References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-12-7269-2012

Constraints on instantaneous ozone production rates and regimes during DOMINO derived using in-situ OH reactivity measurements

Sinha

¹ ² Williams

¹ Diesch

J. M.

³ Drewnick

³ Martinez

¹ Harder

¹ Regelin

¹ Kubistin

¹ Bozem

¹ ⁶ Hosaynali-Beygi

¹ Fischer

¹ Andrés-Hernández

M. D.

⁴ Kartal

⁴ Adame

J. A.

⁵ Lelieveld

Air Chemistry Division, Max-Planck-Institute for Chemistry, Mainz, Germany

Indian Institute of Science Education and Research Mohali, Sector 81, S. A. S. Nagar, Manauli PO, Punjab 140306, India

Particle Chemistry Department, Max-Planck-Institute for Chemistry, Mainz, Germany

Institute of Environmental Physics, University of Bremen, Bremen, Germany

Atmospheric Research and Instrumentation Branch, National Institute for Aerospace Technology (INTA), Mazagón-Huelva, Spain

Institute for Atmospheric Physics, University of Mainz, Mainz, Germany

09 08 2012

12 15 7269 7283

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/12/7269/2012/acp-12-7269-2012.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/7269/2012/acp-12-7269-2012.pdf

In this study air masses are characterized in terms of their total OH reactivity which is a robust measure of the "reactive air pollutant loading". The measurements were performed during the DOMINO campaign (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) held from 21/11/2008 to 08/12/2008 at the Atmospheric Sounding Station – El Arenosillo (37.1° N–6.7° W, 40 m a.s.l.). The site was frequently impacted by marine air masses (arriving at the site from the southerly sector) and air masses from the cities of Huelva (located NW of the site), Seville and Madrid (located NNE of the site). OH reactivity values showed strong wind sector dependence. North eastern "continental" air masses were characterized by the highest OH reactivities (average: 31.4 ± 4.5 s−1; range of average diel values: 21.3–40.5 s−1), followed by north western "industrial" air masses (average: 13.8 ± 4.4 s−1; range of average diel values: 7–23.4 s−1) and marine air masses (average: 6.3 ± 6.6 s−1; range of average diel values: below detection limit −21.7 s−1), respectively. The average OH reactivity for the entire campaign period was ~18 s−1 and no pronounced variation was discernible in the diel profiles with the exception of relatively high values from 09:00 to 11:00 UTC on occasions when air masses arrived from the north western and southern wind sectors. The measured OH reactivity was used to constrain both diel instantaneous ozone production potential rates and regimes. Gross ozone production rates at the site were generally limited by the availability of NOx with peak values of around 20 ppbV O3 h−1. Using the OH reactivity based approach, derived ozone production rates indicate that if NOx would no longer be the limiting factor in air masses arriving from the continental north eastern sector, peak ozone production rates could double. We suggest that the new combined approach of in-situ fast measurements of OH reactivity, nitrogen oxides and peroxy radicals for constraining instantaneous ozone production rates, could significantly improve analyses of upwind point sources and their impact on regional ozone levels.

References 1

Adame, J. A., Lozano, A., Bolivar, J. P., De la Morena, B. A., Contreras, J., and Godoy, F.: Behavior, distribution and variability of surface ozone at an arid region in the south of Iberian Peninsula (Seville, Spain), Chemosphere, 70, 841–849, 2008.

Adame, J. A., Bolivar, J. P., and de la Morena, B. A.: Surface ozone measurements in the southwest of the Iberian Peninsula (Huelva, Spain), Environ. Sci. Pollut. R., 17, 355–368, 2010a.

Adame, J. A., Serrano, E., Bolivar, J. P., and de la Morena, B. A.: On the Tropospheric Ozone Variations in a Coastal Area of Southwestern Europe under a Mesoscale Circulation, J. Appl. Meteorol. Clim., 49, 748–759, 2010b.

Alastuey, A., Querol, X., Plana, F., Viana, M., Ruiz, C. R., de la Campa, A. S., de la Rosa, J., Mantilla, E., and dos Santos, S. G.: Identification and chemical characterization of industrial particulate matter sources in southwest Spain, J. Air Waste Manage., 56, 993–1006, 2006.

