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To investigate halogen heterogeneity in the subcontinental lithospheric mantle (SCLM), we measured the concentrations of Cl, Br, and I in kimberlites and their mantle xenoliths from South Africa, Greenland, China, Siberia, Canada, and Brazil. The samples can be classified into two groups based on halogen ratios: a high-I/Br group (South Africa, Greenland, Brazil, and Canada) and a low-I/Br group (China and Siberia). The halogen compositions were examined with the indices of crustal contamination using Sr and Nd isotopes and incompatible trace elements. The results indicate that the difference between the two groups was not due to different degrees of crustal contamination but from the contributions of different mantle sources. The low-I/Br group has a similar halogen composition to seawater-influenced materials such as fluids in altered oceanic basalts and eclogites and fluids associated with halite precipitation from seawater. We conclude that the halogens of the high-I/Br group are most likely derived from a SCLM source metasomatized by a fluid derived from subducted serpentinite, whereas those of the low-I/Br group are derived from a SCLM source metasomatized by a fluid derived from seawater-altered oceanic crust. The SCLM beneath Siberia and China could be an important reservoir of subducted, seawater-derived halogens, while such role of SCLM beneath South Africa, Greenland, Canada, and Brazil seems limited.

The lithophile elements and isotopic compositions of oceanic basalts suggest they derive from different mantle components. We present new analytical results of un-degassed deep-marine basaltic glasses from various regions, and we find strong linear correlations of R2 ≥ 0.997 between H2O and F as well as H2O and Ce, for which we propose mantle trends. The mantle trends represent global variations of mantle components, ranging from a depleted dry peridotite of mid-ocean ridge basalt (MORB) (DMM, depleted MORB source mantle: H2O = 100 ppm; H2O/Ce = 200; H2O/F = 10) to a hydrous peridotite of Hawaiian ocean island basalt (OIB) of deep mantle origin (FOZO, focal zone: H2O = 750 ppm; H2O/Ce = 200; H2O/F = 18.5). Accordingly, we defined the correlation as a volatile DMM–FOZO trend. Based on our findings, we report novel H2O–F–Ce systematics to discriminate the degree of water depletion in the source mantle and the rehydration of the mantle with recycled surface water through oceanic plate subduction. Using this method, most OIBs are distinguished clearly from the DMM–FOZO trend, and we find that the water in their sources originates from recycled water derived from the hydrated oceanic crust and sediment after various degrees of dehydration (75–95%) in subduction zones.

This study explores key features of bromine and iodine metabolism in the filamentous brown alga and genomics model Ectocarpus siliculosus. Both elements are accumulated in Ectocarpus, albeit at much lower concentration factors (2-3 orders of magnitude for iodine, and

The Kamchatka Peninsula is a prominent and wide volcanic arc located near the northern edge of the Pacific Plate. It has highly active volcanic chains and groups, and characteristic lavas that include adakitic rocks. In the north of the peninsula adjacent to the triple junction, some additional processes such as hot asthenospheric injection around the slab edge and seamount subduction operate, which might enhance local magmatism. In the forearc area of the northeastern part of the peninsula, monogenetic volcanic cones dated at

