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USGS2005

Origin of secondary sulfate minerals on active andesitic stratovolcanoes

Sulfate minerals in altered rocks on the upper flanks and summits of active andesitic stratovolcanoes result from multiple processes. The origin of these sulfates at five active volcanoes, Citlalte??petl (Mexico), and Mount Adams, Hood, Rainier, and Shasta (Cascade Range, USA), was investigated using field observations, petrography, mineralogy, chemical modeling, and stable-isotope data. The four general groups of sulfate minerals identified are: (1) alunite group, (2) jarosite group, (3) readily soluble Fe- and Al-hydroxysulfates, and (4) simple alkaline-earth sulfates such as anhydrite, gypsum, and barite. Generalized assemblages of spatially associated secondary minerals were recognized: (1) alunite+silica??pyrite??kaolinite?? gypsum??sulfur, (2) jarosite+alunite+silica; (3) jarosite+smectite+silica??pyrite, (4) Fe- and Al-hydroxysulfates+silica, and (5) simple sulfates+silica??Al-hydroxysulfates??alunite. Isotopic data verify that all sulfate and sulfide minerals and their associated alteration assemblages result largely from the introduction of sulfur-bearing magmatic gases into meteoric water in the upper levels of the volcanoes. The sulfur and oxygen isotopic data for all minerals indicate the general mixing of aqueous sulfate derived from deep (largely disproportionation of SO2 in magmatic vapor) and shallow (oxidation of pyrite or H2S) sources. The hydrogen and oxygen isotopic data of alunite indicate the mixing of magmatic and meteoric fluids. Some alunite-group minerals, along with kaolinite, formed from sulfuric acid created by the disproportionation of SO2 in a condensing magmatic vapor. Such alunite, observed only in those volcanoes whose interiors are exposed by erosion or edifice collapse, may have ??34S values that reflect equilibrium (350??50 ??C) between aqueous sulfate and H2S. Alunite with ??34S values indicating disequilibrium between parent aqueous sulfate and H2S may form from aqueous sulfate created in higher level low-temperature environments in which SO2 is scrubbed out by groundwater or where H2S is oxidized. Jarosite-group minerals associated with smectite in only slightly altered volcanic rock are formed largely from aqueous sulfate derived from supergene oxidation of hydrothermal pyrite above the water table. Soluble Al- and Fehydroxysulfates form in low-pH surface environments, especially around fumaroles, and from the oxidation of hydrothermal pyrite. Anhydrite/gypsum, often associated with native sulfur and occasionally with small amounts of barite, also commonly form around fumaroles. Some occurrences of anhydrite/gypsum may be secondary, derived from the dissolution and reprecipitation of soluble sulfate. Edifice collapse may also reveal deep veins of anhydrite/gypsum??barite that formed from the mixing of saline fluids with magmatic sulfate and dilute meteoric water. Alteration along structures associated with both hydrothermal and supergene sulfates, as well as the position of paleo-water tables, may be important factors in edifice collapse and resulting debris flows at some volcanoes. ?? 2004 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2004

Inhibition and enhancement of microbial surface colonization: the role of silicate composition

Classical treatment of cell attachment by models of filtration or coulombic attraction assumes that attachment of cells to mineral surfaces would be controlled by factors such as response to predation, collision efficiency, or coulombic attraction between the charged groups at the mineral and cell surfaces. In the study reported here, the passive model of attachment was investigated using a native microbial consortium and a variety of Al- and Fe-bearing silicates and oxides to determine if other controls, such as mineral composition, also influence the interaction between cells and surfaces. Results from in situ colonization studies in an anaerobic groundwater at pH 6.8 combined with most probable number analyses (MPN) of surface-adherent cells demonstrate that electrostatic effects dominate microbial colonization on positively charged oxide surfaces regardless of mineral composition. In contrast, on negatively charged silicate minerals and glasses, the solid phase composition is a factor in determining the extent of microbial colonization, as well as the diversity of the attached community. In particular, silicates containing more than 1.2% Al exhibit less biomass than Al-poor silicates and MPN suggests a shift in community diversity, possibly indicating Al toxicity on these surfaces. When Fe is present in the silicate, however, this trend is reversed and abundant colonization of the surface is observed. Here, microorganisms preferentially colonize those silicate surfaces that offer beneficial nutrients and avoid those that contain potentially toxic elements.

