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USGS2011

Diurnal trends in methylmercury concentration in a wetland adjacent to Great Salt Lake, Utah, USA

A 24-h field experiment was conducted during July 2008 at a wetland on the eastern shore of Great Salt Lake (GSL) to assess the diurnal cycling of methylmercury (MeHg). Dissolved (< 0.45 μm) MeHg showed a strong diurnal variation with consistently decreasing concentrations during daylight periods and increasing concentrations during non-daylight periods. The proportion of MeHg relative to total Hg in the water column consistently decreased with increasing sunlight duration, indicative of photodegradation. During the field experiment, measured MeHg photodegradation rates ranged from 0.02 to 0.06 ng L − 1 h − 1 . Convective overturn of the water column driven by nighttime cooling of the water surface was hypothesized as the likely mechanism to replace the MeHg in the water column lost via photodegradation processes. A hydrodynamic model of the wetland successfully simulated convective overturn of the water column during the field experiment. Study results indicate that daytime monitoring of selected wetlands surrounding GSL may significantly underestimate the MeHg content in the water column. Wetland managers should consider practices that maximize the photodegradation of MeHg during daylight periods.

Utah↗

USGS2011

Experimental determination of the phase boundary between kornelite and pentahydrated ferric sulfate at 0.1MPa

Recent findings of various ferric sulfates on Mars emphasize the importance of understanding the fundamental properties of ferric sulfates at temperatures relevant to that of Martian surface. In this study, the phase boundary between kornelite (Fe2(SO4)3.7H2O) and pentahydrated ferric sulfate (Fe2(SO4)3.5H2O) was experimentally determined using the humidity-buffer technique together with gravimetric measurements and Raman spectroscopy at 0.1MPa in the 36-56??C temperature range. Through the thermodynamic analysis of our experimental data, the enthalpy change (-290.8??0.3kJ/mol) and the Gibbs free energy change (-238.82??0.02kJ/mol) for each water molecule of crystallization in the rehydration of pentahydrated ferric sulfate to kornelite were obtained. ?? 2011 Elsevier B.V.

Chemical Geology↗

USGS2011

Trace and minor element variations and sulfur isotopes in crystalline and colloform ZnS: Incorporation mechanisms and implications for their genesis

Various models have been proposed to explain the formation mechanism of colloform sphalerite, but the origin is still under debate. In order to decipher influences on trace element incorporation and sulfur isotope composition, crystalline and colloform sphalerite from the carbonate-hosted Mississippi-Valley Type (MVT) deposit near Wiesloch, SW Germany, were investigated and compared to sphalerite samples from 52 hydrothermal vein-type deposits in the Schwarzwald ore district, SW Germany to study the influence of different host rocks, formation mechanisms and fluid origin on trace element incorporation. Trace and minor element incorporation in sphalerite shows some correlation to their host rock and/or origin of fluid, gangue, paragenetic minerals and precipitation mechanisms (e.g., diagenetic processes, fluid cooling or fluid mixing). Furthermore, crystalline sphalerite is generally enriched in elements like Cd, Cu, Sb and Ag compared to colloform sphalerite that mainly incorporates elements like As, Pb and Tl. In addition, sulfur isotopes are characterized by positive values for crystalline and strongly negative values for colloform sphalerite. The combination of trace element contents, typical minerals associated with colloform sphalerite from Wiesloch, sulfur isotopes and thermodynamic considerations helped to evaluate the involvement of sulfate-reducing bacteria in water-filled karst cavities. Sulfate-reducing bacteria cause a sulfide-rich environment that leads in case of a metal-rich fluid supply to a sudden oversaturation of the fluid with respect to galena, sphalerite and pyrite. This, however, exactly coincides with the observed crystallization sequence of samples involving colloform sphalerite from the Wiesloch MVT deposit.

