Production of bisphenol A (BPA) analogues such as bisphenol F (BPF) and bisphenol AF (BPAF) has recently increased, due to clear evidence of adverse effects of BPA on humans and wildlife. Bisphenols ...(BPs) have already been released into aquatic environment without previous available information about potential adverse effects of BPs and their potential risk to aquatic ecosystems. In this study, lethal and sublethal effects of BPF and BPAF to bacteria, algae, crustacea and fish embryos were investigated and the results were compared to the adverse effects obtained for BPA. We found that BPAF was the most toxic compound to Daphnia magna, Danio rerio and Desmodesmus subspicatus; the lowest 72 h EC50 (median effective concentration) and 21 d NOEC (no observed effect concentration) values were determined at 2.2 mg/L regarding zebrafish hatching success and 0.23 mg/L of BPAF obtained for growth and reproduction of water fleas, respectively. In most cases, BPA was more toxic to D. magna, D. rerio and D. subspicatus in comparison to BPF, but pigmentation of zebrafish embryos after 48 h of exposure and reproduction of water fleas after 21-day D. magna reproductive test exposure to BPF were much more impaired. Risk quotients (measured environmental concentration/21 d NOEC) showed that BPA, BPF and BPAF are recently not chronically hazardous to the survival, reproduction and growth of water fleas in surface waters. On the other hand, we importantly show that currently present BPAF concentrations in surface waters could cause a potential ecological risk to aquatic organisms. In the near future, higher concentrations of BPF and BPAF in surface waters are anticipated and for this reason further testing using test systems with various aquatic species and endpoints are needed to provide additional information about toxic impacts of BPF and BPAF on aquatic biota.
•Higher toxicity of BPAF in comparison to BPF and BPA.•BPA was more toxic to the majority of tested organisms in comparison to BPF.•BPAF could cause ecological risk to aquatic organisms.•Industrial replacement of BPA with BPAF is questionable.
We reveal that BPAF was found to be more toxic to tested organisms than BPA and BPF and it could cause ecological risk to aquatic organisms.
•Influence of crosslinker/porogen ratio in SPE performance of polymer monoliths.•Simple method to adjust pore structure in robust materials for sample preparation.•Efficient preconcentration of ...bisphenols (EF = 279-375).
Polymer monoliths can be polymerised within different molds, but limited options are available for the preparation of free-standing polymer monoliths for analytical sample preparation, and in particular, solid-phase extraction (SPE). Commercial melamine-formaldehyde sponges can be used as supports for the preparation of polymer monoliths, due its flexibility, giving various shapes to monoliths. Herein, the crosslinker/porogen ratio of highly porous sponge-nested divinylbenzene (DVB) polymer monoliths has been evaluated. Monoliths prepared using different crosslinker/porogen ratios were applied to the extraction of bisphenol F, bisphenol A, bisphenol AF, and bisphenol B. Monoliths containing 50 wt % DVB and 50 wt % porogens presented the highest recovery of bisphenols. Under the optimised conditions, the developed method showed a linear range between 2.5 µg L−1 and 150 µg L−1 for BPA and BPAF, and between 5 µg L−1 and 150 µg L−1 for BPB and BPF. The limits of detection (LOD, S/N = 3) and limits of quantification (LOQ, S/N = 10) ranged from 0.36 µg L−1 to 1.09 µg L−1, and from 1.20 µg L−1 to 3.65 µg L−1, respectively. The recoveries for spiked bisphenols (10 µg L−1) in tap water and water contained in a polycarbonate containers were between 82 % and 114 %.
Distribution of the phenol urinary concentrations adjusted for specific gravity in the SEPAGES cohort during pregnancy (periods second (NT2 = 477) and third trimesters ((NT3 = 456), and infancy (2 ...months (NM2 = 152) and 1 year (NY1 = 100). Compounds with less than 4% detection are not shown (bisphenols F, B, AF and triclocarban). For the bisphenol A infant samples (2 months and 1 year) the concentrations of the conjugated form instead of the total form are presented as external contamination was suspected. Abbreviations: LOD = limit of detection, LOQ = limit of quantification.
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•Phenol concentrations were assessed accurately through the collection of repeated samples.•Pregnancy and early infancy, sensitive yet rarely analyzed periods were studied.•High detection rates of bisphenol A, parabens and triclosan in mothers and infants.•Concentrations for several phenols were higher at 12 months than during pregnancy.•Cashiers had higher bisphenol S but not bisphenol A levels than unemployed women.
