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。     

改性Y沸石催化降解聚苯乙烯的研究

用热重分析方法研究了HY沸石与改性Y沸石(UHY)作为催化降解聚苯乙烯的催化剂对聚苯乙烯催化降解的作用及影响,对聚苯乙烯的催化降解与热降解反应产物进行了比较。结果表明,催化剂的存在能显著地降低聚苯乙烯的降解温度,催化剂的酸量和孔结构对聚苯乙烯的降解温度、活化能、积炭的生成量及裂解产物有很大的影响。     

一株吡啶降解菌的筛选及其降解性能

以吡啶为唯一碳源,从焦化厂活性污泥中分离得到一株对吡啶具有高效降解能力的菌株B1,对其进行了菌种鉴定。通过单因素实验研究了菌株B1适宜的降解条件,对反应过程进行了动力学拟合,并考察了菌株B1对焦化废水中吡啶的降解效果。实验结果表明:菌株B1为革兰氏阴性菌,属于不动杆菌属(Acinetobacter sp.);菌株B1适宜的降解条件为降解温度30℃、初始pH为7、摇床转速150 r/min;菌株B1对吡啶的降解过程符合零级反应动力学模型,当初始吡啶质量浓度为300 mg/L时,降解速率常数最高达到21.103 mg/(L·h);用菌株B1对初始吡啶质量浓度为430 mg/L的实际焦化废水处理74 h后,吡啶降解率可达74.26%。     

Fenton试剂降解氯酚类物质的研究进展

概述了Fenton试剂对氯酚类物质的降解效果及其作用机理,讨论了氯代酚中氯的含量及氯的位置对Fenton试剂降解氯酚类物质难易程度的影响.得出Fenton试剂可以有效地降解氯酚类物质,同时氯代酚中所含氯的数量及氯所处的位置对其降解速率有较大的影响.     

微生物对石油烃的降解机理及影响因素

综述了微生物对链烷烃、环烷烃和芳香烃的降解途径、机理和降解动力学,分析了温度、营养物质、氧及盐度等非生物因素对降解作用的影响。     

外加营养源对氯氰菊酯降解菌GF31降解特性的影响

利用本实验室保存的一株铜绿假单胞菌(Pseudomonas aeruginosa)GF31,考察了外加不同的碳、氮源对菌株降解氯氰菊酯特性的影响.实验结果表明:适量浓度的碳、氮源对降解有明显的刺激作用,外加碳源中葡萄糖的刺激作用最为明显,外加0.8 g/L的葡萄糖,氯氰菊酯降解率提高了13.7%;外加氮源中以蛋白胨对微生物的促进作用最突出,当外加5.0 g/L蛋白胨时,氯氰菊酯降解率从27.5%提高到70.0%;降解5 d后,氯氰菊酯的降解已基本趋于平衡.     

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。     

萘降解菌的筛选及其对多环芳烃的降解

从柴油污染土壤中筛选分离出一株萘降解菌N-3,进行了菌种鉴定及萘双加氧酶基因(nah)验证,并考察了该菌对不同种类多环芳烃(PAHs)的降解能力及降解过程中脱氢酶活性的变化。实验结果表明:该菌为铜绿假单胞菌(Pseudomonas aeruginosa),含有nah基因;当分别对液体培养基中质量浓度为50 mg/L的萘、菲、蒽、芘、芴降解84 h时,菌株N-3对萘、菲、蒽、芘、芴的降解率分别为28.81%,34.83%,36.65%,27.50%,23.47%。菌株N-3的脱氢酶活性与其对不同PAHs的降解率呈一定的正相关性。该菌不仅能有效降解萘,且对其他种类PAHs也有一定降解作用。     

2,5-二氟硝基苯的厌氧降解特性

考察了2,5-二氟硝基苯(2,5-DFNB)的厌氧降解特性及F~-对其厌氧降解过程的影响。实验结果表明:当初始2,5-DFNB质量浓度为5~100 mg/L时,随着降解时间的延长,2,5-DFNB对厌氧消化产甲烷的抑制效应逐渐减弱直至消失;在厌氧降解过程中,2,5-DFNB的降解基本无延滞期,但仅发生了硝基转化,并未实现还原脱氟;2,5-DFNB的厌氧降解动力学符合Andrews模型,最大比降解速率、底物饱和常数、底物抑制常数分别为5.9 mg/(g·h),67.7 mg/L,1 299.6 mg/L;质量浓度为10~80 mg/L的F~-对2,5-DFNB厌氧降解过程影响甚小,而质量浓度大于100 mg/L时则产生了较严重的抑制作用。     

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.