Maxima of interstitial water and gas parameters in ODP Leg 182 sediments

During the drilling of the southern Australian continental margin (Leg 182 of the Ocean Drilling Program), fluids with unusually high salinities (to 106?) were encountered in Miocene to Pleistocene sediments. At three sites (1127, 1129, and 1131), high contents of H2S (to 15%), CH4 (50%), and CO2 (70%) were also encountered. These levels of H2S are the highest yet reported during the history of either the Deep Sea Drilling Project or the Ocean Drilling Program. The high concentrations of H2S and CH4 are associated with anomalous Na+/Cl- ratios in the pore waters. Although hydrates were not recovered, and despite the shallow water depth of these sites (200-400 m) and relative warm bottom water temperatures (11-14°C), we believe that these sites possess disseminated H2S-dominated hydrates. This contention is supported by calculations using the measured gas concentrations and temperatures of the cores, and depths of recovery. High concentrations of H2S necessary for the formation of hydrates under these conditions were provided by the abundant (SO4)2- caused by the high salinities of the pore fluids, and the high concentrations of organic material. One hypothesis for the origin of these fluids is that they were formed on the adjacent continental shelf during previous lowstands of sea level and were forced into the sediments under the influence of hydrostatic head.

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.

3He/4He and 4He/20Ne ratios in pore water and gas in Pacific deep-sea sediments

We have measured the 3He/3He and 3He/20 Ne ratios of thirty-nine pore water and gas samples in deep-sea sediments collected at twelve sites on the Pacific Ocean bottom during the cruises of Deep Sea Drilling Project Legs 87, 89, 90 and 92. The 3He/4He and 4He/20Ne ratios vary from 0.000000215 to 0.00000165 and from 0.29 to 20, respectively. He in the sample is composed of four components: (1) atmospheric He dissolved in seawater; (2) atmospheric He with mantle-derived He in Pacific bottom water; (3) in situ radiogenic He in the sediment; and (4) crustal He in the basement rock. Assuming that the 20Ne contents are constant with the value of seawater, the depth variations in the 4He/20Ne ratios at five Sites, 583D, 594, 597A, 598A and 504B, may provide useful information on 4He flux at the ocean bottom. The estimated 4He fluxes vary from 2000 to 40000 atoms cm**-2 s**-1 and are one to three orders of magnitude less than those calculated from the excess He in deep ocean water. An overall similarity between the geographical distribution of the 3He/4He ratios and heat flow data is found in the study area, between the East Pacific Rise across the Pacific Ocean and the Japanese Islands. The tendency is well explained by a conventional sea-floor spreading model.

Spatial community shift from hard to soft corals in acidified water

Anthropogenic increases in the partial pressure of CO2 (pCO2) cause ocean acidification, declining calcium carbonate saturation states, reduced coral reef calcification and changes in the compositions of marine communities. Most projected community changes due to ocean acidification describe transitions from hard coral to non-calcifying macroalgal communities; other organisms have received less attention, despite the biotic diversity of coral reef communities. We show that the spatial distributions of both hard and soft coral communities in volcanically acidified, semi-enclosed waters off Iwotorishima Island, Japan, are related to pCO2 levels. Hard corals are restricted to non-acidified low- pCO2 (225 µatm) zones, dense populations of the soft coral Sarcophyton elegans dominate medium- pCO2 (831 µatm) zones, and both hard and soft corals are absent from the highest- pCO2 (1,465 µatm) zone. In CO2-enriched culture experiments, high- pCO2 conditions benefited Sarcophyton elegans by enhancing photosynthesis rates and did not affect light calcification, but dark decalcification (negative net calcification) increased with increasing pCO2. These results suggest that reef communities may shift from reef-building hard corals to non-reef-building soft corals under pCO2 levels (550-970 µatm) predicted by the end of this century, and that higher pCO2 levels would challenge the survival of some reef organisms.

Chlorofluorocarbons and noble gas measured on water bottle samples during three POLARSTERN cruises

We use a 27 year long time series of repeated transient tracer observations to investigate the evolution of the ventilation time scales and the related content of anthropogenic carbon (Cant) in deep and bottom water in the Weddell Sea. This time series consists of chlorofluorocarbon (CFC) observations from 1984 to 2008 together with first combined CFC and sulphur hexafluoride (SF6) measurements from 2010/2011 along the Prime Meridian in the Antarctic Ocean and across the Weddell Sea. Applying the Transit Time Distribution (TTD) method we find that all deep water masses in the Weddell Sea have been continually growing older and getting less ventilated during the last 27 years. The decline of the ventilation rate of Weddell Sea Bottom Water (WSBW) and Weddell Sea Deep Water (WSDW) along the Prime Meridian is in the order of 15-21%; the Warm Deep Water (WDW) ventilation rate declined much faster by 33%. About 88-94% of the age increase in WSBW near its source regions (1.8-2.4 years per year) is explained by the age increase of WDW (4.5 years per year). As a consequence of the aging, the Cant increase in the deep and bottom water formed in the Weddell Sea slowed down by 14-21% over the period of observations.

Oxygen isotopes and hydrocarbon composition of gas hydrate and hydrate water from ODP Leg 165 sites

Ocean Drilling Program (ODP) Leg 164 recovered a number of large solid gas hydrate from Sites 994, 996, and 997 on the Blake Ridge. Sites 994 and 997 samples, either nodular or thick massive pieces, were subjected to laboratory analysis and measurements to determine the structure, molecular and isotopic composition, thermal conductivity, and equilibrium dissociation conditions. X-ray computed tomography (CT) imagery, X-ray diffraction, nuclear magnetic resonance (NMR), and Raman spectroscopy have revealed that the gas hydrates recovered from the Blake Ridge are nearly 100% methane gas hydrate of Structure I, cubic with a lattice constant of a = 11.95 ± 0.05 angström, and a molar ratio of water to gas (hydration number) of 6.2. The d18O of water is 2.67 per mil to 3.51 per mil SMOW, which is 3.5-4.0 heavier than the ambient interstitial waters. The d13C and dD of methane are -66 per mil to -70 per mil and -201 per mil to -206 per mil, respectively, suggesting that the methane was generated through bacterial CO2 reduction. Thermal conductivity values of the Blake Ridge hydrates range from 0.3 to 0.5 W/(m K). Equilibrium dissociation experiments indicate that the three-phase equilibrium for the specimen is 3.27 MPa at 274.7 K. This is almost identical to that of synthetic pure methane hydrate in freshwater.