TY - JOUR T1 - Dissolved organic carbon in basalt-hosted deep subseafloor fluids of the Juan de Fuca Ridge flank JF - Earth and Planetary Science Letters Y1 - 2019 A1 - Lin, Huei-Ting A1 - Repeta, Daniel J. A1 - Xu, Li A1 - Rappé, Michael S. KW - aromatic organic compound KW - basaltic basement fluid KW - carbon isotopes KW - dissolved organic carbon KW - Juan de Fuca KW - selective removal KW - subseafloor AB - Marine dissolved organic carbon (DOC) is highly depleted in radiocarbon and thus inferred to be largely refractory to removal processes that operate on less than millennial timescales. However, a growing number of reports have shown that a large fraction of marine DOC can be effectively removed during circulation through submarine hydrothermal systems. What is not clear, however, is whether the DOC that remains in hydrothermal fluids is remnant non-reactive DOC from recharged seawater, or DOC that has been largely produced in the subsurface. We collected and characterized warm (∼65 °C) hydrothermal fluids from deep (18, 40, 73, 200 m) within the basalt-hosted basement of the Juan de Fuca Ridge flank in the Northeast Pacific Ocean. DOC concentrations in hydrothermal fluids were 9 to 18 μM, much lower than measured in local deep seawater (37.5 μM). DOC C values of −683‰ to −856‰ were much lower than the C-dissolved inorganic carbon (DIC) values of −880‰ to −918‰, while DOC C values of −23.6‰ to −27.0‰ were much heavier than that of the particulate organic carbon (POC) pool (‰), suggesting that biological production in the subsurface is not a primary source of DOC. Rather, our data suggest that isotopically enriched DOC are selectively removed from recharged seawater, leaving DOC that is very isotopically depleted in the basaltic basement fluids. Despite the removal of 50–75% of DOC in the subsurface, nuclear magnetic resonance (NMR) functional group analyses indicate that aromatic compounds were added to basaltic basement fluids during passage through the deep subseafloor and may partly contribute to the depleted 14C DOC in the ridge-flank basement fluids. VL - 513 UR - https://linkinghub.elsevier.com/retrieve/pii/S0012821X19300998 ER - TY - JOUR T1 - Allochthonous sources and dynamic cycling of ocean dissolved organic carbon revealed by carbon isotopes JF - GEOPHYSICAL RESEARCH LETTERS Y1 - 2017 A1 - Zigah, Prosper K. A1 - McNichol, Ann P. A1 - Xu, Li A1 - Johnson, Carl A1 - Santinelli, Chiara A1 - Karl, David M. A1 - Repeta, Daniel J. KW - ATLANTIC BIGHT KW - BLACK CARBON KW - C-14 KW - HUMIC SUBSTANCES KW - MATTER KW - NORTH PACIFIC-OCEAN KW - RADIOCARBON ANALYSIS KW - SARGASSO SEA KW - SEAWATER KW - SPECTROMETRY AB - We present concentration and isotopic profiles of total, size, and polarity fractionated dissolved organic carbon (DOC) from Station ALOHA (A Long-term Oligotrophic Habitat Assessment), an oligotrophic site in the North Pacific Ocean. The data show that, between the surface and 3500 m, low molecular weight (LMW) hydrophilic DOC, LMW hydrophobic DOC, and high molecular weight (HMW) DOC constitute 22-33%, 45-52%, and 23-35% of DOC, respectively. LMW hydrophilic DOC is more isotopically depleted (delta C-13 of -23.9 parts per thousand to -31.5 parts per thousand and Delta C-14 of -304 parts per thousand to -795 parts per thousand; mean age of 2850 to 15000 years) than the LMW hydrophobic DOC (delta C-13 of -22 parts per thousand to -23 parts per thousand and Delta C-14 of -270 parts per thousand to -568 parts per thousand; 2470 to 6680 years) and HMW DOC (delta C-13 of similar to-21 parts per thousand and Delta C-14 of -24 parts per thousand to -294 parts per thousand; 135-2700 years). Our analyses suggest that a large fraction of DOC may be derived from allochthonous sources such as terrestrial and hydrothermal DOC and cycle on much longer time scales of > 10000 years or enter the ocean as preaged carbon. VL - 44 IS - 5 ER - TY - JOUR T1 - Hidden cycle of dissolved organic carbon in the deep ocean JF - Proceedings of the National Academy of Sciences Y1 - 2014 A1 - Follett, Christopher L. A1 - Repeta, Daniel J. A1 - Rothman, Daniel H. A1 - Xu, Li A1 - Santinelli, Chiara KW - Carbon cycle KW - carbon isotopes KW - dissolved organic carbon KW - Oceanography KW - radiocarbon AB - Marine dissolved organic carbon (DOC) is a large (660 Pg C) reactive carbon reservoir that mediates the oceanic microbial food web and interacts with climate on both short and long timescales. Carbon isotopic content provides information on the DOC source via [Formula: see text]C and age via [Formula: see text]C. Bulk isotope measurements suggest a microbially sourced DOC reservoir with two distinct components of differing radiocarbon age. However, such measurements cannot determine internal dynamics and fluxes. Here we analyze serial oxidation experiments to quantify the isotopic diversity of DOC at an oligotrophic site in the central Pacific Ocean. Our results show diversity in both stable and radio isotopes at all depths, confirming DOC cycling hidden within bulk analyses. We confirm the presence of isotopically enriched, modern DOC cocycling with an isotopically depleted older fraction in the upper ocean. However, our results show that up to 30% of the deep DOC reservoir is modern and supported by a 1 Pg/y carbon flux, which is 10 times higher than inferred from bulk isotope measurements. Isotopically depleted material turns over at an apparent time scale of 30,000 y, which is far slower than indicated by bulk isotope measurements. These results are consistent with global DOC measurements and explain both the fluctuations in deep DOC