A comparison of measured and theoretical soil acidity diffusion coefficients over a wide range of pH

The soil acidity diffusion coefficients have been measured at two P_co2 levels with values in the range 2–70 × 10^?9 cm² s^?1. The coefficient passed through an ill-defined minimum in the pH range 5–6.5. Theoretical values, calculated on the basis that the only significant acid-base carriers in the soil were the H₃O⁺ -H₂O and H₂CO₃-HCO^?₃ pairs, agreed well with the experimental values over the whole pH range at P_co2= 0.005 atm. Agreement was not so good however at a CO₂ pressure of 0.0003 atm., especially in the neutralalkaline pH range. This was thought to be due to difficulties in maintaining this level of CO₂ throughout the soil samples.     

THE OXIDATION OF IRON SULPHIDES IN SOILS IN RELATION TO THE FORMATION OF ACID SULPHATE SOILS, AND OF OCHRE DEPOSITS IN FIELD DRAINS

Aerating pyritic soils causes acidification and the forrnation of acid sulphate soils, or cat-clay. The Oxidation of pyrite in soils is associated with the deposition in tile drains of a form of ochre quite distinct from that formed by the action of filamentous iron bacteria. Pyrite-derived ochre results from the action of Thiobacillus ferrooxidans, which, below pH 3.5–4.0, catalyses the Oxidation of Fe²⁺ and pyrite. In soils less acid than c. pH 4, pyrite oxidizes relatively slowly by chemical reactions to Fe²⁺ and SO²₄^?. Under these conditions iron enters the drains as Fe²⁺ and is there oxidized by T. ferrooicidans and deposited as hydrated ferric oxide. Once the soil becomes acid enough for T. ferrooxidans to multiply, the rate at which pyrite oxidizes increases several-fold, and at c. pH 3 iron appears in the drainage water in the ferric form. Liming seems to decrease the rate of Oxidation.     

可变电荷土壤表面酸碱模型及其计算机模拟

在假定土壤对酸碱的缓冲作用全由表面基团反应所控制的基础上,建立了一个描述可变电荷土壤酸碱滴定曲线的模型,并在计算机上对实验结果进行了模拟。结果表明,本模型可以较好地描述土壤酸碱滴定曲线,提供土壤的酸强度(K_a)和酸容量(S_t),并可进一步提供土壤的酸缓冲容量曲线。本模型对了解和认识土壤酸化和吸附等过程具有一定的意义。     

THE MEASUREMENT AND MECHANISM OF ION DIFFUSION IN SOILS V. DIFFUSION OF HYDROGEN ION IN SOILS

The linear diffusion of H ion from a series of soil blocks, containing essentially H and Ca only as exchangeable cations, into a sink solution maintained at pH 5·2, has been studied. In three separate series of experiments, first the total concentration of diffusible H, then the amount of diffusible H in the pore solution, and finally the amount of exchangeable H associated with the solid phase have been successively varied. Account has also been taken of the variation in activity ratio: a_H/√a c_a. The effect on the resulting flux and diffusion coefficients of the ion has been related to the H buffer power of the soil. The impedance factor of the ion through the liquid pathway is slightly lower than that for other cations determined in soil. The diffusive flux of H occurs through the liquid pathway, and the contribution of solid-associated H is small, except possibly at low H ion solution concentrations.     

THE RELATIONSHIP BETWEEN OXIDATION-REDUCTION POTENTIALS AND OXYGEN-DIFFUSION LEVELS IN SOME WATERLOGGED ORGANIC SOILS

In valley and blanket-bog peat, oxygen-diffusion rates and corresponding oxidation-reduction potentials have been measured, and the relationship between them expressed graphically. Oxygen-diffusion rates were obtained ‘polarographically’, and the Pt cathode also served as the redox indicator-electrode. Plateau-shifts towards more positive potentials made it necessary to use the reduced voltage setting of ?0.48 v for oxygen determinations. These plateaushifts correlate with a lowering of the oxygen content, and an increase in acidity, or, perhaps, with the type of buffer systems found in peat. The ratio redox potential/oxygen diffusion is not constant. At very low oxygen values there is a relatively large increase in redox potential per unit of oxygen, but, as oxygen approaches 2 × 10^?8 g O₂cm^?2min^?1, the ratio becomes much lower, while variations become more obvious. rH values calculated according to Jeffery (1961), show that, in peat of high iron content at pH 6, the first traces of oxygen correspond to an rH 1.10–1.20 (E₆, 50–120; reduced and oxidized iron probably present), while above 2 × 10^?8 g O₂ cm^?2min^?1 the rH is greater than 1.20 and oxidized iron probably predominates. Thus oxidized soil, as defined by Jeffery, may be maintained at very low oxygen levels. It is suggested that oxygen diffusing from plant roots into these peats will oxidize reduced soil products, and thereby protect the plant.     

