Comparison of soil organic carbon speciation using C NEXAFS and CPMAS 13C NMR spectroscopy

Prietzel, Jörg; Müller, Svenja; Kögel-Knabner, Ingrid; Thieme, Jürgen; Jaye, Cherno; Fischer, Daniel

doi:10.1016/j.scitotenv.2018.02.121

Comparison of soil organic carbon speciation using C NEXAFS and CPMAS ¹³C NMR spectroscopy

Journal Article · Tue Feb 20 00:00:00 EST 2018 · Science of the Total Environment

DOI:https://doi.org/10.1016/j.scitotenv.2018.02.121· OSTI ID:1463852

^[1]; ^[1]; Kögel-Knabner, Ingrid ^[1]; Thieme, Jürgen ^[2]; Jaye, Cherno ^[3]; Fischer, Daniel ^[3]

Munich Univ. of Technology (Germany). Chair of Soil Science and Dept. of Ecology and Ecosystem Management
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Material Measurement Lab.

Here, we compared synchrotron-based C near-edge X-ray absorption fine structure (NEXAFS) and CPMAS ¹³C nuclear magnetic resonance (NMR) spectroscopy with respect to their precision and accuracy to quantify different organic carbon (OC) species in defined mixtures of soil organic matter source compounds. We also used both methods to quantify different OC species in organic surface horizons of a Histic Leptosol as well as in mineral topsoil and subsoil horizons of two soils with different parent material, stage of pedogenesis, and OC content (Cambisol: 15–30 OC mg g^-1, Podzol: 0.9–7 OC mg g^-1). CPMAS ¹³C NMR spectroscopy was more accurate and precise (mean recovery of different C functional groups 96–103%) than C NEXAFS spectroscopy (mean recovery 92–113%). For organic surface and topsoil samples, NMR spectroscopy consistently yielded larger O-alkyl C percentages and smaller alkyl C percentages than C NEXAFS spectroscopy. For the Cambisol subsoil samples both methods performed well and showed similar C speciation results. NEXAFS spectroscopy yielded excellent spectra with a high signal-to-noise ratio also for OC-poor Podzol subsoil samples, whereas this was not the case for CPMAS ¹³C NMR spectroscopy even after sample treatment with HF. Our results confirm the analytical power of CPMAS ¹³C NMR spectroscopy for a reliable quantitative OC speciation in soils with >10 mg OC g^-1. Moreover, they highlight the potential of synchrotron-based C NEXAFS spectroscopy as fast, non-invasive method to semi-quantify different C functional groups in soils with low C content (0.9–10 mg g^-1).

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1463852

Report Number(s):: BNL--207922-2018-JAAM

Journal Information:: Science of the Total Environment, Journal Name: Science of the Total Environment Journal Issue: C Vol. 628-629; ISSN 0048-9697