concentration and the anomalous radiocarbon values of DOC in the Southern Ocean. Collectively these results provide an unprecedented view of the ways in which DOC moves through the marine carbon cycle. VL - 111 UR - http://www.pnas.org/lookup/doi/10.1073/pnas.1407445111https://syndication.highwire.org/content/doi/10.1073/pnas.1407445111 IS - 47 ER - TY - JOUR T1 - 14C and 13C characteristics of higher plant biomarkers in Washington margin surface sediments JF - Geochimica et Cosmochimica Acta Y1 - 2013 A1 - Feng, Xiaojuan A1 - Benitez-Nelson, Bryan C. A1 - Montluçon, Daniel B. A1 - Prahl, Fredrick G. A1 - McNichol, Ann P. A1 - Xu, Li A1 - Repeta, Daniel J. A1 - Eglinton, Timothy I. AB - Plant wax lipids and lignin phenols are the two most common classes of molecular markers that are used to trace vascular plant-derived OM in the marine environment. However, their 13C and 14C compositions have not been directly compared, which can be used to constrain the flux and attenuation of terrestrial carbon in marine environment. In this study, we describe a revised method of isolating individual lignin phenols from complex sedimentary matrices for 14C analysis using high pressure liquid chromatography (HPLC) and compare this approach to a method utilizing preparative capillary gas chromatography (PCGC). We then examine in detail the 13C and 14C compositions of plant wax lipids and lignin phenols in sediments from the inner and mid shelf of the Washington margin that are influenced by discharge of the Columbia River. Plant wax lipids (including n-alkanes, n-alkanoic (fatty) acids, n-alkanols, and n-aldehydes) displayed significant variability in both δ13C (−28.3‰ to −37.5‰) and Δ14C values (−204‰ to +2‰), suggesting varied inputs and/or continental storage and transport histories. In contrast, lignin phenols exhibited similar δ13C values (between −30‰ and −34‰) and a relatively narrow range of Δ14C values (−45‰ to −150‰; HPLC-based measurement) that were similar to, or younger than, bulk OM (−195‰ to −137‰). Moreover, lignin phenol 14C age correlated with the degradation characteristics of this terrestrial biopolymer in that vanillyl phenols were on average ∼500 years older than syringyl and cinnamyl phenols that degrade faster in soils and sediments. The isotopic characteristics, abundance, and distribution of lignin phenols in sediments suggest that they serve as promising tracers of recently biosynthesized terrestrial OM during supply to, and dispersal within the marine environment. Lignin phenol 14C measurements may also provide useful constraints on the vascular plant end member in isotopic mixing models for carbon source apportionment, and for interpretation of sedimentary records of past vegetation dynamics. VL - 105 UR - http://www.sciencedirect.com/science/article/pii/S0016703712006874 N1 - id: 2267 JO - 14C and 13C characteristics of higher plant biomarkers in Washington margin surface sediments ER - TY - JOUR T1 - C-14 and C-13 characteristics of higher plant biomarkers in Washington margin surface sediments JF - GEOCHIMICA ET COSMOCHIMICA ACTA Y1 - 2013 A1 - Feng, Xiaojuan A1 - Benitez-Nelson, Bryan C. A1 - Montluçon, Daniel B. A1 - Prahl, Fredrick G. A1 - McNichol, Ann P. A1 - Xu, Li A1 - Repeta, Daniel J. A1 - Eglinton, Timothy I. AB - Plant wax lipids and lignin phenols are the two most common classes of molecular markers that are used to trace vascular plant-derived OM in the marine environment. However, their C-13 and C-14 compositions have not been directly compared, which can be used to constrain the flux and attenuation of terrestrial carbon in marine environment. In this study, we describe a revised method of isolating individual lignin phenols from complex sedimentary matrices for C-14 analysis using high pressure liquid chromatography (HPLC) and compare this approach to a method utilizing preparative capillary gas chromatography (PCGC). We then examine in detail the C-13 and C-14 compositions of plant wax lipids and lignin phenols in sediments from the inner and mid shelf of the Washington margin that are influenced by discharge of the Columbia River. Plant wax lipids (including n-alkanes, n-alkanoic (fatty) acids, n-alkanols, and n-aldehydes) displayed significant variability in both delta C-13 (-28.3 parts per thousand to -37.5 parts per thousand) and Delta C-14 values (-204 parts per thousand to +2 parts per thousand), suggesting varied inputs and/or continental storage and transport histories. In contrast, lignin phenols exhibited similar delta C-13 values (between -30 parts per thousand and -34 parts per thousand) and a relatively narrow range of Delta C-14 values (-45 parts per thousand to -150 parts per thousand; HPLC-based measurement) that were similar to, or younger than, bulk OM (-195 parts per thousand to -137 parts per thousand). Moreover, lignin phenol C-14 age correlated with the degradation characteristics of this terrestrial biopolymer in that vanillyl phenols were on average similar to 500 years older than syringyl and cinnamyl phenols that degrade faster in soils and sediments. The isotopic characteristics, abundance, and distribution of lignin phenols in sediments suggest that they serve as promising tracers of recently biosynthesized terrestrial OM during supply to, and dispersal within the marine environment. Lignin phenol C-14 measurements may also provide useful constraints on the vascular plant end member in isotopic mixing models for carbon source apportionment, and for interpretation of sedimentary records of past vegetation dynamics. (C) 2012 Elsevier Ltd. All rights reserved. VL - 105 ER -