Abteilung Wasserressourcen und Trinkwasser

Sustainable groundwater use relies on adequate rates of groundwater recharge, which are expected to change with climate change. However, climate impacts on recharge remain uncertain due to a paucity of measurements of recharge trends globally. Here we leverage the relationship between climatic aridity and long-term recharge measurements at 5,237 locations globally to identify regions where recharge is most sensitive to changes in climatic aridity. Recharge is most sensitive to climate changes in regions where potential evapotranspiration slightly exceeds precipitation, meaning even modest aridification can substantially decrease groundwater recharge. Future climate-induced recharge changes are expected to be dominated by precipitation changes, whereby changes in groundwater recharge will be amplified relative to precipitation changes. Recharge is more sensitive to changes in aridity than global hydrological models suggest. Consequently, the effects of climatic changes on groundwater replenishment and their impacts on the sustainability of groundwater use by humans and ecosystems probably exceed previous predictions.

Surface water (SW) - groundwater (GW) interactions exhibit complex spatial and temporal patterns often studied using tracers. However, most natural and artificial tracers have limitations in studying SW–GW interactions, particularly if no significant contrasts in concentrations between SW and GW exist or can be maintained for long durations. In such context, (noble) gases have emerged as promising alternatives to add to the available tracer methods, especially with the recent development of portable mass spectrometers, which enable continuous monitoring of dissolved gas concentrations directly in the field. However, long-duration gas injection into river water presents logistical challenges. To overcome this limitation, we present an efficient and robust diffusion-injection apparatus for labeling large amounts of river water. Our setup allows fine, real-time control of the gas injection rate, and is suitable for extended injection durations and different gas species. To illustrate the effectiveness of our approach, we present a case study where helium (He) is used as an artificial tracer to study river water infiltration into an alluvial aquifer. Our injection of He as a tracer increased the dissolved He concentration of the river water by one order of magnitude compared to air-saturated water concentration for 35 days. This experiment yields valuable information on travel times from the river to a pumping well and on the mixing ratios between freshly infiltrated river water and regional groundwater.

Gas species are widely used as natural or artificial tracers to study fluid dynamics in environmental and geological systems. The recently developed gas equilibrium membrane inlet mass spectrometry (GE-MIMS) method is most useful for accurate and autonomous on-site quantification of dissolved gases in aquatic systems. GE-MIMS works by pumping water through a gas equilibrator module containing a gas headspace, which is separated from the water by a gas-permeable membrane. The partial pressures of the gas species in the headspace equilibrate with the gas concentrations in the water according to Henry's Law and are quantified with a mass spectrometer optimized for low gas consumption (miniRUEDI or similar). However, the fragile membrane structures of the commonly used equilibrator modules break down at water pressures ≳3 bar. These modules are therefore not suitable for use in deep geological systems or other environments with high water pressures. To this end, the SysMoG® MD membrane module (Solexperts AG, Switzerland; “SOMM”) was developed to withstand water pressures of up to 100 bar. Compared to the conventionally used GE-MIMS equilibrator modules, the mechanically robust construction of the SOMM module entails slow and potentially incomplete gas–water equilibration. We tested the gas equilibration efficiency of the SOMM and developed an adapted protocol that allows correct operation of the SOMM for GE-MIMS analysis at high water pressures. This adapted SOMM GE-MIMS technique exhibits a very low gas consumption from the SOMM to maintain the gas–water equilibrium according to Henry's Law and provides the same analytical accuracy and precision as the conventional GE-MIMS technique. The analytical potential of the adapted SOMM GE-MIMS technique was demonstrated in a high-pressure fluid migration experiment in an underground rock laboratory. The new technique overcomes the pressure limitations of conventional gas equilibrators and thereby opens new opportunities for efficient and autonomous on-site quantification of dissolved gases in high-pressure environments, such as in research and monitoring of underground storage of CO₂ and waste deposits or in the exploration of natural resources.

Atmospheric deposition is an important source of the micronutrient selenium for terrestrial ecosystems and food chains. However, the factors determining the total concentrations and chemical forms (speciation) of selenium in atmospheric deposition remain poorly understood. Here, aerosol samples were collected weekly over 5 years at Pic du Midi Observatory (French Pyrenees), alongside highly temporally resolved samples of aerosols, precipitation, and cloud water taken during a 2-month campaign. Firstly, measurements of selenium, other elements, and water isotopes were combined with sophisticated modelling approaches (aerosol-chemistry-climate SOCOL-AERv2 model and air parcel backward trajectories and Lagrangian moisture source analyses). Aerosol selenium measurements agreed well with SOCOL-AERv2-predicted values, and interestingly, higher fluxes of selenium and other elements were associated with deep convective activity during thunderstorms, highlighting the importance of local cloud dynamics in high deposition fluxes. Our results further indicate the coupling of element and water cycles from source to cloud formation, with decoupling during precipitation due to below-cloud scavenging. Secondly, selenium speciation was investigated in relation to sulfur speciation, organic composition, and moisture sources. While in the 5-year aerosol series, selenite (SeIV) was linked to anthropogenic source factors, in wet deposition it was related to pH and Atlantic moisture sources. We also report an organic selenium fraction, tracing it back to a marine biogenic source in both aerosols and wet deposition. With a comprehensive set of observations and model diagnostics, our study underscores the role of weather system dynamics alongside source contributions in explaining the atmospheric supply of trace elements to surface environments.

The extent of littoral influence on lake gas dynamics remains debated in the aquatic science community due to the lack of direct quantification of lateral gas transport. The prevalent assumption of diffusive horizontal transport in gas budgets fails to explain anomalies observed in pelagic gas concentrations. Here, we demonstrate through high-frequency measurements in a eutrophic lake that daily convective horizontal circulation generates littoral-pelagic advective gas fluxes one order of magnitude larger than typical horizontal fluxes used in gas budgets. These lateral fluxes are sufficient to redistribute gases at the basin-scale and generate concentration anomalies reported in other lakes. Our observations also contrast the hypothesis of pure, nocturnal littoral-to-pelagic exchange by showing that convective circulation transports gases such as oxygen and methane toward both the pelagic and littoral zones during the daytime. This study challenges the traditional pelagic-centered models of aquatic systems by showing that convective circulation represents a fundamental lateral transport mechanism to be integrated into gas budgets.

Deforestation reduces the capacity of the terrestrial biosphere to take up toxic pollutant mercury (Hg) and enhances the release of secondary Hg from soils. The consequences of deforestation for Hg cycling are not currently considered by anthropogenic emission inventories or specifically addressed under the global Minamata Convention on Mercury. Using global Hg modeling constrained by field observations, we estimate that net Hg fluxes to the atmosphere due to deforestation are 217 Mg year^–1 (95% confidence interval (CI): 134–1650 Mg year^–1) for 2015, approximately 10% of global primary anthropogenic emissions. If deforestation of the Amazon rainforest continues at business-as-usual rates, net Hg emissions from the region will increase by 153 Mg year^–1 by 2050 (CI: 97–418 Mg year^–1), enhancing the transport and subsequent deposition of Hg to aquatic ecosystems. Substantial Hg emissions reductions are found for two potential cases of land use policies: conservation of the Amazon rainforest (92 Mg year^–1, 95% CI: 59–234 Mg year^–1) and global reforestation (98 Mg year^–1, 95% CI: 64–449 Mg year^–1). We conclude that deforestation-related emissions should be incorporated as an anthropogenic source in Hg inventories and that land use policy could be leveraged to address global Hg pollution.

Nitro-aromatic compounds (NACs) are among the major components of brown carbon (BrC) in the atmosphere, causing negative impacts on regional climate, air quality, and ecological health. Due to the extensive origins, it is still a challenge to figure out the contributions and originating regions for different sources of atmospheric NACs. Here, field observations on fine particulate NACs were conducted at a coastal rural area in Qingdao, China in the winter of 2018 and 2019. The mean total concentrations of fine particulate nitro-aromatic compounds were 125.0 ± 89.5 and 27.7 ± 21.1 ng/m³ in the winter of 2018 and 2019, respectively. Among the measured eleven NACs, nitrophenols and nitrocatechols were the most abundant species. Variation characteristics and correlation analysis showed that humidity and anthropogenic primary emissions had significant influences on the NAC abundances. In this study, two tracing methods of the improved spatial concentration weighted trajectory (SCWT) model and the receptor model of positive matrix factorization (PMF) were combined to comprehensively understand the origins of NACs in fine particles at coastal Qingdao. Four major sources were identified, including coal combustion, biomass burning, vehicle exhaust, and secondary formation. Surprisingly, coal combustion was responsible for about half of the observed nitro-aromatic compounds, followed by biomass burning (∼30%). The results by SCWT demonstrated that the coal combustion dominated NACs mainly originated from the Shandong peninsula and the areas to the north and southwest, while those dominated by biomass burning primarily came from local Qingdao and the areas to the west.

Understanding recharge is an important step in quantifying the sustainability and vulnerability of the groundwater reserve and promoting the adequate implementation of management policies. In southern Brazil, the Guarani Aquifer System (SAG) is increasingly utilised as a source of water for both rural and urban populations and agricultural activities. Being 90% confined, the regional SAG outcrop zones are generally considered the recharge areas, yet local recharge mechanics have yet to be constrained. Water table time series data over a 2-year period from 21 monitoring wells in the southern outcrop zone were investigated to assess the local recharge of the SAG. Recharge estimates calculated using the water table fluctuation (WTF) method were compared to the time series data in terms of auto- and cross-correlation factors. In turn, alluding to the memory effect of the water table that is controlled by the flow pathways to the well and its response to local rainfall events, it is apparent that the local conditions strongly affect water percolating through the unsaturated zone, with evidence of both matrix and preferential flow pathways feeding the monitoring sites. Matrix flow is broadly occurring within the study area, and preferential flow has a more restricted occurrence yet is associated with the highest rate of recharge. Although future studies may quantify the actual recharge amount related to each mechanism, this work explicitly shows that preferential flow mechanisms should not be ignored, providing insight into aquifer sustainability and its vulnerability to modern contaminants.

Isotope source tracing enables to accurately determine the fate of nutrients that are applied with fertilizers to soils. While this approach is well established for major nutrients such as nitrogen, it is not yet established for trace metals. Here, we aimed to determine the fate of the micronutrient zinc (Zn) and the contaminant cadmium (Cd) that were applied with an organic fertilizer to a soil–wheat system. A pot study was conducted in which wheat was grown on an alkaline soil. The soils received green manure and/or soluble Zn fertilizer and were compared with non-fertilized control treatments (n = 4 experimental replicates). The green manure was labelled with the stable isotopes ⁶⁷Zn and ¹¹¹Cd. For an efficient sample throughput, a method was provided and validated to determine enriched stable isotope ratios (⁶⁷Zn:⁶⁶Zn and ¹¹¹Cd:¹¹⁰Cd) and the Zn and Cd concentrations in one analytical run. To this end, single collector ICP-MS analyses and stable isotope mass balances calculations were combined. Applying this method revealed that the addition of green manure increased neither Zn nor Cd concentrations in wheat grains due to biomass dilution effects. Isotope source tracing showed that the largest fraction of these metals in the wheat shoots derived from the soil in all treatments (Zn 87–99 %, Cd 94–98 %). Moreover, the addition of green manure increased the transfer of Zn and Cd from soil to wheat by a factor 1.9 for both elements. This increased transfer was likely related to a nitrogen fertilization effect that increased root and shoot biomass and thereby the soil exploration of the wheat. This study demonstrated how the fate and dynamics of multiple trace metals can be efficiently determined in soil–fertilizer–crop systems using isotope source tracing.

Chlorine has been supplied by the chlor-alkali process that deploys dimensionally stable anodes (DSAs) for the electrochemical chlorine evolution reaction (ClER). The paramount bottlenecks have been ascribed to an intensive usage of precious elements and inevitable competition with the oxygen evolution reaction. Herein, a unique case of Ru²⁺-O₄ active motifs anchored on Magnéli Ti₄O₇ (Ru-Ti₄O₇) via a straightforward wet impregnation and mild annealing is reported. The Ru-Ti₄O₇ performs radically active ClER with minimal deployment of Ru (0.13 wt%), both in 5 m NaCl (pH 2.3) and 0.1 m NaCl (pH 6.5) electrolytes. Scanning electrochemical microscopy demonstrates superior ClER selectivity on Ru-Ti₄O₇ compared to the DSA. Operando X-ray absorption spectroscopy and density functional theory calculations reveal a universally active ClER (over a wide range of pH and [Cl⁻]), through a direct adsorption of Cl⁻ on Ru²⁺-O₄ sites as the most plausible pathway, together with stabilized ClO* at low [Cl⁻] and high pH.

Hydrological Ecosystem Services (HESs), as an important part of ecosystem services, are those services that depend on hydrological processes. HESs vulnerability assessment at the watershed scale is used to explore highly vulnerable areas for management and protection measures. This study aimed at developing a method for HESs vulnerability assessment and achieve a quantitative integrated index under future climate and land use change scenarios. We focused on three regulating HESs, including water flow regulation, erosion regulation, and local climate regulation (LC). An integrated model of Markov chain and automatic cells was used to predict land use changes. Future climate data were estimated using the Climate Change Toolkit (CCT). The Soil and Water Assessment Tool (SWAT) model was developed for HESs vulnerability assessment in the Taleghan Watershed in Iran. The model was calibrated by river discharge using the Sequential Uncertainty Fitting (SUFI-2) and the Parallel Processing option. The results show that sub-watersheds with higher precipitation (PCP) and lower evapotranspiration (ET) are more efficient in water flow and local climate regulation. However, sub-watersheds with lower PCP and higher ET are more vulnerable to erosion. Changes in water flow regulation services and local climate regulation were more consistent with climate changes, and conversely, changes in erosion and sediment regulation services had a very high level of compliance with land use changes. The method applied in this study can easily be adapted to other regions to identify areas with more vulnerability and less resilience in improving the water and soil structure and function in the watershed.

Geogenic groundwater contaminants (GGCs) affect drinking-water availability and safety, with up to 60% of groundwater sources in some regions contaminated by more than recommended concentrations. As a result, an estimated 300–500 million people are at risk of severe health impacts and premature mortality. In this Review, we discuss the sources, occurrences and cycling of arsenic, fluoride, selenium and uranium, which are GGCs with widespread distribution and/or high toxicity. The global distribution of GGCs is controlled by basin geology and tectonics, with GGC enrichment in both orogenic systems and cratonic basement rocks. This regional distribution is broadly influenced by climate, geomorphology and hydrogeochemical evolution along groundwater flow paths. GGC distribution is locally heterogeneous and affected by in situ lithology, groundwater flow and water–rock interactions. Local biogeochemical cycling also determines GGC concentrations, as arsenic, selenium and uranium mobilizations are strongly redox-dependent. Increasing groundwater extraction and land-use changes are likely to modify GGC distribution and extent, potentially exacerbating human exposure to GGCs, but the net impact of these activities is unknown. Integration of science, policy, community involvement programmes and technological interventions is needed to manage GGC-enriched groundwater and ensure equitable access to clean water.

Selenium (Se) is an essential micronutrient for many living organisms particularly due to its unique redox properties. We recently found that the sulfur (S) analog for dimethyl selenide (DMSe), i.e. dimethyl sulfide (DMS), reacts fast with the marine oxidant hypobromous acid (HOBr) which likely serves as a sink of marine DMS. Here we investigated the reactivity of HOBr with dimethyl selenide and dimethyl diselenide (DMDSe), which are the main volatile Se compounds biogenically produced in marine waters. In addition, the reactivity of HOBr with further organic Se compounds was tested, i.e., SeMet (as N-acetylated-SeMet), and selenocystine (SeCys₂ as N-acetylated-SeCys₂), as well as the phenyl-analogs of DMSe and DMDSe, respectively, diphenyl selenide (DPSe) and diphenyl diselenide (DPDSe). Apparent second-order rate constants at pH 8 for the reactions of HOBr with the studied Se compounds were (7.1 ± 0.7) × 10⁷ M⁻¹ s⁻¹ for DMSe, (4.3 ± 0.4) × 10⁷ M⁻¹ s⁻¹ for DMDSe, (2.8 ± 0.3) × 10⁸ M⁻¹ s⁻¹ for SeMet, (3.8 ± 0.2) × 10⁷ M⁻¹ s⁻¹ for SeCys₂, (3.5 ± 0.1) × 10⁷ M⁻¹ s⁻¹ for DPSe, and (8.0 ± 0.4) × 10⁶ M⁻¹ s⁻¹ for DPDSe, indicating a very high reactivity of all selected Se compounds with HOBr. The reactivity between HOBr and DMSe is lower than for DMS and therefore this reaction is likely not relevant for marine DMSe abatement. However, the high reactivity of SeMet with HOBr suggests that SeMet may act as a relevant quencher of HOBr.

The organic matter composition of lake sediments influences important in-lake biogeochemical processes and stores information on environmental changes. Extracting this information is notoriously difficult because of the complexity of the organic matter matrix, which routinely imposes trade-offs between high temporal and analytical detail in the selection of methods of analysis. Here, we demonstrate the potential of diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) for achieving both of these objectives using untreated bulk samples from two Holocene lake-sediment cores from central Sweden. We develop quantitative models for sediment total organic carbon (TOC) with the same predictive abilities as models based on samples diluted with KBr and qualitatively characterize the organic matter using a spectra processing-pipeline combined with principal component analysis. In the qualitative analysis we identified four organic matter sub-fractions and the interpretation of these is supported and further advanced with molecular data from pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Within these organic fractions, compound groups such as aromatics, lignin, aliphatics, proteins and polysaccharides were identified by means of DRIFTS and the analyses and processes outlined here enables rapid and detailed quantitative and qualitative analysis of sediment organic matter. The DRIFTS approach can be used as stand-alone method for OM characterization with high temporal resolution in Holocene sediment records. It may also function as a screening process for more specific analyses of sample subsets, such as when coupled with pyrolysis-GC/MS to further tease apart the OM composition, identify sources and determine degradation status.

N-Nitrosamines are potential human carcinogens frequently detected in natural and engineered aquatic systems. This study sheds light on the role of carbonyl compounds in the formation of N-nitrosamines by nitrosation of five secondary amines via different pathways. The results showed that compared to a control system, the presence of formaldehyde enhances the formation of N-nitrosamines by a factor of 5-152 at pH 7, depending on the structure of the secondary amines. Acetaldehyde showed a slight enhancement effect on N-nitrosamine formation, while acetone and benzaldehyde did not promote nitrosation reactions. For neutral and basic conditions, the iminium ion was the dominant intermediate for N-nitrosamine formation, while carbinolamine became the major contributor under acidic conditions. Negative free energy changes (<−19 kcal mol^-1) and relatively low activation energies (<18 kcal mol^-1) of the reactions of secondary amines with N₂O₃, iminium ions with nitrite and carbinolamines with N₂O₃ from quantum chemical computations further support the proposed reaction pathways. This highlights the roles of the iminium ion and carbinolamine in the formation of N-nitrosamines during nitrosation in the presence of carbonyl compounds, especially in the context of industrial wastewater.

Protection of groundwater resources is essential to ensure quality and sustainable use. However, predicting vulnerability to anthropogenic pollution can be difficult where data are limited. This is particularly true in the Sahel region of Africa, which has a rapidly growing population and increasing water demands. Here we use groundwater measurements of tritium (³H) with machine learning to create an aquifer vulnerability map (of the western Sahel), which forms an important basis for sustainable groundwater management. Modelling shows that arid areas with greater precipitation seasonality, higher permeability and deeper wells or water table generally have older groundwater and less vulnerability to pollution. About half of the modelled area was classified as vulnerable. Groundwater vulnerability is based on recent recharge, implying a sensitivity also to a changing climate, for example, through altered precipitation or evapotranspiration. This study showcases the efficacy of using tritium to assess aquifer vulnerability and the value of tritium analyses in groundwater, particularly towards improving the spatial and temporal resolution.

Urban expansion leads to increasing water pollution, impacting both human health and ecosystems. This decline in water quality often stems from insufficient wastewater treatment, along with runoff from both urban and agricultural areas. Water quality degradation challenges our efforts for sustainable water management and hinders progress toward the UN's Sustainable Development Goals (SDGs), particularly SDG6. Within aquatic environments, the hyporheic zone—the subsurface area where surface water and groundwater mix—plays a crucial role in facilitating pollutant turnover and overall aquatic health. Mixing between surface water and groundwater generates diverse microhabitats in the streambed with varying levels of oxygen, temperature, and chemical composition, which in turn allows diverse microbial communities to strive. The complexity of exchange flows within the hyporheic zone and associated turnover processes of pollutants and nutrients can only be assessed with detailed, cross-disciplinary data sets including data about hydrology, climatology, biogeochemistry, and the subsurface composition. However, integrated data sets of this kind are seldom available. As a result, the drivers behind pollutant dynamics in stream-aquifer systems are still not fully understood. Addressing this knowledge deficit, we present a comprehensive unique data set from an urban stream-aquifer system in Switzerland spanning over 6 months. Incorporating hydrometric, tracer, nutrient, microbial and organic micropollutant data, our data set can help to shed light on the intricate mechanisms governing hyporheic exchange flows, as well as nutrient and organic micropollutant cycling in urban environments.

Microfluidic models are proving to be powerful systems to study fundamental processes in porous media, due to their ability to replicate topologically complex environments while allowing detailed, quantitative observations at the pore scale. Yet, while porous media such as living tissues, geological substrates, or industrial systems typically display a porosity that spans multiple scales, most microfluidic models to date are limited to a single porosity or a small range of pore sizes. Here, a novel microfluidic system with multiscale porosity is presented. By embedding polyacrylamide (PAAm) hydrogel structures through in-situ photopolymerization in a landscape of microfabricated polydimethylsiloxane (PDMS) pillars with varying spacing, micromodels with porosity spanning several orders of magnitude, from nanometers to millimeters are created. Experiments conducted at different porosity patterns demonstrate the potential of this approach to characterize fundamental and ubiquitous biological and geochemical transport processes in porous media. Accounting for multiscale porosity allows studies of the resulting heterogeneous fluid flow and concentration fields of transported chemicals, as well as the biological behaviors associated with this heterogeneity, such as bacterial chemotaxis. This approach brings laboratory studies of transport in porous media a step closer to their natural counterparts in the environment, industry, and medicine.

Mixing controls the fate of any solute entering porous media. Hence, an understanding of the involved processes is essential for assessing subsurface contamination and planning for its protection. However, the three-dimensional mechanisms dominating solute mixing in the presence of several fluid phases in the pore space, and their dependency on phase saturation degree (fraction of the pore volume occupied by a phase) are unknown. Here, we analyze solute mixing in unsaturated porous media at the pore scale using X-ray micro-tomography performed with synchrotron radiation at unprecedented temporal and spatial resolutions for such an investigation. Transport experiments through a synthetic, sand-like porous medium, followed in 4D using a contrast solution, are performed at different liquid phase saturation degrees. The results reveal larger solute's front deformation at lower saturation, which translates into an enhanced mixing with time. Using different topological indexes, defined based on a description of the liquid phase geometry and of the resulting hydrodynamics, we show an increase in the spatial convergence of flow streamlines at lower saturation, which, in turn, leads to a strengthened helical flow inside the liquid phase. Consequently, this increases the number of shear- and vorticity-dominated deformation regions, as characterized by larger negative and positive Q-criterion values, respectively. These findings represent a major step toward understanding the control of both saturation and the system's heterogeneity on solute mixing, essential, among others, to assess reactivity in porous media.

The performance of time series models is assessed using synthetic head series simulated with a numerical model that solves Richards' equation for variably saturated flow. Heads were simulated in a homogeneous unconfined aquifer between two parallel canals; measured daily precipitation and potential evaporation are specified at the land surface and root water uptake is simulated. The head response to a precipitation event is nonlinear and depends on the saturation degree and rainfall before and after the precipitation event while evaporation reduction occurs during summers. Synthetic series were generated for 27 years and three different soil types; the unsaturated zone thickness varies between 0 and >5 m. The synthetic head series were simulated with a linear and nonlinear time series model. Performance of a linear time series model with four parameters, using a scaled Gamma response, gave R² values ranging from 0.67 to 0.96. The nonlinear time series model with five parameters simulates recharge using a root zone reservoir after which the head response to recharge is simulated with a scaled Gamma response function. The nonlinear time series model was able to simulate all synthetic head series very well with R² values above 0.9 for almost all models. The head response of the nonlinear model to a single precipitation event compares well to the response of the variably saturated groundwater model. The provided scripts may be used to simulate synthetic head series for other climates or for systems with additional complexity to assess the performance of other data-driven models.

Chemical oxidants applied in water treatment are electrophiles, which preferentially attack sites with higher electron density. This typically results in less efficient oxidative abatement of organic compounds with electron-withdrawing substituents. In this study, we observed that the permanganate-hydrogen peroxide (Mn(VII)–H₂O₂) process can enhance the abatement of some nitrogenous organic compounds with electron-withdrawing groups more significantly compared to Mn(VII) in absence of H₂O₂. A comparison of the oxidation of aniline and 4-chloroaniline, N,N-dimethylaniline and p-cyano-N,N-dimethylaniline, and hydrazine and acethydrazide for Mn(VII) and the Mn(VII)–H₂O₂ process was performed. It was observed that Mn(VII)–H₂O₂ can specifically enhance the oxidative abatement of the paired target compounds containing electron-withdrawing groups. By addition of Ba²⁺, to block the Mn(VI) reaction, it was demonstrated that Mn(VI) formed in the Mn(VII)–H₂O₂ process, was decisive for inducing the enhanced oxidation. This study reveals an interesting novel application of Mn(VII)–H₂O₂ for oxidative abatement of N-containing electron-deficient organic compounds during water treatment.

Industrial wastewater should be treated with caution due to its potential environmental risks. In this study, a polymerization-based cathode/Fe³⁺/peroxydisulfate (PDS) process was employed for the first time to treat a raw coking wastewater, which can achieve simultaneous organics abatement and recovery by converting organic contaminants into separable solid organic-polymers. The results confirm that several dominant organic contaminants in coking wastewater such as phenol, cresols, quinoline and indole can be induced to polymerize by self-coupling or cross-coupling. The total chemical oxygen demand (COD) abatement from coking wastewater is 46.8% and the separable organic-polymer formed from organic contaminants accounts for 62.8% of the abated COD. Dissolved organic carbon (DOC) abatement of 41.9% is achieved with about 89% less PDS consumption than conventional degradation-based process. Operating conditions such as PDS concentration, Fe³⁺ concentration and current density can affect the COD/DOC abatement and organic-polymer yield by regulating the generation of reactive radicals. ESI-MS result shows that some organic-polymers are substituted by inorganic ions such as Cl^–, Br^–, I^–, NH₄⁺, SCN^– and CN^–, suggesting that these inorganic ions may be involved in the polymerization. The specific consumption of this coking wastewater treatment is 27 kWh/kg COD and 95 kWh/kg DOC. The values are much lower than those of the degradation-based processes in treating the same coking wastewater, and also are lower than those of most processes previously reported for coking wastewater treatment.

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.

This publication summarizes my journey in the field of chemical oxidation processes for water treatment over the last 30+ years. Initially, the efficiency of the application of chemical oxidants for micropollutant abatement was assessed by the abatement of the target compounds only. This is controlled by reaction kinetics and therefore, second-order rate constant for these reactions are the pre-requisite to assess the efficiency and feasibility of such processes. Due to the tremendous efforts in this area, we currently have a good experimental data base for second-order rate constants for many chemical oxidants, including radicals. Based on this, predictions can be made for compounds without experimental data with Quantitative Structure Activity Relationships with Hammet/Taft constants or energies of highest occupied molecular orbitals from quantum chemical computations. Chemical oxidation in water treatment has to be economically feasible and therefore, the extent of transformation of micropollutants is often limited and mineralization of target compounds cannot be achieved under realistic conditions. The formation of transformation products from the reactions of the target compounds with chemical oxidants is inherent to oxidation processes and the following questions have evolved over the years: Are the formed transformation products biologically less active than the target compounds? Is there a new toxicity associated with transformation products? Are transformation products more biodegradable than the corresponding target compounds? In addition to the positive effects on water quality related to abatement of micropollutants, chemical oxidants react mainly with water matrix components such as the dissolved organic matter (DOM), bromide and iodide. As a matter of fact, the fraction of oxidants consumed by the DOM is typically > 99%, which makes such processes inherently inefficient. The consequences are loss of oxidation capacity and the formation of organic and inorganic disinfection byproducts also involving bromide and iodide, which can be oxidized to reactive bromine and iodine with their ensuing reactions with DOM. Overall, it has turned out in the last three decades, that chemical oxidation processes are complex to understand and to manage. However, the tremendous research efforts have led to a good understanding of the underlying processes and allow a widespread and optimized application of such processes in water treatment practice such as drinking water, municipal and industrial wastewater and water reuse systems.

Droughts in Africa have a disproportionate detrimental influence on food security, water supply, social equilibrium and the economy compared to other regions in the World. Crop growth is principally rain-fed with highly seasonal rainfall regimes over most of the Continent. Hydraulic infrastructure and harvest storage are scarce. Drought is primarily initiated by a lack of precipitation, and it spreads slowly to soil moisture, vegetation, streamflow, and groundwater, affecting the entirety hydrological processes across the landscape. This is called drought propagation and it is often characterized within a cascade framework linking the different types of droughts in sequence. In this study we perform continental-scale analysis of the drought cascade over the African Continent using remote sensing data from multiple sources. We examine the spatio-temporal variation of drought types. The drought cascade elements include precipitation, normalized difference vegetation index, total water storage, and surface soil moisture. Drought characteristics and the propagation time lag between different drought types are assessed over Africa. Time series analyses are conducted on the drought indices in order to estimate the behavior of each type of drought across twenty-three basins. Consistent propagation behavior is observed at continental and basin scales. The drought cascade begins with persistent precipitation deficit and translates instantaneously to soil moisture deficit, after one month to vegetation and after two months to total water storage of the hydrological system.

Background: Changes in climate and anthropogenic activities have made water salinization a significant threat worldwide, affecting biodiversity, crop productivity and contributing to water insecurity. The Horn of Africa, which includes eastern Ethiopia, northeast Kenya, Eritrea, Djibouti, and Somalia, has natural characteristics that favor high groundwater salinity. Excess salinity has been linked to infrastructure and health problems, including increased infant mortality. This region has suffered successive droughts that have limited the availability of safe drinking water resources, leading to a humanitarian crisis for which little spatially explicit information about groundwater salinity is available.
Methods: Machine learning (random forest) is used to make spatial predictions of salinity levels at three electrical conductivity (EC) thresholds using data from 8646 boreholes and wells along with environmental predictor variables. Attention is paid to understanding the input data, balancing classes, performing many iterations, specifying cut-off values, employing spatial cross-validation, and identifying spatial uncertainties.
Results: Estimates are made for this transboundary region of the population potentially exposed to hazardous salinity levels. The findings indicate that about 11.6 million people (∼7% of the total population), including 400,000 infants and half a million pregnant women, rely on groundwater for drinking and live in areas of high groundwater salinity (EC > 1500 µS/cm). Somalia is the most affected and has the largest number of people potentially exposed. Around 50% of the Somali population (5 million people) may be exposed to unsafe salinity levels in their drinking water. In only five of Somalia's 18 regions are less than 50% of infants potentially exposed to unsafe salinity levels. The main drivers of high salinity include precipitation, groundwater recharge, evaporation, ocean proximity, and fractured rocks. The combined overall accuracy and area under the curve of multiple runs is ∼ 82%.
Conclusions: The modelled groundwater salinity maps for three different salinity thresholds in the Horn of Africa highlight the uneven spatial distribution of salinity in the studied countries and the large area affected, which is mainly arid flat lowlands. The results of this study provide the first detailed mapping of groundwater salinity in the region, providing essential information for water and health scientists along with decision-makers to identify and prioritize areas and populations in need of assistance.

Water for irrigation use plays a critical role in agriculture via supporting crop growth and maintaining food production worldwide. Irrigation water quality evaluations provide useful information for sustainable water practices in many agricultural regions. In Brunei Darussalam, the quality of irrigation water is still poorly understood. The present study aims to investigate the hydrochemical characteristics of water resources in Brunei Darussalam and evaluate their quality and suitability for irrigation use. A total of fifteen sampling locations were chosen from selected ground and surface water sources found in all four Brunei districts. The water samples' physicochemical properties, including pH, EC, and major cations and anions, were measured and compared with FAO standards. Hydrochemical classification based on the Piper diagram revealed that water mainly belongs to the calcium-, magnesium-, and bicarbonate-type, or Type IV water class. The evaluation of heavy metals (Fe, Zn, Cu, Cr, As, and Cd) showed concentrations within the FAO’s permissible limits. In this regard, iron showed the highest concentration among the investigated metals. Established water quality indices such as SAR, Na%, RSC, MAR, KR, PS, and IWQI were used to evaluate and classify the water’s suitability for irrigation use. Overall, our findings revealed that almost all of the analysed water samples in the study area have low salinity and sodicity risks. However, only 27% of the samples passed the magnesium hazard assessment, and one sample showed a very poor IWQI result. Thus, additional testing and treatment are recommended for these cases. This study provides valuable insights on water quality for present and future utilisation, aiming to contribute to the protection of water resources in Brunei Darussalam.

The Last Glacial Maximum (LGM; ∼26-18 kyr ago) is a time interval of great climatic interest characterized by substantial global cooling driven by radiative forcings and feedbacks associated with orbital changes, lower atmospheric CO2, and large ice sheets. However, reliable proxies of continental paleotemperatures are scarce and often qualitative, which has limited our understanding of the spatial structure of past climate changes. Here, we present a quantitative noble gas temperature (NGT) record of the last ∼40 kyr from the Albian aquifer in Eastern Paris Basin (France, ∼48°N). Our NGT data indicate that the mean annual surface temperature was ∼5 °C during the Marine Isotope Stage 3 (MIS3; ∼40–30 kyr ago), before cooling to ∼2 °C during the LGM, and warming to ∼11 °C in the Holocene, which closely matches modern ground surface temperatures in Eastern France. Combined with water stable isotope analyses, NGT data indicate δD/NGT and δ¹⁸O/NGT transfer functions of +1.6 ± 0.4‰/°C and +0.18 ± 0.04‰/°C, respectively. Our noble-gas derived LGM cooling of ∼9 °C (relative to the Holocene) is consistent with previous studies of noble gas paleothermometry in European groundwaters but larger than the low-to-mid latitude estimate of 5.8 ± 0.6 °C derived from a compilation of noble gas records, which supports the notion that continental LGM cooling was more extreme at higher latitudes. While an LGM cooling of ∼9 °C in Eastern France appears compatible with recent data assimilation studies, this value is greater than most estimates from current-generation climate model simulations of the LGM. Comparing our estimate for the temperature in Eastern France during MIS3 (6.4 ± 0.5 °C) with GCM outputs presents a promising avenue to further evaluate climate model simulations and constrain European climate evolution over the last glacial cycle.

We study the upscaling of pore-scale solute transport in partially saturated porous media at different saturation degrees. The interaction between structural heterogeneity, phases distribution and small-scale flow dynamics induces complex flow patterns and broad probability distributions of flow, which control key aspects of transport, such as residence and arrival times, dispersion, and spatial solute distributions, as well as chemical reactions. A continuous-time random walk (CTRW) framework that integrates the processes of advection, diffusion, and trapping in immobile zones is used to upscale and evaluate the transport of diluted solutes. Results of this model were compared to direct numerical simulations solving the advection-diffusion equation in experimental saturation patterns. The comparison between simulations results, with different Péclet numbers (Pe), and the physics-based upscaled CTRW approach allows for a quantitative analysis of the governing factors of transport in partially saturated porous media. This analysis shows that the fluid phase saturation decreases the advective tortuosity, the media's characteristic length, the fraction of the immobile region, and the mean trapping time. At the same time, for a given saturation degree, the normalized mean trapping time is proportional to the Pe. This suggests that the characteristic trapping length is proportional to the media's characteristic (correlation) length. Moreover, the trapping frequency decreases with increasing Pe.

Due to its important spatiotemporal variability, accurate rainfall monitoring is one of the most difficult issues in semi-arid mountainous environments. Moreover, due to the inconsistent distribution of gauge measurement, the availability of precipitation data is not always secured and totally reliable at the instantaneous time step. As a result, earth observation of precipitation estimations could be an alternative for overcoming this restriction. The current study presents a framework for either the hydro-statistical evaluation and bias correction of the Global Precipitation Measurement (GPM) Integrated Multi-SatellitE Retrievals version 06 Early (IMERG-E), Late (IMERG-L), and Final (IMERG-F) products. On a sub-daily duration, from the Taferiat rain gauge-based station, which was used as a benchmark from 1 September 2014 to 31 August 2018. Statistical analysis was performed to examine each precipitation product’s performance. The results showed that all Post_Real_Time and Real_Time IMERG had a high level of awareness accuracy. The IMERG-L results were statistically similar to the gauge data, succeeded by the IMERG-F and IMERG-E. The Cumulative Distribution Function (CDF) has been employed to adjust the precipitation values of the three IMERG products in order to decrease bias estimation. The three products were then integrated into the "HEC-HMS" hydrological model to assess their dependability in flow modeling. Six flood occurrences were calibrated and validated for each product at 30-minute time steps. With a mean Nash-Sutcliffe coefficient of NSE 0.82, the calibration findings demonstrate that IMERG-F provides satisfactory hydrological performance. With an NSE = 0.80, IMERG-L displayed good hydrological utility, slightly better than IMERG-E with an NSE = 0.77. However, when the flood events were validated using the initial soil conditions, IMERG F and IMERG E overestimated the discharge by 13% and 10%, respectively. While IMERG L passed the validation phase with an average score of NSE = 0.69.

The heterogeneous chemistry of atmospheric aerosols involves multiphase chemical kinetics that can be described by kinetic multi-layer models (KMs) that explicitly resolve mass transport and chemical reactions. However, KMs are computationally too expensive to be used as sub-modules in large-scale atmospheric models, and the computational costs also limit their utility in inverse-modeling approaches commonly used to infer aerosol kinetic parameters from laboratory studies. In this study, we show how machine learning methods can generate inexpensive surrogate models for the kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB) to predict reaction times in multiphase chemical systems. We apply and compare two common and openly available methods for the generation of surrogate models, polynomial chaos expansion (PCE) with UQLab and neural networks (NNs) through the Python package Keras. We show that the PCE method is well suited to determining global sensitivity indices of the KMs, and we demonstrate how inverse-modeling applications can be enabled or accelerated with NN-suggested sampling. These qualities make them suitable supporting tools for laboratory work in the interpretation of data and the design of future experiments. Overall, the KM surrogate models investigated in this study are fast, accurate, and robust, which suggests their applicability as sub-modules in large-scale atmospheric models.

N-nitrosamines are formed during different industrial processes and are of significant concern due to their carcinogenic and mutagenic properties. This study reports concentrations of N-nitrosamines in eight different industrial wastewater treatment plants in Switzerland and the variability of their abundance. Only four N-nitrosamines species, N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosodibutylamine (NDPA) and N-nitrosomorpholine (NMOR) were above the limit of quantification in this campaign. Remarkably high concentrations (i.e. up to 975 μg NDMA/L, 90.7 μg NDEA/L, 1.6 μg NDPA/L and 710 μg NMOR/L) of these N-nitrosamines were detected at seven of eight sites. These concentrations are two to five orders of magnitude higher than those typically detected in municipal wastewater effluents. These results suggest that industrial effluents may be a major source of N-nitrosamines. Although very high concentrations of N-nitrosamine have been detected in industrial discharges, various processes in surface water can partially mitigate their concentrations (e.g. photolysis, biodegradation and volatilization) and hence the risk to human health and aquatic ecosystems. Nevertheless, there is little information on long-term effects on aquatic organisms and therefore the discharge of N-nitrosamines to the environment should be avoided until the impact on ecosystems is assessed. During winter a less efficient mitigation of N-nitrosamines can be expected (lower biological activity, less sunlight) and therefore, emphasis should be put on this season in future risk assessment studies.

Les N-nitrosamines constituent un groupe important d’agents cancérigènes et mutagènes qui peuvent être présents dans les eaux usées. Les concentrations dans les effluents industriels en Suisse sont de plusieurs ordres de grandeur supérieures à celles mesurées dans les eaux usées municipales. Ce constat suggère que les rejets industriels peuvent être une source importante de N-nitrosamines et être responsables des pics de concentration parfois mesurés dans certaines eaux usées municipales.

Although oceans play a key role in the global selenium (Se) cycle, there is currently very little quantitative information available on the distribution of Se concentrations and Se speciation in marine environments. In general, determining Se concentration and speciation in seawater is highly challenging due to very low Se levels ((sub)ng⋅L⁻¹), whereas matrix elements interfering Se pre-concentration and detection are up to the g⋅L⁻¹ levels. In this study, we established a sensitive method for the determination of the various Se chemical fractions present in natural seawater, i.e. selenite (Se^IV), selenate (Se^VI), organic Se^-II + Se⁰ and total Se, using species-specific isotope dilution gas chromatography coupled to inductively coupled plasma mass spectrometry (ID-GC-ICP-MS). We compared different derivatization reagents and optimized specific pre-treatment protocols, including a microwave assisted oxidation protocol for the determination of total Se and organic Se^-II + Se⁰ using H₂O₂. To increase sensitivity, we developed an online pre-concentration method based on large volume injection (LVI) using a programmed temperature vaporization (PTV) inlet. Eventually, the developed method achieved low absolute and methodological detection limits, i.e., respectively, 0.1–0.3 pg and 0.9–3.1 ng.L^-1 for the different fractions. The accuracy of our method was of 2% for a certified reference material (CRM) diluted in artificial seawater while the precision was better than 4% for a freshwater CRM in artificial seawater matrix as well as two common seawater CRMs certified for trace elements excluding Se. As a proof-of-concept, we quantified the various Se fractions in a large number of natural water samples from the Baltic and North Seas, encompassing a wide range of salinity (7–35 psu), which shows that its detection limits are sufficient to determine total Se, Se^IV, Se^VI and organic Se^-II + Se⁰ concentrations in brackish and marine systems.

Stratospheric ozone is expected to recover by the mid-century due to the success of the Montreal Protocol in regulating the emission of ozone-depleting substances (ODSs). In the Arctic, ozone abundances are projected to surpass historical levels due to the combined effect of decreasing ODSs and elevated greenhouse gases (GHGs). While long-term changes in stratospheric ozone have been shown to be a major driver of future surface climate in the Southern Hemisphere during summertime, the dynamical and climatic impacts of elevated ozone levels in the Arctic have not been investigated. In this study, we use two chemistry climate models (the SOlar Climate Ozone Links - Max Planck Ocean Model (SOCOL-MPIOM) and the Community Earth System Model - Whole Atmosphere Community Climate Model (CESM-WACCM)) to assess the climatic impacts of future changes in Arctic ozone on stratospheric dynamics and surface climate in the Northern Hemisphere (NH) during the 21st century. Under the high-emission scenario (RCP8.5) examined in this work, Arctic ozone returns to pre-industrial levels by the middle of the century. Thereby, the increase in Arctic ozone in this scenario warms the lower Arctic stratosphere; reduces the strength of the polar vortex, advancing its breakdown; and weakens the Brewer–Dobson circulation. The ozone-induced changes in springtime generally oppose the effects of GHGs on the polar vortex. In the troposphere, future changes in Arctic ozone induce a negative phase of the Arctic Oscillation, pushing the jet equatorward over the North Atlantic. These impacts of future ozone changes on NH surface climate are smaller than the effects of GHGs, but they are remarkably robust among the two models employed in this study, canceling out a portion of the GHG effects (up to 20 % over the Arctic). In the stratosphere, Arctic ozone changes cancel out a much larger fraction of the GHG-induced signal (up to 50 %-100 %), resulting in no overall change in the projected springtime stratospheric northern annular mode and a reduction in the GHG-induced delay of vortex breakdown of around 15 d. Taken together, our results indicate that future changes in Arctic ozone actively shape the projected changes in the stratospheric circulation and their coupling to the troposphere, thereby playing an important and previously unrecognized role as a driver of the large-scale atmospheric circulation response to climate change.

Many countries maintain nationwide groundwater networks to monitor the status of their groundwater resources. For effective groundwater resource management, it is fundamental to understand the groundwater dynamics measured in the individual monitoring wells. Nationwide monitoring networks typically cover multiple aquifer systems with different degrees of environmental complexity. The analysis of the data of such networks thus requires flexible modeling approaches. In this study, we assessed the applicability and performance of lumped-parameter models using impulse response functions, as implemented in the Pastas software, to simulate hydraulic head data from the nationwide groundwater monitoring network in Switzerland. The selected 28 monitoring wells in the network are situated in unconsolidated, relatively shallow aquifers across Switzerland. Given the very diverse topography in the study area, snowmelt processes affect some aquifers, while groundwater–surface water interactions are important in the valleys. Different linear and nonlinear models were tested to take precipitation and potential evaporation into account, with a new model developed as part of this study to account for the effect of snow processes on recharge generation. After generally good fits in both the calibration and evaluation were achieved, the models were used to identify and quantify which stresses (e.g., precipitation, river stages) control the groundwater dynamics. The results show that precipitation and evaporation explain large parts of the measured dynamics, and about half of the monitoring wells in the network appear to be influenced by river stages. Explicitly accounting for snow processes in the recharge generating process is found to improve the simulation of the head dynamics across Switzerland, particularly for wells in high-altitude aquifers. This study demonstrates for the first time the applicability of lumped-parameter models using impulse response functions to model heads in Switzerland, and more generally, in climatic settings where snow processes are impacting the head dynamics.

