase Fe(III) catalyzes mineral transformation and recrystallization processes. While these processes have been studied extensively as independent systems, the coexistence of iron minerals is common in nature. Yet it remains unclear how coexisting goethite influences ferrihydrite transformation. Here, we reacted ferrihydrite and goethite mixtures with Fe(II) for 24 h. Our results demonstrate that with more goethite initially present in the mixture more ferrihydrite turned into goethite. We further used stable Fe isotopes to label different Fe pools and probed ferrihydrite transformation in the presence of goethite using 57Fe Mössbauer spectroscopy and changes in the isotopic composition of solid and aqueous phases. When ferrihydrite alone underwent Fe(II)-catalyzed transformation, Fe atoms initially in the aqueous phase mostly formed lepidocrocite, while those from ferrihydrite mostly formed goethite. When goethite was initially present, more goethite was formed from atoms initially in the aqueous phase, and nanogoethite formed from atoms initially in ferrihydrite. Our results suggest that coexisting goethite promotes formation of more goethite via Fe(II)-goethite electron transfer and template-directed nucleation and growth. We further hypothesize that electron transfer onto goethite followed by electron hopping onto ferrihydrite is another possible pathway to goethite formation. Our findings demonstrate that mineral transformation is strongly influenced by the composition of soil solid phases.
Philipp, M., Bucheli, T. D., & Kaegi, R. (2022). The use of surrogate standards as a QA/QC tool for routine analysis of microplastics in sewage sludge. Science of the Total Environment, 835, 155485 (9 pp.). doi:10.1016/j.scitotenv.2022.155485, Institutional Repository

The efficient retention of microplastic particles (MP) during wastewater treatment results in their accumulation in the sewage sludge. Thus, sewage sludge represents a key matrix for understanding MP flows between engineered and natural systems. Building on previous reports, we present a sample preparation protocol optimized for digested sewage sludge. The key steps include acid digestion supported by Fenton reagents, enzymatic digestion, and density separation using sodium polytungstate (density of 1.9 gcm−3). We use colored polyethylene (PE) spheres as surrogate standards to assess sample specific recoveries in terms of number and size, based on visible light (vis) microscopy and focal plane array - micro-Fourier transform - infrared (FPA-μ-FT-IR) imaging. The FT-IR spectra of common MP were identical before and after the digestion procedures and morphological changes were observed for polylactide fibers only. Average recovery rates for PE spheres, polypropylene fibers and polyethylene terephthalate fragments extracted from spiked digested sewage sludge and determined using (automated) vis microscopy ranged from 80% to 100%. Similar recovery rates of around 80% were also obtained for PE spheres based on FPA-μ-FT-IR measurements. The median diameters of red and blue PE spheres in dry state and recovered from spiked deionized water and from extracts of spiked digested sewage sludge determined using vis microscopy ranged between 46 μm and 67 μm. These diameters were similar to 54 μm and 61 μm obtained from the FPA-μ-FT-IR measurements of the corresponding deionized water samples and digested sludge extracts and in line with data from the producer (53 μm–63 μm). Using our digestion protocol in combination with surrogate standards, we measured MP number concentrations of around 10,000 #/g in dried, digested sewage sludge, in agreement with recent results from other studies.
Pulido-Reyes, G., Magherini, L., Bianco, C., Sethi, R., von Gunten, U., Kaegi, R., & Mitrano, D. M. (2022). Nanoplastics removal during drinking water treatment: laboratory- and pilot-scale experiments and modeling. Journal of Hazardous Materials, 436, 129011 (13 pp.). doi:10.1016/j.jhazmat.2022.129011, Institutional Repository

Microplastics detected in potable water sources and tap water have led to concerns about the efficacy of current drinking water treatment processes to remove these contaminants. It is hypothesized that drinking water resources contain nanoplastics (NPs), but the detection of NPs is challenging. We, therefore, used palladium (Pd)-labeled NPs to investigate the behavior and removal of NPs during conventional drinking water treatment processes including ozonation, sand and activated carbon filtration. Ozone doses typically applied in drinking water treatment plants (DWTPs) hardly affect the NPs transport in the subsequent filtration systems. Amongst the different filtration media, NPs particles were most efficiently retained when aged (i.e. biofilm coated) sand was used with good agreements between laboratory and pilot scale systems. The removal of NPs through multiple filtration steps in a municipal full-scale DWTP was simulated using the MNMs software code. Removal efficiencies exceeding 3-log units were modeled for a combination of three consecutive filtration steps (rapid sand filtration, activated carbon filtration and slow sand filtration with 0.4-, 0.2- and 3.0-log-removal, respectively). According to the results from the model, the removal of NPs during slow sand filtration dominated the overall NPs removal which is also supported by the laboratory-scale and pilot-scale data. The results from this study can be used to estimate the NPs removal efficiency of typical DWTPs with similar water treatment chains.
Randall, D. G., Brison, A., & Udert, K. M. (2022). High temperatures and CO2 dissolution can cause nitrogen losses from urine stabilized with base. Frontiers in Environmental Science, 10, 998743 (13 pp.). doi:10.3389/fenvs.2022.998743, Institutional Repository

Human urine is rich in valuable nitrogen which can easily be lost due to biological urea hydrolysis and subsequent ammonia volatilization. While this enzymatic reaction can be prevented by alkalizing the urine, recent studies suggest that chemical urea hydrolysis can result in substantial nitrogen losses when drying alkalinized urine at high temperatures. Furthermore, it was previously suggested that CO2 dissolution from the air used to evaporate water from alkalinized urine could result in a pH decrease to values which allows for biological urea hydrolysis and subsequent ammonia losses. This study aimed to determine the kinetics of chemical urea hydrolysis in alkalinized human urine and confirm the effect of CO2 dissolution with controlled laboratory experiments. We measured the change in urea concentration at different temperatures and pH values for real human urine and determined the corresponding rate constants for chemical urea hydrolysis. We showed that the rate constant increases as a function of temperature and that pH has a negligible effect on the rate of chemical urea hydrolysis in the high pH range of alkalized urine (>11). The rate constants for chemical urea hydrolysis in a saturated calcium hydroxide solution were found to be 0.00147 d-1, 0.00595 d-1, 0.0204 d-1 and 0.0848 d-1 for temperatures of 25°C, 40°C, 55°C and 70°C, respectively. The effect of CO2 dissolution on urea hydrolysis was determined by aerating human urine alkalinized with calcium hydroxide (Ca(OH)2). In order to represent biological urea hydrolysis, urease was added to the solution. The computer simulations of the experimental results showed that CO2 dissolution and the subsequent dissociation of carbonic acid to carbonate ions, bicarbonate ions and protons is the main cause of the pH decrease, but CaCO3 precipitation, and NH3 volatilization foster the pH decrease. However, biological urea hydrolysis prevents the pH from decreasing below 9. Residual undissolved Ca(OH)2 was shown to substantially delay the pH decrease. Overall, this work provides valuable insights into the mechanisms of urea hydrolysis in alkalinized urine during dehydration, which can be used to design more efficient decentralized sanitation systems and minimize nitrogen losses.
Rhein, F., Nirschl, H., & Kaegi, R. (2022). Separation of microplastic particles from sewage sludge extracts using magnetic seeded filtration. Water Research X, 17, 100155 (11 pp.). doi:10.1016/j.wroa.2022.100155, Institutional Repository

Microplastic particles (MP) are efficiently retained in wastewater treatment plants and enriched in sewage sludge. For monitoring MP contents in wastewater systems, sewage sludge is thus well suited, but also requires an isolation of MP from the sludge matrix, as other sewage sludge components may interfere with the MP identification and quantification. Although organic matter in sludge samples can be removed through acid and enzymatic digestion procedures, cellulose - mainly from toilet paper - remains in the digests, due to its high chemical resistivity and similar density to MP. We apply the separation concept of magnetic seeded filtration to isolate MP through selective hetero-agglomeration with magnetic seed particles. MP and cellulose differ in their hydrophobic properties and we investigate to what extent these differences can be exploited to selectively form MP-magnetite hetero-agglomerates in the presence of cellulose. These hetero-agglomerates are subsequently separated using a magnet. Five MP types (Polyethylene terephthalate (PET), polypropylene (PP), low density polyethylene (LDPE), polyvinyl chloride (PVC) and polystyrene (PS)) and cellulose particles were mixed in different combinations with both hydrophilic and hydrophobic (silanized) magnetite particles. PET, PP, LDPE and PS only poorly agglomerated with pristine (hydrophilic) magnetite, but efficiently formed hetero-agglomerates with hydrophobic magnetite and were successfully removed from suspensions (80 - 100 %). PVC agglomerated more efficiently with pristine than with hydrophobic magnetite and cellulose only agglomerated to a limited extent with either hydrophilic or hydrophobic magnetite, resulting in a high process selectivity. Results from experiments conducted at different ionic strengths and with hydrophilic and hydrophobic magnetite suggests that the agglomeration process was dominated by hydrophobic interactions. Enzymatic and oxidative treatment of the MP only marginally affected the separation efficiencies and (treated) MP spiked to sewage sludge extracts were successfully recovered using magnetic seeded filtration.
Sam, S. B., Ward, B. J., Niederdorfer, R., Morgenroth, E., & Strande, L. (2022). Elucidating the role of extracellular polymeric substances (EPS) in dewaterability of fecal sludge from onsite sanitation systems, and changes during anaerobic storage. Water Research, 222, 118915 (12 pp.). doi:10.1016/j.watres.2022.118915, Institutional Repository

As the importance of fecal sludge management (FSM) is increasingly being realized, the need for adequately designed and functioning fecal sludge (FS) treatment plants is also increasing. Research to fill this gap is only emerging and dewatering is a key challenge for developing sustainable treatment solutions. This study evaluated the effect of extracellular polymeric substances (EPS) on dewaterability of FS, and how EPS and dewaterability change during anaerobic storage (as a proxy for time in onsite containment). EPS was extracted from FS and activated sludge using Na2CO3 and sonication and added to sludge samples to determine the effect on dewaterability. The results confirmed that an increase in EPS had a direct impact of decreasing FS dewaterability (as capillary suction time). In this context, we evaluated FS degradation during anaerobic storage, the effect of anaerobic storage time on EPS, EPS fractions and particle size distribution, and the effect of variations in these factors on FS dewaterability. Variations in EPS, EPS fraction and particle size distribution during anaerobic storage were less than expected and average VS reduction of 20% was recorded over 7 weeks. Although anaerobic digestion was verified (biogas production), the results indicate that kinetics of degradation of FS is different from wastewater sludges. Comparatively, EPS fractions in FS were 70 – 75% lower and with higher fractions of humic-like substances than wastewater sludges. Although EPS significantly affects FS dewaterability, anaerobic storage time is not a predictor of dewaterability.
Schneider, M. Y., Quaghebeur, W., Borzooei, S., Froemelt, A., Li, F., Saagi, R., … Torfs, E. (2022). Hybrid modelling of water resource recovery facilities: status and opportunities. Water Science and Technology, 85(9), 2503-2524. doi:10.2166/wst.2022.115, Institutional Repository

Mathematical modelling is an indispensable tool to support water resource recovery facility (WRRF) operators and engineers with the ambition of creating a truly circular economy and assuring a sustainable future. Despite the successful application of mechanistic models in the water sector, they show some important limitations and do not fully profit from the increasing digitalisation of systems and processes. Recent advances in data-driven methods have provided options for harnessing the power of Industry 4.0, but they are often limited by the lack of interpretability and extrapolation capabilities. Hybrid modelling (HM) combines these two modelling paradigms and aims to leverage both the rapidly increasing volumes of data collected, as well as the continued pursuit of greater process understanding. Despite the potential of HM in a sector that is undergoing a significant digital and cultural transformation, the application of hybrid models remains vague. This article presents an overview of HM methodologies applied to WRRFs and aims to stimulate the wider adoption and development of HM. We also highlight challenges and research needs for HM design and architecture, good modelling practice, data assurance, and software compatibility. HM is a paradigm for WRRF modelling to transition towards a more resource-efficient, resilient, and sustainable future.
Schwarzfischer, M., Niechcial, A., Lee, S. S., Sinnet, B., Wawrzyniak, M., Laimbacher, A., … Spalinger, M. R. (2022). Ingested nano- and microsized polystyrene particles surpass the intestinal barrier and accumulate in the body. NanoImpact, 25, 100374 (9 pp.). doi:10.1016/j.impact.2021.100374, Institutional Repository

Plastic pollution is a major global challenge of our times, baring a potential threat for the environment and the human health. The increasing abundance of nanoplastic (NP) and microplastic (MP) particles in the human diet might negatively affect human health since they - particularly in patients suffering from inflammatory bowel disease (IBD) – might surpass the intestinal barrier. To investigate whether ingested plastic particles cross the intestinal epithelium and promote bowel inflammation, mice were supplemented with NP or MP polystyrene (PS) particles for 24 or 12 weeks before inducing acute or chronic dextran sodium sulfate (DSS) colitis with continuous plastic administration. Although ingested PS particles accumulated in the small intestine and organs distant from the gastrointestinal tract, PS ingestion did not affect intestinal health nor did it promote colitis severity. Although the lack of colitis-promoting effects of small PS particles might be a relief for IBD patients, potential accumulative effects of ingested plastic particles on the gastrointestinal health cannot be excluded.
Stamm, C., Binder, C. R., Frossard, E., Haygarth, P. M., Oberson, A., Richardson, A. E., … Udert, K. M. (2022). Towards circular phosphorus: the need of inter- and transdisciplinary research to close the broken cycle. Ambio, 51, 611-622. doi:10.1007/s13280-021-01562-6, Institutional Repository

Phosphorus (P) is an essential element to all living beings but also a finite resource. P-related problems center around broken P cycles from local to global scales. This paper presents outcomes from the 9th International Phosphorus Workshop (IPW9) held 2019 on how to move towards a sustainable P management. It is based on two sequential discussion rounds with all participants. Important progress was reported regarding the awareness of P as finite mineable resource, technologies to recycle P, and legislation towards a circular P economy. Yet, critical deficits were identified such as how to handle legacy P, how climate change may affect ecosystem P cycling, or working business models to up-scale existing recycling models. Workshop participants argued for more transdisciplinary networks to narrow a perceived science-practice/policy gap. While this gap may be smaller in reality as illustrated with a Swiss example, we formulate recommendations how to bridge this gap more effectively.
Stetten, L., Hofmann, T., Proux, O., Landrot, G., Kaegi, R., & von der Kammer, F. (2022). Transformation of zinc oxide nanoparticles in freshwater sediments under oxic and anoxic conditions. Environmental Science: Nano, 9(11), 4255-4267. doi:10.1039/d2en00709f, Institutional Repository

The transformation of zinc oxide nanoparticles (ZnO NPs) has been largely investigated in wastewater treatment plants, recognized as important intermediates before the discharge of NPs into the environment. However, considering direct releases of the pristine ZnO NP forms, additional studies on ZnO NP fate in different environmental compartments are encouraged. In this work, we investigated ZnO NP transformation in lacustrine sediments under defined redox conditions. Using X-ray absorption spectroscopy and wet chemical analyses, we followed ZnO NP and Zn2+ fate over a three-month period in sediments incubated under oxic or anoxic sulfide-rich conditions. Under oxic conditions, ZnO NPs were dissolved within a few hours. By contrast, ZnO NP dissolution under anoxic conditions was much slower, with ∼19% of ZnO NPs remaining at the end of the incubation, together with ∼41% of ZnS, ∼15% of Zn adsorbed onto phyllosilicates and ∼27% of Zn-phyllosilicate-like species. The transient formation of Zn–organic complexes under oxic conditions supports that ZnO NP dissolution is driven by organic compounds, followed by Zn adsorption onto phyllosilicates and the subsequent formation of Zn-layered minerals. Under anoxic conditions, ZnO NP dissolution is inhibited by the precipitation of amorphous ZnS and controlled by the progressive growth of ZnS NPs. These results improve the understanding of ZnO NP transformation in slightly alkaline freshwater sediments and highlight the need to assess NP fate under environmentally relevant conditions.
Stoffel, D., Rigo, E., Derlon, N., Staaks, C., Heijnen, M., Morgenroth, E., & Jacquin, C. (2022). Low maintenance gravity-driven membrane filtration using hollow fibers: effect of reducing space for biofilm growth and control strategies on permeate flux. Science of the Total Environment, 811, 152307 (13 pp.). doi:10.1016/j.scitotenv.2021.152307, Institutional Repository

The implementation of centralized drinking water treatment systems necessitates lower operational costs and improved biopolymer removal during ultrafiltration (UF), which can be afforded by gravity-driven membrane (GDM) filtration. However, prior to implementing GDM filtration in centralized systems, biofilm growth in compacted membrane configurations, such as inside-out hollow fiber (HF), and its impact on permeate flux need to be investigated. To this end, we operated modules with distinct limits on available space for biofilm growth: (1) outside-in 1.5 mm 7-capillary HF (non-limited), (2) inside-out 1.5 mm 7-capillary HF (limited), and (3) inside-out 0.9 mm 7-capillary HF (very limited). Here, we observed that the lower the space available for biofilm growth, the lower the permeate flux. To improve GDM performance with inside-out HF, we applied daily shear stress to the biofilm surface with forward flush (FF) or combined relaxation and forward flush (R+FF). We showed that applying shear stress to the biofilm surface was insufficient for controlling flux loss due to low available space for biofilm growth. At the experimental endpoint, we backwashed with a stepwise transmembrane pressure (TMP) increase or a single TMP on all inside-out HF modules, which removed the biofilm from its base. Afterwards, higher fluxes were yielded. We also showed that all modules exhibited a gradual increase in biopolymer removal followed by stabilization between 70 and 90%. Additionally, control of biofilm growth with surface shear stress did not affect biopolymer removal. In summary, the implementation of inside-out HF with GDM filtration is challenged by low available space for biofilm growth, but may be remedied with a regular backwash to remove biofilm from its base. We showed that a wider range of GDM applications are available; making GDM potentially compatible with implementation in centralized systems, if space limitation is taken into consideration for operation optimization.
Szakas, S. E., Lancaster, R., Kaegi, R., & Gundlach-Graham, A. (2022). Quantification and classification of engineered, incidental, and natural cerium-containing particles by spICP-TOFMS. Environmental Science: Nano, 9, 1627-1638. doi:10.1039/d1en01039e, Institutional Repository

Cerium containing nanoparticles (Ce-NPs) from geogenic and anthropogenic sources are frequently found in the environment, and the ability to determine the origins of Ce-NPs relies on the presence of other rare earth elements (REEs), such as La. In this study, we develop a scheme to classify individual natural, incidental, and engineered Ce-containing particles using spICP-TOFMS. Well-characterized CeO2 engineered particles (Ce-ENPs), incidental particles (Ce-INPs) from ferrocerium mischmetal, and natural particles (Ce-NNPs) from ground minerals (bastnaesite and parisite) are used as a model particle system. Based on mixtures of these three Ce-NP types, we demonstrate that the measured signals of Ce, La, and Nd in Ce-NNPs follow Poisson statistics and have conserved element ratios. The Ce-INPs we measure have similar Ce : La mass ratios to those of the Ce-NNPs, and Ce : Nd mass ratios can be used to distinguish these two Ce-NP types. Based on this, we develop particle-type-specific detection limits (LD,sp) for the measurement of La and Nd in Ce-NNPs. Our approach establishes LD,sp values with defined confidence intervals to control false-positive particle-type assignments, and allows us to accurately classify engineered, incidental, and natural Ce-NPs down to effective spherical diameters of 32, 35, and 45 nm, respectively. In pure Ce-NNP suspensions, this approach accurately classifies 68% of all detected Ce-NPs with <4% false assignments. For ternary mixtures of Ce-ENPs, INPs, and NNPs, we classify 56% to 76% of all detected Ce-NPs. We demonstrate a linear response with increasing concentrations of Ce-INPs and Ce-ENPs across approximately three orders of magnitude and can classify particles down to ratios of ∼1:50 for anthropogenic : natural Ce-NPs.
Walpen, N., Joss, A., & von Gunten, U. (2022). Application of UV absorbance and electron-donating capacity as surrogates for micropollutant abatement during full-scale ozonation of secondary-treated wastewater. Water Research, 209, 117858 (11 pp.). doi:10.1016/j.watres.2021.117858, Institutional Repository

Ozonation of secondary-treated wastewater for the abatement of micropollutants requires a reliable control of ozone doses. Changes in the UV absorbance of dissolved organic matter (DOM) during ozonation allow to estimate micropollutant abatement on-line and were therefore identified as feed-back control parameter. In this study, the suitability of the electron-donating capacity (EDC) as an additional surrogate parameter which is independent of optical DOM properties was evaluated during full-scale ozonation. For this purpose, a recently developed EDC analyzer was enhanced to enable continuous on-line EDC and UV absorbance measurements. During a multi-week monitoring campaign at the wastewater treatment plant of Zurich, Switzerland, specific ozone doses were varied from 0.13 to 0.91 mgO3⋅mgDOC-1 and selected micropollutants with different ozone reactivities were analyzed by LC-MS in conjunction with bromate analysis by IC-MS. In agreement with previous laboratory studies, the relative residual UV absorbance and EDC both decreased exponentially as a function of the specific ozone dose and, in comparison to the residual UV absorbance, residual EDC values showed a more pronounced decrease at low specific ozone doses ≤0.34 mgO3⋅mgDOC-1. Logistic regression models allowed to estimate relative residual micropollutant concentrations in the ozonation effluent using either the residual UV absorbance or EDC as explanatory variable. Averaging those models along the explanatory variables allowed to estimate target values in relative residual UV absorbances and EDC for specific micropollutant abatement targets. In addition, both parameters allowed to identify conditions with elevated conversions of bromide to bromate. Taken together, these findings show that the integration of relative residual EDC values as a second control parameter can improve existing absorbance-based ozonation control systems to meet micropollutant abatement targets, particularly for treatment systems where low ozone doses are applied.
Cai, Y., Mitrano, D. M., Hufenus, R., & Nowack, B. (2021). Formation of fiber fragments during abrasion of polyester textiles. Environmental Science and Technology, 55(12), 8001-8009. doi:10.1021/acs.est.1c00650, Institutional Repository

Fiber fragments are one of the dominant types of microplastics in environmental samples, suggesting that synthetic textiles are a potential source of microplastics to the environment. Whereas the release of microplastics during washing of textiles is already well studied, much less is known about the release during abrasion processes. The abrasion of textiles may induce fibrillation of fibers and therefore result in the formation of much finer fiber fragments. The aim of this study was to investigate the influence of abrasion of synthetic textiles on the formation of microplastic fibers and fibrils. Fleece and interlock textile swatches made of polyester were abraded using abrasion tests with a Martindale tester. The microplastic fibers and fibrils formed during abrasion were extracted from the textiles and characterized in terms of number, length, and diameter. The microplastic fibers demonstrated the same diameter than the fibers found in the textiles (fleece: 12.3 μm; interlock: 12.7 μm), while fibrils with a much smaller diameter (fleece: 2.4 μm; interlock: 4.9 μm) were also found. The number of fibrils formed during abrasion in both textiles was higher than the number of microplastic fibers. The majority of the extracted microplastic fibers had a length between 200 and 800 μm, while most fibrils were between 30 and 150 μm, forming two distinct fiber fragment morphologies. The number of microplastic fibers formed during abrasion was 5 to 30 times higher than the number of microplastic fibers that could be extracted from non-abraded samples. The number of fibrils increased after abrasion by more than a factor of 200 for both fabric types. The fibrils formed during abrasion have diameters that fall within the inhalable size for airborne particles. The potential release of fibrils into air during wear of textiles thus raises questions about the human exposure to these materials. Since the Martindale tester can simulate a daily application scenario of textiles over a prolonged period only in a limited way, future studies are needed to establish the correlation between the test results with a real-world scenario.
Carles, L., Wullschleger, S., Joss, A., Eggen, R. I. L., Schirmer, K., Schuwirth, N., … Tlili, A. (2021). Impact of wastewater on the microbial diversity of periphyton and its tolerance to micropollutants in an engineered flow-through channel system. Water Research, 203, 117486 (14 pp.). doi:10.1016/j.watres.2021.117486, Institutional Repository

Wastewater treatment plants (WWTPs) play an important role in retaining organic matter and nutrients but to a lesser extent micropollutants. Therefore, treated wastewater is recognized as a major source of multiple stressors, including complex mixtures of micropollutants. These can potentially affect microbial communities in the receiving water bodies and the ecological functions they provide. In this study, we evaluated in flow-through channels the consequences of an exposure to a mixture of stream water and different percentages of urban WWTP effluent, ranging from 0% to 80%, on the microbial diversity and function of periphyton communities. Assuming that micropollutants exert a selective pressure for tolerant microorganisms within communities, we further examined the periphyton sensitivity to a micropollutant mixture extracted from passive samplers that were immersed in the wastewater effluent. As well, micropollutants in water and in periphyton were comprehensively quantified. Our results show that micropollutants detected in periphyton differed from those found in water, both in term of concentration and composition. Especially photosystem II inhibitors accumulated in periphyton more than other pesticides. Although effects of other substances cannot be excluded, this accumulation may have contributed to the observed higher tolerance of phototrophic communities to micropollutants upon exposure to 30% and 80% of wastewater. On the contrary, no difference in tolerance was observed for heterotrophic communities. Exposure to the gradient of wastewater led to structural differences in both prokaryotic and eukaryotic communities. For instance, the relative abundance of cyanobacteria was higher with increasing percentage of wastewater effluent, whereas the opposite was observed for diatoms. Such results could indicate that differences in community structure do not necessarily lead to higher tolerance. This highlights the need to consider other wastewater constituents such as nutrients and wastewater-derived microorganisms that can modulate community structure and tolerance. By using engineered flow-through channels that mimic to some extent the required field conditions for the development of tolerance in periphyton, our study constitutes a base to investigate the mechanisms underlying the increased tolerance, such as the potential role of microorganisms originating from wastewater effluents, and different treatment options to reduce the micropollutant load in effluents.
Courtney, C., Brison, A., & Randall, D. G. (2021). Calcium removal from stabilized human urine by air and CO2 bubbling. Water Research, 202, 117467 (10 pp.). doi:10.1016/j.watres.2021.117467, Institutional Repository

Stabilization of urine with calcium hydroxide prevents enzymatic urea hydrolysis, thus allowing for maximum nitrogen recovery. The process also produces a calcium phosphate bi-product which has value as a fertilizer. However, the treated solution is saturated with calcium that could ultimately result in calcium carbonate scaling of reverse osmosis membranes during urine concentration. This would result in a decrease in maximum water removal and an increase in operational costs.
This study therefore investigated if bubbling air and carbon dioxide through stabilized urine could remove calcium ions as calcium carbonate. The process was modelled to better understand the mechanisms controlling the reactions in the process. The model was then used to determine the most cost and time efficient operating conditions. Calcium removal of between 85–98% was achieved at air flow rates of 1.5 to 9 L min−1. Increasing the CO2 concentration from 0.04% (air) to 1% decreased the reaction time from 20.5 h to 2.5 h but the cost of CO2 outweighed the shorter operating time. Air bubbling was the more cost-efficient option. It was estimated that 95% of the calcium could be removed in 7.6 h at an air flow rate of 4 L min−1 L−1 of urine and at a cost of $0.65 m−3. It was also determined that even if the pH decreased to below 11, the urine remained stabilized and no enzymatic urea hydrolysis occurred.
Domagała, K., Bell, J., Yüzbasi, N. S., Sinnet, B., Kata, D., & Graule, T. (2021). Virus removal from drinking water using modified activated carbon fibers. RSC Advances, 11(50), 31547-31556. doi:10.1039/d1ra06373a, Institutional Repository

Activated carbon (AC) exhibits superior sorption properties compared to other porous materials, due to well-developed porous structures and high surface areas. Therefore, it is widely applied in its various forms in water purification to remove a diverse range of contaminating species. The presence of viruses in fresh water bodies poses a serious issue for human health. However, AC has not yet been commonly applied to waterborne virus removal. In this study, we present oxidation and copper impregnation treatment procedures of activated carbon fibers (ACFs) that resulted in porous structure and surface chemistry modifications. The effect of these modifications on virus removal was investigated by experimental flow studies and revealed up to 2.8 log10 reduction value (LRV) and 3.6 LRV of MS2 bacterio-phages for non-modified and oxidized ACFs, respectively, emphasizing the advantages of ACF surface functionalization. Copper modified fibers demonstrated a high sensitivity to media composition, resulting in a release of metal and therefore limited virucidal capacity.
Etique, M., Bouchet, S., Byrne, J. M., Thomasarrigo, L. K., Kaegi, R., & Kretzschmar, R. (2021). Mercury reduction by nanoparticulate vivianite. Environmental Science and Technology, 55(5), 3399-3407. doi:10.1021/acs.est.0c05203, Institutional Repository

Mercury (Hg) is a toxic trace element of global environmental concern which has been increasingly dispersed into the environment since the industrial revolution. In aquatic and terrestrial systems, Hg can be reduced to elemental Hg (Hg0) and escape to the atmosphere or converted to methylmercury (MeHg), a potent neurotoxin that accumulates in food webs. FeII-bearing minerals such as magnetite, green rusts, siderite, and mackinawite are recognized HgII reducers. Another potentially Hg-reducing mineral, which commonly occurs in Fe- and organic/P-rich sediments and soils, is the ferrous iron phosphate mineral vivianite (FeII3(PO4)2·8H2O), but its reaction with HgII has not been studied to date. Here, nanoparticulate vivianite (particle size ∼ 50 nm; FeII content > 98%) was chemically synthesized and characterized by a combination of chemical, spectroscopic, and microscopic analyses. Its ability to reduce HgII was investigated at circumneutral pH under anoxic conditions over a range of FeII/HgII ratios (0.1–1000). For FeII/HgII ratios ≥1, which are representative of natural environments, HgII was very quickly and efficiently reduced to Hg0. The ability of vivianite to reduce HgII was found to be similar to those of carbonate green rust and siderite, two of the most effective Hg-reducing minerals. Our results suggest that vivianite may be involved in abiotic HgII reduction in Fe and organic/P-rich soils and sediments, potentially contributing to Hg evasion while also limiting MeHg formation in these ecosystems.
González-Pleiter, M., Edo, C., Aguilera, Á., Viúdez-Moreiras, D., Pulido-Reyes, G., González-Toril, E., … Rosal, R. (2021). Occurrence and transport of microplastics sampled within and above the planetary boundary layer. Science of the Total Environment, 761, 143213 (11 pp.). doi:10.1016/j.scitotenv.2020.143213, Institutional Repository

Nowadays, there is no direct evidence about the presence of microplastics (MPs) in the atmosphere above ground level. Here, we investigated the occurrence, chemical composition, shape, and size of MPs in aircraft sampling campaigns flying within and above the planetary boundary layer (PBL). The results showed that MPs were present with concentrations ranging from 1.5 MPs m−3 above rural areas to 13.9 MPs m−3 above urban areas. MPs represented up to almost one third of the total amount of microparticles collected. Fourier Transform Infrared Spectroscopy allowed identifying seven types of MPs with the highest diversity corresponding to urban areas. Atmospheric transport and deposition simulations were performed using the HYbrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model. Air mass trajectory analyses showed that MPs could be transported more than 1000 km before being deposited. This pioneer study is the first evidence of the microplastic presence above PBL and their potential long-range transport from their point of release even crossing distant borders.
Gruber, W., von Känel, L., Vogt, L., Luck, M., Biolley, L., Feller, K., … Joss, A. (2021). Estimation of countrywide N2O emissions from wastewater treatment in Switzerland using long-term monitoring data. Water Research X, 13, 100122 (12 pp.). doi:10.1016/j.wroa.2021.100122, Institutional Repository

Nitrous oxides (N2O) emissions contribute to climate change and stratospheric ozone depletion. Wastewater treatment is an important, yet likely underestimated, source of N2O emissions, as recent, long-term monitoring campaigns have demonstrated. However, the available data are insufficient to representatively estimate countrywide emission due to the brevity of most monitoring campaigns. This study showed that the emission estimates can be significantly improved using an advanced approach based on multiple continuous, long-term monitoring campaigns. In monitoring studies on 14 full-scale wastewater treatment plants (WWTPs), we found a strong variability in the yearly emission factors (EFs) (0.1 to 8% of the incoming nitrogen load) which exhibited a good correlation with effluent nitrite. But countrywide data on nitrite effluent concentrations is very limited and unavailable for emission estimation in many countries. Hence, we propose a countrywide emission factor calculated from the weighted EFs of three WWTP categories (carbon removal, EF: 0.1-8%, nitrification only: 1.8%, and full nitrogen removal: 0.9%). However, EF of carbon removal WWTPs are still highly uncertain given the expected variability in performance.
The newly developed approach allows representative, country-specific estimations of the N2O emissions from WWTP. Applied to Switzerland, the estimations result in an average EF of 0.9 to 3.6% and total emissions of 410 to 1690 tN2O-N/year, which corresponds to 0.3-1.4% of the total greenhouse gas emissions in Switzerland. Our results demonstrate that better data availability and an improved understanding of long-term monitoring campaigns is crucial to improve current emission estimations. Finally, our results confirm several measures to mitigate N2O emissions from wastewater treatment; year-round denitrification, limiting nitrite accumulation, and stringent control of sludge age in carbon removal plants.
Gruber, W., Niederdorfer, R., Ringwald, J., Morgenroth, E., Bürgmann, H., & Joss, A. (2021). Linking seasonal N2O emissions and nitrification failures to microbial dynamics in a SBR wastewater treatment plant. Water Research X, 11, 100098 (13 pp.). doi:10.1016/j.wroa.2021.100098, Institutional Repository

Nitrous oxide (N2O) is a strong greenhouse gas and causal for stratospheric ozone depletion. During biological nitrogen removal in wastewater treatment plants (WWTP), high N2O fluxes to the atmosphere can occur, typically exhibiting a seasonal emission pattern. Attempts to explain the peak emission phases in winter and spring using physico-chemical process data from WWTP were so far unsuccessful and new approaches are required. The complex and diverse microbial community of activated sludge used in biological treatment systems also exhibit substantial seasonal patterns. However, a potentially causal link between the seasonal patterns of microbial diversity and N2O emissions has not yet been investigated. Here we show that in a full-scale WWTP nitrification failure and N2O peak emissions, bad settleability of the activated sludge and a turbid effluent strongly correlate with a significant reduction in the microbial community diversity and shifts in community composition. During episodes of impaired performance, we observed a significant reduction in abundance for filamentous and nitrite oxidizing bacteria in all affected reactors. In some reactors that did not exhibit nitrification and settling failures, we observed a stable microbial community and no drastic loss of species. Standard engineering approaches to stabilize nitrification, such as increasing the aerobic sludge age and oxygen availability failed to improve the plant performance on this particular WWTP and replacing the activated sludge was the only measure applied by the operators to recover treatment performance in affected reactors. Our results demonstrate that disturbances of the sludge microbiome affect key structural and functional microbial groups, which lead to seasonal N2O emission patterns. To reduce N2O emissions from WWTP, it is therefore crucial to understand the drivers that lead to the microbial population dynamics in the activated sludge.
Hausherr, D., Niederdorfer, R., Morgenroth, E., & Joss, A. (2021). Robustness of mainstream anammox activity at bench and pilot scale. Science of the Total Environment, 796, 148920 (11 pp.). doi:10.1016/j.scitotenv.2021.148920, Institutional Repository

New technologies and processes, such as mainstream anammox, aim to reduce energy requirements of wastewater treatment and improve effluent quality. However, in municipal wastewater (MWW) anammox system are often unstable due to process control disturbance, influent variability, or unwanted nitrite oxidizing bacteria (NOB). This study examines the anammox system by focusing on anammox activity and its robustness in a mainstream environment. An 8 m3 pilot-scale sequencing batch reactor (SBR) receiving pretreated MWW (with external nitrite addition) was seeded with pre-colonized carriers. Within six months at 12–20 °C an anammox activity of 200 gN·m−3·d−1 was achieved. After the startup an anammox activity of 260 ± 83 gN·m−3·d−1 was maintained over 450 days. The robustness of the anammox activity was analyzed through three disturbance experiments. Anammox biofilm on carriers were exposed to dissolved oxygen (DO = 1.6 mg·L−1, intermittent aeration), organic loading rate (OLR, C/N increased from 2:1 to 5:1) and temperature disturbances (20 °C to 12 °C) in triplicate 12 L bench scale reactors. The anammox activity and microbial community was monitored during these disturbances. The DO and OLR disturbance experiments were replicated at pilot scale to investigate upscaling effects. Bench and pilot scale anammox activity were unaffected by the DO disturbance. Similarly, an increase in OLR did not deteriorate the bench and pilot scale anammox activity, if nitrate was available. When, at bench scale, the reactor temperature was reduced from 20 °C to 12 °C overnight, anammox activity decreased significantly, this was not the case for the slow seasonal temperature changes (12–25 °C) at pilot scale where no strong temperature dependency was detected in winter. Metagenomic analysis revealed a broad range of Brocadiaceae species with no single dominant anammox species. Anammox thrive under mainstream conditions and can withstand typical process disruptions.
Hess, A., & Morgenroth, E. (2021). Biological activated carbon filter for greywater post-treatment: Long-term TOC removal with adsorption and biodegradation. Water Research X, 13, 100113 (9 pp.). doi:10.1016/j.wroa.2021.100113, Institutional Repository

Biological activated carbon (BAC) filters can be used to remove residual total organic carbon (TOC) from greywater after a membrane bioreactor. The two main TOC removal processes are adsorption to the granular activated carbon (GAC) and biological degradation. Biodegradation leads to the growth of microorganisms in the filter bed, which can lead to increased pressure loss over the filter bed. However, the roles of sorption and biodegradation in long-term TOC removal and how they complement each other are unclear. We monitored TOC removal from greywater in a BAC filter installed following a membrane bioreactor over more than 900 days. Removal performance depended on the operational time of the BAC filter, the influent TOC concentration, and in the upper part of the filter on the empty bed contact time (EBCT). Across the overall filter, the EBCT did not significantly influence TOC removal, showing that the filter was sufficiently large for the range of flow rates observed. Analysis of the long-term data revealed the equal importance of sorption and biodegradation over the whole operation period and the whole filter bed. Most of the TOC was removed in the upper part of the filter, where biodegradation was the dominant mechanism. In the lower part of the filter, sorption capacity remained and allowed high influent TOC concentrations to be buffered. The generous filter design with low average filtration rates ensured long-term TOC removal. The only maintenance needed was backwashing, which was required only after more than 800 days of operation. Backwashing effectively reduced the pressure loss but had no significant influence on the effluent water quality. Our study shows that BAC filters are a suitable post-treatment step for the treatment of greywater with highly variable flow and TOC concentrations.
Hess, A., Baum, C., Schiessl, K., Besmer, M. D., Hammes, F., & Morgenroth, E. (2021). Stagnation leads to short-term fluctuations in the effluent water quality of biofilters: a problem for greywater reuse?. Water Research X, 13, 100120 (9 pp.). doi:10.1016/j.wroa.2021.100120, Institutional Repository

A key characteristic of decentralized greywater treatment and reuse is high variability in both nutrient concentrations and flow. This variability in flow leads to stagnant water in the system and causes short-term fluctuations in the effluent water quality. Automated monitoring tools provide data to understand the mechanisms underlying the dynamics and to adapt control strategies accordingly. We investigated the fluctuations in a building-scale greywater treatment system comprising a membrane bioreactor followed by a biological activated carbon filter. Short-term dynamics in the effluent of the biological activated carbon filter were monitored with automated flow cytometry and turbidity, and the impact of these fluctuations on various hygiene-relevant parameters in the reuse water was evaluated. Continuous biofilm detachment into the stagnant water in the biological activated carbon filter led to temporarily increased turbidity and cell concentrations in the effluent after periods of stagnation. The fluctuations in cell concentrations were consistent with a model assuming higher detachment rates during flow than during times with stagnant water. For this system, total cell concentration and turbidity were strongly correlated. We also showed that the observed increase in cell concentration was not related to either an increase of organic carbon concentration or the concentration of two opportunistic pathogens, P. aeruginosa and L. pneumophila. Our findings demonstrate that turbidity measurements are sensitive to changes in the effluent water quality and can be used to monitor the fluctuations caused by intermittent flow. Intermittent flow did not lead to an increase in opportunistic pathogens, and this study provides no indications that stagnant water in biological activated carbon filters need be prevented.
Kaegi, R., Gogos, A., Voegelin, A., Hug, S. J., Winkel, L. H. E., Buser, A. M., & Berg, M. (2021). Quantification of individual Rare Earth Elements from industrial sources in sewage sludge. Water Research X, 11, 100092 (11 pp.). doi:10.1016/j.wroa.2021.100092, Institutional Repository

Rare Earth Elements (REEs) are used in increasing amounts in technical applications and consumer products. However, to date, the contribution of industrial sources to the loads of individual REEs in wastewater streams have not been quantified. Here, we determine the REE contents in sludge collected from 63 wastewater treatment plants (WWTPs) across Switzerland. To quantify the industrial fraction of individual REEs in the sewage sludge, we develop two complementary approaches, based on REE ratios and REE pattern fitting. Unspecific (background) inputs, with REE patterns similar to the averaged REE pattern of soils collected across Switzerland, dominate the REE budget of most WWTPs. A few WWTPs receive significant REE inputs from specific industrial sources. Based on population equivalents of Switzerland, we estimate a total annual load of 4200 kg Cerium (Ce, 0.5 g Ce year-1 capita-1), with an industrial contribution of 2000 kg year-1. The latter agrees with estimates of probabilistic mass flow models for engineered nanoscale CeO2 particles discharged to the sewer network. About 7 kg year-1 of Samarium (Sm,total for Switzerland: 184 kg year-1 or 0.02 g Sm year-1 capita-1) and 3 kg year-1 of Europium (Eu,total for Switzerland: 44 kg year-1 or 0.005 g Eu year-1 capita-1) are assigned to industrial inputs from single WWTPs. Gadolinium (Gd) is used in the form of a stable complex as contrast agent in magnetic resonance imaging. Assuming 10% removal of Gd during wastewater treatment, we calculate an annual discharge of 90 kg of Gd from one individual WWTP to surface waters. WWTPs with exceptionally high industrial inputs of specific REEs warrant detailed investigations to identify the respective sources and to assess whether REE concentrations in effluents are elevated to the same degree.
Kaegi, R., Fierz, M., & Hattendorf, B. (2021). Quantification of nanoparticles in dispersions using transmission electron microscopy. Microscopy and Microanalysis, 27(3), 557-565. doi:10.1017/S1431927621000398, Institutional Repository

The quantification of the particle size and the number concentration (PNC) of nanoparticles (NPs) is key for the characterization of nanomaterials. Transmission electron microscopy (TEM) is often considered as the gold standard for assessing the size of NPs; however, the TEM sample preparation suitable for estimating the PNC based on deposited NPs is challenging. Here, we use an ultrasonic nebulizer (USN) to transfer NPs from aqueous suspensions into dried aerosols which are deposited on TEM grids in an electrostatic precipitator of an aerosol monitor. The deposition efficiency of the electrostatic precipitator was ≈2%, and the transport efficiency of the USN was ≈7%. Experiments using SiO2NPs (50-200 nm) confirmed an even deposition of the nebulized particles in the center of the TEM grids. PNCs of the SiO2NPs derived from TEM images underestimated the expected PNCs of the suspensions by a factor of up to three, most likely resulting from droplet coagulation and NP aggregation in the USN. Nevertheless, single particles still dominated the PNC. Our approach results in reproducible and even deposition of particles on TEM grids suitable for morphological analysis and allows an estimation of the PNC in the suspensions based on the number of particles detected by TEM.
Krause, A., Häfner, F., Augustin, F., & Udert, K. M. (2021). Qualitative risk analysis for contents of dry toilets used to produce novel recycling fertilizers. Circular Economy and Sustainability, 1, 1107-1146. doi:10.1007/s43615-021-00068-3, Institutional Repository

