Nitrous Oxide in the North Atlantic Ocean, Global Biogeochem
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A chemical oceanographer's view of nitrous oxide in the ocean Habilitationsschrift vorgelegt von Hermann W. Bange Kiel, Marz 2006 2 Hermann W. Bange: Nitrous oxide in the ocean Hermann W. Bange Forschungseinheit Chemische Ozeanographie Forschungsbereich Marine Biogeochemie IFM-GEOMAR Leibniz-lnstitut fur Meereswissenschaften an der Universitat Kiel Dusternbrooker Weg 20 24105 Kiel Tel.: +49-(0)431-600-4204 Fax: +49-(0)431-600-4202 [email protected] Hermann W. Bange: Nitrous oxide in the ocean 3 "Tatsachlich ist der Fortschritt der Wissenschaften wie ein alter Wilstenpfad ilbersat mit den Gerippen fallengelassener Theorien, die einstmals ewiges Leben zu besitzen schienen. "Arthur Koestler (1905-1983) "All collecting trips to fairly unknown regions should be made twice; once to make mistakes and once to correct them." from 'The log from the Sea of Cortez" by John Steinbeck (1902-1968) 4 Hermann W. Bange: Nitrous oxide in the ocean Hermann W. Bange: Nitrous oxide in the ocean 5 HABILITATION OUTLINE ....•••......•.••.........•..•....••.•...••.....•.••.....••.••.......................•..•• 7 1 INTRODUCTION .••......•......•.....•...•••......••..•..•.•....•.••....••••......•.••••••....................•• 11 2 N20 DISTRIBUTION IN THE WORLD'S OCEANS ...................................................... 14 2.1 Formation and consumption pathways in the ocean ............................... 16 2.2 Depth profiles .......................................................................................... 20 2.3 N20 in the ocean surface layer ................. ~ ............................................. 26 2.4 N20 in coastal areas ............................................................................... 29 2.5 Coastal eutrophication and Fe fertilization .............................................. 31 2.6 N20 isotope studies ................................................................................. 33 2.7 The world's oceans - a major source of atmospheric N20 ...................... 39 3 EQUATIONS TO DESCRIBE THE PHYSICAL PROPERTIES OF OCEANIC N20 .............. .43 3.1 N20 solubility in seawater ...................................................................... .43 3.2 N20 diffusion in water .............................................................................. 44 3.3 Air-sea exchange approaches ................................................................. 45 4 METHODS •.....•.•..•..•.......•••...••.•......••.....••...•....•.•.......•.....••.....•........••.....•.•......• 47 5 OUTLOOK ........................................................................................................ 49 6 ACKNOWLEDGEMENTS ..................................................................................... 56 7 REFERENCES ................................................................................................... 57 ATTACHMENTS ................................................................................................... 66 6 Hermann W. Bange: Nitrous oxide in the ocean Hermann W. Bange: Nitrous oxide in the ocean 7 HABILITATION OUTLINE The two central themes of the publications submitted here in support of my habilitation are: (A) To decipher the distribution and formation processes of oceanic N20 and (B) To quantify the oceanic emissions of N20. During the period of my habilitation (1999-2006, which was delayed by two years due to my move from the Max-Planck-lnstitut fur Chemie, Mainz to the former lnstitut fur Meereskunde, Kiel, now IFM-GEOMAR, Leibniz-lnstitut fur Meereswissenschaften) the following articles have been written: Theme A: Distribution and formation of oceanic N20 1) Bange, H.W., and M.O. Andreae, Nitrous oxide in the deep waters of the world's oceans, Global Biogeochem. Cycles, 13 (4), 1127-1135, 1999. - Describes the N20 distribution in deep waters (>2000m). Identification of the deep water mass agelN20 concentration relationship 2) Bange, H.W., S. Rapsomanikis, and M.O. Andreae, Nitrous oxide cycling in the Arabian Sea, J. Geophys. Res., 106 (C1 ), 1053-1065, 2001. - Presents the N20 distribution and its formation processes in the Arabian Sea based on measurements during four cruises. Suggestion of a four compartment scheme to explain the N20 depth profiles in the central Arabian Sea as a result of nitrification and denitrification processes. Suggestion of an alternative microbial formation process via reduction of 103- near the shelf break along the Arabian Peninsula. 3) * Walter, S., I. Peeken, K. Lochte, A. Webb, and H.W. Bange, Nitrous oxide measurements during EIFEX, the European Iron Fertilization Experiment in the subpolar South Atlantic Ocean, Geophys. Res. Lett., 32, L 23613, doi:10.1029/2005GL024619, 2005. - Describes N20 measurements during a Fe fertilization experiment. In contrast to a previous study no increase in the N20 concentrations during the course of the experiment was found. 