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Dissolved organic matter sorption by mineral constituents of subsoil clay fractions Kaiser, Klaus; Zech, Wolfgang Journal of Plant Nutrition and Soil Science, Vol. 163, Issue 5 https://doi.org/10.1002/1522-2624(200010)163:5<531::AID-JPLN531>3.0.CO;2-N	journal	October 2000
CP-MAS-13C-NMR-Spektren organischer Lagen einer Tangelrendzina Zech, W.; Kögel, Ingrid; Zucker, A. Zeitschrift für Pflanzenernährung und Bodenkunde, Vol. 148, Issue 5 https://doi.org/10.1002/jpln.19851480504	journal	January 1985
Differenzierung der Eisenoxide des Bodens durch Extraktion mit Ammoniumoxalat-Lösung Schwertmann, U. Zeitschrift für Pflanzenernährung, Düngung, Bodenkunde, Vol. 105, Issue 3 https://doi.org/10.1002/jpln.3591050303	journal	January 1964
Variable-Amplitude Cross-Polarization MAS NMR Peersen, O. B.; Wu, X. L.; Kustanovich, I. Journal of Magnetic Resonance, Series A, Vol. 104, Issue 3 https://doi.org/10.1006/jmra.1993.1231	journal	October 1993
Soil phosphorus supply controls P nutrition strategies of beech forest ecosystems in Central Europe Lang, F.; Krüger, J.; Amelung, W. Biogeochemistry, Vol. 136, Issue 1 https://doi.org/10.1007/s10533-017-0375-0	journal	September 2017
Deep soil organic matter—a key but poorly understood component of terrestrial C cycle Rumpel, Cornelia; Kögel-Knabner, Ingrid Plant and Soil, Vol. 338, Issue 1-2 https://doi.org/10.1007/s11104-010-0391-5	journal	May 2010
Analysis of non-cellulosic polysaccharides helps to reveal the history of thick organic surface layers on calcareous Alpine soils Prietzel, Jörg; Dechamps, Nicolas; Spielvogel, Sandra Plant and Soil, Vol. 365, Issue 1-2 https://doi.org/10.1007/s11104-012-1340-2	journal	July 2012
N-15 and C-13 CPMAS and solution NMR studies of N-15 enriched plant material during 600 days of microbial degradation Knicker, H.; Lüdemann, H. -D. Organic Geochemistry, Vol. 23, Issue 4 https://doi.org/10.1016/0146-6380(95)00007-2	journal	April 1995
Organic carbon and sulphur compounds in wetland soils: insights on structure and transformation processes using K-edge XANES and NMR spectroscopy Jokic, Aleksander; Cutler, Jeffrey N.; Ponomarenko, Elena Geochimica et Cosmochimica Acta, Vol. 67, Issue 14 https://doi.org/10.1016/S0016-7037(03)00101-7	journal	July 2003
The use of spin counting for determining quantitation in solid state 13C NMR spectra of natural organic matter Smernik, Ronald J.; Oades, J. Malcolm Geoderma, Vol. 96, Issue 1-2 https://doi.org/10.1016/S0016-7061(00)00006-9	journal	May 2000
13C and 15N NMR spectroscopy as a tool in soil organic matter studies Kögel-Knabner, Ingrid Geoderma, Vol. 80, Issue 3-4 https://doi.org/10.1016/S0016-7061(97)00055-4	journal	November 1997
Applicability of solid-state 13C CP/MAS NMR analysis in Spodosols: chemical removal of magnetic materials Dai, K'o H.; Johnson, Chris E. Geoderma, Vol. 93, Issue 3-4 https://doi.org/10.1016/S0016-7061(99)00072-5	journal	December 1999
Spectroscopic characterization of the structural and functional properties of natural organic matter fractions Chen, Jie; Gu, Baohua; LeBoeuf, Eugene J. Chemosphere, Vol. 48, Issue 1 https://doi.org/10.1016/S0045-6535(02)00041-3	journal	July 2002
Vertical distribution, age, and chemical composition of organic carbon in two forest soils of different pedogenesis Rumpel, C.; Kögel-Knabner, I.; Bruhn, F. Organic Geochemistry, Vol. 33, Issue 10 https://doi.org/10.1016/S0146-6380(02)00088-8	journal	October 2002
