Geochemistry of Atlantis Massif serpentinites

The Lost City hydrothermal system at the southern Atlantis Massif (Mid-Atlantic Ridge, 30°N) provides a natural laboratory for studying serpentinization processes, the temporal evolution of ultramafic-hosted hydrothermal systems, and alteration conditions during formation and emplacement of an oceanic core complex. Here we present B, O, and Sr isotope data to investigate fluid/rock interaction and mass transfer during detachment faulting and exhumation of lithospheric sequences within the Atlantis Massif. Our data indicate that extensive serpentinization was a seawater-dominated process that occurred predominately at temperatures of 150-250 °C and at high integrated W/R ratios that led to a marked boron enrichment (34-91 ppm). Boron removal from seawater during serpentinization is positively correlated with changes in d11B (11-16 per mil) but shows no correlation with O-isotope composition. Modeling indicates that B concentrations and isotope values of the serpentinites are controlled by transient temperature-pH conditions. In contrast to prior studies, we conclude that low-temperature marine weathering processes are insignificant for boron geochemistry of the Atlantis Massif serpentinites. Talc- and amphibole-rich fault rocks formed within a zone of detachment faulting at temperatures of approximately 270-350 °C and at low W/R ratios. Talc formation in ultramafic domains in the massif was subsequent to an early stage of serpentinization and was controlled by the access of Si-rich fluids derived through seawater-gabbro interactions. Replacement of serpentine by talc resulted in boron loss and significant lowering of d11B values (9-10 per mil), which we model as the product of progressive extraction of boron. Our study provides new constraints on the boron geochemical cycle at oceanic spreading ridges and suggests that serpentinization associated with ultramafic-hosted hydrothermal systems may have important implications for the behavior of boron in subduction zone settings.

Chemical and isotope composition of poor fluid from gas-hydrate samples of ODP Site 146-892

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment-water interface at 2-19 m below the seafloor (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2- to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ~17 mbsf. Gas from a sample of this layer was composed of both CH4 and H2S. This sample is the first mixed-gas hydrate of CH4-H2S documented in ODP; it also contains ethane and minor amounts of CO2. Measured temperatures of the recovered core ranged from 2 to -1.8°C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH4-H2S hydrate during recovery without a pressure core sampler. During this dissociation, toxic levels of H2S (delta34S, +27.4?) were released. The delta13C values of the CH4 in the gas hydrate, -64.5 to -67.5? (PDB), together with deltaD values of -197 to -199? (SMOW) indicate a primarily microbial source for the CH4. The delta18O value of the hydrate H2O is +2.9? (SMOW), comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH4-H2S) and depth distribution (2-19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH4-H2S hydrate is primarily confined to the present day active sulfate reduction zone (2-19 mbsf), and that from here down to the BSR depth (19-68 mbsf) the gas hydrate inferred to exist is a >=99% CH4 hydrate, suggest that the mixing of CH4 and H2S is a geologically young process. Because the existence of a mixed CH4-H2S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, tectonically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone.

Chemical and isotopic compositions of Archean magmatic and metasedimentary rocks and minerals from the Podolia domain, Ukrainian Shield

Zircons from the oldest magmatic and metasedimentary rocks in the Podolia domain of the Ukrainian shield were studied and dated by the U-Pb method on a NORDSIM secondary-ion mass spectrometer. Age of zircon cores in enderbite gneisses sampled in the Kazachii Yar and Odessa quarries on the opposite banks of the Yuzhnyi Bug River reaches 3790 Ma. Cores of terrigenous zircons in quartzites from the Odessa quarry as well as in garnet gneisses from the Zaval'e graphite quarry have age within 3650-3750 Ma. Zircon rims record two metamorphic events around 2750-2850 Ma and 1900-2000 Ma. Extremely low U content in zircons of the second age group indicates conditions of the granulite facies metamorphism in Paleoproterozoic within the Podolia domain. Measured data on orthorocks (enderbite-gneiss) and metasedimentary rocks unambiguously suggest existence of the ancient Paleoarchean crust in the Podolia (Dniester-Bug) domain of the Ukrainian shield. They contribute in our knowledge of scales of formation and geochemical features of the primordial crust.

