Darrell Kirk Nordstrom

The effect of sulfate on aluminum concentrations in natural waters: some stability relations in the system Al2O3-SO3-H2O at 298 K

Abstract While gibbsite and kaolinite solubilities usually regulate aluminum concentrations in natural waters, the presence of sulfate can dramatically alter these solubilities under acidic conditions, where other, less soluble minerals can control the aqueous geochemistry of aluminum. The likely candidates include alunogen, Al 2 (SO 4 ) 3 · 17H 2 O, alunite, KAl 3 (SO 4 ) 2 (OH) 6 , jurbanite, Al(SO 4 )(OH) · 5H 2 O, and basaluminite, Al 4 (SO 4 )(OH) 10 · 5H 2 O. An examination of literature values shows that the log K sp = −85.4 for alunite and log K sp = −117.7 for basaluminite. In this report the log K sp = −7.0 is estimated for alunogen and log K sp = −17.8 is estimated for jurbanite. The solubility and stability relations among these four minerals and gibbsite are plotted as a function of pH and sulfate activity at 298 K. Alunogen is stable only at pH values too low for any natural waters ( pH up to the range of 3–5 depending on sulfate activity. Alunite is stable at higher pH values than jurbanite, up to 4–7 depending on sulfate activity. Above these pH limits gibbsite is the most stable phase. Basaluminite, although kinetically favored to precipitate, is metastable for all values of pH and sulfate activity. These equilibrium calculations predict that both sulfate and aluminum can be immobilized in acid waters by the precipitation of aluminum hydroxysulfate minerals. Considerable evidence supports the conclusion that the formation of insoluble aluminum hydroxy-sulfate minerals may be the cause of sulfate retention in soils and sediments, as suggested by Adams and Rawajfih (1977), instead of adsorption.

Stable isotope geochemistry of acid mine drainage: Experimental oxidation of pyrite

Sulfate and water from experiments in which pyrite was oxidized at a pH of 2.0 were analyzed for sulfur and oxygen stable isotopes. Experiments were conducted under both aerobic and anaerobic sterile conditions, as well as under aerobic conditions in the presence of Thiobacillus ferrooxidans, to elucidate the pathways of oxidation. Oxygen isotope fractionation between SO2−4 and H2O varied from +4.0 %. (anaerobic, sterile) to + 18.0 %. (aerobic, with T. ferrooxidans.). The oxygen isotope composition of dissolved oxygen utilized in both chemical and microbially-mediated oxidation was also determined (+11.4 %., by T. ferrooxidans; +18.4 %., chemical). Contributions of water-derived oxygen and dissolved oxygen to the sulfate produced in the oxidation of pyrite could thus be estimated. Water-derived oxygen constituted from 23 to ~ 100 percent of the oxygen in the sulfate produced in the experiments, and this closely approximates the range of contribution in natural acid mine drainage. Oxidation of sulfides in anaerobic, water-saturated environments occurs primarily by chemical oxidation pathways, whereas oxidation of sulfides in well-aerated, unsaturated zone environments occurs dominantly by microbially mediated pathways.

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.

Fluorite solubility equilibria in selected geothermal waters

A~~aet~alculation of chemical equilibria in 351 hot springs and surface waters from selected geothermal areas in the western United States indicate that the solubility of the mineral fluorite, CaF,, provides an equilibrium control on dissolved fluoride activity. Waters that are undersaturated have undergone dilution by non-thermal waters as shown by decreased conductivity and temperature values, and only 2% of the samples are supersaturated by more than the expected error. Calculations also demonstrate that simultaneous chemical equilibria between the thermal waters and calcite as well as fluorite minerals exist under a variety of conditions. Testing for fluorite solubility required a critical review of the thermodynamic data for fluorite. By applying multiple regression of a mathematical model to selected published data we have obtained revised estimates of the pK (10,96), AGY (- 280.08 kcal/mole), AN? (-292.59 kcal/mole), S’ (16.39 cal/deg/mole) and CF (16.16 cal/deg/mole) for CaF, at 25°C and 1 atm. Association constants and reaction enthalpies for fluoride complexes with boron, calcium and iron are included in this review. The excellent agreement between the computer-based activity products and the revised pK suggests that the chemistry of geothermal waters mav also be a guide to evaluating mineral solubility data where major discrepancies are evident.

Fluid inclusions in the Stripa granite and their possible influence on the groundwater chemistry

Fluid inclusions in quartz and calcite of the Proterozoic Stripa granite, central Sweden, demonstrate that the rock and its fracture fillings have a complex evolutionary history. The majority of inclusions indicate formation during a hydrothermal stage following emplacement of the Stripa pluton. Total salinities of quartz inclusions range from 0–18 eq.wt% NaCl for unfractured rock and from 0–10 eq.wt% for fractured rock. Vein calcites contain up to 25 eq.wt% NaCl but the inclusion size is larger and the population density is lower. Homogenization temperatures are 100–150°C for unfractured rock and 100–250° for fractured rock. Pressure corrections, assuming immediate post-emplacement conditions of 2 kbar, give temperatures about 160°C higher. Measurements of fluid-inclusion population-densities in quartz range from about 108 inclusions/cm3 in grain quartz to 109 inclusions/cm3 in vein quartz. Residual porosity from inclusion densities has been estimated to be at least 1% which is two orders of magnitude greater than the flow porosity. Breakage and leaching of fluid inclusions is proposed as an hypothesis for the origin of major solutes (Na-Ca-Cl) in the groundwater. Evidence for the hypothesis is based on (1) mass balance—only a small fraction of the inclusions need to leak to account for salt concentrations in the groundwater, (2) chemical signatures—BrCl ratios of fluid inclusion leachates (0.0101) match those ratios for the deep groundwaters (0.0107), (3) leakage mechanisms—micro-stresses from isostatic rebound or mining activities acting on irregular-shaped inclusions could cause breakage and provide connection with the flow porosity, and (4) experimental studies—water forced through low permeability granites leach significant quantities of salt. This hypothesis is consistent with the available data although alternate hypotheses cannot be excluded.

Introduction to the hydrogeochemical investigations within the International Stripa Project

Abstract The International Stripa Project (1980–1990) has sponsored hydrogeochemical investigations at several subsurface drillholes in the granitic portion of an abandoned iron ore mine, central Sweden. The purpose has been to advance our understanding of geochemical processes in crystalline bedrock that may affect the safety assessment of high-level radioactive waste repositories. More than a dozen investigators have collected close to a thousand water and gas samples for chemical and isotopic analyses to develop concepts for the behavior of solutes in a granitic repository environment. The Stripa granite is highly radioactive and has provided an exceptional opportunity to study the behavior of natural radionuclides, especially subsurface production. Extensive microfracturing, low permeability with isolated fracture zones of high permeability, unusual water chemistry, and a typical granitic mineral assemblage with thin veins and fracture coatings of calcite, chlorite, seriate, epidote and quartz characterize the site. Preliminary groundwater flow modeling indicates that the mine has perturbed the flow environment to a depth of about 3 km and may have induced deep groundwaters to flow into the mine.

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.