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An extensive bio-optical data set obtained from field measurements was used to evaluate the performance of an empirical (Kowalczuk et al. 2005) and two semi- analytical algorithms: Carder et al. (1999) and GSM01 (Maritorena et al. 2002) for estimating CDOM absorption in the Baltic Sea. The data set includes coincident measurements of radiometric quantities and absorption coefficients of CDOM made during 43 cruises between 2000 and 2008. In the first stage of the analysis, the accuracy of the empirical algorithm by Kowalczuk et al. (2005) was assessed using in situ measurements of remote sensing reflectance. Validation results improved when matching points located in Gulf of Gdańsk close to the Vistula River mouth were eliminated from the data set. The calculated errors in the estimation of aCDOM(400) in the first phase of the analysis were Bias = −0.02, RMSE = 0.46 and R2 = 0.70. In the second stage, the empirical algorithm was tested on satellite data from SeaWiFS and MODIS imagery. The satellite data were corrected atmospherically with the MUMM algorithm designed for turbid coastal and inland waters and implemented in the SeaDAS software. The results of the best case scenario for estimating the CDOM absorption coefficient aCDOM(400), based on SeaWiFS data, were Bias = −0.02, RMSE = 0.23 and R2 = 0.40. The validation of the Kowalczuk et al. (2005) empirical algorithm applied to MODIS data led to a less accurate estimate of aCDOM(400): Bias = −0.03, RMSE = 0.19 and R2 = 0.29. This assessment of the accuracy of standard semi-analytical algorithms available in the SeaWiFS and MODIS imagery processing software revealed that both algorithms (GSM 01 and Carder) underestimate CDOM absorption in the Baltic Sea with mean systematic and random errors in excess of 70%. The paper presents examples of the application of the Kowalczuk et al. (2005) empirical algorithm for producing maps of the seasonal distribution of aCDOM(400) in the Baltic Sea between 2004 and 2008.
The standard exponential model for CDOM absorption has been applied to data from diverse waters. Absorption at 440 nm (ag440) ranged between close to zero and 10 m−1, and the slope oft he semilogarithmic absorption spectrum over a minimum range of400 to 440 nm (s440) ranged between <0.01 and 0.04 nm−1. No relationship was found between ag440 or s440 and salinity. Except in the southern Baltic, s440 was found to have a broad distribution (0.0165 ± 0.0035), suggesting that it should be introduced as an additional variable in bio-optical models when ag440 is large. An alternative model for CDOM absorption was applied to available high quality UV-visible absorption spectra from the WisGla river (Poland). This model assumes that the CDOM absorption spectrum comprises distinct Gaussian absorption bands in the UV, similar to those ofb enzene. Five bands were fit to the data. The mean central energy ofal l bands was higher in early summer (E ∼7.2, 6.6, 6.4, 6.2 and 5.5 eV or 172, 188, 194, 200 and 226 nm) than in winter. The higher energy bands were found to decay in both height and width with increasing salinity, while lower energy bands broadened with increasing salinity. s440 was found to be correlated with shape parameters of the bands centred at 6.4 and 5.5 eV. While the exponential model is convenient for optical modelling and remote sensing applications, these results suggest that the Gaussian model offers a deeper understanding ofc hemical interactions affecting CDOM molecular structure.
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