One equation to analyse the pH of soil systems

Starting from the basic equations of chemical equilibrium, an analytical mathematical expression is derived that relates pH to base saturation, concentration of acid anions (SO₄^2?, NO₃^?, etc.) and other properties of the soil and soil solution. The equation is particularly valid in acid soils (low base saturation and relatively large, >100 μmol_c dm^?3, concentration of acid anions) in the range in which cation exchange is the buffering mechanism. Values of pH, alkalinity and degassed pH calculated with the aid of this equation compared well to values measured in three forest-floor horizons; calculated pH values also compared well to values measured on a number of acid soils. The equation is also used to derive analytical mathematical expressions for alkalinity, soil leaching sensitivity (a measure of the sensitivity of a soil solution to become dominated by A1³⁺), and other variables of interest in the context of acidification.     

Saline-alkali soils of Russia

Diagnostics, methods of evaluation, and geography of saline-alkali (soda) soils are discussed. The saline-alkali soils include soils of different genetic types with the following chemical properties: the pH of the water suspensions equal to or higher than 8.5; the total alkalinity exceeding 1.4 meq/100 g of soil and the sum of water-soluble calcium and magnesium; and the presence of soluble “alkaline” salts in the soil profiles, the hydrolysis of which results in the alkaline reaction of the soils. The chemical properties of the saline-alkali soils are largely related to the presence of soda (Na₂CO₃, NaHCO₃) in the soils. According to their morphological properties, saline-alkali soils are divided into two groups: alkaline soils with an undiferentiated profile and without a morphologically pronounced solonetzic (natric) horizon, and alkaline soils with a pronounced natric horizon (solonetzes). Solonetzes, in turn, are divided into (a) alkaline solonetzes (with soda or with soda and neutral salts), (b) solonetzes salinized with neutral salts (saline soils) with increased alkalinity in the solonetzic and lower lying horizons, (c) saline solonetzes throughout the profile, and (d) leached solonetzes containing no soluble salts in the profile and almost no exchangeable sodium in the soil exchange complex (SEC) (“dead” solonetzes). The latter two groups of solonetzes cannot be ranked among the alkaline soils. The alkalinity of the saline-alkali soils under study is due to carbonate and bicarbonate ions (carbonate alkalinity), organic acid anions (organic alkalinity), and borate ions (borate alkalinity). The carbonate alkalinity is due to both soda (Na₂CO₃, NaHCO₃) and CaCO₃.     

Solubility,sorption and desorption of native and added cadmium in relation to properties of soils in New Zealand

Solution cadmium (Cd) concentrations and sorption and desorption of native and added Cd were studied in a range of New Zealand soils. The concentration of Cd in solution and the concentrations and patterns of native soil Cd desorbed and added Cd sorbed and desorbed varied greatly between the 29 soils studied. Correlation analysis revealed that pH was the most dominant soil variable affecting solution Cd concentration and sorption and desorption of native and added Cd in these soils. However, organic matter, cation exchange capacity (CEC) and total soil Cd were also found to be important. Multiple regression analysis showed that the log concentration of Cd in solution was strongly related to soil pH, organic matter and total Cd, which in combination explained 76% of the variation between soils. When data from the present study were combined into a single multiple regression with soil data from a previously published study, the equation generated could explain 81% of the variation in log Cd solution concentration. This reinforces the importance of pH, organic matter and total Cd in controlling solution Cd concentrations. Simple linear regression analysis could at best explain 53% of the total variation in Cd sorption or desorption for the soils studied. Multiple regression analysis showed that native Cd desorption was related to pH, organic matter and total Cd, which in combination explained 85% of the variation between soils. For sorption of Cd (from 2 μg Cd g^–1 soil added), pH and organic matter in combination explained 75% of the variation between soils. However, for added Cd desorption (%), pH and CEC explained 77%. It is clear that the combined effects of a range of soil properties control the concentration of Cd in solution, and of sorption and desorption of Cd in soils. The fraction of potentially desorbable added Cd in soils could also be predicted from a soil’s K_d value. This could have value for assessing both the mobility of Cd in soil and its likely availability to plants.     

