Benthic foraminiferal fauna and isotope record in Holocene sediments of the northwest Indian Ocean

Historically, the Holocene has been considered an interval of relatively stable climate. However, recent studies from the northern Arabian Sea (Netherlands Indian Ocean Program 905) suggested high-amplitude climate shifts in the early and middle Holocene based on faunal and benthic isotopic proxy records. We examined benthic foraminiferal faunal and stable isotopic data from Ocean Drilling Program (ODP) Site 723 and total organic carbon data from ODP Site 724, Oman Margin (808 and 593 m water depths, respectively). At Site 723 the mid-Holocene shift in d18O values of infaunal benthic species Uvigerina peregrina (1.4 per mil) is 3 times larger than that of epifaunal benthic species Cibicides kullenbergi recorded at Site NIOP 905 off Somalia. However, none of the five other benthic species we measured at Hole 723A exhibits such a shift in d18O. We speculate that the late Holocene d18O decrease in U. peregrina represents species-specific changes in ecological habitat or food preference in response to changes in surface and deep ocean circulation. While the stable isotopic data do not appear to indicate a middle Holocene climatic shift, our total organic carbon and benthic faunal assemblage data do indicate that the early Holocene deep Arabian Sea was influenced by increased ventilation perhaps by North Atlantic Deep Water and/or Circumpolar Deep Water incursions into the Indian Ocean, leading to remineralization of organic matter and a relatively weak early Holocene oxygen minimum zone in the northwest Arabian Sea in spite of strong summer monsoon circulation.

Whole rock geochemistry and stable isotopes of rocks, fragments and foraminifers from two ODP Leg 166 holes

Total carbon and carbonate contents, quantitative carbonate mineralogy, trace metal concentrations, and stable isotope compositions were determined on a suite of samples from the Miocene sections at Sites 1006 and 1007. The Miocene section at Site 1007, located at the toe-of-slope, contains a relatively high proportion of bank-derived components and becomes fully lithified at a depth of ~300 meters below seafloor (mbsf). By contrast, Miocene sediments at Site 1006, situated in Neogene drift deposits in the Straits of Florida and composed primarily of pelagic carbonates, do not become fully lithified until a depth of ~675 mbsf. Diagenetic and compositional contrasts between Sites 1006 and 1007 are reflected in geochemical data derived from sediment samples from each site.

Geochemistry of low-temperatuer altered basalts of ODP Hole 136-843B

The mineralogy and chemistry of altered basalts and the stable isotopic compositions of secondary vein carbonates were studied in cores from Ocean Drilling Program Hole 843B, located in 95-Ma crust of the Hawaiian Arch. Millimeter- to centimeter-sized dark alteration halos around veins are 5%-15% altered to celadonite and Fe-oxyhydroxides, plus minor saponite and calcite. Adjacent gray host rocks are about 15% altered to saponite and calcite. The dark halos are enriched in H2O+, CO2, FeT, K2O, MnO, and Fe3+/FeT and depleted in SiO2, Al2O3, MgO, and TiO2 relative to gray host rocks. Brown alteration halos occur around veins where veins are more abundant, and are similar to dark halos, but contain more Fe-oxyhydroxides and exhibit greater Fe2O3T contents and higher Fe3+/FeT. Stable isotopic compositions of vein carbonates are consistent with their precipitation from seawater at temperatures of 5°-40°C. Crosscutting relationships of veins and zoned vein and vesicle fillings reveal a sequence of secondary mineral formation and alteration conditions. Celadonite and Fe-oxyhydroxides formed and dark alteration halos developed relatively early, under oxidizing conditions at low temperatures (<50°C). Saponite formed later at lower seawater/rock ratios and under more reducing conditions. Calcite and pyrite formed last in veins and vesicles from more evolved, seawaterderived fluids at temperatures of 5°-40°C. A second stage of celadonite, with compositions distinct from the early celadonite, also occurred relatively late (within the "calcite stage"), and may be related to refracturing of the crust and introduction of less-evolved seawater solutions into the rocks. Trends to higher K2O contents are attributed to alteration, but high K/Ti, Ba, and Zr contents indicate the presence of enriched or transitional MORB. CO2 contents of Pacific ODP cores exhibit a general increase with age suggesting progressive fixation of CO2 as calcite in the crust, but this could be complicated by local heterogeneities in fracturing and calcite formation in the crust.

