A REVIEW OF A T M O S P H E R I C P O L Y C Y C L I C AROMATIC

H Y D R O C A R B O N S : S O U R C E S , FATE AND BEHAVIOR

S. O. B A E K , R. A. F I E L D , M. E. G O L D S T O N E , P. W. K I R K , J. N. L E S T E R ,
and R. PERRY*
Environmental Engineering Laboratory, Civil Engineering Department, Imperial College, London,
S W 7 2BU, U.K.

(Received October 5, 1990; revised February 28, 1991)

Abstract. A review has been written to assess the sources, fate and behavior of polycyclic aromatic
hydrocarbons (PAH) in the atmosphere. PAH are formed mainly by anthropogenic processes, especially
the combustion of organic fuels. PAH concentration in air will reflect the location of source emitters,
with high concentrations corresponding with urban and industrial areas. PAH are however ubiquitous
contaminants of the environment having been detected in remote areas of the world. This is thought
to be due to long term transport in the atmosphere. PAH can also be subjected to chemical and/
or photochemical change whilst resident in the atmosphere prior to their removal by either wet or
dry deposition.

1. Introduction

In recent years there has been considerable concern regarding the possible adverse
effects on human health of toxic compounds in the atmospheric environment.
Attention has focused particularly on chemical carcinogens in ambient air. Polycyclic
aromatic hydrocarbons (PAH) were one of the first atmospheric pollutants to be
identified as being carcinogenic. This class of compounds is ubiquitous in the urban
atmosphere and has therefore undergone considerable scrutiny.
PAH consist of two or more fused benzene rings in linear, angular or cluster
arrangements. By definition they contain only C and H. PAH can be formed in
any incomplete combustion or high temperature pyrolytic process involving fossil
fuels, or more generally, materials containing C and H (Badger, 1962).
Human exposure to PAH can occur through several environmental pathways
including internal adsorption through food and water (Basu and Saxena, 1978;
Lijinsky and Ross, 1967). Their occurrence in ambient air has however caused
particular concern due to the continuous nature of exposure and the size of population
at risk, especially in urban, suburban and industrial areas. The extent to which
humans are exposed to PAH is a function of several parameters including the
concentration in ambient air, the prevailing atmospheric conditions, their distribution
between the gaseous and particulate phases and the size of the particles with which
the particulate fraction are associated.
In order to assess the significance of PAH in ambient air it is necessary to evaluate

* Author for all correspondence.

Water, Air, and Soil Pollution 60: 279-300, 1991.

© 1991 Kluwer Academic Publishers. Printed in the Netherlands.
280 S.O. BAEKETAL.

the physical and chemical characteristics of airborne PAH as well as to identify

the major emission sources.

2. Sources and Ambient Concentrations

Part of the PAH in the atmosphere arises from natural combustion such as forest
fires and volcanic eruptions (Nikolaou et al., 1984), but emissions from human
activities are the predominant source. The anthropogenic sources of PAH can be
divided into stationary and mobile categories. Within the mobile category, the major
contributors are vehicular petrol and diesel engines. The stationary category
encompasses a wide variety of combustion processes including residential heating,
industrial activities (eg aluminium production and coke manufacture), incineration
and power generation (Hangebrauck et al., 1967; United States (U.S.) National
Academy of Sciences, 1972; Masclet et al., 1988) and may result in high atmospheric
PAH concentrations in the vicinity of the major emitters (U.S. National Academy
of Sciences, 1983). Quantitative data is generally lacking for certain mobile sources
of PAH, including aircraft, ships and two stroke engines such as motorcycles and
lawnmowers.
The amount and range of PAH produced from any pyrolytic process varies widely,
being dependent upon the fuel type and the combustion conditions (Blumer, 1976,
Westerholm, et al., 1988). For example high BaP concentrations seem to arise from
low temperature combustion (Freeman and Cattell, 1990). The contribution of any
PAH source to the atmosphere will depend on a number of factors including the
emission rate of the source, its geographical location and the local climatic conditions
(Harkov and Greenberg, 1985). Ramdahl et al. (1983) reviewed and summarized
PAH emissions factors for each source and developed estimates of PAH emissions.
These estimates are compiled in Table I, together with similar data from Peters
et al. (1981). The values in Table I are however open to debate due to uncertainties
in the emission factors used for the estimation as well as the lack of standardized
procedures for data collection and analysis. These figures may be valid only to
within orders of magnitude. This point is borne out by comparison between columns
(a) and (b) in Table I. Despite the uncertainty of the emission data, the information
in Table I indicates that stationary sources account for approximately 90% of the
annual total PAH emissions with the remainder produced by mobile sources. Mobile
sources are however likely to be the major PAH contributors in urban or suburban
areas, where major stationary sources are not present (U.S. National Academy
of Sciences, 1983).
The data in Table I demonstrates the variation in significance of emission sources
between countries. This data does not show any development of source contributions
in a given area due to its singular sampling period, it does however indicate the
importance of resource availability and subsequent utilization. The increased
availability of wood in the USA into the early eighties resulted in increased PAH
emissions from wood-stoves and fireplaces for home heating (Harkov and Greenberg,
 A REVIEWOF ATMOSPHERICPOLYCYCLICAROMATICHYDROCARBONS 281

TABLE I
Estimated atmospheric emissions of total PAH by source type (t yr -~)

Total PAH emissions

Source type U.S.A. Sweden Norway
(a) (b) (c) (d)

ResidentiM Heating
- Coal & wood burning 3 939 450 96 48
- Oil & Gas burning 17 930 36 15
Sub Total 3 956(36%) 1 380(16%) 132(26%) 63(21%)

Industrial Process
- Coke manufacturing 632 2490 277 43
- Asphalt production 5 4
- Carbon black 3 3
- Aluminium plants - 1000 35 160
- Others 2
Sub Total 640(6%) 3497(41%) 312(62%) 203(69%)

Incineration
Municipal
- - - -
- Commercial 56 50 2 1

Sub Total 56(1%) 50(1%) 2(1%) 1(0%)

Open Burning
- Coal refuse fires 29 100 - -
- Agricultural fires 1 190 400 1 2
- Forest fires 1478 600 1 5
- Others 1 328 - - -
Sub Total 4025(36%) 1 100(13%) 2(1%) 7(2%)

Power generation
- Power plants 13 1 -
- Industrial boilers 75 400 7(1%) l ( 0 % )

Sub Total 88(1%) 401(5%) 7(1%) l(0%)

Mobile Sources
-Gasoline engines 2161 a 2 100a 33 13
-Diesel engines 105 70 14 7
Sub Total 2266(21%) 2170(25%) 47(9%) 20(7%)

Total 11 031 8598 502 294

a This figure was not corrected for cars with emission control devices (approximately 50% when estimated).
(a) data from Peters et al. (1981).
(b)to (d) data from Ramdahl et al. (1983).

