Yin Zhong

Heterogeneous UV/Fenton degradation of TBBPA catalyzed by titanomagnetite: Catalyst characterization, performance and degradation products

Tetrabromobisphenol A (TBBPA), a widely used brominated flame retardant, could negatively affect various aspects of mammalian and human physiology, which triggers effective techniques for its removal. In this work, the degradation characteristics of TBBPA in heterogeneous UV/Fenton reaction catalyzed by titanomagnetite (Fe(3-x)Ti(x)O₄) were studied. Batch tests were conducted to evaluate the effects of titanomagnetite dosage, H₂O₂ concentration and titanium content in magnetite on TBBPA degradation. In the system with 0.125 g L⁻¹ of Fe₂.₀₂Ti₀.₉₈O₄ and 10 mmol L⁻¹) of H₂O₂, almost complete degradation of TBBPA (20 mg L⁻¹) was accomplished within 240 min UV irradiation at pH 6.5. The titanium incorporation obviously enhanced the catalytic activity of magnetite. As shown by the XRD and XANES results, titanomagnetite had a spinel structure with Ti⁴⁺ occupying the octahedral sites. On the basis of the degradation products identified by GC-MS, the degradation pathways of TBBPA were proposed. TBBPA possibly underwent the sequential debromination to form TriBBPA, DiBBPA, MonoBBPA and BPA, and β-scission to generate seven brominated compounds. All of these products were finally completely removed from reaction solution. In addition, the reused catalyst Fe₂.₀₂Ti₀.₉₈O₄ still retained the catalytic activity after three cycles, indicating that titanomagnetite had good stability and reusability. These results demonstrated that heterogeneous UV/Fenton reaction catalyzed by titanomagnetite is a promising advanced oxidation technology for the treatment of wastewater containing TBBPA.

Reductive transformation of tetrabromobisphenol A by sulfidated nano zerovalent iron.

Recent studies showed that sulfidated nano zerovalent iron (S-nZVI) is a better alternative to non-sulfidated nano zerovalent iron (NS-nZVI) commonly used for contaminated site remediation. However, its reactivity with different halogenated pollutants such as tetrabromobisphenol A (TBBPA) remains unclear. In this study, we explored the reductive transformation of TBBPA by S-nZVI and compared it with that by NS-nZVI. The results showed that over 90% of the initial TBBPA (20xa0mgxa0L(-1)) was transformed by S-nZVI within 24xa0h of reaction, which was 1.65 times as high as that for NS-nZVI. The TBBPA transformation by S-nZVI was well described by a pseudo-first-order kinetic model, whilst that by NS-nZVI was well fitted by a three-parameter single exponential decay model. After 11 weeks of aging, S-nZVI was still able to transform up to 56% of the initial TBBPA within 24xa0h of reaction; by contrast, the two-week aged NS-nZVI lost more than 95% of its original capacity to transform TBBPA. Moreover, S-nZVI showed only an approximately 20% decrease in its capacity to transform TBBPA in the seventh cycle, while NS-nZVI was no longer able to transform TBBPA in the fourth cycle. XPS analysis suggested the formation of FeS layer on S-nZVI surface and electrochemical analysis revealed an elevated electron transfer capacity of S-nZVI, which were likely responsible for the superior performances of S-nZVI in TBBPA transformation. While the transformation rate of TBBPA by S-nZVI decreased with increasing initial concentration of TBBPA, it showed an increasing trend with increasing S/Fe ratio and initial concentration of S-nZVI. The study indicated that S-nZVI has the potential to be a promising alternative to NS-nZVI for remediation of TBBPA-contaminated aquatic environments.

Transformation of tetrabromobisphenol A in the presence of different solvents and metals

Solvent-based separation method is presumably an efficient and environmentally beneficial approach for elimination of brominated flame retardants (BFRs) from waste electrical and electronic equipment (WEEE). The overall goal of this study was to evaluate possible effects of organic solvent on the behavior of BFRs during solvent-based processing of WEEE. We initiated a set of batch experiments for examining the rates and possible pathways of transformation of a representative BFR (tetrabromobisphenol A, TBBPA) using acetone, toluene, and methanol as the solvents. Our results showed that toluene and methanol had no effect on the transformation of TBBPA, but approximately 20% of TBBPA (100 mg L(-1)) was transformed by acetone within 2 h at 50°C. Analysis of the products with GC-MS showed that two high-molecular-weight products (MW=586) were major products of the transformation reactions. The role of acetone as a reactant in the transformation of TBBPA was further validated with dueterated acetone. In addition, the effects of co-existing metals in WEEE (i.e., Zn, Cu, and Ni) on the transformation of TBBPA in the solvent systems were investigated. These metals tested were found to greatly enhance the rates of TBBPA transformation. The metal facilitated solvent reactions with TBBPA may lower the extractability of TBBPA by formation of larger and less soluble products, hence potentially increasing the cost for separating the chemical from WEEE.

