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USGS2009

Stable isotope and petrologic evidence for open-system degassing during the climactic and pre-climactic eruptions of Mt. Mazama, Crater Lake, Oregon

Evaluation of the extent of volatile element recycling in convergent margin volcanism requires delineating likely source(s) of magmatic volatiles through stable isotopic characterization of sulfur, hydrogen and oxygen in erupted tephra with appropriate assessment of modification by degassing. The climactic eruption of Mt. Mazama ejected approximately 50 km 3 of rhyodacitic magma into the atmosphere and resulted in formation of a 10-km diameter caldera now occupied by Crater Lake, Oregon (lat. 43°N, long. 122°W). Isotopic compositions of whole-rocks, matrix glasses and minerals from Mt. Mazama climactic, pre-climactic and postcaldera tephra were determined to identify the likely source(s) of H 2 O and S. Integration of stable isotopic data with petrologic data from melt inclusions has allowed for estimation of pre-eruptive dissolved volatile concentrations and placed constraints on the extent, conditions and style of degassing. Sulfur isotope analyses of climactic rhyodacitic whole rocks yield δ 34 S values of 2.8–14.8‰ with corresponding matrix glass values of 2.4–13.2‰. δ 34 S tends to increase with stratigraphic height through climactic eruptive units, consistent with open-system degassing. Dissolved sulfur concentrations in melt inclusions (MIs) from pre-climactic and climactic rhyodacitic pumices varies from 80 to 330 ppm, with highest concentrations in inclusions with 4.8–5.2 wt% H 2 O (by FTIR). Up to 50% of the initial S may have been lost through pre-eruptive degassing at depths of 4–5 km. Ion microprobe analyses of pyrrhotite in climactic rhyodacitic tephra and andesitic scoria indicate a range in δ 34 S from −0.4‰ to 5.8‰ and from −0.1‰ to 3.5‰, respectively. Initial δ 34 S values of rhyodacitic and andesitic magmas were likely near the mantle value of 0‰. Hydrogen isotope (δD) and total H 2 O analyses of rhyodacitic obsidian (and vitrophyre) from the climactic fall deposit yielded values οf −103 to −53‰ and 0.23–1.74 wt%, respectively. Values of δD and wt% H 2 O of obsidian decrease towards the top of the fall deposit. Samples with depleted δD, and mantle δ 18 O values, have elevated δ 34 S values consistent with open-system degassing. These results imply that more mantle-derived sulfur is degassed to the Earth’s atmosphere/hydrosphere through convergent margin volcanism than previously attributed. Magmatic degassing can modify initial isotopic compositions of sulfur by >14‰ (to δ 34 S values of 14‰ or more here) and hydrogen isotopic compositions by 90‰ (to δD values of −127‰ in this case).

Oregon↗
USGS2009

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California. Part II: Solute profiles, gradients and the comparisons of contemporary and long-term weathering rates

