Optical Properties of Mineral Particles and Their Effect on Remote-Sensing Reflectance in Coastal Waters

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Optical Properties of Mineral Particles and Their Effect on Remote-Sensing Reflectance in Coastal Waters Dariusz Stramski Marine Physical Laboratory Scripps Institution of Oceanography University of California at San Diego La Jolla, CA 92093-0238 phone: (858) 534 3353 fax: (858) 534 7641 e-mail: stramski@mpl.ucsd.edu Award #: N000149810003 LONG-TERM GOALS My long-term goal is to develop the base of knowledge necessary to: (i) understand the magnitudes and variability of the optical properties of the ocean; (ii) predict the inherent and apparent optical properties of the ocean including remote-sensing reflectance, given the types and concentration of suspended particles; (iii) retrieve the inherent optical properties and concentration of optically significant constituents of sea water from reflectance measurements. OBJECTIVES The primary objective of this project is to examine the optical properties of mineral particles suspended in seawater. The specific objectives for the reporting period were to measure the absorption properties of mineral particles in the laboratory and to analyze a large data set of absorption measurements taken in various coastal waters. APPROACH Because accurate measurements of true absorption by scattering samples such as mineral particles suspended in seawater are extremely difficult, significant efforts focused on absorption measurements under controlled laboratory conditions using special instrumentation. A major source of error in the measurement of absorption by suspended particles is associated with the fact that not all of the scattered light is collected by the absorption meter due to geometry of instrument. In the previous report we described our effort to develop a method for correcting for the scattering error based on 3-D Monte Carlo simulations of radiative transfer within the measurement system. In this reporting period we took another approach. We measured absorption of mineral samples in laboratory with a dual beam spectrophotometer (Perkin-Elmer Lambda 18) equipped with a 15-cm Spectralon integrating sphere (Labsphere). An important attribute of these measurements is that we placed the sample inside the sphere rather than outside the sphere at the entrance port, which was commonly done in the past. This geometry of measurement allowed us to detect light scattered at nearly all angles (with the exception of a small solid angle around the backward scattering angle of 180 o ). As a result, we can assume that our measurement provided absorption subjected to very small scattering error, and that no 1

Report Documentation Page Form Approved OMB No. 0704-0188 Public reporting burden for the collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing this burden, to Washington Headquarters Services, Directorate for Information Operations and Reports, 1215 Jefferson Davis Highway, Suite 1204, Arlington VA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to a penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. 1. REPORT DATE 30 SEP 2001 2. REPORT TYPE 3. DATES COVERED 00-00-2001 to 00-00-2001 4. TITLE AND SUBTITLE Optical Properties of Mineral Particles and Their Effect on Remote-Sensing Reflectance in Coastal Waters 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e. TASK NUMBER 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) Marine Physical Laboratory,,Scripps Institution of Oceanography,,University of California at San Diego,,La Jolla,,CA, 92093 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR S ACRONYM(S) 12. DISTRIBUTION/AVAILABILITY STATEMENT Approved for public release; distribution unlimited 13. SUPPLEMENTARY NOTES 14. ABSTRACT 11. SPONSOR/MONITOR S REPORT NUMBER(S) 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT a. REPORT unclassified b. ABSTRACT unclassified c. THIS PAGE unclassified Same as Report (SAR) 18. NUMBER OF PAGES 8 19a. NAME OF RESPONSIBLE PERSON Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39-18

