Wildlife ecotoxicology of plant protection products: knowns and unknowns about the impacts of currently used pesticides on terrestrial vertebrate biodiversity.

Agricultural practices are a major cause of the current loss of biodiversity. Among postwar agricultural intensification practices, the use of plant protection products (PPPs) might be one of the prominent drivers of the loss of wildlife diversity in agroecosystems. A collective scientific assessment was performed upon the request of the French Ministries responsible for the Environment, for Agriculture and for Research to review the impacts of PPPs on biodiversity and ecosystem services based on the scientific literature. While the effects of legacy banned PPPs on ecosystems and the underlying mechanisms are well documented, the impacts of current use pesticides (CUPs) on biodiversity have rarely been reviewed. Here, we provide an overview of the available knowledge related to the impacts of PPPs, including biopesticides, on terrestrial vertebrates (i.e. herptiles, birds including raptors, bats and small and large mammals). We focused essentially on CUPs and on endpoints at the subindividual, individual, population and community levels, which ultimately linked with effects on biodiversity. We address both direct toxic effects and indirect effects related to ecological processes and review the existing knowledge about wildlife exposure to PPPs. The effects of PPPs on ecological functions and ecosystem services are discussed, as are the aggravating or mitigating factors. Finally, a synthesis of knowns and unknowns is provided, and we identify priorities to fill gaps in knowledge and perspectives for research and wildlife conservation.

Experimental investigation of the effect of tebuconazole on three biomarkers of innate immunity in the house sparrow (Passer domesticus).

Triazoles are among the most widely used fungicides in the world due to their efficacy against fungal crop diseases and their broad spectrum of action. Intensive use of triazoles has resulted in residual contamination in different compartments of agroecosystems and exposes non-target species to potential sublethal effects. Triazoles are known to be immunomodulators in medicine and therapeutic treatments, but very little data is available on their potential effect on immune parameters of non-target vertebrate species living in agroecosystems. In this study, we experimentally examined the impact of tebuconazole on three immune biomarkers (haemagglutination titre (HA), haemolysis titre (HL), and haptoglobin concentration (Hp)), as well as on the body condition of house sparrows (Passer domesticus). Our results suggest that tebuconazole had very little, if any, effect on the studied immune parameters. However, further studies are needed to better assess the effect of tebuconazole on bird immunity because (1) experimental individuals were kept under optimal conditions and the impact of tebuconazole on immunity may occur under suboptimal conditions, (2) only one concentration of tebuconazole was tested and its effect could be dose-dependent and (3) other complementary immunological biomarkers should be studied, given the complexity of the vertebrate immune system. Current knowledge on the potential effects of triazoles on the immunity of wild farmland vertebrates is still largely insufficient. Further physiological and immune studies should be conducted to better understand the effect of triazole fungicides on farmland birds.

Advancing exposure assessment approaches to improve wildlife risk assessment.

The exposure assessment component of a Wildlife Ecological Risk Assessment aims to estimate the magnitude, frequency, and duration of exposure to a chemical or environmental contaminant, along with characteristics of the exposed population. This can be challenging in wildlife as there is often high uncertainty and error caused by broad-based, interspecific extrapolation and assumptions often because of a lack of data. Both the US Environmental Protection Agency (USEPA) and European Food Safety Authority (EFSA) have broadly directed exposure assessments to include estimates of the quantity (dose or concentration), frequency, and duration of exposure to a contaminant of interest while considering "all relevant factors." This ambiguity in the inclusion or exclusion of specific factors (e.g., individual and species-specific biology, diet, or proportion time in treated or contaminated area) can significantly influence the overall risk characterization. In this review, we identify four discrete categories of complexity that should be considered in an exposure assessment-chemical, environmental, organismal, and ecological. These may require more data, but a degree of inclusion at all stages of the risk assessment is critical to moving beyond screening-level methods that have a high degree of uncertainty and suffer from conservatism and a lack of realism. We demonstrate that there are many existing and emerging scientific tools and cross-cutting solutions for tackling exposure complexity. To foster greater application of these methods in wildlife exposure assessments, we present a new framework for risk assessors to construct an "exposure matrix." Using three case studies, we illustrate how the matrix can better inform, integrate, and more transparently communicate the important elements of complexity and realism in exposure assessments for wildlife. Modernizing wildlife exposure assessments is long overdue and will require improved collaboration, data sharing, application of standardized exposure scenarios, better communication of assumptions and uncertainty, and postregulatory tracking. Integr Environ Assess Manag 2024;20:674-698. © 2023 SETAC.

