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D. Kirk Nordstrom

Publications and source records attributed to D. Kirk Nordstrom.

At least 73 records · Page 4Linked to original sources

Metals fate and transport modelling in streams and watersheds: state of the science and USEPA workshop review

Metals pollution in surface waters from point and non-point sources (NPS) is a widespread problem in the United States and worldwide (Lofts et al. , 2007; USEPA, 2007). In the western United States, metals associated with acid mine drainage (AMD) from hardrock mines in mountainous areas impact aquatic ecosystems and human health (USEPA, 1997a; Caruso and Ward, 1998; Church et al. , 2007). Metals fate and transport modelling in streams and watersheds is sometimes needed for assessment and restoration of surface waters, including mining-impacted streams (Runkel and Kimball, 2002; Caruso, 2003; Velleux et al. , 2006). The Water Quality Analysis Simulation Program (WASP; Wool et al. , 2001), developed by the US Environmental Protection Agency (USEPA), is an example of a model used for such analyses. Other approaches exist and appropriate model selection depends on site characteristics, data availability and modelling objectives. However, there are a wide range of assumptions, input parameters, data requirements and gaps, and calibration and validation issues that must be addressed by model developers, users and decision makers. Despite substantial work on model development, their successful application has been more limited because they are not often used by decision makers for stream and watershed assessment and restoration. Bringing together scientists, model developers, users and decision makers should stimulate the development of appropriate models and improve the applicability of their results. To address these issues, the USEPA Office of Research and Development and Region 8 (Colorado, Montana, North Dakota, South Dakota, Utah and Wyoming) hosted a workshop in Denver, Colorado on February 13–14, 2007. The workshop brought together approximately 35 experts from government, academia and consulting to address the state of the art for modelling metals fate and transport, knowledge gaps and future directions in metals modelling. It focused on modelling metals in high-altitude streams, rivers and watersheds impacted by mine waste that are common in the western United States and require remediation. For example, there are over 100 000 abandoned or inactive mining sites across the United States, encompassing over 500 000 acres of land that may eventually require characterization and remediation, including the possible application of stream or watershed metals fate and transport modelling (USEPA, 1997a). This article provides a general overview of the state of the science on modelling metals fate and transport in streams and watersheds, including a review of presentations and discussions at the USEPA workshop. It builds on previous summaries of metals fate and transport models in aquatic systems, including USEPA (1997b, 2007), Allen (2002), Paquin et al. (2003), Nordstrom (2004) and Maest et al. (2005).

Colorado

What was the groundwater quality before mining in a mineralized region? Lessons from the Questa Project

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department and supported by Molycorp, Inc (currently Chevron Minerals), has completed a 5-year investigation (2001-2006) to determine the pre-mining ground-water quality at Molycorp's Questa molybdenum mine in northern New Mexico. Current mine-site ground waters are often contaminated with mine-waste leachates and no data exists on premining ground-water quality so that pre-mining conditions must be inferred. Ground-water quality undisturbed by mining is often worse than New Mexico standards and data are needed to help establish closure requirements. The key to determining pre-mining conditions was to study the hydrogeochemistry of a proximal natural analog site, the Straight Creek catchment. Main rock types exposed to weathering include a Tertiary andesite and the Tertiary Amalia tuff (rhyolitic composition), both hydrothermally altered to various degrees. Two types of ground water are common in mineralized areas, acidic ground waters in alluvial debris fans with pH 3-4 and bedrock ground waters with pH 6-8. Siderite, ferrihydrite, rhodochrosite, amorphous to microcrystalline Al(OH)3, calcite, gypsum, barite, and amorphous silica mineral solubilities control concentrations of Fe(II), Fe(III), Mn(II), Al, Ca, Ba, and SiO2, depending on pH and solution composition. Concentrations at low pH are governed by element abundance and mineral weathering rates. Concentrations of Zn and Cd range from detection up to about 10 and 0.05 mg/L, respectively, and are derived primarily from sphalerite dissolution. Concentrations of Ni and Co range from detection up to 1 and 0.4 mg/L, respectively, and are derived primarily from pyrite dissolution. Concentrations of Ca and SO4 are derived from secondary gypsum dissolution and weathering of calcite and pyrite. Metal:sulfate concentration ratios are relatively constant for acidic waters, suggesting consistent weathering rates, independent of catchment. These trends, combined with lithology, mineralogy, and mineral solubility controls, provide useful constraints on pre-mining ground-water quality for the mine site where the lithology is known.

