PAH diagnostic ratios for the identification of pollution emission sources.
ABSTRACT Polycyclic aromatic hydrocarbon (PAH) diagnostic ratios have recently come into common use as a tool for identifying and assessing pollution emission sources. Some diagnostic ratios are based on parent PAHs, others on the proportions of alkyl-substituted to non-substituted molecules. The ratios are applicable to PAHs determined in different environmental media: air (gas + particle phase), water, sediment, soil, as well as biomonitor organisms such as leaves or coniferous needles, and mussels. These ratios distinguish PAH pollution originating from petroleum products, petroleum combustion and biomass or coal burning. The compounds involved in each ratio have the same molar mass, so it is assumed they have similar physicochemical properties. Numerous studies show that diagnostic ratios change in value to different extents during phase transfers and environmental degradation. The paper reviews applications of diagnostic ratios, comments on their use and specifies their limitations.
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ABSTRACT: Concentrations of PAHs, PCBs and OCPs in sediments and mussels (caged and/or native) were determined at 16 stations in six major sites of coastal Turkey. The biological effects of pollution were evaluated using sediment toxicity tests and enzyme activity assays. EROD, PROD, GST, AChE, CaE, and GR activities were evaluated using the digestive glands of mussels. The total PAH concentrations in the sediments varied between nd and 79,674ngg(-1) dw, while the total OCP concentrations were in the range of nd to 53.7ngg(-1) dw. The total PAH concentrations in mussels varied between 22.3 and 37.4ngg(-1) ww. The average concentrations of total PCBs in mussels were 2795pgg(-1) ww in the shipyard, 797pgg(-1) ww in Marina 2 and 53pgg(-1) ww in Marina 1 stations. The results of whole-sediment toxicity tests showed a strong correlation between toxicity test results and pollutant concentrations. Selected cytosolic enzyme activities in digestive glands differed significantly depending on localities. These differences in enzyme activities were mainly related to the different pollutant levels of the sampling sites. The micro-organic contaminant profile patterns, toxicity tests and biomarker studies showed that shipyards and shipbreaking yards are the major potential sources of organic pollution in coastal areas.Science of The Total Environment 07/2014; 496C:165-178. · 3.16 Impact Factor
PAH diagnostic ratios for the identification of pollution emission sources
Marek Tobiszewski*, Jacek Namie? snik
Department of Analytical Chemistry, Chemical Faculty, Gda? nsk University of Technology (GUT), ul. G. Narutowicza 11/12, 80-233 Gda? nsk, Poland
a r t i c l e i n f o
Received 15 August 2011
Received in revised form
4 October 2011
Accepted 26 October 2011
Polycyclic aromatic hydrocarbons
Environmental fate of organics
PAH diagnostic ratios
a b s t r a c t
Polycyclic aromatic hydrocarbon (PAH) diagnostic ratios have recently come into common use as a tool
for identifying and assessing pollution emission sources. Some diagnostic ratios are based on parent
PAHs, others on the proportions of alkyl-substituted to non-substituted molecules. The ratios are
applicable to PAHs determined in different environmental media: air (gas þ particle phase), water,
sediment, soil, as well as biomonitor organisms such as leaves or coniferous needles, and mussels. These
ratios distinguish PAH pollution originating from petroleum products, petroleum combustion and
biomass or coal burning. The compounds involved in each ratio have the same molar mass, so it is
assumed they have similar physicochemical properties. Numerous studies show that diagnostic ratios
change in value to different extents during phase transfers and environmental degradation. The paper
reviews applications of diagnostic ratios, comments on their use and specifies their limitations.
? 2011 Elsevier Ltd. All rights reserved.
Polycyclic (or Polynuclear) Aromatic Hydrocarbons (PAHs) are
ubiquitous environmental pollutants. They are human carcinogens
and mutagens, they are toxic to all living organisms. Atmospheric
PAHs may cause respiratory problems, impair pulmonary function
and cause bronchitis (Tsapakis and Stephanou, 2005). The Euro-
pean Community and the U.S. Environmental Protection Agency
have listed them as priority pollutants.
PAHs can originate from natural processes such as biomass
burning, volcanic eruptions and diagenesis (Wang et al., 2007).
However especially in heavily urbanized or industrialized regions,
the majorityof these compounds are anthropogenic: coal and wood
burning, petrol and diesel oil combustion, and industrial processes
(Mostert et al., 2010). Liquid fuels spills are further sources (da Silva
and Bícego, 2010). PAHs are always emitted as a mixture, and the
relative molecular concentration ratios are considered (often only
as an assumption) to be characteristic of a given emission source.
Most diagnostic ratios involve pairs of PAHs with the same molar
massand similar physicochemical properties (see Table 1, data from
Mackay et al., 2006), so they ought to undergo similar environ-
mental fate processes.
Understanding the impact of particular emission sources on the
different compartments of the environment is crucial for proper
risk assessment and risk management. PAH diagnostic ratios may
provide an important tool for the identification of pollution
emission sources. Nevertheless, the unquestioning application of
PAH diagnostic ratios has recently been criticized (Galarneau, 2008;
Katsoyiannis et al., 2007; Zhang et al., 2005): some authors have
applied them unaware of the fact that they are not usually
conservative in the environment.
This paper discusses PAH diagnostic ratios as used for identi-
fying pollution emission sources. It focuses mainly on the parent
(non-substituted) PAHs diagnostic ratios as it is these that are
normally determined. The following sections discuss the applica-
tion of diagnostic ratios to the identification of pollution sources
from samples collected in different environmental compartments.
