免耕和草篱措施对径流中典型农业面源污染物的去除效果

大量施用农业化学物质在提高作物产量的同时,也导致了严重的水体污染.在北京地区不同坡度的径流小区上,通过人工模拟降雨试验,研究免耕、草篱、以及免耕与草篱复合3种措施对农田径流中氮、磷、阿特拉津3种典型农业面源污染物的去除效果.结果表明:免耕措施可减少53%的总氮、51%的总磷和56%的阿特拉津流失;草篱措施可减少68%的总氮、61%的总磷和90%的阿特拉津流失;而免耕与草篱复合措施可减少77%的总氮、76%的总磷和92%的阿特拉津流失.另外,总氯、总磷和阿特拉津流失量均与径流量呈显著的线性正相关关系.本研究证实,免耕和草篱措施均能有效防止氮、磷以及阿特拉津随农田径流流失,对农业面源污染具有较好的防治效果,而这2种措施复合后能使其防治效果进一步增强.     

阿特拉津对绿麦隆吸附-解吸作用的影响

采用批平衡实验,研究绿麦隆在单一及复合污染体系中的吸附-解吸行为。结果表明,无论是单一体系还是复合体系,吸附等温线均可用Freundlich模型进行良好的拟合。随着阿特拉津浓度的增加,土壤对绿麦隆的吸附作用降低,表明绿麦隆和阿特拉津之间存在竞争吸附,这可能与土壤的有机质类型和绿麦隆、阿特拉津的性质、结构有关。解吸实验表明,随着阿特拉津的浓度增加,绿麦隆的解吸作用增加。吸附过程的拟合指数n值大于解吸过程的对应值,即绿麦隆在不同体系中的解吸作用均存在一定的滞后性。应用Freundlich解吸等温线参数对吸附-解吸等温线的滞后作用进行量化,CT、（CT＋0.5AT）、（CT＋1AT）和（CT＋2AT）处理解吸等温线的滞后系数ω分别为165.200,146.132,94.534和85.945,即随阿特拉津浓度增加,绿麦隆解吸等温线的滞后性降低。     

草本植被过滤带对径流中泥沙和除草剂的去除效果

除草剂阿特拉津的大量使用在提高农业生产效率、增加作物产量的同时,也导致了严重的环境污染。该研究通过在土槽上进行浑水冲刷试验,定量研究了禾本科草本植被过滤带（狼尾草Pennisetum alopecuroides (Linn.) Spreng和野古草Arundinella hirta (Thunb.) C. Tanaka）对径流、泥沙、以及阿特拉津的拦截效果。结果表明,禾本科草本植被过滤带能有效拦截径流,拦截率可达88%;并显著降低泥沙和阿特拉津流失量,但其作用效果受泥沙和阿特拉津的进水浓度影响较大。当进水泥沙浓度为20、40、60 g/L时,植被过滤带对泥沙的拦截率分别为95%、93%、85%;当进水阿特拉津浓度为0.3、0.6、0.9 mg/L时,植被过滤带对阿特拉津的拦截率分别为95%、92%、91%。另外,植被过滤带对泥沙和阿特拉津的拦截率随时间延长呈逐渐降低趋势,试验开始后第1、10、20、40、60分钟的泥沙拦截率分别为97%、95%、93%、91%、87%,阿特拉津拦截率分别为97%、93%、90%、86%、84%;同时,阿特拉津出流浓度与径流量有显著相关关系（r1=0.88,r2=0.93,r3=0.94）,表明径流量在一定程度上决定了阿特拉津出流浓度和出流量。研究证实,植被过滤带能有效降低阿特拉津随径流流失量,对阿特拉津引起的农业面源污染具有较好防治效果。     

