Distribution and Fluxes of Calcium Carbonatealong the Continental Margin in the Gulf of Biscay

Compositions of major components in suspended matter,collected by centrifugation, in situ pumping andsediment traps, in the Gulf of Biscay during the OMEXproject were determined and compared. The resultsshow a strong and rapid decrease in the concentrationof biogenic fraction in the upper 200 m of the watercolumn which may be attributed to the preferentialremoval of this component due to the production offaecal pellets and to the formation of marine snow. Concurrent decrease with depth of the organic andinorganic carbon contents demonstrate the importanceof the respiration of organic matter and thedissolution of calcium carbonate in the oceanic carboncycling. Lithogenic and carbonate fluxes across thecontinental slope in the Goban Spur area wereevaluated based on sediment trap records. The rate ofproduction of calcium carbonate in the surface waters(100 g CaCO3 m-2y-1), deduced from theprimary production measurements, is much largercompared to the fluxes of this component observed inthe sediment traps (5–21 g CaCO3 m-2y-1)and to its rate of burial (9–31 gCaCO3 m-2y-1). It strongly suggeststhe occurrence of carbonate dissolution, even inwaters oversaturated with respect to the mineral phaseconsidered. This is likely to be associated with therespiration of organic matter within the faecalpellets, or at the surface of biogenic calcite oraragonite     

CaCO3生物矿化的研究进展——有机质的控制作用

生物CaCO₃是自然界分布最广泛的一类生物矿物,其组成除了无机相的CaCO₃外,还含有少量的有机质,包括水可溶(SM)和水不可溶有机质(IM),SM富含阴离子基团,是控制CaCO₃结晶的重要因素之一。通过有机—无机界面分子识别,有机质选择性地与CaCO₃晶体特定方向的面网相互作用,从而对CaCO₃的生长、形貌、多型及结晶学定向等产生明显的控制作用。有机—无机界面的分子识别机制包括静电、晶格几何匹配和立体化学互补等。仿生矿化的研究为进一步深入了解生物矿化的机理及制造高级复合材料提供了新的方法。     

Stable isotope geochemistry and diagenetic mineralization associated with the Tono sandstone-type uranium deposit in Japan

The Tono sandstone-type uranium mine area, middle Honsyu, Japan is composed of Miocene lacustrine sedimentary rocks in the lower part (18–22 Ma) and marine facies in the upper part (15–16 Ma). Calcite and pyrite occur as dominant diagenetic alteration products in these Neogene sedimentary rocks. The characteristics of calcite and pyrite differ significantly between lacustrine and marine facies. Abundant pyrite, calcite, organic matter, and small amounts of marcasite or pyrrhotite occur in the lacustrine facies, whereas small amounts of calcite and framboidal pyrite, organic matter and no marcasite or pyrrhotite are found within the marine units. The δ¹³C values of calcite in the lacustrine deposits are low (−19 to −6‰ PDB) but those in marine formation are high (−11 to +3‰). This implies that the contribution of marine carbonate is larger in upper marine sedimentary rocks, and carbon in calcite in the lower lacustrine formation was derived both from oxidation of organic matter and from dissolved marine inorganic carbon. The δ³⁴S values of framboidal pyrite in the upper marine formation are low (−14 to −8‰ CDT), indicating a small extent of bacterial seawater sulfate reduction, whereas those of euhedral-subhedral pyrite in the lower lignite-bearing arkose sandstone are high (+10 to +43‰), implying a large extent of closed-system bacterial seawater sulfate reduction. The δ³⁴S and δ¹³C data which deviate from a negative correlation line toward higher δ¹³C values suggest methanogenic CO₂ production. During diagenesis of the lacustrine unit, large amounts of euhedral-subhedral pyrite were formed, facilitated by extensive bacterial reduction of seawater sulfate with concomitant oxidation of organic matter, and by hydrolysis reactions of organic matter, producing CH₄ and CO₂. Uranium minerals (coffinite and uraninite) were also formed at this stage by the reduction of U⁶⁺ to U⁴⁺. The conditions of diagenetic alteration within the lacustrine deposits and uranium mineralization is characterized by low Eh in which nearly equal concentrations of CH₄ and HCO₃ ⁻ existed and reduced sulfur species (H₂S, HS⁻) are predominant among aqueous sulfur species, whereas diagenetic alteration of the marine formations was characterized by a predominance of SO₄ ²⁻ among dissolved sulfur species. Modern groundwater in the lacustrine formation has a low Eh value (−335 mV). Estimated and measured low Eh values of modern and ancient interstitial waters in lacustrine environments indicate that a reducing environment in which U⁴⁺ is stable has been maintained since precipitation of uranium minerals. Received: 9 February 1996 / Accepted: 11 April 1997     

