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1.
There is growing concern about the fate and toxicity of herbicides to non‐target receptors and an increasing need to measure these analytes sensitively. The responses of cellular and immunological biosensors to four commonly used herbicides (atrazine, diuron, mecoprop and paraquat) were investigated. In combination, these sensors assess toxicity and quantify concentrations of herbicides present in extracts from soil. The bioluminescence response of the lux‐marked bacterial biosensor Escherichia coli HB101 was determined in aqueous extracts from soil to indicate toxicity. Smaller concentrations caused a toxic response for all four herbicides recovered from the Insch series than for those recovered from spiked water samples, but this was not a result of biodegradation of herbicides in the soil. This suggests that intrinsic soil factors may be altering the bioavailable fraction of herbicides, making them more toxic than equivalent concentrations in water. Herbicide concentrations were determined using immunological biosensors consisting of stabilized recombinant single chain antibodies (stAbs) specific for the four different groups of herbicides. These stAb fragments retain functionality in organic solvents such as methanol commonly used in soil extraction. Anti‐atrazine, mecoprop, diuron and paraquat stAbs were successfully used to identify and quantify herbicides present in aqueous and methanol extracts from soil. The amounts recovered from immunoassay analysis were compared with chemical analysis using high performance liquid chromatography, and the two methods correlated. These stAb fragments might provide a more rapid and sensitive means of quantifying trace amounts of herbicides and their metabolites in aqueous and methanol extracts from soil.  相似文献   

2.
The impact of two tillage systems, plow tillage (PT) and no-tillage (NT), on microbial activity and the fate of pesticides in the 0–5 cm soil layer were studied. The insecticides carbofuran and diazinon, and the herbicides atrazine and metolachlor were used in the study, which included the incubation and leaching of pesticides from untreated soils and soils in which microorganisms had been inhibited. The mineralization of ring14C labeled pesticides was studied. The study differentiated between biotic and abiotic processes that determine the fate of pesticides in the soil. Higher leaching rates of pesticides from PT soils are explaned by the relative importance of each of these processes. In NT soils, higher microbial populations and activity were associated with higher mineralization rates of atrazine, diazinon and carbofuran. Enhanced transformation rates played an important role in minimizing the leaching of metolachlor and carbofuran from NT soils. The role of abiotic adsorption/retention was important in minimizing the leaching of metolachlor, carbofuran and atrazine from NT soils. The role of fungi and bacteria in the biodegradation process was studied by selective inhibition techniques. Synergistic effects between fungi and bacteria in the degradation of atrazine and diazinon were observed. Carbofuran was also degraded in the soils where fungi were selectively inhibited. Possible mechanisms for enhanced biodegradation and decreased mobility of these pesticides in the upper layer of NT soils are discussed.  相似文献   

3.
为掌握玉米病虫害发生种类和农药使用情况,制定玉米病虫害防治规范。采用定点调查方法,对陇西县玉米病虫害及农药使用情况进行了调查。调查发现,该县玉米主要病害有茎基腐病、锈病、大斑病和小斑病,虫害有玉米螟、蚜虫、红蜘蛛、蓟马、黏虫和地下害虫等。将农药使用情况录入全国农药信息管理系统进行分析,表明在玉米整个生育期,按其类型,除草剂用量最大,其次为杀虫剂和杀菌剂,生长调节剂用量最小;按毒性,低毒农药用量最大,其次为中毒农药,微毒农药用量最小;按种类,以化学农药为主、生物农药为辅;按农药成分,辛硫磷、莠去津用量较大。  相似文献   

