Chemosphere 119 (2015) 820–827

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Occurrence and trends in concentrations of perfluoroalkyl substances(PFASs) in surface waters of eastern China

http://dx.doi.org/10.1016/j.chemosphere.2014.08.0450045-6535/� 2014 Elsevier Ltd. All rights reserved.

⇑ Corresponding authors. Address: SOA Key Laboratory for Polar Science, Polar Research Institute of China, Shanghai 200136, China. Tel.: +86 21 58717635; fax58711663 (M. Cai). Tel.: +49 4152 872330; fax: +49 4152 872332 (Z. Xie).

E-mail addresses: caiminghong@pric.gov.cn (M. Cai), zhiyong.xie@hzg.de (Z. Xie).

Zhibo Lu a,b, Luning Song a,b, Zhen Zhao c, Yuxin Ma a,b,d, Juan Wang a,b, Haizhen Yang a,b, Hongmei Ma d,Minghong Cai d,e,⇑, Garry Codling e, Ralf Ebinghaus c, Zhiyong Xie c,⇑, John P. Giesy e

a College of Environmental Science and Engineering, Tongji University, Shanghai 200092, Chinab State Key Laboratory on Pollution Control and Resource Reuse, Tongji University, Shanghai 200092, Chinac Helmholtz-ZentrumGeesthacht, Centre for Materials and Coastal Research GmbH, Institute of Coastal Research, Max-Planck Strße. 1, D-21502 Geesthacht, Germanyd SOA Key Laboratory for Polar Science, Polar Research Institute of China, Shanghai 200136, Chinae Toxicology Centre and Department of Veterinary Biomedical Sciences, University of Saskatchewan, Saskatchewan, Canada

h i g h l i g h t s

� Perfluorohexanoic acid (PFHxA) wasthe predominant PFASs in some cities.� PFOS represented a small proportion

ofP

PFASs.� More than 4000 kg year�1 PFASs are

discharged into the East China Sea.

g r a p h i c a l a b s t r a c t

a r t i c l e i n f o

Article history:Received 4 May 2014Received in revised form 15 August 2014Accepted 19 August 2014

Handling Editor: I. Cousins

Keywords:PFASsSurface watersThe eastern ChinaSpatial distributionMass flowAsia

a b s t r a c t

Spatial distributions of perfluoroalkyl substances (PFASs) were investigated in surface waters in Shang-hai, Jiangsu and Zhejiang Provinces of eastern China during 2011. A total of 39 samples of surface waters,including 29 rivers, 6 lakes and 4 reservoirs were collected. High performance liquid chromatography/negative electrospray ionization-tandem mass spectrometry (HPLC/(�)ESI-MS/MS) was used to identifyand quantify PFASs. Concentrations of PFAS were greater in Shanghai than that in Zhejiang Province. Con-centrations of the sum of PFASs (

PPFASs) in Shanghai and Kunshan ranged from 39 to 212 ng L�1, while

in Zhejiang Province, concentrations ofP

PFASs ranged from 0.68 to 146 ng L�1. Perfluorooctanoic acid(PFOA) was the prevalent PFAS in Shanghai. In contrast, PFOA and perfluorohexanoic acid (PFHxA) werethe prevalent PFASs in Zhejiang Province. Concentrations of perfluorooctane sulfonate (PFOS) rangedfrom <0.07 to 9.7 ng L�1. Annual mass of

PPFASs transported by rivers that flow into the East China

Sea were calculated to be more than 4000 kg PFASs. Correlation analyses between concentrations of indi-vidual PFASs showed the correlation between PFHxA and PFOA was positive, while the correlationbetween PFHxA and perfluorooctane sulfonamide (FOSA) was negative in Shanghai, which indicated thatPFHxA and PFOA have common sources. Principal component analysis (PCA) was employed to identify

: +86 21

Z. Lu et al. / Chemosphere 119 (2015) 820–827 821

important components or factors that explain different compounds, and results showed that PFHxA andFOSA dominated factor loadings.

� 2014 Elsevier Ltd. All rights reserved.

