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.     

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.     

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.     

Chemical and colloidal stability of sols in the Al2O3-Fe2O3-SiO2-H2O system: their role in podzolization

Concentrations of dialysable silica in equilibrium with Al₂O₃-SiO₂-H₂O sols at pH 4.5–5.0 confirm the formation of a poorly ordered non-dialysable proto-imogolite species with an Al : Si ratio near 2, close to that of imogolite. Sols with Al : Si>2 give nearly constant levels of free silica in solution in the range 2–6 μg/cm³, indicating equilibrium between proto-imogolite and aluminium hydroxide species. These findings indicate that imogolite-like precipitates in acid soils will buffer silica in solution to within this range during leaching episodes. Imogolite is more stable than a previous estimate suggested, and a revised value for its free energy of formation is proposed: ΔG⁰_f(298.15) = -2929.7 kJ/mol. In Fe₂O₃-SiO₂-H₂O sols, the Fe : Si ratio of the non-dialysable species varies smoothly from 11 to 3 as free silica in solution ranges from 4 to 35 μg/cm³. Such sols are much less colloidally stable than hydroxyaluminium silicate sols, but mixed Al₂O₃—Fe₂O₃—SiO₂—H₂O sols are almost as stable as iron-free sols up to a Fe : Al ratio of 1.5. Thus migration of Al and Fe as mixed hydroxide sols can account for the almost constant ratio of Al to Fe with depth in oxalate extracts from Bs horizons of podzols.     

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.     

The solubility characteristics of organic Al precipitates in allophanic Bs horizons could mimic those of Al hydroxides, and indicate the solubility of associated allophanes

It is shown that Al-humate and fulvate precipitates in Bs horizons of pH > 4.6 can be the source of the soluble aluminium which is rapidly released in equilibrium studies to give log₁₀{Al³⁺} + 3pH values near 9.4 at 8°C, so that it is not necessary to postulate an anomalously reactive but sparingly soluble Al(OH)₃ phase. These Al-organic precipitates will have reached equilibrium in the natural soil environment with the more slowly reacting hydroxy-aluminium precipitates present, including proto-imogolite allophane, but can release Al³⁺ much more rapidly than the inorganic precipitates in laboratory equilibrations and soil leaching episodes that yield lysimeter waters. Equilibrium concentrations of Al reported in a range of Bs horizons indicate that the allophanes present are less soluble than proto-imogolite sols prepared in the laboratory and matured for up to 2 years.     

Composition and properties of poorly ordered minerals in Welsh soils. I. Composition

Eleven horizons of acidic soils in mid-Wales developed from Lower Palaeozoic sedimentary rocks were examined. Selective extraction of Al and Si provided evidence against the occurrence of significant quantities of poorly ordered Al-silicates. Fe₀ was weakly correlated with Al₀, but very closely correlated with Al₀ minus Al extracted by cold 5% Na₂CO₃, implying that poorly ordered Al occurs in part as a substituent in Fe oxide and in part in a form unassociated with Fe oxide. Support for this was obtained by analysis of oxide fractions concentrated from aqueous suspensions by sequential ultracentrifugation and through the examination of synthetic Al-substituted Fe oxides. Fe oxide containing Al substituted at an almost constant level was the dominant constituent of the poorly ordered fraction in four of the five Bs horizons examined. The occurrence of Al in this form is an important mechanism by which Al is retained in aerobic but highly acidic Bs horizons.     

Al-Spezies im Sickerwasser saurer Waldböden - Einfluß von Wasserbewegung und Löslichkeitsgleichgewichten