Stable-isotopes and calcium carbonate at DSDP Hole 73-524

This paper presents a compilation of stable-isotope and percentage-of-carbonate data for the Upper Cretaceous/ lower Tertiary hemipelagic sediments from DSDP Leg 73, Site 524.

Interstitial water d13C and sediment geochemistry of ODP Leg 166 sites

A review of interstitial water samples collected from Sites 1003-1007 of the Bahamas Transect along with a shore-based analysis of oxygen and carbon isotopes, minor and trace elements, and sediment chemistry are presented. Results indicate that the pore-fluid profiles in the upper 100 meters below seafloor (mbsf) are marked by shifts between 20 and 40 mbsf that are thought to be caused by changes in sediment reactivity, sedimentation rates, and the influence of strong bottom currents that have been active since the late Pliocene. Pore-fluid profiles in the lower Pliocene-Miocene sequences are dominated by diffusion and do not show significant evidence of subsurface advective flow. Deeper interstitial waters are believed to be the in situ fluids that have evolved through interaction with sediments and diffusion. Pore-fluid chemistry is strongly influenced by carbonate recrystallization processes. Increases in pore-fluid Cl- and Na+ with depth are interpreted to result mainly from carbonate remineralization reactions that are most active near the platform margin. A lateral gradient in detrital clay content observed along the transect, leads to an overall lower carbonate reactivity, and enhances preservation of metastable aragonite further away from the platform margin. Later stage burial diagenesis occurs at slow rates and is limited by the supply of reactive elements through diffusion.

Isotope characterisation of Villars Cave stalagmites

We present a new mid-latitude speleothem record of millennial-scale climatic variability during OIS3 from the Villars Cave that, combined with former published contemporaneous samples from the same cave, gives a coherent image of the climate variability in SW-France between ~55 ka and ~30 ka. The 0.82 m long stalagmite Vil-stm27 was dated with 26 TIMS U-Th analyses and its growth curve displays variations that are linked with the stable isotopes, both controlled by the climatic conditions. It consists in a higher resolved replicate of the previously published Vil-stm9 and Vil-stm14 stalagmites where Dansgaard-Oeschger (DO) events have been observed. The good consistency between these three stalagmites and the comparison with other palaoeclimatic reconstructions, especially high resolution pollen records (ODP 976 from the Alboran Sea, Monticchio Lake record from southern Italy) and the nearby MD04-2845 Atlantic Ocean record, permits to draw a specific climatic pattern in SW-France during the OIS3 and to see regional differences between these sites. Main features of this period are: 1) warm events corresponding to Greenland Interstadials (GIS) that are characterized by low speleothem d13C, high temperate pollen percentages, warm temperatures and high humidity; among these events, GIS#12 is the most pronounced one at Villars characterized by an abrupt onset at ~46.6 ka and a duration of about 2.5 ka. The other well individualized warm event coincides with GIS#8 which is however much less pronounced and occurred during a cooler period as shown by a lower growth rate and a higher d13C; 2) cold events corresponding to Greenland Stadials (GS) that are clearly characterized by high speleothem d13C, low temperate pollen abundance, low temperature and enhanced dryness, particularly well expressed during GS coinciding with Heinrich events H5 and H4. The main feature of the Villars record is a general cooling trend between the DO#12 event ~45.5 ka and the synchronous stop of the three stalagmites at ~30 ka ±1, with a first well marked climatic threshold at ~41 ka after which the growth rate and the diameter of all stalagmites slows down significantly. This climatic evolution differs from that shown at southern Mediterranean sites where this trend is not observed. The ~30 ka age marks the second climatic threshold after which low temperatures and low rainfalls prevent speleothem growth in the Villars area until the Lateglacial warming that occurred at ~16.5 ± 0.5 ka. This 15 ka long hiatus, as the older Villars growth hiatus that occurred between 67.4 and 61 ka, are linked to low sea levels, reduced ocean circulation and a southward shift of the Polar Front that likely provoked local permafrost formation. These cold periods coincide with both low summer 65°N insolation, low atmospheric CO2 concentration and large ice sheets development (especially the Fennoscandian).

