双功能吸附剂的制备及其对水中毒死蜱的降解特性

对具有催化功能的负载Fe（Ⅲ）的活性炭进行了表征,与母体活性炭相比,其比表面积以及微孔体积均有所下降,酸性官能团的量有所增加;考察了普通浸渍法和超声浸渍法制备的双功能活性炭对毒死蜱的吸附和降解性能,结果表明,双功能活性炭对毒死蜱的吸附量有所降低,但对毒死蜱的降解能力增强,超声浸渍法所制备的活性炭对毒死蜱的降解能力要优于普通浸渍法所制备的活性炭。     

Repeated batch and continuous degradation of chlorpyrifos by Pseudomonas putida

The present study was undertaken with the objective of studying repeated batch and continuous degradation of chlorpyrifos (O,O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) using Ca-alginate immobilized cells of Pseudomonas putida isolated from an agricultural soil, and to study the genes and enzymes involved in degradation. The study was carried out to reduce the toxicity of chlorpyrifos by degrading it to less toxic metabolites. Long-term stability of pesticide degradation was studied during repeated batch degradation of chlorpyrifos, which was carried out over a period of 50 days. Immobilized cells were able to show 65% degradation of chlorpyrifos at the end of the 50th cycle with a cell leakage of 112 × 10³ cfu mL^?1. During continuous treatment, 100% degradation was observed at 100 mL h^?1 flow rate with 2% chlorpyrifos, and with 10% concentration of chlorpyrifos 98% and 80% degradation was recorded at 20 mL h^?1 and 100 mL h^?1 flow rate respectively. The products of degradation detected by liquid chromatography–mass spectrometry analysis were 3,5,6-trichloro-2-pyridinol and chlorpyrifos oxon. Plasmid curing experiments with ethidium bromide indicated that genes responsible for the degradation of chlorpyrifos are present on the chromosome and not on the plasmid. The results of Polymerase chain reaction indicate that a ~890-bp product expected for mpd gene was present in Ps. putida. Enzymatic degradation studies indicated that the enzymes involved in the degradation of chlorpyrifos are membrane-bound. The study indicates that immobilized cells of Ps. putida have the potential to be used in bioremediation of water contaminated with chlorpyrifos.     

Influence of the pesticides glyphosate,chlorpyrifos and atrazine on growth parameters of nonochratoxigenic Aspergillus section Nigri strains isolated from agricultural soils

This investigation was undertake to determine the effect of glyphosate, chlorpyrifos and atrazine on the lag phase and growth rate of nonochratoxigenic A. niger aggregate strains growing on soil extract medium at ?0.70, ?2.78 and ?7.06 MPa. Under certain conditions, the glyphosate concentrations used significantly increased micelial growth as compared to control. An increase of about 30% was observed for strain AN 251 using 5 and 20 mg L^?1 of glyphosate at ?2.78 MPa. The strains behaved differently in the presence of the insecticide chlorpyrifos. A significant decrease in growth rate, compared to control, was observed for all strains except AN 251 at ?2.78 MPa with 5 mg L^?1. This strain showed a significant increase in growth rate. With regard to atrazine, significant differences were observed only under some conditions compared to control. An increase in growth rate was observed for strain AN 251 at ?2.78 MPa with 5 and 10 mg L^?1 of atrazine. By comparison, a reduction of 25% in growth rate was observed at ?7.06 MPa and higher atrazine concentrations. This study shows that glyphosate, chlorpyrifos and atrazine affect the growth parameters of nonochratoxigenic A. niger aggregate strains under in vitro conditions.     