Cadmium Release in Soil Solutions at Low Moisture Content

Abstract

Speciation of cadmium (Cd) was studied in four spiked agricultural soils at moisture content corresponding to 1.2 times field moisture capacity (FMC) and in the range from 1.2 FMC to soil–water 1∶10. Cadmium desorption isotherms were nonlinear in all soils, resulting in the decrease in Cd partition coefficient with loading. The Windermere Humic Aqueous Model (WHAM VI) was applied to predict Cd concentration in the solutions, and predicted values were compared with the measured ones. Based on total Cd content in soils, with concentrations of dissolved organic carbon (DOC), calcium (Ca), magnesium (Mg), and sodium (Na) and soil solution pH as the input variables, WHAM VI predicted Cd concentration in soil solutions with the root‐mean‐square error (RMSE) of log[Cd] RMSE_log[Cd]=0.54 (n=37). Using total Cd content in soils, average concentrations of Ca and DOC in soil solutions, and soil pH instead of soil solution pH enabled prediction of Cd concentration in soil solution with RMSE_log[Cd]=0.56. Calculation of Cd concentration as a function of moisture content resulted in RMSE_log[Cd]=0.25 (n=20).     

Oxalic Acid Effect on Potassium Release from Typical Rice Soils of Kashmir

Batch experiments were employed to examine the influence of oxalic acid on release kinetics of potassium (K) from soils along with adsorption and desorption of soil K⁺. The soils used were three rice soils from high-, mid-, and low-altitude zones. The results showed that soil K extracted using 0.2 mol L^–1 oxalic acid was similar to that of 1 mol L^–1 boiling nitric acid (HNO₃). The relation between K release (y) and concentrations of oxalic acid (c) could be best described as y = a + b log c, whereas the best-fit kinetic equation of K release was y = a + b √t. The K release for soils was in the order Bonbagh > Ganasthan > Kreeri. An oxalic acid solution with low pH was able to release more K. Oxalic acid decreased soil K⁺ adsorption and increased desorption, the effect of which tended to be greater at lower pH.     

Adsorption of Cadmium by Indian Soils

Adsorption behaviour of cadmium (Cd) in soils is an important process which exerts a major influence on its uptake by plant roots. Thirteen soils from various parts of India (tropical region), their pH ranging from 4.2 to 8.4, were subjected to Cd treatment at various concentrations (1 to 100 μg ml-1) and equilibrated at room temperature (25 ± 1 °C). The Cd adsorbed by each soil was calculated as the difference between the amount of Cd present in the solution initially and that remaining after equilibration. Results indicated that the adsorption capacity of the soils for Cd increased with an increase in the pH or alkalinity of the soils. The rate of adsorption was, however, found to decrease with increased pH. All the 13 soils used in this study followed linear and Freundlich adsorption isotherms with highly significant positive correlations (r). The neutral and alkaline soils also followed the Langmuir adsorption isotherm, the adsorption maxima being lowest for the neutral soil and highest for the alkaline soil. The adsorption data, in general, indicated that Cd was in a fixed form at higher pH levels. The results are generally similar to those of the temperate regions; however, Cd adsorption capacity of tropical vertisols was comparatively higher than those of temperate vertisols.     

Mapping soil salinity and pH across an estuarine and alluvial plain using electromagnetic and digital elevation model data

