| 1. |
- Altarawneh, Mohammednoor, et al.
(författare)
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Formation of polybrominated dibenzofurans (PBDFs) and polybrominated diphenyl ethers (PBDEs) from oxidation of brominated flame retardants (BFRs)
- 2020
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Ingår i: Journal of Hazardous Materials. - : Elsevier. - 0304-3894 .- 1873-3336. ; 400
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Tidskriftsartikel (refereegranskat)abstract
- Brominated aromatic rings constitute main structural entities in virtually all commercially deployed brominated flame retardants (BFRs). Oxidative decomposition of BFRs liberates appreciable quantities of bromobenzenes (BBzs). This contribution reports experimental measurements for the generation of notorious polybrominated dibenzofurans (PBDFs) and polybrominated diphenyl ethers (PBDEs) from oxidation of monobromobenzene (MBBz). In the light of developed product profiles, we map out reaction pathways and report kinetic parameters for PBDFs and PBDEs formation from coupling reactions of MBBz molecule and its derived ortho-bromophenoxy (o-BPhxy) radical using quantum chemical calculations. The identification and quantitation of product species involve the use of gas chromatograph - triple quadrupole mass spectrometer (GC-QQQMS) operating in the multiple reaction monitoring (MRM) mode. Bimolecular reactions of MBBz and o-BPhxy result in the generation of twelve pre-PBDF intermediates, of which four can also serve as building blocks for the synthesis of PBDEs. These four intermediates are denoted as pre-PBDE/pre-PBDF, with the remaining eight symbolised as pre-PBDF. 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 forming PBDFs. However, experimental measurements demonstrate PBDEs appearing in lower yields as compared to those of PBDFs; presumably due to H- and Br-induced conversion of the PBDEs into PBDFs following a simple ring-closure reaction. High reaction temperatures facilitate loss of ortho Br atom from PBDEs, followed by cyclisation step to generate PBDFs. PBDFs are observed in a narrow temperature range of 700–850 °C, whereas PBDEs form between 550–850 °C. Since formation mechanisms of PBDFs and polybrominated dibenzo-p-dioxins (PBDDs) are typically only sensitive to the bromination at ortho positions, the results reported herein apply also to higher brominated isomers of BBzs.
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| 2. |
- Gao, Qiuju, 1966-
(författare)
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Dioxins and dioxin-like compounds in thermochemical conversion of biomass : formation, distribution and fingerprints
- 2016
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In the transition to a sustainable energy supply there is an increasing need to use biomass for replacement of fossil fuel. A key challenge is to utilize biomass conversion technologies in an environmentally sound manner. Important aspects are to minimize potential formation of persistent organic pollutants (POPs) such as dioxins and dioxin-like compounds.This thesis involves studies of formation characteristics of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and naphthalenes (PCNs) in microwave-assisted pyrolysis (MAP) and torrefaction using biomass as feedstock. The research focuses are on their levels, distributions, fingerprints (homologue profiles and isomer patterns) and the underlying formation pathways. The study also included efforts to optimize methods for extracting chlorinated aromatic compounds from thermally treated biomass. The overall objective was to contribute better understanding on the formation of dioxins and dioxin-like compounds in low temperature thermal processes.The main findings include the following:Pressurized liquid extraction (PLE) is applicable for simultaneous extraction of PCDDs, PCDFs, PCNs, polychlorinated phenols and benzenes from thermally treated wood. The choice of solvent for PLE is critical, and the extraction efficiency depends on the degrees of biomass carbonization.In MAP experiments PCDDs, PCDFs and PCNs were predominantly found in pyrolysis oils, while in torrefaction experiments they were mainly retained in solid chars with minor fractions in volatiles. In both cases, highly chlorinated congeners with low volatility tended to retain on particles whereas the less chlorinated congeners tended to volatize into the gas phase.Isomer patterns of PCDDs, PCDFs and PCNs generated in MAP were more selective than those reported in combustion processes. The presence of isomers with low thermodynamic stability suggests that the pathway of POPs formation in MAP may be governed not only by thermodynamic stabilities but also by kinetic factors.Formation of PCDDs, PCDFs and PCNs depends not only on the chlorine contents in biomass but also the presence of metal catalysts and organic/metal-based preservatives.Overall, the results provide information on the formation characteristics of PCDDs, PCDFs and PCNs in MAP and torrefaction. The obtained knowledge is useful regarding management and utilization of thermally treated biomass with minimum environmental impact.
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| 3. |
- Gao, Qiuju, et al.
(författare)
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Formation of PCDDs and PCDFs in the torrefaction of biomass with different chemical composition
- 2017
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Ingår i: Journal of Analytical and Applied Pyrolysis. - : ELSEVIER SCIENCE BV. - 0165-2370 .- 1873-250X. ; 123, s. 126-133
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Tidskriftsartikel (refereegranskat)abstract
- Torrefaction is a thermal pre-treatment technology used to refine biomass, mainly for energy production purposes. However, there is currently a lack of information on the potential formation of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the torrefaction process. In this study, torrefaction was conducted using five different types of feedstock: stemwood, bark, wood from a discarded telephone pole, cassava stems and particle board. The feedstock as well as the torrefied biomass (chars) and the volatiles (non-condensable and condensable) generated during torrefaction were analyzed for PCDDs and PCDFs. PCDD concentrations in the torrefaction products were about 2-5 fold of those in the feedstocks. Torrefaction of particle board resulted in extensive formation of PCDDs (7200 ng kg(-1)) compared to the other four feedstocks (13-27 ng kg(-1)). Examination of the homologue profiles suggested that the observed PCDDs in the torrefaction products partly originated from new formation and partly physical transformation from volatilization and re-condensation of PCDDs present in the feedstock. Dechlorination of highly chlorinated compounds (HpCDD and OCDD) in the feedstock to form less chlorinated PCDDs was also observed. Compared to PCDDs, the net formation of PCDFs in the torrefaction process was low, except for the telephone pole sample, for which a dramatic increase (44-fold) of PCDFs was observed. PCDDs and PCDFs were mainly retained in the chars, accounting for 76-96% and 39-74% of the total concentration, respectively. It was also found that the highly chlorinated congeners tended to be retained in the chars, whereas the less chlorinated ones were predominantly volatilized into the gas phase.