2. Sources identified by PAH diagnostic ratios
The PAH emission profile for a given source depends on the
processes producing the PAHs (Manoli et al., 2004). During low
temperature processes (e.g. wood burning), low molecular weight
PAHs are usually formed, whereas high temperature processes,
such as the combustion of fuels in engines, emit higher molecular
weight PAH compounds (Mostertet al., 2010). At high temperatures
organic compounds are cracked to reactive radicals, which react to
form stable PAHs during pyrosynthesis. These PAHs are less alky-
lated and their molecules contain more aromatic rings than pet-
rogenic PAHs (Hwang et al., 2003).
PAH diagnostic ratios have been used to distinguish diesel and
gasoline combustion emission (Ravindra et al., 2008a), different
crude oil processing products and biomass burning processes,
including bush, savanna and grass fires (Yunker et al., 2002).
* Corresponding author.
E-mail address: email@example.com (M. Tobiszewski).
Contents lists available at SciVerse ScienceDirect
journal homepage: www.elsevier.com/locate/envpol
0269-7491/$ e see front matter ? 2011 Elsevier Ltd. All rights reserved.
Environmental Pollution 162 (2012) 110e119
PAH diagnostic ratios show intrasource variability but inter-
source similarity (Galarneau, 2008). The search for PAH emission
sources using diagnostic ratios should proceed with the determi-
nation of the ratios for each emission source present in the area
investigated. The PAH ratios calculated for each hypothetical source
are not definitive: for instance, the diagnostic ratio reported by
Manoli et al. (2004) may show strong variations for a particular
source (e.g. BaA/(BaA þCHR) ¼ 0.3e0.6 for cement production) and
be similar for many sources (e.g. FLA/(FLA þ PYR) ¼ 0.4e0.5 for
cement production, metal manufacturing, fertilizer production,
diesel combustion and road dusts). Table 2 lists typical diagnostic
ratios taken from the literature.
3.1. Atmospheric PAH reactivity
Atmospheric PAHs can undergo photolysis and/or oxidation by
reacting with OH radicals, ozone, nitrogen oxides or other strong
oxidising agents (Marr et al., 2006), often with tiny water droplets
mediating heterogeneous oxidation (Raja and Valsaraj, 2006). The
half-lives of photolysis reactions are much lower for PAHs present
in atmospheric particulate matter (PM) than in water or organic
solvents (Niu et al., 2007). If the total decay rate constants of two
PAH compounds used in a diagnostic ratio are significantly
different, the diagnostic ratios change in value for gaseous and
particulate phase PAHs.
The reaction half-lives of ANTand PHE are 2.9 and 150 h on silica
gel, 0.5 and 45 h on alumina, and 48 and 49 h on fly ash, respec-
tively (Behymer and Hites, 1985). Another study of PAH photolysis
on fly ash particles shows that ANT photodegrades faster than PHE
(Niu et al., 2007). ANTadsorbed on particles reacts faster with NO2,
while PHE reacts slightly faster with OH radicals (Esteve et al.,
2004). The literature data suggest that the ANT/(ANT þ PHE) ratio
may be strongly influenced by photoreactions leading to the ratios
close to 0. This was confirmed only when a thick layer of soot was
irradiated: thinner layers showed the opposite behaviour, leading
to values close to 1 (Kim et al., 2009).
The FLA/(FLA þ PYR) ratio seems to be more conservative than
those mentioned above. The respective half-lives of FLA and PYR
are 74 and 21 h for silica gel-adsorbed PAHs, 23 and 31 h for
alumina, and 44 and 46 h for fly ash (Behymer and Hites,1985). PYR
adsorbed on graphite and diesel particles reacts faster with NO2,
but with OH radicals the reaction rates are the same (Esteve et al.,
2004, 2006). PYR adsorbed on fly ash (Niu et al., 2007) and soot
(Kim et al., 2009) decays slightly faster than FLA. Photoreactions are
expected to shift the ratio slightly towards higher values.
The BaA/(BaA þ CHR) ratio also tends to change as a result of
atmospheric photoreactions. The respective half-lives of BaA and
CHR are 4 and 100 h for silica gel, 2 and 78 h for alumina, and 650
and 690 h for carbon black, respectively (Behymer and Hites,1985).
Basic physicochemical constants of PAHs and abbreviations used in the text.
[mg L?1] at 25?C
[Pa m3/mol] at 25?C
aFrom (Hwang et al., 2003).
bFrom (Odabasi et al., 2006).
Diagnostic ratios used with their typically reported values for particular processes.
PAH ratioValue rangeSourceReference
et al., 2008
et al., 2008a
et al., 2008b
Pies et al., 2008
FL/(FL þ PYR)
Fossil fuel combustion
Grass, wood, coal
(ageing of particles)
Grass, wood and
ANT/(ANT þ PHE)
FLA/(FLA þ PYR)De La
et al., 2009
BaA/(BaA þ CHR)0.2e0.35
et al., 2002
et al., 2011
BaP/(BaP þ BeP)
IcdP/(IcdP þ BghiP)
et al., 2002
RET/(RET þ CHR)
Yan et al., 2005
et al., 2009
et al., 2011
et al., 2007
SCOMB e (FLA, PYR, BaA, CHR, BkF, BbF, BaP, IcdP and BghiP); SPAHs e sum of total
non-alkylated PAHs; SLMW e sum of two and three-ring PAHs; SHMW e sum of
four and five ring PAHs.
M. Tobiszewski, J. Namie? snik / Environmental Pollution 162 (2012) 110e119
BaA decays faster when adsorbed on soot, resulting in strong shifts
of the ratio towards low values (Kim et al., 2009).
