Water pressure head and temperature impact on isoxaflutole degradation in crop residues and loamy surface soil under conventional and conservation tillage management

Laboratory incubations were performed in order to evaluate the dissipation of the proherbicide isoxaflutole in seedbed layer soil samples from conventional and conservation tillage systems and in maize and oat residues left at the soil surface under conservation tillage. The effects of temperature and water pressure head on radiolabelled isoxaflutole degradation were studied for each sample for 21 d. Mineralisation of isoxaflutole was low for all samples and ranged from 0.0% to 0.9% of applied ¹⁴C in soil samples and from 0.0% to 2.4% of applied ¹⁴C in residue samples. In soil samples, degradation half-life of isoxaflutole ranged from 9 to 26 h, with significantly higher values under conservation tillage. In residue samples, degradation half-life ranged from 3 to 31 h, with significantly higher values in maize residues, despite a higher mineralisation and bound residue formation than in oat residues. Whatever the sample, most of the applied ¹⁴C remained extractable during the experiment and, after 21 d, less than 15% of applied ¹⁴C were unextractable. This extractable fraction was composed of diketonitrile, benzoic acid derivative and several unidentified metabolites, with one of them accounting for more than 17% of applied ¹⁴C. This study showed that tillage system design, including crop residues management, could help reducing the environmental impacts of isoxaflutole.     

Pesticide residue removal in classic domestic processing of tomato and its effects on product quality

This study was undertaken to evaluate the effectiveness of several household practices (washing with water or acidic, alkaline, and oxidizing solutions, and peeling) in minimizing pesticide residue contamination of tomatoes, as well as the impact on the quality of the treated fruit. Tests were performed using two systemic fungicides (azoxystrobin and difenoconazole) and one contact fungicide (chlorothalonil). Solid-liquid extraction with low temperature partition (SLE/LTP) and liquid-liquid extraction with low temperature partition (LLE/LTP) were used to prepare the samples for pesticides determination by gas chromatography. Washing the tomatoes with water removed approximately 44% of chlorothalonil, 26% of difenoconazole, and 17% of azoxystrobin. Sodium bicarbonate (5%) and acetic acid (5%) solutions were more efficient, removing between 32 and 83% of the residues, while peeling removed from 68 to 88% of the pesticides. The washing solutions altered some fruit quality parameters, including acidity and chroma, and also caused weight loss. Acetic acid (0.15 and 5%) and hypochlorite (1%) solutions had the greatest effect on these parameters.     

Fate in soil of 14C-sulfadiazine residues contained in the manure of young pigs treated with a veterinary antibiotic

The fate of ¹⁴C-labeled sulfadiazine (¹⁴C-SDZ) residues was studied in time-course experiments for 218 days of incubation using two soils (A_p horizon of loamy sand, orthic luvisol; A_p horizon of silt loam, cambisol) amended with fresh and aged (6 months) ¹⁴C-manure [40 g kg^?1 of soil; 6.36 mg of sulfadiazine (SDZ) equivalents per kg of soil], which was derived from two shoats treated with ¹⁴C-SDZ. Mineralization of ¹⁴C-SDZ residues was below 2% after 218 days depending little on soil type. Portions of extractable ¹⁴C (ethanol-water, 9:1, v/v) decreased with time to 4–13% after 218 days of incubation with fresh and aged ¹⁴C-manure and both soils. Non-extractable residues were the main route of the fate of the ¹⁴C-SDZ residues (above 90% of total recovered ¹⁴C after 218 days). These residues were high immediately after amendment depending on soil type and aging of the ¹⁴C-manure, and were stable and not remobilized throughout 218 days of incubation. Bioavailable portions (extraction using CaCl₂ solution) also decreased with increasing incubation period (5–7% after 218 days). Due to thin-layer chromatography (TLC), 500 μg of ¹⁴C-SDZ per kg soil were found in the ethanol-water extracts immediately after amendment with fresh ¹⁴C-manure, and about 50 μg kg^?1 after 218 days. Bioavailable ¹⁴C-SDZ portions present in the CaCl₂ extracts were about 350 μg kg^?1 with amendment. Higher concentrations were initially detected with aged ¹⁴C-manure (ethanol-water extracts: 1,920 μg kg^?1; CaCl₂ extracts: 1,020 μg kg^?1), probably due to release of ¹⁴C-SDZ from bound forms during storage. Consistent results were obtained by extraction of the ¹⁴C-manure-soil samples with ethyl acetate; portions of N-acetylated SDZ were additionally determined. All soluble ¹⁴C-SDZ residues contained in ¹⁴C-manure contributed to the formation of non-extractable residues; a tendency for persistence or accumulation was not observed. SDZ's non-extractable soil residues were associated with the soluble HCl, fulvic acids and humic acids fractions, and the insoluble humin fraction. The majority of the non-extractable residues appeared to be due to stable covalent binding to soil organic matter.     

