A rapid method to determine cation exchange capacity and exchangeable bases in calcareous,gypsiferous, saline and sodic soils

Summary

A simple, single‐step extraction with LiEDTA for the estimation of CEC and exchangeable bases in soils has been developed. Multivalent cations are stripped from the soil adsorption sites by the strongly chelating agent EDTA, and are replaced by Li. In soils without CaCO₃ or water soluble salts, exchangeable divalent cations (Ca, Mg) are chelated by EDTA and exchangeable monovalent cations (Na, K) are replaced in a single extraction step using 0.25–2.5 g of soil and 10.0 ml of extractant.

In calcareous soils the CEC can be determined in the same way, but for the extraction of exchangeable Ca and Mg, another separate extraction is needed because dissolution of calcite by EDTA is unavoidable. This extraction is done with as much NaEDTA as needed to extract only exchangeable Ca and Mg in a 1:2 (m/V) soil/alkaline‐50% (V/V) aethanolic solution to minimize dissolution of calcite.

In gypsiferous soils gypsum is transformed into insoluble BaSO₄ and soluble CaEDTA by LiBaEDTA thus avoiding interference of Ca from dissolution of gypsum, which renders the traditional methods for determining CEC unsuitable for such soils. To determine exchangeable Ca and Mg, Na₄EDTA is used as for calcareous soils.

In saline/sodic soils replacement of Na by Li is incomplete but the Na/Li‐ratio at the complex after extraction is proportional to the molar Na/Li‐ratio in the extracts, so that the CEC and original exchangeable sodium (ESP) content can be calculated. Additional analysis of Cl and, if necessary, SO₄ in the extracts of saline soils can be used to correct for the effect of dissolution of the salts on the sum of exchangeable cations.

This new method is as convenient as the recently developed AgTU (silverthiourea), but is better suitable for calcareous and gypsiferous soils.     

Ionic balance in the interaction of meadow-chestnut soils with saline groundwater under model experimental conditions

The effect of ascending migration of medium and highly saline sodium-sulfate groundwaters on the salinization of nonsaline meadow-chestnut soils was simulated and quantified in model column experiments over 10 months. Sodium from saline water accumulated in the soil as similar amounts of water-soluble and exchangeable compounds in lower soil horizons. Calcium accumulation as CaCl@2 in the topsoil and as gypsum throughout the profile was accompanied by substitution of Na for exchangeable Ca. Magnesium and chlorine mainly accumulated as soluble salts in the topsoil, and sulfate ions accumulated as gypsum through the profile and as soluble salts in the lower part of the column.     

Distribution patterns of soluble salts and gypsum in soils under large-scale irrigation agriculture in Central Asia

Abstract

Soil salinization is a serious problem in the arid and semi-arid regions of Central Asia. To address the problems, we analyzed the dynamics and distribution patterns of salts in both rice-based and cotton-based cropping fields in selected farms of southern Kazakhstan and Uzbekistan with special emphasis on the dynamics of gypsum, which had a lower solubility than Na salts, as an index of water-movement regimes in irrigated fields. Most of the rice-based plots and some of the cotton-based plots exhibited no surface accumulation of soluble salts or gypsum because of repeated washing by a huge amount of irrigation water in the former or comfortable drainage in the latter. These soils are probably free from the risk of secondary salinization under present conditions and management practices. In contrast, uncultivated plots near canals accumulate both soluble salts and gypsum in the surface soil layers, and these salts would not be leached out without a drastic change to a predominantly downward pattern of water movement. In the intermediate stages in terms of soil salinization, some soils accumulated substantial amounts of soluble salts in surface layers but relatively low amounts of gypsum. In this case, periodic irrigation could have washed out most of the gypsum and soluble salts in a downward direction and, consequently, it is possible to leach out the accumulated soluble salts by applying additional irrigation water if necessary. However, there were some cases in which soils accumulated large amounts of gypsum in surface layers as well as soluble salts, suggesting that irrigation/drainage is generally insufficient to remove gypsum with a lower solubility and that these profiles are dominated by an overall upward movement of water. For these soils, drainage facilities should be improved to ensure the efficient leaching of accumulated salts on cropping. Thus, the condition of irrigated plots in terms of the direction of water movement and resulting salt regimes can be well understood from the distribution patterns of both soluble salts (or cations) and gypsum.     

