Constraining the response factors of an extractive electrospray ionization mass spectrometer for near-molecular aerosol speciation
<p>Online characterization of aerosol composition at the near-molecular level is key to understanding chemical reaction mechanisms, kinetics, and sources under various atmospheric conditions. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF)...
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Copernicus Publications
2021
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oai:doaj.org-article:0fc6bfa7216842128b1f9c5fb33cb90f2021-11-04T09:10:28ZConstraining the response factors of an extractive electrospray ionization mass spectrometer for near-molecular aerosol speciation10.5194/amt-14-6955-20211867-13811867-8548https://doaj.org/article/0fc6bfa7216842128b1f9c5fb33cb90f2021-11-01T00:00:00Zhttps://amt.copernicus.org/articles/14/6955/2021/amt-14-6955-2021.pdfhttps://doaj.org/toc/1867-1381https://doaj.org/toc/1867-8548<p>Online characterization of aerosol composition at the near-molecular level is key to understanding chemical reaction mechanisms, kinetics, and sources under various atmospheric conditions. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) is capable of detecting a wide range of organic oxidation products in the particle phase in real time with minimal fragmentation. Quantification can sometimes be hindered by a lack of available commercial standards for aerosol constituents, however. Good correlations between the EESI-TOF and other aerosol speciation techniques have been reported, though no attempts have yet been made to parameterize the EESI-TOF response factor for different chemical species. Here, we report the first parameterization of the EESI-TOF response factor for secondary organic aerosol (SOA) at the near-molecular level based on its elemental composition. SOA was formed by ozonolysis of monoterpene or OH oxidation of aromatics inside an oxidation flow reactor (OFR) using ammonium nitrate as seed particles. A Vocus proton-transfer reaction mass spectrometer (Vocus-PTR) and a high-resolution aerosol mass spectrometer (AMS) were used to determine the gas-phase molecular composition and the particle-phase bulk chemical composition, respectively. The EESI response factors towards bulk SOA coating and the inorganic seed particle core were constrained by intercomparison with the AMS. The highest bulk EESI response factor was observed for SOA produced from 1,3,5-trimethylbenzene, followed by those produced from <span class="inline-formula"><i>d</i></span>-limonene and <span class="inline-formula"><i>o</i></span>-cresol, consistent with previous findings. The near-molecular EESI response factors were derived from intercomparisons with Vocus-PTR measurements and were found to vary from 10<span class="inline-formula"><sup>3</sup></span> to 10<span class="inline-formula"><sup>6</sup></span> ion counts s<span class="inline-formula"><sup>−1</sup></span> ppb<span class="inline-formula"><sup>−1</sup></span>, mostly within <span class="inline-formula">±1</span> order of magnitude of their geometric mean of 10<span class="inline-formula"><sup>4.6</sup></span> ion counts s<span class="inline-formula"><sup>−1</sup></span> ppb<span class="inline-formula"><sup>−1</sup></span>. For aromatic SOA components, the EESI response factors correlated with molecular weight and oxygen content and inversely correlated with volatility. The near-molecular response factors mostly agreed within a factor of 20 for isomers observed across the aromatics and biogenic systems. Parameterization of the near-molecular response factors based on the measured elemental formulae could reproduce the empirically determined response factor for a single volatile organic compound (VOC) system to within a factor of 5 for the configuration of our mass spectrometers. The results demonstrate that standard-free quantification using the EESI-TOF is possible.</p>D. S. WangC. P. LeeJ. E. KrechmerF. MajlufY. TongM. R. CanagaratnaJ. SchmaleJ. SchmaleA. S. H. PrévôtU. BaltenspergerJ. DommenI. El HaddadJ. G. SlowikD. M. BellCopernicus PublicationsarticleEnvironmental engineeringTA170-171Earthwork. FoundationsTA715-787ENAtmospheric Measurement Techniques, Vol 14, Pp 6955-6972 (2021) |
| institution |
DOAJ |
| collection |
DOAJ |
| language |
EN |
| topic |
Environmental engineering TA170-171 Earthwork. Foundations TA715-787 |
| spellingShingle |
Environmental engineering TA170-171 Earthwork. Foundations TA715-787 D. S. Wang C. P. Lee J. E. Krechmer F. Majluf Y. Tong M. R. Canagaratna J. Schmale J. Schmale A. S. H. Prévôt U. Baltensperger J. Dommen I. El Haddad J. G. Slowik D. M. Bell Constraining the response factors of an extractive electrospray ionization mass spectrometer for near-molecular aerosol speciation |