Chemical Geology↗

USGS2005

Major and trace element composition of copiapite-group minerals and coexisting water from the Richmond mine, Iron Mountain, California

Copiapite-group minerals of the general formula AR 4 (SO 4 ) 6 (OH) 2 · n H 2 O, where A is predominantly Mg, Fe 2+ , or 0.67Al 3+ , R is predominantly Fe 3+ , and n is typically 20, are among several secondary hydrous Fe sulfates occurring in the inactive mine workings of the massive sulfide deposit at Iron Mountain, CA, a USEPA Superfund site that produces extremely acidic drainage. Samples of copiapite-group minerals, some with coexisting water, were collected from the Richmond mine. Approximately 200 mL of brownish pore water with a pH of −0.9 were extracted through centrifugation from a 10-L sample of moist copiapite-group minerals taken from pyritic muck piles. The pore water is extremely rich in ferric iron (Fe 3+ =149 g L −1 , Fe T =162 g L −1 ) and has a density of 1.52 g mL −1 . The composition of the pore water is interpreted in the context of published phase relations in the Fe 2 O 3 –SO 3 –H 2 O system and previous work on the chemistry of extremely acid mine waters and associated minerals in the Richmond mine. Two distinct members of the copiapite mineral group were identified in the samples with coexisting water: (1) abundant magnesiocopiapite consisting of platy crystals 10 to 50 μm and (2) minor aluminocopiapite present as smaller platy crystals that form spheroidal aggregates. The average composition ( n =5) of the magnesiocopiapite is (Mg 0.90 Fe 2+ 0.17 Zn 0.02 Cu 0.01 ) ∑1.10 (Fe 3+ 3.83 Al 0.09 ) ∑3.92 (SO 4 ) 6.00 (OH) 1.96 ·20H 2 O. Bulk compositions determined by digestion and wet-chemical analysis are consistent with the microanalytical results. These results suggest that magnesiocopiapite is the least soluble member of the copiapite group under the prevailing conditions. Micro-PIXE analysis indicates that the copiapite-group minerals in this sample sequester Zn (average 1420 ppm), with lesser amounts of Cu (average 270 ppm) and As (average 64 ppm).

Chemical Geology↗

USGS2005

Geochemistry of speleothem records from southern Illinois: Development of (234U)/(238U) as a proxy for paleoprecipitation

Natural waters universally show fractionation of uranium series (U-series) parent-daughter pairs, with the disequilibrium between 234U and 238U (234U)/(238U) commonly used as a tracer of groundwater flow. Because speleothems provide a temporal record of geochemical variations in groundwater precipitating calcite, (234U)/(238U) variations in speleothems provide a unique method of investigating water-rock interaction processes over millennium time scales. We present high precision Thermal Ionization Mass Spectrometric (TIMS) U-series analyses of speleothems and drip waters from Fogelpole Cave in southern Illinois. Data from all speleothems from the cave show an inverse correlation between (234U)/(238U) and U concentration, following the pattern observed in groundwaters globally. Within a 65-cm-long stalagmite, concordant 234U-238 U-230Th and 235U-231Pa ages for 5 samples indicate accurate chronology from 78.5 ka to 30 ka. Notably, (234U)/(238U)o which differs from most speleothems by having (234U)/(238U)o <1, positively correlates with speleothem growth rate. We generalize this to the observation that speleothems globally show (234U)/ (238U)o deviating farther from secular equilibrium at lower growth rates and approaching secular equilibrium at higher grow rates. Based on the Fogelpole observations, we suggest that groundwater (234U)/(238U) is controlled by the U oxidation state, the U concentration of the water and the fluid velocity. A transport model whereby U-series nuclides react and exchange with mineral surfaces can reproduce the observed trend between growth rate and (234U)/(238U)o. Based on this result, we suggest that (234U)/(238U)o in speleothems may record changes in hydrologic flux with time and thus could provide a useful proxy for long term records of paleoprecipitation. ?? 2005 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2005

Gas geochemistry of a shallow submarine hydrothermal vent associated with the El Requesón fault zone, Bahía Concepción, Baja California Sur, México

