Changes in polybrominated diphenyl ether (PBDE) levels in cooked food

Food surveys for levels of toxic chemicals frequently report the levels on an uncooked basis. It is known that cooking may in some conditions decrease the amount of dioxins and related chemicals in food. Surveys of polybrominated diphenyl ether (PBDE) levels in food to date show data from uncooked food only. In this article, it was shown that broiling, with fat dripped from the foods reported here, ground beef, ground lamb, catfish, trout, and salmon, reduces the amount of PBDEs in these foods. This suggests that calculations of food intake need to take into consideration levels in the cooked food rather than in the uncooked food.     

Enhanced debromination of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) by zero-valent zinc with ascorbic acid

• Highly efficient debromination of BDE-47 was achieved in the ZVZ/AA system. • BDE-47 debromination by the ZVZ/AA can be applied to a wide range of pH. • AA inhibits the formation of (hydr)oxide and accelerates the corrosion of ZVZ. • Reduction mechanism of BDE-47 debromination by the ZVZ/AA system was proposed. A new technique of zero-valent zinc coupled with ascorbic acid (ZVZ/AA) was developed and applied to debrominate the 2,2′,4,4′-Tetrabromodiphenyl ether (BDE-47), which achieved high conversion and rapid debromination of BDE-47 to less- or non-toxic forms. The reaction conditions were optimized by the addition of 100 mg/L ZVZ particles and 3 mmol/L AA at original solution pH= 4.00 using the solvent of methanol/H₂O (v:v= 4:6), which could convert approximately 94% of 5 mg/L BDE-47 into lower-brominated diphenyl ethers within a 90 min at the ZVZ/AA system. The high debromination of BDE-47 was mainly attributed to the effect of AA that inhibits the formation of Zn(II)(hydr)oxide passivation layers and promotes the corrosion of ZVZ, which leads to increase the reactivity of ZVZ. Additionally, ion chromatography and gas chromatography mass spectrometry analyses revealed that bromine ion and lower-debromination diphenyl ethers formed during the reduction of BDE-47. Furthermore, based on the generation of the intermediates products, and its concentration changes over time, it was proposed that the dominant pathway for conversion of BDE-47 was sequential debromination and the final products were diphenyl ethers. These results suggested that the ZVZ/AA system has the potential for highly efficient debromination of BDE-47 from wastewater.     

典型污水处理厂中多溴联苯醚的分布特征、迁移及负荷研究

本研究通过对典型污水处理厂各构筑物进行采样分析,研究多溴联苯醚在污水处理厂中的分布、迁移和转化.结果表明,在污水处理厂所有污泥样品中都有PBDEs检出,PBDEs浓度范围在4226.76~9204.14 ng·g-1之间.其中,BDE-209是主导同系物,所占平均比例为83.16%(范围为75.75%~89.48%).该污水处理厂的进水样品中溶解态PBDEs总浓度为183.11 ng·L-1,而出水样品中溶解态PBDEs浓度则降至7.07 ng·L-1,PBDEs的去除率达到96%以上.所有污水样品中BDE-209都是最主要的同系物,所占比例在75.75%~85.68%之间,BDE-99和BDE-47是仅次于BDE-209的另外2种主要同系物.通过对污水处理流程中PBDEs的溶解态和颗粒态分配系数的研究得出,溶解性颗粒物对疏水性有机物在整个污水处理流程中的迁移、转化有重要的影响.该污水厂的日均PBDEs负荷量为21311.2 mg·d-1,污水经初沉池和二沉池处理之后分别有58.07%和39.91%的PBDEs被去除,即一共有97.98%的PBDEs被去除了,最后在出水中只剩2.02%的PBDEs.该污水厂通过出水的日均排放PBDEs的量为430.8 mg,通过脱水污泥日均排放PBDEs的量高达20880.4 mg.土壤在污泥农用之后PBDEs浓度年增加量为25.4μg·kg-1,污泥农用需要百年以上才能达到欧盟的规定限值.     