correction for this error is needed. This assumption was tested with a MgCO 3 sample characterized by high scattering and negligible absorption. In addition, the relatively large size of the integrating sphere ensured that the perturbation of the light field within the sphere due to sample cuvette was negligible. This was tested with samples that absorb but do not scatter light. In these tests, the measurements were made with samples placed outside and inside the sphere. To examine the absorption properties of natural assemblages of marine particles in coastal waters we analyzed a large data set collected during the European project Coastlooc (Coastal Surveillance Through Observation of Ocean Color), which took place in various waters around Europe in 1997-98. The study sites included coastal waters in the Mediterranean, Adriatic Sea, English Channel, North Sea, and Baltic Sea. Some sites represented the waters with significant input of terrestrial material from rivers, for example Rhine, Loire, Seine, Thames, Rhone, Po, and Elbe. Data on total particulate absorption, phytoplankton absorption, non-algal absorption, and dissolved organic matter absorption were included in the analysis. One important task of the analysis was focused on the variability in the magnitude, spectral shape, and regional differentiation of absorption by non-algal particles. Dr. Marcel Babin from France, who has been a visiting scientist in my laboratory since June 2000, played the key role in this work. Dr. Babin was one of the principal investigators of the Coastlooc project. WORK COMPLETED Laboratory tests of our integrating sphere system for measuring absorption was completed. Measurements of absorption spectra of several samples dominated by mineral particles representative of Saharan dust, Spitsbergen fjords with input of particles from glaciers, and Sea of Japan, were made. The analysis of Coastlooc absorption data was completed. The manuscript was submitted for publication (Babin et al., submitted). Two papers resulting from this project were published during the reporting period (Stramski et al., 2001; Loisel et al., 2001). As part of the revision of the paper by Stramski et al., I made a series of new simulations to model the ocean inherent optical properties (IOPs) as a function of the detailed composition of planktonic community. These simulations were focused on blooms of various types of phytoplankton. The other paper (Loisel et al., 2001) compares experimental data with the model for estimating IOPs from apparent optical properties. This model was also developed under this project (Loisel and Stramski, 2000). In addition, I submitted a paper on the effects of growth conditions on phytoplankton optical properties, which is based on my ONR-sponsored research conducted in recent years (Stramski et al., submitted). Finally, two presentations resulting from this project were given at the Ocean Optics XV Conference in Monaco (Stramski and Loisel, 2000; Piskozub and Stramski, 2000). RESULTS Tests of our Perkin-Elmer spectrophotometer with the MgCO 3 samples showed that the scattering error in the absorption measurement is minimal when the sample is placed inside the integrating sphere. Measurements of aqueous solutions of K 2 CrO 4, KMnO 4, and CuSO 4 showed that placing the sample cuvette inside the integrating sphere has negligible effect on the absorption measurement. 2

Measurements of absorption spectra of natural samples dominated by mineral particles showed that absorption declines to zero in the near infrared region of the spectrum, 750-800 nm (Figure 1). This is an important result, which does not support scarce data in the literature showing significant absorption in the near infrared. We conclude that previous literature data (e.g., Bukata et al., 1995) are most likely subject to significant scattering error. 0.06 0.10 Saharan / Japan Sea dust 0.05 0.04 0.03 0.02 0.01 Saharan dust Glacier dust Japan Sea dust 0.08 0.06 0.04 0.02 Glacier dust 0.00 0.00 300 400 500 600 700 800 Wavelength (nm) Figure 1. Absorption spectra of natural samples dominated by mineral particles. [graph: absorption declines to zero as light wavelength increases from the UV to near infrared region of the spectrum] Examples of absorption spectra of non-algal particles measured in various coastal waters around Europe during the Coastlooc project are shown in Figure 2 (left-hand panel). For many Coastlooc stations mineral particles make significant contribution to non-algal absorption. In addition to regional differences in the magnitude of non-algal absorption, the spectral shape also shows some variability. Example spectra from coastal waters in the Mediterranean and English Channel show a spectral feature in the 450-500 nm region, that is a noticeable change in the spectral slope. This feature can likely be attributed to clay minerals associated with the presence of iron oxides. The Baltic Sea samples consistently show steeper slope of the spectrum at wavelengths longer than 440 nm compared to the slope at shorter wavelengths. The origin of this feature remains to be an open question. Regardless of this variability, the exponential function provides a good fit to most of our Coastlooc spectra of nonalgal absorption. The average value of the exponential slope for all these data is 0.0123 nm -1 with the coefficient of variation of 10.3% (Figure 2, right-hand panel). The overall range of the slope parameter is from about 0.009 to 0.018 nm -1. We also found that non-algal absorption shows 3