Salt composition of groundwater and reclaimed solonetzes in the Baraba Lowland

Solonetzes of experimental trials established in 1981 and 1986 in the Baraba Lowland were examined. It was found that gypsum-based ameliorants improve the soil and lead to a decrease in the content of soluble salts in the soil profile. Exchange processes between cations of the soil adsorption complex and calcium of gypsum were particularly intensive in the first years after gypsum application. This resulted in a sharp rise in the content of soluble salts that migrated down the soil profile to the groundwater. In the following years, the reclaimed solonetzes were desalinized under the conditions of relatively stable groundwater level. On the 30th year after single gypsum application, the groundwater level sharply rose (to 50 cm), and the soil was subjected to the secondary salinization; the contents of bicarbonates, carbonates, and sodium in the soils increased. Spring leaching caused some desalinization, but the content of soluble salts in the upper soil meter increased again in the fall. A close correlation between the salt compositions of the groundwater and the reclaimed solonetzes was revealed.     

Gypsum applications to aggregated saline—sodic clay topsoils

Gypsum application was highly efficient as a treatment for reducing amounts of exchangeable sodium and inhibiting clay dispersion in highly structured saline-sodic clay topsoils. Phosphogypsum, applied to the surfaces of aggregates in soil columns treated with simulated rainfall, was dissolved efficiently by frequent intermittent ‘rainfall’. The calcium released by dissolution displaced sodium on the exchange complex within soil aggregates ranging from 7.5 mm to 45 mm in diameter. Of the applied calcium, 64–74% was transferred to ion exchange sites; however, almost one-third of this adsorbed calcium displaced exchangeable magnesium. Comparison of three gypsum treatments, phosphogypsum, rock gypsum, and a saturated gypsum solution (representing a top dressing of highly soluble gypsum), showed that the effectiveness of calcium uptake on the exchange complex followed the order: rock gypsum < saturated solution < phosphogypsum, but differences were small. Application of phosphogypsum caused a 90% reduction in the total amount of dispersed clay released in column leachates, and decreased the maximum clay concentration in the effluents by at least 80%, when compared to soils leached without gypsum treatment.     

Combined application of a straw layer and flue gas desulphurization gypsum to reduce soil salinity and alkalinity

Burying a straw layer and applying flue gas desulphurization(FGD)gypsum are effective practices to ameliorate soil salinization or alkalization and to increase crop yield;however,little information exists on the effects of such integration in saline-alkali soils.A soil column experiment was conducted to investigate the effects of a straw layer plus FGD gypsum on soil salinity and alkalinity.We placed a straw layer(5 cm thick)at a depth of 30 cm and mixed FGD gypsum into the 0–20 cm soil layer at application rates of 7.5,15.0,22.5,and 30.0 t ha^-1,with no straw layer and FGD gypsum as a control(CK).The soil water content in the 0–30 cm soil layer was significantly higher(>7.8%)in the treated soil profiles after infiltration than in the CK,but decreased after evaporation.The electrical conductivity(EC)of the 10–30 cm soil layer was 230.2%and 104.9%higher in the treated soil profiles than in the CK after infiltration and evaporation,respectively,and increased with increasing rates of FGD gypsum application,with Ca^2+and SO4^2-being the main dissolved salts.Compared to those in the CK,the concentrations of Na^+,Cl^-,and HCO3-decreased in the treated soil profiles at depths above 55 cm,but the other soluble ions increased,after infiltration.A similar trend occurred after evaporation for all soluble ions except for HCO3-.The p H and exchangeable sodium percentage in the treated soil profiles were significantly lower than those in the CK over the entire profile,and decreased with increasing FGD gypsum application rates.Therefore,the incorporation of a straw layer plus FGD gypsum can reduce salinity and alkalinity,but the quantity of FGD gypsum should be controlled in saline-alkali soils.     