Ni-MOFs对水中全氟烷基醚磺酸盐的吸附性能及机理

为有效去除水中的全氟烷基醚磺酸盐(F-53B),采用溶剂热法合成二维Ni-MOFs和三维Ni-MOFs材料。采用XRD、FTIR、SEM、N₂吸/脱附实验和热重分析对材料的结构形貌和热稳定性进行了表征,采用动力学和热力学实验以及对比分析,考察了Ni-MOFs对水中F-53B的吸附性能,并进一步结合理论计算探究了可能的吸附机理。结果表明,2种材料均具有明显的晶型,其中Ni是以双齿配位模式与有机骨架进行结合,二维Ni-MOFs呈现分散片层结构,三维Ni-MOFs则呈现出块状结构,二维Ni-MOFs比三维Ni-MOFs具有更高的比表面积、孔隙率和热稳定性。2种材料对F-53B的吸附均符合准二级动力学方程和Freundlich等温方程,二维Ni-MOFs的吸附速率常数和吸附容量分别达到0.002 4 g·(min·mg)⁻¹和451.2 mg·g⁻¹,比三维Ni-MOFs分别高出20%和16%,吸附过程以非均质多层吸附为主,受共存阴离子的影响较小。对F-53B的吸附性能与2种材料的构效有关,活性吸附位点和限域作用决定了二维Ni-MOFs比三维Ni-MOFs更优的吸附特性,吸附过程主要受静电作用控制。以上研究结果表明二维Ni-MOFs对F-53B的吸附性能较好,具有良好的应用前景。     

二价铁活化过硫酸盐降解土壤中十溴联苯醚

研究了Fe2+活化过硫酸钠产生的硫酸根自由基降解土壤中十溴联苯醚（PBDE-209）的效果,分别考察了Na2S2O8的用量、初始pH值、Na2S2O8与Fe2+摩尔比例、反应时间4个因素对降解效果的影响。通过正交实验确定了降解污染物的最优条件。结果表明,在Na2S2O8用量为0.8 mmol·kg-1,初始pH为5,Na2S2O8与Fe2+摩尔比为2：1,反应时间为30 min的最优条件下,降解率达96.36%。分子探针竞争实验表明体系中产生了硫酸根自由基。Fe2+活化过硫酸钠降解PBDE-209反应过程符合一级反应动力学。     

A comparative study on the autoxidation of dimethyl ether (DME) comparison with diethyl ether (DEE) and diisopropyl ether (DIPE)

The Japanese government is planning to introduce DME as a substituted energy for oil and LNG. Introduction of DME could contribute greatly to both the prevention of global warming and the formation of resource-recycling societies. In these circumstances, a safety assessment of DME is very important when DME is used on a large scale. There is a possibility that prolonged exposure in air induces autoxidation to produce explosive organic peroxides during transportation and storage of DME. Therefore, the reactivity of DME with oxygen and the mechanism of the autoxidation were investigated. Accelerating Rate Calorimetry (ARC) was used to evaluate the thermal stability of DME and DIPE, a known peroxide producers, under adiabatic and various atmospheric conditions. In ARC studies of DME under oxygen, exothermic decompositions were detected although its self-heating rate was low in comparison with DIPE. Oven storage tests were carried out and iodimetry was used to measure the concentration of peroxides produced from DME in comparison with DIPE and DEE. However, no products could be found for DME either by GC/MS or by iodimetry, while some evidence of autoxidation of both DEE and DIPE were obtained from these experiments.     

