Aluminum solubility of strongly acidified allophanic Andosols from Kagoshima Prefecture,southern Japan

Abstract

The aluminum solubility of acidified soils both from furrows and under tree canopies of a tea garden was studied using equilibrium experiments in 0.01 mol L^?1 CaCl₂ solution systems. The soils were originally classified as allophanic Andosols. The furrow soils were more severely acidified because of the heavy application of nitrogen fertilizer, especially in the upper soil horizons (pH[H₂O] of 3.6–3.8 in the A1 and 2A2 horizons). These acidified soils were characterized by the dissolution of allophanic materials (allophane, imogolite and allophane-like materials) and by an increase in Al–humus complexes. Ion activity product (IAP) values of the strongly acidified soil horizons were largely undersaturated with respect to imogolite (allophanic clay) or gibbsite. Plots of p(Al³⁺) as a function of pH strongly indicated that Al solubility of the soils was largely controlled by Al–humus complexes, especially in the A1 horizon. In the canopy soils, which were more weakly acidified (pH[H₂O] 4.9–5.0), Al solubility was close to that of gibbsite and allophanic materials, indicating that the solubility is partly controlled by these minerals.     

Mechanisms controlling the mobility of dissolved organic matter, aluminium and iron in podzol B horizons

The processes governing the (im)mobilization of Al, Fe and dissolved organic matter (DOM) in podzols are still subject to debate. In this study we investigated the mechanisms of (im)mobilization of Al, Fe and organic matter in the upper and lower B horizons of two podzols from the Netherlands that are in different stages of development. We equilibrated batches of soil material from each horizon with DOM solutions obtained from the Oh horizon of the corresponding soil profiles. We determined the amount of (im)mobilized Al, Fe and DOM after addition of Al and Fe at pH 4.0 and 4.5 and initial dissolved organic carbon (DOC) concentrations of 10 mg C litre^?1 or 30 mg C litre^?1, respectively. At the combination of pH and DOC concentrations most realistic for the field situation, organic matter was retained in all horizons, the most being retained in the lower B horizon of the well‐developed soil and the least in the upper B horizon of the younger profile. Organic matter solubility seemed to be controlled mainly by precipitation as organo‐metal complexes and/or by adsorption on freshly precipitated solid Al‐ and Fe‐phases. In the lower B horizons, at pH 4.5, solubility of Al and Fe appeared to be controlled mainly by the equilibrium with secondary solid Al‐ and Fe‐phases. In the upper B horizons, the solubility of Al was controlled by adsorption processes, while Fe still precipitated as inorganic complexes as well as organic complexes in spite of the prevailing more acidic pH. Combined with a previous study of eluvial horizons from the same profiles, the results confirm the important role of organic matter in the transport of Al and Fe to create illuvial B horizons initially and subsequently deepening and differentiating them into Bh and Bs horizons.     

Acid deposition in the German solling area: Effects on soil solution chemistry and Al mobilization

The Al chemistry of soil solutions was evaluated in two forest ecosystems in the North-German Solling area which is heavily impacted by acidic deposition. The principal H⁺ buffering process in these soils is the release of Al ions. Within the stand of Norway spruce, Al concentrations increase with soil depth up to 370 umol/L. Ca/Al ratios of the soil solution decrease with depth and suggest high risk of Al toxicity to tree roots and potential antagonistic effects for ion uptake. The Al concentrations of the soil solution in the upper horizons do not appear to be in equilibrium with mineral phases of Gibbsite, Alunite and Jurbanite as suggested by the depth gradients and temporal patterns in ion activity products. Depletion of extractable soil Al in the upper horizons is occuring. The release of Al to the soil solution under these conditions seems to be restricted by kinetic constraints.     

Solubility and standard Gibbs free energy of formation of natural imogolite at 25°c and 1 atm

We carried out a dissolution experiment to determine the solubility and the Gibbs free energy of formation of natural imogolite at 25°C and 1 atm. Purified gelatinous film of natural imogolite, synthetic gibbsite, and imogolite plus gibbsite were equilibrated in 1 mmol L^-1 HCI solutions and Si, Al concentrations and pH were monitored during 700 d. Imogolite plus gibbsite and gibbsite systems reached an equilibrium after 120 d. The logarithmic values of the equilibrium constants of dissolution reactions were 12.10±0.01 for imogolite and 8.01±0.01 for gibbsite. The calculated Gibbs free energy of formation was -2929.19±3.28 kJ mol^-1 for imogolite and -1155.11 ± 1.42 kJ mol^-1 for gibbsite. These values predict that the silicic acid concentration at the imogolite-gibbsite equilibrium would be 0.120 mmol L^-1.     