1985; F r e e m a n a n d C a t t e l l , 1990; B e n n e r e t al., 1989; M c V e e t e y a n d H i t e s , 1988).

Several studies have shown that PAH emissions have undergone long term
v a r i a t i o n s . B e n n e r e t al. (1989) r e p o r t P A H levels l o w e r b y a f a c t o r o f 5 t o 10
in the B a l t i m o r e H a r b o r T u n n e l t h a n t h o s e r e p o r t e d b y F o x a n d S t a l e y (1976).
282 s.O. BAEK ET AL.

They attribute this difference to the increased use of catalytic converters in motor
vehicles. A declining trend in the Benzo (a) pyrene (BaP) concentration of ambient
air has been observed in London since the 1950's (Lawther and Waller, 1976; Phillips,
1983). The annual mean concentration of BaP in central Londen decreased from
46 ng m -3 in 1949/1951 to 4 ng m -3 in 1972/1973 (Commins and Hampton, 1976).
Baek et al. (1991a, b) report that levels of BaP during 1985/1986 were a fifth
of those previously reported for central London by Commins and Hampton (1976)
during 1972/1973. The level of Coronene (COR) however exhibited the least reduction
compared to other PAH. This may be attributed to the prevalence of COR in
motor exhaust. The fall in ambient levels of BaP can be attributed to a reduction
in coal and open burning with a movement to oil and natural gas as energy sources,
as well as to improved combustion technology. PAH emissions from open burning,
especially coal, have been declining in many 'developed' countries primarily as a
result of efforts to control smoke emissions. In the United Kingdom (UK) such
efforts have been centered on the Clean Air Acts of 1958 and 1965 and subsequently
upon a European Community Directive (European Economic Communities, 1980).
The data compiled in Table II and Table III shows that emitted PAH compounds
exhibit seasonal fluctuations and local variations as well as long term changes.
In most cases higher levels are apparent in winter compared to summer and in
urban compared to rural areas (Hoff and Chan, 1987; Lyall et al., 1988; Halkiewicz
et al., 1987; Coutant et al., 1988; Catoggio et al., 1989; Broman et al., 1988). Baek
et al. (1991b) report PAH levels 2 to 4 times higher during winter compared to
summer. Several factors may be involved in the observed variations in ambient
PAH concentrations between summer and winter. Changes in emission patterns
(both stationary and vehicular) and meterological conditions (including shorter
daylight hours and reduced temperature) contribute to the higher PAH levels during
winter (Ramdahl et al., 1982, 1983; Grosjean, 1983; Freeman and Cattell, 1990).
The seasonal variance can be attributed to a large extent to changes in space heating
emissions, volatilization and photochemical activity (Masclet et al., 1986; Lyall et
al., 1988; Catoggio et al., 1989; Pistikopoulos et al., 1990; Freeman and Cattell,
1990; Benner et al., 1989).
The PAH content of a sample of urban air can be considered to be a composite
of the various local sources combined with a contribution from outside that area.
The significance of the external influx will depend upon the size of the area sampled
(Lee et al., 1976). It may be reasonable to expect profiles of PAH in ambient air
to differ quantitatively and qualitatively between cities and within cities. Divergent
profiles of PAH within a city were demonstrated by Grimmer et al. (1980) for
samples in different areas of Essen (Federal Republic of Germany (FRG). Table
III shows that the relative proportions of Cylcopenta (c, d) pyrene (CcdP), Benzo
(c) phenanthrene (BcPH), Benzo(ghi)perylene (BghiP) and COR were enriched in
tunnel samples compared to other areas. The association of BghiP and COR with
vehicle exhaust has been long established (Hangebrauck et al., 1967; Daisey et
al., 1986; Nielsen, 1988; Grimmer et al., 1980; PederSen et al., 1980; Tuominen
 A REVIEW OF A T M O S P H E R I C POLYCYCLIC A R O M A T I C HYDROCARBONS 283

TABLE I1
Concentrations (ng m -3) of selected PAH in the ambient air of the United States of America (U.S.A.)

Location Los Angeles New Jersey

Area Urban a Urban b Urban c Rural c

Source Traffic Traffic Traffic/ Heating
Period 1974-5 1981-82 Residential 1982-3
Season Summer Summer 1982-3 Summer
Winter Winter Summer Winter

PHEN . . . . . .
ANTHR - - 0.0 0.8 - - -
FLUR 0.2 0,7 0.8 1.0 - - -
PYR 0.3 1.2 1,5 1.7 0.1-0.4 1.8-2,8 0.1 0.4
BcPH . . . . . .
CcdP - - - 0.0-0.1 0.4-0.7 0.0 0.l
BaA 0.1 0.6 0.2 0.6 0.1-0.2 0.6-0.9 0.0 0.1
CHRY 0.4 1.6 0.6 1.2 0.2-0.5 0.6-2.4 0.1 0.3
BNTH . . . . . .
BeP 0.6 2.0 0.1 0.6 0,0-0.2 1.1-1.8 0.0 0.3
BbF 0.3 1.3 0.4 1.2 0.2-0.3 0.8-1.1 0.1 0.3
BkF 0.2 0,5 0.2 0.4 0.1-0.2 0.4-0.6 0.0 0.1
BaP 0.3 1.3 0.2 0.6 0.1-0.2 0.7-1,1 0.0 0.2
DahA . . . . . .
BghiP 3.7 10.9 0.3 4.5 0.2-0.6 1.1-1.4 0.0 0.3
I123P 1.0 2.6 - 0,2-0.4 0.9-1.0 0.1 0.2
ANTHN 0.1 0.8 . . . .
COR 1.7 4.4 1.4 4.7 0.1-0,4 0.5-0.6 0.1 0.2

a Gordon (1976).
b Grosjean (1983).
c Greenberg et al. (1985).

