Spectroscopic detection of a ubiquitous dissolved pigment degradation product in subsurface waters of the global ocean

Measurements of light absorption by chromophoric dissolved organic matter (CDOM) from subsurface waters of the tropical Atlantic and Pacific Oceans showed a distinct absorption shoulder at 410-415 nm. This indicates an underlying absorption of a pigment whose occurrence is partly correlated with the apparent oxygen utilization (AOU) but also found in the deep chlorophyll maximum. A similar absorption maximum at similar to 415 nm was also found in the particulate fraction of samples taken below the surface mixing layer and is usually attributed to absorption by respiratory pigments of heterotrophic unicellular organisms. In our study, fluorescence measurements of pre-concentrated dissolved organic matter (DOM) samples from 200-6000 m confirmed a previous study suggesting that the absorption at similar to 415 nm was related to fluorescence at 650 nm in the oxygen minimum zone. The absorption characteristics of this fluorophore was examined by fluorescence emission/excitation analysis and showed a clear excitation maximum at 415 nm that could be linked to the absorption shoulder in the CDOM spectra. The spectral characteristics of the substance found in the dissolved and particulate fraction did not match with those of chlorophyll a degradation products (as found in a sample from the sea surface) but can be explained by the occurrence of porphyrin pigments from either heterotrophs or autotrophs. Combining the observations of the fluorescence and the 415-nm absorption shoulder suggests that there are high concentrations of a pigment degradation product in subsurface DOM of all major oceans. Most pronouncedly we found this signal in the deep chlorophyll maximum and the oxygen minimum zone of tropical regions. The origin, chemical nature, turnover rate, and fate of this molecule is so far unknown.