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Illicit drugs and the environment - A review


ARTICLE in SCIENCE OF THE TOTAL ENVIRONMENT JUNE 2012
Impact Factor: 4.1 DOI: 10.1016/j.scitotenv.2012.05.086 Source: PubMed

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Raktim Pal

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University of Newcastle

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Science of the Total Environment 463464 (2013) 10791092

Contents lists available at ScienceDirect

Science of the Total Environment


journal homepage: www.elsevier.com/locate/scitotenv

Review

Illicit drugs and the environment A review


Raktim Pal a, b, Mallavarapu Megharaj a, b,, K. Paul Kirkbride c, Ravi Naidu a, b,
a
b
c

Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, Adelaide, South Australia 5095, Australia
CRC for Contamination Assessment and Remediation of the Environment, University of South Australia, Australia
Australian Federal Police Forensic and Data Centres, Canberra, Australia

a r t i c l e

i n f o

Article history:
Received 15 March 2012
Received in revised form 28 May 2012
Accepted 28 May 2012
Available online 21 June 2012
Guest Editors: Ravi naidu, Ming Wong
Keywords:
Illicit drug
Emerging contaminant
Wastewater
Surface water
Groundwater
Ecotoxicity

a b s t r a c t
Illicit drugs and their metabolites are the latest group of emerging pollutants. Determination of their concentration in environment (such as water bodies, soil, sediment, air) is an indirect tool to estimate the community level consumption of illicit drug and to evaluate potential ecotoxicological impacts from chronic low
level exposure. They enter the wastewater network as unaltered drugs and/or their active metabolites by
human excretion after illegal consumption or by accidental or deliberate disposal from clandestine drug laboratories. This article critically reviews the occurrence and concentration levels of illicit drugs and their metabolites in different environmental compartments (e.g., wastewater, surface waters, groundwater, drinking
water, and ambient air) and their potential impact on the ecosystem. There is limited published information
available on the presence of illicit drugs in the environment, reports are available mainly from European
countries, UK, USA, and Canada but there is a lack of information from the remainder of the world. Although
the environmental concentrations are not very high, they can potentially impact the human health and ecosystem functioning. Cocaine, morphine, amphetamine, and MDMA have potent pharmacological activities
and their presence as complex mixtures in water may cause adverse effect on aquatic organisms and
human health. However, there is no current regulation demanding the determination of occurrence of
these emerging pollutants in treated wastewater, surface water, drinking water, or atmosphere. Thus, critical
investigation on distribution pattern of this new group of emerging contaminant and their potential harmful
impact on our environment needs immediate attention.
2012 Published by Elsevier B.V.

Contents
1.
2.
3.

Introduction . . . . . . . . . . . . . . . . . . . . . . . .
The potential for distribution of illicit drugs and metabolites in
Illicit drugs in environment . . . . . . . . . . . . . . . . .
3.1.
Wastewater . . . . . . . . . . . . . . . . . . . .
3.2.
Surface water . . . . . . . . . . . . . . . . . . . .
3.3.
Groundwater and drinking water . . . . . . . . . .
3.4.
Sewage sludge . . . . . . . . . . . . . . . . . . .
3.5.
Air . . . . . . . . . . . . . . . . . . . . . . . . .
4.
Ecotoxicity of illicit drugs . . . . . . . . . . . . . . . . .
5.
Methodology used to analyse illicit drugs in environment . .
6.
Conclusion. . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1080
1079
1080
1081
1081
1084
1084
1084
1084
1087
1088
1090
1090
1090

Corresponding authors at: Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, Adelaide, South Australia 5095, Australia.
Tel.: + 61 8 83025041; fax: + 61 883023057.
E-mail addresses: Megharaj.Mallavarapu@unisa.edu.au (M. Megharaj), Ravi.Naidu@crccare.com (R. Naidu).
0048-9697/$ see front matter 2012 Published by Elsevier B.V.
doi:10.1016/j.scitotenv.2012.05.086

1080

R. Pal et al. / Science of the Total Environment 463464 (2013) 10791092

1. Introduction
Drug abuse is a global problem with signicant direct or indirect
adverse impacts on human health and social welfare (Grifths et al.,
2008; Sloan, 2008; Rieckermann and Christakos, 2008; EMCDDA,
2007). Illicit drugs are those for which nonmedical use is prohibited
by the national or international laws (Hall et al., 2008). Illicit drugs
fall into the categories of opioids, cocaine, cannabis, amphetaminetype substances (ATSs), and ecstasy-group substances (Hall et al.,
2008; UNODC, 2007). ATSs (largely amphetamine and methamphetamine) and ecstasy (3,4-methylenedioxymethamphetamine (MDMA))
currently demand the most attention by law enforcement agencies
(Grifths et al., 2008; EMCDDA, 2007; Logan, 2001). Globally, ATSs and
ecstasy are the second most commonly consumed illicit drugs after cannabis, and they are attractive to clandestine laboratory operators due to
the easy availability of the precursor chemicals and their ease of
manufacturing (EMCDDA, 2008; UNODC, 2008a). Although some notable exceptions have occurred in some critical areas, the global markets
for almost every kind of illicit drug showed signs of overall stabilization
in 20052006, in terms of cultivation, production or consumption
(UNODC, 2008b, 2007). However, the use of ATSs continued to exceed
that of heroin and cocaine combined (UNODC, 2008a), and millions of
individuals are reported to be current users of ATS drugs. In fact,
human use of these psychoactive substances is virtually universal
(Grifths et al., 2008).
The methods of administration of illicit drugs are generally oral,
intranasal (snorting powder), by needle injection, or by inhaling
smoke (EMCDDA, 2008; NIDA, 2008). Our environment is the ultimate destination for all these compounds following their metabolism
in the human body and/or accidental or deliberate disposal of illicit
drugs and associated compounds. In common with legal pharmaceuticals, a large proportion of the administered drug may be excreted as
the parent compound and/or metabolites, through human urine and
faeces, and discharged directly into the sewage system (Castiglioni
et al., 2007; Al-Rifai et al., 2007; Roberts and Thomas, 2006; Zuccato
et al., 2005; Daughton, 2001). Additionally, clandestine chemicals
(e.g., drugs, their precursors, by-products, etc.) are also illegally buried in soil, disposed of into sinks and toilets to nd their way into
sewerage systems and public wastewater treatment facilities, or
dumped in public solid waste facilities (Janusz et al., 2003; Scott et
al., 2003). These chemicals undergo diverse processes after their release into the environment, such as sorption, degradation, leaching,
and transport in surface runoff, and interactions with soils, sediments,
groundwater, surface water, with potential implications for humans
and wildlife. Some of the illicit drugs are comparatively more polar
than the pollutants of historic concern and not readily sorbed to
sub-soils, or other materials low in organic matter, and may enter
the surface or ground waters (Jones-Lepp et al., 2004). Cannabinoids
are highly hydrophobic and are found bound to sewage sludge solids
(Daz-Cruz et al., 2009). We reported the degradation pattern of certain parent drugs, precursor, and manufacturing by-products in soil
and their impact on soil microbiological properties (Pal et al., 2011,
2012; Janusz et al., 2003; Scott et al., 2003). Methamphetamine was
found to be relatively persistent with half-life values in soil up to
502 days (Pal et al., 2011).
The term emerging pollutants has been dened as substances that
are not presently known to cause impairments in water systems but
have characteristics such as the ability to bioaccumulate, persistence
in the environment, and toxicity that suggest that they could impact
the integrity of water (Boles and Wells, 2010). Illicit drugs (both plant
derived and synthetic drugs) are the latest group of emerging pollutants
identied in the aquatic environment demanding attention (Boleda et
al., 2009; Kasprzyk-Hordern et al., 2010). These compounds may have
potent pharmacological and biological activities and their presence in
surface waters even at low concentrations, together with the residues
of many therapeutic pharmaceuticals and other organic compounds,

