固相萃取气相色谱法测定地表水中有机磷农药

建立了固相萃取(SPE)气相色谱火焰光度(GC-FPD)检测方法,并且检测了地表水中8种有机磷农药,检测限在0.09～0.26μg/L之间,相对标准偏差为3.1%～9.7%(n=8),加标回收率达到61.3%～103.2%,与传统的气相色谱法相比,该方法具有比较高的重现性和选择性,在地表水有机磷农药的测定中具有很好的应用前景.     

基于固定化AChE的流动注射型酶传感器研究

以固定化鲅鱼脑组织乙酰胆碱酯酶[acetylcholinesterase,AChE(EC 3.1.1.7)]为识别元件,以pH电极为换能器,构建流动注射型AChE酶传感器.该传感器在以磷酸盐缓冲液为载液的条件下具有良好的重现性(RSD=1.427%,n=10)和敏感性,可实现对有机磷化合物的在线监测;对甲基对硫磷具有线性响应的浓度范围为4.29×10-10^-4.29×10^-8mol·L^-1,最低检测限为1.3×10^-     

土壤中两种手性有机氯农药的选择性降解研究

为了更深入的了解和阐释手性有机氯农药在土壤中的转化和环境归趋,采用实验室室内避光培养方法,研究了o,p＇-DDT及o,p＇-DDD 2种手性有机氯农药的外消旋体在水稻土厌氧培养体系和菜园土好氧培养体系中的选择性降解情况。为了更好的利用土壤中土著微生物的活性,我们选择了厌氧微生物比较丰富的水稻土和好氧微生物丰度比较高的菜园土来做培养实验。结果表明实验体系中o,p＇-DDT及o,p＇-DDD在水稻土和菜园土中的降解均没有明显的对映体选择性。这一结果与2种手性化合物不同对映体在自然环境中的含量普遍具有差异性有所不同,说明野外环境条件和室内模拟实验条件的差异会影响手性化合物的降解选择性。在2种体系中,o,p＇-DDT的降解速率均高于o,p＇-DDD的降解速率。这与以前的研究报道一致,DDD比DDT更难降解。通过2个体系的比较,发现DDT的降解速率在厌氧体系中高于好氧体系,而DDD的降解速率与之相反,好氧体系高于厌氧体系。这应该与DDT和DDD 2种化合物的化学结构及2种土壤中微生物群落的差异有关。对于厌氧体系中的2种水稻土,采自中山的水稻土中DDT的降解速率高于江门的水稻土,这应该与中山水稻土有机质含量高于江门的水稻土有关。有机质含量的高低直接反映了土壤中微生物的多少,进而会影响污染物的降解速率。研究发现本实验所用水稻土和菜园土总有机碳含量偏低可能是影响2种化合物的对映体无降解选择性的因素之一。此外,由于本研究采用缓冲溶液将pH 调控在中性,因此本文的土壤 pH 对降解选择性的影响仍有待进一步研究。本研究中好氧体系和厌氧体系对目标物的降解选择性无明显差异。     

阴/非离子表面活性剂强化微米Cu/Fe对水及土壤泥浆中有机氯农药的降解

选择氯丹、硫丹和灭蚁灵为目标污染物,以实际污染场地土壤为对象,研究了表面活性剂强化微米Cu/Fe双金属对水和土壤泥浆中有机氯农药的降解效果。结果表明,非离子表面活性剂Triton X-100(TX-100)强化效果优于阴离子的十二烷基磺酸钠(SDS)。TX-100强化微米Cu/Fe体系能实现水中有机氯农药的快速高效降解,最佳TX-100浓度为0.1 mmol·L-1。处理12 h后,γ-氯丹、硫丹和α-氯丹的降解率接近100%,灭蚁灵的降解率达到85.2%。对于土壤泥浆体系,偏酸性p H值对微米Cu/Fe的还原活性有重要作用。加入TX-100显著促进了微米Cu/Fe双金属对土壤中有机氯农药的还原降解(P0.05)。Cu负载量的提高增强了污染物的降解去除效果。当m(土)∶V(水)为1∶5、土中Fe投加量w为10%、Cu负载量为5.0%、TX-100浓度为5.0 mmol·L-1、p H值为4~5时,处理72 h后,γ-氯丹、硫丹、α-氯丹和灭蚁灵的降解率分别为83.5%、68.1%、86.8%和70.1%。TX-100强化微米Cu/Fe双金属还原降解是一种有效的有机氯农药污染土壤修复技术。     

