High resolution stable isotope and Mg/Ca record of sediment core MD02-2550C2

An early Holocene record from the Gulf of Mexico (GOM) reveals climatic and hydrologic changes during the interval from 10.5 to 7 thousand calendar years before present from paired analyses of Mg/Ca and d18O on foraminiferal calcite. The sea surface temperature record based on foraminiferal Mg/Ca contains six oscillations and an overall ~1.5°C warming that appears to be similar to the September-March insolation difference. The d18O of seawater in the GOM (d18OGOM) record contains six oscillations, including a -0.8 per mil excursion that may be associated with the "8.2 ka climate event" or a broader climate anomaly. Faunal census records from three GOM cores exhibit similar changes, suggesting subcentennial-scale variability in the incursions of Caribbean waters into the GOM. Overall, our results provide evidence that the subtropics were characterized by decadal- to centennial-scale climatic and hydrologic variability during the early Holocene.

Nutrient availability affects the response of juvenile corals and the endosymbionts to ocean acidification

The interactive effects of nutrient availability and ocean acidification on coral calcification were investigated using post-settlement juvenile corals of Acropora digitifera cultured in nutrient-sufficient or nutrient-depleted seawater for 4 d and then exposed to seawater with different partial pressure of carbon dioxide () conditions (38.8 or 92.5 Pa) for 10 d. After the nutrient pretreatment, corals in the high nutrient condition (HN corals) had a significantly higher abundance of endosymbiotic algae than did those in the low nutrient condition (LN corals). The high abundance of endosymbionts in HN corals was reduced as a result of subsequent seawater acidification, and the chlorophyll a per algal cell increased. The photosynthetic oxygen production rate by endosymbionts was enhanced by the acidified seawater regardless of the nutrient treatment, indicating that the reduction in endosymbiont density in HN corals due to acidification was compensated for by the increase in chlorophyll a per cell. Though the photosynthetic rate increased in the acidified conditions for both LN and HN corals, the calcification rate significantly decreased for LN corals but not for HN corals. The acquisition of nutrients from seawater, rather than the increase in alkalinity caused by photosynthesis, might effectively alleviate the negative response of coral calcification to seawater acidification, suggesting that the response of corals and their endosymbionts to ocean acidification can be influenced by nutrient conditions.

Chemical and isotopic compositions of authigenic carbonates from bottom sediments of Northwest Pacific marginal seas

The paper presents data on authigenic carbonate distribution in Holocene - Upper Pleistocene deposits of the Okhotsk, Japan, East China, Philippine and South China Seas. Description of carbonate samples, their chemical and isotope compositions are given. Chemical analysis of the samples indicates that almost all authigenic carbonates are composed of calcite or magnesian calcite; and only in one case, of siderite. Oxygen isotopic composition (d18O) ranges from +37.7 to +26.1 per mil (SMOW); it is, probably, connected with different temperatures of carbonate formation. A distinct geographic regularity is traced. Decrease in d18O values is observed from the cold Okhotsk Sea to the warm South China Sea. A very wide range of carbon isotopic composition (d13C from -42 to +3.8 per mil) indicates different sources of carbonic acid required for formation of these carbonates. As a basis for carbon isotopic composition we can distinguish three sources of carbonic acid in the studied sediments: microbiological methane oxidation, organic matter destruction during sediment diagenesis, and dissolved organogenic limestone. Thus, formation of authigenic carbonates in sediments from the marginal seas of the Northwest Pacific results from: 1) sediment diagenesis, 2) methane oxidation in zones of gas anomalies, 3) their precipitation from the supersaturated by carbonates sea shoal waters of tropical sea lagoons.