Als Strategien zur Anpassung an den Klimawandel eignen sich sowohl die thermische Bewirtschaftung von Grundwasserleitern als auch von Oberflächengewässern. Einerseits lassen sich damit negative Auswirkungen des Klimawandels auf die Wasserressourcen abschwächen. Andererseits besteht ein grosses Potenzial für die gleichzeitige Nutzung von Wärmeenergie. Deshalb sollten Klimawandel-Anpassungsstrategien ein integraler Bestandteil der nachhaltigen Bewirtschaftung von Wasserressourcen sein.

Quantitative Abschätzungen der Auswirkungen des Klimawandels auf Grundwasserressourcen erlauben es, zwischen hydraulischen und thermischen Auswirkungen auf natürliche und künstliche Grundwasserneubildung zu differenzieren. In Zukunft werden vermehrt Auswirkungen von saisonalen Verschiebungen bei der natürlichen Grundwasseranreicherung sowie Anpassungsstrategien der Wasserversorgung zu beobachten sein. Dabei ist zu berücksichtigen, dass einzelne Trinkwasserbrunnen von unterschiedlichen Komponenten der Grundwasserneubildung betroffen sind. Darüber hinaus dürften eine zunehmende künstliche Grundwasseranreicherung in den Sommermonaten und die Interaktion mit Oberflächengewässern während Hochwasserereignissen, die in den Wintermonaten häufiger auftreten werden, die Grundwasseranreicherung und -temperaturen stark beeinflussen.

Les évaluations quantitatives des effets du changement climatique sur les ressources en eaux souterraines permettent de différencier les effets hydrauliques et thermiques sur la recharge naturelle et artificielle des nappes phréatiques. A l’avenir, les effets des décalages saisonniers sur la recharge naturelle des eaux souterraines et les stratégies d’adaptation pour l’approvisionnement en eau seront de plus en plus observés. Il faut tenir compte du fait que les puits d’eau potable individuels sont affectés par différentes composantes de la recharge des eaux souterraines. En outre, l’augmentation de la recharge artificielle des nappes phréatiques durant les mois d’été et l’interaction avec les eaux en surface lors des crues, qui se produiront plus fréquemment pendant les mois d’hiver, devraient fortement affecter la recharge et les températures des eaux souterraines.

The governing hydrological processes are expected to shift under climate change in the alpine regions of Switzerland. This raises the need for more adaptive and accurate methods to estimate river flow. In high-altitude catchments influenced by snow and glaciers, short-term flow forecasting is challenging, as the exact mechanisms of transient melting processes are difficult to model mathematically and are poorly understood to this date. Machine learning methods, particularly temporally aware neural networks, have been shown to compare well and often outperform process-based hydrological models on medium and long-range forecasting. In this work, we evaluate a Long Short-Term Memory neural network (LSTM) for short-term prediction (up to three days) of hourly river flow in an alpine headwater catchment (Goms Valley, Switzerland). We compare the model with the regional standard, an existing process-based model (named MINERVE) that is used by local authorities and is calibrated on the study area. We found that the LSTM was more accurate than the process-based model on high flows and better represented the diurnal melting cycles of snow and glacier in the area of interest. It was on par with MINERVE in estimating two flood events: the LSTM captures the dynamics of a precipitation-driven flood well, while underestimating the peak discharge during an event with varying conditions between rain and snow. Finally, we analyzed feature importances and tested the transferability of the trained LSTM on a neighboring catchment showing comparable topographic and hydrological features. The accurate results obtained highlight the applicability and competitiveness of data-driven temporal machine learning models with the existing process-based model in the study area.

In the Arctic stratosphere, the combination of chemical ozone depletion by halogenated ozone-depleting substances (hODSs) and dynamic fluctuations can lead to severe ozone minima. These Arctic ozone minima are of great societal concern due to their health and climate impacts. Owing to the success of the Montreal Protocol, hODSs in the stratosphere are gradually declining, resulting in a recovery of the ozone layer. On the other hand, continued greenhouse gas (GHG) emissions cool the stratosphere, possibly enhancing the formation of polar stratospheric clouds (PSCs) and, thus, enabling more efficient chemical ozone destruction. Other processes, such as the acceleration of the Brewer–Dobson circulation, also affect stratospheric temperatures, further complicating the picture. Therefore, it is currently unclear whether major Arctic ozone minima will still occur at the end of the 21st century despite decreasing hODSs. We have examined this question for different emission pathways using simulations conducted within the Chemistry-Climate Model Initiative (CCMI-1 and CCMI-2022) and found large differences in the models' ability to simulate the magnitude of ozone minima in the present-day climate. Models with a generally too-cold polar stratosphere (cold bias) produce pronounced ozone minima under present-day climate conditions because they simulate more PSCs and, thus, high concentrations of active chlorine species (ClO_x). These models predict the largest decrease in ozone minima in the future. Conversely, models with a warm polar stratosphere (warm bias) have the smallest sensitivity of ozone minima to future changes in hODS and GHG concentrations. As a result, the scatter among models in terms of the magnitude of Arctic spring ozone minima will decrease in the future. Overall, these results suggest that Arctic ozone minima will become weaker over the next decades, largely due to the decline in hODS abundances. We note that none of the models analysed here project a notable increase of ozone minima in the future. Stratospheric cooling caused by increasing GHG concentrations is expected to play a secondary role as its effect in the Arctic stratosphere is weakened by opposing radiative and dynamical mechanisms.

Hot thermal fluids flow through the Earth's crust and carry valuable information about the deep subsurface. The monitoring of natural tracers transported in geothermal fluids, such as gases or ions, are relevant to better understand the geological processes in the Earth's subsurface and their relation to deep fluid dynamics. Recently developed technologies (e.g., portable gas-equilibrium membrane-inlet mass spectrometry) allow for the continuous monitoring of gas species at a much higher temporal resolution than the sampling procedures commonly used, based on a few individual samples. However, the monitoring of gas species from hot thermal fluids still poses experimental challenges tied to unwanted water vapor condensation in the headspace of the separation module, which irremediably leads to clogging (e.g., of the connecting capillaries) and failure of the detection device. In this contribution, we present two new experimental methods that provide suitable technical conditions to measure gases, even in high temperature geothermal fluids, using a portable gas analyzer. Two sites with different thermal water temperatures (first one ranging from 50 °C to 65 °C and second one close to boiling temperature) were selected. The first method was deployed on the thermal waters of Lavey-les-Bains (Vaud, Switzerland), for which we report results from October 2021. The second method was used in Beppu (Oita Prefecture, Japan), for which we report results from April 2018. Our results show that at both sites, our methods allow for continuous measurements of gas species (N₂, Ar, O₂, Kr, He, CH₄, CO₂ and H₂) in thermal waters. Furthermore, they show that the variability of gas emanation from the two sites can only be adequately described by measurements with high temporal resolution, which both methods allow.

Superoxide radicals (O₂^•-) have been suggested as an important chain carrier in the radical chain reaction that promotes ozone (O₃) decomposition to hydroxyl radicals (^•OH) during ozonation. However, due to the difficulty in measuring transient O₂^•- concentrations, this hypothesis has not been verified under realistic ozonation conditions during water treatment. In this study, a probe compound was used in combination with kinetic modeling to evaluate the role of O₂^•- for O₃ decomposition during ozonation of synthetic solutions with model promotors and inhibitors (methanol and acetate or tert-butanol) and natural waters (one groundwater and two surface waters). By measurement of the abatement of spiked tetrachloromethane (as a O₂^•- probe), the O₂^•- exposure during ozonation was determined. Based on the measured O₂^•- exposures, the relative contribution of O₂^•- to O₃ decomposition, in comparison to OH^-, ^•OH, and dissolved organic matter (DOM), was quantitatively evaluated using kinetic modeling. The results show that water compositions (e.g., the concentration of promotors and inhibitors, and the O₃ reactivity of DOM) have a considerable effect on the extent of the O₂^•--promoted radical chain reaction during ozonation. In general, the reaction with O₂^•- accounted for ∼59-70% and ∼45-52% of the overall O₃ decomposition during ozonation of the selected synthetic solutions and natural waters, respectively. This confirms that O₂^•- plays a critical role in promoting O₃ decomposition to ^•OH. Overall, this study provides new insights on the controlling factors for ozone stability during ozonation processes.

Holocene climate in the high tropical Andes was characterized by both gradual and abrupt changes, which disrupted the hydrological cycle and impacted landscapes and societies. High-resolution paleoenvironmental records are essential to contextualize archaeological data and to evaluate the sociopolitical response of ancient societies to environmental variability. Middle-to-Late Holocene water levels in Lake Titicaca were reevaluated through a transfer function model based on measurements of organic carbon stable isotopes, combined with high-resolution profiles of other geochemical variables and paleoshoreline indicators. Our reconstruction indicates that following a prolonged low stand during the Middle Holocene (4000 to 2400 BCE), lake level rose rapidly ~15 m by 1800 BCE, and then increased another 3 to 6 m in a series of steps, attaining the highest values after ~1600 CE. The largest lake-level increases coincided with major sociopolitical changes reported by archaeologists. In particular, at the end of the Formative Period (500 CE), a major lake-level rise inundated large shoreline areas and forced populations to migrate to higher elevation, likely contributing to the emergence of the Tiwanaku culture.

Mitigation of undesired byproducts from ozonation of dissolved organic matter (DOM) such as aldehydes and ketones is currently hampered by limited knowledge of their precursors and formation pathways. Here, the stable oxygen isotope composition of H₂O₂ formed simultaneously with these byproducts was studied to determine if it can reveal this missing information. A newly developed procedure, which quantitatively transforms H₂O₂ to O₂ for subsequent ¹⁸O/¹⁶O ratio analysis, was used to determine the δ¹⁸O of H₂O₂ generated from ozonated model compounds (olefins and phenol, pH 3-8). A constant enrichment of ¹⁸O in H₂O₂ with a δ¹⁸O value of ∼59‰ implies that ¹⁶O-¹⁶O bonds are cleaved preferentially in the intermediate Criegee ozonide, which is commonly formed from olefins. H₂O₂ from the ozonation of acrylic acid and phenol at pH 7 resulted in lower ¹⁸O enrichment (δ¹⁸O = 47-49‰). For acrylic acid, enhancement of one of the two pathways followed by a carbonyl-H₂O₂ equilibrium was responsible for the smaller δ¹⁸O of H₂O₂. During phenol ozonation at pH 7, various competing reactions leading to H₂O₂ via an intermediate ozone adduct are hypothesized to cause lower δ¹⁸O in H₂O₂. These insights provide a first step toward supporting pH-dependent H₂O₂ precursor elucidation in DOM.

Ozonation of drinking water and wastewater is accompanied by the formation of disinfection byproducts (DBPs) such as low molecular weight aldehydes and ketones from the reactions of ozone with dissolved organic matter (DOM). By applying a recently developed non-target workflow, 178 carbonous and nitrogenous carbonyl compounds were detected during bench-scale ozonation of two lake waters and three secondary wastewater effluent samples and full-scale ozonation of secondary treated wastewater effluent. An overlapping subset of carbonyl compounds (20%) was detected in all water types. Moreover, wastewater effluents showed a significantly higher fraction of N-containing carbonyl compounds (30%) compared to lake water (17%). All carbonyl compounds can be classified in 5 main formation trends as a function of increasing specific ozone doses. Formation trends upon ozonation and comparison of results in presence and absence of the ^•OH radical scavenger DMSO in combination with kinetic and mechanistic information allowed to elucidate potential carbonyl structures. A link between the detected carbonyl compounds and their precursors was established by ozonating six model compounds (phenol, 4-ethylphenol, 4-methoxyphenol, sorbic acid, 3-buten-2-ol and acetylacetone). About one third of the detected carbonous carbonyl compounds detected in real waters was also detected by ozonating model compounds.
Evaluation of the non-target analysis data revealed the identity of 15 carbonyl compounds, including hydroxylated aldehydes and ketones (e.g. hydroxyacetone, confidence level (CL) = 1), unsaturated dicarbonyls (e.g. acrolein, CL = 1; 2-butene-1,4-dial, CL = 1; 4-oxobut-2-enoic acid, CL = 2) and also a nitrogen-containing carbonyl compound (2-oxo-propanamide, CL =1).
Overall, this study shows the formation of versatile carbonous and nitrogenous carbonyl compounds upon ozonation involving ozone and ^•OH reactions. Carbonyl compounds with unknown toxicity might be formed, and it could be demonstrated that acrolein, malondialdehyde, methyl glyoxal, 2-butene-1,4-dial and 4-oxo-pentenal are degraded during biological post-treatment.

We present CAMELS-CH (Catchment Attributes and MEteorology for Large-sample Studies – Switzerland), a large-sample hydro-meteorological data set for hydrologic Switzerland in central Europe. This domain covers 331 basins within Switzerland and neighboring countries. About one-third of the catchments are located in Austria, France, Germany and Italy. As an Alpine country, Switzerland covers a vast diversity of landscapes, including mountainous environments, karstic regions, and several strongly cultivated regions, along with a wide range of hydrological regimes, i.e., catchments that are glacier-, snow- or rain dominated. Similar to existing data sets, CAMELS-CH comprises dynamic hydro-meteorological variables and static catchment attributes.
CAMELS-CH (Höge et al., 2023; available at https://doi.org/10.5281/zenodo.7784632) encompasses 40 years of data between 1 January 1981 and 31 December 2020, including daily time series of stream flow and water levels, and of meteorological data such as precipitation and air temperature. It also includes daily snow water equivalent data for each catchment starting from 2 September 1998. Additionally, we provide annual time series of land cover change and glacier evolution per catchment. The static catchment attributes cover location and topography, climate, hydrology, soil, hydrogeology, geology, land use, human impact and glaciers. This Swiss data set complements comparable publicly accessible data sets, providing data from the “water tower of Europe”.

Artificial tracers are often used for quantitative estimates of solute transport properties in rivers. However, single-injection tracer tests give insights in transport characteristics limited to the ecohydrological conditions at the testing time. Series of time-consuming and laborious tracer tests would be required to properly capture seasonal changes. The present study uses intrinsic diurnal fluctuations of electrical conductivity (EC) caused by discharge of treated wastewater as a tracer to evaluate solute transport processes along a 4.7-km reach of the River Erpe, Germany. By reproducing the fluctuations recorded along the river using the solute transport model one-dimensional transport with inflow and storage, this study investigated the long-term dynamics in solute transport properties. Individual 48-hr curves of EC were used in the steady state configuration of the model to gain 48-hr-integrated estimates of selected transport parameters. Using a sliding window approach in 1-hr steps along the 2,270-hr time series of EC the temporal variability of solute transport between April and June 2016 was assessed. To test the identifiability of parameters using the proposed method, sensitivity analyses and a breakthrough curve analysis of selected 48-hr windows were implemented. With time advancing into the summer, a significant rising trend (Mann-Kendall test p-value < 0.05) of the cross sectional area of the channel was observed and attributed to the growth of macrophytes and a significant slightly decreasing trend for the storage rate was found. The presented method is of high value for river management, as promoting transient storage enhances biogeochemical cycling and benefits water quality.

As climate change adaptation strategies, both Managed Aquifer (MAR) and Surface Water Recharge (MSWR) are not only highly suitable tools to mitigate negative effects on water resources but also bear large potential for concomitant exploitation of thermal energy. They should thus form an integral part of any sustainable water resources management strategy. However, while at global scale general water resource adaptation and mitigation measures are discussed widely, measures that build on thermal exploitation of MAR and MSWR, and which are readily adaptable to various different local and regional scale conditions, have yet to be developed.
Here, based on systematic numerical analyses of the sensitivity of groundwater and surface water recharge as well as water temperatures to climate change, we present adaptable implementation strategies of MAR and MSWR with concomitant exploitation of their thermal energy potential. Strategies and feasibility benchmarks for the exploitation of hydrologic and energetic potentials of MAR and MSWR were developed based on three hydrologically and hydrogeologically contrasting urban study sites near the city of Basel, Switzerland. Our studies show projected trends in the number of days when surface water temperatures exceed 25 °C examined for various streamflow and climate scenarios.
We illustrate that local hydrogeologic settings and hydrological boundary conditions as well as legal aspects affect to which degree MAR and MSWR are suitable solutions as climate change adaptation measures. Optimal situations for exploiting the potential of seasonal heat storage in MAR and MSWR exist where subsurface travel times between the injection and the withdrawal or exfiltration point are between 4 and 8 months and legal limits allow a sufficiently large temperature spread. In such settings, the exploitable water flux and temperature spread of MAR and MSWR reaches a heat potential of 14 to 20 MW (i.e., corresponding to 3 to 7 wind power plants), and energetic exploitation becomes a suitable tool either for local low-temperature heat applications such as heating and hot water or for ecological use as a heat and water buffer in rivers affected by seasonal droughts. As a positive side effect, climate-induced warming of groundwater resources and temperature increases in drinking water withdrawals would be mitigated simultaneously.

Study region: The Baltic countries (Estonia, Latvia, Lithuania), North Eastern Europe.
Study focus: Time series models are a convenient tool for modeling hydraulic head time series due to their parsimonious parameterization and quick calculation time. However, it is unclear how the model structure and the outcome relate to the respective site characteristics. Time series modeling with impulse response functions was used to model the head time series. The correlations between the model performance and the environmental settings and between the model parameters and the environmental settings were analyzed using Spearman rank correlation and Random Forest regression analyses.
New hydrological insights: From the 460 analyzed head time series, 145 were modeled with satisfactory goodness-of-fit in the calibration period, using only precipitation, potential evaporation, and temperature as model inputs. This number decreased to 68 time series with a satisfactory fit in the validation period. Including additional drivers in wells where a substantial influence is characteristic could improve modeling results. The model results suggest that snow processes are affecting head dynamics in many wells in the Baltic countries. Most correlations between the model performance and the environmental setting were observed with the geological and climatic setting of the site. Models performed best in monitoring wells with shallow groundwater and lower precipitation seasonality.

Field-based learning in hydrogeology enables students to develop their understanding and application of practical methodologies, and to enhance many of the generic skills (e.g., teamwork, problem-solving). However, teaching and learning hydrogeology in general, and especially in the field, presents cognitive difficulties, such as the diversity in student education and experience, the hidden nature of water movement and transport of chemicals, and the preexisting students' mental models of the subsurface, in particular. At any given experimental or teaching site there is only one reality for which lecturers can have an approximate conceptual model, including aquifer(s) geometry and functioning (e.g., flow direction). However, students' preconceptions (i.e., mental model), in some cases misconceptions, influence not only their outcome from the learning strategy designed, but also the conceptual model expression (i.e., flow chart, block diagram, or similar) for the study area or site. In practice, two general “teaching challenges” are identified to enable students' transition from the mental to the conceptual model: (1) identify and dispel any prior misconceptions and (2) show how to go from the partial information to the integration of new information for the development of the conceptual model. The inclusion of specific prior-to-field lessons in the classroom is recommended and in general, done. However, introducing a prior-to-field survey to learn about students' backgrounds, and methodologies for the development and expression of hydrogeological conceptual models and for testing multiple plausible conceptual models will help students transition from the mental to the conceptual model.

In this study, the speciation and isotopic composition of Zn were traced across the sediments of a freshwater lake that experienced one hundred years of strong eutrophication, in order to assess the potential of sedimentary Zn isotopes to record such an environmental disturbance. The results indicate that the sedimentary Zn isotope signal varied with the change from pre-eutrophic to eutrophic conditions in the investigated lake. The average δ⁶⁶Zn_JMC value of the dominantly allochthonous lithogenic sediments deposited during the pre-eutrophic period was +0.27‰ ±0.05‰ (i.e. similar to the δ⁶⁶Zn_JMC value of +0.28‰ ±0.05‰ proposed for Bulk Silicate Earth), while enhanced autochthonous biochemical sedimentation during the eutrophic period resulted in significantly lower δ⁶⁶Zn_JMC values down to +0.04‰ ±0.06‰. Synchrotron-based X-ray absorption spectroscopy data revealed a concomitant change in Zn speciation from a dominant fraction of Zn in clay minerals during the pre-eutrophic period to a major fraction of Zn in ZnS during the eutrophic period. A linear regression relating the sedimentary Zn isotope signal to the fraction of Zn in ZnS indicated δ⁶⁶Zn_JMC values of +0.27‰ ±0.06‰ and 0.00‰ ±0.08‰ for Zn in clay minerals and in ZnS, respectively. The enrichment of light Zn in ZnS in the eutrophic sediments is tentatively attributed to enhanced biological uptake of light Zn in the water column, which resulted in an enhanced flux of organic-bound Zn towards the sediments and further transformation of organic Zn into ZnS upon biomass mineralization during early diagenesis. This hypothesis is in agreement with the fractionation towards lighter Zn reported for both biological uptake of Zn and ZnS precipitation. The results of this study emphasize the potential of sedimentary Zn isotopes to register past eutrophic periods in freshwater lakes, and thus to serve as a probe of paleo-environmental conditions and/or past land use at the catchment scale.

Photolysis of molecular oxygen (O₂) sustains the stratospheric ozone layer and is thereby protecting living organisms on Earth by absorbing harmful ultraviolet radiation. In the past, atmospheric O₂ levels were not constant, and their variations are thought to be responsible for the extinction of some species due to the thinning of the ozone layer. Over the Phanerozoic Eon (last ∼500 Mio years), the O₂ volume mixing ratio ranged between 10% and 35% depending on the level of photosynthetic activity of plants and oceans. Previous estimates, mostly performed by simplified 1-D models, showed different ozone (O₃) responses to atmospheric O₂ changes within this range, such as monotonically positive or negative correlations, or displaying a maximum in the O₃ column around a certain O₂ level. Here, we assess the ozone layer sensitivity to atmospheric O₂ varying between 5% and 40% with a state-of-the-art 3-D chemistry-climate model (CCM). Our findings show that the O₃ layer thickness maximizes around the current mixing ratio of O₂, 21% ± 5%, while lower or higher levels of O₂ result globally in a reduction of total column O₃. At low latitudes, the total column O₃ is less sensitive to O₂ variations, because of the "self-healing" effect, namely, a vertical dipole in the tropical ozone response. Mid- and high-latitude O₃ columns that are largely affected by transport of O₃ from the tropics, however, are much more sensitive to O₂ with changes up to 20 DU even for small (±5%) O₂ perturbations. We show that these variations are largely driven by the radiative impact of O₃ on stratospheric temperatures and on the strength of the Brewer-Dobson circulation (BDC), indicating chemistry-radiation-transport feedback. High O₂ cases result in an acceleration of the BDC and vice versa, which always works in favor of the negative part of the O₃ anomaly dipole in the tropics being more effectively transported to the mid- and high-latitudes than the positive one. Although there are other factors strongly influencing O₃/O₂ relationship on the Phanerozoic Eon timescales that have not been considered here, our results and the presented mechanism bring useful insights for other studies focusing on the long-term O₃/O₂ relationship.

Biofilms are aggregates of microorganisms in which cells are embedded in a self-secreted extra-cellular matrix. This surface-attached form of bacterial living is common across numerous natural and technical environments, including sediments, rivers, filters, and membranes. These environments can be categorized as porous media, meaning they consist of a solid matrix with void spaces. Fluid flow through porous media influences biofilm growth through both nutrient availability and shear stress, while in turn; growing biofilms clog pores and change fluid flow directions and velocities. In this thesis, this interplay is studied in detail at the pore-scale to understand fundamental mechanisms, which can drive larger-scale processes. Unravelling the highly complex interplay between biofilm development and local hydrodynamics is important for understanding links between ecological processes, biochemical cycling, and flow and mass transport in bioclogged porous media found among others in subsurface biofilm barriers, bioremediation and wastewater treatment. [...]

The functioning of natural and engineered porous media, like soils and filters, depends in many cases on the interplay between biochemical processes and hydrodynamics. In such complex environments, microorganisms often form surface-attached communities known as biofilms. Biofilms can take the shape of clusters, which alter the distribution of fluid flow velocities within the porous medium, subsequently influencing biofilm growth. Despite numerous experimental and numerical efforts, the control of the biofilm clustering process and the resulting heterogeneity in biofilm permeability is not well understood, limiting our predictive abilities for biofilm-porous medium systems. Here, we use a quasi-2D experimental model of a porous medium to characterize biofilm growth dynamics for different pore sizes and flow rates. We present a method to obtain the time-resolved biofilm permeability field from experimental images and use the obtained permeability field to compute the flow field through a numerical model. We observe a biofilm cluster size distribution characterized by a spectrum slope evolving in time between -2 and -1, a fundamental measure that can be used to create spatio-temporal distributions of biofilm clusters for upscaled models. We find a previously undescribed biofilm permeability distribution, which can be used to stochastically generate permeability fields within biofilms. An increase in velocity variance for a decrease in physical heterogeneity shows that the bioclogged porous medium behaves differently than expected from studies on heterogeneity in abiotic porous media.

Emissions of volatile organic sulfur (S), selenium (Se), bromine (Br), and iodine (I) species from aquatic ecosystems represent an important source of these elements into the atmosphere. Available methods to measure these species are either not sensitive enough or not automated, which hinder a full understanding of species distribution and production mechanisms. Here, we present a sensitive and high-throughput method for the simultaneous and comprehensive quantification of S, Se, Br, and I volatile organic species in atmospheric and aqueous samples using a preconcentration step onto sorbent tubes and subsequent analysis by thermal desorption coupled to gas chromatography and inductively coupled plasma mass spectrometry (TD-GC-ICP-MS). Selected commercially available sorbent tubes, consisting of mixed porous polymer and graphitized black carbon, offered the highest trapping capacity and lowest loss of species when stored at -20 °C for 28 days after sampling. After optimization of the TD-GC-ICP-MS method, absolute detection limits were better than 3.8 pg, 9.1 fg, 313 fg, and 50 fg, respectively, for S, Se, Br, and I species. As a proof of concept, the concentrations of target species were determined in aqueous and continuously collected atmospheric samples during a cruise in the Baltic and North Seas. Moreover, unknown S, Br, and I volatile species were detected in both aqueous and atmospheric samples demonstrating the full potential of the method.

Stratospheric aerosols play important roles in Earth's radiative budget and in heterogeneous chemistry. Volcanic eruptions modulate the stratospheric aerosol layer by injecting particles and particle precursors like sulfur dioxide (SO₂) into the stratosphere. Beginning on 9 April 2021, La Soufrière erupted, injecting SO₂ into the tropical upper troposphere and lower stratosphere, yielding a peak SO₂ loading of 0.3–0.4 Tg. The resulting volcanic aerosol plumes dispersed predominately over the Northern Hemisphere (NH), as indicated by the CALIOP/CALIPSO satellite observations and model simulations. From June to August 2021 and May to July 2022, the NASA ER-2 high-altitude aircraft extensively sampled the stratospheric aerosol layer over the continental United States during the Dynamics and Chemistry of the Summer Stratosphere (DCOTSS) mission. These in situ aerosol measurements provide detailed insights into the number concentration, size distribution, and spatiotemporal variations of particles within volcanic plumes. Notably, aerosol surface area density and number density in 2021 were enhanced by a factor of 2–4 between 380–500 K potential temperature compared to the 2022 DCOTSS observations, which were minimally influenced by volcanic activity. Within the volcanic plume, the observed aerosol number density exhibited significant meridional and zonal variations, while the mode and shape of aerosol size distributions did not vary. The La Soufrière eruption led to an increase in the number concentration of small particles (<400 nm), resulting in a smaller aerosol effective diameter during the summer of 2021 compared to the baseline conditions in the summer of 2022, as observed in regular ER-2 profiles over Salina, Kansas. A similar reduction in aerosol effective diameter was not observed in ER-2 profiles over Palmdale, California, possibly due to the values that were already smaller in that region during the limited sampling period in 2022. Additionally, we modeled the eruption with the SOCOL-AERv2 aerosol–chemistry–climate model. The modeled aerosol enhancement aligned well with DCOTSS observations, although the direct comparison was complicated by issues related to the model's background aerosol burden. This study indicates that the La Soufrière eruption contributed approximately 0.6 % to Arctic and Antarctic ozone column depletion in both 2021 and 2022, which is well within the range of natural variability. The modeled top-of-atmosphere 1-year global average radiative forcing was −0.08 W m⁻² clear-sky and −0.04 W m⁻² all-sky. The radiative effects were concentrated in the tropics and NH midlatitudes and diminished to near-baseline levels after 1 year.

Biogeochemical gas production resulting in free gas phase formation can severely affect groundwater and solute transport in aquifers. Such gas–water interactions are important in aquifers affected by geogenic As, which are commonly associated with biogeochemical CH₄ production. Additionally, the influence of aquitards on As concentrations in contaminated aquifers has recently been challenged. These observations prompted the analysis through a heterogeneous aquitard overlying a high CH₄-gas-producing zone of an As-contaminated aquifer. A sediment core taken through the aquitard was analyzed for noble gases to assess how the aquitard physically contributes to the underlying gas production. Results reveal that the aquitard pore space is unsaturated in two separate layers resulting in hanging pore water constrained by an air-like gas phase. This interlayering of unsaturated and saturated zones identifies the aquitard's stratigraphy as key in determining hydrostatic pressure - a main control of free gas formation (i.e., CH₄) in the underlying aquifer. The partly unsaturated conditions reduce the hydrostatic pressure by 30% compared with fully saturated conditions. To our knowledge, this is the first study applying noble gases to examine the influence of an aquitards physical state on gas production in an underlying aquifer. Further, such partly unsaturated sediment layers of low conductivity might provide preferential pathways for periodic water flow, fostering aquitard–aquifer solute transport. Groundwater samples additionally collected throughout the study site confirm more widespread degassing than previously reported. Up to 90% of the expected atmospheric noble gas concentrations is lost from groundwater immediately below the investigated sediment core.

This work focuses on the application of noble gases as tracers in an arsenic contaminated aquifer situated along the Red River delta in Vietnam. Noble gases are utilised to evaluate the gas and groundwater dynamics in the contaminated aquifer, with the aim to improve knowledge on the physical mechanism(s) controlling As transport and distribution. Since the inert property of noble gases ensures they are solely affected by physical processes, separation from any biogeochemical processes, which additionally affect As mobilisation, can thus be achieved.
The main source of noble gas concentrations in groundwater of the contaminated aquifer, are derived from the atmosphere and are therefore mainly dependant on the local conditions (i.e., temperature, salinity and atmospheric pressure) from the last moment the sampled groundwater parcel was in contact with the atmosphere. Deviation from these expected, atmospherically derived concentrations allows identification of the specific physical processes affecting gas concentrations in groundwater. The major physical processes identified via noble gas analysis in the groundwater of this study are: excess air formation, radiogenic decay and degassing.
The most important of these identified processes relevant to this work is degassing, which refers to the loss of dissolved atmospheric gases in groundwater, as a result of a newly formed free gas phase. Such gas phases can be formed through over-saturation of biogeochemical gases produced within an aquifer. Noble gases in the groundwater partition into the newly produced gas phase or gas bubbles, which is subsequently removed from the aquifer, leaving behind groundwater depleted in atmospheric gases. [...]

Bromine radical (Br) has been hypothesized to be a key intermediate of bromate formation during ozonation. Once formed, Br further reacts with ozone to eventually form bromate. However, this reaction competes with the reaction of Br with dissolved organic matter (DOM), of which reactivity and reaction mechanisms are less studied to date. To fill this gap, this study determined the second-order rate constant (k) of the reactions of selected organic model compounds, a DOM isolate, and monochloramine (NH2Cl) with Br using γ-radiolysis. The kBr of all model compounds were high (kBr > 108 M-1 s-1) and well correlated with quantum-chemically computed free energies of activation, indicating a selectivity of Br toward electron-rich compounds, governed by electron transfer. The reaction of phenol (a representative DOM moiety) with Br yielded p-benzoquinone as a major product with a yield of 59% per consumed phenol, suggesting an electron transfer mechanism. Finally, the potential of NH2Cl to quench Br was tested based on the fast reaction (kBr, NH2Cl = 4.4 × 109 M-1 s-1, this study), resulting in reduced bromate formation of up to 77% during ozonation of bromide-containing lake water. Overall, our study demonstrated that Br quenching by NH2Cl can substantially suppress bromate formation, especially in waters containing low DOC concentrations (1-2 mgC/L).

Excess phosphorus abundance often drives eutrophication and affects surface water quality. Formation of vivianite (Fe₃(PO₄)₂ • 8H₂O) in aquatic sediments acts as a significant sink for phosphate (P), crucial for resorting surface waters. Authigenic vivianite formation, however, can be limited by other ferrous iron containing phases, in particular iron sulfides. Although thermodynamically feasible under suitable conditions, the formation of vivianite from mackinawite has been widely disregarded for authigenic phosphate mineral formation. Here we investigated the formation of vivianite from mackinawite (FeS) in batch experiments in which dissolved sulfide was continuously removed, at P levels between 0 - 5 mM in a pH of 6 to 8. Solid characterizations by electron microscopy, X-ray diffraction as well as Mössbauer and X-ray absorption spectroscopy demonstrates that vivianite was formed at all pH values in P amended experiments. The temporal evolution of dissolved Fe(II) concentrations indicates that the transformation proceeds via the release of the dissolved Fe(II) by FeS dissolution and subsequent vivianite precipitation, over time scales of days. The kinetics of the transformation are controlled by the dissolution rates of FeS. Aging and transformation of FeS, however, compete with vivianite formation. Aging is more pronounced at higher pH but is inhibited by P adsorption. Hence, the effect of pH and P concentration on aging is the main reason for the influence on these parameters on the rates and extent of vivianite formation. Our findings demonstrate that FeS can be an effective iron source for vivianite formation in aquatic sediments when sulfide concentrations decrease due to, for example, changes in external forcing or microbial sulfide oxidation. Formation of vivianite from FeS as an Fe source can also open new perspectives in P recovery in water treatment, for example when Fe is added to digesters to bind H₂S.

Ozonation of natural waters is typically associated with the formation of carbonyl compounds (aldehydes, ketones and ketoacids), a main class of organic disinfection byproducts (DBPs). However, the detection of carbonyl compounds in water and wastewater is challenged by multiple difficulties inherent to their physicochemical properties. A non-target screening method involving the derivatisation of carbonyl compounds with p-toluenesulfonylhydrazine (TSH) followed by their analysis using liquid chromatography coupled to electrospray ionisation high-resolution mass spectrometry (LC-ESI-HRMS) and an advanced non-target screening and data processing workflow was developed. The workflow was applied to investigate the formation of carbonyl compounds during ozonation of different water types including lake water, aqueous solutions containing Suwannee River Fulvic acid (SRFA), and wastewater. A higher sensitivity for most target carbonyl compounds was achieved compared to previous derivatisation methods. Moreover, the method allowed the identification of known and unknown carbonyl compounds. 8 out of 17 target carbonyl compounds were consistently detected above limits of quantification (LOQs) in most ozonated samples. Generally, the concentrations of the 8 detected target compounds decreased in the order: formaldehyde > acetaldehyde > glyoxylic acid > pyruvic acid > glutaraldehyde > 2,3-butanedione > glyoxal > 1-acetyl-1-cyclohexene. The DOC concentration-normalised formation of carbonyl compounds during ozonation was higher in wastewater and SRFA-containing water than in lake water. The specific ozone doses and the type of the dissolved organic matter (DOM) played a predominant role for the extent of formation of carbonyl compounds. Five formation trends were distinguished for different carbonyl compounds. Some compounds were produced continuously upon ozonation even at high ozone doses, while others reached a maximum concentration at a certain ozone dose above which they decreased. Concentrations of target and peak areas of non-target carbonyl compounds during full-scale ozonation at a wastewater treatment plant showed an increase as a function of the specific ozone dose (sum of 8 target compounds ∼ 280 µg/L at 1 mgO₃/mgC), followed by a significant decrease after biological sand filtration (> 64-94% abatement for the different compounds). This highlights the biodegradability of target and non-target carbonyl compounds and the importance of biological post-treatment.

Agronomic biofortification, encompassing the use of mineral and organic nutrient resources which improve micronutrient concentrations in staple crops is a potential strategy to promote the production of and access to micronutrient-dense foods at the farm level. However, the heterogeneity of smallholder farming landscapes presents challenges on implementing agronomic biofortification. Here, we test the effects of zinc (Zn)- and selenium (Se)-containing fertilizer on micronutrient concentrations of wheat (Triticum aestivum L.) and teff (Eragrostis tef (Zucc.) Trotter) grown under different landscape positions and with different micronutrient fertilizer application methods in the western Amhara region of Ethiopia. Field experiments were established in three landscape positions at three sites, with five treatments falling into three broad categories: (1) nitrogen (N) fertilizer rate; (2) micronutrient fertilizer application method; (3) sole or co-application of Zn and Se fertilizer. Treatments were replicated across five farms per landscape position and over two cropping seasons (2018 and 2019). Grain Zn concentration ranged from 26.6 to 36.4 mg kg^-1 in wheat and 28.5-31.2 mg kg^-1 in teff. Grain Se concentration ranged from 0.02 to 0.59 mg kg^-1 in wheat while larger concentrations of between 1.01 and 1.55 mg kg^-1 were attained in teff. Larger concentrations of Zn and Se were consistently attained when a foliar fertilizer was applied. Application of ⅓ nitrogen (N) yielded significantly larger grain Se concentration in wheat compared to a recommended N application rate. A moderate landscape effect on grain Zn concentration was observed in wheat but not in teff. In contrast, strong evidence of a landscape effect was observed for wheat and teff grain Se concentration. There was no evidence for any interaction of the treatment contrasts with landscape position except in teff, where an interaction effect between landscape position and Se application was observed. Our findings indicate an effect of Zn, Se, N, landscape position, and its interaction effect with Se on grain micronutrient concentrations. Agronomic biofortification of wheat and teff with micronutrient fertilizers is influenced by landscape position, the micronutrient fertilizer application method and N fertilizer management. The complexity of smallholder environmental settings and different farmer socio-economic opportunities calls for the optimization of nutritional agronomy landscape trials. Targeted application of micronutrient fertilizers across a landscape gradient is therefore required in ongoing agronomic biofortification interventions, in addition to the micronutrient fertilizer application method and the N fertilizer management strategy.

Bacterial biofilms can form in porous media that are of interest in industrial applications ranging from medical implants to biofilters as well as in environmental applications such as in situ groundwater remediation, where they can be critical locations for biogeochemical reactions. The presence of biofilms modifies porous media topology and hydrodynamics by clogging pores and consequently solutes transport and reactions kinetics. The interplay between highly heterogeneous flow fields found in porous media and microbial behavior, including biofilm growth, results in a spatially heterogeneous biofilm distribution in the porous media as well as internal heterogeneity across the thickness of the biofilm. Our study leverages highly resolved three-dimensional X-ray computed microtomography images of bacterial biofilms in a tubular reactor to numerically compute pore-scale fluid flow and solute transport by considering multiple equivalent stochastically generated internal permeability fields for the biofilm. We show that the internal heterogeneous permeability mainly impacts intermediate velocities when compared with homogeneous biofilm permeability. While the equivalent internal permeability fields of the biofilm do not impact fluid-fluid mixing, they significantly control a fast reaction. For biologically driven reactions such as nutrient or contaminant uptake by the biofilm, its internal permeability field controls the efficiency of the process. This study highlights the importance of considering the internal heterogeneity of biofilms to better predict reactivity in industrial and environmental bioclogged porous systems.

The unsaturated zone, located between the soil surface and the phreatic level, plays an important role in defining the fate of any substance entering the subsoil. In addition to the processes of flow and transport taking place in the liquid phase, surface reactions such as adsorption to the solid phase may occur and increase the residence time of the substance entering the system. In this study, we aim to understand the pore-scale mechanisms that control adsorption in unsaturated systems. We combine 2D pore-scale experimental images with numerical simulations to analyze flow, transport, and adsorption under different liquid saturation degrees. We demonstrate the role of mixing on adsorption at the liquid-solid interfaces by analyzing the deformation in time of a pulse-injected surfactant. We also analyze the impact of the isotherm functional shape and the inclusion of the liquid-gas interfaces as adsorption sites on this surface reaction. The enhancement of mixing as saturation decreases is accompanied by a reduction in the amount of adsorbed mass, located mainly along preferential flow paths, where the solute is primarily transported. For the same isotherm, a nonlinear behavior of adsorption as a function of liquid saturation has been observed. This is explained by the nonlinear variation of the volume fraction of liquid behaving as preferential path or stagnation zone as liquid saturation decreases, despite the linear decrease in the surface area of solids accessible for adsorption.

Models that simulate water flow and quality, particularly related to nitrate ions, are commonly used on a catchment-scale. However, tracking nitrate ions is a challenging task due to the intricate processes that affect them, such as phase exchanges, transformations, and interactions with various environmental media. In general, models capable of carrying out all tasks required to simulate water flow and quality at the same time, are rare. Additionally, most available models focus only on specific compartments of the watershed, such as surface water, topsoil, unsaturated zone, or groundwater. Taken together, these two challenges can lead to oversimplified representations of a system’s hydrology, as catchment internal processes become neglected due to missing information (lack of informative measurements, or models not focusing on all watershed compartments). Attempting to combine these models or to couple different watershed compartments results in complex calculations, increased run times, and a large number of parameters to estimate. Artificial Intelligence (AI) models have been massively used in environmental studies but, so far, the majority of them have been tested theoretically and not under real conditions. To overcome these challenges, stable isotope data are often employed to calibrate and validate internal catchment processes of these models. While water stable isotopes (δ¹⁸O and δ²H of H₂O) have been extensively used in many water flow models, the use of nitrate isotopes (δ¹⁵N and δ¹⁸O of NO₃^-) in water quality models remains poorly explored. Nitrate isotopes can help trace the origin of NO₃^– contamination and disentangle the complex reactions and dynamics that nitrate undergoes during transport. Hence, we propose that incorporating nitrate isotopes into catchment-scale water flow and quality models can substantially enhance the accuracy of these models. This review provides an overview of the current use of catchment hydrological models in predicting flow and fate of solutes. We discuss their limitations and highlight the potential of combining these models with nitrate isotopes. Ultimately, this approach may reduce prediction uncertainties and provide more effective guidance for water management decisions.

Water quality and its impacts on human and ecosystem health presents tremendous global challenges. While oxidative water treatment can solve many of these problems related to hygiene and micropollutants, identifying and predicting transformation products from a large variety of micropollutants induced by dosed chemical oxidants and in situ formed radicals is still a major challenge. To this end, a better understanding of the formed transformation products and their potential toxicity is needed. Currently, no theoretical tools alone can predict oxidatively induced transformation products in aqueous systems. Coupling experimental and theoretical studies has advanced the understanding of reaction kinetics and mechanisms significantly. This perspective article highlights the key progress made concerning experimental and computational approaches to predict transformation products. Knowledge gaps are identified, and the research required to advance the predictive capability is discussed.

An assessment of global groundwater quality is needed in response to the threats posed by anthropogenic and geogenic contaminants. This essay summarises the challenges involved, including a large number of potentially relevant water quality parameters, the poor availability of data in many regions and the complex nature of groundwater systems. Direct monitoring data can sometimes be augmented by indirect methods such as earth observations, and by involving citizen science. A new web portal is being developed to complement existing databases.

The helium isotope ratio (³He/⁴He), concentration ratio of neon-20 to helium-4 (²⁰Ne/⁴He), argon (Ar), krypton (Kr), and xenon (Xe) concentrations were measured in the porewater of surface sediments of several submarine mud volcanoes. From the ³He/⁴He values (0.18–0.93R_A), the estimated He origin is almost 90% crustal He, with little contribution from mantle-derived He. The determined Ar, Kr, and Xe concentrations lie within the solubility equilibrium range expected for temperatures from 83 °C up to 230 °C and are consistent with the temperature range of the dehydration origin of clay minerals. Considering the geothermal gradient in the investigated region (25 °C/km), these gases are considered to have reached dissolution equilibrium at a depth of about 3.3 km to 9.2 km below the seafloor. As the depth of the plate boundary is 18 km below the seafloor, the noble gas signatures are likely to originate from the crust, not from the plate boundary. This is consistent with the results presented by the He isotope ratios.

Grundwasser ist eine wichtige natürliche Ressource, die für die Trinkwasserversorgung, menschliche Aktivitäten, die Landwirtscha und das Funktionieren der Ökosysteme eine entscheidende Rolle spielt. Allerdings stehen die Grundwasserressourcen in der Schweiz aufgrund des Klimawandels vor grossen Herausforderungen. Der vorliegende Artikel gibt Einblick in die vorhergesagten Veränderungen.

An overview of the current state of knowledge on the pollution of agricultural soils with microplastic and nanoplastic (MnP) particles is provided and the main MnP sources are discussed. MnP transport mechanisms from soil to groundwater, as well as the potential impact of MnPs on soil structure are considered, and the relevance of co-contaminants such as agrochemicals is further highlighted. We elaborate on why MnPs in soil and groundwater are understudied and how analytical capabilities are critical for furthering this crucial research area. We point out that plastic fragmentation in soils can generate secondary MnPs, and that these smaller particles potentially migrate into aquifers. The transport of MnP in soils and groundwater and their migration and fate are still poorly understood. Higher MnP concentrations in agricultural soils can influence the sorption behavior of agrochemicals onto soil grains while attachment/detachment of MnPs onto soil grains and MnP-agrochemical interactions can potentially lead to enhanced transport of both MnP particles and agrochemicals towards underlying groundwater systems.

