Arthur J. Spivack

Subseafloor sedimentary life in the South Pacific Gyre

The low-productivity South Pacific Gyre (SPG) is Earths largest oceanic province. Its sediment accumulates extraordinarily slowly (0.1–1 m per million years). This sediment contains a living community that is characterized by very low biomass and very low metabolic activity. At every depth in cored SPG sediment, mean cell abundances are 3 to 4 orders of magnitude lower than at the same depths in all previously explored subseafloor communities. The net rate of respiration by the subseafloor sedimentary community at each SPG site is 1 to 3 orders of magnitude lower than the rates at previously explored sites. Because of the low respiration rates and the thinness of the sediment, interstitial waters are oxic throughout the sediment column in most of this region. Consequently, the sedimentary community of the SPG is predominantly aerobic, unlike previously explored subseafloor communities. Generation of H2 by radiolysis of water is a significant electron-donor source for this community. The per-cell respiration rates of this community are about 2 orders of magnitude higher (in oxidation/reduction equivalents) than in previously explored anaerobic subseafloor communities. Respiration rates and cell concentrations in subseafloor sediment throughout almost half of the world ocean may approach those in SPG sediment.

New insights into deformation and fluid flow processes in the Nankai Trough accretionary prism: Results of Ocean Drilling Program Leg 190

Moore, G. F., Taira, A., Klaus, A., Becker, L., Boeckel, B., Cragg, B. A., Dean, A., Fergusson, C. L., Henry, P., Hirano, S., Hisamitsu, T. et al. (2001). New insights into deformation and fluid flow processes in the Nankai Trough accretionary prism: Results of Ocean Drilling Program Leg 190. Geochemistry, Geophysics, Geosystems, 2, Article No: 2001GC000166.

Endospore abundance, microbial growth and necromass turnover in deep sub-seafloor sediment

Two decades of scientific ocean drilling have demonstrated widespread microbial life in deep sub-seafloor sediment, and surprisingly high microbial-cell numbers. Despite the ubiquity of life in the deep biosphere, the large community sizes and the low energy fluxes in this vast buried ecosystem are not yet understood. It is not known whether organisms of the deep biosphere are specifically adapted to extremely low energy fluxes or whether most of the observed cells are in a dormant, spore-like state. Here we apply a new approach—the d:l-amino-acid model—to quantify the distributions and turnover times of living microbial biomass, endospores and microbial necromass, as well as to determine their role in the sub-seafloor carbon budget. The approach combines sensitive analyses of unique bacterial markers (muramic acid and D-amino acids) and the bacterial endospore marker, dipicolinic acid, with racemization dynamics of stereo-isomeric amino acids. Endospores are as abundant as vegetative cells and microbial activity is extremely low, leading to microbial biomass turnover times of hundreds to thousands of years. We infer from model calculations that biomass production is sustained by organic carbon deposited from the surface photosynthetic world millions of years ago and that microbial necromass is recycled over timescales of hundreds of thousands of years.

Biological formation of ethane and propane in the deep marine subsurface

Concentrations and isotopic compositions of ethane and propane in cold, deeply buried sediments from the southeastern Pacific are best explained by microbial production of these gases in situ. Reduction of acetate to ethane provides one feasible mechanism. Propane is enriched in 13C relative to ethane. The amount is consistent with derivation of the third C from inorganic carbon dissolved in sedimentary pore waters. At typical sedimentary conditions, the reactions yield free energy sufficient for growth. Relationships with competing processes are governed mainly by the abundance of H2. Production of C2 and C3 hydrocarbons in this way provides a sink for acetate and hydrogen but upsets the general belief that hydrocarbons larger than methane derive only from thermal degradation of fossil organic material.

Stable Cl isotopes in subduction-zone pore waters: Implications for fluid-rock reactions and the cycling of chlorine

Stable Cl isotope ratios, measured in marine pore waters associated with the Barbados and Nankai subduction zones, extend significantly (to ∼−8‰) the range of δ 37 Cl values reported for natural waters. These relatively large negative values, together with geologic and chemical evidence from Barbados and Nankai and recent laboratory data showing that hydrous silicate minerals (i.e., those with structural OH sites) are enriched up to 7.5‰ in 37 Cl relative to seawater, strongly suggest that the isotopic composition of Cl in pore waters from subduction zones reflects diagenetic and metamorphic dehydration and transformation reactions. These reactions involve clays and/or other hydrous silicate phases at depth in the fluid source regions. Chlorine therefore cannot be considered geochemically conservative in these systems. The uptake of Cl by hydrous phases provides a mechanism by which Cl can be cycled into the mantle through subduction zones. Thus, stable Cl isotopes should help in determining the extent to which Cl and companion excess volatiles like H 2 O and CO 2 cycle between the crust and mantle.