Impacts of neonicotinoids on biodiversity: a critical review.

Neonicotinoids are the most widely used class of insecticides in the world, but they have raised numerous concerns regarding their effects on biodiversity. Thus, the objective of this work was to do a critical review of the contamination of the environment (soil, water, air, biota) by neonicotinoids (acetamiprid, clothianidin, imidacloprid, thiacloprid, thiamethoxam) and of their impacts on terrestrial and aquatic biodiversity. Neonicotinoids are very frequently detected in soils and in freshwater, and they are also found in the air. They have only been recently monitored in coastal and marine environments, but some studies already reported the presence of imidacloprid and thiamethoxam in transitional or semi-enclosed ecosystems (lagoons, bays, and estuaries). The contamination of the environment leads to the exposure and to the contamination of non-target organisms and to negative effects on biodiversity. Direct impacts of neonicotinoids are mainly reported on terrestrial invertebrates (e.g., pollinators, natural enemies, earthworms) and vertebrates (e.g., birds) and on aquatic invertebrates (e.g., arthropods). Impacts on aquatic vertebrate populations and communities, as well as on microorganisms, are less documented. In addition to their toxicity to directly exposed organisms, neonicotinoid induce indirect effects via trophic cascades as demonstrated in several species (terrestrial and aquatic invertebrates). However, more data are needed to reach firmer conclusions and to get a clearer picture of such indirect effects. Finally, we identified specific knowledge gaps that need to be filled to better understand the effects of neonicotinoids on terrestrial, freshwater, and marine organisms, as well as on ecosystem services associated with these biotas.

Environmental pollution and nutritional quality modulate immune response of the wood mouse (Apodemus sylvaticus) through hormonal disturbances.

Cadmium (Cd) and lead (Pb) are known to enhance immune cell damages and to decrease cellular immunity, promoting higher susceptibility to infectious diseases. Selenium (Se) is an essential element involved in immunity and reactive oxygen species scavenging. This study aimed at evaluating how Cd and Pb and low nutritional (Se) quality modulate immune response to a bacterial lipopolysaccharide (LPS) challenge in wood mice (Apodemus sylvaticus). Mice were trapped near a former smelter in northern France in sites of High or Low contamination. Individuals were challenged immediately after capture or after five days of captivity, fed a standard or a Se-deficient diet. Immune response was measured with leukocyte count and plasma concentration of TNF-α, a pro-inflammatory cytokine. Faecal and plasma corticosterone (CORT), a stress-hormone involved in anti-inflammatory processes, was measured to assess potential endocrine mechanisms. Higher hepatic Se and lower faecal CORT were measured in free-ranging wood mice from High site. LPS-challenged individuals from High site showed steeper decrease of circulating leukocytes of all types, higher TNF-α concentrations, and a significant increase of CORT, compared to individuals from Low site. Challenged captive animals fed standard food exhibited similar patterns (decrease of leukocytes, increase of CORT, and detectable levels of TNF-α), with individuals from lowly contaminated site having higher immune responses than their counterparts from highly polluted site. Animals fed Se-deficient food exhibited lymphocytes decrease, no CORT variation, and average levels of TNF-α. These results suggest (i) a higher inflammatory response to immune challenge in free-ranging animals highly exposed to Cd and Pb, (ii) a faster recovery of inflammatory response in animals lowly exposed to pollution when fed standard food than more exposed individuals, and (iii) a functional role of Se in the inflammatory response. The role of Se and mechanisms underlying the relationship between glucocorticoid and cytokine remain to be elucidated.

Chronic exposure to tebuconazole alters thyroid hormones and plumage quality in house sparrows (Passer domesticus).

