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1.
The behavior of several pesticides in aqueous solution, namely bifenthrin, amethrin (pyrethroid insecticides), endosulfan and endosulfan sulfate (organochlorine pesticides), disulfoton, methyl pyrimiphos, and phorate (organophosphorus pesticides), submitted to the conditions typically employed in water treatment stations was investigated. Continuous pesticide depletion was monitored by solid-phase microextraction sampling followed by gas chromatography–mass spectrometry analysis. The influence of major parameters (sodium hypochloride concentration, solution pH, and exposure time to ultraviolet (UV) light) was, thus, adequately established via two complementary approaches: factorial (23, three variables—two levels) and Doehlert designs. Hence, the sodium hypochloride concentration and the solution pH produced distinct effects depending on the pesticide evaluated (for instance, acidic and basic media caused increasing rates of degradation for the organophosphorus/pyrethroid and organochlorine pesticides, respectively). Conversely, higher rates of degradation were achieved for all of the pesticides investigated when increased exposure times to UV radiation were employed. Finally, the exposure time to UV radiation that lead to complete degradation of disulfoton and endosulfan sulfate (organophosphorus and organochlorine pesticides, respectively) in aqueous media under ordinary conditions employed in water treatment stations was established; disulfoton and endosulfan sulfate were completely degraded after 10 and 40 h, respectively.  相似文献   

2.
为加强有机氯农药(organic chlorinated pesticides,OCPs)的污染预防与控制,该研究分析了新疆典型农业地区有机氯农药的污染状况并对其进行了风险评价。采集表层土壤样品36个,分析其中15种OCPs的残留状况。六六六(Hexachlorocyclohexanes,HCHs)、滴滴涕(dichlorodiphenyltrichloroethanes,DDTs)、氯丹类化合物、硫丹和硫丹盐的质量分数范围分别是0.37～22.82、0.91～858.47、0.15～47.08ng/g、N.D(未检出)～16.27和N.D～73.83ng/g。对OCPs的来源进行分析,发现HCHs来源于历史上工业HCHs的使用或近期林丹的输入,DDT来源于工业品的违法使用和三氯杀螨醇的使用,研究区域氯丹存在新的来源,而硫丹新来源较少。通过主成分分析,从15种OCPs中提取了5个主成分,总方差解释量达到了79.93%。5个主成分分别归因于DDT和工业HCH s的使用、OCPs原料的差异以及研究区域内病虫害的发病特征等。利用灰色关联分析研究区域内OCPs污染状况,结果表明石河子污染水平最高,各研究区域土壤均需要采取进一步的污染控制措施。  相似文献   

3.
This study presents new sample preparation and analytical procedures for the quantification of pesticides on processed tea leaves. The new method includes tea extraction and dispersive solid phase extraction (d-SPE) to prepare gas chromatography (GC) and ultrahigh-performance liquid chromatography (UHPLC)-ready samples, providing a fast and cost-effective solution for time-sensitive industrial analysis to fulfill regulatory requirements. Both GC-negative chemical ionization mass spectrometry (GC-NCI-MS) and UHPLC-tandem mass spectrometry (UHPLC-MS/MS) were employed to produce highly sensitive and reproducible data. Excellent limits of detection (typically below 1 μg/kg for GC and 10 μg/kg for UHPLC), wide linearity ranges, and good recoveries (mostly >70%) were achieved on the selected pesticides. Twenty-seven tea samples purchased from local grocery stores were analyzed using the newly developed methods. Among the pesticides analyzed, endosulfan sulfate and kelthane were the most frequently detected by GC-NCI-MS and imidacloprid and acetamiprid by UHPLC-MS/MS in these teas. The samples were found to be relatively clean, with <1 mg/kg of total pesticide residues. The organic-labeled teas were significantly cleaner than nonorganic ones. The cost per gram of tea did not correlate with pesticide residue levels detected.  相似文献   

4.
A multiyear study in the C-111 canal system and associated sites in Florida Bay was undertaken to determine the potential pesticide risk that exists in South Florida. After the examination of extensive pesticide concentration data in surface water, tissues, and semipermeable membrane devices (SPMDs), canal contamination seems to be derived from the extensive agricultural production that drains into the C-111 canal. The results of this study indicate that runoff from agricultural processes led to quantifiable pesticide residues in both canal and bay surface water, which occasionally exceeded current water quality criteria. The major pesticide of concern was endosulfan, which was detected at 100% of the sites sampled. Endosulfan exposure did not cause any acute effects in fish and crustaceans deployed in field bioassays. Chronic effects were observed in copepods, clams, and oysters but could not be attributed to endosulfan exposure. The decision to alter the C-111 canal flow and allow increased freshwater flow into the adjacent Everglades National Park may result in discharges of pesticides into the Everglades. Continued monitoring in this area is needed during this change in flow regime.  相似文献   