may lead to unexpected pharmacological interactions causing toxic effects to aquatic organisms. In addition, they may cause a wide variety
of environmental and health problems (Zuccato et al., 2008;
Castiglioni et al., 2007; Al-Rifai et al., 2007; Pomati et al., 2006). Analysis
of illicit drugs in wastewater and surface water by means of mass spectrometry and the occurrence of these compounds in environmental waters have been reviewed by Castiglioni et al. (2008) and Postigo et al.
(2008a), respectively. However, the current state of knowledge on the
concentrations, frequency, and geographic distribution patterns of illicit
drugs in the environment (especially water bodies and ambient air) as
reported from various parts of the world has not yet been encapsulated
in a review article.
Water bodies can be considered to be the most susceptible environmental matrices for contamination by illicit drugs and associated compounds, just as they are for legal pharmaceuticals and personal care
products (PPCPs) after their ingestion and excretion, external application, or disposal (Daughton, 2001). Illicit drugs have also the potential
to escape to the atmosphere, but their determination has not attracted
attention. Illicit drugs are suspected to promote long term ill health
effects even when present at low concentrations in the ambient air
(Cecinato et al., 2010). Information on the worldwide prevalence of
illicit drugs is a prerequisite to identify and foster timely plans on
safe and appropriate control measures to prevent their spread in
the environment and to protect human and ecological health. The
aim of this review is to develop a critical overview of the occurrence
and concentrations of the different groups of illicit drugs in aquatic
systems (waste and surface waters) and ambient air worldwide
and their potential ecotoxicological impact on the environment.
2. The potential for distribution of illicit drugs and metabolites in
water
Illicit drugs and their metabolites are continuously discharged into
wastewaters due to human excretion after legal or illegal consumption
or occasional direct disposal of clandestine laboratory wastes into sewage systems (Gonzlez-Mario et al., 2012; Boles and Wells, 2010).
After their consumption, drugs are excreted unaltered and/or as metabolites in urine, faeces, saliva, and sweat and the process of excretion occurs consistently even when illicit drugs are administered via different
methods injecting, smoking, snorting, swallowing and so forth
(Verster, 2010; Vazquez-Roig et al., 2010; Prichard et al., in press). The
proportion of consumed drugs excreted unaltered and as their metabolites in urine and faeces can be summarized as follows: cocaine
(unaltered (19%); benzoylecgonine (3554%); ecgonine methyl ester
(3249%)); amphetamine (unaltered 3040%), methamphetamine
(unaltered 4362%); MDMA (unaltered 65%); heroin (excreted as morphine 42.5%); and THC (unaltered 6590% through faeces and 1025%
through urine) (van Nuijs et al., 2011a; Boles and Wells, 2010;
Gheorghe et al., 2008; Bischoff, 2007). Chiaia et al. (2008) and van
Nuijs et al. (2009a,b) reported that in urine, a large proportion (80%)
of cocaine can be accounted for in the form of benzoylecgonine and
ecgonine methyl ester with both excreted at higher concentration
than cocaine. Amphetamine group compounds are primarily excreted
as the intact drug (Boles and Wells, 2010) but the excretion rate can
change with the pH of urine of that particular user, route of intake,
and dose (van Nuijs et al., 2011a). Although amphetamine and methamphetamine are excreted mostly as unaltered drugs, metabolites of
these drugs are also excreted and several additional metabolites may
form during sewage treatment processes (Boles and Wells, 2010).
The residues of illicit drugs found in consumers' urine that enter
the sewage network with wastewater are only partially removed by
STPs (Zuccato and Castiglioni, 2009). In urine drugs are generally
detected in the ppm range, but in wastewater and surface waters
their concentration is much lower at ppb levels (Verster, 2010).
The decrease in concentration of illicit drugs and their metabolites
in sewage efuents and surface waters depend on the technologies

R. Pal et al. / Science of the Total Environment 463464 (2013) 10791092

used in various wastewater or sewage treatment plant processes


(WWTP/STP), concentrations of drugs, and the nature of the particular compound. For instance, the removal efciency of amphetamine
and methamphetamine strongly depended on the wastewater treatment technology followed at two treatment plants in Cilfynydd and
Coslech, as reported by Boles and Wells (2010). The WWTP at
Cilfynydd used trickling lter beds resulting in 70% removal of the
drugs, while the WWTP at Coslech recorded greater removal efciency (more than 85%) which may be due to the activated sludge treatment. Kasprzyk-Hordern et al. (2009) also reported that activated
sludge treatment removed 100% of amphetamine, cocaine, and
benzoylecgonine, while trickling lter beds showed 95% removal of
amphetamine, only 25% removal of cocaine, and no removal of
benzoylecgonine. The removal efciency of wastewater treatment
technologies also depends on the concentration load and molecular
nature of the drugs and their metabolites as reported by different research group, such as: cocaine (72100%), benzoylecgonine (83100%),
norbenzoylecgonine (65%), amphetamine (5299%), methamphetamine
(4499%), MDMA (4457%), MDA (60%), morphine (7298%), methadone (922%), EDDP (827%) and THC-COOH (1199%) (Zuccato and
Castiglioni, 2009; Bijlsma et al., 2009; Loganathan et al., 2009; HuertaFontela et al., 2008a). In general, Postigo et al. (2010) reported that
the removal efciency increased in the order of amphetamine like
compounds b cannabinoidsb opioids b cocainics. Thus, the potential for
entering the receiving waters depends largely on the removal technologies followed in the WWTP and the molecular nature of drugs and their
metabolites.
3. Illicit drugs in environment
3.1. Wastewater
The prevalence of illicit drug compounds (parent drugs and their
metabolites) in aquatic environments is of signicant interest to environmental scientists. The disposal or excretion of products of illicit
drugs consumed in a given area is mainly into local wastewater and
then on to receiving surface water, soil, and sediments (Castiglioni
et al., 2007; Zuccato et al., 2005). The detection of illicit drug residues
in wastewater is purported to provide evidence-based real-time information on the nature and magnitude of community-wide illicit
drug use (Castiglioni et al., 2008; Bones et al., 2007). As with prescription pharmaceuticals, contamination by illicit drug residues at very
low concentrations appears to be widespread in populated areas,
with potential risks for human health and the environment
(Castiglioni et al., 2007; Zuccato et al., 2008). The environmental
monitoring of illicit drugs in water bodies can be considered to be
very useful from two perspectives epidemiologists can assess the
nature and magnitude of drug abuse over time (Rieckermann and
Christakos, 2008), information on changes in drug abuse trend
(Terzic et al., 2010), and environmental scientists and policy makers
can implement control strategies to protect the environment from biologically active substances.
In contrast to legal pharmaceutical drugs, comprehensive information on the presence of illicit drugs in the aquatic systems is still very limited. Recently, a number of reports have revealed the presence of illicit
drugs in wastewaters from the United States (Jones-Lepp et al., 2004;
Chiaia et al., 2008; Loganathan et al., 2009; Bartelt-Hunt et al., 2009),
Canada (Metcalfe et al., 2010), Italy (Castiglioni et al., 2006, 2007;
Zuccato et al., 2005; Mari et al., 2009), Switzerland (Berset et al., 2010),
Germany (Hummel et al., 2006), Ireland (Bones et al., 2007), UK
(Kasprzyk-Hordern et al., 2008, 2009, 2010), Spain (Huerta-Fontela et
al., 2008a, 2007; Boleda et al., 2007, 2009; Postigo et al., 2008b, 2010,
2011; Bijlsma et al., 2009; Gonzlez-Mario et al., 2010, 2012; Bueno et
al., 2011; Pedrouzo et al., 2011), Belgium (Gheorghe et al., 2008; van
Nuijs et al., 2009a,b,c,d, 2011), France (Karolak et al., 2010), Croatia
(Terzic et al., 2010), and Australia (Irvine et al., 2011; Lai et al., 2011).

1081

The common metabolites of cocaine present in wastewater include


benzoylecgonine, norbenzoylecgonine, norcocaine, cocaethylene, and
ecgonine methyl ester (van Nuijs et al., 2011a). The presence of ecgonine
methyl ester in wastewater was rst reported by van Nuijs et al. (2009a).
In this article we cover the cocainics (cocaine and its metabolites, such
as benzoylecgonine, norbenzoylecgonine, norcocaine, cocaethylene),
opioids (morphine, 6-acetylmorphine, morphine-3-D-glucuronide,
methadone, and 2-ethylidine-1,5-dimethyl-3,3-diphenylpyrrolidine
(EDDP)), cannabinoids (9-tetrahydrocannabinol (THC)), amphetamine
and ecstasy group compounds (amphetamine, methamphetamine, 3,4methylenedioxy amphetamine (MDMA), 3,4-methylenedioxy amphetamine (MDA), 3,4-methylenedioxy ethylamphetamine (MDEA)).
The concentrations (in ng L 1) of the groups of illicit drugs in
wastewaters, as reported from around the world, are compiled in
Tables 1 and 2. We present the data as two categories of illicit drugs
cocainics, opioids, and cannabinoids (Table 1) and amphetamine and
ecstasy group compounds (Table 2). We provide the concentrations of
these compounds both in the inuents and efuents of wastewater
treatment plants (WWTPs) from several countries. The concentrations
in the inuents provide an indication on the likely drug use pattern in
the local community, while that in efuent reects the potential for
the contamination of the receiving water bodies. These compounds
are often only partially removed by the sewage treatment plants
(STPs) and enter the receiving water bodies depending on the removal
efciencies of the treatment plants (Huerta-Fontela et al., 2008a;
Zuccato et al., 2008; Buchberger, 2007), through run-off during wet
weather, landll seepage, aquifer recharge, and drainage from elds
irrigated with efuent (Boles and Wells, 2010; Jones-Lepp et al.,
2004). They may also bind to sewage sludge (biosolids) which may
then be applied to land in agricultural areas (Kaleta et al., 2006).
In Table 1, most of the available data are from European countries
(e.g., Italy, Switzerland, Spain, Belgium, UK, Ireland, and France) and
few from USA and Canada. Due to independent studies by the different research groups, we cannot make direct comparison on the spatial
or temporal pattern of these compounds for any particular country,
but the data provide snapshots on their occurrence. The reported
data on cocaine and its major metabolite benzoylecgonine in the inuents of WWTPs indicated higher concentrations in Spain, Italy,
and Switzerland, while the lowest concentrations were recorded for
France, USA, and Australia. The higher concentrations of the metabolite compared to the parent drug is in accordance with the known
metabolism of cocaine in humans (Zuccato et al., 2005). The substantially lower concentrations of most of the compounds in efuents
than inuents (Table 1) are due to the degradation and/or sorption
of those compounds during the wastewater treatment processes
(Castiglioni et al., 2006). The concentrations in efuents very frequently reported below the limit of quantication but signicant
quantities of cocaine and benzoylecgonine were present in efuents
in Spain and UK. Morphine was reported at relatively high concentrations both in inuents and efuents from Switzerland. The high morphine concentration in the STPs of Switzerland cannot be interpreted
directly as heavy consumption of heroin, as the usage of opiate alkaloids in pain management treatments, over the counter analgesics,
cough suppression preparations, and poppy seeds used in bakery
products might have been contributed (Berset et al., 2010).
The available occurrence levels of amphetamine and ecstasy-group
compounds in wastewaters are presented in Table 2. The prevalence
of methamphetamine and MDMA in the wastewater efuents was initially reported from the United States (Jones-Lepp et al., 2004). In line
with cocainics and opioids, the higher concentrations of amphetamine
in inuents were reported from UK and Spain, methamphetamine
from USA, and MDMA from Spain. The concentrations in efuents
were frequently below the LOQ. Bijlsma et al. (2009) reported the occurrence of amphetamine, MDA, and MDMA from a WWTP in Castellon
province in Spain at the level of 140015,380 ng L 1 (in inuent) and
21010,955 ng L 1 (in efuent). The average concentrations in inuent

