d18O, lithologies, mineralogy and determination of temperature and depth of formation of DSDP Site 69-504 siliceous rocks

Seven opal-CT-rich and five quartz-rich porcellanites and cherts from Site 504 have a range in oxygen-isotope values of 24.4 and 29.4 per mil. In opal-CT rocks, d18O becomes larger with sub-bottom depth and with age. Quartz-rich rocks do not show these trends. Boron, in general, increases with decreasing d18O for porcellanites and cherts considered together, supporting the conclusion that boron is incorporated within the quartz crystal structure during precipitation of the SiO2. Silicification of the chalks at Site 504 began 1 m.y. ago - that is, 5 m.y. after sedimentation commenced on the oceanic crust. Temperatures of chert formation determined from oxygen-isotope compositions reflect diagenetic temperatures rather than bottom-water temperatures, and are comparable to temperatures of formation determined by down-hole measurements. Opal-A in the chalks began conversion to opal-CT when a temperature of 50°C was reached in the sediment column. Conversion of opal-CT to quartz started at 55 °C. Silicification occurred over a stratigraphic thickness of about 10 meters when the temperature at the top of the 10 meters reached about 50°C. It took about 250,000 years to complete the silica transformation within each 10-meter interval of sediment at Site 504. Quartz formed over a stratigraphic range of at least 30 meters, at temperatures of about 54 to 60°C. The time and temperatures of silicification of Site 504 rocks are more like those at continental margins than those in deep-sea, open-ocean deposits.

Stable isotope composition of carbonates in the Tyrrhenian Sea

The Messinian evaporitic succession recovered at ODP Sites 652, 653, and 654 in the Tyrrhenian Sea was generated under various environmental conditions which ranged from brackish to hypersaline, as deduced from the sedimentary facies and stable isotope compositions of the carbonate and sulfate deposits. Water in the basins had to be shallow to undergo such rapid and large geochemical variations. The marine influence was omnipresent in the basin at least during the deposition of sulfate evaporites; seawater or marine brines might have been supplied either by direct input into evaporitic lagoons as at Sites 653 and 654, or by subterraneous infiltration in marginal areas as at Site 652. Episodes of severe dilution by continental waters occurred frequently throughout Messinian times in the more basinal areas at Sites 653 and 654, while a fresh water body was standing permanently at Site 652. The high heat flow present at Site 652 was responsible for a major late authigenesis of iron-rich dolomites, which was initiated during the subsidence of the basin and ended before Pliocene.

(Table 1) Stable carbon and nitrogen isotopic ratios of potential prey species of bearded seals (Erignathus barbatus), Svalbard

Changing patterns of sea-ice distribution and extent have measurable effects on polar marine systems. Beyond the obvious impacts of key-habitat loss, it is unclear how such changes will influence ice-associated marine mammals in part because of the logistical difficulties of studying foraging behaviour or other aspects of the ecology of large, mobile animals at sea during the polar winter. This study investigated the diet of pregnant bearded seals (Erignathus barbatus) during three spring breeding periods (2005, 2006 and 2007) with markedly contrasting ice conditions in Svalbard using stable isotopes (d13C and d15N) measured in whiskers collected from their newborn pups. The d15N values in the whiskers of individual seals ranged from 11.95 to 17.45 per mil, spanning almost 2 full trophic levels. Some seals were clearly dietary specialists, despite the species being characterised overall as a generalist predator. This may buffer bearded seal populations from the changes in prey distributions lower in the marine food web which seems to accompany continued changes in temperature and ice cover. Comparisons with isotopic signatures of known prey, suggested that benthic gastropods and decapods were the most common prey. Bayesian isotopic mixing models indicated that diet varied considerably among years. In the year with most fast-ice (2005), the seals had the greatest proportion of pelagic fish and lowest benthic invertebrate content, and during the year with the least ice (2006), the seals ate more benthic invertebrates and less pelagic fish. This suggests that the seals fed further offshore in years with greater ice cover, but moved in to the fjords when ice-cover was minimal, giving them access to different types of prey. Long-term trends of sea ice decline, earlier ice melt, and increased water temperatures in the Arctic are likely to have ecosystem-wide effects, including impacts on the forage bases of pagophilic seals.