Nomenclatures for PAH: PHEN=phenanthrene, ANTHR=anthracene, FLUR=fluoranthene,

BcPH=benzo(c)phenanthrene, CcdP=cyclo(cd)pyrene, BaA=benzo(a)anthracene, CHRY=chrysene.
BNTH=benzo(b)naphtho(2.1-d)thiophene, BeP=benzo(e)pyrene, BbF=benzo(b)fluoranthene,
BkF=benzo(k)fluoranthene, BaP=benzo(a)pyrene, DahA=dibenz(a,h)anthracene,
BghiP=benzo(ghi)pyrene, I123P=indeno(1,2,3-cd)pyrene, ANTHN=anthracene, COR=coronene.

et al., 1988; M a s c l e t et al., 1986). H o w e v e r b u s h fires in A u s t r a l i a w e r e f o u n d

to e m i t e n h a n c e d levels o f B a P a n d C O R c o m p a r e d w i t h o t h e r fuel s o u r c e s . T h i s
m a y a f f e c t t h e v a l u e o f u s i n g C O R as a m a r k e r f o r m o t o r v e h i c l e e m i s s i o n s in
s o m e a r e a s ( F r e e m a n a n d C a t t e l l , 1990). P y r e n e ( P Y R ) a n d f l u o r a n t h e n e ( F L U R )
a r e c h a r a c t e r i s t i c o f fuel oil b u r n i n g ( M a s c l e t et al., 1986). T h e p r o f i l e s f o r a r e a s
influenced by coal burning and coke production are very similar, being characterised
by relatively high concentrations of Benzo(b)naphto(2, l-d) thiophene (BNTH)
( G r i m m e r et al., 1981). T h e p r o f i l e a n a l y s i s b y F u n k e et al. (1982, c i t e d in S m i t h ,
1984) in o t h e r G e r m a n cities, h o w e v e r , f o u n d t h a t , a p a r t f r o m e l e v a t e d c o n c e n t r a t i o n s
o f P A H in w i n t e r c o m p a r e d to s u m m e r , t h e r e was little d i f f e r e n c e b e t w e e n t h e
p r o f i l e s o f d i f f e r e n t cities. T h e y c o n s i d e r e d t h a t a t m o s p h e r i c t r a n s p o r t , d e g r a d a t i o n
284 S. O . B A E K E T A L .

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 A REVIEW OF A T M O S P H E R I C POLYCYCLIC A R O M A T I C H Y D R O C A R B O N S 285

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286 s.o. BAEK ET AL.

and deposition processes resulted in relatively similar profiles when averaged over
periods of several weeks. Greenberg et al. (1985) also reported that the profile
for PAH in 3 sites in New Yersey were constant both within and between urban
sites for a particular season, indicating the significant effects of prevalent mete-
orological conditions on the distribution of PAH. It is however useful to consider
the overall similarity of PAH samples between many cities, as a function of
comparable levels of emissions from the various sources relative to the size of the
city, as well as of the meteorologcial conditons (Hanna, 1971).
Atmospheric concentrations of PAH can be related to contributing sources by
comparing a profile of them with emission patterns of potential sources (Lee et
al., 1976; Grimmer et al., 1980; Daisey et al., 1986; Hangebrauck et al., 1967).
In order to evaluate the compositional differences in PAH profiles, the concentrations
of PAH are usually standardized into ,a ratio with a specific PAH. Benzo(e)pyrene
(BeP) has frequently been selected as a reference PAH (Table IV) since it is
photochemically stable and predominately found in the particulate phase (Butler
and Crossley, 1981; Daisey et al., 1986). The relative proportions of some PAH
from a given source type vary characteristically over several orders of magnitude
(Table IV). This enhances the potential use for source discrimination, for example
the condensates of vehicle exhausts are relatively enriched in FLUR, PYR, BghiP,
COR and Cede
Recently, despite its limitations in application to reactive species the possibility
of receptor source apportionment modeling was examined using the profiles of
PAH emissions from a variety of sources (Daisey et al., 1986; Pistikopoulos et
al., 1990).

3. Emissions from Vehicle Exhaust

Motor vehicles account for the majority of PAH emissions in urban areas (Freeman
and Cattell, 1990; Tuominen et al., 1988). In general exhaust emissions of PAH
from mobile sources originate by three distinct mechanisms; (i) synthesis from simpler
molecules in the fuel, particularly from aromatic compounds, (ii) storage in engine
deposits and subsequent emission of PAH already in the fuel and (iii) pyrolysis
of lubricant (Gross, 1974). The emission rates of PAH from vehicle exhausts are
dependent upon a large number of factors including; engine type, operating
conditions and composition of both fuel and lubricating oil (Candeli et al., 1983;
Pedersen et aL, 1980).
The effect of engine type is largely determined by the design of the combustion
system, the fuel/air mixture, the temperature within the combustion chamber and
the manufacturing quality. It has been established that different vehicles operated
under the same conditions with the same fuel can emit significantly different amounts
of PAH (Handa et aL, 1979; Lang et al., 1981).
The main engine operating parameters that affect exhaust PAH content are engine
load, air to fuel ratio (AFR) and engine coolant temperature. The latter was found
 A REVIEW OF A T M O S P H E R I C POLYCYCLIC A R O M A T I C H Y D R O C A R B O N S 287

