Use of cholinesterase activity in monitoring chlorpyrifos exposure of steer cattle after topical administration

The aim of this work was to study the pharmacokinetic behavior and the inhibitory effect of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities of chlorpyrifos (CPF) in steer cattle after pour-on administration. Determination of cholinesterase activity in plasma and erythrocyte was carried out according to Ellman kinetic method. CPF was analyzed by gas chromatography. AChE was the predominant form of cholinesterase analyzed, with low levels of BChE in plasma. Following the treatment with CPF, the maximum inhibitory effect on AChE or BChE were 50.88 ± 11.57 and 42.66 ± 12.01%, respectively. The chlorpyrifos plasma concentrations observed were low and they presented a high variability. Chlorpyrifos peak plasma concentration (10.42 ± 4.76 μ g/L) was reached at 8.42 ± 13.97 h. The pesticide was not detected in plasma after 48 h post treatment. The values of area under the curve (AUC) were 118.48 ± 87.46 μ g· h/L and mean resistance time (MRT) were 13.38 ± 10.41 h. The pour-on exposure to the organophosphate chlorpyrifos significantly reduced AChE and BChE activity in steer cattle and the recovery was not reached on 50 days post-treatment.     

Examining the joint toxicity of chlorpyrifos and atrazine in the aquatic species: Lepomis macrochirus, Pimephales promelas and Chironomus tentans

The joint toxicity of chlorpyrifos and atrazine was compared to that of chlorpyrifos alone to discern any greater than additive response using both acute toxicity testing and whole-body residue analysis. In addition, acetylcholinesterase (AChE) inhibition and biotransformation were investigated to evaluate the toxic mode of action of chlorpyrifos in the presence of atrazine. The joint toxicity of atrazine and chlorpyrifos exhibited no significant difference in Lepomis macrochirus compared to chlorpyrifos alone; while studies performed with Pimephales promelas and Chironomus tentans, did show significant differences. AChE activity and biotransformation showed no significant differences between the joint toxicity of atrazine and chlorpyrifos and that of chlorpyrifos alone. From the data collected, the combination of atrazine and chlorpyrifos pose little additional risk than that of chlorpyrifos alone to the tested fish species.     

农药毒死蜱的生态风险及其微生物修复技术研究进展

毒死蜱是替代甲胺磷和对硫磷等高毒农药的高效有机磷杀虫剂,在世界范围得到广泛使用.但是,环境毒理学研究发现,毒死蜱对生态环境具有潜在的危险性,甚至被认为具有干扰内分泌的功能,许多国家对毒死蜱在农产品中的残留量有严格的规定.因此,深入研究毒死蜱的生态风险问题是当务之急.对国内外关于毒死蜱的残留活性、生态毒理、降解机制以及生物修复等方面的研究进行了综述,以期对毒死蜱的合理管理和使用提供科学依据.     

European starling nestling response to chlorpyrifos exposure in a corn agroecosystem

European starling (Sturnus vulgaris) nestlings were used as a surrogate to study the effect of chlorpyrifos application to a corn agroecosystem on songbird reproduction. Chlorpyrifos was applied in a T‐band at 1.3 kg AI/ha, and residues were measured in soil, earthworms, ground‐dwelling insects, and diet items collected from the crop of starling nestlings. Chlorpyrifos levels in soil peaked at 34.2 μg/g, 4 days post‐application, and dissipated to trace levels by 64 days post‐application. Concentrations of chlorpyrifos in earthworms and ground‐dwelling insects reached 0.9 and 0.7 ug/g, respectively. Starling nestling diet items included invertebrates from eight orders with chlorpyrifos concentrations ranging from trace levels to 10.6 μg/g in earthworms. Nestling brain and plasma cholinesterase (ChE) activity and body mass measurements were taken at 3, 8, and 13 days post‐hatch (DPH). Adult starling fecundity was also measured. Body mass differences between treatment and reference site nestlings at 3 and 13 DPH were not significant at α = 0.05. However, 8 DPH nestlings from the Treatment Site had a transient reduction in weight (p = 0.03) when compared with 8 DPH reference nestlings. There were no significant differences in brain or plasma ChE activities of 3, 8, or 13 DPH nestlings. Further, multiple measures of fecundity (i.e., clutch size, hatching percentage, and fledging percentage) indicated that chlorpyrifos application did not affect starling nestling survival to fledging, as the values from the Treatment and Reference Site were nearly identical. This screening‐level study suggests that although one age group of starling nestlings from the Treatment Site weighed less than their Reference Site counterparts, a single T‐band application of chlorpyrifos did not impair starling nesting success.     

