scholarly journals Supplementary material to "Organic aerosol source apportionment in Zurich using an extractive electrospray ionization time-of-flight mass spectrometry (EESI-TOF): Part II, biomass burning influences in winter"

2019 ◽  
Author(s):  
Lu Qi ◽  
Mindong Chen ◽  
Giulia Stefenelli ◽  
Veronika Pospisilova ◽  
Yandong Tong ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Electrospray Ionization ◽  
Source Apportionment ◽  
Biomass Burning ◽  
Time Of Flight ◽  
Organic Aerosol ◽  
Ionization Time ◽  
Flight Mass Spectrometry ◽  
Supplementary Material ◽  
Aerosol Source

scholarly journals Organic aerosol source apportionment in Zurich using an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF-MS) – Part 2: Biomass burning influences in winter

2019 ◽  
Vol 19 (12) ◽  
pp. 8037-8062 ◽  
Author(s):  
Lu Qi ◽  
Mindong Chen ◽  
Giulia Stefenelli ◽  
Veronika Pospisilova ◽  
Yandong Tong ◽  
...  
Keyword(s):  
Electrospray Ionization ◽  
Source Apportionment ◽  
Mass Spectrometer ◽  
Biomass Burning ◽  
Time Of Flight ◽  
Organic Aerosol ◽  
Climate Impacts ◽  
Ionization Time ◽  
Flight Mass Spectrometer ◽  
Tof Ms

Abstract. Real-time, in situ molecular composition measurements of the organic fraction of fine particulate matter (PM2.5) remain challenging, hindering a full understanding of the climate impacts and health effects of PM2.5. In particular, the thermal decomposition and ionization-induced fragmentation affecting current techniques has limited a detailed investigation of secondary organic aerosol (SOA), which typically dominates OA. Here we deploy a novel extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF-MS) during winter 2017 in downtown Zurich, Switzerland, which overcomes these limitations, together with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and supporting instrumentation. Positive matrix factorization (PMF) implemented within the Multilinear Engine (ME-2) program was applied to the EESI-TOF-MS data to quantify the primary and secondary contributions to OA. An 11-factor solution was selected as the best representation of the data, including five primary and six secondary factors. Primary factors showed influence from cooking, cigarette smoke, biomass burning (two factors) and a special local unknown event occurred only during two nights. Secondary factors were affected by biomass burning (three factors, distinguished by temperature and/or wind direction), organonitrates, monoterpene oxidation, and undetermined regional processing, in particular the contributions of wood combustion. While the AMS attributed slightly over half the OA mass to SOA but did not identify its source, the EESI-TOF-MS showed that most (>70 %) of the SOA was derived from biomass burning. Together with significant contributions from less aged biomass burning factors identified by both AMS and EESI-TOF-MS, this firmly establishes biomass burning as the single most important contributor to OA mass at this site during winter. High correlation was obtained between EESI-TOF-MS and AMS PMF factors where specific analogues existed, as well as between total signal and POA–SOA apportionment. This suggests the EESI-TOF-MS apportionment in the current study can be approximately taken at face value, despite ion-by-ion differences in relative sensitivity. The apportionment of specific ions measured by the EESI-TOF-MS (e.g., levoglucosan, nitrocatechol, and selected organic acids) and utilization of a cluster analysis-based approach to identify key marker ions for the EESI-TOF-MS factors are investigated. The interpretability of the EESI-TOF-MS results and improved source separation relative to the AMS within this pilot campaign validate the EESI-TOF-MS as a promising approach to source apportionment and atmospheric composition research.

scholarly journals Organic aerosol source apportionment in Zurich using an extractive electrospray ionization time-of-flight mass spectrometry (EESI-TOF): Part II, biomass burning influences in winter

2019 ◽  
Author(s):  
Lu Qi ◽  
Mindong Chen ◽  
Giulia Stefenelli ◽  
Veronika Pospisilova ◽  
Yandong Tong ◽  
...  
Keyword(s):  
Electrospray Ionization ◽  
Source Apportionment ◽  
Mass Spectrometer ◽  
Biomass Burning ◽  
Time Of Flight ◽  
Relative Sensitivity ◽  
Organic Aerosol ◽  
Climate Impacts ◽  
Atmospheric Composition ◽  
Ionization Time

