Small villages and their sanitary infrastructure-an unnoticed influence on water quantity and a threat to water quality in headwater catchments.

In rural catchments, villages often feature their own, separate urban water infrastructure, including combined sewer overflows (CSOs) or wastewater treatment plants (WWTPs). These point sources affect the water quantity and quality of the receiving low order streams. However, the extent of this impact is rarely monitored. We installed discharge and water quality measurements at the outlet of two small, neighbouring headwater catchments, one that includes a village, a WWTP, and two CSOs, while the other is predominantly influenced by agricultural activities. We also deployed electrical conductivity (EC) loggers at the CSOs to accurately detect discharge times. Discharge from the WWTP and CSOs led to higher peak flows and runoff coefficients during events. Less dilution of EC and increasing ammonium-N (NH4 - N) and ortho-phosphorus (oPO4 - P) concentrations indicate a significant contribution of poorly treated wastewater from the WWTP. During CSO events, water volumes and nutrient loads were clearly elevated, although concentrations were diluted, except for nitrite-N (NO2 - N) and particulate phosphorus (PP). Baseflow nitrate-N (NO3 - N) concentrations were diluted by the WWTP effluent, which led to considerably lower concentrations compared to the more agriculturally influenced stream. Concentrations of oPO4 - P, NH4 - N, and NO2 - N, which are most likely to originate from the WWTP, vary throughout the year but are always elevated. Our study shows the major and variable impact rural settlements can have on stream hydrology and water quality. Point sources should be monitored more closely to better understand the interaction of natural catchment responses and effects caused by sanitary infrastructure.

Influence of age on the concentrations of perfluoroalkyl acids (PFAA) in the tissues of perch (Percafluviatilis).

Globally, perfluoroalkyl acids (PFAA) are ubiquitous due to their almost unlimited applications in industry and households and are detected in a wide variety of matrices.Aquatic ecosystems are of particular importance due to the spread of PFAA via water fluxes. The majority of published studies describe PFAA concentrations in fish or aquatic mammals, but not the dependence of PFAA concentrations in tissues and organs in fish of different ages. Since this is very important for understanding the accumulation behavior of these substances our study systematically investigates the influence of age on the PFAA concentration in the tissues of 74 perches (Perca fluviatilis), a very popular edible fish. Fish are particularly suitable as indicators of PFAA contamination of water because of their uptake via water (gills and skin) and food (predominantly piscivorous diet). The mean total PFAA concentrations (as the sum of the individual concentrations of 11 compounds) were: 114 µg/kg (kidney), 112 µg/kg (heart), 79.9 µg/kg (liver), 78.4 µg/kg (spleen), 64.6 µg/kg (gills) and 21.7 µg/kg (muscle), with longer-chain compounds accounting for 90% of the substances. Perfluorooctanesulfoic acid (PFOS) accounted for the largest percentage of the total PFAA concentration in all tissues at 43-63%. With the exception of the heart and spleen, a significant increase in total concentrations was observed with increasing age of the perch. The strongest correlation was observed for the kidney, followed by the liver and gills. With regard to their consumption as human nutrition the tolerable weekly PFAA intake of 4.4 ng/kg bodyweight and week for the sum of the 4 EFSA PFAA in adults and children was exceeded many times over (860% and 1600% respectively) with an average fish consumption per week. The maximum PFAA levels set in the E.U. since January 2023 were exceeded five times.

Modelling the impacts of climate change on agrochemical fate and transport by water on a catchment scale.

The export of agrochemicals and their transformation products (TPs) following their application in the agricultural fields poses a threat to water quality. Future changes in climatic conditions (e.g. extreme weather events such as heavy rainfall or extended dry periods) could alter the degradation and mobility of agrochemicals. In this research, we use an integrated modelling framework to understand the impact of extreme climate events on the fate and transport of the agrochemical S-Metolachlor and two of its TPs (M-OXA, Metolachlor Oxanilic Acid and M-ESA, Metolachlor Ethyl Sulfonic Acid). This is done by coupling climate model outputs to the Zin-AgriTra agrochemical reactive transport model in four simulation scenarios. 1) Reference (2015-2018), 2) Very dry (2038-2041), 3) Very wet (2054-2057) and 4) High temperature (2096-2099) conditions of a selected RCP8.5 based regional climate scenario. The modelling framework is tested on an agricultural catchment, Wulka, in Burgenland, Austria. The model results indicate that 13-14 % of applied S-Metolachlor is retained in the soil, and around 85 % is degraded into TPs in the different scenarios. In very dry and high-temperature scenarios, degradation is higher, and hence, there is less S-Metolachlor in the soil. However, a large share of formed M-OXA and M-ESA are retained in the soil, which is transported via overland and groundwater flow, leading to a build-up effect in M-OXA and M-ESA river concentrations over the years. Though a small share of S-Metolachlor and TPs are transported to rivers, their river export is affected by the intensity and amount of rainfall. The very wet and high-temperature scenarios show higher S-Metolachlor and TP concentrations at the catchment outlet due to higher river discharge. The reference scenario shows higher river peak concentrations associated with higher overland flow caused by measured hourly rainfall compared to disaggregated daily precipitation data in the other scenarios.