1082

R. Pal et al. / Science of the Total Environment 463464 (2013) 10791092

Table 1
Concentration of cocainics, opioids, and cannabinoids in wastewater.
Compound

Country

Study site

Study period

Concentration (ng L 1)
Inuent

Cocaine

Italy

Switzerland
Italy/Switzerland
Spain

Belgium

UK

Benzoylecgonine

Ireland
France
Croatia
USA
Canada
Italy

Switzerland
Italy/Switzerland
Spain

Germany
Belgium

UK

Ecgonine methyl ester


Norbenzoylecgonine

Ireland
France
Croatia
USA
Canada
Australia
Belgium
Italy
Switzerland
Italy/Switzerland

Cagliari
Latina
Cuneo
Varese
Milan
WWTPs at Florence
Lugano
STPs at Bern, Basel, Geneva, Lucern, Zurich
42 different towns in NE-Spain
Catalonia in NE-Spain
STPs located at east coast
7 different STPs
STP that gives service only to penal complex
WWTP in Castelln province
5 STPs located in NW Spain
STPs located in NW Spain
STP at Almera
WWTPs in Flanders
11 different WWTP
30 different WWTP
37 different WWTP
41 different WWTP
WWTP in Brussel-Noord
WWTP Brussels
Cilfynydd
WWTP Cilfynydd
WWTP Coslech
Ringsend, Shanganagh, Leixlip, Navan
WWTP at different suburbs of Paris
WWTP at city of Zagreb
WWTPs around US
WWTPs serving three Canadian cities
Cagliari
Latina
Cuneo
Varese
Milan
WWTPs at Florence
Lugano
STPs at Bern, Basel, Geneva, Lucern, Zurich
42 different towns in NE-Spain
Catalonia in NE-Spain
STPs located at east coast
7 different STPs
STP that gives service only to penal complex
WWTP in Castelln province
5 STPs located in NW Spain
STPs located in NW Spain
STP at Almera
STP in Vila-Seca
12 German STPs
WWTPs in Flanders
11 different WWTP
30 different WWTP
37 different WWTP
41 different WWTP
WWTP in Brussel-Noord
WWTP Brussels
Cilfynydd
WWTP Cilfynydd
WWTP Coslech
Ringsend, Shanganagh
WWTP at different suburbs of Paris
WWTP at city of Zagreb
WWTPs around US
WWTPs serving three Canadian cities
Metropolitan WWTPs in South Australia
11 different WWTP
Milan
Lugano

2004

Feb 2006
Jul 2006Jun 2007
Mar 2006
JulOct 2009
Apr 2006Jan 2007
AprSep 2006
Jul 2007
Oct 2007Jul 2008
Jun 2008Jan 2009
JunJul 2008
Feb 2011
MayJun 2010
Feb 2006Sept 2007
Aug 2007Jan 2008
20072008
20072008
20072008
Feb 2008
Mar 2009Jan 2010

Nov 2006
MarSep 2009
Oct 2008Aug 2009
2004

Feb 2006
Jul 2006Jun 2007
Mar 2006
JulOct 2009
Apr 2006Jan 2007
AprSep 2006
Jul 2007
Oct 2007Jul 2008
Jun 2008Jan 2009
JunJul 2008
Feb 2011
MayJun 2010
Nov 2009
Mar and Nov 2005
Feb 2006Sept 2007
Aug 2007Jan 2008
20072008
20072008
20072008
Feb 2008
Mar 2009Jan 2010

Nov 2006
MarSep 2009
Oct 2008Aug 2009
Apr 2009Oct 2009
Aug 2007Jan 2008
Feb 2006
Mar 2006

83
76
120
42
421.4
50
218.4
248
2001000c
44700c
79
592
384d
128
608
163
179
474
205
126
189
153
218
346
329
526
521
207
489
4.8282c
52d
235
209823c
640
420
750
390
1132.1
127
547.4
604
2001000d
97500c
810
2149
1310d
556
4750
907
447
2541
78
753
375
485
510
603
831
645
1229
992
1082
290
64849c
178d
1131
2872624c
52
89
36.6
18.8
436.6c

Efuent

Reference
no.a
[1]

b 0.99(LOQb)
10.7
b 15(LOQ)
1100d
17
57
16.8d
540
52
26.55
171

149
128
b 1(LOQ)
93.3
1.25.3c
25d
b 20(LOQ)530c

b 0.92(LOQ)
100.3
96
11500c
216
155
115d
3425
407
189
1010
914
49

1597
1091
13
26.5
7.9149c
79d
62775c

b 0.56(LOQ)
7.5

[2]
[3]
[2]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[26]
[27]
[28]
[12]
[13]
[14]
[15]
[16]
[14]
[29]
[17]
[18]
[18]
[19]
[20]
[30]
[21]
[22]
[1]
[1]
[1]
[1]
[2]
[3]
[2]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[26]
[27]
[28]
[31]
[23]
[12]
[13]
[14]
[15]
[16]
[14]
[29]
[17]
[18]
[18]
[19]
[20]
[30]
[21]
[22]
[24]
[13]
[2]
[2]
[5]

R. Pal et al. / Science of the Total Environment 463464 (2013) 10791092

1083

Table 1 (continued)
Compound

Norbenzoylecgonine
Norcocaine

Cocaethylene

Morphine

Country

Spain
USA
Italy
Switzerland
Italy/Switzerland
USA
Italy
Switzerland
Italy/Switzerland
Spain

Italy
Switzerland
Italy/Switzerland
Germany
Spain

6-Acetylmorphine

Ireland
Croatia
Italy
Switzerland
Italy/Switzerland
Spain

Morphine-3-D-glucuronide
Methadone

Belgium
Croatia
Italy
Switzerland
Italy
Switzerland
Italy/Switzerland
Germany
Spain

Belgium

EDDP

Croatia
USA
Italy
Switzerland
Italy/Switzerland
Spain

Belgium

9-tetrahydrocannabinol

Ireland
Croatia
Italy
Switzerland
Italy/Switzerland
Spain

Study site

Study period

WWTP in Castelln province


WWTPs around US
Milan
Lugano

JunJul 2008
Feb 2006
Mar 2006

WWTPs around US
Milan
Lugano

Feb 2006
Mar 2006

STPs located at east coast


7 different STPs
WWTP in Castelln province
Milan
WWTPs at Florence
Lugano
STPs at Bern, Basel, Geneva, Lucern, Zurich

Jul 2007
Oct 2007Jul 2008
Jul 2008
Feb 2006
Jul 2006Jun 2007
Mar 2006
JulOct 2009

12 German STPs
WWTP
WWTPs in NE-Spain
STPs located at east coast
7 different STPs
STP that gives service only to penal complex
5 STPs located in NW Spain
STPs located in NW Spain
STP at Almera
STP in Vila-Seca
Catalonia in NE-Spain
Swords, Navan
WWTP at city of Zagreb
Milan
Lugano
STPs at Bern, Basel, Geneva, Lucern, Zurich

Mar and Nov 2005


MarJul 2007
MarMay 2007
Jul 2007
Oct 2007Jul 2008
Jun 2008Jan 2009

7 different STPs
STP that gives service only to penal complex
WWTP Brussels
WWTP at city of Zagreb
Milan
Lugano
Milan
Lugano
STPs at Bern, Basel, Geneva, Lucern, Zurich

Oct 2007Jul 2008


Jun 2008Jan 2009
Mar 2009Jan 2010
MarSep 2009
Feb 2006
Mar 2006
Feb 2006
Mar 2006
JulOct 2009

WWTP
WWTPs in NE-Spain
STP that gives service only to penal complex
Catalonia in NE-Spain
STP at Almera
STPs located in NW Spain
11 different WWTP
WWTP Brussels
WWTP at city of Zagreb
WWTPs around US
Milan
Lugano
STPs at Bern, Basel, Geneva, Lucern, Zurich

MarJul 2007
MarMay 2007
Jun 2008Jan 2009
AprMay 2007
MayJun 2010
Feb 2011
Aug 2007Jan 2008
Mar 2009Jan 2010
MarSep 2009
Feb 2006
Mar 2006
JulOct 2009

WWTPs in NE-Spain
STP that gives service only to penal complex
Catalonia in NE-Spain
STP at Almera
STPs located in NW Spain
11 different WWTP
WWTP Brussels
Ringsend, Swords, Leixlip, Navan
WWTP at city of Zagreb
Milan
Lugano