华南红壤的交换性碱和交换性酸

本文提出了一个同时测定土壤的交换性酸和交换性碱的简易方法。将土壤的交换性酸和交换性碱区分为:Na-交换性酸、Ba-交换性酸和SO₄-交换性碱、F-交换性碱。用推荐的方法,在野外对华南地区由不同母质发育的砖红壤、赤红壤、红壤等10个剖面进行了测定。结果表明,红壤类土壤含有相当量的交换性碱,但其数量比交换性酸少。酸性母质发育的土壤的交换性酸和交换性碱量大于由基性岩发育的土壤者。红壤的交换性酸和碱的量随电性盐浓度的增高而增大,浓度大于0.1N后,数量基本不变。     

磷酸盐位用于土壤需磷诊断的研究

土壤磷酸盐位是研究土壤磷有效度的具有相对能量意义的概念,它的提出为研究土壤磷的问题开辟了一条新的途径^[2,3,11].磷位值是土壤有效磷的强度指标,把它运用于土壤需磷诊断上,使它成为指导磷肥施用的有用工具,在当前生产上有一定意义.     

THE MEASUREMENT AND MECHANISM OF ION DIFFUSION IN SOILS

Diffusion coefficients of soil phosphate calculated from flux to chloride form of anion-exchange resin-paper, assuming total depletion of the labile pool at the boundary, were too small and unrealistic. Thus not all the phosphate in the labile pool contributed to the diffusion process while being desorbed at constant pH in the presence of an indifferent anion—Cl—from the resin-paper. Desorption relationships under these conditions, using CaCl₂ at atmospheric CO₂ pressure, were markedly different from the relationship between the long-term ³²P-exchangeable phosphate and the corresponding pore-solution concentrations. In the same soil containing different amounts of labile phosphate, a different desorption relationship was found for each phosphate level. The constant proportionality between amount of phosphate diffusing into resin-paper and square root of time was indicative of a constant concentration at the boundary. The resin-paper: soil system was therefore considered as an infinite composite medium in which diffusion through both resin-paper and soil were rate-limiting. The constant boundary concentrations were estimated by the use of the diffusion coefficients in the resin-paper, the phosphate adsorption isotherm for the resin-paper and the desorption relationship for each phosphate level in the soil. Diffusion coefficients, calculated using the boundary concentration appropriate to each phosphate level, were related to the slopes of the corresponding desorption relationships, resulting in values of the impedance factor similar to those found for K diffusion under similar conditions. The resin-paper method, however, does not provide an accurate enough measure of the diffusion coefficient of soil phosphate to be of any practical use. Until better and simpler methods are found, the diffusion coefficient may be calculated using the slopes of the desorption relationship and the separately determined value of the impedance factor.     

陕西地区土壤中的硒

硒是人和动物体必需的微量元素之一,早已证明,土壤和饲草中过量的硒会导致牲畜中毒而罹患“碱质病”和“盲跚症”,而土壤和饲草硒含量过低则会引起牲畜白肌病等多种缺硒病^[9]。近年来国外又有资料报道食物和饮水中的低硒容易使人体产生癌症、心血管病、关节炎、婴幼儿碎死症等多种疾病^[6]。鉴于在土壤一植物一动物和人的生态系统中,土壤是最基本的因素,因此对土壤硒的研究在许多国家早已受到人们的重视。国内对土壤硒的研究,始于七十年代对人体地方性疾病的研究,现已证实,地方性克山病、大骨节病的发生与环境和机体缺乏硒有密切关系^[1,3,11]。     

苏南水稻土对铜离子专性吸附的初步研究

六十年代以来,土壤对多价离子特别是重金属离子的专性吸附,已日益成为土壤化学领域中一个受人注意的问题。土壤胶体中铁、锰、铝、硅等氧化物及其水合物和土壤有机质是专性吸附的主要载体^{[12,16,17,19,20,21]},它们对许多重金属元素的专性吸附所引起的富集过程,起着控制这些金属元素在土壤溶液和海水中浓度的作用^[9,15,18];一些微盒营养元素在土壤中的移动及其对植物的有效性,也深受土壤中氧化物胶体的专性吸附的影响^[11,14,21]。因此,铁、锰等水合氧化物对重金属离子的专性吸附的研究,不仅是土壤化学领域,而且也是土壤环境保护和地球化学等领域中的重要研究课题。     

