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Bisphenol Analogues in Sediments from Industrialized Areas in the United States, Japan, and Korea: Spatial and Temporal Distributions
Abstract
Bisphenol analogues are used in the production of polycarbonate plastics and epoxy resins. Despite the widespread use of bisphenols, few studies have reported the occurrence of compounds other than bisphenol A (BPA) in sediment. In this study, concentrations and profiles of eight bisphenol analogues were determined using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) in sediments collected from several industrialized areas in the United States (U.S.), Japan, and Korea. The total concentrations of bisphenols (ΣBPs; sum of eight bisphenols) in sediment ranged from below the limit of quantitation (LOQ) to 25 300 ng/g dry weight (dw), with a mean value of 201 ng/g dw. Sediment samples from Lake Shihwa, Korea, contained the highest concentrations of both individual and total bisphenols. Among individual bisphenols, BPA and bisphenol F (BPF) were the predominant compounds, accounting for 64% and 30% of the total bisphenol concentrations in sediment. We also examined vertical profiles of concentrations of bisphenol analogues in sediment cores from the U.S. and Japan. Sediment cores from the U.S. showed a gradual decline in the concentrations of bisphenols as compared to the past decade. BPA concentrations were found to decline in a sediment core from Tokyo Bay, but bisphenol S (BPS) was more frequently detected in core sections that represent the most recent decade, which is consistent with the replacement of BPA with BPS in some applications since 2001 in Japan.
... Laboratory studies sug-gested estrogenic effects of BPA (Staples et al., 1998), what has triggered research exploring the fate of BPA (Im and Löffler, 2016;Shobnam et al., 2021;Staples et al., 1998;Sun et al., 2021). With a K ow of 3.42, BPA has a tendency for sorption, and considerable mass exists in soils, sediments, and landfills (Huang et al., 2014;Kalmykova et al., 2013;Liao et al., 2012). BPA resists anaerobic microbial degradation but is susceptible to abiotic degradation mediated by manganese dioxide (MnO 2 ) in oxic and anoxic environments (Balgooyen et al., 2017;Huang et al., 2018;Im et al., 2015Im et al., , 2014. ...
... BPA degradation yielded products with lower ECOSAR-predicted toxicity (i.e., P1, P3, P13, and P14); however, several (e.g., P2, P5, P6, P7, P8, P11, and P12) have higher predicted toxicity than BPA, and ECOSAR categorizes these compounds as very toxic (LC50/EC50/ChV<1 mg L −1 ). BPA concentrations in impacted environments are generally well below the very toxic level (i.e., ≤ 1 mg L −1 ) (Im and Löffler, 2016;Liao et al., 2012) and it is not likely that Mn(III)-/Mn(IV)-mediated degradation will generate BPA degradation products at concentrations that would result in acute or chronic toxicity (Table S2). Considering the predicted increase in global BPA production and the uncertainties of BPA fate and exposure routes under conditions of environmental change, detailed toxicological studies of BPA transformation products to establish robust risk assessment are warranted (Liao et al., 2012;Research and Markets, 2021). ...
... BPA concentrations in impacted environments are generally well below the very toxic level (i.e., ≤ 1 mg L −1 ) (Im and Löffler, 2016;Liao et al., 2012) and it is not likely that Mn(III)-/Mn(IV)-mediated degradation will generate BPA degradation products at concentrations that would result in acute or chronic toxicity (Table S2). Considering the predicted increase in global BPA production and the uncertainties of BPA fate and exposure routes under conditions of environmental change, detailed toxicological studies of BPA transformation products to establish robust risk assessment are warranted (Liao et al., 2012;Research and Markets, 2021). ...
Bisphenol A (BPA) is a high production volume chemical with potential estrogenic effects susceptible to abiotic degradation by MnO2. BPA transformation products and reaction mechanisms with MnO2 have been investigated, but detailed process understanding of Mn(III)-mediated degradation has not been attained. Rapid consumption of BPA occurred in batch reaction vessels with 1 mM Mn(III) and 63.9 ± 0.7% of 1.76 ± 0.02 μmol BPA was degraded in 1 hour at circumneutral pH. BPA was consumed at 1.86 ± 0.09-fold higher rates in vessels with synthetic MnO2 comprising approximately 13 mol% surface-associated Mn(III) versus surface-Mn(III)-free MnO2, and 10-35% of BPA transformation could be attributed to Mn(III) during the initial 10-min reaction phase. High-resolution tandem mass spectrometry (HRMS/MS) analysis detected eight transformation intermediates in reactions with Mn(III), and quantum calculations proposed 14 BPA degradation products, nine of which had not been observed during MnO2-mediated BPA degradation, suggesting mechanistic differences between Mn(III)- versus MnO2-mediated BPA degradation. The findings demonstrate that both Mn(III) and Mn(IV) can effectively degrade BPA and indicate that surface-associated Mn(III) increases the reactivity of synthetic MnO2, offering opportunities for engineering more reactive oxidized Mn species for BPA removal.
... Launched into production over 50 years ago, epoxy resins aroused enormous interest owing to their valuable properties that distinguished them from other polymeric materials [8][9][10][11]. Due to their unique properties, epoxy resins are applied in many fields of technology; one of the most popular applications is the production of polymer composites that are used as structural elements, including the aviation industry, boatbuilding, construction sector and electric installations [5,6,8,[12][13][14][15]. As a result of their polar nature, epoxy resins offer very high adhesion qualities to many different materials, such as glass, ceramics, metal, concrete, and polymers; they are considered, therefore, as universal adhesives [16][17][18][19]. ...
... Bisphenols (BPs) are produced all over the world in large quantities. They are frequently used in the manufacture of polycarbonate plastics and epoxy resins; such polymers are also used in a variety of consumer products, such as baby feeding bottles, toys, and epoxy liners for food cans [15]. Epoxy resins are also widely used as dental materials, medical adhesive or coatings, bone material and in other medical applications [33,34,39,40,41,42]. ...
... Bisphenols (BPs) are produced all over the world in large quantities. They are frequently used in the manufacture of polycarbonate plastics and epoxy resins; such polymers are also used in a variety of consumer products, such as baby feeding bottles, toys, and epoxy liners for food cans [15]. Epoxy resins are also widely used as dental materials, medical adhesive or coatings, bone material and in other medical applications [33,34,[39][40][41][42]. ...
The aim of this work was to investigate selected biological and toxicity properties of cured
epoxy resin-based compounds based on a bisphenol A epoxy resin, cold-cured by a polyamide and containing two types of metal powders (aluminum and copper). This study involved cytotoxicity analysis, pH measurements, absorbance measurements and sterilization. The cytotoxicity analysis was conducted to determine the harmful degree of the cured epoxy resin. Aimed at identifying toxic agents in cured compounds, the cytotoxicity analysis involved absorbance measurements in an entire wavelength range. Cytotoxicity and absorbance results demonstrated that the extracts of all the tested resin samples had no cytotoxic effects on the cells of living organisms. The absorbance values obtained over the entire wavelength range did not point to the formation of aggregations, which proved that no toxic agents harmful to living organisms were extracted from the resin samples. Based on the results obtained, it can be concluded that all tested compounds, based on epoxy resins,
which are also used as adhesives in various applications, are essentially safe materials when using such formulations in a cured state.
... 1 The global BPA market was about 8 million metric tons in 2016, and a further increase is projected. 2 BPA has been detected in numerous environmental matrices, ranging from 0.5 to 325 ng g −1 (dry weight) in soil, 3 0.2 to 39.1 μg g −1 (dry weight) in dust, 4 1.49 to 13 370 ng g −1 (dry weight) in sediments, 5 and 0.5 to 776 ng L −1 in surface water bodies. 6 The presence of BPA in environmental systems has raised concerns due to the estrogenic properties observed in laboratory studies, 7,8 and the environmental fate of BPA is, therefore, of significant interest. ...
... With an n-octanol−water partition coefficient log K OW of 3.42, 29 BPA has a tendency for sorption to hydrophobic matrices, which are major sinks for, and reservoirs of, BPA in the environment. 3,4 Although BPA sorbed to a porous matrix is considered stable, environmental perturbations could result in the desorption and release of BPA, 30−33 thereby increasing the exposure risk. For example, the presence of co-contaminants (i.e., heavy metals), 30 elevated temperatures, 32 and elevated pH 33 has been shown to increase BPA desorption. ...
... Environmental Implications. Adsorbed BPA occurs in a number of environmental systems and has been reported in soils (0.5−325 ng BPA g −1 , dry weight), 3 sediments (1.49−13 370 ng BPA g −1 , dry weight), 4 and sewage sludge (4−1363 ng BPA L −1 , dry weight), 6 which are considered major sinks and reservoirs for BPA. Although these materials have unique physicochemical properties that distinguish them from SPAC, 35,82 they often possess broadly similar hydrophobic pore structures in the nanometer to micrometer size range. ...
Bisphenol A (BPA), a high production volume chemical and potential endocrine disruptor, is found to be associated with sediments and soils due to its hydrophobicity (log KOW of 3.42). We used superfine powdered activated carbon (SPAC) with a particle size of 1.38 ± 0.03 μm as a BPA sorbent and assessed degradation of BPA by oxidized manganese (Mn) species. SPAC strongly sorbed BPA, and desorption required organic solvents. No degradation of adsorbed BPA (278.7 ± 0.6 mg BPA g-1 SPAC) was observed with synthetic, solid α-MnO2 with a particle size of 15.41 ± 1.35 μm; however, 89% mass reduction occurred following the addition of 0.5 mM soluble Mn(III). Small-angle neutron scattering data suggested that both adsorption and degradation of BPA occurred in SPAC pores. The findings demonstrate that Mn(III) mediates oxidative transformation of dissolved and adsorbed BPA, the latter observation challenging the paradigm that contaminant desorption and diffusion out of pore structures are required steps for degradation. Soluble Mn(III) is abundant near oxic-anoxic interfaces, and the observation that adsorbed BPA is susceptible to degradation has implications for predicting, and possibly managing, the fate and longevity of BPA in environmental systems.
... Bisphenol analogs were developed to replace bisphenol A (BPA) in the plastic industry, and their excessive use in food containers, bottles, and receipts has led to a gradual increase in environmental contamination with BPA analogs globally (Chen et al., 2016a;Liao et al., 2012;Yamazaki et al., 2015;Yang et al., 2014). Previous studies reported that bisphenol analogs, including bisphenol F (BPF), are unsafe for humans and, as BPA, act as endocrine disrupting chemicals that strongly interfere with sex hormones (e.g., estrogen, testosterone, and progesterone) in various organisms (Eladak et al., 2015;Moreman et al., 2017;Mu et al., 2022;Ullah et al., 2019;Ullah et al., 2018). ...
... BPF is present in indoor dust (1-1000 ng/g), sediments (1.44-3.57 μg/kg), soil (249 μg/kg), and water (0.001-2.85 μg/L) (Chen et al., 2016b;Fromme et al., 2002;Liao et al., 2012;Lim et al., 2022;Yamazaki et al., 2015;Yang et al., 2014). Consequently, BPF has also been detected in human urine samples (0.14-1.11 μg/L) in biomonitoring studies (Lehmler et al., 2018;Wang et al., 2019;Zhu et al., 2019). ...
Although bisphenol F (BPF), the main replacement for bisphenol A, has been commonly used in polycarbonate production, its neurotoxicity and the underlying mechanisms remain poorly understood. To address this knowledge gap, this study aimed to assess the neurotoxicity caused by chronic exposure to BPF and to identify its underlying mechanisms. We exposed adult zebrafish chronically to BPF at environmentally relevant concentrations (0.001, 0.01, and 0.1 mg/L) for 4 weeks. The results revealed that with BPF crossing the blood–brain barrier and bioaccumulating in brain tissues, chronic exposure to BPF resulted in anxiety-like behaviors and disruptions in learning and memory function in adult zebrafish. Furthermore, BPF toxicity in the zebrafish brain involved the dysregulation of metabolic pathways for choline and kynurenine in neurotransmitter systems and for 17β-estradiol, cortisol, pregnenolone-sulfate, and Dehydroepiandrosterone (DHEA)-sulfate in neurosteroid systems. RNA-seq analysis revealed that BPF exposure affected metabolic pathways, calcium signaling pathways, neuroactive ligand–receptor interactions, tight junctions, gap junctions, and the gonadotropin-releasing hormone signaling pathway. Our results indicate that chronic exposure to BPF alters the neurochemical profile of the brain and causes neurobehavioral effects, such as anxiety and cognitive decline. Overall, the multimodal approach, including behavioral and neurochemical profiling technologies, has great potential for the comprehensive assessment of potential risks posed by environmental pollutants to human and ecosystem health.
... Results in private houses and drug stores have indicated about the range of exposed dose to bisphenol from 0.29-7.15 ng/kg-bw/day, approximately a half lower than reports in Korea (18.6 ng/kgbw/day), Japan (15.8 ng/kg-bw/day), the USA (12.6 ng/kg-bw/day) [29]. Compared between different groups of age, the higher risk of being impacted by these chemicals in infants and children than the older. ...
... So, working for a long time in this environment without enough safety can lead to negative effects on human health. However, DI values calculated in this work were much lower than the oral reference dose of 50 µg/kg-bw/day established by the EPA and the European Food Safety Authority [3,22,29], suggesting that bisphenol intake via dust ingestion in this study should be in the safety of threshold for Vietnamese. It is necessary to perform further studies with large sample sizes in various microenvironments, even bio-metabolites to assess human exposure to these contaminants. ...
This study has focused on the development of the method LC-MS/MS to determine 2,2-bis(4-hydroxyphenyl)propane (bisphenol A: BPA) and 4,4’-dihydroxydiphenylmethane (bisphenol F: BPF) in indoor samples by using ultrasonication extraction and solid-phase extraction for preparation. The chromatographic procedure was performed on Kinetex C18 2.1 x 150 mm, 2.6 µm column with mobile phases: 2 mM HCOONH4 in MeOH and H2O:MeOH (90:10,…). The method quantification limits (MQL) of BPA and BPF were 15.0 and 12.0 ng/g, respectively. The mean recoveries were 80.4% for BPA and 93.8% for BPF (RSD<15%). The calibration curve for both BPA and BPF was linear over a concentration range of 1.0 to 500 ng/mL (R2 ≥ 0.999). Twenty-one samples were collected from private houses, laboratories, drug stores, and plastic recycling factories in Hanoi. BPA and BPF were found in dust samples with frequencies of 85.7 and 100%, respectively. Concentrations of BPA and BPF in dust samples were in the ranges of <MQL–2230 ng/g (mean: 626) and <MQL–149,000 ng/g (mean: 14,700), respectively. Based on the measured concentration, the human exposure to bisphenol via indoor dust ingestion was estimated for various age groups. The estimated exposure dose for people working at plastic recycling factories was the highest level (23.6 ng/kg-bw/day) but lower than the oral reference dose by the EPA and the European Food Safety Authority (50 µg/kg-bw/day).
