Researchers Database

KUNISUE, Tatsuya

    Center for Marine Environmental Studies Professor
Last Updated :2020/10/13

Researcher Information

J-Global ID

Research Interests

  • 機器分析化学   環境化学   

Research Areas

  • Environmental science/Agricultural science / Environmental effects of chemicals

Academic & Professional Experience

  • 2015/04 - Today  Ehime UniversityCenter for Marine Environmental Studiesバンク長
  • 2014/04 - Today  Ehime UniversityCenter for Marine Environmental Studies教授
  • 2012/04 - 2014/03  Tottori UniversityFaculty of Agriculture教授

Association Memberships

  • American Chemical Society   Society of Environmental Toxicology and Chemistry   JAPAN SOCIETY FOR ENVIRONMENTAL CHEMISTRY   日本内分泌撹乱化学物質学会   Japan Society of Material Cycles and Waste Management   

Published Papers

  • Tatiya Wannomai, Hidenori Matsukami, Natsuyo Uchida, Fumitake Takahashi, Le Huu Tuyen, Pham Hung Viet, Shin Takahashi, Tatsuya Kunisue, Go Suzuki
    Chemosphere 251 126632 - 126632 2020/07 [Peer-reviewed]
     Scientific journal 
    Flame retardants (FRs) from electronic waste (e-waste) are a widespread environmental concern. In our study, in vitro physiologically based extraction tests (PBETs) for FRs were conducted in three different areas where dust remained after processing of e-waste to identify the bioaccessible FRs and quantify their bioaccessibilities of gastrointestinal tract for human as well as to assess the exposure via ingestion of workers in e-waste processing workshops. All 36 FRs were measured and detected in indoor dusts. Among the FRs, the mean concentrations of polybrominated diphenyl ethers (PBDEs) in the floor dust and settled dust were highest, 65,000 ng/g, and 31,000 ng/g, respectively. In contrast, phosphorus containing flame retardants (PFRs) presented the highest mean concentration in the workplace dust samples, 64,000 ng/g. However, the highest bioaccessible concentrations in workplace dust, floor dust, and settled dust were observed for PFRs: 5900, 1600, and 680 ng/g, respectively. This study revealed that the higher bioaccessibility of PFRs versus other compounds was related to the negative correlation between FR concentrations and log KOW (hydrophobicity) values. The fact that hazard indices calculated using measured bioaccessibilities were less than 1 suggested that the non-cancer risk to human health by the FRs exposure via dust ingestion might be low.
  • Akitoshi Goto, Nguyen Minh Tue, Tomohiko Isobe, Shin Takahashi, Shinsuke Tanabe, Tatsuya Kunisue
    Environmental science & technology 54 (9) 5480 - 5488 2020/05 [Peer-reviewed]
     
    Recent screening surveys have shown the presence of unknown halogenated compounds in the marine environment at comparable levels to persistent organic pollutants (POPs). However, their exposure levels and profiles in marine organisms and bioaccumulative potentials remain unclear. The present study performed nontarget/target screening of organohalogen compounds (OHCs) in mussel and sediment samples collected from Hiroshima Bay, Japan, in 2012 and 2018 by using integrated analyses of two-dimensional gas chromatography-high resolution time-of-flight mass spectrometry (GC×GC-HRToFMS) and magnetic sector GC-HRMS. Nontarget analysis by GC×GC-HRToFMS revealed the detection of approximately 60 OHCs including unknown mixed halogenated compounds (UHC-Br3-5Cl) with molecular formulae of C9H6Br3ClO, C9H5Br4ClO, and C9H4Br5ClO in the mussel. Interestingly, UHC-Br3-5Cl concentrations in the mussel samples, which were semi-quantified by GC-HRMS, were comparable to or higher than those of POPs at all the locations surveyed, and their geographical distribution patterns differed from those of other OHCs. These results suggest that UHC-Br3-5Cl are ubiquitous in coastal waters of Hiroshima Bay and derived from a specific source(s). The biota-sediment accumulation factors (BSAFs) of UHC-Br3-5Cl, estimated for a paired sample set of mussel (ng/g lw) and sediment (ng/g TOC), were 1 order of magnitude higher than those for POPs with similar log Kow values, indicating their high bioaccumulative potential.
  • Tanoue Rumi, Margiotta-Casaluci Luigi, Huerta Belinda, Runnalls, Tamsin J, Eguchi Akifumi, Nomiyama Kei, Kunisue Tatsuya, Tanabe Shinsuke, Sumpter John P
    SCIENCE OF THE TOTAL ENVIRONMENT 664 915 - 926 2019/05 [Peer-reviewed]
  • Teruyo Ieda, Shunji Hashimoto, Tomohiko Isobe, Tatsuya Kunisue, Shinsuke Tanabe
    Talanta 194 461 - 468 0039-9140 2019/03 [Peer-reviewed]
     Scientific journal 
    © 2018 Elsevier B.V. We evaluated the possibility of semi-automatic target and non-target screening by comprehensive two-dimensional gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC×GC-HRToFMS) by using estuarine sediment samples. Two-way screening consisting of compound-based (target screening) and data-based (non-target screening) analyses was performed by using two original software programs, including mass-spectral deconvolution software based on non-negative matrix factorization, the NIST Mass Spectral Library, and an in-house accurate mass spectral library with a retention index (RI) for the 1st column. Target screening detected 47 organohalogen compounds, including polychlorinated biphenyls, polybrominated diphenyl ethers and organochlorine pesticides, in the sediment sample. Among about 54,000 peaks detected in the non-target screening, 53.6% showed match factors (MF) of ≥ 700 in an automatic mass spectral library search using the peak-top mass spectra. Both mass error of molecular ions and RI error were calculated automatically for the first-hit compounds in the library search; 0.03% of peaks passed all criteria, namely MF ≥ 700, mass error ≤± 20 ppm, RI error ≤ ± 20, and intensity of molecular ion ≥ 10,000. Two compounds—a phosphorus flame retardant and a brominated phenol—were tentatively identified in the non-target screening process. The advantages of semi-automatic GC×GC-HRToFMS data processing with the two original software programs is its simplicity, high reproducibility, and shortened time for processing a large volume data. The results suggest that an In-source HiRes search—i.e. library matching using accurate mass spectra—is useful and could be applied for non-target screening using high-resolution MS in the future.
  • Joon-Woo Kim, Kwang-Hyeon Chang, Maricar Prudente, Pham Hung Viet, Shin Takahashi, Shinsuke Tanabe, Tatsuya Kunisue, Tomohiko Isobe
    Science of The Total Environment 655 1081 - 1088 0048-9697 2019/03 [Peer-reviewed]
     Scientific journal 
    © 2018 Elsevier B.V. The environmental contamination by benzotriazole ultraviolet stabilizers (BUVSs) has received consider attention due to their long-term and widespread usage in various consumer and industrial products in accordance with solar UV radiation increase. The present study shows the baseline data of BUVSs in human breast milk from several areas in Japan, the Philippines, and Vietnam. Total concentrations of the 8 BUVSs in breast milk ranged from <MDL (method detection limit) to 1100 ng/g lipid wt. in present study. Among the 8 BUVS compounds targeted, the highest concentration of UV-9 was found in breast milk samples collected from Vietnam. The concentrations of BUVSs in human breast milk were significantly higher (p < 0.01) in Vietnam (300 ± 240 ng/g lipid wt.) than in the Philippines (100 ± 130 ng/g lipid wt.) and Japan (28 ± 34 ng/g lipid wt.). The estimated daily intake of BUVSs by infants through breast milk was one or two orders of magnitude lower than the reference dose levels.
  • Nguyen Minh Tue, Takafumi Matsushita, Akitoshi Goto, Takaaki Itai, Kwadwo, Ansong Asante, Samuel Obiri, Saada Mohammed, Shinsuke Tanabe, Tatsuya Kunisue
    Environmental Science and Technology 53 3010 - 3017 2019/02 [Peer-reviewed]
  • Sawako Horai, Yusuke Nakashima, Kanae Nawada, Izumi Watanabe, Tatsuya Kunisue, Shintaro Abe, Fumio Yamada, Robert Sugihara
    Ecological Indicators 91 92 - 104 1470-160X 2018/08 [Peer-reviewed]
     Scientific journal 
    Concentrations of 26 trace elements including essential (Mg, Ca, Cr, V, Mn, Fe, Co, Ni, Cu, Zn, Se, Sr and Mo) and toxic (As, Cd and Pb), were determined in the liver, kidney, brain, hair, muscle, and stomach contents of the small Indian mongooses inhabiting eight areas on three Hawaiian Islands, Oahu, Maui and Hawaii. There were significant differences in concentrations of some metals among the habitats. Cadmium concentrations in mongooses from the macadamia nut orchards on Island of Hawaii were relatively higher than those in populations from other seven areas. Lead concentrations in mongooses from the Ukumehame firing range were significantly higher than those from other areas. Compared to data reported in mongooses from other countries, Pb concentrations in the brain were higher in the animals from Hawaiian islands, but almost similar levels were observed in the liver and kidney. Intriguingly, brain concentrations of Pb in three specimens from the Ukumehame firing range exceeded 3.79 µg g−1 WW, which was the mean cerebral Pb level in rats that caused some toxic symptoms after administration in the previous study. Furthermore, two fetuses exhibited higher brain Pb concentrations than each of their dams. These results prompted us to consider the potential exposure and health effects of Pb derived from firing range operations on the small Indian mongoose and other animal species including human.
  • Jiahua Guo, Shohei Ito, Hoa Thanh Nguyen, Kimika Yamamoto, Rumi Tanoue, Tatsuya Kunisue, Hisato Iwata
    Toxicology and Applied Pharmacology 347 23 - 32 1096-0333 2018/05 [Peer-reviewed]
     Scientific journal 
    Triclosan (TCS), a commonly used antimicrobial compound, has recently been detected in the eggs of wild avian species. Exposure to TCS in rodents is known to interfere with thyroid hormone (TH), disrupt immune responses and cause liver disease. However, no attempt has been made to clarify the effects of TCS in avian species. The aim of this study is therefore to evaluate the toxic effects of in ovo exposure to TCS and explore the molecular mechanism by transcriptome analysis in the embryonic liver of a model avian species, chicken (Gallus gallus). Embryos were treated with graded concentration of TCS (0.1, 1 and 10 μg/g egg) at Hamburger Hamilton Stage (HHS) 1 (1st day), followed by 20 days of incubation to HHS 46. At the administration of 10 μg TCS/g egg, embryo mortality increased from 20% in control to 37% accompanied with 8% attenuation in tarsus length. While liver somatic index (LSI) in TCS treatments was enhanced, statistical difference was only observed at the treatment of 0.1 μg TCS/g egg in females. The up-regulation of several crucial differentially expressed genes (DEGs) in transcriptome analysis suggested that TCS induced xenobiotic metabolism (e.g. CYP2C23a, CYP2C45 and CYP3A37 in males CYP2C45 in females) and activated the thyroid hormone receptor (THR) - mediated downstream signaling (e.g. THRSPB and DIO2 in males THRSPB in females). In females, TCS may further activate the lipogenesis signaling (e.g. ACSL5, ELOVL2) and repress the lipolysis signaling (e.g. ABHD5, ACAT2). A battery of enriched transcription factors in relation to these TCS-induced signaling and phenotypes were found, including activated SREBF1, PPARa, LXRa, and LXRb in males and activated GLI2 in females COUP-TFII was predicted to be suppressed in both genders. Finally, we developed adverse outcome pathways (AOPs) that provide insights into the molecular mechanisms underlying the alteration of phenotypes.
  • Rumi Tanoue, Imari Kume, Yasuo Yamamoto, Kohki Takaguchi, Kei Nomiyama, Shinsuke Tanabe, Tatsuya Kunisue
    Journal of Chromatography A 1539 30 - 40 1873-3778 2018/03 [Peer-reviewed]
     Scientific journal 
    Thyroid hormones (THs), which mainly consist of 3, 3′ 5-triiodo-L-thyronine (T3) and L-thyroxine (T4), play a critical role in regulating biological processes such as growth and metabolism in various animal species. Thus, accurate measurement of T3 and T4, especially physiologically active free (protein-unbound) forms, in serum/plasma is needed for the evaluation of TH homeostasis. However, such high-precision determination of free THs is lacking for non-human species. The present study aimed to develop a highly sensitive and reliable liquid chromatography-tandem mass spectrometry (LC–MS/MS) method for the determination of six free THs in serum/plasma, which is applicable to not only humans but also non-human species. Two different physical separation steps, ultrafiltration (UF) and equilibrium dialysis (ED), were examined to obtain the free TH fraction. Several experimental conditions were carefully optimized and validated for UF or ED using the commercially available bovine serum. As a result, UF at 1100 × g and 37 °C for 30 min with a 30 kDa ultrafiltration device (Centrifree YM-30, Millipore) yielded excellent precision (CV: < 10%). The optimized ED step also yielded high precision (CV: < 10%) and the measurement values were approximately equal to those of UF, but at least 16 h were required to reach equilibrium. Thus, UF combined with LC–MS/MS was finally chosen, in terms of the time needed for the measurement. Acceptable accuracy (recovery: 70%–110%) and intra- and inter-day precision (CV: < 10% and < 12%, respectively) were obtained, when triplicate analyses in three different days were conducted using the bovine serum. The developed analytical method was successfully applied to the determination of free THs in serum/plasma samples of humans, cats, and dogs. Furthermore, comparison with free T4 concentrations measured by a common immunoassay method evidently indicated that the ultrafiltration-LC–MS/MS method developed in this study can increase the specificity and accuracy of TH measurement.
  • Sónia D. Coelho, Tiago Maricoto, M. Ramiro Pastorinho, Takaaki Itai, Tomohiko Isobe, Tatsuya Kunisue, Shinsuke Tanabe, Ana C.A. Sousa, António J.A. Nogueira
    Journal of Geochemical Exploration 183 187 - 190 0375-6742 2017/12 [Peer-reviewed]
     Scientific journal 
    © 2017 Elsevier B.V. Cadmium (Cd) is a non-essential metal widespread in the environment, to which humans are exposed through different routes, being food consumption the most important one. It is considered an endocrine disruptor that is associated with estrogen-dependent diseases with women being particularly susceptible. In order to assess the exposure to this metal through diet intake in premenopausal women, levels of Cd were quantified in 7-days duplicate diet samples provided by 23 women working or studying at University of Aveiro, Portugal. Cd was detected in all analyzed samples with concentrations ranging between 0.007 and 0.21 μg g− 1ww (median: 0.009 μg g− 1ww). The estimated dietary weekly intakes varied from 1.4 to 48 μg kg-bw− 1week− 1(median: 2.3 μg kg-bw− 1week− 1), and 35% of the participants exhibited dietary intakes of Cd higher than the tolerable weekly intake (2.5 μg kg-bw− 1week− 1) set for this metal which suggest health risks for these women.
  • Akitoshi Goto, Nguyen Minh Tue, Masayuki Someya, Tomohiko Isobe, Shin Takahashi, Shinsuke Tanabe, Tatsuya Kunisue
    SCIENCE OF THE TOTAL ENVIRONMENT 599 340 - 347 0048-9697 2017/12 [Peer-reviewed]
     Scientific journal 
    The present study examined the occurrence and potential sources of mono-to octa-brominated dibenzo-p-dioxins/dibenzofurans (Mo-OBDD/Fs) in Tokyo Bay, Japan, using surface sediments and Pb-210-dated sediment cores (covering the period 1895-2000) collected in 2002. The results showed a clear difference in the spatio-temporal trend between PBDFs and PBDDs. The spatial distribution of PBDF concentrations in the surface sediments showed a decreasing trend from the head to the mouth of the bay, which was similar to that of polybrominated diphenyl ethers (PBDEs) reported previously for the same sediment samples. In the sediment cores, PBDF and PBDE concentrations increased drastically after the 1960s and reached the highest levels in the late 1990s. In addition, a significant positive correlation was observed between the concentrations of their predominant congeners, 1,2,3,4,6,7,8-HpBDF and BDE-209. These results indicate that main contamination sources of PBDFs were technical PBDE formulations, especially DecaBDE. In contrast, total PBDDs in the surface sediments were rather uniform in the whole area of the bay. Furthermore, in the sediment cores, PBDD levels showed marginal fluctuation over the past century, with the predominance of 2,7-/2,8-DiBDDs and 1,3,7-/1,3,8-TrBDDs in all the sediment layers. It is noteworthy that these PBDD congeners were also found in the sediment layers corresponding to the pre-industrial era, supporting their natural formation in the coastal environment (C) 2017 Elsevier B.V. All rights reserved.
  • Rumi Tanoue, Luigi Margiotta-Casaluci, Belinda Huerta, Tamsin J. Runnalls, Kei Nomiyama, Tatsuya Kunisue, Shinsuke Tanabe, John P. Sumpter
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 51 (21) 12825 - 12835 0013-936X 2017/11 [Peer-reviewed]
     Scientific journal 
    Recent species-extrapolation approaches to the prediction of the potential effects of pharmaceuticals present in the environment on wild fish are based on the assumption that pharmacokinetics and metabolism in humans and fish are comparable. To test this hypothesis, we exposed fathead minnows to the opiate pro-drug tramadol and examined uptake from the water into the blood and brain and the metabolism of the drug into its main metabolites. We found that plasma concentrations could be predicted reasonably accurately based on the lipophilicity of the drug once the pH of the water was taken into account. The concentrations of the drug and its main metabolites were higher in the brain than in the plasma, and the observed brain and plasma concentration ratios were within the range of values reported in mammalian species. This fish species was able to metabolize the pro-drug tramadol into the highly active metabolite O-desmethyl tramadol and the inactive metabolite N-desmethyl tramadol in a similar manner to that of mammals. However, we found that concentration ratios of O-desmethyl tramadol to tramadol were lower in the fish than values in most humans administered the drug. Our pharmacokinetic data of tramadol in fish help bridge the gap between widely available mammalian pharmacological data and potential effects on aquatic organisms and highlight the importance of understanding drug uptake and metabolism in fish to enable the full implementation of predictive toxicology approaches.
  • Nguyen Minh Tue, Akitoshi Goto, Shin Takahashi, Takaaki Itai, Kwadwo Ansong Asante, Kei Nomiyama, Shinsuke Tanabe, Tatsuya Kunisue
    JOURNAL OF MATERIAL CYCLES AND WASTE MANAGEMENT 19 (4) 1324 - 1332 1438-4957 2017/10 [Peer-reviewed]
     Scientific journal 
    Detailed composition of chlorinated and brominated polycyclic aromatic hydrocarbons (Cl-PAHs and Br-PAHs) generated during informal recycling of e-waste and their toxic relevance are still poorly understood. This study investigated the occurrence of Cl-PAHs and Br-PAHs in surface soil samples from the Agbogbloshie e-waste recycling site (Accra, Ghana) using quantitative gas chromatography-mass spectrometry (GC-MS) and comprehensive two-dimensional GC-time-of-flight mass spectrometry (GC x GC-ToFMS) profiling. The results of GC-MS analysis showed elevated concentrations in open e-waste burning areas (160-220 and 19-46 ng/g dry weight for Cl- and Br-PAHs, respectively) with substantial contribution from unidentified compounds (respectively, more than 36 and 70%, based on the total areas of potential peaks). Cl- and Br-PAHs from e-waste burning had a distinctive composition dominated by ring-ring compounds. Several homologue groups not monitored with GC-MS were found using GC x GC-ToFMS: PAHs with up to 5 Cl or 3Br, mixed halogenated PAHs and chlorinated methylPAHs. The dioxin-like toxic equivalents of the identified Cl-/Br-PAHs in soils, estimated from their in vitro AhR agonist potencies relative to 2,3,7,8-tetrachlorodibenzo-p-dioxin, were much lower than the range reported for chlorinated and brominated dioxins. However, the toxicity of the unidentified halogenated PAHs remained unclear.
  • Shin Takahashi, Nguyen Minh Tue, Chika Takayanagi, Le Huu Tuyen, Go Suzuki, Hidenori Matsukami, Pham Hung Viet, Tatsuya Kunisue, Shinsuke Tanabe
    JOURNAL OF MATERIAL CYCLES AND WASTE MANAGEMENT 19 (4) 1333 - 1341 1438-4957 2017/10 [Peer-reviewed]
     Scientific journal 
    Floor dusts from Vietnamese end-of-life vehicle (ELV)-processing households were investigated to elucidate the contamination levels and exposure risk of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and dioxin-related compounds (DRCs). The concentrations were in order of PBDEs (260-11,000, median 280 ng/g overall) > PCBs (19-2200, median 140 ng/g) > dioxin-like PCBs (8.8-450, median 22 ng/g) >> polybrominated dibenzo-p-dioxin/dibenzofurans (PBDD/Fs, 2000-28,000, median 8500 pg/g) > polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/Fs, 440-4100, median 1800 pg/g) > MoBPCDD/Fs (1.9-1200, median 250 pg/g). Concentrations of PCBs and DRCs were higher than those reported for Vietnamese urban houses, indicating ELV processing as a significant source of these contaminants. Higher concentrations of PCBs relative to PBDEs suggest the abundance of old electrical capacitors/transformers in ELVs. The PBDD/F and PCDD/F profiles were indicative of DecaBDE-containing materials and combustion sources, respectively. PBDFs, PCDFs and DL-PCBs were the most important dioxin-like toxic equivalent (TEQ) contributors. The estimated PCB and TEQ intake doses from dust ingestion approached or exceeded the reference doses for children living in some ELV-processing households, indicating potential health risk. More comprehensive risk assessment of the exposure to PCBs and DRCs is required for residents of informal ELV recycling sites.
  • Shin-ichi Sakai, Junya Yano, Yasuhiro Hirai, Misuzu Asari, Ritsuki Yanagawa, Takeshi Matsuda, Hideto Yoshida, Tetsuji Yamada, Natsuko Kajiwara, Go Suzuki, Tatsuya Kunisue, Shin Takahashi, Keijiro Tomoda, Joachim Wuttke, Paul Maehlitz, Vera Susanne Rotter, Mario Grosso, Thomas Fruergaard Astrup, Julian Cleary, Gil-Jong Oh, Lili Liu, Jinhui Li, Hwong-wen Ma, Ngo Kim Chi, Stephen Moore
    JOURNAL OF MATERIAL CYCLES AND WASTE MANAGEMENT 19 (4) 1295 - 1313 1438-4957 2017/10 [Peer-reviewed]
     
