Chemical composition and sulfur-isotope ratios in DSDP Legs 69-and 70

As part of the geochemical-petrological study of basalts recovered from DSDP Hole 504B (Leg 70) on the southern flank of the Costa Rica Rift, we investigated specially the relationships between the distribution and isotopic composition of sulfur of scattered and vein sulfides on the one hand, and the observed pattern and processes of secondary alterations on the other. The following groups of observations are essential: (1) variations in the contents and isotopic composition of sulfur of different forms of sulfides are clearly interrelated and are observed solely in porous horizons established on the basis of detailed geophysical experiments; (2) the enrichment of sulfides in the light sulfur isotope decreases from the upper to the lower horizons, and within horizons in the direction of the less-altered rock; (3) the increase of d34S values of scattered sulfides in individual permeable zones parallels a decrease in the degree of iron oxidation in the contents of crystallization water, and in the concentrations of Mg, K, and Li in the rock.

Molecular and stable isotope composition of headspace and total hydrogencarbon gases of ODP Leg 104 sites

Molecular and isotope compositions of headspace and total (free + sorbed) hydrocarbon gases from drilled cores of the three ODP Leg 104 Sites 642, 643, and 644 of the Voring Plateau are used to characterize the origin and distribution of these gases in Holocene to Eocene sediments. Only minor amounts of methane were found in the headspace (0.1 to < 0.001 vol%). Although methane through propane are present in all of the total gas samples, different origins account for the concentration and composition variations found. Site 643 at the foot of the outer Voring Plateau represents a geological setting with poor hydrocarbon generating potential, (sediments with low TOC and maturity overlying oceanic basement). Correspondingly, the total gas concentrations are low, typical for background gases (yield C1 - 4 = 31 to 232 ppb, C1/C2+ = 0.6 to 4; delta13C(CH4) -22 per mil to -42 per mil) probably of a diagenetic origin. Holocene to Eocene sediments, which overlie volcanic units, were drilled on the outer Vdring Plateau, at Holes 642B and D. Similar to Site 643, these sediments possess a poor hydrocarbon generating potential. The total gas character (yield C1 - 4 = 20 to 410 ppb; C1/C2+ = 1.7 to 13.3; delta13C(CH4) ca. -23 per mil to -40 per mil) again indicates a diagenetic origin, perhaps with the addition of some biogenic gas. The higher geothermal gradient and the underlying volcanics do not appear to have any influence on the gas geochemistry. The free gas (Vacutainer TM) in the sediments at Site 644 are dominated by biogenic gas (C1/C2+ > 104; delta13C(CH4) -77 per mil). Indications, in the total gas, of hydrocarbons with a thermogenic signature (yield C1 - 4 = 121 to 769 ppb, C1/ C2+ = 3 to 8; delta13C(CH4) = -39 per mil to -71 per mil), could not be unequivocally confirmed as such. Alternatively, these gases may represent mixtures of diagenetic and biogenic gases.

Chemical and isotope compositions of bottom sediments from ODP Leg 168, Eastern Flank of the Juan de Fuca Ridge

Ten sites were drilled in the eastern flank of the Juan de Fuca Ridge (North East Pacific) along a 100 km-long east-west transect during Leg ODP 168. This study focuses on the mineralogical and chemical study of sediments that overly basaltic basement through which seawater circulates. Silicate authigenesis was observed in the sediment layer just above basement at sites located more than 30 km from the ridge axis. This sediment alteration is particularly abundant at ODP Sites 1031 and 1029 where authigenic formation of Fe-Mg rich smectite and zeolite and the dissolution of biogenic calcite are observed. Comparison of the distribution of the alteration in the basal sediment collected along this transect suggests that diffusional transport of aqueous solutes from the basement into the overlying sediment cannot produce the mineralogical and chemical changes in the basal sediments at Sites 1031 located on a basement topographic high, and at Site 1029 located at about 50 km from the ridge axis on a buried basement area. Vertical advection of basement fluid though the sediment section is required to produce this alteration. These processes are still active at Site 1031, based on systematic variations in pore-water profiles and temperatures obtained from stable isotopic data on calcium carbonates and the nature of authigenic minerals. At Site 1029, there is no present-day advection of basement fluids though the sediment section, suggesting that this is a relic site for fluid flow.

