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

The impact of 27 volatile organic compounds (VOCs) on the regional O3 increment was investigated using measurements made at the UK EMEP supersites Harwell (1999–2001 and 2010–2012) and Auchencorth (2012). Ozone at these sites is representative of rural O3 in south-east England and northern UK, respectively. The monthly-diurnal regional O3 increment was defined as the difference between the regional and hemispheric background O3 concentrations, respectively, derived from oxidant vs. NOx correlation plots, and cluster analysis of back trajectories arriving at Mace Head, Ireland. At Harwell, which had substantially greater regional O3 increments than Auchencorth, variation in the regional O3 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 O3 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 O3 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 O3 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 O3 formation. In summary, this work presents a clear methodology for achieving a coherent VOC, regional-O3-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 O3 concentrations

ACTRIS non-methane hydrocarbon intercomparison experiment in Europe to support WMO GAW and EMEP observation networks

The performance of 18 European institutions involved in long-term non-methane hydrocarbon (NMHC) measurements in ambient air within the framework of the Global Atmosphere Watch (GAW) and the European Monitoring and Evaluation Programme (EMEP) was assessed with respect to data quality objectives (DQOs) of ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) and GAW. Compared to previous intercomparison studies the DQOs define a novel approach to assess and ensure a high quality of the measurements. Having already been adopted by GAW, the ACTRIS DQOs are demanding with deviations to a reference value of less than 5% and a repeatability of better than 2% for NMHC mole fractions above 0.1 nmol mol(-1). The participants of the intercomparison analysed two dry gas mixtures in pressurised cylinders, a 30-component NMHC mixture in nitrogen (NMHC_N-2 /at approximately 1 nmol mol(-1) and a whole air sample (NMHC_air), following a standardised operation procedure including zero-and calibration gas measurements. Furthermore, participants had to report details on their instruments and assess their measurement uncertainties. The NMHCs were analysed either by gas chromatography-flame ionisation detection (GC-FID) or by gas chromatography-mass spectrometry (GC-MS). For the NMHC_N-2 measurements, 62% of the reported values were within the 5% deviation class corresponding to the ACTRIS DQOs. For NMHC_air, generally more frequent and larger deviations to the assigned values were observed, with 50% of the reported values within the 5% deviation class. Important contributors to the poorer performance in NMHC_air compared to NMHC_N-2 were a more complex matrix and a larger span of NMHC mole fractions (0.03-2.5 nmol mol(-1)). The performance of the participating laboratories were affected by the different measurement procedures such as the usage of a two-step vs. a one-step calibration, breakthroughs of C-2-C-3 hydrocarbons in the focussing trap, blank values in zero-gas measurements (especially for those systems using a Nafion (R) Dryer), adsorptive losses of aromatic compounds, and insufficient chromatographic separation.Peer reviewe

Estimating the lifetime of black carbon in rural air

As part of its commitment to the European Monitoring and Evaluation Programme (EMEP) of the UNECE, Defra funds two ‘supersites’ in the UK for monitoring air composition. The site at Auchencorth (central Scotland, 15 km south of Edinburgh and 25 km SW of Cockenzie power station) has been operating since 2006, measuring black carbon using a Magee Aethalometer with an inlet cutoff at 2.5 μm (PM2.5). Five-minute data are aggregated to half-hour averages for reporting to EMEP. June 2006 to May 2010 median concentrations were 0.15 μg m-3 with peaks up to 5 μg m-3. Data are distributed log-normally. Even in well-mixed conditions (wind speed > 2 m s-1) concentrations are log-normal with geometric mean and standard deviation of 0.13 μg m-3 and 2.62, respectively. Volatile organic compounds (VOCs) are measured hourly at the site as part of the UK Hydrocarbons network. Based on analysis (Jobson et al., 1999) of the concentration distribution of VOCs measured at the site during well-mixed daytime conditions, black carbon has a lifetime similar to that of butane, i.e. between 20 and 50 days, depending on the average OH concentration (2.5 to 1 x 105 cm-3). Analysis by wind sector allows separation of potential local and long-range sources, which are presumably linked to particle sizes. This method makes several assumptions concerning the relative sources of black carbon and VOCs, but if both pollutant type have similar sources and transport pathways to the measurement site, then VOC distributions can be used to infer black carbon lifetimes. Jobson B.T., McKeenS.A., Parrish D.D., FehsenfeldF.C., Blake D.R., Goldstein A.H., SchaufflerS.M., Elkins J.C., 1999. Trace gas mixing ratio variability versus lifetime in the troposphere and stratosphere: Observations. Journal of Geophysical Research-Atmospheres 104, 16091-16113

