Interstitial-water chemistry and stable isotope record of Prydz Bay sediments

Leg 119 of the Ocean Drilling Program (ODP) provided the first opportunity to study the interstitial-water chemistry of the eastern Antarctic continental margin. Five sites were cored in a northwest-southeast transect of Prydz Bay that extended from the top of the continental slope to within 30 km of the coastline. Geological studies of the cores reveal a continental margin that has evolved through terrestrial, glacial, and glacial-marine environments. Chemical and stable isotopic analyses of the interstitial-waters were performed to determine the types of depositional environments and the diagenetic and hydrologic processes that are operating in this unusual marine environment. Highly compacted glacial sediments provide an effective barrier to the vertical diffusion of interstitial-water solutes. Meteoric water from the Antarctic continent appears to be flowing into Prydz Bay sediments through the sequence of terrestrial sediments that lie underneath the glacial sediments. The large amounts of erosion associated with glacial advances appear to have had the effect of limiting the amount of marine organic matter that is incorporated into the sediments on the continental shelf. Although all of the sites cored in Prydz Bay exhibit depletions in dissolved sulfate with increasing depth, the greatest bacterial activity is associated with a thin layer of diatom ooze that coats the seafloor of the inner bay. Results of alkalinity modeling, thermodynamic calculations, and strontium analyses indicate that (1) ocean bottom waters seaward of Site 740 are undersaturated with respect to both calcite and aragonite, (2) interstitial waters at each site become saturated or supersaturated with respect to calcite and aragonite with increasing depth, (3) precipitation of calcium carbonate reduces the alkalinity of the pore waters with increasing depth, and (4) recrystallization of aragonite to calcite accounts for 24% of the pore-water strontium. Weathering of unstable terrestrial debris and cation exchange between clay minerals and pore fluids are the most probable chemical processes affecting interstitial water cation gradients.

Stable carbon and oxygen isotope ratios of Paleogene planktonic foraminifera from the Maud Rise

The oxygen and carbon isotopic composition has been measured for numerous Paleogene planktonic foraminifer species from Maud Rise, Weddell Sea (ODP Sites 689 and 690), the first such results from the Antarctic. The results provide information about large-scale changes in the evolution of temperatures, seasonally, and structure of the upper water column prior to the development of a significant Antarctic cryosphere. The early Paleocene was marked by cooler surface-water conditions compared to the Cretaceous and possibly a less well developed thermocline. The late Paleocene and early Eocene saw the expansion of the thermocline as Antarctic surface waters became warm-temperate to subtropical. The late Paleocene to early Eocene thermal maximum was punctuated by two brief excursions during which time the entire Antarctic water column warmed and the meridional temperature gradient was reduced. The first of these excursions occurred at the Paleocene/Eocene boundary, in association with a major extinction in deep sea benthic foraminifers. The second excursion occurred within the early Eocene at ~54.0 Ma. These excursions are of global importance and represent the warmest intervals of the entire Cenozoic. The excursions were associated with fundamental changes in deep-water circulation and global heat transport. The thermal maximum of the early Eocene ended with the initiation of a long-term cooling trend at 52.0 Ma. This cooling trend was associated with reduced seasonality, and diminished structure and/or duration of the seasonal thermocline. The cooling trend was punctuated by three major cooling steps at 43.0, 40.0, and -36.0 Ma.

Isotopic and chemical compositions of rocks and minerals from the TAG hydrothermal mound, ODP Site 957

Strontium- and oxygen-isotopic measurements of samples recovered from the Trans-Atlantic Geotraverse (TAG) hydrothermal mound during Leg 158 of the Ocean Drilling Program provide important constraints on the nature of fluid-rock interactions during basalt alteration and mineralization within an active hydrothermal deposit. Fresh Mid-Ocean Ridge Basalt (MORB), with a 87Sr/86Sr of 0.7026, from the basement beneath the TAG mound was altered at both low and high temperatures by seawater and altered at high temperature by near end-member black smoker fluids. Pillow breccias occurring beneath the margins of the mound are locally recrystallized to chlorite by interaction with large volumes of conductively heated seawater (>200°C). The development of a silicified, sulfide-mineralized stockwork within the basaltic basement follows a simple paragenetic sequence of chloritization followed by mineralization and the development of a quartz+pyrite+paragonite stockwork cut by quartz-pyrite veins. Initial alteration involved the development of chloritic alteration halos around basalt clasts by reaction with a Mg-bearing mixture of upwelling, high-temperature (>300°C), black smoker-type fluid with a minor (<10%) proportion of seawater. Continued high-temperature (>300°C) interaction between the wallrock and these Mg-bearing fluids results in the complete recrystallization of the wallrock to chlorite+quartz+pyrite. The quartz+pyrite+paragonite assemblage replaces the chloritized basalts, and developed by reaction at 250-360°C with end-member hydrothermal fluids having 87Sr/86Sr ~0.7038, similar to present-day vent fluids. The uniformity of the 87Sr/86Sr ratios of hydrothermal assemblages throughout the mound and stockwork requires that the 87Sr/86Sr ratio of end-member hydrothermal fluids has remained relatively constant for a time period longer than that required to change the interior thermal structure and plumbing network of the mound and underlying stockwork. Precipitation of anhydrite in breccias and as late-stage veins throughout most of the mound and stockwork, down to at least 125 mbsf, records extensive entrainment of seawater into the hydrothermal deposit. 87Sr/86Sr ratios indicate that most of the anhydrite formed from ~2:1 mixture of seawater and black smoker fluids (65%±15% seawater). Oxygen-isotopic compositions imply that anhydrite precipitated at temperatures between 147°C and 270°C and require that seawater was conductively heated to between 100°C and 180°C before mixing and precipitation occurred. Anhydrite from the TAG mound has a Sr-Ca partition coefficient Kd ~0.60±0.28 (2 sigma). This value is in agreement with the range of experimentally determined partition coefficients (Kd ~0.27-0.73) and is similar to those calculated for anhydrite from active black smoker chimneys from 21°N on the East Pacific Rise. The d18O (for SO4) of TAG anhydrite brackets the value of seawater sulfate oxygen (~9.5?). Dissolution of anhydrite back into the oceans during episodes of hydrothermal quiescence provides a mechanism of buffering seawater sulfate oxygen to an isotopically light composition, in addition to the precipitation and dissolution of anhydrite within the oceanic basement during hydrothermal recharge at the mid-ocean ridges.