Increasing pressures from agriculture and urbanization have resulted in drainage of many floodplains along the eastern Australian coastline, which are underlain by sulphidic sediments, to lower water tables and reduce soil salinity. This leads to oxidation of the sediments with a rapid decline in pH and an increase in salinity. Accurately mapping soil salinity and pH in coastal acid sulphate soil (CASS) landscapes is therefore important. One required map is the extent of highly acidic (i.e. pH < 4.5) areas, so that the application of alkaline amendments (e.g. lime) to neutralize the acid produced can be specifically targeted to the variation in pH. One approach is to use digital soil mapping (DSM) using ancillary information, such as an EM38, digital elevation models (DEM – elevation) and trend surface parameters (east and north). We used an EM38 in the horizontal (EM38h) and vertical (EM38v) modes together with elevation data to develop multiple linear regressions (MLR) for predicting EC_1:5 and pH. For pH, best results were achieved when the EM38 EC_a data were log‐transformed. By comparing MLR models using REML analysis, we found that using all ancillary data was optimal for mapping EC_1:5, whereas the best predictors for pH were north, log‐EM38v and elevation. Using residual maximum likelihood (REML), the final EC_1:5 and pH maps produced were consistent with previously defined soil landscape units, particularly CASS. The DSM approach used is amenable for mapping saline soils and identifying areas requiring the application of lime to manage acidic soil conditions in CASS landscape.     

Reactions of urea phosphate in calcareous and alkaline soils: II. effects on soil sodium and salinity

Abstract

Large areas of agricultural land, containing alkalinity and salinity problems, are potentially suitable for crop production with little alteration of their chemical properties. This study was conducted to determine and compare the effectiveness of urea phosphate (UP) in reducing soil salinity and alkalinity with sulfur foam (SF), phosphoric solution (PHP), and a mixture of SF and UP (Mix) on leaching soil sodium (Na) and salinity on two saline sodic soils (Pima L and Crot CL) in columns. Each of these amendments was applied at rates of one and two equivalent amounts of the exchangeable sodium (Na_ex).

Urea phosphate was as effective as PHP or Mix treatments in reducing soil salinity and alkalinity in Pima and Crot soils. No difference was found between rates of application (1 and 2 equivalent amount of Na_ex) except for soil pH. The decrease in soil salinity was similar to the decrease in pH levels; both decreases followed this order: PHP, UP, Mix, SF, and control treatments. No significant difference was found between SF and control treatments for all parameters. No significant difference was found between treatments for exchangeable Ca (Ca_ex), as both soils contained free CaCO₃. Generally, UP is a potential fertilizer for supplying nitrogen (N) and phosphorus (P) as plant nutrients, and can be used as a soil amendment to control soil salinity and alkalinity.     

Effects on soil and paddy–wheat crops irrigated with waters containing residual alkalinity

Degradation of soils by irrigation with ground waters containing residual alkalinity poses a major threat to agriculture in semi‐arid regions, particularly in South Asia. However, there is a lack of indices to define the soil degradation and crop performance under a monsoon climate. Therefore, an experiment was conducted during 2000–2004 to determine the responses of paddy rice and wheat crops in rotation to irrigation with alkaline waters (AW) having similar salinity (electrolyte concentration 30 me L^?1) but varying ionic constituents (sodium adsorption ratio irrigation water, SARiw 10 and 25; adjusted sodium adsorption ratio, adj.R_Na 13.6 and 29.2; residual sodium carbonate, RSC 5 and 10 me L^?1 and Cl:SO₄ 4:1 and 1:4, respectively). The concentration factors, ECe/ECiw (ratio of electrical conductivity of soil's saturation paste extract to that of the irrigation water) were between 1.1 and 1.8 for soils deprived of rainfall, whereas it was almost 1 for soils not sheltered from rain. Similarly, saturation paste extract, SARe, was between 1.6 and 2.0 times SARiw and 2.0–2.3 times SARiw with and without rainfall, and the exchangeable sodium per cent (ESP) 1.0–1.8 times SARiw. Yields of paddy relative to yields of crops irrigated with good‐quality water, averaged 56–74% during the period 2000–2004 compared with 81–88% for wheat, indicating the greater sensitivity of rice to irrigation with AW. Elevated levels of sulphate rather than chloride in the irrigation water lessened the impacts of the residual alkalinity. Production functions showed that the sodicity (ESP) did not solely explain the variation in crop yields because the salinity stress simultaneously inhibited growth. None of the sodicity indices (RSC, SAR and adj.R_Na) adequately defined the relative impacts of AW, although residual alkalinity (RSC) was a better indicator than either of the other two. The monsoon rains played an important role in alleviating the effects of residual alkalinity. Data presented here should support the development of more reliable criteria for the assessment of sodicity/salinity hazards from AW in semi‐arid regions.     