The spatial and temporal changes in hydrology and pore water elemental and 87 Sr/ 86 Sr compositions are used to determine contemporary weathering rates in a 65- to 226-kyr-old soil chronosequence formed from granitic sediments deposited on marine terraces along coastal California. Soil moisture, tension and saturation exhibit large seasonal variations in shallow soils in response to a Mediterranean climate. These climate effects are dampened in underlying argillic horizons that progressively developed in older soils, and reached steady-state conditions in unsaturated horizons extending to depths in excess of 15 m. Hydraulic fluxes (q h ), based on Cl mass balances, vary from 0.06 to 0.22 m yr -1 , resulting in fluid residence times in the terraces of 10-24 yrs. As expected for a coastal environment, the order of cation abundances in soil pore waters is comparable to sea water, i.e., Na > Mg > Ca > K > Sr, while the anion sequence Cl > NO 3 > HCO 3 > SO 4 reflects modifying effects of nutrient cycling in the grassland vegetation. Net Cl-corrected solute Na, K and Si increase with depth, denoting inputs from feldspar weathering. Solute 87 Sr/ 86 Sr ratios exhibit progressive mixing of sea water-dominated precipitation with inputs from less radiogenic plagioclase. While net Sr and Ca concentrations are anomalously high in shallow soils due to biological cycling, they decline with depth to low and/or negative net concentrations. Ca/Mg, Sr/Mg and 87 Sr/ 86 Sr solute and exchange ratios are similar in all the terraces, denoting active exchange equilibration with selectivities close to unity for both detrital smectite and secondary kaolinite. Large differences in the magnitudes of the pore waters and exchange reservoirs result in short-term buffering of the solute Ca, Sr, and Mg. Such buffering over geologic time scales can not be sustained due to declining inputs from residual plagioclase and smectite, implying periodic resetting of the exchange reservoir such as by past vegetational changes and/or climate. Pore waters approach thermodynamic saturation with respect to albite at depth in the younger terraces, indicating that weathering rates ultimately become transport-limited and dependent on hydrologic flux. Contemporary rates R solute are estimated from linear Na and Si pore weathering gradients b solute such that R solute = frac(q h , b solute ?? S v ) where S v is the volumetric surface area and ?? is the stoichiometric coefficient. Plagioclase weathering rates (0.38-2.8 ?? 10 -15 mol m -2 s -1 ) are comparable to those based on 87 Sr/ 86 Sr mass balances and solid-state Na and Ca gradients using analogous gradient approximations. In addition, contemporary solute gradients, under transport-limited conditions, approximate long-term solid-state gradients when normalized against the mass of protolith plagioclase and its corresponding aqueous solubility. The multi-faceted weathering analysis presented in this paper is perhaps the most comprehensive yet applied to a single field study. Within uncertainties of the methods used, present day weathering rates, based on solute characterizations, are comparable to average long-term past rates as evidenced by soil profiles.

Geochimica et Cosmochimica Acta↗
USGS2009

Modern U-Pb chronometry of meteorites: advancing to higher time resolution reveals new problems

In this paper, we evaluate the factors that influence the accuracy of lead (Pb)-isotopic ages of meteorites, and may possibly be responsible for inconsistencies between Pb-isotopic and extinct nuclide timescales of the early Solar System: instrumental mass fractionation and other possible analytical sources of error, presence of more than one component of non-radiogenic Pb, migration of ancient radiogenic Pb by diffusion and other mechanisms, possible heterogeneity of the isotopic composition of uranium (U), uncertainties in the decay constants of uranium isotopes, possible presence of "freshly synthesized" actinides with short half-life (e.g. 234 U) in the early Solar System, possible initial disequilibrium in the uranium decay chains, and potential fractionation of radiogenic Pb isotopes and U isotopes caused by alpha-recoil and subsequent laboratory treatment. We review the use of 232 Th/ 238 U values to assist in making accurate interpretations of the U-Pb ages of meteorite components. We discuss recently published U-Pb dates of calcium-aluminum-rich inclusions (CAIs), and their apparent disagreement with the extinct nuclide dates, in the context of capability and common pitfalls in modern meteorite chronology. Finally, we discuss the requirements of meteorites that are intended to be used as the reference points in building a consistent time scale of the early Solar System, based on the combined use of the U-Pb system and extinct nuclide chronometers.

Geochimica et Cosmochimica Acta↗
USGS2009

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

The kinetics of iodide (I − ) and molecular iodine (I 2 ) oxidation by the manganese oxide mineral birnessite (δ-MnO 2 ) was investigated over the pH range 4.5–6.25. I − oxidation to iodate ( IO 3 - ) "> (IO3-) proceeded as a two-step reaction through an I 2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I − from solution was first order with respect to I − concentration, pH, and birnessite concentration, such that − d [I − ]/ dt = k [I − ][H + ][MnO 2 ], where k , the third order rate constant, is equal to 1.08 ± 0.06 × 10 7 M −2 h −1 . The data are consistent with the formation of an inner sphere I − surface complex as the first step of the reaction, and the adsorption of I − exhibited significant pH dependence. Both I 2 , and to a lesser extent, IO 3 - "> IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I 2 and IO 3 - "> IO3- , as well as the biophilic nature of I 2 , redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

Geochimica et Cosmochimica Acta↗
USGS2009

The stable carbon isotope biogeochemistry of acetate and other dissolved carbon species in deep subseafloor sediments at the northern Cascadia Margin

