Atmospheric Measurement Techniques www.atmos-meas-tech.net 1867-1381 1867-8548 3 1 2010 10.5194/amt-3-91-2010 http://www.atmos-meas-tech.net/3/91/2010/ http://www.atmos-meas-tech.net/3/91/2010/amt-3-91-2010.html http://www.atmos-meas-tech.net/3/91/2010/amt-3-91-2010.pdf 91 112 2010-01-27 Field inter-comparison of eleven atmospheric ammonia measurement techniques K. von Bobrutzki C. F. Braban D. Famulari S. K. Jones T. Blackall T. E. L. Smith M. Blom H. Coe M. Gallagher M. Ghalaieny M. R. McGillen C. J. Percival J. D. Whitehead R. Ellis J. Murphy A. Mohacsi A. Pogany H. Junninen S. Rantanen M. A. Sutton E. Nemitz en@ceh.ac.uk Centre for Ecology and Hydrology (CEH) Edinburgh, Bush Estate, Penicuik, EH26 0QB, UK Leibniz-Institute for Agricultural Engineering, Potsdam, Germany Department of Geography, King's College London, London, UK Energy Research Foundation of the Netherlands, Petten, The Netherland School of Earth, Atmospheric and Environmental Science, University of Manchester, Manchester, UK Department of Chemistry, University of Toronto, Toronto, Canada Research Group on Laser Physics of the Hungarian Academy of Sciences, Budapest, Hungary Department of Optics and Quantum Electronics, University of Szeged, Szeged, Hungary Department of Physics, University of Helsinki, Helsinki, Finland Eleven instruments for the measurement of ambient concentrations of atmospheric ammonia gas (NH₃), based on eight different measurement methods were inter-compared above an intensively managed agricultural field in late summer 2008 in Southern Scotland. To test the instruments over a wide range of concentrations, the field was fertilised with urea midway through the experiment, leading to an increase in the average concentration from 10 to 100 ppbv. The instruments deployed included three wet-chemistry systems, one with offline analysis (annular rotating batch denuder, RBD) and two with online-analysis (Annular Denuder sampling with online Analysis, AMANDA; AiRRmonia), two Quantum Cascade Laser Absorption Spectrometers (a large-cell dual system; DUAL-QCLAS, and a compact system; c-QCLAS), two photo-acoustic spectrometers (WaSul-Flux; Nitrolux-100), a Cavity Ring Down Spectrosmeter (CRDS), a Chemical Ionisation Mass Spectrometer (CIMS), an ion mobility spectrometer (IMS) and an Open-Path Fourier Transform Infra-Red (OP-FTIR) Spectrometer. The instruments were compared with each other and with the average concentration of all instruments. An overall good agreement of hourly average concentrations between the instruments (<i>R</i>²&gt;0.84), was observed for NH₃ concentrations at the field of up to 120 ppbv with the slopes against the average ranging from 0.67 (DUAL-QCLAS) to 1.13 (AiRRmonia) with intercepts of &minus;0.74 ppbv (RBD) to +2.69 ppbv (CIMS). More variability was found for performance for lower concentrations (&lt;10 ppbv). Here the main factors affecting measurement precision are (a) the inlet design, (b) the state of inlet filters (where applicable), and (c) the quality of gas-phase standards (where applicable). By reference to the fast (1 Hz) instruments deployed during the study, it was possible to characterize the response times of the slower instruments. Asman, W. A. H., Sutton, M. A., and