Publications by authors named "Masanori Terasaki"

27 Publications

  • Page 1 of 1

Degradation of the endocrine-disrupting 4-nonylphenol by ferrate(VI): biodegradability and toxicity evaluation.

Environ Sci Pollut Res Int 2022 Mar 27;29(13):18882-18890. Epub 2021 Oct 27.

Course of Civil and Environmental Engineering, Department of System Innovation Engineering, Faculty of Science and Engineering, Iwate University, Ueda 4-3-5, Morioka, 020-8551, Japan.

4-Nonylphenol (4-NP) is an endocrine-disrupting and persistent chemical and is partially degraded in conventional wastewater treatment processes. Ferrate(VI) can be used as an environment-friendly oxidizing agent to mediate 4-NP degradation. Thus, this paper evaluates the biodegradability of 4-NP and its degradation products after the addition of ferrate(VI). The biodegradability was examined using NP labeled with C as a tracer and activated sludge microorganisms as an inoculum. The addition of ferrate(VI) to the 4-NP solution spiked with the tracer resulted in no remarkable decrease in the concentration of C, indicating incomplete mineralization of 4-NP and formation of degradation products. The degradation products from 4-NP with Fe(VI) were estimated based on mass spectra, which detected a unique peak at m/z 223 at low intensity. Four hydrogen atoms might have been added to 4-NP by degradation with Fe(VI). In addition, the effect of ferrate(VI) concentration on the estrogenic activity of 4-NP in an aqueous solution was investigated using a yeast bioassay. The results show that estrogenic activity was significantly decreased at a mass ratio of Fe(VI) to 4-NP greater than or equal to 2.5.
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http://dx.doi.org/10.1007/s11356-021-17167-1DOI Listing
March 2022

Occurrence and AhR activity of brominated parabens in the Kitakami River, North Japan.

Chemosphere 2020 Jun 7;249:126152. Epub 2020 Feb 7.

Graduate School of Arts and Sciences, Iwate University, Japan. Electronic address:

Parabens are used as preservatives in pharmaceuticals and personal care products (PPCPs). Parabens react with aqueous chlorine, which is used in disinfection processes, leading to the formation of halogenated parabens. In the presence of Br, parabens and HOBr (formed via oxidation of Br) can react to form brominated parabens. Brominated parabens may result in pollution of river water through effluent discharge from sewage treatment plants. The present study involved measuring brominated paraben concentrations in the Kitakami River, northern Japan, which flows through urban and agricultural areas. Aryl hydrocarbon receptor (AhR) agonist activity was also assessed using a yeast (YCM3) reporter gene and HepG2 ethoxyresorufin O-deethylase (EROD) assays. Dibrominated methylparaben (Br2MP), ethylparaben (Br2EP), propylparaben (Br2PP), butylparaben (Br2BP), and benzylparaben (Br2BnP), and monobrominated benzylparaben (Br1BnP) were detected in 25-100% of river samples during the sampling period from 2017 to 2018 at median concentrations of 8.1-28 ng/L; the highest concentrations were measured during the low flow season (November) in urban areas (P < 0.01). In the yeast assay, 12 compounds exhibited AhR activity (activity relative to β-naphthoflavone; 4.4 × 10-7.1 × 10). All monobrominated parabens exhibited higher activity than their parent parabens, however, further bromination reduced or eliminated their activity. In the EROD assay, five compounds caused significant induction of CYP1A-dependent activity at 100 μM (P < 0.05). Monobrominated i-butylparaben (Br1iBP) and s-butylparaben (Br1sBP), Br1BnP, and Br2BP exhibited activity in both yeast and EROD assays. We found novel aspects of brominated parabens originating from PPCPs.
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http://dx.doi.org/10.1016/j.chemosphere.2020.126152DOI Listing
June 2020

Screening data for the endocrine disrupting activities of 583 chemicals using the yeast two-hybrid assay.

Data Brief 2018 Dec 23;21:2543-2546. Epub 2018 Nov 23.

National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-8506, Japan.

We screened 583 chemicals for receptor binding activity to the human estrogen receptor (hER), the Japanese medaka estrogen receptor (medER), and the aryl hydrocarbon receptor (AhR) using the yeast two-hybrid assay. The substances tested included substances that could potentially be produced unintentionally by industrial processes, such as halogenated steroids and phenols. Antagonistic effects on hER and the androgen receptor were also screened. The test chemicals were selected for screening on the basis of chemical structure associated with possible estrogen receptor binding activity. The current study presents the report on the screening of 583 chemicals for different kinds of endocrine disrupting activity.
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http://dx.doi.org/10.1016/j.dib.2018.11.071DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6288393PMC
December 2018

Estrogen agonistic/antagonistic activity of brominated parabens.

Environ Sci Pollut Res Int 2018 Jul 26;25(21):21257-21266. Epub 2018 Jun 26.

Department of Environmental Sciences, Faculty of Humanities and Social Sciences, Iwate University, 3-18-34 Ueda, Morioka, 020-8550, Japan.

