Primary versus diagenetic origin of Blue Lias rhythms (Dorset, UK): evidence from sulphur geochemistry

The question of a primary versus diagenetic origin for the limestone-shale rhythms of the Blue Lias has been addressed through a study of pyrite abundance and isotopic composition. Pyrite is relatively abundant and isotopically light in the central portions of the bioturbated limestones as compared to adjacent, less calcareous, sediment. The abundance of pyrite shows that the limestones were a focus for prolonged sulphate reduction and pyrite formation. The isotopic data indicate that bioturbation oxidized some pyrite to produce isotopically light sulphate, part of which was subsequently reduced back to pyrite before preservation by burial. Acidity generated by pyrite oxidation was buffered in the limestones by carbonate dissolution, hence supersaturation of sulphides could be maintained. By contrast, in adjacent less calcareous sediments, carbonate dissolution was unable to buffer acidity and bioturbational oxidation of pyrite formed iron-rich pore solutions. Continued sulphate reduction in the limestones acted as a sink for iron from the adjacent sediments and, with burial below the zone of bioturbation, the alkalinity so generated caused cementation of the limestones. Diagenetic cementation would be enhanced during an hiatus in sedimentation, an event which might be related to a Milankovitch forcing mechanism, but which would not be recorded in bioturbated, less calcareous sediment, thus leaving an imperfect record. Only cyclicity in pre-diagenetic sedimentation patterns may be safely related to a Milankovitch forcing mechanism as proposed by Weedon.     

Burial of organic carbon and pyrite sulfur in sediments over phanerozoic time: a new theory

In present day marine sediments, almost all of which are deposited in normal oxygenated seawater, rates of burial of organic carbon (C) and pyrite sulfur (S) correlate positively and bear a constant ratio to one another (C/S ～- 3 on a weight basis). By contrast, calculations, based on the isotopic model of Garrels and Lerman (1981), indicate that at various times during the Phanerozoic the worldwide burial ratio must have been considerably different than the present day value. This ratio change is caused by the requirement that, increases in the worldwide mass of organic carbon must be accompanied by equivalent decreases in the mass of sedimentary pyrite sulfur, in order to maintain a roughly constant level of O₂ in the atmosphere. Such apparently contradictory behavior can be explained if the locus of major organic carbon burial has shifted over time from normal marine environments, as at present, to non-marine freshwater, or to euxinic environments, in the geologic past. A shift to predominantly freshwater burial can help explain predicted high C/S ratios in Permo-Carboniferous sediments, and a shift to euxinic environments can help explain predicted low C/S ratios during the early Paleozoic. It is demonstrated that the three environments today exhibit distinguishably different average C/S ratios.     

Early diagenesis of the lower Vectis Formation,Wealden Group Lower Cretaceous,Barremian), Sandown,Isle of Wight

The Vectis Formation was deposited in a restricted lagoonal environment that periodically dried up, as indicated by the presence of desiccation surfaces. The fauna indicates that salinities fluctuated significantly during deposition, from fresh to brackish-marine. Pre-burial berthierine-rich clay replaced faecal pellets in the sediment, infilling desiccation cracks, during re-flooding of the lagoon. Concretions formed by early pyrite and apatite cementation during initial burial in lake sediment, with organic debris of fish and wood, acting as nuclei and a trigger for cementation. With subsequent partial or complete exhumation oxidation of the pyrite occurred, prior to cementation by Mn siderite. All further concretion cementation occurred within the oxic to sub-oxic diagenetic zones. Textural relationships indicate that commonly occurring baryte formedafter pyrite oxidation and represents the last diagenetic mineral phase.     

