Glycosylation of bisphenol A by freshwater microalgae

The endocrine disruptor bisphenol A (BPA, 4,4'-isopropylidenediphenol) is used to manufacture polycarbonate plastic and epoxy resin linings of food and beverage cans, and the residues from these products are then sometimes discharged into rivers and lakes in waste leachates. However, the fate of BPA in the environment has not yet been thoroughly elucidated. Considering the effect of BPA on aquatic organisms, it is important that we estimate the concentration of BPA and its metabolites in the aquatic environment, but there are few data on the metabolites of BPA. Here, we focused on freshwater microalgae as organisms that contribute to the biodegradation or biotransformation of BPA in aquatic environments. When we added BPA to cultures of eight species of freshwater microalgae, a reduction in the concentration of BPA in the culture medium was observed in all cultures. BPA was metabolized to BPA glycosides by Pseudokirchneriella subcapitata, Scenedesmus acutus, Scenedesmus quadricauda, and Coelastrum reticulatum, and these metabolites were then released into the culture medium. The metabolite from P. subcapitata, S. acutus, and C. reticulatum was identified by FAB-MS and (1)H-NMR as bisphenol A-mono-O-beta-d-glucopyranoside (BPAGlc), and another metabolite, from S. quadricauda, was identified as bisphenol A-mono-O-beta-d-galactopyranoside (BPAGal). These results demonstrate that freshwater microalgae that inhabit universal environments can metabolize BPA to its glycosides. Because BPA glycosides accumulate in plants and algae, and may be digested to BPA by beta-glycosidase in animal intestines, more attention should be given to levels of BPA glycosides in the environment to estimate the ecological impact of discharged BPA.     

Viable skin efficiently absorbs and metabolizes bisphenol A

Skin contact has been hypothesized to contribute to human exposure to bisphenol A (BPA). We examined the diffusion and metabolism of BPA using viable skin models: human skin explants and short-term cultures of pig ear skin, an alternative model for the study of the fate of xenobiotics following contact exposure. ¹⁴C-BPA [50-800 nmol] was applied on the surface of skin models. Radioactivity distribution was measured in all skin compartments and in the diffusion cells of static cells diffusion systems. BPA and metabolites were further quantified by radio-HPLC. BPA was efficiently absorbed in short-term cultures, with no major difference between the models used in the study [viable pig ear skin: 65%; viable human explants: 46%; non-viable (previously frozen) pig skin: 58%]. BPA was extensively metabolized in viable systems only. Major BPA metabolites produced by the skin were BPA mono-glucuronide and BPA mono-sulfate, accounting together for 73% and 27% of the dose, in pig and human, respectively. In conclusion, experiments with viable skin models unequivocally demonstrate that BPA is readily absorbed and metabolized by the skin. The trans-dermal route is expected to contribute substantially to BPA exposure in human, when direct contact with BPA (free monomer) occurs.     

Measurement of bisphenol A concentrations in human colostrum

Bisphenol A (BPA), an estrogenic endocrine disrupting chemical, has been reported to affect embryos and alter their postnatal development. In the present study, we measured the concentrations of BPA in human colostrum by a competitive enzyme-linked immunosorbent assay (ELISA) with the aim of understanding the present status of BPA burden in human breast milk in Shizuoka, Japan. Human colostral samples were collected from 101 healthy mothers within three days after delivery. The BPA concentrations of colostral samples were estimated by ELISA after the acetonitrile extraction and solid phase extraction column purification. BPA in 101 samples was detected in the concentration range of 1-7 ng ml(-1). The mean concentration of BPA was 3.41+/-0.13 (mean+/-SD) ng ml(-1). This is the first demonstration as to what BPA concentrations are in human colostrum. The BPA concentrations in colostrum were higher than those in blood sera samples obtained from healthy women in a previous study. In our study, there was no significant correlation between the concentrations of BPA in colostrum and the age and parity of mothers.     

