Seawater carbonate chemistry and dissolution rates by boring microflora during ex situ experiments with dead corals (Porites lobata), 2009

Eight-month-old blocks of the coral Porites lobata colonized by natural Hawaiian euendolithic and epilithic communities were experimentally exposed to two different aqueous pCO2 treatments, 400 ppmv and 750 ppmv, for 3 months. The chlorophyte Ostreobium quekettii dominated communities at the start and at the end of the experiment (65-90%). There were no significant differences in the relative abundance of euendolithic species, nor were there any differences in bioeroded area at the surface of blocks (27%) between pCO2 treatments. The depth of penetration of filaments of O. quekettii was, however, significantly higher under 750 ppmv (1.4 mm) than under 400 ppmv (1 mm). Consequently, rates of carbonate dissolution measured under elevated pCO2 were 48% higher than under ambient pCO2 (0.46 kg CaCO3 dissolved m2/a versus 0.31 kg /m2/a). Thus, biogenic dissolution of carbonates by euendoliths in coral reefs may be a dominant mechanism of carbonate dissolution in a more acidic ocean.

Seawater carbonate chemistry and net dissolution rate for experiment of Shiraho reef

Acidification of the oceans by increasing anthropogenic CO2 emissions will cause a decrease in biogenic calcification and an increase in carbonate dissolution. Previous studies have suggested that carbonate dissolution will occur in polar regions and in the deep sea where saturation state with respect to carbonate minerals (Omega) will be <1 by 2100. Recent reports demonstrate nocturnal carbonate dissolution of reefs, despite a Omega a (aragonite saturation state) value of >1. This is probably related to the dissolution of reef carbonate (Mg-calcite), which is more soluble than aragonite. However, the threshold of Omega for the dissolution of natural sediments has not been clearly determined. We designed an experimental dissolution system with conditions mimicking those of a natural coral reef, and measured the dissolution rates of aragonite in corals, and of Mg-calcite excreted by other marine organisms, under conditions of Omega a > 1, with controlled seawater pCO2. The experimental data show that dissolution of bulk carbonate sediments sampled from a coral reef occurs at Omega a values of 3.7 to 3.8. Mg-calcite derived from foraminifera and coralline algae dissolves at Omega a values between 3.0 and 3.2, and coralline aragonite starts to dissolve when Omega a = 1.0. We show that nocturnal carbonate dissolution of coral reefs occurs mainly by the dissolution of foraminiferans and coralline algae in reef sediments.

Carbonate cycle and its control factors in Kuroshio source region during the last 190ka BP

Two deep sea cores (Ph05-5, 16.05 degrees N, 124.34 degrees E, water depth 3382m and WP3: 22.15 degrees N, 122.95 degrees E, water depth 2700m) retrieved from the Kuroshio source region of the western Philippine Sea were selected to carry out the CaCO3 and calcareous nannofossil faunas study. Based on AMS(14)C data and comparing tire oxygen isotope curve with SPECMAP delta O-18 (Martinson et al., 1987) a stratigraphy was established. And, combining the changes of primary productivity and dissolution index of carbonate, the carbonate cycle and its control factors were analyzed in this region during the last 190ka BP. The carbonate contents showed higher values in the glacial periods and lower values during the interglacial and Holocene periods, which characteristics was similar to the tendency of "Pacific Type" carbonate cycle. However, there were high carbonate contents in the warm period and low values during the cold interval, which displayed the same tendency with the "Atlantic Type" carbonate cycle during the last glacial period (MIS4-2) in the east of Phillipines. The variations of primary productivity and carbonate dissolution index indicated that the carbonate dissolution was a major factor controlling the carbonate content in tire cast of Philippines, and the variations in carbonate contents were mainly affected by the productivity of calcareous organism in the Southeast of Taiwan. The "Atlantic Type" carbonate cycle in the cast of Phillipines during the last glacial period (MIS4-2) was an effect of the process of dissolution combined with the change of primary productivity.

