加速溶剂萃取/凝胶渗透色谱净化/气相色谱-负化学离子源质谱测定生物样品中的四溴联苯醚

建立了一种分析生物样品中四溴联苯醚（BDE-47）的方法.获得了优化的前处理条件和GC/MS检测条件,采用加速溶剂萃取（ASE）-凝胶渗透色谱（GPC）/多层硅胶-氧化铝复合柱净化,气相色谱-质谱（负化学离子源）（GC/NCI-MS）分析.以猪肝为基质的BDE-47加标回收率结果为77.3%—118.7%,相对标准偏差...     

自组装哑铃状Fe3O4微/纳米材料对十溴联苯的热催化降解

多溴联苯(PBBs)是一类新型持久性有机污染物,具有高毒性和生物累积性,对人类健康和生态环境具有潜在危害.为探究PBBs的消减技术和降解机制,利用多元醇介导自组装法制备出了哑铃状形貌的Fe3O4前驱体,将前驱体在氮气氛围下焙烧制得哑铃状Fe3O4微/纳米材料,以十溴联苯(BB209)作为模型化合物进行热催化降解研究.结果发现,哑铃状Fe3O4前驱体生长过程分为无定型粒子的快速成核和初级粒子间相互团聚结晶两个阶段;哑铃状Fe3O4对BB209表现出较高的降解活性,在300℃下反应30 min时,Fe3O4对BB209的降解率几乎已达到100%;在哑铃状Fe3O4降解BB209的产物中检测到一系列的从九溴代联苯到一溴代联苯产物与联苯产物,表明在降解过程中存在加氢脱溴反应路径;在降解产物中鉴定出3种九溴联苯异构体BB206、BB207、BB208,且3种异构体含量的大小顺序为:BB207BB208BB206,表明不同取代位上Br的活性相对大小为:间位对位邻位.     

Sorption isotherms of brominated diphenyl ethers on natural soils with different organic carbon fractions

Sorption isotherms of BDE-28 and BDE-47 on natural soils with different contents of soil organic matter (SOM) were investigated. Due to low water solubility of BDEs and resulted narrow ranges of aqueous equilibrium concentration, the linear distribution model showed similar and good fitting efficiency to the linear portion of nonlinear Freundlich curve. For the same sample, the linear and nonlinear model fitting sorption coefficients were close. At the statistically significant level of 0.05 or 0.1, significant relationships of total organic carbon fraction (fOC) with the fitting sorption coefficients can be observed. As for BDE-28, the relationships of fOC and SOM fractions with the single point partition coefficients at different aqueous concentrations of BDEs were significant; while for BDE-47, the relationships became less significant or insignificant, especially at higher aqueous concentrations. The findings in this study may facilitate more understanding on transport and fate of studied BDEs in soil systems.     

重金属对白腐菌降解十溴联苯醚的影响

考察了重金属(Cu、Cd、Pb)对白腐菌生长及其降解十溴联苯醚(BDE-209)的影响及其机制.结果表明,低浓度重金属(≤1 mg.L-1)可促进白腐菌的生长,高浓度则表现为抑制作用,1 mg.L-1时促进作用大小为:Cd>Pb>Cu;白腐菌可高效降解BDE-209,7 d内对BDE-209(1 mg.L-1)降解率可达69.7%;重金属可显著影响白腐菌对BDE-209的降解(P<0.05),低浓度的Cu(≤1 mg.L-1)和Cd(≤0.5 mg.L-1)对BDE-209的降解表现为促进作用,其中Cu为1 mg.L-1时促进作用最明显,降解率为84.4%,而Pb则为抑制作用;高浓度(>1 mg.L-1)的重金属均会抑制BDE-209的降解,抑制作用大小为Cd>Pb>Cu,且随浓度增大抑制作用增强;降解率与生物量变化不完全正相关.白腐菌对BDE-209的降解过程符合一级反应动力学方程,Cu、Cd存在条件下,随着其浓度的增加,降解速率常数k表现为先增加后减少,Cu为1 mg.L-1时k值达到最大,为0.321 2;Pb存在条件下,k值表现为逐渐减小.进一步研究了重金属对白腐菌胞外酶降解BDE-209的影响,并运用SPSS 17.0对胞外酶降解与菌体降解进行距离相关性分析,结果表明,未添加重金属时胞外酶降解与菌体降解差异不大,其降解率分别为63.7%、69.7%;3种重金属存在条件下其相关系数R值均大于0.9,由此推断胞外酶是起降解作用的主要部分,重金属主要通过影响白腐菌胞外酶的方式作用于BDE-209的降解.     

十溴联苯醚对紫花苜蓿种子萌发及幼苗的影响

为评价十溴联苯醚(BDE-209)对植物的生态毒性效应,探明植物抵抗BDE-209胁迫的反应机制,文章选用紫花苜蓿作为受试植物,考察了不同浓度BDE-209污染土壤对紫花苜蓿种子萌发及幼苗生长的影响,并对幼苗体内的抗氧化酶活性(POD、CAT、SOD)及可溶性蛋白质(SP)对污染物胁迫的响应进行了研究,同时还对植株的根、叶片进行扫描电镜观察。结果表明,BDE-209胁迫处理与各项生长指标呈显著负相关,抑制作用强度依次为根长>鲜重>芽长>发芽率。植株体内的抗氧化酶活性和可溶性蛋白含量随污染物浓度的增加不断上升,符合线性关系,POD、CAT、SOD的活性最大可高达对照的3倍、1.77倍和2.81倍,可溶性蛋白含量可达到对照的1.89倍。扫描电镜结果显示,随着污染物浓度的提高,植物根部发根增多,叶片上气孔密度增大,气孔开度变小。     

