Mechanisms of Arsenic Sequestration by Prosopis juliflora during the Phytostabilization of Metalliferous Mine Tailings.

Phytostabilization is a cost-effective long-term bioremediation technique for the immobilization of metalliferous mine tailings. However, the biogeochemical processes affecting metal(loid) molecular stabilization and mobility in the root zone remain poorly resolved. The roots of Prosopis juliflora grown for up to 36 months in compost-amended pyritic mine tailings from a federal Superfund site were investigated by microscale and bulk synchrotron X-ray absorption spectroscopy (XAS) and multiple energy micro-X-ray fluorescence imaging to determine iron, arsenic, and sulfur speciation, abundance, and spatial distribution. Whereas ferrihydrite-bound As(V) species predominated in the initial bulk mine tailings, the rhizosphere speciation of arsenic was distinctly different. Root-associated As(V) was immobilized on the root epidermis bound to ferric sulfate precipitates and within root vacuoles as trivalent As(III)-(SR)3 tris-thiolate complexes. Molar Fe-to-As ratios of root epidermis tissue were two times higher than the 15% compost-amended bulk tailings growth medium. Rhizoplane-associated ferric sulfate phases that showed a high capacity to scavenge As(V) were dissimilar from the bulk-tailings mineralogy as shown by XAS and X-ray diffraction, indicating a root-surface mechanism for their formation or accumulation.

Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate.

Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3 to 2.3). Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mM kg-1 (3080, 2200, and 2570 mg kg-1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2 fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25-54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe phases, principally ferrihydrite. In surface samples (0-35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO4·nH2O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface.

Metal Lability and Mass Transfer Response to Direct-Planting Phytostabilization of Pyritic Mine Tailings.

Understanding the temporal effects of organic matter input and water influx on metal lability and translocation is critical to evaluate the success of the phytostabilization of metalliferous mine tailings. Trends of metal lability, e.g., V, Cr, Mn, Co, Ni, Cu, Zn, and Pb, were investigated for three years following a direct-planting phytostabilization trial at a Superfund mine tailings site in semi-arid central Arizona, USA. Unamended tailings were characterized by high concentrations (mmol kg-1) of Fe (2100), S (3100), As (41), Zn (39), and Pb (11), where As and Pb greatly exceeded non-residential soil remediation levels established by Arizona. Phytostabilization treatments included a no-compost control, 100 g kg-1 compost with seed, and 200 g kg-1 compost with and without seed to the top 20 cm of the tailings profile. All plots received supplemental irrigation, effectively doubling the mean annual precipitation. Tailings cores up to 90 cm were Collected at the time of planting and every summer for 3 years. The cores were sub-sectioned at 20 cm increments and analyzed via total digestion and an operationally defined sequential extraction for elemental analysis and the calculation of a mass transfer coefficient normalized to Ti as an assigned immobile element. The results indicate that Pb was recalcitrant and relatively immobile in the tailings environment for both the uncomposted control and composted treatments with a maximum variation in the total concentration of 9-14 mmol kg-1 among all samples. Metal lability and translocation above the redox boundary (ca. 30 cm depth) was governed by acid generation, where surficial pH was measured as low as 2.7 ± 0.1 in year three and strongly correlated with the increased lability of Mn, Co, Ni, Cu, and Zn. There was no significant pH effect on the lability of V, Cr, or Pb. Translocation to depths was greatest for Mn and Co; however, Zn, Ni, Cr, and Cu were also mobilized. The addition of organic matter enhanced the mobilization of Cr from the near surface to 40-60 cm depth (pH > 6) over the three-year phytostabilization study compared to the control. The increased enrichment of some metals at 60-90 cm indicates that the long-term monitoring of elemental translocation is necessary to assess the efficacy of phytostabilization to contain subsurface metal contaminants and thereby protect the surrounding community from exposure.

Arsenic and iron speciation and mobilization during phytostabilization of pyritic mine tailings.

