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

Koch, Boris P.; Witt, Matthias; Engbrodt, Ralph; Dittmar, Thorsten; Kattner, Gerhard

doi:10.1016/j.gca.2005.02.027

Cited by 475 publications

(483 citation statements)

References 54 publications

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“…Uniform depth distributions of DOC have also been reported for the Southern Ocean (Wedborg et al, 1998;Wiebinga and de Baar, 1998;Ogawa et al, 1999) and are consistent with our constantly low wa H/C and high I DEG values. The uniform wa H/C ratios are unusual for ocean depth profiles (Kujawinski et al, 2009;Flerus et al, 2012;Hertkorn et al, 2013) but have been also reported by Koch et al (2005) for the southwestern Weddell Sea. Low H/C ratios and high I DEG values in the deep East Atlantic Ocean compared to the surface waters have been interpreted as a signature of reworked and degraded organic matter (Flerus et al, 2012).…”

Section: Ft-icr Ms Age Model Validationsupporting

confidence: 72%

“…Briefly, molecular formulae were calculated from the m/z values with a home-built algorithm allowing for the elemental combinations 12 C 0-50 S 0-1 with a mass accuracy |Dm| 60.5 ppm. The "nitrogen-rule" and elemental ratios O/C 6 1, N/C 6 1, H 6 2C + 2 + N (Koch et al, 2005(Koch et al, , 2007 were applied to all molecular formulae and ambiguously assigned mass peaks were checked with the chemical building block approach (Koch et al, 2007). Due to the high degree of spectral similarity between samples (52% of the mass peaks were present in at least 75% of all samples) detailed data evaluation was based on normalized magnitudes.…”

Section: Ft-icr Ms Data Evaluationmentioning

confidence: 99%

“…It needs to be pointed out that the mean lifetime (s) of the exponential decay of Middle: representation of the same four compounds in the spectrum of a young surface sample, assigned with the degradation rate coefficients. Bottom: full FT-ICR MS spectrum with the typical peak magnitude distribution observed from negative mode ESI analysis of marine DOM (Koch et al, 2005;Gonsior et al, 2011). The color scale of all three figures reflect the ratio k i /k DOC .…”

Section: Degradation Rate Of Bulk Doc Modeled From Spe-dom D 14 Cmentioning

confidence: 99%

“…Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has opened a new analytical window to identify molecular formulae of thousands of marine compounds which are not accessible using standard analytical techniques (e.g., Koch et al, 2005Koch et al, , 2008Hertkorn et al, 2006;Kujawinski et al, 2009;D'Andrilli et al, 2010). Currently, much effort is undertaken to overcome the analytical restrictions of this technique (Kido Soule et al, 2010;Sleighter et al, 2010Sleighter et al, , 2012Tfaily et al, 2011) and to refine the data evaluation algorithms (Kujawinski and Behn, 2006;Koch et al, 2007;Flerus et al, 2011;Tziotis et al, 2011).…”

Section: Introductionmentioning

confidence: 99%

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

Lechtenfeld

Kattner

Flerus

et al. 2014

Geochimica et Cosmochimica Acta

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278

259

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More than 90% of the global ocean dissolved organic carbon (DOC) is refractory, has an average age of 4000-6000 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 dataset 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 D 14 C values from À229& to À495&) 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 1557 mass peaks indicate that numerous DOM molecules cycle on timescales much longer than the turnover of the bulk DOC pool (estimated residence times of up to~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 molecular 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 lM) while the organic radiocarbon was significantly more depleted than that of the East Atlantic, representing average surface water DOM ages of 4920 ± 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 I DEG 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.

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Section: Ft-icr Ms Age Model Validationsupporting

confidence: 72%

Section: Ft-icr Ms Data Evaluationmentioning

confidence: 99%

Section: Degradation Rate Of Bulk Doc Modeled From Spe-dom D 14 Cmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Lechtenfeld

Kattner

Flerus

et al. 2014

Geochimica et Cosmochimica Acta

Self Cite

278

259

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show abstract

“…The recalcitrance of black carbon was further discussed by both Michael Schmidt (see: Preston and Schmidt 2006) and Johannes Lehmann (see: Nguyen et al 2008), with the latter providing evidence that even here interactions with minerals may play an important role in retarding degradation. The only oral presentation in which mineral associations were not considered important, was that of Boris Koch, who discussed the recalcitrance of some marine DOM components (see: Koch et al 2005). The influence of soil biology on stabilization and destabilization of organic matter, whilst recognized implicitly in many presentations, was not addressed explicitly except in the study of Crow et al (2008) (this volume), who report on the influence of earthworm activity on C cycling in forest soils.…”

Section: Conference Highlightsmentioning

confidence: 99%

Mechanisms of organic matter stabilization and destabilization in soils and sediments: conference introduction

Smernik

Skjemstad

2008

Biogeochemistry

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A coupled geochemical and biogeochemical approach to characterize the bioreactivity of dissolved organic matter from a headwater stream

Sleighter

Cory

Kaplan

et al. 2014

J. Geophys. Res. Biogeosci.

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The bioreactivity or susceptibility of dissolved organic matter (DOM) to microbial degradation in streams and rivers is of critical importance to global change studies, but a comprehensive understanding of DOM bioreactivity has been elusive due, in part, to the stunningly diverse assemblages of organic molecules within DOM. We approach this problem by employing a range of techniques to characterize DOM as it flows through biofilm reactors: dissolved organic carbon (DOC) concentrations, excitation emission matrix spectroscopy (EEMs), and ultrahigh resolution mass spectrometry. The EEMs and mass spectral data were analyzed using a combination of multivariate statistical approaches. We found that 45% of stream water DOC was biodegraded by microorganisms, including 31-45% of the humic DOC. This bioreactive DOM separated into two different groups: (1) H/C centered at 1.5 with O/C 0.1-0.5 or (2) low H/C of 0.5-1.0 spanning O/C 0.2-0.7 that were positively correlated (Spearman ranking) with chromophoric and fluorescent DOM (CDOM and FDOM, respectively). DOM that was more recalcitrant and resistant to microbial degradation aligned tightly in the center of the van Krevelen space (H/C 1.0-1.5, O/C 0.25-0.6) and negatively correlated (Spearman ranking) with CDOM and FDOM. These findings were supported further by principal component analysis and 2-D correlation analysis of the relative magnitudes of the mass spectral peaks assigned to molecular formulas. This study demonstrates that our approach of processing stream water through bioreactors followed by EEMs and FTICR-MS analyses, in combination with multivariate statistical analysis, allows for precise, robust characterization of compound bioreactivity and associated molecular level composition.

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

Cited by 475 publications

References 54 publications

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

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

Mechanisms of organic matter stabilization and destabilization in soils and sediments: conference introduction

A coupled geochemical and biogeochemical approach to characterize the bioreactivity of dissolved organic matter from a headwater stream

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