B-type esterases in the snail Xeropicta derbentina: an enzymological analysis to evaluate their use as biomarkers of pesticide exposure

The study was prompted to characterize the B-type esterase activities in the terrestrial snail Xeropicta derbentina and to evaluate its sensitivity to organophosphorus and carbamate pesticides. Specific cholinesterase and carboxylesterase activities were mainly obtained with acetylthiocholine (K_m = 77.2 mM; V_max = 38.2 mU/mg protein) and 1-naphthyl acetate (K_m = 222 mM, V_max = 1095 mU/mg protein) substrates, respectively. Acetylcholinesterase activity was concentration-dependently inhibited by chlorpyrifos-oxon, dichlorvos, carbaryl and carbofuran (IC50 = 1.35 × 10⁻⁵-3.80 × 10⁻⁸ M). The organophosphate-inhibited acetylcholinesterase activity was reactivated in the presence of pyridine-2-aldoxime methochloride. Carboxylesterase activity was inhibited by organophosphorus insecticides (IC50 = 1.20 × 10⁻⁵-2.98 × 10⁻⁸ M) but not by carbamates. B-esterase-specific differences in the inhibition by organophosphates and carbamates are discussed with respect to the buffering capacity of the carboxylesterase to reduce pesticide toxicity. These results suggest that B-type esterases in X. derbentina are suitable biomarkers of pesticide exposure and that this snail could be used as sentinel species in field monitoring of Mediterranean climate regions.     

Comparison of annual dry and wet deposition fluxes of selected pesticides in Strasbourg, France

This work summarizes the results of a study of atmospheric wet and dry deposition fluxes of Deisopropyl-atrazine (DEA), Desethyl-atrazine (DET), Atrazine, Terbuthylazine, Alachlor, Metolachlor, Diflufenican, Fenoxaprop-p-ethyl, Iprodione, Isoproturon and Cymoxanil pesticides conducted in Strasbourg, France, from August 2000 through August 2001. The primary objective of this work was to calculate the total atmospheric pesticide deposition fluxes induced by atmospheric particles. To do this, a modified one-dimensional cloud water deposition model was used. All precipitation and deposition samples were collected at an urban forested park environment setting away from any direct point pesticide sources. The obtained deposition fluxes induced by atmospheric particles over a forested area showed that the dry deposition flux strongly contributes to the total deposition flux. The dry particle deposition fluxes are shown to contribute from 4% (DET) to 60% (cymoxanil) to the total deposition flux (wet + dry).     

Degradation of carbofuran and carbofuran-derivatives in presence of humic substances under basic conditions

The influence of humic aggregates in water solution upon the chemical stability of carbofuran (CF) and the carbofuran-derivatives, 3-hydroxy-carbofuran (HCF) and 3-keto-carbofuran (KCF), has been investigated in basic media. An inhibition upon the basic hydrolysis of 3-hydroxy-carbofuran and 3-keto-carbofuran (∼1.7 and ∼1.5-fold, respectively) was observed and it was rationalized in terms of the micellar pseudophase model. Nevertheless, non-significant effect upon the carbofuran stability was found in the presence of humic substances. These behaviors have been compared with the corresponding ones in other synthetic colloidal aggregates.     

Pesticides and Essential Minerals Modify Endogenous Antioxidants and Cytochrome P450 in Tissues of Rats

Two experiments were conducted in male Sprague Dawley (SD) rats (175–200 g) to determine changes in the activities of endogenous antioxidants superoxide dismutase (SOD), glutathione peroxidase (GPX), cytochrome P450 (ethoxyresorufin deethylase; EROD) and concentrations of glutathione (GSH) in the blood, liver, and small intestinal mucosa (IM). In both experiments, six rats/group were fed diets based on the AIN-93M diet (Control) or the same modified to contain either 500 mg calcium (Low Ca), 7 mg Zn (Low Zn): 2 mg copper (Low Cu), 60 mg zinc (High Zn) or 12 mg copper (High Cu) in the following combination: Control, LCa/LZn, LCa/LZn/LCu, or HZn/HCu, with and without a pesticide mixture containing acephate, endosulfan, and thiram at 25% LD₅₀ for four or two weeks. Pesticides decreased feed intake and weight gain in all groups by 28%. Erythrocyte SOD was higher than control in the HZn/HCu group and in the LCa/LZn/LCu and HZn/HCu groups with pesticide (P# 0.05). Plasma GPX declined by more than 55% in all the groups with and without pesticides compared to the control. The LCa/LZn/LCu and HZn/HCu diets with and without pesticides reduced GPX in the IM by up to 88%, 40%, and 74%, respectively, than the control. Plasma GSH was about 20% higher than the control in most groups with and without pesticides in the diet. Liver and IM GSH were higher than the control in the HZn/HCu group, whereas IM GSH concentrations were lower than the control in the LCa/LZn and LCa/LZn/LCu groups (P#0.05). All three experimental diets with and without pesticides had a significant effect on liver EROD activity (P#0.05). The results indicate that endogenous antioxidants and EROD were independently modified by dietary zinc and copper levels and pesticides.     

Comparative toxicity of some pesticides on human health and some aquatic species

Abstract

Inhibition studies have been carried on the hydrolysis reactions catalyzed by cholinesterases taken from electric eel, human and horse serums by Sevin, Aldrin and Malathion. Three esters of p‐nitrophenol have been used as substrates. The degree of inhibition has been used as a measure of the comparative toxicity of these pesticides on these cholinesterases.     