Many groups or chains of seamounts border, or are associated with, oceanic plateaus but their origin and relationship with plateau volcanism are debated. An example is Ojin Rise Seamounts, a group of ~80 seamounts located northeast of the 147–134 Ma Shatsky Rise, an oceanic plateau that was formed along the trace of a triple junction in the northwest Pacific Ocean. A notable topographic feature of Ojin Rise Seamounts is that they are distributed in such a way that they appear to be connected to another oceanic plateau in the east, the ~100 Ma Hess Rise. Many seamounts are arranged in a NW–SE direction (almost in the same absolute plate motion direction) and some are organized into seamount chains consisting of several volcanic cones connected by a common platform, reflecting a complex volcanic history. Here we report petrography as well as major and trace element, Sr, Nd, Pb, and Hf isotope, and 40Ar-39Ar age data for basalts dredged from five seamounts in the western part of Ojin Rise Seamounts. We found that the 40Ar-39Ar ages of the cones (123.7–120.7 Ma) are distinctly younger than the magnetic lineation age (M9-M7; 134–132 Ma) around the chain. The younger age suggests either a protracted development for the seamount chain, previously proposed to have formed near-ridge, or age difference between the platform and cones. The morphological and age differences are supported by petrography and geochemistry: platform basalts are aphyric, whereas cone basalts are slightly to highly plagioclase-phyric (up to 48 vol%); platform basalts are depleted in trace element and isotope composition, but cone basalts are enriched with high Nb/Ti and 87Sr/86Sr, and low 143Nd/144Nd and 176Hf/177Hf ratios. The depleted signature of the platform basalts is similar to that of the abundant normal type basalts of Shatsky Rise with an isotope composition that overlaps with that of normal mid-ocean ridge basalts (N-MORB), whereas trace elements are enriched (e.g., higher Nb/Zr and Nb/Ti than N-MORB). However, slight geochemical differences between the Ojin platform basalts and Shatsky normal type basalts exist and are expressed in higher 208Pb/204Pb isotope ratios of the former. The depleted signature implies shallow mantle dilution of the (enriched) Shatsky plume tail near a ridge. In contrast, the enriched signature of the cone basalts indicates little contribution from N-MORB source mantle as (enriched) plume volcanism moved away from the ridge. The enriched features (Nb/Zr and 176Hf/177Hf) of the Ojin Rise cone basalts increase with increasing distance from Shatsky Rise and conform with a geochemical evolution model that involves increasing contribution from a highly enriched Hess Rise source component with time.

We report a new, rapid method for the high-precision determination of chlorine isotope ratios in halite and AgCl pellets formed from seawater and igneous rock samples. Use of 266 nm ultra violet-femtosecond laser ablation (UV-FsLA) allowed quantitative sampling of halite and AgCl and enabled precise determination of 37Cl/35Cl isotope ratios (δ37Cl) when coupled with a multiple Faraday collector-inductively coupled plasma mass spectrometer (MFC-ICPMS). We used 36Ar+/38Ar+ as an external standard for the mass bias corrections between 39K+–41K+, 36Ar1H+–38Ar1H+–40Ar1H+, and 35Cl+–37Cl+ with isobaric overlap corrections between K+, ArH+, and Cl+ ions. Overlap of the sulfur (36S+) isobar with 36Ar+ was indirectly monitored and corrected by baseline modelling using the 36Ar+/38Ar+ measurement. These procedures collectively helped accomplish an accurate and high-precision measurement of 37Cl+/35Cl+ ratios. Using the proposed analytical method, δ37Cl ratios in natural halite samples were analysed by direct laser ablation. δ37Cl in JB-1a and JB-3 igneous rocks were analysed as AgCl powder pellets produced by pyrohydrolytic separation and co-precipitation of the separated Cl with silver. The external reproducibility of the δ37Cl measurements was ±0.2‰ 2SD (2 standard deviations) for halite and ±0.4‰ 2SD for AgCl precipitate rivalling that of gas source isotope ratio mass spectrometry. The new analytical protocol enabled a precise and rapid δ37Cl analysis of igneous rock samples as AgCl with as little as 4 μg chlorine from the ∼500 μg chlorine separated. This is the first time that high-precision in situ determination of δ37Cl from halite using 4 μg of chlorine has been reported.

Iodine-131 is one of the most critical radionuclides to be monitored after release from reactor accidents due to the tendency for this nuclide to accumulate in the human thyroid gland. However, there are not enough data related to the reactor accident in Fukushima, Japan to provide regional information on the deposition of this short-lived nuclide (half-life = 8.02 d). In this study we have focused on the long-lived iodine isotope, (129)I (half-life of 1.57 × 10(7) y), and analyzed it by accelerator mass spectrometry (AMS) for surface soil samples collected at various locations in Fukushima Prefecture. In order to obtain information on the (131)I/(129)I ratio released from the accident, we have determined (129)I concentrations in 82 soil samples in which (131)I concentrations were previously determined. There was a strong correlation (R(2) = 0.84) between the two nuclides, suggesting that the (131)I levels in soil samples following the accident can be estimated through the analysis of (129)I. We have also examined the possible influence from (129m)Te on (129)I, and found no significant effect. In order to construct a deposition map of (131)I, we determined the (129)I concentrations (Bq/kg) in 388 soil samples collected from different locations in Fukushima Prefecture and the deposition densities (Bq/m(2)) of (131)I were reconstructed from the results.

