Seasonal variation of endocrine disrupting compounds, pharmaceuticals and personal care products in wastewater treatment plants

Seasonal variation of endocrine disrupting compounds, pharmaceuticals and personal care products in wastewater treatment plants

Science of the Total Environment 442 (2013) 310–316 Contents lists available at SciVerse ScienceDirect Science of the Total Environment journal home...

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Science of the Total Environment 442 (2013) 310–316

Contents lists available at SciVerse ScienceDirect

Science of the Total Environment journal homepage:

Seasonal variation of endocrine disrupting compounds, pharmaceuticals and personal care products in wastewater treatment plants Yong Yu ⁎, Laosheng Wu, Andrew C. Chang Department of Environmental Sciences, University of California, Riverside, CA 92521, USA




► We took influent, effluent and sludge sample from 5 WWTPs in California in 2 seasons. ► We investigated the occurrence of 14 EDCs and PPCPs in the samples. ► Seasonal variations of compounds in the wastewater were significant. ► Most of selected compounds in influents were degraded during the treatment. ► RQ were lower than unity in effluent but higher than unity for 3 chemicals in sludge.

a r t i c l e

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Article history: Received 25 May 2012 Received in revised form 28 August 2012 Accepted 2 October 2012 Available online 22 November 2012 Keywords: Seasonal variation EDCs PPCPs WWTPs

a b s t r a c t The occurrence of 14 endocrine disrupting compounds (EDCs), pharmaceuticals and personal care products (PPCPs) in influents, effluents and sludge from five wastewater treatment plants (WWTPs) in southern California was studied in winter and summer. All 14 compounds were detected in influent samples from the five WWTPs except for estrone. Paracetamol, naproxen and ibuprofen were the dominant compounds, with mean concentrations of 41.7, 35.7 and 22.3 μg/L, respectively. The treatment removal efficiency for most compounds was more than 90% and concentrations in the effluents were relatively low. Seasonal variation of the compounds' concentration in the wastewater was significant: the total concentration of each compound in the wastewater was higher in winter than in summer, which is attributed to more human consumption of pharmaceuticals during winter and faster degradation of the compounds in summer. The highest concentrations of triclosan and octylphenol were detected in sewage sludge, with mean concentrations of 1505 and 1179 ng/g, respectively. Risk quotients (RQs), expressed as the ratios of environmental concentrations and the predicted no-effect concentrations (PNEC), were less than unity for all the compounds except for estrone in the effluents, indicating no immediate ecological risk is expected. However, RQs were higher than unity for 2 EDCs (estrone and octylphenol) and carbamazepine in sludge samples, indicating a significant ecotoxicological risk to human health. Therefore, appropriate treatment of sewage sludge is required before its application. © 2012 Elsevier B.V. All rights reserved.

⁎ Corresponding author at: Department of Environmental Sciences, University of California, 900 University Ave, Riverside, CA 92521, USA. Tel./fax: + 1 951 827 4664. E-mail address: [email protected] (Y. Yu).

0048-9697/$ – see front matter © 2012 Elsevier B.V. All rights reserved.