Comparison of accumulation rates and stable isotope ratios

Since 1979/80, glaciological studies have been carried out at Ekströmisen, Antarctica, including accumulation-stake measurements, snow-pit and shallow-firn-core studies. Snowstratigraphy, chemical properties and stable-isotope ratios (d18O) were investigated. This study focuses on three cores taken between 1982 and 1998. The 1998 core was dated using dielectric profiling, d18O profiles and stake measurements. Accumulation rates showhigh interannual and spatial variability due to the extreme wind influence. No significant trend was found for the last 50 years; during the first half of the 20th century, accumulation decreased. The high spatial and interannual variability, however, means that trends must be interpreted with care. In spite of the highly irregular accumulation distribution, stable-isotope ratios show little spatial variability. The mean annual d18O values of cores B04 and FB0198 agree fairly well for the time period 1955-82 covered by both cores. d18O values have increased during most of the 20th century; since the late 1980s a decrease is observed. This change is not related to air temperature, since mean annual air temperatures at Neumayer show no significant trend over the last two decades.

Stable carbon and oxygen isotope record of Cretaceous planktonic foraminifera from DSDP (Table 1)

The Cretaceous Heterohelix moremani (Cushman) was the only biserial planktonic foraminiferal species from its first appearance in the late Albian up to the Cenomanian/Turonian boundary. Within that time, it increased gradually in abundance relative to other planktonic foraminifera in five Circum-North Atlantic sections. It is generally rare in upper Albian sediments, common in most of the Cenomanian and very abundant in sediments representing the latest Cenomanian Oceanic Anoxic Event. Short-term variations on the overall abundance trend correlate with positive excursions in the bulk carbonate delta13C record. Maximum rain rates of H. moremani during OAE2 show that this species was an opportunist that did well in extreme conditions, but its overall distribution indicates that it is not necessarily a marker for very high palaeoproductivity environments. Stable oxygen and carbon isotope measurements on foraminiferal species indicate that H. moremani was a surface water dweller at least in part of its geographic range, but incorporated 13C out of equilibrium with ambient seawater. It is depleted in delta13C relative to other planktonic foraminifera, which is attributed to vital effects related to its opportunistic character.

Stable carbon and oxygen isotope ratios of Planulina wuellerstorfi from sediments of the Sierra Leone Rise

Causes of change in deep water delta13C can be either global or local in extent. Global causes include (1) climatically-induced changes in the amount of terrestrial biomass which alter the average carbon isotopic composition of the oceanic reservoir (Shackleton, 1977), and (2) erosion and deposition of organic-rich, continental shelf sediments during sea level fluctuations which change the mean oceanic carbon: phosphorus ratio (Broecker, 1982 doi:10.1016/0079-6611(82)90007-6). Regional gradients of delta13C are created by remineralization of organic detritus within the deep ocean itself thus reflecting the distribution of water masses and modern thermohaline flow. Changes in a single geological record of benthic foraminiferal delta13C can result from any combination of these global and abyssal circulation effects. By sampling a large number of cores collected over a wide bathymetric range yet confined to a small geographical region we have minimized the ambiguity. We can assume that each delta13C record was equally affected by global causes of delta13C variation. The differences seen between the delta13C records must, therefore, reflect changes in the distribution of delta13C in the deep ocean. We interpret these differences in distribution in terms of changes in the ocean's abyssal circulation. Benthic foraminiferal carbon isotopic evidence from a suite of Sierra Leone Rise cores indicates that the deeper parts of the eastern Atlantic basins underwent a reduction in [O2] during the maximum of the last glaciation. Reduced advection of O2-rich deep water through low-latitude fracture zones, associated with increased delivery of organic matter to the deep ocean, lowered the delta13C of deep water SumCO2 at all depths below the sill separating the eastern and western Atlantic basins (Metcalf et al., 1964 doi:10.1016/0011-7471(64)91078-2). This decreased advection into the eastern Atlantic Ocean coincides with the overall decrease in deep water production in the North Atlantic during the last glacial maximum (Curry and Lohmann, 1982 doi:10.1016/0033-5894(82)90071-0; Boyle and Keigwin, 1982 doi:10.1126/science.218.4574.784; Schnitker, 1979 doi:10.1016/0377-8398(79)90020-3; Streeter and Shackleton, 1979 doi:10.1126/science.203.4376.168).

