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.     

祁连山七一冰川融水化学组成及演化特征

2006-06～2006-07在祁连山七一冰川采集冰川冰、冰面融水、侧碛河及冰川融水径流样,分析了样品中主要可溶离子浓度、pH及电导率.结果表明,所有样品的pH介于8.05～8.79之间,电导率分布在32.4～134.4 μS·cm-1之间.不同水体中主要可溶离子浓度顺序为:冰面融水＜侧碛河＜七一冰川水文总汇点,水化学类型也由HCO3-Ca2 型演化为(HCO3 SO2-)-(Ca2 Mg2 )型.几乎所有样品中主要可溶阴、阳离子浓度序列为:HCO3＞SO2-4＞CI-＞NO-3,Ca2 ＞Mg2 ＞Na ＞K ,以碳酸盐风化产物为主,也有部分硫酸盐贡献.由于受到各种物理化学因素影响,在水岩作用过程中MG2 和K 浓度增加速率大于Ca2 和Na ,不同于其在地壳中的丰度.七一冰川区融水中离子浓度空间变化主要受水岩作用时间控制,气温影响下的冰川消融量的大小是水化学时间变化的主要控制因素.     

几种天然多孔矿物对钾肥的吸附及缓释效果

以KCl为钾源、斜发沸石、膨润土和凹凸棒石粘土3种天然多孔矿物为缓释载体,进行矿物对钾肥的吸附性能和缓释效果研究。探讨了吸附时间、K+初始浓度与吸附量的关系,确定出K+吸附量最大时的K+初始浓度。用pH=5的HCl溶液和(Ca2++Mg2+)浓度为1.6、3.2、6.4、12.8、19.2、25.6 mmol/L的混合溶液对各矿物缓释肥进行解吸。结果表明:各矿物对K+的吸附在30 min内达到平衡。斜发沸石、膨润土和凹凸棒石粘土对K+的饱和吸附量分别为44.53 mg/g、21.38 mg/g和13.97 mg/g。斜发沸石和膨润土对K+的吸附曲线符合Langmuir吸附等温式,凹凸棒石粘土对K+的吸附曲线总体符合Freundlich等温式。pH=5的HCl溶液对K+的解吸量最小,随解吸溶液中(Ca2++Mg2+)浓度增加,解吸量增大,解吸速率远小于吸附速率。斜发沸石的固钾能力最强,凹凸棒石粘土次之,膨润土相对最弱。     

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.     

Behavior of the herbicide dimepiperate with homoionic clays in aqueous solution

Ｂｅｈａｖｉｏｒｏｆｔｈｅｈｅｒｂｉｃｉｄｅｄｉｍｅｐｉｐｅｒａｔｅｗｉｔｈｈｏｍｏｉｏｎｉｃｃｌａｙｓｉｎａｑｕｅｏｕｓｓｏｌｕｔｉｏｎ￥ＬｉｕＷｅｉｐｉｎｇ；ＷａｎｇＱｉｑｕａｎ；ＳｈａｏＹｉｎｇ；ＪｉＪｉｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉ...     

阳离子强度和阳离子类型对诺氟沙星土壤吸附的影响

以OECD Guideline 106为基础,采用批平衡方法研究不同Ca²⁺离子强度（0.01、0.03、0.05、0.08和0.10 mol/L的CaCl₂溶液）和不同阳离子（0.01 mol/L的NaCl、KCl、NH₄Cl、MgCl₂、CaCl₂、ZnCl₂和AlCl₃溶液）对诺氟沙星在4种土壤（潮土、黄棕壤、水稻土和红壤）中的吸附-解吸影响.结果表明,随着溶液中Ca²⁺离子浓度的增加,诺氟沙星在土壤中的吸附参数K_f值逐渐减小并趋于稳定,两者间存在显著负相关（p≤0.05）.同时,Ca²⁺离子浓度的增加对低浓度诺氟沙星溶液的吸附影响相对高浓度而言不明显. 低pH下,诺氟沙星主要以阳离子形态存在,吸附以阳离子吸附或氢键为主;在兼性离子状态时,则主要以静电吸附和偶极力为主.这是造成4种土壤中诺氟沙星吸附差异的根本原因.在不同离子强度下,土壤溶液中二价Ca²⁺离子存在则对诺氟沙星的活性吸附位点造成竞争性吸附,从而降低诺氟沙星的土壤吸附量.同时,不同阳离子导致诺氟沙星的土壤吸附存在差异.其影响趋势主要为价态的影响,即价态越高,竞争吸附能力越强：M⁺（Na⁺、K⁺、NH^＋₄）2+（Ca²⁺、Mg²⁺、Zn²⁺）3+（Al³⁺）.     

