Sekine, Yurina; Nankawa, Takuya; Yamada, Teppei*; Matsumura, Daiju; Nemoto, Yoshihiro*; Takeguchi, Masaki*; Sugita, Tsuyoshi; Shimoyama, Iwao; Kozai, Naofumi; Morooka, Satoshi
Journal of Environmental Chemical Engineering, 9(2), p.105114_1 - 105114_12, 2021/04
Remediating toxic ion contamination is crucial for protecting human health and the environment. This study aimed to provide a powerful strategy for effectively utilizing bone waste from the food production and preparation industries for removal of toxic ions. Here, we show that immersing pig bone in NaHCO solution produced a carbonated nanohydroxyapatites (C-NHAP). The C-NHAP exhibited high adsorptivity for Sr, Cd, Pb, and Cu. The strontium adsorptivity was about 250 and 4,500 times higher than that of normal bone and synthetic HAP, respectively. The C-NHAP is an eco-friendly, high-performance material that is simple to prepare and should be useful for tackling problems of food waste disposal and environmental pollution.
Tokunaga, Kohei; Takahashi, Yoshio*; Tanaka, Kazuya; Kozai, Naofumi
Chemosphere, 266, p.129104_1 - 129104_10, 2021/03
Radioactive iodine (I) is of great concern owing to its high mobility in the environment and long-term radiotoxicity, but there is a lack of effective techniques for removing iodate (IO) from aqueous solution. The aim of this study is to develop a new technique for removing radioactive iodate from contaminated solution by using barite (BaSO). In the present study, we examined the coprecipitation mechanism of iodate by barite at the molecular level for determining optimum conditions for iodate removal. The results showed that iodate was effectively removed from aqueous solution by coprecipitation, even in the presence of competitive anions in solution. Comparing our method with previous studies, iodate removal efficiency by barite was determined to be about two orders of magnitude greater than that by hydrotalcite-like layered double hydroxide at Cl concentration of 10 mmol L. Extended X-ray absorption fine structure (EXAFS) analysis indicated that incorporated iodate was strongly bound in the crystal lattice of barite by substituting the sulfate site in the structure when the iodine concentration was low. The charge compensation problem from the IO substitution in SO site is achieved by the substitution of Na-IO pairs at the nearest Ba site. Therefore, considering high removal efficiency and strong binding of iodate in barite, coprecipitation with barite is a promising material for removing radioactive iodate from various aqueous solutions contaminated with iodate.
Guo, B.*; Xiong, Y.*; Chen, W.*; Saslow, S. A.*; Kozai, Naofumi; Onuki, Toshihiko*; Dabo, I.*; Sasaki, Keiko*
Journal of Hazardous Materials, 389, p.121880_1 - 121880_11, 2020/05
Tanaka, Kazuya; Kozai, Naofumi; Yamasaki, Shinya*; Onuki, Toshihiko; Kaplan, D. I.*; Grambow, B.
Applied Clay Science, 182, p.105282_1 - 105282_8, 2019/12
In this study, Ni-Zn layered hydroxide salt (LHS) was used for adsorption experiments of ReO, as a surrogate of TcO, in aqueous solutions with various initial Re and sodium salt concentrations. The maximum adsorption amount of Re was estimated at 127.7 mg/g (6.86 10 eq/g) by fitting adsorption isotherm of ReO to Langmuir plot. The adsorption of ReO at neutral pH was a reversible process by anion exchange, and decreased with increasing Cl, NO and SO in solution. EXAFS analysis indicated that ReO was adsorbed as an outer-sphere complex on Ni-Zn LHS. The Ni-Zn LHS is a more robust adsorbent for ReO than the Mg-Al LDH in terms of solution pH and tolerance to competing anions, and may be an effective alternative to the traditional and more limited method of removing aqueous TcO by reductive precipitation.
Kato, Tomoaki*; Yu, Q.*; Tanaka, Kazuya; Kozai, Naofumi; Saito, Takumi*; Onuki, Toshihiko
Journal of Environmental Sciences, 86, p.78 - 86, 2019/12
This paper investigated the fate of the dissolved permanganate in aqueous solution after contact with bacterial cells and metal accumulation during precipitation of Mn oxides. When Mn(VII) was contacted with bacterial cells, cells were damaged and Mn(VII) was reduced by cells to lower valence and precipitated as Mn oxides (biomass Mn oxides). When Co ions were present, Co was incorporated into Mn oxides as Co. These results suggest that Mn(VII) can be used to remove metal ions when introduced to wastewater as disinfectant.
