Sulfide remobilization during low temperature alteration of seafloor basalt

The behavior of sulfide minerals during the physical and chemical changes accompanying seafloor alteration was studied in three basalt flows from the bottom of D.S.D.P. Hole 418A, Leg 53. The rocks are mildly altered, and contain primary, authigenic, and vein sulfide minerals. Sulfide habit, mineralogy, and trace element content are inter-related and are correlated with the extent and type of silicate and oxide alteration. Incipient alteration at > 90°–100°C was accompanied by low temperature reequilibration of pyrrhotite, and locally, by the oxidation of pyrrhotite to pyrite plus magnetite. The dominant stage of alteration, at ≤90°C, is characterized by dissolution and local redistribution of pyrite and chalcopyrite, whose precipitation appears to be controlled by the water/rock ratio and the extent to which the water has been modified by reaction with the basalt. Chalcopyrite was concentrated relative to pyrite by slight changes in fluid composition caused by reaction with other minerals. Concurrent precipitation of smectite causes a net increase in rock volume, tending to restrict seawater access. Calculations of rock cooling rate through time suggest that the most prolonged hydrothermal circulation occurs at low temperatures, giving rise to pervasive low temperature alteration assemblages.     

Authigenic carbonate precipitates from the NE Black Sea: a mineralogical,geochemical, and lipid biomarker study

Carbonate precipitates recovered from 2,000 m water depth at the Dolgovskoy Mound (Shatsky Ridge, north eastern Black Sea) were studied using mineralogical, geochemical and lipid biomarker analyses. The carbonates differ in shape from simple pavements to cavernous structures with thick microbial mats attached to their lower side and within cavities. Low δ¹³C values measured on carbonates (−41 to −32‰ V-PDB) and extracted lipid biomarkers indicate that anaerobic oxidation of methane (AOM) played a crucial role in precipitating these carbonates. The internal structure of the carbonates is dominated by finely laminated coccolith ooze and homogeneous clay layers, both cemented by micritic high-magnesium calcite (HMC), and pure, botryoidal, yellowish low-magnesium calcite (LMC) grown in direct contact to microbial mats. δ¹⁸O measurements suggest that the authigenic HMC precipitated in equilibrium with the Black Sea bottom water while the yellowish LMC rims have been growing in slightly ¹⁸O-depleted interstitial water. Although precipitated under significantly different environmental conditions, especially with respect to methane availability, all analysed carbonate samples show lipid patterns that are typical for ANME-1 dominated AOM consortia, in the case of the HMC samples with significant contributions of allochthonous components of marine and terrestrial origin, reflecting the hemipelagic nature of the primary sediment.     

Daily variability of dissolved inorganic radiocarbon at three sites in the surface ocean

We report radiocarbon measurements of dissolved inorganic carbon (DIC) in surface water samples collected daily during cruises to the central North Pacific, the Sargasso Sea and the Southern Ocean. The ranges of Δ¹⁴C measurements for each cruise (11–30‰) were larger than the total uncertainty (7.8‰, 2-sigma) of the measurements. The variability is attributed to changes in the upper water mass that took place at each site over a two to four week period. These results indicate that variability of surface Δ¹⁴C values is larger than the analytical precision, because of patchiness that exists in the DIC Δ¹⁴C signature of the surface ocean. This additional variability can affect estimates of geochemical parameters such as the air–sea CO₂ exchange rate using radiocarbon.     

Modeling regional landslide susceptibility using dynamic soil moisture profiles

A landslide susceptibility mapping study was performed using dynamic hillslope hydrology. The modified infinite slope stability model that directly includes vadose zone soil moisture (SM) was applied at Cleveland Corral, California, US and Krishnabhir, Dhading, Nepal. The variable infiltration capacity (VIC-3L) model simulated vadose zone soil moisture and the wetness index hydrologic model simulated groundwater (GW). The GW model predictions had a 75% NASH-Sutcliffe efficiency when compared to California’s in-situ GW measurements. The model performed best during the wet season. Using predicted GW and VIC-3L vadose zone SM, the developed landslide susceptibility maps showed very good agreement with mapped landslides at each study region. Previous quasi-dynamic model predictions of Nepal’s hazardous areas during extreme rainfall events were enhanced to improve the spatial characterization and provide the timing of hazardous conditions.     