Determination of chemical-structural changes in vitrinite accompanying luminescence alteration using C-NEXAFS analysis Cody, G. D.; Ade, H.; Wirick, S. Organic Geochemistry, Vol. 28, Issue 7-8 https://doi.org/10.1016/S0146-6380(98)00010-2	journal	May 1998
Complexes of fulvic acid on the surface of hematite, goethite, and akaganeite: FTIR observation Fu, Hongbo; Quan, Xie Chemosphere, Vol. 63, Issue 3 https://doi.org/10.1016/j.chemosphere.2005.08.054	journal	April 2006
Organic carbon distribution, speciation, and elemental correlations within soil microaggregates: Applications of STXM and NEXAFS spectroscopy Wan, Jiamin; Tyliszczak, Tolek; Tokunaga, Tetsu K. Geochimica et Cosmochimica Acta, Vol. 71, Issue 22 https://doi.org/10.1016/j.gca.2007.07.030	journal	November 2007
Changes in water extractable organic matter during incubation of forest floor material in the presence of quartz, goethite and gibbsite surfaces Heckman, Katherine; Vazquez-Ortega, Angelica; Gao, Xiaodong Geochimica et Cosmochimica Acta, Vol. 75, Issue 15 https://doi.org/10.1016/j.gca.2011.05.009	journal	August 2011
Nano-scale investigation of the association of microbial nitrogen residues with iron (hydr)oxides in a forest soil O-horizon Keiluweit, Marco; Bougoure, Jeremy J.; Zeglin, Lydia H. Geochimica et Cosmochimica Acta, Vol. 95 https://doi.org/10.1016/j.gca.2012.07.001	journal	October 2012
Cross polarization-single pulse/magic angle spinning (CPSP/MAS): A robust technique for routine soil analysis by solid-state NMR Courtier-Murias, Denis; Farooq, Hashim; Longstaffe, James G. Geoderma, Vol. 226-227 https://doi.org/10.1016/j.geoderma.2014.03.006	journal	August 2014
Is demineralization with dilute hydrofluoric acid a viable method for isolating mineral stabilized soil organic matter? Sanderman, Jonathan; Farrell, Mark; Macreadie, Peter I. Geoderma, Vol. 304 https://doi.org/10.1016/j.geoderma.2017.03.002	journal	October 2017
Small-scale spatial distribution of phosphorus fractions in soils from silicate parent material with different degree of podzolization Werner, Florian; de la Haye, Tilman René; Spielvogel, Sandra Geoderma, Vol. 302 https://doi.org/10.1016/j.geoderma.2017.04.026	journal	September 2017
Quantitative solid-state 13C NMR with signal enhancement by multiple cross polarization Johnson, Robert L.; Schmidt-Rohr, Klaus Journal of Magnetic Resonance, Vol. 239 https://doi.org/10.1016/j.jmr.2013.11.009	journal	February 2014
Stabilisation of soil organic matter by interactions with minerals as revealed by mineral dissolution and oxidative degradation Eusterhues, Karin; Rumpel, Cornelia; Kleber, Markus Organic Geochemistry, Vol. 34, Issue 12 https://doi.org/10.1016/j.orggeochem.2003.08.007	journal	December 2003
Intimate association between O/N-alkyl carbon and iron oxides in clay fractions of forest soils Schöning, Ingo; Knicker, Heike; Kögel-Knabner, Ingrid Organic Geochemistry, Vol. 36, Issue 10 https://doi.org/10.1016/j.orggeochem.2005.06.005	journal	October 2005
C 1s K-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy for characterizing functional group chemistry of black carbon Heymann, Karen; Lehmann, Johannes; Solomon, Dawit Organic Geochemistry, Vol. 42, Issue 9 https://doi.org/10.1016/j.orggeochem.2011.06.021	journal	October 2011
Environmental Nuclear Magnetic Resonance Spectroscopy: An Overview and a Primer Simpson, André J.; Simpson, Myrna J.; Soong, Ronald Analytical Chemistry, Vol. 90, Issue 1 https://doi.org/10.1021/acs.analchem.7b03241	journal	December 2017
