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

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

水溶性有机物对草萘胺在土壤中吸附与迁移的影响

采用批次吸附试验和土柱淋洗试验,研究了绿肥和污泥中水溶性有机物(DOM)对除草剂草萘胺在黄棕壤和石灰性潮土上吸附和迁移影响.结果表明,供试DOM均能明显降低草萘胺在2种土壤上的吸附,促进草萘胺的迁移,在黄棕壤上效果更明显.在所研究的草萘胺和DOM浓度范围内,绿肥DOM(GM)都比污泥DOM(SS)作用显著.草萘胺的吸附等温线可用Freundlich方程定量描述.绿肥DOM和污泥DOM可分别使黄棕壤中草萘胺吸附量比对照处理(不加DOM)减少22.9%和11.3%,使迁移出土体的草萘胺总量提高了73.42%和26.87%,而使潮土中草萘胺的吸附量减少了9.5%和6.5%,迁移出土体的草萘胺总量增加了43.54%和28.29%.因此,农业土壤中溶解性有机物对农药环境行为有一定影响.     

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.     

利谷隆在土壤中的吸附过程与机理

利谷隆是一种广泛应用的除草剂。本文研究了它在４种不同理化特性土壤中的吸附过程（平衡吸附所需的时间,土壤ｐＨ的影响及吸附等温线）和在单离子饱和粘土矿物上的吸附机理,结果表明：利谷隆在土壤的吸附强度大（Ｋｔ值在３．８８－９３．８４）;达到吸附平衡的短（５ｈ）;ｐＨ值降低,有利于吸附,ｐＨ在４－６范围内变化较明显;另外,利谷隆在土壤中形成氢键、配位键及离子键是可能的。     

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.     

甲磺隆除草剂的测定方法及其吸附行为研究

采用批量平衡法系统研究了甲磺隆除草剂在几种土壤（熟化红壤、砖红壤性红壤、红筋泥、砖红壤）和矿物（高岭石、针铁矿、和Ca²⁺、Al³⁺、Cu²⁺单离子饱和蒙脱石）上的吸附行为.建立了硼酸-硼砂缓冲液体系的毛细管电泳测定甲磺隆的分析方法.甲磺隆在本实验条件下能够与土壤中的杂质达到基线分离,迁移时间为4.6 min.对比实验表明,毛细管电泳法测定甲磺隆与高效液相色谱法具有一致性.然而,毛细管电泳法能显著节省测试时间和成本,在本类吸附实验研究中具有很好的应用价值.吸附实验数据分析表明甲磺隆的吸附行为都可以用Freundlich模型描述,矿物和土壤的K_f值分别在0.82～199.69和1.97～10.48范围.在几种影响甲磺隆吸附的因素中,pH的影响作用最为显著,说明静电作用可能是甲磺隆在土壤及矿物上吸附的主要机理.     

诺氟沙星在4种土壤中的吸附-解吸特征

采用批平衡吸附试验,研究了诺氟沙星在河南封丘潮土、江西鹰潭红壤、苏南常熟水稻土和南京黄棕壤等4种土壤中的吸附行为.结果表明,诺氟沙星的土壤吸附-解吸不同程度地偏离线性模型,但均可用Freundlich模型和Langmuir模型进行良好的线性拟合.其K_f值变化较大,分别为潮土82.0 L/kg、黄棕壤432 L/kg、水稻土5 677 L/kg和红壤8 790 L/kg,显示诺氟沙星在4种土壤中的吸附行为存在较大的差异.此外,诺氟沙星在4种土壤上的解吸过程存在滞后现象.其中,诺氟沙星在红壤中的滞后现象明显与其他3种土壤不同,其滞后系数至少大5倍以上.研究表明4种土壤中诺氟沙星的吸附参数K_f值与土壤pH呈极显著负相关,与土壤溶液中诺氟沙星阳离子形态比例则呈极显著正相关.在不同pH（5～9）下,红壤和水稻土的诺氟沙星吸附参数lgK_d随pH的升高先增加而后降低,黄棕壤和潮土中则不同程度地线性下降.可见,阳离子吸附可能是诺氟沙星土壤吸附的重要机理,而低pH下红壤和水稻土中诺氟沙星的吸附是阳离子吸附和土壤溶液共存阳离子竞争性吸附共同作用的结果.     

