Delliverable 6
6.1.1 WATE
ERMICROPO
OL University
y of the Aeegean, Dep
partment o
of Environ
nment Water and
d Air Quality Laboraatory WAT
TERMICROPOL
INVEST
TIGATION OF ORGA
ANIC MICROPOLLU
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FATE IN WASSTEWATE
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TMENT AN
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DISPOSAL
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ONMENT Wo
ork Pacckage 6 – Disposal to the aquatic environmennt Deliverablle 6.1.1
1 – Techhnical Reeport ‘Inveestigatio
on of Micropol
M
llutants’ Photod
degradaation du
uring Treaated Wasstewaterr Disposal to thee Aquaticc Environ
nment’ Deliv
verable su
ubmission
n date ‐ 28
8.03.13 Deliv
verable lead contraactor–Nattional Tecchnical Un
niversity o
of Athenss Auth
hors: Dan
niel Mamais, Consstantinos Noutsop
poulos, Elleni Koumaki, Marianna Giolldasi, Mattina Marn
neri, Georgge Nikitop
poulos ---------------------------------------------------------------------------------------------------------------------1
Delliverable 6
6.1.1 WATE
ERMICROPO
OL W
WATERM
MICROPO
OL has beeen co‐finnanced byy the Euroopean Uniion (E
European Social Fu
und ‐ ESF)) and Greeek nation
nal funds tthrough the Opeerational P
Program “Educatio
on and Liffelong Leaarning” off the National Strategic Reference F
Frameworrk (NSRF)) – Researrch Fundiing Prograam: THALES Startt date off the pro
oject ‐ 01
1.01.12 End date of tthe projeect ‐ 30.0
09.15 Coorrdinatorr ‐ University of tthe Aegeean Co‐P
Partners – Nation
nal Tech
hnical Un
niversity
y of Atheens Nation
nal and K
Kapodisttrian Uniiversity of Athen
ns http
p://www.aaegean.gr//environm
ment/wateermicropol --------------------------------------------------------------------------------------------------------------------- 2
WATERMICROPOL Deliverable 6.1.1 Contents Summary .............................................................................................................. 4 1. Introduction ................................................................................................... 6 1.1 Endocrine disrupting compounds (EDCs) .......................................................... 7 1.2 Pharmaceutical compounds (Phs) ...................................................................... 11 1.3 Benzotriazoles (BTs) – Benzothiazoles (BThzs) .......................................... 11 2. Objectives ..................................................................................................... 13 3. Materials and Methods ........................................................................... 14 3.1 Chemicals ...................................................................................................................... 14 3.2 Photodegradation Batch Experiments ............................................................. 14 3.3 Analytical Methods .................................................................................................... 15 4. Results and Discussion ........................................................................... 16 4.1 Photodegradation Experiments ........................................................................... 16 4.2 Effect of pH on Photodegradation ...................................................................... 19 5. Conclusions .................................................................................................. 21 References………………………………………………………………………….22 ---------------------------------------------------------------------------------------------------------------- 3
WATERMICROPOL Deliverable 6.1.1 Summary Emerging contaminants are compounds which present significant scientific interest due to their toxicological and chemical characteristics. It has been shown that they are toxic, readily bioavailable to living organisms, able to enter the food chain and hence ultimately exposing humans. In the environment, they are released from domestic, industrial, and agricultural sources. Wastewater treatment plants are a well known source and one of the most significant ways for their transfer to the aquatic environment. In the context of this work, bench scale experiments were performed in order to assess the fate of selected endocrine disrupting compounds (EDCs), pharmaceutical compounds (Phs), benzotriazoles (BTs) and benzothiazoles (BThzs) through their transport to the aquatic environment mainly due to solar irradiation. Bench scale batch experiments were conducted to evaluate the effect of light and pH on the fate of the above micropollutants and their relevant removal kinetics, according to OECD 316 protocol (2008). Solar irradiations were carried out at NTUA, Greece (latitude 37°58' N, altitude 160 m above sea level). For the determination of the target compounds, water samples before and after being irradiated for several time intervals were analyzed. Exposure to sunlight was continuous and similar experiments were carried out in the dark to account for hydrolysis. According to the results photodegradation is the major mechanism for the removal of DFC, KFN, NPX and TCS which shown half‐lives lower than one day. On the other hand, neither IBF nor NP2EO was found to be photodegradated. Finally, regarding the effect of pH on EDCs and Phs, it seems that degradation rate for most of the target compounds is not ---------------------------------------------------------------------------------------------------------------- 4