MarMay 2007
Jun 2008Jan 2009
AprMay 2007
MayJun 2010
Feb 2011
Aug 2007Jan 2008
Mar 2009Jan 2010
Nov 2006
MarSep 2009
Feb 2006
Mar 2006

WWTPs in NE-Spain
Catalonia in NE-Spain
STPs located in NW Spain
7 different STPs

MarMay 2007
AprMay 2007
Feb 2011
Oct 2007Jul 2008

Feb 2011
MayJun 2010
Nov 2009
AprMay 2007
Nov 2006
MarSep 2009
Feb 2006
Mar 2006
JulOct 2009

Concentration (ng L 1)
Inuent

Efuent

290
75.2
13.7
4.3
436.6c
19.5
11.5
5.9
436.6c
78.3
18.1d
150
83.3
12.3
204.4
1007
80200c
310d
300d
54.1
91.8
94.4d
1346
137
21
152

90

25.5278
287d
11.8
10.4
38
510c
2.7d
63
13
12d
2.5
18.1
11.6
49.7
112
1090c
88d
12.7
4704
3.41531
45
28.7
19.1
54
55d
33.7
19.8
91.3
315
1090c
19.7
9262
3.31029
138
40.44
36.8
109
136d
62.7
91.2
6090c
63.8
11.3127
126
18.0d

b 1.92(LOQ)
0.7

b 0.95(LOQ)
0.2
3.6
1.5d
80
b 3.95(LOQ)
55.4
929
40d
25d
51
20.5
46.4d
102
73
545
1281.1
663
53d
b 5.3(LOQ)
b 5.3(LOQ)
b 5(LOQ)

1.8d
b 0.63(LOQ)
b 0.63(LOQ)
9.1
36.2
65
87d
11.4
3.4732
18
17.6

36d
22.6
72.1
294
22.4
2.71150
64
27.45

82.5
124d
b 1.75(LOQ)
7.2
39.2
4.2d
32.2
7.9d

Reference
no.a
[11]
[21]
[2]
[2]
[5]
[21]
[2]
[2]
[5]
[8]
[9]
[11]
[2]
[3]
[2]
[4]
[5]
[23]
[33]
[25]
[8]
[9]
[10]
[26]
[27]
[28]
[31]
[32]
[19]
[30]
[2]
[2]
[4]
[5]
[9]
[10]
[29]
[30]
[2]
[2]
[2]
[2]
[4]
[5]
[33]
[25]
[10]
[32]
[28]
[27]
[13]
[29]
[30]
[21]
[2]
[2]
[4]
[5]
[25]
[10]
[32]
[28]
[27]
[13]
[29]
[19]
[30]
[2]
[2]
[5]
[25]
[32]
[27]
[9]

1084

R. Pal et al. / Science of the Total Environment 463464 (2013) 10791092

were 1400, 1690, and 15,380 ng L 1 for amphetamine, MDA, and


MDMA respectively, while the same in efuent were 210, 680, and
10,955 ng L 1. The high level of amphetamine and especially MDMA
in this study was ascribed to the widespread consumption of these
drugs at a special music event during the study period. At the Cilfynydd
WWTP in UK, amphetamine was recorded in inuents and efuents at
concentrations of 5236 and 127 ng L 1 respectively, while in further
studies the same were 4310 and 201 ng L 1 in Cilfynydd WWTP, and
1196 and 2 ng L 1 in Coslech WWTP (Kasprzyk-Hordern et al., 2008,
2009). The concentration of amphetamine in the inuent samples
from Cilfynydd is remarkably higher than the reports made from
other European countries indicating the possibility of some direct discharge of the compound into the sewage system by the local community served by this WWTP.

of cocaine and benzoylecgonine in surface waters was reported at relatively higher concentrations from Spain, Belgium, and Italy. The concentrations of amphetamine and MDMA were recorded higher in the
surface waters from Spain while methamphetamine was higher in
USA. Although the concentrations of different drugs and their metabolites in surface waters are in the few nanogram per litre range, their
possible effects on wildlife and human health cannot be disregarded
especially on vulnerable populations (Valcrcel et al., 2012). The concentrations of some illicit drugs in natural waters occur at similar
level to other emerging contaminants (e.g., psychiatric drug carbamazepine and the anti-inammatory diclofenac) leading to their inclusion in the list of priority substances of the European Union
Water Framework Directive (Gonzlez-Mario et al., 2010).
3.3. Groundwater and drinking water

3.2. Surface water


Illicit drugs like pharmaceuticals reach surface waters unaltered or
slightly transformed via wastewater efuents from WWTPs (Boleda
et al., 2009, 2011). The illicit drugs and metabolites are generally
very recalcitrant to elimination by physico-chemical and biological
treatment at conventional STPs, especially MDMA (Valcrcel et al.,
2012). Wastewater treatment is only partially effective in removing
pharmaceutically active compounds and therefore efforts have been
made to improve sewage treatments with a tertiary step to efciently
remove all the organic contaminants by advanced oxidization process, ozonation, osmosis, etc. However, most STPs do not include
this treatment due to high cost, which means release of illicit drugs
and metabolites into surface waters and even in drinking waters
(Pedrouzo et al., 2011; Terzic et al., 2010; Valcrcel et al., 2012). The
removal efciencies of STPs for the different compounds vary signicantly and more uniform pattern have been recorded over time for
easily degradable compounds; the removal efciency also varied
with season reecting the inuence of temperature on biotransformation process in sewage treatment (Terzic et al., 2010). The level
of water contamination due to WWTP efuent discharge and their
fate in aqueous environment depend on physico-chemical properties
of pollutants, technology implemented in WWTPs, and climatic conditions such as dilution of wastewater efuent, rainfall, temperature
and level of sun light (Kasprzyk-Hordern et al., 2009).
Thus, illicit drugs and their metabolites are detected in the aquatic
environment (e.g., rivers, lakes, and groundwater) due to their incomplete removal during wastewater treatment and/or by discharge
of manufacturing residues (Al-Rifai et al., 2007; Roberts and
Thomas, 2006; Heberer, 2002). A number of studies have been conducted in different parts of the world to measure concentration levels
of illicit drugs in surface waters, including: Italy (Zuccato et al., 2008,
2005), Germany (Hummel et al., 2006), Ireland (Bones et al., 2007),
UK (Kasprzyk-Hordern et al., 2008, 2009), and Spain (HuertaFontela et al., 2008b, 2007; Boleda et al., 2007, 2009; Vazquez-Roig
et al., 2010; Postigo et al., 2010; Gonzlez-Mario et al., 2010;
Bueno et al., 2011; Valcrcel et al., 2012), Belgium (Gheorghe et al.,
2008; van Nuijs et al., 2009c,d), Switzerland (Berset et al., 2010),
and the USA (Bartelt-Hunt et al., 2009). We have presented the concentration of cocainics, opioids, and cannabinoids in Table 3 and for
amphetamine and ecstasy group compounds in Table 4. The presence

A major concern about the presence of illicit drugs and metabolites in the environment is that drinking water treatment plants
(DWTPs) cannot adequately treat surface or groundwater before it
is supplied as drinking water to the community (Boleda et al., 2009;
Valcrcel et al., 2012). At present there is little information dealing
with the presence of illicit drugs and metabolites in drinking water;
a few recent reports from Spain deal with this issue (Huerta-Fontela
et al., 2008b; Boleda et al., 2009, 2011; Valcrcel et al., 2012) and
groundwater (Jurado et al., 2012) as presented in Table 5.
The case study on Barcelona urban groundwater showed relatively
higher frequencies of detection and concentrations for cocaine,
MDMA, and methadone among different chemical classes of drugs
and metabolites (Jurado et al., 2012). The removal efciency in conventional drinking water treatment showed complete removal for almost all the illicit drugs and metabolites with few exceptions for
benzoylecgonine, methadone, and EDDP (Huerta-Fontela et al.,
2008b; Boleda et al., 2009). However, cocaine, benzoylecgonine,
methadone and its metabolite EDDP were frequently detected in tap
water (Boleda et al., 2011; Valcrcel et al., 2012).
3.4. Sewage sludge
The illicit drugs in sewage sludge, bio-solids, and sediments have
received little attention. First reports on the presence of amphetamine (5300 g kg 1) in sewage sludge of Austria were reported
by Kaleta et al. (2006) and methamphetamine (4 g kg 1 dry
weight) in the bio-solids from Los Angeles, USA by Jones-Lepp and
Stevens (2007). Sorption of illicit drugs in sediments was rst
reported by Wick et al. (2009), the sorption coefcients (Kd,
L kg 1) of morphine and methadone were recorded at 12 and 76. Although there is no report on the occurrence of cannabinoids in sewage sludge, they are likely to be found bound to sewage sludge due
to their high human consumption rate and high hydrophobicity
(Daz-Cruz et al., 2009).
3.5. Air
Illicit drugs have the potential to escape to the ambient air in powder
form during consumption (e.g., cocaine) or handling and as smoke during consumption (e.g., cannabis, methylamphetamine or heroin)

Note to Table 1:
a
Reference no.: [1] Zuccato et al. (2005), [2] Castiglioni et al. (2006), [3] Mari et al. (2009), [4] Berset et al. (2010), [5] Castiglioni et al. (2007), [6] Huerta-Fontela et al. (2008a),
[7] Huerta-Fontela et al. (2007), [8] Postigo et al. (2008b), [9] Postigo et al. (2010), [10] Postigo et al. (2011), [11] Bijlsma et al. (2009), [12] Gheorghe et al. (2008), [13] van Nuijs
et al. (2009a), [14] van Nuijs et al. (2009d), [15] van Nuijs et al. (2009c), [16] van Nuijs et al. (2009b), [17] Kasprzyk-Hordern et al. (2008), [18] Kasprzyk-Hordern et al. (2009),
[19] Bones et al. (2007), [20] Karolak et al. (2010), [21] Chiaia et al. (2008), [22] Metcalfe et al. (2010), [23] Hummel et al. (2006), [24] Irvine et al. (2011)), [25] Boleda et al.
(2007), [26] Gonzlez-Mario et al. (2010), [27] Gonzlez-Mario et al. (2012), [28] Bueno et al. (2011), [29] van Nuijs et al. (2011b), [30] Terzic et al. (2010), [31] Pedrouzo
et al. (2011), [32] Boleda et al. (2009), [33] Wick et al. (2009).
b
Limit of quantication.
c
Range.
d
Median value.

