十溴联苯醚环境修复技术的研究进展

介绍了溴代阻燃剂十溴联苯醚（BDE-209）环境修复技术的研究进展。从光降解、零价铁降解、生物降解3个方面对BDE-209的降解机理和降解后的产物进行了介绍。BDE-209经光照、厌氧微生物、零价铁的脱溴作用后，降解成低溴代联苯醚产物；好氧微生物利用低溴代联苯醚作为生长碳源，将其在酶的作用下开环降解，进入三羧酸循环或彻底分解成CO₂和H₂O。提出应采用多种方法协同作用，更有效地降解多溴联苯醚化合物。     

四溴双酚A降解技术的研究进展

综述了微生物、物理和化学降解技术等几种主要的四溴双酚A（TBBPA）降解技术的研究进展。阐述了各种降解技术的机理和优缺点。指出今后重点的研究方向是：根据不同的反应机理和生长特性分离出微生物降解TBBPA的优势菌种，探索将TBBPA彻底碳化的工艺条件;优化高级氧化法降解TBBPA的反应条件，使之更适于工程应用;将还原法与微生物降解技术或高级氧化法相结合，先将TBBPA快速还原成双酚A，再进一步彻底碳化成CO2和H2O。     

共基质和无机盐对原油降解菌株降解原油效果的影响

从大港油田石油污染土壤中分离筛选出1株原油降解菌X3，对原油的降解率达72．6％，经鉴定X3菌株属于假单胞菌属（Psedomonas）。利用生物摇床对X3菌株降解原油的实验发现，共代谢基质α-乳糖对X3菌株降解原油有促进作用，可使原油降解率提高到80．3％；而葡萄糖和蔗糖对X3菌株降解原油有抑制作用。Fe2＋对X3菌株的降解原油也有促进作用，在α-乳糖和Fe2＋的共同作用下，X3菌株对原油的降解率可达82．3％；K＋和Mg2＋对X3菌株降解原油则有抑制作用。在FeSO4质量浓度为0．2～0．3mg／L时，X3菌株对原油的降解率最高，FeSO4质量浓度继续增加，X3菌株对原油的降解率下降。     

链霉菌(Streptomyces sp.)对吡啶的降解特性

从焦化废水的活性污泥中分离出对溶液中吡啶具有降解效果的链霉菌（Streptomyces sp．），考察了吡啶初始质量浓度、初始pH、降解温度、振荡速度等对吡啶降解效果的影响，初步探讨了该菌降解吡啶的动力学与机理。实验结果表明，该菌对吡啶有很强的耐受力，能以吡啶为惟一碳源和氮源生长。链霉菌在初始pH=8、降解温度30℃、振荡速度100r／min的条件下培养7d后，吡啶的质量浓度从250mg/L降至6．6mg/L，吡啶降解率达97．4％。该菌对吡啶的降解反应符合一级动力学方程，初始质量浓度为100mg／L时的吡啶降解速率常数为0．4011d^-1。紫外一可见光谱分析表明，吡啶经该菌降解后的特征环被破坏。     

高频超声波降解4-氯酚的反应机理及试验研究

探讨了高频超声波（1.7MHz)降解4-氯酚的反应过程和反应机理，研究了高频超声波降解4-氯酚的效果及4-氯酚的初始浓度，高级氧化方法（AOPs)等因素对降解效果的影响。试验结果表明，高频超声波降解4-氯酚为一级反应，超声波空化效应在降解过程中起主导作用。超声波与其他氧化方法联用可大大提高降解效率。具有良好的工业应用前景。     

超声波协同电化学氧化降解苯胺的研究

采用超声波协同电化学氧化法处理苯胺溶液，考察了超声时间、苯胺浓度、溶液pH、电解电压、电解质浓度等因素对苯胺降解率的影响。试验结果表明：在超声波与电化学联合作用下，苯胺降解率随降解时间的延长而提高，苯胺浓度无论是低还是高，声电联合作用完全去除苯胺只需30min左右，电化学单独作用完全去除苯胺约需要120min；苯胺初始浓度较低时，其降解率较高；随着pH的增大，苯胺降解率先降低后提高，pH为10左右苯胺降解率最高；电解质Na2SO4的浓度对苯胺降解率影响不大；电解电压在4～12V范围内，苯胺降解率随电压升高而提高，电压为16V时，其降解率下降。     