Neutralization of atmospheric acid inputs in small spring catchments in the Frankenwald mountains,Germany

Investigations on soil and freshwater acidification are usually focused on well-aerated systems. This study deals with the role of reductive processes for the neutralization of acid soil solution within helocrene springs. Two toposequences consisting each of three profiles (forest soil, margin of fen, fen) were established to study the chemistry of the solid phase (soil pH, CEC, pedogenic Fe- and Al-oxides) and the soil solution in two small spring catchments on three dates during 1991 and 1992. Despite high acid inputs and acidified forest soils the pH of the spring outflow is near neutral, and the soil solid phases of the spring fens are not acidified. The results support the following hypothesis: Aluminum with its corresponding anion sulfate is leached with the soil solution into the water-saturated fens. Dissimilatory iron and sulfate reduction take place within the fen and generate alkalinity. Reduced iron either reacts with sulfide to form pyrite or migrates within the fen profile and precipitates in the uppermost, oxic horizons, consuming part of the generated alkalinity. Due to the higher pH values in the fens the incoming aluminum precipitates releasing acidity. The alkalinity generated exceeds the amount of acidity released by oxidation and precipitation of iron and the precipitation of aluminum. A balance of alkalinity consuming and alkalinity generating processes based on solid phases showed that iron and sulfate reduction can account for at least 67% of the neutralization of acidity entering the fen of one of the catchments. Due to shorter water retention times and higher discharge these processes are of minor importance in the other catchment.     

外源铜和镍在土壤中的化学形态及其老化研究

采用连续提取法测定了外源铜和镍进入田间土壤后的化学形态分布,比较研究了这2种重金属在3种不同类型土壤(红壤,水稻土和潮土)中随老化时间的形态转化和分布.结果表明,外源铜以残留态(40%～60%)和EDTA可提取态(40%)为主;随老化时间,EDTA可提取态、易还原锰结合态及铁铝氧化态向残留态转化;外源镍在酸性红壤中以可交换态(40%)和残留态(30%～50%)为主,在中性水稻土中以EDTA可提取态(30%)和残留态(30%～50%)为主,在碱性潮土中以铁铝氧化态(20%)和残留态(40%)为主.随老化时间,水溶态、可交换态、EDTA可提取态等向残留态转化.土壤pH较低时水溶态和可交换态含量较高,但是同时随老化时间的降低量也明显;pH较高时有利于易还原锰结合态和有机质结合态的转化.     

ELECTRIC CHARGE CHARACTERISTICS OF ANDO A, AND BURIED A, HORIZON SOILS

The electric charge characteristics of four Ando soils (A₁ and μA₁) and a Chernozemic soil (Ap) were studied by measuring retention of NH₄⁺ and Cl^– at different pH values and NH₄Cl concentrations. No positive charge appeared in the Ando soils at pH values 5 to 8.5 except for one containing allophane and imogolite. The magnitude of their negative charge (CEC; meq/l00g soil) was dependent on pH and NH₄Cl concentration (C; N) as represented by a regression equation: log CEC =a pH +b log C +c, where the values of a and b were 0.113–0.342 and 0.101–0.315, respectively. Unlike the Chernozemic soil, Ando soils containing allophane, imogolite, and/or 2:1–2:1:1 layer silicate intergrades and humus showed a marked reduction of cation retention as pH decreased from 7 to 5. This was attributed to the charge characteristics of the clay minerals and to the carboxyl groups in humus being blocked by Al and Fe.     

Diffusion of urea, ammonium and soil alkalinity from surface applied urea

A model for predicting the concentration profiles of urea, ammonium and soil pH in a soil column following diffusion from a surface application of urea is developed, using independently derived parameters, and tested experimentally. The following processes within the model were studied separately under the same conditions as those in the diffusion run. The rate of urea hydrolysis as a function of substrate concentration and pH in the soil solution, and the sorption of urea and ammonium by the soil from solution. A theory for the propagation of changes of pH in soils was applied to describe the diffusion of soil alkalinity arising from urea hydrolysis. These processes were linked by three diffusion equations—for urea, NH₄ and soil alkalinity, which were solved numerically using finite difference methods. There was good agreement between experimental and predicted concentrations of urea and NH₄, and soil pH values at the two times tested.     

