Efficient photocatalytic debromination of 2,2',4,4'-tetrabromodiphenyl ether by Ag-loaded CdS particles under visible light.

Highly active and visible light-driven Ag-loaded CdS photocatalysts were prepared via a hydrothermal synthesis and photodeposition method. The removal and debromination of 2,2',4,4'-tetrabromodiphenyl ether was achieved efficiently using this Ag-loaded CdS under visible light, with a removal efficiency of 100% and a debromination ratio of 44.3% being achieved within 30 min. Both the reaction solvent and the water content were found to have a strong influence on the removal efficiency and the debromination ratio. In addition, the stepwise debromination preference was ortho ≫ para, thereby indicating that the main debromination pathway was electron reduction. The stability and efficiency of these Ag-loaded CdS photocatalysts for the removal of BDE47 were satisfactory, and so our results confirmed the development of a promising visible light-driven catalyst for the removal of polybrominated diphenyl ethers.

Mass-flow-based removal and transformation potentials for TBBPA, HBCDs and PBDEs during wastewater treatment processes.

At a sewage treatment plant, 27 polybrominated diphenyl ethers, 17 methoxylated brominated diphenyl ethers, nine hydroxylated brominated diphenyl ethers, three hexabromocyclododecane diastereomers, and tetrabromobisphenol A were monitored at five major treatment stages (the influent, primary settlement stage, biological reaction stage, secondary settlement stage, and the UV irradiation disinfection stage). Hexabromocyclododecanes were the dominant chemicals, contributing 40% of the total concentrations of the chemicals in the dissolved phase of the sewage. Brominated flame retardant mass flow in the wastewater was lower after than before the biological reaction stage, and more than 70% of the inflowing mass load was removed from the mainstream wastewater by becoming associated with the sludge. More than half of mass loads of parent brominated flame retardants in the wastewater were removed after the treatments, but up to 10% of the initial mass loads remained in the final effluent and was expected to be released into the aquatic environment. The hydroxylated and methoxylated brominated diphenyl ether concentrations decreased by <25%, much less than the polybrominated diphenyl ethers. It is possible that hydroxylated and methoxylated polybrominated diphenyl ethers formed through the transformation of polybrominated diphenyl ethers during the biological reactions of treatment processes.

Sunlight Irradiation of Highly Brominated Polyphenyl Ethers Generates Polybenzofuran Products That Alter Dioxin-responsive mRNA Expression in Chicken Hepatocytes.

We report on two highly brominated polyphenyl ether flame retardants, tetradecabromo-1,4- diphenoxybenzene (TeDB-DiPhOBz) and 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE-209), that formed photolytic degradation products in tetrahydrofuran (THF)/hexane solvent after 21 days of natural sunlight irradiation (SI). These degradation products of SI-TeDB-DiPhOBz and SI-BDE-209 included the numerous polybrominated homologue groups of polybenzofurans and dibenzofurans, respectively. Formation of similar polybenzofuran and dibenzofuran products was also observed following a 3 month exposure of the solid powder forms of TeDB-DiPhOBz and BDE-209 to natural SI. These resulting degradation product mixtures were administered to chicken embryonic hepatocytes (CEH) to determine effects on mRNA expression levels of 27 dioxin-responsive genes. For the solvent-based SI study, equivalent concentrations of 1 or 25 µM of SI-TeDB-DiPhOBz or 1 or 10 µM of SI-BDE-209 resulted in gene expression profiles that were similar to those of the most potent dioxin-like compound, 2,3,7,8-tetrachlorodibenzo-p-dioxin. In addition, a concentration-dependent induction of CYP1A4 and CYP1A5 mRNA was observed following exposure to SI-TeDB-DiPhOBz and SI-BDE-209. Based on ECthreshold values for CYP1A4/5 mRNA expression, relative potency (ReP) values were 1 × 10(-6) and 1 × 10(-5) for SI-TeDB-DiPhOBz and SI-BDE-209, respectively. The SI TeDB-DiPhOBz and BDE-209 powder degradation product mixture also significantly induced CYP1A4 mRNA levels in CEH. Our findings clearly show that the environmental stability of TeDB-DiPhOBz and BDE-209, and possibly other highly brominated polyphenyl ethers, is of great concern from a dioxin-like degradation products and toxicity perspective.

Fate of PBDEs during food processing: Assessment of formation of mixed chlorinated/brominated diphenyl ethers and brominated dioxins/furans.

