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182 Analytical Techniques for Atmospheric Measurement

DeMore, W.B., Sander, S.P., Golden, D.M. et al. (1997) Chemical kinetics and photochemical data

for use in stratospheric modelling. Eval. 11 Jet Propul. Lab., California.

Dobson, G.M.B. & Harrison, D.N. (1926) Measurements of the amount of ozone in the Earth’s

atmosphere and its relation with other geophysical conditions, Proc. R. Soc. London, 110,

660–693.

Dorn, H.P., Callies, J., Platt, U. et al. (1988) Measurement of tropospheric OH concentrations by

laser long-path absorption spectroscopy, Tellus, 40B, 437–445.

Dorn, H.P., Brandenburger, U., Brauers, T. et al. (1996) In-situ detection of tropospheric OH

radicals by folded long-path laser absorption. Results from the POPCORN field campaign in

August 1994, Geophys. Res. Lett., 23, 2537–2540.

Eisinger, M., Richter, A., Ladstatter-Weissenmayer, A. et al. (1997) DOAS zenith sky observations. 1.

BrO measurements over Bremen (53 degrees N) 1993–1994, J. Atmos. Chem., 26, 93–108.

Erle, F., Platt, U. & Pfeilsticker, K. (2000) Measurement of OBrO upper limits in the nighttime

stratosphere, Geophys. Res. Lett., 27, 2217–2220.

Ferlemann, F., Camy-Peyret, C., Fitzenberger, R. et al. (1998) Stratospheric BrO profiles measured

at different latitudes and seasons: Instrument description, spectral analysis and profile retrieval.

Geophys. Res. Lett., 25, 3847–3850.

Ferlemann, F., Bauer, N., Fitzenberger, R. et al. (2000) Differential optical absorption spectroscopy

instrument for stratospheric balloon borne trace-gas studies, Appl. Optics, 39, 2377–2386.

Fiedler, M., Frank, H., Gomer, T. et al. (1993) Ground based spectroscopic measurements of

stratospheric NO

and OClO in Arctic Winter 1989/90, Geophys. Res. Lett., 20, 963–966.

Fish, D.J. & Jones, R.L. (1995) Rotational raman-scattering and the ring effect in zenith-sky spectra,

Geophys. Res. Lett., 22, 811–814.

Fitzenberger, R., Bosch, H., Camy-Peyret, C. et al. (2000) First profile measurements of tropospheric

BrO, Geophys. Res. Lett., 27, 2921–2924.

Friess, U., Wagner, T., Pundt, I. et al. (2001) Spectroscopic measurements of tropospheric iodine

oxide at Neumayer station, Antarctica, Geophys. Res. Lett., 28, 1941–1944.

Friess, U., Hollwedel, J., Konig-Langlo, G. et al. (2004) Dynamics and chemistry of tropospheric

bromine explosion events in the Antarctic coastal region, J. Geophys. Res.-Atmos., 109, art.

no.-D06305.

Gil, M., Puentedura, O., Yela, M. et al. (1996) OClO, NO

and O

total column observations over

Iceland during the winter 1993/94, Geophys. Res. Lett., 23, 3337–3340.

Gil, M., Puentedura, O., Yela, M. et al. (2000) Behaviour of NO

and O

columns during the

eclipse of February 26, 1998, as measured by visible spectroscopy, J. Geophys. Res.-Atmos., 105,

3583–3593.

Glatthor, N., Blom, C.E., von Clarmann, T. et al. (1998) Airborne remote sensing of NO

in the

Arctic winter of 1994–1995 and comparison with a three-dimensional chemical transport model,

J. Geophys. Res.-Atmos., 103, 13 315–13 326.

Goutail, F., Pommereau, J.P., Sarkissian, A. et al. (1994) Total nitrogen dioxide at the Arctic polar

circle since 1990, Geophys. Res. Lett., 21, 1371–1374.

Grainger, J. & Ring, J. (1962) Anomalous Fraunhofer line profiles, Nature, 193, 762.

Harder, H., Camy-Peyret, C., Ferlemann, F. et al. (1998) Stratospheric BrO profiles measured at

different latitudes and seasons: Atmospheric observations, Geophys. Res. Lett., 25, 3843–3846.

Harder, H., Bosch, H., Camy-Peyret, C. et al. (2000) Comparison of measured and modeled

stratospheric BrO: Implications for the total amount of stratospheric bromine, Geophys. Res.

Lett., 27, 3695–3698.

Harrison, A.W. (1979) Midsummer stratospheric NO

at latitude 45 Degrees S, Can. J. Phys., 57,

1110–1117.

