Polycyclic aromatic compounds (PAC) are ubiquitous pollutants in urban air that may pose risks to human health. In order to better assess the health risks associated with this class of compounds, a total of 67 PAC that either have been identified (55) or are suspected to be present (12) in urban aerosol samples were tested for mutagenicity in a forward mutation assay based on human B-lymphoblastoid cells. The cell line used (designated h1A1v2) constitutively expresses the cytochrome P4501A1, which is known to be necessary for the metabolism of many promutagens. The PAC tested included 39 polycyclic aromatic hydrocarbons (PAH). 19 oxygen-containing PAH (oxy-PAH) and nine NO2-substituted PAH (nitro-PAH). A total of 26 PAH were mutagenic. In comparing the minimum mutagenic concentrations of the mutagenic PAH with that of benzo[a]pyrene (B[a]P) it was found that dibenzo[a,l]pyrene (DB[al]P), cyclopenta[c,d]pyrene (CPP), naphtho[2,1-a]pyrene, dibenzo[a,e]pyrene (B[a]P) and 1-methylbenzo[a]pyrene were 24 +/- 21, 6.9 +/- 4.2, 3.2 + 3.0, 2.9 +/- 2.9 and 1.6+/- 1.4 times, respectively, more mutagenic than B[a]P, and that dibenzo[a,k]fluoranthene and B[a]P were approximately equally mutagenic. The 19 other mutagenic PAH were between approximately 2 and approximately 1800 times less mutagenic than B[a]P. Of the oxy-PAH tested only phenalenone, 7H-benz[d,e]anthracen-7-one, 3-nitro-6H-dibenzo[b,d]pyran-6-one, cyclopenta[c,d]pyren-3(4H)-one, 6H-benzo[c,d]pyren-6-one (BPK) and anthanthrenequinone were mutagenic; however, with the exception of BPK, these were over 50 times less active than B[a]P, BPK was approximately 3 times less active than B[a]P. Seven of the nitro-PAH were mutagenic including 9-nitroanthracene, 1-nitropyrene, 2-nitrofluoranthene, 3-nitrofluoranthene, 1,3-dinitropyrene, 1,6-dinitropyrene (1,6-DNP) and 1,8-dinitropyrene. 1,6-DNP was approximately 4 times less active than B[a]P; the six other mutagenic nitro-PAH were between 20 and 380 times less active than B[a]P. These results are discussed in terms of their relevance for determining the most important mutagens in ambient air. Based on reported concentrations of PAC in ambient aerosols, it is possible that CPP, DB[ae]P, DB[al]P and BPK could account for a greater proportion of the mutagenicity than B[a]P in some aerosols.

Human cell mutagenicity of oxygenated, nitrated and unsubstituted polycyclic aromatic hydrocarbons associated with urban aerosols.

The atmospheric chemistry of the 2- to 4-ring polycyclic aromatic hydrocarbons (PAH), which exist mainly in the gas phase in the atmosphere, is discussed. The dominant loss process for the gas-phase PAH is by reaction with the hydroxyl radical, resulting in calculated lifetimes in the atmosphere of generally less than one day. The hydroxyl (OH) radical-initiated reactions and nitrate (NO3) radical-initiated reactions often lead to the formation of mutagenic nitro-PAH and other nitropolycyclic aromatic compounds, including nitrodibenzopyranones. These atmospheric reactions have a significant effect on ambient mutagenic activity, indicating that health risk assessments of combustion emissions should include atmospheric transformation products.