The distribution of chlorpyrifos following a crack and crevice type application in the US EPA Indoor Air Quality Research House

A study was conducted in the US EPA Indoor Air Quality (IAQ) Research House to determine the spatial and temporal distribution of chlorpyrifos following a professional crack and crevice application in the kitchen. Following the application, measurements were made in the kitchen, den and master bedroom over 21 days. Airborne concentrations were collected using both polyurethane foam (PUF) and the OSHA versatile sampler composed of XAD and PUF media located in tandem. Measured airborne concentrations were similar for the two samplers and were higher in the three rooms following the application. The highest measured concentrations were reached during the initial 24-h following application; concentrations subsequently declined over the 21-day study period to levels slightly above background. Spatial and temporal distributions onto surfaces were measured using 10-cm² rayon deposition coupons located on the floor. Sections were cut from existing carpet to determine the total extractable residues. Chlorpyrifos was measured from all matrixes in the kitchen, den and bedroom and the data shows the transport of airborne residues from the point of application to remote locations in the house. The findings are compared and discussed relative to another study conducted in which total release aerosols containing chlorpyrifos were activated in the IAQ research house and the resulting distributions evaluated. For both studies dose estimates were constructed for the exposure pathways using the Stochastic Human Exposure and Dose Estimation Model for pesticides.The United States Environmental Protection Agency has been mandated to examine children's exposure to environmental pollutants such as pesticides. This research specifically reduces uncertainties associated with estimating children's potential exposures to residentially applied pesticides and provides inputs to further evaluate and validate residential exposure models which might be used to reduce exposures and perform risk assessments.     

Structural and metabolic responses of microbial community to sewage-borne chlorpyrifos in constructed wetlands

Long-term use of chlorpyrifos poses a potential threat to the environment that cannot be ignored, yet little is known about the succession of substrate microbial communities in constructed wetlands(CWs) under chlorpyrifos stress. Six pilot-scale CW systems receiving artificial wastewater containing 1 mg/L chlorpyrifos were established to investigate the effects of chlorpyrifos and wetland vegetation on the microbial metabolism pattern of carbon sources and community structure, using BIOLOG and denaturing gradient gel electrophoresis(DGGE) approaches. Based on our samples, BIOLOG showed that Shannon diversity(HV) and richness(S) values distinctly increased after 30 days when chlorpyrifos was added. At the same time, differences between the vegetated and the non-vegetated systems disappeared. DGGE profiles indicated that H Vand S had no significant differences among four different treatments. The effect of chlorpyrifos on the microbial community was mainly reflected at the physiological level. Principal component analysis(PCA) of both BIOLOG and DGGE showed that added chlorpyrifos made a difference on test results.Meanwhile, there was no difference between the vegetation and no-vegetation treatments after addition of chlorpyrifos at the physiological level. Moreover, the vegetation had no significant effect on the microbial community at the genetic level. Comparisons were made between bacteria in this experiment and other known chlorpyrifos-degrading bacteria. The potential chlorpyrifos-degrading ability of bacteria in situ may be considerable.     

Toxic effects of chlorpyrifos on lysozyme activities,the contents of complement C3 and IgM,and IgM and complement C3 expressions in common carp (Cyprinus carpio L.)

Chlorpyrifos is one of the organophosphate pesticides widely used in agricultural practices throughout world. It has resulted in a series of toxicological and environmental problems, such as impacts on many non-target aquatic species, including fish. In the present study, toxic effects of chlorpyrifos on lysozyme activities, contents of IgM and complement C3, and the expressions of IgM and complement C3 at mRNA level in common carp were evaluated by acute exposure of 15 (1/10 LC₅₀) or 75 μg L⁻¹ (1/2 LC₅₀) of chlorpyrifos for 7 d. The results of acute toxicity tests showed that the 96 h-LC₅₀ of chlorpyrifos for common carp was determined to be 149 μg L⁻¹. We also found that chlorpyrifos promoted lysozyme activities at the earlier stages of exposure but inhibited it at the late stages in the serum, hepatopancreas, and spleen of common carp. Furthermore, it was observed that chlorpyrifos-exposure decreased IgM contents in fish serum and spleen while increased it in kidney. No obvious change was found in the contents of complement C3 in fish spleen, while a slight increase of complement C3 was observed in fish serum and kidney after 1 d of chlorpyrifos-exposure. In addition, the results of quantitative real-time PCR showed that IgM and complement C3 expressions were up-regulated at the earlier stage of exposure but down-regulated at later stage. Our results indicate that chlorpyrifos causes immunotoxicity to common carp.     

