Weathering of Fruchtschiefer building stones: mineral dissolution or rock disaggregation?

Building stones manufactured from contact metamorphic slates (Fruchtschiefer slate) from Theuma (Sachsen, Germany) were investigated for mineralogical alterations as well as for changes in porosity and surface roughness due to weathering. After weathering periods of several years to decades, the originally dark gray-colored slates show pale spots of several centimeters in size at the surface of building stones. The dark-colored and light-colored sections of the slate show no differences in mineralogy. Surface weathering did not result in newly precipitated minerals. It was also found that the observed differences in color are not caused by variations in sedimentary organic carbon concentration or in sulfide/sulfate concentrations. Obtained results instead indicate that dark surface sections may show a thin cover of recent organic matter (OM), e.g., living OM, soot, dirt, etc. Microscopic investigations suggested that this cover was exfoliated at light-colored surface sections. The observed disaggregation of the upper 2 mm of the building block material results in an increase in porosity. Porosity of black (unweathered) slate is <2 vol.%. Due to weathering, the slate’s pores with diameters >1 μm show a significant increase in frequency compared to the original pore size distribution. Porosity of weathered rock volumes increased to approx. 8 vol.%. Discolored surface sections show a higher surface roughness (root-mean-square roughness, Rq ~ 1 μm) compared to dark-colored slate surfaces (Rq ~ 200 nm), both data are for cleavage planes. Preferentially, the discolored surface sections are located close to the edges of cut stones. This and the alteration in porosity, pore size, and surface roughness indicate that color changes of the slate are largely influenced by rock disaggregation proceeding from the edges into the center rather than by mineral dissolution/precipitation processes.     

Variable effects of labile carbon on the carbon use of different microbial groups in black slate degradation

Weathering of ancient organic matter contributes significantly to biogeochemical carbon cycles over geological times. The principle role of microorganisms in this process is well recognized. However, information is lacking on the contribution of individual groups of microorganisms and on the effect of labile carbon sources to the degradation process. Therefore, we investigated the contribution of fungi, Gram-positive and Gram-negative bacteria in the degradation process using a column experiment. Investigations were performed on low metamorphic black slates. All columns contained freshly crushed, sieved (0.63-2 mm), not autoclaved black slates. Two columns were inoculated with the lignite-degrading fungus Schizophyllum commune and received a culture medium containing ¹³C labeled glucose, two columns received only this culture medium and two control columns received only water.The total mass balance was calculated from all carbon added to the slate and the CO₂ and DOC losses. Phospholipid fatty acids (PLFA) were extracted to investigate microbial communities. We used both the compound specific ¹⁴C and ¹³C signal of the PLFA to quantify carbon uptake from black slates and the glucose of the culture medium, respectively.The total carbon loss in these columns exceeded the amount of added carbon by approximately 60%, indicating that black slate carbon has been used. PLFA associated with Gram-positive bacteria dominated the indigenous community and took up 22% of carbon from black slate carbon, whereas PLFA of Gram-negative bacteria used only 8% of carbon from the slates. PLFA of Gram-negative bacteria and fungi were both mostly activated by the glucose addition. The added Schizophyllum did not establish well in the columns and was overgrown by the indigenous microbial community. Our results suggest that especially Gram-positive bacteria are able to live on and degrade black slate material. They also benefit from easy degradable carbon from the nutrient broth. In natural environments priming due to root exudates might consequently enhance weathering.     

渝东北黑色页岩元素迁移特征及化学风化程度

黑色页岩是富含有机质和硫化矿物的特殊沉积岩,但人们对其风化过程的元素活动性及矿物风化机制关注较少.为探讨不同地形位置的黑色页岩化学风化过程,采集了渝东北城口某山脊 (A)、近山顶 (B) 和沟谷 (C) 的下寒武统水井沱组黑色页岩风化剖面岩样,利用XRD、XRF和化学分析手段对采集样品的矿物成分、主量元素进行测定分析.元素和矿物的质量迁移系数 (τ) 和质量迁移通量 (M_{j, flux}) 的计算结果表明,黑色页岩风化过程中Ca、Mg和Na元素具有明显的贫化现象,近地表处存在Al元素的富集现象;矿物成分方面,黄铁矿和有机质氧化后形成的酸性水环境,造成方解石、白云石、斜长石等不稳定矿物溶解,并生成含水石膏、铁质氧化物、黏土矿物等次生矿物.不同赋存位置的黑色页岩风化程度有所差异,Na/K-CIA、K/Ca*-Al/Na、A-CN-K和A-CNK-FM图解显示:A剖面处于脱Ca过程的初级风化阶段,B剖面处于脱Ca、Na初期的初等-中等风化阶段,C剖面已发生脱Ca、Na过程,并伴随脱Si作用的中等-强烈风化阶段,结合不同风化指数 (如:CIA、CIW、PIA、MWPI等),得出各剖面的化学风化强弱程度依次为C＞B＞A.      

