Tom A. Al

Carbonate-mineral/water interactions in sulfide-rich mine tailings

The chemical composition and mineralogy of coatings on carbonate minerals from mine tailings have been studied using aqueous geochemical methods, Time-of-Flight Laser-Ionization Mass Spectrometry (TOF-LIMS) and Transmission Electron Microscopy (TEM). The goal is to study major and trace element partitioning between the aqueous and solid phase, and to infer mechanisms that control the concentrations of elements in the pore water of sulfide-rich mine tailings. Pore-water samples and carbonate-mineral grains were collected from four geochemically distinct zones within the tailings. Oxidation of sulfide minerals near the surface results in a large range in pore-water pH (3.85 to 6.98) and aqueous concentrations of metals and sulfate. With increasing depth in the tailings, mineral-water interactions lead to increasing pH, and decreasing concentrations of metals and sulfate. Calculated mineral saturation indices, trends in the abundance of Ca, Fe, Mg and Mn in TOF-LIMS profiles through the secondary coatings, and electron diffraction patterns obtained from the coatings, suggest that precipitation/dissolution of jarosite-group minerals, gypsum, goethite, akaganeite, amorphous Fe oxyhydroxides and siderite control the aqueous Ca, Fe, Na, K and SO4 concentrations. The occurrence of secondary coatings on primary minerals is widespread, and reactions with the secondary minerals, rather than the primary mineral substrate, probably represent the principal controls on trace-element distributions in the pore water. The data indicate that adsorption, surface-complexation and co-precipitation reactions are important controls on the concentrations of trace elements in the pore water. The occurrence of siderite coatings on the surface of ankerite grains suggests that Fe-bearing dolomite-structure carbonate minerals dissolve incongruently. This corroborates inferences made by previous workers that solubility differences between calcite and siderite lead to calcite dissolution and siderite precipitation during acid neutralization. The accumulation of secondary coatings will diminish the rate of mineral-dissolution reactions involving the primary minerals. Consequently, the use of kinetic rate constants obtained from the literature for simulating the dissolution of primary mineral phases such as the carbonates and alumino-silicates will likely overestimate the actual rates.

Aqueous geochemistry and analysis of pyrite surfaces in sulfide-rich mine tailings

Abstract Aqueous geochemical techniques and analysis of pyrite surfaces have been used to study element partitioning between the aqueous and solid phase and to infer mechanisms that limit the concentrations of elements in porewater in a sulfide-rich mine tailings impoundment. Porewater samples and pyrite grains for surface analysis were collected from oxidized and unoxidized zones within the tailings. Surface analyses were conducted using a Time-of-Flight Laser-Ionization Mass Spectrometer (TOFLIMS). The porewater pH at the different sample locations varies from 3.85 to 6.98. High relative abundances of Na, K, Ca, Mg, Al, and Ni occur at the surfaces of the pyrite grains from all of the sample locations. The porewater concentrations of these elements in the low-pH zone may be controlled by precipitation or coprecipitation in secondary mineral coatings on the pyrite surface. Surface abundances of the metals Cu, Ag, Pb, Zn, and Cd are lowest, and porewater concentrations are highest, in the low-pH oxidized tailings. Surface abundances of As are greatest, and porewater concentrations are lowest, in the low-pH sulfide-oxidation zone. These trends vs. pH are consistent with an adsorption model for attenuation of Cu, Ag, Pb, Zn, Cd, and As from the porewater. The porewater Cu and Ag concentrations may be limited by replacement reactions that form secondary Cu and Ag sulfides at the pyrite surface. The highest abundance of C on the surface of the pyrite grains is in the shallow sulfide-oxidation zone; this interval coincides with large abundances of chemolithotrophic bacteria and may reflect populations of iron- and sulfur-oxidizing bacteria such as Thiobacilli.

