几种酰胺类除草剂的光降解及其致突变性

对３种常见的酰胺类除草剂乙胺,异丙甲草胺,丁草胺的光降解进行了研究,采用Ａｍｅｓ试验方法对母体和光降解产物的致突变性进行了检验,结果表明,在紫外灯照射下,这３种除草剂的光降解均较符合一级动力学,其降解速率次序为：异丙草胺〉乙草胺〉丁草胺。     

异丙甲草胺与锌共存对斜生栅藻毒性手性差异影响

为评价重金属与手性农药共存的生物选择性毒性,采用毒性试验标准方法研究了Rac-、S-异丙甲草胺单独及与锌共存对斜生栅藻的手性毒性差异.结果表明,Zn2+存在条件下Rac-、S-异丙甲草胺对斜生栅藻的生长趋势影响与除草剂单独作用时的趋势基本相同,Zn2+的存在降低了高浓度除草剂对斜生栅藻的生长抑制作用,处理初期(24 h)0.30 mg·L-1Rac-和S-异丙甲草胺单独对斜生栅藻生长的抑制率分别为49.61%和59.73%,与Zn2+联合作用其抑制率分别为38.41%和42.52%.Zn2+的存在增加了Rac-和S-异丙甲草胺对斜生栅藻的立体选择性毒性差异,使S-异丙甲草胺急性毒性增大的程度大于Rac-异丙甲草胺毒性的增加;与Zn2+的联合毒性作用类型表现为除草剂在低浓度下为部分相加作用,高浓度下为拮抗作用;除草剂单独及与Zn2+联合作用处理96 h后的斜生栅藻叶绿素含量变化与其生长趋势基本一致.     

Rac-及S-异丙甲草胺对2种微藻毒性特征影响研究

应用急性毒性试验方法,在对映体水平上研究了除草剂Rac-及S-异丙甲草胺对斜生栅藻(Scenedesmus obliquus)和普通核小球藻(Chlorella vulgaris)的急性毒性特征及腐殖酸对除草剂毒性的影响.结果表明,Rac-及S-异丙甲草胺的急性毒性与浓度及暴露时间呈正相关,Rac-及S-异丙甲草胺对微藻细胞的急性毒性存在立体选择性差异.Rac-异丙甲草胺对普通核小球藻和斜生栅藻的EC50,96 h分别是S-异丙甲草胺的2.25和1.81倍,S-异丙甲草胺对微藻细胞的生态毒性较大,而斜生栅藻对Rac-及S-异丙甲草胺的敏感性更强,且Rac-及S-异丙甲草胺对斜生栅藻和普通核小球藻的急性毒性存在一定的线性相关性.腐殖酸的加入能够改变Rac-及S-异丙甲草胺对微藻细胞生态毒性,对S-异丙甲草胺的生态毒性的影响更为明显(P<0.05).     

四种酰胺类除草剂对土壤酶活性的影响

在实验室控制条件下,研究了酰胺类除草剂丁草胺、乙草胺、丙草胺和异丙甲草胺在田间推荐用量下,对土壤过氧化氢酶活性和脱氢酶活性的影响.结果表明,培养初期,4种除草剂对2种酶活性有不同程度的抑制作用,土壤过氧化氢酶活性于第7d就很快恢复,而脱氢酶活性在13d后得以逐渐恢复.添加稻秆可使土壤酶活性提高,土壤脱氢酶比过氧化氢酶活性变化大.4种除草剂对土壤生态环境影响不大,稻秆还田有利于提高土壤中生化过程的活性,缓冲外来污染物对土壤生态的影响.     

粘土矿物,腐殖酸对异丙甲草胺的吸附

除草剂异丙甲草胺被粘土矿（钙蒙脱石）、土壤腐殖酸的吸附研究，表明异丙甲草胺在钙蒙脱石及腐殖酸上的吸附等温线符合Ｆｒｅｕｎｄｌｉｃｈ方程。异丙甲草胺在钙蒙脱石和腐殖酸不同比例的复合物上吸附的研究，表明钙蒙脱石与腐殖酸的相互作用，降低了自身对农药的吸附。研究中初步讨论了其作用机理。     

