Assessment of Dowex 1-X8-based Anion-exchange Procedures for the Separation and Determination of Ruthenium, Rhodium, Palladium, Iridium, Platinum and Gold in Geological Samples by Inductively Coupled Plasma Mass Spectrometry

Abstract

Synthetic multielement solutions of the platinum group metals (PGE: Ru; Rh; Pd; Ir; Pt) and gold, with analysis by ICP-AES and ICP-MS, have been used to study the behaviour of the precious metals on Dowex 1-X8 resin. Simple solutions of precious-metal chlorocomplexes showed near-complete adsorption (>99%) of most elements, and only minor breakthrough of Ru and Ru (≈5%). Solutions pre-treated with acid mixtures typically used to decompose geological samples, demonstrated that perchloric acid adversely affects the adsorption of the PGEs on the resin. Solutions treated with HF–HNO ₃ –HCl maintained good retention of Ir, Pt, Au (>99%), Pd (>94%) and Ru (>90%), but displayed significant loss (up to 40%) of Rh. A two-step procedure was necessary to elute the precious metals from the resin: 0.3 mol l ^{- 1} thiourea prepared in 0.1 mol ^{- 1} HCl removed Ru, Pd, Pt, Au, and some Rh: 12 mol l ^{- 1} HCl eluted remaining Rh and all Ir. Recoveries ranged from 50 to 100%. At low levels, the determination of PGE and Au in the thiourea fraction by ICP-MS was compromised by high levels of total dissolved solids (TDS), which necessitated dilution of the eluate prior to analysis. The TDS was reduced by decomposing thiourea with HNO ₃ and removing SO ₄ ^{2 -} by precipitation of BaSO ₄ , but this led to lower and more erratic results, and increased contamination. An assessment of the optimised procedure employing geological reference materials PTM-1, PTC-1 and SARM7, indicated that acceptable results should be attainable for ICP-MS determination of most elements in geological samples containing high concentrations (>1 µg g ^{- 1} ) of the PGE, for which decomposition of thiourea is unneccessary. The addition of a decomposition step led to low recovery of all elements except Ir, which was present entirely in the HCl eluate. The method is viable for the determination of Ir in a range of geological materials, but modifications will be required if it is to be extended to the other precious metals.