In diesem Artikel liefern wir einen Überblick über den derzeitigen Kenntnisstand zu Mikro- und Nanoplastikpartikeln (MnP) in landwirtschaftlich genutzten Böden einschließlich der wichtigsten Quellen. Die Transportmechanismen und Auswirkungen von MnP in Böden sowie mögliche Eintragspfade ins Grundwasser werden ebenso betrachtet wie die Bedeutung von Co-Kontaminanten. Wir erläutern, warum MnP in Boden und Grundwasser unbedingt weiterer Forschung bedarf und weisen darauf hin, dass durch die Fragmentierung von Plastik sekundäre MnP entstehen, und dass diese kleineren Partikel potenziell in Grundwasserleiter transportiert werden können. MnP in landwirtschaftlich genutzten Böden können das Sorptionsverhalten von Agrochemikalien verändern und die unterschiedliche Bindung/Ablösung von MnP an Bodenkörner und die Wechselwirkungen zwischen MnP und Agrochemikalien können möglicherweise zu einem verstärkten Eintrag von MnP und Agrochemikalien in Grundwassersysteme führen. Es zeigt sich im Allgemeinen, dass der Transport von MnP in Böden und Grundwasser nur unzureichend bekannt ist.

Ozone is a commonly applied disinfectant and oxidant in drinking water and has more recently been implemented for enhanced municipal wastewater treatment for potable reuse and ecosystem protection. One drawback is the potential formation of bromate, a possible human carcinogen with a strict drinking water standard of 10 μg/L. The formation of bromate from bromide during ozonation is complex and involves reactions with both ozone and secondary oxidants formed from ozone decomposition, i.e., hydroxyl radical. The underlying mechanism has been elucidated over the past several decades, and the extent of many parallel reactions occurring with either ozone or hydroxyl radicals depends strongly on the concentration, type of dissolved organic matter (DOM), and carbonate. On the basis of mechanistic considerations, several approaches minimizing bromate formation during ozonation can be applied. Removal of bromate after ozonation is less feasible. We recommend that bromate control strategies be prioritized in the following order: (1) control bromide discharge at the source and ensure optimal ozone mass-transfer design to minimize bromate formation, (2) minimize bromate formation during ozonation by chemical control strategies, such as ammonium with or without chlorine addition or hydrogen peroxide addition, which interfere with specific bromate formation steps and/or mask bromide, (3) implement a pretreatment strategy to reduce bromide and/or DOM prior to ozonation, and (4) assess the suitability of ozonation altogether or utilize a downstream treatment process that may already be in place, such as reverse osmosis, for post-ozone bromate abatement. A one-size-fits-all approach to bromate control does not exist, and treatment objectives, such as disinfection and micropollutant abatement, must also be considered.

In the lowlands of Nepal, as well as in several other South Asian countries, the level of arsenic in groundwater extracted from Quaternary alluvial sediments frequently exceeds the World Health Organization (WHO) drinking water guideline of 10 μg/L. The widely accepted explanation refers to the reductive dissolution of Fe-bearing minerals releasing As-oxyanions from the soil minerals. However, this hypothesis is only to some extent applicable. Given that arsenic and iron in the groundwater are weakly correlated or decoupled and iron(III) (hydr)oxides are scarcely present, a substantial portion of As and Fe has to be retained in clay minerals. The low concentration of iron in groundwater can be explained by the origin of As and Fe in the rocks (leucogranites); in the High Himalayas, they are low in Fe but considerably enriched in Li, B, As, Se, Br, Sr, Mo, Cd, P, and U. This unique geochemical setting has a major impact on the performance of the Kanchan Arsenic Filters (KAFs) used to eliminate As from groundwater in Nepal. Lack of sufficient Fe in groundwater, combined with limited release of iron by corrosion of iron nails, call for an adapted version of these filters. The first results from 20 modified filters show a clear increase in As removal efficiency, achieved mainly by the replacement of old nails, an added upper sand layer over the nails, and elongation of the outlet tube to avoid wet–dry cycles and to keep the nail bed immersed. Proper instructions to the users on the operation and maintenance of filters, by replacing the reactive materials (iron nails) and the lower sand bed regularly, are imperative.

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.

Carbon efflux from soils is the largest terrestrial carbon source to the atmosphere, yet it is still one of the most uncertain fluxes in the Earth’s carbon budget. A dominant component of this flux is heterotrophic respiration, influenced by several environmental factors, most notably soil temperature and moisture. Here, we develop a mechanistic model from micro to global scale to explore how changes in soil water content and temperature affect soil heterotrophic respiration. Simulations, laboratory measurements, and field observations validate the new approach. Estimates from the model show that heterotrophic respiration has been increasing since the 1980s at a rate of about 2% per decade globally. Using future projections of surface temperature and soil moisture, the model predicts a global increase of about 40% in heterotrophic respiration by the end of the century under the worst-case emission scenario, where the Arctic region is expected to experience a more than two-fold increase, driven primarily by declining soil moisture rather than temperature increase.

Knowledge of groundwater residence times (GRT; the time elapsed since surface water infiltration) between losing rivers and pumping wells is crucial for management of water resources in alluvial aquifers. The radioactive noble gas radon-222 (²²²Rn) has been used for decades as a natural indicator of surface water infiltration, as it can provide quantitative information on GRT. However, models using ²²²Rn as a tracer of GRT are often based on a set of highly simplifying assumptions, including spatially homogenous ²²²Rn production and exclusively advective mass transport within the aquifer. In this paper, we use the integrated surface-subsurface hydrological model HydroGeoSphere (HGS) to simulate ²²²Rn transport, production, and decay in a bank filtration context. Spatially variable ²²²Rn production, based on experimental data, is explicitly considered. We show that variable ²²²Rn production rates, coupled with hydrodispersive mixing of groundwater, may lead to large biases in GRT estimates. Under certain transient conditions however, changes in tracer-derived GRTs correlate well with changes in mean groundwater age. Whereas ²²²Rn-derived GRTs may only be reliable under a narrow range of field conditions, ²²²Rn may serve as a powerful tracer of changes in mean GRT even in complex and heterogenous environments.

We study mixing-controlled chemical reactions in unsaturated porous media from a pore-scale perspective. The spatial heterogeneity induced by the presence of two immiscible phases, here water and air, in the pore space generates complex flow patterns that dominate reactive mixing across scales. To assess the impact of different macroscopic saturation states (the fraction of pore volume occupied by water) on mixing-controlled chemical reactions, we consider a fast irreversible reaction between two initially segregated dissolved species that mix as one solution displaces the other in the heterogeneous flow field of the water phase. We use the pore-scale geometry and water distributions from the laboratory experiments reported by Jiménez-Martínez et al. (Geophys. Res. Lett. 42: 5316–5324, 2015). We analyze reactive mixing in three complementary ways. Firstly, we post-process experimentally observed spatially distributed concentration data; secondly, we perform numerical simulations of flow and reactive transport in the heterogeneous water phase, and thirdly, we use an upscaled mixing model. The first approach relies on an exact algebraic map between conservative and reactive species for an instantaneous irreversible bimolecular reaction that allows to estimate reactive mixing based on experimental conservative transport data. The second approach is based on reactive random walk particle tracking simulations in the numerically determined flow field in the water phase. The third approach uses a dispersive lamella approach that accounts for the impact of flow heterogeneity on mixing in terms of effective dispersion coefficients, which are estimated from both experimental data and numerical random walk particle tracking simulations. We observe a significant increase in reactive mixing for decreasing saturation, which is caused by the stronger heterogeneity of the water phase and thus of the flow field. This is consistently observed in the experimental data and the direct numerical simulations. The dispersive lamella model, parameterized by the effective interface width, provides robust estimates of the evolution of the product mass obtained from the experimental and numerical data.

Naturally occurring arsenic in groundwater affects millions of people around the world. In order to assess the extent of this problem, we have used machine learning to create a global prediction map of groundwater arsenic greater than 10 mg/L. The resulting model includes already known arsenic-affected areas as well as new potentially contaminated areas. Combining the global arsenic prediction model with household groundwater-usage statistics, we estimate that 94–220 million people are potentially exposed to high arsenic concentrations in groundwater. As groundwater is increasingly utilized to support a growing population and buffer against increasing water scarcity due to a changing climate, this model will help raise awareness, identify suitable areas for safe wells and guide where testing for arsenic should be prioritized.

Nanoplastik-Partikel (NP) werden bei einer klassischen Wasseraufbereitung bestehend aus Schnell- und Langsamsandfiltration sowie Aktivkohlefiltration gut aus Seewasser entfernt. Eine simulation einer Wasseraufbereitungsanlage ergab ein Eliminationseffizient von > 99,9%. Der Biofilm des Langsamsandfilters ist dabei das wichtigste Element. Die Ozonbehandlung verändert die NP kaum und hat somit keinen Einfluss auf den Rückhalt der NP bei der nachgeschalteten Sandund Aktivkohlefiltration.

Novel adsorbents produced from β-lactoglobulin, a low-cost milk protein, have shown a high affinity to inorganic As(_III) and As(_V). Here, we report an application-oriented investigation of As-removal from synthetic and spiked natural groundwaters with a protein nanofibril carbon composite adsorbent. In batch experiments, removal of both As(V) and As(III) was efficient and not strongly affected by variations in Mg²⁺, Ca²⁺, and HCO₃^-, while phosphate exerted a negative influence. 50-500 mg L^-1 of adsorbent was sufficient to reduce As-concentrations from 50–500 μg L^-1 to less than 10 μg L^-1. Adsorption kinetics were well-described by a second-order rate law. In rapid small scale column tests (RSSCTs) with 1.0 g sieved adsorbent, 100 μg L^-1 As(_III) and As(_V) in spiked tap water could be reduced to <1 μg L^-1 for over 40 000 bed volumes (BVs) and to <10 μg L^-1 for 50 000-70 000 BVs. Heavy metal ions (Cu, Zn, Pb) were also removed, but not nutrient ions such as Na⁺, Mg²⁺, Ca²⁺, Cl^-, SO₄^2-. With 1000 μg L^-1 As(_III,V) and P (phosphate), As and P were removed to <10 μg L^-1 over more than 5800 BVs. After regeneration with 10 mM NaOH, 2400 more BVs could be treated. The composites are an alternative to established Fe(III)(hydr)oxide-based adsorbents. Distinct advantages are high efficiencies for removal of As(_III) and As(_V), low effluent concentrations, and regenerability. The activated carbon carrier can also potentially remove organic compounds and unpleasant odors and tastes.

Recent studies suggested that long-lived photooxidants (LLPO), which are reactive intermediates formed during irradiation of dissolved organic matter (DOM), may consist of phenoxyl radicals derived from phenolic moieties of the DOM. Besides the well-studied excited triplet states of chromophoric DOM (³CDOM*), LLPO presumably are important photooxidants for the transformation of electron-rich contaminants in surface waters. The main objective of this study was to further test the potential role of phenoxyl radical as LLPO. Suwannee River fulvic acid (SRFA) as a model DOM was pre-oxidised using the phenol-reactive oxidants chlorine and ozone, followed by its characterization by the specific UV absorption at 254 nm (SUVA₂₅₄), the ratio of absorbance at λ = 254 nm and λ = 365 nm (E2:E3), and the electron donating capacity (EDC). Subsequently, the photoreactivity of pre-oxidized SRFA was tested using 3,4-dimethoxyphenol (DMOP) as a LLPO probe compound at two initial concentrations ([DMOP]₀ = 0.1 and 5.0 μM). Linear inter-correlations were observed for the relative changes in SUVA₂₅₄, E2:E3, and EDC for increasing oxidant doses. Pseudo-first-order transformation rate constants normalized to the changing SRFA absorption rate (i.e., and for 0.1 and 5.0 µM, respectively) exhibited the following distinct trends: The LLPO-dominated ratio decreased with increasing oxidant dose and with decreasing SUVA₂₅₄ and EDC, while the ³CDOM*-dominated ratio positively correlated with E2:E3. Finally, it was concluded that precursors of ³CDOM* and LLPO are chemically modified differently by pre-oxidation of DOM, and LLPO precursors likely consist of phenolic moieties of DOM, suggesting phenoxyl radicals as LLPO.

Lateral carbon transport through the land-to-ocean-aquatic-continuum (LOAC) represents a key component of the global carbon cycle. This LOAC involves complex processes, many of which are prone to anthropogenic perturbation, yet the influence of natural and human-induced drivers remains poorly constrained. This study examines the radiocarbon (¹⁴C) signatures of particulate and dissolved organic carbon (POC, DOC) and dissolved inorganic carbon (DIC) transported by Swiss rivers to assess controls on sources and cycling of carbon within their watersheds. Twenty-one rivers were selected and sampled during high-flow conditions in summer 2021, a year of exceptionally high rainfall. Δ¹⁴C values of POC range from -446‰ to -158‰, while corresponding ranges of Δ¹⁴C values for DOC and DIC are -377‰ to -43‰ and -301‰ to -40‰, respectively, indicating the prevalence of pre-aged carbon. Region-specific agricultural practices seem to have an influential effect on all three carbon phases in rivers draining the Swiss Plateau. Based on Multivariate Regression Analysis, mean basin elevation correlated negatively with Δ¹⁴C values of all three carbon phases. These contrasts between alpine terrain and the lowlands reflect the importance of overriding ecoregional controls on riverine carbon dynamics within Switzerland, despite high spatial variability in catchment properties.

Karst aquifers are important sources of fresh water on a global scale. The hydrological modelling of karst spring discharge, however, still poses a challenge. In this study we apply a transfer function noise (TFN) model in combination with a bucket-type recharge model to simulate karst spring discharge. The application of the noise model for the residual series has the advantage that it is more consistent with assumptions for optimization such as homoscedasticity and independence. In an earlier hydrological modeling study, named Karst Modeling Challenge (KMC; Jeannin et al., J Hydrol 600:126–508, 2021), several modelling approaches were compared for the Milandre Karst System in Switzerland. This serves as a benchmark and we apply the TFN model to KMC data, subsequently comparing the results to other models. Using different data-model-combinations, the most promising data-model-combination is identified in a three-step least-squares calibration. To quantify uncertainty, the Bayesian approach of Markov-chain Monte Carlo (MCMC) sampling is subsequently used with uniform priors for the previously identified best data-model combination. The MCMC maximum likelihood solution is used to simulate spring discharge for a previously unseen testing period, indicating a superior performance compared to all other models in the KMC. It is found that the model gives a physically feasible representation of the system, which is supported by field measurements. While the TFN model simulated rising limbs and flood recession especially well, medium and baseflow conditions were not represented as accurately. The TFN approach poses a well-performing data-driven alternative to other approaches that should be considered in future studies.

The Chari-Baguirmi region, southeastern of the Lake Chad (Africa), has a wide naturally occurring piezometric depression with values deeper than the expected regional groundwater level. To date, the most widely accepted hypotheses to explain its origin and dynamics are based on lack of rainwater infiltration and exfiltration processes. The code HYDRUS-1D is applied to numerically simulate the hydrological flow processes along the unsaturated zone in two soil profiles located in the central part and on the boundary of this piezometric depression under bare and vegetated soil coverage. The simulated time period is 2004–2015 with 715 mm annual rainfall average. The computed recharge with respect to total precipitation accounts for 21% on the boundary and 12% in the central part, which is limited by thick silty low permeability layer on the top surface. Considering modelling uncertainty and limitations under the simulated climatic conditions, the rainfall effect is observed only at upper soil layers, which leads to low aquifer recharge, while the upward water flux causing water table evaporation is very low. Past climate conditions, capable of developing a drying front to reach the water table after thousands of years of drying and geological structural constraints, may explain the current depressed area.

Known locally as the water mountain, for millennia Japan’s iconic Mt Fuji has provided safe drinking water to millions of people via a vast network of groundwater and freshwater springs. Groundwater, which is recharged at high elevations, flows down Fuji’s flanks within three basaltic aquifers, ultimately forming countless pristine freshwater springs among Fuji’s foothills. Here we challenge the current conceptual model of Fuji being a simple system of laminar groundwater flow with little to no vertical exchange between its three aquifers. This model contrasts strongly with Fuji’s extreme tectonic instability due to its unique location on top of the only known continental trench–trench–trench triple junction, its complex geology and its unusual microbial spring water communities. On the basis of a unique combination of microbial environmental DNA, vanadium and helium tracers, we provide evidence for prevailing deep circulation and a previously unknown deep groundwater contribution to Fuji’s freshwater springs. The most substantial deep groundwater upwelling has been found along Japan’s most tectonically active region, the Fujikawa-kako Fault Zone. Our findings broaden the hydrogeological understanding of Fuji and demonstrate the vast potential of combining environmental DNA, on-site noble gas and trace element analyses for groundwater science.

This study presents first-hand information on the occurrence of persistent organic pollutants (POPs) in the ambient air and surface soil along the Indus flood-plain, Pakistan. The sampling campaign was conducted at 15 site locations during 2014-15, along the Indus River (approximately 1300 km). Composite surface soil samples (N = 15) and passive air samples (N = 15) were collected for the estimation of gaseous POPs as well as air-soil exchange to evaluate the POP emission and distribution or dispersion patterns, source tracking, and contribution of the local and regional sources towards POP accumulation in the Indus River system. Among the studied POPs, levels of DDTs and PCBs were noticeably higher in ambient air (50-560 and 10-1100 pg m-3) and in soil (0.20-350 and 1.40-20 ng g-1), respectively. Regarding the spatial patterns, higher DDT concentrations (ng g-1) were detected in the air and soil samples collected from the wet mountain zone (WMZ) (p < 0.05), followed by the alluvial riverine zone (ARZ), low-lying mountain zone (LLZ), and frozen mountain zone (FMZ). The PCB data did not exhibit significant differences (p > 0.05) for the air samples, while PCB concentrations were significantly higher (p < 0.05) in soil from the LLZ, which may be associated with rapid urbanization and industrial activities in this area. The air-soil exchange of DDTs and PCBs showed net volatilization at most of the studied sites except for a few samples from the FMZ and WMZ. Results of this study about air-soil exchange gradients indicate the long range regional atmospheric transport (LRAT) of POPs to the colder areas (FMZ) of Pakistan, where these act as a secondary source of POPs in these areas.

Millions of people worldwide are exposed to arsenic (As) contaminated groundwater. Despite decades of research and evidence of As mobilisation in anoxic aquifers being caused by reductive dissolution of iron minerals, the mechanisms behind the local scale variability of dissolved As remains unclear. Therefore, the trans-disciplinary AdvectAs project investigates the environmental behaviour and spatial heterogeneity of dissolved As in groundwater in the Red River delta, Vietnam. Here we present the results from hydrochemical and water isotope investigations. In particular, we will show how the large As variability (0.1–510 mg/L) is related to consecutive As (im)mobilisation steps, depending on site hydrology, geology and the interplay of Fe, Mn, S and organic matter cycles. Such complexity of (im)mobilisation processes can be simplified in 5 major hydro(geo) chemical zones, providing a conceptual tool with potential for application at other sites in Asia affected by geogenic As contamination of groundwater.

Surface casing vents divert natural gas migration along oil and gas boreholes to bypass groundwater, with the gas venting to the atmosphere. While this strategy is designed to protect groundwater, it constitutes a source of greenhouse gases to the atmosphere. In instances where gas leakage occurs, the characterization of the molecular and isotopic composition of natural gas emitted from surface casing vent flows can be used to assist in identifying the gas source. We compare concentration measurements of non-hydrocarbon gases (within natural gas) of samples analyzed by laboratory-based gas chromatography (N₂, Ar, CO₂ and O₂) and magnetic sector noble gas mass spectrometry (He, Ar and Kr) with field measurements conducted using a field portable quadrupole mass spectrometer (miniRUEDI). The standard deviation of miniRUEDI concentration results was within plus/minus one standard deviation of samples measured using laboratory-based GC (N₂, O₂, Ar and He) and magnetic sector noble gas mass spectrometry (He, Ar). Additional laboratory-based determination of isotope ratios of methane and argon (δ¹³C_CH4, δ²H_CH4, and ⁴⁰Ar/³⁶Ar) enabled a comparison between information provided by the analysis of reactive gases compared with noble gas isotopes. Gases from different sources displayed quantifiable differences in δ¹³C_CH4 and δ²H_CH4, but these changes may or may not be distinguished if only one sampling event is conducted. By comparison, ⁴⁰Ar/³⁶Ar further enabled the differentiation of various gas sources. The objective of this paper is to discuss the advantages and trade-offs of the three different analysis methods considered, and the feasibility of their application in different environmental monitoring scenarios.

Compared to stratospheric SO₂ injection for climate intervention, alumina particle injection could reduce stratospheric warming and associated adverse impacts. However, heterogeneous chemistry on alumina particles, especially chlorine activation via (Formula presented.), is poorly constrained under stratospheric conditions, such as low temperature and humidity. This study quantifies the uncertainty in modeling the ozone response to alumina injection. We show that extrapolating the limited experimental data for ClONO₂ + HCl to stratospheric conditions leads to uncertainties in heterogeneous reaction rates of almost two orders of magnitude. Implementation of injection of 5 Mt/yr of particles with 240 nm radius in an aerosol-chemistry-climate model shows that resulting global total ozone depletions range between negligible and as large as 9%, that is more than twice the loss caused by chlorofluorocarbons, depending on assumptions on the degree of dissociation and interaction of the acids HCl, HNO₃, and H₂SO₄ on the alumina surface.

Background: Trihalomethanes (THM), a major class of disinfection by-products, are widespread and are associated with adverse health effects. We conducted a global evaluation of current THM regulations and concentrations in drinking water. Methods: We included 120 countries (∼7000 million inhabitants in 2016), representing 94% of the world population. We searched for country regulations and THM routine monitoring data using a questionnaire addressed to referent contacts. Scientific and gray literature was reviewed where contacts were not identified or declined participation. We obtained or estimated annual average THM concentrations, weighted to the population served when possible.
Results: Drinking water regulations were ascertained for 116/120 (97%) countries, with 89/116 (77%) including THM regulations. Routine monitoring was implemented in 47/89 (53%) of countries with THM regulations. THM data with a varying population coverage was obtained for 69/120 (58%) countries consisting of ∼5600 million inhabitants (76% of world's population in 2016). Population coverage was ≥90% in 14 countries, mostly in the Global North, 50–89% in 19 countries, 11–49% among 21 countries, and ≤10% in 14 countries including India, China, Russian Federation and Nigeria (40% of world's population).
Discussion: An enormous gap exists in THM regulatory status, routine monitoring practice, reporting and data availability among countries, especially between high- vs. low- and middle-income countries (LMICs). More efforts are warranted to regulate and systematically assess chemical quality of drinking water, centralize, harmonize, and openly report data, particularly in LMICs.

The quantification of carbon cycling across the groundwater–stream–atmosphere continuum (GSAC) is crucial for understanding regional and global carbon cycling. However, this quantification remains challenging due to highly coupled carbon exchange and turnover in the GSAC. Here, we disentangled carbon cycling processes in a representative groundwater–stream–atmosphere transect by obtaining and numerically simulating high-resolution time series of dissolved He, Ar, Kr, O₂, CO₂, and CH₄ concentrations. The results revealed that groundwater contributed ∼60% of CO₂ and ∼30% of CH₄ inputs to the stream, supporting stream CO₂ and CH₄ emissions to the atmosphere. Furthermore, diurnal variations in stream metabolism (-0.6 to 0.6 mol O₂ m^-2 day^-1) induced pronounced carbonate precipitation during the day and dissolution at night. The significant diurnal variability of biogeochemical processes emphasizes the importance of high-resolution time series investigations of carbon dynamics. This study shows that dissolved gases are promising environmental tracers for discerning and quantifying carbon cycling across the GSAC with high spatiotemporal resolution. Our high-resolution carbon exchange and turnover quantification provides a process-oriented and mechanistic understanding of carbon cycling across the GSAC.

The sealing characteristics of the geological formation located above a CO₂ storage reservoir, the so-called caprock, are essential to ensure efficient geological carbon storage. If CO₂ were to leak through the caprock, temporal changes in fluid geochemistry can reveal fundamental information on migration mechanisms and induced fluid–rock interactions. Here, we present the results from a unique in-situ injection experiment, where CO₂-enriched fluid was continuously injected in a faulted caprock analogue. Our results show that the CO₂ migration follows complex pathways within the fault structure. The joint analysis of noble gases, ion concentrations and carbon isotopes allow us to quantify mixing between injected CO₂-enriched fluid and resident formation water and to describe the temporal evolution of water–rock interaction processes. The results presented here are a crucial complement to the geophysical monitoring at the fracture scale highlighting a unique migration of CO₂ in fault zones.

Logistic regression modelling is a widely used prediction method to generate probability maps
of groundwater arsenic exceeding a selected threshold concentration. In this study, we converted logistic regression modelled probability maps to a pseudo contour map which comprehensively integrated important information of several probability maps of groundwater arsenic concentrations in Gujarat state, India. The pseudo contour map of groundwater arsenic concentrations clearly and intuitively indicates high groundwater arsenic concentrations (>10 mg/L) occurring in Kachchh District and Banas Kantha District and shows groundwater arsenic concentrations in northern and central Gujarat to be slightly higher than near the western
and eastern borders of the state. The cutoffs, where sensitivity equals specificity, is one of the most appropriate criteria of diagnosis of continuous probability results, better ensuring the accuracy of the generation of a pseudo contour map. However, the probability cutoff of each contour is likely different, so that the generated map is pseudo-contour rather than a contour map.

Amides are common constituents in natural organic matter and synthetic chemicals. In this study, we investigated kinetics and mechanisms of the reactions of chlorine with seven amides, including acetamide, N-methylformamide, N-methylacetamide, benzamide, N-methylbenzamide, N-propylbenzamide, and N-(benzoylglycyl)glycine amide. Apparent second-order rate constants for the reactions of the amides with chlorine at pH 8 are in the range of 5.8 × 10^-3 - 1.8 M^-1s^-1 and activation energies in the range of 62-88 kJ/mol. The second-order rate constants for the reactions of chlorine with different amides decrease with increasing electron donor character of the substituents on the amide-N and N-carbonyl-C in the amide structures. Hypochlorite (^-OCl) dominates the reactions of chlorine with amides yielding N-chloramides with species-specific second-order rate constants in the range of 7.3 × 10^-3 - 2.3 M^-1s^-1. Kinetic model simulations suggest that N-chlorinated primary amides further react with HOCl with second-order rate constants in the order of 10 M^-1s^-1. The chlorination products of amides, N-chloramides are reactive towards phenolic compounds, forming chlorinated phenols via electrophilic aromatic substitution (phenol and resorcinol) and quinone via electron transfer (hydroquinone). Meanwhile, N-chloramides were recycled to the parent amides. At neutral pH, apparent second-order rate constants for the reactions between phenols and N-chloramides are in the order of 10^-4-0.1 M^-1s^-1, comparable to those with chloramine. The findings of this study improve the understanding of the fate of amides and chlorine during chlorination processes.

Arsenic enrichment in groundwater resources in deltas and floodplains of large sediment-rich rivers is a worldwide natural hazard to human health. High spatial variability of arsenic concentrations in affected river basins limits cost-effective mitigation strategies. Linking the chemical composition of groundwater with the topography and fluvial geomorphology is a promising approach for predicting arsenic pollution on a regional scale. Here we correlate the distribution of arsenic contaminated wells with the fluvial dynamics in the Amazon basin. Groundwater was sampled from tube wells along the Amazon River and its main tributaries in three distinct regions in Peru and Brazil. For each sample, the major and trace element concentrations were analyzed, and the position of the well within the sedimentary structure was determined. The results show that aquifers in poorly weathered sediments deposited by sediment-rich rivers are prone to mobilization and accumulation of aqueous arsenic and manganese, both in sub-Andean foreland basins, and in floodplains downstream. Two zones at risk are distinguished: aquifers in the channel-dominated part of the floodplain (CDF) and aquifers in the overbank deposits on the less-dynamic part of the floodplain (LDF). Some 70 % of the wells located on the CDF and 20 % on the LDF tap groundwater at concentrations exceeding the WHO guideline of 10 μg/L arsenic (max. 430 μg/L), and 70 % (CDF) and 50 % (LDF) exceeded 0.4 mg/L manganese (max. 6.6 mg/L). None of the water samples located outside the actual floodplain of sediment-rich rivers, or on riverbanks of sediment-poor rivers exceed 5 μg/L As, and only 4 % exceeded 0.4 mg/L Mn. The areas of highest risk can be delineated using satellite imagery. We observe similar patterns as in affected river basins in South and Southeast Asia indicating a key role of sedimentation processes and fluvial geomorphology in priming arsenic and manganese contamination in aquifers.

Anaerobic microbial respiration in suboxic and anoxic environments often involves particulate ferric iron (oxyhydr-)oxides as terminal electron acceptors. To ensure efficient respiration, a widespread strategy among iron-reducing microorganisms is the use of extracellular electron shuttles (EES) that transfer two electrons from the microbial cell to the iron oxide surface. Yet, a fundamental understanding of how EES-oxide redox thermodynamics affect rates of iron oxide reduction remains elusive. Attempts to rationalize these rates for different EES, solution pH, and iron oxides on the basis of the underlying reaction free energy of the two-electron transfer were unsuccessful. Here, we demonstrate that broadly varying reduction rates determined in this work for different iron oxides and EES at varying solution chemistry as well as previously published data can be reconciled when these rates are instead related to the free energy of the less exergonic (or even endergonic) first of the two electron transfers from the fully, two-electron reduced EES to ferric iron oxide. We show how free energy relationships aid in identifying controls on microbial iron oxide reduction by EES, thereby advancing a more fundamental understanding of anaerobic respiration using iron oxides.

Chromium (Cr) contamination in paddy soil-rice systems threatens human health through the food chain. This study used a new dataset of 500 paddy soil and plant tissue samples collected in the rice-growing regions of Sindh and Punjab Provinces of Pakistan. Overall, 97.4% of grain samples exceeded the Cr threshold values of 1.0 mg kg⁻¹, determined by the China National Food Standard (CNFS). The Cr in paddy soil, 62.6% samples exceeding the China natural background threshold value (90 mg kg⁻¹) for Cr concentration in paddy soil, and lower than the (pH-dependant > 7.5 threshold value for Cr 350 mg kg⁻¹) as determined by China Environmental Quality Standards (EQSs) for paddy soil (GB15618-2018). Geographically weighted regression (GWR) modelling showed spatially nonstationary correlations, confirming the heterogeneous relationship between dependent (rice grain Cr) and independent paddy soil (pH, SOM, and paddy soil Cr) and plant tissue variables (shoot Cr and root Cr) throughout the study area. The GWR model was then used to determine the critical threshold (CT) for the measured Cr concentrations in the paddy soil system. Overall, 38.4% of paddy soil samples exceeding CT values confirm that the paddy soil Cr risk prevails in the study area. Furthermore, the GWR model was applied to assess the loading capacity (LC), the difference between the CT, and the actual concentration of Cr in paddy soil. Loading capacity identified potential paddy soil Cr pollution risk to rice grain and assessed the risk areas. Overall LC% of samples paddy soil Cr risk areas grade: low-risk grade I (34.6%); moderate-risk grade II (15.8%); high-risk grade III (11.2%); and very high-risk grade IV (38.4%) have been assessed in the study area. The human health index, total hazard quotient (THQ ≪ 1), indicates no potential health risk originating from Cr exposure to the population. However, the excess Cr level in paddy soil and rice grain is still a concern. The current study's results are also valuable for the national decision-making process regarding Cr contamination in the paddy soil-rice system.

The sedimentary infill of glacially overdeepened valleys (i.e., structures eroded below the fluvial base level) is an excellent but yet underexplored archive with regard to the age, extent, and nature of past glaciations. The ICDP project DOVE (Drilling Overdeepened Alpine Valleys) Phase 1 investigates a series of drill cores from glacially overdeepened troughs at several locations along the northern front of the Alps. All sites will be investigated with regard to several aspects of environmental dynamics during the Quaternary, with focus on the glaciation, vegetation, and landscape history. Geophysical methods (e.g., seismic surveys), for example, will explore the geometry of overdeepened structures to better understand the process of overdeepening. Sedimentological analyses combined with downhole logging, analysis of biological remains, and state-of-the-art geochronological methods, will enable us to reconstruct the erosion and sedimentation history of the overdeepened troughs. This approach is expected to yield significant novel data quantifying the extent and timing of Middle and Late Pleistocene glaciations of the Alps. In a first phase, two sites were drilled in late 2021 into filled overdeepenings below the paleolobe of the Rhine Glacier, and both recovered a trough filling composed of multiphase glacial sequences. Fully cored Hole 5068_1_C reached a depth of 165 m and recovered 10 m molasse bedrock at the base. This hole will be used together with two flush holes (5068_1_A, 5068_1_B) for further geophysical cross-well experiments. Site 5068_2 reached a depth of 255 m and bottomed out near the soft rock–bedrock contact. These two sites are complemented by three legacy drill sites that previously recovered filled overdeepenings below the more eastern Alpine Isar-Loisach, Salzach, and Traun paleoglacier lobes (5068_3, 5068_4, 5068_5). All analysis and interpretations of this DOVE Phase 1 will eventually lay the ground for an upcoming Phase 2 that will complete the pan-Alpine approach. This follow-up phase will investigate overdeepenings formerly occupied by paleoglacier lobes from the western and southern Alpine margins through drilling sites in France, Italy, and Slovenia. Available geological information and infrastructure make the Alps an ideal area to study overdeepened structures; however, the expected results of this study will not be restricted to the Alps. Such features are also known from other formerly glaciated mountain ranges, which are less studied than the Alps and more problematic with regards to drilling logistics. The results of this study will serve as textbook concepts to understand a full range of geological processes relevant to formerly glaciated areas all over our planet.

Space-Lagrangian random walk models conceptualize advective transport in terms of collections of particles undergoing fixed-length steps along flow streamlines. The statistics and correlation structure of the underlying flow velocity statistics determine the transit times of particles undergoing advective transport. Broad velocity distributions lead to broadly distributed step transit times, reproducing commonly observed anomalous transport features such as superdiffusive plume growth, which are not captured by classical Fickian theories. Early space-Lagrangian models considered uncorrelated velocities across steps. These approaches were later extended to account for correlations through a spatial-Markov process. Here, we compare longitudinal dispersion dynamics in an uncorrelated continuous-time random walk with fixed-space steps to a Bernoulli relaxation spatial-Markov model exhibiting exponential decay of spatial velocity correlations along streamlines. We provide rigorous theoretical derivations, validated against numerical simulations. We find that, although the scaling forms of asymptotic dispersion agree between the two models, exact asymptotic equivalence requires employing different correlation lengths, which depend on the underlying Eulerian velocity statistics. The two models become equivalent in the limit of very broad velocity distributions, corresponding to a new quasiballistic regime recently identified in unsaturated porous media, which we rigorously characterize here.

Most people in Ghana have no or only basic access to safely managed water. Especially in rural areas, much of the population relies on groundwater for drinking, which can be contaminated with fluoride and lead to dental fluorosis. Children under the age of two are particularly susceptible to the adverse effects of fluoride and can retain 80-90% of a fluoride dose, compared to 60% in adults. Despite numerous local studies, no spatially continuous picture exists of the fluoride contamination across Ghana, nor is there any estimate of what proportion of the population is potentially exposed to unsafe fluoride levels. Here, we spatially model the probability of fluoride concentrations exceeding 1.0 mg/L in groundwater across Ghana to identify risk areas and estimate the number of children and adults exposed to unsafe fluoride levels in drinking water. We use a set of geospatial predictor variables with random forest modeling and evaluate the model performance through spatial cross-validation. We found that approximately 15% of the area of Ghana, mainly in the northeast, has a high probability of fluoride contamination. The total at-risk population is about 920,000 persons, or 3% of the population, with an estimated 240,000 children (0-9 years) in at-risk areas. In some districts, such as Karaga, Gushiegu, Tamale and Mion, 4 out of 10 children are potentially exposed to fluoride poisoning. Geology and high evapotranspiration are the main drivers of fluoride enrichment in groundwater. Consequently, climate change might put even greater pressure on the area's water resources. Our hazard maps should raise awareness and understanding of geogenic fluoride contamination in Ghana and can advise decision making at local levels to avoid or mitigate fluoride-related risks.

Brunei has made significant progress in agricultural development over the past four decades. However, crop production, such as rice, is still insufficient to meet the demands of the growing population, mainly due to the scarcity of water resources, acidic soils, and advancing environmental deterioration. This study conducted soil and groundwater investigations at three selected rice cultivation sites in Brunei Darussalam. The geoelectrical resistivity method using the vertical electrical sounding (VES) technique delineated subsurface stratigraphy with resistivities ranging from 1 to 180 Ωm in the investigated area. A potential aquifer zone was inferred in one of the surveyed areas with resistivities ranging from 10 to 150 Ωm at depths of about 40 to 60 m below ground level. Groundwater levels were also shallower in irrigated sites compared to non-irrigated sites. Groundwater physicochemical properties revealed high alkalinity and mineralisation, as evident from high magnesium, bicarbonate, ammoniacal nitrogen, and iron, as well as pH values in the water samples, believed to be the effects of leaching of salt ions into the shallow aquifer through infiltration recharge. In addition, soil physicochemical properties showed that the soils near a pumping well were more acidic, had lower moisture, and total nutrients, likely due to the effects of groundwater pumping. Our results demonstrate that future irrigation activities need to consider local aquifer characteristics, groundwater flow paths, and nutrient transport to ensure sustainable development in agricultural areas.

Mitigation measures are needed to prevent large loads of phosphate originating in agriculture from reaching surface waters. Iron-coated sand (ICS) is a residual product from drinking water production. ICS has a high phosphate adsorption capacity and can be placed around tile drains taking no extra space which increases the farmers’ acceptance. The main concern regarding the use of ICS filters below groundwater level is that limited oxygen supply and high organic matter concentrations may lead to the reduction and dissolution of iron (hydr)oxides present and the release of previously adsorbed phosphate. This study aimed to investigate phosphate adsorption on ICS at the onset of iron reduction. First, it was investigated whether simultaneous metal reduction and phosphate adsorption were relevant at two field sites in the Netherlands that use ICS filters around tile drains. Second, the onset of microbially mediated reduction of ICS in drainage water was mimicked in complementary laboratory microcosm experiments by varying the intensity of reduction through controlling the oxygen availability and the concentration of degradable organic matter. After 3 years, ICS filters in the field removed phosphorus under low redox conditions. Over 45 days, the microbial reduction of manganese and iron oxides did not lead to phosphate release confirming field observations. Electron microscopy and X-ray absorption spectroscopy did not evince systematic structural or compositional changes, only under strongly reducing conditions did iron sulfides formed in small percentages in the outer layer of the iron coating. Our results suggest that detrimental effects only become relevant after long operation periods.

Groundwater is an invaluable global resource, but its long-term viability as a resource for consumption, agriculture, and ecosystems depends on precipitation recharging aquifers. How much precipitation recharges groundwaters varies enormously across Earth's surface, yet recharge rates often remain uncertain. Here we use a global synthesis of field-estimated recharge across six continents to show that globally recharge first-order follows a simple function of climatic aridity. We use this relationship to estimate long-term recharge in energy-limited systems outside of permafrost regions. Our aridity-based recharge estimates are consistent with the global field data but, on average, double previous estimates of global models. Our higher recharge estimates are likely caused by preferential groundwater recharge and discharge occurring at grid scales finer than global models. The higher recharge estimates suggest that more groundwater contributes to evapotranspiration and streamflow than previously represented by global hydrological models and global water cycle diagrams.

Labeling groundwater by injecting an artificial tracer is a standard and widely used method to study groundwater flow systems. Noble gases dissolved in groundwater are potentially ideal artificial tracers, as they are not subject to biogeochemical transformations, do not adsorb onto the aquifer matrix, are colorless, and have no negative impact on the quality of groundwater resources. In addition, combining different noble-gas species in multi-tracer tests would allow direct analysis of the spatio-temporal heterogeneity of groundwater flow systems. However, while the handling of noble gases is safe and straightforward for injection into groundwater, conventional methods to analyse dissolved noble gases tend to be impractical for groundwater tracer tests. The sampling and subsequent lab-based analysis of dissolved noble gases are laborious, expensive and time intensive. Therefore, only researchers with access to specialized noble-gas labs have attempted such tracer tests. The recently developed gas-equilibrium membrane-inlet mass spectrometers (GE-MIMS) allow efficient on-site analysis of dissolved gases at high temporal resolution. The GE-MIMS instruments thereby eliminate most of the analytical and logistical constraints of conventional lab-based techniques and therefore provide new opportunities for groundwater tests using artificially injected gases. We used a GE-MIMS to systematically test the applicability of He, Kr, and Xe as artificial groundwater tracers. These gas species were injected into groundwater as Dirac-like pulses at three piezometers located at various locations upstream of a pumping well, where dissolved gas concentrations were continuously monitored with the GE-MIMS instrument. The groundwater travel times observed in these tracer tests ranged from a few hours to several weeks, and were consistent with the groundwater flow field at the experimental test site. Travel times determined from the noble gas tracer tests were also consistent with those obtained traditional dye tracers.

Arsenic (As) is one of the most prolific natural contaminants in water resources, and hence, it has been recognized as an emerging global problem. Arsenic exposure through food exports and imports, such as As-contaminated rice and cereal-based baby food, is a potential risk worldwide. However, ensuring As-safe drinking water and food for the globe is still not stated explicitly as a right neither in the United Nations' Universal Declaration of Human Rights and the 2030 Sustainable Development Goals (SDGs) nor the global UNESCO priorities. Despite these omissions, addressing As contamination is crucial to ensure and achieve many of the declared human rights, SDGs, and global UNESCO priorities. An international platform for sharing knowledge, experience, and resources through an integrated global network of scientists, professionals, and early career researchers on multidisciplinary aspects of As research can act as an umbrella covering the activities of UN, UNESCO, and other UN organizations. This can deal with the mitigation of As contamination, thus contributing to global economic development and human health. This article provides a perspective on the global As problem for sustainable As mitigation on a global scale by 2030.

Lake Kivu is a 485 m deep, Central-East African rift lake with huge amounts of carbon dioxide and methane dissolved in its stably stratified deep waters. In view of future large-scale methane extraction, one-dimensional numerical modelling is an important and computationally inexpensive tool to analyze the evolution of stratification and the content of gases in Lake Kivu. For this purpose, we coupled the physical lake model Simstrat to the biogeochemical library AED2. Compared to an earlier modelling approach, this coupled approach offers several key improvements, most importantly the dynamic evaluation of mixing processes over the whole water column, including a parameterization for double-diffusive transport, and the density-dependent stratification of groundwater inflows. The coupled model successfully reproduces today's near steady-state of Lake Kivu, and we demonstrate that a complete mixing event ∼2000 years ago is compatible with today's physical and biogeochemical state.

The carbonate radical CO₃^•- and the excited triplet states of chromophoric dissolved organic matter play an important role in the photodegradation of some easily oxidized pollutants in surface waters, such as the aromatic amines. Anilines and sulfadiazine are known to undergo back-reduction processes when their degradation is mediated by the excited triplet states of photosensitizers (triplet sensitization). Back-reduction, which inhibits photodegradation, means that phenols or the antioxidant (mostly phenolic) moieties occurring in the natural dissolved organic matter of surface waters reduce, back to the parent compounds, the radical species derived from the mono-electronic oxidation of anilines and sulfadiazine. Here we show that a similar process takes place as well in the case of substrate oxidation by CO₃^•−. The carbonate radical was here produced upon oxidation of HCO₃^-/CO₃^2- by either HO^•, generated by nitrate photolysis, or SO₄^•-, obtained by photolysis of persulfate. Back-reduction was observed in both cases in the presence of phenols, but at different extents as far as the details of reaction kinetics are concerned, and the occurrence of additional reductants might affect the efficacy by which phenols carry out the reduction process. In particular, when the carbonate radicals were produced by NO₃^– photolysis in the presence of HCO₃^-/CO₃^2-, the numerical values of [PhOH]_1/2 (the phenol concentration that halves the photodegradation rate of the substrate) were 2.19 ± 0.23 µM for aniline, 1.15 ± 0.25 µM for 3-chloroaniline, 1.18 ± 0.26 µM for 4-chloroaniline, and 1.18 ± 0.22 µM for 3,4-dichloroaniline. In contrast, when CO₃^•- was produced by photolysis of persulfate in the presence of HCO₃^-/CO₃^2-, the corresponding values were 0.28 ± 0.02 µM for aniline and 0.79 ± 0.10 µM for sulfadiazine. Back-reduction has the potential to significantly inhibit photodegradation by CO₃^•− and excited triplet states in natural waters, and to comparatively increase the importance of HO^•-mediated degradation that is not affected by the same phenomenon.

Mitigation measures are needed for reducing chronic dissolved phosphorus (P) losses from agricultural soils with a legacy of excessive P inputs to surface waters. Since pipe drains are an important pathway for P transport from agricultural soils to surface waters in flat areas, removing P from drainage water can be an effective measure. During a 4.5 year-field experiment, we tested the performance of a pipe drain enveloped with Fe-coated sand for removing soluble P from drainage water. Iron-coated sand is a by-product of the drinking water industry and has a high ability to bind P. The P concentration in the effluent from the enveloped pipe drain remained at a very low level over the entire monitoring period, with a removal percentage amounting to 93% for total P. During the field experiment, the enveloped pipe drain was below the groundwater level for a prolonged time. Nevertheless, no reduction of Fe(III) in the Fe-coated sand occurred during the first two years, most likely due to preferential reduction of Mn oxides present in the coatings of the sand particles, as reflected in elevated effluent Mn concentrations. Thereafter, reductive dissolution of Fe oxides in the coatings caused a gradual increase in the Fe concentration in the enveloped pipe drain effluent over time. Concomitantly, the dissolved Mn concentration decreased, most probably due to the depletion in easily accessible Mn oxides in the Fe-coated sand. The Fe in the Fe-coated sand was identified as silicate-containing ferrihydrite (Fh). The submerged conditions of the enveloped pipe drain neither affected the stability of Fh in the Fe-coated sand nor the ability of this measure to capture P from drainage water. Enveloping pipe drains with Fe-coated sand is an effective method for reducing dissolved P inputs from agricultural soils to surface waters and holds great promise for implementation in practice.

