Community air monitoring for pesticides. Part 3: using health-based screening levels to evaluate results collected for a year

The CA Department of Pesticide Regulation (CDPR) and the CA Air Resources Board monitored 40 pesticides, including five degradation products, in Parlier, CA, to determine if its residents were exposed to any of these pesticides and, if so, in what amounts. They included 1,3-dichloropropene, acrolein, arsenic, azinphos-methyl, carbon disulfide, chlorpyrifos and its degradation product, chlorthalonil, copper, cypermethrin, diazinon and its degradation product, dichlorvos, dicofol, dimethoate and its degradation product, diuron, endosulfan and its degradation product, S-ethyl dipropylcarbamothioate (EPTC), formaldehyde, malathion and its degradation product, methyl isothiocyanate (MITC), methyl bromide, metolachlor, molinate, norflurazon, oryzalin, oxyfluorfen, permethrin, phosmet, propanil, propargite, simazine, SSS-tributylphosphorotrithioate, sulfur, thiobencarb, trifluralin, and xylene. Monitoring was conducted 3 days per week for a year. Twenty-three pesticides and degradation products were detected. Acrolein, arsenic, carbon disulfide, chlorpyrifos, copper, formaldehyde, methyl bromide, MITC, and sulfur were detected in more than half the samples. Since no regulatory ambient air standards exist for these pesticides, CDPR developed advisory, health-based non-cancer screening levels (SLs) to assess acute, subchronic, and chronic exposures. For carcinogenic pesticides, CDPR assessed risk using cancer potency values. Amongst non-carcinogenic agricultural use pesticides, only diazinon exceeded its SL. For carcinogens, 1,3-dichloropropene concentrations exceeded its cancer potency value. Based on these findings, CDPR has undertaken a more comprehensive evaluation of 1,3-dichloropropene, diazinon, and the closely related chlorpyrifos that was frequently detected. Four chemicals—acrolein, arsenic, carbon disulfide, and formaldehyde—sometimes used as pesticides were detected, although no pesticidal use was reported in the area during this study. Their presence was most likely due to vehicular or industrial emissions.     

Impacts of pesticides in a Central California estuary

Recent and past studies have documented the prevalence of pyrethroid and organophosphate pesticides in urban and agricultural watersheds in California. While toxic concentrations of these pesticides have been found in freshwater systems, there has been little research into their impacts in marine receiving waters. Our study investigated pesticide impacts in the Santa Maria River estuary, which provides critical habitat to numerous aquatic, terrestrial, and avian species on the central California coast. Runoff from irrigated agriculture constitutes a significant portion of Santa Maria River flow during most of the year, and a number of studies have documented pesticide occurrence and biological impacts in this watershed. Our study extended into the Santa Maria watershed coastal zone and measured pesticide concentrations throughout the estuary, including the water column and sediments. Biological effects were measured at the organism and community levels. Results of this study suggest the Santa Maria River estuary is impacted by current-use pesticides. The majority of water samples were highly toxic to invertebrates (Ceriodaphnia dubia and Hyalella azteca), and chemistry evidence suggests toxicity was associated with the organophosphate pesticide chlorpyrifos, pyrethroid pesticides, or mixtures of both classes of pesticides. A high percentage of sediment samples were also toxic in this estuary, and sediment toxicity occurred when mixtures of chlorpyrifos and pyrethroid pesticides exceeded established toxicity thresholds. Based on a Relative Benthic Index, Santa Maria estuary stations where benthic macroinvertebrate communities were assessed were degraded. Impacts in the Santa Maria River estuary were likely due to the proximity of this system to Orcutt Creek, the tributary which accounts for most of the flow to the lower Santa Maria River. Water and sediment samples from Orcutt Creek were highly toxic to invertebrates due to mixtures of the same pesticides measured in the estuary. This study suggests that the same pyrethroid and organophosphate pesticides that have been shown to cause water and sediment toxicity in urban and agriculture water bodies throughout California, have the potential to affect estuarine habitats. The results establish baseline data in the Santa Maria River estuary to allow evaluation of ecosystem improvement as management initiatives to reduce pesticide runoff are implemented in this watershed.     

Trends in ambient concentrations of agrochemicals in humans and the environment of the United States

Uses of pesticides and related agrochemicals have been regulated in the United States since 1948. The United States government has supported human and environmental monitoring for pesticides and selected toxic chemicals for the past 15 yr. The initial ambient monitoring systems were designed to determine average concentrations of pesticides and related chemicals in human and environmental media on a nationwide basis and determine changes in these concentrations over time. The results of these surveys showed that almost all of the general human population and various environmental components contained low concentrations of chlorinated pesticides. As the Environmental Protection Agency (EPA) restricted many uses of the chlorinated pesticides, the organophosphorous and carbamate pesticides which replaced them were not as easily monitored by ambient surveys. Special monitoring studies had to be done more frequently to produce data on these compounds which were not as persistent or accumulative in the environment. Currently, a re-evalution has begun to determine pesticide monitoring data needs for the next 5 to 10 yr, modify existing ambient surveys, and plan needed short-term studies to efficiently meet regulatory data needs. Ambient monitoring for trends in chemical levels in humans and the environment will continue in the United States at a reduced level, and many exposure data needs will be met with use-specific monitoring studies.Presented at the International Conference on Environmental Hazards of Agrochemicals in Developing Countries, 8–12 November, 1983 in Alexandria, Egypt.     

