Pyrolysis gas chromatography mass spectrometry: A promising tool for disclosing metal-free tanning agents used in leather industry

Leather represents the principal industrial product derived from the skin of animals. Leather manufacturing has evolved from artisanal practice, making use of vegetable tannins, to industrial production, today mostly based on chromium salts. Chromium tanning accounts for the most efficient and affordable process available on the market, but the environmental pressure caused by heavy metal pollution has pushed towards the development of Metal-Free leather tanning agents. This paper aims at highlighting the potentialities and limits of analytical pyrolysis to characterise metal-free leather samples and to identify the tanning agents. To this aim, thirty-three bovine split leather samples tanned with various metal-free tanning agents (constituted by single or combined formulations of GRANOFIN® F90, glutaraldehyde, tetrakis(hydroxymethyl)phosphonium sulphate, oxazolidine and three different synthetic tannins), provided by bovine split suppliers (Tuscany, Italy) were analysed by flash Pyrolysis coupled with Gas Chromatography - Mass Spectrometry (Py-GC-MS). For most of the tanning formulations, Py-GC-MS was able to determine pyrolytic markers in reference materials, intermediates (wet-white metal-free and metal-free crust) and end-products (metal-free final products). Evolved Gas Analysis coupled with Mass Spectrometry (EGA-MS) was used to evaluate, from the molecular point of view, the thermodegradative profiles of metal-free leathers and compare them with that of chromium tanned leather.