Hydrochemistry, water level, and discharge of water from Samoylov Island, Lena Delta, northeastern Siberia, in 2008

Although ponds make up roughly half of the total area of surface water in permafrost landscapes, their relevance to carbon dioxide emissions on a landscape scale has, to date, remained largely unknown. We have therefore investigated the inflows and outflows of dissolved organic and inorganic carbon from lakes, ponds, and outlets on Samoylov Island, in the Lena Delta of northeastern Siberia in September 2008, together with their carbon dioxide emissions. Outgassing of carbon dioxide (CO2) from these ponds and lakes, which cover 25% of Samoylov Island, was found to account for between 74 and 81% of the calculated net landscape-scale CO2 emissions of 0.2-1.1 g C/m**2/d during September 2008, of which 28-43% was from ponds and 27-46% from lakes. The lateral export of dissolved carbon was negligible compared to the gaseous emissions due to the small volumes of runoff. The concentrations of dissolved inorganic carbon in the ponds were found to triple during freezeback, highlighting their importance for temporary carbon storage between the time of carbon production and its emission as CO2. If ponds are ignored the total summer emissions of CO2-C from water bodies of the islands within the entire Lena Delta (0.7-1.3 Tg) are underestimated by between 35 and 62%.

Mineralogical and stable isotope analyses of carbonates from the eastern Black Sea

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area ("Batumi seep area") located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups. X-ray diffractometry revealed the presence of two different authigenic carbonate phases, i.e. pure aragonitic rims associated with vital microbial mats and high-Mg calcite cementing the hemipelagic sediment. As indicated by the CT images, the initial sediment has been strongly deformed, first plastic then brittle, leading to brecciation of the progressively cemented sediment. The aragonitic rims on the other hand, represent a presumably recent carbonate growth phase since they cover the already deformed sediment. The stable oxygen isotope signature indicates that the high-Mg calcite cement incorporated pore water mixed with substantial hydrate water amounts. This points at a dominant role of high gas/fluid flux from decomposing gas hydrates leading to the deformation and cementation of the overlying sediment. In contrast, the aragonitic rims do not show an influence of 18O-enriched hydrate water. The differences in d18O between the presumably recent aragonite precipitates and the older high-Mg cements suggest that periods of hydrate dissociation and vigorous fluid discharge alternated with times of hydrate stability and moderate fluid flow. These results indicate that shallow-buried gas hydrates are prone to episodic decomposition with associated vigorous fluid flow. This might have a profound impact on the seafloor morphology resulting e.g. in the formation of carbonate pavements and pockmark-like structures but might also affect the local carbon cycle.

Mineralogical, geochemical, and lipid biomarker study of cabonate precipitates at station GeoB9908-1

Carbonate precipitates recovered from 2,000 m water depth at the Dolgovskoy Mound (Shatsky Ridge, north eastern Black Sea) were studied using mineralogical, geochemical and lipid biomarker analyses. The carbonates differ in shape from simple pavements to cavernous structures with thick microbial mats attached to their lower side and within cavities. Low d13C values measured on carbonates (-41 to -32 per mill V-PDB) and extracted lipid biomarkers indicate that anaerobic oxidation of methane (AOM) played a crucial role in precipitating these carbonates. The internal structure of the carbonates is dominated by finely laminated coccolith ooze and homogeneous clay layers, both cemented by micritic high-magnesium calcite (HMC), and pure, botryoidal, yellowish low-magnesium calcite (LMC) grown in direct contact to microbial mats. d18O measurements suggest that the authigenic HMC precipitated in equilibrium with the Black Sea bottom water while the yellowish LMC rims have been growing in slightly 18O-depleted interstitial water. Although precipitated under significantly different environmental conditions, especially with respect to methane availability, all analysed carbonate samples show lipid patterns that are typical for ANME-1 dominated AOM consortia, in the case of the HMC samples with significant contributions of allochthonous components of marine and terrestrial origin, reflecting the hemipelagic nature of the primary sediment.

