504

Journal of Health Science, 57(6) 504–511 (2011)— Minireview —Atmospheric Chemistry of Polycyclic Aromatic
Hydrocarbons and Related Compounds
Takayuki Kameda∗
Institute of Medical, Pharmaceutical and Health Sciences, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920–1192,
Japan(Received August 13, 2011)

Polycyclic aromatic compounds are ubiquitous atmospheric pollutants with toxic, mutagenic, and carcinogenic
properties. They are produced from chemical reactions of their parent compounds in the atmosphere as well asfrom a wide variety of anthropogenic sources such as fuel combustions. The present review is mainly concernedwith several reaction pathways regarding secondary formation of atmospheric polycyclic aromatic hydrocarbon(PAH) derivatives, i.e., formation of mutagenic nitrated PAHs, 1- and 2-nitrotriphenylene, via gas-phase OH or
NO3 radical-initiated reactions of the parent triphenylene, atmospheric formation of hydroxynitropyrenes from a
photochemical reaction of 1-nitropyrene, and photochemical degradation of selected nitrated and oxygenated PAHs
on airborne particles under simulated solar UV-irradiation.
Key words —— polycyclic aromatic compound, secondary formation, photolysis, atmospheric reaction

INTRODUCTION
Polycyclic aromatic hydrocarbons (PAHs) andtheir derivatives, such as nitrated, oxygenated, andhydroxylated derivatives (NPAHs, OPAHs, andOHPAHs), are ubiquitous atmospheric pollutants
with toxic, mutagenic, and carcinogenic properties.1, 2) These compounds are predominantly produced from a wide variety of anthropogenic sources
such as the incomplete combustion of fossil fuels
for industrial plants, heating, as well as diesel powered vehicles.3–5) NPAHs, which generally exhibit
higher mutagenicity and carcinogenicity than theparent PAHs, are also generated from atmosphericreactions of PAHs released into the gas-phase withradical species such as OH and NO3 radicals andnitrogen oxides.6–10) OPAHs and OHPAHs, which
may show biological effects different from mutagenicity and carcinogenicity, are also known tobe secondarily formed via oxidation of PAHs and
NPAHs in the atmosphere.11, 12) These derivatized
PAHs generally have lower volatility than the par∗To whom correspondence should be addressed: Instituteof Medical, Pharmaceutical and Health Sciences, Kanazawa
University, Kakuma-machi, Kanazawa, Ishikawa 920–1192,
Japan. Tel.: +81-76-234-4458; Fax: +81-76-234-4456; E-mail:kameda@p.kanazawa-u.ac.jp

ent PAHs and are likely to be deposited on airborne
particles, especially fine particles, which are easily
taken into the inside of human body, and diffuse into
the atmosphere. Thus, it is necessary to understandthe secondary formation processes of PAH derivatives in order to understand their effects on humans.
In this paper, I briefly review chemical reaction
pathways regarding the secondary formation of thePAH derivatives.

FORMATION OF
NITROTRIPHENYLENES BY
RADICAL-INITIATED REACTIONS
Nitrotriphenylenes (NTPs), which include astrongly mutagenic isomer 2-nitrotriphenylene (2NTP), have been found in airborne particulate samples by several researchers.13– 16) The possibilityof atmospheric formation of NTPs via reactionof triphenylene was pointed out based on seasonal and lateral concentration changes of ambient NTPs.14, 15) Since strongly mutagenic 2-NTP
has been found in the air at concentrations comparable to those of 1-nitropyrene (1-NP) and 2nitrofluoranthene (2-NFR), which are the mostabundant airborne NPAHs,13–16) the contribution
C 2011 The Pharmaceutical Society of Japan

