Pesticide detection in air samples from contrasted houses and in their inhabitants' hair.

In order to identify associations between indoor air contamination and human exposure to pesticides, hair samples from 14 persons (9 adults and 5 children below 12 years) were collected simultaneously with the air of their 5 contrasted houses. Three houses were situated in Alsace (France), one in Lorraine (France) and one in Luxembourg (Luxembourg). Houses were located in urban (n=3), semi-urban (n=1) and rural areas (n=1). Twenty five (25) pesticides were detected at least once in indoor air samples and 20 pesticides were detected at least once in hair samples. The comparison between hair and air samples for the same sampling periods shows that pesticides detected in the two matrices were not necessarily associated. Exposure profiles varied from one home to another but also between inhabitants of the same home, suggesting that exposure can be different between inhabitants of the same home. This study demonstrated the usefulness and the complementarity of hair analysis, for the personalized biomonitoring of people exposure to pesticides, and air analysis, for the identification of airborne exposure and house contamination.

Determination of seven pyrethroids biocides and their synergist in indoor air by thermal-desorption gas chromatography/mass spectrometry after sampling on Tenax TA ® passive tubes.

A method coupling thermal desorption and gas chromatography/mass spectrometry (GC/MS) was developed for the simultaneous determination of 7 pyrethroids (allethrin, bifenthrin, cyphenothrin, imiprothrin, permethrin, prallethrin and tetramethrin) and piperonyl butoxide adsorbed on Tenax TA(®) passive samplers after exposure in indoor air. Thermal desorption was selected as it permits efficient and rapid extraction without solvent used together with a good sensitivity. Detection (S/N>3) and quantification (S/N>10) limits varied between 0.001 ng and 2.5 ng and between 0.005 and 10 ng respectively with a reproducibility varied between 14% (bifenthrin) and 39% (permethrin). The method was used for the comparison indoor air contamination after low-pressure spraying and fumigation application in a rubbish chute situated in the basement of a building.

Analysis of airborne pesticides from different chemical classes adsorbed on Radiello® Tenax® passive tubes by thermal-desorption-GC/MS.

An analytical methodology using automatic thermal desorption (ATD) and GC/MS was developed for the determination of 28 pesticides of different chemical classes (dichlobenil, carbofuran, trifluralin, clopyralid, carbaryl, flazasulfuron, mecoprop-P, dicamba, 2,4-MCPA, dichlorprop, 2,4-D, triclopyr, cyprodinil, bromoxynil, fluroxypyr, oxadiazon, myclobutanil, buprofezin, picloram, trinexapac-p-ethyl, ioxynil, diflufenican, tebuconazole, bifenthrin, isoxaben, alphacypermethrin, fenoxaprop and tau-fluvalinate) commonly used in nonagricultural areas in atmospheric samples. This methodology was developed to evaluate the indoor and outdoor atmospheric contamination by nonagricultural pesticides. Pesticides were sampled passive sampling tubes containing Tenax® adsorbent. Since most of these pesticides are polar (clopyralid, mecoprop-P, dicamba, 2,4-MCPA, dichlorprop, 2,4-D, triclopyr, bromoxynil, fluroxypyr, picloram, trinexapac-p-ethyl and ioxynil), a derivatisation step is required. For this purpose, a silylation step using N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (MtBSTFA) was added before thermal desorption. This agent was chosen since it delivers very specific ions on electronic impact (m/z = M-57). This method was established with special consideration for optimal thermal desorption conditions (desorption temperature, desorb flow and duration; trap heating duration and flow; outlet split), linear ranges, limits of quantification and detection which varied from 0.005 to 10 ng and from 0.001 to 2.5 ng, respectively, for an uncertainty varied from 8 to 30 %. The method was applied in situ to the analysis of passive tubes exposed during herbicide application to an industrial site in east of France.

Coupling ASE, sylilation and SPME-GC/MS for the analysis of current-used pesticides in atmosphere.

An analytical methodology using Accelerated Solvent Extraction (ASE) and a sylilation procedure coupled to Solid Phase Micro-Extraction (SPME) and GC/MS was developed for the determination of 31 pesticides of different chemical classes (urea, phenoxy acids, pyrethrenoïds, etc.) commonly used in non-agricultural areas in atmospheric samples. This methodology was developed to evaluate the outdoor atmospheric contamination by non-agricultural pesticides. Pesticides were simultaneously sampled on glass fibre filters and on XAD-2 resin traps by using a low volume sampler (Partisol) for 1 week. Traps were extracted by Accelerated Solvent Extraction (ASE) with acetonitrile and concentrated to 1 mL by using a rotary evaporator. 500 µL of the extract was dissolved in 19.5 mL of 1.5% NaCl acidified water (pH=3) and SPME extracted by PA fibre for 55 min at 50 °C. Since most of the studied pesticides are polar or thermo-labile, a derivatisation step by injection of 2 µL of MtBSTFA just before SPME desorption was done. MtBSTFA was chosen since it delivers very specific ions on electronic impact (m/z=M-57). Detection limits varied between 5 and 179 ng resin(-1) and between 0.3 and 126 ng filter(-1) corresponding to 2 and 750 pg m(-3) and 30 and 1165 pg m(-3) for 168 m(3) of air pumped through traps. Quantification limits varied between 18 and 595 ng resin(-1) and between 1 and 420 ng filter(-1) corresponding to 107 and 3542 pg m(-3) and 6 and 2500 pg m(-3) for 168 m(3) of air pumped through traps. Uncertainties varied between 7.2% and 39.6% and between 7.2% and 53.4% respectively for filter and resin. The method was used for the analysis of atmospheric samples collected in a background urban site of Strasbourg (east of France) during spring and summer 2010.

