Abstract

In this paper we report the results of a laboratory study for detecting the important atmospheric molecule HCl using a tunable diode laser coupled to a multipass White cell. In contrast to many such prototype studies, the calibration in this work was carried out near the concentration range of interest and verified using three different techniques. Employing a 40-m path length, we have demonstrated a detection limit (SNR = 1) in the 150–230 parts-per-trillion range at pressures around 9 Torr.

© 1984 Optical Society of America

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  1. C. B. Farmer, O. F. Raper, B. D. Robbins, R. A. Toth, C. Muller, “Simultaneous Spectroscopic Measurements of Stratospheric Species: O3, CH4, CO, CO2, N2O, HCl, and HF at Northern and Southern Mid-Latitudes,” J. Geophys. Res. 85, 1621 (1980).
    [CrossRef]
  2. R. Zander, “Recent Observations of HF and HCl in the Upper Stratosphere,” Geophys. Res. Lett. 8, 413 (1981).
    [CrossRef]
  3. H. L. Buijs, G. L. Vail, G. Tremblay, D. J. W. Kendall, “Simultaneous Measurement of the Volume Mixing Ratios of HCl and HF in the Stratosphere,” Geophys. Res. Lett. 7, 205 (1980).
    [CrossRef]
  4. M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).
  5. J. R. Eyre, H. K. Roscoe, “Radiometric Measurement of HCl,” Nature (London) 266, 243 (1977).
    [CrossRef]
  6. C. P. Chaloner, J. R. Drummond, J. T. Houghton, R. F. Jarnot, H. K. Roscoe, “Infra-red Measurements of Stratospheric Composition I. The Balloon Instrument and Water Vapour Measurements,” Proc. R. Soc. London Ser. A 364, 145 (1978).
    [CrossRef]
  7. A. L. Lazrus, B. W. Gandrud, J. Greenberg, J. Bonelli, E. Mroz, W. A. Sedlacek, “Mid-Latitude Seasonal Measurements of Stratospheric Acidic Chlorine Vapor,” Geophys. Res. Lett. 4, 587 (1977).
    [CrossRef]
  8. World Meteorological OrganizationGlobal Ozone Research and Monitoring Project Report No. 11, “The Stratosphere 1981 Theory And Measurements” (1981).
  9. National Research Council Report, Causes and Effects of Stratospheric Ozone Reduction: An Update (National Academy Press, Washington, D.C., 1982).
  10. J. Reid, M. El-Sherbiny, B. K. Garside, E. A. Ballik, “Sensitivity Limits of a Tunable Diode Laser Spectrometer, with Application to the Detection of NO2 at the 100-ppt Level,” Appl. Opt. 19, 3349 (1980).
    [CrossRef] [PubMed]
  11. J. Reid, B. K. Garside, J. Shewchun, M. El-Sherbiny, E. A. Ballik, “High Sensitivity Point Monitoring of Atmospheric Gases Employing Tunable Diode Lasers,” Appl. Opt. 17, 1806 (1978).
    [CrossRef] [PubMed]
  12. D. R. Hastie, G. I. Mackay, T. Iguchi, B. A. Ridley, H. I. Schiff, “Tunable Diode Laser Systems for Measuring Trace Gases in Tropospheric Air,” Environ. Sci. Technol. 17 (8), 352A (1983); Correction, Environ. Sci. Technol. 17 (11), 510A (1983).
    [PubMed]
  13. P. Pokrowsky, W. Herrmann, “Sensitive Detection of Hydrogen Chloride by Derivative Spectroscopy with a Diode Laser,” Proc. Soc. Photo-Opt. Instrum. Eng. 286, 33 (1981).
  14. To describe adequately materials and experimental procedures, it was occasionally necessary to identify commercial products by manufacturer’s name or label. In no instance does such identification imply endorsement by the National Bureau of Standards or the National Center for Atmospheric Research, nor does it imply that the particular products or equipment are necessarily the best available for the purpose.
  15. W. W. Berg, P. D. Sperry, K. A. Rahn, E. S. Gladney, “Atmospheric Bromine in the Arctic,” J. Geophys. Res. 88, 6719 (1983).
    [CrossRef]
  16. W. W. Berg, unpublished work.
  17. N. E. Holden, R. L. Martin, I. L. Barnes, “Isotopic Composition of the Elements 1981,” Pure & Appl. Chem. 55 (7), 1119 (1983).
    [CrossRef]
  18. L. S. Rothman, “AFGL Trace Gas Compilation Edition of August 1980,” AFGL Hanscom AFB, Bedford, Mass. (1980).
  19. C. Young, “Calculation of the Absorption Coefficient for Lines with Combined Doppler and Lorentz Broadening,” J. Quant. Spectrosc. Radiat. Transfer 5, 549 (1965).
    [CrossRef]
  20. L. S. Rothman et al., “AFGL Trace Gas Compilation: 1980 Version,” Appl. Opt. 20, 1323 (1981).
    [CrossRef] [PubMed]
  21. J. A. Mucha, “Correction of Nonlinear Derivative Diode Laser Data in Standard Addition Analysis,” Appl. Spectrosc. 38, 68 (1984).
    [CrossRef]
  22. D. L. Gray, A. G. Robiette, A. S. Pine, “Extended Measurement and Analysis of the V3 Infrared Band of Methane,” J. Mol. Spectrosc. 77, 440 (1979).
    [CrossRef]
  23. R. A. Toth, L. P. Brown, R. H. Hunt, L. S. Rothman, “Line Parameters of Methane from 2385 to 3200 cm−1,” Appl. Opt. 20, 932 (1981).
    [CrossRef] [PubMed]
  24. R. A. Toth, L. R. Brown, R. H. Hunt, “Line Positions and Strengths of Methane in the 2862 to 3000 cm−1 Region,” J. Mol. Spectrosc. 67, 1. (1977).
    [CrossRef]
  25. L. W. Pinkley, K. N. Rao, M. Dang-Nhu, G. Tarrago, G. Poussigue, “Forbidden Lines of the V3 Band of 13CH4: Ground-State Constants,” J. Mol. Spectrosc. 63, 402 (1976).
    [CrossRef]
  26. L. R. Brown, Jet Propulsion Laboratory; private communications based on energy level calculations using data from G. Guelachvili.
  27. J. Reid, D. Labrie, “Second-Harmonic Detection with Tunable Diode Lasers—Comparison of Experiment and Theory,” Appl. Phys. B 26, 203 (1981).
    [CrossRef]
  28. J. A. Mucha, “Standard Addition Technique for Quantitative Trace Gas Analysis Using Derivative Infrared Diode Laser Spectroscopy,” Appl. Spectrosc. 36, 393 (1982).
    [CrossRef]
  29. A. W. Miziolek, “Atmospheric Spectra and the Temperature Dependence of Collisional Cross Sections,” Geophys. Res. Lett. 6, 563 (1979).
    [CrossRef]
  30. V. Dana, J. P. Maillard, “Analysis of the V1 + V3 Band of 14N16O2,” J. Mol. Spectrosc. 71, 1 (1978).
    [CrossRef]
  31. R. A. Toth, R. H. Hunt, “Line Strengths, Spin-Splittings, and Forbidden Transitions in the (101) Band of 14N16O2,” J. Mol. Spectrosc. 79, 182 (1980).
    [CrossRef]

