A preliminary study of carbon system in the East China Sea

In the central part of the East China Sea, the activity of CO₂ in the surface water and total carbonate, pH and alkalinity in the water column were determined in winter and autumn of 1993. The activity of CO₂ in the continental shelf water was about 50 ppm lower than that of surface air. This decrease corresponds to the absorption of about 40 gC/m²/yr of atmospheric CO₂ in the coastal zone or 1 GtC/yr in the global continental shelf, if this rate is applicable to entire coastal seas. The normalized total carbonate contents were higher in the water near the coast and near the bottom. This increase toward the bottom may be due to the organic matter deposited on the bottom. This conclusion is supported by the distribution of pH. The normalized alkalinity distribution also showed higher values in the near-coast water, but in the surface water, indicating the supply of bicarbonate from river water. The residence time of the East China Sea water, including the Yellow Sea water, has been calculated to be about 0.8 yr from the excess alkalinity and the alkalinity input. Using this residence time and the excess carbonate, we can estimate that the amount of dissolved carbonate transported from the coastal zone to the oceanic basin is about 70 gC/m²/yr or 2 GtC/yr/area-of-global-continental-shelf. This also means that the rivers transport carbon to the oceans at a rate of 30 gC/m²/yr of the coastal sea or 0.8 GtC/yr/ area-of-global shelf, the carbon consisting of dissolved inorganic carbonate and terrestrial organic carbon decomposed on the continental shelf.     

Origin of calcium in aerosols over the western North Pacific

Weekly aerosol samples were collected from March 1981 to June 1983 at the six stations in the western North Pacific region and analyzed for Ca and Na. By coupling data with those previously reported for Al (Tsunogai et al., 1985), the following results and conclusion have been obtained. There was a positive correlation between the atmospheric concentration of Al and the concentration of nonsea salt Ca (nssCa). The nssCa/Al ratios from the six stations, however, considerably varied (from 0.84±0.36 to 3.00±1.91), and the ratios were usally larger than those of the crustal average or of usual soil in Japan. The Ca/Al ratios of Asian desert soil and loess vary from 0.52 to 1.29, which are similar to the nssCa/Al ratios of aerosols in the surface air over the western North Pacific region except at Onna, Okinawa. The exception may be due to a local effect of coral. These results suggest that a large part of nonsea salt Ca in the surface air over the western North Pacific is derived from arid regions in Asia and that the nssCa/Al ratio in aerosol varies with that of the source material.     

Geophysical and geochemical observations on actively seeping hydrocarbon gases on the south-eastern Yellow Sea continental shelf

In the southeastern Yellow Sea, active seepage of hydrocarbon gases has been observed by high-resolution (3.5 kHz) seismic profiling both in 1987 and 2001, occurring through a large number of plumes from the topmost pre-Holocene sedimentary layer. It is strong enough to compensate for current speed, extending vertically up to the sea surface. The gas seepage often appears to be explosive to form craters and diapirs, although pockmarks are rare due to the redistribution of mobile palimpsest sands. In core-top seawater and sediments, the gases are characterized by high amounts of C₂, homogenous ¹³C₁ values and a large difference (19.7 on average) between ¹³C₁ (–55.2 to –53.6 PDB) and ¹³C₂ (–36.8 to –32.5 PDB) values. The gases are considered to be generated with a smaller amount of C₁ at the early thermal cracking stage of labile source materials, after which the C₂ gas is enriched in ¹³C by diffusion or biological alternation at the generation or accumulation site. The homogenous ¹³C₁ values may be one of the geochemical characteristics of gases acquired at depth which are less altered in the case of rapid diffusive gas migration to the seafloor.     

Iodine in the surface water of the ocean

Iodine in sea water of the Pacific was determined with special interest in the relation between iodide and iodate in the surface water of the ocean. The result was discussed with reference to the mechanism of iodide formation proposed byTsunogai andSase. The concentration of iodide varies widely from the lower value than the detection limit to 0.21g at./l, while the concentration of total iodine is nearly constant and the mean value is 0.41g at./l. The vertical profile of iodide often shows the maximum in the surface layer. In the surface layer, the concentration of iodide is higher in warm water (0,10g at./l on the average) than that in cold water of lower temperature than 20° C (0.03g at/l). The highest concentration of iodide among the warm waters is found in the surface water of the equatorial area (0.13g at./l) where the biological productivity is also high. Iodide is generally more enriched in the water having higher biological activity even in the cold water. These results are considered to be compatible with the mechanism of iodide formation proposed.     

Regeneration of chemical elements from settling particles collected by sediment trap in Funka Bay,Japan

Sediment trap experiments were carried out 39 times during the years from 1977 to 1981 in Funka Bay, Hokkaido, Japan. The observed total particulate flux varies seasonally, that is, the particulate fluxes in winter and spring are larger than those in summer. The fluxes in all seasons increased with depth. Major components of settling particles are aluminosilicate in winter, biogenic silicate in spring and organic matter and terrestrial material in summer, respectively. The fluxes of each chemical component observed with sediment traps are normalized to that of Al by assuming that the actual flux of Al is equal to the accumulation rate onto the sediment surface. Vertical changes of the normalized flux of each chemical component indicate the following: Fe was not regenerated from the settling particles in the water column. Mn was regenerated from the settling particles in the lower layer exclusively between 80 m depth and the sediment surface. Cd was actively regenerated in the upper layer above 80 m depth. Phosphate was regenerated in the upper layer, while biogenic silicate was in the lower layer. The silicate regeneration, therefore, occurs after phosphate regeneration. The material decomposing in the water column below 40 m has an atomic ratio of P ∶ Si ∶ C = 1 ∶ 52 ∶ 128.     

