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.

Bromate Reduction by Rhodococcus sp. Br-6 in the Presence of Multiple Redox Mediators.

A bromate (BrO3-)-reducing bacterium, designated Rhodococcus sp. strain Br-6, was isolated from soil. The strain reduced 250 µM bromate completely within 4 days under growth conditions transitioning from aerobic to anaerobic conditions, while no reduction was observed under aerobic and anaerobic growth conditions. Bromate was reduced to bromide (Br-) stoichiometrically, and acetate was required as an electron donor. Interestingly, bromate reduction by strain Br-6 was significantly dependent on both ferric iron and a redox dye 2,6-dichloroindophenol (DCIP). Cell free extract of strain Br-6 showed a dicumarol-sensitive diaphorase activity, which catalyzes the reduction of DCIP in the presence of NADH. Following abiotic experiments showed that the reduced form of DCIP was reoxidized by ferric iron, and that the resulting ferrous iron reduced bromate abiotically. Furthermore, activity staining of the cell free extract revealed that one of diaphorase isoforms possessed a bromate-reducing activity. Our results demonstrate that strain Br-6 utilizes multiple redox mediators, that is, DCIP and ferric iron, for bromate reduction. Since the apparent rate of bromate reduction by this strain (60 µM day-1) was 3 orders of magnitude higher than that of known bromate-reducing bacteria, it could be applicable to removal of this probable human carcinogen from drinking water.

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.

Laccase-catalyzed oxidation of iodide and formation of organically bound iodine in soils.

Laccase oxidizes iodide to molecular iodine or hypoiodous acid, both of which are easily incorporated into natural soil organic matter. In this study, iodide sorption and laccase activity in 2 types of Japanese soil were determined under various experimental conditions to evaluate possible involvement of this enzyme in the sorption of iodide. Batch sorption experiment using radioactive iodide tracer ((125)I(-)) revealed that the sorption was significantly inhibited by autoclaving (121 °C, 40 min), heat treatment (80 and 100 °C, 10 min), γ-irradiation (30 kGy), N(2) gas flushing, and addition of reducing agents and general laccase inhibitors (KCN and NaN(3)). Interestingly, very similar tendency of inhibition was observed in soil laccase activity, which was determined using 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as a substrate. The partition coefficient (K(d): mL g(-1)) for iodide and specific activity of laccase in soils (Unit g(-1)) showed significant positive correlation in both soil samples. Addition of a bacterial laccase with an iodide-oxidizing activity to the soils strongly enhanced the sorption of iodide. Furthermore, the enzyme addition partially restored iodide sorption capacity of the autoclaved soil samples. These results suggest that microbial laccase is involved in iodide sorption on soils through the oxidation of iodide.

Iodide oxidation by a novel multicopper oxidase from the alphaproteobacterium strain Q-1.

Alphaproteobacterium strain Q-1 is able to oxidize iodide (I(-)) to molecular iodine (I(2)) by an oxidase-like enzyme. One of the two isoforms of the iodide-oxidizing enzyme (IOE-II) produced by this strain was excised from a native polyacrylamide gel, eluted, and purified. IOE-II appeared as a single band (51 kDa) and showed significant in-gel iodide-oxidizing activity in sodium dodecyl sulfate-polyacrylamide gel electrophoresis without heat treatment. However, at least two bands with much higher molecular masses (150 and 230 kDa) were observed with heat treatment (95°C, 3 min). IOE-II was inhibited by NaN(3), KCN, EDTA, and a copper chelator, o-phenanthroline. In addition to iodide, IOE-II showed significant activities toward phenolic compounds such as syringaldazine, 2,6-dimethoxy phenol, and p-phenylenediamine. IOE-II contained copper atoms as prosthetic groups and had UV/VIS absorption peaks at 320 and 590 nm. Comparison of several internal amino acid sequences obtained from trypsin-digested IOE-II with a draft genome sequence of strain Q-1 revealed that the products of two open reading frames (IoxA and IoxC), with predicted molecular masses of 62 and 71 kDa, are involved in iodide oxidation. Furthermore, subsequent tandem mass spectrometric analysis repeatedly detected peptides from IoxA and IoxC with high sequence coverage (32 to 40%). IoxA showed homology with the family of multicopper oxidases and included four copper-binding regions that are highly conserved among various multicopper oxidases. These results suggest that IOE-II is a multicopper oxidase and that it may occur as a multimeric complex in which at least two proteins (IoxA and IoxC) are associated.

Determination of (129)I and (127)I concentration in soil samples from the Chernobyl 30-km zone by AMS and ICP-MS.