We investigated hydrothermal gas venting associated with a coastal fault zone along the western margin of Bahía Concepción, B.C.S., México. Copious discharge of geothermal liquid (≈ 90 °C) and gas is occurring in the intertidal and shallow subtidal zones (to a depth of 13 m) through soft sediments and fractures in rocks along a &sim;750 m linear trend generally sub-parallel to an onshore fault near Punta Santa Barbara. Hydrothermal activity shows negative correlation with tidal height; temperatures in the area of hydrothermal activity were up to 11.3 °C higher at low tide than at high tide (measured tidal range ≈ 120 cm). Gas samples were collected using SCUBA and analyzed for chemical composition and stable isotope values. The main components of the gas are N 2 (≈ 53%; 534 mmol/mol), CO 2 (≈ 43%; 435 mmol/mol), and CH 4 (≈ 2.2%; 22 mmol/mol). The δ 13 C values of the CH 4 (mean = − 34.3&permil;), and the ratios of CH 4 to C 2 H 6 (mean = 89), indicate that the gas is thermogenic in origin. The carbon stable isotopes and the δ 15 N of the N 2 in the gas (mean = 1.7&permil;) suggest it may be partially derived from the thermal alteration of algal material in immature sedimentary organic matter. The He isotope ratios ( 3 He / 4 He = 1.32 R A ) indicate a significant mantle component (16.3%) in the gas. Here, we suggest the name El Requesón fault zone for the faults that likely formed as a result of extension in the region during the late Miocene, and are currently serving as conduits for the observed hydrothermal activity.

Chemical Geology↗

USGS2006

Useful ion yields for Cameca IMS 3f and 6f SIMS: Limits on quantitative analysis

The useful yields (ions detected/atom sputtered) of major and trace elements in NIST 610 glass were measured by secondary ion mass spectrometry (SIMS) using Cameca IMS 3f and 6f instruments. Useful yields of positive ions at maximum transmission range from 10-4 to 0.2 and are negatively correlated with ionization potential. We quantified the decrease in useful yields when applying energy filtering or high mass resolution techniques to remove molecular interferences. The useful yields of selected negative ions (O, S, Au) in magnetite and pyrite were also determined. These data allow the analyst to determine if a particular analysis (trace element contents or isotopic ratio) can be achieved, given the amount of sample available and the conditions of the analysis. ?? 2005 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2006

Sorption processes affecting arsenic solubility in oxidized surface sediments from Tulare Lake Bed, California

Elevated concentrations of arsenic (As) in shallow groundwater in Tulare Basin pose an environmental risk because of the carcinogenic properties of As and the potential for its migration to deep aquifers that could serve as a future drinking water source. Adsorption and desorption are hypothesized to be the major processes controlling As solubility in oxidized surface sediments where arsenate [As(V)] is dominant. This study examined the relationship between sorption processes and arsenic solubility in shallow sediments from the dry Tulare Lake bed by determining sorption isotherms, pH effect on solubility, and desorption-readsorption behavior (hysteresis), and by using a surface complexation model to describe sorption. The sediments showed a high capacity to adsorb As(V). Estimates of the maximum adsorption capacity were 92 mg As kg- 1 at pH 7.5 and 70 mg As kg- 1 at pH 8.5 obtained using the Langmuir adsorption isotherm. Soluble arsenic [> 97% As(V)] did not increase dramatically until above pH 10. In the native pH range (7.5-8.5), soluble As concentrations were close to the lowest, indicating that As was strongly retained on the sediment. A surface complexation model, the constant capacitance model, was able to provide a simultaneous fit to both adsorption isotherms (pH 7.5 and 8.5) and the adsorption envelope (pH effect on soluble As), although the data ranges are one order of magnitude different. A hysteresis phenomenon between As adsorbed on the sediment and As in solution phase was observed in the desorption-readsorption processes and differs from conventional hysteresis observed in adsorption-desorption processes. The cause is most likely due to modification of adsorbent surfaces in sediment samples upon extensive extractions (or desorption). The significance of the hysteresis phenomenon in affecting As solubility and mobility may be better understood by further microscopic studies of As interaction mechanisms with sediments subjected to extensive leaching in natural environments. ?? 2006 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2006

The geochemical record of the last 17,000 years in the Guaymas Basin, Gulf of California