1984

1983

D. R. Hastie, G. I. Mackay, T. Iguchi, B. A. Ridley, H. I. Schiff, “Tunable Diode Laser Systems for Measuring Trace Gases in Tropospheric Air,” Environ. Sci. Technol. 17 (8), 352A (1983); Correction, Environ. Sci. Technol. 17 (11), 510A (1983).
[PubMed]

W. W. Berg, P. D. Sperry, K. A. Rahn, E. S. Gladney, “Atmospheric Bromine in the Arctic,” J. Geophys. Res. 88, 6719 (1983).
[CrossRef]

N. E. Holden, R. L. Martin, I. L. Barnes, “Isotopic Composition of the Elements 1981,” Pure & Appl. Chem. 55 (7), 1119 (1983).
[CrossRef]

1982

1981

L. S. Rothman et al., “AFGL Trace Gas Compilation: 1980 Version,” Appl. Opt. 20, 1323 (1981).
[CrossRef] [PubMed]

P. Pokrowsky, W. Herrmann, “Sensitive Detection of Hydrogen Chloride by Derivative Spectroscopy with a Diode Laser,” Proc. Soc. Photo-Opt. Instrum. Eng. 286, 33 (1981).

R. Zander, “Recent Observations of HF and HCl in the Upper Stratosphere,” Geophys. Res. Lett. 8, 413 (1981).
[CrossRef]

R. A. Toth, L. P. Brown, R. H. Hunt, L. S. Rothman, “Line Parameters of Methane from 2385 to 3200 cm−1,” Appl. Opt. 20, 932 (1981).
[CrossRef] [PubMed]

J. Reid, D. Labrie, “Second-Harmonic Detection with Tunable Diode Lasers—Comparison of Experiment and Theory,” Appl. Phys. B 26, 203 (1981).
[CrossRef]

1980

R. A. Toth, R. H. Hunt, “Line Strengths, Spin-Splittings, and Forbidden Transitions in the (101) Band of 14N16O2,” J. Mol. Spectrosc. 79, 182 (1980).
[CrossRef]

C. B. Farmer, O. F. Raper, B. D. Robbins, R. A. Toth, C. Muller, “Simultaneous Spectroscopic Measurements of Stratospheric Species: O3, CH4, CO, CO2, N2O, HCl, and HF at Northern and Southern Mid-Latitudes,” J. Geophys. Res. 85, 1621 (1980).
[CrossRef]

H. L. Buijs, G. L. Vail, G. Tremblay, D. J. W. Kendall, “Simultaneous Measurement of the Volume Mixing Ratios of HCl and HF in the Stratosphere,” Geophys. Res. Lett. 7, 205 (1980).
[CrossRef]

