Aluminum status of synthetic Al–humic substance complexes and their influence on plant root growth

Abstract

Aluminum (Al)–humus complexes are abundant in the A horizons of non-allophanic Andosols and contribute to the unique properties of volcanic ash soils, such as high reactivity with phosphate ions and a low bulk density. Natural non-allophanic Andosols commonly show Al toxicity to plant roots. There have been very few studies examining the contribution of Al–humus complexes to the Al toxicity of plant roots, although the complexes are the probable source of the toxic Al. We extracted humic substances from the A horizon of a non-allophanic Andosol using NaOH solution and reacted the humic substances and partially neutralized the AlCl₃ solution at three pH conditions (pH 4.0, 4.5 and 5.5) to prepare pure Al–humic substance complexes. The Al solubility study (equilibrium study in 10^?2 mol L^?1 CaCl₂) and the Al release study (a stirred-flow method using 10^?3 mol L^?1 acetate buffer solution adjusted to pH 3.5) indicated that all the synthetic complexes easily and rapidly release monomeric Al into the liquid phase with slight changes in pH and ion strength, although the Al contents and their extent of polymerization are considerably different among the complexes. A plant growth test was conducted using a medium containing the Al–humic substance complexes and perlite mixture. Root growth in burdock (Arctium lappa) and barley (Hordeum vulgare L.) was reduced equally by all three complex media, and the roots showed the typical injury symptoms of Al toxicity. These results indicate that in soils dominated by Al–humus complexes the Al released from the Al–humus complexes, as well as the exchangeable Al adsorbed by soil minerals, is definitely toxic to plant roots.     

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.     

Efficiency of gypsum application to acid Andosols estimated using aluminum release rates and plant root growth

Abstract

A great deal of information on the efficiency of gypsum or phosphogypsum to ameliorate acidity in highly weathered soils is available, but only limited information is available on the efficiency in acid Andosols, which possess large amounts of active aluminum (Al). We examined the effectiveness of gypsum application to non-allophanic Andosols (one humus-rich A horizon and two B horizons poor in humus) using extractable soil Al analyses (batch and continuous extraction methods) and a cultivation test using burdock (Arctium lappa). With gypsum amendment, pH(H₂O) values of the soil decreased from 4.5–4.7 to 4.2–4.4, whereas the treatment made almost no difference to the values of pH(KCl). Total active Al (acid oxalate-extractable Al) was hardly affected by gypsum for all samples. Potassium chloride-extractable Al definitely decreased with the addition of gypsum in all soils; however, the decrease was small (0.1–1.4 cmol_c kg^?1) and the values still exceeded “the threshold of 2 cmol_c kg^?1” for inducing Al toxicity in sensitive plants (4.4–8.6 cmol_c Al kg^?1). The change in Al solubility with gypsum application represented by Al release rates from soils using continuous extraction methods with a dilute acetate buffer solution (10^?3 mol L^?1, pH 3.5) differed greatly among the soil samples: The release rate of one of the B horizon samples decreased by 71%, certainly showing the insolubilization of Al compounds, whereas the release rates of the A horizon sample showed almost no change. These changes in Al solubility were well correlated with the plant root growth. Root growth was improved with gypsum in the B horizon sample, whereas improvement was not observed in the A horizon soil. The decrease in the rate of Al release of another B horizon soil with gypsum treatment was smaller (by 20–34%), possibly because of lower pH values after gypsum application (pH[H₂O] of 4.2–4.3). In the B horizon soil, root growth improved only slightly. Thus, the effectiveness of gypsum application to acid Andosols appeared to be largely influenced by soil humus contents and slight differences in soil pH values, and corresponded to a decrease in Al release rates using the continuous extraction method.     

Aluminum toxicity of synthetic aluminum–humus complexes derived from non-allophanic and allophanic Andosols and its amelioration with allophanic materials

Natural non-allophanic Andosols often show aluminum (Al) toxicity to Al-sensitive plant roots. The significance of Al–humus complexes to Al toxicity has been emphasized. Allophanic Andosols also possess Al–humus complexes, but they rarely show any toxicity. In the present study, using model substances, we tested the toxicity of Al–humus complexes and its amelioration with allophanic materials. We extracted humic substances from the A horizons of a non-allophanic Andosol and an allophanic Andosol using a NaOH solution, and reacted the humic substances and partially neutralized AlCl₃ solution at pH 4. Allophanic material was purified from commercial Kanuma pumice. Plant growth tests were conducted using a medium containing the Al–humus complexes (50 g kg⁻¹), the allophanic material (0, 90, 180 and 360 g kg⁻¹) and perlite. The root growth of barley ( Hordeum vulgare L.) and burdock ( Arctium lappa ) was reduced in the media containing the Al–humus complexes derived from both the non-allophanic and allophanic Andosols when the allophanic material was not added. With the addition of the allophanic materials, particularly in the 360 g kg⁻¹ treatment, the growth of the barley roots was improved markedly. Although the root growth of the burdock tended to improve with allophanic materials, the effect was weaker than that for barley. Monomeric Al in a solution of the medium was not detected (< 0.05 mg L⁻¹) following the addition of 360 g kg⁻¹ of allophanic materials, whereas 0.8–1.7 mg L⁻¹ Al was recorded without the allophanic material.     

