Pesticide Residues in Organic and Conventional Agricultural Soils across Europe: Measured and Predicted Concentrations.

During the growing season of 2021, 201 soil samples from conventionally and organically managed fields from 10 European countries and 8 cropping systems were taken, and 192 residues of synthetic pesticides were analyzed. Pesticide residues were found in 97% of the samples, and 88% of the samples contained mixtures of at least 2 substances. A maximum of 21 substances were found in conventionally managed fields, and a maximum of 12 were found in organically managed fields. The number and concentration of pesticide residues varied significantly between conventional and organic fields in 70 and 50% of the case study sites, respectively. Application records were available for a selected number of fields (n = 82), and these records were compared to the detected substances. Residues from 52% of the applied pesticides were detected in the soils. Only 21% of the pesticide residues detected in the soil samples were applied during the 2021 growing season. From the application data, predicted environmental concentrations of residues in soil were calculated and compared to the measured concentrations. These estimates turned out not to be accurate. The results of this study show that most European agricultural soils contain mixtures of pesticide residues and that current calculation methods may not reliably estimate their presence.

Current use pesticides in soil and air from two agricultural sites in South Africa: Implications for environmental fate and human exposure.

Concerns about the possible negative impacts of current use pesticides (CUPs) for both the environment and human health have increased worldwide. However, the knowledge on the occurrence of CUPs in soil and air and the related human exposure in Africa is limited. This study investigated the presence of 30 CUPs in soil and air at two distinct agricultural sites in South Africa and estimated the human exposure and related risks to rural residents via soil ingestion and inhalation (using hazard quotients, hazard index and relative potency factors). We collected 12 soil and 14 air samples over seven days during the main pesticide application season in 2018. All samples were extracted, purified and analyzed by high-performance liquid chromatography coupled with tandem mass spectrometry. In soils, nine CUPs were found, with chlorpyrifos, carbaryl and tebuconazole having the highest concentrations (up to 63.6, 1.10 and 0.212 ng g-1, respectively). In air, 16 CUPs were found, with carbaryl, tebuconazole and terbuthylazine having the highest levels (up to 25.0, 22.2 and 1.94 pg m-3, respectively). Spatial differences were observed between the two sites for seven CUPs in air and two in soils. A large dominance towards the particulate phase was found for almost all CUPs, which could be related to mass transport kinetics limitations (non-equilibrium) following pesticide application. The estimated daily intake via soil ingestion and inhalation of individual pesticides ranged from 0.126 fg kg-1 day-1 (isoproturon) to 14.7 ng kg-1 day-1 (chlorpyrifos). Except for chlorpyrifos, soil ingestion generally represented a minor exposure pathway compared to inhalation (i.e. <5%). The pesticide environmental exposure largely differed between the residents of the two distinct agricultural sites in terms of levels and composition. The estimated human health risks due to soil ingestion and inhalation of pesticides were negligible although future studies should explore other relevant pathways.

Effects of biochar on the fate of conazole fungicides in soils and their bioavailability to earthworms and plants.

The study showed novel findings about changes in the fate and bioavailability of conazole fungicides (CFs) after biochar (BC) addition to soil. Two contrasting soils (low- and high-sorbing of CF; L soils, H soils) were amended by three BCs (low-, moderate-, and high-sorbing of CF; L-BC, M-BC, H-BC) at 0.2% and 2% doses. Epoxiconazole (EPC) and tebuconazole (TBC) were then added to the soil-BC mixtures, and their degradation, bioaccumulation in earthworms (Eisenia andrei), and bioconcentration in lettuce (Lactuca sativa) were studied for three months. Also, stir bar sorptive extraction (SBSE) was performed to determine CF (bio)accessibility. The EPC and TBC degradation in the soil-BC mixtures followed usually the first-order decay kinetics. The BC addition prevalently decreased the pesticides degradation in the L soil mixtures but often increased it in the H soil mixtures. In general, EPC degraded less than TBC. BC type and dose roles in the pesticides degradation were unclear. The BC addition significantly reduced pesticide uptake to the earthworms in the L soil mixtures (by 37-96%) and in the H soil mixtures (by 6-89%) with 2% BC. The BC addition reduced pesticide uptake to the lettuce roots and leaves significantly-up to two orders of magnitude, and this reduction was strong in H soil mixtures at 2% of BC. The BC addition reduced the CF (bio)accessibility measured by SBSE in all L soil mixtures and some H soil mixtures with 2% BC. Although not significant, it also seems that the pesticide bioaccumulation, bioconcentration, and (bio)accessibility were decreasing according to the BC type (L-BC > M-BC > H-BC). The pesticide concentrations in the earthworms and lettuce correlated significantly to the SBSE results, which indicates this technique as a possible predictor of biotic uptake. Our results showed that the interactions were hard to predict in the complex soil-BC-pesticide system.