J. Reid, M. El-Sherbiny, B. K. Garside, E. A. Ballik, “Sensitivity Limits of a Tunable Diode Laser Spectrometer, with Application to the Detection of NO2 at the 100-ppt Level,” Appl. Opt. 19, 3349 (1980).
[CrossRef] [PubMed]

1979

D. L. Gray, A. G. Robiette, A. S. Pine, “Extended Measurement and Analysis of the V3 Infrared Band of Methane,” J. Mol. Spectrosc. 77, 440 (1979).
[CrossRef]

A. W. Miziolek, “Atmospheric Spectra and the Temperature Dependence of Collisional Cross Sections,” Geophys. Res. Lett. 6, 563 (1979).
[CrossRef]

1978

V. Dana, J. P. Maillard, “Analysis of the V1 + V3 Band of 14N16O2,” J. Mol. Spectrosc. 71, 1 (1978).
[CrossRef]

J. Reid, B. K. Garside, J. Shewchun, M. El-Sherbiny, E. A. Ballik, “High Sensitivity Point Monitoring of Atmospheric Gases Employing Tunable Diode Lasers,” Appl. Opt. 17, 1806 (1978).
[CrossRef] [PubMed]

C. P. Chaloner, J. R. Drummond, J. T. Houghton, R. F. Jarnot, H. K. Roscoe, “Infra-red Measurements of Stratospheric Composition I. The Balloon Instrument and Water Vapour Measurements,” Proc. R. Soc. London Ser. A 364, 145 (1978).
[CrossRef]

1977

A. L. Lazrus, B. W. Gandrud, J. Greenberg, J. Bonelli, E. Mroz, W. A. Sedlacek, “Mid-Latitude Seasonal Measurements of Stratospheric Acidic Chlorine Vapor,” Geophys. Res. Lett. 4, 587 (1977).
[CrossRef]

J. R. Eyre, H. K. Roscoe, “Radiometric Measurement of HCl,” Nature (London) 266, 243 (1977).
[CrossRef]

R. A. Toth, L. R. Brown, R. H. Hunt, “Line Positions and Strengths of Methane in the 2862 to 3000 cm−1 Region,” J. Mol. Spectrosc. 67, 1. (1977).
[CrossRef]

1976

L. W. Pinkley, K. N. Rao, M. Dang-Nhu, G. Tarrago, G. Poussigue, “Forbidden Lines of the V3 Band of 13CH4: Ground-State Constants,” J. Mol. Spectrosc. 63, 402 (1976).
[CrossRef]

1965

C. Young, “Calculation of the Absorption Coefficient for Lines with Combined Doppler and Lorentz Broadening,” J. Quant. Spectrosc. Radiat. Transfer 5, 549 (1965).
[CrossRef]

Ballik, E. A.

Bangham, M. J.

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

Barnes, I. L.

N. E. Holden, R. L. Martin, I. L. Barnes, “Isotopic Composition of the Elements 1981,” Pure & Appl. Chem. 55 (7), 1119 (1983).
[CrossRef]

Berg, W. W.

W. W. Berg, P. D. Sperry, K. A. Rahn, E. S. Gladney, “Atmospheric Bromine in the Arctic,” J. Geophys. Res. 88, 6719 (1983).
[CrossRef]

W. W. Berg, unpublished work.

Bonelli, J.

A. L. Lazrus, B. W. Gandrud, J. Greenberg, J. Bonelli, E. Mroz, W. A. Sedlacek, “Mid-Latitude Seasonal Measurements of Stratospheric Acidic Chlorine Vapor,” Geophys. Res. Lett. 4, 587 (1977).
[CrossRef]

Bonetti, A.

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

Bradsell, R. H.

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

Brown, L. P.

R. A. Toth, L. P. Brown, R. H. Hunt, L. S. Rothman, “Line Parameters of Methane from 2385 to 3200 cm−1,” Appl. Opt. 20, 932 (1981).
[CrossRef] [PubMed]

Brown, L. R.

R. A. Toth, L. R. Brown, R. H. Hunt, “Line Positions and Strengths of Methane in the 2862 to 3000 cm−1 Region,” J. Mol. Spectrosc. 67, 1. (1977).
[CrossRef]

L. R. Brown, Jet Propulsion Laboratory; private communications based on energy level calculations using data from G. Guelachvili.

Buijs, H. L.

H. L. Buijs, G. L. Vail, G. Tremblay, D. J. W. Kendall, “Simultaneous Measurement of the Volume Mixing Ratios of HCl and HF in the Stratosphere,” Geophys. Res. Lett. 7, 205 (1980).
[CrossRef]

Carli, B.

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

Chaloner, C. P.

C. P. Chaloner, J. R. Drummond, J. T. Houghton, R. F. Jarnot, H. K. Roscoe, “Infra-red Measurements of Stratospheric Composition I. The Balloon Instrument and Water Vapour Measurements,” Proc. R. Soc. London Ser. A 364, 145 (1978).
[CrossRef]

Dana, V.

V. Dana, J. P. Maillard, “Analysis of the V1 + V3 Band of 14N16O2,” J. Mol. Spectrosc. 71, 1 (1978).
[CrossRef]

Dang-Nhu, M.