酸性土壤磷分级新方法建立与生物学评价

土壤磷分级方法可用于估算土壤有效磷数量、不同土壤磷组分库数量及其对土壤有效磷的补充能力。以云南赤红壤、黄红壤及湖北棕红壤为供试材料,运用张守敬方法、蒋柏藩方法及本文提出的新方法,对三种酸性土壤和其石灰改良后的土壤磷进行分级研究,探讨石灰改良对酸性土壤磷组分数量及其生物有效性的影响。结果表明:Ca2-P、Al-P和Fe-P是酸性土壤主要的有效磷源,O-P(闭蓄态磷)也是潜在有效磷源,土壤中活性有机磷库相对比较稳定,可转化为高活性有效磷源供植物吸收利用。与两种经典磷分级方法相比,新方法将O-P划分为O-Al-P和O-Fe-P,O-Fe-P较好地反映了石灰处理与对照之间的土壤磷植物有效性差异。     

THE HIGH- AND LOW-ENERGY PHOSPHATE ADSORBING SURFACES IN CALCAREOUS SOILS

The two-surface Langmuir equation was used to study P adsorption by 24 calcareous soils (pH 7.2-7.6; 0.8-24.2 per cent CaCO₃) from the Sherborne soil series, which are derived from Jurassic limestone. High-energy P adsorption capacities (x″_m) ranged from 140–345 μg P/g and were most closely correlated with dithionite-soluble Fe. Hydrous oxides therefore appear to provide the principal sites, even in calcareous soils, on which P is strongly adsorbed (x″_m 6–51 ml/μg P). The low-energy adsorption capacities (x″_m) ranged from 400–663 μg P/g and were correlated with organic matter contents and the total surface areas of CaCO₃ but not with per cent CaCO₃, pH, or dithionite-soluble Fe. Total surface areas of CaCO₃ in the soils ranged from 4.0 to 8.5 m²/g soil. Low-energy P adsorption capacities agree reasonably with values (100 pg P/m²) for the sorption of phosphate on Jurassic limestones but phosphate was bonded much less strongly by soil carbonates (k″= 0.08–0.45 ml/μg P) than by limestones (k～10.0 ml/μg P). Low-energy P adsorption in these soils is tentatively ascribed to adsorption on sites already occupied by organic anions (and probably also by bicarbonate and silicate ions) which lessen the bonding energy of co-adsorbed P.     

Effectiveness of crop straws,and swine manure in ameliorating acidic red soils: a laboratory study

Purpose

Crop straws and animal manure have the potential to ameliorate acidic soils, but their effectiveness and the mechanisms involved are not fully understood. The aim of this study was to evaluate the effectiveness of two crop (maize and soybean) straws, swine manure, and their application rates on acidity changes in acidic red soils (Ferralic Cambisol) differing in initial pH.

Materials and methods

Two red soils were collected after 21 years of the (1) no fertilization history (CK soil, pH 5.46) and (2) receiving annual chemical nitrogen (N) fertilization (N soil, pH 4.18). The soils were incubated for 105 days at 25 °C after amending the crop straws or manure at 0, 5, 10, 20, and 40 g kg^?1 (w/w), and examined for changes in pH, exchangeable acidity, N mineralization, and speciation in 2 M KCl extract as ammonium (NH₄⁺) and nitrate plus nitrite (NO₃^??+?NO₂^?).

Results and discussion

All three organic materials significantly decreased soil acidity (dominated by aluminum) as the application rate increased. Soybean straw was as effective (sometimes more effective) as swine manure in raising pH in both soils. Soybean straw and swine manure both significantly reduced exchangeable acidity at amendment rate as low as 10 g kg^?1 in the highly acidic N soil, but swine manure was more effective in reducing the total acidity especially exchangeable aluminum (e.g., in the N soil from initial 5.79 to 0.50 cmol₍₊₎ kg^?1 compared to 2.82 and 4.19 cmol₍₊₎ kg^?1 by soybean straw and maize straw, respectively). Maize straw was less effective than soybean straw in affecting soil pH and the acidity. The exchangeable aluminum decreased at a rate of 4.48 cmol₍₊₎ kg^?1 per pH unit increase for both straws compared to 6.25 cmol₍₊₎ kg^?1 per pH unit from the manure. The NO₃^??+?NO₂^? concentration in soil increased significantly for swine manure amendment, but decreased markedly for straw treatments. The high C/N ratio in the straws led to N immobilization and pH increase.