The estrogen agonistic/antagonistic activity of 16 brominated by-products of parabens was assessed by using a yeast two-hybrid assay transfected with the human estrogen receptor α. Characterization of synthetic compounds including novel brominated parabens was performed using H-NMR spectroscopy and high-resolution mass spectrometry. For the agonist assay, five C-C alkylparabens exhibited significant activity (P < 0.05) relative to that of 17β-estradiol, ranging from 3.7 × 10 to 7.1 × 10. In contrast, none of the brominated alkyl parabens exhibited agonistic activity. In the antagonist assay, 12 brominated alkylparabens and butylparaben exhibited significant antagonistic activity (P < 0.05). Their antagonistic activity relative to 4-hydroxytamoxifen ranged from 0.11 to 2.5. The antagonist activity of C-C alkylparabens increased with the number of bromine substitutions. Benzylparaben exhibited both agonistic and antagonistic activity, and these activities dissipated or were weakened with increased bromination. Thus, increased bromination appeared to attenuate the estrogen agonistic activity of most parabens such that it resulted in increased antagonistic activity, a feature of parabens that had not been previously described.
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http://dx.doi.org/10.1007/s11356-018-2600-3DOI Listing
July 2018

Size distribution and sources of 37 toxic species of particulate polycyclic aromatic hydrocarbons during summer and winter in Baoshan suburban area of Shanghai, China.

Sci Total Environ 2016 Oct 17;566-567:1519-1534. Epub 2016 Jun 17.

Faculty of Humanities and Social Sciences, Iwate University, 3-18-34 Ueda, Morioka City, Iwate 020-8550, Japan.

The objectives of this study were to assess the size-segregated distribution and sources of 37 different species of particulate polycyclic aromatic hydrocarbons (PAHs) in a suburban area of Shanghai metropolitan City, China. The ambient particulate sampling was carried out on the rooftop of a five-stories building in Baoshan campus of Shanghai University. An Andersen high-volume air sampler was employed to collect ambient size-segregated particulate matter during summer of August to September and winter of November to December 2015. The high toxic PAHs were determined by a gas chromatography mass spectrometry. The concentrations of total PAHs in suspended particulate matter (SPM) and PM1.1 (suspended particulate matter below 1.1μm in diameter) in the suburban area of Shanghai were 4.58-14.5ng/m(3) and 1.82-8.56ng/m(3), respectively in summer, and 43.6-160ng/m(3) and 23.2-121ng/m(3), separately in winter. 1,8-Naphthalic anhydride (1,8-NA) showed the highest concentration among 37 different species of PAHs in the suburban area of Shanghai. The concentrations of high molecular PAHs (e.g. 5-6 ring PAHs) followed a nearly unimodal size distribution with the highest peaks in PM1.1. The diagnostic ration qualitatively indicated that PAHs in SPM of Shanghai were mainly derived from motor-vehicle or petroleum combustion in summer and from coal and biomass combustion in winter. According to the calculated toxicity equivalency factors based on the methods of Nisbet and Lagoy and the potency equivalency factors (PEF) recommended by U.S. EPA, the highest contributors in the total carcinogenicity of the PAHs in SPM and PM1.1 were dibenzo[a,h]pyrene (46.2% and 45.0% in summer), benzo[a]pyrene (44.4% and 43.8% in winter) and benz[j]aceanthrylene (80.2% and 83.1% in summer and 83.1% and 84.0% in winter), respectively. Therefore, benzo[a]pyrene seemed to be a lower contributor than other carcinogenic PAHs.
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http://dx.doi.org/10.1016/j.scitotenv.2016.06.039DOI Listing
October 2016

In Vitro Transformation of Chlorinated Parabens by the Liver S9 Fraction: Kinetics, Metabolite Identification, and Aryl Hydrocarbon Receptor Agonist Activity.

Chem Pharm Bull (Tokyo) 2016 ;64(6):650-4

Department of Environmental Sciences, Faculty of Humanities and Social Sciences, Iwate University.

We investigated the kinetics of in vitro transformation of a dichlorinated propyl paraben (2-propyl 3,5-dichloro-4-hydroxybenzoate; Cl2PP) by the rat liver S9 fraction and assessed the aryl hydrocarbon receptor (AhR) agonist activity of the metabolite products identified in HPLC and GC/MS analysis and by metabolite syntheses. The results indicated that the chlorination of Cl2PP reduced its degradation rate by approximately 40-fold. Two hydroxylated metabolite products showed AhR agonist activity of up to 39% of that of the parent Cl2PP when assessed in a yeast (YCM3) reporter gene assay. The determination of the metabolic properties of paraben bioaccumulation presented here provides further information on the value of risk assessments of chlorinated parabens as a means to ensure human health and environmental safety.
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http://dx.doi.org/10.1248/cpb.c15-00977DOI Listing
January 2017

Studies on size distribution and health risk of 37 species of polycyclic aromatic hydrocarbons associated with fine particulate matter collected in the atmosphere of a suburban area of Shanghai city, China.

Environ Pollut 2016 Jul 14;214:149-160. Epub 2016 Apr 14.

Faculty of Humanities and Social Sciences, Iwate University, 3-18-34 Ueda, Morioka City, Iwate 020-8550, Japan.