Chemical and isotopic compositions of samples from the Haakon Mosby mud volcano and nearby

Authigenic carbonates in the caldera of an Arctic (72°N) submarine mud volcano with active methane-bearing 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 methanotrophic ones in conditions of excess methane, and sulfate reducers developing on hydrogen, which is an intermediate product of microbial CH4 oxidation. Isotopically light carbon (aver. d13C = -28.9 per mil) of CO2 produced during CH4 oxidation is the main carbonate carbon source. Heavy oxygen isotope ratio (aver. d18O = 5 per mil) in carbonates is inherited from seawater sulfate. Rapid sulfate reduction (up to 12 mg S/dm**3/day) 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. Salinity as well as CO3/Ca and Mg/Ca ratios correspond to the field of non-magnesian calcium carbonate precipitation. Calcite is the dominant carbonate mineral in the methane seep caldera, where it occurs in the paragenetic association with barite. Radiocarbon age of carbonates is about 10 Ka.

Stable carbon and oxygen isotope ratios of carbonates of ODP Site 103-639

A Tithonian sequence of shallow-water limestones, intercalated with siliciclastics and overlain by dolomite, was recovered during drilling at ODP Site 639 on the edge of a tilted fault block. The carbonates were strongly affected by fracturing, dolomitization, dedolomitization, and compaction. The chronology and nature of the fractures, fracture infilling, and diagenesis of the host rock are established and correlated for both the limestone and the dolomite. A first phase of dolomitization affected limestone that was already, at least partially, indurated. In the limestone unit, fractures were filled by calcite and dolomite; most of the dolomite was recrystallized into calcite, except for the upper part. In the dolomitic unit, the first-formed dolomite was progressively recrystallized into saddle dolomite, as fractures were simultaneously activated. The dolomitic textures become less magnesian (the molar ratio mMg/mCa goes from 1.04-0.98 to 0.80), and the d18O (PDB) ranges from -10 per mil to -8 per mil. The varying pores and fissures are either cemented by a calcic saddle dolomite (mMg/mCa ranging from 0.95 to 0.80) or filled with diverse internal sediments of detrital calcic dolomite, consisting of detrital dolomite silt (d18O from -9 per mil to -7 per mil) and laminated yellow filling (with different d18O values that range from -4 per mil to +3 per mil). These internal sediments clearly contain elements of the host rock and fragments of saddle crystals. They are covered by marls with calpionellids of early Valanginian age, which permits dating of most of the diagenetic phases as pre-Valanginian. The dolomitization appears to be related to fracturing resulting from extensional tectonics; it is also partially related to an erosional episode. Two models of dolomitization can be proposed from the petrographic characteristics and isotopic data. Early replacement of aragonite bioclasts by sparite, dissolution linked to dolomitization, and negative d18O values of dolomite suggest a freshwater influence and 'mixing zone' model. On the other hand, the significant presence of saddle dolomite and repeated negative d18O values suggest a temperature effect; because we can dismiss deep burial, hydrothermal formation of dolomite would be the most probable model. For both of these hypotheses, the vadose filling of cavities and fractures by silt suggests emersion, and the different, and even positive, d18O values of the last-formed yellow internal sediment could suggest dolomitization of the top of the sequence under saline to hypersaline conditions. Fracturing resulting in the reopening of porosity and the draining of dolomitizing fluids was linked to extensional tectonics prior to the tilting of the block. These features indicate an earlier beginning to the rifting of the Iberian margin than previously known. Dolomitization, emersion, and erosion correspond to eustatic sea-level lowering at the Berriasian/Valanginian boundary. Diagenesis, rather than sedimentation, seems to mark this global event and to provide a record of the regional tectonic history.