In order to understand the behavior of radionuclides released from the Fukushima Daiichi nuclear power plant, the depth distributions of radiocesium and radioiodine were investigated in a wheat field, a rice paddy, an orchard, and a cedar forest in Koriyama, Fukushima Prefecture. Our results demonstrate that, following the nuclear power plant disaster, more than 90% of the radionuclides were distributed in the upper 6 cm of the soil column in the wheat field and within 4 cm of the surface in the rice paddy, orchard, and cedar forest. According to the measurement of radionuclides in the three adjacent agricultural fields, the variation of deposition densities in the wheat field was smaller than that of the orchard and rice paddy, suggesting that the low permeability of the orchard and paddy soils may cause horizontal migration of radionuclides during the initial deposition. This result indicates that the deposition densities in the wheat field should be appropriate for estimating the amount of fallout in the area. The deposition densities of 134 Cs, 137 Cs, and 131 I in this area were estimated to be 512 ± 76 (SD, n = 5), 522 ± 80 (SD, n = 5), and 608 ± 79 (SD, n = 5) kBq/m 2 (decay corrected to April 1, 2011), respectively. A comparison of the deposition density between the wheat field and the cedar forest suggests that more than half of the radionuclides are distributed in the tree canopies of the evergreen forestland.

A method was developed for the determination of (129)I in soil samples that uses an ICP-MS equipped with an octopole reaction system. Oxygen was used as the reaction gas for reducing the background intensity of m/z 129, principally by (129)Xe(+). The contribution of polyatomic ions, such as (127)IH(2)(+), could be effectively corrected for by assuming a production ratio ((127)IH(2)(+)/(127)I(+) = 3 × 10(-8)). The measured (129)I/(127)I ratios in a NIST standard solution and Fukushima soil samples are consistent with the expected value within the analytical error. This method provides a powerful tool for investigating radioiodine contamination in Fukushima and elsewhere.

The metabolism of bromine in marine brown algae remains poorly understood. This contrasts with the recent finding that the accumulation of iodide in the brown alga Laminaria serves the provision of an inorganic antioxidant - the first case documented from a living system. The aim of this study was to use an interdisciplinary array of techniques to study the chemical speciation, transformation, and function of bromine in Laminaria and to investigate the link between bromine and iodine metabolism, in particular in the antioxidant context. First, bromine and iodine levels in different Laminaria tissues were compared by inductively coupled plasma MS. Using in vivo X-ray absorption spectroscopy, it was found that, similarly to iodine, bromine is predominantly present in this alga in the form of bromide, albeit at lower concentrations, and that it shows similar behaviour upon oxidative stress. However, from a thermodynamic and kinetic standpoint, supported by in vitro and reconstituted in vivo assays, bromide is less suitable than iodide as an antioxidant against most reactive oxygen species except superoxide, possibly explaining why kelps prefer to accumulate iodide. This constitutes the first-ever study exploring the potential antioxidant function of bromide in a living system and other potential physiological roles. Given the tissue-specific differences observed in the content and speciation of bromine, it is concluded that the bromide uptake mechanism is different from the vanadium iodoperoxidase-mediated uptake of iodide in L. digitata and that its function is likely to be complementary to the iodide antioxidant system for detoxifying superoxide. published