5.
Endosulfan, an endocrine disrupting chemical, is a widely used cyclodiene organochlorine pesticide worldwide, and it blocks neuronal GABA(A)-gated chloride channels in mammals and aquatic organisms. Endosulfan and its metabolites, such as endosulfan sulfate, are persistent in environments and are considered as toxic chemicals. For bioremediation of endosulfan, in this study, an attempt was made to isolate an endosulfan and endosulfan sulfate degrading bacterium from endosulfan-polluted agricultural soil. Through repetitive enrichment and successive subculture using endosulfan or endosulfan sulfate as the sole carbon source, a bacterium KS-2P was isolated. The KS-2P was identified as Pseudomonas sp. on the basis of the results of a 16S rDNA sequencing analysis and MIDI test. The degradation ratios for endosulfan or endosulfan sulfate in minimal medium containing endosulfan (23.5 microg mL(-1)) or endosulfan sulfate (21 microg mL(-1)) were 52% and 71%, respectively. Our results suggest that Pseudomonas sp. KS-2P has potential as a biocatalyst for endosulfan bioremediation.  相似文献   

6.
采用气相色谱法检测了海南瓜菜田的33个表层土壤样品中18种有机氯(OCPs)农药残留,并对其进行污染来源分析和初步生态风险评价。结果表明:(1)土壤中的OCPs检出率为90.9%,最高残留量为17.37 ng·g-1,平均值为2.30 ng·g-1;(2)18种OCPs均有检出,六六六(HCHs)、滴滴涕(DDTs)、硫丹类农药的检出率较高,分别为63.6%、57.6%、54.5%;(3)DDTs是主要残留物质,占总OCPs残留量的54.6%,18.2%的土样可能有DDTs新的输入,土壤中HCHs主要来源于过去使用的林丹;(4)与国内其他地区土壤和国家《土壤环境质量标准》(GB 15618—1995)一级标准相比,海南省瓜菜田土壤DDTs和HCHs残留量处于较低水平,生态风险也较低。  相似文献   

7.
采样测定了巢湖东半湖4个样点的表层沉积物中有机氯农药（OCPs）的含量。结果表明,11种有机氯农药在样品中被检出,总含量为8.26～31.73 ng.g^-1;OCPs在沉积物中的垂直分布从上往下大体呈递减趋势;且OCPs的最高含量都出现在上层沉积物中,说明巢湖东半湖沉积物中有机氯农药主要集中在0-3 cm的表层。根据分析,DDTs来自于早期残留或者施用农药后的长期风化残留。沉积物风险评估表明,巢湖东半湖表层沉积物中的有机氯农药存在一定的生态风险。  相似文献   

8.
This study assesses the role of the blue-green algal species present in the soil in the dissipation of endosulfan and its metabolites in the soil environment. Two Anabaena species, Anabaena sp. PCC 7120 and Anabaena flos-aquae, were used in this study. Anabaena sp. PCC 7120 produced three principal biotransformation compounds, chiefly endosulfan diol (endodiol), and minor amounts of endosulfan hydroxyether and endosulfan lactone. Trace amounts of endosulfan sulfate were detected. In comparison, the biotransformation of endosulfan by Anabaena flos-aquae yielded mainly endodiol with minor amounts of endosulfan sulfate. An unknown compound was produced up to 70% from endosulfan spiked in the medium inoculated by A. flos-aquae after 8 days of incubation. Therefore, the endosulfan fate was dependent on the species. Within 1 day of incubation, two Anabaena species produced low amounts of beta-endosulfan after application of alpha-endosulfan. These results suggest the presence of isomerase in the Anabaena species. Further studies using a fermentor to control the medium pH at 7.2 to minimize chemical hydrolysis of endosulfan revealed a major production of endodiol with minor amounts of endosulfan sulfate and the unknown compound. These results showed that the production of the unknown compound might be dependent on the alkaline pH in the medium and that the production of endodiol by A. flos-aquae might be biologically controlled. This study showed that two algal species could contribute in the detoxification pathways of endosulfan in the soil environment.  相似文献   