氟啶胺在土壤中的吸附解吸与淋溶特性

采用批量平衡法研究了氟啶胺在南京黄棕壤、江西红壤、东北黑土中的吸附解吸特性.结果表明,25℃下,氟啶胺在3种供试土壤中的等温吸附-解吸曲线能较好地符合Freundlich模型,其吸附常数分别为南京黄棕壤119.34,江西红壤202.23,东北黑土311.88,与土壤有机质含量、阳离子代换量和粘粒含量有良好的相关性,相关系数分别为0.9973,0.9690,0.8586.土壤对氟啶胺的吸附自由能变化均小于40kJ/mol,属于物理吸附.氟啶胺在3种土壤中均难淋溶.     

湿地土壤对硝基苯的吸附-解吸作用

应用平衡法研究硝基苯在湿地土壤中的吸附-解吸特性.结果表明,湿地土壤对硝基苯具有较强的吸附能力,其吸附行为可以用Linear和Freundlich型吸附等温式描述,不同类型湿地土壤对硝基苯的吸附和解吸能力有所不同.将吸附常数Kf与湿地土壤的理化性质进行相关性分析表明,土壤有机质含量与硝基苯吸附系数显著相关(r=0.888,P<0.01,n=7),其中泥炭沼泽土表层有机质含量最高,其吸附系数也最大(86.44 mg·kg-1).硝基苯在湿地土壤中的吸附自由能变化量为10.68～13.45 kJ·mol-1,表明其吸附以物理吸附为主.不同类型湿地土壤对硝基苯的解吸能力也有一定的差别,其中草甸白浆土的解吸率最大(41.87%),泥炭沼泽土表层解吸率最小(11.79%).     

生物炭对紫色土中氟苯尼考吸附与迁移的影响

氟苯尼考作为我国常用的兽用抗生素在土壤中被广泛检出,在有机质含量低(约<2%)、吸附性能差的紫色土中具有高迁移性,而具有多孔结构的生物炭对其具有较强的阻控能力. 本文采用批量平衡吸附试验与填装土柱淋溶试验,探究生物炭对氟苯尼考在紫色土中吸附与迁移的影响. 结果表明:Freundlich等温吸附模型可较好地刻画氟苯尼考在供试土壤上的吸附行为,其中,紫色土对氟苯尼考的吸附过程更接近于线性吸附(1/n=0.99±0.07),而生物炭施用使得紫色土对氟苯尼考的吸附容量常数(K_f)提高了9.69倍,且非线性增强;两点化学非平衡模型可较好地刻画供试土柱中Br?示踪剂与氟苯尼考的穿透曲线(R2≥0.964,RMSE≤0.09),生物炭施用分别提高了水动力弥散系数、瞬时吸附常数、瞬时吸附交换所占分数及一阶动力学速率系数,但因水土接触时间受限,瞬时吸附常数(K_d-c)远小于分配系数(K_d)和吸附容量常数(K_f);生物炭的施用使得紫色土中氟苯尼考的残留率增加了38%. 研究显示,紫色土中施用生物炭虽然促进了水分运动,但仍可通过提高吸附能力阻控氟苯尼考的迁移.      

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 characteristic of bensulfuron-methyl at variable added Pb^2＋ concentrations on paddy soils

The combined pollution of heavy metal Pb²⁺ and bensulfuron-methyl (BSM), originating from chemical herbicides, in agroecological environments has become commonplace in southern China. The adsorption of BSM on three paddy soils in the presence of Pb²⁺ was examined using high-performance liquid chromatograph (HPLC). Results indicated that adsorption of BSM could accurately be described by a Freundlich isotherm equation with correlation constant (R) > 0.98, irrespective of the presence of spiked Pb²⁺. Of the various factors influencing BSM sorption, soil pH appeared to be the most influential. The constant K_f of Freundlich isotherm equation tended to increase with increasing Pb²⁺ concentration in soil which indicated that the spiked of Pb²⁺ in paddy soils would promote the sorption of BSM. ΔG^θ of BSM in three paddy soils was less than 40 kJ/mol in all treatments, indicating the adsorption of BSM is mainly physical in nature. The elution of soil dissolved organic matter (DOM) enhanced the adsorption of BSM in paddy soils. The mechanisms involved in the promotion effects of the spiked Pb²⁺ on BSM adsorption might be the modified surface characteristics of paddy soil solids due to the soil acidification and the increase of soil organic matter concentration because of DOM binding.     

