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Studies on the Decomposition of Selected Brominated Flame Retardants (BFRs) and Formation of Polybrominated Dibenzo-p-dioxins and Dibenzofurans (PBDD/Fs) and Mixed Halogenated Dibenzo-p-dioxins and Dibenzofurans (PXDD/Fs)

Saeed, Anam (2016) Studies on the Decomposition of Selected Brominated Flame Retardants (BFRs) and Formation of Polybrominated Dibenzo-p-dioxins and Dibenzofurans (PBDD/Fs) and Mixed Halogenated Dibenzo-p-dioxins and Dibenzofurans (PXDD/Fs). PhD thesis, Murdoch University.

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Brominated flame retardants (BFRs) are bromine-bearing hydrocarbons added or applied to materials to increase their fire resistance. As thermal treatment or recycling activities are common disposal methods for BFR-laden objects, it is essential to determine the precise decomposition chemistry of BFRs at elevated temperatures, and their transformation pathways into hazardous pollutants. Sunlight can trigger the photodecomposition of BFRs, either during the life cycle of treated objects, or when emitted to the environment after disposal. Therefore, knowledge of the geometric and electronic structures of BFRs is of chief importance when tracking their fate in the ambient environment.

Although BFR decomposition mainly occurs in a condensed phase, gas phase reactions also contribute significantly to their overall decay and subsequent fragmentation into brominated pollutants. Thermal degradation of BFRs often proceeds in the presence of bromine atoms which inhibit complete combustion. Therefore, under thermal conditions such as smouldering, municipal waste incineration, pyrolysis, thermal recycling, uncontrolled burning and fires, BFRs degrade to form brominated products of incomplete combustion (BPICs). Thermal degradation of BFRs produces potent precursors to polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs). Co-combustion of BFR-containing objects with a chlorine source (e.g., polyvinyl chlorides) results in the emission of significant concentrations of mixed halogenated dibenzo-p-dioxins and dibenzofurans (i.e., PXDD/Fs; X = Br, Cl).

In this thesis, we investigated the thermochemical parameters of bromochlorophenols (BCPhs) and the photodecomposition properties of major BFRs and their derived brominated phenols (BPhs). We scrutinised the formation of brominated and non-brominated products that evolved during the thermal decomposition of major BFR i.e., tetrabromobisphenol A (TBBA), through experimental measurements coupled with accurate quantum chemical calculations. We acquired thermo-kinetic parameters as well as mechanistic routes pertinent to the destruction of TBBA. We illustrated reaction networks for the synthesis of PXDD/Fs from BPhs and chlorinated phenols (CPhs). Similarly, we described pathways leading to the formation of PBDFs and polybrominated diphenylethers (PBDEs) from brominated benzenes (BBzs). We critically reviewed the literature on BFR thermal decomposition with specific foci on underlying mechanisms, decomposition products, the influence of the polymeric matrix, metallic content and operational conditions.

As BCPhs are direct building blocks for the formation of PXDD/Fs, we computed the thermochemical parameters of their complete series. We calculated standard enthalpies of formation, entropies, heat capacities and bond dissociation enthalpies (BDHs) of O-H bonds for the complete series of BCPhs. Values of the acid dissociation constant (pKa) were estimated based on an accurate thermodynamic cycle incorporating solvation and protonation energies. Calculated values of BDHs of O-H bonds in BCPhs vary slightly with the change in degree and pattern of halogenation. Gibbs energies of solvation of BCPhs in water are highly exergonic, with their values increasing with the degree of halogen substitution. Values of pKa dictate that BCPhs characterised by high degrees of halogenation display stronger acidity and dissociate more easily in aqueous media (i.e., they are stronger acids than lower substituted phenols).

Photolysis and photochemical decomposition are important channels for the degradation of halogenated organic pollutants in the environment. Therefore, we performed density functional theory (DFT) and time-dependent density functional theory (TDFT) calculations in order to derive the photodecomposition properties of major deployed BFRs and congeners of BPhs in both gaseous and aqueous media. We clarified the effect of degree and pattern of bromination on the photodebromination of selected brominated aromatic compounds based on several molecular descriptors; namely, geometries of the ground (S0) and electronically first excited (S1) states, values of the HOMO-LUMO energy gap (EH-L) and atomic charges on bromine atoms (qBr). Molecules exhibit different geometries in the S0 and S1 states and C-Br bonds elongate upon S0 → S1 transitions. In agreement with the recent findings on PBDEs, we found that the photoreactivity of bromine atoms in investigated BFRs and BPhs followed the sequence of ortho > meta > para. The bromine atom connected to the ortho-position holds the highest positive atomic charge and, thus, experiences the greatest lengthening of C-Br bonds in the S1 state, in both gaseous and an aqueous media, prompting their reductive debromination. Excitation energies decrease linearly with increasing numbers of bromine substituents, and congeners with a high degree of bromination photodecompose more readily than lower brominated isomers. Computed values of EH-L for major BFRs and their non-brominated molecules inferred that the number of bromine substituents and the nature of the structure (aromatic/non-aromatic) contributes significantly towards the photoreactivity of molecules.

