Evaluation of industrial by-products as soil acidity amendments: chemical and mineralogical implications

Lime, mined gypsum and some gypsum-like by-products have been frequently applied to soil to counter acidity. We have examined the changes in the chemical and mineralogical properties of three acid soils resulting from the application of three industrial by-products (phosphogypsum, red gypsum and sugar foam). We did so in laboratory experiments on suspensions of soil in saturated solutions of the by-products. A sizeable fraction of the Al released by exchange with Ca of the amendments remained on the mineral surfaces as Al polymers, as suggested by changes in the CuCl₂-, oxalic–oxalate- and DTPA-extractable Al contents. Polymerization of Al was promoted by corresponding neutral and basic pH of red gypsum and sugar foam saturated solutions, respectively. Sorption of these Al polymers was particularly favourable in those horizons with more clay fraction and variable-charge clay minerals. On the other hand, in most cases there was little or no detectable sorption of sulphate, thus excluding precipitation of crystalline or amorphous basic Al sulphates to alleviate Al toxicity. Based on the reduction of the Al saturation of the exchange complex in the soils, as well as on the small contents of heavy metals and natural radionuclides of the three by-products, these can be considered effective alternatives to mined gypsum and lime for alleviating soil acidity and reducing toxic concentrations of Al in agricultural, acid soils.     

Soil Fertility,Sugarcane Yield Affected by Limestone,Silicate, and Gypsum Application

The aim of this study was to verify if the application of silicate or lime, in association with gypsum, on sugarcane residue can lead to amendment of subsurface soil acidity, increasing sugarcane yield and profitability. The treatments were: 1 – control (without application of amendments), 2 – gypsum, 3 – dolomitic limestone, 4 – silicate, 5 – dolomitic limestone + gypsum, and 6 – silicate + gypsum. The surface application of gypsum led to reduction in Al (aluminum) contents and Al saturation, and increase in Mg⁺², Ca⁺², K⁺, S–SO₄^?, and base saturation in deeper soil layers, as well as increased yield of stalks, sugar, trash, bagasse, and energy, and greater profit. The application of limestone and silicate, alone or in association with gypsum, amend soil acidity throughout the soil profile. It likewise leads to an increase in stalk, sugar, trash, bagasse, and energy yield, however, application of silicate in association with gypsum leads to the greatest profitability.     

Immobilization of the heavy metals Cd, Cu and Pb in an acid soil amended with gypsum- and lime-rich industrial by-products

In situ stabilization of heavy metals in contaminated soils by the addition of various types of soil amendment is an attractive technique for remediation. We investigated the potential of three industrial by‐products (phosphogypsum, red gypsum and dolomitic residue) for boosting the heavy metal sorption capacity of an acid soil (patents pending, Spanish applications no 200201704 and 200201375) by using sorption isotherm experiments. The three by‐products were found substantially to increase the retention of lead, cadmium and copper on the solid components of the soil. The increase in lead retention of the soil horizons upon the addition of both phosphogypsum and red gypsum was dominated by the formation of anglesite minerals. The dolomitic residue increased the metal retention capacity of the soil horizons through the precipitation of laurionite‐type minerals as well as cadmium and copper hydroxy‐chlorides. In addition to the batch sorption study, we used scanning electron microscopy to investigate the metal sorption processes in the soil by the effect of the treatments. Lead was frequently found to be linked to the edge charges of kaolinite minerals. The three metals were found to be associated with organic matter in the Ap horizon treated with the three by‐products. Finally, the three metals were found to be associated with undissolved dolomitic residue particles.     

