拟除虫菊酯类农药废水处理技术研究进展

拟除虫菊酯类农药废水COD浓度高、毒性大、污染物成分复杂、较难生物降解。通过系统阐述目前国内外各种针对拟除虫菊酯类农药废水处理技术的最新研究动态,分析了各种方法的优缺点,并对此类农药废水处理技术的发展方向进行了展望,可为此类废水处理工艺选择和工程设计提供有益参考。     

农药的微生物降解

阐述了农药对现代农业的重要性,以及对动物、特别是对人类的危害,并介绍了农药的微生物降解过程.     

有机磷农药残留检测技术研究进展

综述了近年来有机磷农药残留检测技术的研究进展,其检测方法主要有色谱法、降解酶法、化学发光技术和生物传感技术.详细介绍了几种生物传感器(如酶传感器、微生物传感器、免疫传感器、压电传感器、纳米传感器和液晶型化学传感器)在有机磷农药检测中的应用,并展望了这一领域的发展趋势.     

农药微生物降解的研究现状与发展策略

本文在农药降解菌的富集分离及农药微生物降解的途径，特别在微生物产生的农药降解酶和农药微生物降解基因操作方面对农药微生物降解的研究现状作了简要综述，提出了农药微生物降解的研究趋势。联系地址：中国科学院广州地球化学研究所，广州五山，５１０６４０津、环草隆、三氯醋酸、氯苯胺灵等。芽孢杆菌属（Ｂａｃｉｌｌｕｓ）：ＤＤＴ、ｒ－ＢＨＣ、艾氏剂、狄氏剂、异狄氏剂、七氯、苯硫磷、对硫磷、甲基对硫磷、杀螟松、毒杀芬、茅草枯、三氯醋酸、利谷隆、灭草隆、毒旁定。节细菌属（Ａｒｔｈｒｏｂａｃｔｅｒ）：ＤＤＴ、艾氏剂、异狄氏剂、七氯、草多索、马拉硫磷、二嗪农、２，４－Ｄ、２甲４氯、茅草枯、三氯醋酸、毒莠定、西玛津、味哺丹［８］。棒状杆菌属（Ｃｏｒｙｎｂｏａｃｔｅｒｉｕｍ）：ＤＤＴ、２，４－Ｄ、２甲４氯、茅草枯、二硝甲酚、百草枯、草枯醚。无色杆菌属（Ａｃｈｒｏｍｏｂａｃｔｅｒ）：ＤＤＴ、西维因、２，４－Ｄ、２甲４氯、２，４，５－Ｔ、氯苯胺灵。土壤杆菌属（Ａｇｒｏｂａｃｔｅｒｉｕｍ）：ＤＤＴ、氯苯胺灵、茅草枯、三氯醋酸、毒莠定。黄杆菌属（Ｆｌａｖｏｂａｃｔｅｒｉｕｍ）：对硫磷、甲基对硫磷、马拉硫磷、二嗪农、毒死蜱、２，４－Ｄ、２甲４氯、     

环境条件对土壤中磺胺间甲氧嘧啶降解的影响

通过在实验室模拟不同的环境条件,研究常用兽药抗生素--磺胺间甲氧嘧啶(SMM)在土壤中的降解动态及其影响因素(如微生物和光照,土壤含水量、药物起始浓度等).结果表明,SMM在土壤中的降解遵循一级反应动力学方程.SMM在土壤中的降解主要是光降解和化学降解,微生物降解只占较小比例;土壤含水量的增加明显加快了SMM的降解速率,因而可以通过降低土壤中SMM残留浓度或提高土壤含水量等方法加速SMM的降解.以降低其对环境土壤和水体的风险;SMM的降解速率随土壤中SMM起始浓度增加而降低,表明土壤中降解微生物对SMM的浓度敏感.     

