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.

Chlorpyrifos degradation and its impacts on phosphorus bioavailability in microplastic-contaminated soil.

Pesticide residues and microplastics (MPs) in agricultural soils are two major concerns for soil health and food safety. The degradation of chlorpyrifos (CPF), an organophosphorus pesticide, releases phosphates. This process may be affected by the presence of MPs in the soil. The combination of CPF and MPs presence in the soil may thus produce interaction effects that alter the soil phosphorus (P) balance. This study explores the degradation pathways of CPF (6 mg kg-1, 12 mg kg-1 of CPF addition) in soils with different levels of polylactic acid MPs (PLA-MPs) (0.0 %, 0.1 %, 0.5 %, 1.0 % w/w), and analyzes soil P fractions and phosphatase enzyme activities to investigate soil P bioavailability under different treatments. Results show that the degradation of CPF fits to a first-order decay model, with half-lives (DT50) ranging from 11.0 to 14.8 d depending on PLA-MPs treatment. The concentration of its metabolite 3, 5, 6-trichloropyridine 2-phenol (TCP) reached a peak of 0.93-1.67 mg kg-1 within 7-14 days. Similarly, the degradation of CPF led to a significant transient increase in P bioavailability within 3-7 days (p < 0.05), with a peak range of 22.55-26.01 mg kg-1 for Olsen-P content and a peak range of 4.63-6.76 % for the proportions of available P fractions (H2O-P+NaHCO3-P+NaOH-P), before returning to prior levels (Olsen-P: 11.28-19.52 mg kg-1; available soil P fractions: 4.15-5.61 %). CPF degradation (6 mg kg-1) was significantly inhibited in soil with 1.0 % PLA-MPs addition. The effects of MPs and CPF on soil P fractions occur at different time frames, implying that their modes of action and interactions with soil microbes differ.

Effects of Microplastics on the Transport of Soil Dissolved Organic Matter in the Loess Plateau of China.

Microplastics (MPs) pollution and dissolved organic matter (DOM) affect soil quality and functions. However, the effect of MPs on DOM and underlying mechanisms have not been clarified, which poses a challenge to maintaining soil health. Under environmentally relevant conditions, we evaluated the major role of polypropylene particles at four micron-level sizes (20, 200, and 500 µm and mixed) in regulating changes in soil DOM content. We found that an increase in soil aeration by medium and high-intensity (>0.5%) MPs may reduce NH4+ leaching by accelerating soil nitrification. However, MPs have a positive effect on soil nutrient retention through the adsorption of PO43- (13.30-34.46%) and NH4+ (9.03-19.65%) and their leached dissolved organic carbon (MP-leached dissolved organic carbon, MP-DOC), thereby maintaining the dynamic balance of soil nutrients. The regulating ion (Ca2+) is also an important competitor in the MP-DOM adsorption system, and changes in its intensity are dynamically involved in the adsorption process. These findings can help predict the response of soil processes, especially nutrient cycling, to persistent anthropogenic stressors, improve risk management policies on MPs, and facilitate the protection of soil health and function, especially in future agricultural contexts.

Response of soybean and maize roots and soil enzyme activities to biodegradable microplastics contaminated soil.

Although biodegradable plastic film is a promising alternative product for reducing polyethylene plastic pollution in agricultural soils, the effects of its residues on plant growth and soil properties remain unclear. In this study, we conducted an experiment to investigate root properties and soil enzyme activities in Poly (butylene adipate-co-terephthalate) microplastics (PBAT-MPs) contaminated soil (0 % (CK), 0.1 %, 0.2 %, 0.5 % and 1 % of dry soil weight) with soybean (Glycine max (Linn.) Merr.) and maize (Zea mays L.). The results show that PBAT-MP accumulation in soil negatively affects root growth, and alter soil enzyme activities, which may then constrain C/N cycling and potential yields. For soybean, the total root length, total root surface area and root biomass decreased by 34 %- 58 %, 34 %- 54 % and 25 %- 40 % at the harvesting stage compared to CK, respectively. The negative effects of PBAT-MPs on maize roots were greater than on soybean roots. The total root length, root surface area and root biomass of maize decreased by 37 %- 71 %, 33 %- 71 % and 24 %- 64 % at the tasseling and harvesting stage, respectively (p < 0.05). Furthermore, a statistical analysis of the data indicates that the inhibition of soybean and maize root growth by PBAT-MP accumulation was mediated by the significantly different impacts of PBAT-MP addition on C-enzyme (ß-xylosidase, cellobiohydrolase, ß-glucosidase) and N-enzyme activities (leucine-aminopeptidase, N-acetyl-ß-glucosaminidase, alanine aminotransferase) in rhizosphere and non-rhizosphere soil, possibly due to interactions with plant-specific root exudates and microbial communities. These findings show the potential risks posed by biodegradable microplastics on the plant-soil system, and suggest that biodegradable plastic film should be applied with caution.