Carbonate mineralogical and isotopic analyses of TV-guided grab samples and TV-guided box corer samples from the Shumagin area

Methane seepage leads to Mg-calcite and aragonite precipitation at a depth of 4,850 m on the Aleutian accretionary margin. Stromatolitic and oncoid growth structures imply encrustation of microorganisms (microbial mats) in the host sediment with a unique growth direction downward into the sediment, forming crust-shaped lithologies. Biomarker investigations of the residue after carbonate dissolution show strong enrichments in crocetane and archaeol, which contain extremely low d13C values. This indicates the presence of methane-consuming archaea, and d13C values of -42 to -51 per mill PDB indicate that methane is the carbon source for the carbonate crusts. Thus, it appears that stromatolitic encrustations of methanotrophic anaerobic archaea probably occurs in a consortium with sulphate-reducing bacteria and that carbonate precipitation proceeds downward into the sediment, where ascending cold fluids provide a methane source. Strontium and oxygen isotope analyses as well as 14C ages of the carbonates suggest that the fluids come from deep within the sediment and that carbonate precipitation began about 3,000 years ago.

Pliocene-Plistocene deposition of carbonate and organic carbon in ODP Hole 159-959C

During Ocean Drilling Program (ODP) Leg 159, four sites (Sites 959-962) were drilled along a depth transect on the Côte d'Ivoire/Ghana Transform Margin. In this study, the Pliocene-Pleistocene history of carbonate and organic carbon accumulation at Hole 959C is reconstructed for the eastern equatorial Atlantic off the Ivory Coast/Ghana based on bulk carbonate, sand fraction, organic carbon, and other organic geochemical records (d13Corg, marine organic matter percentages derived from organic petrology, hydrogen index, C/N). Pliocene-Pleistocene sedimentation off the Ivory Coast/Ghana was strongly affected by low mean sedimentation rates, which are attributed to persistently enhanced bottom-water velocities related to the steep topography of the transform margin. Sand fraction and bulk carbonate records reveal typical glacial/interglacial cycles, preserved, however, with low time resolution. Intermediate carbonate accumulation rates observed throughout the Pliocene-Pleistocene suggest intense winnowing and sediment redistribution superimposed by terrigenous dilution. 'Atlantic-type' sand and carbonate cycles, consistent with records from pelagic areas of the eastern equatorial Atlantic, are encountered at Hole 959C prior to about 0.9 Ma. Total organic carbon (TOC) records are frequently inversely correlated to carbonate contents, indicating mainly productivity-driven carbonate dissolution related to changes in paleoproductivity. During Stages 22-24, 20, 16, 12, 8, and 4, sand and carbonate records reveal a 'Pacific-type' pattern, showing elevated contents during glacials commonly in conjunction with enhanced TOC records. Formation of 'Pacific-type' patterns off the Ivory Coast/Ghana is attributed to drastically increased bottom-water intensities along the transform margin in accordance with results reported from the Walvis Ridge area. Short-term glacial/interglacial changes in paleoproductivity off the Ivory Coast/Ghana are to some extend recognizable during glacials prior to 1.7 Ma and interglacial Stages 21, 19, 13, 9, and 1. Enhanced coastal upwelling during interglacials is attributed to local paleoclimatic and oceanographic conditions off the Ivory Coast/Ghana. Quantitative estimates of marine organic carbon based on organic petrologic and d13Corg records reveal an offset in concentration ranging from 15% to 60%. Highest variabilities of both records are recorded since ~0.9 Ma. Discrepancies between the isotopic and microscopic records are attributed to an admixture of C4 plant debris approaching the eastern equatorial Atlantic via atmospheric dust. Terrestrial organic material likely originated from the grass-savannah-covered Sahel zone in central Africa. Estimated C4 plant concentrations and accumulation rates range from 10% to 37% and from almost zero to 0.006 g/cm**2/k.y., respectively. The strongest eolian supply to the northern Gulf of Guinea is indicated between 1.9 and 1.68 Ma and during glacial isotopic Stages 22-24, 20, 14, and 12. The presence of grass-type plant debris is further supported by organic petrologic studies, which reveal well-preserved cell tissues of vascular plants or tube-shaped, elongated terrestrial macerals showing different levels of oxidation.