The influence of land management on concentrations of dissolved organic carbon and its effects on the mobilization of aluminium and iron in podzol soils in Mid-Wales

Abstract. The aluminium (Al), iron (Fe) and Dissolved Organic Carbon (DOC) contents of the soil solution were monitored in two upland grassland and afforested podzol soils in Mid-Wales. Al organo-metallic complexes predominated in the O horizon leachates of the grassland soil, whereas inorganic monomeric Al forms dominated in the lower mineral horizons. Dissolved organic matter determines the chemistry, solubility, and transport of Al and Fe in the O horizon, and these are under strong biological control. The distributions of organic-Al, Fe and DOC within the soil profile were consistent with traditional podzolization theory. Observed increases in the molar ratios of Al:DOC in solution in the lower soil horizons may be responsible for the small solubility of Al organo-metallic complexes in those horizons. Afforestation increased the concentrations of organic-Al and Fe in the soil solution as compared with the concentrations observed for the grassland soil. Clearcutting further significantly mobilized Al and Fe from the upper soil horizon, primarily by increasing the DOC concentration in the soil water.     

Adapting the Profile Model to Calculate the Critical Loads for East Asian Soils by Including Volcanic Glass Weathering and Alternative Aluminum Solubility System

Adaptation of the steady-state soil chemistry model PROFILE was studied, on the following two parts, to calculate the critical loads for East Asian soils: (1) Dissolution rate coefficients of volcanic glass were derived from published experimental data, and calculated field weathering rate was compared with the rate estimated based on Sr isotope analysis. When BET surface area of sand fraction was regarded as mineral surface area, the calculated rates fairly agreed with the estimate, suggesting that sand fraction surface area is a reasonable estimate of weatherable mineral surface area of volcanic soils. (2) In repeated leaching experiments, Al solubility of a number of Japanese soils was explained by a model which assumed complexation of Al to soil organic matters. Such an Al solubility model is more appropriate for predicting soil chemistry than apparent gibbsite dissolution equilibrium.     

Aluminium solubility related to secondary solid phases in upper B horizons with spodic characteristics

We examined the aluminium solubility in the upper B horizon of podzols and its relation to the solid phase of the soil in 60 samples covering a pH range from 3.8 to 5.1. Solid phases were characterized by extractions with acid oxalate and pyrophosphate (pH 10). The solubility of Al was studied in a batch experiment in which samples were equilibrated with 1 m m NaCl at 8°C for 5 days. We also monitored the dissolution kinetics of Al and Si, in some samples. The oxalate and pyrophosphate extractions suggested that secondary Al was mainly organically bound in most soils, and imogolite-type materials seemed to constitute much of inorganic secondary Al. No single gibbsite or imogolite equilibrium could explain Al³⁺ activities. In all samples Al solubility, defined as log{Al³⁺} + 1.65pH, was closely related to the molar ratio of aluminium to carbon in the pyrophosphate extracts (Al_p/C_p). Solubility increased with the Al_p/C_p ratio until the latter reached ≈ 0.1. This indicated that solubility was controlled by organic complexation, at least when Al_p/C_p was small. Silica dissolved slowly in most soils used in the kinetic experiments. We conclude that imogolite-type materials in the upper B horizon dissolved slowly because of coating with humic substances or ageing or both.     

Modelling of sorption experiments and seepage data of an Amazonian Ultisol subsoil under cropping fallow