... BPS and BPF were the two most frequently-detected BPAAs in estuarine sediments from Europe, Asia, and North America with median/mean concentrations of 0.14-61.4 and 2.15-338 ng/g dw, respectively (Table S9) (Celis-Hernandez et al., 2021;Liao et al., 2012;Liao et al., 2019). Moreover, BPS occurred in water sampled from the PRE, the Puget Sound, and the SFB, while the former also contained measurable levels of BPF, BPB, BPAF, and BPP (Shimabuku et al., 2022;Tian et al., 2020;Zhao et al., 2019). ...
... The climbing sedimentary deposition of PHCZs in the PRE signified aggravation of PHCZ contamination following the fast socioeconomic development surrounding the PRE over the past decades . Contrary to BPA, which declined over time, BPS was more frequently detected in the slices representing the most recent decade in the TKB sediments core, agreeing with the substitution of BPA with BPS since 2001 in Japan (Liao et al., 2012). Additionally, sediment geochemistry may also impact temporal changes in a similar manner as applied to spatial distributions mentioned in the section above (Celis-Hernandez et al., 2021;Shen et al., 2018). ...
Organic contaminants of emerging concern (OCECs) originating from assorted sources have attracted increasing attention latterly as most of them are not under routine surveillance or effective regulation but possess persistent, bioaccumulative, and toxic potential. Massive terrestrial inputs and proximity to intense human activities have elevated OCEC contamination in many estuaries. The present review outlines the current knowledge on the environmental occurrence and fate, as well as bioavailability of nine classes of OCECs, i.e., per- and polyfluoroalkyl substances, alternative halogenated flame retardants, organophosphate esters, chlorinated paraffins, ionic surfactants, phthalate alternatives, polyhalogenated carbazoles, synthetic antioxidants, and bisphenol A alternatives in global estuaries. Available data have documented prevalence of studied OCECs in estuarine compartments from around the world, particularly in North America, Europe, and Asia. Their spatiotemporal trends, vertical distributions in the water column, and multi-media partitioning are mainly dependent on anthropogenic impacts (e.g., production and consumption patterns, urbanization, industrialization, and waste treatment), hydrodynamics, meteorological conditions, characteristics of environmental media and the interactions with OCECs, and physiochemical properties of OCECs. Bioaccumulation and biomagnification have also been reported for many estuarine OCECs, which favor those with moderate hydrophobicity, considerable proteophilicity, and satisfactory resistance to environmental degradation and biological transformation. To comprehensively elucidate OCEC exposure for estuarine ecosystems from the big picture, future research is warranted in various fields, including environmental chemistry and (eco-)toxicology, and may involve more interdisciplinary collaborations.
... Bisphenols are high-production-volume chemicals [5]. Bisphenol A (BPA) and bisphenol S (4,4 -sulfonyldiphenol; BPS) are the most abundant bisphenol congeners detected in humans, with BPS being present in over 80% of human urine samples from the United States [6] and six other Asian countries [6][7][8][9], ranging from 0.07 to 211.9 ng/mL [10]. BPS is also present in foodstuffs [11], indoor dust [12], sewage sludge [13], ground water [14], and sediments from industrialized areas [8]. ...
... Bisphenol A (BPA) and bisphenol S (4,4 -sulfonyldiphenol; BPS) are the most abundant bisphenol congeners detected in humans, with BPS being present in over 80% of human urine samples from the United States [6] and six other Asian countries [6][7][8][9], ranging from 0.07 to 211.9 ng/mL [10]. BPS is also present in foodstuffs [11], indoor dust [12], sewage sludge [13], ground water [14], and sediments from industrialized areas [8]. Growing evidence supports the notion that BPS exposure can affect human health [15][16][17]. ...
The placenta supports fetal growth and is vulnerable to exogenous chemical exposures. We have previously demonstrated that exposure to the emerging chemical bisphenol S (BPS) can alter placental endocrine function. Mechanistically, we have demonstrated that BPS interferes with epidermal growth factor receptor (EGFR) signaling, reducing placenta cell fusion. Extravillous trophoblasts (EVTs), a placenta cell type that aids with vascular remodeling, require EGF to invade into the maternal endometrium. We hypothesized that BPS would impair EGF-mediated invasion and proliferation in EVTs. Using human EVTs (HTR-8/SVneo cells), we tested whether BPS could inhibit the EGF response by blocking EGFR activation. We also evaluated functional endpoints of EGFR signaling, including EGF endocytosis, cell invasion and proliferation, and endovascular differentiation. We demonstrated that BPS blocked EGF-induced phosphorylation of EGFR by acting as a competitive antagonist to EGFR. Transwell assay and a three-dimensional microfluidic chip invasion assay revealed that BPS exposure can block EGF-mediated cell invasion. BPS also blocked EGF-mediated proliferation and endovascular differentiation. In conclusion, BPS can prevent EGF-mediated EVT proliferation and invasion through EGFR antagonism. Given the role of EGFR in trophoblast proliferation and differentiation during placental development, our findings suggest that maternal exposure to BPS may contribute to placental dysfunction via EGFR-mediated mechanisms.
... BPAF and BPS were the second and third predominant BPs, which could be explained by the regulation of BPA. These two chemicals were the main BPA substitutes partially because they are more resistant to biological degradation in aquatic environment (Liao et al., 2012a(Liao et al., , 2012b(Liao et al., , 2012c(Liao et al., , 2012d. ...
Bisphenol analogues (BPs) have gained increasing attention in recent years due to their ubiquitousness in the environment, potential endocrine disrupting properties and ecological impacts. However, very little information is available on the occurrence, partitioning and ecological risks of BPs in marine environments. In the present study, six BPs were investigated in surface water and sediment samples from the Beibu Gulf, South China Sea. Results showed that bisphenol A (BPA) was the predominant BP in both water and sediment samples with levels ranging from 5.26 to 12.04 ng/L in water and 0.56 to 5.22 ng/g dw in sediment samples, followed by bisphenol AF (BPAF: 0.44-0.60 ng/L in water and 0.08-0.66 ng/g dw in sediment samples, respectively) and bisphenol S (BPS: 0.07-0.63 ng/L in water and not detected (ND) to 0.19 ng/g dw in sediment samples, respectively). There is no significant spatial difference of BPs levels between riverine sediment samples and coastal sediment samples. Compared with other studies, the concentrations of BPs from the Beibu Gulf were relatively low. The mean log-transformed sediment-seawater partitioning coefficients (log Koc) ranged from 4.4 (DHBP) to 5.2 (BPAF) and the log Koc values for all the target BPs were generally higher than those reported in freshwater environments. The present study firstly reported the field-based log Koc values for BPB (mean: 4.5) and DHBP (mean: 4.4). The estimated risk quotient (RQ) and 17β-estradiol (E2) equivalent quotient (EEQ) values indicated that the ecological and human health impacts were negligible associated with target BPs. The present study provided reliable and detailed data for completely evaluating contamination level and environmental behaviors of BPs in the Beibu Gulf.
... These chemicals have been found in sediments in China, at concentrations of 270 ng g − 1 for BPA, 47 ng g − 1 for BPS, 4 ng g − 1 for BPB, 27.5 ng g − 1 for BPF, 57.1 ng g − 1 for BPAF, 2.5 ng g − 1 for BPZ or 0.40 ng g − 1 for BPAP (Jin and Zhu, 2016;Liu et al., 2017;Zhao et al., 2020). High concentrations have also been reported in the United States or Japan (106 and 23 ng g − 1 for BPA, 4.65 and 4.46 ng g − 1 for BPS, 27.5 and 9.11 ng g − 1 for BPF or 0.36 ng g − 1 for BPAF respectively (Liao et al., 2012)) as well as in sediments collected in sand beaches around the world (up to 670 ng g − 1 for BPA) (Kwon et al., 2020). In biofilm samples up to 59.3, 1.17, 1.4 and 47.6 ng g − 1 were detected for BPA, BPS, BPAF and TBBPA, respectively, with a detection frequency (DF) of 50% for BPA, BPAF and TBBPA and 75% for BPS (Table 1 and Table S5). ...
Bisphenol A (BPA) is one of the main ubiquitous compounds released from plastics in the environment. This compound, considered an endocrine disruptor, poses a risk to aquatic wildlife and human population, being included in multiple environmental monitoring programmes. Following the regulations restricting BPA use in the last years, BPA-like chemicals have been produced and used as BPA substitutes. However, they are not commonly included in monitoring programs yet and their presence is thus misrepresented, despite showing similar endocrine disrupting potential. In this work, an analytical method for analysing bisphenol A and five of its analogues (Bisphenol S, B, F, AF and Tetrabromobisphenol A) is described, validated for water (riverine, sea and wastewater), sediment, and biota (fish and biofilm) and applied to monitor their presence in the Ebro River Delta (NE Spain). In addition, plastic litter was also collected to evaluate their role as potential source of bisphenols. All compounds except BPF were detected in the analysed samples. Wastewater treatment plants (WWTPs) were discarded as major sources of BPs into the natural aquatic environment, as no BPs were detected in treated effluents. Indeed, the high levels of BPs in the natural environment could be related with direct discharge of raw wastewater from small rural population nucleus. The analysis of riverine plastic leachates yielded 4 out of the 6 BPs analysed, strengthening the hypothesis that plastic debris are also a source of BPs in the natural environment. Whereas Bisphenol S and BPA were detected in water and, to a limited extent, in biota, less polar analogues (mainly BPAF and TBBPA) were not found in any of the water samples. Instead, these hydrophobic BPs were found in fish tissues and biofilm, pointing out plastics and microplastics as their possible vectors. Finally, biofilm demonstrated its potential as sentinel of chemical contamination in freshwater environment.
... Moreover, BPA has been listed as a contaminant item in the latest drinking water quality standard of China, Japan, and European Union (Yuan et al. 2018;Liu et al. 2021a). Due to restrained usage of BPA, bisphenol S (BPS), bisphenol F (BPF), bisphenol AF (BPAF), etc., have been applied as BPA substitutes in a variety of fields (Chen et al. 2016;Liao et al. 2012). All these BPA substitutes have a common structure of two hydroxyphenyl functional groups and are collectively termed as bisphenol analogs (BPs) (Delfosse et al. 2012). ...
Bisphenol analogs (BPs) in livestock urine are important biomarkers to reflect the potential contaminants in food products derived from these animals. Nevertheless, little research has been done on their occurrence in farm animal urine. This work investigated ten BPs in swine and bovine urines collected from two Chinese farms. Results showed that all of these ten BPs were frequently detected in swine and bovine urines. The total mean concentration of the ten BPs (ΣBPs) in sow urines was 59.7 ng/mL, which was significantly higher than that of the boar urine with a mean concentration of 37.0 ng/mL (p < 0.05). On the other hand, the corresponding mean concentration of ΣBPs in dairy cattle urine was 59.6 ng/mL, which was significantly higher than that of the beef cattle urine with 37.0 ng/mL (p < 0.05). The respective mean concentration contribution ratios of BPA to ΣBPs in boar, sow, dairy, and beef cattle urines were only 14.9%, 21.4%, 9.0%, and 14.6%, which clearly indicated that BPA was no longer the dominant BP. The average daily urinary excretion rates of ΣBPs by boar, sow, dairy, and beef cattle were 37.0, 59.8, 167.0, and 36.8 times that of human, which suggested that swine and bovine likely encountered high dosage exposure of BPs in the two Chinese livestock farms. Our results showed that feeds and nutritional supplements as unintentionally added contaminants were the main sources of BPs to swine and bovine. As swine and bovine are important food sources for human being, part of BPs exposed to livestock eventually would enter human body via meat or milk. Therefore, quality controls of these feeds or nutritional supplements are quite important in order to guarantee welfare of livestock as well as protect health of our human beings.
... The mean BPF and BPS concentrations in Korea were 69.7 and 12.37 ng/g, respectively. Other bisphenols were detected at concentrations of 2 ng/g or less (Liao et al. 2012b). Similarly, Lan et al. (2019) detected BPA in sediment samples in China at 521 ng/g. ...
The continuous use of household and personal care products (HPCPs) produces an immense amount of chemicals, such as parabens, bisphenols, benzophenones and alkylphenol ethoxylates, which are of great concern due to their well-known endocrine-disrupting properties. These chemicals easily enter the environment through man-made activities, thus contaminating the biota, including soil, water, plants and animals. Thus, on top of the direct exposure on account of their presence in HPCPs, humans are also susceptible to secondary indirect exposure attributed to the ubiquitous environmental contamination. The aim of this review was therefore to examine the sources and occurrence of these noteworthy contaminants (i.e. parabens, bisphenols, benzophenones, alkylphenol ethoxylates), to summarise the available research on their environmental presence and to highlight their bioaccumulation potential. The most notable environmental contaminants appear to be MeP and PrP among parabens, BPA and BPS among bisphenols, BP-3 among benzophenones and NP among alkylphenols. Their maximum detected concentrations in the environment are mostly in the range of ng/L, while in human tissues, their maximum concentrations achieved μg/L due to bioaccumulation, with BP-3 and nonylphenol showing the highest potential to bioaccumulate. Finally, of another great concern is the fact that even the unapproved parabens and benzophenones have been detected in the environment.
Graphical abstract
... BPZ was chosen for in vivo kinetic studies as it has been detected in human urine 14 and serum 12 samples, food, 35 personal care products, 17 and various environmental matrixes such as sludge 36 and sediment. 37 Furthermore, BPZ has shown considerably higher bioaccumulation than BPA in fish. 22 Notably, data on metabolization of BPA analogues in fish are currently missing, despite this being considered the main route of eliminating parent compounds in vivo 38,39 and, therefore, one of the most important parameters for understanding toxicokinetics in fish. ...
Bisphenol A (BPA) is an industrial chemical, which has raised human health and environmental concerns due to its endocrine-disrupting properties. BPA analogues are less well-studied despite their wide use in consumer products. These analogues have been detected in water and aquatic organisms around the world, with some analogues showing toxic effects in various species including fish. Here, we present novel organ-specific time-course distribution data of bisphenol Z (BPZ) in female zebrafish (Danio rerio), including concentrations in the ovaries, liver, and brain, a rarely sampled organ with high toxicological relevance. Furthermore, fish-specific in vitro biotransformation rates were determined for 11 selected bisphenols. A physiologically based toxicokinetic (PBTK) model was adapted for four of these bisphenols, which was able to predict levels in the gonads, liver, and brain as well as the whole body within a 2-5-fold error with respect to experimental data, covering several important target organs of toxicity. In particular, predicted liver concentrations improved compared to currently available PBTK models. Predicted data indicate that studied bisphenols mainly distribute to the carcass and gonads and less to the brain. Our model provides a tool to increase our understanding on the distribution and kinetics of a group of emerging pollutants.
