Apparent cation-exchange equilibria in podzolic forest soils

The Gaines–Thomas selectivity coefficient, K, was used to express the relation between the cations in solution and the cations in exchange sites in podzolic forest soils. Soil solution was obtained by centrifuging a fresh bulked soil sample. Exchangeable cations HX, AlX, CaX, MgX and KX and effective cation-exchange capacity, CEC_e, were determined with 0.1 m BaCl₂. Apparent values of K indicated a preference of Ca²⁺ over Mg²⁺ and over Al³⁺ in O, A and B horizons (log K_Al–Ca < 0 and log K_Mg–Ca < 0), whereas log K_K–Ca and log K_H–Ca exceeded zero. The horizons were similar with respect to log K_H–Ca, and the differences in log K_Mg–Ca were small. Log K_K–Ca and log K_Al–Ca increased in the horizons in the order O < A < B. Log K_Al–Ca was not significantly correlated with the fraction AlX/CEC_e. Log K_Mg–Ca was positively correlated with the fractions HX/CEC_e and AlX/CEC_e, and negatively correlated with log (CaX/MgX). The selectivity coefficient of binary cation exchange seemed to be applicable to in situ soil solutions. However, the fraction of each cation on exchange sites should be based on the CEC_e rather than on the sum of the two cations. The latter, also, seemed to be acceptable in cases of exchangeable cations with a large relative content in soil, e.g. in Al³⁺–Ca²⁺ exchange in A and B horizons, and in H⁺–Ca²⁺ exchange in O and A horizons.     

THE EQUILIBRIA OF K:Al EXCHANGE IN CLAY MINERALS AND ACID SOILS1

Conventional K: Al exchange isotherms for montmorillonite showed that Al³⁺ was strongly preferred to K⁺ in o-oin solutions. The exchange coefficient, K', calculated using the isotopically exchangeable K, was greater than unity and did not vary with the Al-saturation or with the initial pH of the AlCl₃ solutions. Isotherms for vermiculite, illite, and soils in o·oin solutions also showed Al³⁺-preference but unlike those for montmorillonite were not asymptotic to q_Al/q_o= 1, q_Al being the amount of adsorbed Al and q_o the total adsorbed (Al + K), indicating that some of the isotopically exchangeable K could not easily be exchanged by Al³⁺ ions; this difficultly exchangeable K (DEK) was estimated for each exchanger. K' values for vermiculite, illite, and soils were less than unity and did not vary with Al-saturation or initial pH if the isotopically exchangeable K was corrected for DEK. This showed that K⁺ was adsorbed more strongly than Al³⁺. Strengths of K⁺ adsorption referred to Al³⁺ as the counter-cation were in order: soils > vermiculite, illite > montmorillonite.     

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.     

Solubility control of KCl extractable aluminum in soils with variable charge

Abstract

Solubility and kinetic data indicated that concentrations of aluminum (Al) extracted with 1 M KCl are determined by the solubility of a precipitated A1(OH)₃ phase in soils dominated by variable charge minerals. Kinetic studies examining the release of Al on non‐treated and KCl treated residues indicated the precipitation of an acid‐labile Al phase during the extraction procedure. The log ion activity products estimated for the KCl extracts ranged between 8.1–8.6 for the reaction Al(OH)₃ + 3H⁺ < = > Al³⁺+ 3H₂O, which was similar to the solubility product of several Al(OH)₃phases. The mechanism proposed for Al precipitation indicated that Al released by exchange with added K⁺ hydrolyzed and released H⁺ that was readily adsorbed on surfaces of variable charge minerals. The increased ionic strength of the extracting solution further increased the amount of H⁺adsorbed to the variable charge surface and reduced the H⁺ concentration in the aqueous phase. Consumption of H⁺ induced further hydrolysis of Al, resulting in supersaturation of the extracting solution and formation of polynuclear hydroxy Al species. It was concluded that the 1 M KCl extraction does not quantitatively extract salt exchangeable Al from variable‐charge soils.     

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.     

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.     

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.     