Geochemistry of vein rocks of ODP Hole 118-735B

Rock samples from Hole 735B, Southwest Indian Ridge, were examined to determine the principal vein-related types of alteration that occurred, the nature of fluids that were present, and the temperatures and pressures of these fluids. Samples studied included veined metagabbro, veined mylonitic metagabbro, felsic trondhjemite, and late-stage leucocratic diopside-bearing veins. The methods used were standard petrographic analysis, mineral chemical analysis by electron microprobe, fluid inclusion petrography and analysis by heating/freezing techniques and laser Raman microspectroscopy, and oxygen isotopic analyses of mineral separates. Alteration in lithologic Units I and II (above the level of Core 118-735B-3OR; approximately 140 meters below the seafloor) is dominated by hydration by seawater-derived fluids at high temperature, up to about 700°C, and low water/rock ratio, during and immediately after pervasive ductile deformation. Below Core 118-735B-30R, pervasive deformation is less common, and brittle veining and brecciation are the major alteration styles. Leucocratic centimeter-scale veins, often containing diopside and plagioclase, were produced by interaction of hot (about 500°C) seawater-derived fluid and gabbro. The water/rock ratio was locally high at the veins and breccia zones, but the integrated water/rock ratio for the lower part of the hole is probably low. Accessory hydrous magmatic or deuteric phases formed from magmatic volatiles in some gabbro and in trondhjemite. Most subsequent alteration was affected by fluids that were seawater-derived, based on isotopic and chemical analyses of minerals and analyses of fluid inclusions. Many early-generation fluid inclusions, associated with high-temperature veining, contain appreciable methane as well as saline water. The source of methane is unclear, but it may have formed as seawater was reduced during low water/rock interaction with ultramafic upper mantle or ultramafic and mafic layer 3. Temperatures of alteration were calculated on the basis of coexisting mineral chemistry and isotopic values. Hydrothermal metamorphism commenced at about 720°C and continued to about 550°C. Leucocratic veining took place at about 500°C. Alteration within brecciated horizons was also at about 500° to less than 400°C, and the trondhjemite was altered at about 550° to below 490°C. Pressures calculated from a diopside-bearing vein, based on a combination of fluid inclusion and isotopic analysis, were 90 to 100 MPa. This pressure places the sample, from Core 118-735B-70R in Unit V, at about 2 km below the seafloor.

Carbonate aggregate mineralogy and stable isotopes at DSDP Site 87-583

Crystalline aggregates composed of calcium carbonate were recovered in the uppermost 50 m of Nankai Trough sediments during DSDP Leg 87A. These aggregates decomposed with time to masses of sandy calcite as determined by X-ray diffraction analysis. Petrographic and scanning electron microscopy revealed textures suggestive of a precursor phrase prior to calcite, and this precursor has been tentatively identified as the mineral ikaite, CaCO3*6H2O. Stable isotope data suggest a large component of terrigenous organic matter as the carbon source, consistent with the appearance of these aggregates in highly reducing pyritic sediments containing abundant plant remains. We propose that these nodules formed in euxinic basins on the upper part of the Trough slope under normal seafloor conditions of pressure and temperature. Calculated temperatures of formation of this phase are not unusually low. The specimens from Site 583 are the first reported occurrences of ikaite in active margin sediments.

Investigation of pingos in Kuganguaq delta on Disko Island

The growth and collapse history of two pingos located approximately 18 m a.s.l, and 35 m a.s.l. in Kuganguag, Disko lsland, west-central Greenland were examined. The pingos of this area were formed on Tertiary basalt rocks. One of the pingos is located in the middle of an alluvial fan, the other is on a river bed. Both have already collapsed. The pingo on the river bed had already collapsed at least 3545±60 year BP (14C dating from base of the pond sediments in the pingo crater). Both pingos formed after the sea's retreat as permafrost developed in the newly exposed delta bottom.

Isotopic survey of diagenetic carbonates, at DSDP Leg 63 Holes

Authigenic carbonates, principally calcium-rich dolomites, with extremely variable isotopic compositions were recovered in organic-rich marine sediments during Leg 63 drilling off southern California and Baja California. These carbonates occur as thin layers in fine-grained, diatomaceous sediments and siliceous rocks, mostly deposited during the Neogene. A combination of textural, geochemical, and isotopic evidence indicates these dolomites formed as cements and precipitates in shallow subsurface zones of high alkalinity spawned by abundant CO2 and methane production during progressive microbial decay of organic matter. Depths and approximate temperatures of formation estimated from oxygen isotopes are 87 to 658 meters and 10°C to 50°C, respectively. Within any sedimentary section, dolomites may form simultaneously at several depths or at different times within the same interval. Highly variable carbon isotopes (-30 to +16 per mil) reflect the isotopic reservoir in which the carbonates formed. Oxidation of organic matter through microbial reduction of sulfate at shallow depths favors light-carbon carbonates such as those at Sites 468 and 471; heavy-carbon carbonates at Site 467 most likely formed below this zone where HC**12O3**- is preferentially removed by reduction of CO2 to methane during methanogenesis. An important controlling factor is the sedimentation rate, which dictates both the preservation of organic matter on the sea floor and depth distribution of subsurface zones of organic-matter decay.