... BPF has been used in the manufacturing of food packages and water pipes [10,11]; BPAF is included in electronics and optical fibers, and as a high-performance monomer for polyimides, polyamides and other polymers [9,12,13]. Unfortunately it was found that BPA analogues exert, to some extent, endocrine disruptive effect and these analogues can be even more harmful than BPA, which make them not safe alternatives for BPA [14][15][16]. Additionally, BPA analogues have been proved to be less biodegradable than BPA [17,18]. ...
Due to well-known risks to human and environmental health, the increasing presence of several micropollutants even in very low concentrations in environmental matrices requires sustainable and advanced analytical methods to expand monitoring programs, particularly for water quality control. The objective of this study was to optimise the conditions of the dispersive liquid-liquid microextraction (DLLME) for a combined group of emerging micropollutants (bisphenol A, bisphenol S, bisphenol F, bisphenol AF and benzophenone) in complex water matrices. Ten variables were chosen as the most important for DLLME procedure and the Design of Experiments (DoE) approach was applied to find the most relevant variables and optimise the DLLME procedure. The optimised DLLME was then, applied to real complex water samples including raw and treated wastewaters and surface water in Rio de Janeiro city, Brazil, and the extracted samples were analysed by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The variables vortex mixing time (VMT), Dispersive Solvent Volume (DSV) and Extractor Solvent Volume (ESV) are the most important among the variables evaluated. The recovery efficiencies ranged from 60 to 120% after optimisation the amounts of target compounds found in the five real aqueous matrices varied from 0.005 to 150 μg L⁻¹. The association of optimised DLLME with the UPLC-MS/MS met the validation requirements adopted and generated analytical results of high quality. The advantages of this extraction technique include reduction of cost per analysis; low volume of samples and low volume of solvent required; no need to use cartridges; reduction of waste generation. The method is, therefore, suitable to process large numbers of samples, particularly in countries with limited budgets for environmental monitoring.
... In particular, Ansan and Incheon suffered from the highest environmental contamination caused by several types of organic pollutants due to the highest industrial activities among the cities (Liao et al. 2012b;Moon et al. 2012;Kim et al. 2021b;Lee et al. 2021c;Lee and Moon 2021). In our study, the median concentrations of BPA (0.20-1.67 ng/L), BPF (2.23-3.13 ...
Presence of endocrine disruptors in drinking water is a public and global concern. Bisphenol A (BPA) has been primarily used for polycarbonate plastics and epoxy resins. Due to domestic and global regulations on BPA, other bisphenol analogues (BPs) have been introduced as alternatives. Despite this, few studies have been conducted for human health risks of BPA and their alternatives, such as bisphenol F (BPF) and bisphenol S (BPS), through the consumption of drinking water. The present study aimed to determine seven BPs in three types of drinking water (tap water, purified water, and bottled water) to assess the occurrence, regional differences, source tracking, and potential health risks of BPs. BPA and BPF were detectable in almost all drinking water samples. The BPA concentration in tap water was significantly higher than that observed in purified water, whereas the BPF concentration in purified water was higher than those observed in tap water and bottled water. This result provides a wake-up call to improve the safety of purified water for emerging contaminants, such as BPF. The highest BP concentrations were observed for regions with intensive industrial activities and human populations. The concentration ratios of BPF/BPA in all tap water samples were greater than 1, indicating replacement of BPA with BPF in industrial markets. Boiling increased BPA and decreased BPF and BPS concentrations in tap water. The estimated daily intakes of BPA through consumption of drinking water for all age groups and scenarios (0.36–0.72 ng/kg bw/day) were lower than the tolerable daily intake (4.0 µg/kg bw/day) proposed by the European Food Safety Authority, implying a limited health risk. Toddlers were the highest exposure group for all BPs and scenarios. This is the first comprehensive survey of several BPs in different types of drinking water.
Graphical Abstract
... Among these EDCs are bisphenols, synthetic lipophilic chemicals used in the manufacturing of plastics and epoxy resins (Vandenberg et al., 2007). Bisphenol A (BPA), the most prevalent bisphenol, is ubiquitously found in consumer products, foodstuffs, running and drinking water, and dust samples (Liao et al., 2012a(Liao et al., , 2012bLiao and Kannan, 2013). Despite BPA's short half-life, its ubiquitous exposure is reflected in its presence in >90% of human serum, umbilical cord blood, breast milk, and urine samples tested (Calafat et al., 2009;Mendonca et al., 2014;vom Saal and Welshons, 2014;Huang et al., 2018). ...
Bisphenol A (BPA) is an endocrine disrupting chemical known to promote adipose tissue mass in vivo and adipogenesis in vitro. Whether BPA can affect and reprogram early adipogenic differentiation signals that trigger adipogenic differentiation, remains unknown. We hypothesized that gestational BPA exposure results in a preadipocyte phenotype that leads to accelerated adipogenic differentiation, and that this phenotype is sex specific. Primary ovine fetal preadipocytes were derived from control (C) and BPA-exposed during pregnancy and differentiated in vitro. Gestational BPA enhanced lipid accumulation at early stages of differentiation (48 h) and this was evident in females but not male-derived fetal preadipocytes. After an RNA sequencing approach, samples were compared as follows: 2 groups (C vs. BPA); 2 sexes (female (F) vs. male (M)); and 2 time points (0 h vs. 48 h). Before differentiation, 15 genes were differentially expressed between the C and the BPA-exposed preadipocytes within sex. In BPA-F, extracellular matrix remodeling genes cathepsin K and collagen 5α3 were upregulated compared to C–F. At 48 h, BPA-F had 154 genes differentially expressed vs. C–F and BPA-M had 487 genes differentially expressed vs. C-M. Triglyceride and glycerophospholipid metabolism were the most upregulated pathways in BPA-F. Downregulated pathways were associated with extracellular matrix organization in BPA-exposed preadipocytes. These findings are among the first to demonstrate that gestational BPA can modify the fate of adipocyte precursors by altering pathways associated to extracellular matrix components, an often-disregarded, but required aspect of adipogenic differentiation. This work highlights the need to investigate early adipogenic differentiation changes in other obesogenic chemicals.
... BPAF is unique for its chemical composition (fluorine-substituted) and particularly potent cytotoxicity. BPAF has been used in the production of fluoroelastomers, electronics, optical fibers, and various polymers (such as polyimides, polyamides, polyesters, polycarbonates) in large scales (Liao et al., 2012b;Chen et al., 2016), thus BPAF continues to be released to the environment and expose the human body, and its potential impact on the human health has become a major concern from scientists and the public. ...
Bisphenol compounds (BPs) are ubiquitously existing pollutants. Recent evidence shows that they may be activated by human CYP1A1 for clastogenic effects; however, factors that influence/mediate CYP1A1-activated 4,4′-(hexafluoroisopropylidene)diphenol (BPAF) toxicity, particularly the aryl hydrocarbon receptor (AhR), sulfotransferase (SULT) 1A1 [known to conjugate 2,2-bis(4-hydroxyphenol)-propane (BPA)] and reactive oxygen species (ROS), remain unclear. In this study, a human hepatoma (HepG2) cell line was genetically engineered for the expression of human CYP1A1 and SULT1A1, producing HepG2-hCYP1A1 and HepG2-hSULT1A1, respectively. They were used in the micronucleus test and γ-H2AX analysis (Western blot) (indicating double-strand DNA breaks) with BPAF; the role of AhR in mediating BPAF toxicity was investigated by coexposure of AhR modulators in HepG2 and its derivative C3A (with no genetic modifications but enhanced CYP expression). The results indicated induction of micronuclei by BPAF (≥ 2.5 µM, for 2-cell cycle) in HepG2-hCYP1A1 and C3A, while inactive in HepG2 and HepG2-hSULT1A1; however, BPAF induced micronuclei in HepG2 pretreated with 3,3’,4,4’,5-pentachlorobiphenyl (PCB126, AhR activator), and BAY-218 (AhR inhibitor) blocked the effect of BPAF in C3A. In HepG2-hCYP1A1 BPAF selectively induced centromere-free micronuclei (immunofluorescent assay) and double-strand DNA breaks. In HepG2 cells receiving conditional medium from BPAF-HepG2-hCYP1A1 incubation micronuclei were formed, while negative in HepG2-hSULT1A1. Finally, the intracellular levels of ROS, superoxide dismutase and reduced glutathione in C3A and HepG2-hCYP1A1 exposed to BPAF were all moderately increased, while unchanged in HepG2 cells. In conclusion, like other BPs BPAF is activated by human CYP1A1 for potent clastogenicity, and this effect is enhanced by AhR while alleviated by SULT1A1.
... To fulfill the market demand, bisphenol analogues with chemical structures similar to BPA have been widely used, and some of them are gradually being used as substitutes for BPA (Chen et al. 2016;Delfosse et al. 2012;Liao et al. 2012;Xue et al. 2015;Banderakhshan et al. 2022). Bisphenol F (BPF), bisphenol S (BPS), and bisphenol AF (BPAF) are the major alternatives of BPA in the manufacture of epoxy resins and polycarbonate plastics. ...
Bisphenol analogues (BPs) including bisphenol a (BPA) have been broadly utilized as industrial feedstocks and unavoidably discharged into water bodies. However, there is little published data on the occurrence, distribution, and environmental risks of other BPs in surface water. In this study, ten BPs besides BPA were analyzed in surface water from the Pearl River, South China. Among these detected BPs, BPA, bisphenol F (BPF), bisphenol AF (BPAF), and bisphenol S (BPS) were the most frequently detected compounds. The median concentrations of the measured BPs were ranked in the order of BPA (34.9 ng/L) > BPS (24.8 ng/L) > BPAF (10.1 ng/L) > bisphenol F (BPF) (9.0 ng/L) > bisphenol B (BPB) (7.6 ng/L) > bisphenol C (BPC) (1.2 ng/L). Among them, BPA and BPS were predominant BPs, contributing 68% of the total ten BPs in surface water of the Pearl River. These results demonstrated that BPA and BPS were the most extensively utilized and manufactured BPs in this region. The source analysis of BPs suggested that the BPs may be originated from domestic wastewater, wastewater treatment plant (WWTP) effluent, and the leaching of microplastic in surface water of the Pearl River. The calculated BP-derived estrogenic activity exhibited low to medium risks in surface water, but their combined estrogenic effects with other endocrine disrupting compounds should not be ignored.
... Bisphenols (BPs) are produced all over the world in large quantities. They are frequently used in the manufacture of polycarbonate plastics and epoxy resins, which are used in a variety of consumer products such as baby feeding bottles, toys and epoxy liners for food cans [41]. Epoxy resins are also widely used as dental materials, medical adhesive or coatings, bone material, etc [42,43,44,45,46]. ...
Introduction: Launched into production over 50 years ago, epoxy resins aroused enormous interest owing to their valuable properties that distinguish them from other polymeric materials. The investigation of biological and chemical effects of direct exposure to the materials under study on the human body may help in the organization of work when dealing with this type of materials.
Objectives: The objective of this study is to investigate selected biological and chemical properties of 3 cured epoxy compounds: Epidian 53 epoxy resin with polyaminoamide C curing agent, Epidian 53 epoxy resin with polyaminoamide C curing agent, and aluminum powder, and Epidian 53 epoxy resin with polyaminoamide C curing agent, and copper powder.
Methods: The experimental part of this paper describes the preparation and fabrication of adhesive compound samples, from a liquid state to cured plates. The study involved a cytotoxicity analysis (with an ELSA reader), pH measurements (with a pH meter), absorbance measurement over an entire reference wavelength range, and sterilization (on a specially designed test bench) along with microscopic examination of its effects.
Results: Cytotoxicity and absorbance analysis results demonstrate that extracts of all tested resin samples do not have cytotoxic effect on the cells of living organisms. The absorbance results over the wavelength range do not indicate the formation of aggregations, which proves that no toxic agents harmful to living organisms are extracted from the resin samples.
Conclusion: Results of this study demonstrate that cured epoxy resins are safe materials.
... BPF has been used in the production of lacquers, vanishers, adhesives plastics, water pipes, dental sealants, and food package coatings while BPS has been applied in the manufacturing process of polyvinyl chloride (PVC), thermal printing papers, electronic components, food and beverages containers [13,14]. Given the widespread use of these chemicals, it is not surprising that they have been detected in sediments [15], soils [16], human biofluids [17], food [18,19], wastewater treatment plants effluents [20,21], surface water [8,22], and aquatic organisms [23]. Reports of BPA being quantified in water samples started in the 1990s, with most studies being associated with river sites close to wastewater treatment plants [24]. ...
Bisphenols are used in the production of polycarbonate plastics and epoxy resins. Bisphenol A (BPA) has been widely studied and is believed to act as an endocrine disruptor. Bisphenol F (BPF) and bisphenol S (BPS) have increasingly been employed as replacements for BPA, although previous studies suggested that they yield similar physiological responses to several organisms. Daphnia magna is a common model organism for ecotoxicology and was exposed to sub-lethal concentrations of BPA, BPF, and BPS to investigate disruption to metabolic profiles. Targeted metabolite analysis by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used to measure polar metabolites extracted from D. magna, which are linked to a range of biochemical pathways. Multivariate analyses and individual metabolite changes showed similar non-monotonic concentration responses for all three bisphenols (BPA, BPF, and BPS). Pathway analyses indicated the perturbation of similar and distinct pathways, mostly associated with protein synthesis, amino acid metabolism, and energy metabolism. Overall, we observed responses that can be linked to a chemical class (bisphenols) as well as distinct responses that can be related to each individual bisphenol type (A, F, and S). These findings further demonstrate the need for using metabolomic analyses in exposure assessment, especially for chemicals within the same class which may disrupt the biochemistry uniquely at the molecular-level.
... As a result, BPS is ubiquitous in the environment. In recent years, BPS pollutants can be detected in many canned foods, all kinds of water bodies, and even human blood and neonatal umbilical cord blood (Danzl et al., 2009;Gallart-Ayala et al., 2011;Liao et al., 2012b). Unfortunately, animal experiments revealed to the public that BPS was not as absolutely safe as considered. ...
Bisphenol S (BPS) is an endocrine disruptor which is widely used in commercial plastic products. Previous studies have shown that exposure to BPS has toxic effects on various aspects of mammalian, but there are few reports about reproductive toxicity. In order to investigate the effects of maternal BPS exposure on the reproductive of F1 and F2 female mice, the pregnant mice were orally administered with different dosages of BPS only once every day from 12.5 to 15.5 days post-coitus (dpc). The results showed that maternal BPS exposure to 2 μg per kg of body weight per day (2μg/kg) and 10μg/kg accelerated the meiotic prophase I (MPI) of F1 female mice and the expression of the genes related to meiotic were increased. Further studies showed that maternal BPS exposure resulted in a significant increase in the percentage of oocytes enclosed in primordial follicles in the 3 days post-partum (3 dpp) ovaries of F1 female mice. And at the time of 21 days post-partum (21 dpp) in F1 female mice, the number of antral follicles were significantly lower compare to controls. In the study of five-week female mice of F1, we found that BPS disturbed the folliculogenesis, and the maturation rates and fertilization rates of oocytes were significantly decreased. Of note, maternal BPS exposure disrupted H3K4 and H3K9 tri-methylation levels in F1 ovaries. Maternal BPS exposure only affected the cyst breakdown in F2 female mice. Taken together, our results suggest that, maternal BPS exposure impaired the process of meiosis and oogenesis of F1 and F2 offspring, resulting in abnormal follicular development and serious damage to the reproduction.Maternal BPS exposure damaged the reproductive health of F1 and F2 offspring female mice and resulted in epigenetic alterations of F1 offspring female mice.
