Elucidating the chemical structure of pyrogenic organic matter by combining magnetic resonance, mid-infrared spectroscopy and mass spectrometry

Fire-derived organic matter (pyrogenic organic matter, or PyOM), despite its apparent long term stability in the environment, has recently been reported to degrade faster than previously thought. Current studies have suggested that the composition and structure of PyOM can provide new insights on the mechanisms by which C and N from pyrolyzed biomaterials are stabilized in soils. To better understand the chemical structure of PyOM produced under typical fire conditions in temperate forests, samples of dual-enriched ( 13 C/ 15 N) Pinus ponderosa wood and the charred material produced at 450 C were analyzed by solid state nuclear magnetic resonance (ssNMR), electron paramagnetic resonance (EPR), diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy, and both isotopic and elemental composition (C, H, O, and N). Notably, the use of high magnetic field strengths in combination with isotopic enrichment augmented the NMR detection sensitivity, and thus improved the quality of molecular information as compared with previously reported studies of pyrogenic materials. The key molecular groups of pine wood and the corresponding PyOM materials were determined using magic-angle spinning (MAS) 13 C, 15 N, and 1

[1]  S. Running Is Global Warming Causing More, Larger Wildfires? , 2006, Science.

[2]  Michael W. I. Schmidt,et al.  Black (pyrogenic) carbon: a synthesis of current knowledge and uncertainties with special consideration of boreal regions , 2006 .

[3]  P. Templer,et al.  Stable Isotopes in Plant Ecology , 2002 .

[4]  H. Knicker,et al.  Degradation of grass-derived pyrogenic organic material, transport of the residues within a soil column and distribution in soil organic matter fractions during a 28 month microcosm experiment , 2011 .

[5]  H. Knicker,et al.  Carbon and nitrogen degradation on molecular scale of grass-derived pyrogenic organic material during 28 months of incubation in soil , 2011 .

[6]  S. Maunu,et al.  NMR studies of wood and wood products , 2002 .

[7]  M. Schmidt,et al.  The benzene polycarboxylic acid (BPCA) pattern of wood pyrolyzed between 200°C and 1000°C. , 2010 .

[8]  M. Torn,et al.  Fine Roots vs. Needles: A Comparison of 13C and 15N Dynamics in a Ponderosa Pine Forest Soil , 2006 .

[9]  W. P. Ball,et al.  Evidence for a pore-filling mechanism in the adsorption of aromatic hydrocarbons to a natural wood char. , 2007, Environmental science & technology.

[10]  J. González-Pérez,et al.  Transformations in carbon and nitrogen-forms in peat subjected to progressive thermal stress as revealed by analytical pyrolysis , 2010 .

[11]  J. Skjemstad,et al.  Formation, transformation and transport of black carbon (charcoal) in terrestrial and aquatic ecosystems. , 2006, The Science of the total environment.

[12]  Christopher I. Roos,et al.  Fire in the Earth System , 2009, Science.

[13]  P. Nico,et al.  Dynamic molecular structure of plant biomass-derived black carbon (biochar). , 2010, Environmental science & technology.

[14]  G. Maciel,et al.  Qualitative and quantitative analysis of solid lignin samples by carbon-13 nuclear magnetic resonance spectrometry , 1987 .

[15]  P. Hatcher Chemical structural studies of natural lignin by dipolar dephasing solid-state 13C nuclear magnetic resonance , 1987 .

[16]  R. M. Bustin,et al.  FTIR spectroscopy and reflectance of modern charcoals and fungal decayed woods: implications for studies of inertinite in coals , 1998 .

[17]  S. Opella,et al.  Selection of nonprotonated carbon resonances in solid-state nuclear magnetic resonance , 1979 .

[18]  Jeff Baldock,et al.  Chemical composition and bioavailability of thermally altered Pinus resinosa (Red pine) wood , 2002 .

[19]  G. Maciel,et al.  Carbon-13 nuclear magnetic resonance spectrometry with cross polarization and magic-angle spinning for analysis of lodgepole pine wood , 1982 .

[20]  C. Popescu,et al.  Characterization of Fungal-Degraded Lime Wood by X-Ray Diffraction and Cross-Polarization Magic-Angle-Spinning 13C-Nuclear Magnetic Resonance Spectroscopy , 2010, Applied spectroscopy.

[21]  S. Ogle,et al.  Knowledge gaps in soil carbon and nitrogen interactions – From molecular to global scale , 2011 .

[22]  Y. Imamura,et al.  Analysis of chemical structure of wood charcoal by X-ray photoelectron spectroscopy , 1998, Journal of Wood Science.

[23]  Noel L. Owen,et al.  INFRARED SPECTROSCOPIC STUDIES OF SOLID WOOD , 2001 .

[24]  E. Mills,et al.  The Impact of Climate Change on Wildfire Severity: A Regional Forecast for Northern California , 2004 .

[25]  M. Schmidt,et al.  Determination of the aromaticity and the degree of aromatic condensation of a thermosequence of wood charcoal using NMR , 2011 .

[26]  H. Knicker ''Black nitrogen" - an important fraction in determining the recalcitrance of charcoal , 2010 .

[27]  Robin K. Harris,et al.  NMR Nomenclature: Nuclear Spin Properties and Conventions for Chemical Shifts—IUPAC Recommendations , 2002 .

[28]  B. Xing,et al.  Sorption of organic contaminants by biopolymer-derived chars. , 2007, Environmental science & technology.

[29]  J. Oades,et al.  The use of spin counting for determining quantitation in solid state 13C NMR spectra of natural organic matter: 1. Model systems and the effects of paramagnetic impurities , 2000 .

[30]  R. Pugmire,et al.  Evolution of carbon structure in chemically activated wood , 1995 .

