Improved chromatographic separation of thio-arsenic compounds by reversed-phase high performance liquid chromatography-inductively coupled plasma mass spectrometry

A new group of arsenic species, thio-arsenicals, have recently been reported in several natural samples such as molluscs, algae, and urine. These compounds are the sulfur analogues of oxo-arsenicals, a large group of naturally-occurring compounds, whereby the arsinoyl (AsO) group is substituted by an arsinothioyl group (AsS). The most common separation technique for oxo-arsenicals is anion-exchange HPLC with polymer-based columns, but under these conditions the thio-arsenicals show strong retention, resulting in unacceptably long analysis times and broad peaks. We report the development of a reversed-phase HPLC method, with ICPMS detection, which allows separation of the known thio-arsenicals within 15 min with significantly improved peak shapes. The detection limit is about 0.6 μg As/L based on 10 μL injection volume. Further, we have applied the method to the identification and quantification of thio-arsenic species in two standard reference materials, BCR 710 oyster tissue and NIES 18 human urine.