The absolute concentration of Zn in human fingernail clippings was determined ex vivo using 1064 nm laser-induced breakdown spectroscopy and confirmed by speciated isotope dilution mass spectrometry. A nail testing protocol that sampled across the nail (perpendicular to the direction of growth) was developed and validated by scanning electron microscopy energy-dispersive X-ray spectrometry. Using this protocol, a partial least squares (PLS) regression model predicted the Zn concentration in the fingernails of five people to within an average of 7 ppm. The variation in the Zn concentration with depth into the nail determined by laser-induced breakdown spectroscopy was studied and showed no systematic variation for up to 15 subsequent laser pulses in one location. The effects of nail hydration (dehydrated and over-hydrated) and nail surface roughness were investigated to explain an anomalously large scatter observed in the measurements. This scatter was attributed to the layered nature and fibrous structure of the fingernails, which resulted in non-uniform ablation as determined by scanning electron microscopy. This work demonstrates that a protocol consisting of low pulse energy (<10 mJ) 1064 nm laser pulses incident on human fingernail clippings in an Ar environment can produce quantifiable Zn emission in the laser-induced plasma and that the measured Zn intensity can be used to accurately predict the Zn concentration in human fingernails.
Keywords: LIBS; Laser-induced breakdown spectroscopy; PLS; Zn; fingernails; partial least squares regression.