The aim of this study was to evaluate effects of food processing on PBDE levels, in particular influence of heat treatment on degradation of PBDEs, including possible formation of chlorinated diphenyl ethers or brominated dioxins/furans as degradation products. It was shown that PBDEs heated in the presence of chlorine (from either organic or inorganic sources) formed mixed chlorinated/brominated diphenyl ethers. However, no PCDEs were formed in the presence of lipids. Lipid medium increased stability of PBDEs exposed to UV irradiation. Profile of congeners formed in result of the debromination reaction was significantly different than profiles observed by some other authors in aliphatic organic solvents. Grilling processes increased concentrations (calculated on the fresh product basis) of the studied compounds by 4-8/22-34% for electric/coal grill, respectively. Depending on the congener and on the applied heat treatment, PBDE mass in pork meat after grilling dropped by 26-53%. No detectable quantities of either brominated dioxins or furans were formed during thermal processing of food containing typical levels of PBDEs.

BDE-209: kinetic studies and effect of humic substances on photodegradation in water.

BDE-209 is a brominated flame retardant and a priority contaminant, which has been found in several environmental matrices, namely, in water. To date, there are no quantum yield data for BDE-209 photodegradation by sunlight in water, to allow predicting half-life times in aquatic systems. In this work, the kinetics of BDE-209 photodegradation in water was studied and the influence of different fractions of aquatic humic substances (HS) was evaluated. Aqueous solutions of BDE-209 exposed for different periods of time to simulated sunlight were analyzed by HPLC-UV after being concentrated using dispersive liquid-liquid microextraction (DLLME) or solid-phase extraction (SPE). The photodegradation of BDE-209 in aqueous solution followed pseudo-first-order kinetics. The average quantum yield obtained of 0.010 ± 0.001 (about 20-fold lower than the quantum yield determined in ethanol) allow to predict an outdoor half-life time of 3.5 h. The photodegradation percentage of BDE-209 was not significantly affected by the XAD-4 fraction of HS, but it decreased substantially in the presence of humic and fulvic acids. Light screening by the humic substances could not explain this delay, which is probably the result of the association of the compound with the hydrophobic sites of the humic material.

Photolysis of oxyfluorfen in aqueous methanol.

Photolysis of oxyfluorfen, an herbicide of the nitrodiphenyl ether class, was studied in aqueous methanol under UV and sunlight. UV irradiation was carried out in a borosilicate glass photoreactor (containing 250 ppm oxyfluorfen in 50% aqueous methanol) equipped with a quartz filter and 125 watt mercury lamp (maximum output 254 nm) at 25 ± 1°C. Sunlight irradiation was conducted at 28 ± 1°C in borosilicate Erlenmeyer flasks containing 250 ppm oxyfluorfen in 50% aqueous methanol. The samples from both the irradiated conditions were withdrawn at a definite time interval and extracted to measure oxyfluorfen content by gas chromatography-flame ionization detector for rate study. The half-life values were 20 hours and 2.7 days under UV and sunlight exposure, respectively. Photolysis of oxyfluorfen yielded 13 photoproducts of which three were characterized by infrared spectrophotometer and (1)H NMR and (13)C NMR spectroscopy. The rest of the photoproducts were identified by gas chromatography-mass spectrometry (GC-MS) and thin layer chromatography (TLC). An ionization potential 70 eV was used for electron impact-mass spectrometry (EI-MS) and methane was used as reagent gas for chemical ionization-mass spectrometry (CI-MS). Two of the photoproducts were also synthesized for comparison. The main phototransformation pathways of oxyfluorfen involved nitro reduction, dechlorination, and hydrolysis as well as nucleophiles displacement reaction.

UV-induced formation of bromophenols from polybrominated diphenyl ethers.

Bromophenols (BPs) are both man-made industrial compounds and naturally produced secondary metabolites of algae and sponges. This study explored the formation of BPs by UV irradiation of polybrominated diphenyl ethers (PBDEs). Simulated sunlight (10-80 min) and natural sunlight irradiations (5 days) of BDE-153, BDE-154, BDE-183, BDE-196, and technical octabromodiphenyl ether (DE-79) generated hydrodebrominated PBDEs along with up to 0.7-4 mass % BPs. UV absorption spectra were recorded to show that the para-substituted PBDEs and BPs are those predominately transformed because this structural feature causes a significant bathochromic shift of λmax to higher wavelength. A decrease of higher brominated BPs in favor of lower brominated BPs was observed with time. All possible substitution patterns on the BPs formed by the cleavage of the parent PBDEs and respective hydrodebromination products were observed. The main di- and tribromophenols detected were 2,4-diBP > 2,5-diBP and 2,4,6-triBP > 2,4,5-triBP on average. The irradiation conditions were similar to real-world scenarios and emphasized the environmental relevance of these photolysis products of PBDEs. The meta-substituted BPs can be used as markers to distinguish photolytic PBDE transformation products from naturally produced BPs, which exclusively feature bromo-substitutents in ortho- and para-positions.