We conducted gas phase thermal decomposition of TBBA using a laboratory-scale tubular reactor. Our main focus was to identify pollutants arising in the temperature range of 673 – 1123 K following evaporation of TBBA in the gas phase. The identification and quantitation involved the use of a gas chromatograph – triple quadrupole mass spectrometer (GC-QQQMS) instrument, functioning in multiple reaction monitoring (MRM) and total ion current (TIC) modes. Product analysis revealed that thermal decomposition of TBBA commenced at 723 K. The major decomposition products were HBr, di-tribrominated bisphenols, benzene, phenol, mono-tribrominated congeners of benzene and phenol, brominated and non-brominated alkylated benzenes, benzofuran, bromobenzofuran, dibenzofuran, bromine substituted polyaromatic hydrocarbons (PAHs), biphenyl and biphenylene. We observed that, most of the decomposition products evolved in trivial concentrations at a temperature of 773 K and peaked at around 923 – 973 K. Higher temperatures favour the generation of non-brominated products. In this chapter, we have performed quantum chemical calculations to derive the degradation pathways of TBBA and to illustrate routes for the formation of brominated and non-brominated species.

We constructed formation mechanisms related to the emission of PBDD/Fs in systems involving BFRs. In particular, we investigated formation corridors of (i) PXDD/Fs from the coupling reactions of 2-chlorophenoxy (2-CPhxy) and 2-bromophenoxy (2-BPhxy) radicals, (ii) PBDFs and PBDEs synthesis from the condensation reaction of monobromobenzene (MBBz) and a 2-BPhxy radical. The coupling reactions of 2-BPhxy and 2-CPhxy radicals produce keto-ether (through the additions of a phenoxy O at ortho C(H), C(Cl) and C(Br) sites) and diketo (at ortho positions to C–C bridges) structures. Keto-ethers act as direct intermediates for the formation of dioxin moieties such as dibenzo-p-dioxin (DD), 1-monochlorodibenzo-p-dioxin (1-MCDD), 1-monobromodibenzo-p-dioxin (1-MBDD), 1-bromo-6-chlorodibenzo-p-dioxin (1-B,6-CDD) and 1-bromo-9-chlorodibenzo-p-dioxin (1-B,9-CDD) molecules. Diketo adducts initiate the formation of furan species, i.e., 4-monochlorodibenzofuran (4-MCDF), 4-monobromodibenzofuran (4-MBDF) and 4-bromo-6-chlorodibenzofuran (4-B,6-CDF) compounds, through interconversion and rearrangement reactions. We found that, these mechanisms of formation, commencing from halogenated phenoxy radicals, are largely insensitive to patterns and degrees of halogenation on meta and para sites. It follows that, our developed mechanistic and kinetic factors of reactions involving 2-BPhxy and 2-CPhxy should also apply to higher halogenated phenoxy radicals.

We explored the initial oxidative decomposition pathways of monobromobenzene (MBBz) in the generation of BPhxy radicals and examined the possible dimerisation reactions of MBBz and 2-BPhxy. It was found that, the coupling of MBBz and 2-BPhxy results in the generation of twelve pre-PBDF intermediates, of which four can also serve as building blocks for the synthesis of PBDEs. The resonance-stabilised structure of the o-BPhxy radical accumulates more spin density character on its phenoxy O atom (30.9 %) in reference to ortho-C and para-C sites. Thus, the formation of the pre-PBDE/pre-PBDF structures via O/o-C couplings advances faster, as it requires lower activation enthalpies (79.2 – 84.9 kJ mol-1) than the pre-PBDF moieties, which arise via pairing reactions involving o-C(H or Br)/o-C(H or Br) sites (97.2 – 180.2 kJ mol-1). Kinetic analysis indicates that the O/o-C pre-PBDE/pre-PBDF adducts self-eject the out-of-plane H atoms to produce PBDEs, rather than undergo a three-step mechanism that forms PBDFs. Since the formation mechanisms of PBDFs and PBDDs are typically only sensitive to the bromination at ortho positions, the results reported herein also apply to higher brominated isomers of BBzs.

Overall, this thesis provides novel and comprehensive information on the thermochemical properties of the complete series of BCPhs (potential precursors to PXDD/Fs) and the electronic/structural characteristics of BFRs and their derived BPhs, with regards to their photodecomposition. To gain an insight into the degradation of TBBA once it has evaporated, this thesis examines the pure gas phase decomposition of TBBA and suggests mechanisms by which the experimentally-detected volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) are generated. Furthermore, this thesis explores the role of BPhs and CPhs as building blocks for the formation of PXDD/Fs, and computes their parameters. We also elucidate reaction pathways and thermo-kinetic parameters for PBDFs and PBDEs produced by the oxidation of BBzs.

Publication Type: Thesis (PhD)
Murdoch Affiliation: School of Engineering and Information Technology
Supervisor: Altarawneh, Mohammednoor and Dlugogorski, Bogdan
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