Mechanisms controlling the mobility of dissolved organic matter, aluminium and iron in podzol B horizons

The processes governing the (im)mobilization of Al, Fe and dissolved organic matter (DOM) in podzols are still subject to debate. In this study we investigated the mechanisms of (im)mobilization of Al, Fe and organic matter in the upper and lower B horizons of two podzols from the Netherlands that are in different stages of development. We equilibrated batches of soil material from each horizon with DOM solutions obtained from the Oh horizon of the corresponding soil profiles. We determined the amount of (im)mobilized Al, Fe and DOM after addition of Al and Fe at pH 4.0 and 4.5 and initial dissolved organic carbon (DOC) concentrations of 10 mg C litre^?1 or 30 mg C litre^?1, respectively. At the combination of pH and DOC concentrations most realistic for the field situation, organic matter was retained in all horizons, the most being retained in the lower B horizon of the well‐developed soil and the least in the upper B horizon of the younger profile. Organic matter solubility seemed to be controlled mainly by precipitation as organo‐metal complexes and/or by adsorption on freshly precipitated solid Al‐ and Fe‐phases. In the lower B horizons, at pH 4.5, solubility of Al and Fe appeared to be controlled mainly by the equilibrium with secondary solid Al‐ and Fe‐phases. In the upper B horizons, the solubility of Al was controlled by adsorption processes, while Fe still precipitated as inorganic complexes as well as organic complexes in spite of the prevailing more acidic pH. Combined with a previous study of eluvial horizons from the same profiles, the results confirm the important role of organic matter in the transport of Al and Fe to create illuvial B horizons initially and subsequently deepening and differentiating them into Bh and Bs horizons.     

Contribution of different proton sources to pedogenetic soil acidification in forested ecosystems in Japan

The contribution of different proton sources to pedogenetic soil acidification was evaluated for three Japanese forest soils, i.e. ando soil, podzolic soil and brown forest soil in relation to the respective soil forming processes. Soil acidification rate and net proton generation were quantified based on the theory of proton budget for the respective soil horizon compartments (mainly the O, A and B horizons) by measuring fluxes of solutes entering and leaving the soil horizon compartment and vegetation uptake. Protons were produced by the dissociation of organic acids and nitrification in the O horizon and then consumed by adsorption and decomposition of organic acids and nitrate uptake by vegetation in deeper soil horizons at all plots. Excess uptake of cation over anion by vegetation was highest among proton sources in the whole soil compartment at all plots. Pedogenetic soil acidification was considered to include cation leaching from surface soil horizons due to proton generation by the dissociation of organic acids and nitrification and subsequent cation excess accumulation in wood in the growth stage of forests. In ando soil, andosolization resulted from the low contribution of net proton generation by the dissociation of organic acids as well as a lower soil acidification rate and complete acid neutralization. Dissolved organic carbon (DOC) fluxes in ando soil were lower than those in podzolic soil and brown forest soil due to high adsorption capacity of amorphous materials. In podzolic soil, podzolization resulted from intensive acidification in the O horizon, which derived from net proton generation by the dissociation of organic acids and nitrification as well as cation excess uptake by vegetation due to concentrated fine root biomass in the O horizon, and subsequent high proton efflux to subsoil. The high fluxes of DOC and Al leached from surface soil horizons were considered to contribute to eluviation of Al from surface soil and illuviation in subsoil in podzolic soil. In brown forest soil, brunification resulted from a lower DOC flux from the O horizon due to high decomposition and adsorption by oxides, where podzolization was weakened by high acid neutralization. Thus, the three representative processes involved in the pedogenesis of Japanese forest soils were well characterized by quantification of the respective proton-generating and consuming processes in each soil horizon.     