Wiesloch↗

USGS2011

Atacamite and paratacamite from the ultramafic-hosted Logatchev seafloor vent field (14°45′N, Mid-Atlantic Ridge)

Atacamite and paratacamite are ubiquitous minerals associated with Cu-rich massive sulfides at the Logatchev hydrothermal field (Mid-Atlantic Ridge). In this work we provide new details on the mineralogy and geochemistry of these basic cupric chlorides. Our data support the notion that atacamite and paratacamite formation at submarine vent fields is an alteration process of hydrothermal Cu-sulfides. Secondary Cu-sulfides (bornite, covellite) are unstable at ambient seawater conditions and will dissolve. Dissolution is focused at the sulfide–seawater contact, leading to release of Fe 2+ and Cu + and formation of residual chalcocite through an intermediate Cu 5 S 4 phase. Most of the released Fe 2+ oxidizes immediately and precipitates as FeOOH directly on the chalcocite rims whereas Cu as chloride complexes (CuCl 2− , CuCl 3 2- ) remains in solution at the same Eh. Cuprous–chloride complexes migrate from the reaction zone and upon increasing Eh precipitate as Cu 2 Cl(OH) 3 . As a consequence of this, the sulfide–seawater reaction interface is clearly marked by thin chalcocite–FeOOH bands and the entire assemblage is mantled by atacamite (or paratacamite). Our mineralogical, petrographic, geochemical and isotopic studies suggest that there are two types of atacamite (and/or paratacamite) depending on their mode of precipitation. Type 1 atacamite precipitated directly on the parent sulfides as evidenced by mantling of the sulfides, absence of detrital mineral grains, a preserved conspicuous positive Eu anomaly and a negligible negative Ce anomaly similar to those of the parent sulfide. In addition, Au concentrations are slightly lower than those of the parent sulfides, which suggest minimal transport of Au-ions after their release from the sulfides. Furthermore, the low content of the rare earth elements implies short contact time with the ambient seawater. The Sr–Nd–Pb-isotopic signatures of type 1 atacamite confirm the genetic association with the parent sulfides and indicate formation spatially very close to the latter. Type 2 atacamite precipitated at some distance from the parent sulfides, which means that the cuprous–chloride complexes have moved away from the sulfide alteration zone before precipitation. The evidence for this is absence of direct association of atacamite with sulfides. In addition, this atacamite contains a substantial proportion of detrital minerals, which implies precipitation in the sediments, distal to the parent sulfides. As a consequence of the detrital impurities the contents of elements like Cr, Cs, Hf, Nb, Rb, Th and Zr are higher than in type 1 atacamite (and/or paratacamite). Au contents are lower than those of type 1 atacamite (and/or paratacamite) which implies prolonged Au transport in solution before precipitation. Furthermore, the rare earth element distribution patterns have no positive Eu anomaly suggesting that the positive Eu anomaly of the parent sulfide has been erased after dissolution and prolonged contact of the fluid with ambient seawater (with negative Eu anomaly). Finally, the Sr–Nd-isotope signature differs from that of the parent sulfide and indicates a considerable terrigenous input.

Chemical Geology↗

USGS2011

Sulfur geochemistry and microbial sulfate reduction during low-temperature alteration of uplifted lower oceanic crust: Insights from ODP Hole 735B

Sulfide petrography plus whole rock contents and isotope ratios of sulfur were measured in a 1.5 km section of oceanic gabbros in order to understand the geochemistry of sulfur cycling during low-temperature seawater alteration of the lower oceanic crust, and to test whether microbial effects may be present. Most samples have low SO 4 /ΣS values (≤ 0.15), have retained igneous globules of pyrrhotite ± chalcopyrite ± pentlandite, and host secondary aggregates of pyrrhotite and pyrite laths in smectite ± iron-oxyhydroxide ± magnetite ± calcite pseudomorphs of olivine and clinopyroxene. Compared to fresh gabbro containing 100–1800 ppm sulfur our data indicate an overall addition of sulfide to the lower crust. Selection of samples altered only at temperatures ≤ 110 °C constrains microbial sulfate reduction as the only viable mechanism for the observed sulfide addition, which may have been enabled by the production of H 2 from oxidation of associated olivine and pyroxene. The wide range in δ 34 S sulfide values (− 1.5 to + 16.3‰) and variable additions of sulfide are explained by variable ε sulfate-sulfide under open system pathways, with a possible progression into closed system pathways. Some samples underwent oxidation related to seawater penetration along permeable fault horizons and have lost sulfur, have high SO 4 /ΣS (≥ 0.46) and variable δ 34 S sulfide (0.7 to 16.9‰). Negative δ 34 S sulfate –δ 34 S sulfide values for the majority of samples indicate kinetic isotope fractionation during oxidation of sulfide minerals. Depth trends in sulfide–sulfur contents and sulfide mineral assemblages indicate a late-stage downward penetration of seawater into the lower 1 km of Hole 735B. Our results show that under appropriate temperature conditions, a subsurface biosphere can persist in the lower oceanic crust and alter its geochemistry.

