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Polycyclic Aromatic Compounds

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Polycyclic Aromatic Hydrocarbons in the

Environment: Environmental Fate and
Transformation
a b
Sergio Manzetti
a
Fjordforsk Institute of Science and Technology , Fresvik , Norway
b
Computational Systems and Biology, Biomedical Centre , University
of Uppsala , Uppsala , Sweden
Published online: 26 Jun 2013.

To cite this article: Sergio Manzetti (2013) Polycyclic Aromatic Hydrocarbons in the Environment:
Environmental Fate and Transformation, Polycyclic Aromatic Compounds, 33:4, 311-330, DOI:
10.1080/10406638.2013.781042

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 Polycyclic Aromatic Compounds, 33:311–330, 2013
Copyright C Taylor & Francis Group, LLC
ISSN: 1040-6638 print / 1563-5333 online
DOI: 10.1080/10406638.2013.781042

Polycyclic Aromatic
Hydrocarbons in the
Environment: Environmental
Fate and Transformation
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Sergio Manzetti1,2
1
Fjordforsk Institute of Science and Technology, Fresvik, Norway
2
Computational Systems and Biology, Biomedical Centre, University of Uppsala,
Uppsala, Sweden

Polycyclic aromatic hydrocarbons are toxic and carcinogenic compounds that occur in
the environment and derive from two classes processes: petrogenic and pyrogenic pro-
cesses. The petrogenic part derives from oil- and drilling activities, including oil disas-
ters, spills, and pollution from industrial sites, refineries, and most importantly traffic
exhaust emissions, while the pyrogenic part derives from fires, forest fires, volcanic
eruptions, and incineration. PAHs have long degradation periods, and recent studies
show high accumulated concentrations in soil, aquatic, and atmospheric environments.
Particularly with the advent of the winter season, pollution and pollution migration
increases by the atmospheric influences on smog clouds, from air to soil, air to water
reserves, and from air to humans. This review maps the recent measurements and con-
centrations of PAHs worldwide, with particular focus on highly exposed regions such
as China, India and former Eastern European countries. Monitoring and mapping the
fate of PAH is of particular value to environmental scientists, given the carcinogenic
and toxic properties of several PAHs. As also reported in this review, the carcinogenic-
ity and toxicity varies with the chemical and molecular character of PAHs varies with
size and shape, and the carcinogenic and toxic effect can be higher according to sea-
son, type of fuel and source of pollution, and also by the size of the exposed region/site.
PAHs are an ubiquitous pollutant class that has to be included in climate regulations at
the same level with CO2 and NOx, given their longer half-life and chemical properties
which gives a wide range of toxic derivatives during degradation.

Received 21 January 2013; accepted 26 February 2013.

The author would like to thank Prof David van der Spoel for the guest-researcher posi-
tion at Uppsala University.
Address correspondence to Sergio Manzetti, Fjordforsk Institute of Science and Tech-
nology, Fresvik, 6896, Norway. E-mail: s.manzetti@fjordforsk.no
311
 312 S. Manzetti

Key Words: environmental, fate, pollution, polycyclic aromatic hydrocarbons (PAH),

transformation

INTRODUCTION
Pollution is a common problem related to population increase, urbanization
and industrialization, and imposes a series of challenges in urban planning, de-
mographic development and public health (6). Causing cardiac and pulmonary
complications, stroke, and other health problems (3), pollution represents the
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most critical issue with modernization of society and calls for better knowledge
on the species of pollutants and their environmental transformation, and an
improvement in current fuel and energy policies.
Automobile traffic, industrial activities, and other modern-age activities
represent the main sources for delivering pollutants to air, soil, and water
phases. In these emissions, polycyclic aromatic hydrocarbons (PAHs) represent
a central class of environmental toxins. This review reports on the properties
and environmental fate of PAHs which have increased dramatically in concen-
tration in the environment after the onset of the industrial revolution (16).
This article reports on the recent critical findings on the transformation, eco-
accumulation, and environmental fate of PAHs in order to stimulate the scien-
tific community to reach a consensus in regulating and reducing emissions on
a global scale.

POLYCYCLIC AROMATIC HYDROCARBONS

Polycyclic aromatic hydrobcarbons are a group of molecules which are com-
posed of aromatic units, with the benzene ring as the central unit. PAHs can
be subdivided into two different classes: the petrogenic classes and pyrogenic
classes. The petrogenic group of PAHs, derives from oil- and drilling activities,
including oil disasters, spills, and pollution from industrial sites and refineries.
The majority of the PAHs in the petrogenic class are small PAHs with 2–4 ring
members, such as naphtalene, anthracene, phenanthrene, and chrysene (33).
Small PAHs are frequently associated with acute toxicity and genotoxicity but
low carcinogenicity (28, 53).
The pyrogenic part, however, includes larger PAHs that derive from com-
bustion processes, which are mostly represented by traffic pollution, generic
transport and logistic activities, industrial activities, incineration, and also for-
est fires and volcanic eruptions (37, 73). The pyrogenic part of PAHs includes
members such as pyrene, benzo[a]pyrene, dibenzo(a,h)anthracene, dibenzo[a,
l]pyrene, benzo[ghi]perylene, benzoanthracene, and other medium-sized and
larger PAHs (Figure 1) that are related to high mutagenicitiy and carcinogenic-
ity, rather than acute toxicity, and represent the most hazardous component in
exhaust emissions (42, 74).
 Polycyclic Compounds in the Environment 313
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Figure 1: Structures of common non modified PAHs found in pollution. A: Pyrene; B:

Benzo[a]pyrene; C: Dibenzo[a,l]pyrene; D: Dibenzo[a,h]anthracene; E: benzo[ghi]perylene;
F: Tetraphene (benzoanthracene).

ENVIRONMENTAL TRANSFORMATION OF POLYCYCLIC

AROMATIC HYDROCARBONS
PAHs are slowly transformed in the environment through chemical and bio-
logical processes. The chemical reactions which take place during the trans-
formation and degradation of PAHs are particularly catalyzed by sunlight and
involve volatilization and oxidation, nitration, and other chemical processes
which take place in the interaction between the PAH, the atmosphere, and
aqueous environments (14, 30, 33).
The processes of chemical degradation (Figure 2) occur spontaneously in
the atmosphere, except for the halogenation which is catalyzed by fungal
species through the intervention of the chloroperoxidase enzyme (1). An addi-
tional form of transformed PAHs is the methoxylated PAH form, which is gen-
erated by the fungi Trametes versicolor as a result of the laccase and cathecol-
O-methyltransferase enzymatic activities (76) (Figure 2).
Following Figure 2, the group of nitro-PAHs is generated by the inter-
action with nitrogen oxide and nitric acid found in the atmosphere (62).
 314 S. Manzetti
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Figure 2: Typical PAH-degradation processes exemplified on anthracene. Top two reactions

occur spontaneously, while the two reactions at the bottom occur through fungal
degradation in the environment.

