Distribution characteristics and environmental risk assessment of bisphenol analogues in the lower reaches of the Yangtze River†

Wanyu Li‡ ^ab, Wenxuan Ma‡^c, Jiajun Chang^ab, Yao Xiao^ab, Rui Wang^ab, Zhiliang Zhu^ab, Daqiang Yin^ab, Yue Li^d and Yanling Qiu*^ab
aKey Laboratory of Yangtze River Water Environment, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China. E-mail: ylqiu@tongji.edu.cn; 14lili@tongji.edu.cn
^bShanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China
^cQingdao Ecological Environment Bureau Jiaozhou Branch, Qingdao 266300, China
^dThe Institute of Fishery Machinery and Instruments of the Chinese Academy of Fishery Sciences, Shanghai 200092, China

First published on 25th June 2025

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Environmental significance Bisphenols (BPs) are widely distributed in the environment due to their chemical stability and extensive use. In China, bisphenol (BP) concentrations in water bodies vary significantly. Recent studies showed that BPA remains the dominant BP in lower Yangtze River basin surface water, but analogs like BPS, BPF, and BPAF are becoming more common. The growing environmental concern regarding BP contamination in aquatic systems underscores the urgent need for targeted research on BP in the lower Yangtze River. This study conducted a three-year investigation into the concentrations and risks of bisphenols (BPs) in the lower reaches of the Yangtze River, and explored their potential pollution sources. The findings are intended to offer a robust scientific foundation for the prevention, control, and regulation of emerging pollutants, exemplified by BPs, in the surface waters of this region.

1 Introduction

Bisphenol (BP) compounds, a class of organic compounds containing two phenolic hydroxyl groups, are widely used in industrial production as additives or raw materials due to their excellent solubility, high refractive index, and transparency. Among them, bisphenol A (BPA) is the most extensively utilized, with Asian countries—particularly China, South Korea, and Japan—accounting for the majority of global BPA production.¹ As a critical plasticizer, BPA is incorporated into polycarbonate plastics, thermal paper inks, cosmetics, and food packaging materials. However, BPA exhibits strong estrogenic activity and is recognized as a typical endocrine-disrupting chemical (EDC).² Human exposure to BPA primarily occurs through leaching from food and beverage containers,³ with studies demonstrating adverse health effects such as necrosis, apoptosis, oxidative stress, and genotoxicity in human peripheral blood mononuclear cells, as well as antagonistic interactions with thyroid receptors.⁴ To mitigate risks, the European Union banned BPA in plastic baby bottles in 2011.⁵ Many countries have since adopted BPA analogues—including bisphenol S (BPS), bisphenol F (BPF), and bisphenol AF (BPAF)—as substitutes in plastics and other materials.⁶ Key physicochemical properties of common BPs are summarized in Table S1.† However, emerging evidence indicates that these analogues have similar toxicological profiles to BPA, leading to their classification as emerging pollutants of concern.⁷

Bisphenols (BPs) are widely distributed in the environment due to their chemical stability and extensive use. Research over the past two decades has shown their prevalence in aquatic systems. For example, in São Paulo, Brazil, surface water had the highest BPA concentrations (2–13016 ng L⁻¹), with elevated levels near industrial and densely populated areas.⁸ In Slovenia and Croatia, wastewater treatment plants reported increasing trends of BPA, BPF, and BPS, along with the emergence of new analogues BPB and BPE.⁹ In Czech rivers, the average detection frequency of bisphenol (BP) analogues was 39%. Bisphenol AF (BPAF) showed the highest maximum detected concentration (91 ng L⁻¹), while bisphenol A (BPA) exhibited the highest mean detected concentration (119 ng L⁻¹), with an extreme maximum concentration reaching 800 ng L⁻¹. BPAF followed, with a mean concentration of 91 ng L⁻¹ and a maximum of 205 ng L⁻¹. These results indicate that BPA and BPAF are extensively utilized in the local area.¹⁰ The study by Santhi et al. revealed that the concentrations of BPA in tap water and drinking water were 11.3 ng L⁻¹ and 3.5–59.8 ng L⁻¹, respectively, demonstrating that BPA can migrate from plastic bottles and pipelines into drinking water, posing potential risks to human health.¹¹ A two-year monitoring program of BPs in Indian river water reported a maximum BPA concentration of 1480 ng L⁻¹.¹² In India, a study found widespread detection of BPA, BPS, and BPF in surface waters across 12 states and Delhi, with BPA being the dominant component.¹²