Simultaneous biodegradation of bifenthrin and chlorpyrifos by Pseudomonas sp. CB2

The degradation of bifenthrin (BF) and chlorpyrifos (CP), either together or individually, by a bacterial strain (CB2) isolated from activated sludge was investigated. Strain CB2 was identified as belonging to genus Pseudomonas based on the morphological, physiological, and biochemical characteristics and a homological analysis of the 16S rDNA sequence. Strain CB2 has the potential to degrade BF and CP, either individually or in a mixture. The optimum conditions for mixture degradation were as follows: OD_600nm = 0.5; incubation temperature = 30°C; pH = 7.0; BF-CP mixture (10 mg L^?1 of each). Under these optimal conditions, the degradation rate constants (and half-lives) were 0.4308 d^?1 (1.61 d) and 0.3377 d^?1 (2.05 d) for individual BF and CP samples, respectively, and 0.3463 d^?1 (2.00 d) and 0.2931 d^?1 (2.36 d) for the BF-CP mixture. Major metabolites of BF and CP were 2-methyl-3-biphenylyl methanol and 3,5,6-trichloro-2-pyridinol, respectively. No metabolite bioaccumulation was observed. The ability of CB2 to efficiently degrade BF and CP, particularly in a mixture, may be useful in bioremediation efforts.     

耐盐性毒死蜱降解混合菌的构建及其降解特性

为明确蜡状芽孢杆菌(Bacillus cereus)混合菌株对毒死蜱的降解效果,采用正交实验的方法构建混合菌。以混合菌对毒死蜱的降解率和菌株的生长量为依据,利用单一因素实验考察了不同因素对混合菌降解毒死蜱的影响。结果表明:构建的混合菌中三菌株的体积比为1∶1∶3。在含80 mg/L毒死蜱的反应体系中,最适接菌量为8%(V/V),最适pH为7。在实验浓度下,混合菌对毒死蜱的降解符合一级动力学方程。混合菌对盐分有较高的耐受度,当反应液中氯化钠浓度在20～100 g/L之间时,混合菌对80 mg/L毒死蜱的降解率最高达61%。     

An integrated approach for assessing the migration behavior of chlorpyrifos and carbaryl in the unsaturated soil zone

Chlorpyrifos (O, O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) and carbaryl (1-naphthyl methylcarbamate) are often applied concurrently as insecticides in food production. The aim of this study was to research their migration behavior in a real environment. We researched the leaching of both pesticides by setting up field lysimeters on a farm with the typical soil used in fruit production today. In order to analyze the variables involved in this process, we performed complementary adsorption studies, we performed complementary adsorption studies using batches and undisturbed soil laboratory columns for both compounds. The results for pesticide transport through the lysimeters showed that less than 1% of chlorpyrifos was recovered in the leachates, while almost 17% was recovered for carbaryl. Having completed the experiment in undisturbed laboratory columns, soil analysis showed that chlorpyrifos mainly remained in the first 5 cm, while carbaryl moved down to the lower sections. These results can be explained in view of the sorption coefficient values (K_D) obtained in horizons A and B for chlorpyrifos (393 and 184 L kg^?1) and carbaryl (3.1 and 4.2 L kg^?1), respectively. By integrating the results obtained in the different approaches, we were able to characterize the percolation modes of these pesticides in the soil matrix, thus contributing to the sustainable use of resources.     

A rapid and sensitive fluoroimmunoassay based on quantum dot for the detection of chlorpyrifos residue in drinking water

A rapid and sensitive indirect competitive fluorescence-linked immunosorbent assay (cFLISA) method based on quantum dots as the fluorescence label coupled with secondary antibody (Ab₂) for the detection of chlorpyrifos in drinking water has been developed. The cFLISA method allowed for chlorpyrifos determination in a liner working range of 15.2–205.5 ng mL^?1. The 50 % inhibition value (IC₅₀) and the limit of detection (LOD) of the cFLISA were 50.2 ng mL^?1 and 8.4 ng mL^?1, while the IC₅₀ and the LOD of the conventhional enzyme linked immunosorbent assay (ELISA) were 95.3 ng- mL^?1 and 16.2 ng mL^?1, respectively. When the concentrations of chlorpyrifos were 200, 100 and 50 ng mL^?1, the recoveries ranged from 90.8 % to 108.2 % with a coefficient of variation (CV) of 7.5 %–15.2 %. In water sample analysis, the results of cFLISA were similar to those obtained from a cELISA and a high performance liquid chromatography (HPLC) method, while the detection time by cFLISA was reduced 0.5 h compared with ELISA. It showed that cFLISA could be used as a new screening method for the detection of pesticide residue.     

