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R. Blaine McCleskey

Publications and source records attributed to R. Blaine McCleskey.

108 records · Page 6Linked to original sources

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↗

Ground water to surface water: Chemistry of thermal outflows in Yellowstone National Park

Geothermal waters in the earth’s subsurface boil with steam separation and may mix with dilute ground waters (that may or may not contain sulfuric acid from sulfur oxidation), resulting in a wide range of compositions when they discharge and emerge at the surface. As they discharge onto the ground surface they undergo evaporative cooling, degassing, oxidation, and mineral precipitation. Within this aquatic environment of rapidly changing physical and chemical parameters, numerous microbial communities develop—some of which affect oxidation and mineral precipitation. Microbes are responsible for rapid oxidation of iron and arsenic in thermal outflows, and for catalyzing the production of sulfuric acid from the oxidation of elemental sulfur. The attractive visual display of colors observed in Yellowstone’s geothermal waters reflects this interplay of physical, chemical, and biological phenomena. Oxidation of dissolved sulfide to thiosulfate occurs abiotically, and thiosulfate can be found in many of Yellowstone’s thermal waters—at any pH, temperature, and composition. Polythionates, on the other hand, are rarely found in Yellowstone waters but are associated with sulfur hydrolysis in Cinder Pool. Oxidation rates of iron and arsenic in overflows have been estimated at 1-3 mM/h and 0.04-0.1 mM/h, respectively—orders of magnitude faster than the abiotic rate. The abiotic production of thiosulfate from oxidation of dissolved sulfi de at Angel Terrace and Ojo Caliente is about 3-30 µM/min, faster by 2-3 orders of magnitude than the laboratory rate at 25°C. The partitioning of dissolved sulfide between that volatilized to the air and that oxidized to thiosulfate has been estimated at Angel Terrace and at Ojo Caliente. For the pH range of 6-8 and the temperature range of 50-93°C, 67-86% of the dissolved sulfide is lost to the atmosphere and 10-33% is oxidized to thiosulfate. Only a very small percentage, if any, forms elemental sulfur under these conditions.

Wyoming↗

Preservation of water samples for arsenic(III/V) determinations: An evaluation of the literature and new analytical results

Published literature on preservation procedures for stabilizing aqueous inorganic As(III/V) redox species contains discrepancies. This study critically evaluates published reports on As redox preservation and explains discrepancies in the literature. Synthetic laboratory preservation experiments and time stability experiments were conducted for natural water samples from several field sites. Any field collection procedure that filters out microorganisms, adds a reagent that prevents dissolved Fe and Mn oxidation and precipitation, and isolates the sample from solar radiation will preserve the As(III/V) ratio. Reagents that prevent Fe and Mn oxidation and precipitation include HCl, H 2SO4, and EDTA, although extremely high concentrations of EDTA are necessary for some water samples high in Fe. Photo-catalyzed Fe(III) reduction causes As(III) oxidation; however, storing the sample in the dark prevents photochemical reactions. Furthermore, the presence of Fe(II) or SO 4 inhibits the oxidation of As(III) by Fe(III) because of complexation reactions and competing reactions with free radicals. Consequently, fast abiotic As(III) oxidation reactions observed in the laboratory are not observed in natural water samples for one or more of the following reasons: (1) the As redox species have already stabilized, (2) most natural waters contain very low dissolved Fe(III) concentrations, (3) the As(III) oxidation caused by Fe(III) photoreduction is inhibited by Fe(II) or SO4.

Applied Geochemistry↗

Relative effect of temperature and pH on diel cycling of dissolved trace elements in Prickly Pear Creek, Montana

Diel (24 hr) cycles in dissolved metal and As concentrations have been documented in many northern Rocky Mountain streams in the U.S.A. The cause(s) of the cycles are unknown, although temperature- and pH-dependent sorption reactions have been cited as likely causes. A light/dark experiment was conducted to isolate temperature and pH as variables affecting diel metal cycles in Prickly Pear Creek, Montana. Light and dark chambers containing sediment and a strand of macrophyte were placed in the stream to simulate instream temperature oscillations. Photosynthesis-induced pH changes were allowed to proceed in the light chambers while photosynthesis was prevented in the dark chambers. Water samples were collected periodically for 22 hr in late July 2001 from all chambers and the stream. In the stream, dissolved Zn concentrations increased by 300% from late afternoon to early morning, while dissolved As concentrations exhibited the opposite pattern, increasing 33% between early morning and late afternoon. Zn and As concentrations in the light chambers showed similar, though less pronounced, diel variations. Conversely, Zn and As concentrations in the dark chambers had no obvious diel variation, indicating that light, or light-induced reactions, caused the variation. Temperature oscillations were nearly identical between light and dark chambers, strongly suggesting that temperature was not controlling the diel variations. As expected, pH was negatively correlated ( P < 0.01) with dissolved Zn concentrations and positively correlated with dissolved As concentrations in both the light and dark chambers. From these experiments, photosynthesis-induced pH changes were determined to be the major cause of the diel dissolved Zn and As cycles in Prickly Pear Creek. Further research is necessary in other streams to verify that this finding is consistent among streams having large differences in trace-element concentrations and mineralogy of channel substrate.

