Seasonal variation in the difference between observed and calculated particulate fluxes of Th-234 in Funka Bay,Japan

Particulate fluxes were determined by two methods to elucidate the behavior of settling particles in seawater. One method involves direct observation of fluxes with sediment traps, while in the other method flux is indirectly calculated from the radioactive disequilibrium between U-238 and Th-234 in seawater, which gives net flux. Observations were carried out several times throughout a year in Funka Bay. When linearly extrapolated, the observed gross fluxes of Th-234 did not converge to zero at the surface. In the subsurface water the difference between the observed and calculated fluxes showed a seasonal variation. The observed fluxes roughly coincided with the calculated net fluxes in the summer stratified water but the observedfluxes were much larger than the calculated ones in the convective winter water. Conversely the observed fluxes were smaller than the calculated ones in spring when the water was exchanging. These results suggest that we can apply this two approach method to get information not only on the behavior of settling particles in seawater but also on the physical stability of water.     

The partition of minor transition metals between manganese oxides and seawater

The behavior of transition metals (Co, Ni, Cu and Zn) on precipitation of manganese oxides from seawater pumped up from a well at the site of the Marine Science Museum, Tokai University, and collected from several tanks along the water supply system to an aquarium was investigated. The distribution coefficients of cobalt and nickel between manganese oxides and seawater were different at different sampling points along the water supply system. At sampling points with high rates of manganese oxide precipitation, the distribution coefficients were about one order of magnitude smaller than those at the points with low precipitation rates, while there were no remarkable differences in the distribution coefficients of copper and zinc among the sampling points. The distribution coefficients of minor transition metals, with the exception of copper, observed at the points with low precipitation rates were comparable to those measured experimentally using manganese dioxides.     

A sediment trap experiment in Funka Bay, Japan: “upward flux” of particulate matter in seawater

Sediment trap experiments were carried out ten times in one year (1977) at three depths in Funka Bay. The material obtained in the traps was analyzed for metals, organic elements and radionuclides, together with the suspended matter in the overlying water column. Two groups with extremely different downward fluxes were found, a group with a small flux increasing with depth, and another with a large flux that is rather constant with depth and is observed only in winter. The flux in winter, and sometimes in the bottom layer below the summer thermocline was larger than the net sedimentation rate for total dry matter or for each chemical constituent. The flux was also larger than the net removal flux for ²³⁴Th. A most striking fact is that the specific activity of short-lived ²³⁴Th did not decrease in winter, indicating that the large flux in winter was not caused by the re-suspension of old bottom sediments. The concentration of suspended matter in winter was not much greater than that in other seasons. These results suggest that the downward flux observed in sediment trap experiments is not a net removal rate and that there must be an upward particulate flux in the bay.     

Deep-water circulation in the North Pacific deduced from Si-O diagrams

A simple dissolved silica (Si) and dissolved oxygen (O) diagram method was applied to study the deep-water circulation in the North Pacific and the following results and conclusion have been obtained. In the abyssal water flowing northward in the western Pacific Si increases with a constant ratio of Si to decreasing O(Si/O=–0.30). The water is designated as the main sequence. In the eastern Pacific the Si-O diagram is characteristic of the location and reflects the degrees of mixing with older waters and of alteration due to decomposition of biogenic material. The Bay of Alaska is found to be a great source of silica in the North Pacific and its bottom water spreads out to the central North Pacific north of 40°N, called here the abyssal front. The younger abyssal water in the Aleutian Trench flowing to the eastern North Pacific north of 40°N comes through the north end of the Kuril-Kamchatka Trench instead of the gap in the Emperor Seamounts at about 46°N. The deep water is almost completely homogenized by active isopycnal mixing and advection when the deep water reaches its upper boundary by upwelling in the western North Pacific including the Bering Sea. Thus the high productivity in the Bering Sea is principally caused neither by the direct supply of abyssal water rich in nutrients nor by the extremely active vertical mixing reaching depths greater than 500 m, but it may be caused simply by the shallower upper boundary of the deep water mass in the Bering Sea, from which nutrients are easily transported to the surface.     

Absorption of Atmospheric CO2 and Its Transport to the Intermediate Layer in the Okhotsk Sea

In the southwestern Okhotsk Sea off Hokkaido we observed chemical components related to the carbonate system for 1 year from August 1997 to June 1998. Using the conservative components salinity and water temperature, we confirmed the existence of two water masses flowing into the intermediate layer of the Okhotsk Sea, the East Sakhalin Current Water (ESCW) which becomes denser by mixing of brine water, and the Forerunner of Soya Warm Current Water (FSWW) which becomes denser due to cooling of the saline Kuroshio water. The ΔNTC_x values were calculated by comparing the ESCW and the FSWW with the Pacific Deep Water (PDW). The ΔNTC_x values obtained are 100–110 μmol/kg and 70–100 μmol/kg for the ESCW and the FSWW off Hokkaido, respectively, which are considerably larger than that of the Kuroshio water. These large ΔNTC_x values may be due to both low DIC concentration in the surface water and intense gas exchange under the cold and stormy winter conditions for the ESCW and the cooling of the FSWW as it flows northward. Since the flow rates of dense waters concerned with the ESCW and the FSWW have previously been estimated as 0.9 Sv and 0.2 Sv, respectively, the amount of atmospheric CO₂ absorbed and transported to the intermediate layer turns out to be 3.9−4.1 × 10¹³ gC/yr. This flux is small on a global scale, but the flux divided by the surface layer of the Okhotsk Sea is 30 gC/m²/yr, which is 5 times greater than the mean absorption flux of anthropogenic CO₂ in the world's oceans. It is thus considered that atmospheric CO₂ is efficiently absorbed in the Okhotsk Sea. This revised version was published online in July 2006 with corrections to the Cover Date.     