Stable carbon isotope record of Bahama Bank sediments

The carbon-isotopic composition (d13C) of bulk carbonates, obtained from a transect of sites drilled through platform and periplatform sediments of Holocene to Early Miocene age, has been compared to ascertain whether changes in the d13C can be correlated between sediments of equivalent ages and whether such changes can be related to global changes in the d13C of the dissolved inorganic carbon in the oceans over this time period. Five of the sites were drilled during Leg 166 of the Ocean Drilling Project (1003-1007) in a transect ranging from five km to 25 km away from the platform margin and penetrating sediments of Holocene to Oligocene age that are contained in 17 depositional sequences (A-Q). Two shallow-water sites, Clino and Unda were situated on a extension of the same transect on Great Bahama Bank in a water depth of 10-15 m. With the exception of Unda and Clino, the d13C of the carbonates ranges from +5 per mil in the younger sequences to +1 per mil in the Early Miocene. In each of the sites, the d13C is strongly positively correlated with the percentage of aragonite. As a consequence, the d13C of sequences A through F is strongly correlated, reflecting the decreasing amount of aragonite with increasing depth. In the two platform sites, the d13C is significantly lower in the younger portions of the cores as a result of the influences of meteoric diagenesis during repeated exposure during the Pleistocene. Although the d13C of the individual sequences can be correlated in most instances between the ODP holes, the changes are not related to global changes in the d13C of the oceans which in contrast to the d13C of the platform sediments become isotopically lower towards the present day. Instead variations in the d13C appear to be related to varying mixtures of d13C-rich banktop sediments and pelagic material.

Isotopic geochemistry of granitoids in the Jinshajiang suture zone, SW China

The Jinshajiang suture zone, located in the eastern part of the Tethyan tectonic domain, is noticeable for a large-scale distribution of Late Jurassic to Triassic granitoids. These granitoids were genetically related to the evolution of the Paleo-Tethys Ocean. The Beiwu, Linong and Lunong granitoids occur in the middle zone of the Jinshajiang Suture Zone, and possess similar geochemical features, indicating they share a common magma source. SIMS zircon U-Pb dating reveals the Beiwu, Linong and Lunong granitic intrusions were emplaced at 233.9±1.4 Ma (2 sigma), 233.1 ±1.4 Ma (2 sigma) and 231.0±1.6 Ma (2 sigma), respectively. All of these granitoids are enriched in abundances of Si (SiO2 =65.2-73.5 wt.%), and large-ion-lithophile-elements (LILEs), but depleted in high-field-strength-elements contents (HFSEs, e.g., Nb, Ta, Ti). In addition, they have low P2O5 contents (0.06-0.11 wt.%), A/CNK values ([molecular Al2O3/(CaO+Na2O+K2O)], mostly<1.1) and 10000Ga/Al ratios (1.7-2.2), consistent with the characteristics of I-type granites. In terms of isotopic compositions, these granitoids have high initial 87Sr/86Sr ratios (0.7078-0.7148), Pb isotopic compositions [(206Pb/204Pb)t=18.213-18.598, (207Pb/204Pb)t=15.637-15.730 and (208Pb/204Pb)t=38.323-38.791], zircon d18O values (7. per mil-9.3 per mil) and negative eNd(t) values (-5.1 to -6.7), suggesting they were predominantly derived from the continental crust. Their Nb/Ta ratios (average value=8.6) are consistent with those of the lower continental crust (LCC). However, variable ?Hf(t) values (-8.6 to +2.8) and the occurrences of mafic microgranular enclaves (MMEs) suggest that mantle-derived melts and lower crustal magmas were involved in the generation of these granitoids. Moreover, the high Pb isotopic ratios and elevated zircon d18O values of these rocks indicate a significant contribution of the upper crustal composition. We propose a model in which the Beiwu, Linong and Lunong granitoids were generated under a late collisional or post-collisional setting. It is possible that this collision was completed before Late Triassic. Decompression induced mantle-derived magmas underplated and provided the heat for the anatexis of the crust. Hybrid melts including mantle-derived and the lower crustal magmas were then generated. The hybrid melts thereafter ascended to a shallow depth and resulted in some degree of sedimentary rocks assimilation. Such three-component mixing magmas source and subsequent fractional crystallization could be responsible for the formation of the Beiwu, Linong and Lunong granitoids.

(Table 1) n-alkane distribution, and stable carbon and deuterium isotope ratios of DSDP Hole 10-94

