Characterization of C‐isotope variability in the Delhi Supergroup,northwestern India and the Mesoproterozoic ocean

Marine carbonate rocks of the Delhi Supergroup of northwestern India show little deviation in whole‐rock δ ¹³Ccarb and δ ¹⁸Ocarb values, which generally are around 0 and –10‰ respectively. These narrow ranges and almost constant δ ¹³Ccarb values persist despite close sampling through long sections. The data suggest that the global rate of organic carbon burial was probably constant during deposition of the Delhi Supergroup. The nearly invariant C isotopic profile of the Delhi Supergroup is similar to C isotopic profiles of Mesoproterozoic carbonates older than 1.3 Ga, as reported from different parts of world. Carbonate units on the western margin of the Delhi Supergroup however, have on average moderately positive δ ¹³C values (from 2 to +4.96‰). These high δ ¹³C carbonates may represent the Mesoproterozoic–Neoproterozoic transition (from ～1.25 to ～0.85 Ga), a period characterized by high positive δ ¹³C values globally.     

Carbon,oxygen and strontium isotope geochemistry of Proterozoic carbonate rocks of the Vindhyan Basin,central India

Carbon, oxygen and strontium isotope compositions of carbonate rocks of the Proterozoic Vindhyan Supergroup, central India suggest that they can be correlated with the isotope evolution curves of marine carbonates during the latter Proterozoic. The carbonate rocks of the Lower Vindhyan Supergroup from eastern Son Valley and central Vindhyan sections show δ¹³C values of ∼0‰ (V-PDB) and those from Rajasthan section are enriched up to +2.8‰. In contrast, the carbonate rocks of the Upper Vindhyan succession record both positive and negative shifts in δ¹³C compositions. In the central Vindhyan section, the carbonates exhibit positive δ¹³C values up to +5.7‰ and those from Rajasthan show negative values down to –5.2‰. The δ¹⁸O values of most of the carbonate rocks from the Vindhyan Supergroup show a narrow range between –10 and –5‰ (V-PDB) and are similar to the ‘best preserved’ ¹⁸O compositions of the Proterozoic carbonate rocks. In the central Vindhyan and eastern Son Valley sections, carbonates from the Lower Vindhyan exhibit best-preserved ⁸⁷Sr/⁸⁶Sr compositions of 0.7059±6, which are lower compared to those from Rajasthan (0.7068±4). The carbonates with positive δ¹³C values from Upper Vindhyan are characterized by lower ⁸⁷Sr/⁸⁶Sr values (0.7068±2) than those with negative δ¹³C values (0.7082±6). A comparison of C and Sr isotope data of carbonate rocks of the Vindhyan Supergroup with isotope evolution curves of the latter Proterozoic along with available geochronological data suggest that the Lower Vindhyan sediments were deposited during the Mesoproterozoic Eon and those from the Upper Vindhyan represent a Neoproterozoic interval of deposition.     

High-δ13C Paleoproterozoic Carbonates from the Aravalli Supergroup,Western India

High δ¹³C values up to 11%_PDB occur in Paleoproterozoic dolostones from the Aravalli Supergroup, western India. Correlation of high δ¹³C with high δ¹⁸O up to 23%_SMOW in the studied carbonates suggests that pre-metamorphic δ¹³C values were above 10%_PDB. The data are consistent with worldwide positive excursions in the δ¹³C of marine bicarbonate. The positive excursion was contemporaneous with sedimentation.     

Petrology and stable isotope (S,C, O) studies of selected sedimenthosted basemetal ore deposits in the proterozoic Aravalli-Delhi Fold Belt,Rajasthan

