除草剂阿特拉津(Atrazine)的环境行为综述

阿特拉津（２－氯－４－乙胺基－６－异丙氨基－１，３，５，－三氮苯）是目前应用广泛的化学除草剂之一。在世界许多国家和地区的地表水和地下水中已检出了阿特拉津的残留物。阿特拉津对人类的威胁究竟有多大，已成为目前研究的热点。本文从阿特拉津的检测方法、动力学性质、生化性质及风险评估四个方面进行了综述，并提出了自己的观点。     

低浓度阿特拉津对鲫鱼谷胱甘肽-S转移酶(GSTs)活性的影响

研究不同作用时间和不同暴露浓度下阿特拉津对鲫鱼肝脏、肾脏和肌肉谷胱甘肽-S转移酶(GSTs)活性的影响.结果表明:阿特拉津对鲫鱼各个组织器官GSTs活性产生较强的影响.长期暴露下(24 d),阿特拉津对鲫鱼肝脏和肌肉GSTs活性基本表现为诱导作用,最大诱导率为110.81%和32.54%,且分别在0.1～5.0和1.0～10.0 mg·L-1质量浓度范围内存在剂量-效应关系;对鲫鱼肾脏GSTs活性具有抑制作用,最大抑制率为14.42%,且在所设质量浓度(0～10 mg·L-1)范围内均表现出剂量-效应关系.在10.0 mg·L-1质量浓度暴露下第6-14天内,阿特拉津与鲫鱼肝脏及肌肉GSTs活性间存在时间-效应关系;其他情况下,任何组织器官在试验期间均未表现出时间-效应关系.     

a study of the temporal variability of atrazine in private well water. part i: study design, implementation, and database development

In 1988, the Iowa Department of Natural Resources, along withthe University of Iowa conducted the Statewide Rural WellWater Survey, commonly known as SWRL. A total of 686private rural drinking water wells was selected by use of aprobability sample and tested for pesticides and nitrates. Sixty-eight of these wells, the 10% repeat wells, were additionallysampled in October, 1990 and June, 1991. Starting inNovember, 1991, the University of Iowa, with sponsorshipfrom the United States Environmental Protection Agency,revisited these wells to begin a study of the temporalvariability of atrazine and nitrates in wells. Other wells, whichhad originally tested positive for atrazine in SWRL but werenot in the 10% repeat population, were added to the studypopulation. Temporal sampling for a year-long period beganin February of 1992 and concluded in January of 1993. Allwells were sampled monthly, one subset was sampled weekly,and a second subset was sampled for 14-day consecutiveperiods. Two unique aspects of this study were the use of animmunoassay technique to screen for triazines before gaschromatography/mass spectrometry (GC/MS) analysis andquantification of atrazine, and the use of well owners to samplethe wells. A total of 1771 samples from 83 wells are in thefinal data base for this study. This paper reviews the studydesign, the analytical methodologies, and development of thedata base. A companion paper (Pinsky et al., 1997) discussesthe analysis of the data from this survey.     

两种染料与阿特拉津在沉积物上的竞争吸附

通过批量吸附实验研究了两种染料对阿特拉津(AT)在天然水体沉积物上吸附的影响.结果表明,与对照相比,刚果红(CR)和亚甲基蓝(MB)在实验浓度范围内均与AT发生竞争吸附,分别使AT的吸附率降低了14.29%和30.16%.共存体系的溶液化学条件发生变化时,AT的吸附有所不同.当体系pH值和温度升高时,AT的吸附量减小;而离子强度的升高,促使AT在沉积物上的吸附量增大.     

WALNUT CREEK WATERSHED MONITORING PROJECT,IOWA MONITORING WATER QUALITY IN RESPONSE TO PRAIRIE RESTORATION1

ABSTRACT: Land use and surface water data for nitrogen and pesticides (1995 to 1997) are reported for the Walnut Creek Watershed Monitoring Project, Jasper County Iowa. The Walnut Creek project was established in 1995 as a nonpoint source monitoring program in relation to watershed habitat restoration and agricultural management changes implemented at the Neal Smith National Wildlife Refuge by the U.S. Fish and Wildlife Service. The monitoring project utilizes a paired‐watershed approach (Walnut and Squaw creeks) as well as upstream/downstream comparisons on Walnut for analysis and tracking of trends. From 1992 to 1997, 13.4 percent of the watershed was converted from row crop to native prairie in the Walnut Creek watershed. Including another 6 percent of watershed farmed on a cash‐rent basis, land use changes have been implemented on 19.4 percent of the watershed by the USFWS. Nitrogen and pesticide applications were reduced an estimated 18 percent and 28 percent in the watershed from land use changes. Atrazine was detected most often in surface water with frequencies of detection ranging from 76–86 percent. No significant differences were noted in atrazine concentrations between Walnut and Squaw Creek. Nitrate‐N concentrations measured in both watersheds were similar; both basins showed a similar pattern of detection and an overall reduction in nitrate‐N concentrations from upstream to downstream monitoring sites. Water quality improvements are suggested by nitrate‐N and chloride ratios less than one in the Walnut Creek watershed and low nitrate‐N concentrations measured in the subbasin of Walnut Creek containing the greatest amount of land use changes. Atrazine and nitrate‐N concentrations from the lower portion of the Walnut Creek watershed (including the prairie restoration area) may be decreasing in relation to the upstream untreated component of the watershed. The frequencies of pesticide detections and mean nitrate‐N concentrations appear related to the percentage of row crop in the basins and subbasins. Although some results are encouraging, definitive water quality improvements have not been observed during the first three years of monitoring. Possible reasons include: (1) more time is needed to adequately detect changes; (2) the size of the watershed is too large to detect improvements; (3) land use changes are not located in the area of the watershed where they would have greatest effect; or (4) water quality improvements have occurred but have been missed by the project monitoring design. Longer‐term monitoring will allow better evaluation of the impact of restoration activities on water quality.     

