*********** 012992B.CHM *********** Country: Japan From: Report of oceanographic studies in Japan for the period from 1987-1990- by Japanese National Committee for Physical Sciences of the Ocean- Science Council of Japan. Prepared for IAPSO (International Association for the Physical Sciences of the Sea) for presentation at XX General Assembly of the International Union of Geodesy and Geophysics: Vienna, Austria: August 1991. p. 20-40 II. CHEMICAL OCEANOGRAPHY Shizuo Tsunogai, Faculty of Fisheries, Hokkaido University, Hakodate 041, JAPAN In this four years(1987-1990), chemical oceanographic works in Japan were supported by some fairly large cooperative projects such as "Dynamics of the Deep Ocean Circulation (represented by Prof. T. Teramoto)" and "Formulation and Management of Man -Environment System (represented by Prof. M. Suzuki)" both for scientists in universities besides individual projects proposed to the respective agencies. Chemical oceanographic studies on board R. V. Hakuho Maru of Ocean Research Institute, University of Tokyo carried out in the western North Pacific (KH-87-2), the eastern North Pacific (KH -88- 3) and the equatorial Pacific(KH-90-3). Vessels of other universities and governmental agencies were also well used for research. These projects and cruises have highly stimulated us and brought forth many valuable works, which are listed below. On the other hand, the population of Japanese chemical oceanographers has not so increased. This is due to a small number of laboratories studying chemical oceanography in universities especially in graduate schools. Only one chemical laboratory was newly opened in Department of Marine Science and Technology in Hokkaido Tokai Univ. (Sapporo) in 1988. Recently many governmental research institutes have become aware of the importance of chemical oceanography or the weakness of their chemical division, and gradually reinforced their chemical aspect by employing new scientists. They are Japan Meteorological Agency including Meteorological Research Institute, National Research Institute for Pollution and Resources, Government Industrial Research Institute, National Institute for Environmental Studies, National Institute of Radiological Science, Japan Atomic Energy Research Institute, Japan Marine Science and Technology Center, etc. The scientists in these research institutes will add many fruitful oceanographic works in the next period of four years. The scientists studying in academic positions have also taken an active part in Japanese chemical oceanography. They are belonging to Faculty of Fisheries, Hokkaido Univ.; Ocean Research Institute and Faculty of Science, Univ. of Tokyo: Tokyo Univ. of Fisheries; Faculty of Science, Tokyo Metropolitan Univ.; Faculty of Agriculture, Tokyo Univ. of Agriculture and Technology; Faculty of Marine Sciences. Tokai Univ.; Faculty of Science, Toyama Univ.; Water Research Institute, Nagoya Univ.; Faculty of Biological Resources, Mie Univ.; Faculty of Science, Kyoto Univ.; Faculty of Science and Technology, Kinki Univ.; Faculty of Integrated Arts and Sciences, Hiroshima Univ.; Faculty of Agriculture, Ehime Univ. and Faculty of Science, Univ. of Ryukyus. The studies carried out by them are given below with brief comments.1. General and Physical Oceanography Studied with Chemistry The usefulness of dissolved silica as a tracer of deep water movement has been clarified (Tsunogai, 1987), where the Pacific Deep Water flows from the deep western North Pacific to the deep central and eastern North Pacific via the northern end of the Emperor Sea- mountains along the Kurile and Aleutian Trenches. REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . .6 Citations 2. Physical Chemistry REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . . 1 Citation 3. Chemistry of Anoxic Water The blue tide, Aoshio, was extensively studied by T. Samukawa and his colleagues (Natl. Res. Inst. Poll. Resour.) REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . .5 Citations 4. Analytical Chemistry E. Nakayama (Kyoto Univ.)'s group studied the followings. A column extraction method using macroporous resin impregnated with 7-dodecenyl -8-quinolinol (Chelex-100 column) was utilized for simultaneous preconcentration of common heavy metals as well as other column extraction methods for Co and Cr in seawater. The polarographic catalytic currents obtained in a special electrolytic solution have been applied to the simultaneous determination of W and Mo in oceanic water found to contain ca. 60 pM of Mo. Furthermore, an automated flow-system suitable to the on-board analysis of Mn in seawater was constructed. K. Fujiwara and his colleagues (Hiroshima Univ.) developed new analytical methods of phosphate and As and applied to seawater. The new technique was ozone-gas phase chemiluminescence for As. REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . 