Aspects of formation and degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans

The research progress on the mechanisms of formation and degradation of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) is reviewed. The primary sources of PCDD/Fs are chemical, thermal, photochemical and enzymatic reactions. Most of the thermal sources result in emissions into air. The studies on the photodegradation and biodegradation offer promise for destruction of PCDD/Fs in environment.     

氯酚前驱物气相中形成二噁英类物质（ PCDD/Fs）的研究进展

评述了氯酚前驱物在气相中形成二噁英类物质（PCDD/Fs）的机制,总结了理论上形成PCDD/Fs的主要步骤,包括：氯苯氧基活性基的生成、苯氧基的自缩合作用、产生的初步的中间体经环化作用和脱氯反应形成PCDDs和PCDFs.     

Spatial concentration, congener profiles and inhalation risk assessment of PCDD/Fs and PCBs in the atmosphere of Tianjin, China

Polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were monitored in a seasonal passive sampling scheme during June 2008 and January 2009 to investigate the spatial concentration, congener profiles and evaluate the potential inhalation risk in different functional areas in Tianjin, China. The spatial air concentrations and I-TEQs ranged 1.08×10²–8.19×10³ fg m^?3 (average 2.63×10³ fg m^?3) and 4.08–325 fg I-TEQ m^?3 (average 91.4 fg I-TEQ m^?3) respectively for PCDD/Fs. The concentration and I-TEQs of PCBs were 3.08×10⁴–3.01×10⁵ fg m^?3 (average 1.39×10⁵ fg m^?3) and 1.72–49.6 fg I-TEQ m^?3 (average 18.5 fg I-TEQ m^?3). It is obvious that PCB concentrations were several hundred times higher than the PCDD/Fs. However, the ambient air PCDD/Fs contributed a major part to the total toxicity equivalents, varying from 72.7% to 89.0% (average 81.8%). The atmospheric PCDD/F levels were observed to be higher in winter for most of sampling sites in the downtown. Besides, inhalation risk assessment showed that local residents might suffer more risk near the point sources than those in living area, industrial zones and background area in Tianjin City. However, the total daily dioxin intake was approximately several to hundreds of times lower than the WHO criteria, showing relatively low exposure risks from the impact of industry point sources in Tianjin City.     

Concentrations, profiles and gas-particle partitioning of PCDD/Fs, PCBs and PBDEs in the ambient air of an E-waste dismantling area, southeast China

Polychlorinated diebenzo-p-dioxins （PCDDs）, polychlorinated diebenzofurans （PCDFs）, polychlorinated biphenyls （PCBs） and polybrominated diphenyl ethers （PBDEs） were monitored in the ambient air of Taizhou, an E-waste dismantling area of southeast China to evaluate their concentrations, profiles and gas-particle partitioning. The ∑PCDD/Fs concentrations ranged from 2.91 to 50.6 pg/ma, with an average of 14.3 pg/ma. The I-TEQs for PCDD/Fs were in the range of 0.20-3.45 pg/ma, with an average of 1.10 pg/ma, The ∑PCBs concentrations and TEQs ranged from 4.23 to 11.35 ng/ma, 0.050 to 0.859 pg（TEQ）/ma, respectively. The concentrations of ∑PBDEs ranged from 92 to 3086 pg/ma, with an average of 894 pg/ma, The pollution levels of PCDD/Fs, PCBs and PBDEs were higher than other urban sites, which may be associated with the E-waste dismantling activities. The PCDD/Fs were found exclusively in the particle phase whereas PCBs distributed dominantly in the gas phase. The gas-partilce partitioning was also assessed by correlating the gas-particle partition coefficient （Kp） with the subcooled liquid vapor pressure （pL^0）. The measured particulate sorptions of PCDD/Fs, PCBs and PBDEs were compared with the predictions from Junge-Pankow model and Koa absorption model. The Junge-Pankow model well estimated the particulate fractions of PCBs. However, it underestimated the sorptions of PCDD/Fs and overestimated the fractions of PBDEs. The predicted particulate fractions of PCDD/Fs and PCBs from Koa model fitted well with the measured data.     

