Community air monitoring for pesticides. Part 1: selecting pesticides and a community

The CA Department of Pesticide Regulation (CDPR) developed methods to select pesticides and a community to fulfill criteria for an ambient air monitoring study it conducted as part of the CA Environmental Protection Agency's Environmental Justice Action Plan. Using a scoring system, CDPR evaluated 100 pesticides based on statewide-reported pesticide use, volatility, and priority in CDPR's risk assessment process (indicators of exposure and toxicity) to produce a list of pesticides to consider as candidates for monitoring. The CDPR also evaluated and scored 83 communities based on demographics and health factors, availability of cumulative impacts data, and reported pesticide use to create a list of community candidates. The scores provide relative rankings to distinguish more highly impacted communities from less impacted ones and to identify which pesticides might contribute most to potential adverse health effects. These methods use criteria that can be quantified, validated, and verified in order to provide a transparent and fair selection process. Based on public comments and highest scores, CDPR recommended 40 pesticides (including some of their degradation products) and one community for its yearlong monitoring study. The CDPR then further refined its list of pesticides by soliciting input from local and technical advisory groups. The CDPR plans to use these methods to select pesticides and communities in future monitoring activities.     

Community air monitoring for pesticides—part 2: multiresidue determination of pesticides in air by gas chromatography,gas chromatography–mass spectrometry,and liquid chromatography–mass spectrometry

Two multiresidue methods were developed to determine pesticides in air collected in California. Pesticides were trapped using XAD-4 resin and extracted with ethyl acetate. Based on an analytical method from the University of California Davis Trace Analytical Laboratory, pesticides were detected by analyzing the extract by gas chromatography–mass spectrometry (GC-MS) to determine chlorothalonil, chlorthal-dimethyl, cycloate, dicloran, dicofol, EPTC, ethalfluralin, iprodione, mefenoxam, metolachlor, PCNB, permethrin, pronamide, simazine, trifluralin, and vinclozolin. A GC with a flame photometric detector was used to determine chlorpyrifos, chlorpyrifos oxon, diazinon, diazinon oxon, dimethoate, dimethoate oxon, fonophos, fonophos oxon, malathion, malathion oxon, naled, and oxydemeton. Trapping efficiencies ranged from 78 to 92 % for low level (0.5 μg) and 37–104 % for high level (50 and 100 μg) recoveries. Little to no degradation of compounds occurred over 31 days; recoveries ranged from 78 to 113 %. In the California Department of Food and Agriculture (CDFA) method, pesticides were detected by analyzing the extract by GC-MS to determine chlorothalonil, chlorpyrifos, cypermethrin, dichlorvos, dicofol, endosulfan 1, endosulfan sulfate, oxyfluorfen, permethrin, propargite, and trifluralin. A liquid chromatograph coupled to a MS was used to determine azinphos-methyl, chloropyrifos oxon, DEF, diazinon, diazinon oxon, dimethoate, dimethoate oxon, diuron, EPTC, malathion, malathion oxon, metolachlor, molinate, norflurazon, oryzalin, phosmet, propanil, simazine and thiobencarb. Trapping efficiencies for compounds determined by the CDFA method ranged from 10 to 113, 22 to 114, and 56 to 132 % for 10, 5, and 2 μg spikes, respectively. Storage tests yielded 70–170 % recovery for up to 28 days. These multiresidue methods represent flexible, sensitive, accurate, and cost-effective ways to determine residues of various pesticides in ambient air.     

Vegetated ditches as a management practice in irrigated alfalfa

The organophosphate (OP) insecticides diazinon and chlorpyrifos have been frequently detected in the San Joaquin River, California, USA. Irrigation tail waters are a significant source of OP pesticides in the watershed. This study tested several management practices for reducing offsite movement of chlorpyrifos to surface water from flood irrigated alfalfa. Management practices evaluated include (1) a constructed, vegetated irrigation tailwater return ditch and (2) increased lag time between chlorpyrifos application and start of flood irrigation. Chlorpyrifos concentrations in whole-water samples of irrigation runoff were variable and ranged from 0.22 mug/l to a maximum of 1.67 mug/l. The median concentration reduction at the end of a 200 m vegetated ditch was 38% compared to 1% in an adjacent conventional tail water ditch. Runoff data collected represented first flush runoff from sets that were irrigated between 48 and 144 h after chlorpyrifos application. There was no consistent effect of irrigation lag time on chlorpyrifos concentration in tailwater for lag times of up to 144 h. Consequently these data indicate that delayed irrigation is not an effective management practice for reducing chlorpyrifos off-site movement to surface water in California flood irrigated alfalfa.     

