Increases in pH and soluble salts influence the effect that additions of organic residues have on concentrations of exchangeable and soil solution aluminium

It has been suggested that additions of organic residues to acid soils can ameliorate Al toxicity. For this reason the effects of additions of four organic residues to an acid soil on pH and exchangeable and soil solution Al were investigated. The residues were grass, household compost, filter cake (a waste product from sugar mills) and poultry manure, and they were added at rates equivalent to 10 and 20 t ha^?1. Additions of residues increased soil pH measured in KCl (pH_(KCl)) and decreased exchangeable Al³⁺ in the order poultry manure > filter cake > household compost > grass. The mechanism responsible for the increase in pH differed for the different residues. Poultry manure treatment resulted in lower soil pH measured in water (pH_(water)) and larger concentrations of total (Al_T) and monomeric (Al_mono) Al in soil solution than did filter cake. This was attributed to a soluble salt effect, originating from the large cation content of poultry manure, displacing exchangeable Al³⁺ and H⁺ back into soil solution. The considerably larger concentrations of soluble C in soil solution originating from the poultry manure may also have maintained greater concentrations of Al in soluble complexed form. There was a significant negative correlation (r = ?0.94) between pH_(KCl) and exchangeable Al. Concentrations of Al_T and Al_mono in soil solution were not closely related with pH or exchangeable Al. The results suggest that although additions of organic residues can increase soil pH and decrease Al solubility, increases in soluble salt and soluble C concentrations in soil solution can substantially modify these effects.     

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

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

Der Einfluß der natürlichen organischen Substanzen auf die Metallverteilung zwischen Boden und Bodenlösung in einem sauren Waldboden

The influence of organic matter in the translocation of metals between soil and soil solution of an acid forest soil Water extracts were prepared from soil samples which were collected from a soil profile showing very little variation in the texture down to a depth of 120 cm and thus only little translocation of clay in the soil profile. The aim of the study was to describe the distribution between soil and soil solution of several metals like Cu, Pb, Cd, Zn, Al and Mn as a function of humic substances, electrolyte concentration and pH. From the experimental results the following hypothesis on the reaction mechanisms involving metals and humus derived substances has been deduced. The metals Cu, Fe, Al and Pb are mobilized through complexation by soluble humus substances in addition to the usual pH dependent desorption and dissolution of hydroxides. This mobilization determines the solution concentration of Cu and Fe at pH > 3.7 and Al and Pb at pH > 4.2. Al, Fe and Pb are complexed selectively by high molecular weight humus derived substances which undergo adsorption on soil mineral surfaces. Cu interacts with low molecular weight humus derived substances which are not easily adsorbed by the mineral surfaces. Zn, Cd and Mn primarily undergo sorption and are thus controlled by pH and electrolyte concentration of solutions because their complexation with humus derived substances seems to be weak or nonexistant. It is further postulated that the humus derived substances mobilize Al³⁺ and Fe³⁺ ions. By this, other metals like Cd, Zn, Mn, Ca and Mg can occupy the free exchange sites.     

长期施用有机肥料对紫色水稻土有机无机复合性状的影响

连续九年施用有机肥料，紫色水稻土壤及＜０．００２ｍｍ的有机无机复合体中无定形铁，铝和铬合态铁，铝的含量呈不同程度的增加，铬合态铁和铝间具拮抗作用（ｒ＝０．７９９８ｎ＝７）；土壤的有机质含量增加主要是由于轻组有机质含量增加，而有机无机复合度下降，土壤重组腐殖质的含量为０．２５－０．０１ｍｍ＞＜０．００２ｍｍ＞１－０．２５ｍｍ＞０．０１－０．００２ｍｍ；有机无机复合度及重组腐殖质中松结态与紧结态的比值     

Forms of soluble aluminium in acidic topsoils estimated by ion chromatography and 8-hydroxyquinoline and their correlation with growth of subterranean clover

Labile Al in the soil solution measured by 8-hydroxyquinoline (Al_HQ) was a better predictor of plant growth than trivalent Al (Al_IC³⁺) measured by ion chromatography (IC). HQ reacted with some organic Al complexes which did not separate during chromatography. In the presence of oxalic acid, Al_HQ was greater than Al_IC³⁺, which was the same as the greater than Al³⁺ (Al³⁺_Calc), whereas in the presence of citric acid, Al_HQ was greater than Al_IC³⁺, and both were greater than Al⁺³_Calc, In extracts of soils that had been acidified, Al³⁺_IC was less than Al_HQ, which was similar to Al³⁺_Calc, when it was assumed that the only complexing ligands were OH^? and F^?. The proportion of Al³⁺_IC in the soil solutions decreased more than Al_HQ as the pH increased. Organic ligands appeared to form complexes with Al at the expense of AIF complexes. Forms of Al detected by IC differed in CaCl₂ extracts and soil solutions. Al_HQ in the CaCl₂ extracts and soil solution were closely correlated, although the proportion of Al_HQ was higher in the CaCl₂ extracts. And soil solutions. Al_HQ in the CaCl₂ extracts and soil solution were closely correlated, although the proportion of Al_HQ was higher in the CaCl₂ extracts.     

