Yuichi Horii - Academia.edu (original) (raw)

Papers by Yuichi Horii

Research paper thumbnail of Spatial distribution and accumulation profiles of volatile methylsiloxanes in Tokyo Bay, Japan: Mass loadings and historical trends

Science of The Total Environment, 2021

We investigated mass loading and the spatial distribution of volatile methylsiloxanes (VMSs) incl... more We investigated mass loading and the spatial distribution of volatile methylsiloxanes (VMSs) including four cyclic VMSs (D3-D6; cVMSs, the number refers to the number of SiO bonds) and three linear VMSs (L3-L5; lVMSs) in Tokyo Bay, Japan, which is one of the most industrialized, urbanized, and populated areas in the world. Based on the VMS concentrations determined in eight main inflow rivers to the bay, the mass loading of VMSs via inflow rivers and sewage treatment plants located in Tokyo Bay was estimated at 2700 kg/y for total VMSs. Elevated mass loadings of VMSs were found in three of the rivers, inflowing to the inner west of Tokyo Bay. The distribution and deposition characteristics of VMSs were observed depending on the estuarine condition. Estuarine sediments were found to be efficient and effective traps for VMSs and the salting-out effect is one possible mechanism to explain this phenomenon. The overall profiles of D4, D5, and D6 in surface water and sediment were observed across Tokyo Bay; elevated concentrations were identified in the inner west bay with dispersed low concentrations in the outer bay, except for one hotspot of D4 in the sediment, indicating a major emission route of VMSs via inflow rivers. Additionally, the historical pollution profiles of VMSs in Tokyo Bay were reconstructed based on the VMS concentrations determined in a dated sediment core. VMSs were identified throughout the upper 40 cm of the sediment core (representing the mid 1980s); the profiles correspond with the historical use of VMSs in wash-off personal care-products. The noted decreasing trend of D4 might be a reflection of the early 2000s replacement of D4 with D5 in such products. The elevated VMS concentrations in the estuarine sediment raise concerns about the impact on the aquatic environment.

Research paper thumbnail of Mass balance assessment of polycyclic musks in wastewater treatment plants in Kentucky and Georgia, USA

Wastewater treatment plants (WWTPs) are a source of polycyclic musks in the aquatic environment. ... more Wastewater treatment plants (WWTPs) are a source of polycyclic musks in the aquatic environment. In this study, contamination profiles and mass flow of polycyclic musks,

Research paper thumbnail of Analysis of polychlorinated naphthalenes and dioxin-like compounds in pine needle leaf by high-resolution GC/high-resolution MS

Research paper thumbnail of Source identification of polychlorinated naphthalenes, dioxins and related compounds in pine needles from Tokyo Bay, Japan and Poland

Bunseki kagaku

Pine needles are considered to be a very suitable biomatrix for monitoring long-term ambient air ... more Pine needles are considered to be a very suitable biomatrix for monitoring long-term ambient air concentrations of such atmospheric pollutants as semivolatile and persistent lipophilic compounds. Pine needles were analyzed for polychlorinated naphthalenes (PCNs) and dioxin-like compounds to provide initial evidence on their occurrence in ambient air and any potential connection to possible sources of pollution around Tokyo Bay, Japan and at industrial sites in Poland. The concentrations of PCNs in pine needles around Tokyo Bay and at sites in Poland varied between 250 to 2100 pg/g, wet weight and 520 to 920 pg/g, respectively. Tri-and tetra-CNs were dominating constituents (54 to 83) of PCNs quantified in pine needles from Tokyo Bay and Poland. Octa-CN was a characteristic congener in analysed Polish samples, because the level of this congener from Poland was obviously higher than that from Tokyo Bay. Wet weight normalized concentrations of 2,3,7,8-substituted PCDDs/Fs and planar PCBs in pine needles from Tokyo Bay were 27 to 110 pg/g and 110 to 420 pg/g, respectively ; however, those from Poland were 37 to 125 pg/g and 990 to 1700 pg/g, respectively. Octa-CDD/F were also the predominant congeners, and the planar PCB concentration was significantly greater in samples from Poland. The results of this study suggest the presence of different pollutant sources between Tokyo Bay and industrial sites in Poland. Pine needles should be useful for not only a long-term indicator of ambient air pollution, but also for evaluations of the local, regional and national distributions of lipophilic air pollutants.