The carbon and sulfur cycles and atmospheric oxygen from middle Permian to middle Triassic

The results of a theoretical isotope mass balance model are presented for the time dependence of burial and weathering-plus-degassing fluxes within the combined long-term carbon and sulfur cycles. Averaged data for oceanic δ¹³C and δ³⁴S were entered for every million years from 270 to 240 Ma (middle Permian to middle Triassic) to study general trends across the Permian-Triassic boundary. Results show a drop in the rate of global organic matter burial during the late Permian and a predominance of low values during the early-to-middle Triassic. This overall decrease with time is ascribed mainly to epochs of conversion of high biomass forests to low biomass herbaceous vegetation resulting in a decrease in the production of terrestrially derived organic debris. Additional contributions to lessened terrestrial carbon burial were increased aridity and a drop in sea level during the late Permian which led to smaller areas of low-lying coastal wetlands suitable for coal and peat deposition.Mirroring the drop in organic matter deposition was an increase in the burial of sedimentary pyrite, and a dramatic increase in the calculated global mean ratio of pyrite-S to organic-C. High S/C values resulted from an increase of deposition in marine euxinic basins combined with a decrease in the burial of low-pyrite associated terrestrial organic matter. The prediction of increased oceanic anoxia during the late Permian and early Triassic agrees with independent studies of the composition of sedimentary rocks.Weathering plus burial fluxes for organic carbon and pyrite sulfur were used to calculate changes in atmospheric oxygen. The striking result is a continuous drop in O₂ concentration from ∼30% to ∼13% over a twenty million year period. This drop was brought about mainly by a decrease in the burial of terrestrially derived organic matter. but with a possible contribution from the weathering of older organic matter on land. It must have exerted a considerable influence on animal evolution because of the role of O₂ in respiration. Some examples are the extinction of many vertebrates, loss of giant insects and amphibians, and the restriction of animals to low elevations. It is concluded that the extinction of plants may have contributed to the extinction of animals.     

THE PROBLEM OF UNDERSTANDING THE NOMENCLATURE OF FACIES

Chert-plus-pyrite pebbles have been known for some time in a number of Witwatersrand conglomerates, but their distribution is highly variable. A wide variety of textures in chert-plus pyrite pebbles are documented here, and these textures place constraints on the origin of such pebbles. Replacement of chert pebbles by pyrite is indicated (pyrite grains and aggregates continue across many pebble boundaries), and both distributional and textural evidence favors a post-burial timing for this process. Significant mobility of sulfur after burial is indicated. Whether this replacement was diagenetic or metamorphic is not certain.     

The geochemistry of concretions from the Kimmeridge Clay Formation of southern and eastern England

Concretions from the Kimmeridge Clay Formation are of three types: calcareous concretions, septarian calcareous concretions and pyrite/calcite concretions and nodules, which occur within different mudstone facies. Isotopic and chemical analysis of the concretionary carbonates indicate growth in the Fe-reduction, sulphate-reduction and decarboxylation zones. The septarian concretions show a long and complex history, with early initiation of growth and development spanning several phases of burial, each often resulting in the formation of septaria. Growth apparently ceased in the transitional zone between the sulphate-reduction and the methanogenesis zones. Very early growth in the Fe-reduction zones is also seen in one sample. The non-septarian concretions began growth later within the sulphate-reduction zone and have had a simpler burial history while the pyrite/calcite concretions show carbonate cementation in the sulphate-reduction-methanogenesis transition zone. A ferroan dolomite/calcite septarian nodule with decarboxylation zone characteristics also occurs. Development of concretions appears to be indirectly controlled by the sedimentation rate and depositional environment, the latter determining the organic matter input to the sediments. Calcareous concretions predominate in swell areas and during periods of low sedimentation rate in the basins with poor organic matter preservation and deposition of calcareous mudstones. Pyrite/calcite concretions occur in organic-rich mudstones deposited under higher sedimentation rates in the basins, while the ferroan dolomite nodule grew under very high sedimentation rates.     

