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.     

Microbial community structure and characteristics of the organic matter in soils under Pinus sylvestris, Picea abies and Betula pendula at two forest sites

 Microbial biomass C (C_mic), C mineralization rate, phospholipid fatty acid (PLFA) profiles and community level physiological profiles (CLPPs) using Biolog were determined from the humus and mineral soil layers in adjacent stands of Scots pine (Pinus sylvestris L.), Norway spruce [Picea abies (L.) Karst.] and silver birch (Betula pendula Roth) at two forest sites of different fertility. In addition, the Fourier-transformed infrared (FTIR) spectra were run on the samples for characterization of the organic matter. C_mic and C mineralization rate tended to be lowest under spruce and highest under birch, at the fertile site in all soil layers and at the less fertile site in the humus layer. There were also differences in microbial community structure in soils under different tree species. In the humus layer the PLFAs separated all tree species and in the mineral soil spruce was distinct from pine and birch. CLPPs did not distinguish microbial communities from the different tree species. The FTIR spectra did not separate the tree species, but clearly separated the two sites. Received: 3 December 1999     

Microbial biomass and activity in soil and litter underPinus sylvestris, Picea abies andBetula pendula at originally similar field afforestation sites

Microbial biomass C and N, and activities related to C and N cycles, were compared in needle and leaf litter, and in the uppermost 10 cm of soil under the litter layer in Scots pine (Pinus sylvestris L.), Norway spruce (Picea abies L.) and silver birch (Betula pendula L.) stands, planted on originally similar field afforestation sites 23–24 years ago. The ground vegetation was differentiated under different tree species, consisting of grasses and herbs under birch and pine, and mosses or no vegetation with a thick layer of needles under spruce. The C:N ratio of the soils was 13–21 and the soil pH_{CaCl 2} 3.8–5.2. Both showed little variation under different tree species. Microbial biomass C and N, C mineralization, net ammonification, reduction) did not differ significantly in soil under different tree species either. Birch leaf litter had a higher pH_{CaCl 2} (5.9) than spruce and pine needle litter (pH 5.0 and 4.8, respectively). The C:N ratio of spruce needles was 30, and was considerably higher in pine needles (69) and birch leaves (54). Birch leaves tended to have the highest microbial biomass C and C mineralization. Spruce needles appeared to have the highest microbial biomass N and net formation of mineral N, whereas formation of mineral N in pine needles and birch leaves was negligible. Microbial biomass C and N were of the same order of magnitude in the soil and litter samples but C mineralization was tenfold higher in the litter samples.     

Characteristics of dissolved organic matter and phenolic compounds in forest soils under silver birch (Betula pendula), Norway spruce (Picea abies) and Scots pine (Pinus sylvestris)

The aim was to characterize dissolved organic matter in soils under different tree species. Molecular size distribution and chemical composition of dissolved organic carbon and nitrogen were determined in water extracts from humus layers and mineral soils taken from silver birch ( Betula pendula Roth.), Norway spruce ( Picea abies (L.) Karst.) and Scots pine ( Pinus sylvestris L.) stands. Concentrations of tannins and 15 phenolic acids in the humus layers were measured. Per unit of organic matter, the concentrations of dissolved organic C and N were larger in birch and spruce humus layers than in the pine humus layer. In the underlying mineral soil, the concentrations of dissolved organic C were similar at all sites, but the concentration of dissolved organic N was greater in spruce and pine soils than in birch soil. In all soils, the 10–100 kDa fraction was the most abundant molecular size group and hydrophobic acids the most abundant chemical group of dissolved organic C. In all humus layers, hydrophobic acids and hydrophilic bases were the major components of dissolved organic N. There were only minor differences in the concentrations of total tannins in the humus layers under different tree species. Small-molecule tannins (about < 0.5 kDa) were most abundant in the birch humus, and large-molecule tannins in the pine humus. Coniferous humus contained more ferulic and p -coumaric acids than did the birch humus. The concentrations of 3,4 and 3,5-dihydroxybenzoic acid, vanillic acid and 4-hydroxybenzoic acid were similar in all soils.     

