Geology topics
D. Kirk Nordstrom
Publications and source records attributed to D. Kirk Nordstrom.
A comparison of simultaneous plasma, atomic absorption, and iron colorimetric determinations of major and trace constituents in acid mine waters
Sixty-three water samples collected during June to October 1982 from the Leviathan/Bryant Creek drainage basin were originally analyzed by simultaneous multielement direct-current plasma (DCP) atomic-emission spectrometry, flame atomic-absorption spectrometry, graphite-furnace atomic-absorption spectrometry (GFAAS) (thallium only), ultraviolet-visible spectrometry, and hydride-generation atomic-absorption spectrometry.Determinations were made for the following metallic and semi-metallic constituents: AI, As, B, Ba, Be, Bi, Cd, Ca, Cr, Co, Cu, Fe(11), Fe(total), Li, Pb, Mg, Mn, Mo, Ni, K, Sb, Se, Si, Na, Sr, TI, V, and Zn. These samples were re-analyzed later by simultaneous multielement inductively coupled plasma (ICP) atomic-emission spectrometry and Zeeman-corrected GFAAS to determine the concentrations of many of the same constituents with improved accuracy, precision, and sensitivity. The result of this analysis has been the generation of comparative concentration values for a significant subset of the solute constituents. Many of the more recently determined values replace less-than-detection values for the trace metals; others constitute duplicate analyses for the major constituents. The multiple determinations have yielded a more complete, accurate, and precise set of analytical data. They also have resulted in an opportunity to compare the performance of the plasma-emission instruments operated in their respective simultaneous multielement modes. Flame atomic-absorption spectrometry was judged best for Na and K and hydride-generation atomic-absorption spectrometry was judged best for As because of their lower detection limit and relative freedom from interelement spectral effects. Colorimetric determination using ferrozine as the color agent was judged most accurate, precise, and sensitive for Fe. Cadmium, lead, and vanadium concentrations were too low in this set of samples to enable a determination of whether ICP or DCP is a more suitable technique. Of the remaining elements, Ba, Be, Ca, Cr, Mg, Mn, Sr, and Zn have roughly equivalent accuracy, precision, and detection limit by ICP and DCP. Cobalt and Ni were determined to be better analyzed by ICP, because of lower detection limits; B, Cu, Mo, and Si were determined to be better analyzed by DCP, because of relative freedom from interferences. The determination oral by DCP was far more sensitive, owing to the use of a more sensitive wavelength, compared with the ICP. However, there is a very serious potential interference from a strong Ca emission line near the 396.15 nanometer DCP wavelength. Thus, there is no clear choice between the plasma techniques tested, for the determination oral. The ICP and DCP detection limits are typically between 0.001 and 0.5 milligrams per liter in acid mine waters. For those metals best analyzed by ICP and/or DCP, but below these limits, GFAAS is the method of choice because of its relatively greater sensitivity and specificity. Six of the elements were not determined by DCP, ICP or Zeeman-corrected GFAAS, and are not discussed in this report. These elements are: Bi, Fe(11), Li, Sb, Se, and TI.
Secondary minerals and acid mine-water chemistry
No abstract available.
Solubility-product constant and thermodynamic properties for synthetic otavite, CdCO3(s), and aqueous association constants for the Cd(II)-CO2-H2O system
Considerable disparity exists in the published thermodynamic data for selected species in the Cd(II)-CO 2 -H 2 O system near 25°C and 1 atm pressure. Evaluation of published experimental and estimated data for aqueous cadmium-carbonate species suggests an association constant, pK , of −3.0 ± 0.4 for CdCO 3 0 , about −1.5 for CdHCO 3 + , and −6.4 ± 0.1 for Cd(CO 3 ) 2 2− ( T = 298.15 K ; P = 1 atm; I = 0). Examination of all available data for cadmium-hydrolysis species and β - Cd ( OH ) 2( s ) ) confirms that the consistent set of constants presented by Baes and Mesmer ( Hydrolysis of Cations , 1976) is the best available. The solubility of synthetic otavite, CdCO 3(s) , has been measured in KClO 4 solutions where I ≤ 0.1 M . We calculated pK sp = 12.1 ± 0.1 ( T = 25.0° C ; P = 1 atm; I = 0) from measured concentrations of Cd 2+ , measured P C 02 and pH, our selected set of equilibrium constants, and activity corrections estimated using the Davies equation. Values at 5 and 50°C were 12.4 ± 0.1 and 12.2 ± 0.1, respectively. Based on the new solubility data and the CODATA key values for Cd 2+ and CO 3 2− , a new set of thermodynamic properties is recommended for otavite: ΔG f 0 = −674.7 ± 0.6 kJ / mol ; ΔH f 0 = −751.9 ± 10 kJ / mol ; S 0 = 106 ± 30 J/mol K; and ΔG r 0 for the reaction Cd 2+ + CO 3 2− ⇌ CdCO 3 ( s ) is −69.08 ± 0.57 kJ / mol.
