Geology topics

R. Blaine McCleskey

Publications and source records attributed to R. Blaine McCleskey.

At least 91 records · Page 5Linked to original sources

USGS2010

Ecological distribution and population physiology defined by proteomics in a natural microbial community

An important challenge in microbial ecology is developing methods that simultaneously examine the physiology of organisms at the molecular level and their ecosystem level interactions in complex natural systems. We integrated extensive proteomic, geochemical, and biological information from 28 microbial communities collected from an acid mine drainage environment and representing a range of biofilm development stages and geochemical conditions to evaluate how the physiologies of the dominant and less abundant organisms change along environmental gradients. The initial colonist dominates across all environments, but its proteome changes between two stable states as communities diversify, implying that interspecies interactions affect this organism's metabolism. Its overall physiology is robust to abiotic environmental factors, but strong correlations exist between these factors and certain subsets of proteins, possibly accounting for its wide environmental distribution. Lower abundance populations are patchier in their distribution, and proteomic data indicate that their environmental niches may be constrained by specific sets of abiotic environmental factors. This research establishes an effective strategy to investigate ecological relationships between microbial physiology and the environment for whole communities in situ .

Molecular Systems Biology↗

USGS2010

Source and fate of inorganic solutes in the Gibbon River, Yellowstone National Park, Wyoming, USA: I. Low-flow discharge and major solute chemistry

The Gibbon River in Yellowstone National Park (YNP) is an important natural resource and habitat for fisheries and wildlife. However, the Gibbon River differs from most other mountain rivers because its chemistry is affected by several geothermal sources including Norris Geyser Basin, Chocolate Pots, Gibbon Geyser Basin, Beryl Spring, and Terrace Spring. Norris Geyser Basin is one of the most dynamic geothermal areas in YNP, and the water discharging from Norris is much more acidic (pH 3) than other geothermal basins in the upper-Madison drainage (Gibbon and Firehole Rivers). Water samples and discharge data were obtained from the Gibbon River and its major tributaries near Norris Geyser Basin under the low-flow conditions of September 2006. Surface inflows from Norris Geyser Basin were sampled to identify point sources and to quantify solute loading to the Gibbon River. The source and fate of the major solutes (Ca, Mg, Na, K, SiO 2 , Cl, F, HCO 3 , SO 4 , NO 3 , and NH 4 ) in the Gibbon River were determined in this study and these results may provide an important link in understanding the health of the ecosystem and the behavior of many trace solutes. Norris Geyser Basin is the primary source of Na, K, Cl, SO 4 , and N loads (35–58%) in the Gibbon River. The largest source of HCO 3 and F is in the lower Gibbon River reach. Most of the Ca and Mg originate in the Gibbon River upstream from Norris Geyser Basin. All the major solutes behave conservatively except for NH 4 , which decreased substantially downstream from Gibbon Geyser Basin, and SiO 2 , small amounts of which precipitated on mixing of thermal drainage with the river. As much as 9–14% of the river discharge at the gage is from thermal flows during this period.

Wyoming↗

USGS2010

Source and fate of inorganic solutes in the Gibbon River, Yellowstone National Park, Wyoming, USA. II. Trace element chemistry

The Gibbon River in Yellowstone National Park receives inflows from several geothermal areas, and consequently the concentrations of many trace elements are elevated compared to rivers in non-geothermal watersheds. Water samples and discharge measurements were obtained from the Gibbon River and its major tributaries near Norris Geyser Basin under the low-flow conditions of September 2006 allowing for the identification of solute sources and their downstream fate. Norris Geyser Basin, and in particular Tantalus Creek, is the largest source of many trace elements (Al, As, B, Ba, Br, Cs, Hg, Li, Sb, Tl, W, and REEs) to the Gibbon River. The Chocolate Pots area is a major source of Fe and Mn, and the lower Gibbon River near Terrace Spring is the major source of Be and Mo. Some of the elevated trace elements are aquatic health concerns (As, Sb, and Hg) and knowing their fate is important. Most solutes in the Gibbon River, including As and Sb, behave conservatively or are minimally attenuated over 29 km of fluvial transport. Some small attenuation of Al, Fe, Hg, and REEs occurs but primarily there is a transformation from the dissolved state to suspended particles, with most of these elements still being transported to the Madison River. Dissolved Hg and REEs loads decrease where the particulate Fe increases, suggesting sorption onto suspended particulate material. Attenuation from the water column is substantial for Mn, with little formation of Mn as suspended particulates.