The occurrence of glyphosate, atrazine, and other pesticides in vernal pools and adjacent streams in Washington, DC, Maryland, Iowa, and Wyoming, 2005–2006

Vernal pools are sensitive environments that provide critical habitat for many species, including amphibians. These small water bodies are not always protected by pesticide label requirements for no-spray buffer zones, and the occurrence of pesticides in them is poorly documented. In this study, we investigated the occurrence of glyphosate, its primary degradation product aminomethylphosphonic acid, and additional pesticides in vernal pools and adjacent flowing waters. Most sampling sites were chosen to be in areas where glyphosate was being used either in production agriculture or for nonindigenous plant control. The four site locations were in otherwise protected areas (e.g., in a National Park). When possible, water samples were collected both before and after glyphosate application in 2005 and 2006. Twenty-eight pesticides or pesticide degradation products were detected in the study, and as many as 11 were identified in individual samples. Atrazine was detected most frequently and concentrations exceeded the freshwater aquatic life standard of 1.8 micrograms per liter (microg/l) in samples from Rands Ditch and Browns Ditch in DeSoto National Wildlife Refuge. Glyphosate was measured at the highest concentration (328 microg/l) in a sample from Riley Spring Pond in Rock Creek National Park. This concentration exceeded the freshwater aquatic life standard for glyphosate of 65 microg/l. Aminomethylphosphonic acid, triclopyr, and nicosulfuron also were detected at concentrations greater than 3.0 microg/l.     

硫化学发光检测器-气相色谱法测定废气中挥发性硫化物

采用硫化学发光检测-宽口径石英毛细管柱气相色谱法,建立了废气中羰基硫、硫化氢、二硫化碳、甲硫醇、乙硫醇、甲硫醚、乙硫醚、丙硫醇、异丙硫醇、噻吩及二甲二硫等11种挥发性硫化物的分析方法。硫化学发光检测器的灵敏度、选择性及线性范围均优于传统的火焰光度检测器。进样体积为0.2 ml时,硫化物的检出限为0.03～0.1 mg/m3。实际样品5次测定的相对标准偏差小于5.1%,加标回收率为83.7%～108.8%。测定了某炼油厂酸性水罐尾气、污油罐尾气及瓦斯气中挥发性硫化物,为其恶臭控制与治理提供检测手段和基础数据。     

Pesticide residue level in tea ecosystems of Hill and Dooars regions of West Bengal, India

In the present study we quantified the residues of organophosphorus (e.g. ethion and chlorpyrifos), organochlorine (e.g. heptachlor, dicofol, alpha-endosulfan, beta-endosulfan, endosulfan sulfate) and synthetic pyrethroid (e.g. cypermethrin and deltamethrin) pesticides in made tea, fresh tea leaves, soils and water bodies from selected tea gardens in the Dooars and Hill regions of West Bengal, India during April and November, 2006. The organophosphorus (OP) pesticide residues were detected in 100% substrate samples of made tea, fresh tea leaves and soil in the Dooars region. In the Hill region, 20% to 40% of the substrate samples contained residues of organophosphorus (OP) pesticides. The organochlorine (OC) pesticide residues were detected in 33% to 100% of the substrate samples, excluding the water bodies in the Dooars region and 0% to 40% in the Hill region. The estimated mean totals of studied pesticides were higher in fresh tea leaves than in made tea and soils. The synthetic pyrethroid (SP) pesticide residues could not be detected in the soils of both the regions and in the water bodies of the Dooars. Sixteen percent and 20% of the made tea samples exceeded the MRL level of chlorpyrifos in Dooars and Hill regions respectively. The residues of heptachlor exceeded the MRL in 33% (April) and 100% (November) in the Dooars and 40% (April) and 20% (November) in the Hill region. Based on the study it was revealed that the residues of banned items like heptachlor and chlorpyrifos in made tea may pose health hazards to the consumers.     