洛惠渠灌区水土化学特性分析

为了深入了解洛惠渠灌区土壤盐碱化程度,分别测试了2004年实地采集的63个土壤样品和71个地下水样品,测定项目分别为土壤含盐量、碱化度、阴阳离子含量和地下水化学成分,并分析了该灌区土壤盐碱化现状以及地下水水质状况.结果表明,洛惠渠灌区土壤盐碱化较明显,盐渍化土壤分成盐土和碱土两类,主体成分为钠(钾)、钙的硫酸盐和碳酸盐;而地下水化学类型基本属于氯化钠-硫化钠型.通过计算其钠吸附比和镁系数可以推知该灌区地下水大部分对灌溉作物有不利影响,并且对土壤有进一步碱化的威胁.因此,有效控制该灌区地下水位是治理土壤盐碱化的重要措施,还要考虑不同区域土壤易溶盐含量,作物耐盐碱性等因素.应当综合工程、生物、化学等方法来改良利用盐碱土地,方能起到事半功倍的治理效果.     

准噶尔盆地温带荒漠土壤碱化分级的初步研究

准噶尔盆地温带荒漠碱化土壤是一种典型的脱盐碱化土壤,它受交换性钠(镁)和能产生水解作用的强碱弱酸盐水解引起的碱度的影响。在多年野外调查和碱化土壤特性研究的基础上,利用综合数值分析法对这些土壤进行了研究。提出了准噶尔盆地温带荒漠土壤碱化分级的具体指标和数据,并确定了水解性碱度为分级的第一重要指标。在推动和简化荒漠土壤分级上起了积极的作用。     

Transformation of gray forest soils upon technogenic salinization and alkalization and subsequent rehabilitation in oil-producing regions of the southern Urals

The technogenically induced salinization and alkalization (solonetzization) of gray forest soils results in their transformation into soils similar to natural solonchaks and solonetzes. Their density increases, the structure is disturbed, and the water stability of the aggregates becomes poorer. The humus content decreases, the nutrition regime is deteriorated, and the enzymatic activity is hindered. Under natural conditions, soil desalinization is seen within a ten-year-long period after its contamination with strongly saline oil-field waste water, while soil solonetzization remains very high. The soil properties are regenerated after application of an adequate rate of phosphogypsum and manure. Phosphogypsum applied alone causes a deterioration of the agrophysical properties as it produces an extremely high water stability of aggregates and strong soil compaction.     

Changes in the salinity of solonetzic soil complexes of the Ergeni Upland under long-term anthropogenic impact (soil studies at the Arshan’-Zel’men Experimental Station of the Russian Academy of Sciences)

Unique experiments performed since the 1950s at the Arshan’-Zel’men Experimental Station have formed the basis for afforestation in the dry steppe and semidesert zone without irrigation on the salt-affected soils of solonetzic soil complexes of the Ergeni Upland. Ameliorative measures favored the accumulation of productive moisture in the upper 2-m-thick soil layer, which ensured the growth of trees and the partial leaching of soluble salts to a depth of 1–1.4 m. However, no complete desalinization of the soil profiles took place. The degree of removal of exchangeable sodium from the exchange complex (soil dealkalization) was smaller. The monitoring of changes in the salt status of the soils upon agroforest reclamation was performed until the early 1980s. Our investigations of 2005–2006 showed that the soil amelioration is still in progress: the salt maximum in the profile of the solonetzes descended to a depth of 2.2 m, and the exchangeable sodium was lost from the plow layer (0–40 cm). Plowed soils between forest shelterbelts were also subjected to desalinization and dealkalization of their soil profile, though less intensely than those under the shelterbelts.     

