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1.
通过对碳酸锰氧化实验的结果分析和讨论，建立了一种适合于锰氧化过程的非平衡热力学模型，并利用此模型对硫酸锰氧化过程作了热力学可行性分析，研究结果表明，碳酸锰氧化过程是矿物组合的变化过程，也是锰自身价态的转为过程，整个过程既存在平衡状态，又存在非平衡状态，是一个不可逆的，多相的复杂反应。 相似文献
2.
Manganese oxides precipitated by bubbling air through 0.01 molar solutions of MnCl2, Mn(NO3)2, MnSO4, or Mn(ClO4)2 at a constantly maintained pH of 8.5 to 9.5 at temperatures of 25°C or higher consisted mainly of hausmannite, Mn3O4. At temperatures near 0°C, but with other conditions the same, the product is feitknechtite, βMnOOH, except that if the initial solution is MnSO4 and the temperature is near 0°C the product is a mixture of manganite, γMnOOH and groutite, αMnOOH.All these oxides are metastable in aerated solution and alter by irreversible processes to more highly oxidized species during aging. A two-step nonequilibrium thermodynamic model predicts that the least stable species, βMnOOH, should be most readily converted to MnO2. Some preparations of βMnOOH aged in their native solution at 5°C attained a manganese oxidation state of +3.3 or more after 7 months. Hausmannite aged at 25°C altered to γMnOOH. The latter is more stable than a or βMnOOH, and manganese oxidation states above 3.0 were not reached in hausmannite precipitates during 4 months of aging. Initial precipitation of MnCO3 rather than a form of oxide is likely only where oxygen availability is very low.Composition of solutions and oxidation state and morphology of solids were determined during the aging process by chemical analyses, X-ray and electron diffraction and transmission electron micrographs. 相似文献
3.
James W Murray John G Dillard Rudolf Giovanoli Harald Moers Werner Stumm 《Geochimica et cosmochimica acta》1985,49(2):463-470
The initial solid phase oxidation products formed during the oxidation of aqueous Mn(II) at 25°C were studied as a function of time. The analyses included morphology (TEM), mineralogy (x-ray diffraction), ratio (iodometric method), oxidation state of manganese (XPS), and dissolved manganese. The initial solid formed under our conditions was Mn3O4 (hausmannite) which converted completely to γMnOOH (manganite) after eight months. βMnOOH (feitknechtite) appeared to be an intermediate in this transformation. The ratio was initially 1.37 and increased to 1.49 over the same time span. Throughout the course of this study the XPS analyses showed that the surface of the solids (<50 Å) was dominated by Mn(III). The solution pH and dissolved manganese concentrations were consistent with disproportionation and oxidation reactions that favor the transformation of Mn3O4 to γMnOOH but not to γMnO2. 相似文献
4.
B. Pomerol 《Cretaceous Research》1983,4(1):85-93
In the North Atlantic DSDP/IPOD cores, carbon isotope data on the bulk carbonates show significant fluctuations. In sediments now exposed on land coeval fluctuations in the carbon isotope concentrations are also recorded in pelagic and epeiric facies. For instance, in the Upper Cretaceous chalks of the Paris Basin, there is a major break at the Cenomanian-Turonian boundary. At this time, the manganese content of the chalks was also at a maximum and consequently a positive relation can be demonstrated between δ13C and manganese concentrations. The same positive correlation is also recorded in many pelagic limestones.In the North Atlantic cores, carbon isotope events are related to the black shale facies and to global oceanic anoxic events and one can suppose that in sediments deposited on the continental margins they are also related to mildly anoxic conditions. Considering the manganese geochemistry in carbonate rocks, a high manganese content in such a reducing environment can be found in the sediments only if the Mn concentration of the interstitial solutions are abnormally high. As a high Mn content in marine pore waters is believed to originate from hydrothermal process, Mn and δ13C positive excursions are ultimately related to mid-oceanic ridge activity and to a closely connected phenomenon, the great transgressive pulses during which mid-depth waters may have been anoxic. Consequently, major Mn and carbon isotope events would seem to be useful tools in paleooceanographic reconstructions. 相似文献
5.
