毒死蜱对于隆线溞和中华薄壳介混合种群的影响

研究了毒死蜱对隆线溞(Daphnia carinata)和中华薄壳介(Dolerocypris sinensis)混合种群的种群密度、N-乙酰-β-D-氨基葡萄糖苷酶(NAGase)比活力和隆线溞游离态几丁质酶免疫可反应蛋白(chitinase-IR)的影响。结果表明,在毒死蜱质量浓度高于0.05μg/L的条件下,毒死蜱对两种生物会有抑制作用,并且基本随暴露浓度的升高而增强。不过,随着水中残留的毒死蜱浓度降低,抑制作用会减弱。计算毒死蜱对隆线溞和中华薄壳介的最高无作用浓度(NOEC)和最低有效浓度(LOEC)发现,中华薄壳介对毒死蜱的敏感性高于隆线溞。在生态风险评估工作中,NOEC或LOEC使用时间加权平均浓度会使评价结果更加准确。     

漆酶/香草醛体系生物降解毒死蜱影响因素的研究

研究了漆酶介体体系对有机磷农药毒死蜱生物降解的效果及影响因素.通过对6种介体的试验比较,筛选了合适的介体.在试验条件下,1-羟基苯并三唑(HBT)和2,2’-联氮-二(3-乙基-苯并噻唑-6-磺酸)(ABTS)对漆酶降解毒死蜱存在一定的抑制作用,紫脲酸(VA)和2,6-二甲氧基苯酚(2,6-DMP)对漆酶降解毒死蜱未起促进作用,而天然产物香草醛和愈创木酚可促进漆酶降解毒死蜱,香草醛的促进作用最为明显,选择香草醛作为漆酶介体体系中的介体.研究了漆酶/香草醛体系中,反应时间、漆酶初始酶活、pH、温度、介体投加量及投加方式、毒死蜱初始浓度等因素对毒死蜱生物降解效果的影响.结果表明,控制漆酶初始酶活为0.050 U/mL、pH为5.0、温度30℃,分2次投加香草醛(香草醛与毒死蜱初始值摩尔比分别为40和80)情况下,漆酶/香草醛体系即可在24 h内实现对25 mg/L毒死蜱的有效降解,降解率达98％.     

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.     

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。     

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(P0.05)。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(P0.05)。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537μg·L~(-1)和1 750μg·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。     

一株毒死蜱降解菌的分离鉴定及降解性能研究

从农药厂废水处理池污泥中分离到一株对毒死蜱有较强降解能力的菌株CH3,通过生理生化试验初步将该菌鉴定为哈夫尼菌属(Hafnia sp.)。CH3能以毒死蜱为唯一碳源生长,在温度为30℃,pH为7.0,毒死蜱初始浓度为200 mg/L的条件下,历时6 d,毒死蜱的降解率可达78.5%。菌株最适生长温度为37℃,最适pH值为7.0,最适降解浓度为200 mg/L。对碳、氮源利用广泛,最佳碳源为蔗糖和葡萄糖,对氮源选择性不高,在无机氮源和有机氮源中均能较好地生长。     

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%。     

粪便中温好氧堆肥过程有机物的降解研究

为了生态厕所的推广使用、便于操作和节约能耗,多采用无加热的设施,即在自然条件下(对于小型生态厕所,接近中温条件)的好氧堆肥处理.了解中温好氧堆肥过程有机物的降解特性,对于生态厕所的推广使用和简化设计、操作等具有重要意义.采用密闭式好氧堆肥反应器,模拟中温(35℃)的堆肥温度,以新鲜锯末为空白载体,在含水率为60％以及连...     

