Geochemistry of secondary carbonates in ODP Leg 115 basalts

This report presents the results of a study of the stable isotopic and chemical composition of secondary carbonate minerals precipitated within basalts at Ocean Drilling Program Sites 707 and 715. At Site 715, the secondary carbonates are all composed of calcite and display a narrow range of carbon and oxygen stable isotope ratios, with values ranging from -2.75 per mil to 1.95 per mil PDB and -0.27 per mil to 2.86 per mil PDB, respectively. Strontium, iron, and manganese values of the samples are generally low. The geochemistry of Site 715 samples indicates that they precipitated from seawater-domi- nated fluids, at low temperatures, as is typical of secondary carbonates from most Deep Sea Drilling Project sites. In contrast, at Site 707, aragonite, siderite, and manganese-rich calcite occur as secondary carbonates in addition to calcite. The carbon isotopes of the Site 707 carbonates of all rock types are depleted in 13C. Values range from -2.79 per mil to -16.43 per mil PDB. Oxygen isotope values do not show a wide variation, ranging from -1.78 per mil to 1.17 per mil. The strontium contents of the samples range from 5200 to 8100 ppm for aragonites, and from 145 to 862 ppm for calcites. Iron and manganese contents are high in calcites and siderites and low in aragonites. Site 707 carbonates precipitated at low temperatures in a fairly closed system, in which basalt-seawater interaction has greatly influenced the chemistry of the pore fluids. The reactions occurring within the system before and in conjunction with secondary carbonate precipita- tion include oxidation of isotopically light methane, derived from fluids circulating within the basalts, and reduction of substantial amounts of iron and manganese oxides from the basalts.

Oxygen and carbon isotope data from late calcite and zeolite pore-fill cements at DSDP Site 445

Oxygen isotopic composition of zeolite pore-fill cements in andesitic volcaniclastic sandstones recovered from DSDP Site 445 ranges from +30.1 to +17.8? (SMOW) downhole. This change is controlled by large heat flow from the basement which caused early diagenetic emplacement of zeolites during early basin rifting. d18O-values of late calcite cements range from +25.1 to +27.4? (SMOW); their petrographic relation and inferred temperature of formation suggest that calcite cements were formed during late stages of diagenesis. Isotopic composition in these sandstones is in agreement with mineral paragenesis determined microscopically.

Physical and chemical analysis of firn cores from Ronne Ice Shelf, Antarctica

This data on the distribution of the accumulation rate and 18O content of near-surface layers in the eastern part of the Ronne Ice Shelf, Antarctica, were derived from an analysis of 16 firn cores. The firn cores were drilled along the traverse route of the Filchner-V-Campaign in 1995. The traverse followed an ice flowline of the Foundation Ice Stream and reached the margin of the inland ice, an area which has not yet been investigated. On the ice shelf the accumulation rates decrease with distance from the coast. Ascending to the inland ice the accumulation rates again reach almost coastal values. This regional distribution is in agreement with the temperature gradient along the traverse. The 18O content of the near-surface layers is closely related to the 10 m firn temperature. They strongly decrease from the grounding line towards the inland ice. At the southernmost site at 1100 m a.s.l., the mean d18O value of the firn decreases to -40?. Ice with that isotopic signature was found in cores from the central part of the Ronne Ice Shelf just above the marine ice layer, indicating that it originates from this area. All ice deposited as snow further south was melted beneath the ice shelf after passing the grounding-line area. The time series of accumulation rate and 18O content reveal no climatic trend during the last 30-50 years.

