A sensitive monoclonal antibody-based enzyme-linked immunosorbent assay for chlorpyrifos residue determination in Chinese agricultural samples

A monoclonal antibody-based competitive antibody-coated enzyme-linked immunosorbent assay (ELISA) was developed and optimized for determining chlorpyrifos residue in agricultural products. The IC₅₀ and IC₁₀ of this ELISA were 3.3 ng/mL and 0.1 ng/mL respectively. The average recoveries in six agricultural products were between 79.5% and 118.0%, with the intra-assay coefficient of variation being less than 8 %. The limit of detection for all tested products was 30 ng/g. To the best of our knowledge, this assay has the best specificity among all the published research on ELISAs for chlorpyrifos.     

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.     

Distribution of chlorpyrifos in rice paddy environment and its potential dietary risk

Chlorpyrifos is one of the most extensively used insecticides in China. The distribution and residues of chlorpyrifos in a paddy environment were characterized under field and laboratory conditions. The half-lives of chlorpyrifos in the two conditions were 0.9–3.8 days (field) and 2.8–10.3 days (laboratory), respectively. The initial distribution of chlorpyrifos followed the increasing order of water < straw < soil, and soil was characterized as the major absorber. The ultimate residues in rice grain were below the maximum residue limit (MRL) with a harvest interval of 14 days. The chronic exposure for chlorpyrifos was rather low compared to the acceptable daily intake (ADI = 0.01 mg/kg bw) due to rice consumption. The chronic exposure risk from chlorpyrifos in rice grain was 5.90% and 1.30% ADI from field and laboratory results respectively. Concerning the acute dietary exposure, intake estimated for the highest chlorpyrifos level did not exceed the acute reference dose (ARfD = 0.1 mg/kg bw). The estimated short-term intakes (ESTIs) were 0.78% and 0.25% of the ARfD for chlorpyrifos. The results showed that the use of chlorpyrifos in rice paddies was fairly safe for consumption of rice grain by consumers.     

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.     

以毒死蜱为案例的环境保护综合名录政策的实证研究

通过对毒死蜱生产技术的国内外发展研究,说明山东谦诚公司发明的吡啶双定向氯化合成三氯吡啶酚钠工艺,具有技术先进性、经济合理性、环境可达性,是我国独创的,是毒死蜱生产技术的重大突破。环境保护综合名录认为吡啶双定向氯化合成三氧吡啶酚钠工艺是重大突破,具有技术先进性、经济合理性、环境可达性;通过对产品的全过程控制,分析毒死蜱对人体、作物土壤均有影响但是利大于弊。是可以接受的,被列入环境友好工艺。     

Effects of atrazine on acetylcholinesterase activity in midges (Chironomus tentans) exposed to organophosphorus insecticides

Acetylcholinesterase activity was determined for midge larvae (Chironomus tentans) exposed to either organophosphorus insecticides (OPs) alone or OP insecticides in binary combination with atrazine (200 μg/l). Although atrazine by itself did not reduce the level of acetylcholinesterase activity, atrazine in combination with chlorpyrifos significantly decreased acetylcholinesterase activity as compared to chlorpyrifos only treatments. Although similar trends existed for malathion and methyl parathion, differences were not statistically significant. These results match previously published toxicity data where atrazine, although not acutely toxic even at much higher levels, decreased EC₅₀ values for chlorpyrifos by a magnitude of 4, decreased methyl parathion values by a magnitude of 2, and did not decrease values for malathion.     

毒死蜱在不同土壤腐殖酸上的吸附/解吸特征

通过平衡振荡法研究毒死蜱在不同来源土壤腐殖酸(Has)上的吸附/解吸行为.结果表明,毒死蜱在Has上的等温吸附行为用Freundlich模型描述相对更合理;它们的吸附等温线在实验范围内基本呈直线,且吸附能力很强,顺序为:紫色潮土Has＞黄壤Has＞中性紫色土Has＞酸性紫色土Has＞腐殖土Has;但毒死蜱的解吸率较小,其值均小于26.70%,有明显的滞后现象,尤其是腐殖土Has和紫色潮土Has,固定能力顺序为:紫色潮土Has＞腐殖土Has＞中性紫色土Has＞酸性紫色土Has＞黄壤Has.由于不同来源土壤中Has的组成结构差异明显,它们对毒死蜱的吸附/解吸规律表现出不同的特征.土壤Has对毒死蜱的吸附/解吸行为的影响是多种因素综合作用的结果,具体作用机理尚待进一步研究.     

