Real-Time Gas-Phase Analysis of Mono- to Tri-Chlorobenzenes Generated from Heated MSWI Fly Ashes Containing Various Metal Compounds: Application of VUV-SPI-IT-TOFMS

Fujimori, Takashi; Takaoka, Masaki; Tsuruga, Shigenori; Oshita, Kazuyuki; Takeda, Nobuo

doi:10.1021/es1008888

Cited by 12 publications

(17 citation statements)

References 25 publications

(34 reference statements)

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“…Moreover, highly chlorinated benzenes, such as hexa-and pentachlorobenzenes, are classed as persistent organic pollutants (POPs). In general, CBzs have a one-order higher concentration and a higher volatilization through de novo synthesis than PCDD/Fs (Stieglitz et al, 1989b;Fujimori et al, 2010), indicating the atmospheric impact of CBzs from thermal MSWI process.…”

Section: Introductionmentioning

confidence: 99%

Influence of the Properties of Macromolecular Carbon on de Novo Synthesis of PCDDs, PCDFs, PCBs, and Chlorobenzenes

Fujimori

Nishimura

Oshita

et al. 2014

Aerosol Air Qual. Res.

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We examined the influence of the properties of macromolecular carbon on thermochemical de novo synthesis of toxic chlorinated aromatic compounds (aromatic-Cls), such as polychlorinated dibenzo-p-dioxins (PCDDs), furans (PCDFs), biphenyls (PCBs), and chlorobenzenes (CBzs). Six types of macromolecular carbons were prepared. Some activated carbon samples were modified by chemical solvents, such as nitric acid, hydrogen peroxide, sulfuric acid, and urea solutions, to change the properties of the activated carbon. We characterized six macromolecular carbons by surface area (8.8-1540 m 2 /g), free radicals (N s = not analyzed to 67.0 × 10 19 g -1 , g = 2.0011-2.0098), and functional groups (O-H, C-H, C=O, C=C, C-O, and C-OH). Concentrations of aromatic-Cls at 300-400°C, such as PCDDs, PCDFs, PCBs, and CBzs, were clearly influenced by the type of macromolecular carbon. Their distribution between the ash/gas phases implied that increasing the surface area mainly enhanced the adsorption capacity of macromolecular carbon, while increasing the number of free radicals mainly enhance the reaction activity of macromolecular carbon. The PCDD/PCDF ratio suggested that various modifications of macromolecular carbon contributed to the generation of PCDDs in addition to the catalytic behavior of copper. Under most conditions, the surface area of macromolecular carbon did not have a strong correlation with the generation of PCDDs, PCBs, and CBzs, but it did show have a correlation with the generation of PCDFs. One of the destructive effects of aromatic-Cls resulted from the free radicals in macromolecular carbon. The C=O bond (ca. 1720 cm -1 ) functional group in macromolecular carbon had no strong correlation with the generation of aromatic-Cls, because free radicals had a destructive effect. The functionalities of ether (C-O) or phenolic OH (C-OH) in macromolecular carbon were causative factors in the generation of oxygen-containing aromatic-Cls, such as PCDDs and PCDFs.

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Section: Introductionmentioning

confidence: 99%

Influence of the Properties of Macromolecular Carbon on de Novo Synthesis of PCDDs, PCDFs, PCBs, and Chlorobenzenes

Fujimori

Nishimura

Oshita

et al. 2014

Aerosol Air Qual. Res.

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“…Characterization of PI mass spectra for individual compounds was very limited. VUV-SPI based ion trap TOF/MS method was developed which enabled time-dependent characterization of volatile low-chlorinated benzenes in gas phase in various artificial and environmental processes . Since laser-based systems usually involve high costs and the effort of maintaining a complex system, continuous VUV lamps such as deuterium or krypton discharge lamps pose an option .…”

mentioning

confidence: 99%

“…VUV-SPI based ion trap TOF/MS method was developed which enabled time-dependent characterization of volatile low-chlorinated benzenes in gas phase in various artificial and environmental processes. 24 Since laser-based systems usually involve high costs and the effort of maintaining a complex system, continuous VUV lamps such as deuterium or krypton discharge lamps pose an option. 8 Despite several advantages over other soft ionization techniques reported earlier, the major drawbacks are the relative experimental complexity of the technique and inaccessibility to the standard PI sources until its commercialization in recent past.…”

