Bacterially-mediated authigenesis of clays in phosphate stromatolites

Authigenic clays in close textural relation to carbonate fluorapatite within finely laminated phosphate stromatolites of Upper Jurassic age have been studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and analytical electron microscopy (AEM). Stromatolite laminae consist of hexagonal prisms of francolite (sizes ranging between 0·1 and 1 μm) that are surrounded by poorly crystalline smectite and amorphous Fe–Si–Al oxyhydroxides. Microanalyses show that smectite is Fe rich, with highly variable composition, particularly regarding Fe and Si contents. Smectite has significant beidellitic, montmorillonitic and non-tronitic substitutions. Although the lack of fringe contrast in some areas adjacent to the smectite packets with 1·0–1·3 nm spacing is due to differences in orientation of layers, textural and analytical data clearly indicate the presence of Fe–Si–Al amorphous phases intimately intergrown with smectite. The occurrence of poorly crystalline smectite and associated amorphous phases within microbially precipitated stromatolite laminae, both as envelopes around, and as pore-fillings between extremely small calcium phosphate crystals, demonstrates authigenic smectite growth from a precursor Fe–Si–Al amorphous material. This material is formed in close association with a phosphate-rich precursor. The textural and structural relations, the preservation of chemical precursors of glauconite such as nontronitic montmorillonite, and the presence of Fe–Si–Al amorphous mineral phases, imply crystallization of the observed crystalline phases from synsedimentary (bacterially precipitated) amorphous precursors during early diagenesis in postoxic environments. Carbonate fluorapatite was the first phase to crystallize from the primary gel; smectite and associated amorphous Fe–Si–Al oxyhydroxides were the residual material of the crystallization process. The slow rate of transformation (at low temperatures) from Fe–Si–Al-rich gels to smectite, explains the textural relations between the poorly crystalline phases and the phosphate crystals, as well as the preservation of amorphous substances in relation to clays. Authigenic smectite represents the first step in glauconitization.     

Geochemistry and origin of ferruginous nodules in weathered granodioritic gneisses, Mysore Plateau, Southern India

Fe-nodules occur within saprolites formed from weathering of granodioritic gneisses in the rain-shadow region of the Mysore Plateau adjacent to the Sahyadri Mountains in Southern India. These nodules and their host saprolites were studied for their geochemistry, including chemical speciation, to understand nodule formation and chemical redistribution processes during rock weathering. From their mode of occurrence, and mineralogical and geochemical data, we infer that the nodules originated by a two-stage process in which the initial extensive weathering of gneisses likely facilitated subsequent ferrolysis weathering and nodule formation. Nodules originated by precipitation of goethite, hematite and gibbsite along with several amorphous phases within the matrix of weathered gneisses. This is possible only under hydromorphic conditions, suggesting that parts of the plateau must have gone through a humid phase prior to the present aridity. In the saprolites, Al, Fe, and Ti become enriched because of the removal of Si, Ca, Na, and K. However within the nodule, Fe, Ti, Cr, and Ni are deposited after their chemical transport from the saprolite. Titanium, known for its immobile nature, was also mobilized and concentrated under the conditions of nodule formation. The most important elements in the nodule constitution are Fe, Al, Ti, and Mn, each having both crystalline and amorphous phases. Fe-Ti and Mn oxyhydroxides grain coatings in the saprolites and discrete amorphous Mn and Ti phases in the nodules seem to have scavenged trace elements from the weathering profile. REE were mobilized during weathering and nodule genesis in which Ce and Ti show a strong geochemical coherence. The enrichment of only HREE in saprolite, and both HREE and LREE with significant Ce in the nodule, indicate the control of evolving secondary minerals in the REE redistribution during rock weathering. Strong enrichment of Ce in the weathering profile and in nodules has important implications to the REE chemistry of river waters.     

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.     

Lateritization cycles and their relation to the formation and quality of kaolin deposits in south Kerala, India

Laterite occurs extensively over the crystalline and sedimentary rocks in the midland and lowland areas of south Kerala, India. Two lateritization cycles are identified in this area. Large, good-quality kaolin deposits, composed mostly of kaolinite, are characteristic of the sedimentary sequence in south Kerala. These deposits were formed on deposition of the weathering materials of the khondalites towards the first cycle of lateritization. After deposition and uplift of the sedimentary rocks, another lateritization cycle affected these, as well as the khondalites during pre-Quaternary times with the formation of a planation surface at 25–125 m above sea level having thick laterite profiles. The laterite profiles over the kaolin deposits show higher concentration of Fe-oxides (mostly in the form of hematite) and titania, compared to their concentration in the kaolins. Higher contents of Cr and Ni are also characteristic of the laterite over kaolin deposits. Recrystallization of the kaolinite, appearance of Al, Fe and Si amorphous phases in the kaolin clays and partial removal of Fe and Ti from them are attributed to the second lateritization cycle.     