An integrated mineralogical-geochemical and stable isotopic study of Pb-Zn deposits located at Kayar-Ghugra (Zn-Pb ± Ag), Rampura-Agucha (Zn-Pb, Ag), Dariba-Bethumni (Zn-Pb) and Zawar (Pb-Zn ± Cd, Ag) in Rajasthan is presented in this paper. The Kayar Zn-Pb deposit hosted by (i) phlogopite-tremolite bearing dolomitic carbonates and (ii) scapolite bearing calc-silicates, both belonging to Mesoproterozoic Delhi Supergroup exhibit distinctly different δ¹³C signatures being close to zero permil for the former reflecting deposition in pristine marine environment and much depleted isotopic values for the latter possibly related to post-depositional alterations. The Zn-Pb sulphides of Agucha, hosted in amphibolite facies to lower granulite facies metasedimentary units belonging to the Bhilwara Supergroup have δ³⁴S values that indicate (i) H₂S dominated regime characterized by low fO₂, low pH, wherein the δ³⁴S_(fluid) responsible for mineralisation approximates the δ³⁴S_(sulphide); (ii) the role of seawater in the generation of Agucha ores; (iii) the process of a low temperature oxidation of sulphides in the hydrothermal fluids resulting in the formation of sulphate, by the interaction of ground water; (iv) isotopic disequilibrium in sulphatesulphide pairs that explain oxidation of H₂S by acid groundwater (low pH) and deposition of sulphides at higher temperatures and (v) equilibrium isotopic fractionation of the coexisting sulphides reflecting in a higher concentration of H₂S (>10^?5m) in relation to the total metal content in the hydrothermal fluid $\left( {m_{H_2 S} \geqslant mS_{_{metals} } } \right)$ . Accordingly the concentration of sulphide-sulphate in the hydrothermal solution responsible for the mineralization in Agucha exceeds that of total metals. The sulphides of Bethumni-Rajpura-Dariba belt hosted in low to medium grade siliceous carbonates has a marginally positive (mean of +1.5‰) δ¹³C values. At Sindeswar, broad and widely scattered δ³⁴S values indicate a polymodal sedimentary source of sulphur that recrystallised at rather low temperature of < 50°C possibly during the processes of low temperature bacterial reduction. The C and O-isotopic studies on mineralized and non-mineralized carbonates reveal (i) normal marine depositional signatures for non-mineralized carbonates with possible minor influence of biogenic carbon during deposition and (ii) ore zone carbonates exhibit depleted δ¹³C values presumably due either to the deeper mantle-like source of carbonates or due to post-depositional equilibration with isotopically light meteoric waters. In Zawar belt, sulphides hosted in dolomitic carbonate indicated (i) near identical δ³⁴S values of disseminated galena and pyrite veinlets and depleted values of ?4.6 ‰ for late veins of massive galena of Zawar Mala (ii) pyritepyrrhotite veinlet having enhanced δ³⁴S values when compared to the PbS-ZnS veinlet in Morchia-Magra, Balaria and Baroi mines. The carbon isotopic values for carbonates of Zawar Mala mine area are mostly depleted and those from Balaria and Baroi mines exhibit values of ¹³C close to zero. The generally depleted δ ¹⁸O clustering around ?15 ‰ tally well with the reported Paleoproterozoic carbonates and is attributed to the post-depositional equilibration reactions with isotopically light meteoric waters. It is summarized that the host carbonates for Zn-Pb deposits occurring in different tectono-stratigraphic units in Rajasthan have largely similar but bimodal distribution of δ ¹⁸O and δ¹³C isotopic ratios that suggest normal marine values and much depleted values. Whereas the former seems to be in general agreement with the nature of distribution in the Palaeoproterozoic carbonates the latter is attributed to (i) depositional conditions of the basins that includes absence or presence of biogenic activity (ii) isotopic re-equilibration under different metamorphic recrystallization events and/or (iii) interaction with isotopically lighter meteoric waters. In contrast to the uniformity in the C and O distribution pattern, the S-isotopic distribution in the deposits of Rampura-Agucha, Bethumni-Rajpura-Darbia and Zawar mine areas show marked variations reflecting complex deposit-specific ore-forming processes in the said deposits.     

Diamond growth from oxidized carbon sources beneath the Northern Slave Craton, Canada: A δC-N study of eclogite-hosted diamonds from the Jericho kimberlite

Diamonds from high- and low-MgO groups of eclogite xenoliths from the Jericho kimberlite, Slave Craton, Canada were analyzed for carbon isotope compositions and nitrogen contents. Diamonds extracted from the two groups show remarkably different nitrogen abundances and δ¹³C values. While diamonds from high-MgO eclogites have low nitrogen contents (5-82 ppm) and extremely low δ¹³C values clustering at ∼−40‰, diamonds from the low-MgO eclogites have high nitrogen contents (>1200 ppm) and δ¹³C values from −3.5‰ to −5.3‰.Coupled cathodoluminescence (CL) imaging and SIMS analysis of the Jericho diamonds provides insight into diamond growth processes. Diamonds from the high-MgO eclogites display little CL structure and generally have constant δ¹³C values and nitrogen contents. Some of these diamonds have secondary rims with increasing δ¹³C values from −40‰ to ∼−34‰, which suggests secondary diamond growth occurred from an oxidized growth medium. The extreme negative δ¹³C values of the high-MgO eclogite diamonds cannot be produced by Rayleigh isotopic fractionation of average mantle-derived carbon (−5‰) or carbon derived from typical organic matter (∼−25‰). However, excursions in δ¹³C values to −60‰ are known in the organic sedimentary record at ca. 2.7 and 2.0 Ga, such that diamonds from the high-MgO eclogites could have formed from similar organic matter brought into the Slave lithospheric mantle by subduction.SIMS analyses of a diamond from a low-MgO eclogite show an outer core with systematic rimwards increases in δ¹³C values coupled with decreases in nitrogen contents, and a rim with pronounced alternating growth zones. The coupled δ¹³C-nitrogen data suggest that the diamond precipitated during fractional crystallization from an oxidized fluid/melt from which nitrogen was progressively depleted during growth. Model calculations of the co-variation of δ¹³C-N yielded a partition coefficient (K_N) value of 5, indicating that nitrogen is strongly compatible in diamond relative to the growth medium. δ¹³C values of diamond cores (−4‰) dictate the growth medium had higher δ¹³C values than primary mantle-derived carbon. Therefore, possible carbon sources for the low-MgO eclogite diamonds include oxidized mantle-derived (e.g. protokimberlite or carbonatite) fluids/melts that underwent some fractionation during migration or, devolatilized subducted carbonates.     

