Dissipation of pesticides and responses of bacterial, fungal and protistan communities in a multi-contaminated vineyard soil.

The effect of pesticide residues on non-target microorganisms in multi-contaminated soils remains poorly understood. In this study, we examined the dissipation of commonly used pesticides in a multi-contaminated vineyard soil and its effect on bacterial, fungal, and protistan communities. We conducted laboratory soil microcosm experiments under varying temperature (20°C and 30°C) and water content (20 % and 40 %) conditions. Pesticide dissipation half-lives ranged from 27 to over 300 days, depending on the physicochemical properties of the pesticides and the soil conditions. In both autoclaved and non-autoclaved soil experiments, over 50 % of hydrophobic pesticides (dimethomorph > isoxaben > simazine = atrazine = carbendazim) dissipated within 200 days at 20°C and 30°C. However, the contribution of biodegradation to the overall dissipation of soluble pesticides (rac-metalaxyl > isoproturon = pyrimethanil > S-metolachlor) increased to over 75 % at 30°C and 40 % water content. This suggests that soluble pesticides became more bioavailable, with degradation activity increasing with higher temperature and soil water content. In contrast, the primary process contributing to the dissipation of hydrophobic pesticides was sequestration to soil. High-throughput amplicon sequencing analysis indicated that water content, temperature, and pesticides had domain-specific effects on the diversity and taxonomic composition of bacterial, fungal, and protistan communities. Soil physicochemical properties had a more significant effect than pesticides on the various microbial domains in the vineyard soil. However, pesticide exposure emerged as a secondary factor explaining the variations in microbial communities, with a more substantial effect on protists compared to bacterial and fungal communities. Overall, our results highlight the variability in the dissipation kinetics and processes of pesticides in a multi-contaminated vineyard soil, as well as their effects on bacterial, fungal, and protistan communities.

In vivo tracing of cyromazine and three neonicotinoids in cowpea under field conditions by solid-phase microextraction combined with ultra-performance liquid chromatography-tandem mass spectrometry.

BACKGROUND: Excessive pesticide residues in agricultural products could accumulate in organisms through the food chain, causing potential harm to human health. The investigation of dissipation kinetics and residues of pesticides in crops is crucial for the scientific application of pesticides and the mitigation of their adverse effects on human health. In vivo solid-phase microextraction (in vivo SPME) has unique advantages, but the research on field plants is still lacking and the quantitative correction methods need to be further developed. RESULTS: A method combining in vivo solid-phase microextraction with ultra-performance liquid chromatography-tandem mass spectrometry (in vivo SPME-UPLC-MS/MS) was developed to monitor the presence of acetamiprid, cyromazine, thiamethoxam and imidacloprid in cowpea fruits grown in the field. The sampling rates (Rs) were determined using both in vitro SPME in homogenized cowpea samples and in vivo SPME in intact cowpea fruit samples. The in vivo-Rs values were significantly higher than the in vitro-Rs for the same analyte, which were used for in vivo SPME correction. The accuracy of this method was confirmed by comparison with a QuEChERS-based approach and subsequently applied to trace pesticide residues in field-grown cowpea fruits. The residual concentrations of each pesticide positively correlated with application doses. After 7 days of application at two different doses, all of the pesticides had residual concentrations below China's maximum residue limits. Both experimental data and predictions indicated that a safe preharvest interval for these pesticides is 7 days; however, if the European Union standards are to be met, a safe preharvest interval for cyromazine should be at least 13 days. SIGNIFICANCE: This study highlights the advantages of in vivo SPME for simultaneous analysis and tracking of multiple pesticides in crops under field conditions. This technique is environmentally friendly, minimally invasive, highly sensitive, accurate, rapid, user-friendly, cost-effective, and capable of providing precise and timely data for long-term pesticide surveillance. Consequently, it furnishes valuable insights to guide the safe utilization of pesticides in agricultural production.

Phages in vermicomposts enrich functional gene content and facilitate pesticide degradation in soil.