Ocean drilling has revealed the existence of vast microbial populations in the deep subseafloor, but to date little is known about their metabolic activities. To better understand the biogeochemical processes in the deep biosphere, we investigate the stable carbon isotope chemistry of acetate and other carbon-bearing metabolites in sediment pore-waters. Acetate is a key metabolite in the cycling of carbon in anoxic sediments. Its stable carbon isotopic composition provides information on the metabolic processes dominating acetate turnover in situ. This study reports our findings for a methane-rich site at the northern Cascadia Margin (NE Pacific) where Expedition 311 of the Integrated Ocean Drilling Program (IODP) sampled the upper 190 m of sediment. At Site U1329, δ 13 C values of acetate span a wide range from −46.0‰ to −11.0‰ vs. VPDB and change systematically with sediment depth. In contrast, δ 13 C values of both the bulk dissolved organic carbon (DOC) (−21.6 ± 1.3‰ vs. VPDB) and the low-molecular-weight compound lactate (−20.9 ± 1.8‰ vs. VPDB) show little variability. These species are interpreted to represent the carbon isotopic composition of fermentation products. Relative to DOC, acetate is up to 23.1‰ depleted and up to 9.1‰ enriched in 13 C. Broadly, 13 C-depletions of acetate relative to DOC indicate flux of carbon from acetogenesis into the acetate pool while 13 C-enrichments of pore-water acetate relative to DOC suggest consumption of acetate by acetoclastic methanogenesis. Isotopic relationships between acetate and lactate or DOC provide new information on the carbon flow and the presence and activity of specific functional microbial communities in distinct biogeochemical horizons of the sediment. In particular, they suggest that acetogenic CO 2 -reduction can coexist with methanogenic CO 2 -reduction, a notion contrary to the hypothesis that hydrogen levels are controlled by the thermodynamically most favorable electron-accepting process. Further, the isotopic relationship suggests a relative increase in acetate flow to acetoclastic methanogenesis with depth although its contribution to total methanogenesis is probably small. Our study demonstrates how the stable carbon isotope biogeochemistry of acetate can be used to identify pathways of microbial carbon turnover in subsurface environments. Our observations also raise new questions regarding the factors controlling acetate turnover in marine sediments.

Geochimica et Cosmochimica Acta↗
USGS2009

Determination of diffusion coefficients of hydrogen in fused silica between 296 and 523 K by Raman spectroscopy and application of fused silica capillaries in studying redox reactions

Diffusion coefficients ( D ) of hydrogen in fused silica capillaries (FSC) were determined between 296 and 523 K by Raman spectroscopy using CO 2 as an internal standard. FSC capsules (3.25 × 10 −4 m OD, 9.9 × 10 −5 m ID, and ∼0.01 m long) containing CO 2 and H 2 were prepared and the initial relative concentrations of hydrogen in these capsules were derived from the Raman peak-height ratios between H 2 (near 587 cm −1 ) and CO 2 (near 1387 cm −1 ). The sample capsules were then heated at a fixed temperature ( T ) at one atmosphere to let H 2 diffuse out of the capsule, and the changes of hydrogen concentration were monitored by Raman spectroscopy after quench. This process was repeated using different heating durations at 296 (room T ), 323, 375, 430, 473, and 523 K; the same sample capsule was used repeatedly at each temperature. The values of D (in m 2 s −1 ) in FSC were obtained by fitting the observed changes of hydrogen concentration in the FSC capsule to an equation based on Fick’s law. Our D values are in good agreement with the more recent of the two previously reported experimental data sets, and both can be represented by: ln D = - ( 16.471 ± 0.035 ) - 44589 ± 139 RT ( R 2 = 0.99991 ) "> lnD=-(16.471±0.035)-44589±139RT(R2=0.99991) where R is the gas constant (8.3145 J/mol K), T in Kelvin, and errors at 1 σ level. The slope corresponds to an activation energy of 44.59 ± 0.14 kJ/mol. The D in FSC determined at 296 K is about an order of magnitude higher than that in platinum at 723 K, indicating that FSC is a suitable membrane for hydrogen at temperature between 673 K and room temperature, and has a great potential for studying redox reactions at these temperatures, especially for systems containing organic material and/or sulphur.

