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  • 1
    Publication Date: 2020-02-06
    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.
    Type: Article , PeerReviewed
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  • 2
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    Copernicus Publications (EGU)
    In:  Biogeosciences (BG), 16 (22). pp. 4485-4496.
    Publication Date: 2022-01-31
    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.
    Type: Article , PeerReviewed
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  • 3
    Publication Date: 2023-02-08
    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.
    Type: Article , PeerReviewed
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  • 4
    Publication Date: 2024-02-07
    Description: Nitric oxide (NO) is an atmospheric pollutant and climate forcer as well as a key intermediary in the marine nitrogen cycle, but the ocean’s NO contribution and production mechanisms remain unclear. Here, high-resolution NO observations were conducted simultaneously in the surface ocean and the lower atmosphere of the Yellow Sea and the East China Sea; moreover, NO production from photolysis and microbial processes was analyzed. The NO sea–air exchange showed uneven distributions (RSD = 349.1%) with an average flux of 5.3 ± 18.5 × 10–17 mol cm–2 s–1. In coastal waters where nitrite photolysis was the predominant source (89.0%), NO concentrations were remarkably higher (84.7%) than the overall average of the study area. The NO from archaeal nitrification accounted for 52.8% of all microbial production (11.0%). We also examined the relationship between gaseous NO and ozone which helped identify sources of atmospheric NO. The sea-to-air flux of NO in coastal waters was narrowed by contaminated air with elevated NO concentrations. These findings indicate that the emissions of NO from coastal waters, mainly controlled by reactive nitrogen inputs, will increase with the reduced terrestrial NO discharge.
    Type: Article , PeerReviewed
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  • 5
    Publication Date: 2024-02-07
    Description: To examine the alteration of river-derived sediments through a large estuary and the implications for elemental cycling and global climate, this study analyses lithium (Li) isotopes and elemental concentrations (e.g., Li, Na, Mg, K, Ca, Fe and Al) of both the dissolved load and different phases of the sediment load (i.e., exchangeable, carbonate, oxide, clay and residue) in the Amazon estuary. The results show that river-derived sediments remove Li from the dissolved load, largely due to cation retention in secondary clays. By modelling the Li mass-balance and isotope fractionation, we estimate that the river-derived sediments gain 3–4 μg/g Li from the dissolved load in the Amazon estuary, with a Li isotope fractionation factor (αclay-solution) of approximately 0.975. Considering the whole Amazon estuary, the river-derived sediments remove around 3.6–4.8 × 109 g/yr of Li from the dissolved load. Specifically, around 1.0–1.7 × 108 g/yr of Li is removed from river water (∼1.8–3.0% of the dissolved Li discharge flux of the Amazon River) and around 3.5–4.7 × 109 g/yr of Li is removed from seawater, which represents a significant sink from the ocean. This estuarine Li sink is likely to be related to continental erosion rates; thus, continental weathering and erosion regimes could influence not only riverine Li input, but could also directly affect the Li sink, leading to a dual control on the Li budget and isotope composition in the ocean.
    Type: Article , PeerReviewed
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  • 6
    Publication Date: 2024-02-07
    Description: Nitric oxide (NO) is a short-lived intermediate of the oceanic nitrogen cycle, and it is produced by biological and photochemical processes in the ocean. Nitrogen dioxide (NO2) is a reactive atmospheric compound which has not been determined in the ocean so far. Here, we present the setup and validation of a novel continuous underway measurement system to measure dissolved NO and NO2 in the surface ocean. The system consists of a seawater/gas equilibration component coupled to a chemiluminescence detector. It was successfully deployed during a 12 day cruise to the East China Sea in May 2018. Dissolved NO and NO2 surface concentrations ranged from 〈limit of detection (LOD) to 98 × 10-12 mol L-1 and 〈LOD to 83 × 10-12 mol L-1, respectively. The ECS was supersaturated with NO but significantly undersaturated with NO2, indicating that the surface waters were a source for atmospheric NO but a sink for atmospheric NO2 at the time of our measurements.
    Type: Article , PeerReviewed
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