粘土矿物固定化微生物对土壤中阿特拉津的降解研究

以粘土矿物为载体,采用吸附挂膜法对已筛选的阿特拉津降解菌株进行固定化,并应用固定化微生物降解土壤中的阿特拉津。结果表明,该菌株在粘土矿物上生长良好,根据菌种生理生化特性、环境扫描电镜图片以及16S rDNA基因的相似性分析初步鉴定该菌株为Ochrobactrum sp.。接种降解菌能明显加快阿特拉津在土壤中的降解速率,粘土矿物固定化微生物的降解效果要明显优于游离菌,粘土矿物粒径越小,固定化微生物的降解效果越好,纳米粘土矿物固定化微生物的降解效果要好于原粘土矿物。用一级动力学方程描述阿特拉津在土壤中的降解过程,不同土壤中阿特拉津的降解速率不同。阿特拉津在红壤、砂姜黑土、黄褐土中的降解半衰期（t1/2）分别为36.9、49.1、55.0 d,投加纳米蒙脱石固定化降解菌后的半衰期则分别为16.3、25.3、21.7 d。     

白马河流域除草剂及其代谢产物的时空分布特征与生态风险评价

[目的] 探讨典型除草剂阿特拉津（ATR）及其代谢产物脱乙基阿特拉津（DEA）、脱异丙基阿特拉津（DIA）在作物生长季（6—9月）的污染特征以及时空变化,为农业小流域除草剂的管理、使用与保护决策提供科学依据。[方法] 在白马河流域沿程设立18个采样点,基于实地监测和室内分析,探讨污染物的时空变化特征,并运用熵值法进行生态风险评价。[结果] ①所有采集水样中均有ATR及代谢产物检出,其中ATR在6—7月的地表水样中100%检出,8—9月检出率稍有下降,代谢产物DEA,DIA在前两月检出率较低,后两月检出率增加。②白马河污染物空间分布表明,各污染物浓度最高值大多出现于河流上游和中游,下游浓度均相对较低。这可能与河流下游河道宽阔、水流量大、稀释作用较强有关。③生态风险评价结果显示ATR,DEA和DIA风险等级均为中等,其原因是该河流的水负荷低,稀释能力不足。[结论] 相对于大流域,白马河作为典型农业流域的小支流,水量小、稀释能力不足,造成污染的生态风险高于许多大流域。     

贵州红枫湖溶解有机质不同分离组分的卤代活性研究

饮用水使用氯化消毒产生的消毒副产物给人类健康带来了极大危害。利用XAD树脂与阴、阳离子交换树脂对贵州红枫湖水体中溶解有机质进行了富集分离,分成腐植酸、富里酸、疏水中性物质及亲水酸性、碱性及中性物质6种组分,比较了各组分在加氯消毒过程中卤代活性的大小及其三卤甲烷的生成情况,揭示了有机组分卤代活性与其结构之间的关系,并探讨了它们可能的来源,提出了相应的控制措施。结果表明,红枫湖水体溶解有机质以富里酸组分为主,占分离出总有机碳的56%。氯化消毒实验发现消毒副产物以三氯甲烷和一溴二氯甲烷为主,富里酸的卤代活性最强。结构分析显示各有机组分的卤代活性与紫外吸光系数和酚羟基含量之间具有显著相关性。6种分离组分的消毒副产物生成量中,富里酸是生成三卤甲烷的主要前驱物质,占消毒副产物总量的76%。有机组分的碳稳定同位素值与C/N比值表明,富里酸主要来自陆源有机物,其余组分兼有陆源和内源两种来源。因此,控制陆源污染是减少红枫湖消毒副产物前驱物的有效途径。     

工厂化循环水养殖中臭氧/紫外线反应系统的水处理性能

为增强臭氧在水产应用的安全性,满足工厂化循环水养殖对有机物去除和水体消毒的需要,该文开发O3/UV反应系统。通过试验方法研究该系统臭氧投加溶解区适宜的臭氧投加流量和处理量的关系、紫外辐射剂量配比等工艺参数,及对水质净化效果和水体消毒灭菌效果的影响等。试验结果表明:1)在满足所需水中溶解臭氧浓度的条件下,采用较低臭氧进气流量和较高进水流量有利于提高系统的臭氧溶解率和利用率。该系统在水流量为5 m3/h,臭氧投加量为(8.78±0.60)g/h时可得到水中臭氧溶解质量浓度为1.53 mg/L的臭氧水,臭氧溶解率为82.7%,臭氧利用率为97.7%。2)增加紫外灯的功率和数量均可提高对臭氧的去除率,但增加紫外灯的数量对其性能提升效果更明显。该系统在紫外剂量为1 996 MJ/cm2,对残留臭氧的去除率为83.82%。3)该系统对紫外消光度、总有机碳、水色等指标的去除率相比单独使用臭氧分别提升109.95%、89.77%和51.44%,杀菌率可达97%以上,实现工厂化循环水养殖低臭氧残留条件下的有机物有效去除和消毒杀菌。     