Geosciences Journal

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

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

Questa baseline and pre-mining ground-water quality investigation. 25. Summary of results and baseline and pre-mining ground-water geochemistry, Red River Valley, Taos County, New Mexico, 2001-2005

Active and inactive mine sites are challenging to remediate because of their complexity and scale. Regulations meant to achieve environmental restoration at mine sites are equally challenging to apply for the same reasons. The goal of environmental restoration should be to restore contaminated mine sites, as closely as possible, to pre-mining conditions. Metalliferous mine sites in the Western United States are commonly located in hydrothermally altered and mineralized terrain in which pre-mining concentrations of metals were already anomalously high. Typically, those pre-mining concentrations were not measured, but sometimes they can be reconstructed using scientific inference. Molycorp?s Questa molybdenum mine in the Red River Valley, northern New Mexico, is located near the margin of the Questa caldera in a highly mineralized region. The State of New Mexico requires that ground-water quality standards be met on closure unless it can be shown that potential contaminant concentrations were higher than the standards before mining. No ground water at the mine site had been chemically analyzed before mining. The aim of this investigation, in cooperation with the New Mexico Environment Department (NMED), is to infer the pre-mining ground-water quality by an examination of the geologic, hydrologic, and geochemical controls on ground-water quality in a nearby, or proximal, analog site in the Straight Creek drainage basin. Twenty-seven reports contain details of investigations on the geological, hydrological, and geochemical characteristics of the Red River Valley that are summarized in this report. These studies include mapping of surface mineralogy by Airborne Visible-Infrared Imaging Spectrometry (AVIRIS); compilations of historical surface- and ground- water quality data; synoptic/tracer studies with mass loading and temporal water-quality trends of the Red River; reaction-transport modeling of the Red River; environmental geology of the Red River Valley; lake-sediment chemistry; geomorphology and its effect on ground-water flow; geophysical studies on depth to ground-water table and depth to bedrock; bedrock fractures and their potential influence on ground-water flow; leaching studies of scars and waste-rock piles; mineralogy and mineral chemistry and their effect on ground-water quality; debris-flow hazards; hydrology and water balance for the Red River Valley; ground-water geochemistry of selected wells undisturbed by mining in the Red River Valley; and quality assurance and quality control of water analyses. Studies aimed specifically at the Straight Creek natural-analog site include electrical surveys; high-resolution seismic survey; age-dating with tritium/helium; water budget; ground-water hydrology and geochemistry; and comparison of mineralogy and lithology to that of the mine site. The highly mineralized and hydrothermally altered volcanic rocks of the Red River Valley contain several percent pyrite in the quartz-sericite-pyrite (QSP) alteration zone, which weather naturally to acid-sulfate surface and ground waters that discharge to the Red River. Weathering of waste-rock piles containing pyrite also contributes acid water that eventually discharges into the Red River. These acid discharges are neutralized by circumneutral-pH, carbonate-buffered surface and ground waters of the Red River. The buffering capacity of the Red River, however, decreases from the town of Red River to the U.S. Geological Survey (USGS) gaging station near Questa. During short, but intense, storm events, the buffering capacity is exceeded and the river becomes acid from the rapid flushing of acidic materials from natural scar areas. The lithology, mineralogy, elevation, and hydrology of the Straight Creek proximal analog site were found to closely approximate those of the mine site with the exception of the mine site?s Sulphur Gulch catchment. Sulphur Gulch contains three subcatchments?upper Sulphur Gulch, Blind Gulch, and Spring Gulc

New Mexico

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

Speciation of volatile arsenic at geothermal features in Yellowstone National Park

Geothermal features in the Yellowstone National Park contain up to several milligram per liter of aqueous arsenic. Part of this arsenic is volatilized and released into the atmosphere. Total volatile arsenic concentrations of 0.5–200 mg/m 3 at the surface of the hot springs were found to exceed the previously assumed nanogram per cubic meter range of background concentrations by orders of magnitude. Speciation of the volatile arsenic was performed using solid-phase micro-extraction fibers with analysis by GC–MS. The arsenic species most frequently identified in the samples is (CH 3 ) 2 AsCl, followed by (CH 3 ) 3 As, (CH 3 ) 2 AsSCH 3 , and CH 3 AsCl 2 in decreasing order of frequency. This report contains the first documented occurrence of chloro- and thioarsines in a natural environment. Toxicity, mobility, and degradation products are unknown.