Abstract. Real-time, in situ molecular composition measurements of the organic fraction of fine particulate matter (PM2.5) remain challenging, hindering a full understanding of the climate impacts and health effects of PM2.5. In particular, the thermal decomposition and ionization-induced fragmentation affecting current techniques has limited a detailed investigation of secondary organic aerosol (SOA), which typically dominates OA. Here we deploy a novel extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF-MS) during winter 2017 in downtown Zurich, Switzerland, which overcomes these limitations, together with an Aerodyne high resolution time of flight aerosol mass spectrometer (HR-TOF-AMS) and supporting instrumentation. Positive matrix factorization (PMF) implemented within the Multilinear Engine (ME-2) was applied to the EESI-TOF data to quantify the primary and secondary contributions to OA. An 11-factor solution was selected as the best representation of the data, including 5 primary and 6 secondary factors. Primary factors showed influence from cooking, cigarette smoke, biomass burning (2 factors) and a special local unknown event occurred only during two nights. Secondary factors were affected by biomass burning (3 factors, distinguished by temperature and/or wind direction), organonitrates, monoterpene oxidation, and undetermined regional processing, in particular the contributions of wood combustion. While the AMS attributed slightly over half the OA mass to SOA but did not identify its source, the EESI-TOF showed that most (> 70 %) of the SOA derived from biomass burning. Together with significant contributions from less aged biomass burning factors identified by both AMS and EESI-TOF, this firmly establishes biomass burning as the single most important contributor to OA mass at this site during winter. High correlation was obtained between EESI-TOF and AMS PMF factors where specific analogues existed, as well as between total signal and POA/SOA apportionment. This suggests the EESI-TOF apportionment can be approximately taken at face value, despite ion-by-ion differences in relative sensitivity. The apportionment of specific ions measured by the EESI-TOF (e.g. levoglucosan, nitrocatechol, and selected organic acids), and utilize a cluster analysis-based approach to identify key marker ions for the EESI-TOF factors are investigated. The interpretability of the EESI-TOF results and improved source separation relative to the AMS within this pilot campaign validate the EESI-TOF as a promising approach to source apportionment and atmospheric composition research.

Top-down N-terminal sequencing of Immunoglobulin subunits with electrospray ionization time of flight mass spectrometry

2009 ◽  
Vol 384 (1) ◽  
pp. 42-48 ◽  
Author(s):  
Da Ren ◽  
Gary D. Pipes ◽  
David Hambly ◽  
Pavel V. Bondarenko ◽  
Michael J. Treuheit ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Electrospray Ionization ◽  
Time Of Flight ◽  
Top Down ◽  
Ionization Time ◽  
Flight Mass Spectrometry

scholarly journals Organic aerosol source apportionment in Zurich using an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF-MS) – Part 1: Biogenic influences and day–night chemistry in summer

2019 ◽  
Vol 19 (23) ◽  
pp. 14825-14848 ◽  
Author(s):  
Giulia Stefenelli ◽  
Veronika Pospisilova ◽  
Felipe D. Lopez-Hilfiker ◽  
Kaspar R. Daellenbach ◽  
Christoph Hüglin ◽  
...  
Keyword(s):  
Electrospray Ionization ◽  
Source Apportionment ◽  
Mass Spectrometer ◽  
Time Of Flight ◽  
Organic Aerosol ◽  
Night Time ◽  
Ionization Time ◽  
Flight Mass Spectrometer ◽  
Two Factors ◽  
Tof Ms

Abstract. Improving the understanding of the health and climate impacts of aerosols remains challenging and is restricted by the limitations of current measurement techniques. Detailed investigation of secondary organic aerosol (SOA), which is typically the dominating fraction of the organic aerosol (OA), requires instrumentation capable of real-time, in situ measurements of molecular composition. In this study, we present the first ambient measurements by a novel extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF-MS). The EESI-TOF-MS was deployed along with a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) during summer 2016 at an urban location (Zurich, Switzerland). Positive matrix factorization (PMF), implemented within the Multilinear Engine (ME-2), was applied to the data from both instruments to quantify the primary and secondary contributions to OA. From the EESI-TOF-MS analysis, a six-factor solution was selected as the most representative and interpretable solution for the investigated dataset, including two primary and four secondary factors. The primary factors are dominated by cooking and cigarette smoke signatures while the secondary factors are discriminated according to their daytime (two factors) and night-time (two factors) chemistry. All four factors showed strong influence by biogenic emissions but exhibited significant day–night differences. Factors dominating during daytime showed predominantly ions characteristic of monoterpene and sesquiterpene oxidation while the night-time factors included less oxygenated terpene oxidation products, as well as organonitrates which were likely derived from NO3 radical oxidation of monoterpenes. Overall, the signal measured by the EESI-TOF-MS and AMS showed a good correlation. Further, the two instruments were in excellent agreement in terms of both the mass contribution apportioned to the sum of POA and SOA factors and the total SOA signal. However, while the oxygenated organic aerosol (OOA) factors separated by AMS analysis exhibited a flat diurnal pattern, the EESI-TOF-MS factors illustrated significant chemical variation throughout the day. The captured variability, inaccessible from AMS PMF analysis, was shown to be consistent with the variations in the physiochemical processes influencing chemical composition and SOA formation. The improved source separation and interpretability of EESI-TOF-MS results suggest it to be a promising approach to source apportionment and atmospheric composition research.

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