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confidence: 99%

Molecular Characterization of Volatiles and Petrochemical Base Oils by Photo-Ionization GC×GC-TOF-MS

et al. 2017

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The characterization of organic mixtures by comprehensive two-dimensional gas chromatography (GC×GC) coupled to electron impact (EI) ionization time-of-flight mass spectrometry (TOF-MS) allows the detection of thousands of compounds. However, owing to the exhaustive fragmentation following EI ionization, despite the use of mass spectral libraries, a majority of the compounds remains unidentified because of the lack of parent ion preservation. Thus, soft-ionization energies leading to organic compounds being ionized with limited or no fragmentation, retaining the molecular ion, has been of interest for many years. In this study, photoionization (PI) was evaluated as the ion source for GC×GC-TOF-MS measurements. First, capabilities and limitations of PI were tested using an authentic mixture of compounds of several chemical classes. Ionization energy exhibited by PI, equivalent to 10.8 eV, resulted in significant retention of molecular ion information; [M] for alkanes, ketones, FAMEs, aromatics, [M-H] for chloroalkanes, and [M-HO] for alcohols. Second, considering the potential of PI for hydrocarbons, base oils, complex mixtures of saturated and unsaturated hydrocarbons blended for finished lubricant formulations, were extensively evaluated. Several chemical classes of hydrocarbons were positively identified including a large number of isomeric compounds, both aliphatics and cyclics. Interestingly, branched-alkanes were ionized with lower excess internal energy, not only retaining the molecular ions but also exhibiting unique fragmentation patterns. The results presented herein offer a unique perspective into the detailed molecular characterization of base oils. Such unprecedented identification power of PI coupled with GC×GC-TOF-MS is the first report covering volatiles to low-volatile organic mixtures.

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“…However, information on the occurrence and emission characteristics of both low and highly chlorinated benzenes is still limited, particularly in ash samples. In addition, the abundance of low-chlorinated benzenes, especially in fly ash generated from municipal waste incineration was also reported in previous studies (Fujimori et al 2010(Fujimori et al , 2014. In geographical point of view, most of the studies on the emission of U-POPs including CBzs from industry have been conducted in China (Liu et al 2009(Liu et al , 2013Nie et al 2011Nie et al , 2012Zhang et al 2011), Taiwan (Chen et al 2007), and Japan (Akimoto et al 1997;Murakami et al 2008;Fujimori et al 2010Fujimori et al , 2014.…”

Section: Introductionmentioning

confidence: 54%

“…In addition, the abundance of low-chlorinated benzenes, especially in fly ash generated from municipal waste incineration was also reported in previous studies (Fujimori et al 2010(Fujimori et al , 2014. In geographical point of view, most of the studies on the emission of U-POPs including CBzs from industry have been conducted in China (Liu et al 2009(Liu et al , 2013Nie et al 2011Nie et al , 2012Zhang et al 2011), Taiwan (Chen et al 2007), and Japan (Akimoto et al 1997;Murakami et al 2008;Fujimori et al 2010Fujimori et al , 2014. However, very little information on the CBz emission from industries in Asian developing countries such as Vietnam.…”

Section: Introductionmentioning

confidence: 87%

Levels, profiles, and emission characteristics of chlorobenzenes in ash samples from some industrial thermal facilities in northern Vietnam

Nguyen

Tung

et al. 2018

Environ Sci Pollut Res

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Chlorobenzenes (CBzs) are unintentionally produced organic contaminants from different thermal industrial processes, which have been scarcely surveyed in Asian developing countries including Vietnam. In this study, residue concentrations, profiles, emission factors, and annual emissions of seven chlorobenzene compounds were investigated in fly ash and bottom ash samples of some industrial facilities including brick making plant, steel and zinc production plants, and industrial and municipal waste incinerators in northern Vietnam. Total concentrations of seven CBzs in the ash samples were generally decreased in the order: industrial waste incinerator > municipal waste incinerator > steel-making plant > brick making plant. Emission pattern of CBzs varied considerably among different industrial plants, with 1,2-and 1,3-dichloro-, 1,2,3,4-tetrachloro-, and hexachlorobenzene as predominant compounds in the industrial waste incinerators and steel-making plants. Emission factors of CBzs estimated for the fly ash and bottom ash samples were in the range of 118-2020 and 5.3-22,600 μg ton −1 , respectively. Average annual emissions (AEs) of total seven CBzs estimated for fly ash and bottom ash in the investigated plants were in the range of 154-54,300 and 20,160-161,400 mg year −1 , respectively. The AEs of CBzs estimated for fly ash in the steel-making plant were higher than those in the waste incinerators. Meanwhile, CBz emissions for bottom ash were the highest in the steel-making plant, followed by the industrial and municipal waste incinerators. This is among the first studies on the emission characteristics of both low and highly chlorinated benzenes from industrial activities in Vietnam.

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Real-Time Gas-Phase Analysis of Mono- to Tri-Chlorobenzenes Generated from Heated MSWI Fly Ashes Containing Various Metal Compounds: Application of VUV-SPI-IT-TOFMS

Cited by 12 publications

References 25 publications

Influence of the Properties of Macromolecular Carbon on de Novo Synthesis of PCDDs, PCDFs, PCBs, and Chlorobenzenes

Influence of the Properties of Macromolecular Carbon on de Novo Synthesis of PCDDs, PCDFs, PCBs, and Chlorobenzenes

Molecular Characterization of Volatiles and Petrochemical Base Oils by Photo-Ionization GC×GC-TOF-MS

Levels, profiles, and emission characteristics of chlorobenzenes in ash samples from some industrial thermal facilities in northern Vietnam

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