Occurrence, fate and removal of endocrine disrupting compounds (EDCs) in Turkish wastewater treatment plants

Occurrence, fate and removal of endocrine disrupting compounds (EDCs) in Turkish wastewater treatment plants

Chemical Engineering Journal 277 (2015) 202–208 Contents lists available at ScienceDirect Chemical Engineering Journal journal homepage: www.elsevie...

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Chemical Engineering Journal 277 (2015) 202–208

Contents lists available at ScienceDirect

Chemical Engineering Journal journal homepage: www.elsevier.com/locate/cej

Occurrence, fate and removal of endocrine disrupting compounds (EDCs) in Turkish wastewater treatment plants O.T. Komesli a,⇑, M. Muz b, M.S. Ak c, S. Bakırdere d, C.F. Gokcay c a

Ataturk University, Department of Environmental Engineering, 25250 Erzurum, Turkey Department Effect-Directed Analysis Helmholtz-Zentrum für Umweltforschung GmbH, UFZ Helmholtz Centre for Environmental Research, UFZ Permoserstraße, 15/04318 Leipzig, Germany c Department of Environmental Engineering, Middle East Technical University, 06100 Ankara, Turkey d _ Turkey Yıldız Technical University, Department of Chemistry, 34349 Istanbul, b

h i g h l i g h t s  Investigated the treatability of EDCs in different wastewater treatment plants.  Different removal percentage observed in different plants.  Carbamazepine and diltiazem not absorb onto MBR sludge whereas they can absorbed onto CAS sludge.  EDCs sorbed onto sludge were not effectively degraded in the anaerobic digester environment.  CAS and MBR plants may be associated with the microbial population composition.

a r t i c l e

i n f o

Article history: Received 16 November 2014 Received in revised form 17 April 2015 Accepted 23 April 2015 Available online 29 April 2015 Keywords: Emerging pollutants Endocrine disrupting compounds EDC treatment Conventional treatment

a b s t r a c t Endocrine disrupting compounds, EDCs, are somewhat recently recognized pollutants which are often classed within ‘emerging micropollutants’ in the environment jargon. These compounds are known to interfere with the delicate balance of the endocrine system of animals and man, causing variety of undesirable outcomes. Their sources in natural waters are the domestic and industrial effluents. The main cause of concern with EDCs is their tendency to accumulate in fish causing gender shifts and reduced fecundity. Moreover, their possible interference with the water cycle and concurrent effects on the human endocrine system has been implicated. Increased usage of medication and surfactants in the household; pesticides in agriculture have all add up to the inventory of EDCs in the aqueous systems. Current view in combating EDCs in water cycle is the multi barrier approach. In this concept EDCs are tried to be controlled in effluents as well as in potable drinking waters. Therefore, knowledge on their elimination in classical wastewater treatment plants is vital for establishing sustainable strategies for the future. Five different EDCs were selected as model compounds in this study; two natural hormones, estrone and progesterone, which are constantly discharged by humans; carbamazepine, diltiazem and acetaminophen are pharmaceuticals which are widely used by the community. The 24 h composite samples were analyzed in influents and effluents of 7 full scale biological treatment plants of various modifications of activated sludge process, including one MBR plant. One striking finding was the removals obtained in conventional plants, which were far exceeding those obtained in the mid-scale or lab-scale MBR plants. Carbamazepine and diltiazem, two hydrophobic compounds, were found to sorb onto CAS sludge whereas not onto the MBR sludge. Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction

⇑ Corresponding author. Tel.: +90 312 210 58 65. E-mail addresses: [email protected] (O.T. Komesli), [email protected] com (M. Muz), [email protected] (M.S. Ak), [email protected] (S. Bakırdere), [email protected] (C.F. Gokcay). http://dx.doi.org/10.1016/j.cej.2015.04.115 1385-8947/Ó 2015 Elsevier B.V. All rights reserved.

