Crystallization of single and binary iron‐ and aluminum hydroxides affect phosphorus desorption

In acidic soils, phosphorus availability is affected by its strong affinity for mineral surfaces, especially Fe‐ and Al‐hydroxides. Plant roots have developed adaptive strategies to enhance the availability of phosphorus, including producing and exuding low molecular weight organic acids with a high affinity for phosphorus that competes with high molecular weight organic ligands formed during humification and mineralization. The aim of this study was to characterize the kinetics and mechanism of phosphorus desorption from Fe‐ and Al‐hydroxides of variable crystallinity, as well as binary Fe:Al‐hydroxide mixtures. Long‐term desorption experiments (56 days) were conducted with CaCl₂, CaSO₄, citric acid, and humic acid as competitive sorptives. CaCl₂ and CaSO₄ were selected as general inorganic sorptives and citric and humic acids were selected as organic ligands produced by organisms in the rhizosphere or following humification. The cumulative phosphorus desorption increased following the order CaCl₂ < CaSO₄ < humic acid < citric acid. Amorphous ferrihydrite and Fe‐rich Fe:Al‐hydroxides exhibited much less desorption when exposed to inorganic solutions than the crystalline and Al‐rich Fe:Al‐hydroxide mixtures. Models of the desorption data suggest phosphorus desorption with citric acid is diffusion‐controlled for ferrihydrite and Fe‐rich amorphous Fe:Al‐hydroxides. When humic acid was the sorptive, metal‐organic complexes accumulated in the solution. The results suggest organic compounds, especially citric acid, are more important for liberating phosphorus from Fe‐ and Al‐minerals than inorganic ions present in the soil solution.     

Fractionation of extractable aluminum in acid soils: A review and a proposed procedure

Abstract

Different forms of soil aluminum (Al) are involved in the retention of anions and cations, phytotoxicity of Al in acid soils, CEC reduction and soil physical properties such as aggregate stability and water infiltration. Therefore it is desirable to quantify the different forms of Al in soil especially acidic soils. A rationale was developed from a literature survey to identify the following fractions of Al: (a) exchangeable quantified by 1M KC1 extraction; (b) organic bound quantified by 0.1M CuCl₂ + 0.5M KCl extraction; (c) sorhed Al extractable with 1M NE₄OAc at pH 4.0; (d) amorphous Al oxide and hydroxide and amorphous aluminosilicates (if present) extractable with 0.2M ammonium oxalate at pH 3.0; and (e) interlayered Al extractable with 0. 33M sodium citrate at pH 7.3. Pools (a), (b), and (c) are extracted sequentially. Amorphous Al oxide and hydroxide (pool d) is calculated from ammonium oxalate extractable Al minus (a + b + c). Interlayered Al is calculated from sodium citrate extractable Al minus ammonium oxalate extractable Al. The latter two extractions are done on separate subsamples of soils. From preliminary studies and data for 13 soil samples it is suggested that this fractionation of soil Al is more meaningful than that obtained by the KCl ‐> K₄P₂O₇ ‐> ammonium oxalate > citrate‐bicarbonate‐dithionite extraction sequence.     

Aluminium sulphate solubility in acid forest soils in Denmark

Ion leaching in 3 sandy spruce forest soils of different origin and pH was investigated in the laboratory. Zero-tension lysimeters containing undisturbed soil columns of varying soil depth were subjected to H₂SO₄ loadings for a period of 9 weeks. The analysis of the resulting leachate supports the hypothesis that Al-sulphate minerals may form in acidic soils when exposed to acid (H₂SO₄) deposition. In the B horizon of a glaciofluvial sandy soil (pH 4.2), both H⁺ and sulphate ions were retained to maintain 2pH + PSO₄ = 11.9 in the leachate solutions. This relation between H⁺ and sulphate activity may be due to an adsorption mechanism or a precipitation mechanism. The precipitation mechanism is favored by the good fit of leachate composition to the conditions for jurbanite [AlOHSO₄] formation from gibbsite [Al(OH)₃]. In the B horizon of a sandy till at pH 3.7, the Al in soil solution (0.5 mmol L^?1) was leached with sulphate. As the sulphate load was increased, some sulphate was retained. This may also be due to the dissolution and precipitation of an Al-sulphate mineral. The ion activity products of leachate solutions from the B horizon of this soil were close to the pK_s reported for jurbanite. The conditions for the possible existence and/or formation of Al-sulphate minerals in acidic soils are discussed.     

