生活垃圾焚烧炉中二噁英、氯苯排放特性及关联

为探究二噁英(PCDD/Fs)合适的指示物,本文研究了国内两座生活垃圾焚烧电厂的两台循环流化床炉A、B的PCDD/Fs及氯苯(CBzs)排放特性.同时利用统计分析软件(SPSS)分析了PCDD/Fs浓度、TEQ浓度、CBz浓度之间的相关性.结果显示,在17种有毒PCDD/Fs中,2,3,4,7,8-P5CDF是最主要的二噁英同系物,在焚烧炉A、B中分别占毒性当量(TEQ)的28.97%—49.42%和45.56%—56.23%.氯苯的排放以二氯苯(DCBzs)、三氯苯(Tr CBzs)为主,其浓度是PCDD/Fs的几千倍.当用CBz作PCDD/Fs和TEQ的指示物进行一元线性回归分析时,发现部分指示物有很高的相关系数,R2最高可达0.8642.     

水平球磨机械化学法处置多氯联苯污染土壤的试验

采用中试试验台的水平滚动式球磨机,对高浓度多氯联苯(PCBs)污染土壤进行机械化学法处置.以氧化钙(Ca O)为主要添加剂成分,对比有无石英砂(SiO_2)助剂,混合球磨PCBs污染土壤.使用高分辨气相色谱/质谱联用仪(HRGC/MS)检测,分析球磨机械化学反应前后土壤中PCBs的去除率和二英(PCDD/Fs)的合成率.结果表明,采用水平滚动式球磨机对土壤进行20 h研磨后,对于单一Ca O添加球磨工况,PCBs总量和毒性当量(WHO-TEQ)分别减少了65%和73%;添加石英砂助剂后(Ca O-SiO_2工况),PCBs总量和WHOTEQ的去除率分别达到了74%和78%,证实水平滚动式低速球磨能有效降解PCBs,且SiO_2有助于Ca O添加剂机械化学去除土壤中PCBs.对球磨处理前后的PCDD/Fs生成量进行比较,结果表明,在反应初期的5 h内,部分PCBs氧化为高氯代的PCDFs,导致PCDD/Fs总量和毒性当量(I-TEQ)有所上升;球磨超过5 h后,PCDD/Fs开始发生降解反应.在保证充足的球磨反应时间条件下,机械化学处理PCBs可以克服传统PCBs热处置的首要缺陷——PCDD/Fs的二次合成问题.     

南四湖沉积物中二噁英类化合物的分布

用1 3C同位素内标法 ,高分辨率气相色谱 高分辨率质谱对南四湖表层沉积物中 1 7种含 2 3 7 8 氯代二苯并二英 /呋喃 (PCDD/Fs)及 1 2种共平面多氯联苯 (Co PCBs)的含量、同系物异构体的分布特征、沉积通量、毒性当量及来源进行了初步分析 ,并与山东近海 (日照、烟台、青岛 )的测定结果进行比较 .总Co PCBs含量分别为 5 4 4pg·g- 1 dw (南阳湖 )和 41 4pg·g- 1 dw (微山湖 ) .总PCDD/Fs含量分别为 1 0 6 7pg·g- 1 dw (南阳湖 )和1 47 0pg·g- 1 dw (微山湖 ) .两湖含 2 3 7 8 PCDD/Fs异构体对总毒性当量浓度的贡献基本相同 ,即以四—五氯代异构体为主 .PCDD/Fs含量次序为青岛 >日照 >南四湖 >烟台 .南四湖、日照、烟台近海沉积物中的PCDD/Fs对总TEQ (PCDD/F TEQ PCB TEQ)的贡献为68 8%— 93 0 % .南四湖与山东近海沉积物中PCDDs/PCDFs比值和OCDD %∑百分比表明 ,山东省PCDD/Fs的来源较为一致 ,相对恒定 .除河口处外 ,大气沉降应是南四湖及山东近海PCDD/Fs的主要来源 .     

洞庭湖底泥中二英污染现状及水动力对其分布的影响?

