1. Introduction
Possible errors in the depolarization term were considered by Hoyt (1977), Fröhlich and Shaw (1980), and Young (1980, 1981). The correction proposed by Young (1981) had been accepted for modern Rayleigh scattering calculations in atmospheric applications. In brief, Young (1981) suggested that the value F(air) = (6 + 3ρ)/(6 − 7ρ) = 1.0480 be used rather than the value 1.0608 used by Penndorf (1957). This effect alone reduced Rayleigh scattering values by 1.2%; however, it cannot be applied over the entire spectrum because F(air) is dependent on wavelength. Furthermore, since the depolarization has been measured for the constituents of air (at least in a relative sense), it is possible in principle to estimate the depolarization of air as a function of composition. Bates (1984) and Bucholtz (1995) discussed the depolarization in detail. It appears that currently the best estimates for (6 + 3ρ)/(6 − 7ρ) use the equations given by Bates (1984) for the depolarization of N2, O2, Ar, and CO2 as a function of wavelength. It is therefore possible to calculate the depolarization of air as a function of CO2 concentration.
2. Optical depth
3. Approximations for Rayleigh optical depth
4. Suggested method to calculate Rayleigh optical depth of air
Here we suggest a method for calculation of Rayleigh optical depth that goes back to first principles as suggested by Penndorf (1957) rather than using curve-fitting techniques, although it is true that the refractive index of air is still derived from a curve fit to experimental data. We suggest using all of the latest values of the physical constants of nature, and we suggest including the variability in refractive index, and also the mean molecular weight of air, due to CO2 even though these effects are in the range of 0.1%–0.01%. It should be noted that aerosol optical depths are often as low as 0.01 at Mauna Loa. Since Rayleigh optical depth is of the order of 1 at 300 nm, it is seen that a 0.1% error in Rayleigh optical depth translates into a 10% error in aerosol optical depth. Furthermore, it simply makes sense to perform the calculations as accurately as possible.
We should note that the effects of high concentrations of water vapor on the refractive index of air may be of the same order as CO2 (Edlén 1953, 1966). However, for practical atmospheric situations the total water vapor in the vertical column is small and does not significantly affect the above calculations. Furthermore, the water vapor in the atmosphere is usually confined to a thin layer near the surface, which significantly complicates the calculation, whereas CO2 is generally well mixed throughout the atmosphere.
5. Optical depths of the constituents of air
6. Some example calculations
Using the above equations we now present example calculations to show new values for the scattering cross section (as a function of wavelength) of dry air containing 360 ppm CO2, similar to the presentations of Penndorf (1957) and Bucholtz (1995). In addition we present new values for Rayleigh optical depth for dry air containing 360 ppm CO2 at sea level, 1013.25 mb, and a latitude of 45°; and at Mauna Loa Observatory (MLO) (altitude 3400 m, pressure 680 mb, and a latitude of 19.533°). The results of these calculations are shown in Table 3.
7. Conclusions
We have presented the latest values of the physical constants necessary for the calculation of Rayleigh optical depth. For the most accurate calculation of this quantity it is recommended that users go directly to first principles and that Peck and Reeder’s (1972) formula be used to estimate the refractive index of standard air. Next, we recommend that Penndorf’s (1957) method be used to calculate the scattering cross section per molecule of air, taking into account the concentration of CO2. In most cases the effects of water vapor may be neglected. The recommendations of Bates (1984) were used for the depolarization of air as a function of wavelength. Next the Rayleigh optical depth should be calculated using the atmospheric pressure at the site of interest. Note the importance of taking into account variations of g. We do not necessarily recommend the use of curve-fitting techniques to generate an equation for estimating Rayleigh optical depth because the inaccuracies that arise can equal or even exceed other quantities being estimated, such as aerosol optical depth. Furthermore, all of the above calculations are simple enough to be done in a spreadsheet if desired, or can easily be programmed in virtually any computer language. However, for those who wish to use a simple equation and are satisfied with less accuracy, the techniques used to produce Eqs. (29)–(31) may be of interest. As more accurate estimates of the various parameters discussed above become available, the equations of interest may easily be modified.
In some calculations of optical depth it may be desired to take into account the vertical distribution of the composition of air, particularly CO2. In this case a layer-by-layer calculation may be done using the estimated composition for each layer, and then the total optical depth may be estimated by summing the optical depths for all of the layers.
Acknowledgments
We thank Gail Anderson for her helpful comments concerning curve-fitting techniques.
REFERENCES
Bates, D. R., 1984: Rayleigh scattering by air. Planet. Space Sci.,32, 785–790.
Bucholtz, A., 1995: Rayleigh-scattering calculations for the terrestrial atmosphere. Appl. Opt.,34, 2765–2773.
