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To investigate the formation and leaching potential of degradation products N,N-dimethylsulfamide (DMS) and dimethylsulfamic acid (DMSA) from cyazofamid under real-world agricultural conditions, the fungicide cyazofamid was applied in a potato crop as part of the Danish Pesticide Leaching Assessment Programme (PLAP). Leaching of DMS, DMSA, 4-chloro-5-(4-methylphenyl)-1H-imidazole-2-carbonitrile (CCIM), and 4-chloro-5-(4-methylphenyl)-1H-imidazole-2-carboxylicacid (CTCA) was monitored in water from the variably saturated zone (suction cups) and groundwater for more than two years following the applications. In total, 424 samples were analyzed for the content of the four degradation products. An additional laboratory study was executed in parallel with the field monitoring study. Here, cyazofamid was applied to soil columns and leaching of the four degradation products was studied under controlled conditions. In the EFSA conclusion on cyazofamid, CCIM and CTCA are mentioned as major relevant metabolites; DMS is not mentioned in the risk assessment and DMSA is only included in acute oral toxicity studies and an in vitro bacterial mutation assay. In contrast to the EFSA conclusion on cyazofamid, our studies showed no leaching of the two major metabolites, CTCA and CCIM, but instead, major leaching of DMS and DMSA in both the field and laboratory studies was observed. That is, both DMS and DMSA leached to the groundwater in concentrations >0.1 μg/L for more than half a year. Based on this, we suggest improvements to the current pesticide risk assessment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Contamination of rivers by nitrate and pesticides poses a risk for aquatic ecosystems in lowland catchments that are often intensively used for agriculture. Here, the hyporheic zone, the streambed underneath the stream, plays a vital role due to its efficient self-purification capacity. The present study aims to evaluate the denitrification and transformation potential of 14 pesticides and three transformation products in the hyporheic sediment from a lowland stream with a high N load and by comparing an agricultural straightened section to a natural meandering part of the stream influenced by different groundwater discharges. Batch experiments were set up to evaluate the denitrification and pesticide transformation potentials in hyporheic sediment from two depths (5-15 cm (a) and 15-25 cm (b)). Our results revealed that (i) differences between the agricultural and natural sections of the river did not influence pollutant attenuation, (ii) both the nitrate and pesticide attenuation processes were more rapid in the upper "a" layer compared to the "b" layer due to higher microbial abundance, (iii) high groundwater discharge reduced the denitrification potential while pesticide transformation was unaffected, (iv) denitrification correlated with denitrifier abundance (nirK) in the "b" layer, while this correlation was not seen in the "a" layer, and (v) a microbial community with low diversity can explain limited transformation for the majority of tested pesticides. Overall, our results suggest that high groundwater discharge zones with reduced residence time in the hyporheic zone can be an important source of pesticides and nitrate to surface water., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Hyporheic sediments are influenced by physical, biological, and chemical processes due to the interactions with river water and has been shown to play an important role in the environmental fate of pesticides. Therefore, this study evaluated the bacterial degradation potential of MCPA, metolachlor and propiconazole in hyporheic sediments sampled along a 20 km long stretch of an agriculturally impacted river dominated primarily by water losing conditions. Water physicochemical parameters in the river and nearby groundwater wells were assessed along with pesticide sorption to sediments and bacterial community composition. Degradation and mineralisation batch experiments were set up from six locations (five water losing, one water gaining) using environmentally relevant concentrations of pesticides (10 μg kg -1 ). Highly variable DT 50 values from 11 to 44 days for MCPA, 11-27 days for metolachlor (MTC) and 60-147 days for propiconazole were calculated based on ~140 day studies. Degradation of MTC led to accumulation of the transformation products MOA and MESA in batch experiments. Noteworthy, MESA was detected in the groundwater wells adjacent to the part of the river impacted by losing conditions suggesting that degradation processes in hyporheic sediments may lead to the formation of transformation products (TP) leaching towards groundwater. Further, from propiconazole was identified a persistent transformation product being different from 1,2,4-triazole. Specific calculated DT 50 values could not the linked to bacterial diversity. However, generally all sediment samples were characterised by high bacterial diversity, where approximately 80% of the relative sequence abundances were < 1%, which may increase the likelihood of finding contaminant-degrading genes, thereby explaining the general high contaminant-degrading activity. The studied sediments revealed a high potential to degrade pesticides despite only being exposed to low diffuse pollutant concentrations that is similar to calculated DT 50 values in agricultural soils., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The risk of pesticide leaching from recreational areas