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Title: Composition of Dissolved Organic Matter in Pore Waters of Anoxic Marine Sediments Analyzed by 1H Nuclear Magnetic Resonance Spectroscopy

Abstract

Marine sediments are globally significant sources of dissolved organic matter (DOM) to the oceans, but the biogeochemical role of pore-water DOM in the benthic and marine carbon cycles remains unclear due to a lack of understanding about the molecular composition of DOM. To help fill this knowledge gap, we used 1H nuclear magnetic resonance (NMR) spectroscopy to examine depth variability in the composition of pore-water DOM in anoxic sediments of Santa Barbara Basin, California Borderland. Proton detected spectra were acquired on whole samples without pre-concentration to avoid preclusion of any DOM components from the analytical window. Broad unresolved resonance (operationally assigned to carboxyl-rich alicyclic molecules, or CRAM) dominated all spectra. Most of the relatively well-resolved peaks (attributed to biomolecules or their derivatives) appeared at chemical shifts similar to those previously reported for marine DOM in the literature, but at different relative intensities. DOM composition changed significantly within the top 50 cm of the sediment column, where the relative intensity of CRAM increased, and the relative intensity of resolved resonances decreased. The composition of CRAM itself also changed throughout the entire length of the 4.5-m profile, as CRAM protons became increasingly aliphatic at the expense of functionalized protons. Given that pore-watermore » DOM is generated from sedimentary organic matter that includes pre-aged and degraded material, and that DOM is theoretically subject to microbial reworking in the pore waters for centuries to millennia, these data suggest that marine sediments may be sources of CRAM that are compositionally unique from CRAM generated in the upper ocean.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1439111
Alternate Identifier(s):
OSTI ID: 1518565
Report Number(s):
LLNL-JRNL-751233
Journal ID: ISSN 2296-7745; 172
Grant/Contract Number:  
AC52-07NA27344; OCE-1155562; OCE-1155320; OCE-1155764
Resource Type:
Published Article
Journal Name:
Frontiers in Marine Science
Additional Journal Information:
Journal Name: Frontiers in Marine Science Journal Volume: 5; Journal ID: ISSN 2296-7745
Publisher:
Frontiers Media SA
Country of Publication:
Switzerland
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; pore water; DOM; carbon; NMR; sediment; anoxic; marine; Santa Barbara Basin

Citation Formats

Fox, Christina A., Abdulla, Hussain A., Burdige, David J., Lewicki, James P., and Komada, Tomoko. Composition of Dissolved Organic Matter in Pore Waters of Anoxic Marine Sediments Analyzed by 1H Nuclear Magnetic Resonance Spectroscopy. Switzerland: N. p., 2018. Web. doi:10.3389/fmars.2018.00172.
Fox, Christina A., Abdulla, Hussain A., Burdige, David J., Lewicki, James P., & Komada, Tomoko. Composition of Dissolved Organic Matter in Pore Waters of Anoxic Marine Sediments Analyzed by 1H Nuclear Magnetic Resonance Spectroscopy. Switzerland. https://doi.org/10.3389/fmars.2018.00172
Fox, Christina A., Abdulla, Hussain A., Burdige, David J., Lewicki, James P., and Komada, Tomoko. Fri . "Composition of Dissolved Organic Matter in Pore Waters of Anoxic Marine Sediments Analyzed by 1H Nuclear Magnetic Resonance Spectroscopy". Switzerland. https://doi.org/10.3389/fmars.2018.00172.
@article{osti_1439111,
title = {Composition of Dissolved Organic Matter in Pore Waters of Anoxic Marine Sediments Analyzed by 1H Nuclear Magnetic Resonance Spectroscopy},
author = {Fox, Christina A. and Abdulla, Hussain A. and Burdige, David J. and Lewicki, James P. and Komada, Tomoko},
abstractNote = {Marine sediments are globally significant sources of dissolved organic matter (DOM) to the oceans, but the biogeochemical role of pore-water DOM in the benthic and marine carbon cycles remains unclear due to a lack of understanding about the molecular composition of DOM. To help fill this knowledge gap, we used 1H nuclear magnetic resonance (NMR) spectroscopy to examine depth variability in the composition of pore-water DOM in anoxic sediments of Santa Barbara Basin, California Borderland. Proton detected spectra were acquired on whole samples without pre-concentration to avoid preclusion of any DOM components from the analytical window. Broad unresolved resonance (operationally assigned to carboxyl-rich alicyclic molecules, or CRAM) dominated all spectra. Most of the relatively well-resolved peaks (attributed to biomolecules or their derivatives) appeared at chemical shifts similar to those previously reported for marine DOM in the literature, but at different relative intensities. DOM composition changed significantly within the top 50 cm of the sediment column, where the relative intensity of CRAM increased, and the relative intensity of resolved resonances decreased. The composition of CRAM itself also changed throughout the entire length of the 4.5-m profile, as CRAM protons became increasingly aliphatic at the expense of functionalized protons. Given that pore-water DOM is generated from sedimentary organic matter that includes pre-aged and degraded material, and that DOM is theoretically subject to microbial reworking in the pore waters for centuries to millennia, these data suggest that marine sediments may be sources of CRAM that are compositionally unique from CRAM generated in the upper ocean.},
doi = {10.3389/fmars.2018.00172},
journal = {Frontiers in Marine Science},
number = ,
volume = 5,
place = {Switzerland},
year = {Fri May 25 00:00:00 EDT 2018},
month = {Fri May 25 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.3389/fmars.2018.00172