South Florida Water Management District ambient pesticide monitoring network: 1992 to 2007

The South Florida Water Management District has collected surface water and sediment samples for analysis of over 80 pesticides since 1992. Residues of atrazine and DDE-p,p(') are nearly ubiquitous throughout the sampling area. Surface water concentrations of atrazine at nine of 14 selected monitoring locations exhibited a downward trend and none of the detected concentrations exceeded established levels of concern. Seventy-five percent of the sampled locations had average sediment residues of DDE-p,p(') at levels that may impact sediment-dwelling organisms. Monitoring locations with the highest average DDE-p,p(') concentrations (based on detected values) and the highest percentage of pesticide detections did not exhibit consistent trends. Some locations exhibited increasing trends while trends at other locations showed a decrease in concentrations. Additionally, specific location concentrations for ethion, diazinon, and endosulfan documented periods of surface water quality exceedances. However, product label changes and grower education have substantially contributed to the reduced number of exceedances over time.     

Pesticide residues in dried table grapes from the Aegean region of Turkey

Dried grapes make the ideal low-calorie snack. The formation of gray mold during the drying of the grapes can severely decrease production. Pesticides and fungicides are applied to prevent losses due to pests and mold. Dried grapes from 99 farms in the Aegean region were sampled for pesticide residues. Of the 26 pesticides analyzed for, chlorpyrifos methyl, chlorpyrifos ethyl, deltamethrin, lambda-cyolathrin, dichlofluanid, iprodione, and procymidone were detected in the dried grapes. Only seven samples contained residues above the maximum residue limit. It is important to note that pesticide residues were only present in samples originating from vineyards using conventional farming practices.     

Integrated approach for the quality assessment of freshwater resources in a vineyard area (South Portugal)

An integrated chemical and biological approach for the quality assessment of freshwater resources in a vineyard area of the ??Alentejo?? region (South Portugal) is presented. This includes analysis to 11 pesticide compounds and whole toxicity testing on algae and crustaceans. Simazine, terbuthylazine, terbutryn, desethylatrazine and chlorpyrifos were the most frequently detected pesticides in water collected from wells and drainage channels. Mixtures of up to three compounds in different qualitative combinations were also found. The quality standards for individual pesticides (0.1 ??g L^???1) and pesticides-total (0.5 ??g L^???1) were exceeded in some samples. However, their maximum concentrations were lower than the WHO guidelines, the USEPA health advisory values and the environmental quality standards for priority substances applicable to surface water. In five samples, the herbicides terbuthylazine and terbutryn and the insecticide chlorpyrifos did not pass the toxicity exposure ratio (TER) trigger values specified for aquatic organisms (algae, Daphnia and fish). Maximum toxic effects on Daphnia magna (100%) and Pseudokirchneriella subcapitata (82.56%) were determined in groundwater samples, while in surface water, no toxicity was observed. Concerning effects on Heterocypris incongruens in sediment samples collected at the drainage channels, mortality and growth inhibition values were below 38%. Pro-active management of the use of pesticides is recommended for implementing at the farm and catchment level to reduce inputs into ground- and surface water.     

典型恶臭有机污染自动监测技术与应用探究

对比6种主流有机硫自动监测仪的4种有机硫混标测试结果,表明80%仪器的性能指标能满足国家恶臭排放标准中厂界监测的定量要求。复杂环境适用性研究显示,有机硫化物间测定影响相对较小,高浓度标气有残留,定性受到常见挥发性有机物中个别物质干扰。优选3种检测器为FPD的仪器现场连续实测,结果表明甲硫醇、甲硫醚、二甲二硫醚和二硫化碳为石化园区的有机硫常检出物种;3种仪器的监测数据可较好地反映该石化园区空气恶臭污染特征。     

Evaluation of ozonation technique for pesticide residue removal and its effect on ascorbic acid,cyanidin-3-glucoside,and polyphenols in apple (<Emphasis Type="Italic">Malus domesticus</Emphasis>) fruits