Effects of Natural Soil Acidification on Biodiversity in Boreal Forest Ecosystems

Variations in soil acidity and in biodiversity were analysed in the National Natural Park "Russian North", European Russia. Improving soil quality from podzol, podzolic soil, derno-podzolic soil, brown earth to pararendzina leads to increase in diversity and changes in floristical composition, followed by changing of pine and spruce forest to mixed and birch forests. In PCA ordination species diversity, richness and evenness of trees, shrubs and vascular plants are closely connected with each other, and are represented by the first principal component. They are strongly correlated to the thickness of Al horizon, pH_H20 and pH_CaC12 in organic, surface and subsurface mineral horizons. Only bryophyte species richness and diversity are directly related to the thickness and weight of organic horizon, soil exchangeable acidity, and inversely related to the thickness of Al horizon and pH. Thus, the ordination of the major species diversity variables is highly related to soil pH, suggesting that pH is the best soil related predictor of species diversity parameters. Our study shows that plants notably respond to soil acidification in boreal forest ecosystems.     

Microbial biomass and activity in soil and litter underPinus sylvestris, Picea abies andBetula pendula at originally similar field afforestation sites

Microbial biomass C and N, and activities related to C and N cycles, were compared in needle and leaf litter, and in the uppermost 10 cm of soil under the litter layer in Scots pine (Pinus sylvestris L.), Norway spruce (Picea abies L.) and silver birch (Betula pendula L.) stands, planted on originally similar field afforestation sites 23–24 years ago. The ground vegetation was differentiated under different tree species, consisting of grasses and herbs under birch and pine, and mosses or no vegetation with a thick layer of needles under spruce. The C:N ratio of the soils was 13–21 and the soil pH_{CaCl 2} 3.8–5.2. Both showed little variation under different tree species. Microbial biomass C and N, C mineralization, net ammonification, reduction) did not differ significantly in soil under different tree species either. Birch leaf litter had a higher pH_{CaCl 2} (5.9) than spruce and pine needle litter (pH 5.0 and 4.8, respectively). The C:N ratio of spruce needles was 30, and was considerably higher in pine needles (69) and birch leaves (54). Birch leaves tended to have the highest microbial biomass C and C mineralization. Spruce needles appeared to have the highest microbial biomass N and net formation of mineral N, whereas formation of mineral N in pine needles and birch leaves was negligible. Microbial biomass C and N were of the same order of magnitude in the soil and litter samples but C mineralization was tenfold higher in the litter samples.     

Short-term uptake of <Superscript>15</Superscript>NH<Subscript>4</Subscript><Superscript>+</Superscript> into soil microbes and seedlings of pine,spruce and birch in potted soils

Short-term competition between soil microbes and seedlings of Scots pine (Pinus sylvestris L.), Norway spruce (Picea abies (L.) Karst.) and silver birch (Betula pendula Roth) for N was assessed in a pot study using (¹⁵NH₄)₂SO₄ as a tracer. Seedlings were grown in organic and mineral soil, collected from a podsol soil; 3.18 mg (¹⁵NH₄)₂SO₄ per pot were injected into the soil, corresponding to 4 µg ¹⁵N g^-1 d.m. (dry matter) mineral soil and 17 µg ¹⁵N g^-1 d.m. organic soil. The amounts of N and ¹⁵N in the seedlings and in microbial biomass derived from fumigation-extraction were measured 48 h after addition of ¹⁵N. In the mineral soil, 19–30% of the added ¹⁵N was found in the plants and 14–20% in the microbial biomass. There were no statistically significant differences between the tree species. In the organic soil, 74% of the added ¹⁵N was recovered in the microbial biomass in birch soil, compared to 26% and 17% in pine and spruce soils, respectively. Correspondingly, about 70% of the ¹⁵N was recovered in pine and spruce seedlings, and only 23% in birch seedlings. In conclusion, plants generally competed more successfully for added ¹⁵NH₄ ⁺ than soil microbes did. An exception was birch growing in organic soil, where the greater amount of available C from birch root exudates perhaps enabled micro-organisms to utilise more N.     