酵母菌对Cr(Ⅵ)的生物吸附作用

研究了啤酒酵母对 Cr( )的吸附作用。当 p H=2时吸附效果最好 ,振荡 30 min吸附基本可达平衡。常见离子Na+、Ca2 +、Mg2 +、Cl-等对吸附影响不大。在一定浓度范围酵母菌对 Cr( )的吸附符合 Freundlich和 Langmuin等温吸附模型。随酵母菌和 Cr( )接触时间的增加 ,Cr( )被还原为 Cr( )。     

pH值和离子对诺氟沙星在胡敏酸上吸附特征的影响

根据OECD Guideline 106批平衡实验,研究了pH值、Ca2+浓度和离子类型对诺氟沙星在胡敏酸上吸附特征的影响.结果表明,吸附系数(Kd)随着pH值的增大有先增加后减小的趋势,在pH 4.0和pH 6.0时吸附系数较大.红外光谱表明,pH 3.0有利于诺氟沙星和胡敏酸形成氢键; pH6.0和7.0时胡敏酸的羧基可能与诺氟沙星的氨基形成了肽键.诺氟沙星在胡敏酸上的吸附量和Kd值随着溶液中Ca2+离子浓度的增加而逐渐减小,表明两者之间存在阳离子吸附和竞争吸附.不同类型的阳离子和阴离子的加入都能导致诺氟沙星在胡敏酸的吸附特性存在差异.阳离子的影响趋势主要为价态的影响,即价态越高,在胡敏酸表面吸附位点的吸附能力就越强,对诺氟沙星吸附阻碍作用越显著,表现在诺氟沙星的最大吸附量(Qm)为:M+ (Na+、K+、NH4+) >M2+ (Mg2+、Ca2+、Zn2+);其次受阳离子的离子半径和水解作用的影响.而只有能水解的阴离子才能对诺氟沙星在胡敏酸上的吸附产生明显的阻碍作用.     

丽江-玉龙雪山不同区域大气降水化学特征

2008─2009年在丽江-玉龙雪山地区的丽江市区、玉龙雪山冰川公园索道下部站(索道地区)和白水1号冰川区(冰川区)3个采样点采集了113个降水样品,对其pH、电导率和主要离子(Cl-、SO42-、NO3-、Ca2+、Mg2+、Na+、K+和NH4+)质量浓度进行了分析.结果表明,所有样品实测pH均高于5.6.3个采样点ρ(总离子)平均值为丽江市区>索道地区>冰川区,其中ρ(SO4 2-)和ρ(Ca2+)均最高.丽江市区季风前后各离子质量浓度变化显著,其中海盐离子质量浓度〔ρ(Na+)和ρ(Cl-)〕从季风前期到季风期变化不大,在季风后期增加;ρ(NO3-)、ρ(SO42-)、ρ(NH4+)、ρ(Ca2+)、ρ(K+)和ρ(Mg2+)在季风前期显著高于季风期和季风后期.采用相关分析和主因子分析法对降水中离子来源进行研究,表明SO42-、NO3-和NH4+主要来自局地人类活动的贡献,Na+、K+和Cl-是海洋源贡献,Ca2+和Mg2+主要来源于地表粉尘.      

Adsorption and desorption of Cu~(2+) on paddy soil aggregates pretreated with different levels of phosphate

Interactions between anions and cations are important for understanding the behaviors of chemical pollutants and their potential risks in the environment.Here we prepared soil aggregates of a yellow paddy soil from the Taihu Lake region,and investigated the effects of phosphate(P) pretreatment on adsorption-desorption of Cu~(2+) of soil aggregates,free iron oxyhydrates-removed soil aggregates,goethite,and kaolinite with batch adsorption method.The results showed that Cu~(2+) adsorption was reduced on the aggregates pretreated with low concentrations of P,and promoted with high concentrations of P,showing a V-shaped change.Compared with the untreated aggregates,the adsorption capacity of Cu~(2+) was reduced when P application rates were lower than 260,220,130 and110 mg/kg for coarse,clay,silt and fine sand fractions,respectively.On the contrary,the adsorption capacity of Cu~(2+) was higher on P-pretreated soil aggregates than on the control ones when P application rates were greater than those values.However,the desorption of Cu~(2+) was enhanced at low levels of P,but suppressed at high levels of P,displaying an inverted V-shaped change over P adsorption.The Cu~(2+) adsorption by the aggregate particles with and without P pretreatments was well described by the Freundlich equation.Similar results were obtained on P-pretreated goethite.However,such P effects on Cu~(2+)adsorption-desorption were not observed on kaolinite and free iron oxyhydrates-removed soil aggregates.The present results indicate that goethite is one of the main soil substances responsible for the P-induced promotion and inhibition of Cu~(2+) adsorption.     

