Trends in Analytical Chemistry, Vol. 22, No.

10, 2003 Trends

Analysis and removal of emerging

contaminants in wastewater and
drinking water
Mira Petrović, Susana Gonzalez, Damià Barceló

The occurrence of trace organic contaminants in wastewaters, their large quantities in everyday life, such as
behavior during wastewater treatment and production of drinking water human and veterinary pharmaceuticals,
are key issues in the re-use of water resources. Elimination of different personal care products, surfactants and
classes of emerging contaminants, such as surfactant degradates, phar- surfactant residues, plasticizers and var-
maceuticals and polar pesticides in wastewater-treatment plants (WWTPs) ious industrial additives. The character-
was found to be rather low, so sewage effluents are one of the main istic of these contaminants is that they do
sources of these compounds and their treatment-resistant metabolites. not need to be persistent in the environ-
This article reviews the state-of-the-art in the analysis of several groups of ment to cause negative e¡ects, since their
emerging contaminants (acidic pharmaceuticals, antibacterial agents, high transformation and removal rates
acidic pesticides and surfactant metabolites) in wastewaters. It also dis- can be o¡set by their continuous intro-
cusses the elimination of emerging contaminants in WWTPs applying duction into the environment. One of the
conventional activated sludge treatment (AST) and advanced treatment main sources of emerging contaminants
processes, such as membrane bioreactors (MBRs) and advanced oxidation are untreated urban wastewaters and
processes (AOPs), as well as during production of drinking water. WWTP e¥uents (Fig. 1). Most current
# 2003 Published by Elsevier B.V. WWTPs are not designed to treat these
types of substance and a high portion of
Keywords: Acidic pesticides; Acidic pharmaceuticals; Advanced treatment; Emerging emerging compounds and their metabo-
contaminants; Surfactant degradates; Wastewater treatment
lites can escape elimination in WWTPs
and enter the aquatic environment via
sewage e¥uents.
1. Introduction The partial or complete closure of water
Mira Petrović*, cycles is an essential part of sustainable
Susana Gonzalez,
Damià Barceló Until the beginning of the 1990s, non- water-resource management, and the
Department of Environmental polar hazardous compounds (i.e. persis- increasing scarcity of pristine waters for
Chemistry, IIQAB-CSIC, tent organic pollutants (POPs) and heavy drinking water supply and the growing
c/Jordi Girona 18-26, E-08034 metals) were a focus of interest and consumption of water by industry and
Barcelona, Spain awareness as priority pollutants, so were agriculture should be countered by the
part of intensive monitoring programs. e⁄cient, rational utilization of water
Today, these compounds are less relevant resources. One of the options is to
for the industrialized countries, since a increase the re-use of e¥uents for various
dramatic reduction of emissions has been purposes, especially in industrial and
achieved through the adoption of appro- agro/food production. However, because
priate measures and the elimination of of the high cost of the end-of-pipe
the dominant sources of pollution. approach (i.e. drinking water treatment),
However, the emission of so-called indirect potable re-use requires e⁄cient
‘‘emerging’’ or ‘‘new’’ unregulated con- treatment of wastewaters prior to their
taminants has become an environmental discharge. Thus, the occurrence of trace
problem, and there is widespread con- organic contaminants in wastewaters,
*Corresponding author.
Tel.: +34 93 400 6172; sensus that this kind of contamination their behavior during wastewater treat-
Fax: +34 93 204 5904; may require legislative intervention. This ment and production of drinking water
E-mail: mpeqam@cid.csic.es group mainly comprises products used in are key issues that require further study.