Strontium and carbon isotope stratigraphy of the Late Jurassic shallow marine limestone in western Palaeo-Pacific,northwest Borneo

Strontium and carbon isotope stratigraphy was applied to a 202 m-thick shallow marine carbonate section within the Late Jurassic Bau Limestone at the SSF quarry in northwest Borneo, Malaysia, which was deposited in the western Palaeo-Pacific. Strontium isotopic ratios of rudist specimens suggest that the SSF section was formed between the latest Oxfordian (155.95 Ma) and the Late Kimmeridgian (152.70 Ma), which is consistent with previous biostratigraphy. The δ¹³C_carb values of bulk carbonate range from −0.10 to +2.28‰ and generally show an increasing upward trend in the lower part of the section and a decreasing upward trend in the upper part of the section. A comparable pattern is preserved in the δ¹³C_org isotope record. Limestone samples of the SSF section mainly preserve the initial δ¹³C_carb values, except for the interval 84–92 m, where an apparent negative anomaly likely developed as a result of meteoric diagenesis. Comparing with the Tethyan δ¹³C_carb profile, a negative anomaly in the lower SSF section can be correlated with the lowered δ¹³C values around the Oxfordian/Kimmeridgian boundary. In addition, δ¹³C_carb values of the Bau Limestone are generally ∼1‰ lower than the Tethyan values, but comparable with the values reported from Scotland and Russia, located in Boreal realm during the Late Jurassic. This suggests that either the Tethyan record or the other records have been affected by the δ¹³C values of regionally variable dissolved inorganic carbon (DIC). The Late Jurassic δ¹³C_DIC values are thought to have been regionally variable as a result of their palaeoceanographic settings. This study shows that δ¹³C chemostratigraphy of the Palaeo-Pacific region contributes to an improved understanding of global carbon cycling and oceanography during this time period.     

Stable isotope of some selected Egyptian pectinids and their paleoenvironmental implications

Eight pectinid shells were collected and subjected to quantitative study using δ¹⁸O and δ¹³C isotopic analysis in order to study the paleoenvironment which prevailed during their calcification. The scalerochronological variations in δ¹⁸O and δ¹³C values, among these shells are also discussed. The Early Miocene pectinid shells display highly depleted δ¹⁸O and δ¹³C signature as a result of paleo-meteoric water with heavy rainfall that was produced by Tropical Cyclones when the Mediterranean Sea was open. The Early Pliocene pectinid shells reveal depleted δ¹⁸O values, related to the influx of fresh water influenced by monsoonal activity following the formation of the Tibetan Plateau. Their enrichment in the δ¹³C isotopic excursion is referred to high productivity of the Indian Ocean, which was the main source of the Red Sea water. The Pleistocene pectinid shell shows highly depleted δ¹⁸O and δ¹³C signature with obvious diagenetic shell structure, indicating that a wetter humid climate prevailed during the Early–Middle Pleistocene and long sub-arial exposure of the shell. The Recent Mediterranean pectinid shell displays slight enrichment in δ¹⁸O and δ¹³C values referring to deeper inhabitation of this species with a low temperature and high salinity environment. The scalerochronological variations in both δ¹⁸O and δ¹³C values, along these shells is referred to seasonal variations or kinetic effects.     