甘肃景电灌区次生盐化土壤的性质及其发生机理

本文对甘肃景电灌区次生盐化土壤的理化性质进行了研究 .该区次生盐渍化土壤主要为硫酸盐氯化物和氯化物硫酸盐型 ,水溶性钠离子在阳离子中占绝对优势 .土壤通体碳酸钙含量很高 ,并有少量的石膏 .钠离子饱和度很高 ,具有钠质特性或钠质化现象 ,盐化与钠质化同时进行 .在此基础上对次生盐渍化的机理和改良进行了讨论     

Mechanism of reduction of exchangeable aluminum by gypsum application in acid andosols

Mechanism of reduction of exchangeable aluminum in acid Andosols treated with gypsum was studied by using cation exchange resin methods to determine the amount of polymerized aluminum. Two types of acid Andosols were used as test soils: Kitakami light colored Andosol (fine, mixed, mesic, Andic Dystrochrept) and Kawatabi thick high humic Andosol (medial, mesic mixed Alic Pachic Melanudand). Polymerization of aluminum in the soil solution of both Kitakami and Kawatabi Andosols treated with gypsum was suggested based on an analysis using cation exchange resin methods, whereas that in monomer aluminum solution was not detected. Accumulation of polymerized aluminum in both Kitakami and Kawatabi Andosols was determined by using cation exchange resin, and the amounts of polymer aluminum trapped by the resin and the ratio of polymer aluminum to monomer aluminum were increased with the incubation time. The values of CEC which decreased in the Kitakami Andosol after gypsum treatment were almost equivalent to the amounts of cation exchange sites occupied by polymer aluminum ions which were calculated based on the decrease of the values of Y _l. We conclude that the mechanism of reduction of exchangeable aluminum in strongly acid Andosols treated with gypsum is as follows: firstly, exchangeable aluminum adsorbed on the cation exchange sites of soils may be released into the soil solution due to the increase in the ion strength caused by gypsum application, and then monomer aluminum in soil solution may be polymerized in the presence of soil colloidal materials. Consequently, the polymer aluminum formed in the soil solution may be selectively and irreversibly fixed on the cation exchange sites of 2 : 1 clay minerals.     

Halochemical processes upon washing of calcareous gypsiferous solonchaks

Data on changes in the contents of carbonates, gypsum, and soluble salts upon washing of gypsiferous solonchaks were obtained in laboratory and field experiments. Chemical methods and micromorphological study of thin sections were applied. Stages of the halochemical changes upon the soil washing were identified. It was found that the soil washing results in the formation of secondary magnesium sulfate and pseudomorphic substitution of calcite for gypsum.     

Exchange-induced dissolution of gypsum and the reclamation of sodic soils

A study was undertaken to define the dissolution kinetics of gypsum in the presence of ion exchange resins and to study sodic soil reclamation in laboratory soil columns.
Gypsum pellets were prepared at 1.5 MPa pressure and the time course of their dissolution followed by measuring the electrical conductivity of the solution. Dissolution experiments were carried out in distilled water with and without Na- and Cl-saturated exchange resins or a combination of the two. The results indicate that in the presence of resin the reaction is first order as calcium and/or sulphate are removed from solution by the resin driving the reaction to completion. In water alone the reaction follows second-order kinetics and depends on the rate of mixing as the reaction is transport controlled.
The effect of gypsum placement (uniformly mixed with the entire soil, mixed with the top third of the soil, applied to the soil surface or applied as a saturated gypsum solution) on the efficiency of exchangeable sodium removal, leaching of soluble salts and soil hydraulic conductivity was studied. In addition, the effect of various flow rates on reclamation efficiency was investigated.
The amount of leachate required for reclamation was found to be dependent on gypsum placement, tending to decrease in the order mixed < top third mixed < saturated gypsum solution < gypsum surface application < water. Soil hydraulic conductivity was much higher in the mixed gypsum column than in the gypsum applied on the surface; a result of the higher effective gypsum solubility. Sodic soil electrical conductivity in the presence of solid-phase gypsum is linearly related to the total amount of exchangeable sodium expressed in mol dm⁻³.     