超声波／零价铁降解水中双酚A

研究了超声波／零价铁（US／Fe^0）工艺对水中双酚A（BPA）的降解效果及影响因素。结果表明，US／Fe^0工艺可以有效降解水中的BPA，具有协同作用，且降解过程符合一级动力学规律；Fe^0具有促进和抑制的双重作用；超声功率越大，越有利于BPA的降解；初始浓度较低时，BPA的降解效果较好；弱酸性条件有利于BPA的降解；加入一定量的自由基捕获剂（正丁醇）可以抑制BPA的降解；联合作用2h后，TOC的去除率较低，说明其矿化程度不完全。     

A review on bisphenol A occurrences,health effects and treatment process via membrane technology for drinking water

Massive utilization of bisphenol A (BPA) in the industrial production of polycarbonate plastics has led to the occurrence of this compound (at μg/L to ng/L level) in the water treatment plant. Nowadays, the presence of BPA in drinking water sources is a major concern among society because BPA is one of the endocrine disruption compounds (EDCs) that can cause hazard to human health even at extremely low concentration level. Parallel to these issues, membrane technology has emerged as the most feasible treatment process to eliminate this recalcitrant contaminant via physical separation mechanism. This paper reviews the occurrences and effects of BPA toward living organisms as well as the application of membrane technology for their removal in water treatment plant. The potential applications of using polymeric membranes for BPA removal are also discussed. Literature revealed that modifying membrane surface using blending approach is the simple yet effective method to improve membrane properties with respect to BPA removal without compromising water permeability. The regeneration process helps in maintaining the performances of membrane at desired level. The application of large-scale membrane process in treatment plant shows the feasibility of the technology for removing BPA and possible future prospect in water treatment process.     

Ubiquity of bisphenol A in the atmosphere

Bisphenol A (BPA) is a suspected endocrine disruptor in the environment. However, little is known about its distribution and transport in the atmosphere. Here, the concentrations of BPA in the atmospheric aerosols from urban, rural, marine, and the polar regions were measured using solvent extraction/derivatization and gas chromatography/mass spectrometry technique. The concentrations of BPA (1-17,400 pg m⁻³) ranged over 4 orders of magnitude in the world with a declining trend from the continent (except for the Antarctica) to remote sites. A positive correlation was found between BPA and 1,3,5-triphenylbenzene, a tracer for plastic burning, in urban regions, indicating that the open burning of plastics in domestic waste should be a significant emission source of atmospheric BPA. Our results suggest that the ubiquity of BPA in the atmosphere may raise a requirement for the evaluation of health effects of BPA in order to control its emission sources, for example, from plastic burning.     

Application of ozone for the removal of bisphenol A from water and wastewater – A review

The extensive use of Bisphenol A (BPA) in the plastics industry has led to increasing reports of its presence in the aquatic environment, with concentrations of ng L^?1 to μg L^?1. Various advanced oxidation processes, including ozonation, have been shown to effectively degrade BPA. This paper reviews the current advancements in using ozone to remove BPA from water and wastewater.Most of the published work on the oxidation of BPA by ozone has focused on the efficiency of BPA removal in terms of the disappearance of BPA, and the effect of various operational parameters such as ozone feed rate, contact time and pH; some information is available on the estrogenic activity of the treated water. Due to increasing operational reliability and cost effectiveness, there is great potential for industrial scale application of ozone for the treatment of BPA. However, there is a significant lack of information on the formation of oxidation by-products and their toxicities, particularly in more complex matrices such as wastewater, and further investigation is needed for a better understanding of the environmental fate of BPA.     

Interaction of bisphenol A with dissolved organic matter in extractive and adsorptive removal processes

The fate of endocrine disrupting chemicals (EDCs) in natural and engineered systems is complicated due to their interactions with various water constituents. This study investigated the interaction of bisphenol A (BPA) with dissolved organic matter (DOM) and colloids present in surface water and secondary effluent as well as its adsorptive removal by powdered activated carbons. The solid phase micro-extraction (SPME) method followed by thermal desorption and gas chromatography-mass spectrometry (GC-MS) was utilized for determining the distribution of BPA molecules in water. The BPA removal by SPME decreased with the increased DOM content, where the formation of BPA-DOM complexes in an aqueous matrix was responsible for the reduced extraction of BPA. Colloidal particles in water samples sorbed BPA leading to the marked reduction of liquid phase BPA. BPA-DOM complexes had a negative impact on the adsorptive removal of BPA by powered activated carbons. The complex formation was characterized based on Fourier transform infrared (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy, along with the calculation of molecular interactions between BPA and functional groups in DOM. It was found that the hydrogen bonding between DOM and BPA would be preferred over aromatic interactions. A pseudo-equilibrium molecular coordination model for the complexation between a BPA molecule and a hydroxyl group of the DOM was developed, which enabled estimation of the maximum sorption site and complex formation constant as well as prediction of organic complexes at various DOM levels.     

