GEOTRACES is an international research project on marine biogeochemical cycles of trace elements and their isotopes. GEOTRACES key trace metals in seawater are Al (8-1000 ng/kg), Mn (4-300 ng/kg), Fe (1-100 ng/kg), Cu (30-300 ng/kg), Zn (3-600 ng/kg), and Cd (0.1-100 ng/kg), of which global oceanic distribution will be determined on a number of research cruises. This work introduces a novel method of solid-phase extraction to determine Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in seawater by adjusting the pH of the sample to 6 and carrying out a single preconcentration step. The trace metals were collected from approximately 120 mL of seawater using a column of a chelating resin containing the ethylenediaminetriacetic acid functional group and eluted with approximately 15 mL of 1 M HNO3. Mn and Fe in the eluate were measured by inductively coupled plasma mass spectrometry (ICPMS) using the dynamic reaction cell mode, and the other metals were measured using the standard mode. Using this procedure, the trace metals were collected quantitatively, while >99.9% of alkali and alkaline earth metals in seawater were removed. The procedural blank was <7% of the mean concentration in deep ocean waters, except 16% for Pb. The overall detection limit was <14% of the mean concentration in deep ocean waters. The RSD was <9%. Our values for the trace metals in the certified reference materials of seawater NASS-5 and nearshore seawater CASS-4 agreed with the certified values (except that there is no certified value for Al). This method was also successfully applied to the reference materials of open-ocean seawater produced by the SAFe program. Our Fe concentrations were 5.9 +/- 0.7 ng/kg for surface water (S1) and 50.4 +/- 2.9 ng/kg for deep water (D2), which are in agreement with the interlaboratory averages of 5.4 +/- 2.4 and 50.8 +/- 9.5 ng/L, respectively. The data for other metals were oceanographically consistent.

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Wang et al., 2011 (1) and is converted to δ 97/95 Mo by multiplying 0.67 when the system follows mass-dependent fractionation. Though no commonly-used Mo isotopic standard currently exists (see later), the standards used by different laboratories do appear to be isotopically similar at the level of 0.1-0.2‰. Continental rock samples, such as granite, basalt, and clastic sediments, have δ 98/95 Mo of ~0.1‰ Siebert et al., 2003). Ferromanganese oxides, which scavenge Mo from seawater in oxic conditions, have a light isotopic signature (δ 98/95 Mo = -1.0 to -0.5‰; Siebert et al., 2003), whereas sediments formed in euxinic conditions (aqueous H 2 S concentrations higher than ~11 µM, the action point pro-The molybdenum isotopic composition of the modern ocean (Received September 13, 2011; Accepted January 5, 2012) Natural variations in the isotopic composition of molybdenum (Mo) are showing increasing potential as a tool in geochemistry. Although the ocean is an important reservoir of Mo, data on the isotopic composition of Mo in seawater are scarce. We have recently developed a new method for the precise determination of Mo isotope ratios on the basis of preconcentration using a chelating resin and measurement by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), which allows us to measure every stable Mo isotope . In this study, 172 seawater samples obtained from 9 stations in the Pacific, Atlantic, and Southern Oceans were analyzed, giving global coverage and the first full depth-profiles. The average isotope composition in δ Three-isotope plots for the Mo isotopes were fitted with straight lines whose slopes agreed with theoretical values for mass-dependent isotope fractionation. These results demonstrate that Mo isotopes are both uniformly distributed and follow a mass-dependent fractionation law in the modern oxic ocean. In addition, Mo isotopic analysis revealed that δ 98/95 Mo of the standard used in this study was 0.117 ± 0.009‰ lighter than the Mo standard that was used by Archer and Vance (2008). A common Mo standard is urgently required for the precise comparison of Mo isotopic compositions measured in different laboratories. On the other hand, our results strongly support the possibility of seawater as an international reference material for Mo isotopic composition.

Aluminum (Al), manganese (Mn), cobalt (Co), and lead (Pb) are key trace elements in seawater and thus significant in chemical oceanography research. However, although all of these elements are highly scavenged in the ocean, only a few studies focus on the intercomparison of their distributions. Here, we report the basin-scale and full-depth sectional distributions of these elements observed during three GEOTRACES Japan cruises in the North Pacific. We confirmed that a surface maximum of the dissolved (d) species is not a common feature for the four elements and that the d species have the lowest concentrations in the Pacific Deep Water (PDW) as compared to other oceans. The elements showed different speciations and distributions. The fraction of labile particulate (lp) species was calculated as the difference between the total dissolvable (td) species and d species. The lpM/tdM ratio, where M refers to an element, is highest for Al, at 0.66 ± 0.31 (average ± sd, n = 489), and lowest for Pb, at 0.02 ± 0.08 (n = 575). Further, the distribution of each element is uniquely related to ocean circulation. The tdAl concentration is high in the Equatorial Under Current (EUC), the North Equatorial Current (NEC), and the Lower Circumpolar Deep Water *Manuscript (LCDW). Manganese is supplied from reductive sources such as sediments on the continental shelves around the northern boundary. Cobalt is concentrated in the North Pacific Intermediate Water (NPIW) and in the Equatorial Pacific Intermediate Water (EqPIW) owing to the combined effects of supply from the continental shelves, biogeochemical cycling, and scavenging. Lead shows a subsurface maximum centered at ~35°N and ~200 m depth, implying an association with the formation of the Subtropical Mode Water (SMW) and the Central Mode Water (CMW). Although the subsurface Pb maximum in the Atlantic has diminished over the last three decades owing to the ban on leaded gasoline use, it has been sustained in the North Pacific through the growth of other anthropogenic sources in Asia and Russia. We propose that the enrichment factor of dM, defined as EF(dM) = (dM/dAl) seawater /(M/Al) upper crust , where (M/Al) upper crust is the molar ratio in upper crustal abundance, can be a good parameter for the sources. The median is 1.3  10 2 (n = 436) for EF(dMn), 3.2  10 2 (n = 430) for EF(dCo), and 1.2  10 3 (n = 413) for EF(dPb). The (dPb) found in this study is on the same order of magnitude as the EF values for aerosols found in the literature, suggesting that the deposition of aerosols is a major source for dPb. EFBecause EF(dMn) and EF(dCo) are ten to hundred times higher than the EF for aerosols, sources other than the aerosol deposition are more significant contributors to the concentrations of Mn and Co.

