S CIE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 8 ) 2 6 32 72

a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m

w w w. e l s e v i e r. c o m / l o c a t e / s c i t o t e n v

Priority pollutants in wastewater and

combined sewer overflow
Johnny Gasperi a,, Stphane Garnaud b , Vincent Rocher c , Rgis Moilleron a
a

Universit Paris-Est, Cereve, UMR-MA102 AgroParisTech, 61 avenue du Gal de Gaulle, 94010 Crteil Cedex, France
Mairie de Paris, Direction de la Propret et de l'Eau, Service technique de l'eau et de l'assainissement,
27 rue du Commandeur 75014 Paris, France
c
SIAAP, Direction du Dveloppement et de la Prospective, 82 avenue Klber,92700 Colombes, France
b

AR TIC LE D ATA

ABSTR ACT

Article history:

Implementation of the European Water Framework Directive and its affiliated directives

Received 6 September 2007

requires Member States to improve their understanding of priority pollutants (PPs) in urban

Received in revised form 25 July 2008

areas and obviously within wastewater systems. As a direct consequence, this study is

Accepted 6 August 2008

intended to furnish data on both PP occurrence and the significance of concentrations in

Available online 23 September 2008

wastewater during dry and wet periods within combined sewers. Various sampling sites
within the Paris combined sewer network were selected; for each sample, a total of 66

Keywords:

determinants, including metals, polycyclic aromatic hydrocarbons (PAHs), pesticides,

Combined sewer overflow

organotins, volatile organic compounds, chlorobenzenes, phthalates and alkylphenols,

Priority pollutants

were analysed. A broad range of PPs was observed in wastewater during dry as well as wet

Water Framework Directive

weather periods. Of the 66 elements investigated, 33 and 40 priority substances could be

Wastewater

observed in raw sewage and wet weather effluent, respectively. As expected, a majority of
metals were present in all samples, reflecting their ubiquitous nature. For both periods,
chlorobenzenes and most of the pesticides always remained below the limit of
quantification, while the majority of other organic pollutants assessed were identified
within the g l 1 range. As highlighted by the larger number of substances detected in wet
weather samples and the significance of their concentrations, runoff via atmospheric inputs
and/or surface leaching was found to induce a wider range of PPs (n = 40) and lead to higher
concentrations of certain metals, PAHs, pesticides and other individual compounds. The
data generated during this survey, which constitutes one of the first studies conducted in
Europe to report concentrations for a variety of priority substances in wastewater within
combined sewers, may be used in the future to identify PPs of potential significance for dry
and wet weather periods and targeted for further investigation.
2008 Elsevier B.V. All rights reserved.

1.

Introduction

The European Community strategy to combat surface water

pollution by means of a control policy was set forth in the
European Water Framework Directive 2000/60/EC. Decision no.
2455/2001/EC adopted by the European Parliament and the
Council on November 20, 2001, which established the list of

priority substances in the field of water policy and amended

Directive 2000/60/EC, offered the first list of 33 substances or
groups of substances to be identified as action priorities at
the Community level. Among these priority substances, certain have been identified as priority hazardous substances,
whose emissions, discharges and losses are targeted for phasing out or complete removal. More recently, on July 17, 2006,

Corresponding author. Tel.: +33 1 45 17 16 21; fax: +33 1 45 17 16 27.

E-mail address: gasperi@univ-paris12.fr (J. Gasperi).
0048-9697/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2008.08.015

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SC IE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 8 ) 2 6 32 72

Fig. 1 Paris sewer network sampling sites considered in this study.

the Commission adopted a Directive for the purpose of setting

mandatory environmental quality standards for priority substances that Member States must achieve by 2015, in order to
ensure a satisfactory chemical status for surface water. In
pursuit of this objective through identifying possible pollutant reduction measures, an accurate knowledge base on
these substances in the urban environment, especially within wastewater systems, has definitely proved necessary.
Though a number of studies were undertaken to identify
the occurrence and significance of some PPs in wastewater
systems (Wilkie et al., 1996; Rule et al., 2006a,b,c; Palmquist
and Hanaeus, 2005), most of these efforts focused primarily on
raw sewage, domestic wastewater or wastewater contained in
separate networks that discharge wastewater into combined
systems. Due to the lack of available information on PP levels
in wastewater during dry and wet weather periods within
combined sewers, the need for this study became apparent.
Since the Paris combined sewer may be considered representative of sewerage systems found in many old European
capital cities (London, Madrid, etc.) and therefore capable of
accurately describing a range of PPs within typical combined
sewers in urban areas, this particular network was selected
for the present research project. To provide a good overview
on PP significance within the Paris network, also called Paris
intra-muros (for just the city of Paris without its suburbs,
encompassing 105 km2, 2.15 million inhabitants), investigations were carried out at different network sites on both
dry and wet weather flows (DWF and WWF), as well as on
combined sewer overflows (CSOs). For each sample, a total of
66 determinants including 7 metals (Cd, Cr, Cu, Hg, Ni, Pb and
Zn) and 59 organic compounds or classes of compounds
(organotins, chlorobenzenes, volatile organic compounds

(VOCs), polycyclic aromatic hydrocarbons (PAHs), pesticides,

alkylphenols, phthalates, etc.) were examined, along with the
more routine wastewater quality parameters (total solids,
organic matter, nitrogen, phosphorous, total hydrocarbons,
etc.).
This survey constitutes one of the first studies in Europe to
report data for a variety of priority substances in wastewater
during dry and wet weather periods within combined sewers.
These results are of critical importance since the data
generated for a predetermined number of hazardous substances may be used in the future to identify PPs of potential
significance and/or deserving of further analysis.