1. Introduction

Because of their characteristics of surface activity, chemical sta-bility and hydrophobic and oleophobic amphiphilic nature, perfluo-roalkyl substances (PFASs) during the last half century have beenwidely used in various processes and products, including produc-tion of emulsifiers, surfactants, dust preventive, disposable table-ware additives, and fire-fighting foams (Giesy and Kannan, 2001,2002; Olsen et al., 2005, 2007; Prevedouros et al., 2006; Giesyet al., 2010). Previous studies have documented that widespreadapplication as well as environmental persistence and bioaccumula-tion of terminal degradation products of PFAS precursors haveresulted in global occurrence of PFASs in the atmosphere (Kimet al., 2012), waters (Zushi and Masunaga, 2011), sediments (Naileet al., 2013), not only from urban areas, but from remote areas suchas Qinghai-Tibet Plateau (Shi et al., 2010) and polar regions (Caiet al., 2012a,b). Overall, perfluorooctane sulfonate (PFOS) and per-fluorooctanoic acid (PFOA) were the two most often observed andreported PFASs because of their abundant production and wideuse in fluoropolymer manufacture (Prevedouros et al., 2006).

In 2009, PFOS and its related compounds were listed in Annex Bof the Stockholm Convention (SC) on Persistent Organic Pollutants(POPs) (Wang et al., 2009). Then shorter-chain PFASs (carbon chainlength less than seven), which have lesser toxic potency than the 8-carbon PFASs (Beach et al., 2006; Buhrke et al., 2013), have beenincreasingly used. After the phase-out of PFOS-based chemistries(Olsen et al., 2005), a shift from 8-carbon PFASs to the 4-carbonPFBS has been observed in the PFASs in dated cores from LakeMichigan, in North America in the region where 3 M manufacturedPFOA and PFOS (Codling et al., 2014). Perfluorobutanesuflonate(PFBS) and perfluorobutanoic acid (PFBA) dominated PFASs in theRiver Rhine (Möller et al., 2010), while PFBS was the most preva-lent PFASs in the Netherlands (Kwadijk et al., 2010). In Japan, PFNAhas become the most prevalent PFASs in the Tokyo Bay basin(Zushi et al., 2011). In China, concentrations of some shorter-chainsubstitutes are increasing in surface waters from various industrialareas, such as perfluorohexanoic acid (PFHxA) in Liaoning Province(Sun et al., 2011) and in Tai Lake in Jiangsu Province (Yu et al.,2013), whereas in Hubei Province PFBS and PFBA were the pre-dominant PFASs (Zhou et al., 2013). Current contaminations ofPFASs mainly arise from application of alternatives and consump-tion of stockpiles of longer-chain PFASs.

The Yangtze River delta, one of the most investigated areas inChina, is unique relative to PFASs, because it is located at the junc-tion of eastern coastal developed areas, involving Shanghai andparts of Jiangsu and Zhejiang Provinces. Shanghai, an industrial-ized, densely populated urban area, is situated where the HuangpuRiver receives effluents containing PFASs. To date, investigations ofPFASs in surface waters of cities around the Yangtze River delta (Soet al., 2007; Pan and You, 2010) have focused primarily on PFOAand PFOS, and further comprehensive studies about variation ofdominant PFASs and restructure of PFAS patterns are required.

In the present study, concentrations of 17 PFASs were quanti-fied in 39 surface waters, which were collected in eastern China,including 28 rivers, 7 lakes and 4 reservoirs. The objectives of thisstudy were to: (1) determine concentrations, profiles, patterns ofrelative concentrations and spatial distributions of PFASs in easternChina; (2) identify possible pollution sources in eastern China; (3)calculate discharge loads of PFASs to the East China Sea.

2. Materials and methods

2.1. Sampling

During May to July, 2011, samples of surface water were col-lected from three areas (Shanghai, Jiangsu Province and ZhejiangProvince) of eastern China, including the major rivers, lakes andreservoirs of the region. Details regarding sampling dates, and loca-tions and area description of the investigated areas are given inTable S1. Sampling sites located in Zhejiang Province are abbrevi-ated as ZJ1-ZJ29, while sites located in Shanghai are abbreviatedas SH1–SH8, while sites located in Kunshan, Jiangsu Province areabbreviated as KS1–KS2 (Fig. 1). Samples were divided into twozones, an industrial zone: SH1–SH2 and KS1–KS2; and a mixturefunction zone: ZJ1–ZJ29.