Fluoro‐mobilization of metals in a Slovak forest soil affected by the emissions of an aluminum smelter

Depositions originating from a central Slovak Al smelter may increase metal solubility in adjacent soils because they contain F (mainly HF). The reason for fluoro‐mobilization of metals may be the formation of soluble fluoro‐metal complexes or the mobilization of organic matter and subsequent formation of organo‐metal complexes. The objectives of our work were (1) to assess the extent of metal mobilization by fluoride in a Slovak Lithic Eutrochrept affected by the emissions of an Al smelter and (2) to model the dissolved metal species with the help of a chemical equilibrium model (MINEQL+). The O (Moder), A, and B horizons were equilibrated with solutions at F concentrations of 0, 0.9, 2.7, and 9.0 mmol l^—1. In the extracts, the concentrations of Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, Zn, dissolved organic carbon (DOC), free and complexed F, and the pH and electrical conductivity (EC) were determined. The heavy metal concentrations in the O horizon (Cd: 0.99, Cr: 18.0, Cu: 44, Ni: 26, Pb: 110, and Zn: 84 mg kg^—1) were 2.5 to 9 times larger than those in the A and B horizons. The concentrations of H₂O‐soluble F decreased from the O (261 mg kg^—1) to the A (103 mg kg^—1) and B horizon (92 mg kg^—1). In batch experiments increasing addition of F increased the equilibrium concentrations of Al, Cr, Cu, Fe, Ni, Pb, and DOC in all samples, of Cd in the A, and of K in the B horizon. At the same time the concentrations of complexed F and pH increased whereas EC decreased. Chemical equilibrium modelling indicated that the mobilizing effect of F resulted from the formation of fluoro‐Al complexes and organo‐complexes of all other metals.     

Micro-scale variation of solid-phase properties and soil solution chemistry in a forest podzol and its relation to soil horizons

In order to evaluate micro-scale heterogeneities 55 micro suction cups were placed in an array at 15 mm intervals in a profile face of a cambic podzol. The chemistry of soil solution (mineral anions, pH, UV absorption as a measure for DOC) was compared with solid-phase properties from soil samples (2 cm³ volume), which had surrounded the suction cups. Sequential extraction techniques (water, NF₄Cl, hydroxylamin-hydrochloride, citrate-bicarbonate, oxalate, dithionite-citrate-bicarbonate) and base titrations were applied to characterize the solid phase. Although the average soil solution concentrations between horizons often differed significantly, the spatial distributions of pH and SO₄^2? did not correlate with soil horizon borders. Even if concentration isolines and soil horizon borders were parallel, marked concentration gradients could be observed within individual soil horizons. The less intense the interaction between solute ion and soil matrix, the greater was the variation in solution concentration within a soil horizon. For the soil solid phase only a weak correlation of slow buffer reactions to soil horizons was found. The distribution of extractable Fe and Al was typical for a podzol profile, however, with very steep gradients within single soil horizons. Except for pH, which was related mainly to citrate-bicarbonate extractable aluminium, no solid-phase characteristic showed a clear correlation with soil solution chemistry.     

Modelling the Fate of Chromated Copper Arsenate in a sandy Soil

Afforestation of former agricultural land changes soil characteristics such as pH and organic matter content, which may affect heavy metal solubility in the soil. In this study the effects of different tree species on heavy metal solubility were investigated at four 34 years old adjacent stands of beech (Fagus sylvatica L.), grand fir (Abies grandis Lindl.), Norway spruce (Picea abies (L.) Karst.) and oak (Quercus robur L.) planted on former agricultural land at four different sites in Denmark. The sites differ in soil characteristics and represent two texture classes (loamy sand and sandy loam). Soil pH and soil organic matter content was measured in the 16 stands and soil solution was isolated by centrifugation from three depths at four different occasions. Dissolved organic carbon (DOC), pH in the soil solution and the soil solution concentrations (availability) of Cd, Cu, Ni, Pb and Zn were determined. Analysis of variance showed that the tree species affects soil pH and organic matter content in the topsoil, but not in the lower horizons. Norway spruce and grand fir acidify more than beech and oak, and the highest amount of accumulated soil organic matter is in the topsoil under Norway spruce. The effects of tree species on soil solution pH and DOC resemble the effect on soil pH and organic matter content. Grand fir enhances the solubility of Cd and Zn in the topsoil with the lower solubility found under beech and oak and Norway spruce enhances the solubility of Cu, Ni and Pb in the top horizons. The lowest solubility of Ni and Pb is found under beech and oak, whereas the lowest Cu concentrations in the soil solution are found under grand fir. After 34 years of afforestation no effects of tree species on the concentrations of heavy metals in the soil solution from the C-horizons were found. The tree species effect on the concentration of Cd, Cu and Ni in the soil solution depends on the soil characteristics with the higher concentrations found in sandy loam soils, whereas no effect of site on the solution concentration was found for Pb and Zn. It was not possible to find a clear correlation between the soil solution concentrations of heavy metals, pH and DOC concentration.     