Aqueous Aluminum Species in Acidic Forest Soils - Influence of Water Pathways and Solubility Equilibria In the seepage of three typical Black Forest soils (Haplic Podzol, Dystric Cambisol, Dystric Planosol) the fractions ‘Labile-Monomeric Al’, ‘Stabile-Monomeric Al’ and ‘Acid-soluble Al’ were analyzed. Activities of aqueous Al species and saturation indices (SI) with respect to various Al-bearing minerals were calculated from ‘Labile-Monomeric Al’, using the computer program WATEQF. Al-mobilization/immobilization processes were evaluated by means of AI/CI molar ratios. With 1.5 mg/L in average, the Al_total concentrations are relatively low in all studied soils. In the O-horizon leachates, 70 to 80% of aqueous Al occur as ‘Stabile-Monomeric’ and ‘Acid-soluble’ forms mainly consisting of organo-complexes. This portion decreases in the mineral soil to 35% in the podzol and the planosol as well as to 10% in the Cambisol. Simultaneously, Al³⁺ increases to 40% (planosol), 50 (podzol), and 70% (cambisol). In all horizons, 5 to 15% of Al_total are covered by Al-fluoride-complexes, whereas Al-sulfate-complexes are insignificant. With 5 to 10% monomeric Al-OH-ions play a role only in the subsoil. Aluminum is strongly mobilized in the upper mineral horizons of all studied soils. In the planosol and the cambisol, Al is immobilized in the subsoil. In the subsoil of the podzol, in contrast, Al reveals further mobilization due to a distinct internal production of HNO₃ and H₂SO₄ as a consequence of mineralization of organic matter. In the podzol, rapid percolation in macropores is crucial for Al dynamics, whereas in the planosol the temporal variation of the perched water table. Leachates from all O-horizons and upper mineral horizons as well as from the planosol subsoil are undersaturated with respect to the solubility of all mineral phases considered. With SI > O imogolite appears to be a permanently stable mineral in the subsoils of both podzol and cambisol. There is evidence for the Al(OH)₃ interlayer of Al-chlorites controlling Al dynamics in the subsoil of the podzol. Al(OH)SO₄ type minerals are not likely to regulate aqueous Al activities in any of the studied 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.     

Semiquantitative determination of imogolite and Al-rich allophane (Si / Al ≃ 1 : 2) in some volcanic ash soils in San'in region by a combination of thermogravimetry-differential thermal analysis and trimethylsilylation analysis of soil clays

Abstract

A method to determine the contents of imogolite and Al-rich allophane (Sil Al ? 1 : 2) in volcanic ash soils was presented. The method is based on the (1) assessment of the presence of Al-rich allophane in clays by successsive extraction with dithionite-citrate and oxalate-oxalic acid, (2) trimethylsilylation of soil clay with a mixture of hexamethyldisiloxane, HCl, and isopropyl alcohol, and determination of the content of monomeric Si based on the trimethylsilyl derivative of monomeric orthosilicate anion by gas / liquid chromatography, (3) determination of the total content of imogolite and Al-rich allophane based on the content of monomeric Si from imogolite, (4) determination of the imogolite content by Thermogravimetry (TG )-Differential Thermal Analysis (DTA) based on the weight loss due to endothermic dehydroxylation with maximum values at ca. 386°C, (5) calculation of the Al-rich allophane content by subtracting the imogolite content from the total content of these minerals, and (6) evaluation of the imogolite and Al-rich allophane content of soil by multiplying clay content of soil and the two mineral content of clay. The trimethylsilylation analysis was found to be reproducible, and the estimated total amounts of two minerals in clays by this method were adequately approximated to those evaluated from the amount of Si (= Si_o) extracted with oxalate-oxalic acid after extraction with dithionite-citrate. The variation in the abmldance of two minerals in the soil horizons of volcanic ash soils from the San'in region indicated that this method is suitable for the profile-study of volcanic ash soils.     

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.     

A re-interpretation of 'Aluminium solubility mechanisms in moderately acid Bs horizons of podzolized soils' by Gustafsson et al.

Gustafsson et al. in a recent paper in this Journal reported the effects of adding HCl, AlCl₃ and Si(OH)₄ on the pH and concentrations of Al and Si in 1:1 soil:solution systems at three different temperatures, using samples of soil from an allophanic Bs horizon. Contrary to their conclusions, their observations are compatible with Al in the soil solution being in equilibrium with a proto‐imogolite allophane; it is neither necessary nor even plausible to postulate a hypothetical Al hydroxide. Concentrations of 0.2–0.4 mm Si in the equilibrated solutions at pH 5 could arise from an amorphous silica, probably phytoliths. They cannot come from the allophane.     

