Fabrication of black phosphorus/CdS heterostructure with enhancement photocatalytic degradation activity for tetrabromobisphenol A and toxicity prediction of intermediates.

Black phosphorus nanosheets (BPNs)/CdS heterostructure was successfully synthesized via hydrothermal method. The experimental results indicated that BPNs modified the surface of CdS nanoparticles uniformly. Meanwhile, the BPNs/CdS heterostructure exhibited a distinguished high rate of photocatalytic activity for Tetrabromobisphenol A (TBBPA) degradation under visible light irradiation (λ > 420 nm), the kinetic constant of TBBPA degradation reached 0.0261 min-1 was approximately 5.68 and 9.67 times higher than that of CdS and P25, respectively. Moreover, superoxide radical (•O2-) is the main active component in the degradation process of TBBPA (the relative contribution is 91.57%). The photocatalytic mechanism and intermediates of the TBBPA was clarified, and a suitable model and pathway for the degradation of TBBPA were proposed. The results indicated that the toxicities of some intermediates were higher than the parent pollutant. This research provided an efficient approach by a novel photocatalyst for the removal of TBBPA from wastewater, and the appraisal methods for the latent risks from the intermediates were reported in this paper.

Mechanism investigation and stable isotope change during photochemical degradation of tetrabromobisphenol A (TBBPA) in water under LED white light irradiation.

Light driven degradation is very promising for pollutants remediation. In the present work, photochemical reaction of tetrabromobisphenol A (TBBPA) under LED white light (λ > 400 nm) irradiation system was investigated to figure out the TBBPA photochemical degradation pathways and isotope fractionation patterns associated with transformation mechanisms. Results indicated that photochemical degradation of TBBPA would happen only with addition to humic acid in air bubbling but not in N2 bubbling. For photochemical reaction of TBBPA, singlet oxygen (1O2) was found to be important reactive oxygen species for the photochemical degradation of TBBPA. 2,6-Dibromo-4-(propan-2-ylidene)cyclohexa-2,5-dienone and two isopropyl phenol derivatives were identified as the photochemical degradation intermediates by 1O2. 2,6-Dibromo-4-(1-methoxy-ethyl)-phenol was determined as an intermediate via oxidative skeletal rearrangement, reduction and O-methylation. Hydrolysis product hydroxyl-tribromobisphenol A was also observed in the reductive debromination process. In addition, to deeply explore the mechanism, carbon and bromine isotope analysis were performed using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) and gas chromatography-multicollector inductively coupled plasma mass spectrometry (GC/MC/ICPMS) during the photochemical degradation of TBBPA. The results showed that photochemical degradation could not result in statistically significant isotope fractionation, indicated that the bond cleavage of C-C and C-Br were not the rate controlling process. Stable isotope of carbon being not fractionated will be useful for distinguishing the pathways of TBBPA and tracing TBBPA fate in water systems. This work sheds light on photochemical degradation mechanisms of brominated organic contaminants.

Photodecomposition properties of brominated flame retardants (BFRs).

This study investigates the geometric and electronic properties of selected BFRs in their ground (S0) and first singlet excited (S1) states deploying methods of the density functional theory (DFT) and the time-dependent density functional theory (TDDFT). We estimate the effect of the S0→ S1 transition on the elongations of the C-Br bond, identify the frontier molecular orbitals involved in the excitation process and compute partial atomic charges for the most photoreactive bromine atoms. The bromine atom attached to an ortho position in HBB (with regard to C-C bond; 2,2',4,4',6,6'-hexabromobiphenyl), TBBA (with respect to the hydroxyl group; 2,2',6,6'-tetrabromobisphenol A), HBDE and BTBPE (in reference to C-O linkage; 2,2',4,4',6,6'-hexabromodiphenylether and 1,2-bis(2,4,6-tribromophenoxy)ethane, respectively) bears the highest positive atomic charge. This suggests that, these positions undergo reductive debromination reactions to produce lower brominated molecules. Debromination reactions ensue primarily in the aromatic compounds substituted with the highest number of bromine atoms owing to the largest stretching of the C-Br bond in the first excited state. The analysis of the frontier molecular orbitals indicates that, excitations of BFRs proceed via π→π*, or π→σ* or n→σ* electronic transitions. The orbital analysis reveals that, the HOMO-LUMO energy gap (EH-L) for all investigated bromine-substituted aromatic molecules falls lower (1.85-4.91 eV) than for their non-brominated analogues (3.39-8.07 eV), in both aqueous and gaseous media. The excitation energies correlate with the EH-L values. The excitation energies and EH-L values display a linear negative correlation with the number of bromine atoms attached to the molecule. Spectral analysis of the gaseous-phase systems reveals that, the highly brominated aromatics endure lower excitation energies and exhibit red shifts of their absorption bands in comparison to their lower brominated congeners. We attained a satisfactory agreement between the experimentally measured absorption peak (λmax) and the theoretically predicted oscillator strength (λmax) for the UV-Vis spectra. This study further confirms that, halogenated aromatics only absorb light in the UV spectral region and that effective photodegradation of these pollutants requires the presence of photocatalysts.