Triazoles belong to a family of fungicides that are ubiquitous in agroecosystems due to their widespread use in crops. Despite their efficiency in controlling fungal diseases, triazoles are also suspected to affect non-target vertebrate species through the disruption of key physiological mechanisms. Most studies so far have focused on aquatic animal models, and the potential impact of triazoles on terrestrial vertebrates has been overlooked despite their relevance as sentinel species of contaminated agroecosystems. Here, we examined the impact of tebuconazole on the thyroid endocrine axis, associated phenotypic traits (plumage quality and body condition) and sperm quality in wild-caught house sparrows (Passer domesticus). We experimentally exposed house sparrows to realistic concentrations of tebuconazole under controlled conditions and tested the impact of this exposure on the levels of thyroid hormones (T3 and T4), feather quality (size and density), body condition and sperm morphology. We found that exposure to tebuconazole caused a significant decrease in T4 levels, suggesting that this azole affects the thyroid endocrine axis, although T3 levels did not differ between control and exposed sparrows. Importantly, we also found that exposed females had an altered plumage structure (larger but less dense feathers) relative to control females. The impact of tebuconazole on body condition was dependent on the duration of exposure and the sex of individuals. Finally, we did not show any effect of exposure to tebuconazole on sperm morphology. Our study demonstrates for the first time that exposure to tebuconazole can alter the thyroid axis of wild birds, impact their plumage quality and potentially affect their body condition. Further endocrine and transcriptomic studies are now needed not only to understand the underlying mechanistic effects of tebuconazole on these variables, but also to further investigate their ultimate consequences on performance (i.e. reproduction and survival).

Main conclusions and perspectives from the collective scientific assessment of the effects of plant protection products on biodiversity and ecosystem services along the land-sea continuum in France and French overseas territories.

Preservation of biodiversity and ecosystem services is critical for sustainable development and human well-being. However, an unprecedented erosion of biodiversity is observed and the use of plant protection products (PPP) has been identified as one of its main causes. In this context, at the request of the French Ministries responsible for the Environment, for Agriculture and for Research, a panel of 46 scientific experts ran a nearly 2-year-long (2020-2022) collective scientific assessment (CSA) of international scientific knowledge relating to the impacts of PPP on biodiversity and ecosystem services. The scope of this CSA covered the terrestrial, atmospheric, freshwater, and marine environments (with the exception of groundwater) in their continuity from the site of PPP application to the ocean, in France and French overseas territories, based on international knowledge produced on or transposable to this type of context (climate, PPP used, biodiversity present, etc.). Here, we provide a brief summary of the CSA's main conclusions, which were drawn from about 4500 international publications. Our analysis finds that PPP contaminate all environmental matrices, including biota, and cause direct and indirect ecotoxicological effects that unequivocally contribute to the decline of certain biological groups and alter certain ecosystem functions and services. Levers for action to limit PPP-driven pollution and effects on environmental compartments include local measures from plot to landscape scales and regulatory improvements. However, there are still significant gaps in knowledge regarding environmental contamination by PPPs and its effect on biodiversity and ecosystem functions and services. Perspectives and research needs are proposed to address these gaps.

Long-term monitoring of exposure to toxic and essential metals and metalloids in the tawny owl (Strix aluco): Temporal trends and influence of spatial patterns.

As a result of regulatory decisions, atmospheric deposition of most toxic metals and metalloids (MEs) has decreased in Europe over the past few decades. However, little is known about how this reduction translates into exposure at higher trophic levels in the terrestrial environment where temporal trends may be spatially heterogeneous due to local current or legacy sources of emissions (e.g., industry) or long-range transport of elements (e.g., marine transport). The aim of this study was to characterize temporal and spatial trends of exposure to MEs in terrestrial food webs using a predatory bird, the tawny owl Strix aluco, as a biomonitor. Toxic (Al, As, Cd, Hg, Pb) and essential/beneficial (B, Co, Cu, Mn, Se) elemental concentrations were measured in feathers of nest-captured females from 1986 to 2016, extending a previous study published over the time-series 1986-2005 (n = 1051), in a breeding population in Norway. A drastic decline over time was shown for the toxic MEs (-97 % for Pb, -89 % for Cd, -48 % for Al, and -43 % for As) except Hg. The beneficial elements B, Mn, and Se showed oscillations but an overall decline (-86 %, -34 %, and -12 %, respectively) whereas the essentials Co and Cu did not exhibit significant trends. The distance to potential sources of contamination influenced both the spatial patterns of concentrations in owl feathers and their temporal trends. The accumulation of As, Cd, Co, Mn and Pb was overall higher in the vicinity of sites recorded as polluted, and a greater temporal decrease of As, B, and Cd concentrations was found in the areas of further distance to polluted sites. The decrease of Pb concentrations was sharper further from the coast during the 1980s than in coastal areas, while the opposite was observed for Mn. The levels of Hg and Se were higher in coastal areas, and Hg temporal trends differed according to the distance to the coast. This study highlights the valuable insights provided by long-term survey of wildlife exposure to pollutants and landscape indicators to reveal regional or local patterns and detect unexpected events, data that are crucial for regulation and conservation of ecosystem health.

