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Photoproduction of Nitric Oxide in Seawater

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Photoproduction of Nitric Oxide in Seawater Ocean Sci., 16, 135–148, 2020 https://doi.org/10.5194/os-16-135-2020 © Author(s) 2020. This work is distributed under the Creative Commons Attribution 4.0 License. Photoproduction of nitric oxide in seawater Ye Tian1,2,3, Gui-Peng Yang1,2,3, Chun-Ying Liu1,2,3, Pei-Feng Li3, Hong-Tao Chen1,2,3, and Hermann W. Bange4 1Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Qingdao 266100, China 2Laboratory for Marine Ecology and Environmental Science, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266071, China 3College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, 266100, China 4Chemical Oceanography, Division of Marine Biogeochemistry, GEOMAR – Helmholtz-Zentrum für Ozeanforschung Kiel, Kiel 24105, Germany Correspondence: Chun-Ying Liu ([email protected]) and Hong-Tao Chen ([email protected]) Received: 25 May 2019 – Discussion started: 11 June 2019 Revised: 5 December 2019 – Accepted: 13 December 2019 – Published: 23 January 2020 Abstract. Nitric oxide (NO) is a short-lived intermediate of nation method so far because of its high reactivity with other the oceanic nitrogen cycle. However, our knowledge about substances (Zafiriou et al., 1980; Lutterbeck and Bange, its production and consumption pathways in oceanic environ- 2015; Liu et al., 2017). NO is produced and consumed during ments is rudimentary. In order to decipher the major factors various microbial processes such as nitrification, denitrifica- affecting NO photochemical production, we irradiated sev- tion, and anammox (Schreiber et al., 2012; Kuypers et al., eral artificial seawater samples as well as 31 natural surface 2018). Moreover, it is known that both phytoplankton and seawater samples in laboratory experiments. The seawater zooplankton can metabolize NO, and they are influenced by samples were collected during a cruise to the western trop- ambient (extracellular) NO concentrations (Singh and Lal, ical North Pacific Ocean (WTNP, a N–S section from 36 to 2017; Wang et al., 2017; Astier et al., 2018). 2◦ N along 146 to 143◦ E with 6 and 12 stations, respectively, Apart from (micro)biological processes, NO can be pro- ◦ − and a W–E section from 137 to 161 E along the Equator duced photochemically from dissolved nitrite (NO2 ) in the with 13 stations) from November 2015 to January 2016. NO sunlit surface ocean (Zafiriou and True, 1979; Zafiriou and photoproduction rates from dissolved nitrite in artificial sea- McFarland, 1981): water showed increasing trends with decreasing pH, increas- − hν − ing temperature, and increasing salinity. In contrast, NO pho- NO C H2O −! NO C OH C OH : (R1) −12 −1 −1 2 toproduction rates (average: 0:5 ± 0:2 × 10 mol L s ) q in the natural seawater samples from the WTNP did not Mack and Bolton (1999) reviewed the possible subsequent show any correlations with pH, water temperature, salin- reactions of Reaction (1); for example, the produced NO and ity, or dissolved inorganic nitrite concentrations. The flux hydroxyl radical (OH ) of Reaction (1) could react to pro- induced by NO photoproduction in the WTNP (average: duce HNO2 reverselyq (Reaction 2) and some reactions that − − − 13×10 12 mol m 2 s 1) was significantly larger than the NO consumed NO or its oxides like Reaction (3) to Reaction (8). air–sea flux density (average: 1:8 × 10−12 mol m−2 s−1), in- dicating a further NO loss process in the surface layer. NO C OH ! HNO2 (R2) NO C NO2 ! N2O3 (R3) C ! C C − N2O3 H2O 2H 2NO2 (R4) 1 Introduction NO C NO ! N2O2 (R5) N O C O ! N O (R6) Nitric oxide (NO) is a short-lived intermediate of the oceanic 2 2 2 2 4 nitrogen cycle; see Bange (2008) and Kuypers et al. (2018). 2NO2 ! N2O4 (R7) C ! C C − C − There are only a few reports about the oceanic NO determi- N2O4 H2O 2H NO2 NO3 (R8) Published by Copernicus Publications on behalf of the European Geosciences Union. 