Improved photoelectrocatalytic degradation of tetrabromobisphenol A with silver and reduced graphene oxide-modified TiO2 nanotube arrays under simulated sunlight.

In present study, reductive graphene oxide and silver nanoparticles co-comodified TiO2 nanotube arrays were prepared, and which was investigated to degrade tetrabromobisphenol A. The arrays co-modified with silver nanoparticles and reductive graphene oxide prepared by electrodeposition method exhibited good photoelectrocatalytic degradative activity for tetrabromobisphenol A, and the degradation efficiency reached 99.6% within 80 min. The synergistic effect of high photoresponse of Ag nanoparticles with their high capture ability for photogenerated electrons and the extended wavelength absorption range of reductive graphene oxide resulted in the highest degradation efficiencies. Degradation is postulated to follow a stepwise reductive debromination mechanism.

A DFT/TDDFT study on the mechanisms of direct and indirect photodegradation of tetrabromobisphenol A in water.

Tetrabromobisphenol A (TBBPA) is the most widely used commercial brominated flame retardant. However, the mechanisms underlying the photodegradation of TBBPA remain unclear. Here we use density functional theory and time-dependent density functional theory to examine the photodegradation of the two species of TBBPA in water: TBBPA (neutral form) and TBBPA- (anionic form). The study includes direct photodegradation and indirect photodegradation of TBBPA with ·OH and 1O2. The results of the calculations indicate that indirect photodegradation of TBBPA and TBBPA- with ·OH occurs via OH-addition and Br-substitution. All of the OH-addition and Br-substitution pathways are exothermic. Indirect photodegradation of TBBPA and TBBPA- by 1O2 proceeds via H abstraction by 1O2.Ea was higher for H abstraction of TBBPA than H abstraction of TBBPA-. The mechanisms for the direct photodegradation of TBBPA and TBBPA- include debromination, C1C7/C7C13 cleavage, and cyclization. CBr cleavage was observed in the optimized geometries of TBBPA and TBBPA- at the lowest excited triplet state. However, high Ea values and an endothermic nature indicated that C1C7/C7C13 cleavage and cyclization reactions were not the main pathways. OH-adducts, Br-substitution products, H-abstraction (by 1O2) products, and debromination products were the main products of photodegradation of TBBPA. These findings provide useful information for risk assessment and pollution control of brominated flame retardants.

Experimental and theoretical investigations on debromination pathways of polybrominated biphenyls (PBBs) under ultraviolet light.

Polybrominated biphenyls (PBBs) are brominated flame retardants that are widely used in textiles and electronic products. Recently, many researches have been devoted to determining their concentrations in food and in the environment. Yet, their degradation behavior has been less investigated and is not well understood. Here, we have investigated the debromination pathways of PBBs by (UV) light in the case of 2,4,5-tribrominated biphenyl (PBB-29). Our investigation indicates that para-bromine substituent on PBB-29 was preferentially removed. By means of density functional theory (DFT), we found that the energies of the debromination products, the CBr bond length in the excited state (S1), the Mulliken charge of bromine in S1, and the lowest unoccupied molecular orbital (LUMO) in S1 correlated well with the debromination pathways of PBBs. Further, LUMO-based prediction of PBB debromination pathways in S1 suggests that the bromine substituent on all brominated positions (i.e. ortho-, meta- and para-) can be preferentially removed, as the debromination sequence is not based on the brominated position but on the specific brominated arrangement pattern. In addition, reductive debromination preferentially occurs on the benzene ring that has the highest number of bromine substituents. This study provided useful descriptors to predict the debromination pathways of PBBs, and the theoretical result greatly improve our understanding of photolytic debromination of PBBs.