    Although the 2Rs (reduce and reuse) are considered high-priority approaches, there has not been enough quantitative research on effective 2R management. The purpose of this paper is to provide information obtained through the International Workshop in Kyoto, Japan, on 11-13 November 2015, which included invited experts and researchers in several countries who were in charge of 3R policies, and an additional review of 245 previous studies. It was found that, regarding policy development, the decoupling between environmental pressures and economy growth was recognized as an essential step towards a sustainable society. 3R and resource management policies, including waste prevention, will play a crucial role. Approaches using material/substance flow analyses have become sophisticated enough to describe the fate of resources and/or hazardous substances based on human activity and the environment, including the final sink. Life-cycle assessment has also been developed to evaluate waste prevention activities. Regarding target products for waste prevention, food loss is one of the waste fractions with the highest priority because its countermeasures have significant upstream and downstream effects. Persistent organic pollutants and hazardous compounds should also be taken into account in the situation where recycling activities are globally widespread for the promotion of a material-cycling society.
  • Akitoshi Goto, Nguyen Minh Tue, Masayuki Someya, Tomohiko Isobe, Shin Takahashi, Shinsuke Tanabe, Tatsuya Kunisue
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 51 (20) 11771 - 11779 0013-936X 2017/10 [Peer-reviewed]
     Scientific journal 
    In addition to unintentional formation of polychlorinated (PCDD/Fs), polybrominated (PBDD/Fs), and mixed halogenated (PXDD/Fs) dibenzo-p-dioxins/dibenzofurans during industrial activities, recent studies have shown that several PBDD and PXDD congeners can be produced by marine algal species from the coastal environment. However, multiple exposure status of anthropogenic and naturally derived dioxins in marine organisms remains unclear. The present study examined the occurrence, geographical distribution, and potential sources of PCDD/Fs, PBDD/Fs, and PXDD/Fs using mussels and brown algae collected in 2012 from Seto Inland Sea, Japan. The results showed the widespread occurrence of not only PCDD/Fs but also PBDDs and PXDDs in Seto Inland Sea. The geographical distribution pattern of PBDDs was similar to that of PXDDs, which were obviously different from that of PCDDs and PCDFs, and a significant positive correlation was observed between the levels of their predominant congeners, i.e., 1,3,7-/1,3,8-TrBDDs and DiBMoCDDs. Interestingly, potential precursors of 1,3,7-/1,3,8-TrBDDs and DiBMoCDDs, hydroxylated tetrabrominated diphenyl ethers (6-HO-BDE-47 and 2'-HO-BDE-68) and their mixed halogenated analogue (HO-TrBMoCDE), were also identified in the mussel and brown alga samples collected at the same site, by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC X GCToFMS) analyses. It is noteworthy that residue levels of 1,3,7-/1,3,8-TrBDDs and DiBMoCDDs in the mussel were 30 times higher than those in the brown alga, suggesting the bioaccumulation of these natural dioxins.
  • Kei Nomiyama, Kohki Takaguchi, Hazuki Mizukawa, Yasuko Nagano, Tomoko Oshihoi, Susumu Nakatsu, Tatsuya Kunisue, Shinsuke Tanabe
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 51 (10) 5811 - 5819 0013-936X 2017/05 [Peer-reviewed]
     Scientific journal 
    The adverse effects of elevated polybrominated diphenyl ether (PBDE) levels, reported in the blood of domestic dogs and cats, are considered to be of great concern. However, the tissue distribution of PBDEs and their derivatives in these animals is poorly understood. This study determined the concentrations and profiles of PBDEs, hydroxylated PBDEs (OH-PBDEs), methoxylated PBDEs (MeO-PBDEs), and 2,4,6-tribromophenol (2,4,6-tri-BPh) in the blood, livers, bile, and brains of dogs and cats in Japan. Higher tissue concentrations of PBDEs were found in cats, with the dominant congener being BDE209. BDE207 was also predominant in cat tissues, indicating that BDE207 was formed via BDE209 debromination. BDE47 was the dominant congener in dog bile, implying a species-specific excretory capacity of the liver. OH-PBDE and MeO-PBDE concentrations were several orders of magnitude higher in cat tissues, with the dominant congener being 6OH-BDE47, possibly owing to their intake of naturally occurring MeO-PBDEs in food, MeO-PBDE demethylation in the liver, and lack of UDP-glucuronosyltransferase, UGT1A6. Relatively high concentrations of BDE209, BDE207, 6OH-BDE47, 2'MeO-BDE68, and 2,4,6-tri-BPh were found in cat brains, suggesting a passage through the blood brain barrier. Thus, cats in Japan might be at a high risk from PBDEs and their derivatives, particularly BDE209 and 6OH-BDE47.
  • Ana C. A. Sousa, Sonia D. Coelho, M. Ramiro Pastorinho, Luis Taborda-Barata, Antonio J. A. Nogueira, Tomohiko Isobe, Tatsuya Kunisue, Shin Takahashi, Shinsuke Tanabe
    SCIENCE OF THE TOTAL ENVIRONMENT 574 19 - 23 0048-9697 2017/01 [Peer-reviewed]
     Scientific journal 
    Organotin compounds (OTs) are ubiquitous contaminants with a broad range of applications ranging from biocides and pesticides to catalysts for the production of polyurethane foams and silicones. The deleterious effects of some OTs (particularly tributyltin - TBT) upon wildlife and experimental animals are well documented and include endocrine disruption, immunotoxicity, neurotoxicity, genotoxicity and metabolic dysfunction in which obesity is included. However, virtually no data on the current human exposure levels is available. In order to bridge this gap, we quantified for the first time the levels of OTs in duplicate diet samples from members of the University of Aveiro in Portugal. OTs were detected in 32% of the 28 diet samples analyzed, at relatively low levels. TBT and monobutyltin were detected only in two samples and dibutyltin was detectable in three samples. Dioctyltin was quantified in four samples and monooctyltin in three samples. Phenyltins were below the detection limit in all the diet samples analyzed. Overall, for the vast majority of the samples (89%), the estimated daily intakes (EDI) of organotins through food were much lower than the established tolerable daily intakes (TDI). Hence, for the majority of the participants the risk associated with food ingestion is low. (C) 2016 Elsevier B.V. All rights reserved.
  • Sonia D. Coelho, M. Ramiro Pastorinho, Takaaki Itai, Tomohiko Isobe, Tatsuya Kunisue, Antonio J. A. Nogueira, Shinsuke Tanabe, Ana C. A. Sousa
    SCIENCE OF THE TOTAL ENVIRONMENT 573 603 - 607 0048-9697 2016/12 [Peer-reviewed]
     Scientific journal 
    Lead is a naturally occurring element that with the advent of the industrial era became a serious environmental and public health issue. Leaded gasoline, lead based paints, use of lead in plumbing and water pipes, ceramics with lead-containing glazes and tobacco smoke are potential sources of lead exposure for humans. Despite these multiple sources, food is still considered the most important one for the general non-smoking population. Hence, in the present study, the dietary intake of lead was determined in duplicate diet samples provided by 30 participants working or studying at University of Aveiro, Portugal. Pb was detected in all the analysed samples with values ranging between 0.009 and 0.10 mg kg(-1) ww which correspond to estimated daily intakes between 022 and 3.5 mu g kg-bw(-1) day(-1). Risk estimations disclose that at least 33% and 26.7% of the participants might suffer cardiovascular and nephrotoxic effects, respectively. (C) 2016 Elsevier B.V. All rights reserved.
  • Yutaka TASHIRO, Akitoshi GOTO, Tatsuya KUNISUE, Takuya KURAHASHI, Shinsuke TANABE
    Journal of Environmental Chemistry 126 115 - 122 2016/09 [Peer-reviewed]
  • Tatsuya Kunisue, Shinsuke Tanabe
    Handbook of Environmental Chemistry 49 301 - 334 1867-979X 2016 [Peer-reviewed]
     In book 
    This chapter focuses on the contamination, bioaccumulation, and toxicological effects of dioxins and related compounds (DRCs), such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxinlike polychlorinated biphenyls (DL-PCBs), in Asian developing countries, with a particular emphasis on open dumping sites of municipal waste. A comprehensive investigation of soils has suggested clearly that dumping sites (DS) are potential sources of DRCs, whereas the concentrations of DRCs in soils from urban and agricultural areas in Asian developing countries were comparable to or lower than those in general background soils from developed nations. In India, notably higher concentrations of DRCs were detected in human milk from women residing around DS, compared with those from reference sites (RS) and other Asian developing countries, indicating that the residents around DS ingest greater amounts of DRCs, possibly via the intake of contaminated bovine milk and fish. Elevated concentrations of DRCs were also detected in wild animals inhabiting the Indian DS area, such as crow and pig, and the accumulated DRC profiles suggested direct transfer of these contaminants from contaminated soil. Toxic equivalents (TEQs) of DRCs and the liver to adipose concentration ratios of PCDD/Fs in pigs had statistically significant positive correlations with the levels of hepatic cytochrome P450 (CYP) 1A-like protein, suggesting the induction of CYP1A by DRCs and CYP1A-dependent hepatic sequestration of PCDD/Fs. In addition, decreases in plasma-free thyroxine and immunoglobulin G were observed in pigs from the DS. Thus, DS in developing countries are one of the main challenges for further research due to the long-term effects on environmental quality and human/animal health. The continuous formation of DRCs in DS and their elevated residues detected in breast milk from residents living around such DS warrant effect studies of these contaminants on their offspring. Comprehensive and long-term monitoring programs are urgently needed with proper capacity building in Asian developing countries, to mitigate DRC emission and their risk on ecosystems and human health.
  • Nguyen Minh Tue, Akitoshi Goto, Shin Takahashi, Takaaki Itai, Kwadwo Ansong Asante, Tatsuya Kunisue, Shinsuke Tanabe
    JOURNAL OF HAZARDOUS MATERIALS 302 151 - 157 0304-3894 2016/01 [Peer-reviewed]
     Scientific journal 
    Although complex mixtures of dioxin-related compounds (DRCs) can be released from informal e-waste recycling, DRC contamination in African e-waste recycling sites has not been investigated. This study examined the concentrations of DRCs including chlorinated, brominated, mixed halogenated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs, PBDD/Fs, PXDD/Fs) and dioxin-like polychlorinated biphenyls (DLPCBs) in surface soil samples from the Agbogbloshie e-waste recycling site in Ghana. PCDD/F and PBDD/F concentrations in open burning areas (18-520 and 83-3800 ng/g dry, respectively) were among the highest reported in soils from informal e-waste sites. The concentrations of PCDFs and PBDFs were higher than those of the respective dibenzo-p-dioxins, suggesting combustion and PBDE-containing plastics as principal sources. PXDFs were found as more abundant than PCDFs, and higher brominated analogues occurred at higher concentrations. The median total WHO toxic equivalent (TEOJ concentration in open burning soils was 7 times higher than the U.S. action level (1000 pg/g), with TEQ contributors in the order of PBDFs >> PCDD/Fs > PXDFs. DRC emission to soils over the e-waste site as of 2010 was estimated, from surface soil lightness based on the correlations between concentrations and lightness, at 200 mg (95% confidence interval 93-540 mg) WHO-TEQ over three years. People living in Agbogbloshie are potentially exposed to high levels of not only chlorinated but also brominated DRCs, and human health implications need to be assessed in future studies. (C) 2015 Elsevier B.V. All rights reserved.
  • Hazuki Mizukawa, Kei Nomiyama, Susumu Nakatsu, Hisato Iwata, Jean Yoo, Akira Kubota, Miyuki Yamamoto, Mayumi Ishizuka, Yoshinori Ikenaka, Shouta M. M. Nakayama, Tatsuya Kunisue, Shinsuke Tanabe
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 50 (1) 444 - 452 0013-936X 2016/01 [Peer-reviewed]
     Scientific journal 
    There are growing concerns about the increase in hyperthyroidism in pet cats due to exposure to organo-halogen contaminants and their hydroxylated metabolites. This study investigated the blood contaminants polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) and their hydroxylated and methoxylated derivatives (OH-PCBs, OH-PBDEs, and MeO-PBDEs), in pet dogs and cats. We also measured the residue levels of these compounds in commercially available pet foods. Chemical analyses of PCBs and OH-PCBs showed that the OH-PCB levels were 1 to 2 orders of magnitude lower in cat and dog food products than in their blood, suggesting that the origin of OH-PCBs in pet dogs and cats is PCBs ingested with their food. The major congeners of OH-/MeO-PBDEs identified in both pet food products and blood were natural products (60H-/MeO-BDE47 and 2'OH-/MeO-BDE68) from marine organisms. In particular, higher concentrations of 60H-BDE47 than 2'OH-BDE68 and two MeO-PBDE congeners were observed in the cat blood, although MeO-BDEs were dominant in cat foods, suggesting the efficient biotransformation of 60H-BDE47 from 6MeO-BDE47 in cats. We performed in vitro demethylation experiments to confirm the biotransformation of MeO-PBDEs to OH-PBDEs using liver microsomes. The results showed that 6MeO-BDE47 and 2'MeO-BDE68 were demethylated to 60H-BDE47 and 2'OH-BDE68 in both animals, whereas no hydroxylated metabolite from BDE47 was detected. The present study suggests that pet cats are exposed to MeO-PBDEs through cat food products containing fish flavors and that the OH-PBDEs in cat blood are derived from the CYP-dependent demethylation of naturally occurring MeO-PBDE congeners, not from the hydroxylation of PBDEs.
  • Coelho, S{\'o}nia D, Sousa, Ana CA, Isobe, Tomohiko, Kim, Joon-Woo, Kunisue, Tatsuya, Nogueira, Ant{\'o}nio JA, Tanabe, Shinsuke
    Science of The Total Environment 569 442 - 449 0048-9697 2016 [Peer-reviewed]
     Scientific journal
  • Coelho, S{\'o}nia D, Sousa, Ana CA, Isobe, Tomohiko, Kunisue, Tatsuya, Nogueira, Ant{\'o}nio JA, Tanabe, Shinsuke
    Chemosphere 160 89 - 94 0045-6535 2016 [Peer-reviewed]
     Scientific journal
  • Annamalai Subramanian, Tatsuya Kunisue, Shinsuke Tanabe
    CHEMOSPHERE 137 122 - 134 0045-6535 2015/10 [Peer-reviewed]
     