Deliverable 6.1.1 WATERMICROPOL significantly affected during irradiation under different pH values. Among all target compounds, only TCS removal was affected by pH. ---------------------------------------------------------------------------------------------------------------- 5
WATERMICROPOL Deliverable 6.1.1 1. Introduction Emerging contaminants is a rather diverse and heterogeneous group of chemicals consisting of pharmaceuticals and personal care products, steroids and hormones, drugs, fragrances, surfactants, flame retardants, perfluorinated compounds, complexing agents, etc. Several studies reported the frequent detection of these compounds into the aquatic environment in wastewaters, surface waters, ground waters and in some cases in the drinking water (Kolpin et al., 2002; Benotti et al., 2009; Loos et al., 2009; Bolong et al., 2009; Pojana et al., 2011; Jonkers et al., 2012; MartínezBueno et al., 2012). In the environment, emerging contaminants (ECs) are substances released from domestic, industrial, and agricultural sources (Yan et al., 2010). Wastewater treatment plants (WWTPs) are a well known source and one of the most significant pathways for their transfer to the environment (Nakada et al., 2006, Tan et al., 2007; Stasinakis et al., 2008; Samaras et al., 2009). Beside the fact that these compounds are detected in low concentrations (ng/l) (Ratola et al., 2012), some of them present significant scientific interest due to their toxicological and chemical characteristics. It has been shown that some of these chemicals are toxic, readily bioavailable to living organisms, able to enter the food chain and hence ultimately exposing humans (Katsoyiannis and Samara, 2007). Among synthetic organic compounds which are usually detected in wastewater, benzotriazoles (BTs), benzothiazoles (BTzhs) some endocrine disrupting chemicals (EDCs) containing in everyday use products and pharmaceuticals (PhCs) present significant research interest. A literature review has shown that so far there are limited or no data for the fate of some of these compounds during wastewater treatment and during their disposal to the aquatic environment. This study was focused on 4 different categories of ECs, namely; pharmaceuticals compounds, endocrine disrupting compounds, benzotriazoles and benzothiazoles. ---------------------------------------------------------------------------------------------------------------- 6
WATERMICROPOL Deliverable 6.1.1 1.1 Endocrine disrupting compounds (EDCs) Several synthetic organic compounds have been detected in every‐day products and they are considered suspicious for endocrine disruption. Among them, nonylphenols (NPEs), bisphenol A (BPA) and triclosan (TCS) present significant interest. These compounds are considered as EDCs (Vazquez–Duhalt et al., 2005; Soares et al., 2008), while NP is reported in Directive 2000/60/EU (EU, 2001). NPEs, TCS and BPA are considered as hydrophobic compounds (Birkett and Lester, 2003; Singer et al., 2002). All the aforementioned compounds have been detected in surface, groundwater and wastewater treatment plants, which are considered the major source for their transfer to the environment (Singer et al., 2002; Ying et al., 2002; Stasinakis et al., 2008; Chalew and Halden, 2009; Ratola et al., 2012). The major mechanisms affecting the fate of these compounds are sorption on suspended solids and biotransformation (Singer et al., 2002; Bester, 2003; Heidler and Halden, 2007; Stasinakis et al., 2007; Photitou and Voutsa, 2008; Stasinakis et al., 2010). So far, there are several studies published for the fate of these compounds during photodegradation using filtered xenon arc lamps or sunlight irradiation. Specifically, photodegradation seems to be the major mechanism for TCS removal in the aquatic environment (Singer et al., 2002; Latch et al., 2005; Sanchez – Prado et el., 2006). In another study, Neamtu et al. (2006) reported that the removal of NPEs during photodegradation affected by the concentration of dissolved organic matter and NO3‐
N. Table 1 presents the basic characteristics and the absorption spectrums of the target compounds. ---------------------------------------------------------------------------------------------------------------- 7
