《Pollution Control of Polybrominated Diphenyl Ethers Among New Pollutants（新污染物治理之多溴联苯醚污染控制）》在简要地介绍了多溴联苯醚的污染特征和相关修复技术的基础上，系统总结了作者及其团队针对多溴联苯醚污染控制开展的多溴联苯醚热解过程的污染转化、基于零价铁的多溴联苯醚还原降解、紫外光下多溴联苯醚的直接光降解、多溴联苯醚的光催化降解、多溴联苯醚的微生物降解、多溴联苯醚的化学氧化、表面活性剂洗脱液体系中多溴联苯醚的选择性去除处理等开展的大量应用基础性研究工作。这些研究成果有助于阐明多溴联苯醚的环境过程及其内在机制，并可为多溴联苯醚污染控制与修复提供科学依据和技术支持。

Chapter 1 Occurrence and Pollution Control of PBDEs
　　PBDEs are a class of brominated fire retardant that is widely used in electronic products (circuit boards and plastic enclosures)， foam， carpets， textiles， construction materials， and vehicles (Abbasi et al.， 2019). Due to strict fire safety requirements around the world， large amounts of PBDEs have been produced and applied over the decades. However， as persistent， bioaccumulated， and endocrine- disrupting compounds (Wu et al.， 2020)， PBDEs have attracted more and more attention to their possible hazards and transformation behaviors， especially after they were first detected in biological tissues (Andersson & Blomkvist， 1981).
　　PBDEs are regarded as pollutants that can be released from both point and non-point sources. Point sources include PBDE production and processing bases， as well as waste treatment sites such as e-waste dismantling， dumping， or incineration sites， which release highly concentrated PBDEs and form pollution sites. Non-point sources include the volatilization of PBDEs from commodities into the air， and further transfer faraway or migrate into soil and water by dry or wet deposition， causing background pollution worldwide. The PBDEs in air， soil， and water further accumulate in organisms via the food chain. During these environmental geochemical processes and biochemical processes， the more toxic intermediates can be generated， which results in the risk of human exposure through direct contact and diet (Law et al.， 2014; Wu et al.， 2020). Due to these risks， developed countries introduced policies to restrict the production， use， and treatment， and the Stockholm Convention and Basel Convention were signed to regulate PBDEs and hazardous wastes (Ilankoon et al.， 2018).
　　Reported data show that PBDE concentration in Europe has decreased in recent years; the trend in other areas is not clear due to a lack of data (Law et al.， 2014). In China， the PBDE concentrations of air shows a decreasing trend， and no obvious trend appears in water and soil， while some investigations find increasing PBDE concentration in sediments (Jiang et al.， 2019). Therefore， the monitoring and elimination of PBDEs in the environment is still an issue of major concern.
　　1.1 Occurrence of PBDEs
　　1.1.1 Physiochemical properties of PBDEs
　　The structure of PBDEs is shown in Fig. 1-1. The hydrogen atoms on the benzene rings can be replaced by bromine atoms. The highest-brominated compound is decabro- modiphenyl ether (decaBDE)， and the lowest-brominated compound is monobro- modiphenyl ethers (monoBDEs). Therefore， based on the number of bromine atoms， there are 10 homologues， and each homologue contains 3， 12， 24， 42， 46， 42， 24， 12， 3， and 1 isomers for 1， 2， 3， 4， 5， 6， 7， 8， 9， 10 bromine atoms， respectively. There are 209 homologues in PBDEs， which follow the naming rules developed by Ballschmiter and Zell (1980)， namely BDE-[IUPAC number]. For example， DecaBDE is named BDE-209， and monoBDE has three isomers that are named BDE-1， BDE-2， and BDE-3 for ortho， meta， and para-position substitution of bromine， respectively. The names and their corresponding bromine substitution characteristics are shown in Table 1-1.
　　Fig. 1-1 Structure of PBDEs(m≤5， n≤5).
　　As commonly applied flame retardants， PBDEs are mainly used as additives in plastics. During combustion， flame-retardant additives react with the burning polymer in the vapor phase， disrupting the production of free radicals and shutting down the combustion process. The highly reactive radicals??and??can react in the gas phase with other radicals， such as bromine radicals??resulted from flame-retardant degradation， which decreases the kinetics of the combustion. The PBDEs used in products are commercial mixtures， including pentabromodiphenyl ethers (pentaBDEs)， octabromodiphenyl ethers (octaBDEs)， and decaBDE. The detailed composition profiles of three kinds of mixtures have been reported by La Guardia et al. (2006)， and 39 discrete PBDEs were found in the six commercial products evaluated by GC-MS with electron ionization (EI) and electron-capture negative ionization (ECNI). The main components of pentaBDEs， octaBDEs and decaBDE are given in Table 1-2 (EPA， 2010). The PBDEs are fairly stable compounds， with boiling points of 310–425℃ and
　　low vapor pressures， e.g.， 3.85–13.3 Pa at 20–25℃ (WHO， 1994). Their solubility in water is very poor， ranging from several to hundreds μg/L， and ＜1 μg/L for the higher- brominated diphenyl ethers (Pohl et al.， 2017). The n-octanol/ water partition coefficients (lgKOW) range between 4.28 and 9.9 (WHO， 1994). Physicochemical properties— namely the aqueous solubility， lgKOW， vapor pressure， and Henry’s law constants of the full array of PBDEs—have been estimated by quantitative structure-property relationship analysis by applying the reported data and calculated molecular descriptors (Yue & Li， 2013). Generally， the higher-brominated diphenyl ether