Human excreta are a sustainable, economical source of nutrients, and can be used to produce recycling fertilizer for horticulture by collecting and processing the contents of dry toilets. Herein, we discuss the key categories of risk associated with the main groups of materials commonly found in dry toilets. The study was part of the development of a German product standard for marketable and quality-assured recycling fertilizers from human excreta for use in horticulture. Particular attention is paid to ensuring that the fertilizer is epidemiologically and environmentally harmless and that the quality of the recycling fertilizer is adequate in terms of low pollution and nutrient availability. In sum, the risk of transmissible human pathogens lies within the human excreta, particularly feces; plant materials added during composting are of particular phytosanitary relevance; pharmaceutical residues in excrements and chemical additives are potential sources of pollutants; non-biodegradable contaminants can cause pollution and injury; and the horticultural risks involve mainly the ammonia emission potential and in some cases the salinity effects of urine. These risks can be reduced significantly (i) with education of users around proper operation of dry toilets and the consequences of adding inappropriate waste, (ii) with facilitation of proper use with general waste bins and clear instructions, and importantly (iii) by using modern sanitization and cleaning processes and testing for harmful substances under the guidance of local laws and regulations, ensuring safe and high-quality fertilizers. In conclusion, the benefits of using dry toilet contents to produce fertilizers for use in horticulture are unquestionable. Our analysis highlights the need to support recycling optimization and awareness for the purpose of a sustainable circular economy and to minimize the risk of harm to humans and the environment overall.
Kuehr, S., Diehle, N., Kaegi, R., & Schlechtriem, C. (2021). Ingestion of bivalve droppings by benthic invertebrates may lead to the transfer of nanomaterials in the aquatic food chain. Environmental Sciences Europe, 33(1), 35 (16 pp.). doi:10.1186/s12302-021-00473-3, Institutional Repository

Background: Manufactured nanomaterials (MNMs) are released into the environment in increasing quantities. Consequently, MNMs also reach the aquatic environment, where they can interact with different organisms. Previous studies have already shown that filter-feeding bivalves can ingest nanomaterials from the surrounding water leading to higher concentration of the material. Furthermore, they have been shown to be vectors for environmental chemicals and pathogens to other organisms, as their feces/pseudofeces (F/pF) play a crucial role as a food source for other species. We exposed bivalves (Corbicula sp.) to MNMs and performed experiments to investigate the possible transport of MNMs by their feces to the benthic amphipod Hyalella azteca. Silver (Ag) and gold (Au) nanoparticles (NPs) as well as fluorescent polystyrene nanoparticles were used in this study. They allowed the investigation of the metal content of the bivalves’ feces and the amphipods feeding on it, as well as the localization of the fluorescent particles in the body of the animals.
Results: Examination of the feces by fluorescence microscope and determination of the total metal content by inductively coupled plasma mass spectrometry (ICP-MS) showed a high accumulation of the exposed MNMs in the F/pF. The examination of fecal matter, using transmission electron microscopy confirmed the nanoparticulate character of the metals in the examined fecal matter. After exposure of amphipods to the MNMs containing fecal matter, the fluorescent MNMs were localized in the animals gut. The chronic exposure of juvenile amphipods over 21 days to feces enriched with Au MNMs caused significant effects on the growth of the amphipods. The transfer of both metals (Ag and Au) from the fecal matter to the amphipods was confirmed after total metal measurements.
Conclusion: Probably, for the first time, it has been shown that when exposed to MNMs bivalves can transfer these particles to other benthic species. Transfer is via released F/pF upon which the benthic species feed and thus could ingest the particles. The high concentrations of MNMs in the fecal matter raises concerns about the potential accumulation and transfer of the materials and associated ecotoxicological effects in invertebrates such as benthic amphipods.
Kuehr, S., Kaegi, R., Maletzki, D., & Schlechtriem, C. (2021). Testing the bioaccumulation potential of manufactured nanomaterials in the freshwater amphipod Hyalella azteca. Chemosphere, 263, 127961 (15 pp.). doi:10.1016/j.chemosphere.2020.127961, Institutional Repository

Standardized experimental approaches for the quantification of the bioaccumulation potential of nanomaterials in general and in (benthic) invertebrates in particular are currently lacking. We examined the suitability of the benthic freshwater amphipod Hyalella azteca for the examination of the bioaccumulation potential of nanomaterials. A flow-through test system that allows the generation of bioconcentration and biomagnification factors was applied. The feasibility of the system was confirmed in a 2-lab comparison study. By carrying out bioconcentration and biomagnification studies with gold, titanium dioxide and silver nanoparticles as well as dissolved silver (AgNO3) we were able to assess the bioaccumulation potential of different types of nanomaterials and their exposure pathways. For this, the animals were examined for their total metal body burden using inductively coupled mass spectroscopy (ICP-MS) and for the presence of nanoparticulate burdens using single-particle ICP-MS. The role of released ions was highlighted as being very important for the bioavailability and bioaccumulation of metals from nanoparticles for both examined uptake paths examined (bioconcentration and biomagnification). In 2018 a tiered testing strategy for engineered nanomaterials was proposed by Handy et al. that may allow a waiver of bioaccumulation fish studies using inter alia invertebrates. Data gained in studies carried out with invertebrates like the developed Hyalella azteca test may be included in this proposed tiered testing strategy.
Larsen, T. A., Riechmann, M. E., & Udert, K. M. (2021). State of the art of urine treatment technologies: a critical review. Water Research X, 13, 100114 (20 pp.). doi:10.1016/j.wroa.2021.100114, Institutional Repository

Over the last 15 years, urine treatment technologies have developed from lab studies of a few pioneers to an interesting innovation, attracting attention from a growing number of process engineers. In this broad review, we present literature from more than a decade on biological, physical-chemical and electrochemical urine treatment processes. Like in the first review on urine treatment from 2006, we categorize the technologies according to the following objectives: stabilization, volume reduction, targeted N-recovery, targeted P-recovery, nutrient removal, sanitization, and handling of organic micropollutants. We add energy recovery as a new objective, because extensive work has been done on electrochemical energy harvesting, especially with bio-electrochemical systems. Our review reveals that biological processes are a good choice for urine stabilization. They have the advantage of little demand for chemicals and energy. Due to instabilities, however, they are not suited for bathroom applications and they cannot provide the desired volume reduction on their own. A number of physical-chemical treatment technologies are applicable at bathroom scale and can provide the necessary volume reduction, but only with a steady supply of chemicals and often with high demand for energy and maintenance. Electrochemical processes is a recent, but rapidly growing field, which could give rise to exciting technologies at bathroom scale, although energy production might only be interesting for niche applications. The review includes a qualitative assessment of all unit processes. A quantitative comparison of treatment performance was not the goal of the study and could anyway only be done for complete treatment trains. An important next step in urine technology research and development will be the combination of unit processes to set up and test robust treatment trains. We hope that the present review will help guide these efforts to accelerate the development towards a mature technology with pilot scale and eventually full-scale implementations.
Magyar, P. M., Hausherr, D., Niederdorfer, R., Stöcklin, N., Wei, J., Mohn, J., … Lehmann, M. F. (2021). Nitrogen isotope effects can be used to diagnose N transformations in wastewater anammox systems. Scientific Reports, 11(1), 7850 (12 pp.). doi:10.1038/s41598-021-87184-0, Institutional Repository

Anaerobic ammonium oxidation (anammox) plays an important role in aquatic systems as a sink of bioavailable nitrogen (N), and in engineered processes by removing ammonium from wastewater. The isotope effects anammox imparts in the N isotope signatures (15N/14N) of ammonium, nitrite, and nitrate can be used to estimate its role in environmental settings, to describe physiological and ecological variations in the anammox process, and possibly to optimize anammox-based wastewater treatment. We measured the stable N-isotope composition of ammonium, nitrite, and nitrate in wastewater cultivations of anammox bacteria. We find that the N isotope enrichment factor 15ε for the reduction of nitrite to N2 is consistent across all experimental conditions (13.5‰ ± 3.7‰), suggesting it reflects the composition of the anammox bacteria community. Values of 15ε for the oxidation of nitrite to nitrate (inverse isotope effect, - 16 to - 43‰) and for the reduction of ammonium to N2 (normal isotope effect, 19-32‰) are more variable, and likely controlled by experimental conditions. We argue that the variations in the isotope effects can be tied to the metabolism and physiology of anammox bacteria, and that the broad range of isotope effects observed for anammox introduces complications for analyzing N-isotope mass balances in natural systems.
Mehrabi, K., Kaegi, R., Günther, D., & Gundlach-Graham, A. (2021). Emerging investigator series: automated single-nanoparticle quantification and classification: a holistic study of particles into and out of wastewater treatment plants in Switzerland. Environmental Science: Nano, 8(5), 1211-1225. doi:10.1039/d0en01066a, Institutional Repository

Single particle inductively coupled plasma time-of-flight mass spectrometry (sp-ICP-TOFMS), in combination with online microdroplet calibration, allows for the determination of particle number concentrations (PNCs) and the amount (i.e. mass) of ICP-MS-accessible elements in individual particles. Because sp-ICP-TOFMS analyses of environmental samples produce rich datasets composed of both single-metal nanoparticles (smNPs) and many types of multi-metal NPs (mmNPs), interpretation of these data is well suited to automated analysis schemes. Here, we present a new data analysis approach that includes: 1. automatic particle detection and elemental mass determinations based on online microdroplet calibration, 2. correction of false (randomly occurring) multi-metal associations caused by measurement of coincident but distinct NPs, and 3. unsupervised clustering analysis of mmNPs to identify unique classes of NPs based on their element compositions. To demonstrate the potential of our approach, we analyzed water samples collected from the influent and effluent of five wastewater treatment plants (WWTPs) across Switzerland. We determined elemental masses in individual NPs, as well as PNCs, to estimate the NP removal efficiencies of the individual WWTPs. From WWTP samples collected at two points in time, we found an average of 90% and 94% removal efficiencies of single-metal and multi-metal NPs, respectively. Between 5% to 27% of detected NPs were multi-metal; the most abundant particle types were those rich in Ce-La, Fe-Al, Ti-Zr, and Zn-Cu. Through hierarchical clustering, we identified NP classes conserved across all WWTPs, as well as particle types that are unique to one or a few WWTPs. These uniquely occurring particle types may represent point sources of anthropogenic NPs. We describe the utility of clustering analysis of mmNPs for identifying natural, geogenic NPs, and also for the discovery of new, potentially anthropogenic, NP targets.
Mehrabi, K., Kaegi, R., Günther, D., & Gundlach-Graham, A. (2021). Quantification and clustering of inorganic nanoparticles in wastewater treatment plants across Switzerland. Chimia, 75(7-8), 642-646. doi:10.2533/chimia.2021.642, Institutional Repository

Single particle Inductively Coupled Plasma Time-of-Flight Mass Spectrometry (sp-ICP-TOFMS), in combination with online microdroplet calibration, allows the determination of particle number concentrations (PNCs) and the masses of elements in individual particles. Because sp-ICP-TOFMS analyses of environmental samples produce rich datasets composed of both single-metal nanoparticles (smNPs) and many types of multi-metal NPs (mmNPs), interpretation of these data is well suited to automated analysis schemes. Here, we present a data analysis approach that includes automatic particle detection and elemental mass determinations based on online microdroplet calibration, and unsupervised clustering analysis of mmNPs to identify unique classes of NPs based on their element compositions. To demonstrate the potential of our approach, we analyzed wastewater samples collected from the influent and effluent of five wastewater treatment plants (WWTPs) across Switzerland. We determined elemental masses in individual NPs, as well as PNCs, to estimate the NP removal efficiencies of the individual WWTPs. Through hierarchical clustering, we identified NP classes conserved across all WWTPs; the most abundant particle types were those rich in Ce-La, Fe-Al, Ti-Zr, and Zn-Cu. In addition, we found particle types that are unique to one or a few WWTPs, which could indicate point sources of anthropogenic NPs.
Moraes Schambeck, C., Ribeiro da Costa, R. H., & Derlon, N. (2021). Phosphate removal from municipal wastewater by alginate-like exopolymers hydrogels recovered from aerobic granular sludge. Bioresource Technology, 333, 125167 (10 pp.). doi:10.1016/j.biortech.2021.125167, Institutional Repository

This worked assessed the potential of alginate-like exopolymers (ALE) hydrogels recovered from aerobic granular sludge (AGS) in removing compounds commonly present in municipal wastewater. Batch sorption experiments were performed with ALE hydrogels at different operating conditions. Results showed that ALE hydrogels can only remove phosphate, at removal efficiencies of up to 90.8% and practical loadings of 1.22 ± 0.07 mg PO43--P/g TSALE. Phosphate removal was observed even in the presence of competing ions. Moreover, neutral to acidic pH values strongly impaired the phosphate removal (28.9 ± 0.8% at pH = 6.00), while basic pH at around 8.50 was the most favourable (up to 90.8% at pH = 8.67). However, ALE hydrogels contributed to the increase in COD, total nitrogen and total phosphorus in the bulk liquid, what suggests that ALE need to be further tailored. Therefore, this study demonstrates that ALE represent a relevant approach for the recovery of phosphates from municipal wastewater.
Niederdorfer, R., Fragner, L., Yuan, L., Hausherr, D., Wei, J., Magyar, P., … Bürgmann, H. (2021). Distinct growth stages controlled by the interplay of deterministic and stochastic processes in functional anammox biofilms. Water Research, 200, 117225 (14 pp.). doi:10.1016/j.watres.2021.117225, Institutional Repository

Mainstream anaerobic ammonium oxidation (anammox) represents one of the most promising energy-efficient mechanisms of fixed nitrogen elimination from wastewaters. However, little is known about the exact processes and drivers of microbial community assembly within the complex microbial biofilms that support anammox in engineered ecosystems. Here, we followed anammox biofilm development on fresh carriers in an established 8m3 mainstream anammox reactor that is exposed to seasonal temperature changes (∼25-12°C) and varying NH4+ concentrations (5-25 mg/L). We use fluorescence in situ hybridization and 16S rRNA gene sequencing to show that three distinct stages of biofilm development emerge naturally from microbial community composition and biofilm structure. Neutral modelling and network analysis are employed to elucidate the relative importance of stochastic versus deterministic processes and synergistic and antagonistic interactions in the biofilms during their development. We find that the different phases are characterized by a dynamic succession and an interplay of both stochastic and deterministic processes. The observed growth stages (Colonization, Succession and Maturation) appear to be the prerequisite for the anticipated growth of anammox bacteria and for reaching a biofilm community structure that supports the desired metabolic and functional capacities observed for biofilm carriers already present in the system (∼100gNH4-N m3 d-1). We discuss the relevance of this improved understanding of anammox-community ecology and biofilm development in the context of its practical application in the start-up, configuration, and optimization of anammox biofilm reactors.
Niederdorfer, R., Hausherr, D., Palomo, A., Wei, J., Magyar, P., Smets, B. F., … Bürgmann, H. (2021). Temperature modulates stress response in mainstream anammox reactors. Communications Biology, 4(1), 23 (12 pp.). doi:10.1038/s42003-020-01534-8, Institutional Repository

Autotrophic nitrogen removal by anaerobic ammonium oxidizing (anammox) bacteria is an energy-efficient nitrogen removal process in wastewater treatment. However, full-scale deployment under mainstream conditions remains challenging for practitioners due to the high stress susceptibility of anammox bacteria towards fluctuations in dissolved oxygen (DO) and temperature. Here, we investigated the response of microbial biofilms with verified anammox activity to DO shocks under 20 °C and 14 °C. While pulse disturbances of 0.3 mg L−1 DO prompted only moderate declines in the NH4+ removal rates, 1.0 mg L−1 DO led to complete but reversible inhibition of the NH4+ removal activity in all reactors. Genome-centric metagenomics and metatranscriptomics were used to investigate the stress response on various biological levels. We show that temperature regime and strength of DO perturbations induced divergent responses from the process level down to the transcriptional profile of individual taxa. Community-wide gene expression differed significantly depending on the temperature regime in all reactors, and we found a noticeable impact of DO disturbances on genes involved in transcription, translation, replication and posttranslational modification at 20 °C but not 14 °C. Genome-centric analysis revealed that different anammox species and other key biofilm taxa differed in their transcriptional responses to distinct temperature regimes and DO disturbances.
Reynaert, E., Hess, A., & Morgenroth, E. (2021). Making waves: why water reuse frameworks need to co-evolve with emerging small-scale technologies. Water Research X, 11, 100094 (5 pp.). doi:10.1016/j.wroa.2021.100094, Institutional Repository

Novel technologies allow to reuse or recycle water for on-site applications such as toilet flushing, showering, or hand washing at the household- or building-scale. Many of these technologies have now reached technology readiness levels that require for verification and validation testing in the field. Results from such field tests of decentralized water reuse systems have been published over the past few years, and observed performance is often compared to quality targets from water reuse frameworks (WRFs). An inspection of ten recent journal publications reveals that targets from WRFs are often misinterpreted, and the emphasis of these publications is too often on demonstrating successful aspects of the technologies rather than critically evaluating the quality of the produced water. We hypothesize that some of these misinterpretations are due to ambiguous definition of scopes of WRFs (e.g., "unrestricted urban reuse") and unclear applicability for novel recycling systems that treat the water for applications that go beyond the reuse scopes defined in current WRFs. Additional challenges are linked to the verification of WRF quality targets in small-scale and decentralized systems under economic and organizational constraints. Current WRFs are not suitable for all possible reuse cases, and there is need for a critical discussion of quality targets and associated monitoring methods. As the scope of water reuse has expanded greatly over the past years, WRFs need to address new applications and advances in technology, including in monitoring capacities.
Riechmann, M. E., Ndwandwe, B., Greenwood, E. E., Reynaert, E., Morgenroth, E., & Udert, K. M. (2021). On-site urine treatment combining Ca(OH)2 dissolution and dehydration with ambient air. Water Research X, 13, 100124 (12 pp.). doi:10.1016/j.wroa.2021.100124, Institutional Repository

We present the results of three field tests and three laboratory tests of a new physical-chemical urine treatment system, which can recover all nutrients, while pathogens are inactivated. The system consists of two steps. In the first reactor, biological processes including urea hydrolysis are prevented by mixing fresh urine with calcium hydroxide (Ca(OH)2). Due to the high pH value and the high availability of calcium, phosphate can be recovered by precipitation. The high pH value also fosters the inactivation of microorganisms, including pathogens. In the second reactor, water is evaporated at low energy consumption by blowing unheated ambient air over the stabilized urine. Stabilization in the first reactor was successful in all field and laboratory tests. The pH value remained between 12 and 13, except for short dips due to shortages of Ca(OH)2. Nearly all phosphorus (92-96%) precipitated and could be recovered as calcium phosphate in the first reactor, while nitrogen and potassium overflowed with the urine into the evaporation reactor. The efficiency of the second treatment step was very different for field and laboratory experiments and depended on the duration of the experiment. During a four-day laboratory test, nitrogen recovery was 98%. In contrast, nitrogen recovery was only around 20% in the long-term field experiments. The high nitrogen losses occurred, because biological urea hydrolysis was not inhibited anymore, when the pH value in the second reactor decreased due to the dissolution of high amounts of carbon dioxide from the ambient air. Potassium was not subject to any significant loss, and the measured recovery in the solid evaporation product was 98%. Evaporation rates ranged between 50 g m-2 h-1 (RH = 82±13%, T = 12±6°C) and 130 g m-2 h-1 (RH = 60±19%, T = 24±5°C) in the three field tests. Apart from some disturbances due to low supply of Ca(OH)2, the urine module functioned without any substantial failures and was simple to maintain. The minimum consumption of Ca(OH)2 at full capacity was 6 g·L-1 urine and the electricity demand was 150 Wh kg-1 water evaporated from urine, resulting in operational costs of 0.05 EUR pers-1 d-1.
Russo, S., Besmer, M. D., Blumensaat, F., Bouffard, D., Disch, A., Hammes, F., … Villez, K. (2021). The value of human data annotation for machine learning based anomaly detection in environmental systems. Water Research, 206, 117695 (10 pp.). doi:10.1016/j.watres.2021.117695, Institutional Repository

Anomaly detection is the process of identifying unexpected data samples in datasets. Automated anomaly detection is either performed using supervised machine learning models, which require a labelled dataset for their calibration, or unsupervised models, which do not require labels. While academic research has produced a vast array of tools and machine learning models for automated anomaly detection, the research community focused on environmental systems still lacks a comparative analysis that is simultaneously comprehensive, objective, and systematic. This knowledge gap is addressed for the first time in this study, where 15 different supervised and unsupervised anomaly detection models are evaluated on 5 different environmental datasets from engineered and natural aquatic systems. To this end, anomaly detection performance, labelling efforts, as well as the impact of model and algorithm tuning are taken into account. As a result, our analysis reveals the relative strengths and weaknesses of the different approaches in an objective manner without bias for any particular paradigm in machine learning. Most importantly, our results show that expert-based data annotation is extremely valuable for anomaly detection based on machine learning.
Schulz, K., ThomasArrigo, L. K., Kaegi, R., & Kretzschmar, R. (2021). Stabilization of ferrihydrite and lepidocrocite by silicate during Fe(II)-catalyzed mineral transformation: impact on particle morphology and silicate distribution. Environmental Science and Technology, 56(9), 5929-5938. doi:10.1021/acs.est.1c08789, Institutional Repository

Interactions between aqueous ferrous iron (Fe(II)) and secondary Fe oxyhydroxides catalyze mineral recrystallization and/or transformation processes in anoxic soils and sediments, where oxyanions, such as silicate, are abundant. However, the effect and the fate of silicate during Fe mineral recrystallization and transformation are not entirely understood and especially remain unclear for lepidocrocite. In this study, we reacted (Si-)ferrihydrite (Si/Fe = 0, 0.05, and 0.18) and (Si-)lepidocrocite (Si/Fe = 0 and 0.08) with isotopically labeled 57Fe(II) (Fe(II)/Fe(III) = 0.02 and 0.2) at pH 7 for up to 4 weeks. We followed Fe mineral transformations with X-ray diffraction and tracked Fe atom exchange by measuring aqueous and solid phase Fe isotope fractions. Our results show that the extent of ferrihydrite transformation in the presence of Fe(II) was strongly influenced by the solid phase Si/Fe ratio, while increasing the Fe(II)/Fe(III) ratio (from 0.02 to 0.2) had only a minor effect. The presence of silicate increased the thickness of newly formed lepidocrocite crystallites, and elemental distribution maps of Fe(II)-reacted Si-ferrihydrites revealed that much more Si was associated with the remaining ferrihydrite than with the newly formed lepidocrocite. Pure lepidocrocite underwent recrystallization in the low Fe(II) treatment and transformed to magnetite at the high Fe(II)/Fe(III) ratio. Adsorbed silicate inactivated the lepidocrocite surfaces, which strongly reduced Fe atom exchange and inhibited mineral transformation. Collectively, the results of this study demonstrate that Fe(II)-catalyzed Si-ferrihydrite transformation leads to the redistribution of silicate in the solid phase and the formation of thicker lepidocrocite platelets, while lepidocrocite transformation can be completely inhibited by adsorbed silicate. Therefore, silicate is an important factor to include when considering Fe mineral dynamics in soils under reducing conditions.
Sutherland, C., Reynaert, E., Sindall, R. C., Riechmann, M. E., Magwaza, F., Lienert, J., … Udert, K. M. (2021). Innovation for improved hand hygiene: field testing the Autarky handwashing station in collaboration with informal settlement residents in Durban, South Africa. Science of the Total Environment, 796, 149024 (13 pp.). doi:10.1016/j.scitotenv.2021.149024, Institutional Repository

Safe and accessible water services for hand hygiene are critical to human health and well-being. However, access to handwashing facilities is limited in cities in the Global South, where rapid urbanisation, service backlogs, lack of infrastructure and capacity, and water scarcity impact on the ability of local governments to provide them. Community participation and the co-production of knowledge in the development of innovative technologies, which are aligned with Water, Sanitation and Hygiene (WASH) principles, can lead to more sustainable and socially-acceptable hand hygiene systems. This paper presents the outcomes of the testing of the Autarky handwashing station, a technology that provides onsite treatment and recycling of handwashing water, in an informal settlement in Durban, South Africa. The transdisciplinary research approach adopted enabled the participation of multiple stakeholders with different knowledge systems in the framing, testing and evaluation of the system. The process of co-producing knowledge, as well as the outcomes of the testing, namely high levels of functionality and social acceptability of the technology, supported the WASH principles. The evaluation revealed that the Autarky handwashing station is a niche intervention that improved access to safe and appealing handwashing facilities in an informal settlement. Its novel design, socially desirable features, reliability and ability to save water increased its acceptance in the community. The testing of the system in a real-world context revealed the value of including communities in knowledge production processes for technology innovation. Further work is required to ensure that real-time monitoring of system function is feasible before such systems can be implemented at larger scale.
Sutherland, C., Reynaert, E., Dhlamini, S., Magwaza, F., Lienert, J., Riechmann, M. E., … Sindall, R. C. (2021). Socio-technical analysis of a sanitation innovation in a peri-urban household in Durban, South Africa. Science of the Total Environment, 755, 143284 (12 pp.). doi:10.1016/j.scitotenv.2020.143284, Institutional Repository

The provision of water and sanitation for all that is safe, dignified, reliable, affordable and sustainable is a major global challenge. While centralized sewer-based sanitation systems remain the dominant approach to providing sanitation, the benefits of non-sewered onsite sanitation systems are increasingly being recognised. This paper presents the outcomes of the testing of the Blue Diversion Autarky Toilet (BDAT), a sanitation system providing hygiene and dignity without relying on water and wastewater infrastructure, in a peri-urban household in Durban, South Africa. The BDAT was used by a single household as their only form of sanitation during three months of technical and social testing. An analysis based on technical data in combination with interpretive, qualitative research methods revealed that the BDAT functioned well and achieved high levels of social acceptance in the test household. The flushing, cleanliness and odour-free nature of the sanitation technology, its functionality, the household's previous sanitation experience, and their experience with and understanding of water scarcity, were the main factors underpinning their positive response to this innovation in sanitation. The testing process resulted in broader developmental benefits for the household, including improved basic services due to the upgrading of the electrical and existing sanitation system, social learning, and improved relationships between household members and the local state. A transdisciplinary research process, which emerged through the assessment, enabled the integration of different forms of knowledge from multiple actors to address the complexity of problems related to the development of socially just sanitation. The benefit of engaging with societal actors in sanitation innovation and assessing its outcomes using both the technical and social sciences is evident in this paper.
Tang, X., Pronk, W., Traber, J., Liang, H., Li, G., & Morgenroth, E. (2021). Integrating granular activated carbon (GAC) to gravity-driven membrane (GDM) to improve its flux stabilization: respective roles of adsorption and biodegradation by GAC. Science of the Total Environment, 768, 144758 (10 pp.). doi:10.1016/j.scitotenv.2020.144758, Institutional Repository

As a low-maintenance and cost-effective process, gravity-driven membrane (GDM) filtration is a promising alternative for decentralized drinking water supply, while the low flux impedes its extensive application. In order to address such issue, an integrated process consisting of granular activated carbon (GAC) layer and GDM was developed. The performance of virgin (fresh GAC) or preloaded GAC (saturated GAC) was compared. Flux stabilization was observed both in the fresh and saturated GAC/GDM process during long-term filtration and their stable fluxes were both improved by approximately 50% relative to the GDM control. Moreover, integrating GAC with GDM contributed to efficient removals for dissolved organic compounds (DOC), assimilable organic carbon (AOC) and low molecular weight substances both in fresh and saturated GAC/GDM filtration. Compared to GDM control, coupling GAC to GDM could significantly reduce the concentrations of extracellular polymeric substances (EPS) and total cell counts (TCC) within the biofouling layer, and engineer highly heterogeneous structures of biofouling layer on the membrane surface. In the fresh GAC/GDM process, the improved flux obtained was mainly related to less coverage of biofouling layer and lower EPS concentrations due to efficient removals of membrane foulants by GAC adsorption. The achieved higher stable flux can be maintained during long-term filtration (after GAC saturation) owing to the combined effects of EPS reduction and formation of highly heterogeneous structures of biofouling layer in the saturated GAC/GDM system. Overall, the integrated GAC/GDM process can hopefully facilitate improvements both in the stabilized flux and permeate quality, with practical relevance for GDM applications in decentralized drinking water supply.
Ward, B. J., Andriessen, N., Tembo, J. M., Kabika, J., Grau, M., Scheidegger, A., … Strande, L. (2021). Predictive models using "cheap and easy" field measurements: can they fill a gap in planning, monitoring, and implementing fecal sludge management solutions?. Water Research, 196, 116997 (12 pp.). doi:10.1016/j.watres.2021.116997, Institutional Repository

The characteristics of fecal sludge delivered to treatment plants are highly variable. Adapting treatment process operations accordingly is challenging due to a lack of analytical capacity for characterization and monitoring at many treatment plants. Cost-efficient and simple field measurements such as photographs and probe readings could be proxies for process control parameters that normally require laboratory analysis. To investigate this, we evaluated questionnaire data, expert assessments, and simple analytical measurements for fecal sludge collected from 421 onsite containments. This data served as inputs to models of varying complexity. Random forest and linear regression models were able to predict physical-chemical characteristics including total solids (TS) and ammonium (NH4+-N) concentrations, and solid-liquid separation performance including settling efficiency and filtration time (R2 from 0.51-0.66) based on image analysis of photographs (sludge color, supernatant color, and texture) and probe readings (conductivity (EC) and pH). Supernatant color was the best predictor of settling efficiency and filtration time, EC was the best predictor of NH4+-N, and texture was the best predictor of TS. Predictive models have the potential to be applied for real-time monitoring and process control if a database of measurements is developed and models are validated in other cities. Simple decision tree models based on the single classifier of containment type can also be used to make predictions about citywide planning, where a lower degree of accuracy is required.
Wielinski, J., Gogos, A., Voegelin, A., Müller, C. R., Morgenroth, E., & Kaegi, R. (2021). Release of gold (Au), silver (Ag) and cerium dioxide (CeO2) nanoparticles from sewage sludge incineration ash. Environmental Science: Nano, 8(11), 3220-3232. doi:10.1039/D1EN00497B, Institutional Repository

Engineered nanoparticles (NPs) that are released into wastewater are retained by wastewater treatment plants (WWTPs) and accumulate in sewage sludge. Increasing shares of sludge are incinerated and landfilled, especially in industrialized countries. It is debated whether certain types of NPs can outlive the incineration process and subsequently be released from sewage sludge ash (SSA) landfills. To investigate the release of different types of NPs from SSA, we spiked gold (Au), silver (Ag) and cerium dioxide (CeO2) NPs to a pilot WWTP increasing the Au, Ag and Ce concentrations to 30, 43 and 389 mg kg-1 (dry matter basis) in the digested sludge. The spiked sludge was incinerated in a pilot fluidized bed reactor resulting in SSA with Au, Ag and Ce concentrations of 61, 103 and 854 mg kg-1. In addition, two sludge samples from a full-scale WWTP with Au concentrations of 5 and 16 mg kg-1 were incinerated, resulting in SSA with 9 mg kg-1 and 30 mg kg-1 Au. The spiked Au-NPs remain largely unaltered during the wastewater treatment and incineration process, whereas Ag-NPs and CeO2-NPs undergo transformation. During simulated landfill leaching in columns flushed with 400 to 500 pore volumes of artificial rainwater, Ag and Ce were retained in the ash, whereas about 17% of the spiked Au was released, mainly in particulate form. Lower fractions of mostly particulate Au were released from the ashes (3 and 9%) of unspiked SSA. In conclusion, unaltered Au-NPs significantly leach from landfilled SSA, whereas the incorporation of Ag-NPs and CeO2-NPs as transformed species into the SSA matrix limits the leaching of (nano)particulate and dissolved Ag and Ce compounds.
Wielinski, J., Voegelin, A., Grobéty, B., Müller, C. R., Morgenroth, E., & Kaegi, R. (2021). Transformation of TiO2 (nano)particles during sewage sludge incineration. Journal of Hazardous Materials, 411, 124932 (14 pp.). doi:10.1016/j.jhazmat.2020.124932, Institutional Repository

Titanium dioxide (TiO2) (nano)particles are produced in large quantities and their potential impacts on ecosystems warrants investigations into their fate after disposal. TiO2 particles released into wastewater are retained by wastewater treatment plants and accumulate in digested sludge, which is increasingly incinerated in industrialized countries. Therefore, we investigated the changes of the Ti-speciation during incineration of as-received sludge and of sludge spiked with anatase (d=20–50 nm) or rutile (d=200–400 nm) using X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM). In the as-received sludge, rutile and anatase were the dominant Ti bearing minerals and both remained unaffected by the anaerobic treatment. During incineration, Ti reacts with hematite to members of the hematite-ilmenite solid solution series (Hem-Ilm). Up to 80% of the Ti spiked as anatase transformed into Hem-Ilm, a distorted 6-fold coordinated Ti (Ti(IV)sulfate) and rutile during incineration. Up to 30% and 60% of rutile transformed into Hem-Ilm and Ti(IV)sulfate represented phases in fly and bottom ash, respectively. Fe and Ti were spatially correlated in ash derived from as-received and anatase spiked sludge, whereas only a thin layer of the spiked rutile reacted with Fe, in line with XAS data. This study highlights the transient nature of nano-Ti species during sewage sludge incineration.
Zhang, L., Graham, N., Derlon, N., Tang, Y., Siddique, M. S., Xu, L., & Yu, W. (2021). Biofouling by ultra-low pressure filtration of surface water: the paramount role of initial available biopolymers. Journal of Membrane Science, 640, 119740 (9 pp.). doi:10.1016/j.memsci.2021.119740, Institutional Repository

Biofouling layer (i.e., biofilm) is an inevitable presence for the membrane filtration processes. In this study, we elucidated biofouling formation from the perspective of affecting the attachment of bacteria for the first time, whereby the role of initial available biopolymers was revealed. Results demonstrated that the presence of initial available biopolymers increased the abundance of the genus Caulobacter, which was capable of mineralizing biopolymers; whereas, for the typically oligotrophic species of Polynucleobacter, it exhibited low abundance. Greater concentrations of polysaccharides and proteins were accumulated in the biofouling layer, when provided with initial biopolymers, and the biofilm structure was more heterogeneous with larger pore size and higher thickness. Thereby, the corresponding filtration system exhibited greater permeability and better removal performance of organics. Collectively, the initial available biopolymers altered the attachment conditions for the bacteria, which subsequently impacted the bacterial community, and in turn biofilm composition, physical structure and filtration performance.
Ziemba, C., Sharma, P., Ahrens, T., Reynaert, E., & Morgenroth, E. (2021). Disruptions in loading and aeration impact effluent chlorine demand during biological greywater recycling. Water Research X, 11, 100087 (10 pp.). doi:10.1016/j.wroa.2020.100087, Institutional Repository

Greywater recycling systems designed for high-quality applications, such as hand washing, must deliver microbially safe and aesthetically acceptable water under the challenging operating conditions present where such systems are needed most urgently. As chlorination is the most popular strategy for reducing bacterial concentrations in greywater, understanding chlorination in the context of disruptive and challenging operation is essential to designing robust treatment. In this study, we have examined how disruptions through overall increased loading, interrupted aeration and increased ammonia loading have impacted the chlorine demand of the water produced by a greywater recycling system. We also presented concentrations of significant chemicals that contributed to this chlorine demand. The results indicate that a 1 d period with 8 times (8x) the normal design loading produced a peak chlorine demand of 0.74 mg Cl2/L, which is approximately double the baseline value. While this chlorine demand can be overcome by adding more chlorine, tests involving disruptions in aeration or feeding additional ammonia into the bioreactor produced much greater increases (>30x). The risks of increased chlorine demand on microbial safety can be overcome by limiting ammonia inputs to the system, providing backup systems to ensure sufficient aeration, or through additional anti-bacterial measures that do not depend on maintaining residual chlorine.
Özel Duygan, B. D., Udert, K. M., Remmele, A., & McArdell, C. S. (2021). Removal of pharmaceuticals from human urine during storage, aerobic biological treatment, and activated carbon adsorption to produce a safe fertilizer. Resources, Conservation and Recycling, 166, 105341 (10 pp.). doi:10.1016/j.resconrec.2020.105341, Institutional Repository

Urine has great potential to be an effective fertilizer due to its high nutrient content, however, it can contain potentially worrying pharmaceuticals. Our objective was to study whether urine storage and aerobic biological treatment, i.e. nitrification, was sufficient to remove pharmaceuticals or an additional treatment with activated carbon was necessary to produce a fertilizer from urine. We investigated the abatement of twelve pharmaceuticals, including antibiotics and antivirals, in laboratory experiments representing the treatment steps of anaerobic storage of source-separated human urine, stabilization using partial and full nitrification under acclimatized and non-acclimatized conditions, and treatment of nitrified urine using powdered activated carbon (PAC). Two-month-long-term storage of urine was insufficient to substantially degrade the pharmaceuticals, except for hydrochlorothiazide (>90%). In the partial and full nitrification fed-batch reactors, atazanavir, ritonavir, and clarithromycin were rapidly removed, with biotransformation rate constants greater than 10 L gSS−1d−1. Darunavir, emtricitabine, trimethoprim, N4-acetylsulfamethoxazole, sulfamethoxazole, atenolol, diclofenac, and hydrochlorothiazide were degraded slowly, with biotransformation rate constants of < 1 L gSS−1d−1. With 200 mg PAC L−1, at least 90% of each investigated pharmaceutical was removed. Yeast estrogen screen tests and bioluminescence inhibition tests revealed efficient removal of estrogenicity (99%) and toxicity (56%) using nitrification, and a reduction of 89% and 64%, respectively, using 200 mg PAC L−1. With our study, we provide biotransformation rate constants of compounds never previously investigated. We also show that a combination of nitrification and PAC adsorption enables the production of a safe fertilizer with sufficiently low pharmaceutical concentrations and no removal of beneficial nutrients.
Al-Sid-Cheikh, M., Rowland, S. J., Kaegi, R., Henry, T. B., Cormier, M. A., & Thompson, R. C. (2020). Synthesis of 14C-labelled polystyrene nanoplastics for environmental studies. Communications Materials, 1(1), 97 (8 pp.). doi:10.1038/s43246-020-00097-9, Institutional Repository

Available analytical methods cannot detect nanoplastics at environmentally realistic concentrations in complex matrices such as biological tissues. Here, we describe a one-step polymerization method, allowing direct radiolabeling of a sulfonate end-capped nano-sized polystyrene (nPS; proposed as a model nanoplastic particle representing negatively charged nanoplastics). The method, which produces nanoplastics trackable in simulated environmental settings which have already been used to investigate the behavior of a nanoplastic in vivo in a bivalve mollusc, was developed, optimized and successfully applied to synthesis of 14C-labeled nPS of different sizes. In addition to a description of the method of synthesis, we describe the details for quantification, mass balance and recovery of the labelled particles from complex matrices offered by the radiolabelling approach. The radiolabeling approach described here, coupled to use of a highly sensitive autoradiographic method for monitoring nanoplastic body burden and distributions, may provide a valuable procedure for investigating the environmental pathways followed by negatively charged nanoplastics at low predicted environmental concentrations. Whether the behaviour of the synthetic nPS manufactured here, synthesised using a very common inititator, represents that of manufactured nPS found in the environment, remains to be seen.
Bisinella de Faria, A. B., Besson, M., Ahmadi, A., Udert, K. M., & Spérandio, M. (2020). Dynamic influent generator for alternative wastewater management with urine source separation. Journal of Sustainable Water in the Built Environment, 6(2), 04020001 (26 pp.). doi:10.1061/JSWBAY.0000904, Institutional Repository

The simulation of wastewater treatment plants allows obtaining predictive results when one needs to understand, evaluate, optimize, or design a plant. However, one of the bottlenecks of simulation feasibility is to obtain reliable and dynamic influent data. This difficulty is even more important when alternative scenarios are considered, such as source-separated streams. The present paper offers an influent generator to simulate scenarios where urine is separated at the source and at a user-specified level of retention. The proposed tool contains several blocks to include different contributions (household and industrial wastewater) and, due to its flexibility, allows the user to easily modify the parameters to fit other case studies. The tool allowed generating dynamic, long-term, and predictive data for both urine and wastewater streams. Also, the extensive set of state variables ensured the generation of influents for different modeling platforms.
Bogler, A., Packman, A., Furman, A., Gross, A., Kushmaro, A., Ronen, A., … Bar-Zeev, E. (2020). Rethinking wastewater risks and monitoring in light of the COVID-19 pandemic. Nature Sustainability, 3, 981-990. doi:10.1038/s41893-020-00605-2, Institutional Repository

The COVID-19 pandemic has severely impacted public health and the worldwide economy. Converging evidence from the current pandemic, previous outbreaks and controlled experiments indicates that SARS-CoVs are present in wastewater for several days, leading to potential health risks via waterborne and aerosolized wastewater pathways. Conventional wastewater treatment provides only partial removal of SARS-CoVs, thus safe disposal or reuse will depend on the efficacy of final disinfection. This underscores the need for a risk assessment and management framework tailored to SARS-CoV-2 transmission via wastewater, including new tools for environmental surveillance, ensuring adequate disinfection as a component of overall COVID-19 pandemic containment.
Britschgi, L., Villez, K., Schrems, P., & Udert, K. M. (2020). Electrochemical nitrite sensing for urine nitrification. Water Research X, 9, 100055 (30 pp.). doi:10.1016/j.wroa.2020.100055, Institutional Repository

Sensing nitrite in-situ in wastewater treatment processes could greatly simplify process control, especially during treatment of high-strength nitrogen wastewaters such as digester supernatant or, as in our case, urine. The two technologies available today, i.e. an on-line nitrite analyzer and a spectrophotometric sensor, have strong limitations such as sample preparation, cost of ownership and strong interferences. A promising alternative is the amperometric measurement of nitrite, which we assessed in this study. We investigated the sensor in a urine nitrification reactor and in ex-situ experiments. Based on theoretical calculations as well as a practical approach, we determined that the critical nitrite concentrations for nitrite oxidizing bacteria lie between 12 and 30 mgN/L at pH 6 to 6.8. Consequently, we decided that the sensor should be able to reliably measure concentrations up to 50 mgN/L, which is about double the value of the critical nitrite concentration. We found that the influences of various ambient conditions, such as temperature, pH, electric conductivity and aeration rate, in the ranges expected in urine nitrification systems, are negligible. For low nitrite concentrations, as expected in municipal wastewater treatment, the tested amperometric nitrite sensor was not sufficiently sensitive. Nevertheless, the sensor delivered reliable measurements for nitrite concentrations of 5-50 mgN/L or higher. This means that the amperometric nitrite sensor allows detection of critical nitrite concentrations without difficulty in high-strength nitrogen conversion processes, such as the nitrification of human urine.
Burdon, F. J., Bai, Y., Reyes, M., Tamminen, M., Staudacher, P., Mangold, S., … Stamm, C. (2020). Stream microbial communities and ecosystem functioning show complex responses to multiple stressors in wastewater. Global Change Biology, 26(11), 6363-6382. doi:10.1111/gcb.15302, Institutional Repository

Multiple anthropogenic drivers are changing ecosystems globally, with a disproportionate and intensifying impact on freshwater habitats. A major impact of urbanization are inputs from wastewater treatment plants (WWTPs). Initially designed to reduce eutrophication and improve water quality, WWTPs increasingly release a multitude of micropollutants (MPs; i.e., synthetic chemicals) and microbes (including antibiotic‐resistant bacteria) to receiving environments. This pollution may have pervasive impacts on biodiversity and ecosystem services. Viewed through multiple lenses of macroecological and ecotoxicological theory, we combined field, flume, and laboratory experiments to determine the effects of wastewater (WW) on microbial communities and organic‐matter processing using a standardized decomposition assay. First, we conducted a mensurative experiment sampling 60 locations above and below WWTP discharges in 20 Swiss streams. Microbial respiration and decomposition rates were positively influenced by WW inputs via warming and nutrient enrichment, but with a notable exception: WW decreased the activation energy of decomposition, indicating a "slowing" of this fundamental ecosystem process in response to temperature. Second, next‐generation sequencing indicated that microbial community structure below WWTPs was altered, with significant compositional turnover, reduced richness, and evidence of negative MP influences. Third, a series of flume experiments confirmed that although diluted WW generally has positive influences on microbial‐mediated processes, the negative effects of MPs are "masked" by nutrient enrichment. Finally, transplant experiments suggested that WW‐borne microbes enhance decomposition rates. Taken together, our results affirm the multiple stressor paradigm by showing that different aspects of WW (warming, nutrients, microbes, and MPs) jointly influence ecosystem functioning in complex ways. Increased respiration rates below WWTPs potentially generate ecosystem "disservices" via greater carbon evasion from streams and rivers. However, toxic MP effects may fundamentally alter ecological scaling relationships, indicating the need for a rapprochement between ecotoxicological and macroecological perspectives.
Cai, Y., Yang, T., Mitrano, D. M., Heuberger, M., Hufenus, R., & Nowack, B. (2020). Systematic study of microplastic fiber release from 12 different polyester textiles during washing. Environmental Science and Technology, 54(8), 4847-4855. doi:10.1021/acs.est.9b07395, Institutional Repository

