Clay mineralogy of a soil sequence in slope deposits derived from hauptdolomit (dolomite) in the bavarian alps

Clay mineralogy was determined in a sequence of soils formed in slope deposits derived from Hauptdolomit and ranging from a Mullrendzina (Rendoll) to a Terra fusca (Eutrochrept) and a Parabraunerde-Terra fusca (Hapludalf). Results indicated an alteration of illite to hydroxyl-Al interlayered clay in the course of soil formation. No evidence was found of formation of kaolinite in these soils. This clearly confirms all soils to have been formed under a recent cold humid climate. Furthermore clay mineral weathering starts even before carbonates are dissolved and completely removed from these soils.     

尼日利亚热带雨林地区的内陆山谷中土壤发育和肥力特征: 矿物成分和粒度分布

The particle-size distribution and mineralogical composition of the clay (< 2 μm) and fine-sand (0.25--0.10 mm) fractions in soils of two inland valleys in Abakaliki and Bende, Southeast Nigeria, were investigated to provide basic information on soil-forming processes and agricultural potentials. These soils were silty or clayey, deriving from Cretaceous or Tertiary shale materials. The particle-size distribution and its computation on a clay-free basis revealed relatively remarkable lithologic breaks in a couple of pedons. The effect of lithologic discontinuities on soil mineralogical composition was not, however, conspicuous. Petrographic investigation revealed that quartz predominantly comprised the fine-sand fraction in the soils at both study sites. Nevertheless, the clay mineralogical composition of the soils was a mixture of kaolinite, irregularly interstratified smectite-illite intergrades (S/I), hydroxyl-Al interlayered 2:1 type clays (HICs), vermiculite, smectite, halloysite and illite along with fine-sized quartz in Abakaliki. The soils of Bende predominantly contained smectite, which was partially interlayered with hydroxyl-Al and kaolinite. It is suggested that seasonal floodwater has slowed the disintegration of weatherable clay minerals inherited from the shale, while quartz originating from the sandstone is predominant in the fine-sand fraction. Additionally, a possible soil-forming process observed at the both study sites was ferrolysis, which was indicated by a clear decreasing pattern of HICs downward in the soil profiles. The entry of S/I and vertical distribution patterns for a couple of clay minerals in the pedon suggested that the soils in Abakaliki have developed under the significant influence of aeolian dust delivered by the harmattan. The findings might describe a site-specific deposition pattern of harmattan dusts as well as hydromorphic soil-forming processes in the wetlands of the inland valleys.     

层柱黏土引水体材料及其在干旱地区植树造林中的应用

为解决干旱地区植树造林中的地表干土层和浇水困难问题而提出黏土引水体材料。对原生膨润土进行层柱化处理并测得了其不同交联剂比例下的材料导水性能,采用X射线衍射、热重、孔隙度分析等测试手段对材料的微结构和热性能进行了表征。研究结果表明,对黏土材料进行改性能显著提高其导水性能,材料的比表面积的增大、孔数量的增加以及孔结构的复杂化是其导水性能改善的主要原因。该材料对提升干旱地区地表层下的水分,提高苗木成活率有明显的效果。     

Iron oxide and clay minerals and their relation to colours of red and yellow podzolic soils near Sydney,Australia

The iron oxide and clay minerals in some typical red and yellow podzolic soils from New South Wales have been investigated by X-ray diffraction and infra-red spectroscopy. The dominant iron oxide mineral is goethite containing about 13–14 mol % AlOOH, this being the mineral which gives the yellow soils their characteristic colour. The red soils also contain finely divided hematite which masks the colour of the goethite. Lepidocrocite was not detected in any of the soils examined. The dominant clay minerals are kaolinite and dioctahedral interstratified illite-smectite, the latter being more concentrated in the finer clay fractions, especially in soils developed on calcareous greywacke. In the red podzolic soil developed on Ashfield shale, illite-smectite is strongly interlayered with well-ordered aluminous material. Dickite occurs in this soil.     