Research paper thumbnail of Determination of individual nonylphenol isomers in water samples by using relative response factor method

Research paper thumbnail of Historical records of polychlorinated naphthalenes,-biphenyls,-dibenzo-P-dioxins,-dibenzofurans in a dated sediment core from Lake Kitaura, Japan

Organohalogen compounds, 2002

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Research paper thumbnail of Environmental analysis of chlorinated and brominated polycyclic aromatic hydrocarbons by comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry

Journal of Chromatography A, 2011

Brominated polycyclic aromatic hydrocarbons (Br-PAHs) Comprehensive two-dimensional gas chromatog... more Brominated polycyclic aromatic hydrocarbons (Br-PAHs) Comprehensive two-dimensional gas chromatography (GC × GC) High resolution time-of-flight mass spectrometry (HRTOF-MS) a b s t r a c t A method for the analysis of chlorinated and brominated polycyclic aromatic hydrocarbon (Cl-/Br-PAHs) congeners in environmental samples, such as a soil extract, by comprehensive two-dimensional gas chromatography coupled to a high resolution time-of-flight mass spectrometry (GC × GC-HRTOF-MS) is described. The GC × GC-HRTOF-MS method allowed highly selective group type analysis in the twodimensional (2D) mass chromatograms with a very narrow mass window (e.g. 0.02 Da), accurate mass measurements for the full mass range (m/z 35-600) in GC × GC mode, and the calculation of the elemental composition for the detected Cl-/Br-PAH congeners in the real-world sample. Thirty Cl-/Br-PAHs including higher chlorinated 10 PAHs (e.g. penta, hexa and hepta substitution) and ClBr-PAHs (without analytical standards) were identified with high probability in the soil extract. To our knowledge, highly chlorinated PAHs, such as C 14 H 3 Cl 7 and C 16 H 3 Cl 7 , and ClBr-PAHs, such as C 14 H 7 Cl 2 Br and C 16 H 8 ClBr, were found in the environmental samples for the first time. Other organohalogen compounds; e.g. polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), and polychlorinated dibenzofurans (PCDFs) were also detected. This technique provides exhaustive analysis and powerful identification for the unknown and unconfirmed Cl-/Br-PAH congeners in environmental samples.

Research paper thumbnail of Occurrence and fate of polycyclic musks in wastewater treatment plants in Kentucky and Georgia, USA

Chemosphere, 2007

Wastewater treatment plants (WWTPs) are a potential of source of polycyclic musks in the aquatic ... more Wastewater treatment plants (WWTPs) are a potential of source of polycyclic musks in the aquatic environment. In this study, contamination profiles and mass flow of polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[gamma]-2-benzopyran (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), and HHCB-lactone (oxidation product of HHCB), in two WWTPs, one located in Kentucky (Plant A, rural area) and the other in Georgia (Plant B, urban), USA, were determined. HHCB, AHTN and HHCB-lactone were detected in the influent, effluent, and sludge samples analyzed. The concentrations in wastewater samples varied widely, from 10 to 7,030 ng/l, 13 to 5,400 ng/l, and 66 to 790 ng/l, for HHCB, AHTN, and HHCB-lactone, respectively. Sludge samples contained HHCB at <0.02-36 microg/g dry weight, AHTN at <0.02-7.2 microg/g dry weight, and HHCB-lactone at…

Research paper thumbnail of Workshop of the latest development on the evaluation method of Environmental Fate & Bioaccumulation

Research paper thumbnail of Distribution characteristics of methylsiloxanes in atmospheric environment of Saitama, Japan: Diurnal and seasonal variations and emission source apportionment

Science of The Total Environment

Research paper thumbnail of Isomer-specific analysis of PCN and dioxin-like compounds inDELORs, technical PCB mixtures from former Czechoslovakia

Isomer-specific analysis of PCN and dioxin-like compounds in DELORs, technical PCB mixtures from ... more Isomer-specific analysis of PCN and dioxin-like compounds in DELORs, technical PCB mixtures from former Czechoslovakia

Research paper thumbnail of A Preliminary Study for Combustion of Hexabromocyclododecane (HBCD) and Its By-Products

Miyake Y, Tang L, Kobayashi T, Kameya T, Managaki S, Masunaga S, Fujimine Y, Horii Y and Amagai T... more Miyake Y, Tang L, Kobayashi T, Kameya T, Managaki S, Masunaga S, Fujimine Y, Horii Y and Amagai T Institute for Environmental Sciences, University of Shizuoka, 52-1 Yada Suruga-ku, Shizuoka, Japan; Graduate School of Environment and Information Sciences, Yokohama National University, 79-7 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa, Japan; Otsuka Pharmaceutical Co. Ltd., 224-18 Ebisuno Hiraishi, Kawauchi-cho, Tokushima, Japan; Center for Environmental Science in Saitama, 914 Kamitanadare, Kazo, Saitama 347-0115, Japan

Research paper thumbnail of Accumulation of quaternary ammonium compounds as emerging contaminants in sediments collected from the Pearl River Estuary, China and Tokyo Bay, Japan

Marine Pollution Bulletin

In this work, the distribution of quaternary ammonium compounds (QACs) in two dated sediment core... more In this work, the distribution of quaternary ammonium compounds (QACs) in two dated sediment cores, collected from the Pearl River Estuary (PRE) and Tokyo Bay (TB), were investigated to understand the historical input of QACs and their diagenetic behavior in urban estuarine environments. The vertical variation profiles of QAC concentrations showed that benzylalkyldimethyl ammonium compounds (BACs) and dialkyldimethyl ammonium compounds (DADMACs) were widely used during 1970s and 1980s both in China and Japan. The declining environmental concentrations of QACs suggested a compositional change of commodities and the effectiveness of emission control strategies. For the individual QAC homologues, BAC homologues decreased significantly over time, while DADMAC compositions remained relatively stable. The differences in concentration and composition profiles of BACs and DADMACs in the sediment cores provided useful information on the patterns of use of QACs in China and Japan, as well as their diagenetic behaviors in the sediments.