to only slightly influence PAH emissions, indicating that wall temperature of the
combustion chamber p e r se is not the main cause of the high PAH emission from
cold-started engines (Pedersen et al., 1980). Stenberg et al. (1983) estimated greater
than 5 fold increases of BaP emissions from spark-ignition vehicles during the first
3 to 4 km when ambient temperatures were below 0 °C. This implies that in a
period following a cold start, the engine will be operating on a rich mixture, i.e.
low AFR, as well as higher engine load, both of which are found to increase PAH
emissions considerably (Laity et al., 1973; Pederson et al., 1980). In general larger
quantities of PAH are emitted during acceleration, deceleration or when cruising
at high speeds than when driving at steady average speeds. Of the various engine
operating parameters, changes in the AFR are known to produce the largest effects
on PAH emission. It has been found that the amount of PAH in engine exhaust
decreases with increasing AFR (i.e. leaner mixture), except for a sharp increase
in the vicinity of the 'lean misfiring limit' (Pedersen et al., 1980; Laity et al., 1973).
Since leaner mixtures supply excess O2, more complete combustion occurs, resulting
in lower emission of PAH (Hall et al., 1982).
The aromatic hydrocarbon content of fuel has been the main focus of concern
directed at the composition of fuels, since benzene and its derivatives produce more
PAH than aliphatic hydrocarbons (Hoffman et al., 1965). A number of investigations
have shown that PAH emissions increase as the aromatic content increases (Candeli
et aL, 1974; Begeman and Colucci, 1970; Gross, 1973, 1974; Laity et aL, 1973).
Not all aromatic compounds have the same effect, suggesting the importance of
the individual aromatic constituents in a fuel (Candeli et al., 1974, 1983). The aromatic
fraction in fuels, for either petrol or diesel engines, generally contains a broad
spectrum of aromatic compounds, ranging from C 6 to C10 or C10+, although the
heavier compounds (Cm +) are present only in a low percentage (Candeli et al.,
1974). It was found that benzene derivatives, such as ethyl benzene and xylene,
were better precursors for PAH formation than benzene itself (Candeli et al., 1974,
1983). In general, the greater the content of high-boiling aromatic compounds in
fuels, the higher the PAH content (Hall et al., 1982; Pedersen et al., 1980; Badger,
1962).
An additional fuel parameter likely to affect PAH emission is the content of
Pb alkyls, which are added to petrol as anti-knocking additives. For a given octane
number the Pb and aromatic content of a fuel are not independent of one another,
since the aromatic hydrocarbons also exert a marked anti-knock effect (Griffing,
et al., 1971; Begeman and Colucci, 1970; Candeli et al., 1974; Gross, 1972, 1974;
Lang et al., 1981). The Pb content exerts, in comparison with fuel aromatic content,
only a slight influence on particle-bonded PAH emissions, both as a single variable
and when the fuel aromatic content was changed simultaneously (Pederson et al.,
1980).
During recent years, there has been a considerable change in fuel composition
on a worldwide basis, in particular there has been a decrease in the use of Pb
alkyl anti-knock additives in petrol (Tims, 1983). The Pb content of gasoline in
288 s . o . BAEKET AL.

TABLE V

Pb and aromatic content Of European p r e m i u m petrol (Associated Octel. 1985, 1986, 1987, 1988)

Mean lead content (g L -1) Mean aromatic content (% vol)

1984 1985 1986 1987 1984 1985 1986 1987

UK 0.40 0.40 0.15 0.15 a 31.6 29.9 34.3 31.0 a

FRG 0.15 0.15 0.15 0.15 42.6 39.2 41.8 37.8
France 0.40 0.,40 0.40 0.40 34.0 34.4 29.1 31.2
Italy 0.40 0.40 0.40 0.40 29.4 29.5 29.1 29.9
Benelux b 0.40 a 0.40 0.15 a 0.15 35.4 a 33.7 29.5 40.7
Sweden 0.15 a 0.15 0.15 a 0.15 37.9 a 37.9 a 39.8 a 42.3

a Denotes that samples were collected during winter, all other samples were collected during the
summer.
b Belgium, Netherlands and Luxemburg.

the UK was reduced from 0.40 to 0.15 g L -1 from 1985 to 1986 (Table V). This
change reflects the lowering of maximum limits of Pb in fuels by the European
Community (EC).
In order to maintain the octane quality of petrol whilst reducing Pb content,
the aromatic content of petrol was increased in most countries (CANCAWE, 1983).
The changing situation in European countries with respect to the Pb content of
premium petrol and its associated aromatic content is shown in Table IV. In the
F.R.G., as a result of reducing the Pb content from 0.4 to 0.15 L -1 in 1976, the
aromatic content was increased by approximately 20% (Associated Octel, 1976,
1982), and a similar increase was predicted for other European countries which
intended to reduce the Pb content in petrol to 0.15 L -~ (Hall et al., 1982). The
same reduction of Pb in the UK did not result in any significant increase in aromatics,
mainly because the short chain aliphatic content of the petrol was increased. In
France and Italy high Pb content is associated with low aromatic content and
conversely in Sweden and the FRG low Pb content is associated with high aromatic
content. It has been shown that increasing the aromatic content of petrol significantly
increases the PAH content of the exhaust (Candeli et al., 1983). As a consequnece
the decision to reduce the Pb content of petrol has been a cause of much concern
with respect to possible increase in PAH emissions (Rondia et al., 1983). The decreased
use of Pb in petrol has shifted attention to the use of certain PAH compounds
as motor vehicle emission tracers (Benner et al., 1989).
Less attention has been paid to the content and type of aromatics in diesel fuels
since the aromatic fraction can be lowered significantly without affecting quality,
which may even be improved when the percentage of aromatics is lowered (Candeli
et al., 1983).
It is however uncertain whether the PAH emitted are those which survive the
combustion process or are produced by a rearrangement of PAH present in the
fuel (Handa et al., 1979; Pedersen et al., 1980). Significant 'carry over' effects of
deposits formed during combustion of PAH rich fuels were observed by Griffing
 A REVIEW OF ATMOSPHERIC POLYCYCLIC AROMATIC HYDROCARBONS 289

et al. (1971) and Gross (1972, 1973, 1974). However, Westerholm et al. (1988) report
that up to 95% of the fuel PAH content is decomposed during combustion, emitted
PAH being mainly formed by the combustion process. For example aromatic
compounds produce PAH by dimerization followed by condensation (Bruinsma
and Moulyn, 1988). Pedersen et al. (1980) reported that an approximate 23 times
increase in the BaP content of fuel resulted in only a 3 to 5 fold increase in BaP
exhaust emissions. Westerholm et al. (1988) report that PYR resists combustion
and that 80% of CcP is formed during the combustion process.
PAH are also produced by the combustion of lubricating oil, this source is however
relatively minor under normal operating conditions. The chemical structure of the
lubricant will control the retention capacity for PAH and also its emission
characteristics on combustion. The accumulation of PAH in the lubricant was
explained largely by the presence of PAH deposits in the combustion chamber
(Begeman and Colucci, 1970; Gross, 1974).