Geochimica et Cosmochimica Acta↗
USGS2009

Investigation of thallium fluxes from subaerial volcanism-Implications for the present and past mass balance of thallium in the oceans

A suite of 34 volcanic gas condensates and particulates from Kilauea (Hawaii), Mt. Etna and Vulcano (Italy), Mt. Merapi (Indonesia), White Island and Mt. Nguaruhoe (New Zealand) were analysed for both Tl isotope compositions and Tl/Pb ratios. When considered together with published Tl–Pb abundance data, the measurements provide globally representative best estimates of Tl/Pb = 0.46 ± 0.25 and ε 205 Tl = −1.7 ± 2.0 for the emissions of subaerial volcanism to the atmosphere and oceans (ε 205 Tl is the deviation of the 205 Tl/ 203 Tl isotope ratio from NIST SRM 997 isotope standard in parts per 10,000). Compared to igneous rocks of the crust and mantle, volcanic gases were found to have (i) Tl/Pb ratios that are typically about an order of magnitude higher, and (ii) significantly more variable Tl isotope compositions but a mean ε 205 Tl value that is indistinguishable from estimates for the Earth’s mantle and continental crust. The first observation can be explained by the more volatile nature of Tl compared to Pb during the production of volcanic gases, whilst the second reflects the contrasting and approximately balanced isotope fractionation effects that are generated by partial evaporation of Tl during magma degassing and partial Tl condensation as a result of the cooling and differentiation of volcanic gases.

Geochimica et Cosmochimica Acta↗
USGS2009

Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating

Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., 2 H/ 1 H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., {single bond}OH, {single bond}COOH, {single bond}NH 2 ). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ???2.5 to ???3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong ?? 13 C kerogen vs. ?? 15 N kerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back-reactions between mobile pyrolysis products from the hot zone as they encounter less hot kerogen. Vein and cell filling carbonate is most abundant in highest rank coals where carbonate ?? 13 C VPDB and ?? 18 O VSMOW values are consistent with thermal generation of 13 C-depleted and 18 O-enriched CO 2 from decarboxylation and pyrolysis of organic matter. Lower background concentrations of 13 C-enriched carbonate in thermally unaffected coal may be linked to 13 C-enrichment in residual CO 2 in the process of CO 2 reduction via microbial methanogenesis. Our compilation and comparison of available organic H, C, N isotopic findings on magmatic intrusions result in re-assessments of majors factors influencing isotopic shifts in kerogen during magmatic heating. (i) Thermally induced shifts in organic ??D values of kerogen are primarily driven by the availability of water or steam. Hydrologic isolation (e.g., near Illinois dikes) results in organic D-depletion in kerogen, whereas more common hydrologic connectivity results in organic D-enrichment. (ii) Shifts in kerogen (or coal) ?? 13 C and ?? 15 N values are typically small and may follow sinusoidal patterns over short distances from magmatic contacts. Laterally limited sampling strategies may thus result in misleading and non-representative data. (iii) Fluid transport of chemically active, mobile carbon and nitrogen species and recombination reactions with kerogen result in isotopic changes in kerogen that are unrelated to the original, autochthonous part of kerogen. ?? 2009 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta↗
USGS2009

Diamond dissolution and the production of methane and other carbon-bearing species in hydrothermal diamond-anvil cells

Raman analysis of the vapor phase formed after heating pure water to near critical (355–374 °C) temperatures in a hydrothermal diamond-anvil cell (HDAC) reveals the synthesis of abiogenic methane. This unexpected result demonstrates the chemical reactivity of diamond at relatively low temperatures. The rate of methane production from the reaction between water and diamond increases with increasing temperature and is enhanced by the presence of a metal gasket (Re, Ir, or Inconel) which is compressed between the diamond anvils to seal the aqueous sample. The minimum detection limit for methane using Raman spectroscopy was determined to be ca . 0.047 MPa, indicating that more than 1.4 nanograms (or 8.6 × 10 −11 mol) of methane were produced in the HDAC at 355 °C and 30 MPa over a period of ten minutes. At temperatures of 650 °C and greater, hydrogen and carbon dioxide were detected in addition to methane. The production of abiogenic methane, observed in all HDAC experiments where a gasket was used, necessitates a reexamination of the assumed chemical systems and intensive parameters reported in previous hydrothermal investigations employing diamonds. The results also demonstrate the need to minimize or eliminate the production of methane and other carbonic species in experiments by containing the sample within a HDAC without using a metal gasket.