Adsorption of herbicide triclopyr on homoionic clays

ＡｄｓｏｒｐｔｉｏｎｏｆｈｅｒｂｉｃｉｄｅｔｒｉｃｌｏｐｙｒｏｎｈｏｍｏｉｏｎｉｃｃｌａｙｓＬｉｕＷｅｉｐｉｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＺｈｅｊｉａｎｇＵｎｉｖｅｒｓｉｔｙ，Ｈａｎｇｚｈｏｕ３１００２７，Ｃｈｉｎａ）ＡｌｂａＰｕ...     

Experimental and density functional theory study of the adsorption of N2O on ion-exchanged ZSM-5: Part II. The adsorption of N2O on main-group ion-exchanged ZSM-5

The adsorption and desorption of N2O on main-group ion-exchanged ZSM-5 was studied using temperature-programmed desorption (TPD) and density functional theory (DFT) calculations. TPD experiments were carried out to determine the desorbed temperature Tmax corresponding to the maximum mass intensity of N2O desorption peak and adsorption capacity of N2O on metal-ion-exchanged ZSM- 5s. The results indicated that Tmax followed a sequence of Ba2+ > Ca2+ > Cs+ > K+ > Na+ > Mg2+and the amount of adsorbed N2O on main-group metal cation followed a sequence of Ba2+ > Mg2+ > Ca2+ > Na+ > K+ > Cs+. The DFT calculations were performed to obtain the adsorption energy (Eads), which represents the strength of the interaction between metal cations and the N-end or O-end of N2O. The calculation results showed that the N-end of the N2O molecule was favorably adsorbed on ion-exchanged ZSM-5, except for Cs-ZSM-5. For alkali metal cations, the Eads of N2O on cations followed the order which was the same to that of Tmax: Cs+ > K+ > Na+. The calculated and experimental results consistently showed that the adsorption performances of alkaline-earth metal cations were better than those of alkali metal cations.     

壳聚糖插层累托石的研制及对Cu2+的吸附

以钙基累托石原料制备壳聚糖插层累托石复合吸附剂,并通过红外光谱对其结果进行了表征.研究了复合吸附剂对Cu<'2+>的吸附,分别讨论了复合吸附剂的不同配比、搅拌时间、pH值、投加量和温度对吸附效果的影响.结果表明:当壳聚糖/累托石复合吸附剂1:3的配比,pH 6,吸附时间为30 min,投加量为0.75 g/L和温度为3...     

胡敏酸-针铁矿复合胶体对Pb2+的吸附特征

采用批平衡试验法,研究了胡敏酸-针铁矿复合胶体对Pb2+的等温吸附特征及pH值、离子强度、温度及共存Cd2+对复合胶体吸附Pb2+的影响.结果表明:在相同离子强度和温度条件下,pH值升高,最大吸附量(Smax)和吸附平衡常数(k)均增大,有利于吸附反应的进行.等温吸附方程以Langmuir方程拟合效果最好.当Pb2+平衡浓度为124.7mg/L时,吸附量增幅最大,达35mg/g.复合胶体对Pb2+的吸附动力学方程以Elovich方程拟合效果最好.pH值增大,平衡吸附速率提高.在相同pH值和离子强度条件下,温度升高,最大吸附量、吸附平衡常数、自由能变△G°的绝对值均增加,表明升高温度有利于吸附反应的进行.在相同温度和pH值条件下,复合胶体对Pb2+的吸附量随着离子强度的增加而增加.当存在Cd2+时,复合胶体对Pb2+的吸附量有所降低,但Cd2+对Pb2+竞争吸附影响不大.     

污泥腐殖酸对Cd2+的吸附特性

为了促进污水处理厂剩余污泥的资源化利用,探索S-HA（sludge-based humic acid, 污泥腐殖酸）对溶液中重金属Cd2+的吸附特性.采用国际腐殖酸协会（IHSS）推荐的方法提取S-HA,通过元素分析、FT-IR（傅里叶红外光谱分析）和SEM-EDS（外观形态分析）等方法,考察溶液pH和共存阳离子对吸附过程的影响,并对吸附过程分别进行了吸附动力学模型、等温吸附模型和吸附热力学模型拟合,同时通过对比S-HA吸附前后的红外光谱和扫描电镜-能谱图片,探索S-HA对Cd2+的吸附机制.结果表明:①S-HA表面呈松散的簇团状,含有大量的羧基、醇羟基和酚羟基等含氧官能团,芳香度较高,含有较多的脂肪链结构;S-HA在吸附水中Cd2+的过程中,Cd2+与S-HA表面上的酚羟基、羧基等官能团发生了络合作用.②S-HA对Cd2+的吸附量随溶液pH升高而增加,溶液中Na+、NH₄+和Ca2+等共存阳离子的存在不利于S-HA对Cd2+的吸附,其中Ca2+的存在对S-HA吸附Cd2+影响最大.③S-HA对Cd2+的吸附由快吸附、慢吸附和吸附平衡3个阶段组成,吸附平衡时间为12 h;吸附过程符合准二级动力学模型,其整体吸附速度由液膜扩散和颗粒内扩散共同控制;吸附等温线符合Freundlich等温吸附模型,25℃下的最大吸附量为19.29 mg/g,Cd2+在S-HA上的吸附是自发吸热反应.研究显示:污水处理厂剩余污泥提取的S-HA对Cd2+具有较好的吸附效果;S-HA对Cd2+的吸附过程同时存在着物理吸附和化学吸附;高pH对S-HA吸附Cd2+有促进作用,而高离子强度对S-HA吸附Cd2+有抑制作用.      