2.2. Chemicals and standards

Seventeen PFASs, including perfluoroalkane sulfonates (PFSAs)(C4, C6–C8, and C10), perfluoroalkyl carboxylates (PFCAs) (C4–C14),FOSA were quantified. The nine mass-labeled PFSAs used as inter-nal standards (IS) were 13C-labeled ionic PFSAs and 18O-labeledperfluorohexane sulfonate (PFHxS). 2H-perfluoro-[1,2-13C2]-2-dec-enoic acid (8:2 FTUCA) was used as the injection standard (InjS).Methanol (SupraSolv) and ammonium hydroxide (25%, Suparpur)were purchased from Merck (Darmstadt, Germany). The methanolwas distilled in a glass apparatus before use, and the Milli-Q waterwas pre-cleaned through cartridges to remove any residual PFASsin the water.

2.3. Extraction and analysis

Identification and quantification of PFASs was accomplished byuse of previously published methods (So et al., 2004; Reagen et al.,2008; Naile et al., 2010a). Samples of 1 L were filtered by 0.45 lmGF/C were solid-phase extracted (SPE) using glass funnels and SPEcartridges (Waters Oasis WAX, 150 mg, 6 cm3, 30 mm). After beingspiked with 1 ng IS (50 pg lL�1, 20 lL), the filtrate was loaded ontothe cartridge at a rate of 2 drops per second. The cartridge was thenwashed with 10 mL Milli-Q water to remove the salt and dried by avacuum pump to achieve a better recovery. Dried cartridges wereeluted with 10 mL methanol with 0.1% ammonium hydroxide.Elutes were reduced to 150 lL under a gentle stream of nitrogen(purity >99.999%). Before being injected into the instrument, 1 ng(50 lL, 20 pg lL�1) of mass-labeled 8:2 FTUCA as the InjS wasspiked into the vials.

Instrumental analyses were performed using a high-performance liquid chromatography–negative electrospray ioniza-tion-tandem mass spectrometry system (HPLC/(�)ESI–MS/MS)with a HP 1100 HPLC system (Agilent, Geesthacht, Germany) cou-pled to an API 3000 triple-quadrupole mass spectrometer (AppliedBiosystems/MDS SCIEX, Geesthacht, Germany). The instrumentalsetup is described elsewhere (Ahrens et al., 2009a).

2.4. Quality assurance and quality control

The method detection limit (MDL), recovery of each spikedsample, field blank and duplicate samples were measured(Table S2). Breakthrough of PFASs was tested by using tandem

Fig. 1. Spatial distributions of concentrations of sum-PFASs in surface waters in eastern China.

822 Z. Lu et al. / Chemosphere 119 (2015) 820–827

Oasis WAX cartridges to extract 1 L seawater spiked with 400 pginternal standards. PFASs in the upper cartridge accounted formore than 80% of the sum determined from both cartridges.However, there were no internal standards detectable in the lowercartridge, indicting little breakthrough for PFASs with Oasis WAXcartridge. The MDLs were determined by spiking with 400 pg inter-nal standards in 1 L Millipore water which is pre-cleaned withOasis WAX cartridge. The MDLs were established at a signal-to-noise (S/N) of 10, which ranged from 0.02 ng L�1 (for both PFDAand perfluoroundecanoic acid (PFUnDA)) to 0.14 ng L�1 for PFBA.Overall recoveries ranged from 51 ± 21% for [13C4]-PFOS to78 ± 20% for [18O2]-PFHxS (Table S2). Concentrations werecorrected for recoveries of IS in every sample.

3. Results and discussion

3.1. Spatial distributions and compositions of PFASs in eastern China

Concentrations of the 14 PFASs that were detected at concentra-tions greater than the MDLs are given (Tables S3–S4). Only PFOAand PFHxA were detected in all samples, while perfluorododeca-noic acid (PFDoDA) was detected in only two samples and concen-trations of perfluorodecane sulfonate (PFDS), perfluorotridecanoicacid (PFTrDA) and perfluorotetradecanoic acid (PFTeDA) were lessthan the MDLs. Here, the discussion focuses on only the 13 PFASs,including C4, C6–C8 PFSAs, C4–C11 PFCAs and FOSA.

