Simultaneous Insight into Dissolution and Aggregation of Metal Sulfide Nanoparticles through Single-Particle Inductively Coupled Plasma Mass Spectrometry

Nanoparticles (NPs) and their colloidal aggregates are ubiquitous and play important roles in the transport and release of metals. Knowledge of their dissolution rates and aggregation behavior in solution are crucial for better prediction of their fate in biogeochemical cycling, ecotoxicity, and environmental remediation. There are however significant technical challenges to accurately obtain such information as a result of the heterogeneity and highly dynamic transformation exhibited by NPs, particularly at relatively low particle concentrations in aqueous systems. Here, we quantitatively examine the simultaneous dissolution and aggregation behavior of metal sulfide NPs using single-particle inductively coupled plasma mass spectrometry (spICP–MS). We focus on nickel sulfide (NiS), with additional data presented for copper sulfide (CuS) and cobalt sulfide (CoS). The kinetics of metal release (dissolution and disaggregation) of NiS was fastest under strongly oxidizing conditions (from 0.04 to >3 min–1 with H2O2 ) and were slower under near-neutral (HEPES buffer/H2O) and acidic (1 mM HNO3) conditions (≤0.006 min–1). Metal release kinetics in HNO3 was not faster than in H2O or HEPES, suggesting that the solution pH has an influence over both the dissolution kinetics of individual particles and the NP aggregation states, which in combination affect metal release rates over time. Between different metal sulfides, the measured metal release rates were largely consistent with predictions based on the crystallinity, solubility products, and specific surface areas of the NPs, following an order of CoS > NiS > CuS. The spICP–MS approach described here can be easily applied to the characterization of metal release and aggregation of other NPs at low concentrations (∼105 particles/mL) typically found in natural environments.