Deliverable 6.1.1 WATERMICROPOL Table 1 Target compounds of emerging contaminants. Compound Chemical Structure Chemical Molecular Formula Weight Absorption spectrum Endocrine Disrupting compounds C12H7Cl3O2 Triclosan, TCS 289.54 Bisphenol A, C15H16O2 BPA 228,29 Nonylphenol, ΝΡ Nonylphenolm
C15H24O 220,35 C17H28O2
264
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8
Deliverable 6.1.1 WATERMICROPOL onoethoxylate, NP1EO Nonylphenol diethoxylate, C19H32O3 308 NP2EO Pharmaceuticals Diclofenac, DCF
C14H10Cl2NO2Na 318.10 C13H18O2 Ibuprofen, IBU 206,29 -----------------------------------------------------------------------------------------------------------------
9
Deliverable 6.1.1 WATERMICROPOL C14H14O3 Naproxen, NPX 230,26 Ketoprofen, C16H14O3 KFN 254,28 Benzotriazoles 1‐H‐BTR C6H5N3 119.12 -----------------------------------------------------------------------------------------------------------------
10
WATERMICROPOL Deliverable 6.1.1 1.2 Pharmaceutical compounds (Phs) Non‐steroidal anti‐inflammatory drugs (NSAIDs) are a significant group of pharmaceuticals usually detected in environmental samples. Ibuprofen (IBF), naproxen (NPX), ketoprofen (KTF) and diclofenac (DCF) are representative compounds of NSAIDs which present significant interest. Regarding NSAIDs, there are some indications for toxic effects on aquatic organisms, in cases that are present as mixtures due to synergistic and additive effects (Carballa et al., 2004; Crane et al, 2006; Hernando et al, 2006; Pomati et al., 2008; Pounds et al, 2008; Quinn et al., 2009). NSAIDs present medium to high hydrophobicity (Barcelo and Petrovic, 2007). All the aforementioned compounds have been detected in surface, groundwater and wastewater treatment plants, which are considered the major route for their transfer to the environment (Kolpin, et al., 2002; Benotti et al., 2009; Samaras et al., 2009; Pojana et al., 2011; Ratola et al., 2012). The major mechanism affecting the fate of these compounds is biotransformation (Buser et al., 1999; Hernando et al., 2006; Carballa et al., 2004; Kumagai et al., 2006; Kosjek et al., 2007; Zhang et al., 2008; Mascolo et al., 2010). Regarding the fate of these compounds during photodegradation, it has been reported that half life of IBF and KTF are 600‐900 hours and 0.54 hours respectively (Pal et al., 2011; Matamoros et al., 2009). Also, half life of DFC during winter in latitude 50° N is equal to 5 days (Andreozzi et al., 2003). In addition, it has reported that the removal of NPX and KTF decreases under alkaline conditions (Dominquez et al., 2011) and the removal of DFC during photodegradation affected by the concentration of dissolved organic matter and NO3‐N (Andreozzi et al., 2003). 1.3 Benzotriazoles (BTs) – Benzothiazoles (BThzs) Benzotriazole and benzothiazole have been known for their great versatility. They have already been used as a corrosion inhibitor in the atmosphere and underwater. Also, their derivatives and their effectiveness as drug precursors have been drawing attention. Besides all the application mentioned above, the BTs and BThzs can be used ----------------------------------------------------------------------------------------------------------------11
Deliverable 6.1.1 WATERMICROPOL as antifreezes, heating and cooling systems, in aircraft de‐icing fluids, in the formulation of dishwashing detergents, hydraulic fluids and vapor phase inhibitors as well (Sease,1978; Hart et al., 2004). Additionally, they are used as UV stabilizers in plastic bottles, while they have been included in Directive 98/8/EC as biocides (Reemtsma et al., 2006). Among these compounds, the most often reported is 1H‐
benzotriazole (BTri) and their methylated compounds, 4‐methyl‐benzotriazole (4‐
TTri) and 5‐methylbenzotriazole (5‐TTri). BTs present high polarity, while in neutral pH they are found in non‐ionic form (Hart et al.,2004). As a result they are mainly reported to be ubiquitous in many European countries in surface, groundwater and wastewater treatment plants (Weiss & Reemtsma, 2005; Giger et al., 2006; Loos et al., 2009; Loos et al., 2010; Reemtsma et al., 2010). They have long‐term toxic effects in the aquatic environment (Voutsa et al.,2006), while BTri has presented anti‐estrogenic action (Harris et al., 2007). In a recent study, they were detected in marine organisms, a fact that indicates their tension to bioaccumulate (Nakata et al., 2009). The physicochemical properties of this group have an important role in terms of their fate and occurrence in the wastewater. They present low log Kow (1.59 ± 0.23), high degree of solubility and polarity in water; these characteristics indicate that BTs are difficult to get removed by sorption during conventional treatment. Furthermore, BTs are resistant to biodegradation (Voutsa et al., 2006; Giger et al., 2006; Reemtsma et al., 2010) and this is also a factor that affects their removal during conventional biological treatment. So far, there is a lack of data published for the fate of these compounds during photodegradation and the formation of their metabolites. ---------------------------------------------------------------------------------------------------------------- 12