Human UDP-glucuronosyltransferase isoforms involved in bisphenol A glucuronidation

Bisphenol A (BPA) is one of a number of potential endocrine disruptors which may affect normal hormonal function. In this study, human UDP-glucuronosyltransferase (UGT) isoforms involved in BPA glucuronidation were studied by kinetic analyses using human liver microsomes and recombinant human UGTs expressed in insect cells (UGT1A1, UGT1A3, UGT1A4, UGT1A6, UGT1A9, UGT2B4, UGT2B7, UGT2B15 and UGT2B17). BPA glucuronidation was catalyzed by UGT1A1, UGT1A3, UGT1A9, UGT2B4, UGT2B7 and UGT2B15 as well as by human liver microsomes. Among these UGTs, UGT2B15 showed the highest activity of BPA glucuronidation at low- (1.0 microM) and high- (20 microM) substrate concentrations. Kinetic analyses of BPA glucuronidation were performed by constructing Michaelis-Menten and Eadie-Hofstee plots. The kinetic profile of BPA glucuronidation by pooled human liver microsomes and UGT2B15 was monophasic, the K(m) and V(max) values were 6.39 microM and 4250 pmol min(-1)mg(-1)protein for pooled human liver microsomes, and 8.68 microM and 873 pmol min(-1)mg(-1)protein for UGT2B15, respectively. The K(m) values for BPA glucuronidation by pooled human liver microsomes and UGT2B15 were similar. These findings demonstrate that BPA is mainly glucuronidated by UGT2B15 in human liver microsomes, and suggest that this UGT isoform plays important roles in the detoxification and elimination of BPA.     

Chlorination of bisphenol A: kinetics and by-products formation

The kinetics of initial chlorination of bisphenol A (BPA) was studied between pH 2 and 11 at room temperature (20 +/- 2 degrees C). pH Profile of the apparent second-order rate constant of the reaction of BPA with chlorine were modeled considering the elementary reactions of HOCl with BPA species and an acid-catalyzed reaction. The predominant reactions at near neutral pH were the reactions of HOCl with the two phenolate species of BPA (k = 3.10 x 10(4) M(-1)s(-1) for BPA- and 6.62 x 10(4) M(-1) s(-1) for BPA(2-)). At near neutral pH, half-life times of BPA were calculated to be less than 1.5 h for chlorine residual higher than 0.2 mg l(-1). Chlorination of synthetic treated waters spiked with BPA showed that BPA disappeared within 4 h and that chlorinated bisphenol A congeners were rapidly formed and remained in solution for up to 10-20 h when low chlorine dosages are applied (0.5-1 mg l(-1)). To limit their presence in drinking water networks, it is then necessary to maintain high chlorine residuals that rapidly produce and decompose chlorinated bisphenol A congeners.     

Hydroxylation of bisphenol A by hyper lignin-degrading fungus Phanerochaete sordida YK-624 under non-ligninolytic condition

Bisphenol A (BPA) is one of the representative compounds of the endocrine disrupting compounds group and the highest volume chemicals produced worldwide. As a result, BPA is often detected in many soil and water environments. In this study, we demonstrated the transformation of BPA from liquid cultures inoculated with hyper lignin-degrading fungus Phanerochaete sordida YK-624. Under non-ligninolytic condition, approximately 80% of BPA was eliminated after 7 d of incubation. High-resolution electrospray ionization mass spectra and nuclear magnetic resonance analyses of a metabolite isolated from the culture supernatant suggested that BPA was metabolized to hydroxy-BPA, 4-(2-(4-hydroxyphenyl)propan-2-yl)benzene-1,2-diol, which has a much lower estrogenic activity than BPA. In addition, we investigated the effect of the cytochrome P450 inhibitor piperonyl butoxide (PB) on the hydroxylation of BPA, markedly lower transformation activity of BPA was observed in cultures containing PB. These results suggest that cytochrome P450 plays an important role in the hydroxylation of BPA by P. sordida YK-624 under non-ligninolytic condition.     