    Our group of scientists at the Center for Marine Environmental Studies (CMES), Ehime University, Japan has been carrying-out studies in India from the 1980s on chemicals contamination. Due to its agrarian economy, use of fossil fuels, industries, growing population and urbanization, chemicals such as pesticides, dioxins and related chemicals (DRCs), brominated flame retardants (BFRs), heavy metals, and polyaromatic hydrocarbons (PAHs) are widely spread in India. We have published a review (Subramanian and Tanabe, 2007) covering papers published until 2005, on India. A decade had passed and this is the time to provide an update of the spatial and temporal changes during this period and hence this review. At many instances organochlorines such as DDTs and HCHs showed decreasing trends even though they are still at considerable levels. Novel chemicals such as PCDDs/Fs are seen at municipal solid waste dumping sites of India at levels equivalent to similar locations of the developed world. In the e-waste processing sites in India, especially the informal ones, apart from PCDDs/Fs, some brominated flame retardants (BFRs) and heavy metals were present as contaminants. Metro cities of India showed location specific contamination by HCHs, DDTs, PCDDs/Fs, BFRs, PAHs, etc. Coastal regions of India seem to be still unpolluted when compared to the nearby inland locations. This review is concerned mainly with the chemicals that we (CMES) have been evaluating in India in the past three decades. We suggest the importance of further studies, future directions for policy decisions and also for implementing control measures. (C) 2015 Elsevier Ltd. All rights reserved.
  • Rumi Tanoue, Kei Nomiyama, Haruna Nakamura, Joon-Woo Kim, Tomohiko Isobe, Ryota Shinohara, Tatsuya Kunisue, Shinsuke Tanabe
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 49 (19) 11649 - 11658 0013-936X 2015/10 [Peer-reviewed]
     Scientific journal 
    A fish plasma model (FPM) has been proposed as a screening technique to prioritize potential hazardous pharmaceuticals to wild fish. However, this approach does not account for inter- or intraspecies variability of pharmacokinetic and pharmacodynamic parameters. The present study elucidated the uptake potency (from ambient water), tissue distribution, and biological risk of 20 pharmaceutical and personal care product (PPCP) residues in wild cyprinoid fish inhabiting treated-wastewater-impacted streams. In order to clarify the uncertainty of the FPM for PPCPs, we compared the plasma bioaccumulation factor in the field (BAF(plasma) = measured fish plasma/ambient water concentration ratio) with the predicted plasma bioconcentration factor (BCFplasma = fish plasma predicted by use of theoretical partition coefficients/ambient water concentration ratio) in the actual environment. As a result, the measured maximum BAF(plasma) of inflammatory agents was up to 17 times higher than theoretical BCFplasma values, leading to possible underestimation of toxicological risk on wild fish. When the tissue blood partition coefficients (tissue/blood concentration ratios) of PPCPs were estimated, higher transportability into tissues, especially the brain, was found for psychotropic agents, but brain/plasma ratios widely varied among individual fish (up to 28-fold). In the present study, we provide a valuable data set on the intraspecies variability of PPCP pharmacokinetics, and our results emphasize the importance of determining PPCP concentrations in possible target organs as well as in the blood to assess the risk of PPCPs on wild fish.
  • Hazuki Mizukawa, Kei Nomiyama, Tatsuya Kunisue, Michio X. Watanabe, Annamalai Subramanian, Hisato Iwata, Mayumi Ishizuka, Shinsuke Tanabe
    ENVIRONMENTAL RESEARCH 138 255 - 263 0013-9351 2015/04 [Peer-reviewed]
     Scientific journal 
    The concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and their hydroxylated metabolites (OH-PCBs and OH-PBDEs) were measured in the blood of Eurasian wild pigs (Sus scrofa) from a municipal waste open dumping site (DS) and a reference site (RS) in South India. We showed that contamination with OH-PCBs was higher in female pigs from the DS than in all other adult pigs. The highest OH-PCB concentrations were found in piglets from the DS. Moreover, the hepatic expression levels of CYP1A and CYP2B were higher in piglets than in their dam, implying metabolism of PCBs by cytochrome P450 (CYP) enzymes. The OH-PCB congener profiles differed according to sex and collection sites, possibly because of variations in the expression levels of phase I and phase II enzymes among individual pigs, differences in the exposure sources, and maternal transfer of parent PCBs. The hepatic CYP1A expression levels were positively correlated with the blood concentrations of 4OH-CB107, 4OH-CB162, and 4OH-CB187, implying CYP1A-dependent formation of these OH-PCBs in the pig liver. We found no significant correlations between the blood concentrations of OH-PCBs and thyroid hormones (THs); however, the thyroxin (T-4) levels were lower in pigs from the DS than in pigs from the RS. Our limited dataset suggest that induced CYP enzymes accelerate the metabolism of xenobiotics and endogenous molecules in pigs. Thus, besides parental compounds, the risk of hydroxylated metabolites entering wildlife and humans living in and around municipal open waste dumping sites should be considered. (C) 2015 Elsevier Inc. All rights reserved.
  • Daisuke Imaeda, Kei Nomiyama, Tatsuya Kunisue, Hisato Iwata, Oyuna Tsydenova, Masao Amano, Evgeny A. Petrov, Valeriy B. Batoev, Shinsuke Tanabe
    CHEMOSPHERE 114 1 - 8 0045-6535 2014/11 [Peer-reviewed]
     Scientific journal 
    We have previously demonstrated that Baikal seals (Pusa sibirica) are still being exposed to polychlorinated biphenyls (PCBs), and the population is at risk. In the present study, we measured the residue levels of PCBs and their hydroxylated metabolites (OH-PCBs) in the blood of Baikal seals and assessed the impact of OH-PCBs on the thyroid function. Blood concentrations of PCBs and OH-PCBs were in the range of 2.8130 ng g(-1) wet wt. and 0.71-4.6 ng g(-1) wet wt., respectively. Concentrations of higher-chlorinated OH-PCBs (hexa- to octa-PCBs) were more than 70% to total OH-PCB concentrations, indicating Baikal seals are mostly risked by higher-chlorinated OH-PCBs. High levels of 4OH-CB146 and 4OH-CB187 and low levels of 4OH-CB107/4'OH-CB108 found in Baikal seals were different from those in other phocidae species, suggesting the unique drug-metabolizing enzyme activities and/or contamination sources in this species. Concentrations of some OH-PCBs in males were significantly higher than those in females. These results suggest that these isomers may be preferentially transferred from mother to pup via cord blood. However, concentrations of almost all the isomers were not significantly correlated with the levels of blood total T3 and T4, implying less impact of PCB-related compounds on the thyroid hormone circulation. (C) 2014 Elsevier Ltd. All rights reserved.
  • Kei Nomiyama, Shusaku Hirakawa, Akifumi Eguch, Chika Kanbara, Daisuke Imaeda, Jean Yoo, Tatsuya Kunisue, Eun-Young Kim, Hisato Iwata, Shinsuke Tanabe
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 48 (22) 13530 - 13539 0013-936X 2014/11 [Peer-reviewed]
     Scientific journal 
    We have previously reported that high accumulation of dioxins and related compounds induced cytochrome P450 (CYP 1s) isozymes in the liver of wild Baikal seals, implying the enhanced hydroxylation of polychlorinated biphenyls (PCBs). The present study attempted to elucidate the residue concentrations and patterns of PCBs and hydroxylated PCBs (OH-PCBs) in the livers of Baikal seals. The hepatic residue concentrations were used to assess the potential effects of PCBs and OH-PCBs in combination with the analyses of serum thyroid hormones, hepatic mRNA levels, and biochemical markers. The hepatic expression levels of CYP1 genes were positively correlated with the concentration of each OH-PCB congener. This suggests chronic induction of these CYP1 isozymes by exposure to PCBs and hydroxylation of PCBs induced by CYP 1s. Hepatic mRNA expression monitoring using a custom microarray showed that chronic exposure to PCBs and their metabolites alters the gene expression levels related to oxidative stress, iron ion homeostasis, and inflammatory responses. In addition, the concentrations of OH-PCBs were negatively correlated with l-thyroxine (T-4) levels and the ratios of 3,3',5-triiodo-l-thyronine (T-3)/reverse 3,3',5'-triiodo-l-thyroninee (rT(3)). These observations imply that Baikal seals contaminated with high levels of OH-PCBs may undergo the disruption of mechanisms related to the formation (or metabolism) of T-3 and T-4 in the liver.
  • Satoko Niimi, Mai Imoto, Tatsuya Kunisue, Michio X. Watanabe, Eun-Young Kim, Kei Nakayama, Genta Yasunaga, Yoshihiro Fujise, Shinsuke Tanabe, Hisato Iwata
    ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY 108 95 - 105 0147-6513 2014/10 [Peer-reviewed]
     Scientific journal 
    Hepatic concentrations of persistent organochlorines (OCs) were determined in the common minke whale (Balaenoptera acutorostrata) from the North Pacific. To investigate the effects of OCs on the transcriptome in the minke whale, the present study constructed a hepatic oligo array of this species where 985 unique oligonucleotides were spotted and further analyzed the relationship between the OC levels and gene expression profiles of liver tissues. The stepwise multiple linear regression analysis identified 32 genes that correlated with hepatic OC levels. The mRNA expression levels of seven cytochrome P450 (CYP) genes, CYP1A1, 1A2, 208, 2E1, 3A72, 4A35, and 4V6 showed no clear correlations with the concentration of each OC, suggesting that the accumulated OCs in the liver did not reach levels that could alter CYP expression. Among the genes screened by the custom oligo array analysis, hepatic mRNA expression levels of 16 genes were further measured using quantitative real-time reverse transcription polymerase chain reaction. The mRNA levels of vitamin D-binding protein (DBP) were negatively correlated with non-ortho coplanar polychlorinated biphenyl (PCB) levels. Androgen receptor-associated coregulator 70 (ARA70) expression levels showed a significant positive correlation with concentrations of non-ortho coplanar PCB169. These correlations suggest that coplanar PCB-reduced DBP expression could suppress vitamin D receptor-mediated signaling cascades in peripheral tissues. Alternatively, the suppression of vitamin D receptor signaling cascade could be enhanced through competition with the androgen receptor signaling pathway for ARA70. In addition, a negative correlation between kynureninase and PCB169 levels was also observed, which suggest an enhanced accumulation of an endogenous aryl hydrocarbon receptor agonist, kynurenine in the minke whale population. Further studies are necessary to translate the changes in the transcriptome to toxicological outcomes including the disruption of the nervous and immune systems. (C) 2014 Elsevier Inc. All rights reserved.
  • Akifumi Eguchi, Tatsuya Kunisue, Qian Wu, Pham Thi Kim Trang, Pham Hung Viet, Kurunthachalam Kannan, Shinsuke Tanabe
    ARCHIVES OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY 67 (1) 29 - 41 0090-4341 2014/07 [Peer-reviewed]
     Scientific journal 
    Perchlorate (ClO4 (-)) and thiocyanate (SCN-) interfere with iodide (I-) uptake by the sodium/iodide symporter, and thereby these anions may affect the production of thyroid hormones (THs) in the thyroid gland. Although human exposure to perchlorate and thiocyanate has been studied in the United States and Europe, few investigations have been performed in Asian countries. In this study, we determined concentrations of perchlorate, thiocyanate, and iodide in 131 serum samples collected from 2 locations in Northern Vietnam, Bui Dau (BD; electrical and electronic waste [e-waste] recycling site) and Doung Quang (DQ; rural site) and examined the association between serum levels of these anions with levels of THs. The median concentrations of perchlorate, thiocyanate, and iodide detected in the serum of Vietnamese subjects were 0.104, 2020, and 3.11 ng mL(-1), respectively. Perchlorate levels were significantly greater in serum of the BD population (median 0.116 ng mL(-1)) than those in the DQ population (median 0.086 ng mL(-1)), which indicated greater exposure from e-waste recycling operations by the former. Serum concentrations of thiocyanate were not significantly different between the BD and DQ populations, but increased levels of this anion were observed among smokers. Iodide was a significant positive predictor of serum levels of FT3 and TT3 and a significant negative predictor of thyroid-stimulating hormone in males. When the association between serum levels of perchlorate or thiocyanate and THs was assessed using a stepwise multiple linear regression model, no significant correlations were found. In addition to greater concentrations of perchlorate detected in the e-waste recycling population, however, given that lower concentrations of iodide were observed in the serum of Vietnamese females, detailed risk assessments on TH homeostasis for females inhabiting e-waste recycling sites, especially for pregnant women and their neonates, are required.
  • Michio X. Watanabe, Tatsuya Kunisue, Norifumi Ueda, Masato Nose, Shinsuke Tanabe, Hisato Iwata
    ENVIRONMENT INTERNATIONAL 53 53 - 61 0160-4120 2013/03 [Peer-reviewed]
     Scientific journal 
    Concentrations of persistent organochlorine compounds (OCs) including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) in the liver and adipose tissue of Japanese cadavers were measured, and their toxicokinetics were examined in association with hepatic cytochrome P450 (CYP) 1A protein expression levels. Total 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) were 66 +/- 74 and 65 +/- 57 pg/g lipid weight (mean +/- S.D.) in the liver and adipose tissue, respectively. Total PCBs (sum of 62 congeners targeted), p,p'-dichlorodiphenyl-dichloroethylene (p,p'-DDE) and beta-hexachlorocyclohexane (beta-HCH) were detected at concentrations over 1 mu g/g lipid in both tissues of some specimens. For most of the dioxin-like congeners, total PCBs, p,p'-DDE, oxychlordane, alpha- and beta-HCH, hexachlorobenzene (HCB), and tris(4-chlorophenyl)methane (TCPMe), age-dependent increases in concentrations were found in the adipose tissue of males. No such age-dependent trend was observed in the liver, suggesting that there are different mechanisms underlying the hepatic concentrations of OCs. Immunoblot analyses indicated detectable expression of hepatic CYP1A2 protein, whereas no CYP1A1 protein was detected. The CYP1A2 expression levels were positively correlated with concentrations (on wet weight basis) of 2,3,4,7,8-P5CDF, the dominant TEQ-contributed congeners in the liver, indicating the induction of this CYP. Hepatic CYP1A2 protein levels were strongly correlated with the liver to adipose concentration (L/A) ratios of PCDD/F congeners with more than 5 chlorine atoms. Together with higher concentrations of the congeners in the liver than in the adipose tissue, the observation on L/A ratios of highly chlorinated PCDD/Fs suggests that induced hepatic CYP1A2 protein is involved in their sequestration in this human population, as observed in model animals (rodents). Nonetheless, the magnitude of hepatic sequestration (L/A ratio) of PCDD/Fs in this human population was lower than in other mammals and birds, reported previously. This study emphasizes the fact that toxicokinetics of some OCs can be affected at least partly by CYP1A2 protein levels in humans. For the extrapolation of their toxicokinetics from model animals to humans, knowledge on the induction and sequestration potencies of CYP1A is necessary. (C) 2013 Elsevier Ltd. All rights reserved.
  • Alexander G. Little, Tatsuya Kunisue, Kurunthachalam Kannan, Frank Seebacher
    BMC BIOLOGY 11 26  1741-7007 2013/03 [Peer-reviewed]
     Scientific journal 
    Background: Thyroid hormone (TH) is best known for its role in development in animals, and for its control of metabolic heat production (thermogenesis) during cold acclimation in mammals. It is unknown whether the regulatory role of TH in thermogenesis is derived in mammals, or whether TH also mediates thermal responses in earlier vertebrates. Ectothermic vertebrates show complex responses to temperature variation, but the mechanisms mediating these are poorly understood. The molecular mechanisms underpinning TH action are very similar across vertebrates, suggesting that TH may also regulate thermal responses in ectotherms. We therefore aimed to determine whether TH regulates thermal acclimation in the zebrafish (Danio rerio). We induced hypothyroidism, followed by supplementation with 3,5-diiodothyronine (T-2) or 3,5,3'-triiodothyronine (T-3) in zebrafish exposed to different chronic temperatures. We measured whole-animal responses (swimming performance and metabolic rates), tissue-specific regulatory enzyme activities, gene expression, and free levels of T-2 and T-3. Results: We found that both T-3 and the lesser-known T-2, regulate thermal acclimation in an ectotherm. To our knowledge, this is the first such study to show this. Hypothyroid treatment impaired performance measures in cold acclimated but not warm acclimated individuals, whereas supplementation with both TH metabolites restored performance. TH could either induce or repress responses, depending on the actual temperature and thermal history of the animal. Conclusions: The low sensitivity to TH at warm temperatures could mean that increasing temperatures (that is, global warming) will reduce the capacity of animals to regulate their physiologies to match demands. We suggest that the properties that underlie the role of TH in thermal acclimation (temperature sensitivity and metabolic control) may have predisposed this hormone for a regulatory role in the evolution of endothermy.
  • Tatsuya Kunisue, Zhen Chen, Germaine M. Buck Louis, Rajeshwari Sundaram, Mary L. Hediger, Liping Sun, Kurunthachalam Kannan
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 46 (8) 4624 - 4632 0013-936X 2012/04 [Peer-reviewed]
     Scientific journal 