Effects of metals on the transformation of hexabromocyclododecane (HBCD) in solvents: implications for solvent-based recycling of brominated flame retardants.

The management of electronic wastes (e-wastes) has become a global issue as it may release large quantities of hazardous materials such as heavy metals and brominated flame retardants (BFRs) to the environment. Solvent-based recycling is a newly developed, efficient and environmentally beneficial technology for the removal or recovery of BFRs from e-wastes. However, little is known about the behavior of BFRs in the solvents and to what extent they may be affected by co-existing heavy metals. This study quantified the rates of transformation of hexabromocyclododecane (HBCD), a widely used BFR, in the presence of different solvents (i.e. acetone, methanol or toluene) and metals (i.e. Ni, Cu, Zn, Fe or Al). Our experimental results showed that less than 20% of HBCD was transformed in all pure solvent systems within 24h at 50 degrees C. The presence of Ni greatly increased the transformation of HBCD (45-99%) in these solvent systems, whereas other metals had little or no effect on extraction process. The kinetics study showed that transformation of HBCD in Ni-containing systems followed pseudo-first-order kinetics and that the highest transformation rate constant (1.2+/-0.1h(-1)) of HBCD was recorded in the Ni+acetone system. The formation of HBr and pentabromocyclododecene in the acetone+Ni system suggested that transformation of HBCD proceeded via dehydrobromination. Collectively, these results indicated that acetone should not be applied in the recycling or extraction of HBCD from Ni-rich e-wastes, as debromination of HBCD may occur during these processes, even at mild extraction temperatures.

Abiotic transformation of hexabromocyclododecane by sulfidated nanoscale zerovalent iron: Kinetics, mechanism and influencing factors

Recent studies showed that sulfidated nanoscale zerovalent iron (S-nZVI) is a better reducing agent than nanoscale zerovalen iron (nZVI) alone for reductive dechlorination of several organic solvents such as trichloroethylene (TCE) due to the catalytic role of iron sulfide (FeS). We measured the rates of transformation of hexabromocyclododecane (HBCD) by S-nZVI and compared them to those by FeS, nZVI, and reduced sulfur species. The results showed that: i) HBCD (20xa0mgxa0L-1) was almost completely transformed by S-nZVI (0.5xa0gxa0L-1) within 12xa0h; ii) the reaction with β-HBCD was much faster than with α- and γ-HBCD, suggesting the diastereoisomeric selectivity for the reaction by S-nZVI; and iii) the reaction with S-nZVI was 1.4-9.3 times faster than with FeS, S2- and nZVI, respectively. The study further showed that the HBCD reaction by S-nZVI was likely endothermic, with the optimal solution pH of 5.0, and could be slowed in the presence of Ca2+, Mg2+, NO3-, HCO3- and Cl-, and by increasing ionic strength, solvent content and initial HBCD concentration, or decreasing the S-nZVI dosage. GC-MS analysis showed that tetrabromocyclododecene and dibromocyclododecadiene were the products. XPS spectra indicated that both Fe(II) and S(-II) on the S-nZVI surface were oxidized during the reaction, suggesting that FeS might act as both catalyst and reactant. The study not only demonstrated the superiority of S-nZVI over other well-known reactive reagents, but also provided insight to the mechanisms of the reaction.

Kinetics of tetrabromobisphenol A (TBBPA) reactions with H2SO4, HNO3 and HCl: Implication for hydrometallurgy of electronic wastes

Hydrometallurgy is an acid leaching based process widely used for recovering precious metals from electronic wastes (e-wastes). The effects of acid leaching on the fate of brominated flame retardants (BFRs) in typical hydrometallurgical processes remain largely unknown. This study was aimed at evaluating the fate of tetrabromobisphenol A (TBBPA), a commonly used BFR, in three acid leaching reagents (i.e. H2SO4, HNO3, and HCl) commonly used in hydrometallurgy. It was found that the reactions of TBBPA with concentrated H2SO4 followed a pseudo-zero-order rate and the reaction rates declined rapidly as the concentrations of H2SO4 decreased. In contrast, TBBPA could be easily transformed in less concentrated HNO3 solutions (<21.7 wt%) and the reactions followed a pseudo-first-order rate. The reaction products identified by GC-MS indicated different transformation pathways of TBBPA in H2SO4 and HNO3. HCl or HCl/H2SO4 mixtures (3:1, v/v) did not appear to react with TBBPA, while aqua regia (3:1 HCl/HNO3, v/v) reacted violently with TBBPA and led to almost complete disappearance of TBBPA within a minute. It suggested that HNO3 significantly affected the fate of TBBPA and the use of HNO3 as leaching reagents in hydrometallurgy of e-wastes should be carefully evaluated. Collectively, our findings of distinct fate of TBBPA in different acid leaching reagents provided fundamental information for design of hydrometallurgical treatment of e-wastes to minimize acid reactions with BFRs within plastics matrix and to maximize acid leaching efficiency for metals recycling processes.