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| 4. |
- Hou, Song, et al.
(författare)
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Oxidation of 4-bromo-4'-chlorobiphenyl, model species for forming mixed halogenated aromatic compounds
- 2017
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Ingår i: International Journal of Environment and Pollution. - : InderScience Publishers. - 0957-4352 .- 1741-5101. ; 61:3-4, s. 243-260
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Tidskriftsartikel (refereegranskat)abstract
- This contribution reports results from the gas-phase oxidation of 4-bromo-4'-chlorobiphenyl (4,4'-BCB) in order to fathom the formation of toxic species produced during the combustion of mixed halogenated aromatics. In their own right, mixed polybrominated/polychlorinated biphenyls (PXBs) represent a new class of environmental contaminants, recently detected in food and human tissues. Gas chromatography-quadrupole mass spectrometry (GC-QMS), gas chromatography-quadrupole time of flight mass spectrometry (GC-QTOFMS), Fourier transform infrared spectroscopy (FTIR) and ion chromatography (IC) served to analyse the volatile and semi-volatile organic compounds (V/SVOCs), including mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDD/Fs), and gaseous products including HBr/HCl. The selection of non-ortho substituted PXB as a model species yields a large number of halogenated compounds, including monochloro- and monobromobenzene and higher halogenated benzenes and naphthalenes and derivatives of halogenated benzenes (such as 1-chloro-4-ethynylbenzene). We also detect small amounts of chlorinated and mixed halogenated dibenzofurans. The present study provides insights into the formation of several classes of halogenated and mixed-halogenated pollutants in combustion processes involving both bromine and chlorine sources, such as those of brominated flame retardants and PVC plastics.
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| 5. |
- McNamee, Margaret, et al.
(författare)
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IAFSS agenda 2030 for a fire safe world
- 2019
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Ingår i: Fire Safety Journal. - : Elsevier BV. - 0379-7112. ; 110
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Tidskriftsartikel (refereegranskat)abstract
- The International Association of Fire Safety Science (IAFSS) is comprised of members from some 40 countries. This paper presents the Association's thinking, developed by the Management Committee, concerning pressing research needs for the coming 10 years presented as the IAFSS Agenda 2030 for a Fire Safe World. The research needs are couched in terms of two broad Societal Grand Challenges: (1) climate change, resiliency and sustainability and (2) population growth, urbanization and globalization. The two Societal Grand Challenges include significant fire safety components, that lead both individually and collectively to the need for a number of fire safety and engineering research activities and actions. The IAFSS has identified a list of areas of research and actions in response to these challenges. The list is not exhaustive, and actions within actions could be defined, but this paper does not attempt to cover all future needs.
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| 6. |
- Phan, Duong Ngoc Chau, 1985-
(författare)
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The relationship between fly ash chemistry and the thermal formation of polychlorinated pollutants during waste incineration
- 2013
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) is a major problem in waste incineration. Ideally, rather than relying on air cleaning systems and treatment techniques, their formation should be minimized or, if possible eliminated. The work presented in this thesis was conducted to obtain a deeper understanding of the thermal formation of PCDDs, PCDFs, PCBs, and PCNs during incineration using a 5 kW laboratory scale incinerator and two artificial wastes that were designed to reflect regional differences in waste composition.The first part of the thesis focuses on the validation of a recently-developed flue-gas sampling probe with enhanced cooling capabilities. Artifact formation of PCDDs and PCDFs can occur during the sampling of hot flue gases if the cooling is insufficient. The new probe was successfully used to collect samples at 700 °C without biasing the measured POP levels. The thermal formation of PCDDs, PCDFs, PCBs, and PCNs in the post-combustion zone of the incinerator was then studied by collecting flue gas samples at 400 °C, 300 °C, and 200 °C during the incineration of the two artificial wastes. Highly chlorinated POPs were formed in larger quantities when burning the waste with the higher content of metals and chlorine, which suggests that high metal levels in the waste favor the chlorination of less chlorinated POPs or otherwise facilitate the formation of highly chlorinated polyaromatics, possibly via the condensation of highly chlorinated phenols. The concentrations of these pollutants and the abundance of highly chlorinated homologues increased as the flue gas cooled. Fly ash particles play an important role in thermal POP formation by providing essential elements (carbon, chlorine, etc.) and catalytic sites. The chemical and mineralogical properties of fly ash samples were studied by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy/Energy Dispersive X-ray (SEM/EDX), and X-ray photoelectron spectroscopy (XPS) to determine their impact on thermal POP formation. Orthogonal Partial Least Squares (OPLS) modeling was used to identify correlations between the observed POP distributions and the physicochemical data. This investigation provided new insights into the impact of fly ash chemistry on thermal POP formation.In addition, the POP isomer distribution patterns generated during waste combustion were examined. These patterns are used to “fingerprint” mechanisms of POP formation. It was found that wastes containing large quantities of metals and chlorine favored the formation of highly chlorinated homologues including the very toxic 2,3,7,8-congeners. The data suggest that reducing fly ash emissions might increase the SO2 content of the flue gas and thereby suppress the Deacon process and the formation of harmful highly chlorinated aromatic species.
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