Clay mineralogy, organic carbon burial, and redox evolution in Proterozoic oceans

Clay minerals formed through chemical weathering have long been implicated in the burial of organic matter (OM), but because diagenesis and metamorphism commonly obscure the signature of weathering-derived clays in Precambrian rocks, clay mineralogy and its role in OM burial through much of geologic time remains incompletely understood. Here we have analyzed the mineralogy, geochemistry and total organic carbon (TOC) of organic rich shales deposited in late Archean to early Cambrian sedimentary basins. Across all samples we have quantified the contribution of 1M and 1M_d illite polytypes, clay minerals formed by diagenetic transformation of smectite and/or kaolinite-rich weathering products. This mineralogical signal, together with corrected paleo-weathering indices, indicates that late Archean and Mesoproterozoic samples were moderately to intensely weathered. However, in late Neoproterozoic basins, 2M₁ illite/mica dominates clay mineralogy and paleo-weathering indices sharply decrease, consistent with an influx of chemically immature and relatively unweathered sediment. A late Neoproterozoic switch to micaceous clays is inconsistent with hypotheses for oxygen history that require an increased flux of weathering-derived clays (i.e., smectite or kaolinite) across the Precambrian-Cambrian boundary. Compared to previous studies, our XRD data display the same variation in Schultz Ratio across the late Neoproterozoic, but we show the cause to be micaceous clay and not pedogenic clay; paleo-weathering signals cannot be recovered from bulk mineralogy without this distinction. We find little evidence to support a link between these mineralogical variations and organic carbon in our samples and conclude that modal clay mineralogy cannot by itself explain an Ediacaran increase in atmospheric oxygen driven by enhanced OM burial.     

Quick clay—A case study of chemical perspective in Southwest Sweden

Quick clay, a soil that changes from normal firm ground to a liquid mass when it is disturbed, has been involved in most of the large and serious clay slides in Sweden, Norway and Canada. The location, time of occurrence and size of quick clay slides are difficult to predict and large slides may cause great devastation. Some geochemical studies of Swedish quick clay were done in the 1960s and early 1970s, but no systematic studies of the interrelationships of pore water chemistry, mineralogy, geotechnical properties and other parameters on quick clays in Sweden have been published. Such studies are of national and general interest because of the many combinations of rock flour source areas and sedimentation conditions that occurred across central Sweden and into the Baltic Sea area during deglaciation. In this study, geotechnical properties related to the in situ chemistry at one quick clay site were extensively studied, and spot sampling was conducted at two other locations in Southwest Sweden. In this area the clay minerals mainly are non-expanding phyllosilicate minerals (illite) and primary minerals (quartz, feldspar), which is consistent with previous studies of quick clay mineralogy. Extensive leaching has occurred at all three locations. At the extensively studied site, Surte, the lowest salinity was found at the greatest depth, inferring that the leaching by fresh water was accomplished by water movement upward and laterally through the sediment from the underlying bedrock. This is consistent with the local setting where bedrock hills rise sharply to over 100 m above the marine sediment surface. An artesian pressure would also be anticipated at this location. There is a correlation (negative) between sensitivity and salinity but there is an indication that the maximum salinity or electrical conductivity consistent with the quick clay behaviour is higher than reported elsewhere. However, for high sensitivities the salinity is about the same as reported elsewhere. In the deepest part of the borehole, there is a higher content of Fe and Al in the pore water, indicating reduced state. Further work is needed to confirm the difference in salinity and to investigate the possible interplay of salinity and potential dispersing agents such as the role of anoxic conditions, in this region. Further work is especially needed in the locations where the sediment accumulation occurred under lower salinity conditions. At all three locations, high remoulded shear strength and low sensitivity have been seen near the surface together with a decrease in pore water cation concentrations.     

