Michael B. Parsons

Effects of Soil Composition and Mineralogy on the Bioaccessibility of Arsenic from Tailings and Soil in Gold Mine Districts of Nova Scotia

Bioaccessibility tests and mineralogical analyses were performed on arsenic-contaminated tailings and soils from gold mine districts of Nova Scotia, Canada, to examine the links between soil composition, mineralogy, and arsenic bioaccessibility. Arsenic bioaccessibility ranges from 0.1% to 49%. A weak correlation was observed between total and bioaccessible arsenic concentrations, and the arsenic bioaccessibility was not correlated with other elements. Bulk X-ray absorption near-edge structure analysis shows arsenic in these near-surface samples is mainly in the pentavalent form, indicating that most of the arsenopyrite (As(1-)) originally present in the tailings and soils has been oxidized during weathering reactions. Detailed mineralogical analyses of individual samples have identified up to seven arsenic species, the relative proportions of which appear to affect arsenic bioaccessibility. The highest arsenic bioaccessibility (up to 49%) is associated with the presence of calcium-iron arsenate. Samples containing arsenic predominantly as arsenopyrite or scorodite have the lowest bioaccessibility (<1%). Other arsenic species identified (predominantly amorphous iron arsenates and arsenic-bearing iron(oxy)hydroxides) are associated with intermediate bioaccessibility (1 to 10%). The presence of a more soluble arsenic phase, even at low concentrations, results in increased arsenic bioaccessibility from the mixed arsenic phases associated with tailings and mine-impacted soils.

Mineralogical characterization of arsenic in gold mine tailings from three sites in Nova Scotia

ABSTRACT Chronic exposure to high concentrations of arsenic (As) in windblown and vehicle-raised dust from tailings sites in Nova Scotia poses a potential health risk to recreational users of these areas and to nearby residents. The exposure may involve inhalation of dust, as well as oral ingestion of particles. It is important to understand the mineralogy and morphology of As-bearing dust particles in order to evaluate the risk posed by near-surface particulates in As-bearing tailings fields, as this will influence the stability and toxicity of As in the wastes. Optical mineralogy, scanning electron microscopy, electron microprobe, X-ray diffraction, synchrotron-based micro-X-ray diffraction (μXRD) and micro-X-ray absorption near edge structure (μXANES), and sequential leach extractions were applied to tailings samples from three sites in eastern Nova Scotia. Arsenic occurs naturally in these gold deposits mainly in arsenopyrite (FeAsS). In the near-surface material of the tailings fields, sulphide minerals have almost completely oxidized to secondary minerals such as scorodite (FeAsO4•2H2O) and Ca-Fe arsenates. Iron oxyhydroxides contain variable amounts of As2O5 from trace to 30 wt.% and CaO up to 8 wt.%. The presence of multiple As-hosting solid phases, including relatively soluble Ca-Fe arsenates and Fe oxyhydroxides with adsorbed As has important implications for human health risk assessment and remediation design.

Influence of lead smelter emissions on the distribution of metals in marine sediments from Chaleur Bay, eastern Canada

Metal concentrations in surficial marine sediments collected from many parts of Chaleur Bay are significantly higher than background levels. The bay receives metals from various sources including a Pb smelter, an Hg-cell chlor-alkali plant, and numerous mined and unmined base-metal deposits. This study examines the sources, fluxes, and dispersal patterns of metals released to the bay, and the processes that control the transport and fate of these elements in the marine environment. Bottom sediments collected from 124 sites show the following ranges in metal(oid) concentrations (mg/kg): As, 2.8–74; Cd, 0.02–69; Cu, 3.4–200; Hg, <0.01–2.4; Pb, 0.3–2000; and Zn, 22–3200. Dispersion of smelter effluents and atmospheric emissions by wind and/or nearshore currents has resulted in an area of elevated As, Cd, Cu, Hg, Pb, and Zn concentrations in surficial sediments within c. 10–20 km of the smelter. The concentrations of most metals decrease sharply with increasing distance from the smelter; however, Pb concentrations exceed background levels in surface sediments throughout the bay. Lead isotope ratios suggest that the surface enrichment of Pb throughout the bay is mainly derived from smelter emissions and historical leaded gasoline combustion.

