(Table 1) List of samples with carbonate mineralogy, stable isotope, and accessory-mineral information

Petrographic and stable-isotope (d13C, d18O) patterns of carbonates from the Logatchev Hydrothermal Field (LHF), the Gakkel Ridge (GR), and a Late Devonian outcrop from the Frankenwald (Germany) were compared in an attempt to understand the genesis of carbonate minerals in marine volcanic rocks. Specifically, were the carbonate samples from modern sea floor settings and the Devonian analog of hydrothermal origin, low-temperature abiogenic origin (as inferred for aragonite in serpentinites from elsewhere on the Mid-Atlantic Ridge), or biogenic origin? Aragonite is the most abundant carbonate mineral in serpentinites from the two modern spreading ridges and occurs within massive sulfides of the LHF. The precipitation and preservation of aragonite suggests high Mg2+ and sulfate concentrations in fluids. Values of d18OPDB as high as +5.3 per mill for serpentinite-hosted aragonite and as high as +4.2 per mill for sulfide-hosted aragonite are consistent with precipitation from cold seawater. Most of the corresponding d13C values indicate a marine carbon source, whereas d13C values for sulfide-hosted aragonite as high as +3.6 per mill may reflect residual carbon dioxide in the zone of methanogenesis. Calcite veins from the LHF, by contrast, have low d18OPDB (-20.0 per mill to -16.1 per mill) and d13C values (-5.8 per mill to -4.5 per mill), indicative of precipitation from hydrothermal solutions (~129°-186°C) dominated by magmatic CO2. Calcite formation was probably favored by fluid rock interactions at elevated temperatures, which tend to remove solutes that inhibit calcite precipitation in seawater (Mg2+ and sulfate). Devonian Frankenwald calcites show low d18O values, reflecting diagenetic and metamorphic overprinting. Values of d13C around 0 per mill for basalt-hosted calcite indicate seawater-derived inorganic carbon, whereas d13C values for serpentinite-hosted calcite agree with mantle-derived CO2 (for values as low as -6 per mill) with a contribution of amagmatic carbon (for values as low as -8.6 per mill), presumably methane. Secondary mineral phases from the LHF for which a biogenic origin appears feasible include dolomite dumbbells, clotted carbonate, and a network of iron- and silica-rich filaments.

(Table T1) Calcium carbonate mineralogy and stable isotopic composition of ODP Hole 182-1132C sediments

Petrographic observation and carbonate mineralogic and stable isotopic investigation were conducted on lower Oligocene to middle Miocene sediments recovered during Ocean Drilling Program Leg 182 from Site 1132, located at a water depth of 218.5 m immediately seaward of the shelf-slope break of the eastern Eyre Terrace in the western Great Australian Bight. The middle Miocene section consists of bioclastic packstone and grainstone with an interval of partially silicified nannofossil-foraminiferal chalk and is slightly to densely dolomitized. By contrast, the lower Oligocene to lower Miocene section is characterized by a predominance of planktonic and benthic foraminifers, high porosity, absence of chert, and weak dolomitization. The carbon and oxygen isotopic composition of calcites and dolomites between two sections, however, shows no significant difference.

General responses of Thoracosphaera heimii grown under a range of pCO2

Ocean acidification is considered a major threat to marine ecosystems and may particularly affect calcifying organisms such as corals, foraminifera and coccolithophores. Here we investigate the impact of elevated pCO2 and lowered pH on growth and calcification in the common calcareous dinoflagellate Thoracosphaera heimii. We observe a substantial reduction in growth rate, calcification and cyst stability of T. heimii under elevated pCO2. Furthermore, transcriptomic analyses reveal CO2 sensitive regulation of many genes, particularly those being associated to inorganic carbon acquisition and calcification. Stable carbon isotope fractionation for organic carbon production increased with increasing pCO2 whereas it decreased for calcification, which suggests interdependence between both processes. We also found a strong effect of pCO2 on the stable oxygen isotopic composition of calcite, in line with earlier observations concerning another T. heimii strain. The observed changes in stable oxygen and carbon isotope composition of T. heimii cysts may provide an ideal tool for reconstructing past seawater carbonate chemistry, and ultimately past pCO2. Although the function of calcification in T. heimii remains unresolved, this trait likely plays an important role in the ecological and evolutionary success of this species. Acting on calcification as well as growth, ocean acidification may therefore impose a great threat for T. heimii.

(Table 1) Stable-isotopes of mineral separates and whole-rock powders from altered volcanic rocks of DSDP Hole 62-465A

Hess Rise, in the western Pacific Ocean, formed in the mid-Cretaceous south of the equator and moved north with the Pacific Plate (Lancelot and Larson, 1975; Lancelot, 1978; Valuer et al., 1979). Southern Hess Rise was a volcanic archipelago, at least until late Albian time, after which it subsided to become one of the major aseismic rises in the present western Pacific. A second pulse of volcanic activity apparently occurred in the Campanian-Maastrichtian interval, which may be related to tectonic uplift of Hess Rise (Valuer and Jefferson, this volume). Trachytic rocks underlie 412 meters of carbonate sediments at Site 465 on southern Hess Rise. Twenty-four meters of trachyte were recovered from a 64-meter cored interval. The rocks are relatively homogeneous in texture, color, and composition, indicating that the cored sequence was probably part of only one magmatic event (Seifert et al., this volume). Large (> 5-mm) vesicles and oxidized parts of some flows suggest subaerial or shallow-water extrusions. The rocks are high in silica and relatively rich in Na2O, K2O, and light rare-earth elements. The upper part of the volcanic-rock sequence is a breccia, the fragments cemented by calcite, pyrite, and rare barite. Some of the resultant veins are more than 1 cm thick. In addition to the veins, many vesicles are also filled with these minerals. Brecciation and the number and thickness of veins decrease with depth in the hole. The degree of weathering, as indicated by water content, also decreases with depth.