Mechanism of aluminum release from variable charge soils induced by low-molecular-weight organic acids: Kinetic study

The kinetic curves of aluminum release from two variable charge soils and a kaolinite within 48 h can be divided into three stages: the first stage located within the initial 30 min, at which the release rate of Al was the fastest one and the released Al dominantly originated from exchangeable Al and amorphous Al pools. The Elovich equation fit the kinetics data at this stage fairly well. The moderate and the slow stages occurred within 0.5-2 and 2-48 h, respectively. During these two stages, the released Al was mainly attributed to Al oxides, poorly crystalline kaolinite and easily weathered hydrous mica. The different linear equations also fit the kinetics data at these two stages well. The rate of Al release decreased sharply with time during the fast stage, but the rate remained constant during the moderate and slow stages. In Ultisol, Al oxides were the more important pool for Al release than poorly crystalline kaolinite and easily weathered hydrous mica during the latter two stages. In Oxisol, poorly crystalline kaolinite was the more important Al pool. Compared to the control system, the presence of organic acids increased the rate and quantity of Al release from variable charge soils. The ability of organic acids to accelerate Al release followed the order: oxalic acid > citric acid > malic acid > lactic acid. This is generally in consistent with the magnitude of the stability constants of the Al-organic complexes. The release rate of Al also increased with the rise in concentration of organic acids.     

Minéralogie et bilan de matière de l''altération supergène d''un basalte alcalin du Moyen Atlas Marocain

In the Middle Atlas of Morocco, alkali basaltic flows record successive weathering phases during the Quaternary. In fresh basalt interior and intermediate external zones, the first weathering stage is characterised by glass dissolution and the formation of a Si-Al poorly-crystallised product. Advanced weathering phases are characterised by 10 Å halloysite, kaolinite and goethite, located within the primary minerals or as secondary products in fissures. Olivine and iddingsite are transformed into Si-rich goethite, plagioclase into halloysite and pyroxene into a mixture of halloysite + geothite. Dissolution of Ti-magnetite and ilmenite yielded Ti-rich products. In these conditions, the weathering of basalts and development of a soil matrix are accompanied by the elimination of certain chemical elements, such as Si, Ca, Na and K, and the concentration of Fe and Al. In the soil, clay minerals such as illite and vermiculite, do not have any genetic relationship with weathered basalt and were probably introduced externally.     

REE fractionation and Ce anomalies in weathered Karoo dolerite

Analyses of samples from a weathering profile on Karoo dolerite allow elements to be divided into three groups depending on their behaviour. Si, K, Na, Mg, Ca, Sr, Ba and V are mobilized and removed from weathered products. Fe, Al. Ti, Zr, Hf, Zn, Cu, Sc, Co and Ni are immobile. REE, Y, and to a lesser extent Cr, are mobile and redistributed within the profile without a net loss of these elements from the profile. Large positive Ce anomalies are developed in oxidized weathered products by preferential leaching of the other REE's. Negative Ce anomalies and REE enrichment is a feature of less altered dolerite.     

云南滇池地区风化磷块岩的风化指标研究

长期风化作用使云南滇池地区形成了大面积的风化磷块岩矿石,这种矿石是制取高效磷肥的优质原料。为了圈定这些风化磷块岩矿石,须确定适宜的风化指标。笔者通过风化磷块岩形成过程化学组分变化研究,首次提出将风化指标分为“直接法”和“间接法”两类,进而提出ＣＯ２风化指标为直接法中指标,２Ｐ２Ｏ５＋Ａ．Ｉ＾１）风化指标为间接法中推荐指标。     

The weathering of norite at Black Hill,South Australia

Black Hill is a boulder‐strewn residual of norite standing 45 m above the Murray Plains about 80 km northeast of Adelaide. Between the boulders, the crystalline rock has weathered to a dark‐brown terra rossa‐rendzina soil with calcite, illite, kaolin, and hematite as the principal secondary minerals. At one site on the smooth lower slopes of the outcrop, the material above the norite consists of partially weathered granular fragments with considerable dolomite and some calcite in nodular form. Below the surface, the rock has been weathered along joints to produce the clay mineral nontronite, and between each corestone and this plastic clay there is a zone of laminated but essentially unaltered rock 10–25 cm thick. Pieces of amorphous silica occur sporadically in some joints and on the surface.