R. Pal et al. / Science of the Total Environment 463464 (2013) 10791092

1085

Table 2
Concentration of amphetamine and ecstasy group compounds in wastewater.
Compound

Amphetamine

Country

Italy
Spain

UK

Belgium

Methamphetamine

Croatia
USA
Canada
Italy
Spain

Belgium
USA

MDA

Canada
Australia
Italy
Switzerland
Spain

MDMA

USA
Italy
Switzerland
Spain

Belgium
Croatia
UK
USA

MDEA

Canada
Australia
Italy
Spain

Study site

Milan
Catalonia in NE-Spain
42 different towns in NE-Spain
STPs located at east coast
7 different STPs
STP that gives service only to penal complex
WWTP in Castelln province
STP at Almera
STPs located in NW Spain
Cilfynydd
WWTP Cilfynydd
WWTP Coslech
4 different WWTPs
11 different WWTP
WWTP Brussels
WWTP at city of Zagreb
WWTPs around US
WWTPs serving three Canadian cities
Milan
42 different towns in NE-Spain
STPs located at east coast
7 different STPs
STP that gives service only to penal complex
STP at Almera
11 different WWTP
WWTP Brussels
Nevada
WWTPs around US
Murray WWTP
Omaha, NE
WWTPs serving three Canadian cities
Metropolitan WWTPs in South Australia
Milan
Lugano
42 different towns in NE-Spain
WWTP in Castelln province
STP at Almera
WWTPs around US
Milan
Lugano
STPs at Bern, Basel, Geneva, Lucern, Zurich
Catalonia in NE-Spain
42 different towns in NE-Spain
STPs located at east coast
7 different STPs
STP that gives service only to penal complex
WWTP in Castelln province
STPs located in NW Spain
11 different WWTP
WWTP Brussels
WWTP at city of Zagreb
4 different WWTPs
South Carolina
WWTPs around US
WWTPs serving three Canadian cities
Metropolitan WWTPs in South Australia
Milan
Catalonia in NE-Spain
42 different towns in NE-Spain

Study period

Feb 2006
AprSep 2006
Apr 2006Jan 2007
Jul 2007
Oct 2007Jul 2008
Jun 2008Jan 2009
Jul 2008
MayJun 2010
Feb 2011

Aug 2007Jan 2008


Mar 2009Jan 2010
MarSep 2009
Oct 2008Aug 2009
Feb 2006
Apr 2006Jan 2007
Jul 2007
Oct 2007Jul 2008
Jun 2008Jan 2009
MayJun 2010
Aug 2007Jan 2008
Mar 2009Jan 2010
June 2002Feb 2003
AugDec 2006
AugOct 2006
Oct 2008Aug 2009
Apr 2009Oct 2009
Feb 2006
Mar 2006
Apr 2006Jan 2007
Jul 2008
MayJun 2010
Feb 2006
Mar 2006
JulOct 2009
AprSept 2006
Apr 2006Jan 2007
Jul 2007
Oct 2007Jul 2008
Jun 2008Jan 2009
Jul 2008
Feb 2011
Aug 2007Jan 2008
Mar 2009Jan 2010
MarSep 2009

Concentration (ng L 1)
Inuent

Efuent

14.7
15
3688c
25.9
148d
97
1400
496
64.1
5236
4310
1196
85.9
206
59
7.3d
206
b 3(LOQ)25c
16.2
3277c
8.2
4.6d
87
614
3.5
3.3

b 2.8(LOQb)
b 1(LOQ)
4210c
1.8
25.7d

1.0d
b 1(LODe)14c
3.5
390c
3.1
1.3d

1.05
800
18
b 7(LOQ)65c
587
4.6
b 8.7(LOQ)
3266c
1690
266
5.0
14.2
13.6
26
49
2598c
135
20.4d
61
15,380
25.6
34.5
10.5
3.4d
6.4

July 2002
Oct 2008Aug 2009
Apr 2009Oct 2009
Feb 2006
AprSep 2006
Apr 2006Jan 2007

210
225
14.2
127
201
2

23.2
935
187
1.5
28
6114c

350
b 2(LOD)95c
1.1
0.9
1200c
680

4.4
5.1
b 11(LOQ)
41
2267c
132
12.7d
10,955

2.0d
6.7
0.5
b 3(LOD)32
b 1.64(LOQ)
b 2.1(LOQ)
12

Reference
no.a
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[19]
[20]
[8]
[9]
[9]
[10]
[11]
[21]
[22]
[12]
[13]
[1]
[2]
[4]
[5]
[6]
[19]
[11]
[21]
[14]
[12]
[15]
[16]
[13]
[17]
[1]
[1]
[2]
[7]
[19]
[12]
[1]
[1]
[18]
[2]
[3]
[4]
[5]
[6]
[7]
[20]
[11]
[21]
[22]
[10]
[14]
[12]
[13]
[17]
[1]
[2]
[3]

a
Reference no.: [1] Castiglioni et al. (2006), [2] Huerta-Fontela et al. (2007), [3] Huerta-Fontela et al. (2008a), [4] Postigo et al. (2008b), [5] Postigo et al. (2010), [6] Postigo et al. (2011),
[7] Bijlsma et al. (2009), [8] Kasprzyk-Hordern et al. (2008), [9] Kasprzyk-Hordern et al. (2009), [10] Kasprzyk-Hordern et al. (2010), [11] van Nuijs et al. (2009a), [12] Chiaia et al. (2008),
[13] Metcalfe et al. (2010), [14] Jones-Lepp et al. (2004), [15] Loganathan et al. (2009), [16] Bartelt-Hunt et al. (2009), [17] Irvine et al. (2011), [18] Berset et al. (2010), [19] Bueno et al.
(2011), [20] Gonzlez-Mario et al. (2012), [21] van Nuijs et al. (2011b), [22] Terzic et al. (2010).
b
Limit of quantication.
c
Range.
d
Median value.
e
Limit of detection.

(Daughton, 2011a; Viana et al., 2010). The illicit drugs and their metabolites present in the atmosphere are primarily associated with particulates due to their physico-chemical properties (low vapour pressures,
high to medium polarity, weak alkalinity, and molecular weight range

between 135 and 360 g mol 1) and have been recognised as potentially useful matrix to investigate the illicit drug consumption pattern
(Postigo et al., 2009; Viana et al., 2010). However, the atmospheric
levels of illicit drugs may be more transient and variable than levels in

1086

R. Pal et al. / Science of the Total Environment 463464 (2013) 10791092

Table 3
Concentration of cocainics, opioids, and cannabinoids in surface water.
Compound

Country

Name of river

Study site

Study period

Concentration
(ng L 1)

Reference no.a

Cocaine

Italy

Po
Po
Olona
Lambro
Arno
Thames

2004
2006
2006
2006
2006
Oct 2005

1.2
0.5
44
15
1.7
4.7

[1]
[2]
[2]
[2]
[2]
[2]

Spain

Llobregat

Mezzano, Pavia
Mezzana, Monticelli, Piacenza, Cremona
Downstream of Varese STP
Near its entrance into River Po
Rignano, Limite, Castelfranco, Pisa
New bridge, Shillingford bridge, Chiswick bridge,
House of Parliament, Tilbury of London
Intake of drinking water treatment plant located
in the Llobregat river basin
Intake of a Drinking water treatment plant
Natural park of L'Albufera of Valencia
15 different location along the river basin

May 2006Apr 2007

23.8

[3]

Sep 2006
Apr 2008
Oct 2007Jul 2008

Located in the centre of Spain (Madrid)

Jun 2010
JunJul 2007
20072008
20072008

Nov 2006
Mar 2010
2004
2006
2006
2006
2006
Oct 2005

6
0.5
1.4b
30
44
15.3
22.4
11.9
2
2
29
0.4
25
3.7
183
50
21.8
11.2

[4]
[5]
[6]
[16]
[17]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[1]
[2]
[2]
[2]
[2]
[2]

May 2006Apr 2007

64

[3]

Sep 2006
Apr 2008
Oct 2007Jul 2008

77
7.4
11.4b
316
142
29.2b
96
84
48.5
3b
85
55
12
1.6
0.3
8.4
3.2
1.6
7.39b
3.6
0.4
0.1
1.3
0.2
0.1
0.3b
38
3.5
3
15.8

