Search

An analytical method using high-performance liquid chromatography (HPLC) with fluorescence (FL) detection was developed for simultaneously analyzing 10 polycyclic aromatic hydrocarbons (PAHs) and 18 nitro-derivatives of PAHs (NPAHs). The two-dimensional HPLC system consists of an on-line clean-up and reduction for NPAHs in the 1st dimension, and separation of the PAHs and the reduced NPAHs and their FL detection in the 2nd dimension after column-switching. To identify an ideal clean-up column for removing sample matrix that may interfere with detection of the analytes, the characteristics of 8 reversed-phase columns were evaluated. The nitrophenylethyl (NPE)-bonded silica column was selected because of its shorter elution band and larger retention factors of the analytes due to strong dipole-dipole interactions. The amino-substituted PAHs (reduced NPAHs), PAHs and deuterated internal standards were separated on polymeric octadecyl-bonded silica (ODS) columns and by dual-channel detection within 120 min including clean-up and reduction steps. The limits of detection were 0.1-9.2 pg per injection for PAHs and 0.1-140 pg per injection for NPAHs. For validation, the method was applied to analyze crude extracts of fine particulate matter (PM2.5) samples and achieved good analytical precision and accuracy. Moreover, the standard reference material (SRM1649b, urban dust) was analyzed by this method and the observed concentrations of PAHs and NPAHs were similar to those in previous reports. Thus, the method developed herein has the potential to become a standard HPLC-based method, especially for NPAHs.

Household fuel combustion for cooking is a major source of hazardous pollutants, including polycyclic aromatic hydrocarbons (PAHs) and their nitro derivatives (NPAHs). These pollutants impact indoor air quality and human health. In this study of two rural households in Chiang Mai, Thailand, PM2.5 samples were collected both inside and outside the houses during cooking and noncooking periods. Real-time monitoring of indoor PM2.5 was also conducted. The concentrations of PAHs, NPAHs, levoglucosan (LG), and carbon fractions in the PM2.5 fractions were quantified. The most severe contamination was observed inside the house during cooking with mean concentrations of 9980 ng/m3 and 18,700 pg/m3 for PAHs and NPAHs, respectively. The composition profiles of PAHs and NPAHs showed that benz[a]anthracene, benzo[k]fluoranthrene, and benzo[a]pyrene made the greatest contribution to total PAHs, while 9-nitroanthracene made the greatest contribution to total NPAHs. The correlation coefficient (p

A personal inhalation exposure and cancer risk assessment of rural residents in Lampang, Thailand, was conducted for the first time. This highlighted important factors that may be associated with the highest areal incidence of lung cancer. Personal exposure of rural residents to polycyclic aromatic hydrocarbons (PAHs) and their nitro-derivatives (NPAHs) through inhalation of fine particulate matter (PM2.5) was investigated in addition to stationary air sampling in an urban area. The personal exposure of the subjects to PM2.5 ranged from 44.4 to 316 μg/m3, and the concentrations of PAHs (4.2–224 ng/m3) and NPAHs (120–1449 pg/m3) were higher than those at the urban site, indicating that personal exposure was affected by microenvironments through individual activities. The smoking behaviors of the rural residents barely affected their exposure to PAHs and NPAHs compared to other sources. The most important factor concerning the exposure of rural populations to PAHs was cooking activity, especially the use of charcoal open fires. The emission sources for rural residents and urban air were evaluated using diagnostic ratios, 1-nitropyrene/pyrene, and benzo[a]pyrene/benzo[ghi]perylene. Their analyses showed a significant contribution to emission from residents’ personal activities in addition to the atmospheric environment. Furthermore, the personal inhalation cancer risks for all rural subjects exceeded the USEPA guideline value, suggesting that the residents have a potentially increased cancer risk. The use of open fires showed the highest cancer risk. A reduction in exposure to air pollutants for the residents could potentially be achieved by using clean fuel such as liquid petroleum gas or electricity for daily cooking.

28-2016, 博士論文要旨Abstract 以下に掲載：Air Quality, Atmosphere & Health 2017. Springer. 共著者：Walaiporn Orakij, Chetiyanukornkul T, Kasahara C, Boongla Y, Chuesaard T, Furuuchi M, Hata M, Tang N, Hayakawa K, Toriba A.

We developed a sensitive and selective method to simultaneously analyze 37 polycyclic aromatic hydrocarbon quinones (PAHQs) with GC-MS/MS and applied the method to the analysis of standard atmospheric particulate matter samples. PAHQs were reduced with zinc granules and dithiothreitol (DTT) and the reductants were immediately converted to their silylated derivatives in a test tube. Two trimethylsilyl (TMS) groups were introduced into PAHQs through the one-pot reductive TMS derivatization. The PAHQs were derivatized with a mixed silylation reagent (BSA+TMCS+TMSI; (3:2:3)), which is one of the combinations of TMS-derivatization reagents with the highest reactivity. The derivatives produced different fragmentation between o-PAHQs and p-PAHQs. Therefore, isomers that have the same molecular weight are difficult to separate on a column were separated by the selected reaction monitoring (SRM) mode using the characteristic fragmentations, allowing separation and detection of all PAHQ derivatives in less than 30min. The instrumental detection limit (IDL) of each PAHQ was 1.2-29fg/injection and the method quantification limit (MQL) was 0.8-78μg/kg sample. For quantification, six deuterated PAHQs were used as internal standards to achieve high analytical precision. We applied the developed method to four standard atmospheric particulate matter samples. Results showed that out of 37 PAHQs, 33 compounds were identified and quantified. Moreover, from the 33 PAHQs, 14 were detected for the first time. Similar values were observed for the concentrations of PAHQs that have been quantified in previous reports. This method has the highest practicality in monitoring PAHQs in atmosphere, combustion exhaust gas, and toxicity evaluation. Thus, the method has the potential to become a standard analytical method for such applications.