Chemical species of Al in a gypsum-treated Kitakami Andosol

To examine the possibility that the Al₁₃ polymer ([A10₄Al₁₂(OH)24(H₂0)₁₂]⁷⁺) could be formed in soils after gypsum application, an analytical method using a cation exchange resin and ²⁷Al nuclear magnetic resonance (NMR) spectroscopy was applied to gypsum-treated Kitakami Andosol (fine, mixed, mesic, Andic Dystrochrept). The NMR spectra of the cation exchange resins which retained artificially synthesized hydroxy-AI, showed two broad peaks at 0 and 63 ppm. These results indicated that monomer and/or dimer Al and Al¹³ polymers adsorbed on the cation exchange resin could be detected with ²⁷Al NMR. The amount of polymer Al increased by gypsum application in the Kitakami soil. The NMR spectrum of this resin showed only one peak at 0 ppm indicating that the polymer Al formed in the gypsum treated Kitakami soil was not the Al¹³ polymer.     

Soil properties that affect sulphate adsorption by palexerults in western and central Spain

Abstract

The beneficial action of gypsum in suppressing aluminum (Al) toxicity in Bt horizons of Ultisols is related to the self‐liming effect of the adsorption of sulphate (SO₄ ^2‐) ion. The relationship between SO₄ ^2‐ adsorption by gypsum‐amended soils and some components and properties of 38 surface and subsurface horizons from seven Palexerults in western and central Spain was analyzed. The highest correlations of maximal SO₄ ^2‐ adsorption as determined from langmuir isotherms were with clay, free iron oxyhydroxides (Fe_dcb), and exchangeable Al contents, and pH. Liming reduces SO₄ ²’ ion adsorption; consequently, the joint application of limestone and gypsum to the surface of these soils results in increased availability of gypsum for the subsurface horizons.     

pH and solubility of aluminium in acidic forest soils: a consequence of reactions between organic acidity and aluminium alkalinity

Data from two Podzol O and E horizons, sampled in 1-cm layers at 13 points within 2 m × 2 m plots, were used to test the hypothesis that the composition of hydrogen ions (H) and aluminium (Al) adsorbed to the solid-phase soil organic matter (SOM) determines pH and Al solubility in organic-rich acidic forest soils. Organically adsorbed Al was extracted sequentially with 0.5 m CuCl₂ and organically adsorbed H was determined as the difference between total acidity titrated to pH 8.2 and Al extracted in 0.5 m CuCl₂. The quotient between fractions of SOM sites binding Al and H (N_Al/N_H) is shown to determine the variation in pH and Al solubility. It is furthermore shown that models in which pH and Al solubility are linked via a pH-dependent solubility of an Al hydroxide and in which cation exchange between Al³⁺ and Ca²⁺, rather than cation exchange between Al³⁺ and H⁺, is the main pH-buffering process cannot be used to simulate pH or Al solubility in O and E horizons. The fraction of SOM sites adsorbing Al increased by depth in the lower O and throughout the E horizon at the same magnitude as sites adsorbing H decreased. The fraction of sites binding the cations Ca²⁺ + Mg²⁺ + K⁺ + Na⁺ remained constant. It is suggested that a net reaction between Al silicates (proton acceptors) and protonated functional groups in SOM (proton donors) is the long-term chemical process determining the composition of organically adsorbed H and Al in the lower part of the O and in the E horizon of Podzols. Thus, in the long term, pH and Al solubility are determined by the interaction between organic acidity and Al alkalinity.     

Cation exchange in forest soils: the need for a new perspective

The long‐term sustainability of forest soils may be affected by the retention of exchangeable nutrient cations such as Ca²⁺ and the availability of potentially toxic cations such as Al³⁺. Many of our current concepts of cation exchange and base cation saturation are largely unchanged since the beginnings of soil chemistry over a century ago. Many of the same methods are still in use even though they were developed in a period when exchangeable aluminium (Al) and variable charge were not generally recognized. These concepts and methods are not easily applicable to acid, highly organic forest soils. The source of charge in these soils is primarily derived from organic matter (OM) but the retention of cations, especially Al species, cannot be described by simple exchange phenomena. In this review, we trace the development of modern cation exchange definitions and procedures, and focus on how these are challenged by recent research on the behaviour of acid forest soils. Although the effective cation exchange capacity (CECe) in an individual forest soil sample can be easily shown to vary with the addition of strong base or acid, it is difficult to find a pH effect in a population of different acid forest soil samples. In the very acidic pH range below ca 4.5, soils will generally have smaller concentrations of adsorbed Al³⁺. This can be ascribed to a reduced availability of weatherable Al‐containing minerals and a large amount of weak, organic acidity. Base cation saturation calculations in this pH range do not provide a useful metric and, in fact, pH is modelled better if Al³⁺ is considered to be a base cation. Measurement of exchangeable Al³⁺ with a neutral salt represents an ill‐defined but repeatable portion of organically complexed Al, affected by the pH of the extractant. Cation exchange in these soils can be modelled if assumptions are made as to the proportion of individual cations that are non‐specifically bound by soil OM. Future research should recognize these challenges and focus on redefining our concepts of cation retention in these important soils.     

