土壤有机矿质复合体研究 Ⅶ．土壤结合态腐殖质的形成特点及其结合特征

本文系统剖析了熊毅－傅积平改进区分的土壤结合态腐殖质的形成特点，胡，富组成及其结合特征。结果表明：（１）用０．１ｍｏｌ／ＬＮａＯＨ及０．１ｍｏｌ／ＬＮａＯＨ＋０．１ｍｏｌ／ＬＮａ４Ｐ２Ｏ７混合液连续浸提的松结态（Ｈ１）和稳结态（Ｈ２）腐殖质所占的比例随土壤ｐＨ升高分别呈减少和增加趋势。统计分析显示Ｈ１与游离态铁，铝呈极显著的正相关，与交换性钙呈极显著负相关，Ｈ２则与交换性钙呈极显著正相关，而与游离     

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.     

Humus composition and humification degree of humic acids of alpine meadow soils in the northeastern part of the Qinghai–Tibet Plateau

The characteristics of humus composition are important for understanding the mechanism of carbon storage in the Qinghai–Tibet Plateau. The aim of this study was to characterize the quality of soil organic matter (SOM) in this region. Soil samples from four soil profiles in fenced study sites in the alpine grassland were collected at altitudes of 4200, 4000, 3800, and 3400 m, along the southwest facing slope in the Qilian Mountains. The humus composition and humification degree of the humic acid (HA) were determined by two methods: (1) extraction with 0.5% sodium hydroxide (NaOH) followed by 0.1 M sodium pyrophosphate (Na₄P₂O₇) (OH-PP method); and (2) treating once with 0.1 M hydrochloric acid (HCl) followed by extracting with 0.5% NaOH (Cl-OH method). Physico-chemical analysis revealed higher exchangeable cation content and higher base saturation ratios could be related to slightly acidic to neutral soils, which could be regarded as calcium (Ca)-rich soils. The amounts of combined-form HAs obtained by HCl pretreatment (HA_Cl – HA_OH; ?HA_Cl) were remarkably higher than those extracted with Na₄P₂O₇ (HA_PP), indicating that the combined form of HAs is mainly Ca. In addition, the proportion of HA_PP in the total HAs extracted with both NaOH and Na₄P₂O₇ (HA_OH + HA_PP) obtained in the OH-PP method increased with soil depth and decreasing elevation, indicating that HAs associated with aluminum (Al) and iron (Fe) were distinguished in the subsoils of lower elevation. Therefore, the formation of the organo-mineral complex may contribute to stabilizing SOM in the Qinghai–Tibet Plateau. Moreover, Type A-HA with the highest degree of humification was obtained from the deeper horizons with the Cl-OH method and almost all horizons by extraction with Na₄P₂O₇ in the OH-PP method. Further studies using various spectroscopic analyses are necessary to elucidate the chemical properties of SOM in this region.     

Origin and properties of humus in the subsoil of irrigated rice paddies

Stability of humus in the plow layer soil is considered to affect the quantity and quality of dissolved organic matter leached from the plow layer soil. Therefore, a model experiment was conducted to analyze the effect of soil reduction under submerged conditions on the stability of humus in the plow layer soil. The changes in the stability of humus in the plow layer soil during submerged incubations with and without rice straw application were evaluated based on the changes in the binding type of humus. Binding type of humus in the plow layer soil was analyzed by successive extractions of organic matter with water, 0.25 M Na₂SO₄, 0.1 M Na₄P₂O₇ (pH 7.0), 0.1 M Na₄P₂O₇ (pH 10.5), and 0.1 M Na₄P₂O₇ (pH 10.5) with NaBH₄. Amounts of Fe, Mn, and Mg in each fraction were also determined to estimate the relationships between humus and metals.

