We investigated the production of ammonium by the photodegradation of dissolved organic matter (DOM) in the coastal upwelling system off central Chile (36°S). The mean penetration of solar radiation (Z1%) between April 2011 and February 2012 was 9.4 m, 4.4 m and 3.2 m for Photosynthetically Active Radiation (PAR; 400–700 nm), UV-A (320–400 nm) and UV-B (280–320 nm), respectively. Ammonium photoproduction experiments were carried out using exudates of DOM obtained from cultured diatom species (Chaetoceros muelleri and Thalassiosira minuscule) as well as natural marine DOM. Diatom exudates showed net photoproduction of ammonium under exposure to UVR with a mean rate of 0.56±0.4 µmol L−1 h−1 and a maximum rate of 1.49 µmol L−1 h−1. Results from natural marine DOM showed net photoproduction of ammonium under exposure to PAR+UVR ranging between 0.06 and 0.2 µmol L−1 h−1. We estimated the potential contribution of photochemical ammonium production for phytoplankton ammonium demand. Photoammonification of diatom exudates could support between 117 and 453% of spring-summer NH4 + assimilation, while rates obtained from natural samples could contribute to 50–178% of spring-summer phytoplankton NH4 + requirements. These results have implications for local N budgets, as photochemical ammonium production can occur year-round in the first meters of the euphotic zone that are impacted by full sunlight.

We report the seasonal and single-diurnal variability of potentially active members of the prokaryote community in coastal surface waters off central Chile and the relationship between nitrifiers and solar radiation by combining 16S cDNA-based pyrosequencing, RT-qPCR of specific gene markers for nitrifiers (amoA, for general AOA, AOA-A, AOA-B, Nitrosopumilus maritimus and beta-AOB; and 16S rRNA gene for Nitrospina-like NOB), and solar irradiance measurements. We also evaluated the effects of artificial UVA-PAR and PAR spectra on nitrifiers by RT-qPCR. All nitrifiers (except AOA-B ecotype) were detected via RT-qPCR but AOA was the only group detected by pyrosequencing. Results showed high variability in their transcriptional levels during the day which could be associated to sunlight intensity thresholds in winter although AOA and Nitrospina-like NOB transcript number were also potentially related with environmental substrate availability. Only N. maritimus amoA transcripts showed a significant negative correlation with solar irradiances in both periods. During spring-summer, Nitrospina transcripts decreased at higher sunlight intensities, whereas the opposite was found during winter under natural (in situ) and artificial light experiments. In summary, a nitrifying community with variable tolerance to solar radiation is responsible for daily nitrification, and was particularly diverse during winter in the study area.

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