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Pb and Pb isotope ratios in the modern ocean have been altered significantly by anthropogenic Pb inputs over the past century. Most studies of anthropogenic Pb in the ocean have focused on the North Atlantic and North Pacific Oceans, and the impact of anthropogenic Pb inputs to the Indian Ocean and processes controlling the distribution of Pb in the Indian Ocean are poorly known. This study presents the Pb and Pb isotopic composition (206 Pb/ 207 Pb, 208 Pb/ 207 Pb) of 11 deep stations from the Indian Ocean Japanese GEOTRACES cruise (KH-09-5), from the Bay of Bengal and Arabian Sea to the Southern Ocean (62ºS). The Pb isotope ratios of the Indian Ocean range 1.140-1.190 for 206 Pb/ 207 Pb and 2.417-2.468 for 208 Pb/ 207 Pb, with lower ratios appearing in the shallow waters of the northern Indian Ocean and higher ratios appearing in the deep layers of the Southern Ocean. This result agrees with a previous study on Pb concentrations (Echegoyen et al., 2014) showing that the Indian Ocean, particularly its northern part, is largely perturbed by anthropogenic Pb inputs. 206 Pb/ 207 Pb and 208 Pb/ 207 Pb of the Indian sector Southern Ocean are still lower than natural Pb, showing this region was also affected by anthropogenic Pb. Anomalously low or high 206 Pb/ 207 Pb and 208 Pb/ 207 Pb were observed in the thermocline and shallow waters of the southern Indian Ocean and the Arabian Sea, which are ascribed to water mass distribution (e.g., Subantarctic Mode Water) and evolving Pb isotope ratios of this region as dominant anthropogenic Pb sources change. 206 Pb/ 207 Pb and 208 Pb/ 207 Pb in the Bay of Bengal are higher than those in the Arabian Sea, which might be the result of the anthropogenic Pb inputs from different provenance or seawater exchanging Pb isotopes with natural particles derived from rivers and/or sediments at the basin boundaries.

Understanding the circulation of water masses in the world's oceans is critical to our knowledge of the Earth's climate system. Trace elements and their isotopes have been explored as tracers for the movement of water masses 1 . One type of candidate elements 2 are the high-field-strength elements zirconium (Zr), hafnium (Hf), niobium (Nb) and tantalum (Ta). Here we measure the distributions of dissolved Zr, Hf, Nb and Ta along two meridional sections in the Pacific Ocean that extend from 65 • to 10 • S and from 10 • to 50 • N. We find that all four elements tend to be depleted in surface water. In the deep oceans, their concentrations rise along our transects from the Southern Ocean to the North Pacific Ocean, and show strong correlations with the concentration of silicate. These results indicate that terrigenous sources are important to the budget of Zr, Hf, Nb and Ta in sea water, compared with hydrothermal input. Unexpectedly, the weight ratios for Zr/Hf fall between 45 and 350 and those for Nb/Ta between 14 and 85 in Pacific sea water, higher than the ratios observed in fresh water, in the silicate Earth or in chondritic meteorites. We conclude that the fractionation of Zr/Hf and Nb/Ta ratios will be useful for tracing water masses in the ocean.In the modern ocean, deep water is formed in the northern North Atlantic and the Southern oceans and flows to the Indian and the Pacific oceans. This thermohaline circulation results in an oceanic mixing time in the range 500 to 1,000 years. Silicate (Si(OH) 4 ), a major nutrient, is taken up by diatoms from surface sea water to form siliceous tests, and remineralized from the sinking tests in deep water 3 . The silicate concentration increases with the age of the deep water. Such a biogeochemical cycle is important in controlling the biological productivity in the ocean. An international research collaboration program, GEOTRACES, has been launched recently to determine the global distribution of trace elements and their isotopes (TEIs) and to characterize more completely their biogeochemical cycles 1 . Refractory elements have a low supply to the oceans relative to their abundance in the Earth's crust 2 . They are also rapidly removed from sea water by adsorption on sinking particles, a process referred to as scavenging. These factors result in large variations in the oceanic distributions that typically reflect their sources, making them potential tracers of water masses. For this purpose, rare earth elements (REEs), which occur as carbonate complexes of a trivalent (+3) been measured in iron-manganese (Fe-Mn) crusts and nodules, sediments, and rocks 5-9 . The first dissolved seawater Hf isotope data were recently published 10,11 . Together with neodymium isotope ratios ( 143 Nd/ 144 Nd, expressed as ε Nd ), the Hf-Nd isotope system is used as an excellent proxy to elucidate the past change in continental weathering and/or hydrothermal sources to the ocean. It is now well known that for a given ε Nd , sea water and precipitates, such as ironmagnanese (Fe-Mn) crust...