Hashmonay, R.A., Yost, M.G. & Wu, C.F. (1999) Computed tomography of air pollutants using

radial scanning path-integrated optical remote sensing, Atmos. Environ., 33, 267–274.

UV-Visible Differential Optical Absorption Spectroscopy 183

Hausmann, M. & Platt, U. (1994) Spectroscopic measurement of bromine oxide and ozone in the

high Arctic during Polar Sunrise Experiment 1992, J. Geophys. Res.-Atmos., 99, 25 399–25 413.

Hausmann, M., Brandenburger, U., Brauers, T. et al. (1997) Detection of tropospheric OH radicals

by long-path differential-optical-absorption spectroscopy: Experimental setup, accuracy, and

precision, J. Geophys. Res.-Atmos., 102, 16 011–16 022.

Hebestreit, K., Stutz, J., Rosen, D. et al. (1999) DOAS measurements of tropospheric bromine

oxide in mid-latitudes, Science, 283, 55–57.

Heckel, A., Richter, A., Tarsu, T. et al. (2004) MAX-DOAS measurements of formaldehyde in the

Po-Valley, Atmos. Chem. Phys. Diss., 4, 1151–1180.

Heue, K.-P., Bruns, M., Burrows, J.P. et al. (2003) Airborne multi axis DOAS measurements during

the SCIAVALUES and FORMAT campaigns. Geophys. Res. Abs., 5, 12 405.

Hofzumahaus, A., Aschmutat, U., Brandenburger, U. et al. (1998) Intercomparison of tropospheric

OH measurements by different laser techniques during the POPCORN campaign 1994, J. Atmos.

Chem., 31, 227–246.

Honninger, G. & Platt, U. (2002) Observations of BrO and its vertical distribution during surface

ozone depletion at Alert, Atmos. Environ., 36, 2481–2489.

Honninger, G., von Friedeburg, C. & Platt, U. (2004a) Multi axis differential optical absorption

spectroscopy (MAX-DOAS), Atmos. Chem. Phys., 4, 231–254.

Honninger, G., Bobrowski, N., Palenque, E.R. et al. (2004b) Reactive bromine and sulphur emissions

at Salar de Uyuni, Bolivia, Geophys. Res. Lett., 31, art. no.-L04101.

Honninger, G., Leser, H., Sebastian, O. et al. (2004c) Ground-based measurements of halogen

oxides at the Hudson Bay by active long-path DOAS and passive MAX-DOAS, Geophys. Res.

Lett., 31, art. no.-L04111.

Kattawar, G.W., Young, A.T. & Humphreys, T.J. (1981) Inelastic-scattering in planetary-

atmospheres. 1. The ring effect, without Aerosols, Astrophys. J., 243, 1049–1057.

King, M.D., Dick, E.M. & Simpson, W.R. (2000) A new method for the atmospheric detection of

the nitrate radical NO

, Atmos. Environ., 34, 685–688.

Kourtidis, K., Ziomas, I., Zerefos, C. et al. (2000) Benzene and toluene levels measured with a

commercial DOAS system in Thessaloniki, Greece, Atmos. Environ., 34, 1471–1480.

Kreher, K., Johnston, P.V., Wood, S.W. et al. (1997) Ground-based measurements of tropospheric

and stratospheric BrO at Arrival Heights, Antarctica, Geophys. Res. Lett., 24, 3021–3024.

Laepple, T., Knab, V., Mettendorf, K. et al. (2004) Longpath DOAS tomography on a motorway

exhaust gas plume: Numerical studies and application to data from the BAB II campaign, Atmos.

Chem. Phys. Discuss., 4, 2435–2484.

Leser, H., Honninger, G. & Platt, U. (2003) MAX-DOAS measurements of BrO and NO

in the

marine boundary layer, Geophys. Res. Lett., 30, art. no.-1537.

Liley, J.B., Johnston, P.V., McKenzie, R.L. et al. (2000) Stratospheric NO

variations from a long

time series at Lauder, New Zealand, J. Geophys. Res.-Atmos., 105, 11 633–11 640.

Lumpe, J.D., Fromm, M., Hoppel, K. et al. (2002) Comparison of POAM III ozone measurements

with correlative aircraft and balloon data during SOLVE, J. Geophys. Res.-Atmos., 108, art.

no.-8316.

Ma, L.S., Ye, J., Dube, P. et al. (1999) Ultrasensitive frequency-modulation spectroscopy enhanced

by a high-finesse optical cavity: Theory, and application to overtone transitions of C

and

HD, J. Opt. Soc. Am. B, 16, 2255–2268.