Ammann, C., Brunner, A., Spirig, C., and Neftel, A.: Technical note: Water vapour concentration and flux measurements with PTR-MS, Atmos. Chem. Phys., 6, 4643–4651, http://dx.doi.org/10.5194/acp-6-4643-2006doi:10.5194/acp-6-4643-2006, 2006.

Atkinson, R., Aschmann, S. M., Winer, A. M., and Carter, W. P. L.: Rate Constants for the Gas-Phase Reactions of OH Radicals and O3 with Pyrrole at 295+/-1k and Atmospheric-Pressure, Atmos. Environ., 18, 2105–2107, 1984.

Atkinson, R.: Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes, Atmos. Chem. Phys., 3, 2233–2307, http://dx.doi.org/10.5194/acp-3-2233-2003doi:10.5194/acp-3-2233-2003, 2003.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I – gas phase reactions of O$_\text x$, HO$_\text x$, NO$_\text x$ and SO$_\text x$ species, Atmos. Chem. Phys., 4, 1461–1738, http://dx.doi.org/10.5194/acp-4-1461-2004doi:10.5194/acp-4-1461-2004, 2004.

Butler, T. M., Lawrence, M. G., Taraborrelli, D., and Lelieveld, J.: Multi-day ozone production potential of volatile organic compounds calculated with a tagging approach, Atmos. Environ., 45, 4082–4090, http://dx.doi.org/10.1016/j.atmosenv.2011.03.040doi:10.1016/j.atmosenv.2011.03.040, 2011.

Cantrell, C. A., Shetter, R. E., Lind, J. A., McDaniel, A. H., Calvert, J. G., Parrish, D. D., Fehsenfeld, F. C., Buhr, M. P., and Trainer, M.: An Improved Chemical Amplifier Technique for Peroxy Radical Measurements, J. Geophys. Res., 98, 2897–2909, doi:10.1029/92JD02842, 1993.

Crowley, J. N., Thieser, J., Tang, M. J., Schuster, G., Bozem, H., Beygi, Z. H., Fischer, H., Diesch, J.-M., Drewnick, F., Borrmann, S., Song, W., Yassaa, N., Williams, J., Pöhler, D., Platt, U., and Lelieveld, J.: Variable lifetimes and loss mechanisms for NO3 and N2O$_5$ during the DOMINO campaign: contrasts between marine, urban and continental air, Atmos. Chem. Phys., 11, 10853–10870, http://dx.doi.org/10.5194/acp-11-10853-2011doi:10.5194/acp-11-10853-2011, 2011.

Di Carlo, P., Brune, W. H., Martinez, M., Harder, H., Lesher, R., Ren, X. R., 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, 2004.

Diesch,~J.-M., Drewnick,~F., Zorn,~S R., von~der~Weiden-Reinmüller,~S.-L., Martinez,~M., and Borrmann,~S.: Variability of aerosol, gaseous pollutants and meteorological characteristics associated with changes in air mass origin at the SW Atlantic coast of Iberia, Atmos. Chem. Phys., 12, 3761–3782, http://dx.doi.org/10.5194/acp-12-3761-2012doi:10.5194/acp-12-3761-2012, 2012.

Draxler, R. R. and Rolph, G. D.: HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory), Model access via NOAA ARL READY Website http://ready.arl.noaa.gov/HYSPLIT.php, NOAA Air Resources Laboratory, Silver Spring, MD, USA, 2011.

Fuchs, H., Bohn, B., Hofzumahaus, A., Holland, F., Lu, K. D., Nehr, S., Rohrer, F., and Wahner, A.: Detection of HO2 by laser-induced fluorescence: calibration and interferences from RO2 radicals, Atmos. Meas. Tech., 4, 1209–1225, http://dx.doi.org/10.5194/amt-4-1209-2011doi:10.5194/amt-4-1209-2011, 2011.

Hastie, D. R., Weißenmayer, M., Burrows, J. P., and Harris, G. W.: Calibrated chemical amplifier for atmospheric RO$_\text x$ measurements, Anal. Chem., 63, 2048–2057, 1991.

