新元古代晚期盖帽碳酸盐岩的成因与“雪球地球”的终结机制

新元古代晚期约635 Ma的地球发育了到达赤道附近的冰川作用，地质记录上表现为代表寒冷气候的冰期沉积杂砾岩，直接被代表温暖环境的碳酸盐岩层（常称盖帽碳酸盐岩）覆盖。由于盖帽碳酸盐岩奇特的岩石学和地球化学特征，引起了对其成因认识的巨大争论，提出了“雪球地球”和“甲烷渗漏”等假说。“雪球地球”假设可以解释一些令人困惑的地学现象，如低纬度和低海拔冰川沉积、盖帽碳酸盐岩、碳酸盐δ13C负漂移和条带状铁矿层等，但许多科学家对此提出了质疑。最近对盖帽碳酸盐岩的δ13C分析结果（最低达-41‰）、盖帽碳酸盐岩发育的类似现代冷泉碳酸盐岩沉积组构等似乎支持“甲烷渗漏”假说。     

Chemostratigraphy and lithological characters of Neoproterozoic cap carbonates from the Kuruktag Mountain, Xinjiang, western China

The Neoproterozoic Era includes some of the most largest ice ages in the geological history. The exact number of glaciations is unknown, though there were at least two events of global glaciation. Neoproterozoic glacial deposits in the Kuruktag Mountain, Xinjiang, western China have proven that there had occurred three discrete Neoproterozoic glaciations. Diamictite units occurred in the Bayisi, Tereeken, and Hankalchough formations, carbonate units were recognized among the diamictites and immediately overlied the Bayisi, Tereeken and Hankalchough diamictites. Carbonates at the top of the Bayisi Formation are characterized by the dolo-sility stones with negative δ13C values ranging from -4.10‰ to -8.17‰ (PDB), comparable to the Sturtian cap carbonates that overlie the Sturtian glacial deposits from other Neoproterozoic sequences. Carbonates overlying the Tereeken Formation are characterized by the pinkish cap dolostones (ca. 10 m thick) with negative δ13C values ranging from -2.58‰ to -4.77‰ (PDB), comparable to the Marinoan cap carbonates. The cap is also characterized by tepee-like structures, barite precipitates and pseudomorphous aragonite crystal fan limestones. Carbonates at the top of the Hankalchough Formation are characterized by subaerial exposure crust (vadose pisolite structure, calcareous crust structure) dolostones with negative δ13C values ranging from -4.56‰ to -11.45‰ (PDB) and the calcareous crust dolostones, implying that the Hankalchough cap carbonates differ from either the Sturtian or Marinoan cap carbonates in sedimentary environment and carbon isotopic composition. In addition, it is suggested the Hankalchough glaciation belongs to a terrestrial glaciation and it is the third largest glaciation during the Neoproterozoic period on the Tarim platform.     

Cold seep deposits of Beauvoisin (Oxfordian; southeastern France) and Marmorito (Miocene; northern Italy): microbially induced authigenic carbonates

The relation of two well-known ancient carbonate deposits to hydrocarbon seepage was confirmed by this study. Archaea are found to be associated with the formation of Oxfordian seep carbonates from Beauvoisin and with a Miocene limestone from Marmorito ("tube-worm limestone"). Carbonates formed due to a mediation by archaea exhibit extremely positive or extremely negative δ¹³C_carbonate values, respectively. Highly positive values (+15‰) reflect the use of ¹³C-enriched CO₂ produced by methanogenesis. Low δ¹³C values of the Marmorito carbonates (–30‰) indicate the oxidation of seepage-derived hydrocarbons. Likewise, the δ¹³C content of specific tail-to-tail linked isoprenoids, biomarkers for archaea, was found to be strikingly depleted in these samples (as low as –115‰). The isotopic signatures corroborate that archaea were involved in the cycling of seepage-derived organic carbon at the ancient localities. Another Miocene limestone ("Marmorito limestone") shows a strong imprint of methanotrophic bacteria as indicated by δ¹³C values of carbonate as low as –40‰ and biomarker evidence. Epifluorescence microscopy and field-emission scanning electron microscopy revealed that bacterial biofilms were involved in carbonate aggregation. In addition to lucinid bivalves previously reported from both localities, we infer that sponges from Beauvoisin and tube worms from Marmorito depended on chemosynthesis as well. Low δ¹³C values of nodules related to sponge taphonomy (–27‰) indicate that sponges might have been linked to an enhanced hydrocarbon oxidation. Tube worm fossils from Marmorito closely resemble chemosynthetic pogonophoran tube worms from Recent cold seeps and are embedded in isotopically light carbonate (δ¹³C –30‰). Received: 13 October 1998 / Accepted: 5 February 1999     