Microbiological, chemical, and mineralogical characterization of the kidd creek mine tailings impoundment, Timmins area, Ontario

Bacterial enumeration and geochemical characterization were undertaken at three sites on the sulfide‐rich tailings impoundment at the Kidd Creek metallurgical site, Timmins, Ontario, Canada. The three sites were selected to represent varying degrees of sulfide oxidation to assess the changes in water chemistry, in the mineralogical composition of the tailings, and in bacterial populations as the sulfide oxidation process proceeds under natural field conditions. The first site was characterized as having negligible oxidation‐derived alteration, the pH of the porewater varied from 6.5 to 7.5, and the concentrations of dissolved constituents were similar to those observed in the deeper, unaltered tailings. Mineralogical examination of the tailings grains indicated that the sulfide surfaces were sharp and unreplaced. At this site, the predominant sulfur‐oxidizing bacteria were Thiobacillus thioparus and related species. The second site showed evidence of the onset of acidification, the pH of the near‐surface ...

Three-dimensional density-dependent flow and multicomponent reactive transport modeling of chlorinated solvent oxidation by potassium permanganate.

A popular method for the treatment of aquifers contaminated with chlorinated solvents is chemical oxidation based on the injection of potassium permanganate (KMnO(4)). Both the high density (1025 gL(-1)) and reactivity of the treatment solution influence the fate of permanganate (MnO(4)) in the subsurface and affect the degree of contaminant treatment. The MIN3P multicomponent reactive transport code was enhanced to simulate permanganate-based remediation, to evaluate the pathways of MnO(4) utilization, and to assess the role of density contrasts for the delivery of the treatment solution. The modified code (MIN3P-D) provides a direct coupling between density-dependent fluid flow, solute transport, contaminant treatment, and geochemical reactions. The model is used to simulate a field trial of TCE oxidation in a sandy aquifer that is underlain by an aquitard. Three-dimensional simulations are conducted for a coupled reactive system comprised of ten aqueous components, two mineral phases, TCE (dissolved, adsorbed, and NAPL), reactive organic matter, and including ion exchange reactions. Model parameters are constrained by literature data and a detailed data set from the field site under investigation. The general spatial and transient evolution in observed concentrations of the oxidant, dissolved TCE, and reaction products are adequately reproduced by the simulations. The model elucidates the important role of density-induced flow and transport on the distribution of the treatment solution into NAPL containing regions located at the aquifer-aquitard interface. Model results further suggest that reactions that do not directly affect the stability of MnO(4) have a negligible effect on solution density and MnO(4) delivery.

Paleozoic-aged brine and authigenic helium preserved in an Ordovician shale aquiclude

Consideration of the geosphere for isolation of nuclear waste has generated substantial interest in the origin, age, and movement of fl uids and gases in low-permeability rock formations. Here, we present profi les of isotopes, solutes, and helium in porewaters recovered from 860 m of Cambrian to Devonian strata on the eastern fl ank of the Michigan Basin. Of particular interest is a 240-m-thick, halite-mineralized, Ordovician shale and carbonate aquiclude, which hosts Br–-enriched, post-dolomitic brine (5.8 molal Cl) originating as evaporated Silurian seawater. Authigenic helium that has been accumulating in the aquiclude for more than 260 m.y. is found to be isolated from underlying allochthonous, 3He-enriched helium that originated from the rifted base of the Michigan Basin and the Canadian Shield. The Paleozoic age and immobility of the pore fl uids in this Ordovician aquiclude considerably strengthen the safety case for deep geological repositories, but also provide new insights into the origin of deep crustal brines and opportunities for research on other components of a preserved Paleozoic porewater system.

