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Environmental Pollution 151 (2008) 477e485

www.elsevier.com/locate/envpol

The removal of Polycyclic Aromatic Hydrocarbons in the wastewater

treatment process: Experimental calculations and model predictions
E. Manoli*, C. Samara
Environmental Pollution Control Laboratory, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Greece
Received 31 October 2006; received in revised form 22 March 2007; accepted 15 April 2007

Experimental calculations and model predictions elucidated the removal of PAHs during the wastewater treatment.
Abstract
The removal of PAHs during the wastewater treatment process was examined in an activated sludge mode conventional facility. Concentrations reported are taken from an earlier measuring campaign. Removals of PAHs ranged between 28 and 67% in the primary, <1e61% in the
secondary stage, and 37e89% in the whole process. Significant positive relationships were observed for removal efficiencies and the log Kow of
PAHs in the primary and the log KH of PAHs in the secondary stage. Experimental removals were compared to those obtained from the FATE
model. In the primary stage, predicted removals were lower than those experimentally calculated while in the secondary stage were higher. Predicted removals were apportioned mainly to sorption with negligible contribution from volatilization and biodegradation. Remarkable consistency between experimental and modeled removal efficiencies (20e20%) was observed for almost all PAHs in the whole treatment process.
2007 Elsevier Ltd. All rights reserved.
Keywords: Activated sludge process; FATE model; Polycyclic Aromatic Hydrocarbons; Removal efficiency; Wastewater treatment

1. Introduction
Due to the increased public concern over possible exposure
to pollutants in air and water, increased attention has been given
to the fate of pollutants introduced to wastewater treatment
plants. If these pollutants are not completely mineralized within
a treatment system then it is possible for some fraction of the
pollutant involved to be released into the environment as part
of the final effluent discharge or as a component of the sludges
produced or, indeed, volatilized directly to the atmosphere.
The effective operation of wastewater treatment plants
plays an important role in minimizing the release of organic
pollutants into the aquatic environment. However, nearly all
systems now in operation have been designed from treatability
data that focus on the removal from the wastewater fed to the
system of a few non-specific analytical parameters, such as the

* Corresponding author. Tel.: 30 2310 997 925; fax: 30 2310 997 747.
E-mail address: emanoli@chem.auth.gr (E. Manoli).
0269-7491/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2007.04.009

five-day biochemical oxygen demand (BOD), the chemical

oxygen demand (COD), and suspended solids (SS) (Blackburn, 1987). These parameters are useful in defining the optimization of wastewater treatment plants for the pollutants;
however present trends indicate that effluent standards will
soon be based not only on such parameters but on individual
toxic priority pollutants as well. In fact, such standards have
already been established for some of these pollutants (Byrns,
2001; European Union Draft Directive on sewage sludge,
2000; European Commission, 2001).
The occurrence and fate of pollutants during the wastewater
treatment process has been the subject of several studies
(Petrasek et al., 1983; Rogers, 1996; Pham and Proulx, 1997;
Alcock et al., 1999; Blanchard et al., 2004; Katsoyiannis and
Samara, 2004). However, there is much inconsistency among
reported data. Activated sludge is the most widely used biological wastewater treatment process. Typically a conventional
activated sludge treatment facility contains a primary clarifier
system, an aeration system and a secondary clarifier (Fig. 1).
Some investigators have considered the fate of pollutants on

E. Manoli, C. Samara / Environmental Pollution 151 (2008) 477e485

478

C1

Rvol

Air

Q
Sin

Primary
clarifier

Aeration
Basin
Rbio T

Xa
waste
sludge
Qp

Xp

So

Rsorp1

Secondary
Clarifier

Qe
S

V
waste
sludge

Air
G

Qw

Xv

Rsorp2

Primary Clarifier

So= (QSin) / [Q + QP XP(4.1 x 10-5Kow0.35)]

Aeration Basin and

secondary clarifier

S = (QoSo) / [Qo+ GH/RT + Qw Xv (3.06 x 10-6) Kow0.67 + k1XaV]

