Testing a mechanistic model. X. The effect of pH and electrolyte concentration on borate sorption by a soil

Borate sorption by a soil was measured with 0.01, 0.1, or 1.0 M sodium chloride as background electrolyte and samples of soil with a range of pH values achieved by incubating with either calcium carbonate or hydrochloric acid for 24 h at 60°C.
Borate sorption generally increased with increasing pH. The more concentrated the electrolyte, the steeper the increase. At low pH, increasing the salt concentration decreased borate sorption; at high pH, it increased sorption. There was an intermediate pH at which salt had no effect on borate sorption. The point of zero salt effect on borate sorption was at a higher pH than the point of zero salt effect on pH. This result was explained by a mechanism in which borate ions react with variable charge surfaces which are heterogeneous and for which part of the heterogeneity is in the electric potential of the surfaces. It cannot be explained by mechanisms which do not take into account the effects of the electric potential of the reacting surfaces on the reaction with borate ions. Although the behaviour of borate was broadly consistent with that of other anions, it differed in that about half of the heterogeneity had to be allocated to the binding constant for borate ions. It was suggested that this was because reaction with organic matter was more important for borate than for other anions.     

磷酸根在矿物表面的吸附-解吸特性研究进展

综述了磷酸根在一些常见土壤矿物表面吸附-解吸特性的研究进展.磷酸根在矿物表面的吸附特性受环境pH、离子强度、温度、反应时间、矿物类型等多种因素的共同影响.一般说来,矿物表面的磷吸附量随pH降低而增加,受离子强度的影响较小.磷酸根在矿物表面的吸附动力学过程可分为快速吸附过程和慢速吸附过程,且在弱结晶矿物中存在微孔扩散过程...     

Testing a mechanistic model. II. The effects of time and temperature on the reaction of zinc with a soil

Samples of a soil were mixed with zinc nitrate solutions and incubated from 1 to 30 days at temperatures from 4 to 60°C. The solution concentration of zinc, which would not have changed on brief mixing with the soil at 25°C, was measured. Background electrolytes for this measurement of null-point concentration were both calcium and sodium nitrate. The effect of the temperature at which null-point concentration was measured was also investigated. After incubation with zinc nitrate, desorption of zinc, and sorption of further zinc, were measured. Null-point concentration of zinc decreased with increasing period of incubation, with the rate of decrease greatest at high temperatures of incubation. The effects of both temperature and time were closely described by a model which postulated an initial rapid adsorption of ZnOH⁺ ions onto heterogenous charged surfaces, followed by a diffusive penetration. Increasing the temperature of incubation increased the rate of diffusive penetration and led to low solution concentrations. In contrast, increasing the temperature at which null-points were measured increased the concentration of ZnOH⁺ ions. This was shown to be consistent with a change in position of the equilibrium of the initial, rapid, adsorption reaction. Curves for desorption of zinc were continuous with curves for sorption of further zinc, but neither desorption nor further sorption coincided with the position of the curves relating retention of previously added zinc to concentration. This result was consistent with the model and occurred because desorption must reverse diffusive penetration. However, the model under-predicted the magnitude of both desorption and sorption of further zinc. Desorption in calcium solutions was greater than in sodium solutions, even when the solution concentration of zinc approached zero. This was consistent with exchange diffusion of calcium ions for some of the penetrated zinc.     

