Investigating the role of colloids on the distribution of bisphenol analogues in surface water from an ecological demonstration area, China

Investigating the role of colloids on the distribution of bisphenol analogues in surface water from an ecological demonstration area, China

Science of the Total Environment 673 (2019) 699–707 Contents lists available at ScienceDirect Science of the Total Environment journal homepage: www...

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Science of the Total Environment 673 (2019) 699–707

Contents lists available at ScienceDirect

Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv

Investigating the role of colloids on the distribution of bisphenol analogues in surface water from an ecological demonstration area, China Wei Si a,b, Yuanfei Cai c,d, Jianchao Liu c,⁎, Jie Shen c, Qing Chen e, Chen Chen e, Like Ning f a

Department of Hydrology and Water Resources, Hohai University, Nanjing, Jiangsu, China Business School of Hohai University, Nanjing 210098, China c Key Laboratory of Integrated Regulation and Resources Development, College of Environment, Hohai University, Nanjing 210098, China d Wanjiang University of Technology, Ma'anshan 243031, China e Suzhou Litree Ultra-Filtration Membrane Technology Co. Ltd., China f Key Laboratory of Water Cycle and Related Land Surface Processes, Institute of Geographic Sciences and Natural Resources Research, CAS, Beijing 100101, China b

H I G H L I G H T S

G R A P H I C A L

A B S T R A C T

• The role of colloids on the distribution of BPs in surface water was monitored. • BPs are mainly present in the truly dissolved phase of surface water. • BPA and BPS were the predominant pollutants. • The colloids contributed 4.5–29.5% to the total BPs concentration in water. • Colloids have a strong capacity to bind hydrophobic BPs.

a r t i c l e

i n f o

Article history: Received 28 December 2018 Received in revised form 9 April 2019 Accepted 10 April 2019 Available online 10 April 2019 Editor: Daniel Wunderlin Keywords: Bisphenol analogues Colloidal phase Distribution Environmental risk

⁎ Corresponding author. E-mail address: [email protected] (J. Liu).

https://doi.org/10.1016/j.scitotenv.2019.04.142 0048-9697/© 2019 Elsevier B.V. All rights reserved.

a b s t r a c t Owing to the widespread use of bisphenol analogues (BPs) as substitutes for bisphenol A (BPA), the presence of BPs in multiple environments is of increasing concern. However, there is a limited understanding of the effects of colloids on the distribution and risk assessment of BPs traditionally dissolved in surface water. In this study, seven BPs were investigated in both the truly dissolved (b5 kDa) and colloidal (5 kDa to 1 μm) phases with water, with mean concentrations in the range of 71.6–671 ng/L and 5.84–76.6 ng/L, respectively. BPA and bisphenol S (BPS) were the dominant BPs in both phases, but a clear positive correlation was found between the adsorption contribution proportions of colloids to BPs and their hydrophobicity (octanol-water partition coefficient). The colloids contributed 50.4% of bisphenol AF, 33.4% of tetrabromobisphenol A, 25.2% of bisphenol F, 10.9% of BPA and 9.50% of BPS in the traditionally dissolved phase (b1 μm), which suggests that colloids play an important role in regulating the transformation and transportation of BPs in aquatic environments. Based on BP concentrations in the truly dissolved phase, only moderate risk levels for BPs towards algae, daphnia and fish were posed, and no oestrogenic risk existed in the study area. © 2019 Elsevier B.V. All rights reserved.

