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。     

青海省西宁市和天峻县大气颗粒物中有机氯农药和类二噁英多氯联苯的水平与分布

本研究测定了青海省西宁市与海西蒙古族藏族自治州天峻县夏、冬两季大气颗粒物中有机氯农药(OCPs)和类二噁英多氯联苯(DL-PCBs)的浓度水平.结果表明,青海省大气颗粒物中OCPs主要为DDTs、HCHs.西宁市DDTs和HCHs的平均水平分别为:35 pg·m-3、5.9 pg·m-3(夏季)和93 pg·m-3、11 pg·m-3(冬季),天峻县DDTs和HCHs的平均水平分别为:83pg·m-3、6.4 pg·m-3(夏季)和28 pg·m-3、6.7 pg·m-3(冬季).与亚洲其它地区相比,青海省大气颗粒物中OCPs处于较低水平.西宁市大气颗粒物中DL-PCBs的平均水平分别为:0.52 pg·m-3(夏季),0.99 pg·m-3(冬季),天峻县为:0.58 pg·m-3(夏季)、0.52 pg·m-3(冬季).西宁市夏、冬两季OCPs的平均水平均大于天峻县,而两地DL-PCBs的平均水平相当.本研究中高原地区DL-PCBs的分布特点及变化规律与极地地区的研究相比存在一定的相似性,而DDTs和HCHs则存在差异性.     

Air pollution and young children's inhalation exposure to organophosphorus pesticide in an agricultural community in Japan

Assessment of airborne organophosphorus pesticides in houses of young children (1-6 years old) and childcare facilities was conducted following pesticide applications in an agricultural community in Japan. Trichlorfon and fenitrothion, applied in two separate periods, were frequently detected from outdoor and indoor air. Dichlorvos, the primary degradation product of trichlorfon, was also detected after the application of trichlorfon. Both the outdoors and indoor concentration of applied pesticide were shown to increase with decreasing distance from the pesticide-applied farm. Indoor concentration of these pesticides significantly correlated with outdoor concentration (p=0.001 for trichlorfon and p=0.001 for fenitrothion), indicating infiltration of applied pesticide inside. Ratio of indoor to outdoor concentration (I/O ratio) of fenitrothion was higher for houses with windows open during the application than those with closed windows (median value: 0.74 vs. 0.16, p=0.003). However, a similar trend was not observed for trichlorfon as well as dichlorvos in the first period. Dichlorvos was found to have a higher I/O ratio than trichlorfon during the period, and clear correlation between indoor concentrations of dichlorvos and those of trichlorfon suggested increased decomposition of trichlorfon in the indoor environment. Daily inhalation exposure estimated by using the fixed measurement data and time-activity questionnaire ranged from 0 to 35 ng/kg/day for trichlorfon, from 0 to 26 ng/kg/day for dichlorvos, and from 0 to 44 ng/kg/day for fenitrothion. Median inhalation exposure from indoor air accounted for 74%, 86.3%, and 45% of the daily inhalation exposure, respectively. For kindergarteners or nursery school children, inhalation exposure at childcare facilities was comparable with or more than that at home, indicating that pollution level at childcare facilities had potential of high impact on children's exposure. Estimated daily inhalation exposures were inversely correlated to the proximity of their activity location to the pesticide-applied farm.     

Toxicity of pesticides toward human immune cells U-937 and HL-60

Abstract

The industrialization of the agricultural sector has significantly increased the use of chemicals such as pesticides. Therefore, exposure to them is unavoidable, which makes it necessary to assess their safety for humans at actual exposure doses. This paper aims to determine toxicity of three types of pesticides toward human immune cells (HL-60 and U-937): glyphosate (GLY), deltamethrin (DEL), and chlorothalonil (CHL). Cell viability, membrane integrity, inflammation induction, and antioxidant activity were evaluated to determine differences in cellular response to the tested plant protection agents. In experimental models, all tested substances caused increased mortality of cells after only 24?h. Cell membrane damage was recorded under DEL and CHL influences. The largest disintegration of the cell membrane was due to the action of 100?μg/mL DEL for U-937 and CHL at 1?μg/mL for HL-60. GLY at a concentration of 3,600?μg/mL caused significant peroxidation of U-937 cells’ lipids. CHL-induced inflammation in both types of cells tested. DEL and GLY also induced antioxidant activity in cells. These results lead to the conclusion that the tested pesticides act cytotoxically to the cells of the human immune system in doses to which both farmers and consumers are exposed.     

前驱物结晶体升华成膜法制备TiO2薄膜及其光催化性研究

采用“前驱物结晶体升华成膜法”工艺，使含钛前驱物结晶体草酸氧钛酸以升华的方式，均匀地在玻璃表面形成前驱物薄膜；经过热处理，制备出外观平整透明的玻璃基TiO2薄膜，其薄膜厚度为80-100nm，粒度≤50nm。初步研究了制备条件、薄膜性能和本工艺制备的玻璃基TiO2纳米薄膜对甲基对硫磷的光催化降解性能。