The copper-silver occurrences of Rahmani,Western Sahara,Algeria

The copper-silver occurrences of Rahmani (Western Sahara, Algeria) are located in paleochannel facies of Cambrian sandstones deposited onPan-African volcanics and intrusives. Sulfur isotope analyses were performed on pyrite and copper sulfides in order to trace the origin of the copper-silver mineralization. S isotopic data preclude that bacterial reduction of Cambrian sulfate could have induced the formation of the sulfides. Non-bacterial reduction of sulfate during burial diagenesis is the most valuable explanation for disseminated pyrite. Isotopic ratios on copper sulfides indicate that they result from the reaction of actual or subactual sulfate-bearing surface water with the disseminated pyrite. The origin of copper and silver remains unclear. They are thought to be brought by the downward migrating surface water but their origin could be either the leaching of the Cambrian sandstones or of the weathered volcanics.     

埋藏环境中硫酸盐岩生物岩溶作用的硫同位素证据

为了揭示油气盆地埋藏环境中碳酸盐岩和硫酸盐岩共生时的岩溶发育机制, 以硫酸盐岩为研究对象, 采用室内模拟实验与野外实测资料相结合的方法, 分析了温度、SO₄2-浓度和时间等因素对水-岩-细菌封闭系统内稳定硫同位素的影响, 并指出硫同位素对地球化学作用的指示意义.结果表明, 细菌硫酸盐还原形成的H₂S中硫同位素分馏明显, 并受系统的温度和开放性等因素影响.结合鄂尔多斯盆地奥陶系风化壳中充填的黄铁矿硫同位素特征, 提出了鄂尔多斯盆地奥陶系岩溶的生物成因模式; 揭示了风化壳顶部的黄铁矿化与风化壳下部压释水岩溶共生的机制, 建立了生物岩溶发育的硫同位素地球化学标志.研究成果拓宽了岩溶的压释水成因机制.      

Vitrinite recycling: diagnostic criteria and reflectance changes during weathering and reburial

The aim of this study was first to review or even identify reliable diagnostic criteria to distinguish recycled and autochthonous vitrinite particles and, second, to examine and try to explain the impact of weathering and reburial on optical changes (reflectance) of recycled material. The work was based on indigenous and recycled particles of two sample sets from two wells drilled in the Senegalese margin basin and the Ardèche paleomargin (SE France), respectively. In addition to reflectance measurements, the studied samples have also been analysed by Rock-Eval pyrolysis. For both sample sets, hydrogen index (HI) and oxygen index (OI) values suggest a type III organic matter of dominant terrestrial origin.Two main diagnostic criteria appear particularly useful to identify indigenous and recycled vitrinite particles: the first is the clear genetic relationship between telinite and collotelinite; the second is the presence of pyrite framboid inclusions in indigenous vitrinite. The pyrite–vitrinite association illustrates the relationship between sulphate reduction, pyritisation, and in situ organic matter transformation through gelification process. However, application of both diagnostic criteria requires some additional information about depositional conditions (i.e., anoxicity) and thermal maturity of the studied samples. Weathering has no or only very limited effect on vitrinite reflectance. During their new burial history, recycled vitrinites follow a reflectance evolution path close to that of inertinites and thus appear as transitional materials between vitrinite and inertinite macerals. Consistently, this behaviour implies that recycled vitrinite reflectance changes during burial diagenesis do not solely depend on their chemical composition but, most probably too, on combined chemical and structural changes inherited from their past burial history and from the impact of weathering during their recycling stage.     