Efficient oxidative debromination of decabromodiphenyl ether by TiO2-mediated photocatalysis in aqueous environment.

Direct evidence was first demonstrated for the oxidative degradation of decabromodiphenyl ether (BDE209) in aqueous TiO(2) dispersions under UV irradiation (λ > 340 nm). BDE209 was hardly debrominated over TiO(2) in UV-irradiated acetonitrile dispersions, but the addition of water into the dispersions greatly enhanced its photocatalytic oxidative debromination. The debromination efficiency of BDE209 as high as 95.6% was achieved in aqueous TiO(2) dispersions after 12 h of UV irradiation. The photocatalytic oxidation of BDE209 resulted in generation of aromatic ring-opening intermediates such as brominated dienoic acids, which were further degraded by prolonging UV irradiation time. The photocatalytic oxidative debromination of BDE209 was further confirmed by the observation that the BDE209 degradation in water-acetonitrile mixtures with different water contents was positively correlated with the formation of •OH radicals, but not photogenerated electrons. The use of water not only avoided the scavenging of reactive radicals by organic solvent but also enhanced the adsorption of BDE209 on the surface of TiO(2), both of which favor the contact of BDE209 with photogenerated holes and •OH species. The confirmation of efficient oxidative degradation and debromination of BDE209 is very important for finding new ways to remove polybrominated diphenyl ethers from the environment.

Photocatalytic debromination of preloaded decabromodiphenyl ether on the TiO(2) surface in aqueous system.

There have been serious concerns about polybromodiphenyl ethers (PBDEs) in the environment because of their global distribution and bioaccumulation. Owing to strong hydrophobicity of PBDEs, the regular photocatalytic system, in which the substrate is solvated in the bulk solution, is not applicable to the removal of the PBDEs in water. In this work, the photocatalytic reduction degradation of decabromodiphenyl ether (BDE209), the most-used PBDEs, was investigated in aqueous system, by pre-adsorbing it on the surface of photocatalyst. It was found that the preloaded BDE209 underwent efficient reductive debromination in aqueous system under irradiation with wavelength larger than 360 nm in the presence of electron donors such as methanol. Our experiments further show that such a preloaded system exhibits different characteristics from that in the organic solution. The meta-debrominated intermediate is predominant in the present system, while the ortho-debrominated one is the main nona-BDE products in the organic solution. In addition, different from other photocatalytic system, the pH has little effect on the photocatalytic reaction. We propose that these differences are originated from the formation of overlayer of hydrophobic BDE209 to limit the motion of BDE209 and the access of water and H(+)/OH(-) to the TiO(2) surface.

Levels of polybrominated diphenyl ethers (PBDEs) in dust from personal automobiles in conjunction with studies on the photochemical degradation of decabromodiphenyl ether (BDE-209).

The levels of 21 PBDE congeners were detemined in the dust sampled from 66 personal automobiles. The dominant congener in automobile dust was BDE-209 with a median level of 8.12 µg g⁻¹. Personal vehicle dust samples contained the characteristic profile of the PBDE congeners that comprise the PentaBDE and DecaBDE commercial formulations. Levels of PBDEs in personal automobiles are generally reduced in comparison to our previously reported levels in resale vehicles on dealership lots presumably due to a dilution effect introduced by dust or debris that does not originate from the vehicle. Laboratory photochemical studies were conducted on both automobile dust collected from personal vehicles as well as BDE-209 adsorbed to sodium sulfate. No significant degradation occurred in the personal vehicle dust after 56 days of constant UVA irradiation while significant degradation did occur with BDE-209 adsorbed to sodium sulfate. PBDEs from the degradation of BDE-209 were identified and potential degradation pathways elucidated. Human exposure potential to PBDEs from automobile dust ingestion remains a serious concern in the U.S. population.

Enhanced dissipation of oxyfluorfen, ethalfluralin, trifluralin, propyzamide, and pendimethalin in soil by solarization and biosolarization.

This study was conducted to assess the effects of solarization and biosolarization on the degradation of oxyfluorfen, ethalfluralin, trifluralin, propyzamide, and pendimethalin. The experimental design consisted of 17 L pots filled with clay-loam soil, which were contaminated with the studied herbicides. Then, soil disinfection treatments were applied during the summer season, including a control without disinfection (C), solarization (S), and biosolarization (BS). Soil from five pots per treatment was sampled periodically up to 90 days. Herbicide dissipation rates were higher in both S and BS treatments with regard to the control. Similar dissipation rates were observed under S and BS for most of the herbicides studied, except oxyfluorfen and pendimethalin, which were degraded to a greater extent in the BS than in the S treatment. The obtained results showed that both solarization and biosolarization can be considered, in addition to soil disinfection techniques, such as bioremediation tools for herbicide-polluted soils.