In China, bisphenol (BP) concentrations in water bodies vary significantly. Riverine BP levels ranged from 40–180 ng L⁻¹, while lake systems showed levels of 4–270 ng L⁻¹.¹³ A study analyzing BP levels in 20 drinking water sources across China in 2017 identified BPA as the predominant compound (average: 12.8 ng L⁻¹), followed by BPF and BPAF.¹⁴ In the Pearl River, BPA and BPS were dominant, accounting for 68% of the total BPs.¹⁵ The Yellow River's Lanzhou section had mean BP concentrations of 88 ng L⁻¹ (wet season) and 61.2 ng L⁻¹ (dry season) in water.¹² A study on BPs in the Yellow River during dry seasons revealed elevated levels of BPA and BPAF, exceeding 100 ng L⁻¹.¹⁶ Lake Taihu's BPA levels surged from 8.5 ng L⁻¹ to 97 ng L⁻¹ during 2013–2016.¹⁷ The highest average BPA level in 2016 was observed in April, followed by a sharp decline in November. BPF and BPS exhibited trends similar to BPA, while BPAF showed an inverse pattern (8.2 ng L⁻¹ in April vs. 114 ng L⁻¹ in November).¹⁸ The Nanjing section of the Yangtze River reported average BP concentrations of 393.8 ng L⁻¹ and 300 ng L⁻¹ in two studies, with BPA making up over 80% of the total.^19,20 Zhang et al. analyzed BPs in the Qinhuai River, a major tributary of the lower Yangtze, revealing significantly higher ΣBPs concentrations in the pre-flood period (20.3–472 ng L⁻¹, average: 146 ng L⁻¹) compared to the post-flood period (14.1–105 ng L⁻¹, average: 35.9 ng L⁻¹). ¹³ Recent studies showed that BPA remains the dominant BP in lower Yangtze River basin surface water, but analogs like BPS, BPF, and BPAF are becoming more common. In Lake Taihu, certain BPA analogues now exceeded BPA concentrations.¹⁸ While studies on BPs in the mainstream Yangtze River are limited, extensive investigations in Lake Taihu-located within the Yangtze River basin-provide insights into BP contamination trends in downstream areas. A series of studies on Lake Taihu demonstrate that its BP levels are notably higher compared to other domestic basins, with BPA concentrations exhibiting a yearly increasing trend,^21,22 accompanied by increasing levels of BPA analogs.^21,23,24 Research on the Nanjing section of the Yangtze River further shows that both average and maximum BP concentrations in this region²⁰ substantially exceed those reported for the Pearl River¹⁴ and the Yellow River,¹⁶ while BPS levels are markedly higher than those observed in the Wuhan section of the Yangtze River.²⁵ These findings highlight the emerging environmental concern of BP contamination in aquatic systems and the need for targeted BP research in the lower Yangtze basin.

The lower Yangtze River, spanning 850 km through Jiangxi, Anhui, Jiangsu, and Shanghai, is a vital economic hub with dense industrialization and urbanization. Since the 1970s, rapid development has led to severe aquatic degradation, making it a priority protected catchment area in 2020.²⁶ China has focused on ecological management of the Yangtze River since the 1980s, passing environmental laws and implementing measures with notable success. However, environmental risks remain, especially concerning emerging pollutants such as bisphenols. This study conducted a three-year investigation into the concentrations and risks of bisphenols (BPs) in the lower reaches of the Yangtze River, and explored their potential pollution sources. The findings are intended to offer a robust scientific foundation for the prevention, control, and regulation of emerging pollutants, exemplified by BPs, in the surface waters of this region.