沉积地层中的黄铁矿形态及同位素特征初探——以华南埃迪卡拉纪深水相地层为例

地质历史时期新元古代大气氧含量普遍较低。在硫酸盐还原细菌作用下,作为海洋重要的氧化性离子,陆源硫酸根离子有效促进了深层海水的氧化进程。在此过程中,硫元素在硫酸根和黄铁矿之间发生显著同位素分馏,其分馏程度可反推当时古海洋的氧化还原状态。沉积地层中的黄铁矿普遍具有多种形态,不同形态黄铁矿的形成环境多有不同。如草莓状黄铁矿多形成于底层缺氧水体或沉积物的浅表面,而大颗粒单晶黄铁矿或脉状黄铁矿则多沉积于成岩早期的沉积物孔隙或形成于成岩后期的热液改造。与草莓状黄铁矿不同,大颗粒单晶或脉状黄铁矿的硫同位素组成并不能反映沉积时期的古海洋氧化还原条件。判定沉积地层中不同形态的黄铁矿及形成过程,是获得有效反映海洋沉积环境硫同位素组成特征的基本前提。简要总结了地质历史时期沉积地层中的黄铁矿类型及矿物形成过程,并以华南埃迪卡拉纪蓝田组岩芯样品为例,识别出各个样品中的黄铁矿形态组成特征,对比分析了全岩黄铁矿与样品中大颗粒黄铁矿硫同位素组成差异。研究结果表明:不同岩性样品中黄铁矿的形态种类及含量均存在差异。页岩样品保存有更好形态的自形晶以及草莓状黄铁矿;碳酸盐岩样品中具有较多自形晶以及他形晶黄铁矿,并且其中的少量草莓状黄铁矿遭受后期成岩作用而发生不同程度的晶体蚀变。样品中大颗粒黄铁矿的硫同位素值（δ34S_L-pyr）通常显著高于全岩黄铁矿的硫同位素值（δ34S_T-pyr）,最大差值可达48.5‰。在利用黄铁矿的硫同位素组成来反推当时古海洋环境时,需要区分不同形态黄铁矿,仔细剔除大颗粒黄铁矿,降低成岩期黄铁矿对样品中硫同位素组成的影响。更细致的微区黄铁矿硫同位素分析工作将依赖于SIMS分析测试手段进行。     

桂西北明山卡林型金矿床热液矿物的显微组构与化学成分特征及其对成矿作用的指示

桂西北明山金矿是滇黔桂地区代表性的卡林型金矿之一,矿体受平行于区域性断裂右江断裂的北西西向次级断层控制,赋存于二叠系灰岩之上的中三叠统钙质细砂岩、碳钙质泥质粉砂质岩中。地质、岩相学特征和阴极发光、背散射电子影像、电子探针等分析研究表明,明山金矿发育了3个成矿阶段的热液矿物组合,不同热液矿物普遍具有多世代的特点。热液矿物中见有波状消光、带状消光、毕姆纹、压溶劈理、位错滑移等韧性剪切带粒内应变特征,坑道中也见有黄铁矿石英脉发生韧性变形、又被后期石英脉切断的现象,说明矿床经历了多次的脆-韧性变形。不同矿化期（阶段）的黄铁矿中Au和As的含量表明:沉积期黄铁矿Au、As的含量较低;成岩期黄铁矿中Au的含量高但As含量不高;而成矿期3个阶段的热液黄铁矿中都含较高的As和Au;热液黄铁矿核部包裹的交代残余黄铁矿Au、As含量较高,但变化范围较大,可能是变质成因。紧邻矿体的围岩中成岩黄铁矿从中心向外Au和As的含量逐渐降低,说明其中的As和Au在后来的构造和（或）热液事件中发生了活化迁移,越靠近颗粒边缘元素的活化迁移越强,这表明成矿物质来自于围岩。根据这些事实,推断明山矿区可能在成岩期发生了金的预富集,变形变质早期富含有机质的变质流体活动又使As发生了富集,主变质期流体的广泛渗透交代、活化出先存含金富砷黄铁矿中的Au和As,形成成矿流体。当成矿流体遇到富含活性铁的炭钙质泥质粉砂岩时,形成黄铁矿的同时发生Au的沉淀。     

Arsenic in framboidal pyrite from recent sediments of a shallow water lagoon of the Baltic Sea