Parabens, bisphenol A and triclosan have been forbidden or restricted in specific types of consumer goods in Europe and France. Limited biomonitoring data are available in France since the implementation of these regulations, and exposure data on infants is scarce worldwide. Understanding the predictors of phenol urinary concentrations will help identify potential targets for prevention.
We described levels, variability and predictors of exposure to 12 phenols in pregnant women and infants recruited between 2014 and 2017 in a French couple-child cohort.
Among 479 pregnant women and 150 of their infants, we studied phenol urinary concentrations in within-subject, within-period pools of repeated urine samples collected during the second and third trimesters of pregnancy (up to 42 samples per woman), at 2 months and 12 months (up to 14 samples per infant). Time trends and associations with demographic, protocol, occupational and behavioral factors were studied using interval censored models to accommodate for undetected and unquantified urine concentrations.
Detection rates were above 90% for bisphenol A, ethylparaben, methylparaben, benzophenone-3 and triclosan and below 5% for bisphenol AF, B, F and triclocarban. Median levels of bisphenol A, bisphenol S, methylparaben, ethylparaben and propylparaben at 12 months were similar or higher than during pregnancy. For pregnant women all phenols but benzophenone-3 and bisphenol S showed a linear decrease between 2014 and 2017 (p-values < 0.02). Women with the shortest education (primary and secondary school) had higher urinary concentrations of triclosan (β = 0.58 (95% confidence interval (CI), −0.04; 1.20)), ethyl (β = 0.43 (95%CI, 0.03; 0.84)) and propyl paraben (β = 1.39 (95%CI, 0.55; 2.24)) than those with the longest education. Cashiers had higher conccentrations of bisphenol S (β = 0.99 (95%CI, −0.11; 2.09)) but not of bisphenol A (β = −0.04 (95%CI, −0.26; 0.19)) than unemployed women.
Despite recent regulations, bisphenol A, triclosan and paraben detection rates were high in women and young infants. High bisphenol and paraben median levels at 12 months require further investigation as early infancy is a sensitive period for exposure to environmental contaminants.
Exposure of human fetuses to man-made estrogenic chemicals can occur through several sources. For example, fetal exposure to ethinylestradiol occurs because each year ≈3% of women taking oral ...contraceptives become pregnant. Exposure to the estrogenic chemical bisphenol A occurs through food and beverages because of significant leaching from polycarbonate plastic products and the lining of cans. We fed pregnant CD-1 mice ethinylestradiol (0.1 μg/kg per day) and bisphenol A (10 μg/kg per day), which are doses below the range of exposure by pregnant women. In male mouse fetuses, both ethinylestradiol and bisphenol A produced an increase in the number and size of dorsolateral prostate ducts and an overall increase in prostate duct volume. Histochemical staining of sections with antibodies to proliferating cell nuclear antigen and mouse keratin 5 indicated that these increases were due to a marked increase in proliferation of basal epithelial cells located in the primary ducts. The urethra was malformed in the colliculus region and was significantly constricted where it enters the bladder, which could contribute to urine flow disorders. These effects were identical to those caused by a similar dose (0.1 μg/kg per day) of the estrogenic drug diethylstilbestrol (DES), a known human developmental teratogen and carcinogen. In contrast, a 2,000-fold higher DES dose completely inhibited dorsolateral prostate duct formation, revealing opposite effects of high and low doses of estrogen. Acceleration in the rate of proliferation of prostate epithelium during fetal life by small amounts of estrogenic chemicals could permanently disrupt cellular control systems and predispose the prostate to disease in adulthood.
Information on the occurrence and bioaccumulation of bisphenols and benzophenones in coastal marine invertebrates is limited. In this study, concentrations of eight bisphenol and five benzophenone ...analogues were determined in 186 mollusks collected from coastal areas of the Chinese Bohai Sea during the period 2006–2015. Total concentrations of bisphenols and benzophenones were in range of not detected (nd)–58 (geometric mean: 13.0 ng/g) and nd–59.1 (2.06 ng/g) on a dry-weight basis, respectively. BPA and BPF were the major bisphenols, collectively accounting for >90% of the total concentrations. BP-3 was the predominant benzophenone, representing 74% of the total concentrations. The mollusk species, Meretrix meretrix, accumulated high concentrations of both bisphenols and benzophenones. A steady increase in bisphenol concentrations in mollusks was observed in recent years, whereas no obvious temporal trend was found for benzophenones. The estimated daily intakes of bisphenols through consumption of mollusks were lower than the current reference dose. This study establishes a baseline concentration for bisphenols and benzophenones in mollusks in Chinese coastal waters.