    Benzophenone (BP)-type UV filters are widely used in a variety of personal care products for the protection of skin and hair from UV irradiation. Despite the estrogenic potencies of BP derivatives, few studies have examined the occurrence of these compounds in human matrices. Furthermore, associations among exposure to these compounds and estrogen-dependent diseases (such as endometriosis) have not been examined previously. In this study, we determined the concentrations of five BP derivatives, 2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), 2,4-dihydroxybenzophenone (2,4OH-BP), 2,2'-dihydroxy-4-methoxybenzophenone (2,2'OH-4MeO-BP), 2,2',4,4'-tetrahydroxybenzophenone (2,2',4,4'OH-BP), and 4-hydroxybenzophenone (4OH-BP), in urine collected from 625 women in Utah and California, using liquid chromatography (LC)-tandem mass spectrometry (MS/MS). The association of urinary concentrations of BP derivatives with an increase in the odds of a diagnosis of endometriosis was examined in 600 women who underwent laparoscopy/laparotomy (n = 473: operative cohort) or pelvic magnetic resonance imaging (n = 127: population cohort), during 2007-2009. 2OH-4MeO-BP, 2,4OH-BP, and 4OH-BP respectively were detected in 99.0%, 93.3%, and 83.8% of the urine samples analyzed, whereas the detection rates for 2,2',4,4'OH-BP and 2,2'OH-4MeO-BP were below 6.0%. Significant regional differences (higher concentrations in California) and monthly variations (higher concentrations in July and August) were found for urinary concentrations of 2OH-4MeO-BP and 2,4OH-BP. In addition, urinary concentrations of 2OH-4MeO-BP and 2,4OH-BP tended to be higher in more affluent, older, and leaner women. Adjusted odds ratios (ORs) and 95% confidence intervals (CIs) were estimated for the urinary concentrations of BP derivatives and the odds of an endometriosis diagnosis; ORs increased across quartiles of 2OH-4MeO-BP and 2,4OH-BP concentrations, but a significant trend was observed only between 2,4OH-BP and the odds of an endometriosis diagnosis in the operative cohort (OR = 1.19; 95% CI = 1.01, 1.41). When women in the highest quartile of 2,4OH-BP concentrations were compared with women in the first three quartiles, the OR increased considerably (OR = 1.65; 95% CI = 1.07, 2.53). Given that 2,4OH-BP possesses an estrogenic activity higher than that of 2OH-4MeO-BP, our results invite the speculation that exposure to elevated 2,4OH-BP levels may be associated with endometriosis.
  • Tatsuya Kunisue, Aldfumi Eguchi, Hisato Iwata, Shinsuke Tanabe, Kurunthachalam Kannan
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 45 (23) 10140 - 10147 0013-936X 2011/12 [Peer-reviewed]
     Scientific journal 
    Thyroid hormones (THs) are essential for the regulation of growth and development in both humans and wildlife. Until recently, TH concentrations in the tissues of animals have been examined by immunoassay (IA) methods. IA methods are sensitive, but for TH analysis, they are compromised by a lack of adequate specificity. In this study, we determined the concentrations of six THs, L-thyroxine (T-4), 3,3',5-triiodo-L-thyronine (T-3), 3,3',5'-triiodo-L-thyronine (rT(3)), 3,5-diiodo-L-thyronine (3,5-T-2), 3,3'-diiodo-L-thyronine (3,3'-T-2), and 3-iodo-L-thyronine (3-T-1), in the serum of humans (n = 79) and wild Baikal seals (n = 37), by isotope ([C-13(6)]-T-4)dilution liquid chromatography (LC)-tandem mass spectrometry (MS/MS), and compared the TH levels with those measured by an electrochemiluminescent immunoassay (ECLIA) method. T-3 and T-4 were detected in all serum samples of both humans and Baikal seals, whereas T-1, 3,3'-T-2, and 3,5-T-2 were below the limit of detection (LOD). rT(3) was detected in Baikal seal sera at concentrations higher than T-3 in 28 seal samples, indicating an anomaly in deiodinase activity in Baikal seals. In humans, regression analyses of TH concentrations, measured by ECLIA and LC-MS/MS methods, showed significant correlations for T-4 (r = 0.852) and T-3 (r = 0.676; after removal of a serum sample with abnormal T-3 levels). In Baikal seals, a low correlation coefficient (r = 0.466) for T-4 levels and no correlation for T-3 levels (p = 0.093) were found between ECLIA and LC-MS/MS methods. These results suggest that interference by a nonspecific reaction against anti-T-3 and anti-T-4 antibodies used in the ECLIA can contribute to inaccuracies in TH measurement in Baikal seals. When the relationship between concentrations of THs in sera and dioxin-like toxic equivalents in blubber samples of Baikal seals (n = 19) was examined, a significantly negative correlation was found for serum T-4 levels measured by the LC-MS/MS method, but not for those measured by ECLIA. Thus, our results indicate that the LC-MS/MS method is more reliable and accurate for the elucidation of alteration in circulating TH levels in wildlife, as caused by environmental and physiological factors.
  • Shusaku Hirakawa, Daisuke Imaeda, Kei Nakayama, Masayuki Udaka, Eun-Young Kim, Tatsuya Kunisue, Masako Ogawa, Tomonari Matsuda, Saburo Matsui, Evgeny A. Petrov, Valeriy B. Batoev, Shinsuke Tanabe, Hisato Iwata
    AQUATIC TOXICOLOGY 105 (1-2) 89 - 99 0166-445X 2011/09 [Peer-reviewed]
     Scientific journal 
    We have previously indicated that accumulation of chlorinated dioxins and related compounds (DRCs) induced cytochrome P450 (CYP) 1A1, 1A2 and 1B1 isozymes in the liver of wild Baikal seals (Pusa sibirica). Here we attempt to assess the potential effects of DRCs triggered by the induction of these CYP1 isozymes in this species, using an integrative approach, combining gene expression monitoring and biochemical assays. To screen genes that may potentially respond to the exposure of DRCs, we constructed a custom cDNA oligo array that can target mRNAs in Baikal seals, and monitored hepatic mRNA expression levels in the wild population. Correlation analyses between the hepatic total 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) and mRNA levels supported our previous findings that high accumulation of DRCs induces the transcription of CYP1A1, CYP1A2 and CYP1B1 genes. In addition, our integrative assessment indicated that the chronic exposure to DRCs may alter the hepatic transcript levels of genes related to oxidative stress, Fe ion homeostasis, and inflammatory responses. The expression levels of CYP1A2 showed significant positive correlations with levels of malondialdehyde, a biomarker of lipid peroxidation, and of etheno-dA, a DNA adduct, suggesting that the lipid peroxidation may be enhanced through the production of reactive oxygen species (ROS) triggered by CYP1A2 induction. Moreover, there was a positive correlation between heme oxygenase activities and malondialdehyde levels, suggesting the prompted hems degradation by ROS. Fetuin-A levels, which are suppressed by inflammation, showed a significant negative correlation with TEQ levels, and hepcidin levels, which are conversely increased by inflammation, had significant positive correlations with malondialdehyde and etheno-dA levels, implying the progression of inflammation by DRC-induced oxidative stress. Taken together, we propose here that wild Baikal seals may suffer from effects of chronic exposure to DRCs on the induction of CYP1 isozymes, followed by increased oxidative stress, heme degradation and inflammation. (C) 2011 Elsevier B.V. All rights reserved.
  • Tatsuya Kunisue, Jeffrey W. Fisher, Kurunthachalam Kannan
    ARCHIVES OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY 61 (1) 151 - 158 0090-4341 2011/07 [Peer-reviewed]
     Scientific journal 
    Perchlorate can perturb thyroid hormone (TH) homeostasis by competitive inhibition of iodide uptake by the thyroid gland. Until recently, the effects of perchlorate on TH homeostasis were examined by measuring serum concentrations of THs by immunoassay (IA) methods. IA methods are sensitive, but for TH analysis they are compromised by lack of adequate specificity. In this study, we determined the concentrations of six THs: l-thyroxine (T(4)), 3,3',5-triiodo-l-thyronine (T(3)), 3,3',5'-triiodo-l-thyronine (rT(3)), 3,5-diiodo-l-thyronine, 3,3'-diiodo-l-thyronine, and 3-iodo-l-thyronine in the serum of rats administered perchlorate by isotope ((13)C(6)-T(4))-dilution liquid chromatography-tandem mass spectrometry. The method recoveries for THs spiked into a serum matrix were between 97.0% and 115%, with a coefficient of variation of 2.1% to 9.4%. Rats were placed on an iodide-deficient or iodide-sufficient diet for 2.5 months, and for the last 2 weeks of that period they were provided drinking water either without or with perchlorate (10 mg/kg body weight/day). No significant differences in serum concentrations of T(3) and T(4) were observed between rats given iodide-deficient and iodide-sufficient diets for 2 or 2.5 months. After 24 h of perchlorate exposure, significantly lower concentrations of T(3) and T(4) were found in the serum of rats administered the iodide-deficient diet but not in rats administered the iodide-sufficient diet. However, after 2 weeks of perchlorate exposure, TH levels in rats fed the iodide-sufficient diet were also significantly lower than those in control rats. Our results suggest that perchlorate affects TH homeostasis and that such effects are more pronounced under iodide-deficient nutrition.
  • Zifeng Zhang, Nanqi Ren, Yi-Fan Li, Tatsuya Kunisue, Dawen Gao, Kurunthachalam Kannan
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 45 (9) 3909 - 3916 0013-936X 2011/05 [Peer-reviewed]
     Scientific journal 
    Benzophenones and benzotriazoles are widely used as ultraviolet (UV) light filters and stabilizers in cosmetics, skin creams, and body lotions and as corrosion inhibitors in building materials, automobile components, and automotive antifreeze cooling systems. Benzophenones and benzotriazoles have been reported to occur in the environment. Some of these UV filters have been reported to possess significant estrogenic activity. Despite this, very few studies have examined their occurrence and profiles in the environment. In this work, we determined five benzophenone-type UV filters and two benzotriazole-type corrosion inhibitors, namely, 2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), 2,4-dihydroxybenzophenone (24OH-BP), 2,2'-dihydroxy-4-methoxybenzophenone (2,2'OH-4MeO-BP), 2,2',4,4'-tetrahydroxybenzophenone (2,21,4,4'OH-BP), 4-hydroxybenzophenone (4OH-BP), 1H-benzotriazole (1H-BT), and 5-methyl-1H-benzotriazole (5Me-1H-BT), in sediment and sewage sludge samples, using liquid-liquid extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS). In addition, four benzotriazole-type UV stabilizers, namely, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (UV-326), 2,4-di-t-butyl-6-(5-chloro-2H-benzotriazole-2yl) phenol (UV-327), 2-(2H-benzotriazole-2yl)-4,6-di-t-pentylphenol (UV-328), and 2-(5-t-butyl-2-hydroxyphenyl) benzotriazole (TBHPBT) were determined by gas chromatography (GC)-mass spectrometry (MS). The limits of quantitation (LOQ) were in the ranges of 0.06-0.33 ng g(-1) dry weight (dw) and 0.1-1.65 ng g(-1) dw for sediment and sludge samples, respectively. Recoveries of target compounds spiked into sample matrices and passed through the entire analytical procedure ranged from 70% to 116% (RSD: 3.32-13.8%) and from 82% to 106% (RSD: 2.89-8.09%) for the compounds analyzed by LC-MS/MS and GC-MS, respectively. The methods were applied to the analysis of sediment samples from the Songhua, Saginaw, and Detroit Rivers; the sum concentrations of target compounds were 3.29-9.93, 5.81-22.5, and 190-389 ng g(-1) dw, respectively. Five sludge samples collected from five wastewater treatment plants in northeastern China contained the sum concentrations of target compounds in the range of 104-6370 ng g(-1) dw. The concentration of UV-328 in sludge was the highest (mean: 1300 ng g(-1) dw) among the target compounds. To our knowledge, this is the first work to report the occurrence of 2OH-4MeO-BP, 2,4OH-BP, 2,2'OH-4MeO-BP, 2,2,4,4'OH-BP, and 4OH-BP in sediment and sludge samples.
  • Jing Ma, Jinping Cheng, Wenhua Wang, Tatsuya Kunisue, Minghong Wu, Kurunthachalam Kannan
    JOURNAL OF HAZARDOUS MATERIALS 186 (2-3) 1966 - 1971 0304-3894 2011/02 [Peer-reviewed]
     Scientific journal 
    Hair samples collected from e-waste recycling workers (n = 23 males, n = 4 females) were analyzed to assess occupational exposures to polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) at a large e-waste recycling facility in Taizhou, eastern China. Hair samples from a reference population composed of residents of Shanghai (n = 11) were analyzed for comparison. The mean concentration of Sigma PBDEs (range, 22.8-1020 ng/g dw: mean, 157 ng/g dw) found in hair samples from e-waste recycling workers was approximately 3 times higher than the mean determined for the reference samples. The congener profiles of PBDEs in hair from e-waste recycling workers were dominated by BDE 209, whereas the profiles in the reference-population samples showed comparable levels of BDE 47 and BDE 209. Total PCDD/F concentrations in hair from e-waste workers (range, 126-5820 pg/g dw: mean, 1670 pg/g dw) were approximately 18-fold greater than the concentrations measured in hair from the reference population. Concentrations of PCDFs were greater than concentrations of PCDDs, in all of the hair samples analyzed (samples from e-waste and non-e-waste sites). Tetrachlorodibenzofurans (TCDFs) were the major homologues in hair samples. Overall, e-waste recycling workers had elevated concentrations of both PBDEs and PCDD/Fs, indicating that they are exposed to high levels of multiple persistent organic pollutants. (C) 2010 Elsevier B.V. All rights reserved.
  • Tatsuya Kunisue, Jeffrey W. Fisher, Kurunthachalam Kannan
    ANALYTICAL CHEMISTRY 83 (1) 417 - 424 0003-2700 2011/01 [Peer-reviewed]
     Scientific journal 
    Thyroid hormones (THs) play critical roles in the regulalion of growth and development, including brain development, in both humans and animals. Until recently, TH levels were assayed with measurements in serum, using immunoassay (IA)-based methods. IA methods are sensitive but are compromised by the lack of adequate specificity. Furthermore, measurements of TH levels in blood do not necessarily reflect the levels and profiles found in critical organs such as the brain. Measurement of TH levels in the brain is critical for studies that assess the effects of environmental contaminants on TH homeostasis. In this study, we developed a selective and sensitive method for the analysis of six THs, L.-thyroxine (T(4)), 3,3',5-triiodo-L-thyronine (T(3)), 3,3',5'-triiodo- L-thyronine (rT(3)), 3,5-diiodo-L-thyronine (3,5-T(2)), 3,3'-diiodo-L-thyronine (3,3'-T(2)), and 3-iodo-L-thyronine (3-T(1)), in the brain and thyroid gland (TG) using isotope ([(13)C]T(4))-dilution liquid chromatography (LC)/tandem mass spectrometry (MS/MS). Proteins in the (rat) brain and TG were digested by pronase, and THs were extracted with a solid-phase extraction method and analyzed by LC/MS/MS. The instrumental calibration range for each TH ranged from 0.5 to 200 ng/mL and showed excellent linearity (r > 0.9995). The instrumental detection limits for THs were in the range of 7.5-13.5 pg, in positive ion mode, and 13.5-16.5 pg, in negative ion mode. The optimized procedural recoveries for THs (except for 3-T(1)), spiked into a pig-brain matrix, were between 97.6% and 109%, with a coefficient of variation (CV) of 1.2-8.2%, for the brain, and between 96.4% and 101%, with a CV of 1.8-8.6%, for the TG. Concentrations of THs in the brain and TG of the five rats were 2.20-3.65 ng/g T(4), 1.56-2.20 ng/g T(3), and below the limit of detection (<LOD) for the other THs, in the brain, and 88.9-274 ng/mgT(4), 14.1-49.1 ng/mg T(3), 2.79-12.0 ng/mg rT(3), 0.176-0.535 ng/mg 3,5-T(2), 0.340-0.880 ng/mg 3,3'-T(2), and <LOD for 3-T(1), in the TG. This method can permit more comprehensive evaluation of TH homeostasis in the brain and other critical organs following exposure to environmental contaminants.
  • Govindan Malarvannan, Shin Takahashi, Tokutaka Ikemoto, Tomohiko Isobe, Tatsuya Kunisue, Agus Sudaryanto, Toshihiko Miyagi, Masaru Nakamura, Shigeki Yasumura, Shinsuke Tanabe
    MARINE POLLUTION BULLETIN 63 (5-12) 541 - 547 0025-326X 2011 [Peer-reviewed]
     Scientific journal 
    Two species of fishes (n =52; tilapia and mullet) from industrialized and urbanized areas of Okinawa Island (Manko-Noha river, Hija river and Shikaza river) and from a remote area of Ishigaki Island (Anparu mudflat), Japan were collected between August 2005 and July 2006, and analyzed for five organochlorine compounds (OCs), viz., DDTs, PCBs, CHLs, HCHs and HCB. Concentrations and the contamination patterns of OCs in fishes varied between locations. Considerable residue levels of OCs, especially CHLs and DDTs were found in both fishes from the main Okinawa Island. These levels were relatively higher than the reported values for seafood from Japanese coasts, indicating that even now pollution sources of these contaminants still exist in this region. On the other hand, lower concentrations of OCs were detected in fishes from Ishigaki Island waters than those of other Japanese coastal waters, suggesting that this region is less contaminated by OC contaminants. (C) 2011 Elsevier Ltd. All rights reserved.
  • Govindan Malarvannan, Shin Takahashi, Tomohiko Isobe, Tatsuya Kunisue, Agus Sudaryanto, Toshihiko Miyagi, Masaru Nakamura, Shigeki Yasumura, Shinsuke Tanabe
    MARINE POLLUTION BULLETIN 63 (5-12) 172 - 178 0025-326X 2011 [Peer-reviewed]
     Scientific journal 
    Three species of sea turtles (green. hawksbill and loggerhead turtles) stranded along the coasts or caught (by-catch) around Ishigaki Island and Kochi, Japan were collected between 1998 and 2006 and analyzed for six organohalogen compounds viz., PBDEs, PCBs, DDTs, CHLs, HCHs and HCB. The present study is the first and foremost to report the occurrence of organohalogen compounds in the sea turtles from Japan. Among the compounds analyzed, concentrations of PCBs, DDTs and CHLs were the highest in all the turtle samples. PBDEs were ubiquitously present in all the turtle species. Comparing with the other two species, concentrations of organohalogens in green turtle were relatively low and decreasing trend in the concentrations were noted with increasing carapace length. Concentrations of OCs in sea turtles from the coasts of Ishigaki Island and Kochi were relatively low as compared to those from other locations in the world. (C) 2011 Elsevier Ltd. All rights reserved.