such as golf course turfs is not distinguished in a regulative framework within the EU where the focus is on agricultural soils. But with increasing popularity of golf, and thus, increasing number of golf courses leading to potentially increasing use of pesticides, understanding the processes determining pesticide leaching are critical to ensure optimal quality of both groundwater and golf turf. This study input the measured variation in fate properties of tebuconazole (TBZ) and MCPA as pure active ingredients and commercial products in simulations with realistic hydrological conceptualizations to investigate their implication in leaching assessments. Scenarios with (i) fluctuating and fixed groundwater levels and (ii) preferential flows including fluctuating and fixed groundwater levels were evaluated. The results showed that mobile MCPA leached in higher concentrations by a factor of 1.3 with fluctuating groundwater levels than with fixed groundwater levels. When preferential flow paths were incorporated in the models, the leaching was substantial for MCPA regardless of its formulation as active ingredient or commercial product, while in multiple simulations without preferential pathways there was no leaching of MCPA. Compared to MCPA leaching without preferential flow paths, the leaching concentrations increased up to a factor of 13.9 when preferential flows were included. With preferential flow paths, the increase in leaching concentration from fixed groundwater levels to fluctuating groundwater levels was up to a factor of 2.3 depending on the formulation of MCPA. This study demonstrated that it is imperative to assess fate parameters in the topsoil of golf courses and consider realistic groundwater BC (boundary condition) and the presence of preferential flow paths to obtain representative pesticide leaching risk assessments., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Groundwater is an important drinking water resource. To ensure clean drinking water, managed aquifer recharge (MAR) could be an attractive solution when recharging with treated wastewater. The installation of reactive barriers, e.g. with compost or other organic materials at MAR facilities, may improve pollutant removal. To link pollutant transformation processes and microbiology in reactive barriers, we simulated infiltration through different sand-compost mixtures using laboratory columns with depth-specific sampling of water and barrier material. We also evaluated the effect of inoculation with activated sludge. Our focus was on the simultaneous removal of organic micropollutants and nitrogen species, with parallel monitoring of the development of microbial communities. During 17 weeks of operation, the columns were fed with synthetic wastewater containing five organic micropollutants (1-2 µg/L each) and ammonium (2 mg N/L). Unique communities developed in the columns in relation to barrier material, with high effects of compost addition and minor effect of inoculation. Removal of the micropollutant paracetamol (acetaminophen) occurred in all columns, while sulfamethoxazole was only removed in columns with 50% compost. By contrast, limited removal was observed for sulfadiazine, carbamazepine and diuron, with the latter two displaying transient removal, attributed sorption. Oxygen was depleted within the top few cm of the columns when compost was present, but this was sufficient to remove all ammonium through nitrification. The fate of accumulated nitrate at deeper layers depended on the fraction of compost, with more compost leading to removal of nitrate by denitrification, but also by dissimilatory nitrate reduction to ammonium, hampering the overall nitrogen removal efficiency. Introducing compost as reactive barrier in MAR facilities has a large effect on the microbial communities and processes, but whether it will provide overall cleaner water to the underlying aquifer is uncertain and will depend very much on the type of pollutant., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Small polar organic pollutants have been discovered to be great threats to the groundwater‚ as they often are highly mobile and persistent in the environment. 1,2,4-Triazole and N,N-dimethylsulfamide, two well-known examples of small polar compounds, are frequent pollutants of upper groundwater. Both are degradation products of several fungicides commonly or previously used in agriculture‚ but also in wood-preserving paints. A common trait in the analysis of these small polar compounds is the lack of sufficient pre-concentration methods to lower the limit of detection and enable quantitative analysis at nano-scale concentrations. To date, they are analyzed only by direct injection in HPLC-MS/MS, with detection limits just below the European threshold value for pesticides in groundwater of 0.1 μg/L. Based on a comprehensive method development, a solid phase extraction method was developed. As known LC methods for analysis of 1,2,4-triazole are based on Thermo Fisher's Hypercarb column, emphasis was placed on testing various carbon-based materials. The final, thoroughly validated extraction protocol is based on Supelco's ENVI-Carb Plus cartridges. With extraction recoveries close to 100% for 1,2,4-triazole and N,N-dimethylsulfamide and quantification limits of around 0.003 μg/L, the method enables extraction and quantification of polar pollutants at nano-scale concentration from groundwater samples. In addition, the method is very promising to be used for other small polar pollutants. [ABSTRACT FROM AUTHOR]