Oligomerization of levoglucosan by Fenton chemistry in proxies of biomass burning aerosols

Reactions of levoglucosan with \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ OH^{ \bullet } $$\end{document} produced from Fenton chemistry were studied in solution serving as a proxy for biomass burning aerosols. Two modes of oligomerization (≤2000 u) were observed for reaction times between 1 and 7 days using matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF-MS) and laser desorption ionization time-of-flight mass spectrometry (LDI-TOF-MS). Single-mass unit continuum mass distributions with dominant −2 u patterns were measured and superimposed by a +176/+162 u oligomer series. This latter oligomer pattern was attributed to a Criegee rearrangement (+14 u) of levoglucosan, initiated by \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ OH^{ \bullet } $$\end{document}, forming a lactone (176 u). The acid-catalyzed reaction of any ROH from levoglucosan (+162 u) forms an ester through transesterification of the lactone functionality, whereupon propagation forms polyesters. Proposed products and chemical mechanisms are suggested as sources and precursors of humic-like substances (HULIS), which are known to possess a large saccharic component and are possibly formed from biomass burning aerosols (Andreae, Global Biomass Burning, MIT Press, Cambridge, Massachusetts, 3–21, 1991).