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USGS2008

An hydrothermal experimental study of the cobalt-cobalt oxide redox buffer

Equilibrium aqueous hydrogen concentration and corresponding energies of reaction, ??Grxno(T, P), for the reaction Co(s) + H2O(l) = CoO(s) + H2(aq) have been determined at temperatures between 256 and 355 ??C and at 400 bar. Steady-state concentrations of hydrogen were approached in experiments under conditions of both H2 excess and deficiency containing the solids Co, CoO and liquid water. All experiments were carried out in flexible gold and titanium reactors with the capability of on-line fluid sampling. Measured equilibrium molal concentrations of H2(aq) at 256, 274, 300, 324 and 355 ??C are 0.81(?? 0.01) ?? 10- 3 1.11(?? 0.01) ?? 10- 3, 1.92(?? 0.01) ?? 10- 3, 3.71(?? 0.06) ?? 10- 3, 7.54(?? 0.12) ?? 10- 3, respectively, and corresponding values of ??Grxno(T, P) in units kJ ?? mol- 1 are 31.4(?? 0.1), 31.0(?? 0.1), 29.8(?? 0.1), 27.7(?? 0.5) and 25.5(?? 0.9), respectively. Using published heat capacity data for Co(s) and CoO(s) and - 79.6 J ?? mol- 1 ?? K- 1 for the entropy of formation of CoO we calculated for this study a value for ??GCoO,Tr,Pro = - 214.5(?? 0.9) kJ ?? mol- 1 and ??HCoO,Tr,Pro = - 238.3(?? 0.9) kJ ?? mol- 1 at 25 ??C and 1 bar. The value of ??HCoO,Tr,Pro determined in this study compares well with the reported calorimetric value of - 238.9(?? 1.2) kJ ?? mol- 1 [Boyle, B.J., King, E.G., Conway, K.C., 1954. Heats of formation of nickel and cobalt oxides (NiO and CoO) by combustion calorimetry. Journal of the American Chemical Society, 76, 3835-3837]. ?? 2008 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2008

Photoreduction fuels biogeochemical cycling of iron in Spain's acid rivers

A number of investigations have shown that photoreduction of Fe(III) causes midday accumulations of dissolved Fe(II) in rivers and lakes, leading to large diel (24-h) fluctuations in the concentration and speciation of total dissolved iron. Less well appreciated is the importance of photoreduction in providing chemical energy for bacteria to thrive in low pH waters. Diel variations in water chemistry from the highly acidic (pH 2.3 to 3.1) Río Tinto, Río Odiel, and Río Agrio of southwestern Spain (Iberian Pyrite Belt) resulted in daytime increases in Fe(II) concentration of 15 to 66 µM at four diel sampling locations. Dissolved Fe(II) concentrations increased with solar radiation, and one of the stream sites showed an antithetic relationship between dissolved Fe(II) and Fe(III) concentrations; both results are consistent with photoreduction. The diel data were used to estimate rates of microbially catalyzed Fe(II) oxidation (1 to 3 nmol L − 1 s − 1 ) and maximum rates of Fe(III) photoreduction (1.7 to 4.3 nmol L − 1 s − 1 ). Bioenergetic calculations indicate that the latter rates are sufficient to build up a population of Fe-oxidizing bacteria to the levels observed in the Río Tinto in about 30 days. We conclude that photoreduction plays an important role in the bioenergetics of the bacterial communities of these acidic rivers, which have previously been shown to be dominated by autotrophic Fe(II)-oxidizers such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans . Given the possibility of the previous existence of acidic, Fe(III)-rich water on Mars, photoreduction may be an important process on other planets, a fact that could have implications to astrobiological research.