A large amount of radioiodine isotopes (mainly (131)I, t(1/2) = 8 days) was released from the accident at Chernobyl Nuclear Power Plant (CNPP) in April-May 1986. An increase in childhood-thyroid cancer in the contaminated areas in Belarus, Russia and the Ukraine was demonstrated to be caused by radioiodine released at the time of the accident. However, there is a lack of quantitative data on the (131)I levels in the local environment (e.g. air, plant, soil). At this point, a long-lived iodine isotope, (129)I (t(1/2) = 15.7 million years), also released with a certain ratio to (131)I from CNPP, could be used for estimating the (131)I levels in the environment. In this paper we present analytical results of the (129)I concentrations and (129)I/(127)I atom ratios in soil samples collected from the CNPP exclusion zone (30-km zone), with the aim of assessing current contamination levels and distribution patterns. For the analysis of the iodine fraction in the investigated soil samples, the pyrohydrolysis method was utilized for separation of (127)I and (129)I nuclides, and subsequently their concentration was determined using inductively coupled plasma mass spectrometry (ICP-MS) and accelerator mass spectrometry (AMS), respectively. The concentration of (129)I and the (129)I/(127)I atom ratio in the surface soil samples in the 30 km-zone of CNPP ranged from 4.6 to 170 mBq/kg, and from 1.4 x 10(-6) to 13 x 10(-6), respectively. These values are significantly higher than those from global (129)I fallout, indicating that most of the measured (129)I was due to the deposition of the accident. Stable iodine concentrations in this area were found to be very low (below 1 ppm) for most of the samples, suggesting the environmental iodine levels in this area to be potentially low. The (129)I/(137)Cs activity ratio in surface and sub-surface soils was not so constant, i.e., in the range (7.3-20.2) x 10(-7). This might be due to the different behavior of deposition and/or migration of these nuclides in soil. These results suggest the obtained data of (129)I to be useful for the reconstruction of the (131)I deposition in the contaminated areas.

Hydrogen peroxide-dependent uptake of iodine by marine Flavobacteriaceae bacterium strain C-21.

The cells of the marine bacterium strain C-21, which is phylogenetically closely related to Arenibacter troitsensis, accumulate iodine in the presence of glucose and iodide (I-). In this study, the detailed mechanism of iodine uptake by C-21 was determined using a radioactive iodide tracer, 125I-. In addition to glucose, oxygen and calcium ions were also required for the uptake of iodine. The uptake was not inhibited or was only partially inhibited by various metabolic inhibitors, whereas reducing agents and catalase strongly inhibited the uptake. When exogenous glucose oxidase was added to the cell suspension, enhanced uptake of iodine was observed. The uptake occurred even in the absence of glucose and oxygen if hydrogen peroxide was added to the cell suspension. Significant activity of glucose oxidase was found in the crude extracts of C-21, and it was located mainly in the membrane fraction. These findings indicate that hydrogen peroxide produced by glucose oxidase plays a key role in the uptake of iodine. Furthermore, enzymatic oxidation of iodide strongly stimulated iodine uptake in the absence of glucose. Based on these results, the mechanism was considered to consist of oxidation of iodide to hypoiodous acid by hydrogen peroxide, followed by passive translocation of this uncharged iodine species across the cell membrane. Interestingly, such a mechanism of iodine uptake is similar to that observed in iodine-accumulating marine algae.

Rate of iodine volatilization and accumulation by filamentous fungi through laboratory cultures.

Five strains of basidiomycetes (Lentinula edodes, Coprinus phlyctidosporus, Hebeloma vinosophyllum, Pleurotus ostreatus and Agaricus bisporus), one strain of ascomycete (Hormoconis resinae) and six strains of imperfect fungi (Penicillium chrysogenum, Penicillium roquefortii, Cladosporium cladosporioides, Alternaria alternata, Aspergillus niger and Aspergillus oryzae) were cultured in a liquid medium containing a radioactive iodine tracer ((125)I), and were tested for their abilities to volatilize or accumulate iodine. Of the fungal strains tested, 11 strains volatilized a considerable amount of iodine, with L. edodes showing the highest volatilization rate of 3.4%. The volatile organic iodine species emitted from imperfect fungi cultures was identified as methyl iodide (CH(3)I). In contrast, six fungal strains in 12 strains accumulated a considerable amount of iodine from the medium with concentration factors of more than 1.0. Among these, Alt. alternata and Cl. cladosporioides accumulated more than 40% of the iodine in their hyphae, and showed high concentration factors of 22 and 18, respectively. These results suggest that filamentous fungi have a potential to influence the mobility and speciation of iodine by volatilization and accumulation. Considering their great biomass in soils, filamentous fungi may contribute to the global circulation of stable iodine and also the long-lived radioiodine, (129)I (half-life: 1.6 x 10(7)years), released from nuclear facilities into the environment.