Geochimica et Cosmochimica Acta↗
USGS2009

Oxygen and hydrogen isotope fractionation in serpentine-water and talc-water systems from 250 to 450 °C, 50 MPa

Oxygen and hydrogen isotope fractionation factors in the talc–water and serpentine–water systems have been determined by laboratory experiment from 250 to 450 °C at 50 MPa using the partial exchange technique. Talc was synthesized from brucite + quartz, resulting in nearly 100% exchange during reaction at 350 and 450 °C. For serpentine, D–H exchange was much more rapid than 18 O– 16 O exchange when natural chrysotile fibers were employed in the initial charge. In experiments with lizardite as the starting charge, recrystallization to chrysotile enhanced the rate of 18 O– 16 O exchange with the coexisting aqueous phase. Oxygen isotope fractionation factors in both the talc–water and serpentine–water systems decrease with increasing temperature and can be described from 250 to 450 °C by the relationships: 1000 ln = 11.70 × 10 6 /T 2 − 25.49 × 10 3 /T + 12.48 and 1000 ln = 3.49 × 10 6 /T 2 − 9.48 where T is temperature in Kelvin. Over the same temperature interval at 50 MPa, talc–water D–H fractionation is only weakly dependent on temperature, similar to brucite and chlorite, and can be described by the equation: 1000 ln = 10.88 × 10 6 /T 2 − 41.52 × 10 3 /T + 5.61 where T is temperature in Kelvin. Our D–H serpentine–water fractionation factors calibrated by experiment decrease with temperature and form a consistent trend with fractionation factors derived from lower temperature field calibrations. By regression of these data, we have refined and extended the D–H fractionation curve from 25 to 450 °C, 50 MPa as follows: 1000 ln = 3.436 × 10 6 /T 2 − 34.736 × 10 3 /T + 21.67 where T is temperature in Kelvin. These new data should improve the application of D–H and 18 O– 16 O isotopes to constrain the temperature and origin of hydrothermal fluids responsible for serpentine formation in a variety of geologic settings.

Geochimica et Cosmochimica Acta↗
USGS2010

Mineralogical and chemical characteristics of some natural jarosites

This paper presents a detailed study of the mineralogical, microscopic, thermal, and spectral characteristics of jarosite and natrojarosite minerals. Systematic mineralogic and chemical examination of a suite of 32 natural stoichiometric jarosite and natrojarosite samples from diverse supergene and hydrothermal environments indicates that there is only limited solid solution between Na and K at low temperatures, which suggests the presence of a solvus in the jarosite-natrojarosite system at temperatures below about 140 C. The samples examined in this study consist of either end members or coexisting end-member pairs of jarosite and natrojarosite. Quantitative electron-probe microanalysis data for several natural hydrothermal samples show only end-member compositions for individual grains or zones, and no detectable alkali-site deficiencies, which indicates that there is no hydronium substitution within the analytical uncertainty of the method. In addition, there is no evidence of Fe deficiencies in the natural hydrothermal samples. Hydronium-bearing jarosite was detected in only one relatively young supergene sample suggesting that terrestrial hydronium-bearing jarosites generally are unstable over geologic timescales. Unit-cell parameters of the 20 natural stoichiometric jarosites and 12 natural stoichiometric natrojarosites examined in this study have distinct and narrow ranges in the a- and c-cell dimensions. There is no overlap of these parameters at the 1r level for the two end-member compositions. Several hydrothermal samples consist of fine-scale (2–10 lm) intimate intergrowths of jarosite and natrojarosite, which could have resulted from solid-state diffusion segregation or growth zoning due to variations in the Na/K activity ratio of hydrothermal solutions.

