Risk assessment for the disposal of wastewater containing emerging

micropollutants in Greek aquatic environment

Vasiliki S. Thomaidi, Msc student, Department of Environment, University of the Aegean.

Evangelia I. Iatrou, PhD student, Department of Environment, University of the Aegean.
Athanasios S. Stasinakis, Assistant Professor, Department of Environment, University of the Aegean.
Nikolaos S. Thomaidis, Assistant Professor, Department of Chemistry, University of Athens.

Contact: Dr A.S. Stasinakis, University of the Aegean, 81100 Mytilene, tel: +30 22510 36257, e-mail:
[email protected]
EXECUTIVE SUMMARY

The term emerging micropollutants refers to compounds which are not covered by existing laws on water
quality, they have not been studied enough in the past and it is believed to pose a threat to ecosystems,
human health and safety. These compounds are used in large quantities in our daily life. As a result, they
are detected at high concentrations in raw and treated wastewater and they are released in large quantities
in the environment and especially in surface waters, where they undergo different degrees of
transformation. Some of them remain stable for a long time and it is very difficult to degrade.
The main objectives of this study were to record the concentration levels of emerging contaminants that
have been published in literature for Greek Sewage Treatment Plants (STPs) and to estimate the
environmental risks associated with these compounds to the Greek aquatic environment. Toxicity data
were collected for these compounds after literature review or using ECOSAR program and the risk
quotients (RQ) were calculated for treated wastewater and Greek rivers, dividing Measured Environmental
Concentration (MEC) to Predicted No Effect Concentration (PNEC), for 3 different aquatic organisms:
fish, daphnia magna and algae.
According to the results, monitoring data are available for 48 emerging contaminants in Greek STPs’
effluents. These compounds belong to 6 different classes of synthetic organic micropollutants; namely
pharmaceuticals (PhCs), endocrine disruptors (EDCs), perfluorinated compounds (PFCs), benzotriazoles
(BTrs), benzothiazoles (BThs) and artificial sweeteners. Their concentration levels range between few ng
L-1 (perfluorinated compounds) to some tens of µg L-1 (artificial sweeteners). According to the results of
risk assessment, EDCs seem to be the most dangerous class of the emerging pollutants in both wastewater
and river. Triclosan (in algae) and nonylphenol (in fish) have the highest RQs among EDCs, while the
pharmaceutical compound phenazon (in algae) has the highest RQ of all studied emerging contaminants.
River Soulou seems to face the greatest ecological risk due to the presence of micropollutants.

Keywords: emerging micropollutants; sewage treatment; environmental risk assessment; risk quotient;
ECOSAR; aquatic environment
1. INTRODUCTION

Synthetic organic micropollutants, which are often released into the aquatic environment through
effluents of sewage treatment plants (STPs), can remain stable for a long time without being degraded.
These compounds may be toxic and accumulate in food chain, causing hazards to humans and to the
environment. Emerging micropollutants, belonging to organic micropollutants, have long been present in
the environment, but have not gained scientific attention until recently (Wu et al., 2010). They are used in
large quantities in our daily life and include a wide variety of compounds such as drugs from different
therapeutic groups (PhCs), personal care products (PCPs), endocrine disruptors (EDCs), perfluorinated
compounds (PFCs), flame retardants, industrial additives and reagents, artificial sweeteners,
benzotriazoles (BTrs), benzothiazoles (BThs), nanomaterials, 1,4 dioxane and water disinfection by-
products (Farré et al., 2008; Giger, 2009; Wu et al., 2010; Mahugo-Santana et al., 2011).
PhCs are a class of emerging pollutants that are extensively being used in human and veterinary medicine.
In the European Union about 3000 different substances are used in human medicine, such as analgesic
and anti-inflammatory drugs, lipid regulators, antibiotics, beta-blockers, anti-epileptics, neuroactive
compounds and many others (Fent et al., 2006). The main source of PhCs to aquatic environment is
excretion from humans and animals, although wastewater from manufacturers, hospitals and disposal of
unconsumed medicine are of significance, as well (Houtman, 2010; Ziylan and Ince, 2011).
EDCs are pollutants that have the potential to cause negative effects on the endocrine system of aquatic
and terrestrial organisms (Liu et al., 2009; Yoon et al, 2010). This broad class of chemicals includes
natural estrogens, as well as other industrial compounds, such as alkylphenols and their ethoxylate
oligomers, bisphenol A and triclosan (Bester, 2003; Liu et al., 2009). Alkylphenols and alkylphenol
ethoxylates are used in industrial, agricultural and household applications as detergents, emulsifiers,
wetting agents, dispersants or solubilizers (Pothitou and Voutsa, 2008). BPA is used in a large number of
products, such as protective coatings, CDs, thermal paper, colors (Staples et al., 1998), while triclosan is
used as a bacrericide in toothpaste and detergents, as well as in sports clothing (Bester, 2003).
PFCs are compounds consisting of a hydrophobic alkyl chain (C4 to C16), which is fully fluorinated, and
a hydrophilic end group (EFSA, 2008). The best known applications of PFCs are non-stick pans and
cooking utensils, which are widely known by the brand name TEFAL, fabrics for furniture made of
synthetic fibers, transparent films, foams and food packaging materials (EFSA, 2008; Ahrens, 2011). The
most important and widely-studied PFCs are perfluorooctanoic acid (PFOA) and perfluorooctane
sulfonate (PFOS) (Lin et al., 2010).
BTrs and BThs are polar high production volume chemicals, which have wide industrial and domestic
applications. They are used as corrosion inhibitors in deicing fluids for aircrafts and cars, in brake fluids
and as dishwasher detergents to protect silverware (Weiss και Reemtsma, 2005).
Artificial sweeteners are used primarily for the manufacture of foods for diabetics, but also consumed by
people who care about their diet. Foodstuffs containing artificial sweeteners classified as ‘diet’ or ‘light’.
The most popular artificial sweeteners are cyclamate, saccharin, aspartame, acesulfame-K and sucralose.
The list of authorized artificial sweeteners varies from country to country (Zygler et al., 2009).
The aims of this study were to record the concentration levels of emerging contaminants that have been
published in literature for Greek Sewage Treatment Plants (STPs) and to estimate the environmental risks
associated with these compounds to treated wastewater and Greek rivers. Based on the maximum
concentrations and acute toxicity data, the potential environmental risk due to the disposal of treated
wastewater to Greek rivers was estimated.