Biomass and stable isotope composition of plankton in five size fractions along a zonal transect (24°N) from the Canary Islands to Florida in January-March 2011

The spatial variability of biomass and stable isotopes in plankton size fractions in the upper 200 m was studied in a high spatial resolution transect along 24°N from Canary Islands to Florida (January - March 2011) during Leg 8 of the Malaspina-2010 expedition (http://www.expedicionmalaspina.es) to determine nitrogen and carbon sources. Plankton samples were collected by vertical tows of a microplankton net (40 mm mesh size) and a mesoplankton net (200 mm mesh size) through the upper 200 m of the water column. Sampling was between 10:00 and 16:00 h GMT. Plankton was separated into five size fractions (40 - 200, 200 - 500, 500 - 1000, 1000 - 2000 and > 2000 mm) by gentle filtration of the samples by a graded series of nylon sieves (2000, 1000, 500, 200 and 40 mm). Large gelatinous organisms were removed before filtration. Aliquots for each size fraction were collected on pre-weighed glass-fibre filters, dried (60°C, 48 h) and stored in a desiccator before determination of biomass (dry weight), carbon and nitrogen content and natural abundance of stable carbon and nitrogen isotopes ashore. Vertical advection of waters predominated in lateral zones while the central Atlantic (30-70°W) was characterized by a strong stratification and oligotrophic surface waters. Plankton biomass was low in the central zone and high in both eastern and western sides, with most of the variability due to either large (>2000 µm) and small plankton (<500 µm). Carbon isotopes reflected mainly the advection the deep water in lateral zones. Stable nitrogen isotopes showed a nearly symmetrical spatial distribution in all fractions, with the lowest values (delta15N <1per mill) in the central zone, and were inversely correlated to carbon stable isotopes (delta13C) and to the abundance of the nitrogen-fixer Trichodesmium. Diazotrophy was estimated to account for >50% of organic nitrogen in the central zone, and even >30% in eastern and western zones. The impact of diazotrophy increased with the size of the organisms, supporting the wide participation of all trophic levels in the processing of recently fixed nitrogen. These results indicate that atmospheric sources of carbon and nitrogen prevail over deep water sources in the subtropical North Atlantic and that the zone influenced by diazotrophy is much larger than reported in previous studies.

Stable isotope record of Cretaceous samples of DSDP Hole 71-511

Oxygen isotope data for upper Turonian planktonic foraminifera at Deep Sea Drilling Project Site 511 (Falkland Plateau, 60°S paleolatitude) exhibit an ~2 per mil excursion to values as low as -4.66 per mil (Vienna Peedee belemnite standard; PDB) coincident with the warmest tropical temperature estimates yet obtained for the open ocean. The lowest planktonic foraminifer d18O values suggest that the upper ocean was as warm as 30-32°C. This is an extraordinary temperature for 60°S latitude but is consistent with temperatures estimated from apparently coeval mollusc d18O from nearby James Ross Island (65°S paleolatitude). Glassy textural preservation, a well-defined depth distribution in Site 511 planktonics, low sediment burial temperature (~32°C), and lack of evidence of highly depleted pore waters argue against diagenesis (even solid state diffusion) as the cause of the very depleted planktonic values. The lack of change in benthic foraminifer d18O suggests brackish water capping as the mechanism for the low planktonic d18O values. However, mixing ratio calculations show that the amount of freshwater required to produce a 2 per mil shift in ambient water would drive a 7 psu decrease in salinity. The abundance and diversity of planktonic foraminifera and nannofossils, high planktonic:benthic ratios, and the appearance of keeled foraminifera argue against lower-than-normal marine salinities. Isotope calculations and climate models indicate that we cannot call upon more depleted freshwater d18O to explain this record. Without more late Turonian data, especially from outside the South Atlantic basin, we can currently only speculate on possible causes of this paradoxical record from the core of the Cretaceous greenhouse.

