Comparative toxicity of a brominated flame retardant (tetrabromobisphenol A) on microalgae with single and multi-species bioassays

The potential threat of emerging chemicals to the aquatic flora is a major issue. The purpose of the study was to develop a multispecies microalgae test in order to determine the impact of species interactions on the cytoxicity of an emergent toxic contaminant: the tetrabromobisphenol A (TBBPA). Single and multi-species tests were thus performed to study the effects of this flame retardant on two microalgae (Pseudokirchneriella subcapitata and Nitzschia palea) commonly observed in freshwater. A synthetic medium was designed to allow the growth of both species. The algae were exposed to 1.8, 4.8, 9.2, 12.9 and 16.5 μM of TBBPA for 72 h. After staining with fluorescein diacetate (FDA), viable cells of each alga species were analyzed by flow cytometry based on chlorophyll autofluorescence and intracellular esterase activity. Density and abundance of viable cells were assessed to follow the population growth and the cell viability. In TBBPA treated samples, the growth of the two microalgae was significantly inhibited at the three highest concentrations (9.2, 12.9 and 16.5 μM) in the two tests. At the end of the experiment (t = 72 h), the cell viability was also significantly smaller at these concentrations. The decreases of growth rate and viable cell abundance in TBBPA treated populations of N. palea were significantly higher in multi-species test in comparison with the single-species test. No significant differences were noticed between the two tests for P. subcapitata populations exposed to TBBPA.     

Transformation of tetrabromobisphenol A in the presence of different solvents and metals

Solvent-based separation method is presumably an efficient and environmentally beneficial approach for elimination of brominated flame retardants (BFRs) from waste electrical and electronic equipment (WEEE). The overall goal of this study was to evaluate possible effects of organic solvent on the behavior of BFRs during solvent-based processing of WEEE. We initiated a set of batch experiments for examining the rates and possible pathways of transformation of a representative BFR (tetrabromobisphenol A, TBBPA) using acetone, toluene, and methanol as the solvents. Our results showed that toluene and methanol had no effect on the transformation of TBBPA, but approximately 20% of TBBPA (100 mg L⁻¹) was transformed by acetone within 2 h at 50 °C. Analysis of the products with GC-MS showed that two high-molecular-weight products (MW = 586) were major products of the transformation reactions. The role of acetone as a reactant in the transformation of TBBPA was further validated with dueterated acetone. In addition, the effects of co-existing metals in WEEE (i.e., Zn, Cu, and Ni) on the transformation of TBBPA in the solvent systems were investigated. These metals tested were found to greatly enhance the rates of TBBPA transformation. The metal facilitated solvent reactions with TBBPA may lower the extractability of TBBPA by formation of larger and less soluble products, hence potentially increasing the cost for separating the chemical from WEEE.     

Leaching of brominated flame retardants in leachate from landfills in Japan

Leachate samples were taken from seven different landfills and concentrations of brominated flame retardants (BFRs), i.e. polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA), were quantified. Leaching characteristics of BFRs, especially factors affecting leachability, were clarified to obtain basic information regarding the release of BFRs into the environment. The results obtained for observed levels of the sum of PBDE-47, -99 and -100 were n.d.--4000 pg/l for the raw leachate and n.d. for the treated one, respectively, and those of TBBPA were n.d.--620,000 pg/l for the raw leachate and n.d.--11,000 pg/l for the treated one, respectively. Three sites that not only had crushed material from bulk wastes such as waste electric and electronic equipment, but also were under operation or within a year since closure, indicated a higher concentration of BFRs than the other sites. In particular extremely high concentration of PBDEs was observed at a site with a large amount of organics. Considering the leaching characteristics of BFRs, there exists the possibility that leachability of PBDEs is influenced by the presence of dissolved humic matter (DHM) in the leachate. The high removal efficiency for BFRs in the leachate treatment process was also confirmed.     

