Dermal measurement of exposure to plant protection products: Actual hand exposure from hand washing vs. wearing cotton gloves.

For the authorization of plant protection products, a quantitative non-dietary exposure risk assessment relies on established dermal exposure models, measured mainly using passive dosimetry. Exposure to the hands is determined via hand washing or using cotton gloves as a surrogate for skin. This study compared both methods using operator exposure data available from the Agricultural Operator Exposure Model (AOEM) project report. These data indicate that hand exposure determined using cotton gloves resulted in markedly higher exposure values for all exposure scenarios compared to those determined by hand washes. One explanation for this is that dermal uptake of the residues reduces the amount of residue that can be recovered by hand washing. Uncertainty due to dermal uptake can be addressed by either default assumptions or by specific dermal absorption data. However, this cannot solely account for the large difference observed between the values and is mainly likely to be due to the higher capacity of the cotton gloves vs. human skin to retain residues. The results further indicate that the variability between hand wash samples and cotton glove samples differs between the exposure scenarios. Hence, the level of conservatism related to the use of cotton gloves as surrogate skin remains unknown. In conclusion, this evaluation of the AOEM data indicates that the cotton glove method results in much higher levels of measured hand exposure than the hand wash method. It cannot be excluded that dermal uptake has contributed to that result. However, the findings suggest the higher retention capacity of cotton gloves vs. human skin to be the main impact parameter. The cotton glove method does not provide the results with regards to the protection level that can be expected from the use of protective gloves. Therefore, we believe that the application of the hand wash method is a more accurate measure of exposure levels, if either specific dermal absorption data or, in its absence, default assumptions are applied as adjustment factor.

Transfer of atrazine degradation capability to mineralize aged ¹4C-labeled atrazine residues in soils.

The degradation of environmentally long-term aged (22 years) ¹4C-labeled atrazine residues in soil stimulated by inoculation with atrazine-adapted soil from Belgium, the United States (U.S.), and Brazil at two different moisture regimes (50% WHCmax/slurried conditions) was evaluated. Inoculation of the soil containing the aged ¹4C-labeled atrazine residues with 5, 50, and 100% (w/w) Belgian, U.S., or Brazilian atrazine-adapted soil increased ¹4C-atrazine residue mineralization by a factor of 3.1-13.9, depending upon the amount of atrazine-adapted soil inocula and the moisture conditions. Aged ¹4C-atrazine residue mineralization varied between 2 and 8% for Belgian and between 1 and 2% for U.S. and Brazilian soil inoculum at 50% WHCmax but was increased under slurried conditions, accounting for 8-10% (Belgian soil), 2-7% (Brazilian soil), and 3% (American soil). The results show that an increased degradation of long-term aged ¹4C-labeled atrazine residues is possible by the transfer of atrazine-adapted soil microflora from different soils and regions to non-adapted soil.

Metabolism and persistence of atrazine in several field soils with different atrazine application histories.

To assess the potential occurrence of accelerated herbicide degradation in soils, the mineralization and persistence of (14)C-labeled and nonlabeled atrazine was evaluated over 3 months in two soils from Belgium (BS, atrazine-treated 1973-2008; BC, nontreated) and two soils from Germany (CK, atrazine-treated 1986-1989; CM, nontreated). Prior to the experiment, accelerated solvent extraction of bulk field soils revealed atrazine (8.3 and 15.2 µg kg(-1)) in BS and CK soils and a number of metabolites directly after field sampling, even in BC and CM soils without previous atrazine treatment, by means of LC-MS/MS analyses. For atrazine degradation studies, all soils were incubated under different moisture conditions (50% maximum soil water-holding capacity (WHC(max))/slurried conditions). At the end of the incubation, the (14)C-atrazine mineralization was high in BS soil (81 and 83%) and also unexpectedly high in BC soil (40 and 81%), at 50% WHC(max) and slurried conditions, respectively. In CK soil, the (14)C-atrazine mineralization was higher (10 and 6%) than in CM soil (4.7 and 2.7%), but was not stimulated by slurried conditions. The results revealed that atrazine application history dramatically influences its degradation and mineralization. For the incubation period, the amount of extractable atrazine, composed of residues from freshly applied atrazine and residues from former field applications, remained significantly greater (statistical significance = 99.5 and 99.95%) for BS and CK soils, respectively, than the amount of extractable atrazine in the bulk field soils. This suggests that (i) mostly freshly applied atrazine is accessible for a complex microbial community, (ii) the applied atrazine is not completely mineralized and remains extractable even in adapted soils, and (iii) the microbial atrazine-mineralizing capacity strongly depends on atrazine application history and appears to be conserved on long time scales after the last application.

Accelerated degradation of (14)C-atrazine in brazilian soils from different regions.

The repeated use of a given pesticide may induce a selection of the soil microbial population, resulting in a rapid degradation of the respective xenobiotic. Patterns of atrazine degradation (mineralization, formation of metabolites and nonextractable residues (NER)) were evaluated in two Brazilian soils with a history of atrazine application. Results were compared with those obtained from soils that had no agricultural use or herbicide application history. (14)C-Atrazine mineralization in unsaturated treated soils was high. By the 85th day of incubation, 82% of the applied (14)C-atrazine was mineralized in the Rhodic Hapludox and 74% in the Xanthic Haplustox. Mineralization remained low in nontreated soils (