Pore water acetate and hydrogen, helium and methane gas concentrations in ODP Leg 204 sediments

Acetate and hydrogen concentrations in pore fluids were measured in samples taken at seven sites from southern Hydrate Ridge (SHR) offshore Oregon, USA. Acetate concentrations ranged from 3.17 to 2515 µM. The maximum acetate concentrations occurred at Site 1251, which was drilled on a slope basin to the east of SHR at depths just above the bottom-simulating reflector (BSR) that marks the boundary of gas hydrate stability. Acetate maxima and localized high acetate concentrations occurred at the BSR at all sites and frequently corresponded with areas of gas hydrate accumulation, suggesting an empirical relationship. Acetate concentrations were typically at a minimum near the seafloor and above the sulfate/methane interface, where sulfate-reducing bacteria may consume acetate. Hydrogen concentrations in pressure core samples ranged from 16.45 to 1036 parts per million by volume (ppmv). In some cases, hydrogen and acetate concentrations were elevated concurrently, suggesting a positive correlation. However, sampling of hydrogen was limited in comparison to acetate, so any relationships between the two analytes, if present, were difficult to discern.

Geochemical processes and rare earth element analysis in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reductionas dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE concentrations is evident immediately below the sediment-water interface, which can be related to early diagenetic release of REEs into pore water resulting from the remineralization of particulate organic matter. The highest pore water REE concentrations were measured close to the sediment-water interface at ~2 cm depth. Distinct shale normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shalenormalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.

Isotopic and chemical compositions of DSDP site 18-174 sediments

The Astoria submarine fan, located off the coast of Washington and Oregon, has grown throughout the Pleistocene from continental input delivered by the Columbia River drainage system. Enormous floods from the sudden release of glacial lake water occurred periodically during the Pleistocene, carrying vast amounts of sediment to the Pacific Ocean. DSDP site 174, located on the southern distal edge of the Astoria Fan, is composed of 879 m of terrigenous sediments. The section is divided into two major units separated by a distinct seismic discontinuity: an upper, turbidite fan unit (Unit I), and an underlying finer-grained unit (Unit II). Both units have overlapping ranges of Nd and Hf isotope compositions, with the majority of samples having e-Nd values of -7.1 to -15.2 and eHf values -6.2 to -20.0; the most notable exception is the uppermost sample in the section, which is identical to modern Columbia River sediment. Nd depleted mantle model ages for the site range from 2.0 to 1.2 Ga and are consistent with derivation from cratonic Proterozoic source regions, rather than Cenozoic and Mesozoic terranes proximal to the Washington-Oregon coast. The Astoria Fan sediments have significantly less radiogenic Nd (and Hf) isotopic compositions than present day Columbia River sediment (e-Nd=-3 to -4; [Goldstein, S.J., Jacobsen, S.B., 1987. Nd and Sr isotopic systematics of river water suspended material: implications for crustal evolution. Earth. Planet. Sci. Lett. 87, 249-265; doi:10.1016/0012-821X(88)90013-1]), and suggest that outburst flooding, tapping Proterozoic source regions, was the dominant sediment transport mechanism in the genesis and construction of the Astoria Fan. Pb isotopes form a highly linear 207Pb/204Pb - 206Pb/204Pb array, and indicate the sediments are a binary mixture of two disparate sources with isotopic compositions similar to Proterozoic Belt Supergroup metasediments and Columbia River Basalts. The combined major, trace and isotopic data argue that outburst flooding was responsible for depositing the majority (top 630 m) of the sediment in the Astoria Fan.