氯代有机溶剂共降解研究进展

本文综述了有机氯溶剂的微生物共降解过程。多种多样的微生物能够通过共代谢途径降解有机氯溶剂。共降解是由微生物细胞内的关键酶进行的。影响共降解的主要因素包括关键酶的诱导 ,毒性抑制和自我恢复以及能量供应等。本文对共降解过程的机理和相关的数学模型进行了综合分析。在此基础上 ,提出了一个能够揭示共降解过程各种因素之间内在逻辑关系的结构模型 ,对于从细胞和酶两个层次上认识共降解过程具有重要的指导意义。     

氯代有机溶剂共降解研究进展

本文综述了有机氯溶剂的微生物共降解过程。多种多样的微生物能够通过共代谢途径降解有机氯溶剂。共降解是由微生物细胞内的关键酶进行的。影响共降解的主要因素包括关键酶的诱导,毒性抑制和自我恢复以及能量供应等。本文对共降解过程的机理和相关的数学模型进行了综合分析。在此基础上,提出了一个能够揭示共降解过程各种因素之间的内在逻辑关系的结构模型,对于从细胞和酶两个层次上认识共降解过程具有重要的指导意义。     

乐果好氧降解菌的驯化和筛选

为了获得有效降解有机磷农药乐果的微生物,采用北京大兴黄村施用过乐果的土壤为菌源,以乐果作为唯一碳源和能源分离得到5株对乐果有一定降解能力的细菌。正交实验结果显示:降解菌在温度为40℃,pH值为9,NaCl浓度为0 .5g/L条件下生长良好。     

含氯消毒剂与多类农药的反应活性研究

为了研究农药在饮用水消毒过程中的降解情况,选择了8类使用广泛或者在水源中已检测出有残留的农药,研究其与普遍使用的3种含氯消毒剂(自由氯、氯胺和二氧化氯)的反应活性.实验结果表明,在农药浓度为5μmol/L(少数除外),消毒剂与农药摩尔比为200:1,pH 6.58-6.84,温度25±3℃的条件下,自由氯与除草定、乐果、涕灭威、涕灭威亚砜和灭虫威这5种农药反应很快,在2 min内就将其完全降解,杀线威在60 min内降解了98%;一氯胺只与涕灭威、灭虫威有很高的反应活性,分别在1 min和4 min内将2种农药降解完毕;二氧化氯可以在10 min内完全降解除草定,反应120 min后对涕灭威和灭虫威的降解率分别为75%和81%.3种消毒剂与其他种类农药的反应活性都很低.因此,在使用这3种消毒剂进行饮用水消毒处理时,只能有效降解(或转化)少数种类的农药,而大多数种类的农药将可能维持其化学结构,进入供水管网.     

常见拟除虫菊酯和有机磷农药对鱼类的急性及其联合毒性研究

以崇明岛前卫村中心湖中鲫鱼、鲤鱼、鲢鱼及泥鳅作为实验动物.进行了氯氰菊酯(原药和商品)、氰戊菊酯(原药和商品)、毒死蜱(原药和商品)、甲氰菊酯(商品)、溴氰菊酯(商品)、辛硫磷(商品)以及乙酰甲胺磷(商品)7种供试农药对实验鱼种的急性毒性及联合毒性实验,并检测了前卫村中心湖水体中18种有机磷农药和4种拟除虫菊酯农药,其中检出了1种有机磷农药(毒死蜱)和3种拟除虫菊酯农药(氰戊菊酯、氯氰菊酯、甲氰菊酯).结果表明,在单一农药急性毒性实验中,鲤鱼对供试农药表现较敏感,其次是鲫鱼和鲢鱼,而泥鳅对农药的耐药性最强;7种供试农药中,拟除虫菊酯农药相对于有机磷农药表现出较高的急性毒性,其实验鱼种的半数致死浓度(LC60)皆在μg/L级;对拟除虫菊酯农药(氯氰菊酯,氰戊菊酯)与有机磷农药(辛硫磷、乙酰甲胺磷)进行的联合毒性实验结果表明,除了暴露时间为24、48 h时氰戊菊酯与辛硫磷混配对鲢鱼的毒性实验表现为协同作用外,其余皆为拈抗作用.     

Pesticides in urban multiunit dwellings: hazard identification using classification and regression tree (CART) analysis

