Drivers of Pb, Sb and As release from spent gunshot in wetlands: Enhancement by organic matter and native microorganisms.

In many countries the use of lead-based ammunition is prevalent, and results in exposure and poisoning of waterfowl and other species of birds. In waterfowl hunting areas large quantities of spent shot may be deposited in wetland and terrestrial habitats. These pellets can undergo transformations, which are influenced by various abiotic and biotic factors. In addition to lead (Pb), other elements like antimony (Sb) and arsenic (As) can be leached from Pb shot into the environment. In vitro simulations that included organic matter and microorganisms were utilized to examine elemental leaching from gunshot. We found that leaching efficiency was the greatest in solutions rich in organic matter derived from artificial root exudates (2.69 % for Pb, 1.16 % for Sb, 1.83 % for As), while leaching efficiency was considerably lower in river water (0.04 %). In vitro simulations containing native microorganisms also exhibited greater leaching efficiency (0.49 % for Pb, 0.52 % for Sb, 1.32 % for As) than in ultrapure deionized water and river water. Surface alterations in gunshot included the formation of a weathering crust and secondary phases dominated by carbonates. Spent gunshot is a source of Pb, Sb and As in wetlands that could affect aquatic ecosystems.

Ultramafic geoecosystems as a natural source of Ni, Cr, and Co to the environment: A review.

Ultramafic soils are in equal parts fascinating and dangerous. Developed on rocks derived predominately from the Earth's mantle and metamorphosed at the ocean floors, ultramafic soils form in the places where tectonic forces brought these rocks from mantle depths to the surface. As it is common in nature, both ultramafic rocks and soils are site-specific, and vary in character and composition; however, they have one thing in common, they are enriched in certain elements and three metals in particular form an "ultramafic" triad: Ni, Cr, and Co. These three metals are far from being human-friendly and strict legislative limits are established for maximum allowable concentrations of these metals in soils, but mostly in the case when the metals are of anthropogenic origin. However, ultramafic soils are a natural phenomenon where increased metal content is not the result of pollution, but rather referred as a peculiar geochemical background, therefore there is no reason for their remediation. At the same time, it is not that easy to actually find an ultramafic soil that does not overstep the limits (for the sake of this paper we use median world Regulatory Guidance Values - RGVs). Often, mobile Ni and Co concentrations are above the guidelines when doing tests to estimate the bioavailable fraction (EDTA and DTPA), and high concentrations of Ni are also commonly present in excluder plants (also edible ones). Also waters in ultramafic areas often exceed Ni and Cr(VI) limits. It is therefore expected that the ultramafic metals are present in the food chain and they might constitute a potential health risk. Thus, there is a need for additional research focused on assessment of the potential health consequences of chronic high exposure on naturally occurring Ni, Cr, and Co.

Weathering of historical copper slags in dynamic experimental system with rhizosphere-like organic acids.

This study was undertaken to simulate experimentally the weathering of slags disposed nearby soil rhizosphere. The aim of the research was to differentiate the effect of pH and organics on slags dissolution as well as to indicate weathering sequence of phase components. The studied slags are mainly composed of Fe (34.5 wt%) and Si (17.9 wt%) and contain up to 3761 mg kg-1 of Cu and 3628 mg kg-1 of Zn. The main identified phases are fayalite and glass, whereas sulfides and metallic Cu are volumetrically minor. A 30 days long slag weathering experiment was carried out with artificial root exudates (43.7 mM) and demineralized water at initial pH = 3.5 and pH = 6.7. The highest metal release (up to 10.9% of Zn and 4.6% of Cu) was observed in ARE solution at initial pH 3.5. Dissolution of sulfides and fayalite was mainly driven by pH. Artificial root exudates enhance glass dissolution as compared to demineralized water regardless of initially fixed pH. Based on this study following weathering sequences are delineated: i) under ARE 3.5 conditions: silicates > glass > sulfides, ii) under DW 3.5 conditions: sulfides > silicates > glass, iii) under near-neutral conditions: sulfides > glass > silicates.

Perspectives regarding the use of metallurgical slags as secondary metal resources - A review of bioleaching approaches.

