A novel approach to investigating chlorophyll-a fluorescence quantum yield variability in the Southern Ocean

The apparent fluorescence quantum yield of chlorophyll-a (ΦF ), i.e. the ratio of photons emitted as chlorophyll-a fluorescence to those absorbed by phytoplankton, serves as a first order measure of photosynthetic efficiency and a photophysiological indicator of the resident phytoplankton community. Drivers of ΦF variability, including taxonomy, nutrient availability, and light history, differ in magnitude of influence across various biogeographic provinces and seasons. A Multi-Exciter Fluorometer (MFL, JFE Advantech Co., Ltd.) was selected for use in in situ ΦF derivation and underwent an extensive radiometric calibration for this purpose. Wavelength-specific ΦF was determined for 66 in situ field stations, sampled in the Atlantic Southern Ocean during the austral winter of 2012 and summer of 2013/ 2014. Phytoplankton pigments, macronutrient concentrations, and light levels were simultaneously measured to investigate their influence on ΦF . While no relationship was observed between macronutrient levels and ΦF , an inverse relationship between light and ΦF was apparent. This was likely due to the influence of speciesspecific fluorescence quenching mechanisms employed by local populations. ΦF derived from ocean colour products (Φsat) from the Moderate Resolution Imaging Spectroradiometer (MODIS) were compared to in situ ΦF to assess the performance of three existing Φsat algorithms. Results indicate that accounting for chlorophyll-a fluorescence reabsorption, the inherent optical properties of the surrounding water column, and the sensor angle of observation, is crucial to reducing Φsat uncertainty. A hybrid combination of two of the algorithms performed best, and was used to derive Φsat for stations co-located to in situ iron measurements in the Atlantic Southern Ocean. A significant negative relationship was observed, indicative of the effects of iron availability on quantum yield and its potential as a proxy for iron limitation. However, separating the individual contributions of light, taxonomy, and iron limitation to Φsat variability remains a challenge. A time series analysis of Φsat was also undertaken, which revealed a prominent Φsat seasonal cycle. Ultimately, increased in situ sampling would expedite the development of improved Φsat algorithms; the routine retrieval of Φsat would offer insight into phytoplankton dynamics in undersampled regions such as the climate relevant Southern Ocean