Properties of dissolved organic matter derived from silver birch and Norway spruce stands: Degradability combined with chemical characteristics

Dissolved organic matter (DOM) derived from the humus layer under silver birch (Betula pendula Roth), Norway spruce (Picea abies (L.) Karst.), and mixed stands, and from senescent birch leaves and from spruce needles of the four oldest year-growth were characterized microbiologically and chemically. Samples were collected in the autumn and the solutions were obtained by centrifugation-drainage technique. The degradability of DOM, the availability of DOM to bacteria and fungi, concentrations of phenolic compounds and carbohydrates, and the distribution of carbon and nitrogen into fractions according to the chemical nature and the molecular size were studied. DOM derived from leaves and needles was clearly more labile than DOM derived from the humus layer indicating the importance of studying the DOM originating from fresh litter when assessing the turnover of DOM.DOM derived from spruce needles appeared to differ chemically greatly from all other samples. It had very high concentrations of carbohydrates, probably due to the sampling time, and phenolic compounds. The chemical composition of DOM derived from humus layer did not reflect the composition of DOM derived from needles and leaves. DOM derived from birch leaves degraded more than DOM derived from spruce needles and DOM derived from humus layer collected at the birch sites degraded more than DOM derived from humus layer collected at the spruce sites. The degradability of different compound groups of DOC and DON was studied in a short-term incubation (20 d) of DOM solutions by characterizing the solutions initially and after the incubation. Almost all compound groups appeared to degrade but weak hydrophobic acids, bases, hydrophilic neutrals, the smallest molecular size compounds, carbohydrates, and phenolic compounds degraded the most.     

Comparison of tree species effects on microbial C and N transformations and dissolved organic matter properties in the organic layer of boreal forests

The aim of this study was to determine whether tree species consistently affects soil microbial activities related to C and N cycling and to compare these activities with the characteristics of soil dissolved organic matter (DOM). Samples were taken from the mor-type organic layer (Of+Oh) underlain by podzols of six 20–72-year-old tree-species experiments on different site types in different parts of Finland. Sampling plots were dominated by silver birch (Betula pendula Roth), Norway spruce (Picea abies (L.) Karst) or Scots pine (Pinus sylvestris L., only on four sites). Amounts of C and N in the microbial biomass and rates of C mineralization (CO₂ production) and net N mineralization were determined, and water extracts were analysed for concentrations of DOC and DON and characterized according to molecular size by ultrafiltration and according to chemical composition using a resin fractionation technique. In all older stands, birch, compared to spruce or pine, increased soil pH, NH₄-concentration and amounts of C and N in microbial biomass and decreased the C-to-N ratio and ratio of dissolved organic N (DON)-to-mineral N. Birch had similar effects also in part of the younger stands. Birch also increased the rates of both C and net N mineralization compared to spruce or pine but only on two sites. In all soils, net nitrification was low. The distribution of DOC into different fractions based on chemical composition and molecular size was rather similar in all soils. The most abundant chemical fraction was hydrophobic acids, and the most abundant molecular size fraction was 10–100 kDa. The C-to-N ratio varied but was lowest in hydrophilic bases and in the smallest molecular size class. Mineralization of C was highly and positively correlated with concentration of DOC (Pearson's correlation coefficient r = 0.9, P < 0.01). The results indicated close interactions between microbial processes and dissolved organic matter.     

