Abstract

Measurements of the magnitude and spectral distribution of the Raman-scattering coefficients of pure water (b rw) and seawater (b rs) are presented. Two independent measurements of the spectral distribution of the Raman-scattering coefficient of pure water were made for incident wavelengths ranging from 250 to 500 nm. These measurements revealed a strong dependence of b rw on wavelength that could be represented by a (λ′)-5.3±0.3 relationship, where λ′ is the incident wavelength, or a λ-4.6±0.3 relationship, where λ is the Raman-scattered wavelength, when normalized to units of photons. The corresponding relationships for normalization to energy are (λ′)-5.5±0.4 and λ-4.8±0.3, respectively. These relationships are found to be consistent with resonance Raman theory for an absorption wavelength of 130 nm. The absolute value of b rw for the 3400-cm-1 line was found to be (2.7 ± 0.2) × 10-4 m-1 for an incident wavelength of 488 nm, which is consistent with a number of earlier reports. The difference between the magnitudes of the Raman-scattering coefficients for pure water and seawater was statistically insignificant.

© 1998 Optical Society of America

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    [CrossRef] [PubMed]
  2. S. Sathyendranath, T. Platt, E. P. W. Horne, W. G. Harrison, O. Ulloa, R. Outerbridge, N. Hoepffner, “Estimation of new production in the ocean by compound remote sensing,” Nature (London) 353, 129–133 (1991).
    [CrossRef]
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    [CrossRef]
  4. R. H. Stavn, A. D. Weidemann, “Optical modeling of clear ocean light fields: Raman scattering effects,” Appl. Opt. 27, 4002–4011 (1988).
    [CrossRef] [PubMed]
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    [CrossRef] [PubMed]
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    [CrossRef] [PubMed]
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    [CrossRef]
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    [CrossRef]
  13. S. Sugihara, M. Kishino, N. Okami, “Contribution of Raman scattering to upward irradiance in the sea,” J. Oceanogr. Soc. Jpn. 40(6), 397–404 (1984).
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1997 (2)

1994 (1)

1993 (3)

1992 (2)

1991 (1)

S. Sathyendranath, T. Platt, E. P. W. Horne, W. G. Harrison, O. Ulloa, R. Outerbridge, N. Hoepffner, “Estimation of new production in the ocean by compound remote sensing,” Nature (London) 353, 129–133 (1991).
[CrossRef]

1990 (2)

M. R. Lewis, M.-E. Carr, G. C. Feldman, W. Esaias, C. McClain, “Influence of penetrating solar radiation on the heat budget of the equatorial Pacific Ocean,” Nature (London) 347, 543–545 (1990).
[CrossRef]

B. R. Marshall, R. C. Smith, “Raman scattering and in-water ocean optical properties,” Appl. Opt. 29, 71–84 (1990).
[CrossRef] [PubMed]

1988 (2)

R. H. Stavn, A. D. Weidemann, “Optical modeling of clear ocean light fields: Raman scattering effects,” Appl. Opt. 27, 4002–4011 (1988).
[CrossRef] [PubMed]

T. Platt, S. Sathyendranath, “Oceanic primary production: estimation by remote sensing at local and regional scales,” Science 241, 1613–1620 (1988).
[CrossRef] [PubMed]

1984 (1)

S. Sugihara, M. Kishino, N. Okami, “Contribution of Raman scattering to upward irradiance in the sea,” J. Oceanogr. Soc. Jpn. 40(6), 397–404 (1984).
[CrossRef]

1977 (1)

I. I. Kondilenko, P. A. Korotkov, V. A. Klimenko, O. P. Demyanenko, “Transverse cross section of the Raman scattering of the ν1 vibration of the water molecule in the liquid and gaseous states,” Opt. Spectrosc. (USSR) 43, 384–386 (1977).

1975 (2)

R. B. Slusher, V. E. Derr, “Temperature dependence and cross sections of some Stokes and anti-Stokes Raman lines in ice Ih,” Appl. Opt. 14, 2116–2120 (1975).
[CrossRef] [PubMed]

N. P. Romanov, V. S. Shuklin, “Raman scattering cross section of liquid water,” Opt. Spectrosc. (USSR) 38, 646–648 (1975).