Chemical Geology↗

USGS2011

Volatile abundances and oxygen isotopes in basaltic to dacitic lavas on mid-ocean ridges: The role of assimilation at spreading centers

Most geochemical variability in MOR basalts is consistent with low- to moderate-pressure fractional crystallization of various mantle-derived parental melts. However, our geochemical data from MOR high-silica glasses, including new volatile and oxygen isotope data, suggest that assimilation of altered crustal material plays a significant role in the petrogenesis of dacites and may be important in the formation of basaltic lavas at MOR in general. MOR high-silica andesites and dacites from diverse areas show remarkably similar major element trends, incompatible trace element enrichments, and isotopic signatures suggesting similar processes control their chemistry. In particular, very high Cl and elevated H2O concentrations and relatively light oxygen isotope ratios (~ 5.8‰ vs. expected values of ~ 6.8‰) in fresh dacite glasses can be explained by contamination of magmas from a component of ocean crust altered by hydrothermal fluids. Crystallization of silicate phases and Fe-oxides causes an increase in δ18O in residual magma, but assimilation of material initially altered at high temperatures results in lower δ18O values. The observed geochemical signatures can be explained by extreme fractional crystallization of a MOR basalt parent combined with partial melting and assimilation (AFC) of amphibole-bearing altered oceanic crust. The MOR dacitic lavas do not appear to be simply the extrusive equivalent of oceanic plagiogranites. The combination of partial melting and assimilation produces a distinct geochemical signature that includes higher incompatible trace element abundances and distinct trace element ratios relative to those observed in plagiogranites.

Chemical Geology↗

USGS2011

Uranium and barium cycling in a salt wedge subterranean estuary: The influence of tidal pumping

The contribution of submarine groundwater discharge (SGD) to oceanic metal budgets is only beginning to be explored. Here, we demonstrate that biogeochemical processes in a northern Florida subterranean estuary (STE) significantly alter U and Ba concentrations entering the coastal ocean via SGD. Tidal pumping controlled the distribution of dissolved metals in shallow beach groundwater. Hourly observations of intertidal groundwaters revealed high U and low Ba concentrations at high tide as a result of seawater infiltration into the coastal aquifer. During ebb tide, U decreased and Ba increased due to freshwater dilution and, more importantly, biogeochemical reactions that removed U and added Ba to solution. U removal was apparently a result of precipitation following the reduction of U(VI) to U(IV). A significant correlation between Ba and dissolved organic carbon (DOC) in shallow beach groundwaters implied a common source, likely the mineralization of marine particulate organic matter driven into the beach face by tidal pumping. In deeper groundwaters, where the labile organic matter had been depleted, Ba correlated with Mn. We estimate that net SGD fluxes were − 163 and + 1660 μmol m − 1 d − 1 for U and Ba, respectively (or − 1 and + 8 μmol m − 2 d − 1 if a 200-m wide seepage area is considered). Our results support the emerging concept that subterranean estuaries are natural biogeochemical reactors where metal concentrations are altered relative to conservative mixing between terrestrial and marine endmembers. These deviations from conservative mixing significantly influence SGD-derived trace metal fluxes.