Biofilms are biological viscoelastic gels composed of bacterial cells embedded in a self-secreted polymeric extracellular matrix (ECM). In environmental settings, such as in the rhizosphere and phyllosphere, biofilm colonization occurs at the solid–air interface. The biofilms’ ability to colonize and expand over these surfaces depends on the formation of osmotic gradients and ECM viscoelastic properties. In this work, we study the influence of biofilm ECM components on its viscoelasticity and expansion, using the model organism Bacillus subtilis and deletion mutants of its three major ECM components, TasA, EPS and BslA. Using a multi-scale approach, we quantified macro-scale viscoelasticity and expansion dynamics. Furthermore, we used a microsphere assay to visualize the micro-scale expansion patterns. We find that the viscoelastic phase angle Φ is likely the best viscoelastic parameter correlating to biofilm expansion dynamics. Moreover, we quantify the sensitivity of the biofilm to changes in substrate water potential as a function of ECM composition. Finally, we find that the deletion of ECM components significantly increases the coherence of micro-scale colony expansion patterns. These results demonstrate the influence of ECM viscoelasticity and substrate water potential on the expansion of biofilm colonies on wet surfaces at the air–solid interface, commonly found in natural environments.

Environmental gas tracers allow inferring groundwater travel times and mixing ratios. Their concentrations are commonly interpreted with simplified and indirect approaches that are conceptually at odds with the high degree of complexity found in natural systems. However, the information content of the tracers can potentially be fully explored through the explicit simulation of an advection-dispersion transport equation, for example using integrated surface-subsurface hydrological models (ISSHMs). These integrated models can be used to explicitly simulate environmental tracers in complex environments. ISSHMs are usually variably saturated flow models. However, these models do not explicitly simulate gas partitioning with the aqueous phase, restricting explicit simulation of gas tracers to fully saturated conditions or to tracers with very low solubilities. We propose a mathematical formulation for the production of environmental gas tracers that are emanated in the subsurface. The production is scaled according to gas/water partitioning and water saturation, which is already computed by the model. Therefore, ISSHMs can now be used to their full potential to explicitly simulate tracer concentrations under variably saturated and dynamic conditions. The new formulation has been successfully verified against reference simulations provided with a multi-phase flow and transport model. In addition, explicit simulation of ²²²Rn and ³⁷Ar groundwater concentrations in a synthetic alluvial river-groundwater system was demonstrated, for the first time, with an ISSHM.

The residual non-wetting phase in unsaturated porous media varies the aqueous pore space due to the immiscible characteristics. The varied pore space in turn has significant influence on the mass transfer for aqueous tracer transport through residual unsaturated porous media. In this study, the mass transfer for solute transport through residual unsaturated porous media was investigated. A pore-scale numerical simulation (PSNS) model consisting of both immiscible two-phase flow transport and aqueous-miscible solute transport was developed at pore scale to capture the topology of residual saturation and the tempo-spatial evolution of aqueous tracer in residual unsaturated porous media. The results showed that as the immiscible fluid-fluid displacement pattern varied from compact displacement to capillary fingering, the residual saturation (S_rw) increased and the velocity spatial variability in the residual aqueous flow field was enhanced. Inversion of the advection-dispersion-equation (ADE) model and the continuous-time-random-walk (CTRW) model indicated the typical characteristics of anomalous aqueous tracer transport (i.e., early arrivals and long tails) in breakthrough curves (BTCs) in a range of (S_rw) from 0.098 to 0.542. A non-monotonic relationship was found between the dispersivity and the S_rw. Further, analysis of the overall dispersivity of aqueous tracer in terms of the mobile-immobile-type transport equation showed the coexistence of two mass transfer mechanisms (i.e., the dispersivity of the mobile domain and the solute exchange between the mobile and immobile domains). We introduced a dimensionless dispersivity index to quantify the relative contribution of these two mass transfer mechanisms to the overall dispersivity. However, it was found that the mass transfer of aqueous tracer in residual unsaturated porous media was controlled by the dispersion of aqueous tracer in the mobile domain at low S_rw, whereas it was dominated by the solute exchange between the mobile and immobile domains at high S_rw. Our study not only highlighted the saturation dependence of mass transfer in residual unsaturated porous media, but also emphasized the importance of the influence of saturation topology on mass transfer.

We present noble gas concentrations and helium isotope ratios measured in the pore fluids of two deep-sea sediment cores taken at the Azores Plateau. Ne-Xe concentrations were used to estimate the atmospheric noble gas component within the pore fluids and to then determine the terrigenic helium component. The concentrations of terrigenic ³He indicate the presence of hydrothermal fluids and a mantle He component within the sediment pore space. At both sampling locations, the concentration of terrigenic helium increases with sediment depth. The observed concentration gradients suggest a diffusive transport of He through the sediments. The helium isotope ratio of the source of the terrigenic helium is characterized by a typical mid-ocean ridge basalt (MORB). These results support previous studies suggesting that the pelagic sediments surrounding the Azores host active hydrothermal systems.
Our data indicate that the transport of terrigenic helium takes place diffusively over larger areas of the ocean floor, and that the concentration of terrigenic helium in the pelagic sediments increases towards the Mid-Atlantic Ridge and Terceira Rift.
The data further suggests that in the Azores region the terrigenic noble gas component is only detectable in the sediment pore fluids and cannot be observed in the overlying bottom water. This highlights the potential of measuring noble gas concentrations and isotope ratios in the sediment column to identify hydrothermal activity in the ocean.

The composition of oxidant-reactive dissolved organic nitrogen (DON) is poorly characterized, although its ozonation is likely to form a great variety of disinfection by-products containing a nitrogen-oxygen bond (N-DBPs). In this study, two chemical oxidation procedures were developed: continuous ozonation at pH 7.0 and free available chlorine (FAC) titrations at pH 9.2. The formation of two oxidation products (nitrate (NO₃^-) and chloramines, respectively) was used to quantify and characterize oxidant-reactive nitrogenous moieties in DON. In addition, batch experiments were conducted to study the NO₃^- yields of 30 selected nitrogenous model compounds upon ozonation. The NO₃^- yields of 12 primary and secondary amines were highly variable (17-100%, specific ozone dose of 20 mol_O3/mol_N), 7 amino acids had high NO₃^- yields (≥90%), and tertiary amines as well as pyrrole, acetamide and urea had low NO₃^- yields (≤15%). The mechanisms of NO₃^- formation were further examined with benzylamine and N-methylbenzylamine as model compounds. Our results show that nitroalkanes are the last intermediate products before the formation of NO₃^-, both for primary and secondary amines. The presence of an electron-withdrawing group in the vicinity of the N-atom facilitates the formation of NO₃^- from nitroalkanes. Therefore, the formation of NO₃^- is attributed to amino acids and activated primary and secondary amines. In contrast, all primary and secondary amines were transformed to chloramines upon chlorination, which was determined by a novel oxidative titration with chlorine. To further support the selectivity of this assay, it was demonstrated by derivatization of amine moieties that chloramine formation could be inhibited. 13-45% of the DON of 4 dissolved organic matter isolates and 2 wastewater effluents formed NO₃^- and 0-39% formed chloramines, indicating that the potential for N-DBP formation is high (µM_N/mg_C-level). From differences in the formation of NO₃^- and chloramines the nature of the precursors can be hypothesized (e.g., activated or non-activated primary and secondary amines, partially oxidized nitrogenous compounds). This study highlights the capacity of two novel methods to characterize the oxidant-reactive DON fraction. Our results suggest that this fraction is significant and could form a variety of potentially toxic N-DBPs.

Ozone in the Arctic stratosphere is subject to large interannual variability, driven by both chemical ozone depletion and dynamical variability. Anomalies in Arctic stratospheric ozone become particularly important in spring, when returning sunlight allows them to alter stratospheric temperatures via shortwave heating, thus modifying atmospheric dynamics. At the same time, the stratospheric circulation undergoes a transition in spring with the final stratospheric warming (FSW), which marks the end of winter. A causal link between stratospheric ozone anomalies and FSWs is plausible and might increase the predictability of stratospheric and tropospheric responses on sub-seasonal to seasonal timescales. However, it remains to be fully understood how ozone influences the timing and evolution of the springtime vortex breakdown. Here, we contrast results from chemistry climate models with and without interactive ozone chemistry to quantify the impact of ozone anomalies on the timing of the FSW and its effects on surface climate. We find that ozone feedbacks increase the variability in the timing of the FSW, especially in the lower stratosphere. In ozone-deficient springs, a persistent strong polar vortex and a delayed FSW in the lower stratosphere are partly due to the lack of heating by ozone in that region. High-ozone anomalies, on the other hand, result in additional shortwave heating in the lower stratosphere, where the FSW therefore occurs earlier. We further show that FSWs in high-ozone springs are predominantly followed by a negative phase of the Arctic Oscillation (AO) with positive sea level pressure anomalies over the Arctic and cold anomalies over Eurasia and Europe. These conditions are to a significant extent (at least 50 %) driven by ozone. In contrast, FSWs in low-ozone springs are not associated with a discernible surface climate response. These results highlight the importance of ozone-circulation coupling in the climate system and the potential value of interactive ozone chemistry for sub-seasonal to seasonal predictability.

Large-scale chemical depletion of ozone due to anthropogenic emissions occurs over Antarctica as well as, to a lesser degree, the Arctic. Surface climate predictability in the Northern Hemisphere might be improved due to a previously proposed, albeit uncertain, link to springtime ozone depletion in the Arctic. Here we use observations and targeted chemistry–climate experiments from two models to isolate the surface impacts of ozone depletion from complex downward dynamical influences. We find that springtime stratospheric ozone depletion is consistently followed by surface temperature and precipitation anomalies with signs consistent with a positive Arctic Oscillation, namely, warm and dry conditions over southern Europe and Eurasia and moistening over northern Europe. Notably, we show that these anomalies, affecting large portions of the Northern Hemisphere, are driven substantially by the loss of stratospheric ozone. This is due to ozone depletion leading to a reduction in short-wave radiation absorption, when in turn causing persistent negative temperature anomalies in the lower stratosphere and a delayed break-up of the polar vortex. These results indicate that the inclusion of interactive ozone chemistry in atmospheric models can considerably improve the predictability of Northern Hemisphere surface climate on seasonal timescales.

Oxidative treatment of seawater in coastal and shipboard installations is applied to control biofouling and/or minimize the input of noxious or invasive species into the marine environment. This treatment allows a safe and efficient operation of industrial installations and helps to protect human health from infectious diseases and to maintain the biodiversity in the marine environment. On the downside, the application of chemical oxidants generates undesired organic compounds, so-called disinfection by-products (DBPs), which are discharged into the marine environment. This article provides an overview on sources and quantities of DBP inputs, which could serve as basis for hazard analysis for the marine environment, human health and the atmosphere. During oxidation of marine water, mainly brominated DBPs are generated with bromoform (CHBr₃) being the major DBP. CHBr₃ has been used as an indicator to compare inputs from different sources. Total global annual volumes of treated seawater inputs resulting from cooling processes of coastal power stations, from desalination plants and from ballast water treatment in ships are estimated to be 470-800 × 10⁹ m³, 46 × 10⁹ m³ and 3.5 × 10⁹ m³, respectively. Overall, the total estimated anthropogenic bromoform production and discharge adds up to 13.5-21.8 × 10⁶ kg/a (kg per year) with contributions of 11.8-20.1 × 10⁶ kg/a from cooling water treatment, 0.89 × 10⁶ kg/a from desalination and 0.86 × 10⁶ kg/a from ballast water treatment. This equals approximately 2–6% of the natural bromoform emissions from marine water, which is estimated to be 385-870 × 10⁶ kg/a.

The aim of this research was the analysis of the effect of a dam height raise on the water quality of a tropical reservoir used for drinking water purposes in South East Asia. Analyses of iron, manganese, pH and ammonia were performed over a 5-year period from daily water sampling at the reservoir. In addition, high-frequency monitoring data of nitrate, ammonium, pH and blue-green algae were obtained using a monitoring probe. The results showed that due to the raising of the reservoir water level, previously oxic sediments became submerged, triggering an increase in iron and manganese in particular due to the establishment of reducing conditions. Manganese concentrations with values up to 4 mg L^-1 are now exceeding guideline values. The analysis strongly indicated that both iron and manganese have a seasonal component with higher iron and manganese concentrations during the wet season. Over a three-year period afterwards, concentrations did not go back to pre-raise levels. The change in water quality was accompanied by a change in pH from previous values of around 5 to pH values of around 6.5. Geochemical simulations confirmed the theory that the increasing concentrations of iron and manganese are due to the dissolution of MnO₂ and ferric oxyhydroxides oxidising organic matter in the process. This study showed that changes in reservoir water levels with the establishment of reducing conditions can have long-term effects on the water quality of a reservoir.

Even though lake sediments are globally important organic carbon (OC) sinks, the controls on long-term OC storage in these sediments are unclear. Using a multiproxy approach, we investigate changes in diatom, green algae, and vascular plant biomolecules in sedimentary records from the past centuries across five temperate lakes with different trophic histories. Despite past increases in the input and burial of OC in sediments of eutrophic lakes, biomolecule quantities in sediments of all lakes are primarily controlled by postburial microbial degradation over the time scales studied. We, moreover, observe major differences in biomolecule degradation patterns across diatoms, green algae, and vascular plants. Degradation rates of labile diatom DNA exceed those of chemically more resistant diatom lipids, suggesting that chemical reactivity mainly controls diatom biomolecule degradation rates in the lakes studied. By contrast, degradation rates of green algal and vascular plant DNA are significantly lower than those of diatom DNA, and in a similar range as corresponding, much less reactive lipid biomarkers and structural macromolecules, including lignin. We propose that physical shielding by degradation-resistant cell wall components, such as algaenan in green algae and lignin in vascular plants, contributes to the long-term preservation of labile biomolecules in both groups and significantly influences the long-term burial of OC in lake sediments.

Microorganisms capable of biomineralization can catalyze mineral precipitation by modifying local physical and chemical conditions. In porous media, such as soil and rock, these microorganisms live and function in highly heterogeneous physical, chemical and ecological microenvironments, with strong local gradients created by both microbial activity and the pore-scale structure of the subsurface. Here, we focus on extracellular bacterial biomineralization, which is sensitive to external heterogeneity, and review the pore-scale processes controlling microbial biomineralization in natural and engineered porous media. We discuss how individual physical, chemical and ecological factors integrate to affect the spatial and temporal control of biomineralization, and how each of these factors contributes to a quantitative understanding of biomineralization in porous media. We find that an improved understanding of microbial behavior in heterogeneous microenvironments would promote understanding of natural systems and output in diverse technological applications, including improved representation and control of fluid mixing from pore to field scales. We suggest a range of directions by which future work can build from existing tools to advance each of these areas to improve understanding and predictability of biomineralization science and technology.

Bacterial biofilms are found in several environmental and industrial porous media, including soils and filtration membranes. Biofilms grow under certain flow conditions and can clog pores, thereby redirecting the local fluid flow. The ability of biofilms to clog pores, the so-called bioclogging, can have a tremendous effect on the local permeability of the porous medium, creating a pressure buildup in the system, and impacting the mass flow through it. To understand the interplay between biofilm growth and fluid flow under different physical conditions (e.g., at different flow velocities and pore sizes), in the present study, a microfluidic platform is developed to visualize biofilm development using a microscope under externally-imposed, controlled physical conditions. The biofilm-induced pressure buildup in the porous medium can be measured simultaneously using pressure sensors and, later, correlated with the surface coverage of the biofilm. The presented platform provides a baseline for a systematic approach to investigate bioclogging caused by biofilms in porous media under flow conditions and can be adapted to studying environmental isolates or multispecies biofilms.

Bacteria in porous media, such as soils, aquifers, and filters, often form surface-attached communities known as biofilms. Biofilms are affected by fluid flow through the porous medium, for example, for nutrient supply, and they, in turn, affect the flow. A striking example of this interplay is the strong intermittency in flow that can occur when biofilms nearly clog the porous medium. Intermittency manifests itself as the rapid opening and slow closing of individual preferential flow paths (PFPs) through the biofilm-porous medium structure, leading to continual spatiotemporal rearrangement. The drastic changes to the flow and mass transport induced by intermittency can affect the functioning and efficiency of natural and industrial systems. Yet, the mechanistic origin of intermittency remains unexplained. Here, we show that the mechanism driving PFP intermittency is the competition between microbial growth and shear stress. We combined microfluidic experiments quantifying Bacillus subtilis biofilm formation and behavior in synthetic porous media for different pore sizes and flow rates with a mathematical model accounting for flow through the biofilm and biofilm poroelasticity to reveal the underlying mechanisms. We show that the closing of PFPs is driven by microbial growth, controlled by nutrient mass flow. Opposing this, we find that the opening of PFPs is driven by flow-induced shear stress, which increases as a PFP becomes narrower due to microbial growth, causing biofilm compression and rupture. Our results demonstrate that microbial growth and its competition with shear stresses can lead to strong temporal variability in flow and transport conditions in bioclogged porous media.

Groundwater contamination of geogenic arsenic (As) remains a global health threat, particularly in south-east Asia. The prominent correlation often observed between high As concentrations and methane (CH₄) stimulated the analysis of the gas dynamics in an As contaminated aquifer, whereby noble and reactive gases were analysed. Results show a progressive depletion of atmospheric gases (Ar, Kr and N₂) alongside highly increasing CH₄, implying that a free gas phase comprised mainly of CH₄ is formed within the aquifer. In contrast, Helium (He) concentrations are high within the CH₄ (gas) producing zone, suggesting longer (groundwater) residence times.
We hypothesized that the observed free (CH₄) gas phase severely detracts local groundwater (flow) and significantly reduces water renewal within the gas producing zone. Results are in-line with this hypothesis, however, a second hypothesis has been developed, which focuses on the potential transport of He from an adjacent aquitard into the (CH₄) gas producing zone. This second hypothesis was formulated as it resolves the particularly high He concentrations observed, and since external solute input from the overlying heterogeneous aquitard cannot be excluded.
The proposed feedback between the gas phase and hydraulics provides a plausible explanation of the anti-intuitive correlation between high As and CH₄, and the spatially highly patchy distribution of dissolved As concentrations in aquifers. Furthermore, the increased groundwater residence time would allow for the dissolution of more crystalline As-hosting iron(Fe)-oxide phases in conjunction with the formation of more stable secondary Fe minerals in the hydraulically-slowed (i.e., gas producing) zone; a subject which calls for further investigation.

Ozonation has been applied in water treatment for more than a century, first for disinfection, later for oxidation of inorganic and organic pollutants. In recent years, ozone has been increasingly applied for enhanced municipal wastewater treatment for ecosystem protection and for potable water reuse. These applications triggered significant research efforts on the abatement efficiency of organic contaminants and the ensuing formation of transformation products. This endeavor was accompanied by developments in analytical and computational chemistry, which allowed to improve the mechanistic understanding of ozone reactions. This critical review assesses the challenges of ozonation of impaired water qualities such as wastewaters and provides an up-to-date compilation of the recent kinetic and mechanistic findings of ozone reactions with dissolved organic matter, various functional groups (olefins, aromatic compounds, heterocyclic compounds, aliphatic nitrogen-containing compounds, sulfur-containing compounds, hydrocarbons, carbanions, β-diketones) and antibiotic resistance genes.

Concentrations of naturally occurring fluoride in groundwater exceeding the WHO guideline of 1.5 mg/L have been detected in many parts of Pakistan. This may lead to dental or skeletal fluorosis and thereby poses a potential threat to public health. Utilizing a total of 5483 fluoride concentrations, comprising 2160 new measurements as well as those from other sources, we have applied machine learning techniques to predict the probability of fluoride in groundwater in Pakistan exceeding 1.5 mg/L at a 250 m spatial resolution. Climate, soil, lithology, topography, and land cover parameters were identified as effective predictors of high fluoride concentrations in groundwater. Excellent model performance was observed in a random forest model that achieved an Area Under the Curve (AUC) of 0.92 on test data that were not used in modeling. The highest probabilities of high fluoride concentrations in groundwater are predicted in the Thar Desert, Sargodha Division, and scattered along the Sulaiman Mountains. Applying the model predictions to the population density and accounting for groundwater usage in both rural and urban areas, we estimate that about 13 million people may be at risk of fluorosis due to consuming groundwater with fluoride concentrations >1.5 mg/L in Pakistan, which corresponds to ~6% of the total population. Both the fluoride prediction map and the health risk map can be used as important decision-making tools for authorities and water resource managers in the identification and mitigation of groundwater fluoride contamination.

Amines in fine particles constitute a significant fraction of secondary organic aerosols and have adverse effects on air quality and human health. To understand the chemical composition, variation characteristics, and potential sources of fine particulate amines in the coastal area in northern China, field sampling and chemical analysis were conducted in coastal Qingdao in the winter of 2018 and 2019. A total of 15 major amines were identified and quantified by using an ultra-high-performance liquid chromatography coupled with mass spectrometry. The average concentration of total amines in PM_2.5 samples was approximately 130 ng m⁻³. Dimethylamine was the most abundant species with average fractions of 44.8% and 65.0% in the quantified amines during the two field campaigns, followed by triethylamine (22.9% and 8.7%) and methylamine (8.3% and 4.4%). The amines in PM_2.5 usually exhibited elevated concentrations in the presence of high levels of SO₂ and NO_x or in the condition of high relative humidity. A receptor model of positive matrix factorization was employed and seven major sources were identified, including coal combustion, industrial production, vehicle exhaust, biomass burning, agricultural activities, secondary formation, and marine emission. Surprisingly, most of 15 amines in fine particles primarily originated from the primary emissions of anthropogenic activities particularly related to coal combustion and industrial productions, which should be given close concern to address the amine pollution.

Peracetic acid (PAA) in combination with transition metals has recently gained increasing attention for organic micropollutant abatement. In this study, aqueous Co(II), Cu(II), and Ag(I) were compared for their capacity to activate PAA. Co(II) outperformed Cu(II) or Ag(I) and the optimum conditions were 0.05 mM of Co(II), 0.4 mM of PAA, and pH 3. However, due to a wider applicability in water treatment, pH 7 (i.e., bicarbonate buffer) was selected for detailed investigations. The abatement of different micropollutant surrogates could be described with a second-order rate equation (observed second-order rate constants, k_obs were in the range of 42-132 M^-1 s^-1). For the para-substituted phenols, there was a correlation between the observed second-order rate constants of the corresponding phenolates and the Hammett constants (R² = 0.949). In all oxidation experiments, the reaction rate decreased significantly after 1-2 min, which coincided with the depletion of PAA but also with the deactivation of the Co(II) catalyst by oxidation to Co(III) and subsequent precipitation. It was demonstrated that Co(II) immobilized on a geopolymer-foam performed approximately similarly as aqueous Co(II) but without deactivation due to Co(III) precipitation. This provides a potential option for the further development of heterogeneous catalytic Co(II)/PAA advanced oxidation processes utilizing geopolymers as a catalyst support material.

Iodine is a naturally-occurring halogen in natural waters generally present in concentrations between 0.5 and 100 µg L^-1. During oxidative drinking water treatment, iodine-containing disinfection by-products (I-DBPs) can be formed. The formation of I-DBPs was mostly associated to taste and odor issues in the produced tap water but has become a potential health problem more recently due to the generally more toxic character of I-DBPs compared to their chlorinated and brominated analogues.
This paper is a systematic and critical review on the reactivity of iodide and on the most common intermediate reactive iodine species HOI. The first step of oxidation of I⁻ to HOI is rapid for most oxidants (apparent second-order rate constant, k_app > 10³ M^-1s^-1 at pH 7). The reactivity of hypoiodous acid with inorganic and organic compounds appears to be intermediate between chlorine and bromine. The life times of HOI during oxidative treatment determines the extent of the formation of I-DBPs. Based on this assessment, chloramine, chlorine dioxide and permanganate are of the highest concern when treating iodide-containing waters. The conditions for the formation of iodo-organic compounds are also critically reviewed.
From an evaluation of I-DBPs in more than 650 drinking waters, it can be concluded that one third show low levels of I-THMs (<1 µg L^-1), and 18% exhibit concentrations > 10 µg L^-1. The most frequently detected I-THM is CHCl₂I followed by CHBrClI. More polar I-DBPs, iodoacetic acid in particular, have been reviewed as well.
Finally, the transformation of iodide to iodate, a safe iodine-derived end-product, has been proposed to mitigate the formation of I-DBPs in drinking water processes. For this purpose a pre-oxidation step with either ozone or ferrate(VI) to completely oxidize iodide to iodate is an efficient process. Activated carbon has also been shown to be efficient in reducing I-DBPs during drinking water oxidation.

Eine nachhaltige Wasserversorgung in urbanen Gebieten stellt aufgrund des Nutzungsdrucks sowie vielfältiger anthropogener Einträge eine große Herausforderung dar. Künstliche Grundwasseranreicherung hat das Potenzial, den Wasserbedarf zu decken und ggf. vorhandene Schadstoffkonzentrationen zu verdünnen. Durch hohe Infiltrationsraten kann zudem eine hydraulische Barriere gegenüber Schadstoffen aus anliegenden Nutzungsflächen entstehen. Grundvoraussetzung, um diese Barriere so effektiv wie möglich nutzen zu können, ist die genaue Beschreibung der räumlichen und zeitlichen Verteilung der Schutzfunktion. Im geschilderten Fallbeispiel für ein Trinkwassergewinnungsgebiet in der Nordschweiz präsentieren wir ein einfaches Online-Werkzeug. Es wird genutzt, um die große Menge der erhobenen Daten zu digitalisieren sowie um die Interpretation von Konturenkarten zu ergänzen, indem es die Auswertung erhobener Daten vereinfacht und Grundwasserfließrichtungen und -magnituden visualisiert. Die Ergebnisse können zur Beschreibung komplexerer Fließsysteme genutzt werden, was zu einer effizienteren Grundwasserbeobachtung führt.

A sustainable water supply in urban areas is a major challenge due to increasing water abstraction as well as diverse anthropogenic inputs. Artificial groundwater recharge has the potential to meet water demand and dilute pollutant concentrations that may be present. High infiltration rates can also create a hydraulic barrier to pollutants from adjacent land uses. The basic prerequisite for using this type of barrier as effectively as possible is an accurate description of the spatial and temporal distribution of groundwater recharge. In the presented case study for a drinking water extraction area in northern Switzerland, we introduce a simple online tool which can be used to complement the large amount of collected data and to digitize and interpret contour maps. The tool simplifies the analysis of collected data and helps to visualize groundwater flow directions and magnitudes. The results can be used to describe complex flow systems, leading to more efficient groundwater monitoring.

Für die Erstellung multipler Grundwassermodelle und deren Unsicherheitsanalyse existiert zwar eine Vielzahl an Methoden, aber in der Praxis bleibt dieses Potenzial oftmals ungenützt. Da Standard-Grundwassermessdaten nicht genügend Informationen für das Identifizieren hydraulischer Parameter beinhalten und auch das Hinzuziehen von unkonventionellen Messdaten Parameterunsicherheiten nicht komplett eliminiert, ist eine Unsicherheitsanalyse von Grundwassermodellen unabdingbar. Dieser Artikel zeigt Vorteile und Wege auf, wie dies in der Praxis umgesetzt werden kann.

Viruses, Giardia cysts, and Cryptosporidium parvum oocysts are all major causes of waterborne diseases that can be uniquely challenging in terms of inactivation/removal during water and wastewater treatment and water reuse. Ozone is a strong disinfectant that has been both studied and utilized in water treatment for more than a century. Despite the wealth of data examining ozone disinfection, direct comparison of results from different studies is challenging due to the complexity of aqueous ozone chemistry and the variety of the applied approaches. In this systematic review, an analysis of the available ozone disinfection data for viruses, Giardia cysts, and C. parvum oocysts, along with their corresponding surrogates, was performed. It was based on studies implementing procedures which produce reliable and comparable datasets. Datasets were compiled and compared with the current USEPA Ct models for ozone. Additionally, the use of non-pathogenic surrogate organisms for prediction of pathogen inactivation during ozone disinfection was evaluated. Based on second-order inactivation rate constants, it was determined that the inactivation efficiency of ozone decreases in the following order: Viruses >> Giardia cysts > C. parvum oocysts. The USEPA Ct models were found to be accurate to conservative in predicting inactivation of C. parvum oocysts and viruses, respectively, however they overestimate inactivation of Giardia cysts at ozone Ct values greater than ∼1 mg min L^-1. Common surrogates of these pathogens, such as MS2 bacteriophage and Bacillus subtilis spores, were found to exhibit different inactivation kinetics to mammalian viruses and C. parvum oocysts, respectively. The compilation of data highlights the need for further studies on disinfection kinetics and inactivation mechanisms by ozone to better fit inactivation models as well as for proper selection of surrogate organisms.

Carbon monoxide (CO) is the second most abundant identified product of dissolved organic matter (DOM) photodegradation after CO₂, but its formation mechanism remains unknown. Previous work showed that aqueous photodegradation of methoxy-substituted aromatics (ArOCH₃) produces CO considerably more efficiently than aromatic carbonyls. Following on this precedent, we propose that the methoxy aromatic groups of lignin act as the C source for the photochemical formation of CO from terrestrial DOM via a two-step pathway: formal hydrolytic demethylation to methanol and methanol oxidation to CO. To test the reasonableness of this mechanism, we investigated the photochemistry of eight lignin model compounds. We first observed that initial CO production rates are positively correlated with initial substrate degradation rates only for models containing at least one ArOCH₃ group, regardless of other structural features. We then confirmed that all ArOCH₃-containing substrates undergo formal hydrolytic demethylation by detecting methanol and the corresponding phenolic transformation products. Finally, we showed that hydroxyl radicals, likely oxidants to initiate methanol oxidation to CO, form during irradiation of all models. This work proposes an explicit mechanism linking ubiquitous, abundant, and easily quantifiable DOM functionalities to CO photoproduction. Our results further hint that methanol may be an abundant (yet overlooked) DOM photoproduct and a likely precursor of formaldehyde, formic acid, and CO₂ and that lignin photodegradation may represent a source of hydroxyl radicals.

Radon-222 (²²²Rn) is routinely used as a tracer of surface water (SW) – groundwater (GW) interactions. However, methods that rely on this tracer to quantify SW-GW exchange fluxes, GW residence time, SW-GW mixing ratios, or GW flow velocities usually depend on the assumption of spatially constant ²²²Rn production within aquifers and/or hyporheic sediments. In the present study, we measure the natural variability of ²²²Rn emanation rates in a highly instrumented alluvial aquifer and underline some important issues in assuming homogenous ²²²Rn production in alluvial systems. A robust experimental setup was used to determine ²²²Rn emanation rates from sediments. High-resolution measurements reveal that ²²²Rn emanation rates are highest within the first few meters below the surface. These results have significant implications for the interpretation of ²²²Rn activities in GW, notably in the vicinity of infiltration zones, as changes in hydraulic conditions can lead to variations in ²²²Rn signatures that can only be resolved with proper knowledge of the spatial distribution of ²²²Rn production rates. In such contexts, the assumption of constant ²²²Rn production leads to an inadequate understanding of SW infiltration patterns, and biased ²²²Rn-based estimates of SW-GW exchange.

Naturally occurring, geogenic manganese (Mn) and iron (Fe) are frequently found dissolved in groundwater at concentrations that make the water difficult to use (deposits, unpleasant taste) or, in the case of Mn, a potential health hazard. Over 6000 groundwater measurements of Mn and Fe in Southeast Asia and Bangladesh were assembled and statistically examined with other physicochemical parameters. The machine learning methods random forest and generalized boosted regression modeling were used with spatially continuous environmental parameters (climate, geology, soil, topography) to model and map the probability of groundwater Mn > 400 μg/L and Fe > 0.3 mg/L for Southeast Asia and Bangladesh. The modeling indicated that drier climatic conditions are associated with a tendency of elevated Mn concentrations, whereas high Fe concentrations tend to be found in a more humid climate with elevated levels of soil organic carbon. The spatial distribution of Mn > 400 μg/L and Fe > 0.3 mg/L was compared and contrasted with that of the critical geogenic contaminant arsenic (As), confirming that high Fe concentrations are often associated with high As concentrations, whereas areas of high concentrations of Mn and As are frequently found adjacent to each other. The probability maps draw attention to areas prone to elevated concentrations of geogenic Mn and Fe in groundwater and can help direct efforts to mitigate their negative effects. The greatest Mn hazard is found in densely populated northwest Bangladesh and the Mekong, Red and Ma River Deltas of Cambodia and Vietnam. Widespread elevated Fe concentrations and their associated negative effects on water infrastructure pose challenges to water supply. The Mn and Fe prediction maps demonstrate the value of machine learning for the geospatial prediction modeling and mapping of groundwater contaminants as well as the potential for further constituents to be targeted by this novel approach.

The health of millions of people worldwide is negatively impacted by chronic exposure to elevated concentrations of geogenic fluoride in groundwater. Due to health effects including dental mottling and skeletal fluorosis, the World Health Organization maintains a maximum guideline of 1.5 mg/L in drinking water. As groundwater quality is not regularly tested in many areas, it is often unknown if the water in a given well or spring contains harmful levels of fluoride. Here we present a state-of-the-art global fluoride hazard map based on machine learning and over 400,000 fluoride measurements (10% of which >1.5 mg/L), which is then used to estimate the human population at risk. Hotspots indicated by the groundwater fluoride hazard map include parts of central Australia, western North America, eastern Brazil and many areas of Africa and Asia. Of the approximately 180 million people potentially affected worldwide, most reside in Asia (51–59% of total) and Africa (37-46% of total), with the latter representing 6.5% of the continent’s population. Africa also contains 14 of the top 20 affected countries in terms of population at risk. We also illuminate and discuss the key globally relevant hydrochemical and environmental factors related to fluoride accumulation.

The sustainability of agriculture in the Mediterranean climate is challenged by high irrigation water demands and nitrogen fertilizer losses to the environment, causing significant pressure on groundwater resources and groundwater-dependent ecosystems. Advanced irrigation technologies and improved fertilizer management have been promoted as key solutions to reduce the agricultural impact on aquatic systems. However, it remains unclear how different irrigation-fertilizer practices perform on the long-term under a highly variable climate, such as the Mediterranean one. Here, we conduct hydrological simulations over a fifty-year period to quantify the magnitude and dynamics of groundwater recharge and nitrogen leaching under five real-case irrigation-fertilizer practices observed in Valencia (eastern Spain). The Valencian Region is the largest citrus-producing region of Europe and current irrigation-fertilizer practices reflect the ongoing transformation of irrigation systems from flood to drip irrigation. Our simulations highlight three major implications of the irrigation transformation for groundwater resources. First, the transformation from flood to drip irrigation reduces the recharge fraction (19% vs. 16%) and especially the nitrogen leaching fraction (33% vs. 18%) on the long term. Second, the long-term performance of the two irrigation practices is subject to substantial inter-annual differences controlled by precipitation variability. The sensitivity of recharge and nitrogen leaching to annual meteorological conditions is stronger in drip irrigation, which eventually leads to a similar performance of flood and drip irrigation in wet years if fertilizer inputs are similar. Third, we identify a pronounced year-to-year nitrogen memory in the soil, whereby an enhanced (decreased) nitrogen leaching is observed after anomalously dry (wet) years, affecting the performance of irrigation-fertilizer practices. Overall, the study demonstrates the highly variable nature of the performance of irrigation-fertilizer practices, and the major findings can guide future efforts in designing sustainable water management strategies for agricultural areas with a Mediterranean climate.

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.

Reactive intermediates formed upon irradiation of chromophoric dissolved organic matter (CDOM) contribute to the degradation of various organic contaminants in surface waters. Besides well-studied "short-lived" photooxidants, such as triplet state CDOM (³CDOM*) or singlet oxygen, CDOM-derived "long-lived" photooxidants (LLPO) have been suggested as key players in the transformation of electron-rich contaminants. LLPO were hypothesized to mainly consist of phenoxyl radicals derived from phenolic moieties in the CDOM. To test this hypothesis and to better characterize LLPO, the transformation kinetics of selected target compounds (phenols and anilines) induced by a suite of electron-poor model phenoxyl radicals was studied in aerated aqueous solution at pH 8. The phenoxyl radicals were generated by photosensitized oxidation of the parent phenols using aromatic ketones as photosensitizers. Under steady-state irradiation, the presence of any of the electron-poor phenols lead to an enhanced abatement of the phenolic target compounds (at an initial concentration of 1.0 × 10^-7 M) compared to solutions containing the photosensitizer but no electron-poor phenol. A trend of increasing reactivity with increasing one-electron reduction potential of the electron-poor phenoxyl radical (range: 0.85-1.12 V vs. standard hydrogen electrode) was observed. Using the excited triplet state of 2-acetonaphthone as a selective oxidant for phenols, it was observed that the reactivity correlated with the concentration of electron-poor phenoxide present in solution. The rates of transformation of anilines induced by the 4-cyanophenoxyl radical were an order of magnitude smaller than for the phenolic target compounds. This was interpreted as a reduction of the radical intermediates back to the parent compound by the superoxide radical anion. Laser flash photolysis measurements confirmed the formation of the 4-cyanophenoxyl radical in solutions containing 2-acetonaphthone and 4-cyanophenol, and yielded values of (2.6 - 5.3) × 10⁸ M^-1 s^-1 for the second-order rate constant for the reaction of this radical with 2,4,6-trimethylphenol. These and further results indicate that electron-poor model phenoxyl radicals generated through photosensitized oxidation are useful models to understand the photoreactivity of LLPO as part of the CDOM.

Chlorine dioxide (ClO₂) applications to drinking water are limited by the formation of chlorite (ClO₂^–) which is regulated in many countries. However, when ClO₂ is used as a pre-oxidant, ClO₂^– can be oxidized by chlorine during subsequent disinfection. In this study, a kinetic model for the reaction of chlorine with ClO₂^– was developed to predict the fate of ClO₂^– during chlorine disinfection. The reaction of ClO₂^– with chlorine was found to be highly pH-dependent with formation of ClO₃^– and ClO₂ in ultrapure water. In presence of dissolved organic matter (DOM), 60-70% of the ClO₂^– was transformed to ClO₃^– during chlorination, while the in situ regenerated ClO₂ was quickly consumed by reaction with DOM. The remaining 30-40% of the ClO₂^– first reacted to ClO₂ which then formed chlorine from the DOM-ClO₂ reaction. Since only part of the ClO₂^– was transformed to ClO₃^–, the sum of the molar concentrations of oxychlorine species (ClO₂^– + ClO₃^–) decreased during chlorination. By kinetic modelling, the ClO₂^– concentration after 24 h of chlorination was accurately predicted in synthetic waters but was largely overestimated in natural waters, possibly due to a ClO₂^– decay enhanced by high concentrations of chloride and in situ formed bromine from bromide. Understanding the chlorine-ClO₂^– reaction mechanism and the corresponding kinetics allows to potentially apply higher ClO₂ doses during the pre-oxidation step, thus improving disinfection byproduct mitigation while keeping ClO₂^–, and if required, ClO₃^– below the regulatory limits. In addition, ClO₂ was demonstrated to efficiently degrade haloacetonitrile precursors, either when used as pre-oxidant or when regenerated in situ during chlorination.

Alluvial sand and gravel (ASG) aquifers are highly heterogeneous and exhibit strong, spatially variable anisotropy, often interspersed by buried paleo-channels of increased hydraulic conductivity. Groundwater flow and solute transport is often characterized by preferential flow caused by anisotropic properties in ASG aquifers. Connected ASG subsurface structures such as buried paleo-channels, however, are difficult to reproduce with commonly used techniques, and anisotropy is rarely considered in applied groundwater models. To ease the notoriously difficult problem of how to consider anisotropy, we propose a novel modeling framework based on calibration of an integrated surface-subsurface hydrological model via spatially varying, preferred anisotropy pilot point inversion. The inversion leverages hydraulic and tracer-based observations representing multiple spatial and temporal scales. We demonstrate the applicability of the framework on a real-world ASG site used for drinking water production, and we quantify the information content of observations to identify connected paleo-channels and provide guidance for optimal field-data acquisition.

Surfactants are high-production-volume chemicals that are among the most abundant organic pollutants in municipal wastewater. In this study, sewage sludge samples of 36 Swiss wastewater treatment plants (WWTPs), serving 32% of the country's population, were analyzed for major surfactant classes by liquid chromatography mass spectrometry (LC-MS). The analyses required a variety of complementary approaches due to different analytical challenges, including matrix effects (which can affect adduct ion formation) and the lack of reference standards. The most abundant contaminants were linear alkylbenzene sulfonates (LAS; weighted mean [WM] concentration of 3700 μg g^-1 dry weight), followed by secondary alkane sulfonates (SAS; 190 μg g^-1). Alcohol polyethoxylates (AEO; 8.3 μg g^-1), nonylphenol polyethoxylates (NPEO; 16 μg g^-1), nonylphenol (NP; 3.1 μg g^-1), nonylphenol ethoxy carboxylates (NPEC; 0.35 μg g^-1) and tert-octylphenol (tert-OP, 1.8 μg g^-1) were present at much lower concentrations. This concentration pattern agrees with the production volumes of the surfactants and their fates in WWTPs. Branched AEO homologues dominated over linear homologues, probably due to higher persistence. Sludge concentrations of LAS, SAS, and NP were positively correlated with the residence time in the anaerobic digester. Derivation of the per capita loads successfully revealed potential industrial/commercial emission sources. Comparison of recent versus historic data showed a decrease in NPEO and NP levels by one or two orders of magnitude since their ban in the 1980s. By contrast, LAS still exhibit similar concentrations compared to 30 years ago.

«Grundwasser - das Unsichtbare sichtbar machen», war das Motto des diesjährigen Weltwassertages. Es könnte auch das Motto des Schweizer Grundwasser-Netzwerks, kurz CH-GNet, sein, das im Frühjahr 2020 ins Leben gerufen wurde und derzeit von der Eawag finanziert wird. Die Aufschaltung der CH-GNet-Website im Februar dieses Jahres war ein wichtiger Schritt für die neue Austausch-, Informations- und Vernetzungsplattform. Über die weiteren Pläne und Ziele sprechen Eawag-Forscher und Mitinitiant des Netzwerks Mario Schirmer und der Verantwortliche für CH-GNet Christian Moeck im Interview.

Ultrahigh-resolution Fourier transform mass spectrometry (FTMS) has revealed unprecedented details of natural complex mixtures such as dissolved organic matter (DOM) on a molecular formula level, but we lack approaches to access the underlying structural complexity. We here explore the hypothesis that every DOM precursor ion is potentially linked with all emerging product ions in FTMS² experiments. The resulting mass difference (Δm) matrix is deconvoluted to isolate individual precursor ion Δm profiles and matched with structural information, which was derived from 42 Δm features from 14 in-house reference compounds and a global set of 11 477 Δm features with assigned structure specificities, using a dataset of ∼18 000 unique structures. We show that Δm matching is highly sensitive in predicting potential precursor ion identities in terms of molecular and structural composition. Additionally, the approach identified unresolved precursor ions and missing elements in molecular formula annotation (P, Cl, F). Our study provides first results on how Δm matching refines structural annotations in van Krevelen space but simultaneously demonstrates the wide overlap between potential structural classes. We show that this effect is likely driven by chemodiversity and offers an explanation for the observed ubiquitous presence of molecules in the center of the van Krevelen space. Our promising first results suggest that Δm matching can both unfold the structural information encrypted in DOM and assess the quality of FTMS-derived molecular formulas of complex mixtures in general.

Freely dissolved OCPs and PCBs were measured by using polyethylene passive samplers at 15 sites during 2014 throughout the stretch of the Indus River to investigate the spatial pattern and risk assess. Levels (pg/L) of dissolved ∑OCPs and ∑PCBs ranged from 34 to 1600 and from 3 to 230. Among the detected OCPs, dissolved DDTs (p,p′-DDE, followed by p,p′-DDT) predominated with levels of 0.48 to 220 pg/L. The order of occurrence for other studied OCPs was as follows: HCB, endosulfans, chlordanes, and HCHs. Spatially, dissolved (pg/L) ∑OCPs varied (p < 0.05) as the following: surface water of the alluvial riverine zone (ARZ) showed the highest levels (114) followed by the frozen mountain zone (FMZ) (52.9), low-lying zone (LLZ) (28.73), and wet mountain zone (WMZ) (14.43), respectively. However, our zone-wise PCB data did not exhibit significant differences (p > 0.05). Principal component analysis/multilinear regression results showed pesticide usage in the crop/orchard fields and health sector, electric and electronic materials, and widespread industrial activities as the main source of OCPs and PCBs along the Indus River. Our results showed that OCPs and PCBs contaminated water intake, playing an important role towards the considerable cancer/non-cancer risk (HI and CR values) along the Indus River Flood-Plain.

In den 50 Jahren ihres Bestehens ermöglichte die Nationale Daueruntersuchung der Fliessgewässer (NADUF), zahlreiche Erfolge von Gewässerschutzmassnahmen in der Schweiz quantitativ zu belegen und Zustandsänderungen aufzuzeigen. Dazu gehören reduzierte Einträge von Phosphat, Schwermetallen oder Stickstoffverbindungen in die Gewässer. In der Zukunft stellen sich beim Monitoring neue Herausforderungen wie die Ermittlung der Einträge von organischen Mikroverunreinigungen oder die durch den Klimawandel induzierten Änderungen im aquatischen Ökosystem.