Response of some soils of Galicia (NW Spain) to H2SO4 acidification

This paper presents the results of an acidification experiment, consisting of seven consecutive equilibrations of repesentative soils of Galicia with a H₂SO₄ solution (pH 3). Different responses to soil acidification, such as SO₄ retention and cation release, were evaluated. In soils derived from gabbro and amphibolite, SO₄ retention and Al release were the principal acid neutralization mechanisms, whereas in soils derived from granite, schist, shale and sandstone Al release was the main process. The SO₄ retention was significantly correlated with Al and Fe extracted with dihionite-citrate-bicarbonate and crystalline Fe. The released base cations came mainly from exchange sites, though sometimes also from other sources, probably by mineral weathering. The major sources of Al in these soils were metalorganic complexes and weatherable minerals. Solutions with pHs close to 4 are in equilibrium with gibbsite, kaolinite, jurbanite and alunite; at lower pH values, with jurbanite and alunite.     

Factors affecting the degree of phosphate-removal in the system FeCl3-orthophosphate and nature of the precipitates

In this batch type parametric study the influence of phosphate concentrations on the extent of its removal by constant amount of FeCl₃ at different pH, temperature and aging time is evaluated. The efficiency of FeCl₃ in removing the phosphate is strongly dependent on the pH of the precipitation. At P/Fe molar ratios of higher than 0.5 the pH of maximum phosphate removal is found to be at pH 2.5 and is followed by pH 4, 6 and 9. The optimum pH for maximal phosphate removal greatly varies with the amount of phosphate present relative to that of iron present. It is also observed that maximal phosphate removal by FeCl₃-solution is achieved at P/Fe ratios of more than 1, 0 suggesting that in removal process not only Fe³⁺ but also colloidal hydroxide particles could play an important role. The samples of non-aged synthesized precipitates obtained at P/Fe ratios of 8, 4 and 2 at pH 2.5 are found to have characteristic lines of strengite. The formation of strengite at room temperature from fresh solutions has not previously been reported. Thermally treated precipitates with the characteristic lines of strengite transform into a quartz-like phase which suggests that the loss of the coordinated water leads to a compound like ABO₄ where A and B both are in tetrahedral coordination. Upon heat treatment, the amorphous precipitates, having P/Fe ratios > 0.5, obtained between pH 2.5 and 6 result in a quartzlike phase. However, the characteristic lines of the quartz phase are not of the same intensity. In contrast, the precipitates having P/Fe ratios < 0.5 transform into hematite after heat treatment. The thermally treated products of precipitates obtained at pH 9 are found to have η-Fe₂O₃ phase which indicates that basic phosphates formed at this pH are structurally similar to that of basic sulfates.     

Isolating the influence of pH on the amounts and forms of soil organic phosphorus

Soil pH influences the chemistry, dynamics and biological availability of phosphorus (P), but few studies have isolated the effect of pH from other soil properties. We studied phosphorus chemistry in soils along the Hoosfield acid strip (Rothamsted, UK), where a pH gradient from 3.7 to 7.8 occurs in a single soil with little variation in total phosphorus (mean ± standard deviation 399 ± 27 mg P kg^?1). Soil organic phosphorus represented a consistent proportion of the total soil phosphorus (36 ± 2%) irrespective of soil pH. However, organic phosphorus concentrations increased by about 20% in the most acidic soils (pH < 4.0), through an accumulation of inositol hexakisphosphate, DNA and phosphonates. The increase in organic phosphorus in the most acidic soils was not related to organic carbon, because organic carbon concentrations declined at pH < 4.0. Thus, the organic carbon to organic phosphorus ratio declined from about 70 in neutral soils to about 50 in strongly acidic soils. In contrast to organic phosphorus, inorganic phosphorus was affected strongly by soil pH, because readily‐exchangeable phosphate extracted with anion‐exchange membranes and a more stable inorganic phosphorus pool extracted in NaOH–EDTA both increased markedly as soil pH declined. Inorganic orthophosphate concentrations were correlated negatively with amorphous manganese and positively with amorphous aluminium oxides, suggesting that soil pH influences orthophosphate stabilization via metal oxides. We conclude that pH has a relatively minor influence on the amount of organic phosphorus in soil, although some forms of organic phosphorus accumulate preferentially under strongly acidic conditions.     