Effects of deterministic assembly of communities caused by global warming on coexistence patterns and ecosystem functions.

Seasonal rhythms in biological and ecological dynamics are fundamental in regulating the structuring of microbial communities. Evaluating the seasonal rhythms of microorganisms in response to climate change could provide information on their variability and stability over longer timescales (>20-year). However, information on temporal variability in microorganism responses to medium- and long-term global warming is limited. In this study, we aimed to elucidate the temporal dynamics of microbial communities in response to global warming; to this end, we integrated data on the maintenance of species diversity, community composition, temporal turnover rates (v), and community assembly process in two typical ecosystems (meadows and shrub habitat) on the Qinghai-Tibet Plateau. Our results showed that 21 years of global warming would increase the importance of the deterministic process for microorganisms in both ecosystems across all seasons (R2 of grassland (GL) control: 0.524, R2 of GL warming: 0.467; R2 of shrubland (SL) control: 0.556, R2 of SL warming: 0.543), reducing species diversity and altering community composition. Due to environmental filtration pressure from 21 years of warming, the low turnover rate (v of warming: -3.13/-2.00, v of control: -2.44/-1.48) of soil microorganisms reduces the resistance and resilience of ecological communities, which could lead to higher community similarity and more clustered taxonomic assemblages occurring across years. Changes to temperature might increase selection pressure on specialist taxa, which directly causes dominant species (v of warming: -1.63, v of control: -2.49) primarily comprising these taxa to be more strongly impacted by changing temperature than conditionally (v of warming: -1.47, v of control: -1.75) or always rare taxa (v of warming: -0.57, v of control: -1.33). Evaluation of the seasonal rhythms of microorganisms in response to global warming revealed that the variability and stability of different microbial communities in different habitats had dissimilar biological and ecological performances when challenged with an external disturbance. The balance of competition and cooperation, because of environmental selection, also influenced ecosystem function in complex terrestrial ecosystems. Overall, our study enriches the limited information on the temporal variability in microorganism responses to 21 years of global warming, and provides a scientific basis for evaluating the impact of climate warming on the temporal stability of soil ecosystems.

Response of soil phosphatase activity and soil phosphorus fractions to the application of chloropicrin and azoxystrobin in ginger cultivation.

BACKGROUND: Soil fumigation can change soil nutrient cycling processes by affecting soil beneficial microorganisms, which is a key issue for soil fertility. However, the effect of combined application of fumigant and fungicide on soil phosphorus (P) availability remains largely unclear. We investigated the effects of the fumigant chloropicrin (CP) and the fungicide azoxystrobin (AZO) on soil phosphatase activity and soil P fractions in ginger production using a 28-week pot experiment with six treatments: control (CK), a single application of AZO (AZO1), double applications of AZO (AZO2), CP-fumigated soil without AZO (CP), CP combined with AZO1 (CP + AZO1) and CP combined with AZO2 (CP + AZO2). RESULTS: AZO application alone significantly increased the soil labile P fractions (Resin-P + NaHCO3 -Pi + NaOH-Pi) at 9 weeks after planting (WAP) but decreased the soil phosphatase activity at 28 WAP. CP fumigation significantly reduced the soil phosphatase activity but increased the proportions of soil labile P fractions (Resin-P + NaHCO3 -Pi + NaHCO3 -Po) to total P (TP) by 9.0-15.5% throughout the experiment. The combined application of CP and AZO had a synergistic effect on soil phosphatase activity and soil P fractions compared with a single application. CONCLUSION: Although AZO application and CP fumigation can increase soil available P in the short term, they might negatively affect soil fertility in the long run by inhibiting soil phosphatase activity. Soil microbial activities, especially microorganisms related to P cycling, may be responsible for the variations in soil P availability, but further research is needed. © 2023 Society of Chemical Industry.