土壤矿物和胡敏酸对阿特拉津的吸附-解吸作用研究

选取了6种土壤矿物(蒙脱石、高岭石、钙饱和处理蒙脱石、钙饱和处理高岭石、无定型氧化铁和无定型氧化铝),以及从土壤中提取纯化的3种胡敏酸为材料,采用批量吸附平衡法,研究土壤矿物和胡敏酸对阿特拉津的吸附特性。结果表明,各吸附剂对阿特拉津的吸附均能采用Frundlich方程进行较好地拟合(r≥0.982,p0.01)。胡敏酸对阿特拉津具有最大的吸附性能,其固-液分配系数(Kd值)随平衡浓度(Ce值)的变化基本恒定,吸附等温线呈线性(Frundlich方程常数N≈1),吸附以分配溶解作用为主,吸附可逆性较高。黏土矿物(特别是蒙脱石)对阿特拉津也具有较强的吸附能力,Kd值随Ce值增加而增加,吸附等温线呈S型(N1),吸附主要是通过表面亲水作用。无定型氧化铁铝的Kd值随Ce值增加而降低,当Ce达到一定水平后,Kd趋于恒定,吸附等温线呈L形(N1),吸附主要是通过无定型氧化物表面的羟基与阿特拉津分子间的化学键合作用,吸附可逆性最差。     

气相色谱法同时测定土壤中13种三嗪类除草剂残留量的方法研究

采用气相色谱-氮磷检测器（GC—NPD）方法,建立了同时测定土壤中13种三嗪类除草剂（脱乙基阿特拉津、莠去通、西玛津、莠去津、扑灭津、特丁津、敌草净、赛克津、西草净、莠灭净、扑草净、异丙净、甲氧丙净）残留量的方法。土壤样品用乙腈-水混合提取剂经超声波提取20min,弗罗里硅土（Florisil）固相萃取柱净化后,毛细管柱分离样品,NPD测定。结果表明,13种三嗪类除草剂在0．05-5．0mg·L^-1范围内线性关系良好,相关系数均大于0．999;添加回收率在72．7％～128．2％之间;相对标准偏差在0．4％～20．5％;方法的检出限在0．001-0．005mg·kg^-1之间。     

AQDS加速红壤性水稻土中DDT厌氧脱氯效应研究

电子供体基质和电子穿梭体对电子转移过程有重要影响,进而可能影响厌氧反应体系中2,2-双(4-氯苯基)-1,1,1-三氯乙烷(DDT)还原脱氯降解。为了阐明电子供体基质正丁酸与电子穿梭体蒽醌-2,6-二磺酸盐(AQDS)对红壤性水稻土中DDT还原脱氯效果的影响,本研究采用厌氧土壤培养试验并设定以下5个处理:1灭菌对照,2对照,3正丁酸,4AQDS,5正丁酸+AQDS。结果表明,厌氧培养20 d后,土壤中DDT可提取态残留量减少了85.2%~96.3%。DDT厌氧脱氯降解的主要产物为2,2-双(4-氯苯基)-1,1-二氯乙烷DDD。添加正丁酸在培养前8d显著提高产CH4速率,而对DDT脱氯降解无显著促进作用,第8天之后,随着产CH4速率降低,添加正丁酸处理的DDT脱氯速率逐渐升高。添加AQDS显著增强土壤还原性并加速三价铁氧化物还原生成电子供体二价铁,进而显著促进DDT还原脱氯降解。同时添加正丁酸和AQDS对促进DDT还原脱氯的效果最佳,但是正丁酸和AQDS对加速DDT还原脱氯无显著交互作用。本研究结果对于制定DDT污染土壤的高效原位修复技术方案具有指导意义。     