Y. Yu et al. / Science of the Total Environment 442 (2013) 310–316

1. Introduction Emerging environmental pollutants, pharmaceuticals and personal care products (PPCPs), and endocrine disrupting compounds (EDCs) have attracted much public attention (Wu and Janssen, 2011; Brausch and Rand, 2011; Basile et al., 2011; Boxall et al., 2012). Increasing numbers of water samples obtained from lakes, streams, aquifers and municipal supplies across the world have been found to be contaminated by trace quantities of such residues. These compounds might be excreted by patients and/or be improperly disposed by the users and eventually found their ways into the wastewater treatment plants (WWTPs) (Phillips et al., 2010; Escher et al., 2011; Nelson et al., 2011). The treated effluents of WWTPs that were discharged into surface water bodies could be an important sources for PPCPs and EDCs to enter the aquatic environment, and the fate, transport and potential adverse effects on aquatic biota have been delineated (Kleywegt et al., 2011; Boleda et al., 2011; Abdelmelek et al., 2011). During the wastewater treatment, the pharmaceutical residues may be adsorbed by the mixed liquor suspended solids and subsequently removed from water stream by sedimentation (Jelic et al., 2011). Municipal sewage sludge, the solid fractions separated from the wastewater stream, therefore is potentially a sink of the wastewater-borne PPCPs (Motoyama et al., 2011). The publicly-owned wastewater treatment works (POTWs) in the U.S. generate over 8 million tons (dry weight) of sewage sludge annually, about 41% was applied to land and 17% were landfilled, are potential sources of PCPPs and EDCs in the terrestrial environment and in groundwater (EPA 832-R-06-005, 2006). The concentration of pollutants in influent and effluent of WWTPs are routinely monitored in many countries (Luo et al., 2011; Prasse et al., 2010; Reungoat et al., 2011). However, little attention was on the seasonal variation of PPCPs. From 2001 to 2002, Loraine and Pettigrove (2006) sampled water at four drinking water treatment plants and one wastewater reclamation plant in San Diego, USA for presence of PCPPs and EDCs. Vieno et al. (2005) investigated the occurrences of 5 pharmaceutical residues in the influent and effluent of a WWTP and the recipient river in Aura, Finland during three seasons in 2004. Recently, Sui et al. (2011) followed the presence of 12 PPCPs in two WWTPs in Beijing, China. Results of the studies showed that the concentrations of PPCPs in municipal wastewater and its treated effluents were subject to considerable seasonal variations. It was not sure however the summer verse winter discrepancies in PCPPs and EDCs concentrations of the wastewaters reflected the fluctuations in consumption patterns or in performances of the municipal wastewater treatment systems. The Riverside County was one of the fastest growing regions in the southern California and in the past two decades large numbers of people immigrated from Los Angeles and San Diego Counties. As a part of the water conservation programs, reclaimed wastewaters are routinely used for crop and landscaping irrigation and to lesser extent for groundwater recharging, body-contacting recreational activities and wetland replenishments. During the growing season, much of the reclaimed wastewater goes for irrigation water. In the remaining time, the excess


water is stored. The resulting sewage sludge was also land applied. Through these pathways, PPCPs and EDCs may be uptaken by crop, subsequently affecting the well being of the consumers (Wu et al., 2010; Herklotz et al., 2010; Calderón-Preciado et al., 2011). The seasonal differences in the chemicals' concentrations in the wastewater would invariably affect the amounts of chemicals being transferred along the food chain. It is imperative that the seasonal occurrence of PPCPs and EDCs be understood. We examined the occurrence and fate of selected PPCPs and EDCs in influent, effluent and sewage sludge samples from five WWTPs in Riverside County, California. Specifically, we collected and analyzed the samples from the both summer and winter seasons. The results were used to evaluate the seasonal variation of PPCPs and EDCs from different communities and to assess the potential ecological risks. 2. Materials and methods 2.1. Chemicals and reagents The PPCPs and EDCs used in this study included 4-n-nonylphenol (NP), 4-tert-octylphenol (OP), aspirin (ASP), bisphenol A (BPA), carbamazepine (CBZ), clofibric acid (CFA), diclofenac (DCF), estrone (ETR), gemfibrozil (GFB), ibuprofen (IBP), ketoprofen (KTP), naproxen (NPX), paracetamol (PCM) and triclosan (TCS). Chemical structures, CAS numbers and physicochemical properties of the 14 compounds are shown in the Supplementary data (Table S1). The surrogate standard, [ 2H3]-ibuprofen (D3-IBP) and [ 2H3]-paracetamol (D3-PCM) were purchased from C/D/N Isotopes Inc. (Quebec, Canada). Stock solutions of the reference compounds were prepared in methanol and stored at −20 °C. N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA) (Sigma-Aldrich, St. Louis, MO) was used as the derivatizing reagent. Deionized water was prepared by a Milli-Q water purification system. Oasis HLB (500 mg, 6 mL) was purchased from Waters (Milford, MA). Ethyl acetate, methanol (pesticide grade), and formic acid were purchased from Fisher Scientific (Pittsburgh, PA). 2.2. Sample collection Five WWTPs serving varied communities in Riverside County of California were chosen. The WWTPs employ similar treatment processes: primary (mechanical) process using screens, settling tanks and skimmers to remove particles, coupled with secondary biological treatment. Detailed information of five WWTPs are shown in Table 1. Sampling was carried out during periods of normal weather condition and WWTP running time. In August 2010 (summer) and February 2011 (winter), the flow-proportioned influent, effluent, sewage sludge samples were collected over a 24 hour period of time. Samples were collected on Wednesdays and Thursdays to reflect normal activities of communities. The wastewater samples passed through glass fiber pre-filters, treated with 0.5% sodium azide (w/v), and stored at 4 °C. The sewage

