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Degradation rates of two widely used pesticides were assessed, and acute and chronic effects on a standard invertebrate species investigated. An herbicide (Montana®) and fungicide (Bravo500®) formulations were investigated and results were compared to the isolated active substances of each formulation (glyphosate and chlorothalonil, respectively). Tests were performed using the invertebrate Folsomia candida as test species and an agricultural natural soil. Degradation rate tests were determined under aerobic conditions at 20 ± 2 °C, using an ecologically relevant concentration of 5 mg (a.i.) kg−1 of soil for both chemicals. Results demonstrated degradation half-lives (DT50) of 2.2 days for Montana® and 2.8 days when pure glyphosate was tested. Values of 1.1 and 2.9 days were registered for Bravo500® and its active substance chlorothalonil, respectively. There were no effects on survival for the tested concentrations of both forms of the herbicide (up to 17.3 mg kg−1). However, reproduction was affected, but only by the herbicide formulation, with an estimated EC50 value of 4.63 mg (a.i.) kg−1. Effects were most unlikely related to glyphosate. For chlorothalonil, both tested forms affected survival and reproduction. The estimated LC50 values were 117 mg (a.i.) kg−1 and 73.5 mg (a.i.) kg−1, and the EC50 41.3 mg (a.i.) kg−1 and 14.9 mg kg−1 for the formulation and the active ingredient, respectively. The effects of the active ingredient were significantly stronger, indicating the major influence of the active substance in the effects caused also by the formulation. Overall results demonstrate the importance of evaluating the effects of the formulated chemicals, as they are applied in the field, and not only their isolated active ingredients. Unlabelled Image • Glyphosate and chlorothalonil formulations/active ingredients were studied. • The tested chemicals rapidly degraded in a natural agricultural soil. • Sub- and lethal toxicity of chlorothalonil largely depended on its chemical formulation. • Sensitivity of springtails was pesticide-specific. • Chlorothalonil was the most toxic chemical to Folsomia candida. [ABSTRACT FROM AUTHOR]

Several micropollutants, including caffeine, artificial sweeteners, pharmaceuticals, steroid hormones and a current-use pesticide were analyzed in water samples collected from five groundwater pumping stations in Barbados. The presence of caffeine and three artificial sweeteners (i.e. acesulfame, sucralose, saccharin) in groundwater samples indicated that groundwater was being contaminated by infiltration of wastewater into the karst aquifer. An estrogen (i.e. estrone), three pharmaceuticals (i.e. carbamazepine, trimethoprim, ibuprofen) and a transformation product of the fungicide, chlorothalonil (i.e. 4-hydroxychlorothalonil) were also detected at ng/L concentrations in groundwater collected from two or more pumping sites. The concentrations of carbamazepine and trimethoprim were correlated with the concentrations of caffeine (R2 values of 0.70 to 0.80), indicating pharmaceutical contamination of groundwater by infiltration from domestic wastewater. The concentrations of caffeine were generally higher in groundwater samples collected in June during the wet season relative to the concentrations in samples collected in February during the dry season, indicating that infiltration of contaminants is higher during periods of heavy rainfall. Rapid rates of degradation and relatively slow rates of infiltration may explain why several target analytes were not detected in groundwater. Elevated concentrations of 4-hydroxychlorothalonil > 0.1 μg/L in samples collected at two of the monitoring sites warrant further studies on the sources and the distribution of this compound and other pesticides used in agriculture and for turf-treatment (e.g. golf courses). Overall, more data are needed in order to implement mitigation strategies that are effective in reducing chemical contamination in groundwater in Barbados. Unlabelled Image • Micropollutants of wastewater origin detected in groundwater in Barbados • Caffeine is a promising chemical tracer of wastewater. • A metabolite of the fungicide, chlorothalonil was detected in ground water. • Domestic wastewater, agriculture and golf courses are likely sources. [ABSTRACT FROM AUTHOR]

The fungicide chlorothalonil (CHT) has been widely used in the tea orchard due to its high-efficiency and sterilization. It has been reported that repeated application of CHT inhibits soil nitrification process. However, the acute impact of CHT on soil denitrification and associated N 2 O emissions is unclear. This study evaluated nitrate (NO 3 − ) removal, denitrifying gene abundance and denitrifying enzyme activity of tea orchard soil after a 72-h-exposure to CHT. It was found that increasing CHT from 5 to 25 mg kg −1 suppressed the NO 3 − removal efficiency from 74.6% to 54.1%, but increased N 2 O emissions from 23.1% to 94.8%. Following treatment with 25 mg kg −1 of CHT, the abundances of the nir K, nir S and nos Z genes were reduced by 31.6%, 22.1%, and 50.7%, respectively. Alternatively, the declines of the electron transport system activity (ETSA) value and adenosine triphosphate (ATP) content suggested that CHT had an inhibitory effect on microbial metabolism. Enzyme activity studies further revealed that the decrease of nitrate reductase (NAR), nitrite reductase (NIR) and nitric oxide reductase (NOR) activities was the main reason for the suppression of denitrification by CHT. Furthermore, positive correlations were observed between denitrifying reductase activity and the intracellular metabolism, indicating that the decrease in microbial metabolism should also be responsible for the inhibitory effect of CHT on the denitrifying process. Overall, it was found that the acute exposure of soil to CHT could inhibit the denitrification process and significantly increase N 2 O emissions, which might result in destruction of the soil nitrogen cycle and exacerbation of global warming. [ABSTRACT FROM AUTHOR]