Effects of chronic exposure to toxic metals on haematological parameters in free-ranging small mammals.

Blood circulates through the vascular system to carry oxygen, nutrients and metabolites to and away from tissues, and as such is a key-component of animal physiology. The impacts of metal pollution on blood, however, are poorly documented in free-ranging vertebrates. While the counteracting effect of selenium on mercury toxicity is well known in marine mammals, its potential role against the toxicity of other metals is less studied, especially on terrestrial wildlife. We explored the consequences of chronic exposure to two non-essential metals (cadmium and lead) along a pollution gradient in Northern France, on eleven haematological parameters in two free ranging small mammals, the wood mouse Apodemus sylvaticus and the bank vole Myodes glareolus. We hypothesized that haematology was related to metal concentrations in tissues, and that selenium might exert modulating effects. Concentrations of cadmium and lead in the tissues indicated an increased chronic exposure to and accumulation of metals along the gradient. Some haematological parameters were not explained by any measured variables while some others varied only with gender or age. Red blood cells, red blood cells distribution width, and blood iron concentration, however, decreased with increasing cadmium in the tissues in wood mice. Red blood cells and haemoglobin decreased with increasing renal lead and hepatic cadmium, respectively, in bank voles. Red blood cells distribution width in wood mice increased with cadmium concentrations in the liver but this was counteracted by high selenium levels in the same organ. An interaction of selenium and lead on red blood cells was also observed in bank voles. Further, selenium concentrations were associated with an increase of monocytes in wood mice. The present results show that toxic metals were related to haematology changes, particularly erythrocyte indicators, and that some essential elements like selenium should be measured as well since they may counteract toxic effects.

Pervasive exposure of wild small mammals to legacy and currently used pesticide mixtures in arable landscapes.

Knowledge gaps regarding the potential role of pesticides in the loss of agricultural biodiversity worldwide and mixture-related issues hamper proper risk assessment of unintentional impacts of pesticides, rendering essential the monitoring of wildlife exposure to these compounds. Free-ranging mammal exposure to legacy (Banned and Restricted: BRPs) and currently used (CUPs) pesticides was investigated, testing the hypotheses of: (1) a background bioaccumulation for BRPs whereas a "hot-spot" pattern for CUPs, (2) different contamination profiles between carnivores and granivores/omnivores, and (3) the role of non-treated areas as refuges towards exposure to CUPs. Apodemus mice (omnivore) and Crocidura shrews (insectivore) were sampled over two French agricultural landscapes (n = 93). The concentrations of 140 parent chemicals and metabolites were screened in hair samples. A total of 112 compounds were detected, showing small mammal exposure to fungicides, herbicides and insecticides with 32 to 65 residues detected per individual (13-26 BRPs and 18-41 CUPs). Detection frequencies exceeded 75% of individuals for 13 BRPs and 25 CUPs. Concentrations above 10 ng/g were quantified for 7 BRPs and 29 CUPs (in 46% and 72% of individuals, respectively), and above 100 ng/g for 10 CUPs (in 22% of individuals). Contamination (number of compounds or concentrations) was overall higher in shrews than rodents and higher in animals captured in hedgerows and cereal crops than in grasslands, but did not differ significantly between conventional and organic farming. A general, ubiquitous contamination by legacy and current pesticides was shown, raising issues about exposure pathways and impacts on ecosystems. We propose a concept referred to as "biowidening", depicting an increase of compound diversity at higher trophic levels. This work suggests that wildlife exposure to pesticide mixtures is a rule rather than an exception, highlighting the need for consideration of the exposome concept and questioning appropriateness of current risk assessment and mitigation processes.