  • Tatsuya Kunisue, Shinsuke Tanabe, Tomohiko Isobe, Kenneth M. Aldous, Kurunthachalam Kannan
    JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY 58 (17) 9838 - 9846 0021-8561 2010/09 [Peer-reviewed]
     Scientific journal 
    Intake of a diet rich in phytoestrogens has been associated with a decreased risk for hormone-dependent cancers in humans. Biomonitoring of phytoestrogens in human urine has been used to assess the intake of phytoestrogens. Although studies have reported phytoestrogen levels in urine specimens from the United States and Japan, little is known of human intake of phytoestrogens in other Asian countries. In this study we determined the concentrations of seven phytoestrogens, namely, enterolactone, enterodiol, daidzein, equol, O-desmethylangolensin (O-DMA), genistein, and coumestrol, in 199 human urine samples from three Asian countries, Vietnam (Hanoi and Ho Chi Minh), Cambodia (Phnom Penh), and India (Chennai and Kolkata), using a simple, sensitive, and reliable liquid chromatography (LC)-tandem mass spectrometry (MS/MS) method. The residue levels of phytoestrogens in urine samples from the three Asian countries were compared with the concentrations in 26 urine samples from Japan (Ehime) and 16 urine samples from the United States (Albany), analyzed in this study. Among the phytoestrogens analyzed, isoflavones such as daidzein and genistein were predominant in urine samples from Vietnam; samples from Cambodia and India contained higher concentrations of enterolactone than isoflavones. Urinary concentrations of isoflavones in samples from Hanoi, Vietnam, were notably higher than the concentrations in samples from Cambodia, India, and the United States and similar to the concentrations in samples from Japan. The lowest concentrations of daidzein and the highest concentrations of enterolactone were found in urine samples from India. Concentrations of equol and O-DMA, which are microbial transformation products of daidzein (produced by gut microflora), were notably high in urine samples from Hanoi, Vietnam. The ratios of the concentration of equol or O-DMA to that of daidzein were significantly higher in samples from Hanoi than from Japan, indicating high biotransformation efficiency of daidzein by the population in Hanoi. High concentrations of equol, in addition to isoflavones, in urine have been linked to reduced breast cancer risk in previous studies, and, thus, the Vietnamese population may have potential protective effect against breast cancer. This study suggests that the dietary intake and profiles of phytoestrogens vary considerably, even among Asian countries.
  • Tatsuya Kunisue, Jeffrey W. Fisher, Babatope Fatuyi, Kurunthachalam Kannan
    JOURNAL OF CHROMATOGRAPHY B-ANALYTICAL TECHNOLOGIES IN THE BIOMEDICAL AND LIFE SCIENCES 878 (21) 1725 - 1730 1570-0232 2010/07 [Peer-reviewed]
     Scientific journal 
    Perchlorate can competitively inhibit iodide uptake by the thyroid gland (TG) via the sodium/iodide symporter, consequently reducing the production of thyroid hormones (THs). Until recently, the effects of perchlorate on TH homeostasis are being examined through measurement of serum levels of TH, by immunoassay (IA)-based methods. IA methods are fast, but for TH analysis, they are compromised by the lack of adequate specificity. Therefore, selective and sensitive methods for the analysis of THs in TG are needed, for assessment of the effects of perchlorate on TH homeostasis. In this study, we developed a method for the analysis of six THs: L-thyroxine (T(4)), 3,3',5-triiodo-L-thyronine (T(3)), 3,3',5'-triiodo-L-thyronine (rT(3)), 3,5-diiodo-L-thyronine (3,5-T(2)), 3,3'-diiodo-L-thyronine (3,3'-T(2)), and 3-iodo-L-thyronine (3-T(1)) in TG, using liquid chromatography (LC)-tandem mass spectrometry (MS/MS). TGs used in this study were from rats that had been placed on either iodide-deficient diet or iodide-sufficient diet, and that had either been provided with perchlorate in drinking water (10 mg/kg/day) or control water. TGs were extracted by pronase digestion and then analyzed by LC-MS/MS. The instrumental calibration range for each TH ranged from 1 to 200 ng/ml and showed a high linearity (r > 0.99). The method quantification limits (LOQs) were determined to be 0.25 ng/mg TG for 3-T(1); 0.33 ng/mgTG for 3,3'-and 3,5-T(2); and 0.52 ng/mg TG for rT(3), T(3), and T(4). Rats were placed on an iodide-deficient or -sufficient diet for 2.5 months, and for the last 2 weeks of that period were provided either perchlorate (10 mg/kg/day) in drinking water or control water. Iodide deficiency and perchlorate administration both reduced TG stores of rT(3), T(3), and T(4). In iodide-deficient rats, perchlorate exacerbated the reduction in levels of THs in TG. With the advances in analytical methodology, the use of LC-MS/MS for measurement of hormone levels in TG will allow more comprehensive evaluations of the hypothalamic-pituitary-thyroid axis. (C) 2010 Elsevier B.V. All rights reserved.
  • Michio X. Watanabe, Tatsuya Kunisue, Lin Tao, Kurunthachalam Kannan, Annamalai Subramanian, Shinsuke Tanabe, Hisato Iwata
    ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY 29 (7) 1551 - 1560 0730-7268 2010/07 [Peer-reviewed]
     Scientific journal 
    Dioxins and related compounds (DRCs) and perfluorinated compounds were measured in the livers of pigs (Sus scrofa) collected from an open waste dumping site in South India. Hepatic concentrations of DRCs and perfluorooctanesulfonate (PFOS; up to 200 ng/g wet wt) were significantly higher in male and female pigs, respectively, collected from the dumping site than in those from a reference site. Results suggest that dumping sites are a source of DRCs and PFOS. Hepatic concentrations of DRCs in piglets were higher than in mothers, especially for the congeners with molecular weights in the range of 360 to 400, implying congener-specific maternal transfer of DRCs in swine. Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans and some non-ortho dioxin-like polychlorinated biphenyls (PCBs) in the liver of pigs were higher than those in the adipose fat and muscle of the same specimens. In addition, the liver-to-adipose concentration ratios for each congener had a significant positive correlation with the levels of hepatic cytochrome P450 (CYP)1A-like protein, suggesting congener-specific and CYP1A-dependent hepatic sequestration of DRCs in the swine. Total hepatic 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs; 8.9-350 pg/g fat wt) had a significant positive correlation with CYP1A-like protein expression (r= 0.56, p = 0.012), suggesting the induction of CYP1A by DRCs. However, the total TEQs had a significant negative correlation with CYP4A-like protein (r= -0.49, p= 0.029), suggesting repression of peroxisome proliferator-activated receptor-alpha (PPAR alpha)-mediated signaling pathway by DRCs. Decreases in plasma total thyroxine (T(4)), free T(4), and immunoglobulin (Ig) G were also found in pigs from the dumping site compared with those from the reference site. This study provides insight into the toxicological impacts of DRCs and perfluorinated compounds in wild animals from open waste dumping sites. Environ. Toxicol. Chem. 2010;29:1551-1560. (C) 2010 SETAC
  • Akira Kubota, Mafumi Watanabe, Tatsuya Kunisue, Eun-Young Kim, Shinsuke Tanabe, Hisato Iwata
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 44 (9) 3559 - 3565 0013-936X 2010/05 [Peer-reviewed]
     Scientific journal 
    The present study assesses effects of dioxins and related compounds (DRCs) including polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls (DL-PCBs) on cytochrome P450 1A (CYP1A) expression level in liver of black-footed albatrosses (Phoebastria nigripes) collected from the North Pacific, Total 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-T4CDD) toxic equivalents (TEQs) derived from toxic equivalency factor for birds proposed by World Health Organization were in the range of 2100 to 10 000 pg/g lipid wt (120-570 pg/g wet wt). Simultaneously, microsomal alkoxyresorufin O-dealkylase (AROD) activities, including methoxy-, ethoxy-, pentoxy-, and benzyloxy-resorufin O-dealkylase activities were also measured in the same specimens. Total TEQs and TEQ (on wet wt basis) from some individual DRC congeners had significant positive correlations with AROD activities, suggesting induction of CYP1A by DRCs. Congeners like 2,3,7,8-T4CDD and most of the DL-PCBs that showed no significant positive correlations between the concentrations and AROD activities, exhibited significant negative correlations between AROD activities and the concentration ratio of the congener to a recalcitrant CB169, suggesting preferential metabolism of these congeners by induced CYP1A. As far as we know, this is the first direct evidence revealing that hepatic CYP1A level is elevated with the accumulation of DRCs in the wild black-footed albatross population. The present study gives more robust estimate of impacts of DRCs on CYP1A induction in this rare pelagic species than indexes like hazard quotient and TEQ-threshold comparison that have been so far carried out.
  • Kei Nomiyama, Satoko Murata, Tatsuya Kunisue, Tadasu K. Yamada, Hazuki Mizukawa, Shin Takahashi, Shinsuke Tanabe
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 44 (10) 3732 - 3738 0013-936X 2010/05 [Peer-reviewed]
     Scientific journal 
    In this study, we determined the residue levels and patterns of polychlorinated biphenyls (PCBs) and hydroxylated PCBs (OH-PCBs) in the blood from eight species of toothed whales and three species of baleen whales stranded along the Japanese coast during 1999-2007. Penta- through hepta-chlorinated PCB congeners were the dominant homologue groups in all cetaceans. In contrast, specific differences in the distribution of dominant OH-PCB isomers and homologues were found among the cetacean species. In five species of toothed whales (melon-headed whale, Stejneger's beaked whale, Pacific white-sided dolphin, Blainville's beaked whale, and killer whale), the predominant homologues were OH-penta-PCBs followed by OH-tetra-PCBs and OH-tri-PCBs. The predominant homologues of finless porpoise and beluga whale were OH-penta-PCBs followed by OH-hexa-PCBs and OH-tri-PCBs. The predominant OH-PCB isomers were para-OH-PCBs such as 4'OH-CB26, 4'OH-CB25/4'OH-CB26/4OH-CB31, 4OH-CB70, 4'OH-CB72, 4'OH-CB97, 4'OH-CB101/4'OH-CB120, and 4OH-CB107/4'OH-CB108 in toothed whales. In three baleen whales (common minke whale, Bryde's whale, and humpback whale) and in sperm whale (which is a toothed whale), OH-octa-PCB (4OH-CB202) was the predominant homologue group accounting for 40-80% of the total OH-PCB concentrations. The differences in concentrations and profiles of OH-PCBs may suggest species-specific diets, metabolic capability, and the transthyretin (TTR) binding specificity. These results reveal that the accumulation profiles of OH-PCBs in cetacean blood are entirely different from the profiles found in pinnipeds, polar bear, and humans.
  • Masayuki Someya, Masako Ohtake, Tatsuya Kunisue, Annamalai Subramanian, Shin Takahashi, Paromita Chakraborty, Ramesh Ramachandran, Shinsuke Tanabe
    ENVIRONMENT INTERNATIONAL 36 (1) 27 - 35 0160-4120 2010/01 [Peer-reviewed]
     Scientific journal 
    Concentrations of persistent organic Pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and organochlorine pesticides were measured in human breast milk collected from mothers residing near an open dumping site and a reference site in Kolkata, India during 2004-2005. POPs were detected in all the human milk samples analyzed, suggesting that residents of Kolkata are widely exposed to these contaminants. Concentrations of dioxin-like PCBs in the samples from the dumping site were significantly higher than in the reference site samples, whereas no such difference was found for PCDDs and PCDFs. In addition, significantly higher concentrations of total PCBs were also observed in the samples from the dumping site than the reference site. Interestingly, concentrations of total and dioxin-like PCBs in the breast milk of mothers from the dumping site significantly increased with the number of years of residence near the dumping site. These results indicate that significant pollution sources of PCBs are present in the dumping site of Kolkata and the residents living around are exposed to relatively higher levels of PCBs. When the residue levels of dioxins and related compounds in fish collected from ponds near the Kolkata dumping site and the reference site were measured, it was found that dioxin-like PCB and TEQ levels in fish from the dumping site were notably higher than those from the reference site. This result indicates that fish is a potential source of PCBs for residents living near the Kolkata dumping site. (C) 2009 Elsevier Ltd. All rights reserved.
  • Govindan Malarvannan, Tatsuya Kunisue, Tomohiko Isobe, Agus Sudaryanto, Shin Takahashi, Maricar Prudente, Annamalai Subramanian, Shinsuke Tanabe
    ENVIRONMENTAL POLLUTION 157 (6) 1924 - 1932 0269-7491 2009/06 [Peer-reviewed]
     Scientific journal 
    Human breast milk samples (n = 33) from primipara and multipara mothers from Payatas a waste dump site, and Malate a reference site in the Phillipines were collected in 2004 and analyzed for eight organohalogen compounds, viz., PCBs, DDTs, CHLs, HCHs, HCB, TCPMe, PBDEs and HBCDs. DDTs and PCBs were predominant in all the samples. Overall mean concentrations of PBDEs found in our study were higher (7.5 ng/g lipid wt.) than those reported for Japan and many other Asian countries. Primipara mothers had significantly higher levels of DDTs, CHLs and HCHs than multipara mothers, but not PBDEs and HBCDs. A few individuals accumulated CHLs close to or even higher than the tolerable daily intake guidelines proposed by Health Canada. (C) 2009 Elsevier Ltd. All rights reserved.
  • Kurunthachalam Kannan, Meredith L. Praamsma, John F. Oldi, Tatsuya Kunisue, Ravindra K. Sinha
    CHEMOSPHERE 76 (1) 22 - 26 0045-6535 2009/06 [Peer-reviewed]
     Scientific journal 
    Perchlorate (ClO4-), which is used as an oxidizer in jet and rocket fuels, pyrotechnic devices and explosives, is a widespread contaminant in surface waters and groundwater of many countries. Perchlorate is known to affect thyroid function. Despite the compound's widespread occurrence and potential health effects, perchlorate levels in drinking water in India are not known. In this study, water samples collected from 13 locations in six states (n = 66), and saliva samples collected from four locations in three states (n = 74) in India, were analyzed for perchlorate using high performance liquid chromatography interfaced with tandem mass spectrometry (HPLC-MS/MS). Perchlorate was detected in most (76%) of the water samples analyzed at concentrations above the quantitation limit of 0.02 mu g L-1; concentrations ranged from <0.02 to 6.9 mu g L-1 (mean: 0.42 +/- 1.1 mu g L-1; median: 0.07 mu g L-1). Mean concentrations of perchlorate in drinking water, groundwater, bottled water, surface water and rain water were 0.1, 1.0, <0.02, 0.05 and <0.02 mu g L-1, respectively. From a total of 66 water samples analyzed, only three samples contained perchlorate levels above 1 mu g L-1; all three were groundwater samples. Perchlorate was found in the saliva samples analyzed at concentrations above 0.2 mu g L-1 and up to 4.7 mu g L-1 (mean: 1.3 +/- 1.3 mu g L-1; median: 0.91 mu g L-1). No remarkable differences in perchlorate concentrations were found among the sampling locations of water or saliva or in subgroups stratified by gender or age. Perchlorate concentrations in water samples from India are one to two orders of magnitude lower than the concentrations reported for the United States. (C) 2009 Elsevier Ltd. All rights reserved.
  • Tatsuya Kunisue, Boris Johnson-Restrepo, David R. Hilker, Kenneth M. Aldous, Kurunthachalam Kannan
    ENVIRONMENTAL POLLUTION 157 (3) 910 - 915 0269-7491 2009/03 [Peer-reviewed]
     Scientific journal 
    Polychlorinated naphthalenes (PCNs) are persistent, bioaccumulative, and toxic contaminants. Prior to this study, the occurrence of PCNs in human adipose tissues from the USA has not been analyzed. Here, we have measured concentrations of PCNs in human adipose tissue samples collected in New York City during 2003-2005. Concentrations of PCNs were in the range of 61-2500 pg/g lipid wt. in males and 21910 pg/g lipid wt. in females. PCN congeners 52/60 (1,2,3,5,7/1,2,4,6,7) and 66/67 (1,2,3,4,6,7/1,2,3,5,6,7) were predominant, collectively accounting for 66% of the total PCN concentrations. Concentrations of PCNs in human adipose tissues were 2-3 orders of magnitude lower than the previously reported concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Concentrations of PCNs were not correlated with PCB concentrations. The contribution of PCNs to dioxin-like toxic equivalents (TEQs) in human adipose tissues was estimated to be < 1% of the polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F)-TEQs. (C) 2008 Elsevier Ltd. All rights reserved.
  • Daisuke Imaeda, Tatsuya Kunisue, Yoko Ochi, Hisato Iwata, Oyuna Tsydenova, Shin Takahashi, Masao Amano, Evgeny A. Petrov, Valeriy B. Batoev, Shinsuke Tanabe
    ENVIRONMENTAL POLLUTION 157 (3) 737 - 747 0269-7491 2009/03 [Peer-reviewed]
     Scientific journal 
    This study investigated the accumulation features and temporal trends of PCDD/Fs, dioxin-like PCBs (DL-PCBs) and non-dioxin-like PCBs (NDL-PCBs) in the blubber of Baikal seals collected in 1992 and 2005. DL-PCBs (480-3600 ng/g) and NDL-PCBs (980-35,000 ng/g) were dominant contaminants. Concentrations of PCDDs and PCBs in males were significantly higher than in females. In males, age-dependent accumulation was observed for PCDDs, mono-ortho PCBs and NDL-PCBs. PCDFs and non-ortho PCBs showed no such trends, implying that exposure of seals to these contaminants has been decreasing in recent years. No decreasing temporal trend was observed for PCDDs, mono-ortho PCBs and NDL-PCBs, suggesting that Baikal seals are still exposed to PCDDs and PCBs. TEQs of PCDDs and mono-ortho PCBs in seals collected in 2005 accounted for 62-77% of total TEQs. The TEQ levels in 40% of the specimens exceeded the threshold level for immunosuppression observed in harbor seals (209 pg/g). (C) 2008 Elsevier Ltd. All rights reserved.
  • Tatsuya Kunisue, Shinsuke Tanabe
    CHEMOSPHERE 74 (7) 950 - 961 0045-6535 2009/02 [Peer-reviewed]
     Scientific journal 