Idaho, Montana, Wyoming

Questa baseline and pre-mining ground-water quality investigation. 23. Quantification of mass loading from mined and unmined areas along the Red River, New Mexico

Along the course of the Red River, between the town of Red River, New Mexico, and the U.S. Geological Survey streamflow-gaging station near Questa, New Mexico, there are several catchments that contain hydrothermally altered bedrock. Some of these alteration zones have been mined and others have not, presenting an opportunity to evaluate differences that may exist in the mass loading of metals from mined and unmined sections. Such differences may help to define pre-mining conditions. Spatially detailed chemical sampling at stream and inflow sites occurred during low-flow conditions in 2001 and 2002, and during the synoptic sampling, stream discharge was calculated by tracer dilution. Discharge from most catchments, particularly those with alteration scars, occurred as ground water in large debris fans, which generally traveled downstream in an alluvial aquifer until geomorphic constraints caused it to discharge at several locations along the study reach. Locations of discharge zones were indicated by the occurrence of numerous inflows as seeps and springs. Inflows were classified into four groups, based on differences in chemical character, which ranged from near-neutral water showing no influence of mining or alteration weathering to acidic water with high concentrations of metals and sulfate. Acidic, metal-rich inflows occurred from mined and unmined areas, but the most-acidic inflow water that had the highest concentrations of metals and sulfate only occurred downstream from the mine. Locations of ground-water inflow also corresponded to substantial changes in stream chemistry and mass loading of metals and sulfate. The greatest loading occurred in the Cabin Springs, Thunder Bridge, and Capulin Canyon sections, which all occur downstream from the mine. A distinct chemical character and substantially greater loading in water downstream from the mine suggest that there could be impacts from mining that can be distinguished from the water draining from unmined areas.

New Mexico

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

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

The composition of coexisting jarosite-group minerals and water from the Richmond mine, Iron Mountain, California

Jarosite-group minerals accumulate in the form of stalactites and fine-grained mud on massive pyrite in the D drift of the Richmond mine, Iron Mountain, California. Water samples were collected by placing beakers under the dripping stalactites and by extracting pore water from the mud using a centrifuge. The water is rich in Fe 3+ and SO 4 2− , with a pH of approximately 2.1, which is significantly higher than the extremely acidic waters found elsewhere in the mine. Electron-microprobe analysis and X-ray mapping indicate that the small crystals (<10 μm in diameter) are compositionally zoned with respect to Na and K, and include hydronium jarosite corresponding to the formula (H 3 O) 0.6 K 0.3 Na 0.1 Fe 3 3+ (SO 4 ) 2 (OH) 6 . The proton-microprobe analyses indicate that the jarosite-group minerals contain significant amounts of As, Pb and Zn, and minor levels of Bi, Rb, Sb, Se, Sn and Sr. Speciation modeling indicates that the drip waters are supersaturated with respect to jarosite-group minerals. The expected range in composition of jarosite-group solid-solution in equilibrium with the pore water extracted from the mud was found to be consistent with the observed range in composition.

California

Water-chemistry data for selected springs, geysers, and streams in Yellowstone National Park Wyoming, 2001-2002