Effects of bisphenol A on ammonium assimilation in soybean roots

Bisphenol A (BPA), which is ubiquitous in the environment, is an example of an endocrine-disrupting compound (EDC). Ammonium assimilation has an important function in plant growth and development. However, insufficient information on the potential effect of BPA on ammonium assimilation in plants is available. In this study, the effects of BPA on ammonium assimilation in roots of soybean seedlings were investigated. During the stress period, 1.5 mg L^?1 of BPA improved glutamine synthetase (GS)/glutamate synthase (GOGAT) cycle and glutamate dehydrogenase (GDH) pathway in ammonium assimilation. The amino acid and the soluble protein contents increased in the soybeans. At 17.2 and 50.0 mg L^?1 of BPA, the GS/GOGAT cycle was inhibited and the GDH pathway was promoted. The amino acid content increased and the soluble protein content decreased. During the recovery period, the GS/GOGAT cycle and the GDH pathway recovered at 1.5 and 17.2 mg L^?1 of BPA but not at 50.0 mg L^?1 of BPA. The amino acid content continuously increased and the soluble protein content decreased compared with those in the control treatment. In summary, BPA treatment could affect the contents of soluble protein and amino acid in the soybean roots by regulating ammonium assimilation.     

Fate of 14C-bisphenol A in soils

Bisphenol A (BPA; 2,2-(4,4(')-dihydroxydiphenyl)propane) is predominantly used as an intermediate in the production of polycarbonate plastics and epoxy resins. Traces of BPA released into the environment can reach the soil via application of sewage sludge from wastewater treatment systems that receive wastewaters containing BPA, or from leachate from uncontrolled landfills. The biodegradability of BPA has been previously investigated in several studies designed to simulate surface waters and biological wastewater treatment systems. However, there is little information available about the fate of BPA in soil. Therefore, laboratory soil degradation and batch adsorption studies were conducted with 14C-BPA and four soils according to international guidelines. The soils represented a broad range of physico-chemical properties. An important result of the degradation study was that, independent of the soil type, 14C-BPA was rapidly dissipated and not detectable in soil extracts following 3 days of incubation. Based on this result, a dissipation half-life of less than 3 days was estimated. The major route of dissipation of 14C-BPA in soil was the formation of bound residues that could not be recovered by exhaustive Soxhlet extraction. 14C-BPA was also shown to be transiently converted to up to five metabolites, but within 3 days, neither 14C-BPA nor 14C-metabolites were detectable in the soils. After 120 days incubation, significant amounts (up to 20% of the radioactivity applied) of the parent compound were recovered as 14CO(2). Soil adsorption experiments indicated that the distribution coefficients (K(oc)) were between 636 and 931, classifying BPA as having low mobility for all tested soils. From the results of this study, it was concluded that if BPA reaches the soil compartment, it is not expected to be stable, mobile, or bioavailable.     

Characteristics,sources, and transport of tetrabromobisphenol A and bisphenol A in soils from a typical e-waste recycling area in South China

We studied the tetrabromobisphenol A (TBBPA) and bisphenol A (BPA) patterns and their sources and transport in different land-use soils from Longtang, South China, a typical electronic waste recycling center. We also studied the reductive debromination of TBBPA in paddy soils. TBBPA and BPA concentrations (on a dry weight basis) were undetected–220 and 0.50–325 ng/g, respectively, and both increased, by similar factors, in the following order: pond sediments?<?paddy soils?=?vegetable soils?<?wasteland?<?dismantling sites?<?former open burning sites. BPA concentrations were higher than TBBPA concentrations in all six land-use soils, and they correlated significantly. TBBPA and BPA were transported through the soil profiles, being found at relatively high concentrations in soil 0–40 cm deep, but only at low concentrations in soil 40–80 cm deep. The surface soil concentrations appear to have been strongly affected by crude recycling activities, and former open burning and dismantling sites were the main point sources. The areas surrounding the open burning sites and dismantling sites have been contaminated not only by the dumping of waste residues but also by fly ash deposition, even though the agricultural soils are far from the point pollution sources. Some BPA in the soils is likely to be the reductive debromination product of TBBPA because the long rainy season promotes TBBPA transformation and because BPA can persist for a long time. Incubation experiments confirmed that TBBPA could be transformed into BPA and that BPA could accumulate in waterlogged paddy soils, and this may be why BPA concentrations were higher than TBBPA concentrations in the Longtang area.     