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。     

TiO_2对几种农药在土壤中光降解的催化作用

以太阳光为光源,研究了TiO2添加量、土壤厚度对毒死蜱、苯线磷、克百威、多菌灵在土壤中光催化降解的影响,并分析了毒死蜱、苯线磷初始浓度对其光催化降解的影响。结果表明,这4种农药的光降解均符合准一级动力学方程,随着TiO2添加量从0mg/kg增加到200mg/kg,光催化降解一级动力学常数逐渐增加。这4种农药在不同厚度含有TiO2的土壤中的光催化降解率不同;在土壤厚度较大的情况下,相应的半衰期也较长;在土壤中添加毒死蜱、苯线磷浓度相对较低的情况下,其对应的光催化降解较快。     

Persistence of chlorpyrifos in a mineral and an organic soil

Chlorpyrifos (Lorsban emulsifiable concentrate) was applied at 3.4 kg AI/ha and incorporated into sand and muck soil contained in small field plots. Soil samples were taken at intervals over 2 yr. Radishes and carrots, seeded yearly, served as indicator crops for absorption of insecticide residues. Samples were extracted and analyzed, by gas-liquid chromatography, for chlorpyrifos, oxychlorpyrifos, and 3,5,6-trichloro-2-pyridinol. Chlorpyrifos residues declined rapidly, with 50% of the initial application remaining after 2 and 8 wk in sand and muck, respectively, and 4 and 9% after 1 yr. Pyridinol residues increased to 13 and 39% of the initial chlorpyrifos application in sand and muck after 1 and 8 wk, respectively, and declined thereafter. Oxychlorpyrifos was detected in the 2 soils at very low levels only in immediate posttreatment samples. In the first year of the study low levels (less than 0.1 ppm) of chlorpyrifos and the pyridinol were detected in radishes and carrots.     

Monitoring of pesticide chlorpyrifos residue in farmed fish: investigation of possible sources

Chlorpyrifos, a widely used organophosphorus insecticide having many urban and agricultural pest control uses, is one of the major pesticides detected in Taiwan fishery products. Whereas previous studies examined, this study explored possible sources of chlorpyrifos residue, particularly in farmed fish. Eight hundred fourteen samples of marketable fish were analyzed for chlorpyrifos residues. One hundred thirty-seven samples contained detectable residues, and farmed fish showed higher detection rates (23%) than wild fish. Based on the findings of all media of the eleven aquiculture farms, the existence of chlorpyrifos in the farmed fish were positively related to existence in fish feed. A study of indoor carp confirmed dietary accumulation of chlorpyrifos.     

In-vivo interaction of some organophosphorus insecticides with different biochemical targets in white rats

A comparative study between five organophosphorus insecticides: Leptophos, EPN, Cyanofenphos, Chlorpyrifos and Diazinon, was carried out for acute oral toxicity to white rats and for their in vivo interaction at 1/10th of LD50 doses with the activity of six serum enzymes after 4 wks from oral administration. Leptophos, Chlorpyrifos and diazinon exerted significant inhibition particularly to glutamic oxaloacetic transaminase (GOT), glutamic pyruvic transaminase (GPT), glutamyltransferase (GT) and lactate dehydrogenase (LDH). Adding ascorbic acid in the diet at 0.5% enhanced the acute oral toxicity of leptophos, chlorpyrifos and diazinon. For all the compounds, presence of ascorbic acid protected a number of the monitored serum enzymes from being inhibited except for leptophos. Ascorbic acid caused hypoglycemia with sublethal doses of leptophos, chlorpyrifos, and diazinon. The synergist piperonyl butoxide alone at 750 mg/kg dose inhibited the activity of the six serum enzymes. Presence of ascorbic acid in the diet intensified the inhibitory effect of piperonyl butoxide to all enzymes except for GOT.     

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).     

Feasibility of constructed wetlands for removing chlorothalonil and chlorpyrifos from aqueous mixtures

Chlorpyrifos (an insecticide) and chlorothalonil (a fungicide) are transported in stormwater runoff and can be lethal to receiving aquatic system biota. This study determined removal rates of chlorpyrifos and chlorothalonil in simulated stormwater runoff treated in constructed wetland mesocosms. Using sentinel species, Ceriodaphnia dubia and Pimephales promelas, observed declines in toxicity of the simulated runoff after treatment were 98 and 100%, respectively. First order removal rates were 0.039/h for chlorpyrifos and 0.295/h for chlorothalonil in these experiments. Constructed wetland mesocosms were effective for decreasing concentrations of chlorpyrifos and chlorothalonil in simulated stormwater runoff, and decreasing P. promelas and C. dubia mortality resulting from these exposures. The results from this study indicate that constructed wetlands could be part of an efficient mitigation strategy for stormwater runoff containing these pesticides.     

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.     

