Calcium isotope ratios of porewaters of ODP Leg 204 holes

The calcium isotopic composition of porewaters and authigenic carbonates in the anoxic sediments of a convergent continental margin drilled during Ocean Drilling Program (ODP) provides first insight into the different processes that control Ca geochemistry in clastic marine, organic-rich sedimentary environments. In 4 sites drilled during Leg 204 at Hydrate Ridge (Cascadia Margin, offshore Oregon/USA), sulfate is consumed during anaerobic oxidation of methane and of organic matter via sulfate reduction within the upper meters of the sedimentary section. These reactions promote the precipitation of authigenic carbonates through the generation of bicarbonate, which is reflected in a pronounced decrease in calcium concentration. Although Ca isotope fractionation is observed during carbonate precipitation, Ca concentration in the pore fluids from ODP Leg 204 is decoupled from Ca isotopy, which seems to be mainly controlled by the release of light Ca isotopes that completely overprint the carbonate formation effect. Different processes, such as the release of organically bound Ca, ion exchange and ion pair formation may be responsible for the released light Ca. Deeper within the sedimentary section, additional processes such as ash alteration influence the Ca isotopic composition of the porewater. Two sites, drilled into the deeper core of the accretionary prism, reveal the nature of fluids which have reacted with the oceanic basement. These deep fluids are characterized by relatively high Ca concentrations and low d44/40Ca ratios.

An environmental magnetic study, sedimentological and numerical methods around Tauranga Harbour, New Zealand

Magnetic iron minerals are widespread and indicative sediment constituents in estuarine, coastal and shelf systems. We combine environmental magnetic, sedimentological and numerical methods to identify magnetite-enriched placer-like zones in a complex coastal system and delineate their formation mechanisms. Magnetic susceptibility and remanence measurements on 245 surficial sediment samples collected in and around Tauranga Harbour, the largest barrier-enclosed tidal estuary of New Zealand, reveal several discrete enrichment zones controlled by local hydrodynamic conditions. Active magnetite enrichment takes place in tidal channels, which feed into two coast-parallel nearshore magnetite-enriched belts centered at water depths of 6-10 m and 10-20 m. A close correlation between magnetite content and magnetic grain size was found, where higher susceptibility values are associated within coarser magnetic crystal sizes. Two key mechanisms for magnetite enrichment are identified. First, tide-induced residual currents primarily enable magnetite enrichment within the estuarine channel network. A coast-parallel, fine sand magnetite enrichment belt in water depths of less than 10 m along the barrier island has a strong decrease in magnetite content away from the southern tidal inlet and is apparently related to active coast-parallel transport combined with mobilizing surf zone processes. A second, less pronounced, but more uniform magnetite enrichment belt at 10-20 m water depth is composed of non-mobile, medium-coarse-grained relict sands, which have been reworked during post-glacial sea level transgression. We demonstrate the potential of magnetic methods to reveal and differentiate coastal magnetite enrichment patterns and investigate their formative mechanisms.

Carbon and deuterium isotopes and C ratios in gas hydrates of ODP Leg 204 sites

Sediments at the southern summit of Hydrate Ridge display two distinct modes of gas hydrate occurrence. The dominant mode is associated with active venting of gas exsolved from the accretionary prism and leads to high concentrations (15%-40% of pore space) of gas hydrate in seafloor or near-surface sediments at and around the topographic summit of southern Hydrate Ridge. These near-surface gas hydrates are mainly composed of previously buried microbial methane but also contain a significant (10%-15%) component of thermogenic hydrocarbons and are overprinted with microbial methane currently being generated in shallow sediments. Focused migration pathways with high gas saturation (>65%) abutting the base of gas hydrate stability create phase equilibrium conditions that permit the flow of a gas phase through the gas hydrate stability zone. Gas seepage at the summit supports rapid growth of gas hydrates and vigorous anaerobic methane oxidation. The other mode of gas hydrate occurs in slope basins and on the saddle north of the southern summit and consists of lower average concentrations (0.5%-5%) at greater depths (30-200 meters below seafloor [mbsf]) resulting from the buildup of in situ-generated dissolved microbial methane that reaches saturation levels with respect to gas hydrate stability at 30-50 mbsf. Net rates of sulfate reduction in the slope basin and ridge saddle sites estimated from curve fitting of concentration gradients are 2-4 mmol/m**3/yr, and integrated net rates are 20-50 mmol/m**2/yr. Modeled microbial methane production rates are initially 1.5 mmol/m**3/yr in sediments just beneath the sulfate reduction zone but rapidly decrease to rates of <0.1 mmol/m**3/yr at depths >100 mbsf. Integrated net rates of methane production in sediments away from the southern summit of Hydrate Ridge are 25-80 mmol/m**2/yr. Anaerobic methane oxidation is minor or absent in cored sediments away from the summit of southern Hydrate Ridge. Ethane-enriched Structure I gas hydrate solids are buried more rapidly than ethane-depleted dissolved gas in the pore water because of advection from compaction. With subsidence beneath the gas hydrate stability zone, the ethane (mainly of low-temperature thermogenic origin) is released back to the dissolved gas-free gas phases and produces a discontinuous decrease in the C1/C2 vs. depth trend. These ethane fractionation effects may be useful to recognize and estimate levels of gas hydrate occurrence in marine sediments.