Heavy and light minerals in turbidites from DSDP Hole 19-183, the Aleutian abyssal plain

The Aleutian abyssal plain is a fossil abyssal plain of Paleogene age in the western Gulf of Alaska. The plain is a large, southward-thinning turbidite apron now cut off from sediment sources by the Aleutian Trench. Turbidite sedimentation ceased about 30 m.y. ago, and the apron is now buried under a thick blanket of pelagic deposits. Turbidites of the plain were recovered at site 183 of the Deep Sea Drilling Project on the northern edge of the apron. The heavy-mineral fraction of sand-sized samples is mostly amphibole and epidote with minor pyroxene, garnet, and sphene. The light-mineral fraction is mostly quartzose debris and feldspars. Subordinate lithic fragments consist of roughly equal amounts of metamorphic, plutonic, sedimentary, and volcanic grains. The sand compositions are arkoses in many sandstone classifications, although if fine silt is included with clay as matrix, the sand deposits are feldspathic or lithofeldspathic graywacke. The sands are apparently first-cycle products of deep dissection into a plutonic terrane, and they contrast sharply with arc-derived volcanic sandstones of similar age common on the adjacent North American continental margin. The turbidite sands are stratigraphically remarkably constant in composition, which indicates derivation from virtually the same terrane through a time span approaching 20 m.y. Comparison of Aleutian plain data with the compositions of coeval sedimentary rocks from the northeast Pacific margin shows that the Kodiak shelf area includes possible proximal equivalents of the more distal turbidites. Derivation from the volcaniclastic Mesozoic flysch of the Shumagin-Kodiak shelf is unlikely; more probably the sediments were derived from primary plutonic sources. The turbidites also resemble deposits in the Chugach Mountains and the younger turbidites of the Alaskan abyssal plain and could conceivably have been derived from the coast ranges of southeastern Alaska or western British Columbia. The Aleutian plain sediment most likely was not derived from as far south as the Oregon-Washington continental margin, where coeval sedimentary deposits are dominantly volcaniclastic.

(Appendix) Vertebral number of topsmelt, Atherinops affinis, adults and offspring from different latitudes along the North-American Pacific coast

Organisms that are distributed across spatial climate gradients often exhibit adaptive local variations in morphological and physiological traits, but to what extent such gradients shape evolutionary responses is still unclear. Given the strong natural contrast in latitudinal temperature gradients between the North-American Pacific and Atlantic coast, we asked how increases in vertebral number (VN, known as Jordan's Rule) with latitude would differ between Pacific (Atherinops affinis) and Atlantic Silversides (Menidia menidia), two ecologically equivalent and taxonomically similar fishes with similar latitudinal distributions. VN was determined from radiographs of wild-caught adults (genetic + environmental differences) and its genetic basis confirmed by rearing offspring in common garden experiments. Compared to published data on VN variation in M. menidia (a mean increase of 7.0 vertebrae from 32 to 46°N, VN slope = 0.42/lat), the latitudinal VN increase in Pacific Silversides was approximately half as strong (a mean increase of 3.3 vertebrae from 28 to 43°N, VN slope = 0.23/lat). This mimicked the strong Atlantic (1.11°C/lat) versus weak Pacific latitudinal gradient (0.40°C/lat) in median annual sea surface temperature (SST). Importantly, the relationship of VN to SST was not significantly different between the two species (average slope = -0.39 vertebrae/°C), thus suggesting a common thermal dependency of VN in silverside fishes. Our findings provide novel support for the hypothesis that temperature gradients are the ultimate cause of Jordan's Rule, even though its exact adaptive significance remains speculative. A second investigated trait, the mode of sex determination in Atlantic versus Pacific Silversides, revealed patterns that were inconsistent with our expectation: M. menidia displays temperature-dependent sex determination (TSD) at low latitudes, where growing seasons are long or unconstrained, but also a gradual shift to genetic sex determination (GSD) with increasing latitude due to more and more curtailed growing seasons. Sex ratios in A. affinis, on the other hand, were independent of latitude and rearing temperature (indicating GSD), even though growing seasons are thermally unconstrained across most of the geographical distribution of A. affinis. This suggests that additional factors (e.g., longevity) play an important role in shaping the mode of sex determination in silverside fishes.