Chemical Geology↗

USGS2008

Integrated Fe- and S-isotope study of seafloor hydrothermal vents at East Pacific Rise 9-10°N

In this study, we report on coupled Fe- and S-isotope systematics of hydrothermal fluids and sulfide deposits from the East Pacific Rise at 9–10°N to better constrain processes affecting Fe-isotope fractionation in hydrothermal environments. We aim to address three fundamental questions: (1) Is there significant Fe-isotope fractionation during sulfide precipitation? (2) Is there significant variability of Fe-isotope composition of the hydrothermal fluids reflecting sulfide precipitation in subsurface environments? (3) Are there any systematics between Fe- and S-isotopes in sulfide minerals? The results show that chalcopyrite, precipitating in the interior wall of a hydrothermal chimney displays a limited range of δ 56 Fe values and δ 34 S values, between − 0.11 to − 0.33‰ and 2.2 to 2.6‰ respectively. The δ 56 Fe values are, on average, slightly higher by 0.14‰ relative to coeval vent fluid composition while δ 34 S values suggest significant S-isotope fractionation (− 0.6 ± 0.2‰) during chalcopyrite precipitation. In contrast, systematically lower δ 56 Fe and δ 34 S values relative to hydrothermal fluids, by up to 0.91‰ and 2.0‰ respectively, are observed in pyrite and marcasite precipitating in the interior of active chimneys. These results suggest isotope disequilibrium in both Fe- and S-isotopes due to S-isotopic exchange between hydrothermal H 2 S and seawater SO 4 2− followed by rapid formation of pyrite from FeS precursors, thus preserving the effects of a strong kinetic Fe-isotope fractionation during FeS precipitation. In contrast, δ 56 Fe and δ 34 S values of pyrite from inactive massive sulfides, which show evidence of extensive late-stage reworking, are essentially similar to the hydrothermal fluids. Multiple stages of remineralization of ancient chimney deposits at the seafloor appear to produce minimal Fe-isotope fractionation. Similar affects are indicated during subsurface sulfide precipitation as demonstrated by the lack of systematic differences between δ 56 Fe values in both high-temperature, Fe-rich black smokers and lower-temperature, Fe-depleted vents.

Chemical Geology↗

USGS2008

Geochemical controls of elevated arsenic concentrations in groundwater, Ester Dome, Fairbanks district, Alaska

Ester Dome, an upland area near Fairbanks, Alaska, was chosen for a detailed hydrogeochemical study because of the previously reported elevated arsenic in groundwater, and the presence of a large set of wells amenable to detailed sampling. Ester Dome lies within the Fairbanks mining district, where gold-bearing quartz veins, typically containing 2–3 vol.% sulfide minerals (arsenopyrite, stibnite, and pyrite), have been mined both underground and in open cuts. Gold-bearing veins on Ester Dome occur in shear zones and the sulfide minerals in these veins have been crushed to fine-grained material by syn- or post-mineralization movement. Groundwater at Ester Dome is circumneutral, Ca–HCO 3 to Ca–SO 4 type, and ranges from dilute (specific conductance of 48 µS/cm) to more concentrated (specific conductance as high as 2070 µS/cm). In general, solute concentrations increase down hydrologic gradient. Redox species indicate that the groundwaters range from oxic to sub-oxic (low dissolved oxygen, Fe(III) reduction, no SO 4 reduction). Waters with the highest Fe concentrations, as high as 10.7 mg/L, are the most anoxic. Dissolved As concentrations range from < 1 to 1160 µg/L, with a median value of 146 µg/L. Arsenic concentrations are not correlated with specific conductance or Fe concentrations, suggesting that neither groundwater residence time, nor reductive dissolution of iron oxyhydroxides, control the arsenic chemistry. Furthermore, As concentrations do not covary with other constituents that form anions and oxyanions in solution (e.g., HCO 3 , Mo, F, or U) such that desorption of arsenic from clays or oxides also does not control arsenic mobility. Oxidation of arsenopyrite and dissolution of scorodite, in the near-surface environment appears to be the primary control of dissolved As in this upland area. More specifically, the elevated As concentrations are spatially associated with sulfidized shear zones and localities of gold-bearing quartz veins. Consistent with this interpretation, elevated dissolved Sb concentrations (as high as 59 µg/L), also correlated with occurrences of hypogene sulfide minerals, were measured in samples with high dissolved As concentrations.