Deliverable 6.1.1 WATERMICROPOL 2. Objectives The objective of this Work Package was to investigate the effect of hydrolysis and photodegradation on the fate of EDCs, Phs, BTs and BTzhs according to OECD 316 protocol (2008). In this context, the fate of the target compounds during treated wastewater disposal to the aquatic environment was studied. PFCs were not examined due to their minimal presence in biologically treated wastewater. The experiments of this Work Package were performed at the Sanitary Engineering Laboratory (School of Civil Engineering, National Technical University of Athens) using GC/MS. Additionally, identification of target BTs and BTzhs in water samples were performed at the Laboratory of Analytical Chemistry (Department of Chemistry, National and Kapodistrian University of Athens) using LC‐MS/MS. So far, bench scale batch experiments were conducted to evaluate the effect of light and pH on the fate of the above micropollutants and their relevant removal kinetics. In the next steps and until the end of this Work Package, the assessment of nitrate and humic acid concentrations effect on photodegradation kinetics, the identification of the photodegradation by‐products along with the determination of their toxicity will also be investigated for some target compounds. ---------------------------------------------------------------------------------------------------------------- 13
WATERMICROPOL Deliverable 6.1.1 3. Materials and Methods 3.1 Chemicals Methanol (MeOH) and ethyl acetate were of high performance liquid chromatography (HPLC) grade (Merck, Darmstadt, Germany) and were used as received. Bis(trimethylsilyl) trifluoroacetamide (BSTFA)+1% trimethylchlorosilane (TMCS) and pyridine, used for silylation, were purchased by Supelco (Bellefonte, PA, USA) and Carlo Erba‐SDS (Peypin, France), respectively. BPA (>97%) was purchased from Fluka (Buchs, Switzerland), whereas TCS (>97%) and deuterated BPA (BPA‐16) were purchased from Fluka (Heidelberg, Germany). Analytical standards of NP, NP1EO, IBF, NPX, KFN, DFC, and meclofenamic acid (MFC) were supplied by Dr Ehrenstorfer (Germany). All compounds were used without further purification (minimum purity >99%). Humic acids were purchased from Sigma‐Aldrich (Saint Louis, USA). Stock solutions of individual compounds were prepared in methanol at 1,000 mg L−1 and kept at −18°C. HPLC‐grade water was prepared in the laboratory using a MilliQ/Milli‐RO Millipore system (Millipore, Billerica, Massachusetts USA). Ultra pure HCl (32%) was used for acidification of the samples (Merck, Germany). 3.2 Photodegradation Batch Experiments Solar experiments Solar irradiations were carried out at NTUA, Greece (latitude 37°58' N , altitude 160 m above sea level). Photodegradation batch experiments were performed in triplicates in 2 l reactors according to OECD 316 protocol (2008). Reactors were 2 mm thick Pyrex cylinders of 16 cm high and 14 cm in diameter, whose outer side was covered with two layers of silver foil sheet. All batch experiments were performed in buffered pure water spiked with the target compounds at a concentration of 2000 ng/l. pH adjustment was done with phosphate buffer solution (0.1M) to achieve a pH value of 7. The measured pH never varied by more than 0.2 units during the course of the experiments. ---------------------------------------------------------------------------------------------------------------- 14
Deliverable 6.1.1 WATERMICROPOL Exposure to sunlight was continuous for 17 days and samples were taken at t=0 and in regular intervals (1, 2.5, 4.5, 25, 50, 73, 190 and 408 hrs). Solutions were homogenized with a glass rod and samples collected for GC‐MS analysis. To investigate hydrolysis, similar experiments were carried out in the dark. Solar light measurements The incident solar light intensity was measured with a pyranometer (Kipp and Zonen CM11pyranometer) at spectral range 305 – 2800 nm continually over the irradiation period. 3.3 Analytical Methods For the determination of the EDCs and PhCs, wastewater samples before and after solar exposure were analyzed using a chromatographic method developed by Samaras et al. (2011). Samples were filtered, acidified to pH 2.5, and extracted using C18 SPE cartridges. The eluates of the extraction were evaporated to dryness, and the dried residues were subjected to derivatization reaction using BSTFA (1% TMCS) and pyridine. For the qualitative and quantitative analyses, an Agilent Gas Chromatograph 7890A connected to an Agilent 5975C Mass Selective Detector (MSD) was used. For the determination of BTs and BTzhs an analytical method developed by Asimakopoulos et al. (2012) was used. The analysis of BTs and BTzhs was performed using a Thermo ultra high performance liquid chromatography (UHPLC) Accela system (pump and autosampler) interfaced with a Thermo TSQ Quantum Access triple quadrupole mass spectrometer (Thermo, San Jose, CA, USA). Wastewater characteristics (pH, COD, TSS, turbidity) were determined according to Standard Methods (APHA, 1992). ---------------------------------------------------------------------------------------------------------------- 15