Foraminiferal abundance, carbonat concentration and dissolution index of sediment core W9903B-51GC

In order to investigate the paleoceanographic record of dissolution of calcium carbonate (CaCO3) in the central equatorial Pacific Ocean, we have studied the relationship between three indices of foraminiferal dissolution and the concentration and accumulation of CaCO3, opal, and Corg in Core WEC8803B-GC51 (1.3°N, 133.6°W; 4410 m). This core spans the past 413 kyr of deposition and moved in and out of the lysoclinal transition zone during glacial-interglacial cycles of CaCO3 production and dissolution. The record of dissolution intensity provided by foraminiferal fragmentation, the proportion of benthic foraminifera, and the foraminiferal dissolution index consistently indicates that the past corrosion of pelagic CaCO3 in the central equatorial Pacific does not vary with the observed sedimentary concentration of CaCO3. Although there is a weak low-frequency variation (~100 kyr) in dissolution intensity, it is unrelated to sedimentary CaCO3 concentration. There are many shorter-lived episodes where high CaCO3 concentration is coincident with poor foraminiferal preservation, and where, conversely, low CaCO3 concentration is coincident with superb foraminiferal preservation. Spectral analyses indicate that dissolution maxima consistently lagged glacial maxima (manifest by the SPECMAP delta18O stack) in the 100-kyr orbital band. Additionally, there is no relationship between dissolution and the accumulation of biogenic opal or Corg or between dissolution and the burial ratio of Corg/CINorg (calculated from Corg and CaCO3). Because previous studies of this core strongly suggest that surface water productivity varied closely with CaCO3 accumulation, both the mechanistic decoupling of carbonate dissolution from CaCO3 concentration (and from biogenic accumulation) and the substantial phase shift between dissolution and global glacial periodicity effectively obscure any simple link between export production, CaCO3 concentration, and dissolution of sedimentary CaCO3.

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.

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.

Response of three krill species to hypoxia and warming: An experimental approach to oxygen minimum zones expansion in coastal ecosystems

To understand the adaptation of euphausiid (krill) species to oxygen minimum zones (OMZ), respiratory response and stress experiments combining hypoxia/reoxygenation exposure with warming were conducted. Experimental krill species were obtained from the Antarctic (South Georgia area), the Humboldt Current system (HCS, Chilean coast), and the Northern California Current system (NCCS, Oregon). Euphausia mucronata from the HCS shows oxyconforming or oxygen partial pressure (pO2)-dependent respiration below 80% air saturation (18 kPa). Normoxic subsurface oxygenation in winter posed a "high oxygen stress" for this species. The NCCS krill, Euphausia pacifica, and the Antarctic krill, Euphausia superba maintain respiration rates constant down to low critical pO2 values of 6 kPa (30% air saturation) and 11 kPa (55% air saturation), respectively. Antarctic krill had the lowest antioxidant enzyme activities, but the highest concentrations of the molecular antioxidant glutathione (GSH) and was not affected by 6 h exposure to moderate hypoxia. Temperate krill species had higher SOD (superoxide dismutase) values in winter than in summer, which relate to higher winter metabolic rate (E. pacifica). In all species, antioxidant enzyme activities remained constant during hypoxic exposure at habitat temperature. Warming by 7°C above habitat temperature in summer increased SOD activities and GSH levels in E. mucronata (HCS), but no oxidative damage occurred. In winter, when the NCCS is well mixed and the OMZ is deeper, +4°C of warming combined with hypoxia represents a lethal condition for E. pacifica. In summer, when the OMZ expands upwards (100 m subsurface), antioxidant defences counteracted hypoxia and reoxygenation effects in E. pacifica, but only at mildly elevated temperature (+2°C). In this season, experimental warming by +4°C reduced antioxidant activities and the hypoxia combination again caused mortality of exposed specimens. We conclude that a climate change scenario combining warming and hypoxia represents a serious threat to E. pacifica and, as a consequence, NCCS food webs.