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。     

铁铝氧化物–层状硅酸盐矿物互作对Cr (Ⅵ)和As (Ⅴ)吸附的影响

以高岭石、蒙脱土、针铁矿和三水铝石四种单一典型土壤矿物以及针铁矿-蒙脱石和三水铝石-蒙脱石（质量比为1:1）两种代表性土壤矿物复合体为吸附材料，采用吸附平衡实验、能谱分析（(EDS）、红外光谱、扫描电镜、酸碱滴定和zeta电位测定等方法，研究了铁铝氧化物与层状硅酸盐矿物之间的相互作用对Cr(Ⅵ)和As(Ⅴ)吸附的影响及其机制。吸附平衡实验和EDS实验结果表明，两种复合体对Cr(Ⅵ)和As(Ⅴ)的吸附容量均小于其两种组成矿物单一体系吸附量的平均值，即铁铝氧化物与蒙脱石的互作降低了这些氧化物对Cr(Ⅵ)和As(Ⅴ)的吸附能力。表面性质表征结果表明，与蒙脱石复合后，针铁矿与三水铝石表面的正电荷均被完全中和，电荷符号发生反转。与理论值相比，三水铝石-蒙脱石复合体的表面位点总浓度无明显变化，比表面积减小。针铁矿-蒙脱石复合体的比表面积与理论值无明显差异，但矿物表面位点浓度减小，表面羟基红外吸收峰强度减弱。氧化物与层状硅酸盐矿物互作改变了矿物表面性质，这可能是导致氧化物对Cr(Ⅵ)和As(Ⅴ)的吸附能力降低的主要原因。当评估污染元素在土壤中有效性时应当考虑土壤固相组分间的互作对离子吸附的影响。     

磺胺嘧啶在土壤及土壤组分中的吸附/解吸动力学

抗生素在土壤中的吸附/解吸及迁移过程受其理化性质的强烈影响,其中土壤中的矿物成分,如高岭石、蒙脱石及腐殖酸等是重要控制因素。本文主要研究了磺胺嘧啶在土壤、高岭石、蒙脱石和腐殖酸中的吸附/解吸动力学过程,并对反应前后的高岭石、蒙脱石和腐殖酸进行傅里叶红外光谱(Fourier transform infrared, FTIR)表征,探讨其可能的吸附机理。结果表明:磺胺嘧啶的吸附(解吸)动力学过程,可以分为快速吸附(解吸)、吸附解吸动态平衡和吸附(解吸)平衡3个阶段;磺胺嘧啶在土壤及其3种组分中的吸附(解吸)均可在24 h内达到平衡,其浓度高低会导致土壤及其组分的吸附差异,不同土壤组分中的官能团含量、带电性质及氢键是造成吸附差异的主要原因;分别用伪一级动力学模型、伪二级动力学模型和Elovich模型对其吸附过程进行拟合,其动力学吸附过程更符合伪二级动力学模型,R20.99,主要受控于物理化学吸附;FTIR图谱表明磺胺嘧啶与高岭石以物理吸附为主,并有少量氢键作用,与蒙脱石之间主要以氢键作用完成吸附,而在腐殖酸中存在表面络合和π–π共轭作用。     

几种粘土矿物和一些土壤的钾固定

6种矿物和10个土壤样本固定的钾随加入的钾浓度增加而增加。所有样本固定的迟缓效钾很低,固定的缓效钾随矿物性质和土壤组成而变化,固定能力的顺序是:高岭石<云母<伊利石<蛭石;砖红壤和赤红壤<红壤<潮土和黄土<黄棕壤。以高岭石和蒙脱石为主并含一定量的伊利石和云母的土壤,其粘粒含量明显地影响土壤的固钾力,含较粗粒蛭石多的土壤,固钾力也明显。根据土壤的固钾率,可计算出5种施钾水平的各类土壤固钾量,为合理施用钾肥提供参考意见。     

几种土壤及黏土矿物对多氯联苯吸附特性的研究

采用批量平衡试验,研究了不同土壤及长黏土矿物对多氯联苯吸附特性。结果表明:多氯联苯浓度范围为0.25~5.0mg L-1时,不同土壤及黏土矿物对多氯联苯的吸附均能用Freundlich方程很好地拟合,随着溶液中多氯联苯浓度的增加,土壤及黏土矿物对多氯联苯的吸附量增加;几种土壤对多氯联苯吸附量大小顺序为:红壤>黄褐土>砂姜黑土,土壤有机质、粘粒等对多氯联苯吸附起主要作用,土壤更易吸附高氯代PCB77;黏土矿物对多氯联苯吸附量大小顺序为:纳米蒙脱石>纳米SiO2>凹凸棒石,黏土矿物吸附多氯联苯能力的大小与黏土矿物的比表面积、粒径、层状结构等有关;多氯联苯本身分子的大小影响其在黏土矿物上的吸附;土壤中添加黏土矿物可以提高对多氯联苯的吸附。     

