Modelling the solid–solution distributions of protons, aluminium, base cations and humic substances in acid soils

wham , an equilibrium chemical model for soils, waters and sediments, centred on a discrete-site/ electrostatic model of humic substances (HS), has been used to analysae batch titration data for organic and mineral horizons of acid soils. In most cases, tolerable fits were obtained by optimizing the soil contents of HS and aluminium, while keeping the model parameters (site densities, equilibrium constants, electrostatic terms) fixed. The optimized contents agreed reasonably with those estimated by chemical extraction. For some mineral soil samples, low in HS and high in aluminium, fitting of the titration data was improved by assuming the formation and dissolution of A1(OH)₃ and adjusting its solubility product. Solid-solution distributions of base cations (Na⁺, Mg²⁺, K⁺, Ca²⁺, NH⁺⁴) could be explained by non-specific counterion accumulation, with a small degree of selectivity. The WHAM sub-model for fulvic acid sorption accounted approximately for observed aqueous-phase concentrations of organic carbon and organically-complexed aluminium.     

Partitioning of organic carbon, aluminium and cadmium between solid and solution in soils: application of a mineral–humic particle additivity model

The partitioning of chemical elements between the solid and solution phases in soil is fundamental in understanding processes such as leaching and bioavailability. Here I present a model in which the partitioning of Cd, Al and carbon in both mineral and organic soils can be simulated in the pH range 2–8. A two‐phase additivity approach simulates ion adsorption by the soils using a hydrous ferric oxide and humic type surface. A model for the partitioning of soil humic matter has also been developed in which the NICA–Donnan model calculates humic surface charge. Other key processes represented include mineral solubilization and solution speciation. Methods for deriving model input parameters either from analytical data or by parameter optimization were used. Acid ammonium‐oxalate‐extractable Fe was used to estimate the amount of hydrous ferric oxide, and reactive humic substances were estimated by a scaled down version of the International Humic Substances Society method for the extraction of humic and fulvic acid. For initial calculation the 0.1 m HCl‐extractable Al was used to estimate reactive Al. Optimization of reactive Al improved the fit of both the total dissolved Al data and the adsorbed Cd. The model for the solid–solution partitioning of humic substances could simulate reasonably well the release of carbon in the pH range 4–8 for both the organic and mineral soils.     

Interpretation of humic acid coagulation and soluble soil organic matter using a calculated electrostatic potential

The coagulation of humic substances and its role in controlling the solubility of organic matter in soils are not well understood. We therefore studied the physico‐chemical behaviour of purified humic acid from forest soil coagulated with Na, Ca, Cu, Al at pH 4 and 6, and then modelled the behaviour with the Non‐Ideal Consistent Competitive Adsorption Donnan (NICA‐Donnan) model. We found that the coagulation of humic acid occurs when the Donnan potential is less negative than ?0.08 V. Based on this result, an empirical relation between the Donnan potential of humic acid and its concentration in solution was derived. In addition, the Donnan potential of the dissolved organic matter in the soil solution of six soil profiles from forests was calculated using the NICA‐Donnan model under the assumption that all the dissolved organic matter behaves as humic acid. The measured concentration of dissolved organic matter also decreases in a soil profile, as the calculated potential becomes less negative. The results are in many cases in semi‐quantitative agreement with the predicted concentration based on the humic acid coagulation experiment. Acid soils contain more dissolved organic matter, which may result from the presence of a fairly large fraction of more soluble organic molecules, such as fulvic acid.     

Dissolved organic carbon and decreasing pH mobilize cadmium and copper in soil

When limed farmland is converted to forestry cadmium (Cd), copper (Cu) and other heavy metals can become mobile because of acidification and increased concentration of dissolved humic substances. The influence of pH and dissolved organic C on amounts and rates of Cd and Cu release was investigated in a cultivated soil by extraction with ～ 1 mm hydrochloric acid at pH 3 with and without dissolved organic C in the batch mode with weekly replacement of the extraction solution. After 88 weeks, 35–50% of aqua regia‐extractable Cd was extracted; addition of 10 mm dissolved organic C had no effect on the amount dissolved, but it increased the initial rate of release because the organic matter buffered the suspension at a lower pH. The solubility and release rate of Cd decreased as the geochemically active fraction was depleted. This suggests that Cd occurs in the soil in a continuum of binding strengths ranging from readily available to strongly bound forms. The repeated extractions resulted in distribution coefficients (K_{d dis}) that have log‐linear relationships with pH. This allows prediction of Cd solubility during acidification of soil. Dissolved organic C enhanced the release of Cu from less than 8% (without) to more than 20% (with) of aqua regia‐extractable Cu. Total contents of Cd and Cu cannot be used as measures of the metals' availability during acidification of former limed farmland. Predictions of availability should be based on the solubility as a function of pH and the degree of Cd or Cu depletion from the geochemically active fraction in soil.     