A critical review of the possible adverse effects of biochar in the soil environment.

Biochar has received extensive attention because of its multi-functionality for agricultural and environmental applications. Despite its many benefits, there are concerns related to the long-term safety and implications of its application, mainly because the mechanisms affecting soil and organism health are poorly quantified and understood. This work reviews 259 sources and summarises existing knowledge on biochar's adverse effects on soil from a multiangle perspective, including the physicochemical changes in soil, reduced efficiency of agrochemicals, potentially toxic substances in biochar, and effects on soil biota. Suggestions are made for mitigation measures. Mixed findings are often reported; however, the results suggest that high doses of biochar in clay soils are likely to decrease available water content, and surface application of biochar to sandy soils likely increases erosion and particulate matter emissions. Furthermore, biochar may increase the likelihood of excessive soil salinity and decreased soil fertility because of an increase in the pH of alkaline soils causing nutrient precipitation. Regarding the impact of biochar on (agro)chemicals and the role of biochar-borne toxic substances, these factors cannot be neglected because of their apparent undesirable effects on target and non-target organisms, respectively. Concerning non-target biota, adverse effects on reproduction, growth, and DNA integrity of earthworms have been reported along with effects on soil microbiome such as a shift in the fungi-to-bacteria ratio. Given the diversity of effects that biochar may induce in soil, guidelines for future biochar use should adopt a structured and holistic approach that considers all positive and negative effects of biochar.

Conazole fungicides epoxiconazole and tebuconazole in biochar amended soils: Degradation and bioaccumulation in earthworms.

Biochar usage in agriculture becomes increasingly important for the improvement of soil properties. However, from the perspective of pesticides, biochar can influence exposure to pesticides of both target and non-target organisms and also pesticides' fate in soil. Our study investigated degradation and bioaccumulation (in the Eisenia andrei earthworm) of two conazole fungicides, epoxiconazole and tebuconazole, added to high- and low-sorbing soils (by means of fungicides' sorption measured beforehand) amended with low-, moderate- and high-sorbing biochars at 0.2% and 2% doses. We aimed to investigate the effects of contrasting soil and biochar properties, different doses of biochar in soil-biochar mixtures, and different compounds on the degradation and bioaccumulation. We also wanted to explore if the beforehand determined sorption of fungicides on individual soils and biochars is manifested somehow in their degradation and/or bioaccumulation in soil-biochar mixtures. The biochars' presence in the soils promoted the degradation of fungicides with a clear effect of dose and soil, but less clear effect of biochar or compound. The bioaccumulation factors were higher in low-sorbing soil variants and also decreased with increasing biochar dose. For low-sorbing soil variants, the bioaccumulation was also influenced by the type of biochar corresponding to its sorbing potential and the possible effect on the bioavailability of the fungicides. Our results show that mixing of biochars with soils changes the fate and bioaccumulation of the conazole fungicides. However, the sorption results from original materials are not straightforwardly manifested in the more complex soil-biota system.

Ageing effect on conazole fungicide bioaccumulation in arable soils.

Widely used conazole fungicides (CFs) belong to the most frequently detected pesticides in Central European arable soils. However, data on their environmental behaviour and bioavailability to soil organisms are surprisingly scarce. In the present laboratory microcosm study prochloraz, tebuconazole, epoxiconazole and flusilazole were applied to 12 different agricultural soils at background levels. Bioaccumulation to earthworm E. andrei and lettuce L. sativa roots and leaves was evaluated in non-aged (biota exposure after addition of pesticides) and aged (exposure started three months later) systems. In contrast with expectations from ageing effect (decrease of bioavailability), bioaccumulation in E. andrei was both reduced and enhanced after ageing depending on soil properties. The reduction of bioaccumulation correlated positively to the percentage of clay but negatively to soil organic matter. The affinity of compost worm E. andrei towards organic matter where hydrophobic pesticide molecules are sorbed is discussed as a possible explanation. An apparent effect of ageing (reduction of bioavailability) was particularly observed in lettuce roots, where bioaccumulation was significantly reduced in time. However, bioaccumulation in leaves changed ambiguously in aged variants among CFs, possibly as a combined result of bioconcentration, dilution by plant growth and metabolism. This study brings first insights into how the bioaccumulation of conazole fungicides is affected by sequestration in agricultural soils. The results indicate that in complex systems, the ageing is not necessarily connected with decrease of bioaccumulation.