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.

Photodegradation of 2,4,4'-tribrominated diphenyl ether in various surfactant solutions: kinetics, mechanisms and intermediates.

Currently, photodegradation has been proven to be an important way of eliminating polybrominated diphenyl ethers (PBDEs) from the environment. However, the mechanism of PBDE photodegradation in surfactants by UV light is still unclear. In this study, 2,4,4'-tribrominated diphenyl ether (BDE-28) was selected as the target pollutant to investigate the photodegradation of PBDEs in Triton X-100 (TX-100), sodium dodecylbenzenesulfonate (SDBS) and cetyltrimethylammonium bromide (CTAB) solutions. All photolysis experiments were performed above the critical micelle concentration (CMC). The results showed that photodebromination was the major pathway of BDE-28 photodestruction in different surfactants. From 1.5 CMC to 4 CMC, the photodegradation rates of BDE-28 increased as the concentration of TX-100 increased, and the increased concentration of SDBS has a negative effect on the photodegradation rate of BDE-28 due to the light barrier of SDBS. There was no obvious change in the case of CTAB. BDE-28 was debrominated to 4,4'-dibrominated diphenyl ether (BDE-15), 4-dibrominated diphenyl ether (BDE-3) and diphenyl ether (DE), subsequently. In addition, 2,8-dibrominated dibenzofuran (2,8-BDF), 2-monobrominated dibenzofuran (2-monoBDF), and dibenzofuran (DF) were produced via an intramolecular elimination of HBr from the PBDEs that had an ortho-bromine substituent. Moreover, DF can also be formed from DE and the generated amount of DF in CTAB was higher than that generated in SDBS and TX-100. We have also detected ortho-hydroxydiphenyl and para-hydroxydiphenyl during the photodegradation process.

Tetrabromobisphenol A photoelectrocatalytic degradation using reduced graphene oxide and cerium dioxide comodified TiO2 nanotube arrays as electrode under visible light.

Tetrabromobisphenol A, one of the most important brominated retardants, is an typical persistent organic pollutant and it is of great value to develop rapid and effective degradation method. Present study established a photoelectrodegradation method with CeO2 and reduced graphene oxide co-modified TiO2 nanotube arrays (RGO-CeO2-TiO2 NAs), which were successfully synthesized and characterized with scanning electron microscopy (SEM) and Energy Dispersive X Ray Spectrometry (EDX). The SEM Images revealed that the nanotubes had a diameter of about 100 nm and an obvious layer of CeO2 and RGO on the surface of TiO2 nanotube arrays. The EDX data exhibited the presence of Ce element. The results demonstrated that TBBPA was degraded at a high degradation rate constant of 0.0191 min-1, and photogenerated holes played a major role in the degradation reaction. Significant decrease of degradation efficiency was achieved with the presence of EDTA-2Na(hole scavenger), yet while the existence of t-BuOH(OH scavenger) resulted in less inhibition on the degradation. Besides, RGO-CeO2-TiO2 NAs exhibited good stability with rarely decline of degradation efficiency for ten reused runs. All these indicated that RGO-CeO2-TiO2 NAs were a good catalyst with extraordinary catalytic activity and stability for PEC degradation, and would have great potential in the control and removal of pollutants.

Photodecomposition of tetrabromobisphenol A in aqueous humic acid suspension by irradiation with light of various wavelengths.

The reactive species generated in aqueous 3,3',5,5'-tetrabromobisphenol A (TBBPA)/humic acid (HA) suspensions above the TBBPA pKa (∼7.4), under various light-irradiation conditions, namely ambient and ultraviolet light, were investigated using electron paramagnetic resonance (EPR) spectroscopy and liquid chromatography-mass spectrometry (LC-MS). We confirmed that singlet oxygen and OH radicals are the key reactive oxygen species generated at wavelengths greater than 400 and 300 nm, respectively. The amount of 2,6-dibromo-p-benzosemiquinone anion radicals (2,6-DBSQ(•-)) formed under irradiation at 400 nm increased linearly with respect to irradiation time; the initial reaction rate was 7.03 × 10(-9) mol g(-1) HA s(-1). The rate increased with increasing pH and light intensity. LC-MS and EPR spectroscopy showed that tribromohydroxybisphenol A was formed under irradiation at 300 nm via reaction of OH radicals with TBBPA. This study, for the first time, shows that the main byproducts formed during irradiation at wavelengths above 300 nm are 2,6-DBSQ(•-) and tribromohydroxybisphenol A, generated from singlet oxygen ((1)O2) and OH radicals, respectively. Photodecomposition of TBBPA in the environment may occur by formation of (1)O2 and OH radicals.