IMOGOLITE AND PROTO-IMOGOLITE ALLOPHANE IN SPODIC HORIZONS: EVIDENCE FOR A MOBILE ALUMINIUM SILICATE COMPLEX IN PODZOL FORMATION

Examination by infrared spectroscopy and electron microscopy of the fine clays (<0.5 μm) dispersed at pH 3.5 from H₂O₂-treated soil indicates that imogolite and proto-imogolite allophanes are concentrated in podzolic B₂ and B₃ horizons, and make up at least 6 percent of one B₂ horizon soil, which contains virtually no layer silicate clays. It is argued here that imogolite-type components are the principal source of extractable aluminium and silicon in such horizons, that they may act as cementing agents in indurated horizons, and that proto-imogolite, a soluble aluminium-silicate complex, is the predominant mobile form in which aluminium is transported to B₂ and lower horizons of podzols. Comparison of the amounts of aluminium extracted by acetic acid with those extracted by EDTA indicates that extractable aluminium in Bhg, Bh, and organic-rich A₂ horizons is present principally in organic complexes. It is proposed that the aluminium fulvates concentrated in these horizons are formed in situ.     

Modelling the solid–solution distributions of protons, aluminium, base cations and humic substances in acid soils

wham , an equilibrium chemical model for soils, waters and sediments, centred on a discrete-site/ electrostatic model of humic substances (HS), has been used to analysae batch titration data for organic and mineral horizons of acid soils. In most cases, tolerable fits were obtained by optimizing the soil contents of HS and aluminium, while keeping the model parameters (site densities, equilibrium constants, electrostatic terms) fixed. The optimized contents agreed reasonably with those estimated by chemical extraction. For some mineral soil samples, low in HS and high in aluminium, fitting of the titration data was improved by assuming the formation and dissolution of A1(OH)₃ and adjusting its solubility product. Solid-solution distributions of base cations (Na⁺, Mg²⁺, K⁺, Ca²⁺, NH⁺⁴) could be explained by non-specific counterion accumulation, with a small degree of selectivity. The WHAM sub-model for fulvic acid sorption accounted approximately for observed aqueous-phase concentrations of organic carbon and organically-complexed aluminium.     

Prolonged leaching of mineral forest soils with dilute HCl solutions: the solubility of Al and soil organic matter

Long-term acidification has been shown to result in a considerable decrease in the amount of organically bound soil Al and in a gradual decrease in the solubility of Al. We examined the solubility of soil organic matter (SOM) and Al in four acid mineral soils (one Arenosol Ah, two Podzol Bh, and one Podzol Bs) as they were leached sequentially using a solution containing 0.001 m HCl and 0.01 m KCl. The acid leaching resulted in relative decreases in Al that were 2–6 times greater than for organic C. The organic C and Al dissolved by the acid leaching originated mainly in the pyrophosphate-extractable fraction of the elements. Protonation seems to be a major mechanism in stabilizing the residual SOM, as indicated by small changes in effective cation exchange capacity with the degree of acid leaching. In the samples of Podzol Bh and Arenosol Ah soils the solubility of Al (defined as log₁₀{Al³⁺} + 1.5pH) in equilibrium suspensions (0.01 m KCl) was closely related to the ratio of pyrophosphate-extractable Al to pyrophosphate-extractable organic C. The Podzol Bs sample probably contained a small amount of a surface-reactive Al(OH)₃ phase, which rapidly became depleted by the acid leaching.     

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.     

Aluminium chemistry in two contrasted acid forest soils and headwater streams impacted by acid deposition,Vosges mountains,N.E. France