McFiggans, G., Plane, J.M.C., Allan, B.J. et al. (2000) A modelling study of iodine chemistry in the

marine boundary layer, J. Geophys. Res.-Atmos., 105, 14 371–14 385.

Marquard, L.C., Wagner, T. & Platt, U. (2000) Improved air mass factor concepts for scattered

radiation differential optical absorption spectroscopy of atmospheric species, J. Geophys. Res.-

Atmos., 105, 1315–1327.

Mazurenka, M.I., Fawcett, B.L., Elks, J.M.F. et al. (2003) 410 nm diode laser cavity ring-down

spectroscopy for trace detection of NO

, Chem. Phys. Lett., 367, 1–9.

184 Analytical Techniques for Atmospheric Measurement

McElroy, C.T., McLinden, C.A. & McConnell, J.C. (1999) Evidence for bromine monoxide in the

free troposphere during the Arctic polar sunrise, Nature, 397, 338–341.

McKenzie, R.L. & Johnston, P.V. (1982) Seasonal variations in stratospheric NO

at 45 Degrees S,

Geophys. Res. Lett., 9, 1255–1258.

McKenzie, R.L. & Johnston, P.V. (1983) Stratospheric ozone observations simultaneous with NO

at 45 Degrees S, Geophys. Res. Lett., 10, 337–340.

McKenzie, R.L. & Johnston, P.V. (1984) Springtime stratospheric NO

in Antarctica, Geophys. Res.

Lett., 11, 73–75.

Mount, G.H., Solomon, S., Sanders, R.W. et al. (1988) Observations of stratospheric NO

and O

at Thule, Greenland, Science, 242, 555–558.

Mount, G.H. (1992) The measurement of tropospheric OH by long path absorption. 1. Instrumen-

tation, J. Geophys. Res.-Atmos., 97, 2427–2444.

Mount, G.H., Brault, J.W., Johnston, P.V. et al. (1997) Measurement of tropospheric OH by

long-path laser absorption at Fritz Peak Observatory, Colorado, during the OH Photochemistry

Experiment, Fall 1993, J. Geophys. Res.-Atmos., 102, 6393–6413.

Nakano, Y., Enami, S., Nakamichi, S. et al. (2003) Temperature and pressure dependence study

of the reaction of IO radicals with dimethyl sulfide by cavity ring-down laser spectroscopy,

J. Phys. Chem. A, 107, 6381–6387.

Newman, S.M., Howie, W.H., Lane, I.C. et al. (1998) Predissociation of the A



3/2

state of IO

studied by cavity ring-down spectroscopy, J. Chem. Soc.-Faraday Trans., 94, 2681–2688.

Newman, S.M., Lane, I.C., Orr-Ewing, A.J. et al. (1999) Integrated absorption intensity and Einstein

coefficients for the O



-X



−

(0,0) transition: A comparison of cavity ringdown and high

resolution Fourier transform spectroscopy with a long-path absorption cell, J. Chem. Phys., 110,

10749–10757.

Noxon, J.F. (1975) Nitrogen dioxide in stratosphere and troposphere measured by ground-based

absorption spectroscopy, Science, 189, 547–549.

Noxon, J.F. (1976) Atmospheric nitrogen fixation by lightning, Geophys. Res. Lett., 3, 463–465.

Noxon, J.F., Norton, R.B. & Henderson, W.R. (1978) Observation of atmospheric NO

, Geophys.

Res. Lett., 5, 675–678.

Noxon, J.F., Whipple, E.C. & Hyde, R.S. (1979) Stratospheric NO

. 1. Observational method and

behaviour at mid-latitude, J. Geophys. Res.-Oceans and Atmos., 84, 5047–5065.

Noxon, J.F., Norton, R.B. & Marovich, E. (1980) NO

in the troposphere, Geophys. Res. Lett.,7,

125–128.

Noxon, J.F. (1981) NOx in the mid-Pacific troposphere, Geophys. Res. Lett., 8, 1223–1226.

Noxon, J.F. (1983) NO

and NO

in the mid-Pacific troposphere, J. Geophys. Res.-Oceans and

Atmos., 88, 1017–1021.

Okabe, H. (1978) Photochemistry of Small Molecules, Wiley-Interscience, New York.

O’Keefe, A. & Deacon, D.A.G. (1988) Cavity ringdown optical spectrometer for absorption –

Measurements using pulsed laser sources, Rev. Sci. Instrum., 59, 2544–2551.

Paul, J.B. & Saykally, R.J. (1997) Cavity ringdown laser absorption spectroscopy, Anal. Chem., 69,

A287–A292.

