Boron, carbonate carbon and oxygen isotope analyses of samples from the Yangtze Platform (China), Congo craton (Namibia), and Karatau microcontinent (Kazakhstan) of the Marinoan glaciation

Boron isotope patterns preserved in cap carbonates deposited in the aftermath of the younger Cryogenian (Marinoan, ca. 635 Ma) glaciation confirm a temporary ocean acidification event on the continental margin of the southern Congo craton, Namibia. To test the significance of this acidification event and reconstruct Earth's global seawater pH states at the Cryogenian-Ediacaran transition, we present a new boron isotope data set recorded in cap carbonates deposited on the Yangtze Platform in south China and on the Karatau microcontinent in Kazakhstan. Our compiled d11B data reveal similar ocean pH patterns for all investigated cratons and confirm the presence of a global and synchronous ocean acidification event during the Marinoan deglacial period, compatible with elevated postglacial pCO2 concentrations. Differences in the details of the ocean acidification event point to regional distinctions in the buffering capacity of Ediacaran seawater.

Index properties, calcium carbonate content and opal concentration of ODP Core 167-1016B-17H sediments

Physical properties measurements provide a relatively inexpensive and fast way to obtain high-resolution estimates of the variations in sedimentological properties. To better resolve the validity and cause of the geophysical signals measured by the Ocean Drilling Program (ODP) shipboard multisensor track (MST) instruments, 223 x 10 cm**3 core samples were collected at 4 cm intervals in Core 167-1016B-17H at the California Margin Conception Transect for the measurements of index properties, carbonate content, and opal content. This core was chosen because hole-to-hole stratigraphic correlation of MST data suggested that Core 17H corresponds to a depth interval that displays the greatest range of amplitude of many physical properties.

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.

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.

Late Cenozoic carbonate accumulation rates of ODP Leg 115 samples

The principal paleoceanographic objective of Ocean Drilling Program Leg 115 was to collect a suite of materials that would allow reconstruction of the dynamic features of the late Cenozoic carbonate system in the equatorial Indian Ocean. This goal was achieved with the recovery of sediments from a closely spaced depth transect (1541-4428 m) of five sites (Sites 707 through 711) from on and around the Mascarene Plateau that record the last 50 m.y. of pelagic deposition. More than 2200 measurements of carbonate content are combined here with a highly resolved bio- and magnetostratigraphy to produce the first detailed compilation of bulk, carbonate, and noncarbonate mass accumulation rates (MARs) from the Indian Ocean. These results allow us to recognize three major depositional intervals, each characterized by a distinct depth-dependent pattern of carbonate accumulation: (1) the Paleogene, a time of moderate accumulation rates (0.4-0.7 g/cm**2/1000 yr) and reduced between-site accumulation differences; (2) the early and middle Miocene, a period characterized by greatly reduced carbonate MARs (typically <0.2 g/cm**2/1000 yr) at all sites and a shallow carbonate compensation depth; and (3) the late Miocene to Holocene, a time span marked by the highest bulk and carbonate accumulation rates of the last 50 Ma (1.6-1.8 g/cm**2/1000 yr), and the first appearance of substantial contrasts in carbonate accumulation as a function of the water depth of the drill site. The fundamentally different character of the carbonate system during each of these intervals must represent a regional response to the complex evolution of late Cenozoic oceans and climate.

Biogenic opal and carbonate concentration in late Neogene sediments of ODP Site 114-704