    An analytical method was developed to measure tri- to octa-chlorinated OH-PCBs and pentachlorophenol (PCP) in the whole blood. Further, baseline data on the levels and profiles of these phenolic compounds in Japanese mammals (human, cat, dog, raccoon dog, and northern fur seal) and birds (black-tailed gull, common cormorant, and jungle crow) were obtained. Eighteen identifiable and fifty unknown peaks of OH-PCBs were detected and the major congeners identified were 4'OH-CB101/120, 4OH-CB107/4'OH-CB108, 4OH-CB146, 4OH-CB178, 4OH-CB187, 4'OH-CB172, 4OH-CB202, and 4'OH-CB199. Relatively higher concentrations of OH-PCBs were found in animal species than humans; OH-PCB levels in dog, raccoon dog, black-tailed gull, and common cormorant blood were one order of magnitude higher than in humans. Penta-to hepta-chlorinated OH-PCB congeners were predominant in human blood, but profiles of OH-PCBs in other animals widely varied by species. Elevated composition of tri- and tetra-chlorinated OH-PCBs in cat blood and octa-chlorinated OH-PCBs in dog and raccoon dog blood were observed. In cat blood, elevated PCP concentration was also found. When concentration ratios of OH-PCBs to PCBs were calculated in all the animal blood, the ratios in dog, raccoon dog, and cat were notably higher than in other species. These results indicate that animals other than humans, especially cat and canine species such as dog and raccoon dog, might be at risk from OH-PCBs. (C) 2008 Elsevier Ltd. All rights reserved.
  • Lin Tao, Jing Ma, Tatsuya Kunisue, E. Laurence Libelo, Shinsuke Tanabe, Kurunthachalam Kannan
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 42 (22) 8597 - 8602 0013-936X 2008/11 [Peer-reviewed]
     Scientific journal 
    The occurrence of perfluorinated compounds (PFCs) in human blood is known to be widespread; nevertheless, the sources of exposure to humans, including infants, are not well understood. In this study, breast milk collected from seven countries in Asia was analyzed (n = 184) for nine PFCs, including perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA). In addition, five brands of infant formula (n = 21) and 11 brands of dairy milk (n = 12) collected from retail stores in the United States were analyzed, for comparison with PFC concentrations previously reported for breast milk from the U.S. PFOS was the predominant PFC detected in almost all Asian breast milk samples, followed by perfluorohexanesulfonate (PFHxS) and PFOA. Median concentrations of PFOS in breast milk from Asian countries varied significantly; the lowest concentration of 39.4 pg/mL was found in India, and the highest concentration of 196 pg/mL was found in Japan. The measured concentrations were similar to or less than the concentrations previously reported from Sweden, the United States, and Germany (median, 106-166 pg/mL). PFHxS was found in more than 70% of the samples analyzed from Japan, Malaysia, Philippines, and Vietnam, at mean concentrations ranging from 6.45 (Malaysia) to 15.8 (Philippines) pg/mL. PFOA was found frequently only in samples from Japan; the mean concentration for that country was 77.7 pg/mL. None of the PFCs were detected in the infant-formula or dairy-milk samples from the U.S. except a few samples that contained concentrations close to the limit of detection. The estimated average daily intake of PFOS by infants from seven Asian countries, via breastfeeding, was 11.8 +/- 10.6 ng/kg bw/ day; this value is 7-12 times higher than the estimated adult dietary intakes previously reported from Germany, Canada, and Spain. The average daily intake of PFOA by Japanese infants was 9.6 +/- 4.9 ng/kg bw/day, a value 3-10 times greater than the estimated adult dietary intakes reported from Germany and Canada. The highest estimated daily intakes of PFOS and PFOA by infants from seven Asian countries studied were 1-2 orders of magnitude below the tolerable daily intake values recommended by the U.K. Food Standards Agency.
  • Tatsuya Kunisue, Yumi Higaki, Tomohiko Isobe, Shin Takahashi, Annamalai Subramanian, Shinsuke Tanabe
    ENVIRONMENTAL POLLUTION 154 (2) 272 - 282 0269-7491 2008/07 [Peer-reviewed]
     Scientific journal 
    The present study determined concentrations and patterns of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in specimens of open sea, and Japanese coastal and inland avian species, which have been stored in the Environmental Specimen Bank of Ehime University (es-Bank), to examine the spatial trends. PBDEs and PCBs were detected in all the muscle samples analyzed, suggesting that PBDE pollution has spread even to the remote open sea areas, as in the case of PCBs. Japanese coastal and inland birds accumulated higher concentrations of PBDEs than open sea birds. In addition, higher PBDE/PCB concentration ratios were observed in Japanese coastal and inland birds than in open sea birds, indicating the input of PBDEs into the Japanese terrestrial environment. Compositions of PBDEs varied among avian species with a predominance of BDE47 or BDE153. This could be due to differences in their habitat, food habit and/or biotransformation capacity of PBDEs. (C) 2007 Elsevier Ltd. All rights reserved.
  • Tatsuya Kunisue, Nozomi Takayanagi, Tomohiko Isobe, Shin Takahashi, Susumu Nakatsu, Toshio Tsubota, Keisuke Okumoto, Sumio Bushisue, Kazuyuki Shindo, Shinsuke Tanabe
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 42 (3) 685 - 691 0013-936X 2008/02 [Peer-reviewed]
     Scientific journal 
    The present study investigated concentrations and patterns of brominated flame retardants, such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs), and persistent organochlorines (OCs) in liver and adipose tissues of raccoon dogs (RD: Nyctereutes procyonoides) collected from two metropolises and a local prefecture in Japan during 2001-2006. Relatively high concentrations of PBDEs were found in RD livers, while HBCD levels were the lowest among the measured organohalogen compounds. Among PBDE congeners, BDE 209 was predominant in RDs from all the regions, indicating that pollution derived from the technical decaBDE product is extensive across Japan. On the other hand, concentrations of tetra- to nona-BDE congeners in RDs from a metropolis were significantly higher than those from the other two regions, implying that there were regional differences in the past usage of the technical tetraBDE and octaBDE products. Such a regional difference was also observed for HBCD levels. Lipid-normalized concentration ratios of liver to adipose tissue L/A ratio) for tri to hepta-BDE congeners were lower than 1.0 in the investigated eight RDs, suggesting lipid-dependent accumulation. However, the L/A ratios of BDE 209 exceeded 1.0 in all the specimens, suggesting hepatic retention of this compound. In addition, lipid-dependent accumulation of alpha-HBCD was observed, but the L/A ratios of gamma-HBCD were greater than 1.0 in some specimens. These results indicate that Japanese RDs have been recently exposed to BDE 209 and gamma-HBCD and accumulated both these compounds preferentially in blood-rich organs, probably due to their binding to proteins and/or rapid biotransformation, as reported in experimental rodents.
  • Tatsuya Kunisue, Nozomi Takayanagi, Tomohiko Isobe, Shin Takahashi, Masato Nose, Taketo Yamada, Hiroaki Komori, Nonimasa Arita, Norifumi Ueda, Shinsuke Tanabe
    ENVIRONMENT INTERNATIONAL 33 (8) 1048 - 1056 0160-4120 2007/11 [Peer-reviewed]
     Scientific journal 
    The present study determined concentrations of polybrominated diphenyl ethers (PBDEs) and persistent organochlorines (OCs) in Japanese human adipose tissues collected during 2003-2004. Concentrations of PBDEs in adipose tissues were 1-2 orders of magnitude lower than those of OCs. However, observed PBDE congener levels in this study were relatively higher than those in Japanese human adipose tissues collected during 2000 reported previously, while OC levels were comparable to those in specimens collected during 1999 reported by our group. In addition, no age-dependent accumulation of PBDEs was observed, while OC levels except chlordane compounds increased with age. These results indicate recent human exposure to PBDEs in Japan. Among PBDE congeners accumulated in Japanese adipose tissues, BDE-153 was dominant, but this trend was different from those in human milk (BDE-47) and blood (BDE-209) reported previously in Japan, implying the congener-specific kinetics in human bodies. The significant positive correlations between PBDEs and OCs were observed in Japanese adipose tissues, indicating the similar exposure route of these contaminants for Japanese citizens, probably via fish intake. (C) 2007 Elsevier Ltd. All rights reserved.
  • Tatsuya Kunisue, Takanori Sakiyama, Tadasu K. Yamada, Shin Takahashi, Shinsuke Tanabe
    MARINE POLLUTION BULLETIN 54 (7) 963 - 973 0025-326X 2007/07 [Peer-reviewed]
     Scientific journal 
    Levels of hydroxylated polychlorinated biphenyls (OH-PCBs) and PCBs were measured in the brain of melon-headed whales (MW: Peponocephala electra), striped dolphins (SD: Stenella coerideoalba) and finless porpoises (FP: Neophocaena phocaenoides) stranded along the Japanese coast during 2002-2003. Levels of OH-PCBs (including identified and unknown OH-P5CB, -H6CB, -H7CB and O8CB congeners) in the brain of MW, SD and FP were in the range of 20-290, 21-330 and 170-240 pg/g wet wt., respectively. Observed OH-PCB levels were 2-3 orders of magnitude lower than PCBs in the same individuals. OH-PCBs/PCBs ratios in MW, SD and FP brain were lower than those in blood of humans and wildlife and in the brain of polar bears reported previously. OH-PCBs were also detected in maternal and fetal brain of SID (1 pair), suggesting transfer of OH-PCBs into the fetal brain of odontocete cetaceans. When fetus/dam concentration ratios of 0H-PCB congeners detected in maternal and fetal brain were estimated, the values were higher than those of PCB congeners, implying that OH-PCBs in maternal blood could be more easily transferred into fetal brain via placenta than PCBs. (c) 2007 Elsevier Ltd. All rights reserved.
  • Junya Nagayama, Hitoshi Kohno, Tatsuya Kunisue, Kyoichiro Kataoka, Hiroshi Shimomura, Shinsuke Tanabe, Sadanori Konishi
    CHEMOSPHERE 68 (5) 972 - 976 0045-6535 2007/06 [Peer-reviewed]
     Scientific journal 
    We have investigated the effects of prenatal exposure to dioxin-like compounds (PCDDs, PCDFs and dioxin-like PCBs), PCBs and organochlorine pesticides (DDT, HCH, chlordane, HCB and their metabolites) on the incidence of congenital hypothyroidism and/or cretinism in Fukuoka, Japan from 2001 to 2004. Thirty-four positive neonates of the mass-screening for cretinism were classified into three groups by the pediatrician after the reevaluation of the serum TSH level, that is, negative in reevaluation group, hyper thyroid stimulating hormone (TSH) emia group and cretinism group. One-hundred and two negative neonates of the mass-screening were classified into the normal group. Concentrations of these organochlorine compounds in the breast milk of mothers, which were considered as the indicator of prenatal exposures to them, were gradually increased from the normal group to the cretinism group in the four groups and were around two times higher in the cretinism group than in the normal group. According to the case-control study adjusted for the parity and mother's age, odds ratios of PCBs, DDT and HCB were 10 (p = 0.003), 10 (p = 0.003) and 22 (p = 0.004), respectively and in dioxin-like compounds, PCDFs showed the highest odds ratio, 9.8 (p = 0.005). Based upon those findings, these compounds seemed play an important role in the incidence and/or causation of the cretinism. (c) 2007 Elsevier Ltd. All rights reserved.
  • Annamalai Subramanian, Masako Ohtake, Tatsuya Kunisue, Shinsuke Tanabe
    CHEMOSPHERE 68 (5) 928 - 939 0045-6535 2007/06 [Peer-reviewed]
     Scientific journal 
    Mothers' milk from Chermai (formerly Madras), India and three other places Perungudi, the municipal dumping site of south Chennai area (situated at the suburb of Chennai), Chidambaram, a predominantly agricultural town situated 250 kin south of Chermai and Parangipettai, a fishing village 15 km north of Chidambaram, all situated at or near the southeastern Bay of Bengal coast of India were found to contain measurable concentrations of HCHs, DDTs, PCBs, CHLs and HCB. A notable finding in this study is that Chennai mothers have higher levels of HCHs in their milk and hence may transfer considerably higher amounts of the chemical than the mothers from all the other three places of the present study indicating a higher health risk to Chennai's children. It was also found that the levels of the two organochlorine pesticides (HCHs and DDTs) increased in Chermai mothers' milk in the last decade. Food items collected from Chennai markets did not show any remarkably higher levels of any of the chemicals measured in this study. Levels of the two classical organochlorines (DDTs and HCHs) have declined in many of the food items when compared with our data collected two decades before in the same locations, showing the effectiveness of the recent ban on both these chemicals in the country. The sources, possible health risks and the ways to curtail the effects of HCHs, especially at Chermai, should be investigated further. (c) 2007 Elsevier Ltd. All rights reserved.
  • Nguyen Hung Minh, Tu Binh Minh, Hisato Iwata, Natsuko Kajiwara, Tatsuya Kunisue, Shin Takahashi, Pham Hung Viet, Bui Cach Tuyen, Shinsuke Tanabe
    ARCHIVES OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY 52 (4) 458 - 465 0090-4341 2007/05 [Peer-reviewed]
     Scientific journal 
    Surficial sediment samples were collected from Hochiminh City canals, the Sai Gon-Dong Nai River, and its estuary, one of the most predominant industrial areas in Hochiminh City, southern Vietnam, for determination of selected persistent organic pollutants (POPs). Contamination pattern was as follows: PCBs >= DDTs > HCB > CHLs > HCHs. Concentrations of PCBs and DDTs ranged from 0.50-150 ng/g and 0.15-72 ng/g dry wt, respectively. On the other hand, concentrations of CHLs, HCHs, and HCB were mostly < 2 ng/g dry wt. Levels of the all organochlorines (OCs) in Hochiminh City canals were significantly higher than those in the other areas, indicating the urban areas as major pollution sources to the aquatic environment. The contamination pattern was PCBs > DDTs in the city canals but PCBs < DDTs in the downstream and the estuary, suggesting particularly high contamination by PCBs in the city. Examination of DDTs composition and their ratios demonstrated continuous input of this pesticide to the city canals. However, the combination of our data and those from available literature implies a decreasing trend of PCBs and DDTs in the environment. DDTs concentrations have been reduced 50% after approximately 5 years. Composition of CHLs in the sediment from Hochiminh City canals was comparable to those of common technical mixtures, suggesting continuous input of CHLs to the environment. CHLs might be in use for purposes like termite control, wood preservation, and protection of underground cables. Hazard assessment implies high toxic potential of DDTs for sediments from Hochiminh City canals and suggests the need for better management of municipal discharges.
  • Nguyen Hung Minh, Tu Binh Minh, Natsuko Kajiwara, Tatsuya Kunisue, Hisato Iwata, Pham Hung Viet, Nguyen Phuc Cam Tu, Bui Cach Tuyen, Shinsuke Tanabe
    CHEMOSPHERE 67 (9) 1794 - 1801 0045-6535 2007/04 [Peer-reviewed]
     Scientific journal 
    The Mekong River delta is one of the largest agricultural land in the Southeast Asia. It plays a very important role for agriculture and fisheries in South Vietnam. However, comprehensive studies on the environmental pollution of persistent organic pollutants (POPs) in Mekong River delta have not been carried out in recent years. In this study, we collected sediment samples from the Mekong River to evaluate the contamination and ecological risks caused by several POP's. The contamination pattern of POPs was DDT > PCBs > CHLs > HCHs > HCB. DDTs are the most abundant pollutants, their concentration ranging from 0.01 to 110 ng/g dry wt, followed by PCBs (0.039-9.2 ng/g dry wt). DDTs and PCBs concentrations were higher in sediment from adjacent to urban areas than those from rural and agricultural sites, suggesting urban areas as important point sources of DDTs and PCBs to the river. Ratio of pp'-DDT/p,p'-DDE was lower compared to those previously reported. However, some samples still had the ratio higher than 0.5, indicating recent input of DDT into the aquatic environments. This result shows that although the magnitude of contamination decreased over time, recent inputs of DDTs to the river still occur. Some sediment samples had concentrations of DDT compounds higher than the standards from the Canadian Environmental Quality Guideline, suggesting continuous monitoring for POPs contamination in the Mekong River is necessary. (c) 2006 Elsevier Ltd. All rights reserved.
  • Oyuna V. Tsydenova, Agus Sudaryanto, Natsuko Kajiwara, Tatsuya Kunisue, Valeriy B. Batoev, Shinsuke Tanabe
    ENVIRONMENTAL POLLUTION 146 (1) 225 - 232 0269-7491 2007/03 [Peer-reviewed]
     Scientific journal 
    Human breast milk samples collected during 2003/04 in Buryatia, a Russian autonomous republic, were analyzed in order to assess human exposure to organohalogen compounds including organochlorine pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). When compared with available worldwide data, levels of HCB (23-880 ng/g lipid wt.), PCBs (69-680 ng/g lipid wt.), and HCHs (100-3700 ng/g lipid wt.) were relatively high, indicating elevated human exposure to these organochlorines (OCs) in Buryatia. In contrast to OCs. PBDE concentrations were low (0.46-1.7 ng/g lipid wt.). Out of 14 BDE congeners analyzed, BDE-28, BDE-47, BDE-100, BDE153, BDE-197, and BDE-207 were detected. Estimated daily intakes (EDIs) of HCHs, HCB, CHLs, and PCBs by infants solely from human milk for 100%, 43%, 34%, and 17% of the samples, respectively, exceeded guideline thresholds. Although high EDIs raise concern for possible toxic effects of OCs, women in Buryatia are recommended to breastfeed due to numerous advantages of breastfeeding for mother and child. (c) 2006 Elsevier Ltd. All rights reserved.
  • Shinsuke Tanabe, Tatsuya Kunisue
    ENVIRONMENTAL POLLUTION 146 (2) 400 - 413 0269-7491 2007/03 [Peer-reviewed]
     