Farmworker children's residential non-dietary exposure estimates from micro-level activity time series

Farmworkers' children may have increased pesticide exposure through dermal absorption and non-dietary ingestion, routes that are difficult to measure and model. The Cumulative Aggregate Simulation of Exposure (CASE) model, integrates the complexity of human behavior and variability of exposure processes by combining micro-level activity time series (MLATS) and mechanistic exposure equations. CASE was used to estimate residential non-dietary organophosphate pesticide exposure (i.e., inhalation, dermal, and non-dietary ingestion) to California farmworker children and evaluate the micro-activity approach. MLATS collected from children and distributions developed from pesticide measurements in farmworkers' residences served as inputs. While estimated diazinon exposure was greater for inhalation, chlorpyrifos exposure was greater for the other routes. Greater variability existed between children (σ_B² = 0.22–0.39) than within each child's simulations (σ_W² = 0.01–0.02) for dermal and non-dietary ingestion. Dermal exposure simulations were not significantly different than measured values from dosimeters worn by the children. Non-dietary ingestion exposure estimates were comparable to duplicate diet measurements, indicating this route may contribute substantially to aggregate exposure. The results suggest the importance of the micro-activity approach for estimating non-dietary exposure. Other methods may underestimate exposure via these routes. Model simulations can be used to identify at-risk children and target intervention strategies.     

Impact of chlorpyrifos on cerebrum and cerebellum maturity in suckling rats

The purpose of our study is to assess the effect of chlorpyrifos (CPF) on rat cerebral and cerebellar maturity during the suckling period. Female Wistar rats were given 0.2?g?L^?1 of CPF in drinking water, equivalent to 40?mg?kg^?1 of body weight?day^?1, from day zero until day ten after delivery. In treated pups, plasma butyrylcholinesterase (BuChE) activity was inhibited by 70%. Cerebrum and cerebellum acetyl-cholinesterase (AchE) activities were reduced by 71 and 75%, respectively. The results suggest that CPF was distributed in pup tissues through the milk of lactating mothers, resulting in inhibition of AchE activities. At age 10 days, the CPF-treated pups showed a 28% decrease in body weight, a 23 and 41% decrease in plasma free T₃ and T₄ levels and reduction in cerebral and cerebellar protein content by 36 and 38%, respectively. Consistent histological changes were found in the cerebellum of CPF treated pups, with the external granular layer being markedly developed, the Purkinje cell bodies being poorly differentiated and abnormally distributed into the internal granular layer.     

Distribution of pesticides and bisphenol A in sediments collected from rivers adjacent to coral reefs

To investigate the deteriorating health of coral reefs in Okinawa, Japan, natural sediment samples were analyzed for diuron, Irgarol 1051, chlorpyrifos, and bisphenol A (BPA) which are hazardous to corals. Samples were analyzed by solid-phase extraction (SPE) followed by high-performance liquid chromatography with tandem mass spectrometry (LC–MS–MS). Although diuron and chlorpyrifos usage is only well recorded for farms and not for cities, these chemicals were detected in both rural and urban areas. Additionally, diuron concentration in urban areas was in some cases higher than in rural areas, which might be caused by greater consumption of these chemicals in home gardens in city areas. Irgarol 1051 was detected in downstream river areas, which are situated far from the source sites such as pier or fishery harbor (0.6–3.2 km). This result suggested that Irgarol 1051 could be transported from the river mouths to the sampling sites during flood tides. High BPA concentrations were associated with urban areas (<1.2–22.0 μg kg⁻¹), while low concentrations were associated with rural areas (nd–6.8 μg kg⁻¹). The river sediments under study are delivered to coral reefs in large quantity through runoff caused by typhoons and other heavy rains. The highly hazardous chemicals are carried into coral reefs on these sediments. Therefore, these hazardous chemical substances may already be influencing the coral reefs.