Geochemical properties of Neoproterozoic “cap dolomites” in the Patom paleobasin and problem of their genesis

The characteristic feature of many Upper Neoproterozoic glacial sequences is their “cap carbonates” (CC) resting without visible unconformity upon glaciogenic diamictites. Such an unusual association, peculiar structures and textures, and negative δ¹³C values (approximately −4 ± 2‰) that are atypical of marine carbonates provoked long debates about the nature of these carbonates, which play an important role in the Snowball Earth hypothesis. According to this hypothesis, the Earth was entirely covered by ice during large-scale glaciations, and CC accumulation was related to the global change in geochemical processes. In this work, we discuss data on the chemical and isotopic (C, O, Sr) compositions of CCs, which overlie glacial sediments of the Nichatka and Bol’shoi Patom formations accumulated in different parts of the Neoproterozoic Patom paleobasin (Central Siberia). High concentrations of Fe (up to 6400 ppm), Mn (2320 ppm), and radiogenic Sr (⁸⁷Sr/⁸⁶Sr₀ up to 0.7172) established in CCs indicates a strong influence of the continental flow. Extraordinary Snowball Earth conditions are not necessary for the accumulation of these rocks, geochemical and sedimentological properties of which may be explained by the discharge of thawing waters into partly or completely isolated near-glacier basin, their intermittent freezing, and/or washout of “frozen” carbonates from the surface of thawing glaciers. The peculiar thin-laminated texture of CC may be related to seasonal processes of climatic cycles. They were accumulated in the course of general (relatively long-term) depletion of the atmosphere and hydrosphere in ¹³C, which has nothing to do with the CC formation as a specific type of carbonate sediments. Amplitude and duration of the negative δ¹³C excursion in carbonates associated with the Lower Vendian glacial sediments (665–635 Ma) are appreciably lower than the negative anomaly in rocks of the Zhuya Group that likely correspond to the Shuram-Vonoka Event (∼560−580 Ma ago), which probably marks the crucial point in the Precambrian deglaciation: mass destabilization of methane hydrates and degradation of the Early Vendian psychrosphere in oceans.     

The Darasun gold deposit,Eastern Transbaikal region: Chemical composition,REE patterns,and stable carbon and oxygen isotopes of carbonates from ore veins

The chemistry, REE patterns, and carbon and oxygen isotopic compositions of carbonates from ore veins of the Darasun deposit are discussed. In addition to the earlier described siderite, calcite, and carbonates of the dolomite-ankerite series, kutnahorite is identified. The total REE content in Fe-Mg carbonates of the dolomite-ankerite series (2.8–73 ppm) is much lower than in later calcite (18–390 ppm). δ¹³C of Fe-Mg carbonates and calcite varies from +1.1 to −6.7‰ and from −0.9 to −4.9‰, respectively. δ¹⁸O of Fe-Mg carbonates and calcite varies from +17.6 to 3.6‰ and from +15.7 to −0.5‰, respectively. The REE sum and carbon and oxygen isotopic compositions reveal zonal distribution relative to the central granodiorite porphyry stock. The correlation between the carbon and oxygen isotopic compositions and REE sum reflects variations in the physicochemical formation conditions and composition of ore-forming fluid. The isotopic composition of fluid is calculated, and possible sources of its components are considered. Earlier established evidence for a magmatic source of ore-forming fluid and participation of meteoric water in ore formation is confirmed. Geochemical evidence for interaction of ore-forming fluid with host rocks is furnished. The relationships between the REE sum, on the one hand, and carbon and oxygen isotopic compositions of hydrothermal ore-forming fluid, on the other, are established.     