Chemical Geology↗

USGS2008

Mineralogy and geochemistry of a superhigh-organic-sulfur coal, Yanshan Coalfield, Yunnan, China: Evidence for a volcanic ash component and influence by submarine exhalation

The mineralogy and geochemistry of a superhigh-organic-sulfur (SHOS) coal of Late Permian age from the Yanshan Coalfield, Yunnan Province, southwestern China, have been studied using optical microscope, low-temperature ashing plus X-ray diffraction analysis, scanning electron microscope equipped with energy-dispersive X-ray spectrometer, a sequential chemical extraction procedure, and inductively coupled plasma mass spectrometry. The M9 Coal from the Yanshan Coalfield is a SHOS coal that has a total sulfur content of 10.12%-11.30% and an organic sulfur content of 8.77%-10.30%. The minerals in the coal consist mainly of high-temperature quartz, sanidine, albite, muscovite, illite, pyrite, and trace amounts of kaolinite, plagioclase, akermanite, rutile, and dawsonite. As compared with ordinary worldwide (bituminous coals and anthracite) and Chinese coals, the M9 Coal is remarkably enriched in B (268????g/g), F (841????g/g), V (567????g/g), Cr (329????g/g), Ni (73.9????g/g), Mo (204????g/g), and U (153????g/g). In addition, elements including Se (25.2????g/g), Zr (262????g/g), Nb (20.1????g/g), Cd (2.07????g/g), and Tl (2.03????g/g) are also enriched in the coal. Occurrence of high-temperature quartz, sanidine, muscovite, and illite in the M9 Coal is evidence that there is a volcanic ash component in the coal that was derived from acid volcanic ashes fallen into the swamp during peat accumulation. Occurrence of albite and dawsonite in the coal and strong enrichment of some elements, including F, S, V, Cr, Ni, Mo and U, are attributed to the influence by submarine exhalation which invaded along with seawater into the anoxic peat swamp. Abundances of lithophile elements, including rare earth elements, Nb, Y, Zr, and TiO2, indicate that the silicate minerals in the coal were derived from the northern Vietnam Upland to the south of the basin. ?? 2008 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2009

The structure and stability of aqueous rare-earth elements in hydrothermal fluids: New results on neodymium(III) aqua and chloroaqua complexes in aqueous solutions to 500 °C and 520 MPa

X-ray absorption spectroscopy (XAS) measurements were made at the Nd L3-edge on neodymium(III) aqua and chloroaqua complexes in low pH aqueous solutions from 25 to 500????C and up to 520??MPa. Analysis of the extended X-ray absorption fine structure of the XAS spectra measured from a 0.07??m Nd/0.16??m HNO3 aqueous solution reveals a contraction of the Nd-O distance of the Nd3+ aqua ion at a uniform rate of ~ 0.013????/100????C and a uniform reduction of the number of coordinated H2O molecules from 10.0 ?? 0.9 to 7.4 ?? 0.9 over the range from 25 to 500????C and up to 370??MPa. The rate of reduction of the first-shell water molecules with temperature for Nd3+ (26%) is intermediate between the rate for the Gd3+ aqua ion (22% from 25 to 500????C) and the rates for the Eu3+ (29% from 25 to 400????C) and the Yb3+ aqua ions (42% from 25 to 500????C) indicating an intermediate stability of the Nd3+ aqua ion consistent with the tetrad effect. Nd L3-edge XAS measurements of 0.05??m NdCl3 aqueous solution at 25 to 500????C and up to 520??MPa show that stepwise inner-sphere complexes most likely of the type Nd(H2O)?? - nCln+3 - n occur in the solution at elevated temperatures, where ?? ??? 9 at 150????C decreasing to ~ 6 at 500????C and the number of chloride ions (n) of the chloroaqua complexes increases uniformly with temperature from 1.2 ?? 0.2 to 2.0 ?? 0.2 in the solution upon increase of temperature from 150 to 500????C. Conversely, the number of H2O ligands of Nd(H2O)?? - nCln+3 - n complexes is uniformly reduced with temperature from 7.5 ?? 0.8 to 3.7 ?? 0.3 in the aqueous solution, in the same temperature range. These data show greater stability of neodymium(III) than gadolinium(III) and ytterbium(III) chloride complexes in low pH aqueous solutions at elevated temperatures. Our data suggest a greater stability of aqueous light REE than that of heavy REE chloride complexes in low pH fluids at elevated temperatures consistent with REE analysis of fluids from deep-sea hydrothermal vents. ?? 2008 Elsevier B.V.

