Isotopically Labeled Nanoparticles at Relevant Concentrations: How Low Can We Go? The Case of CdSe/ZnS QDs in Surface Waters.

Analytical barriers impose work at nanoparticles (NPs) concentrations orders of magnitude higher than the expected NPs concentrations in the environment. To overcome these limitations, the use of nontraditional stable isotope tracers incorporated in NPs (spiked-NPs) coupled with HR-ICP-MS has been proposed. The performance and efficiency of this analytical method was assessed in the case of quantum dots (QDs). Multi-isotopically labeled 111Cd77Se/68ZnS QDs were synthesized and their dissemination in natural aquatic matrices (river, estuarine and sea waters) was modeled at very low concentrations (from 0.1 to 5000 ppt). The QD limits of quantification (QD-LOQ) in each matrix were calculated according to the isotopic tracer. In ultrapure and simple medium (HNO3 2%), Zn, Cd, and Se originated from the QDs were quantifiable at concentrations of 10, 0.3, and 6 ppt, respectively, which are lower than the conventional HR-ICP-MS LOQs. In aquatic matrices, the QD-LOQs increase 10-, 130-, and 250-fold for Zn, Cd, and Se, respectively, but remain relevant of environmental concentrations (3.4 ppt ≤ QD-LOQs ≤ 2.5 ppb). These results validate the use of isotopically labeled ENPs at relevant concentrations in experimental studies related to either their fate, behavior, or toxicity in most aquatic matrices.