The study of Niu et al. (2007) shows that the photolytic decay
half life of BghiP on fly ash is 169, while that of IcdP is 182 h. BghiP
(half-life 100e160 h) photodegrades faster than IcdP (half-life
210e1200 h) when adsorbed on soot particles (Kim et al., 2009).
This suggests that particle ageing shifts the IcdP/(IcdP þ BghiP)
ratio towards high values.
BaP is photodegraded more rapidly than its isomer BeP. The
reaction half-lives are 4.7 for BaP and 70 h for BeP bound on silica
gel,1.4 and 100 h if bound on alumina, and 31 and 35 if adsorbed on
fly ash (Behymer and Hites, 1985). Heterogeneous reactions of BaP
adsorbed on diesel or graphite particles with nitrogen oxides are
more rapid, while BeP reacts slightly faster with OH radicals (Esteve
et al., 2004, 2006). Sincethe BaP/(BaP þBeP) ratio is photosensitive,
it is often considered to be a marker of atmospheric particle ageing
and the photodegradation of gaseous and particle PAHs.
Laboratory investigations of photoactivity usually overestimate
environmental reaction rates, but the results of field experiments
show that differences in photodegradation rates may affect some
diagnostic ratios. Akyüz and Çabuk (2010) investigated the photo-
chemical oxidation of PAHs, particularly the changes in the ANT/
(ANT þ PHE) and BaP/BbF ratios during this process. ANT and BaP
are photodegraded faster than their isomers (Esteve et al., 2006).
Because ANTand PHE are gas-phase PAHs (Akyüz and Çabuk, 2010),
they are suitable for investigations of photolysis in the gaseous
phase, whereas BaP and BbF are bound to particles, so their ratio
may be used to investigate the influence of photo processes on PM-
bound PAHs. The faster decay of BaP than BeP adsorbed on PM10
was documented, and BaP decayed faster in months with a larger
number of daylight hours (del Rosario Sienra et al., 2005). The
photodegradation of PAHs adsorbed on particles was reported in
remote areas of Europe, with ANT/(ANT þ PHE) and BaP/
(BaP þ BeP) ratios showing diurnal variations (Alves et al., 2006).
3.2. Gas-particle partitioning
Atmospheric PAHs are pollutants bound either to the gas phase
or to PM. The PAH distribution between PM and the gas phase
depends on the size of the particulates and the organic carbon
content, the PM concentration in the air and the air temperature
(Tasdemir and Esen, 2007). Generally, PAHs lighter than PYR and
FLA tend to be present in the gaseous phase, whereas PAHs heavier
than BaA and CHR are mainly bound on particles.
Information, total concentrations of atmospheric PAHs should be
used to calculate diagnostic ratios (Ströher et al., 2007; Zhao et al.,
2010). Many studies focus on the calculation of diagnostic ratios
based on PAH concentrations in particulates only. It is wrongly
assumed that PAHs emitted as gaseous or particulate-bound
remain in their phase. This approach is contradictory to the parti-
tioning (or repartitioning) of PAHs between gas and particles in the
atmosphere (Tasdemir and Esen, 2007). PAHs related to combus-
tion sources are emitted at high temperatures as gases; when
cooled they condense on particulates (Marr et al., 2006). What is
more, gas-particle partitioning is seasonally dependent, the parti-
tioning constants depending on the ambient air temperature (Esen
et al., 2008). Fig. 1 shows the differences in diagnostic ratios that
might occur, when gas and particle phase are considered
Mantis et al. (2005) determined PAHs in PM10collected at urban
sites in Athens, Greece. The SCOMB/SPAH ratio indicated the
combustion origin of PAHs in particulates and was the highest at
a site with high traffic density. The values of FLA/(FLA þ PYR)
confirmed that the emissions were from petrol engines. The anal-
ysis of BaA/(BaA þ CHR) and BaP/(BaP þ BeP) indicated the faster
decay of BaA and BaP, which suggested that sampling points some
distance from urban areas were affected by urban PAH pollution.
The determination of gas and particle phase PAHs in samples
collected at a Korean industrial complex showed that the PAHs
originated from a combination of traffic, coal burning and
petroleum-related sources. PAH diagnostic ratios were used
together with multivariate statistic methods, which led to the
assessment that coal combustion is the predominant PAH source,
followed by traffic emissions, and petrochemical and steel indus-
tries emissions (Park et al., 2010).
3.3. Impact of particle size
Some studies show that diagnostic ratios do not change with
particle size. The studies of Wang et al. (2006) show that diagnostic
ratios are virtually the same in samples of PM2.5e10 and PM2.5.
Diagnostic ratios applied to fine (<2 mm) and coarse (>2 mm)
particulates collected in Beijing were similar with respect to ANT/
(ANTþ PHE) and IcdP/(IcdP þ BghiP). The values of FLA/(FLA þ PYR)
were 0.05e0.1 higher, those of BeP/(BeP þ BaP) were also slightly
higher, but those of BaA/(BaA þ CHR) were 0.1e0.15 lower for
coarse particles. These diagnostic ratios confirmed that the domi-
nant sources of PAHs were the combustion of coal/wood and diesel
in the summer (Zhou et al., 2005).
Oliveira et al. (2011) calculated diagnostic ratios in four fractions
of PM collected in a roadway tunnel. Such an environment provides
an opportunity to investigate virtually only vehicle emission sour-
ces. The BaP/(BaP þ BeP) ratio indicated ageing of particles with
Fig. 1. Diagnostic ratios calculated for gas and particle phase air samples. Reprinted from Contini et al. (2011). Copyright (2011) with permission from Elsevier.