The solubility of calcite in seawater solutions of various magnesium concentration, It = 0.697 m at 25 °C and one atmosphere total pressure

Stoichiometric solubility constants of calcite in initially supersaturated solutions of various magnesium to calcium concentration ratios but identical ionic strength were determined at 25°C and one atmosphere total pressure.The thermodynamic solubility constant of calcite is used with ion pairing equations to interpret the data reported in this study. Results indicate that even though magnesian calcites, rather than pure calcite, precipitate from seawater solutions containing magnesium ions, the incorporation of MgCO₃ in the calcite crystal lattice does not extensively alter the equilibrium calcium carbonate activity product.The equilibrium activity of the ionic species in solution and the composition of magnesian calcite overgrowths precipitated from solutions of similar composition are used to calculate the solubility of magnesian calcites. The values for magnesian calcite solubilities obtained by this approach are lower than those obtained from the dissolution kinetics of biogenic carbonates.     

东营凹陷古近系湖相细粒混积岩沉积成岩特征

东营凹陷古近系湖相细粒混合沉积岩相类型、沉积环境和成岩演化等方面有待深入研究,利用岩心观察、薄片、X衍射和碳氧同位素等分析手段,明确了细粒混积岩相类型和沉积成岩特征.研究认为:岩石矿物组分和古生物含量的纵向变化较好地反映了沉积环境的变化和混合沉积成因过程,可作为细粒沉积层序四级界面识别标志.泥晶和亮晶方解石经历过显著的碳氧同位素分馏,证实了混积岩中泥晶方解石主要隶属于与甲烷细菌活动生成生物气有关的碳酸盐,透镜状和纹层状亮晶方解石纹层源自脉体方解石充填微裂缝,微裂缝和方解石脉集中形成于早期次干气-生油阶段.阐述了从生烃增压、微裂缝形成、有机质热演化排出有机酸、溶蚀泥晶方解石、方解石重结晶和脉体形成,直至影响临近砂体胶结作用的整个同生演化过程,对中深层页岩油气成藏研究具有重要指导意义.      

Very early diagenesis in a calcareous,organic-rich mudrock from Jordan

The diagenesis in the organic-rich Cretaceous to Eocene Al Hisa Phosphorite Formation (AHP), Muwaqqar Chalk Marl Formation (MCM) and Umm Rijam Chert-Limestone Formation (URC) formations of Jordan can be linked directly to the fluctuating sedimentary environment of this shelf depositional system in the Middle to Late Eocene, and its influence on the composition of the deposited sediment and the early burial diagenetic environment. Most cementation was early, mostly within the first 10 m of burial, perhaps entirely within the first 100 m of burial. We propose that the siliceous cements are derived from biogenic silica, probably of diatoms, deposited in a shelf of enhanced productivity. Volumetrically, the most important processes were the redistribution of biogenic opal-A (diatoms) and calcite to form pervasive, layered and nodular cements. The formation of the silica and carbonate cements is closely linked through the effects their dissolution and precipitation have on pore fluid chemistry and pH. The chert beds have a biogenic silica origin, formed through replacement of diatoms and radiolaria by opal-CT, and subsequently by quartz. Calcite cement has carbonate derived from microbial diagenesis of organic matter and calcium derived from seawater. The Mg for early dolomite may have been generated by replacement of opal-CT by quartz, ore dissolution of unstable high Mg calcite bioclasts. The silica and carbonate diagenetic processes are both linked to microbial diagenesis of organic matter, and are intimately linked in both time and space, with pH possibly influencing whether a silica or a carbonate mineral precipitates. The paucity of metal cations capable of precipitating as sulphides is crucial to the creation of acidic pore water favourable to silica precipitation, either as opal-CT, chalcedony or quartz. The lack of clay minerals as a sink for the Mg required for opal-CT polymerisation is the principal factor responsible for the remarkably early silica cementation. All the diagenetic processes, with the probable exception of the opal-CT to quartz transition are early, almost certainly within the first 10 m of burial, possibly much less. A paragenetic sequence is presented here based on these two cores that should be tested against a wider core distribution to see whether this diagenetic history can be generalised throughout the basin. Warm bottom water temperatures probably led to silica diagenesis at much shallower burial depths than occurs in many other sedimentary basins. Silicified layers, in turn, commonly host fractures, suggesting that mechanical properties of the strata began to differentiate at a very early stage in the burial cycle. This has wide implications for processes linking diagenesis to deformation.     