A preliminary composite depth section was generated for Site 704 by splicing Holes 704A and 704B together over the interval 0-350 mbsf (0-9 m.y.). High-resolution carbonate and opal data from the cores were correlated with the calcium and silicon signals from the GST logging run in Hole 704B to identify missing and disturbed intervals in the cores. Paleomagnetic and biostratigraphic age boundaries were then transferred to the composite depth records to obtain an age model, and sedimentation rates were calculated by linear interpolation between datums. Algorithms relating measured dry-bulk density to carbonate content and depth were generated to produce predicted values of density for every sample. Accumulation rates of bulk, carbonate, opal, and terrigenous sediment components were then computed to generate a record of sediment deposition on the Meteor Rise that has a resolution of better than 200,000 yr for the period from 8.6 to 1.0 m.y. From 8.6 to 2.5 m.y., bulk-accumulation rates on the Meteor Rise averaged less than 2 g/cm**2/1000 yr and were dominated by carbonate deposition. The first significant opal deposition (6.0 m.y.) punctuated a brief (less than 0.6 Ma) approach of the Polar Front Zone (PFZ) northward that heralded a period of increasing severity of periodic carbonate dissolution events (terrigenous maxima) that abruptly terminated at 4.8 m.y. (base of the Thvera Subchron), synchronous with the reflooding of the Mediterranean after the Messinian salinity crisis. From 4.8 to 2.5 m.y., carbonate again dominated deposition, and the PFZ was far south except during brief northward excursions bracketing 4.2-3.9, 3.3-2.9, and 2.8-2.7 m.y. At 2.5 m.y., all components of bulk-accumulation rates increased dramatically (up to 15 g/cm2/1000 yr), and by 2.4 m.y., a pattern of alternating, high-amplitude carbonate and opal cyclicity marked the initiation of rapid glacial to interglaci·l swings in the position of the PFZ, synchronous with the "onset" of major Northern Hemisphere glaciation. Both mass-accumulation rates and the amplitude of the cycles decreased by about 2 m.y., but opal accumulation rates remained high up through the base of the Jaramillo (0.98 m.y.). From 1.9 to 1 m.y., the record is characterized by moderate amplitude fluctuations in carbonate and opal. This record of opal accumulation rates is interpreted as a long-term "Polar Front Indicator" that monitors the advance and retreat of the opal-rich PFZ northward (southward) toward (away from) the Meteor Rise in the subantarctic sector of the South Atlantic Ocean. The timing of PFZ migrations in the subantarctic South Atlantic Ocean is remarkably similar to Pliocene-Pleistocene climate records deduced from benthic oxygen isotope records in the North Atlantic Ocean (Raymo et al., 1989, doi:10.1029/PA004i004p00413; Ruddiman et al., 1989, doi:10.1029/PA004i004p00353). These include northward migrations during "cold" intervals containing strong glacial isotope stages (2.4-2.3, 2.1-2.0, 1.95-1.55, 1.45-1.30 m.y. and at about 1.13 and 1.09 m.y.) and southward migrations during "warm" intervals containing weak glacial and/or strong interglacial stages (2.45-2.40, 2.30-2.10, 2.00-1.95, 1.52-1.45, 1.30-1.18, 1.11, and 1.06-0.93 m.y.). Although our preliminary composite record is not continuous (some stages are obviously missing), there is hope that future work will identify these missing intervals in the as yet incomplete Hole 704B and will extend this high-resolution Southern Hemisphere climate record back to 8.6 m.y.

Seawater carbonate chemistry during experiments with Patella vulgata, 2010

The effect of short-term (5 days) exposure to CO2-acidified seawater (year 2100 predicted values, ocean pH = 7.6) on key aspects of the function of the intertidal common limpet Patella vulgata (Gastropoda: Patellidae) was investigated. Changes in extracellular acid-base balance were almost completely compensated by an increase in bicarbonate ions. A concomitant increase in haemolymph Ca2+ and visible shell dissolution implicated passive shell dissolution as the bicarbonate source. Analysis of the radula using SEM revealed that individuals from the hypercapnic treatment showed an increase in the number of damaged teeth and the extent to which such teeth were damaged compared with controls. As radula teeth are composed mainly of chitin, acid dissolution seems unlikely, and so the proximate cause of damage is unknown. There was no hypercapnia-related change in metabolism (O2 uptake) or feeding rate, also discounting the possibility that teeth damage was a result of a CO2-related increase in grazing. We conclude that although the limpet appears to have the physiological capacity to maintain its extracellular acid-base balance, metabolism and feeding rate over a 5 days exposure to acidified seawater, radular damage somehow incurred during this time could still compromise feeding in the longer term, in turn decreasing the top-down ecosystem control that P. vulgata exerts over rocky shore environments.

Carbonate mineralogy and stable isotope composition of cool-water bryozoans from sediments of ODP Leg 182 sites

The carbon and oxygen isotopic compositions of selected bryozoan skeletons from upper Pleistocene bryozoan mounds in the Great Australian Bight (Ocean Drilling Program Leg 182; Holes 1129C, 1131A, and 1132B) were determined. Cyclostome bryozoans, Idmidronea spp. and Nevianipora sp., have low to intermediate magnesian calcite skeletons (1.5-10.0 and 0.9-6.4 molar percentage [mol%] MgCO3, respectively), but a considerable number include marine cements. The cheilostome Adeonellopsis spp. are biminerallic, principally aragonite, with some high magnesian calcite (HMC) (6.6-12.1 mol% MgCO3). The HMC fraction of Adeonellopsis has lower d13C and similar d18O values compared with the aragonite fraction. Reexamination of modern bryozoan isotopic composition shows that skeletons of Adeonellopsis spp. and Nevianipora sp. form close to oxygen isotopic equilibrium with their ambient water. Therefore, changes in glacial-interglacial oceanographic conditions are preserved in the oxygen isotopic profiles. The bryozoan oxygen isotopic profiles are correlated well with marine isotope Stages 1-8 in Holes 1129C and 1132B and to Stages 1-4(?) in Hole 1131A. The horizons of the bryozoan mounds that yield skeletons with heavier oxygen isotopic values can be correlated with isotope Stages 2, 4(?), 6, and 8 in Hole 1129C; Stages 2 and 4(?) in Hole 1131A; and Stages 2, 4, 6, and 8 in Hole 1132B. These results provide supporting evidence for a model for bryozoan mound formation, in which the mounds were formed during intensified upwelling and increased trophic resources during glacial periods.