Cation binding by acid-washed peat, interpreted with Humic Ion-Binding Model VI-FD

A sample of ombrotrophic peat from Moor House in northern England was extensively extracted with dilute nitric acid (pH 1) to free it of bound cations. Suspensions of the acid‐washed peat (5–30 g l^?1), prepared with different concentrations of background electrolyte (NaCl and KCl), were used to conduct batch acid–base titrations. A strong dependence of proton release on ionic strength (I) was observed, the apparent acid dissociation constant (pK_app) being found to decrease by approximately 1.0 for each tenfold increase in I. This behaviour could not be explained satisfactorily with Humic Ion‐Binding Model VI, a discrete‐site/electrostatic model of cation binding by humic substances, parameterized with data from laboratory studies on isolated samples. More success was obtained by abandoning the impermeable‐sphere electrostatic submodel used in Model VI, and instead assuming the peat to consist of aggregates with fixed internal volume, and with counterion accumulation described by the Donnan model, as proposed by Marinsky and colleagues. The fixed‐volume Donnan model (Model VI‐FD) could also approximately explain other reported results from acid–base titrations of peat, including the effects on the titrations of complexing cations (Al, Ca, Cu). Copper titrations of the Moor House sample were performed using an ion‐selective electrode, with peat suspensions in the acid pH range, at two ionic strengths, and in the presence of Al and Ca. The measured concentrations of Cu²⁺ were in the range 10^?13?10^?5 m . Model VI‐FD provided reasonable fits of the experimental data, after optimization of the intrinsic binding constant for Cu, the optimized value being close to the default value derived previously from data referring to isolated humic substances. The optimized constants for Al and Ca, derived from their competition effects, were also close to their default values. Additional experiments were performed in which the centrifugation‐depletion method was used to measure the binding of a cocktail of metals (Al, Ni, Cu, Zn, Cd, Eu, Pb) at a single pH. The model correctly predicted strong binding of Al, Cu, Eu and Pb, and weaker binding of Ni, Zn and Cd. For the strongly binding metals, the dissolved forms were calculated to be mainly due to complexes with dissolved humic matter, whereas the free ions (Ni²⁺, Zn²⁺, Cd²⁺) dominated for the weakly binding metals. Acid‐washed soil appears to provide a valuable intermediate between isolated humic substances and untreated soil for the investigation of cation binding by natural organic matter in the natural environment.     

Soil organic matter stabilization in acidic forest soils is preferential and soil type-specific

Minerals with large specific surface areas promote the stabilization of soil organic matter (SOM). We analysed three acidic soils (dystric, skeletic Leptic Cambisol; dystric, laxic Leptic Cambisol; skeletic Leptic Entic Podzol) under Norway spruce (Picea abies) forest with different mineral compositions to determine the effects of soil type on carbon (C) stabilization in soil. The relationship between the amount and chemical composition of soil organic matter (SOM), clay content, oxalate‐extractable Fe and Al (Fe_o; Al_o), and dithionite‐extractable Fe (Fe_d) before and after treatment with 10% hydrofluoric acid (HF) in topsoil and subsoil horizons was analysed. Radiocarbon age, ¹³C CPMAS NMR spectra, lignin phenol content and neutral sugar content in the soils before and after HF‐treatment were determined and compared for bulk soil samples and particle size separates. Changes in the chemical composition of SOM after HF‐treatment were small for the A‐horizons. In contrast, for B‐horizons, HF‐soluble (mineral‐associated) and HF‐resistant (non‐mineral‐associated) SOM showed systematic differences in functional C groups. The non‐mineral associated SOM in the B‐horizons was significantly depleted in microbially‐derived sugars, and the contribution of O/N‐alkyl C to total organic C was less after HF‐treatment. The radiocarbon age of the mineral‐associated SOM was younger than that of the HF‐resistant SOM in subsoil horizons with small amounts of oxalate‐extractable Al and Fe. However, in horizons with large amounts of oxalate‐extractable Al and Fe the HF‐soluble SOM was considerably older than the HF‐resistant SOM. In acid subsoils a specific fraction of the organic C pool (O/N‐alkyl C; microbially‐derived sugars) is preferentially stabilized by association with Fe and Al minerals. Stabilization of SOM with the mineral matrix in soils with large amounts of oxalate‐extractable Al_o and Fe_o results in a particularly stable and relatively old C pool, which is potentially stable for thousands of years.     