镰刀菌HJ01对苯酚的降解性能

为了研究真菌对苯酚的降解能力，采用本实验室分离的一株镰刀菌HJ01，考察了外加碳源、降解体系初始pH、温度对HJ01菌体生长量和苯酚降解效果的影响，初步探讨了镰刀菌降解苯酚的动力学与机理。实验结果表明，该菌能以苯酚为惟一碳源生长，添加适量的蔗糖可促进HJ01菌体的生长及苯酚的降解。在蔗糖加入量为3g／L、降解体系初始pH为6．0、温度为30℃的最佳条件下，经HJ01菌处理4d后的质量浓度为420mg／L苯酚废水中的苯酚完全降解。镰刀菌的生长和苯酚降解动力学符合Andrews模型。     

介质阻挡放电低温等离子体协同催化降解苯乙烯

采用介质阻挡放电(DBD)低温等离子体协同催化降解苯乙烯，考察了输入功率、初始苯乙烯质量浓度、气体湿度、停留时间、脉冲频率等因素对苯乙烯降解率和能量效率的影响，建立了苯乙烯降解动力学模型，探讨了苯乙烯的降解机理。结果表明：在输入功率30 W、初始苯乙烯质量浓度464 mg/m³、气体相对湿度30%、停留时间0.18 s、脉冲频率200 Hz的最佳工艺条件下，苯乙烯降解率为62.20%，能量效率为36.10 g/(kW·h);DBD等离子体降解苯乙烯的动力学过程符合准一级动力学模型，相应的反应速率常数为0.109 4 m3^/(W·h)。DBD等离子体降解苯乙烯主要通过活性物种e^-、·O、·OH和NO₂·等对苯乙烯进行氧化。与单独DBD等离子体工艺相比，在相同输入功率下，DBD协同催化工艺能有效提高苯乙烯降解率和矿化率，降低反应器出口O₃浓度。     

固态反应法制备FeHY催化剂及其催化降解活性艳蓝的性能研究

分别以NaY、NH4Y和HY沸石为载体，以乙酰丙酮铁为铁源，采用固态反应法制备了铁负载量均为10%（w）的FeNaY-10、FeNH4Y-10和FeHY-10催化剂。考察了各催化剂对活性艳蓝（KN-R）的降解效果，其中FeHY-10的催化降解效果最佳。采用XRD和FTIR技术对FeHY-10催化剂进行表征。表征结果显示，FeHY催化剂晶体结构仍然保持了Y分子筛特有的孔道结构，铁物种在Y 分子筛表面高度分散。催化降解实验表明，催化降解KN-R的最佳工艺条件为KN-R溶液（质量浓度为300 mg/L）加入量为50 mL、溶液pH为2、催化剂FeHY-25（铁负载量为25%（w））加入量为0.281 3 g、H2O2质量浓度为6.356 g/L、降解温度为35 ℃、降解时间为140 min，在此工艺条件下FeHY催化剂对KN-R的降解率为97.4%。     

铝碳微电解法降解水中邻苯二甲酸酯

采用铝碳微电解法降解水中邻苯二甲酸酯（PAEs）。首先考察了初始废水pH、铝碳质量比和反应时间对邻苯二甲酸二甲酯（DMP）降解率的影响，然后分别考察了超声波频率、其他金属的添加和H₂O₂加入量对铝碳微电解法降解模拟混合PAEs废水中DMP、邻苯二甲酸二乙酯（DEP）和邻苯二甲酸二丁酯（DBP）的影响。实验结果表明：在初始DMP质量浓度为20 mg/L、初始废水pH为12.0、铝碳质量比为1∶1、反应时间为30 min的条件下，DMP降解率达49.94%;在上述最佳反应条件下处理DMP，DEP，DBP的质量浓度分别为20，10，8 mg/L的模拟混合PAEs废水，当超声波频率为80 kHz时，模拟混合PAEs废水中DMP，DEP，DBP的降解率分别为63.38%，32.75%，32.23%，当铝铁质量比为100∶1时，DMP，DEP，DBP的降解率分别为59.61%，37.39%，31.50%;添加铜和H₂O₂对PAEs的降解有抑制作用。     