1971 (1)

1969 (1)

L. R. Painter, R. D. Birkhoff, E. T. Arakawa, “Optical measurements of liquid water in the vacuum ultraviolet,” J. Chem. Phys. 51, 243–251 (1969).
[CrossRef]

Albrecht, A. C.

J. Tang, A. C. Albrecht, “Developments in the theories of vibrational Raman intensities,” in Raman Spectroscopy, H. A. Szymanski, ed. (Plenum, New York, 1970), 33–68.

Arakawa, E. T.

L. R. Painter, R. D. Birkhoff, E. T. Arakawa, “Optical measurements of liquid water in the vacuum ultraviolet,” J. Chem. Phys. 51, 243–251 (1969).
[CrossRef]

Bartlett, J. S.

J. S. Bartlett, “A comparison of models of sea-surface reflectance incorporating Raman scattering by water,” in Ocean Optics XIII, S. G. Ackleson, R. Frouin, eds., Proc. SPIE2963, 592–596 (1997).
[CrossRef]

J. S. Bartlett, “The influence of Raman scattering by seawater and fluorescence by phytoplankton on ocean colour,” M.S. thesis (Dalhousie University, Halifax, Nova Scotia, 1996).

Birkhoff, R. D.

L. R. Painter, R. D. Birkhoff, E. T. Arakawa, “Optical measurements of liquid water in the vacuum ultraviolet,” J. Chem. Phys. 51, 243–251 (1969).
[CrossRef]

Bischel, W. K.

W. K. Bischel, G. Black, “Wavelength dependence of Raman scattering cross sections from 200-600 nm,” in Excimer Lasers—1983, C. K. Rhodes, H. Egger, H. Pummer, eds. (American Institute of Physics, New York, 1983), 181–187.

Black, G.

W. K. Bischel, G. Black, “Wavelength dependence of Raman scattering cross sections from 200-600 nm,” in Excimer Lasers—1983, C. K. Rhodes, H. Egger, H. Pummer, eds. (American Institute of Physics, New York, 1983), 181–187.

Carder, K. L.

Z. Lee, K. L. Carder, S. K. Hawes, R. G. Steward, T. G. Peacock, C. O. Davis, “An interpretation of high spectral resolution remote sensing reflectance,” in Optics of the Air-Sea Interface: Theory and Measurement, L. Estep, ed., Proc. SPIE1749, 49–64 (1992).
[CrossRef]

Carr, M.-E.

M. R. Lewis, M.-E. Carr, G. C. Feldman, W. Esaias, C. McClain, “Influence of penetrating solar radiation on the heat budget of the equatorial Pacific Ocean,” Nature (London) 347, 543–545 (1990).
[CrossRef]

Chang, C. H.

C. H. Chang, L. A. Young, “Seawater temperature measurement from Raman spectra,” Research Note 920, N62269-72-C-0204 (Advanced Research Projects Agency, Washington, D.C., July1972).

Chantry, G. W.

G. W. Chantry, “Polarizability theory of the Raman effect,” in The Raman Effect: Principles, A. Anderson, ed. (Marcel Dekker, New York, 1971), Vol. 1.

Copeland, R. A.

Davis, C. O.

Z. Lee, K. L. Carder, S. K. Hawes, R. G. Steward, T. G. Peacock, C. O. Davis, “An interpretation of high spectral resolution remote sensing reflectance,” in Optics of the Air-Sea Interface: Theory and Measurement, L. Estep, ed., Proc. SPIE1749, 49–64 (1992).
[CrossRef]

Demyanenko, O. P.

I. I. Kondilenko, P. A. Korotkov, V. A. Klimenko, O. P. Demyanenko, “Transverse cross section of the Raman scattering of the ν1 vibration of the water molecule in the liquid and gaseous states,” Opt. Spectrosc. (USSR) 43, 384–386 (1977).

Derr, V. E.

Esaias, W.

M. R. Lewis, M.-E. Carr, G. C. Feldman, W. Esaias, C. McClain, “Influence of penetrating solar radiation on the heat budget of the equatorial Pacific Ocean,” Nature (London) 347, 543–545 (1990).
[CrossRef]

Faris, G. W.

Feldman, G. C.

M. R. Lewis, M.-E. Carr, G. C. Feldman, W. Esaias, C. McClain, “Influence of penetrating solar radiation on the heat budget of the equatorial Pacific Ocean,” Nature (London) 347, 543–545 (1990).
[CrossRef]

Ge, Y.

