应用Langmuir等温式解释我国东北某些土壤对磷酸离子的吸附作用

目前应用Langmuir吸附等温式来探讨土壤对磷酸离子的吸附作用,较为广泛.自从Olsen(1957)系统地报道以来,从机理到结合生产实际的研究已有大量的报道,我国近年来也有研究.由于土壤本身组成的复杂性,多数学者用纯物质(如纯粘土或铁与铝的含水氧化物等)进行吸附等温式的机理研究,已取得了很多结果.     

SPECIFIC ADSORPTION OF SILICATE AND PHOSPHATE BY SOILS

The adsorption of silicate and phosphate from pure and mixed solutions by four soils known to fix phosphate strongly has been measured. The adsorption at constant pH for each acid from its pure solution follows the Langmuir isotherm. The maximum adsorption of silicate by three of the soils from the pure solution occurs at pH 9.2, and the maximum adsorption curve for phosphate by two of the soils from its pure solution has a break in its slope at pH 6.4 and 11.6. These pHs are all just below the pK values for the dissociation of hydrogen ions from the undissociated silicic acid or the acid phosphate anions. The presence of silicate in a mixed solution, which is sufficiently concentrated in both silicate and phosphate to give maximum adsorption of either if in pure solution, does not affect the amount of phosphate adsorbed until the pH is over 6.5–7.0. At this pH the maximum adsorption curve for silicate crosses that for phosphate. The presence of phosphate in the mixed solution always depresses the adsorption of silicate. The maximum amount of silicate-plus-phosphate adsorbed from this mixed solution is either a little less than or equal to the amount of silicate adsorbed from the pure silicate solution if the pH is above 7. When silicate displaces phosphate, or phosphate displaces silicate, more moles of the displacing acid are adsorbed than moles of the displaced acid released. These results for soils are similar to those of Hingston et al. for the adsorption of silicate and phosphate by goethite.     

土壤对磷的吸持特性及其与土壤供磷指标之间的关系

本试验测定了浙江省几种代表性土壤对磷的等温吸持特性。实测值与Frundlich、Langmuir、两项式Langmuir和Temkin方程都很符合,相关系数变化范围在0.919-0.999之间,都达到极显著水平。其中以简单Langmuir等温式与本实验资料最为吻合。从Langmuir方程得到的土壤吸持特性值(k×q_m)被认为与土壤供磷特性有关。几种供试样品的(k×q_m)值是:针铁矿21100>黄筋泥4218>黄筋泥田991>青紫泥798>粉泥田660>高岭石485>老黄筋泥田423>泥质田298。根据土壤吸持特性值以田菁进行盆栽试验来估算作物磷肥需要量,结果表明,供磷强度0.3ppm P基本能满足田菁早期生长的需要。为使不同土壤达到相同的供磷强度,(k×q_m)值大的土壤要求更高的有效磷值。供试土壤的几种磷素指标:E值、Bray1-P值和(NaOH-Na₂C₂O₄)法值对(k×q_m)值的变化比较敏感,而EDTA-P和Olsen-P指标对(k×q_m)值的变化较为迟钝。     

PHOSPHATE ADSORPTION IN ALLOPHANIC SOILS

The kinetics and heats of phosphate adsorption were measured on the <2 μm Na-saturated fractions of three allophanc-rich soils from Japan. Between 50 and 2250 μmol P g^?1 as sodium phosphate were added to the soil fractions at pH 5 and pH 7, and at initial concentrations of 5 and 25 × 10^?4m to avoid aluminium phosphate precipitation. An initial ‘instantaneous’ adsorption associated with exposed sites and, simultaneously, two inverse exponential rates of adsorption on internal and freshly forming external sites were observed. These rates are attributed to changes in the microstructure of allophane and to the desorption of organic matter held on allophanic surfaces. This interpretation is strongly supported by corresponding changes in the heats of adsorption with time. Calorimetry clearly indicates that when very large amounts of phosphate are added, new and very reactive surfaces are progressively exposed. More phosphate was adsorbed when the soil was acid and when the soil contained less organic matter.     

土壤对磷酸离子(H2PO4-)吸附的初步研究

土壤中铁铝氧化物胶体,包括层状粘土矿物边缘裸露的铝醇(Aluminol,Al-OH)和铁醇(Ferrol,Fe-OH)对阴离子的吸附,不仅制约某些植物营养元素的有效性,而且还影响某些阴离子对土壤的污染.所以,日益受到人们的注意.     