Glacial-interglacial sediment record from the North Atlantic

Studies from the subtropical western and eastern Atlantic Ocean, using the 231Pa/230Th ratio as a kinematic proxy for deep water circulation, provided compelling evidence for a strong link between climate and the rate of meridional overturning circulation (MOC) over the last deglaciation. In this study, we present a compilation of existing and new sedimentary 231Pa/230Th records from North Atlantic cores between 1710 and 4550 m water depth. Comparing sedimentary 231Pa/230Th from different depths provides new insights into the evolution of the geometry and rate of deep water formation in the North Atlantic during the last 20,000 years. The 231Pa/230Th ratio measured in upper Holocene sediments indicates slow water renewal above ?2500 m and rapid flushing below, consistent with our understanding of modern circulation. In contrast, during the Last Glacial Maximum (LGM), Glacial North Atlantic Intermediate Water (GNAIW) drove a rapid overturning circulation to a depth of at least ?3000 m depth. Below ~4000 m, water renewal was much slower than today. At the onset of Heinrich event 1, transport by the overturning circulation declined at all depths. GNAIW shoaled above 3000 m and significantly weakened but did not totally shut down. During the Bølling-Allerød (BA) that followed, water renewal rates further decreased above 2000 m but increased below. Our results suggest for the first time that ocean circulation during that period was quite distinct from the modern circulation mode, with a comparatively higher renewal rate above 3000 m and a lower renewal rate below in a pattern similar to the LGM but less accentuated. MOC during the Younger Dryas appears very similar to BA down to 2000 m and slightly slower below.

(Table 1) Strontium concentrations and isotope ratios of anhydrite from DSDP/ODP Hole 504B

In samples from 1575 to 1982 mbsf anhydrite leached from whole-rock powders. 87Sr/86Sr and Sr/Ca determined following methods described in (Teagle et al., 1996, doi:10.2973/odp.proc.sr.148.113.1996, Teagle et al., 1998, doi:10.2973/odp.proc.sr.158.223.1998). For the period of the analysis (Jan. 1994-Dec. 1995) NIST SRM 987 gave 87Sr/86Srs0.710244 +/- 0.000018 (2 sigma, n = 115). Full analytical procedural blanks were <50 pg for Sr. delta18O following (Pickthorn and O´Neil, 1985). Repeated extractions and measurements of samples and standards were reproducible within +/- 0.5.

(Table 6) Selenium isotopic composition of sediment samples from ODP Site 185-1149

Multiple-collector inductively coupled plasma mass spectrometry has been used for the precise measurement of the isotopic composition of Se in geological samples. Se is chemically purified before analysis by using cotton impregnated with thioglycollic acid. This preconcentration step is required for the removal of matrix-interfering elements for hydride generation, such as transitional metals, and also for the quantitative separation of other hydride-forming elements, such as Ge, Sb, and As. The analyte is introduced in the plasma torch with a continuous-flow hydride generation system. Instrumental mass fractionation is corrected with a "standard-sample bracketing" approach. By use of this new technique, the minimum Se required per analysis is lowered to 10 ng, which is one order of magnitude less than the amount needed for the N-TIMS technique. The estimated external precision calculated for the 82Se/76Se isotope ratio is 0.25? (2 sigma), and the data are reported as delta notation (?) relative to our internal standard (MERCK elemental standard solution). Measurements of Se isotopes are presented for samples of standard solutions and geological reference materials, such as silicate rocks, soils, and sediments. The Se isotopic composition of selected terrestrial and extraterrestrial materials are also presented. An overall Se isotope variation of 8? has been observed, suggesting that Se isotopes fractionate readily and are extremely useful tracers of natural processes.

Radiogenic lead and neodymium composition of surface sediments from the Arctic Ocean

Dolomite-rich layers of distinct pinkish colour are used as lithostratigraphic markers in the Amerasian Basin of the Arctic Ocean. However, origin of dolomite present in these sediment units has not been investigated in detail. In this study, lead (Pb) and neodymium (Nd) isotope composition of detrital clay-size fraction from different lithofacies was investigated in core PS72/340-5 recovered at the eastern flank of the Mendeleev Ridge. Prior to the geochemical analyses, grain-size distribution in sediments was analyzed in order to minimize the grain-size effect on the provenance signature. For provenance discrimination, results of isotope measurements were compared with marine surface sediment data and values for the circum-Arctic subaerial provinces. Late Quaternary sediment supply variability in core PS72/340-5 was analysed using the mixing model constrained by two tracers: 207Pb/206Pb and eNd. Variations of sediment isotopic composition are inferred to be due to mixing of volcanic and plutonic components. Usage of Pb isotopic ratios alone does not allow distinction between the volcanic and plutonic sources. Results confirm that, in the frame of the existing age model, over the last 200 ka dolomite-rich pink layers at the southern Mendeleev Ridge were deposited during events associated with intensified iceberg transport from North America. In general, however, late Quaternary sedimentation was mostly controlled by terrigenous input from the Chukchi and East Siberian Seas whereas sediment supply from the Laptev Sea area remained less important and relatively constant at the studied location.

