Characterizing the Stoichiometry of Individual Metal Sulfide and Phosphate Colloids in Soils, Sediments, and Industrial Processes by Inductively Coupled Plasma Time-of-Flight Mass Spectrometry.

Abstract

Size and purity of metal phosphate and metal sulfide colloids can control the solubility, persistence, and bioavailability of metals in environmental systems. Despite their importance, methods for detecting and characterizing the diversity in the elemental composition of these colloids in complex matrices are missing. Here, we develop a single-particle inductively coupled plasma time-of-flight mass spectrometry (sp-icpTOF-MS) approach to characterize the elemental compositions of individual metal phosphate and sulfide colloids extracted from complex matrices. The stoichiometry was accurately determined for particles of known composition with an equivalent spherical diameter of ≥∼200 nm. Assisted by machine learning (ML), the new method could distinguish particles of the copper sulfides covellite (CuS), chalcocite (Cu2S), and chalcopyrite particles (CuFeS2) with 75% (for Cu2S) to 99% (for CuFeS2) accuracy. Application of the sp-icpTOF-MS method to particles recovered from natural samples revealed that iron sulfide (FeS) particles in lake sediment contained ∼4% copper and zinc impurities, whereas pure pyrite (FeS2) was identified in hydraulic fracturing wastewater and confirmed by selected area electron diffraction. Colloidal mercury in an offshore marine sediment was present as pure mercury sulfide (HgS), whereas geogenic HgS recovered from an industrial process contained ∼0.08 wt % silver per Hg, enabling source apportionment of these colloids using ML. X-ray absorption spectroscopy confirmed that Hg was predominantly present as metacinnabar (β-HgS) in the industrial process sample. The determination of impurities in individual colloids, such as zinc and copper in FeS, and silver in HgS may enable improved assessment of their origin, reactivity, and bioavailability potential.