Montana↗

Questa baseline and pre-mining ground-water-quality investigation. 16. Quality assurance and quality control for water analyses

The Questa baseline and pre-mining ground-water quality investigation has the main objective of inferring the ground-water chemistry at an active mine site. Hence, existing ground-water chemistry and its quality assurance and quality control is of crucial importance to this study and a substantial effort was spent on this activity. Analyses of seventy-two blanks demonstrated that contamination from processing, handling, and analyses were minimal. Blanks collected using water deionized with anion and cation exchange resins contained elevated concentrations of boron (0.17 milligrams per liter (mg/L)) and silica (3.90 mg/L), whereas double-distilled water did not. Boron and silica were not completely retained by the resins because they can exist as uncharged species in water. Chloride was detected in ten blanks, the highest being 3.9 mg/L, probably as the result of washing bottles, filter apparatuses, and tubing with hydrochloric acid. Sulfate was detected in seven blanks; the highest value was 3.0 mg/L, most likely because of carryover from the high sulfate waters sampled. With only a few exceptions, the remaining blank analyses were near or below method detection limits. Analyses of standard reference water samples by cold-vapor atomic fluorescence spectrometry, ion chromatography, inductively coupled plasma-optical emission spectrometry, inductively coupled plasma-mass spectrometry, FerroZine, graphite furnace atomic absorption spectrometry, hydride generation atomic spectrometry, and titration provided an accuracy check. For constituents greater than 10 times the detection limit, 95 percent of the samples had a percent error of less than 8.5. For constituents within 10 percent of the detection limit, the percent error often increased as a result of measurement imprecision. Charge imbalance was calculated using WATEQ4F and 251 out of 257 samples had a charge imbalance less than 11.8 percent. The charge imbalance for all samples ranged from -16 to 16 percent. Spike recoveries were performed by spiking ground-water samples from SC2B, SC3A, SC3B, CC2A, and Hottentot with a mixed-element standard and then analyzing them by ICP-OES. The mean recovery for all the constituents by ICP-OES was 103 percent with a standard deviation of 16 percent. Fifteen surface- and ground-water sequential duplicates were collected from Straight Creek, Hottentot, and the Red River from 2002 to 2003. Except for chloride from well SC5B and low concentrations of iron (<0.05 mg/L) and aluminum (<0.01 mg/L), constituents of sequential duplicates are generally within 10 percent of each other. Analytical results from different methods and different laboratories, with rare exceptions, were within 10 percent. Chromium analyses were in poor agreement when comparing analyses from the USGS and a contract laboratory, but USGS analyses by ICP-OES and ICP-MS were usually within 10 percent for chromium concentrations above 0.03 mg/L and analyses by ICP-OES and GFAAS were usually within 15 percent for chromium concentrations as much as 0.1 mg/L. Filtration studies also were performed to study the effects of filtration apparatuses (Minitan, plate, capsule, and syringe), pore sizes, and timing on dissolved metal concentrations. Except for iron and aluminum, constituents with concentrations greater than about 0.05 mg/L were generally not affected by the filtration apparatus, membrane pore-size, and filtration delays. Iron, aluminum, and some dissolved metals concentrations less than about 0.05 mg/L, especially copper, were generally lowest in filtrates from the tangential flow Minitan system containing a filter membrane with a pore size of 10,000 Daltons. As part of a filtration timing study, grab samples were collected from two sites along the Red River and were processed immediately and then again 1 to 3 hours later. Aluminum and iron colloids formed during the delay in the sample collected at the USGS gaging station and, after the delay, 0.1-ìm filtrate aluminum and iron concentrations approached the ultrafiltrate (Minitan) concentrations. In the upstream site below Fawn Lakes, aluminum in the 0.1-ìm filtrate decreased but did not decrease in the 0.45-ìm filtrate, signifying that the colloids formed during the delay are between 0.1 and 0.45 ìm. Dissolved nickel and pH also decreased in both samples during the delay. Except for ferrous iron and barium, a sequential filtration study 2 demonstrated that water collected from the Red River at the gage did not affect dissolved metal concentrations with increasing sample volume passing through a plate filter with 0.45- or 0.1-ìm membranes. Barium and ferrous iron both slightly decreased in the filtrate from the 0.45-ìm filter.