No. 6of 2-NTP to the mutagenicity of airborne particles could be significant. From a public hygienic
point of view, the acquisition of more detailed
data about the environmental occurrence of NTPs
is of great importance. Thus, the formation of 1nitrotriphenylene (1-NTP) and 2-NTP by gas-phase
OH or NO3 radical-initiated reaction of triphenylene was demonstrated using a flow reaction system.17) Nitration of triphenylene with N2 O5 in CCl4
was also examined in order to determine the isomer distribution of NTPs formed via NO3 radicalinitiated nitration of triphenylene and in order topredict rate constants of the gas-phase OH or NO3
radical-initiated reactions of triphenylene.
The formation of 1- and 2-NTP was clearlyshown by HPLC analysis of the products of the gasphase reaction of triphenylene initiated by the OH
radicals. A 2-NTP/1-NTP ratio of 1.22 was obtained for OH radical-initiated nitration. In contrast, the NO3 radical-initiated reaction predominantly gave 2-NTP, with traces of 1-NTP. Since
the amount of 1-NTP formed in the NO3 radicalinitiated reaction was too small to determine, a precise 2-NTP/1-NTP value could not be calculated
and was thus assumed to be a value greater than 1.5.
Preferential production of 2-NTP was also observedin the nitration of triphenylene with N2 O5 in CCl4 ;the yields of 1- and 2-NTP were 6 ± 2% and 35 ±2%, respectively. It has been reported that the reactions of several kinds of PAH with N2 O5 in CCl4 aresimilar in terms of nitro-isomer distribution to gasphase NO3 radical-initiated nitration.18, 19) Thus, theanalogous isomer distribution of NTP (the larger
yield of 2-NTP than 1-NTP) in the gas-phase reaction to that in CCl4 liquid-phase nitration does notcontradict previous findings regarding the nitrationof PAH. The mean 2-NTP/1-NTP ratio in samplesof airborne particles was > 1.55; this value was similar to the values from the radical-initiated reactions
and was much higher than that of the diesel exhaust
particulate (DEP) samples (2-NTP/1-NTP = 0.37).
This finding indicates that the atmospheric radicalinitiated reactions significantly contribute to formation of airborne NTPs, especially 2-NTP. Gas-phaseformation of nitro-PAHs via OH or NO3 radicalinitiated reaction involves the addition of an OH or
NO3 radical to PAH at the carbon atom with thehighest electron density, followed by ortho-additionof NO2 , resulting in loss of water or nitric acid. For
triphenylene, the carbon at the 1-position is the mostelectron-rich;20, 21) therefore, preferential formationof 2-NTP over 1-NTP is expected in the gas-phase505

Fig. 1. Scheme of Formation of 2-NTP from OH or NO3
Radical-initiated Reactions of Triphenylene

radical-initiated reaction (Fig. 1).
The rate constants of gas-phase reactionsof triphenylene with OH and NO3 radicals at
298 K were predicted to be (8.6 ± 1.2) × 10−12
cm3 molecule−1 s−1 and (6.6 ± 1.5) × 10−29 [NO2 ]cm3 molecule−1 s−1 , respectively using a relativerate method in a CCl4 liquid phase-system.22) Basedon the ambient concentration of 2-NTP and the obtained rate constant for the reaction of triphenylene
with the radicals, the atmospheric loss rate of 2NTP relative to 2-NFR, which is the most abundant
NPAH and is also produced from the radical reactions, was successfully estimated, i.e. 2-NTP is lesssusceptible to decomposition than 2-NFR under ambient conditions.

ATMOSPHERIC FORMATION OF
HYDROXYNITROPYRENES FROM A
PHOTOCHEMICAL REACTION OF
PARTICLE-ASSOCIATED 1-NP
1-NP, one of the most abundant NPAHs in
the atmosphere, is a representative NPAH formed
through combustion of fossil fuels such as diesel
fuel. 1-NP taken up by humans and animals istransformed to various metabolites such as hydroxynitropyrenes (OHNPs) in the presence of cytochrome P450 enzymes.23) Several isomers of
OHNP (Fig. 2), such as 1-hydroxy-3-nitropyrene (1OH-3-NP), 1-hydroxy-6-nitropyrene (1-OH-6-NP),and 1-hydroxy-8-nitropyrene (1-OH-8-NP) havealso been observed in airborne particles24, 25) and506

Vol. 57 (2011)

DEP.1, 26, 27) Several studies have found that most
OHNP isomers have lower mutagenic activity thanthe parent 1-NP.23, 27, 28) Recently, however, OHNPs
such as 1-OH-3-NP, 1-OH-6-NP, and 1-OH-8-NP
have been found to act as endocrine disruptors,
i.e. they act as estrogenic, anti-estrogenic, andanti-androgenic compounds,29, 30) which may cause
dysfunction of human and wildlife endocrine systems, abnormal development of reproductive systems, and immunodeficiencies. In view of the influence of OHNPs on human health, we need to learn
more about their environmental concentration levels, sources and behavior. Therefore, the formationof OHNPs including 1-OH-3-NP, 1-OH-6-NP, and1-OH-8-NP from photochemical reactions of 1-NP
was examined by laboratory experiments in order toclarify the occurrence of atmospheric OHNPs.31)
Figure 3 shows a profile of HPLC analysis with