Perliski, L.M. & Solomon, S. (1993) On the Evaluation of air mass factors for atmospheric near-

ultraviolet and visible absorption spectroscopy, J. Geophys. Res.-Atmos., 98, 10 363–10 374.

Perner, D. & Platt, U. (1979) Detection of nitrous acid in the atmosphere by differential optical

absorption, Geophys. Res. Lett., 6, 917–920.

Perner, D., Platt, U., Trainer, M. et al. (1987) Measurements of tropospheric OH concentrations –

A comparison of field data with model predictions, J. Atmos. Chem., 5, 185–216.

Perner, D., Klupfel, T., Parchatka, U. et al. (1991) Ground-Based Uv-Vis Spectroscopy – Diurnal

OClO profiles during January 1990 above Sondre-Stromfjord, Greenland, Geophys. Res. Lett.,

18, 787–790.

UV-Visible Differential Optical Absorption Spectroscopy 185

Perner, D., Roth, A. & Klupfel, T. (1994) Ground-based measurements of stratospheric OClO,

, and O

at Sondre-Stromfjord in Winter 1991/92. Geophys. Res. Lett., 21, 1367–1370.

Petritoli, A., Ravegnani, F., Giovanelli, G. et al. (2002) Off-axis measurements of atmospheric, trace

gases by use of an airborne ultraviolet-visible spectrometer, Appl. Optics, 41, 5593–5599.

Pfeilsticker, K. & Platt, U. (1994) Airborne measurements during the Arctic Stratospheric Exper-

iment – Observation of O

and NO

, Geophys. Res. Lett., 21, 1375–1378.

Pfeilsticker, K., Bosch, H., Camy-Peyret, C. et al. (2001) First atmospheric profile measurements of

UV/visible O

absorption band intensities: Implications for the spectroscopy, and the formation

enthalpy of the O

-O

dimer, Geophys. Res. Lett., 28, 4595–4598.

Plane, J.M.C. & Nien, C.F. (1992) Differential optical absorption spectrometer for measuring

atmospheric trace gases, Rev. Sci. Instrum., 63, 1867–1876.

Plane, J.M.C. & Smith, N. (1995) Atmospheric monitoring by differential optical absorption

spectroscopy, in Clark, R.J.H. & Hester, R.E. (eds), Spectrosc. Environ. Sci., John Wiley, London,

pp. 223–262.

Platt, U., Perner, D. & Patz, H.W. (1979) Simultaneous measurement of atmospheric CH

O, O

and NO

by differential optical absorption, J. Geophys. Res.-Oceans and Atmos., 84, 6329–6335.

Platt, U. & Perner, D. (1980) Direct measurements of atmospheric CH

O, HNO

,NO

, and SO

by differential optical absorption in the near UV, J. Geophys. Res.-Oceans Atmos., 85, 7453–7458.

Platt, U., Perner, D., Harris, G.W. et al. (1980a) Observations of nitrous acid in an urban atmosphere

by differential optical absorption, Nature, 285, 312–314.

Platt, U., Perner, D., Winer, A.M. et al. (1980b) Detection of NO

in the polluted troposphere by

differential optical absorption, Geophys. Res. Lett., 7, 89–92.

Platt, U. & Perner, D. (1983) in Killinger, D.K. & Mooradian, A. (eds), Optical and remote sensing,

Springer-Verlag, Berlin, pp. 97–105.

Platt, U. (1991) Spectroscopic measurement of free radicals (OH, NO

) in the atmosphere, Fresenius

J. Anal. Chem., 340, 633–637.

Platt, U., (1994) Differential optical absorption spectroscopy (DOAS), in Sigrist, M.W. (ed.), Air

monitoring by spectroscopy techniques, John Wiley, London, pp. 27–83.

Platt, U., Marquard, L., Wagner, T. et al. (1997) Corrections for zenith scattered light DOAS,

Geophys. Res. Lett., 24, 1759–1762.

Pommereau, J.P. & Goutail, F. (1988) O

and NO

ground-based measurements by visible

spectrometry during Arctic winter and spring 1988, Geophys. Res. Lett., 15, 891–894.

Pommereau, J.P. & Piquard, J. (1994) Observations of the vertical distribution of stratospheric

OClO, Geophys. Res. Lett., 21, 1231–1234.

Press, W.H., Flannery, T.S. & Vetterlinng, W.T. (1986) Numerical recipes: The art of scientific

computing, University Press, Cambridge.

Preston, K.E., Fish, D.J., Roscoe, H.K. et al. (1998) Accurate derivation of total and stratospheric

vertical columns of NO

from ground-based zenith-sky measurements, J. Atmos. Chem., 30,

163–172.