土壤镉吸附的研究进展

综述了土壤镉吸附的机理和土壤pH、有机质含量、粘粒矿物类型及含量、土壤溶液中竞争性阳离子、共存阴离子、土壤温度等土壤性质对土壤镉吸附的影响；总结了土壤镉的吸附量随土壤pH增加、温度升高及有机质、铁锰氧化物和粘土矿物含量增加而增加的机理；竞争性阳离子的存在抑制镉的吸附，土壤溶液中共存阴离子对镉吸附的影响取决于阴离子种类和土壤类型。     

广西水耕人为土黏粒矿物组成及其空间分布特征

黏粒矿物影响着土壤理化性质，可指示成土因素特征和土壤发生发育过程/强度，也是中国土壤系统分类的基层单元土族矿物学类型划分的重要依据。本研究选择了广西不同纬度和成土母质的18个代表性水耕人为土的剖面，应用X射线衍射（XRD）方法分析了其典型水耕氧化还原层（Br层）的黏粒矿物组成及其空间分布特征，并确定了其中“黏质”剖面的土族控制层段矿物学类型。结果表明：（1）供试土壤的黏粒矿物主要包括高岭石、伊利石、三水铝石、1.42 nm过渡矿物、蒙脱石和蛭石等，依次分别出现在100%、88.9%、72.2%、61.1%、44.4%和38.9%的剖面中。（2）黏粒矿物组成在纬度空间分布上具有明显规律性特征。随着纬度降低，土壤黏粒中的高岭石增加，伊利石、蒙脱石、1.42nm过渡矿物逐渐减少；纬度＞23°N区域内，成土母质对黏粒矿物组成影响明显。（3）纬度23°N是黏粒矿物组成和土族矿物学类型分界线，＜23°N区域，黏粒矿物均以高岭石为主，是“黏质”剖面的土族控制层段的主要矿物学类型；＞23°N区域，黏粒矿物组成以高岭石、蒙脱石、伊利石或1.42 nm过渡矿物为主，因成土母质不同而异，“黏质”剖面的土族控制层段矿物学类型包括高岭石混合型、混合型和伊利石型。     

细菌在两种土壤矿物表面吸附的热力学分析

运用表面热力学方法和扩展的DLVO理论,对两种典型土壤细菌恶臭假单胞菌(Pseudom onasputida)和枯草芽孢杆菌(Bacillus subtilis)在代表性土壤黏粒矿物高岭石和蒙脱石表面的吸附进行了分析,获得了黏粒矿物与细菌作用的疏水自由能变(ΔGH)和静电力自由能变(ΔGEL)及总自由能变(ΔG)。发现疏水自由能为负,显示疏水作用为引力,有利于细菌在黏粒矿物表面的吸附;而静电力自由能为正,表明细菌-矿物间存在静电斥力。疏水自由能显著大于静电力自由能,表明疏水作用在黏粒矿物对细菌吸附时的贡献大于静电力。两种细菌与两种矿物间的总吸附自由能为负值,意味着细菌在矿物表面的吸附是热力学自发过程。高岭石对细菌的吸附自由能大于蒙脱石对细菌的吸附自由能,表明细菌与高岭石间的亲和力较高,吸附更容易发生,这与化学吸附及滴定量热结果一致。表面热力学方法和XDLVO理论在预测细菌-矿物相互作用中有重要意义,但该方法未考虑多种非DLVO效应,如细胞表面多聚物、细菌鞭毛等在吸附反应中的作用,因此还存在一定的局限性,在揭示细菌-矿物相互作用的热力学机理方面还需与其他研究技术结合。     

