PBDF and PBDD from the combustion of bromine containing flame retarded polymers: A survey

The formation of polybrominated dibenzofurans (PBDF) and dibenzodioxins (PBDD) during the pyrolysis of different polymers containing brominated organic flame retardants was investigated. The pyrolyses were conducted at two different temperatures (600°C and 800°C) using three different oven configurations. Both the pyrolysis gases and the solid residues were analysed for PBDF and PBDD.

PBDF were found in almost all samples, but both the concentration and the degree of bromination varied greatly. The largest yields of PBDF in the percent range were measured in the pyrolysis products of polymers containing brominated diphenyl ethers. The other flame retardants generally yielded only a few ppm of PBDF. PBDD are formed only in a few samples and related to the PBDF in very low concentrations.     

废弃高分子聚合物再生转化环境功能材料的研究进展

废弃高分子聚合物造成的环境污染问题日益突出,这类废弃物的绿色循环利用近年来备受关注,其中材料化利用是其再生循环的优选途径。概述了废弃高分子聚合物合成环境功能材料的最新研究进展,重点关注噪声污染控制材料、高性能吸水材料、特殊孔材料、吸附材料、催化材料、黏结材料、还原材料和能源转化材料等。介绍了高分子废弃物在这些功能材料合成中发挥的作用、转化方法、材料性能和应用领域,以期为高分子废弃物的高附加值循环利用提供指导。     

Application of a purge and trap TDS-GC/MS procedure for the determination of emissions from flame retarded polymers

Emissions of volatile organic compounds (VOCs) from different thermoplastic polymers used in electrotechnical applications were investigated using a purge and trap procedure that involved adsorption on Tenax GR. Results were compared to those for an operating TV set monitored in a test chamber. The analyses were in both cases carried out using thermodesorption gas chromatography with mass spectrometric detection (TDS-GC/MS). Substances identified were monomers, volatile additives, or related compounds. Special attention was given to the detection of halogenated compounds. Their origin was studied using reference samples and synthetic standards.     

Novel trends in the thermo-chemical recycling of plastics from WEEE containing brominated flame retardants

Environmental Science and Pollution Research - The amount of plastics from waste electric and electronic equipment (WEEE) has enormously increased nowadays, due to the rapid expansion and...     

Emissions of organophosphate and brominated flame retardants from selected consumer products and building materials

The emissions of selected flame retardants were measured in 1- and 0.02-m³ emission test chambers and 0.001-m³ emission test cells. Four product groups were of interest: insulating materials, assembly foam, upholstery/mattresses, and electronics equipment. The experiments were performed under constant environmental conditions (23°C, 50% RH) using a fixed sample surface area and controlled air flow rates. Tris (2-chloro-isopropyl)phosphate (TCPP) was observed to be one of the most commonly emitted organophosphate flame retardants in polyurethane foam applications. Depending on the sample type, area-specific emission rates (SER_a) of TCPP varied between 20 ng m⁻² h⁻¹ and 140 μg m⁻² h⁻¹.The emissions from electronic devices were measured at 60°C to simulate operating conditions. Under these conditions, unit specific emission rates (SER_u) of organophosphates were determined to be 10–85 ng unit⁻¹ h⁻¹. Increasing the temperature increased the emission of several flame retardants by up to a factor of 500. The results presented in this paper indicate that emissions of several brominated and organophosphate flame retardants are measurable. Polybrominated diphenylethers exhibited an SER_a of between 0.2 and 6.6 ng m⁻² h⁻¹ and an SER_u of between 0.6 and 14.2 ng unit⁻¹ h⁻¹. Because of sink effects, i.e., sorption to chamber components, the emission test chambers and cells used in this study have limited utility for substances low vapour pressures, especially the highly brominated compounds; hexabromocyclododecane had an SER_a of between 0.1 and 29 ng m⁻² h⁻¹ and decabromodiphenylether was not detectable at all.     

Effect of brominated flame retardant on the pyrolysis products of polymers originating in WEEE

Environmental Science and Pollution Research - Chemical recycling is an environmentally friendly method, which is often used for the recycling of plastics included in waste electric and electronic...     

