Analytical development for the assessment of pesticide contaminations in blood and plasma of wild birds: The case of grey partridges (Perdix perdix).

In this study, blood and plasma of grey partridges (Perdix perdix) were analyzed to assess their potential contamination by plant protection products (PPP) and especially pesticide compounds. The group of pesticides selected is composed of a huge variety of compounds. Therefore, in this study, two methods were optimized and validated to analyze 104 compounds including herbicides, insecticides, fungicides and photoprotectors or synergists. Various extraction methods found in the literature were compared and adapted for the extraction of pesticides from blood and plasma. After extraction, samples were concentrated then injected for quantification simultaneously in LC-MS/MS and ATD-GC-MS/MS with an automatic thermal desorption step (ATD). Both LC-MS/MS and ATD-GC-MS/MS analyses were performed using the MRM mode with 2 mass transitions for each compound.The two analytical methods achieved a good linearity for the calibration responses in plasma and blood. Methods allowed sensitive detection and quantification in complex biological matrices such as plasma and blood in both LC and GC. For plasma samples and considering all 104 compounds of the study, the average LOD was 0.005 ng mg-1 in LC-MS/MS and 0.035 ng mg-1 in ATD-GC-MS/MS and the average LOQ was 0.017 ng mg-1 and 0.116 ng mg-1 in LC-MS/MS and ATD-GC-MS/MS respectively. Accordingly, the average LOD for blood samples was 0.011 ng mg-1 in LC and 0.028 ng mg-1 in GC whereas the average LOQ was 0.038 ng mg-1 and 0.094 ng mg-1 in LC-MS/MS and ATD-GC-MS/MS respectively. Those analytical methods were then successfully applied to 70 blood samples and 35 plasma samples.

Glyphosate, AMPA and glufosinate in soils and earthworms in a French arable landscape.

Although Glyphosate-based herbicides are often marketed as environmentally friendly and easily biodegradable, its bioavailability and risks to wildlife raise significant concerns. Among non-target organisms, earthworms which live in close contact with the soil can be directly exposed to pesticides and harmed. We investigated soil contamination and the exposure of earthworms to glyphosate, its metabolite AMPA, and glufosinate in an arable landscape in France, both in treated (i.e. temporary grasslands and cereal fields under conventional farming), and nontreated habitats (i.e. hedgerows, permanent grasslands and cereal fields under organic farming) (n = 120 sampling sites in total). Glyphosate, AMPA and glufosinate were detected in 88%, 58% and 35% of the soil samples, and in 74%, 38% and 12% of the earthworm samples, respectively. For both glyphosate and AMPA, concentrations in soils were at least 10 times lower than predicted environmental concentrations. However, the maximum glyphosate soil concentration measured (i.e., 0.598 mg kg-1) was only 2 to 3 times lower than the concentrations revealed to affect earthworms (survival and avoidance) in the literature. These compounds were found both in conventional and organic farming fields, thus supporting a recent study, and for the first time they were detected in hedgerows and grasslands. However, glyphosate and AMPA were more frequently detected in soils from cereal fields and hedgerows than in grasslands, and median concentrations measured in soils from cereal fields were significantly higher than in the two other habitats. Bioaccumulation of glyphosate and AMPA in earthworms was higher than expected according to the properties of the molecules. Our findings raised issues about the high occurrence of glyphosate and AMPA in soils from cropped and more natural areas in arable landscapes. They also highlight the potential for transfer of these molecules in terrestrial food webs as earthworms are prey for numerous animals.