加速溶剂萃取-气相色谱/串联质谱法测定土壤中20种有机氯农药

建立了用加速溶剂萃取法（ASE）提取、气相色谱-串联质谱法分析土壤中20种有机氯农药的方法。用正己烷和丙酮（1∶1,V/V）的混合溶剂为提取剂,萃取温度100℃,压力1 500 psi,静态提取10 min,循环提取2次,提取液经石墨化碳黑固相萃取柱净化,浓缩后进行GC-MS/MS测定,外标法定量。试验结果表明,采用串联质谱多反应监测模式,降低了背景干扰,当取5 g土壤时,有机氯农药的检出限在0.1~3.0μg/kg之间,低浓度水平（8μg/kg）的基体加标回收率为70.3%~134%,相对标准偏差〈23%。测定方法背景干扰低,灵敏度高,适合土壤中20种有机氯农药残留的同时测定。     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

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.     

桂林会仙岩溶湿地水体与沉积物中有机氯农药污染特征

湿地对环境污染起重要的缓冲作用,但岩溶区岩溶管道的存在会导致污染物沿高度发达的岩溶管道对地下环境产生威胁.因此,认识岩溶地貌环境中的污染物分布特征是污染物生态风险评估与防范的前提.以24种有机氯农药（OCPs）为研究对象,分析了桂林会仙湿地枯水期和丰水期水体和表层沉积物中OCPs的含量组成特征,解析其来源,并开展风险评价.结果表明,水体中ρ（OCPs）范围为3.17~92.50 ng ·L^-1,沉积物中ω（OCPs）范围为1.16~219.52 ng ·g^-1,呈现以六六六（HCHs）和滴滴涕（DDTs）为主的污染特征,水中OCPs含量表现为丰水期高于枯水期,沉积物中OCPs含量枯水期高于丰水期.特征比值法表明OCPs主要为长时间降解残留,部分点位有林丹的新输入.基于蒙特卡洛模拟开展健康风险评价,结果表明,95%分位数水平上,水体中OCPs对人体致癌风险大于1×10^-6,存在潜在健康风险但可接受;非致癌风险均低于1,说明研究区水体中OCPs残留水平不足以对人体造成非致癌风险.     

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.