Fig. 1. Organic sub model material flow diagram and equations. Q, Qo, Qe flow rate to plant, aeration basin and exiting the plant (m3 d1), Sin, So, S individual
organic concentration entering plant, in and exciting the primary clarifier and in the aeration basin/secondary clarifier and exciting the plant (g m3), Qp,
Qw sludge flow rate in primary and secondary clarifier, respectively (m3 d1), Xp, Xv concentration of solids in primary and secondary sludge (g m3),
Xa acclimated active biomass (gvss m3), assumed to be 0.64 of the mixed liquor suspended solids concentration, V aeration basins volume (m3), G gas
volumetric flow rate (m3 d1), Kow octanol-water partition coefficient, K sorption partition coefficient which is a function of the chemicals Kow, k1 apparent
1
3
1
5
first-order biodegradation rate constant (m3 g1
m3 atm K1 mole1),
vss d ), H Henrys constant (atm m mole ), R universal gas constant (8.206 x 10
T aeration basin temperature ( K), Rsorp1, Rsorp2 rate of chemical removal due to primary and secondary sorption respectively (g d1), Rbio, Rvol rate of
chemical removal due to biodegradation and volatilization, respectively (g d1).

passing through the biological reaction stage only (aeration basin and secondary clarifier) (Barton, 1987; Blackburn, 1987;
Namkung and Rittmann, 1987), whilst others (Cowan et al.,
1993; Clark et al., 1995) include in their research the primary
clarifier also, in order to estimate overall removal of certain pollutants and removal due to a specific removal mechanism.
Mathematical models have also been proposed to quantify the
distribution and fate of pollutants in biological treatment plants.
These models consider the major abiotic and biotic processes
which influence the intermediate distribution and eventual
fate of organic compounds (US EPA, 1990; Harrington et al.,
1993; Byrns, 2001). However, further careful modeling and experimental work is needed in determining the most likely fate
mechanisms in treatment systems.
A number of pollutants have been included in priority pollutants lists compiled by the Environmental Protection
Agencies of the USA and Europe with the objective of reducing
the release of these compounds to the environment. Sixteen
Polycyclic Aromatic Hydrocarbons (PAHs) are included in
these lists (Keith and Telliard, 1979; Bedding et al., 1983;
Water Resources Act, 1991).
PAHs are widespread environmental pollutants formed during the incomplete combustion of organic materials, especially
coal, oil, petrol, natural gas and wood. Within the urban environment, PAHs are emitted from vehicles, domestic heaters,
fossil fuelled power plants and industries as a result of the
fuel used or during the processing of raw materials (Wild and
Jones, 1995). PAHs may enter a treatment plant either as part
of an industrial discharge, or as a component of domestic effluent drainage into the sewerage system and urban runoff,

including fossil fuel spillages and atmospheric deposition

(Manoli and Samara, 1999a; Stevens et al., 2003; Blanchard
et al., 2004). Due to their lipophilic and hydrophobic nature,
PAHs enter the wastewater treatment systems notably adsorbed
onto particulate organic matter, and because of this affinity for
particulates, they are effectively removed during the primary
and secondary sedimentation of wastewaters to the sludge
stream (Beck et al., 1996; Busetti et al., 2006). Furthermore,
mass balance investigations have showed substantial losses
(>40%) for the lower molecular weight PAHs during biological
treatment, thus suggesting removal due to air stripping and/or
biodegradation (Manoli and Samara, 1999b). Due to the carcinogenicity and/or mutagenicity of certain members of the PAH
class (IARC, 1987e1991), their presence in treated wastewater
and sludge has been subjected to legislative control (US EPA,
1993; European Union Draft Directive on sewage sludge,
2000; European Commission, 2001; Stevens et al., 2003;
Busetti et al., 2006).
The aim of the present study was to improve knowledge concerning the removal of PAHs during the wastewater treatment
process. For this purpose, PAHs were determined in wastewater
samples collected from various stages of a conventional activated sludge treatment facility. Removal efficiencies, calculated
from actual field data of a previous measuring campaign (Manoli and Samara, 1999b), were investigated in comparison to results obtained from the FATE (Fate and Treatability Estimator)
prediction model. FATE is a user friendly computerized model
which evaluates the fate of various inorganic and organic pollutants (including the 16 EPA PAHs) discharged to conventional
activated sludge Publicly Owned Treatment Works (POTWs).

E. Manoli, C. Samara / Environmental Pollution 151 (2008) 477e485

479

Its development had been supported by the Industrial Technology Division of the US Environmental Protection Agency (US
EPA, 1990). US EPAs guidelines for use of mathematical
models for regulatory assessment and decision making (US
EPA, 1989) were followed wherever applicable during the
development of FATE. The process of calibration/validation of
the FATE model include sensitivity analysis (US EPA, 1990).
Analytical data and plant parameters for calibration and validation were obtained from US EPA (1982) and concerned 50
POTWs. The Sewerage Authority of Thessaloniki, northern
Greece, had expressed a keen interest to use the FATE model
to evaluate the fate and treatability of the pollutants discharged
to the Sewage Treatment Plant (STP) of the city. This was the
main reason for selection of FATE in our study.

where, CIN and COUT are the daily amounts of individual PAH species entering
and exiting each treatment stage, respectively. Potential temporal mismatch of
influent and effluent samples was eliminated by use of 24-h composite samples
as described in the sampling section.

