We analyzed the acute toxicity of the 48% glyphosate (GLY)-based Credit®, the 57.71% dicamba (DIC)-based Kamba®, and the 83.5% 2,4-dichlorophenoxyacetic acid (2,4-D)-based Weedar® Full, alone and as mixtures on the fish Cnesterodon decemmaculatus. Mortality revealed the LC50 96h values of 91.73 mg L−1 (range: 86.80–98.00 mg L−1), 1401.57 mg L−1 (range: 1243.78–1527.35) and 678.04 mg L−1 (range: 639.35–718.04 mg L−1) for GLY, DIC and 2,4-D, respectively. Mean values for the toxic unit (TU) that induced 50% mortality (TU50 96h) of fish exposed to equitoxic mixtures were 1.67 (range: 1.65–1.69) for Credit® and Kamba® and 1.28 (range: 1.20–1.36) for Credit® and Weedar® Full suggesting that both mixtures are antagonic. Non-equitoxic combinations demonstrated an antagonistic interaction of herbicides Credit® and Kamba®, whereas a synergistic effect was observed for Credit® and Weedar® Full formulations. GLY and DIC as a mixture demonstrated lower toxicity on non-target species compared to GLY and 2,4-D in combination, at least for C. decemmaculatus, leading to the conclusion that the former combination could be strongly recommended in further agricultural practices.

Dicamba (DIC) and 2,4-dichlorophenoxyacetic acid (2,4-D) are two of the most applied auxinic herbicides worldwide, both individually and as part of a mixture. However, the toxicity and interactions achieved when applied as a mixture have not yet been characterised. The equitoxic and non-equitoxic acute toxicity exerted by binary mixtures of Banvel® (57.71% DIC) and DMA® (58.4% 2,4-D) on the Neotropical fish Cnesterodon decemmaculatus were evaluated. Results revealed mean values of 1.02 (range, 0.96–1.08) for the toxic unit (TU) that induced 50% mortality (TU50 96 h) to the fish exposed to binary equitoxic mixtures of the commercial formulations Banvel®–DMA®. These results suggest that the mixture is nearly concentration additive. Furthermore, results demonstrated the occurrence of synergistic interaction when non-equitoxic combinations of Banvel®-or DMA®-formulated herbicides were assayed. In this context and regardless of their concentrations, either Banvel®- or DMA®-induced toxicity were synergised by the presence of the counterpart within mixtures. The present study represents the first evidence of the lethality exerted by mixtures of two auxinic herbicides—namely, DIC and 2,4-D—reported to date for fish and other biotic matrices. When C. decemmaculatus is used as the target organism, a synergistic pattern is observed following exposure to a mixture of both herbicides.

Long-term genotoxic effects of two auxinic herbicide formulations, namely, the 58.4% 2,4-dichlorophenoxyacetic acid (2,4-D)-based DMA® and the 57.7% dicamba (DIC)-based Banvel® were evaluated on Cnesterodon decemmaculatus. Primary DNA lesions were analyzed by the single-cell gel electrophoresis methodology. Two sublethal concentrations were tested for each herbicide corresponding to 2.5% and 5% of the LC50₉₆ₕ values. Accordingly, fish were exposed to 25.2 and 50.4 mg/L or 41 and 82 mg/L for 2,4-D and DIC, respectively. Fish were continuously exposed for 28 days with replacement of test solutions every 3 days. Genotoxicity was evaluated in ten individuals from each experimental point at the beginning of the exposure period (0 day) and at 7, 14, 21 and 28 days thereafter. Results demonstrated for first time that 2,4-D-based formulation DMA® induced primary DNA strand breaks after 7–28 days exposure on C. decemmaculatus regardless its concentration. On the other hand, DIC-based formulation Banvel® exerted its genotoxic effect after exposure during 7–14 days and 7 days of 2.5 and 5% LC50₉₆ₕ, respectively. The present study represents the first evidence of primary DNA lesions induced by two widely employed auxinic herbicides on C. decemmaculatus, namely 2,4-D and DIC, following long-term exposure.