Research paper thumbnail of Volatile methylsiloxanes in sewage treatment plants in Saitama, Japan: Mass distribution and emissions

Chemosphere

Wastewater, aeration gas, dewatered sludge, and incineration ash and flue gas (from dewatered slu... more Wastewater, aeration gas, dewatered sludge, and incineration ash and flue gas (from dewatered sludge) were collected from 9 sewage treatment plants (STPs) located in Saitama Prefecture, Japan, and analyzed for seven cyclic and linear volatile methylsiloxanes (VMSs) namely, D3, D4, D5, D6, L3, L4, and L5. The mass loadings and distribution of VMSs in STPs were estimated based on measured concentrations in liquid, solid, and gaseous samples, including incinerated dewatered sludge. Mass loading of ΣVMS varied widely from 21 kg y-1 to 3740 kg y-1, depending on the volume of wastewater treated in each STP. Mass % of ΣVMS distributed in aeration gas was 15% and that in activated sludge was 78%. Approximately 6.6% of ΣVMS remained in the final effluent. Overall, partitioning onto the activated sludge was the dominant removal mechanism for D4, D5, and D6, whereas volatilization was also an important removal mechanism for D4. Incineration was effective to degrade VMSs in dewatered sludge, with a reduction rate of >99%. Activated carbon treatment removed >99% of VMSs from the aeration gas. In Saitama Prefecture, total emission of ΣVMS via STPs was estimated at 434 kg y-1, 86 kg y-1, and 0.065 kg y-1, to aquatic, atmospheric, and terrestrial environments, respectively, which accounted for 83%, 17%, and 0.01% of the total environmental emissions. Our results indicate that majority of VMSs in dewatered sludge can be removed by incineration and emission of VMSs through incineration ash landfill is negligible.

Research paper thumbnail of Main Uses and Environmental Emissions of Volatile Methylsiloxanes

The Handbook of Environmental Chemistry

The main uses and environmental emissions of cyclic methylsiloxanes (CMSs) and linear methylsilox... more The main uses and environmental emissions of cyclic methylsiloxanes (CMSs) and linear methylsiloxanes (LMSs), especially the three volatile CMSs (D4, D5, and D6), were reviewed. This chapter provides information on production, use, concentrations in various products, as well as emission of volatile methylsiloxanes (VMSs) into the environment. Many silicone-based products contain residues of CMSs as impurities, and hence the occurrence of VMSs in silicone-based materials (such as rubber products) has been described. CMSs are mainly used as intermediates in the production of silicone polymers, silicone fluids, elastomers, and resins, all of which have diverse industrial and consumer applications. CMSs are also used directly in personal care products (PCPs), as carriers. The concentrations and profiles of CMSs and LMSs in PCPs and household products from North America, Europe, and Asia varied widely across and within the product categories. The measured concentrations ranged from 0.01% in body wash to 70% (by weight) in deodorants. D5 was the predominant CMS found with high detection frequency in most PCPs. The correlations among VMSs in consumer products suggested incorporation of different blends of silicones to the raw material or as additives in those products. The industrial production of VMSs and direct use of PCPs result in significant emissions of VMSs into the environment. High production volume, high mobility, and environmental persistence of VMSs are causes of concern. VMSs, especially CMSs, were found globally in various environmental matrices including air, water, and sludge. This chapter also provides information on the concentrations and patterns of VMSs in the environment surrounding silicone factories, paper production facilities, and oil fields.

Research paper thumbnail of Effects of characteristics of waste incinerator on emission rate of halogenated polycyclic aromatic hydrocarbon into environments

The Science of the total environment, Jan 2, 2018

We determined the concentrations of halogenated polycyclic aromatic hydrocarbons (XPAHs), some of... more We determined the concentrations of halogenated polycyclic aromatic hydrocarbons (XPAHs), some of which are carcinogenic and/or mutagenic compounds, in fly and bottom ashes and stack gas collected from waste incinerators in Japan. The dominant XPAHs in stack gas were consistent with those in the urban atmosphere. The dioxin-like toxic equivalent (TEQ) concentration ranges of the XPAHs in stack gas, fly ash, and bottom ash were 0.00497-20.5ng-TEQm-3, 0.0541-101ng-TEQg-1, and 0.000914-2.00ng-TEQg-1, respectively. The TEQ concentrations of the XPAHs targeted in this study were higher than those of polychlorinated dibenzo-p-dioxins/dibenzofurans and polychlorinated biphenyls reported in the literature. The annual amounts of XPAHs produced in the waste incinerators ranged from 25.1 to 881g. The mass balance of XPAHs in each waste incinerator was calculated to evaluate the emission rate of XPAHs from waste incinerators. Less than 6.7% of the XPAHs produced in the waste incinerators were e...