Sediments deposited on the western slope of the Guaymas Basin in the central Gulf of California are composed predominantly of detrital clastic material and biogenic silica (biopal), with minor organic material (average of 2.8% organic carbon) and calcium carbonate. The CaCO 3 is derived from calcareous plankton and is highly variable ranging from 0% to 16%. In general, the CaCO 3 content of the sediments varies inversely with the biopal content, reflecting the relative abundance of calcareous and siliceous plankton in the photic zone. Siliceous plankton dominate when winds are predominantly out of the northwest producing strong upwelling. Calcareous plankton indicates weak southeasterly winds that bring warm, tropical Pacific surface water into the Gulf. Based mainly on relative abundances of biopal and CaCO 3 , the sediments deposited over the last 17,000 years in the western Guaymas Basin can be divided into five intervals. In general, the sediments in the intervals with high biopal and low CaCO 3 are laminated, but this is not always true. Unlike most other continental margins of the world with well-developed oxygen minimum zones where highest concentrations of organic carbon and redox-sensitive trace metals occur in laminated sediments, the laminated sediments on the anoxic slope of the western Guaymas Basin do not always have the highest concentrations of organic carbon and trace metals such as Mo and Cd.

Guaymas Basin, Gulf of California↗

USGS2006

Effect of thermal maturation on the K-Ar, Rb-Sr and REE systematics of an organic-rich New Albany Shale as determined by hydrous pyrolysis

Hydrous-pyrolysis experiments were conducted on an organic-rich Devonian-Mississippian shale, which was also leached by dilute HCl before and after pyrolysis, to identify and quantify the induced chemical and isotopic changes in the rock. The experiments significantly affect the organic-mineral organization, which plays an important role in natural interactions during diagenetic hydrocarbon maturation in source rocks. They produce 10.5% of volatiles and the amount of HCl leachables almost doubles from about 6% to 11%. The Rb-Sr and K-Ar data are significantly modified, but not just by removal of radiogenic 40Ar and 87Sr, as described in many studies of natural samples at similar thermal and hydrous conditions. The determining reactions relate to alteration of the organic matter marked by a significant change in the heavy REEs in the HCl leachate after pyrolysis, underlining the potential effects of acidic fluids in natural environments. Pyrolysis induces also release from organics of some Sr with a very low 87Sr/86Sr ratio, as well as part of U. Both seem to have been volatilised during the experiment, whereas other metals such as Pb, Th and part of U appear to have been transferred from soluble phases into stable (silicate?) components. Increase of the K2O and radiogenic 40Ar contents of the silicate minerals after pyrolysis is explained by removal of other elements that could only be volatilised, as the system remains strictly closed during the experiment. The observed increase in radiogenic 40Ar implies that it was not preferentially released as a volatile gas phase when escaping the altered mineral phases. It had to be re-incorporated into newly-formed soluble phases, which is opposite to the general knowledge about the behavior of Ar in supergene natural environments. Because of the strictly closed-system conditions, hydrous-pyrolysis experiments allow to better identify and even quantify the geochemical aspects of organic-inorganic interactions, such as elemental exchanges, transfers and volatilisation, in potential source-rock shales during natural diagenetic hydrocarbon maturation.

Chemical Geology↗

USGS2007

Neoproterozoic diamictite-cap carbonate succession and δ 13 C chemostratigraphy from eastern Sonora, Mexico

Despite the occurrence of Neoproterozoic strata throughout the southwestern U.S. and Sonora, Mexico, glacial units overlain by enigmatic cap carbonates have not been well-documented south of Death Valley, California. Here, we describe in detail the first glaciogenic diamictite and cap carbonate succession from Mexico, found in the Cerro Las Bolas Group. The diamictite is exposed near Sahuaripa, Sonora, and is overlain by a 5 m thick very finely-laminated dolostone with soft sediment folds. Carbon isotopic chemostratigraphy of the finely-laminated dolostone reveals a negative δ 13 C anomaly (down to − 3.2&permil; PDB) characteristic of cap carbonates worldwide. Carbon isotopic values rise to + 10&permil; across &sim; 400 m of section in overlying carbonates of the Mina el Mezquite and Monteso Formations. The pattern recorded here is mostly characteristic of post-Sturtian (ca. ≤ 700 Ma), but pre-Marinoan (ca. ≥ 635 Ma) time. However, the Cerro Las Bolas Group shares ambiguity common to most Neoproterozoic successions: it lacks useful radiometric age constraints and biostratigraphically useful fossils, and its δ 13 C signature is oscillatory and therefore somewhat equivocal.