4. Atmospheric Behavior and Fate

More than one hundred PAH compounds have been identified in urban air (Lee
et al., 1976). These compounds are associated predominantly with particulate matter
(U.S. National Academy of Sciences, 1972, 1983), but are also present in the gaseous
phase. Studies of atmospheric PAH have until rccently concentrated on particulate
matter since gas phase sampling has proved to be difficult (Marty et al., 1984;
Vain Vaeck et al., 1984) and particulate PAH were considered to be the more abundant
and hazardous to human health of the two phases (Lyall et al., 1988; Cautreels
and Van Cawenberghe, 1978).

4.1. FORMATION
The incorporation of PAH into particulates has bcen explained by a general
condensation and adsorption mechanism. PAH are initially generated in the gas
phase, and then adsorbed on pre-existing particles while undergoing condensation
during further cooling of the emission (Thomas et aL, 1963; Van Vaeck et al.,
1984). For the least volatile PAH the gas particle conversion step may be determined
shortly after emission. A considerable fraction of the more volatile PAH will escape
particle incorporation and persist in the atmospheric gas phase (Broddin et aL,
1980).

4.2. GAS P A R T I C L E DISTRIBUTION

The distribution of PAH in the atmosphere between the gas and particulate phases
is determined by several factors, which include; the vapor pressure of the PAH
(as a function of temperature); the amount of fine particles (in terms of available
surface area for adsorption of PAH); the ambient temperature; PAH concentration;
and the affinity of individual PAH for the particles organic matrix (Yamasaki et
al., 1982; Van Vaeck et al., 1984; Baker and Eisenreich, 1990; Tuominen et al.,
290 S. O. BAEK ET AL.

1988; Coutant et al., 1988). A number of studies have demonstrated that atmospheric
PAH concentrations are highly dependent upon the size of airborne particulate
matter, with the greatest concentration being in the respirable size range. DeMaio
and Corn (1966) found that more than 75% by weight of selected PAH from
Pittsburgh air were associated with particles less than 5.0 ~m in aerodynamic
diameter. Van Vaeck et al. (1979, 1984) reported that about 90 to 95% of total
PAH in both urban and surburban areas of Belgium were associated with a size
class less than 3 t~m, with 60 to 70% being present on particles less than 1 ~m
in diameter. Baek et al. (1991a) report a unimodal distribution for particulate PAH,
in contrast to the ambient aerosols with which they were associated. The peaks
of the PAH distributions appear to be exclusively localized between 0.4 and 1.1
~tm. During winter Baek et al. (1991a) estimate that 63 to 82% of particulate PAH
were associated with aerosols of aerodynamic diameter of less than 1.1 ~m. Up
to 95% were associated with particles under 3.3 ~m diameter (Baek et al., 1991a).
Pistikopoulos et al. (1990) report two particle size distribution families for PAH.
One group is associated with particles of less than 1 ~m and corresponds to relatively
non volatile PAH, the other is associated with particles greater than 1 ~m and
corresponds to volatile PAH, except fluoranthene. The first group being formed
by adsorption, the second by condensation (Pistikopoulos et al., 1990).

4.3. ATMOSPHERIC PROCESSES

Once PAH are released into the atmosphere, they are subject to a variety of
atmospheric processes through which their distribution, removal, transport, and
degradation can occur. Thus, the quantity of and distribution of atmospheric PAH
is dependent not only on the magnitude of emissions but also on the stability of
PAH in the atmosphere. The atmospheric phenomena involved in the evolution
of PAH can be summarized as follows: (i) physical removal by dry or wet deposition,
(ii) atmospheric transport and dispersion by the shift of air masses, turbulence
and convection, (iii) atmospheric degradation or conversion either by chemical or
photochemical reactions, and (iv) exchange between the gaseous and particulate
phase by shifting the phase equilibrium (U.S. National Academy of Sciences, 1972;
Masclet et al., 1986).

4.4. DEPOSITION AND TRANSPORT

Since PAH in the atmosphere are mostly associated with particulate matter, their
atmospheric residence time is closely related to the behavior of the carrier particles.
(McVeety and Hites, 1988; Chuang et al., 1987; Baker and Eisenreich, 1990). The
physical removal or transport of airborne particles is a function of the particle
size and meteorological conditions. It has been established that both coarse particles
(larger than 3 to 5 ~m) and nuclei range particles (below 0.1 ~tm) are similarly
limited in their atmospheric residence times, and consequently in their effects,
although their removal mechanisms are different. The former tend to be removed
from the atmosphere by simple sedimentation, such as dry or wet deposition, while
 A REVIEW OF ATMOSPHERIC POLYCYCLIC AROMATIC HYDROCARBONS 291