Gordon, H. R.

Grasselli, J. G.

J. G. Grasselli, W. M. Ritchey, Atlas of Spectral Data and Physical Constants for Organic Compounds, 2nd ed. (CRC Press, Cleveland, Ohio, 1975), Vol. 2.

Haltrin, V. I.

V. I. Haltrin, G. W. Kattawar, “Self-consistent solutions to the equation of transfer with elastic and inelastic scattering in oceanic optics. 1. Model,” Appl. Opt. 32, 5356–5367 (1993).
[CrossRef] [PubMed]

V. I. Haltrin, G. W. Kattawar, A. D. Weidemann, “Modeling of elastic and inelastic scattering effects in oceanic optics,” in Ocean Optics XIII, S. G. Ackleson, R. Frouin, eds., Proc. SPIE2963, 597–602 (1997).
[CrossRef]

Harrison, W. G.

S. Sathyendranath, T. Platt, E. P. W. Horne, W. G. Harrison, O. Ulloa, R. Outerbridge, N. Hoepffner, “Estimation of new production in the ocean by compound remote sensing,” Nature (London) 353, 129–133 (1991).
[CrossRef]

Hawes, S. K.

Z. Lee, K. L. Carder, S. K. Hawes, R. G. Steward, T. G. Peacock, C. O. Davis, “An interpretation of high spectral resolution remote sensing reflectance,” in Optics of the Air-Sea Interface: Theory and Measurement, L. Estep, ed., Proc. SPIE1749, 49–64 (1992).
[CrossRef]

Hoepffner, N.

S. Sathyendranath, T. Platt, E. P. W. Horne, W. G. Harrison, O. Ulloa, R. Outerbridge, N. Hoepffner, “Estimation of new production in the ocean by compound remote sensing,” Nature (London) 353, 129–133 (1991).
[CrossRef]

Hofstraat, J. W.

Horne, E. P. W.

S. Sathyendranath, T. Platt, E. P. W. Horne, W. G. Harrison, O. Ulloa, R. Outerbridge, N. Hoepffner, “Estimation of new production in the ocean by compound remote sensing,” Nature (London) 353, 129–133 (1991).
[CrossRef]

Hu, C.

C. Hu, K. J. Voss, “In situ measurements of Raman scattering in clear ocean water,” Appl. Opt. 36, 6962–6967 (1997).
[CrossRef]

C. Hu, K. J. Voss, “Solar stimulated inelastic light scattering in clear sea water,” in Ocean Optics XIII, S. G. Ackleson, R. Frouin, eds., Proc. SPIE2963, 266–271 (1997).
[CrossRef]

Kato, Y.

Kattawar, G. W.

Kishino, M.

S. Sugihara, M. Kishino, N. Okami, “Contribution of Raman scattering to upward irradiance in the sea,” J. Oceanogr. Soc. Jpn. 40(6), 397–404 (1984).
[CrossRef]

Klimenko, V. A.

I. I. Kondilenko, P. A. Korotkov, V. A. Klimenko, O. P. Demyanenko, “Transverse cross section of the Raman scattering of the ν1 vibration of the water molecule in the liquid and gaseous states,” Opt. Spectrosc. (USSR) 43, 384–386 (1977).

Kondilenko, I. I.

I. I. Kondilenko, P. A. Korotkov, V. A. Klimenko, O. P. Demyanenko, “Transverse cross section of the Raman scattering of the ν1 vibration of the water molecule in the liquid and gaseous states,” Opt. Spectrosc. (USSR) 43, 384–386 (1977).

Korotkov, P. A.

I. I. Kondilenko, P. A. Korotkov, V. A. Klimenko, O. P. Demyanenko, “Transverse cross section of the Raman scattering of the ν1 vibration of the water molecule in the liquid and gaseous states,” Opt. Spectrosc. (USSR) 43, 384–386 (1977).

Latuhihin, M. J.

Lee, Z.

Z. Lee, K. L. Carder, S. K. Hawes, R. G. Steward, T. G. Peacock, C. O. Davis, “An interpretation of high spectral resolution remote sensing reflectance,” in Optics of the Air-Sea Interface: Theory and Measurement, L. Estep, ed., Proc. SPIE1749, 49–64 (1992).
[CrossRef]

Lewis, M. R.

