微波萃取-气相色谱/质谱法测定土壤中的有机氯农药

通过微波萃取提取土壤中的有机氯农药,萃取溶液经浓硫酸脱色、佛罗里硅土柱净化,最后用气相色谱/质谱法分析.以石英砂为基体进行加标回收测定,有机氯农药的回收率在75.5%～103%之间,检出限为0.01μg/kg.     

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.     

The effect of mixtures of organophosphate and carbamate pesticides on acetylcholinesterase and application of chemometrics to identify pesticides in mixtures

Organophosphate (OP) and carbamate (CP) pesticides act by the inhibition of acetylcholinesterase (AChE). This enables the use of this enzyme for the detection of these pesticides in the environment. While many studies have looked at the effect of single pesticides on AChE, the effect of mixtures of pesticides still requires extensive investigation. This is important to evaluate the cumulative risk in the case of simultaneous exposure to multiple pesticides. Therefore we examined the effect of five different pesticides (carbaryl, carbofuran, parathion, demeton-S-methyl, and aldicarb) on AChE activity to determine whether combinations had an additive, synergistic, or antagonistic inhibitory effect. Results indicated that the mixtures had an additive inhibitory effect on AChE activity. The data from the assays of the mixtures were used to develop and train an artificial neural network (ANN) which was then utilised successfully for the identification of pesticides and their concentrations in mixtures. This study is significant because it evaluated mixtures of OPs and CPs where previous studies focused on either OPs or CPs. Previous studies have only examined up to three pesticides while this study evaluated mixtures of five pesticides simultaneously. This is also the first study where an ANN was able to utilise data from the inhibition of a single enzyme to differentiate five different pesticides and their concentrations from mixtures.     

固相微萃取一毛细管气相色谱法快速分析水中有机氯农药

固相微萃取是一种快速、简便、集萃取浓缩进样于一体的样品前处理技术,具有分析时间短、灵敏度高、无需有机溶剂的优点.本工作用固相微萃取富集水中有机氯农药,毛细管气相色谱分离分析,整个分析过程只需30min,检出限可迭0.01至0.1μg/L,已用于降雨、地面水、海洋中有机氯农药含量的测定.     

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.     

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 of organochlorine pesticides in drinking water supplies

The effectiveness of the treatment process for the removal of pesticides in the final water supplies in Delhi has been evaluated. Samples were collected during 2000–2005 from five water treatment plants (WTPs). Analysis was carried out to identify pesticides, which are more commonly encountered in treated drinking water. In most of the treatment plants, the concentrations of lindane, total endosulphan and total DDT were significantly less in the finished water. Monitoring of these less soluble pesticide in the finished water from WTPs was done quarterly to arrive at the quality trends and to plan for the mitigation action, in case the concentration of the parameter exceeded at any site or time.     

固相微萃取-毛细管气相色谱法快速同步分析水中有机氯及有机磷农药

固相微萃取是一种快速、简便,集萃取浓缩进样于一体的样品前处理技术,具有分析时间短、灵敏度高、无需有机溶剂的优点.用固相微萃取富集水中8种有机氯及7种有机磷农药,毛细管气相色谱ECD检测器分离分析,整个分析过程只需26min,检出限可达0.002～1μg/L,已用于地表水中有机氯及有机磷农药含量的测定.     

Incidence of organochlorine pesticides in soils of Shenzhen, China

To determine the incidence of organochlorine pesticides (OCPs) in soil in a rapid urbanization region, soil samples from various land use types in Shenzhen were collected in winter, 2007. The concentration of dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs) ranged from non-detected to 149 ng g(-1) and 19 to 88 ng g(-1), respectively. The highest levels of OCPs were observed in soil from traffic and industry areas, reflecting that intensive human disturbance make the soil pollution accumulation more disperse. HCHs and DDTs profiles revealed that the sources were associated mainly with lindane and technical DDTs, respectively, while HCHs in the soil of Shenzhen might originate from both recent and historical sources. The loss of OCPs by soil erosion will enter surface runoff and impose impact on the water environment. Non-dietary exposure estimation indicates that children were the most sensitive group. The average daily exposure to OCPs for males was more serious than for females. Non-dietary exposure to DDTs and HCHs in residential blocks of Shenzhen were far below the acceptable daily intake recommended by the Food and Agriculture Organization/World Health Organization.     

The distribution of organochlorine pesticides (OCPs) in surface sediments of Bohai Sea Bay,China

The residues of organochlorine pesticides (OCPs) in 19 surface sediments of Bohai Sea Bay were determined in this study. Total OCP concentration in surface sediment ranged from 9.01 to 18.04 ng/g dry weight, with a mean concentration of 12.50 ng/g. These findings are in the mid-range of pesticide concentrations compared to those reported in other regions worldwide. DDTs and HCHs were the predominant species. The α-HCH/β-HCH ratios and the predominant γ-HCH indicate that the technical HCH contamination was due mainly to historical usage, although there appeared to be a fresh input of lindane. The results from \(\left( {\mbox{DDD}\,\mbox{+}\,\mbox{DDE}} \right)\mbox{/}\sum {\mbox{DDTs}} \) and DDD/DDE calculations suggest that the usage of DDT in agricultural activities was not terminated, and the historical/fresh inputs of DDT in these areas could be more easily degraded into DDD under an anoxic condition. PCA implies that the recent usage of DDT could serve as important fresh input sources for OCPs.     