One group of recently recognized emerging pollutants that are being introduced to rivers and lakes by way of domestic wastewaters are the so called endocrine disrupter compounds, EDCs, as defined by Kavlock et al. [1]. These micro contaminants tend to

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mimic hormones and block receptor cites thereby disrupting normal functioning of the endocrine system; for this reason they are often referred under the generic name endocrine disrupter compounds (EDCs). Hormone disrupting compounds enter the environment in many product formulations. There are more than 87,000 known chemicals which may be considered amongst EDCs. These include natural hormones, synthetic hormones and their metabolites, non-steroidal synthetic compounds, plasticizer, flame retardants, surfactants, pesticides, pharmaceutical and personal care products, PPCPs [2]. They may be grouped basing on their estrogenic, androgenic and thyroidal effects. Their harmful effects are on reproduction, growth and development in certain species of wildlife, and are associated with human disorders like cancers and infertility [3]. In estrogenic and androgenic classes, natural estrogen and androgen are mimicked or blocked by EDCs while these compounds may have direct or indirect impacts on thyroids [4]. Estrone, estradiol and estriol are the three common forms of natural hormones secreted by the human body. The maximum estrone concentration found in wastewater is reported as 180 ng/L [5]. Progesterone, which is another form of natural estrogen, became important after its detection in 4.3% of 139 United States streams [6]. It is discharged both by males and females and its maximum concentration in wastewaters is reported as 0.199 lg/L, averaging around 0.11 lg/L [7]. Butyl benzyl phthalate (BBP) is a synthetic polymer constituent widely used in vinyl tiles and in PVC as plasticizer. Its concentration may be expressed in ng/L in municipal wastewaters [8]. Reportedly, it has negative health effect mostly on male species, including decrease in sperm counts, toxicity to testes, prostate, and seminal vesicle [9–12]. Research has since focused on this compound [13–15]. Due to its low water solubility BBP mainly concentrates in sludge [16]; where it ranges between 12 and 1250 mg/kg [17]. A commonly prescribed medication, carbamazepine, CBZ, which is an anti-epileptic and anti-depressant was also studied in another work [18]. This compound was analyzed in influents and secondary effluents collected seasonally from five municipal sewage treatment plants in Tokyo [19], with variable concentration between 10 and 300 ng/L; with a removal efficiency of 0–80%. Average removal efficiency of the amide-type pharmaceuticals, including carbamazepine, was estimated lower than 45% by these authors. In another study, treatment of carbamazepine was investigated in a lab-scale MBR system fed with synthetic wastewater [20]. They found very little elimination of this compound. This observation was consistent with those of Joss et al. [21]. Serrano et al. [22], operating an MBR reactor fed with spiked synthetic wastewater also found no significant removal of CBZ without the addition of pulverized activated carbon to the system. However, addition of activated carbon improved removals by up to 85% [22]. Our lab-scale studies in an SBR unit fed with actual wastewater spiked with CBZ also supports these findings as 77% removal was achieved with this compound. Where a mass balance indicated that biodegradation was not occurred and total removal was due to adsorption onto the sludge only [23]. The other pharmaceutical studied in this work is a blood thinner diltiazem, DTZ. This compound is discharged through urine and may be detected in wastewaters and sediments at concentrations between 0.016 lg/L and 1.48 lg/kg, respectively [24]. The last compound studied was acetaminophen, ATP, also commonly known as paracetamol; which is a pain killer widely prescribed for the cure of common cold and flu [25]. In a toxicity study on Vibrio fishery and Daphnia magna test systems the ‘hazard quotient’ was found greater than unity for acetaminophen suggesting its potential ecological risks [26]. Acetaminophen was also recognized as one of 95 potential contaminants identified by the National Reconnaissance, completed in 1999–2000 in 139 U.S.