Patterns and levels of PCDD/F in a Chinese graphite electrode sludge

The graphite electrode sludge was sampled from a huge chloralkali plant in central China. The total level of PCDD/F was found as high as 378.85 μg/kg sludge (dry weight). The patterns of PCDD/F in each homologue indicated the predominance of tetra-to octa-chlorinated PCDFs. Furthermore, the toxic 2,3,7,8-substituted PCDFs constituted over 80% of the total PCDFs in the sludge and the corresponding PCDDs were only at 15 μg/kg level. The calculated value of the international toxic equivalence (I-TEQ) in sludge was 21.65 μg/kg sludge (dry weight). This typical “dioxin chloralkali pattern” was apparently identified in the sediments near the effluent outlet of the chloralkali plant.     

市政污泥与生活垃圾协同焚烧的二噁英排放特征及毒性当量平衡

于2016年5月和2017年1月，分别对南方某生活垃圾焚烧发电厂开展生活垃圾与市政污泥(分别为0%、5%、10%和15%)协同焚烧试验，探讨市政污泥掺烧对生活垃圾焚烧过程中PCDD/Fs排放的影响.在不同季节中，PCDD/Fs均主要分布于飞灰与炉渣中.受焚烧过程中PCDD/Fs的结构破合与重组的影响，废渣中以2, 3, 4, 7, 8-PeCDF (13.0%~72.1%)单体为主. 2016年5月，每吨焚烧原料(指生活垃圾跟污泥的混合物)混合焚烧排放的PCDD/Fs毒性当量比原料本身含有的增加了14.1~29.2 μg TEQ/t，而2017年1月则降低了9.2~9.9 μg TEQ /t.生活垃圾焚烧过程中加入市政污泥能够提高焚烧材料中的硫元素与氯元素的质量比，从而抑制PCDD/Fs的再合成.综上所述，在保证生活垃圾焚烧发电厂的电力生产条件下，适当的市政污泥与生活垃圾协同焚烧能够降低焚烧过程中的PCDD/Fs排放，从而实现市政垃圾污泥的安全处理处置.     

灰霾天气下北京海淀城区空气中溴代二恶英在不同粒径颗粒物上的分布特征研究

采用大气颗粒物分级采样器在同一地点连续采集灰霾天北京海淀城区空气样品,调研了空气中溴代二恶英（PBDD/Fs）的污染水平和在不同粒径颗粒物上的分布特征。研究结果表明：灰霾天城区空气样品中PBDD/Fs的质量浓度为1 535~6 053 fg/m³;PBDD/Fs的浓度随着颗粒物粒径（aerodynamic diameter,d_ae）的减小而增加,在d_ae<1.0 μm的颗粒物上浓度最高,80%以上的PBDD/Fs分布在d_ae<2.5 μm的颗粒物上;PBDD/Fs在不同粒径颗粒物上的含量不等,但均以高溴代二苯并呋喃（PBDFs）为主,且其所占比例随颗粒物粒径的增加而减小,然而多溴代二苯并-对-二恶英（PBDDs）在不同粒径颗粒物上的分布差异性却不显著。     

西江二恶英的季节变化、通量及来源

用同位素稀释-高分辨色谱／高分辨质谱（HRGC／HRMS）方法对西江（珠江的主干）进行了1a的水相和颗粒相中多氯代二苯并二恶英／呋喃（PCDD／Fs）测定。结果表明，水相中PCDD／Fs的含量范围在1．567-8．008pg／L之间．颗粒物中PCDD／Fs的含量变化在569．4～279．6pg／g之间，经过分析得出其浓度随着西江流量的季节性变化呈现一定的变化规律，即在丰水期此污染物的浓度比在枯水期高。地表径流和干湿沉降对此有很大的贡献。西江中PCDD／Fs年通量为8．55kg，毒性当量通量（I—TEQ）为0．026kg。通过对同系物和同族物分布图对比显示西江PCDD／Fs来源比较复杂，可能是混合来源。其中大气干湿沉降、地表径流和沿岸与漂白有关的工业对此有很大的贡献．是PCDD／Fs进入西江的3个重要途径。     

焚烧烟气和大气中二噁英类气-固分布比较研究

探讨生活垃圾焚烧烟气和周边大气中二噁英类的气-固浓度分布特性。通过采样实测某生活垃圾焚烧厂焚烧烟气和周边大气中二噁英类浓度,比较分析生活垃圾焚烧烟气和周边大气气-固浓度分布特性。焚烧烟气中不同氯取代的二噁英类气-固相分布较均衡,气相二噁英类占主导,质量浓度比例为82%~93%;大气中不同氯取代的二噁英类气-固分布很不均匀,固相二噁英类质量浓度比例为85%。烟气从出口到大气环境二噁英类气-固分配存在动态平衡。影响其动态平衡的2个重要影响参数为:气-固分布系数和颗粒态二噁英粒径分布特征。     

