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AZMAT-15581; No. of Pages 7

Journal of Hazardous Materials xxx (2013) xxx– xxx

Contents lists available at ScienceDirect

Journal of Hazardous Materials

jou rn al hom epage: www.elsev ier .com/ locate / jhazmat

easonal variation in the occurrence and removal of pharmaceuticalsnd personal care products in a wastewater treatment plant iniamen, China

ian Sun1, Min Lv1, Anyi Hu, Xiaoyong Yang, Chang-Ping Yu ∗

ey Laboratory of Urban Environment and Health, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, China

i g h l i g h t s

The occurrence and removal of 50 PPCPs in a WWTP were investigated over one year.39 PPCPs were detected in the influent, 14 PPCPs could be removed >50% in WWTP.Most PPCPs showed higher concentrations in cold seasons in the influent and effluent.Temperature and HRT may contribute to the seasonal variation of PPCP removal.

r t i c l e i n f o

rticle history:eceived 3 September 2013eceived in revised form 6 November 2013ccepted 25 November 2013vailable online xxx

eywords:harmaceuticals and personal careroducts (PPCPs)

a b s t r a c t

The occurrence and seasonal variation of 50 pharmaceuticals and personal care products (PPCPs)in a wastewater treatment plant (WWTP) in Xiamen, China was investigated over a period of oneyear. Among the targets, 39 PPCPs were detected in the influent. The highest concentration wasobserved for acetaminophen, with the average concentration in the influent of 2963.5 ng/L. The sea-sonal variation of PPCPs in the influent was observed. For most pharmaceuticals, highest concentrationswere in March 2013, followed by December 2012, while the concentrations were lower in August2012 and May 2013. Among the detected PPCPs, 14 targets could be removed more than 50% inthe WWTP. The activated sludge treatment process contributed to most of PPCP removal, while

astewaterccurrenceemoval efficiencieseasonal variations

the adsorption to the particles in the primary treatment and the transformation under UV radia-tion in the disinfection treatment also contributed to the PPCP removal. Among the detected PPCPsin the influent, 36 PPCPs could be detected in the final effluent of the WWTP. Significantly higherconcentrations of PPCPs were observed in effluent samples collected in March 2013 compared to otherseasons, suggesting higher concentrations of PPCPs could be discharged into the surrounding seawater
during this period.
. Introduction

Pharmaceuticals and personal care products (PPCPs) are a classf emerging contaminants which include commonly used medic-nal, cosmetic, and personal hygiene products. PPCPs have been

idely detected in the surface, ground, coastal waters and even therinking water [1–3]. Great concerns have been raised about PPCPsue to their potential adverse impacts on the ecological safety anduman health [4].

Please cite this article in press as: Q. Sun, et al., Seasonal variation in the ocin a wastewater treatment plant in Xiamen, China, J. Hazard. Mater. (2013

Previous work indicated that the effluent from wastewaterreatment plants (WWTPs) was one of the major pathways forPCPs to enter the aquatic environment [5]. Large number of

∗ Corresponding author. Tel.: +86 592 6190768.E-mail address: [email protected] (C.-P. Yu).

1 Qian Sun and Min Lv contributed equally to this work.

304-3894/$ – see front matter © 2013 Elsevier B.V. All rights reserved.ttp://dx.doi.org/10.1016/j.jhazmat.2013.11.056

© 2013 Elsevier B.V. All rights reserved.

studies have been carried out to monitor PPCP occurrence in theinfluent and effluent of WWTPs and to evaluate the removal effi-ciencies [2,6–14]. The concentrations of PPCPs in the WWTP canrange from hundreds pg/L to �g/L, depending on the type of PPCPsand wastewater [6]. During the wastewater treatment processes,PPCPs may be adsorbed on the suspended solids, biodegraded bythe microbes, or chemically eliminated by the disinfection pro-cess (e.g. UV or H2O2), and subsequently removed from aquaticphase [15]. The removal rates of PPCPs varied in relation to thechemical properties of the individual PPCP, and the size, operationconditions, technology used, microbial community composition,and method of disinfection of the WWTP [11]. Previous stud-ies have provided fundamental data for the understanding of

currence and removal of pharmaceuticals and personal care products), http://dx.doi.org/10.1016/j.jhazmat.2013.11.056