Significance of DOM in the translocation of cations and acidity in acid forest soils

We estimated the contribution of dissolved organic matter (DOM) to cation leaching and the translocation of acidity in three acid forest soils. The analysis was based on monitored (2 years) concentrations of dissolved organic carbon (DOC) in the field, measured total acidities of DOM, and measured as well as predicted weighted mean dissociation constants of the organic acids. Although the forest floor solutions were strongly acidic (pH 3.47–4.10), a considerable proportion of the organic acids was dissociated and organic anions represented 22–40% of the total anions in the mineral soil input. The flux of DOM-associated exchangeable protons from the forest floor to the mineral soil ranged from 0.35 (Wülfersreuth) to 3.72 (Hohe Matzen) kmol ha^?1 yr^?1. In the subsoil, this organic acidity may be neutralized by microbial decomposition of the organic acids, but a part of the hydrogen ions may dissociate and contribute to acidification of the soil solution and to weathering processes. Due to the pronounced retention of DOM in the mineral subsoil horizons, the contribution of DOM to the output of cations and acidity from the soil is much lower than in the surface horizons but still significant.?     

Zur Dynamik gelöster organischer Substanzen (DOM) in Fichtenökosystemen - Ergebnisse analytischer DOM-Fraktionierung

Dissolved organic matter (DOM) dynamics in spruce forested sites - examinations by analytical DOM fractionation Dissolved organic matter from two spruce forested sites in the Fichtelgebirge (Germany) was divided into different chemical and functional fractions, and the budgets of the fractions obtained were calculated. For both sites hydrophobic acids (HoS), hydrophilic acids (HiS), hydrophobic neutrals (HoN), hydrophilic neutrals (HiN), and hydrophilic bases (HiB) are discriminated concerning their dynamics in the compartments. Most of the HiN and HoN are mobilized by leaching from the forest canopy. Both neutral fractions are netto retained in the forest floor as well as in the mineral soil. In contrast, HoS and HiS are mainly released in the organic layers with a total input of organic acids from the forest floor into the mineral soil of ca 100 kg C (HoS) ha^?1 a^?1, and 50 kg C (HiS) ha^?1 a^?1, respectively. HoS are selectively better retained in the mineral horizons, leading to a mineral soil output of 2.4 – 4.4 kg C (HoS) ha^?1 a^?1, and 2.7 – 6.5 kg C (HiS) ha^?1 a^?1, respectively. It is concluded that the different mobility of the DOM fractions has implications for the mobilization and transport of organic pollutants and heavy metals.     

Soil solution chemistry and element budgets of three Scots pine ecosystems along a deposition gradient in north-eastern Germany

Since 1993 we are studying three Scots pine ecosystems along a deposition gradient in north-eastern Germany (formerly GDR). Dramatic reductions of pollutant emissions are reported for the period since 1989/90. S-deposition is high at the sites Roesa and Taura (25 kg S ha^?1yr^?1) compared to Neuglobsow. Inputs of basic cations, especially Ca, by alkaline dust immissions decrease in the order Roesa > Taura > Neuglobsow. The soil solution data show high concentrations of Ca and SO₄ at Roesa decreasing drastically along the deposition gradient. The elevated pH values reflect the impact of alkaline dust deposition particularly in the organic surface layer at Roesa. The site Taura received less base cation deposition and is marked by the lowest pH values throughout the soil profile combined with increased Al concentrations in the solution of the mineral soil. Thus, the composition of the soil solutions clearly reflects the different deposition regimes of the past. The element budgets show that large amounts of base cations, sulfur, and, at Taura, also aluminum are actually released from the soils that were previously stored.     

Characterization of dissolved organic matter in decomposing Norway spruce and silver birch litter