Enantioselective aquatic toxicity of current chiral pesticides

Chiral pesticides are ubiquitous in the aquatic environment, and their enantioselectivities in aquatic toxicity are known to be complicated. The difference in enantioselective effects between enantiomers may sometimes differ by approximately 100-fold or more, which makes it important to incorporate enantioselective effects into the risk assessment of chiral pesticides. In this paper, we reviewed relevant work on the aquatic toxicity of chiral pesticides with an emphasis on the enantioselective aquatic toxicity under both chronic and acute exposure conditions. We provided a personal account of the importance of studies on molecular mechanisms of developmental toxicity and specific endpoints such as vitellogenin, yolk sac edema and pericardial edema in future research. Given the widespread use of chiral pesticides, we suggest that a more comprehensive understanding of the significance of enantioselective aquatic toxicity will be very helpful in improving risk assessment and regulation of chiral pesticides.     

Persistence and behavior of pesticides in cotton production in Turkish soils

Turkey is the sixth largest producer of cotton in the world. Two of the most commonly applied pesticides used in cotton production are trifluralin and endosulfan. Although both are very effective at controlling pests, their persistence in the environment poses risks to human health and the environment. Four loam soils and one silty-loam soil were studied to evaluate the persistence of trifluralin and endosulfan in relation to soil characteristics. Degradation with trifluralin reached as high as 70% of the applied doses. Soils with the highest organic matter content had the lowest degradation rate, indicating a tighter sorption of trifluralin. Endosulfan degradation was a function of soil type and the specific isomer, with β-endosulfan depicting the highest degradation.     

Hydrology-linked spatial distribution of pesticides in a fjord system in Greenland

A pilot study is presented evaluating selected chlorinated pesticides as chemical tracers for water masses in a sub-Arctic fjord system (Godth?bsfjord, western Greenland). Polyoxymethylene (POM) based passive water samplers were deployed during summer-autumn 2010. The levels of the analysed chlorinated pesticides in the fjord surface waters were found to be low compared to earlier studies. α-Hexachlorocyclohexane (α-HCH) and hexachlorobenzene (HCB) were the predominant contaminants. However, these two compounds have higher levels in oceanic water compared to freshwater influenced fjord waters. These chemicals can thus be considered as indicators for direct atmospheric long-range transport, while the organochlorine pesticides like trans-, cis-chlordane, trans-nonachlor and oxychlordane that are detected in the inner parts of the fjord are indicators for potential freshwater sources such as rivers and glacial meltwater runoff (secondary sources). The average values were 50 pg L(-1) for HCB and 11 pg L(-1) for α-HCH. These concentrations are comparable to levels in fjords in Svalbard (Norwegian Arctic), but lower than in open and/or ice covered oceans in the Canadian Arctic. Two air samplers were deployed for the identification of direct atmospheric contributions. Local contamination sources do not contribute significantly. The study demonstrated the value of passive water sampling devices for comprehensive hydrological characterization of Arctic coastal waters.     

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.     

Pollution by organochlorine pesticides in Navachiste-Macapule,Sinaloa, Mexico

The lagoon system of Navachiste-Macapule is located in northern Mexico, in the state of Sinaloa, with an area of 24,000 ha. The main economic activity in the area is agriculture, and the lagoon lies next to the irrigation district ID-063 which covers 116,615 ha. The purpose of this study is to evaluate the levels of pollution generated by organochlorine pesticides (OC) in the surface sediments of the lagoon and in the agricultural drains of the ID-063 that are supposedly transported into the system as a result of agricultural activities and runoff from adjacent land. For this, between 2006 and 2007, 45 surface sediment samples were collected (warm dry, rainy and cold dry) from 15 sampling sites, during the three climatic seasons. Of these, eight were located inside the lagoon in marine conditions (salinity >31 PSU) and seven in the agricultural drains of the ID-063 in freshwater conditions (salinity <5 PSU). The average concentration of the OC in the sediments was 44.75 ng g^− 1, among which the group of the alicyclic compounds presented the greatest concentrations. The average value of the total organic carbon (TOC) in the sediments of the system was 0.90%. The sediments collected inside the lagoon had an average OC concentration of 18.97 ng g^− 1, and the predominant type of sediment was fine to very fine sand. The average OC concentration in the sediments collected in the agricultural drains was 75.69 ng g^− 1, where fine sediments (silt) were predominant. The presence of methoxychlor, endrin and heptachlor suggested that these compounds were continuously used in the system, even though their use is forbidden in Mexico.