PPCP removal in the WWTP. However, there are clear regionalbiases in the knowledge of PPCPs all over the world [16]. Moreinformation of contamination of PPCPs in different area is stillurgent [16].

dx.doi.org/10.1016/j.jhazmat.2013.11.056


http://www.sciencedirect.com/science/journal/03043894

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mailto:[email protected]


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Most studies were based on short monitoring periods, and it wasifficult to understand the occurrence of PPCPs over an extendederiod of time. The knowledge of the seasonal variation of theccurrence and removal of PPCPs in the WWTP is limited. Vienot al. found the elimination of four antiphlogistics and a lipidegulator decreased significantly in wintertime in Aura, Finland,hich was probably caused by a lower rate of biodegradation [17].astiglioni et al. noticed the removal rates for the total loads ofarget PPCPs were higher in summer compared to winter in Italy18]. Sui et al. examined 12 PPCPs in two WWTPs monthly fromebruary 2009 to January 2010 in Beijing, China. Results showedost PPCPs had higher concentrations in the effluent in the win-

er [19]. Recently, Yu et al. investigated 14 PPCPs in August 2010nd February 2011 in five WWTPs in California, USA, and the totaloncentration of each compound was higher in winter than thatn summer [20]. However, Loraine et al. monitored PPCPs in the

WTP in San Diego, USA. The occurrence and concentrations ofPCPs were higher in summer and early autumn than in winter andpring [21]. The seasonal variations of the occurrence and removalfficiencies were discrepant among these studies. This is probablyue to only a few types of PPCPs were selected in the individ-al study, which made it difficult to compare the occurrence andemoval rates between studies and to understand the occurrencend fate of other PPCPs.

Xiamen is a major city in the southeast of China, with a pop-lation of 3.67 million and a population density of 2333 per km2

n 2011. So far, the information of the occurrence and removal ofPCPs in WWTP in Xiamen is limited. The objective of this studys to examine the occurrence and removal rates of 50 PPCPs in aocal WWTP over a period of one year. We collected and analyzedhe samples of the initial influent, oxidation ditch influent, oxida-ion ditch effluent, and final effluent in August and December 2012,

arch and May 2013. The results were used to evaluate the sea-onal variations of PPCP occurrence and removal efficiencies in the

WTP.

. Materials and methods

.1. Chemicals

The standards were of analytical grade, and were purchasedrom Sigma–Aldrich, Fluka, and Dr. Ehrenstorfer. All the analytesnd their commercial usage are list in the supplemental informa-ion (SI) Table S1. The target analytes were chosen because they arerequently detected based on the reference or commonly used byhe consumers. HPLC grade solvents (methanol and acetone) wererovided by Tedia Co. (OH, US). All the reagent water used in thistudy was Milli-Q unit (Millipore, USA). Stock solutions of individ-al PPCPs were prepared in methanol and standard mixtures wererepared by diluting the stock solution. All the standard solutionsere stored at −20 ◦C in the dark.

.2. Sample collection

Grab samples of wastewater were collected on August 28th andecember 3rd 2012, March 6th and May 30th 2013 from a domes-

ic WWTP in Xiamen, China. Xiamen has a subtropical monsoonlimate. The average temperature are 15, 23, 28, and 14 ◦C, and theverage precipitation are 120, 180, 260, and 30 mm in March, May,ugust and December, respectively [22]. This secondary WWTP isquipped with a primary treatment process, an Orbal oxidation


itch process and a UV disinfection process before final effluent.our liter amble glass bottles were used to sequentially collectastewater samples from the initial influent, influent of oxidationitch, effluent of oxidation ditch, and final effluent of the WWTP.

PRESSaterials xxx (2013) xxx– xxx

The wastewater parameters, including pH, temperature, suspendedsolid (SS), and dissolved oxygen (DO), are list in SI Table S2.