Acid properties of fulvic and humic acids isolated from two acid forest soils under different vegetation cover and soil depth

We studied the acid‐base properties of 16 fulvic acids and 16 humic acids isolated from the surface (3–15 cm) and subsurface (> 45 cm) horizons of two types of acid forest soils, derived respectively from amphibolite and granite rocks, under five different types of vegetation. The observed differences between the contents of humic substances in the two types of soils were related to the degree of Al‐saturation of the soil organic matter, as indicated by the molar ratio between pyrophosphate extractable Al and C. Humic fractions were characterized in terms of elemental composition, and CPMAS ¹³C NMR spectrometry. The contents of carboxylic and phenolic groups were estimated by potentiometric titrations conducted in 0.1 m KNO₃ in a nitrogen atmosphere. The fulvic acids contained more carboxylic groups but less phenolic groups than the humic acids: the ratio of phenolic to carboxylic groups in the humic acids was 0.48 ± 0.10 and in the fulvic acids 0.23 ± 0.05. The mean values of the protonation constants of each of the humic substance fractions can be used as generic parameters for describing the proton binding properties. The fulvic acids isolated from the subsurface horizon of the soil contained between 2.6 and 23% more carboxylic groups, and the humic acids between 8 and 43% more carboxylic groups than those isolated from the surface horizon of the same soil.     

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.     

Use of vermicompost extract as an aluminium inhibitor in aqueous solutions

Abstract

Vermicompost extract (VCE) demonstrated the ability to raise the measured pH level of an acid soil thus showing a potential to limit aluminium toxicity. The relatively high proportion of humic substances (60% of VCE solid matter) suggested the possibility of formation of stable chelates with aluminium ions. A rate‐based colorimetric method was utilised measuring at 585 nm the aluminium‐pyrocatechol violet complex (Al‐PCV₃) after 60 seconds ("toxic”; Al index) and 2 hours ("total”; Al). By artificially altering the pH levels of various VCE:Al solutions, in the absence of soil, the relative and combined effects of pH and chelation on Al level reduction were observed. Inferences were drawn to predict the efficacy of VCE applied to acid soils displaying Al phytotoxicity. These are to be tested in subsequent work. In solutions above pH 6, a 98% reduction of total Al was obtained due to pH effects, whereas at pH 4, a 90% reduction was obtained due to chelation. The trends were similar for “toxic”; Al indices.     

A comparison of extraction procedures for water‐extractable organic matter in soils

The characteristics of dissolved organic matter (DOM) in soils are often determined through laboratory experiments. Many different protocols can be used to extract organic matter from soil. In this study, we used five air‐dried soils to compare three extraction methods for water‐extractable organic matter (WEOM) as follows: (i) pressurised hot‐water‐extractable organic carbon (PH‐WEOC), a percolation at high pressure and temperature; (ii) water‐extractable organic carbon (WEOC), a 1‐hour end‐over shaking; and (iii) leaching‐extractable organic carbon (LEOC), a leaching of soil columns at ambient conditions. We quantified the extraction yield of organic carbon; the quality of WEOM was characterized by UV absorbance, potential biodegradability (48‐day incubation) and parallel factor analysis (PARAFAC) modelling of fluorescence excitation emission matrices (FEEMs). Biodegradation of dissolved organic carbon (DOC) was described by two pools of organic C. The proportions of labile and stable DOC pools differed only slightly between the WEOC and LEOC methods, while PH‐WEOC contains more stable DOC. The mineralization rate constants of both labile and stable DOC pools were similar for the three methods. The FEEMs were decomposed into three components: two humic‐like fluorophores and a tryptophan‐like fluorophore. The effect of extraction method was poorly discriminant and the most similar procedures were PH‐WEOC and LEOC while WEOC extracts were depleted in humic‐like fluorophores. This study demonstrates that WEOM quality is primarily determined by soil characteristics and that the extraction method has a smaller, but still significant, impact on WEOM quality. Furthermore, we observed considerable interaction between extraction procedure and soil type, showing that method‐induced differences in WEOM quality vary with soil characteristics.     