8 Hermann W. Bange: Nitrous oxide in the ocean 4) • Walter, S., H.W. Bange, U. Breitenbach, and D.W.R. Wallace, Nitrous oxide in the North Atlantic Ocean, Global Biogeochem. Cycles, in preparation, 2006. - Summarizes the N20 distribution in the subpolar, subtropical and tropical North Atlantic Ocean. The N20 distribution is attributed to formation via nitrification in the subtropical and tropical Atlantic, whereas mixing processes largely influence N20 in the subpolar Atlantic. 5) * Walter, S., U. Breitenbach, H.W. Bange, G. Nausch, and D.W.R. Wallace, Nitrous oxide water column distribution during the transition from anoxic to oxic conditions in the Baltic Sea, Biogeosci., submitted, 2006. - Shows the effect of rapidly changing 0 2 concentrations on the formation and consumption of N20 in a natural laboratory (i.e. the central Baltic Sea). During the ventilation process by North Sea Water, N20 was produced, but did not reach the atmosphere due the stable stratification of the central Baltic Sea. N20 production rates and nitrification rates were estimated. Theme B: N20 emissions 6) Bange, H.W., M.O. Andreae, S. Lal, C.S. Law, S.W.A. Naqvi, P.K. Patra, T. Rixen, and R.C. Upstill-Goddard, Nitrous oxide emissions from the Arabian Sea: A synthesis, Atmos. Chem. Phys., 1, 61-71, 2001. - Computation of high-resolution (1°latitude x 1°longitude) seasonal and annual N20 concentration fields and subsequent emissions for the Arabian Sea surface layer using a data base of more than 2400 values. 7) Bange, H.W., Air-sea exchange of nitrous oxide and methane in the Arabian Sea: A simple model of the seasonal variability, Indian J. Mar. Sci., 33 (1), 77-83, 2004. - Presents a one-dimensional coupled ocean/atmosphere box model in order to investigate the seasonal variability of N20 in the surface layer of the Arabian Sea. 8) * Walter, S., H.W. Bange, and D.W.R. Wallace, Nitrous oxide in the surface layer of the tropical North Atlantic Ocean along a west to east transect, Geophys. Res. Lett., 31 (23), L23S07, doi:10.1029/2004GL019937, 2004. - Reports continuous N20 surface measurements and the associated N20 emissions to the atmosphere in the tropical North Atlantic Ocean. Hermann W. Bange: Nitrous oxide in the ocean 9 9) Bange, H.W., Nitrous oxide and methane in European coastal waters, Estuar. Coastal Shelf Sci., submitted, 2005. - Overview about the distribution and formation/consumption pathways of N20 in the European coastal waters such as estuaries, deltas, lagoons, fjords, continental shelves etc. Provides a comprehensive data base for a first reasonable assessment of N20 emissions from European coastal areas, which contribute significantly to the global oceanic N20 emissions. 10) Bange, H.W., New Directions: The importance of the oceanic nitrous oxide emissions, Atmos. Environ., 40 (1), 198-199, 2006. - Shows that the often-cited global estimate of oceanic N20 emissions is underestimated. Proposes a considerable upward revision (2x) of the common estimate that has far reaching consequences for the overall budget of atmospheric N20. * these articles are part of the PhD thesis by Sylvia Walter, "N20 in the Atlantic Ocean and the Baltic Sea", 154 pp., University of Kiel, 2006. My contribution to the articles listed above can be assessed as follows: Article no. Conceptual Sample and data Contribution to the contribution analysis written manuscript Theme A 1 1 1 1 2 1 1 1 3 2 2 1 4 2 2 2 5 2 3 2 Theme B 6 1 1 1 7 1 1 1 a 1 2 1 9 1 1 1 10 1 1 1 1 =major contribution; 2 =significant but not major contribution; 3 =small contribution 10 Hermann W. Bange: Nitrous oxide in the ocean Further articles have been written during the time of the habilitation. These articles are closely related to the themes of the habilitation, but are not attached: Bange, H.W., It's not a gas, Nature, 408, 301-302, 2000. Bange, H.W., Gaseous nitrogen compounds (NO, N20, N2, NH3) in the ocean, in Nitrogen in the marine environment, edited by D.G. Capone, D.A. Bronk, M.R. Mulholland, and E.J. Carpenter, submitted, Academic Press I Elsevier, 2006. Bange, H.W., S.W.A. Naqvi, and L.A. Codispoti, The nitrogen cycle in the Arabian Sea, Progr. Oceanogr., 65, 145-158, 2005. Bange, H.W., T. Rixen, A.M. Johansen, R.L. Siefert, R. Ramesh, V. lttekkot, M.R. Hoffmann, and M.O. Andreae, A revised nitrogen budget for the Arabian Sea, Global Biogeochem. Cycles, 14 (4), 1283-1297, 2000. Dahlke, S., S. Wolff, L.-A. Meyer-Reil, H.W. Bange, R. Ramesh, S. Rapsomanikis, and M.O. Andreae, Bodden waters (southern Baltic Sea) as a source of methane and nitrous oxide, in Proceedings in Marine Sciences, Volume 2: Muddy Coast Dynamics and Resource Management,