Late Quaternary planktonic foraminifera of ODP Hole 175-1087A

Planktonic foraminiferal assemblages from the upper Pleistocene part of Hole 1087A (0 to 12.1 meters below seafloor) are investigated to assess the role of global and local climate changes on surface circulation in the southern Benguela region. The benthic stable isotope record indicates that the studied interval is representative of the last four climatic cycles, that is, down to marine isotope Stage (MIS) 12. The species assemblages bear a clear transitional to subpolar character, with Neogloboquadrina pachyderma (d), Globorotalia inflata, and Globigerina bulloides, in order of decreasing abundance, as the dominant taxa. This species association presently characterizes the mixing domain of old upwelled and open ocean waters, seaward of the Benguela upwelling cells. Abundance variation of the dominant foraminiferal species roughly follows a glacial-interglacial pattern down to MIS 8, suggesting an alternation of upwelling strength and associated seaward extension of the belt of upwelled water as a response to global climate changes. This pattern is interrupted from ~250 ka down to MIS 12, where the phase relationship with global climate is ill defined and might be interpreted as a local response of the southern Benguela region to the mid-Brunhes event. Of particular interest is a single pulse of newly upwelled waters at the location of Site 1087 during early MIS 9 as indicated by a peak abundance of sinistral N. pachyderma (s). Variable input of warm, salty Indian Ocean thermocline waters into the southeast Atlantic, a key component of the Atlantic heat conveyor, is indicated by abundance changes of the tropical taxon Globorotalia menardii. From this tracer, we suggest that interocean exchange was hardly interrupted throughout the last 460 k.y., but was most effective at glacial terminations, particularly during Terminations I and II, as well as during the upper part of MIS 12. This maximum input of Indian Ocean waters around the southern tip of Africa is associated with the reseeding of G. menardii in the tropical Atlantic.

Stable isotope record of benthic and planktonic foraminifera from ODP Site 175-1087 in the southern Cape Basin, Atlantic Ocean

High-resolution planktonic and benthic stable isotope records from Ocean Drilling Program Site 1087 off southeast Africa provide the basis for a detailed study of glacial-interglacial (G-IG) cycles during the last 500 k.y. This site is located in the Southern Cape Basin at the boundary of the coastal upwelling of Benguela and close to the gateway between the South Atlantic and the Indian Oceans. It therefore monitors variations of the hydrological fronts associated with the upwelling system and the Atlantic-Indian Ocean interconnections, in relation to global climate change. The coldest period of the last 500 k.y. corresponds to marine isotope Stage (MIS) 12, when surface water temperature was 4°C lower than during the last glacial maximum (LGM) as recorded by the surface-dwelling foraminifer Globigerinoides ruber. The warmest periods occurred during MISs 5 and 11, a situation slightly different to that observed at Site 704, which is close to the Polar Front Zone, where there is no significant difference between the interglacial stages for the past 450 k.y., except the long period of warmth during MIS 11. The planktonic and benthic carbon isotope records do not follow the G-IG cycles but show large oscillations related to major changes in the productivity regime. The largest positive 13C excursion between 260 and 425 ka coincides with the global mid-Brunhes event of carbonate productivity. The oxygen and carbon isotopic gradients between surface and deep waters display long-term changes superimposed on rapid and high-frequency fluctuations that do not follow the regular G-IG pattern; these gradients indicate modifications of the temperature, salinity, and productivity gradients due to changes in the thermocline depth, the position of the hydrological fronts, and the strength of the Benguela Current.

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.