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1. Introduction Due to the adverse health effects of bisphenol A (2,2-bis(4hydroxyphenyl)propane; BPA) on wildlife and humans, BPA has been removed from many products by manufacturers in North America, the European Union, Japan and China (Chen et al., 2016). Some alternative chemicals have been selected to meet market demands. For example, bisphenol analogues (BPs) with two hydroxyphenyl groups have already been used to produce polycarbonate plastics and epoxy resins (Jin and Zhu, 2016). However, BPs could be emitted into the environment by pathways similar to those seen with BPA and may have similar toxicological profiles. Recently, the presence of BPs in various environmental media, such as surface water, sediment and sewage sludge, was confirmed (Liu et al., 2017; Yamazaki et al., 2015). Some studies have reported that concentrations of bisphenol F (bis(4hydroxypheny)methane; BPF) were 2.85 μg/L and 1.30 μg/L in the Tamagawa River of Japan and the Han River of Korea, respectively, while bisphenol S (4,4′-sulfonyldiphenol; BPS) concentrations as high as 7.20 μg/L were found in the Adyar River in India (Yamazaki et al., 2015). In terms of BPs concentrations measured in the surface water of Taihu Lake from September 2013 to November 2016, the pollution levels of BPs increased obviously, with mean concentrations rising from 16 ng/L to 389 ng/L (Jin and Zhu, 2016; Wang et al., 2017a; Yan et al., 2017). Furthermore, while the contribution rates of BPA gradually decreased from 55% to 9.5%, BPF, BPS and bisphenol AF (BPAF) have increased recently, contributing to 76.4% (Liu et al., 2017). Available studies have reported that BPS and BPF also result in endocrine-disrupting effects, nerve toxicity and developmental toxicity (Rochester and Bolden, 2015). Most existing research has focused on the traditionally dissolved phase (b1.0 μm), and the concentrations of BPs in the truly dissolved (b1 nm) and colloidal (1 nm to 1.0 μm) phases have been rarely determined. In the aquatic environment, colloids are ubiquitous and have large specific surface areas and multiple adsorption sites. Previous studies have shown that colloids are significant sinks for pharmaceuticals and oestrogenic chemicals (J. Liu et al., 2018). Between 1% to 45% of these chemicals were associated with colloids in the surface water of the Yangtze River (Yan et al., 2015a), and their environmental behaviours, including degradation and bioavailability were regulated by colloids (Duan et al., 2013; Yan et al., 2015a; Kim et al., 2016). However, as data on the presence of other BPs in colloids of surface water were unavailable, further study on the distribution of BPs in aquatic environments is needed, considering the long-term fate and impact of BPs in the ecosystems. Taihu Lake is the third largest freshwater lake in China and is the main source of drinking water and aquatic products for the surrounding population. Beginning in 2013, BPs have been widely detected in the surface water and sediment of Taihu Lake (Jin and Zhu, 2016; Wang et al., 2017b). With increased industrialization and rapid population growth in the Taihu Lake basin areas, the lake has become a sink for many contaminants (Ji et al., 2018; Nkoom et al., 2018; L.Y. Cao et al., 2017; X. Cao et al., 2017). Thus, it is important to understand the environmental fate of BPs in the aquatic environment around the Taihu Lake and to systematically evaluate their environmental risk. We selected the Wujin National Ecological Demonstration Area of Jiangsu Province, one of the most economically developed regions, located on the northwestern coast of Taihu Lake, for study. We aimed to investigate the distribution of seven BPs in the colloidal and truly dissolved phases in the surface water. Such knowledge is essential to assess the environmental risk of BPs. 2. Materials and methods 2.1. Chemicals Standard substances for BPA, BPF, BPS, BPAF, bisphenol E (BPE), bisphenol Z (BPZ) and tetrabromobisphenol A (TBBPA) were obtained from J&K Chemical Ltd. (Shanghai, China). Methanol, acetone and