Impact of genetic diversity and inbreeding on the life-history of Chironomus midges over consecutive generations

We report results of a multigenerational experiment with Chironomus riparius. Two strains with a high and a low level of genetic variability were exposed to a low, environmentally relevant TBT concentration of 80 μg Sn kg⁻¹ sediment dw nominally (time weighted mean, based on measured concentrations: 4.5 μg Sn kg⁻¹ sediment dw), and various life history traits as well as genetic diversity were monitored for eleven consecutive generations. While TBT effects are hardly visible in the outbred and genetically diverse strain, the inbred and genetically impoverished strain shows a clearly reduced population growth rate compared to the control. Moreover, the impoverished strain shows an increase in fitness over time. Analyses of variation at five microsatellite loci revealed that the level of genetic variation is strongly reduced in the inbred compared to the outbred strain. Moreover, genetic diversity increases over time in the inbred strain. This finding explains the observed increase in fitness in both inbred lineages (control and TBT exposed). The results document that inbreeding and the level of genetic diversity might be of crucial importance in populations under pollution stress. Furthermore, ecotoxicological bioassays have to consider genetic diversity if results between laboratories should be comparable. Our data provides evidence that genetic diversity strongly contributes to the survival of a population exposed to chemical pollution.     

Bioavailability and toxicological potential of sunflower-bound residues of 14C-chlorpyrifos insecticide in rats

Sunflower plants were treated with ¹⁴C-chlorpyrifos under conditions simulating local agricultural practice. Residues present in the oil, methanol extract and cake of the treated sunflower seeds were 7.2, 2.8, and 12 ppm, respectively. When rats fed on sunflower cake containing bound residues for three days, the animals eliminated 46 % of the radioactivity in urine, 25 % in feces and 10 % in the expired air. A further bioavailable amount of 8 % was found in selected organs indicating that the bound residues were highly bioavailable. Chromatographic analysis of urine extract revealed the presence of the parent compound, its oxon, desethyl chlorpyrifos and desethyl chlorpyrifos oxon as free metabolites in addition to a conjugated metabolite. It was liberated by acid hydrolysis and identified as 3,5,6-trichloro-2-hydroxypyridine. Bound residues were found to have biological effects such as inhibition of rat plasma ChE, elevations of liver parameters (ALT, AST, and ALP), decrease in total protein and albumin content suggesting a hepatotoxic potential. A significant increase in the values of creatinine, urea, cholesterol, triglycerides and significant decrease in Catalase and Glutathion-S-Transfrase were observed in treated rats.     