Seawater carbonate chemistry and zooxanthellate coral Cladocora caespitosa boron isotopic and elemental systematics during experiments, 2011

Boron isotopic and elemental systematics are used to define the vital effects for the temperate shallow water Mediterranean coral Cladocora caespitosa. The corals are from a range of seawater pH conditions (pHT ~ 7.6 to ~ 8.1) and environmental settings: (1) naturally living colonies harvested from normal pH waters offshore Levanto, (2) colonies transplanted nearby a subsea volcanic vent system, and (3) corals cultured in aquaria exposed to high (700 µatm) and near present day (400 µatm) pCO2 levels. B/Ca compositions measured using laser ablation inductively coupled mass spectrometry (LA-ICPMS) show that boron uptake by C. caespitosa cultured at different pCO2 levels is independent of ambient seawater pH being mainly controlled by temperature-dependent calcification. In contrast, the boron isotope compositions (delta11Bcarb) of the full suite of corals determined by positive thermal ionisation mass spectrometry (PTIMS) shows a clear trend of decreasing delta11Bcarb (from 26.7 to 22.2 %o) with decreasing seawater pH, reflecting the strong pH dependence of the boron isotope system. The delta11Bcarb compositions together with measurements of ambient seawater parameters enable calibration of the boron pH proxy for C. caespitosa, by using a new approach that defines the relationship between ambient seawater pH (pHsw) and the internally controlled pH at the site of calcification (pHbiol). C. caespitosa exhibits a linear relationship between pHsw and the shift in pH due to physiological processes (deltapH = pHbiol - pHsw) giving the regression deltapHClad = 4.80 - 0.52* pHsw for this species. We further apply this method ("deltapH-pHsw") to calibrate tropical species of Porites, Acropora, and Stylophora reported in the literature. The temperate and tropical species calibrations are all linearly correlated (r2 > 0.9) and the biological fractionation component (deltapH) between species varies within ~ 0.2 pH units. Our "deltapH-pHsw" approach provides a robust and accurate tool to reconstruct palaeoseawater pHsw for both temperate and tropical corals, further validating the boron fractionation factor (alphaB3-B4 = 1.0272) determined experimentally by Klochko et al. (2006) and the boron isotope pH proxy, both of which have been the foci of considerable debate.

AMS 14C dating points, isotopic compositions, Mg/Ca ratios and sea surface temperatures of sediment cores GeoB10029-4 and GeoB10038-4

Quantifying the spatial and temporal sea surface temperature (SST) and salinity changes of the Indo-Pacific Warm Pool is essential to understand the role of this region in connection with abrupt climate changes particularly during the last deglaciation. In this study we reconstruct SST and seawater d18O of the tropical eastern Indian Ocean for the past 40,000 years from two sediment cores (GeoB 10029-4, 1°30'S, 100°08'E, and GeoB 10038-4, 5°56'S, 103°15'E) retrieved offshore Sumatra. Our results show that annual mean SSTs increased about 2-3 °C at 19,000 years ago and exhibited southern hemisphere-like timing and pattern during the last deglaciation. Our SST records together with other Mg/Ca-based SST reconstructions around Indonesia do not track the monsoon variation since the last glacial period, as recorded by terrestrial monsoon archives. However, the spatial SST heterogeneity might be a result of changing monsoon intensity that shifts either the annual mean SSTs or the seasonality of G. ruber towards the warmer or the cooler season at different locations. Seawater d18O reconstructions north of the equator suggest fresher surface conditions during the last glacial and track the northern high-latitude climate change during the last deglaciation. In contrast, seawater ?18O records south of the equator do not show a significant difference between the last glacial period and the Holocene, and lack Bølling-Allerød and Younger Dryas periods suggestive of additional controls on annual mean surface hydrology in this part of the Indo-Pacific Warm Pool.