Aufnahme von Atrazin-Metaboliten durch Hafer neun Jahre nach der Herbizid–Applikation

Uptake of atrazine metabolites by oat plants nine years after the herbicide application The uptake of atrazine metabolites by oats under field conditions was investigated 9 years after the herbicide application. In the spring of 1973 the soil was treated with ¹⁴C-ringlabeled atrazine and cultivated with various plant species each year. The soil was seeded to oats in early May of 1982. In August the oat plants were harvested and analysed. 2-Hydroxy-4-amino-6-isopropylamino-s-triazine and 2-hydroxy-4-ethylamino-6-amino-s-triazine were identified in conjugated form in the plant material. Neither free atrazine nor any other phytotoxic 2-chloro-metabolites could be found.     

Analytical method for the determination of atrazine and its dealkylated chlorotriazine metabolites in water using gas chromatography/mass selective detection

A multiresidue method is reported for the determination of atrazine and its dealkylated chlorotriazine metabolites in water. Water samples are buffered to pH 10 and partitioned in ethyl acetate. Final analysis is accomplished using gas chromatography/mass selective detection (GC/MSD) in the selected ion monitoring (SIM) mode. The limit of detection (LOD) is 0.050 ng and the limit of quantification (LOQ) is 0.10 ppb for 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine (atrazine), 2-amino-4-chloro-6-(isopropylamino)-s-triazine (G-30033), 2-amino-4-chloro-6-(ethylamino)-s-triazine (G-28279), and 2, 4-diamino-6-chloro-s-triazine (G-28273). The mean procedural recoveries were 90, 92, 98, and 85% and the standard deviations were 12, 13, 16, and 20% for atrazine, G-30033, G-28279, and G-28273, respectively (n = 30). The study was conducted under U.S. EPA FIFRA Good Laboratory Practice Guidelines 40 CFR 160 for method validation. The reported procedure accounts for residues of G-28273 in water that are not included in EPA Method 507.     

Analytical method for the determination of atrazine and its dealkylated chlorotriazine metabolites in water using SPE sample preparation and GC-MSD analysis

A method is reported for the determination of atrazine and its dealkylated chlorotriazine metabolites in ground, surface, and deionized water. Water samples are adjusted to pH 3-4 prior to loading onto two SPE cartridges in series: C-18 and C-18/cation exchange mixed-mode polymeric phases. The analytes are eluted from each of the two cartridges separately, and the pooled and concentrated fraction is analyzed using gas chromatography-mass selective detection in the selected ion monitoring mode. The lower limit of method validation is 0.10 micrograms/L (ppb) for 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine (atrazine), 2-amino-4-chloro-6-(isopropylamino)-s-triazine (G-30033, deethylatrazine), 2-amino-4-chloro-6-(ethylamino)-s-triazine (G-28279, deisopropylatrazine), and 2,4-diamino-6-chloro-s-triazine (G-28273, didealkyatrazine). The overall mean procedural recoveries (and standard deviations) are 96 (6.9), 96 (5.5), 95 (6.8), and 100% (10%) for atrazine, G-30033, G-28279, and G-28273, respectively (n = 49). The method validation study was conducted under U.S. EPA FIFRA Good Laboratory Practice Guidelines 40 CFR 160. The reported procedure accounts for residues of G-28273 in water.     