pH和三种阴离子对紫色土亚硒酸盐吸附-解吸的影响

p H和三种竞争性阴离子对紫色土亚硒酸盐吸附-解吸的影响的研究结果表明,随着p H的增大,紫色土对亚硒酸盐的吸附量减少,酸性条件下紫色土对亚硒酸盐吸附量最大。平衡液中加入磷酸氢二钠显著降低了土壤对亚硒酸盐的吸附,硫酸盐对紫色土吸附亚硒酸盐的影响很小,低浓度碳酸氢根离子对紫色土吸附亚硒酸盐具有促进作用,但高浓度的碳酸氢根离子则降低了紫色土吸附亚硒酸盐。磷酸氢根离子和硫酸根离子对亚硒酸盐吸附的影响符合Langmuir和Freundlich拟合方程式,决定系数R2值均在0.90以上。三种阴离子对亚硒酸盐的解吸影响不同,当有磷酸氢根离子和碳酸氢根离子存在时,亚硒酸盐的解吸率增大,而硫酸根离子的存在却对紫色土亚硒酸盐的解吸影响不大。在紫色土地区农业生产中采用含磷酸盐肥料和碱性碳酸氢铵肥料,这些措施可能增加土壤硒的有效性,进而增加植物硒吸收和积累。认识紫色土固液界面硒的吸附-解吸规律,可为提高紫色土地区硒生物有效性,从而进一步提高农产品中硒含量提供科学依据。     

A mechanistic model for describing the sorption and desorption of phosphate by soil

A model of phosphate reaction is constructed and its output compared with observations for the sorption and desorption of phosphate by soil. The model has three components: first, the reaction between divalent phosphate ions and a variable-charge surface; second, the assumption that there is a range of values of surface properties and that these are normally distributed; third, the assumption that the initial adsorption induces a diffusion gradient towards the interior of the particle which begins a solid-state diffusion process. The model closely describes the effects on sorption of phosphate of: concentration of phosphate, pH, temperature, and time of contact. It also reproduces the effects on desorption of phosphate of: period of prior contact, period and temperature of desorption, and soil: solution ratio. The model is general and should apply to other specifically adsorbed anions and cations. It suggests that phosphate that has reacted with soil for a long period is not ‘fixed’ but has mostly penetrated into the soil particles. The phosphorus can be recovered slowly if a low enough surface activity is induced.     

Interaction between Plant Nutrients: II. Effect of Chloride on Activities of Cations in Soil Solution and on Nutrient Uptake by Plants

Abstract

In soil solutions the sum of cations is equivalent to that of anions. Anions are soluble or precipitated as less soluble salts. Therefore, the sum of soluble anions are responsible for the sum of cations in the soil solution. Soluble nitrate anions are unstable as they immobilize in biological materials. Hydrogen carbonate is excreted from plant roots and decomposes into carbon dioxide and carbonate. Carbonate reacts with hydrogen ions and forms complexes and ion pairs with calcium ions. Sulphate and chloride are more stable in the soil solution as anions.

Chloride ions were found to increase the activity of cations in the soil solution and to increase uptake of cations through the entire growth period. Increased absorption of cations increased yield. In temperate climate regions the surplus of chloride leaches from the root zone during winter.     

Observations and modelling of the reactions of 10 metals with goethite: adsorption and diffusion processes

A sample of goethite was mixed for periods which ranged from 2 hours to 8 weeks with solutions of dilute nitrate salts of Pb, Hg, Cd, Zn, Cu, Ni, Co, Mn, Cr and Al. The amount of sorption after each period was measured for an appropriate pH range for each metal. The sorption behaviour was characterized both by using characteristics of the sorption curves such as the pH at which half of the added metal was sorbed (pH₅₀) and by fitting a model in which sorption was mainly characterized by an affinity constant and by a diffusion constant. Initial sorption, whether characterized by the pH₅₀ or by the affinity constant, was closely correlated with the appropriate dissociation constants of the metals. The greater the affinity of the metals for hydroxide ions, the greater their affinity for the goethite surface. The metals differed in the rate at which they continued to react with the goethite. Lead had the slowest continuing reaction, cobalt the fastest. The continuing reaction was due to diffusion into the particles. It was characterized by the fitted diffusion constant and by the change with time in the pH₅₀. For seven of the eight divalent metals, these were correlated with the ionic radius of the metals: the larger the radius, the slower the reaction. For Al and Cr, rates were slower than would be expected from the ionic radii and we suggest this shows that these ions react as the larger M(OH)²⁺ ions. The behaviour of Ni was consistent with oxidation of the surface species and diffusion of Ni(OH)²⁺ ions. The continuing reaction was similar to that observed when metal ions react with soils and suggests that their reaction with iron oxides is important in soils. The results also show that studies in which sorption is measured at only one period of reaction are incomplete and the application of equilibrium models to such results is misleading.     