2.

Materials and methods

2.1.

Sampling sites

Paris intra-muros covers an area of 105 km2 and contains a

population of 2.15 million. The area considered is densely
populated (i.e. approximately 20,500 inhabitants/km2) and
features many small shops, offices and very little industrial
activity. The sewerage system is combined. According to a
surface distribution (41% for roofs, 28% for streets and 31% for
other surfaces including squares, parks and railways), the
impervious surface area has been estimated at roughly 70 km2.
In order to ensure extensive geographic coverage, composite
samples were collected at 4 upstream and 6 downstream sites
of this intra-muros network during one dry and one wet weather
campaign (Fig. 1). The selected sites represented the largest
interceptors of the Paris network. During the dry period, daily
wastewater volume for the 4 upstream sites (the cross-hatched

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S CIE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 8 ) 2 6 32 72

Table 1 Routine wastewater parameters and

corresponding analytical methods
Parameter
BOD5
COD
TS
NH+4
TKN
Ptot
PO3
4
SO2
4
THs

Analytical method
NF EN 1899-1
NF T 90-101
NF EN 872
NF EN ISO 11732
NF EN 25663
NF EN ISO 15681-2
NF EN ISO 15681-2
NF EN ISO 10304-1
NF EN ISO 17993

arrow in Fig. 1) amounted to 37,000 m3, i.e. equivalent to about

47% of the daily volume entering the Paris sewer network. For
the 6 downstream sites (coloured arrow), the daily volume of
sewage reached 770,000 m3, corresponding to some 78% of the
volume exported from the Paris wastewater network.
During the wet period, 4 of the 45 CSO outfalls in Paris were
also equipped. For the rainfall event considered (the mean
precipitation was estimated at 20.1 mm and the return period
at beyond six months), the volume discharged into the Seine
River via the 4 outfalls was evaluated at around 80,000 m3,
corresponding to 23% of the total annual CSO discharge
(using data for the years 2004 and 2005).

2.2.

Routine wastewater parameters

For each sample, routine wastewater parameters, such as total

solids (TS), chemical and biochemical oxygen demand (COD
and BOD5), ammonium (NH+4), total Kjeldahl nitrogen (TKN), total
2
phosphorous (Ptot), orthophosphates (PO3
4 ), sulphates (SO4 ) and
total hydrocarbons (THs), were assessed as an initial step. As
reported in Table 1, these parameters were measured in
accordance with standard French methods.

2.3.

Priority substances

Based on the list established in Decision no. 2455/2001/EC, 9

groups of compounds were selected, accounting for 66 individual substances (Table 2). A total of 7 metals (Cd, Cr, Cu, Hg, Ni,
Pb and Zn) and 59 organic compounds, including organotins
(n = 3), chlorobenzenes (n = 3), VOCs (n = 8), PAHs (n = 16), pesticides (n = 20), alkylphenols (n = 2), phthalates (n = 5), chloroalkanes (sum of C10C13) and 2, 4, 4, 6-pentabromodiphenylether
(BDE-100), were investigated. Analyses were performed by a
laboratory certified by the French Ministry of the Environment,
i.e. COFRAC (French accreditation committee). For international
quality control purposes, the COFRAC calibration certificate is
recognised by other European calibration services (EA European Cooperation for Accreditation). Standardisation of the
accreditation criteria and procedures respect the European
standards for calibration and testing laboratories, as do their
assessment and accreditation.
Analyses were carried out on the total fraction (dissolved +
particulate); organic pollutants were analysed by gas or liquid
chromatography coupled with a mass spectrometer (GCMS
and LCMS) and through the use of high-performance liquid
chromatography with fluorimetric detection (HPLC-Fluo) for

PAHs (Table 2). Metals were measured by inductively-coupled

plasma atomic emission spectroscopy (ICP-AES) and atomic
fluorescence spectroscopy (AFS), in accordance with the NF EN
ISO 11885 and NF EN 13506 methods. The limit of quantification (LOQ) has been specified for each determinant in Tables 3
through 9.

3.

Results and discussion

3.1.