Simultaneous analysis of pesticides from different chemical classes by using a derivatisation step and gas chromatography-mass spectrometry.

This work presents a new method to analyse simultaneously by GC-MS 31 pesticides from different chemical classes (2,4 D, 2,4 MCPA, alphacypermethrin, bifenthrin, bromoxynil, buprofezin, carbaryl, carbofuran, clopyralid, cyprodinil, deltamethrin dicamba, dichlobenil, dichlorprop, diflufenican, diuron, fenoxaprop, flazasulfuron, fluroxypyr, ioxynil, isoxaben, mecoprop-P, myclobutanil, oryzalin, oxadiazon, picloram, tau-fluvalinate tebuconazole, triclopyr, trifluralin and trinexapac-p-ethyl). This GC-MS method will be applied to the analysis of passive samplers (Tenax(®) tubes and SPME fiber) used for the evaluation of the indoor and outdoor atmospheric contamination by non-agricultural pesticides. The method involves a derivatisation step for thermo-labile or polar pesticides. Different agents were tested and MtBSTFA (N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide), a sylilation agent producing very specific fragments [M-57], was retained. However, diuron could not be derivatised and the isocyanate product was used for identification and quantification. Pesticides which did not need a derivatisation step were not affected by the presence of the derivatisation agent and they could easily be analysed in mixture with derivatised pesticides. The method can be coupled to a thermal-desorption unit or to SPME extraction for a multiresidue analysis of various pesticides in atmospheric samples.

Snails as indicators of pesticide drift, deposit, transfer and effects in the vineyard.

This paper presents a field-study of real pesticide application conditions in a vineyard. The objective was to measure the exposure, the transfer and the effects of pesticides on a non-target soil invertebrate, the land snail Helix aspersa. There was no drift of the herbicides (glyphosate and glufosinate) whereas the fungicides (cymoxanil, folpet, tebuconazole and pyraclostrobin) were detected up to 20 m from the treated area. For folpet and particularly tebuconazole, spray deposits on soil (corresponding to losses for the intended target i.e. the vine leaves) were high (41.1% and 88.8% loss of applied dose, respectively). For herbicides, the target was the soil and losses (percentage of compounds which did not reach the soil) were of 22% for glufosinate and 52% for glyphosate. In the study plot, glyphosate was transferred to and accumulated in snail tissues (4 mg kg(-1) dry weight, dw), as was its metabolite AMPA (8 mg kg(-1) dw) which could be in relation with the reduced growth observed in snails. No effects on snail survival or growth were found after exposure to the other organic compounds or to copper and sulphur-fungicides, although transfer of tebuconazole, pyraclostrobin and copper occurred. This study brings original field data on the fate of pesticides in a vineyard agro-ecosystem under real conditions of application and shows that transfer and effects of pesticides to a non-target organism occurred.

Analytical method for assessing potential dermal exposure to pesticides of a non-agricultural occupationally exposed population.

To measure dermal exposure of a non-agricultural occupationally exposed population to pesticides, a new method has been developed for analysis of 13 pesticides from different classes (fungicides, herbicides, insecticides) on dermal patches. The method includes extraction of the patches and analysis of the pesticides by GC-MS and/or HPLC-fluorescence. Water-soluble pesticides (glyphosate and glufosinate) on patches were ultrasonically extracted twice with ultra-pure water for 10 min and analysed by HPLC-fluorescence after derivatisation with FMOC. Organic-soluble pesticides (bifenthrin, cyprodinil, difufenicanil, fludioxonil, oxadiazon, pyriproxyfen, clopyralid, 2,4-D, fluroxypyr, 2,4-MCPA, and triclopyr) were extracted ultrasonically twice for 10 min with 70:30 dichloromethane-acetonitrile and analysed by GC-MS directly or after derivatisation with N-methyl-N-tert-butyldimethylsilyltrifluoroacetamide. Detection limits varied between 3 and 4 µg L(-1) for water-soluble pesticides and between 1 and 10 µg L(-1) for organic-soluble pesticides.