黄河三角洲贝类增养殖区海水中16种除草剂污染特征及评价

本文以黄河三角洲贝类增养殖区为研究对象,选取3个典型区域,采用气相色谱-质谱法分析16种除草剂在海水中的污染状况和分布特征。结果表明,黄河三角洲贝类增养殖区海水中检出阿特拉津等10种除草剂,其中阿特拉津、扑草净、西草净、莠灭净、扑灭津和异丙甲草胺6种除草剂的检出率和平均检出浓度均较高;同区域7月海水中16种除草剂平均检出浓度的总量低于4月和10月;L区域16种除草剂平均检出浓度的总量低于H、K区域;聚类分析发现,扑草净、西草净和莠灭净的分布特征相似,异丙甲草胺与上述3种除草剂的分布特征不同,阿特拉津和扑灭津的分布特征不明显;生态风险分析发现,10月贝类增养殖区海水样品中阿特拉津、异丙甲草胺浓度存在中度风险,4月、7月和10月扑草净浓度存在中度生态风险。     

ASE-GC/MS同时测定土壤中8种酰胺类除草剂

通过优化加速溶剂萃取(ASE)条件、固相小柱净化(SPE)条件和气相色谱质谱(GC/MS)仪器分析条件,建立了"ASE提取-SPE净化-GC/MS分析"同时测定土壤中敌稗、甲草胺、乙草胺、丙草胺、丁草胺、杀草丹、异丙草胺和异丙甲草胺8种酰胺类除草剂残留量的分析方法。土壤样品经正己烷∶丙酮(1∶1)提取,提取液浓缩后经固相小柱净化,气相色谱质谱测定,内标法定量。研究结果表明:8种酰胺类除草剂在0.1~6.0 mg/L范围内线性良好,相关系数在0.995以上,方法检出限在5.0×10~(-3)~9.2×10~(-3)mg/kg之间,对实际土壤样品进行低、中、高浓度分别为0.02、0.05和0.5 mg/kg的加标测定,平行分析(n=6)的相对标准偏差在3.6%~12.5%之间,酰胺类除草剂的平均回收率在64.8%~101.7%之间。该方法灵敏度高、快速准确,适用于土壤中酰胺类除草剂的定性和定量检测,能为批量土壤样品的检测提供科学的方法。     

水华微囊藻对除草剂S-异丙甲草胺胁迫的光合活性响应

随着农业生产的发展,酰胺类除草剂的大量使用造成了一系列环境污染问题.为探究酰胺类除草剂——S-异丙甲草胺对水生生态系统造成的影响,运用浮游植物分类荧光仪(Phyto-PAM),以蓝藻中的水华微囊藻(Microcystis flos-aquae)为受试生物,测定了水华微囊藻在不同ρ(S-异丙甲草胺)胁迫下7 d内光合色素含量及相关叶绿素荧光参数的变化.结果表明:①培养周期内,随ρ(S-异丙甲草胺)的增加水华微囊藻叶绿素a与类胡萝卜素的含量均受到不同程度的抑制.②各S-异丙甲草胺处理组的实际光能转化效率〔Y(Ⅱ)〕在培养后1～5 d均低于对照组,到第7天时均恢复正常水平.③从第3天起,各S-异丙甲草胺处理组最大光能转化效率(F_v/F_m)、半饱和光照强度点(I_k)均高于对照组,并且10、25和50 mg/L S-异丙甲草胺处理组的最大电子传递速率(P_nmax)也高于对照组.④从第5天起,10、25和50 mg/L S-异丙甲草胺处理组的快速光响应曲线均高于对照组.⑤除50 mg/L S-异丙甲草胺处理组的...     

异丙甲草胺及其S型对映体对蚯蚓的急性毒性差异

采用OECD标准滤纸接触法、人工土壤法及自然土壤法研究了异丙甲草胺及其S型对映体对蚯蚓的急性致死作用及手性差异.结果表明,3种方法相比较,滤纸染毒法结果置信区间最大,可靠性较差.自然土壤中Rac-异丙甲草胺及S-异丙甲草胺对蚯蚓的急性毒性大于人工土壤;根据毒性分级,Rac-异丙甲草胺及其S型对映体均属于低毒级农药;3种试验方法所得的Rac-异丙甲草胺及S-异丙甲草胺对蚯蚓的LC50差别不大,表明这2种农药对蚯蚓急性毒性的手性差异较小.     