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•Temporal trends of bisphenols and benzophenones were determined in mollusks.•Geometric mean concentrations of bisphenols and benzophenones in mollusks were 13 and 2.1 ng/g dw.•Meretrix meretrix accumulated high concentrations of both bisphenols and benzophenones.•Bisphenol concentrations increased in mollusks in recent years.
Bisphenols, and especially bisphenol A, are widely used as components of epoxy resins and polycarbonate. Widespread detection and potential health risks have led to bisphenol A being replaced by ...other alternatives, including structurally similar bisphenol analogs. Several bisphenol analogs are suspected to have similar adverse health consequences. This study examined the temporal trends in bisphenol exposure among a group of Japanese women from 1993 to 2016, and assessed the associated health risks.
We used archived single spot urine samples of healthy Japanese women living in the Kyoto area (n = 133) collected in 1993, 2000, 2003, 2009, 2011, and 2016. We measured the concentrations of 10 bisphenols in these samples.
A sharp increase in the detection rates of bisphenol F was observed after 2000. There was a distinct downward trend in urinary bisphenol A concentrations and an upward trend in bisphenol E concentrations after 2009. While the hazard index for all measured bisphenols was below 1 in all subjects, bisphenol F was determined as the most important risk driver after 2000, rather than bisphenol A.
Trends of decreasing bisphenol A and increasing bisphenol E exposure especially after 2011, along with no significant change in the sum of all bisphenol analogs in urine, provide clear evidence that bisphenol A has been replaced by other bisphenols in the study population. We found no significant change in the total exposure to bisphenols during the study period. Bisphenol F might become the most important bisphenol in terms of risk, while cumulative risks due to all bisphenol exposure were deemed insignificant. Considering the accumulating evidence indicating adverse effects at lower exposure levels, further studies are warranted to assess exposure and risk from bisphenol A analogs.
Proportion of the bisphenols that produced the maximum hazard quotient in 1993–2016. Display omitted
•BPA exposure has decreased among a Japanese population during 1993–2016.•BPE exposure increased significantly after 2011 in the study population.•BPF has been the most important risk driver since 2000.•There was unlikely to be a significant health risk posed by BP exposures.
In this study, we investigated for the first time the suitability of supramolecular solvent (SUPRAS)-based microextraction probe for the development of generic and fast sample treatment prior to ...qualitative analysis by ambient mass spectrometry (AMS) based on ASAP (atmospheric solids analysis probe). SUPRAS are nanostructured liquids formed by the self-assembly of amphiphilic aggregates with multiple binding sites and microenvironments of different polarity for the efficient extraction of multiple compounds. Different types of SUPRAS were evaluated as a simple and single step sample treatment for ASAP. The method was applied to the screening of bisphenol A and structural analogues in thermal paper. Optimal results were achieved with SUPRAS synthesized with 1-decanol in mixtures of ethanol:water. SUPRAS (1.1–2 μL) were loaded onto glass probes and placed in contact with samples for 10 s before ASAP analysis. AMS signal peaks (width: 0.2–0.5 min) were easily integrated and normalized with internal standards (RSD: 2–25%). The method was applied to 62 samples of thermal paper. BPA and BPS were the most widely used, this highlighting the progressive industrial replacement of BPA by BPS.
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•SUPRAS microextraction probes are proposed for fast detection of bisphenols by ASAP.•Fast (10 s extraction, 1 min analysis) and simple (probe loading and sample contact).•BPA and BPS were the most abundant in thermal paper.•BPA is progressively being replaced by BPS in the Spanish market.