Effects of tetrabromobisphenol A as an emerging pollutant on wheat (Triticum aestivum) at biochemical levels

Biochemical responses of wheat (Triticum aestivum) to the stress of tetrabromobisphenol A (TBBPA) as an emerging pollutant were examined. The results indicated that reduction of the chlorophyll (CHL) content in wheat leaves could be observed. However, the changes in the CHL content with the increasing TBBPA concentration from 50 to 5000 mg kg(-1) were insignificant (p>0.05). Increased malondialdehyde levels were detected in wheat leaves after both 7-d and 12-d exposures. The changes in the activity of superoxide dismutases (SOD), peroxidases (POD) and catalases (CAT) in wheat leaves irregularly fluctuated with time as the TBBPA concentration increased. However, significant (p<0.05) decrease in the activity of POD and CAT treated with 500 and 5000 mg kg(-1) TBBPA could be observed. Our data also showed that the plant has the capacity to tolerate the oxidative stress, but the capacity would be lost with prolonged exposure and increasing TBBPA concentration. There were no dose-response effects in the changes between the activity of antioxidant enzymes (SOD, POD and CAT) and the concentration of TBBPA. The decrease in the activity of POD and CAT could be considered as good biomarkers of serious stress by TBBPA in soil environment.     

Phytoremediation potential of Spirulina (Arthrospira) platensis: biosorption and toxicity studies of cadmium

This study examines the possibility of using Spirulina (Arthrospira) platensis TISTR 8217 to remove low concentrations of cadmium (less than 100 mg/l) from wastewater. The cyanobacteria were exposed to six different cadmium concentrations for 96 h, and the growth rate was determined using an optical density at 560 nm. The inhibiting concentration (IC50) was estimated using probit analysis. The IC50 at 24, 48, 72, and 96 h were 13.15, 16.68, 17.28, and 18.35 mg/l Cd, respectively. Cellular damage was studied under a light microscope and a transmission electron microscope. Swollen cells and fragmented filaments were observed. Cell injury increased with increasing concentrations of cadmium. Ultrastructural changes were observed in the algae exposed to cadmium concentrations both close to IC50 (14.68 mg/l) and at IC50 (18.35 mg/l). The alterations induced by cadmium were disintegration and disorganization of thylakoid membranes, presence of large intrathylakoidal space, increase of polyphosphate bodies, and cell lysis. In addition, the cadmium adsorption by algal cells was studied. Environmental factors were found to have an effect on biosorption. The uptake of cadmium was not affected by the temperature of the solution, but the sorption was pH dependent. The optimum pH for biosorption of algal cells was 7. The cadmium uptake process was rapid, with 78% of metal sorption completed within 5 min. The sorption data fit well to the Langmuir isotherm. The maximum adsorption capacity for S. platensis was 98.04 mg Cd per g biomass.     

Review of historical aquatic toxicity and bioconcentration data for the brominated flame retardant tetrabromobisphenol A (TBBPA): effects to fish,invertebrates, algae,and microbial communities

This paper summarizes the historical and recent research on the aquatic toxicology and bioconcentration potential of tetrabromobisphenol A (TBBPA), a major flame retardant in electronics. Historical studies on TBBPA are presented in detail, and are compared with more recent research. The historical studies have not been published to date, though they were pivotal in regulatory assessments by the European Union, Canada, and the USA. These assessments have enabled the use of TBBPA as a flame retardant in electronic applications, to the present. The studies were conducted under a Test Rule by the US Environmental Protection Agency in 1987, and were sponsored by member companies of the North American Flame Retardants Alliance (NAFRA) through the American Chemistry Council. The studies were conducted under Good Laboratory Practice procedures, and include 6 acute toxicity tests of TBBPA with fish, invertebrates, algae, and microbes, eight chronic tests, and three bioconcentration studies with fish and invertebrates. Methods and empirical data for each study are detailed in an electronic supplement. Results of the NAFRA studies are compared with recent findings on TBBPA toxicity. Molluscan shell growth may be uniquely sensitive to TBBPA, more sensitive than chronic fish or crustacean toxicity endpoints. Several of the NAFRA studies and several independent studies have reported toxicities exceeding the empirical water solubility limits of TBBPA (in the range of 2.0 mg/L depending on pH). The validity of these results is discussed.     