Chemical Geology↗

USGS2009

The speciation of aqueous zinc(II) bromide solutions to 500 °C and 900 MPa determined using Raman spectroscopy

A Raman spectral study was carried out on 3 solutions of varying concentration and bromide/zinc ratios. Spectra were collected at 11 different temperature-pressure conditions ranging from ambient to 500????C-0.9??GPa. Raman band assignments for zinc(II) bromide species reported in previous studies were used to determine the relative concentrations of ZnBr42-, ZnBr3-, ZnBr2, and ZnBr+ species at various temperatures and pressures. Our results are in close agreement with X-ray absorption spectroscopic (XAS) data, and confirm that the tetrabromo zinc(II) complex, ZnBr42-, is the predominant species up to 500????C in solutions having high Zn concentrations (1??m) and high bromide/zinc molar ratios ([Br]/[Zn] = 8). In agreement with previous solubility and Raman spectroscopic experiments, our measurements indicate that species with a lower number of halide ligands and charge are favored with increasing temperature in dilute solutions, and solutions with low bromide/zinc ratios ([Br]/[Zn] < 2.5). The Raman technique provides an independent experimental means of evaluating the quality of XAS analyses of data obtained from high temperature disordered systems. The combination of these two techniques provides complementary data on speciation and the structure of zinc(II) bromide complexes. The preponderance of the ZnBr42- species in highly saline brines at high temperature is consistent with the predominance of ZnCl42- in chloride-rich brines reported in previous XAS studies. Knowledge of Zn complexing in metal-rich highly saline brines is important for numerical models of ore deposition in high temperature systems such as skarns and porphyry-type deposits. ?? 2008 Elsevier B.V.

Chemical Geology↗

USGS2009

Halogen degassing during ascent and eruption of water-poor basaltic magma

A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO 2 /HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO 2 /HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of < 1??MPa, equivalent to < ~ 35??m in the conduit. Fluid-melt partition coefficients for Cl and F are low (< 1.5); F only degasses appreciably at < 0.1??MPa above atmospheric pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

Chemical Geology↗

USGS2009

Biogeochemical mercury methylation influenced by reservoir eutrophication, Salmon Falls Creek Reservoir, Idaho, USA

Salmon Falls Creek Reservoir (SFCR) in southern Idaho has been under a mercury (Hg) advisory since 2001 as fish in this reservoir contain elevated concentrations of Hg. Concentrations of total Hg (HgT) and methyl-Hg (MeHg) were measured in reservoir water, bottom sediment, and porewater to examine processes of Hg methylation at the sediment/water interface in this reservoir. Rates of Hg methylation and MeHg demethylation were also measured in reservoir bottom sediment using isotopic tracer techniques to further evaluate methylation of Hg in SFCR. The highest concentrations for HgT and MeHg in sediment were generally found at the sediment/water interface, and HgT and MeHg concentrations declined with depth. Porewater extracted from bottom sediment contained highly elevated concentrations of HgT ranging from 11-230??ng/L and MeHg ranging from 0.68-8.5??ng/L. Mercury methylation was active at all sites studied. Methylation rate experiments carried out on sediment from the sediment/water interface show high rates of Hg methylation ranging from 2.3-17%/day, which is significantly higher than those reported in other Hg contaminant studies. Using porewater MeHg concentrations, we calculated an upward diffusive MeHg flux of 197??g/year for the entire reservoir. This sediment derived MeHg is delivered to the overlying SFCR water column, and eventually transferred to biota, such as fish. This study indicates that methylation of Hg is highly influenced by the hypolimnetic and eutrophic conditions in SFCR.