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Cited by: 30 works
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Figures / Tables:

FIGURE 1 FIGURE 1: Pore water DOC concentration profile from Santa Barbara Basin sediments showing data from one multicore (0–50 cm; core 43,1) and three gravity cores (>50 cm; G15, BB26, BB35; Burdige et al., 2016; Komada et al., 2016). All of the data shown were obtained by high-temperature combustion (Burdige andmore » Gardner, 1998). Core G15 was collected in 2012; all others were collected in 2013. Circles represent samples analyzed for DOC concentration only. Blue diamonds and red triangles represent samples whose compositions were analyzed by 1H NMR using a 400 MHz and 600 MHz spectrometer, respectively. One additional sample from 110 cm was analyzed using the 400 MHz instrument, but not plotted here, because DOC concentration is not available.« less

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Works referenced in this record:

Fluxes of dissolved organic carbon from California continental margin sediments
journal, May 1999

  • Burdige, David J.; Berelson, William M.; Coale, Kenneth H.
  • Geochimica et Cosmochimica Acta, Vol. 63, Issue 10
  • DOI: 10.1016/S0016-7037(99)00066-6

Verrucomicrobia Are Candidates for Polysaccharide-Degrading Bacterioplankton in an Arctic Fjord of Svalbard
journal, April 2014

  • Cardman, Z.; Arnosti, C.; Durbin, A.
  • Applied and Environmental Microbiology, Vol. 80, Issue 12
  • DOI: 10.1128/AEM.00899-14

High-precision frequency measurements: indispensable tools at the core of the molecular-level analysis of complex systems
journal, October 2007

  • Hertkorn, N.; Ruecker, C.; Meringer, M.
  • Analytical and Bioanalytical Chemistry, Vol. 389, Issue 5
  • DOI: 10.1007/s00216-007-1577-4

Early diagenesis in differing depositional environments: The response of transition metals in pore water
journal, May 1990

  • Shaw, Timothy J.; Gieskes, Joris M.; Jahnke, Richard A.
  • Geochimica et Cosmochimica Acta, Vol. 54, Issue 5
  • DOI: 10.1016/0016-7037(90)90149-F

Variations in Archaeal and Bacterial Diversity Associated with the Sulfate-Methane Transition Zone in Continental Margin Sediments (Santa Barbara Basin, California)
journal, January 2009

  • Harrison, B. K.; Zhang, H.; Berelson, W.
  • Applied and Environmental Microbiology, Vol. 75, Issue 6
  • DOI: 10.1128/AEM.01812-08

Dissolved organic matter in anoxic pore waters from Mangrove Lake, Bermuda
journal, April 1986

  • Orem, William H.; Hatcher, Patrick G.; Spiker, Elliott C.
  • Geochimica et Cosmochimica Acta, Vol. 50, Issue 4
  • DOI: 10.1016/0016-7037(86)90109-2

Effects of oxygen and redox oscillation on degradation of cell-associated lipids in surficial marine sediments
journal, June 2002