Research paper thumbnail of Mechanism of Formation of Chlorinated Pyrene during Combustion of Polyvinyl Chloride

Environmental science & technology, Jan 7, 2017

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are an emerging class of environmental cont... more Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are an emerging class of environmental contaminants, but the sources of these chemicals in the environment are not well-known. In this study, we developed a kinetic model describing the chlorination of PAHs to elucidate the mechanism of formation of ClPAHs during the combustion of organic waste containing chlorinated compounds and/or chlorine in an incinerator. Pyrene (Pyr) and polyvinyl chloride (PVC) were selected as a model PAH and a model organic substrate, respectively. All combustion experiments were carried out using a model furnace operated under similar experimental conditions. Combustion of PVC in the model furnace produced 1-ClPyr, 1,3-Cl2Pyr, 1,6-Cl2Pyr, 1,8-Cl2Pyr, 1,3,6-Cl3Pyr, and 1,3,6,8-Cl4Pyr. The developed model supported the experimental data on the sequential chlorination of pyrene. The rate constants for the formation of mono- to trichlorinated pyrenes were over 30 times of those for the formation of tetra- ...

Research paper thumbnail of Determination of hexavalent chromium concentration in industrial waste incinerator stack gas by using a modified ion chromatography with post-column derivatization method

Journal of chromatography. A, Jan 25, 2017

An ion chromatography with post-column derivatization with 1,5-diphenylcarbazide (IC-DPC) analyti... more An ion chromatography with post-column derivatization with 1,5-diphenylcarbazide (IC-DPC) analytical method was modified to enable measurement of trace-level hexavalent chromium (Cr(VI)) in air. One of the difficulties in determining trace levels of Cr(VI) in air with conventional IC-DPC methods is co-elution of the solvent and ion peaks due to high concentrations of ionic compounds in the extract. However, by using gradient elution rather than isocratic elution we were able to fully resolve the Cr(VI) ion peak from the solvent peak without the need for diluting the extract, which would have reduced the minimum quantifiable level of the method. With this method, we were able to detect Cr(VI) in air at concentrations of 5.3ng/m(3) (assuming a sampling volume of 1m(3) and a final solution volume of 10mL). Recovery tests at three different concentrations of Cr(VI) (50, 250, 1000ng) were performed with or without fly ash; recovery rates at all the concentrations of Cr(VI), with or witho...

Research paper thumbnail of Occurrence, profiles, and toxic equivalents of chlorinated and brominated polycyclic aromatic hydrocarbons in E-waste open burning soils

Environmental pollution (Barking, Essex : 1987), Jan 23, 2017

We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycycli... more We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and brominated polycyclic aromatic hydrocarbons (Br-PAHs) in e-waste open burning soils (EOBS). In this study, concentrations of 15 PAHs, 26 Cl-PAHs and 14 Br-PAHs were analyzed in EOBS samples. We found that e-waste open burning is an important emission source of Cl-PAHs and Br-PAHs as well as PAHs. Concentrations of total Cl-PAHs and Br-PAHs in e-waste open burning soil samples ranged from 21 to 2800 ng/g and from 5.8 to 520 ng/g, respectively. Compared with previous studies, the mean of total Cl-PAH concentrations of the EOBS samples in this study was higher than that of electronic shredder waste, that of bottom ash, and comparable to fly ash from waste incinerators in Korea and Japan. The mean of total Br-PAH concentrations of the EOBS samples was generally three to four orders of magnitude higher than those in incinerator bottom ash and comparable t...

Research paper thumbnail of Spatial and temporal trends of short- and medium-chain chlorinated paraffins in sediments off the urbanized coastal zones in China and Japan: A comparison study

Environmental pollution (Barking, Essex : 1987), Jan 13, 2017

To examine the impacts of urbanization and industrialization on the coastal environment, and asse... more To examine the impacts of urbanization and industrialization on the coastal environment, and assess the effectiveness of control measures on the contamination by chlorinated paraffins (CPs) in East Asia, surface and core sediments were sampled from the urbanized coastal zones in China and Japan (i.e., Pearl River Delta (PRD), Hong Kong waters and Tokyo Bay) and analyzed for short-chain (SCCPs) and medium-chain CPs (MCCPs). Much higher concentrations of CPs were found in the industrialized PRD than in adjacent Hong Kong waters. Significant correlation between CP concentration and population density in the coastal district of Hong Kong was observed (r(2) = 0.72 for SCCPs and 0.55 for MCCPs, p < 0.05), highlighting the effect of urbanization. By contrast, a relatively lower pollution level of CPs was detected in Tokyo Bay. More long-chain groups within SCCPs in the PRD than in Hong Kong waters and Tokyo Bay implied the effect of industrialization. Comparison of temporal trends betwe...