Interactions of fulvic acid with aluminium and a proto‐imogolite sol: the contribution of E‐horizon eluates to podzolization

The podzolization process is examined in the light of measurements of the solubility characteristics of aluminium fulvate, the extent of dissolution of a proto‐imogolite sol by fulvic acid, the adsorption capacity of proto‐imogolite for fulvic acid and aluminium fulvate, and published evidence. Fulvic acid at 500 mg l^?1 acting on a proto‐imogolite (PI) preparation containing 0.95 mmol l^?1 Al as PI did not bring enough Al into solution at pH 4.5–5.0 over 4–15 months to cause significant precipitation of the fulvic acid. As allophanic Bs horizons of podzols typically have pH ≥ 4.8, fulvic acids entering them in drainage water cannot be quantitatively precipitated by dissolution of Al from the allophane. They are, however, strongly absorbed on the allophane, and this must be the mechanism that removes most of the fulvic acid at the top of the Bs horizon, and which contributes, along with colloidal humus and root decomposition, to the formation of a Bh horizon. We conclude that fulvic acid plays no active role in podzolization, but only recycles Al and Fe, that have been transferred by biological processes to the O horizon, back to the Bh horizon. The podzolization process, which leads to the formation of an allophanic Bs horizon underlying a progressively deepening E horizon, requires the dissolution of Al‐humate and allophanic precipitates at the Bh–Bs interface as well as progressive attack on the more readily weatherable minerals. Inorganic acids, particularly episodic fluxes of nitric acid, could play a major role in this, as well as attack by readily metabolized complexing acids such as oxalic and citric acids released by roots and fungi. In addition to throwing light on the podzolization process, the experimental results provide an explanation of the lower limit to C:Al ratios reported in natural waters, and a check on the applicability of the WHAM chemical equilibrium model to Al–fulvate–proto‐imogolite equilibria. In Ca‐containing fulvate solutions, Al‐fulvate begins to precipitate when C:Al falls below 50, which is also the limiting ratio observed in natural waters. WHAM calculations overestimate by 70–85% the amount of Al‐fulvate formed over 4 months at pH 4.5–5.0 in Ca‐containing fulvate–imogolite systems.     

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.     

Effect of liming on organically complexed aluminum of nonallophanic Andosols from northeastern Japan

Aluminum–humus complexes are believed to be highly stable under natural conditions in nonallophanic Andosols. However, it has been shown that the aluminum complexed with humus is easily released by acidic buffer solutions and possibly controls the aluminum solubility of these soils. Thus, it is highly probable that Al–humus complexes are easily influenced by rather simple chemical treatments. We examined the effects of liming (CaCO₃ treatment) on Al–humus complexes of A and B horizons from Andosols. It was observed that liming reduced the Al release rates from soil samples with pH 3.5 acetate buffer solution and the amounts of the KCl-extractable Al, suggesting the formation of precipitation from easily exchangeable Al. A much larger decrease with liming was also obtained for 0.1 M sodium pyrophosphate-extractable Al (decrease rates of 7–52%) and 0.5 M CuCl₂-extractable Al (decrease rates of 9–43%). These results strongly indicate that liming reduces significant amounts of organically complexed Al as well as the exchangeable Al. The increase in the cation exchange capacity of soils at pH 7 after liming further suggested that the carboxyl group of humus complexed with Al was partly liberated from the Al complexation and became to develop negative charges.     

Characterization of Al/Fe—humus complexes in dystrandepts through comparison with synthetic forms

The Al/Fe—humus complexes in A₁ horizons of Dystrandepts from several parts of Japan were compared with synthetic complexes prepared from hydroxy ions and from two kinds of humic substances and at several pH values. Samples represented 26 A₁ horizons of soils differing in age, including some that had been buried. The comparisons were based chiefly on extractions of the synthetic complexes and the soil samples with solutions of sodium hydroxide-tetraborate and sodium pyrophosphate.The Al—humus complexes in the Dystrandept samples appeared to be similar to those of synthetic complexes prepared at pH 4–5. Those have OH/Al molar ratios of 0.7–2.5 1. Distribution of the data for the soil samples suggested further that the proportions of polymeric hydroxy Al ions increased as soils became older and also if they were buried. The Fe—humus complexes in the soil samples seemed to be like the synthetic complexes prepared with Fe and humus at pH 4–5 for the most part.     