Bisphenol S derivatives (BDs) are being widely used as novel substitutes for BPA and BPA analogues (BPAs), causing pollution in various environmental compartments. However, the occurrence and fate of BDs in coastal waters are currently unknown. To broaden the lens on bisphenols in coastal waters, this study measured a broad suite of 23 bisphenols, including 12 BDs along with BPA and 10 BPAs, in water, suspended particulate matters (SPM), and sediment from eight major outlets of the Pearl River Delta, China (PRD). In addition to BPA and BPAs, all the 12 BDs were detected in the collected samples. The total concentration of 12 BDs ranged from 1.2 to 25 ng/L (median of 4.3 ng/L) in water samples, 0.80-13 ng/g dw (median of 3.0 ng/g dw) in SPM samples and 0.48-3.7 ng/g dw (median of 0.64 ng/g dw) in sediment samples. For most individual BDs, they had comparable concentrations to individual BPAs. In addition, logKd values of the frequently detected bisphenols, including BPA, BPS, BPF, 4-((4-Isopropoxyphenyl)sulfonyl)phenol (BPSIP), 2,4-bis(phenylsulfonyl)phenol (DBSP), and other 9 bisphenols, were significantly correlated with their logKow values (R2 = 0.38, p < 0.05), indicating that the partitioning of bisphenols between the aqueous and SPM phases were strongly influenced by hydrophobic interaction. Based on bisphenols' concentrations in water from the eight outlets of PRD, the estimated input fluxes of novel BDs (1900 kg/y) were found to be even higher than that of BPAs (550 kg/y). This indicates that the riverine input of BDs into the coastal environment is gradually increasing, which should be taken seriously in the future.
Due to the strict rules and restrictions on the utilization of bisphenol A (BPA) around the world, an emerging endocrine disrupting chemical, bisphenol S (BPS) has been widely utilized as a substitute and frequently detected in the environment, even in the human body. Although it has been widely studied in the aquatic systems, the fate and toxicological effect of BPS in soil invertebrates are poorly known. This study presented a comprehensive exploration into the attenuation, bioaccumulation, and physiological distribution of BPS in an ecologically significant soil invertebrate, as well as its subsequent ecotoxicological effect to earthworm for the first time. The E. fetida could promote the BPS attenuation in soil, with degradation rates of 92.8 ± 1.6 % and 98.6 ± 1.1 % at dosage of 1.0 mg/kg dry weight soil (DWS) and 0.1 mg/kg DWS, respectively. The bioaccumulation of BPS in the earthworm was up to 111.6 ± 6.0 mg/kg lipid and 12.9 ± 2.9 mg/kg lipid with the initial dosage of 1.0 mg/kg DWS and 0.1 mg/kg DWS, respectively. Furthermore, BPS could induce oxidative stress and the process of antioxidant defense in earthworm cells at relatively high dose (1.0 mg/kg DWS and 10.0 mg/kg DWS), suggesting potential risks of BPS to the soil environment. This study could contribute to a more in-depth understanding of the fate of BPS in soil-earthworm system, and indicate a necessity for better understanding the environmental fate and ecological risks of BPA substitutes in the future.
Bisphenol A (BPA) is a ubiquitous chemical compound constantly being released into the environment, making it one of the most persistent endocrine-disrupting chemical (EDC) in nature. This EDC has already been associated with developing various pathologies, such as diabetes, obesity, and cardiovascular, renal, and behavioral complications, among others. Therefore, over the years, BPA has been replaced, gradually, by its analog compounds. However, these compounds are structurally similar to BPA, so, in recent years, questions have been raised concerning their safety for human health. Numerous investigations have been performed to determine the effects BPA substitutes may cause, particularly during pregnancy and prenatal life. On the other hand, studies investigating the association of these compounds with the development of cardiovascular diseases (CVD) have been developed. In this sense, this review summarizes the existing literature on the transgenerational transfer of BPA substitutes and the consequent effects on maternal and offspring health following prenatal exposure. In addition, these compounds' effects on the cardiovascular system and the susceptibility to develop CVD will be presented. Therefore, this review aims to highlight the need to investigate further the safety and benefits, or hazards, associated with replacing BPA with its analogs.
Pollution of water resources is a high-priority global issue. Nanocomposite membrane technology is an advanced purification technology that offers superior separation and filtration of organic and inorganic contaminants from water along with prolonged life of the membrane. In this study, iron oxide (Fe2O3) nanoparticles (NPs) were synthesized using the facile sol–gel technique, modified by 3-Aminopropyl tri-ethoxy silane (APTES), and analyzed to identify the structural properties, functional groups, elemental constituents of the NPs, and the surface modification of Fe2O3 NPs by APTES. FTIR, EDX, and XRD analyses demonstrated that Fe2O3 NPs were successfully modified. Then, pristine polyvinylidene Fluoride (PVDF)-Polyethylene glycol (PEG) based membrane and composite membrane blended with modified Fe2O3 NPs were fabricated via non-solvent induced phase inversion (NIPs) technique. The resultant fabricated membranes were analyzed by the contact angle, FESEM, EDX, surface zeta-potential, porosity, flux, resistance to fouling, and bisphenol F (BPF) rejection. The flux, resistance to fouling, and BPF rejection were enhanced with the functionalized Fe2O3 NPs loading increment. Also, the membrane blended with 1.5 wt% of modified Fe2O3 NPs displayed a remarkable performance with fluxes of 125.47 L/m² h and 117.31 L/m² h, least contact angle of 58.5° and superior BPF rejection (90.69%) compared to other membranes. The results of anti-fouling tests indicated a superior flux recovery ratio (FRR) and relative flux reduction (RFR) of 78.83% and 14.05% for membrane with 1.5 wt% Fe2O3 NPs following three cycles of filtration for a complete 5 h which is considerably higher than other membranes.
The UN Environmental Protection Agency has recognized 4-n-Nonylphenol (NP) and bisphenol A (BPA) as among the most hazardous chemicals, and it is essential to minimize their concentrations in the wastewater stream. These industrial chemicals have been witnessed to cause endocrine disruption. This report describes the straightforward hydrothermal approach adopted to produce Ce0.1La0.9MnO3 (CLMO) perovskite’s structure. Several physiochemical characterization approaches were performed to understand the Ce0.1La0.9MnO3 (CLMO) perovskite crystalline phase, element composition, optical properties, microscopic topography, and molecular oxidation state. Here, applying visible photon irradiation, the photocatalytic capability of these CLMO nanostructures was evaluated for the elimination of NP and BPA contaminants. To optimize the reaction kinetics, the photodegradation of NP and BPA pollutants on CLMO, perovskite was studied as a specification of pH, catalyst dosage, and initial pollutant concentration. Correspondingly, 92% and 94% of NP and BPA pollutants are degraded over CLMO surfaces within 120 and 240 min, respectively. Since NP and BPA pollutants have apparent rate constants of 0.0226 min−1 and 0.0278 min−1, respectively, they can be satisfactorily fitted by pseudo-first-order kinetics. The decomposition of NP and BPA contaminants is further evidenced by performing FT-IR analysis. Owing to its outstanding photocatalytic execution and simplistic separation, these outcomes suggest that CLMO is an intriguing catalyst for the efficacious removal of NP and BPA toxicants from the aqueous phase. This is pertinent for the treatment of endocrine-disrupting substances in bioremediation.
Bisphenol AF (BPAF) is one of the substitutes for bisphenol A (BPA), which has endocrine-disrupting, reproductive and neurological toxicity. BPAF has frequently been detected in the aquatic environment, which has been a long-term threat to the health of aquatic organisms. In this study, female marine medaka (Oryzias melastigma) were exposed to 6.7 μg/L, 73.4 μg/L, and 367.0 μg/L BPAF for 120 d. The effects of BPAF on behavior, growth, liver and ovarian histology, gene transcriptional profiles, and reproduction of marine medaka were determined. The results showed that with the increase of BPAF concentration, the swimming speed of female marine medaka showed an increasing trend and then decreasing trend. BPAF (367.0 μg/L) significantly increased body weight and condition factors in females. BPAF (73.4 μg/L and 367.0 μg/L) significantly delayed oocyte maturation. Exposure to 367.0 μg/L BPAF showed an increasing trend in the transcript levels of lipid synthesis and transport-related genes such as fatty acid synthase (fasn), sterol regulatory element binding protein (srebf), diacylglycerol acyltransferase (dgat), solute carrier family 27 member 4 (slc27a4), fatty acid-binding protein (fabp), and peroxisome proliferator-activated receptor gamma (pparγ) in the liver. In addition, 6.7 μg/L BPAF significantly down-regulated the expression levels of antioxidant-related genes [superoxide dismutase (sod), glutathione peroxidase (gpx), and catalase (cat)], and complement system-related genes [complement component 5 (c5), complement component 7a (c7a), mannan-binding lectin serine peptidase 1 (masp1), and tumor necrosis factor (tnf)] were significantly up-regulated in the 73.4 and 367.0 μg/L groups, which implies the effect of BPAF on the immune system in the liver. In the hypothalamic-pituitary-ovarian axis (HPG) results, the transcription levels of estrogen receptor α (erα), estrogen receptor β (erβ), androgen receptor (arα), gonadotropin-releasing hormone 2 (gnrh2), cytochrome P450 19b (cyp19b), aromatase (cyp19a), and luteinizing hormone receptor (lhr) in the brain and ovary, and vitellogenin (vtg) and choriogenin (chg) in the liver of 367.0 μg/L BPAF group showed a downward trend. In addition, exposure to 367.0 μg/L BPAF for 120 d inhibited the spawning behavior of marine medaka. Our results showed that long-term BPAF treatment influenced growth (body weight and condition factors), lipid metabolism, and ovarian maturation, and significantly altered the immune response and the transcriptional expression levels of HPG axis-related genes.
A reliable and sensitive analyzing method was developed and validated for determination of 13 novel bisphenol analogues (BPs) along with bisphenol A (BPA) in organism tissues. The complex organism tissues were treated by ultrasonic-assisted extraction using acetonitrile/formic acid (99:1, v/v), followed by successive purification using enhanced matrix removal-lipid sorbents and primary secondary amine sorbents. The BPs were finally determined by ultra-high performance liquid chromatography-tandem mass spectrometry after derivatization using pyridine-3-sulfonyl chloride. Satisfactory recoveries of 75 - 118% were obtained for the BPs, with good repeatability (RSD < 20%). Matrix interferences were efficiently diminished. The method quantification limits (MQLs) reached 0.003 - 0.1 ng g⁻¹ dry weight (dw). The validated method was successfully applied to a preliminary investigation of the BPs in wild marine organisms collected from the nearshore waters along the coast of Guangdong, China. Besides BPA, novel BPs such as bisphenol F, bisphenol AF, and tetrabromobisphenol A were also detected at < MDL - 15.5 ng g⁻¹ dw. This work laid a strong basis for further in-depth research on bioaccumulation of the novel BPs in the environment.
Mechanisms underlying severe male infertility are still largely elusive. However, recently, a single-cell transcription study by our group identified several differentially expressed coding genes in all the somatic cell types in testes of patients with idiopathic germ cell aplasia (iGCA). Here, we leverage this work by extending the analysis also to the non-coding portion of the genome. As a result, we found that 43 LncRNAs were differentially expressed in the somatic cells of these patients. Interestingly, a significant portion of the overexpressed LncRNAs was found to be a target of TAF9B, a transcription factor known to be involved in germ cell survival. Moreover, several overexpressed LncRNAs were also found to be activated in a mouse model of Sertoli cells treated with bisphenol A, a widespread environmental contaminant, long suspected to impair male fertility. Finally, a literature search for MEG3, a maternally imprinted LncRNA overexpressed as well in our patients, found it to be involved, among other things, in obesity and inflammation, known comorbidities of iGCA, ultimately suggesting that our findings deepen the understanding of the molecular insights coupled not only to the pathogenesis, but also to the clinical course of this class of patients.
Bisphenol A (BPA), a recognized endocrine‐disrupting chemical, is used in the production of epoxy and polycarbonate resins. Since human exposure to BPA has been associated with increased cancer susceptibility, the market has shifted to products often labeled as "BPA free" containing BPA analogs such as bisphenol F (BPF) and bisphenol S (BPS). However, the European legislation on BPF and BPS is still unclear. This study analyzed the effects of BPA, BPF and BPS exposure on human peripheral blood mononuclear cells by using in vitro micronucleus assay. Furthermore, it was investigated the impact of bisphenols exposure on human endogenous retroviruses (HERVs) expression, which are implicated with the pathogenesis of several human diseases. The micronucleus assay revealed a significant genotoxic effect in peripheral blood cells after exposure to BPA and BPF at concentrations of 0.1 μg/mL, 0.05 μg/mL and 0.025 μg/mL, and to BPS at 0.1 μg/mL and 0.05 μg/mL. In addition, BPA exposure seems to upregulate the expression of HERVs, while a downregulation was observed after BPF and BPS treatments. Overall, our data showed the toxic effect of BPA and its analogs on circulating cells in the blood and demonstrated that they could modulate the HERVs expression.
Bisphenol S (BPS) is a contaminant of emerging concern, its exposure and phytotoxicity towards plants, however, is scarce. This study aimed at revealing the BPS translocation in plants and phytotoxicity in the presence of Polystyrene (PS) microplastics. Results found that BPS and PS showed no effect on plant growth, indicating the tolerance of plants towards BPS and PS co-contamination. In addition, plants enriched BPS from soil, and a major part of absorbed BPS was accumulated in roots, as supported by the higher BCF value in roots compared with leaves. Besides, the low TF (<1) suggested the capacity of plants to accumulate BPS in roots, and less translocation to leaves. PS negatively affected the translocation of BPS in plants. PS with large size (5 μm) also increased the distribution of BPS in organelles. Exposure risk assessment suggested low concern of BPS carried in plants to human health. This study underlines the bioaccumulation of BPS in plants, and the effects of PS in the translocation process.