L. W. Pinkley, K. N. Rao, M. Dang-Nhu, G. Tarrago, G. Poussigue, “Forbidden Lines of the V3 Band of 13CH4: Ground-State Constants,” J. Mol. Spectrosc. 63, 402 (1976).
[CrossRef]

Drummond, J. R.

C. P. Chaloner, J. R. Drummond, J. T. Houghton, R. F. Jarnot, H. K. Roscoe, “Infra-red Measurements of Stratospheric Composition I. The Balloon Instrument and Water Vapour Measurements,” Proc. R. Soc. London Ser. A 364, 145 (1978).
[CrossRef]

El-Sherbiny, M.

Eyre, J. R.

J. R. Eyre, H. K. Roscoe, “Radiometric Measurement of HCl,” Nature (London) 266, 243 (1977).
[CrossRef]

Farmer, C. B.

C. B. Farmer, O. F. Raper, B. D. Robbins, R. A. Toth, C. Muller, “Simultaneous Spectroscopic Measurements of Stratospheric Species: O3, CH4, CO, CO2, N2O, HCl, and HF at Northern and Southern Mid-Latitudes,” J. Geophys. Res. 85, 1621 (1980).
[CrossRef]

Gandrud, B. W.

A. L. Lazrus, B. W. Gandrud, J. Greenberg, J. Bonelli, E. Mroz, W. A. Sedlacek, “Mid-Latitude Seasonal Measurements of Stratospheric Acidic Chlorine Vapor,” Geophys. Res. Lett. 4, 587 (1977).
[CrossRef]

Garside, B. K.

Gladney, E. S.

W. W. Berg, P. D. Sperry, K. A. Rahn, E. S. Gladney, “Atmospheric Bromine in the Arctic,” J. Geophys. Res. 88, 6719 (1983).
[CrossRef]

Gray, D. L.

D. L. Gray, A. G. Robiette, A. S. Pine, “Extended Measurement and Analysis of the V3 Infrared Band of Methane,” J. Mol. Spectrosc. 77, 440 (1979).
[CrossRef]

Greenberg, J.

A. L. Lazrus, B. W. Gandrud, J. Greenberg, J. Bonelli, E. Mroz, W. A. Sedlacek, “Mid-Latitude Seasonal Measurements of Stratospheric Acidic Chlorine Vapor,” Geophys. Res. Lett. 4, 587 (1977).
[CrossRef]

Guelachvili, G.

L. R. Brown, Jet Propulsion Laboratory; private communications based on energy level calculations using data from G. Guelachvili.

Harries, J. G.

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

Hastie, D. R.

D. R. Hastie, G. I. Mackay, T. Iguchi, B. A. Ridley, H. I. Schiff, “Tunable Diode Laser Systems for Measuring Trace Gases in Tropospheric Air,” Environ. Sci. Technol. 17 (8), 352A (1983); Correction, Environ. Sci. Technol. 17 (11), 510A (1983).
[PubMed]

Herrmann, W.

P. Pokrowsky, W. Herrmann, “Sensitive Detection of Hydrogen Chloride by Derivative Spectroscopy with a Diode Laser,” Proc. Soc. Photo-Opt. Instrum. Eng. 286, 33 (1981).

Holden, N. E.

N. E. Holden, R. L. Martin, I. L. Barnes, “Isotopic Composition of the Elements 1981,” Pure & Appl. Chem. 55 (7), 1119 (1983).
[CrossRef]

Houghton, J. T.

C. P. Chaloner, J. R. Drummond, J. T. Houghton, R. F. Jarnot, H. K. Roscoe, “Infra-red Measurements of Stratospheric Composition I. The Balloon Instrument and Water Vapour Measurements,” Proc. R. Soc. London Ser. A 364, 145 (1978).
[CrossRef]

Hunt, R. H.

R. A. Toth, L. P. Brown, R. H. Hunt, L. S. Rothman, “Line Parameters of Methane from 2385 to 3200 cm−1,” Appl. Opt. 20, 932 (1981).
[CrossRef] [PubMed]

R. A. Toth, R. H. Hunt, “Line Strengths, Spin-Splittings, and Forbidden Transitions in the (101) Band of 14N16O2,” J. Mol. Spectrosc. 79, 182 (1980).
[CrossRef]

R. A. Toth, L. R. Brown, R. H. Hunt, “Line Positions and Strengths of Methane in the 2862 to 3000 cm−1 Region,” J. Mol. Spectrosc. 67, 1. (1977).
[CrossRef]

Iguchi, T.

D. R. Hastie, G. I. Mackay, T. Iguchi, B. A. Ridley, H. I. Schiff, “Tunable Diode Laser Systems for Measuring Trace Gases in Tropospheric Air,” Environ. Sci. Technol. 17 (8), 352A (1983); Correction, Environ. Sci. Technol. 17 (11), 510A (1983).
[PubMed]

Jarnot, R. F.

C. P. Chaloner, J. R. Drummond, J. T. Houghton, R. F. Jarnot, H. K. Roscoe, “Infra-red Measurements of Stratospheric Composition I. The Balloon Instrument and Water Vapour Measurements,” Proc. R. Soc. London Ser. A 364, 145 (1978).
[CrossRef]

Kendall, D. J. W.

