京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20392号 / 工博第4329号 / 新制||工||1671(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 村田 靖次郎, 教授 近藤 輝幸, 教授 小澤 文幸 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Fireworks on Independence Day have been identified as a nationwide but short-term source of particulate matter in the U.S. No study has specifically examined their impacts on ambient polycyclic aromatic hydrocarbons (PAHs). Based on data between 1990 and 2019 in the Air Quality System, we identified 76 unique events that had PAH measurements on both July 4th days and control days (within 15 days before and after July 4th). We compared concentrations and diagnostic ratios of 16 priority PAHs between event and control days using Wilcoxon signed-rank tests and multivariable regressions. A local PAH monitoring campaign was conducted at eight sites in Memphis, Tennessee, to obtain a close observation of PAH changes. The national geometric mean (GM) concentrations of summed 16 PAHs (ΣPAHs) were similar between event and control days (48.1 ng/m3 vs. 52.8 ng/m3, p = 0.98). About a quarter of events had elevated PAH concentrations compared with control days. Higher diagnostic ratios were found on event days, suggesting more contributions from fireworks sources. PAHs on July 4th were unlikely to cause acute or chronic health effects. While the local monitoring showed a 15% increase of ΣPAHs on July 4th, the difference was not significant (p = 0.62). Elevated PAH concentrations occurred at sites near fireworks sources and without major traffics, but did not occur at those in remote areas or near major interstate highways. In conclusion, this study finds that Independence Day fireworks have negligible impacts on atmospheric PAHs at the national level, and are unlikely to pose significant health risks. The firework effect is localized within a limited geographic scale, suggesting potential needs for local monitoring and control programs.

Polycyclic aromatic hydrocarbons (PAH) are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. Because many of them are highly suspect as etiological agents in human cancer, chemical analysis of PAH is of great environmental and toxicological importance. Current methodology for PAH follows the classical pattern of sample preparation and chromatographic analysis. Sample preparation preconcentrates PAH, simplifies matrix composition, and facilitates analytical resolution in the chromatographic column. Among the several approaches that exist to pre-concentrate PAH from water samples, the Environmental Protection Agency (EPA) recommends the use of solid-phase extraction (SPE). High-performance liquid chromatography (HPLC) and gas chromatographymass spectrometry (GC-MS) are the basis for standard PAH identification and determination. Ultraviolet (UV) absorption and room temperature fluorescence detection are both widely used in HPLC, but the specificity of these detectors is modest. Since PAH identification is solely based on retention times, unambiguous PAH identification requires complete chromatographic resolution of sample components. When HPLC is applied to "unfamiliar" samples, the EPA recommends that a supporting analytical technique such as GC-MS be applied to verify compound identification and to check peak-purity HPLC fractions. Independent of the volume of extracted water, the approximate time required to separate and determine the sixteen "priority pollutants" (EPA-PAH) via HPLC is approximately 60min. If additional GC-MS analysis is required for unambiguous PAH determination, the total analysis time will reach 2-3 hours per sample. If the concentrations of target species are found to lie outside the detector’s response range, the sample must be diluted and the process repeated. These are important considerations iv when routine analysis of numerous samples is contemplated. Parent PAH are relatively inert and need metabolic activation to express their carcinogenicity. By virtue of the rich heterogeneous distribution of metabolic products they produce, PAH provide a full spectrum of the complexity associated with understanding the initial phase of carcinogenesis. PAH metabolites include a variety of products such as expoxides, hydroxyl aromatics, quinines, dihydrodiols, dioepoxides, tetrols and water soluble conjugates. During the past decades tremendous efforts have been made to develop bio-analytical techniques that possess the selectivity and sensitivity for the problem at hand. Depending on the complexity of the sample and the relative concentrations of the targeted metabolites, a combination of sample preparation techniques is often necessary to reach the limits of detection of the instrumental method of analysis. The numerous preparation steps open ample opportunity to metabolite loss and collection of inaccurate data. Separation of metabolites has been accomplished via HPLC, capillary electrophoresis (CE) and GC-MS. Unfortunately, the existence of chemically related metabolic products with virtually identical fragmentation patterns often challenges the specificity of these techniques. This dissertation presents significant improvements in various fronts. Its first original component – which we have named solid-phase nano-extraction (SPNE) - deals with the use of gold nanoparticles (Au NPs) as extracting material for PAH. The advantages of SPNE are demonstrated for the analysis of PAH in water samples via both HPLC1 and Laser-Excited TimeResolved Shpol’skii Spectroscopy (LETRSS).2 The same concept is then extended to the analysis of monohydroxy-PAH in urine samples via SPE- HPLC3 and In-Capillary SPNE-CE.4 The second original component of this dissertation describes the application of Shpol’skii Spectroscopy to the analysis of polar PAH metabolites. The outstanding selectivity and v sensitivity for the direct analysis of PAH at trace concentration levels has made Shpol’skii spectroscopy a leading technique in environmental analysis.5 Unfortunately, the requirement of a specific guest-host combination - typically a non-polar PAH dissolved in an n-alkane - has hindered its widespread application to the field of analytical chemistry. This dissertation takes the first steps in removing this limitation demonstrating its feasibility for the analysis of polar benzo[a]pyrene metabolites in alcohol matrixes.6