Aluminum compounds in soil solutions and their migration in podzolic soils on two-layered deposits

The fractional composition of aluminum compounds was studied in soil solutions obtained using vacuum lysimeters from loamy podzolic soils on two-layered deposits. The concentration of aluminum was estimated in brooks and a river draining the area with a predominance of these soils. In soil solutions, the concentration of aluminum was experimentally determined in the following compounds: (1) organic and inorganic monomers, (2) stable complexes with HAs and FAs together with polymers, and (3) the most stable complexes with HAs and FAs together with fine-crystalline and colloidal compounds. The total Al concentration in soil solutions from forest litter was 0.111–0.175 mmol/l and decreased with depth to 0.05 mmol/l and lower in solutions from the IIBD horizons. More than 90% of the Al in the solutions was bound into complexes with organic ligands. Some amount of Al in solution could occur in aluminosilicate sols. The translocation of Al complexes from the litter through the AE horizon to the podzolic horizon was accompanied by an increase in the ratio between the Al concentration in fraction 2 and the C concentration in the solution. The concentrations of Al_tot in the surface waters varied in the range from 0.015 to 0.030 mmol/l. Most of the Al came to the surface waters from the litter and AE horizons and partially from the podzolic horizon due to the lateral runoff along the waterproof IIBD horizon. Approximate calculations showed that the recent annual removal of Al from the AE and E horizons with the lateral runoff was 7 to 560 mg (3–21 mmol) from 1 m².     

Soil Aluminum Distribution in the Near-Stream Zone at the Bear Brook Watershed in Maine

Near-stream and upslope soil chemical properties were analyzed to infer linkages between soil and surface water chemistry atthe Bear Brook Watershed in Maine [BBWM]. Organic and mineral soil samples were collected along six 20 m transects perpendicular to the stream and one 200 m transect parallel tothe stream. O horizon soils immediately adjacent to the streamhad a significantly higher pH (4.20) and lower soil organic matter percentage (54%) than upslope O horizons (3.84 and 76%,respectively). Additionally, near-stream O horizon soils hadsignificantly higher concentrations of water-soluble Al (2.7 ×),exchangeable Al (2.3 ×), and organically-bound Al (3.9 ×) andsignificantly lower concentrations of exchangeable Ca (0.4 ×) than O horizons upslope. These results suggest that Al can accumulate in non-hydric near-stream zone soils at this site. Mobilization of labile Al from near-stream zone soils duringhydrologic events could play a key role in explaining controls on Al in stream water at BBWM.     

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.     

Major mechanisms in formation of spodic horizons

Current explanations of the formation of spodic horizons do not accomodate all features of the horizons in their natural state. In this paper, a more complete explanation of major mechanisms is proposed, using two principles of colloid chemistry: (1) organic substances may form hydrophylic colloids with surface charges, and (2) the hydrophylic character and negative surface charges determine the dispersibility of the colloids. The hydrophylic character is due to the presence of hydrophylic radicals as parts of the organic compounds in soils. The surface charges are the result of dissociation of -COOH and possibly phenol-OH radicals.The neutralization of the surface charge can in principle occur: (1) through electrostatic or physical adsorption and (2) through chemisorption. The first case is typical for monovalent alkali cations. The adsorbed cations are distributed in a double layer, which favours dispersion. Chemisorption occurs mostly with polyvalent cations. This process corresponds in reality to the formation of organo-metallic compounds. It results in a relatively complete disappearance of the double layer and in the formation of large immobile “polymerized” organo-metallic compounds. Because these compounds contain much hydrophylic water, they form a gel. Transition into the solid state is accompanied by the loss of most of the hydration water. The dehydration may be induced by a decrease in thickness of the double layer. At a certain stage of the dehydration process, Van der Waals bonds and protonic bridges can form and bring about a certain degree of hydrophoby.In soils, mobile organic substances are formed during breakdown of plant remains. If at the top of the mineral soil enough polyvalent cations, especially Al and Fe, are available, the mobile organic substances formed are immobilized immediately and no migration occurs. In case insufficient amounts of Al and/or Fe are available to completely immobilize the mobile compounds, these cations are complexed by the mobile compounds and transported downward. Immobilization may occur at some depth through supplementary fixation of cations, through dessication or on arrival at a level with different ionic concentration.In nature, spodic horizons range from loose, with many roots, to very cemented with few roots. These differences can be related to changes in microstructure. Loose spodic horizons have a predominance of polymorphic pellets and aggregates, whereas organans or monomorphic coatings prevail in cemented horizons. The former horizons have many features suggesting major biological influences during their formation, viz., high numbers of roots, thorough mixing of the organic units with clay and silt, the presence of pedotubules and relatively young mean residence times. The latter horizons have features consistent with organo-metallic compounds immobilized in a gel-state, viz., the coatings are strongly cracked, indicating the transition of a gel into a solid; they contain much Al or Al plus Fe but very little or no Si, and the mean residence time is considerably higher than in loose horizons.The two processes seem to operate simultaneously during the formation of spodic horizons and their relative intensities determine the composition of each spodic horizon at any moment in its evolution. As long as the biological activity predominates, the horizon remains loose; if the accumulation of mobile organo-metallic compounds starts to prevail, the horizon is gradually cemented and fossilized.     

