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@ARTICLE{Zherebker:180975,
author = {A. Zherebker and G. Rukhovich and A. Sarycheva and O. J.
Lechtenfeld and E. N. Nikolaev},
title = {{A}romaticity {I}ndex with {I}mproved {E}stimation of
{C}arboxyl {G}roup {C}ontribution for {B}iogeochemical
{S}tudies},
journal = {Environmental science $\&$ technology},
volume = {56},
number = {4},
issn = {0013-936X},
address = {Columbus, Ohio},
publisher = {American Chemical Society},
reportid = {DKFZ-2022-01700},
pages = {2729 - 2737},
year = {2022},
abstract = {Natural organic matter (NOM) components measured with
ultrahigh-resolution mass spectrometry (UHRMS) are often
assessed by molecular formula-based indices, particularly
related to their aromaticity, which are further used as
proxies to explain biogeochemical reactivity. An aromaticity
index (AI) is calculated mostly with respect to carboxylic
groups abundant in NOM. Here, we propose a new constrained
AIcon based on the measured distribution of carboxylic
groups among individual NOM components obtained by
deuteromethylation and UHRMS. Applied to samples from
diverse sources (coal, marine, peat, permafrost, blackwater
river, and soil), the method revealed that the most probable
number of carboxylic groups was two, which enabled to set a
reference point n = 2 for carboxyl-accounted AIcon
calculation. The examination of the proposed AIcon showed
the smallest deviation to the experimentally determined
index for all NOM samples under study as well as for
individual natural compounds obtained from the Coconut
database. In particular, AIcon performed better than AImod
for all compound classes in which aromatic moieties are
expected: aromatics, condensed aromatics, and unsaturated
compounds. Therefore, AIcon referenced with two carboxyl
groups is preferred over conventional AI and AImod for
biogeochemical studies where the aromaticity of compounds is
important to understand the transformations and fate of NOM
compounds.},
ddc = {333.7},
typ = {PUB:(DE-HGF)16},
doi = {10.1021/acs.est.1c04575},
url = {https://inrepo02.dkfz.de/record/180975},
}