Towards sustainable pesticides

In the light of increasing concern over the environmental impact of pesticides, we look at the evolution of national and international policies for sustainable pesticide use, and the associated data requirements.     

江苏省主要农药产品的环境残留监测方法研究

介绍了江苏省生产的主要农药品种,综述了草甘膦、丁草胺、乙草胺、百草枯和氟乐灵等5种除草剂,代森锰锌、戊唑醇、百菌清、甲基硫菌灵和三环唑等5种杀菌剂,毒死蜱、吡虫啉、氯氰菊酯等3种杀虫剂,以及乙烯利、多效唑等2种植物生长调节剂的生产现状及危害,以及上述农药在水、土壤等环境介质中的检测方法。以期为相关农药残留的检测方法标准化、环境中控制限值的制定、农药类环境事故应急监测以及农药生产与使用的环境监管提供技术支持。     

Analysis of pesticide residues in Peninsular Malaysian waterways

The use of organochlorine pesticides has caused concern due to their effects on human health and the Malaysian aquatic ecosystem, particularly so in view of their persistent and bioaccumulative properties. Since the extent of organochlorine pesticide pollution in Malaysian waterways is unknown except for isolated instances, a systematic survey has now been carried out. Water samples from various rivers were extracted, cleaned up with Florisil and analysed for the individual organochlorine pesticides by gas chromatography (GC) with an electron capture detector (ECD). DDE, DDT and heptachlor were present in all the river water samples of the west coast of Peninsular Malaysia. Other organochlorine pesticides were also identified from the water samples. However, the levels of all these are still below criteria values for Malaysian aquatic life, indicating that organochlorine pesticide pollution is less of a problem than other organic or inorganic pollutants.     

Occurrence of organochlorine pesticides in indoor dust

Organochlorine pesticides are present in the environment and suspected of causing serious health effects. Diet has been the main exposure source, but indoor source release is gaining focus. Within a monitoring study of polychlorinated biphenyls of Danish buildings built during the 1960s and 1970s, we coincidently determined extreme levels of dichlorodiphenyltrichloroethane (DDT) levels in two of ten random samples. This raises concern and further large scale investigations are warranted to confirm this.     

Amperometric Detection of Pesticides Using Polymer Electrodes

Abstact The real time monitoring of some organophosphorus based pesticides is of great concern to environmentalists because the widespread use of pesticides is causing severe health hazards to all living beings and also hampering our ecological balance. The traditional methods of measurement of pesticide residues are time consuming, need sample pre-treatment, and lack desired specificity and accuracy. We have developed an amperometric biosensor for indirect measurement of the pesticide concentration precisely in ppb level. The method is based on the action of two enzymes namely acetylcholine esterase and choline oxidase which are uniquely immobilized in a polymeric porous network directly on the working electrode of a screen-printed sensor. Polyacrylamide matrix has been prepared by copolymerisation of acrylamide andN,N′-methylenebisacrylamide using Potassium peroxodisulphate (K₂S₂O₈) as initiator. A linear relationship was obtained between the range of 0 to 10 ppb.     

我国农田农药流失现状及减控策略

农业面源污染已经成为全球水污染的主要来源,其中具有生物毒性的农药污染物对人体健康和生态环境安全构成了严重威胁。分析了我国农田农药流失现状,指出流失的主要农药品种与用药历史和特点密切相关,水体中检出的有机氯农药主要源于早期农药残留,检出的有机磷农药和长残效除草剂部分种类目前仍在使用。提出从影响农药流失的各个环节入手,制定严密的减控策略。植物缓冲带是拦截农药流失的常用措施,可以实现对农业面源污染的可持续治理。建议实行生态功能区划,严格限制高毒农药的施用,减少化学农药施用量,规范农药喷洒器械和施药技术,从源头上控制农药流失,从而降低农业非点源污染带来的危险。     