2013年9月采集洞庭湖区三口四水入湖口,东、西、南洞庭湖湖区以及出湖口沉积物,采用同位素稀释高分辨气相色谱－高分辨质谱法测定了沉积物中的二英（ PCDD／Fs）．结果表明洞庭湖沉积物中二英的浓度范围为153—7144 pg·g－1 dw （干重）,小河嘴最低,虞公庙最高．对比国内外其他淡水湖泊河流二英浓度,洞庭湖污染程度相对较低．二英污染水平依次为洞庭湖湖区＞出湖口＞入湖口,湖区内污染水平依次为南洞庭湖＞东洞庭湖＞西洞庭湖．主要同类物为OCDD,贡献率范围为77％—97％．PCDD／Fs的污染水平比1995年下降1—2个数量级,但和2004年污染水平相当．沉积物中二英的含量与水的流速成反比．洞庭湖出口处PCDD／Fs浓度相比入湖口和湖区浓度处于中间水平,表明洞庭湖中的二英可能会随水流进入长江中下游．     

典型烧结厂周边土壤多氯联苯的环境污染特征

本文以唐山某典型烧结厂为研究对象,对铁矿石烧结厂排放的烟气及周边土壤样品进行采集,应用同位素稀释高分辨气相色谱-高分辨质谱联用法(HRGC/HRMS)测定了多氯联苯(PCBs)的含量,并研究了PCBs的同类物分布特征.其中烟气样品中类二英PCBs(dl-PCBs)总浓度为1.04—1.77ng·m~(-3),毒性当量值为8.99—19.32pg·WHO-TEQ·m~(-3).烧结厂周边土壤样品中dl-PCBs的总浓度为8.81—403.59pg·g~(-1),毒性当量值为0.05—0.65pg·WHO-TEQ·g~(-1),是背景土壤样品的(0.035pg·WHO-TEQ·g~(-1))的1—19倍.可以看出,该烧结厂周边环境土壤受到了企业所排放PCBs等有毒污染物的影响.大部分土壤样品的同类物分布特征相似;CB-118对土壤dl-PCBs浓度贡献率最大,贡献率为31.74%.CB-101对土壤指示性PCBs浓度贡献率最大,贡献率为52.82%.将土壤样品和烟气样品的同类物分布进行比较发现二者略有不同.尽管都是以低氯代同类物为主,但是烟气样品中最高的同类物是TrCBs,且随着氯代数的增加,浓度呈现明显下降的趋势;而土壤样品PeCBs浓度最高,PeCBs前后都呈现逐级下降的趋势.唐山市此烧结厂周边土壤无论是TEQ值,指示性PCBs总浓度,PCBs总浓度与其它研究相比都处于较高水平.     

青海湖湟鱼(Gymnocypris przewalskii)中PCBs和PCDD/Fs的分析

应用同位素稀释高分辨气相色谱/高分辨质谱(HRGC/HRMS)分析了青海湖湟鱼体内多氯联苯(PCBs)和二噁英(PCDD/Fs)的含量.发现7-9年龄段湟鱼体内平均PCBs总浓度高达3484.9pg·g-1 ww,PCBs的毒性当量为0.41-0.57pgWHO-TEQ·g-1ww.除了PCB-81以外,其它11种二噁英类PCB都被检出,7种具有指示作用的PCB同系物(PCB-28,52,101,138,153,180)的浓度含量占总PCBs浓度的26%.湟鱼体内二噁英基本上未检出.由于青海湖区基本上没有工业污染源,鱼体内的PCBs可能是长距离迁移沉降和生物富集的结果.     

气相色谱-三重四极杆质谱法测定母乳样品中二英类物质的验证

本研究在建立气相色谱-三重四极杆质谱法(GC-MS/MS)测定二噁英同类物(PCDD/Fs)分析方法的基础上,验证了GC-MS/MS测定母乳样品中的17种PCDD/Fs的可行性.结果表明,对于17种PCDD/Fs,GCMS/MS方法在0.1—100 ng·m L~(-1)的浓度范围内具有良好的线性,平均相对响应因子在0.97—1.47之间,标准曲线的相对响应因子的相对标准偏差小于15%.使用标准溶液进行定量检测精密度测试,17种目标化合物的相对标准偏差均低于15%(n=8),证明该方法具有良好的重复性.方法定量限为0.008—0.977 pg·g~(-1)fat,满足母乳样品中PCDD/Fs的痕量分析需求.对19个母乳样品进行前处理后分别使用GC-MS/MS和GC-HRMS分析测定,将GC-MS/MS和GC-HRMS的定量数据利用SPSS进行比较,配对t检验的结果证明两种方法对于各目标化合物和总毒性当量均无显著差异.研究结果表明GC-MS/MS可以用于母乳中17种PCDD/Fs的准确测定.     