Hosaynali Beygi, Z., Fischer, H., Harder, H. D., Martinez, M., Sander, R., Williams, J., Brookes, D. M., Monks, P. S., and Lelieveld, J.: Oxidation photochemistry in the Southern Atlantic boundary layer: unexpected deviations of photochemical steady state, Atmos. Chem. Phys., 11, 8497–8513, http://dx.doi.org/10.5194/acp-11-8497-2011doi:10.5194/acp-11-8497-2011, 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, http://dx.doi.org/10.5194/amt-2-465-2009doi:10.5194/amt-2-465-2009, 2009.

Kartal, D., Andrés-Hernández, M. D., Reichert, L., Schlager, H., and Burrows, J. P.: Technical Note: Characterisation of a DUALER instrument for the airborne measurement of peroxy radicals during AMMA 2006, Atmos. Chem. Phys., 10, 3047–3062, http://dx.doi.org/10.5194/acp-10-3047-2010doi:10.5194/acp-10-3047-2010, 2010.

Keenan, T., Niinemets, Ü., Sabate, S., Gracia, C., and Peñuelas, J.: Seasonality of monoterpene emission potentials in Quercus ilex and Pinus pinea: Implications for regional VOC emissions modeling, J. Geophys. Res., 114, D22202, http://dx.doi.org/10.1029/2009JD011904doi:10.1029/2009JD011904, 2009.

Kirchner, F., Jeanneret, F., Clappier, A., Kruger, B., van den Bergh, H., and Calpini, B.: Total VOC reactivity in the planetary boundary layer 2. A new indicator for determining the sensitivity of the ozone production to VOC and NO$_\text x$, J. Geophys. Res.-Atmos., 106, 3095–3110, http://dx.doi.org/10.1029/2000jd900603doi:10.1029/2000jd900603, 2001.

Kovacs, T. A. and Brune, W. H.: Total OH loss rate measurement, J. Atmos. Chem., 39, 105–122, 2001.

Kovacs, T. A., Brune, W. H., Harder, H., Martinez, M., Simpas, J. B., Frost, G. J., Williams, E., Jobson, T., Stroud, C., Young, V., Fried, A., and Wert, B.: Direct measurements of urban OH reactivity during Nashville SOS in summer 1999, J. Environ. Monit., 5, 68–74, 2003.

Lee, J. D., Young, J. C., Read, K. A., Hamilton, J. F., Hopkins, J. R., Lewis, A. C., Bandy, B. J., Davey, J., Edwards, P., Ingham, T., Self, D. E., Smith, S. C., Pilling, M. J., and Heard, D. E.: Measurement and calculation of OH reactivity at a United Kingdom coastal site, J. Atmos. Chem., 64, 53–76, http://dx.doi.org/10.1007/s10874-010-9171-0doi:10.1007/s10874-010-9171-0, 2009.

Lelieveld, J., Dentener, F. J., Peters, W., and Krol, M. C.: On the role of hydroxyl radicals in the self-cleansing capacity of the troposphere, Atmos. Chem. Phys., 4, 2337–2344, http://dx.doi.org/10.5194/acp-4-2337-2004doi:10.5194/acp-4-2337-2004, 2004.

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.

Lou, S., Holland, F., Rohrer, F., Lu, K., Bohn, B., Brauers, T., Chang, C.C., Fuchs, H., Häseler, R., Kita, K., Kondo, Y., Li, X., Shao, M., Zeng, L., Wahner, A., Zhang, Y., Wang, W., and Hofzumahaus, A.: Atmospheric OH reactivities in the Pearl River Delta – China in summer 2006: measurement and model results, Atmos. Chem. Phys., 10, 11243–11260, http://dx.doi.org/10.5194/acp-10-11243-2010doi:10.5194/acp-10-11243-2010, 2010.

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, http://dx.doi.org/10.5194/acp-9-163-2009doi:10.5194/acp-9-163-2009, 2009.