Onuki, Toshihiko*; Sakamoto, Fuminori; Kozai, Naofumi; Yamasaki, Shinya*; Sasaki, Yoshito; Niizato, Tadafumi
Journal of Nuclear Science and Technology, 56(9-10), p.814 - 821, 2019/09
We used the spent mushroom substrata (SMSs) which are a kind of by-product after growing edible mushrooms for the investigation of radioactive Cs mobility in litter zone in a forest of Fukushima prefecture, Japan. The powder SMS was filled in a plastic net bag of 0.350.55 m, then was placed in a forest for 6 months under three kinds of different conditions without treatment (No treatment), covered with wooden box (With box), and with zeolite placed on upper position of ground surface (With zeolite). We determined the ratio of radioactivity (TF) in the SMS to that of the soil and litter beneath the SMS bags. TFs of "No treatment" and of "With zeolite" were determined between 0.01 and 0.05 for 6 months. On the other hand, TFs of "With box" were lower by one order at 2 and 4 months than those of "No treatment" and of "With zeolite", and nearly the same values as TFs of "No treatment" and "With zeolite" at 6 months. These results clearly indicate that radioactive Cs accumulates in SMS mainly by throughfall. In addition, for a period of several months, fungi contribute to the accumulation of radioactive Cs in the litter zone, even though radioactive Cs was tightly associated with the soil.
Onuki, Toshihiko; Sakamoto, Fuminori; Kozai, Naofumi; Namba, Kenji*; Neda, Hitoshi*; Sasaki, Yoshito; Niizato, Tadafumi; Watanabe, Naoko*; Kozaki, Tamotsu*
Environmental Science; Processes & Impacts, 21(7), p.1164 - 1173, 2019/07
The fate of radioactive Cs deposited after the Fukushima nuclear power plant accident and its associated radiological impacts are largely dependent on its mobility from surface soils to forest ecosystems. We measured the accumulation of radioactive Cs in the fruit bodies of wild fungi in the forest at Iidate, Fukushima, Japan. The transfer factors (TFs) of radioactive Cs from soil to the fruit bodies of wild fungi were between 10 to 10, a range similar to those reported for the fruit bodies collected in Europe after the Chernobyl accident and in parts of Japan contaminated by nuclear bomb test fallout. Comparison of the TFs of the wild mushroom and that of the fungal hyphae of 704 stock strains grown on agar medium containing nutrients and radioactive Cs showed that the TFs of wild mushroom were lower. TF was less than 0.1 after addition of the minerals zeolite, vermiculite, phlogopite, smectite, or illite of 1% weight to the agar medium. These results indicate that the presence of minerals decrease Cs uptake by fungi grown in the agar medium.
Liu, J.; Dotsuta, Yuma; Kitagaki, Toru; Kozai, Naofumi; Yamaji, Keiko*; Onuki, Toshihiko
Proceedings of International Topical Workshop on Fukushima Decommissioning Research (FDR 2019) (Internet), 2 Pages, 2019/05
To decommission the Fukushima Daiichi Nuclear Power Plant (FDNPP), it is necessary to estimate the current status of fuel debris and predicate the possible change under various condition. Some microorganisms may enter the plant due to the seawater injection after accident and future defueling activity. In this study, microbial influence on fuel debris under aerobic condition was experimentally investigated. By culturing some bacteria in the presence of simulant fuel debris in liquid medium, the microbial degradation of fuel debris was observed.
Tanaka, Kazuya; Kozai, Naofumi; Onuki, Toshihiko; Grambow, B.
Journal of Porous Materials, 26(2), p.505 - 511, 2019/04
In this study, we utilized X-ray absorption fine structure spectroscopy to clarify the coordination structure of Re in Mg-Al LDH as a surrogate of Tc. Adsorption experiments of ReO on calcined and uncalcined Mg-Al LDHs were conducted in aqueous solutions with different concentrations of NaCl, NaNO, and NaSO. Calcined Mg-Al LDH showed much higher adsorption than uncalcined one. The adsorption of ReO was reversible, and decreased with increasing concentration of competing anions like Cl, NO, or SO. Analysis of Re L-edge extended X-ray absorption fine structure indicated that ReO was adsorbed as an outer-sphere complex on Mg-Al LDH. The observed Re adsorption-desorption behavior, which was sensitive to the presence of competing anions, was consistent with the formation of outer sphere-complex.
