Mass balance and sources of mercury in Tokyo Bay

The mass balance and sources of mercury in Tokyo Bay were investigated on the basis of observations from December 2003 to January 2005. Estimated input terms included river discharge (70 kg yr⁻¹) and atmospheric deposition (37 kg yr⁻¹), and output terms were evasion (49 kg yr⁻¹), export (13 kg yr⁻¹) and sedimentation (495 kg yr⁻¹). Thus, the outputs (557 kg yr⁻¹) considerably exceeded the inputs (107 kg yr⁻¹). In addition, the imbalance between the inputs and outputs of mercury was much larger than that of other trace metals (Cd, Cr, Cu, Pb and Zn), which suggests that there are other major inputs of mercury to Tokyo Bay. The mercury concentrations in rivers correlated significantly with the concentrations of Al and Fe, major components of soil. In Japan, large amounts of organomercurous fungicides (about 2500 tons as Hg) were used extensively in fields in the past, and most of the mercury was retained in the soil. In this study, the mercury concentration in rivers was measured primarily in ordinary runoff. These observations lead to the hypothesis that field soil discharged into stormwater runoff is a major source of mercury in Tokyo Bay. As a preliminary approach to validating this hypothesis, we measured the concentrations of mercury and other trace metals in river water during a typhoon. The mercury concentrations in stormwater runoff increased to 16–50 times the mean value in ordinary runoff, which is much higher than the increases for other metals. This tends to support the hypothesis.     

Air-sea exchange of mercury in Tokyo Bay

In Tokyo Bay the concentrations of dissolved gaseous mercury (DGM) in the surface seawater and total gaseous mercury (TGM) over the sea were measured during December 2003, October 2004 and January 2005. Based on these data, the evasional fluxes of mercury from the sea surface were estimated using a gas exchange model. In addition, an automatic wet and dry deposition sampler was used to measure the wet and dry depositional fluxes of mercury from December 2003 to November 2004 at three locations in and near Tokyo Bay. The results indicate that the average DGM and TGM levels of seven locations are 52 ± 26 ng m⁻³ and 1.9 ± 0.6 ng m⁻³, respectively, which shows that the surface seawater in Tokyo Bay is supersaturated with gaseous mercury, leading to an average mercury evasional flux of 140 ± 120 ng m⁻²d⁻¹. On the other hand, the annual average wet and dry depositional fluxes of mercury at three locations were 19 ± 3 μg m⁻²yr⁻¹ and 20 ± 9 μg m⁻²yr⁻¹, respectively. These depositional fluxes correspond to the daily average total depositional flux of 110 ± 20 ng m⁻²d⁻¹. Thus, it is suggested that in Tokyo Bay, the evasional fluxes of mercury are comparable to the depositional fluxes.     

Interannual and Decadal Variabilities of NPIW Salinity Minimum Core Observed along JMA’s Hydrographic Repeat Sections

We investigated the variation of the North Pacific Intermediate Water (NPIW) distribution in the western North Pacific, focusing on the intermediate salinity minimum (S < 34.2) core observed along the meridional hydrographic sections including the 137°E repeat section by the Japan Meteorological Agency. This core is a cross-section of a low salinity tongue extending westward along the recirculation in the subtropical gyre. The core size shows remarkable variabilities in interannual and decadal time scales. The salinity change in the density layer during the period of core expansion (shrinking) represents the spatial salinity change in the tongue toward the west (east). Thus, we conclude that the core size variation is associated with the zonal wobble of the tongue having thicker distribution to the east, rather than temporal changes of the water mass itself. The core size at 137°E is well correlated with the meridional gradient of the depth in the isopycnal surface at the salinity minimum representing the recirculation intensity, suggesting a relation with the intensity of the subtropical gyre. A significant lag-correlation between the gradient and the wind forcing over the North Pacific suggests that the first mode baroclinic Rossby waves excited in the central North Pacific propagated westward to change the intensity of the recirculation in interannual time scales. In decadal time scales, it is found that the wind stress curl and heat flux fields in the North Pacific precede the recirculation by about 11 years.     