Identification and Characterization of Arsenic and Metal Compounds in Contaminated Soil, Mine Tailings, and House Dust Using Synchrotron-Based Microanalysis

ABSTRACT A comprehensive understanding of the risk associated with metal-rich soils and other materials includes identification of the solid phases hosting the metals. Synchrotron microanalysis provides a powerful diagnostic tool to characterize metal-bearing particles in mine tailings, soils, lake sediments, windblown dust, and household dust. A near simultaneous combination of X-ray fluorescence, diffraction, and absorption experiments using a microfocused beam can provide information on elemental concentrations, crystal structure, and oxidation state of individual particles. This approach can distinguish multiple metal-hosting minerals and industrial compounds in a single sample. Our objective is to provide examples of the application of this technique to a range of materials representing potential risk to human or ecosystem health. These examples include arsenic-contaminated materials and metal-rich household dust. We have identified grains of scorodite and other arsenate minerals in mine tailings and associated airborne dust, arsenic trioxide in organic soils near an ore roaster, metallurgical products dispersed to the environment, and various metal-rich particles in household dust. A comparison of chemical analysis of individual particles using electron microprobe analysis and synchrotron-based X-ray fluorescence analysis is provided.

Mineralogy and spectral reflectance of soils and tailings from historical gold mines, Nova Scotia

Gold was mined in 64 districts in southern Nova Scotia between 1861 and the early 1940s, followed by limited, intermittent production up to the present. There is extensive dispersion of arsenic- and mercury-bearing mine tailings in the receiving environment downstream from many of these sites. Elevated mercury concentrations, highest near old stamp mill foundations, occur because of the mercury amalgamation process used to extract gold until the 1940s. Arsenic, on the other hand, occurs naturally in arsenopyrite, which is associated with the gold-bearing quartz veins and host rocks. Tailings are composed of fine sand- to silt-sized quartz, feldspar, illite and chlorite, and represent the primary rock-forming minerals in the metasedimentary host rocks of the Cambro-Ordovician Meguma Supergroup. Carbonate and sulphide minerals occur in minor to trace amounts, along with secondary minerals such as scorodite (FeAsO4·2H2O). The extent of tailings dispersal can be mapped through hyperspectral remote sensing methods, as these major mineral components provide an identifiable spectral signature through visible, near infrared and short-wave infrared regions. This paper examines the mineralogy of soils, tills and tailings in the Upper and Lower Seal Harbour gold districts of Nova Scotia. Ground-truthing of space-borne hyperspectral data demonstrates the potential for remote mapping of the spatial extent of these historical mine wastes.

Organic matter control on the distribution of arsenic in lake sediments impacted by ~ 65 years of gold ore processing in subarctic Canada

Climate change is profoundly affecting seasonality, biological productivity, and hydrology in high northern latitudes. In sensitive subarctic environments exploitation of mineral resources led to contamination and it is not known how cumulative effects of resource extraction and climate warming will impact ecosystems. Gold mines near Yellowknife, Northwest Territories, subarctic Canada, operated from 1938 to 2004 and released >20,000t of arsenic trioxide (As2O3) to the environment through stack emissions. This release resulted in elevated arsenic concentrations in lake surface waters and sediments relative to Canadian drinking water standards and guidelines for the protection of aquatic life. A meta-analytical approach is used to better understand controls on As distribution in lake sediments within a 30-km radius of historic mineral processing activities. Arsenic concentrations in the near-surface sediments range from 5mg·kg-1 to over 10,000mg·kg-1 (median 81mg·kg-1; n=105). Distance and direction from the historic roaster stack are significantly (p<0.05) related to sedimentary As concentration, with highest As concentrations in sediments within 11km and lakes located downwind. Synchrotron-based μXRF and μXRD confirm the persistence of As2O3 in near surface sediments of two lakes. Labile organic matter (S1) is significantly (p<0.05) related to As and S concentrations in sediments and this relationship is greatest in lakes within 11km from the mine. These relations are interpreted to reflect labile organic matter acting as a substrate for microbial growth and mediation of authigenic precipitation of As-sulphides in lakes close to the historic mine where As concentrations are highest. Continued climate warming is expected to lead to increased biological productivity and changes in organic geochemistry of lake sediments that are likely to play an important role in the mobility and fate of As in aquatic ecosystems.

Factors Affecting Methylmercury Levels in Surficial Tailings from Historical Nova Scotia Gold Mines

Large quantities of Hg remain in tailings dumps from historical Nova Scotian gold mines. Depth profiles of total Hg (HgT) and methylmercury (MeHg) were compared with geochemical and microbiological variables, to identify factors influencing MeHg levels in tailings. HgT and MeHg were highly variable in tailings (0.2–73.5 μ mol kg− 1 and < dl-56.4 nmol kg− 1, respectively), and were influenced by a complex set of in situ factors. Elevated MeHg was linked with > 5 μ mol kg−1 HgT, organic matter, hydrology, abundance and activity of sulfate reducing bacteria, and demethylation processes. Methylmercury levels in tailings from a wet, bog-like site appeared to undergo seasonal fluctuations, with higher concentrations measured in September and October, and lower concentrations in May. Evaluations of amalgamation tailings should examine MeHg and HgT transport out of low-lying, saturated tailings dumps after snowmelt and major rainfall events, and should take into account the possibility of seasonal variation in MeHg levels in northern regions.