Natural “amorphous” ferric hydroxide

Rusty ferruginous precipitates deposited from soil-borne waters (in drainage ditches, from springs) at various localities, contain a ferric hydroxide rich in carbon and adsorbed water. It has up to 75% dithionite soluble Fe₂O₃, of which between 90 and 100% is oxalate soluble IR spectrograms do not show Fe-OH features in the OH stretching and bending range. X-ray diffraction reveals very broad lines at about 2.5 and 1.5 Å and somewhat sharper lines at 2.22, 1.97 and 1.71 Å, which are characteristic of ferrihydrite (name proposed by Chukhrov et al., 1972). These deposits are found in areas where water has percolated through acid soils rich in low molecular weight organic compounds. Furthermore, as similar material could be prepared in the laboratory by bacterial or H₂O₂ oxidation of ferric citrate solutions, it was concluded that the natural substance is formed by microbial decomposition of soluble iron—organic complexes. Transformation experiments suggest that aging under conditions corresponding to a humid temperate climate causes conversion to goethite. This aging process is greatly retarded by organic and other compounds retained by the hydroxide. No evidence of hematite formation could be found after 2 weeks at 70°C.     

Soils affected by acid mine waters in galicia (N.W. Spain)

Contaminated soils and surface waters, from copper mining in Galicia, are acidic, high in sulphate and increase appreciably in the concentration of elements such as Al, Fe, Ca, Mg, K, Mn, Cu and Zn by contact with soils and fragments of rock of an amphibolic composition. Application of activity data to mineral equilibrium diagrams illustrates the instability of Al-hydroxides and aluminosilicates compared to Al-sulphates of the alunite and jurbanite type, in the waters which are most acid and display sulphate activities close to 10^?2 M. The solution extracted from soils around the spoil heaps reflects the strong influence of the most heavily contaminated run-off waters, with little or no buffering by the solid phase. This aspect may be accounted for by both a brief time of residence and a real decrease of the acid buffering power of these soils, whose primary minerals undergo strong acidolysis. Neoformation of Al-sulphate (and Fe-sulphate) is observed both in soils and in the channels of the contaminated streams, above all the points of contact with non-acid or slightly acid waters.     

Phosphate sorption by synthetic amorphous aluminium hydroxides: a 27Al and 31P solid-state MAS NMR spectroscopy study

The sorption of phosphate on amorphous aluminium hydroxides was investigated using ²⁷Al and ⁷¹P solid-state magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, following the effect of different exposures to soluble phosphate. The spectra obtained were compared with the spectrum of amorphous aluminium phosphate. Aluminium in the unreacted hydroxide had a 100% octahedral co-ordination. When dried at 200°C and exposed to soluble phosphate, very little (maximum 0.1%) amorphous aluminium hydroxide transformed to a tetrahedral co-ordination (A1 bound by oxygen bridges to four P atoms), even after 120d. The tetrahedral co-ordination exists in aluminium phosphate gel, although most of its A1 atoms exhibit an octahedral co-ordination. For the aluminium hydroxide dried at 200°C, no formation of aluminium phosphate in which aluminium is in octahedral co-ordination could be detected, not even when the aluminium hydroxide was exposed to a phosphate solution for 120 d. We concluded that the formation of aluminium phosphate is restricted to the surface of the hydroxide. Most of the phosphate which is bound to the aluminium oxide however may not have formed a ‘bulk solid’ aluminium phosphate, but is adsorbed on the internal and external surface of the oxide. The same amorphous aluminium hydroxide, dried at 70°C instead of 200°C, is converted much more rapidly to aluminium phosphate when exposed to soluble phosphate. We propose a P-induced weathering mechanism to describe P sorption on amorphous aluminium hydroxides at high P concentrations. In addition to NMR, phosphate adsorption experiments conducted on aluminium hydroxides dried at different temperatures produced evidence that the porosity of the aluminium hydroxide aggregated particles can also be a factor controlling the rate of phosphate uptake from solution, if the aggregate is stable (is not resuspended) in solution.     

Use of a coupled equilibrium model to describe the buffering of protons and hydroxyl ions in some acid soils

The buffering of protons and hydroxyl ions in acid soils was studied by the addition of small amounts of HCl, H₂SO₄, and NaOH in consecutive batch experiments using surface soils and subsoils from two Cambisols and one Podzol. A chemical equilibrium model was used to study the main buffer processes. The model included inorganic complexation and multiple cation exchange, and also the solubility of jurbanite and Al(OH)₃ for the subsoils. Buffering of protons was predicted quite well by the model for the surface soil of the Spodi-Dystric and Spodic Cambisols, suggesting that multiple cation exchange was the main buffer process. For the Podzol surface soil, however, the model overestimated proton buffering by cation exchange considerably. Hydroxyl buffering in acid surface soils could be described well by the model for the Podzol soil only. For the Cambisols, hydroxyl buffer reactions included not only cation exchange, but also solubilization of large amounts of organic matter and presumably deprotonation of dissolved organic carbon (DOC). Modelling proton and hydroxyl buffering in subsoils suggested that equilibrium with AJ(OH)₃ was not maintained for the Podzol and spodic Cambisol. Sulphate sorption had to be considered to describe titration experiments in all three soils. The assumption of jurbanite being in equilibrium with soil extracts was useful only for the Spodi-Dystric Cambisol.     