Land use changes have led to the degradation of multiple ecosystem services and affected the quality of aquatic ecosystems. The aims of this study were (i) to assess the expansion of the agricultural border over the native forest of an Argentinean stream basin and (ii) to characterize the surface water quality, considering physicochemical parameters, and pesticide concentrations. The agricultural frontier expansion was estimated through the analysis of satellite image coverage. Samples of surface water were taken bimonthly for 2 years. The native forest cover decreased from 72% in 1987 to 60% in 2017 due to the sustained increase in agricultural activities. In surface water, the concentrations of cations decreased: Na > Ca > K > Mg, whereas those of anions decreased: HCO₃ > > Cl > SO₄ > PO₄. The 84 surface water samples analyzed revealed 25 pesticides, including herbicides (44%), insecticides (28%), and fungicides (28%). Herbicides were detected in more than 60% of the samples. 2,4-D, atrazine, cyproconazole, diazinon, glyphosate, AMPA, and metolachlor were detected in all the study sites and sometimes, 2,4-D, atrazine, dicamba, and metolachlor concentrations exceeded the guideline levels. The high sampling frequency of this study and the two annual cycles of crops in the basin enabled sensing of pesticide molecules and concentrations that had not been previously detected, indicating diffuse contamination. These findings signal an emergent challenge on the Espinal agro-ecosystem integrity due to changes in land use.

To elucidate the inhibitory effects of different herbicides on soil nitrification, eight widely used herbicides, i.e., acetochlor, atrazine, dicamba, isoproturon, paraquat, puma, tribenuron-methyl, and 2,4-dichlorophenoxyacetic acid butyl ester (2,4-Dbe), which represent different chemical taxonomy were selected. Our results indicated that herbicide 2,4-Dbe displayed the best inhibitory effect on nitrification, followed by puma and tribenuron-methyl, whereas the remaining five herbicides exhibited less effect when 10 mg of active ingredient (A.I.) of every herbicide per kg of soil was applied in vegetable-planting soil. The inhibition appeared when 5–100 mg of A.I. 2,4-Dbe was employed, which was enhanced with an increment in its dose in both vegetable-planting and fluvo-aquic soils. However, the inhibitory effect of 10 mg of A. I. 2,4-Dbe exhibited obvious differences in these two types of soils, where the duration of inhibition was shorter as it only continued about a week in fluvo-aquic and calcic cambisols soils with strong nitrification activity but poorer effect as compared to 10 mg of dicyandiamide (DCD). In contrast, the duration of inhibition exceeded 2 months in dryland red and shajiang black soils with a weak nitrification activity which was equivalent to DCD. In addition, comparing with five nitrification inhibitors, 10 mg of 2,4-Dbe had better inhibition than the substituted pyrimidine (AM) and sulfocarbamide (SU), but was equivalent to DCD, nitrapirin, and 3,4-dimethylpyrazole phosphate (DMPP) at their recommended application rates in dryland red soil. These obtained data clearly indicated that 2,4-Dbe could play a stronger role as a nitrification inhibitor in soils.

Winnipeg is a city in the Canadian Prairies with a population of about 600,000. Like many other cities and towns in this region of Canada, the city is surrounded by agriculture. Weekly bulk deposition samples were collected from May to September in 2010 and 2011 and analyzed for 43 pesticides used in Prairie agriculture. Fourteen herbicides, five herbicide metabolites, two insecticides, and two fungicides were detected with 98.5 % of the samples containing chemical mixtures. Glyphosate is the most widely used pesticide in Prairie agriculture and accounted for 65 % of the total pesticide deposition over the 2 years. Seasonal glyphosate deposition was more than five times larger in 2011 (182 mm rain) than 2010 (487 mm rain), suggesting increased glyphosate particulate transport in the atmosphere during the drier year. The seasonal deposition of ten other frequently herbicides was significantly positively correlated with the amount of herbicides applied both in and around Winnipeg (r = 0.90, P < 0.001) and with agricultural herbicide use around Winnipeg (r = 0.63, P = 0.05), but not with agricultural herbicide use province wide (P = 0.23). Herbicides 2,4-D (2,4-dichlorophenoxyacetic acid), dicamba, and mecoprop had known urban applications and were more consistently detected in samples relative to bromoxynil and 2-methyl-4-chlorophenoxyacetic acid (MCPA) whose frequency of detections decreased throughout August and September. The Canadian Water Quality Guidelines for irrigation water were frequently exceeded for both dicamba (75 %) and MCPA (49 %) concentrations in rain. None of glyphosate concentrations in rain exceeded any of the Canadian Water Quality Guidelines established for this herbicide.