M. Tobiszewski, J. Namie? snik / Environmental Pollution 162 (2012) 110e119
increasing PM size, which is explained by the authors with aggre-
gation of particles. The FLA/(FLA þ PYR) ratio was nearly 0.5 in all
fractions, an indication of fuel combustion, while the ANT/
(ANT þ PHE) ratio indicated a fossil fuel contribution, with the
coarse fraction showing lower values. The above applications of
PAH diagnostic ratios confirm that PAHs are emitted with fine
particles and then transferred to coarse fractions by the volatilisa-
tion and condensation or resuspension of particles. The BaA/
(BaA þ CHR) and IcdP/(IcdP þ BghiP) ratios suggested the domi-
nance of diesel over petrol combustion. The authors note that PAH
diagnostic ratios should be used with caution in a closed system
like a roadway tunnel, as there is no sunlight; dispersion, volatili-
sation and sorption are also different, which may influence the
The BaP/(BaP þ BeP) ratio was closer to zero in coarse particles
in the study of Bi et al. (2005), which confirmed the emission of
PAHs with fine particles and their aggregations. In contrast to the
results obtained by Oliveira et al. (2011), other diagnostic ratios
were relatively constant for different sizes of PM. Similarly, the
diagnostic ratios values obtained by PAH determination on PM2.5
and PM2.5e10did not show any significant difference (Akyüz and
Çabuk, 2008), showing coal burning to be the dominant origin in
Zonguldak, Turkey. The diagnostic ratios may change during the
resuspension of street dusts, these changes being greater at higher
wind speeds (Martuzevicius et al., 2011).
Diagnostic ratios can change with the particle size of urban
aerosols (Kavouras and Stephanou, 2002). The SCOMB/SPAHs ratio
increased from 0.3 for 7.2 mm particles to 0.7 for 0.5 mm particles,
while the FLA/(FLA þ PYR) ratio was 0.4 for coarse particles and
0.55 for fine ones. Similar patterns were observed for wood-fire
emitted particles as FLA/(FLA þ PYR) was slightly higher (0.6) in
PM2.5than in PM2.5?10(0.56).
3.4. Seasonal differences
There is ample evidence available to back up the statement that
PAH emission rates and profiles change with the seasons. In the UK
42% of B[a]P and 66% of BghiP total emissions are from seasonal
sources; on the other hand, only 12% of PYR and 7% of FLA are
emitted from seasonal sources (Prevedouros et al., 2004). At the
same time, atmospheric conditions change seasonally, ambient
temperature and insolation being of the greatest importance.
The seasonal changes of diagnostic ratios in China (Guangzhou)
involve lower ANT/(ANT þ PHE) and BaA/(BaA þ CHR) values in
winter months (Yang et al., 2010a). The authors explain these lower
ratios in winter by the strong influence of external sources and
ageing of air masses. Winter FLA/(FLA þ PYR) and IcdP/
(IcdP þ BghiP) ratios were higher than in summer, which was put
down to increased coal and wood burning. On the other hand,
another study showed that the FLA/(FLA þ PYR) ratio was higher in
the non-heating season, while at the same time IcdP/(IcdP þ BghiP)
was lower (Ma et al., 2010).
Ladji et al. (2007) showed that in Algeria winter FLA/
(FLA þ PYR), BaA/(BaA þ CHR) and BaP/(BaP þ BeP) ratios were
much higher than their summer equivalents. The lower summer
values of the latter ratio are explained by the enhanced photo-
degradation of BaP, the authors concluding that the changes in the
first two ratios are due to the dominance of biomass burning in
summer and vehicle emissions in winter. Another study of these
authors (Ladji et al., 2009) showed that ANT/(ANT þ PHE), BaP/
(BaP þ BeP) and IcdP/(IcdP þ BghiP) were lower during the
summer, the first two indicating photochemical decay during the
In contrast to the above-mentioned investigations of seasonal
changes in diagnostic ratios, where sampling points were located
close to potential sources, Dvorska et al. (2011) investigated
seasonal changes of diagnostic ratios in a remote area, taking
atmospheric background PAHs (particles þ gaseous phase) into
consideration. An interesting RET/(RET þ CHR) ratio was presented,
showing that wood burning is dominant in summer months. In the
winter BaA/(BaA þ CHR) and IcdP/(IcdP þ BghiP) are higher, which
was explained by the possible influence of biomass and coal
combustion.Thoughvery low during
(ANT þ PHE) ratio is slightly lower during summer, whereas FLA/
(FLA þ PYR) is higher in the summer months. On the other hand,
the lower summer values of ANT/(ANT þ PHE) and BaA/
(BaA þ CHR) and the higher FLA/(FLA þ PYR) values, apart from
being influenced by seasonal sources, could suggest seasonal
changes in diagnostic ratios occurring as a result of photo-
degradation. This is in agreement with the data presented in
section 3.1 e ANT, BaA and PYR photodegrade faster than their
isomers. Based on long term study, Katsoyiannis et al. (2011) state
thatthe most seasonal ratio isANT/(ANT þ PHE), with higher values
during winter (see Fig. 2). The authors discuss two potential
explanations e higher activity of coal and wood burning during
winter or higher ANT loss from atmosphere and higher volatilisa-
tion of PHE from soil in the summer. They recommend application
of diagnostic ratios for strong, well characterised emission sources
and the samples collected close to the source.
the year, the ANT/
3.5. Pine needles
Atmospheric PAHs can be determined in the wax layer of pine
needles. Because of their ability to accumulate hydrophobic
compounds, pine needles are sometimes treated as passive
dosimeters (Piccardo et al., 2005). Air-octanol partition coefficients
(logKOA) are used to simulate the uptake of organic compounds by
the wax layer. PAHs present in the gas phase are readily taken up by
pine needles; particle-bound PAHs tend to be deposited on soils
(Wang et al., 2009a).