The atmospheric lifetime of black carbon

Black carbon (BC) in the atmosphere contributes to the human health effects of particulate matter and contributes to radiative forcing of climate. The lifetime of BC, particularly the smaller particle sizes (PM2.5) which can be transported over long distances, is therefore an important factor in determining the range of such effects, and the spatial footprint of emission controls. Theory and models suggest that the typical lifetime of BC is around one week. The frequency distributions of measurements of a range of hydrocarbons at a remote rural site in southern Scotland (Auchencorth Moss) between 2007 and 2010 have been used to quantify the relationship between atmospheric lifetime and the geometric standard deviation of observed concentration. The analysis relies on an assumed common major emission source for hydrocarbons and BC, namely diesel-engined vehicles. The logarithm of the standard deviation of the log-transformed concentration data is linearly related to hydrocarbon lifetime, and the same statistic for BC can be used to assess the lifetime of BC relative to the hydrocarbons. Annual average data show BC lifetimes in the range 4–12 days, for an assumed OH concentration of 7 × 105 cm−3. At this site there is little difference in BC lifetime between winter and summer, despite a 3-fold difference in relative hydrocarbon lifetimes. This observation confirms the role of wet deposition as an important removal process for BC, as there is no difference in precipitation between winter and summer at this site. BC lifetime was significantly greater in 2010, which had 23% less rainfall than the preceding 3 years

Actris non-methane hydrocarbon intercomparison experiment in europe to support wmo gaw and emep observation networks

The performance of 18 European institutions involved in long-term non-methane hydrocarbon (NMHC) measurements in ambient air within the framework of the Global Atmosphere Watch (GAW) and the European Monitoring and Evaluation Programme (EMEP) was assessed with respect to data quality objectives (DQOs) of ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) and GAW. Compared to previous intercomparison studies the DQOs define a novel approach to assess and ensure a high quality of the measurements. Having already been adopted by GAW, the ACTRIS DQOs are demanding with deviations to a reference value of less than 5% and a repeatability of better than 2% for NMHC mole fractions above 0.1 nmol mol(-1). The participants of the intercomparison analysed two dry gas mixtures in pressurised cylinders, a 30-component NMHC mixture in nitrogen (NMHC_N-2 /at approximately 1 nmol mol(-1) and a whole air sample (NMHC_air), following a standardised operation procedure including zero-and calibration gas measurements. Furthermore, participants had to report details on their instruments and assess their measurement uncertainties. The NMHCs were analysed either by gas chromatography-flame ionisation detection (GC-FID) or by gas chromatography-mass spectrometry (GC-MS). For the NMHC_N-2 measurements, 62% of the reported values were within the 5% deviation class corresponding to the ACTRIS DQOs. For NMHC_air, generally more frequent and larger deviations to the assigned values were observed, with 50% of the reported values within the 5% deviation class. Important contributors to the poorer performance in NMHC_air compared to NMHC_N-2 were a more complex matrix and a larger span of NMHC mole fractions (0.03-2.5 nmol mol(-1)). The performance of the participating laboratories were affected by the different measurement procedures such as the usage of a two-step vs. a one-step calibration, breakthroughs of C-2-C-3 hydrocarbons in the focussing trap, blank values in zero-gas measurements (especially for those systems using a Nafion (R) Dryer), adsorptive losses of aromatic compounds, and insufficient chromatographic separation