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.     

L-半胱氨酸对酰胺类除草剂的离体脱氯反应与机制

研究了L-半胱氨酸与酰胺类除草剂的反应动力学、热力学及其机制.结果表明,L-半胱氨酸促进酰胺类除草剂的降解,该反应遵循二级动力学方程;除草剂降解速率同除草剂分子的亲电常数线性相关,降低顺序为甲草胺(kL-cysteine=7.65×10-3mol/(L×s))>乙草胺(kL-cysteine=7.23×10-3mol/(L×s))>丁草胺(kL-cysteine=6.01×10-3mol/(L×s))>S-异丙甲草胺(kL-cysteine=2.15×10-3mol/(L×s)),这与其土壤和高效菌降解速率顺序相一致;产物的质谱鉴定表明,L-半胱氨酸取代除草剂分子中氯原子.表明该反应为双分子亲核取代脱氯反应.热力学分析显示,该反应为焓控反应.除草剂间降解速率的差异性由熵变控制,且除草剂的降解速率与反应熵变(ΔS)具有良好的线性关系,ΔS数值越负,除草剂的降解速率越小.分子中N原子上的醚键取代基支链结构及链长度对反应速率影响较大,而芳环取代基结构没有明显影响.     

Adsorption kinetics of the herbicide safeners, benoxacor and furilazole, to activated carbon and agricultural soils

Chloroacetamide herbicides, namely acetochlor and metolachlor, are common herbicides used on corn and soybean fields. Dichloroacetamide safeners, namely benoxacor and furilazole, are commonly used in formulations containing chloroacetamide herbicides. Extensive reports on adsorption of chloroacetamide herbicides are available, yet little information exists regarding adsorption potential of co-applied safeners. Herein, the adsorption and desorption characteristics of selected herbicide safeners to granular activated carbon (GAC) and in agricultural soils are reported. Further, soil column studies were performed to understand the leaching behaviour of the herbicide Dual II Magnum. Equilibrium sorption experiments of safeners to three agricultural soils and one GAC showed that adsorption was best fitted by the Freundlich isotherm. The Freundlich adsorption constant, K_f, for benoxacor and furilazole sorption onto three agricultural soils ranged from 0.1 to 0.27 and 0.1 to 0.13 (mg/g) × (mg/L)?(1/n), respectively. The K_f for benoxacor and furilazole to GAC was 6.4 and 3.4 (mg/g) × (mg/L)?(1/n), respectively, suggesting more favorable sorption of benoxacor to GAC than furilazole to GAC. The sorption to soils was reversible as almost 40%–90% of both safeners was desorbed from three soils. These results were validated in four replicated soil column studies, where S-metolachlor was shown to leach similarly to the safener benoxacor, originating from the herbicide formulation. The leaching of S-metolachlor and benoxacor was influenced by soil texture. Cumulatively, these results show that safeners will move through the environment to surface waters similarly to the active ingredients in herbicides, but may be removed during drinking water treatment via GAC.     

新农药HW-02在土壤中的吸附

采用振荡平衡法研究了新型除草剂HW-02在5种不同土壤中的吸附特性. 结果表明:土壤对HW-02的吸附性强;HW-02在黑钙土、白浆土、草甸土、砂性土和黏壤土等5种土壤中的吸附可用Freundlich等温式较好地描述,其吸附系数(K_F)分别为332.65,103.32,672.97,577.96和289.60,吸附自由能变绝对值(ΔG)分别为16.55,22.73,18.32,18.48和22.86 kJ/mol,说明HW-02在土壤中的吸附以物理吸附为主;HW-02在5种土壤中的有机质吸附常数(K_OM)为796.57～10 197.18,说明其在土壤中迁移性很弱. HW-02在土壤中的吸附系数与土壤w(有机质),pH和w(黏粒)相关性较好,而与阳离子交换量(CEC)的相关性差,说明土壤w(有机质),w(黏粒)和pH是影响HW-02在土壤中吸附的主要因素.      