Relative abundance and isotopic composition of calcite, dolomite and siderite from ODP Leg 164 sites

Authigenic carbonate mineral distributions are compared to pore-water geochemical profiles and used to evaluate diagenesis within sedimentary sections containing gas hydrates on the Blake Ridge (Ocean Drilling Program Sites 994, 995, and 997). Carbonate mineral distributions reveal three distinct diagenetic zones. (1) Carbonate minerals in the upper 20 m are primarily biogenic and show no evidence of diagenesis. The d13C and d18O values of calcite within this zone reflects marine carbonate (~0 per mil Peedee belemnite [PDB]) formed in equilibrium with seawater. (2) Between 20 and 100 mbsf, calcite d13C values are distinctly negative (as low as -7.0 per mil), and authigenic dolomite is common (~2-40 wt%) with d13C values between -3.6 per mil and 13.7 per mil. (3) Below 100 mbsf, dolomite abundance decreases to trace amounts, and disseminated siderite becomes the pervasive (~2-30 wt%) authigenic carbonate. Both siderite textures and stable isotope values indicate direct precipitation from pore fluids rather than dolomite replacement. The d13C and d18O values of siderite vary from 5.0 per mil to 10.9 per mil and 2.9 per mil to 7.6 per mil, respectively. Comparisons between the d13C profiles of dissolved inorganic carbon (DIC) and pore-water concentration gradients, with the d13C and d18O values of authigenic carbonates, delineate a distinct depth zonation for authigenic carbonate mineral formation. Coincidence of the most negative d13CDIC values (<=-38 per mil) and negative d13C values of both calcite and dolomite, with pore-water alkalinity increases, sulfate depletion, and decreases in interstitial Ca2+ and Mg2+ concentrations at and below 20 mbsf, suggests that authigenic calcite and dolomite formation is initiated at the base of the sulfate reduction zone (~21 mbsf) and occurs down to ~100 mbsf. Siderite formation apparently occurs between 120 and 450 mbsf; within, and above, the gas hydrate-bearing section of the sediment column (~200-450 mbsf). Siderite d13C and d18O values are nearly uniform from their shallowest occurrence to the bottom of the sedimentary section. However, present-day pore-water d13CDIC values are only similar to siderite d13C values between ~100 and 450 mbsf. Furthermore, calculated equilibrium d18O values of siderite match the measured 18O values of siderite between 120 and 450 mbsf. This interval is characterized by high alkalinity (40-120 mM) and low Ca2+ and Mg2+ concentrations, conditions that are consistent with siderite formation.

Organic matter composition of Cretaceous sediments of the central Pacific Ocean

Complete records of organic-carbon-rich Cretaceous strata were continuouslycored on the flanks of the Mid-Pacific Mountains and southern Hess Rise in the central North Pacific Ocean during DSDP Leg 62. Organic-carbon-rich laminated silicified limestones were deposited in the western Mid-Pacific Mountains during the early Aptian, a time when that region was south of the equator and considerably shallower than at present. Organic-carbon-rich, laminated limestone on southern Hess Rise overlies volcanic basement and includes 136 m of stratigraphic section of late Albian to early Cenomanian age. This limestone unit was deposited rapidly as Hess Rise was passing under the equatorial high-productivity zone and was subsiding from shallow to intermediate depths. The association of volcanogenic components with organic-carbon-rich strata on Hess Rise in the Mid-Pacific Mountains is striking and suggests that there was a coincidence of mid-plate volcanic activity and the production and accumulation of organic matter at intermediate water depths in the tropical Pacific Ocean during the middle Cretaceous. Pyrolysis assays and analyses of extractable hydrocarbons indicate that the organic matter in the limestone on Hess Rise is composed mainly of lipid-rich kerogen derived from aquatic marine organisms and bacteria. Limestones from the Mid-Pacific Mountains generally contain low ratios of pyrolytic hydrocarbons to organic carbon and low hydrogen indices, suggesting that the organic matter may contain a significant proportion of land-derived material, possibly derived from numerous volcanic islands that must have existed before the area subsided. The organic carbon in all samples analyzed is isotopically light (d13C -24 to -29 per mil) relative to most modern rine organic carbon, and the lightest carbon is also the most lipid-rich. There is a positive linear correlation between sulfur and organic carbon in samples from Hess Rise and from the Mid-Pacific Mountains. The slopes and intercepts of C-S regression lines however, are different for each site and all are different from regression lines for samples from modern anoxic marine sediments and from Black Sea cores. The organic-carbon-rich limestones on Hess Rise, the Mid-Pacific Mountains, and other plateaus and seamounts in the Pacific Ocean are not synchronous but do occur within the same general middle Cretaceous time period as organic-carbon-rich lithofacies elsewhere in the world ocean, particularly in the Atlantic Ocean. Strata of equivalent age in the deep basins of the Pacific Ocean are not rich in organic carbon, and were deposited in oxygenated environments. This observation, together with the evidence that the plateau sites were considerably shallower and closse to the equator during the middle Creataceous suggests that local tectonic and hydrographic conditions may have resulted in high surface-water productivity and the preservation of organic matter in an oxygen-deficient environment where an expanded mid-water oxygen minimum developed and impinged on elevated platforms and seamounts.