苏南城市群河流表层沉积物中二噁英和共平面多氯联苯的浓度水平、来源和生态风险

对25个苏南城市群河流表层沉积物中二噁英及17个样品中共平面多氯联苯的监测表明,PCDD/Fs和dl-PCBs中位值分别为6.61 ng WHO1998TEQ·kg-1和1.43 ng WHO1998TEQ·kg-1,均处于我国和亚洲河流表层沉积物的中等水平.PCDD/Fs和dl-PCBs含量水平与经济发展水平和工业规模呈现正相关.开发区新建企业是PCDD/Fs的新排放源之一.统计分析表明,南通PCDD/Fs的排放以燃煤和农药五氯酚的使用为主,无锡来源于农业活动和少量工业污染源,苏州则受到目前工业排放源的影响,3个城市的PCBs主要来源于历史上PCBs工业品的使用.96%的采样点总毒性当量浓度(TEQ)超过加拿大沉积物质量指导值(ISQGs),88%的采样点超过美国EPA ISQGs,表明苏南城市群表层沉积物PCDD/Fs和dl-PCBs具有一定生态风险.     

北京市冬季大气细颗粒物中二■英的污染特征

为了解北京市大气细颗粒物(PM_(2.5))中二■英(PCDD/Fs)的污染特征,利用中流量大气颗粒物采样器,在北京市3个功能区5个采样点(两个市区点、两个工业区点和一个背景点),同步连续采集了大气细颗粒物PM_(2.5)样品.参照US EPA 1613B标准方法,应用高分辨率气相色谱/高分辨率质谱(HRGC/HRMS),分析了PM_(2.5)中17种PCDD/Fs的浓度水平和区域分布特征,并对PCDD/Fs的污染来源做了初步探讨.结果表明,5个采样点PM_(2.5)的日均质量浓度范围102—146μg·m~(-3),平均日均值119μg·m~(-3),超出国家二级标准(75μg·m~(-3))59%,污染较重.在空间分布上,PM_(2.5)的日均浓度表现为工业区大于背景点大于市区的特征.所有采样点17种PCDD/Fs的总浓度范围∑PCDD/Fs是1.60—4.09 pg·m~(-3),平均值3.23 pg·m~(-3),PCDD/Fs总毒性当量∑TEQ范围是140.54—275.69 fg I-TEQ·m~(-3),平均值233.18 fg I-TEQ·m~(-3).与国内外其他城市相比,北京市大气PM_(2.5)中PCDD/Fs污染处于相当或略高水平.OCDD、OCDF和1,2,3,4,7,8-HpCDF是PCDD/Fs的主要组成成分,分别占总浓度∑PCDD/Fs的10%、19%和24%.对于总毒性当量∑TEQ贡献最大的是2,3,4,7,8-PeCDF,占总毒性当量的48.3%,∑PCDDs/∑PCDFs比值范围为0.19—0.23,平均值0.22,属于典型的"热源"特征.在浓度变化上, PCDDs呈现为随氯取代个数的增加而增加,除OCDF外, PCDFs的各单体浓度也随着取代氯原子个数的增加而增大.在区域分布上,PCDD/Fs浓度表现为工业区高于市区,市区大于背景点,充分体现了局地源的特点.采样期间工业热过程(化石燃料燃烧、电弧炉、烧结和冶炼等)、机动车排放和固体垃圾焚烧是北京冬季大气PM_(2.5)中PCDD/Fs和PM_(2.5)污染水平的主要影响因素.     

北京市大气沉降样品中PCDD/Fs的测定

利用高分辨率气质联用测定北京市大气沉降样品中的二噁英(PCDD/Fs).结果显示,5个样品的总浓度为332-3950 pg·g-1和6.9-85 pgTEQ·g-1.降雪样品浓度高于其它样品,且不同采样点样品呈现不同的分布特征.2,3,4,7,8-PeCDF是主要的TEQ组分.大部分样品同族体浓度以PeCDFs最高,其次是OCDD.∑PCDDs<∑PCDFs,二者之比为0.25-0.56.PCDD/Fs沉降通量为121 pg TEQ·m-2·month-1.北京背景土壤PCDD/Fs组成与大气沉降极为相似.     