Additionally, nitro-PAHs are generated through combustion processes (fuel

combustion, biomass incineration, etc.) (31), leading to the formation of dinitro-
species such as 1,3–1,6-and 1,8-dinitropyrene and mono-nitro-PAHs, which are
known to cause asthma, allergies and lung cancer (54, 70). Nitro-PAHs induce
frameshift mutations, and account for 30–40% of the mutagenicity from diesel
exhaust particulate (22, 50). The mechanisms of adduct formation with the
DNA is based on their formation of guanosine-adducts, in the form of 1-N-
(deoxyguanosin-8-yl) amino-6-nitropyrene (9, 68). These mutations lead to the
G:C -> A:T transitions, G:C -> T:A transversions and single base deletion at
C:G sites (22).
Furthermore, following Figure 2, oxy-PAHs are of equal genotoxicity to
nitro-species (53) and are generated through the interaction between atmo-
spheric oxygen/ozone and PAHs catalyzed by UVA-radiation. Oxy-PAHs are
also generated during partial combustion and cold-start in diesel cars, through
the interaction with oxygen-radicals during combustion (41). Oxy-PAHs have
also been recently found to act as precursors in combustion reactions leading to
the formation of highly toxic species such as polychlorinated biphenyls (PCBs)
polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated didenzofurans
(PCDFs) (21).
 Polycyclic Compounds in the Environment 315
Both species follow certain parameters according to chemical reactivity
and molecular size. These processes can be simplified to the following: (1) with
increasing size of the molecule, the higher its potential in absorbing light en-
ergy becomes, thus increasing its photoreactivity (Figure 2); (2) with higher
aromaticity, the more stable the PAH becomes in the environment (ex vivo –
unaffected by biological activity) and gains a longer half-life (45, 46); (3) with
higher sp2-hybridization (i.e., peripherical carbon-bonds), the more rapid the
transformation rate of the molecule into oxy- and nitro-products becomes (45).
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Cellular Transformation of PAHs

Both oxy- and nitro-PAHs are transformed in the cell upon intoxication,
either through respiratory uptake, ingestion, or dermal uptake. The transfor-
mation path of PAHs in the cell is largely represented by the cytohrome P450
system, being the central unit for the immune machinery for the conversion of
foreign molecular species into solubilized variants (29). The catalytic activitiy
of the P450 system includes the generation of diol-epoxide species of PAHs,
which represent the most mutagenic, carcinogenic, and genotoxic metabolites
of PAHs (38, 72). These metabolites form adducts with guanosine residues in
the DNA (17, 27) which leads to mechanical and steric hindrance abrupting
the DNA-proof-reading activity of polymerase enzymes (59). Chlorinated PAHs
transformed through chlorine-oxygenation by the P450 cytochrome system into
oxy-PAHs as secondary metabolites (29). The conversion of halogenated PAHs
to dehalogenated species co-involves the generation of radical intermediates,
which represent potential genotoxins, including Ar-X-O• form, where X rep-
resents the halogen. These detoxification reactions are known to generated
activated mutagens in the cases of oxy-, nitro-, halo-, and un-modified PAHs,
which cause the toxic responses delineated above.

AGGLOMERATION AND ACCUMULATION

IN THE ENVIRONMENT
The degree of aggregation of pure non-modified PAHs and their particle is re-
lated to a certain extent with their crystal properties and hydrophobicity (47).
Combustion-generated PAH particles on the other hand, include a variety of
chemical modifications such as oxidized groups, nitrated groups, aralkylated
groups, and other modifications including ionic species, which make the pre-
diction and estimation of degrees and size of aggregates far more complex. Of
particular interest, the arrangement of the molecules in pure PAH samples
follows certain crystal geometries (18), inducing stacked and packed arrange-
ments (Figure 3). On the other hand, the crystal properties for oxy-PAHs are
less ordered that for pure hydrophobic PAHs and introduce more complex ge-
ometries and packing arrangements (11). This trend affects also to a certain
extent the patterns of agglomeration of PAH-containing samples, based on the
 316 S. Manzetti
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Figure 3: Crystal lattice arrangements of PAHs. A: Naphtalene; B: Coronene; C: Pyrene; D:

Tribenzopyrene. (Adapted from Desiraju and Gavezzotti (11)). (Color figure available online).

content of PAH in the combustion source and also based on temperature and
pressure under particle formation (e.g., diesel, turbo diesel, and gasoline en-
gines) (12). Upon nucleation (aggregation), the PAHs from exhaust emissions
are entirely in gaseous phase, however upon condensation, the processes of
nucleation determines the size of the particles depending on outside tempera-
tures and the chemical content of the emissions (48).
The sizes of gaseous PAH-particles range around 10 nm in diameter, and
increase toward 30 nm and 100 nm upon cooling, forming a variety of nanopar-
ticles with a higher volatilization potential than larger particles (20). Small
particles have also a higher lung-penetration rate in humans and animals, and
cause severe health adverse effects such as asthma and allergies (40, 57). The
degree of agglomeration and aggregation determines therefore the size and
volatility of PAH-particles, also under complex mixtures with other fuel compo-
nents such as semi-combusted alkanes, alkenes and biodiesel components (47).
Furthermore, the size and shape of the particles can have a functional role on
the fate of PAHs. For instance, carbonaceous materials such as fly ash, carbon
black and soot have all for instance been reported to “protect” adsorbed PAHs
from degradation in the atmosphere, in the aquatic phase and in sediments
(35). Also, slight variations in combustion technology of the same PAH source
(e.g., diesel/gasoline) affect the composition of emitted agglomerates and parti-
cles, and thus their toxicity by alternating the chemical content on the surface
of the particles (24). PAH-containing particles have also a particularly high
affinity for flat surfaces of soot, plastic coatings, and carbonaceous particles
generated in emissions and found in the environment, exerted through their
hydrophobic and aromatic properties.
 Polycyclic Compounds in the Environment 317

ACCUMULATION OF POLYCYCLIC AROMATIC HYDROCARBONS

IN THE ENVIRONMENT, TYPES, AND CONCENTRATIONS
PAH-particles accumulate in trafficked areas such as roads and parking lots
and are quickly transported to the water phase through rain, storms, and
snowmelt, resulting in a contiguous supply of PAHs from combustion sources
to water, soil and air environments (56). The physical state of the PAHs is
mostly is in the solid phase, as between 79% and 93% of PAHs were associated
with suspended solids in a study by Hoffman et al. (25). The sedimentation
and accumulation of PAHs in water sources and river-beds and sea-sediments
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is therefore a central path of the accumulation of PAHs.