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streams [7]. Over 90% of acetaminophen may be removed by conventional activated sludge systems [27]. Studies on EDCs have substantially increased throughout the world; for their effects on human health are suspect. Analysis of EDCs in environment samples is difficult as their concentrations are extremely low, often at ng/L levels [28,29]. The mass spectrometer detector hyphenated with chromatographic separation techniques have often become the method of choice for detecting EDCs at trace levels [30]. In this work, some of the commonly encountered pharmaceutics in wastewaters, namely, diltiazem, carbamazepine and acetaminophen; two commonly discharged natural hormones, progesterone and estrone; and a member of common polymeric constituent, benzyl butyl phthalate (BBP), were selected as the model EDCs for study. Selection of the particular EDCs were made basing on their frequency of occurrence in sludge and wastewater samples. The main objective of this study was therefore set around a survey of the model EDCs in existing full-scale biological treatment plants in Turkey; and to evaluate their capacity to treat these contaminants at the trace levels that they exist in the domestic sewage. Another aim was to assess effectiveness of different configurations of activated sludge in treating these compounds in the effluents. 2. Materials and methods 2.1. Chemicals and reagents All the chemicals used throughout this study were analytical reagent grade. The selected EDCs, diltiazem (>99%), progesterone (>99%), estrone (>99%) were obtained from Sigma, Benzyl Butyl Phthalate (BBP) (>98%) was obtained from Aldrich, carbamazepine (CBZ) (>99%) and acetaminophen (>99%) were provided by Sigma– Aldrich. Dichloromethylsilane used in silylation was obtained from Aldrich (Milwaukee, WI, USA). Glass-fiber pre-filters (0.7 lm pore size, 47 mm diameter) were purchased from PAL Life Sciences (Mexico). High purity methanol, acetonitrile, toluene and acetone were obtained from Merck (Darmstadt, Germany). Ultrapure de-ionized water was produced in the lab by the Milli-Q water purification system (Millipore, USA). Milli-Q water was used in all dilution and sample preparations. In the preparation of mobile phase, ammonia (Merck) and formic acid (Merck) were used. The main stock solutions of analytes were prepared in methanol as 1000 mg/L and stored at 4 °C in refrigerator. In the preparation of working standard solutions, de-ionized water was used and working standards were prepared just before use to prevent decomposition. Physicochemical properties of the selected EDCs are not given here since these are available in various chemical databases. 2.2. Instrument Agilent 6410A type quadrupole MS detector consisting of autosampler, degasser and binary pump equipped with Electrospray Ionization (ESI) attached to Agilent 1200 HPLC was used for the LC–ESI-MS/MS measurements. A Zorbax C-8 (100 mm  3 mm, 3 lm) column was used for the separation of species of interest. Filtration of untreated and treated wastewater samples were performed by Millipore filtration apparatus under vacuum. Milli-Q water was used for all the dilutions and for sample preparations. Oakton pH310 pH-meter was used for pH adjustments. FALC Ultrasonic Bath was used (50 kHz, 160 W) for ultrasound-aided extraction. Details of both apparatuses used and the analysis methods for wastewaters and sludge are published, respectively [28,29].

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Table 1 Concentration of EDCs at influent and effluent samples taken from various WWTPs in ng/L. Name of treatment plant

Sample No.

Diltiazem

Progesterone

Estrone

Inf. Ankara Tatlar WWTP

S-1 S-2 S-3 S-4

6.0 5.4 5.0 11.0

Eskisßehir WWTP

S-1 S-2 S-3 S-4

Antalya Hurma WWTP

Carbamazepine

Acetaminophen

Eff.

Inf.

Eff.

Inf.

5.0 0.7
9.0
4.0
27.0 187.0 67.0 54.0

Eff.

Inf.

Eff.

Inf.

Eff.