Ground water chemistry and geochemical modeling of water-rock interactions at the Osamu Utsumi mine and the Morro do Ferro analogue study sites, Poços de Caldas, Minas Gerais, Brazil
Surface and ground waters, collected over a period of three years from the Osamu Utsumi uranium mine and the Morro do Ferro thorium/rare-earth element (Th/REE) deposits, were analyzed and interpreted to identify the major hydrogeochemical processes. These results provided information on the current geochemical evolution of ground waters for two study sites within the Poços de Caldas Natural Analogue Project. The ground waters are a K–Fe–SO 4 –F type, a highly unusual composition related to intense weathering of a hydrothermally altered and mineralized complex of phonolites. Tritium and stable isotope data indicate that ground waters are of meteoric origin and are not affected significantly by evaporation or water–rock interactions. Recharging ground waters at both study sites demonstrate water of less than about 35 years in age, whereas deeper, more evolved ground waters are below 1 TU but still contain in most cases detectable tritium. These deeper ground waters may be interpreted as being of 35 to 60 or more years in age, resulting mainly from an admixture of younger with older ground waters and/or indicating the influence of subsurface produced tritium. Geochemical processes involving water–rock–gas interactions have been modeled using ground water compositions, mineralogic data, ion plots and computations of speciation, non-thermodynamic mass balance and thermodynamic mass transfer. The geochemical reaction models can reproduce the water chemistry and mineral occurrences and they were validated by comparing the results of thermodynamic mass transfer calculations (using the PHREEQE program, Parkhurst et al., 1980). The results from the geochemical reaction models reveal that the dominant processes are production of CO 2 in the soil zone through aerobic decay of organic matter, dissolution of fluorite, calcite, K-feldspar, albite, chlorite and manganese oxides, oxidation of pyrite and sphalerite, and precipitation of ferric oxides, silica and kaolinite. Gibbsite precipitation can be modeled for the shallow (recharge) water chemistry at Morro do Ferro, consistent with known mineralogy. Recharge waters are undersaturated with respect to barite and discharging waters and deeper ground waters are saturated to supersaturated with respect to barite demonstrating a strong solubility control. Strontium isotope data demonstrate that sources other than calcium-bearing minerals are required to account for the dissolved strontium in the ground waters. These may include K-feldspar, smectite–chlorite mixed-layer clays and goyazite [SrAl 3 (PO 4 ) 2 (OH) 5 • H 2 O]. 1992.
Assessing the solubilities and reaction kinetics of aluminous minerals in soils
The use of chemical thermodynamics and reaction kinetics is necessary to quantitatively model the transformation of aluminous minerals and their dissolved constituents in soils and other geochemical systems. Soils are thermodynamically open systems subject to atmospheric and biological forces and do not attain overall thermodynamic equilibrium with respect to either mass or time. However, local or partial equilibrium conditions may persist for particular minerals and their dissolved constituents. Igneous and metamorphic primary minerals break down chemically to yield disordered gels or colloids and constituent ions, which can then reorganize or precipitate to form more stable hydrous oxides, silicates, carbonates or other mineral species. Naturally-occurring iron and aluminum hydrous oxides and kaolin clays, abundant in highly weathered soils, are commonly believed to be the ultimate, stable end products of weathering reactions, but usually are thermodynamically metastable with respect to more perfectly ordered, synthetic specimens. Thermodynamic stability is no guaranty of mineral persistence; with sufficient time, even the most perfectly crystallized, stable mineral will yield to the solubilizing assault of undersaturated surface waters. All of the dissolution and precipitation reactions of soil minerals are driven by energy differences in the thermodynamic stabilities of reactants and products, and the velocities (or kinetics) of such reactions are regulated by variables of the hydrogeochemical environment.
The production and variability of acid mine drainage at Iron Mountain, California: A superfund site undergoing rehabilitation
No abstract available.
Stoichiometry of mineral reactions from mass balance computations for acid mine waters, Iron Mountain, California
No abstract available.
Groundwater chemistry and water-rock interactions at Stripa
Groundwaters from near surface to a depth of 1232 m in the Stripa granite have been sampled and analyzed for major and trace constituents. The groundwater composition consists of two general types: a typical recharge water of Ca-HCO 3 type (<300 m depth) and a deeper Na-Ca-Cl type (>700 m depth) of high pH (8–10) that reaches a maximum of 1250 mg/L in total dissolved solids (TDS). Intermediate depths show mixtures of the two types that are highly fracture-dependent rather than depth-dependent. Any borehole can vary significantly and erratically in TDS for either a horizontal or vertical direction. The general transition from Ca-HCO 3 type to Na-Ca-Cl type correlates with the depth profile for hydraulic conductivity that drops from 10 −8 m/s to 10 −11 m/s or lower. Thermomechanical stress (from heater experiments) clearly shows an effect on the groundwater composition that could be caused by changing flow paths, leakage of fluid inclusions or both. Dissolution and precipitation of calcite, fluorite and barite, aluminosilicate hydrolysis, and addition of a saline source (possibly fluid inclusion leakage) play the major roles in defining the groundwater composition. The low permeability of the Stripa granite has produced a groundwater composition that appears intermediate between the dilute, shallow groundwaters typical of recharge in a crystalline rock terrain and the saline waters and brines typical of cratonic shield areas at depth.