Binding and detoxification of chlorpyrifos by lactic acid bacteria on rice straw silage fermentation

This investigation examined the reduction of pesticide residues on straw inoculated with lactic acid bacteria (LAB) during ensiling. Lactobacillus casei WYS3 was isolated from rice straw that contained pesticide residues. Non-sterilized rice straw, which was inoculated with L. casei WYS3, showed increased removal of chlorpyrifos after ensiling, compared with rice straw that was not inoculated with L. casei WYS3 or sterilized rice straw. In pure culture, these strains can bind chlorpyrifos as indicated by high-performance liquid chromatography analysis. Viable L. casei WYS3 was shown to bind 33.3–42% of exogenously added chlorpyrifos. These results are similar to those of acid-treated cells but less than those of heat-treated cells, which were found to bind 32.0% and 77.2% of the added chlorpyrifos respectively. Furthermore, gas chromatography–mass spectrometry analysis determined that L. casei WYS3 detoxified chlorpyrifos via P-O-C cleavage. Real-time polymerized chain reaction analysis determined that organophosphorus hydrolase gene expression tripled after the addition of chlorpyrifos to LAB cultures, compared with the control group (without chlorpyrifos). This paper highlights the potential use of LAB starter cultures for the detoxification and removal of chlorpyrifos residues in the environment.     

添加给水厂残泥对稻田土壤中毒死蜱环境赋存及厌氧降解的影响

给水厂残泥(WTR)是给水厂混凝过程产生的安全废弃物,是一种高效低廉的毒死蜱吸附材料。为评估将WTR作为吸附材料添加于土壤中缓解毒死蜱危害的可行性,探究了添加WTR对稻田土壤中毒死蜱环境赋存、厌氧降解及其代谢产物TCP形成的影响。实验结果表明:毒死蜱首要厌氧降解途径是快速水解为TCP,添加WTR显著降低了土壤中毒死蜱与TCP的生物有效性(P<0.05)。72 d厌氧培养时间内,未添加WTR土壤中高达79%的毒死蜱主要以生物可利用态存在;在WTR添加土壤中,72%～95%的毒死蜱以稳定的残渣态存在,但毒死蜱在土壤中的降解速度因此减慢,TCP生成量随之减少。在未添加WTR土壤中,92%以上的TCP以水溶态为主,添加WTR可有效减少其水溶态所占比例,WTR添加量为10%时,其水溶态含量降至47%。随着WTR添加量增加,毒死蜱与TCP由土壤向上覆水迁移的量显著减少(P<0.05)。未添加WTR的土壤水溶液体系上覆水中毒死蜱和TCP浓度分别高达537 μg·L-1和1 750 μg·L-1,添加2%WTR可使其最高浓度分别降低50%。在厌氧滞水的稻田土壤中,WTR主要金属元素(Fe、Al和Mn)稳定性强,二次污染风险较低。综合以上研究结果,WTR适于作为土壤添加物应用于毒死蜱与TCP污染控制。     

The stability of dieldrin,aldrin, lindane,chlorpyrifos and prothiofos in stored roof water

Abstract

The stability of dieldrin, aldrin, lindane, chlorpyrifos and prothiofos was determined in distilled water and in roof water from either galvanised or concrete tanks. Samples were stored in the dark at 23°C. Dieldrin and lindane were stable for the 36 week period. Aldrin dissipated rapidly with a half‐life of 4–5 weeks, with no dieldrin being formed. Chlorpyrifos and prothiofos also broke down, with half‐lives ranging 12–18 weeks and 11–14 weeks respectively. No significant effect of water type was found. For the purpose of domestic usage, an activated carbon filter would be essential otherwise all contaminated water would have to be disposed of safely.     