2. Materials and methods

2.4. The FATE model

2.1. Sampling

FATE has the capability to estimate the treatability of both inorganic and
organic compounds discharged to a POTW. It contains two separate models
which estimate removal of organics and inorganics (US EPA, 1990). The
organic sub-model, applied in this study, uses a steady-state mass balance
approach around the primary clarifier (primary stage) and the aeration basin
and secondary clarifier (secondary stage), considering the major removal
mechanisms that are: sorption in the primary stage and sorption, volatilization
(by air stripping) and biodegradation in the secondary stage.
For an individual organic compound, FATE first calculates a steady-state
concentration in the primary clarifier that is then used as the influent concentration to the aeration basin and secondary clarifier system, where a second
steady-state concentration is calculated. Chlorination is not accounted for in
the model. The mass removal efficiencies due to sorption in the primary and
secondary clarifiers, and due to volatilization and biodegradation in the aeration basin are then calculated as the percent removal by each of these particular mechanisms. Finally, FATE calculates an overall percent removal (US
EPA, 1990). Fig. 1 depicts the organic sub-model material flow diagram, equations and symbols used.
According to FATE (US EPA, 1990), at steady-state (dS=dt 0), the organic pollutant concentration (mg L1) exiting the primary clarifier is:

The study was conducted in the STP of Thessaloniki, northern Greece operating in the conventional activated sludge mode. During the study, the STP
was receiving a dry weather flow of approximately 40 000 m3 d1, consisting
mainly of the domestic effluents of the city, part of the local urban runoff and
a minor contribution (<5%) of industrial discharge. The treated wastewaters
are discharged into the sea not far away from a shell cultivation area.
The major components of the Thessaloniki STP in the study period were:
screens, aerated sand and grease removal units, primary sedimentation tank
(hydraulic load w40 000 m3 d1, retention time 3 h, SS removal 75%), aeration tank with surface aerators (retention time 3 h, mixed liquor suspended
solids concentration w3.5 g L1) secondary sedimentation tank (retention
time 6 h, COD w55 mg L1, BOD w20 mg L1) and finally, a chlorination
unit. The total removal efficiency of the whole treatment is higher than 96,
95 and 92% for SS, BOD and COD respectively. Peak flow rates of wastewater
at the entrance of the treatment plant are reduced by means of a barrier gate
thus keeping the influent flow rate relatively constant.
Wastewater samples were collected from four sampling points along the
treatment process: the influent (E-1), the effluent of the primary sedimentation
tank (E-2), the effluent of the secondary sedimentation tank (E-3), and the final
effluent after chlorination (E-4). Twenty-four hours composite samples were
obtained from each point by combining 4 grab samples collected every 6 h.
Sampling was carried out over 5 consecutive days, excluding Saturdays and
Sundays. Four 5 d sampling campaigns were conducted in two warm (September, October; Temperature range: 15e28  C) and two cold (March, December
Temperature range: 3e14  C) time periods.
Samples were collected in solvent rinsed dark glass bottles with Teflon
caps containing 65 mL of 37% formaldehyde (Bedding et al., 1988). Immediately after collection, wastewater samples were transported to the laboratory in
a portable cooler and were extracted within 48 h for PAH analysis.

2.2. Extraction and analysis

Details about the extraction, clean-up, recovery tests and chromatographic
determination of PAHs are given elsewhere (Manoli and Samara, 1996). Briefly,
total PAHs (sorbed and dissolved) were recovered from wastewater samples after liquid-liquid extraction with cyclohexane, and were determined by HPLC
coupled with programmable fluorescence detection using a Perking Elmer
Pump LC 250 and a Perkin Elmer LC 240 fluorescence detector. Identification
of individual PAHs was based on the comparison of fluorescence and retention
time data between samples and a standard solution (NIST 1647c) containing
the 16 EPA PAHs: naphthalene (Np), acenaphthylene (Acy), acenaphthene
(Ace), fluorene (F), phenanthrene (Ph), anthracene (An), fluoranthene (Fl),
pyrene (Py), benzo[a]anthracene (B[a]An), chrysene (Chry), benzo[b]fluoranthene (B[b]Fl), benzo[k]fluoranthene (B[k]Fl), benzo[a]pyrene (B[a]Py),
dibenzo[a,h]anthracene (dB[a,h]An, benzo[ghi]perylene (B[ghi]Pe) and

indeno[1,2,3-cd]pyrene (IPy). Acenaphthylene, although included in the standard, is only weakly fluorescent, and thus not determined. Instead, benzo[e]pyrene (B[e]Py) was quantified since it is frequently used as a reference PAH.
Detection limits were in the range of 0.17e30 ng L1 for individual PAH species.