Open-File Report↗

A new cation-exchange method for accurate field speciation of hexavalent chromium

A new method for field speciation of Cr(VI) has been developed to meet present stringent regulatory standards and to overcome the limitations of existing methods. The method consists of passing a water sample through strong acid cation-exchange resin at the field site, where Cr(III) is retained while Cr(VI) passes into the effluent and is preserved for later determination. The method is simple, rapid, portable, and accurate, and makes use of readily available, inexpensive materials. Cr(VI) concentrations are determined later in the laboratory using any elemental analysis instrument sufficiently sensitive to measure the Cr(VI) concentrations of interest. The new method allows measurement of Cr(VI) concentrations as low as 0.05 ??g 1-1, storage of samples for at least several weeks prior to analysis, and use of readily available analytical instrumentation. Cr(VI) can be separated from Cr(III) between pH 2 and 11 at Cr(III)/Cr(VI) concentration ratios as high as 1000. The new method has demonstrated excellent comparability with two commonly used methods, the Hach Company direct colorimetric method and USEPA method 218.6. The new method is superior to the Hach direct colorimetric method owing to its relative sensitivity and simplicity. The new method is superior to USEPA method 218.6 in the presence of Fe(II) concentrations up to 1 mg 1-1 and Fe(III) concentrations up to 10 mg 1-1. Time stability of preserved samples is a significant advantage over the 24-h time constraint specified for USEPA method 218.6.

Talanta↗

Questa baseline and pre-mining ground-water quality investigation. 2. Low-flow (2001) and snowmelt (2002) synoptic/tracer water chemistry for the Red River, New Mexico

Water analyses are reported for 259 samples collected from the Red River, New Mexico, and its tributaries during low-flow(2001) and spring snowmelt (2002) tracer studies. Water samples were collected along a 20-kilometer reach of the Red River beginning just east of the town of Red River and ending at the U.S. Geological Survey streamflow-gaging station located east of Questa, New Mexico. The study area was divided into three sections where separate injections and synoptic sampling events were performed during the low-flow tracer study. During the spring snowmelt tracer study, three tracer injections and synoptic sampling events were performed bracketing the areas with the greatest metal loading into the Red River as determined from the low-flow tracer study. The lowflow tracer synoptic sampling events were August 17, 20, and 24, 2001. The synoptic sampling events for the spring snowmelt tracer were March 30, 31, and April 1, 2002. Stream and large inflow water samples were sampled using equal-width and depth-integrated sampling methods and composited into half-gallon bottles. Grab water samples were collected from smaller inflows. Stream temperatures were measured at the time of sample collection. Samples were transported to a nearby central processing location where pH and specific conductance were measured and the samples processed for chemical analyses. Cations, trace metals, iron redox species, and fluoride were analyzed at the U.S. Geological Survey laboratory in Boulder, Colorado. Cations and trace metal concentrations were determined using inductively coupled plasma-optical emission spectrometry and graphite furnace atomic absorption spectrometry. Arsenic concentrations were determined using hydride generation atomic absorption spectrometry, iron redox species were measured using ultraviolet-visible spectrometry, and fluoride concentrations were determined using an ion-selective electrode. Alkalinity was measured by automated titration, and sulfate, chloride, and bromide were analyzed by ion chromatography at the U.S. Geological Survey laboratory in Salt Lake City, Utah.

New Mexico↗

Chemical analyses of ground and surface waters, Ester Dome, central Alaska, 2000-2001

Water analyses are reported for ground and surface waters collected at 33 sites on and near Ester Dome, Fairbanks area, central Alaska during 2000-2001. This interdisciplinary study focused on documenting the temporal and spatial chemical variations in arsenic concentrations to elucidate the processes that lead to elevated arsenic concentrations in ground water. Field parameters and water analyses are reported for 17 domestic wells, 13 monitoring well sites, and 3 surface water sites. Sampling occurred during November 2000, February 2001, May 2001, July 2001, and September 2001. Waters in the study area are primarily Ca-HCO 3 type, with pH values ranging from 5.97 to 7.87. Dissolved arsenic concentrations ranged from less than 3 to 1160 micrograms per liter.