Analysis of historical trend of pollution sources of lead in Tokyo Bay based on lead isotope ratios in sediment core

The historical trend of pollution sources of Pb in Tokyo Bay, Japan was investigated on the basis of Pb isotope ratios in a sediment core. The isotope ratios of anthropogenic Pb decreased gradually with increasing Pb concentration in the 1900s–1970s, suggesting a combination of Pb sources with various isotope ratios. In contrast, the isotope ratios of anthropogenic Pb in the 1980s–2000s showed no significant trend, and corresponded to the Pb isotope ratios in the three principal rivers flowing into the bay. It is probable that river bottom sediments contaminated with Pb are principal sources of anthropogenic Pb in Tokyo Bay.     

Graphitization of carbonaceous matter during metamorphism with references to carbonate and pelitic rocks of contact and regional metamorphisms,Japan

This study is an attempt to correlate the graphitization process of carbonaceous matter during metamorphism with metamorphic grade. Graphitization can be parameterized using crystal structure and chemical and isotopic compositions. The extent of graphitization could be characterized mainly by temperature, duration of metamorphism and rock composition. We compared the graphitization trends for two metamorphic terrains, a contact aureole of the Kasuga area and a regional metamorphic terrain of high-temperature/low pressure type of the Ryoke metamorphic terrain in Northern Kiso area, Central Japan, and for two different lithologies (carbonate and pelite), using X-ray diffractogram, DTA-TG analysis, and chemical and stable isotope analyses. During contact metamorphism, graphitization and carbon isotopic exchange reactions proceeded simultaneously in pelitic and carbonate rocks. The decreases in basal spacing d(002) of the carbonaceous matter in carbonate rocks is greatly accelerated at temperatures higher than about 400° C. Furthermore, carbon isotopic ratios of graphite in carbonate rocks also change to ¹³C-enriched values implying exchange with carbonates. The beginning of this enrichment of ¹³C in the carbonaceous matter coincides with an abrupt increase of the graphitization processes. Carbon isotopic shifting up to 5 in pelites could be observed as metamorphic temperature increased probably by about 400° C. Carbonaceous matter in pelitic rocks is sometimes a mixture of poorly crystallized organic matter and well-crystallized graphite detritus. DTA-TG analysis is an effective tool for the distinction of detrital graphitic material. Two sources for the original carbon isotopic composition of carbonaceous matter in pelites in the Kasuga contact aureole can be distinguished, about-28 and-24 regardless of the presence of detrital graphite, and were mainly controlled by depositional environment of the sediments. Graphitization in limestones and pelitic rocks in regional metamorphism proceeds further than in a contact aureole. In the low-temperature range, the differences in extent of graphitization between the two metamorphic regions is large. However, at temperatures higher than 600° C, the extent of graphitization in both regions is indistinguishable. The degree of graphitization is different in limestones and pelitic rocks from the Ryoke metamorphic terrain. We demonstrate that the graphitization involves a progressive re-construction process of the crystal structure. The sequence of the first appearance of crystal inter planar spacing correlates with the metamorphic grade and indicates the crystal growth of three-dimensional structured graphite.     

A numerical experiment on the variations of western boundary currents: Part II. Response to a moving typhoon

Response of the barotropic western boundary current to typhoon passage is investigated by the use of the numerical models described in Part I. Steady states obtained in Part I are chosen as the initial conditions for undisturbed currents. In these models it is assumed that an axially symmetric typhoon (radius = 100 km, maximum wind speed = 27.4 m/sec) moves parallel to the western boundary.For the model with a flat bottom the boundary flow diminishes its strength and broadens its width after the passage of the typhoon offshore. For the model with a continental slope the effect of the typhoon is significantly different depending on the distance of the path of the typhoon from the western boundary. Specifically the north wind on the continental slope causes the formation of cyclonic vortex, which progresses southwards along the slope in the northern hemisphere. Linear theory of continental shelf waves indicates that the phase speed of the propagation of the vortex is 2.4 m/sec. Anomalies of the water level along the coast are also calculated from geostrophic relationships.     