西辽河平原两种常见土壤颗粒中黏土矿物的组成特征

【目的】土壤是由大小和形态各异的颗粒构成，各级颗粒包含丰富的黏土矿物演化信息。明确西辽河平原黏土矿物组成及演化特征有助于了解该地区土壤发育程度及肥力状况，为当地土壤资源合理利用提供理论依据。【方法】以西辽河平原分布较多的栗钙土和盐碱土为研究对象，采集表层土壤并分离不同粒级的土壤颗粒(<2、0.45～2、0.1～0.45μm)，利用X射线衍射(XRD)和化学分析等方法研究黏土矿物组成及相关土壤指标。【结果】XRD分析结果表明，西辽河平原栗钙土和盐碱土的黏土矿物均以伊利石-蛭石-绿泥石为主，栗钙土中伴有少量高岭石和伊/蒙混层矿物，而盐碱土中含有少量高岭石、蒙脱石和1.4 nm过渡矿物；随粒径减小，栗钙土和盐碱土颗粒中绿泥石、高岭石、蒙脱石(伊/蒙混层矿物)和1.4 nm过渡矿物含量均减少，伊利石和蛭石含量增加；伊利石结晶度在栗钙土、盐碱土以及不同粒级的土壤颗粒中也存在明显差异。盐碱土中伊利石结晶程度较栗钙土弱。随粒径减小，栗钙土和盐碱土中伊利石结晶程度均变弱。化学分析结果表明，西辽河平原盐碱土中Na₂O的含量明显高于栗钙土，栗钙土和盐碱土颗粒的风化程度均随粒径减...     

准噶尔和塔里木盆地盐渍化土壤黏土矿物组成特征及成因

新疆是中国盐渍化土壤主要分布区,本研究在新疆准噶尔盆地和塔里木盆地采集不同盐化程度土壤,利用X-射线衍射仪、透射电镜、X射线荧光光谱技术,研究两个盆地内盐渍化土壤中黏土矿物的分布特点。结果表明:受干旱气候的影响,两大盆地盐渍化土壤中黏土矿物主要包括伊利石、蒙脱石、绿泥石和高岭石,其中塔里木盆地盐渍化土壤中蒙脱石含量极少。土壤次生碳酸盐δ13C和δ18O及黏土矿物D和δ18O测定结果显示,塔里木盆地采样点土壤形成期气候相对准噶尔盆地更干旱,这种干旱气候导致伊利石中K+不易脱去,从而影响蒙脱石形成。在相对湿润的准噶尔盆地,采样点盐渍化土壤中蒙脱石含量较高,且蒙脱石含量随着伊利石含量减少而增加,两者之间达到极显著负相关关系(r=0.81,n=30,P0.01),表明土壤中存在伊利石向蒙脱石的转化过程。准噶尔盆地盐渍化土壤具备伊利石向蒙脱石转化所需要的水分条件和化学组分:①相对湿润气候条件下伊利石发生脱K+;②盐渍化土壤pH8.5,使长石中的Si4+溶解,参与矿物转化过程;③盐渍化土壤溶液中大量Ca2+、Na+和Mg2+可进入伊利石层间占据K+空位,形成蒙脱石。同时,研究结果还显示10 cm以下土层土壤盐分含量与伊利石含量存在极显著负相关关系(r=0.76,n=22,P0.01),表明10 cm以下土体中,盐分的存在利于准噶尔盆地盐渍化土壤中伊利石向蒙脱石转换。因此,气候和盐分含量是新疆两大盆地盐渍化土壤中黏土矿物形成和转化的主要影响因素。     

有机酸对高岭石, 针铁矿和水铝英石吸附镉的影响

Effects of organic acids （oxalic, acetic, and citric） on adsorption characteristics of Cadmium （Cd） on soil clay minerals （kaolinite, goethite, and bayerite） were studied under different concentrations and different pH values. Although the types of organic acids and minerals were different, the effects of the organic acids on the adsorption of Cd on the minerals were similar, i.e., the amount of adsorbed Cd with an initial solution pH of 5.0 and initial Cd concentration of 35 mg L^-1 increased with increasing concentration of the organic acid in solution at lower concentrations, and decreased at higher concentrations. The percentage of Cd adsorbed on the minerals in the presence of the organic acids increased considerably with increasing pH of the solution. Meanwhile, different Cd adsorption in the presence of the organic acids, due to different properties on both organic acids and clay minerals, on kaolinite, goethite, or bayerite for different pHs or organic acid concentrations was found.     

Adsorption of Acrylonitrile on Some Soils and Minerals from Aqueous Solutions

Equilibrium and kinetic studies have been made on the adsorption of acrylonitrile(CH2=CHCN) on three soils and four minerals from aqueous solutions.It was shown that the organic matter was the major factor affecting the adsorption process in the soils.The conformity of the equilibrium data to linear type(one soil) and Langmuir type(two soils) isotherms indicated that different mechanisms were involved in the adsorption.This behavior appears bo be related to the hydrophobicity of soil organic matter due to their composition and E4/E6 ratio of humic acids.The adsorption kinetics were also different among the soils,indicating the difference in porosity of organic matter among the soils,and the kinetics strongly affected the adsorption capacity of soils for acrylonitrile.Acrylonitrile was slightly adsorbed from aqueous solutions on pyrophyllite with electrically neutral and hydrophobic nature,and practically not on montmorillonite and kaolinite saturated with Ca.However,much higher adsorption occurred on the zeolitized coal ash,probably caused by high organic carbon content(107g/kg).     