H. L. Buijs, G. L. Vail, G. Tremblay, D. J. W. Kendall, “Simultaneous Measurement of the Volume Mixing Ratios of HCl and HF in the Stratosphere,” Geophys. Res. Lett. 7, 205 (1980).
[CrossRef]

Labrie, D.

J. Reid, D. Labrie, “Second-Harmonic Detection with Tunable Diode Lasers—Comparison of Experiment and Theory,” Appl. Phys. B 26, 203 (1981).
[CrossRef]

Lazrus, A. L.

A. L. Lazrus, B. W. Gandrud, J. Greenberg, J. Bonelli, E. Mroz, W. A. Sedlacek, “Mid-Latitude Seasonal Measurements of Stratospheric Acidic Chlorine Vapor,” Geophys. Res. Lett. 4, 587 (1977).
[CrossRef]

Mackay, G. I.

D. R. Hastie, G. I. Mackay, T. Iguchi, B. A. Ridley, H. I. Schiff, “Tunable Diode Laser Systems for Measuring Trace Gases in Tropospheric Air,” Environ. Sci. Technol. 17 (8), 352A (1983); Correction, Environ. Sci. Technol. 17 (11), 510A (1983).
[PubMed]

Maillard, J. P.

V. Dana, J. P. Maillard, “Analysis of the V1 + V3 Band of 14N16O2,” J. Mol. Spectrosc. 71, 1 (1978).
[CrossRef]

Martin, R. L.

N. E. Holden, R. L. Martin, I. L. Barnes, “Isotopic Composition of the Elements 1981,” Pure & Appl. Chem. 55 (7), 1119 (1983).
[CrossRef]

Mencaraglia, F.

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

Miziolek, A. W.

A. W. Miziolek, “Atmospheric Spectra and the Temperature Dependence of Collisional Cross Sections,” Geophys. Res. Lett. 6, 563 (1979).
[CrossRef]

Moss, D. G.

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

Mroz, E.

A. L. Lazrus, B. W. Gandrud, J. Greenberg, J. Bonelli, E. Mroz, W. A. Sedlacek, “Mid-Latitude Seasonal Measurements of Stratospheric Acidic Chlorine Vapor,” Geophys. Res. Lett. 4, 587 (1977).
[CrossRef]

Mucha, J. A.

Muller, C.

C. B. Farmer, O. F. Raper, B. D. Robbins, R. A. Toth, C. Muller, “Simultaneous Spectroscopic Measurements of Stratospheric Species: O3, CH4, CO, CO2, N2O, HCl, and HF at Northern and Southern Mid-Latitudes,” J. Geophys. Res. 85, 1621 (1980).
[CrossRef]

Pine, A. S.

D. L. Gray, A. G. Robiette, A. S. Pine, “Extended Measurement and Analysis of the V3 Infrared Band of Methane,” J. Mol. Spectrosc. 77, 440 (1979).
[CrossRef]

Pinkley, L. W.

L. W. Pinkley, K. N. Rao, M. Dang-Nhu, G. Tarrago, G. Poussigue, “Forbidden Lines of the V3 Band of 13CH4: Ground-State Constants,” J. Mol. Spectrosc. 63, 402 (1976).
[CrossRef]

Pokrowsky, P.

P. Pokrowsky, W. Herrmann, “Sensitive Detection of Hydrogen Chloride by Derivative Spectroscopy with a Diode Laser,” Proc. Soc. Photo-Opt. Instrum. Eng. 286, 33 (1981).

Pollitt, J.

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

Poussigue, G.

L. W. Pinkley, K. N. Rao, M. Dang-Nhu, G. Tarrago, G. Poussigue, “Forbidden Lines of the V3 Band of 13CH4: Ground-State Constants,” J. Mol. Spectrosc. 63, 402 (1976).
[CrossRef]

Rahn, K. A.

W. W. Berg, P. D. Sperry, K. A. Rahn, E. S. Gladney, “Atmospheric Bromine in the Arctic,” J. Geophys. Res. 88, 6719 (1983).
[CrossRef]

Rao, K. N.

L. W. Pinkley, K. N. Rao, M. Dang-Nhu, G. Tarrago, G. Poussigue, “Forbidden Lines of the V3 Band of 13CH4: Ground-State Constants,” J. Mol. Spectrosc. 63, 402 (1976).
[CrossRef]

Raper, O. F.

C. B. Farmer, O. F. Raper, B. D. Robbins, R. A. Toth, C. Muller, “Simultaneous Spectroscopic Measurements of Stratospheric Species: O3, CH4, CO, CO2, N2O, HCl, and HF at Northern and Southern Mid-Latitudes,” J. Geophys. Res. 85, 1621 (1980).
[CrossRef]

Reid, J.

Ridley, B. A.