Controls on carbon accumulation and storage in the mineral subsoil beneath peat in Lakkasuo mire, central Finland

What processes control the accumulation and storage of carbon (C) in the mineral subsoil beneath peat? To find out we investigated four podzolic mineral subsoil profiles from forest and beneath peat in Lakkasuo mire in central boreal Finland. The amount of C in the mineral subsoil ranged from 3.9 to 8.1 kg m^?2 over a thickness of 70 cm and that in the organic horizons ranged from 1.8 to 144 kg m^?2. Rates of increase of subsoil C were initially large (14 g m^?2 year^?1) as the upland forest soil was paludified, but decreased to < 2 g m^?2 year^?1 from 150 to 3000 years. The subsoils retained extractable aluminium (Al) but lost iron (Fe) as the surrounding forest podzols were paludified beneath the peat. A stepwise, ordinary least‐squares regression indicated a strong relation (R² = 0.91) between organic C concentration of 26 podzolic subsoil samples and dithionite–citrate–bicarbonate‐extractable Fe (negative), ammonium oxalate‐extractable Al (positive) and null‐point concentration of dissolved organic C (DOC_np) (positive). We examined the ability of the subsoil samples to sorb dissolved organic C from a solution derived from peat. Null‐point concentration of dissolved C (DOC_np) ranged from 35 to 83 mg l^?1, and generally decreased from the upper to the lower parts of the profiles (average E, B and C horizon DOC_np concentrations of 64, 47 and 42 mg l^?1). The DOC_np was positively correlated with percentage of soil C and silt and clay content. The concentration of dissolved organic C in pore water in the peat ranged from 12 to 60 mg l^?1 (average 33 mg l^?1), suggesting that the sorptive capacity of the subsoil horizons for C had been exhausted. We suggest that the increase of C contents in the subsoil beneath mires is related to adsorption of dissolved organic C and slow mineralization under anaerobic conditions.     

Dissolved organic matter sorption by mineral constituents of subsoil clay fractions

The retention of dissolved organic matter in soils is mainly attributed to interactions with the clay fraction. Yet, it is unclear to which extent certain clay‐sized soil constituents contribute to the sorption of dissolved organic matter. In order to identify the mineral constituents controlling the sorption of dissolved organic matter, we carried out experiments on bulk samples and differently pretreated clay‐size separates (untreated, organic matter oxidation with H₂O₂, and organic matter oxidation with H₂O₂ + extraction of Al and Fe oxides) from subsoil horizons of four Inceptisols and one Alfisol. The untreated clay separates of the subsoils sorbed 85 to 95% of the dissolved organic matter the whole soil sorbed. The sorption of the clay fraction increased when indigenous organic matter was oxidized by H₂O₂. Subsequent extraction of Al and Fe oxides/hydroxides caused a sharp decrease of the sorption of dissolved organic matter. This indicated that these oxides/hydroxides in the clay fraction were the main sorbents of dissolved organic matter of the investigated soils. Moreover, the coverage of these sorbents with organic matter reduced the amount of binding sites available for further sorption. The non‐expandable layer silicates, which dominated the investigated clay fractions, exhibited a weak sorption of dissolved organic matter. Whole soils and untreated clay fractions favored the sorption of ”︁hydrophobic” dissolved organic matter. The removal of oxides/hydroxides reduced the sorption of the lignin‐derived ”︁hydrophobic” dissolved organic matter onto the remaining layer silicates stronger than that of ”︁hydrophilic” dissolved organic matter.     

Characterization of Al/Fe—humus complexes in dystrandepts through comparison with synthetic forms

The Al/Fe—humus complexes in A₁ horizons of Dystrandepts from several parts of Japan were compared with synthetic complexes prepared from hydroxy ions and from two kinds of humic substances and at several pH values. Samples represented 26 A₁ horizons of soils differing in age, including some that had been buried. The comparisons were based chiefly on extractions of the synthetic complexes and the soil samples with solutions of sodium hydroxide-tetraborate and sodium pyrophosphate.The Al—humus complexes in the Dystrandept samples appeared to be similar to those of synthetic complexes prepared at pH 4–5. Those have OH/Al molar ratios of 0.7–2.5 1. Distribution of the data for the soil samples suggested further that the proportions of polymeric hydroxy Al ions increased as soils became older and also if they were buried. The Fe—humus complexes in the soil samples seemed to be like the synthetic complexes prepared with Fe and humus at pH 4–5 for the most part.     

