Crystallochemical transformation of phyllosilicates under the impact of cyanobacteria and actinomycetes

The transformation of the crystallochemical structure of phyllosilicates (vermiculite and biotite) under the impact of growing cyanobacterial and actinomycetal associations, as well as monocultures of cyanobacteria and actinomycetes, has been studied. The character of the mineral transformation depends on their crystallochemical structure and the type of biota. The most significant changes take place in the contact zone between minerals and microbial associations; the effect of microbial monocultures is smaller. The transformation of biotite proceeds via the stage of ordered mica-vermiculite (smectite) neoformation (rectorite); the destruction of vermiculite has been identified.     

含钾矿物中钾的释放及其与溶液环境中离子种类的关系

通过室内试验研究探讨5种含K矿物中K在不同溶液中的释放规律(释放量和释放速率).结果表明,不同含K矿物中K释放速率和释放量的顺序均表现为:黑云母>蛭石>金云母≥白云母>钾长石,不同K矿物释K速率在酸溶液中差异最大,其次在钙和钠盐溶液中,在水中的速率差异最小,这主要是受其矿物本身结构的影响.不同离子对含K矿物中非交换态K释放的促进作用差异显著:H~+>>Ca~(3+)>Na~+>H_2O>NH_4~+.随矿物K有效性增加,H~+和Ca~(2+)对矿物K释放的促进作用越大,而且H~+较Ca~(2+)对黑云母、金云母和长石中的K有更突出的促释作用.此外,Ca~(2+)较Na~+显著促进了黑云母和蛭石中K的释放,但对其他矿物中K释放的影响两者无显著差异.NH~+_4则显著抑制了各种矿物中K的释放,对黑云母和蛭石的抑制作用更强于对金云母和白云母的作用.     

富钾植物籽粒苋(Amaranthus spp.)对土壤矿物钾的吸收利用研究

运用土培、石英砂培、有机酸释钾实验及矿物X衍射分析研究了不同基因型籽粒苋(Amaranthusspp.)对土壤矿物钾的吸收利用及其机制。结果表明,籽粒苋能有效地利用土壤和云母(黑云母和金云母)中的钾;籽粒苋品种R104、CX4对钾的吸收量高于一般型品种(CX77);籽粒苋根系能引起云母矿物向蛭石转化;籽粒苋根系分泌物中的草酸比一般有机酸具有更高的释放矿物中钾素的能力。     

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.     

四苯硼钠溶液中含钾矿物非交换态钾的释放特性研究

含钾矿物的全钾含量、非交换态钾总量以及非交换态钾的释放速率因矿物种类而异,且3种参数之间没有必然的相关性。供试5种含钾矿物非交换态钾总量由高到低的顺序是:金云母 5.19% 黑云母3.08% 蛭石2.01% 白云母1.18% 钾长石0.24%,占各矿物全钾的比例分别为:58.4% 、99.7% 、62.5% 、14.2% 和4.98% ,平均达48%。选择较弱提取力的四苯硼钠溶液进行非交换态钾的释放特性研究,5种矿物非交换态钾3d释放累积量顺序为:黑云母 蛭石 金云母 白云母 钾长石;非交换态钾平均释放速率也表现为同样的顺序。上述5种矿物在弱提取力的四苯硼钠溶液中释放3 d,非交换态钾的平均释放速率分别为5.99、2.34、0.52、0.22和0.17 mg/(kgmin),差异明显。如何根据非交换态钾的释放量和释放速率来综合评价矿物钾的生物有效性是未来研究中需要明确的问题。     