Petrology and isotope characteristics of basalts from ODP Hole 111-504B

Petrography and isotope geochemical characteristics of H, O, S, Sr, and Nd have been described for basalts recovered from Hole 504B during Leg 111 of the Ocean Drilling Program. The petrographic and chemical features of the recovered basalts are similar to those obtained previously (DSDP Legs 69, 70, and 83); they can be divided into phyric (plagioclase-rich) and aphyric (Plagioclase- and clinopyroxene-rich) basalts and show low abundances of TiO2, Na2O, K2O, and Sr. This indicates that the basalts belong to Group D, comprising the majority of the upper section of the Hole 504B. The diopside-rich nature of the clinopyroxene phenocrysts and Ca-rich nature of the Plagioclase phenocrysts are also consistent with the preceding statement. The Sr and Nd isotope systematics (average 87Sr/86Sr = 0.70267 ± 0.00007 and average 143Nd/144Nd = 0.513157 ± 0.000041) indicate that the magma sources are isotopically heterogeneous, although the analyzed samples represent only the lowermost 200-m section of Hole 504B. The rocks were subjected to moderate hydrothermal alteration throughout the section recovered during Leg 111. Alteration is limited to interstices, microfractures, and grain boundaries of the primary minerals, forming chlorite, actinolite, talc, smectite, quartz, sphene, and pyrite. In harmony with the moderate alteration, the following alteration-sensitive parameters show rather limited ranges of variation: H2O = 1.1 ±0.2 wt%, dD = - 38 per mil ± 4 per mil, d180 = 5.4 per mil ± 0.3 per mil, total S = 562 ± 181 ppm, and d34S = 0.8 per mil ± 0.3 per mil. Based on these data, it was estimated that the hydrothermal fluids had dD and d180 values only slightly higher than those of seawater, the water/rock ratios were as low as 0.02-0.2, and the temperature of alteration was 300°-400°C. Sulfur exists predominantly as pyrite and in minor quantities as chalcopyrite. No primary monosulfide was detected. This and the d34S values of pyrite (d34S = 0.8 per mil) suggest that primary pyrrhotite was almost completely oxidized to pyrite by reaction with hydrothermal fluids containing very little sulfate.

Mineralogy and geochemistry of Mg-phyllosilicates from Middle Valley, northern Juan de Fuca Ridge

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24 Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of = 0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14 Å with Fe/(Fe+Mg) ratios of ? 0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensiteychlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in d18O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H2O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300° C ± 30° for chlorite-quartz at 32 m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10-11°/m in the vent region.

Isotope ratios of smectites, calcites and whole rocks from DSDP Legs 51 and 52, Atlantic Ocean

Delta180 and 87Sr/86Sr isotopic data from smectites, calcites, and whole rocks, together with published isotopic age determinations, alkali element concentration data and petrographic observations suggest a sequential model of ocean floor alteration. The early stage lasts about 3 m.y. and is characterized by palagonite and smectite formation, and solutions with a large basaltic component, increasing with temperature which varies from 15° to 80° C at DSDP site 418A. Most carbonates are deposited after this stage from solutions with a negligible basaltic Sr component and temperatures of 15° to 40° C. Water of seawater Sr and O isotopic composition is shown to percolate to at least 500 m into the basaltic basement. No evidence was found for continuing exchange of strontium or oxygen after 3 m.y.

Quaternary surface-water stable isotope signal from calcareous nannofossils at DSDP Site 90-593, South Tasman Sea

Oxygen isotope values from calcareous nannofossils in four cores spanning the Quaternary from DSDP Site 593 in Tasman Sea are compared with the delta18O signal of planktonic and benthic foraminifers from the same samples. The classic mid-late Quaternary isotope stages are exhibited with stage 12 particularly well developed. When delta18O values of nannofossils are adjusted for coccolithophore vital effects they indicate larger (by 1-6°C) surface to bottom paleotemperature gradients and greater (by 1-3°C) changes in mean sea-surface temperature between full glacial and interglacial conditions than do delta18O values from planktonic foraminifers. Along with the foraminifers, the nannofossils record a bimodal distribution of delta18O between the early and mid-late Quaternary, indicating a significant change in global ice budget. The delta13C of nannofossils also shows a bimodal distribution, but is opposite to that for the foraminifers. Nannofossil delta18O values record a shift of c. -0.8? at isotope stage 8 corresponding to a major reduction in abundance of the previously dominant gephyrocapsids. A shift in delta13C of c. -1.5? also occurs at stage 8, and a shift in delta13C of c. +1.2? at around stage 14. The delta18O shift in nannofossils is at least a Pacific-wide phenomenon; the delta13C shifts are possibly global. The delta13C signal of nannofossils exhibits an antipathetic relationship to that of benthic foraminifers back to isotope stage 18 but no significant correlation beyond this level to the base of the Quaternary. This is interpreted as reflecting local productivity dominating global influences on delta13C since stage 18 at DSDP Site 593. The difference between nannofossil and benthic foraminifer delta13C signals (Delta13C) tends to be maximum during glacial stages and minimum during interglacials throughout the section, showing a strong correlation with the nannofossil delta180 signal. The increased partitioning of 13C between surface and bottom waters during the glacial periods may indicate heightened productivity in surface waters in the southern Tasman Sea at these times.