Pesticide volatilization and deposition with precipitation is widely documented and has been connected to adverse ecological impact. Here we describe a 3-yr study of current use and legacy pesticides in event-based rain samples within a 123-ha agricultural watershed. Crops in farm fields were documented quarterly with data used to estimate target compound use. The median number of pesticide detections in samples was 6. The fungicide, chlorothalonil which was used most intensively was detected in nearly all samples. It had the highest mean and peak concentrations with total deposition ≈ 0.1% of the estimated amount applied. The insecticide endosulfan also had relatively high use with behavior mirroring chlorothalonil. There was strong seasonal variation in concentration and depositional dynamics with the highest values measured during growing seasons. Similar behavior was observed with other compounds detected in rain samples with a general decrease in deposition and mean concentrations as use decreased. Comparison of measured concentrations to values associated with toxic impact on aquatic organisms indicated that chlorothalonil, endosulfan, chlorpyrifos, malathion and atrazine may contribute to adverse impact. The number of samples exceeding risk endpoints ranged from 1 to 77%. The highest value was for endosulfan; however its on-going phase-out is expected to reduce risks. Another finding was that the wet deposition of the herbicide, metolachlor exceeded measured runoff rates in the watershed by 5-fold. The study has demonstrated that localized pesticide wet deposition may present ecological risks and that volatilization and wet deposition is an important pesticide transport pathway at the local scale. Findings point to the need to include wet deposition in assessments of pesticide ecological risk and environmental fate. [ABSTRACT FROM AUTHOR]

The widespread and increasing application of chlorothalonil (CTN) raises concerns about its non-target impacts, but little information is available on the effect of CTN on the key functional genes related to soil nitrogen (N) cycling, especially in the case of repeated applications. In the present study, a microcosm incubation was conducted to determine CTN residues and the impacts on the abundances of key functional genes related to N cycling after repeated CTN applications. The results demonstrated that repeated CTN applications at the recommended application rate and five times the recommended rate led to the accumulation of CTN residue in soil at concentrations of 5.59 and 78.79 mg kg − 1 , respectively, by the end of incubation. Real time PCR (RT-PCR) revealed that repeated CTN applications had negative effects on the chi A and apr A gene abundances. There were significantly negative correlations between CTN residues and abundances of AOA and AOB genes. In addition, the abundances of key functional genes involved in soil denitrification were declined by repeated CTN applications with the sole exception of the nos Z gene. This study suggests that repeated CTN applications could lead to the accumulation of CTN residue and generate somewhat inconsistent and erratic effects on the abundances of key functional genes related to soil N cycling. [ABSTRACT FROM AUTHOR]

Abstract: Effects of contaminants on behavior may have important consequences on wildlife populations because behaviors such as predation, predator avoidance, reproduction, and social interaction can affect population dynamics. As a common environmental stressor, ultraviolet-B (UVB) radiation causes various deleterious effects and some aquatic organisms actively avoid UVB radiation in water. However, the extent to which environmental contaminants can impair UVB avoidance has not been evaluated, which may cause greater UVB exposure and toxicity. In the present study, we used Xenopus laevis tadpoles to determine if acute exposure to sublethal concentrations of agricultural chemicals can alter tadpole response to UVB radiation. We exposed tadpoles to four pesticides (malathion, endosulfan, α-cypermethrin, and chlorothalonil) for 96h. At the end of the exposure, tadpoles were transferred to tanks divided into UVB and no-UVB areas. We observed tadpoles for 30min and recorded time spent in the UVB area. We compared the proportion of time tadpoles spent in the UVB area among different concentrations for each pesticide. There was no significant difference between FETAX control and solvent control tadpoles. When combined, control tadpoles spent less than half of the time in the UVB area indicating that X. laevis tadpoles exhibit UVB avoidance behavior. Tadpoles exposed to 5μg/L endosulfan spent significantly more time under UVB than control tadpoles. Other pesticides had no effect on tadpole UVB avoidance behavior. Our results suggest that some neurotoxic pesticides can affect UVB avoidance in larval amphibians, which may increase their exposure and subsequently the risk of UVB-induced damage. The present study highlights the importance of examining the interaction between two stressors that co-occur across broad spatial scales and to consider behavioral alteration when evaluating the risk of pesticides to amphibians. [Copyright &y& Elsevier]

