Description: We developed a new method for the determination of dissolved nitric oxide (NO) in discrete seawater samples based on the combination of a purge-and-trap setup and a fluorometric detection of NO. 2,3-diaminonaphthalene (DAN) reacts with NO in seawater to form the highly fluorescent 2,3-naphthotriazole (NAT). The fluorescence intensity was linear for NO concentrations in the range from 0.14 to 19 nmol L−1. We determined a detection limit of 0.068 nmol L−1, an average recovery coefficient of 83.8 % (80.2–90.0 %), and a relative standard deviation of ±7.2 %. With our method we determined for the first time the temporal and spatial distributions of NO surface concentrations in coastal waters of the Yellow Sea off Qingdao and in Jiaozhou Bay during a cruise in November 2009. The concentrations of NO varied from below the detection limit to 0.50 nmol L−1 with an average of 0.26 ± 0.14 nmol L−1. NO surface concentrations were generally enhanced significantly during daytime, implying that NO formation processes such as NO2− photolysis are much higher during daytime than chemical NO consumption, which, in turn, lead to a significant decrease in NO concentrations during nighttime. In general, NO surface concentrations and measured NO production rates were higher compared to previously reported measurements. This might be caused by the high NO2− surface concentrations encountered during the cruise. Moreover, additional measurements of NO production rates implied that the occurrence of particles and a temperature increase can enhance NO production rates. With the method introduced here, we have a reliable and comparably easy to use method at hand to measure oceanic NO surface concentrations, which can be used to decipher both its temporal and spatial distributions as well as its biogeochemical pathways in the oceans.

Description: Nitric oxide (NO) is a short-lived intermediate of the oceanic nitrogen cycle. However, our knowledge about its production and consumption pathways in oceanic environments is rudimentary. In order to decipher the major factors affecting NO photochemical production, we irradiated several artificial seawater samples as well as 31 natural surface seawater samples in laboratory experiments. The seawater samples were collected during a cruise to the western tropical North Pacific Ocean (WTNP, a N-S section from 36 to 2 degrees N along 146 to 143 degrees E with 6 and 12 stations, respectively, and a W-E section from 137 to 161 degrees E along the Equator with 13 stations) from November 2015 to January 2016. NO photoproduction rates from dissolved nitrite in artificial seawater showed increasing trends with decreasing pH, increasing temperature, and increasing salinity. In contrast, NO photoproduction rates (average: 0.5 +/- 0.2 x 10(-12) mol L-1 s(-1)) in the natural seawater samples from the WTNP did not show any correlations with pH, water temperature, salinity, or dissolved inorganic nitrite concentrations. The flux induced by NO photoproduction in the WTNP (average: 13 x 10(-12) mol M-2 S-1) was significantly larger than the NO air-sea flux density (average: 1.8 x 10(-12) Mol M-2 S-1), indicating a further NO loss process in the surface layer.

Description: Nitric oxide (NO) is a short-lived compound of the marine nitrogen cycle; however, our knowledge about its oceanic distribution and turnover is rudimentary. Here we present the measurements of dissolved NO in the surface and bottom layers at 75 stations in the Bohai Sea (BS) and the Yellow Sea (YS) in June 2011. Moreover, NO photoproduction rates were determined at 27 stations in both seas. The NO concentrations in the surface and bottom layers were highly variable and ranged from below the limit of detection (i.e., 32 pmol L−1) to 616 pmol L−1 in the surface layer and 482 pmol L−1 in the bottom layer. There was no significant difference (p〉0.05) between the mean NO concentrations in the surface (186±108 pmol L−1) and bottom (174±123 pmol L−1) layers. A decreasing trend of NO in bottom-layer concentrations with salinity indicates a NO input by submarine groundwater discharge. NO in the surface layer was supersaturated at all stations during both day and night and therefore the BS and YS were a persistent source of NO to the atmosphere at the time of our measurements. The average flux was about 4.5×10−16 mol cm−2 s−1 and the flux showed significant positive relationship with the wind speed. The accumulation of NO during daytime was a result of photochemical production, and photoproduction rates were correlated to illuminance. The persistent nighttime NO supersaturation pointed to an unidentified NO dark production. NO sea-to-air flux densities were much lower than the NO photoproduction rates. Therefore, we conclude that the bulk of the NO produced in the mixed layer was rapidly consumed before its release to the atmosphere.