Water and Atrazine Movement in a Calcareous Compost Applied Soil During Simulated Multiple Storms Events

The retention and movement of water and atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) was investigated in a calcareous soil (Krome) amended with three types of compost: (1) Clean organic waste (COW)- municipal solid waste cleaned of plastic materials and metal containers, (2) Biosolids (BSD)- sludge from municipal waste and (3) Bedminster (BDM)—a mixture containing 75% COW and 25% BSD. The research was conducted in two phases; a column-leaching study (dynamic) and a batch-equilibrium method (static). The column study demonstrated that while applying simulated rain, atrazine, leached out at a slower rate by 41, 24, and 18% from soil amended with BDM, BSD, and COW composts, respectively, during the first simulated storm event. BDM application resulted in lowest water movement and atrazine-leaching rate compared to the other composts tested. This study suggests that adding 134 t ha^?1 of compost to the calcareous soil increased soil water holding capacity, reduced water movement and increased atrazine detention and reduced leaching potential of atrazine thereby reducing the potential for groundwater pollution. This study further demonstrates that soil amendment (particularly BDM) is effective in reducing the leaching potential of atrazine at the low rainfall amounts (corresponding to 0.5 pore volume). However, such amendment may not be effective in preventing leaching under more intense rain conditions or multiple rainfall events (corresponding to 3 or more pore volumes).     

Direct aqueous injection liquid chromatography/electrospray ionization-mass spectrometry/mass spectrometry analysis of water for atrazine, simazine, and their chlorotriazine metabolites

A method is reported for the determination of atrazine, simazine, and their respective dealkylated chlorotriazine metabolites in ground, surface, and finished drinking water. Water samples are diluted 1:4 in an injection vial prior to analysis using liquid chromatography/electrospray ionization-mass spectrometry/mass spectrometry (LC/ESI-MS/MS). The lower limit of method validation is 0.10 microg/L (ppb) for 2-chloro-4-(ethylamino)-6-isopropylamino)-s-triazine (atrazine, G-30027), 2-chloro-4, 6-(diethylamino)-s-triazine (simazine, G-27692), 2-amino-4-chloro-6-(isopropylamino)-s-triazine (deethylatrazine, DEA, or G-30033), 2-amino-4-chloro-6-(ethylamino)-s-triazine (deisopropylatrazine, DIA, or G-28279), and 2,4-diamino-6-chloro-s-triazine (didealkylatrazine, DDA, or G-28273). The overall mean procedural recoveries (and % relative standard deviations) for atrazine, simazine, DEA, DIA, and DDA are 98 (4.4), 102 (3.6), 99 (4.8), 103 (4.0), and 109% (4.8%), respectively, in finished drinking water; 108 (2.7), 104 (5.4), 113 (4.5), 111 (5.2), and 105% (5.3%), respectively, in groundwater; and 96 (6.9), 103 (4.2), 102 (4.4), 102 (5.2), and 102% (8.2%), respectively, in surface water. The method validation was conducted under U.S. EPA FIFRA Good Laboratory Practice Guidelines 40 CFR 160.     

纳米粘土矿物对阿特拉津的吸附-解吸特性研究

采用批量平衡实验,研究了纳米粘土矿物与原粘土矿物对除草剂阿特拉津的吸附解吸特陛。结果表明,粘土矿物对阿特拉津的吸附-解吸均能用Freundlich方程很好地拟合。随着溶液中阿特拉津浓度的增加,粘土矿物对阿特拉津的吸附量增加;粘土矿物粒径越小,吸附量越大,纳米粘土矿物的吸附量显著大于原粘土矿物。粘土矿物对阿特拉津吸附量大小顺序为：纳米SiO2）纳米蒙脱石〉凹凸棒石〉蒙脱石〉SiO2。粘土矿物对阿特拉津的解吸表现出一定的滞后效应,即粘土矿物吸附的阿特拉津越多,解吸的越少。粘土矿物对阿特拉津的解吸率大小顺序为：SiO2〉凹凸棒石〉纳米蒙脱石〉纳米SiO2〉蒙脱石。     

阿特拉津在饱和砂质壤土中非平衡运移的模拟

针对农药阿特拉津在稳定流场饱和砂质壤土中的运移 ,根据平衡与非平衡假设条件下对流—弥散方程数学模型的解析解 ,基于易混合置换实验获得的阿特拉津和示踪溶质Br- 的穿透曲线及批量平衡法求得的阻滞因子 ,应用CXTFIT 2 0软件 ,通过拟合土柱实验中溶质的出流浓度变化 ,估算了模型的有关参数 ,在此基础上模拟分析了实验土柱不同埋深处阿特拉津的出流浓度和累积淋溶量动态 ,结果表明 ,化学非平衡的两点模型对本文实验条件下阿特拉津运移的仿真具有较高的精度     