Knowledge and practices of commercial banana farmers related to pesticide use in Chitwan district, Nepal; a cross-sectional study and meta-analyses.

The exposure of farmers to pesticides due to inadequate safety measures is a concern in low-income countries in Africa and Asia. However, until now, there have been limited studies on the farmers' risk due to pesticide application to fruit crops. The knowledge of farmers' exposure related to pesticide use and their safety practices was studied among 100 banana farmers in three areas (Padampur, Jagatpur, and Thimura) of Chitwan district, Nepal. More than 75% of the farmers complained about problems related to insects. Most frequently used insecticides in the area were chlorpyrifos and cypermethrin. Ten percent (10%) of the applied pesticides were highly hazardous to humans, according to the World Health Organization hazard category, with skin rash being the most common acute symptom reported by 29% of the farmers. Banned organochlorine and organophosphate insecticides, such as endosulfan and triazophos, respectively, are still being used by farmers in the aforementioned areas. Spearman's correlation analysis revealed the lack of knowledge and safety practices among farmers leading to inadequate awareness related to the negative effects of pesticide use on human health and the environment. Therefore, government extension service can play a crucial role in improving banana farmers' knowledge of the toxic effects of pesticides as well as enforcing the Nepali language in the labeling of pesticide containers and packages.

Effect of different polymers of microplastics on soil organic carbon and nitrogen - A mesocosm experiment.

Agricultural microplastic pollution has become a growing concern. Unfortunately, the impacts of microplastics (MPs) on agricultural soil carbon and nitrogen dynamics have not been sufficiently reported. In an attempt to remedy this, we conducted a 105-day out-door mesocosm experiment in a soil-plant system using sandy soils amended with two types of MPs, low-density polyethylene (LDPE-MPs) and biodegradable (Bio-MPs), at concentrations of 0.0% (control), 0.5%, 1.0%, 1.5%, 2.0% and 2.5% (w/w, weight ratio of microplastics to air-dry soil). Soil organic matter (SOM), dissolved organic carbon (DOC), permanganate oxidizable carbon (POXC), available nitrogen (AN) of N-NH4+ and N-NO3-, and dissolved organic nitrogen (DON) were measured on day 46 (D46) and 105 (D105) of the experiment. SOM was also measured after microplastics were mixed into soils (D0). For LDPE-MPs treatments, SOM on D0, D46 and D105 showed no significant differences, while for Bio-MPs treatments, SOM significantly (p < 0.05) decreased from D0 to D46. Compared to the control, soil POXC was significantly (p = 0.001) lowered by 0.5%, 1.0% and 2.5% LDPE-MPs and ≥ 1.0% Bio-MPs on D105. LDPE-MPs showed no significant effects on soil DOC and nitrogen cycling. 2.0% and 2.5% Bio-MPs showed significantly higher (p < 0.001) DOC and DON (on D46 and D105) and ≥1.5% Bio-MPs showed significantly lower (p = 0.02) AN (on D46). Overall, Bio-MPs exerted stronger effects on the dynamics of soil carbon and nitrogen cycling. In conclusion, microplastics might pose serious threats to agroecosystems and further research is needed.

Effects of chloropicrin fumigation and azoxystrobin application on ginger growth and phosphorus uptake.