Table 1 Characteristics of five WWTPs in Riverside County, California. Location


Typical flows (×106 L/day)

44 30 43 29 40

Capacity (×106 L/day)

61 42 61 42 68

Sludge (×103 kg/day dw)

12 8 14 8 10

Secondary treatmenta


Population served (×103)b

180 125 195 100 140

Age profile (%) b20



34 29 40 36 36

58 40 53 45 52

8 31 7 19 12

a OD: oxidation ditch — continuous-flow process using looped channels to create time sequenced anoxic, aerobic, and anaerobic zones; A2/O: continuous-flow suspended-growth process with anaerobic, anoxic, and oxic stages; BP: Bardenpho process, continuous-flow suspended-growth process with alternating anoxic/aerobic/anoxic/aerobic (4 stages); MBP: modified Bardenpho process, BP with addition of an initial anaerobic zone. b Population and age profile from 2010 U.S. Census.


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sludge, approximately 80% water content, were air-dried, finely ground to pass through a sieve with 0.5 mm opening, and stored at 0 °C.

3. Result and discussion 3.1. Occurrence

2.3. Extraction and analysis Two hundred milliliters of influent and 500 mL of effluent samples were spiked with 200 ng surrogate standards. The HLB columns were conditioned with 2 mL methanol and 2 mL deionized water, followed by loading of the sample at a flow rate of 5 mL/min. The cartridges were dried under nitrogen and eluted with 4×1 mL methanol (Yu and Wu, 2011). One gram of prepared sludge sample was spiked with surrogate standards at 200 ng/g dry weight (dw). Five milliliters of methanol containing 1% (v/v) formic acid was added, and successively vortexed for 2 min, ultrasonicated for 20 min, and centrifuged at 3000 rpm for 10 min, then decanted the supernatant. The sludge was extracted two additional times with 4 and 3 mL of solvent. The supernatants were collected and combined. The supernatants were evaporated under a gentle stream of N2 to about 1 mL, and diluted in 100 mL water, then passed through HLB cartridge as described above (Yu and Wu, 2012). The eluates were evaporated to dryness with a gentle stream of nitrogen at 37 °C, and re-dissolved in 900 μL of ethyl acetate, transferred into the GC vial, and 100 μL of MTBSTFA was added. The GC vials were put into GC oven at 70 °C for 60 min for derivatization prior to the GC–MS analysis. The concentrations of analyzed chemicals were determined by using an Agilent 6890N GC coupled with a 5975C MSD, equipped with an Agilent 7683B automatic liquid sampler. Details of the instrumental analysis are described in the text and Table S2 of the Supplementary data.

2.4. Quality assurance and quality control (QA/QC) QA/QC was adhered to ensure the accurate quantification of the target chemicals (Yu and Wu, 2011, 2012). The limit of quantification (LOQ) was set at S/N ratios ≥ 10. All instrumental and procedural blanks were far below LOQ. All the samples were extracted and analyzed in duplicate, and all the analytical results are reported as the average of two values. Recoveries of the 14 target compounds were determined for water and sludge by spiking the samples at 0.2, 1 and 5 ng/mL for wastewater and 40, 300 and 2000 ng/g for sewage sludge. The respective recoveries of 14 target compounds in influent, effluent and sludge samples were shown in Tables S3 and S4 (Supplementary data). Statistical analysis of data (significance level) was carried out with SPSS 16.

