References

ACP

Atmospheric Chemistry and Physics

ACP

Atmos. Chem. Phys.

1680-7324

Copernicus Publications

Göttingen, Germany

10.5194/acp-14-6677-2014

The impact of monoaromatic hydrocarbons on OH reactivity in the coastal UK boundary layer and free troposphere

Lidster

R. T.

¹ Hamilton

J. F.

¹ Lee

J. D.

https://orcid.org/0000-0001-5397-2872

¹ ² Lewis

A. C.

¹ ² Hopkins

J. R.

https://orcid.org/0000-0002-0447-2633

¹ ² Punjabi

¹ Rickard

A. R.

¹ ² Young

J. C.

The Department of Chemistry, The University of York, Heslington, UK

National Centre for Atmospheric Science, University of York, Heslington, York, UK

School of Chemistry, University of Leeds, Leeds, UK

02 07 2014

14 13 6677 6693

2014

This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit https://creativecommons.org/licenses/by/3.0/

This article is available from https://acp.copernicus.org/articles/14/6677/2014/acp-14-6677-2014.html

The full text article is available as a PDF file from https://acp.copernicus.org/articles/14/6677/2014/acp-14-6677-2014.pdf

Reaction with the hydroxyl radical (OH) is the dominant removal mechanism for virtually all volatile organic compounds (VOCs) in the atmosphere; however, it can be difficult to reconcile measured OH reactivity with known sinks. Unresolved higher molecular weight VOCs contribute to OH sinks, of which monoaromatics are potentially an important sub-class. A method based on comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-TOFMS) has been developed that extends the degree with which larger VOCs can be individually speciated from whole air samples (WAS). The technique showed excellent sensitivity, resolution and good agreement with an established gas chromatography–flame ionisation (GC-FID) method, for compounds amenable to analysis on both instruments. Measurements have been made of VOCs within the UK east coast marine boundary layer and free troposphere, using samples collected from five aircraft flights in winter 2011. Ten monoaromatic compounds with an array of different alkyl ring substituents have been quantified, in addition to the simple aromatics, benzene, toluene, ethyl benzene and Σm- and p-xylene. These additional compounds were then included in constrained box model simulations of atmospheric chemistry occurring at two UK rural and suburban field sites in order to assess the potential impact of these larger monoaromatics species on OH reactivity; they have been calculated to contribute an additional 2–6% to the overall modelled OH loss rate, providing a maximum additional OH sink of ~0.9 s−1.

References 1

Apel, E. C., Brauers, T., Koppmann, R., Bandowe, B., Boßmeyer, J., Holzke, C., Tillmann, R., Wahner, A., Wegener, R., Brunner, A., Jocher, M., Ruuskanen, T., Spirig, C., Steigner, D., Steinbrecher, R., Gomez Alvarez, E., Müller, K., Burrows, J. P., Schade, G., Solomon, S. J., Ladstätter-Weißenmayer, A., Simmonds, P., Young, D., Hopkins, J. R., Lewis, A. C., Legreid, G., Reimann, S., Hansel, A., Wisthaler, A., Blake, R. S., Ellis, A. M., Monks, P. S., and Wyche, K. P.: Intercomparison of oxygenated volatile organic compound measurements at the SAPHIR atmosphere simulation chamber, J. Geophys. Res. Atmos., 113, D20307, <a href="http://dx.doi.org/10.1029/2008JD009865">https://doi.org/10.1029/2008JD009865</a>, 2008.

Atkinson, R.: Atmospheric chemistry of VOCs and NOx, Atmos. Environ., 34, 2063–2101, 2000.

Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review, Atmos. Environ., 37, 197–219, 2003.

Bartenbach, S., Williams, J., Plass-Dülmer, C., Berresheim, H., and Lelieveld, J.: In-situ measurement of reactive hydrocarbons at Hohenpeissenberg with comprehensive two-dimensional gas chromatography (GC × GC-FID): use in estimating HO and NO3, Atmos. Chem. Phys., 7, 1–14, <a href="http://dx.doi.org/10.5194/acp-7-1-2007">https://doi.org/10.5194/acp-7-1-2007</a>, 2007.