Isotopic composition of the fine fraction of ODP Site 114-704

Ocean Drilling Program Site 704 in the subantarctic South Atlantic was drilled to investigate the response of the Southern Ocean to climatic and Oceanographic developments during the late Neogene. Stable oxygen and carbon isotopes of fine-fraction (<63 µm) carbonate were analyzed to supplement similar analyses of benthic and planktonic foraminifers. The fine fraction is generally composed primarily of coccoliths, and isotopic analyses of the fine fraction were made to complement the foraminiferal analyses. The isotopic curves thus generated suggest paleoceanographic changes not recognizable by the use of benthic and planktonic foraminifers alone. The global Chron 6 carbon isotope shift, found at 253-244 mbsf (6.39-6.0 Ma) at Site 704 in the planktonic and benthic record, is seen in the fine-fraction d13C record as a gradual decrease from 255 mbsf (6.44 Ma) to 210 mbsf (4.24 Ma). At 170 mbsf, mean d18O values of Neogloboquadrina pachyderma increase by 0.6 per mil-0.7 per mil (Hodell and Ciesielski, 1991, doi:10.2973/odp.proc.sr.114.150.1991), reflecting decreased temperature and increased continental ice volume. Accumulation rates increase by 3.3 times above this depth (which corresponds to an age of 2.5 Ma), suggesting increased upwelling and biologic productivity. Carbon isotopic values of fine-fraction carbonate decrease by about 1.5 per mil at 2.6 Ma; however, no change is recorded in the d13C of N. pachyderma. The fine-fraction d13C shift slightly precedes an average l per mil decrease in d13C in benthic foraminifers. The cause of the benthic d13C shift (most likely due to a change in deep water circulation; Hodell and Ciesielski, 1991) is probably not directly related to the fine-fraction shift. The fine-fraction shift is most likely caused by (1) a change in the upwelling to productivity ratio at this site, with increased upwelling bringing lighter carbon to surface waters, more productivity, and higher sedimentation rates and (2) a change in the particle composition of the fine fraction. The increased upwelling is probably due to a northward migration of the Antarctic Polar Front to a position nearer Site 704.

Geochemistry and soil characteristics of sediment core GeoB4234

Stable isotopes of sedimentary nitrogen and organic carbon are widely used as proxy variables for biogeochemical parameters and processes in the water column. In order to investigate alterations of the primary isotopic signal by sedimentary diagenetic processes, we determined concentrations and isotopic compositions of inorganic nitrogen (IN), organic nitrogen (ON), total nitrogen (TN), and total organic carbon (TOC) on one short core recovered from sediments of the eastern subtropical Atlantic, between the Canary Islands and the Moroccan coast. Changes with depth in concentration and isotopic composition of the different fractions were related to early diagenetic conditions indicated by pore water concentrations of oxygen, nitrate, and ammonium. Additionally, the nature of the organic matter was investigated by Rock-Eval pyrolysis and microscopic analysis. A decrease in ON during aerobic organic matter degradation is accompanied by an increase of the 15N/14N ratio. Changes in the isotopic composition of ON can be described by Rayleigh fractionation kinetics which are probably related to microbial metabolism. The influence of IN depleted in 15N on the bulk sedimentary (TN) isotope signal increases due to organic matter degradation, compensating partly the isotopic changes in ON. In anoxic sediments, fixation of ammonium between clay lattices results in a decrease of stable nitrogen isotope ratio of IN and TN. Changes in the carbon isotopic composition of TOC have to be explained by Rayleigh fractionation in combination with different remineralization kinetics of organic compounds with different isotopic composition. We have found no evidence for preferential preservation of terrestrial organic carbon. Instead, both TOC and refractory organic carbon are dominated by marine organic matter. Refractory organic carbon is depleted in 13C compared to TOC.