30 Citations 5. Gases and Marine Atmosphere The determination of pCO2 of seawater was continued by H. Inoue and his colleagues (Meteorol. Res. Inst.). The time-series measurements in the western North Pacific will give valuable information to the global change studies. T. Suzuki and his colleagues (Hokkaido Univ. ) studied the long- range transport of aerosol of continental origin to the ocean by making an observation network with US scientists. REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . .12 Citations 6. Trace Elements K. Matsunaga and his colleagues (Hokkaido Univ.) have revealed the following. The distribution of trace metals and nutrients in seawater is controlled by biogeochemical process. They examined the mechanism that controls the seasonal variations of Cd and P04 in the euphotic zone in Funka Bay, Japan (Abe and Matsunaga, 1988; Abe et at., 1990 ). They also observed the high Fe(II) concentration, which is extremely unstable in oxic seawater, during a spring bloom (Nakabayashi et at., 1989 ). The behavior of trace metals and nutrients was examined in the Yodo River Estuary, Osaka Bay where red tide outbreaks are observed (Kudo and Matsunaga, 1989). The origin of nutrients rich in the Tsushima current was also investigated (Toya et al., 1988). 6a. Concentration in sea water REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . 12 Citations 6b. Metal-organic ligand complexes REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . .5 Citations 7. Radioisotopes Y. Nozaki and his group (Univ. of Tokyo) continued to measure natural radioisotopes in seawater. Many Japanese works obtained for radioisotopes have been discussed to make clear the behavior of chemical elements in the marine environment, the physical water movement (advection and diffusion) and the biological activity in the ocean. The works in relation to the particulate removal in the ocean are given in Section 11a, although Kusakabe et at. (1988)'s work showed the rapid particulate transport in the biologically active northern North Pacific. Tsunogai et at. (1990) clarified that the coastal sediments are the most important sink of uranium in seawater. 7a. Natural radioisotopes REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . 17 Citations 7b. Artificial radioisotopes REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . .4 Citations 8. Stable Isotopes N. Yoshida(Toyama Univ. ) developed a skillful technique to determine isotopic ratios of nitrogen of N2O, which is a by-product of nitrification and denitrification processes during the biological metabolism. These stable isotopic studied will give valuable information on the oceanic biological activity. REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . .6 Citations 9. Nutrients and Biochemistry T. Saino (Univ. of Tokyo) studied the oceanic biochemical processes chiefly with stable isotopes based on an extensive survey of vertical profile of del-15N in POM, which revealed that the 15N abundance in deep water POM is primarily determined by that in the near surface POM (Saino and Hattori, 1987). Difference between del-15N and del-13C profiles of POM was explained as resulted from the difference of refractory fraction in POC and PON. It is proposed that del-13C and del-15N of POM provide complementary information on POM dynamics (Saino, 1990). K. Kobayashi (Yokohama National Univ.) studied large molecular weight metal complexes dissolved in seawater and freshwater. The concentration of such metal complexes were determined by ultrafiltration/high performance gel chromatography/ICP optical emission spectrometry (or graphite furnace atomic absorption spectrometry) (Kobayashi et at., 1990). A part of such kinds of complexes were proved to be metalloenzymes like alkaline phosphatase (Kobayashi and Haraguchi, 1989). REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . 28 Citations 10. Organic Matter in Seawater The concentration and the composition of dissolved organic nitrogen (DON) were determined in the North Pacific Ocean using newly developed high temperature oxidation method (given in Section 4). The significance of the DON in the geochemical cycle of nitrogen was discussed in relation to the hydrographical conditions, biological production and decomposition by Y. Maita and his colleagues (Hokkaido Univ.). They showed that in the upper water, DON existed as labile nitrogen which can easily be decomposed by oceanic bacteria, i.e. low molecular weight organic nitrogen compounds, whereas in the middle and deep waters, DON existed more as biochemically refractive nitrogen. The vertical variation of DON was small as compared with that of nitrate nitrogen and they suggested that DON was not apparently the major source of nitrate nitrogen. The concentration of dissolved organic carbon (DOC) was measured by Y. Suzuki and his colleagues (Meteorol. Res. Inst.), but the data have not yet been published except one report (Druffel et at.. 1989). K. Hayase (Hiroshima Univ.) studied the fluorescent organic matter in the North Pacific and Sagami Bay, Japan, showing that the vertical profile was similar to that of phosphate of nitrate. REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . 17 Citations 11. Particulates and Sediment Trap Experiments Sediment trap experiments are now actively carried out by various groups, but the published papers are not so many. S. Tsunoga1 and his colleagues (Hokkaido Univ.) discussed the particulate removal of chemical elements by proposing "Train-passengers model" (Tsunogai, 1987) and by introducing the vertical change index for the lateral transport (Tsunogai et al., 1990). They also gave attention to the oceanic carbon cycle (Tsuogai and Noriki. 