Examination into the Accuracy of Exchangeable Cation Measurement in Saline Soils

Abstract

Despite the increasing prevalence of salinity worldwide, the measurement of exchangeable cation concentrations in saline soils remains problematic. Two soil types (Mollisol and Vertisol) were equilibrated with a range of sodium adsorption ratio (SAR) solutions at various ionic strengths. The concentrations of exchangeable cations were then determined using several different types of methods, and the measured exchangeable cation concentrations were compared to reference values. At low ionic strength (low salinity), the concentration of exchangeable cations can be accurately estimated from the total soil extractable cations. In saline soils, however, the presence of soluble salts in the soil solution precludes the use of this method. Leaching of the soil with a prewash solution (such as alcohol) was found to effectively remove the soluble salts from the soil, thus allowing the accurate measurement of the effective cation exchange capacity (ECEC). However, the dilution associated with this prewashing increased the exchangeable calcium (Ca) concentrations while simultaneously decreasing exchangeable sodium (Na). In contrast, when calculated as the difference between the total extractable cations and the soil solution cations, good correlations were found between the calculated exchangeable cation concentrations and the reference values for both Na (Mollisol: y=0.873x and Vertisol: y=0.960x) and Ca (Mollisol: y=0.901x and Vertisol: y=1.05x). Therefore, for soils with a soil solution ionic strength greater than 50 mM (electrical conductivity of 4 dS/m) (in which exchangeable cation concentrations are overestimated by the assumption they can be estimated as the total extractable cations), concentrations can be calculated as the difference between total extractable cations and soluble cations.     

河套灌区乌拉特灌域春季土壤盐碱化空间分布特征

盐碱化状况是干旱区灌区水盐合理调控及水土资源合理利用的基础。为掌握内蒙古河套灌区下游乌拉特灌域春季耕地土壤盐碱化状况的空间分布,通过野外调查采样和实验室检测,对0~20 cm和20~40 cm土层中的全盐量（Total Salt,TS）、pH值、CO32-、HCO3-、Cl-、SO42-、Ca2+、Mg2+、K++Na+含量、交换性Na+含量、阳离子交换量（Cation Exchange Capacity,CEC）、碱化度（Exchangeable Sodium Percentage,ESP）等反映土壤盐碱化特征的指标进行了测定和计算,采用经典统计学、地统计学和多指标综合评价方法对土壤盐碱化指标的空间分布特征进行分析。结果表明：1）0～20 cm土层中的TS含量更大一些,可溶性盐分离子主要以HCO3-、SO42-、Cl-、Na+为主。HCO3-、CEC、交换性Na+和ESP的变异系数在10%～100%之间,属于中等变异,其中交换性Na+和ESP的变异系数接近100%;TS、Cl-、SO42-和Na+的变异系数均大于100%,属于强变异。2）土壤pH、TS和ESP的空间分布规律基本一致,在东西方向上,各指标西部低,东部高;在南北方向上,中间低,南、北两侧高。土壤pH值基本在7.5～8.5之间,从TS空间分布来看,灌域内有32%的土壤存在盐渍化问题,且以轻度盐渍化土为主,约占26%;从ESP分布来看,有97%的土壤存在碱化问题,其中轻度碱化土约占40%,中度碱化土和碱土均约占23%。因此灌域内土壤碱化问题比盐化问题更为突出。3）通过因子分析得出TS、Cl-、Na+、交换性Na+、ESP和CEC是乌拉特灌域土壤盐碱化程度的主要影响因子,公因子综合得分值在-0.78~3.38之间,公因子综合得分能排除指标间个体差异,比较客观地评价土壤盐碱化整体水平。     

Effect of oil contamination on the properties of leached chernozem under model experimental conditions

A model experiment was performed to study the effect of soil contamination with oil on the growth of wheat plants. Neither significant downward migration of oil or oil components, including the most mobile aromatic hydrocarbons, in a column with leached chernozem nor removal of these compounds from the column were observed when the initial oil concentration was below 0.75%. These data confirmed the previous results that oil at a concentration of 0.3% had no negative effect on the growth of wheat. The synergetic effect of oil, soluble salts, and exchangeable sodium should be taken into account in the determination of maximum permissible residual oil content in soils.     