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.     

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.     

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.     

Implications of clay mineralogy to the weathering and chemistry of AP horizons of ando soils in Japan

The clay mineralogy of 22 samples of the Ap horizons of Ando soils was determined by a combination of methods. Of these samples, 15 did and 7 did not contain allophane and imogolite. Opaline silica was found in 4 samples, whereas aluminum—humus complexes, iron oxides and layer silicates were found in all samples. The presence of allophane and imogolite and the absence of opaline silica in a few Ap horizons was related to mixing of A₁ horizons and subsoils by cultivation and to lower supplies of organic matter relative to the amounts of aluminum released from volcanic ash by weathering. The contents of 2:1 and 2:1:1 layer silicates and their intergrades were larger in soils in which quartz predominated in fine fractions. It was inferred that aluminum bound with humus and in allophane-like constituents, rather than aluminum in allophane and imogolite, is important in reactions with phosphate and fluoride.     

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.     

Extractability of manganese and iron oxides in typical Japanese soils by 0.5 mol L−1 hydroxylamine hydrochloride (pH 1.5)

We investigated the extractability of manganese (Mn) and iron (Fe) oxides from typical Japanese soils (Entisols, Inceptisols, and Andisols) by 0.5?mol?L^?1 hydroxylamine hydrochloride (NH₂OH-HCl) extraction (pH 1.5; 16?h shaking at 25°C; soil:solution ratio 1:40), referred as to HH_mBCR, which is Step 2 (used for the reducible fraction) of the modified BCR (Community Bureau of Reference) sequential extraction procedure. The HH_mBCR procedure extracted almost all Mn oxides from the non-Andisol samples, but failed to extract a part of the Mn oxides from some Andisol samples. The procedure extracted most short-range ordered Fe oxides from non-Andisol samples, but it extracted only 7.5% and 13% of the short-range ordered Fe oxides from allophanic and non-allophanic Andisol samples, respectively. This remarkably low extractability of Fe oxides suggests that the HH_mBCR method is not suitable for extracting oxide-occluded heavy metals from Andisols. Since the extraction rate of short-range ordered Fe oxides from various soils with the extractant was negatively correlated with the amounts of oxalate- and pyrophosphate-extractable Al even when the variability of the extraction pH was reduced by increasing the soil:solution ratio from 1:40 to 1:500, the extractability of Fe oxides would be negatively affected by the presence of active Al, including allophane/imogolite, amorphous Al, and Al-humus complexes. Because these Al constituents are abundant in Andisols, they would be at least partially responsible for the lower extractability of Fe oxides by HH_mBCR from Andisols.     

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.     

在实验酸性硫酸盐条件和酸性硫酸盐土壤上可溶性铝的控制

The controls of soluble Al concentration were examined in three situations of acid sulfate conditions:1) experimental acid sulfate conditions by addition of varying amounts of Al(OH)3(gibbsite) into a sequence of H2SO4 solutions;2)experimental acid sulfate conditions by addition of the same sequence of H2SO4 solutions into two non-cid sulfacte soil samples with known amounts of acid oxalate extractable Al; and 3) actual acid sulfate soil conditions.The experiment using gibbsite as an Al-bearing mineral showed that increase in the concentration of H2SO4 solution increased the soluble Al concentration,accompanied by a decrease i the solution pH, Increasing amount of gibbsite added to the H2SO4 solutions also increased soluble Al concentration,but resulted in an increase in solution pH.Within the H2SO4 concentration range of 0.0005-0.5mol L^-1 and the Al(OH)3 range of 0.01-0.5g(in 25 mL of H2SO4 solutions),the input of H2SO4 had the major control on soluble Al Concentration and pH .The availability of Al(OH)3，however,was responsible for the spread fo the various sample points,with a tendency that the samples containing more gibbsite had a higher soluble Al concentration than those containing less gibbsite at equivalent pH levels.The experimental results from treatment of soil samples with H2SO4 solutions and the analytical results of acid sulfate soils also showed the similar trend.     