The results of physico-chemical investigations of an Ultisol subsoil under a 2-year old fallow in eastern Amazonia are presented. Subsoil chemistry was studied using 4 different approaches: i) concentrations of H, Na, K, Ca, Mg, Mn, Al, and Fe in seepage water were measured under field conditions, ii) the equilibrium soil chemistry was studied in sequential batch experiments where the soil was treated with different solutions, iii) results of batch experiments were simulated with a chemical equilibrium model, and iv) the seepage data were calculated using selectivity coefficients obtained by modelling the batch experiments. The model included multiple cation exchange, precipitation/dissolution of Al(OH)₃ and inorganic complexation. Cation selectivity coefficients were pK_x/Ca^sel: X = Na: 0.3, K: 0.8, Mg: ?0.1, and Al: 0.4. The amount of cations sorbed ranged from ?0.2 to 2.0 (K), ?0.7 to 2.3 (Mg), ?1.6 to 1.8 (Ca), ?4.8 to 3.6 (Al) and 0.0 to 8.5 (Na) mmol_c kg^?1. The model predictions were good with values lying within 0.3 pH units (for the pH range 3.7 to 7.2), and 3% of CEC for individual cations. The most important proton buffer reaction seemed to be the dissolution of gibbsite and a large release of Al into the soil solution. When selectivity coefficients obtained by the modelling procedure were used to predict the field data for cation concentrations in the seepage water, they decreased in the following order: Na > K > Ca > Mg > Al. These calculated values were similar to the measured order: Na > Ca > K ≈ Mg > Al. Thus the options for managing these soils should be carefully chosen to avoid soil acidification which may result from inappropriate use of fertilizer during the cropping period.     

Modelling pH buffering and aluminium solubility in European forest soils

The pH buffering and aluminium solubility characteristics of acid soil are important in determining the soil's response to changes in precipitation acidity. The chemistry of soil organic matter (humic substances) plays a key role in both processes, yet is complex and still poorly understood. Nevertheless, models of humic substance chemistry have been developed, one of which is WHAM–S, which contains a model (Model V) of proton and metal binding at discrete sites on humic substances and considers electrostatic effects on the binding strength. Here we have tested the ability of WHAM–S to model solution pH and Al using batch titration studies on organic and mineral soil horizons from forested sites in Norway, Germany and Spain, with ambient pH values from 3.73 to 5.73. We optimized the model predictions by adjusting the amounts of soil aluminium and humic substances within defined limits, taking the contents of copper chloride‐extractable Al and the base‐extractable organic matter as starting values. The model simulated both pH and dissolved Al well with optimized amounts of aluminium and humic substances within the defined limits (root mean squared error for pH from 0.01 to 0.22, for p[Al]_aq (total dissolved Al) from 0.03 to 0.49, five data points). Control of dissolved Al by dissolved organic matter was important particularly at above‐ambient pH. In two mineral horizons we improved the fits by assuming that Al could precipitate as Al(OH)₃. The optimized model also gave reasonable predictions of pH and dissolved Al in supernatants obtained by repeated leaching of the soil horizons. The results show that humic substances dominate the control of pH and dissolved Al in most of the horizons studied. Control by Al(OH)₃ occurs but is the exception.     

Use of a chemical equilibrium model to understand soil chemical processes that influence soil solution and surface water alkalinity

A chemical equilibrium model was applied to soil chemistry data (Spodosols) collected from 30 and 21 forested watersheds in New York and Maine, respectively, during the EPA Pilot Soil Survey. Chemistry data were evaluated between states using lumped series and within New York using three series (Adams, Becket, and Canaan). All New York horizons had soil characteristics that tend to cause lower solution alkalinity in comparison to Maine horizons. Negative alkalinities were produced in all E horizons (? 69 to ? 37 μmol LU^?1) at each of the pCO₂ levels used (0.3 to 2%). All B horizons had negative alkalinities at low PCO₂ levels, which became positive at higher levels, except for the Canaan B and New York Bh horizons, which were negative at all pCO₂ levels. C horizons generated positive alkalinities (1 to 67 μmol L^?1) at most pCO₂ levels. Results indicate the importance of water contact with different horizons and soil series in determining solution alkalinity. Because of degassing effects, solutions with a positive alkalinity will increase in pH after leaving the soil, whereas solutions with a negative alkalinity will remain at low pH (pH < 5.5) and cause the surface water to be acidic. Application of the model to soil chemistry data collected in the northeastern U.S. illustrates the importance of various factors such as pCO₂, Al solubility, base saturation, and exchange coefficients in determining surface water chemistry.     

