Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

Electrochemical Monitoring of Methylparathion Degradation in an Acid Aqueous Medium in Presence of Cu(II)

Abstract

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o, 4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2–7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH ≤ 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 × 10^?3 s^?1 at pH 2, 5.5 × 10^?3 s^?1 at pH 4 and 9.0 × 10^?3 s^?1 at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

微米Cu／Fe对污染土壤洗脱液中有机氯农药的降解

以表面活性剂TritonX-100（TX-100）为洗脱剂,某有机氯农药（organochlorinepesticides,OCPs）污染场地土壤为对象,七氯、氯丹和灭蚁灵为目标污染物,研究微米Cu／Fe双金属对污染土壤洗脱液中OCPs的降解效果。考察了洗脱液中OCPs初始浓度、洗脱液pH值、微米零价铁加入量和cu负载量对Cu／Fe去除OCPs效果的影响。结果表明,微米Cu／Fe可以有效的去除土壤洗脱液中目标污染物。当微米零价铁加入量为1．0g（25g／L）,cu负载量为1．0％,洗脱液pH值为6．89时,Cu／Fe对2号土壤洗脱液中七氯、γ-氯丹、α-氯丹和灭蚁灵的去除效果最好,去除率分别为100．0％、99．3％、80．8％和71．1％。洗脱液中OCPs初始浓度越低,微米零价铁加入量越大,Cu／Fe对OCPs去除率越高;偏酸性条件有利于Cu／Fe对γ-氯丹和灭蚁灵的去除,而α-氯丹在中性条件下去除效果最好;1号土壤和2号土壤洗脱液的最佳铜负载量分别为2．O％和1．0％。     

Anuran Development, Density and Diversity in Relation to Agricultural Activity in the Holland River Watershed, Ontario, Canada (1990–1992)

Significantly lower anuran species diversity and density was recorded in a vegetable growing area relative to upstream and downstream sites in the Holland River watershed, Ontario, Canada. Egg hatching success and tadpole deformity rates of American toads (Bufo americanus americanus), green frogs (Rana clamitans melanota) and northern leopard frogs (Rana pipiens) eggs in water from field sites and control water were assessed. Compared to the control and the upstream site, the total abnormality rate (unhatched eggs plus deformed tadpoles) was higher for American toads in water from the agricultural and downstream sites. Total abnormality was higher in green frog eggs in water from the agricultural site and a downstream site. Trace concentrations of organophosphorus pesticides were detected most often in agricultural zone water and sediments than in upstream and downstream sites. Organochlorine pesticide residues, especially in agricultural zone samples, exceeded the no effect level guidelines for the protection of aquatic life. Ammonia, phosphorus, particulates, BOD and TKN were highest in the agricultural zone. Significant correlations between these parameters and anuran development suggest nutrient run-off as a causal or contributing factor in lower anuran diversity, density and reproductive success of American toads and green frogs in the site dominated by agriculture.     

MODEL FOR PREDICTING TRANSPORT OF PESTICIDES AND THEIR METABOLITES IN THE UNSATURATED ZONE1

ABSTRACT: A finite element model based on Galerkin's upstream weighted residual technique was developed to predict the simultaneous convective-dispersion transport and transformations of pesticides and their metabolites in the unsaturated zone. Transformations of the parent compound and its metabolites were assumed to be first-order reactions for oxidation and hydrolysis, while adsorption of the pesticide species (parent compound and metabolites) to the soil components was assumed to be represented by a linear equilibrium (Freundlich type) isotherm. Volatilization and plant root uptake of pesticides in the solution phase were neglected in the analysis. The proposed model was used to simulate the transport and transformation of aldicarb and its metabolites, aldicarb sulfoxide and aldicarb sulfone, in the soil profile. Several examples are used to demonstrate the accuracy, validity, and applicability of the proposed model. Simulated results indicate that the proposed model can potentially be used to estimate the mass flux of water, and pesticide and pesticide metabolite concentrations in the subsurface environment. However, further verification of the model against actual field data is needed to fully demonstrate the model's potential.     

Sorption of chlorpyrifos and fonofos on four soils and turfgrass thatch using membrane filters

Abstract

Chemical transport in soil is a major factor influencing soil and water contamination. Four soils and turfgrass thatch, representing a wide range of organic carbon OC content were studied to determine sorption K_d and K_f parameters for the insecticides chlorpyrifos and fonofos. The batch equilibrium method was used. The concentration of insecticide was measured in the solution as well as in the solid phase to determine the most accurate sorption data. Four soils and thatch were equilibrated for 24 h at 22 ± 1^OC with aqueous insecticide solutions. Four concentrations of the insecticides, each <50% of their respective water solubilities, were selected for the experiments. After extraction with an organic solvent, the concentration of insecticides in the aqueous solution was determined by gas liquid chromatography using electron capture detection for chlorpyrifos, and nitrogen/phosphorus detection for fonofos. Data obtained were fitted to the log and simple linear form of the Freundlich equation. Mass balance Freundlich isotherm exponents n ranged between 0.82 and 0.93 for chlorpyrifos. 0.82 and 1.21 for fonofos, with r² ≥ 0.97. K_oc (percent of organic carbon %OC normalized Sorption coefficient) values were calculated by using experimentally developed K_d and K_f coefficients in relation to OC levels from 0.29 to 34.85%. K_d and K_f coefficients of both insecticides were positively correlated with OC (r² ≥ 0.96). organic matter OM (r² ≥ 0.96), and cation exchange capacity CEC (r² ≥ 0.90).     

