Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 6 9 2006 10.5194/acp-6-2711-2006 http://www.atmos-chem-phys.net/6/2711/2006/ http://www.atmos-chem-phys.net/6/2711/2006/acp-6-2711-2006.html http://www.atmos-chem-phys.net/6/2711/2006/acp-6-2711-2006.pdf 2711 2726 2006-07-06 Ambient formaldehyde measurements made at a remote marine boundary layer site during the NAMBLEX campaign – a comparison of data from chromatographic and modified Hantzsch techniques T. J. Still S. Al-Haider P. W. Seakins p.w.seakins@chem.leeds.ac.uk R. Sommariva J. C. Stanton G. Mills S. A. Penkett School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK School of Environmental Sciences, University of East Anglia, Norwich, NR4 7TJ, UK Ambient formaldehyde concentrations are reported from the North Atlantic Marine Boundary Layer Experiment (NAMBLEX) campaign at Mace Head on the west coast of Eire during August 2002. The results from two techniques, using direct determination via gas chromatography and the Hantzsch technique, show similar trends but a significant off set in concentrations. For westerly air flows characteristic of the marine boundary layer, formaldehyde concentrations from the gas chromatographic and Hantzsch technique ranged from 0.78–1.15 ppb and 0.13–0.43 ppb, respectively. Possible reasons for the discrepancy have been investigated and are discussed, however, no satisfactory explanation has yet been found. In a subsequent laboratory intercomparison the two techniques were in good agreement. The observed concentrations have been compared with previous formaldehyde measurements in the North Atlantic marine boundary layer and with other measurements from the NAMBLEX campaign. The measurements from the Hantzsch technique and the GC results lie at the lower and upper ends respectively of previous measurements. In contrast to some previous measurements, both techniques show distinct diurnal profiles with day maxima and with an amplitude of approximately 0.15 ppb. Strong correlations were observed with ethanal concentrations measured during NAMBLEX and the ratio of ethanal to formaldehyde determined by the gas chromatographic technique is in good agreement with previous measurements. Some simple box modelling has been undertaken to investigate possible sources of formaldehyde. Such models are not able to predict absolute formaldehyde concentrations as they do not include transport processes, but the results show that oxygenated VOCs such as ethanal and methanol are very significant sources of formaldehyde in the air masses reaching Mace Head. Ayers, G. P., Gillett, R. W., DeServes, C., and Cox, R. A.: Formaldehyde production in clean marine air, Geophys. Res. Lett., 24, 401–404, 1997. Cardenas, L. M., Brassington, D. J., Allan, B. J., Coe, H., Alicke, B., Platt, U., Wilson, K. M., Plane, J. M. C., and Penkett, S. A.: Intercomparison of formaldehyde measurements in clean and polluted atmospheres., J. Atmos. Chem., 37, 53–80, 2000. Carslaw, N., Creasey, D. J., Heard, D. E., Jacobs, P. J., Lee, J. D., Lewis, A. C., McQuaid, J. B., Bauguitte, S., Pilling, M. J., Penkett, S. A., Monks, P. S., and Salisbury, G.: Comparisons of model concentrations of OH, HO$_2$ and RO$_2$ with measurements during EASE 97, J. Geophys. Res., 107(D14), 4190, doi:10.1029/2001JD001568, 2002. Fried, A., Crawford, J., Olsen, J., Walega, J., Potter, W., Wert, B., Jordan, C., Anderson, B., Shetter, R., Lefer, B., Blake, D. R., Blake, N. J., Meinardi, S., Heikes, B., O'Sullivan, D., Snow, J., Fuelberg, H., Kiley, C. M., Sandholm, S., Tan, D., Sachse, G. W., Singh, H. B., Faloona, I., Harward, C. N., and Carmichael, G. R.: Airbourne tuneable diode laser measurements of formaldehyde during TRACE-P. Distributions and model comparisons., J. Geophys. Res., 108(D20), 8798, doi:10.1029/2003JD003451, 2003. Fried, A., Lee, Y.