Dietary iodine intake in residents of northwestern regions of ukraine contaminated by the chernobyl accident.

Daily iodine intake in Ukrainian subjects of northwestern regions was estimated in relation to the health effects on inhabitants after the Chernobyl accident. Total diets were collected from 106 locations for children and adult males by a duplicate portion study. Iodine was rapidly determined by inductively coupled plasma mass spectrometry after chemical separation. Iodine concentration on a dry basis for Ukrainians was 0.11 microg g(-1) and the daily iodine intake was in the range of 2.80-372 microg per person. The median, geometric mean, and standard deviation were 28.1, 32.7, and 2.51 microg, respectively. The yearly trend of the intake had almost no change. Regional differences would be expected to exist among the 10 areas of the Ukraine, but no clear differences appeared in the present findings. Daily iodine intake in Ukrainians was lower than the recommended dietary intake (RDI) allowance (150 microg), and its lack would be related to the high prevalence of goiter in the country.

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.

Accumulation of (137)Cs by rice grown in four types of soil contaminated by the Fukushima Dai-ichi Nuclear Power Plant accident in 2011 and 2012.

The ability to predict radiocesium transfer from soil to agricultural products is necessary for assessing management options in a radiocesium contaminated area. In this study, we evaluated the differences in transfer factors among soil samples and the differences in transfer factors between the first and the second years of contamination in rice. We employed pot experiments using four types of soils that are representative of the agricultural soils present in the Fukushima Prefecture contaminated by (137)Cs released from the Fukushima Dai-ichi Nuclear Power Plant after the March 2011 accident. The experiments were conducted during the 2011 and 2012 growing seasons. The geometric mean of transfer factors for brown rice and inedible rice part was 0.011 and 0.031, respectively, in 2011 and 0.0061 and 0.020, respectively, in 2012. The average decreasing rate of the transfer factor was 40% and 30% in brown rice and inedible rice part, respectively, from 2011 to 2012, presumably owing to the irreversible sorption of (137)Cs to clay minerals.

Transfer factors of radioiodine from volcanic-ash soil (Andosol) to crops.

In order to obtain soil-to-plant transfer factors (TFs) of radioiodine from volcanic-ash soil to agricultural crops, we carried out radiotracer experiments. The mean values of TFs (on a wet weight basis) of radioiodine from Andosol to edible parts of crops were as follows: water dropwort, 0.24; lettuce, 0.00098; onion, 0.0011; radish, 0.0044; turnip, 0.0013 and eggplant, 0.00010. The mean value of the TFs of radioiodine for edible parts of wheat (on a dry weight basis) was 0.00015. We also studied the distributions of iodine in crops. There was a tendency for the TFs of leaves to be higher than those of tubers, fruits and grains. A very high TF was found for water dropwort, because this plant was cultivated under a waterlogged condition, in which iodine desorbed from soil into soil solution with a drop in the Eh value. The data obtained in this study should be helpful to assess the long-lived 129I (half life: 1.57 x 10(7) yr) pathway related to the fuel cycle.

Concentrations of 137Cs and 40K in mushrooms consumed in Japan and radiation dose as a result of their dietary intake.

Mushrooms are known to accumulate radiocesium. To estimate the intake of radiocesium through the eating of mushrooms, about 30 samples belonging to 4 commonly consumed species (Lentinula edodes, Hypsizigus marmoreus, Grifola frondosa, and Tricholoma matsutake), were analyzed for (137)Cs and (40)K. The concentration ranges were 0.060-29 Bq kg(-1) (wet wt) for (137)Cs and 38-300 Bq kg(-1) (wet wt) for (40)K. The geometric mean concentration for (137)Cs was 0.56 Bq kg(-1) (wet wt), and the mean concentration for (40)K was 92 Bq kg(-1) (wet wt). The (137)Cs concentrations in L. edodes cultivated in mushroom beds (sawdust-rice bran media) were lower than those cultivated on bed logs (natural wood with bark). The annual intake of (137)Cs per person through mushrooms was calculated, by using the current analytical results and food consumption data in Japan, to be 3.1 Bq for (137)Cs, which is about 28% of the total dietary intake of this nuclide. The effective dose equivalent of (137)Cs through mushrooms was estimated to be 4.0 currency 10(-8) Sv, which is about the half the value obtained in our previous study. The decrease of the (137)Cs intake through mushrooms is probably related to changes in cultivation methods in recent years, from the use of bed logs to mushroom beds.