Concentrations ofP

PFASs in Shanghai and Kunshan rangedfrom 39 ng L�1 to 212 ng L�1 (Table S4), which were comparablewith those in Shenyang (Sun et al., 2011), but less than those fromWuhan (Wang et al., 2013) and Fuxin, Liaoning (Bao et al., 2011),and greater than those for Vietnam (Kim et al., 2013) and Tokyobay, Japan (Zushi et al., 2011) (Tables 1 and S5). In ZhejiangProvince, concentrations of

PPFASs were a less with a mean of

43 ng L�1 and a range of 0.68–146 ng L�1, which were also lessthan those for Singapore (Nguyen et al., 2011), comparable withLiao River (Yang et al., 2011), but greater than those observed inSeoul and Busan, Korea (Kim et al., 2011) and Huai River (Yuet al., 2013) (Tables 1 and S5). ZJ16 and ZJ17 were collected directlyfrom municipal, sewage outfalls at the inner and outer sluice gateand were considered as spot sources, so they were not included inthe calculation of the mean and range of Zhejiang Province.

Patterns of relative concentrations of PFASs varied among loca-tions, which indicates different potential sources between Zhejiangand Shanghai. PFOA was the most prevalent compound in samplesfrom Shanghai and Kunshan, accounting for 51–86% of

PPFASs

while PFOA and PFHxA dominated concentrations ofP

PFASs inmost industrial locations of Zhejiang Province, which were as greatas 80% and 46%, respectively (Fig. 2).

3.2. Sources of PFASs in Zhejiang Province

In Zhejiang Province, we choose 29 sampling sites includingfour reservoirs, five lakes and twenty river samples to study con-centrations and composition of PFASs. In Zhejiang Province, thegreatest concentration of the

PPFASs, 146 ng L�1, which was

observed in West Lake (ZJ1) in the city of Hangzhou (Table S3),was greater than those in samples from locations in the river. Thereare no known discharges because of the area around West Lake is aprotected region with no industrial development. However, due torapid development of tourism, consumption of water in the WestLake scenic area, especially during the wet season when sampleswere taken, the capacity of the sewage system is exceeded andwastewater can spill out of sanitary sewers and flow into WestLake. Diffuse sources such as urban runoff can also an importantpotential source (Ahrens, 2011). These sources might be the causeof the observed concentrations of PFASs in West Lake.

Table 1Comparison of concentrations of individual PFASs in surface waters in China.

Type Sampling date Site PFOS PFHxA PFOA PFNA PFDAP

PFAS Area description Refs.

Lake 05/2011–07/2011 West Lake 0.35 53 85 0.50 0.20 146 Urban area This study05/2011–07/2011 Tai Lake (n = 2) 2.0–2.8 9.4–10 20–23 1.1–1.2 0.42–0.57 7.7–7.6 Lake inlet This study07/2011 Tai Lake 15 19 56 2.6 1.5 16 Industrial area Yu et al. (2013)

8.5–21 15–31 23–71 1.9–3.8 1.1–2.4 11–2611/2009–12/2009 Tai Lake 27 naa 22 <0.8 <0.3 28 Whole lake Yang et al. (2011)

3.6–394 naa 11–37 <0.8 <0.3 3.9–40002/2009–04/2009 Tai Lake 3.5–9.4 naa 25–34 2.3–3.6 <2.5 –c Lake shore water Qiu et al. (2010)05/2008 Guanting reservoir <0.2–0.52 <1 0.55–2.3 <2 <0.2–0.23 0.70–3.1 Drinking water source Wang et al. (2011)05/2011–07/2011 Tangpu reservoir <0.07 0.15 1.3 0.17 0.070 2.1 Town area This study

Changtan reservoir <0.07 0.12 0.47 0.11 0.050 0.99 Rural areaHongqiao reservoir <0.07 0.21 2.9 0.24 0.10 3.7 Town area/fisheryCengang reservoir 0.69 0.49 7.9 0.41 0.090 11 Town area/fishery