Ratola et al. (2010) calculated ANT/(ANT þ PHE) and FLA/
(FLA þ PYR) ratios and indicated influence of petrogenic sources at
some sites. The ANT and PHE ratio were suspected of having been
changed by the fast photodegradation of ANT, which could point to
the contribution of distant sources. PAHs sorbed on needle surfaces
undergo volatilisation, with rates well correlated with molar
masses, and photodegradation at faster rates than volatilisation.
The half-lives for the complete (photodegradation þ volatilisation)
disappearance from pine needles are 22.4 and 34.5 h for ANT and
PHE, 21.5 and 21.9 h for FLA and PYR, 20.6 and 27 h for BaA and CHR,
and 41.3 and 44.1 h for IcdP and BghiP. Interestingly, BaP with
a half-life of 33.5 h is not the most photodegraded among 252 g
PAHs in pine needles, as the half-life of BkF is 28.3 h (Wang et al.,
2005). These data imply that particularly the ANT/(ANT þ PHE)
and BaA/(BaA þCHR) ratios can be changed by photodegradation in
pine needles. Moreover, washing the needles with water affected
PAH concentrations: the removal of LMW PAHs was explained by
their higher solubilities in water (Sun et al., 2010).
Ratola et al. (2011) obtained very low ANT/(ANT þ PHE) values
that could have resulted from the faster decay of ANT. The FLA/
(FLA þ PYR) ratio indicated a mixed pyrogenic and petrogenic
origin of PAHs in pine needles along the River Ebro. On the basis of
SCOMB/SPAHs and three-ring PAH diagnostic ratios, it was shown
that the influence of combustion processes and photochemical PAH
degradation was stronger at Mexican sites than at Korean and
American ones (Hwang et al., 2003). The analysis of FLA/
(FLA þ PYR) and SCOMB/SPAHs by Sun et al. (2010) categorized
pine needle samples into three groups. Samples from a remote area
had high values of the former ratio but low values of the latter,
which suggests the weak influence of biomass burning; the second
M. Tobiszewski, J. Namie? snik / Environmental Pollution 162 (2012) 110e119
group included samples affected by mainly coal combustion with
FLA/(FLA þ PYR) values between 0.35 and 0.6 and high SCOMB/
SPAHs; the third group displayed low FLA/(FLA þ PYR) values,
industry. Spatial analysis of diagnostic ratios in pine needles in
Cologne showed that most of the area is affected by traffic emis-
sions. Locations impacted by biomass burning were located on the
basis of IcdP þ BghiP and BaP þ BghiP ratios; BaP concentrations
were higher in the area of a petrochemical complex (Lehndorff and
In the same way as pine needles, holm oak (Quercus ilex) leaves
were used as an airborne PAH monitoring tool (De Nicola et al.,
2011). In this study FLA/(FLA þ PYR) and IcdP/(IcdP þ BghiP)
ratios discriminated better between emission sources than ANT/
(ANT þ PHE) and BaA/(BaA þ CHR). The diagnostic ratios involving
ANT and BaA, PAHs easily photodegraded in pine needles, also
failed in holm oak leaves. The FLA/(FLA þ PYR) and IcdP/
(IcdP þ BghiP) ratios indicated the dominance of emissions from
vehicle exhausts in urban areas, while emissions in remote areas
were due mainly to wood and grass burning.
PAHs present in aquatic environment undergo photolysis
(Jacobs et al., 2008), which may alter the values of diagnostic
ratios. Petroleum and combustion-related sources of PAH emis-
sion were identified on the basis of FLA/(PYR þ FLA) and ANT/
(ANT þ PHE) analysis in the aqueous and suspended particulate
matter (SPM) phases of water samples collected in the Yellow
River Delta (Wang et al., 2009b). Similar studies in the Pearl River
Delta revealed mixed petrogenic and pyrogenic sources of water-
and SPM-bound PAHs (Wang et al., 2008). Finding that the BaP/
(BaP þ BeP) ratio was similar to the one in atmospheric particles,
those authors concluded that atmospheric deposition of partic-
ulate matter contributed to PAH water pollution. High concen-
trations of perylene suggested the occurrence of a diagenetic
The study of Elelenwo Creek water in Nigeria did not clearly
distinguish PAH sources: BaA/(BaA þ CHR), ANT/(ANT þ PHE) and
IcdP/(IcdP þ BghiP) indicated combustion as a sourceof waterborne
PAHs, while FLA/(PYR þ FLA) indicated both petroleum combustion
and coal/biomass burning as sources (Opuene et al., 2009).
Tobiszewski et al. (2010) investigated the impact of effluents from
a petrochemical wastewater treatment plant and vehicle emissions
on a local water stream. On the basis of the FLA/(PYR þ FLA) ratio,
supported by the results of multivariate statistical analysis, they
identified sampling points affected by fuel combustion processes,
unburnt petroleum products and biomass burning. Riccardi et al.
(2008) investigated the influence of accidental fuel leaks from
a tank on the groundwater system. The values of ANT/(ANT þ PHE)
and FLA/(PYR þ FLA) suggested that PAHs present in groundwater
originated from fuel leaks, but the pyrolytic origin of PAHs in some
samples was also noted.