Anomalous Large Scavenging of 230Th and 231Pa Controlled by Particle Composition in the Northwestern North Pacific

We report the role of particle composition and lateral particle movement that influences the oceanic distribution of ²³¹Pa and ²³⁰Th. Settling particles were collected during sediment trap experiments. These and surface sediments were obtained from five stations along 38 to 44°N in the northwestern North Pacific. The high total mass flux and seasonal variations in the marginal area of the western North Pacific are controlled by the supply of lithogenic materials and primary productivity. The high content of the lithogenic material in the settling particles in this area contributes to ²³⁰Th_ex fluxes that exceed the local rate of supply. The lithogenic materials are important as a carrier of ²³⁰Th and contribute to the fractionation between ²³⁰Th and ²³¹Pa in the ocean, as the ²³¹Pa_ex/²³⁰Th_ex ratio in the settling particles decreases with increasing ²³²Th concentration. The ²³¹Pa_ex/²³⁰Th_ex ratio in the settling particles collected in the abyssal basin decreases with water depth, which indicates that lateral transport of the lithogenic particles from the marginal area and/or shallower depth plays an important role in determining the ²³¹Pa_ex/²³⁰Th_ex ratio in a population of settling particles and remineralization. This indicates that lateral redistribution of particles and sediment focusing influence the ²³¹Pa_ex/²³⁰Th_ex ratios in surface sediments. Thus, the observations reported here mean that the use of the sediment ²³¹Pa_ex/²³⁰Th_ex ratio as a paleoproductivity proxy will be problematic in the northwestern North Pacific. This revised version was published online in July 2006 with corrections to the Cover Date.     

The rate of oxidation of ferrous iron in seawater and the partition of elements between iron oxides and seawater

At the Minamichita Beach Land (Mihama-cho, Aichi, Japan), seawater is pumped up from underground and is supplied to aquaria. The underground seawater containsca. 2 ppm of Fe (II), 0.1 ppm of Mn (II) and a little dissolved oxygen. Iron oxide is formed in the seawater when aerated. The oxidation rate of Fe (II) was measured to be 1.4×10¹⁴ mol^–3 l ³ min^–1, which is comparable to the lowest values in the literature. The slow rate of Fe (II) oxidation obtained here can be attributed to the presence of organically bound iron in the seawater. The distribution coefficient of cations between seawater and iron oxide phase was in the order of Cu>Ni>Co>Cd>Mn, which is consistent with that predicted from their hydrolysis constants. The adsorption affinity sequence of oxyanions was phosphate >vanadate> molybdate. The difference in phosphate from the prediction of the adsorption theory was attributed to the formation of ferriphosphate on the oxide surface. On the basis of these data, the limitation and usefulness in the application of the distribution coefficients to marine environments were discussed.     

Errors in sampling procedure for the determination of dissolved oxygen by Winkler method

Sources of systematic error in the sampling procedure by Winkler method were examined. In the laboratory experiment, the dissolution of atmospheric oxygen into oxygenfree sea water during sampling amounts to 0.022 ml/l, and the effect of dissolved oxygen in sea water remaining in oxygen bottle is 0.019 ml/l. The effect of reagents added amounts to 0.017 ml/l. In the sampling procedures aboard, the effect of dissolution became bigger, and the table is presented for the correction to the reported value of dissolved oxygen measured by the “Manual of Oceanographic Observation”. The corrected value of dissolved oxygen in the routine analysis may not be correct within 0.02 ml/l.     

Complexation of dimethylsulfide with mercuric ion in aqueous solutions

The tendency of dimethylsulfide (DMS) to form complexes with heavy metal ions in aqueous solutions and the factors that influence it have been investigated. Among five heavy metal ions examined (Cu²⁺, Cd²⁺, Zn²⁺, Pb²⁺ and Hg²⁺), only Hg²⁺ bound significantly with DMS in aqueous solutions in which Hg²⁺ concentration was increased to much higher levels than that of natural seawater. The complexation capacity of Hg²⁺ for DMS was influenced by pH and media. The affinity of Hg²⁺ for DMS was generally lower at high than at low pH, presumably due to the competition of hydroxide ion to form hydroxomercury species. In different solutions, the affinity of Hg²⁺ for DMS followed the following sequence: ultra-purified water > 35‰ NaCl solution > seawater. It seems apparent that chloride had a negative impact on the complexation of DMS by Hg²⁺, owing to the competition of chloride with DMS for complexing Hg²⁺. In addition, the affinity of Hg²⁺ for DMS in the bulk seawater appeared to be higher than that in the surface microlayer seawater. The tendency of Hg²⁺ to form complexes with DMS in aqueous solution can be reduced by the presence of 2 mM amino-acid such as glycine, alanine, serine and cysteine, as these ligands give stable mercury complexes. However, the presence of 2 mM acetate in experimental solutions had no significant effect on the complexation of Hg²⁺ with DMS, even though this ligand has a relatively strong complexing capacity for Hg²⁺. Although mercury ions appeared to have a strong affinity for DMS, the concentration of mercury in seawater is too low to produce a great effect on the distribution of DMS in oceans.