Amino acids in interstitial waters of marine sediments
journal, May 1979

  • Henrichs, Susan M.; Farrington, John W.
  • Nature, Vol. 279, Issue 5711
  • DOI: 10.1038/279319a0

Recalcitrant Dissolved Organic Carbon Fractions
journal, January 2013


Molecular weight distribution of dissolved organic carbon in marine sediment pore waters
journal, October 1998


Organic matter cycling across the sulfate-methane transition zone of the Santa Barbara Basin, California Borderland
journal, March 2016


Marine sequestration of carbon in bacterial metabolites
journal, March 2015

  • Lechtenfeld, Oliver J.; Hertkorn, Norbert; Shen, Yuan
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7711

Chemical composition and cycling of dissolved organic matter in the Mid-Atlantic Bight
journal, January 2002

  • Aluwihare, Lihini I.; Repeta, Daniel J.; Chen, Robert F.
  • Deep Sea Research Part II: Topical Studies in Oceanography, Vol. 49, Issue 20
  • DOI: 10.1016/S0967-0645(02)00124-8

Heterotrophic Archaea dominate sedimentary subsurface ecosystems off Peru
journal, February 2006

  • Biddle, J. F.; Lipp, J. S.; Lever, M. A.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 10
  • DOI: 10.1073/pnas.0600035103

Radiocarbon analysis of neutral sugars in high-molecular-weight dissolved organic carbon: Implications for organic carbon cycling
journal, March 2006


The Size-Reactivity Continuum of Major Bioelements in the Ocean
journal, January 2015


Biogeochemical cycling in an organic-rich coastal marine basin: 11. The sedimentary cycling of dissolved, free amino acids
journal, November 1990


Dynamics and Characterization of Refractory Dissolved Organic Matter Produced by a Pure Bacterial Culture in an Experimental Predator-Prey System
journal, June 2006

  • Gruber, D. F.; Simjouw, J. -P.; Seitzinger, S. P.
  • Applied and Environmental Microbiology, Vol. 72, Issue 6
  • DOI: 10.1128/AEM.02882-05

Chemical and spectroscopic characterization of marine dissolved organic matter isolated using coupled reverse osmosis–electrodialysis
journal, July 2009

  • Koprivnjak, J. -F.; Pfromm, P. H.; Ingall, E.
  • Geochimica et Cosmochimica Acta, Vol. 73, Issue 14
  • DOI: 10.1016/j.gca.2009.04.010

Radiation damping in modern NMR experiments: Progress and challenges
journal, January 2013


Stratification in Recent Sediments of Santa Barbara Basin as Controlled by Organisms and Water Character
journal, May 1961

  • Hülsemann, Jobst; Emery, K. O.
  • The Journal of Geology, Vol. 69, Issue 3
  • DOI: 10.1086/626742

Inefficient microbial production of refractory dissolved organic matter in the ocean
journal, June 2015

  • Osterholz, Helena; Niggemann, Jutta; Giebel, Helge-Ansgar
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8422

Structural characterization of dissolved organic matter: a review of current techniques for isolation and analysis
journal, January 2014

  • Minor, Elizabeth C.; Swenson, Michael M.; Mattson, Bruce M.
  • Environ. Sci.: Processes Impacts, Vol. 16, Issue 9
  • DOI: 10.1039/C4EM00062E

Volatile fatty acid cycling in organic-rich marine sediments
journal, September 1982


Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry
journal, July 2005

  • Koch, Boris P.; Witt, Matthias; Engbrodt, Ralph
  • Geochimica et Cosmochimica Acta, Vol. 69, Issue 13
  • DOI: 10.1016/j.gca.2005.02.027

A mini-electrodialysis system for desalting small volume saline samples for Fourier transform ion cyclotron resonance mass spectrometry: Mini-ED-DOM desalting for FT-ICR MS
journal, December 2011

  • Chen, Hongmei; Stubbins, Aron; Hatcher, Patrick G.
  • Limnology and Oceanography: Methods, Vol. 9, Issue 12
  • DOI: 10.4319/lom.2011.9.582

Redox effects on the microbial degradation of refractory organic matter in marine sediments
journal, November 2013


Two Dimensional Correlation Analysis of Fourier Transform Ion Cyclotron Resonance Mass Spectra of Dissolved Organic Matter: A New Graphical Analysis of Trends
journal, March 2013