Deliverable 6.1.1 WATERMICROPOL 4. Results and Discussion 4.1 Photodegradation Experiments The effect of photodegradation and hydrolysis on the removal of target compounds in aqueous solutions has been examined through bench scale experiments. Removal of the compounds was treated as first‐order kinetics (until 90% degradation been achieved). Experimental half‐lives (T1/2) were determined independently of the k pseudo‐constants.Results for each target group are presented in Figures 1‐2. Dark
Light
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(a) (b) Figure 1 Photodegradation of EDCs under (a) dark conditions and (b) light conditions Light
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(b) Figure 2 Photodegradation of Phs under (a) dark conditions and (b) light conditions ---------------------------------------------------------------------------------------------------------------- 16
Deliverable 6.1.1 WATERMICROPOL From the experimental data photodegradation rates and half‐lives for the substances were obtained, as shown in Table 2. Regarding photodegradation, estimation of rate constants and half‐lives was impossible for IBF, DFC, KFN, NP1EO and NP2EO. Table 2 Kinetic pseudo‐constants (k) and experimental half‐lives (T 1/2) for photodegradation of the target compounds Phs EDCs BTs ‐ BTzhs k (h‐1) T1/2 (h) IBF ‐ ‐ NPX 1.153×10‐1 6.0 DFC ‐ <1 KFN ‐ <0.25 NP 2.1×10‐2 33.0 NP1EO 4.0×10‐3 173.3 NP2EO ‐ ‐ TCS 4.23×10‐1 1.6 BPA 2.0×10‐3 346.6 2‐AMINO‐BTH ‐ ‐ 1‐H‐BTR ‐ ‐ TTRi ‐ ‐ XTRi ‐ ‐ 1‐OH‐BTR 4.2×10‐2 16.5 BTH 1.0×10‐3 69.3 Me‐S‐BTH 1.2×10‐2 57.8 2‐OH‐BTH ‐ ‐ Based on the results, KFN presents the lowest half‐life (<15min) and photo degraded in a very short time which makes it not possible to calculate the rate of photolysis. Also, DCF presents a rapid decline (over 60%) in the first hour of irradiation time. Similar effect of sunlight irradiation on KFN and DCF has also been reported by Matamoros et al. (2009) and Tixier et al. (2003). On the other hand, in the case of IBF, the determination of the kinetic equations, photolysis rate and half‐life were not estimated because the substance did not exceed ---------------------------------------------------------------------------------------------------------------- 17
Deliverable 6.1.1 WATERMICROPOL 50% of removal either under sunlight or in the dark. Finally, NP2EO, which is a very stable substance, showed negligible removal and it was not possible to calculate the rate of removal. These results indicated that the major mechanism of the aforementioned compounds was hydrolysis. Regarding the results for the selected BTs and BTzhs is can be stated that most of these compounds are very stable and shown negligible removal either under sunlight or in the dark conditions. Only, 1‐OH‐BTR exhibits a moderate photodegradation rate of 4.2×10‐2 h‐1 and half‐life value of 16.5h, whereas half‐lives for BTH and Me‐S‐BTH were found to be 69.3 and 57.8h respectively. In Figure 3‐5 indicative results for 1‐
OH‐BTR, BTH and 2‐AMINO‐BTH are presented. 1‐OH‐BTR
Normalized area
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Figure 3 Photodegradation of 1‐OH‐BTR under light and dark conditions BTH
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Figure 4 Photodegradation of BTH under light and dark conditions ---------------------------------------------------------------------------------------------------------------- 18
Deliverable 6.1.1 WATERMICROPOL 2‐AMINO‐BTH
120,00
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Figure 5 Photodegradation of 2‐AMINO‐BTH under light and dark conditions 4.2 Effect of pH on Photodegradation In order to assess the effect of pH on process performance experiments were performed at three pH values (6, 7 and 8). According to the results, it can be observed that most of the compounds were degraded with the same rate in all tested pH values. Figure 6 shows the change in the concentration of TCS during the irradiation time under the different pH values. As shown, TCS exhibits a lower degradation rate when pH value decreases. This result is in agreement with previous studies that reported that half‐life value of TCS under sunlight conditions decreases under alkaline conditions and especially when pH value is higher than pKa (7.9‐8.1) (Sanchez‐Prado et al.,2006; Tixier et al., 2002). ---------------------------------------------------------------------------------------------------------------- 19
