Atmospheric fate of OH initiated oxidation of terpenes. Reaction mechanism of α-pinene degradation and secondary organic aerosol formation

Librando, Vito; Tringali, Giuseppe

doi:10.1016/j.jenvman.2005.01.001

Cited by 68 publications

(57 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Of the monoterpenes, α-pinene is the most abundantly emitted. Many carboxylic acids, organonitrates, and organosulfates associated with α-pinene have been observed in aerosols both in the field and from laboratory oxidation (Kavouras et al, 1998(Kavouras et al, , 1999Yu et al, 1999b;Jaoui and Kamens, 2001;Larsen et al, 2001;Librando and Tringali, 2005;Surratt et al, 2007Surratt et al, , 2008Laaksonen et al, 2008;Zhang et al, 2010). A number of carboxylic acids have been used as particle-phase 7414 N. C. Eddingsaas et al: α-pinene photooxidation particle phase composition tracers of α-pinene oxidation, including pinonic acid, pinic acid, 10-hydroxypinonic acid, terpenylic acid, diaterpenylic acid acetate, and 3-methyl-1,2,3-butanetricarboxylic acid (3-MBTCA).…”

Section: Introductionmentioning

confidence: 99%

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NOx environments

et al. 2012

View full text Add to dashboard Cite

Abstract. The gas-phase oxidation of α-pinene produces a large amount of secondary organic aerosol (SOA) in the atmosphere. A number of carboxylic acids, organosulfates and nitrooxy organosulfates associated with α-pinene have been found in field samples and some are used as tracers of α-pinene oxidation. α-pinene reacts readily with OH and O 3 in the atmosphere followed by reactions with both HO 2 and NO. Due to the large number of potential reaction pathways, it can be difficult to determine what conditions lead to SOA. To better understand the SOA yield and chemical composition from low-and high-NO x OH oxidation of α-pinene, studies were conducted in the Caltech atmospheric chamber under controlled chemical conditions. Experiments used low O 3 concentrations to ensure that OH was the main oxidant and low α-pinene concentrations such that the peroxy radical (RO 2 ) reacted primarily with either HO 2 under low-NO x conditions or NO under high-NO x conditions. SOA yield was suppressed under conditions of high-NO x . SOA yield under high-NO x conditions was greater when ammonium sulfate/sulfuric acid seed particles (highly acidic) were present prior to the onset of growth than when ammonium sulfate seed particles (mildly acidic) were present; this dependence was not observed under low-NO x conditions. When aerosol seed particles were introduced after OH oxidation, allowing for later generation species to be exposed to fresh inorganic seed particles, a number of low-NO x products partitioned to the highly acidic aerosol. This indicates that the effect of seed acidity and SOA yield might be under-estimated in traditional experiments where aerosol seed particles are introduced prior to oxidation. We also identify the presence of a number of carboxylic acids that are used as tracer compounds of α-pinene oxidation in the field as well as the formation of organosulfates and nitrooxy organosulfates. A number of the carboxylic acids were observed under all conditions, however, pinic and pinonic acid were only observed under low-NO x conditions. Evidence is provided for particle-phase sulfate esterification of multi-functional alcohols.

show abstract

Section: Introductionmentioning

confidence: 99%

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NOx environments

et al. 2012

View full text Add to dashboard Cite

show abstract

“…Although 20 limonene chemistry is different from α-pinene in that it caters more towards secondary organic aerosols (SOA) formation, addition of limonene as α-pinene increases HO2 and OH losses by 3-6 %, which is well within the uncertainty of the measurements. Nevertheless, the degradation products from terpene oxidation (shown in Figure 5) further act as sources and sinks for OH and HO2, hence play an important role in the overall HOx chemistry (Calogirou et al, 1999;Librando and Tringali, 2005;Zhang et al, 2015;Wisthaler et al, 2001). Further, increasing/decreasing the terpene concentrations by their 25 measured uncertainties (15 %; Table 1) decreases/increases the OH and HO2 model/measured slope by 2-3 %, which is close to the errors on the regression slopes.…”

Section: Modelling Simulations Of Cyphex Hoxmentioning

confidence: 99%

Oxidation processes in the Eastern Mediterranean atmosphere: Evidence from the Modelling of HOx Measurements over Cyprus