Soil chloropicrin (CP) fumigation helps to increase crop yields by eliminating soil-borne diseases which inhibit plant growth. However, little is known about the effect of the CP fumigation combined with fungicide application on plant growth and nutrient uptake. In this study, we conducted a mesocosm experiment with six treatments: CK (untreated soil), AZO1 (a single application of azoxystrobin (AZO)), AZO2 (double applications of AZO), CP (CP fumigation with no AZO), CP+AZO1 (CP combined with AZO1) and CP+AZO2 (CP combined with AZO2) to investigate the effects of CP fumigation and AZO application on ginger growth and phosphorus (P) uptake. Results showed that a single application of AZO had no significant effect on ginger height, biomass and P uptake whether treated with or without CP fumigation, whereas double applications of AZO combined with CP fumigation significantly improved ginger height and the total amount of P in root (P < 0.05). Meanwhile, AZO residues were similar in all treatments with the same number of applications, with less than 50% remaining in the soil after 7 days applied, indicating that CP fumigation treatment did not influence AZO degradation in ginger cultivation. In addition, although the differences in P use efficiency observed across the different treatments were not significant, they nevertheless suggest that the P budget and soil microbial activity may contribute to those differences. Therefore, further studies should be done to link P cycling with microbial communities, and how these related to fumigation and fungicide application.

Pesticide usage practices and the exposure risk to pollinators: A case study in the North China Plain.

Due to the frequent pesticide applications, bees are suffered from pesticide exposure risks via consumption and direct contact with sprayed drifts. However, if pesticides are misused and the potential exposure risk to bees based on realistic pesticide application data are still little reported. In this study, pesticide application patterns in wheat-maize rotation system, vegetable and apple producing areas, was studied by interviewing farmers in Quzhou County, the North China Plain. The pesticide use status was evaluated by the recommended and actual applied dose and risk quotient (RQ) based Bee-REX model was used to assess the exposure risks of pesticide to bees based on the collected pesticide application data. The results showed that over half (52 %) of farmers in selected sites misused pesticides and orchard owners were frequently misused pesticides. Positive correlations were found between pesticide usage performance and farmers' specialized training experience. Pesticides applied in orchards have caused higher exposure risks to bees with the mean of RQs exceed 120 and 1880 via acute contact and dietary routes, respectively. Pesticide misuse significantly elevates the exposure risk to bees that the mean RQ under misuse scenarios was 5.8 times than that of correct use. Abamectin, fipronil and neonicotinoids contributed most to the pesticide exposure risk to bees. The main findings of this study imply that more sustainable pest and pollinator management strategies, including the moratorium high-risk insecticides and providing diverse flower resources and habitats, are highly needed. Additionally, measures such as implementing farmer educating and training programs should also be put on the agenda.

Pesticide residues in Nepalese vegetables and potential health risks.

We conducted this study in order to assess the pesticide residues in vegetables and examine the related human health risk. Therefore, residues of 23 pesticides (organophosphates, organochlorines, acaricides, fungicides, and insecticides of biological origin) were analysed in the three main vegetable crops grown in Southern Nepal: 27 eggplant, 27 chilli and 32 tomato samples representing (i) conventional (N = 67) and ii) integrated pest management (IPM) fields (N = 19). Pesticide residues were found in 93% of the eggplant samples and in all of the chilli and tomato samples. Multiple residues were observed in 56% of the eggplant samples, 96% of chilli samples and all of the tomato samples. The range (µg/kg) of total detected pesticide residues in eggplants, chillies and tomatoes was 1.71-231, 4.97-507, 13.1-3465, respectively. The most frequently detected pesticides in these vegetables were carbendazim and chloropyrifos. Pesticide residues in 4% of the eggplant, 44% of the tomato and 19% of the chilli samples exceeded the EU maximum residue limits (MRLs). The residues of triazophos, omethoate, chloropyrifos and carbendazim exceeded the EU MRLs. Compared to chilli and eggplant crops, more carbendazim was sprayed onto tomato crops (p < 0.05). We assessed adolescent and adult dietary exposure using hazard quotient (HQ) and hazard index (HI) equations for the identified pesticides. HQ> 1 was observed for chloropyrifos, triazophos and carbendazim in eggplants; profenofos, triazophos, dimethoate, omethoate, chloropyrifos and carbendazim in tomatoes; and dichlorvos and chloropyrifos in chillies. Of all of the HQs, the highest acute HQ (aHQ) was for triazophos (tomato) in adolescents (aHQ=657) and adults (aHQ=677), showing the highest risks of dietary exposure. The cumulative dietary exposure showed a higher HI for organophosphates (HI>83) and a lower HI for organochlorines, acaricides and biological insecticides (HI<1). The concentration of pesticide residues in the vegetable crops from the IPM field was considerably lower, suggesting a greater ability of IPM systems to reduce the dietary risks from exposure to pesticides.