Brown, H. C. and Okamoto, Y.: Electrophilic Substituent Constants, J. Am. Chem. Soc., 80, 4979–4987, <a href="http://dx.doi.org/10.1021/ja01551a055">https://doi.org/10.1021/ja01551a055</a>, 1958.

Calvert, J. G., Atkinson, R., Becker, K. H., Kamens, R. M., Seinfeld, J. H., Wallington, T. J., and Yarwood, G.: The Mechanisms of Atmospheric Oxidation of Aromatic Hydrocarbons, Oxford University Press, 2002.

Chameides, W. L., Fehsenfeld, F., Rodgers, M. O., Cardelino, C., Martinez, J., Parrish, D., Lonneman, W., Lawson, D. R., Rasmussen, R. A., Zimmerman, P., Greenberg, J., Mlddleton, P., and Wang, T.: Ozone Precursor Relationships in the Ambient Atmosphere, J. Geophys. Res., 97, 6037–6055, 1992.

Di Carlo, P., Brune, W. H., Martinez, M., Harder, H., Lesher, R., Ren, X., Thornberry, T., Carroll, M. A., Young, V., Shepson, P. B., Riemer, D., Apel, E., and Campbell, C.: Missing OH Reactivity in a Forest: Evidence for Unknown Reactive Biogenic VOCs, Science, 304, 722–725, <a href="http://dx.doi.org/10.1126/science.1094392">https://doi.org/10.1126/science.1094392</a>, 2004.

Emmerson, K. M., Carslaw, N., Carslaw, D. C., Lee, J. D., McFiggans, G., Bloss, W. J., Gravestock, T., Heard, D. E., Hopkins, J., Ingham, T., Pilling, M. J., Smith, S. C., Jacob, M., and Monks, P. S.: Free radical modelling studies during the UK TORCH Campaign in Summer 2003, Atmos. Chem. Phys., 7, 167–181, <a href="http://dx.doi.org/10.5194/acp-7-167-2007">https://doi.org/10.5194/acp-7-167-2007</a>, 2007.

Goldstein, A. H. and Galbally, I. E.: Known and Unexplored Organic Constituents in the Earth's Atmosphere, Environ. Sci. Technol., 41, 1514–1521, 2007.

Hamilton, J. F. and Lewis, A. C.: Monoaromatic complexity in urban air and gasoline assessed using comprehensive GC and fast GC-TOF/MS, Atmos. Environ., 37, 589–602, 2003.

Heard, D. E. and Pilling, M. J.: Measurement of OH and HO2 in the troposphere, Chem. Rev., 103, 5163–5198, 2003.

Hopkins, J. R., Boddy, R. K., Hamilton, J. F., Lee, J. D., Lewis, A. C., Purvis, R. M., and Watson, N. J.: An observational case study of ozone and precursors inflow to South East England during an anticyclone, J. Environ. Monitor., 8, 1195–1202, 2006.

Hopkins, J. R., Jones, C. E., and Lewis, A. C.: A dual channel gas chromatograph for atmospheric analysis of volatile organic compounds including oxygenated and monoterpene compounds, J. Environ. Monitor., 13, 2268–2276, 2011.

Ingham, T., Goddard, A., Whalley, L. K., Furneaux, K. L., Edwards, P. M., Seal, C. P., Self, D. E., Johnson, G. P., Read, K. A., Lee, J. D., and Heard, D. E.: A flow-tube based laser-induced fluorescence instrument to measure OH reactivity in the troposphere, Atmos. Meas. Tech., 2, 465–477, <a href="http://dx.doi.org/10.5194/amt-2-465-2009">https://doi.org/10.5194/amt-2-465-2009</a>, 2009.

Jenkin, M. E., Saunders, S. M., Wagner, V., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 181–193, <a href="http://dx.doi.org/10.5194/acp-3-181-2003">https://doi.org/10.5194/acp-3-181-2003</a>, 2003.