9.
Pendimethalin [N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine], in the formulation of Prowl (a commercial herbicide), was applied to various crops. Analysis of pendimethalin and its metabolite [4(1-ethylpropyl)amino-2-methyl-3,5-dinitrobenzyl alcohol] was accomplished by utilizing liquid-liquid partitioning, gel permeation chromatography (GPC) for nuts and mint, solid-phase extraction (SPE) cleanup, and gas chromatography (GC) with a nitrogen--phosphorus detector (NPD). Method validation recoveries for fruits, nuts, vegetables, grass, and mint are given for both compounds. Pendimethalin average recoveries ranged from 71% to 126% over two levels of fortification. Pendimethalin metabolite average recoveries ranged from 69% to 123% over two levels of fortification. The quantitation limit for all crops except mint was 0.050 ppm. The quantitation limit for mint and mint oil was 0.10 ppm. Residues greater than the limit of quantitation were found for pendimethalin in apple pomace, fresh and dry fig, grass screenings, mint oil, almond hulls, green onion, and tomato pomace (wet and dry). Residues greater than the limit of quantitation were found for pendimethalin metabolite in grass screenings, grass straw, and almond hulls. All other crop analyses for pendimethalin and its metabolite were below the limit of quantitation.  相似文献   

10.
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   

11.
Climate and soil conditions in South Florida along with an extensive canal system facilitate movement of agricultural pesticides into surface waters. In a two-year study (2002-2004) of the currently used pesticides in South Florida, atrazine, endosulfan, metolachlor, chlorpyrifos, and chlorothalonil were the most frequently detected in the canals and in Biscayne Bay, with average concentrations of 16, 11, 9.0, 2.6, and 6.0 ng/L, respectively. Concentrations of atrazine and chlorpyrifos were highest near corn production. Chlorothalonil and endosulfan concentrations were highest near vegetable production, with no clear trend for metolachlor, which is used on multiple crops. Concentration data were used to calculate an aquatic life hazard potential for the planting period (November) versus the harvest period (March). This analysis indicated that a higher hazard potential occurs during harvest, primarily from the use of endosulfan. These data will also serve to document canal conditions prior to implementation of the Comprehensive Everglades Restoration Plan (CERP).  相似文献   

12.
The characterization of runoff-related pesticide input and the identification of areas of concern in the field are essential for a comprehensive assessment of risk and the planning of mitigation measures. To this end, the agriculturally-derived aqueous and particle-associated pesticide contamination of the Lourens River and its tributaries was measured in a comprehensive design. Sampling was performed in the beginning of April prior to the first rainfall of the wet season and in the middle of April during high water conditions following the first rainfall of 9.6 mm d-1. Pre-runoff samples indicated contamination with endosulfan at levels up to 0.06 μg L-1, while no other pesticides were detectable. Rainfall-induced runoff resulted in an increase in the levels of the pesticides endosulfan, deltamethrin, azinphos-methyl, chlorpyrifos, and procymidone up to levels of 0.35, 1.4, 0.6, 0.19 and 9 μg L-1, respectively in water samples. Endosulfan, azinphos-methyl, and chlorpyrifos were detected at maximum concentrations of 273, 152, and 245 μg kg-1 in suspended sediments. No increased pesticide levels were detected at a control site upstream of the agricultural area. The Lourens River received its contamination via the tributaries discharging the surrounding farming area. Contamination of the six tributaries depended on landuse and slope characteristics and enabled the identification of target sites for risk reduction approaches. Transient pesticide levels exceeded the target water quality limit proposed by the South African Department of Water Affairs and Forestry (DWAF). The Lourens River site downstream of the farming area has been identified as a site where potential toxic conditions could arise.  相似文献   

13.
The soil mobility and dissipation of two pesticides with different physicochemical properties, namely mefenoxam, a systemic fungicide, and pendimethalin a selective herbicide, were determined in bare and tobacco tilled soil columns, which were installed in field conditions for over 125 days. Soil samples were collected at specific time intervals for a 125-day period and the rate of pesticide dissipation and leaching through the soil column was studied. The dissipation half-lives of mefenoxam from the top soil layer in tilled and bare soil columns were estimated at 10.3 and 13.1 days, respectively, while the corresponding half-lives for pendimethalin were 26.7 and 27.5 days, respectively. The dissipation of mefenoxam and pendimethalin from the top soil in tobacco cultivation was faster in comparison with bare soil; however, 120 days after their application, both pesticide residues were detected in the soil. Maximum concentrations of mefenoxam and pendimethalin were observed on the 15th and 33rd day, respectively, in the soil layer of 5–10 cm depth and on the 30th day and 63rd day, respectively, in the soil layer of 10–15 cm depth. Higher concentrations were observed in bare soil columns. The leaching of both pesticides was simulated with the continuous stirred tank reactor (CSTR) in series model. The simulated peak concentration and peak time for both pesticides fitted reasonably well to the experimental values.  相似文献   