2.3. Experimental removal calculation

The percent removal of PAHs in individual treatment stages and the whole
treatment process were calculated using the general equation:
R%

So

CIN  COUT  100

CIN

QSIN


0:35
Q QP XP 4:1  105 KOW

assuming that Q Qo and Rsorp1 QP XP KP So .

Briefly, the sorption removal efficiency, Rsorp1, used in FATE assumes that
the compound partitions according to a linear relationship between the liquid
and solid phase, and this can be described by an empirical relationship,
3 1
kp 5.9  105 (K0.35
VSS), obtained from an experimental
ow ) (units of m g
study which examined the sorption of organic compounds onto wastewater solids
(Dobbs et al., 1989; US EPA, 1990). The statistical measure, R2, for this relationship was determined to be 0.72. Thus, the efficiency of compound removal
0:35
due to sorption can be written as: Rsorp1 Qp Xpw 0:000059  KOW
So , where
Xpw is the concentration of organic solids present in the primary clarifier
sludge (g VSS m3) and is assumed to be 70% of the total solids concentration,
Xp (US EPA, 1990).
Concerning the secondary treatment in FATE (US EPA, 1990), the organic
pollutant concentration (mg L1) exiting the secondary clarifier is:
S

Qo So


0:67 k X V
Qo GH=RT Qw Xv 3:06  106 Kow
1 a

assuming steady-state conditions, Qo Qe , Rbio k1 Xa SV, Rvol GHS=RT

and
0:67
Rsorp2 3:06  106 Qw Xv Kow
S:
Again, the sorption removal efficiency, Rsorp2, assumes that the compound
partitions according to a linear relationship between the liquid and the solid
phase and this partitioning can be described by an empirical relationship,

E. Manoli, C. Samara / Environmental Pollution 151 (2008) 477e485

480

3 1
kp 3.6  106 (K0.67
ow ) (units of m g ), obtained experimentally by MatterMuller (1980).
As the FATE model was developed for conventional diffused aeration activated sludge sewage treatment plants, whereas during the survey the Thessaloniki STP used surface aerators, the total gas flow rate in the aeration basin was
approximated from the oxygenation capacity of the surface aerators
(9250 kg O2 h1) assuming that diffusion systems have a mean oxygen transfer
capacity to the wastewater of 7% (Markadonatos, 1990). A value of
300 000 m3 d1 was therefore used for the gas volumetric flow rate G.
A functional condition of FATE is that the minimum concentration for each
compound in the influent to the primary clarifier should be 0.1 mg L1. This
limit was derived from the calibration and validation algorithms of the model,
taking into account the variable method detection limits for individual pollutants (for PAHs typically 1e10 mg L1) at the different laboratories that provided analytical data to EPA (US EPA, 1990). In the present work, detection
limits of PAHs were considerably lowers (0.17e30 ng L1; Manoli and Samara,
1996). However, the application of the model was restricted to those PAHs and
samples, which were found to meet models requirement. For concentration
values measured in E-1 between 0.06 and 0.1 mg L1, a round-off value of
0.1 mg L1 is calculated.
Furthermore, the model was not applied in cases where chromatographic
interferences did not permit calculation of PAH removals in all treatment
stages. Comparisons between experimentally calculated and predicted removals concern the same sampling dates. Table 1 shows the number of samples
used for experimental removal calculation and the number of samples included
in the model application.

3. Results and discussion

3.1. Experimental removals
Details about PAHs concentrations determined in the influent and the effluent of the treatment stages are given elsewhere
(Manoli and Samara, 1999b). Briefly, all 16 EPA PAHs were
found at quantifiable concentrations in the untreated wastewater (E-1), ranging from a low median of 4.0 ng L1 for
dB[a,h]An to a maximum median value of 2800 ng L1 for
Np. The frequency of occurrence in E-1 was 100% for all
PAHs except Ace that was less frequently detected. The frequency of occurrence in the final effluent (E-4) was <50%