Solubility of jarosite solid solutions precipitated from acid mine waters, Iron Mountain, California
Because of the common occurrence of 15 to 25 mole percent hydronium substitution on the alkali site in jarosites, it is necessary to consider the hydronium content of jarosites in any attempt at rigorous evaluation of jarosite solubility or of the saturation state of natural waters with respect to jarosite. A Gibbs free energy of 3293.5±2.1 kJ mol-1 is recommended for a jarosite solid solution of composition K.77Na.03(H3O).20Fe3(SO4)2(OH)6. Solubility determinations for a wider range of natural and synthetic jarosite solid solutions will be necessary to quantify the binary and ternary mixing parameters in the (K-Na-H3O) system. In the absence of such studies, molar volume data for endmember minerals indicate that the K-H3O substitution in jarosite is probably closer to ideal mixing than either the Na-K or Na-H3O substitution.
Mineral saturation states in natural waters and their sensitivity to thermodynamic and analytical errors
Saturation indices computed with WATEQ4F chemical analyses from a groundwater in crystalline bedrock and a surface water receiving acid mine drainage are frequently at or above saturation with respect to calcite, fluorite, barite, gibbsite and ferrihydrite. Deep granitic groundwaters from Stripa, Sweden, are supersaturated with respect to calcite and fluorite. Acid mine waters from the Leviathan Mine drainage basin in California are supersaturated with respect to barite by about a factor of three. These mine waters also are 10 times supersaturated with respect to the most soluble form of ferric hydroxide but are near saturation with respect to microcrystalline gibbsite. A sensitivity analysis has been performed by varying the analytic and thermodynamic parameters for which the saturation indices are most sensitive. For calcite, fluorite and barite, the supersaturation effect appears to be real because it is only slightly decreased by sources of uncertainty. Apparent supersaturation for gibbsite is most likely caused by the degree of crystallinity on solubility behavior. Apparent supersaturation for ferric hydroxide is likely caused by small colloidal particles (< 0.1 µ m) in the water sample that cannot be removed by standard field filtration, although several other possible explanations cannot be easily excluded.
Book review--"Coupled processes associated with nuclear waste repositories"
No abstract available.
Aqueous pyrite oxidation by dissolved oxygen and by ferric iron
Rates of aqueous, abiotic pyrite oxidation were measured in oxygen-saturated and anaerobic Fe(III)-saturated solutions with initial pH from 2 to 9. These studies included analyses of sulfite, thiosulfate, polythionates and sulfate and procedures for cleaning oxidation products from pyrite surfaces were evaluated. Pyrite oxidation in oxygen-saturated solutions produced (1) rates that were only slightly dependent on initial pH, (2) linear increases in sulfoxy anions and (3) thiosulfate and polythionates at pH > 3.9. Intermediate sulfoxy anions were observed only at high stirring rates. In anaerobic Fe(III)-saturated solutions, no intermediates were observed except traces of sulfite at pH 9. The faster rate of oxidation in Fe(III)-saturated solutions supports a reaction mechanism in which Fe(III) is the direct oxidant of pyrite in both aerobic and anaerobic systems. The proposal of this mechanism is also supported by theoretical considerations regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic pyrite. Results from a study of sphalerite oxidation support the hypothesis that thiosulfate is a key intermediate in sulfate production, regardless of the bonding structure of the sulfide mineral.
Solubility and stability of scorodite, FeAsO4.2H2O: Discussion
Reported solubility data for a synthetic scorodite and the techniques used to prepare the synthetic phase are questioned. (A.M. 70-838, 72-852)-J.A.Z.
The geochemical behavior of aluminum in acidified surface waters
Speciation calculations for aluminum, in water samples taken from a drainage basin containing acid mine waters, demonstrate a distinct transition from conservative behavior for p H. below 4.6 to nonconservative behavior for p H. above 4.9. This transition corresponds to the pK for the first hydrolysis constant of the aqueous aluminum ion and appears to be a consistent phenomenon independent of field location, ionic strength, and sulfate concentration. Nonconservative behavior is closely correlated with the equilibrium solubility of a microcrystalline gibbsite or amorphous aluminum hydroxide.