Aluminium solubility mechanisms in moderately acid Bs horizons of podzolized soils

The processes controlling the retention and release of aluminium in acid forest soils are still subject to controversy, and therefore a universal hypothesis as to what mechanisms are operating has not been firmly established. By studying the Bs horizons of Swedish and Swiss podzolized soils, and by analysing data in the literature, we have found that aluminium hydroxide, and in some cases also poorly ordered imogolite, may control Al solubility in moderately acid (pH > 4.2–4.3) Bs horizons. The strongest evidence in support of the presence of a quickly reacting Al(OH)₃ pool came from the temperature dependence of Al solubility in a Bs horizon, which was consistent with the reaction enthalpy of an Al(OH)₃ phase such as gibbsite, and from the observation that the ion activity product for Al(OH)₃ was the same regardless of whether equilibrium was reached from over‐ or undersaturation. The pool of Al(OH)₃ is commonly small and may be completely dissolved after large additions of acid. This may be explained by the continuing redissolution of reactive Al(OH)₃ to form less soluble imogolite‐type phases. By using the same methods it was found that soil suspensions did not reach equilibrium with poorly ordered imogolite even after 17 days. Thus, imogolite probably does not control Al solubility in the short term in many soils despite the common occurrence of this mineral. This is due to the relatively slow kinetics of imogolite formation and dissolution, especially at low temperatures and at small solution H₄SiO₄ concentrations.     

Squeezed soil-pore solutes — A comparison to lysimeter samples and percolation experiments

This paper presents data on the chemical composition of soil pore fluids that have been obtained by a high-pressure squeezing technique and lysimeter sampling. Cation-exchange capacity has been calculated from cations extracted by a simple percolation method. All pore water concentrations are greatly influenced by the pH in solution. Most pore water concentrations do not simply parallel the corresponding mineralogical and chemical composition of the solids. The depth of the acidification front, as determined by analysis of samples obtained by percolation, is much better reflected in the chemical composition of the squeezed soil pore fluids than in the lysimeter samples. Distinct gradients are seen in Al concentration. In the B-horizons, concentrations of Al are close to the solubility of gibbsite. The pore water concentration profiles of Si and K apparently indicate dissolution of K-silicates, in particular K-feldspar. Contrary to the squeezed pore solutions the sulphate maximum concentration in the soil profile is not recorded by lysimeter samples. Mineral saturation indices show that pore solutions by squeezing are close to the saturation concentrations for K-jarosite and K-alunite. Sulphur-rich phases from the soil are compatible with mixtures of alunite jarosite, zaherite, basaluminite, and hydrobasaluminite. In the upper soil horizons the liquid/solid ratios [calculated as: concentration in solution (µg/ml) * solution fraction in solids (ml/g)/concentration in solids (µg/g)] increase in the order Ph < OC ≈ Zn < Cd and range from 10^?6 to 10^?3, indicating that Ph is most strongly held and still accumulates in the organic top soil. In the underlying deeper mineral horizons the ratios for Pb, Zn, and Cd decrease by one order of magnitude.     

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.     

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.     

Movement of aluminium as an inorganic complex in some podzolised soils,New Zealand

Chemical and mineralogical data are presented for three Spodosols (podzols) and a related Inceptisol (yellow-brown loam). Allophane with an Al/Si atomic ratio close to two is identified in the B horizons of all four soils, and minor amounts of imogolite are present in association with allophane in all but one soil where small-particle gibbsite occurs. Parent materials for these soils are essentially non-vitric. Allophane (Al/Si = 2) has been estimated quantitatively in all soils using oxalate-extractable Si (Si₀) and is selected clay fractions using both Si₀ and infrared spectroscopy. Maximum concentrations of allophane (Al/Si = 2) range from 5% to 18% of fine earth (< 2 mm) fractions and all occur in B horizons. Fe₀ values are low relative to Al₀ values except for the upper horizons of the Inceptisol. Al₀ values peak in B horizons and the ratio pyrophosphate-extractable Al to Al₀ decreases from about 1 in A and upper B horizons to 0.1–0.4 in lower B horizons.An interpretation of the data is consistent with recent proposals that the movement of Al in podzolisation is due primarily to the formation of inorganic complexes with Si. Chemical criteria for spodic horizons should be consistent with the total illuviation of Al and Fe (and perhaps Si), rather than just the organic-bound fraction of Al and Fe in these horizons as indicated by amounts in extractants such as pyrophosphate.     