Degradation of chlorpyrifos by an endophytic bacterium of the Sphingomonas genus (strain HJY) isolated from Chinese chives (Allium tuberosum)

The degradation of chlorpyrifos (CP) by an endophytic bacterial strain (HJY) isolated from Chinese chives (Allium tuberosum Rottl. ex Spreng) was investigated. Strain HJY was identified as Sphingomonas sp. based on morphological, physiological, and biochemical tests and a 16S rDNA sequence analysis. Approximately 96% of 20 mg L^?1 CP was degraded by strain HJY over 15 days in liquid minimal salts medium (MSM). The CP degradation rate could also be increased by glucose supplementation. The optimal conditions for the removal of 20 mg L^?1 CP by strain HJY in MSM were 2% inoculum density, pH 6.0, and 30–35°C. The CP degradation rate constant and half-life were 0.2136 ± 0.0063 d^?1 and 3.2451 ± 0.0975 d, respectively, under these conditions, but were raised to 0.7961 ± 0.1925 d^?1 and 0.8707 ± 0.3079 d with 1% glucose supplementation. The detection of metabolic products and screening for degrading genes indicated that O,O-diethyl O-3,5,6-trichloropyridinol was the major degradation product from CP, while it was likely that some functional genes were undetected and the mechanism responsible for CP degradation by strain HJY remained unknown. Strain HJY is potentially useful for the reduction of CP residues in Chinese chives and may be used for the in situ phytoremediation of CP.     

潜流人工湿地去除毒死蜱、双酚A、4-壬基酚

为研究潜流人工湿地对毒死蜱、BPA及4-NP的去除效果,选取宽叶香蒲、芦苇、花叶香蒲及小香蒲4种湿地植物,通过SPE-HPLC测定进出水中3种污染物的浓度,计算4种植物潜流人工湿地对3种污染物的去除效率。结果表明,水力停留时间3 d,4组植物对毒死蜱、BPA和4-NP去除率均高于60%,各植物组对毒死蜱和4-NP的去除效果之间无显著性差异,宽叶香蒲对BPA的去除率为82.66%,显著高于其余3种植物组62.96%~69.63%。在静态条件下,毒死蜱、BPA和4-NP在模拟系统内降解过程符合一级降解动力学方程,降解方程分别为：c=124.63exp（-t/25.393）+3.7618 ①,c=316.61exp（-t/34.955）+0.56475 ②,c=168.91exp（-t/17.061）+12.133 ③（c,剩余浓度,μg/L;t,停留时间,h）,半衰期分别为18、21和11 h。     

Effect of Dursban 480 EC (chlorpyrifos) and Talstar 10 EC (bifenthrin) on the physiological and genetic diversity of microorganisms in soil

This investigation was undertaken to determine the impact of the insecticides Dursban 480 EC (with organophosphate compound chlorpyrifos as the active ingredient) and Talstar 10 EC (with pyrethroid bifenthrin as the active ingredient) on the respiration activity and microbial diversity in a sandy loam luvisol soil. The insecticides were applied in two doses: the maximum recommended dose for field application (15 mg kg^?1 for Dursban 480 EC and 6 mg kg^?1 for Talstar 10 EC) and a 100-fold higher dose for extrapolation of their effect. Bacterial and fungal genetic diversity was analysed in soil samples using PCR DGGE and the functional diversity (catabolic potential) was studied using BIOLOG EcoPlates at 1, 3, 7, 14, 28, 56 and 112 days after insecticide application. Five bacterial groups (α, β, γ proteobacteria, firmibacteria and actinomycetes) and five groups of fungi or fungus-like microorganisms (Ascomycota, Basidiomycota, Chytridiomycota, Oomycota and Zygomycota) were analysed using specific primer sets. This approach provides high resolution of the analysis covering majority of microorganisms in the soil. Only the high-dose Dursban 480 EC significantly changed the community of microorganisms. We observed its negative effect on α- and γ-proteobacteria, as the number of OTUs (operational taxonomic units) decreased until the end of incubation. In the β-proteobacteria group, initial increase of OTUs was followed by strong decrease. Diversity in the firmibacteria, actinomycetes and Zygomycota groups was minimally disturbed by the insecticide application. Dursban 480 EC, however, both positively and negatively affected certain species. Among negatively affected species Sphingomonas, Flavobacterium or Penicillium were detected, but Achromobacter, Luteibacter or Aspergillus were supported by applied insecticide. The analysis of BIOLOG plates using AWCD values indicated a significant increase in metabolic potential of microorganisms in the soil after the high-dose Dursban application. Analysis of respiration demonstrated high microbial activity after insecticide treatments; thus, microbial degradation was relatively fast. The half-life of the active insecticide compounds were estimated within the range of 25 to 27 days for Talstar and 6 to 11 days for Dursban and higher doses stimulated degradation. The recommended dose levels of both insecticides can be considered as safe for microbial community in the soil.     