Evidence of environmental transfer of tebuconazole to the eggs in the house sparrow (Passer domesticus): An experimental study.

Triazole compounds are among the most widely used fungicides in agroecosystems to protect crops from potential fungal diseases. Many farmland birds spend a significant part of their life cycle in agroecosystems, which may chronically expose them to pesticides. We experimentally tested whether exposure to environmental concentrations of tebuconazole could induce a contamination of the eggs in an agroecosystem sentinel species, the house sparrow (Passer domesticus). Wild-caught adult sparrows were maintained in captivity and exposed (exposed group) or not (control group) for seven months to tebuconazole through drinking water. Eggs were opportunistically collected for the determination of tebuconazole concentration by Liquid Chromatography coupled to tandem Mass Spectrometry in eggs. We found that eggs from exposed parents all contained tebuconazole with a mean concentration of 1.52 ng g-1 dry weight. In eggs from control parents, the tebuconazole concentration was below the limit of quantification (0.23 ng g-1 dry weight) for 11 out of 13 eggs. Thus, our study demonstrates for the first time that environmental exposure of female birds to tebuconazole can translate into egg contamination by this fungicide.

The impact of climate sensitive factors on the exposure to organohalogenated contaminants in an aquatic bird exploiting both marine and freshwater habitats.

To assess how climate-sensitive factors may affect the exposure to organochlorines (OCs) and perfluoroalkyl substances (PFASs), we monitored concentrations in eggs of the common goldeneye (Bucephala clangula) over two decades (1999-2019) in central Norway. The goldeneye alternates between marine and freshwater habitats and is sensitive to climate variation, especially due to alterations in ice conditions which may affect feeding conditions. We assessed how biological factors such as diet (stable isotopes δ13C and δ15N), the onset of egg laying, and physical characteristics such as winter climate (North Atlantic Oscillation: NAOw) influenced exposure. We predicted compounds to show different temporal trends depending on whether they were still in production (i.e. some PFASs) or have been banned (i.e. legacy OCs and some PFASs). Therefore, we controlled for potential temporal trends in all analyses. There were declining trends for α- and γ-hexachlorocyclohexane (HCH), oxychlordane, cis-chlordane, cis-nonachlor, p,p'-dichlorodiphenyltrichloroethane (p.p'-DDT) and less persistent polychlorinated biphenyl (PCB) congeners (e.g. PCB101). In contrast, the dominant compounds, such as p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) and persistent PCB congeners, were stable, whereas hexachlorobenzene (HCB) increased over time. Most OCs were positively related to δ15N, suggesting higher exposure in birds feeding at upper trophic levels. Chlordanes and HCB were positively associated with δ13C, indicating traces of marine input for these compounds, whereas the relationships to most PCBs were negative. Among PFASs, perfluorooctanesulfonamide (PFOSA) and perfluorohexane sulfonic acid (PFHxS) declined. Most PFASs were positively associated with δ13C, whereas there were no associations with δ15N. Egg laying date was positively associated to perfluoroheptanesulfonic acid (PFHpS), perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), suggesting that some of the PFAS load originated from the wintering locations. Although NAOw had little impact on the exposure to organohalogenated contaminants, factors sensitive to climate change, especially diet, were associated with the exposure to OHCs in goldeneyes.

Experimental Exposure to Tebuconazole Affects Metabolism and Body Condition in a Passerine Bird, the House Sparrow (Passer domesticus).