Soil acidification along a topographic gradient on Roundtop Mountain,Quebec, Canada

We examined the effects that different acidic loadings have had on soil chemistry along a toposequence on Roundtop Mountain. Due to fog interception by the forest canopy, the amount of time in the clouds is a major factor determining the amount and chemistry of precipitation reaching the soil and hence, acid precipitation loading is directly related to elevation. Soils on a transect from 520 to 850 m show a pattern of chemistry that corresponds to the loading of acidic deposition. Soil solutions collected at two elevations show different levels of both SO₄ and Cl, two of the anions in fog water as well as differences in concentrations of H ion and Al. Surface horizons of soils located at 850 m have pH in water as low as 3.7; in mineral horizons base saturation is extremely low (<5%) and Al saturation exceeds 95% in many cases. In contrast, lower on the mountain slope (below 650 m), pH is slightly higher (about 4.1) and base saturation rises to over 50% for the same soil horizons. There is a clear relationship between soil acidification and position on the mountain.     

Simulation of solution chemistry in an acidic forest soil

The computer simulation model SOILEQ was used to estimate soil solution chemistry over a 7 week period from October 3 to November 14, 1988 in the soils of a sugar maple forest located near St. Hippolyte, Quebec, Canada. Model parameters for pH-dependent CEC and exchangeable cations were calculated from laboratory measurements while soil solution chemistry, including Al solubility, at the start of the simulation was taken from values obtained from lysimeter samples. Model predictions were compared with values obtained from 12 sets of soil solution collectors over the same time period. Predicted values of Ca, Mg and K in the mineral soil horizons at 25-, 75- and 125-cm depths generally fall within the 95% confidence interval of the median for the measured values. Simulated values of pH and inorganic Al are not as close to the measured values. Some error due to drift is apparent, most notably for base cations in solutions leaving the organic surface horizons, and may be attributable to decomposition of organic matter, not included in the simulation model. The results indicate that other mechanisms that release H* (nitrification, for example) and base cations (mineral weathering or mineralization of organic matter) need to be considered.     

Highly weathered soils in the east coast hinterland of Southern Africa with thick, humus-rich A1 horizons

Strongly weathered red and yellow soils with thick (490–900 mm) humic Al horizons (Haplohumox and Palchumults) derived from sandstones and basic igneous rocks, and occurring near the east coast of Southern Africa, are described and discussed in terms of their distribution, morphology, texture, mineralogy, chemistry, genesis and classification. The high organic matter content (2–5%C) of the Al contributes significantly to a high pH-dependent negative charge, probably to poorer crystallinity of goethite and kaolinite and to the transformation of haematite to goethite. Varying proportions of kaolinite and gibbsite reflect different soil ages within these old landscapes. The yellow colour of aluminous goethite, the main pedogenic iron oxide, is masked in the Al by organic matter and in red B2 horizons by haematite. Temperature may have influenced the broad pattern of occurrence of red and yellow B2 horizons. These soils need not, as previously suggested, have developed from the weathering products of an ancient laterite. Neither Soil Taxonomy nor the South African soil classification system accommodates the soils entirely satisfactorily and possible improvements to the latter are discussed.     

ABSTRACT of the Articles Printed in Journal of the Science of Soil and Manure,Japan

A contrasting occurrence of clay minerals was found within a soil profile which was derived from volcanic materials in the suburbs of Fukuoka-city, Northern Kyushu. The soil profile is located on an isolated terrace, and the morphological characteristics of the soil correspond exactly to Andosols, so-called Kuroboku soils or Humic Allophane soils.

The clay fraction of upper horizons of the soil consists largely of alumina-rich gel-like materials, gibbsite, and layer silicates such as chlorite and chloritevermiculite intergrades, while that of lower horizons is composed of allophane and gibbsite or halloysite. There was no positive indication of allophane in the upper horizons. Corresponding with the clay mineralogical composition, quartz is abundant in the fine sand fraction of the upper horizons, while the mineral is very scarce or none in the lower horizons, suggesting a close relation between the petrological nature of parent volcanic materials and the mineralogical composition of weathering products. The dominant clay mineral in the volcanic 1.10il might be dependent on the petrological nature of parent materials, and allophane is mostly formed from andesitic materials, and alumina-rich gel-like materials and layer silicates have come from quartz andesitic materials. Allophane would transform to gibbsite or halloysite according to weathering conditions, and aluminarich gel-like materials change to gibbsite under a well-drained condition.

The soil materials have been so greatly weathered that some horizons contain gibbsite of even more than 40 per cent or halloysite over 70 per cent. The morphology and mineralogy are quite similar to so-cailed “non-volcanic Kuroboku soils.”