Soil base saturation affects root growth of European beech seedlings§

To assess the potential effects of Al toxicity on the roots of young European beech (Fagus sylvatica L.), seeds were sown in soil monoliths taken from the Ah and B horizons of forest soils with very low base saturation (BS) and placed in the greenhouse. The Ah horizons offered a larger supply of exchangeable cation nutrients than the B horizons. After 8 weeks of growth under optimal moisture conditions, the seedlings were further grown for 14 d under drought conditions. Root‐growth dynamics were observed in rhizoboxes containing soils from the Ah and B horizons. The concentrations of Al³⁺, base cations, and nitrate in the soil solution and element concentrations in the root tissue were compared with above‐ and belowground growth parameters and root physiological parameters. There was no strong evidence that seedling roots suffered from high soil‐solution Al³⁺ concentrations. Within the tested range of BS (1.2%–6.5%) our results indicated that root physiological parameters such as O₂ consumption decreased and callose concentration increased in soils with a BS < 3%. In contrast to the B horizons, seedlings in the Ah horizons had higher relative shoot‐growth rates, specific root lengths, and lengths and branching increments, but a lower root‐to‐shoot ratio and root‐branching frequency. In conclusion, these differences in growth patterns were most likely due to differences in nutrient availability and to the drought application and not attributable to differences in Al³⁺ concentrations in the soil solution.     

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.     

Interactions of aluminium and fulvic acid in moderately acid solutions: stoichiometry of the H+/Al3+ exchange

Complexation with organic matter controls the activity of dissolved Al³⁺ in many soils. The buffering intensity of these soils is largely dependent on the H⁺/Al³⁺ exchange ratio, i.e. the number of protons consumed by the solid phase when one Al³⁺ is released. Here, the H⁺/Al³⁺ exchange ratio was determined from batch titrations using solutions of fulvic acid (FA) as a model for soil organic matter. Aluminium was added, from 1.04 to 6.29 mmol Al per g FA, which is within the range of humus‐bound Al found in the upper B horizon of podzolized soils. Furthermore, pH was varied with NaOH to give values between 3.5 and 5.0. The H⁺/Al³⁺ exchange ratio ranged between 1.49 and 2.23 with a mean of 1.94. It correlated positively with pH and the total concentration of Al present. Theoretically, this can be explained with a partial hydrolysis of bound Al. The slope of logAl (log₁₀ of Al³⁺ activity) against pH generally underestimated the actual exchange ratio, which can partly be attributed to the systems being diluted (100 mg FA l^?1). However, where 4 mmol Al or more had been added per g FA, the logAl slope gradually approached ?3 between pH 4.5 and 5.0. This might be the result of a shift from Al³⁺ activity control by humus complexation to control by Al(OH)₃(s).     