Microplastics in the Terrestrial Ecosystem: Implications for Lumbricus terrestris (Oligochaeta, Lumbricidae).

Plastic debris is widespread in the environment, but information on the effects of microplastics on terrestrial fauna is completely lacking. Here, we studied the survival and fitness of the earthworm Lumbricus terrestris (Oligochaeta, Lumbricidae) exposed to microplastics (Polyethylene, <150 µm) in litter at concentrations of 7, 28, 45, and 60% dry weight, percentages that, after bioturbation, translate to 0.2 to 1.2% in bulk soil. Mortality after 60 days was higher at 28, 45, and 60% of microplastics in the litter than at 7% w/w and in the control (0%). Growth rate was significantly reduced at 28, 45, and 60% w/w microplastics, compared to the 7% and control treatments. Due to the digestion of ingested organic matter, microplastic was concentrated in cast, especially at the lowest dose (i.e., 7% in litter) because that dose had the highest proportion of digestible organic matter. Whereas 50 percent of the microplastics had a size of <50 µm in the original litter, 90 percent of the microplastics in the casts was <50 µm in all treatments, which suggests size-selective egestion by the earthworms. These concentration-transport and size-selection mechanisms may have important implications for fate and risk of microplastic in terrestrial ecosystems.

Soil microeukaryotic communities and phosphorus-cycling microorganisms respond to chloropicrin fumigation and azoxystrobin application.

Fumigants and fungicides are effective at controlling soil-borne pathogens but might also adversely affect soil beneficial microbes, such as soil phosphorus (P) solubilizing microbes, further altering nutrient cycling processes. Therefore, this study investigated the effects of the fumigant chloropicrin (CP) and the fungicide azoxystrobin (AZO) on soil microeukaryotes and P-cycling related soil bacteria through a greenhouse experiment. Soil microeukaryotic communities and bacterial communities containing two phosphomonoesterase encoding genes (phoC and phoD) were analysed using high-throughput sequencing methods. Results showed that, when applied at the field recommended application dosage, the fungicide AZO had no significant influence on the community structure of soil microeukaryotes and phoD-containing bacteria. However, in CP-fumigated soils, the soil microeukaryotic community composition changed from fungi-dominated to protist-dominated. CP fumigation significantly decreased the total phoC/phoD gene copy number but increased the relative abundance of some phoC/phoD-containing bacteria (such as Sinorhizobium and Streptomyces), which are significantly positively correlated to available P compositions in soil. The structural equation model (SEM) confirmed that CP fumigation could affect soil available P content directly by altering phoC-/phoD-containing bacteria, or indirectly by affecting phoC/phoD gene abundance and acid/alkaline phosphatases activity in soil. The inconsistent changes in phoC/phoD-containing bacteria, phoC/phoD gene number, and the phosphomonoesterase activities indicated that enzyme secretion may not be the only way for P solubilizing soil microorganisms to regulate P availability after soil fumigation. The outcome of this study can provide theoretical support for the design of soil beneficial microorganism recovery strategies and the regulation of phosphate fertilizer after soil fumigation.

Exploring the potential of earthworm gut bacteria for plastic degradation.