The dynamics of organic matter in rock fragments in soil investigated by 14C dating and measurements of 13C

Rock fragments in soil can contain significant amounts of organic carbon. We investigated the nature and dynamics of organic matter in rock fragments in the upper horizons of a forest soil derived from sandstone and compared them with the fine earth fraction (<2 mm). The organic C content and its distribution among humic, humin and non‐humic fractions, as well as the isotopic signatures (Δ¹⁴C and δ¹³C) of organic carbon and of CO₂ produced during incubation of samples, all show that altered rock fragments contain a dynamic component of the carbon cycle. Rock fragments, especially the highly altered ones, contributed 4.5% to the total organic C content in the soil. The bulk organic matter in both fine earth and highly altered rock fragments in the A1 horizon contained significant amounts of recent C (bomb ¹⁴C), indicating that most of this C is cycled quickly in both fractions. In the A horizons, the mean residence times of humic substances from highly altered rock fragments were shorter than those of the humic substances isolated in the fine earth. Values of Δ¹⁴C of the CO₂ produced during basal respiration confirmed the heterogeneity, complexity and dynamic nature of the organic matter of these rock fragments. The weak ¹⁴C signatures of humic substances from the slightly altered rock fragments confirmed the importance of weathering in establishing and improving the interactions between rock fragments and surrounding soil. The progressive enrichment in ¹³C from components with high‐¹⁴C (more recent) to low‐¹⁴C (older) indicated that biological activity occurred in both the fine and the coarse fractions. Hence the microflora utilizes energy sources contained in all the soil compartments, and rock fragments are chemically and biologically active in soil, where they form a continuum with the fine earth.     

Sorption of phosphorus by some surface soils from Quebec in relation to their properties

Abstract

Surface horizons from Podzolic and Gleysolic soils were collected in various parts of the province of Quebec, Canada, and equilibrated with various amounts of KH₂PO₄ in 0.01 M CaCl₂ for 48 hours. P sorption data conformed to the linear form of the Langmuir and Freundlich equations. P solubility isotherms showed evidence of hydroxyapatite formation in most samples studied, whereas equilibration solutions of only few samples were saturated with respect to either dicalcium phoshate dihydrate or octocalcium phosphate. These reaction products were associated to soil pH and levels of added phosphate. The average values of the Langmuir sorption maximum for these studied Gleysolic and Podzolic samples were 763 and 1096 μg/g respectively. These values were higher than those obtained by the segmented and modified Freundlich models.

Relationships between the soil characteristics and P sorption parameters were evaluated by regression analysis. Among all variables, oxalate‐extractable Fe plus Al content of the Podzolic samples and the ratio of oxalate—extractable Al to clay of the Gleysolic samples gave the best significant correlation coefficients. Furthermore, soil pH and various ratios such as pyrophosphate‐extractable Fe and Al, oxalate‐extractable Fe and organic matter to clay were found to be significantly correlated only with the P sorption parameters of the Gleysolic samples.     

Die Bedeutung von hohen Aluminiumgehalten für die Humusanreicherung in sauren Waldböden

The role of aluminium on humus accumulation in acid forest soils The impact of soil-borne aluminum on humus accumulation was investigated in a forest soil of the chestnut zone (Castanea sativa) in southern Switzerland (Ticino). Soil samples of two soils formed on bedrocks which differ mainly in their aluminum content were extracted with HNO₃, NH₄Ac.-EDTA, NH₄Cl, KCl, and NH₄F-HCl and analyzed for the most abundant elements. On gneiss which contains up to about 10% of total aluminum the common soil type in this area is a Cryptopodzol. This soil is similar to the nonallophanic Udands. It is rich in wellhumified organic matter and shows dark-colored A_h-, A(E)- and B_h-horizons. The soil samples of these horizons are extremely rich in nonexchangeable aluminum which is, however, extractable with NH₄Ac.-EDTA. It is assumed that this Al is intimately bound to the organic matter. The soil samples of these horizons contain large amounts of HNO₃-extractable phosphorus. Up to 90% of this P appears in the organic fraction. The content of NH₄F-HCl-extractable P is only 0.7 to 3.4 mg/kg. It is concluded that due to excessive Al in the organic matter the humus mineralization is inhibited compared to the Haplumbrepts of the region.     