Research paper thumbnail of Spatial distribution and accumulation profiles of volatile methylsiloxanes in Tokyo Bay, Japan: Mass loadings and historical trends

Science of The Total Environment, 2021

We investigated mass loading and the spatial distribution of volatile methylsiloxanes (VMSs) incl... more We investigated mass loading and the spatial distribution of volatile methylsiloxanes (VMSs) including four cyclic VMSs (D3-D6; cVMSs, the number refers to the number of SiO bonds) and three linear VMSs (L3-L5; lVMSs) in Tokyo Bay, Japan, which is one of the most industrialized, urbanized, and populated areas in the world. Based on the VMS concentrations determined in eight main inflow rivers to the bay, the mass loading of VMSs via inflow rivers and sewage treatment plants located in Tokyo Bay was estimated at 2700 kg/y for total VMSs. Elevated mass loadings of VMSs were found in three of the rivers, inflowing to the inner west of Tokyo Bay. The distribution and deposition characteristics of VMSs were observed depending on the estuarine condition. Estuarine sediments were found to be efficient and effective traps for VMSs and the salting-out effect is one possible mechanism to explain this phenomenon. The overall profiles of D4, D5, and D6 in surface water and sediment were observed across Tokyo Bay; elevated concentrations were identified in the inner west bay with dispersed low concentrations in the outer bay, except for one hotspot of D4 in the sediment, indicating a major emission route of VMSs via inflow rivers. Additionally, the historical pollution profiles of VMSs in Tokyo Bay were reconstructed based on the VMS concentrations determined in a dated sediment core. VMSs were identified throughout the upper 40 cm of the sediment core (representing the mid 1980s); the profiles correspond with the historical use of VMSs in wash-off personal care-products. The noted decreasing trend of D4 might be a reflection of the early 2000s replacement of D4 with D5 in such products. The elevated VMS concentrations in the estuarine sediment raise concerns about the impact on the aquatic environment.

Research paper thumbnail of Mass balance assessment of polycyclic musks in wastewater treatment plants in Kentucky and Georgia, USA

Wastewater treatment plants (WWTPs) are a source of polycyclic musks in the aquatic environment. ... more Wastewater treatment plants (WWTPs) are a source of polycyclic musks in the aquatic environment. In this study, contamination profiles and mass flow of polycyclic musks,

Research paper thumbnail of Analysis of polychlorinated naphthalenes and dioxin-like compounds in pine needle leaf by high-resolution GC/high-resolution MS

Research paper thumbnail of Source identification of polychlorinated naphthalenes, dioxins and related compounds in pine needles from Tokyo Bay, Japan and Poland

Bunseki kagaku

Pine needles are considered to be a very suitable biomatrix for monitoring long-term ambient air ... more Pine needles are considered to be a very suitable biomatrix for monitoring long-term ambient air concentrations of such atmospheric pollutants as semivolatile and persistent lipophilic compounds. Pine needles were analyzed for polychlorinated naphthalenes (PCNs) and dioxin-like compounds to provide initial evidence on their occurrence in ambient air and any potential connection to possible sources of pollution around Tokyo Bay, Japan and at industrial sites in Poland. The concentrations of PCNs in pine needles around Tokyo Bay and at sites in Poland varied between 250 to 2100 pg/g, wet weight and 520 to 920 pg/g, respectively. Tri-and tetra-CNs were dominating constituents (54 to 83) of PCNs quantified in pine needles from Tokyo Bay and Poland. Octa-CN was a characteristic congener in analysed Polish samples, because the level of this congener from Poland was obviously higher than that from Tokyo Bay. Wet weight normalized concentrations of 2,3,7,8-substituted PCDDs/Fs and planar PCBs in pine needles from Tokyo Bay were 27 to 110 pg/g and 110 to 420 pg/g, respectively ; however, those from Poland were 37 to 125 pg/g and 990 to 1700 pg/g, respectively. Octa-CDD/F were also the predominant congeners, and the planar PCB concentration was significantly greater in samples from Poland. The results of this study suggest the presence of different pollutant sources between Tokyo Bay and industrial sites in Poland. Pine needles should be useful for not only a long-term indicator of ambient air pollution, but also for evaluations of the local, regional and national distributions of lipophilic air pollutants.

Research paper thumbnail of Determination of individual nonylphenol isomers in water samples by using relative response factor method

Research paper thumbnail of Historical records of polychlorinated naphthalenes,-biphenyls,-dibenzo-P-dioxins,-dibenzofurans in a dated sediment core from Lake Kitaura, Japan

Organohalogen compounds, 2002

RefDoc Refdoc est un service / is powered by. ...