Polycyclic aromatic hydrocarbons (PAH) are important environmental pollutants generally formed during incomplete combustion of organic matter containing carbon and hydrogen. Introduced into the human body by adsorption through the skin, ingestion or inhalation, the biotransformation processes of PAH lead to the formation of multiple metabolites. Due to the short elimination lifetime from the body, the quantitative determination of monohydroxy-PAH (OH-PAH) in urine samples provides accurate information on recent exposure to environmental PAH. Urine analysis of OH-PAH with established methodology relies on sample clean-up and pre-concentration followed by chromatographic separation and quantification. Although chromatographic techniques provide reliable results in the analysis of OH-PAH, their experimental procedures are time consuming and expensive. Additional problems arise when laboratory procedures are scaled up to handle thousands of samples under mass screening conditions. Under the prospective of a sustainable environment, the large usage of organic solvents is one of the main limitations of current chromatographic methodology. It is within this context that new analytical approaches based on easy-to-use and cost-effective methodology become extremely relevant. This dissertation focuses on the development of screening methodology for the routine analysis of PAH metabolites in numerous samples. It explores the room-temperature fluorescence properties of six metabolites originating from parent PAH included in the Environmental Protection Agency priority pollutants list. 1- hydroxyfluorene, 1-hydroxypyrene, 6-hydroxychrysene, 9-hydroxyphenanthrene, 3- hydroxybenzo[a]pyrene and 4-hydroxybenzo[a]pyrene are used as model biomarkers to investigate the analytical potential of new methods based on solid-phase extraction (SPE) and iii room-temperature fluorescence (RTF) spectroscopy. Quantitative determination of metabolites is carried out either in the eluent extract[1, 2] or on the surface of extraction membranes[3, 4] . The direct determination – i.e., no chromatographic separation - of the six metabolites is based on the collection of excitation-emission matrices and synchronous fluorescence spectra.

Human bodies are in constant interaction with materials containing known and unknown chemicals of hazardous behavior. One group of chemicals are polycyclic aromatic compounds (PACs) which can be present in both indoor and outdoor materials, commonly in plastics. PACs are known for their cancerogenic behavior and thus should be considered and studied in an attempt to decrease human exposure. The following project reports the execution and results from chemical analysis of 48 PACs including parent polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs and dibenzothiophenes (S-PAC), searched for in different materials commonly found indoors. Eleven samples were prepared and analyzed using GC/MS target analysis. 23 out of the 33 parent PAHs targeted were detected and quantified. In addition, 12 out of 15 alkylated PAHs including four dibenzothiophenes (S-PAC) were detectable in the samples. The contents of parent PAHs ranged from 105 ng/g to 6700 ng/g in the samples, with the highest value being present in a laminated artificial leather sample. The alkylated PAHs ranged from 34 ng/g to 3000 ng/g, and a recycled hard plastic contained the highest amount. Amongst the parent PAHs, the dominating compound in the samples was phenanthrene. For the alkylated PAHs, 2-methylnaphtalene was the compound present in the highest mass fraction. When comparing the samples, most similarities in PAC composition could be seen in the artificial leather samples excluding a high content of naphthalene in the laminated leather. The recycled plastic material consisted of the highest variety of PACs. The results presented that none of the samples exceeded the limit values set by EU regulation regarding eight PAHs (PAH8) in consumer products. However, poor recovery in addition to poor resolution of the majority of the high molecular mass compounds suggest further investigation of method optimization.

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