D. R. Hastie, G. I. Mackay, T. Iguchi, B. A. Ridley, H. I. Schiff, “Tunable Diode Laser Systems for Measuring Trace Gases in Tropospheric Air,” Environ. Sci. Technol. 17 (8), 352A (1983); Correction, Environ. Sci. Technol. 17 (11), 510A (1983).
[PubMed]

Robbins, B. D.

C. B. Farmer, O. F. Raper, B. D. Robbins, R. A. Toth, C. Muller, “Simultaneous Spectroscopic Measurements of Stratospheric Species: O3, CH4, CO, CO2, N2O, HCl, and HF at Northern and Southern Mid-Latitudes,” J. Geophys. Res. 85, 1621 (1980).
[CrossRef]

Robiette, A. G.

D. L. Gray, A. G. Robiette, A. S. Pine, “Extended Measurement and Analysis of the V3 Infrared Band of Methane,” J. Mol. Spectrosc. 77, 440 (1979).
[CrossRef]

Roscoe, H. K.

C. P. Chaloner, J. R. Drummond, J. T. Houghton, R. F. Jarnot, H. K. Roscoe, “Infra-red Measurements of Stratospheric Composition I. The Balloon Instrument and Water Vapour Measurements,” Proc. R. Soc. London Ser. A 364, 145 (1978).
[CrossRef]

J. R. Eyre, H. K. Roscoe, “Radiometric Measurement of HCl,” Nature (London) 266, 243 (1977).
[CrossRef]

Rossi, E.

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

Rothman, L. S.

R. A. Toth, L. P. Brown, R. H. Hunt, L. S. Rothman, “Line Parameters of Methane from 2385 to 3200 cm−1,” Appl. Opt. 20, 932 (1981).
[CrossRef] [PubMed]

L. S. Rothman et al., “AFGL Trace Gas Compilation: 1980 Version,” Appl. Opt. 20, 1323 (1981).
[CrossRef] [PubMed]

L. S. Rothman, “AFGL Trace Gas Compilation Edition of August 1980,” AFGL Hanscom AFB, Bedford, Mass. (1980).

Schiff, H. I.

D. R. Hastie, G. I. Mackay, T. Iguchi, B. A. Ridley, H. I. Schiff, “Tunable Diode Laser Systems for Measuring Trace Gases in Tropospheric Air,” Environ. Sci. Technol. 17 (8), 352A (1983); Correction, Environ. Sci. Technol. 17 (11), 510A (1983).
[PubMed]

Sedlacek, W. A.

A. L. Lazrus, B. W. Gandrud, J. Greenberg, J. Bonelli, E. Mroz, W. A. Sedlacek, “Mid-Latitude Seasonal Measurements of Stratospheric Acidic Chlorine Vapor,” Geophys. Res. Lett. 4, 587 (1977).
[CrossRef]

Shewchun, J.

Sperry, P. D.

W. W. Berg, P. D. Sperry, K. A. Rahn, E. S. Gladney, “Atmospheric Bromine in the Arctic,” J. Geophys. Res. 88, 6719 (1983).
[CrossRef]

Swann, N. R.

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

Tarrago, G.

L. W. Pinkley, K. N. Rao, M. Dang-Nhu, G. Tarrago, G. Poussigue, “Forbidden Lines of the V3 Band of 13CH4: Ground-State Constants,” J. Mol. Spectrosc. 63, 402 (1976).
[CrossRef]

Toth, R. A.

R. A. Toth, L. P. Brown, R. H. Hunt, L. S. Rothman, “Line Parameters of Methane from 2385 to 3200 cm−1,” Appl. Opt. 20, 932 (1981).
[CrossRef] [PubMed]

C. B. Farmer, O. F. Raper, B. D. Robbins, R. A. Toth, C. Muller, “Simultaneous Spectroscopic Measurements of Stratospheric Species: O3, CH4, CO, CO2, N2O, HCl, and HF at Northern and Southern Mid-Latitudes,” J. Geophys. Res. 85, 1621 (1980).
[CrossRef]

R. A. Toth, R. H. Hunt, “Line Strengths, Spin-Splittings, and Forbidden Transitions in the (101) Band of 14N16O2,” J. Mol. Spectrosc. 79, 182 (1980).
[CrossRef]

R. A. Toth, L. R. Brown, R. H. Hunt, “Line Positions and Strengths of Methane in the 2862 to 3000 cm−1 Region,” J. Mol. Spectrosc. 67, 1. (1977).
[CrossRef]

Tremblay, G.

H. L. Buijs, G. L. Vail, G. Tremblay, D. J. W. Kendall, “Simultaneous Measurement of the Volume Mixing Ratios of HCl and HF in the Stratosphere,” Geophys. Res. Lett. 7, 205 (1980).
[CrossRef]

Vail, G. L.

H. L. Buijs, G. L. Vail, G. Tremblay, D. J. W. Kendall, “Simultaneous Measurement of the Volume Mixing Ratios of HCl and HF in the Stratosphere,” Geophys. Res. Lett. 7, 205 (1980).
[CrossRef]

Young, C.

C. Young, “Calculation of the Absorption Coefficient for Lines with Combined Doppler and Lorentz Broadening,” J. Quant. Spectrosc. Radiat. Transfer 5, 549 (1965).
[CrossRef]

Zander, R.