for Ace and dB[a,h]An, but all other PAHs were determined
with frequency of 80e100%, suggesting only partial removal
during the treatment process (Manoli and Samara, 1999b).
The determination of B[a]An was not possible in many of
the samples due to chromatographic interferences (Manoli
and Samara, 1999b). Summary data of PAHs concentrations
used for experimental removal calculation are given in Table 1.
The mean removal percentages calculated for each treatment
stage are shown in Fig. 2. In the primary stage, mean removals
ranged between 28% for Np and 67% for B[a]An, with the
5- and 6-ring PAHs exhibiting removals in the range 51e
56%. The experimental removals of PCBs at this treatment
stage of the same STP were found at similar levels (42e62%,
Katsoyiannis and Samara, 2004).
In the secondary treatment (activated sludge bioreactor or
aeration basin and secondary settling tank), mean removals
ranged from <1% for F and dB[a,h]An to 61% for Np with
the 5- and 6-ring PAHs exhibiting removal efficiencies between
<1 and 20%. The removal efficiencies found in the present
study at the secondary stage are in general agreement with
reported values for PAHs (Petrasek et al., 1983; Melcer et al.,
1995), while higher removals (51e75%) have been reported
for PCBs (Katsoyiannis and Samara, 2004).
Chlorination did not appear to significantly affect the removal of PAHs yielding mean removal percentages in general
between <1 and 10% for all PAH compounds. The whole
treatment process (including chlorination), exhibited mean
PAH removals in the range 37% for F to 89% for B[a]An
with the heavier PAHs being between 55% and 75%.
In the primary tank, the removal of hydrophobic organic
compounds, with log Kow, higher than around 4.5, is largely
dominated by sorption on settled sludge and on suspended
matter passing forward to the activated sludge reactor (Pham
and Proulx, 1997; Byrns, 2001). According to Byrns (2001),
compounds with log Kow > 5 are expected to be removed
through sorption on sludge at efficiencies between 60 and

Table 1
Summary data of PAHs concentrations (mg L1) used for experimental removal calculation and for model application in various stages of the treatment process
PAHs

For experimental removal calculation

N

Np
F
Ph
An
Fl
Py
B[a]An
Chry
B[e]Py
B[b]Fl
B[k]Fl
B[a]Py
dB[a,h]An
B[ghi]Pe
IPy
a

20
20
20
20
20
20
20
20
20
20
20
20
20
20
20

For model application

Influent (E-1)

Primary effluent (E-2)

Secondary effluent (E-3)

Chlorination effluent (E-4)

Mean

Median

Mean

Median

Mean

Median

Mean

Median

7.30
0.70
1.70
0.090
0.24
0.47
0.050
0.16
0.36
0.023
0.010
0.022
0.005
0.029
0.015

2.80
0.50
1.00
0.070
0.23
0.22
0.040
0.060
0.22
0.022
0.007
0.020
0.004
0.028
0.014

7.60
0.50
0.57
0.033
0.072
0.12
0.015
0.033
0.10
0.010
0.004
0.010
0.002
0.010
0.006

1.80
0.440
0.590
0.034
0.073
0.11
0.012
0.029
0.090
0.009
0.003
0.009
0.001
0.009
0.006

5.70
0.50
0.18
0.008
0.29
0.70
0.005
0.014
0.060
0.006
0.003
0.006
0.002
0.009
0.006

0.33
0.50
0.17
0.006
0.021
0.060
0.004
0.016
0.060
0.005
0.002
0.004
0.001
0.008
0.005

5.00
0.23
0.20
0.007
0.029
0.060
0.005
0.015
0.060
0.007
0.003
0.005
0.002
0.008
0.005

0.29
0.044
0.19
0.004
0.030
0.050
0.005
0.015
0.050
0.006
0.003
0.004
0.001
0.007
0.006

N number of samples included in the model application.

Na

6
2
16
13
16
17
1
11
e
1
e
1
e
2
e

Influent (E-1)
Mean

Median

5.30
1.25
2.05
0.12
0.29
0.51
0.090
0.28

5.80
1.25
1.10
0.08
0.24
0.21
0.090
0.090

0.070

0.070

0.070

0.070

0.070

0.070

E. Manoli, C. Samara / Environmental Pollution 151 (2008) 477e485

481

120
Secondary treatment
Whole treatment process

Primary treatment
Chlorination
100

% Removal

80

60

40

20

hi

IP
y

]P
e

n
A

dB

[g

]P
y

,h
]

[
B

[k
]F
l

[b
]F
l

]P
y

y
B

[e

hr
C

n
B

]A

Py

Fl

n
A

Ph

Fig. 2. Experimental removal percentages of PAHs in the different treatment stages (mean  SD).

