Although enantioselective sorption to soil particles has been proposed as a mechanism that can potentially influence the availability of individual chiral pesticide enantiomers in the environment, environmental fate studies generally overlook this possibility and assume that only biotic processes can be enantioselective, whereas abiotic processes, such as sorption, are non-enantioselective. In this work, we present direct evidence for the effect of the enantioselective sorption of a chiral pesticide in a natural soil on the availability of the single pesticide enantiomers for transport. Batch sorption experiments, with direct determination of the sorbed amounts, combined with column leaching tests confirmed previous observations that from non-racemic aqueous solutions the sorption of the chiral fungicide metalaxyl on the soil appeared to be enantioselective, and further demonstrated that the enantiomer that was sorbed to a greater extent (R-metalaxyl, Kd = 1.73 L/kg) exhibited retarded leaching compared to its optical isomer (S-metalaxyl, Kd = 1.15 L/kg). Interconversion and degradation of the pesticide enantiomers, which are potential experimental artifacts that can lead to erroneous estimates of sorption and its enantioselectivity, were discarded as possible causes of the observed enantioselective behavior. The results presented here may have very important implications for a correct assessment of the environmental fate of chiral pesticides that are incorporated into the environment as non-racemic mixtures, and also of aged chiral pesticide residues that have been transformed from racemic to non-racemic by biologically-mediated processes.

Sustainable agriculture practices and integrated pest management for avoiding environmental pollution are necessary to maintain a high yield in vineyard areas. Pesticide residues in groundwater in a vineyard area of La Rioja (Spain) have been evaluated in previous years, and they could now have varied after farmers have adopted the different measures recommended. Accordingly, this research's objectives were (i) to evaluate the occurrence and seasonal distribution (spring, summer, and autumn samplings) of pesticides (36) plus their degradation products (DP) (11) in water and soil samples (23 + 15) in La Rioja (Northern Spain), and (ii) to compare the current water quality (2019) with that determined previously (2011). A multi-residue method based on solid phase extraction (for water samples) or solid liquid extraction (for soil samples) and high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS) was used to determine and quantify pesticides. The results reveal the presence in waters of 30 compounds from those selected (15 fungicides + 2 DP, 7 insecticides + 1 DP, and 3 herbicides +2 DP), with 14 of them at concentrations > 0.1 μg L⁻¹ (water quality threshold for human consumption). The highest number of compounds was detected in summer (waters) and spring (soils). The pesticides most frequently detected in water samples were the fungicides metalaxyl, tebuconazole, and boscalid, with the last one being the compound found in the highest number of soil samples. The comparison of water pollution in 2011 and 2019 indicates a significant decrease in the total concentration of herbicides, fungicides and insecticides in 95–100%, 76–90%, and 42–85% of samples in the three campaigns, respectively. The results indicate that an optimized and sustainable use of pesticides in intensive and high-yield agricultural areas could reduce environmental pollution.

The application of nanotechnology in agriculture, pesticide delivery and other related fields increases the occurrence of engineered nanoparticles (ENPs) in soil. Since ENPs have larger surface areas and normally a high adsorption capacity for organic pollutants, they are thought to influence the transport of pesticides in soils and thereafter influence the uptake and transformation of pesticides. The adsorption pattern of racemic-metalaxyl on agricultural soils including kinetics and isotherms changed in the presence of nano-SiO2. The adsorption of racemic-metalaxyl on agricultural soil was not enantioselective, in either the presence or the absence of SiO2. The adsorption of racemic-metalaxyl on SiO2 decreased to some extent in soil-SiO2 mixture, and the absolute decrease was dependent on soil properties. The decreased adsorption of metalaxyl on SiO2 in soil-SiO2 mixture arose from the competitive adsorption of soil-dissolved organic matter and the different dispersion and aggregation behaviors of SiO2 in the presence of soil. Interactions between SiO2 and soil particles also contributed to the decreased adsorption of metalaxyl on SiO2, and the interactions were analyzed by extended Derjaguin–Landau–Verwey–Overbeek theory. The results showed that the presence of nano-particles in soils could decrease the mobility of pesticides in soils and that this effect varied with different soil compositions.