Correction to: Effect of brominated flame retardant on the pyrolysis products of polymers originating in WEEE

Environmental Science and Pollution Research - A Correction to this paper has been published: https://doi.org/10.1007/s11356-021-15862-7     

Analysis of brominated flame retardants in house dust

The main objective of this study was to create a robust analytical method to analyse the flame retardants decabromodiphenylether (BDE-209), hexabromocyclododecane (HBCD), and tetrabromobisphenol-A (TBBPA) in house dust in order to estimate the degree of contamination of indoor environment. A liquid chromatography method equipped with a UV-detector and electro spray-tandem mass spectrometry was used to achieve this result. Applying an external calibration for BDE-209, an internal calibration for TBBPA, and a standard addition method for HBCD low limits of quantification were obtained. The analytical procedure was carried out under exclusion of UV-light as the target compounds potentially degrade when being exposed to UV-light. Empirical data were obtained in addition to the dust samples to estimate potential influences of apartment characteristics. A weak correlation between the number of electric devices and TBBPA was found.     

Analysis of brominated flame retardants in house dust

The main objective of this study was to create a robust analytical method to analyse the flame retardants decabromodiphenylether (BDE-209), hexabromocyclododecane (HBCD), and tetrabromobisphenol-A (TBBPA) in house dust in order to estimate the degree of contamination of indoor environment. A liquid chromatography method equipped with a UV-detector and electro spray-tandem mass spectrometry was used to achieve this result. Applying an external calibration for BDE-209, an internal calibration for TBBPA, and a standard addition method for HBCD low limits of quantification were obtained. The analytical procedure was carried out under exclusion of UV-light as the target compounds potentially degrade when being exposed to UV-light. Empirical data were obtained in addition to the dust samples to estimate potential influences of apartment characteristics. A weak correlation between the number of electric devices and TBBPA was found.     

Quantification of polychlorinated biphenyls in plastic granulates from the recycling of cables - Reference materials and interlaboratory comparison

A procedure for the quantification of the PCB marker congeners 28, 52, 101, 138, 153, 180 in plastic waste form the recycling of cables in the range of content between 0.1 mgkg(-1) and 20 mgkg(-1) was validated. Representative reference materials for laboratory analyses were produced using granulates from different recycling processes. The method development included aspects of grinding, sieving, homogenising as well as the comparison of extraction methods and chromatographic conditions. The validated procedure foresees grinding of the technical sample to an upper particle size limit of 0.50mm followed by extraction with an unpolar solvent such as n-hexane and gas chromatographic determination. LOD and LOQ for individual congeners ranged between 0.01 mgkg(-1) and 0.08 mgkg(-1). Electron capture detection (ECD) and mass selective detection (MS) were equivalent if chromatographic conditions were appropriately selected. The application of MS was advantageous in presence of significant amounts of interfering components which have been found in some cables. Three reference materials containing the marker congeners in the range of 0.1 mgkg(-1)-5 mgkg(-1) were submitted to a final validation intercomparison with 23 selected field laboratories using the developed method. Relative reproducibility standard deviations varied between 15% and 33%.     

微波技术在锂离子电池正极材料高效回收再利用中的研究进展

随着储能市场的快速发展,锂离子电池供求量不断攀升,废旧电池数量也随之大幅增长。废弃电池的不当处置将危及人类健康、阻碍环境和资源的可持续发展,而对其进行资源化回收再利用,尤其是回收其中具有高附加值的正极材料,有利于实现社会、经济、环境等层面的多重效益。对比总结了废旧锂电正极材料传统回收利用工艺的现状和问题,梳理了新兴微波辅助技术在材料回收及资源化利用过程中的应用和研究进展。微波技术由于其独特的加热机制在优化杂质降解、强化碳热还原、提升浸出效率、再生材料等诸多方面体现出显著优势和发展潜力。基于实际问题和数值模拟总结了微波处理技术的局限性,并提出了改进策略,以期对锂电回收体系的改良和发展提供参考。     