Polycyclic aromatic hydrocarbons (PAHs) in suspended particulate matter (SPM) contribute significantly to health risk. Our objectives were to assess the size distribution and sources of 26 PAHs and 11 polycyclic aromatic compounds (PACs) in SPM in the suburban area, Shanghai city, China. Air sampling was carried out on the rooftop of a five-stories building in the campus of Shanghai University. An Andersen high-volume air sampler was employed to collect ambient size-segregated particles from August to September 2015. The toxic particulate PAHs were determined by the gas chromatography mass spectrometry. The concentrations of total PAHs (TPAHs) in SPM and PM1.1 (suspended particulate matter below 1.1 μm) were in the ranges of 4.58-14.5 ng m(-3) and 1.82-8.56 ng m(-3), respectively. 1,8-naphthalic anhydride showed the highest concentrations among 37 species of PAHs and PACs ranging 7.76-47.9 ng m(-3) and 1.50-17.6 ng m(-3) in SPM and PM1.1, respectively. The concentrations of high molecular weight 5-6 ring PAHs followed a nearly unimodal size distribution with the highest peak in PM1.1, while other lower molecular weight PAHs were not dependent on particle sizes. The toxicity analysis indicated that the carcinogenic potency of particulate PAHs primarily existed in PM1.1. Regarding meteorological parameters and other pollutants, the positive effect of humidity and NO2 over PAHs was confirmed. Diagnostic ration indicated that the particulate PAHs in Shanghai were mainly derived from motor-vehicle or petroleum combustion. The highest benzo[a]pyrene equivalent (BaPeq) in SPM and PM1.1 were 2.15 ng m(-3) and 1.43 ng m(-3) calculated by the toxicity equivalency factor, and 69.31 ng m(-3) and 47.81 ng m(-3) estimated by the potency equivalency factors, respectively. The highest contributors in the total carcinogenicity of the particulate PAHs were dibenzo[a,h]pyrene (46.2% and 45.0%) and benz[j]aceanthrylene (80.2% and 83.1%), respectively while benzo[a]pyrene is lower contributor than other carcinogenic PAHs.
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http://dx.doi.org/10.1016/j.envpol.2016.04.002DOI Listing
July 2016

Evaluation of sensitizers found in wastewater from paper recycling areas, and their activation of the aryl hydrocarbon receptor in vitro.

Sci Total Environ 2014 Sep 17;493:156-61. Epub 2014 Jun 17.

Research Center for Environmental Risk, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-8506, Japan.

The in vitro potential of sensitizers and related compounds (SRCs) originating from impurities in waste paper in activating the human aryl hydrocarbon receptor (AhR) α was assessed using yeast reporter gene as well as cytochrome P450 (CYP)1A1 and ethoxyresorufin O-deethylase (EROD) assays. In the yeast assay, eight compounds exhibited agonist activity, and their activity relative to β-naphthoflavone (BNF) ranged from 1.4 × 10(-4) to 8.3 × 10(-2), with the highest activity observed for benzyl 2-naphthyl ether (BNE). In the EROD assay, six compounds caused a more significant induction of CYP1A-dependent activity than did the vehicle control at 50 μM (p<0.01), and their induction levels were 5.1- to 11-fold more potent; 1,2-bis(3-methylphenoxy)ethane (BME) was the most effective inducer. The water from the waste paper recycling area was fractioned using solid-phase extraction (SPE) combined with a C18 disk and florisil cartridge. In gas chromatography-mass spectrometry (GC-MS) analysis, SRCs were detected in the first fraction, at a total concentration of 5.5 μg/L. This fraction also activated AhR, and its activity, expressed as a BNF equivalent value, was 0.42 nM in the yeast assay. The contribution ratio of active compounds accounted for up to 34% and 4.4% observed activity of the fraction and total samples, respectively. To our knowledge, this is the first study to show that paper industry-related compounds, namely aromatic sensitizers, activate AhR by using a yeast assay and HepG2 cells.
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http://dx.doi.org/10.1016/j.scitotenv.2014.05.144DOI Listing
September 2014

Identification of interspecific differences in phase II reactions: determination of metabolites in the urine of 16 mammalian species exposed to environmental pyrene.

Environ Toxicol Chem 2014 Sep 30;33(9):2062-9. Epub 2014 Jul 30.

Laboratory of Toxicology, Department of Environmental Veterinary Science, Graduate, School of Veterinary Medicine, Hokkaido University, Sapporo, Japan; Department of Pharmacology, Faculty of Veterinary Medicine, Kasetsart University, Bangkok, Thailand.

Interspecific differences in xenobiotic metabolism are a key to determining relative sensitivities of animals to xenobiotics. However, information on domesticated livestock, companion animals, and captive and free-ranging wildlife is incomplete. The present study evaluated interspecific differences in phase II conjugation using pyrene as a nondestructive biomarker of polycyclic aromatic hydrocarbon (PAH) exposure. Polycyclic aromatic hydrocarbons and their metabolites have carcinogenic and endocrine-disrupting effects in humans and wildlife and can have serious consequences. The authors collected urine from 16 mammalian species and analyzed pyrene metabolites. Interspecific differences in urinary pyrene metabolites, especially in the concentration and composition of phase II conjugated metabolites, were apparent. Glucuronide conjugates are dominant metabolites in the urine of many species, including deer, cattle, pigs, horses, and humans. However, they could not be detected in ferret urine even though the gene for ferret Uridine 5'-diphospho-glucuronosyltransferase (UDP-glucuronosyltransferase, UGT) 1A6 is not a pseudogene. Sulfate conjugates were detected mainly in the urine of cats, ferrets, and rabbits. Interestingly, sulfate conjugates were detected in pig urine. Although pigs are known to have limited aryl sulfotransferase activity, the present study demonstrated that pig liver was active in 1-hydroxypyrene sulfation. The findings have some application for biomonitoring environmental pollution.
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http://dx.doi.org/10.1002/etc.2656DOI Listing
September 2014

Chronic toxicity of parabens and their chlorinated by-products in Ceriodaphnia dubia.

Environ Toxicol 2015 May-Jun;30(6):664-73. Epub 2013 Dec 27.

Research Center for Environmental Risk, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki, 305-8506, Japan.