0165-9936/$ - see front matter # 2003 Published by Elsevier B.V. doi:10.1016/S0165-9936(03)01105-1 685
Trends
Figure 1. Components of a (partially) closed water cycle with indirect potable re-use.
Many believe that, of all emerging contaminants,
antibiotics are of greatest concern, since their emission
in the environment can increase the occurrence of
resistant bacteria in the environment [1]. However,
other emerging compounds, especially polar ones, such
as acidic pharmaceuticals, acidic pesticides and acidic
metabolites of non-ionic surfactants, also deserve parti-
cular attention. Because of their physico-chemical
properties (high water solubility and often poor degrad-
ability), they are able to penetrate through all natural
¢ltration steps and man-made treatments, thus pre-
senting a potential risk in drinking water supply [2,3].
Di¡erent classes of emerging contaminants, mainly
surfactant degradates, pharmaceuticals and personal
care products (PPCPs) and polar pesticides were found
to have rather low elimination rates and have been
detected in WWTP e¥uents and in the receiving surface
waters. However, for most emerging contaminants,
occurrence, risk assessment and ecotoxicological data
are not available, and it is di⁄cult to predict their fate in
the aquatic environment. Partly, the reason for this is a
lack of analytical methods for their determination at
trace concentrations. Analysis of emerging con-
taminants is a real analytical challenge, not only
because of the diversity of chemical properties of these
compounds, but also because of generally low con-
centrations (usually at part per billion (ppb) or part per
trillion (ppt) levels) and the complexity of matrices.
686 http://www.elsevier.com/locate/trac
Trends in Analytical Chemistry, Vol. 22, No. 10, 2003
This article reviews the state-of-the-art in the analy-
sis of several groups of emerging contaminants (acidic
pharmaceuticals, antibacterial agents, acidic pesticides
and surfactant metabolites) in wastewaters. It discusses
various aspects of current liquid chromatography (LC)
mass spectrometry (MS)-(MS) [LC-MS-(MS)] and gas
chromatography (GC)-MS [GC-MS] methodology, includ-
ing sample preparation. It also surveys the elimination
of emerging contaminants in WWTPs by AST and
applying advanced treatment processes, such as MBRs
and AOPs. In addition, it discusses the elimination in
treatment processes at plants for treating drinking water.
2. Analysis of emerging contaminants in
wastewater
One of the major limitations in the analysis of emerging
contaminants remains the lack of methods for quanti¢-
cation of low concentrations. The prerequisite for
proper risk assessment and monitoring of the quality of
waste, surface and drinking waters is the availability of
multiresidual methods that permit measurement at the
low ng/l level (or even below that). However, these
compounds have received little attention because they
are not on regulatory lists as environmental pollutants.
However, today analytical methodology for di¡erent
groups of emerging contaminants is being developed
Trends in Analytical Chemistry, Vol. 22, No. 10, 2003 Trends

and an increasing number of methods is reported in the

Reference
literature. Still, analysis of this group of contaminants
requires further improvement in terms of sensitivity

[48]

[49]

[50]
[51]

[52]

[53]

[54]
[5]
and selectivity, especially for very complex matrices,
such as wastewater.

0.016–2.18
0.3–4.5

0.4–2.6
0.6–20
(ng/l)

5–56

5–20
LOD
2.1. Acidic pharmaceuticals

20
2
Di¡erent methods, mainly based on LC-MS and GC-MS,
in combination with either polymer or C18-based solid-

Detection

MS–MS

MS–MS
phase extraction (SPE), are being developed for the ana-
lysis of pharmaceutical compounds. However, most

MS

MS

MS

MS

MS

MS
methods are tailored for neutral compounds (e.g. anti-

Chromatographic
biotics) and less complex matrices (surface and ground-
water), while only a limited number of papers describe
procedures applicable to the analysis of polar drugs in

method
wastewater. A survey of analytical methods for the
quanti¢cation of regularly used polar pharmaceuticals

GC

GC

GC

GC
LC

LC

LC

LC
in wastewater matrices is given in Table 1.

(bis (trimethylsilyl)-trifluoroacetamide)
A typical analytical method includes the use of octa-

(N-methyl-N-(tert-butyldimethylsilyl)
decylsilica, polymeric, or hydrophilic-lipophilic balanced
(HBL) supports for o¡-line SPE of water samples, with
either disks or, most frequently, cartridges at low pH

Pentaflorobenzyl bromide
(typically pH=2).
Separation techniques include GC and LC, while, for

trifluoroacetamide)
detection, MS is the technique most widely employed.

Diazomethane
Derivatization

Because of the low volatility of polar pharmaceuticals,

GC-MS analysis requires an additional derivatization,

MTBSTFA
which makes sample preparation laborious and time

BSTFA
consuming, and also increases the possibility of con-
–

–
tamination and errors. Moreover, some compounds are

SPE (MCX or polymeric sorbent)

thermolabile and decompose during GC analysis (e.g.
carbamazepine forms iminostilben as degradation pro-
(C18+polymeric sorbent)

duct) [4].
SPE (polymeric sorbent)

SPE (polar Empore disk)

As a result, use of LC-MS and LC-MS-MS is increasing.
When reviewing the principal methods for the analysis
Table 1. Methods for the analysis of acidic pharmaceuticals in wastewaters

of pharmaceuticals in aqueous environmental samples,

Sequential SPE

Ternes [4] indicated that LC-MS-MS is the technique of

Extraction

SPE (C18)

SPE (C18)
SPE (HLB)

choice for assaying polar pharmaceuticals and their SPE (HLB)

metabolites. However, he pointed out the di⁄culty in
the enrichment step, as well as the low resolution and
signal suppression in the electrospray (ESI) interface
Ibuprofen, naproxen, ketoprofen, tolfenamic acid,
Bezafibrate, clofibric acid, diclofenac, fenoprofen,

Clofibric acid, diclofenac, ibuprofen, phenazone,

gemfibrozil, ibuprofen, inomethacin, ketoprofen,

because of matrix impurities.