Water analyses are reported for one-hundred-twenty-one samples collected from hot springs and their overflow drainages, the Gibbon River, and one ambient-temperature acid stream in Yellowstone National Park (YNP) during 2001-2002. Twenty-five analyses are reported for samples collected during May 2001, fifty analyses are reported for samples collected during September 2001, eleven analyses are reported for samples collected during October 2001, and thirty-five analyses are reported for samples collected during June and July 2002. Water samples were collected and analyzed for major and trace constituents from nine areas of YNP including Norris Geyser Basin, Nymph Lake and Roadside Springs, Lower Geyser Basin, Washburn Springs, Calcite Springs, Crater Hills, Mammoth Hot Springs, West Thumb Geyser Basin, and Brimstone Basin. These water samples were collected and analyzed as part of research investigations in YNP on arsenic redox distribution in hot springs and overflow drainages, the occurrence and distribution of dissolved mercury, and sulfur redox speciation. Most samples were analyzed for major cations and anions, trace metals, and iron, arsenic, nitrogen, and sulfur redox species. Only mercury concentration, pH, and specific conductance were determined for samples collected in October 2001 as they were collected during a reconnaissance field trip. Analyses were performed at the sampling site, in an onsite mobile laboratory, 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, and dissolved hydrogen sulfide were measured onsite at the time of sampling. Alkalinity and acidity were determined by titration, usually within a few days of sample collection. Concentrations of thiosulfate (S 2 O 3 ) and polythionate (S n O 6 ) were determined as soon as possible (generally minutes to hours after sample collection) by ion chromatography in an onsite mobile laboratory vehicle. Total dissolved iron and ferrous iron concentrations often were measured onsite in the mobile laboratory. Concentrations of aluminum, arsenic, barium, beryllium, boron, cadmium, calcium, chromium, cobalt, copper, iron, lead, lithium, magnesium, manganese, molybdenum, nickel, potassium, selenium, silica, sodium, strontium, vanadium, and zinc were determined by inductively coupled plasma-optical emission spectrometry. Trace concentrations of antimony, cadmium, chromium, cobalt, copper, lead, and selenium were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Concentrations of total arsenic and arsenite were determined by hydride-generation atomic-absorption spectrometry using a flow-injection analysis system. Concentrations of total mercury were determined by cold-vapor atomic fluorescence spectrometry. Concentrations of bromide, chloride, nitrate, and sulfate were determined by ion chromatography. Concentrations of ferrous and total iron were determined by the FerroZine colorimetric method. Concentrations of nitrite were determined by colorimetry or chemiluminescence. Concentrations of ammonia 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.

Wyoming

Questa baseline and pre-mining ground-water quality investigation. 14. Interpretation of ground-water geochemistry in catchments other than the Straight Creek catchment, Red River Valley, Taos County, New Mexico, 2002-2003

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department, is investigating the pre-mining ground-water chemistry at the Molycorp molybdenum mine in the Red River Valley, New Mexico. The primary approach is to determine the processes controlling ground-water chemistry at an unmined, off-site but proximal analog. The Straight Creek catchment, chosen for this purpose, consists of the same Tertiary-age quartz-sericite-pyrite altered andesite and rhyolitic volcanics as the mine site. Straight Creek is about 5 kilometers east of the eastern boundary of the mine site. Both Straight Creek and the mine site are at approximately the same altitude, face south, and have the same climatic conditions. Thirteen wells in the proximal analog drainage catchment were sampled for ground-water chemistry. Eleven wells were installed for this study and two existing wells at the Advanced Waste-Water Treatment (AWWT) facility were included in this study. Eight wells were sampled outside the Straight Creek catchment: one each in the Hansen, Hottentot, and La Bobita debris fans, four in a well cluster in upper Capulin Canyon (three in alluvial deposits and one in bedrock), and an existing well at the U.S. Forest Service Questa Ranger Station in Red River alluvial deposits. Two surface waters from the Hansen Creek catchment and two from the Hottentot drainage catchment also were sampled for comparison to ground-water compositions. In this report, these samples are evaluated to determine if the geochemical interpretations from the Straight Creek ground-water geochemistry could be extended to other ground waters in the Red River Valley , including the mine site. Total-recoverable major cations and trace metals and dissolved major cations, selected trace metals, anions, alkalinity; and iron-redox species were determined for all surface- and ground-water samples. Rare-earth elements and low-level As, Bi, Mo, Rb, Re, Sb, Se, Te, Th, U, Tl, V, W, Y, and Zr were determined on selected samples. Dissolved organic carbon (DOC), mercury, sulfate stable isotope composition (δ 34 S and δ 18 O of sulfate), stable isotope composition of water (δ 2 H and δ 18 O of water) were measured for selected samples. Chlorofluorocarbons (CFC) and 3 He and 3 H were measured for age dating on selected samples. Linear regressions from the Straight Creek ground-water data were used to compare ground-water chemistry trends in non-Straight Creek ground waters with Straight Creek alluvial ground-water chemistry dilution trends. Most of the solute trends for the ground waters are similar to those for Straight Creek but there are some notable exceptions. In lithologies that contain substantial pyrite mineralization, acid waters form with similar chemistries to those in Straight Creek and all the waters tend to be calcium-sulfate type. Hottentot ground waters contain substantially lower calcium concentrations relative to those in Straight Creek. This anomaly results from the exposure of rhyolite porphyry in the Hottentot scar and weathering zone. The rhyolite contains less calcium than the altered andesites and tuffs in the Straight Creek catchment and probably does not have the abundant gypsum and calcite. The Hansen ground waters have reached gypsum saturation and have similar calcium, magnesium, and beryllium concentrations as Straight Creek ground waters but have lower concentrations of fluoride, manganese, zinc, cobalt, nickel, copper, and lithium. Lower concentrations of elements related to mineralization at Hansen likely reflect the more distal location of Hansen with respect to intrusive centers that provided the heat source for hydrothermal alteration. The other ground water with water chemistry trends that are outside the Straight Creek trends was from an alluvial well from Capulin Canyon (CC2A). Although it had pH values near 6.0 and most major ions similar to the other Capulin Canyon ground waters, it contained high concentrations of fluoride, manganese, aluminum, iron, beryllium, and zinc similar to a mineralized zone and had low alkalinity. Saturation indices indicate that solubility constraints continue to provide upper limits on some solute concentrations. Siderite, ferrihydrite, calcite, gypsum, rhodochrosite, and barite provide limits for concentrations of Fe(II), Fe(III), Ca, Mn, and Ba, respectively. Beryllium concentrations may be subject to an upper concentration limit by the solubility of Be(OH) 2 but these concentrations probably are not reached in the ground waters. Ground-water isotopic data were consistent with the meteoric water line estimated for precipitation in the Red River Valley, indicating that all the ground waters examined in this study were meteoric, recent in origin, and showed no substantial indication of evaporation. Tritium-helium-3 and chlorofluorocarbon (CFC) age dating were partially successful. Generally, dates were consistent with location and depth of wells. Two samples had good agreement between CFC dates and tritium-helium dates, whereas a third reflected either substantial mixing with younger or older waters or complications arising from excess helium-4. The well at La Bobita appeared to contain a large component of modern water, most likely as a result of mixing with water from Red River alluvial deposits.

