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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 Lab. (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. doi: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. doi: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 = {2018},
month = {5}
}

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

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Cited by: 5 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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