Contents
Preface
Foreword
Chapter 1 Occurrence and Pollution Control of PBDEs 1
1.1 Occurrence of PBDEs 2
1.1.1 Physiochemical properties of PBDEs 2
1.1.2 Legislation of PBDEs 4
1.1.3 History of PBDEs production 6
1.1.4 The release of PBDEs 7
1.1.5 Toxicity of PBDEs 10
1.2 PBDE pollution in the environment 11
1.2.1 Air pollution 11
1.2.2 Water pollution 13
1.2.3 Soil pollution 15
1.2.4 Sediment pollution 17
1.2.5 Biological uptake 18
1.2.6 Human exposure 21
1.3 PBDE prevention and control techniques 23
1.3.1 Chemical methods 23
1.3.2 Biological methods 55
1.4 Main points of interest in this book 58
1.4.1 The mechanism of degradation of PBDEs by pyrolysis 58
1.4.2 The mechanism of degradation of PBDEs by chemical and photochemical methods 60
1.4.3 The mechanism of degradation of PBDEs by selected bacteria 63
1.4.4 The application of physiochemical methods for degradation of PBDEs in surfactant solution 64
Chapter 2 Transformation of PBDEs Under High Temperature 66
2.1 Formation of brominated products from PBDE pyrolysis 67
2.1.1 Effect of pyrolysis temperature 67
2.1.2 Formation mechanisms of PBDFs 69
2.1.3 Formation mechanisms of PBDDs 72
2.1.4 Formation of polybromobenzenes 76
2.2 Formation of chloro-bromo-mixed products from PBDE pyrolysis 79
2.2.1 Formation of PBCDEs 80
2.2.2 Formation of PBCDD/Fs 87
2.2.3 Formation of other products 89
2.2.4 Formation mechanism of PBCDD/Fs 90
Chapter 3 Degradation of PBDEs by Single Zero-valent Metals and Bimetals 97
3.1 Degradation of PBDEs by zero-valent zinc 98
3.1.1 Characterization of zinc powder 98
3.1.2 Debromination of BDE-47 by zinc 98
3.1.3 Effect of pH on the debromination of BDE-47 by zinc 99
3.1.4 Relationships between molecular properties and reaction rate constants 101
3.1.5 The debromination pathway of BDE-47 by zinc 103
3.1.6 Using the SOMO of PBDE anions to predict debromination pathways by e-transfer mechanism 105
3.2 Debromination of PBDEs by n-ZVI and n-ZVI/Pd particles 108
3.2.1 Debromination pathways of PBDEs by n-ZVI and n-ZVI/Pd particles 110
3.2.2 Debromination of PBDEs in a palladium-H2 system 112
3.2.3 Predicting the dominant debromination pathway (e-transfer or H-transfer) of PBDEs 114
3.2.4 Explanation for why Mulliken charges can be used to predict debromination pathways 116
3.3 Debromination of PBDEs in various iron-based bimetallic systems 117
3.3.1 Characterization of different bimetallic particles 118
3.3.2 Influence of metal catalysts on reaction rates for BDE-47 reduction 119
3.3.3 Debromination of BDE-47 in metal-H2 systems 122
3.3.4 Debromination pathways of BDE-47 in various bimetallic systems 123
3.3.5 Debromination pathways of BDE-47 in NaBH4-metal systems 126
3.4 Debromination of PBDEs by zero-valent zinc (ZVZ) and ZVZ-based bimetal (Pd/ZVZ) 130
3.4.1 Characterization of different particles 130
3.4.2 Influence of loading rate of catalysts on reaction rates for BDE-47 debromination 131
3.4.3 The degraded reaction of lightly substituted BDEs in ZVZ and Pd/ZVZ systems 133
3.4.4 Debromination pathway of BDEs in the two materials 135
3.4.5 The different influence on reaction rate of BDE-47 with varied pH in ZVZ and Pd/ZVZ systems 137
Chapter 4 Degradation of PBDEs by UV Light 139
4.1 Debromination behavior of PBDEs by UV light 139
4.1.1 Degradation kinetics of BDE isomers in pure methanol 139
4.1.2 Debromination pathways of BDE-47 and using Mulliken charges to predict them 142
4.1.3 Effect of water content in the degradation of PBDEs 147
4.1.4 Debromination pathways of BDE-47 in different organic solvents 151
4.2 Generation of PBDFs during photolysis of PBDEs under UV light 153
4.2.1 Degradation of PBDEs without an ortho-bromine substituent 154
4.2.2 Degradation of BDEs with one ortho-bromine substituent 156
4.2.3 Degradation of BDEs with two ortho-bromine substituents 158
4.2.4 The photochemical reaction of PBDFs 162
4.2.5 The effect of solvents on the formation of PBDFs during the photolysis of PBDEs 164
4.2.6 Insights into the mechanism of formation of PBDFs from the photolysis of PBDEs using computational chemistry 169
4.3 Photodegradation of decabrominated diphenyl ether in soil suspensions 177
4.3.1 BDE-209 photodegradation in soil suspensions 178
4.3.2 The effect of HA on BDE-209 photodegradation in soil suspensions 180
4.3.3 The effects of metal ions on BDE-209 photodegradation in soil suspensions 181
4.3.4 The products of BDE-209 degradation in soil suspensions 183
Chapter 5 Degradation Behavior of PBDEs by Metal-doped TiO2 187
5.1 Preparation and characterization of four metal-doped TiO2 nanocomposites 188
5.2 Mechanism of photocatalytic debromination of BDE-47 on TiO2 and metal-doped TiO2 190
5.2.1 Enhanced photocatalytic debromination of BDE-47 on TiO2 and metal-doped TiO2 191