Correlations between different acidity forms in amorphous loamy soils of the tundra and taiga zones

Pair correlation coefficients (r) between the acidity parameters for the main genetic horizons of soddy-podzolic soils (SPSs), typical podzolic soils (TPSs), gley-podzolic soils (GPSs), and tundra surfacegley soils (TSGSs) have been calculated on the basis of a previously developed database. A significant direct linear correlation has been revealed between the pH_water and pH_KCl values in the organic and eluvial horizons of each soil, but the degree of correlation decreased when going from the less acidic SPSs to the more acidic soils of other taxons. This could be related to the fact that, under strongly acid conditions, extra Al³⁺ was dissolved in the KCl solutions from complex compounds in the organic horizons and from Al hydroxide interlayers in the soil chlorites. No significant linear correlation has been found between the exchangeable acidity (H _exch) and the activity of the [H]⁺ ions in the KCl extract (a(H⁺)_KCl) calculated per unit of mass in the organic horizons of the SPSs, but it has been revealed in the organic horizons of the other soils because of the presence of the strongest organic acids in their KCl extracts. The high r values between the H _exch and a(H⁺)_KCl in all the soils of the taiga zones have been related to the common source and composition of the acidic components. The correlation between the exchangeable and total (H _tot) acidities in the organic horizons of the podzolic soils has been characterized by high r values because of the common source of the acidity: H⁺ and probably Al³⁺ ions located on the functional groups of organic acids. High r values between the H _exch and a(H⁺)_KCl have been observed in the mineral horizons of all the soils, because the Al³⁺ hydroxo complexes occurring on the surface and in the interlayer spaces of the clay minerals were sources of both acidity forms.     

Acid and mineral components determining the exchangeable acidity in mineral horizons of taiga soils of the Komi Republic

Analysis of acid components in soil-KCl suspension filtrates from the mineral horizons was performed on the basis of analytical data reported between 1958 and 2003, including the data on more than 60 soil profiles (about 300 horizons) from the taiga zone of the Komi Republic. It was shown that the acid ions Al³⁺, H⁺ (exchangeable hydrogen), and Fe³⁺ and the basic ion H₃SiO ₄ ^? are the main components determining the pH of filtrates. Groups of horizons with the predominance of specific ions were separated.     

Influence of Different Forms of Iron and Aluminum on the Nature of Soil Acidity of Some Inceptisols,Alfisols, and Ultisols

Abstract

Fifteen acid soils of Mizoram representing Ultisols and Inceptisols, and Madhya Pradesh, representing Alfisols, were studied to characterize the nature of acidity in relation to different forms of iron (Fe) and aluminum (Al). The mean contents of Fe and Al were extracted by various extracting reagents and were found to be in descending order as followed: dithionite>oxalate>pyrophosphate>ammonium acetate>KCl. The electrostatically bonded EB‐H⁺ and EB‐Al³⁺ acidity comprised 28.3 and 71.7% of exchangeable acidity whereas EB‐H⁺, EB‐Al³⁺, exchangeable, and pH‐dependent acidities comprised 9.8, 30.7, 40.5, and 59.5% of total potential acidity. All forms, of acidity showed significant correlation with pH_k and organic carbon. Among the different forms, Fe and Al caused most of the variations in different forms of soil acidity but the effect of different forms of Al are more active and directly participate in the formation of EB‐H⁺, EB‐Al³⁺, and exchangeable acidity.     

The effect of five years acid treatment on leaching,soil chemistry and weathering of a humo-ferric podzol

This paper describes the effect of treating a nutrient-poor forest soil in monolith lysimeters with H₂SO ₄, pH 3.0, for 4.75 yr. The lysimeters were instrumented with porous cup probes to distinguish processes occurring in each soil horizon. In the A horizon base cation exchange and sulphate absorption were the principal proton- consuming processes whereas lower down the profile Al³⁺ dissolution from hydrous oxides dominated. Acid treatment thus reduced the amount of amorphous Al in the lower horizons, but exchangeable Al was unaffected. Sulphate absorbtion was positively correlated with the distribution of Al hydrous oxides. High rates of nitrification reduced the differences between acid and control monoliths, but acid treatment significantly reduced soil pH down to 75 cm and reduced the levels of exchangeable base cations in the litter and A horizons. Acid treatment increased the leaching rates of base cations and Al. Consideration of the total base cation content shows that acid treatment increased the rate of weathering by 0.7–1.4 k eq ha^?1 yr^?1. The results should be useful in modelling more realistic rates of acid input to similar soils.     

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.     