PCDD/DFs and coplanar PCBs in fly ash samples from various types of incinerators in Taiwan

Polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/DFs) and coplanar polychlorinated biphenyls (Co‐PCBs) were determined in fly ash samples from municipal solid waste (MSW), medical waste (MW), and electricity power plant incinerators in Taiwan. The average concentrations of PCDD/DFs and Co‐PCBs are 7.02 ng‐TEQ/g and 1.06 ng‐TEQ/g, respectively. The contributions to total TEQ are 24% from PCDDs, 64% from PCDFs, and 12% from Co‐PCBs, indicating that PCDFs generate the highest environmental impact and MSW and MW incinerators are potential Co‐PCBs contaminating sources. The levels of PCDD/DFs and Co‐PCBs found in ash samples increase from petroleum‐fired, coal‐fired, large municipal solid waste, small medical waste, to small municipal solid waste incinerators, and are generally lower than those from incinerators built earlier. All fly ash samples analyzed in this study were considered hazardous materials. More research is suggested to establish the relationship between the amounts of PCDD/DFs and Co‐PCBs in fly ash and in flue gas.     

Study on polychlorinated dibenzo‐p‐dioxins and dibenzofurans in rivers and estuaries in Osaka Bay in Japan

In order to search the source of polychlorinated dibenzo‐p‐dioxins (PCDDs) and dibenzofurans (PCDFs) in blue mussel in Osaka bay, sediments from Osaka bay and from rivers running near an urban municipal incinerator were analysed for PCDDs, PCDFs and PCBs. The river and estuary sediments were all found to be contaminated with PCDDs at average levels of 9.8 and 12ppb on the dry basis, PCDFs of 7.8 and 5.1 ppb, and PCBs of 1600 and 1300ppb, respectively. The two sediments contained similar profiles of specific isomers and congeners of PCDDs and PCDFs with each other. In addition, there was observed positive close correlations between PCDD and PCDF levels in the two specimens as well as fly ash from urban municipal incinerators. These allow the conclusion that the main source of the two chemicals in Osaka bay is fly ash from waste incineration.     

利用EIA法快速筛查垃圾焚烧飞灰和烟气中的二恶英毒性水平

基于CAPE技术公司的兔子复合克隆抗体的二恶英(PCDD/F)酶免疫分析试剂盒,建立了快速检测垃圾焚烧飞灰和烟气中PCDD/F毒性(TEQ值)的方法.试剂盒的最低检测限为3.3pg·tube-1(即3.3pgTEQ每EIA试管),线性检测范围为10～30pg·tube-1.样品经甲苯索氏抽提后过硅胶柱连接小碳柱净化处理,TCDD/F的回收率大约为50%,与原飞灰PCDD/F分布模式相比净化处理后样品中的TCDD/F含量明显降低.用净化处理后的飞灰溶液作标准溶液,绘制PCDD/F剂量-效应关系曲线,定量分析了2个飞灰样品和2个烟气样品的TEQ浓度,结果表明分析样品的TEQ实测值(HRGC/HRMS分析获得)与预测值(标准曲线计算值)的相对偏差(Rd)均小于15%,说明用该方法定量分析垃圾焚烧飞灰和烟气中PCDD/F毒性是可行的.     

Dioxin-/Furan-“Verbrennungsprofile” in Abgasen aus Hochtemperaturprozessen

Different mechanisms downstream from high temperature processes lead to the formation of polychlorinated dibenzo(p) dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Independent from any concentrations, these mechanisms cause comparable PCDD/F patterns, the percentage proportion of single congeners or homologous groups related to the total of 17 2,3,7,8-Cl-substituted congeners or with respect to the sum of the homologous groups tetra to octa CDD/F. The characteristics of these so-called “combustion profiles” can help to interpret corresponding data from burning and melting facilities, such as municipal waste incinerators, coal power plants, sintering plants, metal finishing facilities, cement kilns, crematoria, hazardous waste incinerators and landfill gas burners     

Research on low emission MSW gasification and melting system

In order to eliminate secondary pollution caused by municipal solid waste (MSW) incineration, a MSW gasification and melting process is proposed. The process is expected to reduce the emission of pollutants, especially heavy-metals and dioxins. In this paper, the combustible components of MSW and simulated MSW were gasified in a lab-scale fluidized bed at 400°C–700°C when the excess air ratio (ER) was between 0.2 and 0.8. The experimental results indicated that the MSW could be gasified effectively in a fluidized bed at approximately 600°C–700°C when excess air ratio was 0.2–0.4. The melting characteristics of two typical fly ash samples from MSW incinerators were investigated. The results indicated that fly ash of pure MSW incineration could be melted at approximately 1,300°C and that of MSW and coal co-combustion could be melted at approximately 1,400°C. When temperature was over 1,100°C, more than 99.9% of the dioxins could be decomposed and most of the heavy-metals could be solidified in the slag. Based on the above experiments, two feasible MSW gasification and melting processes were proposed for low calorific value MSW: (1) sieved MSW gasification and melting system, which was based on an idea of multi-recycle; (2) gasification and melting scheme of MSW adding coal as assistant fuel.     