Organic fertilizer microbiomes play substantial roles in soil ecological functions, including improving soil structure, crop yield, and pollutant dissipation. However, limited information is available about the ecological functions of phages and phage-encoded auxiliary metabolic genes (AMGs) in orga9nic fertilizers. Here we used a combination of metagenomics and phage transplantation trials to investigate the phage profiles and their potential roles in pesticide degradation in four organic fertilizers from different sources. Phage annotation results indicate that the two vermicomposts made from swine (PV) and cattle (CV) dung had more similar phage community structures than the swine (P) and cattle (C) manures. After vermicomposting, the organic fertilizers (PV and CV) exhibited enriched phage-host pairings and phage AMG diversity in relative to the two organic fertilizers (P and C) without composting. In addition, the number of broad-host-range phages in the vermicomposts (182) was higher than that in swine (153) and cattle (103) manures. Notably, phage AMGs associated with metabolism and pesticide biodegradation were detected across the four organic fertilizers. The phage transplantation demonstrated that vermicompost phages were most effective at facilitating the degradation of pesticide precursor p-nitrochlorobenzene (p-NCB) in soil, as compared to swine and cattle manures (P < 0.05). Taken together, our findings highlight the significance of phages in vermicompost for biogeochemical cycling and biodegradation of pesticide-associated chemicals in contaminated soils.

Dissipation of pesticides by stream biofilms is influenced by hydrological histories.

To evaluate the effects of hydrological variability on pesticide dissipation capacity by stream biofilms, we conducted a microcosm study. We exposed biofilms to short and frequent droughts (daily frequency), long and less frequent droughts (weekly frequency) and permanently immersed controls, prior to test their capacities to dissipate a cocktail of pesticides composed of tebuconazole, terbuthylazine, imidacloprid, glyphosate and its metabolite aminomethylphosphonic acid. A range of structural and functional descriptors of biofilms (algal and bacterial biomass, extracellular polymeric matrix (EPS) concentration, microbial respiration, phosphorus uptake and community-level physiological profiles) were measured to assess drought effects. In addition, various parameters were measured to characterise the dynamics of pesticide dissipation by biofilms in the different hydrological treatments (% dissipation, peak asymmetry, bioconcentration factor, among others). Results showed higher pesticide dissipation rates in biofilms exposed to short and frequent droughts, despite of their lower biomass and EPS concentration, compared to biofilms in immersed controls or exposed to long and less frequent droughts. High accumulation of hydrophobic pesticides (tebuconazole and terbuthylazine) was measured in biofilms despite the short exposure time (few minutes) in our open-flow microcosm approach. This research demonstrated the stream biofilms capacity to adsorb hydrophobic pesticides even in stressed drought environments.

Changes in concentration of pesticide residues in fruits and vegetables during household processing.

Monitoring of pesticide residues in fruits and vegetables and their processed products like jams, pickles, juices, ketchup, dried products and canned products was undertaken. The study was conducted to assess the effect of washing, peeling, heating and cooking on concentration of various pesticides. The stability of various pesticides in samples and their products was assessed. Pesticide residues were extracted using QuEChERS method and analysed by GC-MS. It was observed that pesticides like mancozeb and carbofuron were found to be stable for tomato and potato while chloropyriphos, captan and mancozeb (in other samples) were found to be unstable. It was also observed that peels and pomace showed highest levels of pesticide residues. In this study, washing, peeling and heat processing (boiling and blanching) have been found to be the most effective ways of pesticide residue dissipation.

Untargeted metabolomics as a tool to monitor biocontrol product residues' fate on field-treated Prunus persica.

Evidence of chemical plant protection products' (PPPs) long-term impact has been found in all environmental compartments. Therefore, other types of PPPs are developed to complement chemical PPPs like PPPs from natural sources, namely biocontrol products (BPs). Little is known about those new BPs, and it is important to assess their potential long-term environmental impact. Recently, the Environmental Metabolic Footprinting (EMF) approach was developed. It permits studying sample's entire meta-metabolome (endometabolome and xenometabolome) through a kinetics tracking of metabolomes of treated and untreated samples. Those metabolomes are compared time-by-time to estimate the "resilience time" of the samples after treatment. The current study aims to investigate BP residues' dissipation on peach fruits (Prunus persica). For that, an untargeted Liquid Chromatography-Mass Spectrometry metabolomics approach based on the EMF was optimised to separate the xenometabolome of the PPP from the endometabolome of the fruits. This "new version" of the EMF approach is able to target the BP treatment residues' (xenometabolome) dissipation exclusively. Thus, it is able to determine the time needed to have no more residues in the studied matrix: the "dissipation interval". Field experiment was conducted on peach tree orchard against brown rot treated with (i) a plant extract BP (Akivi); (ii) a reference mineral extract BP (Armicarb®); and (iii) a Chemical reference treatment campaign. Formulated Akivi and its by-products' dissipation was monitored, a degradation kinetics appeared but the sampling did not last long enough to allow the determination of the "dissipation interval". Armicarb® and the Chemical reference's residues and by-products showed a persistence pattern along the sampling kinetics. These results indicate that the EMF approach, formerly developed on soil and sediment, is applicable for fruit matrices and can be used to investigate the fate of complex BP treatment on the matrix through the xenometabolome tracking on treated fruits.