14.
The role of algae in the persistence, transformation, and bioremediation of two endocrine disrupting chemicals, alpha-endosulfan (a cyclodiene insecticide) and its oxidation product endosulfan sulfate, in soil (incubated under light or in darkness) and a liquid medium was examined. Incubation of soil under light dramatically decreased the persistence of alpha-endosulfan and enhanced its transformation to endosulfan sulfate, over that of dark-incubated soil samples, under both nonflooded and flooded conditions. This enhanced degradation of soil-applied alpha-endosulfan was associated with profuse growth of indigenous phototrophic organisms such as algae in soil incubated under light. Inoculation of soil with green algae, Chlorococcum sp. or Scenedesmus sp., further enhanced the degradation of alpha-endosulfan. The role of algae in alpha-endosulfan degradation was convincingly demonstrated when these algae degraded alpha-endosulfan to endosulfan sulfate, the major metabolite, and endosulfan ether, a minor metabolite, in a defined liquid medium. When a high density of the algal inoculum was used, both metabolites appeared to undergo further degradation as evident from their accumulation only in small amounts and the appearance of an endosulfan-derived aldehyde. Interestingly, beta-endosulfan was detected during degradation of alpha-endosulfan by high density algal cultures. These algae were also capable of degrading endosulfan sulfate but to a lesser extent than alpha-endosulfan. Evidence suggested that both alpha-endosulfan and endosulfan sulfate were immediately sorbed by the algae from the medium, which then effected their degradation. Biosorption, coupled with their biotransformation ability, especially at a high inoculum density, makes algae effective candidates for remediation of alpha-endosulfan-polluted environments.  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.
Pesticides applied in extended agricultural fields may be controlled by means of bioindicators, such as honeybees, in which are the pesticides bioaccumulate. Liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) experiments with positive (PI) and negative (NI) ion modes were optimized for the analysis of 22 organophosphorus pesticides in honeybee samples. The extraction required 3 g of sample, which was extracted with acetone. The extract was purified with coagulating solution and reextracted with Cl(2)CH(2). Pesticides studied could be detected by both ionization modes except for parathion, parathion-methyl, and bromophos, which did not give signals in PI mode, and triazophos, which was not detected in NI mode. Fragmentation voltage and vaporizer temperature were optimized to achieve the highest sensitivity. The spectra profile of each pesticide in PI mode showed the [M + H](+) ion as the main signal, whereas in NI mode only fragment ions were shown. The detection limit obtained in selected ion monitoring mode ranged from 1 to 15 microg kg(-1). The average recoveries from spiked honeybees at various concentration levels (0.5-5 mg kg(-1)) exceeded 65% with relative standard deviations of 4-15%. The method was applied to real samples, in which residues of coumaphos and dimethoate were detected.  相似文献   

17.
We studied the influence of spent mushroom substrate (SMS) land application on water resources. Four study sites, including mushroom farms with low or high density land applications of SMS, and two controls, an alfalfa field and a woodland, were instrumented with soilwater lysimeters and groundwater monitoring wells. Water samples were collected during the dormant season (winter) and growing season (spring). Samples were analyzed for a number of water quality parameters, including dissolved organic carbon (DOC), dissolved organic nitrogen (DON), ammonia, chloride, nitrate, nitrite, phosphate, sulfate, aluminum, cadmium, calcium, chromium, copper, iron, lead, magnesium, manganese, mercury, nickel, potassium, silicon, sodium, and zinc. Additional analyses were performed for pesticides commonly used in the cultivation of alfalfa or corn, or for insect control, including methomyl, dimethoate, hexazinone, atrazine, diuron and permethrin.