Dissolved organic matter (DOM) plays an important role in transport, storage and cycling of carbon (C) and nitrogen (N) in forest soils where litter is one of the main sources. The aim was to study the amount and characteristics of DOM leached from freshly fallen litters of silver birch (Betula pendula Roth.), Norway spruce (Picea abies (L.) Karst.) and their mixture during decomposition. DOM was collected after irrigation on eight occasions during 252 days incubation in the laboratory at about 18°C, including one freeze‐thaw cycle. During the incubation about 33–35% of C from birch and spruce litter and 40% of C from their mixture was lost. The total cumulative flux of dissolved organic carbon (DOC) from the mixture of litters was approximately 40% larger than that from single litters. The flux of DOC, DON, phenolic compounds and proteins followed a two‐stage pattern during decomposition. In the first stage the initially large fluxes decreased gradually. In the second stage, after freezing and thawing, the fluxes tended to increase again. Mixing birch and spruce litters and a freeze‐thaw cycle seems to increase the decomposition of litter and result in the increased flux of DOC, DON and phenolic compounds. The flux of hemicelluloses and the degradability of DOM were large at the first leaching occasion and decreased during the incubation. Birch had a 40% larger total flux of easily degradable DOM than spruce, supporting the previous consistent signs of greater microbial biomass and activities related to C and N cycling in soil under birch than under spruce. It is known that recalcitrant DOM might be stabilized whereas labile DOM may promote microbial activity and nutrient cycling. We conclude that the storage and cycling of C and N is affected by both tree species and degradation stage of litter in forest soils.     

Organic matter characteristics and C and N transformations in the humus layer under two tree species, Betula pendula and Picea abies

The aim of this study was to compare the effects of silver birch (Betula pendula Roth) and Norway spruce (Picea abies (L.) Karst.) on soil C and N transformations and on the characteristics of organic matter. Soil samples were taken from the humus layer of a replicated 35-year-old birch-spruce field experiment growing on Vaccinium myrtillus site type in middle-eastern Finland. The soil was a podzol and humus type mor. Soil pH was higher under birch (4.7) than under spruce (4.1). The C-to-N ratio was lower under birch (17) than under spruce (23). Per unit organic matter, microbial biomass C and N, net N mineralization and net nitrification were all higher in birch soil than in spruce soil. The rate of C mineralization (CO₂ production) was, however, the same regardless of tree species. Water-extracts were analyzed for the concentrations of dissolved organic C (DOC) and N (DON) and characterized according to molecular size distribution by ultrafiltration and according to chemical composition using a resin fractionation technique. The concentration of DON, in particular, was higher in birch soil than in spruce soil. The distribution of DOC and DON into different fractions based on molecular size or chemical composition was rather similar in both soils. The concentration of total phenolics, expressed as tannic acid equivalents, was higher in the humus layer under birch than in the humus layer under spruce, because the birch humus layer contained significantly more low-molecular weight (about <0.5 kD) phenolics than the spruce humus layer did. The concentration of proanthocyanidins (condensed tannins) was higher in spruce soil than in birch soil. The concentrations of the five most abundant phenolic acids showed that ferulic and p-coumaric acids were more abundant in spruce soil. Birch soil tended to contain slightly more nonvolatile sesquiterpenes than the spruce soil. The concentration of diterpenes was similar in both soils; but birch soil contained significantly more triterpenes, mainly sterols, than spruce soil did.     

黑土、潮土和红壤可溶性有机质的光谱特征及结构差异

为探究不同类型土壤可溶性有机质(DOM)含量和结构的差异性,选取黑土、潮土和红壤3种土壤的表层土壤(0～20 cm)为研究对象,提取其中的DOM,应用紫外–可见光谱、荧光光谱等技术,分析土壤中DOM的数量和光谱特征.结果显示:3种不同类型土壤中可溶性有机碳(DOC)含量及其与土壤有机碳(SOC)的比值(SOC/DOC)...     

Base Cation Supply in Spruce and Beech Ecosystems of the Strengbach Catchment (Vosges Mountains, N-E France)

In spruce and beech stands, mineral budgets for a rotation period were calculated from measured element fluxes. The release of base cations by mineral weathering was calculated with the steady state soil chemistry model PROFILE. The calcium release rate by weathering of the mineral fine earth was extremely low. For the period of one rotation, mineral weathering cannot provide enough Ca to compensate timber harvesting and leaching. Forest sustainability depends strongly on the amounts of Ca gained from deposition and lost by biomass removal. Magnesium was supplied by atmospheric deposition and mineral weathering. Calculated weathering rates were close to present soil losses. However, as the model assumes that all dissolution reactions are congruent, the computed release rate of Mg from illite might be too high. Main inputs of K to the soil solutions were primarily attributed to canopy leaching and litterfall in upper horizons and to mineral weathering in deeper horizons. The cation budget of the beech stand was much more equilibrated than that of the spruce stand. Given possible changes in silviculture and deposition chemistry, the sustainability of the present stands is rather improbable with respect to their mineral supply.     