Price, P.N. (1999) Pollutant tomography using integrated concentration data from non-intersecting

optical paths, Atmos. Environ., 33, 275–280.

Pundt, I., Pommereau, J.P., Phillips, C. et al. (1998) Upper limit of iodine oxide in the lower

stratosphere, J. Atmos. Chem., 30, 173–185.

Pundt, I., Pommereau, J.P., Chipperfield, M.P. et al. (2002) Climatology of the stratospheric BrO

vertical distribution by balloon-borne UV-visible spectrometry, J. Geophys. Res.-Atmos., 107,

art. no.-4806.

Pundt, I., Mettendorf, K.-U., Laepple, T. et al. (2005) Measurements of trace gas distributions by

long-path DOAS-Tomography: 2D mapping of NO

during the motorway campaign BAB II,

Atmos. Environ., 39, 967–975.

186 Analytical Techniques for Atmospheric Measurement

Richter, A., Eisinger, M., Ladstatter-Weissenmayer, A. et al. (1999) DOAS Zenith sky observations: 2.

Seasonal variation of BrO over Bremen (53 degrees N) 1994–1995, J. Atmos. Chem., 32, 83–99.

Rodgers, C.D. (1976) Retrieval of atmospheric temperature and composition from remote measure-

ments of thermal radiation, Rev. Geophys., 14, 609–624.

Rodgers, C.D. (1990) Characterization and error analysis of profiles retrieved from remote sounding

measurements, J. Geophys. Res.-Atmos., 95, 5587–5595.

Roscoe, H.K., Kerridge, B.J., Pollitt, S. et al. (1990) Intercomparison of remote measurements of

stratospheric NO and NO

, J. Atmos. Chem., 10, 111–144.

Roscoe, H.K., Johnston, P.V., Van Roozendael, M. et al. (1999) Slant column measurements of

and NO

during the NDSC intercomparison of zenith-sky UV-visible spectrometers in June

1996, J. Atmos. Chem., 32, 281–314.

Rothman, L.S., Barbe, A., Benner, D.C. et al. (2003) The HITRAN molecular spectroscopic database:

Edition of 2000 including updates through 2001, J. Quant. Spectrosc. Radiat. Transf., 82, 5–44.

Saiz-Lopez, A. & Plane, J.M.C. (2004) Novel iodine chemistry in the marine boundary layer,

Geophys. Res. Lett., 31, art. no.-L04112.

Saiz-Lopez, A., Plane, J.M.C. & Shillito, J.A. (2004) Bromine oxide in the mid-latitude marine

boundary layer, Geophys. Res. Lett., 31, art. no.-L03111.

Sander, S.P. & Friedl, R.R. (1989) Kinetics and product studies of the reaction ClO + BrO using

flash photolysis ultraviolet absorption, J. Phys. Chem., 93, 4764–4771.

Sanders, R.W., Solomon, S., Mount, G.H. et al. (1987) Visible spectroscopy at McMurdo Station,

Antarctica. 3. Observations of NO

, J. Geophys. Res.-Atmos., 92, 8339–8342.

Sanders, R.W., Solomon, S., Smith, J.P. et al. (1993) Visible and near-ultraviolet spectroscopy at

McMurdo Station, Antarctica. 9. Observations of OClO from April to October 1991, J. Geophys.

Res.-Atmos., 98, 7219–7228.

Sarkissian, A., Vaughan, G., Roscoe, H.K. et al. (1997) Accuracy of measurements of total ozone by

a SAOZ ground-based zenith sky visible spectrometer, J. Geophys. Res.-Atmos., 102, 1379–1390.

Scherer, J.J., Paul, J.B., O’Keefe, A. et al. (1997) Cavity ringdown laser absorption spectroscopy:

History, development, and application to pulsed molecular beams. Chem. Rev., 97, 25–51.

Schiller, C., Wahner, A., Platt, U. et al. (1990) Near UV atmospheric absorption–Measurements of

column abundances during Airborne Arctic Stratospheric Expedition, January–February 1989.

2. OClO observations, Geophys. Res. Lett., 17, 501–504.

Schulz, K.J. & Simpson, W.R. (1998) Frequency-matched cavity ring-down spectroscopy, Chem.

Phys. Lett., 297, 523–529.

Simpson, W.R. (2003) Continuous wave cavity ring-down spectroscopy applied to in situ detection

of dinitrogen pentoxide N

, Rev. Sci. Instrum., 74, 3442–3452.