Degradation of 2,2′,4,4′-tetrabromodiphenyl ether by Pycnoporus sanguineus in the presence of copper ions

The degradation of 2,2′,4,4′-tetrabromodiphenyl ether(BDE-47) by Pycnoporus sanguineus was investigated in order to explore the impact of the heavy metal Cu~(2+) on BDE-47 decomposition and the subsequent formation of metabolites, as well as to further elucidate the degradation mechanism of BDE-47. An increase in degradation rate from 18.63% to49.76% in the first four days and its stabilization at(51.26 ± 0.08)% in the following days of BDE-47 incubation were observed. The presence of Cu~(2+) at 1 and 2 mg/L was found to promote the degradation rate to 56.41% and 60.79%, respectively, whereas higher level of Cu~(2+) (≥ 5 mg/L) inhibited the removal of BDE-47. The similar concentration effects of Cu~(2+) was also found on contents of fungal protein and amounts of metabolites. Both intracellular and extracellular enzymes played certain roles in BDE-47 transportation with the best degradation rate at 27.90% and 27.67% on the fourth and third day, individually. During the degradation of BDE-47, four types of hydroxylated polybrominated diphenyl ethers(OH-PBDEs), i.e., 6′-OH-BDE-47, 5′-OH-BDE-47, 4′-OH-BDE-17, 2′-OH-BDE-28, and two bromophenols, i.e., 2,4-DBP and 4-BP were detected and considered as degradation products. These metabolites were further removed by P. sanguineus at rates of 22.42%,23.01%, 27.04%, 27.96%, 64.21%, and 40.62%, respectively.     

碱性及含硫化合物对十溴联苯醚热降解的影响

将十溴联苯醚（BDE-209）于400~600℃的温度范围内进行热降解,利用GC、GC/MS对产物种类及含量变化进行分析,讨论了温度、时间、碱性化合物和含硫化合物对BDE-209降解以及对溴代二噁英生成的影响.结果表明.温度和时间均是BDE-209热降解和生成溴代二噁英的重要影响因素;热降解40min时,450℃条件下溴代二噁英生成量最多;产物种类证实碱性化合物通过与BDE-209脱溴形成的HBr反应促进降解,且可抑制二噁英的生成;含硫化合物的添加同样促进BDE-209降解,抑制二噁英的形成,其详细的抑制机理有待进一步确定,BDE-209的降解反应有两种情况,即苯环上的脱溴反应和醚键的断裂反应.     

表面活性剂对苏云金芽孢杆菌J-1降解BDE-209的影响

表面活性剂对有机污染物污染的环境有增效修复作用。本文通过考察鼠李糖脂、蔗糖脂肪酸酯和茶皂素对BDE-209的增溶作用、对菌J-1生长的影响及菌J-1对表面活性剂的利用,研究了3种表面活性剂对菌J-1降解BDE-209的影响及机理。结果表明：3种表面活性剂对BDE-209的增溶能力大小为：鼠李糖脂>蔗糖脂肪酸酯>茶皂素。低浓度鼠李糖脂（<100 mg/L ）、蔗糖脂肪酸酯（<50 mg/L）和茶皂素（<50mg/L）都能促进J-1对BDE-209的降解,且促进作用随表面活性剂浓度增加而增强,最高分别可将BDE-209降解率提高23.18%,16.47%和12.64%。3种表面活性剂中、高浓度均对J-1降解BDE-209有抑制作用,当鼠李糖脂、蔗糖脂肪酸酯和茶皂素浓度为1000 mg/L时,J-1对BDE-209的降解率分别降低35.32%、16.54%和27.76％。低浓度表面活性剂的促进作用是增溶和协同代谢的综合效应;中等浓度的蔗糖脂肪酸酯（200-700mg/L）和茶皂素（100-200mg/L）的抑制作用是由于底物竞争或（/和）表面活性剂胶束内裹BDE-209阻碍了菌J-1 与其接触所致;而高浓度表面活性剂的抑制作用是由于表面活性剂对菌J-1的毒害所致。     

树脂D001负载纳米Pd/Fe双金属脱溴2,2＇,4,4＇-四溴联苯醚（BDE-47）的研究

采用大孔树脂D001交换吸附Pd2＋、Fe2＋并在厌氧条件下以硼氢化钠溶液还原吸附的钯铁离子制备成负载纳米Pd/Fe双金属树脂。利用该树脂对2,2＇,4,4＇-四溴联苯醚（BDE-47）进行脱溴反应,探讨了该法的可行性和特性。结果表明：当大孔树脂D001、氯化钯、硫酸亚铁用量分别为0.75 g、2μg和0.2 g时所制备的双金属树脂脱溴水-乙醇溶液中的BDE-47效果最佳,反应遵循准一级动力学,速率常数k约为0.161 d-1,半减期为1.21 d。负载Pd/Fe的D001连续3次脱溴反应都有较好的效果,水-乙醇溶液中超过90%以上的BDE-47在反应6 d后被降解。负载Pd/Fe双金属的树脂可以重复活化再生,但再生2次后其脱溴效率变差,反应6 d只有47.3%的BDE-47被降解。用气相色谱-质谱联用仪和离子色谱仪跟踪Pd/Fe双金属树脂脱溴BDE-47反应,可知产物包括溴离子、三溴联苯醚、二溴联苯醚、一溴联苯醚和联苯醚。