Pharmaceuticals, such as over-the-counter (OTC) medicines, may be an important source of human exposure to several endocrine disruptors, though unnoticed to date. In the present study, we ...investigated the presence of six parabens and nine bisphenol A (BPA) and its analogues in OTC medicines manufactured in China. Parabens and bisphenols were present in more than 90% of the samples. The total measured concentrations of parabens and bisphenols were in the range of non-detectable (ND) to 213 ng/g and ND to 415 ng/g, respectively. Regarding parabens, methyl paraben (MeP) was the predominant analog, accounting for 43 ± 36% of the total amount, followed by ethyl paraben (EtP) (39 ± 35%), and others (< 10%). Bisphenol F and BPA were the predominant bisphenols, accounting for 24 ± 28% and 22 ± 26% of the total amount, respectively. The median values of estimated daily intakes (EDIs) of parabens and bisphenols were the highest for infants (2.96 and 3.14 ng/kg_bw/day, respectively) and the lowest for adults (0.69 and 0.25 ng/kg_bw/day, respectively); moreover, the EDIs of parabens and bisphenols were higher in Chinese patent medicines than in western pediatric medicines. The hazard quotient (HQ) for sum of MeP and EtP (∑(MeP + EtP)) and BPA in three age groups were within the safe zone (HQ < 0.0004). Monte Carlo simulation was applied to predict the human exposure risk of parabens and bisphenols. The predicted ranges of EDIs of parabens and bisphenols were much wider, and the extreme predicted values were observed in all four age groups, which were higher than the acceptable daily intake. The extreme predicted values of ∑(MeP + EtP) and BPA were indicative of carcinogenic risk in toddlers. These results implied potential risks for the Chinese people existed. Considering the huge export of Chinese traditional medicines and western medicines worldwide, and easy access to OTC medicines for the general population, the presence of parabens, bisphenols, and other environmental contaminants in medicines still need to be monitored.
Bisphenols (BPs), which have more than ten kinds of structural analogues, are emerging as the most important endocrine disrupting chemicals that adversely affect human health and aquatic life. A ...tyrosinase nanosensor based on metal–organic frameworks (MOFs) and chitosan was developed to investigate the electrochemical response characteristics and mechanisms of nine kinds of BPs for the first time. The developed tyrosinase nanosensor showed a sensitive response to bisphenol A, bisphenol F, bisphenol E, bisphenol B, and bisphenol Z, and the responsive sensitivities were highly dependent on their respective log K ow values. However, the nanosensor showed no response to bisphenol S (BPS), bisphenol AP (BPAP), bisphenol AF (BPAF), or tetrabromobisphenol A, although BPS, BPAP, and BPAF have structures similar to those of the responsive BPs. The obtained results reveal that the electrochemical response of different BPs is affected not only by the molecular structure, especially the available ortho positions of phenolic hydroxyl groups, but also by the substituent group properties (electron acceptor or electron donor) on the bisphenol framework. The electronic cloud distribution of the phenolic hydroxyl groups, which is affected by the substituent group, determines whether the available ortho positions of phenolic hydroxyl groups can be oxidized by the tyrosinase biosensor. These response mechanisms are very significant as they can be used for predicting the response characteristics of many BPs and their various derivatives and metabolites on biosensors. The unexpected anti-interference ability of the biosensor to nine heavy metal ions was also discovered and discussed. The MOF-chitosan nanocomposite proves to be a promising sensing platform for the construction of diverse biosensors for selective detection of targets even in the presence of a high concentration of heavy metal ions.
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•The miniaturized technique DLLME is interesting as green sample preparation.•The urinary concentrations of BPA are determined in control and diabetic humans.•Free and conjugated ...glucuronidated forms of BPA are analyzed.•The method is validated using a certified reference material of smoking human urine.
The association between bisphenol A (BPA) exposure and adult health status is examined by measuring the urinary BPA concentration using a miniaturized technique based on dispersive liquid-liquid microextraction (DLLME) in combination with gas chromatography-mass spectrometry (GC–MS). Both the free bioactive and the glucuronide conjugated forms of BPA were measured, the glucuronide form usually being predominant. The main analogs of BPA, including bisphenol Z (BPZ), bisphenol F (BPF) and biphenol (BP) were also determined. Several parameters affecting enzymatic hydrolysis, derivatization by in-situ acetylation and the DLLME stages were carefully optimized by means of multivariate designs. DLLME parameters were 2mL urine, 1mL acetone and 100μL chloroform, and hydrolysis was performed using β-glucuronidase and sulfatase at pH 5. No matrix effect was observed and quantification was carried out by aqueous calibration with a surrogate standard. Detection limits were in the range 0.01–0.04ngmL−1. The intraday and interday precisions were lower than 11% in terms of relative standard deviation. Satisfactory values for all compounds were obtained in recovery studies (92–117%) at two concentration levels. Other bisphenols (BPF, BPZ and BP) were not detected in the urine samples, while BPA was the only bisphenol detected in the free form (creatinine adjusted) at concentration levels ranging from the detection limit to 15.9ngg−1, and total BPA was detected at concentrations ranging from 0.46 to 24.5ngg−1 levels. A comparison of the BPA content for both groups of patients revealed that slightly higher mean values were obtained for both free BPA and total BPA for diabetic patients, than for non-diabetic patients. However, a statistical comparison of the contents of BPA revealed that there were no significant differences. The procedure was validated using a certified reference material.
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