Differences in response of two model estuarine crustaceans after lethal and sublethal exposures to chlorpyrifos

This study assessed the in vitro and in vivo effects of an acetylcholinesterase enzyme inhibitor (chlorpyrifos) in two estuarine crustaceans: grass shrimp (Palaemonetes pugio) and mysid (Americamysis bahia). The differences in response were quantified after lethal and sublethal exposures to chlorpyrifos and in vitro assays with chlorpyrifos-oxon. Results from the in vitro experiments indicated that the target enzyme, acetylcholinesterase (AChE), in the two species was similar in sensitivity to chlorpyrifos inhibition with IC50s of 0.98 nM and 0.89 nM for grass shrimp and mysids, respectively. In vivo experiments showed that mysids were significantly more sensitive to chlorpyrifos-induced AChE inhibition after 24 h of exposure. The in vivo EC50s for AChE inhibition were 1.23 μg L^?1 for grass shrimp and 0.027 μg L^?1 for mysids.

Median lethal concentrations (24h LC50 values) were 1.06 μg L^?1 for grass shrimp and 0.068 μg L^?1 for mysids. The results suggest that differences in the response of these two crustaceans are likely related to differences in uptake and metabolism rather than target site sensitivity.     

Simultaneous gas chromatographic determination of chlorpyrifos and its impurity sulfotep in liquid pesticide formulations

An analytical method for simultaneous determination of the active substance (chlorpyrifos) and its relevant impurity (sulfotep) in commercial pesticide formulations has been developed and validated. The proposed method entails extraction of the analytes from samples by sonication with acetone and analysis by gas chromatography-flame ionization detection (GC-FID). The proposed method was characterized by satisfactory accuracy and precision. The repeatability expressed as relative standard deviation (RSD) was lower than the acceptable values calculated from the modified Horwitz equation whereas individual recoveries were in the range of 98–102% and 80–120% for chlorpyrifos and sulfotep, respectively. The limit of quantification (LOQ) for the impurity (sulfotep) was 0.003 mg mL^?1 corresponding to the maximum permitted level according to Food and Agricultural Organization of the United Nations (FAO) specifications for the active substance (chlorpyrifos) being 3 g kg^?1 of the chlorpyrifos content found. The main advantage of the proposed method was a considerable reduction in the analysis time since both analytes were determined based on a single injection into the GC-FID. Analysis of real samples of commercial pesticide formulations confirmed fitness-for-purpose of the proposed method.     

Dissipation,half-lives,and mass spectrometric identification of chlorpyrifos and its two metabolites on field-grown collard and kale

The persistence and fate of chlorpyrifos and its two metabolites, chlorpyrifos-oxon and the 3, 5, 6-trichloro-2-pyridinol (TCP) break-down product were investigated on kale and collard leaves under field conditions. A simultaneous extraction and quantification procedure was developed for chrorpyrifos and its two main metabolites. Residues of chlorpyrifos, chlorpyrifos oxon, and TCP were determined using a gas chromatograph (GC) equipped with an electron capture detector (GC/ECD). Chlorpyrifos metabolites were detectable up to 23 days following application. Residues were confirmed using a GC equipped with a mass selective detector (GC/MSD) in total ion mode. Initial residues of chlorpyrifos were greater on collard (14.5 µg g^?1) than kale (8.2 µg g^?1) corresponding to half-lives (T_1/2) values of 7.4 and 2.2 days, respectively. TCP, the hydrolysis product, was more persistent on collards with an estimated T_1/2 of 6.5 days compared to kale (T_1/2 of 1.9 days).     