The use of plastic mulch films in agriculture leads to the inevitable accumulation of plastic debris in soils. Here, we explored the potential of earthworm gut-inhabiting bacterial strains (Mycobacterium vanbaalenii (MV), Rhodococcus jostii (RJ), Streptomyces fulvissimus (SF), Bacillus simplex (BS), and Sporosarcina globispora (SG) to degrade plastic films (⌀ = 15 mm) made from commonly used polymers: low-density polyethylene film (LDPE-f), polylactic acid (PLA-f), polybutylene adipate terephthalate film (PBAT-f), and a commercial biodegradable mulch film, Bionov-B® (composed of Mater-Bi, a feedstock with PBAT, PLA and other chemical compounds). A 180-day experiment was conducted at room temperature (x̄ =19.4 °C) for different strain-plastic combinations under a low carbon media (0.1× tryptic soy broth). Results showed that the tested strain-plastic combinations did not facilitate the degradation of LDPE-f (treated with RJ and SF), PBAT-f (treated with BS and SG), and Bionov-B (treated with BS, MV, and SG). However, incubating PLA-f with SF triggered a reduction in the molecular weights and an increase in crystallinity. Therefore, we used PLA-f as model plastic to study the influence of temperature ("room temperature" & "30 °C"), carbon source ("carbon-free" & "low carbon supply"), and strain interactions ("single strains" & "strain mixtures") on PLA degradation. SF and SF + RJ treatments significantly fostered PLA degradation under 30 °C in a low-carbon media. PLA-f did not show any degradation in carbon-free media treatments. The competition between different strains in the same system likely hindered the performance of PLA-degrading strains. A positive correlation between the final pH of culture media and PLA-f weight loss was observed, which might reflect the pH-dependent hydrolysis mechanism of PLA. Our results situate SF and its co-culture with RJ strains as possible accelerators of PLA degradation in temperatures below PLA glass transition temperature (Tg). Further studies are needed to test the bioremediation feasibility in soils.

Exposure risk to rural Residents: Insights into particulate and gas phase pesticides in the Indoor-Outdoor nexus.

Rural residents are exposed to both particulate and gaseous pesticides in the indoor-outdoor nexus in their daily routine. However, previous personal exposure assessment mostly focuses on single aspects of the exposure, such as indoor or gaseous exposure, leading to severe cognition bias to evaluate the exposure risks. In this study, residential dust and silicone wristbands (including stationary and personal wearing ones) were used to screen pesticides in different phases and unfold the hidden characteristics of personal exposure via indoor-outdoor nexus in intensive agricultural area. Mento-Carlo Simulation was performed to assess the probabilistic exposure risk by transforming adsorbed pesticides from wristbands into air concentration, which explores a new approach to integrate particulate (dust) and gaseous (silicone wristbands) pesticide exposures in indoor and outdoor environment. The results showed that particulate pesticides were more concentrated in indoor, whereas significantly higher concentrations were detected in stationary outdoor wristbands (p < 0.05). Carbendazim and chlorpyrifos were the most frequently detected pesticides in dust and stationary wristbands. Higher pesticide concentration was found in personal wristbands worn by farmers, with the maximum value of 2048 ng g-1 for difenoconazole. Based on the probabilistic risk assessment, around 7.1 % of farmers and 2.6 % of bystanders in local populations were potentially suffering from chronic health issues. One third of pesticide exposures originated mainly from occupational sources while the rest derived from remoting dissipation. Unexpectedly, 43 % of bystanders suffered the same levels of exposure as farmers under the co-existence of occupational and non-occupational exposures. Differed compositions of pesticides were found between environmental samples and personal pesticide exposure patterns, highlighting the need for holistic personal exposure measurements.

Hidden risk of terrestrial food chain contamination from organochlorine insecticides in a vegetable cultivation area of Northwest Bangladesh.

Organochlorine insecticide (OCI) exposures in terrestrial food chains from historical or current applications were studied in a vegetable production area in northwest Bangladesh. A total of 57 subsoil, 57 topsoil, and 57 vegetable samples, as well as 30 cow's milk samples, were collected from 57 farms. Multiple OCI residues were detected using GC-MS/MS with modified QuEChERS in 20 % of subsoils, 21 % of topsoils, 23 % of vegetables, and 7 % of cow's milk samples. Diversified OCI residues were detected in subsoils (17 residues with a concentration of 179.15 ± 148.61 µg kg-1) rather than in topsoils (3 DDT residues with a concentration of 25.76 ± 20.19 µg kg-1). Isomeric ratios indicate intensive historical applications of OCIs. According to Dutch and Chinese standards, the lower concentrations of individual OCI residues in the soil indicate negligible to slight soil pollution, assuming local farmers follow local pesticide use regulations. However, a maximum of 78.24 µg kg-1 ΣAldrines and 35.57 µg kg-1 ΣHCHs were detected (1-4 residues) in 60 % of brinjal, 28 % of cucumber, 29 % of sponge gourd, and 20 % of lady's finger samples, which could be a result of either historical or current OCI applications, or both. A strong positive correlation between aldrines in subsoils and cucurbit vegetables indicates greater bioaccumulation. Cow milk samples contained up to 6.96 µg kg-1 ΣDDTs, which resulted either from rationing contaminated vegetables or grazing on contaminated land. Individual OCI in both vegetables and cow's milk was below the respective maximum residue limits of US and FAO/WHO CODEX and poses little or no risk to human health. However, combined exposure to multiple pesticides could increase human health risks. A cumulative health risk assessment of multiple pesticide residues is suggested to assess the suitability of those soils for cultivation and grazing, as well as the safety of vegetables and cow's milk for human consumption.