Chlorpyrifos acute exposure induces hyperglycemia and hyperlipidemia in rats

In this study we evaluated the hyperglycemic and hyperlipidemic effects of chlorpyrifos (CPF) after an acute exposure in rats. The mechanisms involved in hyperglycemia induced by CPF were studied. A single dose of CPF (50 mg kg⁻¹, subcutaneous, s.c.) was administered to overnight-fasted rats. Glucose and corticosterone levels, lipid status and paraoxonase (PON1) activity were determined in plasma of rats. Cardiovascular risk factors and the atherogenic index were calculated. Glycogen levels, tyrosine aminotransferase (TAT) and glucose-6-phosphatase (G6Pase) activities were determined in livers of rats. Cerebral acetylcholinesterase (AChE) activity was also determined. CPF caused an increase in glucose and glycogen levels as well as in TAT and G6Pase activities. The CPF exposure caused an increase in corticosterone levels, an inhibition of AChE activity and a reduction of PON1 activity. Regarding the lipid status, CPF induced an increase in triglycerides (TG) and low-density lipoprotein-cholesterol (LDL) levels and a decrease in high-density lipoprotein (HDL) levels associated with an increase of cardiovascular risk factors and the atherogenic index. The present study demonstrated that a single CPF administration caused hyperglycemia and hyperlipidemia in rats. The activation of the gluconeogenesis pathway, probably elicited by hypercorticosteronemia, is involved in the hyperglycemic effect of CPF in rats.     

Chlorpyrifos degradation in a biomixture of biobed at different maturity stages

The biomixture is a principal element controlling the degradation efficacy of the biobed. The maturity of the biomixture used in the biobed affects its overall performance of the biobed, but this is not well studied yet. The aim of this research was to evaluate the effect of using a typical composition of Swedish biomixture at different maturity stages on the degradation of chlorpyrifos. Tests were made using biomixture at three maturity stages: 0 d (BC0), 15 d (BC15) and 30 d (BC30); chlorpyrifos was added to the biobeds at final concentration of 200, 320 and 480 mg kg⁻¹. Chlorpyrifos degradation in the biomixture was monitored over time. Formation of TCP (3,5,6-trichloro-2-pyrinidol) was also quantified, and hydrolytic and phenoloxidase activities measured. The biomixture efficiently degraded chlorpyrifos (degradation efficiency >50%) in all the evaluated maturity stages. However, chlorpyrifos degradation decreased with increasing concentrations of the pesticide. TCP formation occurred in all biomixtures, but a major accumulation was observed in BC30. Significant differences were found in both phenoloxidase and hydrolytic activities in the three maturity stages of biomixture evaluated. Also, these two biological activities were affected by the increase in pesticide concentration. In conclusion, our results demonstrated that chlorpyrifos can be degraded efficiently in all the evaluated maturity stages.     

Conductive-diamond electrochemical oxidation of chlorpyrifos in wastewater and identification of its main degradation products by LC-TOFMS

The electrochemical transformation of the organophosphorous insecticide chlorpyrifos (CPF) was investigated in wastewater. The oxidation of CPF was carried out in a single-compartment electrochemical flow cell working under batch operation mode, using diamond-based material as anode and stainless steel as cathode. In order to evaluate its persistence and degradation pathway, two different concentration levels (1.0 mg L⁻¹ and 0.1 mg L⁻¹) were studied. Liquid chromatography/mass spectrometry was used for evaluation of the initial and electrolyzed solutions. The identification of CPF transformation products was performed by liquid chromatography-time of flight-mass spectrometry (LC-TOFMS). Results showed that CPF is completely removed at the end of treatment time. Analysis by LC-TOFMS allowed the identification of six degradation products (with Mw 154, 170, 197, 305 321 and 333). Three of the identified intermediates (Mw 170, 305 and 321) were completely removed at the end of electrolysis time. Interestingly, the formation of diethyl 3,5,6-trichloropyridin-2yl phosphate (chlorpyrifos oxon) and 3,5,6-trichloropyridin-2-ol was also found in previous reported degradation pathways using different degradation technologies.