4.
Rates of degradation of seven organophosphate nematicides and insecticides were examined in two soils known to show accelerated biodegradation of fenamiphos and one soil known to show accelerated biodegradation of chlorpyrifos. The results indicated that several organophosphate insecticides and one nematicide were susceptible to cross-enhanced degradation in the soil showing accelerated biodegradation of chlorpyrifos. No cross-enhancement was observed in the two soils showing accelerated degradation of fenamiphos. Fumigation resulted in the complete inhibition of pesticide degradation in all soils. The data suggested that the cross-enhancement of selected pesticides in chlorpyrifos-degrading soil was dependent on the structural similarity of the compounds. Mechanisms of degradation of pesticide in soil support this hypothesis, where structurally similar compounds (diazinon, parathion, coumaphos and isazofos) were hydrolysed by microbial activity in chlorpyrifos-degrading soil but the degradation products were accumulated. Enhanced degradation of chlorpyrifos and fenamiphos was found to be stable in the laboratory condition for a period of one year.  相似文献   

5.
Methods were developed to determine OH reaction rates for medium-weight organophosphorus pesticides in the gas phase. A 57-L chamber was constructed that utilized xenon arc irradiation (>290 nm) to photolyze the OH precursor, methyl nitrite. Experiments were performed at elevated temperatures ranging from 60 to 80 degrees C to minimize wall sorption. Solid-phase microextraction (SPME) sampling of the gas phase was employed to assess the simultaneous rate of loss of the pesticides in relation to the rate of loss of two reference substances with known OH rate constants. An internal gas-phase standard (hexachlorobenzene), relatively stable to hydroxyl radicals, was used to assess other processes, which included dilution and wall sorption. The relative reaction rates of the organophosphorus insecticides, diazinon and chlorpyrifos, when compared to reference compounds, were unaffected by various air temperatures between 60 and 80 degrees C. Although both insecticides were expected to react at similar rates on the basis of structural activity model predictions, diazinon reacted 3 times more rapidly than chlorpyrifos and gave estimated environmental OH half-lives of 0.5 and 1.4 h, respectively. The degree of sorption onto the chamber walls was minimal and similar for each of the compounds examined. Experimental gas-phase determinations at elevated temperatures may provide important information that can be used when in the assessment of the potential of airborne pesticide risks to nontarget and ecologically sensitive areas.  相似文献   

6.
Degradation of atrazine and alachlor in saturated aquifer materials and soil was studied in the laboratory. A static aquifer was represented by a set of stagnant flasks and a well-mixed aquifer was simulated by recirculating columns. Water was tested at selected time intervals over six months and analyzed for herbicides and metabolites. Under all conditions, atrazine was more persistent than alachlor. Increased temperature had little effect on atrazine dissipation but did increase alachlor degradation rates, especially in the sterilized treatments. The addition of carbon and nitrogen prolonged the initial period before the onset of degradation in some of the columns. Enhanced mass transfer of the herbicides, nutrients, and oxygen in the recirculating columns dramatically increased dissipation of atrazine and alachlor. The degradation rates of atrazine and alachlor were 2 to 5 times faster in the recirculating columns than in the stagnant flasks. Atrazine was more persistent in the aquifer materials than in the soils, while alachlor dissipation was similar in the soils and recirculating aquifer columns, but was slower in the stagnant flasks. The prolonged persistence of atrazine under static, aquifer conditions (t 1/2 = 206 to 710 days) indicates that natural mechanisms are not sufficient to alleviate the risk of atrazine buildup over time; however, in a well mixed aquifer, atrazine degradation rates should be higher (t 1/2 = 66 to 106 days) and the threat of atrazine accumulation is diminished. Alachlor persistence at low concentrations (< 10 μg L?1) in aquifers should not pose a long-term threat to ground water supplies.  相似文献   