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).     

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.     

Research on the Threshold of Aluminum Toxicity and the Alleviation Effects of Exogenous Calcium,Phosphorus, and Nitrogen on the Growth of Chinese Fir Seedlings under Aluminum Stress

Chinese fir (Cunninghamia Lanceolata Lamb, Hook) is generally considered a superior timber in southern China and other areas in the world. In the past few decades, aluminum (Al) toxicity has become one of biggest stress factors in the production and growth of Chinese fir, although this species prefers an acidic environment. To date, the selection of indicator species for Al toxicity remains critical in the field, and Al toxicity has not been successfully treated by artificially controlling Chinese fir plantations. To assess the Al toxicity risk, the height of the dominant tree, the concentration of calcium (Ca²⁺)/Al³⁺ in soil solution, and the concentration of Ca²⁺?/?[Ca²⁺ + iron (Fe³⁺) + Al³⁺] in litter leached organic acids were introduced. The results indicated that eight plots had suffered Al toxicity. The threshold of Al toxicity was 37.53 mg kg^?1 in soil or 1.39 mmol L^?1 in soil solution, a pH of 4.15, a Ca²⁺?/?(Ca²⁺ + Fe³⁺ + Al³⁺) molar ratio of 0.487, and a Ca²⁺/Al³⁺ molar ratio of 1.599. The positive effects of exogenous nutrition (Ca, phosphorus [P], and nitrogen [N]) on the growth of Cunninghamia lanceolata seedlings was also studied in pot experiments based on results in the field. The cation nutrition can lead to detoxification, and the exogenous nutrition thresholds were Ca²⁺/?Al³⁺ ≥ 2.8, phosphorus (P)/?Al³⁺ ≥ 4.4, ammonium (NH₄ ^?)–nitrogen (N)?/?Al³⁺ ≥ 4.5. The data presented in this study are very helpful for the understanding of the degree of Al toxicity and have notable significance for the management of Chinese fir plantations.     

ALUMINUM SPECIATION OF AMENDED ACID TROPICAL SOIL AND ITS EFFECTS ON PLANT ROOT GROWTH

Exchangeable and soluble soil aluminum (Al) is limiting plant growth in many soils worldwide. This study evaluated the effects of increasing rates of dolomite and magnesium carbonate (MgCO₃) on Al³⁺, pH, dissolved organic carbon, cations, anions, and Al speciation on oil palm Deli dura × AVROS pisifera root growth. Dolomite and MgCO₃ additions significantly raised linearly soil solution pH, magnesium (Mg²⁺), nitrate (NO₃ ^?) and chlorine (Cl^?) concentrations; exponentially decreased the activity of phytotoxic Al species [aluminum (Al³⁺), aluminum sulfate (Al₂SO₄), and aluminum fluoride (AlF₃)]; and reduced manganese (Mn) concentration and activity. High activity of those species exponentially reduced root dry weight. Optimum oil palm growth was achieved at: <50 μM monomeric Al, < 30 μM Mn, and <0.20 unit of the ratio Al+Mn to calcium (Ca)+Mg. High activity of Al species and Mn in acidic soil solution cause significant reduction of the root growth. Soil acidity alleviation either with dolomite or MgCO₃ mitigates the toxic effect of Al and Mn.     

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.     