    In this paper, we concisely reviewed the contamination of persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs), hexachlorobenzene (HCB) in human breast milk collected from Asian countries such as Japan, China, Philippines, Vietnam, Cambodia, India, Malaysia, and Indonesia during 1999-2003. Dioxins, PCBs, CHLs in Japanese, and DDTs in Vietnamese, Chinese, Cambodian, Malaysian, and HCHs in Chinese, Indian, and HCB in Chinese breast milk were predominant. In India, levels of dioxins and related compounds (DRCs) in the mothers living around the open dumping site were notably higher than those from the reference site and other Asian developing countries, indicating that significant pollution sources of DRCs are present in the dumping site of India and the residents there have been exposed to relatively higher levels of these contaminants possibly via bovine milk. (c) 2006 Elsevier Ltd. All rights reserved.
  • Tatsuya Kunisue, Nozonu Takayanagi, Toshio Tsubota, Shinsuke Tanabe
    CHEMOSPHERE 66 (2) 203 - 211 0045-6535 2007/01 [Peer-reviewed]
     Scientific journal 
    The present study determined the accumulation features of persistent organochlorines (OCs) such as polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), and chlordane compounds (CHLs) in wild raccoon dogs (RDs; Nyclereutes procyonoides) collected from Kanagawa prefecture in Japan during 2001. In livers of RDs, CHLs were remarkably dominant (20 times higher than PCBs) followed by PCBs > DDTs > HCHs > HCB, whereas the chemicals in muscles were in the order of CHLs > PCBs > HCHs > DDTs > HCB. The accumulation pattern of OCs in RDs was different from those in Japanese humans and avian species reported previously, which generally accumulate higher levels of DDTs and PCBs than CHLs. This result indicates that RDs have been exposed to relatively high levels of CHLs and have high metabolic and elimination capacity for DDTs. In fact, CHL levels in RDs were higher than those in humans and some avian species, while DDT levels in RDs were much lower than other animals. In particular, extremely high accumulation levels of oxychlordane, which is a metabolite from chlordanes and nonachlors, were observed in RD livers. The higher toxic potency of oxychlordane than parent compounds may suggest that RDs are at high risk by this metabolite. On lipid weight basis, PCBs, HCHs and HCB levels were almost similar in livers and Muscles, suggesting that the tissue distribution of these compounds principally followed the lipid-dependent accumulation. However, accumulation levels of oxychlordane and p,p'-DDD in livers were significantly higher than those in muscles, and concentration ratios of liver to muscle (L/M ratios) of these Compounds were greater than 1.0 in all the specimens. This phenomenon was similar to PCDD/DF congener accumulation patterns observed previously in RDs. When relationships between hepatic TEQs and L/M ratios were examined for oxychlordane and p,p'-DDD, L/M ratios for these compounds significantly increased with hepatic TEQ levels, suggesting their hepatic sequestration in TEQs-dependent manner.
  • Tatsuya Kunisue, Shigeyuki Nakanishi, Nariko Oka, Fumio Sato, Miyako Tsurmi, Shinsuke Tanabe
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 40 (22) 6919 - 6927 0013-936X 2006/11 [Peer-reviewed]
     Scientific journal 
    Concentrations of dioxins and related compounds (DRCs), such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (Co-PCBs), were determined in eggs, nestlings, and adults of black-footed albatross (BfA; Diomedea nigripes) and short- tailed albatross (StA; Diomedea albatrus) collected from the Torishima Island in Japan during 2002, which is one of their breeding grounds. Observed DRC concentrations, especially PCDFs and non-ortho Co-PCBs, in eggs of BfA and StA were relatively higher than those in other oceanic, coastal, and inland wild birds reported recently and were comparable to those in a pooled BfA egg from Midway Atoll in 1993, implying continuous input of these contaminants into open ocean and possible albatross- specific exposure. Concentrations of PCDDs except 12378-P5CDD and high-chlorinated PCDFs in 3-month-old BfA nestling were lower than those in 1-month-old nestling, indicating their developmental dilution. On the other hand, higher levels of T-4-H(6)CDFs and Co-PCBs, especially low-chlorinated congeners such as 2378-T4CDF and T(4)CB77, were found in 3-month-old BfA nestling, suggesting specific exposure to these contaminants, possibly due to their higher transportability than high-chlorinated congeners. Estimated biomagnification factors of almost all the congeners in adults were apparently greater than those in nestlings, except 2378-T4CDF, T(4)CB77, and H-7-O8CDD/Fs. This could be due to preferential metabolism of 2378-T4CDF and T(4)CB77 and lower uptake efficiency of high-chlorinated congeners through the gastrointestinal tract in adults. Toxic equivalents in BfA and StA eggs estimated using WHO-avian toxic equivalency factors exceeded some toxicity thresholds for avian embryos, indicating possible adverse effects of DRCs to albatross embryos.
  • Nguyen Hung Minh, Tu Binh Minh, Natsuko Kajiwara, Tatsuya Kunisue, Hisato Iwata, Pham Hung Viet, Nguyen Phuc Cam Tu, Bui Cach Tuyen, Shinsuke Tanabet
    ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY 25 (10) 2700 - 2708 0730-7268 2006/10 [Peer-reviewed]
     Scientific journal 
    Commercial feeds for aquaculture and catfish samples were collected from the Mekong River Delta, Vietnam, for determination of polybrominated diphenyl ethers (PBDEs) and selected persistent organochlorines, including polychlorinated bi-phenyls (PCBs), DDT and its metabolites (DDTs), chlordane-related compounds (CHLs), hexachlorocyclohexane isomers (HCHs), and hexachlorobenzene (HCB). The most abundant contaminants were DDTs, with concentrations ranging from 10 to 700 ng/g lipid weight, followed by PCBs (1.0-80 ng/g), CHLs (< 0.01-8.2 ng/g), PBDEs (0.12-3.7 ng/g), HCHs (< 0.03-5.1 ng/g), and HCB (< 0.07-3.2 ng/g). Polybrominated diphenyl ethers were detected in all samples, suggesting their widespread contamination in the region. However, PBDE contamination levels in the present catfish specimens were low in comparison to levels worldwide. Interestingly, residue levels of all the contaminants were significantly higher in catfish collected near a municipal dumping site compared to farmed catfish. This suggests that runoffs from the dumping site during floods and rains may have brought pollutants to the surrounding areas. Contamination pattern in aquaculture feeds revealed elevated levels of PCBs and PBDEs in samples from foreign companies, perhaps implying their higher residues in some imported ingredients. Congener profiles of PBDEs and PCBs demonstrated similarity between the farmed catfish and the aquaculture feeds, suggesting these feeds as a major source of pollution to the farmed catfish. On the other hand, the PBDE and PCB profiles in the dumpsite catfish are clearly different from those of the farmed catfish, revealing their exposure to different sources. Risk assessment showed significantly higher intake of the contaminants by people who eat catfish cultured near the dumping areas. Further investigation regarding fate and occurrence of the contaminants in dumping sites is necessary.
  • Natsuko Kajiwara, Tatsuya Kunisue, Satoko Kamikawa, Yoko Ochi, Shinichi Yano, Shinsuke Tanabe
    MARINE POLLUTION BULLETIN 52 (9) 1066 - 1076 0025-326X 2006/09 [Peer-reviewed]
     Scientific journal 
    Blubber and liver samples were obtained for analysis of wide ranges of contaminants from killer whales (Orcinus orca) which were locked away in drifting sea ice on the coast of Rausu, the Shiretoko Peninsula in Eastern Hokkaido, Japan in February 2005. Among the organolialogen compounds analyzed, DDTs were the predominant contaminants with concentrations ranging from 28 to 220 mu g/g on a lipid-weight basis followed by PCBs and other organochlorine pesticides. PBDEs levels were two or three orders of magnitude lower than those of PCBs and DDTs. 2,3,7,8-Tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) derived by WHO mammal-TEF in killer whales were in the range of 110-440 pgTEQ/g. Mono-ortho coplanar PCBs contributed to 75-98% of total TEQs, indicating coplanar PCBs are significant contaminants for risk assessment in this species. The fact that hepatic residue levels of butyltins (from 13 to 770 ng/g wet weight) were much higher than those of phenyltins may be reflecting extensive use of tributyltin as antifouling paint. (c) 2006 Elsevier Ltd. All rights reserved.
  • Tatsuya Kunisue, Masayoshi Muraoka, Masako Ohtake, Agus Sudaryanto, Nguyen Hung Minh, Daisuke Ueno, Yumi Higaki, Miyuki Ochi, Oyuna Tsydenova, Satoko Kamikawa, Tomoyuki Tonegi, Yumi Nakamura, Hiroshi Shimomura, Junya Nagayama, Shinsuke Tanabe
    CHEMOSPHERE 64 (9) 1601 - 1608 0045-6535 2006/08 [Peer-reviewed]
     Scientific journal 
    Contamination levels of persistent organochlorines (OCs) such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), and chlordane compounds (CHLs) was examined in human breast milk collected during 2001-2004 from Fukuoka prefecture in Japan. The concentrations of OCs such as dioxins and related compounds, DDTs, CHLs and HCB in human breast milk from primiparae were comparable to or slightly higher than the data obtained during 1998, indicating that the levels of these contaminants in Japanese human breast milk have not decreased since 1998 and Japanese are continuously exposed to these chemicals, presumably via fish intake. In addition, OC levels in human breast milk from primiparae were significantly higher than those from multiparae, implying elimination of OCs via lactation. Furthermore, significant positive correlations were observed between levels of OCs in human breast milk and the age of primiparae. These results indicate that the mothers with higher age may transfer higher amounts of OCs to the first infant than to the infants born afterwards through breast-feeding, and hence the first born children might be at higher risk by OCs. (c) 2005 Elsevier Ltd. All rights reserved.
  • T Kunisue, MX Watanabe, H Iwata, T Tsubota, F Yamada, M Yasuda, S Tanabe
    ENVIRONMENTAL POLLUTION 140 (3) 525 - 535 0269-7491 2006/04 [Peer-reviewed]
     Scientific journal 
    The present study determined the contamination levels and congener-specific accumulation features of dioxins and related compounds (DRCs) in wild terrestrial mammals such as large Japanese field mice (LJFM), lesser Japanese moles (LJMs), and raccoon dogs (RDs) collected from Kanto region in Japan during 2001. The toxic equivalent quantity (TEQ) levels in the carcasses or adipose tissues were in the order of RDs >= LJMs > LJFM. Comparison of DRC congener profiles in the three species and principal component analysis (PCA) demonstrated a higher contribution of OCIDD, T(4)CB77, and P(5)CB118 in LJMs. Analysis of liver-adipose distribution of DRC congeners in RDs showed that livers contained significantly higher TEQs than adipose tissues, indicating that liver is a depository organ and critical for determining the toxicokinetics of DRCs. As for most T-4, P-5, H6CDD/DFs and for P(5)CB126, H(6)CB169 and mono-ortho PCB congeners, their liver/adipose concentration ratios in RDs revealed a tendency to increase with hepatic TEQ levels, suggesting TEQ-dependent hepatic sequestration. (c) 2005 Elsevier Ltd. All rights reserved.
  • A Sudaryanto, T Kunisue, N Kajiwara, H Iwata, TA Adibroto, P Hartono, S Tanabe
    ENVIRONMENTAL POLLUTION 139 (1) 107 - 117 0269-7491 2006/01 [Peer-reviewed]
     Scientific journal 
    This study determined concentrations of polychlorinated biphenyls (PCBs) and organochlorine compound (OC) pesticides in the milk samples of women from the general population in four locations of Indonesia. The most prevalent residues of OCs were DDTs, PCBs and hexachlorocyclohexane isomers (HCHs), whereas other OCs such as chlordane compounds (CHLs), tris(4-chlorophenyl)methane and hexachlorobenzene were lower. The levels of OCs varied between locations and individuals, with DDTs higher in suburban and rural areas than urban localities, may be due to the differences in food habits and sources between the individuals and locations. Data from Purwakarta site indicated continuing DDT exposure, which may confirm recent usage of DDT in Indonesia. A positive correlation was observed between concentration of OCs in human milk and age of mothers, primiparas women having higher OCs than multiparas, suggesting these parameters play an important role influencing the OC burdens in lactating women. Some individuals accumulated DDTs and HCHs in breast milk close to or even higher than the TDI (tolerable daily intake) guidelines proposed by Health Canada. (c) 2005 Elsevier Ltd. All rights reserved.
  • A Sudaryanto, T Kunisue, S Tanabe, M Niida, H Hashim
    ARCHIVES OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY 49 (3) 429 - 437 0090-4341 2005/10 [Peer-reviewed]
     Scientific journal 
    This study determined the concentrations of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides, and tris(4-chlorophenyl) methane (TCPMe) in human breast milk samples collected in 2003 from primipara mothers living in Penang, Malaysia. OCs were detected in all the samples analyzed with DDTs, hexachlorocyclohexane isomers (HCHs), and PCBs as the major contaminants followed by chlordane compounds (CHLs), hexachlorobenzene (HCB), and TCPMe. The residue levels of DDTs, HCHs, and CHLs were comparable to or higher than those in general populations of other countries, whereas PCBs and HCB were relatively low. In addition, dioxins and related compounds were also detected with a range of dioxin equivalent concentrations from 3.4 to 24 pg-TEQs/g lipid wt. Levels of toxic equivalents (TEQs) were slightly higher than those in other developing countries but still much lower than those of industrialized nations. One donor mother contained a high TEQs level, equal to the mean value in human breast milk from Japan, implying that some of the residents in Malaysia may be exposed to specific pollution sources of dioxins and related compounds. No association was observed between OCs concentrations and maternal characteristics, which might be related to a limited number of samples, narrow range of age of the donor mothers, and/or other external factors. The recently identified endocrine disrupter, TCPMe, was also detected in all human breast milk samples of this study. A significant positive correlation was observed between TCPMe and DDTs, suggesting that technical DDT might be a source of TCPMe in Malaysia. The present study provides a useful baseline for future studies on the accumulations of OCs in the general population of Malaysia.
  • T Kunisue, S Nakanishi, M Watanabe, T Abe, S Nakatsu, S Kawauchi, A Sano, A Horii, Y Kano, S Tanabe
    ENVIRONMENTAL POLLUTION 136 (3) 465 - 476 0269-7491 2005/08 [Peer-reviewed]
     Scientific journal 
    Concentrations of persistent organochlorines (OCs) such as polychlorinated dibenzo-p-dioxin (PCDDs), dibenzofurans (PCDFs), biphenyls, dichlorodiphenyltrichloroethane and their metabolites (DDTs), hexachlorocyclohexane isomers, hexachlorobenzene, and chlordane compounds were determined in genital organs of pet dogs and cats and pet foods from Japan. Levels of OCs in dogs were relatively lower than those in cats, while residue levels in their diets were almost similar, implying that accumulation and elimination mechanisms of these contaminants are different between dogs and cats. When bioconcentration factors (BCFs) were estimated from concentrations of OCs in dogs, cats, and their diets, BCFs of all the OCs except PCDD/DFs exceeded 1.0 in cats. On the other hand, in all the dogs, BCFs of DDTs were below 1.0, suggesting that dogs do not bioconcentrate DDTs. Furthermore, BCFs of all the OCs except PCDD/DFs in dogs were notably lower than those in cats, suggesting that dogs have higher metabolic and elimination capacity for these contaminants than cats. When residue levels of OCs in livers, adipose tissue, and genital organs of two pet dogs were examined, hepatic sequestration of PCDD/DFs and oxychlordane was observed. (c) 2005 Elsevier Ltd. All rights reserved.
  • T Kunisue, M Someya, F Kayama, Y Jin, S Tanabe
    ENVIRONMENTAL POLLUTION 131 (3) 381 - 392 0269-7491 2004/10 [Peer-reviewed]
     Scientific journal 
    The present study determined the concentrations of organochlorines (OCs) such as polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs), hexachlorobenzene (HCB) and tris(4-chlorophenyl)methane (TCPMe) in human breast milk collected from primiparae in Dalian and Shenyang, northeastern China during 2002. In addition, dioxins and related compounds in pooled samples of human breast milk from Dalian and Shenyang were also analyzed. OCs were detected in all the human breast milk samples analyzed in this study. The predominant contaminants in human breast milk were HCHs, DDTs and HCB, and the levels were relatively higher than those in other countries. On the other hand, concentrations of dioxins and related compounds, PCBs, and CHLs were relatively low. Concentrations of OCs in human breast milk from Dalian, which is located along the coast of Bo Hai Strait, were significantly higher than those from Shenyang, implying that the residents in Dalian might be mainly exposed to these contaminants from seafood. When the relationship between concentrations of OCs in human breast milk and age of primiparae was examined, no significant correlation was observed. This might be caused by the limited sample numbers and narrow range of mother's age and/or recent ban of DDT and HCH production and use. Significant correlation between concentrations of TCPMe and DDTs in human breast milk suggested that technical DDT might be a source of TCPMe in the Chinese population. When daily intakes of DDTs and HCHs to infants through human breast milk were estimated, human breast milk from Dalian showed significantly higher contribution than Shenyang, implying that infants in Dalian might be at higher risk by these contaminants. (C) 2004 Elsevier Ltd. All rights reserved.
  • NH Minh, M Someya, TB Minh, T Kunisue, H Iwata, M Watanabe, S Tanabe, PH Viet, BC Tuyen
    ENVIRONMENTAL POLLUTION 129 (3) 431 - 441 0269-7491 2004/06 [Peer-reviewed]
     Scientific journal 
    Despite the ban on persistent organochlorines (OCs) in most of the developed nations, their usage continued until recently in many Asian developing countries including Vietnam, for agricultural purposes and vector-borne disease eradication programs. In this study. we collected human breast milk samples from the two big cities in Vietnam: Hanoi (n = 42) and Hochiminh (n = 44) and determined the concentrations of persistent OCs such as PCBs, DDT and its metabolites (DDTs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB). chlordane compounds (CHLs) and tris-4-chlorophenyl-methane (TCPMe). The contamination pattern of OCs was in the order of DDTs > PCBs > HCHs > CHLsapproximate toHCBapproximate toTCPMe. Compilation of available data indicated that DDT residue levels in human breast milk from Vietnam were among the highest values reported for Asian developing countries as well as developed nations. This result suggests recent usage of DDTs in both north and south Vietnam. Interestingly, in both cities, the p,p'-DDT portion was higher in multiparas than those in primiparas. Considering the fact that the interval between the first and the second child of a mother in Vietnam is usually short, this result probably indicates continuous intake of DDTs in the population. Analysis of infant exposure to DDTs via breast milk suggested that the daily intake rates for number of individuals are close to or above the threshold for adverse effects which may raise concern on children health. (C) 2004 Elsevier Ltd. All rights reserved.
  • T Kunisue, M Someya, Monirith, I, M Watanabe, TS Tana, S Tanabe
    ARCHIVES OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY 46 (3) 405 - 412 0090-4341 2004/04 [Peer-reviewed]
     Scientific journal 
    The present study determined the concentrations of persistent organochlorines (OCs) such as DDT and its metabolites (DDTs), polychlorinated biphenyls (PCBs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), chlordane compounds (CHLs), tris(4-chlorophenyl) methane (TCPMe), and tris(4-chlorophenyl)methanol (TCPMOH) in human breast milk from Cambodia. DDTs, PCBs, HCHs, HCB, CHLs, and TCPMe were detected in almost all the human breast milk samples analyzed, and the concentrations ranged from 310 to 11,000, 6.0 to 87, <0.12 to 21, <0.12 to 8.1, <0.12 to 5.3, and 2.9 to 70 ng/g lipid wt, respectively. TCPMOH was detected in only 10 among 36 samples. Concentrations of DDTs in human breast milk from Cambodia were notably higher than those from developed countries and comparable to those from other developing countries, where usage of DDT for agricultural and public health purposes has been suspected to be continuing still, implying the recent usage of DDT in Cambodia. On the other hand, concentrations of PCBs, HCHs, HCB, and CHLs in human breast milk from Cambodia were 1-2 orders of magnitude less than those from other countries, indicating that Cambodia is one of the less contaminated countries by these OCs. Significant correlation between concentrations of TCPMe and DDTs in human breast milk suggested that exposure to DDT is the source of TCPMe in Cambodian residents. Concentrations of OCs in human breast milk tended to decrease with an increase in the number of children, implying that the first infant would be exposed to higher levels of OCs from breast milk and might be at higher risk by these contaminants, especially DDTs in Cambodia. To our knowledge, this is the first comprehensive study on the residue levels of OCs in human breast milk from Cambodia.
  • S Tanabe, M Watanabe, TB Minh, T Kunisue, S Nakanishi, H Ono, H Tanaka
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 38 (2) 403 - 413 0013-936X 2004/01 [Peer-reviewed]
     Scientific journal 
    Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (coplanar PCBs) were determined in five albatross species collected from the North Pacific and Southern Oceans to assess the north-south differences in residue levels, accumulation patterns, and toxic potential. Black-footed and Laysan albatrosses from the North Pacific Ocean contained higher levels of PCDD/Fs and coplanar PCBs than albatrosses from the Southern Ocean, indicating that emission sources of these contaminants were predominant in the northern hemisphere. Residue levels in albatrosses from the remote North Pacific Ocean far from the point source of pollution were comparable to or higher than those in terrestrial and coastal birds from contaminated areas in developed nations, suggesting the specific exposure and accumulation of PCDD/Fs and coplanar PCBs in albatross. The long life span and ingestion of plastic resin pellets by albatrosses could be the plausible explanations for the elevated accumulation of persistent and lipophilic contaminants including PCDD/Fs and coplanar PCBs in these birds. Relative proportions of PCDFs and coplanar PCBs in albatross were higher than those observed in birds inhabiting terrestrial and coastal areas, suggesting that these toxic chemicals may have higher transportability by air and water than PCDDs. Congener patterns of PCDD/Fs in albatross showed less variability as compared to those in terrestrial species, indicating that contamination patterns of PCDD/Fs were similar within the open ocean environment. Contributions of PCDD/Fs to total TEQs in albatrosses from the open ocean were generally lower than those in terrestrial birds, suggesting different toxic potency of PCDD/Fs and coplanar PCBs on animals inhabiting open ocean and terrestrial environment. Whereas albatrosses from southern oceans retained lower TEQ concentrations, possible adverse effects of PCDD/Fs and coplanar PCBs to black-footed and Laysan albatrosses of the North Pacific Ocean may be suspected from TEQ levels.
  • Monirith, I, T Kunisue, H Iwata, S Tanabe, TS Tana
    MARINE POLLUTION BULLETIN 46 (10) 1341 - 1348 0025-326X 2003/10 [Peer-reviewed]
     Scientific journal
  • NH Minh, TB Minh, M Watanabe, T Kunisue, Monirith, I, S Tanabe, S Sakai, A Subramanian, K Sasikumar, PH Viet, BC Tuyen, TS Tana, MS Prudente
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 37 (8) 1493 - 1502 0013-936X 2003/04 [Peer-reviewed]
     Scientific journal 
    Open landfill dumping areas for municipal wastes in Asian developing countries have recently received particular attention with regard to environmental pollution problems. Because of the uncontrolled burning of solid wastes, elevated contamination by various toxic chemicals including dioxins and related compounds in these dumping sites has been anticipated. In this study, concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (PCBs) were determined in soils from dumping sites in the Philippines, Cambodia, India, and Vietnam. Residue concentrations of PCDD/Fs and coplanar PCBs in dumping site soils were apparently greater than those in soils collected in agricultural or urban areas far from dumping sites, suggesting that dumping sites are potential sources of PCDD/Fs and related compounds. Observed PCDD/F concentrations in soils from dumping sites in the Philippines and Cambodia were comparable or higher than those reported for dioxin-contaminated locations in the world (e.g., near the municipal waste incinerators and open landfill dumping sites). Homologue profiles of PCDD/Fs in dumping site soils from the Philippines and, to a lesser extent, from Cambodia and India reflected patterns of samples representing typical emissions, while profiles of agricultural or urban soils were similar to those of typical environmental sinks. This result suggests recent formation of PCDD/Fs in dumping site areas and that open dumping sites are a potential source of dioxins in Asian developing countries. Uncontrolled combustions of solid wastes by waste pickers, generation of methane gas, and low-temperature burning can be major factors for the formation of dioxins in dumping sites. Elevated fluxes of PCDD/Fs to soils in dumping sites were encountered in the Philippines, Cambodia, India, and Vietnam-Hanoi, and these levels were higher than those reported for other countries. Considerable loading rates of PCDD/Fs in the dumping sites of these countries were observed, ranging from 20 to 3900 mg/yr (0.12-35 mg TEQ/yr). PCDD/F concentrations in some soil samples from the Philippines, Cambodia, India, and Vietnam-Hanoi exceeded environmental guideline values, suggesting potential health effects on humans and wildlife living near these dumping sites. The estimated intakes of dioxins via soil ingestion and dermal exposure for children were higher than those for adults, suggesting greater risk of dioxin exposure for children in dumping sites. To our knowledge, this is the first comprehensive study on PCDD/Fs contamination in open dumping sites of Asian developing countries. On the basis of the result of this study, we have addressed a new environmental issue that open dumping sites are potential sources of PCDD/Fs and related compounds, and dioxin contamination in dumping sites may become a key environmental problem in developing countries.
  • T Kunisue, M Watanabe, A Subramanian, A Sethuraman, AM Titenko, Qui, V, M Prudente, S Tanabe
    ENVIRONMENTAL POLLUTION 125 (2) 157 - 172 0269-7491 2003 [Peer-reviewed]
     Scientific journal 
    Concentrations of organochlorine contaminants including polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs), hexachlo to benzene (HCB) were determined in the resident and migratory birds, which were collected from India, Japan, Philippines, Russia (Lake Baikal) and Vietnam. Accumulation patterns of organochlorine concentrations in resident birds suggested that the predominant contaminants of each country were as follows: Japan-PCBs Philippines-PCBs and CHLs, India-HCHs and DDTs, Vietnam-DDTs, and Lake Baikal-PCBs and DDTs. The migratory birds from Philippines and Vietnam retained mostly the highest concentrations of DDTs among the organochlorines analyzed, indicating the presence of stopover and breeding grounds of those birds in China and Russia. On the other hand, migratory birds from India and Lake Baikal showed different patterns of organochlorine residues, reflecting that each species has inherent migratory routes and thus has exposure to different contaminants. Species which have breeding grounds around the Red Sea and Persian Gulf showed high levels of PCBs, indicating the presence of areas heavily polluted by PCBs in the Middle East. (C) 2003 Elsevier Science Ltd. All rights reserved.
  • TB Minh, T Kunisue, NTH Yen, M Watanabe, S Tanabe, ND Hue, Qui, V
    ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY 21 (10) 2108 - 2118 0730-7268 2002/10 [Peer-reviewed]
     Scientific journal 
    Concentrations of persistent organochlorines (OCs), such as polychlorinated biphenyls (PCBs). 1,1,1 trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), and chlordane compounds (CHLs), were determined in whole-body homogenates of resident and migratory birds collected from the Red River estuary, North Vietnam, during March and October 1997. Contamination pattern was in the order of DDTs > PCBs > HCHs > CHLs > HCB in both resident and migratory birds. Residue concentrations, according to the feeding habit, showed little variability, which may reflect relatively similar trophic levels of the bird species analyzed. Resident birds accumulated greater concentrations of DDTs as compared to migrants. In contrast, HCH residues were greater in migratory species. Higher proportion, of p,p'-DDT to total DDT concentrations were found in many species of residents and migrants, indicating recent exposure to technical DDT in northern Vietnam. Congener-specific PCB analysis showed the predominance of penta- and hevachlorobiphenyls in all the species analyzed. Estimation of hepatic microsomal enzyme activities suggested higher metabolic capacity for PCB congeners in shore birds from Vietnam as compared to higher-trophic predator birds and marine mammals. Comparison of OC residues in avian species in Asia-Pacific revealed that DDT residues in resident birds in North Vietnam are among the highest values reported for the countries surveyed, suggesting recent usage of DDT in Vietnam. Available data for birds, fish, and bivalves from the recent Asia-Pacific Mussel Watch Program suggested that Vietnam might be a potential source of DDT contamination in Asian developing countries. To our knowledge, this is the first study of the OC accumulation in avian species from Vietnam.
  • KQ Sakamoto, T Kunisue, M Watanabe, Y Masuda, H Iwata, S Tanabe, F Akahori, M Ishizuka, A Kazusaka, S Fujita
    ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY 21 (4) 842 - 847 0730-7268 2002/04 [Peer-reviewed]
     Scientific journal 
    Polychlorinated biphenyls (PCBs), including coplanar congeners, hexachlorocyclohexane isomers, chlordane-related compounds, and hexachlorobenzene, were found in the breast muscle of Steller's sea eagles (SSE) and white-tailed sea eagles (WSE) threatened species, collected in Hokkaido, Japan, during the two years from 1998 to 1999. Both PCBs and DDTs were the most notable compounds, with concentrations one to two orders of magnitude higher than the other compounds, that is, from 120 to 39,000 and from 68 to 15,000 ng/g wet weight, respectively. Non-ortho (International Union of Pure and Applied Chemistry [IUPAC] 77, 126, and 169) and mono-ortho (IUPAC 105, 118, and 156)-substituted coplanar PCB congeners amounted to 9.2 to 740 pg/g of 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents derived from the World Health Organization, Paris, France (WHO), toxic equivalent factors. The atmospheric PCBs and DDTs in eastern Siberian cities, such as Khabarovsk and Magadan, have been reported to be much higher than Hokkaido and the North Pacific. Thus, we speculated that the eagles might have been contaminated in these areas, where they spend most of the year except winter, which they spend in eastern Siberia. Adult eagles accumulated more PCBs and DDTs than younger ones. The patterns of PCB congeners were also found to change, depending on the age of the eagle examined; adult eagles showed relatively higher proportions of highly chlorinated PCBs than juvenile eagles did. This difference would be related to the efficiency of the excretion and the metabolism of each PCB congener in the eagles.
  • T Kunisue, TB Minh, K Fukuda, M Watanabe, S Tanabe, AM Titenko
    ENVIRONMENTAL SCIENCE & TECHNOLOGY 36 (7) 1396 - 1404 0013-936X 2002/04 [Peer-reviewed]
     Scientific journal 
    Concentrations of persistent organochlorines (OCs) such as polychlorinated biphenyls (PCBs), DDT and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), and chlordane compounds (CHLs) were determined in whole body soft tissue homogenates and in muscles of resident and migratory birds collected from Lake Baikal, Russia. The residue pattern in both resident and migratory birds was in the following order: PCBs > DDTs > HCHs > CHLs. OC concentrations in migratory birds varied, depending on the feeding habit. The maximum levels of OCs were found inpiscivores, followed by insectivores, omnivores, and herbivores. OC residue levels in Lake Baikal birds were lower than those in the Great Lakes region as well as in other lakes in Europe and Japan. Concentrations of HCHs and DDTs in most of the migratory birds collected in the spring were higher than for those collected in the autumn, indicating a notable accumulation in wintering grounds. Compilation and analysis of the available data in fish and birds from Asia suggested that the tropical and subtropical regions in south Asian countries may be a source of pollution for the wintering accumulation of migratory birds from Lake Baikal. Relatively higher compositions of alpha- and gamma-HCH in total HCHs, p,p'-DDT in total DDTs were observed in some migratory species, indicating recent exposure to HCHs and DDTs in Lake Baikal or wintering areas. PCB isomer patterns were different between residents and migrants,with the predominance of lower chlorinated congeners in migratory species, suggesting recent PCB accumulation in stopover sites during wintering. TEQ concentrations of toxic non- and mono-ortho coplanar PCBs in common terns from Lake Baikal were comparable to those reported in some species from Japan, the United States, and Europe. Relative contributions of non-ortho coplanar congeners to toxic equivalents (TEQs) were predominant, in which CB-126 accounted for the highest toxicity contribution. Estimated TEQ concentrations in the common tern from Lake Baikal exceeded the levels associated with enzyme induction in bald eagles. To our knowledge, this is the first comprehensive study showing the seasonal variations of OC accumulation in the birds from Lake Baikal.