Long-term sulfamethazine leaching simulation in two different soils using the MACRO model.

Physically based models have been part of many risk assessment studies concerning pesticide or nutrient transport within (sub)catchments or at plot scale, but they are only poorly validated for simulating the transport of veterinary medicinal products. Veterinary medicinal products not only pose a risk to the quality of our waters but also tend to accumulate in soils, where they are associated with the appearance of resistant bacteria and long-term leaching. In this study, the physically based leaching model MACRO 5.2 was applied for simulating sulfamethazine (SMZ) transport over a period of more than 10 yr. The model was set up using reversible kinetic adsorption and equilibrium adsorption forming non-extractable residues. Two different calibration periods were used to estimate uncertainties in predicted SMZ leaching associated with calibration based on short-term data. Using the whole period for model calibration, SMZ leaching could be simulated adequately, but parameter ranges were wide due to correlation between the parameters. When using only the first period for calibration, the quality of the prediction strongly depended on the information content of the data set. The calculation of temporal sensitivity indices revealed that the effect of complex sorption parameters on the model output increased with time. Thus, parameters that appeared insensitive in a short-term calibration were required for reliable long-term simulations. In conclusion, a temporal sensitivity analysis beyond the calibration period might identify parameters that were not constrained enough by the calibration procedure. This could help to confirm leaching predictions even for periods without sampling data.

Leaching and Transformation of Perfluoroalkyl Acids and Polyfluoroalkyl Phosphate Diesters in Unsaturated Soil Column Studies.

Per- and polyfluoroalkyl substances (PFAS) are environmentally ubiquitous, anthropogenic substances with adverse effects on organisms, which shows the need to study their environmental fate and leaching behavior. In the present soil columns study, the leaching behavior and fate of nontransformable and transformable (precursors) were investigated. Ten nontransformable PFAS in two different soils, two precursors and two field soils, which were already contaminated with a mixture of PFAS, and two uncontaminated controls, were set up for a time span of 2 years. At the end of the study, the molecular balance could not be closed for nontransformable PFAS. This effect was positively correlated to the fluorinated carbon chain length. The precursors, which were both polyfluoroalkyl phosphate diesters (diPAP), had different transformation products and transformation rates, with a higher rate for 6:2 diPAP than 8:2 diPAP. After 2 years, amounts of diPAP were still found in the soil with no significant vertical movement, showing high adsorption to soils. Transformation products were estimated to be simultaneously formed. They were predominantly found in the percolation water; the amounts left in soil were negligible. Up to half of the initial precursor amounts could not be balanced and were considered missing amounts. The results of contaminated field soil experiments showed the challenge to estimate PFAS leaching without knowing all occurring precursors and complex transformation dynamics. For this purpose, it was shown that a broad examination of contaminated soil with different analytical methods can help with qualitative estimations of leaching risks. For a better quantitative estimation, analytical determination of more PFAS and a quantification of the missing amounts are needed. Environ Toxicol Chem 2022;41:2065-2077. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Degradation and Plant Transfer Rates of Seven Fluorotelomer Precursors to Perfluoroalkyl Acids and F-53B in a Soil-Plant System with Maize (Zea mays L.).

Fluorotelomer precursors in soil constitute a reservoir for perfluoroalkyl acids (PFAAs) in the environment. In the present study, precursor degradation and transfer rates of seven fluorotelomer precursors and F-53B (chlorinated polyfluoroalkyl ether sulfonates) were investigated in pot experiments with maize plants (Zea mays L.). The degradation of fluorotelomer precursors to perfluoroalkyl carboxylic acids (PFCAs) and their uptake spectra corresponded to those of fluorotelomer alcohol (FTOH) in terms of the number of perfluorinated carbon atoms. Short-chain PFCAs were translocated into the shoots (in descending order perfluoropentanoic, perfluorobutanoic, and perfluorohexanoic acid), whereas long-chain PFCAs mainly remained in the soil. In particular, fluorotelomer phosphate diesters (diPAPs) were retained in the soil and showed the highest degradation potential including evidence of α-oxidative processes. F-53B did not degrade to PFAAs and its constituents were mainly detected in the roots with minor uptake into the shoots. The results demonstrate the important role of precursors as an entry pathway for PFCAs into the food chain.

Evaluation of the Transformation and Leaching Behavior of Two Polyfluoroalkyl Phosphate Diesters in a Field Lysimeter Study.