镉与S-异丙甲草胺对斜生栅藻的联合毒性作用

采用毒性标准实验方法研究了Cd2+与S-异丙甲草胺单独及联合作用对斜生栅藻急性毒性、总可溶性蛋白含量、超氧化物歧化酶(SOD)活性和细胞膜通透性的影响.结果表明Cd2+与S-异丙甲草胺单独作用时EC50均随时间的延长而减小,且S-异丙甲草胺的急性毒性大于Cd2+;Cd2+、S-异丙甲草胺的EC50-24h分别为0.27 mg·L-1、0.24 mg·L-1,EC50-96h分别为0.16mg·L-1、0.13 mg·L-1.Cd2+与S-异丙甲草胺联合作用时低浓度表现为协同作用,高浓度表现为拮抗作用.暴露96 h后,Cd2+与S-异丙甲草胺单独及联合作用下,随有毒物质浓度升高,斜生栅藻总可溶性蛋白含量降低,SOD酶活性先激活后抑制,细胞膜通透性逐渐增大.     

Adsorption of chloroacetanilide herbicides on soil (I). Structural influence of chloroacetanilide herbicide for their adsorption on soils and its components

Adsorption of chloroacetanilide herbicide acetochlor,alachlor, metolachlor and propachlor on soils and soil components was determined, and the structural differences of these herbicides were used to explain the order of sorptivity. Adsorption isotherms for all herbicide-soil combinations conformed to the Freundlich equation, and Kf increased with increasing soil organic carbon content. Kd on soil humic acid was greater than that on clay, but association of humic acid with clay reduced the overall adsorption. On all soils and soil humic acids, herbicide adsorption decreased in the order: metolachlor > acetochlor > propachlor > alachlor. On Ca²⁺-montmorrilonite, the order changed to metolachlor > acetochlor > alachlor > propachlor. FT-IR spectra of herbicide-clay or herbicide-humic acid-clay mixtures showed that H-bonding and charge transfer were the primary interaction pathways between these compounds and the surface of clay or humic acids. The different moieties attached to 2-chloro-acetanilide and their unique arrangement may have influenced the binding mechanisms and thus the sorptivity of these herbicides. This study indicates that the structural difference of pesticides in the same classes may be used as a molecular probe to obtain a better understanding of sorption mechanisms of pesticides on soil.     

游离羟基及表面活性剂对乙草胺光解的影响

以高压汞灯为光源,以p-亚硝基-N,N-二甲基苯胺(PNDA)作为·OH自由基的探针,研究了H2O2及表面活性剂0206-B(苯乙烯苯酚聚氧乙烯醚和十二烷基苯磺酸钙混剂)对除草剂乙草胺在水中间接光解作用的影响.结果表明,H2O2对水中乙草胺具有光敏化降解作用,其敏化作用效应与·OH有关;而0206-B对乙草胺具有光猝灭降解作用,光猝灭降解作用效应与0206-B减少水溶液中的·OH自由基含量有关.乙草胺直接光解与H2O2作用的乙草胺间接光解相同的产物有Rf(比移值)为0.12、0.52、0.61、0.72的化合物;H2O2敏化降解抑制了乙草胺直接光解产物Rf为0.04、0.10、0.18、0.21、0.79的化合物产生,但促进乙草胺间接光解Rf为0.45、0.66的新光解产物生成.     

腐殖酸光敏化降解土壤中多环芳烃的动力学

多环芳烃化合物(PAHs)由于致癌、致畸和致突变而受到广泛关注。实验以多环芳烃菲(Phe)和芘(Pyr)为目标污染物,研究了腐植酸和紫外辐射强度对PAHs光降解动力学的影响,及腐植酸光敏化光降解土壤中PAHs的机制.结果表明,腐殖酸光敏化降解Phe和Pyr符合一级动力方程,随着腐殖酸投加量的增加,Phe和Pyr的动力学常数也逐渐增加,半衰期缩短,在添加0、10、20、30、40 mg/kg腐植酸后,Phe的半衰期分别为52.90、47.79、43.86、37.87、34.48 h,Pyr的半衰期分别为45.90、38.50、36.09、30.26、29.74 h;腐殖酸可以将吸收光能传递给土壤中Phe和Pyr使其发生敏化光解,也可以使Phe和Pyr发生光氧化反应;随着辐射强度的增加,PAH光降解速率增加。该研究为应用腐殖酸光敏化降解土壤中PAHs有机污染物提供了参考依据。     

Photodegradation of acetochlor in water and UV photoproducts identified by mass spectrometry