Salicylic acid, ibuprofen, ketoprofen, naproxen,

Ibuprofen, clofibric acid, ketoprofen, naproxen,

Bezafibrate, diclofenac, ibuprofen, gemfibrozil,

Farre¤ et al. [5] compared LC-(ESI)-MS and GC-MS

(after derivatization with BF3-MeOH) for monitoring
some acidic and very polar analgesics (salicylic acid,
Bezafibrate, clofibric acid, ibuprofen

Clofibric acid, naproxen, ibuprofen

ketoprofen, naproxen, diclofenac, ibuprofen and gem¢-

brozil) in surface water and wastewater. Results
diclofenac, meclofenamic acid

showed a good correlation between methods, except for

gem¢brozil, for which derivatization was not com-
bezafibrate, diclofenac

pletely achieved in some samples.

In general, the limits of detection (LODs) achieved
propyphenazone
carbamezapine

with LC-MS-(MS) methods were slightly higher than

Compounds

those obtained with GC-MS methods (see Table 1); how-

diclofenac
naproxen

ever, LC-MS methodology showed advantages in terms

of versatility and sample preparation being less compli-
cated (i.e., derivatization was not needed).

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Trends Trends in Analytical Chemistry, Vol. 22, No. 10, 2003

Table 2 summarizes the quantitation and quali¢er
ions used by the various authors for the determination
of polar drugs in wastewaters using selected ion mon-
itoring (SIM) or multiple reaction monitoring (MRM).
The use of triple-quadrupole MS in LC analysis has sub-
stantially increased the selectivity and the sensitivity of
the determination, resulting in LODs better than those
in single-quadrupole LC-MS. Acidic drugs were usually
detected using an ESI interface under negative ioni-
zation conditions and deprotonated molecules were
chosen as precursor ions. Typical fragmentation pat-
terns obtained with LC-MS-(MS) showed a loss of CO2
(or loss of the acidic moiety), with a limited number of
other fragments. For example, for diclofenac, ibuprofen
and ketoprofen, the product ions generated by loss of
CO2 were the only fragment ions formed.
2.2. Acidic pesticides
Chlorinated phenoxy acid herbicides account for the
majority of pesticides used worldwide, and their pre-
sence in environmental waters is well documented.
However, their behavior during wastewater treatment
has rarely been studied. This group includes, for exam-
ple, mecoprop (MCPP), MCPA, 2,4-D, 2,4-DP 2,4,5-T,
2,4-DB. These compounds are characterized by high
polarity and thermal lability. For these reasons, LC is
generally more suitable for their analysis. However, the
methods used to determine chlorinated phenoxy acid

Table 2. Quantitation and diagnostic ions (m/z) used for the LC-MS and GC-MS, and base peaks of precursor and product ions used for LC-MS-MS analysis
of acidic pharmaceuticals in wastewaters. Data compiled from references listed in Table 1

Compound Analytical method Ionization mode MS MS-MS

SIM ions Precursor (m/z) Product 1 (m/z) Product 2 (m/z)
Ibuprofen LC-MS NI 205, 161
LC-MS-MS NI 205½M-H 161½M-H-CO2  –
a
GC-MS Positive EI 177, 220
161, 343, 386b
263, 278, 234c

Diclofenac LC-MS NI 294, 250, 232

LC-MS-MS NI 294½M-H 205½M-H-CO2  –
a
GC-MS Positive EI 214, 309
214, 216, 475b
352/354/356d

Clofibric acid LC-MS NI 213, 127

LC-MS-MS NI 213½M-H 127½M-H-CO2  85½C4 H5 O2 
a
GC-MS Positive EI 128, 228
128, 130, 394b
128, 143, 286c

Benzafibrate LC-MS NI 360, 274

LC-MS-MS NI 360½M-H 274½M-H-C4 H6 O2  154½M-H-C12 H14 O3 
GC-MS Positive EI 128, 228a
128, 130, 394b

Gemfibrozil LC-MS NI 249, 121

LC-MS-MS NI 249½M-H 121½M-H-C7 H12 O2 

Ketoprofen LC-MS NI 253, 209, 197

LC-MS-MS NI 253½M-H 209½M-H-CO2 
GC-MS Positive EI 209, 268a
311d

Naproxen LC-MS NI 229, 185, 173, 170

LC-MS-MS NI 229½M-H 185½M-H-CO2  170½M-H-C2 H3 O2 
a
GC-MS Positive EI 185, 244
243, 302, 185c
287d
a
Diazomethane derivative.
b
Pentafluorobenzyl derivative.
c
Trimethylsilyl derivative.
d
Tert-butyldimethylsilyl derivative.