Influence of the presence of heavy metals and surface-active compounds on the sorption of bisphenol A to sediment

The effects of different heavy metals (Cd, Pb), cationic surfactants cetyltrimethylammonium bromide (CTAB), anionic surfactant sodium dodecylbenzenesulfonate (SDBS) and the chemistry of the solution (pH and ionic strength) on the sorption of bisphenol A (BPA) to sediment were studied. Results showed that the presence of Cd and Pb caused a significant increase on the sorption of BPA to sediment and the sorption isotherms were in good agreement with Freundlich equation. The effect of surfactants on the adsorption of BPA onto sediment was found to strongly depend on the type of the surfactants. The presence of CTAB promoted BPA sorption and the amount of BPA adsorbed onto sediment increased linearly with concentration of CTAB. In contrast, the presence of anionic surfactant (SDBS) caused a slight reduction on the sorption of BPA. It was also found that the sorption behavior of BPA was affected by solution pH and ionic strength. The larger amount of BPA was absorbed with higher ionic strength and lower pH. This study may provide important insights into the understanding of the transport and fate of BPA in the environment.     

Leaching of bisphenol A (BPA) to seawater from polycarbonate plastic and its degradation by reactive oxygen species

In this study, (1) change in the concentration of bisphenol A (BPA) leached from polycarbonate (PC) tube to control water (BPA free), seawater and river water at 20 and 37 degrees C as a function of time, (2) the fate of BPA caused by addition of H(2)O(2) and Fe(3+) to seawater containing BPA leached from PC tube were assessed. BPA leached from PC tube to all water samples increased with the ascendant of temperature and with the passage of time. The BPA leaching velocity in seawater was the fastest in three samples (11 ng/day for seawater, 4.8 ng/day for river water 0.8 ng/day for control water at 37 degrees C).BPA leaching velocity from PC tube was significantly high at pH 8 (50 mM Na(2)HPO(4)) and increased dose-dependently. There was no difference in the velocity of BPA among the 50 mM phosphate-buffers at pH 6.5, 7.0 and 7.5. BPA was leached three times higher by addition of Na(+) than K(+). However, the higher the K(+) concentration, the larger the BPA leached from PC tube. Na(+) mixed with PO(4)(-) was effective on BPA leaching from PC tube, but not with SO(4)(-) or Cl(-). The results suggested that BPA leaching from PC tube would be attributed to the concentration of bibasic phosphate such as Na(2)HPO(4) and K(2)HPO(4) in water samples. BPA was degraded in both control water and seawater in the presence of radical oxygen species, but the degradation rate was lower in seawater than in control water, suggesting that anti-oxidative system exists in seawater. Neo-synthesized substance in both control water and seawater in the presence of reactive oxygen species was identified as BPA-quinone by LC-MS.     

Photodegradation of bisphenol A in simulated lake water containing algae, humic acid and ferric ions

The photodegradation of bisphenol A (BPA), a suspected endocrine disruptor (ED), in simulated lake water containing algae, humic acid and Fe3+ ions was investigated. Algae, humic acid and Fe3+ ions enhanced the photodegradation of BPA. Photodegradation efficiency of BPA was 36% after 4h irradiation in the presence of 6.5 x 10(9) cells L(-1) raw Chlorella vulgaris, 4 mg L(-1) humic acid and 20 micromol L(-1) Fe3+. The photodegradation efficiency of BPA was higher in the presence of algae treated with ultrasonic than that without ultrasonic. The photodegradation efficiency of BPA in the water only containing algae treated with ultrasonic was 37% after 4h irradiation. The algae treated with heating can also enhance the photodegradation of BPA. This work helps environmental scientists to understand the photochemical behavior of BPA in lake water.     