The 14 compounds we investigated, except for ETR, were found in influents of every WWTP (Table 2). PCM exhibited the highest mean concentration of 41.7 μg/L, followed by NPX and IBP at mean concentrations of 35.7 and 22.3 μg/L, respectively. GFB, OP and TCS were detected in medium concentration levels with means of 4.7, 1.34 and 2.30 μg/L, respectively. The concentrations of ASP, BPA, CBZ, CFA, DCF, ETR, KTP and NP were b0.6 μg/L. Effluents of WWTPs could be the major sources for PPCPs and EDCs in surface waters. However, the WWTP effluent concentrations of PCPPs and EDCs in this study were one to two orders of magnitude lower than those present in the respective influents (Table 2). GFB and PCM were the most abundant in the effluents, with mean concentrations of 151 and 85.5 ng/L, respectively; other compounds had mean concentrations b 60 ng/L. Since influent and effluent samples were collected to cover the same time period, the concentration difference would represent the removal efficiency of treatment processes. The average removal PCPPs and EDCs in wastewater treatment were >90% with the exception of CBZ and CFA, comparable with findings of Rosal et al. (2010) and Lavén et al. (2009). In sewage sludge, TCS was detected at the highest concentrations among all compounds investigated with average of 1430 and 1581 ng/g in summer and winter seasons, respectively. OP was equally abundant having mean concentrations of 1034 and 1325 ng/g in summer and winter seasons, respectively. On mass basis, these two compounds accounted for approximately 75% of the total PCPP and EDC contaminants detected in the sludge samples. The concentration of NP in sewage sludge at sampling location C, 481 to 1307 ng/g, was orders of magnitudes higher that at the remaining locations, 42 to 182 ng/g. The concentrations of BPA, IBP and GFB in sewage sludge were at the medium level with mean concentrations around 100 ng/g. The concentrations of ASP, CFA, DCF, ETR, KTP, NPX and PCM were b 50 ng/g. The concentration ranges were similar to the outcomes of 2001 USEPA National Sewage Sludge Survey (McClellan and Halden, 2010) indicating that the presence of PCPPs and EDCs in the municipal sludge has not significantly changed in the past decade. 3.2. Seasonal variation As shown in Fig. 1, the highest influent concentrations, 218 μg/L of PCM and 210 μg/L of NPX, were both found during the winter season at sampling location C. NPX is a non-steroidal anti-inflammatory drug (NSAID) commonly used for the reduction of pain, fever, inflammation

Table 2 Concentrations of 14 compounds in the WWTPs in two seasons. Influent (μg/L)


Effluent (ng/L)

Sludge (ng/g)










0.17–0.93 0.06–0.6 0.034–0.35 0.057–0.42 0.086–0.58 n.d.–0.16 1.09–8.5 8.6–56.5 0.15–1.3 0.22–0.87 9.3–210 0.08–3.9 0.37–218 0.18–4.4

0.44 0.296 0.115 0.137 0.277 0.097 4.67 22.3 0.563 0.51 35.7 1.34 41.7 2.30

0.36 0.335 0.078 0.0975 0.245 0.11 4.85 19.4 0.495 0.49 16.8 0.895 9.85 2.54

n.d.–70 n.d.–44 n.d.–62 n.d.–81 n.d.–120 n.d.–30 n.d.–650 13–92 n.d.–65 n.d.–50 n.d.–150 n.d.–100 n.d.–210 n.d.–160

29.4 12.6 21.3 26.8 12 3 151 55.8 29 9 30.3 48.4 85.5 48.4

32.5 5 16.5 19 n.d. n.d. 46 52 37.5 n.d. n.d. 50 97.5 39.5

33–75 53–196 n.d.–197 n.d.–135 n.d.–187 n.d.–32 38–172 37–216 n.d.–27 35–1307 8–53 74–3263 n.d.–81 158–3277

49.3 111 66.5 36.4 48.4 10.3 93.3 109 8 258 19.1 1179 26.8 1505

45.5 94.5 33.5 22.5 34.5 n.d. 90.5 103 n.d. 113 13.5 1174 21 1987

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Fig. 1. Concentrations of 14 EDCs and PPCPs in influent of 5 WWTPs in summer and winter.