New Mexico

Questa baseline and pre-mining ground-water quality investigation. 5. Well installation, water-level data, and surface- and ground-water geochemistry in the Straight Creek drainage basin, Red River Valley, New Mexico, 2001-03

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department, is investigating the pre-mining ground-water chemistry at the Molycorp molybdenum mine in the Red River Valley, northern New Mexico. The primary approach is to determine the processes controlling ground-water chemistry at an unmined, off-site, proximal analog. The Straight Creek drainage basin, chosen for this purpose, consists of the same quartz-sericite-pyrite altered andesitic and rhyolitic volcanic rock of Tertiary age as the mine site. The weathered and rugged volcanic bedrock surface is overlain by heterogeneous debris-flow deposits that interfinger with alluvial deposits near the confluence of Straight Creek and the Red River. Pyritized rock in the upper part of the drainage basin is the source of acid rock drainage (pH 2.8-3.3) that infiltrates debris-flow deposits containing acidic ground water (pH 3.0-4.0) and bedrock containing water of circumneutral pH values (5.6-7.7). Eleven observation wells were installed in the Straight Creek drainage basin. The wells were completed in debris-flow deposits, bedrock, and interfingering debris-flow and Red River alluvial deposits. Chemical analyses of ground water from these wells, combined with chemical analyses of surface water, water-level data, and lithologic and geophysical logs, provided information used to develop an understanding of the processes contributing to the chemistry of ground water in the Straight Creek drainage basin. Surface- and ground-water samples were routinely collected for determination of total major cations and selected trace metals; dissolved major cations, selected trace metals, and rare-earth elements; anions and alkalinity; and dissolved-iron species. Rare-earth elements were determined on selected samples only. Samples were collected for determination of dissolved organic carbon, mercury, sulfur isotopic composition (34S and 18O of sulfate), and water isotopic composition (2H and 18O) during selected samplings. One set of ground-water samples was collected for helium-3/tritium and chlorofluorocarbon (CFC) age dating. Several lines of evidence indicate that surface water is the primary input to the Straight Creek ground-water system. Straight Creek streamflow and water levels in wells closest to the apex of the Straight Creek debris fan and closest to Straight Creek itself appear to respond to the same seasonal inputs. Oxygen and hydrogen isotopic compositions in Straight Creek surface water and ground water are similar, and concentrations of most dissolved constituents in most Straight Creek surface-water and shallow (debris-flow and alluvial) aquifer ground-water samples correlate strongly with sulfate (concentrations decrease linearly with sulfate in a downgradient direction). After infiltration of surface water, dilution along the flow path is the dominant mechanism controlling ground-water chemistry. However, concentrations of some constituents can be higher in ground water than can be accounted for by concentrations in Straight Creek surface water, and additional sources of these constituents must therefore be inferred. Constituents for which concentrations in ground water can be high relative to surface water include calcium, magnesium, strontium, silica, sodium, and potassium in ground water from debris-flow and alluvial aquifers and manganese, calcium, magnesium, strontium, sodium, and potassium in ground water from the bedrock aquifer. All ground water is a calcium sulfate type, often at or near gypsum saturation because of abundant gypsum in the aquifer material developed from co-existing calcite and pyrite mineralization. Calcite dissolution, the major buffering mechanism for bedrock aquifer ground water, also contributes to relatively higher calcium concentrations in some ground water. The main source of the second most abundant cation, magnesium, is probably dissolution of magnesium-rich carbonates or silicates.

