Stable isotope evidence for ca. 2.7-Ga-old Archean cap carbonates from the Dharwar Supergroup, southern India

Carbon isotope compositions of carbonate rocks from similar to 2.7-Ga-old Neoarchean Vanivilas Formation of the Dharwar Supergroup presented earlier by us are re-evaluated in this study, besides oxygen isotope compositions of a few silica dolomite pairs. The purpose of such a revisit assumes significance in view of recent field evidences that suggest a glaciomarine origin for the matrix-supported conglomerate member, the Talya conglomerate, which underlies the carbonate rocks of the Vanivilas Formation. An in-depth analysis of carbon isotope data reveals preservation of their pristine character despite the rocks having been subjected to metamorphism to different degrees (from lower greenschist to lower amphibolite facies). The dolomitic member of Vanivilas Formation of Marikanive area is characterized by highly depleted delta C-13 value (up to -5 parts per thousand VPDB) and merits as the Indian example of ca. 2.7-Ga-old cap carbonate. This inference is further supported by estimated low temperature of equilibration documented by a few silica dolomite pairs from the Vanivilas Formation collected near Kalche area. These pairs show evidence for oxygen isotopic equilibrium at low temperatures (similar to 0-20 degrees C) with depleted water (delta O-18 = -21 parts per thousand to -15 parts per thousand VSMOW) of glacial origin. We propose that the mineral pairs were deposited during the deglaciation period when the ocean temperature was in its gradual restoration phase. The dolomite of Marikanive area is the first record of cap carbonates from the Indian subcontinent with Neoarchean antiquity.

Isotopic composition of inorganic carbon as an indicator of benzoate degradation by Pseudomonas putida: temperature, growth rate and pH effects.

Degradation experiments of benzoate by Pseudomonas putida resulted in enzymatic carbon isotope fractionations. However, isotopic temperature effects between experiments at 20 and 30 °C were minor. Averages of the last three values of the CO2 isotopic composition (δ13CCO2(g)) were more negative than the initial benzoate δ13C value (−26.2‰ Vienna Pee Dee Belenite (VPDB)) by 3.8, 3.4 and 3.2‰ at 20, 25 and 30 °C, respectively. Although the maximum isotopic temperature difference found was only 0.6‰, more extreme temperature variations may cause larger isotope effects. In order to understand the isotope effects on the total inorganic carbon (TIC), a better measure is to calculate the proportions of the inorganic carbon species (CO2(g), CO2(aq) and HCO3−) and to determine their cumulative δ13CTIC. In all three experiments δ13CTIC was more positive than the initial isotopic composition of the benzoate at a pH of 7. This suggests an uptake of 12C in the biomass in order to match the carbon balance of these closed system experiments.

The speliothem record of climate variability in Southern Arabia.

Uranium-series dated stalagmites from Oman indicate that pluvial conditions prevailed from 6.3 to 10.5, 78 to 82, 120 to 130, 180 to 200 and 300 to 330 kyr B.P.; all of these periods coincide with peak interglacials. Oxygen (δ18O) and hydrogen (δD) isotope ratios of speleothem calcite and fluid inclusions reveal the source of moisture and provide information on the amount of precipitation, respectively. δ18O and δD values of stalagmites deposited during peak interglacials vary between −8 and −4 ‰ (VPDB) and −53 and −20‰ (Vienna Standard Mean Ocean Water [VSMOW]) respectively, whereas modern stalagmites range from −2.6 to −1.1‰ in δ18O (VPDB) and −7.6 and −3.3‰ in δD (VSMOW), respectively. The growth and isotopic records indicate that during peak interglacial periods, the limit of the monsoon rainfall was shifted far north of its present location and each pluvial period was coinciding with an interglacial stage of the marine oxygen isotope record.