Sulphate and d34S in pore waters and d13C, d18O and mineral composition of carbonate nodules from ODP Leg 188 sites

Carbon and oxygen isotopic compositions of authigenic carbonate nodules or layers reflect the diagenetic conditions at the time of nodule growth. The shallowest samples of carbonate nodules and dissolved inorganic carbon of pore water samples beneath the sulfate reduction zone (0-160 meters below seafloor [mbsf]) at Site 1165 have extremely negative d13C values (-50 per mil and -62 per mil, respectively). These negative d13C values indicate nodule formation in association with anaerobic methane oxidation coupled with sulfate reduction. The 34S of residual sulfate at Site 1165 shows only minor 34S enrichment (+6 per mil), even with complete sulfate reduction. This small degree of apparent 34S enrichment is due to extreme "open-system" sulfate reduction, with sulfate abundantly resupplied by diffusion from overlying seawater. Ten calcite nodules from Site 1165 contain minor quartz and feldspar and have d13C values ranging from -49.7 per mil to -8.2 per mil. The nodules with the most negative d13C values currently are at depths of 273 to 350 mbsf and must have precipitated from carbonate largely derived from subsurface anaerobic methane oxidation. The processes of sulfate reduction coupled with methane oxidation in sediments of Hole 1165B are indicated by characteristic concentration and isotopic (d34S and d13C) profiles of dissolved sulfate and bicarbonate. Three siderite nodules from Site 1166 contain feldspar and mica and one has significant carbonate-apatite. The siderite has d13C values ranging from -15.3 per mil to -7.6 per mil. These siderite nodules probably represent early diagenetic carbonate precipitation during microbial methanogenesis.

Geochemistry of neritic carbonates of ODP Hole 134-831B

Drilling at Bougainville Guyot (Ocean Drilling Program Site 831), New Hebrides Island Arc during Leg 134 revealed that 727.5 m of carbonate overlies an andesite basement. The carbonate cap at Site 831 consists of 20 m of pelagic carbonate overlying 707.5 m of neritic carbonates. The neritic section consists of ~230 m of largely unaltered aragonite sediment that overlies ~497 m of totally calcitized limestone. The deeper portion of the calcitized interval has been pervasively altered by diagenesis. Prior to this study the age distribution of sediments at Bougainville Guyot was poorly known because age diagnostic fossils are sparsely and discontinuously distributed in the sequence. We have used Sr isotopes to provide temporal constraints on the deposition of carbonates at Site 831; these constraints are critical in reconstructing the vertical movement of Bougainville Guyot before its collision with the New Hebrides Island Arc. Overall, the chronostratigraphy of Bougainville Guyot can be subdivided into three intervals: (1) a Pleistocene interval (102.4 to 391.11 meters below sea floor [mbsf]); (2) a Miocene interval (410.31 to 669.53 mbsf); and (3) an Oligocene interval (678.83 to 727.50 mbsf). Strontium isotopic ages of samples increase with increasing depth in the carbonate sequence, except near the bottom of the sequence, where several samples exhibit a consistent reversed age vs. depth trend. Such age reversals are most likely the product of post-depositional rock-water interaction. Preliminary stable isotope data are consistent with diagenetic alteration in the marine and meteoric environments. Several abrupt decreases in d87Sr, and hence age, of sediments are recognized in the carbonate cap at Bougainville Guyot. These disconformities are most likely the product of subaerial exposure in response to relative sea-level fall. Indeed, Sr-isotope ages indicate that 2 to 9 m.y. of sediment deposition is missing across these d87Sr disconformities.