Smelting activity by its very nature produces large amounts of metal-bearing waste, often called metallurgical slag(s). In the past, industry used to dispose of these waste products at dumping sites without the appropriate environmental oversight. Once there, ongoing biogeochemical processes affect the stability of the slags and cause the release of metallic contaminants. Rather than viewing metallurgical slags as waste, however, such deposits should be viewed as secondary metal resources. Metal bioleaching is a "green" treatment route for metallurgical slags, currently being studied under laboratory conditions. Metal-laden leachates obtained at the bioleaching stage have to be subjected to further recovery operations in order to obtain metal(s) of interest to achieve the highest levels of purity possible. This perspective paper considers the feasibility of the reuse of base-metal slags as secondary metal resources. Special focus is given to current laboratory bioleaching approaches and associated processing obstacles. Further directions of research for development of more efficient methods for waste slag treatment are also highlighted. The optimized procedure for slag treatment is defined as the result of this review and should include following steps: i) slag characterization (chemical and phase composition and buffering capacity) following the choice of initial pH, ii) the choice of particle size, iii) the choice of the liquid-to-solid ratio, iv) the choice of microorganisms, v) the choice of optimal nutrient supply (growth medium composition). An optimal combination of all these parameters will lead to efficient extraction and generation of metal-free solid residue.

Metal mobilization from metallurgical wastes by soil organic acids.

Three types of Cu-slags differing in chemical and mineralogical composition (historical, shaft furnace, and granulated slags) and a matte from a lead recovery process were studied with respect to their susceptibility to release Cu, Zn and Pb upon exposure to organic acids commonly encountered in soil environments. Leaching experiments (24-960 h) were conducted with: i) humic acid (20 mg/L) at pH t0 = 4.4, ii) fulvic acid (20 mg/L) at pH t0 = 4.4, iii) an artificial root exudates (ARE) (17.4 g/L) solution at pH t0 = 4.4, iv) ARE solution at pH t0 = 2.9 and v) ultrapure water (pH t0 = 5.6). The results demonstrated that the ARE contribute the most to the mobilization of metals from all the wastes analyzed, regardless of the initial pH of the solution. For example, up to 14%, 30%, 24% and 5% of Cu is released within 960 h from historical, shaft furnace, granulated slags and lead matte, respectively, when exposed to the artificial root exudates solution (pH 2.9). Humic and fulvic acids were found to have a higher impact on granulated and shaft furnace slags as compared to the ultrapure water control and increased the release of metals by a factor up to 37.5 (Pb) and 20.5 (Cu) for granulated and shaft furnace slags, respectively. Humic and fulvic acids amplified the mobilization of metals by a maximal factor of 13.6 (Pb) and 12.1 (Pb) for historical slag and lead matte, respectively. The studied organic compounds contributed to different release rates of metallic contaminants from individual metallurgical wastes under the conditions tested.

Lead isotopes and heavy minerals analyzed as tools to understand the distribution of lead and other potentially toxic elements in soils contaminated by Cu smelting (Legnica, Poland).

Surroundings of the Legnica Cu smelter (Poland) offer insight into the behavior of Pb and other metal(oid)s in heavily contaminated soils in a relatively simple site, where lithogenic and anthropogenic Pb contributions have uniform Pb isotope composition over the time of smelter activity. Distribution of metal(oid)s decreases asymptotically with depth and below 30 cm reaches concentrations typical or lower than those of upper continental crust. Usually, such distribution is interpreted as the decrease in anthropogenic Pb contribution with depth. However, calculations based on Pb isotopes indicate that anthropogenic Pb is probably distributed both as Pb-rich particles of slags and fly ashes and Pb-poor soil solutions. Generally, anthropogenic Pb constitutes up to 100 % of Pb in the uppermost 10 cm of the soils and comes often from mechanical mixing with slag and fly ash particles as well as their weathering products. On the other hand, lower soil horizon contains anthropogenic Pb in various forms, and at depths below 30 cm, most of anthropogenic Pb comes from soil solutions and can constitute from 1 to 65 % of the Pb budget. This is consistent with secondary electron microscope (SEM) analyses of heavy mineral particles showing that, in upper horizons, Pb, Cu, and Zn are contained in various particles emitted from the smelter, which show different stages of weathering. Currently, large portion of these metals may reside in the secondary Fe-hydro-oxides. On the other hand, in deeper soil horizons, anthropogenic Pb is probably dominated by Pb coming from leaching of slag or fly ash particles. Overall, metal(oid) mobility is a dynamic process and is controlled by the soil type (cultivated versus forest) and the composition and the structure of the metal-rich particles emitted from the smelter. High proportions of anthropogenic Pb at depths below 30 cm in some soil profiles indicate that Pb (and probably other metal(oid)s) can be transported down the soil profile and the present concentration of anthropogenic Pb depends on the availability of binding sites.