pH对土壤吸持磷酸根的影响及其原因

本文选择了浙江、江苏15个性质变化范围较大的土壤样品,研究在两种支持电解质、不同pH条件下对磷酸根的吸持反应。结果表明,加碱提高强酸性土壤的pH值,导致交换性铝的水解和羟基铝聚合物的生成,增加对磷的吸持。磷酸根同酸性土壤的反应,可促进交换性铝的水解,释放出H⁺,降低体系的pH。在CaCl₂介质中,当pH>6时,可能有磷酸钙类盐形成,使溶液中磷浓度显著降低。有机质对土壤吸持磷有重要影响。在低pH下有机质通过与Al³⁺形成络合物,阻碍溶液中A1³⁺的水解,并与磷酸根竞争羟基铝化合物表面的反应点位,从而降低酸性土壤对磷酸根的吸附量。     

Describing the effect of time on sorption of phosphate by iron and aluminium hydroxides

Iron and aluminium hydroxides were precipitated both in the presence and absence of kaolinite. The reaction between phosphate and these hydroxides was measured for periods which ranged from 5 min to 72 h. The effect of time on phosphate sorption was examined by plotting the sorption data according to different, simple, kinetic equations such as the first order, second order, the parabolic diffusion equation, the Elovich equation and the modified Freundlich equation. The effect of time on sorption was also examined by the mechanistic model recently developed by Barrow (1983b) for the sorption and desorption of phosphate by soils. The sorption of phosphate by iron and aluminium hydroxides increased with time and the reaction continued through the period of observation without reaching a true equilibrium. Curvilinear relationships were obtained when the data were plotted according to the simple kinetic equations. These simple kinetic equations fail to describe the effect of time on sorption partly because the mechanism is different from that postulated and partly because they do not consider electrostatic effects when phosphate ions react with a charged surface. The mechanistic model of Barrow (1983b), which takes this effect into account, described effect of both concentration and time on phosphate sorption. According to this model, the increase in phosphate sorption with time was caused by a redistribution of adsorbed phosphate into the interior of the particles of iron and aluminium hydroxides by solid-state diffusion.     

A brief discussion on the effect of temperature on the reaction of inorganic ions with soil

Published reports on the effect of temperature on the sorption of ions by soil, or soil constituents, are in conflict with regard to the direction of the effect and its interpretation. It is argued that, in many cases, increased sorption with increased temperature is due to an increased rate of the reaction that follows adsorption. The effects of temperature on the adsorption reaction itself are complex because of separate effects on the ions in solution, on the charge on the surface, and on the affinity of the ions for the surface. On balance, adsorption of anions should decrease with increasing temperature, and adsorption of cations should increase. However, decreased adsorption of cations is possible, particularly at high pH. With one exception, these conclusions are consistent for all published reports seen.     

Cadmium soil sorption at low concentrations: V. Evidence of competition by other heavy metals

Sorption of Cd at low concentrations onto 12 Danish soils (coarse sands to sandy loams) was studied with respect to competitive effects of other heavy metals by means of laboratory batch experiments. Both a mixture of Ni, Co, and Zn and of Cr, Cu, and Pb effectively reduced the sorption of Cd onto the soils. The employed mixtures of competing heavy metals were considered to resemble moderately polluted conditions. Cadmium distribution coefficients were reduced 2 to 14 times due to competition, but at constant concentrations of competing heavy metals the shape of Cd isotherms was not affected. The effect of Ni, Co, and Zn, which like Cd is primarily governed in soil environments by sorption, was also studied individually. Apparently Zn, which is present in relatively higher concentrations than Ni and Co, accounts for most of the observed competition with Cd.     