Wang et al. (2010a) determined PAHs in precipitation samples
collected at the summit of Taishan Mountain in China. On the basis
of an analysis of PHE/(PHE þ ANT), FLA/(FLA þ PYR) and BaA/
(BaA þ CHR) ratios, the authors state that PAHs in precipitation
originate mainly from coal combustion. However, the application of
diagnostic ratios to precipitation water may be risky: for example,
the LMW/HMW ratio may be much higher when measured for
water (fog, cloud) than for corresponding PM2.5and particulate
matter samples (Li et al., 2010). Lighter PAHs are more water
soluble, so they may have been enriched in atmospheric water
compared to particulates.
Analysis of stormwater flowing into the Anacostia River in the
eastern U.S.A. indicated that combustion-related PAHs contributed
more to stormwater PAH contamination. Stormwater had a low
SLMW/SHMW ratio and a high SCOMB/SPAH ratio, which is
characteristic of combustion sources. High BbF/BkF and BaA/CHR
ratios indicate the dominance of vehicle traffic over coal burning as
sources (Hwang and Foster, 2006).
Petrogenic PAHs are usually emitted directly to a water body,
from where they are deposited to the sediments, whereas pyro-
genic PAHs are first emitted into the air; only then do theyenter the
water and ultimately the sediments. PAH accumulation in sedi-
ments is determined by the sediment composition (Ghosh and
Hawthorne, 2010), black carbon content, organic content or grain
Fig. 2. Seasonal variations of ANT/(ANT þ PHE) ratio in a) London b) Glasgow. Reprinted from Katsoyiannis et al. (2011). Copyright (2011) American Chemical Society.
M. Tobiszewski, J. Namie? snik / Environmental Pollution 162 (2012) 110e119
size (Tsapakis et al., 2003). The study of Ghosh and Hawthorne
(2010) shows that the partition coefficients of PAHs between
water and sand, coal/coke, wood and pitch are similar for the
isomers in the ANT/(ANT þ PHE), FLA/(FLA þ PYR), BaA/
(BaA þ CHR) and IcdP/(IcdP þ BghiP) ratios. PAHs sorbed on sedi-
ments are considered to be stabilized by physicochemical associa-
tion with the sediment matrix: they undergo practically no further
changes (Page et al., 1999). On the other hand, PAHs are formed
during diagenetic processes, i.e. the formation of sediments from
organic material (with perylene as the marker compound for
diagenesis) (Ricking and Schulz, 2002). In remote areas the main
source of PAHs in sediments is atmospheric deposition followed by
sedimentation (Tsapakis et al., 2003); the diagnostic ratios are
therefore similar to those reflecting biomass burning, particle
ageing and atmospheric PAH background ratios.
Fang et al. (2003) compared several diagnostic ratios for
assessing the pyrolytic and petrogenic origins of PAHs in harbour
sediments. The FLA/(FLA þ PYR) ratio was found to be a poor
indicator of pyrolytic and petrogenic activities, whereas BaA/
(BaA þ CHR) was a good indicator of pyrolytic pollution emission
sources. The usefulness of PAH diagnostic ratios for source identi-
fication in southwest Taiwan sediments was also assessed on the
basis of the correlations of each ratio with the sum of petrogenic or
pyrolytic PAHs (Jiang et al., 2009). The ANT/(ANT þ PHE) ratio was
useful for identifying petrogenic sources, whereas FLA/(FLA þ PYR),
BaA/(BaA þ CHR) and IcdP/(IcdP þ BghiP) were better for identi-
fying pyrolytic sources.
PAH diagnostic ratios were applied to assess the extent of oil
spills. The results of FLA/(FLA þ PYR), ANT/(ANT þ PHE), BaA/
(BaA þ CHR) analysis indicated the pyrogenic origin of PAHs on the
Spanish northern coastal shelf (Viñas et al., 2010). The results show
no evidence that the sediments were affected by the Prestige oil
spill in 2001. The identification of pollution sources in thevicinityof
a Brazilian petroleum terminal indicated that the area is affected
mainly by combustion. Mixed emission sources were identified in
close proximity to the terminal (da Silva and Bicego, 2010). Simi-
larly, using PAH molecular ratios, McCready et al. (2000) identified
an area in Sydney Harbour with sediments affected by the petro-
leum industry. Diagnostic ratios were used to identify areas con-
taining PAHs in Lake Maryut (Alexandria, Egypt), where sediments
were affected bycombustion processes and the petroleum industry
(Barakat et al., 2010).
Guo et al. (2010) identified coal or biomass burning as the main
pollution sources of sediment PAHs collected from lakes in western
China. Fang et al. (2007) identified used motor oil dumping and
deposition of combustion-related PAHs as the main sources of
sediment contamination in the Kaoping River in Taiwan. Sediment
PAHs were of pyrogenic origin in Barnegat Bay-Little Egg Harbour
Estuary in New Jersey (Vane et al., 2008), the Adriatic Sea (Magi
et al., 2002) and the Huangpu River in China (Liu et al., 2009).
The pyrolytic origin of PAHs in surface sediments in the Pearl River
Delta was in accordance with atmospheric PAHs in the region,
which originated from combustion (Wang et al., 2010c). Wagener
et al. (2010) identified biomass burning and petroleum combus-
tion activities as the main sources of PAHs in tropical bay sedi-
ments. These authors, however, question the sole use of diagnostic
ratios for source identification in tropical areas, owing to the rapid
weathering of petrogenic hydrocarbons there. Rogowska et al.
(2010) found pyrogenic PAHs in the sediments near a ship wreck,
suggesting that these PAHs originated from a fire that took place
before the ship sank.
PAHs originating from asphalt pavements shift the ratios
towards pyrolytic regions (Arens and Depree, 2010). The PAH
content in coal tar is extremely high, as much as 10%, so even
minimal contamination of sediments with pavement material may
lead to a significant input of PAHs to the aquatic environment,
especially in urban areas (Yang et al., 2010b).