Source minerals and formation of partially interlayered vermiculites in Dystrochrepts derived from Tertiary sediments

The formation of partially interlayered vermiculite (PIV) was studied in six Dystrochrepts derived from Tertiary sediments. Mineralogy of silt and clay fractions of gravel and fine earth separated from surface and subsurface samples were determined by X-ray diffraction. PIV, mica, vermiculite and regularly interstratified 1:1 PIV/chlorite (PIV/Ch(l:l)) were the dominant clay minerals. The contents of these minerals were compared between the specific particle-size fractions of gravel and fine earth for each sample and the difference was interpreted in terms of mineral transformation associated with soil formation. PIV was formed from mica and PIV/Ch(l:l) in soils with a pH(KCl) of 3.5 to 4.0 and little organic matter. Vermiculite was formed from mica in surface soils with a low pH (pH(KCl) 3.5) and abundant organic matter. PIV would form directly from mica without an intermediary phase of vermiculite and form from PIV/Ch(l:l) by partial dissolution of interlayers in chlorite layers.     

Review Article. What are the nature and formation conditions of hydroxy‐interlayered minerals (HIMs) in soil?

Primary minerals of the parent material undergo weathering during the formation of terrestrial soils to varying extent. As a result, secondary minerals develop, which comprise, among many others, hydroxy‐interlayered minerals (HIMs). These minerals have formed by interlayering of hydroxy‐metal complexes (especially of Al³⁺, also Mg²⁺, Fe^2+/3+) into micas, expansible 2:1 phyllosilicates and forming oligomers, or by weathering of primary chlorite. The degree of interlayer filling and the stability of these fillings affect several physico‐chemical soil properties, for instance the cation exchange capacity. Although many studies have been conducted on formation, occurrence, and properties of HIMs in soil during the last decades, several challenges still exist. These challenges include analytical identification and quantification of HIMs in soil, the nature of the interlayer filling and the identification of favorable conditions in soil for the formation of HIMs. In order to deepen the understanding of formation, properties, and fate of HIMs in soil, we critically reviewed the available literature. Based on the review, we recommend using a new structural model that enables quantification of hydroxy‐interlayered smectite in soil by X‐ray diffractometry, laboratory experiments on the formation and preservation of different types of interlayers and considering the temporal and spatial dimension of the formation of HIMs in soil in more detail.     

Incipient podzolization and weathering caused by complexation in a forest Cambisol on loess as revealed by a soil solution study

Surface podzolization has so far been diagnosed from morphological observations, selective extraction and mineralogical investigations. We studied this process in two Cambisol profiles developed in loess, one with a fibrimor humus and the other with a dysmoder humus, by characterizing the chemical composition and the complexing properties of the soil solution. The solutions were sampled bimonthly for 3 years at four depths (4, 8, 13, 25 cm) using both zero‐tension and low‐tension capillary‐wick lysimeters. The leachates from the Ah horizon of the soil with fibrimor contained less nitrate, sulphate and calcium than those from the one with a dysmoder because there was less bioturbation and mineralization in it. Both the complexation capacity and the density of ligand binding sites were larger in the soil solutions of the Ah (4 cm) and AB (8 cm) horizons of the soil with the fibrimor. In this soil, the complexing properties of the liquid phase induced a depletion of inorganic monomeric aluminium. In this environment, the hydroxy interlayered 2:1 clay minerals lose their Al‐interlayers and transform into vermiculite and smectite, which in turn weather, producing large amounts of magnesium in the soil solution. This was found to be a major characteristic of weathering by complexation and incipient podzolization in the Cambisol with the fibrimor. In this process, nitric acid probably contributes to mineral dissolution.     

Quantitative determination of minerals in acid forest soils of granite

A procedure for quantifying minerals in particle size fractions of fine earth (< 2 mm) is presented. Mineral fractions of the acid forest soils are characterised by various transition products. Transitional minerals between illite and vermiculite or smectite, polyhydroxy-Al polymers interlayered in smectite and vermiculite, as well as poorly crystalline compounds are present. Normative calculations with standard minerals, generally applied to rocks, cannot be used to quantify precisely minerals of these soil samples. Conventional qualitative and quantitative chemical analyses are therefore completed by microanalyses of well-identifiable minerals. The calculation procedure is based mainly on a system of simultaneous linear equations. These are set up from the chemical contents of a particle size fraction on the one hand and from the corresponding element contents of single minerals on the other hand. The contribution of single minerals to overall parameters can be calculated by programmed algorithms. The methodology was adjusted to different particle size fractions.     