M. R. Lewis, M.-E. Carr, G. C. Feldman, W. Esaias, C. McClain, “Influence of penetrating solar radiation on the heat budget of the equatorial Pacific Ocean,” Nature (London) 347, 543–545 (1990).
[CrossRef]

Marshall, B. R.

B. R. Marshall, R. C. Smith, “Raman scattering and in-water ocean optical properties,” Appl. Opt. 29, 71–84 (1990).
[CrossRef] [PubMed]

B. R. Marshall, “Raman scattering in ocean water,” M.A. thesis (University of California at Santa Barbara, Santa Barbara, Calif., 1989).

McClain, C.

M. R. Lewis, M.-E. Carr, G. C. Feldman, W. Esaias, C. McClain, “Influence of penetrating solar radiation on the heat budget of the equatorial Pacific Ocean,” Nature (London) 347, 543–545 (1990).
[CrossRef]

Mobley, C. D.

C. D. Mobley, Light and Water: Radiative Transfer in Natural Waters (Academic, San Diego, Calif., 1994).

Okami, N.

S. Sugihara, M. Kishino, N. Okami, “Contribution of Raman scattering to upward irradiance in the sea,” J. Oceanogr. Soc. Jpn. 40(6), 397–404 (1984).
[CrossRef]

Outerbridge, R.

S. Sathyendranath, T. Platt, E. P. W. Horne, W. G. Harrison, O. Ulloa, R. Outerbridge, N. Hoepffner, “Estimation of new production in the ocean by compound remote sensing,” Nature (London) 353, 129–133 (1991).
[CrossRef]

Painter, L. R.

L. R. Painter, R. D. Birkhoff, E. T. Arakawa, “Optical measurements of liquid water in the vacuum ultraviolet,” J. Chem. Phys. 51, 243–251 (1969).
[CrossRef]

Peacock, T. G.

Z. Lee, K. L. Carder, S. K. Hawes, R. G. Steward, T. G. Peacock, C. O. Davis, “An interpretation of high spectral resolution remote sensing reflectance,” in Optics of the Air-Sea Interface: Theory and Measurement, L. Estep, ed., Proc. SPIE1749, 49–64 (1992).
[CrossRef]

Platt, T.

S. Sathyendranath, T. Platt, E. P. W. Horne, W. G. Harrison, O. Ulloa, R. Outerbridge, N. Hoepffner, “Estimation of new production in the ocean by compound remote sensing,” Nature (London) 353, 129–133 (1991).
[CrossRef]

T. Platt, S. Sathyendranath, “Oceanic primary production: estimation by remote sensing at local and regional scales,” Science 241, 1613–1620 (1988).
[CrossRef] [PubMed]

S. Sathyendranath, T. Platt, “Angular structure of under-water light field: importance for ocean-colour models,” in Ocean Optics XIII, S. G. Ackleson, R. Frouin, eds., Proc. SPIE2963, 26–31 (1997).
[CrossRef]

Ritchey, W. M.

J. G. Grasselli, W. M. Ritchey, Atlas of Spectral Data and Physical Constants for Organic Compounds, 2nd ed. (CRC Press, Cleveland, Ohio, 1975), Vol. 2.

Romanov, N. P.

N. P. Romanov, V. S. Shuklin, “Raman scattering cross section of liquid water,” Opt. Spectrosc. (USSR) 38, 646–648 (1975).

Sathyendranath, S.

S. Sathyendranath, T. Platt, E. P. W. Horne, W. G. Harrison, O. Ulloa, R. Outerbridge, N. Hoepffner, “Estimation of new production in the ocean by compound remote sensing,” Nature (London) 353, 129–133 (1991).
[CrossRef]

T. Platt, S. Sathyendranath, “Oceanic primary production: estimation by remote sensing at local and regional scales,” Science 241, 1613–1620 (1988).
[CrossRef] [PubMed]

S. Sathyendranath, T. Platt, “Angular structure of under-water light field: importance for ocean-colour models,” in Ocean Optics XIII, S. G. Ackleson, R. Frouin, eds., Proc. SPIE2963, 26–31 (1997).
[CrossRef]

Shuklin, V. S.