Pliocene to Pleistocene calcium carbonate and organic carbon record of ODP Hole 117-722B

Site 722 provides high resolution records of percent CaCO3, magnetic susceptibility, d18O, organic carbon, and coarse fraction for the past 3.4 m.y. from the crest of the Owen Ridge, northwestern Arabian Sea. Within this time interval, most of the carbonate percent variations can be attributed to terrigenous dilution and do not reflect changes in the carbonate system. From the late Pliocene to Present, the average rate of calcium carbonate accumulation increases from 1 to 3 g/cm**2/k.y. and the average accumulation of organic carbon decreases from 75 to 30 mg/cm**2/k.y. The carbonate component is more dissolved in the older interval. The long-term variations in carbonate accumulation may reflect a greater input of organic matter in the late Pliocene, which decomposes to produce CO2 and dissolve carbonate. Magnetic susceptibility and % noncarbonate (100 - CaCO3%) reflect changes in the amount of the lithogenic component in the sediments. The period of variation of lithogenic material is the same period as the original forcing of the regional summer monsoon, however, the timing matches global aridity patterns and global ice volume (sea level) changes. This preliminary analysis suggests that the high frequency variation of lithogenic material persists for at least the last 3.4 m.y. Within the last million years, calcium carbonate accumulation has a large amplitude signal that covaries with major changes in ice volume. Both calcium carbonate and noncarbonate (mostly terrigenous) accumulation are greatest during glacial stages. Interglacial intervals are characterized by low mass accumulation rates, increased foraminifer fragmentation, and increased opal concentration. The accumulation of organic carbon matches the high frequency changes in sedimentation rates. We attribute this high correlation to enhanced preservation of organic carbon by increased sedimentation rate. Of the three major biological components studied, only opal exhibits the variations expected for a biological productivity system forced by monsoonal upwelling driven by changes in northern hemisphere summer radiation.

Late Quaternary siliciclastic/carbonate sedimentation in the Cabricorn Channel

A model is presented for hemipelagic siliciclastic and carbonate sedimentation during the last glacial-interglacial cycle in the Capricorn Channel, southern Great Barrier Reef (GBR). Stable isotope ratios, grainsize, carbonate content and mineralogy were analysed for seven cores in a depth transect from 166 to 2892 m below sea level (mbsl). Results show variations in the flux of terrigenous, neritic and pelagic sediments to the continental slope over the last sea level cycle. During the glacial lowstand terrigenous sediment influenced all the cores down to 2000 mbsl. The percentages of quartz and feldspar in the cores decreased with water depth, while the percentage of clay increased. X-ray diffraction analysis of the glacial lowstand clay mineralogy suggests that the siliciclastic sediment was primarily sourced from the Fitzroy River, which debouched directly into the northwest sector of the Capricorn Channel at this time. The cores also show a decrease in pelagic calcite and an increase in aragonite and high magnesium calcite (HMC) during the glacial. The influx of HMC and aragonite is most likely from reworking of coral reefs exposed on the continental shelf during the glacial, and also from HMC ooids precipitated at the head of the Capricorn Channel at this time. Mass accumulation rates (MARs) are high (13.5 g/cm**/kyr) during the glacial and peak at ~20 g/cm** 3/kyr in the early transgression (16-14 ka BP). MARs then decline with further sea level rise as the Fitzroy River mouth retreats from the edge of the continental shelf after 13.5 ka BP. MARs remain low (4 g/cm**3/kyr) throughout the Holocene highstand. Data for the Holocene highstand indicate there is a reduction in siliciclastic influx to the Capricorn Channel with little quartz and feldspar below 350 mbsl. However, fine-grained fluvial sediments, presumably from the Fitzroy River, were still accumulating on the mid slope down to 2000 mbsl. The proportion of pelagic calcite in the core tops increases with water depth, while HMC decreases, and is present only in trace amounts in cores below 1500 mbsl. The difference in the percentage of HMC in the deeper cores between the glacial and Holocene may reflect differences in supply or deepening of the HMC lysocline during the glacial. Sediment accumulation rates also vary between cores in the Capricorn Channel and do not show the expected exponential decrease with depth. This may be due to intermediate or deep water currents reworking the sediments. It is also possible that present bathymetry data are too sparse to detect the potential role that submarine channels may play in the distribution and accumulation of sediments. Comparison of the Capricorn Channel MARs with those for other mixed carbonate/siliciclastic provinces from the northeast margin of Australia indicates that peak MARs in the early transgression in the Capricorn Channel precede those from the central GBR and south of Fraser Island. The difference in the timing of the carbonate and siliciclastic MAR peaks along the northeast margin is primarily related to differences in the physiography and climate of the provinces. The only common trend in the MARs from the northeast margin of Australia is the near synchronicity of the carbonate and siliciclastic MAR peaks in individual sediment cores, which supports a coeval sedimentation model.