Interlayer materials of partially interlayered vermiculites in Dystrochrepts derived from Tertiary sediments

Interlayer materials of partially interlayered vermiculites (PIV) in 15 Dystrochrepts derived from Tertiary sediments were analysed by dissolution with hot 1/3M sodium citrate or 0.15 M oxalate-oxalic acid in combination with XRD and IR spectroscopy. Both the citrate and oxalate treatments dissolved Al from all soil clays. The dissolution of Al by the citrate treatment paralleled the dissolution of Si and the interlayer collapse of PIV, whereas that by the oxalate treatment did not, indicating that the interlayer materials contain not only Al but Si. The materials dissolved by the citrate treatment had a molar Si/Al ratio ranging from 0.72 to 0.24 that decreased with the increasing interlayering of PIV. Differential IR spectroscopy indicated the dissolution of aluminosilicates possibly having Si-O, Al-OH and Si-O-Al bonds, but not Si-O-Si bonds. The extent of interlayering of PIV showed a good correlation with the amount of Al dissolved by the citrate treatment and increased with increasing soil pH (H₂O) from 4.5 to 5.2 and with decreasing exchangeable Al in soil.
Formation of a hydroxy-Al sheet partially bonded with Si-tetrahedra was suggested as a possible model of the interlayer structure of PIV. The differences between PIV in the studied Inceptisols and other soils are discussed.     

Aluminium chemistry in two contrasted acid forest soils and headwater streams impacted by acid deposition,Vosges mountains,N.E. France

Al chemistry was studied in two acidic watersheds, one with a podzol, the other with an acid brown soil, in the Vosges mountains (N.E. France), by analysing both leaching and centrifugation soil solutions and spring waters over 3 yr. In the podzol, Al was mobilized in the eluvial horizons under the predominant influence of organic acidity, then leached down the profile as organic and F-bound Al. Strong undersaturation with respect to proto-imogolite and imogolite showed that the proto-imogolite theory of podzolization could not apply. Al was transferred from the soil to spring water mostly as Al³⁺ and Al-F. Al³⁺, as well as additional minor species (AlOH²⁺, AlSO₄ ⁺), originated from the redissolution of the top of the spodic horizons under the influence of both soil solution acidity and the occurrence of mobile anions derived from atmospheric deposition. Conversely, in the acid brown soil, Al mobilization was regulated by nitrate and occurred mainly as Al³⁺. Most of Al was retained in the deep soil and only traces of monomeric Al reached spring water. In the podzol eluvial horizons, soil solutions were undersaturated with respect to all relevant mineral phases and their chemical composition agree with the concept of a mobilization of Al from the solid soil organic Al and a control of Al³⁺ activity by complexation reaction with the solid and soluble soil organic matter and F. In the acid brown soil, soil solutions were found to be in equilibrium with natural alunite, and the formation of this mineral, if confirmed, would account for the occurrence of 'open' vermiculites instead of the expected hydroxy-Al interlayered vermiculites. Al solubility control in surface water of both watersheds remains unclear. The Al-F species in both watersheds and the likely control of Al solubility by alunite in the acid brown soil emphasize the influence of acid deposition on Al chemistry in acid watersheds.     

Einfluß pedogener Tonminerale auf die Kinetik (km und Vmax) von alkalischer und saurer Phosphatase

Effect of pedogenic clay minerals on the kinetics (Km and Vmax) of alkaline and acid phosphatase The influence of various pedogenic clay minerals, derived from 5 different Pelosols (=Vertisols), on the activity and kinetics (Km and Vmax) of alkaline and acid phosphatase (AP and SP, respectively) was studied in model experiments. Generally speaking, Vmax of both enzymes decreased with increasing immobilization. Km remained constant or increased considerably depending on the composition of the clay minerals. The changes in Vmax and Km were both clay- and enzyme specific. Immobilization of AP by most clays was reflected by a mixed type of inhibition, while that of SP resulted in a competitive type of interaction. Non-competitive inhibition was recorded with AP after sorption to mixed and interlayered clays of the illite-montmorillonite-chlorite type (profile V) and with SP in the presence of montmorillonite clay (profile I). The types of inhibition were compared with those observed with two- and three-layered clays of sedimentological origin.     