Chemical effects of pH 3 sulphuric acid on a soil profile

Cores of podzolic soil (monolith lysimeters) were treated for 4.8 yr with 1500 mm yr^?1 of either 0.5 mM H₂SO₄ at pH 3, equivalent to 24 g S m^?2 yr^?1 (acid treated) or distilled water (controls). The acid treatment was about 37 times greater than the average annual input of H₃O⁺ from rain at the site from which the monoliths were taken. Acid treatment acidified the litter (from pH(CaCl₂)3.4 to pH(CaCl₂)2.6) and the mineral soil to a depth of 80 cm (mean pH(CaCl₂) decrease of 0.2 unit). In the litter and upper A horizon, ion-exchange reactions provided the main neutralizing mechanism, resulting in a decrease in the reserves of extractable (in 2.5 % acetic acid) Ca, Mg, and Mn of about 70 to 80 %. Dissolution of solid phase Al from hydrous oxides provided most neutralization below this depth. Al3⁺ was the principal soluble Al species throughout the profile. In the litter and upper A horizon, some of the mobilized Al³⁺ was retained on cation exchange sites resulting in an increase in exchangeable Al. Deeper in the profile, where the exchange sites were effectively saturated with Al³⁺, no increase in exchangeable Al occurred, and Al³⁺ was, therefore, available for leaching. Some reversible adsorption of SO₄ ^2?, associated with hydrous Al oxides, occurred in the Bs and C horizons. The results are discussed in relation to possible effects of acid deposition over regions of Europe and N. America.     

Forms and buffering potential of aluminum in tropical and subtropical acid soils cultivated with Pinus taeda L

Purpose

Several interactions between Al and the solid phase of soil influence Al buffering in soil solution. This work evaluated soils cultivated with Pinus taeda L. to determine Al forms in organic and mineral horizons using various extraction methods and to relate acidity with clay mineralogy.

Materials and methods

Organic and mineral horizons of 10 soil profiles (up to 2.1 m deep) in southern Brazil were sampled. Organic horizons were separated into fresh, aged, and fermented/humified litter. The following Al extraction methods were utilized: 0.5 mol L^?1 pH 2.8 CuCl₂–Al complexed in organic matter; 1.0 mol L^?1 KCl–exchangeable Al; water–Al soluble in soil solution; HF concentrated?+?HNO₃ concentrated?+?H₂O₂ 30% (v/v)–total Al. Six sequential extractions were carried out to isolate different forms of amorphous minerals that can buffer Al on soil solution: 0.05 and 0.1 mol L^?1 sodium pyrophosphate; 0.1 and 0.2 mol L^?1 ammonium oxalate; 0.25 and 0.5 mol L^?1 NaOH. Samples of clay were also analyzed by XRD.

Results and discussion

There was a clear effect of litter age on increasing total Al concentration. In the aged litter and fermented and/or humified litter, levels of total Al were 1.4 to 3.8 and 1.5 to 7.8 times greater than in fresh litter, respectively. The CuCl₂ method had higher Al extraction capacity than the KCl method for litter. The lowest Al–pyrophosphate values were observed in the Oxisol, which also had a predominance of gibbsite and the lowest levels of Al–KCl and Al–CuCl₂. There was an inverse relationship between degree of soil weathering and soluble and exchangeable Al in soils. Available Al increased with higher Si proportion in minerals of the clay fraction (2:1?>?1:1?>?0:1).

Conclusions

The worst scenario was soils with the combination of high soluble and exchangeable Al levels and high concentrations of amorphous forms of Al minerals. The best predictors of Al accumulation in the youngest litter horizon were extractions of amorphous minerals with pyrophosphate and NaOH. These extractors are normally used to predict the level of Al buffering in soils. Organic matter had less influence on Al dynamics in soils.

     

Simulated effects of acid deposition on podzolic soils: Consequences of process and parameter aggregation

Solution cation concentrations and base cation leaching were simulated for a homogenous soil block and a soil showing five horizons of a podzolic forest soil. The dynamic model ACIDIC simulated water flow, nutrient uptake for tree growth, and cation exchange between H⁺, Al³⁺, Ca²⁺, Mg²⁺ and K⁺ in forest soil. In the multi-layer simulations exchangeable base cation concentrations changed most in the O horizon. The subsoil had a decisive effect on the pH of the runoff and base cation leaching from the soil. The one-layer model underestimated Ca and Mg leaching and overestimated H⁺ and Al concentrations in the runoff. In the eluvial and the top of illuvial horizon the solution Al / (Ca + Mg) ratio exceeded that in one-layer structure more than 10-fold. Cases with the horizon-specific cation exchange coefficient values and mean coefficient values for all layers showed only minor differences in Al / (Ca + Mg) ratio. The vertical variation in the soil chemical properties should be accounted for even if some details of processes and parameters were unavailable.     