欧美新污染物监测进展及启示

新污染物监测是新污染物环境和健康风险评估及管控的重要基础。欧美发达国家环保部门在20世纪70年代就开展了新污染物监测工作,并且2000年后形成了相应的监测制度,而我国新污染物监测工作正处于业务化起步阶段。通过深入调研欧美国家水中新污染物监测为主的发展历程、监测清单、监测要求等内容,总结出3个特点:建立动态更新的新污染物清单监测机制;将规范的新污染物监测方法作为开展监测的重要前提;充分考虑监测可行性和经济成本。结合我国现阶段新污染物监管需求及监测现状,提出我国新污染物监测工作的3点建议:明晰国家、地方新污染物监测的职责分工,建立优先监测新污染物清单动态更新机制;加强新污染物监测能力建设,建立新污染物监测标准体系;循序渐进开展新污染物监测,注重监测的可行性和可持续性。     

A new system to bioassay pesticides present in the surface microlayer using floating propagules of an aero-aquatic hyphomycetous fungus Pseu doaegerita matsushimae

The surface microlayer often contains pesticides at levels which may be more than one hundred thousand times those sampled in the remainder of the water column. Standard bioassay systems cannot asses these pesticides since no system yet devised has made use of organisms inhabiting the surface microlayer. Using floating propagules of Pseudoaegerita matsushimae, an aeroaquatic hyphomycetous fungus, a bioassay system was devised in which the percentage germinations of such propagules after exposure to various levels of pesticides were plotted to produce a dosegermination scale onto which subsequent data could be fitted. The following pesticides and pesticide mixtures were used: PCP; DDT; Methoxychlor; Bis(tributyl)tin Oxide; Malathion; Captan; 1 part PCP/1 part DDT; 2 parts PCP/1 part DDT; 3 parts PCP/1 part DDT; 2 parts DDT/1 part PCP; 3 parts DDT/1 part PCP; 1 part PCP/1 part Methoxychlor; 2 parts PCP/1 part Methoxychlor; 3 parts PCP/1 part Methoxychlor; 2 parts Methoxychlor/1 part PCP; 3 parts Methoxychlor/1 part PCP. The bioassay system revealed increased sensitivity to pesticides and pesticide mixtures which affected respiratory metabolism. Some pesticide mixtures were more effective in inhibiting germination than their individual components while others appeared much less toxic to the propagules than their unassisted components.     

A novel environmental indicator for monitoring of pesticides

The identification of an indicator for monitoring pesticides is a very effective analytical approach because it allows one to schedule and simplify the analytical routine. In this study, a new indicator has been designed, which has to be able to define a scale of priorities in the pesticides monitoring. A starting equation was developed involving the escaping tendency of a given substance from a phase (based on the Mackay model I level). The reliability of the indicator was tested by application to a model system, consisting of a defined and limited area, choosing water as matrix over a period of 6 years. A group of marker compounds was also defined to implement the predictive efficacy of the indicator. The results obtained by modeling were compared to those obtained by experimentation of the same model system. The indicator was subsequently and appropriately modified creating a new equation, including a kinetic factor, which considers the environmental degradation processes. The effect of the rectified indicator was consistent with the sales data list of compounds, when applied to the markers. The indicator developed in this study, tested as a model on specific area-phase-period (Province of Siena, water phase, 2000?C2006), is applicable to any other area-phase-period, adjusting the partition value of the Mackay model for the case under study.     

Monitoring and risk assessment of pesticides in a tropical river of an agricultural watershed in northern Thailand

The increasing application of pesticides in the uplands of northern Thailand has increased the transfer of pesticides to surface water. To assess the risk of pesticide use for stream water quality, we monitored the concentrations of seven pesticides (atrazine, dichlorvos, chlorpyrifos, dimethoate, chlorothalonil, (α-, β-) endosulfan, cypermethrin) frequently used in the Mae Sa watershed (77 km²) in water and sediment samples over a period of one and a half years (2007–2008). All investigated pesticides were recorded in the river. Chlorpyrifos was detected most often in water samples (75 % at the headwater station), while cypermethrin was most often found in riverbed (86 %) and in all suspended sediment samples. The highest concentrations of the pesticides were detected during the rainy season. About 0.002 to 4.1 % by mass of the applied pesticides was lost to surface water. The risk assessment was based on the risk characterization ratio (RCR). The RCRs of dichlorvos in water, (α-, β-) endosulfan, and cypermethrin in water and sediments were higher than unity indicating that they are likely to pose a threat to aquatic ecosystem. Finally, we discuss the role of sampling design on ecotoxicological risk assessment. Our study shows that pesticide contamination of surface waters is an environmental issue in the Mae Sa watershed and that measures need to be undertaken to reduce the loss of pesticides from soil to surface waters.     

Identification of residual pesticides in water by GC/QPMS

The extensive use of the broad range of pesticides employed to maintain golf courses has prompted serious environmental concerns in Japan since courses tend to be located in mountainous regions, often in close proximity to virgin water sources. Since older empirical methods are not appropriate for substance identification and determination of substance concentrations on the ppb order, gas chromatographyquadrupole mass spectrometry (GC/QPMS) can be employed. A simple extraction of 500 ml of drainage pond water gives a sample which allows identification of pesticides with quantitation on the ppb order using selected ion monitoring (SIM). A sample of drainage pond water from a golf course revealed fenitrothion, funitrothion, chlorothalonil and isoprothiolane in concentrations of 120.1, 20.7, 45.6 and 130.5 ppb, respectively.     