Cohen, E. R., and B. N. Taylor, 1995: The fundamental physical constants. Phys. Today,48, 9–16.
CRC, 1997: Handbook of Chemistry and Physics. D. R. Lide and H. P. R. Frederikse, Eds., CRC Press, 2447 pp.
Dutton, E. G., P. Reddy, S. Ryan, and J. J. DeLuisi, 1994: Features and effects of aerosol optical depth observed at Mauna Loa, Hawaii: 1982–1992. J. Geophys. Res.,99, 8295–8306.
Edlén, B., 1953: The dispersion of standard air. J. Opt. Soc. Amer.,43, 339–344.
——, 1966: The refractive index of air. Metrologia,2, 71–80.
Fröhlich, C., and G. E. Shaw, 1980: New determination of Rayleigh scattering in the terrestrial atmosphere. Appl. Opt.,19, 1773–1775.
Hansen, J. E., and L. D. Travis, 1974: Light scattering in planetary atmospheres. Space Sci. Rev.,16, 527–610.
Harvey, A. H., J. S. Gallagher, and J. M. H. Levelt Sengers, 1998: Revised formulation for the refractive index of water and steam as a function of wavelength, temperature and density. J. Phys. Chem. Ref. Data,27, 761–774.
Hoyt, D. V., 1977: A redetermination of the Rayleigh optical depth and its application to selected solar radiation problems. J. Appl. Meteor.,16, 432–436.
List, R. J., 1968: Smithsonian Meteorological Tables. Smithsonian, 527 pp.
Marshall, B. R., and R. C. Smith, 1990: Raman scattering and in-water ocean optical properties. Appl. Opt.,29, 71–84.
McCartney, E. J., 1976: Optics of the Atmosphere. Wiley, 408 pp.
Nicolet, M., 1984: On the molecular scattering in the terrestrial atmosphere: An empirical formula for its calculation in the homosphere. Planet. Space Sci.,32, 1467–1468.
Owens, J. C., 1967: Optical refractive index of air: Dependence on pressure, temperature and composition. Appl. Opt.,6, 51–59.
Peck, E. R., and K. Reeder, 1972: Dispersion of air. J. Opt. Soc. Amer.,62, 958–962.
Penndorf, R., 1957: Tables of the refractive index for standard air and the Rayleigh scattering coefficient for the spectral region between 0.2 and 20.0 μ and their application to atmospheric optics. J. Opt. Soc. Amer.,47, 176–182.
Seinfeld, J. H., and S. N. Pandis, 1998: Atmospheric Chemistry and Physics, from Air Pollution to Climate Change. Wiley, 1326 pp.
Stephens, G. L., 1994: Remote Sensing of the Lower Atmosphere. Oxford University Press, 523 pp.
Teillet, P. M., 1990: Rayleigh optical depth comparisons from various sources. Appl. Opt.,29, 1897–1900.
van de Hulst, H. C., 1957: Light Scattering by Small Particles. Wiley, 470 pp.
Young, A. T., 1980: Revised depolarization corrections for atmospheric extinction. Appl. Opt.,19, 3427–3428.
——, 1981: On the Rayleigh-scattering optical depth of the atmosphere. J. Appl. Meteor.,20, 328–330.
APPENDIX
Summary of Constants
Values for the constants of nature that have been used in this paper are listed below.
Avogadro’s number = 6.022 136 7 × 1023 molecules mol−1
Molar volume at 273.15 K and 1013.25 mb = 22.4141 L mol−1
Molecular density of a gas at 288.15 K and 1013.25 mb = 2.546 899 × 1019 molecules cm−3
Mean molecular weight of dry air (zero CO2) = 28.9595 gm mol−1
Mean molecular weight of dry air (360 ppm CO2) = 28.9649 gm mol−1
Acceleration of gravity (sea level and 45° latitude) g0(45°) = 980.6160 cm s−2
Mass-weighted air column altitude zc = 0.737 37z + 5517.56
Depolarization factor for dry air with 300 ppm CO2.
Citation: Journal of Atmospheric and Oceanic Technology 16, 11; 10.1175/1520-0426(1999)016<1854:ORODC>2.0.CO;2
Percent error for Eq. (29) fit to the scattering cross-section data in Table 3.
Citation: Journal of Atmospheric and Oceanic Technology 16, 11; 10.1175/1520-0426(1999)016<1854:ORODC>2.0.CO;2
Constituents and mean molecular weight of dry air.
Optical depths of the constituents of air (standard pressure 1013.25 mb and altitude 0 m).
Scattering cross section (per molecule) and Rayleigh optical depth (τR) for dry air containing 360 ppm CO2. Rayleigh optical depths are given for a location at sea level, 1013.25 mb, 45° latitude, and at MLO at altitude 3400 m, pressure 680 mb, and latitude 19.533°
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