Polybrominated diphenyl ethers in e-waste: Level and transfer in a typical e-waste recycling site in Shanghai,Eastern China

Very few data for polybrominated diphenyl ethers (PBDEs) were available in the electronic waste (e-waste) as one of the most PBDEs emission source. This study reported concentrations of PBDEs in e-waste including printer, rice cooker, computer monitor, TV, electric iron and water dispenser, as well as dust from e-waste, e-waste dismantling workshop and surface soil from inside and outside of an e-waste recycling plant in Shanghai, Eastern China. The results showed that PBDEs were detected in the majority of e-waste, and the concentrations of ΣPBDEs ranged from not detected to 175 g/kg, with a mean value of 10.8 g/kg. PBDEs were found in TVs made in China after 1990. The mean concentrations of ΣPBDEs in e-waste made in Korea, Japan, Singapore and China were 1.84 g/kg, 20.5 g/kg, 0.91 g/kg, 4.48 g/kg, respectively. The levels of ΣPBDEs in e-waste made in Japan far exceed the threshold limit of RoHS (1.00 g/kg). BDE-209 dominated in e-waste, accounting for over 93%. The compositional patterns of PBDEs congeners resembled the profile of Saytex 102E, indicating the source of deca-BDE. Among the samples of dust and surface soil from a typical e-waste recycling site, the highest concentrations of Σ₁₈PBDEs and BDE-209 were found in dust in e-waste, ranging from 1960 to 340,710 ng/g and from 910 to 320,400 ng/g, which were 1–2 orders of magnitude higher than other samples. It suggested that PBDEs released from e-waste via dust, and then transferred to surrounding environment.     

Sources and behaviour of polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in Spanish sewage sludge

Presence, sources and behaviour of polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were evaluated in Spanish sewage sludge. A total of 120 samples were seasonally collected from October 2005 to September 2006 at 31 urban wastewater treatment plants (WWTPs). Concentrations of PBDEs (ranging between 57.5 and 2606 ng/g dry weight) were two to three orders of magnitude higher than those obtained for PCDDs (0.17-5.03 ng/g d.w.) and PCDFs (0.05-3.07 ng/g d.w.). All the samples presented International Toxicity Equivalents (I-TEQ) levels (ranging between 2.06 and 44.4 ng/kg d.w.) below the limit values proposed by European Union for land application. Congener patterns evaluation revealed that the use of Deca-BDE commercial mixture seems to be the major source of PBDEs in the sludge. Nevertheless, origin of PCDD/Fs should be related to atmospheric deposition, faeces and presence of PCDD/Fs precursors such as pentachlorophenol in the sludge. No correlations (p > 0.05) were found between pollutant concentrations (PBDEs and PCDD/Fs) and wastewater treatment plant (WWTP) characteristics (capacity nor sludge rate). Lower levels of PBDEs and PCDFs were found in WWTPs using biological nitrogen and phosphorous elimination, suggesting that these compounds are susceptible of microbial elimination. According to our knowledge, this is the first work comparing together both PBDEs and PCDD/Fs sludge patterns.     

Polybrominated diphenyl ethers (PBDEs) in leachates from selected landfill sites in South Africa