金沙江河流悬浮物与沉积物的矿物学特征及其表生地球化学意义

为研究金沙江流域表生风化特征,系统采集了金沙江和岷江流域32件河流悬浮物和河床砂样品,对其进行了矿物组成分析。结果表明,不同江段河流悬浮物、沉积物的矿物组成大致相同,以石英、方解石、斜长石和粘土矿物为主,局部有白云石、钾长石和角闪石等;粘土矿物主要有伊利石、绿泥石、高岭石和蒙脱石。河床沉积物中非粘土矿物碎屑(岩屑)含量明显高于悬浮物。伊利石为铁镁质,Kubler指数在轻微变质范围内,主要来源于三叠系碎屑岩和砂板岩。金沙江、岷江的河流悬浮物矿物组成与流域内出露的碎屑岩、砂板岩、火成岩、碳酸盐岩等的分布有较好的对应关系。河流悬浮物和沉积物的矿物组成及伊利石结晶指数特征表明流域内以物理风化为主。     

Dolomitic slates from Uruguay: petrophysical and petromechanical characterization and deposit evaluation

Slates are internationally known as roof and façade-cladding material since prehistoric times. The methods required to mine and manufacture these dimensional stones are relatively simple in comparison to those utilized in granitic dimensional stones. This has led to a worldwide rentable commercialization of slate in the last centuries and also to the development of characteristic cultural landscapes. In Uruguay several slates are mined and used in architecture, especially as façade cladding and floor slabs. The most important slates regarding their production and utilization are the dolomitic slates. These dolomitic slates are associated with the Neoproterozoic thrust and fold belt of the Dom Feliciano belt. Representative samples have been geochemically and petrographically characterized, as well as petrophysically and petromechanically analyzed. The petrophysical and petromechanical properties were investigated in a very systematic way with respect to the new European standards, showing values comparable to those registered for internationally known slates. Detailed structural and deposit analysis were carried out in Uruguay in order to evaluate the dolomitic slate deposits. The slates are linked to calc-silicate strata in a greenschist facies volcano-sedimentary sequence and the deposits are located in the limb of a regional fold, where bedding and cleavage are parallel. The main lithotype is a layered and fine-grained dolomitic slate with a quite diverse palette of colors: light and dark green, gray, dark gray, reddish and black. The mined slate is split into slabs 0.5–2 cm thick. In the past, the average production in Uruguay was around 4,000 tons/year and a historical maximum of 13,000 tons was reached in 1993 (Oyhantçabal et al. in Z dt Ges Geowiss 158(3):417–428, 2007). The oscillations in the regional demand were the cause of several flourishing and decay cycles in the activity, but our investigation shows a considerable volume of indicated resources and therefore a very good potential.     

Change of black shale organic material surface area during oxidative weathering: Implications for rock-water surface evolution

Black shale oxidative weathering plays a significant role in a variety of processes including acid mine drainage and atmospheric CO₂ control. The modeling of weathering is highly dependent on reactive surface area. In this study it is shown that black shale oxidative weathering is regulated mainly by the external, geometrical surface area of rock polyhedrons and the organic matter’s (OM) internal surface area. The internal rock surface area decreases dramatically during OM dissolution from ∼15 m²/g to ∼5 m²/g. A linear relationship was found between the decrease of internal rock surface area and quantity of OM dissolved. Optical roughness analyses of black and bleached shale surface area reveal the formation of macropores due to the dissolution of mesoporous and probably microporous OM. However, due to deconsolidation, the geometrical external rock polyhedron surface area increases during weathering. Black shale polyhedrons show a doubling of their external surface area as OM decreases. This provokes an increase of the shale volume which is easily accessible by fluids. The increase of the external rock surface area seems to be self-accelerating during weathering. The upscaling of external and internal rock surface area evolution during weathering presented in this study demonstrates the possible application of these results to the improved understanding of a chemical transport in a variety of natural systems.     