Geochimica et Cosmochimica Acta↗
USGS2010

Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state 13 C NMR spectroscopy

We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R 0 from 0.29% to 1.27%). Specific functional groups such as CH 3 , CH 2 , alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as "oil prone" and "gas prone" carbons, have been quantified by 13 C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (???30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ???30 carbons, and of ???20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range 1 H- 13 C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters. ?? 2010 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta↗
USGS2010

Microbial carbon cycling in oligotrophic regional aquifers near the Tono Uranium Mine, Japan as inferred from δ13C and Δ14C values of in situ phospholipid fatty acids and carbon sources

Microorganisms are ubiquitous in deep subsurface environments, but their role in the global carbon cycle is not well-understood. The natural abundance δ 13 C and Δ 14 C values of microbial membrane phospholipid fatty acids (PLFAs) were measured and used to assess the carbon sources of bacteria in sedimentary and granitic groundwaters sampled from three boreholes in the vicinity of the Tono Uranium Mine, Gifu, Japan. Sample storage experiments were performed and drill waters analyzed to characterize potential sources of microbial contamination. The most abundant PLFA structures in all waters sampled were 16:0, 16:1ω7 c , cy 17:0, and 18:1ω7 c . A PLFA biomarker for type II methanotrophs, 18:1ω8 c , comprised 3% and 18% of total PLFAs in anoxic sedimentary and granitic waters, respectively, sampled from the KNA-6 borehole. The presence of this biomarker was unexpected given that type II methanotrophs are considered obligate aerobes. However, a bacterium that grows aerobically with CH 4 as the sole energy source and which also produces 56% of its total PLFAs as 18:1ω8 c was isolated from both waters, providing additional evidence for the presence of type II methanotrophs. The Δ 14 C values determined for type II methanotroph PLFAs in the sedimentary (−861‰) and granite (−867‰) waters were very similar to the Δ 14 C values of dissolved inorganic carbon (DIC) in each water (∼−850‰). This suggests that type II methanotrophs ultimately derive all their carbon from inorganic sources, whether directly from DIC and/or from CH 4 produced by the reduction of DIC. In contrast, δ 13 C values of type II PLFAs in the sedimentary (−93‰) and granite (−60‰) waters indicate that these organisms use different carbon assimilation schemes in each environment despite very similar δ 13 C CH 4 "> δ13CCH4 values (∼−95‰) for each water. The δ 13 C PLFA values (−28‰ to −45‰) of non-methanotrophic bacteria in the KNA-6 LTL water do not clearly distinguish between heterotrophic and autotrophic metabolisms, but Δ 14 C PLFA values indicate that >65% of total bacteria filtered from the KNA-6 LTL water are heterotrophs. Ancient Δ 14 C values (∼−1000‰) of some PLFAs suggest that many heterotrophs utilize ancient organic matter, perhaps from lignite seams within the sedimentary rocks. The more negative range of δ 13 C PLFA values determined for the KNA-6 granitic water (−42‰ to −66‰) are likely the result of a microbial ecosystem dominated by chemolithoautotrophy, perhaps fuelled by abiogenic H 2 . Results of sample storage experiments showed substantial shifts in microbial community composition and δ 13 C PLFA values (as much as 5‰) during 2–4 days of dark, refrigerated, aseptic storage. However, water samples collected and immediately filtered back in the lab from freshly drilled MSB-2 borehole appeared to maintain the same relative relationships between δ 13 C PLFA values for sedimentary and granitic host rocks as observed for samples directly filtered under artesian flow from the KNA-6 borehole of the Tono Uranium Mine.

Tono Uranium Mine↗
USGS2010

Mg isotope constraints on soil pore-fluid chemistry: Evidence from Santa Cruz, California

Mg isotope ratios ( 26 Mg/ 24 Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant 26 Mg/ 24 Mg ratio (expressed as δ26 Mg> δ26 Mg ) at −0.79 ± 0.05‰, identical to seawater δ26 Mg> δ26 Mg . Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ26Mg"> δ26Mg value of 0.11‰, potentially enriched in 26 Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ26 Mg> δ26 Mg , ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ26 Mg> δ26 Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain ( δ26 Mggrass- δ26 Mgrain> δ26 Mggrass- δ26 Mgrain ) of 0.21‰. The deep pore-waters (1–15 m deep) have δ26 Mg> δ26 Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of 24 Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.