Adsorption and desorption of natural organic matter on iron oxide: mechanisms and models Gu, Baohua.; Schmitt, Juergen.; Chen, Zhihong. Environmental Science & Technology, Vol. 28, Issue 1 https://doi.org/10.1021/es00050a007	journal	January 1994
An In-Situ ATR-FTIR Study: The Surface Coordination of Salicylic Acid on Aluminum and Iron(III) Oxides Biber, Madeleine V.; Stumm, Werner. Environmental Science & Technology, Vol. 28, Issue 5 https://doi.org/10.1021/es00054a004	journal	May 1994
Chemical Heterogeneity of Organic Soil Colloids Investigated by Scanning Transmission X-ray Microscopy and C-1s NEXAFS Microspectroscopy Schumacher, Marc; Christl, Iso; Scheinost, Andreas C. Environmental Science & Technology, Vol. 39, Issue 23 https://doi.org/10.1021/es050099f	journal	December 2005
C-1s NEXAFS Spectroscopy Reveals Chemical Fractionation of Humic Acid by Cation-Induced Coagulation Christl, Iso; Kretzschmar, Ruben Environmental Science & Technology, Vol. 41, Issue 6 https://doi.org/10.1021/es062141s	journal	March 2007
Nuclear Magnetic Resonance Spectroscopy and Its Key Role in Environmental Research Simpson, Andre J.; Simpson, Myrna J.; Soong, Ronald Environmental Science & Technology, Vol. 46, Issue 21 https://doi.org/10.1021/es302154w	journal	August 2012
Soft X-ray Spectromicroscopy Study of Mineral-Organic Matter Associations in Pasture Soil Clay Fractions Chen, Chunmei; Dynes, James J.; Wang, Jian Environmental Science & Technology, Vol. 48, Issue 12 https://doi.org/10.1021/es405485a	journal	May 2014
Properties of Fe-Organic Matter Associations via Coprecipitation versus Adsorption Chen, Chunmei; Dynes, James J.; Wang, Jian Environmental Science & Technology, Vol. 48, Issue 23 https://doi.org/10.1021/es503669u	journal	November 2014
Carbon-13 nuclear magnetic resonance of polymers spinning at the magic angle Schaefer, Jacob; Stejskal, E. O. Journal of the American Chemical Society, Vol. 98, Issue 4 https://doi.org/10.1021/ja00420a036	journal	February 1976
Innershell Absorption Spectroscopy of Amino Acids Kaznacheyev, K.; Osanna, A.; Jacobsen, C. The Journal of Physical Chemistry A, Vol. 106, Issue 13 https://doi.org/10.1021/jp013385w	journal	April 2002
Spatial complexity of soil organic matter forms at nanometre scales Lehmann, Johannes; Solomon, Dawit; Kinyangi, James Nature Geoscience, Vol. 1, Issue 4 https://doi.org/10.1038/ngeo155	journal	March 2008
Formation of soil organic matter via biochemical and physical pathways of litter mass loss Cotrufo, M. Francesca; Soong, Jennifer L.; Horton, Andrew J. Nature Geoscience, Vol. 8, Issue 10 https://doi.org/10.1038/ngeo2520	journal	September 2015
Organic matter losses in German Alps forest soils since the 1970s most likely caused by warming Prietzel, Jörg; Zimmermann, Lothar; Schubert, Alfred Nature Geoscience, Vol. 9, Issue 7 https://doi.org/10.1038/ngeo2732	journal	June 2016
Micro-scale heterogeneity of soil phosphorus depends on soil substrate and depth Werner, Florian; Mueller, Carsten W.; Thieme, Jürgen Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-03537-8	journal	June 2017
Assessing the extent of decomposition of natural organic materials using solid-state 13C NMR spectroscopy Baldock, J. A.; Oades, J. M.; Nelson, P. N. Soil Research, Vol. 35, Issue 5 https://doi.org/10.1071/S97004	journal	January 1997
The removal of magnetic materials from surface soils - a solid state 13C CP/MAS NMR study Skjemstad, Jo; Clarke, P.; Taylor, Ja Soil Research, Vol. 32, Issue 6 https://doi.org/10.1071/SR9941215	journal	January 1994