Temporary storage of soil organic matter and acid neutralizing capacity during the process of pedogenetic acidification of forest soils in Kinki District,Japan

Abstract

Pedogenetic acidification processes in forest soils derived from sedimentary rocks under mesic and thermic soil temperature regimes (MSTR and TSTR; corresponding to mean annual soil temperatures of 8–15°C and 15–22°C, respectively) in the Kinki District were investigated based on titratable alkalinity and acidity characteristics and soil solution composition. According to statistical analyses of the soil properties, the titratable alkalinity required to acidify soils to pH 3.0 was considered to be derived from reactions occurring at the surface of amorphous Al oxides, while titratable acidity at a pH ranging from 5.5 to 8.3 results from dissociation of acidic functional groups of soil humus and/or deprotonation of oxide surfaces. These reactions were generally more prevalent in MSTR soils. Based on the soil solution composition and titratable alkalinity and acidity in the soil profiles, two processes were postulated for pedogenetic acidification, that is, eluvi-illuviation of inorganic Al followed by subsequent adsorption of dissolved organic carbon (DOC) onto the precipitates of Al hydroxides and comigration of Al and DOC in the form of organo-mineral complexes. Both processes were conspicuous in MSTR soils and significantly contributed to soil organic matter storage in the subsoil layers. Pedogenetic acidification in forest soils with MSTR was characterized by an accumulation of acidity in the form of amorphous compounds and/or organo-mineral complexes in the B horizon. It seems, to some extent, similar to podzol formation, at least in terms of Al translocation. Amorphous Al hydroxides protect against further acidification through protonation and/or partial monomerization and can, thus, be regarded as a temporary storage of acid neutralizing capacity of the soil, which would be otherwise leached out directly from the soil profile. In contrast, the acid-buffering reactions of TSTR soils seemed to occur, if at all, mostly at or near the soil surface and the contribution of the B-horizon soils was limited.     

Adsorption—desorption and/or precipitation—dissolution processes of zinc in soils

The concentrations of trace and toxic metals in soil solutions are explained by several authors either in terms of adsorption—desorption or precipitation—dissolution reactions in soils. Data have been given for zinc to test the applicability of both concepts. The results show that the concentrations of zinc in equilibrium solutions with soil clay fractions and whole soil samples at pH values below 7 are determined exclusively by adsorption—desorption reactions for various pH's, contents of bound zinc and compositions of soils. At neutral to alkaline pH values precipitation—dissolution reactions of zinc may take place. There is some evidence that formation of zinc silicates may control the zinc concentration in solution provided natural complexing agents are absent, the affinity of the soil for zinc is low and the content of reaching zinc is high (> ～ 100 ppm). Even at pH values above 7, the formation of other zinc compounds is unlikely in most soils because additions of large amounts of zinc are required to ensure saturation of the adsorption sites of different soil components before the zinc concentration in the soil solution can increase sufficiently to bring about the precipitation of definite compounds. Model experiments in CaCO₃-buffered systems showed that the adsorption capacity for specifically adsorbed zinc (in μmole/g) by the following components increased in the order CaCO₃ (0.44), bentonite (44), humic acid (842), amorphous Fe- and Al-oxides (1190, 1310) and δ -MnO₂ (1540) and demonstrated the importance of Mn-, Fe-, and Al-oxides and humic substances for the binding of zinc in soils containing carbonates, and thus indicate the special role of these components in limiting precipitation reactions.     

pH,nitrogen mineralization,and KCl-extractable aluminum as affected by initial soil pH and rate of vetch residue application: results from a laboratory study

Purpose

Initial soil pH determines the direction and magnitude of pH change after residue addition. This study aimed to evaluate the relative importance of initial soil pH and rate of residue application in determining subsequent pH change, nitrogen (N) mineralization, and soil-exchangeable aluminum (Al).