The chronic toxicity of 12 compounds of parabens and their chlorinated by-products was investigated using 7-day Ceriodaphnia dubia test under static renewal condition in order to generate information on how to disinfect by-products of preservatives that are discharged in aquatic systems. The mortality and inhibition of reproduction tended to increase with increasing hydrophobicity and decreased with the degree of chlorination of parabens. The EC50 values for mortality, offspring number, and first brood production ranged between 0.30-3.1, 0.047-12, and 1.3-6.3 mg L(-1) , respectively. For the number of neonates, the most sensitive endpoint, the no-observed-effect concentration (NOEC) and lowest-observed-effect concentration (LOEC) values ranged from 0.63 to 10 mg L(-1) and from 1.2 to 19 mg L(-1) , respectively. Methylparaben (MP), benzylparaben (BnP), and dichlorinated BnP (Cl2 BnP) elicited a significant decrease in offspring numbers even at their lowest concentration tested; the NOEC for these compounds was determined to be less than the lowest test concentration (1.3, 0.04, and 0.63 mg L(-1) for MP, BnP, and Cl2 BnP, respectively). Propylparaben (PP), chlorinated PP, isopropylparaben (iPP), and chlorinated iPP exhibited nonmonotonic concentration-dependent response; their NOEC and LOEC values could not be determined. The multivariate approach involving principal component analysis and hierarchical cluster analysis revealed four groups that corresponded to the toxicological profiles of parabens. Our results suggested that disinfection of parabens by chlorination could reduce aquatic toxicity of original compounds. The findings obtained in our study together with the data available on paraben concentrations in aquatic systems can be used to perform preliminary risk assessment by comparing the predicted environmental concentration (PEC) with the predicted no-effect concentration (PNEC) for the marine aquatic environment. The calculated PEC/PNEC ratios ranged from 0.0012 to 0.2, with the highest value observed in MP. This suggested that there are negligible environmental risks for aquatic organisms at current use levels.
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http://dx.doi.org/10.1002/tox.21944DOI Listing
December 2015

Identification and accumulation of aromatic sensitizers in fish from paper recycling in Japan.

Environ Toxicol Chem 2012 Jun 27;31(6):1202-8. Epub 2012 Apr 27.

Institute for Environmental Sciences, University of Shizuoka, Shizuoka, Japan.

Aromatic sensitizers and related compounds (SRCs) originating from thermal recording material as impurities in waste paper have been detected in aquatic environments near cities where the paper industry is flourishing. In the present study, the levels of exposure to such SRCs and the stable isotope ratios (δ(13)C and δ(15)N) in different fish species (Konosirus punctatus, Takifugu niphobles, and Tribolodon hakonensis) were analyzed. These fish species were collected from the vicinity of waste paper recycling plants in Japan. Eleven SRCs were identified in fish muscle at total concentration levels (ΣSRCs) of 64 to 818 ng/g wet weight (mean 181 ng/L wet wt). The dominant SRCs in the fish samples were 1,1-di(4-methylphenyl)ethane, 1,2-bis(3-methylphenoxy)ethane, and 1,4-dibenzyloxybenzene. Stable isotope ratios showed that, although three species feed on the same trophic level, K. punctatus and T. niphobles live in waters farther offshore than those in which T. hakonensis live. The contributions of various factors to the accumulation were also assessed. The lipid content (r(2) = 0.512, p < 0.001) was found to be the significant factor that influenced accumulation of SRCs in fish. The results also revealed significant positive correlation between the accumulation patterns and SRC components in water (r(2) = 0.512-0.658, all p values <0.05), but they showed negative correlations between the SRCs in fish and log K(OW) values. This suggests that the aqueous route is the predominant route for the accumulation of SRCs in fish. This is the first study on the accumulation of aromatic sensitizers in aquatic biota.
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http://dx.doi.org/10.1002/etc.1812DOI Listing
June 2012

Rat hyperactivity by bisphenol A, but not by its derivatives, 3-hydroxybisphenol A or bisphenol A 3,4-quinone.

Toxicol Lett 2011 Oct 22;206(3):300-5. Epub 2011 Aug 22.

Center for Environmental Risk Research, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba 305-8506, Japan.

Detoxification in the central nervous system is largely unknown. The mechanism of neurotoxicity of bisphenol A, a toxic environmental chemical remains obscure. We examined the effects of bisphenol A, and its derivatives, 3-hydroxybisphenol A and bisphenol A 3,4-quinone on rat behavior as possible metabolites of bisphenol A. A single intracisternal administration of bisphenol A (20 μg equivalent to 87 nmol) into 5-day-old male Wistar rats caused significant hyperactivity at 4-5 weeks of age. It was about 1.3 fold more active in the nocturnal phase than control rats. However, neither 3-hydroxybisphenol A nor bisphenol A 3,4-quinone at the same amount (87 nmol) increased the spontaneous motor activity. Gas chromatographic-mass spectrometric (GC-MS) analyses of the treated brain revealed that 7% of the parent chemical resided in the brain at 8 weeks of age, but its derivatives were not found. This suggested a difference in metabolic turnover of these compounds or a difference in their stabilities. We conclude that bisphenol A per se caused hyperactivity in the rat, eliminating the possibility that possible metabolic forms of bisphenol A, 3-hydroxybisphenol A and bisphenol A 3,4-quinone have the ability to elicit rat hyperactivity, probably because of longer-lasting residence of the parent compound in the brain.
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http://dx.doi.org/10.1016/j.toxlet.2011.08.011DOI Listing
October 2011

The feasibility of using mosquitofish (Gambusia affinis) for detecting endocrine-disrupting chemicals in the freshwater environment.