臭氧-生物活性炭对微污染原水中典型持久性有机物的去除效果

以长三角地区J市典型有机微污染水源P水厂为研究对象,考察了臭氧-生物活性炭深度处理工艺对微污染水源水中有机物的去除效果.结果表明,臭氧-生物活性炭深度处理使高锰酸盐指数、总有机碳(TOC)和UV254的平均去除率分别提升19. 2%、10. 4%和23. 0%.水厂原水中检出8种多环芳烃(polycyclic aromatic hydrocarbon,PAHs)、16种有机氯农药(organochlorine pesticides,OCPs)、5种卤乙酸(haloacetic acids,HAAs),其总浓度分别为53. 9~100. 0、6. 5~41. 8、2. 5×103~1. 1×104ng·L~(-1),臭氧-生物活性炭深度处理对多环芳烃和有机氯农药的平均去除率分别为32. 5%和25. 9%,比常规处理工艺出水的水质有显著提升.卤乙酸的去除率为33. 8%~87. 0%,主要通过常规处理工艺去除;臭氧-生物活性炭深度处理对氯代乙酸略有去除,溴代乙酸有少量生成.     

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.     

Application of the QuEChERS method for the determination of organochlorine pesticide residues in Brazilian fruit pulps by GC-ECD

The Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method was applied to the extraction of 14 organochlorine pesticides (OCPs) residues from commercial fruit pulps available in supermarkets in Fortaleza, Northeastern Brazil. The analyses were carried out by gas chromatography (GC), coupled to an electron-capture detector (ECD), and were confirmed by GC-tandem mass spectrometry (MS). The parameters of the analytical method, such as accuracy, precision, linear range, limits of detection and quantification, were determined for each pesticide. The results showed good linearity (R² ≥ 0.9916) and the overall average recoveries were considered satisfactory obtaining values between 69 and 110%, RSD of 2–15 %, except for hexachlorobenzene (HCB) in açai, acerola and guava pulp samples. The OCPs were detected in guava (α–HCH; lindane) and soursop (α, β–HCH isomers) samples. The QuEChERS method and GC–ECD were successfully used to analyze OCPs in commercially available Brazilian fruit pulps and can be applied in routine analytical laboratories.     

污灌渠中有机氯农药对沿渠土壤的影响

为了研究污水灌渠侧渗对土壤的影响,采用气相色谱-电子捕获检测器(GC-ECD)方法对太原市小店污灌区9个剖面土和2个灌溉污水样进行有机氯化合物(OCPs)分析.结果表明退水渠中有机氯农药主要由六六六(HCHs)组成,滴滴涕(DDTs)及其它有机氯农药含量较低或未检出,在8个离渠较近剖面的地表土中ΣOCPs和HCHs含量一定程度上符合随垂直于渠的直线距离增加而逐步降低的趋势,表明污水渠侧渗对土壤存在着一定影响.8个剖面土壤中的HCHs含量随着深度的增加而降低,在水平方向上,同一深度土壤中的HCHs含量也沿远离渠的直线方向逐步递减.研究区土壤中HCHs含量与TOC之间存在较为显著的正相关性,而与pH之间不存在相关性.     

有机磷农药在环境中的光稳定性及其与分子结构的关系

测定了九种具不同结构特征的有机磷农药的消光系数、光量子产率和在环境中的光稳定性。探讨了分子结构与光稳定性的关系。结果表明,农药光稳定性主要取决于分子是否具有共轭结构及共轭程度大小;共轭程度愈大,农药的紫外光吸收能力愈强,光量子产率愈小。根据分子结构将有机磷农药分为六类。并以此法对30种结构较为简单的农药的光稳定性作了预测。     

南四湖沉积物中有机氯农药和多氯联苯垂直分布特征

通过对采集于南四湖湖区的沉积物柱状样品中有机氯农药（OCPs）和多氯联苯（PCBs）同系物的GC-ECD定量分析测定,并结合²¹⁰Pb同位素定年分析,重建了南四湖湖区有机污染物的污染史.结果表明,样品中OCPs、HCHs、DDTs和PCBs的含量范围分别为1.64～17.9、0.66～12.5、0.24～2.99和7.84～42.8 ng·g^-1.柱状沉积物的沉积速率为0.330 cm·a^-1,平均沉积通量为0.237 g·(cm²·a)^-1,所采集的样品沉积时间为1899～2000年.OCPs和PCBs分别在1960和1970年左右出现浓度峰值,随后含量逐渐下降.污染物来源分析表明,HCHs来源于新的工业HCH和林丹2种工业品,HCH和DDT污染主要源于历史上的使用;PCBs主要来自于造纸漂白过程和焚烧炉排放.生态风险评价结果表明,除β-HCH、γ-HCH和艾氏剂3种污染物在14～16　cm附近、对应沉积时间为1960年左右测试数据略高于风险水平低值,其余污染物的所有数据均低于风险水平低值.整体而言,南四湖柱状沉积物中的OCPs和PCBs含量属于低生态风险水平.