Effects of fifteen PBDE metabolites, DE71, DE79 and TBBPA on steroidogenesis in the H295R cell line

Polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA) are brominated flame retardants that are produced in large quantities and are commonly used in construction materials, textiles, and as polymers in electronic equipment. Environmental and human levels of PBDEs have been increasing in the past 30 years, but the toxicity of PBDEs is not fully understood. Studies on their effects are relatively limited, and show that PBDEs are neurotoxins and potential endocrine disrupters. Hydroxylated (OH) and methoxylated (MeO) PBDEs have also been reported in the adipose tissue, blood and milk of wild animals and humans. In the present study, 15 PBDE metabolites, two BDE mixtures (DE71 and DE79), and TBBPA were studied individually to determine their effects on ten steroidogenic genes, aromatase activity, and concentrations of two steroid hormones (testosterone and 17beta-estradiol) in the H295R human adrenocortical carcinoma cell line. Exposure to 0.05 microM 2'-OH-BDE-68 significantly induced the expression of CYP11A, CYP11B2, CYP17, CYP21, 3betaHSD2, 17betaHSD1, and 17betaHSD4, and the expression of StAR was induced by 6-OH-BDE-90 at the three exposure concentrations. Exposure to DE71 and DE79 resulted in dose-dependent trend towards induction, but these effects were not significant. Exposure to 0.5 microM 2-OH-BDE-123 and 2-MeO-BDE-123 resulted in significantly greater aromatase activity. However, none of the compounds affected sex hormone production at the concentrations tested. Generally, OH-BDEs had a much stronger ability to affect steroidogenic gene expression than MeO-BDEs.     

Tetrabromobisphenol A: tissue distribution in fish, and seasonal variation in water and sediment of Lake Chaohu, China

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardants (BFRs). It has been detected in various environment media and has been approved to be high toxic to aquatic organisms. However, the exposure levels of TBBPA in the main watersheds in China have not been investigated sufficiently. In this study TBBPA concentrations in water, sediment and tissues of four fish species from Lake Chaohu were determined. Spatial and temporal distribution patterns of TBBPA in water and sediment, and the relationship among TBBPA concentrations in fish tissues and fish size were analyzed. The results showed that the maximum TBBPA concentration in sediment was 518 ng/g in March 2008. It is almost the highest value than those ever reported anywhere in the world. In lake water, TBBPA level reached the maximum value of 4.87???g/L in July. Tissue distributions of TBBPA in four fish species were similar, and the mean concentrations in the fish were in the range of 28.5?C39.4 ng/g, much higher than those reported in Japan, Europe, and the United States. The maximum concentrations of TBBPA were found in kidneys where TBBPA concentration was positively correlated with fish size of Cyprinus carpio. Results demonstrated a widespread distribution of TBBPA in Lake Chaohu. The source was mainly inflow rivers near the cities. The distribution coefficient among water, fish, and sediment was 1:28:117. This indicated that sediment was the main repository for TBBPA within Lake Chaohu. Furthermore, TBBPA may pose a potential ecological risk in the lake during summer.     

Waterborne and sediment toxicity of fluoxetine to select organisms

Ecological risk assessments of pharmaceuticals are currently difficult because little-to-no aquatic hazard and exposure information exists in the peer-reviewed literature for most therapeutics. Recently several studies have identified fluoxetine, a widely prescribed antidepressant, in municipal effluents. To evaluate the potential aquatic toxicity of fluoxetine, single species laboratory toxicity tests were performed to assess hazard to aquatic biota. Average LC(50) values for Ceriodaphnia dubia, Daphnia magna, and Pimephales promelas were 0.756 (234 microg/l), 2.65 (820 microg/l), and 2.28 microM (705 microg/l), respectively. Pseudokirchneriella subcapitata growth and C. dubia fecundity were decreased by 0.044 (14 microg/l) and 0.72 microM (223 microg/l) fluoxetine treatments, respectively. Oryias latipes survival was not affected by fluoxteine exposure up to a concentration of 28.9 microM (8.9 mg/l). An LC(50) of 15.2 mg/kg was estimated for Chironomus tentans. Hyalella azteca survival was not affected up to 43 mg/kg fluoxetine sediment exposure. Growth lowest observed effect concentrations for C. tentans and H. azteca were 1.3 and 5.6 mg/kg, respectively. Our findings indicate that lowest measured fluoxetine effect levels are an order of magnitude higher than highest reported municipal effluent concentrations.     

