Differential Fractionation of Rare Earth Elements in Oxidized and Reduced Granitic Rocks: Implication for Heavy Rare Earth Enriched Ion Adsorption Mineralization

Ion adsorption rare earth element (REE) deposits in southern China are the exclusive source of heavy REEs (HREEs) in the world, and this HREE‐enriched character of the deposits is inherited from the REE compositions of the underlying granitic rocks. Such HREE‐enriched rocks form from heavy fractionation of reduced granitic magmas. We explore why reduced granitic magmas are enriched in HREEs during the fractionation, based on the REE geochemistry of granitic rocks and abundance of REEs in their constituent minerals in the southwestern Japan arc of Cretaceous to Paleogene age. The compilation of the whole rock geochemistry and REE compositions of the granitic rocks of the Sanin (oxidized), Sanyo (reduced) and Ryoke (reduced) belts in the southwestern Japan arc indicates that: (i) light REEs (LREEs) decease with fractionation of the granitoids in the Sanin belt but this trend is not clear in the granitoids in the Sanyo belt and LREEs rather increase in the Ryoke granitoids; (ii) Eu decreases with fractionation in all the belts; and (iii) HREEs slightly, but steadily decrease in the Sanin belt but enrich significantly in the Sanyo and Ryoke belts with fractionation. Analytical results of REE concentrations by scanning electron microscope with energy dispersive X‐ray spectroscope and laser ablation‐inductively coupled plasma mass spectrometer in the constituent minerals in a granodiorite sample from the Sanin belt show a moderate concentration of REEs in hornblende (577 ppm) in addition to high concentrations in allanite (~20 %), britholite (~30 %), primary titanite (8922 ppm), apatite (4062 ppm), and zircon (1693 ppm). Because primary titanite and allanite are commonly present in the oxidized granitoids but not in the reduced ones, the REE depletion in the fractionated, oxidized granites is attributed to the crystallization of these minerals. In contrast, scarcity of these minerals in the reduced granitoids enriches REEs, in particular HREEs in the fractionated magmas, which finally precipitate REEs in the granites and pegmatites. Both positive, but different correlation ratios between the Nb and Dy concentrations in the granitoids of the Sanin and Sanyo‐Ryoke belts suggest that columbite–pyrochlore‐group and fergusonite‐group minerals are the major HREE host in the oxidized and reduced granites, respectively.     

Functional roles of interzonal migrating mesozooplankton in the western subarctic Pacific

Grazing experiments and production estimation based on life-history analysis of Neocalanus copepods (N. cristatus, N. plumchrus and N. flemingeri) were carried out in the Oyashio region to understand the carbon flows associated with the interzonal migrating copepods. These copepods, and also Eucalanus bungii, fed on nano- and micro-sized organisms non-selectively throughout the season. However, diatoms were the dominant food resource until May and organisms, such as ciliates were the major resource after May. Daily growth rate was estimated from the Ikeda–Motoda, Huntley–Lopez and Hirst–Sheader models. Since the growth rates were considered to be overestimates for the Huntley–Lopez model and underestimates for the other two models, we applied the weight-specific growth rates previously reported for these species in the Bering Shelf. Surface biomass of Neocalanus increased rapidly in June during the appearance of C5, and a successive increase of overwintering stock was evident in the deeper layer. The deep biomass decreased gradually from September to May during the dormant and reproduction period. N. cristatus has the largest annual mean biomass (2.3 gC m⁻²), followed by N. plumchrus (1.1) and N. flemingeri (0.4). Daily production rate of Neocalanus varied from 0.4 to 363.4 mgC m⁻² day⁻¹, to which N. cristatus was the largest contributor. Annual production was estimated as 11.5 gC m⁻² year⁻¹ for N. cristatus, 5.7 for N. plumchrus and 2.1 for N. flemingeri, yielding annual P/B ratio of 5 for each species. The annual production of Neocalanus accounted for 13.2% of the primary production in the Oyashio region. Their fecal pellets were estimated to account for 14.9% (0.7 gC m⁻² year⁻¹) of sinking flux of organic carbon at 1000-m depth. Moreover, their export flux by ontogenetic vertical migration, which is not measured by sediment trap observations, is estimated to be 91.5% (4.3 gC m⁻² year⁻¹) of carbon flux of sinking particles at 1000-m depth. These results suggest the important role of interzonal migrating copepods in the export flux of carbon.     

