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Atmospheric quinoid polycyclic aromatic hydrocarbons (PAHQs) have adverse health effects as redox-active species in particulate matter (PM). Several PAHQs are known to be very reactive in the dithiothreitol (DTT) assay; however, it is unclear if pyrenequinones, their parent pyrene is one of the most abundant polycyclic aromatic hydrocarbons (PAHs) in the atmosphere, contribute to the loss of DTT in PM extracts. Herein, by employing the DTT assay, we evaluated oxidative potentials of three pyrenequinone isomers (4, 5-pyrenequinone [4, 5-PyQ] and a mixture of 1, 6-/1, 8-pyrenequinones [1, 6-/1, 8-PyQ]), along with 9, 10-phenanthrenequinone (PQN), 1, 2-naphthoquinone (1, 2-NQ), and 1, 4-naphthoquinone (1, 4-NQ), of which DTT loss rates were examined previously. Our results demonstrate that the DTT consumption by ortho-type PAHQs is fast, particularly by 4, 5-PyQ. The order of DTT loss rate by the PAHQs tested in this study was as follows: 4, 5-PyQ ∼ PQN > 1, 2-NQ > 1, 4-NQ ∼ 1, 6-/1, 8-PyQ. 4, 5-PyQ was confirmed to be active in the DTT assay for the first time in this study. The DTT consumption rate by 4, 5-PyQ is 14.6 ± 0.8 mol/min/PAHQ-mol, which is comparable to that of PQN (14.4 ± 0.1 mol/min/PAHQ-mol) known as the most active PAHQs by the DTT assay so far.

CCl4 liquid-phase reaction kinetics of polycyclic aromatic compounds (PACs), including chrysene (CHRY), benz[a]anthracene (BaA), and benzanthrone (BA), with NO3 radicals were investigated at 273 K using a relative rate method with naphthalene (NA) as the reference compound. The obtained relative reaction rates of CHRY, BaA, and BA to NA were 1.76 ± 0.08, 2.27 ± 0.20, 0.75 ± 0.01, respectively. CHRY, BaA, and BA are semi-volatile PACs with four aromatic rings. They are chemically modified into mutagenic nitropolycyclic aromatic compounds via gas-phase OH or NO3 radical-initiated reactions. Based on the PACs relative reactivity in the CCl4 liquid phase-system, the rate constants at 298 K for the gas-phase reaction of CHRY, BaA, and BA with OH radicals and those of CHRY, BaA, and BA with NO3 radicals were estimated to be (in cm3molecule−1s−1): CHRY, (4.4 ± 0.3) × 10−11 and (9.2 ± 3.2) × 10−28 [NO2]; BaA, (5.3 ± 0.5) × 10−11 and (1.3 ± 0.5) × 10−27 [NO2]; BA, (2.3 ± 0.1) × 10−11 and (3.1 ± 1.1) × 10−2...

The formation of hydroxynitrofluoranthene (OHNF) via photochemical reactions of 2-nitrofluoranthene (2-NF) was demonstrated using a UV irradiation system. The photoreaction of 2-NF in acetonitrile/water (3/1, v/v) gave a product that was hydroxynitro-substituted. Moreover, we detected an OHNF isomer, which was found in the 2-NF photoreaction products, in soluble organic fractions of ambient airborne particles collected in Kanazawa, Japan. The atmospheric concentration of the OHNF isomer was estimated to be less than 2 fmol m−3, which was comparable to that of 1-hydroxy-3-nitropyrene, but lower than that of 1-hydroxy-6-nitropyrene by a factor of 10. The results suggests that atmospheric OHNF is partly formed via secondary formation processes, i.e., photochemical reactions of 2-NF appear to have a significant effect on the occurrence of OHNF in the atmosphere.

We investigated polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) in airborne particulates collected at two sites (I and T) in Hanoi city, a typical city where traffic jams were caused by many motorbikes. The mean total concentration of 10 PAHs having 4–6 rings at sites I and T ranged from 9.6–63.7 pmol m−3 and from 24.8–41.9 pmol m−3, respectively. The predominant PAHs determined were 6-ring PAHs: benzo[ghi]perylene (BghiPe), indeno[1,2,3-cd]pyrene (IDP) and 5-ring PAHs: benzo[b]fluoranthene (BbF), benzo[a]pyrene (BaP). The NPAHs with the highest mean concentrations were 9-nitroanthracene (9-NA) (297 ± 134 fmol m−3) at site I and 1-nitropyrene (1-NP) (331 ± 103 fmol m−3) at site T. Both PAH and NPAH concentrations were higher in winter at site I but higher in summer at site T. Diagnostic markers indicated that motorbikes strongly contributed to atmospheric PAHs and NPAHs in Hanoi city. The contribution of PAHs having 6 rings and 7-NBaA in Hanoi city was larger and ...