significant correlation with dry weight of suspended particulate matter in the investigated coastal waters. a NAP (λ) - a NAP (background) (m -1 ) 0.7 0.6 0.5 0.4 0.3 0.2 0.1 North Sea Mediterranean Sea Baltic Sea English Channel (a) Number 50 Total N = 348 40 30 20 10 (b) 0.0 400 500 600 700 0 0.008 0.010 0.012 0.014 0.016 0.018 Wavelength (nm) S NAP (nm -1 ) Figure 2. Examples of absorption spectra of non-algal particles in various coastal waters around Europe (left-hand panel) and frequency distribution of the exponential slope of the non-algal particle absorption spectrum based on all the Coastlooc data from European coastal waters (righthand panel). [graph: absorption spectra of non-algal particles differ in magnitude and spectral shape in various European coastal waters and the average exponential slope of these spectra is 0.0123 nm -1 ]. IMPACT/APPLICATIONS The major impact of this project is to fill the gap in our understanding of light absorption and scattering by mineral particles suspended in seawater. This understanding is prerequisite to advancing numerous applications associated with optical measurements, especially in coastal environments. Although suspended minerals play a major role in coastal optics (for example, they can often be the most important source of backscattering), these particles have been among the least studied components of sea water. At present, the lack of quantitative information on the optical properties of minerals and their variability limits our capabilities to: (1) understand the magnitudes and variability of the bulk optical properties in coastal waters, (2) develop reliable remote sensing algorithms for coastal waters, (3) develop improved methods for optical imaging/detection of underwater targets and bottom objects, and (4) develop and test shallow water radiative transfer models. I anticipate that this project will contribute to advances in these areas of science and applications. In addition, potential future impact is to improve models describing the relationships between the ocean optical properties and seawater components. Present models are typically limited only to two or 4

three components (phytoplankton, detritus, dissolved organic matter) in addition to pure water itself. In this common approach a water body is considered with no regard as to composition of living and non-living particulate matter, for example plankton species or mineral species. This is one important reason for why the present models are unable to explain or predict the substantial optical variability observed in the field. Although a complete optical description incorporating each and every individual component of seawater is clearly unattainable, there is a need to accommodate more components, which would provide a more realistic model. The paper by Stramski et al. (2001) represents a significant step towards to the development of such advanced optical models. TRANSITIONS Parts of my database of the optical properties of marine particles were made available to Dr. Vladimir Haltrin from Naval Research Laboratory at Stennis Space Center, Dr. Cecile Dupouy from Universite Pierre et Marie Curie in France, and Mr. James Coleman from University of Washington (for his masters work). The entire database have been utilized in radiative transfer simulations carried out by Dr. Curtis Mobley from Sequoia Scientific, Inc. RELATED PROJECTS The European project Coastlooc (Coastal Surveillance Through Observation of Ocean Color) provided unique data on absorption properties of marine particles in various coastal waters. REFERENCES Babin, M., D. Stramski, G. M. Ferrari, H. Claustre, A. Bricaud, G. Obolensky, and N. Hoepfner. Variations in the light absorption coefficients of phytoplankton, non-algal particles, and dissolved organic matter in coastal waters around Europe. J. Geophys. Res. (submitted). Bukata, R. P., J. H. Jerome, K. Ya. Kondratyev, and D. V. Pozdnyakov. 1995. Optical Properties and Remote Sensing of Inland and Coastal Waters, CRC Press, Boca Raton. Loisel, H., and D. Stramski. 2000. Estimation of the inherent optical properties of natural waters from irradiance attenuation coefficient and reflectance in the presence of Raman scattering. Appl. Opt. 39: 3001-3011. Loisel, H., D. Stramski, B. G. Mitchell, F. Fell, V. Fournier-Sicre, B. Lamasle, and M. Babin. 2001. Comparison of the ocean inherent optical properties obtained from measurements and inverse modeling. Appl. Opt. 40: 2384-2397. Piskozub, J., and D. Stramski. 2000. The use of scattering error in absorption measurement for estimating the scattering phase function of marine phytoplankton. Ocean Optics XV Conference, Monaco. Stramski, D., and H. Loisel. 2000. Spectral scattering and absorption coefficients of mineral particles suspended in sea water. Ocean Optics XV Conference, Monaco. 5