Modelling the physical and chemical changes in roofing slate caused by weathering processes

This research identifies the changes which takes place in roofing slate due to natural exposure and tries to replicate these changes experimentally. Traditional methods of testing, used by the British and other national standards, concentrate on the properties of unweathered samples and give no information on the relative durability of the different slates. Instead of concentrating on the initial properties, this research focuses on changes in the properties in order to assess durability. The effects of natural weathering were assessed by comparing old, used slates with new slates from the same or a similar source. The new slates were then weathered experimentally by repeated cycles of wetting and drying, and the increase in water absorbency compared with that observed in naturally weathering. Mineralogical differences due to both natural and experimental weathering were also measured using X-ray diffraction analysis. It was found that the effects of experimental weathering, using repeated cycles of wetting and drying, are similar to those observed in natural weathering. These include increased water absorbency and loss of crystallinity of the principal minerals. The greatest changes are found in those slates which are the most vulnerable to weathering, making it possible to identify poor quality slates.     

湘西黑色岩系沉积演化与含矿序列

研究了湘西晚震旦世-早寒武世形成黑色页岩的沉积环境和含矿性.黑色岩系形成于沉积盆地斜坡或以下地带,与海平面上升有关.晚震旦世到早寒武世早中期的沉积层序可划分为三个II级层序.海平面上升的结果使下层海水成为还原环境,有机质得以保存,沉积了大面积的黑色岩系.湘西上震旦统、下寒武统分别构成了黑色页岩 磷块岩 硅质岩组合和磷结核 重晶石 石煤 多金属富集层两个成矿系列,含矿层段集中发育于海平面上升期和凝缩层沉积中,在受海底火山、喷泉活动提供丰富物源的背景条件下,有机质参与元素的迁移、富集作用,经成岩期的转化富集成黑色岩系型矿床.     

湘西震旦—寒武纪交替时期古海洋环境的恢复

前寒武纪至寒武纪的交替时期是地质史和生命史的重要转折。中国南方地区广泛发育了上震旦统、下寒武统的黑色岩系。文中运用沉积学和沉积地球化学的理论和方法对湘西黑色岩系的岩石类型、矿物组成、元素地球化学特征、干酪根的结构以及碳同位素的组成等方面进行了研究 ,讨论了黑色岩系的形成条件 ,恢复了震旦纪 /寒武纪地史转折期的古环境。研究认为 ,湘西地区在晚震旦世和早寒武世地史转折期的生物爆发和高有机质的产率是形成缺氧环境的重要因素之一。     

锗、银、金大型超大型矿床的有机地球化学研究

锗、银、金大型超大型矿床的有机地球化学研究庄汉平（中国科学院地球化学研究所，贵阳５５０００２）关键词有机质—金属相互作用褐煤型超大型锗矿床黑色页岩型银钒矿床卡林型金矿床有机地球化学有机质—金属相互作用是有关超大型矿床基础理论研究的重要内容之一。在以往...     

Importance of porosity and transfer of matter in the rock weathering processes: two examples in central Spain

Some physical properties (bulk and free porosity, pore size distribution), and the chemical composition and mass balance of two deeply weathered profiles one developed on Hercynian granodiorite and the other on pre-Cambrian slates were studied. Hydric and mercury porosimetry, nitrogen adsorption techniques, chemical analyses and XRD techniques were used. On granodiorite, weathering has created increased porosity with a pore diameter <5 μm, whereas on slates the weathering has produced of ca. 1 μm in diameter. These pore sizes have played an important role in the weathering processes. Assuming that weathering preserves volumes, except in the uppermost part of the profiles, it brought about a loss of matter of more than 12% (~300 kg/m³) on granodiorite and ca. 30% (~800 kg/m³) on slates. These changes are related to shifts in the mineralogical evolution, with the appearance of new 2:1 and 1:1 phyllosilicates and Fe oxy-hydroxides as the main authigenic minerals. The release of matter, at least since the upper Neogene until the present, has led to the lowering of relief in a more or less homogeneous way, giving rise to gentle hillsides and flat surfaces below which the current river networks are incised. Porosity studies have the potential to explain several specific landforms as well as affecting landscape development in general.     