Deliverable 6.1.1 WATERMICROPOL 1600
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Figure 6 Photodegradation of TCS under light conditions On the other hand, DCF, NPX, KTP, NP and NP1EO show no significant change in their removal rate with the change of pH. In Figure 7, indicative results for NPX are presented. Moreover, NP2EO presented negligible removals for all pH values, as in the photodegradation experiment. 1800
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Figure 7 Photodegradation of NPX under light conditions ---------------------------------------------------------------------------------------------------------------- 20
WATERMICROPOL Deliverable 6.1.1 5. Conclusions Batch experiments were performed in order to assess the effectiveness of sunlight to remove selected EDCs, Phs, BTs and BThzs from water samples. According to photodegradation and hydrolysis experiments at neutral pH value 7, TCS and most of Phs shown half‐lives values lower than one day. DFC and KFN were found to be very unstable, with half‐live value lower than one hour. This indicates that photodegradation is the major mechanism for the removal of these compounds in the environment. On the other hand, IBF, NP2EO and most of the BTs was found to be very stable either under sunlight or in the dark conditions. Only, 1‐OH‐BTR exhibits a moderate photodegradation rate. Regarding the effect of pH on EDCs and Phs, it seems that degradation rate for most of the target compounds is not significantly affected during irradiation under different pH values. Only TCS exhibited lower degradation rate under acidic conditions. In the next steps and until the end of this Work Package, the assessment of nitrate and humic acid concentrations effect on photodegradation kinetics and the identification of the photodegradation by‐products will also be investigated for some target compounds. Also, additional experiments concerning photodegradation are planning to be performed during winter months to investigate removal kinetics under different sunlight exposure. ---------------------------------------------------------------------------------------------------------------- 21
WATERMICROPOL Deliverable 6.1.1 References Andreozzi R., Raffaele M., Nicklas P., (2003). Pharmaceuticals in STP effluents and their solar photodegradation in the aquatic environment. Chemosphere, 50, 1319‐
1330 APHA – WEF – AWWA (1992) Standard Methods for Water and Wastewater Laboratory Analysis, 18th Edition, Washington D.C., USA Barcelo and Petrovic (2007) Pharmaceuticals and personal care products (PPCPs) in the environment. Analytical Bioanalytical Chemistry 387, 1203‐1214 Benotti et al. (2009) Pharmaceuticals and endocrine disrupting compounds in U.S. drinking water, Environmental Science and Technology 43, 597−603 Bester, (2003) Triclosan in a sewage treatment process‐balances and monitoring data, Water Research, 37, 3891–3896 Birkett& Lester (2003) Endocrine disrupters in wastewater and sludge treatment processes. CRC Press LLC, Florida Bolong et al. (2009) A review of the effects of emerging contaminants in wastewater and options for their removal, Desalination, 239, 229‐246 Buser et al., (1999) Occurrence and Environmental Behavior of the Chiral Pharmaceutical Drug Ibuprofen in Surface Waters and in Wastewater, Environmental Science and Technology 33, 2529‐2535 Carballa et al., (2004) Behavior of pharmaceuticals, cosmetics and hormones in a sewage treatment plant, Water Research, 38, 2918–2926 Chalew and Halden (2009) Environmental exposure of aquatic and terrestrial biota to triclosan and triclocarban, journal of the American water resources association, 45. Crane et al., (2006) Chronic aquatic environmental risks from exposure to human pharmaceuticals, Science of the Total Environment, 367, 23–41 Desbrow et al. (1998) Identification of estrogenic chemicals in STW effluent. 1. Chemical fractionation and in vitro biological screening, Environmental Science and Technology, 32, 1549‐1558 ---------------------------------------------------------------------------------------------------------------- 22
WATERMICROPOL Deliverable 6.1.1 Dominguez, J., Gonzalez, T., Palo, P., Cuerda‐Correa, E., (2011) Removal of common pharmaceuticals present in surface waters by amberlite xad‐7 acrylic‐ester‐resin: Influence of ph and presence of other drugs. Desalination, 269, 231‐238. EU (2001) European Union, Decision No 2455/2001/EC of the European Parliament and of the council of 20 November 2001 establishing the list of priority substances in the field of water policy and amending directive 2000/60/EC, Off. J. L331 (15/12/2001) Giger et al., (2006) Benzotriazole and tolyltriazole as aquatic contaminants. Input and occurrence in rivers and lakes, Environmental Science and Technology, 40, 7186‐