Preliminary studies on the characterization of clay minerals in the Sundarban mangrove core sediments,West Bengal,India

Clay mineral found in rivers, estuaries, and marine sedimentary environments is an important group of minerals which is the by-product of chemical weathering. The main constituents of this fine-grained sediment include mudstones, clay stones, and shales. This is probably the first report of a Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) investigation on the clay minerals to characterize them in the Sundarban mangrove core sediments of Moipith Matla and Belamati Island. This study was carried out in the selected stretch for FTIR and SEM analyses. The study reveals the dominant association of kaolinite with subordinate amount of quartz, illite, and chlorite. The abundance of kaolinite, illite, chlorite, and clay with quartz helps in increasing the sediment in the island region. The geochemical and mineralogical evolution of mangrove sediment results in the interaction of biotic and abiotic parameters, whose balance is conditioned by the climate that governs the hydrologic regime, the sedimentation dynamics, and of the organic matter. This study on the characterization of clay provides substantial impact in the water-holding capacity, productivity, and mineralogical and chemical transformation in order to establish much more and intermediate equilibrium between marine influence and continental contribution, as a part of the estuarine environment.     

Characterization of clay minerals in the Sundarban mangroves river sediments by SEM/EDS

Clay minerals, byproducts of chemical weathering, are important group of minerals found in rivers, estuaries, and marine sedimentary environments, which include mudstones, clay stones, and shales. In the present study, FTIR and SEM investigation on the clay minerals in Sundarban mangrove core sediments collected from Moipith Matla and Belamati Island are carried out. The study indicated the dominant association of kaolinite with subordinate amount of quartz, illite and chlorite. The abundance of kaolinite, illite chlorite and clay with quartz helps in increasing sediment in the islands region. The geochemical and mineralogical evolution of mangrove sediments are results of the interaction of biotic and abiotic parameters, whose balance is conditioned by the climate that governs the hydrologic regime, the sedimentation dynamics and the organic matter. This study on the charaterstation of clay provides us with substantial impact in the water holding capacity, productivity and mineralogical and chemical transformation in order to establish much more and intermediate equilibrium between marine influence and continental contribution, as part of the estuarine environment, than to the tropical climate conditions.     

广西红黏土矿物成分分析

黏土矿物成分对其工程力学性质具有显著的影响。目前,在黏土矿物种类鉴定方面已有一些成熟的方法技术,而对黏土的矿物成分定量分析尚没有成熟的方法。本文基于X射线衍射试验、全化学元素分析、Bogue法和K值法,对广西武鸣、桂林两地红黏土的矿物成分进行了定性鉴定和定量分析。研究结果表明:(1)桂林、武鸣两地红黏土的主要矿物均为高岭石、三水铝石、针铁矿,桂林红黏土还含有一定量的石英。(2)武鸣红黏土的矿物成分及其含量依次为:高岭石(74.0%)、三水铝石(12.53%)、针铁矿(2mm, 2.22%)、针铁矿(2mm, 8.37%)。(3)桂林红黏土的矿物成分及其含量依次为:高岭石(56.59%)、三水铝石(11.44%)、针铁矿(15.61%)、石英(12.45%)。     

