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Pan-European survey on the occurrence of selected polarorganic persistent pollutants in ground water

Robert Loos a,*, Giovanni Locoro a, Sara Comero a, Serafino Contini a,1, David Schwesig b,Friedrich Werres b, Peter Balsaa b, Oliver Gans c, Stefan Weiss c, Ludek Blaha d,Monica Bolchi e, Bernd Manfred Gawlik a

aEuropean Commission, Joint Research Centre, Institute for Environment and Sustainability, Via Enrico Fermi, 21020 Ispra, Italyb IWW Water Centre, Moritzstr. 26, 45476 Muelheim an der Ruhr, GermanycUmweltbundesamt GmbH, Spittelauer Lande 5, 1090 Vienna, AustriadMasaryk University, RECETOX, Kamenice 3, CZ 62500 Brno, Czech Republice Perkin Elmer Italia S.p.A., Via Tiepolo, 24, I 20052 Monza (MI), Italy

a r t i c l e i n f o

Article history:

Received 9 February 2010

Received in revised form

17 May 2010

Accepted 22 May 2010

Available online 1 June 2010

Keywords:

Ground water

Pan-European monitoring

Non-probabilistic sampling

Polar organic contaminants

SPE-LC-MS2

* Corresponding author. Tel.: þ39 0332 78640E-mail address: [email protected]

1 In remembrance of Serafino Contino.0043-1354/$ e see front matter ª 2010 Elsevdoi:10.1016/j.watres.2010.05.032

a b s t r a c t

This studyprovides thefirst pan-European reconnaissance of the occurrence of polar organic

persistent pollutants in European ground water. In total, 164 individual ground-water

samples from 23 European Countries were collected and analysed (among others) for 59

selected organic compounds, comprising pharmaceuticals, antibiotics, pesticides (and their

transformation products), perfluorinated acids (PFAs), benzotriazoles, hormones, alkylphe-

nolics (endocrine disrupters), Caffeine, Diethyltoluamide (DEET), and Triclosan. The most

relevant compounds in terms of frequency of detection and maximum concentrations

detected were DEET (84%; 454 ng/L), Caffeine (83%; 189 ng/L), PFOA (66%; 39 ng/L), Atrazine

(56%; 253 ng/L), Desethylatrazine (55%; 487 ng/L), 1H-Benzotriazole (53%; 1032 ng/L), Meth-

ylbenzotriazole (52%; 516 ng/L), Desethylterbutylazine (49%; 266 ng/L), PFOS (48%, 135 ng/L),

Simazine (43%; 127 ng/L), Carbamazepine (42%; 390 ng/L), nonylphenoxy acetic acid (NPE1C)

(42%; 11 mg/L), Bisphenol A (40%; 2.3 mg/L), PFHxS (35%; 19ng/L), Terbutylazine (34%; 716 ng/L),

Bentazone (32%; 11 mg/L), Propazine (32%; 25 ng/L), PFHpA (30%; 21 ng/L), 2,4-Dinitrophenol

(29%; 122 ng/L), Diuron (29%; 279 ng/L), and Sulfamethoxazole (24%; 38 ng/L). The chemicals

whichwere detectedmost frequently above the European groundwater quality standard for

pesticides of 0.1 mg/Lwere Chloridazon-desphenyl (26 samples), NPE1C (20), Bisphenol A (12),

Benzotriazole (8), N,N0-Dimethylsulfamid (DMS) (8), Desethylatrazine (6), Nonylphenol (6),

Chloridazon-methyldesphenyl (6), Methylbenzotriazole (5), Carbamazepine (4), and Benta-

zone (4). However, only 1.7% of all single analyticalmeasurements (in totale8000) were above

this threshold value of 0.1 mg/L; 7.3% were > than 10 ng/L.

ª 2010 Elsevier Ltd. All rights reserved.

1. Introduction the world. Ground water is the most sensitive and the largest

The growing scarcity of water resources is one of the most

critical environmental problems facing us in many regions of

7; fax: þ39 0332 786351..eu (R. Loos).

ier Ltd. All rights reserved

body of freshwater in the European Union (EU) and, in

particular, also a main source of public drinking water

supplies in many regions. The EU Ground water Directive

.

wat e r r e s e a r c h 4 4 ( 2 0 1 0 ) 4 1 1 5e4 1 2 64116

(GWD) 2006/118/EC on the protection of ground water against

chemical pollution and deterioration (EC, 2006) developed

under Article 17 of the Water Framework Directive (WFD) (EC,

2000) sets out criteria for the assessment of the chemical

status of ground water. This Directive is based on existing

Community quality standards (nitrates, pesticides and

biocides) and on the requirement for Member States to iden-

tify pollutants and threshold values that are representative of

groundwater bodies found as being at risk, in accordancewith

the analysis of pressures and impacts carried out under the

WFD (EC, 2000, 2006).

The quality of ground water, as far as the pesticides

content is concerned, has been traditionally assessed in the

EU in respect to the Drinking Water Directive 98/83/EC (EC,

1998), which establishes the quality criteria of water inten-

ded for human consumption, since this is one of the most

sensitive uses of groundwater. This directive sets amaximum

concentration of 0.1 mg/L for individual pesticides and their

degradation products, and 0.5 mg/L for total pesticides present

in a sample. These values are identical to the ground water

quality standards of the GWD (EC, 2006).