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants, and generate various types of PAH derivatives, such as nitrated PAHs, hydroxylated PAHs, and PAH quinones through chemical reactions in the atmosphere. PAHs are well known to activate the aryl hydrocarbon receptor (AhR), followed by the induction of metabolizing enzymes mainly in the liver, while biological responses to PAH derivatives are not understood well. In this study, we investigated the induction patterns of gene expression of CYP1 family and Phase II metabolizing enzymes in rat H4IIE cells exposed to PAH quinones and their parent PAHs for 24 h. Dibenz[a,h]anthracene and benzo[a]pyrene dramatically induced mRNA expression of CYP1 family, such as cytochrome P450 (Cyp) 1a1, Cyp1a2, and Cyp1b1, and PAH quinones, especially 1,4-chrysenequinone, possess a high potential to induce CYP1 family. As for Phase II enzymes, PAHs induced NAD(P)H: quinone oxidoreductase 1 (Nqo1) and UDP-glucuronosyltransferase (Ugt)1a6, and their i...

A correction method for the determination of atmospheric monohydroxylated derivatives of 1-nitropyrene (hydroxy-1-nitropyrenes, OHNPs) based on their degradation rates during high volume air sampling was established. OHNPs adsorbed directly on a quartz fibre filter (QFF) or on airborne particles collected on a QFF were exposed to ambient air passively or actively in a high volume air sampling system. The influence of ozone flux and exposure time on the degree of degradation of OHNPs was investigated. Up to 50% of OHNPs degraded over 1 h of exposure to ambient air containing ∼60 ppbv of ozone in the active system. The degradation rate constants of OHNPs were found to correlate with the number of ozone molecules passing through the QFF in a unit time (NO3) during high volume air sampling. The chemical loss of OHNPs under high volume air sampling conditions was successfully evaluated by the exposure time and the pseudo-first-order rate constant for OHNP degradation estimated from the correlation with NO3. Co...

Binding activities and estrogenic/antiestrogenic activities of polycyclic aromatic hydrocarbons (PAHs) and hydroxylated PAHs (OHPAHs) having 2 to 6 rings were evaluated by competition assay and yeast two-hybrid assay expressing human estrogen receptor (hER), respectively. PAHs did not bind to hER and did not show any activity. On the other hand, OHPAHs bound to hER and several OHPAHs showed estrogenic or antiestrogenic activity. Relative estrogenic activity (REP E ) and antiestrogenic activity (REP AE ) were calculated from the values of E 2 and 4-hydroxytamoxyfen as positive controls, respectively. Several OHPAHs having 4 rings showed strongly estrogenic activity. 4-Hydroxybenzo[a]anthracene exhibited the strongest estrogenic activity (REP E = 7.5 × 10−3 ) followed by 3-hydroxybenzo[a]anthracene and 2-hydroxychrysene (REP E = 4.2 × 10−3 ). Several other 4-ring OHPAHs showed strongly antiestrogenic activity. 3-Hydroxybenzo[c]phenanthrene exhibited the strongest antiestrogenic activity (REP AE = 190) follo...

Airborne particulates were collected in nine size fractions by using Andersen low-volume air samplers in the cities of Shenyang, Fushun, and Tieling, Liaoning Province, in northeast China, during the period from July 2001 through December 2003. Nine polycyclic aromatic hydrocarbons (PAHs) and seven nitropolycyclic aromatic hydrocarbons (NPAHs) in the airborne particulates were determined. The mean concentrations of the sums of the nine PAHs and seven NPAHs were highest in Fushun, which is an industrial city, and lowest in Shenyang, which is a commercial city, although the consumption of petroleum and coal were largest in Shenyang. The nine fractions were grouped into three groups: > 7 μ m, 2.1–7 μ m and < 2.1 μ m. In each city, more than 50% of the total PAHs and total NPAHs were found in the fine particulate fraction (< 2.1 μ m). In each city, all PAHs and all NPAHs were clearly higher in winter than in summer. The concentration ratio of 1-nitropyrene to pyrene, which is a suitable indicator to identify ...

Concentrations of nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) and polycyclic aromatic hydrocarbons (PAHs) in airborne particles collected at two sites, a residential area and a roadside with high traffic density in Osaka, Japan, in summer and winter were quantified. Five nitro-PAHs, 1-nitropyrene (1-NP), 2-nitropyrene (2-NP), 2-nitrofluoranthene (2-NF), 3-nitrofluoranthene (3-NF), and 2-nitrotriphenylene (2-NTP) and five PAHs, pyrene (Py), fluoranthene (Fl), triphenylene (Tp), benzo[k]fluoranthene (B(k)F), and benzo[a]pyrene (B(a)P) were determined by high-performance liquid chromatography with chemiluminescence and fluorescence detection. At both sites, the mean concentration of 1-NP was higher in winter than in summer. On the contrary, the mean concentrations of 2-NF and 2-NP were higher in summer than in winter. Observed 2-NF/2-NP ratio in the range from 0.40 to 16 suggests that 2-NF and 2-NP were dominantly formed via OH radical initiated reaction in the atmosphere. Nitro-PAH and PAH concen...