Photochemical transformation of tetrabromobisphenol A under simulated sunlight irradiation: Kinetics, mechanism and influencing factors.

A systematic study on photolysis of tetrabromobisphenol A (2,2',6,6'-tetrabromo-4,4'-isopropylidendiphenol, TBBPA) in water was investigated under simulated sunlight irradiation. The results showed that the photolysis of TBBPA followed apparent pseudo-first-order kinetics. The photolysis rate constants (k) changed from 2.80 × 10(-2) to 0.70 × 10(-2)min(-1) with the concentrations of TBBPA varying from 0.1 to 10 mg L(-1). Increasing humic acid (HA) concentration from 0-100 mg L(-1) led to the decrease of k from 2.53 × 10(-2) to 0.39 × 10(-2)min(-1), which was due to the competitive adsorption for photons between HA and TBBPA molecules. The photolysis rate was faster at near-neutral conditions (pH=6 and 7) than that in either acidic or basic conditions. Electron spin resonance (ESR) and reactive oxygen species (ROS) scavenging experiments indicated that TBBPA underwent self-sensitized photooxidation via ROS (i.e., OH, (1)O2 and O2(-)), and the process was mainly controlled by O2(-). After irradiation of 180 min, about 35.0% reduction of TOC occurred accompanied with approximate 99.1% of TBBPA removed. The detection of products (i.e., Br(-), bisphenol A, 2,6-dibromophenol, 2-bromophenol and phenol) revealed that the main photolytic pathways of TBBPA were debromination and breakage of C-C bond.

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.

Sequential reduction-oxidation for photocatalytic degradation of tetrabromobisphenol A: kinetics and intermediates.

C-Br bond cleavage is considered as a key step to reduce their toxicities and increase degradation rates for most brominated organic pollutants. Here a sequential reduction/oxidation strategy (i.e. debromination followed by photocatalytic oxidation) for photocatalytic degradation of tetrabromobisphenol A (TBBPA), one of the most frequently used brominated flame retardants, was proposed on the basis of kinetic analysis and intermediates identification. The results demonstrated that the rates of debromination and even photodegradation of TBBPA strongly depended on the atmospheres, initial TBBPA concentrations, pH of the reaction solution, hydrogen donors, and electron acceptors. These kinetic data and byproducts identification obtained by GC-MS measurement indicated that reductive debromination reaction by photo-induced electrons dominated under N(2)-saturated condition, while oxidation reaction by photoexcited holes or hydroxyl radicals played a leading role when air was saturated. It also suggested that the reaction might be further optimized for pretreatment of TBBPA-contaminated wastewater by a two-stage reductive debromination/subsequent oxidative decomposition process in the UV-TiO(2) system by changing the reaction atmospheres.

Efficient degradation of tetrabromobisphenol A by heterostructured Ag/Bi5Nb3O15 material under the simulated sunlight irradiation.

Heterostructured metallic silver-layered bismuth niobate two-component system (Ag/Bi(5)Nb(3)O(15)) was developed for the first time by a mild hydrothermal method combined with photodeposition. The Ag/Bi(5)Nb(3)O(15) exhibited single-crystalline orthorhombic structure with small particle size (50-200 nm) and octahedral as well as sheet-like shape; additionally, it possessed photoresponse in both UV and visible region. As a novel alternative photocatalysts to TiO(2), the photocatalytic activity of the Ag/Bi(5)Nb(3)O(15) was evaluated by the degradation of tetrabromobisphenol A, a member from the family of the brominated flame retardant, under solar simulating Xe lamp irradiation, and enhanced photocatalytic activity in compared to Bi(5)Nb(3)O(15) itself and Degussa P25 was obtained.

Photodegradation study of decabromodiphenyl ether by UV spectrophotometry and a hybrid hard- and soft-modelling approach.