1987, 1991). K. Taguchi (Mie Univ. ) radiochemically investigated settling particles collected by sediment traps in the high, latitudes of the North Pacific. In the northern North Pacific, including the Bering Sea, the average activity ratio of unsupported 230Th to 231Pa in settling particles was 5.5. whereas that in the Gulf of Alaska in the eastern North Pacific was about 14. It is suggested that 231Pa transported from oligotrophic regions is being actively removed in the biologically productive northern North Pacific (Taguchi et at., 1989). 11a. Inorganic matter REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . .8 Citations 11b. Organic matter REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . 10 Citations 12. Sediments A. Kamatani and his colleagues (Tokyo Univ. of Fisheries ) studied followings. The dissolution kinetics of diatom silica skeletons and diatom ooze from the Antarctic Ocean was investigated at various pH's and temperatures. The slow dissolution rate of the ooze was mostly due to the presence of inhibitors postfixed on the surface layer of silica skeletons, which were partly removed by the acid treatment. The dissolution process could be described by paraboric (?parabolic? PW) kinetics. On the other hand, the dissolution of the silica skeletons which was prepared from living diatom was shown by a simple first order equation. Horizontal distribution of lignin components (CuO degradation products), delta C-13 values, cellulose, polynuclear aromatic hydrocarbons (PAH), alkylbenzene sulfonates (LAS) and linear alkylbenzenes (LABS) have been investigated in the sediments of Tokyo Bay and adjacent areas by R. Ishiwatari and his group (Tokyo Metropol. Univ.). The results have indicated that these materials and parameters are very useful in understanding the behavior of land-derived organic matter in bay and coastal regions. Alkylbenzenes can be used as a tracer of domestic wastes. Land-derived organic matter shows roughly two types of distribution in bay area probably depending on density of carriers. 12a. Inorganic matter and interstitial water REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . .8 Citations 12b. Organic matter REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . 10 Citations 12c. Ferromanganese nodules and authegenic matter REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . .4 Citations 13. Basalt and Hydrothermal Activity on the Ocean Floor T. Gamo and his colleagues (Univ. of Tokyo) studied hydrothermal activity at the Loihi submarine volcano and characterized it from water profiles of dissolved CH4 pH and 3He. Apparently two distinct hydrothermal plumes were identified to suggest that there are at least two chemically independent vent systems in the Loihi area (Gamo et al., 1987). Cold seepage at the Hatsushima Calyptogena community site in the western Sagami Bay was also characterized from high values of CH4 and some trace metals in the bottom seawater. Time scale for CH4 consumption was estimated by applying a vertical diffusion model to CH4 and 222Rn profiles. Anomalously high heat flow was found to accompany with the seepage at the site (Gamo et al., 1988). M. Kusakabe's group (Okayama Univ.) studied followings. Seawater circulation through the oceanic crust at the spreading axes can give a great influence on the chemical and isotopic compositions of the oceanic crust due to extensive hydrothermal alteration. They characterized, in terms of H. 0, S and Sr isotopic variations, the hydrothermally altered rocks from a young oceanic crust drilled off Costa Rica during DSDP/ODP project (Kawahata et at., 1987; Kusakabe et at.. 1989). Upon subduction, such altered crust is dehydrated and supply water responsible for serpentinization of wedge mantle in the forearc region (Sakai et at., 1990). Venting of hot water at the spreading axis of backarc basin was first recognized at Mariana Trough chimney materials and hot waters were found similar to those of the midoceanic ridges except that the backarc chimneys were enriched in Ba and Pb (Kusakabe et al., 1990). REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . 19 Citations 14. Pollution R. Tatsukawa and his coworkers (Ehime Univ.) have been engaged in the research on the distribution, behavior and fate of persistent toxic contaminants (particularly organochlorine compounds and heavy metals) in riverine, estuarine, coastal and open ocean waters from a global point of view. Concomitantly, biological contamination, bioaccumulation and ecotoxicity of these chemicals have also been investigated using wide range of marine organisms such as fish, reptiles. birds and mammals. From the investigations conducted during the recent 4 years, it could be pointed out that the increasing usage and disposal of toxic chemicals in the tropical regions have a greater impact on marine environment, particularly remote ocean areas including polar regions. Furthermore, higher marine organisms such as whales and dolphins were recognized to be most vulnerable to the toxic threat of persistent contaminants due to specific biological and physiological processes like lack of detoxification enzymes. REFERENCES: . . . . . . . . . . . . . . . . . . . . . . . . . 34 Citations ************* END Msg B.CHM *************