7.
The processing factors (pesticide concentration found in olive oil/pesticide concentration found in olives) of azinphos methyl, chlorpyrifos, lambda-cyhalothrin, deltamethrin, diazinon, dimethoate, endosulfan, and fenthion were determined in olive oil production process in various laboratory-scale olive oil extractions based on three- or two-phase centrifugation systems in comparison with samples collected during olive oil extractions in conventional olive mills located at different olive oil production areas in Greece. Pesticide analyses were performed using a multiresidue method developed in our laboratory for the determination of different insecticides and herbicides in olive oil by solid-phase extraction techniques coupled to gas chromatography detection (electron capture detection and nitrogen phosphorus detection), optimized, and validated for olive fruits sample preparation. Processing factors were found to vary among the different pesticides studied. Water addition in the oil extraction procedure (as in a three-phase centrifugation system) was found to decrease the processing factors of dimethoate, alpha-endosulfan, diazinon, and chlorpyrifos, whereas those of fenthion, azinphos methyl, beta-endosulfan, lambda-cyhalothrin, and deltamethrin residues were not affected. The water content of olives processed was found to proportionally affect pesticide processing factors. Fenthion sulfoxide and endosulfan sulfate were the major metabolites of fenthion and endosulfan, respectively, that were detected in laboratory-produced olive oils, but only the concentration of fenthion sulfoxide was found to increase with the increase of water addition in the olive oil extraction process.  相似文献   

8.
The effects of 20 herbicides on denitrification of nitrate in three soils were studied by determining the effects of 10 and 50μgg?1 soil of each herbicide on the amounts of nitrate lost and the amounts of nitrite, N2O and N2 produced when soil samples were incubated anaerobically after treatment with nitrate. The herbicides used were butylate, EPTC, chlorpropham, propham, diuron, linuron, monuron, siduron, alachlor, trifluralin, 2,4-D amine, 2,4-D ester, atrazine, cyanazine, metribuzin, simazine, dalapon, chloramben, dicamba and dinoseb.None of the herbicides studied significantly affected denitrification of nitrate when applied at the rate of 10 μg g?1 soil, but dinoseb increased the ratio of N2 to N2O in the gaseous products of denitrification when applied at this rate. Butylate, EPTC, diuron, simazine and dalapon had no significant effect on denitrification when applied at the rate of 50μgg?1 soil, whereas metribuzin and dinoseb enhanced denitrification when applied at this rate. The influence of the other herbicides on denitrification when applied at the rate of 50μgg?1soil depended on the soil, but all enhanced or inhibited denitrification in at least one soil.  相似文献   

9.
Atrazine [6-chloro-N-ethyl-N′-(1-methyl)-1,3,5 triazine-2,3-diamine] and alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl) acetamide] are agricultural herbicides used in large quantities and, as a consequence, are common contaminants in groundwater and surface water. The retention of these herbicides in soils and their degradation in aqueous environments is highly dependent upon their adsorption to solid surfaces. The adsorption of atrazine and alachlor was investigated on three typical Kansas and underlying aquifers known to be vulnerable to contamination. More alachlor was adsorbed to the soils and sediments than atrazine. The adsorption coefficients for atrazine were 2 to 5 times higher for soils than for aquifer sediments. For alachlor, the adsorption coefficients were 4 to 20 times higher for soil than for aquifer solids. Both linear and Freundlich isotherms represented the adsorption data well in all cases. The slope of the Freundlich isotherms, 1/n, was close to one, with the exception of alachlor adsorption onto the Topeka aquifer sediment (1/n = 0.67). The K d values found in these studies were comparable to the lower range of those reported in the literature.  相似文献   

10.
The presence of pesticides in compost is of interest because of possible health, production and ecological risks. The presence of over 50 pesticides was assessed in raw yard waste, milled yard waste, and a finished compost (yard waste:biosolids) at a commercial compost facility in Florida. These pesticides were comprised of 38 herbicides, eight insecticides and two fungicides. Of the pesticides monitored for in this study, only atrazine, 4,4-DDE, alpha chlordane, gamma chlordane, and endosulfan I were detected, and were only present in raw yard wastes.  相似文献   