the latter are removed predominantly by coagulation with each other and or larger
particles (Whitby and Sverdrup, 1980). Particles in the size range between 0.1 and
3 ~xm, with which airborne PAH are predominantly associated, are known to diffuse
only slowly and have little inertia, and can be expected to remain airborne for
a few days or longer (Lodge et al., 1981). Particles of this size class are not removed
efficiently by rain and may be transferred over long distances, dependent upon
atmospheric conditions (Grover et al., 1977).
The presence of PAH in precipitation appears to be the result of both in-cloud
and below-cloud scavenging of atmospheric PAH (Georgii and Schmitt, 1982; Muller,
1984; Van Noort and Wondergem, 1985). In general, PAH concentrations in
precipitation were found to be higher in winter than in summer, reflecting seasonal
variations of the atmospheric levels. In addition, snow fall appears to be a more
effective sink for PAH than rainfall (Gerogii and Schmitt, 1982; Muller, 1984).
PAH in the gas phase enters rain through gas water partitioning mainly by below
cloud scavenging, whereas those associated with particles are more efficiently
removed within clouds as a result of diffusion, impaction and interception (Van
Noort and Wondergem, 1985; Ligocki et al., 1985; Masclet et al., 1986; Tuominen
et al., 1988). Gas phase PAH are however prone to revolatilize once deposited,
especially from water bodies (Baker and Eisenreich, 1990; McVeety and Hites, 1988).
Masclet et al. (1986) report that wet scavenging van remove up to 60% of PAH
concentration during precipitation events. Dry deposition can be classified into
three mechanisms, diffusion, impaction and sedimentation (Schroeder and Lane,
1988). Estimates of concentration fluxes to wet and particulary dry deposition are
however uncertain, due mainly to the number of chemical and physical variables
involved (Behymer and Hites, 1988).
The association of PAH with the fine fraction of airborne particulate matters
is of importance in terms of their persistence in the atmosphere, where they can
undergo chemical reactions as well as be transported over long distances. Lunde
and Bjorseth (1977) identified 20 different PAH in aerosol samples with different
trajectories collected in southern Norway. High levels of PAH were generally
associated with trajectories from the European continent and the UK (Alfhiem
and Moller, 1979; Daisey and Lioy, 1981). The occurenee of some PAH in remote
pristine areas such as the Arctic and marine atmospheres was explained mainly
by aerial trasnport from distant anthropogenic sources (Marty et aL, 1984; McVeety
and Hites, 1988). The similarity of sediment and air PAH profiles as well as ubiquitous
occurence lead to the conclusion that the transport of PAH is extensive (McVeety
and Hites, 1988; Freeman and Cattell, 1990). PAH will however be depleted by
reaction during transport prior to deposition (Masclet et al., 1986).

4.5. REACTION
A number of experimental studies have demonstrated that many PAH are susceptible
to photochemical and/or chemical oxidation under simulated atmospheric conditions
(Thomas et al., 1963; Pitts et al., 1977, 1985a, b; Nielsen, 1984; Kamens et al.,
292 S. O. BAEK ET AL.

1988). Although results from the laboratory simulation studies are difficult to
extrapolate to the reactivities of PAH under real atmospheric conditions, there
is however potential for chemical transformation of PAH by gas-particle interactions
in emission plumes, exhaust systems or even during atmosphertic transport (U.S.
National Academy of Sciences, 1972; Nielsen et al., 1983; Daisey et al., 1986).
Furthermore, the presence of direct mutagens in ambient aerosols which can not
be explained by PAH alone, may be at least in part due to the transformation
products of PAH (Pitts, 1983; Gibson et al., 1986). Oxy, hydroxy, nitro and
hydroxynitro PAH are possible reaction products (Albei6-Jureti6, 1990; Brorstrom-
Lunden and Lindskog, 1985). Nitro and Oxy PAH reaction products may be present
in the gas phase as well as particulate (Hoff and Chan, 1987).
Photochemical transformation have generally been considered to be the most
important mode of atmospheric decomposition of PAH of both phases (U.S. National
Academy of Sciences, 1972; Masclet et al., 1986; Kamens et al., 1984, 1990). Although
the degradation rates by photolysis of different PAH show a wide variation, it
has become apparent that the extent of photochemical decay is strongly influenced
by the nature of the substrate on which they are adsorbed (Korfmacher et al.,
1980; Valerio and Lazzarotto, 1985; Behymer and Hites, 1988). PAH appear to
be more stable when adsorbed on naturally occurring particles such as soot or
fly-ash than when present in pure form or in solution or adsorbed on silica gel,
alumina or coated on glass surface. (Korfmacher et al., 1980; Hughes et al., 1979).
The physical (color) and chemical (C content) characteristics of the substrate are
important in determining the reactivity of the adsorbed PAH (Behymer and Hites,
1988). The reactivity of the PAH itself is however more important in determining
reactivity than the substrate (Behymer and Hites, 1988). The available PAH on
the substrate surface for reaction is also an important variable (Coutant et al.,
1988; Albei6-Jurei6 et al., 1990). The suppression of photochemical degradation
of PAH on soot or fly-ash has been tentatively explained by physical factors, such
as pore structure and color of the particles, and more strongly by chemical factors
involving the stabilizing effect of transition metal ions present on the particle surface
acting as quenchers of excited states of PAH molecules (Korfmacher et al., 1980;
Behymer and Hites, 1988).
Although irradiation appears to play a major role in the degradation of airborne
PAH (Valerio and Lazzarotto, 1985; Kamens et al., 1990), light is not necessarily
required for the atmospheric decomposition of PAH. Various PAH may also degrade
by non-photochemical pathways such as evaporative or oxidative reactions with
gaseous pollutants (Korfmacher et al., 1981). Korfmacher et al. (1981) found that
fluorene and benzo (a/b) fluorene underwent oxidation without the presence of
light. The non photochemical degradation of PAH is of particular importance not
only because some PAH would be expected to decompose in the atmosphere without
sunlight, but also that certain PAH compounds can be expected to degrade during
sampling and storage in the absence of light (Korfmacher et al., 1981).
A number of experimental studies have shown that PAH can react readily with
 A R E V I E W OF A T M O S P H E R I C P O L Y C Y C L I C A R O M A T I C H Y D R O C A R B O N S 293