三氯乙酸提取硅作为水稻缺硅诊断指标的可行性

Potassium chloride, Na-pyrophosphate,CuCl2,NH4-oxalate,dithionit-citrate-bicarbonate(DCB) and Na-citrate solutions were employed to etract aluminum(Al) and iron(Fe) sequentially and separately from 15 acidic soils located at the Mangshan Mountains,Hunan Province,China,Many evidences showed that separate pyrophosphate extracted mainly KCl-extractable Al,organo-Al complexes and some inorganic Al compounds,whereas separate CuCl2 extracted KCl-extractable Al and some organo-Al complexes,CuCl2 extracted much less amounts of Al than pyrophosphate did from the soils .Separate oxalate did not extract all KCl-pyrophosphate-CuCl2-oxalate seuentially extractable Al and Fe ,Also,separate DCB did not extract all KCl-pyrophosphate-CuCl2-oxalate-DCB sequentially extractable Al. The forms of Al extacted by oxalate and DCB from the soils were majorly noncrystalline.The interlayered materials of 1.4-nm intergrade minerals of the soils were attributed mainly to hydroxy Al polymers.     

Influence of the nature of clay minerals on the fixation of radiocaesium traces in an acid brown earth–podzol weathering sequence

The magnitude of radiocaesium fixation by micaceous clay minerals is affected by their transformation, which depends on weathering in soil. The net retention of radiocaesium traces was quantified by sorption–desorption experiments in the various horizons of four sandy soils forming an acid brown earth–podzol weathering sequence derived from sandy sediments and characterized by marked changes in mineral composition. The features of the 2:1 minerals of the four soils, resulting from an aluminization process in depth and a desaluminization process towards the surface, had a strong influence on Cs⁺ fixation. Beneath the desaluminization front, which deepens from the acid brown earth to the podzol, hydroxy interlayered vermiculite was dominant and the ¹³⁷Cs⁺ fixation was the weakest. At the desaluminization front depth, vermiculite was responsible for the strongest ¹³⁷Cs⁺ fixation. In the upper layers, smectite appeared in the podzolized soils and the ¹³⁷Cs⁺ fixation decreased. The magnitude in Cs⁺ fixation therefore appeared as a tracer of the transformation process affecting the 2:1 clay minerals in the acid brown earth–podzol weathering sequence. This magnitude was positively correlated with the vermiculite content of the studied soil materials estimated by the rubidium saturation method.     

Influence of Aluminum Hydroxide on Potassium Release from Two Colombian Soils

Abstract

The effect of sesquioxides on the mechanisms of chemical reactions that govern the transformation between exchangeable potassium (Kex) and non‐exchangeable K (Knex) was studied on acid tropical soils from Colombia: Caribia with predominantly 2∶1 clay minerals and High Terrace with predominantly 1∶1 clay minerals and sesquioxides. Illite and vermiculite are the main clay minerals in Caribia followed by kaolinite, gibbsite, and plagioclase, and kaolinite is the major clay mineral in High Terrace followed by hydroxyl‐Al interlayered vermiculite, quartz, and pyrophyllite. The soils have 1.8 and 0.5% of K₂O, respectively. They were used either untreated or prepared by adding AlCl₃ and NaOH, which produced aluminum hydroxide. The soils were percolated continuously with 10 mM NH₄OAc at pH 7.0 and 10 mM CaCl₂ at pH 5.8 for 120 h at 6 mL h^?1 to examine the release of Kex and Knex. In the untreated soils, NH₄ ⁺ and Ca²⁺ released the same amounts of Kex from Caribia, whereas NH₄ ⁺ released about twice as much Kex as Ca²⁺ from High Terrace. This study proposes that the small ionic size of NH₄ ⁺ (0.54 nm) enables it to enter more easily into the K sites at the broken edges of the kaolinite where Ca²⁺ (0.96 nm) cannot have access. As expected for a soil dominated by 2∶1 clay minerals, Ca²⁺ caused Knex to be released from Caribia with no release by NH₄ ⁺. No Knex was released by either ion from High Terrace. After treatment with aluminum hydroxide, K release from the exchangeable fraction was reduced in Caribia due to the blocking of the exchange sites but release of Knex was not affected. The treatment increased the amount of Kex released from the High Terrace soil and the release of Knex remained negligible although with Ca²⁺ the distinction between Kex and Knex was unclear. The increase in Kex was attributed to the initially acidic conditions produced by adding AlCl₃ which may have dissolved interlayered aluminum hydroxide from the vermiculite present, thus exposing trapped K as exchangeable K. The subsequent precipitation of aluminum hydroxide when NaOH was added did not interfere with the release of this K, and so was probably formed mostly on the surface of the dominant kaolinite. Measurement of availability of K by standard methods using NH₄ salts could result in overestimates in High Terrace and this may be a more general shortcoming of the methods in kaolinitic soils.     