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Trends in Analytical Chemistry, Vol. 22, No. 10, 2003
herbicides are still dominated by GC with either elec-
tron capture detection (ECD) or MS detection. The main
disadvantage of GC analysis is that it requires prior deri-
vatization step, usually using highly toxic and carcino-
genic diazomethane or, less frequently used, acid
anhydrides, benzyl halides and alkylchloroformates.
The injection-port derivatization with an ion-pair
reagent has been successfully applied [6], as well as in
situ derivatization prior to solid-phase microextraction
(SPME) [7].
Figure 2. MS-MS spectra and the proposed fragmentation pattern of: (a) MCPP (precursor ion m/z 213); (b) Dichlorprop (2,4-DP) (precursor ion m/z 233);
and, (c) 2,4,5-T (precursor ion m/z 253).
Trends
Alternative methods based on LC-ESI-MS have been
proposed. When using LC-MS-(MS), phenoxy acid her-
bicides are detected under negative ionization condi-
tions, typically yielding [M-H]- ion and one abundant
fragment formed by the loss of the acidic moiety [8,9],
as shown in Fig. 2 for MCPP, 2,4DP and 2,4,5T.
Recently, in-tube SPME followed by LC-MS was
applied for the determination of six chlorinated phen-
oxy acid herbicides [10]. With river water, LODs were
5^30 ng/l, but wastewater was not tested.
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Trends
2.3. Antiseptics
Several methods have been proposed for the determina-
tion of triclosan (5-chloro-2-[2,4-dichlorophenoxy]
phenol), which is used as an antiseptic agent in a vast
array of personal care (e.g. toothpaste, acne cream,
deodorant, shampoo, toilet soap) and consumer pro-
ducts (children’s toys, footwear, kitchen cutting
boards).
A method based on diazomethane derivatization and
GC-ECD was applied for quanti¢cation of triclosan in
the wastewater of a slaughterhouse [11].
Lindstro«m et al. [12] detected triclosan and methyl
triclosan in lakes and in a river in Switzerland applying
either SPE (macroporous polymeric adsorbent), dia-
zoethane derivatization, silica clean-up and GC-MS
analysis or passive sampling with semi-permeable
membrane devices (SPMDs). LODs varied with the
sample matrix and were < 0.4 ng/l for surface water,
< 1^2 ng/l for wastewater and < 1^2 ng/g for the
SPMD samples.
Figure 3. Full scan mass spectra of triclosan (in EI and NCI) (reproduced with permission from [14]. # 2003 Elsevier).
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Trends in Analytical Chemistry, Vol. 22, No. 10, 2003
McAvoy et al. [13] used C18 SPE for isolation of
triclosan from wastewater and supercritical £uid CO2
for sludge, followed by derivatization to trimethylsily-
lethers and quantitation by GC-MS. Recovery from
spiked wastewater was in the range 79^88% for in£uent,
from e¥uent 36^87% and from primary sludge 70^90%.
Recently, Agu«era et al. [14] compared the use of GC-
MS, in electron impact ionization (EI) and negative che-
mical ionization (NCI) modes, and LC-ESI-MS-MS for
the analysis of triclosan in urban wastewater and
marine sediments. Mass spectra obtained are shown in
Fig. 3. GC-NCI-MS was found to represent the best
approach for triclosan allowing LODs at ng/l levels with
an adequate identi¢cation criterion (three ions). How-
ever, the LC-MS-MS spectrum obtained for triclosan did
not show fragmentation at all under the di¡erent frag-
mentation conditions assayed, only the molecular
cluster being present. The method yielded higher
LODs M 0.35 mg/l for spiked urban wastewater and
3.5 mg/kg for marine sediment.
Trends in Analytical Chemistry, Vol. 22, No. 10, 2003
2.4. Alkylphenolic compounds
The trace analysis of alkylphenol ethoxylates (APEOs)
and their acidic metabolites by LC-MS or LC-MS-MS
using atmospheric pressure chemical ionization (APCI)
and ESI was recently reviewed by Petrovic et al. [15,16]
and the analytical performances for oligomeric mix-
tures of APEOs discussed. Generally, an ESI interface is
used for the analysis of alkylphenolic compounds
because of its higher sensitivity, especially for alkyl-
phenols and carboxylated compounds.
Alkylphenoxy carboxylates (APECs) were detected in
both NI and PI modes. In the NI mode, using ESI, APECs
give two types of ions:
 one corresponds to the deprotonated molecule
[MH] (m/z 277, 321, 263 and 307, corre-
sponding to nonylphenol carboxylate (NPE1C),
nonylphenol ethoxycarboxylate (NPE2C), octyl-