Reductive dehalogenation of chlorinated dioxins by an anaerobic bacterium

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs and PCDFs) are among the most notorious environmental pollutants. Some congeners, particularly those with lateral chlorine substitutions at positions 2, 3, 7 and 8, are extremely toxic and carcinogenic to humans. One particularly promising mechanism for the detoxification of PCDDs and PCDFs is microbial reductive dechlorination. So far only a limited number of phylogenetically diverse anaerobic bacteria have been found that couple the reductive dehalogenation of chlorinated compounds--the substitution of a chlorine for a hydrogen atom--to energy conservation and growth in a process called dehalorespiration. Microbial dechlorination of PCDDs occurs in sediments and anaerobic mixed cultures from sediments, but the responsible organisms have not yet been identified or isolated. Here we show the presence of a Dehalococcoides species in four dioxin-dechlorinating enrichment cultures from a freshwater sediment highly contaminated with PCDDs and PCDFs. We also show that the previously described chlorobenzene-dehalorespiring bacterium Dehalococcoides sp. strain CBDB1 (ref. 3) is able to reductively dechlorinate selected dioxin congeners. Reductive dechlorination of 1,2,3,7,8-pentachlorodibenzo-p-dioxin (PeCDD) demonstrates that environmentally significant dioxins are attacked by this bacterium.     

垃圾焚烧厂的环境空气、飞灰和土壤二噁英水平研究及风险评价

为评价珠三角某垃圾焚烧厂内工人和周边村民的二噁英健康风险,采集并分析了该垃圾焚烧厂的厂内环境(空气和飞灰)邻近敏感点(邻近村落)环境(空气和土壤)的二噁英(PCDD/Fs)质量水平,运用美国环保署(USEPA)风险评价体系和蒙特卡洛模拟(Monte Carlo simulation)对厂内工人、邻近敏感点村民(成人、青少年和儿童)在呼吸吸入、皮肤接触和经口摄入等暴露途径的健康风险进行评估.结果表明:(1)该垃圾焚烧厂固化飞灰中的PCDD/Fs毒性当量(以I-TEQ计)范围为8.99~240.00 ng TEQ/kg,环境空气中的为0.03~0.20 pg TEQ/m3,邻近敏感点土壤中的为0.81~2.04 ng TEQ/kg. (2)飞灰、厂内环境空气和邻近敏感点环境空气的PCDD/Fs单体分布特征更加接近,土壤中PCDD/Fs单体分布稍有差别. (3)厂内工人和村民(成人、青少年和儿童)的致癌风险(CR)合计第95%值范围为4.55×10-7~6.04×10-6,为可接受风险范围(＜10-5);非致癌风险(HI)合计第95%值范围为4.61×10-3~4.28×10-2,远低于1,非致癌风险极低;(4)厂内工人和成人村民的CR较高, 第95%值分别占风险安全值的60%和39%.厂内工人的CR从环境空气吸入(包括在厂内和敏感点)和飞灰意外经口摄入方式占比最高,分别达55.12%和38.43%;成人村民的CR中从环境空气吸入占主导(占97.79%).建议加强对环境空气二噁英监控和飞灰经口摄入的风险管控.     

EXAMINATION OF POLYCHLORINATED DIBENZO-P-DIOXINS AND POLYCHLORINATED DIBENZOFURANS INTO PROCESS WATER OF KRAFT PULP BLEACHING MILL FROM ASPECT OF ENVIRONMENTAL WATER QUALITY

INTRODUCTIONDuring the 1980s, the fact that chlorine used for pulp bleaching is connected to the release of dioxins1 and chloroform2 into the environment was proven in Canada and other countries. Since that time, each papermaking company has also been implementing a variety of policies designed to reduce dioxins generation. However, the Law Concerning Special Measures against Dioxins took effect in Japan on 15th January 2000. According to the new law, "kraft pulp and sulfite pulp bleac…     

添加剂对改性含钛高炉渣氯化过程的影响

针对高钙镁改性含钛高炉渣氯化过程物料易粘结问题,通过热力学分析及X射线衍射检测研究了添加剂防止粘结的作用机制,并考察了温度、配碳量、气体(N2+Cl2)流量和氯气分压对氯化行为的影响.结果表明:氯化过程中添加剂磷酸优先与CaO作用生成高熔点的Ca3(PO4)2以及后者与CaCl2反应生成Ca5(PO4)3Cl,避免了低熔点钙镁氯化物富集而造成的物料粘结.当反应条件为温度850~900℃、配碳过量15%、气体流量400 mL/min和氯气分压40 kPa,得到最佳的氯化结果,60 min内氯化率可达到90.8%~93.5%.     