Assessing pesticide residues occurrence and risks in water systems: A Pan-European and Argentina perspective.

Freshwater ecosystems face a particularly high risk of biodiversity loss compared to marine and terrestrial systems. The use of pesticides in agricultural fields is recognized as a relevant stressor for freshwater environments, exerting a negative impact worldwide on the overall status and health of the freshwater communities. In the present work, part of the Horizon 2020 funded SPRINT project, the occurrence of 193 pesticide residues was investigated in 64 small water bodies of distinct typology (creeks, streams, channels, ditches, rivers, lakes, ponds and reservoirs), located in regions with high agricultural activity in 10 European countries and in Argentina. Mixtures of pesticide residues were detected in all water bodies (20, median; 8-40 min-max). Total pesticide levels found ranged between 6.89 and 5860 ng/L, highlighting herbicides as the dominant type of pesticides. Glyphosate was the compound with the highest median concentration followed by 2,4-D and MCPA, and in a lower degree by dimethomorph, fluopicolide, prothioconazole and metolachlor(-S). Argentina was the site with the highest total pesticide concentration in water bodies followed by The Netherlands, Portugal and France. One or more pesticides exceeded the threshold values established in the European Water Framework Directive for surface water in 9 out of 11 case study sites (CSS), and the total pesticide concentration surpassed the reference value of 500 ng/L in 8 CSS. Although only 5 % (bifenthrin, dieldrin, fipronil sulfone, permethrin, and terbutryn) of the individual pesticides denoted high risk (RQ > 1), the ratios estimated for pesticide mixtures suggested potential environmental risk in the aquatic compartment studied.

Effects of microplastics and chlorpyrifos on earthworms (Lumbricus terrestris) and their biogenic transport in sandy soil.

Although microplastics (MPs) are ubiquitous in agricultural soil, little is known about the effects of MPs combined with pesticides on soil organisms and their biogenic transport through the soil profile. In this study, we conducted mesocosm experiments to observe the effects of microplastics (polyethylene (LDPE-MPs) and biodegradable microplastics (Bio-MPs)) and chlorpyrifos (CPF) on earthworm (Lumbricus terrestris) mortality, growth and reproduction, as well as the biogenic transport of these contaminants through earthworm burrows. The results showed that earthworm reproduction was not affected by any treatment, but earthworm weight was reduced by 17.6% and the mortality increased by 62.5% in treatments with 28% Bio-MPs. Treatments with 28% LDPE-MPs and 7% Bio-MPs combined with CPF showed greater toxicity while the treatment with 28% Bio-MPs combined with CPF showed less toxicity on earthworm growth as compared to treatments with only MPs. The treatments with 1250 g ha-1 CPF and 28% Bio-MPs significantly decreased the bioaccumulation of CPF in earthworm bodies (1.1 ± 0.2%, w w-1), compared to the treatment with CPF alone (1.7 ± 0.4%). With CPF addition, more LDPE-MPs (8%) were transported into earthworm burrows and the distribution rate of LDPE-MPs in deeper soil was increased. No effect was observed on the transport of Bio-MPs. More CPF was transported into soil in the treatments with LDPE-MPs and Bio-MPs, 5% and 10% of added CPF, respectively. In addition, a lower level of the CPF metabolite 3,5,6-trichloropyridinol was detected in soil samples from the treatments with MPs additions than without MP additions, indicating that the presence of MPs inhibited CPF degradation. In conclusion, Bio-MPs caused significant toxicity effects on earthworms and the different types of MPs combined with CPF affected earthworms differently, and their transport along the soil profile. Thus, further research is urgently needed to understand the environmental risks of MPs and MP-associated compounds in the soil ecosystem.