Dietary deficiency of selenium is a global health threat related to low selenium concentrations in crops. Despite the chemical similarity of selenium to the two more abundantly studied elements sulfur and arsenic, the understanding of its accumulation in soils and availability for plants is limited. The lack of understanding of soil selenium cycling is largely due to the unavailability of methods to characterize selenium species in soils, especially the organic ones. Here we develop a size-resolved multi-elemental method using liquid chromatography and elemental mass spectrometry, which enables an advanced characterization of selenium, sulfur, and arsenic species in soil extracts. We apply the analytical approach to soils sampled along the Kohala rainfall gradient on Big Island (Hawaii), which cover a large range of organic carbon and (oxy)hydroxides contents. Similarly to sulfur but contrarily to arsenic, a large fraction of selenium is found associated with organic matter in these soils. However, while sulfur and arsenic are predominantly found as oxyanions in water extracts, selenium mainly exists as small hydrophilic organic compounds. Combining Kohala soil speciation data with concentrations in parent rock and plants further suggests that selenium association with organic matter limits its mobility in soils and availability for plants.

Bentonite is a common backfill material used in Engineered Barrier Systems (EBS) for radioactive waste disposal. Its thermal, hydraulic, and chemical properties have been extensively studied. However, empirical evidence on the interactions with the free gas phase present in its pore space under conditions close to those prevailing in deep geological repositories (i.e., exposure to multiple gas species at temperature and humidity conditions close to those of freshly backfilled EBS) is scarce. This limits the prediction/assessment of the evolution of the gas composition in EBS. Here we present the outcome of laboratory experiments targeting such gas-bentonite interactions using two different types of bentonite (Italian bentonite; Wyoming bentonite) being exposed to atmospheric air in sealed stainless-steel vessels. The results indicate that gas sorption on bentonite can occur at repository-like conditions and is likely to play a significant role in the overall gas dynamics in the backfill of EBS. Drying of both bentonites was shown to partly re-activate their CO₂ sorption capacity during a subsequent re-hydration phase. Furthermore, the grinding of Wyoming bentonite resulted in the generation of new pyrite surfaces that significantly enhanced O₂ removal from the free gas phase by oxidation. Our initial investigations call for more systematic and extensive series of laboratory experiments in order to quantitatively constrain the different processes involved in gas-bentonite interactions.

Household sand filters (SFs) are widely applied to remove iron (Fe), manganese (Mn), arsenic (As), and ammonium (NH₄⁺) from groundwater in the Red River delta, Vietnam. Processes in the filters probably include a combination of biotic and abiotic reactions. However, there is limited information on the microbial communities treating varied groundwater compositions and on whether biological oxidation of Fe(II), Mn(II), As(III), and NH₄⁺ contributes to the overall performance of SFs. We therefore analyzed the removal efficiencies, as well as the microbial communities and their potential activities, of SFs fed by groundwater with varying compositions from low (3.3 μg L⁻¹) to high (600 μg L⁻¹) As concentrations. The results revealed that Fe(II)-, Mn(II)-, NH₄⁺-, and NO₂⁻-oxidizing microorganisms were prevalent and contributed to the performance of SFs. Additionally, groundwater composition was responsible for the differences among the present microbial communities. We found i) microaerophilic Fe(II) oxidation by Sideroxydans in all SFs, with the highest abundance in SFs fed by low-As and high-Fe groundwater, ii) Hyphomicropbiaceae as the main Mn(II)-oxidizers in all SFs, iii) As sequestration on formed Fe and Mn (oxyhydr)oxide minerals, iv) nitrification by ammonium-oxidizing archaea (AOA) followed by nitrite-oxidizing bacteria (NOB), and v) unexpectedly, the presence of a substantial amount of methane monooxygenase genes (pmoA), suggesting microbial methane oxidation taking place in SFs. Overall, our study revealed diverse microbial communities in SFs used for purifying arsenic-contaminated groundwater, and our data indicate an important contribution of microbial activities to the key functional processes in SFs.

In this study, we report combined Tl isotopic and Tl mineralogical and speciation data from a set of Tl-rich sulfide concentrates and technological wastes from hydrometallurgical Zn extraction. We also present the first evaluation of Tl isotopic ratios over a cycle of sulfide processing, from the ore flotation to pyro- and hydrometallurgical stages. The results demonstrate that the prevailing Tl form in all samples is Tl(I), without any preferential incorporation into sulfides or Tl-containing secondary phases, indicating an absence of Tl redox reactions. Although the Tl concentrations varied significantly in the studied samples (~9–280 mg/kg), the overall Tl isotopic variability was small, in the range of −3.1 to −4.4 ± 0.7 (2σ) ε²⁰⁵Tl units. By combining present ε²⁰⁵Tl results with the trends first found for a local roasting plant, it is possible to infer minimum Tl isotopic effects throughout the studied industrial process. As a result, the use of Tl isotopic ratios as a source proxy may be complicated or even impossible in areas with naturally high/extreme Tl background contents. On the other hand, areas with two or more isotopically contrasting Tl sources allow for relatively easy tracing, i.e., in compartments which do not suffer from post-depositional isotopic redistributions.

The simultaneous presence of liquid and gas in porous media increases flow heterogeneity compared to saturated flows. However, the impact of saturation on flow and transport has so far remained unclear. The presence of gas in the pore space leads to flow reorganization. We develop a theoretical framework that captures the impact of that reorganization on pore-scale fluid velocities. Preferential flow is distributed spatially through a backbone, and flow recirculation occurs in flow dead-ends. We observe, and predict theoretically, that this previously identified flow structure induces a marked change in the scaling of the velocity probability density function compared to the saturated configuration and a sharp transition to strongly anomalous transport. We develop a transport model using the continuous time random walk theory that predicts advective transport dynamics for all saturation degrees. Our results provide a new modeling framework linking phase heterogeneity to flow heterogeneity in unsaturated porous media.

This critical review presents the key factors that control the occurrence of natural elements from the uranium- and thorium-decay series, also known as naturally occurring radioactive materials (NORM), including uranium, radium, radon, lead, polonium, and their isotopes in groundwater resources. Given their toxicity and radiation, elevated levels of these nuclides in drinking water pose human health risks, and therefore understanding the occurrence, sources, and factors that control the mobilization of these nuclides from aquifer rocks is critical for better groundwater management and human health protection. The concentrations of these nuclides in groundwater are a function of the groundwater residence time relative to the decay rates of the nuclides, as well as the net balance between nuclides mobilization (dissolution, desorption, recoil) and retention (adsorption, precipitation). This paper explores the factors that control this balance, including the relationships between the elemental chemistry (e.g., solubility and speciation), lithological and hydrogeological factors, groundwater geochemistry (e.g., redox state, pH, ionic strength, ion-pairs availability), and their combined effects and interactions. The various chemical properties of each of the nuclides results in different likelihoods for co-occurrence. For example, the primordial ²³⁸U, ²²²Rn, and, in cases of high colloid concentrations also ²¹⁰Po, are all more likely to be found in oxic groundwater. In contrast, in reducing aquifers, Ra nuclides, ²¹⁰Pb, and in absence of high colloid concentrations, ²¹⁰Po, are more mobile and frequently occur in groundwater. In highly permeable sandstone aquifers that lack sufficient adsorption sites, Ra is often enriched, even in low salinity and oxic groundwater. This paper also highlights the isotope distributions, including those of relatively long-lived nuclides (²³⁸U/²³⁵U) with abundances that depend on geochemical conditions (e.g., fractionation induced from redox processes), as well as shorter-lived nuclides (²³⁴U/²³⁸U, ²²⁸Ra/²²⁶Ra, ²²⁴Ra/²²⁸Ra, ²¹⁰Pb/²²²Rn, ²¹⁰Po/²¹⁰Pb) that are strongly influenced by physical (recoil), lithological, and geochemical factors. Special attention is paid in evaluating the ability to use these isotope variations to elucidate the sources of these nuclides in groundwater, mechanisms of their mobilization from the rock matrix (e.g., recoil, ion-exchange), and retention into secondary mineral phases and ion-exchange sites.

The adsorption of thallium (Tl) onto phyllosilicate minerals plays a critical role in the retention of Tl in soils and sediments and the potential transfer of Tl into plants and groundwater. Especially micaceous minerals are thought to strongly bind monovalent Tl(_I), in analogy to their strong binding of Cs. To advance the understanding of Tl(_I) adsorption onto phyllosilicate minerals, we studied the adsorption of Tl(_I) onto Na- and K-saturated illite and Na-saturated smectite, two muscovites, two vermiculites and a naturally Tl-enriched soil clay mineral fraction. Macroscopic adsorption isotherms were combined with the characterization of the adsorbed Tl by X-ray absorption spectroscopy (XAS). In combination, the results suggest that the adsorption of Tl(_I) onto phyllosilicate minerals can be interpreted in terms of three major uptake paths: (i) highest-affinity inner-sphere adsorption of dehydrated Tl⁺ on a very low number of adsorption sites at the wedge of frayed particle edges of illite and around collapsed zones in vermiculite interlayers through complexation between two siloxane cavities, (ii) intermediate-affinity inner-sphere adsorption of partially dehydrated Tl⁺ on the planar surfaces of illite and muscovite through complexation onto siloxane cavities, (iii) low-affinity adsorption of hydrated Tl⁺, especially in the hydrated interlayers of smectite and expanded vermiculite. At the frayed edges of illite particles and in the vermiculite interlayer, Tl uptake can lead to the formation of new wedge sites that enable further adsorption of dehydrated Tl⁺. On the soil clay fraction, a shift in Tl(_I) uptake from frayed edge sites (on illite) to planar sites (on illite and muscovite) was observed with increasing Tl(_I) loading. The results from this study show that the adsorption of Tl(_I) onto phyllosilicate minerals follows the same trends as reported for Cs and Rb and thus suggests that concepts to describe the retention of (radio)cesium by different types of phyllosilicate minerals in soils, sediments and rocks are also applicable to Tl(_I).

Sustainability of agricultural systems is at stake, as phosphorus (P) is a non-renewable resource while its global reserves are limited. Stimulating earthworm activity can be a technology to increase the level of readily plant-available phosphate (PO₄). However, conclusive evidence on the mechanisms underlying an earthworm-enhanced PO₄ solubility is yet missing. This study aimed to reveal possibly overlooked pathways by which earthworms affect PO₄ solubility, and quantify the relative importance of all contributing mechanisms. Therefore, we set up a greenhouse pot experiment in which we investigated the large increase in water-extractable PO₄ in casts of three earthworm species (Lumbricus rubellus, Aporrectodea caliginosa, Lumbricus terrestris) in soils with either predominantly Fe- or Al-(hydr)oxides. Oxalate-extractable PO₄ was increased in earthworm casts compared to bulk soil which can be attributed to the mineralisation of natural organic matter (NOM). Surface complexation modelling was used to elucidate the mechanisms that control earthworm-enhanced PO₄ solubility. The results of our modelling showed that the increase in pH in earthworm casts relative to bulk soil affects PO₄ solubility only to a minor extent. Besides NOM mineralisation, two major mechanisms contributing to earthworm-enhanced PO₄ solubility are (i) a decrease in the reactive surface area (RSA) of the metal-(hydr)oxide fraction; and (ii) a decrease in the competition between NOM and PO₄ for binding sites of the metal-(hydr)oxides. As the newly discovered decrease of the RSA was only found for Fe-(hydr)oxide-dominated soils, earthworms have the largest potential to enhance PO₄ solubility in those soils.

Cethyltrimethylammonium chloride (CTMA) is one of the most used quaternary ammonium compounds (QACs) in consumer products. CTMA and other QACs are only partially eliminated in municipal wastewater treatment and they can interact with bacteria in biological processes. Currently, there is only limited information on the antimicrobial efficiency of CTMA in matrices other than standard growth media and if and how CTMA influences conventional chemical disinfection. The results obtained in this study showed that the susceptibility of E. coli to CTMA was significantly enhanced in phosphate-buffered saline, lake water and wastewater compared to broth. In broth, a minimum inhibitory concentration (MIC) of CTMA of 20 mgL^-1 was observed for E. coli, whereas a 4-log inactivation occurred for CTMA concentrations of about 4 mgL^-1 in buffered ultra-purified water, a lake water and wastewater effluent. The impacts of the pre-exposure and the presence of CTMA on inactivation by ozone and monochloramine were tested with three different E. coli strains: AG100 with the efflux pump acrAB intact, AG100A with it deleted and AG100tet with it overexpressed. Pre-exposure of E. coli AG100 to CTMA led to an increased susceptibility for ozone with second-order inactivation rate constants (∼ 10⁶ M^-1s^-1) increasing by a factor of about 1.5. An opposite trend was observed for monochloramine with second-order inactivation rate constants (∼ 10³ M^-1s^-1) decreasing by a factor of about 2. For E. coli AG100tet, the second-order inactivation rate constant decreased by a factor of almost 2 and increased by a factor of about 1.5 for ozone and monochloramine, respectively, relative to the strain AG100. The simultaneous presence of CTMA and ozone enhanced the second-order inactivation rate constants for CTMA concentrations of 2.5 mgL⁻¹ by a factor of about 3. For monochloramine also an enhancement of the inactivation was observed, which was at least additive but might also be synergistic. Enhancement by factors from about 2 to 4.5 were observed for CTMA concentrations > 2.5 mgL^-1.

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 mg_O3⋅mg_DOC^-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 mg_O3⋅mg_DOC^-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.

Arsenic (As) is a toxic element, and elevated levels of geogenic As in drinking water pose a threat to the health of several hundred million people worldwide. In this study, we used microfluidics in combination with optical microscopy and X-ray spectroscopy to investigate zerovalent iron (ZVI) corrosion, secondary iron (Fe) phase formation, and As retention processes at the pore scale in ZVI-based water treatment filters. Two 250 μm thick microchannels filled with single ZVI and quartz grain layers were operated intermittently (12 h flow/12 h no-flow) with synthetic groundwater (pH 7.5; 570 μg/L As(III)) over 13 and 49 days. Initially, lepidocrocite (Lp) and carbonate green rust (GRC) were the dominant secondary Fe-phases and underwent cyclic transformation. During no-flow, lepidocrocite partially transformed into GRC and small fractions of magnetite, kinetically limited by Fe(II) diffusion or by decreasing corrosion rates. When flow resumed, GRC rapidly and nearly completely transformed back into lepidocrocite. Longer filter operation combined with a prolonged no-flow period accelerated magnetite formation. Phosphate adsorption onto Fe-phases allowed for downstream calcium carbonate precipitation and, consequently, accelerated anoxic ZVI corrosion. Arsenic was retained on Fe-coated quartz grains and in zones of cyclic Lp-GRC transformation. Our results suggest that intermittent filter operation leads to denser secondary Fe-solids and thereby ensures prolonged filter performance.

Water treatment with nanofiltration (NF) or reverse osmosis (RO) membranes results in a purified permeate and a retentate, where solutes are concentrated and have to be properly managed and discharged. To date, little is known on how the selection of a semi-permeable dense membrane impacts the dissolved organic matter in the concentrate and what the consequences are for micropollutant (MP) abatement and bromate formation during concentrate treatment with ozone. Laboratory ozonation experiments were performed with standardized concentrates produced by three membranes (two NFs and one low-pressure reverse osmosis (LPRO) membrane) from three water sources (two river waters and one lake water). The concentrates were standardized by adjustment of pH and concentrations of dissolved organic carbon, total inorganic carbon, selected micropollutants (MP) with a low to high ozone reactivity and bromide to exclude factors which are known to impact ozonation. NF membranes had a lower retention of bromide and MPs than the LPRO membrane, and if the permeate quality of the NF membrane meets the requirements, the selection of this membrane type is beneficial due to the lower bromate formation risks upon concentrate ozonation. The bromate formation was typically higher in standardized concentrates of LPRO than of NF membranes, but the tradeoff between MP abatement and bromate formation upon ozonation of the standardized concentrates was not affected by the membrane type. Furthermore, there was no difference for the different source waters. Overall, ozonation of concentrates is only feasible for abatement of MPs with a high to moderate ozone reactivity with limited bromate formation. Differences in the DOM composition between NF and LPRO membrane concentrates are less relevant than retention of MPs and bromide by the membrane and the required ozone dose to meet a treatment target.

Um mit gezielten Massnahmen die Einträge von Pflanzenschutzmitteln in Oberflächengewässern zu verringern, müssen die relevanten Quellen und Eintragspfade bekannt sein. Dazu bestehen immer noch wichtige Wissenslücken. Deshalb wurde untersucht, welche Schlussfolgerungen aus zwölf bestehenden Monitoringstudien hinsichtlich der relevanten Transportwege gezogen werden können und was sich daraus für die Planung zukünftiger Studien und Projekte ableiten lässt.

While drinking water is known to create significant health risk in arsenic hazard areas, the role of exposure to arsenic through food intake is less well understood, including the impact of food trade. Using the best available datasets on crop production, irrigation, groundwater arsenic hazard, and international crop trade flows, we estimate that globally 17.2% of irrigated harvested area (or 45.2 million hectares) of 42 main crops are grown in arsenic hazard areas, contributing 19.7% of total irrigated crop production, or 418 million metric tons (MMT) per year of these crops by mass. Two-thirds of this area is dedicated to the major staple crops of rice, wheat, and maize (RWM) and produces 158 MMT per year of RWM, which is 8.0% of the total RWM production and 18% of irrigated production. More than 25% of RWM consumed in the South Asian countries of India, Pakistan, and Bangladesh, where both arsenic hazard and degree of groundwater irrigation are high, originate from arsenic hazard areas. Exposure to arsenic risk from crops also comes from international trade, with 10.6% of rice, 2.4% of wheat, and 4.1% of maize trade flows coming from production in hazard areas. Trade plays a critical role in redistributing risk, with the greatest exposure risk borne by countries with a high dependence on food imports, particularly in the Middle East and small island nations for which all arsenic risk in crops is imported. Intensifying climate variability and population growth may increase reliance on groundwater irrigation, including in arsenic hazard areas. Results show that RWM harvested area could increase by 54.1 million hectares (179% increase over current risk area), predominantly in South and Southeast Asia. This calls for the need to better understand the relative risk of arsenic exposure through food intake, considering the influence of growing trade and increased groundwater reliance for crop production.

In einer landesweiten Studie wurde Quecksilber in Abwässern und Klärschlämmen analysiert, jährliche Gesamtmengen des abwasserbürtigen Quecksilbers ermittelt und die Einhaltung der gesetzlichen Vorgaben überprüft. Ebenso wurde die durchschnittliche Fracht pro Einwohner und der Beitrag der Abwasserreinigungsanlagen zur Quecksilberbelastung der Oberflächengewässer ermittelt. Auf nationaler Ebene waren diese Kennzahlen bisher nicht bekannt.

Hyporheic exchange (HE) contributes to the biogeochemical turnover of macro- and micro-pollutants in rivers. However, the spatiotemporal complexity and variability of HE hinder understanding of its role in the overall functioning of riverine ecosystems. The present study focuses on investigating the role of bacterial diversity and sediment morphology on HE using a multi-flume experiment. A fully coupled surface–subsurface numerical model was used to highlight complex exchange patterns between surface water and the underlying flow field in the sediments. Under the experimental conditions, the surface water flow induced by bedforms has a prominent effect on both local trajectories and residence time distributions of hyporheic flow paths, whereas mean hyporheic retention times are mainly modulated by average surface flowrates. In case of complex bedform morphologies, the numerical model successfully reproduces the HE estimated by means of salt dilution tests. However, the 2D numerical representation of the system falls short in predicting HE in absence of bedforms, highlighting the intrinsic complexity of water circulation patterns in real scenarios. Finally, results show that higher bacterial diversities in the stream sediments can significantly reduce hyporheic fluxes. This work provides a framework to interpret micropollutants turnover in light of the underlying physical transport processes in the hyporheic zone. The study emphasizes the importance of better understanding the tradeoff between physically driven transport processes and bacterial dynamics in the hyporheic zone to quantify the fate of pollutants in streams and rivers.

The outbreak of the novel coronavirus, severe acute respiratory syndrome (SARS)-CoV-2, has gained unprecedented global attention. SARS-CoV-2, which causes the newly described coronavirus disease 2019 (COVID-19), has affected millions of people and led to over 1.9 million deaths worldwide by the beginning of January 2021. Several governments have opted for lockdown as one of the measures to combat the rapidly increasing number of COVID-19 cases. Academic institutions (i.e.,universities, colleges, research centers and national laboratories), which are home to thousands of students, researchers, technicians, and administrative staff, have strictly followed government regulations. Due to the lockdown, the majority of academics have been facing various challenges, especially in transitioning from classroom to remote teaching and conducting research activities from a home office. This article from an early-career researchers' perspective addresses the common challenges that academic institutions have encountered and possible strategies they have adopted to mitigate those challenges at the individual organizational level. Furthermore, we propose a framework to facilitate the handling of such crisis in any near future at the organizational level. We hope academics, policymakers and (non) government organizations across the globe will find this perspective a call to better improve the overall infrastructure of academic institutions.

Surfactants, after use, enter the environment through diffuse and point sources such as irrigation with treated and non-treated waste water and urban and industrial wastewater discharges. For the group of non-ionic synthetic surfactant alcohol ethoxylates (AEOs), most of the available information is restricted to the levels and fate in aquatic systems, whereas current knowledge of their behavior in soils is very limited. Here we characterize the behavior of different homologs (C12-C18) and ethoxymers (EO3, EO6, and EO8) of the AEOs through batch experiments and under unsaturated flow conditions during infiltration experiments. Experiments used two different agricultural soils from a region irrigated with reclaimed water (Guadalete River basin, SW Spain). In parallel, water flow and chemical transport were modelled using the HYDRUS-1D software package, calibrated using the infiltration experimental data. Estimates of water flow and reactive transport of all surfactants were in good agreement between infiltration experiments and simulations. The sorption process followed a Freundlich isotherm for most of the target compounds. A systematic comparison between sorption data obtained from batch and infiltration experiments revealed that the sorption coefficient (K_d) was generally lower in infiltration experiments, performed under environmental flow conditions, than in batch experiments in the absence of flow, whereas the exponent (β) did not show significant differences. For the low clay and organic carbon content of the soils used, no clear dependence of K_d on them was observed. Our work thus highlights the need to use reactive transport parameterization inferred under realistic conditions to assess the risk associated with alcohol ethoxylates in subsurface environments.

Volcanic activity is a major natural climate forcing and an accurate representation of volcanic aerosols in global climate models is essential. This is a complex task involving many uncertainties in the model design and setup and observations. We analyze the performance of the aerosol-chemistry-climate model SOCOL-AERv2 for three medium-sized volcanic eruptions. We focus on the impact of differences in volcanic plume height and SO₂ estimates on the stratospheric aerosol burden. The influence of internal model variability and dynamics are addressed through an ensemble of free-running and nudged simulations at different vertical resolutions. Comparing the modeled evolution of the stratospheric aerosol loading to satellite measurements reveals a good model performance. However, a conclusive validation is complicated by uncertainties in observations and emission estimates. The large spread in emitted sulfur amount and its vertical distribution consequently lead to differences in simulated aerosol burdens. Varying tropopause heights among free-running simulations add to these differences, modulating the amount of sulfur injected into the stratosphere. In nudged mode, volcanic aerosol burden peaks are well reproduced, however changes in convection and clouds affect SO₂ oxidation paths and cross-tropopause transport, leading to increased background burdens compared to observations. This effect can be reduced by leaving temperatures unconstrained. A higher vertical resolution of 90 levels increases the stratospheric residence time of sulfate aerosol by reducing the diffusion out of the tropical reservoir. We conclude that the model set-up (vertical resolution and free-running vs. nudged) as well as forcing parameters (volcanic emission strength and plume height) contribute equally to the model uncertainties.

Study region: The mesoscale Thur catchment located in the north‐eastern part of Switzerland is a study site in which a range of hydrological research has been conducted.
Study focus: Groundwater recharge is challenging to quantify due to the complexity of hydrogeological processes and limited observations. Because of its spatiotemporal availability, remotely sensed data present an attractive water management tool. Its application in mesoscale catchments (10 – 10⁴ km²) however, remains limited. This study investigated the use of satellite products used in conjunction with ground-based data to determine spatiotemporal variations in water available for groundwater recharge. Gridded components from readily available precipitation, evapotranspiration, and hydrological discharge data were used to generate spatiotemporal maps over a 20-year period.
New hydrological insights for the region: Closure of the water balance found that monthly data displayed a moderate correlation, with improved correlations of obtained seasonal and annual intervals, suggesting that over the long-term the Thur catchment is in a steady state. Maps were generated and trends for the 20-year period assessed. Examination of the gridded water balance components for different hydrological years emphasized the limiting effect of precipitation on recharge. This study highlights the value of remotely sensed data in groundwater recharge estimates, but emphasises the importance of continued ground-based monitoring; the lack of which is a limiting factor in water management where mesoscale catchments are concerned.

Lake Kivu is a deep, meromictic lake in the East-African Rift Valley on the border between Rwanda and the Democratic Republic of the Congo (DRC). It is well-known for its huge reservoir of dissolved carbon dioxide and methane in the permanently stratified deep waters. The reason for this unusual gas reservoir is the intrusion of warm, saline, gas-rich and dense groundwater into the deep water of Lake Kivu. Besides providing carbon dioxide, the deep inflow of dense groundwater also maintains a strong density stratification, which prevents turbulent mixing. Consequently, the diffusive upward transport of carbon dioxide and methane, which is at least partially of biogenic origin, is very weak. For the surrounding population and their countries, the gas reservoir is a potential risk and a natural resource at the same time. Although the gases in the lake are currently still far away from saturation (below 55 %), an extreme mixing event could potentially bring deep water to the surface, where it would outgas and asphyxiate animals and humans in the surroundings. In contrast to the potential risk, the methane in Lake Kivu also represents a valuable energy resource for both Rwanda and the DRC. [...]

Der Kivusee ist ein tiefer, meromiktischer See im ostafrikanischen Graben, der auf der Grenze zwischen Ruanda und der Demokratischen Republik Kongo (DR Kongo) liegt. Er ist weltweit bekannt für sein enormes Vorkommen an Kohlendioxid und Methan, das gelöst im stabil geschichteten Tiefenwasser lagert. Der Grund für dieses ungewöhnliche Gasvorkommen ist der Zufluss von warmem, salz- und kohlendioxidreichem und daher dichtem Grundwasser direkt ins Tiefenwasser des Kivusees. Dieser Zufluss von dichtem Grundwasser sorgt für eine sehr stabile Dichteschichtung, die turbulente Mischung verhindert und den vertikalen Transport von Kohlendioxid und vornehmlich biologisch produziertem Methan praktisch unterbindet. Für die angrenzenden Länder und deren Bevölkerung ist das Gasvorkommen ein potentielles Risiko. Auch wenn der Gasdruck im See momentan noch weit von der Sättigung entfernt ist (unterhalb von 55 %), könnte ein ausserordentliches Mischereignis gasreiches Tiefenwasser an die Oberfläche bringen. Durch den fehlenden Wasserdruck an der Oberfläche würde ein grosser Teil der Gase entweichen und könnte für die in der Nähe des Sees lebenden Menschen und Tiere den Erstickungstod bedeuten. Im Gegensatz zur potentiellen Gefahr durch Ausgasen ist das Methanvorkommen aber auch eine wertvolle Energieressource für Ruanda und DR Kongo. [...]

As compared to the Asian lowlands, environmental exposure to arsenic (As) in West Africa has received little attention. Recent studies have found geogenic As contamination of groundwater in many regions in Burkina Faso. As-contaminated groundwater is used for drinking and increasingly also for the irrigation of staple foods. This study assesses the extent to which irrigation and cooking of staple foods in Burkina Faso influence plant uptake and dietary consumption of As, respectively. Using a greenhouse experimental setup, we evaluated the transfer of As from irrigation water spiked with 0, 100, 500, and 1,000 μg/L As(V) to the organs and edible parts of seven commonly consumed vegetables (amaranth, carrot, green bean, lettuce, okra, spinach, and tomato). Next, we cooked the greenhouse-cultivated vegetables and externally purchased foods with As-free and As-spiked waters. The As content in all plant organs increased with increasing As in the irrigation water. With 500 μg/L, the concentrations of As in the edible parts (ordered from highest to lowest) were as follows: spinach (6.6 ± 0.5 μg/g); lettuce (3.9 ± 0.1 μg/g); carrot (3.5 ± <0.1 μg/g); amaranth (2.2 ± <0.1 μg/g); okra (0.9 ± <0.1 μg/g); green bean (0.8 ± <0.1 μg/g); and tomato (0.2 ± <0.1 μg/g). The edible parts of leafy vegetables irrigated with As-spiked water had a higher average As content (4.9 ± 4.5 μg/g) than root (2.9 ± 2.0 μg/g) and fruit/pod vegetables (0.8 ± 1.1 μg/g). Cooking with an excess volume of As-free water reduced the As content in the cooked vegetables by 39% on average, while cooking with As-contaminated water transferred As to the cooked food. The As content in steamed foods was 8 to 18 times lower than in boiled foods. Based on human health risk estimates, we generally recommend to avoid planting leafy and root vegetables in areas with As concentrations above 100 μg/L in irrigation water. In areas with elevated As contamination, mitigation strategies include the cultivation of fruit/pods vegetables such as tomato and okra and steaming the food instead of boiling.

Novel strategies are required to reduce uncertainties in the assessment of ecosystem transpiration (T). A major problem in modelling T is related to the complexity of constraining canopy stomatal resistance (r_sc), accounting for the main biological controls on T besides non biological controls such as aerodynamic resistances or energy constraints. The novel Earth observation signal sun-induced chlorophyll fluorescence (SIF) is the most direct measure of plant photosynthesis and offers new pathways to advance estimates of T. The potential of using SIF to study ecosystem T either empirically or in combination with complex mechanistic models has already been demonstrated in recent studies. The diversity of environmental drivers determining diurnal and seasonal dynamics in T and SIF independently requires additional investigation to guide further developments towards robust SIF-informed T retrievals. This study consequently aims to identify relevant biotic and abiotic environmental drivers affecting the capability of SIF to inform estimates of ecosystem T. We used observational data from a temperate mixed forest during the leaf-on period and a Penman-Monteith (PM) based modelling framework, and observed varying sensitivities of SIF-informed approaches for diurnal and seasonal T dynamics (i.e. r² from 0.52 to 0.58 and rRMSD from 17 to 19%). We used the PM based modelling framework to investigate systematically the sensitivity of SIF to diurnal and seasonal variations in r_sc when empirically and mechanistically embedded in the models. We used observations and the Soil-Vegetation-Atmosphere-Transfer model SCOPE to study the dependence of SIF and T on abiotic and biotic environmental drivers including net radiation, air temperature, relative humidity, wind speed, and leaf area index. We conclude on the potential of SIF to advance estimates of T and suggest preferring more sophisticated modelling frameworks constrained with SIF and other Earth observation data over the single use of SIF to assess reliably ecosystem T across scales.

Soils and other geologic porous media often have contrasting grain size layers associated with a grain size transition zone between layers. However, this transition zone is generally simplified to a plane of zero thickness for modeling assumption, and its influence has always been neglected in previous studies. In this study, an approach combining a deposition process and a random packing process was developed to generate 3D porous media without and with consideration of the transition zone. The direct numerical models for solving the flow and concentration fields were implemented to investigate the influence of the grain size transition on flow and solute transport. Our results showed that although the transition zone occupied 13.6% of the entire layered porous medium, it had little influence on the distribution of flow velocity at the scale of the entire layered porous medium. However, the transition zone had a significant influence on the local flow field, which was associated with the increased spatial variability of velocity and the varied distribution of flow velocity. This varied local flow field could increase the solute residence time and delay the breakthrough time for solute transport. Although using both the advection-dispersion equation (ADE) and the mobile and immobile (MIM) models to fit the breakthrough curves (BTCs) for solute transport through layered porous media resulted in trivial errors, the ADE model failed to capture the influence induced by the local flow field, especially the influence of the transition zone. In contrast, the MIM model was shown to be able to capture the influence of the transition on solute transport. It was found that the mass transfer rate α⁠, a parameter of the MIM model, was significantly improved by the presence of the transition zone, while it decreased as the transition zone fraction increased. Our study emphasized that the transition zone can vary the local flow field at the pore scale, while it has little influence on the hydraulic properties (e.g., hydraulic conductivity) of the macroscale flow field. However, the local flow field varied by the transition zone has a significant influence on solute transport.

Fractured rocks in the subsurface are ubiquitous, and the dynamics of mass transfer in fractured rocks plays an important role in understanding the problem in engineering geology and environmental geology. In this study, the influence of shear displacement on fluid flow and solute transport in a 3D rough fracture was investigated. A 3D self-affine rough fracture was generated using the modified successive random addition (SRA) technology, and three sheared fractures with different shear displacements were constructed based on the mechanistic model. A direct numerical model based on the Navier-Stokes equation and the advection-diffusion equation was developed to solve the fluid flow and the solute transport. The results showed that shear displacement had a significant influence not only on the fluid flow but also on the solute transport. A global measure of the spatial variability of the flow velocity showed that the heterogeneity became weaker with decreasing shear displacement. All measured BTCs deviated from the Gaussian profile and exhibited the typical anomalous behaviors, such as the long tail and the early arrival. Although the best-fitted results of the advection-dispersion equation (ADE) model and mobile-immobile model (MIM) were generally consistent with those of the BTCs, the MIM was more capable than the ADE model for characterizing the shear-induced anomalous behavior of the BTCs. It was found that the mass exchange process between the immobile and mobile domains was enhanced in the sheared fractures while the fraction of the advection-dominant mobile domain decreased as the shear displacement increased. Furthermore, the deviation of the Taylor dispersion coefficient from the fitted dispersion coefficient by the ADE model and MIM in the sheared fractures was confirmed due to the influence of shear displacement.

Atmospheric deposition is a major source of the nutrients sulfur and selenium to agricultural soils. Air pollution control and cleaner energy production have reduced anthropogenic emissions of sulfur and selenium, which has led to lower atmospheric deposition fluxes of these elements. Here, we use a global aerosol-chemistry-climate model to map recent (2005-2009) sulfur and selenium deposition, and project future (2095-2099) changes under two socioeconomic scenarios. Across the Northern Hemisphere, we find substantially decreased deposition to agricultural soils, by 70 to 90% for sulfur and by 55 to 80% for selenium. Recent trends in sulfur and selenium concentrations in USA streams suggest that catchment mass balances of these elements are already changing due to the declining atmospheric supply. Sustainable fertilizer management strategies will need to be developed to offset the decrease in atmospheric nutrient supply and ensure future food security and nutrition, while avoiding consequences for downstream aquatic ecosystems.

Thallium (Tl) is a highly toxic trace metal. It occurs mostly as soluble monovalent Tl(I) and less frequently as poorly soluble trivalent Tl(III). Laboratory studies have shown that vacancy-containing hexagonal birnessites can sorb Tl with a very high affinity via a mechanism that involves the oxidation of Tl(I) to Tl(III) and strong complexation of Tl(III), whereas other manganese (Mn) oxides bind Tl(I) non-oxidatively and with lower sorption affinity. Information on the mode of Tl uptake by natural Mn oxides in soils, on the other hand, is still limited. In this study, we characterized the association of Tl with Mn oxides and Tl (redox) speciation in a naturally Tl-rich soil using micro-focused synchrotron X-ray absorption near edge structure (XANES) spectroscopy and X-ray fluorescence (XRF) chemical imaging. The results show that most soil Tl was Tl(I) associated with micaceous clay minerals in the soil matrix. High levels of Tl in soil Mn concretions, on the other hand, were mostly identified as Tl(III), suggesting that oxidative Tl uptake by vacancy-containing hexagonal birnessite was the main process of Tl accumulation in soil Mn concretions. The spectroscopic results in combination with chemical extractions and published sorption isotherms for Tl on synthetic Mn oxides suggest that the formation and transformation of natural Mn oxides in soils and sorption competition of Tl with major and trace metal cations determine the extent and mode of Tl uptake by soil Mn oxides. Methodologically, this study compares classical micro-XRF element mapping combined with point XANES analyses for spatially-resolved element speciation with high-resolution chemical imaging of entire sample areas, which is of great interest for the geochemical community in light of diffraction-limited storage ring upgrades to many synchrotron lightsources.

The fate of arsenic (As) in groundwater is determined by multiple interrelated microbial and abiotic processes that contribute to As (im)mobilization. Most studies to date have investigated individual processes related to As (im)mobilization rather than the complex networks present in situ. In this study, we used RNA-based microbial community analysis in combination with groundwater hydrogeochemical measurements to elucidate the behavior of As along a 2 km transect near Hanoi, Vietnam. The transect stretches from the riverbank across a strongly reducing and As-contaminated Holocene aquifer, followed by a redox transition zone (RTZ) and a Pleistocene aquifer, at which As concentrations are low. Our analyses revealed fermentation and methanogenesis as important processes providing electron donors, fueling the microbially mediated reductive dissolution of As-bearing Fe(III) minerals and ultimately promoting As mobilization. As a consequence of high CH₄ concentrations, methanotrophs thrive across the Holocene aquifer and the redox transition zone. Finally, our results underline the role of SO₄²⁻-reducing and putative Fe(II)-/As(III)-oxidizing bacteria as a sink for As, particularly at the RTZ. Overall, our results suggest that a complex network of microbial and biogeochemical processes has to be considered to better understand the biogeochemical behavior of As in groundwater.

High arsenic (As) concentrations in groundwater are a worldwide problem threatening the health of millions of people. Microbial processes are central in the (trans)formation of the As-bearing ferric and ferrous minerals, and thus regulate dissolved As levels in many aquifers. Mineralogy, microbiology and dissolved As levels can vary sharply within aquifers, making high-resolution measurements particularly valuable in understanding the linkages between them. We conducted a high spatial resolution geomicrobiological study in combination with analysis of sediment chemistry and mineralogy in an alluvial aquifer system affected by geogenic As in the Red River delta in Vietnam. Microbial community analysis revealed a dominance of fermenters, methanogens and methanotrophs whereas sediment mineralogy along a 46 m deep core showed a diversity of Fe minerals including poorly crystalline Fe (II/III) and Fe(III) (oxyhydr)oxides such as goethite, hematite, and magnetite, but also the presence of Fe(II)-bearing carbonates and sulfides which likely formed as a result of microbially driven organic carbon (OC) degradation. A potential important role of methane (CH₄) as electron donor for reductive Fe mineral (trans)formation was supported by the high abundance of Candidatus Methanoperedens, a known Fe(III)-reducing methanotroph. Overall, these results imply that OC turnover including fermentation, methanogenesis and CH₄ oxidation are important mechanisms leading to Fe mineral (trans)formation, dissolution and precipitation, and thus indirectly affecting As mobility by changing the Fe-mineral inventory.

Thalliomelane, a new member of the coronadite group (hollandite supergroup), was discovered at Zalas near Cracow in southern Poland (the southern margin of the Cracow–Silesia Monocline) in relics of a preglacial supergene mineralization disseminated in a fault breccia in Middle Jurassic sandy limestone. The mineralization formed at the expense of a sulfide assemblage, which was most likely the source of thallium, related to rejuvenation of Early-Paleozoic fault zones in the Sava phase of the Alpine orogeny. Thalliomelane occurs rarely, and exclusively in the form of fibrous and highly porous tiny aggregates < 50 μm in sizethat fill small fractures and voids in the sandy limestone host rock. Microprobe analyses based on 16 O and 8 octahedral cations per formula unit resulted in the mean empirical formula  (Tl_0.77(10)Ba_0.21(3)K_0.03(1)Na_0.01(0)Pb_0.01(0))_Σ1.03(7)(Mn⁴⁺_7.15(11)Cu²⁺_0.63(4)Co²⁺_0.08(3)Fe³⁺_0.06(3)Ni²⁺_0.03(1)Si₀.₀₃₍₂₎Mg_0.01(1))_Σ8[O_15.67(24)(OH)_0.33(24)], corresponding to the formula Tl(Mn⁴⁺_7.5Cu²⁺_0.5)O₁₆ for the thalliomelane end-member. The mineral crystallizes in the tetragonal system, space group I4/m, and has unit-cell parameters a = 9.8664(12), c = 2.8721(4) Å, V = 279.59(8) ų, Z = 1. The crystal structure of thalliomelane, measured with 3D electron-diffraction, was refined to an R₁ index of 23.74%. Thalliomelane has the hollandite-type structure. The Mn⁴⁺ cations, substituted by Cu²⁺ at an amount of ~0.5 apfu, are octahedrally coordinated by oxygen atoms. Four double chains of edge-sharing (Mn,Cu)-O octahedra share corners with each other to form tunnels along the [001] direction. Tl⁺ cations are located in the tunnels, occupying partially the origin and centre of the unit cell. The formation of thalliomelane was most probably connected to the weathering of a sulfide mineral assemblage under semi-arid to arid climate. It resulted in the release of Tl and other components of the mineralization into water under the influence of Cl-, Br- and I-bearing brines and pore waters from the Carpathian flysch or from sediments of the Carpathian foredeep mobilized by compaction during the Sava phase. Via the interaction of these waters, the primary ores altered mainly into goethite, cuprite, malachite, Mn oxides of the coronadite type, with subordinate Cu sulfates, Pb arsenates, Bi oxy-chlorides, and traces of iodargyrite. This assemblage indicates oxidation at progressively increasing pH of ~8-10 and Eh of the order of +0.4-0.5 V. In this setting, thalliomelane could have formed from a cryptomelane- type Mn oxide in contact with Tl-bearing aqueous solutions through Tl-for-K exchange over time.

Ozonation is increasingly applied in water and wastewater treatment for the abatement of micropollutants (MPs). However, the transformation products formed during ozonation (OTPs) and their fate in biological or sorptive post-treatments is largely unknown. In this project, a high-throughput approach, combining laboratory ozonation experiments and detection by liquid chromatography high-resolution mass spectrometry (LC-HR-MS/MS), was developed and applied to identify OTPs formed during ozonation of wastewater effluent for a large number of relevant MPs (total 87). For the laboratory ozonation experiments, a simplified experimental solution, consisting of surrogate organic matter (methanol and acetate), was created, which produced ozonation conditions similar to realistic conditions in terms of ozone and hydroxyl radical exposures. The 87 selected parent MPs were divided into 19 mixtures, which enabled the identification of OTPs with an optimized number of experiments. The following two approaches were considered to identify OTPs. (1) A screening of LC-HR-MS signal formation in these experiments was performed and revealed a list of 1749 potential OTP candidate signals associated to 70 parent MPs. This list can be used in future suspect screening studies. (2) A screening was performed for signals that were formed in both batch experiments and in samples of wastewater treatment plants (WWTPs). This second approach was ultimately more time-efficient and was applied to four different WWTPs with ozonation (specific ozone doses in the range 0.23-0.55 gO₃/gDOC), leading to the identification of 84 relevant OTPs of 40 parent MPs in wastewater effluent. Chemical structures could be proposed for 83 OTPs through the interpretation of MS/MS spectra and expert knowledge in ozone chemistry. Forty-eight OTPs (58%) have not been reported previously. The fate of the verified OTPs was studied in different post-treatment steps. During sand filtration, 87-89% of the OTPs were stable. In granular activated carbon (GAC) filters, OTPs were abated with decreasing efficiency with increasing run times of the filters. For example, in a GAC filter with 16,000 bed volumes, 53% of the OTPs were abated, while in a GAC filter with 35,000 bed volumes, 40% of the OTPs were abated. The highest abatement (87% of OTPs) was observed when 13 mg/L powdered activated carbon (PAC) was dosed onto a sand filter.

Micropollutants (MP) with varying ozone-reactive moieties were spiked to lake water in the influent of a drinking water pilot plant consisting of an ozonation followed by a biological sand filtration. During ozonation, 227 transformation products (OTPs) from 39 of the spiked 51 MPs were detected after solid phase extraction by liquid chromatography high-resolution mass spectrometry (LC-HRMS/MS). Based on the MS/MS data, tentative molecular structures are proposed. Reaction mechanisms for the formation of a large number of OTPs are suggested by combination of the kinetics of formation and abatement and state-of-the-art knowledge on ozone and hydroxyl radical chemistry. OTPs forming as primary or higher generation products from the oxidation of MPs could be differentiated. However, some expected products from the reactions of ozone with activated aromatic compounds and olefins were not detected with the applied analytical procedure. 187 OTPs were present in the sand filtration in sufficiently high concentrations to elucidate their fate in this treatment step. 35 of these OTPs (19%) were abated in the sand filtration step, most likely due to biodegradation. Only 24 (13%) of the OTPs were abated more efficiently than the parent compounds, with a dependency on the functional group of the parent MPs and OTPs. Overall, this study provides evidence, that the common assumption that OTPs are easily abated in biological post-treatment is not generally valid. Nevertheless, it is unknown how the OTPs, which escaped detection, would have behaved in the biological post-treatment.

In einer Pilotanlage zur Aufbereitung von Seewasser wurden in der Ozonungsstufe 227 Transformationsprodukte detektiert, die aus 39 der insgesamt 51 dem Seewasser zugegebenen Spurenstoffe entstanden waren. Weniger als 20% dieser Transformationsprodukte waren in der nachgeschalteten biologischen Sandfiltration abbaubar. Zudem waren insgesamt nur 13% der im Sandfilter nachgewiesenen Transformationsprodukte besser abbaubar als die Ausgangssubstanzen.