phenol carboxylate (OPE1C), and octylphenol
ethoxycarboxylate (OPE2C), respectively); and,
 the other corresponds to deprotonated alkyl-
phenols [17].
The relative abundance of these two ions depends on
the extraction voltage. In the presence of ammonium
acetate and when using an APCI under PI conditions,
NPE1C gave [M+NH4]+ ions at m/z 296, while NPE2C
gave [M+NH4]+ ion at m/z 340 [18].
LC-ESI-MS was also applied for the analysis of the
dicarboxylated breakdown products [carboxylated
alkylphenoxy carboxylates (CAPECs)] in wastewaters
[19,20]. However, the identi¢cation of these com-
pounds using LC-MS, under conditions giving only
molecular ions, is di⁄cult, since CAnPEmCs have the
same molecular mass as APECs but have one ethoxy
unit less and a shorter alkyl chain (An1PEm1C).
Moreover, since some compounds partly co-elute, the
unequivocal assignment of the individual fragments
can be accomplished only by using LC-MS-MS. Typical
fragmentation patterns obtained with LC-ESI-MS-MS
showed the formation of the carboxy-alkylphenoxy
fragment, with the additionally loss of CO2 or an acetic
acid group, in the case of CA5PE12C leading to m/z 149
and 133 fragments [19].
MS-MS spectra of APECs [19,21,22] show intense
signals at m/z 219 (for NPECs) and m/z 205 (for OPECs),
which are produced after the loss of the carboxylated
(ethoxy) moiety, while sequential fragmentation of the
alkyl chain resulted in ions with m/z 133 and 147.
To overcome the problem of low volatility of acidic
alkylphenolic compounds, various o¡-line and on-line
derivatization protocols have been developed. O¡-line
derivatization to corresponding triemethylsilyl ethers,
methyl ethers, acetyl esters, penta£uorobenzoyl or hep-
ta£uorobutyl esters, respectively, was applied as a
common approach in GC-MS.
Trends
On-line direct GC injection-port derivatization using
ion-pair reagents (tetraalkylammonium salts), has
been also reported [23]. The most signi¢cant ions in
GC-(EI)-MS of methylated NPECs were fragments pro-
duced by rupture of the benzylic bond in the branched
nonyl side-chain [23^25]. GC-CI-MS spectra of the
NPECs with isobutane as reagent gas showed char-
acteristic hydride ion-abstracted fragment ions shifted
by 1 Da from those in the corresponding EI mass spectra
[22]. When using ammonia as reagent gas, intense
ammonia-molecular ion adducts of the methyl esters,
with little or no secondary fragmentation, were repor-
ted for NPECs [26]. The ions selected were as follows:
m/z 246, 310, 354 and 398 for NPE1C, NPE2C,
NPE3C and NPE4C, respectively.
3. Elimination by AST
The present state-of-the-art of wastewater treatment
involves the AST process preceded by conventional
physico-chemical pre-treatment steps. Table 3 sum-
marizes data on the elimination of emerging con-
taminants in WWTPs.
3.1. PPCPs
Daughton and Ternes [1] reviewed the occurrence of
over 50 individual PPCPs (metabolites from more than
10 broad classes of therapeutic agents or personal care
products in environmental samples) mainly in WWTP
e¥uents, surface and ground water and much less fre-
quently in drinking water. Acidic drugs comprised the
major group of PPCPs detected in municipal WWTPs
and, among them, beza¢brate, naproxen, and ibupro-
fen were most abundant (concentrations up to 4.6 mg/l
in German municipal WWTPs).
Tixier et al. [27] found that carbamezapine presented
the highest daily load from the WWTP into Lake Grei-
fensee (Switzerland), followed by diclofenac and
naproxen. Their elimination during passage through a
municipal sewage treatment in most cases was found to
be quite low (see Table 3), in the range 35^90%, and
some compounds, such as carbamazepine, exhibited an
extremely low removal (only 7%) [28]. Consequently,
through sewage e¥uents, PPCPs can enter receiving
surface waters and thus present a risk in the production
of drinking water. For example, clo¢bric acid, a metabo-
lite of three lipid regulating agents (clo¢brate, eto¢brate
and feno¢brate), has been identi¢ed in river and ground
water and even in drinking water at concentrations up
to 165 ng/l [29,30].
3.2. Acidic pesticides
Chlorinated phenoxy acids are widely used in agri-
culture, but also as herbicides on lawns, algicides in
paints and coatings and roof-protection agents in
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Trends Trends in Analytical Chemistry, Vol. 22, No. 10, 2003