11.
Lake Vela (Littoral Centre of Portugal) is considered a natural habitat with community interest and consequently was included in the Natura 2000 Network. However, this freshwater ecosystem has been potentially exposed to diffuse pollution generated by agricultural and livestock activities, which seriously compromise its ecological balance. As part of the Ecological Risk Assessment (ERA) proposed for Lake Vela, this study aimed to evaluate the occurrence of pesticides in different compartments: surface water, groundwater, sediments, and fish tissues. Moreover, to assess potential concerning effects on ecosystem and human health, the measured concentrations of pesticides were compared with regulatory and toxicological benchmarks. The results confirmed the presence of high concentrations of pesticides, including organochloride pesticides banned decades ago, in surface water, groundwater, and sediment. The measured concentrations of pesticides, compared with toxicological benchmarks, indicated that harmful effects are likely for aquatic species due to the presence of alachlor, aldrin, and dieldrin. Additionally, the concentrations of pesticides detected in groundwater were also above the recommended safety levels for drinking water, which constitutes a concern for the local population’s health. Results also showed an accumulation of alachlor in predator and benthic fish species which could represent a risk to human consumers and particularly to the regular fish predators (e.g., otters and birds). This study, as the first exposure characterization performed on the Lake Vela system, constitutes valuable and useful information for the ERA process. Although this preliminary assessment of risks should be continued and confirmed through a weight-of-evidence approach, it had already unraveled how concerning are the problems in this ecosystem and the urgency of implementing restoration measures to guaranty its sustainability. Furthermore, this study reinforces the importance of evaluating similar freshwater ecosystems that are also highly threatened by diffuse pollution.  相似文献   

12.
五种杀虫剂对卵寄生性天敌广赤眼蜂室内安全性评价   总被引：3，自引：0，他引：3  
在实验室条件下分别用药膜法、寄主卵块喷雾法和盆栽法测定了苏云金杆菌等5种杀虫剂菜田防治推荐浓度对广赤眼蜂5种虫态的毒性及雌蜂的残留毒性.不同农药对广赤眼蜂各虫态的毒性存在差异, 对其存活、羽化和寄生能力等有不同程度的影响, 其中对成蜂的毒性最强.苏云金杆菌和啶虫脒对广赤眼蜂5种虫态的杀伤力较低, 对羽化蜂的寿命和翅的发育影响较小或无影响, 同时施药后的残效期较短, 对成蜂的存活和寄生能力的影响较小.阿维菌素除卵和幼虫期处理对广赤眼蜂无影响或影响轻微外, 预蛹和蛹期处理, 羽化率降低, 羽化后雌蜂寿命缩短, 前翅发育不全比例升高, 其不良影响随蜂的发育呈增大趋势; 此外, 喷药后7 d其残留农药对雌蜂的存活和寄生能力仍有较大影响.高效氯氟氰菊酯卵期至蛹期处理广赤眼蜂能显著降低该蜂的羽化率, 成蜂期处理的死亡率在70%以上, 但该药残留毒性期较短, 喷药后5 d成蜂存活和寄生能力基本恢复正常.毒死蜱对各虫期的广赤眼蜂均有极强的杀伤力, 喷药后10 d仍有很高的残留毒性.总之, 苏云金杆菌和啶虫脒对广赤眼蜂无毒或毒性较低, 是生防区理想的配合药剂;阿维菌素和高效氯氟氰菊酯毒性中等, 使用时要尽量避开赤眼蜂成蜂活动期;毒死蜱毒性极强, 生防区应禁止使用.  相似文献   

