(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 1) Cd/Ca and Mn/Ca ratios of benthic foraminifera from DSDP Hole 30-289

The late Miocene carbon shift (~6.2 Myr) -a 0.5-1.0 per mil, d13C decrease in benthic and planktonic foraminifera- has been ascribed to changes in global inventory, deep-ocean circulation, and/or productivity. Cadmium, d13C, and nutrients in the ocean are linked; comparison of d13C and Cd/Ca yields circulation and chemical inventory information not available from either alone. We determined Cd/Ca ratios in late Miocene benthic foraminifera from DSDP Site 289. Results include: (1) late Miocene Pacific Cd/Ca values fall between those of late Quaternary Atlantic and Pacific benthic foraminifera; (2) there are no systematic Cd/Ca offsets between Cibicidoides kullenbergi, Cibicidoides wuellerstorfi and Uvigerina spp.; and (3) there is a very slight Cd/Ca change coincident with d13C. Cd/Ca, slightly higher in younger, isotopically lighter samples, exhibits a smaller increase than predicted if circulation were the primary cause of the carbon shift. The carbon shift may have been due to a long-term shift in the steady-state carbon isotope input or to a change in the sedimentation of organic carbon relative to calcium carbonate.

(Table 1) Oxygen and carbon isotopes for foraminiferal taxa at DSDP Hole 76-540

We analyzed the oxygen and carbon isotopic composition of planktonic and benthic foraminifers picked from 13 late Eocene to late Oligocene samples from DSDP Site 540 (23°49.73'N, 84°22.25'W, 2926 m water depth) from the Gulf of Mexico. An enrichment occurs in 18O of about 0.5 to 0.8 per mil in both benthic foraminifers and surface-dwelling planktonic foraminifers between the latest Eocene and early Oligocene. This early Oligocene maximum is followed by lower 18O values. A 1.2 per mil d13C decrease in both benthic and planktonic foraminiferal data occurs from the late Eocene to the late Oligocene. There is a correspondence of the 13C signal to deep-sea records; however, the amplitude of this change is greater than previously seen in deep-sea cores, possibly as a result of proximity to terrestrial sources of carbon. The covarying isotopic changes in both benthic and planktonic foraminifers suggest global causes, such as ice volume increases and increased terrestrial carbon input to the ocean. However, during the latter part of the record (early-late Oligocene), the increases in the benthic 18O without accompanying increases observed with planktonic foraminifers suggest that changes in only one part of the system occurred; one potential explanation being a decrease in bottom-water temperatures without concomitant changes in the surface waters. The 18O differences between species of planktonic foraminifers and the difference between planktonic and benthic 18O data indicate that diagenesis problems are minimal. These preliminary results are encouraging given that these cores are partially lithified.