Evaluation of thallium isotopic fractionation during the metallurgical processing of sulfides: An update.

In this study, we report combined Tl isotopic and Tl mineralogical and speciation data from a set of Tl-rich sulfide concentrates and technological wastes from hydrometallurgical Zn extraction. We also present the first evaluation of Tl isotopic ratios over a cycle of sulfide processing, from the ore flotation to pyro- and hydrometallurgical stages. The results demonstrate that the prevailing Tl form in all samples is Tl(I), without any preferential incorporation into sulfides or Tl-containing secondary phases, indicating an absence of Tl redox reactions. Although the Tl concentrations varied significantly in the studied samples (~9-280 mg/kg), the overall Tl isotopic variability was small, in the range of -3.1 to -4.4 ± 0.7 (2σ) ε205Tl units. By combining present ε205Tl results with the trends first found for a local roasting plant, it is possible to infer minimum Tl isotopic effects throughout the studied industrial process. As a result, the use of Tl isotopic ratios as a source proxy may be complicated or even impossible in areas with naturally high/extreme Tl background contents. On the other hand, areas with two or more isotopically contrasting Tl sources allow for relatively easy tracing, i.e., in compartments which do not suffer from post-depositional isotopic redistributions.

Thallium and lead variations in a contaminated peatland: A combined isotopic study from a mining/smelting area.

Vertical profiles of Tl, Pb and Zn concentrations and Tl and Pb isotopic ratios in a contaminated peatland/fen (Wolbrom, Poland) were studied to address questions regarding (i) potential long-term immobility of Tl in a peat profile, and (ii) a possible link in Tl isotopic signatures between a Tl source and a peat sample. Both prerequisites are required for using peatlands as archives of atmospheric Tl deposition and Tl isotopic ratios as a source proxy. We demonstrate that Tl is an immobile element in peat with a conservative pattern synonymous to that of Pb, and in contrast to Zn. However, the peat Tl record was more affected by geogenic source(s), as inferred from the calculated element enrichments. The finding further implies that Tl was largely absent from the pre-industrial emissions (>~250 years BP). The measured variations in Tl isotopic ratios in respective peat samples suggest a consistency with anthropogenic Tl (ε205Tl between ~ -3 and -4), as well as with background Tl isotopic values in the study area (ε205Tl between ~0 and -1), in line with detected 206Pb/207Pb ratios (1.16-1.19). Therefore, we propose that peatlands can be used for monitoring trends in Tl deposition and that Tl isotopic ratios can serve to distinguish its origin(s). However, given that the studied fen has a particularly complicated geochemistry (attributed to significant environmental changes in its history), it seems that ombrotrophic peatlands could be better suited for this type of Tl research.

Tracing potential soil contamination in the historical Solvay soda ash plant area, Jaworzno, Southern Poland.

This study of soil conditions was carried out on 30 meadow soil (podzol) samples from the vicinity of the soda ash heap in Jaworzno, supplemented by analyses of 18 samples of waste deposited on the heap. In all samples, the total content of macroelements (Ca and Na) and heavy metals (Cd, Cr, Ni, Pb and Zn) as well as pH were analysed. The element concentrations were measured using inductively coupled plasma optical emission spectrometry (ICP-OES). The materials examined were neutral to ultra-alkaline. Total accumulations (mg kg(-1)) of chemical elements in the soil vary from 130.24 to 14076.67 for Ca, 41.40-926.23 for Na, 0.03-3.34 for Cd, 0.94-103.62 for Cr, 0.94-35.89 for Ni, 3.51-76.47 for Pb and 12.05-279.13 for Zn, whereas quantities of the same elements in the waste samples vary from 171705.13 to 360487.94 for Ca, 517.64-3152.82 for Na, 0.2-9.89 for Cd, 1.16-20.40 for Cr, 1.08-9.79 for Ni, 0.1-146.05 for Pb and 10.26-552.35 for Zn. The vertical distribution of the metals was determined in each soil profile. Despite enrichment of heavy metals in the uppermost horizon on the top of the heap, the results lead to the conclusion that the relation of historical production of soda ash in Jaworzno to current contamination of the local soil environment is insignificant.