PRECISE DETERMINATION OF STABLE CHLORINE ISOTOPIC RATIOS IN LOW-CONCENTRATION NATURAL SAMPLES

Investigation of stable chlorine isotopes in geological materials has been hindered by large sample requirements and/or lack of analytical precision. Here we describe precise methods for the extraction, isolation, and isotopic analysis of low levels of chlorine in both silicate and aerosol samples. Our standard procedure uses 2 μg of Cl for each isotopic analysis. External reproducibility (1 σ) is 0.25%. for the 37Cl35Cl measurements. Chlorine is extracted from silicate samples (typically containing at least 20 μg of Cl) via pyrohydrolysis using induction heating and water vapor as the carrier, and the volatilized chlorine is condensed in aqueous solution. Atmospheric aerosols collected on filters are simply dissolved in water. Prior to isotopic measurement, removal of high levels of SO42−, F−, and organic compounds is necessary for the production of stable ion beams. Sulfate is removed by BaSCO4 precipitation, F− by CaF2 precipitation, and organic compounds are extracted with activated carbon. Chlorine is converted to stoichiometric CsCl by cation exchange, and isotopic ratios are determined by thermal ionization mass spectrometry of Cs2Cl+. We demonstrate that the sensitivity and precision of this method allow resolution of natural variations in chlorine isotopic composition, and thereby provide insight to some fundamental aspects of chlorine geochemistry.

Radiolytic hydrogen and microbial respiration in subsurface sediments.

Radiolysis of water may provide a continuous flux of an electron donor (molecular hydrogen) to subsurface microbial communities. We assessed the significance of this process in anoxic marine sediments by comparing calculated radiolytic H(2) production rates to estimates of net (organic-fueled) respiration at several Ocean Drilling Program (ODP) Leg 201 sites. Radiolytic H(2) yield calculations are based on abundances of radioactive elements (uranium, thorium, and potassium), porosity, grain density, and a model of water radiolysis. Net respiration estimates are based on fluxes of dissolved electron acceptors and their products. Comparison of radiolytic H(2) yields and respiration at multiple sites suggests that radiolysis gains importance as an electron donor source as net respiration and organic carbon content decrease. Our results suggest that radiolytic production of H(2) may fuel 10% of the metabolic respiration at the Leg 201 site where organic-fueled respiration is lowest (ODP Site 1231). In sediments with even lower rates of organic-fueled respiration, water radiolysis may be the principal source of electron donors. Marine sedimentary ecosystems may be useful models for non-photosynthetic ecosystems on early Earth and on other planets and moons, such as Mars and Europa.

Boron isotope fractionation during supercritical phase separation

Abstract Boron isotopic fractionation between vapor and brine phases separated under supercritical conditions has been experimentally examined using a Na-Ca-K-Cl fluid. Experiments were conducted at 425, 440, and 450°C. Phase separation was controlled by adjusting pressure. Fractionation between the coexisting phases was less than 0.5%.. In contrast, fractionation between trigonal and tetrahedral B, at these temperatures, has been predicted to be approximately 8%.. The lack of fractionation suggests that the trigonal/tetrahedral speciation of B is similar in the two phases. Although this result may not be general for other fluid compositions, it is relevant to ridge crest hydrothermal solutions and indicates that the boron isotopic compositions of these solutions reflect the proportions of B from seawater and crustal sources and not phase separation.

Low-temperature alteration of the upper oceanic crust and the alkalinity budget of seawater

Abstract While the input of river-alkalinity into seawater is relatively well known, the complementary acidity production is poorly understood. Using the major-element budget of seafloor alteration of the upper 500 m of 120-Ma-old oceanic crust at DSDP/ODP Sites 417A, 417D and 418A in the central western Atlantic, we estimate the acidity flux associated with the low-temperature weathering of the upper oceanic crust. The acidity flux is calculated based on major-element fluxes and charge-balance considerations. The relevant chemical fluxes from seawater to the upper crust are 4.1 ± 0.1; 1.4 ± 1.4; 2.2 ± 0.6 and −12 ± 2 1011 mol yr−1 for K, Mg, Na and silicate-Ca, respectively. The associated acidity flux is (3.5 ± 3) · 1011 eq yr−1. Relative to continental weathering, these fluxes are significant for K and silicate-Ca, but are minor for Na, Mg and acidity. Thus, riverine fluxes of alkalinity are not significantly balanced by acidity fluxes from low-temperature upper ocean crust alteration.

Cold water coral mounds revealed

The discovery of mounds and reefs hosting cold-water coral ecosystems along the northeastern Atlantic continental margins has propelled a vigorous effort over the past decade to study the distribution of the mounds, surface sediments, the ecosystems they host, and their environments [Hovland et al., 1994; Freiwald and Roberts, 2005].This effort has involved swath bathymetry, remotely operated vehicle deployments, shallow coring, and seismic surveys. Global coverage is difficult to gauge, but studies indicate that cold-water corals may cover as large an area as the better known warm-water corals that form shallow reefs (284,300 square kilometers) [Freiwald et al., 2005]. Cold-water corals occur in a variety of forms and settings, from small isolated colonies or patch reefs to giant mound structures such as those found west of Ireland.