Sonora↗

USGS2007

In situ quantitative analysis of individual H2O-CO2 fluid inclusions by laser Raman spectroscopy

Raman spectral parameters for the Raman ??1 (1285??cm- 1) and 2??2 (1388??cm- 1) bands for CO2 and for the O-H stretching vibration band of H2O (3600??cm- 1) were determined in H2O-CO2 fluid inclusions. Synthetic fluid inclusions containing 2.5 to 50??mol% CO2 were analyzed at temperatures equal to or greater than the homogenization temperature. The results were used to develop an empirical relationship between composition and Raman spectral parameters. The linear peak intensity ratio (IR = ICO2/(ICO2 + IH2O)) is related to the CO2 concentration in the inclusion according to the relation:Mole % C O2 = e- 3.959 IR2 + 8.0734 IRwhere ICO2 is the intensity of the 1388 cm- 1 peak and IH2O is the intensity of the 3600 cm- 1 peak. The relationship between linear peak intensity and composition was established at 350????C for compositions ranging from 2.5 to 50??mol% CO2. The CO2-H2O linear peak intensity ratio (IR) varies with temperature and the relationship between composition and IR is strictly valid only if the inclusions are analyzed at 350????C. The peak area ratio is defined as AR = ACO2/(ACO2 + AH2O), where ACO2 is the integrated area under the 1388??cm- 1 peak and AH2O is the integrated area under the 3600??cm- 1 peak. The relationship between peak area ratio (AR) and the CO2 concentration in the inclusions is given as:Mole % C O2 = 312.5 AR. The equation relating peak area ratio and composition is valid up to 25??mol% CO2 and from 300 to 450????C. The relationship between linear peak intensity ratio and composition should be used for inclusions containing ??? 50??mol% CO2 and which can be analyzed at 350????C. The relationship between composition and peak area ratios should be used when analyzing inclusions at temperatures less than or greater than 350????C (300-450) but can only be used for compositions ??? 25??mol% CO2. Note that this latter relationship has a somewhat larger standard deviation compared to the intensity ratio relationship. Calibration relationships employing peak areas for both members of the Fermi diad (??1 at 1285??cm- 1 and 2??2 at 1388??cm- 1) were slightly poorer than those using only the 2??2 (1388??cm- 1) member owing to interference from quartz peak at approximately 1160??cm- 1. The technique has been applied to natural low-salinity H2O-CO2 inclusions from the Butte, Montana, porphyry copper-molybdenum deposit. Carbon dioxide concentrations obtained range from below detection to 4.2??mol% CO2, and are in good agreement with concentrations determined previously based on microthermometric and petrographic observations. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2007

On the formation and structure of rare-earth element complexes in aqueous solutions under hydrothermal conditions with new data on gadolinium aqua and chloro complexes

Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500????C and at pressures up to 480??MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L3-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO3 aqueous solution at temperatures up to 500????C and at pressures up to 260??MPa shows that the Gd-O distance of the Gd3+ aqua ion decreases steadily at a rate of ??? 0.007??A??/100????C whereas the number of coordinated H2O molecules decreases from 9.0 ?? 0.5 to 7.0 ?? 0.4. The loss of water molecules in the Gd3+ aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb3+ aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd3+ aqua ion relative to other REEs. Gd L3-edge XAFS measurements of 0.006m and 0.1m GdCl3 aqueous solutions at temperatures up to 500????C and pressures up to 480??MPa reveal that the onset of significant Gd3+-Cl- association occurs around 300????C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H2O)??-nCln+3-n occur in the chloride solutions at higher temperatures, where ?? ??? 8 at 300????C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500????C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb3+ aquo ion and chloro complexes in aqueous solutions at up to 500 ??C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd(III) chloro complexes increases steadily with temperature from 0.4 ?? 0.2 to 1.7 ?? 0.3 in the 0.006m chloride solution and from 0.9 ?? 0.7 to 1.8 ?? 0.7 in the 0.1m GdCl3 aqueous solution in the 300-500????C range. Conversely, the number of H2O ligands of Gd(H2O)??-nCln+3-n complexes decreases steadily from 8.9 ?? 0.4 to 5.8 ?? 0.7 in the 0.006m GdCl3 aqueous solution and from 9.0 ?? 0.5 to 5.3 ?? 1.0 in the 0.1m GdCl3 aqueous solution at temperatures from 25 to 500????C. Analysis of our results shows that the chloride ions partially displace the inner-shell water molecules during Gd(III) complex formation under hydrothermal conditions. The Gd-OH2 bond of the partially-hydrated Gd(III) chloro complexes exhibits slightly smaller rates of length contraction (??? 0.005??A??/100????C) for both solutions. The structural aspects of chloride speciation of Gd(III) as measured from this study and of Yb(III) as measured from our previous experiments are consistent with the solubility of these and other REE in deep-sea hydrothermal fluids. ?? 2006 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2007