Microplastic fibers (MPFs) have been found to be a major form of microplastics in freshwaters, and washing of synthetic textiles has been identified as one of their main sources. The aim of this work was to use a panel of 12 different textiles of representative fibers and textile types to investigate the source(s) of the MPF during washing. Using standardized washing tests, textile swatches tailored using five different cutting/sewing methods were washed up to 10 times. The MPF quantity and fiber length were determined using image analysis. The 12 textiles demonstrated great variability in MPF release, ranging from 210 to 72,000 MPF/g textile per wash. The median MPF length ranged from 165 to 841 μm. The number of released MPF was influenced by the cutting method, where scissor-cut samples released 3-21 times higher numbers of MPF than the laser-cut samples. The textiles with mechanically processed surfaces (i.e., fleece) released significantly more (p-value < 0.001) than the textiles with unprocessed surfaces. For all textiles, the MPF release decreased with repeated wash cycles, and a small continuous fiber release was observed after 5-6 washings, accompanied by a slight increase in the fiber length. The decrease in the number of MPF released is likely caused by depletion of the production-inherited MPFs trapped within the threads or the textile structure. The comparison of MPF release from laser-cut samples, which had sealed edges, and the other cutting methods allowed us to separate the contributions of the edge- and surface-sourced fibers from the textiles to the total release. On an average, 84% (range 49-95%) of the MPF release originated from the edges, highlighting the importance of the edge-to-surface ratio when comparing different release studies. The large contribution of the edges to the total release offers options for technical solutions which have the possibility to control MPF formation throughout the textile manufacturing chain by using cutting methods which minimize MPF formation.
Cai, Y., Mitrano, D. M., Heuberger, M., Hufenus, R., & Nowack, B. (2020). The origin of microplastic fiber in polyester textiles: the textile production process matters. Journal of Cleaner Production, 267, 121970 (12 pp.). doi:10.1016/j.jclepro.2020.121970, Institutional Repository

Microplastic fibers (MPF) are often detected in waste water treatment plants and environmental samples, which implies a pathway of MPF release from domestic washing of textiles into the environment. Although there are many textile washing/release studies, it is still unclear to what extent the liberated MPFs originate from processes during washing (e.g. abrasion) or rather from processes earlier in the textile supply chain. Understanding the origin of MPFs is important since different MPF formation mechanisms would lead to different mitigation strategies. Therefore, the aim of our study was to investigate the presence of MPFs in various intermediate and finished polyester textiles products. In this study, we developed a sonication extraction method to quantify and characterize extractable MPFs already present in the textiles (i.e. manufacturing related MPFs). To identify the manufacturing process responsible for the MPF formation, this study included 18 representative products along the textile production line. The extraction dynamics of MPFs for all materials were investigated by ultrasonication. The number of extracted MPFs ranged from 15 MPF/g for a filament to 45'400 MPF/g for a scissor-cut microfiber textile. We found that a rotor yarn exhibited an elevated number of extracted MPFs (4'310 MPF/g) compared to other types of yarns (160-230 MPFs/g), suggesting that the rotor spinning may be a critical step responsible for MPF formation. On average, five times more MPFs could be extracted from textiles with processed surfaces (such as Fleece, Plain brushed and Microfiber) compared to those with unprocessed surfaces. This suggests that abrasive friction during production may be another critical factor for MPF formation. Furthermore, scissor-cut textiles demonstrated three to 31 times higher number of extracted MPFs than laser-cut textiles, enabling us to quantitatively discriminate between the contribution of MPFs from the textile surface opposed to those originating from the textile edges. The majority of the extracted MPFs were found to be between 100 and 800 μm in length. The results of this study may help to reduce the MPF release from textiles by modifications throughout the production and finishing process.
Domagała, K., Jacquin, C., Borlaf, M., Sinnet, B., Julian, T., Kata, D., & Graule, T. (2020). Efficiency and stability evaluation of Cu2O/MWCNTs filters for virus removal from water. Water Research, 179, 115879 (10 pp.). doi:10.1016/j.watres.2020.115879, Institutional Repository

Both multi-walled carbon nanotubes (MWCNTs) and metal or metal oxides have demonstrated virus removal efficacy in drinking water applications. In this study, MWCNTs were coated with copper(I) oxide (Cu2O) using three distinct synthesis procedures (copper ion attachment, copper hydroxide precipitation, and [Cu(NH3)4]2+ complex attachment) and virus removal efficacy (using MS2 bacteriophages) was evaluated. All synthesis procedures resulted in the presence of adsorbed, nanosized Cu2O particles on the MWCNTs, shown using X-ray diffraction. Further, transmission electron microscopy confirmed uniform copper(I) oxide distribution along the MWCNTs for all three materials. Virus removal efficacy was assessed for all three synthesised composites both before and after material conditioning (filtering for at least 24 h/280 mL/h), and accounting for additional MS2 inactivation in the permeate due to continued copper inactivation from dissolved/desorbed copper in permeate (time-control). Material conditioning influenced virus removal, with the first litres of water containing higher concentrations of copper than the sixth litres of water, suggesting excess or non-bonded copper species dissolve from filters. Higher copper dissolution was observed for water at pH 5 than at pH 7, which decreased with time. Copper dissolution most likely caused an associated decrease in copper adsorbed to MWCNTs in the filters, which may explain the observed lower MS2 removal efficacy after conditioning. Additionally, the time-control study (immediately after filtration as compared to 2 h after filtration) highlighted continued MS2 inactivation in the permeate over time. The obtained results indicate that the synthesis procedure influences virus removal efficacy for MWCNTs coated with copper oxides and that virus removal is likely due to not only virus electrostatic adsorption to the coated MWCNTs, but also through antiviral properties of copper which continues to act in the permeate. In conclusion, it is highly important to revise the methods of testing filter materials for virus removal, as well as procedure for virus concentration evaluation.
Dörner, L., Schmutz, P., Kägi, R., Kovalenko, M. V., & Jeurgens, L. P. H. (2020). Electrophoretic deposition of nanoporous oxide coatings from concentrated CuO nanoparticle dispersions. Langmuir, 36(28), 8075-8085. doi:10.1021/acs.langmuir.0c00720, Institutional Repository

Electrophoretic deposition (EPD) of nanoporous oxide coatings is an interesting research avenue owing to the experimental simplicity and broad scope of applications and materials. In this study, the properties of concentrated (up to 5000 mg/L), nonaqueous CuO nanoparticle (NP) dispersions were tailored to produce micrometer-thick, nanoporous CuO films by EPD. In particular, we performed a systematic investigation of the electrophoretic mobilities and size distributions of dispersed CuO aggregates and developing agglomerates in different organic solvents for concentrations ranging from 50 to 5000 mg/L with and without surfactant addition. Time-resolved dynamic light scattering analyses showed that aggregate mobilities and agglomeration rates decrease with increasing hydrocarbon chain length of the organic solvent (from ethanol to hexanol) and thus with increasing viscosity. The highest electrophoretic mobility was obtained for CuO NP aggregates and agglomerates dispersed in ethanol as a solvent. However, the addition of ≥0.5 wt % acetylacetone as a surfactant is required to stabilize these dispersions for subsequent EPD and at the same time introduce a net attractive (electrostatic) interaction between neighboring agglomerates on the substrate to promote layer formation during the EPD step. The produced micrometer-thick nanoporous CuO coatings can serve as high surface area nanostructured materials or nanoporous scaffolds in catalysis, combustion, propellants, and nanojoining.
Frehland, S., Kaegi, R., Hufenus, R., & Mitrano, D. M. (2020). Long-term assessment of nanoplastic particle and microplastic fiber flux through a pilot wastewater treatment plant using metal-doped plastics. Water Research, 182, 115860 (9 pp.). doi:10.1016/j.watres.2020.115860, Institutional Repository

In recent years, several studies have investigated the flux of particulate plastic through municipal waste water treatment plants (WWTP). Challenges related to time consuming analytical methods have limited the number of sampling points and detection limits have hampered quantification of nanoplastic and microplastic fiber fluxes through WWTPs. By synthesizing nanoplastic particles and microplastic fibers labeled with a rare metal (Pd and In, respectively) which can be measured as a proxy for the plastic itself, we have circumvented major analytical pitfalls associated with (micro)plastic measurements. In this study, we spiked the labeled materials to a pilot WWTP mimicking the activated sludge process (nitrification, de-nitrification and secondary clarification). Using a mass flow model for WWTP sludge, we assessed the behavior of particulate plastic in relation to the removal of organic matter. Triplicate samples were collected from the mixed liquor and from the effluent at least twice weekly over the entire experimental run time of 40 d. Our findings show that in discrete grab samples during steady state conditions, at least 98% of particulate plastics were associated with the biosolids. A positive correlation between total suspended solids (TSS) and plastic concentrations was observed in the sludge as well as in the effluent. Because of the strong association between particulate plastic and TSS, TSS removal is likely a good indicator of plastic removal in a full scale WWTP. Therefore, additional process steps in a full-scale WWTP which further reduce the TSS load will likely retain nanoplastic particles and microplastic fibers effectively and consequently increase the removal rates.
Fringer, V. S., Fawcett, L. P., Mitrano, D. M., & Maurer-Jones, M. A. (2020). Impacts of nanoplastics on the viability and riboflavin secretion in the model bacteria Shewanella oneidensis. Frontiers in Environmental Science, 8, 97 (11 pp.). doi:10.3389/fenvs.2020.00097, Institutional Repository

Characterizing the impact of nanoplastics to organism health is important to understand the consequences of the environmental plastic waste problem. This article examines the impact of nano-polystyrene (nano-PS; 159 ± 0.9 nm diameter) to ecologically relevant bacteria Shewanella oneidensis. Bacterial viability was evaluated using a growth-based assay. Riboflavin secretion is a critical cell function of S. oneidensis, serving as an electron mediator in anaerobic respiration and/or as a signaling molecule when the bacteria are under stress. Thus, changes in cellular function were monitored through riboflavin secretion in order to evaluate toxic responses that may not result in cell death. Under aerobic and anaerobic exposures (4, 8, or 12 h), the viability of the S. oneidensis was minimally changed as compared to the control, while the concentration of riboflavin secreted varied with exposure dose. In order to determine if this was a specific response to nanoplastic particles, opposed to a response to either particles or plastic more generally, we exposed the system to colloidal TiO2 nanoparticles and polystyrene and polyethylene thin films. We confirmed that riboflavin secretion trends were specific to nano-PS and not to these other materials, which showed no significant changes. We investigated the association of the nano-PS with ICP-MS using Pd that was chemically incorporated into the model nanoplastics. While 59.2% of the nano-PS were found in the non-cellular culture media, 7.0 and 6.6% was found associated with the loosely and tightly bound extracellular polymeric substance, respectively. There was significantly more nano-PS (10.9%) strongly associated with the cells. Taken together, we found that nano-PS had minimal impacts to viability but caused a significant change in the function of S. oneidensis that can be related to the nano-PS attached or in proximity to the bacterium. These trends are consistent between aerobic and anaerobic cultures, signifying that the stress response of S. oneidensis can be generalized between different environmental compartments. This work highlights that the association of nanoplastic materials with microorganisms may modify the cellular function that could ultimately be an impact to ecosystem health.
Geitner, N. K., Ogilvie Hendren, C., Cornelis, G., Kaegi, R., Lead, J. R., Lowry, G. V., … Wiesner, M. R. (2020). Harmonizing across environmental nanomaterial testing media for increased comparability of nanomaterial datasets. Environmental Science: Nano, 7(1), 13-36. doi:10.1039/c9en00448c, Institutional Repository

The chemical composition and properties of environmental media determine nanomaterial (NM) transport, fate, biouptake, and organism response. To compare and interpret experimental data, it is essential that sufficient context be provided for describing the physical and chemical characteristics of the setting in which a nanomaterial may be present. While the nanomaterial environmental, health and safety (NanoEHS) field has begun harmonization to allow data comparison and re-use (e.g. using standardized materials, defining a minimum set of required material characterizations), there is limited guidance for standardizing test media. Since most of the NM properties driving environmental behaviour and toxicity are medium-dependent, harmonization of media is critical. A workshop in March 2016 at Duke University identified five categories of test media: aquatic testing media, soil and sediment testing media, biological testing media, engineered systems testing media and product matrix testing media. For each category of test media, a minimum set of medium characteristics to report in all NM tests is recommended. Definitions and detail level of the recommendations for specific standardized media vary across these media categories. This reflects the variation in the maturity of their use as a test medium and associated measurement techniques, variation in utility and relevance of standardizing medium properties, ability to simplify standardizing reporting requirements, and in the availability of established standard reference media. Adoption of these media harmonization recommendations will facilitate the generation of integrated comparable datasets on NM fate and effects. This will in turn allow testing of the predictive utility of functional assay measurements on NMs in relevant media, support investigation of first principles approaches to understand behavioral mechanisms, and support categorization strategies to guide research, commercial development, and policy.
Gogos, A., Wielinski, J., Voegelin, A., von der Kammer, F., & Kaegi, R. (2020). Quantification of anthropogenic and geogenic Ce in sewage sludge based on Ce oxidation state and rare earth element patterns. Water Research X, 9, 100059 (8 pp.). doi:10.1016/j.wroa.2020.100059, Institutional Repository

Emissions of Ce from anthropogenic activities (anthropogenic Ce) into urban wastewater systems and the environment result from its widespread industrial use (abrasives, catalysts, nanotechnology). Because Ce in sewage sludge can also be of geogenic origin, the quantification of anthropogenic Ce in sewage sludge remains elusive. In this study, we evaluated the suitability of Ce oxidation state and rare earth element (REE) patterns for the quantification of anthropogenic Ce fractions in sewage sludge. A diverse set of soil samples served to gain baseline information on geogenic Ce. Geogenic Ce in the soils was characterized by high Ce(III) fractions (≥70%) and their REE patterns were comparable to the REE patterns of the upper continental crust. The sewage sludges contained on average ∼80% Ce(IV) (range 18–108%), pointing to the importance of anthropogenic inputs of Ce(IV). The quantification of the anthropogenic Ce fraction based on Ce oxidation state, however, was associated with considerable uncertainty because geogenic and anthropogenic Ce cannot exclusively be assigned to Ce(III) and Ce(IV), respectively. The REE patterns of most sewage sludges indicated a clear enrichment of Ce compared to heavier REE. Based on the assumption that the industrially used Ce is free of (most) other REE, we estimated the fraction of anthropogenic Ce in the sludges based on individual Ce/REE ratios. For the individual sludges the anthropogenic contributions were very variable (10–100%) but consistent fractions were obtained for individual sludges when calculated based on Ce/Dy (dysprosium), Ce/Er (erbium) and Ce/Eu (europium) ratios. Electron microscopy analysis of sludges dominated by anthropogenic Ce revealed that the Ce was mostly contained in nanoscale particles devoid of elements characteristic of Ce-bearing minerals. Thus, anthropogenic Ce contents derived from REE patterns may be used to validate current mass flow models for engineered CeO2 nanoparticles.
Hadengue, B., Scheidegger, A., Morgenroth, E., & Larsen, T. A. (2020). Modeling the water-energy nexus in households. Energy and Buildings, 225, 110262 (10 pp.). doi:10.1016/j.enbuild.2020.110262, Institutional Repository

One third of the global carbon emissions are emitted by the building sector. Over the last decades, space heating loads have decreased in modern buildings, and domestic hot water (DHW) is now oftentimes the largest energy consumer in the household. We developed the WaterHub modeling framework to assess the potential of technologies or measures targeting DHW energy demand. The framework combines process-based technological models and stochastic water demand modeling in a modular way to allow for holistic simulations of complex DHW systems. In two rigorous tests of the modeling framework, we demonstrated the importance of water consumption dynamics in the modeling of DHW systems, showing that static modeling leads to underestimated heat losses and wrong energy consumption predictions. In an exemplary case study, we identified and quantified the synergistic interactions between water boiler temperatures and a drain water heat recovery device, demonstrating the strength of this methodology for optimizing strategies targeting DHW systems. With its modular structure, this open-source modeling framework can be extended to include any DHW-related technology, providing a useful common platform for collaboration between technology developers and water experts.
Hagemann, N., Schmidt, H. P., Kägi, R., Böhler, M., Sigmund, G., Maccagnan, A., … Bucheli, T. D. (2020). Wood-based activated biochar to eliminate organic micropollutants from biologically treated wastewater. Science of the Total Environment, 730, 138417 (11 pp.). doi:10.1016/j.scitotenv.2020.138417, Institutional Repository

Implementing advanced wastewater treatment (WWT) to eliminate organic micropollutants (OMPs) is a necessary step to protect vulnerable freshwater ecosystems and water resources. To this end, sorption of OMP by activated carbon (AC) is one viable technology among others. However, conventional AC production based on fossil precursor materials causes environmental pollution, including considerable emissions of greenhouse gases. In this study, we produced activated biochar (AB) from wood and woody residues by physical activation and evaluated their capability to eliminate OMPs in treated wastewater. Activated biochar produced under optimized conditions sorbed 15 model OMPs, of which most were dissociated at circumneutral pH, to the same or higher extent than commercial AC used as a reference. While wood quality played a minor role, the dosage of the activation agent was the main parameter controlling the capacity of ABs to eliminate OMP. Our results highlight the possibility for local production of AB from local wood or woody residues as a strategy to improve WWT avoiding negative side effects of conventional AC production.
Hess, A., Bettex, C., & Morgenroth, E. (2020). Influence of intermittent flow on removal of organics in a biological activated carbon filter (BAC) used as post-treatment for greywater. Water Research X, 9, 100078 (10 pp.). doi:10.1016/j.wroa.2020.100078, Institutional Repository

Highly variable flow has to be expected in decentralized greywater treatment and can lead to intermittent operation of the treatment system. However, few studies have addressed the influence of variable flow on the treatment performance of a biological activated carbon filter (BAC). In this study, we investigated the influence of intermittent flow using small-scale BAC columns, which treat greywater as a second treatment step following a membrane bioreactor (MBR). Three operating strategies to respond to variable flow were evaluated. The activated carbon was characterized before and after the experiments in terms of biological activity and sorption capacity. The performance of the BAC filters was assessed based on total organic carbon (TOC) removal, TOC fractions and growth potential. No significant differences were observed between constant flow compared to on-off operation with intermittent flow over the range of tested influent concentrations. Peaks with high TOC during 24 h periods were attenuated by sorption and biological degradation. Adsorbed TOC was released after switching back to normal concentrations for influent concentrations more than 5 times higher than usually observed, the BAC functioned as a temporary sink. In line with these results, the high influent TOC values led to increased biological activity in the filter but did not influence the sorption capacity. The experiments showed that intermittent flow does not negatively impact the performance of a BAC and that there is no need for additional equalization tanks to buffer the variable flow, for example in household-scale greywater treatment.
Hildebrandt, L., Mitrano, D. M., Zimmermann, T., & Pröfrock, D. (2020). A nanoplastic sampling and enrichment approach by continuous flow centrifugation. Frontiers in Environmental Science, 8, 89 (13 pp.). doi:10.3389/fenvs.2020.00089, Institutional Repository

Substantial efforts have been undertaken to isolate and characterize plastic contaminants in different sample matrices in the last years as the ubiquitous presence of particulate plastic in the environment has become evident. In comparison, plastic particles <1 µm (nanoplastic) in the environment remain mostly unexplored. Adequate techniques for the enrichment, as well as the detection of nanoplastic, are lacking but are urgently needed to assess the full scope of (potential) nanoplastic pollution. Use of Pd-doped nanoplastic particles constitutes a powerful tool to develop new analytical approaches, as they can be traced accurately and with ease in a variety of complex matrices by highly sensitive, time-efficient and robust ICP-MS(/MS) techniques. In this lab-scale study, for the first time, the capability of continuous flow centrifugation to retain nanoplastic particles (∼160 nm) from ultrapure water, as well as from filtered and unfiltered water from the German Elbe River was evaluated. Depending on the pump rate, the retention efficiency for the nanoplastic particles in ultrapure water ranged from 92% ± 8% (1 L h-1) to 53% ± 5% (5 L h-1) [uc (n = 3)] and from 75% ± 5% to 65% ± 6% (uc) (2.5 L h-1) in river water. Recirculating the water through the system two and three times at the highest tested flow rate led to retention efficiencies >90%. In a proof-of-principle setup, it was demonstrated that operating two continuous flow centrifuges sequentially at different rotational speeds bears the potential to enable size- and density-selective sampling of the colloidal fraction. A significant fraction of the spiked nanoplastic particles [76% ± 5% (uc)] could be separated from a model mixture of natural particles with a well-defined mean size of approximately 3 µm. While the certified reference plankton material used here was quantitatively retained in the first centrifuge rotor together with 23.0% ± 2.2% of the effective dose of the spiked nanoplastic, the remaining fraction of the nanoplastic could be recovered in the second rotor (53% ± 5%) and the effluent [24.4% ± 2.4% (uc)]. Based on the good retention efficiencies and the demonstrated separation potential, continuous flow centrifugation has proven to be a very promising technique for nanoplastic sampling and enrichment from natural water samples.
Hoffmann, S., Feldmann, U., Bach, P. M., Binz, C., Farrelly, M., Frantzeskaki, N., … Udert, K. M. (2020). A research agenda for the future of urban water management: exploring the potential of non-grid, small-grid, and hybrid solutions. Environmental Science and Technology, 54(9), 5312-5322. doi:10.1021/acs.est.9b05222, Institutional Repository

Recent developments in high- and middle-income countries have exhibited a shift from conventional urban water systems to alternative solutions that are more diverse in source separation, decentralization, and modularization. These solutions include non-grid, small-grid, and hybrid systems to address such pressing global challenges as climate change, eutrophication, and rapid urbanization. They close loops, recover valuable resources, and adapt quickly to changing boundary conditions such as population size. Moving to such alternative solutions requires both technical and social innovations to co-evolve over time into integrated socio-technical urban water systems. Current implementations of alternative systems in high- and middle-income countries are promising, but they also underline the need for research questions to be addressed from technical, social, and transformative perspectives. Future research should apply a transdisciplinary research approach through socio-technical "lighthouse" projects that apply alternative urban water systems at scale. Such research should leverage experience from lighthouse projects in a range of socio-economic contexts, identify their potentials and limitations from an integrated perspective, and share their successes and failures across the urban water sector.
Hoffmann, K., Bouchet, S., Christl, I., Kaegi, R., & Kretzschmar, R. (2020). Effect of NOM on copper sulfide nanoparticle growth, stability, and oxidative dissolution. Environmental Science: Nano, 7(4), 1163-1178. doi:10.1039/c9en01448a, Institutional Repository

Metal sulfide nanoparticles have recently been discovered in natural environments subject to fluctuating redox conditions such as wetlands and river floodplains, which are often very rich in natural organic matter (NOM). Strong binding of chalcophile metals like copper by NOM is expected to interfere with sulfide precipitation and is likely to affect the growth of these nanoparticles. We therefore conducted experiments on the formation of copper sulfide nanoparticles (CuxS NPs) in anoxic solutions with varying Cu (50, 500 μmol L-1) and sulfide (100, 1000 μmol L-1) concentrations in the absence and presence of Suwannee River fulvic acid (SRFA, 0, 5, 50 mg C L-1). The size development of the CuxS nanoparticles and their stability were tracked over 4 weeks using transmission electron microscopy (TEM) and size-exclusion chromatography coupled to ICP-MS (SEC-ICP-MS). Additional dissolution experiments were performed in closed containers in the absence and presence of O2 and fulvic acid over several months providing insights into the oxidative dissolution behavior of CuxS. Our results highlight the high colloidal stability of CuxS nanoparticles in anoxic environments irrespective of the NOM concentration. Median particle diameters ranged between a few and a few tens of nanometers with larger particles forming in more concentrated suspensions. At low Cu and S concentrations, fulvic acid restricted particle growth by up to 25% compared to SRFA-free suspensions and metal sulfide clusters even smaller than 1 nm were detected. The CuxS nanoparticles exhibited a remarkable chemical stability against oxidative dissolution and were only dissolved when both fulvic acid and O2 were present.
Hoffmann, K., Christl, I., Kaegi, R., & Kretzschmar, R. (2020). Effects of natural organic matter (NOM), metal-to-sulfide ratio and Mn2+ on cadmium sulfide nanoparticle growth and colloidal stability. Environmental Science: Nano, 7(11), 3385-3404. doi:10.1039/d0en00764a, Institutional Repository

Redox-dynamic environments such as river floodplains and wetlands have been identified as sources of natural metal sulfide nanoparticles (MS NPs). However, little information is available on how their growth and colloidal stability are affected by the concentrations of metals and sulfide in solution, the presence of natural organic matter (NOM), and the possible incorporation of other metal cations such as Fe2+ or Mn2+. Here, we performed experiments on the formation of CdS nanoparticles (CdS NPs) in anoxic solutions with varying Cd (50, 100, 500 μmol L-1) and sulfide (50, 100, 1000 μmol L-1) concentrations in the absence and presence of Suwannee River fulvic acid (SRFA, 0, 5, 50 mg C per L). Additionally, we studied the influence of different metal-to-sulfide ratios and varying Mn2+ (0, 0.1, 0.5, 1 mmol L−1) concentrations on CdS aggregation using dynamic light scattering (DLS), transmission electron microscopy (TEM), and electrophoretic mobility measurements. The incorporation of Mn into the crystal lattice of CdS over 8 weeks was investigated with X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Our results show that after 24 hours, small CdS primary particles with median diameters of a few nanometers (d~TEM = 2-14 nm) formed large aggregates (d~TEM = 167 nm) and that increasing SRFA concentrations progressively constrained the size of these aggregates (down to 19 nm) irrespective of the initial reactant stoichiometry. When NOM was absent or at low concentration, higher metal-to-sulfide ratios (≥1) and Mn2+ concentrations (≥0.5 mmol L-1) led to reduced colloidal stability of the suspensions. We found that in suspensions containing Mn2+, 10-30% of the Cd atoms in the crystal lattice were substituted by Mn during the formation of CdS, which was prevented by NOM.
Jacquin, C., Yu, D., Sander, M., Domagala, K. W., Traber, J., Morgenroth, E., & Julian, T. R. (2020). Competitive co-adsorption of bacteriophage MS2 and natural organic matter onto multiwalled carbon nanotubes. Water Research X, 9, 100058 (12 pp.). doi:10.1016/j.wroa.2020.100058, Institutional Repository

A leading challenge in drinking water treatment is to remove small-sized viruses from the water in a simple and efficient manner. Multi-walled carbon nanotubes (MWCNT) are new generation adsorbents with previously demonstrated potential as filter media to improve virus removal. This study therefore aimed to evaluate the field applicability of MWCNT-filters for virus removal in water containing natural organic matter (NOM) as co-solute to viruses, using batch equilibrium experiments. Contrary to previous studies, our results showed with MS2 bacteriophages single-solute systems that the affinity of MWCNT for MS2 was low, since after 3 h of equilibration only 4 log10 reduction value (LRV) of MS2 (20 mL at an initial concentration of 106 PFU MS2/mL) were reached. Single solute experiments with Suwannee river NOM (SRNOM) performed with environmentally-relevant concentrations showed MWCNT surface saturation at initial SRNOM concentrations between 10 and 15 mgC/L, for water pH between 5.2 and 8.7. These results suggested that at NOM:virus ratios found in natural waters, the NOM would competitively suppress virus adsorption onto MWCNT, even at low NOM concentrations. We confirmed this expectation with SRNOM-MS2 co-solute experiments, which showed an exponential decrease of the MS2 LRV by MWCNT with an increase in the initial SRNOM concentration. More interestingly, we showed that pre-equilibrating MWCNT with a SRNOM solution at a concentration as low as 0.4 mgC/L resulted in a LRV decrease of 3 for MS2, due to the formation of a negatively charged SRNOM adlayer on the MWCNT surface. Complementary batch experiments with natural NOM-containing waters and competition experiments with SRNOM in the presence of CaCl2 confirmed that the presence of NOM in waters challenges virus removal by MWCNT-filters, irrespective of the concentration and type of NOM and also in the presence of Ca2+. We therefore conclude that MWCNT-filters produced with commercially available pristine MWCNT cannot be considered as a viable technology for drinking water virus removal.
Javier, L., Farhat, N. M., Desmond, P., Valladares Linares, R., Bucs, S., Kruithof, J. C., & Vrouwenvelder, J. S. (2020). Biofouling control by phosphorus limitation strongly depends on the assimilable organic carbon concentration. Water Research, 183, 116051 (11 pp.). doi:10.1016/j.watres.2020.116051, Institutional Repository

Nutrient limitation is a biofouling control strategy in reverse osmosis (RO) membrane systems. In seawater, the assimilable organic carbon content available for bacterial growth ranges from about 50 to 400 μg C·L-1, while the phosphorus concentration ranges from 3 to 11 μg P·L-1. Several studies monitored biofouling development, limiting either carbon or phosphorus. The effect of carbon to phosphorus ratio and the restriction of both nutrients on membrane system performance have not yet been investigated.
This study examines the impact of reduced phosphorus concentration (from 25 μg P·L-1 and 3 μg P·L-1, to a low concentration of ≤0.3 μg P·L-1), combined with two different carbon concentrations (250 C L-1 and 30 μg C·L-1), on biofilm development in an RO system. Feed channel pressure drop was measured to determine the effect of the developed biofilm on system performance. The morphology of the accumulated biomass for both carbon concentrations was characterized by optical coherence tomography (OCT) and the biomass amount and composition was quantified by measuring total organic carbon (TOC), adenosine triphosphate (ATP), total cell counts (TCC), and extracellular polymeric substances (EPS) concentration for the developed biofilms under phosphorus restricted (P-restricted) and dosed (P-dosed) conditions.
For both carbon concentrations, P-restricted conditions (≤0.3 μg P·L-1) limited bacterial growth (lower values of ATP, TCC). A faster pressure drop increase was observed for P-restricted conditions compared to P-dosed conditions when 250 μg C·L-1 was dosed. This faster pressure drop increase can be explained by a higher area covered by biofilm in the flow channel and a higher amount of produced EPS. Conversely, a slower pressure drop increase was observed for P-restricted conditions compared to P-dosed conditions when 30 μg C·L-1 was dosed. Results of this study demonstrate that P-limitation delayed biofilm formation effectively when combined with low assimilable organic carbon concentration and thereby, lengthening the overall membrane system performance.
Jimenez, J., Charnier, C., Kouas, M., Latrille, E., Torrijos, M., Harmand, J., … Steyer, J. P. (2020). Modelling hydrolysis: simultaneous versus sequential biodegradation of the hydrolysable fractions. Waste Management, 101, 150-160. doi:10.1016/j.wasman.2019.10.004, Institutional Repository

Hydrolysis is considered the limiting step during solid waste anaerobic digestion (including co-digestion of sludge and biosolids). Mechanisms of hydrolysis are mechanistically not well understood with detrimental impact on model predictive capability. The common approach to multiple substrates is to consider simultaneous degradation of the substrates. This may not have the capacity to separate the different kinetics. Sequential degradation of substrates is theoretically supported by microbial capacity and the composite nature of substrates (bioaccessibility concept). However, this has not been experimentally assessed. Sequential chemical fractionation has been successfully used to define inputs for an anaerobic digestion model. In this paper, sequential extractions of organic substrates were evaluated in order to compare both models. By removing each fraction (from the most accessible to the least accessible fraction) from three different substrates, anaerobic incubation tests showed that for physically structured substrates, such as activated sludge and wheat straw, sequential approach could better describe experimental results, while this was less important for homogeneous materials such as pulped fruit. Following this, anaerobic incubation tests were performed on five substrates. Cumulative methane production was modelled by the simultaneous and sequential approaches. Results showed that the sequential model could fit the experimental data for all the substrates whereas simultaneous model did not work for some substrates.
Keller, A. S., Jimenez-Martinez, J., & Mitrano, D. M. (2020). Transport of nano- and microplastic through unsaturated porous media from sewage sludge application. Environmental Science and Technology, 54(2), 911-920. doi:10.1021/acs.est.9b06483, Institutional Repository

Wastewater treatment plants have been identified as important hubs for small particulate plastic, down to the nanometer scale, from urban areas to the environment. The reuse of sludge as fertilizer in agricultural practices can lead to accumulation of plastic in the soil. In this study, nanoplastic particles and microplastic fibers were synthesized with a passive inorganic tracer to aid in faster and more quantitative analysis using inductively coupled plasma mass spectrometry (ICP-MS). Using the anaerobic digestate of a pilot wastewater treatment plant spiked with metal-doped plastic, the excess sludge was dewatered, ensuring realistic associations between sludge and plastic. The resulting sludge cake was affixed atop an unsaturated porous-medium column of glass beads to assess: (i) the release of particulate plastic from the sludge, and (ii) the accumulation and mobility of plastic and organic matter through the column (analogous to a soil). A total of three particulate plastic treatments were assessed, in triplicate, where the plastic and mobile organic fractions were monitored for 14 pore water volumes. Due to size-limited transport, low deattachment from the sludge and reduced mobility through the column were found for microplastic fibers (>95% retention). However, cotransport between the mobile organic fraction and nanoplastic particles was observed, with 50% of both retained in the column. These results contribute to the understanding of the fate of particulate plastics and to assessing the associated environmental risks of particle mobility and percolation, particularly for nanoplastics.
Köpping, I., McArdell, C. S., Borowska, E., Böhler, M. A., & Udert, K. M. (2020). Removal of pharmaceuticals from nitrified urine by adsorption on granular activated carbon. Water Research X, 9, 100057 (10 pp.). doi:10.1016/j.wroa.2020.100057, Institutional Repository

Nitrification and distillation of urine allow for the recovery of all nutrients in a highly concentrated fertilizer solution. However, pharmaceuticals excreted with urine are only partially removed during these two process steps. For a sustainable and safe application, more extensive removal of pharmaceuticals is necessary. To enhance the pharmaceutical removal, which is already occurring during urine storage, nitrification and distillation, an adsorption column with granular activated carbon (GAC) can be included in the treatment train. We executed a pilot-scale study to investigate the adsorption of eleven indicator pharmaceuticals on GAC. During 74 days, we treated roughly 1000 L of pre-filtered and nitrified urine spiked with pharmaceuticals in two flow-through GAC columns filled with different grain sizes. We compared the performance of these columns by calculating the number of treated bed volumes until breakthrough and carbon usage rates. The eleven spiked pharmaceuticals were candesartan, carbamazepine, clarithromycin, diclofenac, emtricitabine, hydrochlorothiazide, irbesartan, metoprolol, N4-acetylsulfamethoxazole, sulfamethoxazole and trimethoprim. At the shortest empty bed contact time (EBCT) of 25 min, immediate breakthrough was observed in both columns shortly after the start of the experiments. Strong competition by natural organic material (NOM) could have caused the low pharmaceutical removal at the EBCT of 25 min. At EBCTs of 70, 92 and 115 min, more than 660 bed volumes could be treated until breakthrough in the column with fine GAC. The earliest breakthrough was observed for candesartan and clarithromycin. On coarse GAC, only half the number of bed volumes could be treated until breakthrough compared to fine GAC. The probable reason for the later breakthrough with fine GAC is the smaller intraparticle diffusive path length. DOC and UV absorbance measurements at 265 nm indicated that both parameters can be used as indicators for the breakthrough of pharmaceuticals. In contrast to pharmaceuticals and DOC, the nutrient compounds ammonium, nitrate, phosphate, potassium and sulfate were not removed significantly. A comparison with literature values suggests that the amount of GAC needed to remove pharmaceuticals from human excreta could be reduced by nearly two orders of magnitude, if urine were treated on site instead of being discharged and treated in a centralized wastewater treatment plant.
Layer, M., Garcia Villodres, M., Hernandez, A., Reynaert, E., Morgenroth, E., & Derlon, N. (2020). Limited simultaneous nitrification-denitrification (SND) in aerobic granular sludge systems treating municipal wastewater: mechanisms and practical implications. Water Research X, 7, 100048 (13 pp.). doi:10.1016/j.wroa.2020.100048, Institutional Repository

Simultaneous nitrification-denitrification (SND) is, in theory, a key advantage of aerobic granular sludge systems over conventional activated sludge systems. But practical experience and literature suggests that SND and thus total nitrogen removal are limited during treatment of municipal wastewater using AGS systems. This study thus aims at quantifying the extent and understanding the mechanisms of SND during treatment of municipal wastewater with aerobic granular sludge (AGS) systems. Experiments (long-term and batch-tests) as well as mathematical modelling were performed. Our experimental results demonstrate that SND is significantly limited during treatment of low-strength municipal wastewater with AGS systems (14-39%), while almost full SND is observed when treating synthetic influent containing only diffusible substrate (90%). Our simulations demonstrate that the main mechanisms behind limited SND are (1) the dynamics of anoxic zone formation inside the granule, (2) the diffusibility and availability of electron-donors in those zones and (3) the aeration mode. The development of anoxic zones is driven by the utilisation of oxygen in the upper layers of the granule leading to transport limitations of oxygen inside the granule; this effect is closely linked to granule size and wastewater composition. Development of anoxic zones during the aerobic phase is limited for small granules at constant aeration at bulk dissolved oxygen (DO) concentration of 2 mgO2 L-1, and anoxic zones only develop during a brief period of the aerated phase for large granules. Modelling results further indicate that a large fraction of electron-donors are actually utilised in aerobic rather than anoxic redox zones - in the bulk or at the granule surface. Thus, full SND cannot be achieved with AGS treating low strength municipal wastewater if a constant DO is maintained during the aeration phase. Optimised aeration strategies are therefore required. 2-step and alternating aeration are tested successfully using mathematical modelling and increase TN removal to 40-79%, without compromising nitrification, and by shifting electron-donor utilisation towards anoxic redox conditions.
Layer, M., Bock, K., Ranzinger, F., Horn, H., Morgenroth, E., & Derlon, N. (2020). Particulate substrate retention in plug-flow and fully-mixed conditions during operation of aerobic granular sludge systems. Water Research X, 9, 100075 (11 pp.). doi:10.1016/j.wroa.2020.100075, Institutional Repository

Particulate substrate (XB) is the major organic substrate fraction in most municipal wastewaters. However, the impact of XB on aerobic granular sludge (AGS) systems is not fully understood. This study evaluated the physical retention of XB in AGS sequencing batch reactor (SBR) during anaerobic plug-flow and then aerobic fully-mixed conditions. The influence of different sludge types and operational variables on the extent and mechanisms of XB retention in AGS SBR were evaluated. XB mass-balancing and magnetic resonance imaging (MRI) were applied. During the anaerobic plug-flow feeding, most XB was retained in the first few cm of the settled sludge bed within the interstitial voids, where XB settled and accumulated ultimately resulting in the formation of a filter-cake. Sedimentation and surface filtration were thus the dominant XB retention mechanisms during plug-flow conditions, indicating that contact and attachment of XB to the biomass was limited. XB retention was variable and influenced by the XB influent concentration, sludge bed composition and upflow feeding velocity (vww). XB retention increased with larger XB influent concentrations and lower vww, which demonstrated the importance of sedimentation on XB retention during plug-flow conditions. Hence, large fractions of influent XB likely re-suspended during aerobic fully-mixed conditions, where XB then preferentially and rapidly attached to the flocs. During fully-mixed conditions, increasing floc fractions, longer mixing times and larger XB concentrations increased XB retention. Elevated XB retention was observed after short mixing times < 60 min when flocs were present, and the contribution of flocs towards XB retention was even more pronounced for short mixing times < 5 min. Overall, our results suggest that flocs occupy an environmental niche that results from the availability of XB during aerobic fully-mixed conditions of AGS SBR. Therefore, a complete wash-out of flocs is not desirable in AGS systems treating municipal wastewater.
Merle, T., Knappe, D. R. U., Pronk, W., Vogler, B., Hollender, J., & von Gunten, U. (2020). Assessment of the breakthrough of micropollutants in full-scale granular activated carbon adsorbers by rapid small-scale column tests and a novel pilot-scale sampling approach. Environmental Science: Water Research and Technology, 6(10), 2742-2751. doi:10.1039/D0EW00405G, Institutional Repository

This study aimed to compare three approaches for predicting the service life of full-scale GAC adsorbers for the removal of micropollutants. The approaches included (i) rapid small-scale column tests (RSSCTs), (ii) two pilot-scale sampling approaches, and (iii) predictive correlations that consider micropollutant properties and background water matrix characteristics. The RSSCT could predict full-scale performance only if a micropollutant-specific fouling index was applied. At the pilot-scale, water samples were collected (1) over time at the top sampling point only (empty bed contact time (EBCT) of 1 minute) to minimize time to breakthrough (method 1) and (2) at different column depths at a single time point (method 2). Breakthrough curves obtained with method 2 more closely matched those obtained at the full-scale. In addition, method 2 is more convenient since it requires only one sampling campaign. Method 2 was used as a prognostic tool to predict breakthrough curves for micropollutants without full-scale data and a comparison with an existing prediction model gave satisfactory results for 6 out of 13 compounds.
Mitrano, D. M., & Wohlleben, W. (2020). Microplastic regulation should be more precise to incentivize both innovation and environmental safety. Nature Communications, 11(1), 5324 (12 pp.). doi:10.1038/s41467-020-19069-1, Institutional Repository

The presence of plastic in the environment has sparked discussion amongst scientists, regulators and the general public as to how industrialization and consumerism is shaping our world. Here we discuss restrictions on the intentional use of primary microplastics: small solid polymer particles in applications ranging from agriculture to cosmetics. Microplastic hazards are uncertain, and actions are not similarly prioritized by all actors. In some instances, replacement is technically simple and easily justified, but in others substitutions may come with more uncertainty, performance questions and costs. Scientific impact assessment of primary microplastics compared to their alternatives relies on a number of factors, such as microplastic harm, existence of replacement materials and the quality, cost and hazards of alternative materials. Regulations need a precise focus and must be enforceable by these measurements. Policymakers must carefully evaluate under which contexts incentives to replace certain microplastics can stimulate innovation of new, more competitive and environmentally conscious materials.
Moraes Schambeck, C., Girbal-Neuhauser, E., Böni, L., Fischer, P., Bessière, Y., Paul, E., … Derlon, N. (2020). Chemical and physical properties of alginate-like exopolymers of aerobic granules and flocs produced from different wastewaters. Bioresource Technology, 312, 123632 (11 pp.). doi:10.1016/j.biortech.2020.123632, Institutional Repository

The influence of wastewater (WW) composition and the bioaggregates types (floccular vs. aerobic granular sludge - AGS) on the content, physical-chemical, hydrogel and rheological properties of Alginate-Like Exopolymers (ALE) was studied. Results showed that ALE are a complex mixture of proteins, humic acids and polysaccharides. Overall, rather similar ALE content and composition was observed for the different types of sludge. Only the AGS fed with acetate and propionate yielded significantly larger amount of ALE (261 ± 33 mg VSALE/g VSsludge, +49%) and of uronic sugars in ALE (254 ± 32 mgglucuronic acid/g VSALE, +62%) than bioaggregates fed with no/very little volatile fatty acids. Mannuronic acids are involved in the cohesion of the hydrogels. ALE hydrogels elasticity changed significantly with the type/origin of the bioaggregates. ALE hydrogels elasticity from AGS was always higher than from flocs when fed with real WW. Hence, different types of sludge impact the properties of the recovered ALE.
Ranzinger, F., Matern, M., Layer, M., Guthausen, G., Wagner, M., Derlon, N., & Horn, H. (2020). Transport and retention of artificial and real wastewater particles inside a bed of settled aerobic granular sludge assessed applying magnetic resonance imaging. Water Research X, 7, 100050 (9 pp.). doi:10.1016/j.wroa.2020.100050, Institutional Repository

The removal or degradation of particulate organic matter is a crucial part in biological wastewater treatment. This is even more valid with respect to aerobic granular sludge and the impact of particulate organic matter on the formation and stability of the entire granulation process. Before the organic part of the particulate matter can be hydrolyzed and finally degraded by the microorganism, the particles have to be transported towards and retained within the granulated biomass. The understanding of these processes is currently very limited. Thus, the present study aimed at visualizing the transport of particulate organic matter into and through an aerobic granular sludge bed. Magnetic Resonance Imaging (MRI) was successfully applied to resolve the different fractions of a granular sludge bed over time and space. Quantification and merging of 3D data sets allowed for a clear determination of the particle distribution within the granular sludge bed. Dextran coated super paramagnetic iron oxide nanoparticles (SPIONs, dp = 38±10 nm) served as model particles for colloidal particles. Microcrystalline cellulose particles (dp = 1-20 μm) tagged with paramagnetic iron oxide were applied as a reference for toilet paper, which is a major fraction of particulate matter in domestic wastewater. The results were supplemented by the use of real wastewater particles with a size fraction between 28 and 100 μm. Colloidal SPIONs distributed evenly over the granular sludge bed penetrating the granules up to 300 μm. Rinsing the granular sludge bed proved their immobilization. Microcrystalline cellulose and real wastewater particles in the micrometer range accumulated in the void space between settled granules. An almost full retention of the wastewater particles was observed within the first 20 mm of the granular sludge bed. Moreover, the formation of particle layers indicates that most of the micrometer-sized particles are not attached to the biomass and remain mobile. Consequently, these particles are released into the bulk phase when the granulated sludge bed is resuspended.
Reynaert, E., Greenwood, E. E., Ndwandwe, B., Riechmann, M. E., Sindall, R. C., Udert, K. M., & Morgenroth, E. (2020). Practical implementation of true on-site water recycling systems for hand washing and toilet flushing. Water Research X, 7, 100051 (13 pp.). doi:10.1016/j.wroa.2020.100051, Institutional Repository