River 11/2004 Shanghai 12–14 5.0–5.3 230–260 9.0–10 3.3–3.8 –c Urban area/industry area So et al. (2007)12/2008 Hai River, Tianjin 1.1–7.7 naa 4.7–23 0.29–2.2 0.12–1.0 –c Urban area/industry area Pan et al. (2011)08/2009 Fuxin 0.28–0.54 naa 27–668 0.43–16 <0.10–21 370–713 Urban area/industry area Bao et al. (2011)09/2009 Shenyang 0.66–16 1.3–37 9.2–25 <1.30–5.2 <1.08–1.2 17–240 Urban area/industry area Sun et al. (2011)09/2009 Hun River, Liaoning 0.40–3.3 1.3–38 1.8–11 <1.30–1.6 <1.08–0.66 –c Urban area Sun et al., 201111/2009–12/2009 Liao River 0.33 naa 11 <0.8 <0.3 44 Urban and industrial area Yang et al. (2011)

<0.7–6.6 naa <0.7–28 <0.8 <0.3 1.4–1312009 Victoria Harbour,

Hongkong0.030–1.2 0.15–0.97 0.31–1.9 0.032–0.40 0.014–0.31 –c Urban area Loi et al. (2013)

04/2010 Wuhan 52 ndb 81 19 28 204 Urban area/industry area Wang et al. (2013)ndb �89 ndb 2.5–256 ndb �74 ndb �95 8.6–568

03/2011 Huai River 4.7 0.62 18 0.91 0.33 28 Industrial area Yu et al. (2013)1.4–25 <0.10–1.5 6.2–47 0.67–1.4 <0.10–1.0 11–79

05/2011–07/2011 Hangzhou Bay 1.0 25 45 0.69 0.31 77 Coastal area This studyQiantang River 0.41 31 57 0.66 0.31 97 Urban areaCao’e River 0.24 0.76 4.8 0.54 0.37 9.0 Middle streamFenghua River 2.8 2.7 53 1.1 0.48 66 Town areaYong River 1.6 2.4 39 1.0 0.35 53 Town areaYuyao River 3.4 3.2 37 1.5 0.73 64 Town areaOu River <0.07 0.15 0.64 0.12 0.050 1.3 Rural areaFeiyun River 0.24 0.43 1.7 0.090 <0.02 3.3 Rural areaJiao River 5.0 1.0 4.3 0.80 0.33 15 Rural area

05/2011–07/2011 Shanghai 3.0 11 182 2.2 1.3 212 Urban area/industry area This study

a na: Not analysed.b nd: Not detected. MDLs were 0.6–8 ng L�1 for all target analytes in water samples according to Wang et al. (2013). MDLs of individual PFASs were not given in the

literature.c ‘‘–’’: Not given in the literature.

Z. Lu et al. / Chemosphere 119 (2015) 820–827 823

In Zhejiang Province PFOA, PFHxA and PFBS were the most fre-quently detected PFASs. According to the profiles of relative con-centrations, locations ZJ1–ZJ11 were predominated by PFOA andPFHxA, while for locations ZJ12 to ZJ29, PFOA was the predominantPFAS, followed by PFHxA and PFBS. Concentrations of PFOS wereless with a range from <0.07 to 5.0 ng L�1. The results of this studyare different from those of previous studies where PFOA and PFOSwere the two predominant PFASs (Thompson et al., 2011; Yu et al.,2013; Naile et al., 2010b). The greatest concentration of PFOA insamples from Zhejiang Province was 229 ng L�1, was observed atlocation ZJ17, which is located just outside the sluice on the Cao’eRiver. However, when river water flowed inside the sluice (ZJ16),the concentration of PFOA was 90 ng L�1, with concentrations ofother individual PFASs only slightly different. This result indicatesa point source of PFOA in the vicinity of location ZJ17. The greatestconcentration of PFHxA observed was 53 ng L�1, which is greaterthan those measured in Liaoning (Sun et al., 2011) and Hong Kong(Loi et al., 2013) in China, Canada (de Solla et al., 2012) and France(Labadie and Chevreuil, 2011) (Table 1, S5). There were unexpect-edly great concentrations of PFHxA in Zhejiang Province, especiallyat locations ZJ1–ZJ9, which are located in West Lake (53 ng L�1),Jiaxing (25–41 ng L�1) and Huzhou cities (9.4–30 ng L�1)(Table S3). Results of previous studies have shown PFHxA to be amajor constituent of

