PMID- 37656668 OWN - NLM STAT- PubMed-not-MEDLINE LR - 20230924 IS - 1520-6882 (Electronic) IS - 0003-2700 (Print) IS - 0003-2700 (Linking) VI - 95 IP - 37 DP - 2023 Sep 19 TI - Sensitivity Constraints of Extractive Electrospray for a Model System and Secondary Organic Aerosol. PG - 13788-13795 LID - 10.1021/acs.analchem.3c00441 [doi] AB - The quantification of an aerosol chemical composition is complicated by the uncertainty in the sensitivity of each species detected. Soft-ionization response factors can vary widely from molecule to molecule. Here, we have employed a method to separate molecules by their volatility through systematic evaporation with a thermal denuder (TD). The fraction remaining after evaporation is compared between an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) and a scanning mobility particle sizer (SMPS), which provides a comparison between a quantified mass loss by the SMPS and the signal loss in the EESI-TOF. The sensitivity of the EESI-TOF is determined for both a simplified complex mixture (PEG-300) and also for a complex mixture of alpha-pinene secondary organic aerosol (SOA). For PEG-300, separation is possible on a molecule-by-molecule level with the TD and provides insights into the molecule-dependent sensitivity of the EESI-TOF, showing a higher sensitivity toward the most volatile molecule. For alpha-pinene SOA, sensitivity determination for specific classes is possible because of the number of molecular formula observed by the EESI-TOF. These classes are separated by their volatility and are broken down into monomers (O(3-5,6-7,8+)), dimers (O(4-7,8+)), and higher order oligomers (e.g., trimers and tetramers). Here, we show that the EESI-TOF initially measures 60.1% monomers, 32.7% dimers, and 7.2% trimers and tetramers in alpha-pinene SOA, but after sensitivity correction, the distribution of SOA is 37.4% monomers, 56.1% dimers, and 6.4% trimers and tetramers. These results provide a path forward for the quantification of aerosol components with the EESI-TOF in other applications and potentially for atmospheric measurements. FAU - Bell, David M AU - Bell DM AUID- ORCID: 0000-0002-3958-2138 AD - Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen 5232, Switzerland. FAU - Zhang, Jun AU - Zhang J AD - Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen 5232, Switzerland. FAU - Top, Jens AU - Top J AUID- ORCID: 0000-0003-3318-4451 AD - Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen 5232, Switzerland. FAU - Bogler, Sophie AU - Bogler S AD - Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen 5232, Switzerland. FAU - Surdu, Mihnea AU - Surdu M AUID- ORCID: 0000-0003-1815-2750 AD - Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen 5232, Switzerland. FAU - Slowik, Jay G AU - Slowik JG AD - Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen 5232, Switzerland. FAU - Prevot, Andre S H AU - Prevot ASH AUID- ORCID: 0000-0002-9243-8194 AD - Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen 5232, Switzerland. FAU - El Haddad, Imad AU - El Haddad I AUID- ORCID: 0000-0002-2461-7238 AD - Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen 5232, Switzerland. LA - eng PT - Journal Article DEP - 20230901 PL - United States TA - Anal Chem JT - Analytical chemistry JID - 0370536 SB - IM PMC - PMC10515109 COIS- The authors declare no competing financial interest. EDAT- 2023/09/01 18:41 MHDA- 2023/09/01 18:42 PMCR- 2023/09/22 CRDT- 2023/09/01 13:22 PHST- 2023/09/01 18:42 [medline] PHST- 2023/09/01 18:41 [pubmed] PHST- 2023/09/01 13:22 [entrez] PHST- 2023/09/22 00:00 [pmc-release] AID - 10.1021/acs.analchem.3c00441 [doi] PST - ppublish SO - Anal Chem. 2023 Sep 19;95(37):13788-13795. doi: 10.1021/acs.analchem.3c00441. Epub 2023 Sep 1.