Research paper thumbnail of Environmental analysis of chlorinated and brominated polycyclic aromatic hydrocarbons by comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry

Journal of Chromatography A, 2011

Brominated polycyclic aromatic hydrocarbons (Br-PAHs) Comprehensive two-dimensional gas chromatog... more Brominated polycyclic aromatic hydrocarbons (Br-PAHs) Comprehensive two-dimensional gas chromatography (GC × GC) High resolution time-of-flight mass spectrometry (HRTOF-MS) a b s t r a c t A method for the analysis of chlorinated and brominated polycyclic aromatic hydrocarbon (Cl-/Br-PAHs) congeners in environmental samples, such as a soil extract, by comprehensive two-dimensional gas chromatography coupled to a high resolution time-of-flight mass spectrometry (GC × GC-HRTOF-MS) is described. The GC × GC-HRTOF-MS method allowed highly selective group type analysis in the twodimensional (2D) mass chromatograms with a very narrow mass window (e.g. 0.02 Da), accurate mass measurements for the full mass range (m/z 35-600) in GC × GC mode, and the calculation of the elemental composition for the detected Cl-/Br-PAH congeners in the real-world sample. Thirty Cl-/Br-PAHs including higher chlorinated 10 PAHs (e.g. penta, hexa and hepta substitution) and ClBr-PAHs (without analytical standards) were identified with high probability in the soil extract. To our knowledge, highly chlorinated PAHs, such as C 14 H 3 Cl 7 and C 16 H 3 Cl 7 , and ClBr-PAHs, such as C 14 H 7 Cl 2 Br and C 16 H 8 ClBr, were found in the environmental samples for the first time. Other organohalogen compounds; e.g. polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), and polychlorinated dibenzofurans (PCDFs) were also detected. This technique provides exhaustive analysis and powerful identification for the unknown and unconfirmed Cl-/Br-PAH congeners in environmental samples.

Research paper thumbnail of Occurrence and fate of polycyclic musks in wastewater treatment plants in Kentucky and Georgia, USA

Chemosphere, 2007

Wastewater treatment plants (WWTPs) are a potential of source of polycyclic musks in the aquatic ... more Wastewater treatment plants (WWTPs) are a potential of source of polycyclic musks in the aquatic environment. In this study, contamination profiles and mass flow of polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[gamma]-2-benzopyran (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), and HHCB-lactone (oxidation product of HHCB), in two WWTPs, one located in Kentucky (Plant A, rural area) and the other in Georgia (Plant B, urban), USA, were determined. HHCB, AHTN and HHCB-lactone were detected in the influent, effluent, and sludge samples analyzed. The concentrations in wastewater samples varied widely, from 10 to 7,030 ng/l, 13 to 5,400 ng/l, and 66 to 790 ng/l, for HHCB, AHTN, and HHCB-lactone, respectively. Sludge samples contained HHCB at &amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;lt;0.02-36 microg/g dry weight, AHTN at &amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;lt;0.02-7.2 microg/g dry weight, and HHCB-lactone at…

Research paper thumbnail of Workshop of the latest development on the evaluation method of Environmental Fate & Bioaccumulation

Research paper thumbnail of Distribution characteristics of methylsiloxanes in atmospheric environment of Saitama, Japan: Diurnal and seasonal variations and emission source apportionment

Science of The Total Environment

Research paper thumbnail of Isomer-specific analysis of PCN and dioxin-like compounds inDELORs, technical PCB mixtures from former Czechoslovakia

Isomer-specific analysis of PCN and dioxin-like compounds in DELORs, technical PCB mixtures from ... more Isomer-specific analysis of PCN and dioxin-like compounds in DELORs, technical PCB mixtures from former Czechoslovakia

Research paper thumbnail of A Preliminary Study for Combustion of Hexabromocyclododecane (HBCD) and Its By-Products

Miyake Y, Tang L, Kobayashi T, Kameya T, Managaki S, Masunaga S, Fujimine Y, Horii Y and Amagai T... more Miyake Y, Tang L, Kobayashi T, Kameya T, Managaki S, Masunaga S, Fujimine Y, Horii Y and Amagai T Institute for Environmental Sciences, University of Shizuoka, 52-1 Yada Suruga-ku, Shizuoka, Japan; Graduate School of Environment and Information Sciences, Yokohama National University, 79-7 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa, Japan; Otsuka Pharmaceutical Co. Ltd., 224-18 Ebisuno Hiraishi, Kawauchi-cho, Tokushima, Japan; Center for Environmental Science in Saitama, 914 Kamitanadare, Kazo, Saitama 347-0115, Japan

Research paper thumbnail of Accumulation of quaternary ammonium compounds as emerging contaminants in sediments collected from the Pearl River Estuary, China and Tokyo Bay, Japan

Marine Pollution Bulletin

In this work, the distribution of quaternary ammonium compounds (QACs) in two dated sediment core... more In this work, the distribution of quaternary ammonium compounds (QACs) in two dated sediment cores, collected from the Pearl River Estuary (PRE) and Tokyo Bay (TB), were investigated to understand the historical input of QACs and their diagenetic behavior in urban estuarine environments. The vertical variation profiles of QAC concentrations showed that benzylalkyldimethyl ammonium compounds (BACs) and dialkyldimethyl ammonium compounds (DADMACs) were widely used during 1970s and 1980s both in China and Japan. The declining environmental concentrations of QACs suggested a compositional change of commodities and the effectiveness of emission control strategies. For the individual QAC homologues, BAC homologues decreased significantly over time, while DADMAC compositions remained relatively stable. The differences in concentration and composition profiles of BACs and DADMACs in the sediment cores provided useful information on the patterns of use of QACs in China and Japan, as well as their diagenetic behaviors in the sediments.