Glomalin‐related soil protein in French temperate forest soils: interference in the Bradford assay caused by co‐extracted humic substances

Thermostable soil protein, known as glomalin, is an important component of soil carbon stocks. Thought to originate from endomycorrhizal fungi, Glomales, this operationally‐defined fraction of soil organic matter contains proteins of diverse origin as well as non‐protein material, including humic substances. Accumulation results from the balance between production/release and subsequent degradation. Quantification of the protein is subject to uncertainty because of the co‐extraction of other components that interfere with the Bradford assay. We studied 10 topsoils from French temperate forests, taken from the national forest monitoring network (Renecofor). Two fractions were extracted, easily extractable (EE) at neutral pH and total extractable (T) at pH 8. Protein was quantified with the colorimetric Bradford method, either by direct calibration using bovine serum albumin (BSA) or by extrapolation of the standard addition plot of BSA. Solubilized organic matter was characterized by using absorbance at 465 and 665 nm and by three‐dimensional fluorescence excitation‐emission spectroscopy. Neither soil properties nor forest cover influenced glomalin‐related soil protein (GRSP) content. Direct assay gave the GRSP_EE to be about 1 g kg^?1 soil, and GRSP_T in the range 3–10 g kg^?1, accounting for about 2% of soil organic carbon and about 15% of soil nitrogen. Standard addition plots indicated a two to sixfold under‐estimation of protein in total extracts, caused by negative interference with the Bradford assay. The GRSP_EE was correlated significantly with both estimates of GRSP_T. Under‐estimation of GRSP_T by direct assay was not related to the E4:E6 ratio but was correlated significantly with the intensity of absorbance at either 460 or 660 nm and with one of the fluorescence peaks. We conclude that GRSP_EE is not necessarily more recent than GRSP_T and that both fractions may be probes of protein content, but that absolute contents may be under‐estimated because of co‐extracted humic substances.     

IMOGOLITE AND PROTO-IMOGOLITE ALLOPHANE IN SPODIC HORIZONS: EVIDENCE FOR A MOBILE ALUMINIUM SILICATE COMPLEX IN PODZOL FORMATION

Examination by infrared spectroscopy and electron microscopy of the fine clays (<0.5 μm) dispersed at pH 3.5 from H₂O₂-treated soil indicates that imogolite and proto-imogolite allophanes are concentrated in podzolic B₂ and B₃ horizons, and make up at least 6 percent of one B₂ horizon soil, which contains virtually no layer silicate clays. It is argued here that imogolite-type components are the principal source of extractable aluminium and silicon in such horizons, that they may act as cementing agents in indurated horizons, and that proto-imogolite, a soluble aluminium-silicate complex, is the predominant mobile form in which aluminium is transported to B₂ and lower horizons of podzols. Comparison of the amounts of aluminium extracted by acetic acid with those extracted by EDTA indicates that extractable aluminium in Bhg, Bh, and organic-rich A₂ horizons is present principally in organic complexes. It is proposed that the aluminium fulvates concentrated in these horizons are formed in situ.     

Cations adsorbed to soil organic matter — A regulatory factor for the release of organic carbon and hydrogen ions from soils to waters

Surface waters in northern forest ecosystems receive a substantial amount of drainage water from superficial soil horizons enriched in organic matter (SOM). Chemical reactions in the interface between the soil solution andf organic colloides will therefore affect the surface water chemistry. The mobilization of total organic carbon (TOC) and pH was studied as a function of amounts of organically adsorbed Na, Ca and Al in two O and one A horizon, which differed in the likelihood of contributing to the chemistry in runoff, in a forested watershed in northern Sweden. The samples were hydrogen ion saturated, washed and titrated with NaOH, Ca(OH)₂ and Al(OH)₃ in a constant ionic medium of 0.01 M NaCl in order to give rise to a population of manipulated samples differing in the composition of adsorbed cations. The highly humified SOM accumulated in the O_h and A_h horizons of a Gleysol close to the draining stream was stabilized by flocculating Al (95% of adsorbed metal cations), which resulted in a low release of TOC. These horizons showed a high potential of organic carbon solubility when Al was changed for di- or monovalent cations. Calculations suggested that the release of TOC would increase more than ten times if Al was exchanged for Ca upon liming to pH 6.0. The pH values of all horizons were shown to be determined mainly by the composition of adsorbed mono-,di- and trivalent cations.