Fig. 2. Structure of Hydroxynitropyrene

chemiluminescence detection (HPLC/CLD) for the
products from photoreactions of 1-NP in methanol.
Five chromatographic peaks were observed in thechromatogram as symbolized by A, B, C, D, and E.
The retention times of peaks B, C, D, and E were thesame as those of authentic 1-OH-6-NP, 1-OH-8-NP,
1-OH-3-NP, and 1-hydroxy-2-nitropyrene (1-OH-2NP), respectively. When analyzed by LC/MS/MS,a fraction containing the photo-reaction products
also yielded five peaks. By comparing the retention times and the MS/MS spectra of these peaks
with those of the authentic standards, four known
OHNPs, 1-OH-2-NP, 1-OH-3-NP, 1-OH-6-NP, and1-OH-8-NP, were identified. For these compounds,
the molecular-related ion m/z 262 ([M-H]− ) together with the characteristic fragment ions m/z
232 ([M-H-NO]− ) and 216 ([M-H-NO2 ]− ) were detected in a full scan analysis. 1-OH-3-NP, 1-OH6-NP, and 1-OH-8-NP were found in 1-NP photoreaction products for the first time in the study.
The unknown compound that was observed in the
HPLC/CLD chromatogram was also observed in the
LC/MS/MS analysis. This compound also gave acharacteristic MS/MS spectrum with a molecularrelated ion m/z 262 and fragment ions m/z 232 andm/z 216. The similarity between the fragmentation patterns of the unknown compound and known
OHNPs indicates that the unknown compound isFig. 3. Chromatograms of Standard OHNPs (a) and Photoreaction Products of 1-NP (b) Obtained by the HPLC-chemiluminescence
Detection System

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an isomer of OHNP. The structure of the unknown
compound obtained by the preparative scale photoreaction was then determined by analysis of its
1 H-NMR spectrum. On the basis of chemical shifts
and coupling patterns, the unknown compound contained in the photo-reaction products was identified
as 1-hydroxy-5-nitropyrene (1-OH-5-NP).
All the OHNP isomers, which were found in
the 1-NP photo-reaction products, were also identified in ambient airborne particles collected at a
typical residential area in Osaka, Japan. 1-OH-2NP and 1-OH-5-NP were identified in ambient airborne particles for the first time. On the contrary,these two OHNP isomers were not found in Standard Reference Materials (SRM) 1650b and SRM
1975, which are typical DEP samples. The concentrations of the other OHNP isomers in the DEP samples were much lower than the concentration of 1NP. On the other hand, significantly higher concentration ratios of ΣOHNP (= 1-OH-3-NP + 1-OH-6NP + 1-OH-8-NP) to 1-NP were observed in ambi-

ent airborne particles than in the DEP samples. In
ambient airborne particles, the mean ΣOHNP/1-NP
concentration ratio of 1.4 was 35 times higher thanthat in SRM 1650b and 470 times higher than thatin SRM 1975. The diurnal concentration of 1-NP,
which was observed at the site in Osaka, Japan, increased early in the morning and late in the evening,suggesting that automotive emissions contributed tothe occurrence of 1-NP. The OHNP concentrations
also rose in the morning and variations of OHNP
concentrations similar to those of 1-NP were observed during the daytime. However, the concentrations of OHNPs did not increase in the evening rush
hour, and were low at night, i.e. in the absence ofsunlight. These results support the idea that atmospheric OHNPs are predominantly formed via secondary formation processes, i.e. photochemical reactions of 1-NP are expected to have a significant effect on the occurrence of OHNPs in the atmosphere.

Table 1. Quantum Yield, Photolysis Rate Constant, and Estimated Lifetime of the PAH Derivatives on the Earth’s Surface
BaP
BkF
1-OHPyr
1,3-DNP
1,6-DNP
1,8-DNP
1-NP
1-NPer
2-NA
2-NF
2-NFR
2-NTP
3-NBA
3-NFR
3-NPer
4-NP
6-NBaP
6-NC
7-NBaA
9-NA
9-NPh
1,2-BAQ
1,4-CQ
5,6-CQ
9,10-PQ
AcQ
AQ
B[c]P-5,6-Q

Quantum yield
1.96 × 10−6
4.10 × 10−6
3.05 × 10−5
2.22 × 10−9
3.05 × 10−8
1.27 × 10−8
1.31 × 10−5
4.07 × 10−4
3.61 × 10−4
5.07 × 10−5
4.24 × 10−5
2.25 × 10−5
1.28 × 10−5
1.70 × 10−5
8.13 × 10−5
2.21 × 10−5
3.18 × 10−4
1.05 × 10−4
9.09 × 10−4
1.73 × 10−3
1.88 × 10−4
2.02 × 10−55.33 × 10−5
6.38 × 10−5
1.75 × 10−5
2.68 × 10−4
6.02 × 10−5
2.51 × 10−4

See Fig. 4 for compound abbreviations.

