Reactivity-based strategies for photochemical ozone control in Europe

Derwent, R.G.; Jenkin, Michael E.; Passant, Neil; Pilling, Michael J.

doi:10.1016/j.envsci.2007.01.005

Cited by 86 publications

(65 citation statements)

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“…The impact of speciated VOCs on regional ozone increment 8365 tial (OPP) for a range of VOCs using incremental reactivity methods (Luecken and Mebust, 2008;Derwent et al, 2007a;Hakami et al, 2004;Martien et al, 2003), multi-parent assignment (Bowman, 2005) and "tagging" of VOC degradation sequences (Butler et al, 2011). These varying methods were shown to be generally well correlated (Butler et al, 2011;Luecken and Mebust, 2008;Derwent et al, 2010).…”

Section: S Malley Et Almentioning

confidence: 98%

“…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. Previous comparison with other VOC reactivity scales indicated uncertainty in POCP values of up to ±5 POCP units which equates to an average of ±15 % for the measured VOCs in this study (Derwent et al, 2007b).…”

Section: S Malley Et Almentioning

confidence: 99%

“…Summary data for the measured VOCs at Auchencorth and Harwell (note that m-xylene and p-xylene are reported as a single measurement). The rate coefficients at 298 K for reactions of each VOC with OH are taken from Atkinson and Arey (2003), and the POCPs are from Derwent et al (2007a). The "main source" column gives the SNAP sector with the largest contribution of that VOC to UK annual anthropogenic emissions in 2011, with the exception of isoprene which is mainly of biogenic origin (defined in Sect.…”

Section: Driversmentioning

confidence: 99%

“…In Derwent et al (2007a), a VOC POCP was defined as the ratio (multiplied by 100) of the increase in O 3 due to increased emissions of the VOC simulated in a Lagrangian model along a trajectory traversing from central Europe to the UK, relative to the modelled increase in O 3 from the same mass increase in emissions of ethene (the reference POCP VOC assigned a value of 100). Multiple studies have calculated reactivity scales of O 3 production poten-…”

Section: Statementioning

confidence: 99%

“…For each VOC, each of the 288 median monthly-diurnal concentrations was multiplied by the corresponding modelderived photochemical ozone creation potential (POCP) (Derwent et al, 2007a), to weight the observed diurnal variation of VOCs according to their different propensities for O 3 formation. In Derwent et al (2007a), a VOC POCP was defined as the ratio (multiplied by 100) of the increase in O 3 due to increased emissions of the VOC simulated in a Lagrangian model along a trajectory traversing from central Europe to the UK, relative to the modelled increase in O 3 from the same mass increase in emissions of ethene (the reference POCP VOC assigned a value of 100).…”

Section: Statementioning

confidence: 99%

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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: 98%

Section: S Malley Et Almentioning

confidence: 99%

Section: Driversmentioning

confidence: 99%

Section: Statementioning

confidence: 99%

Section: Statementioning

confidence: 99%

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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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Gas‐phase rate coefficients for a series of alkyl cyclohexanes with OH radicals and Cl atoms