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。     

除草剂乙草胺、异丙甲草胺的光降解及其致突变性

对两种常见的酰胺类除草剂乙草胺、异丙甲草胺的光降解进行了研究,采用Ames试验方法对母体及其光降解产物的致突变性进行了检验．结果表明,初始ｐＨ值的变化对这两种除草剂的光降解速率无明显影响,异丙甲草胺比乙草胺更易于发生光降解．乙草胺在光降解前后均表现出无致突变性;异丙甲草胺本身具有致突变性,在光降解过程中未表现出有其它致突变性物质产生．     

农田土壤除草剂污染的修复技术研究进展

除草剂主要用于保护农作物免受杂草的侵害,是现代农业生产中用量最多的一类农药.然而,随着全球粮食需求的增加,除草剂的用量逐年增大,药效也不断增强,导致除草剂在农田土壤中出现累积、迁移转化和毒害作用等问题.为了降低除草剂给土壤-作物系统带来的生态风险,根据除草剂污染特征和区域农业生产规律研发绿色低碳修复技术,是目前生态环境领域需要关注的问题.基于此,整理了近年来关于农田土壤除草剂污染治理的相关报道,重点分析了修复技术的研究进展和应用案例,并对除草剂修复领域未来的发展动态进行了展望.目前应用于农田除草剂的修复技术主要有基于微生物修复、酶修复和植物修复的生物修复技术,以及基于生物炭基材料的吸附固定技术.其中,生物修复技术的发展相对成熟,已经应用于实际农田除草剂的修复治理工作,并形成了成功的修复案例.为了提升对农田土壤除草剂污染的修复效果,修复技术逐渐从单一模式向物理化学-生物多技术耦合模式发展,以充分发挥多技术集成应用的协同作用.     

Adsorption and correlation with their thermodynamic properties of triazine herbicides on soils

IntroductionAdsorptionofherbicidesonsoilfromwaterisanimportantfactoraffectingtheirfate,biologicalactivity,andpersistenceinsoil watersystem .Itisoftenaffectedbyseveralpropertiesofsoil.Betterunderstandingofadsorptionanditsaffectingfactorswillmakeitpossibletoadjusttheherbicidedosageaccordingtosoilproperties,thusreducingtheenvironmentalpollutionofherbicidesintheenvironment.Fig .1　StructuresofthreetriazineherbicidesAmongthepost emergentherbicides,triazineherbicidesaremostcommonlyusedworldwideonco…     

Biodegradation of acetanilide herbicides acetochlor and butachlor in soil

The biodegradation of two acetanilide herbicides, acetochlor and butachlor in soil after other environmental organic matters addition were measured during 35 days lal)oratory incubations. The herbicides were applied to soil alone, soiI-SDBS (sodium dodecylbenzene sulfonate) mixtures and soil-HA (humic acid) mixtures. Herbicide biodegradation kinetics were compared in the different treatment. Biodegradation products of herbicides in soil alone samples were identified by GC/MS at the end of incubation. Addition of SDBS and HA to soil decreased acetochlor biodegradation, but increased butachlor biodegradation. The biodegradation half-life of acetochlor and butachlor in soil alone, soilSDBS mixtures and soil-HA mixtures were 4.6d, 6, ld and 5.4d and 5.3d, 4.9d and 5.3d respectively. The biodegradation products were hydroxyacetochlor and 2-melhvl-6-ethvlaniline for acetochlor, and hvdroxvbutachlor and 2,6-diethvlaniline for butachlor.     

作物植株残体还田土壤对除草剂的截留作用

加入成熟作物植株残体还田的土壤（简称秸秆还田土壤）与自然土壤的土柱淋洗对比实验，研究了玉米秸秆还田土壤对除草剂乙草胺和阿特拉津的截留作用以及水稻秸秆还田土壤对丁草胺的截留作用。结果表明，作物秸秆还田土壤对所研究的三种除草剂有明显的截留作用，在土桩的最上部10cm内，秸秆还田土壤对乙草胺、丁草胺和阿特拉津的截留量分别是自然土壤对其截留量的1.33、1.77和1.88倍。     

