| 1. |
- Merder, Julian, et al.
(författare)
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ICBM-OCEAN : Processing Ultrahigh-Resolution Mass Spectrometry Data of Complex Molecular Mixtures
- 2020
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Ingår i: Analytical Chemistry. - : American Chemical Society (ACS). - 0003-2700 .- 1520-6882. ; 92:10, s. 6832-6838
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Tidskriftsartikel (refereegranskat)abstract
- Untargeted molecular analyses of complex mixtures are relevant for many fields of research, including geochemistry, pharmacology, and medicine. Ultrahigh-resolution mass spectrometry is one of the most powerful tools in this context. The availability of open scripts and online tools for specific data processing steps such as noise removal or molecular formula assignment is growing, but an integrative tool where all crucial steps are reproducibly evaluated and documented is lacking. We developed a novel, server-based tool (ICBM-OCEAN, Institute for Chemistry and Biology of the Marine Environment, Oldenburg-complex molecular mixtures, evaluation & analysis) that integrates published and novel approaches for standardized processing of ultrahigh-resolution mass spectrometry data of complex molecular mixtures. Different from published approaches, we offer diagnostic and validation tools for all relevant steps. Among other features, we included objective and reproducible reduction of noise and systematic errors, spectra recalibration and alignment, and identification of likeliest molecular formulas. With 15 chemical elements, the tool offers high flexibility in formula attribution. Alignment of mass spectra among different samples prior to molecular formula assignment improves mass error and facilitates molecular formula confirmation with the help of isotopologues. The online tool and the detailed instruction manual are freely accessible at www.icbm.de/icbm-ocean.
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| 2. |
- Hawkes, Jeffrey A., et al.
(författare)
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Efficient removal of recalcitrant deep-ocean dissolved organic matter during hydrothermal circulation
- 2015
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Ingår i: Nature Geoscience. - 1752-0894 .- 1752-0908. ; 8:11, s. 856-
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Tidskriftsartikel (refereegranskat)abstract
- Oceanic dissolved organic carbon (DOC) is an important carbon pool, similar in magnitude to atmospheric CO2, but the fate of its oldest forms is not well understood(1,2). Hot hydrothermal circulation may facilitate the degradation of otherwise un-reactive dissolved organic matter, playing an important role in the long-term global carbon cycle. The oldest, most recalcitrant forms of DOC, which make up most of oceanic DOC, can be recovered by solid-phase extraction. Here we present measurements of solid-phase extractable DOC from samples collected between 2009 and 2013 at seven vent sites in the Atlantic, Pacific and Southern oceans, along with magnesium concentrations, a conservative tracer of water circulation through hydrothermal systems. We find that magnesium and solid-phase extractable DOC concentrations are correlated, suggesting that solid-phase extractable DOC is almost entirely lost from solution through mineralization or deposition during circulation through hydrothermal vents with fluid temperatures of 212-401 degrees C. In laboratory experiments, where we heated samples to 380 degrees C for four days, we found a similar removal efficiency. We conclude that thermal degradation alone can account for the loss of solid-phase extractable DOC in natural hydrothermal systems, and that its maximum lifetime is constrained by the timescale of hydrothermal cycling, at about 40 million years(3).
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| 3. |
- Rossel, Pamela E., et al.
(författare)
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Thermally altered marine dissolved organic matter in hydrothermal fluids
- 2017
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Ingår i: Organic Geochemistry. - : PERGAMON-ELSEVIER SCIENCE LTD. - 0146-6380 .- 1873-5290. ; 110, s. 73-86
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Tidskriftsartikel (refereegranskat)abstract
- Hydrothermal vent fluids contain thermally modified dissolved organic matter (DOM) originally entrained from sediments and seawater. We hypothesized that in hydrothermal systems DOM molecular composition is modulated by (i) fluid contribution, (ii) thermal decomposition and pH, and (iii) aspects particular to the vent system. Hence, solid phase extracted (SPE) DOM samples collected along the Mid-Atlantic Ridge (MAR) were molecularly characterized via 15 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The molecular character of an oceanic DOM sample was also determined before and after thermal (300 °C) decomposition at acidic and neutral pH. Multivariate statistical analysis indicated that DOM composition was strongly influenced by fluid contribution (Mg2+ concentration between 12 and 54 mM), which correlated positively with measured temperature (between 8 and 375 °C). In comparison, pH of the fluids (between 2.5 and 6.9) had a minor influence. Seafloor pressure, used as a theoretical maximum fluid temperature at the seafloor, separated the fluids collected at Menez Gwen from deeper locations, due to the higher abundance of peptide, carboxyl-rich alicyclic (CRAM) and aromatic molecular formulae at Menez Gwen. Compared with seawater DOM, thermally decomposed DOM had on average lower molecular mass, lower O/C ratios, fewer double bond equivalents, and fewer CRAM formulae but higher aromaticity - the same molecular features displayed by MAR hydrothermal fluids. The study provides evidence that thermal reworking plays a major role in shaping DOM mixtures from hydrothermal fluids along the MAR, which partly represent thermally reworked marine DOM that survived hydrothermal circulation.
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