Effect of Low Molecular Weight Organic Anions on the Adsorption of NO3− by Variable Charge Soils

Low molecular weight organic acids exist widely in soils and have been implicated in many soil processes. The results in the present paper showed that the presence of organic anions led to a decrease in the adsorption of NO₃⁻. The effect of citrate was much larger than that of oxalate and malate. Among different soils, the effect for Hyper-Rhodic Ferralsol and Rhodic Ferralsol was larger than that for Haplic Acrisol, which was related to the content of iron oxides in these soils. The effect of organic anions decreased with the increases in pH value and the amount of organic anions added. The organic anions depressed the adsorption of NO₃⁻ through two mechanisms, the competition of the organic anions for adsorption sites with NO₃⁻ and the change of soil surface charge caused by the specific adsorption of organic anions.     

Effect of Zn Adsorption on Charge of Variable Charge Soils

The variation in appa rent carge of two typical variable charge soils resulting from Zn adsorption were studied by KCl saturation and NH4NO3 replacement methods.Results showed that zinc were adsorbed specifically to those sites with negative charge.As in different pH ranges,the percantages of specific and electrostatic adsorptions of zine and the mechanisms of specific adsorption were different,the effects of Zn adsorption on apparent charge were varied and could be characterized as:when 1 mmol Zn^2 was adsorbed,a change about 1 mmol in the apparent charge was observed in the low pH range(1),1.4 to 1.5mmol in the moderate pH range(II) and 0.55 to 0.6mmol in the high pH range (III).These experimental data,in terms of soil charge,proved once more author‘s conclusion in the preceding paper(Sun,1993) that in accordance with the behaviors of Zn adsorption by the variable charge soils in relation to pH,three pH ranges with different adsorption mechanisms were delineated;that is,in Range I,specific adsorption was the predominant mechanism,in Ranges II and III,specific and electrostatic adsorptions co-existed,but their specific adsorption mechanisms were not identical.     

Adsorption of Phosphate on Variable Charge Soils

The study about the adsorption of phosphate on four variable charge soils and some minerals revealed that two stage adsorption appeared in the adsorption isotherms of phosphate on 4 soils and there was a maximum adsorption on Al-oxide-typed surfaces between pH 3.5 to pH 5.5 as suspension pH changed from 2 to 9, but the adsorption amount of phosphate decreased continually as pH rose on Fe-oxide typed surfaces. The adsorption amount of phosphate and the maximum phosphate adsorption pH decreased in the order of yellow-red soil > lateritic red soil > red soil > paddy soil, which was coincided with the content order of amorphous Al oxide. The removement of organic matter and Fe oxide made the maximum phosphate adsorption pH rise from 4.0 to 5.0 and 4.5, respectively. The desorption curves with pH of four soils showed that phosphate desorbed least at pH 5. Generally the desorption was contrary to the adsorption with pH changing.     

恒电荷土壤与可变电荷土壤K+的吸附特性

对我国 3种典型可变电荷土壤和 4种恒电荷土壤在不同 K 浓度和 p H下 K 的吸附特性进行了研究。结果表明 ,两类土壤 K 吸附量均随平衡 K 浓度增加而增加 ,在低浓度 (添加K 0 .1～ 1.0 mmol/ L )时两者符合线性 ,在高浓度 (添加 K 0 .5～ 5 .0 mmol/ L )下两者符合Langmuir方程。L angmuir方程的参数 K两类土壤间差异不大 ,但以可变电荷土壤 >恒电荷土壤 ,说明前类土壤 K吸附结合能较大 ,吸附 K 不易解吸 ,K 有效性较低。p H降低使土壤 K 吸附量减少 ,但恒电荷土壤与可变电荷土壤减少的机理不同 ,前者主要是由于 H 与 K 的竟争吸附 ,而后者主要是由于表面负电荷减少而引起的电性引力的改变。     

Adsorption of Potassium and Sodium Ions by Variable Charge Soils

Adsorption of potassium and sodium ions by four typical variable charge soils of South China was studied.The results indicated that the variable charge soils saturated with H and Al showed a much higher preference for potassium ions relative to sodium ions,and this tendence could not be changed by such factors as the pH,the concentration of the cations,the dielectric constant of solvent,the accompanying anions and the iron oxide content etc.,suggesting that this difference in affinity is caused by the difference in the nature of the two cations.It was observed that a negative adsorption of sodium ions by latosol and lateritic red soil in a mixed system containing equal amount of potassium and sodium ions at low pH,which is caused by a competitive adsorption of potassium and sodium ions and repulsion of positive charge on the surfaces of soil particles for cations.The adsorption of potassium and sodium ions increased with the decreases in the dielectric constant of solvent and the iron oxide content.Sulfate affected the adsorption of potassium and sodium ions through changing the surface properties of the soils.     