Sulfur isotope rations in oceanic basement samples

Low temperature alteration of oceanic basement rocks is characterized by net gain of sulfur, which commonly yields low d34S values, suggesting involvement of microbial sulfate reduction. In order to test whether secondary sulfide minerals are consistent with a biogenic source, we apply high precision multiple sulfur isotope analysis to bulk rock sulfide and pyrite isolates from two contrasting types of altered oceanic basement rocks, namely serpentinized peridotites and altered basalts. Samples from two peridotite sites (Iberian Margin and Hess Deep) and from a basalt site on the eastern flank of the Juan de Fuca Ridge yield overlapping d34S values ranging from 0 per mil to -44 per mil. In contrast, sulfides in the basalt site are characterized by relatively low D33S values ranging from -0.06 per mil to 0.04 per mil, compared to those from peridotite sites (0.00 per mil to 0.16 per mil). The observed D33S signal is significant considering the analytical precision of 0.014 per mil (2 sigma). We present a batch reaction model that uses observed d34S and D33S relationships to quantify the effect of closed system processes and constrain the isotope enrichment factor intrinsic to sulfate reduction. The estimated enrichment factors as large as 61 per mil and 53 per mil, for peridotite and basalt sites respectively, suggest the involvement of microbial sulfate reduction. The relatively high D33S values in the peridotite sites are due to sulfate reduction in a closed system environment, whereas negative D33S values in the basalt site reflect open system sulfate reduction. A larger extent of sulfate reduction during alteration of peridotite to serpentinite is consistent with its higher H2 production capacity compared to basalt alteration, and further supports in-situ microbial sulfate reduction coupled with H2 production during serpentinization reactions.

Age determination and paleotemperatures of sediment cores TTR17-1_384B and TTR17-1_436B in the Alboran Sea

Climate conditions in the westernmost Mediterranean (Alboran Sea basin) over the last two millennia have been reconstructed through integration of molecular proxies applied for the first time in this region at such high resolution. Two temperature proxies, one based on isoprenoid membrane lipids of marine Thaumarchaeota (TEXH86-tetraether index of compounds consisting of 86 carbons) and the other on alkenones produced by haptophytes (UK'37 ratio) were applied to reconstruct sea surface temperature (SST). Both records reveal a progressive long term decline in SST over the last two millennia and an increased rate of warming during the second half of the twentieth century. This is in accord with previous temperature reconstructions for the Northern Hemisphere. TEXH86 temperature values are higher than those inferred from UK'37, probably due to differences in the bloom season of haptophytes and Thaumarchaeota, and reflect summer SST. The branched vs. isoprenoid tetraether index (BIT index) suggests a low contribution of soil organic matter (OM) to the sedimentary OM. The stable carbon isotopic composition of long chain n-alkanes indicates a predominant C3 plant contribution, with no major change in vegetation over the last 2000 yr. The distribution of long chain 1,14-diols (most likely sourced by Proboscia species in this setting) provided insight into variation in upwelling conditions during the last 2000 yr and depicts a correlation with the North Atlantic Oscillation (NAO) index, providing evidence of enhanced wind induced upwelling during periods of a persistent positive mode of the NAO.

Distribution of grain size and clay minerals in surface sediments of the Kara Sea (Fig 4, 5)