PPFASs (Sun et al., 2011; Li et al., 2011;

Meyer et al., 2011; Labadie and Chevreuil, 2011; Yu et al., 2013).The prevalence of PFHxA instead of PFOS suggests a transition inproduction of PFASs after restrictions for PFOS and PFOA wereintroduced, such that PFHxA has become a replacement for C8

compounds (Meyer et al., 2011; Yu et al., 2013). Zhejiang Provincehas the largest production of fluorine-based chemicals in China(Fluoroplastics of China, 2011), and the Juhua conglomerate is itsleading enterprise. Juhua has developed a new C6-based waterand oil repellent furnishing product that does not contain C8 com-pounds, use of which is likely responsible for the greater concen-trations of PFHxA observed in this study (Yu et al., 2013).

Locations ZJ10 and ZJ11 are located in the inlets southwest ofTai Lake (Ch: Taihu), which is the third largest freshwater lake inChina. Results of previous studies of Tai Lake (Table 1) indicatedthat concentrations of PFASs have varied as a function of time.From 2009 to 2011, concentrations of

PPFSAs have decreased

(Qiu et al., 2010; Yang et al., 2011; Yu et al., 2013). Concentrationsof PFOS (2.0–2.8 ng L�1) observed in the study, the results of whichare presented here were lesser than those detected in the samelocation in 2009–2010 (3.5–9.4) (Qiu et al., 2010). This can beattributed to voluntary phasing-out of PFOS and its relatedcompounds (Cai et al., 2012b). Based on the results of a contempo-raneous study in 2011 (Yu et al., 2013), PFHxA is becoming the pre-dominant PFASs in Tai Lake. This result suggests increased uses ofC6-based compounds as substitutes for C8 PFASs in ZhejiangProvince.

3.3. Sources of PFASs in Shanghai and Kunshan

Locations SH1–SH8 were on the Huangpu River in Shanghai,which is the largest river in Shanghai and receives sewagedischarges from Shanghai and upper stream, including domestic

Fig. 2. Profile of relative contributions of individual PFASs to sum-PFASs in surfacewaters of eastern China.

824 Z. Lu et al. / Chemosphere 119 (2015) 820–827

sewage and industrial wastewater (Zhang et al., 2013). Differentfrom the situation in Zhejiang Province, in Shanghai and Kushan(KS1–KS2) only PFOA predominated concentrations of

PPFASs

with a mean concentration of 88 ng L�1 (Table S4). After PFOA werePFHxA and PFBS, which were detected with lesser ranges of 4.0–16 ng L�1 and 4.6–12 ng L�1, respectively. PFOS and other individ-ual PFASs also occurred at lesser concentrations. Compared withother industrial areas around the world, Shanghai and Kunshanwere more contaminated by PFOA than those in Vietnam (Kimet al., 2013), Germany, Spanin (Llorca et al., 2012), Tokyo (Zushiet al., 2011), France (Labadie and Chevreuil, 2011) and Tianjin(Pan et al., 2011) and Shenyang in China (Sun et al., 2011)(Table S5), but less than those for Wuhan (Wang et al., 2013) andFuxin (Bao et al., 2011) in China (Table 1). This indicated PFOAwas largely used in industrial production in China, and the fluorinechemical industry was likely the main source of PFASs (Xiao et al.,2012; Yan et al., 2012). The large concentration of 212 ng L�1P

PFASs observed at SH1 might be attributable to discharges fromwastewater plants (WWTPs) in Shanghai, which have been deter-mined to be the major sources of PFASs to surface water (Sunet al., 2011). Compared with results of a previous study in Shanghai(So et al., 2007), at the location, named SH3 in former study, that isnear location SH1 in this study, a decrease of PFOS and PFOA wasobserved (Table 1), confirming that restrictions for C8 compoundsare functioning to reduce releases of C8 chemicals to theenvironment.

3.4. Mass loadings of PFASs to the East Sea

PFASs are expected to mainly remain in the water column andthus can be transported with riverine flows based on their

Table 2Estimated flux of dissolved PFASs in selected rivers of eastern China (kg year�1).