2 Materials and methods

2.1 Sample collection

Water samples were collected in September 2022, September 2023, and September 2024 from representative sections of the lower reaches of the Yangtze River, including cities such as Shanghai, Nantong, Changshu, Zhangjiagang, Changzhou, Taizhou, Yangzhou, Zhenjiang, Nanjing, Ma'anshan, Wuhu, Tongling, Anqing, and Jiujiang. The specific sampling locations are illustrated in Fig. S1–S3.† To minimize plastic contamination, a stainless-steel sampler was employed, and 1 L amber glass bottles were used to reduce photodegradation of target analytes. Prior to sampling, all equipment was rinsed three times with site water. Field blanks (ultrapure water in pre-cleaned bottles) were prepared to monitor background contamination. Collected samples were stored at 4 °C in darkness and processed promptly.

2.2 Sample analysis

2.3 Quality control and assurance

The limit of detection (LOD) for target BPs was defined as the mean process-blank concentration plus three standard deviations (SDs), while the limit of quantification (LOQ) was set as the mean blank concentration plus ten SDs. If the calculated LOQ was lower than the lowest calibration standard, the latter was used as the LOQ. The LLOQ was determined as the lowest standard curve point (0.5 μg L⁻¹). The chromatograms of LLOQ, pure solvent and process blank samples are shown in Fig. S4.†

For each batch of samples, three blanks were also analyzed simultaneously. Surrogate standards (¹³C₁₂-BPF and ¹³C₁₂-BPS) were spiked into all samples to monitor recovery rates (Table S2†). Method performance metrics, including LODs (0.500–4.00 ng L⁻¹) and recoveries (70–120% for most analytes), are summarized in Table S3.† Notably, BPAP exhibited lower recovery, while BPF and BPS showed higher recoveries. Additionally, we also calculated the matrix effect according to formula (2.1)

	(2.1)

Among them, ME_IS: matrix effect factor with internal standard correction; B: peak area of the isotopic marker in the matrix sample; B_IS: peak area of the internal standard in the matrix-spiked group; A: peak area of the isotopic marker in the pure solvent (ultrapure water) standard; A_IS: peak area of the internal standard in the pure solvent standard.

Note: ME_IS <25% is considered an insignificant matrix effect, and ME_IS >50% is a strong matrix effect. A positive value indicates signal enhancement, while a negative value indicates ion suppression.

Based on these criteria, the calculated ME_IS values were −3.29% for ¹³C₁₂-BPF and 12.98% for ¹³C₁₂-BPS, indicating negligible matrix effects in this study.^30,31

2.4 Ecological risk assessment

Predicted no-effect concentrations (PNECs) for BPs were derived using assessment factors (AFs) per EU technical guidelines,³² with toxicity data sourced from the US EPA ECOTOX database. Chronic toxicity endpoints for zebrafish (Danio rerio) were prioritized.

The Risk Quotient (RQ) method was used to evaluate the ecological risk of BPs in the lower reaches of the Yangtze River, and the specific formula was as follows:

RQ = MEC/PNEC	(2.2)

In eqn (2.2), MEC is the concentration of the pollutant in the environmental medium that is actually measured.

According to the RQ value obtained by the risk quotient method, the ecological risk of water bodies can be divided into four categories: ① no risk (RQ < 0.01); ② low risk (0.01 ≤ RQ < 0.1); ③ moderate risk (0.1 ≤ RQ < 1); ④ high risk (RQ > 1).³³

2.5 Health risk assessment

According to eqn (2.3), the estimated daily intake (EDI) of three types of new pollutants in drinking water was calculated separately, and the units were ng·(kg d)⁻¹.

EDI = (C × IR × AP)/BW	(2.3)

In eqn (2.3), C is the concentration of each new contaminant in water (ng L⁻¹), IR is the daily intake of drinking water (L per day), AP is the percentage of gastrointestinal absorption (set to 100% for drinking water), and BW is body weight (kg). In this study, the average concentration of the target contaminant was used to assess the average exposure level, taking into account the effects of age and sex differences on body weight and drinking water intake,^34–36 and the relevant population exposure parameters (Table S4†) were compared to those in the Chinese Population Exposure Parameter Handbook.