In this study, the magnetic urchin‐like NiCo2O4 materials (NiCo2O4‐w) were successfully prepared from the waste during the preparation of NiCo2O4/carbon cloth composite, and further evaluated as a peroxymonosulfate activator for removing bisphenol A (BPA). The effect of various factors such as initial solution pH, peroxymonosulfate (PMS) concentration, catalyst concentration and coexisting ions on the BPA removal were evaluated. The optimal factors were 0.20 g L−1 catalyst, 0.10 g L−1 PMS, 7.14 pH (unadjusted). Moreover, the NiCo2O4‐w exhibited good catalytic effects over wide ranges of pH (3.73 to 12). SO42‐ and H2PO4‐ remarkably inhibited the BPA removal, NO3‐ obviously inhibited the BPA removal, while Cl‐ and HCO3‐ had a little effect on the BPA removal. Singlet oxygen (1O2), superoxide radical (O2• –), hydroxyl radical (•OH) and sulfate radical (SO4• –) participated in the BPA degradation, of which O2• – and 1O2 played the leading role, especially O2• –. Oxygen vacancies, redox cycling pairs of Co(III)/Co(II) and Ni(III)/Ni(II) were responsible for PMS activation. Moreover, the degradation routes of BPA were rationally put forward. This present work not only presents that NiCo2O4‐w has a low‐cost, magnetically recoverable catalyst for high efficient degradation of wastewater containing BPA, but also opens up a new avenues to reduce environmental problems associated with waste treatment during the preparation of heterogeneous catalyst. This article is protected by copyright. All rights reserved.
Bisphenol S (BPS) has been widely applied as a replacement for BPA in industrial application, leading to the frequent detection in the environment. However, its impact on soil microbial communities has not been well reported. Here, effects of BPS exposure on soil microbial communities in the presence of polystyrene (PS) microplastics were revealed. Rapid degradation of BPS occurred with a degradation rate of up to 98.9 ± 0.001 % at 32 d. The presence of BPS reduced the diversity of soil microbial communities, and changed community structures. After BPS treatment, Proteobacteria, and its members Methylobacillus, Rhodobacteraceae and Mesorhizobium became dominant, and were considered as potential biomarkers indicating BPS contamination. Co-occurrence network analysis revealed the increased relationships of certain groups of microbes after BPS treatment. The resultant low stability and resilience towards environment disturbance of microbial community networks implied the biotoxicity of BPS towards soil ecosystems. The degradation and biotoxicity of BPS (p > 0.05) in soil was not affected by the presence of PS. Our findings showed that exposure to BPS could reshape soil microbial communities and impair the robustness of microbial co-occurrence networks.
Bisphenol analogues (BPs) have been widely used in industrial production, and caused harmful effects on biological reproduction and development. The occurrence characteristics of six BPs in multi-matrices, including truly dissolved phase, colloids, suspended particulate matter (SPM), sediment and fish samples from urban river were investigated. Bisphenol A (BPA) and bisphenol S (BPS) were the mostly detected in six BPs in the Yangtze River (Nanjing section). The total average concentration of BPs was 393.8 ng/L in truly dissolved phase, 57.4 ng/L in colloids, 255.2 ng/g in SPM and 34.5 ng/g in sediment. The adsorption capacity of SPM and sediment to BPs were weaker than that of colloids. For the spatial variation, the concentrations of BPs in the surface water of the downstream of urban rivers were 1.3–1.6 times higher than that of the upstream, and the BPs concentrations in the sediments downstream of the sewage treatment plant were significantly higher than that in other sites. In wild fish, muscle has a high accumulative potential for BPs, followed by brain and liver tissues, and BPA was the dominant BPs in brain tissues. Furthermore, BPs concentration in muscle of wild fish with different feeding habits was in the following order: filter-feeding fish > omnivorous fish > herbivorous fish, and which was significantly positively correlated with BPs concentration in traditionally dissolved phase and colloidal phase. Meanwhile, BPs concentration in benthic herbivorous fish might be also controlled by the BPs adsorbed in the sediment. Ecological risk assessment was conducted and demonstrated that BPs might pose a moderate risk to fish, a low risk to algae and daphnias. The detected BPs does not pose a health risk to human trough drinking water and eating fish alone.
Electronic waste (e-waste) pollution is of great concern due to the release of hazardous chemicals during the improper e-waste disposal. Many chemicals leached from e-waste were reported to pose estrogenic effects. To date, little is known regarding the occurrence and biological effects of estrogenic chemicals in sediments near an e-waste area. In this study, an effect-directed analysis (EDA) is applied to determine the estrogenic chemicals in sediments of four sites collected from a typical e-waste recycling city in China. Following screening with the ER-CALUX assay, the extract of sample with the most potent effect was subjected in fractionation using reverse phase liquid chromatography. Based on a target analysis for the active fractions, four compounds, including estrone, 17β-estradiol, 17α-ethinylestradiol and bisphenol A, were identified, and these contributed to 17% of the total toxic effects in the sample. A further nontarget analysis screened four candidates, namely diethylstilbestrol (DES), hexestrol (HES), nandrolone and durabolin, and the total contribution was found to be 48% from the active sample. Specifically, DES and HES were only detected in the active sample and were found to be the primary drivers of estrogenic effects. An examination of the identified chemicals in the four sites indicated that these estrogenic chemicals may originate from e-waste recycling, livestock excretion and domestic waste. These findings uncovered the estrogenic pollutants in sediments from an e-waste area. Considering single endpoint in biological assay is not abundant to screen chemicals with different toxic effects, further EDA studies with multiple endpoints are required to better understand the occurrence of representative or unknown chemicals in e-waste-polluted areas.
Legacy and alternative halogenated flame retardants (HFRs), such as polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), and dechlorane plus (DP), were measured in dated sediments from a highly industrialized lake in Korea. All HFRs were detected in almost all of the sediment depth layers for more than 70 years, indicating a history of long-term contamination. Similar historical trends in PBDEs, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and DP were observed in dated sediments, whereas decabromodiphenylethane (DBDPE), and 2-ethylhexyl-2,3,4,5-octabromo-1,3,3-trimethyl-1-phenylindane (OBIND) concentrations sharply increased since the 1990s. Moreover, the concentration ratios of DBDPE/BDE 209 increased from the early 1990s to the present. Our findings suggest that DBDPE and OBIND have been used as HFR alternatives. The historical record of the concentrations and profiles of legacy and alternative HFRs corresponded with industrial activities, consumption of FRs, and coastal development activities. Inventories of legacy and alternative HFRs were similar to those reported for highly industrialized regions around the globe.
Replacement chemicals for bisphenol A, such as bisphenol F (BPF) are detected in aquatic environments worldwide and can potentially exert negative effects on aquatic organisms. We synthesized peer-reviewed literature reporting molecular and physiological responses in zebrafish following exposure to BPF, as BPF is closely related to BPA structure and is a dominant replacement chemical in the marketplace. Global concentrations of BPF in aquatic environments were compiled and compared to physiological and behavioral impacts reported in zebrafish (e.g., developmental abnormalities, oxidative stress, immunotoxicity, endocrine disruption, and neurotoxicity). Using computational approaches, we elucidate BPF-mediated molecular networks and reveal novel biomarkers associated with BPF exposure. Functional classes of proteins including inflammatory cytokines, ATPases, peroxidases, and aromatic l-amino decarboxylases represent novel, underexplored targets of toxicity. Most revealing of this critical review is that few studies report biological responses to BPF at levels present in aquatic environments. Recommendations for future investigations based on knowledge gaps include: (1) Mechanistic studies in the central nervous system of zebrafish to address neurotoxicity; (2) Behavioral assays in zebrafish that assess the effects of BPF on anxiolytic, social, and fear-related behaviors; (3) Studies that broaden understanding of potential endocrine disrupting effects of BPF, for example insulin signaling is predicted to be sensitive to BPF exposure; (4) Studies into metabolic disruption with a focus on glutathione and aromatic amino acids, based upon pathway analysis data; (5) Studies utilizing mixture exposures with other BPA analogs to reflect environmental conditions more accurately.
Urine was used as a part of a human biomonitoring study based on the excretion kinetics of less-persistent contaminants, such as phthalates and bisphenol A (BPA). Despite the advantages of being non-invasive and easy to collect, urine can show a large variability of concentrations of phthalate metabolites and BPA within a person depending on sampling time. Therefore, it is essential to assess the variability of urinary concentrations for comprehensive sampling design in the context of exposure and risk assessments. In this study, 18 phthalate metabolites and eight BPs were measured in all spot urine (n = 401) collected from 12 participants for seven consecutive days to evaluate within- and between-person variabilities. The intraclass correlation coefficients (ICCs) for all spot urines were poor for monomethyl phthalate (ICC: 0.002) and BPA (0.121) but were moderate for monoethyl phthalate (0.514) and monobenzyl phthalate (0.462). Based on the results of di (2-ethylhexyl) phthalate (DEHP) metabolites, the half-life and differences in metabolic capability seem to affect the ICCs. Urinary mono (2-ethylhexyl) phthalate (MEHP), a primary metabolite of DEHP, was suggested as a short-term exposure marker of DEHP in our study. Creatinine- and specific gravity-adjusted concentrations of phthalate metabolites and BPs resulted in increased ICCs, implying requirements for randomly collected spot urine. Most analytes in the first morning voids (FMVs) were correlated significantly with those in the daily composites, suggesting the feasibility of FMVs to estimate the daily exposure dose. This study facilitates a more comprehensive sampling design and data interpretation strategy for human biomonitoring studies.
Bisphenol AF (BPAF), an endocrine-disrupting chemical, has been detected in various environmental media because of its wide industrial applications. Meanwhile, substances that are known to be toxic to the reproductive system have been observed to interfere with the development of the offspring following parental exposure. This study was aimed at determining the gender-dependent intergenerational effects of BPAF on offspring development following either paternal or maternal exposure of adult zebrafish to an environmental concentration of BPAF. Four-month-old zebrafish (F0) were exposed to 10 μg/L of BPAF for 28 days, the developmental endpoints of F1 embryos were then tested without further treatment with BPAF. The results show that paternal BPAF exposure decreased the hatching rate, increased mortality, and shortened the body lengths of F1 larval offspring. In addition, it changed DNA and m⁶A RNA methylation gene expression levels in F0 testes and F1 larvae. Although maternal exposure increased mortality and enhanced antioxidant enzyme activities in F1 larvae, only DNA methylation gene expression was altered in F0 ovaries and F1 larvae. In addition, a short term BPAF exposure of zebrafish embryos from 4 h post-fertilization (hpf) until 120 hpf similarly impaired the early development of the larvae but only at a level relatively higher than 10 μg/L; and DNA and RNA methylation gene expression was regulated to some extent in BPAF exposure groups. Overall, our results indicate the gender-specific effects of BPAF on offspring development and epigenetic modulations, suggesting a relatively high susceptibility within the exposure window during gametogenesis and early embryonic developmental stages to environmental chemicals.
Rapid urbanization and industrialization have introduced a variety of organic pollutants in the environmental matrices. Some of these chemicals are resistant to degradation and are termed as persistent organic pollutants (POPs). Humans and other living organisms have become highly susceptible to these environmental contaminants. For example, the semi-volatile organic compounds such as bisphenol A (BPA), phthalate esters (PAEs), and styrene monomers (SM) are extensively used in industrial production and served as intermediate complexes in different products used in daily activities. They have been classified as endocrine disruptors; therefore, exposure to these toxins creates various complications in humans and other living organisms in various ecosystems. Consequently, a balance is disturbed in the ecosystems, disintegrating the dependence of organisms on abiotic and biotic factors. This article aims to provide an overview of the commonly used plasticizers and their classification and applications, fate and transport, metabolism and mechanism of action. Subsequently, pollution load in different matrices of the riverine ecosystem has been targeted with special emphasis on the shift in ecological integrity. In addition, concerns over the use of these chemicals and their exposure have been highlighted that reflect a dire need to restrict and minimize their use to retrieve the ecological equilibrium.KeywordsImpactPlasticizersRiverine ecologyMicroplasticSustainability
Endocrine disrupting chemicals are exogenous chemicals which alter the functions of endocrine system. There are very few studies of occurrence and distribution of endocrine disrupting chemicals in water, soil and their potential human health risks under Indian conditions. In the present work, occurrence of eleven endocrine disrupting chemicals namely bisphenol-A, triclosan, triclocarbon, 4-nonylphenol, 4-tert octylphenol, methyl paraben, propyl paraben, butyl paraben, benzyl butyl phthalate, di (2-ethylhexyl) phthalate and di-n-butyl phthalate have been investigated in 20 river water samples, 5 ground water samples and 23 agricultural soil samples collected from 26 sampling points of different agro-climatic zones of India during 2019–2020. Instrument detection and quantification limits of different endocrine disrupting chemicals using LC–MS/MS varied from 0.001 to 0.05 and 0.005–0.1 µg/mL, respectively. Detection frequencies of bisphenol A, 4-nonylphenol, 4-tert octylphenol and di-n-butyl phthalate were 100% in river water samples. In ground water samples di-n-butyl phthalate, benzyl butyl phthalate, di (2-ethylhexyl) phthalate, triclosan, triclocarbon, 4-tert octylphenol, 4-nonylphenol, propyl paraben and butyl paraben and in soils 4-tert octylphenol, 4-nonylphenol, bisphenol-A and di-n-butyl phthalate were detected in 100% sample. High mean concentrations of di (2-ethylhexyl) phthalate were recorded in river waters (2706.135 µg/L), ground waters (3203.33 µg/L) and agricultural soils (1005.490 ng/g). Other chemicals detected in high concentrations were 4-tert octylphenol (180.680–829.93 µg/L), di-n-butyl phthalate (117.492–182.29 µg/L) and bisphenol-A (13.99–228.03 µg/L). Widespread distribution and high concentrations of these chemicals in water and soil is a cause of concern and, therefore, continued monitoring of these chemicals in different environmental matrices is the need of the hour.
Chromatography combined with mass spectrometry is the most commonly used detection technology, and it offers the advantages of high sensitivity and high selectivity. However, the contents of bisphenols (BPs) in water samples are at the ng/L level. Even if the BPs contents are determined by mass spectrometry, the samples must be pretreated and enriched. A quick, easy, inexpensive, effective, rugged, and safe technique (QuEChERS) can offer advantages such as cost effectiveness and time efficiency. The application of QuEChERS is currently extended to the analysis of contaminants in food and water samples. In this work, QuEChERS coupled with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was proposed for the determination of eight BPs in surface water. Method optimization was carried out in terms of process efficiency (PE), which included the matrix effect (ME) and extraction recovery (RE). First, the water samples were extracted with 10 mL ethyl acetate and cleaned with 50 mg primary secondary amine (PSA) and 50 mg graphitized carbon black (GCB). Then, the organic layer was collected and evaporated to dryness under nitrogen flow (40 ℃). Finally, the extracts were redissolved in 0.5 mL of a methanol-water (1∶1, v/v) mixture and subjected to UPLC-MS/MS analysis. Chromatographic separation was accomplished on a Waters ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm) with gradient elution. Methanol and 0.1 mmol/L ammonium bicarbonate aqueous solution were used as the mobile phases. The eight BPs were analyzed by MS/MS with negative electrospray ionization (ESI-) and in the multiple reaction monitoring (MRM) mode. The matrix matching external standard method was used for quantitative determination. The eight compounds could be analyzed within 8 min. Under the optimized conditions, the calibration curves showed good linearities for the eight BPs, and the coefficients of determination (R2) were greater than 0.9990. The limits of detection (LODs, S/N=3) and limits of quantification (LOQs, S/N=10) were in the ranges of 0.1-2.3 ng/L and 0.3-6.1 ng/L, respectively. The average recoveries of the eight BPs in river water samples were 78.8%-116.6%, and the corresponding relative standard deviations (RSDs) were 1.8%-9.0% (n=6). This method was applied to the analysis of BPs pollution in Guangyuan section of Jialing river and its tributaries, and widespread pollution was confirmed. The detection rate of BPA was 100% with a content of 6.15-90.03 ng/L, and the detection rate of BPS was 91%, with the contents being in the range not detected (nd) to 4.63 ng/L. The method established in this study allowed for the rapid enrichment and purification of the eight BPs in water. With its advantages of simplicity, rapidness, high sensitivity, and low cost, the method can be used for the rapid determination of trace BPs in surface water such as lake water and river water.
