Abstract
The research presented herein is the first attempt to probe the chemical nature of lignocellulosic samples by the application of carbon near edge X-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft X-ray technique that principally provides selective interrogation of discrete atomic moieties using photoelectrons of variable energies. The X1A beam line of the National Synchrotron Light Source was employed for the specific purpose of observing carboxylic acid moieties that display a signature absorption band centered at 289 eV. This study caps a larger effort to support the mechanistic basis for lignocellulosic fiber chemical degradation induced by the disproportionation of hydrogen peroxiduring fiber bleaching trials. It is shown that fibers that have been bleached with a hydrogen peroxide phase without removal of resident pendant metals (Mn, Cu, Fe) sustain significant macroscopic damage likely via classical Fenton-type radical reactions, as evidenced by a tensile reduction by over 30%. We present X-ray absorption spectra obtained using a scanning transmission X-ray microscope (STXM) at the end of a 2.5 GeV electron synchrotron that provided 1s → π* contrast-enhanced micrographs illustrating a random distribution of acid functionalities that were principally located on fiber surfaces. Control studies using non-bleached fibers demonstrated that very little signature carboxylic acid absorption patterns were present in the fibers, suggesting that these groups are an incriminating fingerprint for macroscopic fiber strength damage during non-radical suppressed bleaching trials.
Similar content being viewed by others
References
R. Andreozzi A. D’Apuzzo R. Marotta (2002) ArticleTitleOxidation of aromatic substrates in water/goethite slurry by means of hydrogen peroxide Water Res. 36 4691–4698
G.D. Cody R.E. Botto H. Ade S. Behal M. Disko S. Wirick (1995) ArticleTitleInner-shell spectroscopy and imaging of a subbituminous coal: in situ analysis of organic and inorganic microstructure using C(1s)-, Ca(2p)-, and Cl(2s)-NEXAFS Energy Fuels 9 525–533
G.D. Cody R.E. Botto H. Ade S. Wirick (1996) ArticleTitleThe application of soft X-ray microscopy to the in situ analysis of sporinite in coal Int. J. Coal Geo. 32 69–86
G.D. Cody H. Ade S. Wirick G.D. Mitchell A. Davis (1998) ArticleTitleDetermination of chemical-structural changes in vitrinite accompanying luminescence alteration using C-NEXAFS analysis Org. Geochem. 28 441–455
S. Fu X. Chai Q. Hou L.A. Lucia (2004) ArticleTitleA chemical basis for a selectivity threshold to the oxygen delignification of kraft softwood fiber as supported by the use of chemical selectivity agents Ind. Eng. Chem. Res. 43 2291–2295
J. Gacen D. Cayuela I. Gacen (2002) ArticleTitleRapid bleaching of wool with hydrogen peroxide AATCC Rev. 2 28–31
C. Jacobsen S. Williams E. Anderson M.T. Browne C.J. Buckley D. Kern J. Kirz M. Rivers X. Zhang (1991) ArticleTitleDiffraction-limited imaging in a scanning transmission X-ray microscope Opt. Commun. 86 351
C.J. Knill J.F. Kennedy (2002) ArticleTitleDegradation of cellulose under alkaline conditions Carbohydr. Polym. 3 281–300
J. Liden L.-O. Ohman (1997) ArticleTitleRedox stabilization of iron and manganese in the +II oxidation state by magnesium precipitates and some anionic polymers: implications for the use of oxygen-based bleaching chemicals J. Pulp Pap. Sci. 23 193–199
F. Lopez M.E. Eugenio M. J. Diaz (2002) ArticleTitleBleaching of olive tree residues pulp with peracetic acid and comparative study with hydrogen peroxide Industr. Eng. Chem. Res. 41 3518–3525
Y. Ma C.T. Chen G. Meigs K. Randall F. Sette (1997) ArticleTitleHigh-resolution K-shell photoabsorption measurements of simple molecules Phys. Rev. A 44 1848–1859
D.G. Mancosky L.A. Lucia (2001a) ArticleTitleUse of TOF-SIMS for the analysis of surface metals in H2O2-bleached lignocellulosic fibers Pure Appl. Chem. 73 2047–2058
Mancosky D.G., Lucia L.A., Goyal G. and Hanna R. 2001b. Comparison of the brightening response between juvenile and mature black spruce fibers. TAPPI Pulping ConferenceCD.
A.M.M. Taher D.M. Cates (1975) ArticleTitleBleaching cellulose: Part I. A free radical mechanism Text. Chem. Color. 7 220–224
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Mancosky, D.G., Lucia, L.A., Nanko, H. et al. Novel visualization studies of lignocellulosic oxidation chemistry by application of C-near edge X-ray absorption fine structure spectroscopy. Cellulose 12, 35–41 (2005). https://doi.org/10.1007/s10570-004-4369-4
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s10570-004-4369-4