Hydrology, source region, and timing of precipitation are important controls on the climate of the Great Plains of North America and the composition of terrestrial ecosystems. Moisture delivered to the Great Plains varies seasonally and predominately derives from the Gulf of Mexico/Atlantic Ocean with minor contributions from the Pacific Ocean and Arctic region. For this work, we evaluate long-term relationships for the past ~ 35 million years between North American hydrology, climate, and floral change, using isotopic records and average carbon chain lengths of higher plant n-alkanes from Gulf of Mexico sediments (DSDP Site 94). We find that carbon isotope values (d13C) of n-alkanes, corrected for variations in the d13C value of atmospheric CO2, provide minor evidence for contributions of C4 plants prior to the Middle Miocene. A sharp spike in C4 input is identified during the Middle Miocene Climatic Optimum, and the influence of C4 plants steadily increased during the Late Miocene into the Pleistocene - consistent with other North American records. Chain-length distributions of n-alkanes, indicative of the composition of higher plant communities, remained remarkably constant from 33 to 4 Ma. However, a trend toward longer chain lengths occurred during the past 4 million years, concurrent with an increase in d13C values, indicating increased C4 plant influence and potentially aridity. The hydrogen isotope values (dD) of n-alkanes are relatively invariant between 33 and 9 Ma, and then become substantially more negative (75 per mil) from 9 to 2 Ma. Changes in the plant community and temperature of precipitation can solely account for the observed variations in dD from 33 to 5 Ma, but cannot account for Plio-Pleistocene dD variations and imply substantial changes in the source region of precipitation and seasonality of moisture delivery. We posit that hydrological changes were linked to tectonic and oceanographic processes including the shoaling and closure of the Panamanian Seaway, amplification of North Atlantic Deep Water Production and an associated increase of meridional winds. The southerly movement of the Intertropical Convergence Zone near 4 Ma allowed for the development of a near-modern pressure/storm track system, driving increased aridity and changes in seasonality within the North American interior.

Effects of various pollutant mixtures on immune responses of the blue mussel (Mytilus edulis) collected at a salinity gradient in Danish coastal waters, links to supplementary material

The Baltic Sea is a semi-enclosed sea with a steady salinity gradient (3 per mil-30 per mil). Organisms have adapted to such low salinities, but are suspected to be more susceptible to stress. Within the frame of the integrated environmental monitoring BONUS + project "BEAST" the applicability of immune responses of the blue mussel was investigated in Danish coastal waters. The sampling sites were characterised by a salinity range (11-19 per mil) and different mixtures of contaminants (metals, PAHs and POPs), according to chemical analysis of mussel tissues. Variation partitioning (redundancy analysis) was applied to decompose salinity and contamination effects. The results indicated that cellular immune responses (total and differential haemocyte count, phagocytic activity and apoptosis) were mainly influenced by contaminants, whereas humoral factors (haemolytic activity) were mainly impacted by salinity. Hence, cellular immune functions may be suitable as biomarkers in monitoring programmes for the Baltic Sea and other geographic regions with salinity variances of the studied range.

Chemical and isotopic compositions of rocks, ores, and hydrothermal minerals from the Rainbow and Logachev-2 hydrothermal fields

The aim of this paper is to analyze and compare mineralogy and geochemistry of copper-zinc sulfide ores from the Logachev-2 and Rainbow hydrothermal fields of the Mid-Atlantic Ridge (MAR) confined to serpentinite protrusions. It was found that Zn(Fe) and Cu, Fe(Zn) sulfides had been deposited in black smokers pipes almost simultaneously from intermittently flowing, nonequilibrium H2S-low solutions of different temperatures. Pb isotope composition confirmed that the deep oceanic crust had been a source of lead. The ores from the Rainbow field are 20-fold higher in Co than ores restricted to basalts and show a high ratio of Co/Ni=46. The ores from the Rainbow field are enriched in 34S isotope (aver. d34S=10 per mil) because of constant flow of cold sea water into the subsurface zone of the hydrothermal system. Ores from the Logachev-2 field are 8 times higher in gold compared to other MAR regions. Sulfide ores from the Rainbow and Logachev-2 fields have no analogues among MAR ore occurrences in terms of enrichment in valuable components (Zn, Cd, Co, and Au).

Assamblages and cluster analysis from DSDP Hole 22-214 of the eastern Indian Ocean

Multivariate analyses of latest Pliocene through Holocene benthic foraminifera from 61 samples from Deep-Sea Drilling Project (DSDP) Site 214, eastem Indian Ocean were carried out. The 46 highest ranked species were used in R-mode factor analysis which has enabled to the identification of three environmentally significant assemblages at Site 214. Assemblage 1 is characterized by Uvigerina hispido-costata, Osangularia culter , Gavelinopsis lobatulus, Cibicides wuellerstorfi and Karreriella baccata as principal species. This assemblage is inferred to reflect high-energy, well-oxygenated and probably low-organic carbon deep-sea environment at Site 214. Assemblage 2 is defined principally by Globocassidulina pacifica and U. proboscidea and is considered to indicate an organic carbon-rich environment which resulted from high surface productivity irrespective of dissolved oxygen content. Assemblage 3 is marked by Oridorsalis umbonatus, Textularia lythostrota, Hoeglundina elegans, Pyrgo murrhina, and Pullenia quinqueloba as principal species. This assemblage is inferred to indicate a low-organic carbon environment with high pore water oxygen concentration leading to better preservation of deep-sea sediments.