西藏北部西雅尔岗地区白垩-第三系红层的成岩作用及成岩环境

西雅尔岗地区位于羌塘高原腹地，地理范围为东经88°00′至89°00′，北纬32°40′至33°40′.大地构造位置从属于羌塘地块的玛依岗日一阿木冈基底隆断带.在晚白坚一第三纪时期，受青藏高原整沐抬升的影响，沉积了一套巨厚的红色陆屑建造，其基本特征为沉积厚度大、粗粒沉积所占比例高、沉积类型复杂、横向及纵向上相变快、岩石的颜色多为红色及紫色.沉积相类型主要为冲积扇、扇三角洲及湖泊.化石类型卖要为植物〔柏型枝)，孢粉和鸟足印化石.反映了在干操气候条件下，快速堆积的沉积特征. 根据对该区岩石学的研究，发现岩石的矿物组合和结构类型皆因成岩作用的影响而发生了很大的变化.矿物组合的变化是由于沉积后附加的陆源机械渗人粘土，在地表条件下不稳定矿物及岩屑的溶解作用以及在成岩过程中自生矿物的形成作用所造成的.导致结构类型改变的原因是(1)机械渗人的碎屑粘土及自生的粘土矿物形成孔隙间的粘土质“成岩杂基”.而这些孔隙在最初沉积时则没有杂基存在;(2)松散沉积物在成岩过程中，结构颖粒的溶解作用;(3)由于压实及压溶作用而形成粉砂级及其它细小的颗粒;(4)交代作用及重结晶作用.这些成岩过程明显地反映了整个区域岩石的演化历史. 显微镜、扫描电镜的观察以及红外光谱的侧定结果表明该区红层的形成是由于在成岩过程中赤铁矿的沉淀而造成的.在扫描电镜下可清楚地识别出赤铁矿的自生晶形.由此可以断定赤铁矿在其形成过程中显然是起了染色剂的作用.它的形成主要受孔隙水的氧化还原条件所控制，似乎于气候的关系不大，尽管它是产于干旱条件的沉积物中. 基于对该区岩石的成岩作用及成岩历史演化序列的研究，建立了该区沉积后的成岩环境模式，亦即(l)早期的表生成岩浅埋藏环境，该环境明显受到沉积环境、沉积作用控制以及气候因素的影响;(2)晚期的成岩深埋藏环境，该环境则主要受地温梯度、压力、温度和孔隙水的地球化学条件的控制.     

Sm-Nd dating of Fig Tree clay minerals of the Barberton greenstone belt, South Africa

Sm-Nd isotopic data from carbonate-derived clay minerals of the 3.22-3.25 Ga Fig Tree Group, Barberton greenstone belt, South Africa, form a linear array corresponding to an age of 3102 +/- 64 Ma, making these minerals the oldest dated clays on Earth. The obtained age is 120-160 m.y. younger than the depositional age determined by zircon geochronology. Nd model ages for the clays range from approximately 3.39 to 3.44 Ga and almost cover the age variation of the Barberton greenstone belt rocks, consistent with independent evidence that the clay minerals are derived from material of the belt. The combined isotopic and mineralogical data provide evidence for a cryptic thermal overprint in the sediments of the belt. However, the highest temperature reached by the samples since the time of clay-mineral formation was <300 degrees C, lower than virtually any known early Archean supracrustal sequence.     

黏土矿物古气候意义研究的现状与展望

系统地分析了利用海洋沉积物、古土壤、湖盆沉积物中黏土矿物进行古气候环境研究的现状、存在问题和发展趋势。海洋沉积物的物源范围广,影响因素复杂,其中的碎屑黏土矿物所指示的古气候参数只能用于解释母源区的气候变化,而只有自生黏土矿物才能指示沉积区的气候;古土壤形成于特定的地质背景条件下,尤其是发育于火山物质母岩之上的风化自生黏土矿物,可以准确地指示该区的古气候条件;湖盆沉积物的物源范围小,沉积物中的黏土矿物可以更有效地运用于古气候环境的分析。对于沉积物中黏土矿物来源的分析,可以借助晶体中cv空位和tv空位的精细结构特征进行判断;在风化改造的红土剖面研究中,因强烈的化学风化、淋滤和迁移,黏土矿物方法具有独特的优势。风化过程中形成的一些亚种或过渡性黏土矿物,以及同生沉积过程中形成的黏土矿物,对气候环境的变化更加敏感,应加强这方面的研究。此外,在造山带的气候环境演化研究中,自生黏土矿物稳定同位素可以更可靠地指示气候环境的变化。     

Composition and mineralogy of suspended sediment in the fluvio-estuarine zone of the Loire River, France