Kovacs, T. and Brune, W.: Total OH Loss Rate Measurement, J. Atmos. Chem., 39, 105–122, <a href="http://dx.doi.org/10.1023/A:1010614113786">https://doi.org/10.1023/A:1010614113786</a>, 2001.

Kwok, E. S. C. and Atkinson, R.: Estimation of hydroxyl radical reaction-rate constants for gas-phase organic-compounds using a structure-reactivity relationship – an update, Atmos. Environ., 29, 1685–1695, 1995.

Lee, J., Young, J., Read, K., Hamilton, J., Hopkins, J., Lewis, A., Bandy, B., Davey, J., Edwards, P., Ingham, T., Self, D., Smith, S., Pilling, M., and Heard, D.: Measurement and calculation of OH reactivity at a United Kingdom coastal site, J. Atmos. Chem., 64, 53–76, 2009.

Lee, J. D., Lewis, A. C., Monks, P. S., Jacob, M., Hamilton, J. F., Hopkins, J. R., Watson, N. M., Saxton, J. E., Ennis, C., Carpenter, L. J., Carslaw, N., Fleming, Z., Bandy, B. J., Oram, D. E., Penkett, S. A., Slemr, J., Norton, E., Rickard, A. R., K Whalley, L., Heard, D. E., Bloss, W. J., Gravestock, T., Smith, S. C., Stanton, J., Pilling, M. J., and Jenkin, M. E.: Ozone photochemistry and elevated isoprene during the UK heatwave of August 2003, Atmos. Environ., 40, 7598–7613, 2006.

Lewis, A. C., Carslaw, N., Marriott, P. J., Kinghorn, R. M., Morrison, P., Lee, A. L., Bartle, K. D., and Pilling, M. J.: A larger pool of ozone-forming carbon compounds in urban atmospheres, Nature, 405, 778–781, 2000.

Lewis, A. C., Evans, M. J., Hopkins, J. R., Punjabi, S., Read, K. A., Purvis, R. M., Andrews, S. J., Moller, S. J., Carpenter, L. J., Lee, J. D., Rickard, A. R., Palmer, P. I., and Parrington, M.: The influence of biomass burning on the global distribution of selected non-methane organic compounds, Atmos. Chem. Phys., 13, 851–867, <a href="http://dx.doi.org/10.5194/acp-13-851-2013">https://doi.org/10.5194/acp-13-851-2013</a>, 2013.

Logan, J. A., Prather, M. J., Wofsy, S. C., and McElroy, M. B.: Tropospheric Chemistry: A Global Perspective, J. Geophys. Res., 86, 7210–7254, 1981.

Mao, J., Ren, X., Brune, W. H., Olson, J. R., Crawford, J. H., Fried, A., Huey, L. G., Cohen, R. C., Heikes, B., Singh, H. B., Blake, D. R., Sachse, G. W., Diskin, G. S., Hall, S. R., and Shetter, R. E.: Airborne measurement of OH reactivity during INTEX-B, Atmos. Chem. Phys., 9, 163–173, <a href="http://dx.doi.org/10.5194/acp-9-163-2009">https://doi.org/10.5194/acp-9-163-2009</a>, 2009.

Nölscher, A. C., Sinha, V., Bockisch, S., Klüpfel, T., and Williams, J.: Total OH reactivity measurements using a new fast Gas Chromatographic Photo-Ionization Detector (GC-PID), Atmos. Meas. Tech., 5, 2981–2992, <a href="http://dx.doi.org/10.5194/amt-5-2981-2012">https://doi.org/10.5194/amt-5-2981-2012</a>, 2012.

Phillips, J. and Liu, Z.: Comprehensive Two-dimensional Gas Chromatography using an On-Column Thermal Modulator Interface, J. Chromatogr. Sci., 28, 227–231, 1991.