Chemical Geology↗

USGS2009

Fractionation of the platinum-group elments and Re during crystallization of basalt in Kilauea Iki Lava Lake, Hawaii

Kilauea Iki lava lake formed during the 1959 summit eruption of Kilauea Volcano, then crystallized and differentiated over a period of 35??years. It offers an opportunity to evaluate the fractionation behavior of trace elements in a uniquely well-documented basaltic system. A suite of 14 core samples recovered from 1967 to 1981 has been analyzed for 5 platinum-group elements (PGE: Ir, Os, Ru, Pt, Pd), plus Re. These samples have MgO ranging from 2.4 to 26.9??wt.%, with temperatures prior to quench ranging from 1140????C to ambient (110????C). Five eruption samples were also analyzed. Osmium and Ru concentrations vary by nearly four orders of magnitude (0.0006-1.40??ppb for Os and 0.0006-2.01??ppb for Ru) and are positively correlated with MgO content. These elements behaved compatibly during crystallization, mostly likely being concentrated in trace phases (alloy or sulfide) present in olivine phenocrysts or included chromite. Iridium also correlates positively with MgO, although less strongly than Os and Ru. The somewhat poorer correlation for Ir, compared with Os and Ru, may reflect variable loss of Ir as volatile IrF6 in some of the most magnesian samples. Rhenium is negatively correlated with MgO, behaving as an incompatible trace element. Its behavior in the lava lake is complicated by apparent volatile loss of Re, as suggested by a decrease in Re concentration with time of quenching for lake samples vs. eruption samples. Platinum and Pd concentrations are negatively, albeit weakly, correlated with MgO, so these elements were modestly incompatible during crystallization of the major silicate phases. Palladium contents peaked before precipitation of immiscible sulfide liquid, however, and decline sharply in the most differentiated samples. In contrast, Pt appears to have been unaffected by sulfide precipitation. Microprobe data confirm that Pd entered the sulfide liquid before Re, and that Pt is not strongly chalcophile in this system. Occasional high Pt values in both eruption and lava lake samples suggest the presence of unevenly distributed, unidentified Pt-rich trace phases in some Kilauea Iki materials. Estimated mineral (olivine + chromite)/melt D values for Os, Ir, Ru and Pt for equilibrium crystallization for samples from ~ 7 to 27??wt.% MgO are 26, 8.2, 19 and 0.55, respectively. These Os, Ir and Ru estimates are somewhat higher than previous estimates for similar systems. If fractional crystallization is instead assumed, D values are much more similar. Results confirm many prior observations in other mafic systems that olivine (together with included phases) has a major effect on absolute and relative abundances of Re and the PGE. The relatively linear correlations between these elements and MgO potentially permit accurate estimation of the concentrations of these elements in the primary melts of comparable systems, especially in instances where the MgO content of the primary melt is well constrained. ?? 2008 Elsevier B.V.

Chemical Geology↗

USGS2009

Changing sources of strontium to soils and ecosystems across the Hawaiian Islands

Strontium isotope ratios assist ecosystem scientists in constraining the sources of alkaline earth elements, but their interpretation can be difficult because of complexities in mineral weathering and in the geographical and environmental controls on elemental additions and losses. Hawaii is a "natural laboratory" where a number of important biogeochemical variables have either limited ranges or vary in systematic ways, providing a unique opportunity to understand the impact of time, climate, and atmospheric inputs on the evolution of base cation sources to ecosystems. There are three major sources of strontium (Sr) to these ecosystems, each with distinct isotopic compositions: basalt lava, Asian dust, and rainfall. We present Sr isotope and concentration data on both bulk soil digests and NH 4 Ac extracts from soil profiles covering a wide range of environments and substrate ages. Bulk soil material from dry climates and/or young substrate ages with > 80????g g - 1 Sr retain basalt-like Sr isotopic signatures, whereas those with Sr concentrations < 80????g g - 1 can have isotope signatures that range from basalt-like values to the more radiogenic values associated with continental dust. Although both dust accumulation and lava weathering are time- and rainfall-dependent, the overall concentration of Sr drops with increasing leaching even as quartz and mica derived from continental dust sources increase to > 40% by mass. At elevated dust levels, lava-derived Sr is low and dust-derived Sr is the dominant control of 87 Sr/ 86 Sr in bulk soils; however, 87 Sr/ 86 Sr of NH 4 Ac-extractable Sr largely reflects atmospheric deposition of marine aerosol in these situations. Overall, whole-soil Sr isotope values are controlled by complex interactions between Sr provided by lava weathering but partially lost by leaching, and Sr provided by dust but held in more resistant minerals. The isotopic composition of NH 4 Ac-extractable Sr and of the biota is controlled by lava weathering and rainfall contribution of Sr with only minor contributions from radiogenic dust sources. ?? 2009 Elsevier B.V.