Juvenile CO2 in enderbites of Tromøy near Arendal, southern Norway: a fluid inclusion and stable isotope study

The enderbites from Tromøy in the central, granulite facies part of the Proterozoic Bamble sector of southern Norway contain dominantly CO₂ and N₂ fluid inclusions. CO₂ from fluid inclusions in quartz segregations in enderbites was extracted by mechanical (crushing) and thermal decrepitation and the δ¹³C measured. Measurement was also made on samples washed in 10% HCl, oxidized with CuO at high temperatures, and step-wise extracted with progressive heating. Results between the different techniques are systematic. The main results show δ¹³C of -4.5±1.5% for crushing and -7±2% for thermal decrepitation. δ¹³C is about constant for CO₂ extracted at different temperatures and points to a homogeneous isotopic composition. Due to the presence of carbonate particles and/or induced contaminations for the extraction by thermal decrepitation, the results for the crushing experiments are assumed the most reliable for fluid-inclusion CO₂. Very low values of δ¹³C have not been found in enderbite samples and δ¹³C combined with δ¹⁸O of the host quartzes (8-11%) indicates juvenile values. In addition, the fluid inclusions were examined by microthermometry and Raman analysis and host quartz by acoustic emission and cathodoluminescence. CO₂ fluid inclusions have varying densities with a frequency maximum of 0.92 g cm^-3 and generally do not concur with trapping densities at granulite conditions. Textures show that CO₂ must have been trapped in fluid inclusions in one early event, but transformed to different extents during late isothermal uplift without important fractionation of isotope compositions. The present data support a model of intrusion and crystallization of a CO₂-rich enderbitic magma at granuiite conditions.     

Wet-dry seasonal and spatial variations in the δC and δO values of the modern endogenic travertine at Baishuitai, Yunnan, SW China and their paleoclimatic and paleoenvironmental implications

Seasonal and spatial variations in the δ¹³C and δ¹⁸O values of the modern endogenic (thermogene) travertine deposited in a calcite-depositing canal at Baishuitai, Yunnan, SW China were examined to understand their potential for paleoclimatic and paleoenvironmental implications. The sampling sites were set in the upstream, middle reach and downstream of the canal, and the modern endogenic travertine samples were collected semimonthly to measure their δ¹³C and δ¹⁸O values. It was found that both δ¹³C and δ¹⁸O values of the endogenic travertine were low in the warm rainy season and high in the cold dry season, and correlated with each other. The low δ¹⁸O values in warm rainy season were mainly related to the higher water temperature and the lower δ¹⁸O values of rainwater, and the low δ¹³C values are caused by the dilution effect of overland flow with low δ¹³C values in the warm rainy season and the reduced CO₂-degassing of canal-water caused by the dilution effect of the overland flow. The linear negative correlation between the travertine δ¹⁸O (or δ¹³C) values and rainfall amount may be used for paleo-rainfall reconstruction if one knows the δ¹⁸O (or δ¹³C) values of the fossil endogenic travertine at Baishuitai though the reconstruction was not straightforward. It was also found that there was a progressive downstream increase of the δ¹⁸O and δ¹³C values of the travertine along the canal, the former being mainly due to the preferential evaporation of H₂¹⁶O to the atmosphere and the latter to the preferential release of ¹²CO₂ to the atmosphere during CO₂-degassing. However, the downstream increase of the travertine δ¹⁸O and δ¹³C values was less intensive in rainy season because of the reduced evaporation and CO₂-degassing during the rainy season. To conclude, the downstream travertine sites could be more favorable for the paleo-rainfall reconstruction while the upstream travertine sites are more favorable for the paleo-temperature reconstruction. So, this study demonstrates that endogenic travertine, like epigenic (meteogene) tufa, could also be a good candidate for high-resolution paleoclimatic and paleoenvironmental reconstruction.     

Large variations of δ13C values in stalagmites from southeastern China during historical times: implications for anthropogenic deforestation

Variations in speleothem δ¹³C values can reflect changes in overlying surface vegetation, which, over historical time scales, may represent the influence of human activities. Here, we examined δ¹³C variations in two stalagmites growing for the last 2200 years in Shennong Cave, Jiangxi Province, SE China. The two δ¹³C records corroborate well one another and show a prominent 6‰ enrichment of the δ¹³C values from AD 700 to 1100. The isotopic equilibrium for modern calcite and negative correlation between δ¹⁸O and δ¹³C values along the growth axis suggest that the influences of kinetic fractionation are negligible. Varied correlations between Mg/Ca and Sr/Ca ratios and divergent changes between δ¹³C values and Mg/Ca and Sr/Ca ratios from AD 700 to 1100 reveal that the prior calcite precipitation (PCP) and water–rock interaction did not dominate the increase of δ¹³C values. It is plausible that the obvious δ¹³C variation was largely influenced by the changes in vegetation cover overlying the cave. Our δ¹³C results, together with the records of climate and human activity from historical documentary records, suggest that: (i) prior to AD 700, small fluctuations in relatively light δ¹³C values reflect the presence of lush forest coverage above the cave, which was minimally disturbed by human activities; (ii) during AD 700–1100, the drastic increase in δ¹³C values indicates persistent and massive deforestation associated with large‐scale immigration into northern Jiangxi after the Rebellion of An & Shi (AD 755–763) in the Tang Dynasty and the subsequent development of agriculture and economic activity; and (iii) since AD 1100, fluctuations in relatively high δ¹³C values suggest that local vegetation during the last millennium has been sparse. Since the Rebellion of An & Shi, southeastern China was progressively developed, coincident with deforestation and vegetation deterioration caused by human disturbance in the form of deforestation and cultivation.     