13.
The volatile and soil loss profiles of six agricultural pesticides were measured for 20 days following treatment to freshly tilled soil at the Beltsville Agricultural Research Center. The volatile fluxes were determined using the Theoretical Profile Shape (TPS) method. Polyurethane foam plugs were used to collect the gas-phase levels of the pesticides at the TPS-defined critical height above a treated field. Surface-soil (0-8 cm) samples were collected on each day of air sampling. The order of the volatile flux losses was trifluralin > alpha-endosulfan > chlorpyrifos > metolachlor > atrazine > beta-endosulfan. The magnitude of the losses ranged from 14.1% of nominal applied amounts of trifluralin to 2.5% of beta-endosulfan. The daily loss profiles were typical of those observed by others for volatile flux of pesticides from moist soil. Even though heavy rains occurred from the first to third day after treatment, the majority of the losses took place within 4 days of treatment, that is, 59% of the total applied atrazine and metolachlor and >78% of the other pesticides. Soil losses generally followed pseudo-first-order kinetics; however, leaching due to heavy rainfall caused significant errors in these results. The portion of soil losses that were accounted for by the volatile fluxes was ordered as follows: alpha-endosulfan, 34.5%; trifluralin, 26.5%; chlorpyrifos, 23.3%; beta-endosulfan, 14.5%; metolachlor, 12.4%; and atrazine, 7.5%.  相似文献   

14.
The acute toxic effects of diflubenzuron (DFB) on various life stages of the grass shrimp, Palaemonetes pugio, were determined using a static renewal system. It was observed that the larvae and the postlarvae were the most sensitive to acute DFB toxicity; 96-hr LC50's being 1.44 and 1.62 μg L?1 respectively. Also variations among the 96-hr LC50's for these two life stages were the lowest (11.59% for larvae and 30.06% for postlarvae) compared to 68.9% for males and non-Ovgerous females. Ovigerous female grass shrimp (hence the embryos) appeared to be the most resistant to acute toxic effects of DFB with a mean LC50 of 6985 μg L?1. The limitations of LC50 data and the importance of molt-related sensitivity of the different life stages of P. pugio to diflubenzuron are discussed.  相似文献   

15.
In this work, we examined the effect of two different organic wastes, composted sheep manure and coir, on the sorption, persistence, and mobility of three pesticides (alachlor, chlorfenvinphos, and chlorpyrifos) included as priority substances in European Directive 2013/39/EU. With this aim, leaching studies were conducted using disturbed soil columns filled with a typical agricultural soil (hipercalcic calcisol) from a semiarid area (southeastern Spain) to determine their potential for groundwater pollution. The three compounds were found in leachates of unamended soil although in different proportions: 53% (alachlor), 9% (chlorfenvinphos), and 6% (chlorpiryfos). The addition of organic wastes significantly increased the sorption of the studied pesticides. As a consequence, the half-lives of the studied pesticides were higher in amended than in unamended soils. A marked reduction of the amount recovered in leachates was observed in the amended soils, except for chlorpiryfos, whose recoveries barely changed. According to their potential groundwater pollution calculated as the groundwater ubiquity score (GUS) index, alachlor and chlorfenvinphos show medium leachability while chlorpiryfos is unlikely to leach.  相似文献   

16.
Adsorption of the chloroacetanilide herbicides acetochlor, alachlor, metolachlor, and propachlor was determined on soils and soil components, and their structural differences were used to explain their sorptivity orders. On all soils and soil humic acids, adsorption decreased in the order: metolachlor > acetochlor > propachlor > alachlor. On Ca(2+)-saturated montmorillonite, the order changed to metolachlor > acetochlor > alachlor > propachlor. FT-IR differential spectra of herbicide-clay or herbicide-humic acid-clay showed possible formation of hydrogen bonds and charge-transfer bonds between herbicides and adsorbents. The different substitutions and their spatial arrangement in the herbicide molecule were found to affect the relative sorptivity of these herbicides by influencing the reactivity of functional groups participating in these bond interactions. It was further suggested that structural characteristics of pesticides from the same class could be used to improve prediction of pesticide adsorption on soil.  相似文献   