Conclusions

While swine manure continues to be effective for ameliorating soil acidity, crop straw amendment has also shown a good potential to ameliorate the acidity of the red soil. Thus, after harvest, straws should preferably not be removed from the field, but mixed with the soil to decelerate acidification. The long-term effect of straw return on soil acidity management warrants further determination under field conditions.

     

CALCIUM: ALUMINIUM EXCHANGE EQUILIBRIA IN CLAY MINERALS AND ACID SOILS1

Exchange reactions between 0.0in AlCl₃ solutions of different pH and Ca-saturated montmorillonite, vermiculite, illite, and soils from the Park Grass Experiment at Rothamsted and the Deerpark Experiment, Wexford, Ireland, showed that Al³⁺ and Al(OH)₂⁺ were adsorbed from solutions of pH > 4.0 and Al³⁺ and H⁺ from solutions of pH < 3.0. When Al was adsorbed, the cation exchange capacity of Ca-saturated soils and clays increased. Conventional Ca: Al exchange isotherms showed that Al³⁺ was strongly preferred to Ca²⁺ on all soils and clays. The equilibrium constant for Ca: Al exchange, K, was identical for soils before and after oxidizing their organic matter and did not vary, for any exchanger, with Al-saturation or the initial pH of the AlCl₃ solution. This proved the validity of the procedure used for calculating exchangeable Al³⁺. K values for Ca:Al exchange favoured Al³⁺ in the order: vermiculite > Park Grass soil > Deerpark soil > illite > montmorillonite. The influence of surface-charge densities of the clay minerals on this order is discussed and a method proposed and tested for calculating the K value of a soil from its mineralogical composition.     

Principles underlying the practice of determining lime requirements of acid soils by use of buffer methods

Abstract

A buffer is generally a mixture of a weak acid and a salt of the same weak acid. Hence it can neutralize both acids and bases, and thus resists marked changes in pH of a system. Yet systematic change in pH of a buffer caused by addition of an acidic substance can be used to indicate the total acidity represented by the change in buffer pH. Since acid soil is itself a buffer, when it is added to a buffer mixture for the purpose of measuring its acidity or lime requirement (LR), the resulting double‐buffer suspension (soil‐buffer) is a relatively complex system. Much of the complication in interpreting the changes in buffer pH brought about by mixing soil and buffer stems from the facts: i) that much of the acidity is pH‐dependent, and ii) that quick‐test methodology involves reaction of only a fraction of the total soil acidity with the buffer. Marked change in relative amounts of H ions dissociating from the soil‐SMP‐buffer system at soil‐buffer pH 6.9 and above accounts for relatively wide variations between buffer‐indicated and CaCO₃ incubation‐measured LR of low LR soils. Similarly, decreased reactivity of H⁺ in high organic matter soils and increased reactivity of H in acid‐leached soils cause errors in buffer‐indicated LR. Awareness of these principles helps avoid pitfalls of existing buffer methods, and has led to incorporation of the double‐buffer feature for improving the SMP method.     

AVAILABILITY OF POTASSIUM TO RYEGRASS FROM SCOTTISH SOILS II. UPTAKE OF INITIALLY NON-EXCHANGEABLE POTASSIUM

The stable desorption parts of soil Quantity/Intensity isotherms were used to determine the contributions of initially exchangeable and non-exchangeable potassium to plant uptake from ten soils. The activity ratio, AR^K= a_K/√^aC_a, Mg at which K was first taken up from non-exchangeable sources varied from 3 × 10^?3 to 8 × 10^?3 M^1/2 depending on the soil. Uptake rates of two categories of initially non-exchangeable K were linearly related to √times;. The first category appeared to be close to equilibrium with the initially exchangeable K, and gave effective diffusion coefficients of 10^?7 cm² s^?1 for four soils. The second category gave diffusion coefficients from 10^?20 to 10^?22 cm² s^?1, probably came from internal surfaces of micaceous clays, and began to be released at activity ratios below 3 × 10^?4 to 6 × 10^?4 M^1/2 depending on soil type. The soils fell into three groups, broadly consistent with soil series, on their ability to release the second category of potassium.     