On-site wastewater reuse can improve global access to clean water, sanitation and hygiene. We developed a treatment system (aerated bioreactor, ultrafiltration membrane, granular activated carbon and electrolysis for chlorine disinfection) that recycles hand washing and toilet flush water.
Three prototypes were field-tested in non-sewered areas, one in Switzerland (hand washing) and two in South Africa (hand washing, toilet flushing), over periods of 63, 74 and 94 days, respectively.
We demonstrated that the system is able to recycle sufficient quantities of safe and appealing hand washing and toilet flush water for domestic or public use in real-life applications. Chemical contaminants were effectively removed from the used water in all prototypes. Removal efficiencies were 99.7% for the chemical oxygen demand (COD), 98.5% for total nitrogen (TN) and 99.9% for phosphate in a prototype treating hand washing water, and 99.8% for COD, 95.7% for TN and 89.6% for phosphate in a prototype treating toilet flush water. While this system allowed for true recycling for the same application, most on-site wastewater reuse systems downcycle the treated water, i.e., reuse it for an application requiring lower water quality. An analysis of 18 selected wastewater reuse specifications revealed that at best these guidelines are only partially applicable to innovative recycling systems as they are focused on the downcycling of water to the environment (e.g., use for irrigation). We believe that a paradigm shift is necessary and advocate for the implementation of risk-based (and thus end-use dependent) system performance targets to evaluate water treatment systems, which recycle and not only downcycle water.
Russo, S., Lürig, M., Hao, W., Matthews, B., & Villez, K. (2020). Active learning for anomaly detection in environmental data. Environmental Modelling and Software, 134, 104869 (11 pp.). doi:10.1016/j.envsoft.2020.104869, Institutional Repository

Due to the growing amount of data from in-situ sensors in environmental monitoring, it becomes necessary to automatically detect anomalous data points. Nowadays, this is mainly performed using supervised machine learning models, which need a fully labelled data set for their training process. However, the process of labelling data is typically cumbersome and, as a result, a hindrance to the adoption of machine learning methods for automated anomaly detection. In this work, we propose to address this challenge by means of active learning. This method consists of querying the domain expert for the labels of only a selected subset of the full data set. We show that this reduces the time and costs associated to labelling while delivering the same or similar anomaly detection performances. Finally, we also show that machine learning models providing a nonlinear classification boundary are to be recommended for anomaly detection in complex environmental data sets.
Schambeck, C. M., Magnus, B. S., de Souza, L. C. R., Leite, W. R. M., Derlon, N., Bittencourt Guimarães, L., & Ribeiro da Costa, R. H. (2020). Biopolymers recovery: dynamics and characterization of alginate-like exopolymers in an aerobic granular sludge system treating municipal wastewater without sludge inoculum. Journal of Environmental Management, 263, 110394 (11 pp.). doi:10.1016/j.jenvman.2020.110394, Institutional Repository

Alginate-like exopolymers (ALE) are present in the extracellular polymeric substances (EPS) of biological sludge such as aerobic granular sludge (AGS). The recovery of ALE from excess sludge produced by wastewater treatment plants (WWTP) is a relevant approach for the recovery of valuable products of industrial interest. However, little is known about dynamics of ALE content in sludge and associated factors. Thus, this study aimed at assessing the dynamics of EPS and ALE in terms of content, some chemical properties and influencing environmental factors along granulation in a sequencing batch reactor treating municipal wastewater. Results indicated that the EPS content was not correlated with the development of AGS, while the ALE content was higher, more stable and steadily increased after granulation achievement. Overall, 236 ± 27 mg VSALE/g VSsludge was recovered from AGS and 187 ± 94 mg VSALE/g VSsludge from flocs. However, the lower ALE content in flocs may be compensated by the higher sludge production rate in activated sludge systems. Principal component analysis (PCA) revealed that ALE content positively correlates with the nutrient and organic substrate conversion, and with the fraction of large AGS. Microbial analyses indicated that a stable microbial community composition was associated with a higher and more stable ALE content. ALE recovered from both flocs and AGS was endowed with hydrogel property, and no clear difference in their elemental composition and functional groups was observed. Therefore, our study provides insights about quantitative and qualitative aspects of ALE which are helpful for the improvement of waste biological sludge valorization.
Schneider, M. Y., Furrer, V., Sprenger, E., Carbajal, J. P., Villez, K., & Maurer, M. (2020). Benchmarking soft sensors for remote monitoring of on-site wastewater treatment plants. Environmental Science and Technology, 54(17), 10840-10849. doi:10.1021/acs.est.9b07760, Institutional Repository

On-site wastewater treatment plants (OSTs) are usually unattended, so failures often remain undetected and lead to prolonged periods of reduced performance. To stabilize the performance of unattended plants, soft sensors could expose faults and failures to the operator. In a previous study, we developed soft sensors and showed that soft sensors with data from unmaintained physical sensors can be as accurate as soft sensors with data from maintained ones. The monitored variables were pH and dissolved oxygen (DO), and soft sensors were used to predict nitrification performance. In the present study, we use synthetic data and monitor three plants to test these soft sensors. We find that a long solids retention time and a moderate aeration rate improve the pH soft-sensor accuracy and that the aeration regime is the main operational parameter affecting the accuracy of the DO soft sensor. We demonstrate that integrated design of monitoring and control is necessary to achieve robustness when extrapolating from one OST to another in the absence of plant-specific fine-tuning. Additionally, we provide a unique labeled dataset for further feature and data-driven soft-sensor development. Our benchmarking results indicate that it is feasible to monitor OSTs with unmaintained sensors and without plant-specific tuning of the developed soft sensors. This is expected to drastically reduce monitoring costs for OST-based sanitation systems.
Suess, E., Berg, M., Bouchet, S., Cayo, L., Hug, S. J., Kaegi, R., … Buser, A. M. (2020). Mercury loads and fluxes from wastewater: a nationwide survey in Switzerland. Water Research, 175, 115708 (10 pp.). doi:10.1016/j.watres.2020.115708, Institutional Repository

Mercury (Hg) pollution threatens ecosystems and human health. Wastewater treatment plants (WWTPs) play a key role in limiting Hg discharges from wastewaters to rivers and lakes, but large-scale studies to estimate Hg loads and discharge at national levels are scarce. We assessed the concentration, flux, speciation, and removal of Hg in municipal wastewater throughout Switzerland by investigating 64 WWTPs in a pre-study and a subset of 28 WWTPs in the main study. We also studied the behavior and pathways of Hg along the various treatment steps in a state-of-the-art WWTP. The resulting dataset, representative of industrialized countries, provides an overview of (i) current Hg concentration ranges, (ii) average per capita loads, and (iii) wastewater Hg inputs into surface waters. The results allowed estimation of a total Hg (THg) load in Swiss wastewater of 130 ± 30 kg THg/year (15.7 mg/capita/y), of which 96 ± 4% is retained in sewage sludge. About 4.7 ± 0.5 kg THg/year (0.57 mg/capita/y) is discharged with the treated wastewater into surface waters. This corresponds to only 1.5-3% of the THg load carried by the major Swiss rivers, indicating that >95% of riverine Hg originates from other sources. Extrapolation to the population of Europe would yield a total amount of 11,700 kg THg/year in raw wastewater, with some 480 kg THg/year discharged to surface waters. Monomethyl mercury on average accounted for 0.23% of THg, and its fraction remained constant along the different treatment steps.
Svendsen, C., Walker, L. A., Matzke, M., Lahive, E., Harrison, S., Crossley, A., … Spurgeon, D. J. (2020). Key principles and operational practices for improved nanotechnology environmental exposure assessment. Nature Nanotechnology, 15, 731-742. doi:10.1038/s41565-020-0742-1, Institutional Repository

Nanotechnology is identified as a key enabling technology due to its potential to contribute to economic growth and societal well-being across industrial sectors. Sustainable nanotechnology requires a scientifically based and proportionate risk governance structure to support innovation, including a robust framework for environmental risk assessment (ERA) that ideally builds on methods established for conventional chemicals to ensure alignment and avoid duplication. Exposure assessment developed as a tiered approach is equally beneficial to nano-specific ERA as for other classes of chemicals. Here we present the developing knowledge, practical considerations and key principles need to support exposure assessment for engineered nanomaterials for regulatory and research applications.
ThomasArrigo, L. K., Bouchet, S., Kaegi, R., & Kretzschmar, R. (2020). Organic matter influences transformation products of ferrihydrite exposed to sulfide. Environmental Science: Nano, 7(11), 3405-3418. doi:10.1039/d0en00398k, Institutional Repository

In redox-dynamic environments, sorption to poorly-crystalline, nanometer-sized Fe(III)-(oxyhydr)oxides like ferrihydrite influences the biogeochemical cycling of nutrients and trace elements. Under sulfate-reducing conditions, the reductive dissolution of ferrihydrite leads to the release of associated constituents, which may be re-immobilized via sorption to secondary Fe minerals. To date, studies following the kinetics and transformation pathways of Fe(III)-(oxyhydr)oxides upon exposure to dissolved sulfide (S(-II)) have largely focused on pure Fe minerals. However, in nature, Fe(III)-(oxyhydr)oxides are often found in association with organic matter (OM). Because ferrihydrite-OM associations exhibit characteristics and biogeochemical reactivity differing from those of pure ferrihydrite, in this study, we compared sulfidization kinetics and transformation pathways of a pure ferrihydrite to those of ferrihydrite coprecipitated with contrasting organic ligands; polygalacturonic acid, galacturonic acid, and citric acid (C/Fe molar ratio ~0.55). Incorporating aqueous- and solid-phase S and Fe speciation analyses (via wet chemistry techniques and S and Fe X-ray absorption spectroscopy) in addition to X-ray diffraction and electron microscopy, we studied both rapid (<7 days) and long-term (12 months) mineral transformations as well as the impact of varying S(-II)/Fe molar ratios at neutral pH. Our results showed that at low S(-II)/Fe molar ratios (=0.1), poorly-crystalline Fe sulfide minerals (e.g. mackinawite) did not form in any (co)precipitate. In contrast, at higher S(-II)/Fe molar ratios (=0.5), mackinawite rapidly precipitated, with higher contributions detected in the coprecipitates than in the pure ferrihydrite. Aging of the samples led to further mineral transformations, including divergent pyrite and greigite precipitation, and an overall increase in the crystallinity of secondary mineral phases. Still, the fraction of residual ferrihydrite at 12 months was higher in the OM-containing coprecipitates, with the most ferrihydrite preservation observed in coprecipitates comprising carboxyl-poor ligands (galacturonic acid and citric acid). This suggests that the presence of OM inhibited S(-II)-induced ferrihydrite mineral transformations and that the composition of the associated OM influenced mineral transformation pathways. Collectively, these results suggest that further studies regarding sulfidization pathways should include OM in order to better represent environmental conditions.
Tu, K., Puértolas, B., Adobes-Vidal, M., Wang, Y., Sun, J., Traber, J., … Keplinger, T. (2020). Green synthesis of hierarchical metal-organic framework/wood functional composites with superior mechanical properties. Advanced Science, 7(7), 1902897 (9 pp.). doi:10.1002/advs.201902897, Institutional Repository

The applicability of advanced composite materials with hierarchical structure that conjugate metal-organic frameworks (MOFs) with macroporous materials is commonly limited by their inferior mechanical properties. Here, a universal green synthesis method for the in situ growth of MOF nanocrystals within wood substrates is introduced. Nucleation sites for different types of MOFs are readily created by a sodium hydroxide treatment, which is demonstrated to be broadly applicable to different wood species. The resulting MOF/wood composite exhibits hierarchical porosity with 130 times larger specific surface area compared to native wood. Assessment of the CO2 adsorption capacity demonstrates the efficient utilization of the MOF loading along with similar adsorption ability to that of pure MOF. Compression and tensile tests reveal superior mechanical properties, which surpass those obtained for polymer substrates. The functionalization strategy offers a stable, sustainable, and scalable platform for the fabrication of multifunctional MOF/wood-derived composites with potential applications in environmental- and energy-related fields.
Urstoeger, A., Wimmer, A., Kaegi, R., Reiter, S., & Schuster, M. (2020). Looking at silver-based nanoparticles in environmental water samples: repetitive cloud point extraction bridges gaps in electron microscopy for naturally occurring nanoparticles. Environmental Science and Technology, 54(19), 12063-12071. doi:10.1021/acs.est.0c02878, Institutional Repository

The growing use of silver-based nanoparticles (Ag-b-NPs) in everyday products goes hand in hand with their release into the environment, resulting in ng L–1 traces in natural water bodies. In order to assess their fate, possible transformations and ecotoxicology—essential information to proper risk assessment—particle size, shape, and chemical composition have to be determined. Transmission electron microscopy coupled with energy dispersive X-ray spectroscopy (TEM-EDX) is a powerful tool for determining these particle characteristics, but it requires high particle concentrations in order to produce statistically reliable results. In this study, we will present the extraction of Ag-b-NPs at environmentally relevant concentrations down to 5 ng L–1 from artificial as well as environmental water samples via cloud point extraction on a repetitive basis. The combination with an on-grid centrifugation technique ensures an efficient concentration and deposition of the extracted particles onto the TEM grid for subsequent TEM-EDX measurements. Furthermore, electron microscopy investigations were supplemented by single particle inductively coupled plasma mass spectrometry (sp-ICP-MS) measurements. Ag-b-NPs were successfully visualized and characterized at environmentally relevant concentrations of 5 ng L–1 with TEM-EDX and sp-ICP-MS measurements. Their size, shape, and chemical composition were not affected by the sample preparation.
Velimirovic, M., Wagner, S., Monikh, F. A., Uusimäki, T., Kaegi, R., Hofmann, T., & von der Kammer, F. (2020). Accurate quantification of TiO2 nanoparticles in commercial sunscreens using standard materials and orthogonal particle sizing methods for verification. Talanta, 215, 120921 (10 pp.). doi:10.1016/j.talanta.2020.120921, Institutional Repository

The implementation and enforcement of product labeling obligation as required, for example, by the cosmetic product regulation, needs simple and precise validated analytical methods. This also applies to the analysis of nanoparticles in products such as cosmetics. However, the provision of such methods is often hampered by inaccurate sizing due to unwanted nanoparticle changes, interference of matrix components with sizing and interactions between nanoparticles and analytical instrumentation. It is, therefore, necessary to develop appropriate sample preparation methods that preserve NP properties and reduce or remove matrix compounds that interfere with sizing. Further, accurate particle size analysis of samples containing unknown and possibly multiple nanoparticulate constituents is needed. In this study, we evaluated three sample preparation methods to identify and quantify TiO2 nanoparticles in sunscreens. Specifically, we used a combination of ultracentrifugation and hexane washing, thermal destruction of the matrix, and surfactant assisted particle extraction. The method accuracy was assessed by two internal reference samples: pristine TiO2 nanoparticles (NM104) and similar TiO2 nanoparticles dispersed in a sunscreen matrix. The PSDs were determined using an asymmetrical flow field-flow fractionation hyphenated with multi-angle light scattering and inductively coupled plasma-mass spectroscopy. Particle sizing was based on size calibration of the particle retention time in the AF4. Computation of radius of gyration from MALS data was used as an orthogonal particle sizing approach to verify ideal elution and particle size data from the AF4 calibration. Among the three tested sample preparation methods surfactant assisted particle extraction revealed TiO2 nanoparticle recoveries of above 90% and no increase in particle size due to sample preparation was observed. Finally, the sample preparation methods were applied to two commercial sunscreen samples revealing the existence of TiO2-NP < 100 nm. Conclusively, the surfactant assisted particle extraction method can provide valid data for TiO2-NPs in sunscreen and possibly for cosmetic samples of similar matrix.
Villez, K., Vanrolleghem, P. A., & Corominas, L. (2020). A general-purpose method for Pareto optimal placement of flow rate and concentration sensors in networked systems - with application to wastewater treatment plants. Computers and Chemical Engineering, 139, 106880 (14 pp.). doi:10.1016/j.compchemeng.2020.106880, Institutional Repository

The advent of affordable computing, low-cost sensor hardware, and high-speed and reliable communications have spurred ubiquitous installation of sensors in complex engineered systems. However, ensuring reliable data quality remains a challenge. Exploitation of redundancy among sensor signals can help improving the precision of measured variables, detecting the presence of gross errors, and identifying faulty sensors. The cost of sensor ownership, maintenance efforts in particular, can still be cost-prohibitive however. Maximizing the ability to assess and control data quality while minimizing the cost of ownership thus requires a careful sensor placement. To solve this challenge, we develop a generally applicable method to solve the multi-objective sensor placement problem in systems governed by linear and bilinear balance equations. Importantly, the method computes all Pareto-optimal sensor layouts with conventional computational resources and requires no information about the expected sensor quality.
Villez, K., Del Giudice, D., Neumann, M. B., & Rieckermann, J. (2020). Accounting for erroneous model structures in biokinetic process models. Reliability Engineering and System Safety, 203, 107075 (8 pp.). doi:10.1016/j.ress.2020.107075, Institutional Repository

In engineering practice, model-based design requires not only a good process-based model, but also a good description of stochastic disturbances and measurement errors to learn credible parameter values from observations. However, typical methods use Gaussian error models, which often cannot describe the complex temporal patterns of residuals. Consequently, this results in overconfidence in the identified parameters and, in turn, optimistic reactor designs. In this work, we assess the strengths and weaknesses of a method to statistically describe these patterns with autocorrelated error models. This method produces increased widths of the credible prediction intervals following the inclusion of the bias term, in turn leading to more conservative design choices. However, we also show that the augmented error model is not a universal tool, as its application cannot guarantee the desired reliability of the resulting wastewater reactor design.
Wielinski, J., Marafatto, F. F., Gogos, A., Scheidegger, A., Voegelin, A., Müller, C. R., … Kaegi, R. (2020). Synchrotron hard X-ray chemical imaging of trace element speciation in heterogeneous samples: development of criteria for uncertainty analysis. Journal of Analytical Atomic Spectrometry, 35, 567-579. doi:10.1039/C9JA00394K, Institutional Repository

Synchrotron hard X-ray spectroscopy with focussing optics allows recording X-ray fluorescence (XRF) maps at energies around element specific X-ray absorption edges. Stacking multiple XRF maps along the energy axis yields chemical images that contain spatially resolved information on the speciation of the absorber in the sample matrix at the micrometre scale. Short dwell times needed to keep measurement time and radiation-induced sample changes within acceptable limits result in spectral noise that affects the uncertainty in data analysis. In this study, we develop a model to quantify the uncertainty associated with the processing of XRF image stacks using Bayesian inference. To demonstrate the potential of our approach, the model is applied to stacks of XRF maps collected around the copper (Cu) K-edge (pixel size: 3 × 3 μm2, map sizes: 500 × 500 μm2). The investigated samples include digested sewage sludge spiked with either CuO nanoparticles (NP) or dissolved CuSO4 and their corresponding ashes obtained through incineration. The chemical imaging data reveal differences in species distribution between sludge spiked with CuO NP or dissolved Cu. These differences disappear during the incineration process and the resulting ashes exhibit almost identical Cu species distribution. The uncertainty analysis approach developed in this study can be used for data interpretation, but can also be used for the planning of chemical imaging experiments at synchrotron beamlines.
Wigger, H., Kägi, R., Wiesner, M., & Nowack, B. (2020). Exposure and possible risks of engineered nanomaterials in the environment - current knowledge and directions for the future. Reviews of Geophysics, 58(4), e2020RG000710 (25 pp.). doi:10.1029/2020RG000710, Institutional Repository

The consequences that engineered nanomaterials (ENMs) may cause in the environment have been under investigation for more than 15 years. Hundreds of millions of euros/dollars have been invested into safety issues of ENMs, and much progress has been made in the understanding of their fate and effects in the environment. After an initial phase of "observing the effects," research has shifted toward elucidating the mechanisms of fate and ecotoxicological effects. This also included a stronger focus on exposure issues and the development of analytical methods and computational models to predict exposure. First environmental risk assessments for ENM were performed, and much progress has been achieved on the way to nanospecific and material‐specific assessments. The release of ENM from products and their transformation in technical and natural compartments profoundly affect the form in which the ENMs are present in the environment. A crucial aspect in all areas is if there are truly nanospecific issues of the novel‐added functionalities of ENM that are different from dissolved metals, larger particles, or natural particles. This review outlines progress in understanding the environmental dimensions of ENMs and areas that merit further investigation: To what extent are ENMs different from their natural counterparts and how "long" do we need to track them in natural and technical systems? A major challenge will be in developing methods for studying particle‐mediated processes and their effects on ecosystems and organisms in a more general sense, going beyond just ENM, for example, to natural nanoparticles, microplastics, and extracellular vesicles.
Xu, J., Avellan, A., Li, H., Clark, E. A., Henkelman, G., Kaegi, R., & Lowry, G. V. (2020). Iron and sulfur precursors affect crystalline structure, speciation, and reactivity of sulfidized nanoscale zerovalent iron. Environmental Science and Technology, 54(20), 13294-13303. doi:10.1021/acs.est.0c03879, Institutional Repository

The reactivity of sulfidized nanoscale zerovalent iron (SNZVI) is affected by the amount and species of sulfur in the materials. Here, we assess the impact of the Fe (Fe2+ and Fe3+) and S (S2O42-, S2-, and S62-) precursors used to synthesize both NZVI and SNZVI on the resulting physicochemical properties and reactivity and selectivity with water and trichloroethene (TCE). X-ray diffraction indicated that the Fe precursors altered the crystalline structure of both NZVI and SNZVI. The materials made from the Fe3+ precursor had an expanded lattice in the Fe0 body-centered-cubic (BCC) structure and lower electron-transfer resistance, providing higher reactivity with water (∼2-3 fold) and TCE (∼5-13 fold) than those made from an Fe2+ precursor. The choice of the S precursor controlled the S speciation in the SNZVI particles, as indicated by X-ray absorption spectroscopy. Iron disulfide (FeS2) was the main S species of SNZVI made from S2O42-, whereas iron sulfide (FeS) was the main S species of SNZVI made from S2-/S62-. The former SNZVI was more hydrophobic, reactive with, and selective for TCE compared to the latter SNZVI. These results suggest that the Fe and S precursors can be used to select the conditions of the synthesis process and provide selected physicochemical properties (e.g., S speciation, hydrophobicity, and crystalline structure), reactivity, and selectivity of the SNZVI materials.
Xu, J., Avellan, A., Li, H., Liu, X., Noël, V., Lou, Z., … Lowry, G. V. (2020). Sulfur loading and speciation control the hydrophobicity, electron transfer, reactivity, and selectivity of sulfidized nanoscale zerovalent iron. Advanced Materials, 32(17), 1906010 (10 pp.). doi:10.1002/adma.201906910, Institutional Repository

Sulfidized nanoscale zerovalent iron (SNZVI) is a promising material for groundwater remediation. However, the relationships between sulfur content and speciation and the properties of SNZVI materials are unknown, preventing rational design. Here, the effects of sulfur on the crystalline structure, hydrophobicity, sulfur speciation, corrosion potential, and electron transfer resistance are determined. Sulfur incorporation extended the nano-Fe0 BCC lattice parameter, reduced the Fe local vacancies, and lowered the resistance to electron transfer. Impacts of the main sulfur species (FeS and FeS2) on hydrophobicity (water contact angles) are consistent with density functional theory calculations for these FeSx phases. These properties well explain the reactivity and selectivity of SNZVI during the reductive dechlorination of trichloroethylene (TCE), a hydrophobic groundwater contaminant. Controlling the amount and speciation of sulfur in the SNZVI made it highly reactive (up to 0.41 L m-2 d-1) and selective for TCE degradation over water (up to 240 moles TCE per mole H2O), with an electron efficiency of up to 70%, and these values are 54-fold, 98-fold, and 160-fold higher than for NZVI, respectively. These findings can guide the rational design of robust SNZVI with properties tailored for specific application scenarios.
Zeumer, R., Hermsen, L., Kaegi, R., Kühr, S., Knopf, B., & Schlechtriem, C. (2020). Bioavailability of silver from wastewater and planktonic food borne silver nanoparticles in the rainbow trout Oncorhynchus mykiss. Science of the Total Environment, 706, 135695 (12 pp.). doi:10.1016/j.scitotenv.2019.135695, Institutional Repository

Silver nanoparticles (AgNPs) are present in a wide field of applications and consumer products and are likely to be released into the environment, mainly via urban and industrial sewage due to their extensive use. Even though AgNPs are mostly retained within the sludge of wastewater treatment plants (WWTPs), a small amount of mainly sulfidized particles still enters the aquatic environment, where they can be taken up by various aquatic organisms and transferred along the food chain. In this study, uptake and bioavailability of Ag from AgNPs following aqueous and dietary exposure were investigated in the rainbow trout Oncorhynchus mykiss. AgNPs in the effluent of model WWTPs and in tap water were used to perform aqueous exposure studies. No significant Ag uptake into the gills and carcass of the analyzed fish could be found for wastewater-borne AgNPs. However, when added to tap water at a concentration of 12.4 μg L-1, a maximum total Ag tissue concentrations of around 100 μg kg-1 and 50 μg kg-1 in gills and carcass were measured, respectively. For the dietary exposure studies, freshwater zooplankton was exposed to AgNPs, and used for the preparation of food pellets with a total Ag concentration of 121.5 μg kg-1. During the feeding study with rainbow trout significant total Ag concentrations up to 34.3 μg kg-1 could be found in the digestive tract. However, only a limited transfer of Ag through the intestinal walls into the carcass could be detected. AgNPs in plankton and WWTP effluent were characterized by transmission electron microscopy (TEM) in combination with energy dispersive X-ray spectroscopy (EDX) and found to be sulfidized. This transformation most presumably has led to their limited bioavailability for fish. The results emphasize the importance of realistic test conditions for the risk assessment of AgNPs by the use of environmental matrices.
Ziemba, C., Larivé, O., Reynaert, E., Huisman, T., & Morgenroth, E. (2020). Linking transformations of organic carbon to post-treatment performance in a biological water recycling system. Science of the Total Environment, 721, 137489 (8 pp.). doi:10.1016/j.scitotenv.2020.137489, Institutional Repository

Ozone, electrolysis and granular activated carbon (GAC) were examined as potential post-treatments to follow a household-scale biologically activated membrane bioreactor (BAMBi), treating a wash water containing trace urine and feces contamination. Each post-treatment was evaluated for abilities and reaction preferences to remove or transform dissolved organic carbon (DOC), chemical structures that contribute color, and assimilable organic carbon (AOC), which can support bacterial regrowth. Batch treatment with each technology demonstrated an ability to remove ≥95% DOC. Ozone demonstrated a reaction selectivity through increased reaction rates with larger compounds and color-contributing compounds. Electrolysis and GAC demonstrated generally less-selective reactivity. Adding post-treatments to full-scale systems reduced DOC (55-91%), AOC (34-62%), and color (75-98%), without significant reaction selectivity. These reductions in DOC and AOC were not linked to reduction of bacterial concentrations in treated water. Reductions in bacterial concentrations were observed with ozone and electrolysis, but this is credited to oxidation chemicals produced in these systems and not the removal or transformations of organic materials.
Aeppli, M., Vranic, S., Kaegi, R., Kretzschmar, R., Brown, A. R., Voegelin, A., … Sander, M. (2019). Decreases in iron oxide reducibility during microbial reductive dissolution and transformation of ferrihydrite. Environmental Science and Technology, 53(15), 8736-8746. doi:10.1021/acs.est.9b01299, Institutional Repository

Ferrous iron formed during microbial ferric iron reduction induces phase transformations of poorly crystalline into more crystalline and thermodynamically more stable iron (oxyhydr)oxides. Yet, characterizing the resulting decreases in the reactivity of the remaining oxide ferric iron toward reduction (i.e., its reducibility) has been challenging. Here, we used the reduction of six-line ferrihydrite by Shewanella oneidensis MR-1 as a model system to demonstrate that mediated electrochemical reduction (MER) allows directly following decreases in oxide ferric iron reducibility during the transformation of ferrihydrite into goethite and magnetite which we characterized by X-ray diffraction analysis and transmission electron microscopy imaging. Ferrihydrite was fully reducible in MER at both pHMER of 5.0 and 7.5. Decreases in iron oxide reducibility associated with ferrihydrite transformation into magnetite were accessible at both pHMER because the formed magnetite was not reducible under either of these conditions. Conversely, decreases in iron oxide reducibility associated with goethite formation were apparent only at the highest tested pHMER of 7.5 and thus the thermodynamically least favorable conditions for iron oxide reductive dissolution. The unique capability to adjust the thermodynamic boundary conditions in MER to the specific reducibilities of individual iron (oxyhydr)oxides makes this electrochemical approach broadly applicable for studying changes in iron oxide reducibility in heterogeneous environmental samples such as soils and sediments.
Aeppli, M., Kaegi, R., Kretzschmar, R., Voegelin, A., Hofstetter, T. B., & Sander, M. (2019). Electrochemical analysis of changes in iron oxide reducibility during abiotic ferrihydrite transformation into goethite and magnetite. Environmental Science and Technology, 53(7), 3568-3578. doi:10.1021/acs.est.8b07190, Institutional Repository

Electron transfer to ferric iron in (oxyhydr-)oxides (hereafter iron oxides) is a critical step in many processes that are central to the biogeochemical cycling of elements and to pollutant dynamics. Understanding these processes requires analytical approaches that allow for characterizing the reactivity of iron oxides toward reduction under controlled thermodynamic boundary conditions. Here, we used mediated electrochemical reduction (MER) to follow changes in iron oxide reduction extents and rates during abiotic ferrous iron-induced transformation of six-line ferrihydrite. Transformation experiments (10 mM ferrihydrite-FeIII) were conducted over a range of solution conditions (pHtrans = 6.50 to 7.50 at 5 mM Fe2+ and for pHtrans = 7.00 also at 1 mM Fe2+) that resulted in the transformation of ferrihydrite into thermodynamically more stable goethite or magnetite. The changes in iron oxide mineralogy during the transformations were quantified using X-ray diffraction analysis. MER measurements on iron oxide suspension aliquots collected during the transformations were performed over a range of pHMER at constant applied reduction potential. The extents and rates of iron oxide reduction in MER decreased with decreasing reaction driving force resulting from both increasing pHMER and increasing transformation of ferrihydrite into thermodynamically more stable iron oxides. We show that the decreases in iron oxide reduction extents and rates during ferrihydrite transformations can be linked to the concurrent changes in iron oxide mineralogy.
Arhin, S. G., Banadda, N., Komakech, A. J., Pronk, W., & Marks, S. J. (2019). Application of hybrid coagulation–ultrafiltration for decentralized drinking water treatment: impact on flux, water quality and costs. Water Science and Technology: Water Supply, 19(7), 2163-2171. doi:10.2166/ws.2019.097, Institutional Repository

Decentralized membrane-based water treatment represents an attractive and viable approach to safe water supply in low-income areas, but its widespread adoption requires cost-effective antifouling strategies. Although the antifouling mechanisms of Al-based coagulants have been widely investigated, there is little data about their impact on costs and treatment efficiency for decentralized membrane-based systems. In this study, a comparative assessment of two decentralized ultrafiltration (UF) units with and without polyaluminum chloride (PACl) coagulation was undertaken to evaluate the influence of coagulation on the fouling, water quality, and costs nexus. The results showed that PACl suppressed both total fouling and hydraulically irreversible fouling. A matched-pair analysis also revealed that PACl improved the permeate quality by enhancing the removal of particulates and dissolved organics. Compared with the conventional UF system, the hybrid coagulation–UF system contributed to a 21% increase in the flux rate, allowing for a 27% reduction in membrane area and thus, providing cost benefits in terms of both capital and operating costs. These results suggest that PACl coagulation is potentially a cost-effective antifouling method for decentralized membrane-based water systems.
Bakshi, M., Liné, C., Bedolla, D. E., Stein, R. J., Kaegi, R., Sarret, G., … Larue, C. (2019). Assessing the impacts of sewage sludge amendment containing nano-TiO2 on tomato plants: a life cycle study. Journal of Hazardous Materials, 369, 191-198. doi:10.1016/j.jhazmat.2019.02.036, Institutional Repository

Increasing evidence indicates the presence of engineered nanoparticles (ENPs) in sewage sludge derived from wastewater treatment. Land application of sewage sludge is, therefore, considered as an important pathway for ENP transfer to the environment. The aim of this work was to understand the effects of sewage sludge containing nano-TiO2 on plants (tomato) when used as an amendment in agricultural soil. We assessed developmental parameters for the entire plant life cycle along with metabolic and bio-macromolecule changes and titanium accumulation in plants. The results suggest that the sewage sludge amendment containing nano-TiO2 increased plant growth (142% leaf biomass, 102% fruit yield), without causing changes in biochemical responses, except for a 43% decrease in leaf tannin concentration. Changes in elemental concentrations (mainly Fe, B, P, Na, and Mn) of plant stem, leaves and, to a lesser extent fruits were observed. Fourier-transformed infrared analysis showed maximum changes in plant leaves (decrease in tannins and lignins and increase in carbohydrates) but no change in fruits. No significant Ti enrichment was detected in tomato fruits. In conclusion, we evidenced no acute toxicity to plants and no major implication for food safety after one plant life cycle exposure.
Blumensaat, F., Leitão, J. P., Ort, C., Rieckermann, J., Scheidegger, A., Vanrolleghem, P. A., & Villez, K. (2019). How urban storm- and wastewater management prepares for emerging opportunities and threats: digital transformation, ubiquitous sensing, new data sources, and beyond – a horizon scan. Environmental Science and Technology, 53(15), 8488-8498. doi:10.1021/acs.est.8b06481, Institutional Repository

Ubiquitous sensing will create many opportunities and threats for urban water management, which are only poorly understood today. To identify the most relevant trends, we conducted a horizon scan regarding how ubiquitous sensing will shape the future of urban drainage and wastewater management. Our survey of the international urban water community received an active response from both the academics and the professionals from the water industry. The analysis of the responses demonstrates that emerging topics for urban water will often involve experts from different communities, including aquatic ecologists, urban water system engineers and managers, as well as information and communications technology professionals and computer scientists. Activities in topics that are identified as novel will either require (i) cross-disciplinary training, such as importing new developments from the IT sector, or (ii) research in new areas for urban water specialists, for example, to help solve open questions in aquatic ecology. These results are, therefore, a call for interdisciplinary research beyond our own discipline. They also demonstrate that the water management community is not yet prepared for the digital transformation, where we will experience a data demand, i.e. a “pull” of urban water data into external services. The results suggest that a lot remains to be done to harvest the upcoming opportunities. Horizon scanning should be repeated on a routine basis, under the umbrella of an experienced polling organization.
Burdon, F. J., Munz, N. A., Reyes, M., Focks, A., Joss, A., Räsänen, K., … Stamm, C. (2019). Agriculture versus wastewater pollution as drivers of macroinvertebrate community structure in streams. Science of the Total Environment, 659, 1256-1265. doi:10.1016/j.scitotenv.2018.12.372, Institutional Repository

Water pollution is ubiquitous globally, yet how the effects of pollutants propagate through natural ecosystems remains poorly understood. This is because the interactive effects of multiple stressors are generally hard to predict. Agriculture and municipal wastewater treatment plants (WWTPs) are often major sources of contaminants for streams, but their relative importance and the role of different pollutants (e.g. nutrients or pesticides) are largely unknown. Using a 'real world experiment' with sampling locations up- and downstream of WWTPs, we studied how effluent discharges affected water quality and macroinvertebrate communities in 23 Swiss streams across a broad land-use gradient.
Variation partitioning of community composition revealed that overall water quality explained approximately 30% of community variability, whereby nutrients and pesticides each independently explained 10% and 2%, respectively. Excluding oligochaetes (which were highly abundant downstream of the WWTPs) from the analyses, resulted in a relatively stronger influence (3%) of pesticides on the macroinvertebrate community composition, whereas nutrients had no influence. Generally, the macroinvertebrate community composition downstream of the WWTPs strongly reflected the upstream conditions, likely due to a combination of efficient treatment processes, environmental filtering and organismal dispersal. Wastewater impacts were most prominently by the Saprobic index, whereas the SPEAR index (a trait-based macroinvertebrate metrics reflecting sensitivity to pesticides) revealed a strong impact of arable cropping but only a weak impact of wastewater.
Overall, our results indicate that agriculture can have a stronger impact on headwater stream macroinvertebrate communities than discharges from WWTP. Yet, effects of wastewater-born micropollutants were clearly quantifiable among all other influence factors. Improving our ability to further quantify the impacts of micropollutants requires highly-resolved water quality and taxonomic data with adequate spatial and temporal sampling. These improvements would help to better account for the underlying causal pathways that drive observed biological responses, such as episodic contaminant peaks and dispersal-related processes.
Christiaens, M. E. R., Udert, K. M., Arends, J. B. A., Huysman, S., Vanhaecke, L., McAdam, E., & Rabaey, K. (2019). Membrane stripping enables effective electrochemical ammonia recovery from urine while retaining microorganisms and micropollutants. Water Research, 150, 349-357. doi:10.1016/j.watres.2018.11.072, Institutional Repository

Ammonia recovery from urine avoids the need for nitrogen removal through nitrification/denitrification and re-synthesis of ammonia (NH3) via the Haber-Bosch process. Previously, we coupled an alkalifying electrochemical cell to a stripping column, and achieved competitive nitrogen removal and energy efficiencies using only electricity as input, compared to other technologies such as conventional column stripping with air. Direct liquid-liquid extraction with a hydrophobic gas membrane could be an alternative to increase nitrogen recovery from urine into the absorbent while minimizing energy requirements, as well as ensuring microbial and micropollutant retention. Here we compared a column with a membrane stripping reactor, each coupled to an electrochemical cell, fed with source-separated urine and operated at 20 A m−2. Both systems achieved similar nitrogen removal rates, 0.34 ± 0.21 and 0.35 ± 0.08 mol N L−1 d−1, and removal efficiencies, 45.1 ± 18.4 and 49.0 ± 9.3%, for the column and membrane reactor, respectively. The membrane reactor improved nitrogen recovery to 0.27 ± 0.09 mol N L−1 d−1 (38.7 ± 13.5%) while lowering the operational (electrochemical and pumping) energy to 6.5 kWhe kg N−1 recovered, compared to the column reactor, which reached 0.15 ± 0.06 mol N L−1 d−1 (17.2 ± 8.1%) at 13.8 kWhe kg N−1.
Increased cell concentrations of an autofluorescent E. coli MG1655 + prpsM spiked in the urine influent were observed in the absorbent of the column stripping reactor after 24 h, but not for the membrane stripping reactor. None of six selected micropollutants spiked in the urine were found in the absorbent of both technologies.
Overall, the membrane stripping reactor is preferred as it improved nitrogen recovery with less energy input and generated an E. coli- and micropollutant-free product for potential safe reuse. Nitrogen removal rate and efficiency can be further optimized by increasing the NH3 vapor pressure gradient and/or membrane surface area.
Domagała, K., Borlaf, M., Traber, J., Kata, D., & Graule, T. (2019). Purification and functionalisation of multi-walled carbon nanotubes. Materials Letters, 253, 272-275. doi:10.1016/j.matlet.2019.06.085, Institutional Repository

Purifying and functionalising multi-walled carbon nanotubes (MWCNTs) are important processes for providing property modifications, improving handling and enhancing reactivity. The removal of impurities allows avoiding synthesis process interferences and the formation of by-products. During the process it is possible to change the MWCNT properties, e.g. providing enhanced hydrophilicity and better chemical reactivity. In this work, a two-step procedure of MWCNT functionalisation with non-oxidative and oxidative agents is presented. Firstly, hydrochloric acid was used to remove catalyst impurities, which remain after the synthesis process. Secondly, nitric acid was employed to oxidise the MWCNT surfaces and incorporate carboxylic groups onto the surface.
Dörner, L., Cancellieri, C., Rheingans, B., Walter, M., Kägi, R., Schmutz, P., … Jeurgens, L. P. H. (2019). Cost-effective sol-gel synthesis of porous CuO nanoparticle aggregates with tunable specific surface area. Scientific Reports, 9, 11758 (15 pp.). doi:10.1038/s41598-019-48020-8, Institutional Repository

CuO nanoparticles (NPs) are applied in various key technologies, such as catalysis, energy conversion, printable electronics and nanojoining. In this study, an economic, green and easy-scalable sol-gel synthesis method was adopted to produce submicron-sized nanoporous CuO NP aggregates with a specific surface area > 18 m²/g. To this end, a copper-carbonate containing precursor was precipitated from a mixed solution of copper acetate and ammonia carbonate and subsequently calcinated at T ≥ 250 °C. The thus obtained CuO nanopowder is composed of weakly-bounded agglomerates, which are constituted of aggregated CuO NPs with a tunable size in the range of 100–140 nm. The CuO aggregates, in turn, are composed of equi-axed primary crystallites with a tunable crystallite size in the range of 20–40 nm. The size and shape of the primary CuO crystallites, as well as the nanoporosity of their fused CuO aggregates, can be tuned by controlled variation of the degree of supersaturation of the solution via the pH and the carbonate concentration. The synthesized submicron-sized CuO aggregates can be more easily and safely processed in the form of a solution, dispersion or paste than individual NPs, while still offering the same enhanced reactivity due to their nanoporous architecture.
Gogos, A., Wielinski, J., Voegelin, A., Emerich, H., & Kaegi, R. (2019). Transformation of cerium dioxide nanoparticles during sewage sludge incineration. Environmental Science: Nano, 6, 1765-1776. doi:10.1039/C9EN00281B, Institutional Repository

Production volumes of cerium dioxide nanoparticles (CeO2 NP) are predicted to increase in the near future, which will result in increasing amounts of CeO2 NP discharged into wastewater systems and their accumulation in the sewage sludge. At the same time, thermal treatments of sewage sludge, especially incineration, are gaining in importance. Therefore, knowledge on the physical–chemical transformations of CeO2 NP during wastewater treatment and sludge incineration is critical for assessing possible (eco-) toxicological effects related to the increased use of CeO2 NP. We, thus, incinerated unspiked municipal sewage sludge as well as sludge spiked with CeO2 of different particle sizes (4 nm (CeO2-s1), 26 nm (CeO2-s2) and >16 μm (CeO2-s3)) in a pilot fluidized bed reactor to investigate the (size dependent) transformation of CeO2 under conditions mimicking full-scale incineration facilities. We used Ce K- and LIII-edge X-ray absorption spectroscopy (XAS) complemented by analytical electron microscopy to assess the changes in Ce speciation and to characterize the morphology of the pristine and the transformed Ce-(nano)particles. After one week of incubation in digested sludge under anaerobic conditions, CeO2-s1 already showed partial reduction (≈40%) to a Ce(III)-phase. Cerium dioxide of larger particle size (CeO2-s2 and -s3) was less reactive and did not show any detectable reduction within the same reaction time. Incineration of the sludge in general led to a further reduction of Ce, irrespective of whether the Ce was spiked (CeO2-s1, CeO2-s2, CeO2-s3) or already present in the sludge. Reduction during incineration was nearly complete for CeO2-s1 but much less pronounced for CeO2-s2 and -s3. Ce(IV) in larger (primary-) particle sizes thus was more resistant to reduction during anaerobic digestion and incineration. In addition, elemental distribution maps of the CeO2-s1 fly ash revealed elevated Ce signal intensities evenly distributed over areas of several 100 nm. The complementary results obtained from spectroscopic and microscopic analyses indicate that incineration led to the reductive decomposition of the initial CeO2-s1 NP and the sequestration of Ce(III) into a mineralogical phase with probably allanite-like local Ce(III) coordination. Our results, thus, highlight the importance of particle size and the surrounding matrix both affecting the transformation of CeO2 during sewage sludge incineration.
Gruber, W., Villez, K., Kipf, M., Wunderlin, P., Siegrist, H., Vogt, L., & Joss, A. (2019). N2O emission in full-scale wastewater treatment: proposing a refined monitoring strategy. Science of the Total Environment, 699, 134157 (9 pp.). doi:10.1016/j.scitotenv.2019.134157, Institutional Repository