Schjorring, J. K.: Ammonia: emission, atmospheric transport and deposition, New Phytol., 139, 27–48, 1998. Bacon, T., Webber, K., and Carpio, R. A.: Contamination monitoring for ammonia, amines, and acid gases utilizing ion mobility spectroscopy (IMS), Proc. SPIE-Int. Soc. Opt. Eng., Metrology, Inspection and Process Control for Microlithography XII, ISBN~0-8194-2777-2, 3332, 550–559, 1998. Berden, G., Peeters, R., and Meijer, G.: Cavity ring-down spectroscopy: Experimental schemes and applications, Int. Rev. Phys. Chem., 19, 565–607, 2000. Blatter, A., Neftel, A., Dasgupta, P. K., and Simon, P. K.: A combined wet effluent denuder and mist chamber system for deposition measurements of NH₃, NH₄, HNO$_3^-$ and NO₃, in: Physicochemical Behaviour of Atmospheric Pollutants, edited by: Angeletti, G. and Restelli, G., European Commission, Brussels, 767–772, 1994. Breitenbach, L. P. and Shelef, M.: Development of a method for the analysis of NO₂ and NH₃ by NO$^-$ measuring instruments, J. Air Pollut. Control Assoc., 23, 128–131, 1973. Cantrell, C. A.: Technical Note: Review of methods for linear least-squares fitting of data and application to atmospheric chemistry problems, Atmos. Chem. Phys., 8, 5477–5487, 2008. Cowen, K., Summer, A. L., Dindal, A., Riggs, K., Willenberg, Z., Hatfield, J., Pfeffer, R., and Scoggin, K.: Environmental Technology Verification Report. Pranalytica, Inc. Nitrolux 1000 Ambient NH₃ Analyser, ETV, 2004. Duyzer, J. H., Verhagen, H. L. M., Weststrate, J. H., Bosveld, F. C., and Vermetten, A. W. M.: The dry deposition of ammonia onto a Douglas fir forest in the Netherlands, Atmos. Environ., 29, 1241–1253, 1994. Eden, P.: Weather log August 2008, R. Met. S., Weather, 63, 11, 322–348, doi:10.1002/wea.347, 2008. Eiceman, G. A. and Karpas, Z.: Ion Mobility Spectrometry, CRC Press, Boca Raton, FL, 1994. Erisman, J. W., Otjes, R., Hensen, A., Jongejan, P., van den Bulk, P., Khlystov, A., Moels, H., and Slanina, S.: Instrument development and application in studies and monitoring of ambient NH₃, Atmos. Environ., 35, 1913–1922, 2001. Fangmeier, A., Hadwiger-Fangmeier, A., van der Eerden, L., and Jäger, H.-J.: Effects of atmospheric ammonia on vegetation – a review, Environ. Pollut., 86, 43–82, 1994. Fehsenfeld, F. C., Huey, L. G., Leibrock, E., Dissly, R., Williams, E., Ryerson, T. B., Norton, R., Sueper, D. T., and Hartsell, B.: Results from an informal intercomparison of ammonia measurement techniques, J. Geophys. Res., 107(D24), 4812, doi: 10.1029/2001JD001327, 2002. Ferm, M.: Atmospheric ammonia and ammonium transport in Europe and critical loads: a review, Nutr. Cycl. Agroecosys., 51, 5–17, 1998. Ferm, M.: Method for determination of atmospheric NH₃, Atmos. Environ., 13, 1385–1393, 1979. Gall, R., Perner, D., and Ladstatter-Weissenmayer, A.: Simultaneous determination of NH₃, SO₂, NO and NO₂ by direct UV-absorption in ambient air, Fresen. J. Anal. Chem., 340, 646–649, 1991. Galle, B., Bergquist, B., Ferm, M., Törnquist, K., Griffith, D. W. T., Jensen, N. O., and Hansen, F.: Measurement of ammonia emissions from spreading of manure using gradient FTIR techniques, Atmos. Environ., 34, 4907–4915, 2000. Genfa, Z. and Dasgupta, P. K.: A Continuous Film-Recirculable