Evaluation of two-phase sample transport upon ablation of gelatin as a proxy for soft biological matrices using nanosecond laser ablation - inductively coupled plasma - mass spectrometry.

ABSTRACT

BACKGROUND: Recent papers on LA-ICP-MS have reported that certain elements are transported in particulate form, others in gaseous form and still others in a combination of both upon ablation of C-based materials. These two phases display different transport behaviour characteristics, potentially causing smearing in elemental maps, and could be processed differently in the ICP which raises concerns as to accuracy of quantification and emphasizes the need for matrix-matching of external standards. This work aims at a better understanding of two-phase sample transport by evaluating the peak profile changes observed upon varying parameters such as laser energy density and wavelength. RESULTS: It is demonstrated that upon ablation of gelatin, elements are transported predominantly in particulate phase, but already at low laser energy density, a significant fraction of some elements is transported in the gaseous phase, which is even more expressed at higher energy density. This behaviour is element-specific since the ratio of the signal intensity for the analyte element transported in gas phase to the total signal intensity was 0 % for 23Na, 43 % for 66Zn and as high as 95 % for 13C using a 193 nm laser. The results also suggest an effect of the laser wavelength, as all elements show either the same or higher amount of gas phase formation upon ablating with 213 nm versus 193 nm. It was even established that elements that fully occur in particulate form upon ablation using 193 nm laser radiation are partly converted into gaseous phase when using 213 nm. SIGNIFICANCE: This work provides a thorough investigation of the underexposed phenomenon of two-phase sample transport upon ablation of biological samples upon via LA-ICP-MS. It is shown that for some elements a fraction of the ablated material is converted and transported in the gas phase, which can lead to significant smearing effects. As such, it is important to evaluate element-specific peak profiles on beforehand and, if necessary, adapt instrument settings and slow down data acquisition.