Calcium carbonate, isotopes and Rock-Eval pyrolysis at DSDP Holes 77-535 and 77-540

At DSDP Sites 534 (Central Atlantic) and 535 and 540 (Gulf of Mexico), and in the Vocontian Basin (France), Lower Cretaceous deposits show a very pronounced alternation of limestone and marl. This rhythm characterizes the pelagic background sedimentation and is independent of detritic intercalations related to contour and turbidity currents. Bed-scale cycles, estimated to be 6000-26,000 yr. long, comprise major and minor units. Their biological and mineralogic components, burrowing, heavy isotopes C and O, and some geochemical indicators, vary in close correlation with CaCO3 content. Vertical changes of frequency and asymmetry of the cycles are connected with fluctuations of the sedimentation rate. Plots of cycle thickness ("cyclograms") permit detailed correlations of the three areas and improve the stratigraphic subdivision of Neocomian deposits at the DSDP sites. Small-scale alternations, only observed in DSDP cores, comprise centimetric to millimetric banding and millimetric to micrometric lamination, here interpreted as varvelike alternations between laminae that are rich in calcareous plankton and others rich in clay. The laminations are estimated to correspond to cycles approximately 1,3, and 13 yr. in duration. The cyclic patterns appear to be governed by an interplay of continental and oceanic processes. Oceanic controls express themselves in variations of the biogenic carbonate flux, which depends on variations of such elements as temperature, oxygenation, salinity, and nutrient content. Continental controls modulate the influxes of terrigenous material, organic matter, and nutrients derived from cyclic erosion on land. Among the possible causes of cyclic sedimentation, episodic carbonate dissolution has been ruled out in favor of climatic fluctuations with a large range of periods. Such fluctuations are consistent with the great geographic extension shown by alternation controls and with the continuous spectrum of scales that characterizes limestone-marl cycles. The climatic variations induced by the Earth's orbital parameters (Milankovitch cycles) could be connected to bed-interbed alternations.

Foraminifer, coarse fraction and carbonate characteristics of sediments from ODP Leg 198 sites on Shatsky Rise

Holes 1209A and 1211A on Southern High, Shatsky Rise contain expanded, nearly continuous records of carbonate-rich sediment deposited in deep water of the equatorial Pacific Ocean during the Paleocene and Eocene. In this study, we document intervals of carbonate dissolution in these records by examining temporal changes in four parameters: carbonate content, coarse size fraction (>38 µm), benthic foraminiferal abundance, and planktonic foraminiferal fragmentation ratio. Carbonate content is not a sensitive indicator of carbonate dissolution in the studied sections, although rare intervals of low carbonate may reflect times of relatively high dissolution. The proportion of coarse size fraction does not accurately record carbonate dissolution either because the relative abundance of nannofossils largely determines the grain-size distribution. Benthic abundance and fragmentation covary (r**2 = 0.77) and are probably the best indicators for carbonate dissolution. For both holes, records of these parameters indicate two episodes of prominent dissolution. The first of these occurs in the upper Paleocene (~59-58 Ma) and the second in the middle to upper Eocene (~45-33.7 Ma). Other intervals of enhanced carbonate dissolution are located in the upper Paleocene (~56 Ma) and in the upper lower Eocene (~51 Ma). Enhanced preservation of planktonic foraminiferal assemblages marks the start of both the Paleocene and Eocene epochs.

