Assessment of potential dermal and inhalation exposure of workers to the insecticide imidacloprid using whole-body dosimetry in China

In China, although improvements to the pesticide registration process have beenmade in last thirty years, no occupational exposure data are required to obtain a commercial license for a pesticide product. Consequently, notably little research has been conducted to establish an exposure assessment procedure in China. The present study monitored the potential dermal operator exposure from knapsack electric sprayer wheat field application of imidacloprid in Liaocheng City, Shandong Province and in Xinxiang City, Henan Province, China, using whole-body dosimetry. The potential inhalation exposure was determined using a personal air pump and XAD-2 sample tubes. The analytical method was developed and validated, including such performance parameters as limits of detection and quantification, linear range, recovery and precision. The total potential dermal and inhalation exposures were 14.20, 16.80, 15.39 and 20.78 mL/hr, respectively, for the four operators in Liaocheng and Xinxiang, corresponding to 0.02% to 0.03% of the applied volume of spray solution. In all trials, the lower part (thigh, lower leg) of the body was the most contaminated, accounting for approximately 76% to 88% of the total exposure. The inhalation exposure was less than 1% of the total exposure. Such factors as the application pattern, crop type, spray equipment, operator experience and climatic conditions have been used to explain the exposure distribution over the different parts of the body. As indicated by the calculated Margin of Exposure, the typical wheat treatment scenarios when a backpack sprayer was used are considered to be safe in terms of imidacloprid exposure.     

Imidacloprid induced alterations in oxidative stress,biochemical, genotoxic,and immunotoxic biomarkers in non-mammalian model organism Galleria mellonella L. (Lepidoptera: Pyralidae)

Imidacloprid (IMI), a neonicotinoid insecticide, is widely used to control pests in agriculture. We investigated the changes in antioxidant enzyme activities, lipid peroxidation levels, biochemical effects, genotoxic effect, and immunotoxic effect of sublethal doses (0.25, 0.50, 0.75, and 1.00?µg) of IMI at different time periods (24, 48, 72, and 96?h) on a model organism, Galleria mellonella L. The results indicated that there were dose-dependent increases in both antioxidant enzyme activities (SOD and CAT) and MDA levels. Protein content was not affected by IMI at 24th and 48th, whereas it was decreased by the highest dose of IMI (1.00?µg) at 72nd and 96th h. Lipid and carbohydrate contents were reduced with increasing doses of IMI. Micronucleus frequency significantly increased in all IMI doses. All IMI doses caused a significant decrease in THC at 24th, 48th, and 72nd h. Our results can help to illustrate the effects of IMI in target organisms and indirectly may aid to discover potential risk of it on nontarget organisms. Future studies, at molecular levels, will be helpful in understanding the mechanism of action of IMI on these biomarkers.     

Direct determination of neonicotinoid insecticides in an analytically challenging crop such as Chinese chives using selective ELISAs

ABSTRACT

Easy-to-use commercial kit-based enzyme-linked immunosorbent assays (ELISAs) have been used to detect neonicotinoid dinotefuran, clothianidin and imidacloprid in Chinese chives, which are considered a troublesome matrix for chromatographic techniques. Based on their high water solubility, water was used as an extractant. Matrix interference could be avoided substantially just diluting sample extracts. Average recoveries of insecticides from spiked samples were 85–113%, with relative standard deviation of <15%. The concentrations of insecticides detected from the spiked samples with the proposed ELISA methods correlated well with those by the reference high-performance liquid chromatography (HPLC) method. The residues analyzed by the ELISA methods were consistently 1.24 times that found by the HPLC method, attributable to loss of analyte during sample clean-up for HPLC analyses. It was revealed that the ELISA methods can be applied easily to pesticide residue analysis in troublesome matrix such as Chinese chives.     

Co-metabolic transformation of the neonicotinoid insecticide imidacloprid by the new soil isolate Pseudoxanthomonas indica CGMCC 6648