In general, ground water is contaminated by sewage

wastewaters through leakage from decrepit sewer pipes, the

past practice of sewage infiltration to underground, leakages

on industrial sites or animal farms, through application of

sewage sludge from municipal waste water treatment plants

(WWTPs) on agricultural fields, urban and rural storm water

runoff, infiltration by contaminated river water, and inten-

tional application of pesticides or artificial fertilizers onto soils

(Dıaz-Cruz and Barcelo, 2008).

In the year 2000, the US Geological Survey performed

a national reconnaissance of pharmaceuticals and other

organic waste water contaminants in ground and drinking

water sources (Barnes et al., 2008; Focazio et al., 2008). In this

study, water samples were collected from a network of 47

ground water sites across 18 US States, and 65 organic

compounds were analysed. The most frequently detected

compoundswere DEET (Diethyltoluamide), an insect repellant

(frequency of detection 35%), Bisphenol A (30%), Tri(2-chlor-

oethyl)-phosphate (30%, fire retardant), Sulfamethoxazole

(23%, veterinary and human antibiotic), Carbamazepine (20%),

Tetrachloroethylene (24%, solvent), 1,7-Dimethylxanthine

(16%; caffeine metabolite), and 4-Octylphenol mono-

ethoxylate (19%). Pesticides were identified before as common

contaminants in shallow ground water (Kolpin et al., 1998),

having been found at 54% of 1034 sites sampled in agricultural

and urban settings across the United States. Of the 46 pesti-

cide compounds examined, 39 were detected, and the most

frequently detected compounds were Atrazine (38%), Dese-

thylatrazine (34%), Simazine (18%), Metolachlor (15%), and

Prometon (14%).

In Europe, the chemical monitoring of ground water has

received somewhat less attention compared to surface

waters, and comprehensive monitoring surveys are urgently

necessary. Few local studies however proved that persistent

micropollutants like carbamazepine or clofibric acid may

enter the ground water nearly un-attenuated by bank filtra-

tion of affected surface waters or by infiltration or artificial

recharge of treated wastewater into ground water (Heberer

et al., 2004; Clara et al., 2004).

The presence of pesticides in European ground waters has

been reported (in the scientific literature) in Greece

(Papastergiou and Papadopoulou-Mourkidou, 2001;

Papadopoulou-Mourkidou et al., 2004), Italy (Guzzella et al.,

2006), Portugal (Goncalves et al., 2007), and Spain

(Hildebrandt et al., 2008; Rodriguez-Mozaz et al., 2004). Liter-

ature published by national environmental agencies provides

more knowledge about the occurrence of pesticides or phar-

maceuticals in ground water (Hanke et al., 2007; BAFU, 2009).

Pharmaceutical compounds were found in ground waters

from Austria (Clara et al., 2004), Germany (Heberer and Stan,

1997; Heberer et al., 1998; Heberer, 2002; Redderson et al.,

2002; Osenbruck et al., 2007; Sacher et al., 2001; Ternes et al.,

2007), and France (Bruchet et al., 2005; Rabiet et al., 2006).

The pharmaceuticals most frequently and at the highest

concentration levels found were Carbamazepine (Clara et al.,

2004; Heberer et al., 2004; Osenbruck et al., 2007; Rabiet et al.,

2006; Sacher et al., 2001; Ternes et al., 2007), Diclofenac

(Heberer and Stan, 1997; Heberer et al., 1998; Heberer, 2002;

Redderson et al., 2002; Rabiet et al., 2006; Sacher et al., 2001),

Ibuprofen (Heberer and Stan, 1997; Heberer et al., 1998;

Heberer, 2002; Redderson et al., 2002; Rabiet et al., 2006),

Ketoprofen (Heberer and Stan, 1997; Heberer et al., 1998;

Heberer, 2002; Redderson et al., 2002; Rabiet et al., 2006),

Naproxen (Rabiet et al., 2006), Clofibric acid, Fenofibrate,

Gemfibrozil, N-(phenylsulfonyl)-sarcosine, Propyphenazone

(Heberer and Stan, 1997; Heberer et al., 1998; Heberer, 2002;

Redderson et al., 2002), Caffeine, Paracetamol (Rabiet et al.,

2006), Sotalol, Phenazone, Iopamidol, Amidotrizoic acid,

Anhydro-erythromicin, Sulfamethoxazole (Sacher et al., 2001;

Ternes et al., 2007), and X-ray contrast agents (Bruchet et al.,

2005; Ternes and Hirsch, 2000; Ternes et al., 2007).

Bisphenol A and Nonylphenol have been reported to be

frequent industrial ground water pollutants in Austria

(Hohenblum et al., 2004), Germany (Osenbruck et al., 2007;

Reinstorf et al., 2008), and Spain (Latorre et al., 2003).

