Investigating the sensitivity difference of gaseous and particulate carbon in two-phase sample transport in LA-ICP-MS†

LA-ICP-MS is a widely used analytical technique for elemental analysis of different solid samples, including carbon-based samples. To compensate for matrix-effects and instrumental drifts during analysis, application of an internal standard is recommended. For carbon-based samples, the application of carbon as an internal standard seems reasonable but is typically not recommended due to the so-called two-phase sample transport where ablated carbon is transported both as particulate and gaseous species. The quantitative deviations in the sensitivity of particulate and gaseous carbon have not been accessible so far but would provide useful insights into the application of carbon as an internal standard. More precisely, if similar sensitivity for particulate and gaseous carbon species is found, application as an internal standard would not be restricted. To investigate this, we analyze the two-phase sample transport of carbon upon ablation of 5 different polymers, which all form different ratios of particulate and gaseous carbon species. Amongst the studied materials, it has been observed that 2 samples provide almost exclusive formation of a gas phase. Correlating these observed signals for selected polymers with the ablated mass of carbon allows us to calculate the sensitivity of gaseous carbon species as 13.8 cts per pg. Using a mass balance approach, we estimated the sensitivity of particulate carbon for the 3 other polymers, where we find significant differences in sensitivity ranging from 1.69 cts per pg to 14.06 cts per pg. This indicates that the sensitivity for particulate carbon species is highly dependent on the sample matrix, resulting in sensitivity differences up to a factor of 7. All in all, the findings of this study support the results of carbon being an inadequate choice for an internal standard in LA-ICP-MS.