7.0 58.0 43.0 9.0

78.0 16.0 95.0 14.0

4.0 3.0 75. 4.0

357.0 747.0 300.0 575.0

7.0 5.0 6.0 5.0

6.0 1.0 12.0

5.0 4.0 3.0

71.0 41.0
40.0 20.0
59.0 30.0 61.0
6.0 2.0
874.0 748.0 71.0 21.0

6.0 2.0
S-1 S-2 S-3 S-4

15.0
8.0
5.0 3.0

0.026

11.0



Antalya Lara WWTP

S-1 S-2 S-3 S-4





31.0
23.0
8.0

21.0 47.0 34.0

Kemer WWTP

S-1 S-2 S-3 S-4



5.0 5.0 5.0

35.0
21.0
10.0
6.0


2.3. Properties and parameters of treatment plants The 24 h composite influent and effluent samples were obtained from Ankara Tatlar, Hurma, Lara, Kemer, Konacık, Eskisßehir Wastewater Treatment Plants, and WWTPs. Sludge samples were obtained as grab samples from the recycle (RAS) lines. Of the treatment plants studied two were located in the city of Antalya with capacities of 75,000 m3/d, Hurma WWTP, and 31,000 m3/d, Lara WWTP. Both plants are nutrient removing, BNR type activated sludge plants with 25–30 days SRT, having 5-stage Bardenpho configurations without primary sedimentation. Tatlar WWTP is a conventional activated sludge plant having a capacity of 765,000 m3/d, operating at 3–5 days SRT, for treating domestic wastewaters from the city of Ankara. Excess sludge in this plant is anaerobically digested in a battery of digesters located at the cite. Another plant was also situated in Antalya province, Kemer. These were conventional plants with 13,000 and 10,000 m3/d flow handling capacities, operating in parallel. This plant has 16– 17 days SRT. Eskisßehir WWTP is a BNR type wastewater treatment plant having a capacity to treat 62,590 m3/d wastewater. Sludge samples from this plant were obtained from the belt press. Finally Konacik WWTP is a membrane bioreactor designed to serve with a maximum capacity of 3200 m3/d. The plant has an anoxic tank prior to aeration and mixed liquor from aeration tank is re-circulated to the anoxic tank for de-nitrification. The plant operates at 25 days SRT and is equipped with a battery of eight static membrane modules with 0.038 lm pore size. The anaerobic digester in Ankara-Tatlar plant is composed of eight identical tanks operated at 37 °C with a steady HRT of 25 days. Excess sludge from activated sludge unit is first thickened by holding for two days in gravity thickeners and then fed to the digesters. Grab sampling of incoming and outgoing sludge was carried out once during this study from the inlet and outlet of the digester unit. 3. Results and discussion 3.1. Treatment of EDCs in conventional treatment plants The highest wastewater EDC concentrations, in ng/L, observed in this study were 14.5 for diltiazem, 93 for carbamazepine, 860

for acetaminophen, 185 for estrone and 20 for progesterone. The influent, effluent and sludge EDC concentrations, as recorded in different treatment plants at different periods of the year, are depicted in Table 1 and Fig. 1. Due to marked differences between hydraulic residence times and SRTs employed in the sampled plants, and that composite sampling could only cover 24 h, it was not possible to calculate a reliable mass balance for plants of this sizes. Therefore interpretation on the wastewater and sludge samples could not be based on quantitative data; though this has been carried out in a lab-scale unit not presented here [31]. As it was seen from Table 1, frequency of occurrence of each compound mostly measured in Ankara Tatlar WWTP. Most of the compounds in Treatment plants near to Meditation region was under limit of detection. The EDC removals calculated for the plants studied are collectively presented in Fig. 2. From this figure it can be seen that although estrone is a natural hormone and known to be amenable to biodegradation [32], yet it was found that its removal was variable between 20% and 80% in most treatment plants, except for Hurma and Konacik plants, where it was 100 and zero percent, respectively. Konacik plant is a membrane plant but much smaller in capacity. From Table 2, it can be seen that estrone appreciably accumulated in the sludge samples from Ankara-Tatlar and Eskisehir plants, whereas estrone was absent in sludge samples from Kemer, Lara and Hurma plants. There are no particular differences between the former and latter plants accept for the geographic location i.e. latter plants are situated on the warm Mediterranean coast. From Fig. 1 it can be seen that progesterone, which is also a natural hormone, was detected in only two of the plants, namely Ankara-Tatlar and Antalya–Lara plants. Therefore it can be generalized as it is removed by 100% in most treatment plants, except for Ankara-Tatlar plant, where treatment was merely 50%. Yet again progesterone was found to have accumulated in the sludge of Ankara plant whereas it was absent in the sludge samples from Lara plant. This may be due to short SRT (3–5 days) employed in the former plant. In all other plants where progesterone was not detectable in sludge, SRT was greater than 17 days. From Fig. 1 it can readily be seen that acetaminophen, which is a commonly used pharmaceutical for cold and ache treatment, is totally removed in all the plants sampled. Although this compound

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Fig. 1. The removals of target EDCs obtained in the full-scale plants.