Aluminium Toxicity Risk for Pinus pinaster in Acid Soils (Galicia,NW Spain)

The influence of bedrock on aluminium toxicity and aluminium speciation in the soil solution was studied in four Pinus pinaster plots. Growth and biomass parameters in the acidic soils were also evaluated in relation to different Al toxicity indices. The plots were developed over slate, biotitic schist, mica schist and granite. Samples of rhizospheric and non‐rhizospheric soil, 1‐year‐old needles and roots were collected in each study plot. Total Al, reactive Al, acid‐soluble Al, non‐labile and labile Al and Al species (Al³⁺, Al‐OH, Al‐F and Al‐SO₄) were determined in soil solution. Reactive Al dominated over the acid‐soluble Al, and the non‐labile Al predominated over the labile Al in all soils, but particularly over mica schist. In the biotitic schist soil, the Al forms and total Al were lower, whereas concentrations were always higher over mica schist. The Al forms considered most toxic were Al³⁺ and Al‐OH, and Al concentrations were highest over slate and mica schist. Al toxicity indices in soil, needle and roots showed a risk of toxicity in mica schist, slate and granite. The stand site indices over slate and mica schist were lower, consistent with the high labile Al and Al³⁺ + Al‐OH in soil solution. Despite the high stand site index over granite, the growth efficiency was low, in accordance with very low ratios of Ca/Al in needles or fine roots. This confirmed the adaptation of maritime pine to granitic substrates. Copyright © 2016 John Wiley & Sons, Ltd.     

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.     

Effects of fertilization practices on aluminum fractions and species in a wheat soil

Purpose

To better understand the effect of fertilizer practices on soil acidification and soil organic matter (SOM) stocks in a rice-wheat system, a field experiment was conducted to (i) investigate the influence of fertilizer practices on the Al forms in solid phases and the distribution of Al species in water extracts and (ii) explore the relationship between the Al forms, the quantity and composition of SOM, and soil acidity.

Materials and methods

Seven fertilizer treatments including CL (no fertilizer), NK, PK, NPK, N₂PK (PK and 125 % of N), NP₂K (NK and 125 % of P), and organic fertilizer (OF) were applied to induce various changes in pH and SOM composition (i.e., total C and N contents, C/N ratio, and SOM recalcitrant indices) in a rice-wheat system. After 6-year cultivation, different pools of Al forms (i.e., amorphous Al; organically bound Al of varying stability; exchangeable Al; water-soluble inorganic Al³⁺, Al-OH, Al-F, Al-SiO₃, and Al-SO₄; and organic Al monomers) were quantified and related with SOM composition and soil pH during the wheat phase.

Results and discussion

Fertilizer types significantly changed soil pH and SOM composition and which explained 84 % of the variance of Al forms using redundancy analysis. An interaction between soil pH and SOM quality on Al forms also existed but only accounted for a very small (6 %) portion of the variation. Compared to CL and chemical fertilizer, OF practice with relative low SOM stabilization is likely to favor the formation of amorphous Al in order to bind more SOM. The decrease in exchangeable acidity and water-extractable Al via hydroxyl-Al precipitation but not in the form of organo-aluminum complexes evidenced this phenomenon. In contrast, chemical fertilizer input increased exchangeable Al and water extract Al (especially Al³⁺), partly at the expense of organically bound Al. The destabilization of organic-aluminum complexes was a mechanism of pH buffering evidenced by the increased soluble Al-dissolved organic matter (DOM) as soil pH decreases. Further, the magnitude of this trend was much greater for elevated N input compared with P input.

Conclusions

Chemical fertilizer with relative high SOM stabilization favored the formation of exchangeable Al and soluble Al resulting in soil acidification, whereas OF with relative low SOM stabilization tended to transform exchangeable Al and soluble Al to amorphous Al, thereby alleviating soil acidification and enhancing C stocks in a rice-wheat system.

     

CALCIUM: ALUMINIUM EXCHANGE EQUILIBRIA IN CLAY MINERALS AND ACID SOILS1

Exchange reactions between 0.0in AlCl₃ solutions of different pH and Ca-saturated montmorillonite, vermiculite, illite, and soils from the Park Grass Experiment at Rothamsted and the Deerpark Experiment, Wexford, Ireland, showed that Al³⁺ and Al(OH)₂⁺ were adsorbed from solutions of pH > 4.0 and Al³⁺ and H⁺ from solutions of pH < 3.0. When Al was adsorbed, the cation exchange capacity of Ca-saturated soils and clays increased. Conventional Ca: Al exchange isotherms showed that Al³⁺ was strongly preferred to Ca²⁺ on all soils and clays. The equilibrium constant for Ca: Al exchange, K, was identical for soils before and after oxidizing their organic matter and did not vary, for any exchanger, with Al-saturation or the initial pH of the AlCl₃ solution. This proved the validity of the procedure used for calculating exchangeable Al³⁺. K values for Ca:Al exchange favoured Al³⁺ in the order: vermiculite > Park Grass soil > Deerpark soil > illite > montmorillonite. The influence of surface-charge densities of the clay minerals on this order is discussed and a method proposed and tested for calculating the K value of a soil from its mineralogical composition.     

