A standardized method for assessment of oxidative transformations of brominated phenols in water

The term persistence has been used to confusion since it is used as a conceptual parameter without a uniform definition. Work is therefore being done in order to unite ideas and describe persistence based on the chemical reactivity and chemico-physical properties of compounds via investigation of the main degradation pathways in the environment; photolysis, hydrolysis-substitution-elimination (hse), oxidation, reduction and radical reactions. The present work is focused on developing a method to determine oxidative degradation rates of chemicals and thereby measurement of their susceptibility to undergo oxidation reactions. The method based on potassium permanganate works well for water soluble compounds and is easy, robust, inexpensive and reproducible. By using the method and varying the analysed substances, the degradation rates for brominated phenols, two chlorinated phenols and high volume production compounds such as tetrabromobisphenol A (TBBPA), tetrachlorobisphenol A (TCBPA) and bisphenol A (BPA) have been determined at pH 7.6+/-0.2. The reaction rates of the two halogenated BPA's are particularly fast, giving half-lives in seconds. The other test compounds have slower reaction rates but easily measured under the reaction conditions applied. The reactions are temperature dependent. There is evidence that pK(a) and the substitution pattern of the halogens affects the rate of the reactions. The method is robust and applicable for reaction rate constant measurements of present and potential future environmental contaminants.     

超/亚临界水中四溴双酚A的脱溴降解特性研究

在超/亚临界水及其碱溶液中对四溴双酚A进行了水热脱溴降解研究。考察了温度、时间和碱类型对降解特性的影响。结果表明,在纯水中温度是影响四溴双酚A降解的关键参数,350℃下反应180 min和400℃反应30 min,脱溴率分别达到98.7%和96.7%,降解产物中苯酚和4-丁基苯酚分别占50%和20%以上,另外还有少量的烷基酚;向反应体系中加入碱不仅可以中和反应过程中产生的氢溴酸以保护超临界反应釜,而且可以在较低温度下实现高的脱溴率,产物中苯酚含量达50%以上、4-异丙烯基苯酚占10%左右,可以实现脱溴同时回收化工产品的目的。与传统的热解技术相比,超/亚临界水处理TBBPA具有明显的优势,本研究为含溴电子废弃物的清洁高附加值资源化利用提供了一条新的途径。     

四溴双酚A对土壤酶活性的影响

采用室内模拟试验方法,研究了四溴双酚A对土壤多酚氧化酶、过氧化氢酶和脱氢酶活性的影响.结果表明,四溴双酚A对土壤多酚氧化酶和过氧化氢酶有一定的激活效应,这可能是土壤微生物在受到外源四溴双酚A胁迫时产生了应激反应,通过增加多酚氧化酶和过氧化氢酶的产生量来降低四溴双酚A及其代谢、中间产物对其产生的危害;同时,四溴双酚A对土壤脱氢酶产生一定的抑制效应,表明其对土壤微生物活性具有一定的抑制作用,但在试验设置的四溴双酚A浓度范围内基本未达到显著水平(P>0.05).     

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.     

Photochemical behavior of chlorsulfuronR in water and in adsorbed phase

The photochemistry of the herbicide chlorsulfuron^R (2-chloro-N-[[4-methoxy-6-methyl-1.3.5-triazinyl-2-amino]carbonyl]benzene sulfonamide) was investigated in methanol, distilled water, natural creek-water, on silica gel and on montmorillonit surfaces. The rate of degradation was determined in outdoor and indoor experiments simulating tropospheric conditions (λ>290 nm). Two major photoproducts were identified in all cases.     

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.     

假单胞菌好氧降解四溴双酚A的特性

为了解四溴双酚A(TBBPA)的好氧降解特性,采用选择富集法从活性污泥中分离出一株能够高效降解四溴双酚A的菌株。根据其形态、生理生化特性及16S rDNA核苷酸序列分析,该菌株被鉴定为假单胞菌属(Pseudomonas sp.)。研究结果表明,该菌株可通过好氧共代谢方式实现四溴双酚A的降解,葡萄糖是四溴双酚A降解的最佳碳源,其最优降解条件为葡萄糖8 g/L,牛肉膏0.5 g/L,pH值为7.0,培养温度为35℃,摇床转速为150 r/min。在该条件下其生物降解过程符合一级动力学模型,6 d后的降解率高达95.6%。LC-MS结果表明,四溴双酚A在好氧降解过程中会生成异丙苯酚类物质。     

Fate of tetrabromobisphenol A and hexabromocyclododecane brominated flame retardants in soil and uptake by plants