Bisphenol analogues (BPs) are heavily used and negatively affect the health of human beings, however, there is little knowledge regarding human exposure to BPs other than BPA. This study aims to assess human exposure to BPs through investigating pooled urine and wastewater samples. Twenty-four pooled urine samples were prepared from 960 specimens (classified by age and gender). Wastewater samples were collected from six major wastewater treatment plants (WWTPs) in Guangzhou, South of China. BPA, BPS, and BPAF were widely detected in urine samples, with a median concentration of 0.96, 0.42, and 0.15 μg/L, respectively. Median urinary levels of BPA and BPS were higher in males than females (p > 0.05). In addition, BPA and BPS urinary levels in young adults (15–30 years old) were greater than those in children (0–15 years old) (p > 0.05). Nevertheless, most of the BPs were detected in wastewater samples, of which BPA and BPS were predominant BPs, with a median concentration of 1.0 and 0.29 μg/L. The average per capital mass loads of ΣBPs on the weekdays of mix typed WWTP was much higher than those of the weekends. Nonetheless, the average loads of ΣBPs on the weekdays of domestic WWTP was slightly lower than those of the weekends. This indicated that important sources of BPs might include industrial wastewater and household cleaning products. Urinary BPA, BPS, and BPAF accounted for less than 5% per capital mass loads in wastewater, suggesting that much of the BPA, BPS, and BPAF in municipal wastewater originate non-human excretion. Hence, the wastewater-based epidemiology (WBE) approach based on parent compounds is not available for assessing human exposure to BPs, neither for other industrial chemicals with diverse sources in municipal wastewater. These results contributes to the development of an efficient surveillance system which can provide insight in the trends of human exposure of BPs.
Advanced oxidation processes (AOPs) based on the metal-organic frameworks (MOFs) and peroxymonosulfate (PMS) have been demonstrated as promising methods for the degradation of contaminants. In this study, the degradation of bisphenol AF (BPAF) by activated PMS via amino-modified metal-organic frameworks (AMOF) was investigated thoroughly. BPAF could be efficiently removed (94.1%) in the optimal condition. The decontamination of BPAF could be accelerated significantly with the increasing temperature, and a highly stable degradation performance was observed at a wide pH range. Quenching experiments and electron paramagnetic resonance (EPR) tests revealed that sulfate radical (SO4–•), hydroxyl radical (HO•), singlet oxygen (¹O2), and superoxide radical (O2–•) were produced synergistically in the AMOF/PMS system. Chloride ion (Cl–) exhibited a dual influence on BPAF removal, while other anions and NOM could hinder the degradation rate mildly. A total of fifty-two intermediates were identified using UHPLC-MS/MS method and four main degradation pathways were proposed based on the density functional theory (DFT) calculation, including the frontier molecular orbital theory (FMO), natural population analysis (NPA), and Fukui function. Finally, the Quantitative Structure Activity Relationship (QSAR) method for Toxicity Estimation Software Tool (TEST) was applied to estimate the accurate toxicity of BPAF and degradation byproducts. This study exhibited the promising potential for the decontamination of BPAF in the water via the AMOF based AOPs.
In this work, degradation of bisphenol F (BPF), bisphenol AF (BPAF) and bisphenol S (BPS) by peroxymonosulfate (PMS) with TiO2 nano-tubes arrays (TiO2NTAs) under simulated sunlight irradiation was investigated and compared for the first time. All three bisphenols exhibited appreciable degradation following the order of BPS < BPAF < BPF, and acidic conditions were more conducive to their degradation. The SO4•-, ·OH, h⁺ and •O2⁻ were all identified in three bisphenols degradation processes. Among these, SO4•- and •O2⁻ were proven to play a dominant role in BPF oxidation process, but SO4•- and h⁺ were confirmed as the main reactive species for BPAF and BPS removal. Owing to the different reactive species worked in different bisphenols degradation processes, the influences of inorganic anions on three bisphenols degradation were also different. By analyzing the oxidation intermediates of the three bisphenols, it was found that there were some common degradation pathways including bond-cleavage and hydroxylation of the benzene ring shared by three bisphenols. Besides, some specific degradation pathways were also identified, for example, the self-coupling was found in BPF and BPS degradation process, while the benzene ring splitting was occurred only in BPAF transformation process
Bisphenol analogues (BPs), triclocarban (TCC), and triclosan (TCS) are well-known environmental endocrine disrupters. Many studies have characterized their occurrence in the freshwater environment. However, their environmental behaviors in the coastal marine environment remain poorly understood. Here, matched seawater and sediment samples were collected from the East China Sea, and analyzed for 13 BPs (including halogenated derivatives of bisphenol A), TCC, and TCS. Bisphenol A (BPA; mean 23 ng/L) was the predominant BP in seawaters, followed by tetrabromobisphenol A (TBBPA; 2.3 ng/L) and bisphenol S (BPS; 2.2 ng/L). Seawater concentrations of TCS (<LOD–8.7 ng/L) were much higher (p < 0.01) than that of TCC (<LOD–0.33 ng/L). In sediments BPA was still the major BP (mean 13 ng/g dw, dry weight), followed by bisphenol F (1.6 ng/g dw) and BPS (0.69 ng/g dw). All sediment samples contained measurable TCC (0.12–6.6 ng/g dw), while TCS was occasionally detected. For the first time, this study reports the environmental occurrence of bisphenol M and 4,4′-sulfonylbis (2-aminophenol) (a first discovered BPS analogue) in seawaters and sediments. Spatially, inshore seawater and sediment samples contained higher (p < 0.01) BPA and BPS concentrations, compared with offshore samples. The mean log-transformed sediment-seawater partitioning coefficients (log Koc) ranged from 2.3 (TBBPA) to 4.0 (TCC). The log Koc values of BPA, BPS, and BPAF were lower than those previously reported in the freshwater environment. Overall, this study provides first data on the spatial distribution patterns and partitioning behaviors of BPs, TCC, and TCS in marine environment.
Bisphenol A and its derivatives are recognized as endocrine disruptors based on their complex effects on estrogen receptor (ER) signaling. While the effects of bisphenol derivatives on ERα have been thoroughly evaluated, how these chemicals affect ERβ signaling is less well understood. Herein, we sought to identify novel ERβ ligands using a radioligand competitive binding assay to screen a chemical library of bisphenol derivatives. Many of the compounds identified showed intriguing dual activities as both ERα agonists and ERβ antagonists. Docking simulations of these compounds and ERβ suggested that they bound not only to the canonical binding site of ERβ, but also to the coactivator binding site located on the surface of the receptor, suggesting that they act as coactivator binding inhibitors (CBIs). Receptor-ligand binding experiments using wild-type and mutated ERβ support the presence of a second ligand-interaction position at the coactivator binding site in ERβ, and direct binding experiments of ERβ and a coactivator peptide confirmed that these compounds act as CBIs. Our study is the first to propose that bisphenol derivatives act as CBIs, presenting critical insight for the future development of ER signaling-based drugs and their potential to function as endocrine disruptors.
Bisphenol A (BPA) is used as a monomer in a number of consumer products, including baby bottles and sippy cups. Some jurisdictions around the world (including Canada) have regulated the production, advertising or selling polycarbonate baby bottles with BPA. Following the ban, makers have opted for alternative materials to BPA [named BPA analogues, BPAAs], which may not be as safe as promoted. The objective of this project was to conduct a migration study in baby bottles and sippy cups, and analyze 16 BPAAs, as a follow-up on the BPA migration study conducted by Health Canada in 2009. Baby bottles (20 brands) and sippy cups (13 brands) were tested for migration of BPAAs. The most commonly detected analytes in baby bottles were BPS, BPA, BPF, BPAF, BPM and BPTMC with detection frequency (DF) of more than 50%. In sippy cups, only BPA, BPS and BPF were frequently detected. The mean concentration of BPA in baby bottle leachate was 31.5 ng/L in water simulant whereas a 1.4-fold increase was seen in 50% EtOH simulant. Similarly, a 1.4-fold increase was seen in the mean concentration of BPS in 50% EtOH simulant, when compared to the mean concentration of 2.33 ng/L in water simulant. Increasing median concentration was observed for BPA as the ethanol content of the simulant increased (water<10% EtOH<50% EtOH). The concentration of BPS and BPA was higher in sippy cups than that in their matched brand of baby bottles with the 50% EtOH simulant. Although most of the target analytes were detected in baby bottles, their concentrations were low and no migration was observed for any of the analytes with increasing incubation time. Therefore, it is likely that known BPA analogues are not present in the polymers used in the manufacture of most of the baby bottle brands sold in Canada.
Bisphenol A (BPA) is a chemical compound commonly used in the production of plastics for daily lives and industry. As BPA is well known for its adverse health effects, several alternative materials have been developed. This study comprehensively analyzed the toxicity of BPA and its three substitutes including bisphenol S (BPS), bisphenol F (BPF), and tetramethyl bisphenol F (TMBPF) on aging, healthspan, and mitochondria using an in vivo Caenorhabditis elegans (C. elegans) model animal and cultured mammalian fibroblast cells. C. elegans treated with 1 mM BPA exhibited abnormalities in the four tested parameters related to development and growth, including delayed development, decreased body growth, reduced reproduction, and abnormal tissue morphology. Exposure to the same concentration of each alternative including TMBPF, which has been proposed as a relatively safe BPA alternative, detrimentally affected at least three of these events. Moreover, all bisphenols (except BPS) remarkably shortened the organismal lifespan and increased age-related changes in neurons. Exposure to BPA and BPF resulted in mitochondrial abnormalities, such as reduced oxygen consumption and mitochondrial membrane potential. In contrast, the ATP levels were noticeably higher after treatment with all bisphenols. In mammalian fibroblast cells, exposure to increasing concentrations of all bisphenols (ranging from 50 µM to 500 µM) caused a severe decrease in cell viability in a dose-dependent manner. BPA increased ATP levels and decreased ROS but did not affect mitochondrial permeability transition pores (mPTP). Notably, TMBPF was the only bisphenol that caused a significant increase in mitochondrial ROS and mPTP opening. These results suggest that the potentially harmful physiological effects of BPA alternatives should be considered.
Bisphenol A (or BPA) is a toxic endocrine disrupting chemical that is released into the environment through modern manufacturing practices. BPA can disrupt the production, function and activity of endogenous hormones causing irregularity in the hypothalamus-pituitary-gonadal glands and also the pituitary-adrenal function. BPA
has immuno-suppression activity and can downregulate T cells and antioxidant genes. The genotoxicity and cytotoxicity of BPA is paramount and therefore, there is an immediate need to properly detect and remediate its influence. In this review, we
discuss the toxic effects of BPA on different metabolic systems in the human body, followed by its mechanism of action. Various novel detection techniques (LC-MS, GCMS, capillary electrophoresis, immunoassay and sensors) involving a pretreatment
step (liquid-liquid microextraction and molecularly imprinted solid-phase extraction) have also been detailed. Mechanisms of various remediation strategies, including biodegradation using native enzymes, membrane separation processes, photocatalytic
oxidation, use of nanosorbents and thermal degradation has been detailed. An overview of the global regulations pertaining to BPA has been presented. More investigations are required on the efficiency of integrated remediation technologies rather than standalone methods for BPA removal. The effect of processing operations on BPA in food matrices is also warranted to restrict its transport into food products
A group of compounds structurally similar to bis(4-hydroxyphenyl)propane (bisphenol A, BPA) are called bisphenols (BPs), and some of them can partially replace BPA in industrial applications. The production and consumption of BPs other than BPA, especially those of bis(4-hydroxyphenyl)methane (bisphenol F, BPF) and bis(4-hydroxyphenyl)sulfone (bisphenol S, BPS), have increased recently, leading to their detection as contaminants in the aquatic environment. The three compounds tested 100% positive for estrus response in 1936 and concerns about their health risks have been increasing. Abundant data on degradation of bisphenols (BPs) has been published, but results for biodegradation of BPs in seawater are lacking. However, several research groups have focused on this topic recently. In this study, the biodegradation behaviors of three BPs, namely BPA, BPF and BPS, in seawater were investigated using TOC Handai (TOC, potential test) and river (sea) die-away (SDA, simulation test) methods, which are both a kind of river-die-away test. The main difference between the tests is that indigenous microcosms remain in the sampled raw seawater for the SDA experiments, but they are removed through filtration and dispersed into artificial seawater for the TOC experiments. The BPs, except for BPS, were degraded using both methods. The SDA method produced better biodegradation results than the TOC method in terms of degradation time (both lag and degradation periods). Biodegradation efficiencies were measured at 75-100% using the SDA method and 13-63% using the TOC method. BPF showed better degradation efficiency than BPA, BPF was > 92% and BPA 83% depleted according to the SDA tests. BPS degradation was not observed. As a conclusion, the biodegradability of the three BPs in seawater could be ranked as BPF > BPA > BPS. BPF is more biodegradable than BPA in seawater and BPS is more likely to accumulate in the aquatic environment. BPS poses a lower risk to human health and to the environment than BPA or BPF but it is not amenable to biodegradation and might be persistent and become an ecological burden. Thus other degradation methods need to be found for the removal of BPS in the environment.
For decades, studies of endocrine-disrupting chemicals (EDCs) have challenged traditional concepts in toxicology, in particular the dogma of "the dose makes the poison," because EDCs can have effects at low doses that are not predicted by effects at higher doses. Here, we review two major concepts in EDC studies: low dose and nonmonotonicity. Low-dose effects were defined by the National Toxicology Program as those that occur in the range of human exposures or effects observed at doses below those used for traditional toxicological studies. We review the mechanistic data for low-dose effects and use a weight-of-evidence approach to analyze five examples from the EDC literature. Additionally, we explore nonmonotonic dose-response curves, defined as a nonlinear relationship between dose and effect where the slope of the curve changes sign somewhere within the range of doses examined. We provide a detailed discussion of the mechanisms responsible for generating these phenomena, plus hundreds of examples from the cell culture, animal, and epidemiology literature. We illustrate that nonmonotonic responses and low-dose effects are remarkably common in studies of natural hormones and EDCs. Whether low doses of EDCs influence certain human disorders is no longer conjecture, because epidemiological studies show that environmental exposures to EDCs are associated with human diseases and disabilities. We conclude that when nonmonotonic dose-response curves occur, the effects of low doses cannot be predicted by the effects observed at high doses. Thus, fundamental changes in chemical testing and safety determination are needed to protect human health.