5.1. Sediment cores
Analysis of PAHs in sediment cores and calculation of diagnostic
ratios may supply information on the historical trends of the
activities of PAH pollution sources. Based on the SMePHE/PHEratio,
the input of PAHs to Swedish sediment cores was investigated from
1600 to the present. There was a decrease in the ratios, suggesting
a shift towards higher temperature combustion, i.e. coal burning
rather than wood burning (Elmquist et al., 2007). Diagnostic ratios
calculated for PAHs determined in sediment cores from Central
Park Lake in New York City gave information about pollution inputs
from the late 1800s to the year 2000 (Yan et al., 2005). An increase
in total PAH concentrations was noted around 1900, together with
a decrease in the RET/(RET þ CHR) and FLA/(FLA þ PYR) ratios,
suggesting a change from softwood burning to other sources of
energy. The FLA/(FLA þ PYR) ratio decreased throughout the 20th
century, indicating a shift from coal/biomass burning to petroleum
product combustion. Kuo et al. (2011) investigated the RET/
(RET þ CHR) ratio at three locations in Puget Sound from 1775 to
2000. Two of the locations were influenced by wood burning
during that period, whereas at the third there was a change from
wood burning to petroleum combustion.
Diagnostic ratios were calculated for PAHs determined in
mussels inhabiting bottom sediments. The advantage of monitoring
PAHs in mussel tissue over sediments is that the mussel concen-
tration represents a time-weighted average and the bioavailable
form of PAHs (Flemming et al., 2008). The PAH profiles of sediment
and mussel samples are often similar (Guinan et al., 2001). The
diagnostic ratios calculated for PAHs determined in mussels were
used to assess the extentof oil spills. Mussels from areas affected by
the Prestige oil spill had much the same FLA/(FLA þ PYR) ratio (0.18)
as the ratio of these PAHs in the oil itself (0.22). Sampling locations
unaffected by the oil spill were easily identified, as the ratio was
much higher (0.49) (Soriano et al., 2006). Six diagnostic ratios were
used to assess oil pollution in Guanabara Bay. Although the results
were not definitive, most of the sampling sites were categorized as
affected by oil contamination, even at locations far from known oil
pollution sources (Francioni et al., 2007). Oil was also identified as
a PAH source affecting mussels inhabiting coastal waters near
Ushuaia (Argentina). The high concentrations of lighter PAHs
indicated that the mussels were exposed to fresh petroleum
hydrocarbons (Amin et al., 2011). Four diagnostic ratios applied to
mussel samples collected at Mundau Lagoon (Brazil) showed the
PAH source to be pyrogenic, with a stronger contribution during
one of three sampling campaigns (Maioli et al., 2010).
Although PAH diagnostic ratios are frequently applied to soil
samples, little is known about the stability of these ratios with
regard to soil PAHs. The main source of PAHs in soils is atmospheric
deposition (Mostert et al., 2010), diagnostic ratios values may
depend on soil sampling site altitude (Brändli et al., 2008). PAHs
mayundergodesorption: FLA and PYR are desorbed at similar rates,
but PHE is desorbed faster than ANT (Enell et al., 2005). PAHs
present in soil can be degraded by native bacteria and fungi (Zhang
et al., 2006), resulting in a (possibly selective) decrease of
concentration over time, with rates depending on soil type, organic
carbon and nutrient content, humidity and aeration (Sabaté et al.,
M. Tobiszewski, J. Namie? snik / Environmental Pollution 162 (2012) 110e119
2006; Zhang et al., 2006). The results of microbial PAH degradation
studies indicate that PHE may be degraded faster than ANT, and FLA
faster than PYR (Sabaté et al., 2006). PAHs (especially NP and PHE)
are also considered to be formed in soils by biogenic processes
(Cabrerizo et al., 2011).
Mutsazawa et al. (2001) investigated the photodegradation of
PAHs emitted with diesel particles deposited on soils and found
that FLA and PYR were rather stable, but that PYR degraded faster
on most of the model soils. Under natural conditions, the photo-
degradation of PAHs bound to diesel particles deposited on soils is
expected to be very slow.
The application of FLA/(PYR þ FLA) and BaA/(BaA þ Chry) ratios
to Indian agricultural soils showed that these PAHs were emitted
during grass, wood or coal burning. A sample taken in an urban
area, at a location temporally flooded by an oil-polluted river,
showed a PAH profile characteristic of liquid fuel contamination
(Agarwal et al., 2009). PAH diagnostic ratios were applied to assess
possible pollution sources of agricultural soils in Poland. The
interpretation of IcdP/(IcdP þ BghiP) and FLA/(FLA þ PYR) ratios
(shown in the Fig. 3) implied that coal, wood and/or grass burning
were the prevailing sources of PAH pollution in the soil
(Maliszewska-Kordybach et al., 2008). This could be explained by
the fact that coal is still the dominant energy source in Poland. An
investigation of river bank soils along the Mosel and Saar in Ger-
many also showed the PAHs to be pyrogenic. The conclusions were
drawn on the basis of five diagnostic ratios supported by principal
component analysis and n-alkane molecular markers (Pies et al.,
The study by Marusenko et al. (2010) conducted in a desert
region in Arizona showed that PAHs in soil samples collected next
to a highway were derived from traffic-related sources: 80% of
samples were categorized as fuel combustion related. PAH levels in
arid areas were lower than in locations where soils are rich in
organic matter. On the basis of FLA/(FLA þ PYR) and ANT/
(ANT þ PHE), another study identified wood and tyre burning
together with the brick making industry as the main sources
contributing to PAHs present in soils in the El Paso area of Texas (De
La Torre-Roche et al., 2009).
