In-Situ Imaging Mass Spectrometry Analysis of Melanin Granules in the Human Hair Shaft

The elemental composition of melanin granules and other components of the hair shaft was determined by multi-isotope imaging mass spectrometry, a method with unique advantages for the visualization and quantification of stable isotopes and the elemental composition in study of the fine structure of biologic samples. We mapped and quantified the chemical composition of hair cross-sections using secondary ions generated from naturally occurring 16 O, 12 C 14 N, 32 S, and 34 S with a maximum lateral resolution of 35 nm. Based on these elemental maps of unprecedented resolution we obtained simultaneously the chemical fingerprints and the structural features, such as cuticle, melanin granules, the macro fibrils of the cortex, and small sulfur-rich domains in the medulla, in the hair cross-section. We found an intriguing distribution of 16 O, 12 C 14 N, and 32 S in melanin granules that we interpret as a highly anisotropic pattern of oxidation.