Due to the apparent lack of a representative European

overview on the occurrence of organic micropollutants in

ground water, the Joint Research Centre’s Institute for Envi-

ronment and Sustainability (JRC-IES) organized a pan-Euro-

pean survey on the occurrence of selected polar organic

pollutants in European groundwaters. Fig. 1 displays a map of

the investigated ground water sampling sites.

2. Materials and methods

2.1. Sampling and transport

The investigated ground water monitoring stations were

proposed upon invitation by the individual participating EU

Member State laboratories (see acknowledgments) and finally

selected by the JRC. It is important to mention that there were

no strict selection criteria for the sampling sites such as

“representative” or “contaminated”; most monitoring

stations, however were “official” monitoring stations also

used for drinking water abstraction. The sampling was then

synchronized in a time window of 8 weeks in autumn 2008.

Sampling was performed by the participants using pre-

cleaned and conditioned sample containers provided by the

Fig. 1 e European map of the ground water monitoring sites. Note that some coordinates from Austria and Poland are

missing.

wat e r r e s e a r c h 4 4 ( 2 0 1 0 ) 4 1 1 5e4 1 2 6 4117

JRC. Upon sampling, the samples were dispatched under

cooled conditions (4 �C in cooling boxes) within 48h to the JRC

Ispra Site (Italy) for further processing. In total, 164 European

ground water sampling stations were screened, giving a rela-

tively good spatial overviewon the occurrence of polar organic

chemicals in European ground water. It must be noted,

however, that the results of this exercise cannot be seen as

a statement of the ground water quality in the Member States

or as a characterization of a single sampling station. The

campaign reflects more a comprehensive picture (“snapshot”)

of typical ground water scenarios in Europe and the data are

hence useful to draw a baseline for comparison and bench-

marking purposes. By asking Member States for support, we

are following a non-probabilistic approach, which may intro-

duce on a national level a strong bias. Thus for instance, the

map in Fig. 1 shows that several regions (e.g. Germany, France,

and Spain) were strongly under-represented. On average, i.e.

at a continental scale, however a good sample pool for the

European situation was obtained. All results described here-

after refer to the samples shipped to the facilities of the JRC’

IES-Laboratory and analysed by the same laboratory bymeans

of SPE-LC-MS2.

Methanol pre-cleaned 1 L PE or PP plastic bottles were

provided to all laboratories and sampling teams. The partici-

pants were asked to fill these bottles, leaving a small air head-

space, and storing them in a fridge atw 4 �C before dispatch by

fast courier to Ispra (Italy). The samples were shipped cooled

with freezing elements in styrofoam boxes, arrived within

48 h, and were extracted within two weeks after sampling.

Intermediate storage between the time of arrival and extrac-

tion was done at 4 �C using a laboratory refrigerator.

2.2. Solid-phase extraction (SPE)

The water samples were extracted at the JRC by solid-phase

extraction (SPE) with Oasis� HLB (200 mg) cartridges. The

water was not filtered, but decanted into a 1 L glass bottle

(Schott-Duran). Before extraction, the samples (1 L) were

spiked with the internal standard (50 mL), which contained the

labeled substances PFOA 13C4, PFOS 13C4, PFNA 13C5,

wat e r r e s e a r c h 4 4 ( 2 0 1 0 ) 4 1 1 5e4 1 2 64118

Carbamazepine d10, Simazine 13C3, Atrazine13C3, Ibuprofen

13C3, Nonylphenol 13C6, Octylphenol 13C6, Estrone d2, 2,4-D d3,

MCPA d3, and Triclosan 13C12. The spiking level in the water

samples was 5 ng/L for PFOA 13C4, PFOS 13C4, PFNA 13C5, Octyl-

and Nonylphenol 13C6, and 50 ng/L for the other labeled

compounds. The glass bottles were closed, and then the

samples were mixed by shaking.

The SPE procedure for the clean-up and concentration of

water samples was performed automatically using an

AutoTraceª SPE workstation (Caliper Life Sciences). 200 mg

(6mL) Oasis� HLB columns (Waters) were used. The cartridges

were activated and conditioned with 5 mLmethanol and 5 mL

water at a flow-rate of 5 mL/min. The water samples (950 mL;

50 mL was pumped through the tubes before for cleaning)

were passed through the wet cartridges at a flow-rate of 5 mL/

min, the columns rinsedwith 2mLwater (flow 3mL/min), and

the cartridges dried for 30 min using nitrogen at 0.6 bar.

Elution was performed with 6 mL methanol. Evaporation of

the extracts with nitrogen to 500 mL was performed at

a temperature of 35 �C in a water bath using a TurboVapª II

Concentration Workstation (Caliper Life Sciences).

2.3. Liquid chromatography tandem mass spectrometry(LC-MS2)

Analyses were performed by reversed-phase liquid chroma-

tography (RP-LC) followedbyelectrospray ionization (ESI)mass

spectrometry (MS) detection using atmospheric-pressure

ionization (API) with a triple-quadrupole MSeMS system (Agi-

lent 1100 HPLC and Waters Quattro Micro MSeMS). Quantita-

tive LC-MS2 analysis was performed in three separate LC-MS2

runs (methods 1-3) in the multiple reaction monitoring (MRM)

mode. Method 1 comprised the compounds in the negative

ionization mode, method 2 those in the positive ionization

mode, and method 3 alkylphenolic compounds and estrogens

whichwereanalysedwithadifferentHPLCmobile phase.More

analytical details can be found in Loos et al. (2007, 2008a, 2009).