The concentration and accumulation of species of PAHs depends on the
sites of exposure. In a study by Neary and Boving (56), the most predomi-
nant PAHs found in a detention pond after several days of exposure to rain
and storms were naphtalene, acenaphthylene, and fluorene. The concentra-
tions of these were in respective order 8.1 μg/L, 3.2 μg/L, and 2.7 μg/L in the
water samples from the pond. Other PAHs were also found at lower concentra-
tions: phenanthrene (1.8 μg/L), acenapthene (1.9 μg/L), anthracene (1.6 μg/L),
chrysene (1.2 μg/L), pyrene (1.1 μg/L), and benzo[a]anthracene (1.5 μg/L). The
subdivision of these PAHs and their adsorption to the surface of particles was
found to be subdivided into two categories roughly: the low molecular weight
PAHs (2–3 rings) which adsorbed to the sand-fraction on road runoff, while
heavy weight PAHs (6–7 rings) were largely adsorbed to the surfaces of finer
particles (36). A large portion of the PAH emissions enters also the atmosphere
during summer and hot seasons as an evaporated phase, particularly the low-
weight PAHs and also volatile organic compounds (VOC). Volatile organic com-
pounds are represented by a large aromatic fraction (75%) and their fate is a
major concern because of their volatilization and quick transfer from source
to air. Such compounds have also a bioaccumulative potential and can accu-
mulate in the smallest organisms such as amoeba, diatoms and algae, and
gradually enter the food chain. In a recent Italian study (13), the yearly por-
tion of wastewater delivered to four waste treatment plants from petrochemi-
cal, pharmaceutical, agroindustrial, metal plating, and oil-refining industries
was reported to be between 4.900–118.000 m3/day, where the most commonly
occurring VOCs were benzene, xylene, toluene, ethylbenzene, chlorotoluene,
and 1,2,4-trimethylbenzene. These volatile substances were found at concen-
trations below 2 μg/L, however phenanthrene, fluorene, and naphtalene were
ubiquitous in all wastewater samples, and found at higher concentrations, well
above their detection limit. Their relative frequency of occurrence at one site
was represented by naphtalene (95%), phenanthrene (85%), fluorene (71%),
acenapthene (57%), fluoranthene, pyrene, and tetraphene (all 44%) and other
PAHs of less frequent occurrence. The pattern of occurrence of these individ-
ual PAHs in the wastewater samples (13) is similar to the samples from the
 318 S. Manzetti

detention pond studied by Neary and Boving (56), where naphtalene, fluorene,
and acenapthene are all in overrepresented categories.
Interestingly, naphtalene is entirely in the liquid phase, while the other
are predominantly found the solid phase, as sediments and aggregates (13).
Removal efficiency of both VOC and PAHs in the wastewater treatment plants
varies in accord with the wastewater plant. One wastewater plant could re-
move as little as 71% of benzene through volatilization, 44% for toluene, 42%
for xylene, and 43% and 15% for o-xylene (for two different plants). The in-
fluent concentrations ranged between 0.035 μg/L–3.54 μg/L for the mentioned
VOCs, and this interval implied a potential release of 2.14 μg/L of toluene in
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the environment after treatment at the wastewater plant. The partly purified
wastewater is then released in rivers and seas, and enters the food chain, with
its non purified components, such as 2.5 μg/L of toluene as worst case scenario
from wastewater plant B in the study (13).
Similar figures were found for naphtalene, which was removed at only 24%
rate at wastewater plant B from the influent, representing an effluent concen-
tration of naphtalene of 0.11 μg/L, poured into rivers, lakes, and seas. Con-
sidering the several wastewater plants with low efficiency of purification of
PAHs and VOCs, it is expected that partly purified wastewater is an addi-
tional source of release of VOCs and PAHs into the environment, which can
reach as much as 2.14 μg/L of VOC, and up to 0.2 μg/L of PAHs in water (vide
supra). Altogether with exhaust emissions, pollution and industrial activities,
the end-point of environmental deposition of PAHs is in the soil, sea beds, river
banks, and also fjord basins (as observed also in Norwegian fjords) (44).

Inter-phase Transport of Polycyclic Aromatic Hydrocarbons

and Seasonal Variations
Recent studies of air- and soil samples show that phenanthrene and fluo-
rene are among the most occurring PAHs, and are found at increasing concen-
trations from rural to semiurban and urban locations (4, 49). The concentra-
tions of PAHs found in air samples are at ng/m3 levels and reachseveral μg/g
for soil samples (4, 49). The accumulation of PAHs is mainly in the soil however
the air acts as their primary transport vector (49). The various tranposrt paths
through air, including air-to-soil and soil-to-air are thus key process in the en-
vironmental pathways of PAHs, on both a regional and global scale. Air-to-soil
transport occurs primarily through the deposition of aerosols via gravitational
effects, wet deposition, and adsorption to soil constituents (8). Wind currents,
storms and low-pressure systems contribute to the transport PAHs from their
original source of pollution, such as urban regions, to urban peripheries, rural
regions, open seas and semi-rural areas (51). The transport is also reported to
occur across open plateaus, such as in the flat regions at the Canadian border
(60).
 Polycyclic Compounds in the Environment 319
Figure 4 shows an illustration of the transport of PAHs across the sev-
eral phases in the environment. Air-to-soil transfer of PAHs includes concen-
trations (in decreasing order) of benzo[ghi]perylene> benzo[b]fluoranthene>
benzo[a]anthracene¿ chrysene> fluoranthene at industrial sites during
all seasons, and concentrations of [ghi]perylene,>benzo[b]fluoranthene>
chrysene>benzo[a]anthracene in agricultural and roadside regions (49). The
industrial and roadside regions are affected by the highest PAH concentra-
tions all year, both in air and soil samples, with minor reduction during the
summer season. In equatorial parts of the earth, the monsoon season affects
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also the PAH levels in the air and soil phases, by reducing the amount of PAHs
in both phases, however not as much as summer seasons do in tropical parts of
the planet. Dry summer seasons with reduced humidity result in an increase
in particulate matter with adsorbed PAHs (49).
Another study on air-to-soil transfer was conducted in Turkey (10), sam-
pling PAHs in the soil near the Izmir bay. The magnitude and direction of air-
to-soil fluxes was reported, including the assessment of the deposition mecha-
nism and the effect on the air-to-soil flux. The results showed a predominance

Figure 4: Migration and bioaccumulation patterns of the most recurring polycyclic aromatic
hydrocarbons. The chart does not include chemical transformation processes, only transport
and migration patterns of unmodified PAHs (not oxidized or nitrated). The chart also depicts
the pathways of bio-distribution of the given PAHs, from source to living organisms. Heavy
PAHs (larger than 4–5 rings) in soil-to-air migration patterns are also expected to take part in
a reverse direction, depending on meteorological factors. (Color figure available online).
 320 S. Manzetti

of phenanthrene in both the gas and particle (solid) phase, followed by fluoran-
thene, fluorene, and pyrene, with respective concentrations of 11.7, 4.1, 3.7,
and 2.4 ng/m3 in the gas-phase for sub-urban areas, and of 40.8, 12.5, 27.3,
20.2 ng/m3 in gas-phase in urban areas. A comparison of the concentration
ranges observed in Turkey, showed that the affected reagion was considerably
more affect than urban Athens, which is known to be heavily exposed to traf-
fic (43). The observed concentrations were also reported to be rather similar
to downtown Rome (63), and to urban sites of London and Manchester (20).
The result from Turkey also indicate the PAHs with low to medium molecular
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weight (3–5 rings) were more abundant in the gas-phase than in particle state,
as in consensus with other reported studies therein. Air-to-soil rates where
furthermore reported to be highest for phenanthrene and fluorene, followed
by pyrene and fluorene with a significant rate reported also for chrysene and
benzo[b]fluorene (10).
In context with inter-phase transport of PAHs, the soil-to-air fugacity fac-
tor is a central measurement for the rate of transfer of PAHs from soil to air
and is dependent on the temperature and the organic carbon-to-water compo-
nent. The organic carbon-to-water component delineates the relative subdivi-
sion of PAHs in the aqueous and solid phases. The low-weight PAHs (naph-
talene, anthracene) and middle weight PAHs (chrysene, fluorene) have the
tendency to move from the soil to the air, as also with certain mid-weight
PAHs (chrysene, fluroanthene). Other PAHs which also migrated from soil to
air are acenaphtylene and phenanthrene (49). PAHs which do not migrate
from soil to air are however benzo[a]anthracene, benzo[b]fluoranthene and
benzo[ghi]perylene, given their greater molecular weight (49). During the sum-
mer season, the migration from soil to air is high for PAHs with the high fu-
gacity values, whereas during winter seasons the migration is reduced. Mid-
weight PAHs such as chrysene and fluoranthene migrate from soil to air only
during summer, while lower molecular weight PAHs (2–4 rings) migrate also
during winter (49). The complete group of PAHs, including low-weight, mid-
weight, and heavy-weight PAHs in a particle-bound or unbound state is de-
nominated as PAHs.