The dark‐brown soil appears to be related to the present environment but the nontronite in the joint weathering, the dolomite, and the amorphous silica are all consistent with the norite having been inundated, possibly during the Miocene marine transgression.

Calculations based on the retention of elements such as aluminium, potassium, titanium, and iron have been used to predict quantitatively the amount of certain minerals such as quartz, calcite, and dolomite introduced to the weathering profiles.     

Extent of diagenetic transformations in severely altered biogenic silica deposits from Tunisia: new insights from mineralogy and geochemistry

Sedimentary biogenic silica from Redeyef in Gafsa basin (southern Tunisia) was analysed for its ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra and complemented by X-ray diffraction and SEM observations. The ²⁹Si MAS NMR spectrum is characterized by the abundance of hydroxylated silicon, displayed in resonance intensities and reflects a clear tendency towards dissolution of diatomaceous amorphous silica and the occurrence of the hydrated silica, which is the main component that ensures the diagenetic transition via the mechanism of dissolution–precipitation to other more crystalline silica phases, after the lost of its hydroxyls groups (water) by heating (burial). ²⁷Al MAS NMR reveals two coordinations of Al; the octahedrally coordinated Al suggests the presence of clay relics trapped during crystal growth or a microcrystalline zeolite (clinoptilolite detected by SEM observations), while the tetrahedrally coordinated Al suggests the presence of minor quantities of minerals with tetrahedral Al, such as an Al-rich fluid and/or minerals such as feldspars.     

吉林东部花岗岩区地下水化学成分及其对岩石风化作用的制约

在吉林东部花岗岩区地下水化学成分和化学类型研究的基础上,以Na作为参比元素,确定了花岗岩风化过程中22种主量元素和微量元素的相对活动顺序。花岗岩区地下水的地球化学类型属低矿化度(变化范围为69.51×10-6~386.49×10-6,平均值为199.48×10-6)的HCO3-Ca和HCO3-Na-Ca型。花岗岩风化过程中元素的活动性顺序(RM)从大到小依次为:B、Ca、Mo、Zn、Sr、Na、Mg、Cr、Cu、Ni、K、Co、Li、V、As、Ba、Si、Y、Fe、Ti、Al、Mn。风化产物中的粘土矿物主要为高岭土、蒙脱石,反映出本区花岗岩的风化淋滤程度较弱的特点。     

吉林东部花岗岩风化的地球化学

描述了吉林东部花岗岩风化壳的特征。研究了花岗岩风化过程中主要造岩矿物的变化特点;建立了主要造岩矿物的风化序列。研究了主量元素、微量元素及稀土元素的地球化学行为;探讨了影响风化过程中元素行为的主要因素。计算了风化速率。     

Germanium-silicon fractionation in the weathering environment

We present a detailed study of germanium behavior in the soil weathering environment as an important step toward using the Ge/Si system as a tracer of silicate weathering processes in both modern and ancient environments. Intensely weathered soils developed on Hawaiian basalts have bulk soil Ge/Si ratios 2 to 10 times higher than fresh basalt (e.g., 10 to 25 μmol/mol vs. 2.5 μmol/mol). Soil Ge concentrations increase with Si, and decrease with Fe, suggesting that Ge sequestration is related to accumulation of secondary soil silicates, rather than retention in soil Fe oxy-hydroxides. Sequential extractions of these soils suggest that Ge/Si fractionation takes place by Ge sequestration during the initial precipitation of secondary soil aluminosilicates (principally allophane). Further Si loss and changes in mineralogy as these soils age result in little additional Ge/Si fractionation. Ge/Si ratios in granitic soils and saprolites are strongly influenced by relative weathering rates of primary minerals. Kaolinite has a Ge/Si ratio (5.9 μmol/mol) higher than the plagioclase from which it forms (3.1 μmol/mol), whereas accumulation of primary quartz (Ge/Si 0.5 μmol/mol) prevents granitic soils from attaining high Ge/Si ratios. Laboratory synthesis of allophane confirms that Ge is preferentially partitioned into the solid phase upon precipitation of secondary aluminosilicates from solution.     