Sioris, C.E. & Evans, W.F.J. (1999) Filling in of Fraunhofer and gas-absorption lines in sky spectra

as caused by rotational Raman scattering, Appl. Optics, 38, 2706–2713.

Smith, J.P. & Solomon, S. (1990) Atmospheric NO

. 3. Sunrise disappearance and the stratospheric

profile. J. Geophys. Res.-Atmos., 95, 13 819–13 827.

Smith, J.P., Solomon, S., Sanders, R.W. et al. (1993) Atmospheric NO

. 4. Vertical profiles at

middle and polar latitudes at sunrise, J. Geophys. Res.-Atmos., 98, 8983–8989.

Smith, N., Plane, J.M.C., Nien, C.F. et al. (1995) Nighttime radical chemistry in the San-Joaquin

Valley, Atmos. Environ., 29, 2887–2897.

Solomon, S., Schmeltekopf, A.L. & Sanders, R.W. (1987a) On the interpretation of zenith sky

absorption measurements, J. Geophys. Res.-Atmos., 92, 8311–8319.

Solomon, S., Mount, G.H., Sanders, R.W. et al. (1987b) Visible spectroscopy at McMurdo-Station,

Antarctica. 2. observations of OClO, J. Geophys. Res.-Atmos., 92, 8329–8338.

Solomon, S., Miller, H.L., Smith, J.P. et al. (1989a) Atmospheric NO

. 1. Measurement technique

and the annual cycle at 40-Degrees-N, J. Geophys. Res.-Atmos., 94, 11 041–11 048.

UV-Visible Differential Optical Absorption Spectroscopy 187

Solomon, S., Sanders, R.W., Mount, G.H. et al. (1989b) Atmospheric NO

. 2. Observations in polar

regions, J. Geophys. Res.-Atmos., 94, 16 423–16 427.

Stutz, J. & Platt, U. (1996) Numerical analysis and estimation of the statistical error of differential

optical absorption spectroscopy measurements with least-squares methods, Appl. Optics, 35,

6041–6053.

Stutz, J. & Platt, U. (1997) Improving long-path differential optical absorption spectroscopy with

a quartz-fiber mode mixer, Appl. Optics, 36, 1105–1115.

Stutz, J., Ackermann, R., Fast, J.D. et al. (2002) Atmospheric reactive chlorine and bromine at the

Great Salt Lake, Utah, Geophys. Res. Lett., 29, art. no.-1380.

Syed, M.Q. & Harrison, A.W. (1980) Ground based observations of stratospheric nitrogen dioxide,

Can. J. Phys., 58, 788–802.

Tuckermann, M., Ackermann, R., Golz, C. et al. (1997) DOAS-observation of halogen radical-

catalysed arctic boundary layer ozone destruction during the ARCTOC-campaigns 1995 and

1996 in Ny-Alesund, Spitsbergen, Tellus Ser. B-Chem. Phys. Meteorol., 49, 533–555.

Vanroozendael, M., Fayt, C., Bolsee, D. et al. (1994) Ground-based stratospheric NO

monitoring

at Keflavik (Iceland) during EASOE, Geophys. Res. Lett., 21, 1379–1382.

VanRoozendael, M., DeMaziere, M., Hermans, C. et al. (1997) Ground-based observations of

stratospheric NO

at high and mid-latitudes in Europe after the Mount Pinatubo eruption,

J. Geophys. Res.-Atmos., 102, 19 171–19 176.

Vaughan, G., Roscoe, H.K., Bartlett, L.M. et al. (1997) An intercomparison of ground-based UV-

visible sensors of ozone and NO

, J. Geophys. Res.-Atmos., 102, 1411–1422.

von Friedeburg, C., Wagner, T., Geyer, A. et al. (2002) Derivation of tropospheric NO

profiles

using off-axis differential optical absorption spectroscopy measurements during sunrise and

comparison with simulations, J. Geophys. Res.-Atmos., 107, art. no.-4168.

Vountas, M., Rozanov, V.V. & Burrows, J.P. (1998) Ring effect: Impact of rotational Raman

scattering on radiative transfer in earth’s atmosphere, J. Quant. Spectrosc. Radiat. Transf., 60,

943–961.

Wagner, T., Otten, C., Pfeilsticker, K. et al. (2000) DOAS moonlight observation of atmospheric

in the Arctic winter, Geophys. Res. Lett., 27, 3441–3444.

Wagner, T., von Friedeburg, C., Wenig, M. et al. (2002) UV-visible observations of atmospheric

O-4 absorptions using direct moonlight and zenith-scattered sunlight for clear-sky and cloudy

sky conditions, J. Geophys. Res.-Atmos., 107, art. no.-4424.