A modified method for estimating vertical profiles of turbulent dissipation rate using density inversions in the Kuril Straits

To address the lack of directly measured turbulence data in the Kuril Straits, an existing method was modified to indirectly estimate continuous vertical profiles of turbulent energy dissipation rate ε by using density inversions. A linear relationship was confirmed between directly measured ε and indirectly estimated ε from the existing method, where most of the detected density inversions were discarded as noise. The existing method thus yielded large gaps in the vertical profiles, and the gaps were much greater than the observed mean autocorrelation vertical length scale of about 10 m. To reduce these gaps and produce reasonable estimates for vertical ε profiles, the quality tests were carefully re-examined with directly measured ε data, and one of the quality tests (the water mass test) was excluded because the test rejects real density inversions even with large ε. With this modification, and interpolation and smoothing of the indirectly estimated ε with the mean correlation length scale, continuous vertical ε profiles were obtained. These profiles have an error factor of 3.3 corresponding to one standard deviation of the ratio between directly observed and estimated data, and 95 % of the data were within a factor of 10.5, with the overall correlation coefficient between smoothed directly measured ε and estimated ε equal to 0.80. This method could be useful for areas where 10^?9 < ε < 10^?6.5 W/kg, and where vertical distances between adjacent density inversions are mostly less than the mean autocorrelation scale.     

Electrical conductivity measurement of gneiss under mid- to lower crustal P–T conditions

We conducted electrical conductivity measurements perpendicular and parallel to mineral foliation in dry gneiss at up to 1000 K and a constant pressure of 1 GPa. The analyzed gneisses were obtained from the Higo metamorphic belt, Kyushu, Japan. As the metamorphic conditions of these rocks have been well determined by previous studies, we were able to select samples that were representative of the middle to lower crust. Prior to the conductivity measurements, the samples were maintained at the maximum temperature for a long period, until the electrical conductivity had stabilized. Our experiment results reveal linear and reproducible conductivity data between temperatures of 600 and 1000 K. Conductivity measured perpendicular and parallel to foliation differ by an order of magnitude over the same temperature window. A plausible explanation for this discrepancy in conductivity is the contrasting configuration of minerals in the two sample orientations, as observed by backscattered electron image (BEI) and electron probe microanalysis (EPMA). We evaluated the conductivity and computed activation energy for each of the samples and compared the results with those of previous studies; our results are consistent with the conductivity values reported for other types of rocks. We also compared the experiment results with data derived from electromagnetic (EM) soundings. Electrical conductivity measurements undertaken perpendicular to foliation can account for the subsurface conductivity structure beneath central Kyushu, Japan.     

An empirical probabilistic approach for constraining the uncertainty of long-term solute transport predictions in fractured rock using in situ tracer experiments

Although radionuclide tracer tests have been carried out for over 30  years, the role of tracer tests in radioactive waste repository performance assessment (PA) has been questioned due to the differences between the time scales for tracer tests and PA. The possibility of using in situ tracer tests to constrain PA time scale (over 10,000  years) solute transport has been demonstrated using a systematic “microstructural model” approach to define advective and retentive materials. A series of simulations were conducted of the “TRUE-1” sorbing solute transport experiments in a well-characterized block of fractured granite. These experiments were then used to constrain the uncertainty of long-term transport on the same pathways, using a gradient several orders of magnitude smaller. The comparison of uncertainty of this long-term transport, with and without this conditioning step, provided a measure of the ability of tracer tests to reduce PA time-scale uncertainty. Although this approach for quantifying uncertainty reduction is somewhat empirical, it does indicate the potential usefulness of tracer experiments in reducing the uncertainty of the key PA time-scale transport parameters such as the flow wetted surface, provided that immobile zone properties such as sorption (Kd), porosity and diffusivity are available.