3.2. Seasonal variations of removal

Several investigators have found large temporal variations in
PAH removals during primary treatment (US EPA, 1982; Petrasek et al., 1983; Hannah et al., 1986; Melcer et al., 1995). In the
present study, seasonal variations of PAH removals in the different treatment stages were examined by applying the one-way
ANOVA and the non-parametric ManneWhitney U procedures
on seasonally classified data. Both procedures led to similar
results (Table 2) that indicate significant seasonal variation
for some PAHs in the primary stage, which is reduced in the
secondary stage and almost disappear in the whole treatment
process. The highest removal percentages for almost all PAHs
in the primary stage and the whole treatment process were

Removal (%)

(a)

80

y = 6.3646x + 16.243
R2 = 0.597 P < 0.01

60
40
20
0
2

Log Kow

(b)
Removal (%)

65%, while for compounds with log Kow values between 3.6
and 5, lower removals are expected (15e50%) due to this
mechanism. The removal values found in the present study
for PAHs are in good agreement with these predictions.
In the secondary stage, biosorption, biotransformation/biodegradation and volatilization are considered as the most
likely removal processes. Sorption of PAHs to bacterial cells
is complex possibly involving both active surface reactions
and non-specific partitioning phenomena (Stringfellow and
Alvarez-Cohen, 1999). Within the activated sludge stage, the
injection of diffused air may induce transfer to the atmosphere.
This air stripping depends on the compounds Henrys law
constant, KH. Biotransformation may also occur reaching a plateau around a log Kow value of 3e3.5 and then falls rapidly as
sorption to sludge and sludge wastage dominates the removal
at high Kow (Byrns, 2001). Considering the log Kow and the
log KH values of PAHs, both mechanisms are expected to be
important only for the lower weight PAHs. Indeed, these
PAHs exhibited substantial losses in their mass balance calculation (Manoli and Samara, 1999b).
In Fig. 3a, the percent removals of PAHs in the primary
treatment stage have been plotted against the compounds
log Kow values. Although it seems that there is a plateau implying about constant % removal for compounds with
log Kow  5, a linear relationship between primary removal
and log Kow is statistically significant (R2 0.597, P < 0.01).
This relationship suggests that sorption on sludge particles is
a major removal mechanism for the most hydrophobic PAHs
in the primary treatment. Significant linear relationship
(R2 0.898, P < 0.01) was also obtained between secondary
removal and the log KH values of PAHs (Fig. 3b). Given that
losses of PAHs in the secondary treatment were also found to
correlate significantly with log KH (Manoli and Samara,
1999b), this finding reveals that air stripping is important for
the more volatile species.

80
60

y = 10.003x + 26.946
R2 = 0.898 P < 0.01

40
20
0
-3

-2

-1

Log KH
Fig. 3. Percent removal of PAHs in: (a) primary treatment versus the compounds log Kow; and (b) secondary treatment versus the compounds log KH.

E. Manoli, C. Samara / Environmental Pollution 151 (2008) 477e485

482

Table 2
Seasonal variation of the removal of PAHs at various stages of the treatment process

Primary
Secondary
Overall (including chlorination)

An

Ph

Fl

Py

Chry

B[e]Py

B[b]Fl

B[k]Fl

B[a]Py

dB[a,h]An

B[ghi]Pe

IPy


















: significant at P < 0.01. : significant at P < 0.05. : not significant at P < 0.05.

observed during the fourth sampling campaign (cold period),

while the lowest removal percentages were found during the
first campaign (warm period). Since these two campaigns
were associated with the highest and the lowest PAHs concentrations in the primary influent (E-1) (Manoli and Samara,
1999b), some kind of relationship between removal and influent
concentrations might be implied.
3.3. Removal dependence on influent concentration
Table 3 presents the Spearman correlation coefficients between PAH concentration in the influent wastewater (E-1)
and removal percentages during each treatment stage. It can
be seen that for most PAHs, the removal percentages during
primary treatment are significantly correlated with the compounds concentrations in the untreated influent. The same
can also be observed for the combined (primary plus secondary) treatment, as well as for the overall treatment including
chlorination. This relationship should probably be attributed
to the hydrophobic nature of PAHs that are mainly removed
from wastewater through sorption on sludge particles.
Fig. 4 presents the removal efficiencies of individual PAHs
in primary treatment as a function of the compounds concentrations in the influent. A logarithmic relationship, significant
Table 3
Spearman correlation coefficients between PAHs concentrations in the influent
(E-1) and removal percentages in each treatment stage
PAHs

Np
Ace
F
Ph
An
Fl
Py
B[a]An
Chry
B[e]Py
B[b]Fl
B[k]Fl
B[a]Py
dB[a,h]An
B[ghi]Pe
IPy