PVTx properties of the CO 2 -H 2 O and CO 2 -H 2 O-NaCl systems below 647 K: assessment of experimental data and thermodynamic models

Evaluation of CO 2 sequestration in formation brine or in seawater needs highly accurate experimental data or models of pressure–volume–temperature-composition ( PVTx ) properties for the CO 2 –H 2 O and CO 2 –H 2 O–NaCl systems. This paper presents a comprehensive review of the experimental PVTx properties and the thermodynamic models of these two systems. The following conclusions are drawn from the review: (1) About two-thirds of experimental data are consistent with each other, where the uncertainty in liquid volumes is within 0.5%, and that in gas volumes within 2%. However, this accuracy is not sufficient for assessing CO 2 sequestration. Among the data sets for liquids, only a few are available for accurate modeling of CO 2 sequestration. These data have an error of about 0.1% on average, roughly covering from 273 to 642 K and from 1 to 35 MPa; (2) There is a shortage of volumetric data of saturated vapor phase. (3) There are only a few data sets for the ternary liquids, and they are inconsistent with each other, where only a couple of data sets can be used to test a predictive density model for CO 2 sequestration; (4) Although there are a few models with accuracy close to that of experiments, none of them is accurate enough for CO 2 sequestration modeling, which normally needs an accuracy of density better than 0.1%. Some calculations are made available on www.geochem-model.org .

Chemical Geology↗

USGS2007

High arsenic concentrations and enriched sulfur and oxygen isotopes in a fractured-bedrock ground-water system

Ground water with high arsenic concentrations (up to 26.6????mol L- 1) has sulfate enriched in 34S and 18O in the fractured-bedrock, ground-water system of the Kelly's Cove watershed, Northport, Maine, USA. The ranges of sulfur and oxygen isotope values in aqueous sulfate, ??34S[SO4] and ??18O[SO4], at the Kelly's Cove watershed are + 3.4 to + 4.9??? and - 2.0 to + 6.7???, respectively. These isotope values are strikingly similar to those of the Goose River, Maine watershed which has ??34S[SO4] and ??18O[SO4] ranges of + 3.7 to + 4.6 ??? and - 2.6 to + 7.5???, respectively. In both systems, high arsenic concentrations occur with high ??34S[SO4] and ??18O[SO4] values, yet redox conditions and underlying rock types are quite different. The isotope values of sulfide minerals, ??34S[min], from four bedrock cores vary over short distances and range from - 5.1 to + 7.5???. The ??34S[SO4] values are controlled by the ??34S[min] values with minor input of atmospheric SO4. The much narrower range in ??34S[SO4] values than ??34S[min] values is probably due to sufficient ground-water mixing at a scale greater than the ??34S[min] variability. The ??34S[SO4] values are about 2??? higher than the average ??34S[min] value and fall within the range of ??34S[min] values, indicating only minor fractionation due to bacterial reduction of SO4. The highest ??18O[SO4] values were measured in the downgradient, confined, arsenic-rich ground water. High ??18O[SO4] values there cannot be due to aeration by atmospheric oxygen, but may arise from reoxidation of reduced SO4 products. The enrichment factors of ??18O in SO4 compared to H2O, + 7.2 to + 15.5???, in the Kelly's Cove ground water and the negligible 34S enrichment is very similar to those derived from experimental data of anaerobic sulfide oxidation in the presence of Mn and Fe oxides. Sea level at the Kelly's Cove watershed was approximately 80??m above present sea level about 13 000??years before present, imposing reducing conditions on that area of the watershed. Sea level dropped approximately 60??m below present sea level about 11 000??years before present, allowing for possible oxidation of sulfide minerals and precipitation of arsenic in ferric oxyhydroxides during aeration of the ground-water system. Under present redox conditions, there is evidence that bacteria reduction of ferric oxyhydroxides releases arsenic. The fractionation of 18O in the SO4 during anaerobic oxidation of sulfide in the presence of Mn and Fe oxides and subsequent release of arsenic during Mn and Fe oxide reduction may explain the relationship between high arsenic concentrations and elevated 18O[SO4] at Kelly's Cove. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2007

Separation of copper, iron, and zinc from complex aqueous solutions for isotopic measurement

