Formation of 2,3,7,8‐tetrabromodibenzodioxin and ‐furan by thermolysis of polymers containing brominated flame retardants

Several plastic products which are used in areas exposed to fire hazards contain flame retardants. A group of important flame retardants are brominated aromatic compounds, and it is believed that they thermally generate polybrominated dibenzodioxins (PBrDD) and dibenzofurans (PBrDF).

The formation of 2,3,7,8‐Tetrabromodibenzodioxin (TBrDD) and ‐Tetrabromodibenzofuran (TBrDF) from various plastics with brominated flame retardants under different thermolysis conditions is presented. At 600 °C, 2,3,7,8‐TBrDD and ‐TBrDF in concentrations of 0.01–7 and 0.01–6 ppm, respectively, are formed from plastics containing decabromodiphenylether or polybromodiphenylether as flame retardant. With increasing temperature the concentration of these isomers decreases until they are no longer detectable above 800 °C (detection limit: 0.01 ppm).

The hypothetical reaction pathways for the formation of 2,3,7,8‐TBrDD and ‐TBrDF by thermolysis of decabromodiphenylether are proposed.

The solubility and photochemical properties of 2,3,7,8‐TBrDD in different solvents are given.     

Dispersive liquid–liquid microextraction of cadmium(II) for preconcentration prior to flame atomic absorption spectrometric detection in water

A dispersive liquid–liquid microextraction procedure for cadmium(II) as its 2-(5-bromo-2-pyridylazo)-5-diethylamino-phenol chelate is presented. Carbon tetrachloride and methanol were used as extraction and dispersive solvents, respectively. After phase separation, the preconcentrated-separated cadmium(II) is determined by flame atomic absorption spectrometry with a microinjection technique. The factors which affected the extraction efficiency, i.e. the pH of the sample solution and the volumes of reagent and sample were investigated. The effects of some alkali, alkali earth, and transition metal ions, and of some anions on the recovery of cadmium were also studied. A preconcentration factor of 250 was obtained for a sample volume of 50?mL under optimum conditions. The method was validated by analysis of certified reference materials and applied to some water samples from Turkey.     

Assessment of lead and cadmium residues in farmed fish in Machakos and Kiambu counties,Kenya

Lead (Pb) and cadmium (Cd) concentrations were determined in muscle, gonad, liver and brain of tilapia fish caught from fish ponds in Machakos and Kiambu counties in Kenya. A total of 217 fish samples were randomly sampled from the two counties. Acid digestion method and atomic absorption spectrophotometer were used for analysis. Heavy metal concentrations varied significantly depending on the type of tissue analyzed. Generally, the highest concentration of Pb was detected in brain and the liver. Fish organs contained Pb in the following order: brain > liver > muscle > gonad, while Cd followed the order: brain > liver > gonad > muscle. Kiambu county recorded higher concentration of the studied heavy metals compared to Machakos county although statistically there was no difference. Lead and Cd content in both counties studied exceeded the maximum allowable limit. The study recommended controlling industrial and agricultural effluents into surface water and proper sitting of ponds to minimize the risk of contamination of farmed fish by heavy metals.     

饮用水中二级胺的气相色谱快速检测方法研究

以二甲胺、二乙胺、甲乙胺、吗啉和N-甲基苄胺5种二级胺代表物质为例,分别使用气相色谱-氢火焰(GC-FID)技术和气相色谱-质谱(GC-MS)技术检测饮用水中二级胺质量浓度。结果表明,使用优化的预处理方法处理后进样分析,5种代表物质的线性范围在20~2 000μg/L,相对标准偏差(RSD)≤0.46%,最低检出限在3.18~24.19μg/L。FID比MSD具有较强优势。该方法对于直链脂肪类和杂环类的二级胺都有良好的检测效果,可用于对饮用水二级胺类物质的检测。     

直线管道煤尘爆炸火焰传播规律的试验研究

为提供煤尘爆炸事故预防和缓解所需的科学依据,对煤尘爆炸火焰传播过程进行试验研究。所用试验装置,其主要部分为直径0.3 m的圆形管道与断面边长为80 mm的方形管道对接形成的一个长2 m的爆炸腔体。在其中共进行9次煤尘爆炸试验。结果表明,煤尘爆炸火焰传播具有速度快,波动大,稳定性较差的特点,火焰区长度远大于扬尘区长度,最大火焰速度和传播距离与煤尘量均不存在正比例关系,但存在一个特定的煤尘质量浓度。在这个特定质量浓度处,最大火焰速度达到最大值。当煤尘质量浓度大于这个特定质量浓度时,火焰传播速度曲线整体下降,暂时缺氧被认为是导致这一情况的重要因素。     

基于层次分析法的电缆燃烧性能综合指标评价体系

目前对于电缆燃烧性能评价方法大多采用延燃性作为单一评价指标,但是电缆的燃烧性能还应包括生烟性、毒性和腐蚀性等方面.国内外大量试验证明锥形量热计试验结果与全尺寸试验结果相关性较好,利用锥形量热计对真实火灾情况下电缆燃烧性能进行评价较为合理.本文在锥形量热计燃烧试验基础上,构建了电缆燃烧性能综合指标评价体系,并运用层次分析法确定各指标的权重.该体系为电缆燃烧性能评价研究提供一种新的尝试,也可为以后的阻燃电缆分级体系建立提供一些参考.     