Ozonated water dip technique was evaluated for the detoxification of six pesticides, i.e., chlorpyrifos, cypermethrin, azoxystrobin, hexaconazole, methyl parathion, and chlorothalonil from apple fruits. Results revealed that ozonation was better than washing alone. Ozonation for 15 min decreased residues of the test pesticides in the range of from 26.91 to 73.58%, while ozonation for 30 min could remove the pesticide residues by 39.39–95.14 % compared to 19.05–72.80 % by washing. Cypermethrin was the least removed pesticide by washing as well as by ozonation. Chlorothalonil, chlorpyrifos, and azoxystrobin were removed up to 71.45–95.14 % in a 30-min ozonation period. In case of methyl parathion removal, no extra advantage could be obtained by ozonation. The HPLC analysis indicated that ozonation also affected adversely the ascorbic acid and cyanidin-3-glucoside content of apples. However, 11 polyphenols studied showed a mixed trend. Gallic acid, 3,4-dihydroxybenzoic acid, catechin, epicatechin, p-coumaric acid, quercetin-3-O-glucoside, quercetin, and kaempferol were found to decrease while syringic acid, rutin, and resveratrol were found to increase in 30-min ozonation.     

Investigation on diazinon and oxydemeton-methyl residues in cucumbers grown in Kerman greenhouses

Pesticides are considered as the most polluting substances. The residue of pesticides in agricultural crops, especially in greenhouse harvests, has been reported critical. Cucumber, considered as a vegetable, is an agricultural product which is commonly found in the Iranian food basket. The current study aims to assess the level of diazinon and oxydemeton-methyl existing in cucumbers sampled from Kerman greenhouses. The pesticide residue was extracted by acetone and dichloromethane. The extracts were cleaned up according to the solid-phase extraction method. The pesticide residues were then determined by capillary gas chromatography with nitrogen-phosphorus detection. The recoveries were 83 and 85 %, the limit of detection was 0.028 and 0.034 mg/kg, and the limits of qualification were 0.093 and 0.113 mg/kg for diazinon and oxydemeton-methyl in cucumber samples, respectively. The median of diazinon residue was detected 0.582 mg/kg, which was 11.64 times the national maximum residue limit (MRL) (0.05 mg/kg), and the median for oxydemeton-methyl was 1.910 mg/kg, being 1.91 times the MRL (1 mg/kg).     

气质联用法测定环境空气中有机硫化物

采用 SUMMA罐采集空气样品，在预浓缩系统中经3级冷阱捕集后，用气相色谱-质谱联用技术测定环境空气中7种痕量有机硫化物。对试验条件进行优化，使得甲硫醇、乙硫醇、甲硫醚、二硫化碳、噻吩、乙硫醚和二甲二硫醚等7种有机硫化物在21．47μg/m3～336．43μg/m3范围内线性良好。试验表明，7种有机硫化物的方法检出限为0．004μg/m3～0．036μg/m3；标准气体平行测定6次结果的 RSD为2．7％～6．2％，加标回收率为92．2％～97．5％。用该方法测定实际空气样品，并与傅立叶红外光谱法测定的结果进行比对，结果令人满意。     

Characterizing agrochemical patterns and effective BMPs for surface waters using mechanistic modeling and GIS

Monitoring programs in the agriculturally intense San Joaquin River Valley of California have periodically found organophosphate (OP) insecticide concentrations, predominantly chlorpyrifos, diazinon and methidathion, at levels high enough to cause mortality for the aquatic invertebrate Ceriodaphnia dubia. These detections are likely the result of off-site movement from treated fields. However, the relative significance and magnitude of off-site transport pathways cannot be readily deduced from monitoring data alone. Therefore, a comprehensive modeling system has been constructed to estimate temporal and spatial pesticide source magnitudes and to follow the pesticide dissipation pathways once in surface water. The USEPA models HSPF and PRZM3 were used for the hydrology and non-point source predictions, respectively. Spray drift was accounted for using the mechanistic model AgDrift. The Orestimba Creek Watershed in the San Joaquin Valley was characterized and used as a typical watershed for this region. Representative transport pathways were ranked and quantified, and numerical implementation of best management practices (BMPs) determined which practice may have the highest likelihood for reducing pesticide loadings. Approximately 85% of the predicted chlorpyrifos mass detected between May 1, 1996, and April 30, 1997 resulted from drift, with the largest contributions coming from walnut orchards immediately adjacent to Orestimba Creek. Various simulated drift mitigation measures suggest chlorpyrifos mass loadings can be decreased by over 90% depending upon the type of mitigation chosen. Imposed drift BMPs should be effective in reducing chlorpyrifos levels found in surface waters of the San Joaquin valley if the Orestimba creek watershed is considered representative of watersheds found in this area of California.     