Stratotype of the Lower Riphean, the Burzyan Group of the Southern Urals: Lithostratigraphy, paleontology, geochronology, Sr- and C-isotopic characteristics of its carbonate rocks

The main objective of this work is the generalization of lithostratigraphic, biostratigraphic and isotopic-geochronological data characterizing carbonate rocks from type succession of the broadly acknowledged chronostratigraphic subdivision of the Lower Riphean, such as the Burzyan Group of the Southern Urals and its analogs. Using an original approach to investigation of the Rb-Sr and Pb-Pb isotopic systems in carbonates and strict criteria of their retentivity, we studied the least altered (“best”) samples of the Burzyan carbonates, which retain the ⁸⁷Sr/⁸⁶Sr ratio of the sedimentation environment. As long ago as 1550 ± 30 and 1430 ± 30 Ma, that ratio corresponded to 0.70460–0.70480 and 0.70456–0.70481. The results confirm the influx of the mantle material predominantly into the World Ocean of the Early Riphean. The influence of meteoric diagenesis was likely responsible for local declines of δ¹⁸O in the Burzyan carbonates down to the values of −2.5 to −1.5‰ V-PDB. In the “best” samples, this parameter ranges from −0.7 to 0‰, which is consistent with the assumption that δ¹⁸O values (0 ± 1‰) characterized the stasis of the carbonate carbon isotopic composition in oceanic water 2.06–1.25 Ga ago. C-isotopic data on carbonate from the Paleoproterozoic-Lower Riphean boundary formations of the Urals, India, North America and Siberia suggest that the mentioned stasis ended by the commencement of the Early Riphean ca. 1.6–1.5 Ga ago. In the least altered carbonates of the Early Riphean, the δ¹⁸O variation range corresponds to 4.0–4.5‰.     

Origin of ultramafic-hosted magnesite on Margarita Island,Venezuela

Ultramafic-hosted deposits of magnesite (MgCO₃) have been studied on Margarita Island, Venezuela, to elucidate the source of carbon and conditions of formation for this type of ore. Petrographic, mineralogic, and δ¹⁸O data indicate that magnesite precipitated on Margarita in near-surface environments at low P and T. δ¹³C ranges from −9 to −16‰ PDB within the magnesite and −8 to −10‰ PDB within some calcite and dolomite elsewhere on the island. The isotopically light dolomite fills karst and the calcite occurs as stock-work veins which resemble the magnesite deposits. These carbon isotopic ratios are consistent with a deep-seated source rather than an overlying source from a zone of surficial weathering. However, there is not much enrichment of precious metals and no enrichment of heavy rare-earth elements, as would be expected if the carbon had migrated upward as aqueous carbonate ions. The carbon probably has risen as a gaseous mixture of CO₂ and CH₄ which partially dissolved in near-surface water before leaching cations and precipitating as magnesite and other carbonates. The process probably is ongoing, given regional exhalation of carbonaceous gases.     

Microscale carbon isotope variability in ALH84001 carbonates and a discussion of possible formation environments

The carbonates in martian meteorite ALH84001 preserve a record of aqueous processes on Mars at 3.9 Ga, and have been suggested to contain signatures of ancient martian life. The conditions of the carbonate formation environment are critical for understanding possible evidence for life on Mars, the history of water on Mars, and the evolution of the martian atmosphere. Despite numerous studies of petrographic relationships, microscale oxygen isotope compositions, microscale chemical compositions, and other minerals associated with the carbonates, formation models remain relatively unconstrained. Microscale carbon isotope analyses of ALH84001 carbonates reveal variable δ¹³C values ranging from +27 to +64‰. The isotopic compositions are correlated with chemical composition and extent of crystallization such that the Mg-poor, early-formed carbonates are relatively ¹³C depleted and the Mg-rich, later forming carbonates, are ¹³C enriched. These data are inconsistent with many of the previously proposed environments for carbonate formation, and a new set of hypotheses are proposed. Specifically, two new models that account for the data involve low temperature (<100°C) aqueous processes: (1) the carbonates formed during mixing of two fluids derived from separate chemical and isotopic reservoirs; or (2) the carbonates formed from high pH fluids that are exposed to a CO₂-rich atmosphere and precipitate carbonate, similar to high pH springs on Earth.     

Use of Regenerated Scales and Scale Marginal Increments as Indicators of Recent Dietary History in Fish

The potential of teleost scales as indicator tissues of recent dietary history was investigated in the estuarine fish, Notolabrus celidotus. Treatment fish were fed a ¹⁵N-enriched bivalve diet (δ¹⁵N = 108.8‰) for up to 90 days to examine integration of the dietary source signature in scale margin, regenerated scale, and dorsal muscle tissues. Regenerated scales exhibited the greatest and most rapid enrichment in δ¹⁵N (to 53.4 ± 5.0‰) of the tissues examined. Scale margin δ¹⁵N signatures also increased significantly from 14.5‰ to 30.9 ± 6.0‰, while muscle tissue only increased by 2.8‰ after 90 days. Dietary contribution models suggested that isotopic equilibration of dietary nitrogen would be most rapid in regenerated scales, followed by scale marginal increments and then muscle. In conclusion, teleost scales hold considerable potential as novel, nondestructive indicators of recent dietary history, yet currently face constraints from uncertainties in isotopic integration mechanisms.     