Calcite dissolution driven by benthic mineralization in the deep-sea: in situ measurements of Ca2+, pH,pCO2 and O2

In situ measured microprofiles of Ca²⁺, pCO₂, pH and O₂ were performed to quantify the CaCO₃ dissolution and organic matter mineralization in marine sediments in the eastern South Atlantic. A numerical model simulating the organic matter decay with oxygen was used to estimate the calcite dissolution rate. From the oxygen microprofiles measured at four stations along a 1300-m isobath of the eastern African margin and one in front of the river Niger at a water depth of 2200 m the diffusive oxygen uptake (DOU) and oxygen penetration depth (OPD) was calculated. DOU rates were in the range of 0.3 to 3 mmol m⁻² d⁻¹ and showed a decrease with increasing water depth, corresponding to an increase in OPD. The calculated amount of degradated organic matter is in the range of 1 to 8.5 gC m⁻² a⁻¹. The metabolic CO₂, released from mineralization of the organic matter drives calcite dissolution in these sediments overlain by calcite-supersaturated water. Fluxes across the sediment water interface calculated from the in situ Ca²⁺ microprofiles were 0.6 mmol m⁻² d⁻¹ for two stations at a water depth of 1300 m. The ratio of calcite dissolution flux and organic C degradation is 0.53 and 0.97, respectively. The microprofiles indicate that CO₂ produced within the upper oxic sediment layer dissolves up to 85% of the calcite rain to the seafloor. Modeling our O₂, pH and Ca²⁺ profiles from one station predicted a calcite dissolution rate constant for this calcite-poor site of 1000 mol kgw⁻¹ a⁻¹ (mol per kg water and year), which equals 95% d⁻¹. This rate constant is at the upper end of reported in situ values.     

Methane-derived high-Mg calcite submarine cement in Holocene nodules from the Fraser Delta, British Columbia, Canada

Carbonate nodules and slabs in late Holocene shelly terrigenous deposits of the modern Fraser River delta (～49°N) are formed close to the seafloor by precipitation from saline pore waters of mainly fibrous to bladed crystals of high-Mg (～ 10–20 mol% MgCO₃) calcite cement as coalescing isopachous crusts on grains. Previous reports that the cement is low-Mg calcite are not supported by this study. Highly negative δ¹³C values of ? 7 to ? 59‰ for the cements indicate that the bulk of their carbonate carbon was derived from the microbiological degradation of organic matter in the deltaic deposits during shallow burial. In particular, the production of biogenic methane (CH₄) by anaerobic bacterial fermentation, its upward migration, chemical or biological oxidation to CO₂ and neutralization in the near-surface sediment, and diffusion to microenvironments relatively enriched in organic components, are a possible set of conditions influencing the process and sites of carbonate cementation. Methane-derived Mg-calcite appears also to be the major submarine cement in several other modern occurrences of lithified shallow-water terrigenous sands and muds at non-tropical latitudes.     

Global Radiation and Onset of Stratification as Forcing Factors of Seasonal Carbonate and Organic Matter Flux Dynamics in a Hypertrophic Hardwater Lake (Sacrower See,Northeastern Germany)