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Atmospheric Chemistry of Gas-phase Polycyclic Aromatic Hydrocarbons: Formation of Atmospheric Mutagens

Since the use of diesel engines is still increasing, the contribution of their incomplete combustion products to air pollution is becoming ever more important. The presence of irritating and genotoxic substances in both the gas phase and the particulate phase constituents is considered to have significant health implications. The quantity of soot particles and the particle-associated organics emitted from the tail pipe of a diesel-powered vehicle depend primarily on the engine type and combustion conditions but also on fuel properties. The quantity of soot particles in the emissions is determined by the balance between the rate of formation and subsequent oxidation. Organics are adsorbed onto carbon cores in the cylinder, in the exhaust system, in the atmosphere and even on the filter during sample collection. Diesel fuel contains polycyclic aromatic hydrocarbons (PAHs) and some alkyl derivatives. Both groups of compounds may survive the combustion process. PAHs are formed by the combustion of crankcase oil or may be resuspended from engine and/or exhaust deposits. The conversion of parent PAHs to oxygenated and nitrated PAHs in the combustion chamber or in the exhaust system is related to the vast amount of excess combustion air that is supplied to the engine and the high combustion temperature. Whether the occurrence of these derivatives is characteristic for the composition of diesel engine exhaust remains to be ascertained. After the emission of the particles, their properties may change because of atmospheric processes such as aging and resuspension. The particle-associated organics may also be subject to (photo)chemical conversions or the components may change during sampling and analysis. Measurement of emissions of incomplete combustion products as determined on a chassis dynamometer provides knowledge of the chemical composition of the particle-associated organics. This knowledge is useful as a basis for a toxicological evaluation of the health hazards of diesel engine emissions.

Combustion of diesel fuel from a toxicological perspective. I. Origin of incomplete combustion products.

While it is known that urban airborne particles typically contain trace levels of bacterial mutagens and rodent carcinogens, little work has been done to identify chemicals in such particles that can genetically alter human cells. In this paper, we describe the analysis of an organic extract of a Washington, DC, airborne particle sample (SRM 1649) for human cell mutagens. Due to the chemical complexity of the extract, a bioassay-directed fractionation method was used to separate mutagenic constituents into chemically simplified fractions. Mutagenicity testing was done using the h1A1v2 cell line, a line of human B-lymphoblastoid cells that have been engineered to overexpress the human cytochrome P4501A1. Chemical analysis of mutagenic fractions was accomplished using GC−MS and HPLC−UV techniques. Our results indicate that ∼20% of the total mutagenicity the extract was accounted for in two fourth-order fractions that contained ∼3% of the total extract mass. These fractions were composed largely of polycycli...

Human lymphoblast mutagens in urban airborne particles

http://eportfolio.lib.ksu.edu.tw/user/T/0/T093000204/repository/Measurements%20of%20nitro-PAH%20in%20the%20atmospheres%20of%20two%20cities.pdf

Measurements of nitro-PAH in the atmospheres of two cities

Three different approaches to the liquid chromatographic detection of nitro polynuclear aromatic hydrocarbons in air and diesel particulate extracts are presented, based on differential pulse (LCDPD) and amperometric (LCEC) electrochemical detection and fluorescence detection following online reduction to the amine (LCFI). The particulate extraction/fractionation procedure for each detection approach is discussed. The operational advantages of oxygen removal with a platinum oxygen scrubber (all three types of detection), the use of modulated pulse detection, and wavelength-programmed fluorescence detection are explored. 1-Nitropyrene is determined in Standard Reference Material (SRM) 1650 diesel particulate matter and in several other round robin samples by all three methods. Results are compared to those obtained by other techniques (gas chromatography/mass spectrometry) and by other laboratories (LCFI). Additionally, 2-nitrofluorene, 9-nitroanthracene, 7-nitrobenz(a)anthracene, and 6-nitrobenzo(a)pyrene are determined in SRM 1650 by LCFI. The detection limits for 1-nitropyrene (expressed as picograms) are 5200 (LCDPD), 60 (LCEC), and 10 (LCFI).

Determination of nitro polynuclear aromatic hydrocarbons in air and diesel particulate matter using liquid chromatography with electrochemical and fluorescence detection.

W. A. MacCrehan

Papers

Determination of nitro polynuclear aromatic hydrocarbons in air and diesel particulate matter using liquid chromatography with electrochemical and fluorescence detection.