Reactivity Scales as Comparative Tools for Chemical Mechanisms

Derwent, R.G.; Jenkin, Michael E.; Pilling, Michael J.; Carter, William; Kaduwela, A. P.

doi:10.3155/1047-3289.60.8.914

Cited by 31 publications

(34 citation statements)

References 24 publications

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“…These varying methods were shown to be generally well correlated (Butler et al, 2011;Luecken and Mebust, 2008;Derwent et al, 2010). The Derwent et al (2007a) POCPs are appropriate to use in this study as they were calculated under simulated north-western European conditions.…”

Section: S Malley Et Almentioning

confidence: 97%

The impact of speciated VOCs on regional ozone increment derived from measurements at the UK EMEP supersites between 1999 and 2012

et al. 2015

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Abstract. The impact of 27 volatile organic compounds (VOCs) on the regional O 3 increment was investigated using measurements made at the UK EMEP supersites Harwell (1999Harwell ( -2001Harwell ( and 2010Harwell ( -2012 and Auchencorth (2012). Ozone at these sites is representative of rural O 3 in southeast England and northern UK, respectively. The monthlydiurnal regional O 3 increment was defined as the difference between the regional and hemispheric background O 3 concentrations, respectively, derived from oxidant vs. NO x correlation plots, and cluster analysis of back trajectories arriving at Mace Head, Ireland. At Harwell, which had substantially greater regional O 3 increments than Auchencorth, variation in the regional O 3 increment mirrored afternoon depletion of anthropogenic VOCs due to photochemistry (after accounting for diurnal changes in boundary layer mixing depth, and weighting VOC concentrations according to their photochemical ozone creation potential). A positive regional O 3 increment occurred consistently during the summer, during which time afternoon photochemical depletion was calculated for the majority of measured VOCs, and to the greatest extent for ethene and m+p-xylene. This indicates that, of the measured VOCs, ethene and m+p-xylene emissions reduction would be most effective in reducing the regional O 3 increment but that reductions in a larger number of VOCs would be required for further improvement.The VOC diurnal photochemical depletion was linked to anthropogenic sources of the VOC emissions through the integration of gridded anthropogenic VOC emission estimates over 96 h air-mass back trajectories. This demonstrated that one factor limiting the effectiveness of VOC gridded emissions for use in measurement and modelling studies is the highly aggregated nature of the 11 SNAP (Selected Nomenclature for Air Pollution) source sectors in which they are reported, as monthly variation in speciated VOC trajectory emissions did not reflect monthly changes in individual VOC diurnal photochemical depletion. Additionally, the major VOC emission source sectors during elevated regional O 3 increment at Harwell were more narrowly defined through disaggregation of the SNAP emissions to 91 NFR (Nomenclature for Reporting) codes (i.e. sectors 3D2 (domestic solvent use), 3D3 (other product use) and 2D2 (food and drink)). However, spatial variation in the contribution of NFR sectors to parent SNAP emissions could only be accounted for at the country level. Hence, the future reporting of gridded VOC emissions in source sectors more highly disaggregated than currently (e.g. to NFR codes) would facilitate a more precise identification of those VOC sources most important for mitigation of the impact of VOCs on O 3 formation.In summary, this work presents a clear methodology for achieving a coherent VOC, regional-O 3 -impact chemical climate using measurement data and explores the effect of limited emission and measurement species on the understanding of the regional VOC contribution to O 3 concentrat...

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Section: S Malley Et Almentioning

confidence: 97%

The impact of speciated VOCs on regional ozone increment derived from measurements at the UK EMEP supersites between 1999 and 2012

et al. 2015

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“…In the present work, a set of manganese oxide catalysts has been prepared, by the so-called "Solution Combustion Synthesis" (SCS) method, and tested for the total oxidation of ethylene, propylene and toluene. These compounds were chosen as probe molecules for the catalytic activity tests because they are often found in industrial exhausts and have a high POCP (photochemical ozone creation potential) [1,35,36]. The structural and surface properties of the prepared catalysts were then investigated by means of complementary physico-chemical techniques.…”

Section: Introductionmentioning

confidence: 99%

Mesoporous manganese oxides prepared by solution combustion synthesis as catalysts for the total oxidation of VOCs

Piumetti

Fino

Russo

2015

Applied Catalysis B: Environmental

446

179

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“…The efficiency with which O 3 and SOA can be formed from diesel or gasoline emissions is dependent on the mass of available organic carbon, and the reactivity and volatility of that material (Gros et al, 2007;Jimenez et al, 2009;Donahue et al, 2012). To quantify this requires individual speciation of VOCs in order that each property can be properly estimated.…”

Section: Introductionmentioning

confidence: 99%

Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities

Dunmore¹,

Hopkins²,

Lidster³

et al. 2015

Preprint

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Article:Dunmore, R. E. orcid.org/0000-0002-9114-1823, Hopkins, J. R., Lidster, R. T. et al. (5 more authors) (2015) Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities. Atmospheric Chemistry and Physics. pp. 9983-9996. ISSN 1680-7324 Abstract. Hydrocarbons are key precursors to two priority air pollutants, ozone and particulate matter. Those with two to seven carbons have historically been straightforward to observe and have been successfully reduced in many developed cities through air quality policy interventions. Longer chain hydrocarbons released from diesel vehicles are not considered explicitly as part of air quality strategies and there are few direct measurements of their gaseous abundance in the atmosphere. This study describes the chemically comprehensive and continuous measurements of organic compounds in a developed megacity (London), which demonstrate that on a seasonal median basis, diesel-related hydrocarbons represent only 20-30 % of the total hydrocarbon mixing ratio but comprise more than 50 % of the atmospheric hydrocarbon mass and are a dominant local source of secondary organic aerosols. This study shows for the first time that 60 % of the winter primary hydrocarbon hydroxyl radical reactivity is from diesel-related hydrocarbons and using the maximum incremental reactivity scale, we predict that they contribute up to 50 % of the ozone production potential in London. Comparing real-world urban composition with regulatory emissions inventories in the UK and US highlights a previously unaccounted for, but very significant, under-reporting of diesel-related hydrocarbons; an underestimation of a factor ∼ 4 for C 9 species rising to a factor of over 70 for C 12 during winter. These observations show that hydrocarbons from diesel vehicles can dominate gas phase reactive carbon in cities with high diesel fleet fractions. Future control of urban particulate matter and ozone in such locations requires a shift in policy focus onto gas phase hydrocarbons released from diesels as this vehicle type continues to displace gasoline world-wide. PM load (Robinson et al.

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Reactivity Scales as Comparative Tools for Chemical Mechanisms

Abstract: Incremental ozone impacts or reactivities have been calculated for selected organic compounds using a Master Chemical Mechanism (MCMv3

Cited by 31 publications

References 24 publications

The impact of speciated VOCs on regional ozone increment derived from measurements at the UK EMEP supersites between 1999 and 2012

The impact of speciated VOCs on regional ozone increment derived from measurements at the UK EMEP supersites between 1999 and 2012

Mesoporous manganese oxides prepared by solution combustion synthesis as catalysts for the total oxidation of VOCs

Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities

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