典型土壤组分及其与丁草胺除草剂作用的红外光谱研究

运用红外光谱法对3种典型土壤(红壤、潮土和黑土)的矿物质、胡敏酸及其与丁草胺的吸附附着物进行了研究.结果表明,江西红壤为高岭石型矿物质,在3 703,3 628,1 089,1 035,914,696及471 cm-1处有特征吸收峰.北京潮土和黑龙江黑土为蒙脱土型矿物质,在1 432和872 cm-1处有特征吸收峰,而在3 703和3 628 cm-1处吸收较弱或微弱.不同土壤中胡敏酸的组成基本相同,均在3 420,2 935,2 847,1 724,1 660及1 035 cm-1处有明显吸收,表明其含有缔合羟基、芳烃、羰基、醇、酚及酸等.丁草胺与土壤胡敏酸的吸附机理主要是在胡敏酸的羰基及酚醇羟基上形成氢键.      

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.     

荧光猝灭滴定法研究土壤腐殖质与氨基甲酸酯类农药相互作用

为研究氨基甲酸酯类农药在溶解有机质参与下的迁移转化过程,利用荧光猝灭滴定法研究了土壤HS(腐殖质)与氨基甲酸酯类农药的相互作用. 结果表明,呋喃丹和西维因的荧光都能不同程度地被FA(富里酸)和HA(腐殖酸)猝灭,主要猝灭机理为静电结合猝灭. 采用静态猝灭模型计算出氨基甲酸酯类农药与HS的K(结合常数),lg K由大到小为呋喃丹-HA(4.96)>西维因-HA(4.93)>呋喃丹-FA(4.72)>西维因-FA(4.68). HA与氨基甲酸酯类农药的lg K明显大于FA与氨基甲酸酯类农药,表明HS与氨基甲酸酯类农药间的作用力有疏水作用. 进一步研究表明,氢键作用对HS与氨基甲酯类农药结合有一定的影响.      

灭草松在土壤中吸附的支配因素

通过振荡平衡法测定了灭草松在6种土壤中的吸附等温线,计算了灭草松在吸附过程中平均偏摩尔自由能的变化值.结果表明灭草松在其中5种土壤上的吸附等温线为直线,分配常数Kd 0.14～0.31mL·g^-;土壤吸附灭草松的强弱次序为:德清水稻土＞安吉水稻土(pH4.79)＞余杭水稻土＞临安红壤＞安吉水稻土(pH7.36)＞德清黄壤.土壤性质与分配常数的相关分析,发现支配灭草松在土壤上吸附的主要因素是pH值和土壤有机质含量.灭草松在土壤上的吸附主要是中性灭草松及其阴离子在土壤有机质中的分配,与有机质性质关系不大.     

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

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Single and joint stress of acetochlor and Pb on three agricultural crops in northeast China

In order to evaluate ecological risk of agrochemicals in agricultural environment, single and joint toxic effects of an important herbicide and a typical heavy metal on root elongation of crops were investigated. Seeds of the three crops including wheat （Triticum aestivum）, Chinese cabbage （Brassica pekimensis） and soybean （Glycine max） as the main crops in northeast China were exposed to acetochior as a herbicide and lead （Pb） as a heavy metal using the pot-culture method, and meadow brown soil as one of the main soils distributed in northeast China was applied in the investigation. The results indicated that the interactive effects of the two pollutants on root elongation of the three crops were very complicated although they had markedly significant （P〈0.01） linear interrelationships based on the regression analyses. When the concentration of added Pb^2＋ reached 200 mg/kg, acetochlor and Pb had an antagonistic effect on the inhibition of root elongation of the three crops. However, acetochlor and Pb had significantly （P〈0.05） synergic effects on the inhibition of root elongation when concentration of added Pb^2＋ was up to 1000 mg/kg. At the low concentration of added Pb, joint toxicity of acetochlor and Pb was more dependent on the concentration of Pb. Among the three crops, wheat was the most sensitive to the toxicity of Pb and Chinese cabbage was the most sensitive to the toxicity of acetochlor.     