Gypsic pedofeatures and elementary pedogenetic processes of their formation

Elementary pedogenetic processes forming gypsic pedofeatures in gypsiferous soils are discussed. Several groups of such processes are distinguished: (1) weathering of gypsum-bearing rocks; (2) gypsum formation associated with weathering of sulfuric (pyritic) rocks; (3) precipitation of gypsum owing to the inflow of soil solutions saturated with Ca and SO₄ and their evaporative concentration; (4) gypsum formation owing to exchange reactions in soils between calcium in the exchange complex and sodium sulfate solutions; (5) gypsum formation upon interaction of calcium carbonates with sodium sulfate water resulting in the loss of CaCO₃ and gypsum accumulation (decalcification process); (6) colluvial and alluvial redeposition of gypsum in the landscape with its accumulation in the subordinate positions, where gypsiferous soils are formed; and (7) eolian deposition of gypsum on the soil surface with the formation of gypsum-bearing horizons. The micromorphological specificity of the gypsic pedofeatures reflects the processes of their destruction and/or accumulation in the soil profiles. It is shown that gypsum accumulation in soils is a pedogeochemical process that manifests itself in different natural zones upon the presence of gypsum sources.     

Dynamics of Sodium in Saline and Sodic Soils

Abstract

Soil salinization and sodication affect large areas of agricultural land in the world. Amelioration of these soils to make them suitable for agricultural production depends on understanding sodium dynamics and chemical interactions governing nutrient availability. Three locations in eastern Croatia were characterized to the 5‐m depth. The two solonetz‐solonchak soils were alkaline, whereas the solonetz soil had near‐neutral A/E horizon and alkaline deeper horizons. Electrical conductivity of the saturated extract (ECe) was greater than 4 dS m^?1 in the top horizons in the solonetz‐solonchak soils. The solonetz soil had 2.8–4.7 dS m^?1 in shallow A/E, CG, and G horizons and up to 6.3 dS m^?1 below 1.5 m. Highly alkalinized sodic horizons (exchangeable sodium percentage, ESP >20) had 24–47% Ca²⁺ and 27–33% Mg²⁺ on the cation exchange complex. Sodium adsorption ratio (SAR) was high (18–26) in the P horizon and even more so in Bt,na horizon (35–36) of solonetz‐solonchak soils. A strong negative exponential relationship existed between soluble Ca²⁺ and SAR (SAR increased greatly when Ca²⁺ dropped to around 3 mg dm^?3). An increase in pH to greater than 8.4 resulted in an exponential increase in SAR. Leaching of Na⁺ with successive volumes of water was similarly effective for the P and Bt,na horizons in the solonetz‐solonchak soils, but SAR remained greater than 15 even after six successive cycles of leaching. In conclusion, extensive amelioration of tested soils with gypsum and leaching will be required to overcome poor physical and chemical characteristics caused by various degrees of alkalization and sodication to bring these soils into production.     

滨海盐渍土的碱化问题

滨海盐渍土是否有碱化问题,特别是在开垦利用以后,土壤是否会向碱化方向演化,这是很多生产单位所关心的问题。对此,过去已做了不少工作。有人认为滨海盐渍土由于长期受海水浸渍,土壤胶体表面吸附着大量的钠离子,因此有比较高的碱化度,盐渍程度愈重则碱化度愈高,随着土壤脱盐同时脱碱,当不致进一步碱化^[3]。也有人认为滨海盐债土耕垦后不会发生碱化,其碱化度随改良利用年限而降低^[1]。还有人在滨海盐溃土耕垦种稻后,观测到在土壤脱盐过程中,土壤pH值和总碱度有所增高,认为土壤发生了碱化^[2,5]1)。我们就这一间题曾先后对浙江上虞、乐清,江苏东台、大丰、滨海、灌云以及辽宁兴城、锦县、大洼等县的滨海地区进行了调查研究和室内试验。