03 at ambient concentrations (Pitts et al., 1986; Brorstrom et al., 1983; Peters and
Seifert, 1980; Albei6-Jureti6 et al., 1990). Alebi6-Jureti6 et al. (1990) identify quinones
and epoxides as possible products of such reactions. The kinetics of the dark reaction
of several PAH towards 03 has been shown to be extremly fast under simulated
atmospheric conditions. Lane and Katz (1977) reported a half life of 0.62 hr for
BaP exposed to an 03 level of 190 ppb, irradiation appearing not to affect this
reactivity significantly. Peters and Seifert (1980) investigated the effect of 03
concentration on the loss of BaP under high volume sampling. They found the
lifetime of BaP to be inversley correlated with the ambient 03 concentration. The
reaction of PAH adsorbed on diesel particulates with ppm levels of 03 was
investigated by Van Vaeck and Van Cauwenberghe (1984). BaP and Benzo(a)an-
thracene (BaA) were found to be the most reactive PAH investigated, with conversion
yields of 60 and 50%, respectively. Pitts et al. (1986) demonstrated that five PAH,
found at ng m -3 levels in ambient particulate organic matter, reacted with ozone
in the range 50 to 300 ppb, regardless of the relative humidity of the simulated
system. These results implied that significant degradation of PAH may take place
in 03 polluted atmospheres, such as the Los Angeles air basin where ambient ozone
levels of 200 ppb are quite often exceeded at downwind smog receptor sites. Grosjean
et al. (1983) have however questioned the environmental relevance of PAH reactions
with 03 and other atmospheric pollutants. BaP, perylene and 1- nitropyrene showed
no significant degradation when exposed to 100 ppb of 03 at 50% relative humidity.
Other researchers also attach negliable importance to 03 reaction with PAH
(Atkinson and Aschmann, 1986; Coutant et al., 1988; De Raat et al., 1990).
Chemical reactions of PAH with NO x are particularly important since these
compounds are usually emitted simultaneously with PAH from combustion sources
(Hughes et al., 1979; Pitts et al., 1978; Siak et al., 1985) and may result in the
conversion of noncarcinogenic PAH to mutagenic nitro-PAH compounds (Pitts et
al., 1985a,b; Schroeder and Lane, 1988). The rate of reaction was found to be
highly dependent upon the chemical structure of the individual PAH and the nature
• of the substrate on which the PAH are adsorbed (Nielsen et al., 1983). In addition,
the reactions were facilitated by the acidity of the surface, particularly the presence
of nitric acid (Nielsen, 1984; Grosjean et al., 1983). Differences in the reactivity
of individual PAH towards nitrating agents appeared to be generally in agreement
with the order expected for electrophilic nitro substitution of aromatic systems
(Nielsen, 1984; Butler and Crossley, 1981, Dewar et al., 1956a,b; Albei6-Jureti6
et al., 1990). There is a great deal of evidence for atmospheric nitration of PAH,
the occurrence of nitro-PAH in samples collected in the atmosphere might however
also be the result of artefact formation during high-volume sampling (Brorstrom-
Lunden and Lindskog, 1985). A number of authors do however indicate the
production of nitroarenes from the atmospheric reaction of PAH (Gibson, 1986;
Atkinson et al., 1987; Pitts et al., 1985a,b; Arey et al., 1988; Sweetman et al.,
1986). Pitts et al. (1987) report the atmospheric presence of 2-nitrofluoranthene
(2-NOz-FL) and 2-nitropyrene (2-NO2-PYR). Atkinson et al. (1987) indicate that
294 S. O. BAEK ET AL,

2-NO2-FL and 2-NO2-PYR are not emitted from combustion sources, although
Liberti and Ciccioli (1986) report the production of both compounds from the
manufacture of C electrodes. The nitration of PAH can be initiated by homogenous
gas phase reaction with OH (at the site of highest electron density) followed by
NO2 addition and the loss of H20. The product nitro-PAH then condenses on
the surface of ambient particles (Pitts et al., 1987). Nitro-PAH may also be produced
by the reaction of PAH with dinitrogen pentoxide (N205) (Pitts et al., 1985b,c,d,
1987; Kamens et al., 1990). The latter reaction is however believed to be of less
significance with estimates of PAH lifetimes in the order of weeks compared to
that of hours for reaction with OH (Pitts et al., 1987; Atkinson et al., 1987).
Atmospheric degradation of PAH may also occur by reaction with SO x or their
acid derivatives, particularly in aerosols or when adsorbed on particles (U.S. National
Academy of Sciences, 1972; Hughes et al., 1979). It is uncertain whether PAH
react with SO x in the atmosphere, even at very much higher concentrations than
normally found in ambient air (Nielsen et al., 1983; Leinster and Evans, 1986).
Little is known about the products from the reaction of PAH with SO x in
environmental samples. PAH related sulphonic acids have been found in laboratory
experiments, but no evidence is yet available for their presence as atmospheric
particulates (Brorstrom-Lunden and Lindskog, 1985). One of the reasons for this
may be that the sulphonic acids are water soluble, and hence they may not appear
in organic solvent extracts of the particulate matter (Olufsen and Bjorseth, 1983).

4.6. GAS P A R T I C L E DISTRIBUTION

Another important mode of the atmospheric evolution of PAH is their temperature-

dependent partition between gaseous and particulate phase (Yamasaki et al., 1982).
It appears from several studies that both the gas particle distribution and particle
size distribution of PAH are subject to seasonal variations (Tuominen et al., 1988;
McVeety and Hites, 1988). These variations may be attributed not only to changes
in emission profiles but also to changes in the gas-particle partition as a result
of differences in ambient temperature, vapor pressure and particulate concentration
(Coutant et al., 1988; McVeety and Hites, 1988; Masclet et al., 1986; Chuang et
al., 1987) as well as the adsorption surface (Natusch and Tomkins, 1978). Precipitation
removes particulate PAH more efficiently than the gas phase and this may affect
the gas particle distribution (Masclet et al., 1986). During colder weather, the
contribution of gaseous PAH to the total PAH is generally smaller (Broddin et
al., 1980; Marty et al., 1984) and proportionally more PAH are found in the smaller
(respirable) particles (Van Vaeck et al., 1979; Lyall et al., 1988; Baasel and Allen,
1981). The concentration at the submicron range can be explained by the con-
densation mechanism, since larger specific surface areas are associated with such
particles (De Wiest and Della Fiorentina, 1975; Van Vaeck and Van Cawenberghe,
1985).
The dilution of the gaseous and particulate phase emission during transport
through the atmosphere can also cause a redistribution of the gas-particle partition.
 A REVIEW OF A T M O S P H E R I C P O L Y C Y C L I C A R O M A T I C H Y D R O C A R B O N S 295

