Human hair is an organ that connects fundamental and applied research with everyday life through the cosmetic industry. Yet, the accurate compositional description of the human hair medulla is lacking due to their small size and difficulty with microextraction. Medullas are thus generally classified based on morphology. We investigated the chemical composition of the human hair medulla using synchrotron based infrared microspectroscopy. We confirmed that lipid signatures dominate the medulla infrared spectrum having 3–20 times higher lipid concentration compared to their surrounding cortex. Human hair medullas contain a mixture of non-esterified and esterified lipids, and carboxylate soaps in various proportions.

We reveal the first direct spectroscopic evidence that medulla carboxylates are coordinated to calcium since they exhibit the specific calcium carboxylate signature. Using a representative sample, we observed a strong compositional variability between medullas that was unreported before. We detected calcium carboxylates in 76% of the medullas with one order of magnitude concentration variability between samples. All medullas contained esters with esterification varying by a factor of 30.

Moreover, we detected the presence of crystalline calcium stearate in 9% of the medullas. We described a series of spectral markers to characterize medullas based on their lipid composition and propose to classify medullas in four to five groups. Our analysis provides a more detailed understanding of the chemical composition of human hair medullas that may impact cosmetics and biology. The origin and biological meaning of these variations must still be investigated.