Abstract: Pesticides are typically applied as mixtures and or sequentially to soil and plants during crop production. A common scenario is herbicide application at planting followed by sequential fungicide applications post-emergence. Fungicides depending on their spectrum of activity may alter and impact soil microbial communities. Thus there is a potential to impact soil processes responsible for herbicide degradation. This may change herbicide efficacy and environmental fate characteristics. Our study objective was to determine the effects of 4 peanut fungicides, chlorothalonil (2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile), tebuconazole (α-[2-(4-chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol), flutriafol (α-(2-fluorophenyl)-α-(4-fluorophenyl)-1H-1,2,4-triazole-1-ethanol), and cyproconazole (α-(4-chlorophenyl)-α-(1-cyclopropylethyl)-1H-1,2,4-triazole-1-ethanol) on the dissipation kinetics of the herbicide, metolachlor (2-chloro-N-(6-ethyl-o-tolyl)-N-[(1RS)-2-methoxy-1-methylethyl]acetamide), and on the soil microbial community. This was done through laboratory incubation of field treated soil. Chlorothalonil significantly reduced metolachlor soil dissipation as compared to the non-treated control or soil treated with the other fungicides. Metolachlor DT50 was 99days for chlorothalonil-treated soil and 56, 45, 53, and 46days for control, tebuconazole, flutriafol, and cyproconazole-treated soils, respectively. Significant reductions in predominant metolachlor metabolites, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOA), produced by oxidation of glutathione-metolachlor conjugates were also observed in chlorothalonil-treated soil. This suggested that the fungicide impacted soil glutathione-S-transferase (GST) activity. Fungicide DT50 was 27–80days but impacts on the soil microbial community as indicated by lipid biomarker analysis were minimal. Overall study results indicated that chlorothalonil has the potential to substantially increase soil persistence (2-fold) of metolachlor and alter fate and transport processes. GST mediated metabolism is common pesticide detoxification process in soil; thus there are implications for the fate of many active ingredients. [Copyright &y& Elsevier]

Elevated NO3 − and chlorothalonil (CTN) have been found in production nursery recycling ponds. Bacillus cereus strain NS1 isolated from nursery recycling pond sediment was assessed for its ability to reduce NO3 − and degrade CTN in a mineral medium. The results showed that the efficiency of NO3 − reduction and CTN degradation by B. cereus strain NS1 were related to the nature of organic carbon sources added to the medium. In the medium amended with 100 mg/L yeast extract, 86% of NO3 − (100 mg/L) and 99% of CTN (78 μg/L) were simultaneously removed by B. cereus strain NS1 during the first day of the experiment. It took 6 days for the removal of 82–93% of NO3 − and 87–91% of CTN in the media containing glucose and acetate. B. cereus strain NS1 needed organic carbon as energy sources and electron donors to respire NO3 −, and simultaneously degrade CTN. These results suggest that B. cereus strain NS1 may have great potential to remediate NO3 − and CTN contaminated water in nursery recycling ponds. [Copyright &y& Elsevier]

This study considered the inputs of antifouling paint booster biocides into the aquatic environment directly from painted hulls and high pressure hosing operations, the occurrence of booster biocides in marinas, harbours and docks, and the influence of degradation and water–sediment partition on their environmental fate. Irgarol 1051, the Irgarol 1051 degradation product GS26575, diuron, and the diuron degradation products 1-(3-chlorophenyl)-3,1-dimethylurea (CPDU), 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU) and 1-(3,4-dichlorophenyl)urea (DCPU) were all detected at measurable concentrations in surface waters. Irgarol 1051, GS26575 and diuron were also detected in bottom sediments. A preliminary study of biocide input during both normal use and foreshore hull hosing showed that hosing may be a significant point source input and also be a cause for future concern since much of this input is in the form of paint particles. Field based measurements and laboratory experiments showed that Irgarol 1051 and diuron persist in the water column, due to a low affinity to partition onto sedimentary material and high resistance to degradation. Other biocides such as chlorothalonil, dichlofluanid, and Sea-Nine 211 were all found to be rapidly removed from the water column and be less persistent. [Copyright &y& Elsevier]

Current-use pesticides (CUPs) are widely used in agriculture, and some are listed as persistent organic pollutants (POPs) due to their bioaccumulative and toxic properties. China is one of the largest producers and users of pesticides in the world. However, very limited data are available about the environmental fates of CUPs. Four CUPs (trifluralin, chlorothalonil, chlorpyrifos, and dicofol) in surface seawater and low atmospheric samples taken during research cruises on the Bohai Sea in August and December 2016 and February 2017 were analyzed, we added the spring data sampled in May 2012 to the discussion of seasonal variation. In our study, chlorpyrifos was the most abundant CUPs in the gas phase with a mean abundance of 59.06±126.94pgm -3 , and dicofol had the highest concentration dissolved in seawater (mean: 115.94±123.16pgL -1 ). The concentrations of all target compounds were higher during May and August due to intensive use and relatively high temperatures in the spring and summer. Backward trajectories indicated that air masses passing through the eastern coast of the Bohai Sea contained high concentrations of pollutants, while the air masses from the Bohai and Yellow Seas were less polluted. The high concentration of pollutants in seawater was not only influenced by high yields from the source region of production or usage, but also by input from polluted rivers. Volatilization from surface water was found to be an important source of trifluralin and chlorpyrifos in the air. Air-sea gas exchange of chlorothalonil underwent strong net deposition (mean FRs: 51.67), which was driven by higher concentrations in air and indicates that the Bohai Sea acted as a sink for chlorothalonil., (Copyright © 2017 Elsevier B.V. All rights reserved.)