The measurement of Cu, Fe, and Zn isotopes in natural samples may provide valuable information about biogeochemical processes in the environment. However, the widespread application of stable Cu, Fe, and Zn isotope chemistry to natural water systems remains limited by our ability to efficiently separate these trace elements from the greater concentrations of matrix elements. In this study, we present a new method for the isolation of Cu, Fe, and Zn from complex aqueous solutions using a single anion-exchange column with hydrochloric acid media. Using this method we are able to quantitatively separate Cu, Fe, and Zn from each other and from matrix elements in a single column elution. Elution of the elements of interest, as well as all other elements, through the anion-exchange column is a function of the speciation of each element in the various concentrations of HCl. We highlight the column chemistry by comparing our observations with published studies that have investigated the speciation of Cu, Fe, and Zn in chloride solutions. The functionality of the column procedure was tested by measuring Cu, Fe, and Zn isotopes in a variety of stream water samples impacted by acid mine drainage. The accuracy and precision of Zn isotopic measurements was tested by doping Zn-free stream water with the Zn isotopic standard. The reproducibility of the entire column separation process and the overall precision of the isotopic measurements were also evaluated. The isotopic results demonstrate that the Cu, Fe, and Zn column separates from the tested stream waters are of sufficient purity to be analyzed directly using a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), and that the measurements are fully-reproducible, accurate, and precise. Although limited in scope, these isotopic measurements reveal significant variations in δ 65 Cu (− 1.41 to + 0.30‰), δ 56 Fe (− 0.56 to + 0.34‰), and δ 66 Zn (0.31 to 0.49‰) among samples collected from different abandoned mines within a single watershed. Hence, Cu, Fe, and Zn isotopic measurements may be a powerful tool for fingerprinting specific metal sources and/or examining biogeochemical reactions within fresh water systems.

Chemical Geology↗

USGS2007

Hydrothermal nontronite formation at Eolo Seamount (Aeolian volcanic arc, Tyrrhenian Sea)

A sediment core containing a yellowish-green clay bed was recovered from an area of extensive hydrothermal deposition at the SE slope of the Eolo Seamount, Tyrrhenian Sea. The clay bed is composed of pure nontronite (described for the first time in the Tyrrhenian Sea), which appears to be the most aluminous nontronite ever found among the seafloor hydrothermal deposits. The high Al content suggests precipitation from Al-containing hydrothermal solutions. The REE distribution of the Eolo nontronite has a V-shape pattern. The heavy REE enrichment is in part due to their preferential partitioning in the nontronite structure. This enrichment was possibly further enhanced by the HREE preferential sorption on bacterial cell walls. The light REE enrichment is the result of scavenging uptake by one of the nontronite precursors, i.e., poorly-ordered Fe-oxyhydroxides, from the hydrothermal fluids. Oxygen isotopic composition of the nontronite yields a formation temperature of 30????C, consistent with a low-temperature hydrothermal origin. The relatively radiogenic Nd isotopic signature of the nontronite compared to the present-day Mediterranean seawater indicates that approximately half of Nd, and presumably the rest of the LREE, are derived from local volcanic sources. On the other hand, 87Sr/86Sr is dominated by present-day seawater Sr. Scanning electron microscopy investigation revealed that the nontronite is composed of aggregates of lepispheres and tube-like filaments, which are indicative of bacteria assisted precipitation. Bacteria inhabiting this hydrothermal site likely acted as reactive geochemical surfaces on which poorly-ordered hydrothermal Fe-oxyhydroxides and silica precipitated. Upon aging, the interactions of these primary hydrothermal precipitates coating bacterial filaments and cell walls likely led to the formation of nontronite. Finally, the well-balanced interlayer and layer charges of the crystal lattice of seafloor hydrothermal nontronite decrease its sorption capacity to zero. Thus the ubiquitous nontronite precipitation along the active plate boundaries and around the hot spots has no significant impact on oceanic trace element chemistry. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2008

Deposition of talc - kerolite-smectite - smectite at seafloor hydrothermal vent fields: Evidence from mineralogical, geochemical and oxygen isotope studies