最近13万年来黄土高原黄土剖面中绿泥石的化学风化与古气候变迁

对黄土高原不同纬度地区的4个黄土—古土壤剖面和lO个现代土壤样品中绿泥石的化学风化进行研究，发现黄土—古土壤剖面中的绿泥石在最近13万年发生了明显的化学风化，其风化程度受剖面位置和气候控制；黄土—古土壤剖面中ω(绿泥石 高岭石)／ω(伊利石)的比值与磁化率之间具有良好的负相关关系，绿泥石的化学风化与古土壤中铁氧化物矿物的形成和磁化率的增强之间有成因联系；黄土高原现代地表样品中ω(绿泥石 高岭石)／ω(伊利石)比值与现代年平均温度和年平均降水量有着良好的相关关系。认为ω(绿泥石 高岭石)／ω(伊利石)的比值可作为新的指示夏季风变化的替代性指标，对于定量重建古气候的变迁历史具有重要意义。     

Geochemistry and mineralogy of marine and non-marine Namurian black shales from the Tansley Borehole, Derbyshire

The Namurian black shales studied have a good palaeontological control. Pyrite, illite and organic matter are higher in the marine shales, and siderite and kaolinite are higher in the non-marine shales. The distribution of the diagenetic iron minerals is attributed to anionic activities controlled by salinity. The same control could account for the observed clay-mineral distribution by differential flocculation. The major element geochemistry closely reflects the above mineral variation. Mn and Zr are higher in the non-marine shales due to siderite and zircon respectively. Co, Cr, Rb, Y and Ba are not significantly different and a detrital source, mainly clay minerals, is suggested. In the marine shales the elements Pb, Cu, V, Ni, Sr and Zn are significantly higher. Using a discriminant function analysis the palaeosalinity groups are separated and the contribution of each element to the separation is calculated. The present element locations are thought, from correlation analysis, to be pyrite and organic matter. By analogy with experimental work and modern environments, the element enrichment is mainly attributed to reactions involving organic matter and oxyhydroxide material in environments in which salinity and slow rates of sedimentation were important factors. The element enrichment cannot be related directly to seawater concentrations, unlike some black shales, and the accumulation rates for Pb and Cu are thought to be unusually high.     

Redox sensitivity of P cycling during marine black shale formation: Dynamics of sulfidic and anoxic, non-sulfidic bottom waters

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (∼15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ∼15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H₂S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ∼90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ∼15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS⁻ production.     

Geochemical study of different-aged mining dump materials in the Freiberg mining district, Germany

Historical mining dumps are useful archives for the investigation of weathering processes. The objective of this study was to investigate the weathering behavior of waste-rock material derived from the 800-year-old silver ore mining in Freiberg, Germany. For identifying time-dependent weathering indices, dumped material of four dumps of different ages and corresponding rock was examined regarding the geochemical composition. The dumped material is characterized by high contents of heavy metal containing sulfidic ores, such as pyrite, arsenopyrite, sphalerite and galena. Acid mine drainage is produced by the oxidative weathering of the sulfide minerals and causes the increased dissolving of soluble metals with increasing age of dumps. As a result of these weathering processes, a clear depletion of chalcophile elements in the older dump material (800 years) compared to the youngest dump (100 years) was observed. In the soil horizons downstream the dumps, high quantities of heavy metals (e.g., up to 12,000 ppm As, 3,300 ppm Pb, 640 ppm Zn), mainly adsorbed on organic matter, were determined and indicate a time-dependent element transfer from the dumps into their surrounding soils.     

Sodic metasomatism in a dacite weathering profile in Pinxiang, Guangxi, China

The Pinxiang weathering profile is well developed on Early Triassic dacite lavas of the Baisi Formation. At the top of the profile is developed a red clay zone which is characterized mineralogically by kaolinite, iron oxide minerals, quartz, and a small amount of illite, montmorillonite and vermiculite. In going downwards the red clay zone gives way to a saprolite zone in which plagioclase pseudomorphs have been well preserved although replaced by kaolinite. Beneath the saprolite zone is the saprock zone characterized by less weathering for dacite. At the bottom of the weathering profile is the parent material, dacite, which is composed mainly of plagioclase, quartz, K-feldspar and biotite which have been largely altered into chlorite owing to submarine extrusion of dacite lavas. Some layers in the weathering profile show obvious sodium enrichment and potassium depletion relative to others. In the Al2O3-(CaO* Na2O)-K2O triangular diagram, the weathering trends of these layers in the middle stage are remarkably deviated from normal ones. Both mineralogy and micro-morphology of these layers indicate such deviation resulted from sodic metasomatism of orthoclase.     