Environ Toxicol Chem 2011 Dec 14;30(12):2778-85. Epub 2011 Oct 14.

Research Center for Environmental Risk, National Institute for Environmental Studies, Tsukuba, Ibaraki, Japan.

We evaluated the utility of gene-transcriptional responses in the liver of mosquitofish (Gambusia affinis), a species introduced to many countries and therefore widely available, for detecting endocrine-disrupting activity in water. Exposure to β-naphthoflavone, an aryl hydrocarbon receptor (AhR) agonist, significantly increased the transcript of the cytochrome P4501A gene (cyp1a), peaking at 24 h, in both sexes at concentrations of 10 µg/L or more. 17β-Estradiol (E(2) ) at 500 ng/L increased the number of males showing gene transcription of precursors of yolk protein, vitellogenin (Vtga, Vtgb, and Vtgc), at 24, 48, and 72 h. Exposure for 48 h to bisphenol A (BPA), an estrogen mimic, also increased vtg-positive males at 1 mg/L or more. Leachate from a Japanese stable-type landfill significantly increased vtg-positive males after 48 h exposure, and the in vitro activity of the leachate against the estrogen receptor (ER) was estimated as an E(2) equivalent of 240 ng/L by yeast transfected with the ER. Chemical analysis showed that major contributors to the ER activation were BPA and 4-tert-octylphenol. This leachate and drainage water from a control-type landfill had AhR activities, estimated by yeast with the AhR, but had no significant effect on cyp1a transcription. These results showed that mosquitofish are suitable for detecting in vivo AhR and ER effects, but are insensitive to E(2).
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http://dx.doi.org/10.1002/etc.669DOI Listing
December 2011

Assessment of thyroid hormone activity of halogenated bisphenol A using a yeast two-hybrid assay.

Chemosphere 2011 Sep 8;84(10):1527-30. Epub 2011 May 8.

Institute for Environmental Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan.

The thyroid hormone agonist/antagonist activities of halogenated derivatives of bisphenol A (BPA) were assessed using a yeast two-hybrid assay incorporating the human thyroid hormone α (TRα), both with and without possible metabolic activation by rat liver S9 preparation. In the absence of the rat liver S9 preparation, 3,3',5,5'-tetrabromobisphenol A (TBBPA), 3,3',5,5'-tetrachlorobisphenol A (TCBPA), and 3,3',5-trichlorobisphenol A (3,3',5-triClBPA) exhibited agonist activity, whereas 3-chlorobisphenol A (3-ClBPA), 3,5-dichlorobisphenol A (3,5-diClBPA), 3,3'-dichlorobisphenol A (3,3'-diClBPA), and BPA did not. The activities of TBBPA and TCBPA increased markedly (7.6-fold and 3.1-fold, respectively) after their metabolic activation with the rat liver S9 preparation. TBBPA, TCBPA, and 3,3',5-triClBPA inhibited the binding of triiodothyronine (T3) to TRα at 2×10(-5) M without rat liver S9 treatment and 4×10(-6) M with rat liver S9 treatment, demonstrating their T3 antagonist activity. These results revealed that metabolic activation by rat liver S9 significantly increased the agonist/antagonist potential of some halogenated BPAs.
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http://dx.doi.org/10.1016/j.chemosphere.2011.04.045DOI Listing
September 2011

A novel estrogenic compound transformed from fenthion under UV-A irradiation.

J Hazard Mater 2010 Apr;176(1-3):685-91

Graduate School of Nutritional and Environmental Sciences, University of Shizuoka, 52-1, Yada, Suruga-ku, Shizuoka 422-8526, Japan.

The photo-transformed products of fenthion well-known as one of the most photosensitive organophosphorus insecticides and their estrogenic activities were investigated using a yeast two-hybrid assay incorporating the human estrogen receptor alpha (hERalpha). We identified fenthion sulfoxide and 3-methyl-4-methylsulfinylphenol (MMS) as the major transformed products and 3-methyl-4-(methylthio)phenol (MMP) as the minor product under UV-A irradiation. Further, significant estrogenic activity was observed in the solution irradiated for 160 min; this activity was evaluated as 18 pM converted to 17beta-estradiol (E(2)) equivalent concentration. By using authentic standards, it was found that MMP possessed weak estrogenic activity; its activity was evaluated as 1.7x10(-6) times compared with that of E(2). However, it was also revealed that the activity due to MMP was only 13%. From high-performance liquid chromatography (HPLC) and nuclear magnetic resonance (NMR) spectroscopies, we newly identified a significant estrogenic compound transformed from fenthion, O,O-dimethyl S-[3-methyl-4-(methylthio)phenyl]phosphorothioate, S-aryl fenthion.
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http://dx.doi.org/10.1016/j.jhazmat.2009.11.086DOI Listing
April 2010

Development and validation of chemical and biological analyses to determine the antiestrogenic potency of resin acids in paper mill effluents.

Environ Sci Technol 2009 Dec;43(24):9300-5

Institute for Environmental Sciences, University of Shizuoka, Yada 52-1, Suruga-ku, Shizuoka 422-8526, Japan, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-8506, Japan, and Shizuoka Institute of Environment and Hygiene, 4-27-2 Kita-Ando, Aoi-ku, Shizuoka 420-8637, Japan.

