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。     

官厅水库沉积物表层中的有机氯农药分布特征及风险评价

采用气相色谱法对北京市官厅水库沉积物表层中持久性有机氯农药(OCPs)的残留状况进行了调查,并对有机氯农药污染水平和生态风险作出评价。结果表明:沉积物中有机氯农药总含量为8.48 ng/g～24.40 ng/g,其中HCHs和DDTs的含量较高,分别为1.11 ng/g～7.73 ng/g和2.97 ng/g～10.52 ng/g,其组分特征为来自环境的残留。与沉积物风险评估低值(ERL)和风险评估中值(ERM)对比评价沉积物中有机污染物的风险程度,官厅水库沉积物表层中的有机氯农药存在一定的生态风险。     

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).     

惠州农业土壤、灌溉水和农产品中有机氯农药的残留

用气相色谱法(GC-ECD)对惠州市51个农业土壤样品、12个灌溉水样品和21个农产品样品中的HCHs和DDTs残留量进行了测定.HCHs平均含量分别为土壤1.66μg/kg、灌溉水5.86ng/L、农产品24.74μg/kg;DDTs平均含量分别为土壤4.98μg/kg、灌溉水2.06ng/L、农产品41.72μg/kg,土壤中有机氯农药通过多种方式进入到水体及农产品中.从HCHs和DDTs异构体组成可以看出,环境中绝大多数农药残留是由于历史上使用造成的,个别地区可能还有新的污染输入.同其它地区相比,惠州农业土壤和灌溉水中的有机氯农药残留水平较低,但农产品尤其是蔬菜中DDTs富集程度较高.     

浸润线缓慢上升对滑坡剩余推力的影响规律

地下水浸润线变化对滑坡下滑力、抗滑力和剩余推力的影响甚大。基于传力系数法,建立了浸润线缓慢上升时剩余推力改变量的计算模型,探讨了滑面倾角、浸润线角度和滑面内摩擦角与倾角正切比对浸润线缓慢上升前后滑坡剩余推力改变量的影响规律;将浸润线缓慢上升时剩余推力由增大到减小的分界点称为剩余推力变化临界点,分析了剩余推力变化达到临界点时的浸润线倾角分布规律;提出了剩余推力变化的临界线,确定了浸润线缓慢上升时剩余推力的增大区域和减小区域。     

Principal component analysis for soil contamination with organochlorine compounds

In order to investigate the distribution pattern of individual organochlorine compounds in soil samples collected from the sites (Canary Island – Spain, China, Germany, India, Romania, Russia, Serbia, Swiss, UK) affected by industrial activities to the more remote areas, principal component analysis was performed on the data taken from literature. Loading plots pointed out the strong correlation among the variables. Score plots revealed similar PCB- and OCP-soil patterns for majority of the investigated sites. Nevertheless, the temporal differences of PCB-soil loads have been identified: the late 1990s and early 2000s concentrations are similar to those of the early 1940s, and they are below the levels existed in 1980. The most pronounced PCB concentrations characterized the soil from 1966. For OCPs the influence of sites location on the detected concentration has been revealed: China and India were characterized by comparably higher loads of DDX (DDT and its metabolites) and of HCH-isomers, respectively.     

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.     

Sensitivity of veliger larvae of Mytilus edulis and mussel of various sizes to chlorination

The blue mussel Mytilus edulis is one of the dominant fouling organisms in cooling water systems. In this work, how veliger larvae and different size groups of the mussels responded against chlorine dosage was examined. Veliger larvae mortality was studied at different residual chlorine concentrations (0.05–0.5 mg L^?1), and it was found that a chlorine dose of 0.5 mg L^?1 is 4 times as effective as 0.05 mg L^?1 and twice as effective as 0.1 mg L^?1. Mortality of 100% for three size groups (1.4, 14, and 25 mm) and relative physiological activities of two size groups (14 and 25 mm) were observed. The exposure duration for 100% mortality of mussels decreased with the increasing residual chlorine concentration (0.1–4.0 mg L^?1). Mussel size was also found to be an important factor, considering that the continuation times for mussel mortality were 28 h for the 1.4 mm and 410 h for the 25 mm size groups. All size groups showed progressive reduction in physiological activities, such as oxygen consumption, foot activity, and byssus thread production with increasing chlorine dose (0.05–1.0 mg L^?1); the two data-sets were strongly correlated with each other. The results of this study should be of significance for optimizing the chlorine content, and minimize the environmental threat to industries where mussels are the dominant fouling organisms.     

黄土残塬区不同种植类型下耕地土壤肥力与经济效益耦合关系研究

塬地农田作为黄土高原地区发展种植业的最佳区域,近年来由于人类对农业种植类型的不合理选择,使得该区域土壤保肥持水的水平降低,且已对作物生长及农业经济发展产生严重威胁,故本文旨在研究该区域不同种植类型下耕地土壤肥力和经济效益耦合关系,从而选取合适的种植类型。本研究选取晋西南塬地4种典型样地类型（玉米、棉花、马铃薯、荒地）为研究对象,对2019年、2020年全生育期（3—10月）土壤肥力及产值产量进行测定,基于实验数据采用耦合协调度模型综合分析各作物种植下肥力、经济效益状况及耦合协调度。结果表明：（1）不同种植类型下土壤肥力有显著差异,其中马铃薯种植下土壤肥力最高;（2）不同生育期土壤肥力变化有异,除土壤含水量外各肥力指标在快速发育期含量最高而生长中期显著降低,土壤含水量在快速发育期含量最低;（3）各土壤肥力指标含量在20—40 cm土层较高,土壤含水量在0—20 cm土层含量较低;（4）各种植类型下经济效益排序为棉花＞马铃薯＞玉米＞荒地,其中棉花经济效益分别为马铃薯、玉米和荒地的1.17倍、1.36倍和3.40倍;（5）马铃薯种植下耦合协调度最高,棉花和玉米次之,荒地最低。综上,马铃薯种植对肥力改善具有重要意义,而以经济创收为目的的优势种植类型为棉花。农业的可持续发展要求经济创收和地力保护相协调,本研究表明马铃薯为晋西南黄土残塬区兼顾经济增长和农业环境保护的最佳种植类型,应积极推广种植。以上各作物类型种植下在快速发育期应及时灌溉以减小水分对肥力改善和作物产量的限制。该研究对黄土残塬区耕地种植类型的合理选择、科学施灌及促进农业可持续发展等具有重要意义。     

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.