Chapter 9

Residues of Clofibric Acid, Ibuprofen and Diclofenac

in the Aquatic Environment and their Elimination in
Sewage Treatment and Drinking Water Production
C. Zwiener . F. H. Frimmel

9.1
Introduction

Pharmaceuticals belong to the emerging issues in environmental chemistry. They are

produced and administered for human and animal medical care. Due to the amount
and type of application pharmaceuticals can reach the aquatic environment, in par-
ticular the ones used for medicine and veterinary drugs (Halling-S0rensen et al.1998).
Being produced and applied with the aim of causing a biological effect, their occur-
rence in the environment is of ecotoxicological interest. In particular this is of impor-
tance for the antibiotics, but also for antineoplastics, hormones (compounds with en-
docrinic effects) and for various compounds and metabolites that have already been
detected in sewage plant effluents and surface water in considerable concentrations
(e.g. bezafibrate, clofibric acid, ibuprofen, carbamazepine, iopamidol) (Heberer 2002a;
Ternes 2001; Kiimmerer 2001; Ternes and Hirsch 2000; Stumpf et al. 1999; Hirsch et al.
1999). More than 80 compounds, pharmaceuticals and several metabolites, have been
detected in the aquatic environment in nine different countries of Europe, in Brazil,
the US and Canada.
The occurrence of pharmaceuticals in surface waters can be directly correlated to
the proportion of treated and untreated municipal wastewater. 36 out of 55 selected
pharmaceuticals have been found in effluents of sewage treatment plants with maxi-
mum concentrations in the fig rl range for the antiepileptic drug carbamazepine, the
antiphlogistics diclofenac and ibuprofen and with concentrations above 10 Ilg rl for
the X-ray contrast media iopamidol and iopromide (Table 9.1). In samples from 40 Ger-
man rivers those compounds have been found still at concentrations in the range be-
tween 0.5 and 2.8 fig rl (Ternes 2001).
The measured concentrations can be even higher in urban areas with high munici-
pal sewage water discharges and low surface water flows. Groundwater wells located
near contaminated surface waters can show concentrations of pharmaceutical residues
in the low fig rl range (Table 9.2). That has been shown for the particular situation of
the city of Berlin (Heberer 2002b). There is also a potential risk of drinking water con-
tamination if groundwater is used for drinking water supply. For example clofibric acid
has been measured in several drinking water samples from the Berlin water works in
the range of several tens of nanograms per litre (Heberer et al. 1998; Heberer and Stan
1996).
Those examples clearly reveal that pharmaceuticals which are not readily biode-
gradable in sewage treatment and which are persistent and highly mobile in the aquatic
environment can be tracked from municipal sewage water to drinking water. In this
context also caffeine, a constituent of a variety of beverages (e.g. coffee, tea) and of

K. Kümmerer (ed.), Pharmaceuticals in the Environment

© Springer-Verlag Berlin Heidelberg 2004
122 C. Zwiener . F. H. Frimmel

Table 9.1. Estimated amounts of some selected pharmaceuticals applied in Germany and concentra-
tions found in secondary effluents and surface waters (from Heberer and Stan 1998; Stumpf et aI. 1996;
Hirsch et al. 1999; Ternes 2001)

Agent Applied mass Concentration in Concentration in

(t a- 1) sewage effluents surface water
(I-Ig 1-1) (I-Ig 1- 1)

Lipid regulators
Clofi bric acid 15 ... 21 0.46 ... 1.56 0.005 ... 030
Bezafibrate 38 ... 57 0.25 ... 4.56 0.005 ... 038
Gemfibrozil l.5 a 0.51

Antiphlogistics
Ibuprofen 48 ... 96 0.05 ... 335 0.05 ... 0.28
Diclofenac 48 ... 72 0.005 ... 1.59 0.005 ... 0.49
Phenazone 0.41 a 0.95 a
Acetylsalic. acid 23 ... 116 0.05 ... 1.51 <0.05

Betablockers
Bisoprolol 112 037 a 2.9 a
Metoprolol 50 2.2' 2.2 a

Antieplleptic
Carbamazepine 6.9a l.la

Antibiotics
Clarithromycin l.3 ... 2.6 0. 24a 0.26a
Erythromycin 3.9 ... 19.8 6.00a 1.70a
Roxithromycin 3.1 ... 6.2 l.OOa 0.56a
Sulfamethoxazole 16.6 ... 76 2.00a 0.48a
Trimethoprim 33 ... 15 0.66a 0. 20 a

X-ray contrast
lopamidol 15 a 2.8 a
lopromide l30 11 a 0.9a

a Maximum values.

numerous food products (e.g. chocolate, dairy desserts) has been proposed as chemi-
cal marker for domestic wastewater (Buerge et al. 2003). Caffeine concentrations in
lakes correlated well with the anthropogenic burden of wastewaters.
The same principle can be applied for selected high-volume pharmaceutical com-
pounds like X-ray contrast media, which show high persistence and mobility in the
aquatic environment. It should be added that X-ray contrast media are not therapeu-
tically active compounds and therefore of less toxicological and ecotoxicological con-
cern (Mutschler 1996). However, the precautionary principle states that drinking wa-