2.3. Sample analysis

Samples were prepared according to EPA Method 1694 [23]with slight modification. The target PPCPs were enriched and puri-fied by the solid phase extraction (SPE) technique. Details of thesample preparation are provided in SI. The prepared samples wereanalyzed by liquid chromatography triple quadrupole mass spec-trometry (LC-QqQ MS) using multiple reaction monitoring (MRM)mode. Details of the instrument parameters are provided in SI.

2.4. Quality assurance and quality control (QA/QC)

QA/QC was conducted to ensure the identification and quan-tification of the PPCPs. Identification of PPCPs was performed byLC–MS/MS with MRM, using the 2 highest characteristic precursorion/product ion transition pairs (SI Table S1). The ratios of prod-uct transitions were calculated to ensure correct identification. Themethod detection limits (MDLs) were in the range of 0.02–1 ng/L (SITable S1). An instrumental blank, procedural blank, sample dupli-cate, blank spike, and matrix spike, were applied for each batch.Details are provided in SI.

2.5. Data analysis

The removal efficiency of each PPCP in the WWTP was calculatedas ([influent] − [effluent])/[influent] × 100. The removal efficiencyof each PPCP in the activated sludge treatment process wascalculated as ([oxidation ditch influent] − [oxidation ditch efflu-ent])/[oxidation ditch influent] × 100. Friedman test was conductedby PAST v 2.17 to compare the seasonal variation of PPCP concen-trations in different sampling sites. Spearman’s rank correlationanalysis was conducted by PAST v 2.17 to evaluate the correlationbetween PPCP concentrations and temperature, hydraulic reten-tion time, or other parameters.

3. Results and discussion

3.1. PPCP occurrence and seasonal variation in the influent

Among the 50 PPCP targets, 39 PPCPs were detected in the initialinfluent of the WWTP. The total concentrations of each PPCP of thefour samplings are showed in Fig. 1a. However, the concentrationsof 11 PPCPs, including clofibric acid, sotalol, sarafloxacin, sul-famerazine, clenbuterol, danofloxacin, pirenzepine, ethenzamide,sulfamethoxine, octocrylene, and camphor (3-4′-methy-ben-2-one), were below the MDLs. The highest concentration wasobserved for acetaminophen, with the average concentration in theinfluent of 2963.5 ng/L. In addition, caffeine, bisphenol A, propylparaben, methyl paraben, metoprolol, ibuprofen, ketoprofen, andfenoprofen, also showed higher concentrations in the influent, withthe average concentrations more than 100 ng/L.

PPCPs showed seasonal variations in the influents (Fig. 1b).Significantly higher concentrations were found in the influent sam-ples in March 2013 compared to the samples collected in August2012, December 2012, and May 2013, with p value of 0.0003,0.002, and 0.008, respectively. In addition, higher concentrations(p = 0.03) were also observed in the influent samples in December2012 compared to the samples collected in August 2012. However,


no significant difference (p = 0.3) of PPCP concentrations betweenAugust 2012 and May 2013 was observed. This result suggestedhigher concentrations of PPCPs in the influent were observed inthe cold seasons.


ARTICLE IN PRESSG Model

HAZMAT-15581; No. of Pages 7

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The highest concentrations for the anti-inflammatory or anal-esic drugs, including acetaminophen, ibuprofen, indomethacine,efenamic acid, codeine, naprofen, and crotamiton, were observed

n March 2013, followed by December 2012. For example,he acetaminophen concentrations were 2360, 3200, 5320 and74 ng/L; the ibuprofen concentrations were 135, 184, 446 and83 ng/L, in August, December 2012, and March, May 2013,espectively. Similarly, for the detected antibiotics, including sul-amethoxazole, sulfadiazine, enrofloxacin, and sulfamethazine, theighest concentrations were also observed in March 2013, with thenly exception of sulfameter. Similar seasonal trend of antibioticsas observed by Sui et al. [19]. The concentrations of gemfibrozilere 0.5, 16, 11, 2.6 ng/L, in August, December 2012, and March,ay 2013, respectively. The increased gemfibrozil concentration in

old seasons was consistent with the fact that blood lipids patientsend to rise in winter [24]. It agreed with the study on the seasonalariation of gemfibrozil in southern California [20]. In addition,he concentrations of caffeine, metoprolol, triclosan, aspartame,ropranolol, and loratadine, were also higher in March 2013, fol-

owed by December 2012. For bisphenol A, the concentrations were210, 383, 821, 1480 ng/L in August, December 2012, and March,ay 2013, respectively. Both residential and industrial wastewa-

er might contribute to the bisphenol A load in the WWTP, sinceisphenol A is a widely used plasticizer. However, the highest con-entration of benzophenone-3 was observed in May 2013, this isrobably due to the more usage of sunscreens in summer [21].