R. Zander, “Recent Observations of HF and HCl in the Upper Stratosphere,” Geophys. Res. Lett. 8, 413 (1981).
[CrossRef]

Appl. Opt.

R. A. Toth, L. P. Brown, R. H. Hunt, L. S. Rothman, “Line Parameters of Methane from 2385 to 3200 cm−1,” Appl. Opt. 20, 932 (1981).
[CrossRef] [PubMed]

Appl. Opt.

Appl. Phys. B

J. Reid, D. Labrie, “Second-Harmonic Detection with Tunable Diode Lasers—Comparison of Experiment and Theory,” Appl. Phys. B 26, 203 (1981).
[CrossRef]

Appl. Spectrosc.

Environ. Sci. Technol.

D. R. Hastie, G. I. Mackay, T. Iguchi, B. A. Ridley, H. I. Schiff, “Tunable Diode Laser Systems for Measuring Trace Gases in Tropospheric Air,” Environ. Sci. Technol. 17 (8), 352A (1983); Correction, Environ. Sci. Technol. 17 (11), 510A (1983).
[PubMed]

Geophys. Res. Lett.

R. Zander, “Recent Observations of HF and HCl in the Upper Stratosphere,” Geophys. Res. Lett. 8, 413 (1981).
[CrossRef]

Geophys. Res. Lett.

H. L. Buijs, G. L. Vail, G. Tremblay, D. J. W. Kendall, “Simultaneous Measurement of the Volume Mixing Ratios of HCl and HF in the Stratosphere,” Geophys. Res. Lett. 7, 205 (1980).
[CrossRef]

A. L. Lazrus, B. W. Gandrud, J. Greenberg, J. Bonelli, E. Mroz, W. A. Sedlacek, “Mid-Latitude Seasonal Measurements of Stratospheric Acidic Chlorine Vapor,” Geophys. Res. Lett. 4, 587 (1977).
[CrossRef]

A. W. Miziolek, “Atmospheric Spectra and the Temperature Dependence of Collisional Cross Sections,” Geophys. Res. Lett. 6, 563 (1979).
[CrossRef]

J. Geophys. Res.

C. B. Farmer, O. F. Raper, B. D. Robbins, R. A. Toth, C. Muller, “Simultaneous Spectroscopic Measurements of Stratospheric Species: O3, CH4, CO, CO2, N2O, HCl, and HF at Northern and Southern Mid-Latitudes,” J. Geophys. Res. 85, 1621 (1980).
[CrossRef]

W. W. Berg, P. D. Sperry, K. A. Rahn, E. S. Gladney, “Atmospheric Bromine in the Arctic,” J. Geophys. Res. 88, 6719 (1983).
[CrossRef]

J. Mol. Spectrosc.

R. A. Toth, L. R. Brown, R. H. Hunt, “Line Positions and Strengths of Methane in the 2862 to 3000 cm−1 Region,” J. Mol. Spectrosc. 67, 1. (1977).
[CrossRef]

L. W. Pinkley, K. N. Rao, M. Dang-Nhu, G. Tarrago, G. Poussigue, “Forbidden Lines of the V3 Band of 13CH4: Ground-State Constants,” J. Mol. Spectrosc. 63, 402 (1976).
[CrossRef]

D. L. Gray, A. G. Robiette, A. S. Pine, “Extended Measurement and Analysis of the V3 Infrared Band of Methane,” J. Mol. Spectrosc. 77, 440 (1979).
[CrossRef]

V. Dana, J. P. Maillard, “Analysis of the V1 + V3 Band of 14N16O2,” J. Mol. Spectrosc. 71, 1 (1978).
[CrossRef]

R. A. Toth, R. H. Hunt, “Line Strengths, Spin-Splittings, and Forbidden Transitions in the (101) Band of 14N16O2,” J. Mol. Spectrosc. 79, 182 (1980).
[CrossRef]

J. Quant. Spectrosc. Radiat. Transfer

C. Young, “Calculation of the Absorption Coefficient for Lines with Combined Doppler and Lorentz Broadening,” J. Quant. Spectrosc. Radiat. Transfer 5, 549 (1965).
[CrossRef]

Nature (London)

J. R. Eyre, H. K. Roscoe, “Radiometric Measurement of HCl,” Nature (London) 266, 243 (1977).
[CrossRef]

Proc. R. Soc. London Ser. A

C. P. Chaloner, J. R. Drummond, J. T. Houghton, R. F. Jarnot, H. K. Roscoe, “Infra-red Measurements of Stratospheric Composition I. The Balloon Instrument and Water Vapour Measurements,” Proc. R. Soc. London Ser. A 364, 145 (1978).
[CrossRef]

Proc. Soc. Photo-Opt. Instrum. Eng.

P. Pokrowsky, W. Herrmann, “Sensitive Detection of Hydrogen Chloride by Derivative Spectroscopy with a Diode Laser,” Proc. Soc. Photo-Opt. Instrum. Eng. 286, 33 (1981).

Pure & Appl. Chem.

