Emission of volatile halogenated compounds, speciation and localization of bromine and iodine in the brown algal genome model Ectocarpus siliculosus.

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 < 1 order of magnitude for bromine) than e.g. in the kelp Laminaria digitata. Iodide competitively reduces the accumulation of bromide. Both iodide and bromide are accumulated in the cell wall (apoplast) of Ectocarpus, with minor amounts of bromine also detectable in the cytosol. Ectocarpus emits a range of volatile halogenated compounds, the most prominent of which by far is methyl iodide. Interestingly, biosynthesis of this compound cannot be accounted for by vanadium haloperoxidase since the latter have not been found to catalyze direct halogenation of an unactivated methyl group or hydrocarbon so a methyl halide transferase-type production mechanism is proposed.

In vivo speciation studies and antioxidant properties of bromine in Laminaria digitata reinforce the significance of iodine accumulation for kelps.

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.

Atmospheric fallout of (129)I in Japan before the Fukushima accident: regional and global contributions (1963-2005).

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.

Genesis of ultra-high-Ni olivine in high-Mg andesite lava triggered by seamount subduction.

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 <1 Ma were found. Despite their limited spatiotemporal occurrence, remarkable variations were observed, including primitive basalt and high-Mg andesite containing high-Ni (up to 6300 ppm) olivine. The melting and crystallization conditions of these lavas indicate a locally warm slab, facilitating dehydration beneath the forearc region, and a relatively cold overlying mantle wedge fluxed heterogeneously by slab-derived fluids. It is suggested that the collapse of a subducted seamount triggered the ascent of Si-rich fluids to vein the wedge peridotite and formed a peridotite-pyroxenite source, causing the temporal evolution of local magmatism with wide compositional range.

Analysis of 129I in the soils of Fukushima Prefecture: preliminary reconstruction of 131I deposition related to the accident at Fukushima Daiichi Nuclear Power Plant (FDNPP).

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.

Determination of 129I in Fukushima soil samples by ICP-MS with an octopole reaction system.

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.

Variations of 129I in the atmospheric fallout of Tokyo, Japan: 1963-2003.

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.