formic acid were purchased from Merck Corporation (Darmstadt, Germany). 2.2. Sample collection The study area and location of 38 sampling sites are shown in Fig. 1 and Table S1. Among the 38 sampling sites, five sites (S1–S5) were distributed along Taihu Lake, thirteen sites (S6–S18) were distributed in the rivers of the industrial and agricultural region, seven sites (S19– S25) were distributed in urban rivers, six sites (S26–S31) were along Gehu Lake, and seven sites (S32–S38) were distributed in the rivers of the agricultural region. In all sample sites, water samples (2 L) were collected in triplicate in August 2018, according to the technical specifications of surface water monitoring (SEPAC, 2003). After transport to the laboratory in a cooler with dry ice, water samples were filtered through 1.0 μm-glass fibre filters and subdivided into the traditionally dissolved phase and particulate fractions. The traditionally dissolved phase was further divided into colloidal phase and truly dissolved fractions using a cross-flow cell and a 5 kDa-polyether sulfone membrane (Yan et al., 2016). At the end of isolation, the colloidal phase and truly dissolved phase were prepared for extraction. 2.3. Sample extraction and instrument analysis BPs in the truly dissolved phase and colloidal phase were extracted and analysed based on the previous study (Yang et al., 2014). Briefly, the extraction of BPs from the truly dissolved phase and colloidal phase was performed by a solid-phase extraction (SPE) system using HLB cartridges preconditioned with 6 mL methanol and 6 mL formic acid solution with pH = 3. The pH values of both phases were preacidified to 5 by 1 mol/L formic acid. Water samples were passed through the HLB cartridges at a flow rate of 5 mL/min. Subsequently, the cartridges were rinsed with 6 mL of methanol/water (30:70, v/v) and 6 mL of water to remove interferences. The analytes were eluted using 9 mL of methanol with 2% ammonia. After evaporating to dryness under a gentle stream of nitrogen, the extracts were reconstituted with 1 mL methanol. The BPs were identified and quantified using LC-MS/MS (LC: Waters Acquity ultra-high-performance liquid chromatograph, MS: Waters Acquity Xevo TQ triple quadrupole mass spectrometer) with multiple reaction monitoring (MRM). The column temperature was 40 °C with a flow rate of 0.3 mL/min, and the injection volume was 5 μL. Further details on the analytical procedures can be found in the Supplementary information (SI), Tables S2 and S3. 2.4. Quality assurance and quality control A matrix-matched external standard method was used to quantify the concentrations of BPs. The sensitivity of the method was evaluated by the limit of detection (LOD) and limit of quantitation (LOQ). The LODs and LOQs of the BPs in water were 0.16–3.30 ng/L and 0.53–11.10 ng/L, respectively (Table S4). The calibration curves showed good linearity in a concentration range of 1–200 ng/mL (R2 N 0.998). Recoveries were in the range of 72.1–113.2% for the water samples, and the relative standard deviations were b20% (Table S4). Detailed information is given in the SI. 2.5. Parameter measurement and statistical analysis The eco-toxicity of the selected BPs in the truly dissolved phase of surface water was assessed using the risk quotient (RQ) method on algae, invertebrates and fish (Backhaus and Karlsson, 2014). The oestrogen equivalent concentrations (EEQ) were calculated based on measured concentrations of BPs with a known oestrogen equivalency factor (EEF) (Y.Y. Liu et al., 2018). Detailed calculation methods are described in the SI. The mean, median and concentration ranges were used

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Fig. 1. Study area and sampling sites of surface water from the Wujin National Ecological Demonstration Area.

to describe the results. SigmaPlot 12.5 and SPSS Statistics 20 were used for statistical analysis and graphics. 3. Results and discussion 3.1. Truly dissolved phase of water The BP concentration range, mean and median in surface water from the Wujin district are shown in Table 1, and the detailed data are presented in Fig. 2. Five of the seven BPs were detected in the study area, with detection frequencies of 16.0%–100%, whereas BPE and BPZ were never detected. Among these detected compounds, BPA, BPS and BPAF were the most widely detected (100%), followed

by BPF (95.0%) and TBBPA (16.0%). The total concentrations of detected BPs (ΣBPs) in the truly dissolved phase ranged from 71.6 to 671 ng/L (mean: 260 ng/L). BPA was the dominant BP, with a mean concentration of 196 ng/L, followed by BPS (56.1 ng/L), BPF (5.82 ng/L), TBBPA (2.55 ng/L) and BPAF (1.43 ng/L). Spatially, the compositional profiles of BPs in the truly dissolved phase from Taihu Lake (except S5), Gehu Lake, the urban region and the agricultural region were generally similar to each other, with BPA as the predominant BP (mean contribution of 81.8%), followed by BPS (mean 12.5%) and BPF (4.70%). However, BPS, with mean concentrations ranging from 6.56 ng/L to 293 ng/L, made a higher contribution (48.3%) to the ΣBPs in the truly dissolved phase from the industrial and agricultural region (except S13, S14 and S15) than in other

Table 1 Concentrations of detected BPs in the truly dissolved phase and colloidal phase samples. Compounds