岩性不均一的灰岩风化壳发育特征——贵阳花溪剖面粒度分布特征的指示

通过贵阳花溪夹泥质薄层的灰岩风化壳剖面的粒度分布特征的研究,结合矿物成分分析,揭示出岩性不均一的灰岩风化壳的发育特征: 灰岩作为剖面主体的成土母岩,风化早期,其以碳酸盐矿物的大量溶蚀及酸不溶物的残余积累为特征,同时方解石的溶解也延缓了酸不溶物的风化; 后期,随着易溶盐类消失殆尽,酸不溶物作为风化主体,开始了类似其它岩类的风化过程。而灰岩中的泥质薄层夹层,作为风化壳的次要组分,在灰岩风化过程中,由于存在巨大的体积缩小变化,泥质薄层被错断并被灰岩的风化产物所包裹,延缓了其风化发育进程。于是,各端元组分由于所处的微环境的差异,受风化溶液的影响程度不同,按照各自的风化方向和演化方式进行。随着风化程度不断增强,泥质薄片的包裹体分解,端元组分逐渐混合、趋同,风化壳趋于均质化,以统一的风化成土作用向表生稳定的矿物转变。      

Chemical alteration in the micro weathering environment within a spheroidally-weathered anorthosite boulder

A chemical and mineralogical study of the innermost rindlets of a spheroidally weathered boulder from the Wichita Mountains, Oklahoma details incipient alteration of minerals along solution channels. Alteration products in plagioclase areas are highly aluminous, whereas ferruginous residuum is commonly found in olivine alteration zones. Alteration of plagioclase along solution channels results in sharp weathering contacts as contrasted with wider zones of “limonite” bordering solution channels in olivine. In certain instances, cores of fresh olivine are surrounded by limonite indicating that diffusion may play a role in this type of alteration.Mobility of sesquioxides is evidenced by aluminum-rich debris adjacent to mafic materials in solution channels and iron-bearing material in channels cutting through plagioclase. Not resolved is whether the movement of sesquioxides in solution channels is by transport of colloidal particulates or by diffusion of dissolved species.Calcic plagioclase alters to calcite along the innermost solution channel. It is postulated that solution, exterior to the boulder and undersaturated with respect to calcite, enters the rind system via solution channels. Cut off from the CO₂ reservoir of the atmosphere by the narrow confines of this solution channel, the solution reacts with the bytownite to precipitate calcite.Apart from the occurrence of calcite, no crystalline weathering products were found in the innermost rindlet samples. A poorly crystallized illite was identified in the outermost rindlet. These findings suggest that initial alteration products on weathering rinds are amorphous and that, with time, these products attain a degree of identifiable crystallinity.     

广东惠东地区离子吸附型稀土矿床地球化学特征

摘要：运用岩石地球化学方法,对广东惠东地区离子吸附型稀土矿床的地球化学特征进行研究。结果显示,风化壳中元素含量及配分特点总体上取决于母岩,但稀土元素在继承母岩稀土元素的基础上含量进一步富集,且各风化层中元素含量变化与风化作用之间具有一定相关性。WIG指数相较于CIA指数能更有效地描述风化壳风化强度,风化壳中稀土元素迁出富集与WIG指数及元素迁移系数具有一定规律性,轻稀土元素多在全风化层上部富集,而重稀土元素在全风化层下部及半风化层明显迁入富集,Ce、Eu均具明显负异常。     

Stoichiometry of smectite dissolution reaction

The dissolution stoichiometry of smectite-rich bentonites SAz-1, STx-1 and SWy-1 was studied at 50°C and pH 2 and 3 using flow-through reactors. In addition to smectite, these samples contain considerable amounts of silica phases (quartz, cristobalite and/or amorphous silica). As a result, the molar Al/Si ratios of the bulk samples are significantly lower than those of the pure smectite.Smectite dissolution was highly incongruent during the first few hundred to few thousand hours of the experiments. Release rates of Si, Mg, Ca and Na underwent a distinct transition from an initial period of rapid release to significantly lower release rate at steady state. A reversed trend was observed for release of Al, which gradually increased from very low starting release rate to higher release rate at steady state. At steady state the ratio of released Al to released Si was found to be constant and independent of the experimental conditions. We suggest that this ratio represents the Al/Si ratio of the smectite itself, and it is not influenced by the presence of accessory phases in the sample.The rapid release of calcium, sodium and magnesium from the interlayer sites is explained by ion-exchange reactions, whereas the fast release of silicon is explained by dissolution of amorphous silica. We interpret the initial slow release of Al as the result of inhibition of smectite dissolution due to coating or cementation of the smectite aggregates by amorphous silica. As the silica is dissolved, the aggregates fall apart and more smectite surfaces are exposed, resulting in an increase in the smectite dissolution rate. Thereafter, the system approaches steady state, in which the major tetrahedral and octahedral cations of smectite are released congruently.     