Nitrogen, Oxygen and Argon Dissolved in the Northern North Pacific in Early Summer

Major gases dissolved in seawater were accurately determined with a shipboard gas chromatographic method. The standard deviations were 0.28, 0.34 and 0.36% for N₂, O₂ and Ar, respectively. The method was applied to water from the northwestern North Pacific Ocean collected in May to June 2000. We got 127 duplicate seawater samples from the surface 200 m layer at 11 stations. The O₂ concentrations obtained by this method agreed with those given by the Winkler method. All the seawater samples from the surface 200 m, especially those from the upper 30 m, were supersaturated with respect to atmospheric N₂ and Ar concentrations. In the topmost 30 m layer, the degrees of supersaturation in the inventory were 2.7–4.3% for N₂ (ΔN₂) and 1.7–2.6% for Ar (ΔAr), and their ratios, ΔN₂/ΔAr, ranged from 1.53 to 1.81. This supersaturation seems to be chiefly due to air bubbles injected into the water and dissolved due to the water pressure, because the N₂/Ar ratio of the air is around 2. The amounts of air bubbles dissolved in the upper 30 m water were relatively large, with mean value of 0.41 ml/kg or 18.4 μmol/kg. The ΔN₂, ΔAr and ΔN₂/ΔAr values were all positively well correlated with the wind velocities averaged for the last 24 hours prior to sampling, allowing the conclusion to be drawn that the weaker the wind velocity, the dissolved gas composition approaches in equilibrium with the air; while the stronger the wind velocity, it approaches in the air composition. This revised version was published online in July 2006 with corrections to the Cover Date.     

CFC Indicating Renewal of the Japan Sea Deep Water in Winter 2000–2001

The distributions of CFC (chlorofluorocarbon) in the water column was determined twice in 2000 and 2001 in the northwestern Japan Sea. In 2000 the CFC-11 concentration decreased almost exponentially with depth from 6 pmol/kg at a few hundred m deep to 0.3 pmol/kg or less at the bottom of about 3400 m depth at three stations (40–41°N, 132–133°E) about 300 km off Vladivostok. In 2001 the CFC-11 concentration increased sharply up to 2 pmol/kg in the bottom water, while it did not increase at a station (42.0°N, 136.5°E) about 450 km away to the northeast. This is due to the renewal of the bottom water which is replaced by the surface water flowing down along the continental slope, as suggested by Tsunogai et al. (1999), who proposed the continental shelf pump. Furthermore, an increase in the CFC-11 concentration was observed throughout the entire water column above 3000 m depth, although the proportion of the increase was about 20%, which was one order of magnitude smaller than that in the bottom water. The increase in inventory is almost four times larger than that in the bottom water below 3000 m depth which is equivalent to about 1/6 of the total inventory found in 2000. The increase also means that 3% of the deep water was replaced by the recent surface water, or, if the turnover occurs every year, that the turnover time of the deep water to be about 30 years. This revised version was published online in July 2006 with corrections to the Cover Date.     

Origins of hydrocarbons in the Sagara oil field, central Japan

Abstract   We collected free-gas and in situ fluid samples up to a depth of 200.6 m from the Sagara oil field, central Japan (34°44'N, 138°15'E), during the Sagara Drilling Program (SDP) and measured the concentrations and stable carbon isotopic compositions of CH₄ and C₂H₆ in the samples. A combination of the CH₄/C₂H₆ ratios with the carbon isotope ratios of methane indicates that the hydrocarbon gases are predominantly of thermogenic origin at all depths. The isotope signature of hydrocarbon gases of δ¹³      < δ¹³     suggests that these gases in the Sagara oil field are not generated by polymerization, but by the decomposition of organic materials.     

Chemical Assessment of Oceanic and Terrestrial Sulfur in the Marine Boundary Layer over the Northern North Pacific during Summer

Dimethylsulfide (DMS) in surface seawater and the air, methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ²–) in aerosol, and radon-222 (Rn-222) were measured in the northern North Pacific, including the Bering Sea, during summer (13 July – 6 September 1997). The mean atmospheric DMS concentrations in the eastern region (21.0 ± 5.8 nmole/m³ (mean ± S.D.), n=30) and Bering Sea (19.9 ± 9.8 nmole/m³, n=10) were higher than that in the western region (11.1 ± 6.4 nmole/m³, n=31) (p<0.05), although these regions did not significantly differ in the mean DMS concentration in surface seawater. Mean sea-to-air DMS flux in the eastern region (21.0 ± 10.4 mole/m²/day, n=19) was larger than those in the western region (11.3 ± 16.9 mole /m²/day, n=22) and Bering Sea (11.2 ± 7.8 mole/m²/day, n=7) (p<0.05). This suggests that the longitudinal difference in atmospheric DMS was produced by that in DMS flux owing to wind speed, while the possible causes of the higher DMS concentrations in the Bering Sea include (1) later DMS oxidation rates, (2) lower heights of the marine boundary layer, and (3) more inactive convection. The mean MSA concentrations in the eastern region (1.18 ± 0.84 nmole/m³, n=35) and Bering Sea (1.17 ± 0.87 nmole/m³, n=13) were higher than that in the western region (0.49 ± 0.25 nmole/m³, n=28) (p < 0.05). Thus the distribution of MSA was similar to that of DMS, while the nss-SO₄ ²– concentrations were higher near the continent. This suggests that nss-SO₄ ²– concentrations were regionally influenced by anthropogenic sulfur input, because the distribution of nss-SO₄ ²– was similar to that of Rn-222 used as a tracer of continental air masses.