A monitoring study of workers handling pesticides in warehouses and godowns

Abstract

Monitoring observations made on 60 operators involved in pesticide application work in godowns and warehouses and 60 matched control workers are reported. Occupational exposure history and medical history are noted. Biochemical investigations, plasma and RBC cholinesterase estimations are included along with medical examination of the workers. Workers were found to be mostly exposed to Celphos, DDVP, Malathion, Pyrethrum, etc, and the use of protective devices were very limited. Cases of significant reduction in plasma and RBC cholinesterase activity were found. Frequency of symptoms like dizziness, headache, lachrymation, burning sensation in eyes, nausea and anorexia, etc, were much more in the exposed workers. No cases of clinical poisoning attributable to occupational exposure to pesticides were reported by the workers.     

Pesticide concentration variations correlated with well bore volume removal in shallow coastal plain ground water

Abstract

The effects of well bore volume removal (V_n) on the concentration of alachlor [2‐chloro‐N‐(2,6‐diethylphenyl)‐N‐(methoxy methyl) acetamide] and prometon (6‐methoxy‐N,N'‐bis(1‐methylethyl)‐1,3,5‐triazine‐2,4‐diamine] in ground water obtained from three monitoring wells installed in the Coastal Plain region of North Carolina was investigated. Seasonal effects were also investigated by conducting the exercise in February and May. In the majority of cases, the lowest pesticide concentrations occurred in the initial well bore volume (V₁ = stagnant water). Removal of additional well bore volumes (V₂ to V₁₀) from two of the wells resulted in pesticide concentrations that did not vary substantially. This indicates that a representative aquifer sample was obtainable, in most cases from these wells, after removal of the initial well bore volume. In contrast, a third well required the purging of two well bore volumes before a stable alachlor concentration was achieved. Seasonal effects of bore volume removal vs. pesticide concentrations for the three wells were not significant (P > 0.05). It was concluded that a protocol for improved accuracy in pesticide analyses of ground water can be obtained by establishing a pesticide concentration‐purging (well bore volume) relationship for each well.     

Sensitivity of agricultural runoff loads to rising levels of CO2 and climate change in the San Joaquin Valley watershed of California

The Soil and Water Assessment Tool (SWAT) was used to assess the impact of climate change on sediment, nitrate, phosphorus and pesticide (diazinon and chlorpyrifos) runoff in the San Joaquin watershed in California. This study used modeling techniques that include variations of CO₂, temperature, and precipitation to quantify these responses. Precipitation had a greater impact on agricultural runoff compared to changes in either CO₂ concentration or temperature. Increase of precipitation by ±10% and ±20% generally changed agricultural runoff proportionally. Solely increasing CO₂ concentration resulted in an increase in nitrate, phosphorus, and chlorpyrifos yield by 4.2, 7.8, and 6.4%, respectively, and a decrease in sediment and diazinon yield by 6.3 and 5.3%, respectively, in comparison to the present-day reference scenario. Only increasing temperature reduced yields of all agricultural runoff components. The results suggest that agricultural runoff in the San Joaquin watershed is sensitive to precipitation, temperature, and CO₂ concentration changes.     

Absorption of current use pesticides by snapping turtle (Chelydra serpentina) eggs in treated soil

Reptiles often breed within agricultural and urban environments that receive frequent pesticide use. Consequently, their eggs and thus developing embryos may be exposed to pesticides. Our objectives were to determine (i) if turtle eggs are capable of absorbing pesticides from treated soil, and (ii) if pesticide absorption rates can be predicted by their chemical and physical properties. Snapping turtle (Chelydra serpentina) eggs were incubated in soil that was treated with 10 pesticides (atrazine, simazine, metolachlor, azinphos-methyl, dimethoate, chlorpyrifos, carbaryl, endosulfan (I and II), captan, and chlorothalonil). There were two treatments, consisting of pesticides applied at application rate equivalents of 1.92 or 19.2 kg a.i/ha. Eggs were removed after one and eight days of exposure and analyzed for pesticides using gas chromatography coupled with a mass selective detector (GC-MSD) or high performance liquid chromatography (HPLC). Absorption of pesticides in eggs from soil increased with both magnitude and duration of exposure. Of the 10 pesticides, atrazine and metolachlor generally had the greatest absorption, while azinphos-methyl had the lowest. Chlorothalonil was below detection limits at both exposure rates. Our preliminary model suggests that pesticides having the highest absorption into eggs tended to have both low sorption to organic carbon or lipids, and high water solubility. For pesticides with high water solubility, high vapor pressure may also increase absorption. As our model is preliminary, confirmatory studies are needed to elucidate pesticide absorption in turtle eggs and the potential risk they may pose to embryonic development.     

Pesticide Environmental Accounting: a method for assessing the external costs of individual pesticide applications

The Pesticide Environmental Accounting (PEA) tool provides a monetary estimate of environmental and health impacts per hectare-application for any pesticide. The model combines the Environmental Impact Quotient method and a methodology for absolute estimates of external pesticide costs in UK, USA and Germany. For many countries resources are not available for intensive assessments of external pesticide costs. The model converts external costs of a pesticide in the UK, USA and Germany to Mediterranean countries. Economic and policy applications include estimating impacts of pesticide reduction policies or benefits from technologies replacing pesticides, such as sterile insect technique. The system integrates disparate data and approaches into a single logical method. The assumptions in the system provide transparency and consistency but at the cost of some specificity and precision, a reasonable trade-off for a method that provides both comparative estimates of pesticide impacts and area-based assessments of absolute impacts.