Removal of tetrabromobisphenol A by conventional activated sludge, submerged membrane and membrane aerated biofilm reactors

The goal of this study was to compare removal efficiencies of tetrabromobisphenol A (TBBPA) using typical wastewater treatment technologies, and to identify the most significant mechanisms of removal. Two types of municipal wastewater reactors were studied: a full-scale conventional activated sludge (CAS) reactor with tertiary treatment; and three pilot-scale membrane bioreactors (MBRs) having different sludge retention times (SRTs). All four reactors were fed the same influent. A third reactor type, a membrane aerated biofilm reactor (MABR) was fed tap water, ammonia, and TBBPA. TBBPA in municipal influent ranged from 1 to 41 ng L⁻¹ (n = 10). The CAS effluent had an average TBBPA concentration of 0.7 ± 1.3 ng L⁻¹ (n = 3). Effluent concentrations from the MBRs were an average of 6 ± 6 ng L⁻¹ TBBPA (n = 26). Significant TBBPA removal was observed in the MABR throughout the 5 week of study (p ? 0.05). Removal of TBBPA from wastewater treatment was found to be due to a combination of adsorption and biological degradation. Based on experimental results, nitrification is likely a key process therein. No significant relationship between removal of TBBPA and SRT was identified (p ? 0.05).     

Occurrences and inventories of heavy metals and brominated flame retardants in wastes from printed circuit board production

Pollutants including heavy metals and brominated flame retardant were detected in 10 types of production wastes from a typical printed circuit board manufacturing plant, and their inventories were estimated. Rinsing water from etching process had the highest concentrations of copper (665.51 mg/L), lead (1.02 mg/L), nickel (3.60 mg/L), chromium (0.97 mg/L), and tin (1.79 mg/L). Powdered solid waste (SW) from the cut lamination process contained the highest tetrabromobisphenol-A (TBBPA) levels (49.86 mg/kg). Polybrominated diphenyl ethers (PBDEs) were absent in this plant, in agreement with the international regulations of PBDE phase out. The pollutant inventories in the wastes exhibited in the order of copper >?>?zinc?>?tin?≈?nickel?>?lead?>?chromium >?>?TBBPA. The potential environmental impact of pollutants in SW during production and disposal were further investigated. A high partitioning of pollutant concentration between the total suspended particle and SW (?0.10?K _TS?相似文献   

Physicochemical and toxicological characteristics of urban aerosols during a recent Indonesian biomass burning episode

Air particulate matter (PM) samples were collected in Singapore from 21 to 29 October 2010. During this time period, a severe regional smoke haze episode lasted for a few days (21–23 October). Physicochemical and toxicological characteristics of both haze and non-haze aerosols were evaluated. The average mass concentration of PM_2.5 (PM with aerodynamic diameter of ≤2.5 μm) increased by a factor of 4 during the smoke haze period (107.2 μg/m³) as compared to that during the non-smoke haze period (27.0 μg/m³). The PM_2.5 samples were analyzed for 16 priority polycyclic aromatic hydrocarbons (PAHs) listed by the United States Environmental Protection Agency and 10 transition metals. Out of the seven PAHs known as potential or suspected carcinogens, five were found in significantly higher levels in smoke haze aerosols as compared to those in the background air. Metal concentrations were also found to be higher in haze aerosols. Additionally, the toxicological profile of the PM_2.5 samples was evaluated using a human epithelial lung cell line (A549). Cell viability and death counts were measured after a direct exposure of PM_2.5 samples to A459 cells for a period of 48 h. The percentage of metabolically active cells decreased significantly following a direct exposure to PM samples collected during the haze period. To provide further insights into the toxicological characteristics of the aerosol particles, glutathione levels, as an indirect measure of oxidative stress and caspase-3/7 levels as a measure of apoptotic death, were also evaluated.     

Bioaccumulation and physiological effects of tetrabromobisphenol A in coontail Ceratophyllum demersum L

Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants. In the present study, the accumulation of TBBPA and its consequent biological responses were examined in coontail (Ceratophyllum demersum L.) over 14 days' exposure. Most of the TBBPA was accumulated after 4d exposure and TBBPA concentration in plant increased with increasing TBBPA concentration in growth solution (R(2)=0.99). By using electron paramagnetic resonance (EPR), we found that the TBBPA exposure significantly increased total free radicals generation in the plants. A good positive relationship (R(2)=0.99) was found between the free radicals formation and accumulation level of TBBPA in plant. Lipid peroxidation was enhanced and chlorophyll content showed declined after TBBPA exposure. The activities of superoxide dismutase (SOD), peroxidase (POD), and the contents of glutathione were also detected. The results suggest that TBBPA accumulation in C. demersum induces oxidative stress and the level of tolerance depends on the antioxidative capacity of the plants.     