BPA BPS BPF BPAF TBBPA a

Truly dissolved phase (ng/L)

Colloidal phase (ng/L)

Mean

Median

Range

DFa (%)

Mean

Median

Range

DF (%)

196 56.1 5.82 1.43 2.55

140 29.7 3.44 0.97 2.20

47.8–633 6.56–293 0.48–36.7 0.05–8.21 0.30–6.10

100 100 95.0 100 16.0

21.2 4.46 1.27 1.31 0.94

14.9 3.33 0.80 0.90 0.92

1.08–65.6 0.08–25.7 0.05–5.57 0.07–9.49 0.40–1.53

100 100 95.0 100 16.0

DF: detection frequency.

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Fig. 2. Concentrations of BPs and their percentage composition in the truly dissolved phase of surface water.

regions, where BPA comprised 49.4% of the ΣBPs. Similar results were also found in the tributaries of Taihu Lake located at Changzhou, where BPS was the highest BPA alternative, contributing 40.3% of total BPs (Liu et al., 2017). The pollution levels of BPS in the Taihu Lake basin were higher than those reported for the Pearl

River Delta, however, where BPF was the dominant BP (mean contribution of 78.8%), with levels one to two orders of magnitude higher than BPA (Yamazaki et al., 2015). The above results show a clear difference in the use of BPs in different regions and indicate that BPS has been widely used and/or manufactured in the Taihu Lake basin.

Fig. 3. Score plot of principal component analysis of BPs in the truly dissolved phase of surface water.

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Principal component analysis (PCA) was employed for BPs in the truly dissolved phase of surface water to identify the sources of the detected BPs. As shown in Fig. 3, 99.5% of the total variation in the dataset can be explained by PC1 (85.5%) and PC2 (13.7%). In all datasets, at least three clusters could be identified in the score plot of PCA: (1) S7, S8 and S16–S18, which had a high positive correlation (R N 0.967) and similar contamination profiles, manifesting the dominance of BPS; (2) S5 and S9–S11, which had the same pollution levels of BPA and BPS; and (3) all other sampling sites (S1–S4, S6, S12–S15 and S19–S38), which had higher loading values of PC1 in the components plot and featured BPA. Most of the surface water from Taihu Lake (except S5), Gehu Lake and the survey rivers clustered in the form of a short arc, suggesting that the BPs profiles in the surface water in these regions are similar, and a similar source of BPs in the surface water exists. S5, located in the estuarine area of Taihu Lake, has similar congener profiles with the inflowing river (S9–S11). The above results suggest that tributaries of Taihu Lake and Gehu Lake contribute more to the pollution levels of BPs in both lakes. 3.2. Colloidal phase of water Aquatic colloids, defined as particles ranging from 1 nm to 1 μm, are ubiquitous in natural aquatic systems and could regulate the fate and behaviour of contaminants. The concentrations of BPs in the colloidal phase samples are shown in Fig. 4. The results illustrate that the average concentrations of ΣBPs in the colloids ranged from 5.84 ng/L to 76.6 ng/L, which are clearly lower than those in the truly dissolved phase; this also indicates the high biological availability of BPs. As with the truly dissolved phases, high BPs concentrations were found in the colloids at S3 of Taihu Lake (76.6 ng/L) and S27 of Gehu Lake (64.3 ng/L). The monomer distribution of BPs in colloids was also very