17.
An interlaboratory study was conducted to compare pesticide recovery from Empore C(18) and Speedisks C(18)XF solid phase extraction disks after shipping. Four pesticides were used for the comparison of the two disk extraction materials: atrazine, diazinon, metolachlor, and tebuconazole. These pesticides were chosen to provide a range of physiochemical properties. Water samples were extracted onto the disk types and shipped to a cooperating laboratory for elution and analysis. The mean recoveries from Empore disks were atrazine, 95%; diazinon, 91%; metolachlor, 92%; and tebuconazole, 83%. The recoveries from Speedisks C(18)XF were atrazine, 89%; diazinon, 87%; metolachlor, 86%; and tebuconazole, 79%. Means for each of the pesticides using the different disk types were not statistically different (alpha = 0.05), but results were more variable when using Speedisks C(18)XF as compared to Empore disks. Reasons for the increased variability are discussed, but overall results indicate that Speedisks C(18)XF could be used as an alternative to Empore disks. Speedisks C(18)XF are enclosed in a plastic housing, so they can be used more easily in remote sampling sites without the possibility of glassware breakage, no prefiltration of samples is needed, and there are realignment problems that can be associated with the Empore disks.  相似文献   

18.
Extraction of several nitrogen-containing pesticides from water on solid-phase C18 cartridges was rapid and accurate. One analyst can extract greater than 48 samples/day. Recovery efficiencies were 77, 95, 92, 90, and 99% with detection limits of 0.20, 0.05, 0.05, 0.20, and 0.10 micrograms/L for carbofuran, atrazine, simazine, alachlor, and, cyanazine, respectively. Extraction of the atrazine and simazine dealkylation products (deethylatrazine and deethylsimazine) was less efficient, e.g., 26 and 9%, respectively. Comparisons with 10 U.S. Geological Survey samples gave similar results.  相似文献   

19.
为解决食品中毒死蜱残留检测过程中步骤繁琐,灵敏度低的问题,采用高富集因子的针式滤器固相微萃取结合高灵敏度的酶抑制-数字图像比色法对毒死蜱进行快速检测。该研究以石墨烯纳米片作为固相吸附剂装入针式滤器,随后通过注射器重复抽打针式滤器的方法实现样品中毒死蜱的富集。酪氨酸酶能够将邻氨基苯酚和氯化铁体系氧化为黄色,毒死蜱会抑制酪氨酸酶的活性,从而会间接影响邻氨基苯酚和氯化铁体系的显色,通过数字图像比色法实现毒死蜱的定量分析。结果表明：毒死蜱在0.005～0.1 mg/L范围内线性良好,R2>0.99。在矿泉水、茶水和果汁中的测定下限为0.005 mg/L。样品加标后的萃取率为86.6%～92.5%,相对标准偏差为3.2%～6.9%。该方法有助于开发农药的快速前处理和检测技术。  相似文献   

20.
Particulates (ashes) arising from the burning of crop residues are potentially effective adsorbents for pesticides in agricultural soils. To determine the long-term adsorptive sustainability of ashes, a wheat (Triticum aestivum L.) ash was aged under environmentally relevant conditions (in CaCl(2) solution at room temperature and pH 7) in soil extract for 1 month and in a soil (1% ash) for a period of up to 12 months. The aged ash and ash-amended soil were used to sorb diuron from water. The diuron sorption was also measured in the presence of atrazine as a competing pesticide. There was no observed microbial impact on the stability of the wheat ash in soil. All isotherms with the ash were nonlinear type-I curves, suggestive of the surface adsorption. On a unit mass basis, the ash in soil extract was 600-10000 times more effective than the soil in sorbing diuron. Adsorption of dissolved soil organic matter (DOM) during aging on the ash surfaces reduced the diuron adsorption by 50-60%. Surface competition from the atrazine adsorption also reduced the ash adsorption of diuron by 10-30%. A total of 55-67% reduction in diuron sorption by the ash-amended soil was observed. Due to its high initial adsorptivity, the ash fraction of the aged ash-amended soil contributed >50% to the total diuron sorption. Thus, the wheat ash aged in the soil remained highly effective in adsorbing diuron. As crop residues are frequently burned in the field, pesticides in agricultural soils may be highly immobilized due to the presence of ashes.  相似文献   

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