Arsenic is a redox‐sensitive element of environmental relevance and often enriched in iron sulphides. Because sediments from the Achterwasser lagoon, a part of the estuarine system of the river Oder, south‐west Baltic Sea, show unexpectedly high pyrite concentrations of up to 7·5 wt% they were used to investigate the influence of authigenic pyrite on the mobility and burial of As in the coastal environment. Micro‐X‐ray‐fluorescence measurements of 106 micrometre‐sized pyrite framboids from the anoxic sediments show highly variable As concentrations ranging from 6 to 1142 μg g^?1. Even within a 1 cm thick layer, the As concentration of different framboids varies greatly and no clear depth trend is visible throughout the 50 cm long sediment core. Pyrite can account for 9 to 55% (average 22%) of the total As budget of the sediments and the degree of trace metalloid pyritization for As ranges from 26 to 61%, indicating that authigenic pyrite formation is an important process in the geochemical cycling of As in coastal sediments. High‐resolution micro‐X‐ray fluorescence mapping of single pyrite grains shows that As is distributed inhomogeneously within larger framboids, suggesting changing pore water composition during pyrite growth. X‐ray absorption near edge structure spectra indicate that As is usually present as As(‐I) substituting S in the pyrite lattice. However, in samples close to the sediment/water interface a considerable part of As is in higher valence states (+III/+V). This can be explained by frequent re‐suspension of the surficial sediments to the oxic water column due to wave action and subsequent re‐deposition, leading to the adsorption of As oxyanions onto pyrite. Although reduced As(‐I) becomes more important in the deeper samples, reflecting decreasing redox potential and a longer time since deposition, the occurrence of oxidized As species (AsIII/AsV) in pyrite in the anoxic part of the sediment suggests formation under dysoxic conditions.     

Burial Records of Reactive Iron in Cretaceous Black Shales and Oceanic Red Beds from Southern Tibet

One of the new directions in the field of Cretaceous research is to elucidate the mechanism of the sedimentary transition from the Cretaceous black shales to oceanic red beds. A chemical sequential extraction method was applied to these two types of rocks from southern Tibet to investigate the burial records of reactive iron. Results indicate that carbonate-associated iron and pyrite are relatively enriched in the black shales, but depleted or absent in red beds. The main feature of the reactive iron in the red beds is relative enrichment of iron oxides （largely hematite）, which occurred during syn-depostion or early diagenesis. The ratio between iron oxides and the total iron indicates an oxygen-enriched environment for red bed deposition. A comparison between the reactive iron burial records and proxies of paleo-productivity suggests that paleo-productivity decreases when the ratio between iron oxides and the total iron increases in the red beds. This phenomenon could imply that the relationship between marine redox and productivity might be one of the reasons for the sedimentary transition from Cretaceous black shale to oceanic red bed deposition.     

基于共生金属硫化物硫同位素分馏程度约束热液活动温度：以川中下寒武统龙王庙组为例

硫循环及硫同位素(δ³⁴S)分馏研究对地表圈层的成岩作用具有重要意义,其中多种金属硫化物中硫同位素的分馏程度可以约束成矿热流体温度,进而作为地温计证据约束热液活动。四川盆地龙王庙组储集层内的热液改造影响着该储集层的非均质性,本研究着重讨论目的层中与热液成因白云石所伴生的黄铁矿(FeS₂)-黄铜矿(CuFeS₂)成矿现象：基于详尽的岩石学证据,应用纳米二次离子探针(NanoSIMS)对金属硫化物内部硫同位素分布进行测定,并基于热力学驱动下的硫化物间平衡分馏程度计算其成矿温度,进而约束层段内热液活动过程。研究发现：(1)微区硫同位素分布显示黄铁矿(FeS₂)与黄铜矿(CuFeS₂)沉淀过程中不仅存在热力学分馏,还存在动力学分馏现象,其中动力学分馏程度可以达到40.1‰,应用NanoSIMS微区测定手段可以有效剔除动力学分馏数据影响,获取热力学平衡分馏数据;(2)黄铁矿(FeS₂)与黄铜矿(CuFeS₂)成矿过程或利用不同的硫源,其中黄铁矿...     