Manganese valence imaging in Mn minerals at the nanoscale using STEM-EELS

Abstract Electron energy loss spectroscopy (EELS) was used with scanning transmission electron microscopy (STEM) to quantify the average Mn valence in natural minerals at the nanometer scale. A method was developed to calibrate the energy-loss scale accurately, providing a comparison between STEMEELS and the X-ray absorption spectroscopy methods that investigate the L-edge chemical shift as Mn valence changes. The chemical-shift measurements were consistent with data reported by previous researchers from both X-ray and electron energy-loss spectroscopy. The L3/L2 white-line intensity ratios also were consistent with previous work. A calibration curve for Mn valence was produced using the L3/L2 white-line intensity ratios from measurements of synthetic standards. The average Mn valence was determined because it is not possible to distinguish Mn3+ from mixtures of Mn2+ and Mn4+ using either method. The white-line intensity method was implemented in automated software that allows for rapid processing of point spectra, and 1-D and 2-D spectrum images. Point analyses of two natural pyrolusite samples indicated a Mn valence of 4.0, and point analyses of romanechite and manganite gave values of 3.8 and 3.4, respectively. An interface between braunite and bementite was used to illustrate 1-D and 2-D spectrum-imaging capabilities. The measured valence of Mn in the braunite and bementite was 2.9 and 2.0, respectively; both consistent with theoretical values. The braunitebementite sample demonstrated the heterogeneity of Mn valence common to natural minerals and the advantages of acquiring quantitative valence information in a known spatial context.

A technique for estimating one-dimensional diffusion coefficients in low-permeability sedimentary rock using X-ray radiography: Comparison with through-diffusion measurements

The measurement of diffusive properties of low-permeability rocks is of interest to the nuclear power industry, which is considering the option of deep geologic repositories for management of radioactive waste. We present a simple, non-destructive, constant source in-diffusion method for estimating one-dimensional pore diffusion coefficients (D(p)) in geologic materials based on X-ray radiography. Changes in X-ray absorption coefficient (Deltamicro) are used to quantify changes in relative concentration (C/C(0)) of an X-ray attenuating iodide tracer as the tracer solution diffuses through the rock pores. Estimated values of D(p) are then obtained by fitting an analytical solution to the measured concentration profiles over time. Measurements on samples before and after saturation with iodide can also be used to determine iodide-accessible porosity (phi(I)). To evaluate the radiography method, results were compared with traditional steady-state through-diffusion measurements on two rock types: shale and limestone. Values of D(p) of (4.8+/-2.5)x10(-11) m(2).s(-1) (mean+/-standard deviation) were measured for samples of Queenston Formation shale and (2.6+/-1.0)x10(-11) m(2).s(-1) for samples of Cobourg Formation limestone using the radiography method. The range of results for each rock type agree well with D(p) values of (4.6+/-2.0)x10(-11) m(2).s(-1) for shale and (3.5+/-1.8)x10(-11) m(2).s(-1) for limestone, calculated from through-diffusion experiments on adjacent rock samples. Low porosity (0.01 to 0.03) and heterogeneous distribution of porosity in the Cobourg Formation may be responsible for the slightly poorer agreement between radiography and through-diffusion results for limestones. Mean values of phi(I) for shales (0.060) and limestones (0.028) were close to mean porosity measurements made on bulk samples by the independent water loss technique (0.062 and 0.020 for shales and limestones, respectively). Radiography measurements offer the advantage of time-saving for diffusion experiments because the experiment does not require steady-state conditions and also allows for visualization of the small-scale heterogeneities in diffusive properties within rocks at the mm to cm scale.

Three dimensional imaging of porosity and tracer concentration distributions in a dolostone sample during diffusion experiments using X-ray micro-CT.