Levels of PAHs in Urban Regions

The concentrations of PAHs in samples at urban sites vary accord-
ing with population, traffic, industrial activity, and sampling site. The ma-
jor metropolises in the world as Los Angeles, Djakarta, Chicago, and Seoul
belong to the same class of pollution levels (32, 59, 76). In Seoul the con-
centrations of 24 pyrogenic PAHs in air, soil, water, and plant samples are
considered as high (32). The concentration of gaseous PAHs in air sam-
ples ranges between 6–59ng/m3 according to season (32). The measure-
ments from Seoul include naphtalene, 2- & 1-methylnaphtalene, biphenyl,
2,6-dimethylnaphtalene, acenaphtylene, acenaphtene, fluorene, anthracene,
pyrene, chrysene, tetraphene, benzo[b]fluoranthene, perylene, benzo[x]pyrene,
 Polycyclic Compounds in the Environment 321
phenanthrene and other PAHs, with phenanthrene at the highest concentra-
tion (1.4–2.3ng/m3) of the gaseous PAHs.

PAHs in Solid Phase /Soil Samples

PAHs in their particle-bound state are also measured at high con-
centrations by Kim et al (32) with the given measurements: indeno[1,2,3-
cd]pyrene > benzo[b]fluoranthene > benzo[ghi]perylene>fluoranthene >
pyrene > phenanthrene > chrysene > benzo[a]pyrene. Indeno[1,2,3-cd]pyrene
and benzo[b]fluoranthene had respective concentrations of 0.19–7.5ng/m3 and
0.25–5.2ng/m3, while benzo[a]pyrene which is the most carcinogenic was mea-
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sured at 0.067–2.3ng/m3 (32). Soil samples taken from Seoul showed also
high concentrations of phenanthrene (53–85 ng/g dry weight), fluoranthene
(99–150 ng/g dw), pyrene (63–120 ng/g dw), benzo[b]fluoranthene (88–230 ng/g
dw), benzo[a]pyrene (22–75 ng/g dw), and the particularly high concentra-
tions of indeno[1,2,3-cd]pyrene and benzo[ghi]perylene with concentrations of
90–290 ng/g dw and 64–240 ng/g dry-weight respectively (32). Also, a signif-
icant deposition on plant leaves shown in the same study, reported an over-
representation of phenanthrene (16–810 ng/g dw), fluoranthene (24–410 ng/g
dw) and pyrene (17–210 ng/g dw) detected on the surface of pine needles and
Mongolian oak leaves (32). Deposition on plant leaves is a central avenue in
the PAH life cycle, and was also studied by Navarro-Ortega et al. (55), who
measured up to 488 ng/g of phenanthrene and 106 ng/g of pyrene, with 14
other PAHs summing up to a maximum concentration of 837 ng/g PAHs on
pine needles in urban and rural areas in Spain.
Soil samples taken from the industrial region around the industrial city
of Shuitou in China show similar levels with the soil samples taken in the
metropolis Seoul, indicating that Seoul as a urban site is particularly loaded
with PAHs in the soil and can be compared to a full-industry city in soil-profile.
Chinese urban areas are also particularly prone to extensively high concentra-
tion of gaseous and particle-bound PAHs (75).

Air Samples of PAHs

Air samples taken on roadside areas in Los Angeles showed particularly
high concentrations of PAHs, where the concentrations detected were in the
range of 50–300 ng/m3 depending on site and season (77). In the industrial
town of Shuitou in China where crop loss, fewer adults who pass the phys-
ical exams for the National Army admissions, unusual diseases, and over-
all deterioration in living environment is reported. The concentrations mea-
sured at this site inair-, soil-, water-, and vegetation-samples of 15 PAHs
were critically high (39). In this study, the water-, soil-, and sediment samples
were prioritized as main causes of environmental degeneration, where water
samples from the Aojiang River contained a minimum of 909.9 ng/l PAH
to a maximum of 1519.8 ng/l. These concentrations were also higher than
concentrations measured at of other sites: Missisippi river, 12–430 ng/l (52),
 322 S. Manzetti

Susquehanna River, 12–130 ng/l (34) and the Pearl river in South China with
a total PAH concentration of 21.7–138 ng/l (26). Rainfall concentrations can
reach as high as 6614 ng/l rainwater in the region of South China, with
phenanthrene and anthracene as the dominant PAHs (26).
The highest concentrations of PAHs in air samples measured were
of 329 ng/m3 in the city of Guangzhou, where phenanthrene, fluoranthene,
pyrene, benzo[b]fluorene, benzo[a]pyrene were the overrepresented PAHs
among the 16 PAHs studied (75). The third of these peak values was ob-
served in air samples taken from Bangkok, where the average concentrations
of PAHs were measured to 111 ng/m3 (2). Only New Dehli has higher concen-
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trations than any other air sample study reviewed, with peak concentrations
of PAHs of 511.9, 672, and 1344.4 ng/m3 (64, 66, 67). Generally speaking,
PAH-profiles of air, soil, water and vegetation samples from urban regions in-
dicate specific patterns (Table 1 and Figure 5). These patterns denote that
the principal deposition of PAHs is on the vegetation, and secondary in the
soil. The mechanism of this transport is exerted by the lifecycle of the vegeta-
tion, which acts as a transported of the adsorbed PAHs to the soil in autumn
and winter. Proceeding through snow-melting, the PAHs are then transported
towards water sources, ending in sedimentation. Warmer and equatorial re-
gions experience instead an end-point deposition of PAHs to the soil and dust
particles.

PAHs in Sediments
Sediment concentrations in lakes and rivers are usually proportional with
soil concentrations, whereas waterways and ponds are within reach from the

Table 1: Reported concentrations taken from 5 sites in different studies: air, soil,
water, and vegetation samples. Sites are arranged in decreasing order of
concentration. Asterisk indicates averaged value. Sediment samples are not
shown in this table given the larger variation among water systems analyzed for
PAH content, rivers, deltas, ponds, lakes, and ocean bays.

Medium Site 1> Site 2> Site 3> Site 4> Site 5 Ref.