This study combined chemical analysis and bioassays of paper mill effluents and their components in order to determine their antiestrogenic activity. The bioassay comprised a yeast two-hybrid assay incorporating the estrogen receptor alpha (hERalpha) and an hERalpha competitive enzyme-linked immunosorbent assay (ELISA). Samples were fractionated by solid phase extraction (SPE) with a C18 disk and a Florisil cartridge to obtain four fractions. The final fraction, eluted with methanol from the Florisil cartridge after pre-extraction by the C18 disk, was the most active in the two-hybrid assay, and its antiestrogenic potency, expressed as the equivalent concentration to 4-hydroxytamoxifen (OHT), was 277 nM. Seven resin acids had antiestrogenic activity in the active fraction as determined by gas chromatography/mass spectrometry (GC/MS), and their concentration levels ranged from 0.11 to 12 microg/L. All the resin acids exhibited greater activity than OHT; their activity relative to OHT ranged from 2.8- to 4.0-fold in the yeast two-hybrid assay. Based on the chemical analysis data and relative potency of resin acids from the yeast two-hybrid assay, the contribution ratio of resin acids accounted for 72% of the observed antiestrogenic activity of the extract. Furthermore, no resin acid showed any affinity for the estrogen receptor in the ELISA. This study showed that analysis combining the SPE method and the yeast two-hybrid assay is likely to be effective for the comprehensive monitoring of resin acids in paper mill industrial discharge areas.
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http://dx.doi.org/10.1021/es9025479DOI Listing
December 2009

Acetylcholinesterase inhibitory activity and chemical composition of commercial essential oils.

J Agric Food Chem 2009 May 9;57(10):4313-8. Epub 2009 Apr 9.

Institute for Environmental Sciences, University of Shizuoka, Yada 52-1, Suruga-ku, Shizuoka 422-8526, Japan.

Commercially available essential oils extracted from Artemisia dracunculus L., Inula graveolens L., Lavandula officinalis Chaix, and Ocimum sanctum L. and the components of these oils were screened by the microplate assay method for determining their acetylcholinesterase (AChE) inhibitory activity. The composition profiles of the oils were characterized by gas chromatography-mass spectrometry (GC-MS) analysis, and the relationships between the oil components and the AChE inhibitory activity of the oils were outlined. The results showed that all of the oils, except that of A. dracunculus from Hungary, exhibited AChE inhibitory activity, and the A. dracunculus oil from France showed the most potent inhibitory activity [50% inhibition concentration (IC(50)) = 0.058 mg/mL]. The AChE inhibitory activity of I. graveolens oil has not been reported to date, and this study is the first to reveal this activity in the oil. Among the essential oil components, five components, namely, 1,8-cineole, α-pinene, eugenol, α-terpineol, and terpinen-4-ol, showed AChE inhibitory activity, with IC(50) values of 0.015, 0.022, 0.48, 1.3, and 3.2 mg/mL, respectively. Eugenol, in particular, was found to be a potent AChE inhibitor along with determination of the IC(50) value, a finding that has been reported for the first time in this study. However, the ratio of the contribution of the active components, including a novel AChE inhibitor, to the observed AChE inhibitory activity of the essential oils was not very high. The results of this study raise concerns about the AChE inhibitory activity of widely produced and readily accessible commercial essential oils.
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http://dx.doi.org/10.1021/jf804013jDOI Listing
May 2009

Acute toxicity of parabens and their chlorinated by-products with Daphnia magna and Vibrio fischeri bioassays.

J Appl Toxicol 2009 Apr;29(3):242-7

Institute for Environmental Sciences, University of Shizuoka, Yada 52-1, Suruga-ku, Shizuoka 422-8526, Japan.

The acute toxicity of 21 parabens and their chlorinated derivatives was investigated by means of two toxicity bioassays: Daphnia magna immobilization test and the inhibition of bioluminescence of Vibrio fischeri. The median effective concentration (EC(50)) values of the tested parabens ranged from 2.2 to 62 mg l(-1) in the D. magna test and from 0.0038 to 5.9 mg l(-1) in the V. fischeri test at 15 min after exposure. The toxicity of dichlorinated methyl- and n-propylparaben, the most commonly used preservatives in cosmetics, toward D. magna was 3.9- and 2.8-fold that of their corresponding parent compounds. Toxicity toward D. magna showed a linear relationship with log P, indicating that toxicity increases with increasing hydrophobicity. On the other hand, the correlations of toxicity toward V. fischeri with hydrophobicity and with the degree of chlorination were poor. In addition, the results of the present study indicated that the V. fischeri test was more sensitive than the D. magna test for the determination of the acute toxicity of parabens. A complete assessment of the ecological and toxicological risks of parabens may require the examination of chlorinated parabens as well as the parent pollutants, as described in the present study.
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http://dx.doi.org/10.1002/jat.1402DOI Listing
April 2009

Evaluation of estrogenic activity of parabens and their chlorinated derivatives by using the yeast two-hybrid assay and the enzyme-linked immunosorbent assay.

Environ Toxicol Chem 2009 Jan;28(1):204-8

Institute for Environmental Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan.