N. P. Romanov, V. S. Shuklin, “Raman scattering cross section of liquid water,” Opt. Spectrosc. (USSR) 38, 646–648 (1975).

Slusher, R. B.

Smith, R. C.

Stavn, R. H.

Steward, R. G.

Z. Lee, K. L. Carder, S. K. Hawes, R. G. Steward, T. G. Peacock, C. O. Davis, “An interpretation of high spectral resolution remote sensing reflectance,” in Optics of the Air-Sea Interface: Theory and Measurement, L. Estep, ed., Proc. SPIE1749, 49–64 (1992).
[CrossRef]

Sugihara, S.

S. Sugihara, M. Kishino, N. Okami, “Contribution of Raman scattering to upward irradiance in the sea,” J. Oceanogr. Soc. Jpn. 40(6), 397–404 (1984).
[CrossRef]

Szymanski, H. A.

J. Tang, A. C. Albrecht, “Developments in the theories of vibrational Raman intensities,” in Raman Spectroscopy, H. A. Szymanski, ed. (Plenum, New York, 1970), 33–68.

Takuma, H.

Tang, J.

J. Tang, A. C. Albrecht, “Developments in the theories of vibrational Raman intensities,” in Raman Spectroscopy, H. A. Szymanski, ed. (Plenum, New York, 1970), 33–68.

Ulloa, O.

S. Sathyendranath, T. Platt, E. P. W. Horne, W. G. Harrison, O. Ulloa, R. Outerbridge, N. Hoepffner, “Estimation of new production in the ocean by compound remote sensing,” Nature (London) 353, 129–133 (1991).
[CrossRef]

Voss, K. J.

Weidemann, A. D.

R. H. Stavn, A. D. Weidemann, “Raman scattering in ocean optics: quantitative assessment of internal radiant emission,” Appl. Opt. 31, 1294–1303 (1992).
[CrossRef] [PubMed]

R. H. Stavn, A. D. Weidemann, “Optical modeling of clear ocean light fields: Raman scattering effects,” Appl. Opt. 27, 4002–4011 (1988).
[CrossRef] [PubMed]

V. I. Haltrin, G. W. Kattawar, A. D. Weidemann, “Modeling of elastic and inelastic scattering effects in oceanic optics,” in Ocean Optics XIII, S. G. Ackleson, R. Frouin, eds., Proc. SPIE2963, 597–602 (1997).
[CrossRef]

R. H. Stavn, A. D. Weidemann, “Raman scattering effects in ocean optics,” in Ocean Optics IX, M. A. Blizard, ed., Proc. SPIE925, 131–139 (1988).
[CrossRef]

Xu, X.

Young, L. A.

C. H. Chang, L. A. Young, “Seawater temperature measurement from Raman spectra,” Research Note 920, N62269-72-C-0204 (Advanced Research Projects Agency, Washington, D.C., July1972).

Appl. Opt. (10)

R. B. Slusher, V. E. Derr, “Temperature dependence and cross sections of some Stokes and anti-Stokes Raman lines in ice Ih,” Appl. Opt. 14, 2116–2120 (1975).
[CrossRef] [PubMed]

R. H. Stavn, A. D. Weidemann, “Optical modeling of clear ocean light fields: Raman scattering effects,” Appl. Opt. 27, 4002–4011 (1988).
[CrossRef] [PubMed]

B. R. Marshall, R. C. Smith, “Raman scattering and in-water ocean optical properties,” Appl. Opt. 29, 71–84 (1990).
[CrossRef] [PubMed]

R. H. Stavn, A. D. Weidemann, “Raman scattering in ocean optics: quantitative assessment of internal radiant emission,” Appl. Opt. 31, 1294–1303 (1992).
[CrossRef] [PubMed]

Y. Ge, H. R. Gordon, K. J. Voss, “Simulation of inelastic-scattering contributions to the irradiance field in the ocean: variation in Fraunhofer line depths,” Appl. Opt. 32, 4028–4036 (1993).
[PubMed]

V. I. Haltrin, G. W. Kattawar, “Self-consistent solutions to the equation of transfer with elastic and inelastic scattering in oceanic optics. 1. Model,” Appl. Opt. 32, 5356–5367 (1993).
[CrossRef] [PubMed]