Air (ng/m3) 59 58 34 32 24 (32)

Air (ng/m3) 329.4 305.4 239.5 238.9 229.3 (75)
Air (ng/m3) 167.2 163.6 107.2 71.6 29.18 (2)
Soil (ng/g) 1700 1100 1100 870 760 (32)
Soil (ng/g) 1934.8 1841.6 1796.8 986.4 696.3 (39)
Soil (ng/g) 1147 — 613∗ — 124 (55)
Water (ng/l) 21 23 32 15 13 (32)
Water (ng/l) 1519.8 1444.2 1287 1234 1179 (39)
Water (ng/l) 430 85 77 25 12 (52)
Vegetation (ng/g) 2100 1800 1400 1200 710 (32)
Vegetation (ng/g) 3538.6 3251.1 2909.2 2462.1 2043.2 (39)
Vegetation (ng/g) 837 — 290∗ — 44 (55)
 Polycyclic Compounds in the Environment 323
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Figure 5: A comparison of the concentration of PAH’s taken at five different sites in five
different countries. A dominant pattern of high concentrations at Chinese sites is evident in
all different environmental phases, with soil and vegetation reaching maximum values.

primary PAH emission sources; industry and traffic pollution. Concentrations

in river deltas and bays are also closely related to the soil concentrations of
the surroundings. Sediment samples from 15 different sites in river sediments
around Shuitou (China) had similar levels to soil samples, with an average
concentration of 800 ng/g sediment (39). The peak values of the concentration
of PAHs in sediment samples reached as much as 2605.5 ng/g, and pyrene,
phenanthrene, and acenapthene were the most recurring PAHs among the
PAHs analyzed (32).
 324 S. Manzetti

Seasonal Variations and Effects on the Migration Patterns

of Polycyclic Aromatic Hydrocarbons
PAH concentrations increase during winter seasons, given the increase in
fuel combustion for heating, reduction in wind speeds, and lower humidity and
rain, particularly in the coldest regions. In winter seasons, the particulate level
is also higher due to increased condensation and lower volatilization of gaseous
PAHs and “sticky” hydrophobic compounds such as solid-state PAHs (chrysene,
benzo[a]pyrene, pyrene, and heavy PAHs). Higher concentrations of particle-
bound PAHs in winter reach as high as 70% the equivalent concentration dur-
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ing summer in certain urban regions (32). During soil-to-air transfer, the fu-
gacity of the volatile PAHs plays a central role in their environmental fate as
mentioned above. Fugacity for soil-to-air transfer is given by the formula:

0.411ϕOM K OA
fs = ,
CSSRT

where Cs is the soil concentration of PAHs (ng/kg dw), R is the universal gas
constant (8.314 Pa m3/molK), T is the absolute temperature (K), ϕOM is the
fraction of organic matter in the soil (dry weight), and KOA is the dimensionless
coefficient for organic carbon.
When the PAH are transferred from source to air, through gasification or
through co-gasification from a partly dissolved state and from a liquid phase,
the given factors in the formula play a central role in the efficiency of PAH dif-
fusion from one phase to the other. This is, as seen in the formula, dependent
on temperature as well, and implies thus a seasonal variation in the fugacities
of PAH from one phase to the other. For instance, during winter seasons, the
measured PAHs with the highest fugacities in urban regions are (in decreas-
ing order): benzo[b]fluoranthene > benzo[e]pyrene > benzo[k]fluoranthene >
benzo[a]pyrene > chrysene > benzo[a]anthracene > pyrene > fluroanthene >
phenanthrene and anthracene (19).
For the other seasons, the patterns of distribution of PAHs vary, par-
ticularly for summers which show lower fugacities for the three top PAHs
ranked. Perylene, indeno[1,2,3, cd]pyrene, benzo[ghi]perylene, and dibenzoan-
thracene have the lowest fugacities all year around, given their higher molec-
ular weights. The fugacity of PAHs increases also with their higher solubility
(19), particularly accounting for oxy- and nitro-PAHs. The most soluble and
the low-molecular weight PAHs are thus also the most fugacious, and purely
hydrophobic mid-weight compounds as chrysene and benzo[a/e]pyrene display
lower fugacity than for instance chlorodane and other modified PAHs (19).
During the autumn season, the increase of rainfall facilitates the transport
of PAHs from the air back to soil, and an estimated 10–15% of the aerosol and
gaseous PAHs returns to the soil (Ni et al, 2011), which is the averagely most
contaminated phase by PAHs (5, 7, 32, 34, 52, 60, 77).
 Polycyclic Compounds in the Environment 325
Although Figure 5 depicts exemplary concentrations of PAH soil-deposition
in the environment, the concentrations found in Shenzhen (China), Hong Kong
(China), and Tallin (Estonia) in 2010, 2007, 1999, reach, respectively, the as-
tonishing concentrations of 17.676 ng/g, 19.500 ng/g, and 26.300 ng/g PAHs,
which can be classified as alarming (5.7). The deposition in the soil is partic-
ularly detrimental independently on the seasonal variations, given its close
relationship to water-sources and farming grounds. The soil is the primary ac-
cumulator of PAHs given its extended holding capacity of organic pollutants
(5). A secondary effect from soil deposition, particularly during summer, is the
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transport of volatile and fugacious PAHs from the soil to air and thus to liv-
ing organisms via inhalation. The PAHs represented in this class of seasonal
migration are fluorene > acenapthylene > phenanthrene > acenapthene > an-
thracene > fluoranthene > pyrene > benzo[a]pyrene and chrysene (5).
Pollution-exposed areas in colder countries are on the other hand fre-
quently associated to high toxicity and rising PAH concentrations during
spring seasons in meltwater and sediments (69). The snow melting caused by
the onset of the spring leads to the release of large quantities of PAHs trapped
in snow and ice along roads and near industrial sites, increasing the PAH con-
centration in soils, water, and sediments (Figure 4).

CONCLUSIONS
PAHs are ubitquitos pollutants with vast genotoxic species, where several are
carcinogenic. This study reviews the environmental patterns of pollutions,
sites of exposure, transformation paths and seasonal effects on inter-phase
transfer of PAHs. The vast accumulated amount of data, both in this study and
in others, should trigger legislators and environmental ministries to include
PAHs as equally important pollutants as climate gases, given their ubiquitous
and toxic nature.

REFERENCES
1. Aburto, J., J. Correa-Basurto, and E. Torres. “Atypical Kinetic Behavior of
Chloroperoxidase-Mediated Oxidative Halogenation of Polycyclic Aromatic Hydrocar-
bons.” Arch Biochem. Biophys. 480 (2000): 33–40.
2. Boonyatumanond, R., M. Murakami, G. Wattayakorn, A. Togo, and H. Takada.
“Sources of Polycyclic Aromatic Hydrocarbons (PAHs) in Street Dust in a Tropical Asian
Mega-City, Bangkok, Thailand.” Sci. Total Environ. 384 (2007): 420–32.
3. Brook, R. D., S. Rajagopalan, C. A. Pope 3rd, J. R. Brook, A. Bhatnagar, A. V. Diez-
Roux, F. Holguin, Y. Hong, R. V. Luepker, M. A. Mittleman, A. Peters, D. Siscovick,
S. C. Smith Jr., L. Whitsel, and J. D. Kaufman. “American Heart Association Council
on Epidemiology and Prevention, Council on the Kidney in Cardiovascular Disease,
and Council on Nutrition, Physical Activity and Metabolism. Particulate Matter Air
Pollution and Cardiovascular Disease: An Update to the Scientific Statement from the
American Heart Association.” Circulation 121 (2010): 2331–78.
 326 S. Manzetti

4. Cabrerizo, A., J. Dachs, C. Moeckel, M. J. Ojeda, G. Caballero, D. Barceló, and

K. C. Jones. “Ubiquitous Net Volatilization of Polycyclic Aromatic Hydrocarbons from
Soils and Parameters Influencing Their Soil-Air Partitioning.” Environ. Sci. Technol. 45
(2011): 4740–7.
5. Cao, S. P., H. G. Ni, P. H. Qin, and H. Zeng. “Occurrence and Human Non-Dietary
Exposure of Polycyclic Aromatic Hydrocarbons in Soils from Shenzhen, China.” J. Env-
iron. Monit. 12 (2010): 1445–50.
6. Correia, A. W., C. A. Pope 3rd, D. W. Dockery, Y. Wang, M. Ezzati, and F. Dominici.
“Effect of Air Pollution Control on Life Expectancy in the United States: An Analysis of
545 U.S. Counties for the Period from 2000 to 2007.” Epidemiology 24 (2013): 23–31.
7. Chung, M. K., R. Hu, K. C. Cheung, and M. H. Wong. “Pollutants in Hong Kong
Downloaded by [University of Arizona] at 01:56 29 August 2013

Soils: Polycyclic Aromatic Hydrocarbons.” Chemosphere 67 (2007): 464–73.