Stable isotopes (H-2, O-18 and C-13) in groundwaters from the northwestern portion of the Guarani Aquifer System (Brazil)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Taxon-specific δ13C analysis of chitinous invertebrate remains in sediments from Strandsjön, Sweden

Taxon-specific stable carbon isotope (δ13C) analysis of chitinous remains of invertebrates can provide valuable information about the carbon sources used by invertebrates living in specific habitats of lake ecosystems (for example, sediments, water column, or aquatic vegetation). This is complementary to δ13C of sedimentary organic matter (SOM), which provides an integrated signal of organic matter produced in a lake and its catchment, and of diagenetic processes within sediments. In a sediment record from Strandsjön (Sweden) covering the past circa 140 years, we analyzed SOM geochemistry (δ13C, C:Natomic, organic carbon content) and δ13C of chitinous invertebrate remains in order to examine whether taxon-specific δ13C records could be developed for different invertebrate groups and whether these analyses provide insights into past changes of organic carbon sources for lacustrine invertebrates available in benthic and planktonic compartments of the lake. Invertebrate taxa included benthic chironomids (Chironomus, Chironomini excluding Chironomus, Tanytarsini, and Tanypodinae), filter-feeders on suspended particulate organic matter (Daphnia, Plumatella and Cristatella mucedo), and Rhabdocoela. δ13C of chironomid remains indicated periodic availability of 13C-depleted carbon sources in the benthic environment of the lake as δ13C values of the different chironomid taxa fluctuated simultaneously between -34.7 and -30.5‰ (VPDB). Daphnia and Bryozoa showed parallel changes in their δ13C values which did not coincide with variations in δ13C of chironomids, though, and a 2-3‰ decrease since circa AD 1960. The decrease in δ13C of Daphnia and Bryozoa could indicate a decrease in phytoplankton δ13C as a result of lower lake productivity, which is in accordance with historical information about the lake that suggests a shift to less eutrophic conditions after AD 1960. In contrast, Rhabdocoela cocoons were characterized by relatively high δ13C values (-30.4 to -28.2‰) that did not show a strong temporal trend, which could be related to the predatory feeding mode and wide prey spectrum of this organism group. The taxon-specific δ13C analyses of invertebrate remains indicated that different carbon sources were available for the benthic chironomid larvae than for the filter-feeding Daphnia and bryozoans. Our results therefore demonstrate that taxon-specific analysis of δ13C of organic invertebrate remains can provide complementary information to measurements on bulk SOM and that δ13C of invertebrate remains may allow the reconstruction of past changes in carbon sources and their δ13C in different habitats of lake ecosystems.

Geochemical and palynological results of IODP Hole 302-M0004A from Lomonosov Ridge, Arctic Ocean

Several episodes of abrupt and transient warming, each lasting between 50,000 and 200,000 years, punctuated the long-term warming during the Late Palaeocene and Early Eocene (58 to 51 Myr ago) epochs**1,2. These hyperthermal events, such as the Eocene Thermal Maximum 2 (ETM2) that took place about 53.5 Myr ago**2, are associated with rapid increases in atmospheric CO2 content. However, the impacts of most events are documented only locally**3,4. Here we show, on the basis of estimates from the TEX86' proxy, that sea surface temperatures rose by 3-5 °C in the Arctic Ocean during the ETM2. Dinoflagellate fossils demonstrate a concomitant freshening and eutrophication of surface waters, which resulted in euxinia in the photic zone. The presence of palm pollen implies**5 that coldest month mean temperatures over the Arctic land masses were no less than 8 °C, in contradiction of model simulations that suggest hyperthermal winter temperatures were below freezing**6. In light of our reconstructed temperature and hydrologic trends, we conclude that the temperature and hydrographic responses to abruptly increased atmospheric CO2 concentrations were similar for the ETM2 and the better-described Palaeocene-Eocene Thermal Maximum**7,8, 55.5 Myr ago.

Salinity of the Eocene Arctic Ocean from oxygen isotope analysis of fish bone carbonate

Stable isotope analysis was performed on the structural carbonate of fish bone apatite from early and early middle Eocene samples (~55 to ~45 Ma) recently recovered from the Lomonosov Ridge by Integrated Ocean Drilling Program Expedition 302 (the Arctic Coring Expedition). The d18O values of the Eocene samples ranged from -6.84 per mil to -2.96 per mil Vienna Peedee belemnite, with a mean value of -4.89 per mil, compared to 2.77 per mil for a Miocene sample in the overlying section. An average salinity of 21 to 25 per mil was calculated for the Eocene Arctic, compared to 35 per mil for the Miocene, with lower salinities during the Paleocene Eocene thermal maximum, the Azolla event at ~48.7 Ma, and a third previously unidentified event at ~47.6 Ma. At the Azolla event, where the organic carbon content of the sediment reaches a maximum, a positive d13C excursion was observed, indicating unusually high productivity in the surface waters.