Mid-Pleistocene benthic foraminiferal record in the Southwest Pacific

Benthic foraminiferal faunas from three bathyal sequences provide a proxy record of oceanographic changes through the mid-Pleistocene transition (MPT) on either side of the Subtropical Front (STF), east of New Zealand. Canonical correspondence analyses show that factors related to water depth, latitude and climate cycles were more significant than oceanographic factors in determining changes in faunal assemblage composition over the last 1 Ma. Even so, mid-Pleistocene faunal changes are recognizable and can be linked to inferred palaeoceanographic causes. North of the largely stationary STF the faunas were less variable than to the south, perhaps reflecting the less extreme glacial-interglacial fluctuations in the overlying Subtropical Surface Water. Prior to Marine Isotope Stage (MIS) 21 and after MIS 15, the northern faunas had fairly constant composition, but during most of the MPT faunal composition fluctuated in response to climate-related food-supply variations. Faunal changes through the MPT suggest increasing food supply and decreasing dissolved bottom oxygen. South of the STF, beneath Subantarctic Surface Water, mid-Pleistocene faunas exhibited strong glacial-interglacial fluctuations, inferred to be due to higher interglacial nutrient supply and lower oxygen levels. The most dramatic faunal change in the south occurred at the end of the MPT (MIS 17- 12). with an acme of Abditodentrix pseudothalmanni, possibly reflecting higher carbon flux and lower bottom oxygen. This study suggests that the mid-Pleistocene decline and extinction of a group of elongate, cylindrical deep-sea foraminifera may have been related to decreased bottom oxygen concentrations as aresult of slower deep-water currents.

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.

Sedimentology and planktonioc foraminifera of core SU90-08

The observation by Heinrich (1988) that, during the last glacial period, much of the input of ice-rafted detritus to the North Atlantic sediments may have occurred as a succession of catastrophic events, rekindled interest on the history of the northern ice sheets over the last glacial period. In this paper, we present a rapid method to study the distribution of these events (both in space and time) using whole core low-field magnetic susceptibility. We report on approximately 20 cores covering the last 150 to 250 kyr. Well-defined patterns of ice-rafted detritus appear during periods of large continental ice-sheet extent, although these are not always associated within their maxima. Most of the events may be traced across the North Atlantic Ocean. For the six most recent Heinrich layers (HL), two distinct patterns exist: HL1, HL2, HL4, HL5 are distributed along the northern boundary of the Glacial Polar Front, over most of the North Atlantic between ~40° and 50°N; HL3 is more restricted to the central and eastern part of the northern Atlantic. The Nd-Sr isotopic composition of the material constituting different Heinrich events indicates the different provenance of the two patterns: HL3 has a typical Scandinavia-Arctic-Icelandic 'young crust' signature, and the others have a large component of northern Quebec and northern West Greenland 'old crust' material. These isotopic results, obtained on core SU-9008 from the North American basin, are in agreement with the study by Jantschik and Huon (1992), who used K-Ar dating of silt- and clay-size fractions of an eastern basin core (ME-68-89). These data confirm the large spatial scale of these events, and the enormous amount of ice-rafted detritus they represent.

Stable isotopes of foraminifers, mineralogy and ages of sediment core GeoB1523-1

Today the western tropical Atlantic is the most important passage for cross-equatorial transfer of heat in the form of warm surface water flowing from the South into the North Atlantic. Circulation changes north of South America may thus have influenced the global thermohaline circulation system and high northern latitude climate. Here we reconstruct late Quaternary variations of western equatorial Atlantic surface circulation and Amazon lowland climate obtained from a multiproxy sediment record from Ceará Rise. Variations in the illite/smectite ratio suggest drier climatic conditions in the Amazon Basin during glacials relative to interglacials. The 230Thex-normalized fluxes and the 13C/12C record of organic carbon indicate that sea level fluctuations, shelf topography, and changes of the surface circulation pattern controlled variations and amplitude of terrigenous sediment supply to the Ceará Rise. We attribute variations in thermocline depth, reconstructed from vertical planktic foraminiferal oxygen isotope gradients and abundances of the phytoplankton species Florisphaera profunda, to changes in southeast trade wind intensity. Strong trade winds during ice volume maxima are associated with a deep western tropical Atlantic thermocline, strengthening of the North Brazil Current retroflection, and more vigorous eastward flow of surface waters.

Stable isotope record of DSDP Hole 81-552A in the northeastern Atlantic Ocean

Oxygen and carbon isotope ratios in benthic foraminifers have been determined at 10 cm intervals through the top 59 m of DSDP Hole 552A. This provides a glacial record of remarkable resolution for the late Pliocene and Pleistocene. The major glacial event which marked the onset of Pleistocene-like glacial-interglacial alternations was at about 2.4 m.y. ago. These very high-resolution data do not support the notion of significant Northern Hemisphere glaciation between 3.2 and 2.4 m.y. ago.

Sulfur contents and S, C and O isotopic compositions in serpentinized peridotites at ODP Site 153-920

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated d34S_sulfide (3.7 to 12.7?). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400°C alone cannot account for both the high sulfur contents and high d34S_sulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (~400°C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ~300°C. Serpentinization produces highly reducing conditions and significant amounts of H2 and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in 13C (up to 4.5?) at temperatures above 250°C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 mln ton seawater S per year. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates.