太原市PM_(2.5)中溴代阻燃剂的污染特征及人体暴露水平

2013年10月至2014年7月,在太原城区,分4个月采集大气细颗粒物,每个月选取4个样品,分析了颗粒物上8种多溴联苯醚(PBDEs)和6种新型溴代阻燃剂(NBFRs)的浓度与组成。结果表明,大气PM2.5样品中PBDEs和NBFRs总浓度算术平均值分别为(10.9±10.3)pg·m-3和(22.3±24.7)pg·m-3,其中BDE-209、HBB和DBDPE是溴代阻燃剂中的主要污染物。季节变化来看,秋季样品中总PBDEs和总NBFRs的浓度要高于其他季节,夏季最低;化合物组成上,秋季样品中BDE-209含量较低,而NBFRs中HBB含量较高。相关分析显示,溴代阻燃剂的变化与颗粒物浓度和有机质的相关性不大,与大气温度与无显著性相关,而主要与气团来源有关。城市儿童的吸入暴露量约为成人的2~3倍,反映出PM2.5中溴代阻燃剂对城镇居民尤其是儿童的潜在健康危害仍不容忽视。     

气相色谱-三重四极杆质谱法测定人体血清中新型溴代阻燃剂

新型溴代阻燃剂(NBFRs)作为多溴二苯醚(PBDEs)的替代品,具有优良的防火性能.但有研究发现,NBFRs可能存在神经毒性和发育毒性等作用,从而对人体造成潜在的健康风险.血清作为人体内暴露的重要生物标志物,对评估健康风险具有重要意义.目前关于人体血清中NBFRs的健康风险研究较少,且血清中NBFRs含量低,前处理程序繁琐,基质复杂,给NBFRs的分析检测带来了很大困难.本研究建立并优化了人体血清中五溴苯(PBBz)、五溴甲苯(PBT)及十溴二苯基乙烷(DBDPE)等9种NBFRs的前处理,及气相色谱-三重四极杆质谱检测方法.血清样品经乙酸乙酯提取后,再经HLB固相萃取柱和弗罗里土-硅胶复合柱净化.采用电子轰击离子源(EI)和多反应监测(MRM)模式进行仪器分析.实验结果表明,血清样品中9种NBFRs的平均加标回收率在74%—136%之间,相对标准偏差小于21%.实际血清样品测试发现,内标物的回收率稳定在72%—126%之间,具有良好的检测效果.该方法前处理流程简单、稳定性好、灵敏度高,能广泛用于人体血清中NBFRs的分析.     

新型溴代阻燃剂(NBFRs)的生态毒性效应研究进展

由于传统的溴代阻燃剂(brominated flame retardants, BFRs),如多溴二苯醚(PBDEs)和六溴环十二烷(HBCD)等具有较高的生态风险,作为替代物的新型溴代阻燃剂(novel BFRs, NBFRs)被越来越多地生产和使用,如六溴苯(HBB)、五溴甲苯(PBT)、十溴二苯乙烷(DBDPE)、1,2-双(2,4,6-三溴苯氧基)乙烷(BTBPE)、四溴邻苯二甲酸双(2-乙基己基)酯(TBPH)和2,3,4,5,6,-五溴乙苯(PBEB)等。大量的NBFRs的生产、使用和废弃,导致其不可避免地释放到环境中,对生态环境和人类健康造成潜在的威胁。已有研究发现很多NBFRs不仅具有急性毒性、肝脏毒性、内分泌干扰毒性和发育毒性等毒性效应,也具有生物富集、积累和放大效应,存在生态风险。但目前缺乏系统和总结性的研究概述,故基于现有的研究结果,本文综述了有代表性的NBFRs的毒性效应研究内容和问题,并提出今后主要的研究方向。     

潍坊市滨海开发区人群血清中溴代阻燃剂浓度水平的时间变化趋势

本研究以溴系阻燃剂生产源区潍坊市滨海开发区作为研究区域,对潍坊市人群血清中PBDEs和NBFRs的浓度水平分布及时间变化趋势进行了分析.潍坊市人群血清样本中的PBDEs浓度(100.52-795.62 ng·g-1 1w(lipid weight,脂重),2016年;85.55-913.12 ng·g-1 1w,201...     

多溴联苯醚、六溴环十二烷和四溴双酚A在环境中污染现状的研究进展

作为最主要的三大传统溴系阻燃剂(BFRs),多溴联苯醚(PBDEs)、六溴环十二烷(HBCD)、四溴双酚A(TBBPA)具有半挥发性、环境持久性和远距离传输性,目前在全球各种环境介质、生物体内广泛存在.毒理学研究表明,PBDEs、HBCD、TBBPA均具有明显的生物毒性和致癌性,对生态环境和人体健康存在潜在危害.本文简要概述了PBDEs、HBCD、TBBPA的使用现状,综述了全球范围内非生物体(灰尘、水体、土壤、沉积物、污泥)和生命体内(植物、动物、人体)等3种传统BFRs的污染水平、特征、暴露途径和毒性,并讨论了当前存在问题,最后对PBDEs、HBCD、TBBPA的未来研究进行了初步展望.     

多溴联苯醚在啮齿类动物体内的代谢动力学研究进展

多溴联苯醚(PBDEs)是一类持久性有机污染物(POPs),其作为一种广泛使用的溴化阻燃剂在环境中普遍存在.PBDEs对生物体和人体存在内分泌干扰等毒性危害,正受到人们越来越多的关注.然而目前PBDEs对人体造成的影响都是由动物实验(主要是啮齿类动物)外推而得,因此研究不同的PBDEs同系物在啮齿类动物体内的代谢动力学...     

室内环境中多溴联苯醚的污染特征和暴露风险研究进展

多溴联苯醚(polybrominated diphenyl ethers,PBDEs)是一类常见的溴代阻燃剂,具有生育毒性、生殖毒性以及致癌性等慢性毒性.作为典型的溴代阻燃剂,多溴联苯醚常被加入到各种产品中以提高产品的安全性,但在各种商业产品的使用过程中,多溴联苯醚会不可避免地逸出至室内环境中,存在于空气或者灰尘中被人体摄入.研究表明,人类一生有80%—90%的时间处于室内环境中,因此,通过了解目前室内环境中多溴联苯醚的污染现状,进而评估通过室内环境暴露多溴联苯醚对人体的潜在危害极为重要.本文总结了室内环境中多溴联苯醚的浓度水平、组成特征以及人体暴露风险,并对未来的研究提出建议.     

环境空气中六溴环十二烷研究进展

六溴环十二烷(HBCDs)是一种添加型溴系阻燃剂,广泛应用于建筑隔热材料、纺织品涂层、电气和电子产品中.其为继多溴联苯醚、四溴双酚A之外的世界第三大溴代阻燃剂.HBCDs具有持久性有机污染物的长距离迁移性、生物累积性及毒性等特征,引起了全球关注.2013年5月HBCDs已被增列入《斯德哥尔摩公约》附件A中.HBCDs在环境各介质及生物体内均有检出,近年来,在室内空气和灰尘中也检出了大量HBCDs,其已成为人体暴露的一个重要来源.本文对大气环境及室内空气与灰尘中HBCDs的采样与分析方法、污染水平与来源,及人体暴露概况进行了综合阐释,并对其未来研究方向进行了展望,以期为我国大气和室内环境中HBCDs的研究工作提供参考.     

气相色谱-负化学离子源-质谱法分析母乳中多溴联苯醚

多溴联苯醚(PBDEs)是一种广泛使用的含溴阻燃剂.它和多氯联苯(PCBs)是一类具亲脂性、生物难降解性和高富集性的有机污染物,对人体健康具有一定的危害.     

高效液相色谱-串联质谱法分析六溴环十二烷对映异构体

六溴环十二烷（HBCD）是除十溴联苯醚、四溴双酚A之外的世界第三大阻燃剂产品,主要用作添加性的阻燃剂添加在热塑性塑料中.HBCD为添加型阻燃剂,易从产品中释放进入环境.HBCD的难降解性及高辛醇-水分配系数使其在动物体脂肪组织中具有潜在生物累积性,能够对动物体内分泌和免疫参数产生影响,导致人体基因重组     

Influence of aeration intensity on the performance of A/O-type sequencing batch MBR system treating azo dye wastewater

Among the numerous parameters affecting the membrane bioreactor (MBR) performance, the aeration intensity is one of the most important factors. In the present investigation, an anoxic/aerobic-type (A/O-type) sequencing batch MBR system, added anoxic process as a pretreatment to improve the biodegradability of azo dye wastewater, was investigated under different aeration intensities and the impact of the aeration intensity on effluent quantity, sludge properties, extracellular polymeric substances (EPS) amount generated as well as the change of permeation flux were examined. Neither lower nor higher aeration intensities could improve A/O-type sequencing batch MBR performances. The results showed 0.15 m³·h^-1 aeration intensity was promising for treatment of azo dye wastewater under the conditions examined. Under this aeration intensity, chemical oxygen demand (COD), ammonium nitrogen and color removal as well as membrane flux amounted to 97.8%, 96.5%, 98.7% and 6.21 L·m^-2·h^-1, respectively. The effluent quality, with 25.0 mg·L^-1COD, 0.84 mg·L^-1 ammonium nitrogen and 8 chroma, could directly meet the reuse standard in China. In the meantime, the sludge relative hydrophobicity, the bound EPS, soluble EPS and EPS amounts contained in the membrane fouling layer were 70.3%, 52.0 mg·g^-1VSS, 38.8 mg·g^-1VSS and 90.8 mg·g^-1VSS, respectively, which showed close relationships to both pollutant removals and membrane flux.     

低碳氮比废水好氧颗粒污泥系统稳定性及微生物种群多样性研究

低碳氮比(C/N)废水处理是含氮废水处理中的难题之一.本实验在C/N为4:1和2:1(COD和NH₄⁺-N浓度分别为400 mg·L^-1和100 mg·L^-1,400 mg·L^-1和200 mg·L^-1)条件下,考察好氧颗粒污泥系统对低碳氮比废水的处理效果、长期运行稳定性,研究C/N对好氧颗粒微生物结构变化的影响.研究结果表明,在C/N为4:1的废水中接种活性污泥培养好氧颗粒污泥,形成的颗粒沉降性能良好,MLSS为4.94 g·L^-1,SVI30为40 mL·g^-1,COD去除率90%以上,氨氮去除率接近100%.降低碳氮比,即C/N为2:1后,好氧颗粒的物理及硝化性能无明显变化,MLSS为11.38 g·L^-1,SVI₃₀/SVI₅维持在1左右,COD去除率大于85%,氨氮去除率98%.碳氮比降低使颗粒微生物多样性减少,其中陶厄氏菌受影响较小,而硝化功能菌出现更替:噬氢菌、食酸菌、里德拜特氏菌消失,鞘氨醇单胞菌、束缚杆菌等成为优势菌种.实验表明,该低碳氮比条件下好氧颗粒污泥系统能够稳定运行,且具有优良的处理性能.     

硝酸钙投加频次对污泥生物调理效果的影响

在接种了反硝化菌的剩余污泥中投加硝酸钙药剂,利用反硝化菌消耗NO₃^-进行反硝化作用去除污泥中易生物降解的有机物,利用Ca²⁺的中和、架桥作用,改善污泥的脱水性能.固定NO₃^-总投加浓度为100 mg·g^-1 TS,在6 d的时间内,按1次、2次、3次、6次的投加频次向污泥中投加硝酸钙.结果表明,1次投加对污泥脱水性能的提升最显著,较对照组而言,污泥CST降低了65.0%,SRF降低了73.2%,污泥脱水性能明显改善;投加硝酸钙后,污泥胞外聚合物中蛋白质含量大幅降低,S层、L层蛋白质分别从13.47 mg·L^-1、11.66 mg·L^-1降低至0.52 mg·L^-1、1.43 mg·L^-1;投加硝酸钙的污泥Zeta电位更趋于电中性.研究还发现,一次性投加硝酸钙产生了更多NO₂^-,有利于污泥结合水,即微生物细胞质的释放.释放出的有机碳被反硝化菌用作碳源,又增强了反硝化效果,从而促进了污泥EPS的破坏与降解,从而改善了污泥的脱水性能.     

Cultivation of aerobic granular sludge in a conventional,continuous flow,completely mixed activated sludge system

Aerobic granules were formed in a conventional, continuous flow, completely mixed activated sludge system (CMAS). The reactor was inoculated with seed sludge containing few filaments and fed with synthetic municipal wastewater. The settling time of the sludge and the average dissolved oxygen (DO) of the reactor were 2 h and 4.2 mg·L^-1, respectively. The reactor was agitated by a stirrer, with a speed of 250 r·min^-1, to ensure good mixing．The granular sludge had good settleability, and the sludge volume index (SVI) was between 50 and 90 mL·g^-1. The laser particle analyzer showed the diameter of the granules to be between 0.18 and 1.25 mm. A scanning electron microscope (SEM) investigation revealed the predominance of sphere-like and rod-like bacteria, and only few filaments grew in the granules. The microbial community structure of the granules was also analyzed by polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE). Sequencing analysis indicated the dominant species were α, β, and γ-Proteobacteria, Bacteroidetes, and Firmicutes. The data from the study suggested that aerobic granules could form, if provided with sufficient number of filaments and high shear force. It was also observed that a high height-to-diameter ratio of the reactor and short settling time were not essential for the formation of aerobic granular sludge.     

Occurrence and removal of selected polycyclic musks in two sewage treatment plants in Xi’an, China

Polycyclic musks are widely used for cosmetics and other personal care and household cleaning products. The occurrence and removal of two representative polycyclic musks, galaxolide (HHCB) and tonalide (AHTN) were investigated in three different processes of two sewage treatment plants (STPs) in Xi’an, China. The samples were preconcentrated by solid phase extraction procedure and analyzed using a gas chromatography mass spectrometry (GC/MS) by a modified procedure. The HHCB was in the range of 82.8 to 182.5 ng·L^-1 in the influents and 22.6 to 103.9 ng·L^-1 in the effluents. The AHTN ranged from 11.0 to 19.3 ng·L^-1 in the influents and 2.2 to 8.8 ng·L^-1 in the effluents. The removal efficiency of the two musks varied in the ranges of 43.1%–70.4% for HHCB and 54.2%–84.4% for AHTN. Concentrations of the two musks in aqueous phase of three processes slightly increased along the primary process, and significantly removed during the biologic treatment processes, revealing that the selected musks could be remarkably removed in varied activated sludge processes. Advanced processes of activated sludge did not show a significant superiority on selected musk removal compared to the conventional process. The selected musk removal mainly resulted from the adsorption function of activated sludge. There was no significant change of HHCB/AHTN ratios along the treatment flow, indicating that each sewage treatment structure had a similar removal efficiency for the two musks.     

Fermentative hydrogen production from beet sugar factory wastewater treatment in a continuous stirred tank reactor using anaerobic mixed consortia

A low pH, ethanol-type fermentation process was evaluated for wastewater treatment and bio-hydrogen production from acidic beet sugar factory wastewater in a continuous stirred tank reactor (CSTR) with an effective volume of 9.6 L by anaerobic mixed cultures in this present study. After inoculating with aerobic activated sludge and operating at organic loading rate (OLR) of 12 kgCOD?m^-3·d^-1, HRT of 8h, and temperature of 35°C for 28 days, the CSTR achieved stable ethanol-type fermentation. When OLR was further increased to 18 kgCOD?m^-3·d^-1 on the 53rd day, ethanol-type fermentation dominant microflora was enhanced. The liquid fermentation products, including volatile fatty acids (VFAs) and ethanol, stabilized at 1493 mg·L^-1 in the bioreactor. Effluent pH, oxidation-reduction potential (ORP), and alkalinity ranged at 4.1–4.5, -250–(-290) mV, and 230–260 mgCaCO₃?L^-1. The specific hydrogen production rate of anaerobic activated sludge was 0.1 L?gMLVSS^-1·d^-1 and the COD removal efficiency was 45%. The experimental results showed that the CSTR system had good operation stability and microbial activity, which led to high substrate conversion rate and hydrogen production ability.     

Reduction of hexavalent chromium with scrap iron in a fixed bed reactor

The reduction of hexavalent chromium by scrap iron was investigated in continuous long-term fixed bed system. The effects of pH, empty bed contact time (EBCT), and initial Cr(VI) concentration on Cr(VI) reduction were studied. The results showed that the pH, EBCT, and initial Cr(VI) concentration significantly affected the reduction capacity of scrap iron. The reduction capacity of scrap iron were 4.56, 1.51, and 0.57 mg Cr(VI)·g^-1 Fe⁰ at pH 3, 5, and 7 (initial Cr(VI) concentration 4 mg·L^-1, EBCT 2 min, and temperature 25°C), 0.51, 1.51, and 2.85 mg Cr(VI)·g^-1 Fe⁰ at EBCTs of 0.5, 2.0, and 6.0 min (initial Cr(VI) concentration 4 mg·L^-1, pH 5, and temperature 25°C), and 2.99, 1.51, and 1.01 mg Cr(VI)·g^-1 Fe⁰ at influent concentrations of 1, 4, and 8 mg·L^-1 (EBCT 2 min, pH 5, and temperature 25°C), respectively. Fe(total) concentration in the column effluent continuously decreased in time, due to a decrease in time of the iron corrosion rate. The fixed bed reactor can be readily used for the treatment of drinking water containing low amounts of Cr(VI) ions, although the hardness and humic acid in water may shorten the lifetime of the reactor, the reduction capacity of scrap iron still achieved 1.98 mg Cr⁶⁺·g^-1 Fe. Scanning electron microscope equipped with energy dispersion spectrometer and X-ray diffraction were conducted to examine the surface species of the scrap iron before and after its use. In addition to iron oxides and hydroxide species, iron-chromium complex was also observed on the reacted scrap iron.     

高效液相色谱-串联质谱法同时检测水体中26种药物及个人护理品

通过优化固相萃取条件和高效液相色谱-串联质谱参数,建立了可以同时检测地表水和地下水中26种典型药物及个人护理品(pharmaceuticals and personal care products,PPCPs),包括磺胺类、大环内酯类、喹诺酮类、酰胺醇类、精神类、消炎止痛类以及个人护理品的检测方法.通过将水样pH值调节至7,利用HLB固相萃取柱对水样中PPCPs进行富集,以甲醇和含0.005%甲酸的水溶液作为正离子模式流动相,甲醇和含0.5 mmol·L^-1乙酸铵的水溶液作为负离子模式流动相进行梯度洗脱,采用多反应监测的质谱扫描模式(MRM)分析测定.26种PPCPs的检出限为0.007—1.78 ng·L^-1,定量限为0.02—5.68 ng·L^-1,回收率为52.28%—115.24%.利用该方法检测北京潮白河地表水和地下水中PPCPs的浓度,结果表明,地表水中PPCPs的含量普遍高于地下水,磺胺甲恶唑、舒必利、咖啡因、卡马西平和布洛芬在地表水和地下水中的含量相对较高,检测浓度分别高达147.83、52.48、78.35、166.58、30.63 ng·L^-1.     

Selective recovery of Cu2+ and Ni2+ from wastewater using bioelectrochemical system

As the bioelectrochemical system, the microbial fuel cell (MFC) and the microbial electrolysis cell (MEC) were developed to selectively recover Cu²⁺ and Ni²⁺ ions from wastewater. The wastewater was treated in the cathode chambers of the system, in which Cu²⁺ and Ni²⁺ ions were removed by using the MFC and the MEC, respectively. At an initial Cu²⁺ concentration of 500 mg·L^-1, removal efficiencies of Cu²⁺ increased from 97.0%±1.8% to 99.0%±0.3% with the initial Ni²⁺ concentrations from 250 to 1000 mg·L^-1, and maximum power densities increased from 3.1±0.5 to 5.4±0.6 W·m^-3. The Ni²⁺ removal mass in the MEC increased from 6.8±0.2 to 20.5±1.5 mg with the increase of Ni²⁺ concentrations. At an initial Ni²⁺ concentration of 500 mg·L^-1, Cu²⁺ removal efficiencies decreased from 99.1%±0.3% to 74.2%±3.8% with the initial Cu²⁺ concentrations from 250 to 1000 mg·L^-1, and maximum power densities increased from 3.0±0.1 to 6.3±1.2 W·m^-3. Subsequently, the Ni²⁺ removal efficiencies decreased from 96.9%±3.1% to 73.3%±5.4%. The results clearly demonstrated the feasibility of selective recovery of Cu²⁺ and Ni²⁺ from the wastewater using the bioelectrochemical system.     

十溴联苯醚(BDE-209)对土壤跳虫的急、慢性毒性效应

为揭示溴代阻燃剂对土壤生态系统的潜在危害,采用回避实验和繁殖实验评价了十溴联苯醚(BDE-209)对2种土壤跳虫Folsomia candida和Folsomia fimetaria的急/慢性毒性。48h的急性回避实验中,BDE-209对F.candida和F.fimetaria产生毒性效应的EC_(50)值分别为1.27和0.79mg·kg~(-1),LOEC值均小于0.5mg·kg~(-1)。慢性繁殖实验中,BDE-209对F.candida和F.fimetaria繁殖毒性的EC_(50)值分别为0.81和0.56mg·kg~(-1),LOEC值分别为<0.25和<0.5mg·kg~(-1)。研究表明,土壤BDE-209污染对跳虫的繁殖和环境行为有显著影响,且在较低暴露浓度下(0.25mg·kg~(-1))即对跳虫繁殖产生抑制效应;有性生殖的F.fimetaria比孤雌生殖的F.candida对BDE-209污染的毒性响应更为敏感。