Foraminiferal abundance, carbonat concentration and dissolution index of sediment core W9903B-51GC

In order to investigate the paleoceanographic record of dissolution of calcium carbonate (CaCO3) in the central equatorial Pacific Ocean, we have studied the relationship between three indices of foraminiferal dissolution and the concentration and accumulation of CaCO3, opal, and Corg in Core WEC8803B-GC51 (1.3°N, 133.6°W; 4410 m). This core spans the past 413 kyr of deposition and moved in and out of the lysoclinal transition zone during glacial-interglacial cycles of CaCO3 production and dissolution. The record of dissolution intensity provided by foraminiferal fragmentation, the proportion of benthic foraminifera, and the foraminiferal dissolution index consistently indicates that the past corrosion of pelagic CaCO3 in the central equatorial Pacific does not vary with the observed sedimentary concentration of CaCO3. Although there is a weak low-frequency variation (~100 kyr) in dissolution intensity, it is unrelated to sedimentary CaCO3 concentration. There are many shorter-lived episodes where high CaCO3 concentration is coincident with poor foraminiferal preservation, and where, conversely, low CaCO3 concentration is coincident with superb foraminiferal preservation. Spectral analyses indicate that dissolution maxima consistently lagged glacial maxima (manifest by the SPECMAP delta18O stack) in the 100-kyr orbital band. Additionally, there is no relationship between dissolution and the accumulation of biogenic opal or Corg or between dissolution and the burial ratio of Corg/CINorg (calculated from Corg and CaCO3). Because previous studies of this core strongly suggest that surface water productivity varied closely with CaCO3 accumulation, both the mechanistic decoupling of carbonate dissolution from CaCO3 concentration (and from biogenic accumulation) and the substantial phase shift between dissolution and global glacial periodicity effectively obscure any simple link between export production, CaCO3 concentration, and dissolution of sedimentary CaCO3.

TOC, carbonate, opal composition and trace element concentration from ODP Holes 175-1082A and 175-1084A

Distinctive light-dark color cycles in sediment beneath the Benguela Current Upwelling System indicate repetitive alternations in sediment delivery and deposition. Geochemical proxies for paleoproductivity and for depositional conditions were employed to investigate the paleoceanographic processes involved in creating these cycles in three mid-Pleistocene intervals from ODP Sites 1082 and 1084. Concentrations of total organic carbon (TOC) vary between 3.5 and 17.1%. Concentrations of CaCO3 vary inversely to TOC and Al, which suggests that both carbonate dissolution and terrigenous dilution contribute to the light-dark cycles. Opal concentrations are independent of both TOC and CaCO3, therefore eliminating diatom production and lateral transport of shelf material as causes of the light-dark cycles. d13Corg and d15Ntot values do not vary across light-dark sediment intervals, implying that the extent of relative nutrient utilization did not change. The stable d15Ntot values represent a balanced change in nitrate supply and export production and therefore indicate that productivity was elevated during deposition of the TOC-rich layers. Parallel changes in concentrations of indicator trace elements and TOC imply that changes in organic matter delivery influenced geochemical processes on the seafloor by controlling consumption of pore water oxygen. Cu, Ni, and Zn are enriched in the darker sediment as a consequence of greater organic matter delivery. Redox-sensitive metals vary due to loss (Mn and Ba) or enrichment (Mo) under reducing conditions created by TOC oxidation. Organic matter delivery impacts subsequent geochemical changes such as carbonate dissolution, sulfate reduction and the concentration of metals. Thus, export production is considered ultimately responsible for the generation of the color cycles.