Prediction of heavy metal contents and displacement in soils

Under laboratory conditions, the availability of cadmium, lead and copper in an Orthic Luvisol was investigated when applied to the soil at various initial concentrations. The metals were applied separately or concurrently with the other two heavy metal ions in order to bring about competition for the adsorption sites. The presence of competing metals increased the general availability especially of cadmium in the soil. Lead and copper were to a lesser extent also affected by the competition of other ions. On the basis of our ion-competition results we developed a longterm trend model suitable to predict the consequences of regular heavy metal loading (e.g. in the form of sewage sludge). The model takes into consideration the annual precipitation and the water suction profile of the soil. On the basis of the model predictions it has to be concluded that the threshold values for heavy metals in the sewage sludge regulation (Switzerland) are too high.     

Testing a mechanistic model. IV. Describing the effects of pH on zinc retention by soils

Samples of two soils were incubated at 60°C for 24 h with several levels of either calcium carbonate or hydrochloric acid. Zinc retention was then measured on subsamples of the treated soil over 24 h at 25°C. The results were compared with published experiments (Bar-Yosef, 1979; Harter, 1983) in which zinc retention was also measured over a range of concentrations and pH values, but using different experimental conditions. Zinc retention increased as pH increased. In all cases, this effect could be described by assuming that the ZnOH⁺ ion was retained and the effect of pH was due to the increased proportion of this ion in solution. Over most of the pH range it was not necessary to assume any contribution from a decrease in the electrostatic potential of the reacting surfaces with increasing pH. This contrasts with the effects of pH on phosphate and fluoride retention and suggests that the materials that react with zinc differ from those that react with anions. The shape of plots of zinc retention against ZnOH⁺ concentration was reproduced using a model in which it was assumed that there was a range of values of electrostatic potential. A similar model had previously been used for anions. Zinc would tend to react with the most negative end of this range and phosphate with the least negative end. This further suggests that zinc and anions may react with different materials.     

Inorganic anion sorption and interactions with phosphate sorption by hydrous ferric oxide gel

The sorption of inorganic anions by hydrous ferric oxide gel (Fe gel) from 10 ^?1 M NaClO₄ at pH 6.5 decreased in the order: orthophosphate (H₂PO₄)>arsenate (H₂AsO₄) = selenite (HseO3) > silicate (H₄SiO₄) > molybdate (MoO²₄^?) > sulphate (SO²₄^?) > selenate(SeO²₄^?)>chloride (Cl^?) = nitrate (NO^?₃). When each anion was added to Fe gel with an equimolar quantity of H₂PO^?₄, there was no detectable effect of SO²₄^?, SeO²₄^?, Cl^?, and NO^?₃ on the amount of H₂PO^?₄ sorbed. Other anions depressed H₂PO₄ sorption in the order H₂AsO₄ >HseO₃ > H₄SiO₄ > MoO²₄. At the lowest level of anion addition (500 mmol kg ^?1), H₂PO₄ sorption was depressed by no more than 6% of the sorption level in the absence of a competing anion. In contrast, at the highest level of anion addition (1700 mmol kg-¹ of each), H₂AsO₄ decreased H₂PO₄ sorption by 44%. The sorption of SO₄^? was completely eliminated when this anion was added with equimolar amounts of H₂PO₄. The ability of anions to compete with H₂PO₄ for sorption sites could not be explained solely by the results obtained for the sorption of each anion alone. Thus, H₂AsO₄ was more competitive than H₂PO₄ when added together, even though more H₂PO₄ than H₂AsO₄ was sorbed when each anion was added alone. Although H₂PO₄ was sorbed in larger amounts, there is no evidence to suggest that H₂PO₄. H₂AsO₄, and HseO₃ were sorbed on different sites.     