Wyoming↗

USGS2009

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV Acid-sulfate waters

Many waters sampled in Yellowstone National Park, both high-temperature (30-94 ??C) and low-temperature (0-30 ??C), are acid-sulfate type with pH values of 1-5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H2S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH < 2.7. Field pH measurements were predominantly used because the charge imbalance was <??10%. When the charge imbalance was generally >??10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H2S or S2O3 oxidation, CO2 degassing, and the temperature-dependence of pK2 for H2SO4. Charge imbalances are shown to be dependent on a speciation model for pH values <3. The highest SO4 concentrations, in the thousands of mg/L, result from evaporative concentration at elevated temperatures as shown by the consistently high ??18O values (-10??? to -3???) and a ??D vs. ??18O slope of 3, reflecting kinetic fractionation. Low SO4 concentrations (<100 mg/L) for thermal waters (>350 mg/L Cl) decrease as the Cl- concentration increases from boiling which appears inconsistent with the hypothesis of H2S oxidation as a source of hydrothermal SO4. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid-sulfate water analyses are occasionally high in As, Hg, and NH3 concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO4, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone's acid waters but have not been observed in acid rock drainage of the same pH.

Applied Geochemistry↗

USGS2009

Mercury isotopic composition of hydrothermal systems in the Yellowstone Plateau volcanic field and Guaymas Basin sea-floor rift

To characterize mercury (Hg) isotopes and isotopic fractionation in hydrothermal systems we analyzed fluid and precipitate samples from hot springs in the Yellowstone Plateau volcanic field and vent chimney samples from the Guaymas Basin sea-floor rift. These samples provide an initial indication of the variability in Hg isotopic composition among marine and continental hydrothermal systems that are controlled predominantly by mantle-derived magmas. Fluid samples from Ojo Caliente hot spring in Yellowstone range in δ 202 Hg from - 1.02&permil; to 0.58&permil; (± 0.11&permil;, 2SD) and solid precipitate samples from Guaymas Basin range in δ 202 Hg from - 0.37&permil; to - 0.01&permil; (± 0.14&permil;, 2SD). Fluid samples from Ojo Caliente display mass-dependent fractionation (MDF) of Hg from the vent (δ 202 Hg = 0.10&permil; ± 0.11&permil;, 2SD) to the end of the outflow channel (&delta 202 Hg = 0.58&permil; ± 0.11&permil;, 2SD) in conjunction with a decrease in Hg concentration from 46.6pg/g to 20.0pg/g. Although a small amount of Hg is lost from the fluids due to co-precipitation with siliceous sinter, we infer that the majority of the observed MDF and Hg loss from waters in Ojo Caliente is due to volatilization of Hg 0 (aq) to Hg 0 (g) and the preferential loss of Hg with a lower δ 202 Hg value to the atmosphere. A small amount of mass-independent fractionation (MIF) was observed in all samples from Ojo Caliente (Δ 199 Hg = 0.13&permil; ±1 0.06&permil;, 2SD) but no significant MIF was measured in the sea-floor rift samples from Guaymas Basin. This study demonstrates that several different hydrothermal processes fractionate Hg isotopes and that Hg isotopes may be used to better understand these processes.