Triazole compounds are among the most widely used fungicides in agroecosystems to protect crops from potential fungal diseases. Triazoles are suspected to have an impact on nontarget species due to their interactions with nonfungal sterol synthesis, and wild birds are likely to be contaminated by triazole fungicides because many of them live in agroecosystems. We experimentally tested whether exposure to environmental concentrations of a triazole could alter key integrative traits (metabolic rates and body condition) of an agroecosystem sentinel species, the house sparrow (Passer domesticus). Wild-caught adult sparrows were maintained in captivity and exposed (exposed group) or not (control group) for 7 continuous months to tebuconazole through drinking water. The metabolic rates of exposed and control sparrows were then measured at two different temperatures (12 °C and 25 °C), which correspond, respectively, to the thermoregulation and thermoneutrality temperatures of this species. We found that exposed sparrows had lower resting metabolic rates (i.e., measured at thermoneutrality, 25 °C) than controls. However, the thermoregulatory metabolic rates (i.e., measured at 12 °C) did not differ between exposed and control sparrows. Although the body mass and condition were not measured at the beginning of the exposure, sparrows at the time of the metabolic measurements 7 months after the onset of such exposure had a higher body condition than controls, supporting further the idea that tebuconazole affects metabolic functions. Our study demonstrates for the first time that the use of tebuconazole can alter metabolism and could potentially lead to adverse effects in birds. Environ Toxicol Chem 2022;41:2500-2511. © 2022 SETAC.

Ecosystem specific accumulation of organohalogenated compounds: A comparison between adjacent freshwater and terrestrial avian predators.

Insight into processes determining the exposure of organohalogenated contaminants (OHCs) in wildlife might be gained from comparing predators in different ecosystems. This study compared two avian predator species with similar food chain lengths: the goldeneye duck (Bucephala clangula) and the tawny owl (Strix aluco) breeding in adjacent freshwater- and terrestrial ecosystems in central Norway. We measured lipophilic organochlorines (OCs) and protein-bound perfluorinated substances (PFASs) in eggs of the two species over 21 years (1999-2019). Across years, the proportional distribution of OCs (∼90% of the ΣOHC load) relative to PFASs (∼10%) was similar in the two species. Moreover, ΣOC concentrations were similar between the species, but PFAS compounds were 2-12 times higher in the goldeneyes than in tawny owls. OC-pesticides dominated in tawny owls (∼60% of ΣOC), whereas persistent polychlorinated biphenyl (PCBs) congeners were the main OC components in goldeneyes (∼70% of ΣOC). The lipid-normalized concentrations of most OC-pesticides and the less persistent PCB101 declined significantly in both species. Hexachlorobenzene (HCB), p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE), and more persistent PCBs decreased in tawny owls, while they tended to increase in goldeneyes. The increase in HCB was particulary robust. Among the PFASs, contrasted temporal trends were found across the species for four out of 11 compounds: PFOS declined while most perfluorocarboxylic acids (PFCAs) increased in tawny owls. In contrast, most PFASs were stable in goldeneyes. Moreover, there was no annual covariance between the OHC exposure in the two species: i.e., high concentrations in one species in a given year did not translate into high concentrations in the other. Hence, the two avian predators in adjacent ecosystems seem to be subject to different processes determining the OHC exposure, probably related to variation in diet and climate, long-range transport of different contaminants, and emissions of pollution locally.

Field mixtures of currently used pesticides in agricultural soil pose a risk to soil invertebrates.

Massive use of pesticides in conventional agriculture leads to accumulation in soil of complex mixtures, triggering questions about their potential ecotoxicological risk. This study assessed cropland soils containing pesticide mixtures sampled from conventional and organic farming systems at La Cage and Mons, France. The conventional agricultural field soils contained more pesticide residues (11 and 17 versus 3 and 11, respectively) and at higher concentrations than soils from organic fields (mean 6.6 and 10.5 versus 0.2 and 0.6 µg kg-1, respectively), including systemic insecticides belonging to neonicotinoids, carbamate herbicides and broad-spectrum fungicides mostly from the azole family. A risk quotient (RQi) approach evaluated the toxicity of the pesticide mixtures in soil, assuming concentration addition. Based on measured concentrations, both conventional agricultural soils posed high risks to soil invertebrates, especially due to the presence of epoxiconazole and imidacloprid, whereas soils under organic farming showed negligible to medium risk. To confirm the outcome of the risk assessment, toxicity of the soils was determined in bioassays following standardized test guidelines with seven representative non-target invertebrates: earthworms (Eisenia andrei, Lumbricus rubellus, Aporrectodea caliginosa), enchytraeids (Enchytraeus crypticus), Collembola (Folsomia candida), oribatid mites (Oppia nitens), and snails (Cantareus aspersus). Collembola and enchytraeid survival and reproduction and land snail growth were significantly lower in soils from conventional compared to organic agriculture. The earthworms displayed different responses: L. rubellus showed higher mortality on soils from conventional agriculture and large body mass loss in all field soils, E. andrei showed considerable mass loss and strongly reduced reproduction, and A. caliginosa showed significantly reduced acetylcholinesterase activity in soils from conventional agriculture. The oribatid mites did not show consistent differences between organic and conventional farming soils. These results highlight that conventional agricultural practices pose a high risk for soil invertebrates and may threaten soil functionality, likely due to additive or synergistic "cocktail effects".