Impacts of climate-induced changes on the distribution of pesticides residues in water and sediment of Lake Naivasha, Kenya

This study reports evidence of increased chlorpyrifos contamination in sediment and water in Lake Naivasha following its intensive application in the horticultural farms in the catchment area. Analytical results show that levels of chlorpyrifos residues were influenced by climate-induced rainfall pattern with higher levels reported during period of heavy precipitation with significant decrease during low rainfall. On average, the levels ranged between 14.8 and 32.8 ng g^?1 in sediment during rainy season compared to a range of 8.5–16.6 ng g^?1 in the dry season. Additionally, the mean concentration of chlorpyrifos in water ranged between 8.61 and 22.4 μg L^?1 during rainy season and below detection limit (bdl) ?13.6 μg L^?1 in dry season as quantified by enzyme-linked immunosorbent assay. Meanwhile, independent t test analysis indicated that there was significant difference in concentration at p?≤?0.05 between the seasons with respect to sediment and water samples. This demonstrated that climate-induced variations had considerable influence on contamination. While diazinon and carbofuran were equally applied intensively, their levels were below the detection limit in the all the samples analyzed. ELISA results were validated by the capillary-HPLC photodiode-array detector instrument analysis, and statistical comparison showed no significant difference between them. It was evident that chlorpyrifos residues determination in water and sediment by ELISA can be a useful strategy in environmental management and monitoring program, and a complimentary analytical tool to high performance liquid chromatography. Levels of chlorpyrifos detected in sediment and water were found to exceed recommended criteria for protection of aquatic life and preservation of water quality and may be hazardous if not regularly monitored.     

便携式气相色谱法快速测定恶臭气体样品中的硫化物

建立一种利用便携式气相色谱仪快速、简便地测定恶臭气体样品中硫化物的方法,对硫化氢、甲硫醇、甲硫醚及二硫化碳能实现良好分离,光离子化检测器PID可实现甲硫醇、甲硫醚、二硫化碳的快速定性、定量分析,还能避免高浓度二氧化硫对测定的干扰,检出限分别为0.05、0.03、0.02ppm,精密度好,相对标准偏差RSD分别小于11.6%、7.89%和2.14%,经实际应用,效果良好。     

Solid-phase microextraction coupled to gas chromatography-mass spectrometry for the study of soil adsorption coefficients of organophosphorus pesticides

A solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) method for the simultaneous determination of the organophosphorus pesticides (OPPs), phorate, diazinon, methyl-parathion, fenitrothion, malathion, fenthion, ethyl-parathion and methidathion, has been developed to study their soil/water distribution. The method was used in conjunction with a conventional 'batch equilibrium method' to assess the soil adsorption coefficients (Koc) of the target compounds in different soil samples with known organic carbon content. Contrary to traditional techniques, the present method is fast, solvent-free and highly sensitive, thus permitting the assessment of the Koc values of the target compounds even at low soil concentration levels, close to those encountered in real field contamination, where the Freudlich adsorption isotherms can be considered to be linear. The estimated Koc values were found to be in good agreement with those reported in the literature.     