Influence of pH on the formation of the hydroxy Al-montmorillonite complex

The presence of so-valled chlorite-like minerals has been reported in many soils of not only acid but also of alkaline reaction (1). The minerals have been designated by, many terms, for example, dioctahedral vermiculite (2), dioctahedral analogue of vermiculite (3), 14A mineral (4), chlorite-like mineral (5), interstratified chlorite-vermiculite (6), intergradient chlorite-expansible 2:1 layer silicate, intergradient chlorite-vermiculite, intergradient chlorite-vermiculite-montmorillonite, intergrade, or interlayered vermiculite (7), and 2: 1-2: 2 intergrade (1). The minerals designated by these terms are evidently of the same category, and some of them are synonymous. Although they are of intermediate properties, between true chlorite and true vermiculite or montomorillonite, they could be regarded as an independent group of minerals in the course of pedochemical weathering. Jackson (1), for instance, has given the minerals the position of “weathering index 9”, placing them between vermiculite and kaolin as equivalent to montmorillonite, or secondary chlorite and kaolin in his weathering sequence. An explanation of the diagenesis of the minerals has been recently attempted by synthesis of the chlorite-like structures from montmorillonite (8), (9) and vermiculite (10) and mineralogical analyses of soil clay fractions (7).     

Fixation of radiocaesium traces in a weathering sequence mica → vermiculite → hydroxy interlayered vermiculite

Radiocaesium fixation in soils is reported to occur on frayed edge sites of micaceous minerals. The weathering of mica in acid soils may therefore influence the Cs⁺ fixation process and thereby the mobility of the radiopollutant. We produced a laboratory weathering model biotite → trioctahedral vermiculite → oxidized vermiculite → hydroxy interlayered vermiculite (HIV) and quantified the Cs⁺ fixation of each mineral both in a fixed K⁺–Ca²⁺ background and in acid conditions. The transformation process was achieved through K depletion by Na-tetraphenylboron, oxidation with Br₂ and Al-intercalation using NaOH and AlCl₃. In a constant K⁺–Ca²⁺ background, vermiculite fixed 92–95% of the initial ¹³⁷Cs⁺ contamination while biotite and HIV fixed only 18–33%. In acid conditions, the interlayer occupancy by either potassium (biotite) or hydroxy-Al groups (HIV) strongly limited Cs⁺ fixation to 1–4% of the initial ¹³⁷Cs⁺ contamination. Cs⁺ fixation occurred on vermiculitic sites associated with micaceous wedge zones. Though both oxidized and trioctahedral vermiculites fixed similar Cs⁺ amounts in a constant K⁺–Ca²⁺ background (92–95%), the oxidized vermiculite retained much more radiocaesium in acid conditions (78–84% against 54–59%), because of its dioctahedral character.     

A stepwise change of frayed edge site content in biotite in response to the gradual release of potassium from the interlayers

ABSTRACT

Radiocesium (RCs) is selectively adsorbed on weathered micaceous minerals (mica) in soils. Although it is clear that weathered mica has selective adsorption sites for RCs, which have been called ‘frayed edge sites (FES),’ the relationship between the degree of mica weathering and the FES content has not been fully investigated. To evaluate the effect of mica weathering on its FES content, we investigated the changes in the FES content with the release of K⁺ from biotite samples by using sodium tetraphenylborate solution. The FES content was estimated from radiocesium interception potential. The vermiculitic layer charge (Vt charge) was also determined as an indicator of the degree of mica weathering. The amount of K extracted from biotite increased from 154 to 803 mmol kg^?1 as the condition of the K extraction was more intensive (i.e., longer time, lower solid/liquid ratio, and higher temperature). As K⁺ was removed to a greater extent, the FES content increased from 3.96 to 11.5 mmol kg^?1, whereas the Vt charge value increased from 17.1 to 329 mmol kg^?1. At the earlier stage of mica weathering, the formation of FES was proportional to the increasing amount of K⁺ released and to the Vt charges. However, at the later stage of mica weathering, when vermiculite was detected by an X-ray diffraction analysis, FES was not necessarily increased in proportion to the increase in K⁺ released and the amount of Vt charge. These findings indicated that although mica weathering largely increased the FES, the increase was not continuous throughout the weathering stage but evident at the earlier stage of weathering.     