Chemical Geology↗

USGS2009

In situ measurements of microbially-catalyzed nitrification and nitrate reduction rates in an ephemeral drainage channel receiving water from coalbed natural gas discharge, Powder River Basin, Wyoming, USA

Nitrification and nitrate reduction were examined in an ephemeral drainage channel receiving discharge from coalbed natural gas (CBNG) production wells in the Powder River Basin, Wyoming. CBNG co-produced water typically contains dissolved inorganic nitrogen (DIN), primarily as ammonium. In this study, a substantial portion of discharged ammonium was oxidized within 50 m of downstream transport, but speciation was markedly influenced by diel fluctuations in dissolved oxygen (> 300 µM). After 300 m of transport, 60% of the initial DIN load had been removed. The effect of benthic nitrogen-cycling processes on stream water chemistry was assessed at 2 locations within the stream channel using acrylic chambers to conduct short-term (2–6 h), in-stream incubations. The highest ambient DIN removal rates (2103 µmol N m − 2 h − 1 ) were found at a location where ammonium concentrations > 350 µM. This occurred during light incubations when oxygen concentrations were highest. Nitrification was occurring at the site, however, net accumulation of nitrate and nitrite accounted for < 12% of the ammonium consumed, indicating that other ammonium-consuming processes were also occurring. In dark incubations, nitrite and nitrate consumption were dominant processes, while ammonium was produced rather than consumed. At a downstream location nitrification was not a factor and changes in DIN removal rates were controlled by nitrate reduction, diel fluctuations in oxygen concentration, and availability of electron donor. This study indicates that short-term adaptation of stream channel processes can be effective for removing CBNG DIN loads given sufficient travel distances, but the long-term potential for nitrogen remobilization and nitrogen saturation remain to be determined.

Chemical Geology↗

USGS2009

Metalliferous sediments from Eolo Seamount (Tyrrhenian Sea): Hydrothermal deposition and re-deposition in a zone of oxygen depletion

A sediment core taken from the south-east slope of the Eolo Seamount is composed of alternating red-brown and light-brown to bluish-grey layers with signs of re-deposition in the middle-upper section. The red-brown layers are Fe-rich metalliferous sediments formed as a result of low-temperature (??? 77????C) hydrothermal discharge, whereas the bluish-grey layers most probably originated from background sedimentation of Al-rich detrital material. The metalliferous layers are composed mainly of Si-rich goethite containing some Al. Co-precipitation of hydrothermally released SiO 4 4- and Fe 2+ as amorphous or poorly crystalline Fe-Si-oxyhydroxides explains the high Si concentration in goethite. The elevated Al content of the goethite is fairly unusual, but reflects the extremely high background Al content of the Tyrrhenian seawater due to the high eolian terrigenous flux from the Sahara desert. The Sr and Nd isotope data suggest that the Eolo metalliferous sediments are the product of a 3-component mixture: hydrothermal fluid, seawater, and detrital material (Saharan dust and Aeolian Arc material). The enrichment in Fe, P, As, Mo, Cd, Be, Sb, W, Y, V, depletion in REE and transition elements (Cu, Co, Ni, Zn) and the REE distribution patterns support the low-temperature hydrothermal deposition of the metalliferous layers. The hydrothermal field is located in a seawater layer of relative O 2 depletion, which led to a significant fractionation of the hydrothermally emitted Fe and Mn. Fe-oxyhydroxides precipitated immediately around the vents whereas Mn stayed in solution longer and the Mn-oxides precipitated higher up on the seamount slope in seawater with relatively higher O 2 levels. High seismic activity led to sediment re-deposition and slumping of the Mn-rich layers down slope and mixing with the Fe-rich layers. ?? 2009 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2009

Strontium isotope record of seasonal scale variations in sediment sources and accumulation in low-energy, subtidal areas of the lower Hudson River estuary