Estimating Watershed Level Nonagricultural Pesticide Use From Golf Courses Using Geospatial Methods1

Abstract: Limited information exists on pesticide use for nonagricultural purposes, making it difficult to estimate pesticide loadings from nonagricultural sources to surface water and to conduct environmental risk assessments. A method was developed to estimate the amount of pesticide use on recreational turf grasses, specifically golf course turf grasses, for watersheds located throughout the conterminous United States (U.S.). The approach estimates pesticide use: (1) based on the area of recreational turf grasses (used as a surrogate for turf associated with golf courses) within the watershed, which was derived from maps of land cover, and (2) from data on the location and average treatable area of golf courses. The area of golf course turf grasses determined from these two methods was used to calculate the percentage of each watershed planted in golf course turf grass (percent crop area, or PCA). Turf‐grass PCAs derived from the two methods were used with recommended application rates provided on pesticide labels to estimate total pesticide use on recreational turf within 1,606 watersheds associated with surface‐water sources of drinking water. These pesticide use estimates made from label rates and PCAs were compared to use estimates from industry sales data on the amount of each pesticide sold for use within the watershed. The PCAs derived from the land‐cover data had an average value of 0.4% of a watershed with minimum of 0.01% and a maximum of 9.8%, whereas the PCA values that are based on the number of golf courses in a watershed had an average of 0.3% of a watershed with a minimum of <0.01% and a maximum of 14.2%. Both the land‐cover method and the number of golf courses method produced similar PCA distributions, suggesting that either technique may be used to provide a PCA estimate for recreational turf. The average and maximum PCAs generally correlated to watershed size, with the highest PCAs estimated for small watersheds. Using watershed specific PCAs, combined with label rates, resulted in greater than two orders of magnitude over‐estimation of the pesticide use compared to estimates from sales data.     

Toxicity of carbaryl,diquat dibromide,and fluoranthene,individually and in mixture,to larval grass shrimp,Palaemonetes pugio

This study examined the toxicity of two pesticides (carbaryl and diquat dibromide) and one polycyclic aromatic hydrocarbon (fluoranthene), both singly and in mixture, to grass shrimp larvae (Palaemonetes pugio). These three chemicals are all present in coastal environments and can easily enter estuarine ecosystems. Fluoranthene was the most toxic chemical with a 96-h LC₅₀ value of 32.45 μ g/L, followed by carbaryl (43.02 μ g/L) and diquat dibromide (1624 μ g/L). In the chemical mixture tests, the binary carbaryl/diquat dibromide mixture and the ternary carbaryl/diquat dibromide/fluoranthene mixture had additive results.     

碳源对工业污染场地土壤中HCHs和DDTs降解的促进作用

我国对有机氯农药的大量需求使得在农药生产、加工和分装等过程中造成了许多城镇中存在有机氯农药污染场地,限制了土地的后续开发利用.本研究选取3种类型的碳源组成有机修复剂A、B、C,添加到受有机氯工业污染场地土壤中进行微生物降解试验,并对比了3种修复剂的效果.试验过程中,反应体系水分含量为50％,添加零价金属调节氧化还原电位,采用好氧/厌氧交替循环方式进行生物降解.实验结果表明:3种修复剂对HCHs和DDTs的降解都有显著促进作用.与DDTs相比,HCHs较易降解.90 d内,添加修复剂(A、B、C)的处理中∑HCH的浓度分别从73.37~85.71 mg·kg^-1降解到了15.88~38.21 mg·kg^-1.与未添加修复剂的对照相比较,∑HCH的降解率提高了19%~52%,90 d内,ΣHCH的降解率最高可达81%.添加修复剂(A、B、C)的处理中ΣDDT的浓度分别从91.68~119.79 mg·kg^-1降解到了45.1~60.7 mg·kg^-1,相对未添加修复剂的对照试验,∑DDT的降解率提高了39%~45%,30 d内∑DDT的降解率最高可达到51%,但30 d后降解效率无明显增加.就不同类型碳源的促进作用来看,C/N最高,而含水率最低的修复剂B的效果最好,而C/N比最低而含水率最高的修复剂A效果最差.     

有机氯农药污染土壤的Fenton氧化修复研究

研究了Fenton氧化对某实际有机氯农药污染场地土壤的修复效果。结果显示:Fenton氧化能够快速有效地降解污染土壤中的六氯和DDTs。当Fe2+浓度为80 mmol/L,Fe2+与H2O2的摩尔浓度比为1∶5,水土比10∶1时,反应6 h,土壤中六氯和总DDT的去除率分别为:96.7%和78.2%。每方土的修复成本估算为951元。