三峡地区陡山沱早期水体性质的稀土元素和锶同位素制约

通过分析三峡地区九龙湾剖面新元古代盖帽碳酸盐岩的稀土元素和锶同位素组成,对新元古代“雪球地球”事件结束后水体的性质提供了制约。盖帽碳酸盐岩的REE配分模式具有轻重稀土元素亏损的特征,存在轻微Y正异常以及较高的Y/Ho值,没有明显的La异常。这些特征与受淡水影响的陆缘盆地、湖泊等沉积环境相似,而不同于正常海水。这表明盖帽碳酸盐岩不是正常的海相沉积物,而是发育在淡水与海水混合环境中的沉积物。盖帽碳酸盐岩具有较高的87Sr/86Sr值,这是由于新元古代“雪球地球”事件结束后大量陆源风化物的输入引起的。因此,盖帽碳酸盐岩较高的87Sr/86Sr值不能代表当时全球海水信息,只能反映局部混合水体的信息。轻微的Ce负异常显示陡山沱组早期水体处于弱氧化状态。盖帽碳酸盐岩的REE和Sr同位素综合特征表明在新元古代“雪球地球”事件结束后,陡山沱组早期水体是携带大量陆源风化物的冰融水与海水混合的水体,而且此时的混合水体处于弱氧化状态。     

Major shoreline retreat and sediment starvation following Snowball Earth

While cap dolostones are integral to the Snowball Earth hypothesis, the current depositional model does not account for multiple geological observations. Here we propose a model that rationalises palaeomagnetic, sequence‐stratigraphic and sedimentological data and supports rapid deglaciation with protracted cap dolostone precipitation. The Snowball Earth hypothesis posits that a runaway ice‐albedo can explain the climate paradox of Neoproterozoic glacial deposits occurring at low palaeolatitudes. This scenario invokes volcanic degassing to increase atmospheric greenhouse gases to a critical threshold that overcomes the albedo effect and brings the planet back from the ice‐covered state. Once this occurs, Earth should shift rapidly from a snowball to an extreme greenhouse. However, cap dolostone units overlying glacial sediments, typically interpreted as transgressive deposits, exhibit multiple magnetic reversals indicating they accumulated in >10⁵ years. By reviewing modern post‐glacial systems, sequence stratigraphic concepts and principles of sedimentology, we suggest that cap dolostones are not restricted to the transgression but rather represent sediment starvation following a major landward shoreline migration associated with the demise of Snowball Earth. Thus, the duration in which cap dolostone accumulated is not directly coupled to the timescale of the Snowball Earth deglaciation.     

Carbon and oxygen isotopic composition of car- bonate cements of different phases in terrigenous siliciclastic reservoirs and significance for their origin： A case study from sandstones of the Triassic Yanchang Formation, southwestern Ordos Basin, China

Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope （their δ^18O values range from -0.3‰- -0.1‰） and lighter oxygen isotope （their δ^18O values range from -22.1‰- -19.5‰）. Generally, they are closely related to the direct precipitation of oversaturated calcium carbonate from alkaline lake water. This kind of cementation plays an important role in enhancing the anti-compaction ability of sandstones, preserving intragranular volume and providing the mass basis for later disso- lution caused by acidic fluid flow to produce secondary porosity. Ferriferous calcites are characterized by relatively light carbon isotope with δ^13C values ranging from -8.02‰ to -3.23‰, and lighter oxygen isotope with δ^18O values ranging from -22.9‰ to -19.7‰, which is obviously related to the decarboxylation of organic matter during the late period of early diagenesis to the early period of late diagenesis. As the mid-late diagenetic products, ferriferous cal- cites in the study area are considered as the characteristic authigenic minerals for indicating large-scaled hydrocarbon influx and migration within the clastic reservoir. The late ankerite is relatively heavy in carbon isotope with δ^13C values ranging from -1.92‰ to -0.84‰, and shows a wide range of variations in oxygen isotopic composition, with δ^18O values ranging from -20.5‰ to -12.6‰. They are believed to have nothing to do with decarboxylation, but the previously formed marine carbonate rock fragments may serve as the chief carbon source for their precipitation, and the alkaline diagenetic environment at the mid-late stage would promote this process.     

