Estimation of net accumulation and removal of fluorescent dissolved organic matter in different Baltic Sea water masses

Abstract

This study aimed to detect non-conservative processes that affect the distribution of fluorescent dissolved organic matter (FDOM) in the Baltic Sea. An extensive data set comprised of 408 FDOM data, optical and physical profiles, and the development of a water masses balance model allowed us to ascertain the sources of mixing anomalies. These were seen as second-order deviations in the FDOM distribution as a function of salinity in three layers: surface water, Baltic Sea Winter Water, and deep water. The difference between modeled and measured FDOM values at three different excitation/emission wavelengths allowed to show the strength of non-conservative processes, such as photochemical and microbial decomposition (negative residual values) or extracellular release of dissolved organic matter from phytoplankton, heterotrophic uptake and release from anoxic sediments (positive residual values). Humic-like FDOM fractions displayed positive residuals in all seasons for intermediate and deep layers and negative residuals in surface waters. Largest accumulation rates of humic-like fractions were reached in the Gulf of Gdańsk during summer in intermediate and deep layers, while the greatest removal in surface waters was observed during spring in the Bornholm and Gotland Basins and during summer in the Gulf of Gdańsk, probably due to photodegradation. Positive residuals of the protein-like fraction were observed at the surface in summer and autumn in the Gulf of Gdańsk, probably linked to the abundance of phytoplankton and also due to the low molecular weight by-products of photodegradation of humic-like components. Spatial transects revealed an increase in humic-like residuals with depth and a strong correlation with apparent oxygen utilization, increasing with higher fluorescence and exhibiting an asymptotic trend. A relationship was found between the protein-like fractions and phytoplankton biomass proxies. A generalized concept for FDOM cycling in the Baltic Sea was proposed, highlighting photobleaching as the dominant non-linear process determining the efficiency of humic-like FDOM removal. The protein-like component was found to be more efficiently taken up by aerobic prokaryotes at the surface. Microbial utilization and reworking of organic matter, release from sediments, and a decade-long stagnation of bottom water masses, all contribute to the observed accumulation of FDOM in mesohaline deep waters below the permanent pycnocline in the Baltic Sea.