R. H. Stavn, “Effects of Raman scattering across the visible spectrum in clear ocean water: a Monte Carlo study,” Appl. Opt. 32, 6853–6863 (1993).
[CrossRef] [PubMed]

G. W. Faris, R. A. Copeland, “Wavelength dependence of the Raman cross section for liquid water,” Appl. Opt. 36, 2686–2688 (1997).
[CrossRef] [PubMed]

C. Hu, K. J. Voss, “In situ measurements of Raman scattering in clear ocean water,” Appl. Opt. 36, 6962–6967 (1997).
[CrossRef]

G. W. Kattawar, X. Xu, “Filling in of Fraunhofer lines in the ocean by Raman scattering,” Appl. Opt. 31, 6491–6500 (1992).
[CrossRef] [PubMed]

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Figures (7)

Fig. 1
Fig. 1

Correction curves for the PTI spectrofluorometer with the polarizers in place for (a) the excitation optics and (b) the emission optics.

Fig. 2
Fig. 2

(a) Spectra resulting from Raman scattering by pure water for incident wavelengths ranging from 250 to 500 nm at a bandpass of 5 nm. These measurements were made with a PTI spectrofluorometer. (b) Relationship between the peak areas, normalized to energy units, for Raman scattering by pure water at a 5-nm bandpass and the incident wavelength for six water samples (solid circles). The data are best fit by a (λ′)-5.33 power law (solid curve, r2 = 0.996).

Fig. 3
Fig. 3

Peak areas of Raman scattering, normalized to energy units, as a function of the incident wavelength (solid circles). These measurements were made with a Hitachi spectrofluorometer. The data are normalized at 475 nm. The solid curve shows the best fit of (λ′)-5.5 (r2 = 0.90).

Fig. 4
Fig. 4

Comparison of the wavelength dependence of Raman scattering by pure water normalized to energy units as a function of the scattered wavelength from various sources. Each of the curves shown were normalized at an incident wavelength of (a) 488 nm (or a scattered wavelength of 584 nm) and (b) 250 nm (or a scattered wavelength of 273 nm). The thick solid curve shows the results presented in this paper (curve t). The thin solid curves show the results from previously published measurements by Sugihara et al.13 (curve S) and Faris and Copeland27 (curve F). The dashed curves show the theoretical relationships of λ-4 from Placzek30 (curve P), two resonance Raman relationships (for wavelengths far from the absorption band [Eq. (4), curve f] and near the absorption band [Eq. (5), curve n], and the relationship of (λ′)-4 that has been used in previous studies (curve p).

Fig. 5
Fig. 5

Spectra resulting from Raman scattering for an incident wavelength of 488 nm with bandpasses ranging in value from 3.5 to 6 nm for (a) benzene and (b) pure water.

Fig. 6
Fig. 6

Relationship between the peak areas of the Raman peaks and the bandpass for pure water (filled circles) and benzene (open circles). The data for each substance were fit by quadratics yielding Φ w = 707β2 for pure water (with an r2 determination coefficient of 0.95) and Φ b = 512β2 for benzene (r2 = 0.97).

Fig. 7
Fig. 7

Peak areas for Raman scattering by pure seawater plotted against peak areas for Raman scattering by pure water at the same wavelength (filled circles). The solid line is the 1:1 line. The r2 determination coefficient for the peak areas is 0.98, with a slope of 0.97 ± 0.02.

Tables (2)

Tables Icon

Table 1 Exponents in the Wavelength Dependence of Raman Scattering by Pure Water

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Table 2 Values Used for the Calculation of the Raman-Scattering Coefficients brw(488) for Pure Water and brs(488) for Pure Seawater

Equations (7)

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C ex λ = I ref λ / I rhod λ .
C em λ = I lamp λ / I em λ .
I corr λ ,   λ = I meas λ ,   λ C ex λ C em λ .
b rw λ     ν 4 ν 2 - ν 2 2 ,
b rw λ     ν 4 ν 2 + ν 2 2 ν 2 - ν 2 4 .
d σ w d Ω 90 ° = Φ w Φ b n w n b 2 T b T w d b d w M w M b 1 + ρ w 1 + ρ b d σ b d Ω 90 ° ,
b rw λ = 800 N π 3 d σ w λ d Ω 90 ° 1 + 2 ρ w 1 + ρ w ,

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