Table 3. Elimination at WWTPs (AST). Data complied from references [12,28,36,51,54–57]

Compound Average Effluent Main degradation Observation
elimination (%)a concentrations products
(g/l)
Non-ionic surfactants
Alkylphenol ethoxylates 90–99 <0.1–350 APEC, CAPEC, AP Primary degradation fast; ultimate
degradation less than 40%,
with metabolites being potential
endocrine disruptors

Pharmaceuticals
Ibuprofen 65–90 0.37–0.60 (3.4)b
Diclofenac 69–75 0.06–0.81 (2.1) Rapid photodegradation
Clofibric Acid 34–51 0.12–0.36 (1.6) Degradation product of
lipid-regulating agents
Benzafibrate 83 1.1–2.2 (4.6)
Naproxen 45–66 0.27–0.61 (2.6)
Ketoprofen 69 0.02–0.38 (0.87)
Gemfibrozil 46–69 0.31–0.40 (1.9)
Carbamazepine 7 0.30–2.1 (6.3) Low removal rate

Antiseptics
Triclosan 44–92 0.070–0.650 Methyl triclosan Possible photodegradation

Pesticides
MCPP and MCPA – 20–400 2–Methyl-4-Cl-phenol Application period (mid-March
until mid-May)
2,4-D – <20 2,4-Dichlorphenol
2,4,5-T – <20 2,4-D; 2,4-dichlorphenol
a
Primary elimination of the parent compound.
b
Range of average values detected (in parentheses: maximum concentration detected).

£at-roof sealants. As a result, residues of these sub- 3.3. Alkylphenolic surfactants

stances are introduced into the aquatic system through
di¡erent pathways. For example, in the catchment area of
Lake Greifensee, 65% of MCPP originated from WWTPs
and the remaining 35% from di¡use sources [31].
Degradation of acidic pesticides under laboratory
conditions is well studied, but there are few publica-
tions dealing with their behavior in real WWTPs. Gen-
erally, AST was found to be ine¡ective in removing
chlorinated phenoxy acid herbicides from settled sew-
age. However, under laboratory conditions MCPP
proved to be biodegradable (nearly 100%); however,
this requires a long adaptation time (lag-phase) of acti-
vated sludge [32]. In real WWTPs, this presents a major
di⁄culty since, like the majority of herbicides, MCPP is
applied only during a short growth period of plants,
which means that WWTPs that contain a non-adapted
activated sludge, receive shock-loads of herbicides,
which will not be eliminated.
A long acclimatization period (about 4 months) was
also observed in a bench-scale study using sequencing
batch reactors before 2,4-D biodegradation was estab-
lished [33]. Subsequently, at steady-state operation,
all reactors achieved practically complete removal
( > 99%) of 2,4-D.
Although their environmental acceptability is strongly
disputed, APEOs are still among the most widely used
non-ionic surfactants. Currently, under optimized con-
ditions, more than 90^95% of these surfactants are
eliminated by conventional biological wastewater
treatment (normally AST). Even if such high elimina-
tion rates are achieved, the principal problem is the for-
mation of treatment-resistant metabolites out of the
parent surfactants. The widespread incidence of APEO-
derived compounds in treated wastewaters and the sub-
sequent disposal of e¥uents into aquatic system raise
concerns about the impact of these compounds on the
environment. Studies have shown that their neutral
(alkylphenols and short ethoxy chain ethoxylates) and
acidic treatment-resistant metabolites (APECs) possess
the ability to mimic natural hormones by interacting
with the estrogen receptor.
It was estimated that 60^65% of all nonylphenolic
compounds introduced into WWTPs are discharged
into the environmentM 19% as carboxylated deriva-
tives, 11% as lipophilic nonylphenol ethoxylate
(NP1EO) and nonylphenol diethoxylate (NP2EO), 25%
as nonylphenol (NP) and 8% as non-transformed
nonylphenol ethoxylates (NPEOs) [34].