This work presents an exploratory study of the photochemical degradation process of decabromodiphenyl ether (decaBDE) and gives an interpretation of the kinetic pathway, species and effects of the key factors involved in the degradation process. Use of lowly brominated diphenyl ethers (PBDE) has been banned by the EU and there seems to be evidence of the photolytic degradation of highly brominated PBDEs into lowly brominated congeners. Hence, the importance of knowing the photodegradation process of decaBDE. The photodegradation was investigated under UV light by UV-spectrophotometric monitoring. A novel hybrid data analysis approach, based on the combination of hard- and soft-spectrophotometric multivariate curve resolution, was applied to elucidate the mechanism of the degradation process, to resolve kinetic profiles and pure spectra of the photodegradation products and to evaluate the rate constants. The photodegradation process could be described with a kinetic model based on three consecutive first-order reactions and a decrease of the degradation process was observed as solvent polarity increased. Complementary identification of photodegradation products by gas chromatography coupled to mass spectrometry using negative chemical ionization (GC-NCI-MS) is attempted. This work presents a novel attempt of describing in a comprehensive way the photochemical degradation process of decaBDE, with all successive steps and related rate constants. This study proves also the potential of the proposed hybrid data analysis methodology as a general strategy to interpret the evolution of these photochemical reactions.

Oxidation of flame retardant tetrabromobisphenol A by singlet oxygen.

Wide use of flame retardants can pose an environmental hazard, and it is of interest to investigate how they may degrade. We report here that 3,3',5,5'-tetrabromobisphenol A (TBBPA) is subject to photosensitized oxidation involving singlet molecular oxygen ((1)O2). By using visible light and rose bengal or methylene blue as 102 photosensitizers, we have found that TBBPA is a 102 quencher. The quenching rate constant, k(q), depends on TBBPA ionization (pK = 7.4). In acetonitrile, where TBBPA is undissociated, the kq value is 6.1 x 10(5) M(-1) s(-1) for a TBBPA monomer and decreases to 2.9 x 10(4) M(-1) s(-1) for TBBPA dimers and/or aggregates. TBBPA dissociates in aqueous solutions, and its kq value is 1.44 x 10(9) M(-1) s(-1) in alkaline solution, decreasing to 3.9 x 10(8) M(-1) s(-1) at pH 7.2. The strong 102 quenching by TBBPA anion initiates an efficient oxidation of TBBPA, which results in oxygen consumption in aqueous micellar (e.g., Triton X-100) solutions containing photosensitizer. This oxygen consumption is mediated by transient radical species, which we detected by using EPR spectroscopy. We observed two major radicals and one minor radical generated from TBBPA by reaction with 102 at pH 10. One was identified as the 2,6-dibromo-p-benzosemiquinone radical (a2H = 2.36 G, g = 2.0056). A second radical (aH = 2.10 G, g = 2.0055) could not be identified butwas probably a 2,6-dibromo-p-benzosemiquinone radical containing an EPR-silent substituent at the 3-position. Spin trapping with 5,5-dimethyl-1-pyrroline N-oxide (DPMO) showed that other minor radicals (hydroxyl, carbon-centered) are also generated during the reaction of TBBPA with (1)O2. The photosensitized production of radicals and oxygen consumption were completely inhibited by the azide anion, an efficient physical (1)O2 quencher. Because TBBPA is a stable compound that at neutral pH does not absorb much of the atmosphere-filtered solar radiation, its photosensitized oxidation by (1)O2 may be the key reaction initiating or mediating TBBPA degradation in the natural environment.

Photochemical degradation of six polybrominated diphenyl ether congeners under ultraviolet irradiation in hexane.

The photodegradation of six individual PBDE congeners (BDE-28, 47, 99, 100, 153, 183) in hexane was investigated under UV light in the sunlight region, employing a mercury lamp filtered with Pyrex glass. All photodegradation reactions followed the pseudo-first-order kinetics, with the half-lives ranging from 0.26h for BDE-183 to 6.46h for BDE-100. The photochemical reaction rates of PBDEs decreased with decreasing number of bromine substituents in the molecule, also in some cases were influenced by the PBDE substitution pattern. Principal photoproducts detected were less brominated PBDEs, and no PBDE-solvent adducts were found. Consecutive reductive debromination was confirmed as the main mechanism for the photodegradation of PBDEs in hexane. In general, debromination firstly occurred on the more substituted rings, when the numbers of bromine atoms on the two phenyl rings were unequal. For less brominated PBDEs, the photoreactivity of bromines at various positions of phenyl rings decreased in the order: ortho>para; while for higher brominated PBDEs, the difference became not significant.