Reductive transformation of hexabromocyclododecane (HBCD) by FeS.

Both iron monosulfide (FeS) and brominated flame retardants (BFRs) are widely found at relatively high levels in anoxic sediments, but little is known about the reactions of FeS with BFRs. Prior studies showed that FeS was variously reactive with chlorinated organic pollutants in many anoxic environments. It is intuitive that FeS is also reactive with BFRs under anoxic conditions. This study was initiated to test such a hypothesis by quantifying the rates of reductive transformation of tetrabromobisphenol A (TBBPA), decabrominated diphenyl ether (decaBDE) and hexabromocyclododecane (HBCD) using synthetic FeS as the reactive agent. The results showed that over 90% of HBCD was transformed by FeS within 24xa0h, whereas both TBBPA and decaBDE were found nonreactive within 2 days. The transformation of HBCD followed a pseudo-first-order rate kinetic and the observed rate constants were dependent on the initial concentrations of FeS and HBCD. The transformation rates of β- and γ-HBCD were significantly faster than that of α-HBCD. Analysis of bromine ion and other transformation products suggested that sequential dibromoelimination to form 1,5,9-cyclododecatriene was likely to be a dominant pathway for the reductive transformation of HBCD by FeS. Surface characterization of FeS by XPS indicated that both Fe(II) and S(-II) on the FeS surface might have contributed considerably to the transformation of HBCD. These findings imply that FeS may play an important role in natural attenuation of HBCD and that it may be used as a reactive agent for treating HBCD-contaminated sediments.

Diastereoisomer-specific biotransformation of hexabromocyclododecanes by a mixed culture containing Dehalococcoides mccartyi strain 195

Hexabromocyclododecane (HBCD) stereoisomers may exhibit substantial differences in physicochemical, biological, and toxicological properties. However, there remains a lack of knowledge about stereoisomer-specific toxicity, metabolism, and environmental fate of HBCD. In this study, the biotransformation of (±)α-, (±)β-, and (±)γ-HBCD contained in technical HBCD by a mixed culture containing the organohalide-respiring bacterium Dehalococcoides mccartyi strain 195 was investigated. Results showed that the mixed culture was able to efficiently biotransform the technical HBCD mixture, with 75% of the initial HBCD (∼12 μM) in the growth medium being removed within 42 days. Based on the metabolites analysis, HBCD might be sequentially debrominated via dibromo elimination reaction to form tetrabromocyclododecene, dibromocyclododecadiene, and 1,5,9-cyclododecatriene. The biotransformation of the technical HBCD was likely diastereoisomer-specific. The transformation rates of α-, β-, and γ-HBCD were in the following order: α-HBCD > β-HBCD > γ-HBCD. The enantiomer fractions of (±)α-, (±)β-, and (±)γ-HBCD were maintained at about 0.5 during the 28 days of incubation, indicating a lack of enantioselective biotransformation of these diastereoisomers. Additionally, the amendment of another halogenated substrate tetrachloroethene (PCE), which supports the growth of strain 195, had a negligible impact on the transformation patterns of HBCD diastereoisomers and enantiomers. This study provided new insights into the stereoisomer-specific transformation patterns of HBCD by anaerobic microbes and has important implications for microbial remediation of anoxic environments contaminated by HBCD using the mixed culture containing Dehalococcoides.

Solvent effects on quantitative analysis of brominated flame retardants with Soxhlet extraction

Reliable quantifications of brominated flame retardants (BFRs) not only ensure compliance with laws and regulations on the use of BFRs in commercial products, but also is key for accurate risk assessments of BFRs. Acetone is a common solvent widely used in the analytical procedure of BFRs, but our recent study found that acetone can react with some BFRs. It is highly likely that such reactions can negatively affect the quantifications of BFRs in environmental samples. In this study, the effects of acetone on the extraction yields of three representative BFRs [i.e., decabrominated diphenyl ether (decaBDE), hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA)] were evaluated in the Soxhlet extraction (SE) system. The results showed that acetone-based SE procedure had no measureable effect for the recovery efficiencies of decaBDE but could substantially lower the extraction yields for both TBBPA and HBCD. After 24xa0h of extraction, the recovery efficiencies of TBBPA and HBCD by SE were 93 and 78% with acetone, 47 and 70% with 3:1 acetone:n-hexane, andxa082 and 94% with 1:1 acetone:n-hexane, respectively. After 72xa0h of extraction, the extraction efficiencies of TBBPA and HBCD decreased to 68 and 55% with acetone, 0 and 5% with 3:1 acetone/n-hexane mixtures, andxa00 and 13% with 1:1 acetone/n-hexane mixtures, respectively. The study suggested that the use of acetone alone or acetone-based mixtures should be restricted in the quantitative analysis of HBCD and TBBPA. We further evaluated nine alternative solvents for the extraction of the three BFRs. The result showed that diethyl ether might be reactive with HBCD and may not be considered as the alternative to acetone used solvents for the extraction of HBCD.