Routine wastewater parameters

Regardless of the wastewater parameters under consideration, no difference was observed between the upstream and
downstream sites during the dry weather campaign. These
initial results provide key information since they suggest
that the quality of wastewater remains quite homogeneous
throughout the Paris intra-muros sewer network. Though this
result was not previously demonstrated at the Paris citywide
scale, the trend could have been expected given that the
effluent entering the Paris network originates from upstream
suburban catchments displaying similar population densities
and land uses as those found in Paris intra-muros. Moreover,
no concentration difference was noticed during the rainfall
event either between upstream and downstream sites or
among the various sites and the CSO outfalls. To a lesser extent, a similar trend had already been recorded for the two
periods by Kafi-Benyahia et al. (2008) between different Paris
urban catchments that cover smaller land areas (ranging from
42 to 2581 ha).
Since no concentration difference could be detected between sites, the data were mixed for dry (n = 10) and wet (n = 13)
weather periods. As illustrated in Fig. 2, raw sewage reveals an
organic strength, indicated by the BOD5 and COD concentrations (median values of 140 and 380 mg O2 l 1, respectively). In
comparison with household wastewater, TS, BOD5 and COD
concentrations appear to be relatively low (Palmquist and
Hanaeus, 2005). Within the Paris sewer network, these differences serve to highlight: i) the sedimentation of a suspended solid fraction during wastewater transfer; and ii) the
dilution of wastewater by parasitic water (Gasperi et al., 2007).
The COD/BOD5 ratio, which is used to determine the difficulty
of organic substances to undergo degradation, was evaluated
in the 2.53.3 range, implying that such wastewater is easily to
moderately easily biodegradable (Tchobanoglous et al., 2003).

Table 2 Pollutants considered in this study and

corresponding analytical methods
Selected group

No. in each package

Analytical method

Metals
Organotins
Chlorobenzenes
VOCs
PAHs
Pesticides
Alkylphenols
Phthalates
Others
66

7
3
3
8
16
20
2
5
2

ICP-AES/AFS
GCMS
GCMS
GCMS
HPLC-Fluo
GCMS/LCMS
GCMS
GCMS
GCMS

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Table 3 Concentrations of metals (in g l 1) in dry and wet weather flows

Dry weather flows

LOQ
(g l 1)

Cd
Cr
Cu
Hg
Ni
Pb
Zn

Median

1
10
10
0.01
10
0.2
10

Wet weather flows/CSOs

Range

1.0
b
51
0.12
b
17
361

Min

Max

b
b
20
0.07
b
b
224

2.4
25
95
0.29
18
43
1320

Median

b
b
68
0.10
b
39
682

50
15
100
100
10
90
100

%a

Range
Min

Max

b
b
38
b
b
10
248

2.1
158
1180
0.45
19
117
3525

23
8
100
92
8
100
100

b = below the limit of quantification.

Frequency of occurrence (%) for the substance in dry (n = 10) and wet weather flows (n = 13).

caused by the erosion of in-sewer deposits formed within

sewers during dry periods (Gromaire, 1998). Lastly, only total
hydrocarbons are distinguishable due to the presence of higher
WWF concentrations than those observed in raw sewage. This
finding confirms the high levels of hydrocarbons found in runoff
resulting from lubricant spills, eroded tire particles and gas
exhaust (Gasperi et al., 2005; Ngabe et al., 2000).

In addition, the concentrations for all parameters resemble

those reported in the literature for wastewater within combined sewers in Spain (Suarez and Puertas, 2005) or France
(Saget, 1994; Gromaire, 1998; Kafi-Benyahia, 2006).
A comparison of DWF and WWF concentrations allows
differentiating three groups of parameters (Fig. 2). The first,
3
which includes BOD5, TKN, NH+4, SO2
4 , PO4 , exhibits higher DWF
concentrations than those observed during the wet period; this
feature underscores the fact that wastewater constitutes the
major source for these pollutants. In the literature, it has been
well documented that most of these elements originate mainly
from human sources (especially via urine and faeces) and from
different activities such as washing and cooking (Wilkie et al.,
1996; Tchobanoglous et al., 2003; Palmquist and Hanaeus, 2005).
The second group pertains to COD, TS and Ptot and moreover
presents comparable DWF and WWF concentrations. While
urban runoff contains rather low COD, SS and Ptot concentrations (Gromaire, 1998; Zhao et al., 2007), wastewater dilution by
means of runoff should induce even lower WWF concentrations: this trend however was not observed, a result potentially

3.2.

Metals

As previously mentioned for wastewater parameters, no

significant spatial change in metal concentrations was observed across sampling points. Metal concentrations have
been listed for both the dry and wet weather campaigns in
Table 3. Cu, Hg, Pb and Zn were detected above the limit of
quantification in almost all cases, with the highest concentrations noticed for Zn and Cu. In contrast, other metals (Cr, Cd
and Ni) were only detectable on a few occasions (around 50%
for Cd and b20% for Ni and Cr). On the whole, concentrations
for these elements were either close to or less than the limit of

Table 4 Concentrations of PAHs (in g l 1) in dry and wet weather flows

LOQ
(g l 1)

N
P
A
Fluo
Pyr
B(a)A
Chry
B(a)P
B(b)F
B(k)F
D(ah)A
BP
IP
Methyl-N
Methyl-Fluo
B(1,2)F

0.05
0.02
0.02
0.01
0.02
0.02
0.02
0.01
0.02
0.03
0.02
0.01
0.03
0.10
0.02
0.02

Dry weather flows

Median

b
b
b
0.03
b
b
b
0.02
0.02
b
b
0.02
0.02
b
b
b

Wet weather flows/CSOs

%a

Range
Min

Max

b
b
b
0.03
b
b
b
b
b
b
b
b
b
b
b
b

b
b
0.02
0.09
b
0.02
b
0.05
0.06
0.03
b
0.03
0.04
b
b
b

0
0
22
100
0
10
0
78
78
33
0
78
78
0
0
0

b = below the limit of quantification.

a
Frequency of occurrence (%) for the substance in dry (n = 10) and wet weather flows (n = 13).