A 2-year (October 2003–October 2005) high-resolution sediment trap study was conducted in Sacrower See, a dimictic hardwater lake in northeastern Germany. Geochemical and diatom data from sediment trap samples were compared with a broad range of limnological and meteorological parameters to quantify the impact of single parameters on biochemical calcite precipitation and organic matter production. Our goals were to disentangle how carbonaceous varves and their sublaminae form during the annual cycle to better understand the palaeorecords and to detect influences of dissolution, resuspension as well as of global radiation and stratification on lake internal particle formation. Total particle fluxes in both investigated years were highest during spring and summer. Sedimentation was dominated by autochthonous organic matter and biochemically precipitated calcite. Main calcite precipitation occurred between April and July and was preceded and followed by smaller flux peaks caused by resuspension during winter and blooms of the calcified green algae Phacotus lenticularis during summer. In some of the trap intervals during summer up to 100% of the precipitated calcite was dissolved in the hypolimnion. High primary production due to stable insolation conditions in epilimnic waters began with stratification of the water column. Start and development of stratification is closely related to air and water surface temperatures. It is assumed that global radiation influences the onset and stability of water column stratification and thereby determining the intensity of primary production and consequently of timing and amount of calcite precipitation which is triggered by phytoplanktonic CO₂ consumption. Sediment fluxes of organic matter and calcite are also related to the winter NAO-Index. Therefore these fluxes will be used as a proxy for ongoing reconstruction of Holocene climate conditions.     

Ca isotopes in carbonate sediment and pore fluid from ODP Site 807A: The Ca(aq)-calcite equilibrium fractionation factor and calcite recrystallization rates in Pleistocene sediments

The calcium isotopic compositions (δ⁴⁴Ca) of 30 high-purity nannofossil ooze and chalk and 7 pore fluid samples from ODP Site 807A (Ontong Java Plateau) are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor (α_s−f) between calcite and dissolved Ca²⁺ and the rates of post-depositional recrystallization in deep sea carbonate ooze. The value of α_s−f at equilibrium in the marine sedimentary section is 1.0000 ± 0.0001, which is significantly different from the value (0.9987 ± 0.0002) found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean. We hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for Ca isotope fractionation during calcite precipitation. We describe a steady state model that offers a unified framework for explaining Ca isotope fractionation across the observed precipitation rate range of ∼14 orders of magnitude. The model attributes Ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface. This model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation. The Ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly-deposited carbonate ooze is 30-40%/Myr, and decreases with age to about 2%/Myr in 2-3 million year old sediment. The recrystallization rates determined from Ca isotopes for Pleistocene sediments are higher than those previously inferred from pore fluid Sr concentration and are consistent with rates derived for Late Pleistocene siliciclastic sediments using uranium isotopes. Combining our results for the equilibrium fractionation factor and recrystallization rates, we evaluate the effect of diagenesis on the Ca isotopic composition of marine carbonates at Site 807A. Since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite, the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation. Accordingly, diagenesis produces a maximum shift in δ⁴⁴Ca of +0.15‰ for Site 807A sediments but will have a larger impact where sedimentation rates are low, seawater circulates through the sediment pile, or there are prolonged depositional hiatuses.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.     

A geochemical evaluation of perennial spring activity and associated mineral precipitates at Expedition Fjord,Axel Heiberg Island,Canadian High Arctic

Two groups of perennial springs are observed in the Canadian High Arctic at Expedition Fjord on Axel Heiberg Island at Colour Peak and Gypsum Hill. Saline discharge (∼1.3–2.5 molal NaCl) produces a variety of calcite (travertine) and gypsum-rich precipitates. Saturation index calculations of the spring waters at Colour Peak suggest CO₂ degassing from the waters causes calcite precipitation. Gypsum precipitation dominates at Gypsum Hill, where spring waters have lower alkalinity and higher SO₄ concentrations. Mineral accumulations form both channel and rimstone pool morphologies as a result of varying slope conditions. At Colour Peak, confined flow in steep slope areas develop massive structures in contrast to more friable, porous accumulations in areas where waters fan out on shallower slopes; these morphological variations lead to corresponding varying apparent rates of mineral precipitation. Mineral precipitation at Gypsum Hill is far less notable as a result of lower discharge rates and annual degradation by icing formation. Microscopic observations and geochemical analyses of the channel precipitates at Colour Peak reveal alternating light (calcite spar) and dark (anhedral microcrystalline calcite combined with organic matter and non-carbonate minerals) laminae. Rimstone pools forming in lower sections of spring discharge are composed of accumulations of large euhedral calcite crystals interbedded with allochthonous inputs. High concentration of dissolved solids is responsible for slow travertine precipitation rates, which occurs during winter. This precipitation is further retarded during summer months by the introduction of crystal growth inhibitors such as Fe³⁺ and deposition of organic matter and soil sediments.     