Characteristics of Clay Minerals in Podzols and Podzolic Soils

The clay minerals in Podzols and podzolic soils developed under coniferous forests in the Subarctic and Cool-temperate zones are characterized by the predominance of smectite and/or mica-smectite interstratified minerals in the eluvial horizons and chlorite-vermiculite intergrade in the illuvial horizons. A large amount of vermiculite is present in the eluvial horizons of some podzolic soils in the Cool-temperate zone. The illuvial horizons of these soils also contain free iron oxides such as goethite. Imogolite and allophane are present in the illuvial horizons of several soils derived from volcanic ashes. It is suggested that the critical bioclimate for the release of interlayered aluminum from the 2:1-type minerals lies between the Cool- and Warm-temperate zone. In the eluvial horizons of Podzols and podzolic soils, mica minerals and chlorite, as primary minerals, have been transformed to smectite through the pedogenic process. Based on previous studies on the structure and degradation of the dioctahedral mica minerals, it is considered that smectite is transformed from 1M-type mica minerals directly, and from 2M-type mica minerals via mica-smectite interstratifled minerals. The formation of a smectite lattice in the eluvial horizon should be a clay-mineralogical indicator of podzolization.     

Root-induced irreversible transformation of a trioctahedral mica in the rhizosphere of rape

The ability of the roots of rape (Brassica napus) to promote the transformation and dissolution of a phlogopite mica was studied in the rhizosphere. Rape was cropped for 1 to 32 d on 2–105 μm phlogopite as sole source of both K and Mg. The chemical balance of K and Mg revealed that rape was able to induce a significant release of interlayer-K after 4 d, and even a significant release of octahedral-Mg after 8 d of cropping. After 32 d, the root-induced release amounted to 80 and 21 g kg^?1 of total-K and -Mg, respectively. The weathering products sampled in the close proximity of the roots were analysed by X-ray diffractometry (XRD), and by energy dispersive X-ray (EDX) microanalysis of resin-embedded samples prepared for transmission electron microscopy. The XRD analysis of K-saturated, oriented plates showed that part of the vermiculite formed by root activity behaved as a typical hydroxy-aluminous interlayered vermiculite (HIV). The EDX microanalysis revealed that the release of interlayer-K which occurred during the vermiculitization was compensated mostly by A1 and Mg originating from the octahedral sheet of the phlogopite. Such crystallographic and crystallochemical changes necessarily involved an acid dissolution of the mica structure, which may be related to the root-induced pH decrease encountered simultaneously in the rhizosphere. Proton excretion by rape roots was thus the probable mechanism involved in the root-induced irreversible transformation of the phlogopite.     