废铅蓄电池回收的节能降碳案例分析

为了解我国废铅蓄电池回收过程的节能降碳现状,以典型废铅蓄电池回收工艺为研究对象,分析了废铅蓄电池回收过程的产品综合能耗和碳排放情况。结果表明,案例企业的单位产品综合能耗 (当量能耗) 为98.35 kgce·t⁻¹;天然气消耗是最大的能耗来源;铅膏熔炼工序是废铅蓄电池回收过程中产品综合能耗和碳排放量最大的工序;焦粉作为还原剂进入熔炼工序的排放是最主要的碳排放源。在燃料燃烧、能源作为原材料、净购入电力和热力方面,能耗和碳排放量核算是线性相关的,在上述方面寻求节能措施可使废铅蓄电池回收企业实现同时降碳。此外,碳酸盐引起的过程排放和耗能工质也会影响企业的节能降碳效果,建议在后续的核算指南中进行统一规定。本研究结果可为废铅蓄电池回收过程的节能降碳提供参考。     

Analysis of Ah receptor pathway activation by brominated flame retardants

Brominated flame-retardants (BFRs) are used as additives in plastics to decrease the rate of combustion of these materials, leading to greater consumer safety. As the use of plastics has increased, the production and use of flame-retardants has also grown. Many BFRs are persistent and have been detected in environmental samples, raising concerns about the biological/toxicological risk associated with their use. Most BFRs appear to be non-toxic, however there is still some concern that these compounds, or possible contaminants in BFRs mixtures could interact with cellular receptors. In this study we have examined the interaction of decabromodiphenyl ether, Firemaster BP4A (tetrabromobisphenol A), Firemaster PHT4 (tetrabromophthalic anhydride), hexabromobenzene, pentabromotoluene, decabromobiphenyl, Firemaster BP-6 (2,2^′,4,4^′,5,5^′-hexabromobiphenyl) and possible contaminants of BFR mixtures with the Ah receptor. Receptor binding and activation was examined using the Gel Retardation Assay and increased expression of dioxin responsive genes was detected using the reporter gene based CALUX assay. The results demonstrate the ability of BFRs to activate the AhR signal transduction pathway at moderate to high concentrations as assessed using both assays. AhR-dependent activation by BFRs may be due in part to contaminants present in commercial/technical mixtures. This was suggested by our comparative analysis of Firemaster BP-6 versus its primary component 2,2^′,4,4^′,5,5^′-hexabromobiphenyl. Some technical mixtures of brominated flame-retardants contain brominated biphenyls, dioxins or dibenzofurans as contaminants. When tested in the CALUX assay these compounds were found to be equivalent to, or more active than their chlorinated analogues. Relative effective potency values were determined from dose response curves for these brominated HAHs.     

Brominated flame retardants in the hair and serum samples from an e-waste recycling area in southeastern China: the possibility of using hair for biomonitoring

Hair samples and paired serum samples were collected from e-waste and urban areas in Wenling of Zhejiang Province, China. The PBDE and DBDPE concentrations in hair and serum samples from e-waste workers were significantly higher than those of non-occupational residents and urban residents. BDE209 was the dominating BFRs in hair and serum samples from the e-waste area, while DBDPE was the major BFRs from the urban area. Statistically significant correlations were observed between hair level and serum level for some substances (BDE209, DBDPE, BDE99, BDE47, BDE28, and BDE17), although the PBDE congener profiles in hair were different from those in the serum. A statistically significant positive correlation between the PBDE concentrations and the working age, as well as gender difference, was observed in e-waste workers. Different sources of PBDEs and DBDPE in three groups were identified by principal component analysis and spearman correlation coefficient. Hair is suggested to be a useful matrix for biomonitoring the PBDE exposure in humans.     

Combustion of flame retardants

2,4,6-Tribromoaniline (TBA) is used in the preparation of various dyes, polymers, and, in combination with antimony trioxide, as a flame retardant in the textile and plastic industry. Pyrolysis studies of TBA done previously in our laboratory indicated the presence of some potentially toxic nitrogen analogs of dioxins. Combustion of TBA was further studied using a flame to simulate the conditions of an incinerator; it was observed that, along with the formation of phenazines, small but significant amounts of brominated benzidines and carbazoles were also formed.     