Analysis of Pesticides Using a Polyppyrole Modified Electrode

Electrochemical methods can provide fast, sensitive and sometimes real time detection of pesticides. In the course of this work, a dispersed mercury electrode has been used to detect pesticides electrochemically. The electrode was prepared by depositing a thin mercury film on a glassy carbon disc and then coating a layer of polypyrrole on the disc. The effect of coating thickness on detection sensitivity was studied. A thin mercury film of 0.34 µm dispersed by one cycle polymerization of pyrrole was preferred. The influence of electrolyte, pH and organic solvent content on pesticide response was also investigated. The polypyrrole dispersed mercury electrode (Hg-PPy/GC) was not suitable for a pH above 6 but it can tolerate acetonitrile up to 10% at which concentration the mercury film coated glassy carbon electrode (Hg/GC) failed to response. Methyl parathion, methyl azinphos, parathion and fenitrothion were detected. The sensitivity of the dispersed mercury electrode was similar to a normal thin mercury film electrode in this case. A good response can be obtained for 1 ppm pesticides using fast linear sweeping voltammetry.     

Characterization of Benthic Communities and Physical Habitat in the Stanislaus, Tuolumne, and Merced Rivers, California

The primary goal of this study was to characterize physical habitat and benthic communities (macroinvertebrates) in the Stanislaus, Tuolumne and Merced Rivers in California’s San Joaquin Valley in 2003. These rivers have been listed as impaired water bodies (303 (d) list) by the State of California due to the presence of organophosphate (OP) insecticides chlorpyrifos and diazinon, Group A pesticides (i.e., organochlorine pesticides), mercury, or unknown toxicity. Based on 10 instream and riparian physical habitat metrics, total physical habitat scores in the Stanislaus River ranged from 124 to 188 (maximum possible total score is 200). The highest total habitat score was reported at the upstream site. Tuolumne River physical habitat scores ranged from 86 to 167. Various Tuolumne River physical habitat metrics, including total habitat score, increased from downstream to upstream in this river. Merced River physical habitat scores ranged from 121 to 170 with a significant increase in various physical habitat metrics, including total habitat score, reported from downstream to upstream. Channel flow (an instream metric) and bank stability (a riparian metric) were the most important physical habitat metrics influencing the various benthic metrics for all three rivers. Abundance measures of benthic macroinvertebrates (5,100 to 5,400 individuals) were similar among the three rivers in the San Joaquin watershed. Benthic communities in all three rivers were generally dominated by: (1) Baetidae species (mayflies) which are a component of EPT taxa generally considered sensitive to environmental degradation; (2) Chironomidae (midges) which can be either tolerant or sensitive to environmental stressors depending on the species; (3) Ephemerellidae (mayflies) which are considered sensitive to pollution stress; and (4) Naididae (aquatic worms) which are generally considered tolerant to environmental stressors. The presence of 117 taxa in the Stanislaus River, 114 taxa in the Tuolumne River and 96 taxa in the Merced River implies that the benthic communities in these streams are fairly diverse but without a clear definition of benthic community expectations it is unknown if these water bodies are actually impaired.     

Ionic liquid-based dispersive liquid–liquid microextraction for the determination of formaldehyde in wastewaters and detergents

Spectrophotometry in combination with ionic liquid-based dispersive liquid–liquid microextraction (DLLME) was applied for the extraction and determination of formaldehyde in real samples. The method is based on the reaction of formaldehyde with methyl acetoacetate in the presence of ammonia. The variation in the absorbance of the reaction product was measured at 375?nm. An appropriate mixture of ethanol (disperser solvent) and ionic liquid, 1-hexyl-3-methylimidazoliumhexafluoro-phosphate [C₆MIM][PF₆] (extraction solvent) was rapidly injected into a water sample containing formaldehyde. After extraction, sedimented phase was analyzed by spectrophotometry. Under the optimum conditions, the calibration graph was linear in the range of 0.1–20?ng?mL^?1 with the detection limit of 0.02?ng?mL^?1 and limit of quantification of 0.08?ng?mL^?1 for formaldehyde. The relative standard deviation (RSD%, n?=?5) for the extraction and determination of 0.8?ng?mL^?1 of formaldehyde in the aqueous samples was 2.5%. The results showed that DLLME is a very simple, rapid, sensitive, and efficient analytical method for the determination of trace amounts of formaldehyde in wastewaters and detergents, and suitable results were obtained.