2.4. Direct injection UPLC-MS/MS

Due to the polarity of certain pesticide degradation products

(e.g. DMS), conventional sample preparation methods such as

solid-phase extraction (SPE) and liquideliquid extraction (LLE)

are not applicable. Therefore, direct injection of samples in

a UPLC-ESI-MS/MS system was performed for the analysis of

DMS, Chloridazon-desphenyl and Chloridazon-methylde-

sphenyl. Calibration was done by internal standardization

using deuterium labeled DMS d6 and15N2 labeled metabolites

(Kowal et al., 2009). All experiments were carried out on

a Waters Acquity UPLC� ultra performance liquid chroma-

tography coupled with an electrospray ionization tandem

mass spectrometric system TQD-MS/MS (Waters, Milford,

USA). The UPLC columns HSS C18 2.1 � 100 mm (for DMS) and

BEH Shield C18 2.1� 50mmwere used (Waters). Particle size of

both column types were 1.8 mm. Detection was in the positive

ESI-MS mode. The m/z values of the precursor ions, product

ions, and the collision-induced dissociation (CID) energy for

the quantification transitions in the multiple reaction moni-

toring (MRM) mode are listed in Table S1.

2.5. Selection of the target compounds

Pharmaceuticals and pesticides selected are among the most

commonly used substances inmedicine and agriculture. They

were identical to the chemicals studied before in our EU-wide

monitoring survey on surface waters (Loos et al., 2009). Some

additional compounds, mainly pesticides, were added to this

ground water exercise. Focus was given to (relatively)

persistent chemicals, in order to study their environmental

behavior and fate, i.e. their infiltration potential into ground

water. DEET (Diethyltoluamide) (Costanzo et al., 2007) was

included in this survey because it was in US ground water the

most frequently detected compound (Barnes et al., 2008). N,

N0-Dimethylsulfamid (DMS), Chloridazon-desphenyl, and

Chloridazon-methyldesphenyl were analysed by IWW Water

Centre in Germany, because these herbicide metabolites have

been found in German ground waters (Buttiglieri et al., 2009;

Kowal et al., 2009).

2.6. Analytical quality control

Analytical quality control measures were described before

(Loos et al., 2009). The absolute recoveries for the chemicals

including the internal standards were determined with spike

experiments in the concentration range of 10 and 100 ng/L

using Milli-Q water (replication n ¼ 6); they were in the range

of 50e90%. The limits of detection (LODs) for the SPE-LC-MS2

procedure were calculated from the mean concentration of

the blank of real water samples plus three times the standard

deviation. The measurement uncertainty is estimated to be

around 25e50%. The analytical details are given in Table S1. In

addition, in 2009 we participated in the 3rd interlaboratory

study on perfluorinated compounds in water, fish, and sludge

(organized by Stefan van Leeuwen, Institute for Environ-

mental Studies (IVM), VU University Amsterdam, NL). More-

over, the samples from Austria were cross-checked by

Umweltbundesamt Vienna for some compounds such as

Bentazone, Atrazine, Terbutylazine, and Sulfamethoxazole.

3. Results and discussion

3.1. SPE-LC-MS2 analysis of the target compounds

The analytical details (MRM transitions, MS parameters,

retention times, recoveries, and LODs ¼ reporting limits) for

the polar organic chemicals investigated in this study are

given in Table S1 (supporting information). Fig. 2 shows

exemplary LC-MS2 chromatograms of two impacted ground

water samples in positive (A) and negative (B) ionization

modes, demonstrating that in these samples benzotriazoles,

different pesticides and their degradation products, Sulfa-

methoxazole, Carbamazepine, perfluorinated acids (PFAs),

Mecoprop and Diclofenac were detected.

3.2. Chemical compounds identified

A summary of the analytical results for the polar organic

chemicals measured in the 164 ground water samples

across Europe is given in Table 1. In total 59 different

Fig. 2 e MRM-LC-MS2 chromatograms of two impacted ground water samples. Positive (A) and negative (B) ionization

modes; Hypersil Gold column 100 3 2.1 mm, 3 mm particles; eluants: water (0.1% acetic acid) and acetonitrile; gradient start

with 90% water; flow-rate 250 ml/min.

wat e r r e s e a r c h 4 4 ( 2 0 1 0 ) 4 1 1 5e4 1 2 6 4119

organic chemical compounds were analysed. The maximum

number of compounds detected at any site was 29, and the

median number of detections per site was 12. There was no

sample free of organic chemicals; in five samples only 3

compounds were found. However, it should be noted that

the reporting limit (¼LOD) was in the low ng/L range for

most chemicals.

3.3. Frequency of detection and maximumconcentrations

The compounds in Table 1 are sorted by their frequency of

detection. The most frequently detected compounds were

DEET, Caffeine, PFOA, Atrazine, Desethylatrazine, 1H-Benzo-

triazole, Methylbenzotriazole, Desethylterbutylazine, PFOS,

Table 1 e Summary of analytical results for polar organic pollutants in EU ground waters.