Veracity of Neoproterozoic negative C-isotope values: The termination of the Shuram negative excursion

There is widespread interest in the Neoproterozoic period of the Earth's history (1000 to 542 Ma) because of unprecedented δ¹³C fluctuations to < − 10‰ PDB through thick (> 1000 m) succession of stratigraphically complex sedimentary rocks deposited during tens of millions of years. In contrast, Phanerozoic large negative C-isotope excursions have been interpreted as the result of diagenetic fluid mixing during carbonate stabilization and burial and are less enigmatic due to the excellent biostratigraphic control on their timing and duration.The Ediacaran Nafun Group of Oman (part of the Huqf Supergroup spanning the Cryogenian–Early Cambrian) contains a large δ¹³C negative excursion (the Shuram excursion) reaching values as negative as − 12‰ at the base of the Shuram Formation. A steady recovery to positive values occurs over the entire Shuram and half through the overlying Buah Formation, suggesting a duration on the order of tens of My. Based on trace metal, chemostratigraphic and sedimentological analyses, the carbon isotope record obtained from the Buah Formation of northern Oman indicates a systematic and reproducible shift of δ¹³C values from − 6‰ to + 1‰ in 1 — a demonstrably diagenetic altered carbonate-cemented siliciclastic facies, and 2 — a least diagenetically altered stromatolitic facies. The identical reproducible isotopic pattern in these time-equivalent sections combined to the presence of exceptionally preserved δ¹⁸O values around − 2 to + 1‰ associated with the most negative δ¹³C values rules out isotopic resetting by diagenetic fluids as a mechanism to explain these values.It is concluded that it is possible to retain depositional δ¹³C values in demonstrably diagenetically altered carbonates. This raises the issue of the ability to recognize diagenetic alteration of C-isotopic values in Neoproterozoic rocks where a robust time frame to support reproducibility is not available. The results of this study provide strong support to a non diagenetic origin of the negative Shuram C-isotope excursion, believed to be the most profound (in terms of amplitude and duration) in the Earth's history.     

Global nature of the Paleoproterozoic Lomagundi carbon isotope excursion: A review of occurrences in Brazil,India, and Uruguay

Positive carbon isotope excursion is reported from Paleoproterozoic carbonates of the Aravalli Supergroup (northwestern India), the Minas Supergroup (Brazil), and new sections of the Paso Severino Formation (Uruguay). The 2.42 Ga Gandarela Formation, Minas Gerais, Brazil, contains red carbonate-facies BIF grading into dolostones and limestones and yielding δ¹³C values ranging from −1.6 to +0.4‰ V-PDB. The positive C-isotope excursion (up to + 11‰ V-PDB) in marine shallow-water carbonates in India and Brazil (Jhamarkotra Formation in northwestern India, and Cercadinho and Fecho do Funil formations in Minas Gerais State, Brazil) is comparable to that observed in 2.22–2.1 Ga carbonate successions worldwide that were deposited during the Lomagundi excursion. In Uruguay, δ¹³C values up to +11.6‰ V-PDB in the deep-water Paso Severino Formation of the Piedra Alta Terrane are compatible with deposition at ca. 2.15 Ga, as indicated by the 2146 ± 7 Ma U–Pb age of dacites occurring at the top of the unit. Negative δ¹³C values are also present in carbonates of the Paso Severino Formation, but an origin related to organic-matter remineralization cannot be ruled out. Thin carbonate beds in the Rio Itapicuru greenstone belt, Bahia State, Brazil, are associated, as in the Paso Severino Formation, with deep-water black shales and have carbon isotope values up to +9‰ V-PDB. High metamorphic grade carbonates of the Jacurici terrane in the Medrado-Ipueira area, Bahia, Brazil, have carbon isotope values up to +6.9‰ V-PDB, consistent with their minimum age of 2085 ± 5 Ma inferred from the intrusive contact with and the age of the Medrado norite. No evidence was found in India, Brazil, or Uruguay for Paleoproterozoic glacial events recognized in the 2.45–2.22 Ga sedimentary successions worldwide. Unconformities between the Gandarela and Cercadinho formations in Brazil and the banded gneissic Complex and the Lower Aravalli Supergroup in India might explain the absence of glacial record. Compositional and isotopic data presented here for studied Paleoproterozoic carbonate successions allow their integration into the global record of the Paleoproterozoic evolution as well as correlation with other successions of similar age. The study highlights the global nature of the Lomagundi excursion. Furthermore, it indicates that the Lomagundi excursion is recorded in both shallow-water (Aravalli and Minas supergroups) and deep-water carbonates (Paso Severino Formation and Rio Itapicuru greenstone belt) negating a significant impact of stromatolite productivity and hypersaline conditions on carbon isotope values of carbonates deposited in shallow-water, open-marine and isolated basins.     