Coccoliths and carbonate grain-size compositions in sediment samples from the Mid-Atlantic Ridge

This study presents a differentiated carbonate budget for marine surface sediments from the Mid-Atlantic Ridge of the South Atlantic, with results based on carbonate grain-size composition. Upon separation into sand, silt, and clay sub-fractions, the silt grain-size distribution was measured using a SediGraph 5100. We found regionally characteristic grain-size distributions with an overall minimum at 8 µm equivalent spherical diameter (ESD). SEM observations reveal that the coarse particles (>8 µm ESD) are attributed to planktic foraminifers and their fragments, and the fine particles (<8 µm ESD) to coccoliths. On the basis of this division, the regional variation of the contribution of foraminifers and coccoliths to the carbonate budget of the sediments are calculated. Foraminifer carbonate dominates the sediments in mesotropic regions whereas coccoliths contribute most carbonate in oligotrophic regions. The grain size of the coccolith share is constant over water depth, indicating a lower susceptibility for carbonate dissolution compared to foraminifers. Finally, the characteristic grain-size distribution in fine silt (<8 µm ESD) is set into context with the coccolith assemblage counted and biometrically measured using a SEM. The coccoliths present in the silt fraction are predominantly large species (length > 4 µm). Smaller species (length < 4 µm) belong to the clay fraction (<2 µm ESD). The average length of most frequent coccolith species is connected to prominent peaks in grain-size distributions (ESD) with a shape factor. The area below Gaussian distributions fitted to these peaks is suggested as a way to quantitatively estimate the carbonate contribution of single coccolith species more precisely compared to conventional volume estimates. The quantitative division of carbonate into the fraction produced by coccoliths and that secreted by foraminifers enables a more precise estimate for source/sink relations of consumed and released CO2 in the carbon cycle. The allocation of coccolith length and grain size (ESD) suggests size windows for the separation or accumulation of distinct coccolith species in investigations that depend on non to slightly-mixed signals (e.g., isotopic studies).

Coral-algae metabolism and diurnal changes in the CO2-carbonate system of bulk sea water

Precise measurements were conducted in continuous flow seawater mesocosms located in full sunlight that compared metabolic response of coral, coral-macroalgae and macroalgae systems over a diurnal cycle. Irradiance controlled net photosynthesis (Pnet), which in turn drove net calcification (Gnet), and altered pH. Pnet exerted the dominant control on [CO3]2- and aragonite saturation state (Omega arag) over the diel cycle. Dark calcification rate decreased after sunset, reaching zero near midnight followed by an increasing rate that peaked at 03:00 h. Changes in Omega arag and pH lagged behind Gnet throughout the daily cycle by two or more hours. The flux rate Pnet was the primary driver of calcification. Daytime coral metabolism rapidly removes dissolved inorganic carbon (DIC) from the bulk seawater and photosynthesis provides the energy that drives Gnet while increasing the bulk water pH. These relationships result in a correlation between Gnet and Omega arag, with Omega arag as the dependent variable. High rates of H+ efflux continued for several hours following mid-day peak Gnet suggesting that corals have difficulty in shedding waste protons as described by the Proton Flux Hypothesis. DIC flux (uptake) followed Pnet and Gnet and dropped off rapidly following peak Pnet and peak Gnet indicating that corals can cope more effectively with the problem of limited DIC supply compared to the problem of eliminating H+. Over a 24 h period the plot of total alkalinity (AT) versus DIC as well as the plot of Gnet versus Omega arag revealed a circular hysteresis pattern over the diel cycle in the coral and coral-algae mesocosms, but not the macroalgae mesocosm. Presence of macroalgae did not change Gnet of the corals, but altered the relationship between Omega arag and Gnet. Predictive models of how future global changes will effect coral growth that are based on oceanic Omega arag must include the influence of future localized Pnet on Gnet and changes in rate of reef carbonate dissolution. The correlation between Omega arag and Gnet over the diel cycle is simply the response of the CO2-carbonate system to increased pH as photosynthesis shifts the equilibria and increases the [CO3]2- relative to the other DIC components of [HCO3]- and [CO2]. Therefore Omega arag closely tracked pH as an effect of changes in Pnet, which also drove changes in Gnet. Measurements of DIC flux and H+ flux are far more useful than concentrations in describing coral metabolism dynamics. Coral reefs are systems that exist in constant disequilibrium with the water column.