Temporal Trends of Organochlorine and Perfluorinated Contaminants in a Terrestrial Raptor in Northern Europe Over 34 years (1986-2019).

Fourteen legacy organochlorine (OC) contaminants and 12 perfluoroalkyl substances (PFASs) were measured in eggs of tawny owls (Strix alueco) in central Norway (1986-2019). We expected OCs to have reached stable equilibrium levels due to bans, and that recent phase-out of some PFASs would have slowed the increase of these compounds. ∑OC comprised on average approximately 92% of the measured compounds, whereas ∑PFAS accounted for approximately 8%. However, whereas the ∑OC to ∑PFAS ratio was approximately 60 in the first 5 years of the study, it was only approximately 11 in the last 5 years. Both OC pesticides and polychlorinated biphenyls (PCBs) showed substantial declines over the study period (~85%-98%): hexachlorocyclohexanes and chlordanes seemed to be levelling off, whereas p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) and hexachlororbenzene (HCB), and most PCB congeners still seemed to decline at a more or less constant rate. While the concentration of perfluorooctane sulfonic acid (PFOS), the dominating PFAS, was reduced by approximately 43%, other perfluorinated sulfonates (PFSAs) showed only minor changes. Moreover, the median concentrations of seven perfluorinated carboxylic acids (PFCAs) increased approximately five-fold over the study period. Perfluorononanoic acid and perfluoroundecanoate acid, however, seemed to be levelling off in recent years. In contrast, perfluorododecanoic acid, perfluorodecanoate acid, perfluorotridecanoic acid, and perfluorotetradecanoic acid seemed to increase more or less linearily. Finally, perfluorooctanoic acid (PFOA) was increasingly likely to be detected over the study period. Hence, most legacy OCs and PFOS have not reached a lower threshold with stable background levels, and voluntary elimination of perfluoroalkyl carboxylates still has not resulted in declining levels in tawny owls in central Norway. Environ Toxicol Chem 2022;41:1508-1519. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Ultrasound-assisted QuEChERS-based extraction using EDTA for determination of currently-used pesticides at trace levels in soil.

It is essential to monitor pesticides in soils as their presence at trace levels and their bioavailability can induce adverse effects on soil's ecosystems, animals, and human health. In this study, we developed an analytical method for the quantification of traces of multi-class pesticides in soil using liquid chromatography-tandem mass spectrometry. In this way, 31 pesticides were selected, including 12 herbicides, 9 insecticides, and 10 fungicides. Two extraction techniques were first evaluated, namely, the pressurized liquid extraction and the QuEChERS procedure. The latest one was finally selected and optimized, allowing extraction recoveries of 55 to 118%. The role of the chelating agent EDTA, which binds preferentially to soil cations that complex some pesticides, was highlighted. Coupled with liquid chromatography-tandem mass spectrometry, the procedure displayed very high sensitivity, with limits of quantification (LOQ) in the range 0.01-5.5 ng/g. A good linearity (R2 > 0.992) was observed over two orders of magnitude (LOQ-100 [Formula: see text] LOQ) with good accuracy (80-120%) for all compounds except the two pyrethroids lambda-cyhalothrin and tau-fluvalinate (accuracy comprised between 50 and 175%) and the cyclohexanedione cycloxydim (accuracy < 35%). Good repeatability and reproducibility were also achieved. The method was finally successfully applied to 12 soil samples collected from 3 land-use types. Among the 31-targeted pesticides, 24 were detected at least once, with concentration levels varying from LOQ to 722 ng/g. Many values were below 0.5 ng/g, indicating that the developed method could provide new knowledge on the extremely low residual contents of some pesticides.