Florida↗

USGS2011

Mineral transformations associated with goethite reduction by Methanosarcina barkeri

To investigate the interaction between methanogens and iron-containing minerals in anoxic environments, we conducted batch culture experiments with Methanosarcina barkeri in a phosphate-buffered basal medium (PBBM) to bioreduce structural Fe(III) in goethite with hydrogen as the sole substrate. Fe(II) and methane concentrations were monitored over the course of the bioreduction experiments with wet chemistry and gas chromatography, respectively. Subsequent mineralogical changes were characterized with X-ray diffraction (XRD) and scanning electron microscopy (SEM). In the presence of an electron shuttle anthraquinone-2,6-disulfonate (AQDS), 30% Fe(III) in goethite (weight basis) was reduced to Fe(II). In contrast, only 2% Fe(III) (weight basis) was bioreduced in the absence of AQDS. Most of the bioproduced Fe(II) was incorporated into secondary minerals including dufrénite and vivianite. Our data implied a dufrénite–vivianite transformation mechanism where a metastable dufrénite transformed to a more stable vivianite over extended time in anaerobic conditions. Methanogenesis was greatly inhibited by bioreduction of goethite Fe(III). These results have important implications for the methane flux associated with Fe(III) bioreduction and ferrous iron mineral precipitation in anaerobic soils and sediments.

Chemical Geology↗

USGS2011

Calibration of Nu-Instruments Noblesse multicollector mass spectrometers for argon isotopic measurements using a newly developed reference gas

The greatest challenge limiting 40 Ar/ 39 Ar multicollection measurements is the availability of appropriate standard gasses to intercalibrate detectors. In particular, use of zoom lens ion-optics to steer and focus ion beams into a fixed detector array (i.e., Nu Instruments Noblesse) makes intercalibration of multiple detectors challenging because different ion-optic tuning conditions are required for optimal peak shape and sensitivity at different mass stations. We have found that detector efficiency and mass discrimination are affected by changes in ion-optic tuning parameters. Reliance upon an atmospheric Ar standard to calibrate the Noblesse is problematic because there is no straightforward way to relate atmospheric 40 Ar and 36 Ar to measurements of 40 Ar and 39 Ar if they are measured on separate detectors. After exploring alternative calibration approaches, we have concluded that calibration of the Noblesse is best performed using exactly the same source, detector, and ion-optic tuning settings as those used in routine 40 Ar/ 39 Ar analysis. To accomplish this, we have developed synthetic reference gasses containing 40 Ar, 39 Ar and 38 Ar produced by mixing gasses derived from neutron-irradiated sanidine with an enriched 38 Ar spike. We present a new method for calibrating the Noblesse based on use of both atmospheric Ar and the synthetic reference gasses. By combining atmospheric Ar and synthetic reference gas in different ways, we can directly measure 40 Ar/ 39 Ar, 38 Ar/ 39 Ar, and 36 Ar/ 39 Ar correction factors over ratios that vary from 0.5 to 460. These correction factors are reproducible to better than ± 0.5‰ (2σ standard error) over intervals spanning ~ 24 h but can vary systematically by ~ 4% over 2 weeks of continuous use when electron multiplier settings are held constant. Monitoring this variation requires daily calibration of the instrument. Application of the calibration method to 40 Ar/ 39 Ar multicollection measurements of widely used sanidine reference materials ACs-2, FCs-2, and TCs-2 demonstrate that calculated 40 Ar*/ 39 Ar K can be accurately corrected to yield model 40 Ar/ 39 Ar ages consistent with those reported by Earthtime 40 Ar/ 39 Ar laboratories. Replicate analyses of 8–12 single-crystal sanidine ages are reproduced to within 1–2‰ (2σ standard error) under optimal analytical conditions. This calibration technique is applicable over a wide range of isotopic ratios and signal sizes. Finally, the reference gas has the added advantage of facilitating straightforward characterization of electron multiplier dead time over a wide dynamic range.