Biofilters have been shown to be efficient for removing pollutants from different water effluents, but little information is available about their capacity to remove highly polar pesticides from agricultural run-off waters. In this study, we assess the capacity of three different biofilter-supporting materials (sand, peat soil, and pine bark) to remove five phenoxyacid herbicides (mecoprop, dicamba, MCPA, dichlorprop and 2,4-D) and five non-ionic pesticides (atrazine, simazine, fenitrotion, diazinon, and alachlor) from real agricultural run-off waters. The experimental design included three columns 120 cm in length and 15 cm in diameter, each filled with 100 cm of one of the selected supporting materials. After 30 days of acclimation, the columns were fed with agricultural run-off water spiked at 10 μg L⁻¹ with each of the studied pesticides for 20 days at a hydraulic loading rate (HLR) of 0.32 m day⁻¹. The results show that the sand filter was the best supporting material for removing phenoxyacid herbicides (77% on average), whereas peat soil and pine bark were best for removing non-ionic pesticides (72% on average). The attenuation of mecoprop and dichlorprop correlated negatively with the enantiomeric fraction. Therefore, this study shows that the use of waste-to-product materials in biofilter systems is a good solution for removing pollutants from agricultural run-off waters.

Pesticides might increase the production of reactive oxygen species (ROS). Dicamba (DIC) and 2,4-dichlorophenoxyacetic acid (2,4-D) are auxinic herbicides commonly applied in agroecosystems to control unwanted weeds. We analysed the oxidative damage exerted on the fish Cnesterodon decemmaculatus by an acute exposure to DIC- and 2,4-D-based herbicides formulations Banvel® and DMA®, respectively. The Endo III- and Fpg-modified alkaline comet assay was employed for detecting DNA damage caused by oxidative stress, whereas enzymatic and non-enzymatic biomarkers such as the activities of catalase (CAT), glutathione-S-transferase (GST), acetylcholinesterase (AChE), and glutathione content (GSH) were used to assess antioxidant response to these two herbicides. At the DNA level, results demonstrate that both auxinic herbicides induce oxidative damage at purines level. An increase on CAT and GST activities were detected in 48 h- and 96 h-treated specimens with both auxinics. GSH content decreased in fish exposed to DIC during 48 h and to 2,4-D after 96 h of exposure. Additionally, a diminished AChE activity in specimens treated with DIC and 2,4-D was observed only after 96 h. Total protein content decreased in fish exposed to both auxinics during 96 h. These results represent the first evaluation of oxidative damage related to DIC and 2,4-D exposure on a fish species as the Neotropical freshwater teleost C. decemmaculatus.

This study investigates the impact of humic acid (HA) on the toxicity of selected herbicides and their binary mixtures to aquatic plants. The focus was on two auxin simulators (2,4-D and dicamba) and two photosynthetic inhibitors (atrazine and isoproturon). The results suggested that the addition of HA to the standard synthetic medium does not affect Lemna minor growth nor the toxicity of atrazine, but increases the toxicity of 2,4-D and the binary mixture of atrazine and 2,4-D. The addition of HA to the standard synthetic medium reversibly decreased the growth (biomass) of Myriophyllum aquaticum and enhanced the toxicity of individually tested herbicides (isoproturon and dicamba) as well as their binary mixture. The results showed delayed toxic effects of auxin simulators, especially 2,4-D in the Lemna test. The recovery after the exposure to individual photosystem II inhibitors (atrazine and isoproturon) is fast in both plant species, regardless of the presence of HA. In the case of selected mixtures (atrazine + 2,4-D and isoproturon + dicamba), recovery of both plant species was noted, while the efficiency depended on the herbicide concentration in the mixture rather than the presence or absence of HA.

Acidic herbicides are used to control broad-leaved weeds. They are stable, water-soluble, and with low binding to soil are found frequently in surface waters, often at concentrations above the EU Drinking Water Directive limit of 0.10 μg L⁻¹. This presents a problem when such waters are abstracted for potable supplies. Understanding their sources, transport and fate in river catchments is important. We developed a new Chemcatcher® passive sampler, comprising a 3M Empore™ anion-exchange disk overlaid with a polyethersulphone membrane, for monitoring acidic herbicides (2,4-D, dicamba, dichlorprop, fluroxypyr, MCPA, MCPB, mecoprop, tricolpyr). Sampler uptake rates (Rₛ = 0.044–0.113 L day⁻¹) were measured in the laboratory. Two field trials using the Chemcatcher® were undertaken in the River Exe catchment, UK. Time-weighted average (TWA) concentrations of the herbicides obtained using the Chemcatcher® were compared with concentrations measured in spot samples of water. The two techniques gave complimentary monitoring data, with the samplers being able to measure stochastic inputs of MCPA and mecoprop occurring in field trial 1. Chemcatcher® detected a large input of MCPA not found by spot sampling during field trial 2. Devices also detected other pesticides and pharmaceuticals with acidic properties. Information obtained using the Chemcatcher® can be used to develop improved risk assessments and catchment management plans and to assess the effectiveness of any mitigation and remediation strategies.