Equilibria of weak acids and organic Al complexes explain activity of H+ and Al3+ in a salt extract of exchangeable cations

Two sequential extractions with unbuffered 0.1 m BaCl₂ were done to study the release of salt-exchangeable H⁺ and Al from mineral horizons of five Podzols and a Cambisol. Released Al was found to have a charge close to 3+ in all horizons and in both extractions. This finding was supported by the near-equality of the titrated exchangeable acidity (EA_T) and the sum of exchangeable acids (EA = H_e + 3Al_e, calculated from the pH and Al concentration of the extract). The ratio between EA of the second and the first extraction was over 0.50 in the Bs2 and C horizons and smaller in the other horizons. H⁺ was assumed to be in equilibrium with weak acid groups, and the modified Henderson–Hasselbach equation, pK_HH = pH ? n log (α/(1 ? α)), was used to explain pH of the extract. The degree of dissociation (α) was calculated as the ratio between effective and potential cation exchange capacity. Value of the empirical constant n was found to be near unity in most horizons. When the monoprotic acid dissociation was assumed in all horizons, pK_HH had the same value in both extractions. For Al³⁺, two equilibrium models were evaluated, describing (i) complexation reactions of Al³⁺ with soil organic matter, and (ii) equilibrium with Al(OH)₃. Apparent equilibrium constants were written as (i) pK_o = xpH ? pAl³⁺, and (ii) log Q_gibbs= log Al³⁺ ? 3log H^+. The two extractions gave an average reaction stoichiometry x close to 2 in all horizons. Results suggest that an equilibrium with organic Al complexes can be used to express dissolved Al³⁺, aluminium being apparently bound to bidentate sites. The value of log Q_gibbs was below the solubility of gibbsite (log K_gibbs = 8.04) in many horizons. In addition, log Q_gibbs of the second extraction was greater than that of the first extraction in all horizons except the C horizon. This indicates that equilibrium with Al(OH)₃ cannot explain dissolved Al³⁺ in the soils. We propose that the models of pK_HH and pK_o can be used to simulate exchangeable H⁺ and Al³⁺ in soil acidification models.     

Soil tests for aluminum toxicity in the presence of organic matter: Laboratory development and assessment

Abstract

Al toxicity in plants is related to the activity of Al³⁺ and Al‐hydroxy monomers in the soil solution, whereas Al complexed with ligands such as fluoride (F), sulphate (SO₄ ^2‐), and oxalate is not toxic. Estimation of toxic Al relies on measurement of “labile”; Al after short contact times with colorimetric reagents or cation‐exchange resins. However, shifts in equilibrium may result in non‐toxic forms of Al reacting with the complexing agent or resin.

A series of laboratory experiments tested the degree to which labile Al is related to Al³⁺ in simplified media and compared methods of estimating labile Al in the presence of organic ligands and in soils. Cation‐exchange resins extracted more than the theoretical concentration of Al³⁺ from solutions containing a range of concentrations of OH^‐ and SO₄ ^2‐. More Al was extracted in 15 s by 8‐hydroxy‐quinoline than by Chelex‐100 from solutions of Al‐humate at pH 4. In sands which had been spiked with Al and organic matter, the estimation of labile Al varied with both the method of measurement and type of extract. The cations present in commonly used soil‐extracting chloride solutions can decrease the proportion of organically complexed Al.     

Speciation and mobilization of aluminium and cadmium in podzols and cambisols of S. Sweden

Processes governing the mobilization of Al and Cd in podzols and cambisols of S. Sweden having different tree layer vegetation (Picea abies, Fagus sylvatica, or Betula pendula) were investigated. Speciation of Al and Cd in soil solutions were performed by a column cation exchange procedure (cf. Driscoll, 1984) in combination with thermodynamic calculations. Podzols in spruce and beech stands were characterized by a high release of organic compounds from the O/Ah horizons, resulting in a high organic complexation of Al (c. 93%) in the soil solution from the E horizon (15 cm lysimeters). Organic complexes were mainly adsorbed/precipitated in the upper Bh horizon and the overall transport of Al at 50 cm depth was governed by a pH dependent dissolution of a solid-phase Al pool. In the cambisols, inorganic Al forms were predominant at both 15 and 50 cm depth, and Al solubility was closely related to solution pH. Secondary minerals like synthetic gibbsite, jurbanite, kaolinite or imogolite could generally not explain measured solution Al³⁺ activities. Results instead indicated that the relatively large organically bound solid-phase Al pools present in both soil types could do so. The column fractionation procedure could be used only qualitatively for Cd, but results strongly indicated that Cd-organo complexes contributed significantly to the overall mobilization of Cd in the podzol E horizons. In all other soil solutions, Cd²⁺ was the predominant species. Both solid-phase and solution chemistry suggests that ion exchange processes controlled the Cd²⁺ activities in these solutions. All reactive solidphase Cd was extractable by NH₄Cl and Cd²⁺ activities could in most cases effectively be modeled by the use of ion exchange equations. Solubilized Al³⁺ efficiently competed for exchange sites and played an important role for the Cd mobilization in these soils.     