Fibrous calcite from the Ordovician of Tennessee: preservation of marine oxygen isotopic composition and its implications

Three categories of fibrous calcite from early to middle Caradoc platform-marginal buildups in east Tennessee can be delineated using cathodoluminescent microscopy, minor element chemistry and stable C-O isotopic composition. Bright luminescent fibrous cement has elevated Mn (>1000 p.p.m.), negative δ¹³C and intermediate δ¹⁸O values relative to other types of fibrous calcite. This cement reflects fibrous calcite that interacted with reducing Mn-rich fluids. Dully luminescent fibrous cement has elevated Fe (>400 p.p.m.), positive δ¹³C and negative δ¹⁸O values relative to other fibrous cements. This cement was stabilized by burial fluids. Nonluminescent fibrous cement has low Mn and Fe (generally below 400 p.p.m.) and positive δ¹³C and δ¹⁸O values relative to other types of fibrous calcite. The latter cement is interpreted to be the best material for determining the isotopic composition of calcite precipitated in equilibrium with early to middle Caradoc seawater, which is δ¹³C=1% PDB and δ¹⁸O=?4 to ?5‰ PDB. Results from this study and Ashgillian brachiopods indicate that the average δ¹⁸O composition of the Ordovician ocean, during nonglacial periods, was probably never more negative than ?3‰ SMOW. Assuming an Ordovician seawater δ¹⁸O value of ?1‰ SMOW, Holston Formation fibrous cements would have precipitated at temperatures between 27 and 36 °C, which is near the upper temperature limit for metazoans. A seawater δ¹⁸O value of ?2‰ SMOW yields temperatures ranging from 23 to 31 °C, while a ?3‰ SMOW value yields temperatures of 18–26 °C.     

Sources of fine-sized organic matter in North Atlantic Heinrich Layers: δC and δN tracers

Organic carbon (OC) and total nitrogen (TN) concentrations and stable isotope ratios (δ¹³C, δ¹⁵N) of fine (<50 μm) size fractions of deep-sea sediments from the central North Atlantic were employed to identify changes in sources of organic matter over the past 50 ka BP. Ambient glacial sediments are characterised by values that reflect mixtures of marine and terrestrial inputs (averages ± 1σ: OC/TN = 7.6 ± 0.8; δ¹³C = −22.8 ± 1.0‰; δ¹⁵N = 5.5 ± 0.6‰). δ¹³C, OC, and TN concentrations shift to higher values during the Holocene, indicating a gradual decrease of fine terrigenous supply to the North Atlantic. The unchanged δ¹⁵N record between last glacial and Holocene stages indicates that the central North Atlantic region remained oligotrophic at least during the past 50 ka BP, but additional studies are required to support this result in terms of nitrogen oceanic budget. During the phases of enhanced ice-rafted detrital supply corresponding to prominent Heinrich events (HL₁, HL₂, HL₄, and HL₅), fine-sized sedimentary organic matter has lower OC and TN concentrations, contrasting sharply with those of ambient glacial sediments. Lower δ¹³C (down to −28‰) and δ¹⁵N (down to 1.6‰) values and high OC:TN ratios (up to 14.7 ± 1.1) are found for HL₁, HL₂, and with lesser extent for HL₄. These values reflect enhanced detrital supply originating from poorly differentiated soil horizons that characterise periglacial climate conditions and from organic matter-bearing rock sources of the underlying geological basement. During HL₅, only the δ¹³C offset records the input of fine size ice-rafted organic matter. Gradually changing soil development conditions during the time interval covering HL₅ to HL₁ (marine isotope stages 5 to 2), as well as varying erosion levels, have been hypothesized on the basis of constant δ¹³C, increasing OC/TN and decreasing δ¹⁵N values.     