Evaluating the S-isotope fractionation associated with Phanerozoic pyrite burial

This study examines the sulfur isotope record of seawater sulfate proxies using δ³⁴S and Δ³³S to place constraints on the average global fractionation (Δ³⁴S_py) associated with pyrite formation and burial and the exponent λ that relates variations of the ³⁴S/³²S to variations of the ³³S/³²S. The results presented here use an analysis of the sulfur isotope record from seawater sulfate proxies and sedimentary sulfide to extract this quantity as the arithmetic difference between δ³⁴S of seawater sulfate and contemporaneous sulfide. It also uses an independent method that draws on inferences about the Δ³³S evolution of seawater sulfate to evaluate this further. These two methods yield similar results suggesting that Δ³⁴S_py and λ changed over the course of the Phanerozoic from slightly lower values of Δ³⁴S_py (lower values of λ) in the early Phanerozoic (Cambrian-Permian) to higher values of Δ³⁴S_py (higher values of λ) starting in the Triassic. This change of Δ³⁴S_py and the exponent λ is interpreted to reflect a change in the proportion of sulfide that was reoxidized and processed by bacterial disproportionation on a global scale. The revised record of Δ³⁴S_py also yields model pyrite burial curves making them more closely resemble model evolution curves for other element systems and global sea level curves. It is suggested that possible links to sea level may occur via changes in the area of submerged continental shelves which would provide additional loci for pyrite burial.The slightly different constraints used by the two approaches to calculate this fractionation may allow for additional information to be obtained about the sulfur cycle with future studies. For instance, the correspondence of these results suggests that the inferred variation of ³⁴S/³²S of pyrite is real, and that there is no significant missing sink of fractionated sulfur at the resolution of the present study (such as might be associated with organic sulfur). Burial of organic sulfur may, however, have been important at some times in the Phanerozoic and shorter timescale deviations between results provided by these methods may be observed with higher resolution sampling. If observed, this would suggest either that the record for pyrite (or less likely sulfate) is biased, or that another sink (possibly as organic sulfur) was important during these times in the Phanerozoic.     

华南李家沱剖面寒武纪纽芬兰世海水氧化还原性质演化及其驱动因素

大气-海洋含氧量的演化对埃迪卡拉纪-寒武纪转折期的后生动物大爆发事件具有重要影响.为探讨寒武纪纽芬兰世中国南方海洋氧化还原性质的演化及其初级生产力、海水硫酸盐浓度等演化驱动因素, 分析了李家沱剖面纽芬兰世留茶坡组和小烟溪组微量元素、有机碳含量、有机碳同位素、总硫含量、黄铁矿硫同位素等.该剖面沉积于斜坡-盆地环境且出露齐全.该剖面上V/Sc、Th/U及Mo、U、V、Ni、Cu等元素的富集系数呈现出5个变化旋回, 其中留茶坡组中上部和小烟溪组中部各存在一氧化环境段, 其余层段处于缺氧环境, 而Re/Mo则显示仅在小烟溪组中部水体出现过短暂的氧化环境和含有游离H₂S的硫化环境, 其余层段处于没有游离H₂S的缺氧非硫化环境.Ba、Ni、Cu、Zn、Cd等微量元素的富集系数及TOC表明: 留茶坡组的有机质沉降量和埋藏量都明显小于上覆小烟溪组; 而在小烟溪组中, 其中部有机质的沉降量和埋藏量最低, 下部最高, 上部次之.TOC/TS、TS以及黄铁矿硫同位素的垂向演化趋势等都显示李家沱剖面纽芬兰世大都处于低海水硫酸盐浓度环境.低海水硫酸盐浓度是造成李家沱剖面纽芬兰世缺氧水体未富集游离H₂S的主要原因.大气含氧量的升高是导致李家沱剖面小烟溪组中部出现短暂氧化环境以及近硫化环境的主要原因.      