Al chemistry was studied in two acidic watersheds, one with a podzol, the other with an acid brown soil, in the Vosges mountains (N.E. France), by analysing both leaching and centrifugation soil solutions and spring waters over 3 yr. In the podzol, Al was mobilized in the eluvial horizons under the predominant influence of organic acidity, then leached down the profile as organic and F-bound Al. Strong undersaturation with respect to proto-imogolite and imogolite showed that the proto-imogolite theory of podzolization could not apply. Al was transferred from the soil to spring water mostly as Al³⁺ and Al-F. Al³⁺, as well as additional minor species (AlOH²⁺, AlSO₄ ⁺), originated from the redissolution of the top of the spodic horizons under the influence of both soil solution acidity and the occurrence of mobile anions derived from atmospheric deposition. Conversely, in the acid brown soil, Al mobilization was regulated by nitrate and occurred mainly as Al³⁺. Most of Al was retained in the deep soil and only traces of monomeric Al reached spring water. In the podzol eluvial horizons, soil solutions were undersaturated with respect to all relevant mineral phases and their chemical composition agree with the concept of a mobilization of Al from the solid soil organic Al and a control of Al³⁺ activity by complexation reaction with the solid and soluble soil organic matter and F. In the acid brown soil, soil solutions were found to be in equilibrium with natural alunite, and the formation of this mineral, if confirmed, would account for the occurrence of 'open' vermiculites instead of the expected hydroxy-Al interlayered vermiculites. Al solubility control in surface water of both watersheds remains unclear. The Al-F species in both watersheds and the likely control of Al solubility by alunite in the acid brown soil emphasize the influence of acid deposition on Al chemistry in acid watersheds.     

Soil solution aluminium activity related to theoretical A1 mineral solubilities in four Australian soils

Four soils were treated with HNO₃, CaCO₃ and K₂SO₄ to enable observation of the response of the soil solution composition and the solution A1 ion activity (Al³⁺) to the treatments and to time. The clay fraction of three of the soils was dominated by illite, kaolinite and quartz. The fourth was minated by kaolinite and iron oxides. The initial pH in 0.01 M CaCl₂ varied between 4.0 and 5.0 and the organic carbon content from 0.7 to 1.1%. The soil solutions from soils dominated by kaolinite, illite and quartz were generally supersaturated with respect to quartz and well ordered kaolinite, and unsaturated with respect to illite. The soil solutions from the soil dominated by kaolin and iron oxide were generally unsaturated with respect to quartz but still saturated with respect to ell crystallized kaolin. Within mineral groups such as Al₂SiO₅ compounds, A1₂Si₂O₅(OH)₄ (kaolinite group), and Al(OH)₃ (A1 oxide) minerals, the more soluble forms became less supersaturated or unsaturated with time for many treatments. Lime treatment usually increased the ion activity product of AI(OH)₃ in all soils, and of minerals with the composition, Al₂SiO₅, in the illite/kaolinite soils. Acid treatment reduced the apparent solubility of Al(OH)₃, and the A1 silicates in the Al₂SiO₅, and Al₂, Si₂, O₅,(OH)₄, mineral groups on all soils. These results are interpreted to indicate that lime treatment led to the formation of trace quantities of more soluble A1 minerals that subsequently controlled (Al³⁺), whereas acid treatment dissolved trace quantities of such minerals leaving less soluble minerals to control (Al³⁺). The results suggest that, in mineral soils such as these, (Al³⁺) is under the control of inorganic dissolution and precipitation processes. These processes conform to expectations given the free energy of various inorganic aluminium compounds. Furthermore the sequence of dissolution and formation processes appears to be governed by the Gay-Lussac—Ostwald step rule.     

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.     

Silicon,aluminum, and oxalic acid interactions in two California forest soils

Abstract

The release of solid‐phase soil aluminum (Al) from two soils was studied under acidic conditions and also in the presence of monosilicic acid. The soils support mixed‐conifer forests in the mid‐elevation Western Sierra Nevada in northern California, but differ in their state of development and mineralogy as shown by Al, iron (Fe), and silicon (Si) concentrations. The pyrophosphate‐extractable Al (Al_p) pool, which was a main source of released Al, decreased after a two‐month leaching with nitric (HNO₃) or oxalic (HO₂C‐CO₂H) acids. Addition of monosilicic acid (SiO₂.XH₂O) to the acid extractants resulted in a further decrease of Al. Solution monosilicic acid was removed from solution by sorption on Fe oxides/hydroxides in the soil with the higher dithionite‐extractable Fe pool. In the less developed soil with lower pedogenic Fe, the formation of short‐range‐ordered aluminosilicates, even in the presence of a strong Al chelator, was responsible for the removal of a portion of the monosilicic acid from solution. Pedogenic Fe inhibited the formation of short‐range‐ordered aluminosilicates more than the presence of a strong Al chelator. Both the solution phase and surface reactions are important in the pedogenic formation of alumino‐silicate minerals.