Bejan

Winiberg

Mortimer

et al. 2018

Int J of Chemical Kinetics

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The rate coefficients of the reactions of OH radicals and Cl atoms with three alkylcyclohexanes compounds, methylcyclohexane (MCH), trans-1,4-dimethylcyclohexane (DCH), and ethylcyclohexane (ECH) have been investigated at (293 ± 1) K and 1000 mbar of air using relative rate methods. A majority of the experiments were performed in the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC), a stainless steel chamber using in situ FTIR analysis and online gas chromatography with flame ionization detection (GC-FID) detection to monitor the decay of the alkylcyclohexanes and the reference compounds. The studies were undertaken to provide kinetic data for calibrations of radical detection techniques in HIRAC. The following rate coefficients (in cm 3 molecule −1 s −1 ) were obtained for Cl reactions: k (Cl+MCH) = (3.51 ± 0.37) × 10 -10 , k (Cl+DCH) = (3.63 ± 0.38) × 10 −10 , k (Cl+ECH) = (3.88 ± 0.41) × 10 −10 , and for the reactions with OH radicals: k (OH+MCH) = (9.5 ± 1.3) × 10 -12 , k (OH+DCH) = (12.1 ± 2.2) × 10 −12 , k (OH+ECH) = (11.8 ± 2.0) × 10 −12 . Errors are a combination of statistical errors in the relative rate ratio (2 ) and the error in the reference rate coefficient. Checks for possible systematic errors were made by the use of two reference compounds, two different measurement techniques, and also three different sources of OH were employed in this study: photolysis of CH 3 ONO with black lamps, photolysis of H 2 O 2 at 254 nm, and nonphotolytic trans-2-butene ozonolysis. For DCH, some direct laser flash photolysis studies were also undertaken, producing results in good agreement with the relative rate measurements. Additionally, temperature-dependent rate coefficient investigations were performed for the reaction of methylcyclohexane with the OH radical over the range 273-343 K using the relative rate method; the resulting recommended Arrhenius expression is k (OH + MCH) = (1.85 ± 0.27) × 10 -11 exp((-1.62 ± 0.16) kJ mol −1 /RT) cm 3 molecule −1 s −1 . The kinetic data are discussed in terms of OH and Cl reactivity trends, and comparisons are made with the existing literature values and with rate coefficients from structure-activity relationship methods. This is the first study on the rate coefficient determination of the reaction of ECH with OH radicals and chlorine atoms, respectively. K E Y W O R D Scalibration of OH detector, kinetics, OH and Cl structure activity relationships, substituent effect 544

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Gas‐phase kinetics, POCPs, and an investigation of the contributions of VOCs to urban ozone production in the UK

Holland

Khan

Derwent³

et al. 2023

Int J of Chemical Kinetics

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Ambient concentrations of 22 volatile organic compounds (VOCs) measured at London Marylebone Road (LMR), an urban traffic site, and London Eltham (LE), an urban background site, were analyzed over a period of 23 years to assess the impact of pollution control strategies. A significant decrease in ambient concentration is seen for the majority of VOCs analyzed with total VOC burden decreasing by 76% and 59% for LMR and LE, respectively, across the period studied. This is likely as a result of legislative controls. This analysis was extended to consider the dominant contribution of VOCs to ozone formation at the sites utilizing photochemical ozone creation potential (POCP) values.Similarly, the overall reactivity of the VOC burden at the sites has resulted in a significant decrease of 11% and 7% per year in ozone formation potential (OFP) for LMR and LE, respectively. At LMR, the declines in OFP for VOCs associated with road traffic emissions are all in good agreement at 11%-13% decrease per year. Reasonable agreement is also seen at LE with a decrease of 6%-11% per year in OFP of the VOCs related to traffic sources. VOCs related to non-traffic sources, namely ethane and propane from natural gas leakage, did not see a significant decline over the study period at either site. The variation and composition of the overall VOC burden was compared across three decadal time periods (1997-2000, 2001-2010, 2011-2019) and saw an increase in significance of these pollutants at both sites. At LMR, ethane and propane moved from the fifth and eleventh largest contributors to total VOC burden in 1997-2000 to the first and second largest contributors in 2011-2019. At LE, a similar trend is seen with ethane and propane becoming the first and second largest contributors in the most recent time period, up from second and eighth at the beginning of the dataset. The similarity between these sites suggests such pollutants are not sufficiently controlled under current legislation. The increase in significance of ethane and propane was mirrored in their contribution to ozone generation potential at both sites but ethene continues to dominate in contribution to OFP. At LMR, etheneThis is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

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Reactivity-based strategies for photochemical ozone control in Europe

Cited by 86 publications

References 9 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

Gas‐phase rate coefficients for a series of alkyl cyclohexanes with OH radicals and Cl atoms

Gas‐phase kinetics, POCPs, and an investigation of the contributions of VOCs to urban ozone production in the UK

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