James W. Ball

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 pH below 4.6 to nonconservative behavior for pH 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.

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-HCO3 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-HCO3 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.

Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis

Abstract A method has been developed for separating the Cr dissolved in natural water from matrix elements and determination of its stable isotope ratios using solid-source thermal-ionization mass spectrometry (TIMS). The separation method takes advantage of the existence of the oxidized form of Cr as an oxyanion to separate it from interfering cations using anion-exchange chromatography, and of the reduced form of Cr as a positively charged ion to separate it from interfering anions such as sulfate. Subsequent processing of the separated sample eliminates residual organic material for application to a solid source filament. Ratios for 53 Cr/ 52 Cr for National Institute of Standards and Technology Standard Reference Material 979 can be measured using the silica gel-boric acid technique with a filament-to-filament standard deviation in the mean 53 Cr/ 52 Cr ratio for 50 replicates of 0.00005 or less.

Chemical Models, Computer Programs and Metal Complexation in Natural Waters

It has been about 22 years since the first publication of a paper on the speciation of a natural water (Garrels and Thompson, 1962) and about 15 years since the appearance of papers in which computers were used to model the chemistry of water-mineral reactions (Helgeson, et al., 1969, 1970). The use of computers to solve chemical equilibrium problems for aqueous systems has expanded enormously and “chemical modeling” is now a common phrase describing the application of physico-chemical principles to the interpretation of natural hydrogeochemical systems (Jenne, 1979). Nordstrom, et al. (1979) reviewed computerized chemical models for aqueous systems but in the last five years there have been significant advances in electrolyte theory and evaluated thermodynamic data which have found applications in chemical modeling. The number of computer programs has nearly doubled since the 1979 review paper and an attempt is made in this paper to inventory these programs, review the shortcomings of some of the traditional methods of calculating speciation and suggest avenues for improvement in the chemical models which could be incorporated into the programs.

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park, Wyoming, USA. III. An anion-exchange resin technique for sampling and preservation of sulfoxyanions in natural waters

A sampling protocol for the retention, extraction, and analysis of sulfoxyanions in hydrothermal waters has been developed in the laboratory and tested at Yellowstone National Park and Green Lake, NY. Initial laboratory testing of the anion-exchange resin Bio-Rad™ AG1-X8 indicated that the resin was well suited for the sampling, preservation, and extraction of sulfate and thiosulfate. Synthetic solutions containing sulfate and thiosulfate were passed through AG1-X8 resin columns and eluted with 1 and 3 M KCl, respectively. Recovery ranged from 89 to 100%. Comparison of results for water samples collected from five pools in Yellowstone National Park between on-site IC analysis (U.S. Geological Survey mobile lab) and IC analysis of resin-stored sample at SUNY-Stony Brook indicates 96 to 100% agreement for three pools (Cinder, Cistern, and an unnamed pool near Cistern) and 76 and 63% agreement for two pools (Sulfur Dust and Frying Pan). Attempts to extract polythionates from the AG1-X8 resin were made using HCl solutions, but were unsuccessful. Bio-Rad™ AG2-X8, an anion-exchange resin with weaker binding sites than the AG1-X8 resin, is better suited for polythionate extraction. Sulfate and thiosulfate extraction with this resin has been accomplished with KCl solutions of 0.1 and 0.5 M, respectively. Trithionate and tetrathionate can be extracted with 4 M KCl. Higher polythionates can be extracted with 9 M hydrochloric acid. Polythionate concentrations can then be determined directly using ion chromatographic methods, and laboratory results indicate recovery of up to 90% for synthetic polythionate solutions using AG2-X8 resin columns.

Determination of dissolved boron in fresh, estuarine, and geothermal waters by d.c. argon-plasma emission spectrometry

Abstract A d.c. argon-plasma emission spectrometer is used to determine dissolved boron in natural (fresh and estuarine) water samples. Concentrations ranged from 0.02 to 250 mg l -1 . The emission—concentration function is linear from 0.02 to 1000 mg l -1 . Achievement of a relative standard deviation of ⩽ 3% requires frequent restandardization to offset sensitivity changes. Dilution may be necessary to overcome high and variable electron density caused by differences in alkali-metal content and to avoid quenching of the plasma by high solute concentrations of sodium and other easily ionized elements. The proposed method was tested against a reference method and found to be more sensitive, equally or more precise and accurate, less subject to interferences, with a wider linear analytical range than the carmine method. Analyses of standard reference samples yielded results in all cases within one standard deviation of the means.

Specific-lon electrode determinations of sulfide preconcentrated from San Francisco Bay waters

Measurements of low-level dissolved-sulfide concentrations in estuarine water from San Francisco Bay have been made using the sulfide-specific electrode after preservation, separation, and preconcentration of the sulfide species. The separation and preconcentration were acheived by coprecipitation of ZnS with Zn(OH)2 followed by collection and dissolution of the precipitate, giving concentration factors up to 160-fold Preconcentration provided sulfide solutions that were adequately measurable within the practical working range of the specific-ion electrode The sulfide detection limit with the preconcentration step is 0 02 μg/l Spike recoveries in the range of 81 to 10 1% have been achieved for laboratory-prepared samples having S2− concentrations as low as 0 6 μg/l and 84 to 100% for an estuarine sample spiked in the field with 2 μg/l (S(−II) Positive correlations have been found between dissolved S(−II) concentrations and concentrations of dissolved Cd, Cu, and Ni, negative correlations have been found between bisulfide (HS−) activity and activities of Cd2+, Cu2+, and Ag+ species

Mineral saturation states in natural waters and their sensitivity to thermodynamic and analytic errors. Etat de saturation des minéraux dans les eaux naturelles et sensibilité des tests aux données thermodynamiques et aux erreurs analytiques

Saturation indices computed with WATEWF~O~ 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. Deepgranitic groundwaters from Stripa, Sweden,arc supersaturated with respect tocalcite 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 peformed 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 pm) in the water sample that cannot be removed by standard field filtration, although several other possible explanations cannot be easily excluded. Mineral saturation, Sensitivity analysis, Calcite, Fluorite, Barite, Gibbsite, Femhydrite, Speciation, Saturation indices