Drop Gas-Liquid Equilibration Device. Measurement of Trace gaseous NH₃, Anal. Chem., 72, 3165–3170, 2000. Griffith, D. W. T. and Galle, B.: Flux measurements of NH₃, N₂O and CO₂ using dual beam FTIR spectroscopy and the flux-gradient technique, Atmos. Environ., 34, 1087–1098, 2000. Griffith, D. W. T.: Synthetic calibration and quantitative analysis of gas phase infrared spectra, Appl. Spectrosc., 50, 59–70, 1996. Grisar, R., Preier, H., Schmidtke, G., and Restelli, G.: Monitoring of gaseous pollutants by tunable diode lasers, EC Air pollution Report 3, CEC, Brussels, Belgium, 1987. Harren, F. J. M., Cotti, G., Oomens, J., and te Lintel Hekkert, S.: Photoacoustic Spectroscopy, in: Trace Gas Monitoring, Encyclopedia of Analytical Chemistry, edited by: Meyers, R. A., John Wiley & Sons Ltd, Chichester, 2203–2226, 2000. Hill Jr., H. H., Slems, W. F., St. Louis, R. H., and McMinn, D. G.: Ion Mobility Spectrometry, Anal. Chem., 62, 1201A–1209A, 1990. Husted, S., Hebbern, C. A., Mattsson, M., and Schjoerring, J. K.: A critical experimental evaluation of methods for determination of NH$_4^+$ in plant tissue, xylem sap and apoplastic fluid, Physiol. Plant., 109, 167–179, 2000. Janson, R., Rosman, K., Karlsson, A., and Hansson, H.-C.: Biogenic emissions and gaseous precursors to forest aerosols, Tellus, 53B, 423–440, 2001. Keuken, M. P., Schoonebeek, C. A. M., van Wensveen-Louter, A., and Slanina, J.: Simultaneous sampling of NH₃, HNO₃, HCl, SO₂ and H₂O₂ in ambient air by wet annular denuder system, Atmos. Environ., 22, 2541–2548, 1988. Kim, S., Huey, L. G., Stickel, R. E., Tanner, D. J., Crawford, J. H., Olson, J. R., Chen, G., Brune, W. H., Ren, X., Lesher, R., Wooldridge, P. J., Bertram, T. H., Perring, A., Cohen, R. C., Lefer, B. L , Shetter, R. E., Avery, M., Diskin, G., and Sokolik, I.: Measurement of HO₂NO₂ in the free troposphere during the intercontinental chemical transport experiment – North America 2004, J. Geophys. Res., 112, D12S01, doi:10.1029/2006JD007676, 2007. Krupa, S. V.: Effects of atmospheric ammonia (NH$_3)$ on terrestrial vegetation: a review, Environ. Pollut., 124, 179–221, 2003. Lammel, G.: Determination of NH₃ and nitric acid using a diffusion denuder method, Fresen. J. Anal. Chem., 340, 684–686, 1991. Langford, A. O., Goldan, P. D., and Fehsenfeld, F. C.: A Molybdenum Oxide Annular Denuder System for Gas Phase Ambient NH₃ Measurements, J. Atmos. Chem., 8, 359–376, 1989. Marcy, T. P., Gao, R. S., Northway, M. J., Popp, P. J., Stark, H., and Fahey, D. W.: Using chemical ionization mass spectrometry for detection of HNO₃, HOl, and ClONO₂ in the atmosphere, Int. J. Mass Spectrom., 243, 63–70, 2005. McManus, J. B., Nelson, D. D., Shorter, J. H., Zahniser, M. S., Mueller, A., Bonetti, Y., Beck, M., Hofstetter, D., and Faist, J.: Quantum cascade lasers for open- and closed-path measurement of trace gases, in: Diode lasers and applications in atmospheric sensing, edited by: Fried, A., Proc. SPIE 4817, 22–33, 2002. McManus, J. B., Shorter, J. H., Nelson, D. D., and Zahniser, M. S.: Sensors Compact Quantum Cascade Laser Instrument for Rapid, High Sensitivity Measurements of Trace Gases in Air, Sensors, 2007 IEEE, 1341–1344, 2007. Mennen, M. G., van Elzakker, B. G., van