Model - data comparison of western African rainfall evolutions during the Last Interglacial (130-115 ka)

This dataset characterizes the evolution of western African precipitation indicated by marine sediment geochemical records in comparison to transient simulations using CCSM3 global climate model throughout the Last Interglacial (130-115 ka). It contains (1) defined tie-points (age models), newly published stable isotopes of benthic foraminifera and Al/Si log-ratios of eight marine sediment cores from the western African margin and (2) annual and seasonal rainfall anomalies (relative to pre-industrial values) for six characteristic latitudinal bands in western Africa simulated by CCSM3 (two transient simulations: one non-accelerated and one accelerated experiment).

Mid-Pliocene palynomorph record of the North Atlantic

The mid-Pliocene was an episode of prolonged global warmth and strong North Atlantic thermohaline circulation, interrupted briefly at circa 3.30 Ma by a global cooling event corresponding to marine isotope stage (MIS) M2. Paleoceanographic changes in the eastern North Atlantic have been reconstructed between circa 3.35 and 3.24 Ma at Deep Sea Drilling Project Site 610 and Integrated Ocean Drilling Program Site 1308. Mg/Ca ratios and d18O from Globigerina bulloides are used to reconstruct the temperature and relative salinity of surface waters, and dinoflagellate cyst assemblages are used to assess variability in the North Atlantic Current (NAC). Our sea surface temperature data indicate warm waters at both sites before and after MIS M2 but a cooling of ~2-3°C during MIS M2. A dinoflagellate cyst assemblage overturn marked by a decline in Operculodinium centrocarpum reflects a southward shift or slowdown of the NAC between circa 3.330 and 3.283 Ma, reducing northward heat transport 23-35 ka before the global ice volume maximum of MIS M2. This will have established conditions that ultimately allowed the Greenland ice sheet to expand, leading to the global cooling event at MIS M2. Comparison with an ice-rafted debris record excludes fresh water input via icebergs in the northeast Atlantic as a cause of NAC decline. The mechanism causing the temporary disruption of the NAC may be related to a brief reopening of the Panamanian Gateway at about this time.

n-Alkane analyses from an transect of marine surface sediments off southwest Africa

An isobathic transect of marine surface sediments from 1°N to 28°S off southwest Africa was used to further evaluate the potential of the chain length distribution and carbon stable isotope composition of higher plant n-alkanes as proxies for continental vegetation and climate conditions. We found a strong increase in the n-C29-33 weighted mean average d13C values from -33 per mil near the equator to around -26 per mil further south. Additionally, C25-35n-alkanes reveal a southward trend of increasing average chain length from 30.0 to 30.5. The data reflect the changing contribution of plants employing different photosynthetic pathways (C3 and C4) and/or being differently influenced by the environmental conditions of their habitat. The C4 plant proportions calculated from the data (ca. 20% for rivers draining the rainforest, to ca. 70% at higher latitude) correspond to the C4 plant abundance in continental catchment areas postulated by considering prevailing wind systems and river outflows. Furthermore, the C4 plant contribution to the sediments correlates with the mean annual precipitation and aridity at selected continental locations in the postulated catchment areas, suggesting that the C4 plant fraction in marine sediments can be used to assess these environmental parameters.