Chlorpyrifos degradation in Turkish soil

Degradation of chlorpyrifos was evaluated in laboratory studies. Surface (0-15 cm) and subsurface (40-60 cm) clay loam soils from a pesticide-untreated field were incubated in biometer flasks for 97 days at 25 degrees C. The treatment was 2 micrograms g-1 [2,6-pyridinyl-14C] chlorpyrifos, with 74 kBq radioactivity per 100 g soil flask. Evolved 14CO2 was monitored in KOH traps throughout the experiment. Periodically, soil subsamples were also methanol-extracted [ambient shaking, then supercritical fluid extraction (SFE)], then analyzed by thin-layer chromatography. Total 14C and unextractable soil-bound 14C residues were determined by combustion. From the surface and subsurface soils, 41 and 43% of the applied radiocarbon was evolved as 14CO2 during 3 months incubation. The time required for 50% loss of the parent insecticide in surface and subsurface soils was about 10 days. By 97 days, chlorpyrifos residues and their relative concentration (in surface/subsurface) as % of applied 14C were: 14CO2 (40.6/42.6), chlorpyrifos (13.1/12.4), soil-bound residues (11.7/11.4), and 3,5,6-trichloropyridinol (TCP) (3.8/4.8). Chlorpyrifos was largely extracted by simple shaking with methanol, whereas TCP was mainly removed only by SFE. The short persistence of chlorpyrifos probably relates to the high soil pH (7.9-8.1).     

Reference values for acetyl and butyrylcholinesterases in cattle under actual management conditions,hepatic and renal function by application of chlorpyrifos

Chlorpyrifos is an anticholinesterase organophosphate insecticide widely used in Argentina in the production of food derived from animal, fruit and horticultural origin and is reported as a residue within these products. Local reference values for acetyl and butyrylcholinesterase were determined in Aberdeen Angus bovine and cross bred cattle (n = 25), a requirement to be able to evaluate toxicity of commercial organophosphate and carbamate formulations. The activity of cholinesterase enzymes presented an overall mean of 2,183.00 ± 485.6 IU L^?1 for erythrocyte acetylcholinesterase and 203.1 ± 42.06 IU L^?1 for plasma butyrylcholinesterase, which are used as reference values for meat steers within a system of intensive production in a semi-arid region. The toxic potential of chlorpyrifos in steers of the same breeds (n = 12) was assessed applying chlorpyrifos 15.00% Tipertox® in a single therapeutic dose of 7.50 mg kg^?1 by topical route. Prior to application and then on day 1 and day 21 post-application, both blood cholinesterases, serum chlorpyrifos concentration by ultra-high resolution liquid chromatography with mass detector, analysis of blood counts, total proteins, liver enzymes, urea and creatinine were evaluated. The mean plasma concentration of chlorpyrifos was 27.90 ug L^?1 at 24 h. The findings indicate that the therapeutic treatment of castrated male bovines treated with chlorpyrifos, applied by pour-on according to the manufacturer's instructions, does not cause changes in the variables evaluated.     

Biodegradation of chlorpyrifos by either single or combined cultures of some soilborne plant pathogenic fungi

Abstract

Biodegradation of chlorpyrifos was studied in liquid culture media amended with either single or combined eight different plant pathogenic fungi isolated from the continuous cropping wheat fields. The average recovery of chlorpyrifos from the liquid media was found to be 86.1%. The detection limit of chlorpyrifos by the analytical method used was 19 ppb. Data showed that the growth of mixed fungi at concentrations up to 200 ppm of chlorpyrifos was higher than in the control treatment. Chlorpyrifos concentrations declined in the medium of combined fungi more than it did in the medium of any single fungus with increase in the incubation period. The amount of chlorpyrifos recovered was 79.8 ppm (39.9%) in the combined fungal cultures after 21 days. However, those recovered from the media of Fusarium graminearum, F. oxysporum, Rhizoctonia solani, Cladosporhim cladosporiodes, Cephalosporium sp., Trichoderma viridi, Alternaria alternata, and Cladorrhinum brunnescens, ranged from 48.0 to 74.8%. The half‐life value (T_1/2) for chlorpynfos was 15.8 day in the medium amended with mixed fungi. However, for the single cultures it ranged from 19.3 to 33.0 day.