Median

b
0.06
b
0.14
b
0.06
0.14
0.06
0.08
0.04
b
0.05
0.04
b
b
b

%a

Range
Min

Max

b
b
b
0.04
b
0.03
b
b
b
b
b
b
b
b
b
b

b
0.42
0.06
0.50
0.53
0.19
0.33
0.24
0.24
0.13
b
0.18
0.13
b
b
0.12

0
54
33
100
46
100
69
92
92
85
0
92
62
0
0
31

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Table 5 Concentrations of pesticides (in g l 1) in dry and wet weather flows

LOQ
(g l 1)

Alachlor
Atrazine
Chlorfenvinphos
Chlorpyrifos
Diazinon
Dichlorvos
Diflufenican
Diuron
-endosulfan
-endosulfan
-HCH
-HCH
Isoproturon
Lindane
Oxadiazon
Pentachlorophenol
Propiconazole
Simazine
Terbutryn
Trifluralin

0.06
0.06
0.06
0.06
0.02
0.02
0.02
0.02
0.03
0.03
0.03
0.03
0.06
0.03
0.02
0.15
0.06
0.06
0.06
0.06

Dry weather flows

Median

b
b
b
b
b
b
b
0.24
b
b
b
b
b
b
b
b
b
b
b
b

Range

Wet weather flows/CSOs

%

Min

Max

b
b
b
b
b
b
b
0.03
b
b
b
b
b
b
b
b
b
b
b
b

b
b
b
0.10
b
0.07
0.03
0.47
b
b
b
b
b
b
b
0.36
b
b
b
b

0
0
0
11
0
11
11
100
0
0
0
0
0
0
0
33
0
0
0
0

Median

b
b
b
b
b
NA b
b
1.40
b
b
b
b
b
b
0.15
b
0.15
b
b
b

%a

Range
Min

Max

b
b
b
b
b
NA
b
0.09
b
b
b
b
b
b
b
b
b
b
b
b

b
b
b
b
1.05
NA
2.75
16.00
b
b
b
b
b
b
0.54
b
0.21
b
0.16
b

0
0
0
0
15

23
100
0
0
0
0
0
0
77
0
57
0
31
0

b = below the limit of quantification.

a
Frequency of occurrence (%) for the substance in dry (n = 10) and wet weather flows (n = 13).
b
Not analysed due to an analytical problem.

quantification in dry weather flows (Table 3). These results are

in good agreement with the low Cr levels reported in domestic
wastewater by Comber and Gunn (1996). Furthermore, concentrations of the other metals were recorded at similar
levels, as was also reported in the literature (Rule et al., 2006a;
Garnaud, 1999).
The ubiquity of metals in raw sewage reveals a complex
mixture of diffuse sources. Many of these elements are used as
chemical additives in a wide array of consumer products, e.g.
food and drink containers, household cleaning and personal
care products (Chino et al., 1991; Comber and Gunn, 1996). In
addition, significant quantities of metal enter into a variety of
metal finishing processes and are incorporated into household appliances, pipes, fitting and surface finishes (Rule et al.,
2006a).

As opposed to the first elements, WWF concentrations for

Cu, Pb and Zn are raised by a factor extending from 2 to 6.
These differences may be linked to either: i) the high metal
concentrations found in runoff, or ii) in-sewer deposit erosion
(Gromaire, 1998). A recent study conducted by Kafi-Benyahia
(2006), focusing on evaluating the contributions of wastewater, runoff and in-sewer deposit erosion to WWF pollutant
loads in the Paris sewer, revealed that a major proportion of Cu
originates from deposit erosion, while runoff proves to be the
major source of Cd, Pb and Zn. The presence of these metals in
runoff is in fact known with precision. For street runoff,
vehicles and vehicle leaching constituted the leading contributors to metal loads (Legret and Pagotto, 1999; Srme and
Lagerkvist, 2002). For roof runoff, the majority of roofs within
Paris intra-muros are equipped with metallic materials such as

Table 6 Concentrations of VOCs (in g l 1) in dry and wet weather flows

LOQ
(g l 1)

Benzene
Toluene
Dichloroethane
Dichloromethane
Chloroform
Trichloroethylene
Tetrachloroethylene
Hexachlorobutadiene

1.0
1.0
3.0
20
1.0
1.0
1.0
0.05

Dry weather flows

Median

b
b
b
b
8.5
b
1.6
b

Wet weather flows/CSOs

%a

Range
Min

Max

b
b
b
b
b
b
b
b

b
3.2
b
86
25
1.8
4.0
b

0
30
0
20
90
20
60
0

b = below the limit of quantification.

