The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosol
The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of secondary organic aerosol (SOA) formed during the chamber photo-oxidation of β-caryophyllene/NO<sub>x</sub> mixtures were investigated. Nucleation of β-caryophyllene SO...
| Main Authors: | , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Copernicus Publications
2012-07-01
|
| Series: | Atmospheric Chemistry and Physics |
| Online Access: | http://www.atmos-chem-phys.net/12/6417/2012/acp-12-6417-2012.pdf |
| _version_ | 1819280452172644352 |
|---|---|
| author | M. R. Alfarra J. F. Hamilton K. P. Wyche N. Good M. W. Ward T. Carr M. H. Barley P. S. Monks M. E. Jenkin A. C. Lewis G. B. McFiggans |
| author_facet | M. R. Alfarra J. F. Hamilton K. P. Wyche N. Good M. W. Ward T. Carr M. H. Barley P. S. Monks M. E. Jenkin A. C. Lewis G. B. McFiggans |
| author_sort | M. R. Alfarra |
| collection | DOAJ |
| description | The effect of photochemical ageing and initial precursor concentration on
the composition and hygroscopic properties of secondary organic aerosol
(SOA) formed during the chamber photo-oxidation of β-caryophyllene/NO<sub>x</sub>
mixtures were investigated. Nucleation of β-caryophyllene SOA particles occurred almost immediately after oxidation
was initiated and led to the formation of fresh SOA with a relatively
simpler composition than has been reported for monoterpenes. The SOA yield
values ranged from 9.5–26.7% and 30.4–44.5% using a
differential mobility particle sizer (DMPS) and an aerosol mass spectrometer
(AMS) mass based measurements, respectively. A total of 20 compounds were
identified in the SOA by LC-MS/MS, with the most abundant compounds
identified as β-caryophyllonic acid and β-caryophyllinic
acid/β-nocaryophyllonic acid. The O:C and H:C elemental ratios of
products identified in the condensed phase ranged from 0.20 to 1.00 and 1.00
to 2.00, with average values of 0.39 and 1.58, respectively. The increase in
the O:C ratio was associated with a decrease in the saturation concentration
of the identified compounds. The compounds identified in the lower initial
concentration experiments were more oxidised compared to those that were
found to be more abundant in the higher initial concentration experiments
with average O:C ratios of 0.51 and 0.27, respectively. Photochemical ageing
led to a more complex SOA composition with a larger contribution coming from
lower molar mass, higher generation products, where both double bonds had
been oxidised. This effect was more evident in the experiments conducted
using the lower initial precursor concentration; a finding confirmed by the
temporal behaviour of key organic mass fragment measured by an Aerosol Mass
Spectrometer. Although the composition changed with both initial precursor
concentration and ageing, this had no significant measurable effect on the
hygroscopic properties of the SOA formed. The latter finding might have been
influenced by the difference in pre-treatment of the semivolatile-containing
particles prior to their measurements. |
| first_indexed | 2024-12-24T00:44:01Z |
| format | Article |
| id | doaj.art-11b388edfe8842e49a44330b90a9c083 |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-12-24T00:44:01Z |
| publishDate | 2012-07-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-11b388edfe8842e49a44330b90a9c0832022-12-21T17:23:51ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242012-07-0112146417643610.5194/acp-12-6417-2012The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosolM. R. Alfarra0J. F. Hamilton1K. P. Wyche2N. Good3M. W. Ward4T. Carr5M. H. Barley6P. S. Monks7M. E. Jenkin8A. C. Lewis9G. B. McFiggans10Centre for Atmospheric Science, School of Earth Atmospheric and Environmental Sciences, University of Manchester, UKDepartment of Chemistry, University of York, UKAtmospheric Chemistry Group, Department of Chemistry, University of Leicester, UKCentre for Atmospheric Science, School of Earth Atmospheric and Environmental Sciences, University of Manchester, UKDepartment of Chemistry, University of York, UKAtmospheric Chemistry Group, Department of Chemistry, University of Leicester, UKCentre for Atmospheric Science, School of Earth Atmospheric and Environmental Sciences, University of Manchester, UKAtmospheric Chemistry Group, Department of Chemistry, University of Leicester, UKAtmospheric Chemistry Services, Okehampton, Devon, UKNational Centre for Atmospheric Science, University of York, Heslington, York, UKCentre for Atmospheric Science, School of Earth Atmospheric and Environmental Sciences, University of Manchester, UKThe effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of secondary organic aerosol (SOA) formed during the chamber photo-oxidation of β-caryophyllene/NO<sub>x</sub> mixtures were investigated. Nucleation of β-caryophyllene SOA particles occurred almost immediately after oxidation was initiated and led to the formation of fresh SOA with a relatively simpler composition than has been reported for monoterpenes. The SOA yield values ranged from 9.5–26.7% and 30.4–44.5% using a differential mobility particle sizer (DMPS) and an aerosol mass spectrometer (AMS) mass based measurements, respectively. A total of 20 compounds were identified in the SOA by LC-MS/MS, with the most abundant compounds identified as β-caryophyllonic acid and β-caryophyllinic acid/β-nocaryophyllonic acid. The O:C and H:C elemental ratios of products identified in the condensed phase ranged from 0.20 to 1.00 and 1.00 to 2.00, with average values of 0.39 and 1.58, respectively. The increase in the O:C ratio was associated with a decrease in the saturation concentration of the identified compounds. The compounds identified in the lower initial concentration experiments were more oxidised compared to those that were found to be more abundant in the higher initial concentration experiments with average O:C ratios of 0.51 and 0.27, respectively. Photochemical ageing led to a more complex SOA composition with a larger contribution coming from lower molar mass, higher generation products, where both double bonds had been oxidised. This effect was more evident in the experiments conducted using the lower initial precursor concentration; a finding confirmed by the temporal behaviour of key organic mass fragment measured by an Aerosol Mass Spectrometer. Although the composition changed with both initial precursor concentration and ageing, this had no significant measurable effect on the hygroscopic properties of the SOA formed. The latter finding might have been influenced by the difference in pre-treatment of the semivolatile-containing particles prior to their measurements.http://www.atmos-chem-phys.net/12/6417/2012/acp-12-6417-2012.pdf |
| spellingShingle | M. R. Alfarra J. F. Hamilton K. P. Wyche N. Good M. W. Ward T. Carr M. H. Barley P. S. Monks M. E. Jenkin A. C. Lewis G. B. McFiggans The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosol Atmospheric Chemistry and Physics |
| title | The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosol |
| title_full | The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosol |
| title_fullStr | The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosol |
| title_full_unstemmed | The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosol |
| title_short | The effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β-caryophyllene secondary organic aerosol |
| title_sort | effect of photochemical ageing and initial precursor concentration on the composition and hygroscopic properties of β caryophyllene secondary organic aerosol |
| url | http://www.atmos-chem-phys.net/12/6417/2012/acp-12-6417-2012.pdf |
| work_keys_str_mv | AT mralfarra theeffectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT jfhamilton theeffectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT kpwyche theeffectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT ngood theeffectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT mwward theeffectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT tcarr theeffectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT mhbarley theeffectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT psmonks theeffectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT mejenkin theeffectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT aclewis theeffectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT gbmcfiggans theeffectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT mralfarra effectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT jfhamilton effectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT kpwyche effectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT ngood effectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT mwward effectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT tcarr effectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT mhbarley effectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT psmonks effectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT mejenkin effectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT aclewis effectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol AT gbmcfiggans effectofphotochemicalageingandinitialprecursorconcentrationonthecompositionandhygroscopicpropertiesofbcaryophyllenesecondaryorganicaerosol |