[31]  P. Granger,et al.  NMR Nomenclature. Nuclear Spin Properties and Conventions for Chemical Shifts (IUPAC Recommendations 2001) , 2002 .

[32]  J. Weiland,et al.  Study of chemical modifications and fungi degradation of thermally modified wood using DRIFT spectroscopy , 2003, Holz als Roh- und Werkstoff.

[33]  J. Skjemstad,et al.  Synthesis and characterisation of laboratory-charred grass straw (Oryza sativa) and chestnut wood (Castanea sativa) as reference materials for black carbon quantification , 2006 .

[34]  J. Baldock,et al.  Impact of remote protonation on 13C CPMAS NMR quantitation of charred and uncharred wood. , 2002, Solid state nuclear magnetic resonance.

[35]  M. Schmidt,et al.  Black carbon in soils and sediments: Analysis, distribution, implications, and current challenges , 2000 .

[36]  John Gaunt,et al.  Bio-char Sequestration in Terrestrial Ecosystems – A Review , 2006 .

[37]  Andrew E. Bennett,et al.  Heteronuclear decoupling in rotating solids , 1995 .

[38]  I. Kögel‐Knabner,et al.  Characterization of alkyl carbon in forest soils by CPMAS 13C NMR spectroscopy and dipolar dephasing , 1989 .

[39]  E. Goldberg Black carbon in the environment : properties and distribution / Edward D. Goldberg , 1985 .

[40]  B. Fung,et al.  An improved broadband decoupling sequence for liquid crystals and solids. , 2000, Journal of magnetic resonance.

[41]  J. Lehmann Bio-energy in the black , 2007 .

[42]  M. Kleber,et al.  Molecular-level interactions in soils and sediments: the role of aromatic pi-systems. , 2009, Environmental science & technology.

[43]  J. Gray,et al.  Climatic information from 18O/16O analysis of cellulose, lignin and whole wood from tree rings , 1977, Nature.

[44]  J. Oades,et al.  The use of spin counting for determining quantitation in solid state 13C NMR spectra of natural organic matter: 2. HF-treated soil fractions , 2000 .

[45]  Anna V. McBeath,et al.  Variation in the degree of aromatic condensation of chars , 2009 .

[46]  M. Torn,et al.  Biological degradation of pyrogenic organic matter in temperate forest soils , 2012 .

[47]  G. Maciel,et al.  Structural resolution in the carbon-13 nuclear magnetic resonance spectrometric analysis of coal by cross polarization and magic-angle spinning , 1982 .

[48]  Claudia I. Czimczik,et al.  Effects of charring on mass, organic carbon, and stable carbon isotope composition of wood , 2002 .

[49]  M. Schmidt,et al.  Stable isotopic analysis of pyrogenic organic matter in soils by liquid chromatography-isotope-ratio mass spectrometry of benzene polycarboxylic acids. , 2011, Rapid communications in mass spectrometry : RCM.

[50]  Derek Stewart,et al.  Estimation of wood density and chemical composition by means of diffuse reflectance mid-infrared Fourier transform (DRIFT-MIR) spectroscopy. , 2006, Journal of agricultural and food chemistry.

[51]  Haiping Yang,et al.  Characteristics of hemicellulose, cellulose and lignin pyrolysis , 2007 .

[52]  S. Leavitt,et al.  Environment and paleoecology of a 12 ka mid-North American Younger Dryas forest chronicled in tree rings , 2008, Quaternary Research.

[53]  F. González-Vila,et al.  A new conceptual model for the structural properties of char produced during vegetation fires , 2008 .

[54]  Sirkka Liisa Maunu 13C CPMAS NMR Studies of Wood, Cellulose Fibers, and Derivatives , 2009 .

[55]  Markus Leuenberger,et al.  Reducing uncertainties in δ13C analysis of tree rings: Pooling, milling, and cellulose extraction , 1998 .

[56]  P. Granger,et al.  Nuclear Spin Properties and Conventions for Chemical Shifts (IUPAC Recommendations 2001 ) , 2007 .

[57]  A. Casadevall,et al.  Protection of Melanized Cryptococcus neoformans from Lethal Dose Gamma Irradiation Involves Changes in Melanin's Chemical Structure and Paramagnetism , 2011, PloS one.

[58]  Amy M. P. Oen,et al.  How quality and quantity of organic matter affect polycyclic aromatic hydrocarbon desorption from Norwegian harbor sediments , 2006, Environmental toxicology and chemistry.

[59]  K. Zilm,et al.  Chemical shift referencing in MAS solid state NMR. , 2003, Journal of magnetic resonance.

[60]  J. Lehmann,et al.  Ameliorating physical and chemical properties of highly weathered soils in the tropics with charcoal – a review , 2002, Biology and Fertility of Soils.

[61]  Albert A Koelmans,et al.  Black carbon: the reverse of its dark side. , 2006, Chemosphere.

[62]  M. Torn,et al.  Centennial black carbon turnover observed in a Russian steppe soil , 2008 .

[63]  Michael A. Wilson,et al.  Carbon distribution in coals and coal macerals by cross polarization magic angle spinning carbon-13 nuclear magnetic resonance spectrometry , 1984 .

[64]  J. Satrio,et al.  Characterization of biochar from fast pyrolysis and gasification systems , 2009 .

[65]  S. Leavitt,et al.  Method for batch processing small wood samples to holocellulose for stable-carbon isotope analysis , 1993 .

[66]  Michael A. Wilson,et al.  Structural analysis of geochemical samples by solid-state nuclear magnetic resonance spectrometry. Role of paramagnetic material , 1987 .

[67]  P. Vitousek,et al.  Mineralogical controls on soil black carbon preservation , 2012 .