Improving Assessments of Chlorophyll Concentration From In Situ Optical Measurements

Florescence as a chlorophyll proxy has poor accuracy because it is dependent on specific absorption (effective molar absorptivity of packaged chlorophyll in living cells) and fluorescence quantum yield, both of which are highly variable. Absorption is a better proxy, as it is only dependent on specific absorption for packaged chlorophyll, although excepted accuracy in using a nominal specific absorption for all phytoplankton is still about 50%. Bricaud et al. (1995), Ciotti et al. (2002), Mouw et al. (2010), etc. have shown, however, that specific absorption is closely related to the average size of phytoplankton due to the relative packaging effect. Through other methods that have been developed over the years (Morel 1973; Diehl and Haart 1980; Boss et al. 2001; Slade and Boss 2015), it has been shown that measurements of spectral particulate attenuation (i.e., light transmission), and perhaps spectral particulate backscattering, can be used as simple proxies for the average size of the particle field. We therefore test the hypothesis that information on average particle size may be used to better estimate specific absorption for packaged chlorophyll, possibly enabling more accurate retrievals of chlorophyll concentration from optical measurements. The required optical measurements can be made with compact commercial off-the-shelf sensors with high sampling frequency that can be operated from autonomous vehicles; as a result, derived chlorophyll concentration could be resolved at far higher temporal and spatial frequency than is currently possible through extracting chlorophyll from discretely collected samples. This study examines the relationship between specific absorption and the attenuation spectral slope in extensive datasets from Case I and Case II waters found globally in an attempt to assess the link between pigment packaging and phytoplankton size dynamics and the impact on improving the derivation of chlorophyll from in situ optical measurements.