7192 Harris et al., (2007) Benzotriazole is antiestrogenic in vitro but not in vivo. Environmental Toxicology Chemistry 26, 2367–2372 Hart et al., (2004) Sorption and partitioning parameters of benzotriazole compounds, Microchemical Journal, 77, 9‐17 Heidler&Halden (2007) Mass balance assessment of triclosan removal during conventional sewage treatment, Chemosphere, 66, 362–369 Hernando et al., (2006) Environmental risk assessment of pharmaceutical residues in wastewater effluents, surface waters and sediments, Talanta, 69, 334–342 Jonkers et al. (2012) Occurrence and sources of selected phenolic endocrine disruptors in Ria de Aveiro, Portugal, Environmental Science and Pollution Research , 17, 834‐843 Katsoyiannis A. & Samara C. (2007) Ecotoxicological evaluation of the wastewater treatment process of the sewage treatment plant of Thessaloniki, Greece, Journal of Hazardous Materials 141, 614–621 Kim J., Korshin G.V., Velichenko A.B., (2005) Comparative study of electrochemical degradation and ozonation of nonylphenol. Water Research, 39, 2527 – 2534 Kolpin, et al. (2002) Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. Streams, 1999−2000: A national reconnaissance. Environmental Science and Technology 36, 1202−1211 Kosjek et al., (2007) Removal of pharmaceutical residues in a pilot wastewater treatment plant, Analytical Bioanalytical Chemistry 387, 1379–1387 Kumagai et al.., (2006) Influences of Drugs on the Oxygen Uptake Rate and Biosorption of Activated Sludge, Biol. Pharm. Bull., 29, 183—186 ---------------------------------------------------------------------------------------------------------------- 23
Deliverable 6.1.1 WATERMICROPOL Latch D.E., Packer J.L., Stender B.L., VanOverbeke J., Arnold W.A., McNeill K., (2005) Aqueous photochemistry of triclosan: formation of 2,4‐dichlorophenol, 2,8‐
dichlorodibenzo‐p‐dioxin, and oligomerization products. Environmental Toxicology and Chemistry. 24, 517–525 Loos et al. (2009) EU‐wide survey of polar organic persistent pollutants in European river waters, Environmental Pollution, 157, 561‐568 Loos et al. (2009) EU‐wide survey of polar organic persistent pollutants in European river waters, Environmental Pollution, 157, 561‐568 Loos et al., (2010) Occurrence of polar organic contaminants in the dissolved water phase of the Danube River and its major tributaries using SPE‐LC‐MS(2) analysis, Water Research, 44, 2325‐2335 Martínez Bueno et al. (2012) Occurrence and persistence of organic emerging contaminants and priority pollutants in five sewage treatment plants of Spain: two years pilot survey monitoring, Environmental Pollution 164, 267–273 Mascolo et al., (2010) Biodegradability of pharmaceutical industrial wastewater and formation of recalcitrant organic compounds during aerobic biological treatment, Bioresource Technology, 101, 2585–2591 Matamoros V., Duhec A., Albaiges J., Bayona J.M., 2009. Photodegradation of Carbamazepine, Ibuprofen, Ketoprofen and 17α‐Ethinylestradiol in Fresh and Seawater. Water Air and Soil Pollution, 196, 161 – 168. Nakata et al., (2009) Occurrence and concentrationsof benzotriazole UV stabilizers in marine organisms and sediments from the Ariake Sea,Japan. Environmental Science and Technology 43, 6920‐6926 Neamtu M. and Frimmel F. (2006). Photodegradation of endocrine disrupting chemical nonylphenol by simulated solar UV‐irradiation. Science of the Total Environment, p. 295‐306. OECD (2008) OECD guidelines for the testing of chemicals. Phototrnaformation of chemicals in water – Direct Photolysis. Protocol 316, 3/10/08. Pal A., Gin Y.H. K., Lin Y.C.A., Reinhard M., (2010) Impacts of emerging organic contaminants on freshwater resources: Review of recent occurrences, sources, fate and effects. Science of the Total Environment, 408, 6062–6069 ---------------------------------------------------------------------------------------------------------------- 24
WATERMICROPOL Deliverable 6.1.1 Pojana et al. (2011) Occurrence of environmentally relevant pharmaceuticals in Italian drinking water treatment plants. International Journal of Environmental Analytical Chemistry, 91, 537‐552 Pomati et al., (2008) Effects and interactions in an environmentally relevant mixture of pharmaceuticals. Toxicology Science 102, 129–137 Pothitou & Voutsa, (2008) Endocrine disrupting compounds in municipal and industrial wastewater treatment plants in Northern Greece, Chemosphere, 73, 1716–1723 Pounds et al., (2008) Acute and chronic effects of ibuprofen in the mollusc Planorbiscarinatus (GastropodaPlanorbidae), Ecotoxicology and Environmental Safety, 70, 47–52 Quinn et al., (2009) Evaluation of the acute, chronic and teratogenic effects of a mixture of eleven pharmaceuticals on the cnidarian, Hydra attenuate. Science Total Environment 407, 1072–1079 Ratola et al. (2012) Occurrence of organic microcontaminants in the wastewater treatment process. A mini review. Journal of Hazardous Materials, vol.239‐240, 1‐