Chemical LOD [ng/L] Freq [%] max [ng/L] Average [ng/L] med [ng/L] Per90 [ng/L]

DEET 0.4 83.5 454 9 1 9

Caffeine 1.0 82.9 189 13 4 32

PFOA 0.4 65.9 39 3 1 6

Atrazine 0.4 56.1 253 8 1 24

Desethylatrazine (DEA) 0.4 54.9 487 17 1 50

1H-Benzotriazole 1.0 53.0 1032 24 1 40

Methylbenzotriazole 1.0 51.8 516 20 4 42

Desethylterbutylazine (DET) 0.4 49.4 266 7 0 12

PFOS 0.4 48.2 135 4 0 11

Simazine 0.5 43.3 127 7 0 17

Carbamazepine 0.5 42.1 390 12 0 20

NPE1C 0.5 41.5 11 316 263 0 127

Bisphenol A 1.0 39.6 2299 79 0 73

PFHxS 0.4 34.8 19 1 0 5

Terbutylazine 0.3 33.5 716 6 0 2

Bentazone 0.4 31.7 10 550 116 0 15

Propazine 0.3 31.7 25 1 0 2

PFHpA 0.4 29.9 21 1 0 1

2,4-Dinitrophenol 1.0 29.3 122 4 0 6

Diuron 0.3 28.7 279 3 0 3

Sulfamethoxazole 0.5 24.4 38 2 0 4

PFDA 0.4 23.8 11 0 0 1

tert-Octylphenol (OP) 0.4 23.2 41 1 0 2

Metolachlor 0.3 20.7 209 2 0 2

Nitrophenol 4.0 20.1 152 4 0 8

Isoproturon 0.2 20.1 22 0 0 0

Hexazinone 0.3 17.7 589 4 0 1

Chloridazon-desphenyl 50 16.5 13 000 176.9 0 217

PFBS 0.3 15.2 25 0 0 1

PFNA 0.4 15.2 10 0 0 0

Mecoprop 0.2 13.4 785 7 0 1

N,N’-Dimethylsulfamid (DMS) 50 11.6 52 000 332 0 50

Nonylphenol (NP) 30.0 11.0 3850 83 0 39

Ketoprofen 1.0 10.4 2886 26 0 2

Diazinon 0.3 9.1 1 0 0 0

MCPA 0.1 7.9 36 0 0 0

Chlortoluron 0.3 7.9 91 1 0 0

Ibuprofen 0.2 6.7 395 3 0 0

Chloridazon-methyldesphenyl 50 6.1 1200 19.1 0 0

Methabenzthiazuron 0.3 5.5 104 1 0 0

Dichlorprop 0.1 4.9 3199 36 0 0

Diclofenac 0.2 4.9 24 0 0 0

Alachlor 0.3 4.9 27 0 0 0

2,4-D 0.1 3.7 12 0 0 0

2,4,5-T 0.2 3.7 3 0 0 0

Linuron 0.3 2.4 293 2 0 0

Triclosan 2.0 1.8 9 0 0 0

Estrone 1.0 0.6 4 0 0 0

Number of samples, 164; LOD ¼ limit of detection; freq ¼ frequency of detection [%]; max ¼ maximum concentration; med ¼ median

concentration; Per90¼ 90th percentile [%]; priority compounds of theWFD in blue. In green: Pesticidemetabolites analysed by IWWWater centre

(Germany). (For interpretation of the references to colour in this Table legend, the reader is referred to the web version of this article).

Not included are Naproxen, Propanil, Fenarimol, Bezafibrate, Gemfibrozil, PFHxA, PFUnA, Metoxuron, Carbaryl, and Molinate which were not

detected.

wat e r r e s e a r c h 4 4 ( 2 0 1 0 ) 4 1 1 5e4 1 2 64120

Simazine, Carbamazepine, NPE1C, Bisphenol A, PFHxS, Ter-

butylazine, Bentazone, Propazine, PFHpA, 2,4-Dinitrophenol,

Diuron, and Sulfamethoxazole.

The average frequency of detection for all compounds was

25%. A comparison with the results from the surface water

campaign (Loos et al., 2009), where the average frequency of

detection was 61%, shows a higher chemical contamination of

surface water in comparison to ground water.

Some compounds were found at high concentration levels

in the mg/L range. These chemicals detected at the highest

single concentration levels were N,N0-Dimethylsulfamid

(DMS) (52 mg/L; in one sample), Chloridazon-desphenyl (13 mg/

L), NPE1C (11 mg/L), Bentazone (11 mg/L), Nonylphenol (3.8 mg/L),

Dichlorprop (3.2 mg/L), Ketoprofen (2.9 mg/L), Bisphenol A

(2.3 mg/L), and 1H-Benzotriazole (1.0 mg/L) (see boxeplot

diagrams in Fig. 3).