Effect of herbicide acetochlor on cytochrome P450 monooxygenases and GST of earthworms Eisenia fetida

To assess the sublethal toxicity of the herbicide acetochlor to earthworms and to find out biomarkers possible inducted under acetochlor exposure, Eiseniafetida was exposed to artificial soils supplemented with different concentrations of acetochlor（5, 10, 20, 40 and 80 mg/kg soil）. Effects of the acetochlor on cytochrome P450 monooxygenases p-nitroanisole O-demethylase（ODM）, aldrin epoxidase（AE） and glutathione-S-transferases （GSTs） activities were determined. The results revealed cytochrome P450 monooxygenases were elevated with increasing concentrations of acetochlor, and the AE activity increased significantly compared with control at the concentration of 80 mg/kg （P〈0.05）. However, ODM activity from E. fetida was not induced significantly by acetochlor at all treatments（P〉0.05）. Sodium dodecyl sulfate-polyacryamide gel electrophoresis（SDS-PAGE） showed that one protein band was visualized and no evident differences were found in protein profiles between treatments and control. The GST activity increased significantly with longer duration（P〈0.05） and increasing concentrations of acetochlor exposure（P〈0.05）. This study showed that the monooxygenases and GSTs activities in E. fetida could be induced by acetochlor, and thus, the AE and GST could be used in sublethal assays for soil contamination surveys and GST could be used as biomarkers of acetochlor exposure in E. fetida.     

滇池泥炭土对两种抗生素和双酚A的吸附

用不同浓度NaOH溶液处理采集自云南滇池的泥炭土,研究处理前后的泥炭土对两种抗生素磺胺甲恶唑（SMX）、卡马西平（CBZ）及双酚A（BPA）的吸附机理,并深入探讨3种污染物及泥炭土性质对吸附特性的影响.吸附等温线拟合结果表明,Freundlich模型对3种物质在泥炭土上的吸附等温线有较好的拟合优度.3种物质中,BPA的非线性指数n值最低,这可能是由于其不对称的结构特征导致.随着处理泥炭土的NaOH浓度增加,3种吸附质在泥炭土上的吸附顺序为BPA > CBZ > SMX,BPA的吸附最高可能是由于其含有两个酚羟基,与泥炭土有较强的极性作用导致,而CBZ的吸附比SMX的吸附高是由憎水性作用引起.NaOH处理后并没有增加泥炭土对这3种吸附质的吸附,说明对于离子型化合物,吸附过程和机理复杂,BPA蝴蝶状结构及苯环上含有两个羟基可能导致其在泥炭土上出现特异性吸附,这导致其吸附系数最高;NaOH处理后泥炭土的有机碳含量增加但比表面积可能降低,从而使3种污染物的吸附降低.因此,本研究3种离子型化合物在泥炭土上的吸附受到吸附质的官能团及溶解度、泥炭土的有机碳含量及官能团等多种因素的影响.     

Adsorption of acetanilide herbicides on soil and its components. II. Adsorption and catalytic hydrolysis of diethatyl-ethyl on saturated Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite

Adsorption and catalytic hydrolysis of the herbicide diethatyl-ethyl [N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ester] on homoionic Na⁺-, K⁺-, Ca²⁺-, and Mg²⁺-montmorillonite clays were investigated in water solution. The Freundlich adsorption coefficient, Kf, got from isotherms on clay followed the order of Na⁺ K⁺ > Mg²⁺ Ca²⁺. Analysis of FT-IR spectra of diethatyl-ethyl adsorbed on clay suggests probable bonding at the carboxyl and amide carbonyl groups of the herbicide. The rate of herbicide hydrolysis in homoionic clay suspensions followed the same order as that for adsorption, indicating that adsorption may have preceded and thus caused hydrolysis. Preliminary product identification showed that hydrolysis occurred via nucleophilic substitution at the carboxyl carbon, causing the cleavage of the ester bond and formation of diethatyl and its dechlorinated derivative, and at the amide carbon, yielding an ethyl ester derivative and its acid.These pathways also suggest that hydrolysis of diethatyl-ethyl was catalyzed by adsorption on the clay surface.