Molecular transformation and degradation of refractory dissolved organic matter in the Atlantic and Southern Ocean.

Lechtenfeld, Oliver J., Kattner, Gerhard, Flerus, Ruth, Leigh McCallister, S., Schmitt-Kopplin, Philippe and Koch, Boris P. (2014) Molecular transformation and degradation of refractory dissolved organic matter in the Atlantic and Southern Ocean. Open Access Geochimica et Cosmochimica Acta, 126 . pp. 321-337. DOI 10.1016/j.gca.2013.11.009.

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Supplementary data:

Abstract

More than 90% of the global ocean dissolved organic carbon (DOC) is refractory, has an average age of 4,000–6,000 years and a lifespan from months to millennia. The fraction of dissolved organic matter (DOM) that is resistant to degradation is a long-term buffer in the global carbon cycle but its chemical composition, structure, and biochemical formation and degradation mechanisms are still unresolved. We have compiled the most comprehensive molecular data set of 197 Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analyses from solid-phase extracted marine DOM covering two major oceans, the Atlantic sector of the Southern Ocean and the East Atlantic Ocean (ranging from 50° N to 70° S). Molecular trends and radiocarbon dating of 34 DOM samples (comprising Δ14C values from -229 to -495‰) were combined to model an integrated degradation rate for bulk DOC resulting in a predicted age of >24 ka for the most persistent DOM fraction. First order kinetic degradation rates for 1,557 mass peaks indicate that numerous DOM molecules cycle on timescales much longer than the turnover of the bulk DOC pool (estimated residence times of >100 ka) and the range of validity of radiocarbon dating. Changes in elemental composition were determined by assigning molecular formulae to the detected mass peaks. The combination of residence times with molecular information enabled modelling of the average elemental composition of the slowest degrading fraction of the DOM pool. In our dataset, a group of 361 molecular formulae represented the most stable composition in the oceanic environment (“island of stability”). These most persistent compounds encompass only a narrow range of the elemental ratios H/C (average of 1.17 ± 0.13), and O/C (average of 0.52 ± 0.10) and molecular masses (360 ± 28 and 497 ± 51 Da). In the Weddell Sea DOC concentrations in the surface waters were low (46.3 ± 3.3 μM) while the organic radiocarbon was significantly more depleted than that of the East Atlantic, indicating average surface water DOM ages of 4,920 ± 180 a. These results are in accordance with a highly degraded DOM in the Weddell Sea surface water as also shown by the molecular degradation index IDEG obtained from FT-ICR MS data. Further, we identified 339 molecular formulae which probably contribute to an increased DOC concentration in the Southern Ocean and potentially reflect an accumulation or enhanced sequestration of refractory DOC in the Weddell Sea. These results will contribute to a better understanding of the persistent nature of marine DOM and its role as an oceanic carbon buffer in a changing climate.

Document Type: Article
Keywords: dissolved organic carbon (DOC), Atlantic Ocean, Southern Ocean
Research affiliation: OceanRep > GEOMAR > FB2 Marine Biogeochemistry > FB2-BI Biological Oceanography
Refereed: Yes
Open Access Journal?: No
DOI etc.: 10.1016/j.gca.2013.11.009
ISSN: 0016-7037
Expeditions/Models/Experiments:
Date Deposited: 11 Dec 2013 08:49
Last Modified: 19 Jun 2017 11:55
URI: http://oceanrep.geomar.de/id/eprint/22608

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