Transformation of dilative and contractive landslide debris into debris flows—An example from marin County, California

The severe rainstorm of January 3, 4 and 5, 1982, in the San Francisco Bay area, California, produced numerous landslides, many of which transformed into damaging debris flows. The process of transformation was studied in detail at one site where only part of a landslide mobilized into several episodes of debris flow. The focus of our investigation was to learn whether the landslide debris dilated or contracted during the transformation from slide to flow.

The landslide debris consisted of sandy colluvium that was separable into three soil horizons that occupied the axis of a small topographic swale. Failure involved the entire thickness of colluvium; however, over parts of the landslide, the soil A-horizon failed separately from the remainder of the colluvium.

Undisturbed samples were taken for density measurements from outside the landslide, from the failure zone and overlying material from the part of the landslide that did not mobilize into debris flows, and from the debris-flow deposits. The soil A-horizon was contractive and mobilized to flows in a process analogous to liquefaction of loose, granular soils during earthquakes. The soil B- and C-horizons were dilative and underwent 2 to 5% volumetric expansion during landslide movement that permitted mobilization of debris-flow episodes.

Several criteria can be used in the field to differentiate between contractive and dilative behavior including lag time between landsliding and mobilization of flow, episodic mobilization of flows, and partial or complete transformation of the landslide.     

Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ∼2-7), with adsorption increasing with pH to a maximum at pH ∼6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO₅H_n)ⁿ⁻⁸ monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1pK basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere RCOOCu⁺ surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K RCOOCu⁺ = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.     

Short chain ladderanes: Oxic biodegradation products of anammox lipids

Anammox, the microbial anaerobic oxidation of ammonium by nitrite to produce dinitrogen gas, has been recognized as a key process in both the marine and freshwater nitrogen cycles, and found to be a major sink for fixed inorganic nitrogen in the oceans. Ladderane lipids are unique anammox bacterial membrane lipids that have been used as biomarkers for anammox bacteria in recent and past environmental settings. However, the fate of ladderane lipids during diagenesis is as of yet unknown. In this study, we performed oxic degradation experiments (at 20-100 °C) with anammox bacterial biomass to simulate early diagenetic processes occurring in the water column and at the sediment-water interface. Abundances of C₁₈ and C₂₀ ladderane lipids decreased with increasing temperatures, testifying to their labile nature. The most abundant products formed were ladderane lipids with a shorter alkyl side chain (C₁₄ and C₁₆ ladderane fatty acids), which was unambiguously established using two-dimensional NMR techniques on an isolated C₁₄-[3]-ladderane fatty acid. The most pronounced production of these short-chain lipids was at 40 °C, suggesting that degradation of ladderane lipids was microbially mediated, likely through a β-oxidation pathway. An HPLC-MS/MS method was developed for the detection of these ladderane alteration products in environmental samples and positively tested on various sediments. This showed that the ladderanes formed during degradation experiments also naturally occur in the marine environment. Thus, short-chain ladderane lipids may complement the original longer-chain ladderane lipids as suitable biomarkers for the detection of anammox processes in past depositional environments.     

Breadth and depth in research on health disparities: commentary on the work of Nancy Krieger

Geocoding and spatial analysis of data describing populations and health events are important methods in health social science now carried out using GIS technology. This commentary considers Nancy Krieger’s work on health disparities in light of the various ways individuals and organizations use geocoded population and health data: analyzing spatial patterns of health and disease including health disparities, aggregating data spatially, assessing health status of individuals based on characteristics of aggregates, modeling neighborhood contextual factors affecting health, designing observation and intervention studies, and delivering health interventions and services. The extent to which her work addresses each of these purposes is considered. The strengths and limitations of the research including choice of spatial analytic units and techniques as reported in the published work are discussed. Krieger’s work, with her colleagues, has used standard methods of spatial analysis to raise the profile of GIS and spatial analysis in the public health community.     

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.