is reported as highly biodegradable and do not tend to adsorb onto solid matrixes due its fairly hydrophilic nature (log Kow = 0.46) [33]; yet from Tables 1 and 2 it is understood that acetaminophen appreciably sorbs onto the sludge in all the plants sampled. Another discrepancy with the lab studies is noticed in carbamazepine. This compound is reportedly recalcitrant and was not removed appreciably during lab studies. Whereas from Fig. 1 it can be seen that carbamazepine was completely, around 100%, removed in all the actual sized plants sampled in this study. From Tables 1 and 2 it is readily seen that CBZ was primarily removed from the effluents by sorption onto the sludge. Considering the hydrophobic nature of this compound, Kow = 2.80 this is somewhat expected. Treatment of Diltiazem in the sampled plants was variable between 40% and 100%, as deduced from Fig. 1. The lowest, 40%, was observed in Antalya–Lara and the highest, 100%, in Eskisßehir. Diltiazem is also known as highly biodegradable compound, as deduced from our mass balance studies carried on a lab-scale SBR reactor [31]. The Kow value for this compound, 2.60, is close to that of carbamazepine and similar adsorptive behavior is expected of this compound. Nevertheless, from Tables 1 and 2 it

is readily seen that diltiazem too, was heavily adsorbed onto sludge. 3.2. Treatment of EDCs in MBR plant Treatment of EDCs in an MBR plant was studied in medium sized Konacik plant. The plant was operating efficiently producing denitrified and sterile effluents with below 25 mg/L COD and less than 10 mg/L suspended solids. Effluent samples were drawn from the influent and effluent and sludge samples were obtained from the press filter unit. During the course of the study effluents and sludge were sampled seven times at different periods and the results of EDC analysis in wastewater samples are presented in Fig. 2; along with sludge analysis results. As can be deduced from Fig. 2, only diltiazem, carbamazepine and acetaminophen could be detected in the effluents. It is readily seen from this figure that both diltiazem and carbamazepine, were not at all removed by this plant; whereas, acetaminophen, which is a biodegradable compound, was completely removed from the effluents. Sludge analysis shown in Fig. 2 indicates that both DTZ and CBZ could not be recovered in sludge samples, suggesting that these compounds

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Fig. 2. Recorded concentrations of EDCs in influent, effluent and sludge in Konacık MBR-type plant.

Table 2 Concentration of EDCs at sludge samples taken from various WWTPs in lg/kg. Name of treatment plant

Sample No

Diltiazem

Progesterone

Estrone

Carbamazepine

Acetaminophen

Ankara Tatlar WWTP

S-1 S-2 S-3 S-4

0.021 0.013 0.017 0.048

0.009 0.004 0.003 0.0013

0.043 0.095
0.12 0.097 0.053 0.074

1.24 0.96 1.13 0.87

Eskisßehir WWTP

S-1 S-2 S-3 S-4

0.025

1.02 0.31 0.014
0.69 0.78 0.74 0.62

1.19 0.85 0.98 0.775

Antalya Hurma WWTP

S-1 S-2 S-3 S-4

8.04


1.09 0.47 0.53 1.63

2.49 0.98
Antalya Lara WWTP

S-1 S-2 S-3 S-4

0.87 0.054


3.03 1.18 1.82 2.06

1.35 1.02 1.59
Kemer WWTP

S-1 S-2 S-3 S-4

3.55 1.02 0.64 1.37



0.96
10.5
did not adsorb onto the sludge. However acetaminophen was present in all the sludge samples, though at minute quantities. Acetaminophen concentration was around 1–3.5 ppb in wastewaters whereas it was merely 1–3.5 ng/kg in sludge. The EDC analysis results from MBR plant contradicts those from the conventional plants in that both CBZ and DTZ, which were completely removed in large scale conventional plants by sorption onto sludge, were not removed at all in the MBR plant. This observation with CBZ is in accord with the lab-scale results presented in the literature [20] and in other MBR results that we have obtained at the-pilot scale (unpublished data). This strange behavior is

difficult to explain but may be associated with the biomass composition of sludge. For example, MBRs operate at high MLVSS concentrations but without selection pressure on bacteria for sedimentation, since sludge is separated from the liquid by filtration and not by settling; whereas, a selection pressure is exerted on sludge in conventional plants towards sedimentation. 3.3. Treatment of EDCs during anaerobic digestion None of the WWTPs sampled were equipped with sludge digestion units, except for Ankara Tatlar plant. As can be seen in Fig. 3,