Weathering processes and pickeringite formation in a sulfidic schist: A consideration in acid precipitation neutralization studies

Extremely low abrasion pH values (2.8–3.3) characterize the weathering products of the Partridge Formation, a Middle-Ordovician metamorphosed, black, sulfidic shale. The local occurrence is observed of two sulfates that are rare in the Northeast: pickeringite and jarosite. X-ray diffraction studies of the weathering residues and the sulfate efflorescences have also identified dioctahedral and trioctahedral illite, kaolinite, vermiculite, and an 11–12 Å phase, thought to be a type of randomly-interstratified biotite-vermiculite. From the mineralogical studies, qualitative weathering processes for the schist are formulated. A probable mechanism for the intense chemical weathering of the schist appears to be oxidation of iron sulfides to form iron oxide-hydroxides, sulfates, and sulfuric acid. This natural weathering process is proposed as an analog to anthropogenic low pH rock weathering resulting from acid precipitation. In the Northeast,natural weathering rates, may, in places, significantly affect the water chemistry and mineralogy used to quantify total (natural plus anthropogenic) weathering and leaching rates.     

A Review of Study on Fe-C Interaction and Their Adsorption Properties to Soil Heavy Metal

Nowadays, the Fe-C coprecipitate mechanism is recognized by more and more scholars and becomes the hot topic in the environmental science. On the basis of discussing the interaction between iron oxide and organic matter, and the adsorption research progress of Fe-C complexes on heavy metals, the immobilization potential of Fe-C complexes on heavy metals in polluted soil were illustrated. The surface properties and physical characterizations of iron oxide are changed regularly with the interaction of organic matter, which lead to the higher adsorption capacity of Fe-C complexes in contrast to single iron oxide. Besides, the influences of pH values, organic matter types and surface properties of iron oxides on the adsorption capacity of Fe-C complexes on heavy metals were discussed. The excellent adsorption performance of Fe-C complexes in certain conditions will provide important theoretical basis for contaminated soil remediation.     

Geochemistry of Miocene lacustrine sediments from the Sokolov Coal Basin (Czech Republic)

Sediments of the upper part of the Sokolov Formation of the Sokolov Brown Coal Basin consist mostly of brown lacustrine clays and claystones enriched in organic matter (2–18% TOC). The lower portion of the stratigraphic profile is formed mostly by kaolinite–illite clays and claystones, while the montmorillonite content increases in the upper portion. The change in the lithology of sediments is caused by the gradual erosion of the weathering crust in the source areas of the clastic material. Inversion of the weathering profile during erosion is manifested geochemically in a decrease in the Al₂O₃/Na₂O ratio and an increase in the SiO₂/Al₂O₃, Na₂O/K₂O and K₂O/TiO₂ ratios from the base to the top of the studied part of the Sokolov Formation. The amounts of trace elements (La, Ce, Nb, Zr, Cr, V, Sn) also decrease in the same direction. On the other hand, the amounts of Rb and Sr increase. The organic matter of the upper part of the Sokolov Formation consists primarily of Types I and II kerogen. Only near the base of the studied part of the formation, i.e., in the coal stringer, kerogen of Type III prevails. The extremely low degree of thermal maturity permits determination of the source of the organic matter and characterization of its accumulation environment. The organic material in the sediments is predominantly of algae origin. Relatively high amount of pentacyclic triterpanes of the hopane series indicates either the occurrence of cyanobacteria as primary producers or bacterial reworking during sedimentation and diagenesis. Organic matter accumulated under the conditions of a fresh-water lake or lake with slightly elevated salinity, in a dysoxic aqueous environment. The alternation of organic carbon-rich layers with layers low in organic matter is explained in terms of changes in the degree of dysoxia of the aqueous environment and a variation in the intensity of oxidation and mineralization of the organic material.     

碳酸盐岩红色风化壳中的氧化铁矿物

氧化铁矿物是碳酸盐岩红色风化壳的主要矿物成分和重要结构单元。运用X射线衍射、透射电镜、扫描电镜、穆斯堡尔谱和电子探针等方法对碳酸盐岩红色风化壳中的氧化铁矿物进行了系统研究。碳酸盐岩红色风化壳中的氧化铁矿物主要有针铁矿、赤铁矿和磁赤铁矿。氧化铁矿物组合、含量和化学成分随成土环境和风化强度在剖面中呈明显的规律性变化,这为碳酸盐岩风化成土作用、红色风化壳成因与环境问题的深入研究提供了重要的矿物学依据。