8. Cousins, I. T. and K. C. Jones. “Air–Soil Exchange of Semi-Volatile Organic Com-
pounds (SOCs) in the UK.” Environ. Pollut. 102 (1998): 105–18.
9. Delclos, K. B., R. P. Walker, K. L. Dooley, P. P. Fu, and F. F. Kadlubar. “Carcinogen-
DNA Adduct Formation in the Lungs and Livers of Preweanling CD-1 Male Mice Fol-
lowing Administration of [3H]-6-nitrochrysene, [3H]-6-aminochrysene, and [3H]-1,6-
dinitropyrene.” Cancer Res. 47 (1987): 6272–7.
10. Demircioglu, E., A. Sofuoglu, and M. Odabasi. “Particle-phase dry deposition and
Air-Soil Gas Exchange of Polycyclic Aromatic Hydrocarbons (PAHs) in Izmir, Turkey.”
J Haz. Mater. 186 (2011): 328–35.
11. Desiraju, G. R. and C. A. Gavezzotti. “Crystal Structures of Polynuclear Aromatic
Hydrocarbons. Classification, Rationalization and Prediction from Molecular Struc-
ture.” Acta Cryst. B45 (1989): 473–82.
12. Eiguren-Fernandez, A. and A. H. Miguel. “Size-Resolved Polycyclic Aromatic Hy-
drocarbon Emission Factors from On-Road Gasoline and Diesel Vehicles: Temperature
Effect on the Nuclei-Mode.” Environ. Sci. Technol. 46 (2012): 2607–15.
13. Fatone, F., S. Di Fabio, D. Bolzonella, and F. Cecchi. “Fate of Aromatic Hydro-
carbons in Italian Municipal Wastewater Systems: An Overview of Wastewater Treat-
ment using Conventional Activated-Sludge Processes (CASP) and Membrane Bioreac-
tors (MBRs).” Water Res. 45 (2011): 93–104.
14. Fu, P. P., Q. Xia, X. Sun, and H. Yu. “Phototoxicity and Environmental Trans-
formation of Polycyclic Aromatic Hydrocarbons (PAHs)-Light-Induced Reactive Oxygen
Species, Lipid Peroxidation, and DNA Damage.” J. Environ. Sci. Health C Environ. Car-
cinog. Ecotoxicol. Rev. 30 (2012): 1–41.
15. Fujita, E. M., D. E. Campbell, B. Zielinska, W. P. Arnott, and J. C. Chow. “Concen-
trations of Air Toxics in Motor Vehicle-Dominated Environments.” Res. Rep. Health Eff.
Inst. 156 (2011): 3–77.
16. Gabrieli, J., P. Vallelonga, G. Cozzi, P. Gabrielli, A. Gambaro, M. Sigl, F. Decet, M.
Schwikowski, H. Gäggeler, C. Boutron, P. Cescon, and C. Barbante. “Post 17th-Century
Changes of European PAH Emissions Recorded in High-Altitude Alpine Snow and Ice.”
Environ. Sci. Technol. 44 (2010): 3260–6.
17. Gamper, H. B., K. Straub, M. Calvin, and J. C. Bartholomew. “DNA Alkylation
and Unwinding Induced by benzo[a]pyrene Diol Epoxide: Modulation by Ionic Strength
and Superhelicity.” PNAS 77 (1980): 2000–4.
18. Gavezzotti, A. and G. R. Desiraju. “A Systematic Analysis of Packing Energies
and Other Packing Parameters for Fused-Ring Aromatic Hydrocarbons.” Acta Cryst.
B44 (1988): 427–434.
 Polycyclic Compounds in the Environment 327
19. Golding, C. J., F. A. P. C. Gobas, and G. F. Birch. “A Fugacity Approach for As-
sessing the Bioaccumulation of Hydrophobic Organic Compounds from Estuarine Sed-
iment.” Environ. Tox. Chem. 27 (2008): 1047–54.
20. Halsall, C. J., P. J. Coleman, B. J. Davis, V. Burnett, K. S. Waterhouse, P. Harding-
Jones, and K. C. Jones. “Polycyclic Aromatic Hydrocarbons in U.K. Urban Air,” Environ.
Sci. Technol. 28 (1994): 2380–6.
21. Hajizadeh, Y., J. A. Onwudili, and P. T. Williams. “PCDD/F Formation from oxy-
PAH Precursors in Waste Incinerator Flyash.” Chemosphere 85 (2011): 1672–81.
22. Hashimoto, A. H., K. Amanuma, K. Hiyoshi, H. Takano, K. Masumura, T. Nohmi,
and Y. Aoki. “In vivo Mutagenesis in the Lungs of gpt-delta Transgenic Mice Treated
Intratracheally with 1,6-dinitropyrene.” Environ. Mol. Mutagen. 47 (2006): 277–
Downloaded by [University of Arizona] at 01:56 29 August 2013