Manganese carbonate deposits in Japanese Jurassic sedimentary rocks were studied petrogeochemically. The deposits are characteristically composed of spheroidal micronodules, up to 1 mm in diameter, and always contain well-preserved radiolarian shells. Chemical elemental composition and mineralogical characteristics indicate that the micronodules contain rhodochrosite in a mixed carbonate phase composition (Mn86.7?92.2Ca2.2?2.9Mg2.6?6.7Fe2.6?5.6)CO3 Carbon and oxygen isotope values, which range from ?7.99 to ?4.78‰ and ?4.05 to 0.28‰ relative to PDB, respectively, suggest that the manganese carbonate was precipitated in a suboxic zone. The micronodules closely resemble agglutinated benthic foraminifera in shape. We suggest that agglutinated foraminiferal tests composed of radiolarian shells accumulated selectively on the sediment surface during redeposition of bottom sediments and were replaced by manganese carbonate in suboxic diagenetic conditions of manganese reduction. 相似文献
6.
碳酸盐矿物的阴极发光特征与其成分有关。笔者用阴极发光与电子探针微区分析法对砂岩中碳酸盐矿物进行测试分析 ,其结果表明碳酸盐矿物的阴极发光与微量元素含量有如下规律 :①碳酸盐矿物在铁含量高于猝灭下限或锰含量低于激活下限时 ,不具有阴极发光性 ;②铁的猝灭下限约为 0 0 4mol,锰的激活下限为小于 7× 10 - 5mol;③铁 /锰比值越高 ,越不利于碳酸盐矿物阴极发光 ;但是铁 /锰比值小于 1的碳酸盐一定具有阴极发光 ;④铁或锰二者之一含量很少时不利于碳酸盐矿物的阴极发光。 相似文献
7.
Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn47.7 Ca45.1 Mg7.2) CO3. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations. 相似文献
8.
Claudia L. Caldeira Virginia S.T. Ciminelli Kwadwo Osseo-Asare 《Geochimica et cosmochimica acta》2010,74(6):1777-1789
The mechanism of pyrite oxidation in carbonate-containing alkaline solutions at 80 °C was investigated with the help of rate experiments, thermodynamic modeling and diffuse reflectance infrared spectroscopy (DRIFTS). Pyrite oxidation rate increased with pH and was enhanced by addition of bicarbonate/carbonate ions. The carbonate effect was found to be limited to moderately alkaline conditions (pH 8-11). Metastable Eh-pH diagrams, at 25 °C, indicate that soluble iron-carbonate complexes (FeHCO3−, FeCO30, Fe(CO3)(OH)− and FeCO32−) may coexist with pyrite in the pH range of 6-12.5. Above pH 11 and 13, the Fe(II) and Fe(III) hydroxocomplexes, respectively, become stable, even in the presence of carbonate/bicarbonate ions. Surface-bound carbonate complexes on iron were also identified with DRIFTS as products of pyrite oxidation in addition to iron oxyhydroxides and soluble sulfate species. The conditions under which thermodynamic and DRIFTS analyses indicate the presence of carbonate compounds also correspond to those in which the fastest rate of pyrite oxidation in carbonate solutions was observed. Following the Singer-Stumm model for pyrite oxidation in acidic solutions, it is assumed that Fe(III) is the preferred pyrite oxidant under alkaline conditions. We propose that carbonate ions facilitate the electron transfer from soluble iron(II)-carbonate to O2, increase the iron solubility, and provide buffered, favorable alkaline conditions at the reaction front, which in turn favors the overall kinetics of pyrite oxidation. Therefore, the electron transfer from sulfur atoms to O2 is facilitated by the formation of the cycle of Fe(II)-pyrite/Fe(III)-carbonate redox couple at the pyrite surface. 相似文献
9.