136 Y. Tian et al.: Photoproduction of nitric oxide in seawater − Table 1. Photoproduction rates (R), methods, average NO concentrations, NO2 concentrations, and average flux densities of NO in different regions. − Regions R Methods NO NO2 Flux Sampling date References (mol L−1 s−1) (mol L−1) (µmol L−1) (mol m−2 s−1) Seto Inland Sea, Japan 8.7–38:8 × 10−12 DAF-2 120 × 10−12 0.5–2 3:55 × 10−12 5–9 October 2009 Olasehinde et al. (2010) Seto Inland Sea, Japan 1.4–9:17 × 10−12 DAF-2 3–41 × 10−12 0–0.4 0:22 × 10−12 September 2013 and Anifowose and Sakugawa June 2014 (2017) Kurose River, Japan 9.4–300 × 10−12 DAF-2 – - – – Olasehinde et al. (2009) Kurose River (K1 4 × 10−12 DAF-2 1:6 × 10−12 0.06 – Monthly 2013 Anifowose et al. (2015) station), Japan Jiaozhou Bay – DAN 157 × 10−12 – 7:2 × 10−12 June, July, and Tian et al. (2016) August 2010 Jiaozhou Bay and – DAN (160 ± 130) – 10:9 × 10−12 8–9 March 2011 Xue et al. (2012) its adjacent waters ×10−12 Coastal water off 1:52 × 10−12 DAN 260 × 10−12 0.75 – November 2009 Liu et al. (2017) Qingdao Central equatorial > 10−12 Chemilumi- 46 × 10−12 0.2 2:2 × 10−12 R/V Knorr 73/7 Zafiriou and McFarland Pacific nescence (1981) The northwest (0:5 ± 0:2) ×10−12 DAF-2 49 × 10−12 0.06 1:8 × 10−12 15 November 2015 to This study Pacific Ocean 26 January 2016 Besides, in natural sunlit seawater, photolyzed dissolved ni- in Kurose River (average: 499 × 10−12 mol L−1 s−1) were trate (NO−) could be a source of NO through NO− (Reac- the largest, which might be due to an increase in nitrite 3 C 2 tion 9); during the process of ammonium (NH =NH3) ox- being released into the river because of agricultural activ- − − 4 idation into NO2 and NO3 , NO might be an intermedi- ity during the study time. However, NO concentration was ate (Joussotdubien and Kadiri, 1970), or NO could be pro- about 1:6 × 10−12 mol L−1, at the lowest level, which was duced through amino-peroxyl radicals (NH2O2) through Re- because of higher scavenging rate in river water. Anifowose actions (10) to (14) (Laszlo et al., 1998; Clarkeq et al., 2008). et al. (2015) found that NO lifetime, which was defined as the reciprocal of first-order scavenging rate constant of NO − hν − 1 (Olasehinde et al., 2010) in Kurose River, was only 0.25 s. NO −! NO C O2 (R9) 3 2 2 The lifetime of NO showed an increasing trend from river C − 2− ! − C − OH HCO3 =CO3 CO3 H2O=OH (R10) (several seconds) via inland sea (dozens of seconds) to open q q sea (dozens to hundreds of seconds), reviewed in Anifowose OH C NH3 ! NH2 C H2O (R11) and Sakugawa (2017). However, NO showed higher concen- CO q− C NH ! NHq C HCO− (R12) 3 3 2 3 tration levels in coastal waters than in open sea; higher photo- q C ! q NH2 O2 NH2O2 (R13) production rates in coastal waters than open sea, or other pro- q q NH2O2 ! NO C H2O (R14) duction processes in coastal waters, might account for this. q q In this study, we present the results of our measurements Table 1 summarizes studies about photochemical production of NO photoproduction in laboratory experiments using ar- of NO measured in the surface waters of the equatorial Pa- tificial and natural seawater samples. The major objectives cific Ocean (Zafiriou et al., 1980; Zafiriou and McFarland, of our studies were (i) to decipher the factors affecting NO 1981), the Seto Inland Sea (Olasehinde et al., 2009, 2010; photoproduction in seawater, (ii) to determine the photopro- Anifowose and Sakugawa, 2017), the Bohai Sea and Yellow duction rates of NO from samples collected during a cruise to Sea (Liu et al., 2017; Tian et al., 2019), and the Kurose River the western tropical North Pacific Ocean (WTNP), and (iii) to (Japan) (Olasehinde et al., 2009; Anifowose et al., 2015). NO quantify the role of photoproduction as a source of NO in the concentration was determined by the balance of the produc- surface waters of the WTNP. tion and the removal process; thus, changes in NO produc- tion and removal rates could influence NO concentration in the seawater. In the surface seawater, the photochemical pro- cess was regarded as the main production process (Zafiriou and McFarland, 1981; Olasehinde et al., 2010; Anifowose et al., 2015). In Table 1, NO photoproduction rates varied among different seawater samples: the photoproduction rates Ocean Sci., 16, 135–148, 2020 www.ocean-sci.net/16/135/2020/ Y. Tian et al.: Photoproduction of nitric oxide in seawater 137 2 Methods at a constant temperature of 20 ◦C by controlling the tem- perature of a thermostat water bath (LAUDA Dr. R. Wobser 2.1 Determination of dissolved NO in aqueous samples GmbH & Co. KG, Germany). The height of the cylindrical quartz cuvette used for irradiation was 70 mm and the in- For the measurements of dissolved NO, we applied the ner diameter was 14 mm with the volume about 10 mL. The method described by Olasehinde et al. (2009). In brief, optical pathlength was 70 ± 1 mm. During the experiment, NO in the aqueous samples was determined by trapping the quartz cuvette, filled with 10 mL sample and blocked by it with added 4,5-diaminofluorescein (DAF-2, chromato- a PTFE stopper, was installed in the simulator and a little graphic grade from Sigma-Aldrich, USA) and measuring the higher than the water bath surface.
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