2. MATERIALS AND METHODS

2.1 Occurrence of emerging micropollutants in Greek Sewage Treatment Plants (STPs)

In this study, data related to the existence of emerging micropollutants in Greek STPs were collected.
After literature review, effluents concentrations were recorded and the maximum concentration for each
substance was selected, since the risk assessment is based on the most adverse case (worst-case scenario).
The maximum concentration value corresponds to the value of MEC (Measured Environmental
Concentration), which is used in the risk assessment calculations, according to the Technical Guidance
Document of the European Commission (2003).

2.2 Environmental Risk Assessment

Toxicity data were collected for the emerging contaminants and the risk quotients (RQ) were calculated
for treated wastewater, dividing Measured Environmental Concentration (MEC) to Predicted No Effect
Concentration (PNEC), for 3 different aquatic organisms: fish, daphnia magna and algae.

RQ = (1)

In cases that RQ is less than 1, no ecotoxicological risk for the aquatic environment is indicated, while in
cases that RQ is greater than 1, ecotoxicological risk for the aquatic environment is indicated and further
research is required.
According to the Technical Guidance Document of the European Commission (2003), PNEC was
calculated by dividing the LC50 or EC50 value by an appropriate assessment factor. Since only short-term
toxicity data were available, an assessment factor of 1000 was applied on the lowest LC50 or EC50 value.

PNEC = (2)

In order to collect LC50 or EC50 values for all the emerging micropollutants, a literature review was
initially held. In cases that there were no data in the literature, ECOSAR program was used to predict LC50
or EC50 values. The ECOSAR program is used to predict the aquatic toxicity of compounds based on the
similarity of structure to compounds for which the aquatic toxicity has been previously measured. Most
calculations in the ECOSAR program are based on various physicochemical constants and especially on
the octanol/water partition coefficient (Kow).
To calculate risk quotients (RQ) in Greek rivers, data about the average effluents flows of 24 Greek STPs
and the average water flows of the corresponding rivers were collected. The concentrations of
micropollutants in rivers were estimated, according to the dilution factor of the STP effluents.

3. RESULTS AND DISCUSSION

3.1 Emerging pollutants in Greek Sewage Treatment Plants (STPs)

So far, there is a limited number of published works related to the presence of emerging micropollutants in
Greek aquatic environment. According to the results of the current study, 48 emerging contaminants have
been detected in Greek STPs, belonging in 6 different classes of organic micropollutants: pharmaceuticals
(PhCs), phenolic endocrine disruptors (EDCs), perfluorinated compounds (PFCs), benzotriazoles (BTrs),
benzothiazoles (BThs) and artificial sweeteners. Their concentration levels range between few ng L-1
(perfluorinated compounds) to some tens of µg L-1 (artificial sweeteners). The maximum concentrations of
the compounds in treated wastewater (MEC) are shown in Figure 1.