树木年轮及其根部土壤元素含量的对数线性相关模型的验证及应用

Nine Platanus acerifolia(Ait),Willd.trees growing in the Nanjing Children Teacher‘s School,Nanjing,China ,were selected to determine the contents of 13 chemical elements both in the 1994‘s growth rings,C(Z,t),and in the soils near the roots,C′(Z,t),of the trees ,The results showed that the relationship be-tween C(Z,t) and C′(Z,t) followed the logarithmic liner correlation moedl.lgC′(Z,t),=a(Z) b(Z)lgC(Z,t),Based on this model the chrono-sequences of chemical element contents in the soils were reproduced fromt those ih the tree rings;i.e., the dynamic variations in the chemical element contents of the soils at the sites were trced.In this study the chrono-sequences of the chemical elements including Cd,Pb,Mn,Co and Zn in the soils near the roots of a Platanus acerifolia tree from 1957 to 1994 were established ,and the background values of Cd,Pb,Mn,Co and Zn in the soil were calcuated by taking the lowest values of the chrono-sequences of the element conents as upper limits of the background values.     

Les vermiculites hydroxy-alumineuses du Massif Armoricain (France) approches mineralogique,microanalytique et thermodynamique

Hydroxy-aluminous vermiculites have been identified in samples of soils and weathering products from the Armorican Massif of France by a combination of mineralogic, microanalytic and thermodynamic techniques.The hydroxy-aluminous vermiculites behave originally as intergrades between vermiculites sensu stricto and chlorites. The interlayered aluminum responsible for the intergrade behaviour cannot be removed by means of ammonia oxalate but can be by sodium citrate. After such a treatment the mineral loses its intergrade behaviour and acquires the behaviour of sensu stricto vermiculite. The extracting solution contains 12 mg of aluminum per gramme of clay in the studied sample.Further evidence on the nature of the aluminous vermiculites follows from microanalysis in situ. Such in situ quantitative microanalysis makes it possible to establish the structural formulae of minerals. This technique has been applied to weathering products of micas. The data obtained indicate that these weathering products are vermiculites and that one part of the aluminum must be in interlayer positions.The thermodynamic study of equilibrium between waters and aluminous vermiculites needs to be set in a multidimensional space Rⁿ. In such space the chemical composition of a water is represented by one point. Waters in equilibrium with a given mineral are situated in a (n ? 1) dimension hyperplan. For a given population of waters and minerals a program can calculate water-hyperplan distances. The use of this program shows that one part of the examined waters is compatible with the equilibrium with aluminous vermiculites.     

Phytotoxicity of organic acids as influenced by montmorillonite,hydroxy‐Al montmorillonite and phosphate fertilization

Abstract

The germination and growth of wheat seedlings were studied at pH 5.5 in liquid growth media with organic acids in concentrations ranging from 800 to 1200 ppm, before and after interaction of the organic acids with montmorillonite and hydroxy‐Al montmorillonite. Germination was not affected by the organic acids, but subsequent growth was dependent on the kind and concentration of organic acid in the growth medium. Acetic acid was more inhibitory than citric acid. Gallic acid polymerized at pH 5.5 and was phytotoxic at 1200 ppm. Interaction of organic acids with montmorillonite and hydroxy‐Al montmorillonite reduced the concentration of organic acids in solution by adsorption. Despite this reduction in concentration the phytotoxicity of the growth media was enhanced after the interaction. This was caused by the dissolution of surface Al and the effect was more pronounced in cases where hydroxy‐Al interlayered montmorillonite was the adsorbent. Additions of P as KH₂PO₄ alleviated the phytotoxicity of organic acids but not the associated Al toxicity. The amount of P lost by adsorption or precipitation was dependent on the form of Al in the growth media.     

Characterization of clay–organic-matter complexes resistant to oxidation by peroxide

In an acid soil, amounts or organic carbon resistant to peroxidation with hydrogen peroxide were strongly related to the proportions of expandable phyllosilicate (vermiculite, smectite) in the clay fraction, as measured by its K₂O content and cation exchange capacity. This was taken to indicate that a substantial part of the organic matter resistant to oxidation was interlayered. The organic compounds in the clay-organic matter complexes were identified by Pyrolysis Field Ionization Mass Spectrometry (Py-FIMS). Alkyl-aromatics as well as carbohydrates, phenols, lignins, lipids and N-compounds were found in the C-horizon sample, whereas mainly alkyl-aromatics and N-compounds, more resistant to chemical oxidation, were associated with the A₁ and B_w fine-clay fraction. This was interpreted as being due either to the evolution of the clay-associated compounds paralleling the mineralogical transformations, or to the selective adsorption of the more stable components.