Chemical Geology↗

USGS2012

The effect of diagenesis and fluid migration on rare earth element distribution in pore fluids of the northern Cascadia accretionary margin

Analytical challenges in obtaining high quality measurements of rare earth elements (REEs) from small pore fluid volumes have limited the application of REEs as deep fluid geochemical tracers. Using a recently developed analytical technique, we analyzed REEs from pore fluids collected from Sites U1325 and U1329, drilled on the northern Cascadia margin during the Integrated Ocean Drilling Program (IODP) Expedition 311, to investigate the REE behavior during diagenesis and their utility as tracers of deep fluid migration. These sites were selected because they represent contrasting settings on an accretionary margin: a ponded basin at the toe of the margin, and the landward Tofino Basin near the shelf's edge. REE concentrations of pore fluid in the methanogenic zone at Sites U1325 and U1329 correlate positively with concentrations of dissolved organic carbon (DOC) and alkalinity. Fractionations across the REE series are driven by preferential complexation of the heavy REEs. Simultaneous enrichment of diagenetic indicators (DOC and alkalinity) and of REEs (in particular the heavy elements Ho to Lu), suggests that the heavy REEs are released during particulate organic carbon (POC) degradation and are subsequently chelated by DOC. REE concentrations are greater at Site U1325, a site where shorter residence times of POC in sulfate-bearing redox zones may enhance REE burial efficiency within sulfidic and methanogenic sediment zones where REE release ensues. Cross-plots of La concentrations versus Cl, Li and Sr delineate a distinct field for the deep fluids (z > 75 mbsf) at Site U1329, and indicate the presence of a fluid not observed at the other sites drilled on the Cascadia margin. Changes in REE patterns, the presence of a positive Eu anomaly, and other available geochemical data for this site suggest a complex hydrology and possible interaction with the igneous Crescent Terrane, located east of the drilled transect.

Vancouver↗

USGS2012

CO 2 –rock–brine interactions in Lower Tuscaloosa Formation at Cranfield CO 2 sequestration site, Mississippi, U.S.A.

A highly integrated geochemical program was conducted at the Cranfield CO 2 -enhanced oil recovery (EOR) and sequestration site, Mississippi, U.S.A.. The program included extensive field geochemical monitoring, a detailed petrographic study, and an autoclave experiment under in situ reservoir conditions. Results show that mineral reactions in the Lower Tuscaloosa reservoir were minor during CO 2 injection. Brine chemistry remained largely unchanged, which contrasts with significant changes observed in other field tests. Field fluid sampling and laboratory experiments show consistently slow reactions. Carbon isotopic composition and CO 2 content in the gas phase reveal simple two-end-member mixing between injected and original formation gas. We conclude that the reservoir rock, which is composed mainly of minerals with low reactivity (average quartz 79.4%, chlorite 11.8%, kaolinite 3.1%, illite 1.3%, concretionary calcite and dolomite 1.5%, and feldspar 0.2%), is relatively unreactive to CO 2 . The significance of low reactivity is both positive, in that the reservoir is not impacted, and negative, in that mineral trapping is insignificant.

Mississippi↗

USGS2012

Multiple age components in individual molybdenite grains

Re–Os geochronology of fractions composed of unsized, coarse, and fine molybdenite from a pod of unusual monazite–xenotime gneiss within a granulite facies paragneiss, Hudson Highlands, NY, yielded dates of 950.5 ± 2.5, 953.8 ± 2.6, and 941.2 ± 2.6 Ma, respectively. These dates are not recorded by co-existing zircon, monazite, or xenotime. SEM–BSE imagery of thin sections and separated grains reveals that most molybdenite grains are composed of core and rim plates that are approximately perpendicular. Rim material invaded cores, forming irregular contacts, probably reflecting dissolution/reprecipitation. EPMA and LA-ICP-MS analyses show that cores and rims have different trace element concentrations (for example, cores are relatively enriched in W). On the basis of inclusions of zircon with metamorphic overgrowths, we conclude that molybdenite cores and rims formed after high-grade regional metamorphism. The discovery of cores and rims in individual molybdenite grains is analogous to multi-component U-Pb geochronometers such as zircon, monazite, and titanite; thus, molybdenite should be carefully examined before dating to ensure that the requirement of age homogeneity is fulfilled.