-N., Frost, G., Wert, B., Henry, B., Drummond, J. R., Hubler, G., and Jobson, T.: Airborne formaldehyde measurements over the North Atlantic during the 1997 NARE campaign: Instrument comparisons and distributions., J. Geophys. Res., 107, 4039, doi:10.1029/2000JD260, 2002. Fried, A., Wang, Y., Cantrell, C., Wert, B., Walega, J., Ridley, B., Atlas, E., Shetter, R., Lefer, B., Coffey, M. T., Hannigan, J., Blake, D. R., Blake, N. J., Meinardi, S., Talbot, R., Dibb, J., Scheuer, E., Wingenter, O., Snow, J., Heikes, B., and Ehhalt, D.: Tunable diode laser measurements of formaldehyde during the TOPSE 2000 study: Distribution, trends and model comparisons, J. Geophys. Res., 108(D4), 8365, doi:10.1029/2002JD002208, 2003. Frost, G. J., Fried, A., Lee, Y.-N., Wert, B., Henry, B., Drummond, J. R., Evans, M. J., Fehsenfeld, F. C., Goldan, P. D., Holloway, J. S., Hubler, G., Jakoubek, R., Jobson, B. T., Knapp, K., Kuster, W. C., Roberts, J., Rudolph, J., Ryerson, T. B., Stohl, A., Stroud, C., Sueper, D. T., Trainer, M., and Williams, J.: Comparisons of box model calculations and measurements of formaldehyde from the 1997 North Atlantic Regional Experiment, J. Geophys. Res., 107(D8), 4060, doi:10.1029/2001JD000896, 2002. Gilpin, T., Apel, E., Fried, A., Wert, B., Calvert, J. G., Zhang, G. F., Dasgupta, P., Harder, J. W., Heikes, B., Hopkins, B., Westberg, H., Kleindienst, T., Lee, Y. N., Zhou, X. L., Lonneman, W., and Sewell, S.: Intercomparison of six ambient formaldehyde measurement techniques, J. Geophys. Res., 102(D17), 21 161–21 188, 1997. Grossmann, D., Moortgat, G. K., Kibler, M., Schlomski, S., Bachmann, K., Alicke, B., Geyer, A., Platt, U., Hammer, M.-U., Vogel, B., Mihelcic, D., Hofzumahaus, A., Holland, F., and Volz-Thomas, A.: Hydrogen peroxide, organic peroxides, carbonyl compounds and organic acids measured at Pabstthum during BERLIOZ, J. Geophys. Res., 108(D4), 8250, doi:10.1029/2001JD001096, 2003. Hak, C., Pundt, I., Trick, S., Kern, C., Platt, U., Dommen, J., Ordonez, C., Prevot, A. S. H., Junkermann, W., Astorga-Llorens, C., Larson, B. R., Mellqvist, J., Strandberg, A., Yu, Y., Galle, B., Kleffman, J., Lorzer, J. C., Braathen, G. O., and Volkamer, R.: Intercomparison of four different in-situ techniques for ambient formaldehyde measurements in urban air, Atmos. Chem. Phys., 5, 2897–2945, 2005. Harris, G. W., Klemp, D., Zenker, T., and Burrows, J. P.: Tuneable diode laser measurements of trace gases during the 1988 \textitPolarstern cruise., J. Atmos. Chem., 15, 315–326, 1992. Heard, D. E., Carpenter, L. J., Creasey, D. J., Hopkins, J. R., Lee, J. D., Lewis, A. C., Pilling, M. J., Seakins, P. W., Carslaw, N., and Emmerson, K. M.: High levels of the hydroxyl radical in the winter urban troposphere, Geophys. Res. Lett., 31(18), L18112, doi:10.1029/2004GL020544, 2004. Heard, D. E., Read, K. A., Methven, J., et al.: The North Atlantic Marine Boundary Layer Experiment (NAMBLEX), Mace Head, summer 2002, campaign overview, Atmos. Chem. Phys., 6 2241–2272, 2006. Hopkins, J. R., Lewis, A. C., and Read, K. A.: A two-column method for long-term monitoring of non-methane hydrocarbons and oxygenated volatile organic compounds, J. Environ. Monit., 5, 8–13, 2003. Hopkins, J. R., Still, T., Al-Haider, S., Fisher, I. R., Lewis, A. C., and Seakins, P. W.: A Simplified Apparatus for Ambient Formaldehyde Detection via GC-pHID, Atmos. Environ., 37, 2557–2563, 2003. Hunter, M. C., Bartle, K. D., Lewis, A. C., McQuaid, J. B., Myers, P., Seakins, P. W., and Van Tilburg, C.: The use of the Helium Ionization Detector for Gas Chromatographic Monitoring of Trace Atmospheric Components, J. High Res. Chrom., 21, 75–78, 1998. Hunter, M. C., Bartle, K. D., Seakins, P. W., and Lewis, A. C.: Direct measurement of atmospheric formaldehyde using gas chromatography-pulsed discharge ionisation detection, Analytical Communications, 36, 101–104, 