Rapid Alkalization in Lake Inawashiro, Fukushima, Japan: Implications for Future Changes in the Carbonate System of Terrestrial Waters

The global carbon cycle, one of the important biogeochemical cycles controlling the surface environment of the Earth, has been greatly affected by human activity. Anthropogenic nutrient loading from urban sewage and agricultural runoff has caused eutrophication of aquatic systems. The impact of this eutrophication and consequent photosynthetic activity on CO₂ exchange between freshwater systems and the atmosphere is unclear. In this study, we focused on how nutrient loading to lakes affects their carbonate system. Here, we report results of surveys of lakes in Japan at different stages of eutrophication. Alkalization due to photosynthetic activity and decreases in PCO₂ had occurred in eutrophic lakes (e.g., Lake Kasumigaura), whereas in an acidotrophic lake (Lake Inawashiro) that was impacted by volcanic hot springs, nutrient loading was changing the pH and carbon cycling. When the influence of volcanic activity was stronger in the past in Lake Inawashiro, precipitation of volcanic-derived iron and aluminum had removed nutrients by co-precipitation. During the last three decades, volcanic activity has weakened and the lake water has become alkalized. We inferred that this rapid alkalization did not result just from the reduction in acid inputs but was also strongly affected by increased photosynthetic activity during this period. Human activities affect many lakes in the world. These lakes may play an important part in the global carbon cycle through their influence on CO₂ exchange between freshwater and the atmosphere. Biogeochemical changes and processes in these systems have important implications for future changes in aquatic carbonate systems on land.     

The layered structure of lunar maria: Identification of the HF-radar reflector in Mare Serenitatis using multiband optical images

Comparison of the Lunar Radar Sounder (LRS) data to the Multiband Imager (MI) data is performed to identify the subsurface reflectors in Mare Serenitatis. The LRS is FM-CW radar (4–6 MHz) and the 2 MHz bandwidth leads to the range resolution of 75 m in a vacuum, whereas the sampling interval in the flight direction is about 75 m when an altitude of the spacecraft with polar orbit is nominal (100 km). Horizontally continuous reflectors were clearly detected by LRS in limited areas that consist of about 9% of the whole maria. The typical depth of the reflectors is estimated to be a few hundred meters. Layered structures of mare basalts are also discernible on some crater walls in the MI data of the visible bands (VIS). The VIS range has nine wavelengths of 415, 750, 900, 950, and 1000 nm, and their spatial resolution is 20 m/pixel at a nominal altitude. The stratigraphies around Bessel and Bessel-H craters in Mare Serenitatis are examined in this paper. It was revealed that the subsurface reflectors lie on the boundaries between basalt units with different chemical compositions. In addition, model calculations using the simplified radar equation indicate that the subsurface reflectors are not compositional interfaces but layer boundaries with a high-porosity contrast. These results suggest that the detected reflectors in Mare Serenitatis are regolith accumulated during so long hiatus of mare volcanisms enough for chemical composition of magma to change, not instantaneously. Therefore combination of the LRS and MI data has a potential to reveal characteristics of a series of magmatism forming each lithostratigraphic unit in Mare Serenitatis and other maria.     

Assignment of groundwater level at the wastewater collecting pipe for a landfill groundwater simulation: utilization of the two-dimensional saturated–unsaturated groundwater numerical model

In order to understand the effects of a landfill operation on groundwater flow behavior, a 2D horizontal groundwater simulation model was carried out. The model saved the memory of computer and time consumption, comparing it with the 3D groundwater flow model. However, the greatest difficulty is the assignment of the collecting pipe boundary at the study site. Therefore, a 2D vertical model was applied to calculate the change of the groundwater table above the collecting pipe. This paper focuses on examining the validation of the assignment of the collecting pipe boundary by applying the results of the 2D vertical model. The 2D horizontal model was coupled with the recharge model to solve the partial differential equation of groundwater flow. The finite difference method and iterative successive over relaxation were applied. The drainage volume of leachate collection was summed up in the whole landfill site and compared with the average volume of treated wastewater. The study demonstrated that the results of the 2D vertical model validated and can be applied to the 2D horizontal groundwater flow simulation.     

Vertical distributions of large ontogenetically migrating copepods in the Oyashio region during their growing season

Neocalanus flemingeri, Neocalanus plumchrus, Neocalanus cristatus and Eucalanus bungii are large and dominant mesozooplankton occurring throughout the subarctic Pacific. They are an important trophic link and transporter of organic matter to the mesopelagic zone. Vertical distributions of these copepods were investigated from March to October 2000 in the Oyashio region of the western subarctic Pacific. Neocalanus plumchrus and N. flemingeri were distributed in the surface layer (0–50 m) and N. cristatus and E. bungii in the subsurface layer (50–100 m). However, when examined in detail, clear seasonal and vertical differences were observed. Neocalanus plumchrus was concentrated in the top 20 m from late April to the end of July, and N. flemingeri showed a little deeper distribution from May to July. Neocalanus cristatus showed a deeper distribution than that of grazing individuals of E. bungii from April to early July, but grazing individuals of E. bungii (C3–C6) showed a deeper distribution than that of N. cristatus from the end of July to October. Early copepodites of E. bungii were distributed much shallower than late copepodite stages and overlapped with copepodites of N. plumchrus and N. flemingeri. These results suggest that the four species of large copepods have established habitat segregation by season, vertical distribution and food resource partitioning in the Oyashio region as well as other regions of the North Pacific.     