2.6 Data processing

3 Results and discussion

3.1 Concentrations of BPs

The detection status of BPs in the lower reaches of Yangtze River during September 2022, 2023, and 2024 is presented in Table 3. Among the nine target BPs, the detection rates of BPA and BPE were both 100% across all three years, while the detection rates of BPS, BPF, and BPAP were all above 50%. BPZ and BPAF were detected only in 2024, at a relatively low frequency. The detection of BPP and BPB was observed in the years 2022 and 2024. Notably, BPP exhibited relatively low detection rates in both years. In contrast, BPB demonstrated a substantial increase in detection frequency in 2024. The total concentrations of the nine BPs (∑₉BPs) in the lower reaches of the Yangtze River during September 2022, 2023, and 2024 were 28.6–165 ng L⁻¹ (mean: 67.2 ng L⁻¹; median: 59.3 ng L⁻¹), 8.30–87.9 ng L⁻¹ (mean: 28.0 ng L⁻¹; median: 24.2 ng L⁻¹) and 35.2–62.8 ng L⁻¹ (mean: 46.8 ng L⁻¹; median: 45.7 ng L⁻¹), respectively.

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Among the detected BPs, BPA consistently exhibited the highest mean concentrations across all three years: 27.6 ng L⁻¹ in 2022, 13.7 ng L⁻¹ in 2023, and 21.9 ng L⁻¹ in 2024. BPS and BPF followed, with mean concentrations ranging from 4.18 to 25.7 ng L⁻¹. The remaining BPs had mean concentrations near the detection limits, approximately one order of magnitude lower than that of BPA. Although BPA accounted for approximately 50% of the total concentration, the combined contribution of BPA analogues (BPS, BPF, and BPAP) reached 51–58%, surpassing BPA's dominance. This shift reflects the growing production and usage of BPA alternatives.

3.2 Spatial distribution of BPs

As shown in Fig. 1, in September 2022, elevated Σ₉BPs concentrations were observed at sites Y1 to Y6 (Yangtze River Tongling–Nanjing section), with BPS as the dominant compound. Site Y6 exhibited the highest Σ₉BPs concentration, primarily driven by BPS and BPA. Located at the Nanjing Jianjiang North Estuary water source area, Site Y6 is adjacent to the Nanjing Chemical Industrial Park, which hosts multiple chemical and petrochemical companies. The elevated Σ₉BPs levels at this site may be attributed to discharges of chemical wastewater containing bisphenol analogues from the industrial park, resulting in suboptimal water quality despite its designation as a water source. At sites Y7 to Y14 (Yangtze River Nanjing–Zhangjiagang section), Σ₉BPs concentrations varied significantly, with BPS or BPA predominating at different locations, likely influenced by diverse industrial wastewater sources. Sites Y15 to Y20 (Zhangjiagang–Shanghai section), situated in the Yangtze River estuary, showed relatively lower Σ₉BPs levels dominated by BPA, potentially due to the diluting effects of seawater.

In contrast to the 2022 findings, the analytical results of water samples collected in September 2023 (Fig. 2) revealed no significant differences in Σ₉BPs concentrations among most sampling sites, except for site Y12, which exhibited elevated Σ₉BPs levels dominated by BPA—consistent with its 2022 profile. Y12 is a monitoring section adjacent to the Taixing Economic Development Zone, a large-scale industrial park specializing in chemical new materials, new energy, and high-end equipment manufacturing (marine and ship engineering). Given that a significant proportion of BPs originate from industrial waste discharges, the consistently higher Σ₉BPs concentrations at Y12 in both 2022 and 2023 are likely attributable to emissions from this industrial cluster.

The analytical results of Yangtze River water samples collected in September 2024, expanded to include cities at the middle-lower Yangtze River transition zone (e.g., Jiujiang), are shown in Fig. 3. Except for elevated Σ₉BPs concentrations at sites Y14, Y9, Y24, and Y23, no significant differences were observed among other sampling sites. For the closely clustered sites Y21–Y23, Σ₉BPs concentrations showed minimal variation but exhibited a gradual upward trend. In September 2024, the Yangtze River basin entered the late flood season, characterized by reduced precipitation in the middle-lower reaches and declining upstream inflow. These hydrological conditions likely led to decreased flow rates in the Jiujiang-Hukou section, weakening pollutant dilution capacity and thereby increasing BP concentrations per unit water volume. Concurrently, Poyang Lake entered its recession period due to falling Yangtze water levels, diminishing the backwater effect from the lake on the mainstream Yangtze near Hukou. This further reduced flow velocity, contributing to pollutant retention in the area.