83.
23. Häkkinen, J., E. Vehniäinen, and A. Oikari. “High Sensitivity of Northern Pike
Larvae to UV-B but no UV-photoinduced Toxicity of Retene.” Aquat. Toxicol. 66 (2004):
393–404.
24. Hesterberg, T. W., C. M. Long, S. N. Sax, C. A. Lapin, R. O. McClellan, W. B. Bunn,
and P. A. Valberg. “Particulate Matter in New Technology Diesel Exhaust (NTDE) is
Quantitatively and Qualitatively Very Different from that Found in Traditional Diesel
Exhaust (TDE).” J. Air Waste Manage. Assoc. 61 (2011): 894–913.
25. Hoffman, E. J., G. L. Mills, J. S. Latimer, and J. G. Quinn. “Urban Runoff as a
Source of Polycyclic Aromatic Hydrocarbons to Coastal Waters.” Environ. Sci. Technol.
18 (1984): 580–7.
26. Huang, D., P. Peng, Y. Xu, Y. Deng, and H. Deng. “Distribution and Deposition
of Polycyclic Aromatic Hydrocarbons in Precipitation in Guangzhou, South China.” J.
Environ. Sci. 21 (2009): 654–60.
27. Huberman, E., L. Sachs, S. K. Yang, and V. Gelboin. “Identification of Mutagenic
Metabolites of benzo(a)pyrene in Mammalian Cells.” PNAS 73 (1976): 607–11.
28. IARC. Overall Evaluation of Carcinogenicity: An Updating of IARC Monographs
Volumes 1 to 42, Supplement 7. (Lyon, France: International Agency for Research on
Cancer, 1987).
29. Isin, E. M. and F. P. Guengerich. “Complex Reactions Catalyzed by Cytochrome
P450 Enzymes.” Biochim. Biophys. Acta. 1770 (2007): 314–29.
30. Kamens, R. M., Z. Guo, J. N. Fulcher, and D. A. Bell. “The Influence of Humidity,
Sunlight, and Temperature on the Daytime Decay of Polyaromatic Hydrocarbons on
Atmospheric Soot Particles.” Environ. Sci. Technol. 22 (1988): 103–8.
31. Karavalakis, G., V. Boutsika, S. Stournas, and E. Bakeas. “Biodiesel Emissions
Profile in Modern Diesel Vehicles. Part 2: Effect of Biodiesel Origin on Carbonyl, PAH,
Nitro-PAH and Oxy-PAH Emissions.” Sci. Total Environ. 409 (2011): 738–47.
32. Kim, D., B. M. Kumfer, C. Anastasio, I. M. Kennedy, and T. M. Young. “Environ-
mental Aging of Polycyclic Aromatic Hydrocarbons on Soot and its Effect on Source
Identification.” Chemosphere 76 (2009): 1075–81.
33. Kim, S. K., D. S. Lee, W. J. Shim, U. H. Yim, and Y. S. Shin. “Interrelationship
of Pyrogenic Polycyclic Aromatic Hydrocarbon (PAH) Contamination in Different Envi-
ronmental Media.” Sensors (Basel) (2009): 9582–602.
34. Ko, F. C. and J. E. Baker. “Seasonal and Annual Loads of Hydrophobic Organic
Contaminants from the Susquehanna River Basin to the Chesapeake Bay.” Mar. Pollut.
Bull. 48 (2004): 840–51.
 328 S. Manzetti

35. Korfmacher, W. A., D. F. Natusch, D. R. Taylor, G. Mamantov, and E. L. Wehry.

“Oxidative Transformations of Polycyclic Aromatic Hydrocarbons adsorbed on Coal Fly
Ash.” Science 207 (1980): 763–5.
36. Krein, A. and M. Schorer. “Road Runoff Pollution by Polycyclic Aromatic Hydro-
carbons and its Contribution to River Sediments.” Water Res. 34 (2000): 4110–15.
37. Kuang, Y. W., G. Y. Zhou, D. Z. Wen, J. Li, and F. F. Sun. “Analysis of Polycyclic
Aromatic Hydrocarbons in Tree-Rings of Masson Pine (Pinus massoniana L.) from Two
Industrial Sites in the Pearl River Delta, South China.” J. Environ. Monit. 13 (2011):
2630–7.
38. Levin, W., A. Wood, R. Chang, D. Ryan, P. Thomas, H. Yagi, D. Thakker, K. Vyas, C.
Boyd, S. Y. Chu, A. Conney, and D. Jerina. “Oxidative Metabolism of Polycyclic Aromatic
Downloaded by [University of Arizona] at 01:56 29 August 2013

Hydrocarbons to Ultimate Carcinogens.” Drug Metab. Rev. 13 (1982): 555–80.

39. Li, J., X. Shang, Z. Zhao, R. L. Tanguay, Q. Dong, and C. Huang. “Polycyclic Aro-
matic Hydrocarbons in Water, Sediment, Soil, and Plants of the Aojiang River Waterway
in Wenzhou, China.” J. Haz. Mater. 173 (2010): 75–81.
40. Li, N., C. Sioutas, A. Cho, D. Schmitz, C. Misra, J. Sempf, M. Wang, T. Oberley,
J. Froines, and A. Nel. “Ultrafine Particulate Pollutants Induce Oxidative Stress and
Mitochondrial Damage.” Environ. Health Perspect. 111 (2003): 455–60.
41. Lies, K. H., A. Hartung, A. Postulka, H. Gring, and J. Schulze. “Composition of
diesel Exhaust with Particular Reference to Particle Bound Organics Including Forma-
tion of Artifacts.” Dev. Toxicol. Environ. Sci. 13 (1986): 65–82.
42. Lorenzi, D., J. A. Entwistle, M. Cave, and J. R. Dean. “Determination of Poly-
cyclic Aromatic Hydrocarbons in Urban Street Dust: Implications for Human Health.”
Chemosphere 83 (2011): 970–7.
43. Mandalakis, M., M. Tsapakis, A. Tsoga, and E. G. Stephanou. “Gas-Particle Con-
centrations and Distribution of Aliphatic Hydrocarbons, PAHs, PCBs and PCDD/Fs in
the Atmosphere of Athens (Greece).” Atmos. Environ. 36 (2002): 4023–35.
44. Manzetti, S. and J. H. Stenersen. “A Critical View of the Environmental Condition
of the Sognefjord.” Mar. Pollut. Bull. 60 (2010): 2167–74.
45. Manzetti, S. Quantum Chemical Toxicology: Theory, Methods and Application to
Nanoparticles and Molecular Carcinogens. (New York: Lambert Academic Publishers,
2012).
46. Manzetti, S. “Ecotoxicity of Polycyclic Aromatic Hydrocarbons, Aromatic Amines
and Nitroarenes from Molecular Properties.” Environ. Chem. Lett. 10 (2012): 349–61.
47. Manzetti, S., O, Andersen, and J. Czerwinski. “Biodiesel, Fossil Diesel and Their
Blends; Chemical and Toxicological Properties,” in Biodiesel: Blends, Properties and
Applications, eds. J. M. Marchetti and Z. Fang. (New York: Nova Science Publishers,
Inc., 2011).
48. Martins, L. D., C. R. da Silva Júnior, M. C. Solci, J. P. Pinto, D. Z. Souza. P. Vas-
concellos, A. L. Guarieiro, L. L. Guarieiro, E. T. Sousa, and J. B. de Andrade. “Particle
Emission from Heavy-Duty Engine Fuelled with Blended Diesel and Biodiesel.” Envi-
ron. Monit Assess. 184 (2012): 2663–76.
49. Masih, A., J. Masih, and A. Taneja. “Study of Air-Soil Exchange of Polycyclic Aro-
matic Hydrocarbons (PAHs) in the North-Central Part of India—A Semi Arid Region.”
J. Environ. Monit. 14 (2012): 172–80.
50. McCoy, E. C., E. J. Rosenkranz, H. S. Rosenkranz, and R. Mermelstein. “Nitrated
Fluorene Derivatives are Potent Frameshift Mutagens.” Mutat. Res. 90 (1981): 11–
20.
 Polycyclic Compounds in the Environment 329
51. Melymuk, L., M. Robson, P. A. Helm, and M. L. Diamond. “PCBs, PBDEs, and
PAHs in Toronto Air: Spatial and Seasonal Trends and Implications for Contaminant
Transport.” Sci. Total Environ. 429 (2012): 272–80.
52. Mitra, S. and T. S. Bianchi. “A Preliminary Assessment of Polycyclic Aromatic
Hydrocarbon Distributions in the Lower Mississippi River and Gulf of Mexico.” Mar.
Chem. 82 (2003): 273–88.
53. National Toxicology Program. “NTP 12th Report on Carcinogens.” Rep. Carcinog.
12 (2011): iii–499.
54. Nakagawa, R., S. Kitamori, K. Horikawa, K. Nakashima, and H. Tokiwa. “Identi-
fication of Dinitropyrenes in Diesel-Exhaust Particles. Their Probable Presence as the
Major Mutagens.” Mutat. Res. 124 (1983): 201–11.
Downloaded by [University of Arizona] at 01:56 29 August 2013