Neoproterozoic cap carbonates: a critical appraisal of existing models and the plumeworld hypothesis

Evidence for glaciation during the mid-late Neoproterozoic is widespread on Earth, reflecting three or more ice ages between 730 Ma and 580 Ma. Of these, the late Neoproterozoic Marinoan glaciation of approximately 635 Ma stands out because of its ubiquitous association with a characteristic, microcrystalline cap dolostone that drapes glacially influenced rock units worldwide. The Marinoan glaciation is also peculiar in that evidence for low altitude glaciation at equatorial latitudes is compelling. Three models have been proposed linking abrupt deglaciation with this global carbonate precipitation event: (i) overturn of an anoxic deep ocean; (ii) catastrophically accelerated rates of chemical weathering because of supergreenhouse conditions following global glaciation (Snowball Earth Hypothesis); and (iii) massive release of carbonate alkalinity from destabilized methane clathrates. All three models invoke extreme alkalinity fluxes into seawater during deglaciation but none explains how such alkalinity excess from point sources could be distributed homogeneously around the globe. In addition, none explains the consistent sequence of precipitation events observed within cap carbonate successions, specifically: (i) the global blanketing of carbonate powder in shallow marine environments during deglaciation; (ii) widespread and disruptive precipitation of dolomite cement; followed by (iii) localized barite precipitation and seafloor cementation by aragonite. The conceptual model presented here proposes that low latitude deglaciation was so massive and abrupt that the resultant meltwater plume could extend worldwide, physically separating the surface and deep ocean reservoirs for ≥10³ years. It is proposed that cap dolostones formed primarily by microbially mediated precipitation of carbonate whitings during algal blooms within this low salinity plumeworld rather than by abiotic precipitation from normal salinity seawater. Many of the disruption features that are characteristic of cap dolostones can be explained by microbially mediated, early diagenetic dolomitization and cementation. The re-initiation of whole ocean circulation degassed CO₂ into the atmosphere in areas of upwelling, triggering localized, abiotic CaCO₃ precipitation in the form of aragonite fans that overlie cap dolostones in NW Canada and Namibia. The highly oxygenated shallow marine environments of the glacial and post-glacial Neoproterozoic world provided consistently favourable conditions for the evolutionary development of animals and other oxygenophiles.     

重庆秀山南沱冰期后的海陆环境变化

扬子地区发育地层所记录的南沱冰期在时间上与Marinoan冰期相当,被认为是"雪球事件"的产物,受到广泛关注。借助于重庆秀山长河桥剖面的南沱组冰碛岩上覆陡山沱组盖帽白云岩和页岩样品的精细采集,选取冰碛岩之上2.5 m内的地层进行同位素比值和元素含量测试,并尝试性的使用酸不溶物的元素地球化学数据,对冰期后可能出现的环境变化进行了综合分析,结果表明:盖帽白云岩C同位素数据基本符合海水分层混合模式特征;U/Th值也反映出该地区在雪球后经历了由缺氧-贫氧环境向贫氧-氧化环境的迅速转变,可能反映了雪球后缺氧富有机质的深部大洋水随上升洋流上涌并被迅速氧化的过程;强烈的Eu正异常的出现,可能与埃迪卡拉纪海底火山、热液活动频繁出现或近源热液活动相关;盖帽碳酸盐岩样品中出现Ce轻微负异常,表明其形成于弱氧化环境;87Sr/86Sr值和Y/Ho值均呈现伴有大量陆源碎屑物输入的特点;盖帽碳酸盐岩的酸不溶物可以反映当时的大陆风化背景,其化学蚀变指数（CIA）稳定在72左右,说明当时的大陆环境具有温暖湿润的特征,化学风化作用强度中等。综上所述,在南陀冰期结束后,秀山长河桥剖面的沉积环境经历了缺氧-贫氧环境向贫氧-氧化环境的迅速转变,同时,随着上升洋流的出现原有的冰期海水分层被迅速破坏,并可能伴随着地表径流的不断增强,同时热液活动在这一时期也频繁发生。在这一时期,剖面附近的大陆环境也迅速由冰期过渡为温暖湿润的环境。     