RONOCO: FAAM, <a href="http://www.faam.ac.uk/index.php/campaigns/current-campaigns/85-ronoco">http://www.faam.ac.uk/index.php/campaigns/current-campaigns/85-ronoco</a>, 2009–2011.

Sadanaga, Y., Yoshino, A., Watanabe, K., Yoshioka, A., Wakazono, Y., Kanaya, Y., and Kajii, Y.: Development of a measurement system of OH reactivity in the atmosphere by using a laser-induced pump and probe technique, Rev. Sci. Instr., 75, 2648–2655, <a href="http://dx.doi.org/10.1063/1.1775311">https://doi.org/10.1063/1.1775311</a>, 2004.

Saxton, J. E., Lewis, A. C., Kettlewell, J. H., Ozel, M. Z., Gogus, F., Boni, Y., Korogone, S. O. U., and Serca, D.: Isoprene and monoterpene measurements in a secondary forest in northern Benin, Atmos. Chem. Phys., 7, 4095–4106, <a href="http://dx.doi.org/10.5194/acp-7-4095-2007">https://doi.org/10.5194/acp-7-4095-2007</a>, 2007.

Sinha, V., Williams, J., Crowley, J. N., and Lelieveld, J.: The comparative reactivity method - a new tool to measure total OH reactivity in ambient air, Atmos. Chem. Phys., 8, 2213–2227, <a href="http://dx.doi.org/10.5194/acp-8-2213-2008">https://doi.org/10.5194/acp-8-2213-2008</a>, 2008.

Sinha, V., Williams, J., Lelieveld, J., Ruuskanen, T., Kajos, M., Patokoski, J., Hellen, H., Hakola, H., Mogensen, D., Boy, M., Rinne, J., and Kulmala, M.: OH Reactivity Measurements within a Boreal Forest: Evidence for Unknown Reactive Emissions, Environ. Sci. Technol., 44, 6614–6620, <a href="http://dx.doi.org/10.1021/es101780b">https://doi.org/10.1021/es101780b</a>, 2010.

Stone, D., Evans, M. J., Commane, R., Ingham, T., Floquet, C. F. A., McQuaid, J. B., Brookes, D. M., Monks, P. S., Purvis, R., Hamilton, J. F., Hopkins, J., Lee, J., Lewis, A. C., Stewart, D., Murphy, J. G., Mills, G., Oram, D., Reeves, C. E., and Heard, D. E.: HOx observations over West Africa during AMMA: impact of isoprene and NOx, Atmos. Chem. Phys., 10, 9415–9429, <a href="http://dx.doi.org/10.5194/acp-10-9415-2010">https://doi.org/10.5194/acp-10-9415-2010</a>, 2010.

Stone, D., Whalley, L. K., and Heard, D. E.: Tropospheric OH and HO2 radicals: field measurements and model comparisons, Chem. Soc. Rev., 41, 6348–6404, <a href="http://dx.doi.org/10.1039/C2CS35140D">https://doi.org/10.1039/C2CS35140D</a>, 2012.

Xu, X., Stee, L. L. P., Williams, J, Beens, J., Adahchour, M., Vreuls, R. J. J., Brinkman, U. A., and Lelieveld, J.: Comprehensive two-dimensional gas chromatography (GC × GC) measurements of volatile organic compounds in the atmosphere, Atmos. Chem. Phys., 3, 665–682, <a href="http://dx.doi.org/10.5194/acp-3-665-2003">https://doi.org/10.5194/acp-3-665-2003</a>, 2003a.

Xu, X., Williams, C., Plass-Dülmer, H., Berresheim, H., Salisbury, G., Lange, L., and Lelieveld, J.: GC × GC measurements of C7–C11 aromatic and n-alkane hydrocarbons on Crete, in air from Eastern Europe during the MINOS campaign, Atmos. Chem. Phys., 3, 1461-1475, <a href="http://dx.doi.org/10.5194/acp-3-1461-2003">https://doi.org/10.5194/acp-3-1461-2003</a>, 2003b.