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Treatment of EDCs in during anaerobic digeson in sludge samples taken from Ankara Wastewater Treatment Plant 400

Digester influent 350

Concentraon (µg/kg)

Digester effluent 300 250 200 150 100 50 0 Dilazem

Carbamazepine

Estrone

Progesterone Acetaminophen

BBP

Compounds Fig. 3. EDCs removed during the anaerobic digestion of excess sludge.

difference in EDC concentrations between ingoing and outgoing sludges to the anaerobic digester in Ankara Tatlar plant was not significant. In other words the selected EDCs that are sorbed onto the sludge were not efficiently removed in anaerobic digesters. Of the target EDCs, Estrone and Progesterone, being biodegradable natural organic compounds, were evidently already degraded by the time sludge reached the digester. Also elevated concentrations of the target EDCs observed in sludge were noteworthy and were indicative of the need to consider effective sludge treatment for EDCs control in the environment. For example, recently reported ozone-assisted sludge digestion processes can effectively digest sludge and remove EDCs sorbed onto sludge at the same time [30,34]. 4. Conclusion It has been shown in this study that EDCs, which are allegedly environmentally suspect causing gender shifts or cancer in man and biota, are actually treatable by conventional treatment processes. Those which are biodegradable, such as natural hormones or acetaminophen, may completely be eradicated from the environment while those which are not degradable simply change phases during treatment. For example, carbamazepine and diltiazem, where former is totally recalcitrant, are effectively removed from effluents by conventional biological treatment by accumulating in the biological sludge. This, in turn calls for effective sludge digestion since EDC-laden sludge pose risk of soil contamination when it is used as soil conditioner. Results presented here on activated sludge type treatment plants contradict with those from the lab studies and from the medium-scale MBR plants. For example, in the medium scale MBR plant (Konacik), whose results are presented in Fig 2, carbamazepine and diltiazem appeared untreatable and did not adsorb onto sludge; whereas, both compounds were found completely treatable in conventional activated sludge type treatment plants simply by adsorption onto sludge. It can be hypothesized that discrepancy between the results of the conventional and MBR plants may be associated with the microbial population composition. For example, conventional plants heavily rely on settleable microorganisms for operation and exert a selective pressure on microbes in that direction. Whereas in MBR plants selection pressure on microbes for aggregation and settleability is minimal since sludge is removed from the effluents by filtration. The change in microbial composition may also shift hydrophobicity of sludge; i.e.

conventional sludge being more hydrophobic and pose increased adsorption capacity for hydrophobic constituents. This remains to be explored. Another noteworthy finding was on anaerobic digestion of sludge, where most EDCs sorbed onto sludge were not effectively degraded in the anaerobic digester environment. From the data presented here on conventional plants it is implicit that there is no substantial evidence to cause for alarm with regards the EDCs in wastewaters, as long as these receive proper treatment in conventional plants. However, threat from sludge, which concentrates these compounds, is evident. Therefore every effort should be deployed to de-contaminate sludge before applying on land.

Acknowledgments This work was supported by the National Scientific Technology Council of Turkey-TUBITAK with a Grant number 108Y272.