3.3 Annual comparison of BPs

The concentrations of the five major BPs detected over the three years are plotted in Fig. 4 to assess year-to-year September rainy season differences. Compared to September 2022, the mean concentrations of all detected BPs (except BPE) decreased in 2023 and 2024. Specifically, the mean concentrations of BPA and BPF in 2022 were double those observed in 2023 and 1.5 times higher than those recorded in 2024. Similarly, the mean concentration of BPS in 2022 was three times that of 2023 and 2.5 times that of 2024. One-way ANOVA was conducted to evaluate temporal differences in BPs concentrations, with time as the factor and BP concentrations as the dependent variable. The results revealed statistically significant variations (p < 0.05) for BPA, BPS, BPF, BPE, and BPAP in September across the three years.

The observed decline in BPs concentrations in 2023 and 2024 may be linked to hydrological conditions. In 2022, the lower Yangtze River experienced its most severe meteorological drought since comprehensive records began in 1961, resulting in extremely low water levels during the flood season. By contrast, September 2023 coincided with the wet season, characterized by significantly higher rainfall and increased river discharge compared to 2022, which likely diluted BPs concentrations. In 2024, reduced water levels compared to 2023 may explain the slight rebound in BPs concentrations. These findings are consistent with the research by Zhang et al., who reported lower BPs concentrations in the Qinhuai River (a major tributary of the lower Yangtze) during flood seasons due to dilution effects from increased rainfall.¹³ This consistency underscores the critical role of hydrological dynamics in shaping BP distribution patterns.

3.4 Source analysis of BPs

To identify the sources of BPs in the lower Yangtze River, statistical correlation analysis was applied to the dataset of detected BPs. Spearman correlation coefficients were calculated pairwise for the five major BPs, and the results are summarized in Fig. 5. Significant correlations were observed among BPA, BPF, BPE, and BPAP, suggesting the potential presence of common sources. In contrast, BPS showed no significant correlations with the others, indicating distinct origins. Research by Zhang et al. highlights untreated industrial wastewater and urban stormwater runoff as major contributors to riverine BPs.¹³ In this study, elevated BPA concentrations at site Y12 (near the Taixing Economic Development Zone) likely originate from wastewater discharges of industrial facilities within the zone, which hosts multiple chemical plants. This finding aligns with the hypothesis that industrial effluents from the wastewater treatment plants in the zone constitute a primary source of BPA at this site.

3.5 Ecological risk assessment of BPs

In this study, BPB and BPP were excluded from ecological risk assessment due to insufficient toxicity data, low concentrations, and low detection rates. The toxicity endpoints and PNEC values for all BPs are listed in Table S5.†

Risk quotient (RQ) values for BPs in the lower Yangtze River are shown in Fig. 6. Notably, BPS exhibited RQ values consistently exceeding 0.1(0.1–8.6), and the RQ values exceeding threshold levels with significant dispersion were omitted from the graphical representation. BPA posed low ecological risks (RQ ≥ 0.01) at some sites in 2022 and 2024, with average concentrations reaching low-risk thresholds in those years. In 2023, all BPA RQ values were <0.01, indicating negligible risk. As discussed earlier, drought in 2022 and reduced water levels in 2024 likely elevated BPA concentrations at specific sites, increasing associated risks. BPF showed low risk (RQ ≥ 0.1) only at site Y21 in September 2022, while BPE and BPAP posed no significant risks during the three-year study. BPS demonstrated markedly higher ecological risks than other BPs, with RQ values ranging from 0.102 to 7.57. At all sites where BPS was detected, concentrations corresponded to moderate or high risks. This elevated risk may stem from limited BPS toxicity data and the high sensitivity of zebrafish to BPS, resulting in a significantly lower PNEC value compared to that of other BPs. These findings highlight the pressing necessity for intensified research into the toxicity of BPS, as well as for more stringent monitoring of its environmental presence. Zhang et al. reported similar patterns in the Qinhuai River basin, where BPS posed high risks to invertebrates (average RQ = 1.30), and BPA showed moderate risks in the pre-flood season.¹³ Compared to findings from other studies, the ecological risks associated with BPs in the lower Yangtze are relatively low. However, the moderate-to-high risks posed by BPS to fish warrant immediate attention to mitigate potential adverse impacts on aquatic ecosystems.