Wahner, A., Ravishankara, A.R., Sander, S.P. et al. (1988) Absorption cross-section of BrO between

312 and 385 nm at 298 and 223 K, Chem. Phys. Lett., 152, 507–512.

Wahner, A., Jakoubek, R.O., Mount, G.H. et al. (1989) Remote sensing observations of daytime

column NO

during the Airborne Antarctic Ozone Experiment, August 22 to October 2, 1987,

J. Geophys. Res.-Atmos., 94, 16 619–16 632.

Wahner, A., Callies, J., Dorn, H.P. et al. (1990a) Near UV atmospheric absorption measurements of

column abundances during airborne Arctic Stratospheric Expedition, January–February 1989.

1. Technique and NO

observations, Geophys. Res. Lett., 17, 497–500.

Wahner, A., Callies, J., Dorn, H.P. et al. (1990b) Near UV atmospheric absorption measurements of

column abundances during Airborne Arctic Stratospheric Expedition, January–February 1989.

3. BrO observations, Geophys. Res. Lett., 17, 517–520.

Wang, P., Bruns, M., Richter, A. et al. (2003) Validation of SCHIAMACHY with AMAX-DOAS

measurements from the DLR Falcon, Geophys. Res. Abs., 5, 9341.

Weaver, A., Solomon, S., Sanders, R.W. et al. (1996) Atmospheric NO

. 5. Off-axis measure-

ments at sunrise: Estimates of tropospheric NO

at 40 degrees N, J. Geophys. Res.-Atmos., 101,

18 605–18 612.

Wheeler, M.D., Newman, S.M., Ishiwata, T. et al. (1998) Cavity ring-down spectroscopy of the



3/2

-X



3/2

transition of BrO, Chem. Phys. Lett., 285, 346–351.

188 Analytical Techniques for Atmospheric Measurement

Wittrock, F., Muller, R., Richter, A. et al. (2000) Measurements of iodine monoxide (IO) above

Spitsbergen, Geophys. Res. Lett., 27, 1471–1474.

Wittrock, F., Oetjen, H., Richter, A. et al. (2004) MAX-DOAS measurements of atmospheric trace

gases in Ny-Alesund, Atmos. Chem. Phys. Diss., 3, 6109–6145.

Xie, P., Liu, W., Fu, Q. et al. (2004) Intercomparison of NOx, SO

, and aromatic hydrocarbons

measured by a commercial DOAS system and traditional point monitoring techniques, Adv.

Atmos. Sci., 21, 211–219.

Ye, J., Ma. L.S. & Hall, J.L. (1998) Ultrasensitive detections in atomic and molecular physics:

Demonstrations in molecular overtone spectroscopy, J. Opt. Soc. Am. B, 15, 6–15.

Yokelson, R.J., Burkholder, J.B., Fox, R.W. et al. (1994) Temperature dependence of the NO

absorption-spectrum, J. Phys. Chem., 98, 13 144–13 150.

Zhu, L. & Johnston, G. (1995) Kinetics and products of the reaction of the vinoxy radical with O

J. Phys. Chem., 99, 15 114–15 119.

Chapter 4

Fluorescence Methods

Ezra C. Wood and Ronald C. Cohen

4.1 Introduction

Fluorescence is among the most sensitive analytical tools and consequently is applied

widely in chemistry, physics, biology, and Earth and atmospheric sciences. The high

sensitivity derives from the ability to configure fluorescence instruments so that they

have high efficiency for detecting photons emitted by the molecule of interest and

simultaneously a zero or near zero background signal. Fluorescence experiments have

become more widely available and are applied in a broader range of applications as

laser excitation sources, detectors and optical filters have become more reliable and less

expensive. The decreases in size, weight and power consumption of laser sources are

continuing to fuel the evolution of instrument design.

Fluorescence has been applied to measurements of atmospheric trace gases such

as OH, NO, NO

, Cl, Br, CO, PAHs and other molecules. Perhaps the most famous

example is the anti-correlation of ClO with O

measured in the Antarctic vortex during

the austral spring of 1987 (Anderson et al., 1989), which strongly confirmed the role

of chlorofluorocarbon (CFC) emissions in the chemistry of the ozone hole (Anderson

et al., 1991). Fluorescence measurements of OH, HO

, ClO, BrO, NO and NO

were

used to quantify the rate of stratospheric ozone removal in unprecedented detail in

1992 (Wennberg et al., 1994b). These observations showed that, in contrast to previous

modeling, the catalytic cycles involving the hydrogen oxides accounted for up to 50% of

the total photochemical ozone loss at an altitude of 20 km.