Lake Son Kol geochemistry, µXRF, biogeochemistry and pollen record

In general, a moderate drying trend is observed in mid-latitude arid Central Asia since the Mid-Holocene, attributed to the progressively weakening influence of the mid-latitude Westerlies on regional climate. However, as the spatio-temporal pattern of this development and the underlying climatic mechanisms are yet not fully understood, new high-resolution paleoclimate records from this region are needed. Within this study, a sediment core from Lake Son Kol (Central Kyrgyzstan) was investigated using sedimentological, (bio)geochemical, isotopic, and palynological analyses, aiming at reconstructing regional climate development during the last 6000 years. Biogeochemical data, mainly reflecting summer moisture conditions, indicate predominantly wet conditions until 4950 cal. yr BP, succeeded by a pronounced dry interval between 4950 and 3900 cal. yr BP. In the following, a return to wet conditions and a subsequent moderate drying trend until present times are observed. This is consistent with other regional paleoclimate records and likely reflects the gradual Late Holocene diminishment of the amount of summer moisture provided by the mid-latitude Westerlies. However, climate impact of the Westerlies was apparently not only restricted to the summer season but also significant during winter as indicated by recurrent episodes of enhanced allochthonous input through snowmelt, occurring before 6000 cal. yr BP and at 5100-4350, 3450-2850, and 1900-1500 cal. yr BP. The distinct ~1500-year periodicity of these episodes of increased winter precipitation in Central Kyrgyzstan resembles similar cyclicities observed in paleoclimate records around the North Atlantic, likely indicating a hemispheric-scale climatic teleconnection and an impact of North Atlantic Oscillation (NAO) variability in Central Asia.

Great Barrier Reef coral element/Ca and stable isotope data and U-Th ages from IODP Expedition 325

Tropical south-western Pacific temperatures are of vital importance to the Great Barrier Reef (GBR), but the role of sea surface temperatures (SSTs) in the growth of the GBR since the Last Glacial Maximum remains largely unknown. Here we present records of Sr/Ca and d18O for Last Glacial Maximum and deglacial corals that show a considerably steeper meridional SST gradient than the present day in the central GBR. We find a 1-2 °C larger temperature decrease between 17° and 20°S about 20,000 to 13,000 years ago. The result is best explained by the northward expansion of cooler subtropical waters due to a weakening of the South Pacific gyre and East Australian Current. Our findings indicate that the GBR experienced substantial meridional temperature change during the last deglaciation, and serve to explain anomalous deglacial drying of northeastern Australia. Overall, the GBR developed through significant SST change and may be more resilient than previously thought.

Organic geochemistry of sediments from North Alex Mud Vulcano

Hydrocarbon seeps are ubiquitous at gas-prone Cenozoic deltas such as the Nile Deep Sea Fan (NDSF) where seepage into the bottom water has been observed at several mud volcanoes (MVs) including North Alex MV (NAMV). Here we investigated the sources of hydrocarbon gases and sedimentary organic matter together with biomarkers of microbial activity at four locations of NAMV to constrain how venting at the seafloor relates to the generation of hydrocarbon gases in deeper sediments. At the centre, high upward flux of hot (70 °C) hydrocarbon-rich fluids is indicated by an absence of biomarkers of Anaerobic Oxidation of Methane (AOM) and nearly constant methane (CH4) concentration depth-profile. The presence of lipids of incompatible thermal maturities points to mixing between early-mature petroleum and immature organic matter, indicating that shallow mud has been mobilized by the influx of deep-sourced hydrocarbon-rich fluids. Methane is enriched in the heavier isotopes, with values of d13C ~-46.6 per mil VPDB and dD ~-228 per mil VSMOW, and is associated with high amounts of heavier homologues (C2+) suggesting a co-genetic origin with the petroleum. On the contrary at the periphery, a lower but sustained CH4 flux is indicated by deeper sulphate-methane transition zones and the presence of 13C-depleted biomarkers of AOM, consistent with predominantly immature organic matter. Values of d13C-CH4 ~-60 per mil VPDB and decreased concentrations of 13C-enriched C2+ are typical of mixed microbial CH4 and biodegraded thermogenic gas from Plio-Pleistocene reservoirs of the region. The maturity of gas condensate migrated from pre-Miocene sources into Miocene reservoirs of the Western NDSF is higher than that of the gas vented at the centre of NAMV, supporting the hypothesis that it is rather released from the degradation of oil in Neogene reservoirs. Combined with the finding of hot pore water and petroleum at the centre, our results suggest that clay mineral dehydration of Neogene sediments, which takes place posterior to reservoir filling, may contribute to intense gas generation at high sedimentation rate deltas.