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Trends in Analytical Chemistry, Vol. 22, No. 10, 2003
However, contrary to the general belief that NPECs
are the refractory metabolites, Di Corcia et al. [35]
found that CAPECs are the dominant products of NPEO
biotransformation. By averaging data relative to the
treated e¥uents of ¢ve major activated sludge WWTPs
of Rome (Italy) over 4 months, relative abundances of
NPEOs (nEO =1 and 2), NPECs and CAPECs were found
to be respectively 10  2%, 24  5% and 66  7%.
The concentrations of the acidic metabolites, NPECs
and CAPECs typically are in the low mg/l range. How-
ever, high values (up to several hundred mg/l) are detec-
ted in e¥uents of WWTPs receiving industrial
wastewaters, especially from tannery, textile, pulp and
paper industries [36].
4. Elimination by modern WWTPs
Although adopted as the best available technology; bio-
logical treatment e¡ects only partial removal of a wide
range of emerging contaminants, especially polar ones,
which are discharged into the ¢nal e¥uent. Thus, it has
become evident that the application of more enhanced
technologies may be crucial to ful¢ll the requirements
to recycle municipal and industrial wastewaters as
drinking water. In recent years, there have been studies
of new technologies for not only wastewater treatment
but also production of drinking water. Among them
membrane treatment, using both biological (MBRs) and
non-biological processes (reversed osmosis, ultra¢ltra-
tion, nano¢ltration), and AOPs are most frequently
considered as they may be appropriate for removing
trace concentrations of emerging polar contaminants.
4.1. Membrane processes
MBR technology is considered the most promising
development in microbiological wastewater treatment.
Now, when economic reasons no longer limit the appli-
cation of MBRs in industrial and municipal WWTPs [37],
and new requirements are being set for wastewater treat-
ment, MBRs may be key in direct or indirect recycling of
wastewaters, because of two of their characteristics:
(a) the low sludge load in terms of BOD, so that the
bacteria are forced to mineralize poorly degrad-
able organic compounds; and
(b) the long life of the sludge gives the bacteria time
to adapt to the treatment-resistant substances
[38,39].
However, although many articles have reported on
the application of MBRs to the treatment of urban and
industrial wastewaters, there are few papers reporting
on the behavior of emerging contaminants during MBR
treatment, and all of those deal with nonylphenolic
compounds.
Trends
Using an MBR unit that comprises three bioreactors
and an external ultra¢ltration unit followed by gran-
ular activated carbon (GAC) adsorption, Witgens et al.
[40] reported the removal of more than 90% of NP in
wastewater from a waste-dump leachate plant. The use
of a set of laboratory nano¢ltration membranes resul-
ted in the retention of more than 70% of NP and this
process was regarded as an alternative for the ¢nal
treatment of MBR e¥uents.
Li et al. [41] used GC-MS and LC-MS-MS to assess the
elimination e⁄ciency in a membrane-assisted biologi-
cal WWTP. The results showed that, compared to con-
ventional WWTPs, membrane-assisted biological
treatment with biomass concentrations of about 20 g/l
could improve the e⁄ciency of eliminating NPEOs (and
other ionic and non-ionic surfactants), but could not
entirely stop the discharge with the permeates.
4.2. Treatment by AOPs
There have been studies of AOPs, which use a combi-
nation of ozone with other oxidation agents (UV radia-
tion, hydrogen peroxide, TiO2) to enhance the
degradation of polar pharmaceuticals [42^44] and
NPEO metabolites [45].
Ternes et al. [44] used a pilot plant for ozonation and
UV disinfection of e¥uents from a German municipal
WWTP containing antibiotics, beta blockers, anti-
phlogistics, lipid-regulator metabolites, musk frag-
rances and iodinated X-ray contrast media. When
10^15 mg/l ozone was used (contact time, 18 min), no
pharmaceuticals were detected. However, the ionic
iodinated X-ray contrast compounds exhibited removal
e⁄ciencies no higher than 14%.
In another study [43], ozonation was demon-
strated to be a suitable tool for carbamazepine abate-
ment, even under the process conditions usually
adopted in drinking water facilities. However, despite
good primary elimination, a low degree of mineraliza-
tion was observed and there was no proper total carbon
balance, even after prolonged ozonation, which
indicated the presence of unidenti¢ed degradation
products.
However, the degradation e⁄ciency of an AOP is lim-
ited by the radical scavenging capacity of the matrix of
the treated water. Thus, for su⁄cient degradation of the
pharmaceuticals ( > 90%) from wastewater, the ozone
concentration has to be equal to the dissolved organic
carbon (DOC) value [42], which means that economic
considerations have to underpin the feasibility of the
process for wastewater treatment.
Recently, using a laboratory-scale reactor, Ike et al.
[45] determined that the e¡ectiveness of ozone treat-
ment in the degradation of NPEO metabolites follows
the order: NPE1C > > NP > NP1EO. Acidic metabolites
were completely degraded within 4^6 min (initial con-
centration, 0.4^1.0 mg/l), the NP concentrations were
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Trends Trends in Analytical Chemistry, Vol. 22, No. 10, 2003