New York↗

USGS2012

Inter-laboratory calibration of natural gas round robins for δ 2 H and δ 13 C using off-line and on-line techniques

Compound-specific carbon and hydrogen isotopic compositions of three natural gas round robins were calibrated by ten laboratories carrying out more than 800 measurements including both on-line and off-line methods. Two-point calibrations were performed with international measurement standards for hydrogen isotope ratios (VSMOW and SLAP) and carbon isotope ratios (NBS 19 and L-SVEC CO 2 ). The consensus δ 13 C values and uncertainties were derived from the Maximum Likelihood Estimation (MLE) based on off-line measurements; the consensus δ 2 H values and uncertainties were derived from MLE of both off-line and on-line measurements, taking the bias of on-line measurements into account. The calibrated consensus values in ‰ relative to VSMOW and VPDB are: NG1 (coal-related gas): Methane: δ 2 H VSMOW = − 185.1‰ ± 1.2‰, δ 13 C VPDB = − 34.18‰ ± 0.10‰ Ethane: δ 2 H VSMOW = − 156.3‰ ± 1.8‰, δ 13 C VPDB = − 24.66‰ ± 0.11‰ Propane: δ 2 H VSMOW = − 143.6‰ ± 3.3‰, δ 13 C VPDB = − 22.21‰ ± 0.11‰ i-Butane: δ 13 C VPDB = − 21.62‰ ± 0.12‰ n-Butane: δ 13 C VPDB = − 21.74‰ ± 0.13‰ CO2: δ 13 C VPDB = − 5.00‰ ± 0.12‰ NG2 (biogas): Methane: δ 2 H VSMOW = − 237.0‰ ± 1.2‰, δ 13 C VPDB = − 68.89‰ ± 0.12‰ NG3 (oil-related gas): Methane: δ 2 H VSMOW = − 167.6‰ ± 1.0‰, δ 13 C VPDB = − 43.61‰ ± 0.09‰ Ethane: δ 2 H VSMOW = − 164.1‰ ± 2.4‰, δ 13 C VPDB = − 40.24‰ ± 0.10‰ Propane: δ 2 H VSMOW = − 138.4‰ ± 3.0‰, δ 13 C VPDB = − 33.79‰ ± 0.09‰ All of the assigned values are traceable to the international carbon isotope standard of VPDB and hydrogen isotope standard of VSMOW.

Chemical Geology↗

USGS2012

A graphical method to evaluate predominant geochemical processes occurring in groundwater systems for radiocarbon dating

A graphical method is described for identifying geochemical reactions needed in the interpretation of radiocarbon age in groundwater systems. Graphs are constructed by plotting the measured 14 C, δ 13 C, and concentration of dissolved inorganic carbon and are interpreted according to specific criteria to recognize water samples that are consistent with a wide range of processes, including geochemical reactions, carbon isotopic exchange, 14 C decay, and mixing of waters. The graphs are used to provide a qualitative estimate of radiocarbon age, to deduce the hydrochemical complexity of a groundwater system, and to compare samples from different groundwater systems. Graphs of chemical and isotopic data from a series of previously-published groundwater studies are used to demonstrate the utility of the approach. Ultimately, the information derived from the graphs is used to improve geochemical models for adjustment of radiocarbon ages in groundwater systems.

Chemical Geology↗

USGS2012

Carbon dioxide and hydrogen sulfide degassing and cryptic thermal input to Brimstone Basin, Yellowstone National Park, Wyoming

Brimstone Basin, a remote area of intense hydrothermal alteration a few km east of the Yellowstone Caldera, is rarely studied and has long been considered to be a cold remnant of an ancient hydrothermal system. A field campaign in 2008 confirmed that gas emissions from the few small vents were cold and that soil temperatures in the altered area were at background levels. Geochemical and isotopic evidence from gas samples ( 3 He/ 4 He ~ 3R A , δ 13 C-CO 2 ~ − 3&permil;) however, indicate continuing magmatic gas input to the system. Accumulation chamber measurements revealed a surprisingly large diffuse flux of CO 2 (~ 277 t d -1 ) and H 2 S (0.6 t d -1 ). The flux of CO 2 reduces the 18 O content of the overlying cold groundwater and related stream waters relative to normal meteoric waters. Simple isotopic modeling reveals that the CO 2 likely originates from geothermal water at a temperature of 93 ± 19 °C. These results and the presence of thermogenic hydrocarbons (C1:C2 ~ 100 and δ 13 C-CH 4 = − 46.4 to − 42.8&permil;) in gases require some heat source at depth and refute the assumption that this is a “fossil” hydrothermal system.

