Seawater carbonate chemistry near the Island of Ischia, Italy, 2008

We present the first study of the effects of ocean acidification on settlement of benthic invertebrates and microfauna. Artificial collectors were placed for 1 month along pH gradients at CO2 vents off Ischia (Tyrrhenian Sea, Italy). Seventy-nine taxa were identified from six main taxonomic groups (foraminiferans, nematodes, polychaetes, molluscs, crustaceans and chaetognaths). Calcareous foraminiferans, serpulid polychaetes, gastropods and bivalves showed highly significant reductions in recruitment to the collectors as pCO2 rose from normal (336-341 ppm, pH 8.09-8.15) to high levels (886-5,148 ppm) causing acidified conditions near the vents (pH 7.08-7.79). Only the syllid polychaete Syllis prolifera had higher abundances at the most acidified station, although a wide range of polychaetes and small crustaceans was able to settle and survive under these conditions. A few taxa (Amphiglena mediterranea, Leptochelia dubia, Caprella acanthifera) were particularly abundant at stations acidified by intermediate amounts of CO2 (pH 7.41-7.99). These results show that increased levels of CO2 can profoundly affect the settlement of a wide range of benthic organisms.

(Table 1) Uranium and Thorium concentrations, activity ratios and calcium carbonate content of DSDP Site 54-424

The geochemical behaviour of uranium and thorium in metalliferous sediments and hydrothermal deposits has been widely studied and the main results have been summarised by Boström and Rydell. These isotopes may be used to clarify how the metal-rich solutions are introduced into sediment cover and seawater. Using radiochemistry followed by alpha spectrometry, we have measured uranium concentrations as high as several hundred p.p.m., which must clearly be associated with ocean ridge thermal activity, in sediments interbedded between the basaltic basement and the green hydrothermal mud at DSDP Site 424. These high uranium concentrations indicate the path followed by the hydrothermal fluid which, debouching at the sediment-water interface, formed the green mud.

Mineralogic, elemental, and stable isotopic composition of bulk carbonate sediments from ODP Leg 166 sites

An intensive mineralogic and geochemical investigation was conducted on sediments recovered during Ocean Drilling Program Leg 166 from the western Great Bahama Bank at Sites 1006, 1008, and 1009. Pleistocene through middle Miocene sediments recovered from Site 1006, the distal location on the Leg 166 transect, are a mixture of bank-derived and pelagic carbonates with lesser and varying amounts of siliciclastic clays. A thick sequence of Pleistocene periplatform carbonates was recovered near the platform edge at Sites 1008 and 1009. Detailed bulk mineralogic, elemental (Ca, Mg, Sr, and Na), and stable isotopic (d18O and d13C) analyses of sediments are presented from a total of 317 samples from all three sites.

Pliocene stable isotope and carbonate stratigraphy at DSDP Holes 85-572C and 85-573A

Holes 572C and 573A provide high resolution (about 5000-yr. sampling interval) records of oxygen and carbon isotope stratigraphy (Globigerinoides sacculifera) and carbonate stratigraphy for the Pliocene of the equatorial Pacific. These data enable detailed correlation of carbonate events between sites and provide additional resolution to the previous carbonate stratigraphy. Comparison of calcium carbonate and d18O data reveal a "Pacific-type" carbonate stratigraphy throughout the Pliocene. The d18O data have two modes of variability with a boundary at 2.9 Ma. The planktonic d18O record does not have a steplike enrichment at 3.2 Ma, which is observed in benthic records elsewhere, suggesting that this event does not represent the proposed initiation of northern hemispheric glaciation. Hole 572C does record a distinct d18O enrichment event at about 2.4 Ma, which has been previously associated with the onset of major ice rafting in the North Atlantic.

Carbonate content in lower Cretaceous sediments of ODP Hole 123-765C

Sediments recovered during Ocean Drilling Program (ODP) Leg 123 from the Argo Abyssal Plain (AAP) consist largely of turbidites derived from the adjacent Australian continental margin. The oldest abundant turbidites are Valanginian-Aptian in age and have a mixed (smarl) composition; they contain subequal amounts of calcareous and siliceous biogenic components, as well as clay and lesser quartz. Most are thin-bedded, fine sand- to mud-sized, and best described by Stow and Piper's model (1984) for fine-grained biogenic turbidites. Thicker (to 3 m), coarser-grained (medium-to-coarse sand-sized) turbidites fit Bouma's model (1962) for sandy turbidites; these generally are base-cut-out (BCDE, BDE) sequences, with B-division parallel lamination as the dominant structure. Parallel laminae most commonly concentrate quartz and/or calcispheres vs. lithic clasts or clay, but distinctive millimeter- to centimeter-thick, radiolarian-rich laminae occur in both fine- and coarse-grained Valanginian-Hauterivian turbidites. AAP turbidites were derived from relatively deep parts of the continental margin (outer shelf, slope, or rise) that lay below the photic zone, but above the calcite compensation depth (CCD). Biogenic components are largely pelagic (calcispheres, foraminifers, radiolarians, nannofossils); lesser benthic foraminifers are characteristic of deep-water (abyssal to bathyal) environments. Abundant nonbiogenic components are mostly clay and clay clasts; smectite is the dominant clay species, and indicates a volcanogenic provenance, most likely the Triassic-Jurassic volcanic suite exposed along the northern Exmouth Plateau. Lower Cretaceous smarl turbidites were generated during eustatic lowstands and may have reached the abyssal plain via Swan Canyon, a submarine canyon thought to have formed during the Late Jurassic. In contrast to younger AAP turbidites, however, Lower Cretaceous turbidites are relatively fine-grained and do not contain notably older reworked fossils. Early in its history, the northwest Australian margin provided mainly contemporaneous slope sediment to the AAP; marginal basins adjacent to the continent trapped most terrigenous detritus, and pronounced canyon incisement did not occur until Late Cretaceous and, especially, Cenozoic time.