The lower concentrations of most PPCPs in August 2012 anday 2013 (Fig. 1b) might be due to the dilution effect. The

aily processing capacity for the WWTP was 49.8, 43.4, 35.3,7.1 thousand cubic meters for August 28th and December 3rd

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samplings (a), the relative distributions percentage in different seasons (b).

2012, March 6th and May 30th 2013, respectively. A marginalnegative correlation was observed between the concentrationsof anti-inflammatory (e.g. acetaminophen, ibuprofen, antipyrine,indomethacine, codeine, naprofen, crotamiton), antibiotics (e.g.sulfamethoxazole and sulfameter) and other PPCPs (e.g. caffeine,metoprolol, triclosan, aspartame, carbamazepine, and propranolol)in the influent and the daily processing capacity (p = 0.083, r = −1 or−0.8). It suggested that the seasonal variation of these PPCP concen-trations was probably due to the dilution. The relative high waterconsumption in the warm season might accordingly dilute the PPCPconcentrations in the WWTP. In addition, Xiamen is a subtropicalcity in the southeast China, and the wet seasons are from May toSeptember and the dry seasons are from the October to April nextyear [25]. The high precipitation in August and May might dilutethe PPCP concentrations in the wastewater.

3.2. PPCP removal efficiencies and seasonal variation

Fig. 2 shows the removal efficiencies of each PPCP afterpassing through all the wastewater treatment processes. Napro-fen, acetophenol, enrofloxacin, losartan, fluoxetine, miconazole,loratadine, gibenclamide, cyclophosphamid mono, thiabendazole,sulfameter, and benzyl paraben were not included in the figurebecause the low detection frequency.

Acetaminophen and caffeine, which were present at the highestconcentrations in the influent, were removed more than 99%


in the WWTP (Fig. 2). Although acetaminophen (Fig. 3a) andcaffeine concentrations (SI Fig. 1a) in the initial influent andin the influent of oxidation ditch were within �g/L level, theconcentrations were below the MDLs or with ng/L level in the




4 Q. Sun et al. / Journal of Hazardous Materials xxx (2013) xxx– xxx

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ffluent. The oxidation ditch treatment contributed 50.5–82.1%f the total removal, indicating the removal through micro-ial degradation and adsorption by activated sludge. The highemoval efficiencies of acetaminophen and caffeine were in


ccordance with the previous study [7,10,12,17]. The removalfficiencies of bisphenol A (SI Fig. S1h), ibuprofen (SI Fig. S1i)nd fenoprofen (SI Fig. S1b) were 81.9–93.2%, 68.5–91.0% and4.2–100%, respectively, and the activated sludge treatment

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contributed to more than 50% of the total removal. Consistentlyhigh removal efficiencies for these PPCPs have also been reported[7,9,12]. The removal efficiencies of propyl paraben (SI Fig. S1d) andmethyl paraben (Fig. 3b) were 63.3–98.2% and 81.6–91.0%, respec-


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Q. Sun et al. / Journal of Hazardous Materials xxx (2013) xxx– xxx 5

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ig. 4. Total measured concentrations of each PPCP in the effluent during the four samf metoprolol in May 2013 was invalid and not included in this figure.

data now shown) were 89.7–97.1%. Previous studies reportedhe average removal efficiencies of codeine in the WWTPs wereess than 50%, with the relative standard deviation ranging frompproximate 15 to 75% [8,10]. However, the removal efficiencies inhis study were 72.1–91.0% (Fig. 3c). The high removal efficienciesere due to the high removal efficiencies in the activated sludge

reatment, which were 53.0–83.2%.The selected antibiotics could be moderately removed in the