Transformation of Trioctahedral Mica in the Upper Mineral Horizon of Podzolic Soil during the Two-Year-Long Field Experiment

An experiment on transformation of biotite (fraction <1 μm) particles placed into containers with different permeability in the AEL horizon of podzolic soil was performed in order to estimate the contribution of different factors to the transformation of biotite in the modern soil. After two-year-long incubation in the AEL horizon, biotite was transformed into vermiculite, mixed-layer biotite–vermiculite, and pedogenic chlorite. The most intense vermiculitization of the biotite took place under the impact of fungal hyphae and, to a lower degree, fine plant roots and components of the soil solution. The formation of labile structures from biotite was accompanied by thinning of the mica crystallites, the disturbance of the homogeneity of layers, the removal of interlayer K, the removal and oxidation of octahedral Fe, the increase in the sum of exchangeable cations, and the appearance of exchangeable Al. The process of chloritization was definitely diagnosed upon the action of plant roots and fungal hyphae on the biotite. Strong complexing anions released by fungal hyphae partly inhibited chloritization. Chloritization led to a decrease in the cation exchange capacity of vermiculitic structures.     

Comparison of silicate minerals as sources of potassium for plant nutrition in sandy soil

Given the cost of conventional fertilizers and increasing demand as a result of increasing population growth, new sources of potassium (K) for plant nutrition need to be considered. Readily soluble nutrients are rapidly lost from well‐drained soils, and so it is appropriate to consider silicate minerals that release K slowly during weathering. In this paper, we compare the availability to plants grown in sandy soils of K from microcline (feldspar), biotite (mica) and nepheline syenite (nepheline + microcline) using leek (Allium ampeloprasum var. porrum L.) as a model plant. Pot experiments were carried out under controlled environmental conditions using natural and artificial soil. The performance of the minerals was compared with treatment with KCl and a negative control (no K added). Plant shoot diameter was measured weekly to assess growth rates. After 10 weeks, plant dry mass and soil and plant contents of soluble K were measured to determine offtake; mineralogical changes in biotite‐treated soils were assessed. Results for artificial and natural soil differed, reflecting differences in their mineralogy. With no added K, plant growth ceased after 2 weeks. Growth rates were greatest for KCl, followed by biotite; linear growth continued for 5 weeks in the natural soil and for the entire 10 weeks in the artificial soil. Growth rates with nepheline syenite (natural soil) and microcline (both soils) did not differ significantly from the negative control, but for nepheline syenite, leek shoot K content was significantly greater, demonstrating availability of K from this source. X‐ray diffraction analysis showed that biotite reacted to form vermiculite.     

Nonexchangeable potassium extraction and associated structural changes of mica dominant clay minerals

Abstract

Six mica dominant soils representing a landform sequence were used for the present investigation. The effect of extraction of nonexchangeable potassium (K) by boiling 1 M HNO₃ treatment and its associated structural changes of micaceous clay minerals was studied by employing x‐ray diffraction technique. Potassium release was rapid in the first three extractions and slowed down to a constant rate thereafter in all the clay samples. The first extraction contributed about 45.57–62.69% towards the total K release. The calculated values of rate constant (first order) decreased sharply from 0.065–0.025 min^‐1 after third extraction and reached a constant value thereafter. The calculated integral width of first order reflection of mica peak (10Å) decreased considerably with nitric acid treatment, but no such effect was observed in 5Å peak. The differential x‐ray diffraction (DXRD) traces showed that the HNO₃ treatment dissolved finer particles of mica particularly trioctahedral component and mixed layer minerals, smectite, chlorite and vermiculite.     

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.     