and stiffness caused by a variety of conditions. PCM (i.e. acetaminophen) is a widely used over-the-counter analgesic (pain reliever) and antipyretic (fever reducer). Moreover, wastewater at sampling location C had the highest IBP level among all WWTPs we sampled. IBP is another NSAID used for relief of symptoms of arthritis, fever, and pain, especially where there is an inflammatory component. Sampling locations A and C were comparable in terms of service area, population served, wastewater flows (Table 1). Even the age distributions of the residents were similar. Yet the concentration levels of these compounds in the wastewater flow of location C were considerably higher than that of location A, especially during winter (pb 0.01). Location C served a mixed municipality of industrial, commercial and residential components, while Location A is primarily a residential community with auxiliary commercial establishments. Obviously, the commercial and industrial wastewater flows may not contribute much to the pharmaceutical loads, but they could contribute antibacterial agent, industrial detergent and plasticizer to location C. Hospital wastewater could be another factor (Escher et al., 2011). There were 3 hospitals in the service area of location C and one hospital in the service area of location A. Clearly, hospital was a significant contributor of pharmaceutical in the wastewaters. Location B that served a retirement community also exhibited high concentrations of the PCPPs. In addition, the wastewater influent of location B recorded the highest concentration of GFB. For 10 of the 14 compounds, their concentrations in the influents were higher in winter than summer (p b 0.05). PCM was detected on the average 81.5 μg/L, while the mean concentration in summer was merely 1.87 μg/L (p b 0.01). The mean concentration of NPX in winter was 3.5 times as that in summer (p b 0.01). Similarly, IBP was detected

at 13.3 and 31.3 μg/L for summer and winter, respectively (p b 0.01). The high concentration of GFB in winter was consistent with the fact that blood lipids of patients tend to rise in winter (Ockene et al., 2004) thus an increased dosage of GFB would be expected. As shown in Table S5, ratios of concentrations in influent between summer and winter from the five WWTPs were differ from 1, showed a significant difference between two seasons. The seasonal variation of PCPP concentrations indicated the consumption patterns of these pharmaceuticals during winter because of higher incidences of flu or other ailments. There appeared to be seasonal fluctuations even though the PCPPs and EDCs concentrations in the treated effluents were relatively low (Fig. 2). Of the 14 compounds detected in effluents, 12 were found at higher concentrations in the winter (pb 0.05). The total mass concentrations of PCPPs and EDCs on summer effluent vs. winter effluent were 354 vs. 770 ng/L, respectively. In the winter season, 5 compounds (GFB, IBP, KTP, OP and TCS) were always detected yet CFA, DCF, ETR and NP were detectable only in one out of the five sampling locations (20%). The concentrations of GFB in effluents were always higher than those of other compounds, summer and winter, with maximum concentration up to 650 ng/L. In the summer season, only IBP was detected at all of the WWTPs we sampled, while 7 compounds (BPA, DCF, ETR, KTP, NP, NPX and OP) were detected in less than one out of the five sampling locations (b20%). The seasonal differences of PCPP concentration in the treated effluents seem to reflect the performance of treatment processes in these compounds were more effectively removed in warmer temperature of summer. However, due to the low concentrations in effluents, most ratios of removal efficiencies between summer and


Y. Yu et al. / Science of the Total Environment 442 (2013) 310–316

Fig. 2. Mean concentrations of 14 EDCs and PPCPs in effluent of summer and winter. The bar represents the range of concentration in different WWTPs.

winter were around 1 (Table S5), showed no significant differences were observed. 3.3. Fate analysis We determined the fate of the six most frequently detected compounds, namely GFB, IBP, NPX, OP, PCM and TCS, in the wastewater treatment process based on the mass balance that: F ww  ðC in −C ef Þ ¼ S  C sl þ Q bi


where Fww is wastewater flows (L/day), Cin and Cef are respectively concentrations in influent and effluent (μg/L), S is sewage sludge (kg/day), Csl is concentrations in sewage sludge (μg/kg), and Qbi is the portion reduced by degradation (μg). For GFB, IBP, NPX, and PCM, more than 99% of the mass in influents were degraded during the course of the wastewater treatment (Fig. 3) and the seasonal difference was not significant. The trends were essentially the same at all of the sampling locations. For TCS, as much as 12 and 44% of the mass in the influents were recovered in the sewage sludge fraction of the summer and winter seasons, respectively. OP is the degradation product of octylphenol ethoxylates (OPEO). We did not track OPEO in the course of wastewater treatment. During the summer, the amount of OP in sewage sludge fraction was orders of magnitude higher than the mass in the influents resulting in negative degradation as shown in Fig. 3. It was an indication that OPEO in the influent stream was rapidly degraded during the wastewater treatment processes to OP which was subsequently adsorbed by the suspended solids, ending up in the sewage sludge fraction.