A multiresidue analytical method on air and rainwater for assessing pesticide atmospheric contamination in untreated areas.

The use of pesticides in agriculture to protect crops against pests and diseases generates environmental contamination. The atmospheric compartment contributes to their dispersion at different distances from the application areas and to the exposure of organisms in untreated areas through dry and wet deposition. A multiresidue analytical method using the same TD-GC-MS analytical pipeline to quantify pesticide concentrations in both the atmosphere and rainwater was developed and tested in natura. A Box-Behnken experimental design was used to identify the best compromise in extraction conditions for all 27 of the targeted molecules in rainwater. Extraction yields were above 80% except for the pyrethroid family, for which the recovery yields were around 40-59%. TD-GC-MS proved to be a good analytical solution to detect and quantify pesticides in both target matrices with low limits of quantification. Twelve pesticides (six fungicides, five herbicides and one insecticide) were quantified in rainwater at concentrations ranging from 0.5 ng·L-1 to 170 ng·L-1 with a seasonal effect, and a correlation was found between the concentrations in rainwater and air. The calculated cumulative wet deposition rates are discussed regarding pesticide concentrations in the topsoil in untreated areas for some of the studied compounds.

Vegetation shapes aboveground invertebrate communities more than soil properties and pollution: a preliminary investigation on a metal-contaminated site.

Pollution with trace metals (TM) has been shown to affect diversity and/or composition of plant and animal communities. While ecotoxicological studies have estimated the impact of TM contamination on plant and animal communities separately, ecological studies have widely demonstrated that vegetation is an important factor shaping invertebrate communities. It is supposed that changes in invertebrate communities under TM contamination would be explained by both direct impact of TM on invertebrate organisms and indirect effects due to changes in plant communities. However, no study has clearly investigated which would more importantly shape invertebrate communities under TM contamination. Here, we hypothesized that invertebrate communities under TM contamination would be affected more importantly by plant communities which constitute their habitat and/or food than by direct impact of TM. Our analysis showed that diversity and community identity of flying invertebrates were explained only by plant diversity which was not affected by TM contamination. Diversity of ground-dwelling (GD) invertebrates in spring was explained more importantly by plant diversity (27% of variation) than by soil characteristics including TM concentrations (8%), whereas their community identity was evenly explained by plant diversity and soil characteristics (2-7%). In autumn, diversity of GD invertebrates was only explained by plant diversity (12%), and their identity was only explained by soil characteristics (8%). We conclude that vegetation shapes invertebrate communities more importantly than direct effects of TM on invertebrates. Vegetation should be taken into account when addressing the impacts of environmental contamination on animal communities.

A method to assess glyphosate, glufosinate and aminomethylphosphonic acid in soil and earthworms.

A new sensitive and selective analytical methodology to quantify glyphosate (GLY), aminomethylphosphonic acid (AMPA), and glufosinate (GLU) in both soil and earthworms (Allolobophora chlorotica) was developed. The extraction and purification methods were optimized. The samples were extracted with various aqueous solutions (HNO3, H2O, KOH and borate buffer) and derivatized with 9-Fluorenylmethyl chloroformate (FMOCCl). To optimize the extraction step, a method to remove the excess FMOCCl was applied based on liquid-liquid extraction with diethyl ether. The purification of derivatized extracts was carried out using XLB solid phase extraction (SPE) cartridges before internal standard quantification by liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS). The elution step was optimized to obtain the best recoveries possible, which was with acidic methanol (1% formic acid) (67% for GLY, 70% for GLU and 65% for AMPA). The extraction and purification method followed by analysis of the two herbicides and AMPA in soils using LC/MS/MS determined limit of quantification (LOQ) values of 0.030 µg g - 1 for GLY, 0.025 µg g - 1 for AMPA and 0.020 µg g - 1 for GLU . For earthworms, LOQ were 0.23 µg g - 1 for GLY, 0.20 µg g - 1 for AMPA and 0.12 µg g - 1 for GLU. . The developed method was applied to determine these compounds in natural soils and earthworms.