Effects of bacterial counts and temperature on the biodegradation of bisphenol A in river water

Total 15 surface river waters were collected from thirteen different rivers to investigate a relationship of bacterial counts and temperature to the degradation of bisphenol A (BPA). Autoclaved and non-autoclaved river water samples were spiked with 0.2 mg/l BPA. The spiked samples were placed at temperatures of 4, 20, and 30 degrees C and analyzed by high performance liquid chromatography. BPA was degraded at all temperatures in the non-autoclaved samples. However, BPA in the autoclaved samples was not changed at all temperatures for 20 d. These results show that the primary factor of BPA degradation in river water is bacteria. Moreover, three groups [group A (> 10000 CFU/ml), group B (2000-10000 CFU/ml), and group C (< 2000 CFU/ml)], were made on the basis of bacterial counts of the samples. Half-lives for BPA degradation in groups A, B, and C were 2, 3, and 6 d at 30 degrees C and were 4, 5, and 7 d at 20 degrees C, respectively. But at 4 degrees C, the loss of BPA was about 40%, 20%, and 10% in groups A, B, and C for 20 d, respectively. Bacterial counts exerted an influence on BPA degradation in river water with temperature. Our results also show that BPA-degrading bacteria are widely distributed in river waters.     

Assessment of bisphenol A released from reusable plastic, aluminium and stainless steel water bottles

Bisphenol A (BPA) is a ubiquitous high volume industrial chemical that is an estrogen and an environmental endocrine disrupting chemical. Bisphenol A is used extensively in the production of consumer goods, polycarbonate plastics, epoxy resins and coatings used to line metallic food and beverage cans. There is great concern regarding the possible harmful effects from exposures that result from BPA leaching into foods and beverages from packaging or storage containers. The objective of this study was to independently assess whether BPA contamination of water was occurring from different types of reusable drinking bottles marketed as alternatives to BPA-containing polycarbonate plastics. Using a sensitive and quantitative BPA-specific competitive enzyme-linked immunosorbent assay we evaluated whether BPA migrated into water stored in polycarbonate or copolyester plastic bottles, and different lined or unlined metallic reusable water bottles. At room temperature the concentration of BPA migrating from polycarbonate bottles ranged from 0.2 to 0.3 mg L⁻¹. Under identical conditions BPA migration from aluminium bottles lined with epoxy-based resins was variable depending on manufacturer ranging from 0.08 to 1.9 mg L⁻¹. Boiling water significantly increased migration of BPA from the epoxy lined bottles. No detectable BPA contamination was observed in water stored in bottles made from Tritan™ copolyester plastic, uncoated stainless steel, or aluminium lined with EcoCare™. The results from this study demonstrate that when used according to manufacturers’ recommendations reusable water bottles constructed from “BPA-free” alternative materials are suitable for consumption of beverages free of BPA contamination.     

Leaching of bisphenol A (BPA) from polycarbonate plastic to water containing amino acids and its degradation by radical oxygen species

In this study, (1) the change in the concentration of bisphenol A (BPA) leached from polycarbonate plastic (PCP) tube to water samples containing phosphate, sodium barbital, glycine, methionine or albumin at 37 degrees C as a function of time, and (2) the degradation rate of BPA leached from PCP tube to amino acid solutions in the presence of radical oxygen species (ROS) were investigated. The BPA leaching velocity (BPA-LV) from PCP tube to 50 mM glycine at pH 6 or 7 was twice that to control water, and the leaching was enhanced above pH 8. At pH 11, BPA-LV was significantly higher in 50 mM glycine and methionine solutions than in 50 mM NaOH. These results indicate that basic pH and amino acids contained in water could accelerate BPA leaching. The BPA-LV in phosphate buffer was different from the BPA-LVs in other buffers (barbital and glycine) at the same pH. BPA leached to the glycine or methionine solutions at pH 11 was degraded time dependently in a similar manner as the control water in the presence of ROS. The degradation of leached BPA was inhibited in the glycine solution, but was accelerated in the methionine solution. However, degradation of BPA added to freshly prepared methionine was inhibited in a similar manner to BPA in glycine. BPA degradation could be influenced by some kinds of amino acids, but glycine and methionine might be involved in BPA degradation in different ways.