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.     

Aluminum speciation in soil solutions: Equilibrium calculations

A computer simulation was done to illustrate how the equilibrium solubility and speciation of Al in well-aerated soil solutions may be affected by pH (from 2.0 to 10.0), organic acids (citric, oxalic, phthalic, and salicylic acid), metal ions (K, Mg, Ca, Al, Fe), inorganic ligands (F, OH, SO₄, PO₄, CO₃, and SiO₃), and type of Al-containing solid [kaolinite, gibbsite, or amorphous Al(OH)₃] thought to be present. The simulation indicated that the type of Al-oxide/hydroxide considered has a substantial influence on the inorganic and organic equilibrium composition of the soil solution, and on the occurrence (or non-occurrence) of other Al-minerals such as KA1₃(SO₄)₂(OH)₆ (alunite) and Al(SO₄)(OH)-5H₂O (jurbanite).     

Phosphorus and aluminium solubility relationships in acidic lowbush blueberry barren soils in Maine

Lowbush blueberry (Vaccinium angustifolium) is a native plant that is not cultivated, but managed in areas of sufficient plant density to provide commercial yields. A cropping systems study was initiated to compare how organic and three levels of conventional (low, medium and high input) management practices affected soil properties at 12 grower fields in the lowbush blueberry barrens of Maine. The fields under organic and low‐conventional treatments did not receive any fertilizer inputs. The high and medium conventional treatment fields received optimal and reduced diammonium phosphate inputs, respectively. Three measurements of soil P (modified‐Morgan soil test, oxalate extractable and total P) showed no significant effect of management treatment on the phosphorus status of the soils. This suggests that soil P may be leaching below the 0–10 cm rooting zone which was investigated in this study. Equilibrium chemical speciation of soil/water extracts showed that gibbsite was controlling the solubility of Al in these barren soils and that P was undersaturated with respect to amorphous Al(OH)₂PO₄. A laboratory one‐point P sorption study showed that dissolved organic matter derived from the organic pad sampled from the study sites did not inhibit the adsorption of the added P. This suggests that addition of carbon‐rich soil amendments such as compost may not increase P bioavailability of these acidic soils with high Al (oxy)hydroxide (gibbsite) mineral content.     

Importance of Noncrystalline Hydroxide Phases in Sequential Extractions to Fractionate Antimony in Acid Soils

Abstract

Sequential extraction techniques have been used to make inferences about speciation of phosphorus (P) and to a lesser extent arsenic (As) in soils. However, sequential extraction studies on the less‐abundant group V element, antimony (Sb), are limited. In this work, a widely used P sequential extraction scheme was modified and used to extract P, As, and Sb from two acidic soils from the Macleay River floodplain, NSW, that were enriched with Sb (26.9 and 23.0 mg kg^?1). An ammonium oxalate–oxalic acid step was included in the extraction sequence to dissolve the noncrystalline iron (Fe) and aluminium (Al) hydroxide phase. It extracted 30 to 47% of Sb, indicating the importance of this fraction, which may be mobilized in the floodplain by acid sulfate soil processes and periodic waterlogging. The original method overestimated P, As, and Sb in the residual fraction (30–71%). Relative efficiency values of extracts for P, As, and Sb were compared, and inferences about phase distributions were made. The results suggest some potential in using extractions to assess bioavailability of Sb in soil.     

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).     

SOIL ORGANIC MATTER STUDIES: EXTRACTION WITH FORMIC ACID/DIMETHYL SULPHOXIDE MIXTURES AND FRACTIONATION WITH Zr(IV)

Mixtures of the dipolar organic solvents formic acid (FA) and dimethyl sulphoxide (DMSO) were used to extract organic matter from soils. At 100 °C optimum extraction from a calcareous clay loam was with 80/20 v/v FA/DMSO, corresponding to a maximum in dielectric constant. Extraction of seven soils with boiling FA/H, O (107 °C) and FA/DMSO (112 °C) indicated that similar amounts of C and N are generally dissolved by the two solvent mixtures. However, FA/DMSO was about twice as efficient as FA/H₂O for the ver-miculite-rich, calcareous, organic clay loam, removing 66 per cent of its C and 54 per cent of its N. Zr(IV) hydroxide in acidic aqueous acetone was a better flocculant than Ti(IV) for the dissolved organic matter. Model compound studies, together with hydrolytic and NMR studies, indicated that Zr precipitates carbohydrate-like but not aromatic organic components. The quantity of Zr sorbed to the organic matter corresponds closely with its C.E.C. determined by Ba retention.     