Many units in public housing or other low-income urban dwellings may have elevated pesticide residues, given recurring infestation, but it would be logistically and economically infeasible to sample a large number of units to identify highly exposed households to design interventions. Within this study, our aim was to devise a low-cost approach to identify homes in public housing with high levels of pesticide residues, using information that would allow the housing authority and residents to determine optimal strategies to reduce household exposures. As part of the Healthy Public Housing Initiative, we collected environmental samples from 42 public housing apartments in Boston, MA, in 2002 and 2003 and gathered housing characteristics; for example, household demographics and self-reported pesticide use information, considering information available with and without a home visit. Focusing on five organophosphate and pyrethroid pesticides, we used classification and regression tree analysis (CART) to disaggregate the pesticide concentration data into homogenous subsamples according to housing characteristics, which allowed us to identify households and associated networks impacted by the mismanagement of pesticides. The CART analysis demonstrated reasonable sensitivity and specificity given more extensive household information but generally poor performance using only information available without a home visit. Apartments with high concentrations of cyfluthrin, a pyrethroid of interest given that it is a restricted use pesticide, were more likely to be associated with Hispanic residents who resided in their current apartment for more than 5 yr, consistent with documented pesticide usage patterns. We conclude that using CART as an exploratory technique to better understand the home characteristics associated with elevated pesticide levels may be a viable approach for risk management in large multiunit housing developments.     

Pyrethroid residue dynamics in insects depends on the circadian clock

Many factors may affect pesticide effectiveness against pests. One of the factors that should be considered is circadian rhythmicity. In this study, we evaluated daily variations in pyrethroid susceptibility in the house cricket, Acheta domesticus L. Crickets were exposed to a standard dose of ß-cyfluthrin at different times of a day, and pesticide residue levels were evaluated using gas chromatography. Results demonstrate that the time of pyrethroid disappearance is correlated with the circadian clock, with the highest decomposition rate at night. Furthermore, crickets also showed the highest resistance to the insecticide at night, expressed as a high survival rate. Moreover, ß-cyfluthrin induced significant changes in thermal preferences of intoxicated crickets. This is the first report showing that pyrethroid residue levels in the crickets' body depend on its circadian clock.     

Pyrethroid insecticides in urban salmon streams of the Pacific Northwest

Urban streams of the Pacific Northwest provide spawning and rearing habitat for a variety of salmon species, and food availability for developing salmon could be adversely affected by pesticide residues in these waterbodies. Sediments from Oregon and Washington streams were sampled to determine if current-use pyrethroid insecticides from residential neighborhoods were reaching aquatic habitats, and if they were at concentrations acutely toxic to sensitive invertebrates. Approximately one-third of the 35 sediment samples contained measurable pyrethroids. Bifenthrin was the pyrethroid of greatest concern with regards to aquatic life toxicity, consistent with prior studies elsewhere. Toxicity to Hyalella azteca and/or Chironomus dilutus was found in two sediment samples at standard testing temperature (23 °C), and in one additional sample at a more environmentally realistic temperature (13 °C). Given the temperature dependency of pyrethroid toxicity, low temperatures typical of northwest streams can increase the potential for toxicity above that indicated by standard testing protocols.     

Assessment of the impact of pesticide residues on microbiological and biochemical parameters of tea garden soils in India

The main aim of this study was to assess the impact of pesticidal residues on soil microbial and biochemical parameters of the tea garden soils. The microbial biomass carbon (MBC), basal (BSR) and substrate induced respirations (SIR), beta-glucosidase activity and fluorescein diacetate hydrolyzing activity (FDHA) of six tea garden soils, along with two adjacent forest soils (control) in West Bengal, India were measured. The biomass and its activities and biochemical parameters were generally lower in the tea garden soils than the control soils. The MBC of the soils ranged from 295.5 to 767.5 micro g g(- 1). The BSR and SIR ranged from 1.65 to 3.08 mu g CO2-C g(- 1) soil h(- 1) and 3.08 to 10.76 micro g CO2-C g(- 1)h(- 1) respectively. The beta-glucosidase and FDHA of the soils varied from 33.3 and 76.3 micro g para-nitrophenol g(- 1) soil h(- 1) and 60.5 to 173.5 micro g fluorescein g(- 1)h(- 1)respectively. The tea garden soils contained variable residues of organophosphorus and organochlorine pesticides, which negatively affected the MBC, BSR, SIR, FDHA and beta -glucosidase activity. Ethion and chlorpyriphos pesticide residues in all the tea garden soils varied from 5.00 to 527.8 ppb and 17.6 to 478.1 ppb respectively. The alpha endosulfan, beta endosulfan and endosulfan sulfate pesticide residues in the tea garden soils ranged from 7.40 to 81.40 ppb, 8.50 to 256.1 ppb and 55 to 95.9 ppb respectively. Canonical correlation analysis shows that 93% of the total variation was associated with the negative impact of chlorpyriphos, beta and alpha endosulfan and endosulfan sulfate on MBC, BSR and FDHA. At the same time ethion had negative impact on SIR and beta-glucosidase. Data demonstrated that the pesticide residues had a strong impact on the microbial and biochemical components of soil quality.     