Chemical analyses were performed on soil water extracted from two cores taken from a sandy calcareous soil near Delhi, Ontario. Calcite saturation is attained within the unsaturated zone over short distances and short periods of time, whereas dolomite undersaturation persists to the groundwater table. The progressive dissolution of dolomite by soil water, within the unsaturated zone, after calcite saturation is reached results in calcite supersaturation.Deposition of iron and manganese oxyhydroxide phases occurs at the carbonate leached/unleached zone boundary. This is a result of soil water neutralization due to carbonate dissolution during infiltration but may also reflect the increased rate of oxidation of dissolved ferrous and manganous ions at higher pH's. The role of bacteria in this process has not been investigated.The depth of the carbonate leached/unleached zone boundary in a calcareous soil has important implications for 14C groundwater dating. The depth of this interface at the study site (?2 m) does not appear to limit 14C diffusion from the root zone to the depth at which carbonate dissolution occurs. Thus, soil water achieves open system isotopic equilibrium with the soil CO2 gas phase. It is calculated that in soils with similar physical properties to the study soil but with depths of leaching of 5 m or more, complete 14C isotopic equilibration of soil water with soil gas would not occur. Soil water, under these conditions would recharge to the groundwater exhibiting some degree of closed system 14C isotopic evolution. 相似文献
10.
GERNOT ARP CHRISTIAN OSTERTAG‐HENNING SELÇÜK YÜCEKENT JOACHIM REITNER VOLKER THIEL 《Sedimentology》2008,55(5):1227-1251
Fossil stromatolites may reveal information about their hydrochemical palaeoenvironment, provided that assignment to a specific microbial community and a corresponding biogeochemical mechanism of formation can be made. Tithonian stromatolites of the Münder Formation at Thüste, north Germany, have traditionally been considered as formed by intertidal cyanobacterial communities. However, thin sections of the stromatolites show elongated angular traces of former gypsum crystals in a dense arrangement, but no algal or cyanobacterial filament traces. Moreover, high Fe2+ and Mn2+ contents, oxygen‐isotope and sulphur‐isotope ratios of carbonate‐bound sulphates, and sulphurized hydrocarbon biomarkers of the stromatolitic carbonate indicate that CaCO3 precipitation occurred near the oxic–anoxic interface as a result of intensive bacterial sulphur cycling rather than photosynthetic activity. Furthermore, anaerobic oxidation of methane by Archaea may have driven CaCO3 precipitation in deeper parts of the biofilm community, as reflected by high concentrations of squalane with a strongly negative δ13C in conjunction with evaporite pseudomorphs showing extremely low δ13CCarb ratios. Consequently, the Thüste stromatolites are now interpreted as having initially formed by gypsum impregnation of biofilms. Subsequently, early Mg‐calcitic calcitization within the biofilms occurred because of combined bacterial iron, manganese and sulphate reduction, with an increasing contribution of anaerobic oxidation of methane with depth. This model plausibly explains the prominent preservation of signals derived from oxygen‐independent metabolic pathways, whereas virtually no geochemical record exists for an aerobic community that may, nevertheless, have prevailed at the stromatolite surface. Photic‐zone stromatolites with a prominent signal of anaerobic oxidation of methane may be common in, and indicative of, oxygen‐depleted sulphate‐bearing environments with high rates of methane production, conditions that possibly were fulfilled at the Archaean to Proterozoic transition. 相似文献
11.
天津蓟县中元古界高于庄组中臼齿状构造的层序地层位置及其成因的初步研究 总被引：18，自引：11，他引：18
天津蓟县剖面的中元古界高于庄组为一套厚度约为1 600m的碳酸盐岩地层，包括四个段：第一段以潮坪相叠层石白云岩为主；第二段主要为含锰白云岩；第三段发育较多的纹理化石灰岩和泥晶灰岩；第四段则以叠层石岩礁（叠层石生物丘和生物层）的发育为特点。根据岩相到岩相序列可在该套碳酸盐岩地层中识别出L-M型、潮下型、环潮坪型米级旋回层序。根据米级旋回层序的有序垂直叠加形式所反映出的沉积相序列可以把高于庄组划分为13个三级层序（SQ1至SQ13），并进一步归为4个二级层序。在以灰岩为主的高于庄组第三段中，其中的第三个三级层序（SQ11）中部的灰岩层中发育臼齿状构造。这种臼齿状构造以特别的形态、富含有机质、易硅化等特点可能表明了前寒武纪碳酸盐岩沉积作用的一些基本特征：第一、在浅水环境中发育叠层石而在较深水环境（中缓坡）中发育臼齿状构造，臼齿状构造就象叠层石一样是一种极为特别的与生物沉积作用相关的沉积构造；第二、在发育叠层石的潮坪环境中有利于发生白云石化作用，发育臼齿状构造的地层则以灰岩为主，这从一个侧面反映了前寒武纪白云岩似乎又不是原生白云岩。实际上，这些特征本身即代表了一些前寒武纪沉积学问题，随着研究的深入对这些问题将会得出更加接近自然事实的答案。 相似文献
12.