Talc, kerolite-smectite, smectite, chlorite-smectite and chlorite samples from sediments, chimneys and massive sulfides from six seafloor hydrothermal areas have been analyzed for mineralogy, chemistry and oxygen isotopes. Samples are from both peridotite- and basalt-hosted hydrothermal systems, and basaltic systems include sediment-free and sediment-covered sites. Mg-phyllosilicates at seafloor hydrothermal sites have previously been described as talc, stevensite or saponite. In contrast, new data show tri-octahedral Mg-phyllosilicates ranging from pure talc and Fe-rich talc, through kerolite-rich kerolite-smectite to smectite-rich kerolite-smectite and tri-octahedral smectite. The most common occurrence is mixed-layer kerolite-smectite, which shows an almost complete interstratification series with 5 to 85% smectitic layers. The smectite interstratified with kerolite is mostly tri-octahedral. The degree of crystal perfection of the clay sequence decreases generally from talc to kerolite-smectite with lower crystalline perfection as the proportion of smectite layers in kerolite-smectite increases. Our studies do not support any dependence of the precipitated minerals on the type/subtype of hydrothermal system. Oxygen isotope geothermometry demonstrates that talc and kerolite-smectite precipitated in chimneys, massive sulfide mounds, at the sediment surface and in open cracks in the sediment near seafloor are high-temperature (> 250????C) phases that are most probably the result of focused fluid discharge. The other end-member of this tri-octahedral Mg-phyllosilicate sequence, smectite, is a moderate-temperature (200-250????C) phase forming deep within the sediment (??? 0.8??m). Chlorite and chlorite-smectite, which constitute the alteration sediment matrix around the hydrothermal mounds, are lower-temperature (150-200????C) phases produced by diffuse fluid discharge through the sediment around the hydrothermal conduits. In addition to temperature, other two controls on the precipitation of this sequence are the silica activity and Mg/Al ratio (i.e. the degree of mixing of seawater with hydrothermal fluid). Higher silica activity favors the formation of talc relative to tri-octahedral smectite. Vent structures and sedimentary cover preclude complete mixing of hydrothermal fluid and ambient seawater, resulting in lower Mg/Al ratios in the interior parts of the chimneys and deeper in the sediment which leads to the precipitation of phyllosilicates with lower Mg contents. Talc and kerolite-smectite have very low trace- and rare earth element contents. Some exhibit a negative or flat Eu anomaly, which suggests Eu depletion in the original hydrothermal fluid. Such Eu depletion could be caused by precipitation of anhydrite or barite (sinks for Eu2+) deeper in the system. REE abundances and distribution patterns indicate that chlorite and chlorite-smectite are hydrothermal alteration products of the background turbiditic sediment. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2008

The effect of acid rain and altitude on concentration, δ34S, and δ18O of sulfate in the water from Sudety Mountains, Poland

The analyses of sulfate content, δ 34 S and δ 18 O of dissolved sulfate, and δ 18 O of water were carried out in a 14 km 2 crystalline massif located in the Sudety Mountains (SW Poland) to 1) assess the amount of the sulfate delivered to the surface and groundwater systems by modern atmospheric precipitation, 2) determine the effect of altitude on these parameters, and 3) investigate their seasonal variations. In April and November of 2002, August 2003, and March and September of 2005, samples of water were collected from springs and streams of the massif. During these seasons, sulfate contents and δ 18 O(SO 4 2− ) values varied from 5.80 to 18.00 mg/l and from 3.96 to 8.23&permil;, respectively, showing distinctively higher values of δ 18 O(SO 4 2− ) in wet seasons. The δ 34 S(SO 4 2− ) values had a relatively narrow range from 4.09 to 5.28&permil; and were similar to those reported for organic matter in soil and the canopy throughfall in the Sudety Mountains. Sulfate content, δ 34 S(SO 4 2− ), δ 18 O(SO 4 2− ), and δ 18 O(H 2 O) values revealed a remarkable dependence on the altitude. The calculated altitude effects for five season averages of these parameters were − 1.00 mg/l/100 m, − 0.18&permil;/100 m, − 0.27&permil;/100 m, and − 0.17&permil;/100 m, respectively. This dependence on the altitude resulted mainly from the mixing of sulfates of different origins such as anthropogenic sulfate, sulfate produced in the soil within the weathered zone of the massif, and that one from the tree canopy. The oxygen isotope mass balance indicates that, in the study area, about one third of the sulfate delivered to the surface and groundwater by modern precipitation comes from anthropogenic pollution. Further interaction of meteoric water within the weathered rocks causes a continuous decrease of δ 18 O(SO 4 2− ) values resulting from biological transformation of the sulfate due to plant vegetation and decomposition of organic matter.

Sudety Mountains↗