All agricultural sites had elevated salt concentrations relative to the woodland site. The mushroom farm where SMS was applied in high concentrations had salt concentrations in the soilwater that were 10 to 100 times higher than the other agricultural sites. Of particular note were ammonium, nitrate, chloride, sulfate, calcium, magnesium, sodium, and potassium. Each of these were also elevated in the groundwater. The high salt concentrations were reflected in measurements of electrical conductivity. DOC and DON concentrations were also elevated in the soilwater and groundwater. Groundwater from each agricultural site, including the agricultural control, exceeded the primary drinking water standard for nitrate.

No pesticide residues were detected in well or lysimeter water collected at either site amended with SMS. Water samples collected from the woodland and at the alfalfa field not receiving SMS contained part per trillion quantities of a few pesticides.  相似文献   

18.
The dissipation rate of seven currently used soybean and corn pesticides in two tropical soils (Ustox and Psamments) of Brazil was studied in a laboratory incubation experiment. Dissipation half-lives of pesticides ranged between 2 (monocrotofos) and 90 days (endosulfan-beta). The contrasting clay contents of the studied tropical soils (130 versus 470 g of clay kg(-1) of soil) did not influence the dissipation dynamics of pesticides substantially. Mineralization to CO(2) was high [up to 78% of the applied radioactivity (AR)] for the studied organophosphorus compounds and deltamethrin, which also formed considerable amounts of bound residues (>20% of AR) during the 80 days of incubation. The highest portion of nonextractable residues was found for alachlor and simazine (55-60% of AR). In contrast, the nonpolar trifluralin and endosulfan formed only small amounts of bound residues (mostly <20% of AR) but showed the highest dissipation half-lives (>14 days) in the studied soils, also due to a low mineralization rate. When endosulfan-sulfate, as the main metabolite of endosulfan, was considered, the half-life time of endosulfan compounds (sum of -alpha, -beta, and -sulfate) was enhanced to >160 days in both soils. In comparison with the laboratory experiments, dissipation half-life times of chlorpyrifos, endosulfan-alpha, and trifluralin were shortened by a factor of 10-30 in field trials with the same soils, which was related to the volatilization potential of pesticides from soils.  相似文献   

19.
Evaluation of a previously published gel permeation chromatographic (GPC) procedure was undertaken to determine whether it can be used for additional organochlorine pesticides. After repeatability studies of many pesticides, the following compounds were approved for inclusion in the U.S. Department of Agriculture Domestic Residue Monitoring Program: coumaphos-S, stirophos, chlorpyrifos, ronnel, carbophenothion, chlorfenvinphos, phosalone, kepone, captan, linuron, and endosulfan I and II. Recoveries ranged from 54% for captan to 123% for ronnel. Ranges of CVs varied from 0-9.5% for carbophenothion to 7.1-47.7% for kepone. Although the minimum acceptable recovery of 50% was attained for all 12 pesticides, the anticipated CV of 20% was waived to include chlorpyrifos, endosulfan I and II, and kepone. For a multiresidue procedure involving approximately 40 compounds, these results were within the acceptable criteria.  相似文献   

20.
The environmental behavior, movement, distribution, persistence, and runoff by rainfall of the pesticides acetochlor, atrazine, chlorpyrifos, and propisochlor were studied under field conditions during a five-month period at normal weather conditions. The pesticide concentrations in soil depths of 0-5 and 5-20 cm, and in sediment and runoff water samples (collected from an artificial reservoir built in the lower part of the experimental plot) were measured every second week and following every runoff event. The contamination of a stream running across the lowest part of the plot was also monitored. The weather conditions were also recorded at the experimental site. The pesticide residues were quantified by a capillary gas chromatograph equipped with a nitrogen phosphorus selective detector (GC-NPD). There was a consistent decrease in pesticide residues in the 0-5 cm soil layer with time after spaying. At 140 days after treatment only atrazine and chlorpyrifos were present; acetochlor and propisochlor were not detected in this soil layer. Atrazine and chlorpyrifos in the soil at a depth of 5-20 cm were detectable during the whole experimental interval, whereas acetochlor and propisochlor concentrations were below the limit of detection. Pesticide losses by the surface runoff process and the contamination of the stream were closely related to the time of rainfall elapsed after treatment and amount of rain at the experimental plots. Losses were primarily dependent on surface rainfall volume and intensity. The maximum detected residues of atrazine and acetochlor in stream water were 1 order of magnitude higher than the maximum residue limit specified by the European Union (EU) for environmental and drinking water (0.1 microg/L for individual compounds and 0.5 microg/L for total pesticides). Chlorpyrifos and propisochlor were not detected in this matrix.  相似文献   

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