Geochemistry and radiolarian distribution of sediment core MD96-2073

A combination of changes in the species composition of the radiolarian populations, and in the sediment chemical composition (content and mass accumulation rates of carbonate, organic carbon, and selected major and trace elements, with special attention paid to Ba) is used to reconstruct the variations in upwelling activity over the last 250 kyr in the Socotra gyre area (Somali-Socotra upwelling system, NW Indian Ocean). In the Socotra gyre (Core MD 962073 at 10°N), the variations in upwelling intensity are reconstructed by the upwelling radiolarian index (URI) while the thermocline/surface radiolarian index (TSRI) testifies to productivity variations during non-upwelling intervals. Despite an origin related both to marine and terrigenous inputs, the geochemical records of organic carbon, silica, and trace elements (Ba, P, Cu, and Zn) normalized to Al are controlled by the variations in surface paleoproductivity. The data indicate a continuous increase in upwelling intensity during the last 250 kyr with a maximum activity within the MIS 3, while high productivity periods in between the upwelling seasons occurred both during glacial and interglacial intervals. A comparison of our data with published observations from another gyre of the Somalian upwelling area located at 5°N in the Somali gyre area shows differences regarding periods of upwelling activity and their geochemical imprint. Three hypotheses are proposed to explain these differences: (1) changes in the planktonic community, resulting in more silica-rich deposits in the Socotra gyre, and more carbonate-rich deposits in the Somali gyre, that are controlled by differences in the source water of the upwelling; (2) a more important terrigenous input in the southern gyre; and (3) a different location of the sites relative to the geographic distribution of the upwelling gyres and hydrologic fronts.

The last occurrence of Proboscia curvirostris in the North Atlantic marine isotope stage 9-8

Well-preserved diatoms are present in high sedimentation rate Pleistocene cores retrieved on Ocean Drilling Program (ODP) Legs 151, 152, 162 and IMAGES cruises of R/V Marion Dufresne from the North Atlantic. Investigation of the stratigraphic occurrence of diatom species shows that the youngest diatom event observed in the area is the last occurrence (LO) of Proboscia curvirostris (Jousé) Jordan and Priddle. P. curvirostris is a robust species that can easily be identified in the sediments, and therefore can be a practical biostratigraphic tool. We have mapped its areal distribution, and found that it stretches from 40°N to 80°N in the North Atlantic. Further, we have correlated the LO P. curvirostris to the oxygen isotope records of six cores to refine the age of this biostratigraphic event. The extinction of P. curvirostris is latitudinally diachronous through Marine Isotope Stages (MIS) 9 to 8 within the North Atlantic. This is closely related to the paleoceanography of the area. P. curvirostris first disappeared within interglacial MIS 9 (324 ka) from the northern areas that are most sensitive to climatic forcing, like the East Greenland current and the sea-ice margin. It survived in mid-North Atlantic until the conditions of the MIS 8 (glaciation) became too severe (260 ka). In the North Pacific at ODP Site 883 the LO P. curvirostris falls within MIS 8. The observed overlap in age between the North Atlantic and the North Pacific strongly suggests that the extinction of P. curvirostris is synchronous between these oceans.

Distribution of Pliocene diatom faunas in the Northwest Pacific

High-resolution quantitative diatom data are tabulated for the early part of the late Pliocene ( 3.25 to 2.08 Ma ) at DSDP Site 580 in the northwestern Pacific. Sample spacing averages 11 k.y. between 3.1 and 2.8 Ma, but increases to 14 to 19 k.y. prior to 3.1 Ma and after 2.8 Ma. Q-mode factor analysis of the middle Pliocene assemblage reveals four factors which explain 92.4% of the total variance of the 47 samples studied between 3.25 and 2.55 Ma. Three of the factors are closely related to modern subarctic, transitional, and subtropical elements, while the fourth factor, which is dominated by Coscinodiscus marginatus and the extinct Pliocene species Neodenticula kamtschatica, appears to correspond to a middle Pliocene precursor of the subarctic water mass. Knowledge of the modern and generalized Pliocene paleoclimatic relationships of various diatom taxa is used to generate a paleoclimate curve ("Twt") based on the ratio of warm-water (subtropical) to cold-water diatoms with warm-water transitional taxa (Thalassionema nitzschioides, Thalassiosira oestrupii, and Coscinodiscus radiatus) factored into the equation at an intermediate (0.5) value. The "Twt" ratios at more southerly DSDP Sites 579 and 578 are consistently higher (warmer) than those at Site 580 throughout the Pliocene, suggesting the validity of the ratio as a paleoclimatic index. Diatom paleoclimatic data reveal a middle Pliocene (3.1 to 3.0 Ma) warm interval at Site 580 during which paleotemperatures may have exceeded maximum Holocene values by 3 °- 5.5 °C at least three times. This middle Pliocene warm interval is also recognized by planktic foraminifers in the North Atlantic, and it appears to correspond with generalized depleted oxygen isotope values suggesting polar warming. The diatom "Twt" curve for Site 580 compares fairly well with radiolarian and silicoflagellate paleoclimatic curves for Site 580, planktic foraminiferal sea-surface temperature estimates for the North Atlantic, and benthic oxygen isotope curves for late Pliocene, although higher resolution studies on paired samples are required to test the correspondence of these various paleoclimatic indices.