  • Abdulla, Hussain A. N.; Sleighter, Rachel L.; Hatcher, Patrick G.
  • Analytical Chemistry, Vol. 85, Issue 8
  • DOI: 10.1021/ac303221j

Bulk Chemical Characteristics of Dissolved Organic Matter in the Ocean
journal, March 1992


The molecularly-uncharacterized component of nonliving organic matter in natural environments
journal, October 2000


Chemical characterization of high molecular weight dissolved organic matter in fresh and marine waters
journal, March 2002


The effect of early diagenesis on the Fe isotope compositions of porewaters and authigenic minerals in continental margin sediments
journal, April 2006

  • Severmann, Silke; Johnson, Clark M.; Beard, Brian L.
  • Geochimica et Cosmochimica Acta, Vol. 70, Issue 8
  • DOI: 10.1016/j.gca.2006.01.007

Direct 1H NMR spectroscopy of dissolved organic matter in natural waters
journal, January 2008

  • Lam, Buuan; Simpson, André J.
  • The Analyst, Vol. 133, Issue 2
  • DOI: 10.1039/B713457F

Sedimentation and climatic patterns in the Santa Barbara Basin during the 19th and 20th centuries
journal, January 1977


Solid-state 13C NMR studies of dissolved organic matter in pore waters from different depositional environments
journal, January 1987


Early diagenesis of amino acids and organic matter in two coastal marine sediments
journal, January 1987


Pacific carbon cycling constrained by organic matter size, age and composition relationships
journal, November 2016

  • Walker, Brett D.; Beaupré, Steven R.; Guilderson, Thomas P.
  • Nature Geoscience, Vol. 9, Issue 12
  • DOI: 10.1038/ngeo2830

A Physical-Chemical Study of the Flushing of the Santa Barbara Basin1: Flushing of the Santa Barbara Basin
journal, May 1971


The Fate of Terrestrial Organic Carbon in the Marine Environment
journal, January 2012


Dissolved organic carbon production and consumption in anoxic marine sediments: A pulsed-tracer experiment
journal, November 2001

  • Hee, Carol A.; Pease, Tamara K.; Alperin, Marc J.
  • Limnology and Oceanography, Vol. 46, Issue 8
  • DOI: 10.4319/lo.2001.46.8.1908

Combining reverse osmosis and electrodialysis for more complete recovery of dissolved organic matter from seawater
journal, September 2007


Using Two-Dimensional Correlations of 13 C NMR and FTIR To Investigate Changes in the Chemical Composition of Dissolved Organic Matter along an Estuarine Transect
journal, November 2010

  • Abdulla, Hussain A. N.; Minor, Elizabeth C.; Hatcher, Patrick G.
  • Environmental Science & Technology, Vol. 44, Issue 21
  • DOI: 10.1021/es100898x

Sediment Pore Waters
book, January 2015


Molecular insights into the microbial formation of marine dissolved organic matter: recalcitrant or labile?
journal, January 2014


Direct Hydrodynamic Radius Measurement on Dissolved Organic Matter in Natural Waters Using Diffusion NMR
journal, January 2012

  • Zheng, Gang; Price, William S.
  • Environmental Science & Technology, Vol. 46, Issue 3
  • DOI: 10.1021/es202809e

An intercomparison of three methods for the large-scale isolation of oceanic dissolved organic matter
journal, April 2014


Characterization of a major refractory component of marine dissolved organic matter
journal, June 2006

  • Hertkorn, Norbert; Benner, Ronald; Frommberger, Moritz
  • Geochimica et Cosmochimica Acta, Vol. 70, Issue 12
  • DOI: 10.1016/j.gca.2006.03.021

Spectroscopic characterization of oceanic dissolved organic matter isolated by reverse osmosis coupled with electrodialysis
journal, December 2015


Spatial and Temporal Offsets Between Proxy Records in a Sediment Drift
journal, October 2002


Deep sub-seafloor prokaryotes stimulated at interfaces over geological time
journal, July 2005

  • Parkes, R. John; Webster, Gordon; Cragg, Barry A.
  • Nature, Vol. 436, Issue 7049
  • DOI: 10.1038/nature03796

A major biopolymeric component to dissolved organic carbon in surface sea water
journal, May 1997