Modified activated carbon with interconnected fibrils of iron-oxyhydroxides using Mn2 + as morphology regulator, for a superior arsenic removal from water

The arsenic removal efficiency of iron-modified activated carbons depends greatly on the number of available iron oxide surface sites, which are given by the surface area of the anchored particles. In this sense, aiming the generation of an adsorbent with superior arsenic adsorption capacity, we developed a protocol to anchor interconnected fibrils of iron oxyhydroxides, using Mn^2 + as a morphology regulator. The protocol was based on a microwave-assisted hydrothermal method, using bituminous based activated carbon and both Fe^2 + and Mn^2 + ions in the hydrolysis solution. The elemental analysis of modified carbons revealed that Mn does not anchor to the carbon. However, when Mn is included in the hydrolysis solution, the iron content in the activated carbon increased up to 3.5?wt%, without considerable decreasing the adsorbent surface area. Under specific hydrothermal conditions, the Mn^2 + promoted the formation of iron oxide nanoparticles shaped as interconnected fibrils. This material showed a superior arsenic adsorption capacity in comparison to similar iron modified activated carbons (5?mg As/g carbon, at 2?mg As/L), attributed to the increase in quantity and availability of active sites located on the novel interconnected fibrils of iron oxyhydroxides nanostructures.     

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。     

深海适冷菌Pseudoalteromonas sp.SM9913胞外多糖对Pb~(2+)和Cu~(2+)的吸附性能研究

采用深海适冷菌Pseudoalteromonas sp. SM9913分泌的胞外多糖(EPS)分别对Pb2+和Cu2+进行吸附,研究了多糖用量、pH、吸附时间和共存离子对EPS吸附性能的影响及EPS对Pb2+和Cu2+的吸附热力学.结果表明,EPS对Pb2+和Cu2+的吸附量随EPS投加量的增加而减小.EPS对Pb2+和Cu2+的最佳吸附pH分别为4.5～5.5和4.5～6.0. EPS对Cu2+的吸附平衡时间为90 min,对Pb2+的吸附平衡时间则长达180 min.共存离子Ca2+、Mg2+、Na+、K+的加入均降低了EPS对Pb2+的吸附量,Ca2+、Mg2+的加入降低了EPS对Cu2+的吸附量,但低浓度的Na+和实验范围浓度的K+不仅没有降低反而增加了EPS对Cu2+的吸附量.Freundlich和Dubinin-Radushkevich方程均能较好地描述SM9913胞外多糖吸附Pb2+和Cu2+的热力学过程,由Dubinin-Radushkevich方程得到SM9913胞外多糖对Pb2+和Cu2+的最大吸附量分别为243.3 mg/g (10℃) 和36.7 mg/g (40℃).胞外多糖吸附金属离子前后的红外光谱分析表明,多聚糖中C-O-C、乙酰基和羟基是起主要吸附作用的官能团.     

北京大气PM10中水溶性金属盐的在线观测与浓度特征研究

研究了北京大气可吸入气溶胶（PM10）中水溶性金属盐的变化特征,并对其来源进行了分析。钠盐、钾盐、镁盐、钙盐浓度的变化范围分别为：0.5～1.4μg/m3、0.5～2.5μg/m3、0.1～0.5μg/m3、0.6～5.8μg/m3,不同水溶性金属盐最高值和最低值出现季节不同。水溶性金属盐没有明显的采暖期和非采暖期的差异,说明冬季采暖不是它们的主要来源。海盐和土壤源是北京大气PM10中Na+的主要来源,K+的主要来源包括秸秆燃烧和生物质排放,土壤源是Mg2+和Ca2+的重要来源。水溶性金属盐的日变化规律不同。降水对Na+、K+、Mg2+、Ca2+的清除分别为10％～70％、20％～80％、10％～77％、5％～80％。