Determination of the residue behavior of isocycloseram in Brassica oleracea and soil using the QuEChERS method coupled with HPLC.

Isocycloseram is a new isoxazoline insecticide that can efficiently control the diamondback moth in cruciferous crops. The aim of this study was to establish a method for the determination of isocycloseram residues in/on cabbage and in the soil using HPLC-UV at 264 nm. A field test was conducted in December 2019 and 2020 to monitor isocycloseram dissipation in Jiangxi, China. Acetonitrile was used to extract isocycloseram from cabbage and soil. C18 and GCB were used to purify cabbage extracts, whereas soil extracts did not require purification. At the addition level of 0.01-1.0 mg/kg, the average recoveries in cabbage and soil were 91.81-109.95% and 89.89-104.08% respectively. After having applied 10% isocycloseram DC, isocycloseram dissipated faster in the cabbage matrix. Isocycloseram residues on cabbage leaves could be removed through simple cleaning methods, especially by soaking in 2% citric acid.

Pesticide treatment in biobed systems at microcosms level under critical moisture and temperature range using an Orthic Solonchaks soil from southeastern Mexico amended with corn husk as support.

Agriculture effluents from cleaning and handling equipment used in pesticide applications can contaminate superficial and groundwater sources when not correctly disposed of. Biobeds using soil enriched with amendments represent a viable technology to control and minimize pesticide pollution of soil and water in farmlands. They are usually installed outdoors without protection, making them vulnerable to rain flooding, lack of moisture, drought, and intense heat or cold. Temperature (T) and moisture (M) of the biomixture are considered two of the most important physical factor affecting pesticide dissipation. This study aimed to evaluate the effect of T and M on the dissipation of five of the most used pesticides (carbofuran, atrazine, 2,4-D, diazinon, and glyphosate) in Yucatan State, Mexico. Three experiments using miniaturized biobeds considering optimal temperature and moisture (T of 30 ± 2 °C and 90% water holding capacity [WHC]) were performed. The optimal dissipation time and the effect of T, M variations, and volatilization was determined. The optimal dissipation time was over 14 days. Carbofuran was the least dissipated pesticide and glyphosate the most. The primary factor affecting pesticide dissipation was T (P < 0.05), reaching rates of dissipation of 99% at 45 °C. Variations of M in the biomixture were not significant on pesticide dissipation (P > 0.05). The white-rot fungi were observed; its presence was related to increments of T. Head Space analysis (at 45 °C) showed low pesticide volatilization (≤0.03%) for all pesticide used were quantified; water vapor condensation could reduce the pesticide volatilization for experimental conditions.

Improved dissipation kinetic model to estimate permissible pre-harvest residue levels of pesticides in apples.

Prediction of residual concentrations of applied pesticides during the pre-harvest period may be required to ensure the safety of agricultural products. In this study, time-dependent dissipation trends of carbaryl (CB), kresoxim-methyl (KM), flubendiamide (FB), flufenoxuron (FN), bitertanol (BT), and chlorantraniliprole (CN) applied to apples at recommended and threefold greater doses were modeled to estimate pre-harvest residue limit concentrations (CPHRL) indicating permissible pesticide concentrations during the pre-harvest period. Double-exponential (DE) model results best fit the dissipation trends of all tested pesticides (correlation coefficients of 0.91-0.99) compared to zero-, first-, and second-order models. Among the pesticides examined, CB half-lives in apples of 2.9 and 6.6 days were the shortest, while those of FN (21.1-32.7 days) were the longest. The CPHRL values for each pesticide in apples were estimated with DE model parameter values and could be used to determine harvest dates for safe apples with pesticide concentrations below their maximum residue limits. Application of the DE model for CPHRL calculation provides more accurate information for farmers to produce agricultural products safe from pesticide residues.