WTP. The average removal rates for sulfadiazine (Fig. 3d), sul-amethoxazole, and sulfamethazine were 82.6%, 52.4%, and 62.3%,espectively. However, the activated sludge treatment attributedo less than 50% of the total removal. Previous studies reportedhe removal of triclosan and triclocarban in the range of 50–100%26,27]. Triclosan has a Kow of 4.8 and pKa of 7.9, while triclo-arban has a Kow of 4.2 and pKa of 12.7, which indicated theossibility for adsorption to the solid phase [26]. The present studyhowed that the average removal rates of triclosan and triclo-arban were 17.4% and −18.5%. The possible reason for the pooremoval of triclosan and triclocarban in the oxidation ditch coulde due to their persistence on the sludge particles and also the

ack of triclosan- and triclocarban-degrading bacteria in the micro-ial community of the activated sludge. However, the reductionf triclosan (SI Fig. S2a) and triclocarban (SI Fig. S2b) concentra-ions was observed during the disinfection process. It is confirmedhat these antimicrobial agents may be removed in the presence


f UV radiation [28,29]. Previous study showed the removal effi-iency of PPCPs by the conventional treatment processes was notatisfactory, suggesting the advanced steps to be applied to con-rol the PPCPs [16]. Results from the present study indicated that

s (a), the relative distributions percentage in different seasons (b). The concentration

the UV disinfection process could improve the removal of somePPCPs.

Previous study showed that the removal of carbamazepine wasconsistently lower than 30% in 20 studies [30], and similar removalefficiencies were observed in the present study. The low removalrate of carbamazepine can be explained by its persistent proper-ties and water-soluble nature [7]. The low sorption constant on theactivated sludge (Kd) and pseudo first-order degradation rate con-stant (Kbio) value suggested that the adsorption and biodegradationof carbamazepine was low [12]. In addition, the concentrations ofPPCPs, including indomethacine, mefenamic, sildenafil, crotami-ton, diazepam, and propranolol, appeared to increase during thetreatment process in some samples, and therefore, had negativeremoval efficiencies. The low removal efficiencies of these PPCPswere in accordance with previous studies [7,27,31,32], indicatingthe resistance of these PPCPs during the wastewater treatment pro-cesses. Another possible reason was that some PPCPs entered theWWTPs as conjugates and were then cleaved during treatment,leading to an apparent increase in concentrations of the PPCP dur-ing the treatment processes [33].

The seasonal variation of PPCP removal rates during theactivated sludge treatment process was observed. The removalefficiencies of acetaminophen (Fig. 3a), caffeine (Fig. S1a), and feno-profen (Fig. S1b) were consistently high during the activated sludgetreatment between seasons, and the high removal efficiencies con-


tributed to the high elimination in WWTP. The removal efficienciesof propyl paraben (Fig. S1d), ketoprofen (Fig. S1c), diclofenac acid(Fig. S1e), codeine (Fig. 3c), indomethacine, and crotamiton (figurenot shown) in the activated sludge treatment showed a marginal


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ositive correlation (p = 0.083) with sewage temperature, with cor-elation coefficient value of 1, 1, 0.8, 0.8, 0.8, and 0.8, respectively.he lower sewage temperature (SI Table S2) might reduce theicrobial activity and decrease the removal efficiencies in the acti-

ated sludge treatment process, which would subsequently affecthe removal rates in the WWTP [17–20]. However, since Xiamens in the subtropical zone, the measured sewage temperatures inhe oxidation ditch were 29.5, 21.8, 20.4, 27.4 ◦C in August andecember 2012, March and May 2013, respectively. The wastewa-

er temperature in the cold seasons and warm seasons had lessifference compared to the study in Beijing, China, where the tem-eratures were 10–14 ◦C in winter and 25–27 ◦C in summer [19],

n which case the seasonal variation in activated sludge removalfficiencies was more significant.