Haruma, Toshikatsu*; Yamaji, Keiko*; Ogawa, kazuyoshi*; Masuya, Hayato*; Sekine, Yurina; Kozai, Naofumi
PLOS ONE (Internet), 14(2), p.e0212644_1 - e0212644_16, 2019/02
Miscanthus sinensis Andersson is a pioneer plant species that grows naturally at mining sites. can detoxify aluminium (Al) by producing phytosiderophores. Root-endophytic Chaetomium cupreum, which produces microbial siderophores, enhances Al tolerance in M. sinensis. We identified the siderophore produced by C. cupreum as oosporein. It was revealed that oosporein could detoxify Al. Inoculation test of C. cupreum onto M. sinensis in acidic mine soil showed that C. cupreum promoted seedling growth, and enhanced Al tolerance.
Yu, Q.*; Tanaka, Kazuya; Kozai, Naofumi; Sakamoto, Fuminori; Tani, Yukinori*; Onuki, Toshihiko
ACS Earth and Space Chemistry (Internet), 2(8), p.797 - 810, 2018/08
Most of Mn oxides are biogenic and known to adsorb cesium (Cs) on the surface. This study investigated structural transformation of biogenic birnessite by accommodating commonly occurring natural heavy metals (Zn, Ni) during the formation of Mn oxides and the influence of those metals on the adsorption behavior of Cs on Mn oxides. It was found that the presence of heavy metals during bio-oxidation of Mn(II), followed by exposure to a low pH aqueous solution, increased the number of available layer vacancies, which consequently increased the adsorption capacity of Cs in the final product birnessite.
Sekine, Yurina; Kim, S. B.*; Zhang, Y.*; Bandodkar, A. J.*; Xu, S.*; Choi, J.*; Irie, Masahiro*; Ray, T. R.*; Kohli, P.*; Kozai, Naofumi; et al.
Lab on a Chip, 18(15), p.2178 - 2186, 2018/08
The rich composition of solutes and metabolites in sweat and its relative ease of collection upon excretion from skin pores make this class of biofluid an attractive candidate for point of care analysis. Here, we present a complementary approach that exploits fluorometric sensing modalities integrated into a soft, skin-interfaced microfluidic system which, when paired with a simple smartphone-based imaging module, allows for in-situ measurement of important biomarkers in sweat. A network array of microchannels and a collection of microreservoirs pre-filled with fluorescent probes that selectively react with target analytes in sweat (e.g. probes), enable quantitative, rapid analysis. Field studies on human subjects demonstrate the ability to measure the concentrations of chloride, sodium and zinc in sweat, with accuracy that matches that of conventional laboratory techniques.
Tokunaga, Kohei; Kozai, Naofumi; Takahashi, Yoshio*
Journal of Hazardous Materials, 359, p.307 - 315, 2018/07
In the present study, we looked at the removal efficiency of Sr by using barite (BaSO) under various experimental conditions to develop techniques for the direct removal of Sr from seawater. The uptake of Sr by barite was found to be dependent on pH, saturation state, and [Ba]/[SO] ratio in initial aqueous solution, showing that most of the aqueous Sr can be removed from the aqueous solution by adjusting these parameters. However, the effects of ionic strength and competitive ions were negligible, suggesting the effectiveness of its application to removal of Sr from seawater. Batch experiments were also conducted in a seawater system, and a rather high removal efficiency of Sr from seawater (more than 90%) was achieved. Considering its high removal and retention efficiency of Sr in seawater systems, barite is a reliable material for the removal of Sr from seawater.
Kozai, Naofumi; Sakamoto, Fuminori; Tanaka, Kazuya; Onuki, Toshihiko; Sato, Takahiro*; Kamiya, Tomihiro*; Grambow, B.
Chemosphere, 196, p.135 - 144, 2018/04
Transformation of heavy elements by microbes such as bacteria and fungi has been an intense research subject; however, little is known about that of protozoa. This study investigated interaction of a representative protozoa, , with heavy elements (Eu(III), Pb(II), U(VI)). Non-destructive elemental analysis by micro-PIXE hardly detected those elements on living cells after sorption experiments but clearly detected on the cells that were killed with a fixative beforehand. Chromatographic analysis of aquatic species of those heavy elements after the sorption experiments revealed a fraction of those elements bound to a glycoprotein dissolved from the cell surface of living cells to form soluble pseudocolloid. These findings suggest that complexation of heavy elements with the dissolved surface glycoprotein reduced the sorption of those heavy elements on living cells.