Apparent cation-exchange equilibria in podzolic forest soils

The Gaines–Thomas selectivity coefficient, K, was used to express the relation between the cations in solution and the cations in exchange sites in podzolic forest soils. Soil solution was obtained by centrifuging a fresh bulked soil sample. Exchangeable cations HX, AlX, CaX, MgX and KX and effective cation-exchange capacity, CEC_e, were determined with 0.1 m BaCl₂. Apparent values of K indicated a preference of Ca²⁺ over Mg²⁺ and over Al³⁺ in O, A and B horizons (log K_Al–Ca < 0 and log K_Mg–Ca < 0), whereas log K_K–Ca and log K_H–Ca exceeded zero. The horizons were similar with respect to log K_H–Ca, and the differences in log K_Mg–Ca were small. Log K_K–Ca and log K_Al–Ca increased in the horizons in the order O < A < B. Log K_Al–Ca was not significantly correlated with the fraction AlX/CEC_e. Log K_Mg–Ca was positively correlated with the fractions HX/CEC_e and AlX/CEC_e, and negatively correlated with log (CaX/MgX). The selectivity coefficient of binary cation exchange seemed to be applicable to in situ soil solutions. However, the fraction of each cation on exchange sites should be based on the CEC_e rather than on the sum of the two cations. The latter, also, seemed to be acceptable in cases of exchangeable cations with a large relative content in soil, e.g. in Al³⁺–Ca²⁺ exchange in A and B horizons, and in H⁺–Ca²⁺ exchange in O and A horizons.     

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.     

Effects of experimental acidification and alkalinization on soil and growth and health of Acer saccharum Marsh.

Experimental application of eight acidifying, neutral, or alkalizer compounds (range: –16 to 16 kmol ha^–1 of acid‐neutralizing capacity [ANC]) was realized in two northern hardwood stands having significantly different soil base saturation (BS) (a “poor” and a “rich” site) to assess responses of soil physico‐chemical properties, and nutrition, growth, and health of sugar maple (Acer saccharum Marsh.) trees in the short (3 y) and longer term (10 y). The treatments influenced the main indicators of acidity in the forest floor (soil exchangeable‐Ca saturation [S_Ca], BS, exchangeable‐acidity saturation [S_H+Al], and the S_Ca/S_H+Al ratio) at both sites, their values increasing (decreasing for S_H+Al) along the ANC treatment gradient in both the short and longer term, except for pH. Base saturation of the upper 15 cm of the mineral B horizons of soils was influenced at the two sites 10 y after treatment application. Although ANC treatments affected nutrient concentrations of tree foliage in the short term, their effect was no longer detectable after 10 y at the two sites. Growth, however, was strongly related to ANC treatments after 10 y, but only at the poor site. From 1990 to 2000, the basal‐area growth rate of trees at the poor site was (mean ± SE) –0.62 ± 0.28 cm² y^–2 tree^–1 for the most negative ANC treatment to +0.90 ± 0.20 cm² y^–2 tree^–1 for the most positive ANC treatment. A climatic‐stress episode occurring in 1995/96 appeared to accentuate the growth decline of trees subjected to the most negative ANC treatment at the poor site. The experimental results support the hypothesis that atmospheric acid deposition load can cause forest soil base‐cation depletion, acidification, and predispose sugar maple to health and growth decline in the longer term in base‐cation‐poor soils, and that the phenomenon may be reversible by adding alkalizers.     