Deep-sea sediment core PS2644 record from the southern Greenland Sea

The PS2644 deep-sea core sequence, retrieved from the northwestern margin of Iceland and covering the last 86 ka, exhibits high sedimentation rates during the last glacial cycle that allow the clear distinction of Greenland stadial (GS)/ interstadial (GI) cycles in the various proxy records. Abundance records of rhyolitic, basaltic and tachylytic tephra grains reveal several maxima. Tephra grains of all types were geochemically analyzed in 44 levels. A total of 92 tephras with a distinctive character have been defined within the glacial sequence of gravity core PS2644-5, whereas the Holocene record is dominated by reworked Vedde Ash grains and not suitable for tephra stratigraphic work. Of the 92 tephras only 19 geochemical populations have been linked with confidence to previously defined tephras such as from the Vedde Ash, Faeroe Marine Ash Zones (FMAZ) II and III and North Atlantic Ash Zone (NAAZ) II. For the glacial period informal names were given to 78 new tephras, most of which are basaltic tephras. Several of these layers have a unique geochemical character and might become new chronostratigraphic markers in the North Atlantic region. Linking the tephra populations to the volcanic system producing them, respectively, revealed that Icelandic eruptions dominate with 83 tephra geochemical populations and Jan Mayen with 9. Around 48% of the informal tephra layers linked to the Icelandic volcanic province are produced from either the Grimsvötn or the Veidivötn-Bardarbunga volcanic systems. The intervals spanning from Greenland Stadial (GS) 3 to Greenland Interstadial (GI) 4 (24.5-29 ka BP), from GI 8 to GS 10 (36.9-40.5 ka BP) and from GI 14 to GI 15.2 (50-56 ka BP) are the periods with the highest number of eruptions, all of which are associated with known tephra zones.

Sedimentation rate calculations and isotopic analysis on sediment cores along the IODP Expedition 311 transect

The oceanographic and tectonic conditions of accretionary margins are well-suited for several potential processes governing methane generation, storage and release. To identify the relevant methane evolution pathways in the northern Cascadia accretionary margin, a four-site transect was drilled during Integrated Ocean Drilling Program Expedition 311. The d13C values of methane range from a minimum value of -82.2 per mil on an uplifted ridge of accreted sediment near the deformation front (Site U1326, 1829 mbsl, meters below sea level) to a maximum value of -39.5 per mil at the most landward location within an area of steep canyons near the shelf edge (Site U1329, 946 mbsl). An interpretation based solely on methane isotope values might conclude the 13C-enrichment of methane indicates a transition from microbially- to thermogenically-sourced methane. However, the co-existing CO2 exhibits a similar trend of 13C-enrichment along the transect with values ranging from -22.5 per mil to +25.7 per mil. The magnitude of the carbon isotope separation between methane and CO2 (Ec = 63.8 ± 5.8) is consistent with isotope fractionation during microbially mediated carbonate reduction. These results, in conjunction with a transect-wide gaseous hydrocarbon content composed of > 99.8% (by volume) methane and uniform dDCH4 values (-172 per mil ± 8) that are distinct from thermogenic methane at a seep located 60 km from the Expedition 311 transect, suggest microbial CO2 reduction is the predominant methane source at all investigated sites. The magnitude of the intra-site downhole 13C-enrichment of CO2 within the accreted ridge (Site U1326) and a slope basin nearest the deformation front (Site U1325, 2195 mbsl) is ~ 5 per mil. At the mid-slope site (Site U1327, 1304 mbsl) the downhole 13C-enrichment of the CO2 is ~ 25 per mil and increases to ~ 40 per mil at the near-shelf edge Site U1329. This isotope fractionation pattern is indicative of more extensive diagenetic alteration at sites with greater 13C-enrichment. The magnitude of the 13C-enrichment of CO2 correlates with decreasing sedimentation rates and a diminishing occurrence of stratigraphic gas hydrate. We suggest the decreasing sedimentation rates increase the exposure time of sedimentary organic matter to aerobic and anaerobic degradation, during burial, thereby reducing the availability of metabolizable organic matter available for methane production. This process is reflected in the occurrence and distribution of gas hydrate within the northern Cascadia margin accretionary prism. Our observations are relevant for evaluating methane production and the occurrence of stratigraphic gas hydrate within other convergent margins.