Determination of Sr/Sr mass-dependent isotopic fractionation and radiogenic isotope variation of Sr/Sr in the Neoproterozoic Doushantuo Formation

We measured both mass-dependent isotope fractionation of δ⁸⁸Sr (⁸⁸Sr/⁸⁶Sr) and radiogenic isotopic variation of Sr (⁸⁷Sr/⁸⁶Sr) for the Neoproterozoic Doushantuo Formation that deposited as a cap carbonate immediately above the Marinoan-related Nantuo Tillite. The δ⁸⁸Sr and ⁸⁷Sr/⁸⁶Sr compositions showed three remarkable characteristics: (1) high radiogenic ⁸⁷Sr/⁸⁶Sr values and gradual decrease in the ⁸⁷Sr/⁸⁶Sr ratios, (2) anomalously low δ⁸⁸Sr values at the lower part cap carbonate, and (3) a clear correlation between ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr values. These isotopic signatures can be explained by assuming an extreme greenhouse condition after the Marinoan glaciation. Surface seawater, mixed with a large amount of freshwater from continental crusts with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios, was formed during the extreme global warming after the glacial event. High atmospheric CO₂ content caused sudden precipitation of cap carbonate from the surface seawater with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios. Subsequently, the mixing of the underlying seawater, with unradiogenic Sr isotope compositions and normal δ⁸⁸Sr ratios, probably caused gradual decrease of the ⁸⁷Sr/⁸⁶Sr ratios of the seawater and deposition of carbonate with normal δ⁸⁸Sr ratios. The combination of ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr isotope systematics gives us new insights on the surface evolution after the Snowball Earth.     

Carbon and Oxygen Isotopes and Formation Conditions of the Upper Famennian Shale-Bearing Rocks in the Pripyat Trough,Southern Belarus

The behavior of stable carbon and oxygen isotopes in carbonates during the deposition and diagenesis of sediments in the bioproductive Upper Famennian Pripyat Trough (southern Belarus) is discussed. Limestones and clayey limestones (Corg 0.92 ± 0.11%) are characterized by very low δ13C values (–9.6 ± 0.3‰). Parental sediments of these rocks were deposited in the shallow-water zone during slow downwarping episodes of the seafloor. Lithification of the sediments took place in oxidative conditions of the diagenesis zone. Organic matter was actively oxidized by free oxygen. Carbon dioxide with isotopically light organic carbon formed in this process was used during the crystallization of diagenetic carbonates that are visually indiscernible from the sedimentational variety. Marls, clayey marls, and carbonate-bearing clays (Corg 6.02 ± 0.80%) are characterized by δ13C values as high as –3.5 ± 0.6‰. In combustible shales (Corg >10%), δ13C value is ‒1.2 ± 0.6‰). The clayey rocks mark the episodes of sedimentation in relatively deep-water conditions that appear during the uncompensated sagging of the basin floor. The diagenetic zone with free oxygen was significantly decreased or absent at all. Here, oxygen of marine sulfates was the main or single oxidizer of organic matter (sulfate reduction). The sulfate oxygen is a weaker oxidizing agent than free oxygen. Therefore, much more organic matter was retained and fossilized in clayey rocks than in carbonate rocks. Organic carbon released during the sulfate reduction and mobilized later for the diagenetic carbonate formation was insufficient for the significant decrease of δ13C values relative to the marine carbonate standard. Isotopic composition of carbonate oxygen in the studied rocks is invariable and does not depend on the content of clay and organic matter. In these rocks, δ18O values are at the level (approximately –5‰) shown for the Famennian in the Global Chemostratigraphic Chart. This fact is consistent with the supposition that oxygen isotope composition of atmospheric precipitates, which influenced the rock formation via continental flow, is close to that of sea water in low latitudes where the territory of Belarus was located in the Late Devonian.     

Carbon and oxygen isotopic composition of the Vendian-Cambrian carbonate rocks and paleoecological reconstructions

The carbon isotopic composition of carbonate rocks is widely used for the reconstruction of sedimentation paleoenvironment. Of special interest is the study of the Upper Proterozoic-Cambrian interval—the turning point in the Earth’s geological evolution. Rocks of this age show the widest variations in the carbon isotopic composition of carbonates typically correlated with epochs of global glaciations and change in the CO₂ regime. In this paper, we attempted to show that carbon isotopic variations often indicate postsedimentary alterations of carbonates and reflect the specific geochemical transformations of the rocks. Study of variations of carbon and oxygen isotopic compositions in the Vendian-Cambrian rocks provide insight into lithogenetic processes.     