Wyoming↗

USGS2009

Geochemistry of standard mine waters, Gunnison County, Colorado, July 2009

In many hard-rock-mining districts water flowing from abandoned mine adits is a primary source of metals to receiving streams. Understanding the generation of adit discharge is an important step in developing remediation plans. In 2006, the U.S. Environmental Protection Agency listed the Standard Mine in the Elk Creek drainage basin near Crested Butte, Colorado as a superfund site because drainage from the Standard Mine enters Elk Creek, contributing dissolved and suspended loads of zinc, cadmium, copper, and other metals to the stream. Elk Creek flows into Coal Creek, which is a source of drinking water for the town of Crested Butte. In 2006 and 2007, the U.S. Geological Survey undertook a hydrogeologic investigation of the Standard Mine and vicinity and identified areas of the underground workings for additional work. Mine drainage, underground-water samples, and selected spring water samples were collected in July 2009 for analysis of inorganic solutes as part of a follow-up study. Water analyses are reported for mine-effluent samples from Levels 1 and 5 of the Standard Mine, underground samples from Levels 2 and 3 of the Standard Mine, two spring samples, and an Elk Creek sample. Reported analyses include field measurements (pH, specific conductance, water temperature, dissolved oxygen, and redox potential), major constituents and trace elements, and oxygen and hydrogen isotopic determinations. Overall, water samples collected in 2009 at the same sites as were collected in 2006 have similar chemical compositions. Similar to 2006, water in Level 3 did not flow out the portal but was observed to flow into open workings to lower parts of the mine. Many dissolved constituent concentrations, including calcium, magnesium, sulfate, manganese, zinc, and cadmium, in Level 3 waters substantially are lower than in Level 1 effluent. Concentrations of these dissolved constituents in water samples collected from Level 2 approach or exceed concentrations of Level 1 effluent suggesting that water-rock interaction between Levels 3 and 1 can account for the elevated concentration of metals and other constituents in Level 1 portal effluent. Ore minerals (sphalerite, argentiferous galena, and chalcopyrite) are the likely sources of zinc, cadmium, lead, and copper and are present within the mine in unmined portions of the vein system, within plugged ore chutes, and in muck piles.

Colorado↗

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

Water-chemistry data for selected springs, geysers, and streams in Yellowstone National Park, Wyoming, 2003-2005

Water analyses are reported for 157 samples collected from numerous hot springs, their overflow drainages, and Lemonade Creek in Yellowstone National Park (YNP) during 2003–2005. Water samples were collected and analyzed for major and trace constituents from ten areas of YNP including Terrace and Beryl Springs in the Gibbon Canyon area, Norris Geyser Basin, the West Nymph Creek thermal area, the area near Nymph Lake, Hazle Lake, and Frying Pan Spring, Lower Geyser Basin, Washburn Hot Springs, Mammoth Hot Springs, Potts Hot Spring Basin, the Sulphur Caldron area, and Lemonade Creek near the Solfatara Trail. These water samples were collected and analyzed as part of research investigations in YNP on arsenic, antimony, and sulfur redox distribution in hot springs and overflow drainages, and the occurrence and distribution of dissolved mercury. Most samples were analyzed for major cations and anions, trace metals, redox species of antimony, arsenic, iron, nitrogen, and sulfur, and isotopes of hydrogen and oxygen. Analyses were performed at the sampling site, in an on-site mobile laboratory vehicle, or later in a U.S. Geological Survey laboratory, depending on stability of the constituent and whether it could be preserved effectively. Water samples were filtered and preserved onsite. Water temperature, specific conductance, pH, Eh (redox potential relative to the Standard Hydrogen Electrode), and dissolved hydrogen sulfide were measured onsite at the time of sampling. Acidity was determined by titration, usually within a few days of sample collection. Alkalinity was determined by titration within 1 to 2 weeks of sample collection. Concentrations of thiosulfate and polythionate were determined as soon as possible (generally minutes to hours after sample collection) by ion chromatography in an on-site mobile laboratory vehicle. Total dissolved-iron and ferrous-iron concentrations often were measured onsite in the mobile laboratory vehicle. Concentrations of dissolved aluminum, arsenic, boron, barium, beryllium, calcium, cadmium, cobalt, chromium, copper, iron, potassium, lithium, magnesium, manganese, molybdenum, sodium, nickel, lead, selenium, silica, strontium, vanadium, and zinc were determined by inductively-coupled plasma-optical emission spectrometry. Trace concentrations of dissolved antimony, cadmium, cobalt, chromium, copper, lead, and selenium were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Dissolved concentrations of total arsenic, arsenite, total antimony, and antimonite were determined by hydride-generation atomic-absorption spectrometry using a flow-injection analysis system. Dissolved concentrations of total mercury and methyl mercury were determined by cold-vapor atomic-fluorescence spectrometry. Concentrations of dissolved chloride, fluoride, nitrate, bromide, and sulfate were determined by ion chromatography. Concentrations of dissolved ferrous and total iron were determined by the FerroZine colorimetric method. Concentrations of dissolved nitrite were determined by colorimetry or chemiluminescence. Concentrations of dissolved ammonium were determined by ion chromatography, with reanalysis by colorimetry when separation of sodium and ammonia peaks was poor. Dissolved organic carbon concentrations were determined by the wet persulfate oxidation method. Hydrogen and oxygen isotope ratios were determined using the hydrogen and CO 2 equilibration techniques, respectively.