18 Reemtsma et al. (2006) Polar pollutant entry into the water cycle by municipal wastewater: a European perspective. Environmental Science and Technology 40, 5451–5458 Reemtsma et al., (2010) Polar pollutants in municipal wastewater and the water cycle: Occurrence and removal of benzotriazoles, Water Research, 44, 596‐604 Rosenfeldt E.J., Linden K.G., (2004). Degradation of endocrine disrupting chemicals bisphenol A, ethinylestradiol, and estradiol during UV photolysis and advanced oxidation processes. Environmental Science and Technology 38, 5476–5483. Samaras et al. (2009) Determination of selected non‐steroidal anti‐inflammatory drugs in wastewater by gas chromatography‐mass spectrometry. International Journal of Environmental Analytical Chemistry 90, 219‐229 Samaras et al. (2011) An analytical method fro the simultaneous trace determination of acidic pharmaceuticals and phenolic endocrine disrupting chemicals in wastewater adn sewage sludge by gas chromatography ‐ mass spectometry, Analytical Bioanalytical Chemistry 399, 2549‐2561 ---------------------------------------------------------------------------------------------------------------- 25
WATERMICROPOL Deliverable 6.1.1 Sanchez‐Prado L., Llompart M., Lores M., Garcıa‐Jares C., Bayona J. and Cela R. (2006). Monitoring the photochemical degradation of triclosan in wastewater by UV light and sunlight using solid‐phase microextraction. Chemosphere, p. 1338‐1. Sease, (1978) Benzotriazole: A Review for Conservators, Studies in Conservation. 23, 76–85
Singer et al. (2002) Triclosan: occurrence and fate of a widely used biocide in the aquatic environment: field measurements in wastewater treatment plants, surface waters, and lake sediments, Environmental Science Technology 36, 4998–
5004 Soares et al. (2008) Nonylphenol in the environment: A critical review on occurrence, fate, toxicity and treatment in wastewaters. Environment International 34, 1033‐
1049 Stasinakis et al. (2010) Removal of selected endocrine disrupters in activated sludge systems: Effect of sludge retention time on their sorption and biodegradation. Bioresource Technol. 101, 2090‐2095 Stasinakis et al., (2007) Investigation of triclosan fate and toxicity in continuous‐flow activated sludge systems, Chemosphere, 68, 375–381 Stasinakis et al., (2008) Occurrence and fate of endocrine disrupters in Greek sewage treatment plants, Water research, 42, 1796 – 1804 Tan et al. (2007) Modelling of the fate of selected endocrine disruptors in a municipal wastewater treatment plant in South East Queensland, Australia, Chemosphere, 69, 644‐654 Tixier C., Singer H.P., Canonica, S., Müller S.R., 2002. Phototransformation of triclosan in surface waters: a relevant elimination process for this widely used biocide – laboratory studies, field measurements, and modeling. Environmental Science and Technology, Volume 36: 3482 – 3489. Tonnesen H.H., (2004)Photostability of Drugs and Drug Formulations. Boca Raton, Florida, 2nd edition, ISBN 0‐415‐30323‐0, Boca Raton London New York Washington, D.C Vazquez‐Duhalt et al. (2005) Nonylphenol, an integrated vision of a pollutant. Scientific review. Appl. Ecol. Environ. Res. 4, 1–25 ---------------------------------------------------------------------------------------------------------------- 26
WATERMICROPOL Deliverable 6.1.1 Voutsa et al., (2006) Benzotriazoles, alkylphenols and bisphenol A in municipal wastewaters and in the Glatt River, Switzerland. Environ. Sci. Pollut. Res. 13, 333–
341 Weiss & Reemtsma, (2005) Determination of benzotriazole corrosion inhibitors from aqueous environmental samples by liquid chromatography‐electrospray ionization‐tandem mass spectrometry, Analytical Chemistry, 77, 7415‐7420 Weiss et al., (2006) Discharge of three benzotriazole corrosion inhibitors with municipal wastewater and improvements by membrane bioreactor treatment and ozonation, Environmental Science & Technology, 40, 7193‐7199 Yan et al. (2010) Emerging contaminants of environmental concern: Source, transport, fate, and treatment, Practice Periodical of Hazardous, Toxic, and Radioactive Waste Management, 14, 2‐20 Ying et al., (2002) Environmental fate of alkylphenols and alkylphenolethoxylates — a review, Environment International, 28, 215– 226 Zhang et al., (2008) Carbamazepine and diclofenac: Removal in wastewater treatment plants and occurrence in water bodies, Chemosphere, 73, 1151–1161 ---------------------------------------------------------------------------------------------------------------- 27