Fig. 3 e Box-plot diagrams for the target compounds. Not

included are DMS (max. 52 mg/L in one sample; freq. 12%),

Chloridazon-desphenyl (max. 13 mg/L; freq. 17%),

Chloridazon-methyldesphenyl (max. 1.2 mg/L; freq. 6%) due

to their higher LODs of 50 ng/L; BTA [ Benzotriazole,

wat e r r e s e a r c h 4 4 ( 2 0 1 0 ) 4 1 1 5e4 1 2 6 4121

Fig. 3 shows boxeplot diagrams of the analytical results of

all ground water samples. The chemicals are sorted in three

groups according to their maximum concentration levels

detected. The chemicals with the highest concentrations

measured are not necessarily among the most frequently

detected compounds. For example, although several

compounds such as Nonylphenol, Dichlorprop, Ketoprofen,

DMS, and Chloridazon-desphenyl were detected infrequently,

they had single maximum concentrations which exceeded

1 mg/L (Table 1; Fig. 3). However, it should be noted that the

frequency of detection of DMS and Chloridazon-desphenyl

with a LOD of 50 ng/L cannot be directly compared to that of

the other substances with LODs around 1 ng/L.

Accordingly, compounds found with high frequency are

not those found in the highest concentrations. The best

example for this category is PFOA with a high frequency of

detection of 66%, but amaximum concentration of only 39 ng/

L. Another example is DEET, which was found in 84% of the

samples (with a reporting limit of 0.4 ng/L); the concentration

levels of DEET however were inmost cases relatively low, only

15 times higher than 10 ng/L.

3.4. Chemicals exceeding 0.1 mg per liter

The compounds which were detected in the ground waters

most frequently at “elevated” concentration levels, i.e. above

the European ground water quality standard (for pesticides) of

0.1 mg/L (EC, 2006), and above 10 ng/L are depicted in Fig. 4.

Chloridazon-desphenyl was the chemical compound which

exceeded this threshold value of 0.1 mg/L most frequently (26

times), followed by NPE1C (20 times), the transformation

product of NPEO surfactants, Bisphenol A (12 times), 1H-Ben-

zotriazole (8 times), DMS (8 times), Desethylatrazine (6 times),

Nonylphenol (6 times),Chloridazon-methyldesphenyl (6 times),

Methylbenzotriazole (5 times), and so on.

In addition, chemicals which were detected often above

the level of 10 ng/L were Caffeine (48 times), Carbamazepine

(31 times), Atrazine (28 times), Simazine (26 times), Dese-

thylterbutylazine (21 times), Bentazone (20 times), Non-

ylphenol (18 times), PFOS (17 times), and DEET (15 times) (see

Fig. 4B).

3.5. Compounds detected with low frequency

Of the 59 organic chemical compounds analysed, nearly all

were detected at least once. The substances which were not

detected at all in the ground water samples were Naproxen,

Propanil, Fenarimol, Gemfibrozil, PFHxA, PFUnA, Metoxuron,

Carbaryl, and Molinate; Benzafibrate and Estrone were only

TBA [ Terbutylazine, MBTA [ Methylbenzotriazole,

DEA [ Desethylatrazine, Carbamaz. [ Carbamazepine,

DET [ Desethylterbutylazine, DNP [ 2,4-Dinitrophenol,

MBT [ Methabenzthiazuron, Chlortol. [ Chlortoluron,

TertOP [ Tert.-Octylphenol,

Sulfamet. [ Sulfamethoxazole, D24D [ 2,4-D,

T245T [ 2,4,5-T; the box is determined by the 25th and

75th percentiles. The whiskers are determined by the 5th

and 95th percentiles.

Fig. 4 e Number of detections >0.1 mg/L and >10 ng/L.

wat e r r e s e a r c h 4 4 ( 2 0 1 0 ) 4 1 1 5e4 1 2 64122

detected once. Other compounds with a relatively low

frequency of detection were Triclosan (1.8%), Linuron (2.4%),

2,4,5-T (3.7%), 2,4-D (3.7%), Alachlor (4.9%), Diclofenac (4.9%),

Dichlorprop (4.9%), Methabenzthiazuron (5.5%), Chloridazon-

methyldesphenyl (6.1%), Ibuprofen (6.7%), Chlortoluron (7.9%),

MCPA (7.9%), and Diazinon (9.1%).

3.6. Pharmaceuticals

The most relevant pharmaceutical compound for ground

water infiltration found in this study was Carbamazepine; it

was detected in 42% of the samples, with a maximum

concentration of 390 ng/L (Table 1). Carbamazepine was

detected several times in other ground water studies (Clara

et al., 2004; Drewes et al., 2002; Heberer et al., 2004;

Osenbruck et al., 2007; Rabiet et al., 2006; Sacher et al., 2001).

Its persistent character is well established, and it also has

been proposed as a possible anthropogenic marker in the

aquatic environment (Clara et al., 2004; Fenz et al., 2005). The

secondmost important pharmaceutical compound for ground

water infiltration was Sulfamethoxazole (Barber et al., 2009),

with a detection frequency of 24%, but a relatively low

maximum concentration of 38 ng/L.