[4]
[5]
[6]
[16]
[17]
[18]
[7]
[8]
[9]
[14]
[10]
[11]
[11]
[13]
[2]
[2]
[2]
[2]
[18]
[2]
[2]
[2]
[2]
[2]
[2]
[6]
[2]
[2]
[2]
[2]

10b
5.5
6.0
4.1
9.8b
89
16
1.74b
2.2
0.5
8.6
3.4

[14]
[15]
[5]
[19]
[6]
[16]
[17]
[18]
[13]
[2]
[2]
[2]

Llobregat
Ebro
Sar
Henares
Belgium

UK

Benzoylecgonine

Ireland
Switzerland
Italy

Spain

Taff
Taff
Broadmeadow, Liffey
Po
Po
Olona
Lambro
Arno
Thames
Llobregat
Llobregat
Ebro
Sar
Henares
Tagus

Different rivers and brooks


28 different rivers and brooks (N = 43)
Abcercynon, Pontypridd, Trefforest estate
Abcercynon and Pontypridd
22 rivers or creek
Mezzano, Pavia
Mezzana, Monticelli, Piacenza, Cremona
Downstream of Varese STP
Near its entrance into River Po
Rignano, Limite, Castelfranco, Pisa
New bridge, Shillingford bridge, Chiswick bridge,
House of Parliament, Tilbury of London
Intake of drinking water treatment plant located
in the Llobregat river basin
Intake of a Drinking water treatment plant
Natural park of L'Albufera of Valencia
15 different location along the river basin
Located in the centre of Spain (Madrid)

Belgium
Different rivers and brooks
28 different rivers and brooks (N = 43)
Germany
UK

Norbenzoylecgonine

Switzerland
Italy

Norcocaine

Spain
Italy

Cocaethylene

Italy

Morphine

Spain
Italy

Germany
Spain

Methadone

Switzerland
Italy

Rhine, Mosel, Lahn


Taff
Taff
Ely
Po
Olona
Lambro
Arno
Tagus
Olona
Lambro
Arno
Olona
Lambro
Arno
Ebro
Olona
Lambro
Arno
Thames
Rhine, Saar, Mosel, Lahn
Llobregat
Llobregat
Llobregat
Ebro
Sar
Henares
Tagus
Po
Olona
Lambro

Abcercynon, Pontypridd, Trefforest estate


Abcercynon and Pontypridd
Talbot green and Peterson-super-Ely
22 rivers or creek
Mezzana, Monticelli, Piacenza, Cremona
Downstream of Varese STP
Near its entrance into River Po
Rignano, Limite, Castelfranco, Pisa
Downstream of Varese STP
Near its entrance into River Po
Rignano, Limite, Castelfranco, Pisa
Downstream of Varese STP
Near its entrance into River Po
Rignano, Limite, Castelfranco, Pisa
15 different location along the river basin
Downstream of Varese STP
Near its entrance into River Po
Rignano, Limite, Castelfranco, Pisa
New bridge, Shillingford bridge, Chiswick bridge,
House of Parliament, Tilbury of London
Intake of a Drinking water treatment plant
Natural park of L'Albufera of Valencia
15 different location along the river basin
Located in the centre of Spain (Madrid)
22 rivers or creek
Mezzana, Monticelli, Piacenza, Cremona
Downstream of Varese STP
Near its entrance into River Po

Jun 2010
Jun 2010
JunJul 2007
20072008
20072008
Mar and Nov 2005

Mar 2010
2006
2006
2006
2006
Jun 2010
2006
2006
2006
2006
2006
2006
Oct 2007Jul 2008
2006
2006
2006
Oct 2005
Mar and Nov 2005
MarMay 2007
Apr 2008
2007
Oct 2007Jul 2008
Jun 2010
Jun 2010
Mar 2010
2006
2006
2006

R. Pal et al. / Science of the Total Environment 463464 (2013) 10791092

1087

Table 3 (continued)
Compound

Country

Methadone
Spain

EDDP

Switzerland
Italy

Spain

Name of river

Study site

Study period

Concentration
(ng L 1)

Reference no.a

Arno
Llobregat
Llobregat
Henares
Tagus

Rignano, Limite, Castelfranco, Pisa


Intake of a Drinking water treatment plant

2006
MarMay 2007
2007
Jun 2010
Jun 2010
Mar 2010
2006
2006
2006
2006
MarMay 2007
2007
Jun 2010
Jun 2010
Mar 2010
2006
2006
2006
Oct 2005

4.8
6.4
2.4
7
2.58b
1.7
1
18
9.9
4.3
12.3
6.0
35
7.57b
4.9
0.3
3.7
0.5
1

[2]
[15]
[19]
[17]
[18]
[13]
[2]
[2]
[2]
[2]
[15]
[19]
[17]
[18]
[13]
[2]
[2]
[2]
[2]

MarMay 2007
Oct 2007Jul 2008

24
5.5b

[15]
[6]

Po
Olona
Lambro
Arno
Llobregat
Llobregat
Henares
Tagus

Switzerland
9-tetrahydrocannabinol

Po
Lambro
Arno
Thames
Spain

Llobregat
Ebro

Located in the centre of Spain (Madrid)


22 rivers or creek
Mezzana, Monticelli, Piacenza, Cremona
Downstream of Varese STP
Near its entrance into River Po
Rignano, Limite, Castelfranco, Pisa
Intake of a Drinking water treatment plant
Located in the centre of Spain (Madrid)
22 rivers or creek
Mezzana, Monticelli, Piacenza, Cremona
Near its entrance into River Po
Rignano, Limite, Castelfranco, Pisa
New bridge, Shillingford bridge, Chiswick bridge,
House of Parliament, Tilbury of London
Intake of a Drinking water treatment plant
15 different location along the river basin

a
Reference no.: [1] Zuccato et al. (2005), [2] Zuccato et al. (2008), [3] Huerta-Fontela et al. (2008b), [4] Huerta-Fontela et al. (2007), [5] Vazquez-Roig et al. (2010), [6] Postigo et al.
(2010), [7] Gheorghe et al. (2008), [8] van Nuijs et al. (2009d), [9] van Nuijs et al. (2009c), [10] Kasprzyk-Hordern et al. (2008), [11] Kasprzyk-Hordern et al. (2009), [12] Bones et al.
(2007), [13] Berset et al. (2010), [14] Hummel et al. (2006), [15] Boleda et al. (2007), [16] Gonzlez-Mario et al. (2010), [17] Bueno et al. (2011), [18] Valcrcel et al. (2012), [19] Boleda
et al. (2009).
b
Median value.

wastewater making it complex to use as a tool to detect drug abuse pattern (Daughton, 2011a).
The determination of illicit drugs and metabolites in the atmosphere
has not received much attention and the data are extremely scarce
worldwide. Reports are available in scientic literatures on the measurement of illicit drugs in ambient air only from the cities of Italy,
Spain, Portugal, Chile, Brazil, Serbia, and Algeria. Initially, Hannigan et
al. (1998) detected the presence of cocaine in outdoor air during a bioassay directed chemical analysis of Los Angeles airborne particulate
matter using a human cell mutagenicity assay. The available reports
on the concentration of illicit drugs and metabolites have been presented in Table 6. The samples collected from Algiers, Algeria and
Panevo, Serbia tested for cocaine were recorded below detection limit
(Cecinato et al., 2009a). The concentrations of benzoylecgonine, heroin,
6-acetylmorphine, 9-tetrahydrocannabinol (THC), amphetamine,
methamphetamine, and MDMA were generally recorded in low
pg m 3 range, but cocaine up to the low ng m 3 level was detected.
The results indicated the maximum occurrence of cocaine in the ambient
air followed by THC. The concentrations of synthetic illicit drugs in ambient air are relatively low.
The objective of air monitoring is mainly to detect illicit drug
usage pattern rather than concern regarding public health impacts
because the cumulative lifetime doses (e.g., cocaine 0.3 mg), even
in contaminated areas, are much less than one drug dose (Cecinato
et al., 2010; Daughton, 2011a). However, possible health hazard derived from chronic exposure to such low ambient concentrations
and potential effects of short or medium term exposures on specic
risk groups (children, elderly, and asthmatics) needs attention
(Viana et al., 2011; Cecinato et al., 2011).
4. Ecotoxicity of illicit drugs
Illicit drugs are being continuously discharged into aquatic environment due to their high production and consumption and thus continuous monitoring of sewage efuents would minimize their undesirable
effects on environment (Valcrcel et al., 2012). Many reports are available on the occurrence level of illicit drugs in water worldwide, however,
the ecotoxicity of illicit drugs has received less attention compared to licit
pharmaceuticals especially with regard to low level mixed stressor