Occurrence of pesticides in surface water bodies: a critical analysis of the Italian national pesticide survey programs

In recent years, several monitoring programs have been established as a consequence of EU Directives which include requirements for monitoring the quality of water resources (drinking water, groundwater and surface water). Plant protection products (PPPs) are an obvious target for monitoring activities, since they are directly released into the environment. In Italy, the National Environmental Protection Agency (ISPRA ex APAT) has recently published two reports containing the results of the National Plans for Control of Environmental Effects of PPP. These documents contain the collection of monitoring data related to the presence of PPP residues in surface water and groundwater. The first objective of this work was to critically analyze the results of monitoring campaigns on pesticide residues in surface waters in Italy. In particular, the paper focuses on whether and how the Italian approach satisfies the requirements of the Water Framework Directive, whether they are representative of the whole national territory, and how the utilized approach is appropriate for the characterization of risk to surface water. Starting from this analysis, some considerations about the limits of environmental monitoring as a tool for managing risk were highlighted.     

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.     

occurrence and distribution of nitrate and pesticides in bowdle aquifer, south dakota

A shallow aquifer in central South Dakota was monitored for thepresence of nitrate and pesticides. A total of 593 nitrate samples and428 pesticide samples were analyzed from nine different sites and 14wells between 1989 and 1994. Nested wells were installed at four sitesto characterize the distribution pattern of nitrate and pesticidemovement in ground water. Nitrate concentrations and pesticidedetections were qualitatively compared with area precipitation and watertable fluctuations. The results indicate that nitrates tend to betransported by a leaching mechanism in a matrix flow and may appearin ground water within months after the fertilizer application in thefields. The pesticide movement is primarily controlled by geologicaland chemical characteristics of medium and pesticides.     

Spatial Relationships Between Water Quality and Pesticide Application Rates in Agricultural Watersheds

Pesticide applications to agricultural lands in California, USA, are reported to a central data base, while data on water and sediment quality are collected by a number of monitoring programs. Data from both sources are geo-referenced, allowing spatial analysis of relationships between pesticide application rates and the chemical and biological condition of water bodies. This study collected data from 12 watersheds, selected to represent a range of pesticide usage. Water quality parameters were measured during six surveys of stream sites receiving runoff from the selected watershed areas. This study had three objectives: to evaluate the usefulness of pesticide application data in selecting regional monitoring sites, to provide information for generating and testing hypotheses about pesticide fate and effects, and to determine whether in-stream nitrate concentration was a useful surrogate indicator for regional monitoring of toxic substances. Significant correlations were observed between pesticide application rates and in-stream pesticide concentrations (p < 0.05) and toxicity (p < 0.10). In-stream nitrate concentrations were not significantly correlated with either the amount of pesticides applied, in-stream pesticide concentrations, or in-stream toxicity (all p > 0.30). Neither total watershed area nor the area in which pesticide usage was reported correlated significantly with the amount of pesticides applied, in-stream pesticide concentrations, or in-stream toxicity (all p > 0.14). In-stream pesticide concentrations and effects were more closely related to the intensity of pesticide use than to the area under cultivation.     

Assessment of organochlorine pesticide residues in Indian flue-cured tobacco with gas chromatography-single quadrupole mass spectrometer

Presence of pesticide residues in tobacco increases health risk of both active and passive smokers, apart from the imminent potential health problems associated with it. Thus, monitoring of pesticide residue is an important issue in terms of formulating stringent policies, enabling global trade and safeguarding the consumer’s safety. In this study, a gas chromatography-single quadrupole mass spectrometry (GC-MS) method based upon quantifier-qualifier ions (m/z) ratio was employed for detecting and assessing ten organochlorine pesticide residues (α-HCH, β-HCH, γ-HCH, δ-HCH, 2,4-DDT, 4,4-DDT, endrin, α-endosulfan, β-endosulfan and endosulfan sulphate) in 152 flue-cured (FC) tobacco leave samples from two major tobacco growing states, Karnataka and Andhra Pradesh, of India. In the majority of samples, pesticide residue levels were below the limit of quantification (LOQ). In few samples, pesticide residues were detected and they found to comply with the guidance residue levels (GRL) specifications of the Cooperation Center for Scientific Research Relative to Tobacco (CORESTA). Detection of the phase out pesticides like DDT/HCH might be due to transfer of persistent residues from the environmental components to the plant. This is the first report on these ten organochlorine pesticide residues in Indian FC tobacco.