In the troposphere, fluorescence measurements of OH have confirmed that our under-

standing of the sources and sinks of the Earth’s major oxidant is approximately correct in

a wide range of environs. Measurements of the OH lifetime have indicated the existence

of unmeasured biogenic volatile organic compounds (VOCs) (Di Carlo et al., 2004).

A more quantitative description of OH and other HO

compounds remains actively

sought after.

Fluorescence has long been used to observe NO via its chemiluminescent reaction with

ozone (Chapter 7). The application of this technique to the measurement of NO

has

made indirect detection of a wide suite of nitrogen oxides possible, resolving the identity

of the ‘missing NO

’ and leading to new insights into the chemistry of organic nitrates

(Day et al., 2002, 2003).

190 Analytical Techniques for Atmospheric Measurement

In this chapter, we describe the fundamental principles that guide the development

of instrumentation for detection of these species, emphasizing the common themes and

areas where the application requires deviation from these commonalities. Useful scientific

applications require instruments to be both highly sensitive and capable of demon-

strating specificity, so that false signals from other species present in the atmosphere

during a measurement are negligible or easily quantified. It is also crucial to have a

calibration strategy that is accurate, precise over long time periods and transferable. In

Sections 4.3–4.5 we review applications to specific molecules with attention to the above

design criteria. Both direct detection methods and indirect strategies involving conversion

of certain molecules (e.g. HO

or HNO

) to those that can be detected by fluorescence

techniques (e.g. OH or NO

) are discussed. We conclude this chapter with an outlook

on future progress.

4.2 Basic aspects of ﬂuorescence measurements

4.2.1 Molecular and atomic photophysics

Fluorescence is the spontaneous emission of light resulting from the relaxation of an atom

or molecule from an excited state to a lower state. Most atoms and small molecules

absorb strongly in the ultraviolet (UV) region of the electromagnetic spectrum, corre-

sponding to the energy gap between bound electronic states. These absorption spectra

and subsequent fluorescence are unique and are generally characterized by a number

of discrete peaks, which provide a convenient means by which measurements can be

tailored to individual compounds. Although some large molecules exhibit fluorescence

(e.g. naphthalene, synthetic dye molecules, tryptophan), in general, fluorescence is less

efficient for larger compounds because quenching and internal conversion are competitive

with emission.

Figure 4.1 depicts the major photophysical processes for a diatomic molecule such as

OH. The solid arrow depicts excitation from the ground electronic state,

X, to the first

electronically excited state,

A. The molecule can lose this electronic energy by fluorescence

or by quenching. The wavy arrow depicts fluorescence and the corresponding transition

to a vibrational level on the ground potential energy curve. The energy can also be

‘quenched’ by collisions with bath molecules (M), most commonly nitrogen and oxygen,

as depicted by the dashed arrow. Quenching removes energy and converts it to thermal

motion or internal excitation of a non-fluorescent species. In some cases only vibrational

energy is removed and the molecule remains on potential energy surface

A (not depicted

in Figure 4.1). Emission that follows vibrational quenching in the

A state or whose final

destination is a vibrationally excited state of the

X state is red-shifted from the excitation

wavelength.

In addition to quenching, which suppresses fluorescence, the electronically excited

molecule may undergo the collisionless processes of internal conversion, intersystem

crossing or dissociation. In internal conversion, the energy of the excited electronic

state is converted to rotational and vibrational energy of the ground electronic state.

An intersystem crossing occurs when the molecule switches to an isoenergetic state of

different spin multiplicity. Finally, the molecule can dissociate if it enters an unbound

Fluorescence Methods 191

Figure 4.1 Schematic diagram of the potential energy curves of a diatomic molecule such as OH.

Excitation, emission (ﬂuorescence), and quenching are represented by the solid, wavy, and dashed arrows,

respectively.

(repulsive) state either by direct excitation or after conversion from a bound excited

state (predissociation). Following excitation of an ensemble of molecules, the population

of the excited state will decay exponentially with a characteristic lifetime , defined as



−1

= 

−1

+

−1

+

−1

+

−1

ISC

+

−1

DIS

where the terms on the right hand side are the rate

constants for decay of the excited state due to emission, quenching, internal conversion,

intersystem crossing and predissociation, respectively. The value of 

depends on the

strength of the transition.

4.2.2 The ﬂuorescence signal

The fluorescence signal S (photon counts/s) is governed by the equation

S = RQC (4.1)

where R is the excitation rate, Q is the fluorescence quantum yield, and C is the collection

efficiency of the instrument. The excitation rate is

R = E



1 −exp−cl



 T Pd



(4.2)