Adsorption of Potassium and Calcium Ions by Variable Charge Soils

Interactions of potassium and calcium ions with four typical variable charge soils in South China were examined by measuring pK-0.5pCa value with a potassium ion-selective electrode and a calcium ion-selective electrode,and pK value with a potassium ion-selective electrode.The results showed that adsorption of potassium and calcium ions increased with soil suspension pH,and the tendency of the pK-0.5pCa value changing with pH differed with respect to pH range and potassium to calcium ratio.Adsorption of equal amount of calcium and potassium ions led to release of an identical number of protons,suggesting similar adsorption characteristics of these two ions when adsorbed by variable charge soils.Compared with red soil,latosol and lateritic red soil had higher adsorption selectivities for calcium ion.The red soil had a greater affinity for potassium ion than that for calcium ion at low concentration,which seems to result from its possession of 2:1 type minerals,such as vermiculite and mica with a high affinity for potassium ion.The results indicated that adsorption of potassium and calcium ions by the variable charge soils was chiefly caused by the electrostatic attraction between the cations and the soil surfaces.Moreover,it was found that sulfate could affect the adsorption by changing soil surface properties and by forming ion-pair.     

Zn Adsorption by Variable Charge Soils in Relation to pH

Zn adsorption by pure oxides or in the presence of a high concentration of inner electrolyte has been extensively studied.But,in studies on Zn adsorption in the complicated soil system,especially in variable charge soils,profound knowledge about the absorption mechanism still lacks.In this paper,taking Zn ion adsorption by two typical variable charge soils as the object of the study,author discusses the relation between Zn adsorption and pH and possible adsorption mechanisms.The results showed that in the low pH range where the amount of Zn adsorbed did not exceed 50% of Zn added,the specific adsorption was the diminant mechanism.The species of Zn specifically adsorbed was free Zn^2 ion.In the middle and high pH ranges,the mechanisms of specific and electrostatic adsorptions co-existed,accounting for about 70% and 30%,respectively.Noteworthily,in the high pH range,the hydroxyl Zn ion (ZnOH^ ) from Zn^2 hydrolysis probably was a preferable species for specific absorption.     

Adsorption of Chloride, Nitrate and Perchlorate by Variable Charge Soils

Two cells consisting of a chloride-selective electrode and a nitrate-selective electrode or of a chloride-selective electrode and a perchlorate-selective electrode were directly put in the soil suspension to determine the concentration ratios Cl-/ NO3- or Cl-/ ClO4- for studying the adsorption of the three anions by variable charge soils. It was found that all the concentration ratios CCl- / CNO3- and CCl- / CClO4- in suspension were smaller than unity when soil samples were in equilibrium with mixed KCl and KNO3 or KCl and KClO4 solutions of equal concentration. The order of the amount of chloride, nitrate and perchlorate adsorbed by variable charge soils was Cl-> NO3-> ClO4- when the soils adsorbed these anions from the solution containing equal concentrations of Cl-, NO3- and ClO4-. Such factors as the pH of the suspension, the iron oxide content of the soil etc. could affect the amounts and the ratios of anions adsorbed.     

红壤中低分子量有机酸的吸附特征

应用平衡法研究了红壤对草酸、柠檬酸、酒石酸和苹果酸的吸附行为。结果表明:红壤对有机酸的吸附量随着有机酸平衡溶液浓度的增加而增加,有机酸种类不同,吸附量也不同。有机酸在红壤中的吸附行为均可以很好地用Langmuir、Freundlich和Temkim方程描述,其中以Langmuir方程的拟合效果最好。红壤对有机酸均具有较高的吸附率,在0.5～20mmolL-1初始浓度范围内,草酸、柠檬酸、酒石酸和苹果酸的吸附率最大分别可达89.2%、77.5%、67.4%和47.1%。红壤对柠檬酸、酒石酸和苹果酸的吸附率均随着有机酸初始浓度的增加先急剧下降(<5mmolL-1),之后缓慢下降至趋于平稳;草酸的吸附率则随着初始浓度的增加而增加,在3mmolL-1左右时达到最大,随后降低至趋于平稳。     

A Model for Anion Electric Adsorption on Variable Charge Soils

A model was established for anion electric adsorption on variable charge surfaces and an equation to describe the relationship of adsorption amount with equalibrium concentration and suspension pH was derived according to the principles of surface reaction between variable charge surface and anions.The adsorption behaviours of nitrate and chloride on variable charge soils were modelled and the results showed that the model could describe the adsorption of nitrate very well.     