The fluvio-tidal transition of suspended sediment in terms of mineralogy and composition in the Loire River drainage basin, the largest French river basin, was investigated in the fluvial zone at Montjean and in the tidal zone at Mauves-Thouaré, for a complete seasonal cycle. At Montjean, where the river experiences unidirectional flow, the composition and mineralogy (especially clays and clay minerals) of river suspended material (RSM) are governed by the river discharge, upstream contributions, climatic conditions and microbiological activities. However, due to reversing tidal and river currents at Thouaré, in the zone of tidal dynamics, these relations are changed. In the downstream direction sand and clay content in the RSM decrease while the silt content increases. Among clay minerals, between these two observation stations, montmorillonite remains constant, kaolinite diminishes, and the other minerals increase downstream. Combustible material (organic) and nitrate (NO₃) contents in the RSM increase whereas the phosphate (PO₄^3-) and CaCO₃ contents decline considerably during transport. At the head of the tidal zone, where the river flow encounters the tidal influence, there is a relatively stationary water mass (tidal slack) where sands, clays, phosphate, carbonate and silica are deposited by physical and chemical processes. Physical sedimentation takes place by simple gravitational deposition (sands), and by sorting and complicated differential settling (clays); chemical sedimentation takes place by precipitation (calcite-CaCO₃; apatite-Ca₅ (PO₄)³ (OH,F,Cl); coagulation of dissolved silica-SiO₂) in connection with seasonal algal bloom and eutrophic events.     

Correlations between mineralogical and chemical compositions of fine stream sediments: application to geochemical exploration in tropical rain forests, Bolívar State, Venezuela

In this work we have studied stream sediments that differ in hydrodynamic energy of depositional environments and in the lithologies of source areas. The first type consists of sediment sampled in stream channels in a relatively high energy environment (samples CS); the other type is from sediments deposited laterally, along margins of channels, where stream energy decreases (samples LS). Eighteen CS samples and 36 LS samples, sieved to 230 mesh, taken from streams and rivers that drain different lithologies, were analyzed for mineralogical and chemical compositions.Samples CS and LS have different chemical compositions, although they are composed of the same minerals. CS samples have low concentrations of absorbing phases (e.g., clay and Fe-Mn oxides), low total and extractable Cu, Co, Ni and Cr, and high zircon and quartz. Conversely, LS samples have greater abundances of absorbing phases, transition elements, and lower zircon and quartz. The sample types can be discriminated by compositional differences in Zr, Si and Al.Differences in proportions of minerals of the fine sediment samples (Fe-Mn oxides, clays, quartz and zircon) result from differences in source areas and hydrodynamic characteristics of depositional sites. It is difficult, if not impossible, to collect all samples from sites with exactly the same hydrodynamic conditions or from the same source area; it is therefore necessary to classify samples according to mineralogical compositions, and to know proportions of absorber phases, clays and oxides, to the inert phase, quartz, before interpretation.     

Some quantitative indices of material composition of clay portion of rocks and their relation to weathering

Alumina :sodium, potassium :sodium, and (001):(002) ratios, as in hydromicas, increase progressively in the clay fraction of weathered crust, depending on the degree of weathering, regardless of petrographic type of the original rock. Chemical and structural changes caused by weathering are expressed also in mineralogical composition of the clay fraction. The latter relationship is obscured in clays from coastal sediments and is disturbed in marine clays, although the alumina-sodium and the other two ratios are still suited as criteria of “maturity” of the clay substance, in either case. In the case of terrigenic-chemogenic or chemogenic rocks from high-salinity sedimentation basins, neither of the foregoing criteria or relations are found to be valid, because of the masking effect of allothigenic clays. —V.P. Sokoloff.     

Particle Size Distributions of Clay-rich Sediments and Pure Clay Minerals: A Comparison of Grain Size Analysis with Sedimentation Field-Flow Fractionation

Two clay-rich coastal sediment samples have been characterised together with three pure clays identified as major components of the sediment samples. The mineralogy of the sediments was determined by X-ray diffraction, and their bulk properties measured (organic carbon content, leachable iron and manganese, surface area and cation exchange capacity). A simple approach is used to model the properties of the sediments from those of their pure clay components. Good agreement is found for cation exchange capacity and specific surface area indicating that the clay minerals are the most important constituents influencing the sediments' surface properties. Particle size distributions were assessed by conventional grain size analysis, and also by Sedimentation Field-Flow Fractionation (SedFFF). These two approaches yield sharply differing size distributions; in particular, conventional grainsize analysis indicates a much greater proportion of submicron particles. Similar results are obtained from analysis of pure clays. The most likely reason for this is artifacts introduced in the unavoidable 1 m prefractionation used for SedFFF.     