In this paper, we summarize data on terrigenous sediment supply in the Kara Sea and its accumulation and spatial and temporal variability during Holocene times. Sedimentological, organic-geochemical, and micropaleontological proxies determined in surface sediments allow to characterize the modern (riverine) terrigenous sediment input. AMS-14C dated sediment cores from the Ob and Yenisei estuaries and the adjacent inner Kara Sea were investigated to determine the terrigenous sediment fluxes and their relationship to paleoenvironmental changes. The variability of sediment fluxes during Holocene times is related to the post-glacial sea-level rise and changes in river discharge and coastal erosion input. Whereas during the late/middle Holocene most of the terrigenous sediments were deposited in the estuaries and the areas directly off the estuaries, huge amounts of sediments accumulated on the Kara Sea shelf farther north during the early Holocene before about 9 cal kyr BP. The maximum accumulation at that time is related to the lowered sea level, increased coastal erosion, and increased river discharge. Based on sediment thickness charts, echograph profiles and sediment core data, we estimate an average Holocene (0-11 cal kyr BP) annual accumulation of 194,106 t/yr of total sediment for the whole Kara Sea. Based on late Holocene (modern) sediment accumulation in the estuaries, probably 12,106 t/yr of riverine suspended matter (i.e. about 30% of the input) may escape the marginal filter on a geological time scale and is transported onto the open Kara Sea shelf. The high-resolution magnetic susceptibility record of a Yenisei core suggests a short-term variability in Siberian climate and river discharge on a frequency of 300-700 yr. This variability may reflect natural cyclic climate variations to be seen in context with the interannual and interdecadal environmental changes recorded in the High Northern Latitudes over the last decades, such as the NAO/AO pattern. A major decrease in MS values starting near 2.5 cal kyr BP, being more pronounced during the last about 2 cal kyr BP, correlates with a cooling trend over Greenland as indicated in the GISP-2 Ice Core, extended sea-ice cover in the North Atlantic, and advances of glaciers in western Norway. Our still preliminary interpretation of the MS variability has to be proven by further MS records from additional cores as well as other high-resolution multi-proxy Arctic climate records.

Sedimentology and geochemistry of ODP Site 184-1144

We analyzed sediment from Ocean Drilling Program (ODP) Site 1144 in the northern South China Sea to examine the weathering response of SE Asia to the strengthening of the East Asian Monsoon (EAM) since 14 ka. Our high-resolution record highlights the decoupling between continental chemical weathering, physical erosion and summer monsoon intensity. Mass accumulation rates, Ti/Ca, K/Rb, hematite/goethite and 87Sr/86Sr show sharp excursions from 11 to 8 ka, peaking at 10 ka. Clay minerals show a shorter-lived response with a higher kaolinite/(illite + chlorite) ratio at 10.7-9.5 ka. However, not all proxies show a clear response to environmental changes. Magnetic susceptibility rises sharply between 12 and 11 ka. Grain-size becomes finer from 14 to 10 ka and then coarsens until ~7 ka, but is probably controlled by bottom current flow and sealevel. Sr and Nd isotopes show that material is dominantly eroded from Taiwan with a lesser flux from Luzon, while clay mineralogy suggests that the primary sources during the Early Holocene were reworked via the shelf in the Taiwan Strait, rather than directly from Taiwan. Erosion was enhanced during monsoon strengthening and caused reworking of chemically weathered Pleistocene sediment largely from the now flooded Taiwan Strait, which was transgressed by ~8 ka, cutting off supply to the deep-water slope. None of the proxies shows an erosional response lasting until ~6 ka, when speleothem oxygen isotope records indicate the start of monsoon weakening. Although more weathered sediments were deposited from 11 to 8 ka when the monsoon was strong these are reworked and represent more weathering during the last glacial maximum (LGM) when the summer monsoon was weaker but the shelves were exposed.

Paleomagnetic and age determinations on rocks from Nares Strait

The Nares Strait controversy concerns the debate about whether or not a major sinistral transcurrent fault (the Wegener Fault) separates northern Greenland and Canada. To date no firm evidence has been found for the proposed 200 km sinistral offset, and to the contrary, geological correlations, mainly involving Paleozoic rocks across the Nares Strait, suggest that total left-lateral motion is no more than 70 km. The E-W trending Thule (Greenland) and Devon Island (Canada) dyke swarms lie on opposite sides of Baffin Bay and are offset sinistrally about 200 km, suggesting that if their correlation is established a convincing case for the Wegener Fault can be made. Paleomagnetic, geochemical and petrographic data allow, but do not yet establish, the correlation. Paleomagnetic results for Canadian sites (VGP = 6.9°N, 181.8 °E, A95 = 12.7°, N = 5) and Greenland sites (VGP = 11.5 °N, 178.3 °E, A95 = 13.8°, N = 4) are not significantly different at the 95 % confidence level. These levels are too large to resolve whether or not the Thule and Devon Island swarms have been offset. Geochemical data reveal a distinct and identical pattern in incompatible elements, while petrographically, the dykes are indistinguishable. U-Pb geochronological results for a Canadian dyke (720.2 ±2.0 Ma) and a Thule dyke (720.4 ±2.7 Ma) are identical within error and clearly identify the two sets of dykes as being parts of the same magmatic episode.