Influence of methanol and hexane on soil adsorption of atrazine

The increasing frequency of chemically contaminated groundwater, occurring as a result of improperly managed waste disposal or accidental spills, presents a need for research on the fate of chemical mixtures in the soil. The batch equilibration technique was used to measure adsorption of ¹⁴C ring-labeled atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) for a Palouse silt loam (Pachic Ultic Haploxeroll) and a Pembroke silty clay loam (Typic Paleudalf). The solution phase consisted of mixtures of methanol-water and hexane-water containing up to 33.3 % organic solvent by volume. Aqueous solubility limited atrazine concentrations to 100 μmol L^?1 except for an additional isotherm determined in 33.3 methanol-water at up to 1542 μmol L^?1 The Freundlich adsorption coefficient indicated that the Palouse adsorbed more atrazine than the Pembroke with K values of 4.95 and 0.54, respectively. Both soils showed a significant decrease in K as the percentage methanol increased. Adsorption isotherms from a 33. 3 methanol-water system were of the Freundlich type for atrazine concentrations of 0.25 to 1542 μmol L^?1. In the hexane-water systems, K decreased as the fraction of hexane increased and the Pembroke soil adsorbed less atrazine than the Palouse soil. These results suggest that the introduction of nonaqueous solvents such as methanol and hexane decreased adsorption and increased the potential for atrazine mobility.     

Direct aqueous injection LC-ESI/MS/MS analysis of water for 11 chloro- and thiomethyltriazines and metolachlor and its ethanesulfonic and oxanilic acid degradates

A multianalyte method is reported for the determination of atrazine, simazine, propazine, and their respective dealkylated chlorotriazine metabolites; ametryn and prometryn and their respective dealkylated thiomethyltriazine metabolites; and S-metolachlor and its ethanesulfonic and oxanilic acid degradates in deionized, ground, surface, and finished drinking water. Water samples are analyzed using direct aqueous injection (DAI) liquid chromatography-electrospray ionization/mass spectrometry/mass spectrometry (LC-ESI/MS/MS). No preanalysis sample manipulation is required other than transfer of a small portion of sample to an injection vial. The lower limit of the method validation is 0.050 microg/L (ppb) for all analytes except 2,4-diamino-6-chloro- s-triazine (didealkylatrazine, DDA, or G-28273). For this compound the LLMV is 0.50 microg/L (ppb). The overall mean procedural recoveries (and percent relative standard deviations) for all water types for all analytes ranged from 95 to 101% (4.5-11%). The method validation was conducted under U.S. EPA FIFRA Good Laboratory Practice Guidelines 40 CFR 160.     

Preparation of antibodies and development of an enzyme-linked immunosorbent assay for determination of dealkylated hydroxytriazines

The development of an indirect competitive enzyme-linked immunosorbent assay (ELISA) for dealkylated hydroxytriazines is reported here for the first time. The assay uses polyclonal antibodies raised against N-(4-amine-6-hydroxy-[1,3,5]triazin-2-yl)-4-aminobutanoic acid (hapten 2g) conjugated to keyhole limpet hemocyanin by the active ester method. The immunizing hapten was synthesized by first introducing the amino group to the triazine ring in a protected form in order to increase its solubility in organic media. Subsequent steps consisted of reacting this compound with an appropriate spacer arm, followed by removal of the protecting group in acidic media. The resulting assay uses a homologous competitor hapten coupled to conalbumin by the mixed anhydride method. Coating antigens prepared using a homologous covalent coupling procedure failed to produce competitive immunoassays. The assay tolerates media with high ionic strength (up to 70 mS cm(-)(1)) and basic pH values (7.5-9.5 units). Under the optimized conditions, this ELISA is specific for dealkylated hydroxytriazines, reaching suitable limits of detection.