Characterizing lignin: Combining lignin phenol, methoxy quantification, and dual stable carbon and hydrogen isotopic techniques

doi:10.1016/j.orggeochem.2019.07.003

	Characterizing lignin: Combining lignin phenol, methoxy quantification, and dual stable carbon and hydrogen isotopic techniques
	Lee, Hyejung ; Feng, Xiaojuan1 ; Mastalerz, Maria 2; Feakins, Sarah J.
	2019
发表期刊	ORGANIC GEOCHEMISTRY
ISSN	0146-6380
卷号	136
摘要	Lignin is a major structural plant biochemical and biogeochemical compound present in peat and lignite. Its monomeric (phenolic) and polymeric structures include varying amounts of ether-bonded methyl groups (i.e., methoxy or -OCH3). These methoxy groups are generally underused targets for both structural characterization and isotopic analyses. We analyzed the quantity and C and H isotopic composition of methoxy groups within a range of substrates including lignin phenols, lignin, wood, peat, lignite, and sub-bituminous and bituminous coal. We used the Zeisel method to cleave the ether bonds with hydroiodic acid to yield iodomethane which can be analyzed by gas chromatography (GC). Finding inconsistent transfer and isotope effects associated with room temperature headspace injections, we instead used iso-octane as a solvent for the iodomethane analyte (the liquid method). Using the liquid method, we obtained a linear response by GC-flame ionization detection (GC-FID) for iodomethane and a linear calibration and 85 +/- 6% recovery of methyl from methoxy groups from solid standards of phenolic compounds of known stoichiometry. We introduced quantification via lignin phenolic compounds to calibrate both analytical and experimental yield. Methyl yields provided structural information and confirmed that lignin oxidation products (LOPs) from copper oxide oxidation underestimate the number of methoxy-bearing phenols (yield < 0.3 of expected based on stoichiometry); in combination the two approaches provide structural information and quantification. We found that concentrations of methyl from methoxy groups in geologic sediments (lignite, sub-bituminous and bituminous coal) initially increase with diagenesis as lignin to cellulose ratio increases, and then decline to low concentrations during coalification, offering new possibilities for characterizing the transformation of peat and lignite. We assessed an array of plant biochemicals and established that natural and synthetic methoxy groups span a broad range of dual stable carbon and hydrogen isotopic compositions indicating scope for biogeochemical and forensic applications. (C) 2019 Elsevier Ltd. All rights reserved.
关键词	Lignin Lignite Methoxy Stable carbon and hydrogen isotopes
学科领域	Geochemistry & Geophysics
DOI	10.1016/j.orggeochem.2019.07.003
收录类别	SCI
语种	英语
WOS关键词	GEOGRAPHICAL ORIGIN ; DELTA-H-2 VALUES ; ORGANIC-MATTER ; RAPID METHOD ; WHOLE WOOD ; RATIOS ; CELLULOSE ; FRACTIONATION ; TEMPERATURES ; DELTA-C-13
WOS研究方向	Geochemistry & Geophysics
WOS记录号	WOS:000482176500004
出版者	PERGAMON-ELSEVIER SCIENCE LTD
文献子类	Article
出版地	OXFORD
EISSN	1873-5290
资助机构	American Chemical Society Petroleum Research FundAmerican Chemical Society [53747-ND2] ; USC Provost fellowship ; USC Earth Science Department graduate student research funding
作者邮箱	feakins@usc.edu
引用统计	被引频次：22[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.ibcas.ac.cn/handle/2S10CLM1/19422
专题	植被与环境变化国家重点实验室
作者单位	1.[Lee, Hyejung; Feakins, Sarah J.] Univ Southern Calif, Dept Earth Sci, Los Angeles, CA 90007 USA 2.Chinese Acad Sci, Inst Bot, State Key Lab Vegetat & Environm Change, Beijing 100093, Peoples R China 3.Indiana Univ, Indiana Geol & Water Survey, Bloomington, IN 47405 USA
推荐引用方式 GB/T 7714	Lee, Hyejung,Feng, Xiaojuan,Mastalerz, Maria,et al. Characterizing lignin: Combining lignin phenol, methoxy quantification, and dual stable carbon and hydrogen isotopic techniques[J]. ORGANIC GEOCHEMISTRY,2019,136.
APA	Lee, Hyejung,Feng, Xiaojuan,Mastalerz, Maria,&Feakins, Sarah J..(2019).Characterizing lignin: Combining lignin phenol, methoxy quantification, and dual stable carbon and hydrogen isotopic techniques.ORGANIC GEOCHEMISTRY,136.
MLA	Lee, Hyejung,et al."Characterizing lignin: Combining lignin phenol, methoxy quantification, and dual stable carbon and hydrogen isotopic techniques".ORGANIC GEOCHEMISTRY 136(2019).

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