Yu, Q.*; Onuki, Toshihiko*; Kozai, Naofumi; Sakamoto, Fuminori; Tanaka, Kazuya; Sasaki, Keiko*
Chemical Geology, 470, p.141 - 151, 2017/10
In this work, the Cs retention onto two types of Mn oxide was investigated. We found that Todorokite has sorption sites with a higher selectivity for Cs than birnessite. When the initial Cs concentration was 10 mol/L for the sorption experiments, approximately 34% of the sorbed Cs was residual in the todorokite after the extraction using 1 M NaCl and NHCl; this value was much higher than the results for the Cs-sorbed birnessite. These results strongly suggest that todorokite contributes to the fixation of radioactive Cs in soils.
Onuki, Toshihiko; Kozai, Naofumi; Sakamoto, Fuminori; Utsunomiya, Satoshi*; Kato, Kenji*
Chemistry Letters, 46(5), p.771 - 774, 2017/05
The sorption behavior of Np(V) by the microbe consortia and by a single pure culture of Fe reducing bacterium was studied at pH between 3 and 7 in resting cell conditions. The sorption of Np(V) by the Fe reducing bacterium obtained in the inert condition and by the consortia in aerated condition were higher than by the Fe reducing bacterium in aerobic condition at pH below 5, strongly suggesting presence of other mechanism than the adsorption on microbial cell surface, i.e. reduction to Np(IV).
Sekine, Yurina; Motokawa, Ryuhei; Kozai, Naofumi; Onuki, Toshihiko; Matsumura, Daiju; Tsuji, Takuya; Kawasaki, Riku*; Akiyoshi, Kazunari*
Scientific Reports (Internet), 7(1), p.2064_1 - 2064_8, 2017/05
A calcium (Ca)-deficient hydroxyapatite was investigated for its potential to remove Sr from environmentally relevant water. We conducted sorption tests on solutions having Mg and Ca as competing cations at the Sr concentration of 0.05 mmol/L. The Ca-deficient hydroxyapatite maintained its high Sr sorption ratio: the sorption ratio was above 80% in the presence of Mg and Ca in the concentrations between 0.1 to 1.0 mmol/L, whereas stoichiometric hydroxyapatite showed a lower ratio even in the presence of small amounts of Mg and Ca. The bonding states of Sr onto the Ca-deficient hydroxyapatite were evaluated by extended X-ray absorption fine structure measurements. The results indicated that there are specific sorption sites in Ca-deficient hydroxyapatite where Sr could be stably and preferentially immobilized.
Yamasaki, Shinya*; Tanaka, Kazuya; Kozai, Naofumi; Onuki, Toshihiko
Applied Geochemistry, 78, p.279 - 286, 2017/03
This study examined the rate constant for the U(VI) reduction process by three flavin analogues, which are redox-active biomolecules secreted from anaerobic bacteria, to elucidate their substituent group effect on the U(VI) reduction rate by electrochemical methods. The formation of the U(IV) was monitored by UV-vis spectrometry in the presence of the flavins. The rate constant for the U(VI) reduction by the flavins was determined. The apparent reduction potential of U(VI) increased about 0.2 V in the presence of the mediators, which strongly suggests that the biological electron mediator makes the U(VI) reduction possible even under more oxidative conditions.
Onuki, Toshihiko; Aiba, Yukitoshi*; Sakamoto, Fuminori; Kozai, Naofumi; Niizato, Tadafumi; Sasaki, Yoshito
Scientific Reports (Internet), 6, p.29866_1 - 29866_6, 2016/07
We here first report the direct accumulation pathway of radioactive Cs from contaminated wood logs to the fruit-bodies of shiitake mushrooms through the basal portion of the stipe by using spectroscopy, autoradiography, and X-ray micro CT techniques.
Yu, Q.; Onuki, Toshihiko; Tanaka, Kazuya; Kozai, Naofumi; Yamasaki, Shinya*; Sakamoto, Fuminori; Tani, Yukinori*
Geochimica et Cosmochimica Acta, 174, p.1 - 12, 2016/02
Although microorganisms possess high sorption capability for lanthanides (Lns), their biological response affecting Lns migration is unclear. We investigated the effects of microbial activity on transformation of Lns by contact of Lns with Aeremonium strictum under metabolically active condition with Mn(II). A biomolecule that specifically complex to Ce(IV) was found to be released from the fungal cell, facilitating the desorption of Ce(IV) from Mn oxide. This biomolecule was not associated with any other trivalent Lns or Fe, which differed from those non-nuclide-specific organic substances released from resting cells, as reported previously.