中国土壤中粘粒矿物的分布规律

土壤粘粒部分的组成和性质在土壤发生学及土壤肥力特性的研究中都占很重要的位置。过去认为土壤粘粒中的无机物都是非晶形的,自从伦琴射线衍射应用到土壤学研究中后,大家都公认土壤粘粒部分含有晶形结构的矿物。     

Mineralogy of a podzol formed in sandy materials in northern denmark

This paper deals with possible mineralogical changes from one particle size fraction to another and from one horizon to another in a Typic Haplorthod. X-ray diffraction and chemical analysis were the main methods used. The investigation indicates that a large part of the fine material in the soil is developed during weathering in situ. Less resistant minerals seem to be protected by being parts of rock fragments in coarser fractions, but once freed from that protection they quickly undergo fragmentation into finer particles. Most of the sand and silt fractions are quartz. The K-feldspar content ranges between about 10 and 20%, the Na-feldspar content from about 15 to 30% and the Ca-feldspar content is very small. The clay minerals are mostly kaolinite and mica and in the A2 horizon, expandable 2:1 minerals containing both smectite and vermiculite layers. The B horizon contains 14 A minerals that resemble interstratified vermiculite—chlorite. In the C horizon both vermiculite—chlorite and clorite occur.     

Transformation of micas of various crystal chemistry under influence of cyanobacteria and actinomycetes association

The ability of experimental cyanobacteria and actinomycetes associations to change the structure of micas has been revealed. It was noticed that the rates of mineral transformation depend on their crystalchemical composition??the structure of biotite??trioctahedral mica that transformed sustainably under the influence of cyanobacteria and actinomycetes association??s growth, which was detected by the emergence of mixed-layered biotite-vermiculite formation in the fraction sample. In the case of dioctahedral mica??muscovite??the significant transformational changes under the influence of association has not been revealed. The symmetry and high clearness of mineral reflexes after the association??s growth indicates a high tolerance of muscovite to biological weathering.     

Desorption and Transformation of Nitroaromatic (TNT) and Nitramine (RDX and HMX) Explosive Residues on Detonated Pure Mineral Phases

Explosive compounds, including known toxicants 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), are loaded to soils during military training. Their fate in soils is ultimately controlled by soil mineralogical and biogeochemical processes. We detonated pure mineral phases with Composition B, a mixture of TNT and RDX, and investigated the fate of detonation residues in aqueous slurries constructed from the detonated minerals. The pure minerals included Ottawa sand (quartz and calcite), microcline feldspar, phlogopite mica, muscovite mica, vermiculite clay, beidellite (a representative of the smectite clay group), and nontronite clay. Energy-dispersive X-ray spectrometry, X-ray diffraction, and gas adsorption surface area measurements were made of the pristine and detonated minerals. Batch slurries of detonated minerals and deionized water were sampled for 141?days and TNT, RDX, and TNT transformation products were measured from the aqueous samples and from the mineral substrates at day?141. Detonated samples generally exhibited lower gas adsorption surface areas than pristine ones, likely from residue coating, shock-induced compaction, sintering, and/or partial fusion. TNT and RDX exhibited analyte loss in almost all batch solutions over time but loss was greater in vermiculite, beidellite, and phlogopite than in muscovite and quartz. This suggests common phyllosilicate mineral substrates could be used on military training ranges to minimize off-site migration of explosive residues. We present a conceptual model to represent the physical and chemical processes that occurred in our aqueous batches over time.     

Radiocesium interception potential (RIP) of smectite and kaolin reference minerals containing illite (micaceous mineral) as impurity

Cesium-137 (¹³⁷Cs) is strongly adsorbed on clay minerals, especially on illite. The adsorption of Cs⁺ on reference clay minerals, however, has not been fully investigated in relation to the presence of illite. The objective of this study was to clarify the effect of impurities (i.e., illite and vermiculite), present in reference smectite group minerals and kaolin minerals, on the retention of Cs⁺. The clay mineralogy of the reference minerals was characterized by X-ray diffraction (XRD). The radiocesium interception potential (RIP) was measured as an index of the Cs⁺ retention ability of clays. The content of illite in clay was represented by the total potassium (K) content given that illite is a major source of K in the clay fraction. The content of vermiculite in clay was represented by the Cs fixation capacity induced by Cs saturation followed by heating of samples at 110°C. Metabentonite and beidellite gave extremely high RIP values compared with other smectite group minerals, although a peak for illite (at 1.0 nm) was not observed in XRD analysis. The reference smectite and kaolin minerals showed a range of RIP values, even though their RIP values are theoretically zero. The RIP values had a significant positive correlation with the total K content of all the reference clay minerals (r_s = 0.621*). This indicated that the retention ability for ¹³⁷Cs depended more on the content of illite, as impurity, rather than the type of bulk mineral. Hence, the contribution of illite to the magnitude of the RIP was elucidated by the combination of measurement of total K content and XRD analysis.     