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similar to that of the truly dissolved phase, and BPA was still the dominant BP, followed by BPS. PCA was performed to determine the potential source of BPs in colloids (Fig. S1). The PCA result of colloids showed that component 1 and component 2 contributed to 85.7% and 10.5% of the total variance, respectively. All samples (except S20 and S38) from colloids were clustered in the first quadrant in the form of an arc, manifesting the dominance of BPA and BPS. Sampling site S38 had similar levels of detected BPs. To evaluate the potential importance of the colloids in the traditionally dissolved phase, the adsorption contribution proportions of colloids to BPs were calculated. Overall, the colloids contributed 4.50%–29.5% to the total BPs concentration in the traditionally dissolved phase (Fig. S2). These results were similar to previous studies, where 4%–45% of pharmaceuticals are associated with colloids, and the sorption capacities are clearly higher than suspended particulate matter (Duan et al., 2013). In terms of each BP, the mean contribution proportions of the colloids were 50.4% of BPAF, 33.4% of TBBPA, 25.2% of BPF, 10.9% of BPA and 9.50% of BPS (Fig. 5A), indicating that colloids are a potential reservoir of BPAF, TBBPA and BPF in aquatic systems. Until now, no reference data on the BPs distribution in colloids have been reported, and thus our results were not compared with other areas. The presence of 42 emerging contaminants (ECs) in the traditionally dissolved phase was investigated in the Yangtze River Estuary, where it was found that colloids act as a significant sink for ECs in aquatic environments, with 0.73%–42.29% of ECs being colloid-associated in the traditionally dissolved phase and a BPA contribution of colloids around 11% (Yan et al., 2015a), in agreement with our results. Based on reported logKow values of BPs, the relationships between logKow and contribution rates were evaluated (Fig. 5B), and a significant positive relationship was found in the present study. These results suggest that the association of BPs with colloids is due to hydrophobic interactions. Because of the

Fig. 4. Concentrations of BPs and their percentage composition in the colloids of surface water.

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Fig. 5. Contribution rates of colloids to the total BPs in the traditionally dissolved phase (A) and the relationships between logKow and contribution rates of colloids (B).

relatively low logKow value of BPS (1.65), although BPS was detected widely in the truly dissolved phase of all sampling sites, it had low contribution rates in the colloidal phase. However, a moderately high logKow leads to easy binding with colloids, causing relatively higher concentrations of BPAF and TBBPA in the colloids, as also found in previous work (Liu et al., 2016). These results indicate that colloids play an important part in absorbing the BPs and could further influence the transformation, transportation and bioavailability of BPs in aquatic systems (Yan et al., 2015b; Zhang et al., 2015), which should be taken into account for the development of eco-environmental risk assessments and the establishment of water quality criteria of contaminants in natural waters. 3.3. Comparison between sites and with other studies based on the traditionally dissolved phase Information on the occurrence of BPs in the truly dissolved phase of surface water was not found; thus, we hereby compared BPs concentrations in the traditionally dissolved phase, including the truly dissolved phase and colloidal phase, with those from all over the world. The incidence of BPs in the traditionally dissolved phase is shown in Fig. S3. The total concentrations of detected BPs (ΣBPs) in the traditionally dissolved phase ranged from 98.8 to 726 ng/L (mean concentration: 288 ng/L). BPA was the dominant BP, with a mean concentration of

217 ng/L, followed by BPS (60.5 ng/L), BPF (7.13 ng/L), TBBPA (3.49 ng/L) and BPAF (2.70 ng/L). Spatially, the concentrations of BPs in the industrial/agricultural region (S13–15), Taihu Lake (S1–S5) and Gehu Lake (S26–S31) showed higher pollution levels, at mean concentrations of 593, 393 and 288 ng/L, respectively. Our survey found several plastic plants, garment factories and industrial parks located near S13, S14 and S15. In these regions, BPA was the highest congener (contribution of 88%–96%), indicating that BPA may be still used or manufactured in these processing plants. These results also suggest that some parts of the two lakes have become a sink for BPs, especially for Taihu Lake. At present, only a few studies have reported the concentrations of BPs in the traditionally dissolved phase of surface water from all over the world (Table 2). Compared to the data of BPs concentrations in Taihu Lake measured in September 2013, the mean concentrations of BPs increased significantly in 2016 and 2018, with the concentration of BPA rising from 8.5 ng/L to 217 ng/L, that of BPS from 6.0 ng/L to 120 ng/L, that of BPF from 0.83 ng/L to 140 ng/L and that of BPAF from 0.28 ng/L to 114 ng/L. The total concentrations of BPs, including BPA, BPF and BPS in the Taihu Lake basin, were similar to those from the Pearl River Delta (ranging from 107 ng/L to 987 ng/L), but clearly higher than those from the Liaohe River basin. As the main source of drinking water and aquatic products for the surrounding residents, the increased pollution of BPs should be paid more attention. In terms of monomers, the mean concentration of BPA (217 ng/L) in the surface water from the Wujin district was higher than those reported in Table 2 (except in several rivers of India). The mean concentration of BPS (60.5 ng/L) in the surface water of the Wujin district was much higher than those from Taihu Lake detected in September 2013, May 2015 and November 2016; Luoma Lake, Liaohe River and Hunhe River in China; and three rivers and Tokyo Bay in Japan; it was much lower than those from the Taihu Lake detected in April 2016, the Pearl River in China, and the Adyar River and Buckingham Canal in India. For BPF, the mean concentration was 7.13 ng/L, which was lower than those from Taihu Lake detected in 2016, and 2 orders of magnitude lower than those detected in the Pearl River in China, Han River in Korea and Tamagawa River in Japan. BPAF levels were much lower than that in the Taihu Lake in November 2016, but similar to those in other surface waters, listed in Table 2. The above results present a clear difference in the use and discharge of BPs in different regions, but generally, BPA alternatives are used and/or manufactured in these regions, and BPS and BPF were the predominant congeners.