exposure, potential harmful effect on non-target aquatic systems, or


their bioconcentration in biota (Binelli et al., 2012; Daughton, 2011b).
Wastewaters are a major source of pharmaceuticals in the aquatic environment and thus biota are exposed to the unknown chronic effects of
these chemicals (Gagn et al., 2006). The presence of illicit drugs and
their metabolites needs attention from an ecotoxicological perspective
because their possible negative effect on aquatic organisms, biota and
the ecosystem might be comparable with therapeutic drugs (van Nuijs
et al., 2011b). Most illicit drugs (e.g., amphetamines and opiates) are chiral compounds and chirality of these compounds may be a major parameter determining their potency and possible toxicity (Kasprzyk-Hordern
et al., 2010).
The information on ecotoxicity of illicit drugs in the scientic literature is scant and not systematic. Only few reports are available until
now on ecotoxicity of amphetamine, cocaine, and morphine on aquatic
organisms. The toxicity of amphetamine sulfate to freshly isolated rainbow trout hepatocytes and Daphnia was reported and the results revealed relatively high toxicity among the 50 reference chemicals used
by the Multicentre Evaluation of In vitro Cytotoxicity (Lilius et al.,
1994). The behavioural screening of cocaine sensitivity in mutagenized
zebrash (Danio renio) showed defects resulting from mutation in distinct genes that affect dopaminergic signalling in the retina and brain
(Darland and Dowling, 2001). The study on cyto-genotoxic effect of cocaine on mollusk Zebra mussel (Dreissena polymorpha) showed signicant primary DNA damage, increase in micronucleated cells and
marked rise in apoptosis (Binelli et al., 2012). The immunotoxic effect
of morphine on freshwater mussel (Elliptio complanata) showed reduced
phagocytic and intracellular esterase activity, cell adherence, and lipid
peroxidation (Gagn et al., 2006). The pharmacokinetics of morphine
into winter ounder (Pseudopleuronectes americanus) and sea water acclimated rainbow trout (Oncorhynchus mykiss) was reported by measuring the change in plasma morphine concentration for 100 h (Newby et
al., 2006). This study showed signicant intra-specic variation between
shes and the metabolism of morphine in sh was approximately one
order of magnitude slower than it is in mammals and the differences
may be due to mass specic differences in cardiac output.
The only available report on ecotoxicity of illicit drugs on soil microbial quality indicated mostly stimulatory effect of methamphetamine
on dehydrogenase activity and insignicant toxicity on potential

1088

R. Pal et al. / Science of the Total Environment 463464 (2013) 10791092

Table 4
Concentration of amphetamine and ecstasy group compounds in surface water.
Compound

Country

Name of river

Study site

Study period

Concentration
(ng L 1)

Reference no.a

Amphetamine

Spain

Llobregat

Intake of drinking water treatment plant located


in the Llobregat river basin
Natural park of L'Albufera of Valencia
15 different location along the river basin
Located in the centre of Spain (Madrid)
Abcercynon, Pontypridd, Trefforest estate
Abcercynon and Pontypridd
Talbot green and Peterson-super-Ely
Downstream of Varese STP
Near its entrance into River Po
House of Parliament, Tilbury of London
Intake of drinking water treatment plant located
in the Llobregat river basin
15 different location along the river basin

May 2006Apr 2007

20

[1]

Apr 2008
Oct 2007Jul 2008
Jun 2010

2006
2006

3.38
6.8b
309
4
5
1
1.7
2.1

[2]
[3]
[9]
[4]
[5]
[5]
[6]
[6]

May 2006Apr 2007

1.3

[1]

Oct 2007Jul 2008


Jun 2010
AugOct 2006

0.4b
3.22b
16.6

[3]
[10]
[7]

2006
Oct 2005

1.2
3

[6]
[6]

May 2006Apr 2007

9.2

[1]

2006
2006
2006
2006
Oct 2005

0.2
1.7
1.1
1.0
3.6

[6]
[6]
[6]
[6]
[6]

May 2006Apr 2007

14.1

[1]

Sep 2006
Apr 2008
Oct 2007Jul 2008
Jun 2010

3
0.9
1.0b
2.07b

[8]
[2]
[3]
[10]

UK

Methamphetamine

Italy

Spain

Ebro
Henares
Taff
Taff
Ely
Olona
Lambro
Llobregat
Ebro
Tagus

USA
MDA

MDMA

Italy

Arno
Thames

Spain

Llobregat

Italy

Po
Olona
Lambro
Arno
Thames

Spain

Llobregat
Llobregat
Ebro
Tagus

Upstream and downstream of Loup, Big Blue,


Wood river, and Salt creek
Rignano, Limite, Castelfranco, Pisa
New bridge, Shillingford bridge, Chiswick bridge,
House of Parliament, Tilbury of London
Intake of drinking water treatment plant located
in the Llobregat river basin
Mezzana, Monticelli, Piacenza, Cremona
Downstream of Varese STP
Near its entrance into River Po
Rignano, Limite, Castelfranco, Pisa
New bridge, Shillingford bridge, Chiswick bridge,
House of Parliament, Tilbury of London
Intake of drinking water treatment plant located
in the Llobregat river basin
Intake of a Drinking water treatment plant
Natural park of L'Albufera of Valencia
15 different location along the river basin

a
Reference no.: [1] Huerta-Fontela et al. (2008b), [2] Vazquez-Roig et al. (2010), [3] Postigo et al. (2010), [4] Kasprzyk-Hordern et al. (2008), [5] Kasprzyk-Hordern et al. (2009),
[6] Zuccato et al. (2008), [7] Bartelt-Hunt et al. (2009), [8] Huerta-Fontela et al. (2007), [9] Bueno et al. (2011), [10] Valcrcel et al. (2012).
b
Median value.

nitrication activity of two South Australian soils up to 1000 g g 1


(Scott et al., 2003).
Thus, it is reasonable to assume from the available reports that the
stimulatory or inhibitory effects of illicit drugs depend on the chemical and the test organism.
5. Methodology used to analyse illicit drugs in environment
Development in analytical technology has allowed trace level determination of different illicit drugs and metabolites from various environmental matrices. This has aided in assessing the trend and
pattern of illicit drug abuse (known as sewage epidemiology), their
distribution pattern in waters, and potential impact on human health
and ecosystem. However, such assessment may be inuenced by the
efciency of the analytical technology employed for their determination. The screening of illicit drugs and metabolites in water has become widespread since the reports published on the presence of
methamphetamine and MDMA in wastewaters from USA (JonesLepp et al., 2004) and cocaine in Po River, Italy (Zuccato et al., 2005).
The four basic factors that affect the quality of environmental data
are sample collection, sample preservation, analysis, and recording;
improper actions in any one area may result in poor data from which
poor judgements might be drawn, for example with increasing accuracy
of chemical analytical techniques, inappropriate sampling increasingly
represents the major source of inaccuracy (Ort et al., 2010a). The
widely applied techniques for water analysis involve grab sampling
(Chiaia et al., 2008) and time integrated sampling (Jones-Lepp et al.,
2004) but Ort et al. (2010b) recommended ow proportional sampling
as best practice.

Both gas chromatography mass spectrometry (GC-MS) and liquid


chromatography mass spectrometry (LC-MS) have been used to detect illicit drugs, but solid phase extraction SPE (SPE by mixed reversed phase cation exchange cartridges using Oasis MCX, HLB or
Strata-XC TM sorbent) for sample preparation followed by high pressure liquid chromatography tandem mass spectrometry (LC-MS/MS)
has widely been accepted technique of choice for determination of illicit drugs and metabolites from environmental matrices (Castiglioni
et al., 2008). However, determination of illicit drugs and metabolites
in water by SPE, derivatisation and gas chromatography ion trap tandem mass spectrometry has also been proposed (Gonzlez-Mario et
al., 2010). The application of SPE and LC-MS/MS for simultaneous
analysis of a wide variety of illicit drugs (e.g., amphetamines,
cocainics, opioids, and cannabinoids) in wastewater was proposed
by Castiglioni et al. (2006). All these methods commonly used offline SPE; however, the limitations of this technique include low and
variable analyte recovery plus time and cost involved (Chiaia et al.,
2008). The rst fully automated method based on on-line SPELCMS/MS for the multianalyte determination of most relevant illicit
drugs and their metabolites was developed by Postigo et al.
(2008b). Chiaia et al. (2008) and Berset et al. (2010) showed the possibility of direct large volume injection eliminating the need for off- or
on-line SPE for the analysis of a wide range of illicit drugs in wastewater. A time-weighted polar organic chemical integrative sampler applying microliquid chromatography electrospray ion trap mass
spectrometry was described to detect illicit drugs in treated sewage
efuents (Jones-Lepp et al., 2004). An overview from published studies on sample preparation and LC methods for analysis of illicit drugs
and metabolites in waters has been reported (Castiglioni et al., 2008;

R. Pal et al. / Science of the Total Environment 463464 (2013) 10791092

1089

Table 5
Concentration of illicit drugs and their metabolites in groundwater and tap water.
Compound

Country

Study site

Study period

Concentration
(ng L 1)

Reference no.a

(a) Groundwater
Cocaine
Benzoylecgonine
Cocaethylene
Morphine
Methadone
EDDP
MDMA

Spain
Spain
Spain
Spain
Spain
Spain
Spain

Barcelona
Barcelona
Barcelona
Barcelona
Barcelona
Barcelona
Barcelona

MayDec
MayDec
MayDec
MayDec
MayDec
MayDec
MayDec

3.8
1.5
0.1
1.4
7.4
0.7
3.9

[1]

(b) Tap water


Cocaine

Spain

Different 43 cities
Cazalegas reservoir

20082009
Jun 2010

Different 43 cities
Cazalegas reservoir

20082009
Jun 2010

Different 43 cities
Different 43 cities
Cazalegas reservoir
DWTP from Toledo City

20082009
20082009
Jun 2010
Jun 2010

Different 43 cities
Cazalegas reservoir

20082009
Jun 2010

0.4
2.11
0.1
0.6
0.4
2.47
0.2
4.5
0.2
0.2
0.47
0.99
0.1
0.2
0.4
0.34
0.4
0.1
0.4

[2]
[3]
[2]
[2]
[2]
[3]
[2]
[2]
[2]
[2]
[3]
[3]
[2]
[2]
[2]
[3]
[2]
[2]
[2]

2010
2010
2010
2010
2010
2010
2010

Benzoylecgonine

Europe
Latin Americac
Spain

Cocaethylene
Methadone

Europeb
Latin Americac
Spain
Spain

EDDP

Europeb
Latin Americac
Spain
b

Europe
Japan
Latin Americac
a
b
c

Reference no.: [1] Jurado et al. (2012), [2] Boleda et al. (2011), [3] Valcrcel et al. (2012).
Includes large cities in Austria, France, Germany, Iceland, Slovakia, Switzerland, and United Kingdom.
Cities in Argentina, Brazil, Chile, Colombia, Panama, Peru, and Uruguay.