Photolytical transformation rates of individual polybrominated diphenyl ethers in technical octabromo diphenyl ether (DE-79).

Polybrominated diphenyl ethers (PBDEs) are of environmental concern due to their persistence, potential to bioaccumulate, and possible toxic effects, especially for the lower brominated homologues. Reductive debromination under UV light has been identified as the main abiotic pathway for PBDE transformation. Although the kinetics and transformation products have been determined for individual PBDE congeners in different matrices, no effort has been made to determine the kinetics of these congeners when technical mixtures are exposed to UV light. We irradiated technical octabromodiphenyl ether (DE-79) in a perdeuterated solvent to determine the photolytic transformation kinetics of native PBDE congeners. Each deuterium that replaced bromine resulted in a shift to higher masses compared to the native congener, which was measured by gas chromatography with electron ionization mass spectrometry in the selected ion monitoring mode (GC/EI-MS-SIM). Tri-, tetra-, and pentabromodiphenyl ether products (BDE 28, BDE 47, BDE 49, BDE 99, BDE 100) could be proportioned to higher brominated precursors as a function of irradiation time. The kinetics of UV-irradiated single PBDE congeners matched well with results of previous studies of single congeners. However, when the same congeners were irradiated in the technical DE-79 mixture, their half-lives were longer by 20-160%. This study indicates that individually irradiated PBDE congeners behave differently than if present as a mixture. This result should be taken into account in models predicting the environmental fate of PBDEs and most likely also the mixtures of other contaminant groups.

TiO2-mediated photocatalytic debromination of decabromodiphenyl ether: kinetics and intermediates.

In this work, we report the rapid photoreductive debromination of decabromodiphenyl ether (BDE209) byTiO2. The degradation of BDE209 is a stepwise process, and the bromines at the ortho positions are much more susceptible than those at the para positions. The photocatalytic degradation kinetics of BDE209 was further investigated under different reaction conditions (various solvents, in the presence of H2O, acids, or bases). A possible photoreductive debromination pathway was proposed on the basis of the identified reaction intermediates and density functional theory (DFT). This study provides a potential application of photocatalysis in removal of PBDE contamination.

Quantitative structure-property relationship studies for direct photolysis rate constants and quantum yields of polybrominated diphenyl ethers in hexane and methanol.

The direct photolysis of 18 individual polybrominated diphenyl ethers (PBDEs) substituted with 1-7 bromine atoms was investigated in hexane and methanol under UV irradiation. Based on the determined photolysis rate constants (k(p)) and calculated quantum yields (Phi), four quantitative structure-property relationship (QSPR) models were developed by partial least squares (PLS) method and 20 fundamental molecular structural descriptors. The fitting results showed that all of four QSPR models had good predictability and correlations between observed and predicted photolysis data were significant. The predominant molecular descriptors governing photolysis rate constants of PBDEs in hexane were Mw; Sm; qBr; and qBr+], while in methanol the significant variables were alpha, TE, M(w) and S(m). In terms of the QSPR models for quantum yields of PBDEs in hexane and methanol, the governing molecular descriptors were almost the same. Molecular weight (M(w)) and three atomic charge descriptors (qBr, qH, qBr) were all presented in the four QSPR models, implying that photolysis rate constants and quantum yields were affected by the bromination degree and substitution pattern of PBDE molecules.

Photolytic degradation of polybromodiphenyl ethers under UV-lamp and solar irradiations.

Polybromodiphenyl ethers (PBDEs) are widely used flame retardant additives and have been mainly used in polymers for many plastic and electronic products. PBDEs have been found to bioaccumulate in both aquatic and terrestrial ecosystems and even human bodies. The technical product with the highest use is decabrominated diphenyl ether (BDE-209). Therefore, we chose to examine the solar and UV-lamp degradation of BDE-209. A linear increase of the photodegradation rate constant for BDE-209 was observed with the solar light intensity. The degradation reactions follow the pseudo-first-order kinetics. The photodegradation of BDE-209 produced other less brominated diphenyl ethers under ultraviolet light exposure, suggesting that the photodegradation of BDE-209 is a sequential dehalogenation mechanism. BDE-209 underwent rapid reductive debromination in these photodecomposition experiments. The formation rate constants of three nonabromodiphenyl ethers increase with the order of BDE-206, BDE-207 and BDE-208, indicating debromination mainly occurred at para>meta>ortho positions. These findings of the process properties and reductive debromination mechanism of the photolytic degradation of PBDEs can facilitate the design of remediation processes and also aid in predicting their fate in the environment.