朱兆奇 《中国地球化学学报》1989,8(1):54-64
Under and climate conditions the chemical weathering of manganese ores is govermed by the fugacities of O2,CO2 and S2 in the atmosphere and soils.Manganese minerals exhibit solid phase transformations without migration of Fe and Mn.Under tropical and subtropical humid climate condi-tions low-valent Mn is instable and apt to be oxidized into high valency state.High-valent Mn miner-als are stable and easy to form secondary high-grade Mn ores.Secondary concentration is possible for Mn ores in carbonate formations,while those in clastic rocks tend to migrate and may be washed away.Such differences are the main obstacles in prospecting Mn ore deposits. 相似文献
13.
《Geochimica et cosmochimica acta》1999,63(13-14):2001-2007
Stable oxygen isotope ratios of foraminiferal calcite are widely used in paleoceanography to provide a chronology of temperature changes during ocean history. It was recently demonstrated that the stable oxygen isotope ratios in planktonic foraminifera are affected by changes of the seawater chemistry carbonate system: the δ18O of the foraminiferal calcite decreases with increasing CO32− concentration or pH. This paper provides a simple explanation for seawater chemistry dependent stable oxygen isotope variations in the planktonic foraminifera Orbulina universa which is derived from oxygen isotope partitioning during inorganic precipitation. The oxygen isotope fractionation between water and the dissolved carbonate species S = [H2CO3] + [HCO3−] + [CO32−] decreases with increasing pH. Provided that calcium carbonate is formed from a mixture of the carbonate species in proportion to their relative contribution to S, the oxygen isotopic composition of CaCO3 also decreases with increasing pH. The slope of shell δ18O vs. [CO32−] of Orbulina universa observed in culture experiments is −0.0022‰ (μmol kg−1)−1 (Spero et al., 1997), whereas the slope derived from inorganic precipitation is −0.0024‰ (μmol kg−1)−. The theory also provides an explanation of the nonequilibrium fractionation effects in synthetic carbonates described by Kim and O’Neil (1997) which can be understood in terms of equilibrium fractionation at different pH. The results presented here emphasize that the oxygen isotope fractionation between calcium carbonate and water does not only depend on the temperature but also on the pH of the solution from which it is formed. 相似文献
14.
Highly negative δC13 values, ?18 to ? 40%., for carbonate cements found in Recent barrier and beach sands of the Mississippi River Delta complex strongly suggest that considerable carbon is furnished to the CaCO3 cements by either chemical or biological oxidation of CH4. These cemented sands are commonly found on beaches of the Chandeleur barrier island chain and other sites along the Louisiana coast where Holocene sands are rapidly transgressing over highly organic marsh deposits. Generation of CH4 from underlying anoxic marsh sediments, followed by vertical migration and oxidation to CO2 in the porous overlying sand, appears to be the unique set of conditions regulating this process of carbonate cementation. 相似文献
15.