Table 6
Concentration of illicit drugs and their metabolites in ambient air.
Compound

Country

Study site

Study period

Concentration
(pg m 3)

Reference no.a

Cocaine

Italy

Different urban and semiurban areas of Rome


Rome, Bari, and Milan
Rome and Montelibretti
Rome and other cities
Ermesinde, Oporto
Santiago
Sao Paulo, Piracicaba, Araraquara, Ouro Preto
Barcelona and Madrid
Barcelona and Madrid
Barcelona and Madrid
Barcelona and Madrid
Barcelona, Madrid, and Corua
Barcelona and Madrid
Barcelona and Madrid
Barcelona and Madrid
Barcelona and Madrid
Barcelona, Madrid, and Corua
Rome
Montelibretti
Bari
Barcelona and Madrid
Barcelona and Madrid
Barcelona and Madrid
Barcelona and Madrid
Barcelona, Madrid, and Corua
Barcelona and Madrid
Barcelona and Madrid
Barcelona, Madrid, and Corua
Barcelona and Madrid
Barcelona and Madrid
Barcelona, Madrid, and Corua

20032006
2008
Sep 2007
2009
20062007
Jun 2007
20022003
Nov 2007Jan 2008
Sep 2007Jan 2008
Nov 2007Jan 2008
Sep 2007Jan 2008
20082009
Nov 2007Jan 2008
Sep 2007Jan 2008
Nov 2007Jan 2008
Sep 2007Jan 2008
20082009
SepOct 2008
SepOct 2008
Mar 2007
Nov 2007Jan 2008
Sep 2007Jan 2008
Nov 2007Jan 2008
Sep 2007Jan 2008
20082009
Nov 2007Jan 2008
Sep 2007Jan 2008
20082009
Nov 2007Jan 2008
Sep 2007Jan 2008
20082009

1098b
13267b
687b
9116b
148
2800
47590b
305.61
204480b
23.5
1429
b DL(2.49)29b
83.7
b DL84.0b
22.8
b DL22.8b
b DL(7.36)32b
44104b
3058b
39
33.2
2744b
2.02
1.42.3b
b DL(1.05)15b
3.49
0.93.5b
b DL(2.73)10b
2.90
b DL2.9b
b DL(1.26)5b

[1]
[4]
[5]
[6]
[4]
[4]
[4]
[2]
[7]
[2]
[7]
[8]
[2]
[7]
[2]
[7]
[8]
[3]
[3]
[3]
[2]
[7]
[2]
[7]
[8]
[2]
[7]
[8]
[2]
[7]
[8]

Portugal
Chile
Brazil
Spain
Benzoylecgonine

Spain

Heroin

Spain

6-Acetylmorphine

Spain

9-tetrahydrocannabinol

Italy

Spain
Amphetamine

Spain

Methamphetamine

Spain

MDMA

Spain

DL = Detection limit.
a
Reference no.: [1] Cecinato and Balducci (2007), [2] Postigo et al. (2009), [3] Balducci et al. (2009), [4] Cecinato et al. (2009a), [5] Cecinato et al. (2009b), [6] Cecinato et al.
(2010), [7] Viana et al. (2010), [8] Viana et al. (2011).
b
Range of mean concentrations of data either from different cities or seasons.

1090

R. Pal et al. / Science of the Total Environment 463464 (2013) 10791092

Table 7
A list on the patterns of main problem drugs in different parts of the world.
Compound

Opiates
Cannabis
Cocaine type
Amphetamines type
stimulants
Others

Occurrence level (%)


N. America

S. America

Europe

Africa

Asia

Oceania

9.8
35.3
31.2
12.4

2.6
30.8
54
2.2

60.1
18.9
9.1
11.9

15.7
63.6
9.6
5.2

63.3
11.5
0.4
19.1

32.6
47.3
0.4
18.2

11.3

10.4

5.9

5.7

1.5

Postigo et al., 2008a). The conrmation of the identity of compounds


detected at the limit of quantication level is of great importance to
avoid false positive interpretation; the most popular approach for
conrmation is based on the careful examination of analyte mass
spectral information (Bijlsma et al., 2009). Castiglioni et al. (2008)
pointed out that the main difculty in the analytical techniques is
the low concentration level of drugs plus complexity of the matrix.
The analysis of illicit drugs and metabolites in ambient air has
currently been recognised as an alternate tool to sewage epidemiology
for estimation of drug abuse and their impact on human health. However, as these airborne residues can arise from a variety of mechanism
they cannot be directly ascribed to consumption. Cocaine was rst
detected in the air of two Italian cities and the determination of cocaine
in carbonaceous aerosol samples was performed by solvent extraction
followed by clean up through column chromatography and analysis in
high resolution gas chromatography mass spectrometry (HRGC-MS)
(Cecinato and Balducci, 2007). Postigo et al. (2009) developed the rst
analytical method for multianalyte determination of a group of illicit
drugs and metabolites in airborne particulates based on pressurized
liquid extraction of atmospheric particles collected by high volume
sampler equipped with quartz microber lter followed by their
analysis in liquid chromatography tandem mass spectrometry (LCMS/MS). The method simultaneously determined compounds from
ve different chemical classes, such as cocainics, opioids, cannabinoids,
amphetamines, and lysergic compounds.
6. Conclusion
Human excretion is one of the major sources of illicit drugs into
the environment. Large proportions of consumed parent drugs and/
or their active metabolites are discharged into domestic wastewater
through urine or faeces (Zuccato and Castiglioni, 2009). The literatures indicate that benzoylecgonine, ecgonine methyl ester, MDMA,
methamphetamine, amphetamine and morphine are the most abundant residues in efuents of WWTPs. In accordance with the concentration levels recorded in the efuents of WWTPs, all six compounds
showed more frequent occurrence in surface water than other compounds. Although the environmental concentrations of even the
most abundant illicit drugs and their metabolites are low, compounds
such as morphine, amphetamine, and MDMA have potent pharmacological activities and their presence as complex mixtures in surface
waters may be toxic to aquatic organisms and risks to human health
and the aquatic environment cannot be ignored (Zuccato and
Castiglioni, 2009). As the affects of drug and metabolite residues
upon the environment are largely unknown no guideline values are
available for the permissible concentrations of illicit drugs and their
metabolites in surface water.
Our review of the available literature revealed that data and information on illicit drugs in waste and river water are mostly available
from the European countries such as Italy, Switzerland, Spain, Belgium,
Ireland, France, Germany, Craotia, and the UK and a few from the USA,
Canada, and Australia. There is a lack of information regarding Asia, Africa, and also Oceania yet drug use is now recognised as a global problem (Grifths et al., 2008). ATS use stabilized in developed countries

after 2001 but is still increasing in developing countries (UNODC,


2008a). ATS manufacture has undergone signicant growth since
2001 in several countries including China, the Philippines, Canada,
Czech Republic, Australia, New Zealand, South Africa, Indonesia, Malaysia, and Turkey (UNODC, 2008a). Methamphetamine is manufactured
throughout East and South-East Asia, North America, and Oceania. Amphetamine production remains concentrated largely in Europe (which
accounted for 79% of amphetamine laboratories reported in 2006)
while ecstasy is manufactured primarily in North America, Western Europe, Oceania, East and South-East Asia (UNODC, 2008b; EMCDDA,
2008). In Table 7, a worldwide pattern for main problem drugs has
been compiled (UNODC, 2008c). The table shows that the opioids are
most popular in Asia and Europe, cannabis in Africa, cocaine in North
and South America, and amphetamine type stimulants in Asia, Oceania,
North America, and Europe. In Europe, in the northern and central European countries generally, the amphetamine group drugs are most popular, while cocaine use predominated in the west and southern Europe
(EMCDDA, 2008). The abovementioned evidence for the near universal
manufacture and consumption of illicit drugs also indicates the likelihood of widespread environmental contamination by these pollutants.
However, there is a lack of information from a large part of the world
on occurrence patterns, fate, and their impact on different environmental compartments. Considering the fact that the information on the environmental contamination by illicit drugs are yet conned to a limited
number of countries, more research is needed to establish their occurrence in waste and surface waters in areas outside Europe and North
America. The results in Table 7 provide a starting point for the selection
of the drugs (and their metabolites) that should be researched in the
water bodies on each continent.
Acknowledgements
This work was supported by a National Drug Law Enforcement Research Fund, an initiative of the National Drug Strategy.
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