Bisphenol A (BPA) is a base chemical used extensively in many consumer products. BPA and its analogues are present in environmental and human samples. Many endocrine-disrupting chemicals, including BPA, have been shown to activate the pregnane X receptor (PXR), a nuclear receptor that functions as a master regulator of xenobiotic metabolism. However, the detailed mechanism by which these chemicals activate PXR remains unknown.
We investigated the mechanism by which BPA interacts with and activates PXR and examined selected BPA analogues to determine whether they bind to and activate PXR.
Cell-based reporter assays, in silico ligand-PXR docking studies, and site-directed mutagenesis were combined to study the interaction between BPA and PXR. We also investigated the influence of BPA and its analogues on the regulation of PXR target genes in human LS180 cells.
We found that BPA and several of its analogues are potent agonists for human PXR (hPXR) but do not affect mouse PXR activity. We identified key residues within hPXR's ligand-binding pocket that constitute points of interaction with BPA. We also deduced the structural requirements of BPA analogues that activate hPXR. BPA and its analogues can also induce PXR target gene expression in human LS180 cells.
The present study advances our understanding of the mechanism by which BPA interacts with and activates human PXR. Activation of PXR by BPA may explain some of the adverse effects of BPA in humans.
Bisphenol A (BPA) and bisphenol F (BPF) are widely used to manufacture plastics and epoxy resins. Both compounds have been shown to be present in the environment and are food contaminants, with, as a result, a low but chronic exposure of humans. However, the fate and possible bioactivation of these compounds at the level of human cell lines was not completely elucidated yet. In this study, we investigated the ability of human cells (intestinal cell line: LS174T, hepatoma cell line: HepG2, and renal cell line: ACHN) to biotransform BPA and BPF, and focused on the cytotoxicity and genotoxicity of these two bisphenols, through the use of a novel and efficient genotoxic assay based on the detection of histone H2AX phosphorylation. BPA and BPF were extensively metabolized in HepG2 and LS174T cell lines, with stronger biotransformation capabilities in intestinal cells than observed in liver cells. Both cell lines produced the glucuronide as well as the sulfate conjugates of BPA. Conversely, the ACHN cell line was found to be devoid of any metabolic capabilities for the two examined bisphenols. Cytotoxicity was tested for BPA, BPF, as well as one metabolite of BPF produced in vivo in rat, namely dihydroxybenzophenone (DHB). In the three cell lines used, we observed similar ranges of toxicity, with DHB being weakly cytotoxic, BPF exhibiting an intermediary cytotoxicity, and BPA being the most cytotoxic compound tested. BPA and DHB were not found to be genotoxic, whatever the cell line examined. BPF was clearly genotoxic in HepG2 cells. These results demonstrate that some human cell lines extensively metabolize bisphenols and establish the genotoxic potential of bisphenol F.
Bisphenol A (BPA), identified as an endocrine disruptor, is an industrially important chemical that is used as a raw material in the manufacture of many products such as engineering plastics (e.g., epoxy resins/polycarbonate plastics), food cans (i.e., lacquer coatings), and dental composites/sealants. The demand and production capacity of BPA in China have grown rapidly. This trend will lead to much more BPA contamination in the environmental media and in the general population in China. This paper reviews the current literature concerning the pollution status of BPA in China (the mainland, Hong Kong, and Taiwan) and its potential impact on human health. Due to potential human health risks from long-term exposure to BPA, body burden of the contaminant should be monitored.
Bisphenol A (BPA) is one of the highest-volume chemicals produced worldwide, and human exposure to BPA is thought to be ubiquitous. Thus, there are concerns that the amount of BPA to which humans are exposed may cause adverse health effects. Importantly, results from a large number of biomonitoring studies are at odds with the results from two toxicokinetic studies.
We examined several possibilities for why biomonitoring and toxicokinetic studies could come to seemingly conflicting conclusions.
We examined > 80 published human biomonitoring studies that measured BPA concentrations in human tissues, urine, blood, and other fluids, along with two toxicokinetic studies of human BPA metabolism.
The > 80 biomonitoring studies examined included measurements in thousands of individuals from several different countries, and these studies overwhelmingly detected BPA in individual adults, adolescents, and children. Unconjugated BPA was routinely detected in blood (in the nanograms per milliliter range), and conjugated BPA was routinely detected in the vast majority of urine samples (also in the nanograms per milliliter range). In stark contrast, toxicokinetic studies proposed that humans are not internally exposed to BPA. Some regulatory agencies have relied solely on these toxicokinetic models in their risk assessments.
Available data from biomonitoring studies clearly indicate that the general population is exposed to BPA and is at risk from internal exposure to unconjugated BPA. The two toxicokinetic studies that suggested human BPA exposure is negligible have significant deficiencies, are directly contradicted by hypothesis-driven studies, and are therefore not reliable for risk assessment purposes.
An environmentally friendly sample pretreatment system based on solid-phase microextraction (SPME) for the sensitive determination of bisphenol A (BPA), bisphenol S (BPS) and biphenol (BP) is described. Two derivatisation reactions to obtain volatile derivatives are compared. Derivatisation with acetic anhydride (AA) was performed in situ in a 5-mM Na2CO3/NaHCO3 buffer solution and analytes were extracted by direct immersion (DI) using a PA fibre (85 µm) at 90°C for 40 min with stirring at 1,500 rpm. For derivatisation with bis-(trimethylsilyl)trifluoroacetamide (BSTFA), the analytes were first extracted by DI using the PA fibre at 70°C for 40 min with stirring at 500 rpm. The fibre was then removed, dried in a nitrogen stream for 2 min and introduced into the headspace of BSTFA at 50°C for 30 s. After derivatisation, the analytes were desorbed in the injection port of the GC in the splitless mode at 280°C for 4 min. The separation was carried out by coupling gas chromatography with mass spectrometry in the selected ion monitoring mode, GC-MS(SIM). The method allowed the determination of the migrating levels of bisphenols found in food cans, and it was validated for linearity, detection and quantitation limits, selectivity, accuracy and precision. Detection limits ranged from 3 to 16 pg mL−1, depending on the compound, at a signal-to-noise ratio of 3. Recoveries obtained for spiked samples were satisfactory for all compounds. Levels of BPA were higher than those of BPS and the lowest contents were found for BP.
Figure
The amounts of bisphenols migrated from food cans are very low
Long-term environmental effects of chemical exposure have long been of concern and, more recently, chemicals which cause changes to the sexual development of exposed organisms have been identified. It is thought that low-level exposure to a wide range of chemicals may be affecting endocrine function, leading to a reduction in fertility and an increase in reproductive cancers. Endocrine Disrupting Chemicals reviews the scientific evidence and attempts to put the subject into context. Along with an overview of the issue, there is discussion of the specialised aspects in relation to wildlife; environmental oestrogens and male reproduction; and naturally occurring oestrogenic substances. With contributions from representatives of the Medical Research Council's Institute for Environment and Health and the US Environmental Protection Agency, the articles provide a comprehensive and detailed review of current issues. This book will be of interest to a wide readership, including industrial and environmental scientists, managers and policy makers.
Sediment and water samples collected from 32 locations in Ulsan Bay and adjacent inland areas were analyzed for polycyclic aromatic hydrocabons (PAHs), nonylphenol (NP), octylphenol (OP), bisphenol A (BPA), organochlorine (OC) pesticides (HCB, HCHs, CHLs, and DDTs), and polychlorinated biphenyls (PCBs) to characterize their spatial distribution and contamination status. PAHs were detected in nearly all sediment and water extracts from Ulsan Bay and its inland locations. The sedimentary PAH concentrations ranged from 17 to 3,100 ng/g on a dry weight basis (DW), which were predominated by two- and three-ring aromatic hydrocarbons in river and/or stream, and four- to six-ring compounds in Ulsan Bay sediment. Concentrations of PAHs in pore water samples were generally two or three orders magnitude less than those of corresponding sediment samples. Maximum concentrations of NP, OP, and BPA in sediments were 1,040, 120, and 54 ng/g DW, respectively. Concentrations of OP and BPA were, on average, 5- to 13-fold less than those of NP. PCB concentrations in sediment ranged from 1.4 to 77 ng/g DW, which were predominated by lower chlorinated congeners such as di- through pentachlorinated biphenyls. Among different OC pesticides analyzed, concentrations of DDTs were the greatest, ranging from 0.02 to 41.9 ng/g DW. NP concentrations were greater at inner locations proximal to municipal wastewater discharges into rivers and/or streams, whereas the concentrations of PCBs and PAHs were great near the sites of high industrial activities. Sediment-pore water partitioning coefficients correlated with those of reported K oc or K ow values for selected PAHs in Ulsan Bay, but these varied by an order of magnitude for stream and/or river sediments.
Masan Bay, located on the southeast coast of Korea, is a long and narrow inlet of a semi-closed bay that receives industrial and municipal wastewaters from the cities of Masan and Changwon. In this study, sediments collected from 28 locations on Masan Bay were analyzed for total organic carbon (TOC), nonylphenol (NP), octylphenol (OP), bisphenol A (BPA), organochlorine pesticides (HCB, HCHs, CHLs, and DDTs), individual polychlorinated biphenyl (PCB) congeners, and 16 polycyclic aromatic hydrocabons (PAHs) to characterize their spatial distribution and contamination status. Concentrations of NP in sediment ranged from 113 to 3890 ng/g on a dry weight basis (dry wt), whereas concentrations of OP and BPA were, on average, 20−110-fold less than those of NP. PAHs were predominated by 4−6-ring compounds with concentrations in the range of 54.1−1100 ng/g dry wt. Concentrations of PCBs in sediment, which were predominated by tetra- and pentachlorobiphenyl congeners, ranged from 10.3 to 148 ng/g, dry wt. Among different OC pesticides analyzed, concentrations of DDTs were the greatest, ranging from 0.4 to 12.6 ng/g dry wt. NP concentrations were greater at coastal locations proximal to the discharges of creeks from inland areas, whereas the concentrations of PCBs and PAHs were greater near the sites of industrial and shipping activities. Concentrations of target analytes were not related to TOC. Although the mean concentrations of PCBs and PAHs in sediments were less than the suggested sediment quality guidelines (SQG), their concentrations in some locations were close to or above the SQG for toxic effects in benthic organisms.
Bisphenol A has been reported to be a ubiquitous contaminant in indoor dust, and human exposure to this compound is well documented. Information on the occurrence of and human exposure to other bisphenol analogues is limited. In this study, eight bisphenol analogues, namely 2,2-bis(4-hydroxyphenyl)propane (BPA), 4,4'-(hexafluoroisopropylidene)diphenol (BPAF), 4,4'-(1-phenylethylidene)bisphenol (BPAP), 2,2-bis(4-hydroxyphenyl)butane (BPB), 4,4'-dihydroxydiphenylmethane (BPF), 4,4'-(1,4-phenylenediisopropylidene)bisphenol (BPP), 4,4'- sulfonyldiphenol (BPS), and 4,4'-cyclohexylidenebisphenol (BPZ), were determined in indoor dust samples (n = 156) collected from the United States (U.S.), China, Japan, and Korea. Samples were extracted by solid-liquid extraction, purified by automated solid phase extraction methods, and determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The total concentrations of bisphenols (∑BPs; sum of eight bisphenols) in dust were in the range of 0.026-111 μg/g (geometric mean: 2.29 μg/g). BPA, BPS, and BPF were the three major bisphenols, accounting for >98% of the total concentrations. Other bisphenol analogues were rare or not detected, with the exception of BPAF, which was found in 76% of the 41 samples collected in Korea (geometric mean: 0.0039 μg/g). The indoor dust samples from Korea contained the highest concentrations of both individual and total bisphenols. BPA concentrations in dust were compared among three microenvironments (house, office, and laboratory). The estimated median daily intake (EDI) of ∑BPs through dust ingestion in the U.S., China, Japan, and Korea was 12.6, 4.61, 15.8, and 18.6 ng/kg body weight (bw)/day, respectively, for toddlers and 1.72, 0.78, 2.65, and 3.13 ng/kg bw/day, respectively, for adults. This is the first report on the occurrence of bisphenols, other than BPA, in indoor dust.
Sediment from the upper Detroit and lower Rouge Rivers in southeastern Michigan, USA, were analyzed to examine the distribution of polychlorinated naphthalenes (PCNs), biphenyls (PCBs), dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs) as well as polycyclic aromatic hydrocarbons (PAHs) and alkylphenolic compounds such as butylphenol, octylphenol, and nonylphenol (NP). Sediments from a non–point source location in Lake Michigan were also analyzed for target compounds. Concentrations of target compounds in the upper Detroit and lower Rouge Rivers varied considerably among locations, and notable spatial variation existed. Concentrations of PCNs and PCDDs/PCDFs in sediments from the upper Detroit and lower Rouge Rivers ranged from 0.08 to 187 ng/g and 69 to 1420 pg/g dry weight, respectively. Total PCBs, PAHs, and NP concentrations ranged from 8 to 25,000, 17 to 44,000, and <10 to 60,000 ng/g dry weight, respectively. Concentrations of all target compounds except PCNs were significantly correlated with total organic carbon content of sediments. Similarly, concentrations of PCBs, PCDDs, and PCDFs were significantly correlated with each other. The distribution of organic contaminants in the upper reaches of the Detroit River and lower Rouge River suggested the presence of localized, but multiple, sources of contamination for each compound class. Conners Creek combined sewer overflow has been identified as one of the potential sources for the upper Detroit River, where the highest concentrations PCBs and PCDDs/PCDFs were found. Polycyclic aromatic hydrocarbon and NP concentrations were consistently high in sediment from the lower Rouge River. Analysis of data from selected locations suggested that PCNs contributed a greater proportion of the dioxin-like activity than PCBs and PCDDs/PCDFs contributed.