X-ray micro-computed tomography (micro-CT) techniques for measuring the three-dimensional (3-D) distributions of diffusion-accessible porosity (φ(d)) and temporal tracer-concentrations (C(t)) within a dolostone sample subjected to solute diffusion are developed and tested in this work. The φ(d) and C(t) measurements are based on spatially resolved changes in X-ray attenuation coefficients in sequentially acquired 3-D micro-CT datasets using two (calibration and relative) analytical approaches. The measured changes in X-ray attenuation coefficient values are a function of the mass of X-ray absorbing potassium-iodide tracer present in voxels. Mean φ(d) values of 3.8% and 6.5% were obtained with the calibration and the relative approaches, respectively. The detection limits for φ(d) measurements at individual voxel locations are 20% and 36% with the calibration and the relative methods, respectively. The detection limit for C(t) are 0.12 M and 0.22 M with the calibration and the relative approaches, respectively. Results from the calibration method are affected by a beam-hardening artifact and although results from the relative approach are not affected by the artifact, they are subject to high detection limits. This work presents a quantitative assessment of micro-CT data for studies of solute transport. Despite limitations in precision and accuracy, the method provides quantitative 3-D distributions of φ(d) and C(t) that reflect solute diffusion in heterogeneous porous geologic media.

STORM-WATER HYDROGRAPH SEPARATION OF RUN OFF FROM A MINE-TAILINGS IMPOUNDMENT FORMED BY THICKENED TAILINGS DISCHARGE AT KIDD CREEK, TIMMINS, ONTARIO

The Kidd Creek CuZn sulphide mine is located near Timmins, Ontario. Mill tailings are thickened and deposited as a thickened slurry in a circular, conical-shaped pile with an area of approximately 1200 ha. Deposition of tailings as a thickened slurry results in a relatively uniform grain-size distribution and hydraulic conductivity, and a thick tension-saturated zone above the water table. The tailings are drained by numerous small, ephemeral stream channels, which have developed in a radial pattern. During storms, water from these streams collects in catchment ponds where it is held before treatment. The contribution of tailings pore water to the run off is of interest because of the potential for discharge of pore water containing high concentrations of Fe(II)-acidity, metals and SO4 to the stream. Hydraulic head measurements, measurements of water-table elevation and groundwater flow modelling were conducted to determine the mechanisms responsible for tailings pore water entering the surface streams. Chemical hydrograph separation of storm run off in one of these streams, during three rainfall events, using Na and Cl as conservative tracers, indicates that the integrated tailings pore water fraction makes up between less than 1 % and 20% of the total hydrograph. This range is less than the maximum fraction of tailings pore water of 22–65% reported for run off from a conventional tailings deposit. At this site, preferential flow through permeable fractures may be the dominant mechanism causing discharge of tailings pore water to storm run off. Estimates of the mass of Fe(II) that discharges to the surface run off from the pore water range up to 2800 mg s−1 during a moderate intensity, long duration rainfall event. The greatest potential for discharge of significant masses of solutes derived from the pore water exists during long duration rainfall events, when the water table rises to the surface over large areas of the tailings impoundment.

The hydrogeology of a tailings impoundment formed by central discharge of thickened tailings : implications for tailings management

Abstract The Kidd Creek Cu–Zn sulfide mine is located near Timmins, Ontario. Mill tailings are thickened and deposited as a slurry in a circular impoundment with an area of approximately 1200 ha. Deposition of tailings as a thickened slurry from a central discharge ramp results in a conical-shaped tailings deposit with low perimeter dykes, a uniform grain-size distribution, uniform and low hydraulic conductivity, and a tension-saturated zone above the water table up to 5 to 6 m thick. These characteristics provide benefits over conventionally disposed tailings with respect to tailings management. The thick tension-saturated zone within the tailings limits the thickness of unsaturated tailings that are susceptible to rapid sulfide oxidation. The conical shape of the deposit results in the formation of a recharge area near the centre of the impoundment and discharge in the peripheral areas. In contrast, the elevated nature of many conventional, unthickened tailings impoundments results in recharge over most of the surface of the impoundment, with discharge occurring outside the impoundment through large containment dykes. Three-dimensional pore water flow modelling suggests that approximately 90% of the total discharge from the thickened tailings occurs within the tailings impoundment. When discharge is confined within the impoundment, there is improved control over low-quality effluent, and an opportunity to design passive control measures to reduce treatment costs and minimize environmental impacts.