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Referenztyp Zeitschriften
DOI / URL Link
Titel (primär) Molecular formula assignment for dissolved organic matter (DOM) using high-field FT-ICR-MS: chemical perspective and validation of sulphur-rich organic components (CHOS) in pit lake samples
Autor Herzsprung, P.; Hertkorn, N.; von Tümpling, W.; Harir, M.; Friese, K.; Schmitt-Kopplin, P.;
Journal / Serie Analytical and Bioanalytical Chemistry
Erscheinungsjahr 2016
Department SEEFO; FLOEK;
Band/Volume 408
Heft 10
Sprache englisch;
POF III (gesamt) T31;
Keywords DOM; FT-ICR-MS Formula assignment CHOS/CHON molecular series Validation
UFZ Querschnittsthemen RU2;
Abstract Molecular formula assignment is one of the key challenges in processing high-field Fourier transform ion cyclotron resonance mass spectrometric (FT-ICR-MS) datasets. The number of potential solutions for an elemental formula increases exponentially with increasing molecular mass, especially when non-oxygen heteroatoms like N, S or P are included. A method was developed from the chemical perspective and validated using a Suwannee River Fulvic Acid (SRFA) dataset which is dominated by components consisting exclusively of C, H and O (78 % CHO). In order to get information on the application range and robustness of this method, we investigated a FT-ICR-MS dataset which was merged from 18 mine pit lake pore waters and 3 river floodplain soil waters. This dataset contained 50 % CHO and 18 % CHOS on average, whereas the former SRFA dataset contained only 1.5 % CHOS. The mass calculator was configured to allow up to five nitrogen atoms and up to one sulphur atom in assigning formulas to mass peaks. More than 50 % multiple-formula assignments were found for peaks with masses > 650 Da. Based on DBE − O frequency diagrams, many CHO, CHOS1, CHON1 and CHON1S1 molecular series were ultimately assigned to many m/z and considered to be reliable solutions. The unequivocal data pool could thus be enlarged by 523 (6.8 %) CHOS1 components. In contrast to the method validation with CHO-rich SRFA, validation with sulphur-rich pit lake samples showed that formulas with a higher number of non-oxygen heteroatoms can be more reliable assignments in many cases. As an example: CHOS molecular series were reliable and the CHO classes were unreliable amongst other molecular classes in many multiple-formula assignments from the sulphur-rich pit lake samples.
ID 17213
dauerhafte UFZ-Verlinkung http://www.ufz.de/index.php?en=20939&ufzPublicationIdentifier=17213
Herzsprung, P., Hertkorn, N., von Tümpling, W., Harir, M., Friese, K., Schmitt-Kopplin, P. (2016):
Molecular formula assignment for dissolved organic matter (DOM) using high-field FT-ICR-MS: chemical perspective and validation of sulphur-rich organic components (CHOS) in pit lake samples
Anal. Bioanal. Chem. 408 (10), 2461 - 2469