The fate of tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereomers (α-, β-, and γ-HBCD) and uptake by plants (cabbage and radish) was investigated. In a short-term (8 weeks) experiment, sorption to soil matrix resulted in 90% decline in recovery of these compounds in the experimental soil. However, nearly 50% of initial HBCDs recovered in mixed cabbage-radish treatments, which suggested that interspecific plant interactions might enhance the bioavailability of HBCDs. Although both plant species could uptake TBBPA and HBCDs, cabbage showed greater accumulating ability. Up to 3.5-10.0-fold higher HBCD concentrations were observed than TBBPA concentrations in all plant tissues, and the distribution of HBCDs in plant tissues was diastereomer-specific. The predominance of α-HBCD in shoot tissues for both species might be attributed to diastereomer-specific translocation of HBCDs, shift in diastereomer pattern and/or selective metabolization of γ-HBCD within plants. The results showed that strong sorption to soil particles reduced the potential of human exposure to BFRs in the soil. However, plants increased the exposure risk by uptaking these compounds and by enhancing their bioavailability. The results also provide insight into transport mechanisms of TBBPA and HBCD diastereomers in soil-plant systems.     

Rate constants for reactions of singlet oxygen with phenols and other compounds in water

Rate constants for some environmentally important organic model compounds reacting with singlet oxygen in water have been determined in laboratory experiments using rose bengal as a sensitizer. Dimethylfuran, furfuryl alcohol, 2,3-dimethyl-2-butene and diethylsulfide react about three times faster in water than in non-aqueous solutions. Phenolic compounds react faster at higher pH values. Their rate constants exactly increase with their degree of dissociation. Rate constants for the ionized species of these phenolic compounds are greater than 10⁸M⁻¹s⁻¹. In natural surface water under solar irradiation reaction with singlet oxygen is important only for a few classes of especially reactive organic compounds.     

Exposure to polybrominated diphenyl ethers and tetrabromobisphenol A among computer technicians

This study investigates exposure to polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA), which are used as flame retardants in electronic equipment, in a group of technicians with intense computer work. Thirteen PBDE congeners and TBBPA were quantified in serum from 19 computer technicians. Previously investigated groups of hospital cleaners with no computer experience, and clerks working full-time at computer screens were used for comparison. The computer technicians had serum concentrations of BDE-153, BDE-183 and BDE-209 that were five times higher than those reported among hospital cleaners and computer clerks. The median levels observed among the computer technicians were 4.1, 1.3, and 1.6 pmol/g lipid weight, respectively. In contrast, for BDE-47 there was no difference between the computer technicians and the others. BDE-100, BDE-203, and three structurally unidentified octa-BDEs and three nona-BDEs, were present in almost all samples from the computer technicians. Further, TBBPA was detected in 8 out of 10 samples. The levels of BDE-153, BDE-183, and one of the octa-BDEs were positively correlated with duration of computer work among technicians. On a group level an exposure gradient was observed, from the least exposed cleaners to the clerks, and to the highest exposed group of computer technicians. A dose (duration of computer work)-response relationship among computer technicians was demonstrated for some higher brominated PBDE congeners. Thus, it is evident that PBDEs used in computers and electronics, including the fully brominated BDE-209, contaminate the work environment and accumulate in the workers tissues.     

Removal of phenols from water accompanied with synthesis of organobentonite in one-step process

A novel technology of wastewater treatment was proposed based on simultaneously synthesis of organobentonite and removal of organic pollutants such as phenols from water in one-step, which resulted that both surfactants and organic pollutants were removed from water by bentonite. The effects of contact time, pH and inorganic salt on the removal of phenols were investigated. Kinetic results showed that phenols and cetyltrimethylammonium bromide (CTMAB) could be removed by bentonite in 25 min. The removal efficiencies were achieved at 69%, 92% and 99%, respectively, for phenol, p-nitrophenol and beta-naphthol at the initial amount of CTMAB at about 120% cation exchange capacity of bentonite. Better dispersion property and more rapid bentonite sedimentation were observed in the process. The results indicated that the one-step process is an efficient, simple and low cost technology for removal of organic pollutants and cationic surfactants from water. The proposed technology made it possible that bentonite was applied as sorbent for wastewater treatment in industrial scale.     

Chlorinated phenols as contaminants of soil and water in the vicinity of two Finnish sawmills

Contamination of soil and water in the vicinity of two sawmills using preservative against blue staining fungi that contained chlorophenols was studied. The soil around the treatment basins was found to contain up to 70 mg chlorophenols per kg and that in the storage area for treated lumber up to 6 mg per kg. Contamination extended to a depth of at least 2 meters near the treatment basins. Surface water inside the sawmill area was found to contain the same chlorophenols as those used in wood preservation, plus some additional isomers. The ground water and lake water around the sawmill areas was found to be contaminated by wood preservative.     