Deposition versus photochemical removal of PBDEs from Lake Superior air.

Analysis of a sediment core collected from Siskiwit Lake, located on a remote island in Lake Superior, provides evidence that polybrominated diphenyl ethers (PBDEs) are removed effectively from the atmosphere via deposition processes during long-range transport. A mass balance model based on photochemical rate constants and data from atmospheric samples was created to understand the relative importance of various photochemical and deposition processes in removing PBDEs from the atmosphere. Photolysis rate constants were derived from UV absorption spectra of 25 PBDEs recorded in isooctane over the range of 280-350 nm at 298 K. Photolysis decays measured for BDE-3 and -7 in the gas phase were substantial compared to a well-defined chemical actinometer, indicating that their photolysis quantum yields are significant. Dibenzofuran production was observed when PBDE congeners containing ortho-bromines were photolyzed in helium. From estimates of removal rates of PBDEs from the lower troposphere, we find that wet and dry deposition accountfor >95% of the removal of BDE-209, while photolysis accounts for -90% of the removal of gas-phase congeners such as BDE-47. These results help explain the deposition patterns of PBDEs found in lake and river sediments and have important implications concerning the inclusion of photolysis as a fate process in multimedia models.

Photolytic transformation of polybrominated biphenyls leading to the structures of unknown hexa- to nonabromo-congeners.

Polybrominated biphenyls (PBBs) have been used as flame-retardants mainly in the 1970s. Nowadays, they are found as ubiquitous contaminants in environmental samples. 2,2',4,4',5,5'-hexabromobiphenyl (PBB 153) is one of the persistent organic pollutants whose global ban is currently under discussion. Like the polychlorinated biphenyls (PCBs), 209 PBB congeners are existing in theory. However, only approximately 40 PBBs have been identified to date. In this work, we therefore used UV light, a sun simulator and natural sunlight for the photochemical debromination of PBB 209. All techniques led to the reductive debromination of PBB 209 albeit at different speed. Shifts of bromine substituents were not observed. Normal phase and reversed phase high performance liquid chromatography (HPLC) was used for the isolation of 12 reaction products some of which could be identified by (1)H NMR (PBB 202, 201, 197, 208, and 207). The other isolates (PBB 179, 178, 176, 199, 197, 196, and 194) were identified by realization of photolytic transformation studies with all isolates followed by comparison and evaluation of the obtained product spectra. In this way, we were able to establish (relative) retention times of the three nonabromobiphenyls, 9 of the 12 octabromobiphenyls, 14 of the 24 heptabromobiphenyl, and 16 of the 42 hexabromobiphenyls. Data on 24 PBBs are presented for the first time. Evaluation of the samples showed that Br was alternately removed from both phenyl rings and that positions with two vicinal Br substituents were most affected. Likewise, ortho-substituted PBBs were enriched.

Quantitative structure-property relationships for direct photolysis of polybrominated diphenyl ethers.

Using semiempirical quantum chemical descriptors, by partial least squares (PLS) regression, quantitative structure-property relationships (QSPRs) were established for direct photolysis quantum yields (Phi) and rate constants (k) of polybrominated diphenyl ether congeners dissolved in water/methanol and methanol solutions, respectively, and irradiated by artificial ultraviolet A light. Q(cum)(2), a parameter indicating robustness and predictive abilities of PLS models, for the significant QSPR models is larger than 0.702. The gap of frontier molecular orbital energies (E(LUMO)-E(HOMO)) and the most positive Mulliken atomic charges on a hydrogen atom (q(H+)) are two main molecular structural factors governing the logPhi values. logPhi increases with increasing E(LUMO)-E(HOMO) and q(H+) values. logk is mainly related to bromination degree and pattern which can be characterized by molecular weight (Mw), average molecular polarizability (alpha), and average Mulliken atomic charges on bromine atoms (q(Br)). logk increases with bromination degree (Mw, alpha) and q(Br).