A new imidacloprid (IMI) degrading bacterium Z-9 (deposited number CGMCC 6648) was isolated and identified as Pseudoxanthomonas indica by 16S rRNA gene analysis. Two metabolites were identified as olefin and 5-hydroxy IMI by liquid chromatography-mass spectrometry and nuclear magnetic resonance analysis. P. indica CGMCC 6648 degraded 70.1% of IMI (1.22 mmol L^?1) and formed 0.93 mmol L^?1 5-hydroxy IMI and 0.05 mmol L^?1 olefin IMI in 6 days and in the presence of 100 mmol L^?1 glucose. The half-life of IMI degradation was 3.6 days. P. indica CGMCC 6648 transforms IMI via a co-metabolism mechanism and different carbohydrates have significant effects on 5-hydroxy IMI formation, whereas different organic acids have substantial effects on olefin IMI production. Lactose is the best co-substrate for IMI degradation and 5-hydroxy IMI formation with 0.77 mmol L^?1 degraded and 0.67 mmol L^?1 formed in 48 h, respectively. Pyruvate is the best co-substrate for olefin IMI formation with 0.17 mmol L^?1 produced in 96 h for all carbon sources tested. Pyruvate significantly stimulates the conversion of 5-hydroxy IMI to olefin IMI, whereas glucose slightly inhibits this reaction. P. indica CGMCC 6648 rapidly degrades IMI and forms olefin IMI, which may enhance its potential for biodegradation of IMI and increase its insecticidal activity, which can decrease the IMI dosage required.     

Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

Sorption–desorption of imidacloprid onto a lacustrine Egyptian soil and its clay and humic acid fractions

Sorption–desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption–desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kd_ads, varied according to its initial concentration and was ranged 40–84 for HA, 14–58 for clay and 1.85–4.15 for bulk soil. Freundlich sorption coefficient, Kf_ads, values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ～800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/n_ads values <1 for all sorbents. Values of the hysteresis index (H) were <1, indicating the irreversibility of imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.     

催化湿式氧化法处理吡虫啉农药废水

自制了Cu／Mn，Cu／Ce，Cu／Ni，Ce／Mn，Ce／Ag等催化剂，经过性能比较，选择催化活性较高且金属溶出量较小的Cu／Ni作催化剂。用催化湿式氧化法处理吡虫啉农药废水，考察了各种因素对处理效果的影响。实验结果表明：在进水pH为6．93、Cu／Ni加入量为4．0g、反应温度为190oC、氧分压为1．6MPa、反应时间为120min的条件下，COD去除率为95％；处理后废水的BOD5／COD从0．093增至0．590，可生化性明显改善。     

吡虫啉的光解水解和土壤降

在实验室测定了吡虫啉的光解、不同ｐＨ条件下的水解与在东北黑土等３种不同土壤中的降解。试验结果表明，在３００Ｗ低压汞灯下，吡虫啉水相溶液的光解呈一级反应动力学反应，光解半衰期为６．８１ｈ；在ｐＨ５、ｐＨ７、ｐＨ９的缓冲溶液中的水解半衰期分别为３０．６、１３．６与８．０ｄ；在东北黑土、太湖水稻土和江西红壤中的降解半衰期分别为１０．７、１１．１和４．１ｄ。     

吡虫啉防治家白蚁的试验研究

10%吡虫啉可湿性粉剂与河沙混合成含有效成分(%)0.10、0.05、0.025、0.0125,家白蚁饲养其上,48～72h内100%死亡,浓度越高,死亡越快;白蚁也不能穿过以上述浓度配制的长10cm沙土管,对照则穿行自如;以上述浓度药液浸的杉木块,也完全防止白蚁取食,对照则严重被食.在室外(2004.5～2005.5),家白蚁不能通过含0.05%及0.10%药液淋浇(1000ml/40×50cm)的土壤,去取食试区中心的无药木块.吡虫啉可湿性粉剂不用有机溶剂,无刺激气味,运储施工方便,可以认为它是当前最高效的环保型白蚁防治药剂,并建议生产中以0.05%(10%可湿性粉剂稀释200倍)用于室内防治,0.10～0.05%(稀释100～200倍)用于室外防治.     

FeCl3改性污泥生物炭对水中吡虫啉的吸附性能研究

以脱水污泥为原料,制备污泥生物炭（SBC）和FeCl₃改性污泥生物炭（Fe-SBC）处理低浓度吡虫啉（IMI）废水（浓度为10 mg·L^-1）,考察SBC和Fe-SBC对IMI的吸附性能及影响因素,并探究其吸附机理.采用SEM、XRD、FTIR、BET及元素分析等探得污泥生物炭FeCl₃改性成功.Fe-SBC对IMI的最大吸附量为4.915 mg·g^-1,是SBC的1.97倍,表现出更好的IMI吸附性能.pH和离子强度的变化对Fe-SBC的吸附性能影响较小,最大波动幅度分别为4.4%和7.8%.两种生物炭对IMI的吸附均符合准二级动力学模型,Freundlich模型可以更好地描述其等温吸附曲线.热力学研究表明,SBC吸附IMI是非自发吸附,而Fe-SBC是自发吸附.Fe-SBC对IMI的吸附机理包括静电作用力、氢键作用力及π-π键相互作用力.多次热解再生后的Fe-SBC对IMI的去除率仍可达93.088%.