Abstract

1-Nitropyrene (1-NP), 2-NP and 2-nitrofluoranthene (2-NFR) are useful markers for studying the atmospheric behaviors of polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs). However, present methods for measuring trace levels of these compounds are lesssensitive and laborious. Here we describe several improvements to a previously reported high-performance liquid chromatography-chemiluminescence detection system that allows it to determine trace levels of 1-, 2-NPs and 2-NFR. The proposed system was equipped with a reducer column packed with Pt/Rh instead of zinc whose life-time was limited. The combination of Cosmosil MS-II (monomeric ODS) and AR-II (polymeric ODS) columns was used instead of polymeric ODS columns as the separator column to improve the separation. An ethanol mixture with acetate buffer (pH 5.5) was used in place of an acetonitrile mixture with the same buffer to activate the reducer column. The same ethanol mixture was used as the mobile phase for the clean-up column. The switching time of the column switching valve was optimized to concentrate the amino-derivatives of above NPAHs quantitatively on the concentrator column. The concentrations of bis(2,4,6-trichlorophenly) oxalate and hydrogen peroxide in the chemiluminescence reagent solution were optimized to 0.4 mM and 30 mM, respectively, to increase the sensitivity. Under the above conditions, the detection limits (S/N=3) of 1-, 2-NPs and 2-NFR were 1 fmol (0.25 pg), 10 fmol (2.5 pg) and 4 fmol (1 pg), respectively. The proposed system was effectively used to determine trace levels of 1-, 2-NPs and 2-NFR in airborne particulates collected at Noto Peninsula. The atmospheric concentrations of 1-, 2-NPs and 2-NFR were not more than sub pg <TEX>$m^{-3}$</TEX> levels. They were higher in winter (January) than in summer (July). In both seasons, the concentrations were in decreasing order, [2-NFR]>[1-NP]>[2-NP].

Highlights

  • Among the air pollutants exhausted from the combustion of fossil fuels such as petroleum and coal, polycyclic aromatic hydrocarbons (PAHs) show carcinogenicity and/or mutagenicity (Tokiwa et al, 1980), endocrine disrupting activity (Kizu et al, 2000) or reactive oxygen species producing activity (Motoyama et al, 2009)

  • We developed an high-performance liquid chromatography (HPLC)-chemiluminescence detection (CLD) system for the simultaneous determination of more than 20 Nitropolycyclic aromatic hydrocarbons (NPAHs) by introducing the reducer column packed with Pt/Rh instead of zinc, since Pt/Rh catalyzed the reduction of NPAHs

  • In our previous HPLC-CLD system using the reducer column packed with Pt/Rh, the retention time of 2-NFR was close to that of 2-NP (Tang et al, 2005)

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Summary

Introduction

Among the air pollutants exhausted from the combustion of fossil fuels such as petroleum and coal, polycyclic aromatic hydrocarbons (PAHs) show carcinogenicity and/or mutagenicity (Tokiwa et al, 1980), endocrine disrupting activity (Kizu et al, 2000) or reactive oxygen species producing activity (Motoyama et al, 2009). Nitropolycyclic aromatic hydrocarbons (NPAHs) such as 1-nitropyrene (1-NP) and 1,3-dinitropyrene are exhausted from the combustion of fossil fuels, and their mutagenicity was much stronger than that of benzo[a]pyrene. The authors developed a highly sensitive determination method for NPAHs in environmental samples such as airborne particulates and particulates exhausted from automobiles by using high-performance liquid chromatography (HPLC) with chemiluminescence detection (CLD) (Hayakawa et al, 1995, 1991; Imaizumi et al, 1990).

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