Frequency of occurrence (%) for the substance in dry (n = 10) and wet weather flows (n = 13).

Median

1.0
b
b
b
1.8
1.1
3.9
b

%a

Range
Min

Max

b
b
b
b
1.1
b
b
b

1.0
6.7
b
477
3.0
8.3
58
b

85
46
0
8
100
62
77
0

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Table 7 Concentrations of organotin compounds (in ng l 1) in dry and wet weather flows
Dry weather flows

LOQ
(ng l 1)

Median

Range
Min

Dibutyltin
Monobutyltin
Tributyltin

5
5
5

15
20
b

Wet weather flows/CSOs

%

Median

Max

9
10
b

22
27
12

100
100
20

16
28
b

%a

Range
Min

Max

b
b
b

36
57
50

92
100
31

b = below the limit of quantification.

Frequency of occurrence (%) for the substance in dry (n = 10) and wet weather flows (n = 13).

lead fittings and zinc sheets (about 80% according to Gromaire,

1998), thereby leading to high metal concentrations.

3.3.

Polycyclic aromatic hydrocarbons

Table 4 gives PAH concentrations in dry and wet weather

flows. A total of 13 PAHs, including naphthalene (N), phenanthrene (P), anthracene (A), fluoranthene (Fluo), pyrene (Pyr),
benzo(a)anthracene (B(a)A), chrysene (chry), benzo(a)pyrene
(B(a)P), benzo(b)fluoranthene (B(b)F), benzo(k)fluoranthene (B
(k)F), dibenz(ah)anthracene (D(ah)A), benzo(ghi)perylene (BP),
indeno(cd)pyrene (IP) and three alkylated PAHs methylnaphthalene (methyl-N), methyl-2-fluoranthene (methylFluo) and benzo(1,2)fluorene (B(1,2)F), were analysed for each
sample.
Concentrations of Fluo, B(a)P, B(b)F, BP and IP were detectable in raw sewage, but these levels were always situated
at either near or below the limit of quantification, while 8 PAHs
(N, P, Pyr, Chry, D(ah)A and alkylated PAHs) were never
detectable (Table 4). The minimum, median and maximum
total concentrations (expressed as a sum of the 13 analysed)
were determined to be 0.03, 0.14 and 0.32 g l 1, respectively.
The main compound contributing to total load was Fluo,
whose median contribution amounted to 39%. The greatest
frequency of occurrence was also observed for Fluo, followed
by B(a)P, B(b)F, BP and IP (78%). The predominance of these
PAHs indicates the presence of pyrolytic origins since some
authors have reported that pyrolytic inputs are characterised
by the abundance of high molecular weight compounds (Soclo
et al., 2000; Wang et al., 1999). As compared to PAH concentrations reported in the literature for domestic wastewater, total
concentrations measured in sewage appeared to be slightly
less than those reported by Palmquist and Hanaeus (2005)
(from 0.02 to 0.89 g l 1) or by Gasperi et al. (2006) (from 0.24 to
3.09 g l 1). In terms of PAH origins, a recent study conducted
by Gasperi et al. (2007) revealed at the scale of the Marais

catchment (42 ha, Paris) that domestic inputs provided the

major contribution to PAH loads within combined sewers
during dry periods.
During wet periods, a greater proportion of PAHs (12 of the
16 analysed PAHs) were detectable in most samples (Table 4).
As demonstrated by the minimum, median and maximum
total WWF concentrations reaching values of 0.1, 1.0 and
1.97 g l 1 respectively, runoff induces much higher PAH levels
than those for DWF. As for metals, this finding results from: i)
in-sewer erosion during the storm event, and ii) high PAH
concentrations during runoff. Gasperi et al. (2007), who assessed the PAH contributions of runoff and in-sewer erosion at
the scale of this same Marais catchment indicated that 34%
of total WWF loads (sum of the 16 US-EPA PAHs) originated
from runoff, while in-sewer erosion contributed 55%. The high
PAH levels in runoff are mainly attributed to their presence in
fuels and their generation during fossil fuel combustion.
As previously mentioned for DWF, the PAH patterns characterised by the predominance of heavy PAHs attest to the
pyrolytic origins of PAHs (Soclo et al., 2000). The impact of
pyrolytic contamination is also suggested by the presence of
Chry and B(a)A, which are considered to be combustion
process markers. The predominance of pyrolytic origins is
certainly linked to the high density of combustion sources
within the Paris metropolitan area. The Paris conurbation does
indeed generate heavy road traffic; consequently, diesel- and
gasoline-powered vehicles are responsible for emitting great
quantities of PAH into the environment. In addition to these
mobile sources, aromatic compounds are introduced in the
environment through contamination by various kinds of point
sources, such as residential heating. Although aromatic
fingerprinting is indicative of major pyrolytic contamination,
the presence of alkylated derivatives would suggest traces of
petrogenic inputs, thus potentially reflecting the emission of
unburned lubricating oils by road traffic exhaust (Yunker et al.,
1996).