Mineral matter in coals and their reactions during coking

Degradation of coke in the blast furnace is influenced by its inherent mineral matter, the formation of which is itself dependent upon the nature of the coal mineral matter. To date few studies have been made of coke mineralogy and its relationship to the mineralogy of the parent coal. In this study the effect of carbonisation on coal mineral matter has been investigated by a detailed quantitative mineralogical examination of nine cokes and their parent coals. The quantitative analysis was performed on X-ray diffraction patterns of the mineral matter of cokes and coals, using SIROQUANT^™. Coke mineralogy and its composition varied strongly between cokes, more strongly than variations in elemental composition of the ash. The mineral matter in the studied cokes consisted of crystalline mineral phases and also significant levels of amorphous phase (ranging between 44 and 75%). Decomposition of clays such as kaolinite, montmorillonite, illite and chamosite produced the amorphous phase and some of the crystalline mineral phases such as mullite, γ-alumina, spinel, cristobalite and leucite. The type of association of mineral matter in coals had an important role in how the clays decomposed. For example, association of kaolinite with silica-bearing minerals in intimate intermixture favoured formation of mullite over γ-alumina. Akermanite and diopside result from reaction of kaolinite with associated calcium bearing minerals (calcite, dolomite or ankerite). Quartz, fluorapatite and the three polymorphs of TiO₂ (anatase, brookite and rutile) were the coal minerals that were least affected during carbonisation, as they were also found in the cokes, yet even they were affected in some cases.     

Discrete element modeling of shear wave propagation in carbonate precipitate–cemented particles

Bioremediation is widely used to improve ground soil by introducing calcium carbonate (CaCO₃). Shear wave velocity (Vs) is usually adopted to evaluate effect but the microscopic mechanism is unclear. The discrete element method (DEM), a promising tool for simulating the behaviors of cohesive and noncohesive materials, was used in this study to simulate Vs evolution and wave propagation path of sand reinforced by calcite precipitates. Two basic calcite precipitate forms are proposed for representing individual calcite precipitation (CaCO₃-P) and calcite aggregation (CaCO₃-C). Contact cementation between adjacent sand grain pairs was the primary association pattern for calcite precipitates at a low calcite content. At a higher calcite content, the preferential shear wave propagation pathway is the clusters cemented by CaCO₃-C. With calcite content increasing from 0 to 9%, the coordination number and average contact force increased. Vs increased from 169.73 to 2132.64 m/s but had high variability due to the spatial distribution. The results suggest that the calibrated DEM model can elucidate the microscopic mechanisms and evaluate the enhancement effect of microorganism-reinforced soil.

     

Impact of Montmorillonite and Calcite on Release and Adsorption of Cyanobacterial Fatty Acids at Ambient Temperature

Minerals might act as important sorbents of sedimentary organic matter and reduce biodegradation, which favors the formation of hydrocarbon source rocks in the earth's history. Since most organic matter is degraded during the sinking process, at ambient temperature, it is important to investigate the adsorption capacity of different minerals during this process, to assess the organic loss from primary productivity to sedimentary organic matter. In this study, montmorillonite and calcite have been selected to study the impact of different minerals on the release, adsorption, and deposition of cyanobacterial (Synechococcus elonpata) fatty acids (FAs) at ambient temperature. Gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS) have been utilized to detect the variation in fatty acids. Primary results suggest that minerals have a different impact on dissolved organic matter. Montmorillonite can specifically enhance the release of fatty acids from cyanobacterial cells by lowering the pH values of the solution. The adsorption of the dissolved organic matter by montmorillonite will also be enhanced under a lower pH value. Conjunction of fatty acids with montmorillonite to form a complex will favor the sinking and preservation of these organics. Selective adsorption is observed among fatty acids with different carbon numbers. In contrast, calcite does not show any impact on the release and adsorption of organic matter even though it is reportedly capable of acting as a catalyst during the transformation of organic matter at high temperature. The primary data bridge a link between primary productivity and sedimentary organic matter, suggesting the relative importance of claystones in the formation of hydrocarbon source rocks in the earth's history.     