(Table 2) Mineralogy, stable isotopes, and mineral percentages of the carbonate fraction of samples from the South China Sea

Chemoherm carbonates, as well as numerous other types of methane seep carbonates, were discovered in 2004 along the passive margin of the northern South China Sea. Lithologically, the carbonates are micritic containing peloids, clasts and clam fragments. Some are highly brecciated with aragonite layers of varying thicknesses lining fractures and voids. Dissolution and replacement is common. Mineralogically, the carbonates are dominated by high magnesium calcites (HMC) and aragonite. Some HMCs with MgCO3 contents of between 30-38 mol%-extreme-HMC, occur in association with minor amounts of dolomite. All of the carbonates are strongly depleted in d13C, with a range from -35.7 to -57.5 per mil PDB and enriched in d18O (+ 4.0 to + 5.3 per mil PDB). Abundant microbial rods and filaments were recognized within the carbonate matrix as well as aragonite cements, likely fossils of chemosynthetic microbes involved in carbonate formation. The microbial structures are intimately associated with mineral grains. Some carbonate mineral grains resemble microbes. The isotope characteristics, the fabrics, the microbial structure, and the mineralogies are diagnostic of carbonates derived from anaerobic oxidation of methane mediated by microbes. From the succession of HMCs, extreme-HMC, and dolomite in layered tubular carbonates, combined with the presence of microbial structure and diagenetic fabric, we suggest that extreme-HMC may eventually transform into dolomites. Our results add to the worldwide record of seep carbonates and establish for the first time the exact locations and seafloor morphology where such carbonates formed in the South China Sea. Characteristics of the complex fabric demonstrate how seep carbonates may be used as archives recording multiple fluid regimes, dissolution, and early transformation events.

Carbonate record of ODP Leg 167 sites

One of the expected scientific results of Ocean Drilling Program Leg 167 was to reconstruct the Neogene history of biogenic calcium carbonate accumulation in the northeastern Pacific along the California margin (Lyle, Koizumi, Richter, et al., 1997). This aims to constrain inorganic carbon burial rates, deep-water hydrography in the North Pacific, and linkages between deep Atlantic and Pacific circulation and carbonate accumulation or dissolution patterns. Data are presented for four sites. Two of them are located in the California bight-East Cortez Basin (Site 1012: 32°16.970?N 118°23.024?W, 1773 m) and San Nicholas Basin (Site 1013: 32°48.040??, 118°53.992?W, 1564 m). The others are the dedicated Hole 1017E at Site 1017 (34°32.099?N, 121°6.430?W, 955 m) and Site 1019 in the Eel River Basin (41¢X40.972?N, 124°55.975?W, 977 m). Reconstruction of paleo-sea-surface temperatures (SST) by determining the alkenone unsaturation index of the extractable organic matter is an independent technique and helps to verify oxygen-isotope-based estimates. Results from the uppermost 600 cm of the dedicated Hole 1017E are expected to reveal the local temperature history of the last 30 k.y.

Carbonate chemistry, temperature and salinity of Lady Elliot Island Reef 2009-2010

Ocean acidification leads to changes in marine carbonate chemistry that are predicted to cause a decline in future coral reef calcification. Several laboratory and mesocosm experiments have described calcification responses of species and communities to increasing CO2. The few in situ studies on natural coral reefs that have been carried out to date have shown a direct relationship between aragonite saturation state (Omega arag) and net community calcification (Gnet). However, these studies have been performed over a limited range of Omega arag values, where extrapolation outside the observational range is required to predict future changes in coral reef calcification. We measured extreme diurnal variability in carbonate chemistry within a reef flat in the southern Great Barrier Reef, Australia. Omega arag varied between 1.1 and 6.5, thus exceeding the magnitude of change expected this century in open ocean subtropical/tropical waters. The observed variability comes about through biological activity on the reef, where changes to the carbonate chemistry are enhanced at low tide when reef flat waters are isolated from open ocean water. We define a relationship between net community calcification and Omega arag, using our in situ measurements. We find net community calcification to be linearly related to Omega arag, while temperature and nutrients had no significant effect on Gnet. Using our relationship between Gnet and Omega arag, we predict that net community calcification will decline by 55% of its preindustrial value by the end of the century. It is not known at this stage whether exposure to large variability in carbonate chemistry will make reef flat organisms more or less vulnerable to the non-calcifying physiological effects of increasing ocean CO2 and future laboratory studies will need to incorporate this natural variability to address this question.