Intermediate-Volatility Organic Compounds: A Potential Source of Ambient Oxidized Organic Aerosol

Presto, Albert A.; Miracolo, Marissa A.; Kroll, J. H.; Worsnop, Douglas R.; Robinson, Allen L.; Donahue, Neil M.

doi:10.1021/es803219q

Cited by 109 publications

(113 citation statements)

References 33 publications

Supporting

Mentioning

101

Contrasting

Order By: Relevance

“…SOA formation from some IVOCs has been established experimentally, e.g. naphthalene and heptadecane are two IVOCs whose SOA formation has been investigated in some detail in the Caltech and Carnegie Mellon chambers (Chan et al, 2009;Presto et al, 2009). Unfortunately many IVOCs and SVOCs are not separable by GC-MS and appear in the "unresolved complex mixture" (UCM), which led to the need to parameterize their amounts and SOA formation .…”

Section: Introductionmentioning

confidence: 99%

Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

et al. 2010

View full text Add to dashboard Cite

Abstract. It has been established that observed local and regional levels of secondary organic aerosols (SOA) in polluted areas cannot be explained by the oxidation and partitioning of anthropogenic and biogenic VOC precursors, at least using current mechanisms and parameterizations. In this study, the 3-D regional air quality model CHIMERE is applied to estimate the potential contribution to SOA formation of recently identified semi-volatile and intermediate volatility organic precursors (S/IVOC) in and around Mexico City for the MILAGRO field experiment during March 2006. The model has been updated to include explicitly the volatility distribution of primary organic aerosols (POA), their gas-particle partitioning and the gas-phase oxidation of the vapors. discrepancies with the total OA measurements. Model improvements in OA predictions are associated with the bettercaptured SOA magnitude and diurnal variability. The predicted production from anthropogenic and biomass burning S/IVOC represents 40-60% of the total measured SOA at the surface during the day and is somewhat larger than that from commonly measured aromatic VOCs, especially at the T1 site at the edge of the city. The SOA production from the continued multi-generation S/IVOC oxidation products continues actively downwind. Similar to aircraft observations, the predicted OA/ CO ratio for the ROB case increases from 20-30 µg sm −3 ppm −1 up to 60-70 µg sm −3 ppm −1 between a fresh and 1-day aged air mass, while the GRI case produces a 30% higher OA growth than observed. The predicted average O/C ratio of total OA for the ROB case is 0.16 at T0, substantially below observed value of 0.5. A much better agreement for O/C ratios and temporal variability (R 2 =0.63) is achieved with the updated GRI treatment. Both treatments show a deficiency in regard to POA ageing with a tendency to over-evaporate POA upon dilution of the urban plume suggesting that atmospheric HOA may be less volatile than assumed in these parameterizations. This study highlights the important potential role of S/IVOC chemistry in the SOA budget in this region, and highlights the need for further improvements in available parameterizations. The agreement observed in this study is not sufficient evidence to conclude that S/IVOC are the major missing SOA source in megacity environments. The model is still very underconstrained, andPublished by Copernicus Publications on behalf of the European Geosciences Union.

show abstract

Section: Introductionmentioning

confidence: 99%

Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

et al. 2010

View full text Add to dashboard Cite

show abstract

“…These compounds have been labeled intermediate volatile organic compounds (IVOCs) to distinguish them from more volatile organic compounds (VOCs) associated with spark ignition engine exhaust. IVOCs are defined as having a saturation vapor pressure between 1.33 × 10 −4 and 1.33 × 10 −1 hPa (10 −4 and 10 −1 Torr) at 25 • C (Robinson et al, 2007;Presto et al, 2009). For the n-alkanes this vapor pressure range corresponds to dodecane (C 12 ) through to octadecane (C 18 ) and compounds within this vapor pressure range comprise a large fraction of diesel fuel and exhaust (Han et al, 2008;Schauer et al, 1999;Siegl et al, 1999;Gentner et al, 2012).…”

Section: Introductionmentioning

confidence: 99%

Measuring long chain alkanes in diesel engine exhaust by thermal desorption PTR-MS