酸性条件下可变电荷土壤对铜吸附动力学特征

用自行设计的动力学装置,研究了酸性条件下Cu在可变电荷土壤表面的反应动力学吸附特征。结果表明,在酸性条件下,Cu吸附过程分为快反应和慢反应。从一级动力学方程拟合的参数可知,3种土壤的最大吸附量依次为砖红壤〉赤红壤〉红壤,Cu最大吸附量随酸度增加显著下降;用Elovich方程和抛物线扩散方程常数b值,解释离子的表观扩散速率,3种土壤的b值依次为砖红壤〉赤红壤〉红壤,且随酸度的增大而降低。从相关系数的比较看,Elovich方程在描述Cu的吸附数据比一级动力学方程和抛物线扩散方程要差。在Cu吸附过程中,pH为5．5和4．3时,红壤和赤红壤流出液中有质子释放,质子的释放可能涉及铜离子的水解;而砖红壤在pH为5．5有质子的释放,pH4-3时有质子的消耗。当原液pH为3.3和3．8时,都存在质子的消耗。3种土壤H＋的消耗过程有较大的区别,砖红壤上快速消耗H＋鱼-远远大于红壤和赤红壤。反应初期,H＋质子的消耗是快速反应,主要包括土壤交换阳离子的缓冲作用、土壤表面的质子化及硫酸根专性吸附释放的羟基中和H＋质子;而以后的反应中,H＋质子对矿物的溶解是一缓慢过程。     

低分子量有机酸对可变电荷土壤和矿物表面化学性质的影响

低分子量有机酸是土壤中广泛存在的,它们参与土壤中许多化学过程,在营养元素活化、解铝毒和矿物风化等方面发挥重要作用。本文综述了可变电荷土壤和矿物对低分子量有机酸的吸附及这类有机酸对土壤的表面电荷、动电性质和土壤吸附无机阴、阳离子的影响,为从事相关研究工作的同志提供参考。     

离子强度对可变电荷表面吸附性铜离子解吸的影响:可变电荷土壤

为进一步了解离子强度对可变电荷表面吸附性铜离子连续性解吸的影响,研究两种可变电荷土壤在去离子水和0.1 mol·L~(-1)NaNO_3溶液中吸附铜离子后,依次在去离子水和浓度由低到高的NaNO_3溶液中连续解吸时,离子强度变化对不同pH段铜离子解吸的影响。结果表明,解吸过程中离子强度变化方向对解吸分值随pH升高的变化趋势的影响完全不同,当离子强度由大变小时,解吸分值曲线的总体趋势是随着pH的升高而降低,反之,曲线呈现为钟形,且当去离子水第一次解吸在0.1mol·L~(-1)NaNO_3溶液中吸附的铜离子时,两种可变电荷土壤的第一次去离子水解吸均可出现重吸附现象,但铁质砖红壤解吸分值绝对值要小于红壤。整个解吸过程中,两种可变电荷土壤的铜离子吸附性铜离子的解吸特征与高岭石基本相似,但可变电荷土壤与高岭石以及两种可变电荷土壤之间,解吸分值的变化规律均存在一定的差异性,可变电荷土壤中的氧化铁含量多少被认为是导致这些差异的主要原因。     

Effects of Low Molecular Weight Organic Anions on the Release of Arsenite and Arsenate from a Contaminated Soil

Low-molecular-weight-organic-anions (LMWOAs) are important exudates of plants and may influence the mobility and bioavailability of metals or metalloids. In the present study the effects of selected LMWOAs, citrate, malate and oxalate, on the release of arsenite (As(III)) and arsenate (As(V)) in a contaminated soil were investigated. The organic anions have significant influence upon the release of arsenic from the soil, and a linear relationship exits between the released arsenic and the concentration of LMWOAs in the extractants. pH effects on the arsenite and arsenate adsorption were not significant over the range from 3 to 7. The amounts of arsenite and arsenate released were significantly correlated with the release of Fe, Mn and Al, suggesting that arsenic was mainly released from Fe-, Mn- and Al-oxides or hydroxides in soil. The ratio of released arsenite to arsenate was not influenced by LMWOAs.     