Wyoming↗

USGS2008

Ground- and surface-water chemistry of Handcart Gulch, Park County, Colorado, 2003-2006

As part of a multidisciplinary project to determine the processes that control ground-water chemistry and flow in mineralized alpine environments, ground- and surface-water samples from Handcart Gulch, Colorado were collected for analysis of inorganic solutes and water and dissolved sulfate stable isotopes in selected samples. The primary aim of this study was to document variations in ground-water chemistry in Handcart Gulch and to identify changes in water chemistry along the receiving stream of Handcart Gulch. Water analyses are reported for ground-water samples collected from 12 wells in Handcart Gulch, Colorado. Samples were collected between August 2003 and October 2005. Water analyses for surface-water samples are reported for 50 samples collected from Handcart Gulch and its inflows during a low-flow tracer injection on August 6, 2003. In addition, water analyses are reported for three other Handcart Gulch stream samples collected in September 2005 and March 2006. Reported analyses include field parameters (pH, specific conductance, temperature, dissolved oxygen, and Eh), major and trace constituents, oxygen and hydrogen isotopic composition of water and oxygen and sulfur isotopic composition of dissolved sulfate. Ground-water samples from this study are Ca-SO4 type and range in pH from 2.5 to 6.8. Most of the samples (75 percent) have pH values between 3.3 and 4.3. Surface water samples are also Ca-SO4 type and have a narrower range in pH (2.7?4.0). Ground- and surface-water samples vary from relatively dilute (specific conductance of 68 ?S/cm) to concentrated (specific conductance of 2,000 ?S/cm).

Colorado↗

USGS2007

Thioarsenates in geothermal waters of Yellowstone National Park: Determination, preservation, and geochemical importance

Mono-, di-, tri-, and tetrathioarsenate, as well as methylated arsenic oxy- and thioanions, were determined besides arsenite and arsenate in geothermal waters of Yellowstone National Park using anion-exchange chromatography inductively coupled plasma mass spectrometry. Retention time match with synthetic standards, measured S:As ratios, and molecular electrospray mass spectra support the identification. Acidification was unsuitable for arsenic species preservation in sulfidic waters, with HCl addition causing loss of total dissolved arsenic, presumably by precipitation of arsenic-sulfides. Flash-freezing is preferred for the preservation of arsenic species for several weeks. After thawing, samples must be analyzed immediately. Thioarsenates occurred over a pH range of 2.1 to 9.3 in the geothermal waters. They clearly predominated under alkaline conditions (up to 83% of total arsenic), but monothioarsenate also was detected in acidic waters (up to 34%). Kinetic studies along a drainage channel showed the importance of thioarsenates for the fate of arsenic discharged from the sulfidic hot spring. The observed arsenic speciation changes suggest three separate reactions: the transformation of trithioarsenate to arsenite (major initial reaction), the stepwise ligand exchange from tri- via di- and monothioarsenate to arsenate (minor reaction), and the oxidation of arsenite to arsenate, which only becomes quantitatively important after thioarsenates have disappeared.