Name Discharge (m3 s�1) PFOS

Huangpu River 320.3 30Qiantang River 470.3 6.1Cao’e River 143.6 1.0Yong River 111.0 5.6Fenghua River 53.5 4.8Yuyao River 52.1 5.5Jiao River 163.9 26Ou River 619.9 0.78Feiyun River 126.8 0.96

a PPFAS includes PFBS, PFHxS, PFHpS, PFOS, PFBA, PFPA, PFHxA, PFHpA, PFNA, PFDA

solubilities and persistences (Boulanger et al., 2005). The area stud-ied is a typical source of PFAS emission in east China. To evaluatethe emissions of PFASs from the source area to the coastal watersof China and ultimately to the global marine environment,discharges of PFASs were calculated (Eq. (1); Sun et al., 2011).

Mass flow ¼ Cwater � Fwater ð1Þ

where Cwater is PFAS concentration in water (ng L�1) and Fwater is theriver flux. For samples for which a particular PFAS could not bedetected, a surrogate concentrations equivalent to half of MDLswere used. Mass flow of PFASs in this study just indicated dissolvedfraction of PFASs from rivers to the sea, regardless of form ofcompounds in seawater.

Dissolved concentrations of PFASs, measured at mouths of riversin each basin were used along with average annual discharges toestimate loads to the East China Sea, without consideration of sea-sonal differences in discharges (Table 2). The Huangpu and Qian-tang Rivers (SH1 and ZJ7) exhibited relatively large mass flows ofP

PFASs of 2146 and 1445 kg year�1, respectively, to the East ChinaSea. The Huangpu River transported 1841 kg PFOA year�1, followedby Qiantang River and Yong River (ZJ22) with 849 kg year�1 and137 kg year�1, respectively (Table 2). A discharge of 461 kgPFHxA year�1 came from the Qiantang River, followed by107 kg year�1 from the Huangpu River, which indicates that theQiantang River contributed more PFHxA to the East China Sea everyyear. All the rivers studied flow directly into the East China Sea,expect the Huangpu River, which joins the Yangtze River before itfinally runs into the East China Sea. Thus, more than 4000 kg of dis-solved PFASs were discharged annually into the East China Sea.

In comparison with other rivers in the world, the mass flow ofP

PFASs of Huangpu River (2146 kg year�1) was greater than thoseof the Ebro River with a loading of 31 kg

PPFASs year�1 (Sánchez-

Avila et al., 2010) and the Elbe River with a loading of113 kg year�1 to North sea (Ahrens et al., 2009b), but lesser thanthose of the Po River in Italy, which had a loading of2628 kg

PPFASs year�1 (Loos et al., 2008). Alternatively, mass

loadings of other individual PFASs in present study were less thanPFOA and PFHxA, especially for PFOS. The flux of PFASs of the Han-jiang River in Wuhan, China was 69.8 m3 s�1, but the great concen-tration of PFOS in waters of the Hanjiang River resulted in arelatively great flux of 130 kg PFOS year�1 (Wang et al., 2013),which was greater than any river in present study. Mass flowevaluation is essential to determine the pollution of a river andto the ocean rather than the concentration or the flux singly.

3.5. Correlations between concentrations of individual PFASs andinfluence factor analysis

Relationships among PFASs and identification of sources ofPFASs in surface waters of eastern China were investigated byuse of pairwise correlations and factor analyses. Two regions,Shanghai and Kunshan (n = 10) and Zhejiang Province (n = 29),

PFOA PFNA PFHxAP

PFASa

1841 22 107 2146849 9.8 461 144522 2.3 3.4 41137 3.5 8.4 18589 1.8 4.5 11261 2.5 5.2 10622 4.1 5.3 7913 2.2 3.0 246.8 0.3 1.7 13

, PFUnDA and FOSA.