We assessed the estrogen agonist activities of 21 parabens and their chlorinated derivatives by using yeast two-hybrid assays incorporating either the human or medaka (Oryzias latipes) estrogen receptor alpha (hERalpha and medERalpha, respectively), and by using hERalpha competitive enzyme-linked immunosorbent assay (ER-ELISA). In the two-hybrid assay with hERalpha, five parabens and three chlorinated derivatives exhibited estrogenic activity, and their relative activity (17beta-estradiol [E2] = 1) ranged from 2.0 x 10(-5) to 2.0 x 10(-4), with the highest activity observed in i-butylparaben. In the medERalpha assay, six parabens and six chlorinated derivatives exhibited estrogenic activity and their relative activity ranged from 2.7 x 10(-5) to 3.5 x 10(-3), with the highest activity observed in benzylparaben, its monochlorinated derivative, i-butylparaben, and n-butylparaben. Although medERalpha demonstrated an activity to E2 that was three times lower than that demonstrated by hERalpha, medERalpha has a higher sensitivity to parabens than hERa (1.3-8.9 times). Five parabens and two chlorinated derivatives exhibited a binding affinity to ERa in the ER-ELISA; of the parabens, i-butylparaben exhibited the strongest binding affinity. The yeast two-hybrid assay and the ER-ELISA also revealed that many of the assayed chlorinated parabens were much weaker than the parent compound. In addition, the results mainly showed that parabens with a bulk substituent (e.g., i-butyl and benzyl groups) had a higher activity than those with a sterically small substituent. It is considered that derivatization masks the apparent estrogenic activity of parabens, but the resulting chlorinated compounds may represent a potential hazard and therefore other toxicity tests should be performed to determine the toxicity of the chlorinated derivatives.
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http://dx.doi.org/10.1897/08-225.1DOI Listing
January 2009

Occurrence and estrogenicity of phenolics in paper-recycling process water: pollutants originating from thermal paper in waste paper.

Environ Toxicol Chem 2007 Nov;26(11):2356-66

Institute for Environmental Sciences, University of Shizuoka, Yada 52-1, Suruga-ku, Shizuoka 422-8526, Japan.

Eight phenolics were detected in samples collected from areas where paper-recycling process water is discharged. The detected concentration levels were up to 270 microg/L and 230 microg/g in water samples and sediment samples, respectively, obtained from both the outfall of the paper-recycling process water and its downstream areas. In particular, totarol (compound 4), 2,4-bis(1-phenylethyl)phenol (compound 6), 4,4'-butylidenebis(6-t-butyl-m-cresol) (compound 7), 2,4-bis(1-phenylethyl)-6-chlorophenol (compound 8), and 4-hydroxy-4'-isopropoxydiphenyl sulfone (compound 9) were identified for the first time as environmental pollutants. The estrogenicities of the identified compounds were assessed by yeast two-hybrid assays incorporating either the human or medaka fish (Oryzias latipes) estrogen receptor alpha (hERalpha and medERalpha, respectively) and an estrogen receptor competitive enzyme-linked immunosorbent assay (ER-ELISA) both with and without metabolic activation by a rat liver S9 mix. Bisphenol A (compound 3) and 2-naphthol (compound 1) exhibited activity in the assays of both hERalpha and medERalpha without the S9 mix. The relative activity (%) to 17beta-estradiol was 0.0015% for compound 3 and 0.0009% for compound 1 in the hERalpha assay and 0.027% for compound 3 and 0.0093% for compound 1 in the medERalpha assay. These compounds were attenuated by the S9 mix. The binding affinity was evaluated using an ER-ELISA. Compounds 3, 4, 6, and 7 exhibited affinity without the S9 mix. After exposure to the S9 mix, however, the binding affinity of compound 7 was eliminated by the S9 mix; those of compounds 3, 4, and 6 were attenuated; and that of compound 8 exhibited affinity. A comprehensive assessment of the estrogenicities of the phenolics originating from thermal paper and their implications for an aquatic environment may require an examination of the components of the phenolics, as in the present study.
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http://dx.doi.org/10.1897/06-642R.1DOI Listing
November 2007

Organic pollutants in paper-recycling process water discharge areas: first detection and emission in aquatic environment.

Environ Pollut 2008 Jan 23;151(1):53-9. Epub 2007 May 23.

Institute for Environmental Sciences, University of Shizuoka, Yada 52-1, Suruga-ku, Shizuoka 422-8526, Japan.

In this study, eight compounds have been identified and quantified from the samples collected from paper-recycling process water discharge areas. In particular, five aryl hydrocarbons, including a novel chlorinated aryl ether, were identified for the first time as environmental pollutants. In the effluent stream, concentration levels of up to 1600 microg L(-1) and 190 microg g(-1) were detected in the surface water and surface sediment, respectively. The results of this study have raised concerns regarding the organic chemicals used in thermal paper and the environmental consequences of their release.
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http://dx.doi.org/10.1016/j.envpol.2007.03.012DOI Listing
January 2008

Identification and estrogenic characterization of impurities in commercial bisphenol A diglycidyl ether (BADGE).

Chemosphere 2006 Oct 2;65(5):873-80. Epub 2006 May 2.

Institute for Environmental Sciences, University of Shizuoka, 52-1 Yada, Shizuoka, Japan.

A sample of commercial BADGE was fractioned by HPLC and eight impurities including novel propyl derivatives (2), (5) and (6) were identified by NMR spectrometry, FAB-MS and GC-MS. The estrogenicity, both agonist and antagonist, of fractions containing these impurities was measured with a yeast two-hybrid assay incorporating the human (hER alpha) and a competitive binding assay for hER alpha (ELISA). In the yeast two-hybrid assay, estrogenic antagonist activity was found in two fractions, while estrogenic agonist activity was not found in any. In the ELISA method, the binding affinity to hER alpha was found in three fractions. It is probable that a comprehensive assessment of the estrogenic properties of commercial BADGE, and their implications for human health, will require examination of all its components as described here.
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http://dx.doi.org/10.1016/j.chemosphere.2006.03.015DOI Listing
October 2006

Estrogenic activity of impurities in industrial grade bisphenol A.

