An Eco-Friendly Chemistry for Gold Extraction using Supercritical Carbon Dioxide

A number of exciting challenges, opportunities and unanswered questions remain concerning the chemistry, geochemistry, medical, industrial and analytical applications of gold and its compounds.1 Among the challenges presented is the need for extraction methods for gold, at process and indeed analytical scales, that avoid the use of organic solvents or hazardous reagents. Extensive environmental contamination has occurred in the Brazilian Amazon from the mercury-gold amalgamation process. Major problems with the cyanidation process are the relatively slow dissolution kinetics and the health and environmental problems associated with it. With innovation and technical changes, a cleaner way for solubilising and extracting this versatile precious metal can be found. This cleaner future may lie in supercritical fluid science. Interestingly, geochemical studies of gold solubility and speciation in hydrothermal solutions have highlighted the importance of supercritical conditions and sulphur species in the deposition of gold in natural environments. Gold solubility in supercritical brines is far higher than previously supposed while interest in the high content of carbon dioxide in the mineralizing fluids is growing. 2,3 In recent years, also, there has been a tremendous amount of attention paid in analytical chemistry and in industry, to the area of supercritical fluid extraction (SFE) of organic and metallic species. 4 This interest has been fuelled by the introduction of more stringent environmental control and the subsequent need for cleaner solvents and processes to replace established ones. Carbon dioxide is the substance of choice for SFE because of its moderate critical parameters (Tc = 31oC, Pc = 73atm), inertness and availability in pure form. It is an excellent extraction medium for non-polar and moderately polar species, and with careful ligand design, it can be used for analytical and process scale metal extraction from solution and solid phases. In general, the dissolution of a metal in supercritical CO2 (sc-CO2) requires that the charge on the metal ion be neutralised on complexation by the ligand or through a form of ion pairing (analogous to the situation where metal ions are extracted into organic solvents, such as methyl isobutyl ketone or toluene). In this way, then, many chelating agents such as dithiocarbamates and hydroxamic acids have been utilised to extract metal ions such as Cu and Fe into sc- CO2, the process greatly enhanced by the use of fluorinated ligand derivatives. 5-7 In this review paper, we show that supercritical conditions and complexation with sulphur donor atoms, important in the natural deposition of gold, can form the basis of a clean, eco-friendly chemistry for gold extraction. Analytical scale extractions of gold from a variety of matrices can be conveniently used to assess the efficiency of any new proposed ligand.