Stramski, D., A. Bricaud, and A. Morel. 2001. Modeling the inherent optical properties of the ocean based on the detailed composition of planktonic community. Appl. Opt. 40: 2929-2945. Stramski, D., A. Sciandra, and H. Claustre. Effects of temperature, nitrogen, and light limitation on the optical properties of the marine diatom Thalassiosira pseudonana. Limnol. Oceanogr. (submitted). PUBLICATIONS Stramski, D., and C. D. Mobley. 1997. Effects of microbial particles on oceanic optics: A database of single-particle optical properties. Limnol. Oceanogr. 42: 538-549. Mobley C. D., and D. Stramski. 1997. Effects of microbial particles on oceanic optics: Methodology for radiative transfer modeling and example simulations. Limnol. Oceanogr. 42: 550-560. Jonasz, M., G. Fournier, and D. Stramski. 1997. Photometric immersion refractometry: A method for determining the refractive index of marine microbial particles from beam attenuation. Appl. Opt. 36: 4214-4225. Reynolds, R. A., D. Stramski, and D. A. Kiefer. 1997. The effect of nitrogen-limitation on the absorption and scattering properties of the marine diatom Thalassiosira pseudonana. Limnol. Oceanogr. 42: 881-892. Berwald, J., D. Stramski, C. D. Mobley, and D. A. Kiefer. 1998. The effect of Raman scattering on the average cosine and the diffuse attenuation coefficient of irradiance in the ocean. Limnol. Oceanogr. 43: 564-576. Bogucki, D., J. A. Domaradzki, D. Stramski, and J. R. V. Zaneveld. 1998. Comparison of nearforward light scattering on oceanic turbulence and particles. Appl. Opt., 37: 4669-4677. Stramski, D., and D. A. Kiefer. 1998. Can heterotrophic bacteria be important to marine light absorption? J. Plankton Res. 20: 1489-1500. Stramski, D. 1999. Refractive index of planktonic cells as a measure of cellular carbon and chlorophyll a content. Deep-Sea Res. 46: 335-351. Stramska, M., D. Stramski, B. G. Mitchell, and C. D. Mobley. 2000. Estimation of the absorption and backscattering coefficients from in-water radiometric measurements. Limnol. Oceanogr. 45: 628-641. Loisel, H., and D. Stramski. 2000. Estimation of the inherent optical properties of natural waters from irradiance attenuation coefficient and reflectance in the presence of Raman scattering. Appl. Opt. 39: 3001-3011. Loisel, H., D. Stramski, B. G. Mitchell, F. Fell, V. Fournier-Sicre, B. Lamasle, and M. Babin. 2001. Comparison of the ocean inherent optical properties obtained from measurements and inverse modeling. Appl. Opt. 40: 2384-2397. 6

Stramski, D., A. Bricaud, and A. Morel. 2001. Modeling the inherent optical properties of the ocean based on the detailed composition of planktonic community. Appl. Opt. 40: 2929-2945. Terrill, E. J., Melville, W. K., and D. Stramski. 2001. Bubble entrainment by breaking waves and their influence on optical scattering in the upper ocean. J. Geophys. Res. 106 (C8): 16815-16823. Babin, M., D. Stramski, G. M. Ferrari, H. Claustre, A. Bricaud, G. Obolensky, and N. Hoepfner. Variations in the light absorption coefficients of phytoplankton, non-algal particles, and dissolved organic matter in coastal waters around Europe. J. Geophys. Res. (submitted). Stramski, D., A. Sciandra, and H. Claustre. Effects of temperature, nitrogen, and light limitation on the optical properties of the marine diatom Thalassiosira pseudonana. Limnol. Oceanogr. (submitted). PATENTS None 7