N. E. Holden, R. L. Martin, I. L. Barnes, “Isotopic Composition of the Elements 1981,” Pure & Appl. Chem. 55 (7), 1119 (1983).
[CrossRef]

Other

L. S. Rothman, “AFGL Trace Gas Compilation Edition of August 1980,” AFGL Hanscom AFB, Bedford, Mass. (1980).

W. W. Berg, unpublished work.

L. R. Brown, Jet Propulsion Laboratory; private communications based on energy level calculations using data from G. Guelachvili.

To describe adequately materials and experimental procedures, it was occasionally necessary to identify commercial products by manufacturer’s name or label. In no instance does such identification imply endorsement by the National Bureau of Standards or the National Center for Atmospheric Research, nor does it imply that the particular products or equipment are necessarily the best available for the purpose.

World Meteorological OrganizationGlobal Ozone Research and Monitoring Project Report No. 11, “The Stratosphere 1981 Theory And Measurements” (1981).

National Research Council Report, Causes and Effects of Stratospheric Ozone Reduction: An Update (National Academy Press, Washington, D.C., 1982).

M. J. Bangham, A. Bonetti, R. H. Bradsell, B. Carli, J. G. Harries, F. Mencaraglia, D. G. Moss, J. Pollitt, E. Rossi, N. R. Swann, unpublished manuscript available from A. Bonetti, U. Florence, Italy (1980).

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Figures (8)

Fig. 1
Fig. 1

Schematic of optical system.

Fig. 2
Fig. 2

Schematic of electronics.

Fig. 3
Fig. 3

Schematic of Kintek permeation calibration system reproduced by permission of Kintek Corp., Texas City, Tex. 77590.

Fig. 4
Fig. 4

Plot of second harmonic signal as a function of the [HCl] in a 16-cm cell. The total pressure is 8.9 Torr.

Fig. 5
Fig. 5

Second harmonic spectra from various trace concentrations of HCI based on the IR ratio technique (cell path length = 40 m, pressure = 8.9 Torr, flow = 0.8 liter/min). The concentrations represent total HCl in normal isotopic abundance. This figure is continuous in time, except for an 11-min gap between (C) and (D). In (A) [HCl] = 6.2 ppb, (B) [HCl] = 8.5 ppb, while (C) and the right-hand side of (D) show the slow cell equilibrium for the same input concentration. In (C) this concentration reached 12.0 ppb. At the left of (D), the flow of HCl was stopped, and pure diluent air was added to the White cell.

Fig. 6
Fig. 6

Second harmonic response as a function of the volume mixing ratio for HCl in normal isotopic abundance at 8.9 Torr based on four different determinations. The temperature is 297 K. The points [HCl]IR (▲) and [HCl]CH4 (◆) are based on IR ratioing techniques using HCI and CH4, respectively, as the reference gas. The point [HCl]NAA (■) is based on the quantitative trapping of HCl on nylon filters followed by neutron activation analysis for Cl. The [HCl]permeation response curve (●) is based on the Kintek permeation calibration system. All determinations except [HCl]NAA were performed simultaneously as discussed in the text. The uncertainties shown are the measurement standard deviations. The uncertainties in the concentration determinations are shown for a few representative points. For readers more familiar with other concentration units, 1 ppb = 1627-ng m−3 (STP). Both points indicated by open squares are permeation calibrations taken before equilibrium was established with all the surfaces in the White cell. The encircled points on the Y axis are residual HCl concentrations obtained by addition of NH3 into the diluent air flow.

Fig. 7
Fig. 7

Calculated properties of the second harmonic signal for HCl using a Voigt absorption line profile (γL = 0.0011 cm−1 and γD = 0.00301 cm−1) as a function of the modulation parameter m. The insert displays a plot of H2(ν,m) as a function of frequency. The peak-to-peak signal defined by H2 = P + N was used throughout this analysis. The maximum value of P is 0.419 (R = 1.8) and occurs at m = 2.2.

Fig. 8
Fig. 8

Comparison between theoretical and experimental response factor ratios (RF) as a function of CH4 modulation parameter. The corresponding modulation parameter for HCl was fixed at its experimental value of 0.62. The pressure was ~8.9 Torr in all cases.

Equations (10)

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[ HCl ] = 1 α v P L ln ( I 0 / I ) .
I 0 H 2 α v [ HCl ] P L .
[ HCl ] IR = [ HCl ] s = [ HCl ] r S s ( I 0 ) r L r S r ( I 0 ) s L s .
[ HCl ] CH 4 = [ HCl ] s = [ CH 4 ] S s ( I 0 ) r ( H 2 · α v ) r S r ( I 0 ) s ( H 2 · α v ) s .
m = a / γ v .
ν ( t ) = ν ¯ + a cos ω t .
ν ( t ) = ν ¯ + m γ v cos θ .
X = ( ν - ν 0 ) γ D ( ln 2 ) 1 / 2 ,
Y = γ L γ D ( ln 2 ) 1 / 2 .
H 2 ( ν , m ) = 2 Π α v 0 π α v ( ν ¯ + m γ v cos θ , Y ) cos 2 θ d θ .

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