可变电荷土壤中特殊化学现象及其微观机制的研究进展

综述了近年来可变电荷土壤化学研究的进展,着重总结了可变电荷土壤中的盐吸附、铁铝氧化物对土壤自然酸化的抑制作用和离子强度对离子专性吸附的影响等特殊化学现象及其微观机制的研究进展。用颗粒表面扩散层重叠导致有效电荷数量减小的原理解释了盐吸附现象和铁铝氧化物对土壤自然酸化的抑制作用。阐明了可变电荷土壤和矿物中介质离子强度影响离子专性吸附的机制,用四层吸附模型解释了离子专性吸附随离子强度增大而增加的现象,并根据胶体zeta电位随离子强度改变而变化的趋势进一步证明了离子强度增大使胶体专性吸附面上静电电位的绝对值减小,是离子专性吸附随离子强度增大而增加的主要原因。带电颗粒表面双电层结构和双电层相互作用的深入研究,有助于阐明可变电荷土壤中一些特殊化学现象的微观机理,从而进一步完善土壤化学理论。     

Influence of anions on dispersion and physical properties of the A horizon of a Red-brown earth

Three groups of anions were distinguished in order of effectiveness with respect to the dispersion and flocculation of soil samples treated with Fe(III) polycations: phosphate and fulvate citrate, oxalate, silicate and tartrate and salicylate, catechol, aspartate, lactate and acetate. This was also the order of the amount of anion adsorbed by the soil. The addition of phosphate and fulvate to soil samples with a net charge of zero lowered the zero point of charge producing particles with a net negative charge. This increased the amount of dispersible clay present from 0 to 9% by weight of soil. The sorption of phosphate and fulvate by soil samples with a net positive charge reduced the zero point of charge and caused flocculation of dispersed clay. Electrophoretic and electron microscopic studies confirmed the dispersion-flocculation phenomena.Treatments which produced dispersed clay led to increased bulk densities, plastic limits and moduli of rupture but lower porosities, water holding capacities and hydraulic conductivities. The sorption of anions on soil samples with a net charge of zero reduced friability.     

Modeling of Salt Sorption in Volcanic Ash Soil

Groundwater pollution by nitrate from agricultural fields is a worldwide problem. To improve the understanding of nitrate transport processes through volcanic ash soils overlying groundwater aquifers, salt sorption experiments were performed. Salt sorption is the process that involves the simultaneous use of cation and anion adsorption mechanisms without changing the pH. Prepared six different concentrations of potassium chloride (KCl) solutions were mixed with soil samples. Anion and cation contents of the liquid and solid phases were determined. Experiments were performed in triplicate of six kinds of KCl solutions for three types of soils. Thus, total 54 of samples were analyzed. Relationships between ionic strength and sorption capacity increments of cations and anions were determined. The results show that if ionic strength of the infiltrating solution to the volcanic ash soil is known, the ECEC (effective cation exchange capacity) and EAEC (effective anion exchange capacity) can be reliably estimated. The resulting prediction equations can be included to improve reactive transport simulation models. Consequently, it will be possible to better understand solute transport with changing sorption capacity for the solid soil phase.     

不同相伴阴离子对镉污染红壤的微生物活性影响

通过外加醋酸镉和氯化镉的室内培养试验研究了相伴阴离子对镉污染红壤微生物活性的影响。结果表明 ,在相同镉浓度下相伴OAc- 对镉污染红壤的微生物生物量碳、基础呼吸和代谢商以及脲酶和酸性磷酸酶活性的抑制作用大于相伴Cl- ,统计分析显示 ,镉相伴OAc- 与Cl- 除对红黄泥的代谢商未达明显影响外 ,对供试红壤的其它微生物活性指标均达到显著差异 (p <0 0 5 )。用醋酸镉处理的土壤有效态镉含量明显高于氯化镉处理。钾盐试验结果表明 ,相伴OAc- 与Cl- 对土壤微生物活性没有产生明显抑制作用 ,OAc- 甚至还存在一定的刺激效应。可见 ,相伴OAc- 对镉污染红壤的微生物毒害作用大于相伴Cl- ,其直接原因可能是用醋酸镉处理的生物有效性镉明显高于氯化镉处理所致。     