A PHOSPHATE SORPTION INDEX FOR SOILS

Phosphate sorption isotherms covering a wide concentration range (10^?6 to 5 × 10^?3m phosphate) were determined for 42 soil samples at 20 °C by a standardized technique. The slope of a plot of the sorption, x, against the logarithm of the equilibrium solution phosphate concentration, log c, measured at c= 10^?4M, proved a suitable reference index to characterize the phosphate sorbing properties of the soils. Several single-point methods were tested by statistical correlation against this reference index. Of these, the sorption, x, from one addition of 150 mg P/100 g soil gave r= 0.951, but r= 0.974 when the equilibrium concentration was also taken into account in the quotient x/log c. This quotient is therefore suggested as a simple yet adequate way of indicating a fundamental soil property, its phosphate sorption isotherm.     

CADMIUM ADSORPTION BY SOILS

The Langmuir adsorption equation was found to describe Cd adsorption from dilute solutions at 5°C and 25°C for ten soils from Tuscany. The calculated Langmuir adsorption maxima (Q) and bonding energy coefficients (K) were well correlated with CEC and organic matter content. On the basis of the temperature effect on Q and K, the mechanism of Cd adsorption is discussed.     

从磷酸盐位探讨土壤中磷的固定机制及其有效度问题

最近几年来,我国矿质磷肥施用量年年都有大幅度增加。但从同位素研究及全国试验结果来看,一般作物当季对过磷酸钙中磷的回收率只有10-30%左右(中国科学院南京土坡研究所,1978)。     

ADSORPTION OF PHOSPHATE BY GIBBSITE

The effects of the salts were studied using I per cent suspensions of gibbsite at pH 5.5 and 26°C. At 480μM phosphate and I mM calcium, the kinetic pattern was an initial rapid adsorption reaction, which approached equilibrium in 24 h, revealing a slower reaction. Adsorption isotherms determined at 24 h, with a range of final phosphate concentrations from 0.1 to 1000 μ in solution, were not affected by 20 mM sodium or potassium chloride or 10 mM magnesium chloride. Increasing calcium chloride from o to 20 TIM increased the adsorption of phosphate over the range from 1 to 100 μM final phosphate concentration. At lower (0.1 μM) and higher (1000 μM) phosphate, the effect of calcium was smaller. These results help to explain several effects of the various cations on the adsorption of phosphate by clays and soils, when effects of neutral salts on pH are also considered.     

FLUORIDE ADSORPTION BY ILLINOIS SOILS

Fourteen surface and 6 subsurface horizons of Illinois soils adsorbed significant amounts of F^? with release of OH^?. At low concentrations, adsorption was described by both Langmuir and Freundlich isotherms. The calculated Langmuir adsorption capacities were related to pH, clay, organic carbon, and amorphous aluminum contents. Two soils with different gross chemical properties behaved in essentially the same manner, with adsorption maxima occuring between pH 5.5 and 6.5. The similarity between adsorption at different pH values for the soils and those for bauxite, allophane and synthesized ‘soil chlorite’, and the lack of adsorption maxima between pH 5.5 and 6.5 for pure kaolinite and montmorillonite, suggest that F^? adsorption in the soils is due primarily to the presence of amorphous aluminum oxyhydroxides which are common weathering products in these soils.     

几种土壤对砷酸盐的吸附

砷化合物一般都具有毒性,它对环境的污染引起人们的重视.砷污染土壤后,被土壤吸附、贮存.同时,通过植物的摄取,可进入动物和人体中.植物吸收的砷量和受害的程度,不仅与土壤砷的水平有关,而且还受土壤吸附砷的状况的影响.中国科学院南京土壤研究所试验研究指出,按土壤对砷的吸附量的差异而规定各种土壤的最大允许残留量.     

PHOSPHATE ADSORPTION BY SYNTHETIC AMORPHOUS ALUMINOSILICATES

Phosphate adsorption isotherms were determined for four synthetic amorphous aluminosilicate gels with A1: A1 + Si molar ratios of 0.29 to 0.88. The concomitant silicate release and acid consumed to maintain the pH of the suspensions constant were also measured. The adsorption isotherms were analysed applying a two-term Langmuir equation–assuming two types of sites. The experimental points fitted the predicted adsorption curves only up to a certain amount of phosphate adsorbed. The deviation at high phosphate adsorption values suggested the presence of more than two types of adsorption site. A comparison of phosphate adsorbed with the silicate released and acid consumed to maintain the pH constant indicated that, for a 3 h reaction time at concentrations below about 10 μmol cm^?3, phosphate exchanges mainly with aquo and hydroxo ligands and with adsorbed silicate. At higher concentrations phosphate is adsorbed (i) on sites arising from the disruption of hydroxy aluminium polymers in the gels and (ii) by the displacement of structural silicate.     