Jiafei Xiao Jingyang He Haiying Yang Chengquan Wu Jianbin Xu Yantao Li 《Resource Geology》2019,69(3):227-248
The Datangpo‐type manganese ore deposits, which formed during the Nanhuan (Cryogenian) period and are located in northeastern Guizhou and adjacent areas, are one of the most important manganese resources in China, showing good prospecting potential. Many middle‐to‐large deposits, and even super‐large mineral deposits, have been discovered. However, the genesis of manganese ore deposits is still controversial and remains a long‐standing source of debate; there are several viewpoints including biogenesis, hydrothermal sedimentation, gravity flows, cold‐spring carbonates, etc. Geochemical data from several manganese ore deposits show that there are positive correlations between Al2O3 and TiO2, SiO2, K2O, and Na2O, and strong negative correlations between Al2O3 and CaO, MgO, and MnO in black shales and manganese ores. U, Mo, and V show distinct enrichment in black shales and inconspicuous enrichment in Mn ores. Ba and Rb show strong positive correlations with K2O in manganese ores. Cu, Ni, and Zn show clear correlations with total iron in both manganese ores and black shales. ∑REE of manganese ores has a large range with evident positive Ce anomalies and positive Eu anomalies. The Post Archean Australian Shale (PAAS) normalized rare earth element (REE) distribution patterns of manganese ores present pronounced middle rare earth element (MREE) enrichment, producing “hat‐shaped” REE plots. ∑REE of black shales is more variable compared with PAAS, and the PAAS‐normalized REE distribution patterns appear as “flat‐shaped” REE plots, lacking evident anomaly characteristics. δ13C values of carbonate in both manganese ores and the black shales show observable negative excursions. The comprehensive analysis suggests that the black shales formed in a reducing and quiet water column, while the manganese ores formed in oxic muddy seawater, which resulted from periodic transgressions. There was an oxidation–reduction cycle of manganese between the top water body and the bottom water body caused by the transgressions during the early Datangpo, which resulted in the dissolution of manganese. Through the exchange of the euphotic zone water and the bottom water, and episodic inflow of oxygenated water, the manganese in the bottom water was oxidized to Mn‐oxyhydroxides and rapidly buried along with algae. In the early diagenetic stage, Mn‐oxyhydroxides were reduced and dissolved in the anoxic pore water and then transformed into Mn‐carbonates by reacting with HCO3? from the degradation of organic matter or from seawater. In the intervals between transgressions, continuous supplies of terrigenous clastics and the high productive rates of organic matter in the euphotic zone resulted in the deposition of the black shales enriched in organic matter. 相似文献
16.
Ulrich Kramm 《Contributions to Mineralogy and Petrology》1973,41(2):179-196
The Southern Venn-Stavelot Massif is characterized by Ordovician and Devonian rocks very rich in manganese and aluminum, which
are attacked by a low grade regional metamorphism. The assemblages 1 (phengite, paragonite, chlorite, chloritoid, garnet,
quartz, hematite, rutile) and 2 (phengite, paragonite, chlorite, kaolinite (andalusite, pyrophyllite), garnet, quartz, hematite,
rutile) are of basic interest for the formation of chloritoid. As the two rock types are isofaciell and quasi-identical in
chemistry except for the iron oxides, there is clear evidence for the influence of
on the chloritoid formation at its lower p-T stability limit. This can be shown by a discussion of the phase relations of chloritoid, garnet, kaolinite, chlorite and
phengite in respect to the oxidation ratio mol 2 Fe2O3x 100/2 Fe2O3+ FeO of the host rocks. Especially chloritoid and chlorite change their chemistry in a characteristic way with rising oxidation
ratio in getting richer and richer in manganese and magnesium (chloritoid) and magnesium (chlorite). A simultaneous increase
in trivalent iron in these phases is supposed. At an oxidation ratio of 85–90 the
stability limit of chloritoid is reached. The increasing substitution of manganese and magnesium up to this limit should
have a stabilizing effect. In a rough estimate the oxygen partial pressure is supposed to be in the order of 10−10 atm at the stability limit of chloritoid assuming a temperature of metamorphism between 360–400° C. Rocks with oxidation
ratios between 90 and 100 are characterized by the presence of kaolinite. If the oxidation ratio is still higher (all iron
as Fe3+, parts of the manganese in the trivalent state), the rocks belong to assemblage 3 (phengite, paragonite, chlorite, viridine,
(kaolinite), (garnet), quartz, hematite, braunite, rutile).
Dedicated to Prof. Dr. K. Jasmund at his 60. birthday. 相似文献
17.