| description |
<p>Online characterization of aerosol composition at the
near-molecular level is key to understanding chemical reaction mechanisms,
kinetics, and sources under various atmospheric conditions. The recently
developed extractive electrospray ionization time-of-flight mass
spectrometer (EESI-TOF) is capable of detecting a wide range of organic
oxidation products in the particle phase in real time with minimal
fragmentation. Quantification can sometimes be hindered by a lack of
available commercial standards for aerosol constituents, however. Good
correlations between the EESI-TOF and other aerosol speciation techniques
have been reported, though no attempts have yet been made to parameterize
the EESI-TOF response factor for different chemical species. Here, we report
the first parameterization of the EESI-TOF response factor for secondary
organic aerosol (SOA) at the near-molecular level based on its elemental
composition. SOA was formed by ozonolysis of monoterpene or OH oxidation of
aromatics inside an oxidation flow reactor (OFR) using ammonium nitrate as
seed particles. A Vocus proton-transfer reaction mass spectrometer
(Vocus-PTR) and a high-resolution aerosol mass spectrometer (AMS) were used
to determine the gas-phase molecular composition and the particle-phase bulk
chemical composition, respectively. The EESI response factors towards bulk
SOA coating and the inorganic seed particle core were constrained by
intercomparison with the AMS. The highest bulk EESI response factor was
observed for SOA produced from 1,3,5-trimethylbenzene, followed by those
produced from <span class="inline-formula"><i>d</i></span>-limonene and <span class="inline-formula"><i>o</i></span>-cresol, consistent with previous findings. The
near-molecular EESI response factors were derived from intercomparisons with
Vocus-PTR measurements and were found to vary from 10<span class="inline-formula"><sup>3</sup></span> to 10<span class="inline-formula"><sup>6</sup></span> ion counts s<span class="inline-formula"><sup>−1</sup></span> ppb<span class="inline-formula"><sup>−1</sup></span>, mostly within <span class="inline-formula">±1</span> order of magnitude of
their geometric mean of 10<span class="inline-formula"><sup>4.6</sup></span> ion counts s<span class="inline-formula"><sup>−1</sup></span> ppb<span class="inline-formula"><sup>−1</sup></span>. For aromatic
SOA components, the EESI response factors correlated with molecular weight
and oxygen content and inversely correlated with volatility. The
near-molecular response factors mostly agreed within a factor of 20 for
isomers observed across the aromatics and biogenic systems. Parameterization
of the near-molecular response factors based on the measured elemental
formulae could reproduce the empirically determined response factor for a
single volatile organic compound (VOC) system to within a factor of 5 for the configuration of our mass
spectrometers. The results demonstrate that standard-free quantification
using the EESI-TOF is possible.</p> |
| format |
article |
| author |
D. S. Wang C. P. Lee J. E. Krechmer F. Majluf Y. Tong M. R. Canagaratna J. Schmale J. Schmale A. S. H. Prévôt U. Baltensperger J. Dommen I. El Haddad J. G. Slowik D. M. Bell |
| author_facet |
D. S. Wang C. P. Lee J. E. Krechmer F. Majluf Y. Tong M. R. Canagaratna J. Schmale J. Schmale A. S. H. Prévôt U. Baltensperger J. Dommen I. El Haddad J. G. Slowik D. M. Bell |
| author_sort |
D. S. Wang |
| title |
Constraining the response factors of an extractive electrospray ionization mass spectrometer for near-molecular aerosol speciation |
| title_short |
Constraining the response factors of an extractive electrospray ionization mass spectrometer for near-molecular aerosol speciation |
| title_full |
Constraining the response factors of an extractive electrospray ionization mass spectrometer for near-molecular aerosol speciation |
| title_fullStr |
Constraining the response factors of an extractive electrospray ionization mass spectrometer for near-molecular aerosol speciation |
| title_full_unstemmed |
Constraining the response factors of an extractive electrospray ionization mass spectrometer for near-molecular aerosol speciation |
| title_sort |
constraining the response factors of an extractive electrospray ionization mass spectrometer for near-molecular aerosol speciation |
| publisher |
Copernicus Publications |
| publishDate |
2021 |
| url |
https://doaj.org/article/0fc6bfa7216842128b1f9c5fb33cb90f |
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