Particulate and dissolved metal(loid) release from mine tailings is of concern in (semi-) arid environments where tailings can remain barren of vegetation for decades and, therefore, become highly susceptible to dispersion by wind and water. Erosive weathering of metalliferous tailings can lead to arsenic contamination of adjacent ecosystems and increased risk to public health. Management via phytostabilization with the establishment of a vegetative cap using organic amendments to enhance plant growth has been employed to reduce both physical erosion and leaching. However, prior research suggests that addition of organic matter into the oxic weathering zone of sulfide tailings has the potential to promote the mobilization of arsenate. Therefore, the objective of the current work was to assess the impacts of phytostabilization on the molecular-scale mechanisms controlling arsenic speciation and lability. These impacts, which remain poorly understood, limit our ability to mitigate environmental and human health risks. Here we report on subsurface biogeochemical transformations of arsenic and iron from a three-year phytostabilization field study conducted at a Superfund site in Arizona, USA. Legacy pyritic tailings at this site contain up to 3 g kg-1 arsenic originating from arsenopyrite that has undergone oxidation to form arsenate-ferrihydrite complexes in the top 1 m. Tailings were amended in the top 20 cm with 100, 150, or 200 g kg-1 (300-600 T ha-1) of composted organic matter and seeded with native halotolerant plant species. Treatments and an unamended control received irrigation of 360 ± 30 mm y-1 in addition to 250 ± 160 mm y-1 of precipitation. Cores to 1 m depth were collected annually for three years and sectioned into 20 cm increments for analysis by synchrotron iron and arsenic X-ray absorption spectroscopy (XAS) coupled with quantitative wet chemical and mass balance methods. Results revealed that > 80% of arsenic exists in ammonium oxalate-extractable and non-extractable phases, including dominantly ferrihydrite and jarosite. Arsenic release during arsenopyrite oxidation resulted in both downward translocation and As(V) attenuation by stable Fe(III)(oxyhydr)oxide and Fe(III) (hydroxy)sulfate minerals over time, highlighting the need for sampling at multiple depths and time points for accurate interpretation of arsenic speciation, lability, and translocation in weathering profiles. Less than 1% of total arsenic was highly-labile, i.e. water-extractable, from all treatments, depths, and years, and more than 99% of arsenate released by arsenopyrite weathering was attenuated by association with secondary minerals. Although downward translocation of both arsenic and iron was detected during phytostabilization by temporal enrichment analysis, a similar trend was measured for the uncomposted control, indicating that organic amendment associated with phytostabilization practices did not significantly increase arsenic mobilization over non-amended controls.

Phytostabilization of mine tailings using compost-assisted direct planting: Translating greenhouse results to the field.

Standard practice in reclamation of mine tailings is the emplacement of a 15 to 90cm soil/gravel/rock cap which is then hydro-seeded. In this study we investigate compost-assisted direct planting phytostabilization technology as an alternative to standard cap and plant practices. In phytostabilization the goal is to establish a vegetative cap using native plants that stabilize metals in the root zone with little to no shoot accumulation. The study site is a barren 62-hectare tailings pile characterized by extremely acidic pH as well as lead, arsenic, and zinc each exceeding 2000mgkg(-1). The study objective is to evaluate whether successful greenhouse phytostabilization results are scalable to the field. In May 2010, a 0.27ha study area was established on the Iron King Mine and Humboldt Smelter Superfund (IKMHSS) site with six irrigated treatments; tailings amended with 10, 15, or 20% (w/w) compost seeded with a mix of native plants (buffalo grass, arizona fescue, quailbush, mountain mahogany, mesquite, and catclaw acacia) and controls including composted (15 and 20%) unseeded treatments and an uncomposted unseeded treatment. Canopy cover ranging from 21 to 61% developed after 41 months in the compost-amended planted treatments, a canopy cover similar to that found in the surrounding region. No plants grew on unamended tailings. Neutrophilic heterotrophic bacterial counts were 1.5 to 4 orders of magnitude higher after 41months in planted versus unamended control plots. Shoot tissue accumulation of various metal(loids) was at or below Domestic Animal Toxicity Limits, with some plant specific exceptions in treatments receiving less compost. Parameters including % canopy cover, neutrophilic heterotrophic bacteria counts, and shoot uptake of metal(loids) are promising criteria to use in evaluating reclamation success. In summary, compost amendment and seeding, guided by preliminary greenhouse studies, allowed plant establishment and sustained growth over 4years demonstrating feasibility for this phytostabilization technology.