Martinez, M., Harder, H., Kovacs, T. A., Simpas, J. B., Bassis, J., Lesher, R., Brune, W. H., Frost, G. J., Williams, E. J., Stroud, C. A., Jobson, B. T., Roberts, J. M., Hall, S. R., Shetter, R. E., Wert, B., Fried, A., Alicke, B., Stutz, J., Young, V. L., White, A. B., and Zamora, R. J.: OH and HO2 concentrations, sources, and loss rates during the Southern Oxidants Study in Nashville, Tennessee, summer 1999, J. Geophys. Res.-Atmos., 108, 4617, http://dx.doi.org/10.1029/2003JD003551doi:10.1029/2003JD003551, 2003.

Martinez, M., Harder, H., Kubistin, D., Rudolf, M., Bozem, H., Eerdekens, G., Fischer, H., Klüpfel, T., Gurk, C., Königstedt, R., Parchatka, U., Schiller, C. L., Stickler, A., Williams, J., and Lelieveld, J.: Hydroxyl radicals in the tropical troposphere over the Suriname rainforest: airborne measurements, Atmos. Chem. Phys., 10, 3759-3773, http://dx.doi.org/10.5194/acp-10-3759-2010doi:10.5194/acp-10-3759-2010, 2010.

Monks, P. S., Granier, C., Fuzzi, S., Stohl, A., Williams, M. L., Akimoto, H., Amann, M., Baklanov, A., Baltensperger, U., Bey, I., Blake, N., Blake, R. S., Carslaw, K., Cooper, O. R., Dentener, F., Fowler, D., Fragkou, E., Frost, G. J., Generoso, S., Ginoux, P., Grewe, V., Guenther, A., Hansson, H. C., Henne, S., Hjorth, J., Hofzumahaus, A., Huntrieser, H., Isaksen, I. S. A., Jenkin, M. E., Kaiser, J., Kanakidou, M., Klimont, Z., Kulmala, M., Laj, P., Lawrence, M. G., Lee, J. D., Liousse, C., Maione, M., McFiggans, G., Metzger, A., Mieville, A., Moussiopoulos, N., Orlando, J. J., O'Dowd, C. D., Palmer, P. I., Parrish, D. D., Petzold, A., Platt, U., Poschl, U., Prevot, A. S. H., Reeves, C. E., Reimann, S., Rudich, Y., Sellegri, K., Steinbrecher, R., Simpson, D., ten Brink, H., Theloke, J., van der Werf, G. R., Vautard, R., Vestreng, V., Vlachokostas, C., and von Glasow, R.: Atmospheric composition change – global and regional air quality, Atmos. Environ., 43, 5268–5350, 2009.

Ren, X. R., Harder, H., Martinez, M., Lesher, R. L., Oliger, A., Shirley, T., Adams, J., Simpas, J. B., and Brune, W. H.: HO$_\text x$ concentrations and OH reactivity observations in New York City during PMTACS-NY2001, Atmos. Environ., 37, 3627–3637, 2003.

Ren, X. R., Brune, W. H., Oliger, A., Metcalf, A. R., Simpas, J. B., Shirley, T., Schwab, J. J., Bai, C. H., Roychowdhury, U., Li, Y. Q., Cai, C. X., Demerjian, K. L., He, Y., Zhou, X. L., Gao, H. L., and Hou, J.: OH, HO2, and OH reactivity during the PMTACS-NY Whiteface Mountain 2002 campaign: Observations and model comparison, J. Geophys. Res.-Atmos., 111, D10S03, http://dx.doi.org/10.1029/2005JD006126doi:10.1029/2005JD006126, 2006.

Sadanaga, Y., Yoshino, A., Kato, S., Yoshioka, A., Watanabe, K., Miyakawa, Y., Hayashi, I., Ichikawa, M., Matsumoto, J., Nishiyama, A., Akiyama, N., Kanaya, Y., and Kajii, Y.: The importance of NO2 and volatile organic compounds in the urban air from the viewpoint of the OH reactivity, Geophys. Res. Lett., 31, L08102, http://dx.doi.org/10.1029/2004GL019661doi:10.1029/2004GL019661, 2004a.

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. Instrum., 75, 2648–2655, 2004b.