济阳坳陷奥陶系碳酸盐岩及缝洞充填方解石C、O同位素特征及其意义

对济阳坳陷奥陶系碳酸盐原岩及孔洞缝中充填方解石进行了C、O同位素测定,结果表明孔洞缝充填方解石的δ¹³C和δ¹⁸O值比原岩偏负。奥陶系三山子组和马家沟组孔缝中充填的方解石C、O同位素演化有很大区别,前者的δ¹³C和δ¹⁸O值均为负值,δ¹³C向较高负值偏移,δ¹⁸O值向较低负值偏移;马家沟组八陡段孔缝充填方解石的δ¹³C和δ¹⁸O值也多为负值,δ¹³C向较正值方向偏移,δ¹⁸O值向较高负值偏移。奥陶系碳酸盐岩孔缝充填方解石形成于大气淡水环境和埋藏成岩环境,次生孔洞可能主要形成于早期表生阶段,裂缝形成于中-新生代的构造运动,方解石主要充填于埋藏环境中。次生孔缝的主要形成时期早于油气大量运移期,对古潜山油藏的形成有利。     

Microbial hydrocarbon gases in the Witwatersrand Basin, South Africa: Implications for the deep biosphere

In this study, compositions and δ¹³C and δ²H isotopic values of hydrocarbon gases from 5 mines in the Witwatersrand basin, South Africa, support the widespread occurrence of microbially produced methane in millions of years-old fissure waters. The presence of microbial methane is, to a large extent, controlled by the geologic formations in which the gases are found. Samples from the Witwatersand Supergroup have the largest microbial component based on δ¹³C and δ²H signatures and CH₄/C₂+ values. Based on mixing between a microbial CH₄ component and a more ¹³C-enriched and ²H-depleted C₂+-rich end member, conservative estimates of the % contribution of microbial CH₄ to the gas samples range from >90% microbial CH₄ at Beatrix, Masimong, and Merriespruit, to between 5 and 80% microbial CH₄ at Evander, and <18% microbial CH₄ at Kloof. The Witwatersrand basin’s history of thermal alteration of organic-rich ancient sedimentary units suggests a thermogenic origin for this ¹³C-enriched end member. Alternatively, the potential for an abiogenic origin similar to hydrocarbon gases produced by water-rock interaction at other Precambrian Shield mines is discussed. Microbial methane is predominantly found in paleo-meteoric fissure waters with δ¹⁸O and δ²H values that fall on the meteoric waterline, and have temperatures between 30 to 40°C. In contrast, fissure waters with a larger component of nonmicrobial hydrocarbon gases show a trend towards more enriched δ¹⁸O and δ²H values that fall well above the meteoric waterline, and temperatures of 45 to 60°C. The enrichment in ¹⁸O and ²H in these samples, and their high salinity, are similar to the isotopic and compositional characteristics of saline groundwaters and brines produced by water-rock interaction at Precambrian Shield sites elsewhere. The reported 100 Ma ages of fissure waters from the Witwatersrand and Ventersdorp formations suggest that these microbial hydrocarbon gases are the product of in situ methanogenic communities in the deep subsurface of the Witswaterand basin. Small subunit ribosomal RNA genes were amplified using archaeal-specific primer sets from DNA extracts derived from several of these waters. Fissure waters with a high proportion of microbial methane also contained sequences resembling those of known methanogens.     

Preservation of biosignatures in metaglassy volcanic rocks from the Jormua ophiolite complex,Finland

Evidence of microbially-mediated alteration of basaltic glass is preserved in originally glassy basalts (rims of pillow lavas, hyaloclastite breccias, and chilled margins of dykes) from the well-preserved 1.95 Ga Jormua ophiolite complex (JOC) of Northeastern Finland. Although textural evidence of microbial alteration is commonly observed in relic glass from recent oceanic crust and some ophiolites, these textures have been destroyed during greenschist to lower amphibolite facies regional metamorphism and deformation of the JOC. However, another robust biosignature is found in the generally depleted δ¹³C values of disseminated carbonate extracted from originally glassy basalts, relative to crystalline samples. The same distribution of δ¹³C values is well documented in samples from recent oceanic crust as well as ophiolites of Phanerozoic age. This characteristic contrast in the δ¹³C values of disseminated carbonate is interpreted to result from microbe-induced fractionation during oxidation of organic matter. X-ray mapping of initial alteration zones has identified residual carbon associated with highly-concentrated S that is unrelated to carbonate. We attribute these biosignatures to microbially-mediated alteration of originally glassy material prior to ophiolite emplacement.     