Geochemical and isotopic composition of organic matter in the Kupferschiefer of the Polish Zechstein basin: relation to maturity and base metal mineralization

max vs the present depth of the Kupferschiefer, soluble organic matter (SOM) yields, and relative proportions of saturated and aromatic hydrocarbons of the SOM provide evidence for an oxidative alteration of organic matter in highly mineralized Kupferschiefer samples near the Rote F?ule zones. This is confirmed by differences in the composition of the saturated and aromatic hydrocarbon fractions of the soluble organic matter: Saturated hydrocarbons from Rote F?ule samples are dominated by short-chain n-alkanes and higher abundances of pristane and phytane relative to heptadecane (n-C17) and octadecane (n-C18), respectively, compared with samples more distant to the Rote F?ule zone. Compositional changes of the aromatic hydrocarbon fractions with decreasing distance to that zone are characterized by the occurrence of polycyclic aromatic hydrocarbons and elevated ratios of phenanthrene to methylphenanthrenes that are attributed to demethylation reactions and resulted in a decrease of the methylphenanthrene index (MPI 1). Kupferschiefer samples from the barren zone of the Polish Basin do not show these alteration patterns. The observed variations in organic matter composition with burial depth are consistent with changes due to increasing thermal maturation. Maturity assessment is achieved from MPI 1 and the methyldibenzothiophene ratio (MDR). From the relationship between the maturity of organic matter in terms of vitrinite reflectance values and depth of the Kupferschiefer strata, a continuous increase in reflectance of vitrinite is obtained within the Polish Basin. The alteration pattern of organic matter related to base metal mineralization of the Kupferschiefer corresponds to changes in the isotopic composition of organic carbon and calcite. Kerogen within, or close to, Rote F?ule zone is enriched in ¹³C caused by the preferential release of isotopically light organic compounds through progressive degradation of organic matter. The opposite tendency towards lower δ ¹³C and δ ¹⁸O values of calcite provides evidence for isotopic exchange between carbonate and the oxidizing, ore-bearing solutions and for organic matter remineralization. In contrast, organic matter and calcite from the Kupferschiefer do not show regular trends in δ ¹³C with increasing thermal maturation. Received: 25 June 1999 / Accepted: 1 December 1999     

Diagenesis of the Sedimentary Rocks Enclosing Coaly Layers in Gavatha Area,Lesvos Island,Based on Silica Polymorph‘s Transformations

A Tertiary non-marine stratigraphic sequence composed of carbonates(limestone),siliceous carbonates,coaly layers overlain by pyroclastic rocks and lavas,outcrops in the Gavatha area of northwestern Lesvos Island.Pure earbonates eonsist almost completely of calcite,the siliceous carbonate sediments of quartz,opal-CT and calcite,the shales of quartz,opal CT, K-feldspar,smecite-illite and ealcite,and the coaly layers of organic matter,quartz,opal-CT,feldspars and pyrite,Geochemical data indicate that smectite-illite,feldspars and associated elements(La,Zr,Y,Ba,Ce)are the products of alteration of volcanic rocks in a subtropical area A combination of sources in suggested for the formation of silica polymorphs:(a) biogenic or non-biogenic silica(opal-A) that was originally present in the form of diatiom frustules of in the form of inorganically prccipitated silica;(b)transformation o opall-A to opal-CT and quartz opal-C from alteration of volcanic glass of intercalated tuffites and overlying volcanics;and(c)opal-CT deposited primarily from hydrothermal solutions.     

Coupled uranium mineralisation and bacterial sulphate reduction for the genesis of the Baxingtu sandstone-hosted U deposit,SW Songliao Basin,NE China