Degradation of atrazine,metolachlor, and pendimethalin in pesticide‐contaminated soils: Effects of aged residues on soil respiration and plant survival

Abstract

This study was conducted to determine the effects of pesticide mixtures on degradation patterns of parent compounds as well as effects on soil microbial respiration. Bioavailability of residues to sensitive plant species was also determined. Soil for this study was obtained from a pesticide‐contaminated area within an agrochemical dealer site. Degradation patterns were not affected by the presence or absence of other herbicides in this study. Atrazine concentrations were significantly lower at 21 through 160 days aging time compared to day 0 concentrations. Metolachlor and pendimethalin concentrations were not significantly different over time and remained high throughout the study. Microbial respiration was suppressed in treated soils from day 21 to day 160. Soybean and canola were the most successful plant species in the germination and survival tests. Generally, with increased aging of pesticides in soil, germination time decreased. Survival time of plants increased over time for some treatments indicating possible decreased bioavailability of pesticide residues. In some cases, survival time decreased at the longer 160‐day aging period, possibly indicating a change in bioavailability, perhaps as the result of formation of more bioavailable and phytotoxic metabolites. No interactive effects were noted for mixtures of pesticides compared to individually applied pesticides in terms of degradation of the parent compound or on seed germination, plant survival, or microbial respiration.     

Assessment of the impact of pesticide residues on microbiological and biochemical parameters of tea garden soils in India

The main aim of this study was to assess the impact of pesticidal residues on soil microbial and biochemical parameters of the tea garden soils. The microbial biomass carbon (MBC), basal (BSR) and substrate induced respirations (SIR), β -glucosidase activity and fluorescein diacetate hydrolyzing activity (FDHA) of six tea garden soils, along with two adjacent forest soils (control) in West Bengal, India were measured. The biomass and its activities and biochemical parameters were generally lower in the tea garden soils than the control soils. The MBC of the soils ranged from 295.5 to 767.5 μ g g^{? 1}. The BSR and SIR ranged from 1.65 to 3.08 μ g CO₂-C g^{? 1} soil h^{? 1} and 3.08 to 10.76 μ g CO₂-C g^{? 1}h^{? 1} respectively. The β -glucosidase and FDHA of the soils varied from 33.3 and 76.3 μ g para-nitrophenol g^{? 1} soil h^{? 1} and 60.5 to 173.5 μ g fluorescein g^{? 1}h^{? 1}respectively. The tea garden soils contained variable residues of organophosphorus and organochlorine pesticides, which negatively affected the MBC, BSR, SIR, FDHA and β -glucosidase activity. Ethion and chlorpyriphos pesticide residues in all the tea garden soils varied from 5.00 to 527.8 ppb and 17.6 to 478.1 ppb respectively. The α endosulfan, β endosulfan and endosulfan sulfate pesticide residues in the tea garden soils ranged from 7.40 to 81.40 ppb, 8.50 to 256.1 ppb and 55 to 95.9 ppb respectively. Canonical correlation analysis shows that 93% of the total variation was associated with the negative impact of chlorpyriphos, β and α endosulfan and endosulfan sulfate on MBC, BSR and FDHA. At the same time ethion had negative impact on SIR and β -glucosidase. Data demonstrated that the pesticide residues had a strong impact on the microbial and biochemical components of soil quality.     

Degradation of atrazine, metolachlor, and pendimethalin in pesticide-contaminated soils: effects of aged residues on soil respiration and plant survival

This study was conducted to determine the effects of pesticide mixtures on degradation patterns of parent compounds as well as effects on soil microbial respiration. Bioavailability of residues to sensitive plant species was also determined. Soil for this study was obtained from a pesticide-contaminated area within an agrochemical dealer site. Degradation patterns were not affected by the presence or absence of other herbicides in this study. Atrazine concentrations were significantly lower at 21 through 160 days aging time compared to day 0 concentrations. Metolachlor and pendimethalin concentrations were not significantly different over time and remained high throughout the study. Microbial respiration was suppressed in treated soils from day 21 to day 160. Soybean and canola were the most successful plant species in the germination and survival tests. Generally, with increased aging of pesticides in soil, germination time decreased. Survival time of plants increased over time for some treatments indicating possible decreased bioavailability of pesticide residues. In some cases, survival time decreased at the longer 160-day aging period, possibly indicating a change in bioavailability, perhaps as the result of formation of more bioavailable and phytotoxic metabolites. No interactive effects were noted for mixtures of pesticides compared to individually applied pesticides in terms of degradation of the parent compound or on seed germination, plant survival, or microbial respiration.     