Nitrous oxide (N2O) emissions from wastewater treatment contribute significantly to greenhouse gas emissions. They have been shown to exhibit a strong seasonal and daily profile in previously conducted monitoring campaigns. However, only two year-long online monitoring campaigns have been published to date. Based on three monitoring campaigns on three full-scale wastewater treatment plants (WWTPs) with different activated sludge configurations, each of which lasted at least one year, we propose a refined monitoring strategy for long-term emission monitoring with multiple flux chambers on open tanks. Our monitoring campaigns confirm that the N2O emissions exhibited a strong seasonal profile and were substantial on all three plants (1-2.4% of the total nitrogen load). These results confirm that N2O is the most important greenhouse gas emission from wastewater treatment. The temporal variation was more distinct than the spatial variation within aeration tanks. Nevertheless, multiple monitoring spots along a single lane are crucial to assess representative emission factors in flow-through systems. Sequencing batch reactor systems were shown to exhibit comparable emissions within one reactor but significant variation between parallel reactors. The results indicate that considerable emission differences between lanes are to be expected in cases of inhomogeneous loading and discontinuous feeding. For example, N2O emission could be shown to depend on the amount of treated reject water: lanes without emitted <1% of the influent load, while parallel lanes emitted around 3%. In case of inhomogeneous loading, monitoring of multiple lanes is required. Our study enables robust planning of monitoring campaigns on WWTPs with open tanks. Extensive full-scale emission monitoring campaigns are important as a basis for reliable decisions about reducing the climate impact of wastewater treatment. More specifically, such data sets help us to define general emission factors for wastewater treatment plants and to construct and critically evaluate N2O emission models.
Hoppe, M., Schlich, K., Wielinski, J., Köser, J., Rückamp, D., Kaegi, R., & Hund-Rinke, K. (2019). Long-term outdoor lysimeter study with cerium dioxide nanomaterial. NanoImpact, 14, 100170 (9 pp.). doi:10.1016/j.impact.2019.100170, Institutional Repository

Fate and impact of cerium dioxide nanomaterials (CeO2 NM) in soil remains uncertain. Most of the recent environmental studies used high doses of CeO2 NM in short-term laboratory experiments and stated soil as large sink for NM. Recent studies covering the life cycle of plants found evidence for particle uptake in crop plants, and triggered concern about NM entering the food chain. Here, we present a 25 months outdoor lysimeter study that investigates the translocation, biological impact, and transformation of CeO2 NM in soils cultivated with different crops (wheat (Triticum aestivum L.), canola (Brassica napus L.), and barley (Hordeum vulgare L.)). Low doses of CeO2 NM (NM-212, 10 and 50 mg CeO2 NM kg−1 soil) were applied to a Cambisol by sewage sludge or artificial rainwater. To simulate ploughing, the CeO2 NM was mixed into the first 20 cm of the lysimeter soil. Three weeks after the NM application by sewage sludge and five days after the latest NM application by artificial rainwater wheat seeds were sown.
We found no vertical Ce translocation to deeper soil layers as well as negligible release of Ce into percolating water, confirming that soil is a sink for CeO2 NM. Furthermore, no inhibition of the NM sensitive ammonium oxidizing bacteria (AOB) was observed which implies a low bioavailability of CeO2 NM in soil. The detected Ce root uptake for canola (Ce < 35.7 mg kg−1) and barley (Ce < 61.8 mg kg−1) indicates that physico-chemical conditions in the rhizosphere or the aging of the NM in soil can remobilize the applied CeO2 NM to some extent. One can speculate that the obtained reduction of Ce4+ to Ce3+ (≈ 50% after 25 months) was coupled to different conditions (ionic strength, pH, water content, soil organic matter content) in the rhizosphere and necessary for the root accumulation of Ce.
Due to negligible mobility in the soil-water interface, as well as non-toxicity to AOB, the environmental risk of the tested CeO2 NM appears to be low, compared to other highly mobile emergent pollutants. Nonetheless, further long-term investigations need to focus on the speciation and localization of NM in plants to clarify uptake and impact of NM to crops.
Jafari, M., Derlon, N., Desmond, P., van Loosdrecht, M. C. M., Morgenroth, E., & Picioreanu, C. (2019). Biofilm compressibility in ultrafiltration: a relation between biofilm morphology, mechanics and hydraulic resistance. Water Research, 157, 335-345. doi:10.1016/j.watres.2019.03.073, Institutional Repository

Poroelastic fluid-structure interaction models were coupled to experimental data to determine the effects of biofilm spatial distribution of mechanical and hydraulic properties on the biofilm hydraulic resistance and compressibility in membrane filtration processes. Biofilms were cultivated on ultrafiltration membranes for 20 and 30 days under high (0.28 bar) and low (0.06 bar) transmembrane pressure (TMP), in dead-end filtration mode. Subsequently, biofilms were subjected to a compression/relaxation cycles by step-wise TMP changes. Structural deformation of biofilms during compression was observed in-situ using optical coherence tomography.
Experimental results show that the observed increase in the biofilm hydraulic resistance during compression is not necessarily accompanied by a detectable biofilm thickness reduction. A dual-layer biofilm model with a dense base and porous top layer could explain these observed results. Because porosity controls indirectly the mechanical response of biofilms under compression, results could be described without assuming a gradient in mechanical properties within the biofilm. The biofilm surface roughness did not significantly influence the water flux in this study. However, the fraction of biofilm base layer directly exposed to bulk liquid could be a good indicator in the determination of water flux. The main implications of this study for the design and operation of low-pressure membrane systems (e.g., MF and UF with fouling layer being the main filtration resistance) lays in the selection of favorable operational TMP and biofilm morphology.
Laureni, M., Weissbrodt, D. G., Villez, K., Robin, O., de Jonge, N., Rosenthal, A., … Joss, A. (2019). Biomass segregation between biofilm and flocs improves the control of nitrite-oxidizing bacteria in mainstream partial nitritation and anammox processes. Water Research, 154, 104-116. doi:10.1016/j.watres.2018.12.051, Institutional Repository

The control of nitrite-oxidizing bacteria (NOB) challenges the implementation of partial nitritation and anammox (PN/A) processes under mainstream conditions. The aim of the present study was to understand how operating conditions impact microbial competition and the control of NOB in hybrid PN/A systems, where biofilm and flocs coexist. A hybrid PN/A moving-bed biofilm reactor (MBBR; also referred to as integrated fixed film activated sludge or IFAS) was operated at 15 °C on aerobically pre-treated municipal wastewater (23 mgNH4-N L–1). Ammonium-oxidizing bacteria (AOB) and NOB were enriched primarily in the flocs, and anammox bacteria (AMX) in the biofilm. After decreasing the dissolved oxygen concentration (DO) from 1.2 to 0.17 mgO2 L–1 - with all other operating conditions unchanged - washout of NOB from the flocs was observed. The activity of the minor NOB fraction remaining in the biofilm was suppressed at low DO. As a result, low effluent NO3– concentrations (0.5 mgN L–1) were consistently achieved at aerobic nitrogen removal rates (80 mgN L–1 d–1) comparable to those of conventional treatment plants. A simple dynamic mathematical model, assuming perfect biomass segregation with AOB and NOB in the flocs and AMX in the biofilm, was able to qualitatively reproduce the selective washout of NOB from the flocs in response to the decrease in DO-setpoint. Similarly, numerical simulations indicated that flocs removal is an effective operational strategy to achieve the selective washout of NOB. The direct competition for NO2– between NOB and AMX - the latter retained in the biofilm and acting as a "NO2-sink" - was identified by the model as key mechanism leading to a difference in the actual growth rates of AOB and NOB (i.e., μNOB < μAOB in flocs) and allowing for the selective NOB washout over a broad range of simulated sludge retention times (SRT = 6.8–24.5 d). Experimental results and model predictions demonstrate the increased operational flexibility, in terms of variables that can be easily controlled by operators, offered by hybrid systems as compared to solely biofilm systems for the control of NOB in mainstream PN/A applications.
Layer, M., Adler, A., Reynaert, E., Hernandez, A., Pagni, M., Morgenroth, E., … Derlon, N. (2019). Organic substrate diffusibility governs microbial community composition, nutrient removal performance and kinetics of granulation of aerobic granular sludge. Water Research X, 4, 100033 (16 pp.). doi:10.1016/j.wroa.2019.100033, Institutional Repository

Basic understanding of formation of aerobic granular sludge (AGS) has mainly been derived from lab-scale systems with simple influents containing only highly diffusible volatile fatty acids (VFA) as organic substrate. This study compares start-up of AGS systems fed by different synthetic and municipal wastewaters (WW), characterised by increasing complexity in terms of non-diffusible organic substrate. Four AGS reactors were started with the same inoculum activated sludge and operated for one year. The development of AGS, settling characteristics, nutrient and substrate removal performance as well as microbial community composition were monitored. Our results indicate that the higher the content of diffusible organic substrate in the WW, the faster the formation of AGS. The presence of non-diffusible organic substrate in the influent WW led to the formation of small granules and to the presence of 20–40% (% of total suspended solids) of flocs in the AGS. When AGS was fed with complex influent WW, the classical phosphorus and glycogen accumulating organisms (PAO, GAO) were outcompeted by their fermentative equivalents. Substrate and nutrient removal was observed in all reactors, despite the difference in physical and settling properties of the AGS, but the levels of P and N removal depended on the influent carbon composition. Mechanistically, our results indicate that increased levels of non-diffusible organic substrate in the influent lower the potential for microbial growth deep inside the granules. Additionally, non-diffusible organic substrates give a competitive advantage to the main opponents of AGS formation – ordinary heterotrophic organisms (OHO). Both of these mechanisms are suspected to limit AGS formation. The presented study has relevant implications for both practice and research. Start-up duration of AGS systems treating high complexity WW were one order of magnitude higher than a typical lab-scale system treating VFA-rich synthetic WW, and biomass as flocs persisted as a significant fraction. Finally, the complex synthetic influent WW – composed of VFA, soluble fermentable and particulate substrate - tested here seems to be a more adequate surrogate of real municipal WW for laboratory studies than 100%-VFA WW.
Mansfeldt, C., Achermann, S., Men, Y., Walser, J. C., Villez, K., Joss, A., … Fenner, K. (2019). Microbial residence time is a controlling parameter of the taxonomic composition and functional profile of microbial communities. ISME Journal, 13(6), 1589-1601. doi:10.1038/s41396-019-0371-6, Institutional Repository

A remaining challenge within microbial ecology is to understand the determinants of richness and diversity observed in environmental microbial communities. In a range of systems, including activated sludge bioreactors, the microbial residence time (MRT) has been previously shown to shape the microbial community composition. However, the physiological and ecological mechanisms driving this influence have remained unclear. Here, this relationship is explored by analyzing an activated sludge system fed with municipal wastewater. Using a model designed in this study based on Monod-growth kinetics, longer MRTs were shown to increase the range of growth parameters that enable persistence, resulting in increased richness and diversity in the modeled community. In laboratory experiments, six sequencing batch reactors treating domestic wastewater were operated in parallel at MRTs between 1 and 15 days. The communities were characterized using both 16S ribosomal RNA and non-target messenger RNA sequencing (metatranscriptomic analysis), and model-predicted monotonic increases in richness were confirmed in both profiles. Accordingly, taxonomic Shannon diversity also increased with MRT. In contrast, the diversity in enzyme class annotations resulting from the metatranscriptomic analysis displayed a non-monotonic trend over the MRT gradient. Disproportionately high abundances of transcripts encoding for rarer enzymes occur at longer MRTs and lead to the disconnect between taxonomic and functional diversity profiles.
Mitrano, D. M., Beltzung, A., Frehland, S., Schmiedgruber, M., Cingolani, A., & Schmidt, F. (2019). Synthesis of metal-doped nanoplastics and their utility to investigate fate and behaviour in complex environmental systems. Nature Nanotechnology, 14, 362-368. doi:10.1038/s41565-018-0360-3, Institutional Repository

Research on the distribution and effects of particulate plastic has intensified in recent years and yet, due to analytical challenges, our understanding of nanoplastic occurrence and behaviour has remained comparatively elusive. However, process studies could greatly aid in defining key parameters for nanoplastic interactions within and transfers between technical and environmental compartments. Here we provide a method to synthesize nanoplastic particles doped with a chemically entrapped metal used as a tracer, which provides a robust way to detect nanoplastics more easily, accurately and quantitatively in complex media. We show the utility of this approach in batch studies that simulate the activated sludge process of a municipal waste water treatment plant and so better understand the fate of nanoplastics in urban environments. We found that the majority of particles were associated with the sludge (>98%), with an average recovery of over 93% of the spiked material achieved. We believe that this approach can be developed further to study the fate, transport, mechanistic behaviour and biological uptake of nanoplastics in a variety of systems on different scales.
Németh, Z., Szekeres, G. P., Schabikowski, M., Schrantz, K., Traber, J., Pronk, W., … Graule, T. (2019). Enhanced virus filtration in hybrid membranes with MWCNT nanocomposite. Royal Society Open Science, 6(1), 181294 (14 pp.). doi:10.1098/rsos.181294, Institutional Repository

Membrane separation is proved to be a powerful tool for several applications such as wastewater treatment or the elimination of various microorganisms from drinking water. In this study, the efficiency of inorganic composite-based multi-walled carbon nanotube (MWCNT) hybrid membranes was investigated in the removal of MS2 bacteriophages from contaminated water. With this object, multi-walled carbon nanotubes were coated with copper(I) oxide, titanium(IV) oxide and iron(III) oxide nanoparticles, respectively, and their virus removal capability was tested in both batch and flow experiments. Considering the possible pH range of drinking water, the filtration tests were carried out at pH 5.0, 7.5 and 9.0 as well. The extent of MS2 removal strongly depended on the pH values for each composite, which can be due to electrostatic interactions between the membrane and the virus. The most efficient removal (greater than or equal to 99.99%) was obtained with the Cu2O-coated MWCNT membrane in the whole pH range. The fabricated nanocomposites were characterized by X-ray diffraction, specific surface area measurement, dynamic light scattering, zeta potential measurement, Raman spectroscopy, transmission electron microscopy and scanning electron microscopy. This study presents a simple route to design novel and effective nanocomposite-based hybrid membranes for virus removal.
Nürenberg, G., Kunkel, U., Wick, A., Falås, P., Joss, A., & Ternes, T. A. (2019). Nontarget analysis: a new tool for the evaluation of wastewater processes. Water Research, 163, 114842 (11 pp.). doi:10.1016/j.watres.2019.07.009, Institutional Repository

Strategies to determine the removal efficiency of micropollutants in wastewater treatment plants (WWTPs) are widely discussed. Especially the evaluation of the potential benefit of further advanced treatment steps such as an additional tertiary treatment based on ozonation or activated carbon have come into focus. Such evaluation strategies are often based on the removal behavior of known micropollutants via target or suspected analysis. The utilization of nontarget analysis is considered to lead to a more comprehensive picture as also unknown or not expected micropollutants are analyzed. Here, the results of an evaluation via target and nontarget analysis were compared for biological treatment (BT) processes of eleven full-scale WWTPs and three different post-treatments (PTs): one sand filter (SF) and two granular activated carbon (GAC) filters. The similarity of the determined removals from target and nontarget analysis of the BTs increased significantly by excluding easily degradable "features" from the nontarget evaluation. A similar ranking of the removal trends for the BTs could also be achieved by comparing this new subset of nontarget features with a set of nine readily to moderately biodegradable micropollutants. This observation suggests that a performance ranking of BTs based either on target or nontarget analysis is plausible. In contrast to the BTs, the evaluation of the three PTs revealed that the difference of feature removal between SF and the two GACs was small, but large for the target analytes with substantially higher removal effciencies for the GACs compared to the SF. In addition to the removal behavior, the nontarget analysis provided further information about the number and quantity of transformation products (TPs) in the effluent from the BTs. For all BTs more than half (55–67%) of the features detected in the effluent were not found in the influent. A comparable proportion of TPs was also detected after GAC and sand filtration due to their microbial activities.
Ohmura, K., Thürlimann, C. M., Kipf, M., Carbajal, J. P., & Villez, K. (2019). Characterizing long-term wear and tear of ion-selective pH sensors. Water Science and Technology, 80(3), 541-550. doi:10.2166/wst.2019.301, Institutional Repository

Today, the development and testing of methods for fault detection and identification in wastewater treatment research relies on two important assumptions: (i) that sensor faults appear at distinct times in different sensors and (ii) that any given sensor will function near-perfectly for a significant amount of time following installation. In this work, we show that such assumptions are unrealistic, at least for sensors built around an ion-selective measurement principle. Indeed, long-term exposure of sensors to treated wastewater shows that sensors exhibit fault symptoms that appear simultaneously and with similar intensity. Consequently, this suggests that future research should be reoriented towards methods that do not rely on the assumptions mentioned above. This study also provides the first empirically validated sensor fault model for wastewater treatment simulation, which is useful for effective benchmarking of both fault detection and identification methods and advanced control strategies. Finally, we evaluate the value of redundancy for remote sensor validation in decentralized wastewater treatment systems.
Pronk, W., Ding, A., Morgenroth, E., Derlon, N., Desmond, P., Burkhardt, M., … Fane, A. G. (2019). Gravity-driven membrane filtration for water and wastewater treatment: a review. Water Research, 149, 553-565. doi:10.1016/j.watres.2018.11.062, Institutional Repository

Gravity-driven membrane (GDM) filtration has been investigated for almost 10 years. The technology is characterized not only by relatively lower transmembrane pressures which can be achieved by gravity (extremely low energy consumption), but also by the phenomenon of flux stabilization: A biofilm is allowed to form on the membrane and a stabilization of flux occurs which is related to biological processes within the biofilm layer on the membrane. This enables stable operation during a year or longer without any cleaning or flushing. Initially, the technology was developed mainly for household drinking water treatment, but in the meantime, the research and application has expanded to the treatment of greywater, rainwater, and wastewater as well as the pretreatment of seawater for desalination. This review covers the field from the rather fundamental research on biofilm morphology and microbial community analysis to the impact of feedwater composition, process parameters and organic removal performance. Not only household applications, but also for community-scale treatment and full-scale applications are discussed. In addition, the application potential is highlighted in comparison to conventional ultrafiltration. Finally, an overall assessment is illustrated and the research and development needs are identified.
Pulido-Reyes, G., Briffa, S. M., Hurtado-Gallego, J., Yudina, T., Leganés, F., Puntes, V., … Fernández-Piñas, F. (2019). Internalization and toxicological mechanisms of uncoated and PVP-coated cerium oxide nanoparticles in the freshwater alga: Chlamydomonas reinhardtii. Environmental Science: Nano, 6(6), 1959-1972. doi:10.1039/c9en00363k, Institutional Repository

Due to the wide range of applications of cerium oxide nanoparticles (CeO2NPs), a risk assessment of their biological effects using environmentally relevant species becomes highly important. There are contradictory reports on the effects of CeO2NPs, which may be related to the use of different types of nanoparticles (NPs) and coatings. CeO2NPs may act as an oxidant causing toxicity or as an antioxidant able to scavenge free radicals. As a consequence of such complexity, the toxicological behaviour of these NPs is still poorly understood. Moreover, little is known about the internalization process of CeO2NPs in algae. There is evidence of CeO2NP-internalization by the green alga Chlamydomonas reinhardtii, but the mechanism and route of uptake are still unknown. In this study, we used uncoated and different polyvinylpyrrolidone (PVP)-coated CeO2NPs with the aim of identifying their toxicological mechanisms to C. reinhardtii and exploring their possible internalization. Our results showed that PVP coated-CeO2NPs significantly increased the formation of reactive oxygen species in exposed cells, indicating that oxidative stress is an important toxicity mechanism for these particles. Direct contact and damage of the cellular membrane was identified as the mechanism causing the toxicity of uncoated NPs. From experiments with endocytosis inhibitors, clathrin-dependent endocytosis was revealed as the main internalization route for all NPs. However, as uncoated CeO2NPs led to severe cellular membrane damage, direct passage of NPs through membrane holes could not be discarded. To our knowledge, this is the first report with evidence of direct linking between NP internalization and a specific endocytic pathway. The results presented here will help to unravel the toxicological mechanism and behaviour of CeO2NPs and provide input information for the environmental health and safety assessment of CeO2NPs.
Regmi, P., Stewart, H., Amerlinck, Y., Arnell, M., García, P. J., Johnson, B., … Rosso, D. (2019). The future of WRRF modelling – outlook and challenges. Water Science and Technology, 79(1), 3-14. doi:10.2166/wst.2018.498, Institutional Repository

The wastewater industry is currently facing dramatic changes, shifting away from energy-intensive wastewater treatment towards low-energy, sustainable technologies capable of achieving energy positive operation and resource recovery. The latter will shift the focus of the wastewater industry to how one could manage and extract resources from the wastewater, as opposed to the conventional paradigm of treatment. Debatable questions arise: can the more complex models be calibrated, or will additional unknowns be introduced? After almost 30 years using well-known International Water Association (IWA) models, should the community move to other components, processes, or model structures like 'black box' models, computational fluid dynamics techniques, etc.? Can new data sources – e.g. on-line sensor data, chemical and molecular analyses, new analytical techniques, off-gas analysis – keep up with the increasing process complexity? Are different methods for data management, data reconciliation, and fault detection mature enough for coping with such a large amount of information? Are the available calibration techniques able to cope with such complex models? This paper describes the thoughts and opinions collected during the closing session of the 6th IWA/WEF Water Resource Recovery Modelling Seminar 2018. It presents a concerted and collective effort by individuals from many different sectors of the wastewater industry to offer past and present insights, as well as an outlook into the future of wastewater modelling.
Russo, S., Li, G., & Villez, K. (2019). Automated model selection in principal component analysis: a new approach based on the cross-validated ignorance score. Industrial and Engineering Chemistry Research, 58(30), 13448-13468. doi:10.1021/acs.iecr.9b00642, Institutional Repository

Principal component analysis (PCA) is by far the most widespread tool for unsupervised learning with high-dimensional data sets. It is popularly studied for exploratory data analysis and online process monitoring. Unfortunately, fine-tuning PCA models and particularly the number of components remains a challenging task. Today, this selection is often based on a combination of guiding principles, experience, and process understanding. Unlike the case of regression, where cross-validation of the prediction error is a widespread and trusted approach for model selection, there are no tools for PCA model selection enjoying this level of acceptance. In this work, we address this challenge and evaluate the utility of the cross-validated ignorance score with both simulated and experimental data sets. Application of this model selection criterion is based on the interpretation of PCA as a density model, as in probabilistic principal component analysis. With simulation-based benchmarking, it is shown to be (a) the overall best performing criterion, (b) the preferred criterion at high noise levels, and (c) very robust to changes in noise level. Tests on experimental data sets suggest that the ignorance score is sensitive to deviations from the PCA model structure, which suggests the criterion is also useful to detect of model-reality mismatch.
Salas, P., Odzak, N., Echegoyen, Y., Kägi, R., Sancho, M. C., & Navarro, E. (2019). The role of size and protein shells in the toxicity to algal photosynthesis induced by ionic silver delivered from silver nanoparticles. Science of the Total Environment, 692, 233-239. doi:10.1016/j.scitotenv.2019.07.237, Institutional Repository

Because of their biocide properties, silver nanoparticles (AgNPs) are present in numerous consumer products. The biocidal properties of AgNPs are due to both the interactions between AgNP and cell membranes and the release of dissolved silver (Ag+). Recent studies emphasized the role of different nanoparticle coatings in complexing and storing Ag+. In this study, the availability of dissolved silver in the presence of algae was assessed for three AgNPs with different silver contents (59%, 34% and 7% of total Ag), silver core sizes and casein shell thicknesses. The impact of ionic silver on the photosynthetic yield of Chlamydomonas reinhardtii was used as a proxy to estimate the amount of ionic silver toxically active during in vivo assays. The results showed that cysteine, a strong silver ligand, mitigated the toxicity of AgNPs in all cases, demonstrating the key role of Ag+ in this toxicity. The results showed that the AgNPs presenting an intermediate level of silver (34%) were 10 times more effective in terms of total mass (EC50 ten times smaller) than those presenting more (59%) or less (7%) silver. The higher toxicity was due to the higher release of Ag+ under biotic conditions due to the high surface/mass ratio of the nanoparticle silver core. Protein shells played a minor role in altering the availability of Ag+, probably acting as intermediate reservoirs. This study highlighted the utility of a very sensitive biological endpoint (i.e., algal photosynthesis) for the optimization of ionic silver delivery by nanomaterials.
Schmiedgruber, M., Hufenus, R., & Mitrano, D. M. (2019). Mechanistic understanding of microplastic fiber fate and sampling strategies: synthesis and utility of metal doped polyester fibers. Water Research, 155, 423-430. doi:10.1016/j.watres.2019.02.044, Institutional Repository

The increased use of synthetic textiles in the last decades, coupled with recent emphasis on the accumulation of (micro)plastic across multiple environmental compartments, has garnered interest into how microplastic fibers are released into the environment. In particular, polyester textiles washed in the home have shown to release microplastic fibers but challenges with microplastic fiber analysis, including time and difficulty of sample preparation and measurement, has limited mechanistic studies on fiber fate and transport studies. In this study, we provide a method to synthesize fibers with an embedded inorganic (In) fingerprint which can be used as a tracer for ease of analysis and show the utility of this approach to assess the affinity for heteroaggregation between microplastic fibers and other particles in a heterogeneous suspension, as well as approximate the fate of microplastic fibers in batch studies using activated sludge from a municipal wastewater treatment plant (WWTP). Total In content in the fibers was measured to be 0.2 % by weight, which was low enough to not change fiber dynamics for fate and transport studies (e.g. density, etc.) but provided sensitive detection limits by ICP-MS. Fiber length was 510 μm ± 410 μm and 30 μm in diameter. The incorporated metal remained stable inside the polymer when suspended in water and in activated sludge, with < 0.1 % In leaching over two months. In batch experiments, the majority of fibers were associated with the sludge ( > 99.9 %), with a mass balance of > 95 % recovery achieved on average across batches. Fiber removal linearly increased with contact times of up to 10 min, suggesting interactions between plastics and organic matter is a metric that should be considered closely in this and other environmental contexts for fate and transport.
Schneider, M. Y., Carbajal, J. P., Furrer, V., Sterkele, B., Maurer, M., & Villez, K. (2019). Beyond signal quality: the value of unmaintained pH, dissolved oxygen, and oxidation-reduction potential sensors for remote performance monitoring of on-site sequencing batch reactors. Water Research, 161, 639-651. doi:10.1016/j.watres.2019.06.007, Institutional Repository

Sensor maintenance is time-consuming and is a bottleneck for monitoring on-site wastewater treatment systems. Hence, we compare maintained and unmaintained sensors to monitor the biological performance of a small-scale sequencing batch reactor (SBR). The sensor types are ion-selective pH, optical dissolved oxygen (DO), and oxidation-reduction potential (ORP) with platinum electrode. We created soft sensors using engineered features: ammonium valley for pH, oxidation ramp for DO, and nitrite ramp for the ORP. Four soft sensors based on unmaintained pH sensors correctly identified the completion of the ammonium oxidation (89–91 out of 107 cycles), about as many times as soft sensors based on a maintained pH sensor (91 out of 107 cycles). In contrast, the DO soft sensor using data from a maintained sensor showed slightly better (89 out of 96 cycles) detection performance than that using data from two unmaintained sensors (77, respectively 82 out of 96 correct). Furthermore, the DO soft sensor using maintained data is much less sensitive to the optimisation of cut-off frequency and slope tolerance than the soft sensor using unmaintained data. The nitrite ramp provided no useful information on the state of nitrite oxidation, so no comparison of maintained and unmaintained ORP sensors was possible in this case. We identified two hurdles when designing soft sensors for unmaintained sensors: i) Sensors’ type- and design-specific deterioration affects performance. ii) Feature engineering for soft sensors is sensor type specific, and the outcome is strongly influenced by operational parameters such as the aeration rate. In summary, the results with the provided soft sensors show that frequent sensor maintenance is not necessarily needed to monitor the performance of SBRs. Without sensor maintenance monitoring smalls-scale SBRs becomes practicable, which could improve the reliability of unstaffed on-site treatment systems substantially.
Seviour, T., Derlon, N., Simonsen Dueholm, M., Flemming, H. C., Girbal-Neuhauser, E., Horn, H., … Lin, Y. (2019). Extracellular polymeric substances of biofilms: suffering from an identity crisis. Water Research, 151, 1-7. doi:10.1016/j.watres.2018.11.020, Institutional Repository

Microbial biofilms can be both cause and cure to a range of emerging societal problems including antimicrobial tolerance, water sanitation, water scarcity and pollution. The identities of extracellular polymeric substances (EPS) responsible for the establishment and function of biofilms are poorly understood. The lack of information on the chemical and physical identities of EPS limits the potential to rationally engineer biofilm processes, and impedes progress within the water and wastewater sector towards a circular economy and resource recovery. Here, a multidisciplinary roadmap for addressing this EPS identity crisis is proposed. This involves improved EPS extraction and characterization methodologies, cross-referencing between model biofilms and full-scale biofilm systems, and functional description of isolated EPS with in situ techniques (e.g. microscopy) coupled with genomics, proteomics and glycomics. The current extraction and spectrophotometric characterization methods, often based on the principle not to compromise the integrity of the microbial cells, should be critically assessed, and more comprehensive methods for recovery and characterization of EPS need to be developed.
Silva, M. O. D., Desmond, P., Derlon, N., Morgenroth, E., & Pernthaler, J. (2019). Source community and assembly processes affect the efficiency of microbial microcystin degradation on drinking water filtration membranes. Frontiers in Microbiology, 10, 843 (15 pp.). doi:10.3389/fmicb.2019.00843, Institutional Repository

Microbial biofilms in gravity-driven membrane (GDM) filtration systems can efficiently degrade the cyanotoxin microcystin (MC), but it is unclear if this function depends on the presence of MC-producing cyanobacteria in the source water habitat. We assessed the removal of MC from added Microcystis aeruginosa biomass in GDMs fed with water from a lake with regular blooms of toxic cyanobacteria (ExpL) or from a stream without such background (ExpS). While initial MC removal was exclusively due to abiotic processes, significantly higher biological MC removal was observed in ExpL. By contrast, there was no difference in MC degradation capacity between lake and stream bacteria in separately conducted liquid enrichments on pure MC. Co-occurrence network analysis revealed a pronounced modularity of the biofilm communities, with a clear hierarchic distinction according to feed water origin and treatment type. Genotypes in the network modules associated with ExpS had significantly more links to each other, indicating that these biofilms had assembled from a more coherent source community. In turn, signals for stochastic community assembly were stronger in ExpL biofilms. We propose that the less “tightly knit” ExpL biofilm assemblages allowed for the better establishment of facultatively MC degrading bacteria, and thus for higher overall functional efficiency.
 
Surette, M. C., Nason, J. A., & Kaegi, R. (2019). The influence of surface coating functionality on the aging of nanoparticles in wastewater. Environmental Science: Nano, 6(8), 2470-2483. doi:10.1039/C9EN00376B, Institutional Repository

Efforts to predict the environmental fate of engineered nanomaterials (ENMs) are frequently based on the physiochemical properties and behavior of the ENMs in their pristine, “as-produced” state. However, it is well-established that ENMs can be physically, biologically, and chemically transformed, resulting in altered physiochemical properties and behavior. Wastewater treatment plants (WWTPs) represent an important stage in an ENM's life-cycle where they can be transformed. To better understand the properties of ENMs discharged from WWTPs into surface waters, we investigated how the transformation processes of aggregation and corona formation are influenced by the surface coating applied to ENMs during their manufacture. Using 40 nm gold nanoparticles coated with polyethylene glycol, lipoic acid, or branched polyethylenimine as model ENMs, batch experiments were performed to investigate aggregation and corona formation during the primary clarification and activated sludge treatment stages. A tangential flow filtration system was used to evaluate if the initial transformations were altered as the aquatic chemistry of the background matrix was changed, mimicking the varying conditions ENMs would experience during transport through a WWTP. Using a combination of corroborative techniques including dynamic light scattering, phase analysis light scattering, ultraviolet-visible light spectroscopy, and transmission electron microscopy, we find that the model ENMs aggregated in each wastewater matrix, regardless of the initial surface coating. Differences in the UV-vis spectra indicate that the nature of the corona acquired by the ENMs differed as a function of the surface coating of the pristine ENMs. In addition, initial ENM transformations during exposure to the influent wastewater persisted even as the background matrix changed. These results support the finding that ENMs discharged from WWTPs will not resemble their pristine analogs. Furthermore, the corona acquired by ENMs in WWTPs may vary in relation to their pristine properties and be dictated by conditions during early stage exposures.
ThomasArrigo, L. K., Kaegi, R., & Kretzschmar, R. (2019). Ferrihydrite growth and transformation in the presence of ferrous iron and model organic ligands. Environmental Science and Technology, 53(23), 13636-13647. doi:10.1021/acs.est.9b03952, Institutional Repository

Ferrihydrite (Fh) is a poorly crystalline Fe(III)-oxyhydroxide found in abundance in soils and sediments. With a high specific surface area and sorption capacity at circumneutral pH, ferrihydrite is an important player in the biogeochemical cycling of nutrients and trace elements in redox-dynamic environments. Under reducing conditions, exposure to Fe(II) induces mineral transformations in ferrihydrite; the extent and trajectory of which may be greatly influenced by organic matter (OM). However, natural OM is heterogeneous and comprises a range of molecular weights (MWs) and varied functional group compositions. To date, the impact that the chemical composition of the associated OM has on Fe(II)-catalyzed mineral transformations is not clear. To address this knowledge gap, we coprecipitated ferrihydrite with model organic ligands selected to cover a range of MWs (25 000–50 000 vs <200 Da) as well as carboxyl content (polygalacturonic acid (PGA) > citric acid (CA) > galacturonic acid (GA)). Coprecipitates (C:Fe ≈ 0.6) were reacted with 1 mM 57Fe(II) for 1 week at pH 7, with time-resolved solid-phase analysis (via X-ray diffraction, X-ray absorption spectroscopy, and electron microscopy) revealing that all ligands inhibited Fe(II)-catalyzed ferrihydrite mineral transformations and the formation of crystalline secondary mineral phases compared to a pure ferrihydrite. For carboxyl-rich coprecipitates (Fh-PGA and Fh-CA), mineral transformations were less inhibited than in the carboxyl poor Fh-GA, and a crystalline lepidocrocite "shell" was formed surrounding the residual ferrihydrite core. However, Fe isotope analysis revealed that all coprecipitates underwent near complete atom exchange. Collectively, our results highlight that ferrihydrite is indeed an active mineral phase in redox-dynamic environments, but that its stability under reducing conditions, and thus capacity for nutrient and trace element retention, depends on the chemical characteristic of the associated OM, specifically OM-induced changes in the particle surface charge and the distribution of organic functional groups.
Thürlimann, C. M., Udert, K. M., Morgenroth, E., & Villez, K. (2019). Stabilizing control of a urine nitrification process in the presence of sensor drift. Water Research, 165, 114958 (10 pp.). doi:10.1016/j.watres.2019.114958, Institutional Repository

Sensor drift is commonly observed across engineering disciplines, particularly in harsh media such as wastewater. In this study, a novel stabilizing controller for nitrification of high strength ammonia solutions is designed based on online signal derivatives. The controller uses the derivative of a drifting nitrite signal to determine if nitrite-oxidizing bacteria (NOB) are substrate limited or substrate inhibited. To ensure a meaningful interpretation of the derivative signal, the process is excited in a cyclic manner by repeatedly exposing the NOB to substrate-limited and substrate-inhibited conditions. The resulting control system successfully prevented nitrite accumulations for a period of 72 days in a laboratory-scale reactor. Slow disturbances in the form of feed composition changes and temperature changes were successfully handled by the controller while short-term temperature disturbances are shown to pose a challenge to the current version of this controller. Most importantly, we demonstrate that drift-tolerant control for the purpose of process stabilization can be achieved without sensor redundancy by combining deliberate input excitation, qualitative trend analysis, and coarse process knowledge.
Uusimaeki, T., Wagner, T., Lipinski, H. G., & Kaegi, R. (2019). AutoEM: a software for automated acquisition and analysis of nanoparticles. Journal of Nanoparticle Research, 21(6), 122 (11 pp.). doi:10.1007/s11051-019-4555-9, Institutional Repository

The era of research on (engineered) nanomaterials (NM) has been thriving for more than a decade and has delivered many beneficial applications, but also raised concerns about potential negative impacts on human health and ecosystems. The precautionary principle, hence, calls for a regulation of certain types of NM, which in consequence requires their unambiguous identification. Most of the currently available definitions of NM rely on an evaluation of the size of the constituent particles and therefore methods have to be developed to measure this parameter. Transmission electron microscopy (TEM) is one of the most promising techniques, as its resolving power well covers the nanosize range. However, limited automation of TEM analyses and possible user bias are major drawbacks of the technique and currently put severe constraints on its broader applications in nanometrology.
Therefore, the goal of this study was to develop a software code, referred to as AutoEM, to automatically acquire TEM images, measure particle sizes and extract the respective particle size distributions (PSD) of (nano)-materials. The AutoEM software also incorporates methods for elemental analyses of individual particles using electron energy loss and energy dispersive X-ray spectroscopy (EELS/EDX) allowing the extraction of element-specific PSDs. Additionally automated acquisition of energy-filtered images (EFTEM) is implemented in the AutoEM software, which can be used, e.g., to derive thickness maps and, thus, to evaluate the thickness of individual (plate-like) particles.
Verleysen, E., Wagner, T., Lipinski, H. G., Kägi, R., Koeber, R., Boix-Sanfeliu, A., … Mast, J. (2019). Evaluation of a TEM based approach for size measurement of particulate (nano)materials. Materials, 12(14), 2274 (20 pp.). doi:10.3390/ma12142274, Institutional Repository

An approach for the size measurement of particulate (nano)materials by transmission electron microscopy was evaluated. The approach combines standard operating procedures for specimen preparation, imaging, and image analysis, and it was evaluated on a series of certified reference materials and representative test materials with varying physical properties, including particle size, shape, and agglomeration state. The measurement of the median value of the minimal external particle diameter distribution was intra-laboratory validated. The validation study included an assessment of the limit of detection, working range, selectivity, precision, trueness, robustness, and ruggedness. An uncertainty that was associated to intermediate precision in the range of 1–7% and an expanded measurement uncertainty in the range of 7–20% were obtained, depending on the material and image analysis mode. No bias was observed when assessing the trueness of the approach on the certified reference materials ERM-FD100 and ERM-FD304. The image analysis method was validated in an inter-laboratory study by 19 laboratories, which resulted in a within-laboratory precision in the range of 2–8% and a between-laboratory precision of between 2% and 14%. The automation and standardization of the proposed approach significantly improves labour and cost efficiency for the accurate and precise size measurement of the particulate materials. The approach is shown to be implementable in many other electron microscopy laboratories.
Villez, K., Billeter, J., & Bonvin, D. (2019). Incremental parameter estimation under rank-deficient measurement conditions. Processes, 7(2), 75 (33 pp.). doi:10.3390/pr7020075, Institutional Repository

The computation and modeling of extents has been proposed to handle the complexity of large-scale model identification tasks. Unfortunately, the existing extent-based framework only applies when certain conditions apply. Most typically, it is required that a unique value for each extent can be computed. This severely limits the applicability of this approach. In this work, we propose a novel procedure for parameter estimation inspired by the existing extent-based framework. A key difference with prior work is that the proposed procedure combines structural observability labeling, matrix factorization, and graph-based system partitioning to split the original model parameter estimation problem into parameter estimation problems with the least number of parameters. The value of the proposed method is demonstrated with an extensive simulation study and a study based on a historical data set collected to characterize the isomerization of a-pinene. Most importantly, the obtained results indicate that an important barrier to the application of extent-based frameworks for process modeling and monitoring tasks has been lifted.
Voegelin, A., Senn, A. C., Kaegi, R., & Hug, S. J. (2019). Reductive dissolution of As(V)-bearing Fe(III)-precipitates formed by Fe(II) oxidation in aqueous solutions. Geochemical Transactions, 20(2) (13 pp.). doi:10.1186/s12932-019-0062-2, Institutional Repository

Iron(III)-precipitates formed by the oxidation of dissolved Fe(II) are important sorbents for major and trace elements in aquatic and terrestrial systems. Their reductive dissolution in turn may result in the release of associated elements. We examined the reductive dissolution kinetics of an environmentally relevant set of Fe(II)-derived arsenate-containing Fe(III)-precipitates whose structure as function of phosphate (P) and silicate (Si) content varied between poorly-crystalline lepidocrocite, amorphous Fe(III)-phosphate, and Si-containing ferrihydrite. The experiments were performed with 0.2–0.5 mM precipitate-Fe(III) using 10 mM Na-ascorbate as reductant, 5 mM bipyridine as Fe(II)-complexing ligand, and 10 mM MOPS/5 mM NaOH as pH 7.0 buffer. Times required for the dissolution of half of the precipitate (t50%) ranged from 1.5 to 39 h; spanning a factor 25 range. At loadings up to ~ 0.2 P/Fe (molar ratio), phosphate decreased the t50% of Si-free precipitates, probably by reducing the crystallinity of lepidocrocite. The reductive dissolution of Fe(III)-phosphates formed at higher P/Fe ratios was again slower, possibly due to P-inhibited ascorbate binding to precipitate-Fe(III). The slowest reductive dissolution was observed for P-free Si-ferrihydrite with ~ 0.1 Si/Fe, suggesting that silicate binding and polymerization may reduce surface accessibility. The inhibiting effect of Si was reduced by phosphate. Dried-resuspended precipitates dissolved 1.0 to 1.8-times more slowly than precipitates that were kept wet after synthesis, most probably because drying enhanced nanoparticle aggregation. Variations in the reductive dissolution kinetics of Fe(II) oxidation products as reported from this study should be taken into account when addressing the impact of such precipitates on the environmental cycling of co-transformed nutrients and contaminants.
Ward, B. J., Traber, J., Gueye, A., Diop, B., Morgenroth, E., & Strande, L. (2019). Evaluation of conceptual model and predictors of faecal sludge dewatering performance in Senegal and Tanzania. Water Research, 167, 115101 (13 pp.). doi:10.1016/j.watres.2019.115101, Institutional Repository

Unpredictable dewatering performance is a barrier to the effective management and treatment of faecal sludge. While mechanisms of dewatering in sludges from wastewater treatment are well understood, it is not clear how dewatering of faecal sludge fits into the framework of existing knowledge. We evaluate physical-chemical parameters, including EPS and cations, and demographic (source), environmental (microbial community), and technical factors (residence time) as possible predictors of dewatering performance in faecal sludge, and make comparisons to the existing conceptual model for wastewater sludge. Faecal sludge from public toilets took longer to dewater than sludge from other sources, and had turbid supernatant after settling. Slow dewatering and turbid supernatant corresponded to high EPS and monovalent cation concentrations, conductivity, and pH, but cake solids after dewatering was not correlated with EPS or other factors. Faecal sludges with higher EPS appeared less stabilised than those with lower EPS, potentially a result of inhibition of biological degradation due to high urine concentrations. However, distinct microbial community compositions were also observed in samples with higher and lower EPS concentrations. Higher EPS faecal sludge was comparable in dewatering behaviour and EPS content to anaerobically digested and primary wastewater sludges. However lower EPS faecal sludges had different dewatering behaviour than wastewater sludges and may be governed by different mechanisms.
Wielinski, J., Gogos, A., Voegelin, A., Müller, C., Morgenroth, E., & Kaegi, R. (2019). Transformation of nanoscale and ionic Cu and Zn during the incineration of digested sewage sludge (biosolids). Environmental Science and Technology, 53(20), 11704-11713. doi:10.1021/acs.est.9b01983, Institutional Repository

Engineered nanoparticles (NP) discharged to sewers are efficiently retained by wastewater treatment plants and accumulate in the sewage sludge, which is commonly digested. The resulting biosolids are either used as fertilizer or incinerated. In this study, we address the transformation of Cu and Zn during sewage sludge incineration and evaluate whether the form of Cu or Zn (nanoparticulate versus dissolved) added to the digested sewage sludge affects the fate of the metals during incineration. We spiked CuO-NP, dissolved CuSO4, ZnO-NP, or dissolved ZnSO4 into anaerobically digested sewage sludge to reach Cu and Zn concentrations of ≈2500 and ≈3700 mg/kg and maintained the sludge under mesophilic, anaerobic conditions for 24 h. Subsequently, the sludge was incinerated in a pilot fluidized bed reactor. The speciation of Cu and Zn in the sludge, derived from X-ray absorption spectroscopy measurements, was dominated by sulfidic species, with >90% of Cu and >60% of Zn coordinated to reduced sulfur groups. In the ash, both Cu (>60%) and Zn (≈100%) were coordinated to oxygen. The chemical speciation of Cu and Zn in the ashes was independent of whether they were spiked in the dissolved or nanoparticulate form and closely matched the speciation of Cu and Zn observed in ashes from full-scale incinerators.
Worms, I. A. M., Chmiel, H. E., Traber, J., Tofield-Pasche, N., & Slaveykova, V. I. (2019). Dissolved organic matter and associated trace metal dynamics from river to lake, under ice-covered and ice-free conditions. Environmental Science and Technology, 53(24), 14134-14143. doi:10.1021/acs.est.9b02184, Institutional Repository