Testing a mechanistic model. VII. The effects of pH and of electrolyte on the reaction of selenite and selenate with a soil

The pH of samples of a soil was altered by mixing them either with acid or lime, and incubating the moistened samples at 60°C for a day. The sorption of selenate and of selenite was then measured using as background electrolytes, 0.01 M, 0.1 M and 1.0 M sodium chloride and also 0.01 M calcium chloride. The results were compared with previous studies with phosphate and fluoride. Selenite was sorbed more strongly than selenate, but not as strongly as phosphate or fluoride. Sorption of both selenite and selenate decreased with increasing pH. This decrease was more marked for selenate than for selenite; more marked in a sodium system than in a calcium one; and more marked with a dilute background electrolyte than a concentrated one. Under certain conditions, the steeper curves for the dilute electrolyte crossed the curves for the concentrated electrolyte giving points of zero salt effect. For selenite, these points of zero salt effect occurred near pH 6 and the greater the sorption the lower the pH for zero salt effect. For phosphate, the analogous value was near pH 5. For selenate, if a point of zero salt effect occurred, it was at such a high pH and such a low amount of sorption that it could not be measured. Thus, the larger the amount of sorption the lower the pH for the point of zero salt effect. This generalization applied both within and between different kinds of sorbates. The results were closely described by a model that had previously been applied to phosphate and fluoride. The model postulates that ions react with charged surfaces. The electric potentials of the reacting surfaces are affected by the identity and concentration of the background electrolyte and this produces the interactions between pH and electrolyte concentration. The model also postulates that there is a distribution of electric potentials. Anions react with surfaces which occur in the more positive tail of this distribution. The smaller the amount of the reaction the more positive the potential of the reacted surface and, therefore, the higher the pH required to decrease this potential to zero.     

Phosphorus retention and release of anions and organic carbon by two Andisols

Andisols can absorb large amounts of phosphorus rapidly, and then release it slowly, yet the mechanisms by which they retain P and release it for plant growth are poorly understood. Ligand exchange of organic compounds from Al–humic complexes by P and/or Si release – due to breakdown of allophanic microstructure to provide sorption sites – might account for the retention of P, but its extent is not known. We applied a soil column flow-through technique to quantify the release of anions and organic carbon (C) associated with P sorption by two andic soils, and we related the anion release to possible mechanisms for the retention of P. Phosphate (H₂PO₄^–, HPO₄^2–) sorption and concurrent anion desorption were obtained by passing a 1-g P 1^–1 (32 mmol KH₂PO₄ in 1 mm CaCl₂) solution through the soil columns (25 cm³). Total dissolved P, Fe, Al, S, Ca, Mg, K, Mn, organic C and pH were determined in the eluent. Changes in eluent pH and the patterns of the retention of P and corresponding concentrations of Al, Si and organic C in the eluent were similar for the two Andisols. The general pattern and changes in pH of the eluent coincided with changes in the patterns of release of organic C and Si and the rate of P retention. Release of silica accounted for < 6% of the P sorbed and had only a minor role in P retention in these two Andisols. Release of organic C, however, accounted on a molar basis for 40% and 83%, respectively, of the P sorbed. Direct measurements of the pH of the eluent and release of anions and organic C concurrent to P retention contribute to rapid assessment of the controlling mechanisms of P retention. The results indirectly confirm the hypothesis of ligand exchange of solution P with organic complexes held on allophanic surfaces. The organic C release, however, is not specifically related to either the fast or the slow P retention phase. The shift in the controlling P retention reaction associated with a change from the fast to the slow P retention phase is clearly indicated by an abrupt change of the pH of the eluent. This shift, in previous studies identified graphically by a change in slope of the P sorption isotherm, can be identified directly by measuring the pH of the matrix.