Comparative hersistence of chlorpyrifos in a mineral soil after granular and drench applications

Abstract

Lorsban 15G (15% chlorpyrifos) at 1.6 and 2.2 g a.i./10 m row, and Lorsban 4E (40.7% chlorpyrifos) at 2.0 g a.i./10 m row were applied respectively to a silt loam soil as a band treatment at seeding and as a drench after seeding. The rate of disappearance of chlorpyrifos [Q,Q‐diethyl Q‐(3,5,6‐trichloro‐2‐pyridinyl) phosphorothioate] was relatively fast in the first 15 days but slowed down considerably thereafter regardless of the methods of application and application rates; and there was a statistically significant (p=0.05) linear relationship between the natural logarithm of chlopyrifos concentration and time. Based on the linear regression equations, the calculated pseudo‐first‐order rate constants were 0.041 day^‐1 and 0.044 day^‐1 respectively for the band treatments at 1.6 and 2.2 g a.i./10 m row; and 0.040 day^‐1 for the drench. The calculated half‐lives for all three treatments were similar and they ranged frcm 15.8 days to 17.3 days. The degradation product 3,5,6‐trichloro‐2‐pyridinol (TP) was detected in soil but not 3,5_/6‐trichloro‐2‐methoxypyridine (TMP). The concentration of TP increased steadily to a peak and declined thereafter. The highest mean concentration of TP was 2.21 ppm (dry wt) detected 29 days after band treatment at the high rate. After 90 days the concentration of TP decreased to 0.43 ppm (dry wt).     

Persistence of granular and EC formulations of chlorpyrifos in a mineral and an organic soil incubated in open and closed containers

Abstract

Samples of a mineral soil (Plainfield sand) and an organic soil (muck) were treated with granular and EC formulations of chlorpyrifos and incubated at 27±1°C and 65±5% RH in open and closed containers. Duplicate samples of each soil‐formulation‐container combination were analyzed for residual chlorpyrifos during a 23 wk period. The disappearance rates observed demonstrate that the relative importance of formulation and containment on overall persistence depends on soil type. For the mineral soil, disappearance was slower from closed containers and formulation had only a slight effect while, in the organic soil the granular formulation disappeared slower than the EC and there was little difference between open and closed containers. The relative importance of degradation and volatilization in the disappearance of chlorpyrifos from soil is discussed.     

Urinary dialkyl phosphate levels before and after first season chlorpyrifos spraying amongst farm workers in the Western Cape,South Africa

The study investigated urinary levels of dialkyl phosphates resulting from pesticide exposure amongst 40 farm workers. Workers were tested (urinary dialkyl phosphate levels, anthropometry, short exposure questionnaire) before and after the first day of seasonal chlorpyrifos spraying. Median baseline urinary dialkyl phosphates was high amongst both non-applicators (1587.5 μg/g creatinine, n = 8) and applicators (365.6 μg/g creatinine, n = 9). There was not much evidence of an increase in post-spray dialkyl phosphates levels from pre-spray levels amongst both applicators and non-applicators. Hours mixing, spraying, driving a tractor and hours worked by non-applicators were not significantly associated with an increase in post-spray dialkyl phosphate levels, adjusting for age, height, weight, gender, use of empty pesticide containers and self-reported kidney problems. Past applicator status was weakly positively associated with pre-spray dialkyl phosphate levels adjusting for age, height, weight, and gender, self-reported kidney problems, smoking and alcohol (β= 1019.5, p = 0.307, R²= 0.28). The high dialkyl phosphate levels call for an epidemiological investigation into the health effects of organophosphorous pesticides.     

Measurement of transferable chemical residue from nylon carpet using the California roller and a new mega-California roller

Human chemical exposures resulting from transfer of surface deposition on indoor nylon carpets may be estimated by measuring transferable residues (μ g chemical/cm² carpet). A weighted roller developed at California Department of Food and Agriculture (CDFA) has been extensively used to sample transferable residue for estimates of human exposure in risk characterization. A modified roller has been developed to evaluate the influence of pressure on transferable chemical residue since weight and force (or pressure, kg/m²) may vary person-to-person and activity-to-activity. A 30.5 cm diameter roller was used to apply 60 to 2100 kg/m² to bracket pressures exerted by humans on a flat nylon-carpeted surface. Measurements of transferable cyfluthrin residues were made after 1, 7, and 21 days. Total Soxhlet extractable cyfluthrin residues were relatively constant during the test period. Residue transferability decreased during the study period. Modest increases in the transferability of surface residues were observed over the broad range of pressures applied by the modified roller.