The present study investigates the changes in dissolved organic matter (DOM) composition and its influences on trace metal dispersion from the Shuya River (SR) in the Petrozavodsk Bay of Lake Onega during ice-covered and ice-free periods. Humic substances (HS) found in the SR dominated the composition of DOM through the river-bay-lake continuum in both periods. When the bay was ice-covered, both the aromaticity and the size of HS varied in the water column according to a horizontal stratification and decreased in the bay, while under ice-free conditions, they decreased along the river-lake gradient, suggesting in both cases a decrease in the proportion of HS with high aromatic character. These findings were associated with an overall decrease in the proportion of HS components that have the highest molecular masses. The quantification of metal bound to HS revealed that these characteristics were associated with a decrease in the binding capacity of the HS for Fe and Al but not Cu while dispersing in the bay to the lake. Pb was found to bind on HS, but its behavior in the bay could not be related to the HS dispersion nor to the changes in HS properties.
Xu, J., Wang, Y., Weng, C., Bai, W., Jiao, Y., Kaegi, R., & Lowry, G. V. (2019). Reactivity, selectivity, and long-term performance of sulfidized nanoscale zerovalent iron with different properties. Environmental Science and Technology, 53(10), 5936-5945. doi:10.1021/acs.est.9b00511, Institutional Repository

Sulfidized nanoscale zerovalent iron (SNZVI) has desirable properties for in situ groundwater remediation. However, there is limited understanding of how the sulfidation type and particle properties affect the reactivity and selectivity of SNZVI toward groundwater contaminants, or how reactivity changes as the particles age. Here, SNZVI synthesized by either a one-step (SNZVI-1) or two-step (SNZVI-2) process were characterized, and the reactivity of both fresh and aged (1d to 60 d) nanoparticles was assessed. The measured S/Fe ratio was 5.4 ± 0.5 mol % for SNZVI-1 and 0.8 ± 0.1 mol % for SNZVI-2. XPS analysis indicates S2-, S22-, and Sn2- species on the surface of both SNZVI-1 and SNZVI-2, while S22- is the dominant species inside of the SNZVI nanoparticles. SNZVI-1 particles were hydrophobic (contact angle = 103 ± 3°), while the other materials were hydrophilic (contact angles were 18 ± 2° and 36 ± 3° for NZVI and SNZVI-2, respectively). SNZVI-1, with greater S content and hydrophobicity, was less reactive with water than either NZVI or SNZVI-2 over a 60 d period, resulting in less H2 evolution. It also had the highest reactivity with TCE and the lowest reactivity with nitrate, consistent with its higher hydrophobicity. In contrast, both NZVI and SNZVI-2 were reactive with both TCE and nitrate. Both types of SNZVI remained more reactive after aging in water over 60 d than NZVI. These data suggest that the properties of the SNZVI made from a one-step synthesis procedure may provide better reactivity, selectivity, and longevity than that made from a two-step process.
Zanini, M., Cingolani, A., Hsu, C. P., Fernández-Rodríguez, M. Á., Soligno, G., Beltzung, A., … Isa, L. (2019). Mechanical phase inversion of Pickering emulsions via metastable wetting of rough colloids. Soft Matter, 15(39), 7888-7900. doi:10.1039/C9SM01352K, Institutional Repository

The possibility to invert emulsions from oil-in-water to water-in-oil (or vice versa) in a closed system, i.e. without any formulation change, remains an open fundamental challenge with many opportunities for industrial applications. Here, we propose a mechanism that exploits particle surface roughness to induce metastable wetting and obtain mechanically-responsive Pickering emulsions. We postulate that the phase inversion is driven by an in situ switch of the particle wettability from metastable positions at the interface following the input of controlled mechanical energy. Oil-in-water emulsions can be prepared at low energy using mildly hydrophobic rough colloids, which are dispersed in water and weakly pinned at the interface, and switched to water-in-oil emulsions by a second emulsification at higher energy, which triggers the relaxation of the particle contact angle. The same principle is demonstrated for the complementary emulsions using mildly hydrophilic colloids initially dispersed in oil. Our experiments and simulations support that the delicate interplay between particle surface design during synthesis and the energy of the emulsification process can encode a kinetic pathway for the phase inversion. Both organic and inorganic nanoparticles can be used, allowing for the future implementation of our strategy in a broad range of smart industrial formulations.
Zheng, Y., Mutzner, L., Ort, C., Kaegi, R., & Gottschalk, F. (2019). Modelling engineered nanomaterials in wet-weather discharges. NanoImpact, 16, 100188 (8 pp.). doi:10.1016/j.impact.2019.100188, Institutional Repository

The impacts of the unintended release of engineered nanomaterials (ENMs) and the resulting exposure to the ecosystems are still poorly understood and intensively debated. In current mass flow models, a global transfer coefficient is used to account for ENMs discharged from sewer systems to surface waters during rain events.
However, different types of sewer systems and specific ENM applications likely require a more elaborate approach to quantify ENM loads entering surface waters during rain events. Therefore, we evaluated the impact of distinguishing between different application areas of ENMs (indoor/outdoor) and different types of sewer systems (combined/separate) on the loads of selected ENMs passing through wastewater systems and reaching the surface water. We applied a dynamic mass flow analysis to eight substances (TiO2, ZnO, Ag, SiO2, FeOx, CuO, CeO2 and carbon black) for six different sewer system configurations. To estimate the runoff from streets and facades, we used a hydrological model developed for dissolved substances. For areas with separate sewer systems only and ENMs predominantly used in and released from outdoor applications (e.g. CuO, carbon black), up to ~80% of the annual loads entering the sewer systems never reach a sewage treatment plant. Those ENMs are directly discharged to surface waters via stormwater outlets. For combined sewer systems and ENMs mainly applied indoors (e.g. Ag, ZnO), the percentage of ENM bypassing sewage treatment plants remains below 2%. Although the model is setup for Switzerland and other geographical areas will show for example different rain characteristics, the relative importance of the different release pathways will broadly remain the same and the results should, therefore, be transferrable to other countries.
Ziemba, C., Khavkin, M., Priftis, D., Acar, H., Mao, J., Benami, M., … Herzberg, M. (2019). Antifouling properties of a self-assembling glutamic acid-lysine zwitterionic polymer surface coating. Langmuir, 35(5), 1699-1713. doi:10.1021/acs.langmuir.8b00181, Institutional Repository

There is a need for the development of antifouling materials to resist adsorption of biomacromolecules. Here we describe the preparation of a novel zwitterionic block copolymer with the potential to prevent or delay the formation of microbial biofilms. The block copolymer comprised a zwitterionic (hydrophilic) section of alternating glutamic acid (negatively charged) and lysine (positively charged) units and a hydrophobic polystyrene section. Cryo-TEM and dynamic-light-scattering (DLS) results showed that, on average, the block copolymer self-assembled into 7-nm-diameter micelles in aqueous solutions (0 to 100 mM NaCl, pH 6). Quartz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM), and contact angle measurements demonstrated that the block copolymer self-assembled into a brush-like monolayer on polystyrene surfaces. The brush-like monolayer produced from a 100 mg/L block copolymer solution exhibited an average distance, d, of approximately 4-8 nm between each block copolymer molecule (center to center). Once the brush-like monolayer self-assembled, it reduced EPS adsorption onto the polystyrene surface by ∼70% (mass), reduced the rate of bacterial attachment by >80%, and inhibited the development of thick biofilms. QCM-D results revealed that the EPS molecules penetrate between the chains of the brush and adsorb onto the polystyrene surface. Additionally, AFM analyses showed that the brush-like monolayer prevents the adhesion of large (>d) hydrophilic colloids onto the surface via hydration repulsion; however, molecules or colloids small enough to fit between the brush polymers (<d) were able to be adsorbed onto the surface via van der Waals interactions. Overall, we found that the penetration of extracellular organelles, as well as biopolymers through the brush, is critical for the failure of the antifouling coating, and likely could be prevented through tuning of the brush density. Stability and biofilm development testing on multiple surfaces (polypropylene, glass, and stainless steel) support practical applications of this novel block copolymer.
Ziemba, C., Larivé, O., Deck, S., Huisman, T., & Morgenroth, E. (2019). Comparing the anti-bacterial performance of chlorination and electrolysis post-treatments in a hand washing water recycling system. Water Research X, 2, 100020 (10 pp.). doi:10.1016/j.wroa.2018.100020, Institutional Repository

Innovative solutions are necessary to enable the decentralized recycling of greywater for applications requiring high-quality water, such as hand washing. While physical barriers such as ultrafiltration membranes effectively prevent the passage of bacteria, and chemical and biological treatments can effectively reduce the carbon content of the treated water, there exists a knowledge gap regarding the application of anti-bacterial strategies to prevent the growth of harmful bacteria following treatment. In this study, the effluent water from a household-scale greywater treatment system was fed to seven parallel experimental post-treatment tanks: three receiving direct chlorination with free chlorine residuals of 0.2, 1 or 5 mg Cl2/L, three with chlorine produced through electrolysis at the same residual concentrations, and one control with no chlorine added. For increasing concentrations of direct chlorination, the median total cell count (TCC) values were 9 × 104, 2.9 × 104 and 1.8 × 103 cells/mL, respectively. Electrolysis treatment produced very similar TCC concentrations, 8.8 × 104, 1.1 × 104 and 2.3 × 103 cells/mL. The TCC concentrations were lower than the concentration of the water entering each tank (~3 × 105 cells/mL). Intact cell count (ICC) measurements indicated that the viable cell concentrations, were less than 10% of the TCC values. Though electrolysis treatment can produce powerful oxidants, such as hydroxyl radical, there was no evidence that electrolysis in this system provided additional benefits beyond chlorine production for control of total or intact cell counts. Oxidation of bacteria by chlorine was the dominant anti-bacterial mechanism in our system. Monitoring of dissolved organic carbon (DOC) and assimilable organic carbon (AOC) did not suggest that carbon-limitation significantly impacted cell counts when chlorination or electrolysis treatment was applied. This work demonstrates that either direct chlorination or electrolysis treatment are able to reduce bacteria concentrations over long-term operation of a hand washing water treatment system. We recommend selecting chlorine residual targets such that a chlorine residual is maintained during periods of challenging operating conditions. We observed that a target residual of 1 mg Cl2/L, in our system, maintained the TCC below the concentration found in Zürich drinking water.
Achermann, S., Falås, P., Joss, A., Mansfeldt, C., Men, Y., Vogler, B., & Fenner, K. (2018). Trends in micropollutant biotransformation along a solids retention time gradient. Environmental Science and Technology, 52(20), 11601-11611. doi:10.1021/acs.est.8b02763, Institutional Repository

For many polar organic micropollutants, biotransformation by activated sludge microorganisms is a major removal process during wastewater treatment. However, our current understanding of how wastewater treatment operations influence microbial communities and their micropollutant biotransformation potential is limited, leaving major parts of observed variability in biotransformation rates across treatment facilities unexplained. Here, we present biotransformation rate constants for 42 micropollutants belonging to different chemical classes along a gradient of solids retention time (SRT). The geometric mean of biomass-normalized first-order rate constants shows a clear increase between 3 d and 15 d SRT by 160% and 87%, respectively, in two experiments. However, individual micropollutants show a variety of trends. Rate constants of oxidative biotransformation reactions mostly increased with SRT. Yet, nitrifying activity could be excluded as primary driver. For substances undergoing other than oxidative reactions, i.e. mostly substitution-type reactions, more diverse dependencies on SRT were observed. Most remarkably, characteristic trends were observed for groups of substances undergoing similar types of initial transformation reaction, suggesting that shared enzymes or enzyme systems that are conjointly regulated catalyze biotransformation reactions within such groups. These findings open up opportunities for correlating rate constants with measures of enzyme abundance, which in turn should help to identify genes or gene products associated with the respective biotransformation reactions.
Arhin, S. G., Banadda, N., Komakech, A. J., Pronk, W., & Marks, S. J. (2018). Optimization of hybrid coagulation-ultrafiltration process for potable water treatment using response surface methodology. Water Science and Technology: Water Supply, 18(3), 862-874. doi:10.2166/ws.2017.159, Institutional Repository

In order to optimize the operating conditions for a combined polyaluminum chloride (PACl) coagulation/flocculation and ultrafiltration process for treating potable water, the main, second order and interaction effects of PACl dose and flocculation retention time (FRT) on permeate turbidity, UV254 and membrane permeability were investigated using a 100 kDa hollow fiber membrane operated in the dead-end mode. A multilevel factorial design was used to determine the relevant ranges of the two factors for optimization. A 22 central composite design (CCD) was then used to develop mathematical correlation models for the optimum operating conditions. The main effect of PACl dose was the most significant factor on all the responses. For permeability, both the main effect of FRT and FRT – PACl dose interactions were found to be insignificant. The optimum PACl dose and FRT for the feed water were 20 mg/L and 14 min respectively. Corresponding permeate turbidity, UV254 and permeability were 0.15 ± 0.01 NTU, 0.003 ± 0.001 cm−1 and 62.0 ± 9.52 Lm−2h−1 bar−1 respectively. Experimental validation runs confirmed the reliability of the predicted optimal conditions thus implying that CCD models can be used to predict/optimize the quality and quantity of permeate from hybrid coagulation-ultrafiltration systems for potable water treatment.
Bourgin, M., Beck, B., Boehler, M., Borowska, E., Fleiner, J., Salhi, E., … McArdell, C. S. (2018). Evaluation of a full-scale wastewater treatment plant upgraded with ozonation and biological post-treatments: abatement of micropollutants, formation of transformation products and oxidation by-products. Water Research, 129, 486-498. doi:10.1016/j.watres.2017.10.036, Institutional Repository

To protect the ecosystem and drinking water resources in Switzerland and in the countries of the downstream catchments, a new Swiss water protection act entered into force in 2016 aiming to reduce the discharge of micropollutants from wastewater treatment plants (WWTPs). As a consequence, selected WWTPs must be upgraded by an advanced treatment for micropollutant abatement with suitable and economic options such as (powdered) activated carbon treatment or ozonation. WWTP Neugut (105′000 people equivalent) was the first WWTP in Switzerland to implement a long-term full-scale ozonation. Differing specific ozone doses in the range of 0.35–0.97 g O3/g DOC were applied to determine the adequate ozone dose to fulfill the requirements of the Swiss water protection act. Based on this assessment, a specific ozone dose of 0.55 g O3/g DOC is recommended at this plant to ensure an average abatement of the twelve selected indicator substances by ≥80% over the whole treatment. A monitoring of 550 substances confirmed that this dose was very efficient to abate a broad range of micropollutants by >79% on average. After ozonation, an additional biological post-treatment is required to eliminate possible negative ecotoxicological effects generated during ozonation caused by biodegradable ozonation transformation products (OTPs) and oxidation by-products (OBPs). Three biological treatments (sand filtration, moving bed, fixed bed) and granular activated carbon (GAC, fresh and pre-loaded) filtration were evaluated as post-treatments after ozonation. In parallel, a fresh GAC filter directly connected to the effluent of the secondary clarifier was assessed. Among the three purely biological post-treatments, the sand filtration performed best in terms of removal of dissolved organic carbon (DOC), assimilable organic carbon (AOC) and total suspended solids (TSS). The fresh activated carbon filtration ensured a significant additional micropollutants abatement after ozonation due to sorption. The relative abatement of the indicator substances ranged between 20 and 89% after 27′000 bed volumes (BV) and was still substantial at 50′000 BV. In an identical GAC filter running in parallel and being fed with the effluent of the secondary clarifier, the elimination was less efficient. Seven primary OTPs (chlorothiazide and six N-oxides) formed during ozonation could be quantified thanks to available reference standards. Their concentration decreased with increasing specific ozone doses with the concomitant formation of other OTPs. The seven OTPs were found to be stable compounds and were not abated in the biological post-treatments. They were sorbed in the fresh GAC filter, but less efficiently than the corresponding parent compounds. Two OBPs, bromate (BrO3−) and N-nitrosodimethylamine (NDMA), were formed during ozonation but did not exceeded 5 μg/L for bromate and 30 ng/L for NDMA at the recommended specific ozone dose of 0.55 g O3/g DOC. NDMA was well abated in all post-treatments (minimum 41% during fixed bed filtration, maximum 83% during fresh GAC filtration), while bromate was very stable as expected.
Carrel, M., Morales, V. L., Beltran, M. A., Derlon, N., Kaufmann, R., Morgenroth, E., & Holzner, M. (2018). Biofilms in 3D porous media: delineating the influence of the pore network geometry, flow and mass transfer on biofilm development. Water Research, 134, 280-291. doi:10.1016/j.watres.2018.01.059, Institutional Repository

This study investigates the functional correspondence between porescale hydrodynamics, mass transfer, pore structure and biofilm morphology during progressive biofilm colonization of a porous medium. Hydrodynamics and the structure of both the porous medium and the biofilm are experimentally measured with 3D particle tracking velocimetry and micro X-ray Computed Tomography, respectively. The analysis focuses on data obtained in a clean porous medium after 36 h of biofilm growth. Registration of the particle tracking and X-ray data sets allows to delineate the interplay between porous medium geometry, hydrodynamic and mass transfer processes on the morphology of the developing biofilm. A local analysis revealed wide distributions of wall shear stresses and concentration boundary layer thicknesses. The spatial distribution of the biofilm patches uncovered that the wall shear stresses controlled the biofilm development. Neither external nor internal mass transfer limitations were noticeable in the considered system, consistent with the excess supply of nutrient and electron acceptors. The wall shear stress remained constant in the vicinity of the biofilm but increased substantially elsewhere.
Carrel, M., Morales, V. L., Dentz, M., Derlon, N., Morgenroth, E., & Holzner, M. (2018). Pore-scale hydrodynamics in a progressively bioclogged three-dimensional porous medium: 3-D particle tracking experiments and stochastic transport modeling. Water Resources Research, 54(3), 2183-2198. doi:10.1002/2017WR021726, Institutional Repository

Biofilms are ubiquitous bacterial communities that grow in various porous media including soils, trickling, and sand filters. In these environments, they play a central role in services ranging from degradation of pollutants to water purification. Biofilms dynamically change the pore structure of the medium through selective clogging of pores, a process known as bioclogging. This affects how solutes are transported and spread through the porous matrix, but the temporal changes to transport behavior during bioclogging are not well understood. To address this uncertainty, we experimentally study the hydrodynamic changes of a transparent 3-D porous medium as it experiences progressive bioclogging. Statistical analyses of the system's hydrodynamics at four time points of bioclogging (0, 24, 36, and 48 h in the exponential growth phase) reveal exponential increases in both average and variance of the flow velocity, as well as its correlation length. Measurements for spreading, as mean-squared displacements, are found to be non-Fickian and more intensely superdiffusive with progressive bioclogging, indicating the formation of preferential flow pathways and stagnation zones. A gamma distribution describes well the Lagrangian velocity distributions and provides parameters that quantify changes to the flow, which evolves from a parallel pore arrangement under unclogged conditions, toward a more serial arrangement with increasing clogging. Exponentially evolving hydrodynamic metrics agree with an exponential bacterial growth phase and are used to parameterize a correlated continuous time random walk model with a stochastic velocity relaxation. The model accurately reproduces transport observations and can be used to resolve transport behavior at intermediate time points within the exponential growth phase considered.
Corominas, L., Garrido-Baserba, M., Villez, K., Olsson, G., Cortés, U., & Poch, M. (2018). Transforming data into knowledge for improved wastewater treatment operation: a critical review of techniques. Environmental Modelling and Software, 106, 89-103. doi:10.1016/j.envsoft.2017.11.023, Institutional Repository

The aim of this paper is to describe the state-of-the art computer-based techniques for data analysis to improve operation of wastewater treatment plants. A comprehensive review of peer-reviewed papers shows that European researchers have led academic computer-based method development during the last two decades. The most cited techniques are artificial neural networks, principal component analysis, fuzzy logic, clustering, independent component analysis and partial least squares regression. Even though there has been progress on techniques related to the development of environmental decision support systems, knowledge discovery and management, the research sector is still far from delivering systems that smoothly integrate several types of knowledge and different methods of reasoning. Several limitations that currently prevent the application of computer-based techniques in practice are highlighted.
Correia, M., Uusimäki, T., Philippe, A., & Loeschner, K. (2018). Challenges in determining the size distribution of nanoparticles in consumer products by asymmetric flow field-flow fractionation coupled to inductively coupled plasma-mass spectrometry: the example of Al2O3, TiO2, and SiO2 nanoparticles in toothpaste. Separations, 5(4), 56 (25 pp.). doi:10.3390/separations5040056, Institutional Repository

According to the current European regulation on cosmetics, any ingredient present as a nanomaterial should be indicated in the ingredient list. There is a need for analytical methods capable of determining the size of the relevant ingredients and thus assessing if these are nanomaterials or not. An analytical method based on asymmetric flow field-flow fractionation (AF4) and inductively coupled plasma-mass spectrometry (ICP-MS) was developed to determine the size of particles present in a commercial toothpaste. Multi-angle light scattering (MALS) was used for on-line size determination. The number-based particle size distributions (PSDs) of the particles were retrieved upon mathematical conversion of the mass-based PSDs recovered from the AF4-ICP-MS fractograms. AF4-ICP-MS allowed to separate and detect Al2O3 and TiO2 particles in the toothpaste and to retrieve a correct TiO2 number-based PSD. The potential presence of particles in the lower size range of the Al2O3 mass-based PSD had a strong impact on sizing and nanomaterial classification upon conversion. AF4 coupled with ICP-MS and MALS was found to be a powerful approach for characterization of different particles in a multiple-particle system such as toothpaste. Confirmation of particle size by a secondary method such as single particle ICP-MS or hydrodynamic chromatography was crucial.
Desmond, P., Best, J. P., Morgenroth, E., & Derlon, N. (2018). Linking composition of extracellular polymeric substances (EPS) to the physical structure and hydraulic resistance of membrane biofilms. Water Research, 132, 211-221. doi:10.1016/j.watres.2017.12.058, Institutional Repository

The effect of extracellular polymeric substances (EPS) on the meso-scale physical structure and hydraulic resistance of membrane biofilms during gravity driven membrane (GDM) filtration was investigated. Biofilms were developed on the surface of ultrafiltration membranes during dead-end filtration at ultra-low pressure (70 mbar). Biofilm EPS composition (total protein, polysaccharide and eDNA) was manipulated by growing biofilms under contrasting nutrient conditions. Nutrient conditions consisted of (i) a nutrient enriched condition with a nutrient ratio of 100:30:10 (C: N: P), (ii) a phosphorus limitation (C: N: P ratio: 100:30:0), and (iii) a nitrogen limitation (C: N: P ratio: 100:0:10). The structure of the biofilm was characterised at meso-scale using Optical Coherence Tomography (OCT). Biofilm composition was analysed with respect to total organic carbon, total cellular mass and extracellular concentrations of proteins, polysaccharides, and eDNA. 2D-confocal Raman mapping was used to characterise the functional group composition and micro-scale distribution of the biofilms EPS. Our study reveals that the composition of the EPS matrix can determine the meso-scale physical structure of membrane biofilms and in turn its hydraulic resistance. Biofilms grown under P limiting conditions were characterised by dense and homogeneous physical structures with high concentrations of polysaccharides and eDNA. Biofilm grown under nutrient enriched or N limiting conditions were characterised by heterogeneous physical structures with lower concentrations of polysaccharides and eDNA. For P limiting biofilms, 2D-confocal Raman microscopy revealed a homogeneous spatial distribution of anionic functional groups in homogeneous biofilm structures with higher polysaccharide and eDNA concentrations. This study links EPS composition, physical structure and hydraulic resistance of membrane biofilms, with practical relevance for the hydraulic performances of GDM ultrafiltration.
Desmond, P., Morgenroth, E., & Derlon, N. (2018). Physical structure determines compression of membrane biofilms during Gravity Driven Membrane (GDM) ultrafiltration. Water Research, 143, 539-549. doi:10.1016/j.watres.2018.07.008, Institutional Repository

Increasing transmembrane pressure (TMP) can compress and increase the hydraulic resistance of membrane biofilms. The purpose of the present study is to evaluate how compression of membrane biofilms occurs and how structural rearrangement can affect hydraulic resistance. Biofilms with heterogeneous and homogeneous physical structures were grown in membrane fouling simulators (MFS) in dead-end mode for 20 days with either (i) a nutrient enriched condition with a nutrient ratio of 100:30:10 (C: N: P), (ii) a phosphorus limitation (C: N: P ratio: 100:30:0), or (iii) river water (C: N: P ratio: ca. 100:10:1). The structural and hydraulic response of membrane biofilms to (a) changes in transmembrane pressures (0.06-0.1-0.5-0.1-0.06 bar) and (b) changes in permeate flux (10-15-20-15-10 L/m2/h) were investigated. Optical coherence tomography (OCT) was used to monitor biofilm structural response, and OCT images were processed to quantify changes in the mean biofilm thickness and relative roughness. Nutrient enriched and river water biofilms had heterogeneous physical structures with greater surface roughness (Ra' > 0.2) than homogeneous P limiting biofilms (Ra' < 0.2). Compression of biofilms with rough heterogeneous structures (Ra' > 0.2) was irreversible, indicated by irreversible decrease in surface roughness, partial relaxation in mean biofilm thickness and irreversible increase in hydraulic resistance. Compression of homogeneous biofilm (Ra' < 0.2) was on the other hand reversible, indicated by full relaxation of the biofilms structure and restoration of initial hydraulic resistance. Hydraulic response (i.e., change in the specific biofilm resistance) did not correspond with the change in physical structure of heterogeneous biofilms. The presented study provides a fundamental understanding of how biofilm physical structure can affect the biofilm's response to a change in TMP, with practical relevance for the operation of GDM filtration systems.
Desmond, P., Böni, L., Fischer, P., Morgenroth, E., & Derlon, N. (2018). Stratification in the physical structure and cohesion of membrane biofilms – implications for hydraulic resistance. Journal of Membrane Science, 564, 897-904. doi:10.1016/j.memsci.2018.07.088, Institutional Repository

This study aimed at evaluating stratification of hydraulic resistance over the depth of membrane biofilms developed during gravity driven membrane (GDM) ultrafiltration. Biofilms were grown in membrane fouling simulators (MFS) for 25 days under 3 contrasting influent conditions: nutrient enriched, phosphorus limiting, and river water influent. Shear rheology was used to determine the biofilms material characteristics (e.g., elasticity, yield stress). Optical coherence tomography (OCT) was used to determine the response of the biofilms physical structure (e.g., thickness) to increased hydraulic shear stress from 0 up to 2.6 Pa. Stratification was observed in nutrient enriched and river water biofilms and which partially detached by erosion of their rough top layer under low shear conditions. A cohesive base layer remained attached to the membrane surface under high shear conditions, indicating stratification in cohesion over the biofilms depth. Erosion of the top layer only resulted in a slight decrease in the biofilm hydraulic resistance indicating that the very cohesive and thin base layer also represent significant hydraulic resistance. Conversely, P limiting biofilms had uniform structural and mechanical characteristics, detaching by sloughing and peeling at low and high shear stress respectively. Biofilms formed under phosphorus limiting conditions had equal elasticity, yet a lower yield stress compared to nutrient enriched and river water biofilms respectively and were more susceptible to detachment. The scientific implication of the presented work demonstrates that biofilm detachment is influenced by both the structural (surface heterogeneity) and material characteristics (e.g., yield stress), with practical relevance for hydraulic resistance during GDM filtration.
Falås, P., Jewell, K. S., Hermes, N., Wick, A., Ternes, T. A., Joss, A., & Nielsen, J. L. (2018). Transformation, CO2 formation and uptake of four organic micropollutants by carrier-attached microorganisms. Water Research, 141, 405-416. doi:10.1016/j.watres.2018.03.040, Institutional Repository

A tiered process was developed to assess the transformation, CO2 formation and uptake of four organic micropollutants by carrier-attached microorganisms from two municipal wastewater treatment plants. At the first tier, primary transformation of ibuprofen, naproxen, diclofenac, and mecoprop by carrier-attached microorganisms was shown by the dissipation of the target compounds and the formation of five transformation products using LC-tandem MS. At the second tier, the microbial cleavage of the four organic micropollutants was confirmed with 14C-labeled micropollutants through liquid scintillation counting of the 14CO2 formed. At the third tier, microautoradiography coupled with fluorescence in situ hybridization (MAR-FISH) was used to screen carrier-attached microorganisms for uptake of the four radiolabeled micropollutants. Results from the MAR-FISH screening indicated that only a small fraction of the microbial community (≤1‰) was involved in the uptake of the radiolabeled micropollutants and that the responsible microorganisms differed between the compounds. At the fourth tier, the microbial community structure of the carrier-attached biofilms was analyzed by 16S rRNA gene amplicon sequencing. The sequencing results showed that the MAR-FISH screening targeted ∼80% of the microbial community and that several taxonomic families within the FISH-probed populations with MAR-positive signals (i.e. Firmicutes, Gammaproteobacteria, and Deltaproteobacteria) were present in both biofilms. From the broader perspective of organic micropollutant removal in biological wastewater treatment, the MAR-FISH results of this study indicate a high degree of microbial substrate specialization that could explain differences in transformation rates and patterns between micropollutants and microbial communities.
Giese, B., Klaessig, F., Park, B., Kaegi, R., Steinfeldt, M., Wigger, H., … Gottschalk, F. (2018). Risks, release and concentrations of engineered nanomaterial in the environment. Scientific Reports, 8(1), 1565 (8 pp.). doi:10.1038/s41598-018-19275-4, Institutional Repository

For frequently used engineered nanomaterials (ENMs) CeO2-, SiO2-, and Ag, past, current, and future use and environmental release are investigated. Considering an extended period (1950 to 2050), we assess ENMs released through commercial activity as well as found in natural and technical settings. Temporal dynamics, including shifts in release due to ENM product application, stock (delayed use), and subsequent end-of-life product treatment were taken into account. We distinguish predicted concentrations originating in ENM use phase and those originating from end-of-life release. Furthermore, we compare Ag- and CeO2-ENM predictions with existing measurements. The correlations and limitations of the model, and the analytic validity of our approach are discussed in the context of massive use of assumptive model data and high uncertainty on the colloidal material captured by the measurements. Predictions for freshwater CeO2-ENMs range from 1 pg/l (2017) to a few hundred ng/l (2050). Relative to CeO2, the SiO2-ENMs estimates are approximately 1,000 times higher, and those for Ag-ENMs 10 times lower. For most environmental compartments, ENM pose relatively low risk; however, organisms residing near ENM 'point sources' (e.g., production plant outfalls and waste treatment plants), which are not considered in the present work, may be at increased risk.
Gogos, A., Voegelin, A., & Kaegi, R. (2018). Influence of organic compounds on the sulfidation of copper oxide nanoparticles. Environmental Science: Nano, 5(11), 2560-2569. doi:10.1039/C8EN00523K, Institutional Repository

Dissolved organic matter (DOM) influences the colloidal properties of engineered nanomaterials (ENMs) and impacts their transport and transformation in the environment. Sulfidation affects the fate and the ecological effects of released chalcophile ENMs. For copper oxide nanoparticles (CuO-NPs), the sulfidation and its kinetics have been described. However, the influence of DOM on this reaction has not been investigated yet. In wastewater systems, having high bisulfide contents, the DOM mainly consists of proteins, polysaccharides and humic substances. We therefore investigated the influence of the organic compounds bovine serum albumin (BSA, model protein), alginate (ALG, model polysaccharide), and polyacrylic acid (PAA, natural organic matter analogue) as well as that of natural humic acid (HA) and filtered wastewater (FW) on the sulfidation of CuO-NPs. Experiments were conducted in solutions buffered to pH 8.0 at concentrations of 1.3 mM CuO and ∼3.2 mM HS−. Increasing amounts of organic compounds were added to reach concentrations of 10–1000 mg L−1. Reacted CuO-NPs were collected at selected time points and characterized using Cu K-edge X-ray absorption spectroscopy and analytical electron microscopy. The sulfidation of the CuO-NPs was complete after 3 h in all experiments, except in the presence of 1000 mg L−1 BSA where ∼30% of CuO remained untransformed. Complete sulfidation of the CuO-NPs as observed in experiments conducted in FW suggests quantitative sulfidation of CuO-NPs in real wastewater. Without organic compounds, initially formed amorphous CuxS transformed into covellite over time. The presence of BSA, HA, ALG, and FW (but not PAA) hampered this transformation resulting in higher fractions of CuxS after sulfidation. Different amounts of CuxS with sizes of 10 kDa up to 10 nm formed during sulfidation depending on the type of organic compound. The properties of the CuxS-NPs formed by CuO-NP sulfidation must be considered when assessing their environmental impact.
Gondikas, A., Von Der Kammer, F., Kaegi, R., Borovinskaya, O., Neubauer, E., Navratilova, J., … Hofmann, T. (2018). Where is the nano? Analytical approaches for the detection and quantification of TiO2 engineered nanoparticles in surface waters. Environmental Science: Nano, 5(2), 313-326. doi:10.1039/c7en00952f, Institutional Repository

Detecting and quantifying engineered nanoparticles (ENPs) in complex environmental matrices requires the distinction between natural nanoparticles (NNPs) and ENPs. The distinction of NNPs and ENPs for regulatory purposes calls for cost-efficient methods, but is hampered by similarities in intrinsic properties, such as particle composition, size, density, surface chemistry, etc. Titanium dioxide (TiO2) ENPs, for instance, are produced in very large quantities but Ti also commonly occurs naturally in nano-scale minerals. In this work, we focus on utilizing particle size and composition to identify ENPs in a system with a significant background concentration of the target metal. We have followed independent approaches involving both conventional and state-of-the-art analytical techniques to detect and quantify TiO2 ENPs released into surface waters from sunscreen products and to distinguish them from Ti-bearing NNPs. To achieve this, we applied single particle inductively coupled plasma mass spectrometry with single-element (spICPMS) and multi-element detection (time-of-flight) spICP-TOFMS, together with transmission electron microscopy (TEM), automated scanning electron microscopy (autoSEM), and bulk elemental analyses. A background concentration of Ti-bearing NPs (approximately 5 × 103 particles per ml), possibly of natural origin, was consistently observed outside the bathing season. This concentration increased by up to 40% during the bathing season. Multi-element analysis of individual particles using spICP-TOFMS revealed that Al, Fe, Mn, and Pb are often present in natural Ti-bearing NPs, but no specific multi-element signatures were detected for ENPs. Our data suggests that TiO2 ENPs enter the lake water during bathing activities, eventually agglomerating and sedimenting. We found adhesion of the TiO2 ENPs to the air-water interface for short time periods, depending on wind conditions. This study demonstrates that the use of spICP-TOFMS and spICPMS in combination with other conventional analytical techniques offers significant advantages for discriminating between NNPs and ENPs. The quantitative data produced in this work can be used as input for modeling studies or as a benchmark for analysis protocols and model validations.
Hagemann, N., Spokas, K., Schmidt, H. P., Kägi, R., Böhler, M. A., & Bucheli, T. D. (2018). Activated carbon, biochar and charcoal: linkages and synergies across pyrogenic carbon's ABCs. Water, 10(2), 182 (19 pp.). doi:10.3390/w10020182, Institutional Repository

Biochar and activated carbon, both carbonaceous pyrogenic materials, are important products for environmental technology and intensively studied for a multitude of purposes. A strict distinction between these materials is not always possible, and also a generally accepted terminology is lacking. However, research on both materials is increasingly overlapping: sorption and remediation are the domain of activated carbon, which nowadays is also addressed by studies on biochar. Thus, awareness of both fields of research and knowledge about the distinction of biochar and activated carbon is necessary for designing novel research on pyrogenic carbonaceous materials. Here, we describe the dividing ranges and common grounds of biochar, activated carbon and other pyrogenic carbonaceous materials such as charcoal based on their history, definition and production technologies. This review also summarizes thermochemical conversions and non-thermal pre- and post-treatments that are used to produce biochar and activated carbon. Our overview shows that biochar research should take advantage of the numerous techniques of activation and modification to tailor biochars for their intended applications.
Jafari, M., Desmond, P., van Loosdrecht, M. C. M., Derlon, N., Morgenroth, E., & Picioreanu, C. (2018). Effect of biofilm structural deformation on hydraulic resistance during ultrafiltration: A numerical and experimental study. Water Research, 145, 375-387. doi:10.1016/j.watres.2018.08.036, Institutional Repository

Biofilm formation in membrane systems negatively impacts the filtration system performances. This study evaluated how biofilm compression driven by permeate flow increases the hydraulic resistance and leads to reduction in permeate flux. We analysed the effect of biofilm compression on hydraulic resistance and permeate flux through computational models supported by experimental data. Biofilms with homogeneous surface structure were subjected to step-wise changes in flux and transmembrane pressure during compression and relaxation tests. Biofilm thickness under applied forces was measured non-invasively in-situ using optical coherence tomography (OCT). A numerical model of poroelasticity, which couples water flow through the biofilm with biofilm mechanics, was developed to correlate the structural deformation with biofilm hydraulics (permeability and resistance). The computational model enabled extracting mechanical and hydrological parameters corresponding to the experimental data. Homogeneous biofilms under elevated compression forces experienced a significant reduction in thickness while only a slight increase in resistance was observed. This shows that hydraulic resistance of homogeneous biofilms was affected more by permeability decrease due to pore closure than by a decrease in thickness. Both viscoelastic and elastoplastic models could describe well the permanent biofilm deformation. However, for biofilms under study, a simpler elastic model could also be used due to the small irreversible deformations. The elastic moduli fitting the measured data were in agreement with other reported values for biofilm under compression. Biofilm stiffening under larger flow-driven compression forces was observed and described numerically by correlating inversely the elastic modulus with biofilm porosity. The importance of this newly developed method lies in estimation of accurate biofilm mechanical parameters to be used in numerical models for both membrane filtration system and biofouling cleaning strategies. Such model can ultimately be used to identify optimal operating conditions for membrane system subjected to biofouling.
Kah, M., Kookana, R. S., Gogos, A., & Bucheli, T. D. (2018). A critical evaluation of nanopesticides and nanofertilizers against their conventional analogues. Nature Nanotechnology, 13(8), 677-684. doi:10.1038/s41565-018-0131-1, Institutional Repository

Among a wide range of possible applications of nanotechnology in agriculture, there has been a particular interest in developing novel nanoagrochemicals. While some concerns have been expressed regarding altered risk profile of the new products, many foresee a great potential to support the necessary increase in global food production in a sustainable way. A critical evaluation of nanoagrochemicals against conventional analogues is essential to assess the associated benefits and risks. In this assessment, recent literature was critically analysed to determine the extent to which nanoagrochemicals differ from conventional products. Our analysis was based on 78 published papers and shows that median gain in efficacy relative to conventional products is about 20–30%. Environmental fate of agrochemicals can be altered by nanoformulations, but changes may not necessarily translat controls. Currently, there is no comprehensive study in the literature that evaluates efficacy and environmental impact of nanoagrochemicals under field conditions. This is a crucial knowledge gap and more work will thus be necessary for a sound evaluation of the benefits and new risks that nanoagrochemicals represent relative to existing products.
Kampe, S., Kaegi, R., Schlich, K., Wasmuth, C., Hollert, H., & Schlechtriem, C. (2018). Silver nanoparticles in sewage sludge: bioavailability of sulfidized silver to the terrestrial isopod Porcellio scaber. Environmental Toxicology and Chemistry, 37(6), 1606-1613. doi:10.1002/etc.4102, Institutional Repository

Silver nanoparticles (AgNPs) are efficiently converted during the wastewater‐treatment process into sparingly soluble Ag sulfides (Ag2S). In several countries, sewage sludge is used as a fertilizer in agriculture. The bioavailability of sulfidized Ag to the terrestrial isopod Porcellio scaber was investigated. Sewage sludge containing transformed AgNPs was obtained from a laboratory‐scale sewage‐treatment plant operated according to Organisation for Economic Co‐operation and Development (OECD) guideline 303a. The results of transmission electron microscopy with energy dispersive X‐ray of sludge samples suggest that AgNPs were completely transformed to Ag2S. Adult isopods were exposed to OECD 207 soil substrate amended with the AgNP spiked sludge for 14 d (uptake phase) followed by an elimination phase in unspiked soil of equal duration. Most of the Ag measured in P. scaber at the end of the uptake phase was found in the hindgut (71%), indicating that only a minor part of the estimated Ag content was actually assimilated by the isopods with 16.3 and 12.7% found in the carcass and hepatopancreas, respectively. As a result of this, the Ag content of the animals dropped following transition to unspiked sludge within 2 d to one‐third of the previously measured Ag concentration and remained stable at this level until the end of the elimination period. The present study shows that Ag2S in sewage sludge is bioavailable to the terrestrial isopod P. scaber.
Kassotaki, E., Pijuan, M., Joss, A., Borrego, C. M., Rodriguez-Roda, I., & Buttiglieri, G. (2018). Unraveling the potential of a combined nitritation-anammox biomass towards the biodegradation of pharmaceutically active compounds. Science of the Total Environment, 624, 722-731. doi:10.1016/j.scitotenv.2017.12.116, Institutional Repository

In the past few years, anaerobic ammonium oxidation-based processes have attracted a lot of attention for their implementation at the mainstream line of wastewater treatment plants, due to the possibility of leading to energy autarky if combined with anaerobic digestion. However, little is known about the potential degradation of micropollutants by the microbial groups responsible of these processes and the few results available are inconclusive. This study aimed to assess the degradation capability of biomass withdrawn from a combined nitritation/anaerobic ammonium oxidation (combined N/A) pilot plant towards five pharmaceutically active compounds (ibuprofen, sulfamethoxazole, metoprolol, venlafaxine and carbamazepine). Batch experiments were performed under different conditions by selectively activating or inhibiting different microbial groups: i) regular combined N/A operation, ii) aerobic (optimal for nitrifying bacteria), iii) aerobic with allylthiourea (an inhibitor of ammonia monooxygenase, enzyme of ammonia oxidizing bacteria), iv) anoxic (optimal for anaerobic ammonium oxidizing bacteria), v) aerobic with acetate (optimal for heterotrophic bacteria) and vi) anoxic with acetate (optimal for heterotrophic denitrifying bacteria). Ibuprofen was the most biodegradable compound being significantly degraded (49–100%) under any condition except heterotrophic denitrification. Sulfamethoxazole, exhibited the highest removal (70%) under optimal conditions for nitrifying bacteria but in the rest of the experiments anoxic conditions were found to be slightly more favorable (up to 58%). For metoprolol the highest performance was obtained under anoxic conditions favoring anammox bacteria (62%). Finally, carbamazepine and venlafaxine were hardly removed (≤ 10% in the majority of cases). Taken together, these results suggest the specificity of different microbial groups that in combination with alternating operational parameters can lead to enhanced removal of some micropollutants.
Lindeboom, R. E. F., Ilgrande, C., Carvajal-Arroyo, J. M., Coninx, I., Van Hoey, O., Roume, H., … Vlaeminck, S. E. (2018). Nitrogen cycle microorganisms can be reactivated after Space exposure. Scientific Reports, 8(1), 13783 (7 pp.). doi:10.1038/s41598-018-32055-4, Institutional Repository

Long-term human Space missions depend on regenerative life support systems (RLSS) to produce food, water and oxygen from waste and metabolic products. Microbial biotechnology is efficient for nitrogen conversion, with nitrate or nitrogen gas as desirable products. A prerequisite to bioreactor operation in Space is the feasibility to reactivate cells exposed to microgravity and radiation. In this study, microorganisms capable of essential nitrogen cycle conversions were sent on a 44-days FOTON-M4 flight to Low Earth Orbit (LEO) and exposed to 10−3–10−4 g (gravitational constant) and 687 ± 170 µGy (Gray) d−1 (20 ± 4 °C), about the double of the radiation prevailing in the International Space Station (ISS). After return to Earth, axenic cultures, defined and reactor communities of ureolytic bacteria, ammonia oxidizing archaea and bacteria, nitrite oxidizing bacteria, denitrifiers and anammox bacteria could all be reactivated. Space exposure generally yielded similar or even higher nitrogen conversion rates as terrestrial preservation at a similar temperature, while terrestrial storage at 4 °C mostly resulted in the highest rates. Refrigerated Space exposure is proposed as a strategy to maximize the reactivation potential. For the first time, the combined potential of ureolysis, nitritation, nitratation, denitrification (nitrate reducing activity) and anammox is demonstrated as key enabler for resource recovery in human Space exploration.
Meyer, G., Frossard, E., Mäder, P., Nanzer, S., Randall, D. G., Udert, K. M., & Oberson, A. (2018). Water soluble phosphate fertilizers for crops grown in calcareous soils – an outdated paradigm for recycled phosphorus fertilizers?. Plant and Soil, 424(1-2), 367-388. doi:10.1007/s11104-017-3545-x, Institutional Repository