3.6 Health risk assessment of BPs

According to the previous research results of researchers in our research group,²⁹ we reasonably speculate that BPs do exist in drinking water. In this study, Y3, Y4, Y6, Y11, Y18, Y21 and Y22 are all water source locations, and therefore health risks were evaluated for water intake points designated as drinking water sources in the lower Yangtze River: six sites (Y4, Y6, Y11, Y16, Y18, and Y22) in September 2022, two sites (Y6 and Y11) in September 2023, and two sites (Y3 and Y21) in September 2024. The estimated daily intake (EDI) of BPs via drinking water for different age groups was calculated using eqn (2.2), with the results shown in Fig. 7.

Among all BPs, BPA exhibited the highest average EDI values (0.58–1.93 ng (kg d)⁻¹) across age groups, peaking in September 2022 (0.99–1.93 ng (kg d)⁻¹). BPS followed closely behind, with EDIs ranging from 0.01 to 1.60 ng (kg d)⁻¹, also reaching its maximum in September 2022 (0.82–1.61 ng (kg d)⁻¹). BPE, BPAP, and BPF showed minimal exposure, with maximum EDIs below 0.55 ng (kg d)⁻¹.

While all measured BPA concentrations complied with China's Sanitary Standards for Drinking Water (≤0.01 mg L⁻¹),³⁷ the EDI values for BPA exceeded the European Food Safety Authority's revised temporary tolerable daily intake (t-TDI) of 0.2 ng (kg d)⁻¹,³⁸ suggesting potential health risks under this stricter guideline. These findings highlight the need to reassess exposure thresholds and strengthen the monitoring of BPs in drinking water sources to safeguard public health.

4 Conclusions

(1) Occurrence of BPs in the lower Yangtze River

Over three years (2022–2024), nine target BPs were detected with frequencies of 8.3–100%. ∑₉BPs concentrations were the highest in 2022, decreased in 2023, and increased again in 2024. BPA had the highest levels, followed by BPS and BPF. Compared to global studies, the BP levels in this study were relatively low. Elevated concentrations were observed near specific locations in 2022, but no clear spatial trends were seen in 2023 or 2024. Significant variations were noted for BPA, BPS, BPF, BPE, and BPAP within the three-year time span, likely related to changes in rainfall and water levels.

(2) Source analysis

Correlation analysis indicated that BPS had no significant association with BPA, BPF, BPE, or BPAP, implying distinct sources. Conversely, BPA, BPF, BPE, and BPAP likely share common origins, such as wastewater treatment plants and urban runoff.

(3) Ecological risks

Ecological risk assessments showed low risks for BPA at specific sites and for BPF at one site, with BPE and BPAP posing negligible risks. In contrast, BPS consistently posed moderate-to-high risks at all detected sites, necessitating urgent mitigation measures.

(4) Human health risks

EDI values for BPs in drinking water sources exceeded the European Food Safety Authority's revised t-TDI for BPA, indicating potential health risks for all age groups. Health assessments for other BPs remain limited due to the lack of established t-TDI values.

Data availability

The risk assessment factor related data used in this paper are available at: https://publications.jrc.ec.europa.eu/repository/handle/JRC23785.

Author contributions

Wanyu Li: conceptualisation, data curation, formal analysis, investigation, methodology, resources, writing-original draft, writing-review editing. Wenxuan Ma: data curation, investigation, methodology, resources. Jiajun Chang: resources. Yao Xiao: methodology, resources. Rui Wang: funding acquisition. Zhiliang Zhu: funding acquisition. Daqiang Yin: funding acquisition. Yue Li: methodology. Yanling Qiu: funding acquisition, project administration, supervision, writing-review editing.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This study was funded by the National Key Research and Development Project of China (2021YFC3200801).

Notes and references

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Footnotes

† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d5em00294j

‡ These authors contributed equally to the work and are co-first authors.

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