EFFECT OF SOIL pH AND ORGANIC MATTER ON LABILE ALUMINIUM IN SOILS UNDER PERMANENT GRASS

The rates of extraction of Na, K, Mg, Ca, and Al with 1M NH₄ NO₃ from the mineral-and organic-rich layers of some Park Grass (Rothamsted) soils were measured at the pH of the soil. Below pH 3.7 exchangeable Al, derived from the kinetics curve, increases with decreasing soil pH and is less in the organic-rich layer. The sum of the basic exchangeable cations, ∑(Na + K + Mg + Ca), increases with increasing soil pH and is more in the organic-rich layer. The extraction of exchangeable Al obeys first order kinetics, the rate constant being similar for all the soils (mean value 36 ± 7 × 10^?6|s^?1), which implies that exchangeable Al is released from surfaces with similar properties for the adsorption of Al, and that the rate is not affected by soil pH and organic matter. The rate of extraction of non-exchangeable Al is the same in the mineral-and organic-rich layers of each soil, and is maximal at about pH 3.7, decreasing sharply at more and less acid pH values.     

Solubilization of phosphate by rice plants growing in reduced soil: prediction of the amount solubilized and the resultant increase in uptake

Previous work has shown that rice plants growing in reduced soil are able to solubilize P by inducing an acidification in the rhizosphere through H⁺ produced in Fe²⁺ oxidation by root–released O₂, and by the direct release of H⁺ from the roots to balance excess intake of cations over anions. In this paper, equations for the diffusion and interaction of P and acid in soil are developed to predict the resultant increase in P uptake by the roots. Good agreement was obtained between the profiles of P and pH in the rhizosphere measured in the previous experiments, and those predicted using the equations with independently measured parameter values. The equations showed that solubilization accounted for over 80% of the P taken up. Measurements of the solubilization parameters in a range of reduced rice soils showed that H⁺ addition increased the quantity of P that could be desorbed per unit weight of soil and the concentration of P in solution, in all the soils tested. The quantity of P solubilized per unit H⁺ added at a given solution P concentration varied about 50–fold between soils, with a median of 11.9 mmol P per mol H⁺. The native soil solution P concentration varied 50–fold (median = 0.91 UM) and the soil pP buffer power (the quantity of P desorbed per unit decrease in –log of the P concentration in solution) varied 100–fold (median = 0.36 mmol kg^?1 pP^?1); the soil pH buffer power varied 7–fold (median = 0.075 mmol kg^?1 pH^?1). Calculations indicated that, in most of the soils tested, rice plants would depend upon solubilization for the bulk of their P.     

RATE PROCESSES IN THE DESORPTION OF PHOSPHATE FROM SOILS BY ION-EXCHANGE RESINS

Phosphate extracted by ion-exchange resins in the chloride and sodium forms from a deep river-gravel soil under widely varying conditions is always from the isotopically exchangeable or‘labile’ pool. At any reaction time, a constant fraction of this pool is desorbed by the chloride form of the anion-exchange resin alone, irrespective of the pH and phosphate manuring of the soil. If, however, a sodium: cation exchange resin is included, increasing fractions of the‘labile pool’ are desorbed with decreasing soil acidity. Phosphate desorption by the anion-exchange resin alone and with the cation exchange resin is shown to be‘particle-diffusion’ controlled in the anion exchange resin and neither a‘chemical reaction’ nor a‘film-diffusion’ mechanism. Over the pH range 4·5–8·5, values between 4·8 and 0·9 × 10^-9 cm² sec^-1 were calculated for the interdiffusion coefficient of the phosphate: chloride exchange process in the resin. The isotopically exchangeable phosphate in the soils seems to behave like sparingly soluble or weakly dissociating compounds towards ion-exchange resins and its rate of desorption depends on the nature and composition of the resins.     

Measuring and simulating pH buffer capacity of calcareous soils using empirical and mechanistic models

ABSTRACT

We studied (i) the pH buffer capacity (pHBC) of calcareous soils varied widely in calcite and texture, (ii) the contribution of soil properties to pHBC and (iii) the significance of using a model based on calcite dissolution to estimate the pHBC of calcareous soils. The pHBC of soils was measured by adding several rates of HCl to soils (100–6500 mM H⁺ kg^–1), in a 0.01 M CaCl₂ background and an equilibration time of 24 h. The pHBC (mM H⁺ kg^–1 pH^?1) varied from 55 to 3383, with the mean of 1073. The pHBC of the soils was strongly correlated with soil CaCO₃ equivalent (calcite) (r = 0.94), sand (r = ?0.72), silt (r = 0.60), EC (r = 0.63), pH (r = 0.55), and weakly (r = 0.37) but significantly with clay content. The attained pHBC values indicated that calcite was probably the main buffer system in these soils. The chemical equilibrium model successfully predicted pH titration curves based on calcite dissolution, indicating buffering of acid inputs in the calcareous soils is dominated by calcite dissolution. The model can be used to simulate acidification of calcareous soils and to provide information for making environmental management decisions.