The successive extraction of humus indicated that the amount of organic carbon which was extractable with the (NaBH₄ +0.1 M Na₄P₂O₇) solution decreased while that of the 0.1 M Na₄P₂O₇ (pH 7.0}-extractable organic carbon increased during submerged incubation with rice straw application. The origin of the increase in the amount of organic carbon in the Na₄P₂O₇ (pH 7.0)-extractable fraction during submerged incubation was investigated further by another incubation experiment using ¹³C-glucose as a reducing agent. Atom- 13C% analysis showed that the contribution of organic carbon derived from compounds other than glucose to the increase in the contents of humic acids and fulvic acids in the Na₄P₂O₇ (pH 7.0)-extractable fractions was ca. 80%. Therefore, it was concluded that the binding type of humus changed from (NaBH₄ + Na₄P₂O₇)-extractable to Na₄P₂O₇ (pH 7.0)-extractable humus under reducing conditions. Since the amounts of organic carbon and Fe increased in the Na₄P₂O₇ (pH 7.0)-extractable fraction and decreased in the (NaBH₄ +0.1 M Na₄P₂O₇)-extractable fraction simultaneously, iron reduction was presumably associated with the change in the binding type of humus in submerged paddy soil.     

红壤中铝的形态

以改进的连续分级提取方法,用１ｍｏｌ／Ｌ,ＫＣｌ,０．２ｍｏｌ／Ｌ,ＨＣｌ,０．１ｍｏｌ／Ｌ Ｎａ４Ｐ２Ｏ７（ｐＨ８．５）,ＤＣＢ溶液,０．３３ｍｏｌ／Ｌ,柠檬酸钠和０．５ｍｏｌ／Ｌ ＮａＯＨ为提取剂,把红壤中可提取的非晶态铝区分为交换态铝,肿附态无机羟基铝,有机配合态铝,氧化铁结合态铝,层间铝和非晶态铝硅酸盐。     

A reassessment of podzol formation processes

Translocated (oxalate-soluble) Al and Fe are present predominantly in inorganic forms in the B₂ horizons of the five pcdzol profiles examined: A1 as imogolite and proto-imogolite allophanes, and Fe as a separate oxide phase. Below the top few cm of the B₂ horizon, over 75 per cent of the extractable (acid-plus alkali-soluble) organic matter is present as Al-fulvates, largely sorbed on allophanic material. The Bh horizons of the Iron Humus Podzol and Iron Podzol intergrades are distinguished by very high levels of organically bound Fe (soluble in EDTA solution), five to ten times more than in immediately adjacent A₂ or B₂ horizons, and also by larger humic acid contents than in comparable B₂, levels in typical Iron Podzols. Inorganic forms of translocated Al and Fe are probably absent from two of the three Bh horizons examined, and also from the Bhg horizon overlying the thin iron pan in the Peaty Podzol. The organic matter in this Bhg horizon is saturated with Al rather than Fe. Chemical and physical processes which could lead to evolution of a profile along the genetic sequence, Iron Podzol, Iron Humus Podzol, Peaty Podzol, are postulated. During the formation of an Iron Podzol, positively charged inorganic sols carry aluminium, silicon and iron from the A₂ and deposit them in the B₂ horizon; subsequently, with the development of an H layer, colloidal humus migrates through the A₂ and precipitates on the positive colloids at the top of the B₂ horizon to form a Bh horizon, in which remobilized ferric species are trapped by the organic matter. In higher rainfall areas, occasional waterlogging above the oxide-impregnated B₂ leads to a thin iron pan, separating permanently oxidizing conditions below from seasonally waterlogged and reducing conditions above.     

A comparison of the effectiveness of various extractants for determining humus quality in a calcareous soil

Abstract

Humic substances from an Argentinian chesnut (Mollisol) soil were extracted with Na‐Dowex A‐1 resin, 0.1 N NaOH and 0.1 M Na₄P₂O₇ without decalcification and with 0.1 N NaOH after decalcification. Humic to fulvic (Ch/Cf) acid and E₄/E₆ ratios of the extracts were determined and compared.

A simpler and more rapid procedure than the classical ones for extracting and characterizing soil humus is proposed. The procedure is based on the use of a chelating resin as extractant and on the direct determination of analytical properties of humus in aliquots of the extract.     