Research paper thumbnail of Volatile methylsiloxanes in sewage treatment plants in Saitama, Japan: Mass distribution and emissions

Chemosphere

Wastewater, aeration gas, dewatered sludge, and incineration ash and flue gas (from dewatered slu... more Wastewater, aeration gas, dewatered sludge, and incineration ash and flue gas (from dewatered sludge) were collected from 9 sewage treatment plants (STPs) located in Saitama Prefecture, Japan, and analyzed for seven cyclic and linear volatile methylsiloxanes (VMSs) namely, D3, D4, D5, D6, L3, L4, and L5. The mass loadings and distribution of VMSs in STPs were estimated based on measured concentrations in liquid, solid, and gaseous samples, including incinerated dewatered sludge. Mass loading of ΣVMS varied widely from 21 kg y-1 to 3740 kg y-1, depending on the volume of wastewater treated in each STP. Mass % of ΣVMS distributed in aeration gas was 15% and that in activated sludge was 78%. Approximately 6.6% of ΣVMS remained in the final effluent. Overall, partitioning onto the activated sludge was the dominant removal mechanism for D4, D5, and D6, whereas volatilization was also an important removal mechanism for D4. Incineration was effective to degrade VMSs in dewatered sludge, with a reduction rate of >99%. Activated carbon treatment removed >99% of VMSs from the aeration gas. In Saitama Prefecture, total emission of ΣVMS via STPs was estimated at 434 kg y-1, 86 kg y-1, and 0.065 kg y-1, to aquatic, atmospheric, and terrestrial environments, respectively, which accounted for 83%, 17%, and 0.01% of the total environmental emissions. Our results indicate that majority of VMSs in dewatered sludge can be removed by incineration and emission of VMSs through incineration ash landfill is negligible.

Research paper thumbnail of Main Uses and Environmental Emissions of Volatile Methylsiloxanes

The Handbook of Environmental Chemistry

The main uses and environmental emissions of cyclic methylsiloxanes (CMSs) and linear methylsilox... more The main uses and environmental emissions of cyclic methylsiloxanes (CMSs) and linear methylsiloxanes (LMSs), especially the three volatile CMSs (D4, D5, and D6), were reviewed. This chapter provides information on production, use, concentrations in various products, as well as emission of volatile methylsiloxanes (VMSs) into the environment. Many silicone-based products contain residues of CMSs as impurities, and hence the occurrence of VMSs in silicone-based materials (such as rubber products) has been described. CMSs are mainly used as intermediates in the production of silicone polymers, silicone fluids, elastomers, and resins, all of which have diverse industrial and consumer applications. CMSs are also used directly in personal care products (PCPs), as carriers. The concentrations and profiles of CMSs and LMSs in PCPs and household products from North America, Europe, and Asia varied widely across and within the product categories. The measured concentrations ranged from 0.01% in body wash to 70% (by weight) in deodorants. D5 was the predominant CMS found with high detection frequency in most PCPs. The correlations among VMSs in consumer products suggested incorporation of different blends of silicones to the raw material or as additives in those products. The industrial production of VMSs and direct use of PCPs result in significant emissions of VMSs into the environment. High production volume, high mobility, and environmental persistence of VMSs are causes of concern. VMSs, especially CMSs, were found globally in various environmental matrices including air, water, and sludge. This chapter also provides information on the concentrations and patterns of VMSs in the environment surrounding silicone factories, paper production facilities, and oil fields.

Research paper thumbnail of Effects of characteristics of waste incinerator on emission rate of halogenated polycyclic aromatic hydrocarbon into environments

The Science of the total environment, Jan 2, 2018

We determined the concentrations of halogenated polycyclic aromatic hydrocarbons (XPAHs), some of... more We determined the concentrations of halogenated polycyclic aromatic hydrocarbons (XPAHs), some of which are carcinogenic and/or mutagenic compounds, in fly and bottom ashes and stack gas collected from waste incinerators in Japan. The dominant XPAHs in stack gas were consistent with those in the urban atmosphere. The dioxin-like toxic equivalent (TEQ) concentration ranges of the XPAHs in stack gas, fly ash, and bottom ash were 0.00497-20.5ng-TEQm-3, 0.0541-101ng-TEQg-1, and 0.000914-2.00ng-TEQg-1, respectively. The TEQ concentrations of the XPAHs targeted in this study were higher than those of polychlorinated dibenzo-p-dioxins/dibenzofurans and polychlorinated biphenyls reported in the literature. The annual amounts of XPAHs produced in the waste incinerators ranged from 25.1 to 881g. The mass balance of XPAHs in each waste incinerator was calculated to evaluate the emission rate of XPAHs from waste incinerators. Less than 6.7% of the XPAHs produced in the waste incinerators were e...