ecological risk. The RQ must remain below unity to ensure an acceptable risk to the environment (EU Ad Hoc Working Party, III/5504/94 Draft 4, 1994). In the meantime PNECs are base on eco-toxicity data that would vary according to the experimental situations. However, PPCPs are designed for exerting a long-term biological effect, so that standardized acute bioassays are not the most appropriate basis for the ecotoxicological risk assessment of PPCPs (Ferrari et al., 2004). Therefore, to reduce the uncertainties of standardized acute toxicity tests in risk assessment for some chemicals, we employed the strictest standard, i.e. the lowest PNEC values, to calculated the RQs of the effluents based on PNECs of water (PNECwater) appeared in the published technical literature (Flippin et al., 2007; Triebskorn et al., 2004; Tauxe-Wuersch et al., 2005; Quinn et al., 2008; Stuer-Lauridsen et al., 2000; Capdevielle et al., 2008; Ferrari et al., 2003; Lin et al., 2008; Xu et al., 2011). The RQs for all of the PCPP and EDC compounds were less than the unity, except for ETR (Fig. 4). PNEC for the sewage sludge (PNECsludge) may be estimated from PNECwater using the following equation: PNECsludge ¼ K d  PNECwater


where Kd is the soil–water distribution coefficient of a PCPP or EDC.

3.4. Environmental implications Based on the outcomes of our investigation, most PCPP and EDC compounds were effectively removed during the treatment process and concentrations in the effluents were at least one order of magnitude lower than the concentrations in the influents. PCPPs and EDCs have been detected in water bodies around the world. The potential dietary intakes would definitely be less than a therapeutic dosage. Do they still present certain degrees of harm to human and/or ecological health over the long run? It remains an open question (Boxall et al., 2012; Brausch et al., 2012). The European Union guidelines employ the risk quotient (RQ), ratio of the environmental concentration vs. predicted no-effect concentration (PNEC), to evaluate the

Fig. 3. The mass balance of selected compounds in WWTPs. The bar represents the range of degradation percentage in different WWTPs.

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Fig. 4. The RQ of 14 EDCs and PPCPs in effluent and sludge.

The Kd in turn may be calculated based on Karickhoff (1981) for sorption of hydrophobic pollutants on environmental matrices: K d ¼ f oc  0:411  K ow


where foc is the organic carbon content of sludge, and the average foc of 5 sludge was 41%. The PNECsludge of ASP and PCM were not lipophilic compounds and were not included. In the sewage sludge (Fig. 4), the RQs for the PPCPs were less than unity except CBZ. However, the RQs for ETR and OP were 3.9 and 12, respectively, and RQs for BPA and NP were higher than 0.7, indicating potential ecotoxicological risk unless they would be degraded shortly after land application of the sewage sludge. 4. Conclusions This work investigated the occurrence and seasonal variation of EDCs and PPCPs in influent, effluent and sludge from 5 WWTPs in southern California. Fate analysis showed that most compounds were removed by degradation. Potential risks to the environment are expected due to the land application and landfill of sludge. As this study focused on WWTPs, further research is necessary to study their occurrence in aquatic environment and organism. More attention is also needed to better understand their fate in aquatic environment and their risk to public health associated with wastewater irrigation and sludge land application. Acknowledgment We thank Frederick Ernst for his help during the sample collection. Appendix A. Supplementary data Supplementary data to this article can be found online at http:// References Abdelmelek SB, Greaves J, Ishida KP, Cooper WJ, Song WH. Removal of pharmaceutical and personal care products from reverse osmosis retentate using advanced oxidation processes. Environ Sci Technol 2011;45:3665–71. Basile T, Petrella A, Petrella M, Boghetich G, Petruzzelli V, Colasuonno S, et al. Review of endocrine-disrupting-compound removal technologies in water and wastewater treatment plants: an EU perspective. Ind Eng Chem Res 2011;50:8389–401. Boleda MR, Galceran MT, Ventura F. Behavior of pharmaceuticals and drugs of abuse in a drinking water treatment plant (DWTP) using combined conventional and ultrafiltration and reverse osmosis (UF/RO) treatments. Environ Pollut 2011;159: 1584–91.

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