In this study, 6:2 and 8:2 polyfluoroalkyl phosphate diester (diPAP) were individually investigated in lysimeters under near-natural conditions. Leachate was sampled for 2 years, as was the soil after the experiment. In the leachate of the diPAP-spiked soils, perfluorocarboxylic acids (PFCAs) of different chain lengths were detected [23.2% (6:2 diPAP variant) and 20.8% (8:2 diPAP variant) of the initially applied molar amount]. After 2 years, the soils still contained 36-37% 6:2 diPAP and 41-45% 8:2 diPAP, respectively, in addition to smaller amounts of PFCAs (1.5 and 10.6%, respectively). Amounts of PFCAs found in the grass were low (<0.1% in both variants). The recovery rate of both 6:2 diPAP and 8:2 diPAP did not reach 100% (63.9 and 83.2%, respectively). The transformation of immobile diPAPs into persistent mobile PFCAs and their transport into the groundwater shows a pathway for human exposure to hazardous PFCAs through drinking water and irrigation of crops.

Combined leaching and plant uptake simulations of PFOA and PFOS under field conditions.

Per- and polyfluoroalkyl substances (PFASs) are used in industrial production and manufacturing but were repeatedly detected in agricultural soils and therefore in cash crops in recent years. Dissipation of perfluoroalkyl acids (PFAAs), a sub-group of PFASs, in the environment was rather attributed to the formation of non-extractable residues (NER) than to degradation or transformation. Currently, there are no models describing the fate of PFAAs in the soil-plant continuum under field conditions, which hampers an assessment of potential groundwater and food contamination. Therefore, we tested the ability of the pesticide-leaching model MACRO to simulate the leaching and plant uptake of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in a field lysimeter using two concepts of adsorption: a kinetic two-side sorption concept usually applied for pesticide leaching (scenario I) and the formation of NER (scenario II). The breakthrough of substances could be simulated adequately in scenario II only. Scenario I, however, was not able to reproduce sampled leaching concentrations. Plant uptake was simulated well in the first year after contamination but lacked adequacy in the following years. The model results suggest that more than 90% of PFOA and PFOS are in the pool of NER after 8 years, which is more compared with other studies. However, since NER formation was hypothesized to be a kinetic process and our study used a PFASs leaching time series over a period of 8 years, the results are reasonable. Further research is required on the formation of NER and the uptake of PFAAs into plants in order to gain a better model performance and extend the simulation approach to other PFAAs.

Concentrations and Distribution Patterns of Perfluoroalkyl Acids in Sewage Sludge and in Biowaste in Hesse, Germany.

A total of 201 sewage sludge and 45 biowaste samples were examined for 14 different perfluoroalkyl acids (PFAA). For perfluorooctanesulfonic acid, maximum concentrations of 698 µg/kg dry weight were measured in sewage sludge and for perfluorohexanesulfonic acid 29.0 µg/kg dry weight were found in biowaste. Looking at the fingerprints of both these matrixes it can be see that long-chain PFAA make up 85.9% of the total concentration in sewage sludge whereas short-chain PFAA only account for 14.1%. In contrast, the trend in biowaste is just the opposite, with 53.2% long-chain and 46.8% short-chain PFAA. These results lead to the conclusion that sewage sludge functions as a sink for long-chain PFAA, and the plants preferentially take up short-chain PFAA from the sludge/soil, as seen by the concentrations found in biowaste. It can be calculated that the total yearly amount of PFAA spread onto agricultural lands amount to 15.3 kg.

Experimental and in silico assessment of fate and effects of the antipsychotic drug quetiapine and its bio- and phototransformation products in aquatic environments.

The antipsychotic drug quetiapine (QUT) has been frequently detected in sewage treatment plants. However, information on the fate of QUT in aquatic environments and its behavior during UV treatment is limited. In this study, QUT is shown not to be readily biodegradable in the Closed Bottle Test and the Manometric Respirometry Test according to OECD guidelines. The main biotransformation product (BTP) formed in the tests, a carboxylic acid derivative, was identified by means of high-resolution mass spectrometry. This BTP is presumably a human metabolite and showed higher detection rates than QUT in a river sampling campaign conducted in northern Germany. UV elimination kinetics of QUT at different initial concentrations (226.5, 45.3, 11.3, and 2.3 µmol L-1) were faster at lower initial concentrations. All seven phototransformation products (PTPs) could be still identified at initial concentration of 11.3 µmol L-1. The photolytic mixture generated after 128 min of photolysis of QUT was not better biodegradable than QUT. Initial UV treatment of QUT led to the formation of several additional BTPs. Four of them were identified. The bacterial cytotoxicity and genotoxicity before and after phototransformation of QUT in a modified luminescent bacteria test (LBT) and the umu-test (ISO/FDIS 13829) showed cytotoxic effects in the LBT for QUT. Furthermore, PTPs had similar cytotoxic effects on luminescent bacteria. The umu-test did not reveal any genotoxic activity for QUT or PTPs. In conclusion, the release of QUT into sewage treatment plants and aquatic environments could result in the formation of a main BTP. Additional UV treatment of QUT would lead to the formation of additional BTPs. Moreover, treatment did not result in lower toxicity to tested organisms. In conclusion, UV treatment of QUT should be considered critically as a potential treatment for QUT in aquatic systems.