3.2 Risk assessment in treated wastewater and Greek rivers

To estimate the environmental risks associated with emerging contaminants to the Greek aquatic
environment, RQ values were calculated. According to the results, 59% of the compounds present in the
effluents of STPs do not pose any risk to aquatic organisms. The RQ values for compounds that have
RQ > 1 in treated wastewater are summarized in Table 1. The class of emerging contaminants
that seems to present the greater risk to aquatic organisms is EDCs. Overall, the substances in this
class have RQ > 1 for fish, while for daphnia magna and algae, the only substances with RQ < 1
are tOP and BPA. Extremely high are the RQ values for TCS (in algae) and NP (in fish). In the
class of PhCs, SMX (in algae), DCF (in fish), GFZ (in fish) and PHZ (in algae) seem to possess
environmental risks, while PHZ have the highest RQ of all studied emerging pollutants. All PFCs
and BThs have RQ < 1, whereas one compound of the class of BTrs (5-MeBTri) and two
compounds of the class of artificial sweeteners (SUC and CYC) have RQ > 1 in algae. As it was
expected, for most emerging contaminants, the most sensitive aquatic organisms seem to be algae
(Table 1).
Figure 1. Maximum concentrations of emerging contaminants that have been detected in treated wastewater of Greek STPs
Table 1. Risk Quotients (RQ) for emerging contaminants having RQ values greater than 1 in
treated wastewater of Greek STPs
Compound Abbreviation RQ = MEC/PNEC
Fish Daphnia magna Algae
Sulfamethoxazole SMX 0.0007 0.040 13.3
Diclofenac DCF 1.32 0.318 0.483
(*) (*)
Phenazon PHZ 0.193 0.070 19830(*)
Gemfibrozil GFZ 1.89 0.136 0.425
Triclosan TCS 26.5 17.6 4914
Nonylphenol NP 857 66.8 30.1
4-n-nonylphenol 4-n-NP 12.5(*) 13.4(*) 6.08(*)
Nonylphenol monoethoxylate NP1EO 31.6 21.0 22.1(*)
Nonylphenol diethoxylate NP2EO 53.9 24.3 32.2(*)
4-t-octylphenol tOP 1.43 0.183 0.105(*)
Bisphenol A BPA 6.96 0.282 0.440
5-methyl-1H-benzotriazole 5-MeBTri 0.262 0.071 1.33(*)
Sucralose SUC 0.006(*) 0.012(*) 72.9(*)
Cyclamate CYC 0.002(*) 0.002(*) 2.67(*)
(*) Calculated with ECOSAR program (ECOWIN v.1.00)
All other values calculated with experimental acute toxicity data

The RQ values for compounds that have RQ > 1 in Greek rivers are summarized in Table 2.
According to the results, PHZ and TCS have RQ > 1 in all studied rivers and pose a possible ecological
risk in algae, while except of Evros and Alfeios, in all other rivers NP has RQ > 1 and possess risk in fish.
In contrast, DCF, GFZ, tOP, 5-MeBTri and CYC, which in the effluents of STPs seem to cause toxicity to
aquatic organisms, in rivers seem to possess no risk, due to the high dilution factor of the STP effluents.
The greatest problem is presented in river Soulou (Ptolemaida), where 8 substances (SMX, PHZ, TCS,
NP, NP1EO, NP2EO, BPA and SUC) seem to cause toxicity to aquatic organisms, due to the low dilution
factor (1:3) of the STP effluents.