Alaska↗

A new cation-exchange method for accurate field speciation of hexavalent chromium

A new cation-exchange method for field speciation of Cr(VI) has been developed to meet present stringent regulatory standards and to overcome the limitations of existing methods. The new method allows measurement of Cr(VI) concentrations as low as 0.05 micrograms per liter, storage of samples for at least several weeks prior to analysis, and use of readily available analytical instrumentation. The sensitivity, accuracy, and precision of the determination in waters over the pH range of 2 to 11 and Fe concentrations up to 1 milligram per liter are equal to or better than existing methods such as USEPA method 218.6. Time stability of preserved samples is a significant advantage over the 24-hour time constraint specified for USEPA method 218.6.

Water-Resources Investigations Report↗

Metal interferences and their removal prior to the determination of As(T) and As(III) in acid mine waters by hydride generation atomic absorption spectrometry

Hydride generation atomic absorption spectrometry (HGAAS) is a sensitive and selective method for the determination of total arsenic (arsenic(III) plus arsenic(V)) and arsenic(III); however, it is subject to metal interferences for acid mine waters. Sodium borohydride is used to produce arsine gas, but high metal concentrations can suppress arsine production. This report investigates interferences of sixteen metal species including aluminum, antimony(III), antimony(V), cadmium, chromium(III), chromium(IV), cobalt, copper(II), iron(III), iron(II), lead, manganese, nickel, selenium(IV), selenium(VI), and zinc ranging in concentration from 0 to 1,000 milligrams per liter and offers a method for removing interfering metal cations with cation exchange resin. The degree of interference for each metal without cation-exchange on the determination of total arsenic and arsenic(III) was evaluated by spiking synthetic samples containing arsenic(III) and arsenic(V) with the potential interfering metal. Total arsenic recoveries ranged from 92 to 102 percent for all metals tested except antimony(III) and antimony(V) which suppressed arsine formation when the antimony(III)/total arsenic molar ratio exceeded 4 or the antimony(V)/total arsenic molar ratio exceeded 2. Arsenic(III) recoveries for samples spiked with aluminum, chromium(III), cobalt, iron(II), lead, manganese, nickel, selenium(VI), and zinc ranged from 84 to 107 percent over the entire concentration range tested. Low arsenic(III) recoveries occurred when the molar ratios of metals to arsenic(III) were copper greater than 120, iron(III) greater than 70, chromium(VI) greater than 2, cadmium greater than 800, antimony(III) greater than 3, antimony(V) greater than 12, or selenium(IV) greater than 1. Low recoveries result when interfering metals compete for available sodium borohydride, causing incomplete arsine production, or when the interfering metal oxidizes arsenic(III). Separation of interfering metal cations using cation-exchange prior to hydridegeneration permits accurate arsenic(III) determinations in acid mine waters containing high concentrations of interfering metals. Stabilization of the arsenic redox species for as many as 15 months is demonstrated for samples that have been properly filtered and acidified with HCl in the field. The detection limits for the method described in this report are 0.1 micrograms per liter for total arsenic and 0.8 micrograms per liter for arsenic(III).

Water-Resources Investigations Report↗

Water-chemistry data for selected springs, geysers, and streams in Yellowstone National Park, Wyoming, 1999-2000