Influence of the application of sewage sludge on the degradation of pesticides in the soil

A study was made of the influence of the application of sewage sludge on the degradation of pesticides in the soil. Two kinds of sludge were used, with different characteristics, one from an urban treatment plant and one from a food processing plant. Three organophosphorus insecticides, fenitrothion, diazinon and dimethoate, were studied. The relative importance was determined of the chemical and biological degradation processes, which involved experiments on soil and sterile soil samples. A comparative study was also made of the degradation of pesticide residues and the evolution of the microbial population. The application of sludge seems to have a complex effect on the degradation of pesticides, determined by the bioavailability and biodegradability of their active ingredient. The biodegradation of pesticide residues brings about alterations in the microorganism population of the soil.     

Estimation of measurement uncertainty associated to the determination of pesticide residues: a case study

In the analytical analysis the measurement uncertainty is a quantitative indicator of the confidence describing the range around a reported or experimental result within which the true value can be expected. Several approaches can be used to estimate the measurement uncertainty associated to the analysis of pesticide residues: a) the top-down, the estimation can be referred to default values; b) the bottom-up the estimation is related to the uncertainty sources. Concerning the bottom-up approach, the following contributions have been investigated: weight of sample, calibration solutions, final volume of sample and intermediate repeatability studies. The commodity/residue combination selected in this study was celery/tau-fluvalinate pesticide. Tau-fluvalinate is a broad-spectrum insecticide in the pyrethroid class of pesticides. The Maximum Residue Limit (MRL) of tau-fluvalinate in celery has been set at 0.01 mg/kg. The tau- Fluvalinate showed two chromatographic peaks. Since the individual standards are not available, the two peaks were integrated separately and the instrumental responses were added. The total residue was calculated on the basis of resulted peaks. The present work aims to compare the uncertainty estimated by experimental data using repeated analysis (n = 12) of a real sample and a spiked sample. The relative expanded uncertainty for two data set, incurred and spiked, was 22 % and 20 %, respectively. No differences were observed from repeated determinations of real samples and spiked samples.     

Dissipation of chlorpyrifos in two soil environments of semi-arid India

The dissipation of chlorpyrifos (20 EC) at environment-friendly doses in the sandy loam and loamy sand soils of two semi-arid fields and the presence of pesticide residues in the harvested groundnut seeds, were monitored. The movement of chlorpyrifos through soil and its binding in the loamy sand soil was studied using 14C chlorpyrifos. Chlorpyrifos was moderately stable in both loamy sand and sandy loam soils, with half-life of 12.3 and 16.4 days, respectively. With 20 EC treatments the dissipation was slower for standing crop than seed treatment, indicative of the high degradation rates in the bioactive rhizosphere. In soil, 3,5,6-trichloro-2-pyridinol (TCP) was the principal breakdown product. Presence of 3,5,6-trichloro-2-methoxypyridine (TMP), the secondary metabolite, detected in the rhizospheric samples during this study, has not been reported earlier in field soils. The rapid dissipation of the insecticide from the soil post-application might have resulted from low sorption due to the alkalinity of the soil and its low organic matter content, fast topsoil dissipation possibly by volatilization and photochemical degradation, aided by the low water solubility, limited vertical mobility due to confinement of residues to the upper 15 cm soil layers and microbial mineralization and nucleophilic hydrolysis. Contrary to the reports of relatively greater mobility of its metabolites in temperate soils, TMP and TCP remained confined to the top 15 cm soil. The formation of bound residues (half-life 13.4 days) in the loamy sand soil was little and not "irreversible." A decline in bound residues could be correlated to decreasing TCP concentration. Higher pod yields were obtained from pesticide treated soils in comparison to controls. Post-harvest no pesticide residues were detected in the soils and groundnut seeds.