Chemical and mineralogical properties of sandy and loamy-sandy ochreous brown earths in relation to incipient podzolization in a brown earth—podzol evolutive sequence

Chemical and mineralogical properties of ochreous brown earths have been studied with particular reference to: (1) the distribution within the profiles of Fe and Al compounds; (2) the occurrence of smectite-like clay minerals in surface horizons. Ochreous brown earths studied belong to a developmental sequence of forest soils, from acid brown earths to ferric podzols, developed on sandy or loamy-sandy acid parent materials. In such a soil sequence, both selective chemical and mineralogical data show clearly that podzolization is already active in ochreous brown earths, whereas such an incipient podzolization is quite undetectable by direct morphological observations. The distribution patterns of amorphous Fe and Al hydrous oxides and organic associations, clearly show the intergrade character of ochreous brown earths, when compared with the vertical distribution of Fe and Al forms in acid brown earths and podzolized soils. The Fe/Al ratio of both an NH₄-oxalate extract and an NaOH/Na-tetraborate extract buffered at pH 9.7, measured in the A₁B diagnostic horizon of ochreous brown earths, is a particularly appropriate and useful genetic criterion for the detection of incipient podzolization. Moreover, the presence of expansible clay minerals (degradation smectites) in the clay-sized fraction of the surface horizons of ochreous brown earths (A₁ and A₁B) can be considered as supplementary evidence of incipient podzolization.     

Electrofocusing: A new method for characterization of soil humic matter

Electrofocusing in polyacrylamide gel was carried out on humic substances extracted by 0.1 n NaOH, 0.1m Na₄P₂O₇, and by the method of Burns, El Sayed and McLaren (1972) from the upper and lower organic horizons of an alpine podsol. The electrophoretic patterns were characteristic of both humus origin and extractions procedure. The best resolution of the isoelectric bands for the humus were obtained by the Burns-McLaren procedure. The ionic component does not have much influence on the distribution of humus constituents within the electrophoretic pattern, but the presence of phosphate appears to be essential to obtain good separations.     

Assessing the extraction and quantification of amorphous silica in soils of forest and grassland ecosystems

Many studies have highlighted the importance of the Amorphous Silica (ASi) pool to the overall mass balance in the biogeosphere. In order to advance our knowledge of measurements and quantification of this pool, it is necessary to compare the ability of different extractants to dissolve ASi in soils and to test methods developed in the aquatic sciences to soils systems. The methods used in this work included three acid extraction techniques (0.2 m NH₄‐oxalate, 0.1 m NH₄‐citrate and 0.5 m NH₄‐acetate) and two alkaline extraction techniques (0.094 m Na₂CO₃ and 0.5 m NaOH), which are more commonly used for the measurement of ASi in aquatic sediments. Our results indicate that the amount of Si extracted from phytolith samples with the acid methods was two orders of magnitude less than the amount of extracted by alkaline extractions. When applied to natural soil samples, these extractions show that the acid techniques are only able to extract loosely‐bound components such as adsorbed Si and Si bound in amorphous matrices with Al and Fe. While Na₂CO₃ or NaOH extracted the same amount of ASi in Podzols, Na₂CO₃ was able to extract only part of the ASi extracted with NaOH in Chernozems. Pre‐treatment of the samples with 0.1 m HCl before the Na₂CO₃ extraction did not increase amounts of ASi extracted. The present work suggests that alkaline methods used commonly for ASi on aquatic sediment samples can be used on a wide variety of soils.     

Sequential extractions and 31P-NMR spectroscopy of phosphorus forms in animal manures, whole soils and particle-size separates from a densely populated livestock area in northwest Germany

The solubility and forms of phosphorus (P) were investigated in manures from chicken and pigs, eight whole soil samples and clay-, silt-, and sand-size separates from an arable and a grassland soil. Total P (P_t) in liquid pig manure (16.2 g kg^–1) and dry chicken manure (26.2 g kg^–1) was distributed between residual P (39–41% P_t), H₂SO₄–P (17–27% P_t), labile resin- and NaHCO₃–P (24–39% P_t), and NaOH-P (3–10% P_t). Most soils had larger proportions of NaOH-P and residual P, indicating reactions of manure-derived P compounds with pedogenic oxides and humic substances. Clay-size separates had the highest P-concentrations in all fractions and were particularly enriched in exchangeable and labile P forms. Solution ³¹P-nuclear magnetic resonance (NMR) spectra of 0.5 M NaOH extracts from manures and some soil samples showed greater signal intensities for orthophosphate and monoester P than 0.1 M NaOH extracts. This can be explained by alkaline hydrolysis phosphate diesters at higher NaOH concentrations and/or by preferential extraction of diesters at lower concentrations. The ³¹P-NMR spectra showed differences between the two manures and confirmed that increasing proportions of ester-P can be expected if they are spread to soils. The NaOH extracts of soil samples were characterized by large proportions of orthophosphate-P (mean 77% of assigned P compounds), which seemed to be slightly enriched in clay fractions whereas the extracts from silt contained more ester-P. Sequential extractions and ³¹P-NMR spectroscopy both showed that these excessively manured soils are likely to lose large amounts of P. Received: 15 July 1996     