3.7. Pesticides

It is obvious from Table 1 that pesticides are among the most

relevant and important chemicals found in European ground

water samples. DEET, an important insecticide, was the most

frequently detected compound in this study. Other relevant

Sample

AA01522

mins3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0

%

0

100

%

0

100

%

0

100

%

0

100

%0

100

%

0

100239 > 1392.29e3

6.1 9.6

227 > 2123.88e4

6.1

239 > 1393.45e3

6.1

227 > 2121.02e4

6.1

239 > 1393.15e3

6.1

227 > 2121.17e3

Sample

AA01150

Sample

AA01514

Bisphenol A

154 ng/L

Bisphenol A 13

C12

50 ng/L

Bisphenol A 13

C12

50 ng/L

Bisphenol A 13

C12

50 ng/L

Bisphenol A

Bisphenol A

1138 ng/L

Fig. 5 e MRM chromatograms of Bisphenol A in ground water.

wat e r r e s e a r c h 4 4 ( 2 0 1 0 ) 4 1 1 5e4 1 2 6 4123

pesticides (herbicides) or degradation products (metabolites)

detected were Atrazine, Desethylatrazine, Desethylterbutyla-

zine, Simazine, Terbuylazine, Bentazone, Propazine, Diuron,

Chloridazon-desphenyl (and methyldesphenyl), Mecoprop,

DMS, MCPA, and Dichlorprop (see Table 1). The pesticides

which exceeded the EU standard for ground water of 0.1 mg/L

most frequently were Chloridazon-desphenyl, DMS, Dese-

thylatrazine, Chloridazon-methyldesphenyl, Bentazone,

Desethylterbutylazine, DEET, and Dichlorprop (see Section

3.4. and Fig. 4); 29% of the samples contained at least one

pesticide exceeding the EU limit value of 0.1 mg/L, and 10% of

Fig. 6 e MRM chromatograms of

the ground water samples exceeded the sum limit value for

pesticides of 0.5 mg/L.

3.8. Nonylphenol ethoxycarboxylates (NPECs)

Degradation products of widely used nonylphenol ethoxylate

(NPEO) surfactants (mostly in industrial applications) include

nonylphenol (NP), nonylphenolmono- to triethoxylates (NP1-

3EO), and nonylphenol mono- and diethoxycarboxylates

(NPE1C and NPE2C). To the best of our knowledge, there are

only two publications on the occurrence of NPECs in ground

Triclosan in ground water.

wat e r r e s e a r c h 4 4 ( 2 0 1 0 ) 4 1 1 5e4 1 2 64124

water (Ahel et al., 1996; Swartz et al., 2006), which report the

apparent persistence of NPE1C and NPE2C in ground water.

NPEC oxidation products have also been observed in incuba-

tions of NPEOs with anaerobic marine sediments (Ferguson

and Brownawell, 2003), which may explain the larger NPE2C

concentrations measured by Swartz et al. (2006) in deeper

suboxic/anoxic wells relative to the shallowest well.

In our ground water monitoring study, NPE1C was among

the most relevant compounds detected, with a frequency of

detection of 42%, and a maximum concentration level of

11.3 mg/L. Our monitoring results on NPE1C in ground water

are therefore supporting these findings by Ahel et al. (1996)

and Swartz et al. (2006), and show that the NPEO carboxyl-

ates (NPECs) are persistent chemicals widespread in European

ground waters.

In addition, it is interesting to note that Octylphenol was

more often detected than Nonylphenol (detection frequency

of 23% versus 11%). Octylphenol levels were however in all

cases low; it was detected only 5 times at > 10 ng/L (max.

41 ng/L). The reporting limit of NP was >50 ng/L due to labo-

ratory blanks (Loos et al., 2008b).

3.9. Bisphenol A

Bisphenol A is one of the most highly produced chemicals

worldwide used in the production of polycarbonate plastics

and epoxy resins (Klecka et al., 2009; Oehlmann et al., 2008). In

this study, Bisphenol A was one of the most relevant

compounds detected in European ground waters, i.e. in terms

of frequency of detection (40%), and maximum concentration

levels (2.3 mg/L). Fig. 5 shows exemplary MRM chromatograms

of Bisphenol A (together with its internal standard Bisphenol

A 13C12) in two ground water samples (sample AA01522:

1138 ng/L; sample AA01150: 154 ng/L), and one example for

a negative detection.

Our results are in good agreement to the Austrian ground

water study from the year 2000, where the most abundant

industrial chemicals found in ground water samples were

Bisphenol A and NP (maximum concentrations 930 ng/L and

1500 ng/L, respectively) (Hohenblum et al., 2004). Note that in

ground water of the German city Halle, Bisphenol A and NP

levels were higher (e1 mg/L in several places) than the concen-

trations in river water of the River Saale (Osenbruck et al.,

2007; Reinstorf et al., 2008). A possible reason for this might

be the efficient removal of Bisphenol A (>80%) during waste-

water treatment (e.g. Clara et al., 2005). The ubiquitous pres-

ence of Bisphenol A in urban ground water results from

a combination of local river water infiltration, sewer exfiltra-

tion, and urban stormwater recharge/runoff (Osenbruck et al.

(2007). It appears that Bisphenol A is persistent under anaer-

obic conditions in ground water (Ying et al., 2003).