Environ Sci Technol 2005 May;39(10):3703-7

Institute for Environmental Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan.

The estrogenicities of 10 compounds found as impurities in industrial grade bisphenol A (BPA) were measured by yeasttwo-hybrid assays incorporating the human estrogen receptor alpha(hERalpha) orthe medaka fish (Oryziaslatipes) estrogen receptor alpha (medERalpha). Five impurities showed greater activity than BPA itself in an agonist assay for hERalpha. p-Cumylphenol, the most active of the impurities in the hERalpha assay, was 12 times as active as BPA. The REC10 (10% relative effective concentration: 10% of the activity of 10(-8)M 17,B-estradiol) was 710 nM. Five impurities showed greater activity than BPA in an agonist assay for medERa: 4,4'-(1,3-dimethylbutylidene) bisphenol and 2-(4'-hydroxy-phenyl)-2,4,4-trimethylchroman were nearly equipotent and 9 times as active as BPA, and the REC10 values of these compounds in the medERalpha assay were 280 and 320 nM, respectively. Comparison of the experimentally determined estrogenicities of mixtures of BPA and 4,4'-(1,3-dimeth-ylbutylidene) bisphenol and those calculated by the concentrations addition (CA) method confirmed the suitability of the method for the prediction of the estrogenicities of the mixtures of BPA and its phenolic analogues. The measured estrogenicities of four samples of industrial grade BPA and laboratory grade (pure) BPA were not significantly different in either the hERalpha assay or the medERalpha assay (p > 0.05 in each case). We conclude that the impurities in industrial grade BPA, although some are of much higher estrogenic activity than BPA itself, do not significantly increase the estrogenicity of the industrial compound and therefore do not increase possible adverse health effects from such activity.
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http://dx.doi.org/10.1021/es048932gDOI Listing
May 2005

The reaction of bisphenol A 3,4-quinone with DNA.

Biochem Biophys Res Commun 2004 Jun;319(2):556-61

Endocrine Disrupter Research Laboratory, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-8506, Japan.

The 3,4-quinone of the estrogen-active compound bisphenol A (BPA), characterized by a single crystal X-ray structure determination, has been shown by (1)H NMR spectroscopy to react with herring testes DNA, and with deoxyguanosine (dG), in aqueous buffer at pH 7, to form a BPA 3,4-quinone-guanine-N7 adduct (BPAQ-N7-Gua). Presumably this adduct resulted from decomposition (by loss of deoxyribose) of an initially formed, but unstable, BPAQ-N7-dG adduct. Chemical synthesis if BPAQ-N7-Gua, in up to 60% yield, was achieved by the reaction of BPAQ and dG in aqueous acetic acid. Characterization of this product, by NMR spectroscopy and high resolution mass spectrometry, allowed the monitoring (by (1)H NMR spectroscopy) of the reaction of BPAQ with DNA and with dG. The relevance of this adduct formation to the potential mutagenicity and carcinogenicity of BPA will depend upon confirmation of the necessary metabolic oxidative transformation of BPA in vivo.
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http://dx.doi.org/10.1016/j.bbrc.2004.05.024DOI Listing
June 2004

Impurities in industrial grade 4,4'-isopropylidene diphenol (bisphenol A): possible implications for estrogenic activity.

Chemosphere 2004 May;55(6):927-31

Endocrine Disrupter Research Laboratory, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-8506, Japan.

Fifteen trace impurities, including a novel cyclohexene derivative, have been identified and quantified in samples of an industrial grade of the oestrogen-active compound 4,4'-isopropylidene diphenol (bisphenol A). All of these compounds, like bisphenol A itself, possess phenolic hydroxyl groups para to other substituents and all thus might also have oestrogenic properties. Published studies on the endocrine disrupting properties of bisphenol A have not considered potentially active impurities but full assessment of the oestrogenicity of bisphenol A, as it is used commercially, will become possible when adequate supplies of these compounds are available through synthesis.
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http://dx.doi.org/10.1016/j.chemosphere.2003.11.063DOI Listing
May 2004

A new pathway to aspartic acid from urea and maleic acid affected by ultraviolet light.

Orig Life Evol Biosph 2002 Apr;32(2):91-8

Department of Chemistry, University of Tsukuba, Tsukuba 305-8571, Japan.

The photochemistry of a mixture of urea and maleic acid, which are thought to have been widely present on the primitive Earth, was studied in order to examine a possibility of the formation of amino acids. When an aqueous solution of urea and maleic acid was irradiated with an ultraviolet light of wavelength 172 nm, urea was revealed to be rather resistant to photochemical decomposition. In contrast, maleic acid was completely decomposed within 4 h, reflecting the reactivity of a C-C double bond in the molecule. In the reaction mixture, 2-isoureidosuccinic acid was detected. The acid was considered to be formed by addition of an isoureido radical which had been produced from urea by the action of a hydroxyl radical, to a C-C double bond of maleic acid. The isoureido group of the product was revealed to undergo thermal rearrangement to afford 2-ureidosuccinic acid (N-carbamoylaspartic acid). The result suggested a novel pathway leading to the formation of aspartic acid from non-amino acid precursors, possibly effected by UV-light on the primitive Earth. The formation of ureidocarboxylic acids is of another significance, since they are capable of undergoing thermal polymerization, resulting in formation of polyamino acids.
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http://dx.doi.org/10.1023/a:1016067303182DOI Listing
April 2002
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