Wyoming↗

USGS2007

Diel mercury-concentration variations in streams affected by mining and geothermal discharge

Diel variations of concentrations of unfiltered and filtered total Hg and filtered methyl Hg were documented during 24-h sampling episodes in water from Silver Creek, which drains a historical gold-mining district near Helena, Montana, and the Madison River, which drains the geothermal system of Yellowstone National Park. The concentrations of filtered methyl Hg had relatively large diel variations (increases of 68 and 93% from morning minima) in both streams. Unfiltered and filtered (0.1-μm filtration) total Hg in Silver Creek had diel concentration increases of 24% and 7%, respectively. In the Madison River, concentrations of unfiltered and filtered total Hg did not change during the sampling period. The concentration variation of unfiltered total Hg in Silver Creek followed the diel variation in suspended-particle concentration. The concentration variation of filtered total and methyl Hg followed the solar photocycle, with highest concentrations during the early afternoon and evening and lowest concentrations during the morning. None of the diel Hg variations correlated with diel variation in streamflow or major ion concentrations. The diel variation in filtered total Hg could have been produced by adsorption–desorption of Hg 2+ or by reduction of Hg(II) to Hg 0 and subsequent evasion of Hg 0 . The diel variation in filtered methyl Hg could have been produced by sunlight- and temperature-dependent methylation. This study is the first to examine diel Hg cycling in streams, and its results reinforce previous conclusions that diel trace-element cycling in streams is widespread but often not recognized and that parts of the biogeochemical Hg cycle respond quickly to the daily photocycle.

Montana↗

USGS2007

Selected water-quality data for the Standard Mine, Gunnison County, Colorado, 2006-2007

Mine drainage and underground water samples were collected for analysis of inorganic solutes as part of a 1-year, hydrogeologic investigation of the Standard Mine and vicinity. The U.S. Environmental Protection Agency has listed the Standard Mine in the Elk Creek drainage near Crested Butte, Colorado, as a Superfund Site because discharge from the Standard Mine enters Elk Creek, contributing dissolved and suspended loads of zinc, cadmium, copper, and other metals to Coal Creek, which is the primary drinking-water supply for the town of Crested Butte. Water analyses are reported for mine-effluent samples from Levels 1 and 5 of the Standard Mine, underground samples from Levels 3 and 5 of the Standard Mine, mine effluent from an adit located on the Elk Lode, and two spring samples that emerged from waste-rock material below Level 5 of the Standard Mine and the adit located on the Elk Lode. Reported analyses include field parameters (pH, specific conductance, water temperature, dissolved oxygen, and redox potential) and major constituents and trace elements.

Open-File Report↗

USGS2007

Questa baseline and pre-mining ground-water quality investigation. 19. Leaching characteristics of composited materials from mine waste-rock piles and naturally altered areas near Questa, New Mexico