Putten, E. M., Uiterwijk, J. W., Regts, T. A., van Hellenmond, J., Wyer, G. P., Otjes, R. P., Verhage, A. J. L., Wouters, L. W., Heffels, C. J. G. Roemer, F. G., van den Beld, L., and Tetteroo, J. E. H.: Evaluation of automatic ammonia monitors for application in an air quality monitoring network, Atmos. Environ., 30, 3239–3256, 1996. Milford, C., Sutton, M. A., Allen, A. G., Karlsson, A., Davison, B. M., James, J. D., Rosman, K., Harrison, R. M., and Sape, J. N.: Marine and land-based influence on atmospheric ammonia and ammonium over Tenerife, Tellus B, 52, 273–289, 2000. Milford, C., Theobald, M. R., Nemitz, E., and Sutton, M.: Dynamics of NH₃ exchange in response to cutting and fertilising an intensively-managed grassland, Water, Air, Soil Pollut., 1, 167–176, 2001. Milford, C., Theobald, M. R., Nemitz, E., Hargreaves, K. J., Horvath, L., Raso, J., Dämmgen, U., Neftel, A., Jones, S. K., Hensen, A., Loubet, B., Cellier, P., and Sutton, M. A.: Ammonia fluxes in relation to cutting and fertilization of an intensively managed grassland derived from an inter-comparison of gradient measurements, Biogeosciences, 6, 819–834, 2009. Mozurkewich, M.: The Dissociation-Constant of Ammonium-Nitrate and Its Dependence on Temperature, Relative-Humidity and Particle-Size, Atmos. Environ., 27, 261–270, 1993. Myles, L., Meyers, T. P., and Robinson, L.: Atmospheric NH₃ measurement with an ion mobility spectrometer, Atmos. Environ., 40, 5745–5752, 2006. Neuman, J. A., Parrish, D. D., Trainer, M., Ryerson, T. B., Holloway, J. S., Nowak, J. B., Swanson, A., Flocke, F., Roberts, J. M., Brown, S. S., Stark, H., Sommariva, R., Stohl, A., Peltier, R., Weber, R., Wollny, A. G., Sueper, D. T., Hubler, G., and Fehsenfeld, F. C.: Reactive nitrogen transport and photochemistry in urban plumes over the North Atlantic Ocean, J. Geophys. Res., 111, D23S54, doi:10.1029/2005JD007010, 2006. Norman, M., Hansel, A., and Wisthaler, A.: O$^2+$ as reagent ion in the PTR-MS instrument: detection of gas-phase ammonia, Intern. J. Mass Spectrom., 265, 382–287, 2007. Norman, M., Spirig, C., Wolff, V., Trebs, I., Flechard, C., Wisthaler, A., Schnitzhofer, R., Hansel, A., and Neftel, A.: Intercomparison of ammonia measurement techniques at an intensively managed grassland site (Oensingen, Switzerland), Atmos. Chem. Phys., 9, 2635–2645, 2009. Nowak, J. B., Huey, L. G., Russell, A. G., Tian, D., Neuman, J. A., Orsini, D., Sjostedt, S. J., Sullivan, A. P., Tanner, D. J., Nenes, A., Edgerton, E., and Fehsenfeld, F. C.: Analysis of urban gas phase ammonia measurements from the 2002 Atlanta Aerosol Nucleation and Real-Time Characterization Experiment (ANARChE), J. Geophys. Res., 111, D17308, doi:10.1029/2006JD007113, 2006. Nowak, J. B., Neumann, J. A., Kozai, K., Huey, L. G., Tanner, D. J., Holloway, J. S., Ryerson, T. B., Frost, G. J., McKeen, S. A., and Fehsenfeld, F. C.: A chemical ionization mass spectrometry technique for airborne measurements of NH₃, J. Geophys. Res., 112, D10S02, doi:10.1029/2006JD007589, 2007. Pogány, A., Mohácsi, &#x00C1;., Varga, A., Bozóki, Z., Galbács, Z., Horváth, L., and Szabó, G.: A compact NH₃ detector with sub-ppb accuracy using near-infrared photoacoustic spectroscopy and preconcentration