Compound-Specific Isotope Analysis (CSIA) is employed to investigate the biodegradation of metalaxyl in soil and plant. By studying the degradation of metalaxyl in unsterilized and sterilized soil with two initial concentrations of metalaxyl, microbial degradation has the most significant effect on the degradation of metalaxyl in soil. In addition, biodegradation and isotope fractionation of metalaxyl in water spinach with root application and leaf application are investigation by CSIA. It is shown that both absorption and degradation of metalaxyl in the roots and leaves of water spinach can cause the shift of δ¹³C values. Specifically, the δ¹³C values decreased during absorption while increased in degradation of metalaxyl in the roots and leaves of water spinach, indicating that the lighter isotope is absorbed in the absorption process at first and then degraded. Furthermore, the relationship between carbon isotope ratios and residual concentration of metalaxyl can be described by the Rayleigh equation, and the biodegradation rate of metalaxyl could be calculated by using CSIA without measuring the concentration of metalaxyl both in soil and plant. Therefore, the use of CSIA can quantitatively assess the degradation behavior of pesticide pollution in the environment and provide a certain scientific evidence and technical support in the process of environmental remediation.

One of the consequences of phytosanitary treatments applied to crops is the generation of a great volume of agro-wastewater having pesticide residues. These pollutants can be considered a serious threat to the environment and human health due to their capacity to affect distant areas remaining for a long time after their application. We have assessed the degradation of five pesticides in agro-waste water produced in two farms by the cleaning pesticide containers and phytosanitary treatment equipment used in the farms. For this purpose, a pilot facility was installed in both farms and advanced oxidation treatments were conducted using natural sunlight by means of Na₂S₂O₈ and heterogeneous photocatalysis (TiO₂/Na₂S₂O₈). The remaining percentages obtained at the end of the experiments ranged from 5 to 90.1% for chlorantraniliprole, 5 to 82.3% for difenoconazole, 0.02 to 19.1% for metalaxyl, 1.4 to 74.4% for myclobutanil, and 0.3 to 61% for triadimenol. We observed a correlation between the higher remaining percentages and the total initial concentration of pollutant because of other commercial formulations applied in the farms. The results showed that this equipment could be used to eliminate or reduce the presence of pesticide residues in agro-waste water using an innovative facility installed in the farms and a renewable and economical source of energy (sunlight).

The biomixture composition and the presence of a grass layer in a biobed bioremediation system can improve the performance of these systems to minimize pesticide point-source contamination. In this study, a novel biomixture composed with organic wastes from vineyards and wine industries (vermicompost of winery wastes and vine shoots) and top soil (W) was elaborated. The impact of three pesticides, commonly used in vineyards, on its microbial activity and on the development of turfgrass was determined in a short-term experiment. Moreover, the dissipation of the assayed pesticides was evaluated to stablish their distribution patterns between the turfgrass and the biomixture. For comparison, the original biomixture composed with top soil, peat, and straw (P) was also studied. After 15 days of pesticide application, the development of the turfgrass in both biomixtures was similar. However, the oxidoreductases (dehydrogenase and ortho-diphenol oxidase) and the hydrolytic (FDA and β-glucosidase) enzyme activities were greater in W-biomixture than in P-biomixture. The dissipation of metalaxyl and imidacloprid recorded in the W-biomixtures was significantly greater than in the P-biomixtures. The pesticide dissipation in W-biomixtures followed the same order of their octanol water partition coefficients. Except for tebuconazole, the lower biological activity in the P-biomixture would explain the limited pesticide dissipation. In the grassed biomixtures, most (> 83%) of the non-dissipated imidacloprid and tebuconazole remained in the biomixtures, while metalaxyl was rapidly translocated to the aerial part of the turfgrass. Our results show the potential capability of the novel biomixture as an alternative to the original one in a biobed.

Fungicides are used to prevent foliar diseases on a wide range of vegetable, field, fruit, and ornamental crops. They are generally more effective as protective rather than curative treatments, and hence tend to be applied before infections take place. Less than 1% of US soybeans were treated with a fungicide in 2002 but by 2006, 4% were treated. Like other pesticides, fungicides can move-off of fields after application and subsequently contaminate surface water, groundwater, and associated sediments. Due to the constant pressure from fungal diseases such as the recent Asian soybean rust outbreak, and the always-present desire to increase crop yields, there is the potential for a significant increase in the amount of fungicides used on US farms. Increased fungicide use could lead to increased environmental concentrations of these compounds. This study documents the occurrence of fungicides in select US streams soon after the first documentation of soybean rust in the US and prior to the corresponding increase in fungicide use to treat this problem. Water samples were collected from 29 streams in 13 states in 2005 and/or 2006, and analyzed for 12 target fungicides. Nine of the 12 fungicides were detected in at least one stream sample and at least one fungicide was detected in 20 of 29 streams. At least one fungicide was detected in 56% of the 103 samples, as many as five fungicides were detected in an individual sample, and mixtures of fungicides were common. Azoxystrobin was detected most frequently (45% of 103 samples) followed by metalaxyl (27%), propiconazole (17%), myclobutanil (9%), and tebuconazole (6%). Fungicide detections ranged from 0.002 to 1.15 μg/L. There was indication of a seasonal pattern to fungicide occurrence, with detections more common and concentrations higher in late summer and early fall than in spring. At a few sites, fungicides were detected in all samples collected suggesting the potential for season-long occurrence in some streams. Fungicide occurrence appears to be related to fungicide use in the associated drainage basins; however, current use information is generally lacking and more detailed occurrence data are needed to accurately quantify such a relation. Maximum concentrations of fungicides were typically one or more orders of magnitude less than current toxicity estimates for freshwater aquatic organisms or humans; however, gaps in current toxicological understandings of the effects of fungicides in the environment limit these interpretations.

