Département Chimie de l’environnement

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%.

Aquatic pesticide pollution from both agricultural and urban pest control is a concern in many parts of the world. Making an accurate assessment of pesticide exposure is the starting point to protecting aquatic ecosystems. This in turn requires the design of an effective monitoring program. Monitoring is also essential to evaluate the efficacy of mitigation measures aimed to curb pesticide pollution. However, empirical evidence for their efficacy can be confounded by additional influencing factors, most prominently variable weather conditions. This review summarizes the experiences gained from long-term (>5 years) pesticide monitoring studies for detecting trends and provides recommendations for their improvement. We reviewed articles published in the scientific literature, with a few complements from selected grey literature, for a total of 20 studies which fulfill our search criteria. Overall, temporal trends of pesticide use and hydrological conditions were the two most common factors influencing aquatic pesticide pollution. Eighteen studies demonstrated observable effects to surface water concentrations from changes in pesticide application rates (e.g., use restriction) and sixteen studies from interannual variability in hydrological conditions during the application period. Accounting for seasonal- and streamflow-related variability in trend analysis is important because the two factors can obscure trends caused by changes in pesticide use or management practices. Other mitigation measures (e.g., buffer strips) were only detectable in four studies where concentrations or loads were reduced by > 45%. Collecting additional agricultural (e.g., pesticide use, mitigation measures) and environmental (e.g., precipitation, stream flow) data, as well as establishing a baseline before the implementation of mitigation measures have been consistently reported as prerequisites to interpret water quality trends from long-term monitoring studies, but have rarely been implemented in the past.

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

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