sampling, Environ. Sci. Technol., 43, 826–830, 2009. Pushkarsky, M. B., Webber, M. E., and Patel, C. K. N.: Ultra-sensitive ambient ammonia detection using CO₂ laser-based photoacoustic spectroscopy, Appl. Phys. B-Lasers O., 77, 381–385, 2003. Pushkarsky, M. B., Webber, M. E., Baghdassarian, O., Narasimhan, L. R., and Patel, C. K. N.: Laserbased photoacoustic ammonia sensor for industrial applications, Appl. Phys. B-Lasers O. special issue: Trends in Laser Sources, Spectroscopic Techniques and Their Applications to Trace Gas Detection, 75, 391–396, 2002. Rella, C.: Picarro's NH₃ analyzer for Ambient Air Monitoring, 6. Nationales NH₃-Treffen. Hannover, Deutschland, 19/20~November, 2008. Rothmann, L. S., Rinsland, C. P., Goldman, A., Massie, S. T., Edwards, D. P., Flaud, J. M., Perrin, A., Camy-Peyret, C., Danna, V., Mandin, J. Y., Schroeder, J., McCann, A., Gamache, R. R., Wattson, R. B., Yoshino, K., Chance, K. V., Jucks, K. W., Brown, L. R., Nemtchinov, V., and Varanasi, P.: The HITRAN molecular spectroscopic database and HAWKS (HITRAN atmospheric workstation), 1996 Ed., J. Quant. Spectrosc. Ra., 60, 665–710, 1998. Schwab, J. J., Li, Y., Bae, M.-S., Demerjian, K. L., Hou, J., Zhou, X., Jensen, B., and Pryor, S. C.: A laboratory intercomparison of real-time gaseous ammonia measurement methods, Environ. Sci. Technol., 41, 8412–8429, 2007. Shaw, W. J., Spicer, C. W., and Kenny, D. V.: Eddy correlation fluxes of trace gases using a tandem mass spectrometer, Atmos. Environ., 32, 2887–2898, 1998. Simon, P. K. and Dasgupta, P. K.: Wet effluent denuder coupled liquid/ion chromatography systems: annular and parallel plate denuders, Anal. Chem., 65, 1134–1139, 1993. Simon, P. K., Dasgupta, P. K., and Vecera, Z.: Wet effluent denuder coupled liquid/ion chromatography systems, Anal. Chem., 63, 1237–1242, 1991. Slusher, D. L., Pitteri, S. J., Haman, B. J., Tanner, D. J., and Huey, L. G.: A chemical ionization technique for measurement of pernitric acid in the upper troposphere and the polar boundary layer, Geophys. Res. Lett., 28, 3875–3878, 2001. Sunner, J., Nicol, G., and Kebarle, P.: Factors Determining Relative Sensitivity of Analytes in Positive Mode Atmospheric-Pressure Ionization Mass-Spectrometry, Anal. Chem., 60, 1300–1307, 1988. Sutton, M., Fowler, D., Burkhardt, J. K., and Milford, C.: Vegetation atmosphere exchange of ammonia: canopy cycling and the impacts of elevated nitrogen inputs, Water,Air Soil Poll., 85, 2057–2063, 1995. Sutton, M. A., Nemitz, E., Milford, C., Fowler, D., Moreno, J., San Jose, R., Wyers, G. P., Otjes, R. P., Harrison, R., Husted, S., and Schjoerring, J. K.: Micrometeorological measurement of net NH₃ fluxes over oilseed rape during two vegetation periods, Agric. For. Meteorol., 105, 351–369, 2000a. Sutton, M. A., Dragosits, U., Tang, Y. S., and Fowler D.: Ammonia emissions from non agricultural sources in the UK, Atmos. Environ., 34, 855–869, 2000b. Sutton, M. A., Tang, Y. S., Dragosits, U., Fournier, N., Dore, T., Smith, R. I., Weston K. J., and Fowler D.: A spatial analysis of atmospheric ammonia and ammonium in the UK, The Scientific World 1 (S2), 275–286, 2001. Sutton, M. A., Nemitz, E. , Erisman, J. W., Beier, C., Butterbach Bahl, K., Cellier, W. de