The sunlight photodegradation half-lives of 20 mg/L acetochlor were 151, 154 and 169 days in de-ionized water, river water and paddy water, respectively. When exposed to ultraviolet (UV) light, acetochlor in aqueous solution was rapidly degraded. The half-lives were7.1, 10.1, and 11.5 min in de-ionized water, river water and paddy water, respectively. Photopreduets of acetochlor were identified by gas chromatography/mass spectrometry(GC/MS) and found at least twelve photoproducts resulted from dechlorination with subsequent hydrtrxylation and cyclization processes. The chemical structures of ten photoproducts were presumed on the basis of mass spectrum interpretation and literature data. Photoproducts are identified as 2-ethyl-6-methylaniline; N, N-diethylaniline ; 4, 8-dimethyl-2-oxo- 1,2,3,4- tetrahydroquino-line; 2-oxo-N-(2-ethyl-6-methylphenyl)-N-(ethoxymethyl) acetamide; N-(ethoxymethyl)-2‘-ethyl-6‘-methylformanilide; 1-hydroxyaeetyl-2-ethoxyl-7-ethylind ole; 8-ethyl-l-ethoxymethyl-2-oxo-1, 2, 3, 4-tetrahydroquinoline; 4, 8-dimethyl-l-ethoxymethyl-2-oxo-1, 2, 3, 4-tetrahydroquinoline; 2-hydroxy-2‘-ethyl-6‘-methyl-N-(ethoxymethyl) acetanilide and a compound related to acetochlor. The other two photoproducts were detected by GC/MS although their chemical structure was unknown.     

Degradation of duloxetine: Identification of transformation products by UHPLC-ESI(+)-HRMS/MS, in silico toxicity and wastewater analysis

Duloxetine (DUL), an antidepressant drug, has been detected in surface water and wastewater effluents, however, there is little information on the formation of its transformation products (TPs). In this work, hydrolysis, photodegradation (UV irradiation) and chlorination experiments were performed on spiked distillated water, under controlled experimental conditions to simulate abiotic processes that can occur in the environment and wastewater treatment plants (WWTPs). Eleven TPs, nine from reaction with UV light and two from chlorine contact, were formed and detected by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry, and nine of them had their chemical structures elucidated upon analyses of their fragmentation patterns in MS/MS spectra. The formation and degradation of the TPs were observed. The parent compound was completely degraded after 30?min in photodegradation and after 24?hr in chlorination. Almost all TPs were completely degraded in the experiments. The ecotoxicity and mutagenicity of the TPs were predicted based on several in silico models and it was found that a few of these products presented more ecotoxicity than DUL itself and six TPs showed positive mutagenicity. Finally, wastewater samples were analyzed and DUL and one TP, possibly formed by chlorination process, were detected in the effluent, which showed that WWTP not only did not remove DUL, but also formed a TP.     

Adsorption of chloroacetanilide herbicides on soil and its components Ⅲ. Influence of clay acidity, humic acid coating and herbicide structure on acetanilide herbicide adsorption on homoionic clays

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT-IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca2 + -, Mg2 + -. Al3 + -and Fe3 + -saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, Kf decreased in the order of metolachlor ＞ acetolachlor ＞ alachlor ＞ propachlor on the same clay. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H-bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg2+ ＜ Ca2+ ＜ Al3+ ≤ Fe3+ which coincided with the iucreasing aciditv of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H-bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay-to-humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.     

Adsorption of chloroacetanilide herbicides on soil and its components Ⅲ. Influence of clay acidity, humic acid coating and herbicide structure on acetanilide herbicide adsorption on homoionic clays

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT-IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca²⁺-, Mg²⁺ -. Al³⁺ -and Fe³⁺ -saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, Kf decreased in the order of metolachlor ＞ acetolachlor ＞ alachlor ＞ propachlor on the same clay. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H-bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg²⁺ ＜ Ca²⁺ ＜ Al³⁺ ≤ Fe³⁺ which coincided with the iucreasing aciditv of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H-bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay-to-humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.     

Adsorption-desorption behavior of acetochlor to soils in the presence of some environmental substances

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Rhodococcus sp. T3-1菌株降解乙草胺的特性

以乙草胺为唯一碳源,通过摇瓶培养研究了Rhodococcus sp.T3-1对乙草胺的降解特性.结果表明,菌株T3-1降解乙草胺的最适温度为37℃,且其在pH值6~10的范围内对100mg/L乙草胺的降解率均在96%~97%之间.该菌株在接种量为5%条件下,14h内可将200mg/L的乙草胺降解95.5%;乙草胺的降解速率与乙草胺初始浓度呈负相关,与菌株T3-1的初始接种量呈正相关.菌株T3-1还可以降解丁草胺,但不能降解丙草胺、异丙草胺和吡草胺.