The goal of this study is to compare and contrast the leachability of metals and the acidity from individual mine waste-rock piles and natural erosional scars in the study area near Questa, New Mexico. Surficial multi-increment (composite) samples less than 2 millimeters in diameter from five waste-rock piles, nine erosional-scar areas, a less-altered site, and a tailings slurry-pipe sample were analyzed for bulk chemistry and mineralogy and subjected to two back-to-back leaching procedures. The first leaching procedure, the U.S. Geological Survey Field Leach Test (FLT), is a short-duration leach (5-minute shaking and 10-minute settling) and is intended to leach readily soluble materials. The FLT was immediately followed by an 18-hour, end-over-end rotation leaching procedure. Comparison of results from the back-to-back leaching procedures can provide information about reactions that may take place upon migration of leachates through changing geochemical conditions (for example, pH changes), both within the waste-rock and scar materials and away from the source materials. For the scar leachates, the concentrations of leachable metals varied substantially between the scar areas sampled. The scar leachates have low pH (pH 3.2-4.1). Under these low-pH conditions, cationic metals are solubilized and mobile, but anionic species, such as molybdenum, are less soluble and less mobile. Generally, metal concentrations in the waste-rock leachates did not exceed the upper range of those metal concentrations in the erosional-scar leachates. One exception is molybdenum, which is notably higher in the waste-rock leachates compared with the scar leachates. Most of the waste-rock leachates were at least mildly acidic (pH 3.0-6.2). The pH values in the waste-rock leachates span a large pH range that includes some pH-dependent solubility and metal-attenuation reactions. An increase in pH with leaching time and agitation indicates that there is pH-buffering capacity in some of the waste-rock piles. As pH increased in the waste-pile leachates, concentrations of several metals decreased with increasing time and agitation. Similar pH-dependent reactions may take place upon migration of the leachates in the waste-rock piles. Bulk chemistry, mineralogy, and leachate sulfur-isotope data indicate that the Capulin and Sugar Shack West waste-rock piles are compositionally different from the younger Sugar Shack South, Sugar Shack Middle, and Old Sulphur Gulch piles. The Capulin and Sugar Shack West piles have the lowest-pH leachates (pH 3.0-4.1) of the waste-pile samples, and the source material for the Capulin and Sugar Shack West piles appears to be similar to the source material for the erosional-scar areas. Calcite dissolution, in addition to gypsum dissolution, appears to produce the calcium and sulfate concentrations in leachates from the Sugar Shack South, Sugar Shack Middle, and Old Sulphur Gulch piles.

Scientific Investigations Report↗

USGS2006

Thermodynamic properties and crystal structure refinement of ferricopiapite, coquimbite, rhomboclase, and Fe2(SO4)3(H2O)5

Enthalpies of formation of ferricopiapite [nominally Fe4.67(SO4)6(OH)2 (H2O)20]. coquimbite [Fe2(SO4)3(H2O)9], rhomboclase [(H3O)Fe(SO4)2 (H2O)3], and Fe2(SO4)3(H2O)5 were measured by acid (5 N HCl) solution calorimetry. The samples were characterized by wet chemical analyses and synchrotron powder X-ray diffraction (XRD). The refinement of XRD patterns gave lattice parameters, atomic positions, thermal factors, and occupancies of the sites. The calculated formulae differ slightly from the nominal compositions: Fe4.78(SO4)6 (OH)2.34(H2O)20.71 (ferricopiapite), (Fe1.47Al0.53)(SO4)3 (H2O)9.65 (coquimbite), (H3O)1.34Fe(SO4)2.17 (H2O)3.06 (rhomboclase), and Fe2(SO4)3 (H2O)5.03. All thermodynamic data are given per mole of these formulae. The measured standard enthalpies (in kJ/mol) of formation from the elements (crystalline Fe, Al, S, and ideal gases O2 and H2) at T = 298.15 K are -4115.8??4.1 [Fe2(SO4)3 (H2O)5.03], -12045.1??9.2 (ferricopiapite), -5738.4??3.3 (coquimbite), and -3201.1??2.6 (rhomboclase). Standard entropy (S??) was estimated as a sum of entropies of oxide, hydroxide, and sulfate components. The estimated S?? (in J/mol.K) values for the iron sulfates are 488.2 [Fe2(SO4)3 (H2O)5.03], 1449.2 (ferricopiapite), 638.3 (coquimbite), and 380.1 (rhomboclase). The calculated Gibbs free energies of formation (in kJ/mol) are -3499.7??4.2 [Fe2(SO4)3 (H2O)5.03], -10089.8??9.3 (ferricopiapite), -4845.6??3.3 (coquimbite), and -2688.0??2.7 (rhomboclase). These results combined with other available thermodynamic data allow construction of mineral stability diagrams in the FeIII2(SO4)3-FeII SO4-H2O system. One such diagram is provided, indicating that the order of stability of ferric sulfate minerals with decreasing pH in the range of 1.5 to -0.5 is: hydronium jarosite, ferricopiapite, and rhomboclase. ?? 2006 E. Schweizerbart'sche Verlagsbuchhandlung.