除草剂草萘胺在土壤中的降解与吸附行为

采用色谱学(HPLC和GC-MS)和光谱学(UV和Ft-IR)方法研究了除草剂草萘胺在3种土壤(黑土、砖红壤和黄棕壤)中的降解和吸附行为,并对草萘胺土壤中降解的影响因素、降解产物和吸附机理进行了分析.结果表明,在本实验条件下,草萘胺降解速率随土壤温度(15～35℃)和有机质含量(r=0.9794)增加而加快;灭菌条件下的半衰期约是未灭菌时的3倍,土壤微生物是影响草萘胺在土壤中降解的主要因素;草萘胺在黄棕壤中的降解途径可能是脱烷基,降解产物可能为/v-甲基-2-(1-萘氧基)丙酰胺和/V-乙基-2-(1-萘氧基)丙酰胺.草萘胺在黄棕壤、砖红壤和黑土上的吸附系数(Kf)值分别为1.29、3.43和13.36,3种土壤上的吸附自由能(AG)均小于40U·mol-1,即以物理吸附为主,其吸附行为可用Freundlich模型描述.红外光谱学研究进一步证实了3种土壤对草萘胺吸附容量差异是黑土,砖红壤,黄棕壤.     

除草剂苄嘧磺隆在土壤中的吸附

应用平衡法研究了除草剂苄嘧磺隆在8种土壤中的吸附特性．结果表明,土壤对苄嘧磺隆有很强的吸附性,且随供试土壤理化性质的差异其吸附性呈明显变化．苄嘧磺隆在土壤中的吸附符合Fruendlich方程,其在土壤中的吸附常数Kf与土壤有机质、粘粒含量呈显著正相关(r＝0．7393*和0．7751*,p＜0．05),与土壤pH呈显著负相关(r＝0．7068*,p＜0．05)．苄嘧磺隆在土壤上的吸附自由能为11．45—13．38KJ／mol,表明苄嘧磺隆在土壤中的吸附以物理作用为主。     

Impacts of soil organic matter, pH and exogenous copper on sorption behavior of norfloxacin in three soils

Norfloxacin (Nor) sorption and the factors (soil organic matter (SOM), pH, and exogenous copper (Cu) influencing the sorption were investigated in a black soil (soil B), a fluvo-aquic soil (soil F), and a red soil (soil R). With increasing of Nor concentrations, sorption amount of norfloxacin increased in both the bulk soils and their SOM-removed soils, but the sorption capacity in SOM-removed soils was higher than that of their corresponding bulk soils, indicating that the process of norfloxacin sorption in soil was influenced by the soil properties including SOM. The sorption data in all bulk soils and SOM-removed soils were fitted to Freundlich and Langmuir models. The correlation coefficients suggested that the experimental data fitted better to Freundlich equation than to Langmuir equation. Furthermore, the data from soil F and SOM-removed F could not be described by Langmuir equation. The norfloxacin sorption amount decreased in soil B and soil F, whereas it increased in soil R as solution pH increased. The maximum KD and KOC were achieved in soil R when the equilibrium solution pH was 6. And the norfloxacin sorption was also influenced by the exogenous Cu2+ ions, which depended on the soil types and Cu2+ concentrations. With increasing of Cu2+ concentrations in solution, generally, sorption amount, KD and KOC for norfloxacin in soils increased and were up to a peak at 100 mg/L Cu2+, and then the sorption amount decreased regardless of norfloxacin levels.     

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.     

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.     

灭草松和莠去津在土壤中的竞争吸附

采用振荡平衡法测定了低浓度范围内(＜30 mg·L-1)灭草松和莠去津单、双溶质在4种土壤中的吸附等温线.单溶质吸附结果表明,4种土壤中灭草松存在不吸附、吸附2种类型,吸附等温线类型有L和C型;莠去津的吸附等温线有L、S和C型;有机质、矿物质及农药疏水性是影响灭草松和莠去津在土壤中吸附的重要因素.通过比较单溶质和双溶质溶液中灭草松和莠去津的等温吸附线,发现混合溶液中它们的吸附行为相互之间随土壤类型不同存在竞争、无影响和协同作用,并且竞争程度与溶质浓度有关.用理想溶液吸附理论(IAST)和单溶质吸附等温线参数,模拟了双溶质溶液中灭草松和莠去津的吸附等温线,结果显示,该模型不能很好的预测实验结果.进一步结合吸附机理分析认为,不同土壤中的竞争结果是由于2种农药在其中共同占有吸附点的情况不同造成的.     

除草剂普杀特在土壤—水两相中的吸附-脱附和光解

 为了解普杀特农药进入自然界的环境行为，特别是它在不同土壤—水体系中的分配和归宿，研究了其在8种土壤上的吸附 脱附过程，并且通过模拟太阳光探讨了普杀特在水相中的光解情况。结果表明，普杀特在土壤上的吸附 脱附与土壤的理化性质密切相关，高有机质、低pH值的土壤具有强吸附能力；其吸附、脱附均可用Freundlich方程描述，但脱附等温线要滞后于吸附线。太阳光中紫外部分的光有利于普杀特光解，其光解可用假一级动力学方程表示。