贡嘎山海螺沟冰川退缩区土壤序列矿物组成变化

阐明土壤中矿物随时间变化的机制是理解矿物风化和土壤发育的基础。利用X射线衍射法对贡嘎山海螺沟冰川退缩区土壤矿物组成随成土作用时间变化进行了定量分析。结果表明,冰川退缩区成土母质的矿物组成同质性较高,以硅酸盐矿物为主(约90%),包括:斜长石(28.5%)、石英(24.5%)、黑云母、钾长石、普通辉石、角闪石、绿泥石、蛭石;并有少量碳酸盐矿物,如方解石(8%)、白云石(2.3%);以及磷酸盐矿物磷灰石(2.1%)。退缩区土壤的矿物组成总体呈新发育土壤特征,随着成土年龄的增加,方解石逐渐被风化成为草酸钙石,角闪石、黑云母、磷灰石和绿泥石含量逐渐降低,长英质矿物的相对含量有所增加。成土作用中矿物组成的变化受植被原生演替和土壤p H的影响,快速发育的植被导致土壤p H迅速降低,风化程度增强。     

Biotite weathering in podzolic soil under conditions of a model field experiment

The biotite changes in the 1–5 μm fraction after its occurrence in the F, H, AE, and E horizons of a pale-podzolic soil for five years under conditions of a model field experiment were assessed by X-ray diffraction analysis. It was found that the main changes of the biotite in all the horizons included the degradational transformation of its crystal lattice to interstratified mica-vermiculite structures and vermiculite. The intensity of this process gradually decreased from the F horizon down the profile in parallel with the decrease in the amount of roots and the abundance and activity of microbiota. Chloritized structures were present among the products of the biotite weathering in the H, AE, and E horizons; the degree of chloritization gradually increased from the H horizon to the E horizon. The main identified products of the biotite weathering in the AE and E horizons formed during the 5 years of the model experiment were identified in the clay and fine-silt fractions from these horizons of the native pale-podzolic soils. Therefore, the vermiculite, soil chlorite, and mixed-layer illite-vermiculite minerals in the soils studied could be considered as products of the recent soil functioning. The obtained results and literature data showed that the weathering of biotite resulted in the formation of K- and Al-buffer systems.     

Smectite formation produced by weathering in a coarse granite saprolite in Galicia (NW Spain)

Weathering of a calcalkaline granite was studied in the south of Galicia (NW Spain) where the average annual precipitation is 1400 mm and the average annual temperature is 12°C. The original rock contains perthitic K-feldspars, plagioclases with inclusions of muscovite and opaque minerals, quartz and chloritized biotite, with apatite, zircon, sphene and opaques as accessories. In the saprolite the structure of the rock is preserved, the plagioclases show up to grade 4 weathering and the biotites, between 2 and 3. Weathering in quartz and potassium feldspar crystals is manifested only by fracturing. Biotite changes following the parallel linear model and its weathering products are interstratified biotite–vermiculite and iron oxyhydroxides. The plagioclases change to a microgranular material by pseudomorphic transformation. This material, which substitutes the plagioclase, includes small clearly delimited units which retain zones with the optic characteristics of muscovite. X-ray diffraction analyses of microsamples show that they are formed by 1:1 diocthaedral phyllosilicate, smectite and a small quantity of mica. From these facts we concluded that smectite is formed inside the plagioclase crystals, and probably originates from the inclusions of muscovite contained in these crystals, as it is suggested by the microscopic study which shows the increase in volume which occurs when the crystals of muscovite are transformed.