Composition and fate of mine- and smelter-derived particles in soils of humid subtropical and hot semi-arid areas.

We studied the heavy mineral fraction, separated from mining- and smelter-affected topsoils, from both a humid subtropical area (Mufulira, Zambian Copperbelt) and a hot semi-arid area (Tsumeb, Namibia). High concentrations of metal(loid)s were detected in the studied soils: up to 1450mgAskg(-1), 8980mgCukg(-1), 4640mgPbkg(-1), 2620mgZnkg(-1). A combination of X-ray diffraction analysis (XRD), scanning electron microscopy (SEM/EDS), and electron probe microanalysis (EPMA) helped to identify the phases forming individual metal(loid)-bearing particles. Whereas spherical particles originate from the smelting and flue gas cleaning processes, angular particles have either geogenic origins or they are windblown from the mining operations and mine waste disposal sites. Sulphides from ores and mine tailings often exhibit weathering rims in contrast to smelter-derived high-temperature sulphides (chalcocite [Cu2S], digenite [Cu9S5], covellite [CuS], non-stoichiometric quenched Cu-Fe-S phases). Soils from humid subtropical areas exhibit higher available concentrations of metal(loids), and higher frequencies of weathering features (especially for copper-bearing oxides such as delafossite [Cu(1+)Fe(3+)O2]) are observed. In contrast, metal(loid)s are efficiently retained in semi-arid soils, where a high proportion of non-weathered smelter slag particles and low-solubility Ca-Cu-Pb arsenates occur. Our results indicate that compared to semi-arid areas (where inorganic contaminants were rather immobile in soils despite their high concentrations) a higher potential risk exists for agriculture in mine- and smelter-affected humid subtropical areas (where metal(loid) contaminants can be highly available for the uptake by crops).

Reliability of chemical microanalyses for solid waste materials.

The investigation of solid speciation of metals and metalloids is required for accurate assessment of the hazardous properties of solid waste materials from high-temperature technologies (slag, bottom ash, fly ash, air-pollution-control residues). This paper deals with the problem of reliability of microanalyses using a combination of electron microprobe analysis (EPMA) and scanning electron microscopy (SEM) only. These methods do not permit to detect nanophases in host-crystals and lead to erroneous interpretation of analytical results, considering the elements of nanophases as belonging to the crystal structure of the main phase. More detailed analysis using transmission electron microscopy (TEM) on foils prepared by focused ion beam (FIB) can be used to solve this analytical problem. In this study, lamellar aggregates of potassium-rich clinopyroxenes were detected in copper smelting slags by a combination of SEM and EPMA. However, FIB-TEM indicated the presence of leucite inclusions (tens to hundreds nm in size) within the clinopyroxene lamellae. Based on examples from smelting slags and other solid waste materials, recommendations for standard SEM and EPMA applications and the need for methods with higher resolution for mineralogical investigation of waste materials are discussed.

Mineralogy of air-pollution-control residues from a secondary lead smelter: environmental implications.

The mineralogy and solubility of air-pollution-control (APC) residues from a secondary lead (Pb) smelter have been studied on samples from the Príbram smelter, Czech Republic, recycling car batteries, with the emphasis on their potential environmental effect. The presence of dominant anglesite (PbSO4) and laurionite (Pb(OH)Cl) was observed in a sintered residue from after-burning chambers (800-1000 degrees C). In contrast, low-temperature Pb-bearing phases, such as KCl x 2PbCl2 and caracolite (Na3Pb2(SO4)3Cl), were detected in the major APC residue from bag-type fabric filters. Metallic elements, zinc (Zn), cadmium (Cd), and tin (Sn) were found homogeneously distributed within this residue. The formation of anglesite, cotunnite (PbCl2), (Zn,Cd)2SnO4, and (Sb,As)2O3 was observed during the sintering of this APC residue at 500 degrees C in a rotary furnace. The 168 h leaching test on filter residue, representing the fraction that may escape the flue gas treatment system, indicated rapid release of Pb and other contaminants. Caracolite and KCl x 2PbCl2 are significantly dissolved, and anglesite and cotunnite form the alteration products, as was confirmed by mineralogical analysis and PHREEQC-2 modeling. The observed Pb-bearing chlorides have significantly higher solubility than anglesite and, following emission from the smelter stack, can readily dissolve, transferring Pb into the environmental milieu (soils, water, inhabited areas).