Sadanaga, Y., Yoshino, A., Kato, S., and Kajii, Y.: Measurements of OH reactivity and photochemical ozone production in the urban atmosphere, Environ. Sci. Technol., 39, 8847–8852, 2005. \hack

Seinfeld, J. H. and Pandis. S. N.: Chapter 6, Atmospheric Chemistry and Physics – From Air Pollution to Climate Change, Second Edition ed., John Wiley & Sons, Inc, New Jersey, USA, 2006.

Shirley, T. R., Brune, W. H., Ren, X., Mao, J., Lesher, R., Cardenas, B., Volkamer, R., Molina, L. T., Molina, M. J., Lamb, B., Velasco, E., Jobson, T., and Alexander, M.: Atmospheric oxidation in the Mexico City Metropolitan Area (MCMA) during April 2003, Atmos. Chem. Phys., 6, 2753–2765, http://dx.doi.org/10.5194/acp-6-2753-2006doi:10.5194/acp-6-2753-2006, 2006.

Sinha, V., Williams, J., Crutzen, P. J., and Lelieveld, J.: Methane emissions from boreal and tropical forest ecosystems derived from in-situ measurements, Atmos. Chem. Phys. Discuss., 7, 14011–14039, http://dx.doi.org/10.5194/acpd-7-14011-2007doi:10.5194/acpd-7-14011-2007, 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, http://dx.doi.org/10.5194/acp-8-2213-2008doi:10.5194/acp-8-2213-2008, 2008.

Sinha, V., Custer, T. G., Kluepfel, T., and Williams, J.: The effect of relative humidity on the detection of pyrrole by PTR-MS for OH reactivity measurements, Int. J. Mass Spectrom., 282, 108–111, 2009.

Sinha, V., Williams, J., Lelieveld, J., Ruuskanen, T. M., Kajos, M. K., 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, 2010.

Sommariva, R., Brown, S. S., Roberts, J. M., Brookes, D. M., Parker, A. E., Monks, P. S., Bates, T. S., Bon, D., de Gouw, J. A., Frost, G. J., Gilman, J. B., Goldan, P. D., Herndon, S. C., Kuster, W. C., Lerner, B. M., Osthoff, H. D., Tucker, S. C., Warneke, C., Williams, E. J., and Zahniser, M. S.: Ozone production in remote oceanic and industrial areas derived from ship based measurements of peroxy radicals during TexAQS 2006, Atmos. Chem. Phys., 11, 2471–2485, http://dx.doi.org/10.5194/acp-11-2471-2011doi:10.5194/acp-11-2471-2011, 2011.

Song, W. Williams, J., Yassaa, N., Martinez, M., Carnero, J. A. A., Hidalgo, P. J., Bozem, H., Lelieveld, J.: Winter and summer characterization of biogenic enantiomeric monoterpenes and anthropogenic BTEX compounds at a Mediterranean Stone Pine forest site, J. Atmos. Chem., 68, 233–250, http://dx.doi.org/10.1007/s10874-012-9219-4doi:10.1007/s10874-012-9219-4, 2011.

Sörgel, M., Regelin, E., Bozem, H., Diesch, J. M., Drewnick, F., Fischer, H., Harder, H., Held, A., Hosaynali-Beygi, Z., Martinez, M., and Zetzsch, C.: Quantification of the unknown HONO daytime source and its relation to NO2, Atmos. Chem. Phys., 11, 10433–10447, http://dx.doi.org/10.5194/acp-11-10433-2011doi:10.5194/acp-11-10433-2011, 2011.

Staudt, M., Bertin, N., Frenzel, B., and Seufert, G.: Seasonal variation in amount and composition of monoterpenes emitted by young Pinus pinea trees - Implications for emission modeling, J. Atmos. Chem., 35, 77–99, http://dx.doi.org/10.1023/a:1006233010748doi:10.1023/a:1006233010748, 2000.

Yoshino, A., Sadanaga, Y., Watanabe, K., Kato, S., Miyakawa, Y., Matsumoto, J., and Kajii, Y.: Measurement of total OH reactivity by laser-induced pump and probe technique – comprehensive observations in the urban atmosphere of Tokyo, Atmos. Environ., 40, 7869–7881, 2006.