European Journal of Mineralogy↗

USGS2006

Questa baseline and pre-mining ground-water quality investigation. 20. Water chemistry of the Red River and selected seeps, tributaries, and precipitation, Taos County, New Mexico, 2000-2004

As part of a multi-year project to infer the pre-mining ground-water quality at Molycorp's Questa mine site, surface-water samples of the Red River, some of its tributaries, seeps, and snow samples were collected for analysis of inorganic solutes and of water and sulfate stable isotopes in selected samples. The primary aim of this study was to document diel, storm event, and seasonal variations in water chemistry for the Red River and similar variations in water chemistry for Straight Creek, a natural analog site similar in topography, hydrology, and geology to the mine site for inferring pre-mining water-quality conditions. Red River water samples collected between 2000 and 2004 show that the largest variations in water chemistry occur during late summer rainstorms, often monsoonal in nature. Within hours, discharge of the Red River increased from 8 to 102 cubic feet per second and pH decreased from 7.80 to 4.83. The highest concentrations of metals (iron, aluminum, zinc, manganese) and sulfate also occur during such events. Low-pH and high-solute concentrations during rainstorm runoff are derived primarily from alteration 'scar' areas of naturally high mineralization combined with steep topography that exposes continually altered rock because erosion is too rapid for vegetative growth. The year 2002 was one of the driest on record, and Red River discharge reflected the low seasonal snow pack. No snowmelt peak appeared in the hydrograph record, and a late summer storm produced the highest flow for the year. Snowmelt was closer to normal during 2003 and demonstrated the dilution effect of snowmelt on water chemistry. Two diel sampling events were conducted for the Red River, one during low flow and the other during high flow, at two locations, at the Red River gaging station and just upstream from Molycorp's mill site. No discernible diel trends were observed except for dissolved zinc and manganese at the upstream site during low flow. Straight Creek drainage water was sampled periodically from 2001 to 2004 at the down stream end of surface drainage near the point at which it disappeared into the debris fan. This water has a minimal range in pH (2.7 to 3.2) but a substantial concentration range in many solutes; for example, sulfate concentrations varied from 525 to 2,660 mg/L. Many elements covary with sulfate suggesting that dilution is the primary control of the range in solute concentrations. A transect of water samples higher in the scar area were collected in October of 2003. They had a lower range in pH (2.44 to 3.05) and higher solute concentrations than those collected periodically from lower in the catchment. Water isotopes for the upper transect samples indicated slight evaporation, and in part, may account for the higher solute concentrations. Drainage waters also were collected from Hottentot, Junebug, Hansen, Little Hansen, and Goat Hill Gulch drainages. Most constituents from other scar drainage waters showed ranges of concentration similar to those of the Straight Creek waters. An exception was water collected from Goat Hill Gulch, which has some of the highest concentrations of any surface-water sample collected but also contained waste-rock leachates.

New Mexico↗

USGS2005

Seasonality of diel cycles of dissolved trace-metal concentrations in a Rocky Mountain stream

Substantial diel (24-h) cycles in dissolved (0.1-μm filtration) metal concentrations were observed during summer low flow, winter low flow, and snowmelt runoff in Prickly Pear Creek, Montana. During seven diel sampling episodes lasting 34–61.5 h, dissolved Mn and Zn concentrations increased from afternoon minimum values to maximum values shortly after sunrise. Dissolved As concentrations exhibited the inverse timing. The magnitude of diel concentration increases varied in the range 17–152% for Mn and 70–500% for Zn. Diel increases of As concentrations (17–55%) were less variable. The timing of minimum and maximum values of diel streamflow cycles was inconsistent among sampling episodes and had little relation to the timing of metal concentration cycles, suggesting that geochemical rather than hydrological processes are the primary control of diel metal cycles. Diel cycles of dissolved metal concentrations should be assumed to occur at any time of year in any stream with dissolved metals and neutral to alkaline pH.

Environmental 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

Diel behavior of iron and other heavy metals in a mountain stream with acidic to neutral pH: Fisher Creek, Montana, USA

Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe 2+ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters.

Montana↗