Argiles et zéolites dans l'altération d'un volcan bouclier en milieu tropical (Le Piton des Neiges,La Réunion)

The drilling of a gallery through the Roche-Écrite massif (Reunion Island) allowed to sample the old formations of the ‘Piton des Neiges’ volcano. The mineralogical study of the alteration products of the formations showed significant variations of the zeolites/clay minerals ratio depending on the location of the rocks in the volcano. The abundance of zeolites in the formation near the surface hydrographic network or the underground water drainage system seems to be due to the physicochemical processes favouring zeolites in more open systems in their competition with secondary clays. To cite this article: L. Bret et al., C. R. Geoscience 335 (2003).     

The chemistry and mineralogy of the clay fraction of sediments from the southern Barents Sea

The separated clay fraction (material <μ) of surface and sub-surface sediment samples from the southwestern Barents Sea is described. The partitioning of the major and minor elements within the different grain-size fractions of the sediment and between detrital and non-detrital phases demonstrates that the clay chemistry of these oxic shelf sediments is terrigenous in origin.The clays are a variable mixture of micaceous debris and illite with chloritic material, minor expandable clay and occasional kaolinite. Carbonate debris and amphibole occur locally. The semi-quantitative analysis suggests the existence of a considerable variation in the relative content of the principal mineralogical components and this is confirmed by the investigation of the major and minor elements. The terrigenous chemistry provides a more sensitive index of clay variability and allows the recognition of three distinct petrographic provinces.     

鄂尔多斯盆地杭锦旗地区上古生界砂岩中储层粘土矿物特征分析

鄂尔多斯盆地杭锦旗地区上古生界砂岩储层中普遍发育粘土矿物,根据岩心薄片观察,自然γ能谱测井交会图识别出的粘土矿物类型有高岭石、伊利石、蒙脱石、绿泥石。薄片分析按粘土矿物形成方式划出沉积粘土和成岩粘土(蚀变、转变及化学成因粘土),以及按其产出状态尚划出构造(骨架)粘土和结构(填隙)粘土,并定量分析出构造粘土和结构粘土含量在多数层段分别为20%以上与10%~18%。依据自然γ能谱测井分析采用多元线性逐步回归分析法,查明各粘土矿物含量同T h,U,K质量分数之间的相关系数都大于0.85,建立了粘土矿物定量计算模型X=a-b×T h c×U d×T h/K还对储层中粘土矿物进行预测及粘土矿物的纵向分布特征分析。     

The influence of particle size variations on the magnetic properties of sediments from the north-eastern Irish Sea

This paper considers the magnetic properties of a range of recent and contemporary sediments from the north eastern part of the Irish Sea. Principal component ordinations of the results show a close link between magnetic property variations and particle size. The magnetic properties of a subset of samples, particles sized by a combination of sieving and pipette analysis, confirm that variations in ferrimagnetic (‘magnetite’) grain size parallel those in particle size, despite the fact that the magnetic grains in the fine grades have diameters 1–2 orders of magnitude smaller than those of the particle size fraction in which they occur. This is best explained by postulating that the fine magnetic grains occur in the clay fraction but are present in declining concentrations in the coarser grades up to 4ø as an artefact of the pipette method. Most samples have a biomodal distribution of magnetic minerals, with a coarse mode associated with heavy minerals in the sands or coarse silts, and a fine mode in the clays. Magnetic susceptibility (x) and saturation isothermal remanent magnetization (SIRM) largely pick out the coarse mode where present; anhysteretic remanent magnetization (ARM) largely picks out the fine mode. The results open up the possibility of normalizing samples from these environments for particle size and, more specifically, clay content, by means of ARM or ARM/x values. The most likely source for the uniform and almost exclusive stable single domain magnetite, which dominates the magnetic properties of the clays, is thought to be bacterial magnetosomes. The measurements as a whole do not appear to hold much promise for discriminating sediment source types.     