The removal efficiencies of sulfadiazine (Fig. 3d) and caffeineFig. S1a) in the oxidation ditch were higher in December 2012nd March 2013 compared to August 2012 and May 2013. Thisesult indicated that temperature was not the only parameter toffect the PPCP removal in the oxidation ditch in this study. Theydraulic retention time in the oxidation ditch was 10.3, 11.8, 14.5,nd 9.0 h for the sampling date at August 2012, December 2012,arch 2013, and May 2013, respectively. A marginal positive corre-

ation (p = 0.083) was observed between the removal efficiencies ofaffeine and sulfadiazine in the oxidation ditch and hydraulic reten-ion time. This result suggested that the higher daily processingapacity in the warm seasons might reduce the hydraulic retentionime of PPCPs in the treatment process and accordingly reduced theemoval efficiencies of some PPCPs [34].

.3. PPCPs in the effluent

Among the 39 PPCP detected in the influent, 36 PPCPs wereetected in the final effluent of the WWTP. The PPCP concentrations

n the effluent were in the range of <MDLs ∼ 304 ng/L (Fig. 4a). Theighest concentrations were observed for ketoprofen, bisphenol, triclosan, ibuprofen, and triclocarban, with the average con-entrations of 95.0, 80.5, 60.0, 48.6, 42.4 ng/L, respectively. OtherPCPs had the average concentrations less than 20 ng/L. Signifi-antly higher concentrations of PPCPs were observed in effluentamples collected in March 2013 compared to August 2012 anday 2013, with p value of 0.006 and 0.03 (Fig. 4b). The high PPCP

oncentrations in the effluent in March might be due to the highoncentrations in the influent and the low removal efficiencies.his result suggested higher concentrations of PPCPs could be dis-harged into the surrounding seawater in the early March.

. Conclusions

The occurrence and removal efficiencies of PPCPs in a WWTPn Xiamen, China were investigated over a period of one year.mong the 50 targets, 39 PPCPs were detected in the initial influent,ith the concentrations of <MDLs ∼ 5320 ng/L. Acetaminophen,

affeine, bisphenol A, and ibuprofen were the dominant com-ounds in the influent, with average concentrations of 2964, 2109,74, and 237 ng/L, respectively. 14 PPCPs could be removal morehan 50% in the WWTP. The activated sludge treatment processontributed to most of the removal of PPCPs, while the adsorptiono the particles in the primary treatment and the transformationnder UV radiation in the disinfection treatment also contributedo the PPCP removal. The seasonal variations of PPCP occurrencend removal were detected. In the influent, most pharmaceuticals


howed higher concentration in the cold seasons than the warmeasons. The lower dilution rate in the cold seasons owing to theess water consumption and precipitation might contribute theigher PPCP concentrations. The seasonal variations of the PPCP

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PRESSaterials xxx (2013) xxx– xxx

removal were also observed due to both the temperature effect onthe microbial activity of activated sludge and the precipitation andwater consumption effect on the hydraulic retention time of PPCPsin the treatment processes. The PPCP concentrations in the effluentwere in the range of <MDLs ∼ 304 ng/L. Significantly higher con-centrations of PPCPs were observed in effluent samples collectedin March 2013 compared to the other seasons, suggesting higherconcentrations of PPCPs could be discharged into the surroundingseawater during this period.

Acknowledgements

We thank Mr. Lifeng Lin for his help in LC–MS maintenance.We appreciated Mr. Xiang Cai for his help in the sampling. Thiswork was supported by the National Science Foundation of China(41201490, 41106096), the Natural Science Foundation of FujianProvince, China (2011J05035), Science and Technology Innovationand Collaboration Team Project of the Chinese Academy of Sciences,Technology Foundation for Selected Overseas Chinese Scholar ofMOHRSS, China, Science and Technology Planning Project of Xia-men, China (3502Z20120012), and the CAS/SAFEA InternationalPartnership Program for Creative Research Teams (KZCX2-YW-T08).

Appendix A. Supplementary data

Supplementary data associated with this article can be found,in the online version, at http://dx.doi.org/10.1016/j.jhazmat.2013.11.056.

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seasonal variation in the occurrence and removal of pharmaceuticals and personal care products in a...

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