Steven Creighton Thomas Stachel Sergei Matveev Heidi Höfer Catherine McCammon Robert W. Luth 《Contributions to Mineralogy and Petrology》2009,157(4):491-504
The oxidation state, reflected in the oxygen fugacity (fO2), of the subcratonic lithospheric mantle is laterally and vertically heterogeneous. In the garnet stability field, the Kaapvaal
lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO2 FMQ-2 at 110 km to FMQ-4 at 210 km. Oxidation accompanying metasomatism has obscured this crystal-chemical controlled depth-fO2 trend in the mantle beneath Kimberley, South Africa. Chondrite normalized REE patterns for garnets, preserve evidence of
a range in metasomatic enrichment from mild metasomatism in harzburgites to extensive metasomatism by LREE-enriched fluids
and melts with fairly unfractionated LREE/HREE ratios in phlogopite-bearing lherzolites. The metasomatized xenoliths record
redox conditions extending up to Δlog fO2 = FMQ, sufficiently oxidized that magnesite would be the stable host of carbon in the most metasomatized samples. The most
oxidized lherzolites, those in or near the carbonate stability field, have the greatest modal abundance of phlogopite and
clinopyroxene. Clinopyroxene is modally less abundant or absent in the most reduced peridotite samples. The infiltration of
metasomatic fluids/melts into diamondiferous lithospheric mantle beneath the Kaapvaal craton converted reduced, anhydrous
harzburgite into variably oxidized phlogopite-bearing lherzolite. Locally, portions of the lithospheric mantle were metasomatized
and oxidized to an extent that conversion of diamond into carbonate should have occurred.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
18.
The oxidation of carbonate green rust, GR(CO32−), in NaHCO3 solutions at T = 25°C has been investigated through electrochemical techniques, FTIR, XRD, TEM and SEM. The used GR(CO32−) samples were made of either suspended solid in solution or a thin electrochemically formed layer on the surface of an iron disc. Depending on experimental conditions, oxidation occurs, with or without major modifications of the GR(CO32−) structure, suggesting the existence of two pathways: solid-state oxidation (SSO) leading to a ferric oxyhydroxycarbonate as the end product, and a dissolution-oxidation-precipitation (DOP) mechanism leading to ferric oxihydroxides such as lepidocrocite, goethite, or ferrihydrite. A formula was proposed for this ferric oxyhydroxycarbonate, Fe6IIIO(2+x)(OH)(12-2x)(H2O)x(CO3), assuming that the solid-state oxidation reaction is associated to a deprotonation of the water molecules within the interlayers, or of the hydroxyl groups in the Fe(O,H) octahedra layers. The DOP mechanism involves transformation via solution with the occurrence of soluble ferrous-ferric intermediate species. A discussion about factors influencing the oxidation of carbonate green rust is provided hereafter. The ferric oxyhydroxycarbonate can be reduced back to GR(CO32−) by a reverse solid-state reduction reaction. The potentiality for a solid-state redox cycling of iron to occur may be considered. The stability of the ferric oxyhydroxycarbonate towards thermodynamically stable ferric phases, such as goethite and hematite, was also studied. 相似文献
19.
20.
Authigenic carbonates in methane seeps from the Norwegian sea: Mineralogy, geochemistry, and genesis
A. Yu. Lein A. I. Gorshkov N. V. Pimenov Yu. A. Bogdanov P. Vogt O. Yu. Bogdanova V. M. Kuptsov N. V. Ul’yanova A. M. Sagalevich M. V. Ivanov 《Lithology and Mineral Resources》2000,35(4):295-310
Authigenic carbonates in the caldera of an Arctic (72°N) submarine mud volcano with active CH4bearing fluid discharge are formed at the bottom surface during anaerobic microbial methane oxidation. The microbial community
consists of specific methane-producing bacteria, which act as methanetrophic ones in conditions of excess methane, and sulfate
reducers developing on hydrogen, which is an intermediate product of microbial CH4 oxidation. Isotopically light carbon (δ13Cav =−28.9%0) of carbon dioxide produced during CH4 oxidation is the main carbonate carbon source. Heavy oxygen isotope ratio (δ18Oav = 5%0) in carbonates is inherited from seawater sulfate. A rapid sulfate reduction (up to 12 mg S dm−3 day−1) results in total exhausting of sulfate ion in the upper sediment layer (10 cm). Because of this, carbonates can only be
formed in surface sediments near the water-bottom interface. Authigenic carbonates occurring within sediments occur do notin situ. Salinity, as well as CO
3
2−
/Ca and Mg/Ca ratios, correspond to the field of nonmagnesian calcium carbonate precipitation. Calcite is the dominant carbonate
mineral in the methane seep caldera, where it occurs in the paragenetic association with barite. The radiocarbon age of carbonates
is about 10000 yr. 相似文献