3.4. Assessment of potential risk in study area 3.4.1. Risk quotient In view of the high biological availability and wide detection of BPs in the truly dissolved phase of surface water, the exposure of aquatic organisms to BPs may cause some adverse effects on the ecosystem. To demonstrate their potential impact, a screening level risk assessment for the detected compounds was performed based on toxicity data of algae, daphnids and fish (Table S5), along with the environmental concentrations of BPs in the truly dissolved phase. The toxicity data for the most sensitive aquatic organisms for PNEC calculation are provided in Table 3. The RQ values of each detected BP were calculated and are shown in Table S6. According to the common risk ranking criteria (i.e., low risk 0.01 b RQ b 0.1; medium risk 0.1 b RQ b 1; high risk 1 b RQ) (Liu et al., 2015), a large majority of RQ values for detected BPs were below 0.1, indicating little risk to the relevant sensitive aquatic organisms posed by BPs in the study area. The RQ values of BPA exceeded 0.1 for all sensitive aquatic organisms only in Taihu Lake (S2 and S3), the industrial area (S13, S14 and S15) and Gehu Lake (S26 and S27), and the RQ values of TBBPA were N0.1 for daphnids and fish at sampling site S35, suggesting medium risk to these aquatic organisms. According to previous studies, the adverse impacts of BPA on the growth status of Selenastrum capricornutum, the motion activity of Daphnia magna and

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Table 2 The mean (median) and minimum-maximum concentrations of BPs in other sampling locations. Sampling locations

Time

Concentrations (ng/L) in traditionally dissolved phase

Wujin district

2018a (08)

Taihu Lake

2013 (09)

Taihu Lake

2015 (05)

Taihu Lake

2015 (11)

Taihu Lake

2016 (04)

Taihu Lake

2016 (11)

Luoma Lake

2016 (04)

Liaohe River

2013 (09)

Hunhe River

2013 (09)

Pearl River

2013 (07)–2014 (03)

West River 20 source water China

2017 (11)

Several Rivers, Bay (Japan)

2013 (07)–2014 (03)

Several Rivers (Korea) Several Rivers, Lake (India) a b

References

BPA

BPS

BPF

BPAF

TBBPA

217 (157) 73.5–678 8.5 (7.9) 4.2–14 9.7 (7.3) 3.9–33.2 92.6 (53.2) 28–565 97 28–560 25.7 (23.8) 19.4–68.5 86 49–110 47 (29) 5.9–141 40 (42) 4.4–107 73 (73) ND–98 43 (43) ND–43 12.8 (10.5) ND–34.9 104 ND–431 105.7 1.0–272 551 ND–1950

60.5(32.1) 7.80–319 6.0 (2.0) 0.28–67 2.6 (0.94) 0.32–27.3

7.13 (4.61) 1.14–40.1 0.83 (0.5) ND–5.6 1.24 (1.1) 0.5–3.28

2.70 (2.05) 0.30–17.7 0.28 (0.2) 0.13–1.1 0.27 (0.1) 0.06–2

3.49 (3.00) 1.71–7.12

(Jin and Zhu, 2016) (Wang et al., 2017a) 26.2 (11.8) 11.8–40.7

120 4.5–1600 15.9 (6.6) 41–157 21 ND–94 14 (8.9) 0.22–52 11 (8.4) 0.61–46 135 (135) ND–135 ND 1.1 (0.4) ND–5.2 5.3 ND–15 41 ND–42 2174 ND–7200