2014

View full text Add to dashboard Cite

Abstract.A method using thermal desorption sampling and analysis by proton transfer reaction mass spectrometry (PTR-MS) to measure long chain alkanes (C 12 -C 18 ) and other larger organics associated with diesel engine exhaust emissions is described. Long chain alkanes undergo dissociative proton transfer reactions forming a series of fragment ions with formula C n H 2n+1 . The PTR-MS is insensitive to nalkanes less than C 8 but displays an increasing sensitivity for larger alkanes. Fragment ion distribution and sensitivity is a function of drift conditions. At 80 Td the most abundant ion fragments from C 10 to C 16 n-alkanes were m/z 57, 71 and 85. The mass spectrum of gasoline and diesel fuel at 80 Td displayed ion group patterns that can be related to known fuel constituents, such as alkanes, alkylbenzenes and cycloalkanes, and other compound groups that are inferred from molecular weight distributions such as dihydronapthalenes and naphthenic monoaromatics. It is shown that thermal desorption sampling of gasoline and diesel engine exhausts at 80 Td allows for discrimination against volatile organic compounds, allowing for quantification of long chain alkanes from the abundance of C n H 2n+1 fragment ions. The total abundance of long chain alkanes in diesel engine exhaust was measured to be similar to the total abundance of C 1 -C 4 alkylbenzene compounds. The abundance patterns of compounds determined by thermal desorption sampling may allow for emission profiles to be developed to better quantify the relative contributions of diesel and gasoline exhaust emissions on organic compounds concentrations in urban air.

show abstract

“…Aerosols are major constituents of the troposphere, with effects on human health (Pope and Dockery, 2006), urban and regional photochemistry (Jacobson, 1999), precipitation patterns (Rosenfeld et al, 2008), and directly or indirectly on climate (Kanakidou et al, 2005;Forster et al, 2007). Air samples collected in diverse environments show that the mass of organic aerosols (OA) often exceeds that of aerosol sulfate, nitrate, and soot combined (Zhang et al, 2007;Jimenez et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

et al. 2011

View full text Add to dashboard Cite

Abstract. The evolution of organic aerosols (OA) in Mexico City and its outflow is investigated with the nearly explicit gas phase photochemistry model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), wherein precursor hydrocarbons are oxidized to numerous intermediate species for which vapor pressures are computed and used to determine gas/particle partitioning in a chemical box model. Precursor emissions included observed C3-10 alkanes, alkenes, and light aromatics, as well as larger n-alkanes (up to C25) not directly observed but estimated by scaling to particulate emissions according to their volatility. Conditions were selected for comparison with observations made in March 2006 (MILAGRO). The model successfully reproduces the magnitude and diurnal shape for both primary (POA) and secondary (SOA) organic aerosols, with POA peaking in the early morning at 15-20 µg m −3 , and SOA peaking at 10-15 µg m −3 during mid-day. The majority (≥75 %) of the model SOA stems from reaction products of the large n-alkanes, used here as surrogates for all emitted hydrocarbons of similar volatility, with the remaining SOA originating mostly from the light aromatics. Simulated OA elemental composition reproduces observed H/C and O/C ratios reasonably well, although modeled ratios develop more slowly than observations suggest. SOA chemical composition is initially dominated by δ-hydroxy ketones and nitrates from the large alkanes, with contributions from peroxy acyl nitrates and, at later times when NOx is lower, organic hydroperoxides. The simulated plume-integrated OA Correspondence to: J. Lee-Taylor (julial@ucar.edu) mass continues to increase for several days downwind despite dilution-induced particle evaporation, since oxidation chemistry leading to SOA formation remains strong. In this model, the plume SOA burden several days downwind exceeds that leaving the city by a factor of >3. These results suggest significant regional radiative impacts of SOA.

show abstract

Intermediate-Volatility Organic Compounds: A Potential Source of Ambient Oxidized Organic Aerosol

Cited by 109 publications

References 33 publications

Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

Measuring long chain alkanes in diesel engine exhaust by thermal desorption PTR-MS

Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

Contact Info

Product

Resources

About