The role of microplastic aging on chlorpyrifos adsorption-desorption and microplastic bioconcentration.

Microplastics (MPs) in soil undergo different aging processes such as photoaging, mechanical abrasion and biodegradation, leading to alterations in the surface properties of MPs. In this study, we investigated the adsorption-desorption of chlorpyrifos (CPF) on pristine and UV light-aged low-density polyethylene (LDPE) and biodegradable (Bio) MPs that were derived from plastic mulch films. We also tested the bioconcentration of pristine and aged MPs (LDPE- and Bio-MPs aged under UV light and LDPE-MPs aged in three different soils) associated with CPF by earthworms (Lumbricus terrestris). The results showed that UV-aged MPs showed higher CPF adsorption capacities than pristine MPs, with the adsorption capacities at 184.9 ± 5.3, 200.5 ± 1.8, 193.0 ± 8.7, and 215.9 ± 1.1 µg g-1 for pristine LDPE-, UV-aged LDPE-, pristine Bio- and UV-aged Bio-MPs, respectively. The desorption rate of CPF from UV-aged LDPE-MPs within 48 h was lower than the desorption from pristine ones (28.8 ± 7.7% vs. 40.0 ± 3.9%), while both pristine and UV-aged Bio-MPs showed very low CPF desorption rates. A 4-day Petri dish experiment showed that UV-aged MPs were significantly less concentrated in earthworm casts than pristine counterparts (52% and 36% lower for UV-aged LDPE- and Bio-MPs), while UV-aged MPs with adsorbed CPF were concentrated significantly more than UV-aged MPs without CPF. Interestingly, LDPE-MPs aged in soil with a high carbon, nitrogen, and carbon-to-nitrogen ratio were significantly more concentrated in earthworm casts than pristine LDPE-MPs. In conclusion, UV-aged MPs acted as stronger vectors for CPF than pristine MPs. The bioconcentration of MPs differed significantly due to microplastic aging, as well as the combined effect with CPF. Moreover, LDPE-MPs aged in soil with enriched carbon and nitrogen were significantly concentrated in earthworm casts. Further studies on the environmental behaviours of aged MPs associated with other pollutants in soil, especially soils high in carbon and nitrogen, are needed.

Degradation of commercial biodegradable plastics and temporal dynamics of associated bacterial communities in soils: A microcosm study.

Biodegradable plastics (BDPs) have been introduced to replace conventional fossil-based non-biodegradable plastics in agricultural production to reduce the accumulation of plastic debris in soils. However, the degradation performance of commercially available BDP products in real soils and the response of soil microbial communities to biodegradation remain unclear. Here, we explored the degradation characteristics of a commercial BDP product (made from starch, polylactic acid (PLA) and polybutylene adipate terephthalate (PBAT)) in different soils in a microcosm system over a period of 360 days. Temporal dynamics of associated bacterial communities in different soil niches (control soil, plastic surface soil and bulk soil (soil without close contact with plastics)) were profiled. Weight loss reached 42.0±1.2% to 48.0±2.2% in different soils after 360 days. The degradation of BDP followed the same pattern in different soils characterized by two distinct stages. In the first stage (day 0-30), BDPs experienced major weight loss (35.8-41.9%) which coincided with a drastic increase in the soil dissolve organic carbon (1.53-2.25 times the control soil) and the forming of distinct bacterial communities in the plastic surface soil. Thermalgravimetric analysis (TGA) and fourier transform infrared (FTIR) analysis confirmed the fast depletion of starch in this stage. In addition, observations with naked eyes and scanning electron microscope confirmed intensive microbial colonization on BDP surfaces. In the second stage (day 30-360), the degradation of remaining PLA and PBAT continued at a relatively slow rate. Meanwhile bacterial communities in the plastic surface soil started to gradually recover from the disturbance caused by fast biodegradation in the first stage in a soil-dependent manner. Our findings indicate that the degradation performance of BDPs was limited by the degradation rate of relatively recalcitrant components and the temporal dynamics of associated soil bacterial communities synchronized with the degradation of BDPs.