Identification of microbial species present in a pesticide dissipation process in biobed systems using typical substrates from southeastern Mexico as a biomixture at a laboratory scale.

Biobed systems are an important option to control point pollution in agricultural areas. Substrates used and microbial diversity present in a biomixture perform an essential function in pesticide dissipation. In this study, the effects of soil (50% of volume/volume [V/V] proportion for all biomixtures) and four soil-based biomixtures (miniaturized biobeds; addition of novel substrates from southeastern Mexico) on dissipation of high concentrations of 2,4-dichlorophenoxyacetic acid (2,4-D), atrazine, carbofuran, diazinon, and glyphosate and on microbial diversity in biomixtures were evaluated. Small residual amounts of all pesticides at 20 (<2%) and 41 (<1%) days were observed; however, the lowest efficiency rates were observed in soil. Glyphosate was the only pesticide that completely dissipated in soil and biomixtures. Archaea, bacteria, and fungi were identified in biobeds, with bacteria being the most diverse microorganisms according to the identified species. The presence of white-rot fungi (normally related to pesticide degradation in biomixtures) was observed. Effects of the pesticide type and of biomixtures on pesticide dissipation were significant (P<0.05); however, only the effect of biomixtures on microbial diversity was significant (P<0.05); microbial diversity and richness had a significant effect on the residual amount of pesticides (P<0.05). Microbial diversity in terms of phyla was directly related to physicochemical parameters such as organic matter, lignin, water-holding capacity, and pH of soil and biomixtures.

Novel insights in biopurification system for dissipation of a pesticide mixture in repeated applications.

A biopurification system based on the adsorption and degradation capacity of a biomixture to degrade a mixture of pesticides (atrazine, chlorpyrifos, iprodione; 50 mg kg-1 each) in repeated applications (0, 30, and 60 days) was evaluated. Tanks of 1 m3 packed with a biomixture (ρ 0.29 g mL-1) with and without vegetal cover were used. The biomixture contained soil, peat, and wheat straw in a proportion 1:1:2 by volume, respectively. Pesticide concentrations, biological activities (urease, phenoloxidase, and dehydrogenase), and microbial community changes (DGGE and qPCR) were evaluated periodically. Pesticide dissipation was higher in tanks with vegetal cover (> 95%) and no variation was observed after the three applications; contrarily, pesticide dissipation decreased in the tank without vegetal cover after each application. The presence of vegetal cover decreased the half-life of pesticides by at least twice. Biological activities were in general not affected by the application and reapplication of pesticides in the same treatment; however, they exhibited some differences between tanks containing and lacking the vegetal cover. High similarity between microbial groups (actinobacteria, bacteria, and fungi) was observed, suggesting no influence ascribable to the successive pesticide applications. The number of copies of bacteria and actinobacteria remained almost constant during the assay. However, the number of copies of fungi was significantly higher in the uncontaminated tank without vegetal cover.

Atrazine, chlorpyrifos, and iprodione effect on the biodiversity of bacteria, actinomycetes, and fungi in a pilot biopurification system with a green cover.

The use of biopurification systems can mitigate the effects of pesticide contamination on farms. The primary aim of this study was to evaluate the effect of pesticide dissipation on microbial communities in a pilot biopurification system. The pesticide dissipation of atrazine, chlorpyrifos and iprodione (35 mg kg-1 active ingredient [a.i.]) and biological activity were determined for 40 days. The microbial communities (bacteria, actinomycetes and fungi) were analyzed using denaturing gradient gel electrophoresis (DGGE). In general, pesticide dissipation was the highest by day 5 and reached 95%. The pesticides did not affect biological activity during the experiment. The structure of the actinomycete and bacterial communities in the rhizosphere was more stable during the evaluation than that in the communities in the control without pesticides. The rhizosphere fungal communities, detected using DGGE, showed small and transitory shifts with time. To conclude, rhizosphere microbial communities were not affected during pesticide dissipation in a pilot biopurification system.

Agricultural effluent treatment in biobed systems using novel substrates from southeastern Mexico: the relationship with physicochemical parameters of biomixtures.