十溴联苯醚（BDE-209）对成年大鼠甲状腺激素的影响

多溴联苯醚(PBDEs)是现代工业中广泛应用的溴系阻燃剂,PBDEs具有持久性有机卤素污染物(Organohalogen Contaminants,OHCs)和内分泌干扰物(Endocrine Disrupters,EDs)的化学物理特性.PBDEs的生物毒性也是国际上环境生态科学的关注热点.论文建立了十溴联苯醚(BDE-209)暴露剂量的成年大鼠模型,测定了不同暴露剂量的实验动物血清甲状腺激素(Thyroid hormones,THs)水平,初步研究了PBDEs污染物对生物体甲状腺激素的影响.BDE-209的量-效关系研究结果显示,TT4、FT4和TT3浓度均随着暴露剂量的提高而下降,这可能是BDE-209对甲状腺合成分泌T4、T3起到了抑制作用.不同BDE-209暴露剂量下,TT4~FT4以及TT4~TT3的正相关系数大于FT3~TT3以及FT3~FT4,这意味着BDE-209暴露对于T4从甲状腺激素转运结合蛋白(Transthyretin,TTR)的分离与脱碘过程影响不明显,而影响了结合态T3从TTR的分离过程以及FT4的脱碘过程,从而对甲状腺激素的平衡具有干扰效应.采用基准点分析法,研究了BDE-209对于甲状腺干扰相对效应的时间-效应关系,实验表明由于甲状腺的应激作用,对于毒物具有自我防御功能,BDE-209对甲状腺的干扰效应在5~8d后才有所显现,持续时间至少为14d.     

连通容器气体密闭爆炸与泄爆过程的实验研究

利用球型容器与管道组合,开展连通容器气体爆炸与泄爆实验,分析连通条件下,火焰在管道中的传播过程及其对起爆容器和传爆容器的压力影响。实验结果表明:连通容器气体爆炸中,火焰从起爆容器到传爆容器传播经历了一段不断加速,但加速度不断减小的过程;泄爆过程中,火焰传播过程与密闭爆炸时基本一致。管道中火焰加速传播,使得传爆容器的爆炸压力和强度相较于作为起爆容器时均明显增加,危险更大,采用与起爆容器相同的泄爆面积,无法满足对连通容器中传爆容器的泄爆。同时,泄爆是一个快速的能量泄放过程应选择合理的泄爆方式,防止二次危害。     

东江表层沉积物中的有机磷系阻燃剂

采用索氏抽提,HLB固相萃取柱分离净化和气相色谱质谱联用仪(GC-MS-EI/SIM)的分析方法对采自东江的17个沉积物中的8种有机磷系阻燃剂(OPFRs)的浓度及分布进行研究.结果表明,所有样品中均检测到了OPFRs,其总浓度为1.52~86.17ng/g.三(1-氯-2-丙基)磷酸酯(TCPP)为最主要污染物,最高浓度达51.64ng/g,其后为三苯基磷酸酯(TPP)、三(2-氯乙基)磷酸酯(TCEP)、三(1,3-二氯异丙基)磷酸酯(TDCP),最高浓度分别为22.03,9.51,6.09ng/g,而其他烷基类OPFRs除三乙基磷酸酯(TEP)外未被检出.OPFRs总浓度和与总有机碳(TOC)存在极显著的相关性(r=0.74,P＜0.001),说明沉积物中TOC的含量对有机氯代磷系阻燃剂的分布起重要作用.尽管东江沉积物中的OPFRs含量(均值25.43ng/g)远低于多溴联苯醚(PBDEs)含量(均值588ng/g),但随着PBDEs的全球禁用,相关有机磷系阻燃剂的污染态势需要引起更多关注.     

溴代阻燃剂对氧化亚铁硫杆菌浸提废旧电脑主板覆层铜的影响

以破碎至10~20目(0.84~2.00 mm)的废旧电脑主板颗粒为试验材料,分为未处理(未去除溴代阻燃剂的主板颗粒)、处理(去除30%溴代阻燃剂的主板颗粒)、加萃取物(处理主板颗粒和萃取物)、对照4组. 以CCl₄作为萃取剂,采用固液萃取技术,分析了在微生物作用下不同处理组中ρ(Cu2+)、ρ(Fe3+)、E_h(氧化还原电位)和pH的变化,以考察溴代阻燃剂对氧化亚铁硫杆菌(Thiobacillus ferrooxidans)浸Cu率的影响. 结果表明:随着浸提时间的增加,氧化亚铁硫杆菌对未处理、处理和加萃取物3组的浸Cu率不同,其中处理组最好,加萃取物组最差. 浸提过程中,ρ(Fe3+)、E_h和pH与微生物活性、浸Cu率显著相关,表现为微生物活性越好,ρ(Cu2+)和pH越大,ρ(Fe3+)和E_h越小. 浸提24和168 h,处理组的浸Cu率比未处理组分别提高了14.11%和17.37%; 而加萃取物组的浸Cu率比未处理组分别降低了27.69%和21.67%. 表明废旧电脑主板中的溴代阻燃剂是影响微生物浸Cu率的重要因素之一. 为进一步提高浸Cu率,必须考虑溴代阻燃剂对微生物生长的影响.