Determination of carbon in microplastics and single cells by total consumption microdroplet ICP-TOFMS

Abstract

Recently, spICP-MS analyses of microplastics have demonstrated that the detection capabilities of ICP-MS are sufficient to determine the size and composition of such materials. However, solution nebulization or microdroplet generation limits the sizes of droplets, microparticles, or cells that can be efficiently introduced into commonly used horizontal ICP-MS configurations. Therefore, we introduced the development of a downward-pointing ICP coupled to a time-of-flight mass spectrometer (ICP-TOFMS), which enables quantitative transport of large microdroplets (diameters up to 90 µm) into the ICP. Here, we report the capabilities of downward ICP-TOFMS for the quantitative analysis of single cells and microplastic particles. For calibration of element mass amount per particle or cell, microdroplets (70 µm diameter) composed of multielement solutions were measured by ICP-TOFMS. Microplastic beads (polystyrene) and spleenocyte cells were then also embedded in microdroplets and measured by ICP-TOFMS with ion optics optimized to determine the signals from ¹²C+ and other isotopes of interest, including ¹⁴⁰Ce, ¹⁵³Eu, ¹⁶⁵Ho, and ¹⁷⁵Lu from the REE beads and ³¹P for the cells. The results achieved using the prototype instrument of a vertical downward-pointing ICP-TOFMS demonstrate that such a plasma configuration is well suited to analyze microplastics and single cells. For single microbead and cell analyses, the critical mass for carbon was 4.8 pg, and the mean determined carbon mass amounts were 14 and 23 pg, respectively. For the microbead analysis, the detected carbon mass corresponds to a particle diameter of 2.93 ± 0.24 µm, which is consistent with the scanning (transmission) electron microscopy–determined diameter of 2.97 ± 0.04 µm. Furthermore, in the analysis of spleenocyte cells, carbon and phosphorus masses were determined to be correlated.