Copper, silver, and gold exploitation has been a foundation of economic and socio-cultural development of Andean societies, at least for the last three millennia. The main centers of pre-colonial metallurgy are well-known from archeological artifacts, but temporal gaps inherent in this record handicap a finer understanding of the modalities of ore exploitation by succeeding civilizations. A continuous record over time of trace metals emitted during ore smelting operations make lake sediments excellent candidates to fill those gaps. Two millennia of metallurgy were reconstructed from atmospherically derived metals together with lead (Pb) isotope ratios in two dated sediment cores from Lake Titicaca. The first evidence for metallurgy is found during the apogee of the Tiwanaku state (AD 800-1150), with a higher copper (Cu) accumulation that can be attributed to the smelting of local Cu ores, based on Pb isotopic fingerprinting. During the Late Intermediate Period (AD 1150-1450), recorded peaks in metal deposition that persisted for ∼ twenty years show that mining activities were intensive but discontinuous. Pb isotope ratios suggest diversified extractive activities, mainly located in the southern part of the central Altiplano. Finally, the most intense mining epoch began during the Inca Empire (ca. AD 1500) and lasted until the end of the Colonial Period (AD 1830), with unprecedented metal deposition over this interval. Pb isotope fingerprinting shows that mining operations occurred mainly in the Lake Titicaca and Potosi areas and were responsible for metal emissions recorded in the entire Altiplano, as evidenced by other studies.

The release of CO₂ from the soil into the atmosphere, due to soil respiration, is a major, yet poorly understood flux that regulates the terrestrial carbon balance. In particular, the apparent insensitivity of soil respiration to emerging combined extreme events of heatwave and drought makes terrestrial ecosystems likely to shift from being carbon sinks to sources. Limited understanding of the interactions underlying this response represents one of the key sources of uncertainty in forecasts of atmospheric CO₂. Here, we explore plant–microbe–soil interactions under heat and drought using a millifluidic setup that enables direct observations of hydration and oxygen content (the primary factors controlling soil respiration) in the root zone. Our observations reveal movement of water between soil regions via roots (termed root hydraulic redistribution), creating soil respiration hotspots and becoming a carbon source under combined heat and drought.

We present noble gas concentrations determined in pore water of deep-sea sediments close to a recently discovered hydrothermal vent site, consisting of a mound structure and several black smokers, located in the northern Guaymas Basin, Gulf of California. Noble gases were used as tracers to identify the origin of fluids within the sediment pore space and to gain insight into transport dynamics of hydrothermal fluids in this region. Our data suggest that Guaymas Basin bottom water is the only source of pore water in the pelagic sediment body close to the hydrothermal vent field. In particular, there is no evidence of any direct (diffusive or advective) transport of hydrothermal fluids through the deep-sea sediments surrounding the black smoker system. This finding implies that at this black smoker site hydrothermal fluids are transported upwards from the fluid source in very narrow pathways below the smokers. Thus, the fluids are only injected into the ocean directly through the chimneys of the black smokers and no additional emission from the surrounding sediment takes place. Helium isotope data show that during a more active phase of the vent field in the past (supposedly representing the early onset of the black smokers 5-6 kyrs ago), bottom water with a different isotopic signature was incorporated into the sediment column.

The application of oxidants for disinfection or micropollutant abatement during drinking water and wastewater treatment is accompanied by oxidation of matrix components such as dissolved organic matter (DOM). To improve predictions of the efficiency of oxidation processes and the formation of oxidation products, methods to determine concentrations of oxidant-reactive phenolic, olefinic or amine-type DOM moieties are critical.
Here, a novel selective oxidative titration approach is presented, which is based on reaction kinetics of oxidation reactions towards certain DOM moieties. Phenolic moieties were determined by oxidative titration with ClO₂ and O₃ for five DOM isolates and two secondary wastewater effluent samples. The determined concentrations of phenolic moieties correlated with the electron-donating capacity (EDC) and the formation of inorganic ClO₂-byproducts (HOCl, ClO₂⁻, ClO₃⁻). ClO₂-byproduct yields from phenol and DOM isolates and changes due to the application of molecular tagging for phenols revealed a better understanding of oxidant-reactive structures within DOM.
Overall, oxidative titrations with ClO₂ and O₃ provide a novel and promising tool to quantify oxidant-reactive moieties in complex mixtures such as DOM and can be expanded to other matrices or oxidants.

Combining iron with a tetraamido-macrocyclic ligand (Fe-TAML) as a catalyst and with hydrogen peroxide (H₂O₂) as the bulk oxidant is a process that has been suggested for the oxidative abatement of micropollutants during water treatment. In this study, the reactivity of the Fe-TAML/H₂O₂ system was evaluated by investigating the degradation of a group of electron-rich organic model compounds with different functional groups in a secondary wastewater effluent. Phenolic compounds and a polyaromatic ether are quickly and substantially abated by Fe-TAML/H₂O₂ in a wastewater effluent. For tertiary amines, a moderate rate of abatement was observed. Primary and secondary amines, aromatic ethers, aromatic aldehydes, and olefins are oxidized too slowly in the investigated Fe-TAML/H₂O₂ systems to be significantly abated in a secondary wastewater effluent. Trichlorophenol is readily oxidized to chloromaleic acid and chlorofumaric acid, which support a one-electron transfer reaction as the initial step of the reaction between Fe-TAML/H₂O₂ and the target compound. Fe-TAML/H₂O₂ does not oxidize bromide to hypobromous acid; however, iodide is oxidized to hypoiodous acid, and as a consequence, the H₂O₂ consumption is accelerated by a catalytic reaction in iodide-containing water. Overall, Fe-TAML/H₂O₂ is a rather selective oxidant, which makes it an interesting system for the abatement of electron-rich phenolic-type pollutants.

Mercury (Hg) records in sediment archives inform past patterns of Hg deposition and the anthropogenic contribution to global Hg cycling. Natural climate variations complicate the interpretation of past Hg accumulation rates (HgARs), warranting additional research. Here, we investigated Hg stable isotopes in a ca. 8k year-long sediment core of Lake Titicaca and combined isotopic data with organic biomarkers and biogeochemical measurements. A wet period in the early Holocene (8000–7300 BP) induced strong watershed erosion, leading to a high HgAR (20.2 ± 6.9 μg m^–2 year^–1), which exceeded the 20th century HgAR (8.4 ± 1.0 μg m^–2 year^–1). Geogenic Hg input dominated during the early Holocene (f_geog = 79%) and played a minor role during the mid- to late Holocene (4500 BP to present; f_geog = 20%) when atmospheric Hg deposition dominated. Sediment Δ²⁰⁰Hg values and the absence of terrestrial lignin biomarkers suggest that direct lake uptake of atmospheric Hg(0), and subsequent algal scavenging of lake Hg, represented an important atmospheric deposition pathway (42%) during the mid- to late Holocene. During wet episodes of the late Holocene (2400 BP to present), atmospheric Hg(II) deposition was the dominant source of lake sediment Hg (up to 82%). Sediment Δ¹⁹⁹Hg values suggest that photochemical reduction and re-emission of Hg(0) occurred from the lake surface. Hg stable isotopes show promise as proxies for understanding the history of Hg sources and transformations and help to disentangle anthropogenic and climate factors influencing HgAR observed in sediment archives.

Study region: Northeastern Iran.
Study focus: In northeastern Iran, water needed for municipal and agricultural activities mainly comes from groundwater resources. However, it is subject to substantial anthropogenic and geogenic contamination. We characterize the sources of groundwater contamination by employing an integrated approach that can be applied to the identification of large-scale contamination sources in other regions. An existing dataset of georeferenced water quality parameters from 676 locations in northeast of Iran was analyzed to investigate the geochemical properties of groundwater. Gridding of the parameters graphically illustrates the areas affected by high concentrations of As, Cl⁻, Cr, Fe, Mg²⁺, Na⁺, NO₃⁻, Se, and SO₄^2-. We then identified potential anthropogenic and geogenic contamination sources by employing random forest (RF) regression modeling.
New hydrological insights for the region: Random forest (RF) models show that the major ions, As, Cr, Fe, and Se content of groundwater are mainly determined by geology in the study area. Modeling also links groundwater NO₃⁻ contamination with sewage discharge into aquifers as well as the application of nitrogenous and animal-waste fertilizers. Areas of high salinity result from evaporate deposits and irrigation return flow. Medium to high non-carcinogenic health risk is found in areas with high concentrations of geogenic As and Cr in groundwater. Our approach can be applied elsewhere to analyze regional groundwater quality and associated health risks as well as identify potential sources of contamination.

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.

Groundwater is a major drinking water resource, providing on average 50% of domestic water supply worldwide; in several European countries, this can even be as high as 70-100%. Although groundwater is better protected from anthropogenic influences than surface waters, a broad variety of chemicals used in agriculture, households, and industry have been detected in groundwater in the ngL^-1 to μgL^-1 range. Chemicals may enter groundwater via seepage after pesticide application to agricultural soils, from leaky sewers, or from the infiltration of wastewater-impacted surface waters. Natural attenuation processes such as sorption and (bio)transformation do not sufficiently retain polar, mobile, and persistent micropollutants (MPs) and may even lead to the formation of polar transformation products (TPs). Compared to the large number of chemicals potentially released into the aquatic environment, previous research and monitoring programs focused only on a few compounds so that groundwater quality with regard to organic MPs is largely unknown. [...]

Grundwasser ist eine wichtige Trinkwasserressource, welche weltweit 50% des Wasserbedarfs von Haushalten bereitstellt und in mehreren europäischen Ländern sogar 70-100%. Obwohl Grundwasser besser vor anthropogenen Einflüssen geschützt ist als Oberflächengewässer, wurden im Grundwasser zahlreiche Chemikalien aus der Landwirtschaft, Haushalten und Industrie im ngL^-1 bis μgL^-1 Bereich nachgewiesen. Chemikalien können mit dem Sickerwasser ins Grundwasser eingetragen werden infolge der Anwendung von Pestiziden auf  landwirtschaftlichen Böden, aufgrund undichter Abwasserkanäle oder durch die Infiltration von mit Abwasser belasteten Oberflächengewässern. Natürliche Prozesse wie Sorption und (Bio-) Transformation halten polare, mobile und persistente Spurenstoffe nicht ausreichend zurück und können sogar zur Bildung polarer Transformationsprodukte (TPs) führen. Im Vergleich zur grossen Zahl an Chemikalien, die möglicherweise in den Wasserkreislauf freigesetzt werden, umfassten bisherige Untersuchungen und Monitoringprogramme nur wenige Verbindungen, so dass die Grundwasserqualität in Bezug auf organische Spurenstoffe weitgehend unbekannt ist. [...]

Structure, reactivity and physico-chemical properties of polyhalogenated compounds determine their up-take, transport, bio-accumulation, transformation and toxicity and their environmental fate. In technical mixtures of chlorinated paraffins (CPs), these properties are distributed due to the presence of thousands of homologues. We hypothesized that roles of CP dehalogenation reactions, catalyzed by the haloalkane dehalogenase LinB, depend on structural properties of the substrates, e.g. chlorination degree and carbon-chain length. We exposed mixtures of chlorinated undecanes, dodecanes and tridecanes in-vitro to LinB from Sphingobium Indicum bacteria. These single-chain CP-materials also contain small amounts of chlorinated olefins (COs), which can be distinct by mathematical deconvolution of respective mass-spectra. With this procedure, we obtained homologue-specific transformation kinetics of substrates differing in saturation degree, chlorination degree and carbon chain-length. For all homologues, two-stage first-order kinetic models were established, which described the faster conversion of reactive material and the slower transformation of more persistent material. Half-lifes of 0.5–3.2 h and 56–162 h were determined for more reactive and more persistent CP-material. Proportions of persistent material increased steadily from 18 to 67% for lower (Cl₆) to higher (Cl₁₁) chlorinated paraffins and olefins. Conversion efficiencies decreased with increasing chlorination degree from 97 to 70%. Carbon-chain length had only minor effects on transformation rates. Hence, the conversion was faster and more efficient for lower-chlorinated material, and slower for higher-chlorinated and longer-chained CPs and COs. Current legislation has banned short-chain chlorinated paraffins (SCCPs) and forced a transition to longer-chain CPs. This may be counterproductive with regard to enzymatic transformation with LinB.

Short-chain chlorinated paraffins (SCCPs) are listed as persistent organic pollutants (POPs) under the Stockholm Convention. Such substances are toxic, bioaccumulating, transported over long distances and degrade slowly in the environment. Certain bacterial strains of the Sphingomonadacea family are able to degrade POPs, such as hexachlorocyclohexanes (HCHs) and hexabromocyclododecanes (HBCDs). The haloalkane dehalogenase LinB, expressed in certain Sphingomonadacea, is able to catalyze the transformation of haloalkanes to hydroxylated compounds. Therefore, LinB is a promising candidate for conversion of SCCPs. Hence, a mixture of chlorinated tridecanes was exposed in vitro to LinB, which was obtained through heterologous expression in Escherichia coli. Liquid chromatography mass spectrometry (LC-MS) was used to analyze chlorinated tridecanes and their transformation products. A chloride-enhanced soft ionization method, which favors the formation of chloride adducts [M+Cl]^- without fragmentation, was applied. Mathematical deconvolution was used to distinguish interfering mass spectra of paraffinic, mono-olefinic and di-olefinic compounds. Several mono- and di-hydroxylated products including paraffinic, mono-olefinic and di-olefinic compounds were found after LinB exposure. Mono- (rt = 5.9–6.9 min) and di-hydroxylated (rt = 3.2–4.5 min) compounds were separated from starting material (rt = 7.7–8.5 min) by reversed phase LC. Chlorination degrees of chlorinated tridecanes increased during LinB-exposure from n_Cl = 8.80 to 9.07, indicating a preferential transformation of lower chlorinated (Cl_<9) tridecanes. Thus, LinB indeed catalyzed a dehalohydroxylation of chlorinated tridecanes, tridecenes and tridecadienes. The observed hydroxylated compounds are relevant CP transformation products whose environmental and toxicological effects should be further investigated.

Iron minerals are the most important arsenic host in As-contaminated deltaic sediments. Arsenic release from Fe minerals to groundwater exposes millions of people worldwide to a severe health threat. To understand the coupling of Fe mineralogy with As (im)mobilization dynamics, we analyzed the geochemistry and mineralogy of a 46 m long sediment core drilled into the redox transition zone where a high As Holocene aquifer is juxtaposed to a low As Pleistocene aquifer in the Red River delta, Vietnam. We specifically concentrated on mm- to cm-scale redox interfaces within the sandy aquifer. Various Fe phases, such as Fe- and Mn- bearing carbonates, pyrite, magnetite, hematite and Fe-hydroxides (goethite, lepidocrocite) with distinct As concentrations were identified by a combination of high-resolution microscopic, magnetic and spectroscopic methods. The concentration of As and its redox species in the different Fe-minerals were quantified by microprobe analysis and synchrotron X-ray absorption. We developed a conceptual model integrating Fe-mineral transformations and related As (im)mobilization across the redox interfaces. Accordingly, As is first mobilized via the methanogenic dissolution of Fe(III) (oxyhydr)oxide mineral coatings on sand grains when reducing groundwater from the Holocene aquifer intruded into the Pleistocene sands. This stage is followed by the formation of secondary Fe(II)-containing precipitates (mainly Fe- and Mn-bearing carbonates with relatively low As < 70 μg/g), and minor pyrite (with high As up to 5800 μg/g). Due to small-scale changing redox conditions these Fe(II) minerals dissolve again and the oxidative behavior of residual Fe(III)-phases in contact with the reducing water leads to the formation of abundant Fe(III)/Fe(II) (oxyhydr)oxides especially at the studied redox interfaces. Microcrystalline coatings and cementations of goethite, magnetite and hematite have intermediate to high As sorption capacity (As up to 270 μg/g) creating a key sorbent responsible for As (im)mobilization at interfingering redox fronts. Our observations suggest a dynamic system at the redox interfaces with coupled redox reactions of abiotic and biotic origin on a mm to cm-scale. In a final stage, further reduction creates magnetite with low As sorption capacity as important secondary Fe-mineral remaining in reduced gray Pleistocene aquifer sands while considerable Fe and As is released into the groundwater. The presented redox-dependent sequence of Fe phases at redox interfaces provides new insights of their role in As (im)mobilization in reducing aquifers of south and southeast Asia.

This study focuses on the effects of ozonation on the optical and photochemical properties of dissolved organic matter (DOM). Upon ozonation, a decrease in light absorption properties of DOM was observed concomitantly with a large increase in singlet oxygen (¹O₂) and hydroxyl radical (˙OH) quantum yields (Φ_¹O2 and Φ_˙OH, respectively). The decrease in absorbance was linked to the reaction of DOM chromophores with ozone and ˙OH, formed as a secondary oxidant, while the increase in Φ_¹O2 and Φ_˙OH are linked to the formation of quinone-like moieties from the reaction of ozone with phenolic DOM moieties. Investigations using benzoic acid as a ˙OH probe and methanol as a ˙OH scavenger indicated that not only is ˙OH formed, but that other hydroxylating species (˙OH-like) are also produced upon DOM photo-irradiation.

Transported chemical reactions in unsaturated porous media are relevant to environmental and industrial applications. Continuum scale models are based on equivalent parameters derived from analogy with saturated conditions and cannot appropriately account for incomplete mixing. It is also unclear how the third dimension controls mixing and reactions. We obtain three-dimensional (3D) images by magnetic resonance imaging using an immiscible nonwetting liquid as a second phase and a fast irreversible bimolecular reaction. We study the impact of phase saturation on the dynamics of mixing and the reaction front. We quantify the temporally resolved effective reaction rate and describe it using the lamellar theory of mixing, which explains faster than Fickian (t^0.5) rate of product formation by accounting for the deformation of the mixing interface between the two reacting fluids. For a given Péclet, although stretching and folding of the reactive front enhance as saturation decreases, enhancing the product formation, the product formation is larger as saturation increases. After breakthrough, the extinction of the reaction takes longer as saturation decreases because of the larger nonmixed volume behind the front. These results are the basis for a general model to better predict reactive transport in unsaturated porous media not achievable by the current continuum paradigm.

Chemical disinfectants employed in water and wastewater treatment can produce a variety of transformation products, including carbonyl compounds (e.g., saturated and unsaturated aldehydes and ketones). Experiments conducted under conditions relevant to chlorination at drinking water treatment plants and residual chlorine application in distribution systems indicate that α,β-unsaturated carbonyl compounds readily react with free chlorine and free bromine over a wide pH range but react slowly with combined chlorine (i.e., NH₂Cl). For nearly all of the 11 α,β-unsaturated carbonyl compounds studied, the apparent second-order rate constants for the reaction with free chlorine increased in a linear manner with hypochlorite (OCl^–) concentrations, yielding species-specific second-order rate constants for the reaction with OCl^– ranging from 0.21 to 12 M^–1 s^–1. Predictions based on the second-order rate constants indicate that a substantial fraction (i.e., >60%) of several of the more prominent α,β-unsaturated carbonyls (e.g., acrolein, crotonaldehyde) will be transformed to an appreciable extent in distribution systems by free chlorine. Products from the reaction of chlorine with acrolein, crotonaldehyde, and methyl vinyl ketone were tentatively identified using nuclear magnetic resonance (NMR) and gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC–HRT-MS). These products lacked unsaturated carbons and, in some cases, contained multiple halogens.

Urban groundwater management requires a thorough and robust scientific understanding of flow and transport processes. ³H/³He apparent ages have been shown to efficiently help provide important groundwater-related information. However, this type of analysis is expensive as well as labor- and time-intensive, and hence limits the number of potential sampling locations.
To overcome this limitation, we established an inter-relationship between ³H/³He apparent groundwater ages and ⁴He concentrations analyzed in the field with a newly developed portable gas equilibrium membrane inlet mass spectrometer (GE-MIMS) system, and demonstrated that the results of the simpler GE-MIMS system are an accurate and reliable alternative to sophisticated laboratory based analyses. The combined use of ³H/³He lab-based ages and predicted ages from the ³H/³He–⁴He age relationship opens new opportunities for site characterization, and reveals insights into the conceptual understanding of groundwater systems.
For our study site, we combined groundwater ages with hydrochemical data, water isotopes (¹⁸O and ²H), and perchloroethylene (PCE) concentrations (1) to identify spatial inter-aquifer mixing between artificially infiltrated groundwater and water originating from regional flow paths and (2) to explain the spatial differences in PCE contamination within the observed groundwater system. Overall, low PCE concentrations and young ages occur when the fraction of artificially infiltrated water is high. The results obtained from the age distribution analysis are strongly supported by the information gained from the isotopic and hydrochemical data. Moreover, for some wells, fault-induced aquifer connectivity is identified as a preferential flow path for the transport of older groundwater, leading to elevated PCE concentrations.

In the lowlands of Nepal (Terai), the WHO drinking water guideline concentration of 10 μg/L for arsenic (As) is frequently exceeded. Since their introduction in 2006, iron-assisted bio-sand filters (Kanchan filters) are widely used to treat well water in Nepal. The filters are constructed on the basis of As-removal with corroding zero-valent iron (ZVI), with water flowing through a filter bed of iron nails placed above a sand filter. According to several studies, the performance of Kanchan filters varies greatly and depends on the size of the iron nails, filter design, water composition, and operating conditions, leading to concerns about their actual efficiency. This study examined 38 Kanchan household filters for which insufficient As-removal was reported, to evaluate the reasons for limited removal efficiency and to define measures for improved performance. The measured arsenic removal ranged from 6.3% to 98.5%. The most relevant factors were the concentrations of As and Fe in the raw water, with the best removal efficiency observed for water with low As (123 µg/L) and high Fe (5.0 mg/L). Although the concentrations of other elements, pH, flow rates, and contact time with ZVI also played a role, the combined evidence indicated that the reactivity of the frequently drying nail beds between filtrations was insufficient for efficient As-removal. Optimized filters with added top layers of sand and raised water outlets with flow restrictions to keep nails permanently immersed and to increase contact times, should be able to achieve higher and more consistent arsenic removal efficiencies.

Recently, we suggested that hypobromous acid (HOBr) is a sink for the marine volatile organic sulfur compound dimethyl sulfide (DMS). However, HOBr is also known to react with reactive moieties of dissolved organic matter (DOM) such as phenolic compounds to form bromoform (CHBr₃) and other brominated compounds. The reaction between HOBr and DMS may thus compete with the reaction between HOBr and DOM. To study this potential competition, kinetic batch and diffusion-reactor experiments with DMS, HOBr, and DOM were performed. Based on the reaction kinetics, we modeled concentrations of DMS, HOBr, and CHBr₃ during typical algal bloom fluxes of DMS and HOBr (10^-13 to 10^-9 M s^-1). For an intermediate to high HOBr flux (≥10^-11 M s^-1) and a DMS flux ≤10^-11 M s^-1, the model shows that the DMS degradation by HOBr was higher than for photochemical oxidation, biological consumption, and sea–air gas exchange combined. For HOBr fluxes ≤10^-11 M s^-1 and a DMS flux of 10^-11 M s^-1, our model shows that CHBr₃ decreases by 86% compared to a lower DMS flux of 10^-12 M s^-1. Therefore, the reaction between HOBr and DMS likely not only presents a sink for DMS but also may lead to suppressed CHBr₃ formation.

To assess the risks associated with cyanobacterial blooms, the persistence and fate processes of cyanotoxins and other bioactive cyanobacterial metabolites need to be evaluated. Here, we investigated the reaction with photochemically produced singlet oxygen (¹O₂) for 30 cyanopeptides synthesized by Dolichospermum flos aquae, including 9 anabaenopeptins, 18 microcystins, 2 cyanopeptolins, and 1 cyclamide. All compounds were stable in UVA light alone but in the presence of a photosensitizer we observed compound-specific degradation. A strong pH effect on the decay was observed for 18 cyanopeptides that all contained tyrosine or structurally related moieties. We can attribute this effect to the reaction with ¹O₂ and triplet sensitizer that preferentially react with the deprotonated form of tyrosine moieties. The contribution of ¹O₂ to indirect phototransformation ranged from 12 to 39% and second-order rate constants for 9 tyrosine-containing cyanopeptides were assessed. Including the pH dependence of the reaction and system-independent second-order rate constants with ¹O₂ will improve the estimation of half-lives for multiclass cyanopeptide in surface waters. Our data further indicates that naturally occurring triplet sensitizers are likely to oxidize deprotonated tyrosine moieties of cyanopeptides and the specific reactivity and its pH dependence needs to be investigated in future studies.

Although phosphate (PO₄^3-) may play a decisive role in enriching toxic arsenic (As) in the groundwater of many Asian deltas, knowledge gaps exist regarding its interactions with As. This study investigates the simultaneous immobilisation of PO₄^3- and As in aquifer sediments at a redox transition zone in the Red River Delta of Vietnam. The majority of PO₄^3- and As was found to be structurally bound in layers of Fe(III)-(oxyhydr)oxide precipitates, indicating that their formation represents a dominant immobilisation mechanism. This immobilisation was also closely linked to sorption. In the surface sorbed sediment pools, the molar ratios of total P to As were one order of magnitude higher than found in groundwater, reflecting a preferential sorption of PO₄^3- over As. However, this competitive sorption was largely dependent on the presence of Fe(III)-(oxyhydr)oxides. Ongoing contact of the aquifer sediments with iron-reducing groundwater resulted in the reductive dissolution of weakly crystalline Fe(III)-(oxyhydr)oxides, which was accompanied by decreased competition for sorption sites between PO₄^3- and As. Our results emphasise that, to be successful in the medium and long term, remediation approaches and management strategies need to consider competitive sorption between PO₄^3- and As and dynamics of the biogeochemical Fe-cycle.

We study pore-scale dynamics of reactive transport in heterogeneous, dual-porosity media, wherein a reactant in the invading fluid interacts chemically with the surface of the permeable grains, leading to the irreversible reaction A_aq + B_s → C_aq. A microfluidic porous medium was synthesized, consisting of a single layer of hydrogel pillars (grains), chemically modified to contain immobilized enzymes on the grain surfaces. Fluorescence microscopy was used to monitor the spatiotemporal evolution of the reaction product C_aq at different flow rates (Péclet values) and to characterize the impact on its transport. The experimental setup enables delineation of three key features of the temporal evolution of the reaction product within the domain: (i) the characteristic time until the rate of C_aq production reaches steady state, (ii) the magnitude of the reaction rate at steady state, and (iii) the rate at which C_aq is flushed from the system. These features, individually, are found to be sensitive to the value of the Péclet number, because of the relative impact of diffusion (vs advection) on the production and spatiotemporal evolution of C_aq within the system. As the Péclet number increases, the production of C_aq is reduced and the transport becomes more localized within the vicinity of the grains. The dual-porosity feature causes the residence time of the transported species to increase, by forming stagnant zones and diffusive-dominant regions within the flow field, thus enhancing the reaction potential of the system. Using complementary numerical simulations, we explore these effects for a wider range of Péclet and Damköhler numbers and propose nonlinear scaling laws for the key features of the temporal evolution of C_aq.

Biological N₂ fixation was key to the expansion of life on early Earth. The N₂-fixing microorganisms and the nitrogenase type used in the Proterozoic are unknown, although it has been proposed that the canonical molybdenum-nitrogenase was not used due to low molybdenum availability. We investigate N₂ fixation in Lake Cadagno, an analogue system to the sulfidic Proterozoic continental margins, using a combination of biogeochemical, molecular and single cell techniques. In Lake Cadagno, purple sulfur bacteria (PSB) are responsible for high N₂ fixation rates, to our knowledge providing the first direct evidence for PSB in situ N₂ fixation. Surprisingly, no alternative nitrogenases are detectable, and N₂ fixation is exclusively catalyzed by molybdenum-nitrogenase. Our results show that molybdenum-nitrogenase is functional at low molybdenum conditions in situ and that in contrast to previous beliefs, PSB may have driven N₂ fixation in the Proterozoic ocean.

Agricultural irrigation is the major water consumer in the Mediterranean region. In response to the growing pressure on freshwater resources, more efficient irrigation technologies have been widely promoted. In this study, we assess the impact of the ongoing transition from flood to drip irrigation on future hydroclimatic regimes under various climate change scenarios, with a particular focus on actual evapotranspiration and groundwater recharge in the Mediterranean region of Valencia, Spain. Hydroclimatic predictions for the near‐term future (2020‐2049) and the mid‐term future (2045‐2074) were made under two emission scenarios (RCP 4.5 and RCP 8.5) using a hydrological model that was forced with data from five GCM‐RCM combinations and field‐based irrigation volume and frequency observations. Our findings suggest that climate change could lead to statistically significant changes in the regional hydroclimatic regime despite projection uncertainties. Major changes include a statistically significant decrease in mean groundwater recharge of up to ‐6.6% under flood irrigation and ‐9.3% under drip irrigation and contrasting changes in mean actual evapotranspiration for flood and drip irrigation in the order of +1% and ‐2.1%, respectively. Since sustainably available water resources in the Valencia region are entirely allocated, the expected changes and associated uncertainties create a challenging context for future water management. Our simulations further indicate that, rather than climate change, the choice of irrigation technique may have a greater impact on actual evapotranspiration and groundwater recharge. Our findings therefore highlight the importance of considering both climate change and irrigation technique when assessing future water resources in irrigated Mediterranean agriculture.

Hydrological models have traditionally been used for the prediction in ungauged basins despite the related challenge of model parameterization. Short measurement campaigns could be a way to obtain some basic information that is needed to support model calibration in these catchments. This study explores the potential of such field campaigns by i) testing the relative value of continuous water-level time series and point discharge observations for model calibration, and by ii) evaluating the value of point discharge observations collected using expert knowledge and active learning to guide when to measure streamflow. The study was based on 100 gauged catchments across the contiguous United States for which we pretended to have only limited hydrological observations, i.e., continuous daily water levels and ten daily point discharge observations from different hypothetical field trips conducted within one hydrological year. Water level data were used as a single source of information, as well as in addition to point discharge observations, for calibrating the HBV model. Calibration against point discharge observations was conducted iteratively by continually adding new observations from one of the ten field measurements. Our results suggested that the information contained in point discharge observations was especially valuable for constraining the annual water balance and streamflow response at the event scale, improving predictions based solely on water levels by up to 50% after ten field observations. In contrast, water levels were valuable to increase the accuracy of simulated daily streamflow dynamics. Informative discharge sampling dates were similar when selected with either active learning or expert knowledge and typically clustered during seasons with high streamflow.

The replacement of flood-irrigation systems by drip-irrigation technology has been widely promoted with the aim of a more sustainable use of freshwater resources in irrigated agriculture. However, evidence for an irrigation efficiency paradox emphasizes the need to improve our understanding of the impacts of irrigation transformations on water resources. Here, we developed a distributed hydrological modeling approach to investigate the spatiotemporal effect of flood and drip irrigation on groundwater recharge. The approach recognizes differences in the water balance resulting from the localized application of water in surface drip-irrigated fields and the more extensive application of water in flood irrigation. The approach was applied to the semi-arid Mediterranean region of Valencia (Spain) and calibrated using a multi-objective framework. Multiple process scales were addressed within the framework by considering the annual evaporative index, monthly groundwater level dynamics, and daily soil moisture dynamics. Daily simulations from 1994 to 2015 suggested that, in our hydroclimatic conditions, (a) annual recharge is strongly related to annual rainfall, which had a four times higher impact on recharge than the type of irrigation practice, (b) flood-irrigated recharge tends to exceed drip-irrigated recharge by 10% at annual time scales, (c) however, recharge response to a particular precipitation event is smaller in flood irrigation than in drip irrigation, and (d) 8–18 rainfall events could generate more than half of the annual recharge in drip and flood irrigation, respectively. Our results highlight the importance of understanding the hydrological dynamics under different irrigation practices for supporting irrigation infrastructure policies.

Model parameter values for ungauged catchments can be regionalized from hydrologically similar gauged catchments. Achieving reliable and robust predictions in ungauged catchments by regionalization, however, is still a major challenge. Here, we conduct a comparative assessment of 19 regionalization approaches based on previously published literature to contribute new insights into their performance in different geographic regions. The approaches use geographical information, physical catchment attributes, hydrological signatures, or a combination thereof to select donor catchments and to subsequently transfer their entire parameter sets to the ungauged receiver catchment. Each regionalization approach was tested in a leave-one-out cross-validation with a bucket-type catchment model (the HBV model) using 671 gauged catchments in the United States with a diverse hydroclimatology. We then evaluated regionalization performance for several hydrograph aspects, compared it against calibration and regionalization benchmarks, and linked it to catchment descriptors. The results of this large-sample regionalization study can be summarized in three major lessons: (a) Catchments can benefit from a well-chosen regionalization approach independent of their geographic region and independent of how well they can be modeled or regionalized at best. (b) Almost perfect donors exist for most catchments and an excellent relative model performance can be reached for most catchments with current regionalization approaches. This implies that there is considerable potential for improvement in the prediction in ungauged catchments. (c) The ranking of regionalization approaches depends on how the predicted hydrographs are evaluated. These findings indicate that a multi-criteria evaluation is essential for a robust assessment of regionalization performance.

Understanding the mixing between surface water and groundwater as well as groundwater travel times in vulnerable aquifers is crucial to sustaining a safe water supply. Age dating tracers used to infer apparent travel times typically refer to the entire groundwater sample. A groundwater sample, however, consists of a mixture of waters with a distribution of travel times. Age dating tracers only reflect the proportion of the water that is under the dating range of the used tracer, thus their interpretation is typically biased. Additionally, end-member mixing models are subject to various sources of uncertainties, which are typically neglected. In this study, we introduce a new framework that untangles groundwater mixing ratios and travel times using a novel combination of in-situ noble gas analyses. We applied this approach during a groundwater pumping test carried out in a pre-alpine Swiss valley. First, we calculated transient mixing ratios between recently infiltrated river water and regional groundwater present in a wellfield, using helium-4 concentrations combined with a Bayesian end-member mixing model. Having identified the groundwater fraction of recently infiltrated river water (F_rw) consequently allowed us to infer the travel times from the river to the wellfield, estimated based on radon-222 activities of F_rw. Furthermore, we compared tracer-based estimates of F_rw with results from a calibrated numerical model. We demonstrate (i) that partitioning of major water sources enables a meaningful interpretation of an age dating tracer of the water fraction of interest and (ii) that the streambed has a major control on the estimated travel times.

Radiokrypton dating using the long-lived natural isotope ⁸¹Kr has been developed for determining the age of ancient groundwater. ⁸¹Kr is attractive for this purpose because it is generally thought to be produced solely in the upper atmosphere. Its 229,000-year half-life, a spatially homogeneous distribution in the atmosphere, and the absence of anthropogenic sources makes it an ideal tracer to determine ages up to ∼1.3 million years. As a noble gas, it is inert and thus not subject to interfering geochemical reactions that may alter the age information. We sought to date groundwater samples collected from deep (0.6–1.9 km) rock fractures in the Kaapvaal Craton, South Africa. Previous studies using other dating methods have estimated groundwater ages at these sites in the 1–100 million year range. Surprisingly, three of the four samples collected from flowing boreholes in gold and diamond mines showed ⁸¹Kr isotopic abundances at 2–5 times the atmospheric value. This is the first time that underground production of ⁸¹Kr has been detected, indicating that ⁸¹Kr can be generated underground in measurable quantities in contrast to the long-held paradigm that such production is insignificant in natural rocks. A radionuclide production and release model is proposed in order to quantify the importance of different factors that affect the concentrations of ⁸¹Kr in the groundwater. It is not only the high effective uranium content of the rock but also a higher ⁸¹Kr fission yield than previously anticipated that are likely causing the elevated ⁸¹Kr values in this case. In less extreme environments with average crustal composition (i.e. moderate U concentration), however, we anticipate that the underground production minimally affects groundwater ⁸¹Kr dating as demonstrated.

Uncertainty estimation plays an important part in practical hydrogeology. With most of the subsurface unobservable, attempts at system characterization will invariably be incomplete. Uncertainty estimation, then, must quantify the influence of unknown parameters, forcings, and structural deficiencies. In this endeavor, numerical modeling frameworks can resolve a high degree of subsurface complexity and its associated uncertainty. Where boundary uncertainty is concerned, however, numerical frameworks can be restrictive. The interdependence of grid discretization and its enclosing boundaries render exploration of uncertainties in their extent or nature challenging. The analytic element method (AEM) may be an interesting complement, as it is computationally efficient, economic with its parameter count, and does not require enclosure through finite boundaries. These properties make AEM well suited for uncertainty estimation, particularly in data-scarce settings or exploratory studies. In this study, we explore the use of AEM for flow field uncertainty estimation, with a particular focus on boundary uncertainty. To induce diverse, uncertain regional flow more easily, we propose a new element based on a Möbius transformation. We include this element in a simple Python-based AEM toolbox and benchmark it against MODFLOW. Coupling AEM with a Markov Chain Monte Carlo routine using adaptive proposals, we explore its use in a synthetic case study. We find that AEM permits efficient uncertainty estimation for groundwater flow fields, which may form a basis for stochastic Lagrangian transport modeling or can support advanced model design by informing the placement of numerical model boundaries.

The sustainable management of groundwater demands a faithful characterization of the subsurface. This, in turn, requires information which is generally not readily available. To bridge the gap between data need and availability, numerical models are often used to synthesize plausible scenarios not only from direct information but also additional, indirect data. Unfortunately, the resulting system characterizations will rarely be unique. This poses a challenge for practical parameter inference: Computational limitations often force modelers to resort to methods based on questionable assumptions of Gaussianity, which do not reproduce important facets of ambiguity such as Pareto fronts or multi‐modality. In search of a remedy, an alternative could be found in Stein Variational Gradient Descent (SVDG), a recent development in the field of statistics. This ensemble‐based method iteratively transforms a set of arbitrary particles into samples of a potentially non‐Gaussian posterior, provided the latter is sufficiently smooth. A prerequisite for this method is knowledge of the Jacobian, which is usually exceptionally expensive to evaluate. To address this issue, we propose an ensemble‐based, localized approximation of the Jacobian. We demonstrate the performance of the resulting algorithm in two cases: a simple, bimodal synthetic scenario, and a complex numerical model based on a real‐world, pre‐alpine catchment. Promising results in both cases - even when the ensemble size is smaller than the number of parameters - suggest that Stein Variational Gradient Descent can be a valuable addition to hydrogeological parameter inference.

Accidental spills or illegal discharges of pesticides in aquatic ecosystems can lead to exposure levels that strongly exceed authorized pesticide concentrations, causing major impacts on aquatic ecosystems. Such short-term events often remain undetected in regular monitoring programs with infrequent sampling. In early spring 2015, we identified a catastrophic pesticide spill with the insecticide cypermethrin in the Holtemme River, Germany. Based on existing pre-event macroinvertebrate community data, we monitored the effects and recovery of the macroinvertebrate community for more than two years after the spill. Strong short-term effects were apparent for all taxa with the exception of Chironomidae and Tubificidae. Effects could also be observed on the community level as total abundance, taxa number and biomass strongly decreased. Total abundance and taxa number showed a fast recovery. Regarding long-term effects, the total biomass remained substantially below the pre-contamination level (76%) until the end of the study. Also the abundances of three taxa (Gammarus, Leuctra, Limnius Ad.) did not return to levels prior to the spill even after 26 months. This lack of the taxon-specific recovery was likely due to their long generation time and a low migration ability due to a restricted connectivity between the contaminated site and uncontaminated stream sections. These factors proved to be stronger predictors for the recovery than the pesticide tolerance. We revealed that the biological indicators SPEARpesticides and share of Ephemeroptera, Plecoptera and Trichoptera (EPT) are not suitable for the identification of such extreme events, when nearly all taxa are eradicated. Both indicators are functioning only when repeated stressors initiate long-term competitive replacement of sensitive by insensitive taxa. We conclude that pesticide spills can have significant long-term effects on stream macroinvertebrate communities. Regular ecological monitoring is imperative to identify such ecosystem impairments, combined with analytical chemistry methods to identify the potential sources of spills.

Dissolved organic matter (DOM) plays a crucial role in the photochemical transformation of organic contaminants in natural aquatic systems. The present study focuses on the characterization of a specific effect previously observed for electron-rich phenols, consisting in an acceleration of the DOM-photosensitized transformation of target compounds at low concentrations (< 1 µM). This effect was hypothesized to be caused by DOM-derived "long-lived" photooxidants (LLPO). Pseudo-first-order rate constants for the transformation of several phenols, anilines, sulfonamide antibiotics and phenylureas photosensitized by Suwannee River fulvic acid were determined under steady−state irradiation using the UVA and visible wavelengths from a medium-pressure mercury lamp. A significant enhancement (by a factor of 2.4 − 16) of the first-order transformation rate constant of various electron-rich target compounds was observed for an initial concentration of 0.1 μM compared to 5 μM . This effect points to a relevant reactivity of these compounds with LLPO. For phenols and anilines the enhancement effect occurred only above certain standard one-electron oxidation potentials. From these data series the standard one-electron reduction potential of LLPO was estimated to be in the range of 1.0 − 1.3 V versus the standard hydrogen electrode. LLPO are proposed to mainly consist of phenoxyl radicals formed by photooxidation of electron-poor phenolic moieties of the DOM. The plausibility of this hypothesis was successfully tested by studying the photosensitized transformation kinetics of 3,4-dimethoxyphenol in aqueous solutions containing a model photosensitizer (2-acetonaphthone) and a model electron-poor phenol (4-cyanophenol) as DOM surrogates.

We examined the uptake of Tl(I) by two hexagonal birnessites and related phase transformations in laboratory experiments over 12 sequential additions of 0.01 M Tl(I)/Mn at pH 4.0, 6.0, and 8.0. The Tl-reacted Mn oxides were characterized for their structure, Tl binding, and morphology using X-ray diffraction, X-ray photoelectron and X-ray absorption spectroscopies, and transmission electron microscopy. Very limited Tl oxidation was observed in contrast to previous works, where equal Tl(I)/Mn was added in a single step. Instead, both birnessites transformed into a 2 × 2 tunneled phase with dehydrated Tl(I) in its tunnels at pH 4, but only partially at pH 6, and at pH 8.0 they remained layered. The first four to nine sequential Tl(I)/Mn additions resulted in lower residual dissolved Tl⁺ concentrations than when the same amounts of Tl(I)/Mn were added in single steps. This study thus shows that the repeated reaction of hexagonal birnessites with smaller Tl(I)/Mn at ambient temperature triggers a complete phase conversion with Tl(I) as the sole reacting cation. The novel pathway found may be more relevant for contaminated environments and may help explain the formation of minerals like thalliomelane [Tl⁺(Mn_7.5⁴⁺Cu_0.5²⁺)O₁₆]; it also points to the possibility that other reducing species trigger similar Mn oxide transformation reactions.

Although mining and mineral processing are vital for many economies in the Global South, they are associated with enormous challenges of managing potentially devastating environmental impacts. In contexts where environmental oversight agencies often lack financial and personal capacities to fulfill their role, community-based monitoring might be a valid alternative to monitor potential environmental impacts. In this study, we present the setup and the implementation of a citizen science project to monitor water quality parameters in a river downstream of a coal mining area in Hwange, Western Zimbabwe. In a joint effort over 1.5 years, community monitors and scientists took close to 800 water samples in the Deka River and effluent channels. The data allowed identifying sources of pollution and relating these to past and present mining activities. The primary source of acid mine drainage came from abandoned underground mine sites. Illegal mine water dumping from active mine sites accentuated the problem and resulted in fish kills and food risks for the local population. Concentrations of manganese, nickel and arsenic were exceeding national fresh water guidelines and international drinking water standards. Manganese concentrations exceeded guidelines by a factor of 70 resulting in a public health risk. In this study, we showed that community-based monitoring offers a promising approach to establish a high-quality dataset for assessing mining-related risks if the implementation of sampling protocols is followed tightly. The monitoring scheme significantly improves the collection and interpretation of water quality data in challenging contexts where governmental institutions and industrial players are not enforcing environmental standards.

Aquifer natural recharge estimations are a prerequisite for understanding hydrologic systems and sustainable water resources management. As meteorological data series collection is difficult in arid and semiarid areas, satellite products have recently become an alternative for water resources studies. A daily groundwater recharge estimation in the NW part of the Lake Chad Basin, using a soil–plant-atmosphere model (VisualBALAN), from ground- and satellite-based meteorological input dataset for non-irrigated and irrigated land and for the 2005–2014 period is presented. Average annual values were 284 mm and 30°C for precipitation and temperature in ground-based gauge stations. For the satellite-model-based Lake Chad Basin Flood and Drought Monitor System platform (CHADFDM), average annual precipitation and temperature were 417 mm and 29°C, respectively. Uncertainties derived from satellite data measurement could account for the rainfall difference. The estimated mean annual aquifer recharge was always higher from satellite- than ground-based data, with differences up to 46% for dryland and 23% in irrigated areas. Recharge response to rainfall events was very variable and results were very sensitive to: wilting point, field capacity and curve number for runoff estimation. Obtained results provide plausible recharge values beyond the uncertainty related to data input and modelling approach. This work prevents on the important deviations in recharge estimation from weighted-ensemble satellite-based data, informing in decision making to both stakeholders and policy makers.

