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Understanding paper degradation: identification of products of cellulosic paper decomposition at the wet-dry “tideline” interface using GC-MS

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Abstract

Cellulose paper degradation products forming in the “tideline” area at the wet-dry interface of pure cellulose paper were analyzed using gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) and high-resolution electrospray ionization-mass spectrometry (ESI-MS, LTQ Orbitrap) techniques. Different extraction protocols were employed in order to solubilize the products of oxidative cellulose decomposition, i.e., a direct solvent extraction or a more laborious chromophore release and identification (CRI) technique aiming to reveal products responsible for paper discoloration in the tideline area. Several groups of low molecular weight compounds were identified, suggesting a complex pathway of cellulose decomposition in the tidelines formed at the cellulose-water-oxygen interface. Our findings, namely the appearance of a wide range of linear saturated carboxylic acids (from formic to nonanoic), support the oxidative autocatalytic mechanism of decomposition. In addition, the identification of several furanic compounds (which can be, in part, responsible for paper discoloration) plus anhydro carbohydrate derivatives sheds more light on the pathways of cellulose decomposition. Most notably, the mechanisms of tideline formation in the presence of molecular oxygen appear surprisingly similar to pathways of pyrolytic cellulose degradation. More complex chromophore compounds were not detected in this study, thereby revealing a difference between this short-term tideline experiment and longer-term cellulose aging.

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Acknowledgments

SS thanks the Chateaubriand Fellowship Program for the financial support for this research. SS also thanks the Office of Scientific and Academic Cooperation at the French Embassy in Israel for the support. We thank Agilent Technologies (Les Ulis, France) for providing the GC-MS equipment necessary to complete the project.

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Correspondence to Anne-Laurence Dupont or Richard B. Cole.

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Sladkevich, S., Dupont, AL., Sablier, M. et al. Understanding paper degradation: identification of products of cellulosic paper decomposition at the wet-dry “tideline” interface using GC-MS. Anal Bioanal Chem 408, 8133–8147 (2016). https://doi.org/10.1007/s00216-016-9916-y

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