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.     

Determination of free Al3+ in soil solutions by capillary electrophoresis

Colorimetric and ion exchange methods are commonly used to distinguish and measure Al species in natural waters. Unfortunately they also include weakly complexed Al species in their ‘reactive' or ‘labile' Al fractions and thus are of limited value for the estimation of free Al³⁺. Capillary electrophoresis (CE) has the potential for direct measurement of Al³⁺, and its performance has been verified experimentally. The method also detected the stable and positively charged AlOx⁺ complex formed with oxalic acid. It was compared with a colorimetric and an ion exchange method by analysing artificial solutions containing low molecular weight organic acids as well as soil extracts and seepage waters and was found to be the only method closely matching the theoretically calculated values of free Al³⁺. In samples from the upper soil horizons of an acid forest soil less than 14% of total Al was present as free Al³⁺, whereas the colorimetric method found more than 65%, and the ion exchange method more than 80% of total Al in a ‘reactive' or ‘labile' form. The latter methods thus would seriously overestimate Al toxicity, whereas using CE Al toxicity is likely to be only slightly underestimated.     

The role of organic acids in the soil solution chemistry of a podzolized soil

The soil solution chemistry of a podzolized soil in the north of Sweden was monitored for four years using percolation lysimeters. Weak organic acids were a major constituent of the soil solution and are important because of their ability to form complexes with aluminium. Dissolved organics leached from the mor layer enhance the weathering rate in the eluvial horizon by forming complexes with aluminium, especially during the autumn when the leaching of dissolved organics was greatest. The weak organic acids were titrated and their pK_a values were evaluated. Aluminium was speciated with an ion-exchange method and by applying equilibrium calculations. Formation constants for the organic aluminium complexes were calculated to be log K_Along=5.42±0.32 m ^?1 (n=13) in spring and summer and log K_Alorg=4.87±0.14 m ^?1 (n=6) in autumn. Equilibria of Al³⁺ with solid phases were also examined using solubility constants. Percolation lysimeters below undisturbed and cut-off mor layers were compared.     

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.     

Identification and Characterization of High Acid Tolerant and Aluminum Resistant Yeasts Isolated from Tea Soils

From acidic tea soils of Kagoshima Prefecture in Japan, some soil properties were determined and 38 strains of acid tolerant microorganisms were isolated. Different Al³⁺ concentrations were applied to YG media to estimate Al resistance. Selected microbial strains could grow strongly in the liquid media in the presence of 100 mM Al³⁺ and survive even in 300 mM Al³⁺ at pH 3.0. Their base sequences of 28S rDNA-D1/D2 were determined and sequence data were searched using the Basic Local Alignment Search Tool (BLAST) system. The results of sequencing revealed that the isolates belong to two different species, Cryptococcus sp. and Candida palmioleophila. When cultivated with various Al³⁺ concentrations, the yeast growth was inhibited at a concentration of 200 mM. Pre-cultivation of these strains with 0–30 mM Al³⁺ did not promote the growth response caused by Al³⁺. Inductively-Coupled Plasma-Mass Spectrometry (ICP-MS) was used to assess the elimination of Al. The amount of Al remaining in culture media was decreased considerably after cultivation. Due to a capacity for resistance to significant Al concentrations as well as high Al elimination, these acid tolerant and Al resistant yeasts may have potential applications in the bio- and phyto-remediation of Al and acid-contaminated soils.     

Forms of Al in soil and soil solution in a long‐term fertilizer application experiment

Under the conditions of a long‐term fertilizer experiment, this study aimed to determine the contents of total and exchangeable aluminium in soil as well as the Al concentration in the soil solution. Additionally, Al speciation was evaluated with the use of the MINTEQA2 software. The results obtained indicated that under the conditions of long‐term application of different mineral fertilizers or farmyard manure, the soil reaction changed to a great extent (pH 3.58–6.78). At the same time, the content of total Al in soil fluctuated from 18.85 to 22.13 g/kg and that of exchangeable Al ranged from 1.42 to 102.66 mg/kg. The concentration of Al in the soil solution was highly differentiated (5.19–124.07 μmol/L) as well as that of free aluminium ions (Al³⁺) (0–16.9 μmol/L). In acidic soils, aluminium complexes with organic matter are the predominant forms of Al in the soil solution. In soils with neutral soil reaction, there were no free aluminium ions. Soil liming and addition of organic amendment were the treatments that restricted the presence of toxic aluminium forms in soil.