Photolysis rate constant (s−1 )2.22 × 10−5
9.89 × 10−6
2.38 × 10−4
8.15 × 10−5
1.75 × 10−4
2.23 × 10−4
7.85 × 10−5
1.42 × 10−3
1.01 × 10−3
3.26 × 10−4
1.05 × 10−4
1.02 × 10−4
5.23 × 10−5
8.56 × 10−5
1.65 × 10−4
7.31 × 10−5
1.38 × 10−3
5.93 × 10−4
2.12 × 10−3
3.15 × 10−3
4.79 × 10−4
4.74 × 10−5
7.63 × 10−5
9.86 × 10−5
2.23 × 10−4
2.35 × 10−4
8.38 × 10−5
4.33 × 10−4

Lifetime (h)
74.6
125.3
9.3
15.3
7.6
5.8
17.8
1.0
1.6
6.6
17.4
21.1
22.2
17.8
9.9
21.5
1.0
2.8
0.9
0.5
4.3
34.9
15.8
11.6
7.1
7.0
22.7
4.5

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PHOTOCHEMICAL DECOMPOSITION
OF SELECTED NITRO- AND OXY-PAHS
ON AIRBORNE PARTICLES UNDERSIMULATED SOLAR UV-IRRADIATIONAs in the case of 1-NP, photoinduced decomposition is a dominant pathway for the degradation ofparticle-associated PAH derivatives.32, 33) Solar radiation in UV region can modify PAH derivatives
to form new compounds, which may exhibit different types of biological effects such as disruption of endocrine systems and production of reactive oxygen species (ROS) in human body.34) Thus,
it is necessary to understand the photodecomposition of PAH derivatives in order to understand theireffects on humans. However, the rate constants andthe quantum yields regarding the photolysis of thederivatized PAHs, which are the most significant
factors for the photodecomposition, had not beenstudied well. Thus, photodecomposition experiments for selected OPAHs and NPAHs including 3nitrobenzanthrone (3-NBA), a nitrated aromatic ketone that is strongly mutagenic,35) were conducted
on a glass surface as a simple model of airborne particles and the photolysis rate constants and the quantum yields for the PAHs derivatives in the systemwere determined.36) Furthermore, the atmospheric
lifetime of the compounds due to photodecomposition was estimated using the actinic flux on theearth’s surface, photolysis rate constants, and quantum yields obtained in the study.
The largest photolysis rate constant was observed for 9-nitroanthracene (9-NA), while 4nitropyrene (4-NP) and 3-NBA were found themost stable of the nitrated compounds under UVirradiation (Table 1). It is hypothesized that photoreactivity of NPAHs is governed by the orientation of the nitro group, i.e. NPAHs having perpendicular nitro groups are more easily photodecomposed than those having parallel ones.12, 37) The fast photodegradation observedfor 9-NA, 6-nitrobenzo[a]pyrene (6-NBaP), and 7nitrobenz[a]anthracene (7-NBaA), which have aperpendicular nitro group, was consistent withthe hypothesis (Fig. 4). The photoreaction products of NPAHs were reported to include quinoid
PAHs,12) as well as photoreaction products of
PAHs. Benzo[c]phenanthrene-5,6-quinone (B[c]P5,6-Q) which has a similar photolysis rate constant to 9-nitrophenanthrene (9-NPh) degraded thefastest of the seven OPAHs we tested.
1,2-

Fig. 4. Structures of PAH Derivatives Examined in the Photodecomposition Experiment

Benzanthraquinone (1,2-BAQ) was the most resistant to photodecomposition of all the substituted
PAHs examined in the study. Although previous
studies for the photostability of OPAHs were quite
limited, Cvrěková and Ciganek reported that 9,10phenanthraquinone (9,10-PQ) was less stable than

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anthraquinone (AQ) under UV irradiation,38) that is
consistent with our results.
Photolysis rate constants of the tested compounds under irradiation of sunlight were estimatedbased on the actinic flux on the earth’s surface 39)
and the quantum yields obtained in the study. Atmospheric lifetimes of the compounds due to photodecomposition were calculated to be 0.5–22 hr
for NPAHs and 4.5–35 hr for OPAHs using the obtained photolysis rate constants. OPAHs were foundto be more stable against photo irradiation than
NPAHs. This finding indicates that the risk induced by OPAHs is critical for human health, because we may be continuously exposed by OPAHs
due to their longer residence time in the atmosphere.
Recently, it has been found that ROS, which cancause severe oxidative stress connected with inflammatory processing, are produced in larger amounts
via chain reactions induced by quinoid PAHs in thehuman body.34) Further studies on the biological effects and the atmospheric formation and decomposition mechanisms for OPAHs are required.
Acknowledgements These researches were supported by The Ministry of Education, Culture,
Sports, Science and Technology (MEXT)/Japan Society for the Promotion of Science (JSPS) Grant-inAid for Scientific Research (21200031, 22510010,
20710003), the Sumitomo Foundation (073150),
and the Environment Research and Technology Development Fund (RF-0905) of the Ministry of theEnvironment, Japan. I thank Prof. Kazuichi
Hayakawa of Kanazawa University and Prof. Hiroshi Bandow of Osaka Prefecture University for
helpful discussion and kind support throughout myworks.

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