Estimation of sampling uncertainty for determination of pesticide residues in plant commodities

In order to provide residue data for refining the estimated sampling uncertainty, a coordinated research program was initiated for performing field studies on residues in individual items of leafy vegetables, small and large crops. The trials were carried out in 13 countries with 3 small fruits, 5 large crops, 2 medium/large crops and 3 leafy vegetables. The 25 pesticide active ingredients applied represented the dicarboximide (3), organophosphorus (8), synthetic pyrethroids (5), phthalimides (2), organochlorine (1) and other types of pesticides (6). In addition, 11 supervised field trials were performed in grapes and lettuce by the pesticide manufacturers, and their results were provided for evaluation. The studies represented actual agriculture practice around the world, and provide reliable data for estimation of sampling uncertainty. Based on the 12346 residue data, the best estimate for the relative sampling uncertainty for composite samples, assuming sample size of 10 for small crops and leafy vegetables and 5 for large crops, with 95% confidence limits in brackets are: small commodities: 0.25 (0.20–0.29); Brassica leafy vegetables: 0.20 (0.16–0.24); large commodities: 0.33 (0.29–0.38).     

Distribution and persistence of carbaryl in some terrestrial and aquatic components of a forest environment

Abstract

An oil‐based formulation of carbaryl (1‐naphthyl N‐methyl‐carbamate) (Sevin‐2‐Oil) was applied twice by a fixed‐wing aircraft at a dosage rate of 280 g of A.I./ha/application to a coniferous forest near Allardville, New Brunswick. The highest concentrations of the chemical in fir foliage, litter and forest soil 1 h after application were respectively 4.20, 1.21 and 0.59 ppm (fresh weight). The residues dissipated rapidly and the DT50 values obtained from the depletion curves were 2.3 d for foliage and 1.5 d for litter and soil samples. Very low levels (<0.1 ppm) of carbaryl persisted in foliage and litter beyond the 10 d sampling period. The maximum residue level found in stream water was 0.314 ppm and more than 50% of it had dissipated within 1 h. Low but detectable levels (0.001 ppm) of the chemical persisted in water until the end of the 10 d sampling period. Sediment samples contained a maximum level of 0.04 ppm, which dissipated below the detection limit within 5 h. Brook trout and slimy sculpins captured in the stream 1 d after the spray contained on average about 0.04 ppm of carbaryl and none of it was found in 3 d postspray samples.     

Limitations in the determination of maximum residue limits and highest residues of pesticides: Part I

The pesticide usages are controlled by comparing residue concentrations in treated commodities to legally permitted maximum levels (MRLs) determined based on supervised trials designed to reflect likely maximum residues occurring in practice following authorised use. The number of trials available may significantly affect the accuracy of estimated maximum residues. We conducted a study with synthetic lognormal distributions with mean of 1 and standard deviations of 0.8 and 1.0, which reflect the residue distributions observed in practice. The likely residues in samples were modelled by drawing random samples of size 3, 5, 10 and 25 from the synthetic populations. The results indicate that the estimations of highest residues (HR), used for calculation of short-term intake, and the MRLs, serving as legal limits, are very uncertain based on 3–5 trials indicated by the calculated HR_0.975/HR_0.025 and MRL_0.975/MRL_0.025 ratios of 12 and 9, and 13 and 10, respectively, which question the suitability of such trials for the intended purpose. As the 95% range of HR and MRL rapidly decreases with number of trials, ideally ≥15 but minimum 6–8 trials should be used for estimation of HR and MRL according to the current typical practice of Codex Alimentarius.     

Phosmet residues in an orchard and adjacent recreational area 1

Abstract

Two cover sprays of phosmet were applied to an orchard adjoining a camping area and a bird sanctuary with a resident goose population. Insecticide residues were monitored on orchard leaves, orchard ground cover, ground cover in the camp‐site and along the adjacent lakeshore. Despite attempts to minimize drift, significant spray residues were found outside the target area. Residues on ground cover and leaves were reduced by sprinkler irrigation subsequent to spray application.     

Distribution,fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, ¹⁴C- and ¹³C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied ¹⁴C was mineralized. The bioavailable, water extractable portion was low (9 % of applied ¹⁴C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied ¹⁴C was incorporated into organo-clay complexes as NER, whereas 9 % of applied ¹⁴C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.