reduced by 75^80% in 6 min, while only 25^50% of
NP1EO was eliminated in the same time.
5. Elimination in drinking water-treatment
plants
The occurrence of organic micro-contaminants in raw
water and their removal in the course of production of
drinking water and possible formation of disinfection
by-products are key issues in relation to the quality of
drinking water. Although, compounds discussed in this
review are currently not regulated in drinking water
directives, precautionary principles should be
employed, and the removal of all organic micro-con-
taminants should be as high as possible. However, sev-
eral studies have shown that the removal of emerging
polar contaminants during drinking water treatment is
incomplete.
The elimination of selected pharmaceuticals (clo¢bric
acid, diclofenac, carbamezapine, beza¢brate) during
drinking water treatment was investigated in the
laboratory, at the pilot-plant scale and in real water-
works in Germany [46]. Sand ¢ltration under aerobic
and anoxic conditions, as well as £occulation using
iron(III) chloride, did not signi¢cantly eliminate the
target pharmaceuticals, while ozonation was quite
e¡ective in eliminating these polar compounds. Diclofe-
nac and carbamezapine were reduced by more than
90%, beza¢brate was eliminated by 50%, while clo¢bric
acid was stable even at high ozone doze. Filtration with
granular activated carbon (GAC) under waterworks con-
ditions was very e¡ective in removing pharmaceuticals,
apart from clo¢bric acid, less of which was adsorbed.

Figure 4. Fate of nonylphenolic compounds during production of drinking water. (a) Total concentration of nonylphenolic compounds and their elimination
during different treatment steps at waterworks Sant Joan Despì (Barcelona, Spain); (b) Average composition (calculated on a molar basis) of nonylphenolic
compounds in raw water; and, (c) Average composition (calculated on a molar basis) of nonylphenolic compounds in pre-chlorinated water.

694 http://www.elsevier.com/locate/trac
Trends in Analytical Chemistry, Vol. 22, No. 10, 2003
The behavior of polar alkylphenolic compounds dur-
ing processing of contaminated water in waterworks
and their possible occurrence in treated water was
rarely considered to be of interest and there are hardly
any data available for drinking water.
The elimination of neutral and acidic nonylphenolic
compounds and their brominated and chlorinated deri-
vatives during drinking water-treatment processes at
the waterworks that supply drinking water to Barce-
lona (Spain) was investigated utilizing a very sensitive
LC-MS-MS method [47]. The concentration of total
nonylphenolic compounds M NPECs (nEO=0^1), NPEOs
(nEO=0^1) and NP M in raw water from the Llobregat
river entering the waterworks was in the range
8.3^21.6 mg/l, with NPE2C being the most abundant
compound. Pre-chlorination reduced the concen-
tration of short-ethoxy chain NPECs and NPEOs by
25^35%, and of NP by almost 90%. However, this
reduction was partly because of their transformation
to halogenated derivatives. After pre-chlorination,
halogenated nonylphenolic compounds represented
approximately 13% of the total metabolite pool, of
which 97% were in the form of brominated acidic
metabolites. The e⁄ciency of further treatment steps to
eliminate nonylphenolic compounds (calculated for the
sum of all short-ethoxy chain metabolites, including
halogenated derivatives) was as follows:
 settling and £occulation followed by rapid sand
¢ltration (7%);
 ozonation (87%);
 GAC ¢ltration (73%); and,
 ¢nal disinfection with chlorine (43%), resulting
in overall elimination in the range 96^99%
(mean 98% for four sampling dates), as shown in
Fig. 4.
6. Conclusions
The application of advanced LC-MS and GC-MS tech-
nologies to environmental analysis has allowed the
determination of a broader range of compounds and
thus permitted more comprehensive assessment of
environmental contaminants. Among the various com-
pounds considered as emerging pollutants, acidic phar-
maceuticals, surfactant degradates and acidic
pesticides are of particular concern, because of both
their ubiquity in the aquatic environment and health
concerns.
Elimination of these emerging contaminants during
wastewater and drinking water treatment is not satis-
factory, so control of improved treatment has to be
strict to ensure that the proportion of these micro-con-
taminants removed is as high as possible. Thus, in view
Trends
of the possible re-use of WWTP e¥uents, more research
is needed to evaluate the fate of emerging contaminants
and their e¡ects in the aquatic environment. Moreover,
as disinfection processes (either chlorination or ozona-
tion) potentially shift the assessment of the risk of
human consumption of the parent compound to its
degradation products, generic analytical protocols will
have to be developed for the simultaneous determina-
tion of parent compounds and their metabolites.
Acknowledgements
The work described in this article was supported by the
EU Project P-THREE (EVK1-CT-2002-00116) and by
the Spanish Ministerio de Ciencia y Tecnologia
(PPQ2002-10945-E). M. Petrovic acknowledges the
‘‘Ramon y Cajal’’ contract from the Spanish MCyT. S.
Gonzalez acknowledges the grant from the Spanish
MCyT (PPQ2001-1805-CO3-01).
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