Management and performance of Taiwan's waste recycling fund

Taiwan's resource recycling program was formally established in 1989, starting with the mandatory recycling of polyethylene terephthalate bottles. The number of mandatory regulated materials was extended to 8 categories with 27 items by 2002. Because of false data reporting, financial scandal, lack of transparency of the system, and the demand from parliament, the recycling policy has gradually changed from entirely privatized to being nationalized. Currently, the structure is built on six main bodies: fund management committee, consumers, industries responsible, recyclers, fee reviewing committee, and auditing agents. The industries that are responsible submit a fee, which is set by the fee reviewing committee, to the waste recycling fund (WRF), which is operated by the fund management committee. The auditing agents routinely check the responsible industries by documentation review as well as on-site counting to ensure that the fee is correctly submitted. The WRF provides initiatives to collect and dispose of the end-of-life products. The fund is split into a trust fund and a nonbusiness fund to deal with the collection, disposal, and treatment of the listed materials. The latter deals with the supporting works and ensures that the system runs effectively. The ratio of trust fund to nonbusiness fund is 80-20%. It is no doubt that the current practice achieves some improvements. Household waste has been reduced by 22%. And, most importantly, the benefit-to-cost ratio was as high as 1.24. However, similar to other state-owned systems, the resource recycling program has been criticized for false reporting from the responsible industries, a rigid system, and complicated procedures. To build a sustainable enterprise, the recycling program should be privatized as the recycling market and operating procedures are well established and fully mature.     

阻燃剂废水的处理及回收利用

采用电化学氧化、电气浮与Fenton强氧化性协同作用的电解Fenton法预处理难降解阻燃剂废水(CODCr=17108mg/L),CODCr去除率达98.34%,色度去除率达74.19%。其适宜操作条件是:pH=2.0～2.6;电流密度10.8～14.3A/dm2;H2O2起始摩尔浓度27～42mmol/L;FeSO4起始质量浓度660～990mg/L;电解5h。处理后取废水50mL,HCl(1∶1)67mL,NaAlO230g,FeCl3·6H2O4g,加热回流反应2h制成聚合氯化铝铁无机高分子絮凝剂(Al2O39.93%、Fe2O30.75%、盐基度68.0%左右)。该絮凝剂在pH=7～9时有良好的絮凝效果。     

电子与电器废弃物资源化处理技术

当今世界电子、电器工业快速发展,层出不穷的技术创新与持续膨胀的市场需求加速了电子与电器设备的更新换代,产生了大量的电子与电器废弃物(WEEE).鉴于WEEE所带来的严重的环境问题及其所含有的金属、贵金属、塑料及玻璃等高利用价值的材料,对WEEE进行资源化再循环处理已成为人们关注的热点.WEEE组成材料在密度、铁磁性、导电性等物理性质方面的较大差异使采用环境友好的机械物理方法对其进行资源化再循环处理成为可能.就WEEE拆解及其所含物质机械物理分离研究进展进行了综述.     

电子与电器废弃物资源化处理技术

当今世界电子、电器工业快速发展，层出不穷的技术创新与持续膨胀的市场需求加速了电子与电器设备的更新换代，产生了大量的电子与电器废弃物（WEEE）。鉴于WEEE所带来的严重的环境问题及其所含有的金属、贵金属、塑料及玻璃等高利用价值的材料，对WEEE进行资源化再循环处理已成为人们关注的热点。WEEE组成材料在密度、铁磁性、导电性等物理性质方面的较大差异使采用环境友好的机械物理方法对其进行资源化再循环处理成为可能。就WEEE拆解及其所含物质机械物理分离研究进展进行了综述。     

CO2捕集回收技术研究

主要介绍了常用的胺化合物吸收法、钙基吸收剂法、金属氧化物法等CO2捕集回收技术的最新研究进展及存在的问题,综合对比了各种方法的优缺点:胺化合物吸收法吸收速率快,但再生能耗较高,因此开发"高效低耗"的复合吸收剂成为研究的重点;钙基吸收剂法在高温环境下对CO2的吸收有较好的效果,但吸收剂的碳酸化转化率及热稳定性是有待解决的关键问题;金属氧化物法具有高的CO2吸收效率,但成本较高.在此基础上,探索了CO2捕集回收技术改进工艺,提出改善吸收剂性能、开发高效低耗的CO2选择性吸收剂将成为今后CO2捕集回收技术的研究方向.