Atmospheric fallout samples collected from Tokyo between 1963 and 2003 were analyzed using accelerator mass spectrometry (AMS) in order to determine (129)I/(127)I ratios and to examine the deposition rate of (129)I and its secular variation in Tokyo. The (129)I/(127)I ratios in the atmosphere during 1963-1977 ranged from 1 × 10(-8) to 2 × 10(-8). This is roughly 4 orders of magnitude higher than pre-atomic levels, possibly due to atmospheric nuclear weapons tests. The calculated monthly atmospheric deposition rates of (129)I differed from those produced by nuclear fallout of (90)Sr and (137)Cs, indicating that the variations in (129)I deposition are not influenced exclusively by either nuclear bomb testing or by the Chernobyl accident. After 1978, high (129)I depositions (up to 0.13 mBq/m(2)/month) were observed. The (129)I depositions started to increase markedly at the latter half of the 1970s. The secular variation of the estimated annual (129)I deposition in Tokyo showed a close relationship between the annual atmospheric discharge of (129)I from the Tokai Reprocessing plant. Therefore, the atmospheric fallout collected from Tokyo after the late 1970s is influenced primary by the (129)I discharge from the Tokai Reprocessing plant.

Atmospheric (129)I deposition was studied in different locations of Japan (Akita, Tsukuba, Tokyo, and Ishigaki Island) with samples collected between 1963 and 2005 in order to understand the distribution and sources of this nuclide and provide a reference deposition level prior to the Fukushima accident. Over this time period, the deposition pattern of (129)I in Tsukuba and Tokyo (on the Pacific side) differed from that of Akita (on the Japan Sea side). The primary source of deposition in Tsukuba and Tokyo is related to the (129)I discharge from domestic reprocessing in Tokai-mura. In contrast, the time-series pattern of deposition in Akita seems to have been influenced by (129)I discharges from reprocessing facilities in Europe and the transport of this radionuclide by westerly winds to coastlines of the Japan Sea. The (129)I deposition in Ishigaki (one of the southernmost islands in Japan) is influenced primarily by oceanic air masses (easterly winds), and deposition was 1 order of magnitude lower than that observed in Tsukuba and Tokyo. Cumulative (129)I deposition in Tokyo before the Fukushima accident was estimated at 13 mBq/m(2). The results of this study on deposition contribute to understanding the deposition levels of (129)I prior to the accident.

A method was developed for the determination of 129I in soil samples using a Triple Quadrupole ICP-MS, with the objective of investigating radioiodine released by the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident. The determination of 129I by ICP-MS is capable of providing a high sample throughput compared to other methods. Nonetheless, the high background caused by 129Xe impurities in argon plasma gas and polyatomic ions such as 127IH2+ and 127ID+ has made it difficult to carry out determinations of this isotope by conventional ICP-MS instruments. In this study, oxygen was used as a reaction gas for reducing the background intensity of m/z 129, principally by 129Xe. The contribution of polyatomic ions such as 127IH2+ and 127ID+ could be effectively corrected for by assuming a production ratio of 5 × 10−9. The detection limit for 129I in solution was successfully improved. The measured 129I/127I ratios in NIST SRM 3231 Level II standard solution are consistent with the certified value of 0.981 × 10−8 within the analytical error, suggesting the reliability of the method to the measurement of 129I/127I. In order to confirm the applicability of this method to the measurement of 129I/127I ratios of Fukushima soils, samples were collected for analysis from 5–60 km away from the FDNPP. Prior to the ICP-MS measurement iodine fractions were separated from soil by pyrohydrolysis and were purified by solvent extraction. The 129I/127I ratios in the samples are consistent with values determined by accelerator mass spectrometry (AMS) within the analytical error. This method provides a powerful tool for the investigation of radioiodine contamination in Fukushima and elsewhere.

Strontium-Neodymium isotopes and 28 elements for Kimberlites from China (Shandong and Liaoning) and from South Africa (Kimberley area) have been measured to estimate their chemical characteristics and magma sources. The eSr and eNd values for Chinese kimberlites were, respectively, +1.0 to +93.0 and ‐4.3 to +0.2. The isotopic signature for all Shandong samples revealed very similar to those of Group I kimberlites (South African samples), whereas the Liaoning samples were categorized as Transitional. Although primitive mantle-normalized trace element patterns of the mean values of Group I Shandong and South African samples all resembled those of other Group I kimberlites, their HREE concentrations differed slightly. Shandong samples were depleted in HREEs. Our model calculation demonstrated that the kimberlites would be produced by partial melting with degree of less than 1%. Furthermore, Shandong samples were possibly generated from source rock in which the mineral contents differed slightly (specifically the proportion of garnet) from those of other regions.