Carbon and oxygen isotope chemostratigraphies of the Yangtze platform,South China: Decoding temperature and environmental changes through the Ediacaran

Multicellular animals first appeared on the earth during the Ediacaran period. However, the relationship between the abrupt biological evolution and environmental changes is still ambiguous. In order to examine seawater temperature and the carbon cycle through the Ediacaran, we analyzed the carbon and oxygen isotope compositions of carbonate rocks from drill cores from the Three Gorges area, South China. Importantly, the core samples include the Nantuo tillite, corresponding to the Marinoan glaciation, through the Doushantuo to the lower Dengying Fms. in ascending order.The δ¹³C profile displays five positive and five negative anomalies (PI-1 to 5 and NI-1 to 5), and the oxygen isotopes display very high absolute values around 0‰ with the highest at + 1.83‰. The combined δ¹⁸O and δ¹³C chemostratigraphies display both positive and negative correlations between the δ¹⁸O and δ¹³C values. The occurrence of the negative correlations supports the preservation of primary δ¹⁸O and δ¹³C values.The sample NI-4 has a negative correlation of the δ¹⁸O and δ¹³C excursions. The correlation supports a primary signature for both δ¹⁸O and δ¹³C variations. The positive δ¹⁸O excursion, accompanied by evidence of a eustatic sea-level fall, provides direct evidence for global cooling in the mid-Ediacaran; the 580 Ma Gaskiers Glaciation is a potential candidate for this global cooling event. The negative δ¹³C excursion was possibly caused by an increase in remineralization of dissolved organic carbon (DOC) due to enhanced continental weathering during the glaciation.Sample NI-5 is characterized by very low δ¹³C values, down to ? 10‰, corresponding to the Shuram-Wonoka-Pertatataka Excursion. The cause of the δ¹³C negative excursion is still not clear. However, a ubiquitous occurrence in excursions worldwide, and the lower δ¹³C values in deeper sections favor the enhancement of remineralization and respiration rather than secondary alteration, a restricted sea environment and lithification in coastal areas.     

Stable isotopic signatures of superposed fluid events in granulite facies marbles of the Rauer Group, East Antarctica

The role of volatiles in the stabilization of the lower (granulite facies) crust is contentious. Opposing models invoke infiltration of CO₂-rich fluids or generally vapour-absent conditions during granulite facies metamorphism. Stable isotope and petrological studies of granulite facies metacarbonates can provide constraints on these models. In this study data are presented from metre-scale forsteritic marble boudins within Archaean intermediate to felsic orthogneisses from the Rauer Group, East Antarctica. Forsteritic marble layers and associated calcsilicates preserve a range of ¹³C- and ¹⁸O-depleted calcite isotope values (δ¹³C= -9.9 to -3.0% PDB, δ¹⁸O = 4.0 to 12.1% SMOW). A coupled trend of ¹³C and ¹⁸O depletion (～2%, ～5%, respectively) from core to rim across one marble layer is inconsistent with pervasive CO₂ infiltration during granulite facies metamorphism, but does indicate localized fluid-rock interaction. At another locality, more pervasive fluid infiltration has resulted in calcite having uniformly low, carbonatite-like δ¹⁸O and δ¹³C values. A favoured mechanism for the low δ¹⁸O and δ¹³C values of the marbles is infiltration by fluids that were derived from, or equilibrated with, a magmatic source. It is likely that this fluid-rock interaction occurred prior to high-grade metamorphism; other fluid-rock histories are not, however, ruled out by the available data. Coupled trends of ¹³C and ¹⁸O depletion are modified to even lower values by the superposed development of small-scale metasomatic reaction zones between marbles and internally folded mafic (?) interlayers. The timing of development of these layers is uncertain, but may be related to Archaean high-temperature (>1000d?C) granulite facies metamorphism.     

Variations of the Ca/Ca ratio in seawater during the past 24 million years: evidence from δCa and δO values of Miocene phosphates

The Ca isotope variation of 11 Miocene and Pleistocene, authigenic, marine phosphates is rather small compared to the corresponding variation in δ¹⁸O values. The δ⁴⁴Ca values are not correlated with the δ¹⁸O values and, therefore, they are not temperature controlled. It is likely that the δ⁴⁴Ca values of the phosphorites reflect the variation in the δ⁴⁴Ca values of paleo-seawater but, in contrast to Sr, not the isotopic composition of seawater itself. Furthermore, Ca and Sr isotopic compositions are decoupled with decreasing stratigraphic age of the phosphate peloids with Sr isotopic compositions changing to more radiogenic values while Ca isotopic compositions remain rather stable. All samples have δ⁴⁴Ca values below present-day seawater values, suggesting that phosphate formation discriminates against heavy Ca isotopes.Phosphorites and carbonaceous sediments have a similar Ca isotopic variation during the Miocene. A systematic and more or less constant shift between marine carbonates and phosphates is observed: the phosphate samples are slightly less enriched in ⁴⁰Ca compared to carbonates. This shift has been related to a mineral-dependent kinetic mass fractionation during precipitation from seawater. The rather stable δ⁴⁴Ca value for the 19 to 9 Ma old phosphorites points to a constant δ⁴⁴Ca fractionation of about 1.1 between seawater and phosphorites during the past and suggests steady-state conditions for the Mid-Miocene seawater (sedimentation flux equals erosion flux).