Riboflavin-photosensitized degradation of atrazine in a freshwater environment

The effect of the photosensitizer riboflavin (0, 10, 50, 100 microM) on the fate of atrazine (10 mg/l) in a freshwater environment was studied. It was found that at 100 microM riboflavin significantly enhanced the degradation of atrazine and more than 80% of atrazine in a natural water environment was depleted in 72 h. The relative contribution of microbial assemblages and the freshwater matrix to the degradation of atrazine and the degradation kinetics of atrazine were compared under different experimental conditions. The products and pathways of atrazine transformation were studied with GC-MS and HPLC with a photodiode array detector. The results show that dealkylation and alkyl chain oxidation are involved in the degradation of atrazine.     

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.     

Exposure assessment of French women and their newborns to tetrabromobisphenol-A: occurrence measurements in maternal adipose tissue, serum, breast milk and cord serum

A French monitoring study was initiated to evaluate the exposure of fetus and newborn to brominated flame retardants (BFR). A previously developed multi-residue analytical method was used for measuring the main classes of BFR (tetrabromobisphenol-A, and tri- to decabomodiphenyl ethers) in various human biological matrices. Analyzed samples (maternal and cord serum, adipose tissue and breast milk) were collected from 93 volunteer women during caesarean deliveries. TBBPA was detected in 44% of the analyzed breast milk samples, at levels varying from 0.06 to 37.34 ng g(-1) lipid weight, but was not detected in adipose tissue. This compound was also detected in 30% of the analyzed serum samples, with similar average values in maternal and cord serum (154 pg g(-1) fresh weight versus 199 pg g(-1) fresh weight, respectively). The interpretation of the collected data permitted the demonstration of (1) a significant exposure to TBBPA both for mothers and fetuses and (2) a possible risk of overexposure of newborns through breastfeeding.     

ROS and CDPK-like kinase-mediated activation of MAP kinase in rice roots exposed to lead

Lead (Pb2+) is a cytotoxic metal ion in plants, the mechanism of which is not yet established. The aim of this study is to investigate the signalling pathways that are activated by elevated concentrations of Pb2+ in rice roots. Root growth was stunted and cell death was accelerated when exposed to different dosages of Pb2+ during extended time periods. Using ROS-sensitive dye and Ca2+ indicator, we demonstrated that Pb2+ induced ROS production and Ca2+ accumulation, respectively. In addition, Pb2+ elicited a remarkable increase in myelin basic protein (MBP) kinase activities. By immunoblot and immunoprecipitation analysis, 40- and 42-kDa MBP kinases that were activated by Pb2+ were identified to be mitogen-activated protein (MAP) kinases. Pre-treatment of rice roots with an antioxidant and a NADPH oxidase inhibitor, glutathione (GSH) and diphenylene iodonium (DPI), effectively reduced Pb2+-induced cell death and MAP kinase activation. Moreover, calcium-dependent protein kinase (CDPK) antagonist, W7, attenuated Pb2+-induced cell death and MAP kinase activation. These results suggested that the ROS and CDPK may function in the Pb2+-triggered cell death and MAP kinase signalling pathway in rice roots.     

Photochemical transformations of tetrabromobisphenol A and related phenols in water

A method was developed for studies of the phototransformation at UV irradiation of aqueous solutions of tetrabromobisphenol A (TBBPA), tribromobisphenol A (TriBBPA), tetrachlorobisphenol A (TCBPA), 2,4-dichlorophenol at various pHs as well as 2-chlorophenol, 2-bromophenol, 3,4-dichlorophenol and bisphenol A at pH 11. The absorbance spectra of the compounds and the emission spectra of the light-source were determined and used to calculate disappearance quantum yields of the photochemical reactions that were taking place. No major differences between the disappearance quantum yields of TBBPA and TCBPA were observed at pH 10, while the disappearance quantum yield of TriBBPA was approximately two times higher. The rate of decomposition of TBBPA was six times higher at pH 8 than at pH 6. Identification of the degradation products of TBBPA and TriBBPA, by GC-MS analysis and by comparison to synthesised reference compounds, indicated that TBBPA and TriBBPA decompose via different mechanisms. Three isopropylphenol derivatives; 4-isopropyl-2,6-dibromophenol, 4-isopropylene-2,6-dibromophenol and 4-(2-hydroxyisopropyl)-2,6-dibromophenol, were identified as major degradation products of TBBPA while the major degradation product of TriBBPA was tentatively identified as 2-(2,4-cyclopentadienyl)-2-(3,5-dibromo-4-hydroxyphenyl)propane.