Grain-size distributions and bulk chemistry of sediment core MD00-2361

The terrigenous fraction of sediments from a deep-sea sediment core recovered from the northwestern Western Australian continental slope offshore North West Cape, SE Indian Ocean, reveals a history of Western Australian climate throughout the last 550 ka. End-member modelling of a data set of grain-size distributions (n = 438) of the terrigenous sediment fraction allows to interpret the record in terms of aeolian and fluvial sediment deposition, both related to palaeo-environmental conditions in the North West Cape area. The data set can be best described by two aeolian end members and one fluvial one. Changes in the ratio of the two aeolian end members over the fluvial one are interpreted as aridity variations in northwestern Western Australia. These grain-size data are compared with bulk geochemical data obtained by XRF scans of the core. Log-ratios of the elements Zr/Fe and Ti/Ca, which indicate a terrigenous origin, corroborate the grain-size data. We postulate that the mid- to late Quaternary near North West Cape climate was relatively arid during the glacial and relatively humid during the interglacial stages, owing to meridional shifts in the atmospheric circulation system. Opposite to published palaeo-environmental records from the same latitude (20°S) offshore Chile and offshore Namibia, the Australian aridity record does not show the typical southern hemisphere climate variability of humid glacials and dry interglacials, which we interpret to be the result of the relatively large land mass of the Australian continent, which emphasises a strong monsoonal climatic system.

(Table 1) Light minerals in sand at DSDP Leg 84 holes

The Middle America active continental margin is the best-sampled active plate margin to date, having been drilled during Legs 84, 67, and 66. With nine sites drilled on the continental slope of Guatemala and an additional site drilled on the Costa Rican slope, a summary of slope sediments and sedimentary processes can be made. Sediments are easily subdivided into a thick apron of Neogene and Quaternary volcanically derived hemipelagic and turbidite mud and mudstone and a thinner, more varied assemblage of mostly Paleogene mudstone, radiolarian mudstone, and limestone. This latter assemblage may contain hiatuses or be completely lacking between slope deposits and basement. Cores from the foot of the continental slope (Core 567A-19) consist of Campanian micrite. The pre-Neogene section is much thicker and of more terrigenous provenance beneath the forearc basin landward of the forearc structural high than on the continental slope. Sedimentary processes of the Neogene and Quaternary slope sediments include reworking of hemipelagic and turbidite deposits. Redeposition by slumping, plastic flow, and turbidity current-documentable through benthic foraminiferal analysis-occurs in intracanyon and canyon settings. Erosion by slumping and by turbidity current and deposition of mud or sand in canyons and in local depressions on the continental slope and different rates of sediment accumulation result in dramatic thickness variations of lithologic units over small distances in localized pockets of sand in small filled canyons on the slope or in sediment ponds, and in high-relief basement topography. The age of sediment overlying igneous basement ranges from Cretaceous to Quaternary. Gas hydrate was visible or inferred present at every site drilled during Leg 84. Nevertheless, except for a small amount in the last core, it was not recovered in sufficient quantities to be visible at Site 568, a site specifically chosen for the study of hydrate and located near Site 496, which was abandoned during Leg 67 because of the dangerous abundance of hydrates. The association of hydrate with porous, coarser sediment results in a distribution as localized and unpredictable as the slope sands off Guatemala, which do not occur in beds coherent enough to produce acoustic reflection. Although the normal lithologic section at Sites 567 and 496 limits the volume of sediment that could be part of an accretionary prism offshore Guatemala and the volume of sediment in the Trench axis is not sufficient to argue for significant accumulation of Cocos Plate sediments, the varied lithology and attenuated thickness of pre-Neogene sediment seaward of the forearc structural high do not exclude earlier accretion from the history of the Guatemalan continental margin.