Wang et al. (2010b) determined PAH compounds in soils in
Bejing and Tianjin and applied ANT/(PHE þ ANT) and FLA/
(PYR þ FLA) ratios after calibration using the rectification factors
introduced by Zhanget al. (2005). The results showed that the main
sources of soil PAHs in Bejing and Tianjinwere coal, grass and wood
burning. Wang et al. (2007) studied PAHs compounds in Dalian
(China) soils. Based on ANT/(ANT þ PHE) and FLA/(FLA þ PYR)
ratios, the authors concluded that PAHs determined in soil samples
collected at traffic sites were derived from petroleum combustion.
PAHs detected at rural and suburban sampling locations were
emitted during wood and coal burning. Similarly, the analysis of
surface soil samples collected in the vicinity of Shanghai revealed
the pyrogenic origin of PAHs. The FLA/(FLA þ PYR), ANT/
(ANT þ PHE), BaA/(BaA þ CHR) ratios indicated biomass and coal
burning to be the predominant sources of PAHs, while the IcdP/
(IcdP þ BghiP) ratio was indicative of the contribution of petroleum
combustion sources (Liu et al., 2010).
Plachá et al. (2009) investigated the origin of PAHs in urban,
agricultural and forest soils in the eastern Czech Republic. They
simultaneously applied five diagnostic ratios e ANT/(ANT þ PHE),
BaA/(BaA þ CHR), FLA/(FLA þ PYR), IcdP/(IcdP þ BghiP) and BaP/
BghiP, all of which confirmed the pyrogenic origin of PAHs in the
soils. Bucheli et al. (2004) studied the concentrations of PAH
compounds in various (agricultural, grassland, forest) soils in
Switzerland. The ANT/(ANT þ PHE), BaP/BghiP and SCOMB/SPAH
ratios were the smallest in remote areas, indicating the minimal
influence of traffic-related sources. One sampling point located in
an urban area, located close to the emission source, showed “the
clearest” diagnostic ratio pattern, related to traffic emissions. The
authors found a correlation between FLA/(FLA þ PYR) and other
ratios and the carbon black content in forest soil. This was
explained by their origin from local forest fires and wood burning.
The study of Brändli et al. (2008) confirmed pyrogenic origin of
PAHs in Swiss soils. However, the ratio ANT/(ANT þ PHE) indicated
petrogenic origin of PAHs, which is improbable result. The authors
question applicability of this ratio, as well as reliability of BaP/BghiP
ratio, which indicated traffic origin of soil PAHs, which is also
PAH diagnostic ratios confirm atmospheric deposition as the
main pathway of soil pollution by PAHs. These ratios from most
studies identify the sources of PAHs in soils as pyrogenic. PAH
diagnostic ratios maybe an efficient supporting tool in studying the
mechanisms of PAH transport to the soil and assessing the range of
influence of particular emission sources on the surrounding area.
7. Sewage sludge
Diagnostic ratios were calculated on the basis of PAH concen-
trations in sewage sludge from Paris sewers (Blanchard et al., 2004)
and wastewater treatment plants in Beijing (Dai et al., 2007). The
application of molecular diagnostic ratios to identify PAH sources in
sewage sludge has been criticized (Katsoyiannis et al., 2007). This is
the case when the treatment of wastewater involves the intensive
sorption, volatilisation and biodegradation of PAHs. The authors
indicate FLA/(FLA þ PYR) ratio as relatively stable throughout the
treatment processes. The second reason is the mixing of waste-
waters originating from an area that could be affected by different
sources. Mansuy-Huault et al. (2009) state that a detailed inter-
pretation of PAH diagnostic ratios applied to samples collected at
a wastewater treatment plant is not possible.
PAH diagnostic ratios should be used with caution, as their
values may change during the environmental fate of these
compounds. They should therefore be used only after the applica-
tion of correction factors partially taking account of changes due to
phase transport and degradation. The correction factors are only an
estimate, however. If the investigated medium is a multiphase one,
the PAHs used for calculating diagnostic ratios should be deter-
mined in the total sample (i.e. gaseous þ particles for air samples,
water þ suspension for water samples).
Fig. 3. Diagnostic ratios applied for identification of PAH pollution sources in Polish
soils. Reprinted from Maliszewska-Kordybach et al. (2008). Copyright (2008) with
permission from Elsevier.
M. Tobiszewski, J. Namie? snik / Environmental Pollution 162 (2012) 110e119
It is useful to estimate PAH emission profiles for suspected
emission sources present in the area investigated. To some extent
this prevents misinterpretations due to wrong assumptions of
diagnostic ratios for particular sources. More than one diagnostic
ratio should be used to confirm the results. However, the fact that
contradictory results are obtained with different diagnostic ratios
does not mean that the results are wrong; light PAHs are emitted
from different sources than heavy ones. To confirm the results
obtained with PAH diagnostic ratios they could be supported by
other molecular markers.
The FLA/(FLA þ PYR) and IcdP/(IcdP þ BghiP) ratios are more
conservative than ANT/(ANT þ PHE) and BaA/(BaA þ CHR), which
(ANT þ PHE) ratio is sensitive to environmental changes and its
values for the identification of particular processes lie within
a narrow range, which makes it hard to use.
Marek Tobiszewski expresses his gratitude for the financial
(POKL.04.01.01-00-368/09) and for financial support in the form of
a grant awarded by the Polish Ministry of Science and Higher
Education (NN 523 562838).
The authors express their gratitude for the financial support
from the Foundation for Polish Science, MISTRZ Programme.
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