Fig. 3. Plot of PC1 and PC2 from principal component analysis (PCA) of PFASs as variables for two areas in eastern China. (Blue arrow means vector resultant of PC1 and PC2.)(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Z. Lu et al. / Chemosphere 119 (2015) 820–827 825

were analyzed by use of Spearman rank correlation analysis(Table S6). In Zhejiang Province, except for FOSA, most of the PFASswere positively correlated, regardless of whether they were PFSAsor PFCAs, which indicates common sources for most of the PFASs.However, for Shanghai and Kunshan, no correlations were foundbetween concentrations of PFASs (C4, C6–C8), but strong correla-tions were observed among longer-chain PFCAs (>C6). PFOA cameprimarily from industrial manufacture while PFHpA, PFNA, PFDAand PFUnDA were possibly from degradation of fluorotelomer alco-hols (FTOHs) (So et al., 2007; Möller et al., 2010) because concen-trations of those compounds were less in the study area. In theShanghai-Kunshan region, PFHxA was positively correlated withPFOA (r = 0.661, p = 0.05) but negatively correlated with FOSA(r = �0.677, p = 0.05). Therefore, it is likely that PFHxA and FOSAwere released from different sources. Results of Principle Compo-nent Analyses (PCA) also shows the same result (Fig. 3). Two prin-cipal components were extracted from the composition data, fromZhejiang Province, Shanghai and Kunshan (n = 39). Longer-chainPFCAs (C > 8) were positively loaded together into the first princi-pal component (PC1). Concentrations of PFHxA were significantlyand positively associated with the second principal component(PC2), while concentrations of FOSA were negatively loaded toPC2 (Fig. 3). Results of previous studies have shown that FOSAwas related to degradation of precursors like N-ethylperfluorooc-tane sulfonamide (N-EtFOSA) and perfluorooctane sulfonamideacetate (FOSAA) (Rhoads et al., 2008; Plumlee et al., 2009). Similarto PFOA, PFHxA was probably released directly from industriesduring manufacture or use, a conclusion which is consistent withthose of previous studies, which indicating that greater concentra-tions of PFHxA or PFOA precursors in WWTPs probably came fromindustrial sources (Xiao et al., 2012). The result was agreementwith the conclusion that PFHxA was used as new material inmanufacture industry of Zhejiang Province, China.

4. Conclusions

Concentrations of 17 PFASs were measured in surface waters at39 sampling sites in eastern China. Comparing the results with

those of previous studies, concentrations of PFOS were generallyless, but relatively great concentrations of PFHxA were observed.This confirms that global restrictions on manufacture and use ofPFOS, imposed by the Stockholm Convention on Persistent OrganicPollutants (POPs) are having an effect on concentrations of PFOS insurface waters of eastern China. The appearance of relatively greatconcentrations of PFHxA in Zhejiang Province is likely the result ofusing PFHxA or ammonium perfluorohexanoate, APFHx as replace-ments for PFOA or ammonium perfluorooctanoate, APFO in fluoro-polymer polymerization. PFHxA, also PFBS are considered to be lesshazardous because of their lesser acute toxicity and potential forbioaccumulation compared to compounds, such as PFOA and PFOS,but like the longer-chain homologues they are also persistent inthe environment. Thus, the current increasing global productionand use of these chemicals and their potential precursors will leadto increasing widespread environmental and human exposure tothese chemicals, more attention should be paid to their ecologicalrisk because of their increasing discharge volume and property oflong-range transportation by its precursors. It is important toremain vigilant because there are uncertainties and knowledgegaps about the shorter chain homologues and that the long-termaccumulations of these products in the environment need to beassessed.

Acknowledgments

This research was supported by the National Natural ScienceFoundation of China (Nos. 41376189 and 41276202), Science Foun-dation of Shanghai Municipal Government (No. 12ZR1434800),State Key Laboratory of Pollution Control and Resource ReuseFoundation (Tongji University) (No. PCRRY11016). Ralf Ebinghauswas supported by Chinese Academy of Science Visiting Professor-ships Program of 2013 (No. 2013T2Z0032). John P. Giesy was sup-ported by the program of 2012 ‘‘Great Level Foreign Experts’’(#GDW20123200120) funded by the State Administration of For-eign Experts Affairs, the P.R. China to Nanjing University and theEinstein Professor Program of the Chinese Academy of Sciences.He was also supported by the Canada Research Chair program, a

826 Z. Lu et al. / Chemosphere 119 (2015) 820–827

Visiting Distinguished Professorship in the Department of Biologyand Chemistry and State Key Laboratory in Marine Pollution, CityUniversity of Hong Kong.

Appendix A. Supplementary material

Supplementary data associated with this article can be found, inthe online version, at http://dx.doi.org/10.1016/j.chemosphere.2014.08.045.

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