Paleocene radiolarian distribution and biostratigraphy from offshore eastern New Zealand

A 100-m-thick Paleocene sequence of mainly pelagic sediments at ODP Site 1121, on the eastern flanks of the Campbell Plateau, contains few to common radiolarians of relatively low diversity in the lower 40 m (Early to early Late Paleocene) and abundant, diverse radiolarian assemblages in the upper 60 m (mid-Late Paleocene). The 150 taxa recorded from the entire Paleocene interval are thought to under-represent the actual species diversity by at least one half as many morphotypes have not been differentiated below the level of genus. Assemblages in the lower 40 m are similar to those described from onland New Zealand and DSDP Site 208 (northern Lord Howe Rise); they are correlated with South Pacific radiolarian zones RP4 and RP5. Assemblages in the upper 60 m differ from other known Late Paleocene assemblages in the great abundance of plagiacanthids and cycladophorids. Similarities are noted with later Cenozoic cool-water assemblages. This upper interval is correlated with South Pacific zone RP6, as revised herein, based on comparison with faunas from Site 208 and Marlborough, New Zealand. The interval is also correlated with the upper part of North Atlantic zone RP6 (RP6b-c) based on the presence of Aspis velutochlamydosaurus, Plectodiscus circularis and Pterocodon poculum. Other species, such as Buryella tetradica and Buryella pentadica, are valuable for local correlation but exhibit considerable diachroneity between the Pacific, Indian and Atlantic Oceans. An age model for the Paleocene interval at Site 1121, based on well-constrained nannofossil and radiolarian datums, indicates that the rate of compacted sediment accumulation doubles from 15 to 30 mm/ka at the RP5/RP6 zonal boundary. In large part this is due to a sudden and pronounced increase in accumulation rates for all siliceous fossils; radiolarians and larger diatoms increase from <100 to >10 000 specimens/cm2/ka. This apparent increase in biosiliceous productivity is age-equivalent to a mid-Paleocene cooling event (57-59 Ma) identified from global stable isotope records that is associated with the heaviest delta13C values for the entire Cenozoic.

Lithium concentrations and isotope composition of basalt samples from ODP/DSDP Sites from Costa Rica Rift

Ocean Drilling Program (ODP) Hole 504B near the Costa Rica Rift is the deepest hole drilled in the ocean crust, penetrating a volcanic section, a transition zone and a sheeted dike complex. The distribution of Li and its isotopes through this 1.8-km section of oceanic crust reflects the varying conditions of seawater alteration with depth. The upper volcanic rocks, altered at low temperatures, are enriched in Li (5.6-27.3 ppm) and have heavier isotopic compositions (delta7Li=6.6-20.8?) relative to fresh mid-ocean ridge basalt (MORB) due to uptake of seawater Li into alteration clays. The Li content and isotopic compositions of the deeper volcanic rocks are similar to MORB, reflecting restricted seawater circulation in this section. The transition zone is a region of mixing of seawater with upwelling hydrothermal fluids and sulfide mineralization. Li enrichment in this zone is accompanied by relatively light isotopic compositions (-0.8-2.1?) which signify influence of basalt-derived Li during mineralization and alteration. Li decreases with depth to 0.6 ppm in the sheeted dike complex as a result of increasing hydrothermal extraction in the high-temperature reaction zone. Rocks in the dike complex have variable isotopic values that range from -1.7 to 7.9?, depending on the extent of hydrothermal recrystallization and off-axis low-temperature alteration. Hydrothermally altered rocks are isotopically light because 6Li is preferentially retained in greenschist and amphibolite facies minerals. The delta7Li values of the highly altered rocks of the dike complex are complementary to those of high-temperature mid-ocean ridge vent fluids and compatible to equilibrium control by the alteration mineral assemblage. The inventory of Li in basement rocks permits a reevaluation of the role of oceanic crust in the budget of Li in the ocean. On balance, the upper 1.8 km of oceanic crusts remains a sink for oceanic Li. The observations at 504B and an estimated flux from the underlying 0.5 km of gabbro suggest that the global hydrothermal flux is at most 8*10**9 mol/yr, compatible with geophysical thermal models. This work defines the distribution of Li and its isotopes in the upper ocean crust and provides a basis to interpret the contribution of subducted lithosphere to arc magmas and cycling of crustal material in the deep mantle.