3.10. Triclosan

Triclosan, a widely used antimicrobial agent in personal care

products (Xie et al., 2008), was only detected in 3 ground water

samples (1.8% frequency) at low concentrations between 7

and 9 ng/L. Two of these samples are shown in the MRM

chromatograms of Fig. 6 together with the internal standard

Triclosan 13C12.

3.11. EUeUS ground water study comparison

A comparison of the results of this European ground water

monitoring survey with the American US study by Barnes

et al. (2008) and Focazio et al. (2008) shows a good agreement

for several organic compounds. For instance, in both studies

DEET was the most frequently detected compound. Also

Bisphenol A, Caffeine, 5-Methyl-1H-benzotriazole and Sulfa-

methoxazole were detected relatively frequently in both the

US and Europe. However, it must be noted that the absolute

frequency of detection for the compounds is not comparable

for both studies, because the reporting limit was higher in the

US-study. It is remarkable that Triclosanwas in the US ground

water study by Barnes et al. (2008) within the most frequent

detected compounds (but not in Europe), with a frequency of

detection of 15% at a reporting limit of 1 mg/L. Thus, much

higher Triclosan levels were found in the US, compared to

Europe. The analytical results for pesticides are aswell in good

agreement to an (older) US-wide monitoring study from 1993

to 1995 (Kolpin et al., 1998), where the most frequently

detected compounds were Atrazine, Desethylatrazine, Sima-

zine, Metolachlor, and Prometon.

4. Conclusions

In this ground water monitoring study 59 polar organic

contaminants could be analysed at 164 locations in 23 Euro-

pean countries. Themost relevant chemicals found for ground

water infiltration and contamination/pollution were Caffeine,

DEET, PFOA, Atrazine (and metabolites), Benzotriazoles, Ter-

butylazine (andmetabolites), PFOS, Simazine,Carbamazepine,

NPE1C, Bisphenol A, Nonylphenol, Bentazone, Chloridazon-

desphenyl, Chloridazon-methyldesphenyl, and N,N0-Dime-

thylsulfamid (DMS). Compared to river surface water, ground

water was in general less contaminated, with an average

frequency of detection for all compounds of 25%. Some

compounds such as Chloridazon-desphenyl, NPE1C, Bisphenol

A, Benzotriazoles, DMS, Desethylatrazine, Nonylphenol, and

Chloridazon-methyldesphenyl were detected in several

samples at high concentration levels in the mg/L range,

exceeding the European ground water quality standard for

pesticides of 0.1 mg per liter. For organic chemicals other than

pesticides however no threshold limit values exist in Europe.

TheMember States of the EU shall develop such limit values in

the coming years. The results of this monitoring survey are

a valuable help for identifying possible relevant compounds.

Some compounds such as Bisphenol A and Nonylphenol were

found in some ground waters at even higher concentration

levels than in surface water. More routine ground water

monitoring should be performed to identify possible “hot spot”

areas of pollution for protecting human and ecosystemhealth.

Acknowledgements

This pan-European sampling exercise received considerable

support from a significant number of participants and

involved institutions, whose concrete help is gratefully

wat e r r e s e a r c h 4 4 ( 2 0 1 0 ) 4 1 1 5e4 1 2 6 4125

acknowledged here: BRGM (France), Environment Agency

(United Kingdom), Environmental Protection Agency (Ireland),

Umweltbundesamt GmbH (Austria), IWW Rheinisch-West-

falisches Institut fur Wasser (Germany), DGRNE (Belgium),

KIWA Water Research (The Netherlands), IAREN- Instituto da

Agua da Regiao Norte (Portugal), University of Cyprus

(Cyprus), Bundesamt fur Umwelt e BAFU (Switzerland),

Statens forurensningstilsyn e SFT (Norway), GEUS - The

National Geological Survey of Denmark and Greenland

(Denmark), Water Research Institute (Slovak Republic), IRTA

Aquatic Ecosystems (Spain), Naturvardsverket (Sweden),

Maves Ltd (Estonia), University of Santiago de Compostela

(Spain), Finnish Environment Institute SYKE (Finland), Envi-

ronmental Agency of the Republic of Slovenia (Slovenia),

Vlaamse Milieumaatschappij (Belgium), Central Directorate

for Environment and Water e VKKI (Hungary), Czech Hydro-

meteorological Institute (Czech Republic), Ministry of Envi-

ronment of Ukraine (Ukraine), TUBITAK MRC CEI (Turkey),

Technical University of Crete (Greece), Administration de la

Gestion de l’Eau (Luxembourg), Bulgarian Academy of

Sciences (Bulgaria), Comune di Milano (Italy), Geological

Survey of Sweden (Sweden), Umhverfisstofnun e Environ-

ment Agency of Iceland (Iceland), Institute of Nuclear Chem-

istry and Technology (Poland), Amt der Steiermarkischen

Landesregierung (Austria), RIVM (The Netherlands).

In addition an important number of persons at the various

sampling stations has contributed to the success of this

campaign. Thanks to all of them.

Appendix. Supplementary data

Supplementary data associated with this article can be found,

in the online version, at doi:10.1016/j.watres.2010.05.032.

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