Misuse of pesticides in farming activities leads to contamination of drinking water sources and is responsible for animal and human health problems. The biobeds are practicable option to minimize contamination by pesticides during preparation, use and washing of equipment for pesticide treatments. This research aimed at testing substrate mixtures to optimize biobed efficiency to remove pesticides under the climate of the Yucatan (México). Agricultural soil and 11 mixtures adding vegetable compost, sisal pulp, corn stover and seaweed were tested under controlled conditions. Each biomixture was exposed to a mixture of five pesticides (2,4-diclorophenoxyacetic acid "2,4-D" [1.08 mg cm-3], atrazine [2.50 mg cm-3], carbofuran [0.23 mg cm-3], diazinon [0.34 mg cm-3], and glyphosate [0.36 mg cm-3]) in a period of 41 days. Monitoring of the dissipation of pesticide residues showed that pesticides were quickly dissipated in soil at microcosm level experiment, while at two critical times of 20 and 41 days, all mixtures of substrates (biomixtures) were efficient in dissipation of high concentrations of pesticide in a short time (>99%). Time, biomixture and type of pesticide were shown to be the main parameters influencing pesticide dissipation (P < 0.05). Several other physicochemical parameters of the biomixtures, such as organic matter (OM), lignin, water holding capacity (WHC), and pH, were also significant on pesticide dissipation (P < 0.05), being pH the most significant.

Dissipation, metabolism and sorption of pesticides used in fruit-packaging plants: Towards an optimized depuration of their pesticide-contaminated agro-industrial effluents.

Wastewaters from the fruit-packaging industry constitute a serious point source contamination with pesticides. In the absence of effective depuration methods, they are discharged in municipal wastewater treatment plants or spread to land. Modified biobeds could be an applicable solution for their treatment. We studied the dissipation of thiabendazole (TBZ), imazalil (IMZ), ortho-phenylphenol (OPP), diphenylamine (DPA) and ethoxyquin (EQ), used by the fruit-packaging industry, in anaerobically digested sewage sludge, liquid aerobic sewage sludge and in various organic substrates (biobeds packing materials) composed of soil, straw and spend mushroom substrate (SMS) in various volumetric ratios. Pesticide sorption was also determined. TBZ and IMZ showed higher persistence especially in the anaerobically digested sewage sludge (DT50=32.3-257.6d), in contrast to OPP and DPA which were rapidly dissipated especially in liquid aerobic sewage sludge (DT50=1.3-9.3d). EQ was rapidly oxidized mainly to quinone imine (QI) which did not persist and dimethyl ethoxyquinoline (EQNL, minor metabolite) which persisted for longer. Sterilization of liquid aerobic sewage sludge inhibited pesticide decay verifying the microbial nature of pesticide dissipation. Organic substrates rich in SMS showed the highest dissipation capacity with TBZ and IMZ DT50s of ca. 28 d compared to DT50s of >50 d in the other substrates. TBZ and IMZ showed the highest sorption affinity, whereas OPP and DPA were weakly sorbed. Our findings suggest that current disposal practices could not guarantee an efficient depuration of effluents from the fruit-packaging industry, whereas SMS-rich biobed organic substrates show efficient depuration of effluents from the fruit-packaging industry via accelerated dissipation even of recalcitrant fungicides.

Abiotic partitioning of clothianidin under simulated rice field conditions.

BACKGROUND: Clothianidin is registered for pre- and post-flood application in Californian rice fields for control of the rice seed midge, Cricotopus sylvestris, and the rice water weevil, Lissorhoptrus oryzophilus. The objective was to characterize air-water and soil-water partitioning of clothianidin under simulated Californian rice field conditions. RESULTS: Clothianidin was confirmed to be non-volatile (from water) via the gas purge method, as no loss from the aqueous phase was observed at 22 and 37 °C; an upper-limit KH value was calculated at 2.9 × 10(-11) Pa m(3) mol(-1) (20 °C). Soil-water partitioning was determined by the batch equilibrium method using four soils collected from rice fields in the Sacramento Valley, and sorption affinity (Kd ), sorbent capacity, desorption and organic-carbon-normalized distribution (Koc ) were determined. Values for pH, cation exchange capacity and organic matter content ranged from 4.5 to 6.6, from 5.9 to 37.9 and from 1.25 to 1.97% respectively. The log Koc values (22 and 37 °C) ranged from 2.6 to 2.7, while sorption capacity was low at 22 °C and decreased further at 37 °C. Hysteresis was observed in soils at both temperatures, suggesting that bound residues do not readily desorb. CONCLUSIONS: Soil-water and air-water partitioning will not significantly reduce offsite transport of clothianidin from flooded rice fields via drainage.