Wyoming↗

USGS2013

Volatile ﬂuxes through the Big Bend section of the San Andreas Fault, California: helium and carbon-dioxide systematics

To investigate the source of volatiles and their relationship to the San Andreas Fault System (SAFS), 18 groundwater samples were collected from wells near the Big Bend section of the SAFS in southern California and analyzed for helium and carbon abundance and isotopes. Concentrations of 4 He, corrected for air-bubble entrainment, vary from 4.15 to 62.7 (× 10 − 8 ) cm 3 STP g − 1 H 2 O. 3 He/ 4 He ratios vary from 0.09 to 3.52 R A (where R A = air 3 He/ 4 He), consistent with up to 44% mantle helium in samples. A subset of 10 samples was analyzed for the major volatile phase (CO 2 ) — the hypothesized carrier phase of the helium in the mantle–crust system: CO 2 / 3 He ratios vary from 0.614 to 142 (× 10 11 ), and δ 13 C (CO 2 ) values vary from − 21.5 to − 11.9‰ (vs. PDB). 3 He/ 4 He ratios and CO 2 concentrations are highest in the wells located in the Mil Potrero and Cuddy valleys adjacent to the SAFS. The elevated 3 He/ 4 He ratios are interpreted to be a consequence of a mantle volatile flux though the SAFS diluted by radiogenic He produced in the crust. Samples with the highest 3 He/ 4 He ratios also had the lowest CO 2 / 3 He ratios. The combined helium isotope, He–CO 2 elemental relationships, and δ 13 C (CO 2 ) values of the groundwater volatiles reveal a mixture of mantle and deep crustal (metamorphic) fluid origins. The flux of fluids into the seismogenic zone at high hydrostatic pressure may cause fault rupture, and transfer volatiles into the shallow crust. We calculate an upward fluid flow rate of 147 mm a − 1 along the SAFS, up to 37 times higher than previous estimates (Kennedy et al., 1997). However, using newly identified characteristics of the SAFS, we calculate a total flux of 3 He along the SAFS of 7.4 × 103 cm 3 STP a − 1 (0.33 mol 3 He a − 1 ), and a CO 2 flux of 1.5 × 10 13 cm 3 STP a − 1 (6.6 × 10 8 mol a − 1 ), ~ 1% of previous estimates. Lower fluxes along the Big Bend section of the SAFS suggest that the flux of mantle volatiles alone is insufficient to cause the super hydrostatic pressure in the seismogenic zone; however, results identify crustal (metamorphic) fluids as a major component of the CO 2 volatile budget, which may represent the additional flux necessary for fault weakening pressure in the SAFS.

California↗

USGS2013

Mass fractionation of noble gases in synthetic methane hydrate: Implications for naturally occurring gas hydrate dissociation

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

Chemical Geology↗

USGS2013

Introduction to the special issue on ‘Frontiers in gas geochemistry’

The study of the geochemistry of gases pervades the Earth and Environmental Sciences. This is due in no small measure to the well-established thermodynamic properties of gases which allow their application to a variety of processes occurring over a wide spectrum of natural conditions. In this respect, both major and associated minor gases have been proven useful: indeed, the trace gases have been particularly important given their role as sensitive geochemical tracers. Examples where gas geochemistry places key constraints on geochemical processes include the degassing history of the solid Earth to form the atmosphere and oceans, the origin and migration characteristics of hydrocarbon deposits, the scale of climate variability, the P–T characteristics of geothermal reservoirs, and the dynamics of the earthquake cycle and volcanic activity, to name but a few. This volume continues this rich tradition with an eclectic selection of papers aimed at exploring and exploiting gas geochemistry over a myriad set of research themes.

Chemical Geology↗