1999. Jacob, D. J., Heikes, B., Fan, S. M., Logan, J. A., Mauzerall, D. L., Bradshaw, J. D., Singh, H. B., Gregory, G. L., Talbot, R., Blake, D. R., and Sachse, G. W.: Origin of ozone and NO$_\rm x$ in the tropical troposphere: A photochemical analysis of aircraft observations over the South Atlantic basin, J. Geophys. Res., 101(D19), 24 235–24 250, 1996. Lewis, A. C., Hopkins, J. R., Carpenter, L. J., Stanton, J. C., Read, K. A., and Pilling, M. J.: Sources and sinks of acetone, methanol, and acetaldehyde in North Atlantic air, Atmos. Chem. Phys., 5, 1963–1974, 2005. Liu, S. C., Trainer, M., Carrol, M. A., Hubler, G., Montzka, S. A., Norton, R. B., Ridley, B., Walega, J., Atlas, E., Heikes, B., Huebert, B. J., and Warren, W.: A study of the photochemistry and ozone budget during the Mauna Loa Observatory Photochemistry Experiment, J. Geophys. Res., 97(D10), 10 463–10 471, 1992. Norton, E. G., Vaughan, G., Methven, J., Coe, H., Brooks, D., Gallagher, M., and Longley, I.: Boundary layer structure and decoupling from synoptic scale flow during NAMBLEX, Atmos. Chem. Phys., 6, 433–445, 2006. Pope, F. D., Smith, C. A., Davis, P. R., Shallcross, D. E., Ashfold, M. N. R., and Orr-Ewing, A. J.: Photochemistry of formaldehyde under tropospheric conditions, Faraday Discuss., 130, 59–73, doi:10.1039/b419227c, 2005. Qian, H. B., Turton, D., Seakins, P. W., and Pilling, M. J.: A Laser Flash Photolysis/IR Diode Laser Absorption Study of the Reaction of Chlorine Atoms with Selected Alkanes, Int. J. Chemical Kinetics, 34, 86–94, 2002. Ramacher, B., Rudolph, J., and Koppmann, R.: Hydrocarbon measurements during tropsopheric ozone depletion events: Evidence for halogen chemistry., J. Geophys. Res., 104, 3633–3653, 1999. Saunders, S. M., Jenkin, M. E., Derwent, R. G., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3: Tropospheric degradation of non-aromatic VOC., Atmos. Chem. Phys., 3, 161–180, 2003. Seakins, P. W., Orlando, J. J., and Tyndall, G. S.: The Rate Coefficients and Fraction of Vibrationally Excited HCl from the Reactions of Chlorine Atoms with Methanol, Ethanol, Acetaldehyde and Formaldehyde., Phys. Chem. Chem. Phys., 6, 2224–2229, 2004. Solberg, S., Dye, C., Schmidbauer, N., Herzog, A., and Gehrig, R.: Carbonyls and nonmethane hydrocarbons at rural European sites from the Mediterranean to the Arctic, J. Atmos. Chem., 25, 33–66, 1996. Sommariva, R.: Understanding Field Measurements through a Master Chemical Mechanism, School of Chemistry, Leeds, University of Leeds, 2004. Sommariva, R., Haggerstone, A. L., Carpenter, L. J., Carslaw, N., Creasey, D. J., Heard, D. E., Lee, J. D., Lewis, A. C., Pilling, M. J., and Zador, J.: OH and HO$_2$ chemistry in clean marine air during SOAPEX-2, Atmos. Chem. Phys., 4, 839–856, 2004. Tanner, R. L., Zielinska, B., Uberna, E., Harsfield, G., and McNichol, A. P.: Concentrations of carbonyl compounds and the carbon isotopy of formaldehyde at a coastal site in Nova Scotia during the NARE summer intensive, J. Geophys. Res., 101(D22), 28 961–28 970, 1996. Wagner, V., Schiller, C., and Fischer, H.: Formaldehyde measurements in the marine boundary layer of the Indian Ocean during the 1999 INDOEX cruise, J. Geophys. Res., 106(D22), 28 529–28 538, 2001. Wagner, V., von Glasow, R., Fischer, H., and Crutzen, P. J.: Are formaldehyde measurements in the marine boundary layer suitable for testing the current understanding of CH$_4$ photooxidation?, J. Geophys. Res., 107(D3), 4029, doi:10.1029/2001JD000722, 2002. Weller, R., Schrems, O., Boddenberg, A., Gab, S., and Gautrois, M.: Meridional distribution of hydroperoxides and formaldehyde in the marine boundary layer of the Atlantic (48$^\circ$ N–35$^\circ$ S) measured during the Albatross campaign, J. Geophys. Res., 105, 14 401–14 412, 2000. Zhou, X. L., Lee, Y.-N., Newman, L., Chen, X. H., and Mopper, K.: Tropospheric formaldehyde concentration at the Mauna Loa observatory during MLOPEX 2, J. Geophys. Res., 101(D9), 14 711–14 719, 1996.