  • Aluwihare, Lihini I.; Repeta, Daniel J.; Chen, Robert F.
  • Nature, Vol. 387, Issue 6629
  • DOI: 10.1038/387166a0

Substrate specificity in polysaccharide hydrolysis: Contrasts between bottom water and sediments
journal, July 2000


A simple and efficient method for the solid-phase extraction of dissolved organic matter (SPE-DOM) from seawater: SPE-DOM from seawater
journal, June 2008

  • Dittmar, Thorsten; Koch, Boris; Hertkorn, Norbert
  • Limnology and Oceanography: Methods, Vol. 6, Issue 6
  • DOI: 10.4319/lom.2008.6.230

Microbial production of recalcitrant dissolved organic matter: long-term carbon storage in the global ocean
journal, July 2010

  • Jiao, Nianzhi; Herndl, Gerhard J.; Hansell, Dennis A.
  • Nature Reviews Microbiology, Vol. 8, Issue 8
  • DOI: 10.1038/nrmicro2386

Linked changes in marine dissolved organic carbon molecular size and radiocarbon age: DOC MOLECULAR SIZE AND RADIOCARBON AGE
journal, October 2016

  • Walker, B. D.; Primeau, F. W.; Beaupré, S. R.
  • Geophysical Research Letters, Vol. 43, Issue 19
  • DOI: 10.1002/2016GL070359

Dilution limits dissolved organic carbon utilization in the deep ocean
journal, March 2015


Major Structural Components in Freshwater Dissolved Organic Matter
journal, December 2007

  • Lam, Buuan; Baer, Andrew; Alaee, Mehran
  • Environmental Science & Technology, Vol. 41, Issue 24
  • DOI: 10.1021/es0713072

Two Chemically Distinct Pools of Organic Nitrogen Accumulate in the Ocean
journal, May 2005


The biogeochemical cycling of dissolved organic nitrogen in estuarine sediments
journal, December 1998


Dissolved organic carbon dynamics in anaerobic sediments of the Santa Monica Basin
journal, June 2013

  • Komada, Tomoko; Burdige, David J.; Crispo, Sabrina M.
  • Geochimica et Cosmochimica Acta, Vol. 110
  • DOI: 10.1016/j.gca.2013.02.017

Seasonal variations in production and consumption rates of dissolved organic carbon in an organic-rich coastal sediment
journal, November 1994


On the hydrogen and oxygen content of marine phytoplankton
journal, September 1995


Dissolved organic matter in Chesapeake Bay sediment pore waters
journal, April 2001


Combining reverse osmosis and pulsed electrical current electrodialysis for improved recovery of dissolved organic matter from seawater
journal, October 2008


Modeling studies of dissolved organic matter cycling in Santa Barbara Basin (CA, USA) sediments
journal, December 2016


Fundamental Concepts of NMR in Paramagnetic Systems. Part II: Relaxation Effects
journal, July 1990


Works referencing / citing this record:

Microbial Processing of Sediment‐Derived Dissolved Organic Matter: Implications for Its Subsequent Biogeochemical Cycling in Overlying Seawater
journal, November 2019

  • Cai, Ruanhong; Zhou, Wenchu; He, Chen
  • Journal of Geophysical Research: Biogeosciences, Vol. 124, Issue 11
  • DOI: 10.1029/2019jg005212

Microbial Processing of Sediment‐Derived Dissolved Organic Matter: Implications for Its Subsequent Biogeochemical Cycling in Overlying Seawater
journal, November 2019

  • Cai, Ruanhong; Zhou, Wenchu; He, Chen
  • Journal of Geophysical Research: Biogeosciences, Vol. 124, Issue 11
  • DOI: 10.1029/2019jg005212

Molecular Composition of Dissolved Organic Matter in Sediment Porewater of the Arctic Deep-Sea Observatory HAUSGARTEN (Fram Strait)
journal, June 2020

  • Rossel, Pamela E.; Bienhold, Christina; Hehemann, Laura
  • Frontiers in Marine Science, Vol. 7
  • DOI: 10.3389/fmars.2020.00428

Direct noninvasive 1 H NMR analysis of stream water DOM: Insights into the effects of lyophilization compared with whole water
journal, September 2019

  • Whitty, Stephanie D.; Waggoner, Derek C.; Cory, Rose M.
  • Magnetic Resonance in Chemistry
  • DOI: 10.1002/mrc.4935