Table 8 Concentrations of alkylphenols (in g l 1) in dry and wet weather flows

LOQ
(g l 1)

4-para-nonylphenol
para-tert-octylphenol

0.03
0.01

Dry weather flows

Median

b
0.13

Wet weather flows/CSOs

%a

Range
Min

Max

b
0.06

b
0.35

0
100

b = below the limit of quantification.

a
Frequency of occurrence (%) for the substance in dry (n = 10) and wet weather flows (n = 13).

Median

b
0.20

%a

Range
Min

Max

b
0.09

0.04
0.62

31
100

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Table 9 Concentrations of phthalates (in g l 1) in dry and wet weather flows

LOQ
(g l 1)

Diethylexyl phthalate (DEHP)

Dimethyl phthalate (DMP)
Diethyl phthalate (DEP)
Di-n-butyl phthalate (DnBP)
Benzylbutyl phthalate (BBP)

0.10
0.10
0.10
0.10
0.10

Dry weather flows

Median

27
b
3.29
0.18
b

Range

Wet weather flows/CSOs

%

Min

Max

16
b
0.82
b
b

57
b
5.95
0.35
0.22

100
0
100
67
33

Median

22
NA b
b
0.54
b

%a

Range
Min

Max

5
NA
b
b
b

188
NA
2.90
0.68
0.32

100

38
50
17

b = below the limit of quantification.

a
Frequency of occurrence (%) for the substance in dry (n = 10) and wet weather flows (n = 13).
b
Not analysed due to an analytical problem.

3.4.

Pesticides

For each sample, a total of 20 pesticides were analysed, i.e.:

diuron, oxadiazon, propiconazole, terbutryn, diflufenican,
diazinon, atrazine, chlorfenvinphos, chlorpyrifos, dichlorvos,
alachlor, -endosulfan, -endosulfan, -HCH, -HCH, isoproturon, lindane, pentachlorophenol, simazine and trifluralin.
Table 5 provides the DWF and WWF concentrations for each
compound, as well as its respective frequency of occurrence.
Most pesticides went undetected within all of the foul
wastewater samples (Table 5); this result, which agrees with
findings cited by Rule et al. (2006b) at the scale of a 6 km2 urban
catchment, reflects the sporadic presence of pesticides within
combined sewers. Such a result is unsurprising given the limited
number of likely routes of entry for pesticides into urban water
systems. During dry periods, the disposal of waste chemicals into
sewers and street cleaning water would indeed constitute the
only possible sources. The pesticide inputs through street cleaning water are indeed possible since the City of Paris' Street
Cleaning Services wash frequently street gutters and pavements.
Furthermore, the use of many of these pesticides is now banned;
hence their presence would no longer be expected. Of the 5
detectable pesticides, only diuron was actually detected in all
samples, with concentrations ranging from 0.03 to 0.47 g l 1
(Table 5), while the frequency of occurrence for the other
compounds (chlorpyrifos, dichlorvos, diflufenican and pentachlorophenol) was recorded between 11% and 33%. The marked
presence of diuron in Paris wastewater is attributed to its ex-

tensive use in the city, as this pesticide accounted for more than
31% of the total contribution from municipal service organizations (Blanchoud et al., 2007). Diuron is in fact commonly used in
road and railway maintenance, municipal uses and private parks.
During wet periods, pesticide patterns were observed to
evolve. Chlorpyrifos, dichlorvos and pentachlorophenol, initially detected in wastewater, were then no longer detectable.
Diflufenican was more often quantified at higher concentration
levels. For diuron, WWF concentrations appeared to be much
higher than those observed for wastewater. The higher levels in
WWF may be attributed to the greater leaching of urban surfaces
by runoff (streets, gutters and pavements) during the storm
event. Blanchoud (2001) revealed that 80% to 100% of the diuron
applied on impervious surfaces could potentially be remobilized
during a rainfall event. Lastly, 4 pesticides, i.e. diazinon, oxadiazon, propiconazole and terbutryn, were also detected in
WWF, with frequencies of occurrence ranging between 15% and
77% (Table 5). Most of these components are herbicides used as
preemergent and/or postemergent control agents for mainly
grasses and many types of annual weeds. As for diuron, the
leaching of urban surfaces during rainfall events is the most
likely explanation for the presence of these compounds in wet
weather flows.

3.5.

Volatile organic compounds (VOCs)

Table 6 lists VOC concentrations for both dry and wet periods,
along with the frequency of occurrence for each compound. In

Fig. 2 DWF and WWF concentrations (in mg l 1) for routine wastewater parameters.