California↗
USGS2010

Rate of formation and dissolution of mercury sulfide nanoparticles: The dual role of natural organic matter

Mercury is a global contaminant of concern due to its transformation by microorganisms to form methylmercury, a toxic species that accumulates in biological tissues. The effect of dissolved organic matter (DOM) isolated from natural waters on reactions between mercury(II) (Hg) and sulfide (S(-II)) to form HgS (s) nanoparticles across a range of Hg and S(-II) concentrations was investigated. Hg was equilibrated with DOM, after which S(-II) was added. Dissolved Hg (Hg aq ) was periodically quantified using ultracentrifugation and chemical analysis following the addition of S(-II). Particle size and identity were determined using dynamic light scattering and X-ray absorption spectroscopy. S(-II) reacts with Hg to form 20 to 200nm aggregates consisting of 1-2 nm HgS (s) subunits that are more structurally disordered than metacinnabar in the presence of 2 x 10 -9 to 8 x 10 -6 M Hg and 10 (mg C)L -1 DOM. Some of the HgS(s) nanoparticle aggregates are subsequently dissolved by DOM and (re)precipitated by S(-II) over periods of hours to days. At least three fractions of Hg-DOM species were observed with respect to reactivity toward S(-II): 0.3 &mu;mol reactive Hg per mmol C (60 percent), 0.1 &mu;mol per mmol C (20 percent) that are kinetically hindered, and another 0.1 &mu;mol Hg per mmol C (20 percent) that are inert to reaction with S(-II). Following an initial S(-II)-driven precipitation of HgS (s) , HgS (s) was dissolved by DOM or organic sulfur compounds. HgS (s) formation during this second phase was counterintuitively favored by lower S(-II) concentrations, suggesting surface association of DOM moieties that are less capable of dissolving HgS (s) . DOM partially inhibits HgS(s) formation and mediates reactions between Hg and S(-II) such that HgS (s) is susceptible to dissolution. These findings indicate that Hg accessibility to microorganisms could be controlled by kinetic (intermediate) species in the presence of S(-II) and DOM, undermining the premise that equilibrium Hg species distributions should correlate to the extent or rate of Hg methylation in soils and sediments.

Geochimica et Cosmochimica Acta↗
USGS2010

Influence of sea level rise on iron diagenesis in an east Florida subterranean estuary

Subterranean estuary occupies the transition zone between hypoxic fresh groundwater and oxic seawater, and between terrestrial and marine sediment deposits. Consequently, we hypothesize, in a subterranean estuary, biogeochemical reactions of Fe respond to submarine groundwater discharge (SGD) and sea level rise. Porewater and sediment samples were collected across a 30-m wide freshwater discharge zone of the Indian River Lagoon (Florida, USA) subterranean estuary, and at a site 250 m offshore. Porewater Fe concentrations range from 0.5 μM at the shoreline and 250 m offshore to about 286 μM at the freshwater–saltwater boundary. Sediment sulfur and porewater sulfide maxima occur in near-surface OC-rich black sediments of marine origin, and dissolved Fe maxima occur in underlying OC-poor orange sediments of terrestrial origin. Freshwater SGD flow rates decrease offshore from around 1 to 0.1 cm/day, while bioirrigation exchange deepens with distance from about 10 cm at the shoreline to about 40 cm at the freshwater–saltwater boundary. DOC concentrations increase from around 75 μM at the shoreline to as much as 700 μM at the freshwater–saltwater boundary as a result of labile marine carbon inputs from marine SGD. This labile DOC reduces Fe-oxides, which in conjunction with slow discharge of SGD at the boundary, allows dissolved Fe to accumulate. Upward advection of fresh SGD carries dissolved Fe from the Fe-oxide reduction zone to the sulfate reduction zone, where dissolved Fe precipitates as Fe-sulfides. Saturation models of Fe-sulfides indicate some fractions of these Fe-sulfides get dissolved near the sediment–water interface, where bioirrigation exchanges oxic surface water. The estimated dissolved Fe flux is approximately 0.84 μM Fe/day per meter of shoreline to lagoon surface waters. Accelerated sea level rise predictions are thus likely to increase the Fe flux to surface waters and local primary productivity, particularly along coastlines where groundwater discharges through sediments.

