Resumen de Optical propertiers of the dissolved organic matter as tracers of microbiological and geochemical processes in marine ecosystems
Oceans store 685 Pg of organic carbon of which 662 Pg are in a dissolved form. The diversity of compounds that make up the dissolved organic matter (DOM) pool and the low concentration of each compound make the chemical characterization of this material a difficult task. For that reason, less than 11% of the oceanic DOM has been identified. A variable fraction of the DOM ¿between 20% in the open ocean and 70% in coastal areas- absorbs UV and visible radiation and it is known as coloured DOM (CDOM). A sub-fraction of the CDOM emits the absorbed radiation as fluorescence, although with a low quantum yield (around 1%), and this is called fluorescent DOM (FDOM). The study of the CDOM and FDOM pools, combining the spectroscopy of absorption and fluorescence, allows us to obtain knowledge about (i) the molecular structure of the DOM (i.e., aromaticity and average molecular weigh) and (ii) its biological and photochemical reactivity in a relatively simple, fast and economic way. This can be done through the study of the production, utilization and/or chemical alteration of the different chromophores and fluorophores in response to the activity of the microorganisms and the solar radiation in the ocean. The work that has resulted in this thesis has involved both laboratory experiments and field studies. Some experiments have deepened our knowledge of (or focused on??) the microbiological sources of the CDOM and FDOM. For example, our work has shown that marine phytoplankton produces a fluorophore at Ex/Em 320/410 nm which is consumed by marine bacteria which at the same time produce another absorbing fluorophore at Ex/Em 340/440. These ¿humic-like¿ fluorophores, known in the literature as ¿pico-M¿ and ¿pico-C¿, are considered to be characteristic of marine and continental ecosystems, respectively. This work suggests that differentiation is mostly due to the type of cells that produce them: eukaryotic and prokaryotic cells. Furthermore, DOM isolated by tangential ultrafiltration (> 1 KDa) from different aquatic environments has also been characterized. Significant changes were observed in the aromaticity and average molecular weigh of the samples depending on whether they were of continental or marine origin and also on the exposition to the sunlight before sampling. Moreover, controlled experiments were performed in order to study the response of these materials to natural radiation. These experiments showed degradation of the humic-like fluorophores ¿peak-M¿ and ¿peak-C¿ and the formation of another protein-like fluorophores, known in literature as ¿pico-T¿. When the marine bacteria were cultivated using the irradiated materials as substrate a rapid recovery of the humic-like fluorophores was observed. This recovery was proportional to the initial fluorescence of the materials before irradiation. Finally, we have also studied the relative importance of the processes that involve the mixing between water masses of continental and marine origin, microbial production and photochemical degradation on the CDOM and FDOM distribution of two distinct coastal ecosystem: the ¿Ría de Vigo¿ and the Blanes Bay. The Ría de Vigo, enclosed in the Iberian upwelling system, is periodically affected by downwelling and upwelling events. Microbial production was the dominant process during the donwelling period while the photochemical decomposition predominated during upwellings. On the other hand, Blanes Bay, in the oligotrophic Northwest Mediterranean Sea, possesses a seasonal cycle determined by natural radiation. This is characterized by the accumulation of chromophores and fluorophores absorbing at < 300 nm and the photochemical decomposition of those absorbing at > 300nm during the summer season.