Strontium isotope ( 87 Sr/ 86 Sr) profiles in sediment cores collected from two subtidal harbor slips in the lower Hudson River estuary in October 2001 exhibit regular patterns of variability with depth. Using additional evidence from sediment Ca/Sr ratios, 137 Cs activity and Al, carbonate (CaCO 3 ), and organic carbon (OC sed ) concentration profiles, it can be shown that the observed variability reflects differences in the relative input and trapping of fine-grained sediment from seaward sources vs. landward sources linked to seasonal-scale changes in freshwater flow. During high flow conditions, the geochemical data indicate that most of the fine-grained sediments trapped in the estuary are newly eroded basin materials. During lower (base) flow conditions, a higher fraction of mature materials from seaward sources with higher carbonate content is trapped in the lower estuary. Results show that high-resolution, multi-geochemical tracer approaches utilizing strontium isotope ratios ( 87 Sr/ 86 Sr) can distinguish sediment sources and constrain seasonal scale variations in sediment trapping and accumulation in dynamic estuarine environments. Low-energy, subtidal areas such as those in this study are important sinks for metastable, short-to-medium time scale sediment accumulation. These results also show that these same areas can serve as natural recorders of physical, chemical, and biological processes that affect particle and particle-associated material dynamics over seasonal-to-yearly time scales. ?? 2009.

Chemical Geology↗

USGS2009

Spatial and seasonal variations in mercury methylation and microbial community structure in a historic mercury mining area, Yolo County, California

The relationships between soil parent lithology, nutrient concentrations, microbial biomass and community structure were evaluated in soils from a small watershed impacted by historic Hg mining. Upland and wetland soils, stream sediments and tailings were collected and analyzed for nutrients (DOC, SO 4 = , NO 3 - ), Hg, MeHg, and phospholipid fatty acids (PLFA). Stream sediment was derived from serpentinite, siltstone, volcanic rocks and mineralized serpentine with cinnabar, metacinnabar and other Hg phases. Soils from different parent materials had distinct PLFA biomass and community structures that are related to nutrient concentrations and toxicity effects of trace metals including Hg. The formation of MeHg appears to be most strongly linked to soil moisture, which in turn has a correlative relationship with PLFA biomass in wetland soils. The greatest concentrations of MeHg (> 0.5??ng g - 1 MeHg) were measured in wetland soils and soil with a volcanic parent (9.5-37????g g - 1 Hg). Mercury methylation was associated with sulfate-reducing bacteria, including Desulfobacter sp. and Desulfovibrio sp., although these organisms are not exclusively responsible for Hg methylation. Statistical models of the data demonstrated that soil microbial communities varied more with soil type than with season.

Chemical Geology↗

USGS2009

Processes affecting δ34S and δ18O values of dissolved sulfate in alluvium along the Canadian River, central Oklahoma, USA

