% IMPORTANT: The following is UTF-8 encoded. This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.
@ARTICLE{Priestley:894242,
author = {Priestley, Michael and Bannan, Thomas J. and Le Breton,
Michael and Worrall, Stephen D. and Kang, Sungah and
Pullinen, Iida and Schmitt, Sebastian and Tillmann, Ralf and
Kleist, Einhard and Zhao, Defeng and Wildt, Jürgen and
Garmash, Olga and Mehra, Archit and Bacak, Asan and
Shallcross, Dudley E. and Kiendler-Scharr, Astrid and
Hallquist, Åsa M. and Ehn, Mikael and Coe, Hugh and
Percival, Carl J. and Hallquist, Mattias and Mentel, Thomas
F. and McFiggans, Gordon},
title = {{C}hemical characterisation of benzene oxidation products
under high- and $low-{NO}\<sub\>\<i\>x\</i\>\</sub\>$
conditions using chemical ionisation mass spectrometry},
journal = {Atmospheric chemistry and physics},
volume = {21},
number = {5},
issn = {1680-7324},
address = {Katlenburg-Lindau},
publisher = {EGU},
reportid = {FZJ-2021-03122},
pages = {3473 - 3490},
year = {2021},
abstract = {Aromatic hydrocarbons are a class of volatile organic
compounds associated with anthropogenic activity and make up
a significant fraction of urban volatile organic compound
(VOC) emissions that contribute to the formation of
secondary organic aerosol (SOA). Benzene is one of the most
abundant species emitted from vehicles, biomass burning and
industry. An iodide time-of-flight chemical ionisation mass
spectrometer (ToF-CIMS) and nitrate ToF-CIMS were deployed
at the Jülich Plant Atmosphere Chamber as part of a series
of experiments examining benzene oxidation by OH under high-
and low-NOx conditions, where a range of organic oxidation
products were detected. The nitrate scheme detects many
oxidation products with high masses, ranging from
intermediate volatile organic compounds (IVOCs) to extremely
low volatile organic compounds (ELVOCs), including C12
dimers. In comparison, very few species with C≥6 and O≥8
were detected with the iodide scheme, which detected many
more IVOCs and semi-volatile organic compounds (SVOCs) but
very few ELVOCs and low volatile organic compounds (LVOCs).
A total of 132 and 195 CHO and CHON oxidation products are
detected by the iodide ToF-CIMS in the low- and high-NOx
experiments respectively. Ring-breaking products make up the
dominant fraction of detected signal and 21 and 26 of the
products listed in the Master Chemical Mechanism (MCM) were
detected. The time series of highly oxidised (O≥6) and
ring-retaining oxidation products (C6 and double-bond
equivalent = 4) equilibrate quickly, characterised by a
square form profile, compared to MCM and ring-breaking
products which increase throughout oxidation, exhibiting
sawtooth profiles. Under low-NOx conditions, all CHO
formulae attributed to radical termination reactions of
first-generation benzene products, and first-generation
auto-oxidation products are observed. Several N-containing
species that are either first-generation benzene products or
first-generation auto-oxidation products are also observed
under high-NOx conditions. Hierarchical cluster analysis
finds four clusters, of which two describe photo-oxidation.
Cluster 2 shows a negative dependency on the NO2/NOx ratio,
indicating it is sensitive to NO concentration and thus
likely to contain NO addition products and alkoxy-derived
termination products. This cluster has the highest average
carbon oxidation state (OSC¯¯¯¯¯¯¯) and the lowest
average carbon number. Where nitrogen is present in a
cluster member of cluster 2, the oxygen number is even, as
expected for alkoxy-derived products. In contrast, cluster 1
shows no dependency on the NO2/NOx ratio and so is likely to
contain more NO2 addition and peroxy-derived termination
products. This cluster contains fewer fragmented species, as
the average carbon number is higher and OSC¯¯¯¯¯¯¯
lower than cluster 2, and more species with an odd number of
oxygen atoms. This suggests that clustering of time series
which have features pertaining to distinct chemical regimes,
for example, NO2/NOx perturbations, coupled with a priori
knowledge, can provide insight into identification of
potential functionality.},
cin = {IEK-8},
ddc = {550},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {2111 - Air Quality (POF4-211)},
pid = {G:(DE-HGF)POF4-2111},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000626739700004},
doi = {10.5194/acp-21-3473-2021},
url = {https://juser.fz-juelich.de/record/894242},
}