Mallik¹,

Tomsche²,

Bourtsoukidis³

et al. 2018

Preprint

View full text Add to dashboard Cite

Abstract. The Mediterranean is a climatically sensitive region located at the crossroads of air masses from three continents: 15Europe, Africa and Asia. The chemical processing of air masses over this region has implications not only for the air quality, but also for the long-range transport of air pollution. To obtain a comprehensive understanding of oxidation processes over the Mediterranean, atmospheric concentrations of the hydroxyl radical (OH) and the hydroperoxyl radical (HO2) were measured during an intensive field campaign (CYprus PHotochemistry EXperiment, CYPHEX-2014) in the north-west of Cyprus in the summer of 2014. Very low local anthropogenic and biogenic emissions around the measurement location 20 provided a vantage point to study the contrasts in atmospheric oxidation pathways under highly processed marine air masses and those influenced by relatively fresh emissions from mainland Europe.The CYPHEX measurements were used to evaluate OH and HO2 simulations using a photochemical box model (CAABA/MECCA) constrained with CYPHEX observations of O3, CO, NOx, hydrocarbons, peroxides and other major HOx (OH + HO2) sources and sinks in a low NOx environment (<100 pptv NO). The model simulations for OH showed very good 25 agreement with in-situ OH observations. Model simulations for HO2 also agreed fairly well with in-situ observations except when pinene levels exceeded 80 pptv. Different schemes to improve the agreement between observed and modelled HO2, including changing the rate coefficients for the reactions of terpene generated peroxy radicals (RO2) with NO and HO2 as well as the autoxidation of terpene generated RO2 species, are explored in this work. The main source of OH in Cyprus was its primary production from O3 photolysis during the day and HONO photolysis during early morning. Recycling contributed 30 about one-third of the total OH production, and the maximum recycling efficiency was about 70 %. CO, which was the largest OH sink was also the largest HO2 source. Lowest HOx production and losses occurred when the air masses had higher residence time over the oceans.Atmos. Chem. Phys. Discuss., https://doi.org/10. 5194/acp-2018-25 Manuscript under review for journal Atmos. Chem. Phys. Air pollution and HOx chemistryThe chemical and photochemical processing of air pollutants, in conjunction with local emissions, meteorology and atmospheric transport, strongly influences the air quality over a region. The regional air quality impacts human health, agriculture, the overall condition of the biosphere and subsequently the climate. Studies attribute 2-4 million premature 5 deaths globally to outdoor air pollution (Silva et al., 2013;Lelieveld et al., 2015). Oxidants in the Earth's atmosphere prevent the pollutants released into it from building up to toxic levels. These oxidants not only convert many toxic pollutants into less toxic forms (e.g. CO to CO2) but also help in their removal (e.g. NOx and SO2 are converted into soluble HNO3 and H2SO4 respectively), although some toxic chemicals may s...

show abstract

“…Optical spectroscopic methods, most notably Fourier transform infrared (FTIR), are suitable for simple gas phase molecule identification (Librando and Tringali, 2005;Larsen et al, 2001). Sample collection on filters or cartridges followed by chromatographic separation and mass spectrometric analysis has been the most widely applied method (Larsen et al, 2001;Jaoui and Kamens, 2003;Forstner et al, 1997).…”

Section: J F Bennett Et Almentioning

confidence: 99%

“…Continuing advances in methods of preparing derivatives of target compounds (Claeys et al, 2007;Temime et al, 2007;Chiappini et al, 2006) and in chromatography, such as 2-D methods (Hamilton et al, 2005), continue to widen the classes of compounds that can be analyzed. Mass spectrometry is now the most common chromatographic detector with MS/MS (Librando and Tringali, 2005) and MS n (Larsen et al, 2001) analysis being more widely applied.…”

Section: J F Bennett Et Almentioning

confidence: 99%

A laboratory flow reactor with gas particle separation and on-line MS/MS for product identification in atmospherically important reactions

2009

View full text Add to dashboard Cite

Abstract.A system to study the gas and particle phase products from gas phase hydrocarbon oxidation is described. It consists of a gas phase photochemical flow reactor followed by a diffusion membrane denuder to remove gases from the reacted products, or a filter to remove the particles. Chemical analysis is performed by an atmospheric pressure chemical ionization (APCI) triple quadrupole mass spectrometer. A diffusion membrane denuder is shown to remove trace gases to below detectable limits so the particle phase can be studied. The system was tested by examining the products of the oxidation of m-xylene initiated by HO radicals. Dimethylphenol was observed in both the gas and particle phases although individual isomers could not be identified. Two furanone isomers, 5-methyl-2(3H)furanone and 3-methyl-2(5H)furanone were identified in the particulate phase, but the isobaric product 2,5 furandione was not observed. One isomer of dimethyl-nitrophenol was identified in the particle phase but not in the gas phase.

show abstract

Atmospheric fate of OH initiated oxidation of terpenes. Reaction mechanism of α-pinene degradation and secondary organic aerosol formation

Cited by 68 publications

References 41 publications

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NO<sub>x</sub> environments

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NO<sub>x</sub> environments

Oxidation processes in the Eastern Mediterranean atmosphere: Evidence from the Modelling of HO<sub>x</sub> Measurements over Cyprus

A laboratory flow reactor with gas particle separation and on-line MS/MS for product identification in atmospherically important reactions

Contact Info

Product

Resources

About

Atmospheric fate of OH initiated oxidation of terpenes. Reaction mechanism of α-pinene degradation and secondary organic aerosol formation

Cited by 68 publications

References 41 publications

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NO&lt;sub&gt;x&lt;/sub&gt; environments

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NO&lt;sub&gt;x&lt;/sub&gt; environments

Oxidation processes in the Eastern Mediterranean atmosphere: Evidence from the Modelling of HO&lt;sub&gt;x&lt;/sub&gt; Measurements over Cyprus

A laboratory flow reactor with gas particle separation and on-line MS/MS for product identification in atmospherically important reactions

Contact Info

Product

Resources

About

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NO<sub>x</sub> environments

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NO<sub>x</sub> environments

Oxidation processes in the Eastern Mediterranean atmosphere: Evidence from the Modelling of HO<sub>x</sub> Measurements over Cyprus