This can result in a desorption of some constituents of the particulate matter to

the gas phase, the so called 'aerodynamic dilution' effect (De Wiest and Della
Fiorentina, 1975). The exchange between the gaseous and particulate phases
represents an important feature of the ageing process of an aerosol (Van Vaeck
and Van Cawenberghe, 1985, Van Vaeck et al., 1984). This exchange may superimpose
on or interfere with the size distribution shift of PAH within the accumulation
mode during long term transport (Van Vaeck et al., 1979). PAH species with a
molecular weight below that of below pyrene exist to a large extent in the gas
phase (Puppet al., 1974; Cautreels and Van Cawenberghe, 1978; Hoff and Chan
1987; Baker and Eisenreich, 1990; Tuominen et al., 1988; Halkiewicz et al., 1987).
Back et al. (1991a) report that PAH with a molecular weight of less than 234
are 50% or more of this groups total concentration during the summer, these values
decrease by about half during the winter. Gas phase PAH above or equal to a
molecular weight of 252 constitute less than 20% of the total for such weights,
even during the summer (Baek et al., 1991a). On average 47% of the total PAH
were reported as gaseous by Back et al. (1991a,b). Back et al. (1991b) report that
three ring PAHs are predominantly gaseous, four ring PAH a mixture of both
phases and five and six ring PAH primarily particulate. PYR was estimated to
be 50% gaseous at 30 °C by Westerholm et al. (1988). De Raat et al. (1990) report
volatility as more important than reaction in determining the PAH profile.

5. Sampling Effects

A number of problems exist with the collection of PAH on filters. It is now realized
that PAH with lower molecular weights exist in the gas phase to a significant degree.
Early measurements of PAH only utilized filters which may not have collected
much of the vapor phase (Leinster and Evans, 1986; Yamaski et al., 1982; Thrane
and Mikalsen, 1981). Several types of filter materials have been used for sampling
PAH from the ambient atmosphere. Among these are glass fibre, cellulose, organic
membranes and silver membranes. Due to good mechanical strength and relatively
low cost, glass fibre filters have been most commonly used for high-volume sampling
(Van Vaeck et al., 1979; Back et al., 1991a,b,c). PAH samples may also be collected
by cascade impaction onto substrates. This method is able to distinguish between
particle sizes of PAH. Due to the low concentrations of PAH in ambient air, even
at urban locations, large volumes of air must usually be sampled to yield sufficient
mass of PAH for accurate analysis. Back et al. (1991c) report that filtration and
impaction methods yield particulate PAH levels which are generally within 20%
of each other. The early use of particulate samples may have lead to an under-
estimation of total PAH concentrations. The importance of measuring both phases
is now realized (Tuominen et al., 1990; Baek et al., 1991a,b,c). PAH on filters
and substrates may be stripped by the air stream or may react on the collection
medium (Leinster and Evans, 1986; Chuang et al., 1987; Back et al., 1991a). Coutant
et al. (1988) found extensive losses from spiked filters when placed under high
296 s.O. BAEK ET AL.

volume sampling conditions, 30 to 90% of PHEN and 10% of BaP were lost after
a 24 hr period. These findings agree with similar data from Freeman and Cattell
(1990) who report a 50% loss for PHEN after a 24 hr sampling period. This indicates
that volatilization (and potentially reaction) losses during sampling are strongly
dependent upon molecular weight. The temperature and volume of air sampled
as well as PAH concentration are also important variables (Leinster and Evans,
1986; Van Vaeck et al., 1984; McLachlan et al., 1990; Van Vaeck and Van
Cawenberghe, 1985; Coutant et aL, 1988). Volatilization has been reported for PAH
up to Chrysene (Van Vaeck et al., 1984; Westerholm et al., 1988) and can be caused
by the disturbance of gas particle equilibrium, with the possibility of both desorption
of aerosol and adsorption of gas on the filter or substrate (Van Vaeck et aL, 1984).
Volatilization and reaction losses can be expected with both impaction and filtration
collection methods, but the literature is unclear concerning their significance. The
use of isokinetic samplers for particulate PAH may remove some of the problems
inherent with high volume sampling (Bidleman, 1988) and shorter sampling times
may also decrease volatilization and artefact formation (Schwartz et al., 1981).
Polyurethane foam (PUF) plugs have been used as backup absorbants for high
volume sampling, but these can interfere with PAH analysis (Chuang et al., 1987).
The retention efficiency of PUF plugs may also vary with respect to temperature
and humidity (Keller and Bidleman, 1984). Polymeric resins such as Bondapak
C18 Porasil (Lindgren et al., 1980), XAD-2 (Chuang et al., 1987), Chromosorb
102 (Jackson and Cupps, 1978) and Tenax GC/TA (Van Vaeck et al., 1984; Baek
et al., 1990a,b,c) have been used as adsorbants for volatile PAH. Polymeric resins
are however limited to low volume sampling due to high back up pressures in
the sampling system. To offset the lower flow rate of sampled air the collection
period has to be increased to an order of weeks (Van Vaeck et al., 1984).
Losses can also occur during sample storage. Leinster and Evans (1986) estimate
that 32% of BaP is lost over 1 yr. However Thrane et al. (1985) found no PAH
losses in 6 months when stored below -20 °C whilst covered in foil. Sverdrup et
al. (1990) report the importance of storage container, temperature, and light to
the storage losses of PAH samples. Chrysene was found to be stable for 120 days
when stored in teflon coated glass dishes at -79 °C in the dark.

6. Conclusion

PAH in the atmosphere are predominantly of anthropogenic origin. Once the major
atmospheric sources of PAH have been identified a number of other variables must
also be considered. Combustion conditions, fuel composition, geographical location,
climate and emission rates all affect PAH concentrations in the atmosphere. Trends
in the atmospheric levels of the various PAH compounds have been observed both
in the long and short term. After PAH compounds are released into the atmosphere
they undergo a variety of processes, namely removal, transport and degradation
(reaction). Whilst resident in the atmosphere PAH may undergo chemical and
 A REVIEW OF ATMOSPHERIC POLYCYCLIC AROMATIC HYDROCARBONS 297

photochemical reactions with other atmospheric gases such as 03, NO x and SO x.

The degradation of PAH can produce compounds which can be more or less
mutagenic and carcinogenic than the parent PAH.

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