Influence of Aluminum Hydroxide on Potassium Release from Two Colombian Soils

Abstract

The effect of sesquioxides on the mechanisms of chemical reactions that govern the transformation between exchangeable potassium (Kex) and non‐exchangeable K (Knex) was studied on acid tropical soils from Colombia: Caribia with predominantly 2∶1 clay minerals and High Terrace with predominantly 1∶1 clay minerals and sesquioxides. Illite and vermiculite are the main clay minerals in Caribia followed by kaolinite, gibbsite, and plagioclase, and kaolinite is the major clay mineral in High Terrace followed by hydroxyl‐Al interlayered vermiculite, quartz, and pyrophyllite. The soils have 1.8 and 0.5% of K₂O, respectively. They were used either untreated or prepared by adding AlCl₃ and NaOH, which produced aluminum hydroxide. The soils were percolated continuously with 10 mM NH₄OAc at pH 7.0 and 10 mM CaCl₂ at pH 5.8 for 120 h at 6 mL h^?1 to examine the release of Kex and Knex. In the untreated soils, NH₄ ⁺ and Ca²⁺ released the same amounts of Kex from Caribia, whereas NH₄ ⁺ released about twice as much Kex as Ca²⁺ from High Terrace. This study proposes that the small ionic size of NH₄ ⁺ (0.54 nm) enables it to enter more easily into the K sites at the broken edges of the kaolinite where Ca²⁺ (0.96 nm) cannot have access. As expected for a soil dominated by 2∶1 clay minerals, Ca²⁺ caused Knex to be released from Caribia with no release by NH₄ ⁺. No Knex was released by either ion from High Terrace. After treatment with aluminum hydroxide, K release from the exchangeable fraction was reduced in Caribia due to the blocking of the exchange sites but release of Knex was not affected. The treatment increased the amount of Kex released from the High Terrace soil and the release of Knex remained negligible although with Ca²⁺ the distinction between Kex and Knex was unclear. The increase in Kex was attributed to the initially acidic conditions produced by adding AlCl₃ which may have dissolved interlayered aluminum hydroxide from the vermiculite present, thus exposing trapped K as exchangeable K. The subsequent precipitation of aluminum hydroxide when NaOH was added did not interfere with the release of this K, and so was probably formed mostly on the surface of the dominant kaolinite. Measurement of availability of K by standard methods using NH₄ salts could result in overestimates in High Terrace and this may be a more general shortcoming of the methods in kaolinitic soils.     

Chemical Fractions of Mn in Acidic Soils and Selection of Suitable Soil Extractants for Assessing Mn Availability to Maize (Zea Mays L.)

Twenty surface (0–15 cm) samples of acidic soils were analyzed for water soluble (WS), exchangeable (EX), lead displaceable (Pb-disp.), acid soluble (AS), manganese (Mn) oxide occluded (MnOX), organically bound (OB), amorphous Fe oxide occluded (AFeOX), crystalline iron (Fe) oxide occluded (CFeOX) and residual (RES) fractions of Mn, and also for extractable Mn in some common soil extractants: (diethylenetriaminepentaacetic acid (DTPA) (pH 7.3), DTPA (pH 5.3), AB-DTPA (pH 7.6), Mehlich-3 (pH 2.0), Modified Olsen, 0.005 M calcium chloride (CaCl₂), 1 M magnesium chloride (MgCl₂) and ion exchange resins. The WS-Mn fraction showed a significant and positive correlation with Mn extractable in DTPA (pH 5.3) and AB-DTPA (pH 7.6), while both WS-Mn and EX-Mn fractions correlated significantly and positively with Mn concentration and uptake by maize plants grown in these soils. The AB-DTPA (pH 7.6) and DTPA (pH 5.3) appeared suitable to assess the availability of Mn in acidic soils.     

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.     

Soils of slopes and bottomland positions of the small stream valley in the central forest reserve: Chemical properties and clay mineralogy

Pale-podzolic soils occupying slope positions in a small stream valley are more acidic and contain less pedogenic chlorites in the clay fraction than those soils occupying uplands. These characteristics are thought to be caused by more intensive leaching of matter from eluvial horizons due to intensive lateral interflow of soil water. Soddy-gleyic soils of the stream bottomland are rich in organic matter and have a slightly acidic reaction in the A1 horizon and an alkaline reaction in the calcareous subsoil. Both factors lead to accumulation of Fe_ox and Al_ox supplied to bottomland positions from uplands and slopes and those formed in situ.