SYNTHETIC ALLOPHANE AND IMOGOLITE

In order to prepare allophane and imogolite in the laboratory, solutions containing l–2× 10^–3 M orthosilicic acid and 4–0.5 × 10^–3 M A1C1₃ (SiO₂/Al₂O₃ molar ratio; 0.5, 1.0, 2.0, 4.0 and 8.0) were heated at 95–100°C for 113 hours after addition of NaOH (NaOH/Al molar ratio; 1.0, 2.0, 2.8 and 3.0). Boehmite was found in the precipitates from all solutions with initial SiO₂/Al₂O₃ ratios of 0.5. Imogolite was found with allophane II in the products from solutions with SiO₂/Al₂O₃ ratios of 1.0 or greater and with NaOH/Al ratios of 2.8 or less (final pH 5.0), whereas allophane I was found in the precipitates from solutions with the same SiO₂/Al₂O₃ ratios but with the NaOH/Al ratio of 3.0 (final pH = 5.0–6.3). The mode of formation, chemical composition, infrared spectra, electron micrographs, electron diffraction patterns and differential thermal analysis curves of synthetic imogolite and allophanes (I and II) were compared with those of their natural counterparts.     

长期施用有机肥料对紫色水稻土有机无机复合性状的影响

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

FTIR‐spectroscopic characterization of humic acids and humin fractions obtained by advanced NaOH,Na4P2O7, and Na2CO3 extraction procedures

Aim of our study was the development of the methodological basis for the characterization of humic fractions of a long‐term field experiment. Humic acids (HAs) were extracted from three layers of a nontilled soil using three different extractants (1 M NaOH, 0.1 M Na₄P₂O₇, 1 M Na₂CO₃), and the humin fraction was enriched. NaOH as extractant for FTIR analysis of humic substances yields higher resolved IR spectra, especially in the important regions of stretching vibrations including aromatic and aliphatic groups and in the fingerprint area including amides, aliphats, and aromats than the other extractants. The NaOH extraction has lower extraction yields as compared to Na₄P₂O₇ and Na₂CO₃ and represents a different part of the soil organic matter (SOM). This is reflected by lower C : N ratios and higher E₄ : E₆ and fulvic acid–to–humic acid ratios as compared to the other extractants. The FTIR band areas of HA fraction obtained by NaOH showed an increase of the aromatic and carbonyl groups and a decrease of amide groups with increasing soil depth. Aliphatic groups showed contradicting results: The bands of the stretching vibrations increased, and the band of the bending vibrations decreased. We assume that band interactions in the bending vibrations were responsible for that phenomenon under the assumption of an increase of aliphatic groups with increasing soil depth. The IR bands of the enriched humin fraction showed a decreasing trend in case of both aliphatic bands deriving from stretching vibrations and an increase of aromatic characteristics with depth. Our study led to the conclusion that HA fractions obtained by 1 M NaOH represent a small and dynamic fraction indicated by the measured yields in combination with values of N_t, C : N, E₄ : E₆ ratios, and ratios of fulvic acids (FA) to HA. The humin fraction has a high contribution to the total organic C and represents a more stabilized fraction of SOM which still shows changes in its aromatic and aliphatic characteristics with soil depth.     