Geochimica et Cosmochimica Acta↗
USGS2011

Geochemistry of hydrothermal fluids from the PACMANUS, Northeast Pual and Vienna Woods hydrothermal fields, Manus Basin, Papua New Guinea

Processes controlling the composition of seafloor hydrothermal fluids in silicic back-arc or near-arc crustal settings remain poorly constrained despite growing evidence for extensive magmatic–hydrothermal activity in such environments. We conducted a survey of vent fluid compositions from two contrasting sites in the Manus back-arc basin, Papua New Guinea, to examine the influence of variations in host rock composition and magmatic inputs (both a function of arc proximity) on hydrothermal fluid chemistry. Fluid samples were collected from felsic-hosted hydrothermal vent fields located on Pual Ridge (PACMANUS and Northeast (NE) Pual) near the active New Britain Arc and a basalt-hosted vent field (Vienna Woods) located farther from the arc on the Manus Spreading Center. Vienna Woods fluids were characterized by relatively uniform endmember temperatures (273–285 °C) and major element compositions, low dissolved CO 2 concentrations (4.4 mmol/kg) and high measured pH (4.2–4.9 at 25 °C). Temperatures and compositions were highly variable at PACMANUS/NE Pual and a large, newly discovered vent area (Fenway) was observed to be vigorously venting boiling (358 °C) fluid. All PACMANUS fluids are characterized by negative &#x3B4; D H 2 O "> δDH 2 O values, in contrast to positive values at Vienna Woods, suggesting substantial magmatic water input to circulating fluids at Pual Ridge. Low measured pH (25 °C) values (∼2.6–2.7), high endmember CO 2 (up to 274 mmol/kg) and negative &#x3B4; 34 S H 2 S "> δ 34 S H2 S values (down to −2.7‰) in some vent fluids are also consistent with degassing of acid-volatile species from evolved magma. Dissolved CO 2 at PACMANUS is more enriched in 13 C (−4.1‰ to −2.3‰) than Vienna Woods (−5.2‰ to −5.7‰), suggesting a contribution of slab-derived carbon. The mobile elements (e.g. Li, K, Rb, Cs and B) are also greatly enriched in PACMANUS fluids reflecting increased abundances in the crust there relative to the Manus Spreading Center. Variations in alkali and dissolved gas abundances with Cl at PACMANUS and NE Pual suggest that phase separation has affected fluid chemistry despite the low temperatures of many vents. In further contrast to Vienna Woods, substantial modification of PACMANUS/NE Pual fluids has taken place as a result of seawater ingress into the upflow zone. Consistently high measured Mg concentrations as well as trends of increasingly non-conservative SO 4 behavior, decreasing endmember Ca/Cl and Sr/Cl ratios with increased Mg indicate extensive subsurface anhydrite deposition is occurring as a result of subsurface seawater entrainment. Decreased pH and endmember Fe/Mn ratios in higher Mg fluids indicate that the associated mixing/cooling gives rise to sulfide deposition and secondary acidity production. Several low temperature (⩽80 °C) fluids at PACMANUS/NE Pual also show evidence for anhydrite dissolution and water–rock interaction (fixation of B) subsequent to seawater entrainment. Hence, the evolution of fluid compositions at Pual Ridge reflects the cumulative effects of water/rock interaction, admixing and reaction of fluids exsolved from silicic magma, phase separation/segregation and seawater ingress into upflow zones.

Manus Basin↗
USGS2011

Reduction of structural Fe(III) in nontronite by methanogen Methanosarcina barkeri

Clay minerals and methanogens are ubiquitous and co-exist in anoxic environments, yet it is unclear whether methanogens are able to reduce structural Fe(III) in clay minerals. In this study, the ability of methanogen Methanosarcina barkeri to reduce structural Fe(III) in iron-rich smectite (nontronite NAu-2) and the relationship between iron reduction and methanogenesis were investigated. Bioreduction experiments were conducted in growth medium using three types of substrate: H 2 /CO 2 , methanol, and acetate. Time course methane production and hydrogen consumption were measured by gas chromatography. M. barkeri was able to reduce structural Fe(III) in NAu-2 with H 2 /CO 2 and methanol as substrate, but not with acetate. The extent of bioreduction, as measured by the 1,10-phenanthroline method, was 7–13% with H 2 /CO 2 as substrate, depending on nontronite concentration (5–10 g/L). The extent was higher when methanol was used as a substrate, reaching 25–33%. Methanogenesis was inhibited by Fe(III) reduction in the H 2 /CO 2 culture, but enhanced when methanol was used. High charge smectite and biogenic silica formed as a result of bioreduction. Our results suggest that methanogens may play an important role in biogeochemical cycling of iron in clay minerals and may have important implications for the global methane budget.

Geochimica et Cosmochimica Acta↗