Research paper thumbnail of Mechanism of Formation of Chlorinated Pyrene during Combustion of Polyvinyl Chloride

Environmental science & technology, Jan 7, 2017

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are an emerging class of environmental cont... more Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are an emerging class of environmental contaminants, but the sources of these chemicals in the environment are not well-known. In this study, we developed a kinetic model describing the chlorination of PAHs to elucidate the mechanism of formation of ClPAHs during the combustion of organic waste containing chlorinated compounds and/or chlorine in an incinerator. Pyrene (Pyr) and polyvinyl chloride (PVC) were selected as a model PAH and a model organic substrate, respectively. All combustion experiments were carried out using a model furnace operated under similar experimental conditions. Combustion of PVC in the model furnace produced 1-ClPyr, 1,3-Cl2Pyr, 1,6-Cl2Pyr, 1,8-Cl2Pyr, 1,3,6-Cl3Pyr, and 1,3,6,8-Cl4Pyr. The developed model supported the experimental data on the sequential chlorination of pyrene. The rate constants for the formation of mono- to trichlorinated pyrenes were over 30 times of those for the formation of tetra- ...

Research paper thumbnail of Determination of hexavalent chromium concentration in industrial waste incinerator stack gas by using a modified ion chromatography with post-column derivatization method

Journal of chromatography. A, Jan 25, 2017

An ion chromatography with post-column derivatization with 1,5-diphenylcarbazide (IC-DPC) analyti... more An ion chromatography with post-column derivatization with 1,5-diphenylcarbazide (IC-DPC) analytical method was modified to enable measurement of trace-level hexavalent chromium (Cr(VI)) in air. One of the difficulties in determining trace levels of Cr(VI) in air with conventional IC-DPC methods is co-elution of the solvent and ion peaks due to high concentrations of ionic compounds in the extract. However, by using gradient elution rather than isocratic elution we were able to fully resolve the Cr(VI) ion peak from the solvent peak without the need for diluting the extract, which would have reduced the minimum quantifiable level of the method. With this method, we were able to detect Cr(VI) in air at concentrations of 5.3ng/m(3) (assuming a sampling volume of 1m(3) and a final solution volume of 10mL). Recovery tests at three different concentrations of Cr(VI) (50, 250, 1000ng) were performed with or without fly ash; recovery rates at all the concentrations of Cr(VI), with or witho...

Research paper thumbnail of Occurrence, profiles, and toxic equivalents of chlorinated and brominated polycyclic aromatic hydrocarbons in E-waste open burning soils

Environmental pollution (Barking, Essex : 1987), Jan 23, 2017

We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycycli... more We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and brominated polycyclic aromatic hydrocarbons (Br-PAHs) in e-waste open burning soils (EOBS). In this study, concentrations of 15 PAHs, 26 Cl-PAHs and 14 Br-PAHs were analyzed in EOBS samples. We found that e-waste open burning is an important emission source of Cl-PAHs and Br-PAHs as well as PAHs. Concentrations of total Cl-PAHs and Br-PAHs in e-waste open burning soil samples ranged from 21 to 2800 ng/g and from 5.8 to 520 ng/g, respectively. Compared with previous studies, the mean of total Cl-PAH concentrations of the EOBS samples in this study was higher than that of electronic shredder waste, that of bottom ash, and comparable to fly ash from waste incinerators in Korea and Japan. The mean of total Br-PAH concentrations of the EOBS samples was generally three to four orders of magnitude higher than those in incinerator bottom ash and comparable t...

Research paper thumbnail of Spatial and temporal trends of short- and medium-chain chlorinated paraffins in sediments off the urbanized coastal zones in China and Japan: A comparison study

Environmental pollution (Barking, Essex : 1987), Jan 13, 2017

To examine the impacts of urbanization and industrialization on the coastal environment, and asse... more To examine the impacts of urbanization and industrialization on the coastal environment, and assess the effectiveness of control measures on the contamination by chlorinated paraffins (CPs) in East Asia, surface and core sediments were sampled from the urbanized coastal zones in China and Japan (i.e., Pearl River Delta (PRD), Hong Kong waters and Tokyo Bay) and analyzed for short-chain (SCCPs) and medium-chain CPs (MCCPs). Much higher concentrations of CPs were found in the industrialized PRD than in adjacent Hong Kong waters. Significant correlation between CP concentration and population density in the coastal district of Hong Kong was observed (r(2) = 0.72 for SCCPs and 0.55 for MCCPs, p < 0.05), highlighting the effect of urbanization. By contrast, a relatively lower pollution level of CPs was detected in Tokyo Bay. More long-chain groups within SCCPs in the PRD than in Hong Kong waters and Tokyo Bay implied the effect of industrialization. Comparison of temporal trends betwe...