4. CONCLUSIONS

The concentrations of 48 emerging contaminants in Greek STP’s effluents have been monitored. Their
levels range between few ng L-1 (perfluorinated compounds) to some tens of µg L-1 (artificial sweeteners).
According to the results of risk assessment, EDCs present the highest risk of all emerging pollutants in
both wastewater and river. Triclosan (in algae) and nonylphenol (in fish) have the highest RQs among
EDCs, while the pharmaceutical compound phenazon (in algae) has the highest RQ of all studied
emerging contaminants. River Soulou seems to face the greatest ecological risk, due to the low dilution
factor (1:3) of the STP effluents.
Table 2. Risk Quotients (RQ) for compounds that have RQ > 1 in Greek rivers
Rivers RQ for Fish RQ for Daphnia Magna
TCS NP NP1EO NP2EO BPA TCS NP NP1EO NP2EO
Soulou (Ptolemaida) 8.83 286 10.5 18.0 2.32 5.87 22.3 7.00 8.10
Aisonas (Katerini) 2.41 77.9 2.87 4.90 0.633 1.60 6.07 1.91 2.21
Lithaios (Trikala) 2.41 77.9 2.87 4.90 0.633 1.60 6.07 1.91 2.21
Erkynas (Leivadia) 1.89 61.2 2.26 3.85 0.497 1.26 4.77 1.50 1.74
Sakoulevas (Florina) 1.77 57.1 2.11 3.59 0.464 1.17 4.45 1.40 1.62
Vozvozis (Komotini) 1.66 53.6 1.98 3.37 0.435 1.10 4.18 1.31 1.52
Evrotas (Sparti) 1.47 47.6 1.76 2.99 0.387 0.978 3.71 1.17 1.35
Aggitis (Drama) 1.20 39.0 1.44 2.45 0.316 0.800 3.04 0.955 1.10
Kalamas (Ioannina) 0.541 17.5 0.645 1.10 0.142 0.359 1.36 0.429 0.496
Peneios (Karditsa) 0.262 8.49 0.313 0.534 < 0.1 0.174 0.661 0.208 0.241
Karpenisiotis (Karpenisi) 0.199 6.44 0.238 0.405 < 0.1 0.132 0.502 0.158 0.183
Peneios (Larisa) 0.187 6.04 0.223 0.380 < 0.1 0.124 0.470 0.148 0.171
Loudias (Giannitsa) 0.115 3.73 0.137 0.234 < 0.1 < 0.1 0.290 < 0.1 0.106
Peneios (Kalampaka) < 0.1 3.14 0.116 0.197 < 0.1 < 0.1 0.245 < 0.1 < 0.1
Strymonas (Serres) < 0.1 3.00 0.110 0.188 < 0.1 < 0.1 0.234 < 0.1 < 0.1
Alfeios (Pyrgos) < 0.1 2.69 < 0.1 0.169 < 0.1 < 0.1 0.210 < 0.1 < 0.1
Aliakmonas (Veroia) < 0.1 1.41 < 0.1 < 0.1 < 0.1 < 0.1 0.110 < 0.1 < 0.1
Titarisios (Tyrnavos) < 0.1 1.14 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1
Gallikos (Kilkis) < 0.1 1.08 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1
Aheloos (Agrinio) < 0.1 1.04 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1
Arahthos (Arta) < 0.1 0.982 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1
Aliakmonas (Kastoria) < 0.1 0.939 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1
Alfeios (Krestena) < 0.1 0.449 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1
Evros (Orestiada) < 0.1 0.359 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1

Rivers RQ for Algae

PHZ SMX TCS NP NP1EO NP2EO SUC
Soulou (Ptolemaida) 6610 4.43 1640 10.0 7.37 10.7 24.3
Aisonas (Katerini) 1800 1.21 447 2.74 2.01 2.93 6.63
Lithaios (Trikala) 1800 1.21 447 2.74 2.01 2.93 6.63
Erkynas (Leivadia) 1420 0.950 351 2.15 1.58 2.30 5.21
Sakoulevas (Florina) 1320 0.887 328 2.01 1.47 2.15 4.86
Vozvozis (Komotini) 1240 0.831 307 1.88 1.38 2.01 4.56
Evrotas (Sparti) 1100 0.739 273 1.67 1.23 1.79 4.05
Aggitis (Drama) 901 0.605 223 1.37 1.00 1.46 3.31
Kalamas (Ioannina) 405 0.271 100 0.614 0.451 0.657 1.49
Peneios (Karditsa) 196 0.132 48.7 0.298 0.219 0.319 0.722
Karpenisiotis (Karpenisi) 149 0.100 36.9 0.226 0.166 0.242 0.548
Peneios (Larisa) 140 < 0.1 34.6 0.212 0.156 0.227 0.513
Loudias (Giannitsa) 86.2 < 0.1 21.4 0.131 < 0.1 0.140 0.317
Peneios (Kalampaka) 72.6 < 0.1 18.0 0.110 < 0.1 0.118 0.267
Strymonas (Serres) 69.3 < 0.1 17.2 0.105 < 0.1 0.113 0.255
Alfeios (Pyrgos) 62.4 < 0.1 15.5 < 0.1 < 0.1 0.101 0.229
Aliakmonas (Veroia) 32.6 < 0.1 8.08 < 0.1 < 0.1 < 0.1 0.120
Titarisios (Tyrnavos) 26.4 < 0.1 6.55 < 0.1 < 0.1 < 0.1 < 0.1
Gallikos (Kilkis) 25.1 < 0.1 6.22 < 0.1 < 0.1 < 0.1 < 0.1
Aheloos (Agrinio) 24.1 < 0.1 5.96 < 0.1 < 0.1 < 0.1 < 0.1
Arahthos (Arta) 22.7 < 0.1 5.63 < 0.1 < 0.1 < 0.1 < 0.1
Aliakmonas (Kastoria) 21.7 < 0.1 5.38 < 0.1 < 0.1 < 0.1 < 0.1
Alfeios (Krestena) 10.4 < 0.1 2.57 < 0.1 < 0.1 < 0.1 < 0.1
Evros (Orestiada) 8.30 < 0.1 2.06 < 0.1 < 0.1 < 0.1 < 0.1
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