Snowmelt contributes a significant fraction of groundwater recharge in snow‐dominated regions, making its accurate quantification crucial for sustainable water resources management. While several components of the hydrological cycle can be measured directly, catchment‐scale recharge can only be quantified indirectly. Stable water isotopes are often used as tracers to estimate snowmelt recharge, even though estimates based on stable water isotopes are biased due to the large variations of δ²H and δ¹⁸O in snow and the difficulty to measure snowmelt directly. To overcome this gap, a new tracer method based on on‐site measurements of dissolved He, ⁴⁰Ar, ⁸⁴Kr, N₂, O₂ and CO₂ is presented. The new method was developed alongside classical tracer methods (stable water isotopes, ²²²Rn, ³H/³He) in a highly instrumented boreal catchment. By revealing (noble gas) recharge temperatures and excess air, dissolved gases allow (i) the contribution of snowmelt to recharge, (ii) the temporal recharge dynamics, and (iii) the primary recharge pathways to be identified. In contrast to stable water isotopes, which produced highly inconsistent snowmelt recharge estimates for the experimental catchment, dissolved gases produced consistent estimates even when the temperature of snowmelt during recharge was not precisely known. As dissolved gases are not controlled by the same processes as stable water isotopes, they are not prone to the same biases and represent a highly complementary tracer method for the quantification of snowmelt recharge dynamics in snow‐dominated regions. Furthermore, an observed systematic depletion of N₂ in groundwater provides new evidence for the pathways of biological N‐fixation in boreal forest soils.

The magnitude of global cooling during the Last Glacial Maximum (LGM, the coldest multimillennial interval of the last glacial period) is an important constraint for evaluating estimates of Earth’s climate sensitivity^1,2. Reliable LGM temperatures come from high-latitude ice cores^3,4, but substantial disagreement exists between proxy records in the low latitudes^1,5–8, where quantitative low-elevation records on land are scarce. Filling this data gap, noble gases in ancient groundwater record past land surface temperatures through a direct physical relationship that is rooted in their temperature-dependent solubility in water^9,10. Dissolved noble gases are suitable tracers of LGM temperature because of their complete insensitivity to biological and chemical processes and the ubiquity of LGM-aged groundwater around the globe^11,12. However, although several individual noble gas studies have found substantial tropical LGM cooling^13–16, they have used different methodologies and provide limited spatial coverage. Here we use noble gases in groundwater to show that the low-altitude, low-to-mid-latitude land surface (45 degrees south to 35 degrees north) cooled by 5.8 ± 0.6 degrees Celsius (mean ± 95% confidence interval) during the LGM. Our analysis includes four decades of groundwater noble gas data from six continents, along with new records from the tropics, all of which were interpreted using the same physical framework. Our land-based result broadly supports a recent reconstruction based on marine proxy data assimilation¹ that suggested greater climate sensitivity than previous estimates^5–7.

We combine results of high-resolution microfluidic experiments with extensive numerical simulations to show how the flow patterns inside a "swiss-cheese" type of pore geometry can be systematically controlled through the intrinsic rheological properties of the fluid. Precisely, our analysis reveals that the velocity field in the interstitial pore space tends to display enhanced channeling under certain flow conditions. This observed flow "localization", quantified by the spatial distribution of kinetic energy, can then be explained in terms of the strong interplay between the disordered geometry of the pore space and the nonlinear rheology of the fluid. Our results disclose the possibility that the constitutive properties of the fluid can enhance the performance of chemical reactors and chromatographic devices through control of the channeling patterns inside disordered porous media.

Geogenic arsenic (As) contamination of groundwater is a health threat to millions of people worldwide, particularly in alluvial regions of South and Southeast Asia. Mitigation measures are often hindered by high heterogeneities in As concentrations, the cause(s) of which are elusive. Here we used a comprehensive suite of stable isotope analyses and hydrogeochemical parameters to shed light on the mechanisms in a typical high-As Holocene aquifer near Hanoi where groundwater is advected to a low-As Pleistocene aquifer. Carbon isotope signatures (δ¹³C-CH₄, δ¹³C-DOC, δ¹³C-DIC) provided evidence that fermentation, methanogenesis and methanotrophy are actively contributing to the As heterogeneity. Methanogenesis occurred concurrently where As levels are high (>200 µg/L) and DOC-enriched aquitard pore water infiltrates into the aquifer. Along the flowpath to the Holocene/Pleistocene aquifer transition, methane oxidation causes a strong shift in δ¹³C-CH₄ from -87‰ to +47‰, indicating high reactivity. These findings demonstrate a previously overlooked role of methane cycling and DOC infiltration in high-As aquifers.

This paper features the new atmosphere-ocean-aerosol-chemistry-climate model, SOlar Climate Ozone Links (SOCOL) v4.0, and its validation. The new model was built by interactively coupling the Max Planck Institute Earth System Model version 1.2 (MPI-ESM1.2) (T63, L47) with the chemistry (99 species) and size-resolving (40 bins) sulfate aerosol microphysics modules from the aerosol-chemistry-climate model, SOCOL-AERv2. We evaluate its performance against reanalysis products and observations of atmospheric circulation, temperature, and trace gas distribution, with a focus on stratospheric processes. We show that SOCOLv4.0 captures the low- and midlatitude stratospheric ozone well in terms of the climatological state, variability and evolution. The model provides an accurate representation of climate change, showing a global surface warming trend consistent with observations as well as realistic cooling in the stratosphere caused by greenhouse gas emissions, although, as in previous model versions, a too-fast residual circulation and exaggerated mixing in the surf zone are still present. The stratospheric sulfur budget for moderate volcanic activity is well represented by the model, albeit with slightly underestimated aerosol lifetime after major eruptions. The presence of the interactive ocean and a successful representation of recent climate and ozone layer trends make SOCOLv4.0 ideal for studies devoted to future ozone evolution and effects of greenhouse gases and ozone-destroying substances, as well as the evaluation of potential solar geoengineering measures through sulfur injections. Potential further model improvements could be to increase the vertical resolution, which is expected to allow better meridional transport in the stratosphere, as well as to update the photolysis calculation module and budget of mesospheric odd nitrogen. In summary, this paper demonstrates that SOCOLv4.0 is well suited for applications related to the stratospheric ozone and sulfate aerosol evolution, including its participation in ongoing and future model intercomparison projects.

Landuse change and climate change are the main drivers of hydrological processes. The purpose of this study was to analyse the separate and combined future effects of climate and landuse changes on water balance components on different spatial and temporal scales using the integrated hydrological Soil and Water Assessment Tool model. The study focused on the changes and relationship between water yield (WYLD) and sediment yield (SYLD) in the heterogeneous Taleghan Catchment in Iran. For future climate scenarios, RCP 4.5 and RCP 8.5 of GFDL-ESM2M GCM were used for 2020-2040. A Markov chain model was used to predict landuse change in the catchment. The results indicated an increase in precipitation and evapotranspiration. The findings also showed that the relationship between WYLD and SYLD is direct and synergic. Climate change has a stronger effect on WYLD than landuse change, whereas landuse change has a stronger effect on SYLD. The conversion of rangelands to barren land is the most critical landuse change that could increase SYLD. The highest increase in WYLD and SYLD in scenario RCP4.5 resulted from the combined effects of climate and landuse change. We estimated WYLD of about 295 mm and SYLD of around 17 t/ha. The proposed methodology is universal and can be applied to similar settings to identify the most vulnerable regions. This can help prioritize management strategies to improve water and soil management in watersheds.

Substituted para-benzoquinones and hydroquinones are ubiquitous transformation products that arise during oxidative water treatment of phenolic precursors, for example through ozonation or chlorination. The benzoquinone structural motive is associated with mutagenicity and carcinogenicity, and also with induction of the oxidative stress response through the Nrf2 pathway. For either endpoint, toxicological data for differently substituted compounds are scarce. In this study, oxidative stress response, as indicated by the AREc32 in vitro bioassay, was induced by differently substituted para-benzoquinones, but also by the corresponding hydroquinones. Bioassays that indicate defense against genotoxicity (p53RE-bla) and DNA repair activity (UmuC) were not activated by these compounds. Stability tests conducted under incubation conditions, but in the absence of cell lines, showed that tested para-benzoquinones reacted rapidly with constituents of the incubation medium. Compounds were abated already in phosphate buffer, but even faster in biological media, with reactions attributed to amino- and thiol-groups of peptides, proteins, and free amino acids. The products of these reactions were often the corresponding substituted hydroquinones. Conversely, differently substituted hydroquinones were quantitatively oxidized to p-benzoquinones over the course of the incubation. The observed induction of the oxidative stress response was attributed to hydroquinones that are presumably oxidized to benzoquinones inside the cells. Despite the instability of the tested compounds in the incubation medium, the AREc32 in vitro bioassay could be used as an unspecific sum parameter to detect para-benzoquinones and hydroquinones in oxidatively treated waters.

The commonly observed heterogeneous and erratic emissions of methane from lacustrine sediments are difficult to quantify. The combined analysis of methane and noble gas concentrations in the pore water opens a novel route to analyse and quantify such emissions and was used in this work to explore the gas dynamics in the sediments of two lakes with different hydro-geochemical settings. In the hypertrophic Lake Rot the microbial activity in the sediment pore water results in a virtually continuous gas bubble formation and emission. By determining noble gas concentration gradients and the maximum methane supersaturation, the minimum methane emission from the sediment was quantified. The gas evolution in the pore water of the sediments of artificial Lake Lungern is strongly affected by annual lake level variations of up to 20 meters. Noble gas concentrations allow past gas dynamics at different lake levels to be traced back. At "hot spots" of bubble emission microbial methane from deeper sediments was released in response to the decreasing hydrostatic pressure, i.e. man-induced lake level drop.
Within zones of the sediment that seasonally fall dry, the oxygen supply to the sediment was inferred from the noble gas excess observed in the pore water, which is due to dissolving air bubbles which entered the sediment during the dry period.
These case studies demonstrate the potential of the combined analysis of noble gas and CH₄ concentrations for exploring the gas dynamics in lacustrine sediments. The feasibility of this method under different conditions calls for an application in other aquatic environments, such as wetlands and oceans.

Nghiên cứu trình bày kết quả về sự biến đổi nồng độ asen (As) trong nước ngầm dọc theo một mặt cắt tại khu vực gần trung tâm thành phố Hà Nội. Kết quả cho thấy, nước ngầm tại khu vực này không đủ an toàn để sử dụng cho mục đích ăn uống, với 64% số mẫu có nồng độ As vượt quá tiêu chuẩn cho phép của Tổ chức Y tế thế giới (WHO) về nồng độ As trong nước ăn uống. Sự biến đổi As dọc theo mặt cắt nghiên cứu phụ thuộc mạnh vào đặc điểm trầm tích của từng vùng tương ứng. Ngoài As, nước ngầm tại đây cũng bị ô nhiễm bởi nồng độ cao của Fe, Mn và amoni. Nghiên cứu cũng cho thấy mối tương quan thuận giữa As với các thành phần thể hiện tính khử cho môi trường nước là DOC (cacbon hữu cơ hòa tan), NH4 + và CH4. Tuy mối tương quan giữa As với Fe và Mn không rõ ràng theo một chiều hướng, nhưng với các kết quả đã đạt được có thể khẳng định, sự hình thành của As trong nước ngầm ở khu vực nghiên cứu là theo cơ chế khử hòa tan các khoáng Fe dưới điều kiện khử.

In this study, the authors report detailed results of the variation of arsenic in groundwater along a transect in an area near the Hanoi city centre. The results showed that 64% of collected samples exceeded the WHO guideline value for arsenic concentration in drinking water. The arsenic concentration varied in a wide range, strongly depending on the sediment characteristics of each zone along the transect. Aside from As, groundwater in this area also was contaminated by elevated concentrations of Fe, Mn, and ammonium. The study also pointed out a positive correlation between As and reductive chemical species, namely DOC, NH₄⁺, and CH₄ in groundwater. Although there is no clear trend in the correlation between As and Fe, Mn, it can be concluded that the formation of arsenic in groundwater in the study area was due to the reductive dissolution of As-bearing iron minerals under the presence of organic matter.

Land-use changes often have significant impact on the water cycle, including changing groundwater/surface-water interactions, modifying groundwater recharge zones, and increasing risk of contamination. Surface runoff in particular is significantly impacted by land cover. As surface runoff can act as a carrier for contaminants found at the surface, it is important to characterize runoff dynamics in anthropogenic environments. In this study, the relationship between surface runoff and groundwater recharge in urban areas is explored using a top-down water balance approach. Two empirical models were used to estimate runoff: (1) an updated, advanced method based on curve number, followed by (2) bivariate hydrograph separation. Modifications were added to each method in an attempt to better capture continuous soil-moisture processes and explicitly account for runoff from impervious surfaces. Differences between the resulting runoff estimates shed light on the complexity of the rainfall–runoff relationship, and highlight the importance of understanding soil-moisture dynamics and their control on hydro(geo)logical responses. These results were then used as input in a water balance to calculate groundwater recharge. Two approaches were used to assess the accuracy of these groundwater balance estimates: (1) comparison to calculations of groundwater recharge using the calibrated conceptual HBV Light model, and (2) comparison to groundwater recharge estimates from physically similar catchments in Switzerland that are found in the literature. In all cases, recharge is estimated at approximately 40–45% of annual precipitation. These conditions were found to closely echo those results from Swiss catchments of similar characteristics.

Carbon capture and storage (CCS) may play a significant role in reducing greenhouse gas emissions. Noble gases are potential tracers to monitor subsurface CO₂ storage sites and verify their containment. Naturally occurring noble gases have been used successfully to refute alleged CO₂ leakage in the past.
We present results from several sampling campaigns at two Norwegian CO₂ capture facilities, the demonstration plant Technology Centre Mongstad (TCM) and the natural gas processing plant with CO₂ capture and storage on Melkøya. The gas streams in the capture plants were monitored with a combination of on-site mass spectrometry and subsequently analysed discrete samples. This allows us to define the factors controlling noble gas concentrations in captured CO₂, to monitor temporal variation of noble gas concentrations and finally evaluate the potential to use noble gases as inherent environmental tracers for labelling CO₂ in storage reservoirs.
At both sites, CO₂ is captured using amine gas treatment. Noble gas concentrations in the gas streams were observed to decrease by several orders of magnitude during the processing. Isotopic ratios are air-like for CO₂ captured after natural gas combustion at TCM and natural gas-like for CO₂ captured from natural gas processing on Melkøya. Further, we detected a solubility trend caused by the amine solvent at TCM with higher solubility for heavier noble gases.
We find that the relative concentrations of noble gases in the captured CO₂ are defined by the gas from which the CO₂ is captured and the design of the amine gas treatment process. Both factors were observed to cause temporal variation in the captured CO₂.
Using mixing and noble gas partitioning calculations we show that the significant depletion in noble gas concentrations, together with degassing of noble gas enriched formation water, means that the injected CO₂ will inherit the noble gas signature of the storage formation, even following the injection of significant CO₂ volumes. Any CO₂ leaked from the storage formation is thus likely to have a crustal noble gas signature, characteristic of the storage site, which can be targeted for monitoring.

Dissolved organic matter (DOM) has a dual role in indirect phototransformations of aquatic contaminants by acting both as a photosensitizer and an inhibitor. Herein, the pH dependence of the inhibitory effect of DOM and the underlying mechanisms were studied in more than 400 kinetic irradiation experiments over the pH range of 6-11. Experiments employed various combinations of one of three DOM isolates, one of two model photosensitizers, the model antioxidant phenol, and one of nine target compounds (TCs), comprising several aromatic amines, in particular anilines and sulfonamides, and 4-cyanophenol. Using model photosensitizers without antioxidants, the phototransformation of most TCs increased with increasing pH, even for TCs for which pH did not affect speciation. This trend was attributed to pH-dependent formation yields of TC-derived radicals and their re-formation to the parent TC. Analogous trends were observed with DOM as a photosensitizer. Comparison of model and DOM photosensitizer data sets showed increasing inhibitory effects of DOM on TC phototransformation kinetics with increasing pH. In systems with anilines as a TC and phenol as a model antioxidant, pH trends of the inhibitory effect could be rationalized based on the reduction potential difference (ΔE_red) of phenoxyl/phenol and anilinyl/aniline couples. Our results indicate that the light-induced transformation of aromatic amines in the aquatic environment is governed by the pH-dependent inhibitory effects of antioxidant phenolic moieties of DOM and pH-dependent processes related to the formation of amine oxidation intermediates.

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.

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.

Geogenic arsenic contamination in groundwaters poses a severe health risk to hundreds of millions of people globally. Notwithstanding the particular risks to exposed populations in the Indian sub-continent, at the time of writing, there was a paucity of geostatistically based models of the spatial distribution of groundwater hazard in India. In this study, we used logistic regression models of secondary groundwater arsenic data with research-informed secondary soil, climate and topographic variables as principal predictors generate hazard and risk maps of groundwater arsenic at a resolution of 1 km across Gujarat State. By combining models based on different arsenic concentrations, we have generated a pseudo-contour map of groundwater arsenic concentrations, which indicates greater arsenic hazard (> 10 μg/L) in the northwest, northeast and south-east parts of Kachchh District as well as northwest and southwest Banas Kantha District. The total number of people living in areas in Gujarat with groundwater arsenic concentration exceeding 10 μg/L is estimated to be around 122,000, of which we estimate approximately 49,000 people consume groundwater exceeding 10 µg/L. Using simple previously published dose–response relationships, this is estimated to have given rise to 700 (prevalence) cases of skin cancer and around 10 cases of premature avoidable mortality/annum from internal (lung, liver, bladder) cancers—that latter value is on the order of just 0.001% of internal cancers in Gujarat, reflecting the relative low groundwater arsenic hazard in Gujarat State.

Organic micropollutants (MPs) are increasingly detected in water resources, which can be a concern for human health and the aquatic environment. Ultraviolet (UV) radiation based advanced oxidation processes (AOP) such as low-pressure mercury vapor arc lamp UV/H₂O₂ can be applied to abate these MPs. During UV/H₂O₂ treatment, MPs are abated primarily by photolysis and reactions with hydroxyl radicals (^•OH), which are produced in situ from H₂O₂ photolysis. Here, a model is presented that calculates the applied UV fluence (H_calc) and the ^•OH exposure (CT_•OH,calc ) from the abatement of two selected MPs, which act as internal probe compounds. Quantification of the UV fluence and hydroxyl radical exposure was generally accurate when a UV susceptible and a UV resistant probe compound were selected, and both were abated at least by 50 %, e.g., iopamidol and 5-methyl-1H-benzotriazole. Based on these key parameters a model was developed to predict the abatement of other MPs. The prediction of abatement was verified in various waters (sand filtrates of rivers Rhine and Wiese, and a tertiary wastewater effluent) and at different scales (laboratory experiments, pilot plant). The accuracy to predict the abatement of other MPs was typically within ±20 % of the respective measured abatement. The model was further assessed for its ability to estimate unknown rate constants for direct photolysis (k_UV,_MP) and reactions with ^•OH (k•_OH,_MP). In most cases, the estimated rate constants agreed well with published values, considering the uncertainty of kinetic data determined in laboratory experiments. A sensitivity analysis revealed that in typical water treatment applications, the precision of kinetic parameters (k_UV,_MP for UV susceptible and for UV resistant probe compounds) have the strongest impact on the model's accuracy.

Permanganate (MnO₄^-, Mn(VII)) is widely applied at the initial stage of water treatment to, e.g., abate taste and odor compounds, Mn(II) and Fe(II). However, its selectivity limits its application for micropollutant abatement. Hydrogen peroxide (H₂O₂), which is commonly applied in advanced oxidation processes, was found to quickly react with Mn(VII) in the pH-range 6.0-8.5. A lag-phase was followed by a rapid reduction of Mn(VII) to Mn(VI), with a proposed catalysis by the deprotonated form of Mn(VI), for the electron transfer of the [H₂O₂-OMnO₃]^- complex. At molar [H₂O₂]₀:[Mn(VII)]₀ ratios ≤ 1 and pH 7.5, a one-electron reduction of Mn(VII) by H₂O₂ potentially formed Mn(VI) and superoxide radical (O₂^•-), with O₂^•- yields approaching 100% based on the consumed Mn(VII). Mn(VII)-H₂O₂ significantly enhanced the abatement of the Mn(VII)-resistant compound ciprofloxacin and its transformation products, and quenching of Mn(VI) by Ba²⁺ completely inhibited this enhancement effect. At molar [H₂O₂]₀:[Mn(VII)]₀ ratios of 2-10, O₂^•- yields of 145-245% indicate that other H₂O₂-reactive manganese species might also be formed. Among them, Mn(II) was found to produce O₂^•- by reaction with H₂O₂ at a relatively low rate with overstoichiometric yields. Overall, this study provides evidence that a combination of Mn(VII) with H₂O₂ might be a novel option for enhanced micropollutant abatement in water treatment.

The success of geological carbon storage depends on the assurance of permanent containment for injected carbon dioxide (CO₂) in the storage formation at depth. One of the critical elements of the safekeeping of CO₂ is the sealing capacity of the caprock overlying the storage formation despite faults and/or fractures, which may occur in it. In this work, we present an ongoing injection experiment performed in a fault hosted in clay at the Mont Terri underground rock laboratory (NW Switzerland). The experiment aims to improve our understanding of the main physical and chemical mechanisms controlling (i) the migration of CO₂ through a fault damage zone, (ii) the interaction of the CO₂ with the neighboring intact rock, and (iii) the impact of the injection on the transmissivity in the fault. To this end, we inject CO₂-saturated saline water in the top of a 3 m thick fault in the Opalinus Clay, a clay formation that is a good analog of common caprock for CO₂ storage at depth. The mobility of the CO₂ within the fault is studied at the decameter scale by using a comprehensive monitoring system. Our experiment aims to close the knowledge gap between laboratory and reservoir scales. Therefore, an important aspect of the experiment is the decameter scale and the prolonged duration of observations over many months. We collect observations and data from a wide range of monitoring systems, such as a seismic network, pressure temperature and electrical conductivity sensors, fiber optics, extensometers, and an in situ mass spectrometer for dissolved gas monitoring. The observations are complemented by laboratory data on collected fluids and rock samples. Here we show the details of the experimental concept and installed instrumentation, as well as the first results of the preliminary characterization. An analysis of borehole logging allows for identifying potential hydraulic transmissive structures within the fault zone. A preliminary analysis of the injection tests helped estimate the transmissivity of such structures within the fault zone and the pressure required to mechanically open such features. The preliminary tests did not record any induced microseismic events. Active seismic tomography enabled sharp imaging the fault zone.

Low bioavailability of iron due to poor solubility of iron(hydr)oxides limits the growth of microorganisms and plants in soils and aquatic environments. Previous studies described accelerated dissolution of iron(hydr)oxides under continuous illumination, but did not distinguish between photoreductive dissolution and non-reductive processes in which photogenerated Fe(II) catalyzes ligand-controlled dissolution. Here we show that short illuminations (5-15 min) accelerate the dissolution of iron(hydr)oxides by ligands during subsequent dark periods under anoxic conditions. Suspensions of lepidocrocite (Lp) and goethite (Gt) (1.13 mM) with 50 μM EDTA or DFOB were illuminated with UV-A light of comparable intensity to sunlight (pH 7.0, bicarbonate-CO₂ buffered solutions). During illumination, the rate of Fe(II) production was highest with Gt-EDTA; followed by Lp-EDTA > Lp-DFOB > Lp > Gt-DFOB > Gt. Under anoxic conditions, photochemically produced Fe(II) increased dissolution rates during subsequent dark periods by factors of 10-40 and dissolved Fe(III) reached 50 μM with DFOB and EDTA. Under oxic conditions, dissolution rates increased by factors of 3-5 only during illumination. With DFOB dissolved Fe(III) reached 35 μM after 10 h of illumination, while with EDTA it peaked at 15 μM and then decreased to below 2 μM. The observations are explained and discussed based on a kinetic model. The results suggest that in anoxic bottom water of ponds and lakes, or in microenvironments of algal blooms, short illuminations can dramatically increase the bioavailability of iron by Fe(II)-catalyzed ligand-controlled dissolution. In oxic environments, photostable ligands such as DFOB can maintain Fe(III) in solution during extended illumination.

Dissolution of Fe(III) phases is a key process in making iron available to biota and in the mobilization of associated trace elements. Recently, we have demonstrated that submicromolar concentrations of Fe(II) significantly accelerate rates of ligand-controlled dissolution of Fe(III) (hydr)oxides at circumneutral pH. Here, we extend this work by studying isotope exchange and dissolution with lepidocrocite (Lp) and goethite (Gt) in the presence of 20 or 50 μM desferrioxamine-B (DFOB). Experiments with Lp at pH 7.0 were conducted in carbonate-buffered suspensions to mimic environmental conditions. We applied a simple empirical model to determine dissolution rates and a more complex kinetic model that accounts for the observed isotope exchange and catalytic effect of Fe(II). The fate of added tracer ⁵⁷Fe(II) was strongly dependent on the order of addition of ⁵⁷Fe(II) and ligand. When DFOB was added first, tracer ⁵⁷Fe remained in solution. When ⁵⁷Fe(II) was added first, isotope exchange between surface and solution could be observed at pH 6.0 but not at pH 7.0 and 8.5 where ⁵⁷Fe(II) was almost completely adsorbed. During dissolution of Lp with DFOB, ratios of released ⁵⁶Fe and ⁵⁷Fe were largely independent of DFOB concentrations. In the absence of DFOB, addition of phenanthroline 30 min after tracer ⁵⁷Fe desorbed predominantly ⁵⁶Fe(II), indicating that electron transfer from adsorbed ⁵⁷Fe to ⁵⁶Fe of the Lp surface occurs on a time scale of minutes to hours. In contrast, comparable experiments with Gt desorbed predominantly ⁵⁷Fe(II), suggesting a longer time scale for electron transfer on the Gt surface. Our results show that addition of 1–5 μM Fe(II) leads to dynamic charge transfer between dissolved and adsorbed species and to isotope exchange at the surface, with the dissolution of Lp by ligands accelerated by up to 60-fold.

Human endeavours into deep space exploration and the prospects of establishing colonies on nearby planets would invariably involve components of bioregenerative life support for food production, cabin atmosphere renewal, and waste recycling. Growing plants and their microbiomes in porous media under different gravitational fields may present new challenges due to effects of liquid distribution on gaseous exchange with roots and microorganisms. We provide the first direct evidence that capillary driven liquid reconfiguration in porous media under reduced gravity conditions reduces oxygen diffusion pathways and enhances anoxic conditions within bacterial hotspots. Parabolic flight experiments using model porous media inoculated with aerobic and facultative anaerobic bacteria reveal the systematic enhancement of anoxic conditions during the reduced gravity periods in the presence but not in the absence of bacterial activity. The promotion of anoxic conditions under reduced gravity may lead to higher nitrous oxide and methane emissions relative to Earth conditions, on the other hand, anoxic conditions could be beneficial for perchlorate bioremediation of Martian soil. The results highlight changes in soil bacterial microhabitats under reduced gravity and the challenges of managing bioregenerative life support systems in space.

The miniRUEDI is a portable mass spectrometer system designed for on-site analysis of gases in the environment during field work and at remote locations. For many gas species (e.g., He, Ar, Kr, N₂, O₂, CO₂) the ion-current peak-heights measured with the mass spectrometer can usually be calibrated in terms of the partial pressures by simple peak-height comparison relative to a gas standard with well known partial pressures. However, depending on the composition of the analysed gases, the ion currents measured at certain m/z ratios may result from overlapping signals of multiple species (for example CH₄, O₂ and N₂ at m/z = 15 and 16; or Ne, Ar and H₂O at m/z = 20).
Here, we present a method extension to the existing miniRUEDI peak-height comparison in order to resolve such overlap interferences:
• We developed and tested a data processing procedure for accurate deconvolution and compensation of such mass-spectrometric overlap interferences.
• The method was incorporated into the miniRUEDI open-source software (ruediPy).
• The method substantially improves the analytical accuracy in situations where mass-spectrometric interferences cannot be avoided.

Groundwater contaminated with geogenic arsenic (As) is frequently used as drinking water in Burkina Faso, despite adverse health effects. This study focused on testing low-cost filter systems based on zero-valent iron (ZVI), which have not yet been explored in West Africa for As removal. The active ZVI bed was constructed using small-sized iron nails, embedded between sand layers. Household filters were tested for nine months in a remote village relying on tube well water with As concentrations of 400 - 1350 μg/L. Daily filtered volumes were 40 - 60 L, with flow rates of ~10 L/h. In parallel, downscaled laboratory filter columns were run to find the best set-up for optimal As removal, with special attention given to the influence of input pH, flow rate and water/nail contact time. Arsenic removal efficiencies in the field were 60 - 80% in the first six months of operation. The laboratory experiments revealed that trapped air in the nail layer greatly lowered As removal due to preferential flow and decreased water/nail contact time. Measures taken to avoid trapped air led to a partial improvement in the field filters, but effluent As remained >50 μg/L. Similar structural modifications were however very successful in the laboratory columns, where As removal efficiencies were consistently > 95% and effluent concentrations frequently < 10 μg/L, despite inflow As > 1000 μg/L. A constantly saturated nail bed and careful flow control is necessary for optimal As removal. Slow flow and longer pauses between filtrations are important for sufficient contact times and for transformation of brown amorphous Fe-hydroxides to dense magnetite with incorporated As(V). This preliminary study has shown that nail-based filters have the potential to achieve As removal >90% in a field context if conditions (filter bed saturation, flow rate, pauses between filtrations) are well controlled.

Lake Kivu is a 485 m deep tropical rift lake in East-Africa and well-known for its very high concentrations of dissolved carbon dioxide and methane in the stratified deep waters. In view of future large-scale methane extraction for power production, there is a need for predicting the evolution of gas concentrations and lake stability using numerical modelling. However, knowledge about the geochemical origin and transport processes affecting dissolved gases in the lake is still partially missing. Due to their inert nature, the analysis of dissolved noble gases can help to shed light on such questions. To learn more about transport processes in Lake Kivu, we extended a well-established sampling method for dissolved noble gases to work in the lake's high gas pressure waters. The results of our analysis show a distinct non-atmospheric isotopic signal in the deep waters (below 250 m) with ³He/⁴He and ⁴⁰Ar/³⁶Ar ratios ~250% and ~20% higher than air saturated water (ASW). Moreover, the gas concentration profiles reveal a striking lack of atmospheric noble gases in the deep waters with respect to ASW. While Ne is depleted by ~45%, the more soluble ³⁶Ar and Kr even decrease by ~70%. In contrast, ⁴He concentrations increase with depth by a factor of up to ~600. We attribute this excess He and the increases in ³He/⁴He and ⁴⁰Ar/³⁶Ar to the inflow of magmatic gases into Lake Kivu, along with a significant contribution of radiogenic ⁴He. To explain the depletion of atmospheric noble gases, we present and discuss three different scenarios, namely continuous outgassing, the inflow of depleted groundwater and a large past outgassing event. Due to the best agreement with our observations, we conclude that the inflow of depleted groundwater is likely responsible for the observed atmospheric noble gas depletions.

This study documents the development of a semi-distributed hydrological model aimed at reflecting the dominant controls on observed streamflow spatial variability. The process is presented through the case study of the Thur catchment (Switzerland, 1702 km²), an alpine and pre-alpine catchment where streamflow (measured at 10 subcatchments) has different spatial characteristics in terms of amounts, seasonal patterns, and dominance of baseflow. In order to appraise the dominant controls on streamflow spatial variability and build a model that reflects them, we follow a two-stage approach. In a first stage, we identify the main climatic or landscape properties that control the spatial variability of streamflow signatures. This stage is based on correlation analysis, complemented by expert judgement to identify the most plausible cause–effect relationships. In a second stage, the results of the previous analysis are used to develop a set of model experiments aimed at determining an appropriate model representation of the Thur catchment. These experiments confirm that only a hydrological model that accounts for the heterogeneity of precipitation, snow-related processes, and landscape features such as geology produces hydrographs that have signatures similar to the observed ones. This model provides consistent results in space–time validation, which is promising for predictions in ungauged basins. The presented methodology for model building can be transferred to other case studies, since the data used in this work (meteorological variables, streamflow, morphology, and geology maps) are available in numerous regions around the globe.

Flow of non-Newtonian fluids through topologically complex structures is ubiquitous in most biological, industrial and environmental settings. The interplay between local hydrodynamics and the fluid's constitutive law determines the distribution of flow paths. Consequently the spatial heterogeneity of the viscous resistance controls mass and solute transport from the micron to the meter scale. Examples range from oil recovery and groundwater engineering to drug delivery, filters and catalysts. Here we present a new methodology to map the spatial variation of the local viscosity of a non-Newtonian fluid flowing through a complex pore geometry. We use high resolution image velocimetry to determine local shear rates. Knowing the local shear rate in combination with a separate measurement of the fluid's constitutive law allows to quantitatively map the local viscosity at the pore scale. Our experimental results - which closely match with three-dimensional numerical simulations - demonstrate that the exponential decay of the longitudinal velocity distributions, previously observed for Newtonian fluids, is a function of the spatial heterogeneity of the local viscosity. This work sheds light on the relationship between hydraulic properties and the viscosity at the pore scale, which is of fundamental importance for predicting transport properties, mixing, and chemical reactions in many porous systems.

Selenium (Se) is an essential dietary element for humans and animals, and the atmosphere is an important source of Se to soils. However, estimates of global atmospheric Se fluxes are highly uncertain. To constrain these uncertainties, we use a global model of atmospheric Se cycling and a database of more than 600 sites where Se in aerosol has been measured. Applying Bayesian inference techniques, we determine the probability distributions of global Se emissions from the four major sources: anthropogenic activities, volcanoes, marine biosphere, and terrestrial biosphere. Between 29 and 36 Gg of Se are emitted to the atmosphere every year, doubling previous estimates of emissions. Using emission parameters optimized by aerosol network measurements, our model shows good agreement with the aerosol Se observations (R² = 0.66), as well as with independent aerosol (0.59) and wet deposition measurements (0.57). Both model and measurements show a decline in Se over North America in the last two decades because of changes in technology and energy policy. Our results highlight the role of the ocean as a net atmospheric Se sink, with around 7 Gg yr^-1 of Se transferred from land through the atmosphere. The constrained Se emissions represent a substantial step forward in understanding the global Se cycle.

An estimated 0.5–1 billion people globally have inadequate intakes of selenium (Se), due to a lack of bioavailable Se in agricultural soils. Deposition from the atmosphere, especially through precipitation, is an important source of Se to soils. However, very little is known about the atmospheric cycling of Se. It has therefore been difficult to predict how far Se travels in the atmosphere and where it deposits. To answer these questions, we have built the first global atmospheric Se model by implementing Se chemistry in an aerosol–chemistry–climate model, SOCOL-AER (modeling tools for studies of SOlar Climate Ozone Links – aerosol). In the model, we include information from the literature about the emissions, speciation, and chemical transformation of atmospheric Se. Natural processes and anthropogenic activities emit volatile Se compounds, which oxidize quickly and partition to the particulate phase. Our model tracks the transport and deposition of Se in seven gas-phase species and 41 aerosol tracers. However, there are large uncertainties associated with many of the model's input parameters. In order to identify which model uncertainties are the most important for understanding the atmospheric Se cycle, we conducted a global sensitivity analysis with 34 input parameters related to Se chemistry, Se emissions, and the interaction of Se with aerosols. In the first bottom-up estimate of its kind, we have calculated a median global atmospheric lifetime of 4.4 d (days), ranging from 2.9 to 6.4 d (2nd–98th percentile range) given the uncertainties of the input parameters. The uncertainty in the Se lifetime is mainly driven by the uncertainty in the carbonyl selenide (OCSe) oxidation rate and the lack of tropospheric aerosol species other than sulfate aerosols in SOCOL-AER. In contrast to uncertainties in Se lifetime, the uncertainty in deposition flux maps are governed by Se emission factors, with all four Se sources (volcanic, marine biosphere, terrestrial biosphere, and anthropogenic emissions) contributing equally to the uncertainty in deposition over agricultural areas. We evaluated the simulated Se wet deposition fluxes from SOCOL-AER with a compiled database of rainwater Se measurements, since wet deposition contributes around 80 % of total Se deposition. Despite difficulties in comparing a global, coarse-resolution model with local measurements from a range of time periods, past Se wet deposition measurements are within the range of the model's 2nd–98th percentiles at 79 % of background sites. This agreement validates the application of the SOCOL-AER model to identifying regions which are at risk of low atmospheric Se inputs. In order to constrain the uncertainty in Se deposition fluxes over agricultural soils, we should prioritize field campaigns measuring Se emissions, rather than laboratory measurements of Se rate constants.

Widespread seafloor methane venting has been reported in many regions of the world oceans in the past decade. Identifying and quantifying where and how much methane is being released into the ocean remains a major challenge and a critical gap in assessing the global carbon budget and predicting future climate [C. Ruppel, J. D. Kessler. Rev. Geophys. 55, 126-168 (2017)]. Methane hydrate (CH₄ · 5.75H₂O) is an ice-like solid that forms from methane-water mixture under elevated-pressure and low-temperature conditions typical of the deep marine settings (>600-m depth), often referred to as the hydrate stability zone (HSZ). Wide-ranging field evidence indicates that methane seepage often coexists with hydrate-bearing sediments within the HSZ, suggesting that hydrate formation may play an important role during the gas-migration process. At a depth that is too shallow for hydrate formation, existing theories suggest that gas migration occurs via capillary invasion and/or initiation and propagation of fractures (Fig. 1). Within the HSZ, however, a theoretical mechanism that addresses the way in which hydrate formation participates in the gas-percolation process is missing. Here, we study, experimentally and computationally, the mechanics of gas percolation under hydrate-forming conditions. We uncover a phenomenon-crustal fingering-and demonstrate how it may control methane-gas migration in ocean sediments within the HSZ.

Thallium (Tl) is a hazardous trace metal that can harm human and environmental health. Tl pollution can result from the mining and smelting of Tl-bearing minerals, but also the natural weathering of Tl-bearing sulfide minerals may induce Tl release to the environment. In this study, hydrothermal deposits hosted in dolostone rocks sited along fossil thermal springs in the Lodares region (Soria province, central Spain) were studied. In this hydrothermal mineralization zone, Tl association with primary minerals, identified Tl-bearing secondary products resulting from natural weathering of primary minerals, as well as the dispersion from its natural source along a seasonal small streambed were explored. Samples were analyzed by chemical, microscopic and spectroscopic techniques and epithermal pyrite, sphalerite, galena and barite and secondary gypsum, jarosite, scorodite, anglesite, goethite, epsomite and elemental sulfur produced by both inorganic and bacterial processes were found. The highest Tl contents were found in hydrothermal pyrite (188 mg kg^-1), jarosite (142 mg kg^-1), Mn-oxides (27 mg kg^-1) or kerogen (13 mg kg^-1). Feldspar was identified by electron probe microanalysis as potential host phase of Tl. XANES results confirmed the association of Tl(I) with metal sulfides in pyrite-rich samples and highlighted the role of jarosite-like minerals for Tl(I) sequestration upon pyrite oxidation, even in carbonate-rich samples at near-neutral pH. In addition to micaceous minerals, jarosite-group minerals and K-feldspars may contribute to the natural attenuation of Tl in soils and sediments.

Experimental reconstruction of temperature - altitude in the past remain often elusive. With the development of a combined vacuum crushing and sieving system (CVCS), it is now possible to determine paleotemperatures from the noble gases dissolved in minute amounts of water from inclusions in speleothems that have grown under a broad range of climatic conditions. Here we present noble gas temperature (NGT) estimates during the last deglaciation, which are based on two stalagmites from Milandre Cave (stalagmite M6) and Grotte aux Fées de Vallorbe (stalagmite GEF1), Jura Mountains, Switzerland. The caves are located at different geographical altitudes (Milandre Cave: 373 m a.s.l. and Grotte aux Fées de Vallorbe: 895 m a.s.l.) and thus allow for a reconstruction of the respective temperature - altitude gradients within Switzerland during the last deglaciation. Our reconstruction shows that the past temperature - altitude gradients are within 1σ error in agreement with the modern temperature - altitude gradient, suggesting that the local temperature - altitude gradient was rather stable over time.
In addition to the noble gas analysis, we complemented our study with deuterium (δD_FI) and oxygen isotope (δ¹⁸O_FI) measurements of fluid inclusion water. In combination with NGTs, this allows us to reconstruct the past δ¹⁸O_FI - δD_FI / temperature relation. These reconstructions show that the temporal temperature sensitivity of δ¹⁸O_FI and δD_FI (Δ(δ¹⁸O_FI) / Δ(T) and Δ(δD_FI) / Δ(T)) seems to be stable over time and therefore support the use of water isotopes for temperature reconstructions in Switzerland.

Arsenic groundwater contamination threatens the health of millions of people worldwide, particularly in South and Southeast Asia. In most cases, the release of arsenic from sediment was caused by microbial reductive dissolution of arsenic-bearing iron(III) minerals with organic carbon being used as microbial electron donor. Although in many arsenic-contaminated aquifers high concentrations of methane were observed, its role in arsenic mobilization is unknown. Here, using microcosms experiments and hydrogeochemical and microbial community analyses, we demonstrate that methane functions as electron donor for methanotrophs, triggering the reductive dissolution of arsenic-bearing iron(III) minerals, increasing the abundance of genes related to methane oxidation, and ultimately mobilizing arsenic into the water. Our findings provide evidence for a methane-mediated mechanism for arsenic mobilization that is distinct from previously described pathways. Taking this together with the common presence of methane in arsenic-contaminated aquifers, we suggest that this methane-driven arsenic mobilization may contribute to arsenic contamination of groundwater on a global scale.

Natural organic matter (NOM) can contribute to arsenic (As) mobilization as an electron donor for microbially-mediated reductive dissolution of As-bearing Fe(III) (oxyhydr)oxides. However, to investigate this process, instead of using NOM, most laboratory studies used simple fatty acids or sugars, often at relatively high concentrations. To investigate the role of relevant C sources, we therefore extracted in situ NOM from the upper aquitard (clayey silt) and lower sandy aquifer sediments in Van Phuc (Hanoi area, Vietnam), characterized its composition, and used 100-day microcosm experiments to determine the effect of in situ OM on Fe(III) mineral reduction, As mobilization, and microbial community composition. We found that OM extracted from the clayey silt (OMC) aquitard resembles young, not fully degraded plant-related material, while OM from the sandy sediments (OMS) is more bioavailable and related to microbial biomass. Although all microcosms were amended with the same amount of C (12 mg C/L), the extent of Fe(III) reduction after 100 days was the highest with acetate/lactate (43 ± 3.5% of total Fe present in the sediments) followed by OMS (28 ± 0.3%) and OMC (19 ± 0.8%). Initial Fe(III) reduction rates were also higher with acetate/lactate (0.53 mg Fe(II) in 6 days) than with OMS and OMC (0.18 and 0.08 mg Fe(II) in 6 days, respectively). Although initially more dissolved As was detected in the acetate/lactate setups, after 100 days, higher concentrations of As (8.3 ± 0.3 and 8.8 ± 0.8 μg As/L) were reached in OMC and OMS, respectively, compared to acetate/lactate-amended setups (6.3 ± 0.7 μg As/L). 16S rRNA amplicon sequence analyses revealed that acetate/lactate mainly enriched Geobacter, while in situ OM supported growth and activity of a more diverse microbial community. Our results suggest that although the in situ NOM is less efficient in stimulating microbial Fe(III) reduction than highly bioavailable acetate/lactate, it ultimately has the potential to mobilize the same amount or even more As.

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.

Monomethylmercury (MMHg) concentrations in aquatic biota from Lake Titicaca are elevated although the mercury (Hg) contamination level of the lake is low. The contribution of sediments to the lake MMHg pool remained however unclear. In this work, seven cores representative of the contrasted sediments and aquatic ecotopes of Lake Titicaca were sliced and analyzed for Hg and redox-sensitive elements (Mn, Fe, N and S) speciation in pore-water (PW) and sediment to document early diagenetic processes responsible for MMHg production and accumulation in PW during organic matter (OM) oxidation. The highest MMHg concentrations (up to 12.2 ng L⁻¹ and 90% of THg) were found in subsurface PWs of the carbonate-rich sediments which cover 75% of the small basin and 20% of the large one. In other sediment facies, the larger content of OM restricted MMHg production and accumulation in PW by sequestering Hg in the solid phase and potentially also by decreasing its bioavailability in the PW. Diagenetically reduced S and Fe played a dual role either favoring or restricting the availability of Hg for biomethylation. The calculation of theoretical diffusive fluxes suggests that Lake Titicaca bottom sediments are a net source of MMHg, accounting for more than one third of the daily MMHg accumulated in the water column of the Lago Menor. We suggest that in the context of rising anthropogenic pressure, the enhancement of eutrophication in high altitude Altiplano lakes may increase these MMHg effluxes into the water column and favor its accumulation in water and biota.

The majority of Brunei's drinking water is sourced from river water. Increases in population, and industrialization are putting more and more pressure on water resources not only in Brunei but worldwide. The management of water resources under a changing climate is of key importance. The goal of this study was to investigate if current water quality changes in Brunei can be related to climatic change. The study investigated time series data from water quality parameters as well as rainfall data measured over a 3-year period. The time series data was analysed using auto-correlation and partial auto-correlation functions. The results showed changes in climate evident from a decrease in precipitation and increase in rainfall intensity. These changes can be correlated with changes in water quality in particular a rise in aluminium concentrations. The highest correlation was observed between turbidity and colour, with a Pearson correlation coefficient greater than 0.8. The results from cross correlation showed that pH values tend to be low before the occurrence of rainfall, due to a dropping of water levels and the likely exposure of acid sulphate soils. Low pH values were correlated with higher aluminium concentrations which have been rising consistently throughout the observation period. The rise in aluminium concentration is correlated with a rise in abstraction from the river during the time period which underlines the importance of water management in a changing climate.