Effects of pH and aluminosilicate composition on KMg exchange selectivity of amorphous aluminosilicates

The KMg cation exchange selectivity of some allophanic soil clays, imogolite and a range of synthetic hydrous oxides and amorphous aluminosilicates was studied using solutions 0.05N with respect to KCl and MgCl₂. The preference of the aluminosilicates for Mg²⁺ increased with pH, which is in qualitative agreement with the predictions based on double-layer theory. Large quantitative discrepancies indicated, however, specific interaction of potassium with aluminosilicates of low and intermediate Al/(Al + Si) molar ratio. The potassium selectivity of these materials probably arises from swelling-pressure effects and steric restriction on the entry of the larger hydrated Mg²⁺ into channels in the aluminosilicate aggregates. Hydrous oxides of iron and aluminium were found to specifically adsorb magnesium at alkaline pH values and evidence indicates that specific adsorption by these materials also occurred in soil clays and in Fe(NO₃)₃-treated synthetic aluminosilicates.     

THE CATEGORIES OF ALUMINIUM- AND IRON-HUMUS COMPLEXES IN ANDO SOILS DETERMINED BY SELECTIVE DISSOLUTION

Thirty-three samples of Ando soils were extracted by sodium pyrophosphate (O.IM; pH 10) and by dithionite-citrate. The Al, Fe, and C contents of these two extracts offer a means of differentiating the status of humus in relation to Al and Fe in the different horizons. The humus that forms at first in the Al horizon has a very low complexing ability for Al and Fe and little is dissolved by pyrophosphate. The humus evolves with time or pedogenesis into forms that complex Al and Fe released from volcanic ash by weathering, and which are dissolved by pyrophosphate. In the old horizons, the humus further reacts with additional Al and Fe, some of which may be present as hydrous oxides or allophane-like constituents, allophane and imogolite. This reaction probably makes the humus less soluble in pyrophosphate.     

Speciation and Solubility Control of Aluminium in Soils Developed from Slates of the River Sor Watershed (Galicia,NW Spain)

The Al species in the soid and liquid phases were studied in eight soils developed from slates in a watershed subjected to acid deposition. From soil solution data the mechanisms possibly controlling Al solubility are also discussed. The soils are acidic, organic matter rich and with an exchange complex saturated with Al. In the solid phase, more than 75% of non-crystalline Al was organo-Al complexes, mostly highly stable. In the soil solutions, monomeric inorganic. Al forms were predominant and fluoro-Al complexes were the most abundant species, except in soil solutions of pH<4.8 and Al L/F ratio >3, in which Al³⁺ predominated and sulphato-Al complexes were relatively abundant. The most stable phases were kaolinite, gibbsite and non-crystalline Al hydroxides. In most samples, Al solubility was controlled by Al-hydroxides. Only in a few cases (solutions of pH 4-5, Al³⁺ activity >40 µmol L-¹ and SO₄ content >200 µmol L-¹), Al-sulphates such as jurbanite also could exert some control over Al solubility. In adition to these minerals, a possible role of organo-Al complexes or the influence of adsorption reactions of sulphate is considered, especially for samples with very low Al³⁺ content (<0.5 µmol L-¹).     

Solubility characteristics of proto-imogolite sols: how silicic acid can de-toxify aluminium solutions

Proto-imogolite sols can be considered as highly dispersed forms of proto-imogolite allophane, the most widespread type of allophane in volcanic and non-volcanic soils world-wide. The solubility characteristics of such sols define the conditions of precipitation of allophanes in soils, and the maximum concentrations of aluminium released during acidic episodes from soils, such as podzols, that contain allophane. Direct measurement of Al, Si and pH values in equilibrium with proto-imogolite sols, approached from higher and lower pH, indicated a solubility equation: where log*K_so lay in the range 7.14 to 7.23 after equilibration for 4–24 weeks at 22 + 2°C in 17 of the 20 systems studied. The mean value of log *K_SO at 298 K was calculated as 7.02. This value indicates that proto-imogolite will be more stable than amorphous aluminium hydroxides at H₄SiO₄ concentrations above 5 × 10^?6m , but less stable than bayerite below 10^?3m H₄SiO₄, and than gibbsite below 10^?2m . Proto-imogolite is more stable than micro-crystalline gibbsite in 10^?4m H₄SiO₄, a typical minimum concentration in soil solutions and streams in landscapes where podzols are present. The rapid formation of proto-imogolite effectively prevents the formation of gibbsite seeds in soil, except in highly leached and warm environments, i.e. in older landscapes in the tropics. Although the presence of 10^?4m silicic acid has been found to eliminate the acute toxicity to fish exhibited by solutions containing 6–7 μm Al at pH 4.96, little or no proto-imogolite would form under these conditions. Silicic acid would, however, prevent the precipitation of aluminium hydroxides, and could inhibit the formation of the A1₁₃ polycation. These polymeric species are a likely cause of the increased toxicity exhibited by partially neutralized aluminium solutions.