Seawater Nd and Pb isotopic record in central Pacific and Caribbean sediments

The shoaling and final closure of the Central American Seaway (CAS) resulted in a major change of the global ocean circulation and has been suggested as an essential driver for strengthening of Atlantic Meridional Overturning Circulation (AMOC). The exact timing of CAS closure is key to interpreting its importance. Here we present a reconstruction of deep and intermediate water Nd and Pb isotope compositions obtained from fossil fish teeth and the authigenic coatings of planktonic foraminifera in the eastern equatorial Pacific (Ocean Drilling Program (ODP) Site 1241) and the Caribbean (ODP Sites 998, 999, and 1000) covering the final stages of CAS closure between 5.6 and 2.2 Ma. The data for the Pacific site indicate no significant Atlantic/Caribbean influence over this entire period. The Caribbean sites show a continuous trend to less radiogenic Nd isotope compositions during the Pliocene, consistent with an enhancement of Upper North Atlantic Deep Water (UNADW) inflow and a strengthening of the AMOC. Superimposed onto this long-term trend, shorter-term changes of intermediate Caribbean Nd isotope signatures approached more UNADW-like values during intervals when published reconstructions of seawater salinity suggested complete closure of the CAS. The data imply that significant deep water exchange with the Pacific essentially stopped by 7 Ma and that shallow exchange, which still occurred at least periodically until approximately 2.5 Ma, may have been linked to the strength of the AMOC but did not have any direct effect on the intermediate and deep Caribbean Nd isotope signatures through mixing with Pacific waters.

Osmium isotopic composition and platinum group element concentrations in sediments from ODP Hole 145-886C

Paired analyses of Os isotope composition and concentration of bulk sediment and leachable Os in a metalliferous pelagic clay sequence from the North Pacific, ODP Site 886C, are used to reconstruct the marine Os isotope record and the particulate meteoritic Os flux between 65.5 and 78 Ma. Measured 187Os/188Os of bulk sediments ranges from approximately 0.64 to 0.32 and those of leach analyses are very similar to bulk analyses. Hydrogenous Os dominates the sedimentary Os inventory throughout most of the studied interval. As a result the measured 187Os/188Os of leachable Os approximates that of contemporaneous seawater. The ODP 886C record shows rising 187Os/188Os in the deepest portion of the core, with a local maximum of 0.66 close to 74 Ma. The 67-72 Ma portion of the record is characterized by nearly constant 187Os/188Os ratios close to 0.6. The structure of the marine Os isotope record from ODP 886C differs markedly from the seawater 87Sr/86Sr curve, which rises monotonically throughout the time interval studied here. Calculated particulate meteoritic Os fluxes are between 0.5 and 2 pg/cm**2/kyr throughout most of the studied interval. Two discrete intervals of the core (one of which is within Cretaceous Tertiary, boundary KTB interval) are characterized by higher fluxes of meteoritic Os. Excluding these two intervals, the average background flux of particulate meteoritic Os is roughly half of that estimated from analyses of Cenozoic marine sediments. These are the first Os isotope data to provide evidence of resolvable temporal variations in the background flux of particulate meteoritic material to the Earth.

Dinoflagellate cyst abundances at DSDP Site 94-607 from the North Atlantic (Appendix B)

The climatic deterioration related to the onset of Northern Hemisphere glaciations (circa 2.52 Ma BP) must have lead to reorganization and relocation of species associations and may have enhanced species turnover. The present study investigates how this deterioration affects the dinoflagellate cyst and acritarch assemblages from two locations, DSDP Site 607 (North Atlantic) and the Singa section (southern Italy). The records from these locations cover the interval from 2.8 to 2.2 Ma with at least a 5 ka resolution and they have been correlated to the Milankovitch periodicities on a cycle to cycle basis by means of integrated high resolution stable isotope, calcium carbonate, foraminiferal, palynological and magnetostratigraphical datasets. In the present study this high resolution stratigraphic framework is used for a detailed correlation of events occurring in each of the depositional sequences. It also enables further assessment of the palaeoenvironmental preferences of some dinoflagellate cyst forms. Comparison of the two palynological records reveals a close correspondence in the timing of major assemblage changes and extinction events, confirming their Milankovitch cycle based correlation. A close link between periods of Northern Hemisphere cooling (at oxygen isotope stages 110, 104 and 100-96) and increased dinoflagellate cyst turnover appears to be present for both DSDP Site 607 and the Singa section. The turnover events can also be recognized in the records of planktic foraminifera and calcamous nannoplankton. Comparison of the Singa section with Site 607 and with other time equivalent marine palynological data sets, shows that some oceanic taxa respond similarly over a large area. The biostratigraphical implications are discussed. Notably the last occurrence of Invertocystu lucrymosa appears to be a valuable marker for isotope stage 110 in the Mediterranean and North Atlantic.