Influence of soil composition on adsorption of glyphosate and phosphate by contrasting Danish surface soils

The herbicide glyphosate and inorganic phosphate are strongly adsorbed by inorganic soil components, especially aluminium and iron oxides, where they seem to compete for the same adsorption sites. Consequently, heavy phosphate application may exhaust soil's capacity to bind glyphosate, which may lead to pollution of drain‐ and groundwater. Adsorption of phosphate and glyphosate to five contrasting Danish surface soils was investigated by batch adsorption experiments. The different soils adsorbed different amounts of glyphosate and phosphate, and there was some competition between glyphosate and phosphate for adsorption sites, but the adsorption of glyphosate and phosphate seemed to be both competitive and additive. The competition was, however, less pronounced than found for goethite and gibbsite in an earlier study. The soil's pH seemed to be the only important factor in determining the amount of glyphosate and phosphate that could be adsorbed by the soils; consequently, glyphosate and phosphate adsorption by the soils was well predicted by pH, though predictions were somewhat improved by incorporation of oxalate‐extractable iron. Other soil factors such as organic carbon, the clay content and the mineralogy of the clay fraction had no effect on glyphosate and phosphate adsorption. The effect of pH on the adsorption of glyphosate and phosphate in one of the soils was further investigated by batch experiments with pH adjusted to 6, 7 and 8. These experiments showed that pH strongly influenced the adsorption of glyphosate. A decrease in pH resulted in increasing glyphosate adsorption, while pH had only a small effect on phosphate adsorption.     

山东主要果园土壤的粘土矿物组成及其吸附特性

研究了山东主要果园土壤中粘土矿物的组成、类型及其对P、K和Cu、Zn、Pb金属元素的吸附特性。结果表明：山东主要果园土壤的粘土矿物类型存在着明显的差异,淋溶较强,酸度较大的棕壤（简育湿润淋溶土）中粘土矿物以高岭石占优势,对P的吸附较强,但对K＋吸附固定较弱。含游离C aCO3较高的潮土（淡色潮湿雏形土）和褐土（简育干润淋溶土）,对P有较强的吸附和沉淀作用,使土壤磷的有效性降低。而砂姜黑土（钙积潮湿变性土）由于含有较高的蒙脱石和1.4 nm过渡矿物,对K＋具有很强的吸附和晶穴固定作用,因此砂姜黑土中磷肥和钾肥的有效性均较低,在施肥上应采取集中施肥和保持较湿润土壤环境等措施,以提高养分有效性。砂姜黑土和潮土对Cu、Zn、Pb金属元素的吸附显著地大于棕壤和褐土,主要的影响因素是不同土壤的粘粒含量和粘土矿物的类型的差异。同一土壤对Pb的吸附量远远大于对Zn和Cu的吸附量,主要取决于金属元素本身的化学性质和胶体的吸附特性。     

磷的吸附和表面电荷特征及其与华南地区某些土壤矿物的关系

The phosphate adsorption and surface charge characteristics of the tropical and subtropical soils derived from different parent materials in China were determined, and their relations to soil mineralogy were analysed. The results showed that all soil phosphate adsorption curves were well fitted by Freundlich equation and Langmuir equation. The maximum buffering capacity of P ranged from 66 to 9 880 mg kg^-1, with an increasing order of purple soil, skeletal soil, red soil, lateritic red soil, yellow soil and latosol; and the highest value was 149 times the lowest value, which indicated great differences among these soils in phosphate adsorption and supplying characteristics. The pH₀ (zero point of charge) values obtained by salt titration-potential titration varied from 3.03 to 5.49, and the highest value was found in the latosol derived from basalt whereas the lowest value was found in the purple soil. The correlation analysis indicated that the main minerals responsible for phosphate adsorption in the soils were gibbsite, amorphous iron oxide and kaolinite; and the pH₀ was mainly controlled by kaolinite, gibbsite and oxides.     