COPPER ADSORPTION BY ALKALINE SOILS

The adsorption of copper by four alkaline soils of northwest India was investigated using 0.05m CaCI₂ as supporting electrolyte. The adsorption data conformed to the competitive Langmuir adsorption equation although there was possibliity of copper hydroxide or carbonate precipitation at higher concentrations of added copper. The adsorption capacities of soils were related to CEC, clay content and CaCO₃ equivalent of soil. The free energy changes for adsorption and for interaction were negative and positive respectively.     

ADSORPTION OF HERBICIDE-DERIVED p-CHLOROANILINE RESIDUES IN SOILS: A PREDICTIVE EQUATION

Relationships between the adsorption of p-chloroaniline and the original adsorbate concentration were investigated for five soils ranging in organic matter content from 1.7 to 8.1 per cent and in clay content from 0.5 to 21 per cent. Adsorption data were analyzed applying the linear form of the Freundlich equation. To evaluate the general relationship between adsorption of p-chloroaniline by soils and the solution concentration (C₀), values of partition coefficient (Kp), reflecting the magnitude of distribution of chemical at equilibrium between soil colloids and solution were calculated. The experiments showed that the regression parameters were significantly correlated with the soil organic matter content. A comparison of the experimental results obtained with other soils and the calculated values gave satisfactory agreement.     

不同土壤对钾的选择吸附特性

用K Ca交换平衡法对砖红壤、红壤、土、黑土和水稻土K的选择吸附特性研究结果表明 :KG 和KV 系数随着K Ca平衡体系中吸附相中钾与钙比率的变化而改变 ,其曲线特征说明土壤胶体存在着对K亲和力不同的吸附点位。在低钾饱和度时 ,土壤对K的高选择吸附主要归于粘粒矿物楔形区域电荷点位吸附 ,五种土壤楔形区域相对吸附点位顺序为 :黑土 >土 >水稻土 >红壤 >砖红壤 ,该相对吸附点位顺序与土壤含有风化云母和蛭石有关。在高钾饱和度时 ,五种土壤对K的吸附主要发生于粘粒矿物的晶层表面电荷点位 ,粘粒矿物的晶层表面电荷起源也许起决定作用 ,此时KG 选择系数的大小顺序为 :砖红壤 >红壤 >黑土 >土 >水稻土     

土壤磷酸盐吸持作用的研究

18个供试土样,在较宽的磷浓度范围内(0—100μmP/g土),它们的吸磷特征与Langmuir,Freundlich和Temkin方程式都有很好的相关性(r值大多在0.97以上),尤以Langmuir方程式最佳。各供试土样吸磷能力差异很大,其最大M从大约300μg P/g土(黑垆土)到1500/μg P/g土(砖红壤),火山灰土则高达5000μg P/g土。当加入100μm P/g土时,上述各土壤吸磷量分别占加入磷量的10%,47%和95%左右。土壤粘粒含量以及无定形和结晶态游离氧化铁铝含量均各与M显著相关。土粒的比面可作为单一的指标,它能较妥切而综合地反映土壤的吸磷能力。有机质对土壤吸磷能力的影响是复杂的,它可以增加或减少M值。耕作施肥特别是红壤旱改水多年后,显著地降低了原土壤的M和K值。砂潮新成土上不同施肥处理小区的吸磷等温线表明,土壤中新增加的粗有机物质对磷的吸持作用多发生在磷浓度较高的范围内,它是以吸附量高而吸附结合能低为特征的。     

土壤对重金属离子的竞争吸附

本文研究了理化性质不同的黄棕壤、红壤和砖红壤对Zn、Ni、Co的竞争吸附。采用含有不同重金属离子量的0.05molL^₁Ca(NO₃)₂溶液平衡,pH为5.5。结果表明,其吸附量的顺序:黄棕壤>砖红壤>红壤。对各离子的选择性为:Zn>Ni≥Co。竞争吸附的机制与非竞争吸附有明显的不同。其特征首先表现在吸附量上,竞争吸附要比非竞争吸附高得多。特别明显的,土壤去掉游离氧化铁后其吸附量不但不降,反而有不同程度的增加,Zn²⁺表现尤为突出;影响吸附量很大的陪伴阴离子作用受到严重抑制;反映土壤与重金属离子间作用能力大小的pH₅₀的变化符合吸附等温线的特点。其次根据土壤对重金属离子的吸附和解吸的情况,可以认为,红壤胶体表面吸附位数量远不及黄棕壤和砖红壤,但高能吸附位的比例高。