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.

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.

Isotopic composition of interstitial fluids and origin of methane at DSDP Leg 84 Holes

CH4 and CO2 species in pore fluids from slope sediments off Guatemala show extreme 13C-enrichment (d13C of -41 and +38 per mil, respectively) compared with the typical degree of 13C-enrichment in pore fluids of DSDP sediments (d13C of - 60 and + 10 per mil). These unusual isotopic compositions are believed to result from microbial decomposition of organic matter, and possibly from additional isotopic fractionation associated with the formation of gas hydrates. In addition to the isotopic fractionation displayed by CH4 and CO2, the pore water exhibits a systematic increase in d18O with decrease in chlorinity. As against seawater d18O values of 0 and chlorinity of 19 per mil, the water collected from decomposed gas hydrate from Hole 570 had a d18O of + 3.0 per mil and chlorinity of 9.5 per mil. The isotopic compositions of pore-fluid constituents change gradually with depth in Hole 568 and discontinuously with depth in Hole 570.

Gas hydrates at DSDP Leg 84

On DSDP Leg 84, gas hydrates were found at three sites (565, 568, and 570) and were inferred, on the basis of inorganic and organic geochemical evidence, to be present at two sites (566 and 569); no evidence for gas hydrates was observed at Site 567. Recovered gas hydrates appeared as solid pieces of white, icelike material occupying fractures in mudstone or as coarse-grained sediment in which the pore space exhibited rapid outgassing. Also a 1.05-m-long core of massive gas hydrate was obtained at Site 570. Downhole logging indicated that this hydrate was actually 3 to 4 m thick. Measurements of the amount of methane released during the decomposition of these recovered samples clearly showed that gas hydrates had been found. The distribution of evolved hydrocarbon gases indicated that Structure I gas hydrates were present because of the apparent inclusion of methane and ethane and exclusion of propane and higher molecular weight gases. The water composing the gas hydrates was fresh, having chlorinities ranging from 0.5 to 3.2 per mil. At Sites 565, 568, and 570, where gas hydrates were observed, the chlorinity of pore water squeezed from the sediment decreased with sediment depth. The chlorinity profiles may indicate that gas hydrates can often occur finely dispersed in sediments but that these gas hydrates are not recovered because they do not survive the drilling and recovery process. Methane in the gas hydrates found on Leg 84 was mainly derived in situ by biogenic processes, whereas the accompanying small amounts of ethane likely resulted from low-temperature diagenetic processes. Finding gas hydrates on Leg 84 expands observations made earlier on Leg 66 and particularly Leg 67. The results of all of these legs show that gas hydrates are common in landward slope sediments of the Middle American Trench from Mexico to Costa Rica.

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.

Mineralogy and isotopic composition of sulfur in ODP Hole 118-735B gabbros

Sulfide mineralogy, sulfur contents, and sulfur isotopic compositions were determined for samples from the 500-m gabbroic section of Ocean Drilling Program Hole 735B in the southwest Indian Ocean. Igneous sulfides (pyrrhotite, chalcopyrite, pentlandite, and troilite) formed by accumulation of immiscible sulfide droplets and crystallization from intercumulus liquids. Primary sulfur contents average around 600 ppm, with a mean sulfide d34S value near 0 per mil, similar to the isotopic composition of sulfur in mid-ocean ridge basalt glass. Rocks from a 48-m interval of oxide gabbros have much higher sulfur contents (1090-2530 ppm S) due to the increased solubility of sulfur in Fe-rich melts. Rocks that were locally affected by early dynamothermal metamorphism (e.g., the upper 40 m of the core) have lost sulfur, averaging only 90 ppm S. Samples from the upper 200 m of the core, which underwent subsequent hydrothermal alteration, also lost sulfur and contain an average of 300 ppm S. Monosulfide minerals in some of the latter have elevated d34S values (up to +6.9 per mil), suggesting local incorporation of seawater-derived sulfur. Secondary sulfides (pyrrhotite, chalcopyrite, pentlandite, troilite, and pyrite) are ubiquitous in trace amounts throughout the core, particularly in altered olivine and in green amphibole. Pyrite also locally replaces igneous pyrrhotite. Rocks containing secondary pyrite associated with late low-temperature smectitic alteration have low d34S values for pyrite sulfur (to - 16.6 per mil). These low values are attributed to isotopic fractionation produced during partial oxidation of igneous sulfides by cold seawater. The rocks contain small amounts of soluble sulfate (6% of total S), which is composed of variable proportions of seawater sulfate and oxidized igneous sulfur. The ultimate effect of secondary processes on layer 3 gabbros is a loss of sulfur to hydrothermal fluids, with little or no net change in d34S.