Primary Secondary Primary and Chlorination Overall

treatment treatment secondary
treatment
treatment
(including
chlorination)

0.848
0.871
0.848
0.756
0.818
0.866
0.756
0.696
0.702
0.792
0.705
0.526

0.627

0.886
0.877
0.952
0.815
0.764

0.786
0.552
0.931
0.886
0.835
0.687

0.713
0.699
0.681
0.603
0.606
0.841
0.616
0.567

0.805
0.693
0.695
0.851
0.722
0.898
0.726
0.768

0.606

Bold italics: correlation coefficients are significant at the 99% confidence level; Normal: correlation coefficients are significant at the 95% confidence level; Blank: correlation coefficients are not significant at the 95%
confidence level.

at the P < 0.01 level for almost all species, was observed, similar to those previously found for several persistent organic
pollutants in the same STP (Katsoyiannis et al., 2006). It
should be mentioned that the FATE model assumes independence of the removal efficiency at any stage from the compounds concentrations in the influent, and this might be
a reason for discrepancy between experimental and predicted
removals.
3.4. Calculated vs. predicted removals
Summary data of PAH concentrations used as inputs in the
FATE model are given in Table 1. Figs. 5, 6a and 7 present the
removals of PAHs for the primary, secondary and the whole
treatment process (without chlorination), respectively, that
were predicted by FATE against the experimental values
obtained from those samples where PAH concentrations met
requirements for model application.
In primary clarification (Fig. 5), for all PAH species, predicted removals (15e70%) were lower and less variable than
the experimental values (28e77%). Lower model underestimations were found for Chry, B[b]Fl, B[a]Py and B[ghi]Pe.
Primary removals underestimated by 40e50% were also observed for other organic pollutants using FATE (Katsoyiannis
et al., 2006). However, in both approaches, removal percentages increased from the lighter to the heavier PAHs suggesting that sorption is the major removal mechanism at this
stage.
In the secondary treatment stage (Fig. 6a), good agreement
between model predictions and experimental values could be
observed only for Np, whereas for all other PAHs, predicted
values (28% for B[ghi]Pe e64% for F) were significantly
higher than those calculated. High removal percentages
(43e96%) have been predicted by Byrns (2001) even without
considering biodegradation of PAHs. It should be noted that
significant model overestimations were also observed for
PCBs and organochlorine pesticides by applying FATE in
the Thessalonikis STP (Katsoyiannis et al., 2006). This
was attributed to the model assumption that the removal efficiency is independent from the compounds concentration in
the influent wastewater, something that was revealed to be
untrue for the low concentration levels, as well as to the possible effect of dissolved organic carbon, parameter not considered in FATE, that favors removal of organic pollutants
in the dissolved phase rather than through sorption on sludge
particles (Katsoyiannis and Samara, 2005).
The FATE predictions for individual removal mechanisms
considered for this stage (Fig. 6b) indicated that PAHs are

E. Manoli, C. Samara / Environmental Pollution 151 (2008) 477e485

90

60
An
R2 = 0,51
P<0.01

30

60

B[ ]Py
2

R = 0,32
P<0.05

30

100

200

300

30

25

500

1000

75

50

B[ghi]Pe
R2 = 0,37
P<0.01

25

1500

B[k]Fl
2

R = 0,41
P<0.01

30

0
0

25

50

75

100

75

75

75

Removal (%)

100

Removal (%)

100

50
dB[ah]An
R2 = 0,52
P<0.01

25

0
0

250

500

750 1000

R2 = 0,63
P<0.01
25

10

75

75

25

Ph
R2 = 0,85
P<0.01

25

20

Conc. (ng/L)

40

500

750

Py
R2 = 0,68
P<0.01

50

25

0
0

Removal (%)

75

Removal (%)

100

50

250

Conc. (ng/L)

100

R = 0,35
P<0.01

40

Fl

100

IPy

30

50

Conc. (ng/L)

20

0
0

Conc. (ng/L)

50

10

Conc. (ng/L)

100

25

90

60

Conc. (ng/L)

Chry
R2 = 0,66
P<0.01

60

90

Conc. (ng/L)

50

30

Conc. (ng/L)

0
0

R2 = 0,50
P<0.01

30

90

Removal (%)

R = 0,46
P<0.01

Removal (%)

Removal (%)

B[e]Py
2

Removal (%)

60

100

100

50

B[b]Fl

Conc. (ng/L)

Conc. (ng/L)

75

60

0
0

Removal (%)

Removal (%)

90

Removal (%)

Removal (%)

90

483

0
0

2000

4000

Conc. (ng/L)

6000

1000

2000

Conc. (ng/L)

Fig. 4. PAHs removal efficiencies in the primary treatment stage vs. concentration in untreated wastewater.

removed mainly due to sorption in secondary sludge (28e

62%), whereas the percentages attributed to volatilization and
biodegradation were very low (<1e2% and <1e4%, respectively). Low removals due to volatilization were also predicted
by Byrns (2001) (1.1% for Ace, 0.5% for An and around 0% for
Py and B[a]Py, reaching 22% only for Np).