Acid deposition in the German solling area: Effects on soil solution chemistry and Al mobilization

The Al chemistry of soil solutions was evaluated in two forest ecosystems in the North-German Solling area which is heavily impacted by acidic deposition. The principal H⁺ buffering process in these soils is the release of Al ions. Within the stand of Norway spruce, Al concentrations increase with soil depth up to 370 umol/L. Ca/Al ratios of the soil solution decrease with depth and suggest high risk of Al toxicity to tree roots and potential antagonistic effects for ion uptake. The Al concentrations of the soil solution in the upper horizons do not appear to be in equilibrium with mineral phases of Gibbsite, Alunite and Jurbanite as suggested by the depth gradients and temporal patterns in ion activity products. Depletion of extractable soil Al in the upper horizons is occuring. The release of Al to the soil solution under these conditions seems to be restricted by kinetic constraints.     

Properties of dissolved organic matter related to soil organic matter quality and nitrogen additions in Norway spruce forest floors

The quality of dissolved organic matter (DOM) is highly variable and little information is available on the relation of DOM quality to the structure and composition of its parent soil organic matter (SOM). The effect of increasing N inputs to forest soils on the structure and composition of both SOM and DOM also remains largely unclear. Here we studied the release of DOM, its specific UV absorption and two humification indices (HIX) derived from fluorescence spectra from Oa material of 15 North- and Central-European Norway spruce (Picea abies (L.) Karst.) stands. The Oa material was incubated aerobically at 15 °C and water holding capacity over a period of 10 months and extracted monthly with an artificial throughfall solution. Soil respiration was determined weekly. The influence of mineral N inputs on composition of DOM and on respiration rates was investigated on periodically NH₄NO₃-treated Oa samples of eight selected sites. Release of dissolved organic carbon (DOC) from untreated Oa material samples ranged from 0.0 to 58.6 μg C day⁻¹ g C⁻¹ and increased with increasing C-to-N ratio. One HIX and UV absorption of DOM were negatively correlated to the degree of oxidation of lignin-derived compounds and positively to the C-to-N ratio and – HIX only – to the aromatic C content of SOM. Mineral N addition had no distinct effect on respiration rates. In six of eight samples the N-treatment caused an increase in specific UV absorption or one HIX of DOM. However, these effects were not statistically significant. Addition of mineral N did not affect the rates of DOM release. Our results show that properties of SOM largely determine the amount and quality of DOM in forest floors. Changes of DOM quality due to mineral N additions are likely, but we cannot confirm significant changes of DOM release.     

Mobilization and immobilization of dissolved organic matter in forest soils

Field and laboratory studies combined with destructive and nondestructive analytical methods were used to characterize dissolved organic matter (DOM) in acid forest soils. DOM is produced in significant amounts in the forest canopy and in the forest floor. A major part of the organic solutes are lignocellulose-degradation products being strongly microbially altered in the course of ligninolysis. The release of lignin-derived moieties into the soil solution is controlled by their degree of biooxidation. Microorganisms contribute also directly to the organic solutes through the release of microbial metabolites. DOM released from the forest floor passes the upper mineral soil almost conservatively, whereas in the subsoil most DOM is removed from solution. Immobilization of DOM is mainly due to sorption on Fe and Al oxides. The highly oxidized lignin-derived moieties are preferentially removed from the soil solution whereas the saccharides are relatively enriched. We conclude that DOM in the forest soil output to the hydrosphere is a result of (1) the release of microbially degraded lignocellulose compounds and of microbial metabolites into the forest floor solution and (2) selective sorptive removal of the lignin-derived constituents in the subsoil.     

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

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