Sixty-seven water analyses are reported for samples collected from 44 hot springs and their overflow drainages and two ambient-temperature acid streams in Yellowstone National Park (YNP) during 1990-2000. Thirty-seven analyses are reported for 1999, 18 for June of 2000, and 12 for September of 2000. These water samples were collected and analyzed as part of research investigations in YNP on microbially mediated sulfur oxidation in stream water, arsenic and sulfur redox speciation in hot springs, and chemical changes in overflow drainages that affect major ions, redox species, and trace elements. Most samples were collected from sources in the Norris Geyser Basin. Two ambient-temperature acidic stream systems, Alluvium and Columbine Creeks and their tributaries in Brimstone Basin, were studied in detail. Analyses were performed at or near the sampling site, in an on-site mobile laboratory truck, or later in a USGS laboratory, depending on stability of the constituent and whether or not it could be preserved effectively. Water temperature, specific conductance, pH, Eh, dissolved oxygen (D.O.), and dissolved H2S were determined on-site at the time of sampling. Alkalinity, acidity, and F were determined within a few days of sample collection by titration with acid, titration with base, and ion-selective electrode or ion chromatography (IC), respectively. Concentrations of S2O3 and SxO6 were determined as soon as possible (minutes to hours later) by IC. Concentrations of Br, Cl, NH4, NO2, NO3, SO4, Fe(II), and Fe(total) were determined within a few days of sample collection. Densities were determined later in the USGS laboratory. Concentrations of Li and K were determined by flame atomic absorption spectrometry. Concentrations of Al, As(total), B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), K, Li, Mg, Mn, Na, Ni, Pb, Se, Si, Sr, V, and Zn were determined by inductively-coupled plasma-optical emission spectrometry. Trace concentrations of Cd, Cr, Cu, Pb, and Sb were determined by Zeeman-corrected graphitefurnace atomic-absorption spectrometry. Trace concentrations of As(total) and As(III) were determined by hydride generation atomic-absorption spectrometry using a flow-injection analysis system. Concentrations of Cl, NO3, Br, and SO4 were determined by IC. Concentrations of Fe(II) and Fe(total) were determined by the ferrozine colorimetric method. Concentrations of NO2 were determined by colorimetry using matrix-matched standards. Concentrations of NH4 were determined by IC, with reanalysis by colorimetry where separation of Na and NH4 peaks was poor. Dissolved organic carbon (DOC) concentrations were determined by the wet persulfate oxidation method.

Wyoming↗

Rapid arsenite oxidation by Thermus aquaticus and Thermus thermophilus: Field and laboratory investigations

Thermus aquaticus and Thermus thermophilus, common inhabitants of terrestrial hot springs and thermally polluted domestic and industrial waters, have been found to rapidly oxidize arsenite to arsenate. Field investigations at a hot spring in Yellowstone National Park revealed conserved total arsenic transport and rapid arsenite oxidation occurring within the drainage channel. This environment was heavily colonized by Thermus aquaticus. In laboratory experiments, arsenite oxidation by cultures of Thermus aquaticus YT1 (previously isolated from Yellowstone National Park) and Thermus thermophilus HB8 was accelerated by a factor of over 100 relative to abiotic controls. Thermus aquaticus and Thermus thermophilus may therefore play a large and previously unrecognized role in determining arsenic speciation and bioavailability in thermal environments.

Environmental Science & Technology↗

Water-Chemistry and On-Site Sulfur-Speciation Data for Selected Springs in Yellowstone National Park, Wyoming, 1996-1998

Fifty-eight water analyses are reported for samples collected from 19 hot springs and their overflow drainages and one ambient-temperature acid stream in Yellowstone National Park (YNP) during 1996-98. These water samples were collected and analyzed as part of research investigations on microbially mediated sulfur oxidation in stream waters and sulfur redox speciation in hot springs in YNP and chemical changes in overflow drainages that affect major ions, redox species, and trace elements. The research on sulfur redox speciation in hot springs is a collaboration with the State University of New York at Stony Brook, Northern Arizona University, and the U.S. Geological Survey (USGS). One ambient-temperature acidic stream system, Alluvium Creek and its tributaries in Brimstone Basin, was studied in detail. Analyses were performed adjacent to the sampling site, in an on-site mobile laboratory truck, or later in a USGS laboratory, depending on stability and preservability of the constituent. Water temperature, specific conductance, pH, Eh, dissolved oxygen (D.O.), and dissolved H2S were determined on-site at the time of sampling. Alkalinity and F were determined within a few days of sample collection by titration and by ion-selective electrode, respectively. Concentrations of S2O3 and SxO6 were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Concentrations of Cl, SO4, and Br were determined by IC within a few days of sample collection. Concentrations of Fe(II) and Fe(total) were determined by ultraviolet/visible spectrophotometry within a few days of sample collection. Densities were determined later in the USGS laboratory. Concentrations of Li, Na, and K were determined by flame atomic absorption (Li) and emission (Na, K) spectrometry. Concentrations of Al, As(total), B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), Mg, Mn, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace concentrations of Cd, Se, As(total), Ni, and Pb were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Trace concentrations of As(total) and As(III) were determined by hydride generation using a flow-injection analysis system.

Open-File Report↗

New method for the direct determination of dissolved Fe(III) concentration in acid mine waters

A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II) ≫ Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction−oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), Al(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand (14 mg/L). Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2 μg/L (40 nM) using GFAAS and 20 μg/L (0.4 μM) by colorimetry.

Environmental Science & Technology↗