Vries, P., Cotrufo, F., Skiba, U., Di Marco, C., Jones, S., Laville, P., Soussana, J. F., Loubet, B., Twigg, M., Famulari, D., Whitehead, J., Gallagher, M. W., Neftel, A., Flechard, C. R., Herrmann, B., Calanca, P. L., Schjoerring, J. K., Daemmgen, U., Horvath, L., Tang, Y. S., Emmett, B. A., Tietema, A., Peñuelas, J., Kesik, M., Brueggemann, N., Pilegaard, K., Vesala, T., Campbell, C. L., Olesen, J. E., Dragosits, U., Theobald, M. R., Levy, P., Mobbs, D. C., Milne, R., Viovy, N., Vuichard N., Smith, J. U., Smith, P., Bergamaschi, P., Fowler, D., and Reis, S.: Challenges in quantifying biosphere-atmosphere exchange of nitrogen species, Environ. Pollut., 150, 125–139, 2007. Thomas, R. M., Trebs, I., Otjes, R., Jongejan, P. A. C., ten Brink, H., Phillips, G., Kortner, M., Meixner, F. X., and Nemitz, E.: An automated analyzer to measure surface-atmosphere exchange fluxes of water soluble inorganic aerosol compounds and reactive trace gases, Environ. Sci. Technol., 43(5), 1412–1418, 2009. Tittel, F. K., Richter, D., and Fried, A.: Mid-infrared laser applications in spectroscopy, in: Topics in Applied Physics vol. 89, edited by: Sorokina, I. T. and Vodopyanov, K. L., Springer-Verlag, 445–516, 2003. Warland, J. S., Dias, G. M., and Thurtell, G. W.: A tunable diode laser system for ammonia flux measurement over multiple plots, Environ. Pollut., 114, 215–221, 2001. Warneck, P.: Chemistry of the Natural Atmosphere, Academic Press, New York, 1988. Wert, B. P., Fried, A., Henry, B., and Cartier, S.: Evaluation of inlets used for the airborne measurement of formaldehyde, J. Geophys. Res., 107(D13), 4163, doi:10.1029/2001JD001072, 2002. Whitehead, J. D., Longley, I. D., and Gallagher, M. W.: Seasonal and diurnal variation in atmospheric NH₃ in an urban environment measured using a quantum cascade laser absorption spectrometer, Water Air Soil Pollut., 183, 317–329, 2007. Whitehead, J. D., Twigg, M., Famulari, D., Nemitz, E., Sutton, M. A., Gallagher, M. W., and Fowler, D.: Evaluation of Laser Absorption Spectroscopic Techniques for Eddy Covariance Flux Measurements of NH₃, Environ. Sci. Technol., 42, 2041–2046, 2008. Wiebe, H. A., Anlauf, K. G., Tuazon, E. C., Winer, A. M., Biermann, H. W., Appel, B. R., Solomon, P. A., Cass, G. R., Ellestad, T. G., Knapp, K. T., Peake, E., Spicer, C. W., and Lawson, P. A.: A comparison of measurements of atmospheric ammonia by filter packs, transition-flow reactors, simple and annular denuders and Fourier-Transform Infrared-Spectroscopy, Atmos. Environ. A-Gen., 1019–1028, 1990. Williams, E. J., Sandholm, S. T., Bradshaw, J. D., Schendel, J. S., Langford, A. O., Quinn, P. K., LeBel, P. J., Vay, S. A., Roberts, P. D., Norton, R. B., Watkins, B. A., Buhr, M. P., Parrish, D. D., Calvert, J. G., and Fehsenfeld, F. C.: An intercomparison of five ammonia measurement techniques, J. Geophys. Res., 97, 591–611, 1992. Wyers, G. P., Otjes, R. P., and Slanina, J.: A continious flow denuder for the measurement of ambient concentrations and surface fluxes of NH₃, Atmos. Environ., 27A, 2085–2090, 1993. Yokelson, R. J., Christian, T. J., Bertschi, I. T., and Hao, W. M.: Evaluation of adsorption effects on measurements of ammonia, acetic acid and methanol, J. Geophys. Res., 108, 46–49, 2003.