Books etc

  • The Handbook of Environmental Chemistry
    Kunisue, T, Tanabe, S (Joint work, Dioxin and Related Compounds - Contamination issues in Asian developing countries)
    vol 49. Springer 2016 9783319238883 301-334

Conference Activities & Talks

MISC

Awards & Honors

  • 2018/05 日本環境化学会 第27回環境化学学術賞
     
    受賞者: 国末 達也
  • 2015/04 愛媛大学理学部 ベストレクチャー賞
     
    受賞者: 国末 達也
  • 2010 Elsevier Highly Cited Author Award 2007-2010
     
    受賞者: KUNISUE Tatsuya

Research Grants & Projects

  • 新規環境汚染物質の水圏生物濃縮機構・時空間トレンドの解明とリスク評価
    日本学術振興会:基盤研究(A) 一般
    Date (from‐to) : 2019/04 -2022/03 
    Author : 国末 達也
  • ベトナムの廃棄物および工業・生活排水に由来する有害化学物質の動態とリスク評価
    日本学術振興会:国際共同研究加速基金(国際共同研究強化(B))
    Date (from‐to) : 2018 -2021/03 
    Author : 国末 達也
  • 多様な動物種に 適用できる内因性ホルモンの高精度分析法の開発
    日本学術振興会:挑戦的萌芽研究
    Date (from‐to) : 2014 -2017/03 
    Author : 国末 達也
  • 室内残留性化学物質の探索と影響評価-コンパニオンアニマルを指標動物として-
    日本学術振興会:基盤研究(B)
    Date (from‐to) : 2013 -2016/03 
    Author : 国末 達也

Social Contribution

  • 内分泌かく乱化学物質
    Date (from-to) : 2019/01
    Role : Lecturer
    Sponser, Organizer, Publisher  : 高大連携授業
    Event, Program, Title : 愛媛県立松山南高等学校スーパーサイエンスハイスクール環境教育学
    High school students 愛媛大学
  • 内分泌かく乱化学物質
    Date (from-to) : 2018/01
    Role : Lecturer
    Sponser, Organizer, Publisher  : 高大連携授業
    Event, Program, Title : 愛媛県立松山南高等学校スーパーサイエンスハイスクール環境教育学
    High school students 愛媛大学
  • 生命と環境における分子科学
    Date (from-to) : 2017/07
    Role : Lecturer
    Event, Program, Title : 平成29年度教員免許状更新講習
    Teachers 愛媛大学
  • 内分泌かく乱化学物質
    Date (from-to) : 2017/02
    Role : Lecturer
    Sponser, Organizer, Publisher  : 高大連携授業
    Event, Program, Title : 「愛媛県立松山南高等学校スーパーサイエンスハイスクール環境教育学」
    High school students 愛媛大学
  • 環境汚染物質化学
    Date (from-to) : 2016/09/23-2016/09/27
    Role : Lecturer
    Sponser, Organizer, Publisher  : 鳥取大学
    Event, Program, Title : 集中講義
    College students
  • 環境汚染物質化学
    Date (from-to) : 2015/09/24-2015/09/29
    Role : Lecturer
    Sponser, Organizer, Publisher  : 鳥取大学
    Event, Program, Title : 集中講義
    College students
  • LC-MS/MSを用いた甲状腺ホルモン測定と環境毒性学への応用
    Date (from-to) : 2014/12
    Role : Lecturer
    Sponser, Organizer, Publisher  : 本化学会中国四国支部 愛媛地区化学講演会
    愛媛大学

愛媛大学教員活動実績

教育活動(B)

担当授業科目(B01)

  • 2019, the first semester, under graduate, 卒業研究Ⅰ
  • 2019, the first semester, master course, 環境化学特論
  • 2019, the first semester, master course, 環境化学特論
  • 2019, the first semester, master course, 化学ゼミナールⅠ
  • 2019, the first semester, master course, 化学ゼミナールⅢ
  • 2019, the first semester, master course, 分子科学課題演習I
  • 2019, the first semester, under graduate, 環境科学セミナーIII
  • 2019, the first semester, under graduate, コース英語I


Copyright © MEDIA FUSION Co.,Ltd. All rights reserved.