The Baxingtu deposit is a typical redox front tabular-shaped uranium deposit hosted in sandstones of the Late Cretaceous Yaojia Formation deposited within a braided river environment during the post-rift stage of the Songliao Basin, in northeast China. This study proposes the first metallogenic model for the Baxingtu deposit and provides new data on genetic processes involved in the uranium mineralisation of sandstone-type deposits that were characterised through petrographic observations, whole-rock geochemistry, and geochemical and/or mineralogical study of iron disulphide, uranium minerals, Fe-Ti oxides (EPMA, LA-ICP-MS), and organic matter (REP). The δ³⁴S value has been measured in situ by SIMS on the different generations of iron disulphide.Within regional primary reduced sandstones, pre-ore uranium enrichment (U_mean = 7.6 ppm in whole rock) was identified on altered Fe-Ti oxides along with minor concentrations on organic matter (respectively 26.3% and 1.3% of the whole-rock U content), which together represent a significant source of uranium for the mineralisation. Additional pre-ore uranium concentrations may also be associated with clay minerals. Petrographic observations and REP data indicate that organic matter occurring in the host-sandstone is mainly inherited from land plants and corresponds to type III or type IV kerogens. Ore-stage iron disulphides largely occur as framboids and in replacement of organic matter or also as sub-idiomorphic to idiomorphic cement and crystal. Trace element signatures detected within framboids are likely indicative of formation mainly from a single event. Framboids and iron disulphide in replacement of organic matter have a light sulphur isotope signature characterised by δ³⁴S values from −72.0 to −6.2‰, suggesting that sulphur originated from bacterial sulphate reduction, which was mainly responsible for (1) the liberation of U from Fe-Ti oxides and organic matter, (2) the generation of ore-stage iron disulphides, (3) the bioreduction of uranium and (4) the production of a secondary H₂S-rich reducing barrier also involved in uranium reduction. Uranyl and sulphate ions were transported through the host sandstone by low-temperature oxygenated groundwater and U(IV) was precipitated at the redox interface as nano to microcrystals of pitchblende and coffinite, dominantly associated with bacterial substrate and as intergrowth with biogenic iron disulphide or directly associated with organic matter and residual Ti-Fe oxides. The uranium mineralisation does not replace ore-stage iron disulphides. Therefore, the combined mineralogical, geochemical, and isotopic characteristics of the Baxingtu tabular uranium deposit characterise dominantly biogenic processes for the genesis of the uranium mineralisation.     

Germanium/silica ratios in diagenetic chert nodules from the Ediacaran Doushantuo Formation,South China

Germanium/silica (Ge/Si) ratios of dolostone- and mudstone-hosted chert nodules from the Ediacaran (635–542 Ma) Doushantuo Formation in the Yangtze Gorges area, South China, are reported. These chert nodules typically have a calcite rim, a pyrite rim, and a silica core, the latter sometimes containing disseminated pyrite. The silica core was precipitated by early diagenetic replacement of carbonate and silty/muddy sediments. Two types of chert nodules are identified based on their mineralogy and geochemistry. Type-1 chert nodules are poor in disseminated pyrite in the silica core. They also have low Al, and show a strong positive correlation between Al contents and Ge/Si with a near-zero or negative intercept. In contrast, Type-2 chert nodules contain abundant disseminated pyrite in the silica core and show a weakly positive correlation between Ge/Si ratios and Al contents (with a large positive intercept on the Ge/Si axis). The Ge/Si of Doushantuo nodules are greater than those of Cretaceous deep-sea cherts, suggesting that the Ge/Si ratio of Ediacaran seawater/porewater was greater than the Cretaceous due to the more effective discrimination against Ge by inorganic opal precipitation relative to biogenic opal precipitation. The positive correlation between Ge/Si and Al can be interpreted using a mixing model with a pure chert (characterized by a low Ge/Si ratio) and an Al-rich endmember (characterized by a high Ge/Si ratio). The latter is most likely represented by a clay component, but the model-based estimate of the Ge/Si ratio inferred for the Al-rich (clay) endmember is much higher than that of Phanerozoic clay minerals. These high Ge/Si ratios for the clay endmember may be related to the generally high Ge/Si ratio of Ediacaran seawater, but could also be related to clay–organic matter interactions. Organic matter absorbed to clays could provide an additional source of Ge because certain organic molecules are known to have a high affinity for Ge due to their strong metal ion-chelating properties. The high Ge/Si ratio of the Al-rich endmember in Type-1 chert nodules suggests that Ge in porewaters from which these cherts precipitated may have been dominated by Ge–organic complexes. The low Ge/Si ratio inferred for the Al-rich endmember in Type-2 chert nodules is therefore taken to indicate that Ge was released from organic matter, perhaps due to anaerobic degradation of organic matter (accompanied by the formation of pyrite), and was redistributed between clay–organic endmembers and pure chert, resulting in a non-zero intercept in the Ge/Si vs. Al₂O₃ plots. These observations suggest that a strong terrestrial influence in a restricted sedimentary basin or a high content of dissolved organic carbon in Ediacaran seawater and porewater may have contributed to the dominance of Ge–organic complexes in the Doushantuo basin in the Yangtze Gorges area.