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raw sewage, chloroform and tetrachloroethylene were the

only solvents found at levels greater than the limit of
quantification. Median concentrations were evaluated at 8.5
and 1.6 g l 1, respectively (Table 6). According to Wilkie et al.
(1996), chlorination practices may constitute a potential
source of chloroform in sewage. For tetrachloroethylene, its
widespread use as a degreasing agent and solvent provides
one of the most likely explanations for its presence in
wastewater. Owing to its excellent degreasing properties,
tetrachloroethylene is indeed present in numerous household
products, including automobile cleaners, suede protectors,
paint removers and strippers, etc.
The concentrations of toluene, dichloromethane and trichloroethylene, for which the frequency of occurrence varied
from 20% to 30%, were also marginally higher, reflecting the
possible greater local use of these solvents. Trichloroethylene
solvents display attractive degreasing properties and are used
in similar products. On the whole, the VOC levels found in this
study for raw sewage agree closely with results reported by
Rule et al. (2006c) for influents at 30 wastewater treatment
plants (WWTP) in the United Kingdom.
Like for DWF, the WWF concentrations of dichloroethane,
dichloromethane and hexachlorobutadiene were nearly entirely
below the limit of quantification. Benzene was present predominantly around the limit of quantification (1 g l 1), and chloroform, trichloroethylene and tetrachloroethylene were detectable
in most samples with concentrations in the 158 g l 1 range.
Although commercial or industrial operations discharging into
municipal sewers are commonly considered as the main sources
of tetrachloroethylene, the higher WWF concentrations of this
compound may reflect the impact of runoff via surface leaching
and/or atmospheric inputs (Table 6). Considering that VOCs easily
become airborne in the atmosphere due to their high vapour
pressure, the gas-phase washout by rain, which is generally
considered as a major mechanism for removal from the atmosphere, could appear as a major contributor to VOC loads in
combined sewer overflow.

3.6.

Chlorobenzenes

For dry and wet weather periods, concentrations of hexachlorobenzene, pentachlorobenzene and trichlorobenzene were
always less than the limits of quantification, ranging from
0.01 to 0.05 g l 1. This observation corroborates previous
results published by Rule et al. (2006b). The low levels of
chlorobenzene in samples could reflect their removal or their
use as intermediate compounds in the chemical industry, with
a low probability of discharge into sewer systems. Furthermore, pentachlorobenzene is no longer produced within the
European community and therefore should not be detected in
any of the samples.

3.7.

Organotins

Concentrations (in ng l 1) of di- (DBT), mono- (MBT) and tributyltin (TBT) are reported in Table 7. Regardless of the period
considered, DBT and MBT were detectable in all samples above
the limit of quantification, while TBT was observed in just a few
samples (Table 7). The DWF concentrations, varying over the 9
22 ng l 1 and 1027 ng l 1 ranges for DBT and MBT respectively,

lie close to those found by Thomaidis et al. (2007) for WWTP

influents in Greece. The presence of tributyltin compounds in
raw sewage can probably be explained by their use as main
active ingredients in biocides for controlling a broad spectrum of
organisms (wood treatment and preservation, antifungal action
in textiles and industrial water systems, etc.).
During wet periods, these concentrations appeared to be
slightly higher than dry period observations. Surprisingly,
marginally high concentrations of organotins, i.e. 340, 260 and
12 ng l 1 of DBT, MBT and TBT for DWF and 3850, 4540 and 50 ng
l 1 for WWF, were recorded at 1 of the 4 upstream sampling
sites. A subsequent and more detailed investigation on this site
should allow identifying the origin of contamination.

3.8.

Alkylphenols

Among the alklyphenols, 4-para-nonylphenol (NP) and paratert-octylphenol (OP) were investigated. For both periods, OP
proved to be the predominant substance as regards frequency of
occurrence, whereas NP occurred in a smaller number of samples (0% and 31% for DWF and WWF, respectively). OP was
detected in raw sewage at concentrations ranging from 0.06 to
0.35 g l 1 (with a median of 0.13 g l 1), while the WWF concentrations were found between 0.09 and 0.69 g l 1 (Table 8).
Concerning foul wastewater, this concentration range is
comparable to values reported in the literature for wastewater
(Ying et al., 2002). No data could be found however in the
literature for these alkylphenols in wet weather flows. NP and
OP are endocrine-disrupting chemicals and, as such, can mimic natural hormones in aquatic organisms, causing adverse
impacts on their reproductive system. Yet, the presence of these
compounds in wastewater may primarily result from the
degradation of alkylphenol polyethoxylates, which are widely
used as nonionic surfactants (Ying et al., 2002). In Europe,
alkylphenol polyethoxylates are indeed used in numerous
industrial, commercial and laboratory detergents, industrial
processes and some pesticide formulations. Their presence
might also be tied to the direct use of alkylphenols as plasticizers
in plastics.

3.9.