Assessment of lacustrine/fluvial clays as liners for waste disposal (Lake Van Basin, Turkey)

Potential use of lacustrine/fluvial type clays in Lake Van Basin (Turkey) as liner material is investigated by studying their chemical, mineralogical and technological properties. The results show dominant clay minerals being Ca-smectite along with illite, swelling chlorite, and chlorite. Na-smectite, palygorskite, and kaolin group minerals with lesser quantities are also determined in some samples. Cation exchange capacities of samples are between 12 and 23?meq/100?g; plasticity index is between 13 and 39%; calculated hydraulic conductivity is between 2.7?×?10^?9 and 4.5?×?10^?11; volumetric swelling capacity is between 6 and 10%. It is concluded that clays in the basin have suitable properties to be used as liner materials, with some localities having better clays as liner materials than the others. The results also indicate economical potential of fluvial/lacustrine clays and highlight their important role in sustainable development of environmentally sensitive areas, among them the Lake Van Basin itself.     

Patterns of rare earth and other trace elements in Paleogene and Miocene clayey sediments from the Mondego platform (Central Portugal)

In the present study the origin of clay deposits occurring in an inland platform, in central Portugal, was investigated by their mineralogical and chemical composition. The clay deposits, exploited for ceramic industry are composed of silt-clay facies, the Monteira Member and the Arroça Member, which are assigned to the Coja Formation (Paleogene) and the Campelo Formation (Miocene), respectively. These clayey facies show almost compositional homogeneity, especially concerning texture. The mineralogical composition of the Monteira Member displays slightly higher content in smectite and interstratified clay minerals, which is supported by the chemical composition of samples analyzed. Both members present similar REE patterns, displaying an intense weathering record and little variation in the source area composition. Minor element geochemistry suggests low content in heavy minerals and transition metals. REE patterns and ratios of geochemical parameters support the dominant metasedimentary provenance, with a granite source contribution and also mature recycled sediments of continental origin. The study results’ suggest that the clays of these two members have the same source in terms of lithology and recycled sediments from the Hesperian massif. During the deposition of the Arroça Member, a major remobilization of the Monteira Member is suggested, explaining the geochemical similarity of both facies.     

Influence of the Laurentide Ice Sheet and relative sea‐level changes on sediment dynamics in the Estuary and Gulf of St. Lawrence since the last deglaciation

Physical properties, grain size, bulk mineralogy, elemental geochemistry and magnetic parameters of three sediment piston cores recovered in the Laurentian Channel from its head to its mouth were investigated to reconstruct changes in detrital sediment provenance and transport related to climate variability since the last deglaciation. The comparison of the detrital proxies indicates the succession of two sedimentary regimes in the Estuary and Gulf of St. Lawrence (EGSL) during the Holocene, which are associated with the melting history of the Laurentide Ice Sheet (LIS) and relative sea‐level changes. During the early Holocene (10–8.5 cal. ka BP), high sedimentation rates together with mineralogical, geochemical and magnetic signatures indicate that sedimentation in the EGSL was mainly controlled by meltwater discharges from the local retreat of the southeastern margin of the LIS on the Canadian Shield. At this time, sediment‐laden meltwater plumes caused the accumulation of fine‐grained sediments in the ice‐distal zones. Since the mid‐Holocene, postglacial movements of the continental crust, related to the withdrawal of the LIS (c. 6 cal. ka BP), have triggered significant variations in relative sea level (RSL) in the EGSL. The significant correlation between the RSL curves and the mineralogical, geochemical, magnetic and grain‐size data suggest that the RSL was the dominant force acting on the sedimentary dynamics of the EGSL during the mid‐to‐late Holocene. Beyond 6 cal. ka BP, characteristic mineralogical, geochemical, magnetic signatures and diffuse spectral reflectance data suggest that the Canadian Maritime Provinces and western Newfoundland coast are the primary sources for detrital sediments in the Gulf of St. Lawrence, with the Canadian Shield acting as a secondary source. Conversely, in the lower St. Lawrence Estuary, detrital sediments are mainly supplied by the Canadian Shield province. Finally, our results suggest that the modern sedimentation regime in the EGSL was established during the mid‐Holocene.