Al,Fe, and Si compounds in Tamm and Mehra-Jackson extracts from mucky-peaty-podzolic gley soil: Contents,reserves, and profile and particle-size distributions

Equal or comparable contents of Fe and Al extractable by Tamm and Mehra-Jackson solutions have been revealed in all the horizons of a loamy mucky-peaty-podzolic gley soil on binary deposits. The content of Si extractable by the Mehra-Jackson solution has exceeded that of oxalate-soluble Si by an order of magnitude. The distributions of Al in the Tamm solutions from the entire soil and its fractions of 1–5 and >5 μm are of accumulative type with a maximum in the mucky H horizon and a gradual decrease of the content with depth in relation with the analogous distribution of Al-organic complexes. The maximum content of oxalate-soluble Al in the clay fraction has been found in the eluvial ELg horizon, which can be due to the partial dissolution of Al hydroxide interlayers in soil chlorites. The distribution of Fe in the entire soil has two maximums, in the H horizon due to the accumulation of Fe-organic complexes and in the concretion-rich ELnn,g horizon due to the accumulation of Fe hydroxides. Depletion of oxalate-soluble Fe in the eluvial ELg horizon has been observed in all the fractions, which can be related to its mobilization and removal under strongly acidic conditions and the development of reductive processes, as well as the enrichment of the concretion-rich horizon with these compounds because of an increase in pH and the development of conditions favorable for water stagnation and Fe segregation.     

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.     

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.     

Aluminum compounds in calcium chloride extracts from podzolic soil and their possible sources

Aluminum concentrations in organoaluminum complexes, mineral polymers, Al(H₂O) ₆ ³⁺ , Al(OH)(H₂O) ₅ ²⁺ , Al(OH)₂(H₂O) ₄ ⁺ , AlH₃SiO ₄ ²⁺ , and Al(OH)₃(H₂O) ₃ ⁰ extracted with 0.001 M CaCl₂ from the main genetic horizons of a podzolic soil on two-layered deposits were determined experimentally and calculated from thermodynamic equations. It was found that aluminum bound in organic complexes was predominant in extracts from the AE horizon, and mineral polymer aluminum compounds prevailed in extracts from the E and IIBD horizons. In the AE horizon, organoaluminum compounds were a major source of aluminum, which passed into solution predominantly by exchange reactions. In the E horizon, aluminum hydroxide interlayers in soil chlorites were the main source of aluminum, which passed into solution by dissolution reactions. In extracts from the IIBD horizon, aluminum was solubilized by the dissolution of aluminosilicates inherited from the parent rock.     