Types of Crystalline Iron Oxides and Phosphate Adsorption in Variable Charge Soils

The types,contents and morphologies of crystalline Fe oxides and their relations to phosphate adsorption on the clay fractions in soils with varable charge in southern China were investigated by means of XRD,TEM,EMA and chemical analysis methods.Results indicated that the types and contents of crystalline Fe oxides varied with the soils examined.The dominant crystaline Fe oxide was hematite in the latosols and goethites in the red soils.In yellow-brown soils,the only crystalline Fe oxide was goethite.The difference between Ald and Alo came mainly from the Al Substituting for Fe in the Fe oxides.The crystal morphology of goethite appeared mainly as subrounded flat or iso-dimensional rather than acicular particles,Hematities occurred in plates of various thickness,Their MCDa/MCDc ratios in the latosols and red soils were generally above 1.5 and below 1.5,respectively.The MCD values of goethites and hematites were 15-25nm and 20-35nm,and their specific surface areas were 80-120m^2/g and 35-75m^2/g,respectively.The goethite crystals were generally smaller,Variations of the total amounts of crystalline Fe oxides in clay fractions were not related to plhophats adsorption.The types,contents and morphologies of crystalline Fe oxides in the soils remarkably affected phosphate adsorption characteristics of the soils.The phosphate adsorption of goethite was much greater than that of hematite,The higher th MCDa/MCDc ratio of hematite,the lower the phosphate adsorption.     

外源低分子量有机酸对土壤中钙素迁移特征的影响

论文采用室内土柱模拟的方法,研究了草酸和柠檬酸2种外源低分子量有机酸对土壤中钙素迁移特征的影响。研究结果表明:添加草酸在淋溶前期抑制了土壤钙素的淋失,在后期则促进了土壤钙素的淋失;添加柠檬酸则极大地促进了土壤钙素的淋失。增加2种低分子量有机酸的浓度均可促进土壤中钙素的淋失。对土壤钙素淋失的作用为柠檬酸草酸。其中添加草酸和柠檬酸解离产生的H+对钙素的淋失影响相对较大。施入2种有机酸后促进了钙素的淋失,减少了土柱剖面土壤全钙的含量,但淋洗后仍增加了土壤剖面有效钙的含量。     

暗棕壤中低分子有机酸的吸附与生物降解研究

低分子有机酸在森林生态系统中普遍存在,在根际和多种成土过程中发挥重要作用,但有机酸发挥作用的能力和效率与其在土壤中的吸附与降解等行为关系密切。本文研究了草酸、柠檬酸和苹果酸等低分子有机酸在森林暗棕壤A1层和B层的吸附及生物降解行为,结果表明,低分子有机酸加入到暗棕壤后迅速被土壤固相颗粒所吸附,其中对草酸的吸附远强于柠檬酸和苹果酸,三种低分子有机酸在暗棕壤A1层的吸附率强于B层;草酸、柠檬酸和苹果酸加入到森林暗棕壤后还能迅速被微生物降解,其中对草酸的降解远低于柠檬酸和苹果酸,暗棕壤对草酸较强的吸附作用可能是其生物降解率较低的主要原因,且三种低分子有机酸在A1层暗棕壤中的生物降解率高于B层。     

Contribution of Iron and Aluminum Oxides to Electrokinetic Characteristics of Variable Charge Soils in Relation to Surface Charge

The contribution of iron and aluminum oxides to electrokinetic characteristics of variable charge soils was studied through determination of electrophoretic mobilities of the red soils treated with either removal of iron oxides or coating of aluminum oxides,and of those deferrated under natural conditions.After removal of the iron oxides,zeta potentials of the latosol and the red earth decreased obviously with a shift of IEP to a lower pH,from 6.4 to 5.3 and 4.1 to 2.4 for the former and the latter,respectively,and the electrokinetic change for the latosol was greater than for the red earth.Zeta potentials of the kaolinite sample increased markedly after coated with iron oxides.The striking effect of iron oxides on electrokinetix properties of the soils was also demonstrated by the electrokinetic differences between the samples from the red and white zones of a plinthitic horizon formed naturally,and between the samples from the gley and bottom horizons of a paddy soil derived from a red earth.The coatings of aluminum oxides on the latosol and the yellow earth made their zeta potentials rise pronouncedly and their IEFs move toward higher pHs,from 6.2 to 6.8 and 4.3 to 5.3 for the former and the latter,respectively.The samples with different particle sizes also exhibited some electrokinetic variation.The experiment showed that the effects of iron and aluminum oxides were closely related to the pH and type of the soils.