Carbon Isotopic Profile Across the Bilara Group Rocks of Trans-Aravalli Marwar Supergroup in Western India: Implications for Neoproterozoic — Cambrian Transition

The rocks of Marwar Supergroup in the trans-Aravalli sector in western India are presumed to span the time interval between Neoproterozoic and early Cambrian. This, predominantly unfossiliferous, marine sedimentary sequence is characterized by a lower arenaceous facies (Jodhpur Group), middle carbonate facies (Bilara Group) and upper argillaceous— arenaceous facies (Nagaur Group) rocks. The sedimentation has been essentially in a shallow basin, described either as the fore-land slope of the rising Aravalli mountains or a sag-basin which developed and evolved due to subsidence of the updomed crust during Neoproterozoic Malani magmatism that failed to open rifts. The carbon isotopic profile for the Bilara Group carbonate rocks in the lower part shows marked oscillations and broadly negative δ¹³C character with negative anomalies as low as <−4.3‰_PDB, observed near the base of Dhanapa Formation (lower unit) and <−6.5‰_PDB in the overlying Gotan Formation (middle unit). The upper part of the profile shows a gradual positive shift. The carbon isotopic signatures of the Bilara Group rocks can be correlated with the end-Neoproterozoic — early Cambrian (Vendian — Tommotian) carbon isotopic evolution curve. Extremely low δ¹³C values indicate the glaciation related cold climatic postulates of the end-Neoproterozoic, followed by the warmer climatic conditions as indicated by the positive shift. The carbon isotopic data for Gotan Formation carbonates, at variance with the globally observed δ¹³C trends for early Tertiary, do not support the recently proposed Tertiary age for the Bilara Group.     

Hypogene Zn carbonate ores in the Angouran deposit,NW Iran

The world-class Angouran nonsulfide Zn–Pb deposit is one of the major Zn producers in Iran, with resources estimated at about 18 Mt at 28% Zn, mainly in the form of the Zn carbonate smithsonite. This study aims to characterize these carbonate ores by means of their mineralogy and geochemistry, which has also been extended to the host rocks of mineralization and other local carbonate rock types, including the prominent travertines in the Angouran district, as well as to the local spring waters. Petrographical, chemical, and stable isotope (O, H, C, Sr) data indicate that the genesis of the Zn carbonate ores at Angouran is fairly distinct from that of other “classical” nonsulfide Zn deposits that formed entirely by supergene processes. Mineralization occurred during two successive stages, with the zinc being derived from a preexisting sulfide ore body. A first, main stage of Zn carbonates (stage I carbonate ore) is associated with both preexisting and subordinate newly formed sulfides, whereas a second stage is characterized by supergene carbonates (Zn and minor Pb) coexisting with oxides and hydroxides (stage II carbonate ore). The coprecipitation of smithsonite with galena, pyrite and arsenopyrite, as well as the absence of Fe- and Mn-oxides/hydroxides and of any discernible oxidation or dissolution of the sphalerite-rich primary sulfide ore, shows that the fluids responsible for the main, stage I carbonate ores were relatively reduced and close to neutral to slightly basic pH with high fCO₂. Smithsonite δ¹⁸O_VSMOW values from stage I carbonate ore range from 18.3 to 23.6‰, while those of stage II carbonate ore show a much smaller range between 24.3 and 24.9‰. The δ¹³C values are fairly constant in smithsonite of stage I carbonate ore (3.2–6.0‰) but show a considerable spread towards lower δ¹³C_VPDB values (4.6 to −11.2‰) in stage II carbonate ore. This suggests a hypogene formation of stage I carbonate ore at Angouran from low-temperature hydrothermal fluids, probably mobilized during the waning stages of Tertiary–Quaternary volcanic activity in an environment characterized by abundant travertine systems throughout the whole region. Conversely, stage II carbonate ore is unambiguously related to supergene weathering, as evidenced by the absence of sulfides, the presence of Fe-Mn-oxides and arsenates, and by high δ¹⁸O values found in smithsonite II. The variable, but still relatively heavy carbon isotope values of supergene smithsonite II, suggests only a very minor contribution by organic soil carbon, as is generally the case in supergene nonsulfide deposits.