The last few decades have seen dramatic growth in the scale of production and the use of polybrominated diphenyl ethers (PBDEs) as flame retardants. Consequently, PBDEs such as BDE -28, -47, -66, -71, -75, -77, -85, -99, -100, -119, -138, -153, -154, and -183 have been detected in various environmental matrices. Generally, in South Africa, once the products containing these chemicals have outlived their usefulness, they are discarded into landfill sites. Consequently, the levels of PBDEs in leachates from landfill sites may give an indication of the general exposure and use of these compounds. The present study was aimed at determining the occurrence and concentrations of most common PBDEs in leachates from selected landfill sites. The extraction capacities of the solvents were also tested. Spiked landfill leachate samples were used for the recovery tests. Separation and determination of the PBDE congeners were carried out with a gas chromatograph equipped with Ni63 electron capture detector. The mean percentage recoveries ranged from 63% to 108% (n=3) for landfill leachate samples with petroleum ether giving the highest percentage extraction. The mean concentrations of PBDEs obtained ranged from ND to 2670pgl(-1), ND to 6638pgl(-1), ND to 7230pgl(-1), 41 to 4009pgl(-1), 90 to 9793pgl(-1) for the Garankuwa, Hatherly, Kwaggarsrand, Soshanguve and Temba landfill sites, respectively. Also BDE -28, -47, -71 and BDE-77 were detected in the leachate samples from all the landfill sites; and all the congeners were detected in two of the oldest landfill sites. The peak concentrations were recorded for BDE-47 at three sites and BDE-71 and BDE-75 at two sites. The highest concentration, 9793+/-1.5pgl(-1), was obtained for the Temba landfill site with the highest BOD value. This may suggest some influence of organics on the level of PBDEs. Considering the leaching characteristics of brominated flame retardants, there is a high possibility that with time these compounds may infiltrate into the groundwater around the sites since most of the sites are not adequately lined.     

电动力学作用下多溴联苯醚在土壤中的迁移特性

以4，4′-二溴联苯醚(BDE-15)为研究对象，探讨了电极电压、初始土壤pH、β-环糊精加入量、NaCl加入量等工艺条件对多溴联苯醚在土壤中迁移效果的影响。实验结果表明:在电极电压为5~15V范围内，随着电极电压的升高，土壤中BDE-15的迁移效果增强;初始土壤为酸性时、加入β-环糊精或NaCl后，土壤中BDE-15的迁移效果均增强。本实验选择的最佳工作条件为:电极电压15V，初始土壤pH3，β-环糊精的加入量3g，NaCl加入量5g。     

PCBs,PBDEs and dioxin-related compounds in floor dust from an informal end-of-life vehicle recycling site in northern Vietnam: contamination levels and implications for human exposure

Floor dusts from Vietnamese end-of-life vehicle (ELV)-processing households were investigated to elucidate the contamination levels and exposure risk of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and dioxin-related compounds (DRCs). The concentrations were in order of PBDEs (260–11,000, median 280 ng/g overall) > PCBs (19–2200, median 140 ng/g) > dioxin-like PCBs (8.8–450, median 22 ng/g) ? polybrominated dibenzo-p-dioxin/dibenzofurans (PBDD/Fs, 2000–28,000, median 8500 pg/g) > polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/Fs, 440–4100, median 1800 pg/g) > MoBPCDD/Fs (1.9–1200, median 250 pg/g). Concentrations of PCBs and DRCs were higher than those reported for Vietnamese urban houses, indicating ELV processing as a significant source of these contaminants. Higher concentrations of PCBs relative to PBDEs suggest the abundance of old electrical capacitors/transformers in ELVs. The PBDD/F and PCDD/F profiles were indicative of DecaBDE-containing materials and combustion sources, respectively. PBDFs, PCDFs and DL-PCBs were the most important dioxin-like toxic equivalent (TEQ) contributors. The estimated PCB and TEQ intake doses from dust ingestion approached or exceeded the reference doses for children living in some ELV-processing households, indicating potential health risk. More comprehensive risk assessment of the exposure to PCBs and DRCs is required for residents of informal ELV recycling sites.     

In-use polybrominated diphenyl ether (PBDE) stocks and atmospheric emissions in Japan

We estimated the in-use stocks of polybrominated diphenyl ethers (PBDEs) in Japan using a population balance model. The estimation is based on the domestic demand of PBDEs and the assumed survival rate of these products. Two cases relevant to the future regulation of commercial deca-BDE are considered, namely (1) deca-BDE declines at the same rate as the current rate of decline, and (2) deca-BDE is discontinued after 2020. The estimates of the decreasing rates of in-use penta-, octa-, and deca-BDE stocks were proportional with the measured decreases in the atmospheric concentrations of these substances. The in-use penta- and octa-BDE stocks could be depleted in the near future (500 and 60 tonne in 2013, and an estimated 20 and <1 tonne in 2020, respectively). Relevant to case 1, the in-use stocks of deca-BDE-containing products would be 28,000 tonne in 2013 and an estimated 1900 tonne in 2040, providing an ongoing source of deca-BDE emission to the environment. On the other hand, relevant to case 2, most of the deca-BDE would be phased out by 2040. The atmospheric emissions of deca-BDE were predicted at 84–841 kg/year in 2013 and an estimated 43–425 kg/year in 2020.     