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.     

Photochemical Reactivity of Perchloroethylene: A New Appraisal

Perchloroethylene (PCE), a solvent used in dry cleaning, has been suspected of contributing significantly to photochemical ozone/oxidant (O₃/O_x) problems in urban atmospheres. Past evidence, however, was neither complete nor consistent. To interpret more conclusively the past evidence, and further understand PCE's role in the O₃O_x problem, a smog chamber testing program was conducted. The program's objectives were: (a) to explain the mechanism of the PCE reaction in smog chamber atmospheres, and (b) to extrapolate the smog chamber findings regarding PCE reactivity to the real atmosphere. Results showed that in smog chambers, PCE reacts and forms O₃/O_x following what appears to be a Cl instigated photooxidation mechanism rather than the OH initiated mechanism accepted in current smog chemistry. The evidence, collectively, strongly supported this conclusion even though the source of Cl atoms could not be identified with confidence. It was further concluded that in the real atmosphere neither the Cl instigated nor the OH instigated photooxidations of PCE can generate substantial concentrations of O₃/O_x. In fact, PCE contributes less to the ambient O₃/O_x problem than equal concentrations of ethane.     

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).     

Factors affecting photooxidation of oil constituents in the marine environment. I. Photochemical transformations of dimethylnaphthalenes in an aqueous environment in the presence and absence of oil

Photooxidation studies of 1,3-, 1,4-, 1,8- and 2,3-dimethylnaphthalene (DMN) suspended in and layered on seawater and distilled water have been performed in the presence and absence of crude Ekofisk oil, methylene blue and dibenzothiophene. With the exception of 2,3-DMN which was very insensitive to the reaction conditions, the course of reaction was, generally, influenced by the structure of the substrate, the salinity of the water, the oil and the presence of sulfur-containing compounds. In the absence of oil the photooxidation was fairly inefficient and took place exclusively in benzylic positions. In the presence of oil oxidation of the naphthalene moiety predominated due to abundant formation of singlet oxygen.     

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.     

Levels and distributions of polybrominated diphenyl ethers,hexabromocyclododecane, and tetrabromobisphenol A in sediments from Taihu Lake,China

The concentrations and distribution of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), and tetrabromobisphenol A (TBBPA) were investigated in 28 sediment samples collected from Taihu Lake, Eastern China. The results showed that all three classes of compounds were detected in 28 sediment samples but that PBDEs were the main contaminants in the study area. The total PBDE concentrations ranged from 3.77 to 347 ng/g dry weight (dw) with a mean value of 72.8 ng/g dw, whereas the concentrations ranged from 0.168 to 2.66 and from 0.012 to 1.30 ng/g dw for HBCD and TBBPA, respectively. In all of the sediment samples, BDE-209 was the predominant congener, accounting for 95.9 to 98.6 % of the total PBDEs, which indicated that commercial mixtures of deca-BDEs were the main sources of PBDE contamination. Higher concentrations of PBDEs were found in samples collected from Meiliang Bay and Gonghu Bay near the inflow river, which suggested that inflow runoff might play an important role in the PBDE levels in Taihu Lake sediments.     

Screening of endocrine-disrupting phenols, herbicides, steroid estrogens, and estrogenicity in drinking water from the waterworks of 35 Italian cities and from PET-bottled mineral water

We investigated contamination by endocrine-disrupting chemicals in drinking water from 35 major Italian cities and five popular Italian brands of bottled mineral water. The quality of Italian drinking water was assessed by combing chemical analysis with bioassay to quantify specific estrogenic contaminants and to characterize the actual biological effect of the mixture of chemicals present in drinking water including the contribution of not targeted compounds. The selected contaminants were natural and synthetic steroid estrogens, alkylphenols and bisphenol A, linuron, triazine herbicides, and their metabolites. A specific analytical method was developed based on solid phase extraction of 1 L of water and concentration to 100 μL for quantification by electrospray ionization liquid chromatography tandem mass spectrometry, achieving quantification limits of 0.05–0.36 ng/L for herbicides and 0.64–7.70 ng/L for steroids and phenols. No steroid estrogens were detected in any of the samples, while bisphenol A and nonylphenols were detected in the ranges of 0.82–102.00 and 10.30–84.00 ng/L respectively. Herbicides and their degradation products, when present, were found from slightly above the quantification limits up to 49.91 ng/L, mainly from cities in northern Italy. Chemical analyses were complemented by the performance of a bioassay for the determination of the estrogenic activity in the extracts based on the transactivation of estrogen receptor α-transfected reporter HeLa-ERE-Luciferase-Neomycin cell line. Activity was generally low with maximum estrogenicity of 13.6 pg/L estradiol equivalents.