Yusuke Fukami

A key driver to develop stable tungsten (W) isotope geochemistry is its unique relationship with molybdenum (Mo). Here, we establish a combined double-spike (DS) method for W (180W-184W spike) and Mo (97Mo-100Mo spike) to perform simple, efficient, and robust isotope measurements of these two chemically analogous elements in single sample aliquots. Based on previous column chemistry, we optimized two-stage anion-exchange procedures to remove matrix elements, particularly the critical interference of Ta and Hf on 180W, and to collect sharply separated W and Mo fractions. The obtained recoveries are quantitative for both elements, and their purities are sufficiently high to achieve high-precision measurements comparable to previous DS measurements of individual elements. The reproducibility of our isotope measurements for in-house standard solutions (2SD) was ±0.02‰ for δ186W and ±0.03‰ for δ98Mo. We applied our method to 27 geological reference materials including 10 igneous rocks (AGV-2, JA-3, JR-1, JB-1, JB-1a, JB-2, JB-3, W-2a, TDB-1, and WGB-1), 9 sediments (Nod-A-1, Nod-P-1, JMn-1, JMS-1, JMS-2, CRM7302-a, HISS-1, MESS-4, and PAC-3), and 8 sedimentary and metasedimentary rocks (SDC-1, SDO-1, SBC-1, SCO-1, SCO-2, JSL-1, JSL-2, and IOC-1) to produce a comprehensive data set. The data set confirmed the accuracy of our measurements and expanded the reference materials available for interlaboratory comparisons of δ186W and δ98Mo. The data set also indicates potential pitfalls in sample preparations for particular sample types and shows several variations of W and Mo isotopes possibly related to low-/high-temperature geochemical processes. Our new method, plus the reference data set, will facilitate the development of stable isotope geochemistry for W and Mo.

We examine the historical changes of 236U/238U and 235U/238U in a sediment core collected in Tokyo Bay and elucidate the anthropogenic sources of uranium in the 1960s-2000s. Uranium-236 was detected in samples deposited in the 1960s-2000s, and the 236U/238U ratio of the sediment core shows peak values in the 1970s. The 235U/238U isotopic ratios in samples deposited in the early 1960s are almost identical to that of natural uranium, implying that the 236U might have originated from global fallout. A decrease in 235U/238U was observed in the late 1960s-2000s, suggesting that depleted uranium from nuclear fuel reprocessing increased the 236U/238U ratios in the sediment. The 236U/238U values in sediments from the 1980s-2000s were lower than those in the 1970s but considerably higher than those in the 1960s, suggesting that the main source of depleted uranium still remains around Tokyo Bay. Our results demonstrated that the depleted uranium released in the 1970s should be considered as an important end-member when using uranium isotopic ratios as environmental tracers in closed aquatic environments around industrial cities.

We present the first report of the concentrations and stable isotope compositions of Te in the surface layer of ferromanganese crusts collected from the slope of two seamounts in the Northwest Pacific Ocean, Takuyo-Daigo and Takuyo-Daisan, which cover water depths from 1000 to 5500 m. The Te concentration in the surface layer of the ferromanganese crusts sharply decreases with increasing depth at shallow regions, but this decrease becomes more gradual at deeper regions. The Te isotope composition exhibits two trends that become (1) lighter with increasing water depth at shallow depths and (2) heavier with increasing water depth at greater depths. These profiles are the same for the two seamounts and indicate two types of correlations between the concentration and isotope composition with water depth. The turning points are located at approximately 2000 m for Takuyo-Daigo and 3200 m for Takuyo-Daisan, which likely correspond to different oxygen minimum zones. Co-precipitation processes with Fe and oxidation involving Mn may be responsible for the variation of Te concentration and isotope composition with water depth. These processes are also related to a change of the dissolved oxygen concentration in ambient seawater. The Te isotope compositions in ferromanganese crusts may therefore serve as a potential proxy for changes of the oxygen minimum zone of paleoceans.

We examine the temporal changes of 236U/238U and 235U/238U in atmospheric deposition from samples collected in Tokyo and Akita from 1963 to 1979 and elucidate the spatial distribution and historical changes of the anthropogenic sources of uranium in Japan. The 236U/238U ratio of atmospheric deposition in Tokyo peaked in 1963 and again during the 1970s, while the corresponding 235U/238U ratios of atmospheric deposition during the second peak period were lower than that of natural uranium. The 236U/238U ratios of atmospheric deposition in Akita samples peaked in 1963. The 235U/238U ratios in Akita samples were almost identical to that of the natural uranium ratios. These results suggest that the peak of 236U/238U in 1963 corresponds to what is recognized as representative for global fallout. The increase of 236U/238U and the decrease of 235U/238U observed simultaneously in the 1970s indicate that depleted uranium has subsequently been released into the environment around Tokyo. The cumulative deposition density of 236U for atmospheric fallout samples collected in Tokyo from 1968 to 1979 is an order of magnitude larger than that of the global fallout, suggesting that the depleted uranium in the 1970s is a major component of 236U in Tokyo and should be considered as an end-member when using 236U as an environmental tracer in the industrial city. This knowledge can facilitate future research using 236U as an effective environmental tracer.