Biopurification systems (BPS) are employed for the treatment of pesticide-containing wastewaters. In this work, a biomixture (active core of BPS) complemented by the addition of the fungus Trametes versicolor was evaluated for the elimination of a mixture of pesticides under different treatment conditions. The biomixture achieved high removal of all the pesticides assayed after 16 d: atrazine (68.4%, t₁/₂: 9.6 d), carbendazim (96.7%, t₁/₂: 3.6 d), carbofuran (98.7%, t₁/₂: 3.1 d) and metalaxyl (96.7%, t₁/₂: 3.8 d). Variations in the treatment conditions including addition of the antibiotic oxytetracycline and co-bioaugmentation with a bacterial consortium did not significantly affect the removal performance of the biomixture. Bacterial and fungal community profiles determined by DGGE analyses revealed changes that responded to biomixture aging, and not to antibiotic or pesticide addition. The proposed biomixture exhibits very efficient elimination during simultaneous pesticide application; moreover, the matrix is highly stable during stressful conditions such as the co-application of antibiotics of agricultural use.

Metalaxyl, an important phenylamide fungicide, is widely used for controlling fungal diseases caused by pathogens of the orders Peronosporales and Pythiales. Under laboratory conditions, metalaxyl was applied to soil samples at the recommended field rate (1×FR) and double of recommended field rate (2×FR) for two and three times. Soil subsamples were taken at 0, 1, 3, 7, 14, 28, and 45 days after the last application of metalaxyl for determination of metalaxyl residues and 7, 14, 28, and 56 days for enumeration of cultivable microorganisms and DGGE profile of soil microbial community. Soil incubation experiments revealed that metalaxyl was degraded faster in the third application than in the second application of the fungicide, half-lives of metalaxyl decreasing from 16.2 to 9.9 days for recommended field rate and 22.1 to 20.0 days for double of recommended field rate. Soil bacterial and fungal populations decreased in the first 14 days and then recovered to the control levels; population of actinomycetes did not alter in the first 28 days but increased at the end of the experiment after the second application. However, after the third treatment, temporary increase in soil bacteria population, nonsignificant inhibition effect on fungal population, and obvious stimulation effect on actinomycetes number were observed. DGGE results showed that successive inputs of metalaxyl altered the bacterial community structure. There were differences in the persistence and effects of metalaxyl on microbial community between the second and the third metalaxyl treatments.

The effects of a five-pesticide mixture on pesticide accumulation, phytohormone levels (indole-3-acetic acid, gibberellic acid, jasmonic acid, and salicylic acid), pigment contents (total chlorophyll and carotenoid), antioxidant enzyme (catalase and guaiacol peroxidase) activities, lipid peroxidation product (malondialdehyde), and DNA profiles were investigated in the leaves of Veronica beccabunga. Laboratory-acclimatized plants were treated with a mix of five pesticides (atrazine, disulfoton, chlorpyrifos, metalaxyl, and ethion) in doses of 50 ppt, 1 ppb, 100 ppb, and 1 ppm for 1, 3, and 6 days. The accumulation of each pesticide, from highest to lowest, was as follows: chlorpyrifos, atrazine, metalaxyl, disulfoton, and ethion. The amounts of total chlorophyll and protein decreased with increased pesticide concentration. Antioxidant enzyme activities and malondialdehyde amount increased linearly with increasing pesticide exposure. However, the highest pesticide concentration caused decreases in guaiacol peroxidase (POD) activity and malondialdehyde (MDA) content at all treatment times. Both jasmonic and salicylic acid levels increased with pesticide exposure and decreased gradually after. It was also determined that application of the pesticide mixture affected the DNA profiles of V. beccabunga. The most band changes were detected on the sixth day of treatment.