饮用水中内分泌干扰物阿特拉津UV光氧化研究

采用单独紫外光氧化工艺去除饮用水中低浓度阿特拉津,研究了不同影响因素对阿特拉津降解效果的影响,并分析了阿特拉津的降解机理.结果表明:单独紫外光氧化对阿特拉津有很好的去除效果,在光强为205μW/cm²条件下,光解120min后,阿特拉津去除率为92.38%.阿特拉津的光解过程符合一级反应动力学模型.通过提高紫外照射光强,可以在短时间内提高阿特拉津的去除率.阿特拉津的初始浓度对光解反应基本没有影响.自来水中的有机物及多种离子的存在会降低阿特拉津的光解速率.紫外光氧化阿特拉津主要降解途径是脱氯反应,反应速率很快.羟基化产物(OHA)是主要的中间产物.OHA在紫外光作用下可以继续发生脱烷基反应,生成OHDIA和OHDEA,反应速率非常缓慢.反应液中pH值的变化与中间产物的形成过程有很好的相关性.     

掺Fe金红石TiO2的制备及其可见光催化活性的评价研究

为提高金红石型TiO2的可见光吸收性能和光催化活性,以FeC2O4为Fe源,用浸渍法制备了掺铁金红石TiO2光催化剂。采用XRD、UV-Vis等手段对催化剂进行表征;以阿特拉津为目标污染物,在Vis/H2O2条件下对其催化活性进行了评估。结果表明,Fe以Fe2O3的形式负载在金红石型TiO2的表面;掺铁后金红石型TiO2显著拓宽了其可见光的吸收范围;煅烧温度为400℃时制得的光催化剂Fe-R-400℃的粒径结构和光催化活性最好。以Fe质量分数为1%的Fe-R-400℃作为光催化剂,控制反应体系的初始pH=3,催化剂投加质量浓度为1 g/L,H2O2初始浓度为1 mmol/L,经可见光照射反应15 min后,对初始质量浓度为10 mg/L的阿特拉津的去除率可达95.7%。催化剂循环试验表明,Fe在金红石TiO2表面负载比较牢固,催化剂具有较好的稳定性和重复使用性能。     

Agro-waste biosorbents: Effect of physico-chemical properties on atrazine and imidacloprid sorption

Low cost agro-waste biosorbents namely eucalyptus bark (EB), corn cob (CC), bamboo chips (BC), rice straw (RS) and rice husk (RH) were characterized and used to study atrazine and imidacloprid sorption. Adsorption studies suggested that biosorbents greatly varied in their pesticide sorption behaviour. The EB was the best biosorbent to sorb both atrazine and imidacloprid with K_F values of 169.9 and 85.71, respectively. The adsorption isotherm were nonlinear in nature with slope (1/n) values <1. The Freundlich constant Correlating atrazine/imidacloprid sorption parameter [K_F.(1/n)] with the physicochemical properties of the biosorbents suggested that atrazine adsorption correlated significantly to the aromaticity, polarity, surface area, fractal dimension, lacunarity and relative C-O band intensity parameters of biosorbents. Probably, both physisorption and electrostatic interactions were responsible for the pesticide sorption. The eucalyptus bark can be exploited as low cost adsorbent for the removal of these pesticides as well as a component of on-farm biopurification systems.     

高效液相色谱三重四级杆串联质谱联用直接进样法测定饮用水水源中的阿特拉津研究

采用高效液相色谱三重质谱联用直接进样法测定地表水中的阿特拉津,样品经0.2μm滤膜过滤后直接上机测定,前处理无需消耗有机溶剂。选用SunFire C18(5μm*4.6 mm*150 mm)色谱柱,流动相为0.1%甲酸乙腈∶0.1%甲酸水=7∶3,流速为0.5 ml/min;质谱条件为电喷雾离子源(ESI+)电离,采用串联质谱多反应监测方式(MRM)检测。该法测定饮用水水源中阿特拉津的最低检出限为0.018μg/L,精密度为0.4%~1.0%,准确度为-0.2%~-6.6%,线性范围为0.5μg/L~100.0μg/L,相关系数为0.999 8,线性良好,能满足环境监测工作的实际应用。     

基因工程菌生物强化膜-生物反应器工艺启动期影响因素研究

基因工程菌生物强化膜-生物反应器工艺经过启动期之后,可以实现对阿特拉津的高效稳定去除,去除率在90%以上.不同条件下,启动期最短2 d,最长可达12 d.阿特拉津初始进水负荷、运行温度和工程菌接种密度,对启动期具有显著影响.增加阿特拉津初始进水负荷、提高运行温度和增加基因工程菌接种密度,可以实现快速启动.进水水质对启动期影响不大,在人工配水和实际污水2种进水条件下,启动期基本相同,而且稳定期2种进水的阿特拉津去除情况也没有差异,说明进水水质对启动期和稳定期阿特拉津的去除影响都不大.