Despite the discrepancies observed in individual treatment

stages, experimental and predicted removals of PAHs in the
overall (primary plus secondary) treatment process (Fig. 7) exhibited remarkable consistency for most PAH compounds with
calculated values within 20% and 20% of corresponding
model predictions. Larger inconsistency was observed for F,

E. Manoli, C. Samara / Environmental Pollution 151 (2008) 477e485

484
100

120
Calculated

Predicted

Removal (%)

Removal (%)

Calculated

100

80
60
40

Predicted

80
60
40
20

20

]P
y
B[
gh
i]P
e

Fl

B[

B[
b]

Ch
ry

]A
n

Py

[g

B[

Fl

An

Ph

Np

hi
]P
e

]P
B

[b

hr

]F

n
C

]A

Py

Fl

n
A

Ph

p
N

0
0

Fig. 5. Calculated and predicted removals of PAHs during the primary treatment of wastewaters (mean  SD). Comparisons concern the same samples.

for which the models prediction was by 40% overestimated

compared to the calculated removal.
Evaluation of the precision of FATE has indicated that the
model is only expected to predict a value within an order of
magnitude of the measured result with a probability of 80%.
The total removal of compounds primarily removed by sorption
may be slightly overpredicted, while compounds primarily removed by volatilization and biodegradation may be slightly
underpredicted (US EPA, 1990), something that can be observed in Fig. 7.
4. Conclusions
The removal of Polycyclic Aromatic Hydrocarbons (PAHs)
from municipal wastewater was examined in a conventional
activated sludge wastewater treatment plant. Two approaches

Removal (%)

(a)

100
Calculated

Predicted

80
60
40
20
e
[g

hi

]P

]P
y

B[

[b
]
B

Removal (%)

(b)

Fl

y
C
hr

]A
n
[

Py

Fl

A
n

Ph

N
p

80
Sorption

Volatilization

Biodegradation

60
40

Fig. 7. Calculated and predicted removals of PAHs in the whole (primary and
secondary) treatment process (mean  SD). Comparisons concern the same
samples.

were employed: experimental removal calculations based on

actual field data (sampling/analysis of wastewater samples),
and the FATE (Fate and Treatability Estimator) model application. Experimental removals of individual PAHs ranged between 28 and 67% in the primary stage, between <1 and
61% in the secondary stage, and between 37 and 89% in the
whole treatment process. Significant relationship was observed
between removal efficiency and log Kow of PAHs in the primary stage suggesting that these compounds are principally
removed through sorption to sludge particles and transfer to
the sludge processing systems. Significant relationship was
also observed between removal efficiencies and the log KH
of PAHs in the secondary stage.
Good agreement between the experimentally calculated
percent removals of PAHs and those predicted by the FATE
model was observed for the whole treatment process (primary
and secondary). However, when the separate treatment stages
are concerned, there were significant inconsistencies between
experimental values and model outputs. According to the
model predictions, lower removals of PAHs would be expected
in the primary treatment than those experimentally found. On
the other hand, the predicted removals in the secondary stage
were higher than experimental efficiencies. These discrepancies are possibly related with the fact that FATE was calibrated for total removal (US EPA, 1990), but there were not
enough data available for calibration by removal mechanism,
therefore calibration of individual removal mechanisms was
bases on best engineering judgment. Nevertheless, the availability of effluent concentration data allowed FATE to be calibrated for total removal (US EPA, 1990). It could be suggested
that further work, both modelling and experimental, is needed
to precisely determine the fate mechanisms of wastewater contaminants in treatment systems.
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20

hr
y
B
[b
]F
l
B
[
]P
y
B
[g
hi
]P
e

]A
n

Py

B[

Fl

A
n

Ph

Fig. 6. (a) Calculated and predicted removals of PAHs during the secondary
treatment of wastewater (mean  SD). Comparisons concern the same samples. (b) Model estimations for the relative contribution of mechanisms to
the removal of PAHs in the secondary treatment step.

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