New Mexico

Questa baseline and pre-mining ground-water quality investigation. 12. Geochemical and reactive-transport modeling based on tracer injection-synoptic sampling studies for the Red River, New Mexico, 2001-2002

Reactive-transport processes in the Red River, downstream from the town of Red River in north-central New Mexico, were simulated using the OTEQ reactive-transport model. The simulations were calibrated using physical and chemical data from synoptic studies conducted during low-flow conditions in August 2001 and during March/April 2002. Discharge over the 20-km reach from the town of Red River to the USGS streamflow-gaging station near the town of Questa ranged from 395 to 1,180 L/s during the 2001 tracer and from 234 to 421 L/s during the 2002 tracer. The pH of the Red River ranged from 7.4 to 8.5 during the 2001 tracer and from 7.1 to 8.7 during the 2002 tracer, and seep and tributary samples had pH values of 2.8 to 9.0 during the 2001 tracer and 3.8 to 7.2 during the 2002 tracer. Mass-loading calculations allowed identification of several specific locations where elevated concentrations of potential contaminants entered the Red River . These locations, characterized by features on the north side of the Red River that are known to be sources of low-pH water containing elevated metal and sulfate concentrations, are: the initial 2.4 km of the study reach, including Bitter Creek, the stream section from 6.2 to 7.8 km, encompassing La Bobita well and the Hansen debris fan, Sulphur Gulch, at about 10.5 km, the area near Portal Springs, from 12.2 to 12.6 km, and the largest contributors of mass loading, the 13.7 to 13.9 km stream section near Cabin Springs and the 14.7 to 17.5 km stream section from Shaft Spring to Thunder Bridge, Goathill Gulch, and Capulin Canyon. Speciation and saturation index calculations indicated that although solubility limits the concentration of aluminum above pH 5.0, at pH values above 7 and aluminum concentrations below 0.3 mg/L inorganic speciation and mineral solubility controls no longer dominate and aluminum-organic complexing may occur. The August 2001 reactive-transport simulations included dissolved iron(II) oxidation, constrained using measured concentrations of dissolved iron(II) and dissolved iron(total). Both simulations included precipitation of amorphous Al(OH) 3 and hydrous ferric oxide as Fe(OH) 3 , and sorption of copper and zinc to the precipitated hydrous ferric oxide. Simulations revealed that hydrogen, iron, aluminum, copper, and zinc were non-conservative and that mineral precipitation can account for iron and aluminum concentrations. Copper and zinc concentrations can be accounted for by simulating their sorption to hydrous ferric oxide forming in the water column of the Red River , although hydrous manganese oxides also may be important sorption substrates.

New Mexico

Chapter A6. Section 6.5. Reduction-Oxidation Potential (Electrode Method)

Reduction-oxidation (redox) potential--also referred to as Eh--is a measure of the equilibrium potential, relative to the standard hydrogen electrode, developed at the interface between a noble metal electrode and an aqueous solution containing electroactive chemical species. Measurements of Eh are used to evaluate geochemical speciation models, and Eh data can provide insights on the evolution and status of water chemistry in an aqueous system. Nevertheless, the measurement is fraught with inherent interferences and limitations that must be understood and considered to determine applicability to the aqueous system being studied. For this reason, Eh determination is not one of the field parameters routinely measured by the U.S. Geological Survey (USGS). This section of the National Field Manual (NFM) describes the equipment and procedures needed to measure Eh in water using a platinum electrode. Guidance as to the limitations and interpretation of Eh measurement also is included. Each chapter of the National Field Manual is published separately and revised periodically. Newly published and revised chapters will be announced on the USGS Home Page on the World Wide Web under 'New Publications of the U.S. Geological Survey.'

Techniques of Water-Resources Investigations