Chemistry of altered basaltic glass shards and zeolites of volcaniclastic sediments from ODP Hole 157-953C

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.

Strontium and boron geochemistry of ODP sites at Hydrate Ridge, eastern Pacific Ocean

ODP Leg 204, which drilled at Hydrate Ridge, provides unique insights into the fluid regime of an accretionary complex and delineates specific sub-seafloor pathways for fluid transport. Compaction and dewatering due to smectite-illite transition increase with distance from the toe of the accretionary prism and bring up fluids from deep within the accretionary complex to sampled depths (<= 600 mbsf). These fluids have a distinctly non-radiogenic strontium isotope signature indicating reaction with the oceanic basement. Boron isotopes are also consistent with a deep fluid source that has been modified by desorption of heavy boron as clay minerals change from smectite to illite. One of three major horizons serves as conduit for the transport of mainly fluid. Our results enable us to evaluate fluid migration pathways that play important roles on massive gas hydrate accumulations and seepage of methane-rich fluids on southern Hydrate Ridge.

(Table 2) Concentrations and D/L values for three amino acids in bulk foraminifera from ODP Sites 182-1126 and 182-1127

A number of studies have shown that methanogens are active in the presence of sulfate under some conditions. This phenomenon is especially exemplified in carbonate sediments of the southern Australian continental margin. Three sites cored during Ocean Drilling Program (ODP) Leg 182 in the Great Australian Bight have high concentrations of microbially-generated methane and hydrogen sulfide throughout almost 500 m of sediments. In these cores, the sulfate-reducing and methanogenic zones overlap completely; that is, the usual sulfate-methane transition zone is absent. Amino acid racemization data show that the gassy sediments consist of younger carbonates than the low-gas sites. High concentrations of the reduced gases also occur in two ODP sites on the margin of the Bahamas platform, both of which have similar sedimentary conditions to those of the high-gas sites of Leg 182. Co-generation of these reduced gases results from an unusual combination of conditions, including: (1) a thick Quaternary sequence of iron-poor carbonate sediments, (2) a sub-seafloor brine, and (3) moderate amounts of organic carbon. The probable explanation for the co-generation of hydrogen sulfide and methane in all these sites, as well as in other reported environments, is that methanogens are utilizing non-competitive substrates to produce methane within the sulfate-reducing zone. Taken together, these results form the basis of a new model for sulfate reduction and methanogenesis in marine sediments. The biogeochemical end-members of the model are: (1) minimal sulfate reduction, (2) complete sulfate reduction followed by methanogenesis, and (3) overlapping sulfate reduction and methanogenesis with no transition zone.

(Table 1) Determined and theoretical chemical composition of thaumasite of ODP Hole 135-841B

Hole 841B was drilled in the forearc region of the Lau Basin at a water depth of 4810 m. The hole penetrated a roughly 500-m-thick series of Miocene volcanic sediments with a number of basaltic to andesitic units (sills?) varying in thickness between 7 cm and 17 m. The volcanics are slightly to moderately altered and contain analcite, chabazite, natrolite-thompsonite, heulandite (?), prehnite, and quartz as secondary phases. In addition, thaumasite [Ca3Si(OH)6 * 12H2O](SO4)(CO3) was identified in the altered sequence. Sulfur isotope data of two thaumasite separates (+23.5 per mil and +21.1 per mil d34S) indicate a seawater origin of the sulfate sulfur. It is suggested that thaumasite is a product of low-temperature (<60 °C), seawater-derived CaCl2-rich fluids that were almost identical in composition to those presently circulating in the sub-seafloor.

Rare earth element concentrations and geochemistry of carbonate minerals from the Logatchev Hydrothermal Field and the Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like 87Sr/86Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~100 °C), and yet its 87Sr/86Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine-talc fault schists form north of the LHF. These calcites show unradiogenic 87Sr/86Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.

(Table S1) Trace element and isotopic compositions of anhydrites sampled in the Manus Basin, Papua New Guinea

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REEN patterns measured in anhydrite from mid-ocean ridge deposits. The REEN patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. 87Sr/86Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate d34S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate d34S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO2 degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.

Soil, snow, weather, and sub-surface storage data from a mountain catchment in the rain-snow transition zone

A comprehensive hydroclimatic data set is presented for the 2011 water year to improve understanding of hydrologic processes in the rain-snow transition zone. This type of dataset is extremely rare in scientific literature because of the quality and quantity of soil depth, soil texture, soil moisture, and soil temperature data. Standard meteorological and snow cover data for the entire 2011 water year are included, which include several rain-on-snow events. Surface soil textures and soil depths from 57 points are presented as well as soil texture profiles from 14 points. Meteorological data include continuous hourly shielded, unshielded, and wind corrected precipitation, wind speed, air temperature, relative humidity, dew point temperature, and incoming solar and thermal radiation data. Sub-surface data included are hourly soil moisture data from multiple depths from 7 soil profiles within the catchment, and soil temperatures from multiple depths from 2 soil profiles. Hydrologic response data include hourly stream discharge from the catchment outlet weir, continuous snow depths from one location, intermittent snow depths from 5 locations, and snow depth and density data from ten weekly snow surveys. Though it represents only a single water year, the presentation of both above and below ground hydrologic condition makes it one of the most detailed and complete hydro-climatic datasets from the climatically sensitive rain-snow transition zone for a wide range of modeling and descriptive studies.