References [1] R.J. Kavlock, G.P. Daston, C. DeRosa, Research needs for the risk assessment of health and environmental effects of endocrine disruptors: a report of the US EPA-sponsored workshop, Environ. Health Perspect. 104 (4) (1996) 715–740. [2] F.A. Caliman, M. Gavrilescu, Pharmaceuticals, personal care products and endocrine disrupting agents in the environment – a review, Clean Soil Air Water 37 (4–5) (2009) 277–303. [3] AWWA Research Foundation (AwwaRF). Featured Topics, EDC, PhACs, PCPs, 2005. [4] S.A. Snyder, P. Westerhoff, Y. Yoon, D.L. Sedlak, Pharmaceuticals, personal care products and endocrine disruptors in water: implications for the water industry, Environ. Eng. Sci. 20 (2003) 449–469. [5] K. Komori, H. Tanaka, Y. Okayasu, M. Yasojima, C. Sato, Analysis and occurrence of estrogen in wastewater in Japan, Water Sci. Technol. 50 (5) (2004) 93–100. [6] E. Barron, M. Deborde, S. Rabouana, P. Mazellier, B. Legube, Kinetic and mechanistic investigations of progesterone reaction with ozone, Water Res. 40 (2006) 2181–2189. [7] D.W. Kolpin, E.T. Furlong, M.T. Meyer, E.M. Thurman, S.D. Zaugg, L.B. Barber, Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999–2000: a national reconnaissance, Environ. Sci. Technol. 36 (2002) 1202–1211. [8] J. Vikelse, M. Thomsen, E. Johansen, Sources of phthalates and nonylphenols in municipal waste water. NERI Technical Report No. 225, National Environmental Research Institute, Denmark, 1998. [9] M. Ema, E. Miyawaki, Effects on development of the reproductive system in male offspring of rats given butyl benzyl phthalate during late pregnancy, Reprod. Toxicol. 16 (2002) 71–76. [10] M. Ema, E. Miyawaki, A. Hirose, E. Kamata, Decreased anogenital distance and increased incidence of undescended testes in fetuses of rats given monobenzyl phthalate, a major metabolite of butyl benzyl phthalate, Reprod. Toxicol. 17 (2003) 407–412.

208

O.T. Komesli et al. / Chemical Engineering Journal 277 (2015) 202–208

[11] R. Moral, R. Wang, I.H. Russo, D.A. Mailo, C.A. Lamartiniere, J. Russo, The plasticizer butyl benzyl phthalate induces genomic changes in rat mammary gland after neonatal/prepubertal exposure, BMC Genomics 8 (2007) 453. [12] S.H. Swan, K.M. Main, F. Liu, S.L. Stewart, R.L. Kruse, A.M. Calafat, C.S. Mao, J.B. Redmon, C.L. Ternand, S. Sullivan, J.L. Teague, Decrease in anogenital distance among male infants with prenatal phthalate exposure, Environ. Health Perspect. 113 (2005) 1056–1061. [13] C.G. Bornehag, J. Sundell, C.J. Weschler, T. Sigsgaard, B. Lundgren, M. Hasselgren, L. Hagerhed-Engman, The association between asthma and allergic symptoms in children and phthalates in house dust: a nested casecontrol study, Environ. Health Perspect. 112 (2004) 1393–1397. [14] P.S. Liu, Y.Y. Chen, Butyl benzyl phthalate blocks Ca2+ signaling coupled with purinoceptor in rat PC12 cells, Toxicol. Appl. Pharmacol. 210 (2006) 136–141. [15] M. Nakai, Y. Tabira, D. Asai, Y. Yakabe, T. Shimyozu, M. Noguchi, M. Takatsuki, Y. Shimohigashi, Binding characteristics of dialkyl phthalates for the estrogen receptor, Biochem. Biophys. Res. Commun. 254 (1999) 311–314. [16] M.J. Bauer, R. Herrmann, Estimation of the environmental contamination by phthalic acid esters leaching from household wastes, Sci. Total Environ. 208 (1997) 49–57. [17] C.A. Staples, D.R. Peterson, T.F. Parkerton, W.J. Adams, The environmental fate of phthalate esters: a literature review, Chemosphere 35 (1997) 667–749. [18] G. Nentwig, M. Oetken, J. Oehlmann, Effects of Pharmaceuticals on Aquatic Invertebrates the Example of Carbamazepine and Clofibric Acid. Pharmaceuticals in the Environment. Sources, Fate, Effects and Risks, second ed., Springer-Verlag, Berlin, Heidelberg, 2004 (16. Chapter). [19] N. Nakada, T. Tanishima, H. Shinohara, K. Kiri, H. Takada, Pharmaceutical chemicals and endocrine disrupters in municipal wastewater in Tokyo and their removal during activated sludge treatment, Water Res. 40 (2006) 3297– 3303. [20] R. Reif, S. Suárez, F. Omil, J.M. Lema, Fate of pharmaceuticals and cosmetic ingredients during the operation of a MBR treating sewage, Desalination 221 (2008) 511–517. [21] A. Joss, S. Zabczynski, A. Göbel, B. Hoffmann, D. Löffler, C.S. McArdell, T.A. Ternes, A. Thomsen, H. Siegrist, Biological degradation of pharmaceuticals in municipal wastewater treatment: proposing a classification scheme, Water Res. 40 (2006) 1686–1696. [22] D. Serrano, S. Suárez, J.M. Lema, F. Omil, Removal of persistent pharmaceutical micropollutants from sewage by addition of PAC in a sequential membrane bioreactor, Water Res. 45 (2011) 5323–5333. [23] M. Muz, M.S. Ak, O.T. Komesli, C.F. Gokcay, Removal of endocrine compounds in a lab-scale anaerobic/aerobic SBR unit, Environ. Technol. 35 (9) (2014) 1055–1063.