The δ 34 S and δ 18 O values for dissolved sulfate in groundwater are commonly used in aquifer studies to identify sulfate reservoirs and describe biogeochemical processes. The utility of these data, however, often is compromised by mixing of sulfate sources within reservoirs and isotope fractionation during sulfur redox cycling. Our study shows that, after all potential sulfate sources are identified and isotopically characterized, the δ 34 S SO4 and δ 18 O SO4 values differentiate processes such as sulfate-source mixing, sulfide oxidation, barite dissolution, and organosulfur decomposition. During bacterial reduction of sulfate, the values reflect kinetic sulfur isotope fractionation and exchange of oxygen isotopes between sulfate and water. Detailed analysis of the chemistry (Cl and SO 4 concentrations) and isotopic composition (δ 2 H H2O and δ 18 O H2O ) of groundwater in an alluvial aquifer in Central Oklahoma, USA allowed the identification of five distinct end members that supply water to the aquifer (regional groundwater flowing into the study area, river water, leachate from a closed landfill that operated within the site, rain, and surface runoff). The δ 34 S SO4 and δ 18 O SO4 values in each end member differentiated three sources of sulfate: sulfate dissolved from Early to Late Permian rocks within the drainage basin (δ 34 S SO4 = 8–12&permil; and δ 18 O SO4 = 10&permil;), iron sulfides oxidized by molecular oxygen during low water-table levels (δ 34 S SO4 = − 16&permil; and δ 18 O SO4 = 10&permil;), and organosulfur compounds (predominately ester sulfates) from decomposition of vegetation on the surface and from landfill trash buried in the alluvium (δ 34 S SO4 = 8&permil; and δ 18 O SO4 = 6&permil;). During bacterial reduction of these sulfate sources, similar isotope fractionation processes are recorded in the parallel trends of increasing δ 34 S SO4 and δ 18 O SO4 values. When extensive reduction occurs, the kinetic sulfur isotope fractionation (estimated by ε H2S–SO4 = − 23&permil;) results in the steady increase of δ 34 S SO4 values to greater than 70&permil;. Equilibrium isotope fractionation during exchange of sulfate oxygen and water oxygen, a process not commonly observed in field-based studies, is documented in δ 18 O SO4 values asymptotically approaching 21&permil;, the value predicted for conditions at the study site ( ε SO4–H2O = 27&permil;). These results show that recognition of all potential sulfate sources is a critical first step to resolving complexities in δ 34 S SO4 and δ 18 O SO4 data. The approach taken in this study can be used in other aquifer systems where the identification of multiple sulfate sources and sulfur redox cycling is important to understanding natural processes and anthropogenic influences.

Oklahoma↗

USGS2009

Assessment of diel chemical and isotopic techniques to investigate biogeochemical cycles in the upper Klamath River, Oregon, USA

The upper Klamath River experiences a cyanobacterial algal bloom and poor water quality during the summer. Diel chemical and isotopic techniques have been employed in order to investigate the rates of biogeochemical processes. Four diel measurements of field parameters (temperature, pH, dissolved oxygen concentrations, and alkalinity) and stable isotope compositions (dissolved oxygen-?? 18 O and dissolved inorganic carbon-?? 13 C) have been performed between June 2007 and August 2008. Significant diel variations of pH, dissolved oxygen (DO) concentration, and DO-?? 18 O were observed, due to varying rates of primary productivity vs. respiration vs. gas exchange with air. Diel cycles are generally similar to those previously observed in river systems, although there are also differences compared to previous studies. In large part, these different diel signatures are the result of the low turbulence of the upper Klamath River. Observed changes in the diel signatures vs. sampling date reflect the evolution of the status of the algal bloom over the course of the summer. Results indicate the potential utility of applying diel chemical and stable isotope techniques to investigate the rates of biogeochemical cycles in slow-moving rivers, lakes, and reservoirs, but also illustrate the increased complexity of stable isotope dynamics in these low-turbulence systems compared to well-mixed aquatic systems. ?? 2009 Elsevier B.V.

Chemical Geology↗

USGS2010

Reactive solute-transport simulation of pre-mining metal concentrations in mine-impacted catchments: Redwell Basin, Colorado, USA

With the increased importance of water resources in the western United States and many areas worldwide, the remediation of impacts from historical mining becomes ever more important. A possible process of making decisions about remediation for a catchment might include identification of principal sources of metals in the catchment, classification of the sources as natural or anthropogenic, and simulations to evaluate different options for removal of anthropogenic sources. The application of this process is based on understanding the pre-mining conditions in the catchment, so that remediation goals appropriately correct for the impacts of mining. A field experiment in Redwell Basin, Colorado, provided a setting to demonstrate this process and to evaluate pre-mining concentrations through reactive solute-transport modeling. The field experiment provided spatially detailed stream and inflow samples that were the basis for model calibration. Only two inflows along the study reach were affected by mining or mine exploration. To simulate pre-mining conditions, these inflows were removed from the model calibration; the result was a simulation of the stream with all the non-mining inputs. At a point downstream from the two mining inflows, the simulated pre-mining pH would have been 5.1, up from the measured 3.8. At the higher pH, the streambed likely would have been coated with Al precipitate. Simulated pre-mining Zn and Cu would have been 1300 µg/L and 18 µg/L, lower than the measured concentrations of 3340 and 93 µg/L. Despite these changes, the pre-mining conditions would not have met aquatic-life standards.

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