55. Navarro-Ortega, A., N. Ratola, A. Hildebrandt, A. Alves, S. Lacorte, and D. Bar-

celó. “Environmental Distribution of PAHs in Pine Needles, Soils, and Sediments.” En-
viron. Sci. Pollut. Res. Int. 19 (2012): 677–88.
56. Neary, K. and T. B. Boving. “The Fate of the Aqueous Phase Polycyclic Aro-
matic Hydrocarbon Fraction in a Detention Pond System.” Environ. Pollut. 159 (2011):
2882–90.
57. Nel, A. E., D. Diaz-Sanchez, D. Ng, T. Hiura, and A. Saxon. “Enhancement of Aller-
gic Inflammation by the Interaction between Diesel Exhaust Particles and the Immune
System.” J. Aller. Clin. Immunol. 102 (1998): 539–54.
58. Ni, H. G., P. H. Qin, S. P. Cao, and H. Zeng. “Fate Estimation of Polycyclic Aromatic
Hydrocarbons in Soils in a Rapid Urbanization Region, Shenzhen of China.” J. Environ.
Monit. 13 (2011): 313–8.
59. Nordenskjöld, M., S. Söderhäll, P. Moldéus, and B. Jernström. “Differences in
the Repair of DNA Strand Breaks Induced by 9-hydroxy-benzo(a)pyrene and trans-
7,8-dihydro-7,8-dihydroxy-benzo(a)pyrene in Cultured Human Fibroblasts.” Biochem.
Biophys. Res. Commun. 85 (1978): 1535–41.
60. Panther, B. C., M. Q. Hooper, and N. J. Tapper. “A Comparison of Air Particulate
Matter and Associated Polycyclic Aromatic Hydrocarbons in Some Tropical and Tem-
perate Urban Environments.” Atmosph. Environ. 33 (1999): 4087–99.
61. Petersen, D. G., F. Reichenberg, and I. Dahllöf. “Phototoxicity of Pyrene Affects
Benthic Algae and Bacteria from the Arctic.” Environ. Sci. Technol. 42 (2008): 1371–6.
62. Pitts, J. N. Jr, K. A. Van Cauwenberghe, D. Grosjean, J. P. Schmid, D. R. Fitz, W. L.
Belser, G. P. Knudson, and P. M. Hynds. “Atmospheric Reactions of Polycyclic Aromatic
Hydrocarbons: Facile Formation of Mutagenic Nitro Derivatives.” Science 202 (1978):
515–9.
63. Possanzini, M., V. Di Palo, P. Gigliucci, M. C. T. Sciano, and A. Cecinato “Determi-
nation of Phase-Distributed PAH in Rome Ambient Air by Denuder/GC–MS Method.”
Atmos. Environ. 38 (2004): 1727–34.
64. Sarkar, S. and P. S. Khillare. “Profile of PAHs in the Inhalable Particulate Frac-
tion: Source Apportionment and Associated Health Risks in a Tropical Megacity.” Env-
iron. Monit. Assess. 185 (2013): 1199–213.
65. Schirmer, K., A. G. J. Chan, B. M. Greenberg, D. G. Dixon, and N. C. Bols. “Ability
of 16 Priority PAHs to be Photocytotoxic to a Cell Line from the Rainbow Trout Gill.”
Toxicology 127 (1998): 143–55.
66. Sharma, H., V. K. Jain, and Z. Khana. “Characterization and Source Identifica-
tion of Polycyclic Aromatic Hydrocarbons (PAHs) in the Urban Environment of Delhi.”
Chemosphere 66 (2007): 302–10.
 330 S. Manzetti

67. Sharma, H., V. K. Jain, and Z. H. Khan. “Atmospheric Polycyclic Aromatic Hydro-
carbons (PAHs) in the Urban Air of Delhi during 2003.” Environ. Monit. Assess. 147
(2008): 43–55.
68. Smith, B. A., N. F. Fullerton, R. H. Heflich, and F. A. Beland. “DNA Adduct Forma-
tion and T-lymphocyte Mutation Induction in F344 Rats Implanted with Tumorigenic
Doses of 1,6-dinitropyrene.” Cancer Res. 55 (1995): 2316–24.
69. Tixier, G., Q. Rochfort, L. Grapentine, J. Marsalek, and M. Lafont. “Spatial and
Seasonal Toxicity in a Stormwater Management Facility: Evidence Obtained by Adapt-
ing an Integrated Sediment Quality Assessment Approach.” Water Res. 46 (2012):
6671–82.
70. Tokiwa, H., T. Otofuji, K. Horikawa, S. Kitamori, H. Otsuka, Y. Manabe, T. Ki-
Downloaded by [University of Arizona] at 01:56 29 August 2013

nouchi, and Y. Ohnishi. “1,6-Dinitropyrene: Mutagenicity in Salmonella and Carcino-

genicity in BALB/c Mice.” J. Nat. Cancer Instit. 73 (1984): 1359–63.
71. Utesch, D., K. Eray, and E. Diehl. “Phototoxicity Testing of Polycyclic Aromatic
Hydrocarbons (PAH) in Mammalian Cells in vitro.” Polycycl. Arom. Comp. 10 (1996):
11–121.
72. Vepachedu, S. R., N. Ya, H. Yagi, J. M. Sayer, and D. M. Jerina. “Marked Differ-
ences in Base Selectivity between DNA and the Free Nucleotides upon Adduct Forma-
tion from Bay- and Fjord-Region Diol Epoxides.” Chem. Res. Toxicol. 13 (2000): 883–90.
Erratum in: Chem. Res. Toxicol. 14 (2001): 148.
73. Wang, C., H. Sun, Y. Chang, Z. Song, and X. Qin. “PAHs Distribution in Sediments
Associated with Gas Hydrate and Oil Seepage from the Gulf of Mexico.” Mar Pollut Bull.
62 (2011): 2714–23.
74. Wang, D.G., M. Yang, H. L. Jia, L. Zhou, and Y. F. Li. “Polycyclic Aromatic Hydro-
carbons in Urban Street Dust and Surface Soil: Comparisons of Concentration, Profile,
and Source.” Arch. Environ. Contam. Toxicol. 56 (2009): 173–80.
75. Yang, Y., P. Guo, Q. Zhang, D. Li, L. Zhao, and D. Mu. “Seasonal Variation, Sources
and Gas/Particle Partitioning of Polycyclic Aromatic Hydrocarbons in Guangzhou,
China.” Sci. Total Environ. 408 (2010): 2492–500.
76. Zeng, J., X. Lin, J. Zhang, H. Zhu, H. Chen, and M. H. Wong. “Successive Trans-
formation of benzo[a]pyrene by Laccase of Trametes Versicolor and Pyrene-Degrading
Mycobacterium Strains.” Appl. Microbiol. Biotechnol. 97 (2012): 3183–94.
77. Zhu, Y., D. C. Fung, N. Kennedy, W. C. Hinds, and A. Eiguren-Fernandez “Mea-
surements of Ultrafine Particles and Other Vehicular Pollutants inside a Mobile Expo-
sure System on Los Angeles Freeways.” J. Air Waste Manage. Assoc. 58 (2008): 424–34.