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
13C NMR studies of organic matter in whole soils: I. Quantitation possibilities Kinchesh, P.; Powlson, D. S.; Randall, E. W. European Journal of Soil Science, Vol. 46, Issue 1 https://doi.org/10.1111/j.1365-2389.1995.tb01819.x	journal	March 1995
Improvement of 13C and 15N CPMAS NMR spectra of bulk soils, particle size fractions and organic material by treatment with 10% hydrofluoric acid Schmidt, M. W. I.; Knicker, H.; Hatcher, P. G. European Journal of Soil Science, Vol. 48, Issue 2 https://doi.org/10.1111/j.1365-2389.1997.tb00552.x	journal	June 1997
Soil organic matter stabilization in acidic forest soils is preferential and soil type-specific Spielvogel, S.; Prietzel, J.; Kgel-Knabner, I. European Journal of Soil Science, Vol. 59, Issue 4 https://doi.org/10.1111/j.1365-2389.2008.01030.x	journal	August 2008
Iron Oxide Removal from Soils and Clays by a Dithionite-Citrate System Buffered with Sodium Bicarbonate Mehra, O. P. Clays and Clay Minerals, Vol. 7, Issue 1 https://doi.org/10.1346/CCMN.1958.0070122	journal	January 1958
Radiocarbon Dating for Determination of Soil Organic Matter Pool Sizes and Dynamics Paul, E. A.; Follett, R. F.; Leavitt, S. W. Soil Science Society of America Journal, Vol. 61, Issue 4 https://doi.org/10.2136/sssaj1997.03615995006100040011x	journal	January 1997
Soil Organic Matter Composition in the Subhumid Ethiopian Highlands as Influenced by Deforestation and Agricultural Management Solomon, D.; Fritzsche, F.; Tekalign, M. Soil Science Society of America Journal, Vol. 66, Issue 1 https://doi.org/10.2136/sssaj2002.6800	journal	January 2002
Carbon K-Edge NEXAFS and FTIR-ATR Spectroscopic Investigation of Organic Carbon Speciation in Soils Solomon, Dawit; Lehmann, Johannes; Kinyangi, James Soil Science Society of America Journal, Vol. 69, Issue 1 https://doi.org/10.2136/sssaj2005.0107dup	journal	January 2005
Carbon (1s) NEXAFS Spectroscopy of Biogeochemically Relevant Reference Organic Compounds Solomon, Dawit; Lehmann, Johannes; Kinyangi, James Soil Science Society of America Journal, Vol. 73, Issue 6 https://doi.org/10.2136/sssaj2008.0228	journal	January 2009
ATTEMPTS TO IMPROVE SOLID STATE ¹³ C NMR SPECTRA OF WHOLE MINERAL SOILS Arshad, M. A.; Ripmeester, J. A.; Schnitzer, M. Canadian Journal of Soil Science, Vol. 68, Issue 3 https://doi.org/10.4141/cjss88-057	journal	August 1988

Cited By (1)

Relationship between macropores and soil organic carbon fractions under long‐term organic manure application Xu, Lingying; Wang, Meiyan; Tian, Yutian Land Degradation & Development, Vol. 31, Issue 11 https://doi.org/10.1002/ldr.3525	journal	January 2020

Similar Records

Using [sup 13]C CPMAS NMR to assess effects of cultivation on the organic matter of particle size fractions in a grassland soil

Journal Article · Fri Dec 31 23:00:00 EST 1993 · Soil Science; (United States) · OSTI ID:7174145

Evolution of organic matter during composting of different organic wastes assessed by CPMAS {sup 13}C NMR spectroscopy

Journal Article · Tue Mar 15 00:00:00 EDT 2011 · Waste Management · OSTI ID:21550346

Radiocarbon enrichment of soil organic matter fractions in New Zealand soils

Journal Article · Wed Jun 01 00:00:00 EDT 1977 · Soil Sci.; (United States) · OSTI ID:7098169

Related Subjects

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY
54 ENVIRONMENTAL SCIENCES
C functional groups
Direct non-invasive SOC speciation
Method comparison
Mineral soil
Organic surface soil
Soil organic matter