Département Chimie de l’environnement

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.

Pesticides used in agriculture can end up in nearby streams and can have a negative impact on nontarget organisms such as aquatic invertebrates. During registration, bioaccumulation potential is often investigated using laboratory tests only. Recent studies showed that the magnitude of bioaccumulation in the field substantially differs from laboratory conditions. To investigate this discrepancy, we conducted a field bioaccumulation study in a stream known to receive pollutant loadings from agriculture. Our work incorporates measurements of stream pesticide concentrations at high temporal resolution (every 20 min), as well as sediment, leaves, and caged gammarid analyses (every 2-24 h) over several weeks. Of 49 investigated pesticides, 14 were detected in gammarids with highly variable concentrations of up to 140 ± 28 ng/g_ww. Toxicokinetic modeling using laboratory-derived uptake and depuration rate constants for azoxystrobin, cyprodinil, and fluopyram showed that despite the highly resolved water concentrations measured, the pesticide burden on gammarids remains underestimated by a factor of 1.9 ± 0.1 to 31 ± 3.0, with the highest underestimations occurring after rain events. Including dietary uptake from polluted detritus leaves and sediment in the model explained this underestimation only to a minor proportion. However, suspended solids analyzed during rain events had high pesticide concentrations, and uptake from them could partially explain the underestimation after rain events. Additional comparison between the measured and modeled data showed that the pesticide depuration in gammarids is slower in the field. This observation suggests that several unknown mechanisms may play a role, including lowered enzyme expression and mixture effects. Thus, it is important to conduct such retrospective risk assessments based on field investigations and adapt the registration accordingly.

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.

Wicked problems exceed traditional sectoral and jurisdictional boundaries and involve multiple actors as stakeholders, victims, and culprits. Wicked problems inherently feature uncertainty and knowledge gaps. Science plays a crucial role in generating evidence for solving these problems and contributing to societal transformation. However, researchers may perceive and study problems detached from practitioners' perceptions of the world. We use the example of smallholder pesticide management in Uganda and the three types of knowledge approach, a framework borrowed from transdisciplinary research, to disentangle knowledge gaps. To identify these gaps, we integrated and co-produce knowledge in a two-day participatory workshop applying design thinking. Our results show, that a transition towards safe pesticide management depends on changes in the system, such as a revision and implementation of exiting regulation or professionalization of agro-dealers. Furthermore, this transition is only possible if interventions address target groups beyond the individual farmers (e.g. agro-dealers or district government officials). Compared to existing academic knowledge, co-produced knowledge provides a broader systemic perspective and yields more fine grained insights about potential new pathways. This investigation confirms, that practitioners’ knowledge is more fine-grained and detailed, thus exemplifying how knowledge integration is essential to avoid a gap between what researchers investigate and what practitioners need.