北京市夏季大气气溶胶 PM2.5和 PM10成分特征?

对北京市城区2012年夏季大气对气溶胶进行每日PM2.5和PM10石英膜采样,得到了可溶性离子质量浓度和16种元素的质量浓度,并结合气象观测值进行了分析.结果显示,采样期间,PM2.5质量浓度为9.58~210.42μg·m-3,平均值102.81μg·m-3;PM10质量浓度为33.75~288.33μg·m-3,平均值159.66μg·m-3.PM2.5和PM10质量浓度都与采样点能见度、风速呈负相关,与相对湿度呈正相关.质子荧光分析(PIXE)结果显示,S、K、Ca和Fe在PIXE可分析元素中含量较高,在PM2.5和PM10都占89%.且元素Ca、Ti、Sc、Cr、Fe主要存在于粗粒子(PM2.5~10)中,而元素S、Cu、Zn、As、Br、Pb主要存在于细粒子(PM2.5)中.富集因子分析表明,元素K、Ca、Ti、V、Mn、Ni主要为地壳来源,元素S、Cl、Cu、Zn、As、Br、Pb主要来自于人为源.SO2-4、NO-3、NH+43种可溶性离子总质量浓度占PM2.5浓度的43.5%,占PM10浓度的25.4%.     

机械激活辅助熔盐法制备碳氮化钛研究

文章以氯化铵为氮源,采用机械激活辅助熔盐法制备碳氮化钛,研究结果表明,反应温度的升高和球磨激活时间的延长,均有助于减少副产物含量。所得TiC0.7N0.3颗粒尺寸在0.5μm-2μm之间。同传统固态合成法相比,采用该方法合成TiC0.7N0.3粉体的反应温度大幅降低,反应时间也大幅缩短。     

DD402/FGH95扩散偶中单晶合金γ′相筏形化与其形成元素的扩散

通过研究不同温度时热等静压(HIP)多元扩散偶DD402/FGH95中的Al,Ta和Ti元素的扩散规律，发现DD402单晶中存在Al和Ta元素的上坡扩散．因此单晶中在近结合界面处形成了Al ,Ta和Ti元素的富集区以及γ′相的筏形化．对Al和Ta元素的扩散流量及扩散深度进行计算．计算结果与试验结果相吻合．     

含铍含氟硫化铋精矿氯化浸出液中铋、铍、铁物种研究

柿竹园含铍含氟铋精矿成分十分复杂，其氯化浸出液中铋、铍、铁等分别与配位体Ｃｌ－，Ｆ－，ＳＯ２－４形成配合物，物种多达４０余种．因此，弄清这些物种的分配和行为，对于该精矿的冶金过程机理及工艺研究都具有重要意义．本文根据同时平衡原理和电中性原理，建立铋、铍、铁及氯浓度平衡和电荷平衡方程，然后用电子计算机联解，求得了各物种分配，并从理论上分析了几种主要元素在干馏过程中的行为，用以指导干馏工艺研究，实验结果与分析结果彼此符合较好．从而使Ｂｉ－Ｂｅ，Ｂｉ－Ｆｅ分离工艺难题得以解决．     

Ac_2O-PCl_3-S_2Cl_2催化乙酸制备高纯度氯乙酸

以乙酸为原料,采用Ａｃ２Ｏ－ＰＣｌ３－Ｓ２Ｃｌ２为催化剂,进行催化氯化制备高纯度氯乙酸,产品含量≥９８．５％。同时讨论了反应温度,催化剂用量等工艺条件对氯化反应及产品质量的影响。     

Fabrication of a Polyamide/Polysulfone Hollow Fiber Composite Membrane

Introduction Appliedtomembraneseparationtechnology,components canbeseparatedmechanicallywhenasolutiongoesthrough asemipermeablemembrane.Themembranecanbesheet,spiralwound,tubeorhollowfiber,amongwhichhollow fiberisofthehighestspecificsurfaceandthusthemost effective.Thebestknownliquid phasemembraneprocessesare reverseosmosis(RO),ultrafiltration(UF),microfiltration(MF),dialysis,andelectrodialysis(ED).However,over thepastfewyears,anewmembraneprocesscalled nanofiltration(NF)hasemergedthatpromise…