140 ND–1600 78 (30) 25.6–723 6.8 3.5–14 NDb ND 773 (757) 448–1110 64 (64) ND–105 2.2 (ND) ND–12.6 638 ND–2850 633 ND–1300 91.5 ND–289

This study

8.2 0.7–23 114 (111) 110–140 17 12–84 1.9 (1.0) 0.5–9.6 2.4 (0.94) 0.61–11 ND

(Liu et al., 2016) (Yan et al., 2017) (Liu et al., 2017) (Yan et al., 2017) (Jin and Zhu, 2016) (Jin and Zhu, 2016) (Yamazaki et al., 2015)

ND 3.0 (0.1) ND–10.8 ND

(Zhang et al., 2019) (Yamazaki et al., 2015)

ND ND

Year (Month). ND: not detected.

the body pigmentation and hatching success of fish embryos might exist (Staples et al., 1998; Tišler et al., 2016). In addition, BPs occur in the surface water as multi-component mixtures. Due to the similar molecular structure of BPs, they have similar action patterns (Ullah et al., 2018). The total mixture RQ of detected BPs was calculated to characterize the worst-case scenario, and the results are shown in Fig. 6A. For the surface water of the study area, the RQTotal ranged from 0.0211 to 0.2617 for algae, from 0.0144 to 0.3965 for daphnia and from 0.0249 to 0.4099 for fish, respectively. Generally, fish are the most sensitive species, followed by daphnia and algae. In particular, mean contribution values of all compounds for the RQTotal declined according to the following order: BPA (82.7%) N TBBPA (6.4%) N BPS (5.0%) N BPF (4.4%) N BPAF (1.5%), which was similar with that in Taihu Lake (Yan et al., 2017). From the perspective of spatial

distribution, the RQTotal of BPs gradually increased in a wave from the western agricultural regions to the eastern industrial regions, which indicates that the eco-toxicity risk is directly related to the economic structure. However, this evaluation focused on the classic mixture concept of Concentration Addition, which may underestimate or overestimate the risk of BPs to aquatic organisms due to the lack of data on the joint ecotoxicity of such chemical cocktails. 3.4.2. Estrogenic activity assessment Many ecotoxicological studies have reported that BPs revealed oestrogenic activity by binding to the oestrogen receptors on aquatic organisms (L.Y. Cao et al., 2017; X. Cao et al., 2017; Moreman et al., 2017; Song et al., 2014). To estimate the oestrogenic activity of BPs, the 17βoestradiol equivalency quantity (E2EQ) approach was used according

Table 3 Aquatic toxicity data of the BPs to the most sensitive aquatic species. Compound

Non-target organism

Test endpoint

Toxicity data (mg/L)

PNEC (ng/L)

Reference

EEF Ref. (Ruan et al., 2015)

BPA

Algae Daphnias Fish Algae Daphnias Fish Algae Daphnias Fish Algae Daphnias Fish Algae Daphnias Fish

72 h-EC50 48 h-EC50 48 h-EC50 96 h-EC50 48 h-EC50 72 hpf-EC50 72 h-IC50 21 d-NOEC 48 h-EC50 72 h-IC50 21 d-NOEC 72 hpf-EC50 EC50 EC50 EC50

2.2 (Growth) 3.9 (Immobility) 3.6 (Pigmentation) 6.9 55 (Immobility) 155 (Mortality) 22.1 (Growth) 0.84 (Reproduction) 1.1 (Pigmentation) 3.0 (Growth) 0.23 (Reproduction) 0.92 (Mortality) 0.198 0.023 0.023

2200 3900 3600 6900 55,000 155,000 22,100 8400 1100 3000 2300 920 198 23 23

(Debenest et al., 2010) (Staples et al., 1998) (Tišler et al., 2016) (US EPA, 2011)a (Chen et al., 2002) (Moreman et al., 2017) (Tišler et al., 2016) (Tišler et al., 2016) (Tišler et al., 2016) (Tišler et al., 2016) (Tišler et al., 2016) (Moreman et al., 2017) (US EPA, 2011) (US EPA, 2011) (US EPA, 2011)

1.07 × 10−4

BPS

BPF

BPAF

TBBPA

a

The toxicity data was calculated from the ecological structure activity relationships (ECOSAR) model.