[24] P.E. Stackelberg, J. Gibs, E.T. Furlong, M.T. Myer, S.T. Zaugg, R.L. Lippincott, Efficiency of conventional drinking-water-treatment processes in removal of pharmaceuticals and other organic compounds, Sci. Total Environ. 337 (2–3) (2007) 255–272. [25] B.D. Gusseme, L. Vanhaecke, W. Verstraete, N. Boon, Degradation of acetaminophen by Delftia tsuruhatensis and Pseudomonas aeruginosa in a membrane bioreactor, Water Res. 45 (2011). 1829–183. [26] Y. Kim, K. Choi, J. Jung, S. Park, P.G. Kim, J. Park, Aquatic toxicity of acetaminophen, carbamazepine, cimetidine, diltiazem and six major sulfonamides, and their potential ecological risks in Korea, Environ. Int. 33 (3) (2007) 370–375. [27] M. Gomez, G. Garralon, F. Plaza, R. Vilchez, E. Hontoria, M.A. Gomez, Rejection of endocrine disrupting compounds (bisphenol A, bisphenol F and triethyleneglycol dimethacrylate) by membrane technologies, Desalination 212 (2007) 79–91. [28] M.S. Sönmez, M. Muz, O.T. Komesli, S. Bakırdere, C.F. Gökçay, Ultra trace determination of selected endocrine disrupter compounds in sludge samples using HPLC–ESI-MS/MS after ultrasound-aided sequential extraction, Clean 40 (9) (2012) 980–985. [29] M. Muz, M.S. Sönmez, O.T. Komesli, S. Bakırdere, C.F. Gökçay, Determination of selected natural hormones and endocrine disrupting compounds in domestic wastewater treatment plants by liquid chromatography electrospray ionization tandem mass spectrometry after solid phase extraction, Analyst 137 (4) (2012) 884–889. [30] H. Noppe, K. De Wasch, S. Poelmans, N. Van Hoof, T. Verslycke, C.R. Janssen, H.F. Brabander, Development and validation of an analytical method for detection of estrogens in water, Anal. Bioanal. Chem. 382 (2005) 91–98. [31] M. Muz, M.S. Ak, O.T. Komesli, C.F. Gokcay, An ozone assisted process for treatment of EDC’s in biological sludge, Chem. Eng. J. 217 (2013) 273–280. [32] J. Shi, Q. Chen, X. Liu, X. Zhan, J. Li, Z. Li, Sludge/water partition and biochemical transformation of estrone and 17-estradiol in a pilot-scale stepfeed anoxic/oxic wastewater treatment system, Biochem. Eng. J. 74 (2013) 107–114. [33] A.L. Yu-Chen, L. Chih-Ann, T. Hsin-Hsin, N.C. Sridhara, Potential for biodegradation and sorption of acetaminophen, caffeine, propranolol and acebutolol in lab-scale aqueous environments, J. Hazard. Mater. 18 (2010) 242–250. [34] M.S. Ak, M. Muz, O.T. Komesli, C.F. Gokcay, Enhancement of bio-gas production and xenobiotics degradation during anaerobic sludge digestion by ozone treated feed sludge, Chem. Eng. J. 230 (2013) 499–505.