根瘤菌存在下土壤胶体和矿物对镉的吸附

Experiments were conducted to study the adsorption of Cd on two soil collids(red soil and yellowbrown soil) and three variable-charge minerals (goethite,noncrystalline Fe oxide and kaolin) in the absence and presence of rhizobia.The tested strain Rhizobium fredii C6,tolerant to 0.8 mmol L^-1 Cd,was selected from 30 rhizobial strains.Results showed that the isotherms for the adsorption of Cd by examined soil colloids and minerals in the presence of rhizobia could be described by Langmuir equation.Within the range of the numbers of rhizobial cells studied,the amount of Cd adsorbed by each system increased with increasing rhizobial cells,Greater increases for the adsorption of Cd were found in red soil and kaolin systems.Rhizobia influence on the adsorption of Cd by examined soil colloids and minerals was different from that on the adsorption of Cu.The presence of rhizobia increased the adsorption affinity of soil colloids and minerals for Cd,particularly for the goethite and kaolin systems.The discrepancies in the influence of rhizobia on the adsorbability and affinity of selected soil colloids and minerals for Cd suggesed the different interactions of rhizobia with various soil components.It is assumed that bacterial biomass plays an important role in controlling the mobility and bioavailability of Cd in soils with kaolinite and goethite as the major colloidal compnents,such as in variable-charge soil.     

A comparative study of Cd,Cr(III), Cr(VI), Hg,and Pb uptake by minerals and soil materials

The pH dependency of Cd, Cr(III), Cr(VI), Hg, and Pb uptake by 14 different types of minerals and soil materials has been studied. The solids were interacted with metal solutions separately in a batch procedure, and the percentage of metal uptake of different metal-solid combinations was compared and evaluated. The results were quantified by the pH values at which 10, 50 and 90% of the metal uptake took place. Physical and chemical characteristics of the solids were correlated with metal uptake. The results verify the importance of geochemical parameters of soils such as organic content, type of clay mineral, presence of complexing ions, and redox-potential for controlling metal uptake. Retention of Cd, Cr(VI), Hg, and Pb was found to be strongly dependent on organic content of the materials studied. Montmorillonite (in bentonite and smectite) showed the highest uptake of Cd, Cr(III) and Pb among all minerals and soil materials, while illite and kaolinite showed lower uptake than the soils. At low pH, the uptake percentage of Cr(VI) by organic soils was higher than that of any of the other metal ions. The uptake of Hg was low in comparison to other cations, which may be explained by formation of soluble Hg(CI)₂° or Hg(CI)⁴ _2? complexes.     

邻苯二甲酸和水杨酸在可变电荷土壤中的吸附行为

研究了2种低分子量有机酸邻苯二甲酸和水杨酸在2种代表性可变电荷土壤红壤和砖红壤中的吸附行为。结果表明,可变电荷土壤对有机酸的吸附容量较大,对邻苯二甲酸的吸附亲和力大于对水杨酸的亲和力,在砖红壤中2种有机酸的吸附量大于在红壤中的,这与土壤的游离铁、铝氧化物的含量一致。土壤氧化铁在有机酸吸附中起着重要作用,粘土矿物如高岭石对有机酸的吸附量很小。有机酸的吸附涉及专性吸附和静电吸附2种机制,并以前者为主。当pH小于4.5时,pH的改变对有机酸的吸附影响不大;当pH大于4.5时,有机酸的吸附量随pH的增加而减小。     

Adsorption of phthalic acid and salicylic acid by two variable charge soils as influenced by sulphate and phosphate

Low‐molecular‐weight (LMW) organic acids exist widely in soils, especially in the rhizosphere, and the adsorption of these acids may affect their reactions in soils. The adsorption behaviour of phthalic acid and salicylic acid by two variable charge soils (a Rhodic Ferralsol and a Haplic Acrisol) was investigated. Both soils exhibited great adsorption capacity for these organic acids, with a greater affinity for phthalic acid. The Rhodic Ferralsol adsorbed more organic acids of both kinds than the Haplic Acrisol, which was consistent with the content of iron and aluminum oxides in the two soils. The iron oxides in these soils played a significant role in adsorption of the organic acids, whilst the soil aluminosilicate minerals, such as kaolinite, showed a small adsorption capacity. The presence of phosphate and sulphate caused a decrease in the adsorption of both organic acids because of their competition with them for sorption sites. The phosphate showed a bigger inhibition on the adsorption than sulphate as a result of a greater amount of phosphate adsorbed by the soils. The adsorption of both organic acids was affected by pH only slightly at pH < 4.5. However, the adsorption decreased with the increase in pH at pH > 4.5. A similar trend was observed for the phosphate system, but the opposite was seen for the sulphate system. This suggests that the inhibition of sulphate on the adsorption of the organic acids decreased with the increase in pH, because the adsorption of sulphate decreased strongly with increasing pH.