工程菌处理高纯二甲醚生产废水的研究

工程菌LEY7是以假单胞菌D3 菌株 (Pseudomonassp.D3 )为受体 ,以缓慢牙孢杆菌 3RM2 菌株 (Bacilluslentus 3RM2 ) ,假单胞菌W1 (Pseudomonassp .W1 )和W2 (Pseudomonassp .W2 )为供体 ,用多基因转化原生质球构建而成。工程菌LEY7能同时降解 4种化合物。用工程菌LEY7处理化工废水 ,工艺采用二级氧化。处理效果 :进水COD =10 0 0mg/L ,处理后出水COD在 10 0mg/L以下。COD去除率达到 90 %以上。     

加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱测定土壤和沉积物中8种多溴联苯醚

建立了土壤和沉积物中8种多溴联苯醚(PBDEs,BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183和BDE-209)加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱(ASE-GC-MS-MS)的分析方法。通过优化加速溶剂萃取与弗罗里硅土在线净化和串联质谱多反应监测模式的条件,较好地去除基质干扰,并提高了三重四极杆串联质谱定性的准确性及定量的灵敏性。该方法采用改进的色谱柱能同时分析包括高溴代联苯醚BDE-209在内的8种PBDEs,其浓度范围为1～100 ng/mL(BDE-209为10～1 000 ng/mL),线性良好,线性回归系数均大于0.997。方法检出限为0.004～0.1 ng/g,方法回收率为75%～110%,方法精密度为2.4%～15.6%。适于批量处理土壤和沉积物中含有多组分痕量PBDEs的样品。     

Factors influencing on the bioaccessibility of polybrominated diphenyl ethers in size-specific dust from air conditioner filters

Size-specific concentrations and bioaccessibility of polybrominated diphenyl ethers (PBDEs) in dust from air conditioner filters were measured, and the factors influencing the PBDE bioaccessibility were determined. Generally, the PBDE concentrations increased with decreasing dust particle size, and BDE209 (deca-BDE) was generally the predominant congener. The bioaccessibility ranged from 20.3% to 50.8% for tri- to hepta-BDEs, and from 5.1% to 13.9% for BDE209 in dust fractions of varied particle size. The bioaccessibility of most PBDE congeners decreased with increasing dust particle size. The way of being of PBDE (adsorbed to dust surface or incorporated into polymers) in dust significantly influenced the bioaccessibility. There was a significant negative correlation between the tri- to hepta-BDE bioaccessibility and organic matter (OM) contents in dust. Furthermore, tri- to hepta-BDE bioaccessibility increased with increasing polarity of OMs, while with decreasing aromaticity of OMs. The tri- to hepta-BDE bioaccessibility significantly positively correlated with the surface areas and pore volumes of dust. Using multiple linear regression analysis, it was found that the OM contents and pore volumes of dust were the most important factors to influence the tri- to hepta-BDE bioaccessibility and they could be used to estimate the bioaccessibility of tri- to hepta-BDEs according to the following equation: bioaccessibility (%) = 45.05 − 0.49 × OM% + 1.79 × pore volume. However, BDE209 bioaccessibility did not correlate to any of these factors.     

辽宁省淡水鱼类体内多溴联苯醚和六溴环十二烷的富集特征及健康风险评估

分析了辽宁省4个典型城市淡水鱼类中多溴联苯醚（PBDEs）和六溴环十二烷（HBCDs）的富集特征,并进行了健康风险评估。结果表明：淡水鱼类体内PBDEs和HBCDs检出率均为100%,PBDEs和HBCDs的平均质量分数分别为9.73 和21.81 ng/g（脂重）。PBDEs中的单体BDE 183、BDE 209和BDE 153在辽河流域不同鱼类的同源种中占优势,分别占PBDEs的26.8%～40%,17%～44%和14%～22%。在HBCDs的3种同系物中,α-HBCD是主要的单体,其相对贡献率为45.15%~84.71%。辽河流域的工厂企业生产活动对淡水鱼类产生了影响,居民通过消费水产品摄入PBDEs和HBCDs。健康风险评估结果显示：PBDEs和HBCDs的健康风险指数均＜1,说明当地水产品中PBDEs和HBCDs的非致癌风险处于可接受水平。