Background and aims The current paradigm for phosphorus (P) fertilizers applied to calcareous soil is that almost entirely water soluble P fertilizers are efficient and sparingly soluble P fertilizers are not efficient P sources for crops. We hypothesize that this paradigm does not apply to recycled P fertilizers and that other P pools can explain the plant use of recycled P fertilizers on calcareous soil.
Methods We applied 33P isotopic dilution method to evaluate recycled P fertilizers based on plant P uptake from fertilizer relative to plant uptake from a water soluble P reference fertilizer. The predictability of fertilizer effectiveness based on sequentially extracted P forms and X-ray diffraction pattern of recycled fertilizers derived from sewage sludge, human urine and organic waste was evaluated.
Results The plant experiments showed that tested recycled P fertilizers including compost were more effective than rock phosphate. The water insoluble P contained in urine based products was almost as effective as a fully water soluble P fertilizer. The tested recycled P fertilizers are characterized by complex P compounds differing in solubility which were so far not considered in the water and citric acid extraction methods. The fraction of resin- and NaHCO3 extractable fertilizer P explained effectiveness of P fertilizer applied to the calcareous and to an acidic soil.
Conclusion We concluded that water solubility is not required when P forms in recycled products are comparable to reactions products of rock phosphate based fertilizers in soil. Alternatives to fully water soluble P fertilizers are available to supply P to crops grown on calcareous soil efficiently.
Neidhardt, H., Winkel, L. H. E., Kaegi, R., Stengel, C., Trang, P. T. K., Lan, V. M., … Berg, M. (2018). Insights into arsenic retention dynamics of Pleistocene aquifer sediments by in situ sorption experiments. Water Research, 129, 123-132. doi:10.1016/j.watres.2017.11.018, Institutional Repository

The migration of arsenic (As) enriched groundwater into Pleistocene aquifers as a consequence of extensive groundwater abstraction represents an increasing threat to the precious water resources in Asian delta regions. Pleistocene aquifer sediments are typically rich in FeIII-(hydr)oxides and are capable to adsorb high amounts of As. This results in a pronounced accumulation of As in Pleistocene aquifers, where high As groundwater infiltrates from adjacent Holocene aquifers. However, As retention by Pleistocene aquifers over long-term time scales remains largely unknown. We studied As sorption in situ by placing natural Pleistocene sediments and pure mineral phases directly inside groundwater monitoring wells at a study site near Hanoi (Vietnam). This in situ exposure allows for constant flushing of the samples with unaltered groundwater and the establishment of undisturbed sorption equilibria similar to those in local aquifer sediments, which is not readily attainable in traditional laboratory sorption experiments. The groundwaters in our experimental wells were characterized by different As concentrations (0.01–6.63 μmol/L) and redox states, reaching from suboxic to anoxic conditions (Eh of +159 to −4 mV). Results show that adsorption is the dominant As retention mechanism, independent from the respective groundwater chemistry (i.e. concentrations of dissolved P, HCO3− and Si). Whilst most of the As sorbed within the first week, sorption further increased slowly but consistently by 6–189%, respectively, within six months. Hence, the As sorption behavior of Pleistocene aquifer sediments should be determined over longer periods to avoid an underestimation of the As sorption capacity. Accompanying desorption experiments revealed that about 51% of the sorbed As was remobilized within six months when exposed to low As groundwater. We therefore conclude that a considerable proportion of the As accumulated in the aquifer sediments is prone to remobilization once the As concentrations in migrating groundwater decline. Remobilization of As should be considered in local water management plans to avoid contamination of precious groundwater resources with this As legacy.
Nowack, B., & Mitrano, D. M. (2018). Procedures for the production and use of synthetically aged and product released nanomaterials for further environmental and ecotoxicity testing. NanoImpact, 10, 70-80. doi:10.1016/j.impact.2017.12.001, Institutional Repository

The use of pristine, as-produced engineered nanomaterials (ENMs) to examine environmental behavior or toxicity is convenient, but it is the aged or released ENMs that are much more likely to be present in the environment and these are the materials to which organisms will ultimately be exposed. When determining which aging processes are most relevant, a life cycle perspective can be useful to gain insight into how ENMs will be used, released from products and move through technical and environmental systems. While there are a few pristine nanomaterial standards or test materials available, procedures to create appropriate aged or released ENM standards for subsequent fate or effect studies are more rare. Whereas the aging and release processes of ENMs are studied to quite some extent, procedures for the production of these materials for further testing are still in the initial phases. Here we review the available aging and release procedures representing various stages of the product life cycle that were developed in order to collect the aged and released materials for further use. There are three main groups of aged/released materials: 1) laboratory aging of pristine ENM, 2) collection of ENMs released from nano-products, and 3) fragmentation of the product matrix combined with aging. Here, the various aging and release paradigms that may be followed are presented, each of which comes with pros and cons in terms of how close the aging parameters are to simulating real world situations and how applicable they are to different product matrices or release mechanisms. The further use of the aged/released materials in fate or effect studies is also presented when possible. We can conclude that some aging/release procedures exist which have applicability for different research questions and specific ENM/matrix/product combinations and life cycle stages, but additional research is warranted to expand the procedures for producing synthetically aged and product released ENMs to cover additional areas of interest.
Part, F., Berge, N., Baran, P., Stringfellow, A., Sun, W., Bartelt-Hunt, S., … Huber-Humer, M. (2018). A review of the fate of engineered nanomaterials in municipal solid waste streams. Waste Management, 75, 427-449. doi:10.1016/j.wasman.2018.02.012, Institutional Repository

Significant knowledge and data gaps associated with the fate of product-embedded engineered nanomaterials (ENMs) in waste management processes exist that limit our current ability to develop appropriate end-of-life management strategies. This review paper was developed as part of the activities of the IWWG ENMs in Waste Task Group. The specific objectives of this review paper are to assess the current knowledge associated with the fate of ENMs in commonly used waste management processes, including key processes and mechanisms associated with ENM fate and transport in each waste management process, and to use that information to identify the data gaps and research needs in this area. Literature associated with the fate of ENMs in wastes was reviewed and summarized. Overall, results from this literature review indicate a need for continued research in this area. No work has been conducted to quantify ENMs present in discarded materials and an understanding of ENM release from consumer products under conditions representative of those found in relevant waste management process is needed. Results also indicate that significant knowledge gaps associated with ENM behaviour exist for each waste management process investigated. There is a need for additional research investigating the fate of different types of ENMs at larger concentration ranges with different surface chemistries. Understanding how changes in treatment process operation may influence ENM fate is also needed. A series of specific research questions associated with the fate of ENMs during the management of ENM-containing wastes have been identified and used to direct future research in this area.
Pradas del Real, A. E., Castillo-Michel, H., Kaegi, R., Larue, C., de Nolf, W., Reyes-Herrera, J., … Sarret, G. (2018). Searching for relevant criteria to distinguish natural vs. anthropogenic TiO2 nanoparticles in soils. Environmental Science: Nano, 5(12), 2853-2863. doi:10.1039/c8en00386f, Institutional Repository

Nanosized TiO2 is one of the most produced nanomaterials. Agricultural soils are a major compartment of accumulation of TiO2-NPs after release from consumer products into the sewer system, due to the use of sewage sludge as a soil amendment. TiO2 is naturally present in soils, and distinguishing between anthropogenic and natural TiO2 in soils is thus important to assess the risks associated with the increased use of nano-TiO2. Methods to distinguish these materials in complex matrices such as soils are currently lacking. The purpose of this study was, therefore, to search for characteristic physical and chemical properties of natural and engineered nano-TiO2, based on a combination of bulk, micro and nanofocused X-ray fluorescence and X-ray absorption spectroscopy, transmission electron microscopy, X-ray diffraction and chemical analyses. Digested sewage sludge, agricultural soil and sludge-amended soil were studied by these techniques. The particle size distribution was not a relevant criterion since the sludge and the sludge-amended soil contained a variety of nanometer- and micrometer sized Ti-containing particles. Both the sludge and the soil contained a mixture of rutile and anatase, with a minor proportion of amorphous TiO2. In the sludge, there was no trend relating particle size and Ti mineralogy. The morphology of the TiO2 particles proved to be different in the two matrices, with smooth faceted particles in the sludge and rough irregular ones in the soil. In addition, natural TiO2 particles were included in micro and macroaggregates of the soil and formed intricate assemblages with minerals and organic compounds. In the sludge, TiO2 formed homo and heteroaggregates of simpler structure, richer in organic matter. Thus, the study of the morphology of TiO2 particles and their status in unperturbed mineral-organic assemblages may provide some insights into their origin. The observed differences may attenuate over time, due to the incorporation of the sludge material within the soil structure.
Rittmann, B. E., Boltz, J. P., Brockmann, D., Daigger, G. T., Morgenroth, E., Helleshøj Sørensen, K., … Vanrolleghem, P. A. (2018). A framework for good biofilm reactor modeling practice (GBRMP). Water Science and Technology, 77(5), 1149-1164. doi:10.2166/wst.2018.021, Institutional Repository

A researcher or practitioner can employ a biofilm model to gain insight into what controls the performance of a biofilm process and for optimizing its performance. While a wide range of biofilmmodeling platforms is available, a good strategy is to choose the simplest model that includes sufficient components and processes to address the modeling goal. In most cases, a onedimensional biofilm model provides the best balance, and good choices can range from handcalculation analytical solutions, simple spreadsheets, and numerical-method platforms. What is missing today is clear guidance on how to apply a biofilm model to obtain accurate and meaningful results. Here, we present a five-step framework for good biofilm reactor modeling practice (GBRMP). The first four steps are (1) obtain information on the biofilm reactor system, (2) characterize the influent, (3) choose the plant and biofilm model, and (4) define the conversion processes. Each step demands that the model user understands the important components and processes in the system, one of the main benefits of doing biofilm modeling. The fifth step is to calibrate and validate the model: System-specific model parameters are adjusted within reasonable ranges so that model outputs match actual system performance. Calibration is not a simple 'by the numbers' process, and it requires that the modeler follows a logical hierarchy of steps. Calibration requires that the adjusted parameters remain within realistic ranges and that the calibration process be carried out in an iterative manner. Once each of steps 1 through 5 is completed satisfactorily, the calibrated model can be used for its intended purpose, such as optimizing performance, trouble-shooting poor performance, or gaining deeper understanding of what controls process performance.
Senn, A. C., Hug, S. J., Kaegi, R., Hering, J. G., & Voegelin, A. (2018). Arsenate co-precipitation with Fe(II) oxidation products and retention or release during precipitate aging. Water Research, 131, 334-345. doi:10.1016/j.watres.2017.12.038, Institutional Repository

The co-precipitation of arsenate (As(V)) with Fe(III)-precipitates is of great importance in water treatment and critically affects the fate of As in environmental systems. We studied the effects of dissolved phosphate (P; 0-1 mM), silicate (Si; 0 or 0.5 mM) and Ca (0, 0.5 and 4 mM) on the sequestration of 7 μM As(V) by Fe(III)-precipitates formed by the oxidation of 0.5 mM Fe(II) in aerated bicarbonate-buffered solutions with an initial pH of 7.0 as well as the retention or release of As(V) after precipitate aging for 30 d at 40 °C. Dissolved As(V) concentrations in fresh precipitate suspensions greatly varied as a function of the initial dissolved P/Fe ratio ((P/Fe)init) and the concentrations of Ca and Si. Limited As(V) removal was observed at (P/Fe)init that exceeded the critical ratio (P/Fe)crit above which exclusively (Ca-)Fe(III)-phosphate forms. Effective As(V) removal was observed at (P/Fe)init < (P/Fe)crit, where initial formation of (Ca-)Fe(III)-phosphate is followed by the formation of Si-ferrihydrite in Si-containing electrolytes and of poorly-crystalline lepidocrocite and hydrous ferric oxide in the Si-free electrolytes. The retention of As(V) and P by fresh Fe(III)-precipitates was most effective in systems containing both Ca and Si. In the Si- and Ca-free electrolytes at (P/Fe)init of ~0.2–0.6, the rapid onset of precipitate aging with conversion of Fe(III)-phosphate to ferrihydrite resulted in a substantial remobilization of As(V) (up to 55% of initially precipitated As(V)). Ca reduced As remobilization during aging by stabilizing Ca-Fe(III)-phosphate and promoting Ca-phosphate formation, and Si by stabilizing Si-ferrihydrite against transformation. Consequently, also after aging, the lowest dissolved As(V) and P fractions were observed in precipitate suspensions containing both Ca and Si.
Szekeres, G. P., Németh, Z., Schrantz, K., Németh, K., Schabikowski, M., Traber, J., … Graule, T. (2018). Copper-coated cellulose-based water filters for virus retention. ACS Omega, 3(1), 446-454. doi:10.1021/acsomega.7b01496, Institutional Repository

Despite recent efforts in modernization of water treatment facilities, the problem of access to healthy drinking water for hundreds of millions of people has still not been solved. A water filter based on Cu-coated nanofibrillated cellulose with controlled porosity was prepared by the "paper-making" method. We have optimized the proper mass and ratio of functionalized and pure nanofibrillated cellulose for the preparation of the filter. MS2 bacteriophages were used to model human pathogenic virions. We tested our filter material in batch experiments and the fixed filters in flow experiments. The fabricated Cu-coated nanofibrillated cellulose filters were characterized by scanning electron microscopy, X-ray diffraction, specific surface area measurement (Brunauer–Emmett–Teller), dynamic light scattering, and inductively coupled plasma mass spectroscopy. Our measurements proved that the fixation of cellulose nanofibers plays a significant role in the degree of virus retention and it greatly enhances the efficiency of the filtration. By using these functionalized water filters, we were able to achieve a virus retention of at least 5 magnitudes (5Log) at three different pH values: 5.0, 7.5, and 9.
Tang, X., Ding, A., Pronk, W., Ziemba, C., Cheng, X., Wang, J., … Liang, H. (2018). Biological pre-treatments enhance gravity-driven membrane filtration for the decentralized water supply: linking extracellular polymeric substances formation to flux stabilization. Journal of Cleaner Production, 197(1), 721-731. doi:10.1016/j.jclepro.2018.06.155, Institutional Repository

Gravity-driven membrane (GDM) filtration is a promising technology for decentralized drinking water treatment due to its low energy requirements and simple operation. The reduced flux observed in GDM systems relative to other membrane treatment techniques remains a vital obstacle to their wider application. With the goal of further improving membrane flux and permeate quality, three simple and practical technologies have been examined as pre-treatments for GDM systems, (i) slow filtration with granular activated carbon (GAC), expected to remove both biodegradable and non-biodegradable contaminants, (ii) slow filtration with modified fiber ball (MFB), expected to promote biodegradation of organic compounds and (iii) microfiltration (MF), expected to reject suspended substances and particles. Results indicated that stable permeability increased by approximately 230%, 150% and 100% in GDM systems employing GAC, MFB and MF pre-treatments compared to the control. The dissolved organic compounds (DOC) were removed by approximately 60% and 30% in GAC/GDM and MFB/GDM, while MF/GDM and GDM control were not effective at DOC removal. Correlations between the stable flux and extracellular polymeric substances (EPS) concentration (R2 > 0.9) indicated that reduction of EPS should be responsible for the flux improvements. Tracing the fate of florescent foulants illustrated that the EPS was mainly secreted/converted by the microbes colonizing within the bio-fouling layer of the GDM system. During long-term filtration, assimilable organic compounds (AOC) which can serve as nutrients for the growth of microbes within the bio-fouling layer were efficiently consumed (>50%) by the biological pre-treatments. This reduction in AOC was linked with a reduction in the growth/activity of bacteria within the bio-fouling layer of GDM system and a reduction in EPS accumulation. Overall, biological pre-treatments can significantly enhance the flux and water quality produced by a GDM system without significantly increasing the operation and maintenance. These improvements in flux and water quality can hopefully spark wider adoption of GDM as an economical and environmentally-friendly technology for decentralized drinking water treatment.
Tang, X., Pronk, W., Ding, A., Cheng, X., Wang, J., Xie, B., … Liang, H. (2018). Coupling GAC to ultra-low-pressure filtration to modify the biofouling layer and bio-community: flux enhancement and water quality improvement. Chemical Engineering Journal, 333, 289-299. doi:10.1016/j.cej.2017.09.111, Institutional Repository

An integrated gravity-driven membrane (GDM) and granular activated carbon (GAC) filtration process was operated for 193 days to investigate the influence of integrated GAC on the flux stabilization, permeate quality, composition of the biofouling layer and eukaryotic community compared with a GDM control system. The results revealed that the presence of GAC resulted in a strongly increased stable flux (6 L m−2 h−1, compared to 2 L m−2 h−1 in the GDM control). Furthermore, the GAC/GDM system exhibited a significant removal of dissolved organic compounds (DOC) (50–70%) due to the adsorption and biodegradation process. By contrast, the DOC in the permeate of the control was approximately 20–30% higher than in the raw water, which was attributed to the hydrolysis of high-MW compounds. Furthermore, the composition of the biofouling layer attached on the membrane surface was significantly influenced by the presence of GAC, leading to a reduction of accumulated organic compounds by 60%. Likewise, the extracellular polymeric substances (EPS) were obviously reduced in the GAC/GDM system, especially the tightly bound EPS in the biofilm and EPS deposited in membrane pores. Additionally, the GAC could function as a eukaryotic pre-incubator, resulting in a higher diversity of the eukaryotic community and improving predation in the biofouling layer. Furthermore, a more porous, heterogeneous and permeable biofouling layer was observed in GAC/GDM. The higher flux in GAC/GDM system was attributed to (i) lower organic foulants (especially EPS) accumulated in the biofouling layer and membrane pores and (ii) highly heterogeneous structures due to improved activity of eukaryotes in the biofouling layer. These results are essential to develop robust maintenance-free, cost-effective and energy-efficient drinking water treatments.
Thalmann, B., von Gunten, U., & Kaegi, R. (2018). Ozonation of municipal wastewater effluent containing metal sulfides and metal complexes: kinetics and mechanisms. Water Research, 134, 170-180. doi:10.1016/j.watres.2018.01.042, Institutional Repository

Ozonation can be applied to mitigate the discharge of organic micropollutants from municipal wastewater treatment plants (WWTPs) to the aquatic environment. The toxicity of metals also present in WWTP effluents strongly depends on their speciation. Therefore, knowledge on the change of the metal speciation during ozonation of a WWTP effluent is essential to assess possible negative impacts. The kinetics and the stoichiometries of the reactions of ozone with three metal sulfides (ZnS, CuS and CdS) and metal-ethylenediaminetetraacetate (EDTA)/nitriloriacetic acid (NTA) complexes of Cu(II), Cd(II), Ni(II), Zn(II), Mg(II) and Pb(II) were investigated. With a stoichiometric factor of 2.6–3.9 moles of ozone per mole of sulfide and apparent second-order rate constants at pH 8 > 104 M−1 s−1, a complete oxidation of the sulfides and a concomitant release of the respective metals is expected during ozonation of a WWTP effluent for enhanced micropollutant abatement. The apparent second-order rate constants at pH 8 for the reactions of metal-EDTA complexes with ozone ranged from 42 M−1s−1 to 2.0 × 104 M−1s−1 and increased in the order Cd(II) < Cu(II) < Mg(II) < Ni(II) < Zn(II). Approximately 40% of Cd(II)-EDTA spiked to a WWTP effluent was oxidized at typical specific ozone doses of 0.5–0.7 gO3/gDOC. For the other metal-EDTA complexes a significantly higher fraction was oxidized. The bioavailable fraction determined by the diffusive-gradient thin films (DGT) method in the WWTP effluent increased during ozonation, due to the oxidative release of the metal ions. Algal toxicity (chlamynomodas reinhardtii) tests with CuS/CdS spiked WWTP effluent revealed a high tolerance toward Cu and Cd in the respective media. A toxic response was only observed at Cu concentrations above 10 μM, which is above typical WWTP effluent concentrations. Biological post-treatment after ozonation generally reduced the bioavailability of the metals, which resulted in a lower toxicity. Therefore, the biological post-treatment serves as an additional barrier to protect the downstream ecology of receiving waters.
Thürlimann, C. M., Dürrenmatt, D. J., & Villez, K. (2018). Soft-sensing with qualitative trend analysis for wastewater treatment plant control. Control Engineering Practice, 70, 121-133. doi:10.1016/j.conengprac.2017.09.015, Institutional Repository

Ammonia control in municipal wastewater treatment plants typically requires maintenance-intensive instrumentation. A low maintenance alternative is sought for small- to medium-scale applications. To this end, a pH-based soft-sensor is proposed to detect ammonia peak load events. This soft-sensor is based on a newly developed technique for qualitative trend analysis and is combined with a rule-based controller. The use of qualitative trend analysis makes this soft-sensor tolerant towards sensor drifts and thereby reduces the maintenance effort. The method allows controlling any process in which relative changes in the measured output are informative about the system output.
Ulmer, P., Kaegi, R., & Müntener, O. (2018). Experimentally derived intermediate to silica-rich arc magmas by fractional and equilibrium crystallization at 1·0 GPa: an evaluation of phase relationships, compositions, liquid lines of descent and oxygen fugacity. Journal of Petrology, 59(1), 11-58. doi:10.1093/petrology/egy017, Institutional Repository

Differentiation of hydrous primary, mantle-derived magmas is a fundamental process to generate evolved intermediate to SiO2-rich compositions forming the bulk of the continental and island arc crust. This study focuses on the results of equilibrium and fractional crystallization experiments at 1·0 GPa using two different primary magmas representing deep (90 km) and shallow (35 km) mantle extraction depths. Experiments on a hydrous high-Mg basalt were conducted at graphite-saturated and more oxidized conditions (NNO to NNO + 2, where NNO is nickel–nickel oxide buffer) to exploit the influence of fO2 on phase assemblages and the evolution of derivative liquids. The liquid line of descent (LLD) was simulated from liquidus to near-solidus conditions ranging from 1330°C to 720°C. H2O contents varied from about 2·0 to more than 10 wt %. The LLD covers the entire compositional range from high-Mg basalt to high-silica rhyolite and evolves from metaluminous to peraluminous compositions at 56–60 wt % SiO2 under oxidizing conditions. The observed crystallization sequences and the LLD reveal contrasting behavior depending on oxidation state, H2O content and equilibrium versus fractional crystallization. Equilibrium crystallization of high-Mg basalt under reducing conditions is initially dominated by olivine fractionation followed by Cr-rich spinel, clinopyroxene (cpx), and orthopyroxene (opx). Finally, between 1060 and 1000°C, amphibole formed by a peritectic reaction consuming cpx + olivine and forming amphibole + opx, resulting in 16% silica-undersaturated trachy-basaltic liquid. Equilibrium crystallization of the same composition under oxidizing conditions is characterized by strongly enhanced olivine and cpx fractionation and suppression of opx only occurring as a result of the peritectic amphibole-forming reaction at and below 1040°C. The liquid at 980°C is a peraluminous, alkali-poor, high-Al andesite representing ∼15% residual liquid. Fractional crystallization of the high-Mg basalt under oxidizing conditions evolves through fractionation of early olivine joined by cpx at 1200°C, followed by opx and hercynitic spinel (1140–1080°C) and amphibole at 1050°C coexisting with cpx (and spinel) to 980°C. At 950°C both garnet and plagioclase (plag) join amphibole as liquidus phases. This paragenesis (plus ilmenite and apatite) persists to 750°C with 16% residual liquid relative to the initial basaltic composition. Liquids evolve continuously from basalt to rhyolite, crossing the metaluminous–peraluminous boundary at about 60 wt % SiO2. Fractional crystallization of the basaltic andesite starting material differs at high temperature, where opx and cpx are the liquidus phases (1200–1080°C), followed by amphibole at the expense of opx. Below 950°C the phase assemblage is identical except at the lowest temperature (720°C), where quartz saturates in a high-silica rhyolitic liquid representing 20% of the initial basaltic andesite. Liquid compositions of the two starting compositions converge below 950°C, with the exception of K2O, which behaves incompatibly along the liquid line of descent. The H2O-undersaturated fractional crystallization experiments on the high-Mg basaltic composition under relatively reducing conditions evolve towards tholeiitic or alkalic compositions owing to early plagioclase (at 1140°C) and abundant opx (at 1110°C) crystallization followed by garnet–cpx–plag–ilmenite at 1080°C. Closed-system equilibrium crystallization under relatively oxidized conditions is characterized by significant expansion of the olivine stability field (>250°C, 1280–1000°C) relative to more reducing conditions, causing depletion of the liquid in ferrous iron and increase of ferric iron. The resulting fO2 of the coexisting basaltic liquids increases by more than 3 log units from about NNO + 2 to NNO + 5·5 over the temperature range >1200–1040°C, potentially offering an explanation for the more oxidized character of hydrous arc magmas as opposed to low-H2O tholeiitic magmas.
Wielinski, J., Müller, C., Voegelin, A., Morgenroth, E., & Kaegi, R. (2018). Combustion of sewage sludge: kinetics and speciation of the combustible. Energy and Fuels, 32(10), 10656-10667. doi:10.1021/acs.energyfuels.8b02106, Institutional Repository

Combustion of sewage sludge has become a viable route for sewage sludge management especially as the agricultural use of sewage sludge has become increasingly difficult due to more stringent requirements regarding the quality of sewage sludge. Combustion of digested sewage sludge in dedicated monocombustion facilities is advantageous, as it substantially reduces the volume of the sludge and still allows for a recovery of phosphorus from the sewage sludge ash at a later stage. Despite increasing amounts of sewage sludge being combusted, knowledge on the respective combustion kinetics is still fragmentary. The goal of this study was, therefore, to identify the major combustion reactions of sewage sludge, assess their Arrhenius parameters (activation energy and pre-exponential factor), and assign suitable reference compounds to the individual reactions. For that purpose, experiments were conducted using a thermogravimetric analyzer (TGA). With matrix inversion, we identified 10 individual reactions. Despite the apparent kinetic compensation most likely caused by insufficient precision of the TGA temperature setting, we were able to relate the major reactions of sewage sludge combustion to the combustion of individual reference compounds. In addition to cellulose and lignin, which dominated the weight loss with 35% and 20%, respectively, hemicellulose, xylan, alginate, and calcite were identified. The dominant fraction of cellulose is consistent with recent studies identifying cellulose mainly originating from toilet paper as a major organic constituent in wastewater. As the identified model compounds explain more than 80% of the total weight loss observed, our approach allows a rough speciation of the combustibles of sewage sludge based on TGA experiments.
Ziemba, C., Larivé, O., Reynaert, E., & Morgenroth, E. (2018). Chemical composition, nutrient-balancing and biological treatment of hand washing greywater. Water Research, 144, 752-762. doi:10.1016/j.watres.2018.07.005, Institutional Repository

On-site biological hand washing water treatment can improve global access to safe hand washing water, but requires a thorough understanding of the chemical composition of the water to be treated, and an effective treatment strategy. This study first presents a detailed characterization of the individual inputs to hand washing water. We demonstrate (1) that soap is likely the most significant input in hand washing water, representing ∼90% of mass loading, and (2) that inputs to hand washing water have low concentrations of biologically-essential macro- and micro-nutrients (nitrogen, phosphorus, potassium, copper, zinc, molybdenum and cobalt) with respect to carbon, which may impair biological carbon removal. This study next formulates a recipe that recreates a representative composition of hand washing water and develops a procedure to identify and supplement nutrients in which this recipe is estimated to be deficient. Batch testing of the nutrient-supplemented hand washing water with an inoculum of planktonic bacteria demonstrated improved assimilable organic carbon removal (99% vs. 86% removal) and produced lower final DOC concentrations (1.7 mgC/L vs. 3.5 mgC/L) compared to realistic (nutrient-deficient) washing water. Supplementing nutrients did promote cell growth (50x higher final total cell count). Full-scale testing in a biologically activated membrane bioreactor (BAMBi) system treating 75 L/day of nutrient-supplemented hand washing water showed that long-term operation (100 days) can deliver effective carbon removal (95%) without detrimental fouling or other disruptions caused by cell growth. This work demonstrates that biological treatment in a BAMBi system, operated with appropriate nutrient-balancing offers an effective solution for decentralized treatment of light greywater.
Altun, A. O., Bond, T., Pronk, W., & Park, H. G. (2017). Sensitive detection of competitive molecular adsorption by surface-enhanced raman spectroscopy. Langmuir, 33(28), 6999-7006. doi:10.1021/acs.langmuir.7b01186, Institutional Repository

Surface adsorption plays a critical role in a wide variety of fields from surface catalysis to molecular separation. Despite the importance, limited access to simultaneously sensitive and selective detection mechanisms has hampered the acquisition of comprehensive and versatile experimental data needed to understand the complex aspects of mixture adsorption, calling for a molecular detection method capable of obtaining the surface adsorption isotherms over a wide range of concentrations as well as distinguishing the competitive adsorption of different adsorbates. Here, we test surface-enhanced Raman spectroscopy (SERS) as an effective analysis tool of surface adsorption phenomena. Using a sensitive SERS substrate, we characterize the adsorption isotherms of chemical species of various binding energies. We obtained the isotherms for strongly binding species in a concentration range from subpicomolar to micromolar. A log-sigmoidal dependency of the SERS signals to the analyte concentration could be modeled by surface binding theories accurately using molecular dynamics simulations, thereby bringing out the potential capability of sensitive SERS for describing a single-compound adsorption process. SERS also enabled the determination of competitive adsorption isotherms from a multiple-compound solution for the first time. The successful demonstration of the sensitive and selective characterization of surface adsorption lends SERS adaptability to a cheap, facile, and effective solution for chemical analysis.
Auvinen, H., Kaegi, R., Rousseau, D. P. L., & Du Laing, G. (2017). Fate of Silver Nanoparticles in Constructed Wetlands - a Microcosm Study. Water, Air, and Soil Pollution, 228(3) (11 pp.). doi:10.1007/s11270-017-3285-9, Institutional Repository

Nano-enabled materials are produced at growing volumes which increases the likelihood of nanoparticles being released into the environment. Constructed wetlands (CWs) are likely to receive wastewater containing nanoparticles leaching from products during usage. Therefore, we investigate the retention of silver nanoparticles (Ag-NPs) in microcosms simulating CWs treating domestic wastewater. The effects of aeration and organic matter content on the Ag-NP removal efficiencies are studied in particular. CWs remove most of the Ag (80-90%) and the largest fraction of Ag is found in/on the biofilm. Detailed electron microscopy analyses suggest that Ag-NPs are transformed into Ag2S in all microcosm experiments. The good correlation between total suspended solids (TSS) and the Ag concentration measured in the effluent indicates that Ag-NPs are bound to the solids in the effluent. Aeration of the microcosms does not affect the release of Ag-NPs from the systems but increasing organic matter leads to increased amounts of Ag passing the CWs, correlating with the increased release of TSS from the CWs. These results suggest that Ag-NPs are retained with the (suspended) solids in CWs and that the removal efficiency of TSS is an important factor determining the discharge of Ag-NPs from CWs.
Benstoem, F., Nahrstedt, A., Boehler, M., Knopp, G., Montag, D., Siegrist, H., & Pinnekamp, J. (2017). Performance of granular activated carbon to remove micropollutants from municipal wastewater - a meta-analysis of pilot- and large-scale studies. Chemosphere, 185, 105-118. doi:10.1016/j.chemosphere.2017.06.118, Institutional Repository

For reducing organic micropollutants (MP) in municipal wastewater effluents, granular activated carbon (GAC) has been tested in various studies. We did systematic literature research and found 44 studies dealing with the adsorption of MPs (carbamazepine, diclofenac, sulfamethoxazole) from municipal wastewater on GAC in pilot- and large-scale plants. Within our meta-analysis we plot the bed volumes (BV [m3 water/m3 GAC]) until the breakthrough criterion of MP-BV20% was reached, dependent on potential relevant parameters (empty bed contact time EBCT, influent DOC DOC0 and manufacturing method). Moreover, we performed statistical tests (ANOVAs) to check the results for significance. Single adsorbers operating time differs i.e. by 2500% until breakthrough of diclofenac-BV20% was reached (800-20,000 BV). There was still elimination of the “very well/well” adsorbable MPs such as carbamazepine and diclofenac even when the equilibrium of DOC had already been reached. No strong statistical significance of EBCT and DOC0 on MP-BV20% could be found due to lack of data and the high heterogeneity of the studies using GAC of different qualities. In further studies, adsorbers should be operated[20,000 BV for exact calculation of breakthrough curves, and the following parameters should be recorded: selected MPs; DOC0; UVA254; EBCT; product name, manufacturing method and raw material of GAC; suspended solids (TSS); backwash interval; backwash program and pressure drop within adsorber. Based on our investigations we generally recommend using reactivated GAC to reduce the environmental impact and to carry out tests on pilot scale to collect reliable data for process design.
Boltz, J. P., Johnson, B. R., Takács, I., Daigger, G. T., Morgenroth, E., Brockmann, D., … Derlon, N. (2017). Biofilm carrier migration model describes reactor performance. Water Science and Technology, 75(12), 2818-2828. doi:10.2166/wst.2017.160, Institutional Repository

The accuracy of a biofilm reactor model depends on the extent to which physical system conditions (particularly bulk-liquid hydrodynamics and their influence on biofilm dynamics) deviate from the ideal conditions upon which the model is based. It follows that an improved capacity to model a biofilm reactor does not necessarily rely on an improved biofilm model, but does rely on an improved mathematical description of the biofilm reactor and its components. Existing biofilm reactor models typically include a one-dimensional biofilm model, a process (biokinetic and stoichiometric) model, and a continuous flow stirred tank reactor (CFSTR) mass balance that [when organizing CFSTRs in series] creates a pseudo two-dimensional (2-D) model of bulk-liquid hydrodynamics approaching plug flow. In such a biofilm reactor model, the user-defined biofilm area is specified for each CFSTR; thereby, Xcarrier does not exit the boundaries of the CFSTR to which they are assigned or exchange boundaries with other CFSTRs in the series. The error introduced by this pseudo 2-D biofilm reactor modeling approach may adversely affect model results and limit model-user capacity to accurately calibrate a model. This paper presents a new sub-model that describes the migration of Xcarrier and associated biofilms, and evaluates the impact that Xcarrier migration and axial dispersion has on simulated system performance. Relevance of the new biofilm reactor model to engineering situations is discussed by applying it to known biofilm reactor types and operational conditions.
Boltz, J. P., Smets, B. F., Rittmann, B. E., Van Loosdrecht, M. C. M., Morgenroth, E., & Daigger, G. T. (2017). From biofilm ecology to reactors: a focused review. Water Science and Technology, 75(8), 1753-1760. doi:10.2166/wst.2017.061, Institutional Repository

Biofilms are complex biostructures that appear on all surfaces that are regularly in contact with water. They are structurally complex, dynamic systems with attributes of primordial multicellular organisms and multifaceted ecosystems. The presence of biofilms may have a negative impact on the performance of various systems, but they can also be used beneficially for the treatment of water (defined herein as potable water, municipal and industrial wastewater, fresh/brackish/salt water bodies, groundwater) as well as in water stream-based biological resource recovery systems. This review addresses the following three topics: (1) biofilm ecology, (2) biofilm reactor technology and design, and (3) biofilm modeling. In so doing, it addresses the processes occurring in the biofilm, and how these affect and are affected by the broader biofilm system. The symphonic application of a suite of biological methods has led to significant advances in the understanding of biofilm ecology. New metabolic pathways, such as anaerobic ammonium oxidation (anammox) or complete ammonium oxidation (comammox) were first observed in biofilm reactors. The functions, properties, and constituents of the biofilm extracellular polymeric substance matrix are somewhat known, but their exact composition and role in the microbial conversion kinetics and biochemical transformations are still to be resolved. Biofilm grown microorganisms may contribute to increased metabolism of micro-pollutants. Several types of biofilm reactors have been used for water treatment, with current focus on moving bed biofilm reactors, integrated fixed-film activated sludge, membrane-supported biofilm reactors, and granular sludge processes. The control and/or beneficial use of biofilms in membrane processes is advancing. Biofilm models have become essential tools for fundamental biofilm research and biofilm reactor engineering and design. At the same time, the divergence between biofilm modeling and biofilm reactor modeling approaches is recognized.
Carr, G., Blanch, A. R., Blaschke, A. P., Brouwer, R., Bucher, C., Farnleitner, A. H., … Blöschl, G. (2017). Emerging outcomes from a cross-disciplinary doctoral programme on water resource systems. Water Policy, 19(3), 463-478. doi:10.2166/wp.2017.054, Institutional Repository

Interdisciplinary research and education programmes in water science are intended to produce groundbreaking research, often with an emphasis on societal relevance, and prepare future water resource experts to work across disciplines. This paper explores the emerging outcomes from an ongoing doctoral programme currently in its seventh year. Within the programme, there is both cross-disciplinary and mono-disciplinary research. Three questions are explored: (i) whether cross-disciplinary research leads to more innovative scientific findings than monodisciplinary research, (ii) whether cross-disciplinary researchers develop professional skills that benefit their future careers, and (iii) whether cross-disciplinary research produces findings of greater societal relevance than monodisciplinary research. Various indicators are used to measure research and education outcomes. Analysis of journal impact factors and citation rates of Institute of Scientific Information indexed publications suggests that crossdisciplinary research findings are more innovative. Comparison between graduate research profile and their career destinations suggests that researchers who learn to work across the disciplines continue to work this way in their post-doctoral positions. Analysis of media interest in research findings or their impact on policy suggests that both types of research are of societal value, but researchers often expand their understanding of a societal interest topic by bringing in new research fields.
Carrel, M., Beltran, M. A., Morales, V. L., Derlon, N., Morgenroth, E., Kaufmann, R., & Holzner, M. (2017). Biofilm imaging in porous media by laboratory X-ray tomography: combining a non-destructive contrast agent with propagation-based phase-contrast imaging tools. PLoS One, 12(7), e0180374 (18 pp.). doi:10.1371/journal.pone.0180374, Institutional Repository

X-ray tomography is a powerful tool giving access to the morphology of biofilms, in 3D porous media, at the mesoscale. Due to the high water content of biofilms, the attenuation coefficient of biofilms and water are very close, hindering the distinction between biofilms and water without the use of contrast agents. Until now, the use of contrast agents such as barium sulfate, silver-coated micro-particles or 1-chloronaphtalene added to the liquid phase allowed imaging the biofilm 3D morphology. However, these contrast agents are not passive and potentially interact with the biofilm when injected into the sample. Here, we use a natural inorganic compound, namely iron sulfate, as a contrast agent progressively bounded in dilute or colloidal form into the EPS matrix during biofilm growth. By combining a very long source-to-detector distance on a X-ray laboratory source with a Lorentzian filter implemented prior to tomographic reconstruction, we substantially increase the contrast between the biofilm and the surrounding liquid, which allows revealing the 3D biofilm morphology. A comparison of this new method with the method proposed by Davit et al (Davit et al., 2011), which uses barium sulfate as a contrast agent to mark the liquid phase was performed. Quantitative evaluations between the methods revealed substantial differences for the volumetric fractions obtained from both methods. Namely, contrast agent—biofilm interactions (e.g. biofilm detachment) occurring during barium sulfate injection caused a reduction of the biofilm volumetric fraction of more than 50% and displacement of biofilm patches elsewhere in the column. Two key advantages of the newly proposed method are that passive addition of iron sulfate maintains the integrity of the biofilm prior to imaging, and that the biofilm itself is marked by the contrast agent, rather than the liquid phase as in other available methods. The iron sulfate method presented can be applied to understand biofilm development and bioclogging mechanisms in porous materials and the obtained biofilm morphology could be an ideal basis for 3D numerical calculations of hydrodynamic conditions to investigate biofilm-flow coupling.
Derlon, N., Thürlimann, C., Dürrenmatt, D., & Villez, K. (2017). Batch settling curve registration via image data modeling. Water Research, 114, 327-337. doi:10.1016/j.watres.2017.01.049, Institutional Repository

To this day, obtaining reliable characterization of sludge settling properties remains a challenging and time-consuming task. Without such assessments however, optimal design and operation of secondary settling tanks is challenging and conservative approaches will remain necessary. With this study, we show that automated sludge blanket height registration and zone settling velocity estimation is possible thanks to analysis of images taken during batch settling experiments. The experimental setup is particularly interesting for practical applications as it consists of off-the-shelf components only, no moving parts are required, and the software is released publicly. Furthermore, the proposed multivariate shape constrained spline model for image analysis appears to be a promising method for reliable sludge blanket height profile registration.
Ding, A., Liang, H., Li, G., Szivak, I., Traber, J., & Pronk, W. (2017). A low energy gravity-driven membrane bioreactor system for grey water treatment: permeability and removal performance of organics. Journal of Membrane Science, 542, 408-417. doi:10.1016/j.memsci.2017.08.037, Institutional Repository

Synthetic grey water was treated with a low-pressure gravity-driven membrane bioreactor (GDMBR) system. The system was operated without any direct shear at the membrane surface and without any cleaning or flushing. In order to reduce energy consumption, one reactor was operated without aeration and the results were compared with an aerated reactor. Although the dissolved oxygen content was low (0.4–0.6 mg/L) in the non-aerated system, a stable permeability was observed at a level of around 20 L/m2 h bar (flux of 1 L/m2 h). The fouling resistance was dominated by the bio-fouling layer, which could be removed hydraulically. In comparison to the aerated system, the bio-fouling layer grown without aeration exhibited a lower biological activity, was thicker and had a lower surface roughness. Furthermore, the stable permeability of the aerated system was higher (40 L/m2 h bar), which could be explained by a lower content and load of extracellular polymeric substances (including extracellular polysaccharides and proteins). In comparison to filtration through a non-fouled membrane, the rejection of biopolymers and humic substances was strongly enhanced, which shows that the bio-fouling layer acts as a secondary membrane. The energy consumption was 0.02–0.04 kWh/m3, which is substantially less than for normal MBRs, and even less than for the traditional activated sludge process. These results show that grey water can be treated in a membrane reactor without any cleaning and flushing and even without any aeration, which makes the process suitable for decentralized wastewater treatment and considerably reduces the energy consumption.
Fumasoli, A., Bürgmann, H., Weissbrodt, D. G., Wells, G. F., Beck, K., Mohn, J., … Udert, K. M. (2017). Growth of Nitrosococcus-related ammonia oxidizing bacteria coincides with extremely low pH values in wastewater with high ammonia content. Environmental Science and Technology, 51(12), 6857-6866. doi:10.1021/acs.est.7b00392, Institutional Repository

Ammonia oxidation decreases the pH in wastewaters where alkalinity is limited relative to total ammonia. The activity of ammonia oxidizing bacteria (AOB), however, typically decreases with pH and often ceases completely in slightly acidic wastewaters. Nevertheless, nitrification at low pH has been reported in reactors treating human urine, but it has been unclear which organisms are involved. In this study, we followed the population dynamics of ammonia oxidizing organisms and reactor performance in synthetic fully hydrolyzed urine as the pH decreased over time in response to a decrease in the loading rate. Populations of the β-proteobacterial Nitrosomonas europaea lineage were abundant at the initial pH close to 6, but the growth of a possibly novel Nitrosococcus-related AOB genus decreased the pH to the new level of 2.2, challenging the perception that nitrification is inhibited entirely at low pH values, or governed exclusively by β-proteobacterial AOB or archaea. With the pH shift, nitrite oxidizing bacteria were not further detected, but nitrous acid (HNO2) was still removed through chemical decomposition to nitric oxide (NO) and nitrate. The growth of acid-tolerant γ-proteobacterial AOB should be prevented, by keeping the pH above 5.4, which is a typical pH limit for the N. europaea lineage. Otherwise, the microbial community responsible for high-rate nitrification can be lost, and strong emissions of hazardous volatile nitrogen compounds such as NO are likely.
Gogos, A., Thalmann, B., Voegelin, A., & Kaegi, R. (2017). Sulfidation kinetics of copper oxide nanoparticles. Environmental Science: Nano, 4(8), 1733-1741. doi:10.1039/C7EN00309A, Institutional Repository