The natural enrichment of ferruginous weathering products and its implication for water quality in the Hunchun Basin, China

In order to evaluate the extent of a natural enrichment of Fe and Mn over the whole of the Hunchun Basin, the stability of Fe-Mn mineral phases, their status, the weathering rate of source materials, and soil characteristics were determined. A variety of samples were collected from sediments, soil profiles, and surface soils. In the solutions after a sequentially selective dissolution using sodium pyrophosphate (p), acid oxalate (o), and dithionite-citrate-bicarbonate (d), Si, Al and Fe were dominant in the d and p fractions, and Mn in the o and p fractions. The results showed that the existing phases and status of Fe and Mn were distinctly different, and that the abundance of amorphous Mn phases made thermodynamic calculation difficult. An application of these ferruginous weathering products was therefore made to understand basin development. The first terrace of the Hunchun River is more active than the second terrace, which can be inferred from it having a higher value in Fe_d/Fe_t. Amorphous Fe phases such as Fe(OH)₃ and Fe₃(OH)₈ were controlling factors of Fe in the thermodynamic calculations. The transformation of the amorphous Fe phases to more stable phases was hindered by high contents of smectite and gibbsite, amorphous opaline produced from rice roots, and organic phosphate pesticides or fertilizers in soils. Source-rock deduction using water samples suggested granitic weathering. Precipitation around the Hunchun Basin is gradually becoming more acidic. Therefore, in the future it is inevitable that ecological and environmental problems related to the Fe phases mentioned above will occur in the drinking water supply for this area, especially in that of the first terrace.     

从岩石到土壤再到水系沉积物：风化过程的岩性地球化学基因

不活动元素的稳定性使得风化岩石、土壤和水系沉积物等风化产物能够保留新鲜母岩的元素特征,它们之间的含量变化趋势有可能从母岩传递到其风化产物中,这类似于生物学中基因遗传。仿照生物学中基因的特性提出了地球化学基因的概念及其构建方法,为了比较地球化学基因的相似程度进而提出基因相似度的概念及其计算方法。以风化过程中11种不活动元素为例,基于中国酸性岩、中性岩、基性岩的元素丰度数据构建了表征岩石及其风化产物地球化学特性的岩性地球化学基因,其元素序列为：Al2O3→SiO2→P→Ti→La→Fe2O3→Th→Zr→Nb→Y→U。利用豫西熊耳山地区安山岩风化剖面、残坡积—沟系土剖面、化探详查水系沉积物和区域化探水系沉积物4种比例尺尺度的样品对构建的岩性地球化学基因进行了检验,结果发现岩性地球化学基因在风化过程中具有很好的遗传性(从岩石到风化产物)和继承性(从土壤到其源岩),利用岩性地球化学基因可以对土壤样品进行物源示踪。源自同一母岩的水系沉积物和土壤之间在岩性地球化学基因方面具有很好的相似性(同源风化产物之间)。基于中国区域化探水系沉积物调查数据,可以构建岩性地球化学基因库来对岩石及其风化产物样品进行溯源分析,在地质、环境、法庭等科学领域具有潜在应用前景。     

云南滇池地区磷块岩的风化门限及风化磷矿的成矿模式探讨

滇池地区下寒武统磷块岩以碳酸盐类磷块岩为主。原生矿多属中低品位矿，风化后富集。磷块岩经历风化强弱可用风化成熟度来表示，风化磷块岩是风化成熟期的产物，表明矿石风化进入了风化门限之内。根据磷块岩的特点及风化磷块岩形成机制初步建立的本区风化磷块岩的成矿模式将磷块岩的风化分三个阶段，不同的风化阶段，磷块岩的风化成熟度存在明显的差异，风化磷块岩是前两个风化阶段的产物。