Tephrostratigraphy and radiometric dating of authigenic carbonates

At convergent margins, fluids rise through the forearc in response to consolidation of the upper plate and dewatering of the subducting plate, and produce various cold-seep-related features on the seafloor (mud diapirs, mud mounds). At the Central American forearc, authigenic carbonates precipitated from rising fluids within such structures during active venting while typical mixed-mud sediments were ejected onto the surrounding seafloor where they became intercalated with normal pelagic background sediments, indicating that mud mounds evolved unsteadily through alternating active and inactive phases. Intercalated regional ash layers from Plinian eruptions at the Central American volcanic arc provide time marks that constrain the ages of mud ejection activity. U/Th dating of drill core samples of authigenic carbonate caps of mud mounds yields ages agreeing well with those constrained by ash layers and showing that carbonate caps grow inward rather than outward during active venting. Both dating approaches show that offshore Nicaragua and Costa Rica (1) active and inactive phases can occur simultaneously at neighboring mounds, (2) mounds along the forearc have individual histories of activity, but there are distinct time intervals when nearly all mounds have been active or inactive, (3) lifetimes of mounds reach several hundred thousand years, and (4) highly active periods last 10-50 k.y. with intervening periods of >10 k.y. of relative quiescence.

Organic geochemistry of DSDP Site 467

Results of the analyses of twenty-three samples from the Middle Miocene to Lower Pliocene strata from DSDP Site 467, offshore California, are presented. The analyses were performed with the aim of determining the origin of the organic matter, the stratigraphic section's hydrocarbon generation potential and extent of organic diagenesis. Organic carbon contents are an order of magnitude greater than those typically found in deep sea sediments, suggesting an anoxic depositional environment and elevated levels of primary productivity. Hydrocarbon generation potentials are above average for most samples. The results of elemental analyses indicate that the kerogens are primarily composed of type II organic matter and are thermally immature. Analysis of the bitumen fractions confirms that the samples are immature. In cores from 541 to 614 meters, the gas chromatograms of the C15+ non-aromatic hydrocarbon fractions are dominated by a single peak which was identified as 17*(H), 18*(H), 21beta(H)-28, 30-bisnorhopane. This interval is the same area in which the highest degrees of anoxia are observed as reflected by the lowest pristane/phytane ratios. This correlation may have some implications with regard to the origin of the bisnorhopane and its possible use as an indicator of anoxic depositional conditions within thermally immature sediments.

Stable isotopes, Mg/Ca ratios and sea surface temperatures on foraminifera from sediment cores off equatorial Peru during the last ~17kyr

The complex deglacial to Holocene oceanographic development in the Gulf of Guayaquil (Eastern Equatorial Pacific) is reconstructed for sea surface and subsurface ocean levels from (isotope) geochemical proxies based on marine sediment cores. At sea surface, southern sourced Cold Coastal Water and tropical Equatorial Surface Water/Tropical Surface Water are intimately related. In particular since ~10 ka, independent sea surface temperature proxies capturing different seasons emphasize the growing seasonal contrast in the Gulf of Guayaquil, which is in contrast to ocean areas further offshore. Cold Coastal Water became rapidly present in the Gulf of Guayaquil during the austral winter season in line with the strengthening of the Southeast Trades, while coastal upwelling off Peru gradually intensified and expanded northward in response to a seasonally changing atmospheric circulation pattern affecting the core locations intensively since 4 ka BP. Equatorial Surface Water, instead, was displaced and Tropical Surface Water moved northward together with the Equatorial Front. At subsurface, the presence of Equatorial Under Current-sourced Equatorial Subsurface Water was continuously growing, prominently since ~10-8 ka B.P. During Heinrich Stadial 1 and large parts of the Bølling/Allerød, and similarly during short Holocene time intervals at ~5.1-4 ka B.P. and ~1.5-0.5 ka B.P., the admixture of Equatorial Subsurface Water was reduced in response to both short-term weakening of Equatorial Under Current strength from the northwest and emplacement by tropical Equatorial Surface Water, considerably warming the uppermost ocean layers.