Sources, compositions, and historical records of polycyclic aromatic hydrocarbons (PAHs) in sediment cores collected from the Yellow Sea and the South China Sea were analyzed to investigate the influence of anthropogenic activities. The occurrence of PAHs was mainly derived from various combustion sources, especially the combustion of biomass and domestic coal. Uniform composition of sedimentary PAHs (52-62% of phenanthrene, benzo[b]fluoranthene, indeno[1,2,3-cd]pyrene, and benzo[g,h,i]perylene) suggested air-borne mixtures intractable to degradation. The concentrations of the sum of 15 PAHs (16 priority pollutants designed by the United States Environmental Protection Agency minus naphthalene; designed as Σ(15)PAH) in Yellow Sea sediment cores were generally higher than those in the South China Sea. The profiles of Σ(15)PAH concentrations recorded in the sediment cores closely followed historical socioeconomic development in China. In general, Σ(15)PAH concentrations started to increase from the background pollution level posed by agricultural economy at the turn of 20th century. In addition, a Σ(15)PAH concentration reduction was observed during the Chinese Civil War (1946-1949) and Great Cultural Revolution (1966-1976), suggesting them as setbacks for economic development in Chinese history. Increasing PAH emissions as a result of increasing coal combustion associated with the rapid urbanization and industrialization since the implementation of the Reform and Open Policy (since 1978) accounted for the fast growth of Σ(15)PAH concentrations in sediment cores. The decline of Σ(15)PAH concentrations from subsurface maximum until sampling time was inconsistent with current-day economic development in China, and may possibly suggest emission reductions due to decreasing proportional use of domestic coal and increasing consumption of cleaner energies (natural gas and liquefied petroleum gas).
As concern regarding the toxic effects of bisphenol A (BPA) grows, BPA in many consumer products is gradually being replaced with compounds such as bisphenol S (BPS). Nevertheless, data on the occurrence of BPS in human specimens are limited. In this study, 315 urine samples, collected from the general populations in the United States, China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam, were analyzed for the presence of total BPS (free plus conjugated) concentrations by high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). BPS was detected in 81% of the urine samples analyzed at concentrations ranging from below the limit of quantitation (LOQ; 0.02 ng/mL) to 21 ng/mL (geometric mean: 0.168 ng/mL). The urinary BPS concentration varied among countries, and the highest geometric mean concentration [1.18 ng/mLor 0.933 μg/g creatinine (Cre)] of BPS was found in urine samples from Japan, followed by the United States (0.299 ng/mL, 0.304 μg/g Cre), China (0.226 ng/mL, 0.223 μg/g Cre), Kuwait (0.172 ng/mL, 0.126 μg/g Cre), and Vietnam (0.160 ng/mL, 0.148 μg/g Cre). Median concentrations of BPS in urine samples from the Asian countries were 1 order of magnitude lower than the median concentrations reported earlier for BPA in the same set of samples, with the exception of samples from Japan. There were no significant differences in BPS concentrations between genders (male versus female), or among age groups (categorized as ≤ 19, 20-29, 30-39, 40-49, and ≥ 50 years), or races (Caucasian versus Asian). The daily intake (EDI) of BPS was estimated on the basis of urinary concentrations using a simple pharmacokinetic approach. The median EDI values of BPS in Japan, China, United States, Kuwait, Vietnam, Malaysia, India, and Korea were 1.67, 0.339, 0.316, 0.292, 0.217, 0.122, 0.084, and 0.023 μg/person, respectively. This is the first study to report the occurrence of BPS in human urine.
As the evidence of the toxic effects of bisphenol A (BPA) grows, its application in commercial products is gradually being replaced with other related compounds, such as bisphenol S (BPS). Nevertheless, very little is known about the occurrence of BPS in the environment. In this study, BPS was analyzed in 16 types of paper and paper products (n = 268), including thermal receipts, paper currencies, flyers, magazines, newspapers, food contact papers, airplane luggage tags, printing paper, kitchen rolls (i.e., paper towels), and toilet paper. All thermal receipt paper samples (n = 111) contained BPS at concentrations ranging from 0.0000138 to 22.0 mg/g (geometric mean: 0.181 mg/g). The overall mean concentrations of BPS in thermal receipt papers were similar to the concentrations reported earlier for BPA in the same set of samples. A significant negative correlation existed between BPS and BPA concentrations in thermal receipt paper samples (r = -0.55, p < 0.0001). BPS was detected in 87% of currency bill samples (n = 52) from 21 countries, at concentrations ranging from below the limit of quantification (LOQ) to 6.26 μg/g (geometric mean: 0.029 μg/g). BPS also was found in 14 other paper product types (n = 105), at concentrations ranging from <LOQ to 8.38 μg/g (geometric mean: 0.0036 μg/g; detection rate: 52%). The estimated daily intake (EDI) of BPS, through dermal absorption via handling of papers and currency bills, was estimated on the basis of concentrations and frequencies of the handling of papers by humans. The median and 95th percentile EDI values, respectively, were 4.18 and 11.0 ng/kg body weight (bw)/day for the general population and 312 and 821 ng/kg bw/day for occupationally exposed individuals. Among the paper types analyzed, thermal receipt papers were found to be the major sources of human exposure to BPS (>88%). To our knowledge, this is the first report on the occurrence of BPS in paper products and currency bills.
Concentrations of polybrominated diphenyl ethers (PBDEs) were determined in water and sediment collected from the artificial Lake Shihwa and surrounding creeks. Total concentrations of 23 PBDE congeners in water and sediment ranged from 0.16 to 11.0ngL(-1) and from 1.3 to 18700ngg(-1)dryweight, respectively. The concentrations of BDE 209 in water and sediment were 1-2 orders of magnitude higher than the total concentrations of other PBDE congeners. The concentrations of total PBDEs and BDE 209 in sediments were the highest compared to previously reported worldwide levels. The highest concentrations of PBDEs in water and sediments were found in creeks near industrial complexes. The PBDE concentrations gradually decreased with increasing distance from the creeks to the inshore and then offshore regions of the lake. BDE 209 was a major congener, accounting for 80% of the total PBDEs in water and sediment, consistent with a high consumption of deca-BDE for the brominated flame retardant market in Korea. Non-parametric multidimensional scaling ordination showed that surrounding creeks are major pathways of PBDE contamination associated with deca-BDE technical mixtures used in industrial complexes around Lake Shihwa. A significant correlation between total organic carbon and total PBDE concentration was found in sediments, and the correlation coefficients for individual PBDE congeners relatively increased from lower to higher brominated congeners.
Endocrine disruptor chemicals (EDCs), which are predominantly present in the environment, are able to mimic or antagonise the biological activity of hormones primarily through the interaction with specific receptors. The main consequences are adverse effects on the growth and development of reproductive organs, the induction of cancer and effects on neuronal differentiation. In this study, we investigated the ability of certain EDCs, Bisphenol A (BPA), Bisphenol B (BPB), Bisphenol F (BPF), 4-n Nonylphenol (NP) and Octylphenol (OP), belonging to a homogeneous group of phenol origin, to interfere with specific cellular processes, namely, proliferation, by using MCF-7 breast carcinoma cells, and differentiation, by using murine bone marrow dendritic cells. We correlated the data on cell growth with the stimulation of cell cycle progression, which could become a step in the development of cancer, and we established a proliferation ranking between the tested EDCs: NP>BPA>OP>BPB>BPF. In addition, we investigated the ability of NP, BPA and OP to induce the differentiation of dendritic cells, the powerful antigen-presenting cells of the immune system. The differentiation and activation of these cells could affect a well-regulated immune response and determine an allergic sensitisation. We found that BPA and NP were active in determining differentiation.
In 2011, the European Commission has restricted the use of Bisphenol A in plastic infant feeding bottles. In a response to this restriction, Bisphenol S is now often used as a component of plastic substitutes for the production of babybottles. One of the major concerns leading to the restriction of Bisphenol A was its weak estrogenic activity. By using two highly standardised transactivation assays, we could demonstrate that the estrogenic activity of Bisphenol A and Bisphenol S is of a comparable potency. Furthermore, some insights about the structure-activity relationships of these two chemicals and their metabolites could be gained from in silico predictions of their relative estrogen receptor-binding affinities and their liver phase-I biotransformation.
Although in vitro studies have indicated that Bisphenol AF (BPAF) might be a more dangerous endocrine disruptor than Bisphenol A (BPA), no information on reproductive toxicity in animals is available. In this study, the effects of BPAF exposure on the testis and the related mechanisms of toxicity were investigated. Sprague-Dawley (SD) male rats were exposed to BPAF (0, 2, 10, 50 and 200 mg/kg/d) for 14 days. Total cholesterol levels in serum were decreased in rats given a dose of 50 and 200 mg/kg/d. BPAF concentration in the testes increased with increasing doses of BPAF. Reduced serum testosterone and increased luteinizing hormone (LH) and follicle-stimulating hormone (FSH) levels were observed in rats in the higher dose groups. Furthermore, BPAF exposure resulted in a dramatic decline in genes and protein involved in cholesterol biosynthesis, transport and steroid biosynthesis. Similarly, the testicular mRNA levels of inhibin B, estrogen receptor (ERα) and luteinizing hormone receptor (LHR) also decreased in rats given a dosage of 200 mg/kg/d BPAF. Together, these data demonstrate that BPAF-induced inhibition of testosterone production primarily resulted from the alteration of genes and proteins in the testosterone biosynthesis pathway.
We have studied the distribution and value of phenolic endocrine disrupting chemicals (EDCs) in surface sediment samples taken from Anzali Wetland, Iran. These samples were collected from 22 stations during the time span of June-May 2010. In each of the sampling stations, we detected 4-nonylphenol (4-NP), octylphenol (OP), and bisphenol A (BPA) with maximal concentrations of 29, 4.3, and 7 μg g(-1) dry weight (dw), respectively. High levels of alkylphenols (APs) and BPA were also found near urban areas. Furthermore there were no significant differences between those stations in terms of the detected levels. One of the important factors in controlling the fate of these compounds in the aquatic environment appeared to be Total Organic Carbon (TOC). Hierarchical cluster analysis showed differences in the biomarker characteristics of EDCs and TOC between the stations. Our findings indicate that EDCs are ubiquitous in sediments from northeast Wetlands of Iran, contaminating the aquatic habitats in this area.
This paper describes an improved method for the extraction and analysis of seven endocrine disrupting chemicals with wide-ranging polarities from water and sediments using gas chromatography–tandem mass spectrometry (GC–MS/MS). The analytes were 4-tert-octylphenol, 4-nonylphenol, bisphenol A, estrone, 17β-estradiol, 17α-ethynylestradiol and 16α-hydroxyestrone. The optimised GC–MS/MS method produces increased selectivity and sensitivity compared to GC–MS, with limit of detection ranging from 0.01 to 0.49 ng L−1 in water and from 0.05 to 0.14 ng g−1 in sediment. Extraction from aqueous samples was performed by solid-phase extraction (SPE) and from sediment samples by microwave-assisted extraction (MAE). The improved method for the clean-up of sediment extracts carried out by SPE enhanced EDC recovery (86–102%) while reducing matrix interference and sample drying time. Derivatisation of final sample extracts was achieved using N,O-bis(trimethylsilyl)trifluoroacetamide and pyridine, and their stability was enhanced by reconstituting the derivatised extracts with hexane. The method was validated by spiking experiments which showed good recovery and reproducibility. The method was applied to samples taken from the Medway estuary in Kent, UK, where non-conservative behaviour of EDCs was demonstrated.
This work presents two analytical methods developed for measuring three components of polyethersulphone (PES) and applying them to the migration testing of 30 baby bottles made of PES. The study also provides migration results under the same conditions for bisphenol A (BPA) from 40 polycarbonate baby bottles using a well-established method adapted to low concentrations. For PES bottles, migration of diphenyl sulphone (DPS), 4,4'-dichlorodiphenyl sulphone (DCPS) and 4,4'-dihydroxydiphenyl sulphone (DHPS; also known as bisphenol S) was carried out using two different analytical methods with detection limits of 0.1-0.3 µg/kg, and, therefore, much below their respective European Commission Directive 2002/72/EC legislative migration limits of 50-3000 µg/kg, respectively. In parallel, 40 bottles made of polycarbonate were analysed for the migration of BPA using a method validated at EU level and modified to give a lower detection limit of 0.1 µg/kg. Migration tests were conducted into the simulant for milk 50% EtOH (as per Commission Regulation No. 321/2011 of 1 April 2011) according to the test conditions from the guidelines on test conditions for articles in contact with foodstuffs (with a focus on kitchenware) prepared by the EU Reference Laboratory and its network of National Reference Laboratories. None of the 30 bottles made of PES released any detectable amounts of DCPS or DHPS and only two bottles released a very low amount of DPS of ~1 µg/kg in the milk food simulant compared to a regulatory limit of 3000 µg/kg. For PC bottles, 32 bottles of 40 (80%) did not release BPA above the LOD of 0.1 µg/kg (in any of the three migration tests performed on each bottle). The other 20% of bottles exhibited only very minor migration, where the highest level in the first migration test was 1.83 µg/kg and most bottles did not release detectable BPA in the second and third test. Only one bottle, with a migration level of 1.08 µg/kg, in the first test still showed a detectable level in the last migration test (i.e. 0.42 µg/kg). It is important to note that the legal limit (European Commission Directive 2002/72/EC) was still 600 µg/kg for polycarbonate bottles at the time of purchase, preceding the precautionary ban taking effect from 1 June 2011 (Commission Directive 2011/8/EU; Commission Regulation No. 321/2011). This confirms that the likelihood of migration of BPA is very low and remains at very minute amounts. The results also suggest the absence of release from PES bottles based on the set of bottles investigated.
Bisphenol A (BPA) is used in a variety of consumer products, including some paper products, particularly thermal receipt papers, for which it is used as a color developer. Nevertheless, little is known about the magnitude of BPA contamination or human exposure to BPA as a result of contact with paper and paper products. In this study, concentrations of BPA were determined in 15 types of paper products (n = 202), including thermal receipts, flyers, magazines, tickets, mailing envelopes, newspapers, food contact papers, food cartons, airplane boarding passes, luggage tags, printing papers, business cards, napkins, paper towels, and toilet paper, collected from several cities in the USA. Thermal receipt papers also were collected from Japan, Korea, and Vietnam. BPA was found in 94% of thermal receipt papers (n = 103) at concentrations ranging from below the limit of quantitation (LOQ, 1 ng/g) to 13.9 mg/g (geometric mean: 0.211 mg/g). The majority (81%) of other paper products (n = 99) contained BPA at concentrations ranging from below the LOQ to 14.4 μg/g (geometric mean: 0.016 μg/g). Whereas thermal receipt papers contained the highest concentrations of BPA (milligram-per-gram), some paper products, including napkins and toilet paper, made from recycled papers contained microgram-per-gram concentrations of BPA. Contamination during the paper recycling process is a source of BPA in paper products. Daily intake (DI) of BPA through dermal absorption was estimated based on the measured BPA concentrations and handling frequency of paper products. The daily intake of BPA (calculated from median concentrations) through dermal absorption from handling of papers was 17.5 and 1300 ng/day for the general population and occupationally exposed individuals, respectively; these values are minor compared with exposure through diet. Among paper products, thermal receipt papers contributed to the majority (>98%) of the exposures.
Bisphenol A (BPA) is an industrial chemical used in the manufacture of polycarbon