Cycles of nutrient trace elements in the Phanerozoic ocean

Availability of nutrients in the ocean can be a major factor affecting bioproductivity, burial of carbon and release of oxygen. However, the nutrient trace element (TE) composition of the palaeo-ocean cannot be measured directly. Here we present a comprehensive global dataset on the TE content of marine sedimentary pyrite in black shales, dating back 700 million years, and demonstrate a systematic cyclic evolution of pyrite TE composition with time. The nutrient TE, molybdenum, selenium, cadmium and thallium measured in pyrite, and phosphorus measured on whole rock, rise sharply at 560 to 550 Ma followed by several cycles of TE variation through the Palaeozoic and into the Mesozoic. A number of factors could explain the trends. We suggest that variations in continental uplift, erosion and nutrient flux rates were possible drivers of the oceanic nutrient cycles. The cyclic patterns through the Phanerozoic suggest periods of nutrient-rich oceans that fostered key evolutionary events, followed by nutrient-poor oceans that encompass several major mass extinction events.     

Occurrence and morphology of pyrite in Bulgarian coals

Coals with different degrees of coalification (ranging from lignite to anthracite) from seven Bulgarian coal basins have been investigated. The forms of pyrite and their distribution have been established. The types found are: massive pyrite, represented by the homogeneous, cluster-like and microconcretionary varieties; framboidal pyrite, appearing in inorganic and bacterial forms; euhedral pyrite, which is either isolated or clustered; anhedral pyrite, in its infilling and replacement varieties; and infiltrational pyrite, as a replacement or infilling mineral.Most of the forms of the euhedral, framboidal and massive pyrite developed during peat deposition. The anhedral replacement pyrite formed in the peat bed during early diagenesis. Infiltrational pyrite filled fractures and cleats formed during the diagenesis, catagenesis and metagenesis.Both similarities and differences with respect to the distribution of the pyrite types have been determined between coals of different ranks from Bulgarian coal basins. These differences are due to: the presence of Fe and S in the rocks adjacent to ancient peat bogs; the activities of ground and surface waters which brought Fe and S into the peat bogs; the geochemical character (pH and Eh) of the peat bogs and the sulphur bacteria development; and the tectonic situation during diagenesis, catagenesis and metagenesis.     

Covariance of C- and O-isotopes with magnetic susceptibility as a result of burial diagenesis of sandstones and carbonates: an example from the Lower Devonian La Vid Group,Cantabrian Zone,NW Spain

The burial diagenesis of sandstones, limestones, and dolostones of the Lower Devonian La Vid Group in the Cantabrian Zone (NW Spain) reveal a covariance of carbon and oxygen isotope values with magnetic susceptibility. Also, strontium isotopes, and to a minor degree Fe, follow this trend. The main carriers of the magnetic susceptibility appear to be diagenetic Fe-carbonates, i.e., siderite, ferroan dolomite, and ankerite, which occur as cements in primary and secondary voids, as well as in fractures. In some layers, especially at the top of the succession there occurs additionally secondary Fe-chlorite and pyrite. The Fe-carbonates were formed during upward migration of a reducing, iron-bearing, petroliferous fluid that was depleted in ¹³C and carried radiogenic Sr. Similar geochemical covariance and/or correlations can be expected in other sedimentary successions affected by the migration of petroliferous formation fluids.     

黑色页岩水岩化学作用实验研究

水岩作用是黑色页岩化学风化的重要途径,并与岩体矿物组分、工程性质及地质环境有着密切的联系。利用自制的流通实验装置对取自三江县团结电站附近的寒武系清溪组黑色页岩与富含溶解氧去离子水的化学反应进行试验模拟研究,并利用离子分析仪、电感耦合等离子体质谱仪对反应后溶液离子浓度进行分析,使用扫描电子显微镜观察反应前后岩样微观特征,结合岩样渗透系数的变化监测,对岩样中黄铁矿氧化动力学速率以及受黄铁矿氧化影响形成的酸性环境下硅元素释放速率进行计算分析。结果表明,黄铁矿氧化行为使得岩体渗透率降低约70%,在黑色页岩自身矿物化学组分和岩石物理性质的共同影响下,所含黄铁矿氧化速率与纯黄铁矿颗粒的氧化速率非常接近,同时黄铁矿氧化形成的酸性溶液可溶蚀岩体中石英和伊利石,由于两者含量未能精确测定,因此所测得硅元素释放速率仅表示两者溶解的总反应速率。