Effect of natural organic soil solutes on weathering rates of soil minerals

The rate at which minerals in the soil weather is affected by pH and concentration of organic solutes (DOC). The rates of release of Al, Ca, Fe, K, Mg, Na, P and Si from a mineral soil sample to solutions of natural organic solutes and HCI (control) were determined at pH 3 and 4 for up to 17 weeks. Soil solutions were collected by centrifuging materials of O horizons from various soil types under four tree species (spruce, birch, oak, beech) and passed through a cation-exchange resin to yield H⁺-saturated organic solutes. The acceleration of the elements' release by the organic solutes was shown directly by the relative ligand effect (RLE), that is, the release rate in the organic solute solution divided by the release rate in the HCI solution (control) at the same pH. The RLE was greater at pH 4 than at pH 3, and it decreased for the elements in the order Fe > Ca > Mg > Al ≈ Si > K ≈ Na. This indicates that natural organic solutes are more important weathering agents at higher than lower pH and for weathering of mafic minerals rich in Ca, Fe and Mg than of felsic minerals such as K- and Na-feldspars. For all elements and at both pHs, RLE was strongly correlated with the concentration of DOC, which was also closely correlated with titratable acidity of the organic solutes. The important effect of soil type and tree species in producing weathering-promoting organic solutes therefore seems to be expressed through the concentration and not the composition of the organic soil solutes.     

Elemental patterns in roots and foliage of mature spruce across a gradient of soil aluminium

Tissue concentrations of Al in red and Norway spruce trees were compared across 5 sites in North America and Europe as part of an investigation of Al biogeochemistry in forested ecosystems (ALBIOS). Fine roots and foliage were sampled and analyzed for Al, Ca, Mg, and P, and the chemistry of soil and soil solutions was characterized at each plot by horizon. Sites exhibited a wide range in soil Al saturation and in concentrations of Al and sulfate in lysimeter solutions. Aluminium concentrations in roots were two orders of magnitude higher than those in foliage. Fine roots (<1.0 mm) from B horizons had the highest Al concentrations and appeared to be the best phytoindicators of plant-available Al. Aluminium concentrations in fine roots from B horizons were highly correlated with soil solution monomeric Al, and with Al in 0.01 M SrC₂. soil extracts. Stronger soil Al extractants were generally poor predictors of concentrations of Al in plant tissue. Sites with higher levels of plant-available Al supported spruce trees with correspondingly lower foliar levels of Ca and Mg. As such, these field sites provided circumstantial evidence that Al may be interfering with Ca and Mg uptake and transport. No evidence was found of Al interference with P uptake or transport at these sites.     

Mobilization of dissolved organic matter, aluminium and iron in podzol eluvial horizons as affected by formation of metal-organic complexes and interactions with solid soil material

Interactions with dissolved organic matter (DOM) are generally believed to play a crucial role in the translocation of Al and Fe in acid sandy soils. Binding of Al and Fe to DOM affects their mobility in soils by altering sorption equilibria of charged sites on solid soil material, inducing precipitation of organo‐metallic complexes and preventing the formation of inorganic Al and Fe phases. The relative importance of the different processes, especially with respect to the translocation of Al, Fe and organic matter in podzols, remains unresolved. We determined the effect of the presence of solid soil material from the eluvial (AhE and AE, respectively) horizons of a Fimic Anthrosol and a Haplic Podzol on the metal‐to‐organic carbon (M/C) ratio in solution and the formation of dissolved organic Al and Fe complexes. Furthermore, we assessed the resulting influence on the mobilization of Al, Fe and DOM. Even under considerable metal loading, the M/C ratios and ‘free’ metal fractions in solution remained low and relatively constant, due to an apparent buffering by the solid phase and the formation of organo‐metal complexes in solution. The M/C ratios remained so low that significant precipitation of organo‐metal complexes due to saturation with metals was not found. The apparent buffering by the solid phase can be explained by a strong release of organic matter from solid soil material and adsorption of non‐complexed Al and Fe on solid organic matter upon metal addition. Adsorption of organo‐metal complexes most likely played only a minor role. The observations confirm the expected mobilization of Al, Fe and DOM in eluvial horizons and seem to indicate that even under fluctuating input of Al, Fe and DOM the soil solution will have a constant composition with respect to M/C ratios and percentage of Al and Fe present in dissolved organo‐metal complexes.     