Influence of surface‐applied poultry manure on topsoil and subsoil acidity and salinity: A leaching column study

It has been suggested that surface applications of animal manure can ameliorate both top and subsoil acidity. For that reason, the effects of surface incorporation (0–5 cm) of a high rate of poultry manure to an acid soil on pH and exchangeable and soluble Al in the top‐ and subsoil were investigated in a leaching column study. During the experimental period of 108 d, columns received a total of 875 mm with leaching events occurring after 9, 37, 58, and 86 d. Incorporation of poultry manure into the surface 5 cm resulted in a large rise in pH measured in both 1M KCl and in soil solution. This liming effect was attributed primarily to the substantial CaCO₃ content of poultry manure. In the 15–45 cm layer, pH_KCl was not significantly different between poultry manure and control treatments but surprisingly, soil‐solution pH was substantially less in the poultry‐manure treatments. Exchangeable Al was significantly less in poultry manure than in control in all soil layers although the effect was most marked in the 0–5 cm layer. However, although concentrations and activities of monomeric Al (Al_mono), and the proportion of total Al present as Al_mono, in soil solution were lower under poultry manure than in control in the 0–5 cm layer, the reverse was, in fact, the case in lower soil horizons. 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. Indeed, electrical conductivity and concentrations of Ca²⁺, Mg²⁺_, K⁺, and Na⁺ in soil solution were substantially higher in the poultry‐manure than in the control treatments at all soil depths. Poultry‐manure applications also resulted in substantial increases in the concentrations of Ca²⁺_, Mg²⁺_, K⁺, Na⁺, Al_mono, NH , and NO in leachates, particularly at the fourth leaching. It was concluded that although surface application of poultry manure can raise soil pH in the topsoil, increases in soluble‐salt concentrations in soil solution can greatly modify this effect in the subsoil.     

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).     

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.     

Soil base saturation affects root growth of European beech seedlings§

To assess the potential effects of Al toxicity on the roots of young European beech (Fagus sylvatica L.), seeds were sown in soil monoliths taken from the Ah and B horizons of forest soils with very low base saturation (BS) and placed in the greenhouse. The Ah horizons offered a larger supply of exchangeable cation nutrients than the B horizons. After 8 weeks of growth under optimal moisture conditions, the seedlings were further grown for 14 d under drought conditions. Root‐growth dynamics were observed in rhizoboxes containing soils from the Ah and B horizons. The concentrations of Al³⁺, base cations, and nitrate in the soil solution and element concentrations in the root tissue were compared with above‐ and belowground growth parameters and root physiological parameters. There was no strong evidence that seedling roots suffered from high soil‐solution Al³⁺ concentrations. Within the tested range of BS (1.2%–6.5%) our results indicated that root physiological parameters such as O₂ consumption decreased and callose concentration increased in soils with a BS < 3%. In contrast to the B horizons, seedlings in the Ah horizons had higher relative shoot‐growth rates, specific root lengths, and lengths and branching increments, but a lower root‐to‐shoot ratio and root‐branching frequency. In conclusion, these differences in growth patterns were most likely due to differences in nutrient availability and to the drought application and not attributable to differences in Al³⁺ concentrations in the soil solution.     

Field application of industrial by-products as Al toxicity amendments: chemical and mineralogical implications

Lime, gypsum and various gypsum‐like by‐products have long been applied to soil surfaces as ameliorants of soil acidity and aluminium and manganese toxicity. We examined changes in chemical and mineralogical properties at two different depths in two acid soils one year after the application of gypsum, phosphogypsum + dolomitic residue, red gypsum + dolomitic residue, sugar foam, and sugar foam + mined gypsum. All treatments were found to increase the proportion of Ca²⁺ and decrease those of Al³⁺ and Mn²⁺ in the exchange complex of the surface and subsurface horizons, thus reducing its effective Al and Mn saturation. However, the mined gypsum treatment resulted in losses of Mg²⁺ from the Ap horizon of the soils, and the sugar foam treatment was not so effective with the AB horizons as the other treatments. The combined application of both gypsum‐like by‐products and the dolomitic residue proved the most effective choice with a view to reducing the effective Al and Mn saturation of the exchange complex in the Ap and AB horizons. In addition, both treatments reduced Mg²⁺ losses at both depths. Finally, all treatments resulted in the formation and retention on mineral and organic surfaces of a large fraction of the Al³⁺ released by exchange with Ca²⁺ as Al polymers. This is quite consistent with the observed changes in the CuCl₂‐, oxalate‐ and DTPA‐extractable Al contents as well as by SEM and EDS analyses. Based on these results, the use of the appropriate mixtures of these by‐products is an effective alternative to that of mined gypsum and lime to alleviate soil acidity and reduce toxic concentrations of Al³⁺ and Mn²⁺ in agricultural acid soils.