1.06 × 10−6

1.08 × 10−4

7.23 × 10−4

8.91 × 10−6

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treatment processes was not incorporated into the current estimations. Third, combined action of some of the contaminants was not taken into account in the estimation, which would add uncertainty in the estimations. 4. Conclusions In this study, the presence and distribution of seven BPs in the traditionally dissolved phase of surface water from an ecological demonstration area were investigated. The results showed that BPA, BPS, BPAF and BPF were widespread (detection rates N95%) and increased yearly in the Taihu Lake basin. Water samples from the industrial region, Taihu Lake and Gehu Lake presented comparatively higher total concentrations of BPs than did other river networks. BPA and BPS were the major contaminants in the truly dissolved phase, with mean concentrations of 196 ng/L and 56.1 ng/L, respectively. We first estimated the adsorption potential of the colloidal phase for detected BPs. The adsorption contribution proportions of colloid to BPAF, TBBPA, BPF, BPA and BPS were 50.4%, 33.4%, 25.2%, 10.9% and 9.50%, respectively, which had a clear positive correlation with logKow. Colloids, as the main portion of the traditionally dissolved phase, showed significant binding capacity for hydrophobic pollutants, and therefore, the impacts of colloids on the environmental fate and risk assessment of BPs should be fully considered. Although eco-toxicity and oestrogenic risk presented low or medium levels based on current survey data, increasing detection frequencies and concentrations of BPs have been reported in the abiotic environment in Taihu Lake basin. Moreover, some BPs have approximated or surpassed BPA in concentrations in some environmental samples, likely reflecting a shift from BPA to other substitutes in some applications. However, current scientific knowledge is apparently insufficient to elucidate source, fate and effects, and human exposure assessments of BPs, these efforts are important to regulate the environmental BPA leakage at the macro-scale. Acknowledgments Fig. 6. Total RQ of BPs for algae, daphnids and fish (A) and E2EQ of BPs (B) in the truly dissolved phase of surface water.

to the EEF (Table 3), where E2EQ N 1.0 ng E2/L indicates that chemicals may elicit negative effects on the endocrine systems of aquatic organisms. The sums of E2EQ (E2EQTotal) for BPs at each sampling site were calculated and are presented in Fig. 6B. The results show that E2EQTotal in water ranged from 0.007 to 0.074 ng E2/L, and BPA was the predominant contributor to oestrogenic activity (mean contribution of 90.4%), followed by BPAF (5.0%), BPF (4.2%) and BPS (0.4%). As a whole, the E2EQTotal values of BPs were less than the threshold of 1.0 ng E2/L, indicating no oestrogenic risk observed from these BPs in the study area. The results are comparable to a prior study of Taihu Lake, where the E2EQTotal of BPs was 0.094 ng E2/L, and no oestrogenic effect from the detected BPs was found on local residents' health through water ingestion (Liu et al., 2017). According to the water intake of the Chinese population, the daily intake EEQ (DIEEQ) of BPs was estimated for children (under 3 years old) and adults (male and female), and the results are presented in Table S7 (Liu et al., 2017). The mean EEQ levels for children and adults ranged from 6.4 × 10−4 to 1.9 × 10−3 ng/kg/d and from 6.7 × 10−4 to 7.2 × 10−4, respectively, which were much lower than the acceptable daily intake of E2 for humans of 50 ng/kg/d (JECFA, 1999) and similar to other published EEQ levels of BPs in the Taihu Lake basin, China (Liu et al., 2017; Yan et al., 2017). However, uncertainly analysis is a common component of risk assessment. First, the current calculation only considers water ingestion intake and does not account for BPs exposure from other types of foods and non-dietary routes, which may lead to underestimation of the risks associated with BPs. Second, raw water is usually treated by drinking water treatment plants, which can influence contaminant levels. In the present study, reduction of

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