Sulfidation of copper oxide nanoparticles (CuO NPs) in urban wastewater systems is expected to influence their impact on the environment. However, the kinetics of this reaction has not been studied to date and the reaction mechanism remains largely unexplored. We therefore investigated the sulfidation kinetics of CuO NPs reacted with bisulfide (HS−) at concentrations relevant to wastewater systems. Pristine CuO NPs (50 nm, 7.7 μM) were reacted with HS− (26.4–105.6 μM) in oxic solutions buffered to pH 8.0. The reaction progress was monitored using silver nitrate to quench the reaction and selectively dissolve the copper sulfides (Cux) and zincon to spectrophotometrically quantify the released Cu2+. In addition, the reaction products were characterized at selected time points using analytical electron microscopy and X-ray absorption spectroscopy (XAS). The sulfidation rate of the CuO NPs was best described by a pseudo first order rate law and the corresponding half-life times ranged between 1 and 6 minutes. XAS results showed that crystalline CuO NPs rapidly transformed into amorphous CuxS and gradually into crystalline CuS (covellite). The comparable size of pristine and transformed primary particles, the similar morphology of their aggregates, and the initial formation of CuO–CuxS core–shell structures revealed by analytical electron microscopy suggest that the initial sulfidation occurred via a direct conversion reaction mechanism. Our findings suggest that CuO NPs released from various sources into wastewater will rapidly transform into amorphous CuxS and eventually recrystallize into covellite.
Hernandez, E., Nowack, B., & Mitrano, D. M. (2017). Polyester textiles as a source of microplastics from households: a mechanistic study to understand microfiber release during washing. Environmental Science and Technology, 51(12), 7036-7046. doi:10.1021/acs.est.7b01750, Institutional Repository

Microplastic fibers make up a large proportion of microplastics found in the environment, especially in urban areas. There is good reason to consider synthetic textiles a major source of microplastic fibers, and it will not diminish since the use of synthetic fabrics, especially polyester, continues to increase. In this study we provide quantitative data regarding the size and mass of microplastic fibers released from synthetic (polyester) textiles during simulated home washing under controlled laboratory conditions. Consideration of fabric structure and washing conditions (use of detergents, temperature, wash duration, and sequential washings) allowed us to study the propensity of fiber shedding in a mechanistic way. Thousands of individual fibers were measured (number, length) from each wash solution to provide a robust data set on which to draw conclusions. Among all the variables tested, the use of detergent appeared to affect the total mass of fibers released the most, yet the detergent composition (liquid or powder) or overdosing of detergent did not significantly influence microplastic release. Despite different release quantities due to the addition of a surfactant (approximately 0.025 and 0.1 mg fibers/g textile washed, without and with detergent, respectively), the overall microplastic fiber length profile remained similar regardless of wash condition or fabric structure, with the vast majority of fibers ranging between 100 and 800 μm in length irrespective of wash cycle number. This indicates that the fiber staple length and/or debris encapsulated inside the fabric from the yarn spinning could be directly responsible for releasing stray fibers. This study serves as a first look toward understanding the physical properties of the textile itself to better understand the mechanisms of fiber shedding in the context of microplastic fiber release into laundry wash water.
Jacquin, C., Lesage, G., Traber, J., Pronk, W., & Heran, M. (2017). Three-dimensional excitation and emission matrix fluorescence (3DEEM) for quick and pseudo-quantitative determination of protein- and humic-like substances in full-scale membrane bioreactor (MBR). Water Research, 118, 82-92. doi:10.1016/j.watres.2017.04.009, Institutional Repository

The goal of this study is to help filling the research gaps linked to the on-line application of fluorescence spectroscopy in wastewater treatment and data processing tools suitable for rapid correction and extraction of data contained in three-dimensional fluorescence excitation-emission matrix (3DEEM) for real-time studies. 3DEEM was evaluated for direct quantification of Effluent Organic Matter (EfOM) fractions in full-scale MBR bulk supernatant and permeate samples. Principal Component Analysis (PCA) was used to investigate possible correlations between conventional Lowry and Dubois methods, Liquid Chromatography coupled to Organic Carbon and Organic Nitrogen Detection (LC-OCD-OND) and 3DEEM. 3DEEM data were analyzed using the volume of fluorescence (Φ) parameter from the Fluorescence Regional Integration (FRI) method. Two mathematical correlations were established between LC-OCD-OND and 3DEEM data to quantify protein-like and humic-like substances. These correlations were validated with supplementary data from the initial full-scale MBR, and were checked with samples from other systems (a second full-scale MBR, a full-scale conventional activated sludge (CAS) and a laboratory-scale MBR). While humic-like correlation showed satisfactory prediction for a second full-scale MBR and a CAS system, further studies are required for protein-like estimation in other systems. This new approach offers interesting perspectives for the on-line application of 3DEEM for EfOM quantification (protein-like and humic-like substances), fouling prediction and MBR process control.
Kaegi, R., Englert, A., Gondikas, A., Sinnet, B., von der Kammer, F., & Burkhardt, M. (2017). Release of TiO2 – (nano) particles from construction and demolition landfills. NanoImpact, 8, 73-79. doi:10.1016/j.impact.2017.07.004, Institutional Repository

A large fraction of engineered nanomaterials (ENM) will be deposited in landfills and it is assumed that ENM are securely locked in landfill sites and cannot leach into the environment (e.g. surface waters). However, experimental evidence supporting this assumption is lacking, as current production volumes of ENM are still too small and/or analytical techniques not sensitive enough to allow for the detection and quantification of ENM in landfill leachates. TiO2 particles are currently used in large quantities, for example in construction materials such as paints and renders as white pigments and their sizes extend into the nano-size range. We, therefore, selected TiO2 particles as a surrogate to assess the potential release of ENM from construction and demolition (C & D) landfill sites. We collected leachate samples from a landfill over one year and used complementary analytical techniques, including inductively coupled plasma (ICP) – optical emission spectroscopy (OES), automated scanning electron microscopy (auto SEM), transmission electron microscopy (TEM) and single particle ICP - mass spectrometry (spICPMS) to quantify TiO2 particles in landfill leachates. Total elemental Ti contents were mostly around a few tens of μg L− 1 and were strongly correlated with total suspended solids. Based on the volumetric discharge of the landfill leachate water from the landfill, we estimate a total amount of ~ 0.5 kg of TiO2 particles that are released annually from the landfill. Ti concentrations derived from ICP-OES measurements were in good agreement with quantifications based on TiO2 particles detected by auto SEM analyses. spICPMS measurements indicated a number concentration of Ti-containing particles in the order of 105 mL− 1 and TEM analyses dominantly revealed nanoscale TiO2 particles with a spherical shape typically observed for TiO2 particles used as white pigments. In addition, angular TiO2 particles with a well-defined crystal habitus were detected, suggesting that also natural TiO2 particles of comparable sizes are present in the landfill leachates. The results from this study indicate that (nanoscale) TiO2 particles are released from C & D landfill sites (~ 5 g/year). Although the amount of TiO2 particles released from C & D landfill sites may still be rather low, these particles may serve as proxy for assessing the future release of ENM from C & D landfill sites, which may become relevant as an increasing use of ENM is predicted for construction materials in general.
Kraas, M., Schlich, K., Knopf, B., Wege, F., Kägi, R., Terytze, K., & Hund-Rinke, K. (2017). Long-term effects of sulfidized silver nanoparticles in sewage sludge on soil microflora. Environmental Toxicology and Chemistry, 36(12), 3305-3313. doi:10.1002/etc.3904, Institutional Repository

The use of silver nanoparticles (AgNPs) in consumer products such as textiles leads to their discharge into wastewater and consequently to a transfer of the AgNPs to soil ecosystems via biosolids used as fertilizer. In urban wastewater systems (e.g., sewer,wastewater treatment plant [WWTP], anaerobic digesters) AgNPs are efficiently converted into sparingly soluble silver sulfides (Ag2S), mitigating the toxicity of the AgNPs. However, long-termstudies on the bioavailability and effects of sulfidized AgNPs on soilmicroorganisms are lacking. Thus we investigated the bioavailability and long-term effects of AgNPs (spiked in a laboratory WWTP) on soil microorganisms. Before mixing the biosolids into soil, the sludges were either anaerobically digested or directly dewatered. The effects on the ammonium oxidation process were investigated over 140 d. Transmission electron microscopy (TEM) suggested an almost complete sulfidation of the AgNPs analyzed in all biosolid samples and in soil, with Ag2S predominantly detected in long-term incubation experiments. However, despite the sulfidation of the AgNPs, soil ammonium oxidation was significantly inhibited, and the degree of inhibition was independent of the sludge treatment. The results revealed that AgNPs sulfidized under environmentally relevant conditions were still bioavailable to soil microorganisms. Consequently, Ag2S may exhibit toxic effects over the long term rather than the short term.
Lepot, M., Aubin, J. B., Clemens, F. H. L. R., & Mašić, A. (2017). Outlier detection in UV/Vis spectrophotometric data. Urban Water Journal, 14(9), 908-921. doi:10.1080/1573062X.2017.1280515, Institutional Repository

UV/Vis spectrophotometers have been used to monitor water quality since the early 2000s. Calibration of these devices requires sampling campaigns to elaborate relations between recorded spectra and measured concentrations. In order to build robust calibration data sets, several spectra must be recorded per sample. This study compares two approaches – principal component analysis and data depth theory – to identify outliers and select the most representative spectrum (MRS) among the repetitively recorded spectra. Detection of samples that contain outliers is consistent between the methods in more than 70% of the samples. Identification of spectra as outliers is consistent in more than 95% of the cases. The identification of MRS differs depending on the approach used. In their current form, both of the proposed approaches can be used for outlier detection and identification. Further studies are suggested to combine the methods and develop an automated ranking and sorting system.
Mašić, A., Billeter, J., Bonvin, D., & Villez, K. (2017). Extent computation under rank-deficient conditions. In D. Dochain, D. Henrion, & D. Peaucelle (Eds.), IFAC-PapersOnLine: Vol. 50. 20th IFAC world congress. Proceedings (pp. 3929-3934). doi:10.1016/j.ifacol.2017.08.367, Institutional Repository

The identification of kinetic models can be simplified via the computation of extents of reaction on the basis of invariants such as stoichiometric balances. In the extent space, one can identify the structure and the parameters of reaction rates individually, which significantly reduces the number of parameters that need to be estimated simultaneously. So far, extent-based modeling has only been applied to cases where all the extents can be computed from measured concentrations. This generally excludes its application to many biological processes for which the number of reactions tends to be larger than the number of measured quantities. This paper shows that, in some cases, such restrictions can be lifted. In addition, this study demonstrates the applicability of extent-based model identification using laboratory experimental data.
Mašić, A., Srinivasan, S., Billeter, J., Bonvin, D., & Villez, K. (2017). Identification of biokinetic models using the concept of extents. Environmental Science and Technology, 51(13), 7520-7531. doi:10.1021/acs.est.7b00250, Institutional Repository

The development of a wide array of process technologies to enable the shift from conventional biological wastewater treatment processes to resource recovery systems is matched by an increasing demand in predictive capabilities. Mathematical models are excellent tools to meet this demand. However, obtaining reliable and fit-for-purpose models remains a cumbersome task due to the inherent complexity of biological wastewater treatment processes. In this work, we present a first study in the context of environmental biotechnology that adopts and explores the use of extents as a way to simplify and streamline the dynamic process modeling task. In addition, the extent-based modeling strategy is enhanced by optimal accounting of nonlinear algebraic equilibria and nonlinear measurement equations. Finally, a thorough discussion of our results aims at demonstrating the benefits of extent-based modeling and its potential to turn environmental process modeling into a highly automated task.
Mašić, A., Srinivasan, S., Billeter, J., Bonvin, D., & Villez, K. (2017). Shape constrained splines as transparent black-box models for bioprocess modeling. Computers and Chemical Engineering, 99, 96-105. doi:10.1016/j.compchemeng.2016.12.017, Institutional Repository

Empirical model identification for biological systems is a challenging task due to the combined effects of complex interactions, nonlinear effects, and lack of specific measurements. In this context, several researchers have provided tools for experimental design, model structure selection, and optimal parameter estimation, often packaged together in iterative model identification schemes. Still, one often has to rely on a limited number of candidate rate laws such as Contois, Haldane, Monod, Moser, and Tessier. In this work, we propose to use shape-constrained spline functions as a way to reduce the number of candidate rate laws to be considered in a model identification study, while retaining or even expanding the explanatory power in comparison to conventional sets of candidate rate laws. The shape-constrained rate laws exhibit the flexibility of typical black-box models, while offering a transparent interpretation akin to conventionally applied rate laws such as Monod and Haldane. In addition, the shape-constrained spline models lead to limited extrapolation errors despite the large number of parameters.
McCall, A. K., Palmitessa, R., Blumensaat, F., Morgenroth, E., & Ort, C. (2017). Modeling in-sewer transformations at catchment scale – implications on drug consumption estimates in wastewater-based epidemiology. Water Research, 122, 655-668. doi:10.1016/j.watres.2017.05.034, Institutional Repository

To which extent illicit drugs are transformed during in-sewer transport, depends on a number of factors: i) substance-specific transformation rates, ii) environmental conditions, iii) point of discharge (location of drug user) and iv) sewer network properties, primarily hydraulic residence time (HRT) and the ratio of biofilm contact area to wastewater volume (A/Veq).
Assessing associated uncertainties typically requires numerous simulations. Therefore, we propose a new two-step modeling framework: 1) Quantify hydrodynamic conditions. This computationally demanding step was performed once in SWMM to derive HRT and A/Veq for each potential point of discharge (node) in three catchments of different size. 2) Estimate biomarker loss. In this step, Monte Carlo simulations were performed for defined scenarios. Depending on assumptions about drug user distribution and prevalence, a number of nodes was sampled. For each node an empirical first-order transformation model was applied with flow-path-corresponding HRT and A/Veq from step 1. Biotic and abiotic transformation rates were sampled from distributions combining variability of different biofilms.
In our modeling study, median losses were >30% for amphetamine, 6-monoacetylmorphine and 6-acetylcodeine in all three catchments with high uncertainty (5%–100% loss), which would imply a systematic underestimation of consumption when neglecting in-sewer processes. Median losses for 21 other investigated biomarkers were <10% with different uncertainty ranges – “no substantial transformation” was confirmed for nine substances in a real sewer segment with a 2-h residence time. Transferability of these results must be tested for other catchments. To further reduce uncertainty, mainly additional knowledge on transformation rates, particularly in biofilm, and their distribution across a sewer network is needed to update model input objectively. Our approach allows efficient testing and, furthermore, can be expanded for many other human biomarkers. Accounting for biomarker stability during in-sewer transport will avoid biased estimates and further improve wastewater-based epidemiology.
Mehrabi, K., Nowack, B., Arroyo Rojas Dasilva, Y., & Mitrano, D. M. (2017). Improvements in nanoparticle tracking analysis to measure particle aggregation and mass distribution: a case study on engineered nanomaterial stability in incineration landfill leachates. Environmental Science and Technology, 51(10), 5611-5621. doi:10.1021/acs.est.7b00597, Institutional Repository

Numerous nanometrology techniques have been developed in recent years to determine the size, concentration, and a number of other characteristics of engineered nanomaterials (ENM) in environmental matrices. Among the many available techniques, nanoparticle tracking analysis (NTA) can measure individual particles to create a size distribution and measure the particle number. Therefore, we explore the possibility to use these data to calculate the particle mass distribution. Additionally, we further developed the NTA methodology to explore its suitability for analysis of ENM in complex matrices by measuring ENM agglomeration and sedimentation in municipal solid waste incineration landfill leachates over time. 100 nm Au ENM were spiked into DI H2O and synthetic and natural leachates. We present the possibility of measuring ENM in the presence of natural particles based on differences in particle refractivity indices, delineate the necessity of creating a calibration curve to adjust the given NTA particle number concentration, and determine the instruments linear range under different conditions. By measuring the particle size and the particle number distribution, we were able to calculate the ENM mass remaining in suspension. By combining these metrics together with transmission electron microscopy (TEM) analyses, we could assess the extent of both homo- and heteroagglomeration as well as particle sedimentation. Reporting both size and mass based metrics is common in atmospheric particle measurements, but now, the NTA can give us the possibility of applying the same approach also to aqueous samples.
Merle, T., Pronk, W., & von Gunten, U. (2017). MEMBRO3X, a novel combination of a membrane contactor with advanced oxidation (O3/H2O2) for simultaneous micropollutant abatement and bromate minimization. Environmental Science and Technology Letters, 4(5), 180-185. doi:10.1021/acs.estlett.7b00061, Institutional Repository

Ozonation is a water treatment process for disinfection and/or micropollutant abatement. However, ozonation of bromide-containing water leads to bromate (BrO3–) formation, a potential human carcinogen. A solution for mitigating BrO3– formation during abatement of micropollutants is to minimize the ozone (O3) concentration. This can be achieved by dosing ozone in numerous small portions throughout a reactor in the presence of H2O2. Under these conditions, O3 is rapidly consumed to form hydroxyl radical (·OH), which will oxidize micropollutants. To achieve this goal, a novel process (“MEMBRO3X”) was developed in which ozone is transferred to the water through the pores of polytetrafluoroethylene (PTFE) hollow fiber membranes. When compared to the conventional peroxone process (O3/H2O2), the MEMBRO3X process shows better performance in terms of micropollutant abatement and bromate minimization for groundwater and surface water treatment. For a groundwater containing 180 μg/L bromide, a 95% abatement of the ozone-resistant probe compound p-chlorobenzoic acid yielded <0.5 μg/L BrO3–, whereas in the conventional peroxone process, 8 μg/L BrO3– was formed. In addition, the efficacy of the MEMBRO3X process was demonstrated with river water and lake water.
Mkhize, N., Taylor, M., Udert, K. M., Gounden, T. G., & Buckley, C. A. (2017). Urine diversion dry toilets in eThekwini Municipality, South Africa: acceptance, use and maintenance through users' eyes. Journal of Water Sanitation and Hygiene for Development, 7(1), 111-120. doi:10.2166/washdev.2017.079, Institutional Repository

This study was part of the VUNA project aimed to develop an affordable sanitation system that produces a valuable fertiliser, reduces pollution of water resources and promotes health. Urine diversion dry toilets (UDDTs) simplify the on-site hygienisation of faeces and allow for nutrient recovery from urine. Social acceptance is vital for the implementation of the UDDT, because sanitation is only effective if the system not only provides a well-designed toilet and effective waste management, but also offers users a facility that caters to their needs and is sensitive to their cultural lifestyle. This study used qualitative and quantitative methods to investigate acceptance, use and maintenance of UDDTs. Key findings indicate lower levels of acceptance of UDDTs among the elderly, who are accustomed to traditional pit toilets. The users aspire to own a flush toilet, perceived to be indicative of household wealth. A dominant concern was emptying the pit and the quality of the building material. Community interventions are required that will promote acceptance, understanding and encourage proper use and maintenance of the UDDT, and may need some technology modification. There is an urgent need for increased community participation to address users' perceptions, attitudes and behaviour concerning the UDDT.
Moll, J., Klingenfuss, F., Widmer, F., Gogos, A., Bucheli, T. D., Hartmann, M., & van der Heijden, M. G. A. (2017). Effects of titanium dioxide nanoparticles on soil microbial communities and wheat biomass. Soil Biology and Biochemistry, 111, 85-93. doi:10.1016/j.soilbio.2017.03.019, Institutional Repository

Titanium dioxide nanoparticles (TiO2 NPs) are the most produced NPs worldwide and have great potential to be utilized in agriculture as additives for plant protection products. However, concerns have been raised that some NPs may negatively affect crops and soil microbial communities, including beneficial microbes such as arbuscular mycorrhizal fungi. Here we tested two different TiO2 NPs (P25, E171) and a bulk TiO2 (particle size >100 nm) for their effects on the diversity and community composition of soil microorganisms. In addition we tested whether increasing concentrations of TiO2 NPs had effects on wheat growth and yield. Microbial diversity was analyzed using Illumina Miseq paired-end sequencing of ribosomal markers (prokaryotic 16SV3V4 and fungal ITS2 of the ribosomal RNA operon). Application of TiO2 NPs altered the detected prokaryotic but not fungal community structure. Prokaryotic community structure differed significantly between the three NP treatments and the control treatment without NP, although differences were smaller compared to those between the positive and the negative control. Specific microbial taxa responded positively or negatively to particular TiO2 NP treatments and, thus, may be used as bio-indicators for TiO2 NPs. No negative effects on wheat growth and on arbuscular mycorrhizal root colonization were detected, and no evidence for a dose-response relationship between wheat performance and TiO2 NP concentration was found. Overall, these results reveal that prokaryotes are more sensitive than fungi to the TiO2 NP treatments.
Nguyen, M. T., Allemann, L., Ziemba, C., Larivé, O., Morgenroth, E., & Julian, T. R. (2017). Controlling bacterial pathogens in water for reuse: treatment technologies for water recirculation in the Blue Diversion Autarky Toilet. Frontiers in Environmental Science, 5, 90 (13 pp.). doi:10.3389/fenvs.2017.00090, Institutional Repository

The Blue Diversion AUTARKY Toilet is a urine-diverting toilet with on-site treatment. The toilet is being developed to provide a safe and affordable sanitation technology for people who lack access to sewer-based sanitation. Water used for personal hygiene, hand washing, and flushing to rinse urine- and feces-collection bowls is treated, stored, and recycled for reuse to reduce reliance on external water supplies. The system provides an opportunity to investigate hygiene of water for reuse following treatment. Treatment in the toilet includes a Biologically Activated Membrane Bioreactor (BAMBi) followed by a secondary treatment technology. To identify effective secondary treatment, three options, including granular activated carbon (GAC) only, GAC+chlorine (sodium hypochlorite), and GAC+electrolysis are considered based on the bacterial inactivation and growth inhibition efficiency. Four different hygiene-relevant bacteria are tested: Escherichia coli, Enterococcus faecalis, Pseudomonas aeruginosa, and Salmonella typhimurium. Our evaluation demonstrates that—despite treatment of water with the BAMBi—E. coli, P. aeruginosa, and S. typhimurium have the potential to grow during storage in the absence of microbial competition. Including the indigenous microbial community influences bacterial growth in different ways: E. coli growth decreases but P. aeruginosa growth increases relative to no competition. The addition of the secondary treatment options considerably improves water quality. A column of GAC after the BAMBi reduces E. coli growth potential by 2 log10, likely due to the reduction of carbon sources. Additional treatments including chlorination and electrolysis provide further safety margins, with more than 5 log10 inactivation of E. coli. However, reactivation and/or regrowth of E. coli and P. aeruginosa occurs under in the absence of residual disinfectant. Treatment including the BAMBi, GAC, and electrolysis appear to be promising technologies to control bacterial growth during storage in water intended for reuse.
Praetorius, A., Gundlach-Graham, A., Goldberg, E., Fabienke, W., Navratilova, J., Gondikas, A., … von der Kammer, F. (2017). Single-particle multi-element fingerprinting (spMEF) using inductively-coupled plasma time-of-flight mass spectrometry (ICP-TOFMS) to identify engineered nanoparticles against the elevated natural background in soils. Environmental Science: Nano, 4(2), 307-314. doi:10.1039/c6en00455e, Institutional Repository

The discrimination of engineered nanoparticles (ENPs) from the natural geogenic background is one of the preeminent challenges for assessing their potential implications. At low ENP concentrations, most conventional analytical techniques are not able to take advantage of inherent differences (e.g. in terms of composition, isotopic signatures, element ratios, structure, shape or surface characteristics) between ENPs and naturally occurring nanoscale particles (NNPs) of similar composition. Here, we present a groundbreaking approach to overcome these limitations and enable the discrimination of man-made ENPs from NNPs through simultaneous detection of multiple elements on an individual particle level. This new analytical approach is accessible by an inductively-coupled plasma time-of-flight mass spectrometer (ICP-TOFMS) operated in single-particle mode. Machine learning is employed to classify ENPs and NNPs based on their unique elemental fingerprints and quantify their concentrations. We demonstrate the applicability of this single-particle multi-element fingerprinting (spMEF) method by distinguishing engineered cerium oxide nanoparticles (CeO2 ENPs) from natural Ce-containing nanoparticles (Ce-NNPs) in soils at environmentally relevant ENP concentrations, orders of magnitude below the natural background.
Schmitt, R. J. P., Morgenroth, E., & Larsen, T. A. (2017). Robust planning of sanitation services in urban informal settlements: an analytical framework. Water Research, 110, 297-312. doi:10.1016/j.watres.2016.12.007, Institutional Repository

New types of sanitation services are emerging to tackle the sanitation crisis in informal settlements. These services link toilet facilities to semi-decentralized treatment plants via frequent, road-based transport of excreta. However, information for the planning of such sanitation services is scarce, and their future operating conditions are highly uncertain. The key questions of this paper are therefore: a) what are the drivers behind success or failure of a service-based sanitation system in informal settlements and b) on what scales and under which conditions can such a system operate successfully? To answer these questions, already at an early stage of the planning process, we introduce a stochastic model to analyze a wide range of system designs under varying technical designs, socio-economic factors, and spatial condition. Based on these initial results, we design a sanitation service and use the numeric model to study its reliability and costs over a wide range of scales, i.e., system capacities, from very few to many hundred users per semi-decentralized treatment unit. Key findings are that such a system can only operate within a narrow, but realistic range of conditions. Key requirements are toilet facilities, which can be serviced rapidly, and a flexible workforce. A high density of facilities will also lower the costs. Under these premises, we develop a road-based sanitation service and model its functionality in different settings and under many scenarios. Results show that the developed sanitation system using a single vehicle is scalable (100–700 users), can provide reliable service, and can be cheap (<1.5 c/p/day). Hence, this paper demonstrates opportunities for road-based sanitation in informal settlements and presents a quantitative framework for designing such systems.
Senn, A. C., Kaegi, R., Hug, S. J., Hering, J. G., Mangold, S., & Voegelin, A. (2017). Effect of aging on the structure and phosphate retention of Fe(III)-precipitates formed by Fe(II) oxidation in water. Geochimica et Cosmochimica Acta, 202, 341-360. doi:10.1016/j.gca.2016.12.033, Institutional Repository

Iron(III)-precipitates formed by Fe(II) oxidation in aqueous solutions affect the cycling and impact of Fe and other co-precipitated elements in environmental systems. Fresh Fe(III)-precipitates are metastable and their transformation into more stable phases during aging may result in the release of initially co-precipitated ions. Phosphate, silicate, Mg and Ca play key roles in determining the structure and composition of fresh Fe(III)-precipitates. Here we examine how these ions affect the structure and phosphate retention of Fe(III)-precipitates formed by oxidation of 0.5 mM dissolved Fe(II) at pH 7.0 after aging for 30 days at 40 °C.
Iron K-edge X-ray absorption spectroscopy (XAS) shows that aged precipitates consist of the same structural units as fresh precipitates: Amorphous Fe(III)- or Ca-Fe(III)-phosphate, ferrihydrite, and poorly crystalline lepidocrocite. Mg, Ca, and dissolved phosphate stabilize (Ca-)Fe(III)-phosphate against transformation into ferrihydrite. Silicate further attenuates (Ca-)Fe(III)-phosphate transformation. The crystallinity of lepidocrocite formed in phosphate- and silicate-free solutions slightly increases during aging. The transformation of Fe(III)- and Ca-Fe(III)-phosphate into ferrihydrite and ongoing ferrihydrite crystallization during aging result in the release of co-precipitated phosphate. Dissolved Ca on the other hand limits phosphate concentrations to values consistent with solubility control by octacalciumphosphate. Owing to the combined effects of Ca and silicate, phosphate is most effectively retained by Fe(III)-precipitates formed and aged in Ca- and silicate-containing solutions. The results from this study contribute to an improved understanding of the formation and transformation of Fe(III)-precipitates and emphasize that the complexity of Fe(III)-precipitate dynamics in the presence of multiple interfering solutes must be considered when addressing their impact on major and trace elements in environmental systems.
Soltermann, F., Abegglen, C., Tschui, M., Stahel, S., & von Gunten, U. (2017). Options and limitations for bromate control during ozonation of wastewater. Water Research, 116, 76-85. doi:10.1016/j.watres.2017.02.026, Institutional Repository

Wastewater treatment plants (WWTPs) are important point sources for micropollutants, which are harmful to freshwater organisms. Ozonation of wastewater is a powerful option to abate micropollutants, but may result in the formation of the potentially toxic oxidation by-product bromate in bromide-containing wastewaters. This study investigates options to reduce bromate formation during wastewater ozonation by (i) reducing the bromide concentration of the wastewater, (ii) lowering the ozone dose during wastewater treatment and (iii) adding hydrogen peroxide to limit the lifetime of ozone and quench the intermediates of the bromate formation pathway. Two examples demonstrate that a high share of bromide in wastewater can originate from single point sources (e.g., municipal waste incinerators or landfills). The identification of major point sources requires laborious sampling campaigns, but may facilitate the reduction of the bromide load significantly. To reduce the bromate formation by lowering the ozone dose interferes with the aim to abate micropollutants. Therefore, an additional treatment is necessary to ensure the elimination of micropollutants. Experiments at a pilot-plant illustrate that a combined treatment (ozone/powdered activated carbon) allows to eliminate micropollutants with low bromate yields. Furthermore, the addition of hydrogen peroxide was investigated at bench-scale. The bromate yields could be reduced by ∼50% and 65% for a hydrogen peroxide dose of 5 and 10 mg L−1, respectively. In conclusion, there are options to reduce the bromate formation during wastewater ozonation, however, they are not simple with sometimes limited efficiency.
Tarpeh, W. A., Udert, K. M., & Nelson, K. L. (2017). Comparing ion exchange adsorbents for nitrogen recovery from source-separated urine. Environmental Science and Technology, 51(4), 2373-2381. doi:10.1021/acs.est.6b05816, Institutional Repository

Separate collection of urine, which is only 1% of wastewater volume but contains the majority of nitrogen humans excrete, can potentially reduce the costs and energy input of wastewater treatment and facilitate recovery of nitrogen for beneficial use. Ion exchange was investigated for recovery of nitrogen as ammonium from urine for use as a fertilizer or disinfectant. Cation adsorption curves for four adsorbents (clinoptilolite, biochar, Dowex 50, and Dowex Mac 3) were compared in pure salt solutions, synthetic urine, and real stored urine. Competition from sodium and potassium present in synthetic and real urine did not significantly decrease ammonium adsorption for any of the adsorbents. Dowex 50 and Dowex Mac 3 showed nearly 100% regeneration efficiencies. Estimated ion exchange reactor volumes to capture the nitrogen for 1 week from a four-person household were lowest for Dowex Mac 3 (5 L) and highest for biochar (19 L). Although Dowex Mac 3 had the highest adsorption capacity, material costs ($/g N removed) were lower for clinoptilolite and biochar because of their substantially lower unit cost.
Thürlimann, C. M., & Villez, K. (2017). Input estimation as a qualitative trend analysis problem. Computers and Chemical Engineering, 107, 333-342. doi:10.1016/j.compchemeng.2017.04.011, Institutional Repository

The study of techniques for qualitative trend analysis (QTA) has been a popular approach to address challenges in fault diagnosis of engineered processes. Such challenges include the lack of reliable extrapolation of available models and lack of representative data describing previously unseen circumstances. Many of these challenges appear in biological systems even when normal operation can be assumed. It is for this reason that QTA techniques have also been proposed for the purpose of fault detection, automation, and dynamic modeling. In this work, we adopt a shape-constrained spline function method for the purpose of unknown input estimation. Thanks to data collected at laboratory-scale in a biological reactor for urine nitrification, this novel approach has been demonstrated successfully for the first time.
Tobias, R., O'Keefe, M., Künzle, R., Gebauer, H., Gründl, H., Morgenroth, E., … Larsen, T. A. (2017). Early testing of new sanitation technology for urban slums: the case of the Blue Diversion Toilet. Science of the Total Environment, 576, 264-272. doi:10.1016/j.scitotenv.2016.10.057, Institutional Repository

The toilets used most in informal urban settlements have detrimental consequences for the environment and human health due to the lack of proper collection and treatment of toilet waste. Concepts for safe, sustainable and affordable sanitation systems exist, but their feasibility and acceptance have to be investigated at an early stage of development, which is difficult due to the high costs of building working models. In this paper, we present an approach to estimate acceptance in a valid and representative form with only one working model, and apply it to test an innovative zero-emission toilet with recycling of wash water. Four basic principles were specified for investigation and nine hypotheses formulated to test the feasibility and acceptance of these principles: source separation of urine and feces with subsequent collection for resource recovery; provision of wash water in a separate cycle with on-site recovery through a membrane bioreactor; a convenient and attractive overall design; and a financially sustainable business plan. In Kampala (Uganda), in 2013, data was collected from 22 regular users, 308 one-time users and a representative sample of 1538 participants. Qualitative data was collected from the users, who evaluated their likes, perceived benefits, social norms and expected ease of use based on verbal and visual information. Most of the hypotheses were confirmed, indicating the feasibility and acceptance of the basic principles. Source separation and on-site water recovery were found to be feasible and accepted, provided users can be convinced that the emptying service and water recovery process work reliably. In the survey, the toilet was evaluated favorably and 51% of the participants agreed to be placed on a bogus waiting list. However, some design challenges were revealed, such as the size of the toilet, hiding feces from view and improving the separation of urine and water
Vriens, B., Voegelin, A., Hug, S. J., Kaegi, R., Winkel, L. H. E., Buser, A. M., & Berg, M. (2017). Quantification of element fluxes in wastewaters: a nationwide survey in Switzerland. Environmental Science and Technology, 51(19), 10943-10953. doi:10.1021/acs.est.7b01731, Institutional Repository

The number and quantities of trace elements used in industry, (high-tech) consumer products, and medicine are rapidly increasing, but the resulting emissions and waste streams are largely unknown. We assessed the concentrations of 69 elements in digested sewage sludge and effluent samples from 64 municipal wastewater treatment plants as well as in major rivers in Switzerland. This data set, representative of an entire industrialized country, presents a reference point for current element concentrations, average per-capita fluxes, loads discharged to surface waters, and economic waste-stream values. The spatial distribution of many individual elements could be attributed either to predominant geogenic or to anthropogenic inputs. Per-capita element fluxes ranged from <10 μg day−1 (e.g., Au, In, and Lu) to >1 mg day−1 (e.g., Zn, Sc, Y, Nb, and Gd) and >1 g day−1 (e.g., for P, Fe, and S). Effluent loads of some elements contributed significantly to riverine budgets (e.g., 24% for Zn, 50% for P, and 83% for Gd), indicating large anthropogenic inputs via the wastewater stream. At various locations, precious metal concentrations in sludge were similar to those in profitable mining ores, with total flux values of up to 6.8 USD per capita per year or 15 USD per metric ton of dry sludge.
Völker, J., Vogt, T., Castronovo, S., Wick, A., Ternes, T. A., Joss, A., … Wagner, M. (2017). Extended anaerobic conditions in the biological wastewater treatment: higher reduction of toxicity compared to target organic micropollutants. Water Research, 116, 220-230. doi:10.1016/j.watres.2017.03.030, Institutional Repository

Extended anaerobic conditions during biological wastewater treatment may enhance the biodegradation of micropollutants. To explore this, we combined iron-reducing or substrate-limited anaerobic conditions and aerobic pilot-scale reactors directly at a wastewater treatment plant. To investigate the detoxification by these processes, we applied two in vitro bioassays for baseline toxicity (Microtox) and reactive toxicity (AREc32) as well as in vivo bioassays with aquatic model species in two laboratory experiments (Desmodesmus subspicatus, Daphnia magna) and two on-site, flow-through experiments (Potamopyrgus antipodarum, Lumbriculus variegatus). Moreover, we analyzed 31 commonly occurring micropollutants and 10 metabolites.
The baseline toxicity of raw wastewater was effectively removed in full-scale and reactor scale activated sludge treatment (>85%), while the oxidative stress response was only partially removed (>61%). A combination of an anaerobic pre-treatment under iron reducing conditions and an aerobic nitrification significantly further reduced the residual in vitro toxicities by 46–60% and outperformed the second combination consisting of an aerobic pre-treatment and an anaerobic post-treatment under substrate-limiting conditions (27–43%). Exposure to effluents of the activated sludge treatment did not induce adverse in vivo effects in aquatic invertebrates. Accordingly, no further improvement in water quality could be observed. Compared to that, the removal of persistent micropollutants was increased. However, this observation was restricted to a limited number of compounds and the removal of the sum concentration of all target micropollutants was relative low (14–17%).
In conclusion, combinations of strictly anaerobic and aerobic processes significantly enhanced the removal of specific and non-specific in vitro toxicities. Thus, an optimization of biological wastewater treatment can lead to a substantially improved detoxification. These otherwise hidden capacities of a treatment technology can only be uncovered by a complementary biological analysis.
Weissbrodt, D. G., Holliger, C., & Morgenroth, E. (2017). Modeling hydraulic transport and anaerobic uptake by PAOs and GAOs during wastewater feeding in EBPR granular sludge reactors. Biotechnology and Bioengineering, 114(8), 1688-1702. doi:10.1002/bit.26295, Institutional Repository

New-generation bioprocesses using granular sludge aim for a high-rate removal of nutrients from wastewater with low footprint. Achieving enhanced biological phosphorus removal (EBPR) relies on the design of sludge beds and wastewater feeding conditions to optimally load the biomass and to select for polyphosphate- (PAOs) over glycogen-accumulating organisms (GAOs) and over other heterotrophs. A hydraulic–metabolic mathematical model was developed to elucidate the impact of hydraulic transport patterns and environmental conditions on the PAO/GAO competition during up-flow feeding through an EBPR granular sludge bed. Tracer experiments highlighted plug-flow regimes with dispersion under both rapid (9 mh-1, Rebed = 1.6, Pez = 7.2, Pet = 4.6) and slow (0.9 mh-1, Rebed = 0.2, Pez = 21.3, Pet = 3.4) feeding. Non-turbulent regimes (Rebed << 103) promote a safe implementation of simultaneous fill/draw. Feeding time, pH, and temperature significantly impacted bacterial competition for carbon uptake under anaerobic slow feeding. Feeding duration should be designed to avoid full depletion of intracellular storage polymers within static granules. PAOs bear twice longer feeding than GAOs by using both polyphosphate and glycogen hydrolysis to sustain anaerobic C-uptake. Alkaline conditions (pH 7.25–8.0) by, e.g., dosing lime in the feed select for PAOs independently of temperature (10−30°C). A twice higher bed is required for full anaerobic conversions at 10 rather than 20°C. Biosystem responses for anaerobic C-uptake can be anticipated using the model toward designing robust anaerobic selectors to manage the microbial resource in EBPR granular sludge. Biotechnol. Bioeng. 2017;114: 1688–1702.
Wells, G. F., Shi, Y., Laureni, M., Rosenthal, A., Szivák, I., Weissbrodt, D. G., … Morgenroth, E. (2017). Comparing the resistance, resilience, and stability of replicate moving bed biofilm and suspended growth combined nitritation–anammox reactors. Environmental Science and Technology, 51(9), 5108-5117. doi:10.1021/acs.est.6b05878, Institutional Repository

Combined partial nitritation–anammox (PN/A) systems are increasingly being employed for sustainable removal of nitrogen from wastewater, but process instabilities present ongoing challenges for practitioners. The goal of this study was to elucidate differences in process stability between PN/A process variations employing two distinct aggregate types: biofilm [in moving bed biofilm reactors (MBBRs)] and suspended growth biomass. Triplicate reactors for each process variation were studied under baseline conditions and in response to a series of transient perturbations. MBBRs displayed elevated NH4+ removal rates relative to those of suspended growth counterparts over six months of unperturbed baseline operation but also exhibited significantly greater variability in performance. Transient perturbations led to strikingly divergent yet reproducible behavior in biofilm versus suspended growth systems. A temperature perturbation prompted a sharp reduction in NH4+ removal rates with no accumulation of NO2– and rapid recovery in MBBRs, compared to a similar reduction in NH4+ removal rates but a high level of accumulation of NO2– in suspended growth reactors. Pulse additions of a nitrification inhibitor (allylthiourea) prompted only moderate declines in performance in suspended growth reactors compared to sharp decreases in NH4+ removal rates in MBBRs. Quantitative fluorescence in situ hybridization demonstrated a significant enrichment of anammox in MBBRs compared to suspended growth reactors, and conversely a proportionally higher AOB abundance in suspended growth reactors. Overall, MBBRs displayed significantly increased susceptibility to transient perturbations employed in this study compared to that of suspended growth counterparts (stability parameter), including significantly longer recovery times (resilience). No significant difference in the maximal impact of perturbations (resistance) was apparent. Taken together, our results suggest that aggregate architecture (biofilm vs suspended growth) in PN/A processes exerts an unexpectedly strong influence on process stability.
Wu, B., Suwarno, S. R., Tan, H. S., Kim, L. H., Hochstrasser, F., Chong, T. H., … Fane, A. G. (2017). Gravity-driven microfiltration pretreatment for reverse osmosis (RO) seawater desalination: microbial community characterization and RO performance. Desalination, 418, 1-8. doi:10.1016/j.desal.2017.05.024, Institutional Repository

A pilot gravity-driven microfiltration (GDM) reactor was operated on-site for over 250 days to pretreat seawater for reverse osmosis (RO) desalination. The microbial community analysis indicated that the dominant species in the pilot GDM system (~ 18.6 L/m2 h) were completely different from those in the other tested GDM systems (~ 2.7–17.2 L/m2 h), operating on the same feed. This was possibly due to the differences in available space for eukaryotic movement, hydraulic retention time (i.e., different organic loadings) or operation time (250 days vs. 25–45 days). Stichotrichia, Copepoda, and Pterygota were predominant eukaryotes at genus level in the pilot GDM. Furthermore, the GDM pretreatment led to a significantly lower RO fouling potential in comparison to the ultrafiltration (UF) system. This was attributed to the fact that GDM filtration produced a permeate with less amount of assimilable organic carbon (AOC) and biopolymers. Accordingly, lower amount of organic foulants (biopolymers and low molecular weight neutrals) and less biofilm formation on the GDM-RO membrane were observed. Although α-proteobacteria were dominant in both RO fouling layers, their bacterial community compositions at genus level were significantly different. Thalassobius had higher abundance in the GDM-RO fouling layers, while Erythrobacter and Hyphomonas were more predominant in the UF-RO fouling layers.
Wu, B., Christen, T., Tan, H. S., Hochstrasser, F., Suwarno, S. R., Liu, X., … Fane, A. G. (2017). Improved performance of gravity-driven membrane filtration for seawater pretreatment: implications of membrane module configuration. Water Research, 114, 59-68. doi:10.1016/j.watres.2017.02.022, Institutional Repository

As a low energy and chemical free process, gravity-driven membrane (GDM) filtration has shown a potential for seawater pretreatment in our previous studies. In this study, a pilot submerged GDM reactor (effective volume of 720 L) was operated over 250 days and the permeate flux stabilized at 18.6 ± 1.4 L/m2h at a hydrostatic pressure of 40 mbar. This flux was higher than those in the lab-scale GDM reactor (16.3 ± 0.2 L/m2h; effective volume of 8.4 L) and in the filtration cell system (2.7 ± 0.6 L/m2h; feed side volume of 0.0046 L) when the same flat sheet membrane was used. Interestingly, when the filtration cell was submerged into the GDM reactor, the flux (17.2 L/m2h) was comparable to the submerged membrane module. Analysis of cake layer morphology and foulant properties indicated that a thicker but more porous cake layer with less accumulation of organic substances (biopolymers and humics) contributed to the improved permeate flux. This phenomenon was possibly associated with longer residence time of organic substances and sufficient space for the growth, predation, and movement of the eukaryotes in the GDM reactor. In addition, the permeate flux of the submerged hollow fibre membrane increased with decreasing packing density. It is thought that the movement of large-sized eukaryotes could be limited when the space between hollow fibres was reduced. In terms of pretreatment, the GDM systems effectively removed turbidity, viable cells, and transparent exopolymer particles from the feed seawater. Importantly, extending the reactor operation time produced a permeate with less assimilable organic carbon and biopolymers. Thus, the superior quality of the GDM permeate has the potential to alleviate subsequent reverse osmosis membrane fouling for seawater treatment.
Zöllig, H., Remmele, A., Morgenroth, E., & Udert, K. M. (2017). Removal rates and energy demand of the electrochemical oxidation of ammonia and organic substances in real stored urine. Environmental Science: Water Research and Technology, 3(3), 480-491. doi:10.1039/c7ew00014f, Institutional Repository

The separate collection and treatment of urine allows for an environmentally friendly and cost-efficient management of the nutrients contained in urine. The primary goal should be to recover all these nutrients. However, in some cases it will be economically or ecologically more sensitive to recover only the phosphorus, while nitrogen is removed together with organic substances (measured as chemical oxygen demand, COD) and pathogens. In this study, we investigated the use of galvanostatic electrolysis for the removal of nitrogen and COD from real stored urine. Non-active type boron-doped diamond (BDD) and active type thermally decomposed iridium oxide film (TDIROF) anodes were evaluated using batch experiments. On both anodes, ammonia was exclusively removed by indirect oxidation with active