Crop use and profile distribution of phosphorus in soils that developed on mafic rocks in southern Portugal

The phytoavailability of soil phosphorus (P) depends on the different forms in which it occurs and how these forms change after the application of P fertiliser to the soil. Forms of P in the A, B and C horizons of eleven pedons that developed on mafic rocks were characterised by a fractionation method before and after fertilisation with single superphosphate, and a micropot experiment was conducted to assess the short-term use of P fertiliser by rye (Secale cereale L.). The main sources of P to the crop were (i) phosphate adsorbed on mineral surfaces and pedogenic Fe, Al or Ca phosphates in the A horizon and (ii) Ca-phosphates in B and C horizons. In the C horizons, poor in Fe/Al phases and clay, the precipitated Ca-P showed low solubility, resulting in a reduction in shoot biomass. The apparent P recovery by rye was similar in the A (36%) and B (29%) but decreased in the C (15%) horizons. The partial factor productivity (g g^?1) decreased from the A (58) to B (11) and C (5) horizons. P phytoavailability decreased with increasing profile depth because the transformation of P fertiliser to poorly soluble Ca-P forms increased with depth.     

Aluminum and iron(III) species in the soil solution including organic complexes with citrate and humic substances

The solubility of Al and Fe in soil is of relevance for their toxicity and availability, respectively, to plant roots. Humic substances as the main part of stable soil organic matter and citrate which is often excreted by P deficient plants are strong complexants of Al and Fe(III). Therefore, equations were developed to calculate the Al and Fe(III) species distribution in the soil solution in the presence of humic substances and citrate as organic ligands. Calculations in the pH range 4.0–7.0 showed that at higher pH humic-Al complexes were the most important species whereas AlOH-citrate^? dominated between pH 4.0 and 5.4. Free monomeric Al and AlSO₄⁺ were of minor relevance. Iron(III) species calculations showed that humic-Fe complexes were the main species in the pH range 4.0–7.0. But if mugineic acid, a Fe complexing phytosiderophore released into the rhizosphere by graminaceous plant species, was present in the soil solution (10^?6 M), Fe-mugineic acid complexes accounted for most of the Fe in solution. Fe-citrate^? was relevant at lower pH but contributed little to Fe(III) species at pH > 6.0. The results demonstrate the strong importance of the considered organic ligands for Fe and Al in the soil solution.     

Forms and pedogenetic distribution of extractable iron and aluminum in selected soils of Nigeria

The content of various forms of Fe and Al in six well-drained soil profiles sampled from different parts of Nigeria was determined by selective extraction methods. Dithionite-Fe (total free Fe oxides) content increases with the increase of depth. The oxalate-extractable Fe (amorphous Fe oxides) constitutes less than 10% of the total free Fe oxides throughout the profiles. The active Fe ratio decreases with the increase of profile depth, suggesting that larger proportions of Fe oxides are present as crystalline forms in the lower horizons of these well-drained profiles. Little or no relationships were found in the case of Al.The constant clay/dithionite-Fe ratio within the four profiles from the wetter southern part of Nigeria indicates the co-migration of clay and Fe oxides from the A horizon into the B horizon (lessivage). However, this relationship was not observed in the two soil profiles sampled from the drier northern part of the country.The need for expansion or alteration of the present U.S.D.A. system of soil classification is emphasized.     

The seasonal variation in soil water acid neutralizing capacity in peaty podzols in Mid-Wales

Between 1985 and 1990, bulk precipitation and soil solution from the organic (Oh) and mineral (Bs) horizons of a well developed podzol were regularly sampled at a moorland catchment in Mid-Wales. Samples were analysed for pH, major cations, major anions, and dissolved organic carbon (DOC). Acid neutralizing capacity (ANC) was estimated by the charge balance method. Average monthly ANC of soil solutions from the Oh horizon varied seasonally, with a maximum in July and a minimum in February. In contrast, H⁺ concentrations varied little. Solute deposition, dominated by sodium and chloride, also varied seasonally with a winter maximum, which is reflected in the soil solution chemical composition. In the Oh horizon during winter, the increase in base cation (Na) concentrations led to release of H⁺ through ion exchange. ANC declined in the absence of any buffering mechanism. In summer, the depletion of exchangeable acidity that occurred in winter, was replenished by H⁺ produced by the dissociation of organic acids. During this period, organic anions contribute to an increase in ANC, while H⁺ concentrations remained similar to those in winter. These processes probably influenced the acidity and ANC of Bs horizon soil solutions but to a lesser extent than in the Oh horizon. Other mechanisms such as weathering and ion exchange involving H⁺ and Al may buffer solution acidity in the mineral soil.