Agronomic Implications of the Application of Lime plus Gypsum By‐products to a Hyperdistric Acrisol from Western Spain

Abstract: A laboratory experiment involving the use of leaching columns reproducing the topmost portion of a Hyperdystric Acrisol (FAO 1998 FAO. 1998. World reference base for soil resources, Rome: FAO, ISRIC, and ISSS. (World Soil Resources Report No. 84) [Google Scholar]) or plinthic Palexerult (Soil Survey Staff 2003 Soil Survey Staff. 2003. Soil taxonomy: A basic system of soil classification for making and interpreting soil surveys, Washington, D.C.: U.S. Government Printing Office. (Agriculture Handbook No. 436) [Google Scholar]) treated in its Ap horizon with sugar foam wastes and phosphogypsum was conducted. The amendments increased the contents in exchangeable calcium (Ca) of the Ap horizon and, to a lesser extent, also that of the AB horizon. However, the contents in exchangeable magnesium (Mg) and sodium (Na) decreased as much in Ap as they did in AB; by contrast, the potassium (K) content exhibited a less marked decrease. The potassium chloride (KCl)–extractable aluminium (Al) of the Ap horizon was dramatically decreased much more than that of the AB horizon by the amendments. In the soil solution from Ap, the amendments raised the pH and decreased the Al concentration; in that from AB, however, they caused an initial pH decrease, a tendency that reversed as the gypsum was leached and eventually led to the pH exceeding that in the soil solution from control. The first few water extractions exhibited increased Mg concentration. This trend was reversed in the second leaching cycle, where the concentrations of Mg in the amended columns were lower than those in the controls. In the soil solution, the variation of the Ca and sulphate (SO₄ ^2–) concentrations was influenced by the salt‐sorption effect. The total Al content in soil solution from AB increased during the first leaching cycle and then decreased during the second. The amendments decreased the activities of Al³⁺, AlOH⁺², and Al(OH)₂ ⁺ in the Ap horizon and increased those of Al³⁺, AlSO₄ ⁺, Al(SO₄)₂ ^?, and AlF⁺² in the first leaching cycle in the AB horizon. The productivity of the Ap horizon after the treatments was assessed using a wheat crop (T. aestivum, var. ‘Jabato’) in a greenhouse.     

SOIL PROPERTY CHANGES FOLLOWING IRRIGATION WITH COALBED NATURAL GAS WATER: ROLE OF WATER TREATMENTS,SOIL AMENDMENTS AND LAND SUITABILITY

Saline‐sodic water is a by‐product of coalbed natural gas (CBNG) production in the Powder River Basin of Wyoming, USA and is being beneficially used in places as irrigation water. This study evaluated effects of 2 years of natural precipitation on soil properties of a hay field after the cessation of managed irrigation with CBNG water. The hay field had been irrigated with only CBNG water [CBNG(NT)], CBNG water amended with gypsum [CBNG(G)] or gypsum plus sulfur via a sulfur burner [CBNG(GSB)] in combination with soil amendments—gypsum ( +G ), elemental sulfur ( +S ), and both ( +GS ). Results indicated that infiltration rates were the lowest on fields irrigated with CBNG(NT), followed by CBNG(G) and CBNG(NT) +G treatments (12·2, 13·2, and 13·5 cm h⁻¹, respectively). The CBNG(GSB) +GS treatment had the highest infiltration rates (33·5 cm h⁻¹). By the second year, salinity and sodicity of treated soils had decreased in the A‐horizon of most CBNG‐water irrigated plots, whereas in Bt₁‐ and Bt₂‐horizons salinity generally decreased but sodicity increased; S and GS soil amended plots had higher profile salinities compared with NT and G soil treatments. Although Na⁺ leaching was observed in all fields that received soil and/or water amendments, CBNG(GSB) +GS plots had the lowest sodicity in the A‐ and Bt₁‐horizons. Effective managed irrigation requires knowledge of site‐specific soil properties, plant suitability, water chemistry, and amendments that would be needed to treat the CBNG waters and soils. This study indicates the greatest success was realized when using both soil and water amendments. Copyright © 2011 John Wiley & Sons, Ltd.     