Phthalates

For this group of chemicals, five substances were assessed:

diethylhexyl phthalate (DEHP), dimethyl phthalate (DMP),
diethyl phthalate (DEP), di-n-butyl phthalate (DnBP), and benzylbutyl phthalate (BBP). The concentrations and frequencies of
occurrence have been listed for both periods in Table 9. DEHP
was detectable in all samples tested and represented the
predominant phthalate (approximately 90% of all phthalates).
DWF and WWF concentrations of DEHP in this study were
within the 1657 g l 1 and 5188 g l 1 ranges, which lies in the
higher range of what was found in the literature (Fromme et al.,
2002; Vogelsang et al., 2006).
DEP was also present in most samples, while DnBP (50%
67%) and BBP (17%33%) exhibited a lower frequency of
occurrence. Among the compounds considered, only DMP
was never detected in raw sewage. These results agree with
those reported by Fromme et al. (2002) and Vogelsang et al.
(2006) for sewage effluent. As for other chemicals, the presence
of phthalates was expected since these compounds are widely

S CIE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 8 ) 2 6 32 72

used throughout industry and within households, particularly

as additives in plastics, including pipes used for plumbing
purposes. High concentrations of phthalates and more specifically DEHP, which represents the main plasticizer used in
household materials, were thus expected.
In comparison with dry period results, DEP, DnBP and BBP
reflected a lower frequency of occurrence in wet weather
effluents. While BBP exhibited a similar concentration range
between both periods, DnBP and to a lesser extent DEHP
showed higher maximum WWF concentrations than those
observed during the dry period. These data did not provide
clear answers as regards the influence of surface runoff on
phthalate concentrations.

3.10.

Other organic chemicals

This last group of organic chemicals includes chloroalkanes, in

reference to the sum of C10C13 and 2, 2, 4, 4, 6-pentabromodiphenylether (BDE-100). During both dry and wet weather flows,
concentrations remained entirely above the limit of quantification, i.e. b3 g l 1 for chloroalkanes and b0.03 g l 1 for BDE-100.
As regards chloroalkanes, Rule et al. (2006c) also reported levels
lying below 1 g l 1. This lack of chloroalkanes may be accounted
for by their phasing out in France and their removal from the
market since 2004 (INERIS, 2005). Although chloroalkanes may
still be used as intermediates in the chemical industry, the
probability of discharge into sewer systems also remains limited.
For BDE-100, the levels found in this study are much lower than
the values cited by Anderson and MacRae (2006) for WWTP
influents of the Orono conurbation (US), with a mean concentration at 0.44 g l 1 (n= 2). According to these authors, BDE-100
did not constitute the predominant PBDE in WWTP influents,
in comparison with congeners BDE-47 and BDE-99 (1.64 and
1.60 g l 1, respectively).

4.

Conclusion

The implementation of European Water Framework Directive

2000/60/EC and its affiliated directives requires Member States
to improve their knowledge of priority substances within the
urban environment. To achieve the stated objective, information on the occurrence of PPs in urban areas and especially
within wastewater systems has had to be collected. This study
was therefore designed to provide information on PP occurrence and significance of concentrations in wastewater and
during wet weather flows within combined sewers. The data
generated during this survey, which constitutes one of the
first studies in Europe to report concentrations for a variety of
priority substances in wastewater during both dry and wet
weather periods, could be used in the future to identify PPs of
potential significance and worthy of further investigation.
This work has served, first and foremost, to confirm that a
large range of PPs are indeed present in wastewater. Of the 66
elements measured, 33 and 40 priority substances were observed
in raw sewage and wet weather effluents, respectively. As expected, most metals were present in all samples, reflecting their
ubiquitous nature. For both dry and wet periods, chlorobenzenes
and most pesticides were entirely below the limit of quantification (varying from 0.01 to 0.06 g l 1), while the majority of the

271

other organic pollutants analysed in the Paris intra-muros network

were found to be in the g l 1 range, with the exception of DEHP
(whose concentrations reached as high as 20 g l 1). As highlighted by the greater number of substances detected in WWF
samples and the significance of their concentrations, runoff
via atmospheric inputs and/or urban surface leaching induces a
wider range of PPs (n=40) and leads to higher WWF concentrations in the case of certain metals (Cu, Pb and Zn), PAHs (34 ring
PAHs), pesticides (diuron and oxadiazon, and to lesser extent
diazinon, propiconazole and terbutryn) and organotin compounds (MBT and DBT). With the exception of metals and PAHs,
for which mass balances within the Paris network were
previously performed by Kafi-Benyahia (2006) and Gasperi et al.
(2007) for a number of rainfall events, no data are today available
on most PPs for the purpose of clearly apportioning the contributions of atmospheric inputs, runoff and in-sewer deposit
erosion to WWF loads within combined sewers. At present,
one of the most critical issues probably consists of investigating
the occurrence and significance of PPs in: i) atmospheric inputs,
ii) runoff for various types of urban surfaces, and iii) in-sewer
sediments within combined sewers in order to more effectively
determine the contributions of each input. In the case of combined sewer systems, such information will soon be of prime
importance in the effort to prioritise the control at the source
interventions eventually required during implementation of the
various directives.

Acknowledgements
The authors gratefully acknowledge the Paris's Municipality
and the Parisian sewer services (Direction de la Propret et
de l'Eau) for their scientific supports during this research
project.

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