Physical behavior of the SEEDS iron-fertilized patch by sulphur hexafluoride tracer release

The first iron (Fe) – fertilization experiment in the western North Pacific was carried out using SF₆ to trace the Fe-fertilized water mass. A solution in 10,800 liters of seawater of 350 kg of Fe and 0.48 M of SF₆ tracer was released into the mixed layer over a 8 × 10 km area. On the first underway transects through the patch after the Fe release, we observed a significant increase of dissolved Fe (ave. 2.89 nM). The fertilized patch was traced for 14 days by on-board SF₆ analysis. A Lagrangian frame of reference was maintained by the use of a drogued GPS buoy released at the center of the patch. The patch moved westward at a rate of 6.8 km d⁻¹. Mixed layer depth increased from 8.5 to 15 m during the experiment. Horizontal diffusivity was determined by the change of SF₆ concentration in the patch. The horizontal diffusivity increased during the experiment. We evaluate here the fate of Fe in a Fe-fertilized patch using the dilution rate determined from sulphur hexafluoride (SF₆) concentration. Dissolved Fe concentrations subsequently decreased rapidly to 0.15 nM on Day 13. However, the dissolved Fe half-life of 43 h was relatively longer than in previous Fe-enrichment studies, and we observed a larger increase of the centric diatom standing stock and corresponding drawdown of macro-nutrients and carbon dioxide than in the previous studies. The most important reason for the larger response was the phytoplankton species in the western North Pacific. In addition, the smaller diffusivity and shallower mixed layer were effective to sustain the higher dissolved Fe concentration compared to previous experiments. This might be one reason for the larger response of diatoms in SEEDS.     

Mineralogical and textural variation of silica minerals in hydrothermal flow-through experiments: Implications for quartz vein formation

We conducted hydrothermal flow-through experiments at 430 °C and 31 MPa to investigate the mechanism of silica precipitation on granite under crustal conditions. Two experiments were performed using different input solutions: a single-component Si solution, and a multi-component solution with minor Al, Na, and K. The degree of supersaturation with respect to quartz, Ω = C_Si/C_Si,Qtz,eq, where C_Si and C_Si,Qtz,eq indicate Si concentration in solutions and the solubility of quartz within water, respectively, decreased from 3-3.5 to <1.1 along the flow path. A variety of silica minerals formed during the experiments (opal-A, opal-C, chalcedony, and quartz), and their occurrences and modal abundances changed in response to Ω and the presence of additives in the solution.For near-equilibrium solutions (Ω < ∼1.2), silica precipitation occurred in a simple way in both experiments, being restricted to overgrowths on pre-existing quartz surfaces in the granite. At higher saturation levels (Ω > ∼1.2), silica minerals were deposited on other surfaces in addition to quartz. In the single-component experiment, the dominant silica minerals changed in the order of opal-A → opal-C → quartz with decreasing Si concentration along the flow path. In contrast, in the multi-component experiment, quartz and minor chalcedony formed throughout the entire reaction vessel. This finding indicates that impurities (Na, K, and Al) in the solutions inhibited the precipitation of opal and enhanced the direct nucleation of quartz. The systematic appearance of metastable silica minerals were examined by nucleation processes and macroscopic precipitation kinetics. Our experimental results indicate that different precipitation mechanisms yield contrasting textures, which in turn suggests that vein textures can be used as indicators of solution chemistry within the fracture.     

Impact of climate change on runoff from a mid‐latitude mountainous catchment in central Japan

Hydrologic balance in high‐altitude, mid‐latitude mountain areas is important in terms of the water resources available to associated lowlands. This study examined how current and historical shifts in precipitation (P) patterns and concurrent increases in temperature (T) affected runoff (Q) and other hydrologic components in a mid‐latitude mountain catchment of central Japan, using a combination of long‐term data and a simplified hydrologic model, along with their stochastic treatment. The availability of intensive meteorological and hydrological data from the period 1997–2001 allowed the derivation of key relationships for the current climate that tie the forcing term to the parameters or state variables. By using the data recorded in the period 1965–2001, the force for driving the historical simulation was generated. Based on this model and historical shifts in P and T, the probability density functions of Q (pdf(Q)) was computed. A main novelty in this study is that such a stochastic representation, which is useful for considering the influence of projected shifts in environmental factors on the hydrologic budget, was provided. Despite the large increase in the rate of T in winter and spring, pdf(Q) in spring and summer varied appreciably during the time studied mainly because of an increase in snowmelt. An interannual change in whole‐year Q was robust to shifts in T because while Q in spring increased, in summer it decreased, implying a crucial effect of global warming on mountain hydrologic regimes is change in the timing of Q. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of Selenium in Twenty-Eight Geological Reference Materials by Atomic Absorption Spectrometry

Twenty-eight geological reference samples have been analysed for selenium using atomic absorption spectrometry with hydride generation and quartz cell atomizer and/or with solvent extraction and carbon tube atomizer. Data are presented for 5 CCRMP, 6 USGS, 3 NBS, 6 NIM and 8 GSJ reference materials.