The solubility of aluminium in two Swedish acidified forest soils: An evaluation of lysimeter measurements using batch titration data

This paper presents aluminium (Al)-solubility data for two acid forest soils (Inceptisol and Spodosol), obtained in connection with lysimeter measurements (tension-cup and zero-tension lysimeters) and batch equilibrium experiments. The solubility of Al obtained in the batch experiments was used as a reference to test whether Al³⁺in soil solutions collected by the lysimeters was in equilibrium with secondary forms of solid-phase Al (Al(OH)₃or organically bound Al). The relation between pH and Al³⁺activity found for the zero-tension lysimeter solutions collected from the Inceptisol agreed well with that obtained in the batch experiment. This suggests that Al³⁺in the lysimeter solutions were in, or close to, equilibrium with the solid phase, whether this was organically bound Al (A horizon) or an Al(OH)₃phase (B horizon). For the tension-cup lysimeters, solutions obtained from the Inceptisol B and Spodosol Bs1 horizons were generally close to equilibrium with respect to secondary solid-phase Al (apparently Al(OH)₃; average ion activity product was 10^9.3and 10^8.8, respectively), whereas the Inceptisol A and Spodosol Bh solutions were not. The Al solubility in Inceptisol A and Spodosol Bh horizons was consistently higher than that obtained in the batch equilibrium experiment, indicating that the sampled solution partly originated from the underlying horizons. Thus, tension-cup lysimeters should be used with care in soils (or in parts of soil profiles) having steep solute concentration gradients because the soil volume from which the sample is drawn with this lysimeter type seems to be poorly defined.     

Soil organic matter stabilization in acidic forest soils is preferential and soil type-specific

Minerals with large specific surface areas promote the stabilization of soil organic matter (SOM). We analysed three acidic soils (dystric, skeletic Leptic Cambisol; dystric, laxic Leptic Cambisol; skeletic Leptic Entic Podzol) under Norway spruce (Picea abies) forest with different mineral compositions to determine the effects of soil type on carbon (C) stabilization in soil. The relationship between the amount and chemical composition of soil organic matter (SOM), clay content, oxalate‐extractable Fe and Al (Fe_o; Al_o), and dithionite‐extractable Fe (Fe_d) before and after treatment with 10% hydrofluoric acid (HF) in topsoil and subsoil horizons was analysed. Radiocarbon age, ¹³C CPMAS NMR spectra, lignin phenol content and neutral sugar content in the soils before and after HF‐treatment were determined and compared for bulk soil samples and particle size separates. Changes in the chemical composition of SOM after HF‐treatment were small for the A‐horizons. In contrast, for B‐horizons, HF‐soluble (mineral‐associated) and HF‐resistant (non‐mineral‐associated) SOM showed systematic differences in functional C groups. The non‐mineral associated SOM in the B‐horizons was significantly depleted in microbially‐derived sugars, and the contribution of O/N‐alkyl C to total organic C was less after HF‐treatment. The radiocarbon age of the mineral‐associated SOM was younger than that of the HF‐resistant SOM in subsoil horizons with small amounts of oxalate‐extractable Al and Fe. However, in horizons with large amounts of oxalate‐extractable Al and Fe the HF‐soluble SOM was considerably older than the HF‐resistant SOM. In acid subsoils a specific fraction of the organic C pool (O/N‐alkyl C; microbially‐derived sugars) is preferentially stabilized by association with Fe and Al minerals. Stabilization of SOM with the mineral matrix in soils with large amounts of oxalate‐extractable Al_o and Fe_o results in a particularly stable and relatively old C pool, which is potentially stable for thousands of years.