Chemical significance of aluminium extracted from three horizons of an acid forest soil, using chloride salt solutions

Aluminium is usually important in exchange reactions in acid soil, but amounts extracted are strongly affected by procedure. We examined the impact of proton release, following salt addition, on Al removal from three horizons (Oe, Oa and A₁₂) of an acid, brown forest soil. The Al was first extracted with either 1 M KC1, 1 m NH₄C1 or 0.5 m CuCl₂ on the three horizons limed to pH 5.5. For any lime addition, both the pH drop following salt addition and the amounts of extracted Al were greater with CuCl₂ than with KC1 or NH₄C1. For the Oa and A₁₂ horizons there was a single inverse linear relation between amount of Al extracted and the pH of final extract, independent of the extracting cation. In the Oe horizon CuCl₂ extracted constant amounts of Al, whereas the quantity of Al removed by KC1 or NH₄C1 increased linearly as pH declined below pH 3.6. Extra Al was mobilized following unbuffered KC1 extraction, a side effect induced by the extracting procedure itself. Al mobilization increased with increasing H⁺ additions. In the Oe horizon, equilibrium was established rapidly (≤ 24 h), and decreasing the pH of the soil-KCl suspensions to 2.0 resulted in extracted Al amounts equal to or slightly greater than those obtained with CuCl₂ solutions. Al amounts extracted with acidified KC1 solutions from the A₁₂ were close to those obtained using CuCl₂ solutions at similar pH in the extract. In the samples from the A₁₂ layer, increasing the equilibration time resulted in increasing proton consumption and equivalent release of Al ions in the extract.     

CHANGES IN MOLECULAR WEIGHT DISTRIBUTION OF SOIL ORGANIC MATTER DURING SOIL DEVELOPMENT

Ten different topsoils representing members of three soil chronosequences were pre-treated with 0.1 M HC1 and extracted with neutral 0.1 M Na₄P₂O₇ followed by 0.5 M NaOH. Extracts were purified and fractionated into five different nominal molecular weight fractions using gel filtration. With increasing soil development, the proportion of large molecules (>200 000) in the organic matter decreased with an increase in the proportion of intermediate size molecules (200 000 – 10 000). This effect was more evident in the mild Na₄P₂O₇ extracts than in the subsequent NaOH extracts, and in soils of the Manawatu chronosequence than in those of the other two chronosequences and are attributed to changes in the nature and humification of soil organic matter during soil development.     

Phosphate fixation by ando soils different in their clay mineral composition

The phosphate fixation capacity at pH 4.5 and an equilibrium concentration of 250 mM phosphate was measured. The soil samples were divided into five groups according to their clay mineralogical composition. The first group soils contain opaline silica and allophanelike constituents, and some unidentified minerals, the second opaline silica and crystalline layer .i1icates, the third opaline silica and crystalline layer silicates with additional allophanelike constituents or aluminarich gel-like materials, the fourth allophanelike constituents, allophane and imogolite and the fifth crystalline layer silicates, allophanelike constituents and alumina-rich gel-like materials, plus some halloysite-like minerals, respectively. The first group soils had phosphate fixation capacities of 3,000 to 8,000, the second group soils 1,000 to 3,000, the third group loib 2,000 to 13,000, the fourth group soils 8,000 to 15,000 and the fifth group soil. 5,000 to 12,000 mg P₂O₅/100 g oven-dry soil, respectively. The fourth group soils in which allophane and imogolite predominated showed the highest phosphate fixation capacity.

The fractions which dissolved from almost all soil samples by treatments with 6% H₂O₂ Na₂S₂O₄-NaHCO₂-Na citrate and 2% Na₂CO₃ were estimated to have very high phosphate fixation capacities (8,000 to 19,000 mg P₂O₅/100 g dry-matter), and there was not much difference among the soil samples examined. Iron and aluminum combined with humus, allophanelike constituents, alumina-rich gel-like materials and halloysite-like minerals in addition to allophane and imogolite contribute to the phosphate fixation of Ando soils.     