Field investigation of the quality of fresh and aged leachates from selected landfills receiving e-waste in an arid climate

The management of electronic waste (e-waste) is a serious problem worldwide and much of it is landfilled. A survey of four selected landfills in an arid region of South Australia was conducted to determine the proportion of e-waste in municipal waste and the properties of each landfill site. Leachate and groundwater samples were collected upgradient and downgradient of the landfills for analysis of polybrominated diphenyl ethers (PBDEs) and 14 metals and metalloids, including Al, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Ni, Pb, Sb, V and Zn. Our data demonstrate that the selected landfills in South Australia continue to receive municipal waste containing in excess of 6%, or 25,000 tonnes per year, of e-waste. The leachates and groundwater collected from the landfills contained significantly elevated concentrations of Pb with the highest concentration in groundwater of 38 μg/l, almost four times higher than the Australian drinking water guideline of 10 μg/l. The presence of PBDEs was detected in both leachate and groundwater samples. Total PBDEs values of 2.13–59.75 ng/l in leachate samples were 10 times higher than in groundwater samples, which recorded a range of 0.41–6.53 ng/l at all sites. Moreover, the concentrations of metals and metalloids in sampled groundwater contained elevated levels of Al, As, Fe, Ni and Pb that exceeded Australian drinking water guideline values. For these reasons potential leaching of these contaminants is of concern and while difficult to attribute elevated contaminant levels to e-waste, we do not recommend continued disposal of e-waste in old landfills that were not originally designed to contain leachates. The survey also revealed temporal variation in the electrical conductivity and concentrations of As, Cd and Pb present in leachates of landfills in arid Mediterranean climates. These results are consistent with the marked variations in rainfall patterns observed for such climates. The solute concentration (EC and other ions including As, Cd and Pb) declines in the leachates during wet winter months (June to September), in contrast to tropical countries where such changes are observed during wet summer months.     

Extraction of polybrominated diphenyl ethers contained in waste high impact polystyrene by supercritical carbon dioxide

A new recycling process for the supercritical CO₂ (sc-CO₂) extraction of polybrominated diphenyl ethers from waste high impact polystyrene (HIPS) was developed in this paper. HIPS was first dissolved in d-limonene. The remaining decabromo diphenyl ether (decaBDE) particles in solution were then removed by centrifugation, and the PBDEs in the centrifugate solution were further extracted by sc-CO₂. The influence of temperature and pressure, the volume ratio of sc-CO₂ to plastic solution, and the concentration of decaBDE in the solution on the separating efficiency were investigated. The decaBDE particles in 20 % of the HIPS solution can be removed by centrifugation at a speed of 10,000 r/min at 30 °C. The suitable sc-CO₂ fluid conditions were 65 °C and 20 MPa, and the optimum volume ratio of the sc-CO₂ to the HIPS solution was 2:1. More than 97 % of the PBDEs were successfully removed, and the concentration of PBDE residues in the recycled HIPS was reduced to lower than 0.1 % (dry) by this recycling process.     

Chemical hazards associated with treatment of waste electrical and electronic equipment

This review paper summarizes the existing knowledge on the chemical hazards associated with recycling and other end-of-life treatment options of waste electrical and electronic equipment (e-waste). The hazards arise from the presence of heavy metals (e.g., mercury, cadmium, lead, etc.), flame retardants (e.g., pentabromophenol, polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol-A (TBBPA), etc.) and other potentially harmful substances in e-waste. If improperly managed, the substances may pose significant human and environmental health risks. The review describes the potentially hazardous content of e-waste, examines the existing e-waste management practices and presents scientific data on human exposure to chemicals, workplace and environmental pollution associated with the three major e-waste management options, i.e., recycling, incineration and landfilling. The existing e-waste management practices and associated hazards are reviewed separately for developed and developing countries. Finally, based on this review, the paper identifies gaps in the existing knowledge and makes some recommendations for future research.