Retrospective evaluation of 131I deposition density and thyroid dose in Poland after the Chernobyl accident.

The 131I deposition in Poland after the Chernobyl accident on 26 April 1986 was evaluated from the determined 129I deposition and the estimated 129I/131I ratio at the time of the arrival of fallout. Concentrations of 129I and 127I were determined by neutron activation analysis in uncultivated soils from 16 locations in Poland. Determination of 137Cs in soils was carried out by gamma spectrometry. The atomic ratio of 129I/131I at the time of fallout arrival was estimated using the 129I/131I ratio at the time of the accident, which, on the basis of the core inventory data, was assumed to be 22.8. It was estimated from the time of fallout arrival and from the weighed mean atomic ratio that the 129I/131I ratio for Poland was 32.8. The calculated 131I deposition ranged from 63.2 to 729 kBq m(-2). High deposition of 131I occurred in the locations with rainfall but occasionally also in locations without rainfall. Committed equivalent doses from 131I were evaluated for 5-y-old children, 10-y-old children, and adults using the computer model CLRP for the situations with and without countermeasures including iodine prophylaxis. The highest thyroid doses from inhalation and ingestion without countermeasures were 178 mSv, 120 mSv, and 45 mSv for 5-y-old children, 10-y-old children, and adults, respectively. The countermeasures reduced these doses by about 30%.

Studies with natural and anthropogenic iodine isotopes: iodine distribution and cycling in the global environment.

Iodine is an important trace element in geological and biological processes. We summarize here recent results and new data of experiments and observations carried out to improve the understanding of concentration levels and behavior of natural and anthropogenic iodine nuclides in the global environment. The distribution of stable iodine in the Earth's crust was estimated using concentration data in a suite of representative samples and the influence of subduction on the marine iodine cycle was investigated using (129)I systematics on iodine-rich brines from Japan. The importance of microorganisms for the natural iodine cycle is shown in recent studies of iodine sorption on soil and of iodine volatilization from terrestrial and marine environments. Levels of anthropogenic (129)I were measured in samples collected around a spent fuel reprocessing plant in Japan.

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.

Dietary iodine and bromine intakes in Ukrainian subjects.

Dietary iodine and bromine intakes in Ukrainian subjects were estimated in relation to the health effects on inhabitants after the Chernobyl accident. Two hundred and eighty-six total diets were collected from twenty-five regions for Ukrainians by a duplicate portion study. Iodine and bromine were rapidly determined by inductively coupled plasma mass spectrometry after chemical separation. The range, median, and geometric mean of iodine intakes were 2.86-698, 44.7, and 48.1 microg per person per day, respectively. Those of bromine were 0.627-16.9, 2.97, and 2.92 mg per person per day, respectively. Daily intakes of both elements in Ukrainians were lower than previously reported values. The iodine intake in areas contaminated by the Chernobyl accident was lower than that in non-contaminated areas. The low iodine intake in both areas would be related to the high prevalence of goiters throughout the whole country. The low bromine intakes indicated Ukrainians were not exposed to bromine-containing foods.

Dissimilatory iodate reduction by marine Pseudomonas sp. strain SCT.

Bacterial iodate (IO(3)(-)) reduction is poorly understood largely due to the limited number of available isolates as well as the paucity of information about key enzymes involved in the reaction. In this study, an iodate-reducing bacterium, designated strain SCT, was newly isolated from marine sediment slurry. SCT is phylogenetically closely related to the denitrifying bacterium Pseudomonas stutzeri and reduced 200 microM iodate to iodide (I(-)) within 12 h in an anaerobic culture containing 10 mM nitrate. The strain did not reduce iodate under the aerobic conditions. An anaerobic washed cell suspension of SCT reduced iodate when the cells were pregrown anaerobically with 10 mM nitrate and 200 microM iodate. However, cells pregrown without iodate did not reduce it. The cells in the former category showed methyl viologen-dependent iodate reductase activity (0.31 U mg(-1)), which was located predominantly in the periplasmic space. Furthermore, SCT was capable of anaerobic growth with 3 mM iodate as the sole electron acceptor, and the cells showed enhanced activity with respect to iodate reductase (2.46 U mg(-1)). These results suggest that SCT is a dissimilatory iodate-reducing bacterium and that its iodate reductase is induced by iodate under anaerobic growth conditions.