Materials and methods

An incubation experiment was conducted for 102 days on a Plinthudult soil and a Paleudalf soil, where pH gradients were produced after application of direct current (DC). Rates of vetch applications were 0, 5, 15, 30, and 50 g kg^?1 soil.

Results and discussion

Increasing rates of vetch application caused greater increases in soil pH, but no consistent increase in soil pH at higher initial pH range (4.40～6.74), because of nitrification. There was a positive correlation between alkalinity production and the initial soil pH at day 14, while correlations became negative at days 56 and 102. Mineral N accumulated as NH₄ ⁺–N in low pH soils, due to limited nitrification, while NO₃ ^?–N dominated in higher pH soils. Application of vetch decreased KCl-extractable Al, probably because of complexation of Al by organic matter and precipitation of Al as a result of increased pH, reductions in Al concentration increased with increasing rates of vetch application. However, this amelioration effect on Al concentration weakened with time in higher pH soils.

Conclusions

Application of vetch residue can significantly increase soil pH and concentrations of mineral N and reduce exchangeable Al. These amelioration effects are enhanced with increased rate of vetch addition and vary with time depending on the initial pH of the soil.     

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。     

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。     

Salinization,alkalinization and sodification in Punjab (Pakistan): characterization of the geochemical and physical processes of degradation

Evidence of soil degradation impeding soil tillage and irrigation in cultivated soils in Pakistan is identified, described and represented in a general process of degradation. Based on a chemical analysis of soil characteristics, it is shown that a more general geochemical degradation process may occur in these soils. Two paths of salinization, i.e. neutral salinization and alkalinization inducing a process of sodification, are identified. The wide range of chemical properties of soils and corresponding geochemical processes can be explained by the great diversity of quality in irrigation water that is taken either from the canal or from the groundwater. The basic module of a geochemical model AQUA (Vallès and DeCockborne, 1992) is calibrated with the help of a study of the soil geochemical properties (identification of minerals, characterization of exchanges) and then used to assess the effect of four different water qualities on sandy and loamy soils. Based on these scenarios, the salinity, alkalinity and sodicity hazard of irrigation water is assessed by taking into account simultaneously the electrical conductivity and the residual alkalinity (calcite-residual alkalinity, residual sodium carbonates) or irrigation water and the soil cation exchange capacity: these three indicators appear the most relevant in the context of the study. Copyright © 1999 John Wiley & Sons, Ltd.     

SOIL ALKALINITY. I. EQUILIBRIA AND ALKALINITY DEVELOPMENT

Theoretical relationships between pH, CO₂ partial pressure and alkalinity (bicarbonate + carbonate concentrations) have been shown to apply to solutions and calcite and soil suspensions. The exchange of Na onto three Ca clays shows that Ca is preferred but with negative free energies of exchange. With decreasing total electrolyte concentration, the preference for Ca increases, so that only when the concentration is above 10^-3M will significant amounts of exchangeable Na be found in soils. The preference for Ca is illite > montmorillonite > vermiculite. Dilution of the mixed Na-Ca clay suspensions causes exchange, desorption of Na and. in some cases Ca. This desorbed or ‘alkaline’ Na (and Ca) is replaced by H some of which attacks the clays. The apparent hydrolysis coefficient, KG = H adsorbed (Na)/Na adsorbed (H), varies between 5 and 9 × 10⁵, increases with increase in electrolyte concentration and varies in the order vermiculite > illite > montmorillonite. The concentration of alkaline Na + Ca increases with increasing ESP, and with clay type in the same order as the KG values. The pH calculated from the alkaline Na + Ca, assumed equal to the alkalinity was equal to measured values except for montmorillonite where the calculated values were low. Magnesium release by acid attack of the montmorillonite may explain the differences. Vermiculite rich soils will be most likely to accept exchangeable Na and to hydrolyse and develop alkalinity.