The Effectiveness of Zn Leaching from EAFD Using Caustic Soda

Electric arc furnace dust (EAFD) is a toxic waste which is mainly rich in iron oxide, zinc, and lead. Hydrometallurgical extraction of zinc from Jordanian EAFD in alkaline medium was investigated; NaOH, NaHCO₃, and Na₂CO₃ were used as leaching agents. The pH values for the prepared solutions were 8.3, 8.2, and 12.55 for NaHCO₃, Na₂CO₃, and NaOH, respectively. The effect of NaOH concentration (1, 3, 5, 7, and 9 M), contact time (5 min to 3 h), temperature (20, 40, and 60), and solid-to-liquid ratio (SLR; 20, 40, 80, and 120 mg/ml) on the leachability of zinc from EAFD were tested. The initial EAFD and the resulting leach residues were characterized using X-ray diffraction (XRD) and X-ray fluorescence (XRF). EAFD contained 25.9% Zn, 18.0% Fe, and 3.2% Pb. A maximum zinc recovery of 92.9% was achieved using 6 M NaOH at 60 °C with solid loading of 20 g/L and 3 h leaching time. NaHCO₃ and Na₂CO₃ were not efficient leaching agents for Zn extraction since the recoveries were only 2.6 and 4.5%, respectively. Zn and Pb were depleted in the residues with an E-factor of 0.5–0.6 and 0.1–0.25, respectively. Iron was enriched in the residues; the E-factor was around 2. The EAFD contained mainly zincite, franklinite, and magnetite. After 3 h leaching, only traces of zincite exist in the residues, while sylvite and halite were completely dissolved.     

Selenite fixation by soil particle-size separates

The fixation of selenite by clay- (< 2 μm), silt- (2–20 μm) and sand-size (20–2000 μm) separates from two arable soils was examined in solutions of ⁷⁵Se-labelled sodium selenite using a Se/sample ratio of 1/10⁶. Size separates were isolated by ultrasonic dispersion and gravity sedimentation. Selenite fixation was determined after equilibration periods ranging from 5 min to 26 h. Hydrogen peroxide-treated samples were included to examine the effect of organic matter on selenite fixation capacity.
The relative distribution of native Se, C, dithionite/citrate-extractable Fe and Al between size separates was similar. Concentrations in clay were four to nine times higher than in whole soils, silt showing two to five times higher concentrations and sand being very low in Se, C, Fe and Al.
After 1 h, clay, silt and sand fixed 64–65%, 45–61% and <5% of the selenite added, respectively. The fixation on whole soils was 14–18%. After 1 day, fixation on clay, silt, sand and whole soil increased to 78–87%, 67–79%, 3–14% and 31–39%, respectively.
Hydrogen peroxide-treatment reduced the selenite fixation capacity of whole soil, silt and sand to very low levels. Fixation on peroxide-treated clay was in accord with values for pure clay minerals reported in the literature. Generally, the fixation capacity of peroxide-treated natural clay and pure clay minerals was only half that observed for intact clay-size separates, demonstrating the importance of organic matter in soil selenite fixation capacity.     

Extractability and dissolution kinetics of pure and soil-added synthesized aluminium hydroxy sulphate minerals

Various extractants used in current analytical procedures for the fractionation of sulphur (S) in soils were compared with respect to their ability to dissolve Al hydroxy sulphate minerals of defined composition (basaluminite, K alunite, mixtures of basaluminite and Na alunite). The minerals were synthesized and aged in the laboratory at 20°C and 50°C. The dissolution kinetics at 20°C of these Al hydroxy sulphates in deionized water, 0.02M HCl and 0.02M NaOH were also investigated. The dissolution stability of the Al hydroxy sulphate minerals increased in the order basaluminite < K alunite < Na alunite. The dissolving power of the reagents used increased in the order H₂O ≤ 0.016M KH₂PO₄? 0.02M HCl ≈ acidic NH₄ oxalate ≈ 0.5M NaHCO₃ < Na₂ CO₃/NaHCO₃ < 0.1M NH₄F < 0.5M NH₄F < 0.05M NaOH ≤ 0.05M LiOH. In Al hydroxy sulphate-containing soils, inorganic S is probably understimated and ester sulphate S overestimated, if the inorganic S pool is assessed by extraction with KH₂PO₄, Ca(H₂PO₄)₂ or NaHCO₃ solutions. The dissolution of all studied Al hydroxy sulphates, particularly that of K and Na alunite, in H₂O and 0.02 M HCl is strongly delayed by kinetic restraints. Thus it seems unlikely that Al³⁺ or SO^2?₄ activites in soil solutions are strictly regulated by precipitation/dissolution equilibria of these minerals except for horizons with extraordinarily slow seepage water movement.