The photolytic chlorination of n-alkanes in presence of sulfuryl chloride (SO₂Cl₂) was explored to produce new standard materials. Five mixtures of chlorinated tetradecanes were synthesized with chlorination degrees (m_Cl,EA) varying from 43.7% to 59.4% (m/m) based on elemental analysis. Chlorine-enhanced negative chemical ionization mass spectrometry (CE–NCI–MS) forcing the formation of chloride-adduct ions [M+Cl]^- was applied to characterize these materials which all contained tetra-to deca-chlorinated paraffins. Deconvolution of respective mass spectra revealed the presence of chlorinated olefins (COs). CO levels were highest in materials, which were exposed longest. All synthesized materials also contained two classes of polar impurities, tentatively assigned as sulfite- and sulfate-diesters with molecular formulas of C₁₄H_28-xO₃SCl_x (x = 1-4) and C₁₄H_28-xO₄SCl_x (x = 3–6), respectively. MS data were in accordance with the proposed structures but further work is needed to deduce their constitutions. These compounds are thermolabile and were not detected with GC-MS methods. We could remove these sulfur-containing impurities from the CPs with normal-phase liquid chromatography. In conclusion, single-chain CP materials were synthesized via chlorination of n-alkanes with sulfuryl chloride, but these materials contained reactive side products which should be removed to gain non-reactive and stable CP materials suitable as standards and for fate and toxicity studies.

Groundwater is a much safer and more dependable source of drinking water than surface water. However, natural (geogenic) hazardous elements can contaminate groundwater and lead to severe health problems in consumers. Arsenic concentrations exceeding the WHO drinking water guideline of 10 μg/L globally affect over 220 million people and can cause arsenicosis (skin lesions and cancers). Fluoride, while preventing caries at low concentrations, has detrimental effects when above the WHO drinking water guideline of 1.5 mg/L and puts several hundred million people at risk of dental and skeletal fluorosis. In this article, we report on the geochemistry and occurrence of arsenic and fluoride in groundwater and on the development of global and regional risk maps that help alert governments and water providers to take appropriate mitigation measures for the provision of safe drinking water. We then summarize research on the removal of arsenic and fluoride from drinking water, focusing on adapted technologies for water treatment. Finally, we discuss the applicability of various measures in a larger context and future challenges in reaching the goal of access to safe drinking water for all.

We present a set of multiphase flow simulations where supercritical CO₂ (scCO₂) displaces water at hydrostatic conditions within three-dimensional discrete fracture networks that represent paths for potential leakage through caprock above CO₂ storage reservoirs. The simulations are performed to characterize and compare the relative impact of hydraulic and structural heterogeneity in fractured media on the initial movement of scCO₂ through these caprock formations. In one scenario, intrinsic fracture permeabilities are varied stochastically within a fixed network structure. In another scenario, we generate multiple independent, identically distributed network realizations with varying fracture network densities to explore a wide range of geometric and topological configurations. Analysis of the simulations indicates that network structure, specifically connectivity and the presence of hanging fractures, plays a larger role in controlling the displacement of water by scCO₂ than variations in local hydraulic properties. We identify active surface area of the network as a single-phase feature that could provide a lower bound on the percentage of the network surface area reached by scCO₂.

Multiphase flow is ubiquitous in subsurface energy applications and natural processes, such as oil recovery, CO₂ sequestration, and water flow in soils. Despite its importance, we still lack a thorough understanding of the coupling of multiphase flow and reaction of transported fluids with the confining media, including rock dissolution and mineral precipitation. Through the use of geomaterial microfluidic flow experiments and high-performance computer simulations, we identify key pore-scale mechanisms that control this coupling. We compare the reactivity of fractured limestone with CO₂-saturated brine (single phase) and a mixture of supercritical (sc) CO₂ and CO₂-saturated brine (multiphase). We find that the presence of scCO₂ bubbles significantly changes both the flow dynamics and the resulting reaction patterns from a single-phase system, spatially homogenizing the rock dissolution. In addition, bubbles redirect oversaturated fluid into low-velocity regions, thereby enhancing carbonate precipitation occurs.

The impact of phases distribution on mixing and reaction is hardly assessable experimentally. We use a multiple point statistical method, which belongs to the family of machine learning algorithms, to generate simulations of phases distributions from data out of laboratory experiments. The simulations honour the saturation of the laboratory experiments, resemble the statistical distributions of several geometric descriptors and respect the physics imposed by capillary forces. The simulated phases distributions are used to compute solute transport. The breakthrough curves reveal that different phases distributions lead to broad ranges of early arrival times and long-term tailings as saturation decreases. For a given saturation, a similar long-term scaling of mixing area, interface length, and corresponding reactivity is observed regardless of phases distribution. However, phases distribution has a clear impact on the final values (before breakthrough) of area of mixing, interface length and mass of reaction product.

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.

Chlorothalonil, a fungicide applied for decades worldwide, has recently been banned in the European Union (EU) and Switzerland due to its carcinogenicity and the presence of potentially toxic transformation products (TPs) in groundwater. The spread and concentration range of chlorothalonil TPs in different drinking water resources was examined (73 groundwater and four surface water samples mainly from Switzerland). The chlorothalonil sulfonic acid TPs (R471811, R419492, R417888) occurred more frequently and at higher concentrations (detected in 65-100% of the samples, ≤2200 ngL^-1) than the phenolic TPs (SYN507900, SYN548580, R611968; detected in 10-30% of the samples, ≤130 ngL^-1). The TP R471811 was found in all samples and even in 52% of the samples above 100 ngL^-1, the drinking water standard in Switzerland and other European countries. Therefore, the abatement of chlorothalonil TPs was investigated in laboratory and pilot-scale experiments and along the treatment train of various water works, comprising aquifer recharge, UV disinfection, ozonation, advanced oxidation processes (AOPs), activated carbon treatment, and reverse osmosis. The phenolic TPs can be abated during ozonation (second order rate constant k_O3 ∼10⁴ M^-1s^-1) and by reaction with hydroxyl radicals (OH) in AOPs (k_OH ∼10⁹ M^-1s^-1). In contrast, the sulfonic acid TPs, which occurred in higher concentrations in drinking water resources, react only very slowly with ozone (k_O3 <0.04 M^-1s^-1) and OH (k_OH <5.0 × 10⁷ M^-1s^-1) and therefore persist in ozonation and OH-based AOPs. Activated carbon retained the very polar TP R471811 only up to a specific throughput of 25 m³kg^-1 (20% breakthrough), similarly to the X-ray contrast agent diatrizoic acid. Reverse osmosis was capable of removing all chlorothalonil TPs by ≥98%.

This study identifies causes of rising arsenic (As) concentrations over 17 years in an inter-montane aquifer system located just north of the Trans-Mexican-Volcanic-Belt in the Mesa central physiographic region that is extensively developed by long-screened production wells. Arsenic concentrations increased by more than 10 µg/L in 14% (3/22) of re-sampled wells. Similarly, in a larger scale analysis wherein As concentrations measured in 137 wells in 2016 were compared to interpolated, baseline concentrations from 246 wells in 1999, As concentrations rose more than 10 µg/L in 30% of wells. Between 1999 and 2016, the percentage of all wells sampled in each basin-wide sampling campaign exceeding the World Health Organization's 10 µg/L drinking water limit increased from 38 to 64%. Principal Components Analysis (PCA), step-wise multiple regression, and Random Forest modeling (RF) revealed that high As concentrations are closely associated with high pH and temperature, and high concentrations of fluoride (F), molybdenum (Mo), lithium (Li), sodium (Na) and silica (Si), but low calcium (Ca) and nitrate (NO₃) concentrations. Pumping-induced mixing with hot, geothermally impacted groundwater generates alkaline water through hydrolysis of silicate minerals. The rising pH converts oxyanion sorption sites from positive to negative releasing As (and Mo) to pore waters. The negative correlation between nitrate and As concentrations can be explained by conservative mixing of shallow, young groundwater with geothermally influenced groundwater. Therefore water carrying an anthropogenic contaminant dilutes water carrying geogenic contaminants. This process is enabled by long well screens. Over-exploitation of aquifers in geothermal regions for agriculture can drive As concentrations in water from production wells to toxic levels even as the total dissolved solids remain low.

Phosphorus (P) immobilization has potential for reducing diffuse P losses from legacy P soils to surface waters and for regenerating low-nutrient ecosystems with a high plant species richness. Here, P immobilization with iron oxide sludge application was investigated in a field trial on a noncalcareous sandy soil. The sludge applied is a water treatment residual produced from raw groundwater by Fe(II) oxidation. Siliceous ferrihydrite (Fh) is the major Fe oxide type in the sludge. The reactive surface area assessed with an adapted probe ion method is 211-304 m² g^-1 for the Fe oxides in the sludge, equivalent to a spherical particle diameter of ~6-8 nm. This size is much larger than the primary Fh particle size (~2 nm) observed with transmission electron microscopy. This can be attributed to aggregation initiated by silicate adsorption. The surface area of the indigenous metal oxide particles in the field trial soils is much higher (~1100 m² g^-1), pointing to the presence of ultra-small oxide particles (2.3 ± 0.4 nm). The initial soil surface area was 5.4 m² g^-1 and increased linearly with sludge application up to a maximum of 12.9 m² g^-1 when 27 g Fe oxides per kg soil was added. In case of a lower addition (~10-15 g Fe oxides per kg soil), a 10-fold reduction in the phosphate (P-PO₄) concentration in 0.01 M CaCl₂ soil extracts to 0.3 µM was possible. The adapted probe ion method is a valuable tool for quantifying changes in the soil surface area when amending soil with Fe oxide-containing materials. This information is important for mechanistically predicting the reduction in the P-PO₄ solubility when such materials are used for immobilizing P in legacy P soils with a low P-PO₄ adsorption capacity but with a high surface loading.

Reports that promote persulfate-based advanced oxidation process (AOP) as a viable alternative to hydrogen peroxide-based processes have been rapidly accumulating in recent water treatment literature. Various strategies to activate peroxide bonds in persulfate precursors have been proposed and the capacity to degrade a wide range of organic pollutants has been demonstrated. Compared to traditional AOPs in which hydroxyl radical serves as the main oxidant, persulfate-based AOPs have been claimed to involve different in situ generated oxidants such as sulfate radical and singlet oxygen as well as nonradical oxidation pathways. However, there exist controversial observations and interpretations around some of these claims, challenging robust scientific progress of this technology toward practical use. This Critical Review comparatively examines the activation mechanisms of peroxymonosulfate and peroxydisulfate and the formation pathways of oxidizing species. Properties of the main oxidizing species are scrutinized and the role of singlet oxygen is debated. In addition, the impacts of water parameters and constituents such as pH, background organic matter, halide, phosphate, and carbonate on persulfate-driven chemistry are discussed. The opportunity for niche applications is also presented, emphasizing the need for parallel efforts to remove currently prevalent knowledge roadblocks.

Aromatic amines are relevant aquatic organic contaminants whose photochemical transformation is affected by dissolved organic matter (DOM). The goal of this study is to elucidate the underlying mechanism of the inhibitory effect of DOM on such reactions. The selected model aromatic amine, 4-(dimethylamino)benzonitrile (DMABN), was subjected to laser flash photolysis in the presence and absence of various model photosensitizers. The produced radical cation (DMABN•+) was observed to react with several phenols and different types of DOM on a time scale of ∼100 μs. The determined second-order rate constants for the quenching of DMABN•+ by phenols were in the range of (1.4-26) × 108 M-1 s-1 and increased with increasing electron donor character of the aromatic ring substituent. For DOM, quenching rate constants increased with the phenolic content of the DOM. These results indicate the reduction of DMABN•+ to re-form its parent compound as the basic reaction governing the inhibitory effect. In addition, the photosensitized oxidation of the sulfonamide antibiotic sulfadiazine (SDZ) was studied. The observed radical intermediate of SDZ was quenched by 4-methoxyphenol less effectively than DMABN•+, which was attributed to the lower reduction potential of the SDZ-derived radical compared to DMABN•+.

Hypochlorous acid (HOCl) is typically assumed to be the primary reactive species in free available chlorine (FAC) solutions. Lately, it has been shown that less abundant chlorine species such as chlorine monoxide (Cl₂O) and chlorine (Cl₂) can also influence the kinetics of the abatement of certain organic compounds during chlorination. In this study, the chlorination as well as bromination kinetics and mechanisms of 12 olefins (including 3 aliphatic and 9 aromatic olefins) with different structures were explored. HOCl shows a low reactivity towards the selected olefins with species-specific second-order rate constants <1.0 M⁻¹s⁻¹, about 4-6 orders of magnitude lower than those of Cl₂O and Cl₂. HOCl is the dominant chlorine species during chlorination of olefins under typical drinking water conditions, while Cl₂O and Cl₂ are likely to play important roles at high FAC concentration near circum-neutral pH (for Cl₂O) or at high Cl⁻ concentration under acidic conditions (for Cl₂). Bromination of the 12 olefins suggests that HOBr and Br₂O are the major reactive species at pH 7.5 with species-specific second-order rate constants of Br₂O nearly 3-4 orders of magnitude higher than of HOBr (ranging from <0.01 to >10³ M⁻¹s⁻¹). The reactivities of chlorine and bromine species towards olefins follow the order of HOCl < HOBr < Br₂O < Cl₂O ≈ Cl₂. Generally, electron-donating groups (e.g., CH₂OH- and CH₃-) enhances the reactivities of olefins towards chlorine and bromine species by a factor of 3-10², while electron-withdrawing groups (e.g., Cl-, Br-, NO₂-, COOH-, CHO-, -COOR, and CN-) reduce the reactivities by a factor of 3-10⁴. A reasonable linear free energy relationship (LFER) between the species-specific second-order rate constants of Br₂O or Cl₂O reactions with aromatic olefins and their Hammett σ⁺ was established with a more negative ρ value for Br₂O than for Cl₂O, indicating that Br₂O is more sensitive to substitution effects. Chlorinated products including HOCl-adducts and decarboxylated Cl-adduct were identified during chlorination of cinnamic acid by high-performance liquid chromatography/high resolution mass spectrometry (HPLC/HRMS).

X-ray tomographic microscopy is a well-established analysis technique in different fields of the Earth Sciences to access volumetric information of the internal microstructure of a large variety of opaque materials with high-spatial resolution and in a non-destructive manner. Synchrotron radiation, with its coherence and high flux, is required for pushing the temporal resolution into the second and sub-second regime and beyond, and therefore moving from the investigation of static samples to the study of fast dynamic processes as they happen in 3D. Over the past few years, several hardware and software developments at the TOMCAT beamline at the Swiss Light Source contributed to establishing its highly flexible and user-friendly fast tomography endstation, making a large variety of new dynamic in situ and operando investigations possible. Here we present an overview of the different devices, including an in-house developed detector, a new highly efficient macroscope and a programmable fast rotation stage. Their tight interplay and synchronization are key for lifting experimental design compromises and follow dynamic processes with high spatial and temporal resolution unfolding over prolonged periods of time, as often required by many applications. We showcase these new capabilities for the Earth Sciences community by presenting three different geological studies, which make use of different sample environments. With a tri-axial deformation rig, chemo-mechanical-hydraulic feedbacks between gypsum dehydration and halite deformation have been studied, while the spatio-temporal evolution of a solute plume has been investigated for the first time in 3D with a flow cell. A laser-based heating system available at the beamline provides access to the high temperatures required to address bubble growth and collapse as well as bubble-bubble interaction and coalescence in volcanological material. With the integration of a rheometer, information on bubble deformation could also be gained. In the near future, upgrades of most large-scale synchrotron radiation facilities to diffraction-limited storage rings will create new opportunities, for instance through sub-second tomographic imaging capabilities at sub-micron length scales.

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.

Groundwater recharge indicates the existence of renewable groundwater resources and is therefore an important component in sustainability studies. However, recharge is also one of the least understood, largely because it varies in space and time and is difficult to measure directly. For most studies, only a relatively small number of measurements is available, which hampers a comprehensive understanding of processes driving recharge and the validation of hydrogeological model formulations for small- and large-scale applications.
We present a new global recharge dataset encompassing >5000 locations. In order to gain insights into recharge processes, we provide a systematic analysis between the dataset and other global-scale datasets, such as climatic or soil-related parameters. Precipitation rates and seasonality in temperature and precipitation were identified as the most important variables in predicting recharge. The high dependency of recharge on climate indicates its sensitivity to climate change. We also show that vegetation and soil structure have an explanatory power for recharge. Since these conditions can be highly variable, recharge estimates based only on climatic parameters may be misleading.
The freely available dataset offers diverse possibilities to study recharge processes from a variety of perspectives. By noting the existing gaps in understanding, we hope to encourage the community to initiate new research into recharge processes and subsequently make recharge data available to improve recharge predictions.

A null‐space Monte‐Carlo (NSMC) approach was applied to account for uncertainty in the calibration of the hydraulic conductivity (K) field for a three‐dimensional groundwater flow model of a major water supply system in Switzerland. The approach generates different parameter realizations of the K field using the pilot point methodology. Subsequently, particle tracking (PT) was applied to each calibrated model, and the resulting particles are interpreted as the spatial pathline density distribution of multiple sources. The adopted approach offers advantages over classical PT which does not provide a means for treating uncertainty originating from the incomplete description of subsurface heterogeneity. Uncertainty in the K field is shown to strongly influence the spatial pathline distribution. Pathline spreading is particularly evident in locations where the information content of the head observations does not sufficiently constrain the estimated parameters. Despite the predictive uncertainty, the pumped drinking water at the study site is most likely dominated by artificially‐infiltrated groundwater originating from the local infiltration canals. The model suggests that within the well field, the central pumping wells could be extracting regional groundwater, although the probability is relatively low. Nevertheless, a rigorous uncertainty assessment is still required since only a few realizations resulted in flow paths that support the field observations. Model results should therefore not be based on only one model realization; rather, an uncertainty analysis should be carried out to provide a sufficiently large suite of equally probable simulations that include all potential sources and pathways.

We investigate the impact of pore-scale heterogeneity on reactive mixing using experimental data from inert fluid-fluid displacement in a quasi 2-D porous medium. We interpret the invading and defending fluids as the conservative components A + C and B + C of the instantaneous irreversible bimolecular chemical reaction A + B → C and determine the reaction product C . We find strong growth of the reaction rate at short and intermediate times due to deformation of the mixing interface and heterogeneity-induced increase of the mixing area. This behavior is captured by a dispersive lamella approach that quantifies the mixing dynamics at the interface in terms of temporally evolving effective dispersion coefficients. The latter capture the dominant controls on the evolution of the mixing interface, namely, advective heterogeneity and transverse mixing. Reactive transport formulations based on constant hydrodynamic dispersion coefficients are not able to describe the observed behavior due to the lack of complete mixing on the support scale, which is required for these approaches to hold. These results shed some new light on the origins of heterogeneity-induced mixing and reaction dynamics in porous media and their systematic upscaling.

Naturally occurring arsenic in groundwater affects millions of people worldwide. We created a global prediction map of groundwater arsenic exceeding 10 micrograms per liter using a random forest machine-learning model based on 11 geospatial environmental parameters and more than 50,000 aggregated data points of measured groundwater arsenic concentration. Our global prediction map includes known arsenic-affected areas and previously undocumented areas of concern. By combining the global arsenic prediction model with household groundwater-usage statistics, we estimate that 94 million to 220 million people are potentially exposed to high arsenic concentrations in groundwater, the vast majority (94%) being in Asia. Because groundwater is increasingly used to support growing populations and buffer against water scarcity due to changing climate, this work is important to raise awareness, identify areas for safe wells, and help prioritize testing.

Groundwater is a critical resource in India for the supply of drinking water and for irrigation. Its usage is limited not only by its quantity but also by its quality. Among the most important contaminants of groundwater in India is arsenic, which naturally accumulates in some aquifers. In this study we create a random forest model with over 145,000 arsenic concentration measurements and over two dozen predictor variables of surface environmental parameters to produce hazard and exposure maps of the areas and populations potentially exposed to high arsenic concentrations (>10 µg/L) in groundwater. Statistical relationships found between the predictor variables and arsenic measurements are broadly consistent with major geochemical processes known to mobilize arsenic in aquifers. In addition to known high arsenic areas, such as along the Ganges and Brahmaputra rivers, we have identified several other areas around the country that have hitherto not been identified as potential arsenic hotspots. Based on recent reported rates of household groundwater use for rural and urban areas, we estimate that between about 18-30 million people in India are currently at risk of high exposure to arsenic through their drinking water supply. The hazard models here can be used to inform prioritization of groundwater quality testing and environmental public health tracking programs.

The spatio-temporal dynamics of denitrification in groundwater are still not well understood due to a lack of efficient methods to quantify this biogeochemical reaction pathway. Previous research used the ratio of N₂ to argon (Ar) to quantify net production of N₂ via denitrification by separating the biologically-generated N₂ component from the atmospheric-generated components. However, this method does not allow to quantify the atmospheric components accurately since the differences in gas partitioning between N₂ and Ar are being neglected. Moreover, conventional (noble) gas analysis in water is both expensive and labor-intensive. We overcome these limitations by using a portable mass spectrometer system, which enables a fast and efficient in situ analysis of dissolved (noble) gases in groundwater. By analyzing a larger set of (noble) gases (N₂, He, Ar and Kr) combined with a physically meaningful excess air model, we quantified N₂ originating from denitrification. Consequently, we were able to study the spatio-temporal dynamics of N₂ production due to denitrification in riparian groundwater over a six-month period. Our results show that denitrification is highly variable in space and time, emphasizing the need for spatially and temporally resolved data to accurately account for denitrification dynamics in groundwater.

Despite decades of research on the fate of phenolic compounds when water is disinfected with hypochlorous acid (HOCl), there is still considerable uncertainty regarding the formation mechanisms and identity of ring cleavage products, especially at higher chlorine doses. This study focuses on the formation of electrophilic ring cleavage products - a class of compounds that poses potential health risks at relatively low concentrations - from the reactions of phenols with chlorine. By monitoring the formation of products of reactions between ring cleavage products and the model nucleophile N-α-acetyl-lysine, we identified the α,β-unsaturated dialdehyde 2-butene-1,4-dial (BDA) and its chlorinated analogue, chloro-2-butene-1,4-dial (Cl-BDA), after the chlorination of phenol, para- and ortho-substituted chlorophenols (2-Cl, 4-Cl, 2,4-diCl-, 2,6-diCl, and 2,4,6-triCl-phenol), and 3,5-di-Cl-catechol. Maximum yields of BDA were observed when chlorine was present in large excess (HOCl/phenol ratios of 30:1 to 50:1), with yields ranging from 18% for phenol to 46% for 3,5-diCl-catechol. BDA and Cl-BDA formation was also observed during the chlorination of brominated phenols. For methyl-substituted phenols, the presence of methyl substituents in both positions ortho to the hydroxy group inhibited BDA and Cl-BDA formation, but the chlorination of cresols and 2,3-dimethylphenol yielded methyl- and dimethyl-BDA species. This study provides new insights into the formation of reactive and toxic electrophiles during chlorine disinfection. It also provides evidence for the importance of phenoxy radicals produced by one-electron transfer reactions initiated by chlorine in the production of dicarbonyl ring cleavage products.

Plastic pollution has increased in line with the increased plastic production over the last 60 years, having reached all environments globally and potentially affecting drinking water supplies [1, 2, 3]. For example, microplastics have recently been detected in both potable water sources and bottled water for consumption [4], leading researchers to question the efficacy of current water treatment practices. [...]

The increasing use of wireless sensor networks and remote sensing permits real‐time access to environmental observations. Data assimilation frameworks tap into such data streams to autonomously update and gradually improve numerical models. In hydrogeology, such methods are relevant in areas of long‐term interest in water quality and quantity, for example, in drinking water production. Unfortunately, accurate hydrogeological predictions often demand a degree of geological realism, which is difficult to reconcile with the operational limitations of many data assimilation frameworks. Alluvial aquifers, for example, are sometimes characterized by paleo‐channels of unknown extent and properties, which may act as preferential flow paths. Gradually optimizing such fields in real‐time or quasi‐real‐time settings is a formidable task. Besides subsurface properties, ill‐specified model forcings are a further source of predictive bias, which an optimizer could learn to compensate. In this study, we explore the use of a quasi‐online optimizer based on the iterative batch importance sampling framework for a groundwater model of a field site near Valdobbiadene, Italy. This site is characterized by the presence of paleo‐channels and heavily exploited for drinking water production and irrigation. We use Markov chain Monte Carlo steps to explore new parameterizations while maintaining consistency between states and parameters as well as conformance to a multipoint statistics training image. We also optimize a preprocessor designed to compensate for potential bias in the model forcing. We achieve promising and geologically consistent quasi‐real‐time optimization, albeit at the loss of parameter uncertainty.

It has been reported that persistent cyanide pollution occurs in artisanal small-scale gold mining (ASGM) catchment areas in Burkina Faso. In the present study, logistic regression (LR) and Regression Kriging (RK) methods were applied to predict cyanide pollution hazard at the catchment level as well as to determine the most vulnerable areas to prioritize for restoration of degraded ecosystems. Soil samples were collected from two ASGM sites in Burkina Faso: the northern Zougnazagmiline site and the southern Galgouli site. Free cyanide (FCN) concentration in each sample was measured and the use of the LR and RK methods identified the relationships between pollution sources and pathways. However, RK was able to identify more areas with a high cyanide hazard than LR. Nevertheless, the two methods reveal that the cyanidation zones and catchments outlets within the two catchments are where the highest risk of cyanide pollution occurs, with probabilities of 0.8 and 1 in Zougnazagmiline and Galgouli, respectively.

Ozonation of drinking and wastewater relies on ozone (O₃) and hydroxyl radical (^•OH) as oxidants. Both oxidants react with dissolved organic matter (DOM) and alter its composition, but the selectivity of the two oxidants and mechanisms of reactivity with DOM moieties are largely unknown. The reactions of O₃ and ^•OH with two DOM isolates were studied by varying specific ozone doses (0.1-1.3 mg-O₃/mg-C) at pH 7. Additionally, conditions that favor O₃ (i.e., addition of an ^•OH scavenger) or ^•OH (i.e., pH 11) were investigated. Ozonation decreases aromaticity, apparent molecular weight, and electron donating capacity (EDC) of DOM with large changes observed when O₃ is the main oxidant (e.g., EDC decreases 63-77% for 1.3 mg-O₃/mg-C). Both O₃ and ^•OH react with highly aromatic, reduced formulas detected using high-resolution mass spectrometry (O:C = 0.48 ± 0.12; H:C = 1.06 ± 0.23), while ^•OH also oxidizes more saturated formulas (H:C = 1.64 ± 0.26). Established reactions between model compounds and O₃ (e.g., addition of one to two oxygen atoms) or ^•OH (e.g., addition of one oxygen atom and decarboxylation) are observed and produce highly oxidized DOM (O:C > 1.0). This study provides molecular-level evidence for the selectivity of O₃ as an oxidant within DOM.

The generation of hydroxyl radicals (^•OH) during the chlorination of air saturated solutions of different hydroxyphenols (hydroquinone, resorcinol, catechol, gallic and tannic acids) at pH 7 has been determined by the formation of phenol (in presence of benzene in excess) or 2-hydroxyterephthalic acid (in presence of terephthalic acid). Formation of ^•OH was only detected during the chlorination of o- or p-hydroxyphenols, compounds that react with chlorine by electron transfer forming the corresponding semiquinones/quinones. In aerated solutions, oxygen is reduced by the semiquinone to the superoxide radical, O₂^•-, which reacts with HOCl to ^•OH. Compared to the studied o-hydroxyphenols, the lower reactivity of hydroquinone towards chlorine favours the reaction between chlorine and O₂^•-, and its ^•OH formation potential is ∼50 times higher. The extent of ^•OH generated increased with the concentration of the hydroxyphenol and chlorine, but the ^•OH yield (moles formed per mole of hydroxyphenol eliminated), decreased due to the formation of the quinone, that acts as O₂^•- scavenger. The yield was almost not affected by the pH (6 ≤ pH ≤ 7.5), whereas a strong impact of dissolved O₂ was observed. The ^•OH production was null in absence of O₂ and 2.5-3 times higher at oxygen saturated conditions compared to air-saturated. Contrary to chlorination, during bromination of hydroquinone ^•OH was not formed, which can be attributable to a much faster consumption of the oxidant, with no chance for O₂^•- to react with bromine.
Formation of ^•OH during the chlorination of different NOM extracts (SRHA, SRFA, PLFA and Nordic Lake NOM) and water from Lake Greifensee (Switzerland) was also studied using terephthalic acid as ^•OH scavenger. For SRHA, SRFA and Nordic Lake NOM (all of allochthonous origin and presenting high electron-donating capacity, EDC), ^•OH yields expressed as moles formed per mole of DOC₀ (%), were between 1.1 and 2.0, similar to that of hydroquinone (∼1.5). For PLFA and Lake Greifensee water (autochthonous, lower EDC) much lower ^•OH yields were observed (0.1-0.3). Both chlorination rate and EDC, the later favouring the formation/stabilization of O₂^•-, seem to be key factors involved in ^•OH generation during the chlorination of NOM. A mechanism for these findings is proposed based on kinetic simulations of hydroquinone chlorination at pH 7.

Temporal changes in groundwater chemistry can reveal information about the evolution of flow path connectivity during crustal deformation. Here, we report transient helium and argon concentration anomalies monitored during a series of hydraulic reservoir stimulation experiments measured with an in situ gas equilibrium membrane inlet mass spectrometer. Geodetic and seismic analyses revealed that the applied stimulation treatments led to the formation of new fractures (hydraulic fracturing) and the reactivation of natural fractures (hydraulic shearing), both of which remobilized (He, Ar)-enriched fluids trapped in the rock mass. Our results demonstrate that integrating geochemical information with geodetic and seismic data provides critical insights to understanding dynamic changes in fracture network connectivity during reservoir stimulation. The results of this study also shed light on the linkages between fluid migration, rock deformation and seismicity at the decameter scale.

Pre-oxidation is commonly used to mitigate the formation of byproducts during post-disinfection. A comparative study of the impact of four pre-oxidants, ozone (O₃), chlorine dioxide (ClO₂), permanganate (Mn(_VII)) and ferrate (Fe(_VI)), on the formation of trihalomethanes (THMs), haloacetonitriles (HANs) and adsorbable organic halogens (AOX) in chlorinated synthetic and real waters was conducted. The pre-oxidant doses were based on their impact on natural organic matter reactivity measured by the electron donating capacity before chlorination. The influence of pH (6.5-8.1) and bromide (0-500 μg L^-1) was evaluated in terms of disinfection byproduct (DBP) formation and theoretical toxicity assessment (based on THM and HAN formation). All oxidants were efficient in mitigating chlorinated DBPs, except Mn(VII) which had little impact on THM formation. O₃ was generally more efficient than the other oxidants in mitigating AOX and THM formation, all pre-oxidants readily reduced the formation of HANs (>45% reduction at high dose). pH depression improved AOX mitigation by O₃ and Fe(_VI) but diminished Mn(_VII) efficiency for all DBPs. Pre-oxidation was less efficient in mitigating brominated DBPs and generally enhanced the bromine substitution factor. Although HANs were formed at low concentrations compared to THMs, they dominated the calculated toxicity, particularly the brominated HANs. The increased dibromoacetonitrile formation after pre-oxidation was a major factor counteracting the benefits of the overall DBP mitigation. In the presence of bromide, the pre-oxidant dose should be optimized to decrease the reactivity of the matrix while controlling the toxicity induced by formation of brominated DBPs, notably brominated HANs.

Pre-oxidation is often used before disinfection with chlorine to decrease the reactivity of the water matrix and mitigate the formation of regulated disinfection byproducts (DBPs). This study provides insights on the impact of oxidative pre-treatment with chlorine dioxide (ClO₂), ozone (O₃), ferrate (Fe(VI)) and permanganate (Mn(VII)) on Suwannee River Natural Organic Matter (SRNOM) properties characterized by the UV absorbance at 254 nm (UV₂₅₄) and the electron donating capacity (EDC). Changes in NOM reactivity and abatement of DBP precursors are also assessed. The impact of pre-oxidants (based on molar concentration) on UV₂₅₄ abatement ranked in the order O₃ > Mn(VII) > Fe(VI)/ClO₂, while the efficiency of pre-oxidation on EDC abatement followed the order Mn(VII) > ClO₂ > Fe(VI) > O₃ and two phases were observed. At low specific ClO₂, Fe(VI) and Mn(VII) doses corresponding to < 50% EDC abatement, a limited relative abatement of UV₂₅₄ compared to the EDC was observed (~ 8% EDC abatement per 1% UV₂₅₄ abatement). This suggests the oxidation of phenolic-type moieties to quinone-type moieties which absorb UV₂₅₄ and don't contribute to EDC. At higher oxidant doses (> 50% EDC abatement), a similar abatement of EDC and UV₂₅₄ (~ 0.9-1.2% EDC abatement per 1% UV₂₅₄ abatement) suggested aromatic ring cleavage. In comparison to the other oxidants, O₃ abated the relative UV₂₅₄ more effectively, due to a more efficient cleavage of aromatic rings. For a pre-oxidation with Mn(VII), ClO₂ and Fe(VI), similar correlations between the EDC abatement and the chlorine demand or the adsorbable organic halide (AOX) formation were obtained. In contrast, O₃ pre-treatment led to a lower chlorine demand and AOX formation for equivalent EDC abatement. For all oxidants_, trihalomethane formation was poorly correlated with both EDC and UV_254. The EDC abatement was found to be a pre-oxidant-independent surrogate for haloacetonitrile formation. These results emphasize the benefits of combining EDC and UV₂₅₄ measurement to understand and monitor oxidant-induced changes of NOM and assessing DBP formation.

Chlorophyll is frequently used as a proxy for autochthonous production in lakes. This use of chlorophyll concentrations in sediments to infer historical changes in lake primary production relies heavily on the assumption that preservation is sufficient to reflect the productivity in a meaningful way. In this study, we use a series of freeze cores from a lake with annually laminated sediments to assess how reliable down-core trends in chlorophyll are, and to what extent chlorophyll is degraded in the sediment. A striking consistency in the down-core chlorophyll trends in four sediment cores collected in different years (1983, 1992, 2002 and 2010) shows that the sediment preserves a consistent chlorophyll signal over longer timescales. However, there are also clear signs that diagenetic processes within the sediment affect the chlorophyll concentration in sediment layers younger than 10–15 years. This implies that care is needed when interpreting chlorophyll trends in recent sediments. Further, our data show that high-performance liquid chromatography (HPLC) and visible reflectance spectroscopy (VRS) detect similar chlorophyll concentrations for recently dried samples. A third analytical technique, pyrolysis–gas chromatography/mass spectrometry, which provides semi-quantitative values for chlorophyll, also produce a temporal trend that is highly correlated with data from the two quantitative techniques. For samples that have been stored dried at room temperature for several years there is, however, a large discrepancy between the two quantitative techniques. The VRS method is more robust with regards to degradation during storage, while HPLC results demonstrate clear storage effects.

Oxidative treatment of iodide-containing waters can lead to a formation of potentially toxic iodinated disinfection byproducts (I-DBPs). Iodide (I^-) is easily oxidized to HOI by various oxidation processes and its reaction with dissolved organic matter (DOM) can produce I-DBPs. Hydrogen peroxide (H₂O₂) plays a key role in minimizing the formation of I-DBPs by reduction of HOI during H₂O₂-based advanced oxidation processes or water treatment based on peracetic acid or ferrate(VI). To assess the importance of these reactions, second order rate constants for the reaction of HOI with H₂O₂ were determined in the pH range of 4.0-12.0. H₂O₂ showed considerable reactivity with HOI near neutral pH (k_app = 9.8 × 10³ and 6.3 × 10⁴ M^-1s^-1 at pH 7.1 and 8.0, respectively). The species-specific second order rate constants for the reactions of H₂O₂ with HOI, HO₂^- with HOI, and HO_2^- with OI^- were determined as k_H2O2+HOI = 29 ± 5.2 M^-1s^-1, k_HO2^-_+HOI = (3.1 ± 0.3) × 10⁸ M^-1s^-1, and k_HO2^-_+OI^- = (6.4 ± 1.4) × 10⁷ M^-1s^-1, respectively. The activation energy for the reaction between HOI and H₂O₂ was determined to be E_a = 34 kJ mol^-1. The effect of buffer types (phosphate, acetate, and borate) and their concentrations was also investigated. Phosphate and acetate buffers significantly increased the rate of the H₂O₂-HOI reaction at pH 7.3 and 4.7, respectively, whereas the effect of borate was moderate. It could be demonstrated, that the formation of iodophenols from phenol as a model for I-DBPs formation was significantly reduced by the addition of H₂O₂ to HOI- and phenol-containing solutions. During water treatment with the O₃/H₂O₂ process or peracetic acid in the presence of I^-, O₃ and peracetic acid will be consumed by a catalytic oxidation of I^- due to the fast reduction of HOI by H₂O₂. The O₃ deposition on the ocean surface may also be influenced by the presence of H₂O₂, which leads to a catalytic consumption of O₃ by I^-.

Disinfection by-products (DBPs) in drinking water have been associated with increased cancer risk but single DBPs cannot explain epidemiological cancer occurrences. To test if combined effects of DBPs are plausible to explain epidemiological evidence for adverse health effects, we assessed if mixture effects of DBPs can be predicted using the concentration addition (CA) model. We prepared 12 mixtures of DBPs (trihalomethanes, halonitromethanes, haloacetonitriles, haloketones, haloacetic acids, chloral hydrate, haloacetamides, 3-chloro-4-(dichloromethyl)-5-hydroxy-5H-furan-2-one (MX)) in equipotent concentration ratios. We determined effect concentrations with three reporter gene bioassays (AREc32, ARE-bla, and p53-bla) based on human cell lines and one bacterial assay (Microtox). The experimental effect concentrations agreed well with the effect concentrations predicted with the CA model, which suggests that the CA model is applicable for reactive DBPs despite different molecular mechanisms because the reporter gene assays are only detecting one mechanism each. Modelling of mixture effects of DBPs in ratios detected in drinking water revealed that haloacetonitriles, haloketones, and mono-haloacetic acids contributed the most to the total effect indicating a higher health relevance of these DBP groups. In drinking water samples the sum of the detected DBPs explained <6% of effect in most cases. The CA model could be applied to prioritize DBPs for further risk assessments to potentially close the gap between toxicological cancer risk predictions and epidemiological findings.

Geogenic arsenic (As) contamination of groundwater poses a major threat to global health, particularly in Asia. To mitigate this exposure, groundwater is increasingly extracted from low-As Pleistocene aquifers. This, however, disturbs groundwater flow and potentially draws high-As groundwater into low-As aquifers.
Here we report a detailed characterisation of the Van Phuc aquifer in the Red River Delta region, Vietnam, where high-As groundwater from a Holocene aquifer is being drawn into a low-As Pleistocene aquifer. This study includes data from eight years (2010–2017) of groundwater observations to develop an understanding of the spatial and temporal evolution of the redox status and groundwater hydrochemistry.
Arsenic concentrations were highly variable (0.5-510 μg/L) over spatial scales of <200 m. Five hydro(geo)chemical zones (indicated as A to E) were identified in the aquifer, each associated with specific As mobilisation and retardation processes. At the riverbank (zone A), As is mobilised from freshly deposited sediments where Fe(III)-reducing conditions occur. Arsenic is then transported across the Holocene aquifer (zone B), where the vertical intrusion of evaporative water, likely enriched in dissolved organic matter, promotes methanogenic conditions and further release of As (zone C). In the redox transition zone at the boundary of the two aquifers (zone D), groundwater arsenic concentrations decrease by sorption and incorporations onto Fe(II) carbonates and Fe(II)/Fe(III) (oxyhydr)oxides under reducing conditions. The sorption/incorporation of As onto Fe(III) minerals at the redox transition and in the Mn(IV)-reducing Pleistocene aquifer (zone E) has consistently kept As concentrations below 10 μg/L for the studied period of 2010–2017, and the location of the redox transition zone does not appear to have propagated significantly. Yet, the largest temporal hydrochemical changes were found in the Pleistocene aquifer caused by groundwater advection from the Holocene aquifer. This is critical and calls for detailed investigations.

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.

In the ICO₂P-project the overall aim is to develop an innovative and cost-effective monitoring scheme for CO₂ capture and storage operations, implementing new methods for in situ noble gas measurements. The first step is to establish a basis for fluid source identification by recording temporal variance of noble gas composition in CO₂ product. Studies of noble gases related to CCS typically include few, single point samples. In ICO₂P, a portable mass spectrometer (i.e. miniRUEDI) is utilized to directly measure real time variability of the noble gas content in CO₂ gas streams at operating CCS facilities. The first study was performed at the Technology Centre Mongstad (TCM) in Norway, a large-scale test facility for post-combustion CO₂ capture operations. During an open scientific test campaign for amine-based capture (TSA-MEA), noble gases (He, Ar, Kr) as well as CO₂, N₂, O₂ concentrations in the CO₂ product stream were recorded every 10 to 15 minutes during a 5-day period. He concentrations (<0.001ppm)were depleted post-capture and too low for temporal variation measurements in the CO₂ product line. Ar concentrations (0.15 – 0.65 ppm) were significantly higher and temporal variation was successfully recorded in the CO₂ product line. Ar was found to be sensitive to capture operations, e.g. CO₂ recycling ratio. This new approach will provide knowledge of the uniqueness and variability of inherent noble gas fingerprints and depletion/absorption during CCS operations and provide grounds for comparison between fluid origins needed in leakage detection schemes at CO₂ storage sites.

Five-membered nitrogen-containing heterocyclic compounds (azoles) belong to potential moieties in complex structures where transformations during ozonation can occur. This study focused on the azole-ozone chemistry of pyrrole, imidazole, and pyrazole as model compounds. Reaction kinetics and ozonation products were determined by kinetic and analytical methods including NMR, LC-HRMS/MS, HPLC-UV, and IC-MS. Analyses of reactive oxygen species (¹O₂, ^•OH, H₂O₂), quantum chemical computations (Gibbs energies), and kinetic simulations were used to further support the proposed reaction mechanisms. The species-specific second-order rate constants for the reactions of ozone with pyrrole and imidazole were (1.4 ± 1.1) × 10⁶ M^-1 s^-1 and (2.3 ± 0.1) × 10⁵ M^-1 s^-1, respectively. Pyrazole reacted more slowly with ozone at pH 7 (k_app = (5.6 ± 0.9) × 10¹ M^-1 s^-1). Maleimide was an identified product of pyrrole with a 34% yield. Together with other products, formate, formamide, and glyoxal, C and N mass balances of ~50% were achieved. Imidazole reacted with ozone to cyanate, formamide, and formate (~100% yields per transformed imidazole, respectively) with a closed mass balance. For pyrazole, a high ozone:pyrazole molar stoichiometry of 4.6 was found, suggesting the transformation products contributed to the over-stoichiometric consumption of ozone (e.g., hydroxypyrazoles). Glyoxal and formate were the only identified transformation products (C mass balance: 65%). Overall, the identified major products are suspected to hydrolyze and/or be biodegraded and thereby abated by a biological post-treatment typically following ozonation. However, as sub-structures of more complex compounds (e.g., micropollutants), they might be more persistent during the biological post-treatment.

We collected bottom water samples and unconsolidated sediment samples for noble-gas analysis in the water column as well as in the pore water phase along the Nankai Trough to assess the sources and fluxes of seafloor fluid emission at the local/regional scale. The results indicate that terrigenic He emission is rather variable in terms of fluxes and isotope signatures. The largest He fluxes are detected at a previously investigated cold seep site where terrigenic He is mainly of crustal origin. High He isotope ratios detected at shallower depths in the Kumano Basin indicate that mantle fluids are able to migrate from the deep sediment column up to the seafloor. Our findings are in line with the detection of mantle He in fluids recovered by IODP (International Ocean Discovery Program) deep-drilling operations and make the case that even seafloor volatile screening and monitoring might provide useful insights on the relation between fluid dynamics and tectonic/seismic activity in the investigated region for future forecasting of earthquakes.

Soils on the Erzmatt (Switzerland) formed on hydrothermally mineralized dolomite rock and are naturally Tl-rich. In this study, we investigated if variations in the stable Tl isotope ratios in soil samples from different profiles can be linked to data on the extractability and speciation of soil Tl and whether the isotopic data allow drawing conclusions on the geochemical processes that affected Tl over the course of soil formation. In two soil profiles, we observed a marked accumulation of the heavy ²⁰⁵Tl isotope in the B horizons, with ε²⁰⁵Tl values that were up to 7 higher than in the underlying bedrock. This ²⁰⁵Tl enrichment, however, was neither reflected in the speciation of Tl nor its chemical fractionation. Furthermore, exchangeable soil Tl in the B horizons was found to be much isotopically lighter than the bulk soil Tl. These findings suggest that the observed isotopic shift may be linked to cyclic Tl mobilization and immobilization processes over the period of rock weathering and soil formation. Oxidative Tl uptake by Mn-oxides associated with a ²⁰⁵Tl enrichment, continuous weathering of the Tl(III)-containing phases, followed by a Tl(I) remobilization (leading to enrichment in ²⁰⁵Tl) are suggested to be responsible for the binding of the heavy Tl isotope fraction into other phases, mainly illite (a dominant Tl host), which is not normally expected. Hence, our results show that the Tl isotopic fractionation data measured in a dynamic multi-phase (soil) system can potentially serve as a proxy for tracing redox-controlled processes, but their use for phase or the sorption process identification is much more complicated.