Fate and bioavailability of four conazole fungicides in twelve different arable soils - Effects of soil and pesticide properties.

The objective of this study is to characterize changes in the fate, behaviour and bioavailability of four conazole fungicides - CFs (prochloraz - PRO, tebuconazole - TEB, epoxiconazole - EPO, flusilazole - FLU) in 12 diverse agricultural soils in complex microcosm systems consisting of agriculturally-used fluvisols, plants (Lactuca sativa), earthworms (Eisenia fetida) and passive samplers (SPME, Empore™ discs, silicone rubber). Due to great variability of the data and other methodological problems, the in-matrix passive samplers failed to be indicators of pore-water concentration and (bio)availability/(bio)accessibility of CFs. A dissipation of all CFs followed the first order kinetics (usually after initial lag phase) with large span of resulting half-lives (7-670 d) depending on soils and compounds. In many soils, the model revealed the ending plateau, which indicates the non-degradable or slowly-degradable residues. The half-lives and the residues were generally higher for EPO and FLU, than for PRO and TEB. Greater but slower total dissipation of CFs was observed in soils with higher percentage of organic matter. Earthworm concentrations were highest at first sampling time (14 days) and considerably decreased afterwards often resulting in PRO concentration below LOQ. Earthworm uptake was influenced by amount of organic matter and soil texture. Accumulation to lettuce roots was generally higher than to leaves and differed greatly among CFs. Concentration shoot to root ratios were generally the lowest for FLU (0.04) and highest for TEB (0.37). PRO was not detected in lettuce leaves during experiment. The study brings new results on fate and bioavailability of CFs in soils.

Currently and recently used pesticides in Central European arable soils.

Although large amounts of pesticides are used annually and a majority enters the soil to form short- or long-term residues, extensive soil surveys for currently used pesticides (CUPs) are scarce. To determine the status of CUPs' occurrence in arable land in Central Europe, 51 CUPs and 9 transformation products (TPs) were analysed in 75 arable soils in the Czech Republic (CR) several months after the last pesticide application. Moreover, two banned triazines (simazine and atrazine) and their TPs were analysed because of their frequent detection in CR waters. Multi-residue pesticide analysis on LC-MS/MS after soil QuEChERS extraction was used. The soils contained multiple pesticide residues frequently (e.g. 51% soils with ≥5 pesticides). The levels were also noticeable (e.g. 36% soils with ≥3 pesticides exceeding the threshold of 0.01mg/kg). After triazine herbicides (89% soils), conazole fungicides showed the second most frequent occurrence (73% soils) and also high levels (53% soils with total conazoles above 0.01mg/kg). Frequent occurrence was found also for chloroacetanilide TPs (25% of soils), fenpropidin (20%) and diflufenican (17%). With the exception of triazines' negative correlation to soil pH, no clear relationships were found between pesticide occurrence and soil properties. Association of simazine TPs with terbuthylazine and its target crops proved the frequent residues of this banned compound originate from terbuthylazine impurities. In contrast, frequent atrazine-2-hydroxy residue is probably a legacy of high atrazine usage in the past. The occurrence and levels of compounds were closely associated with their solubility, hydrophobicity and half-life. The results showed links to CR water-monitoring findings. This study represents the first extensive survey of multiple pesticide residues in Central European arable soils, including an insight into their relationships to site and pesticide properties.

Ecotoxicity of arsenic contaminated sludge after mixing with soils and addition into composting and vermicomposting processes.

Sludge coming from remediation of groundwater contaminated by industry is usually managed as hazardous waste despite it might be considered for further processing as a source of nutrients. The ecotoxicity of phosphorus rich sludge contaminated with arsenic was evaluated after mixing with soil and cultivation with Sinapis alba, and supplementation into composting and vermicomposting processes. The Enchytraeus crypticus and Folsomia candida reproduction tests and the Lactuca sativa root growth test were used. Invertebrate bioassays reacted sensitively to arsenic presence in soil-sludge mixtures. The root elongation of L. sativa was not sensitive and showed variable results. In general, the relationship between invertebrate tests results and arsenic mobile concentration was indicated in majority endpoints. Nevertheless, significant portion of the results still cannot be satisfactorily explained by As chemistry data. Composted and vermicomposted sludge mixtures showed surprisingly high toxicity on all three tested organisms despite the decrease in arsenic mobility, probably due to toxic metabolites of bacteria and earthworms produced during these processes. The results from the study indicated the inability of chemical methods to predict the effects of complex mixtures on living organisms with respect to ecotoxicity bioassays.