危险废物焚烧设施二噁英类排放特征及周边土壤污染调查

调查了13座不同类型的危险废物焚烧设施及二噁英类排放模式及部分设施土壤的污染水平.结果表明,排放浓度同焚烧处理量没有显著的关系.4—6氯代PCDD/Fs和7—8氯代PCDD/Fs呈现出了不同的排放特征.4—6氯代PCDF/PCDD比值为60.58±1.98(95%置信区间),较通用的总PCDF/总PCDD比值更适于描述危险废物焚烧设施二噁英排放的特征.使用PCA及聚类分析方法将设施排放模式归类为3种模式.分布模式同焚烧设施炉型、处理量以及尾气处理方式等因素相关性并不显著.2,3,4,7,8PeCDF对I-TEQ的贡献为35%—45%,并与I-TEQ具有很高的相关性.厂区土壤中二噁英浓度水平约为8—14ngI-TEQ.kg-1,周边土壤浓度为1—4ngI-TEQ.kg-1左右,均处于较低水平,调查设施周边土壤的使用目前尚无明显风险.危险废物设施对周边土壤的环境风险需要进一步评估.     

Polychlorinated dibenzo p-dioxins and dibenzofurans emissions in a primary copper smelter in China

Metallurgical production is the largest polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) emission source in China. However, PCDD/F monitoring and research are rarely conducted on primary metallurgical production. In this study, a demonstration primary copper smelter in China was selected to investigate PCDD/F characteristics and control. Samples were collected from major PCDD/F release points in the smelter process (fly ashes and waste water sludge). Specific analysis of PCDD/F congeners was carried out using a high resolution gas chromatography/high resolution mass spectrometry method. The results showed that PCDD/Fs might be unintentionally produced in the primary copper smelter processes, with sample concentrations of 180–6110 pg/g dry wt; highly chlorinated PCDD/F homologues were predominant. The toxicity of all the samples was calculated to be 120 pg WHO TEQ/g, fly ashes from the refining process furnaces air pollution control device and sludge were hazardous waste with higher PCDD/F toxicity. Both precursor formation and de novo synthesis were found to contribute to PCDD/F formation in the smelter process. PCDD/F characteristics and formation were compared with reported secondary copper smelters. Life-cycle control of PCDD/F was proposed for retrofitting of this smelter and for similar plants in China's primary copper production sector, including control at the PCDD/F formation, removal and disposal stages.     

Spatial distribution of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in soil around a municipal solid waste incinerator

Municipal solid waste incinerators (MSWIs) are usually considered to be important sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). To examine the influence of PCDD/Fs emissions from a MSWI on the surrounding environment, 21 soil samples were collected from various sampling sites distributed at distances of 300–1,700 m away from the stack of a MSWI. International Toxic Equivalent (I-TEQ) concentrations ranged from 0.47 to 2.07 pg I-TEQ g^?1, with average and median concentrations of 1.08 and 1.05 pg I-TEQ g^?1, respectively. Comparison of the results presented herein with other worldwide studies suggested that the concentrations of PCDD/Fs in the ambient soil were relatively low, indicating a limited impact on the surrounding environment. The emission concentrations from the incinerator were the critical factor in generating an environmental impact on the surrounding environment. An exponential function was developed, indicating a slight decline in TEQs of PCDD/Fs with increasing distance from the MSWI stack. The ordinary kriging interpolation technique was selected to create a contour map, which intuitively showed that a limited surrounding area (≤1,000 m from the stack) was obviously influenced by the MSWI.     

The Distribution and Impacts of Dioxins and Polychlorinated Biphenyls in the Taiwan Er-Jen River

The distribution and impacts of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) and polychlorinated biphenyls (PCBs) in the Taiwan Er-Jen River were investigated by monitoring fish distribution and measuring PCDD/DFs and PCBs levels in sediment and fish samples. Most of the fish collected are pollution-resistant species such as Oreochromis spp, Liza macrolepsis, Channa spp and Megalops cyprinoides. the most polluted river sections are in the upstream where large amount of waste effluents from households, livestock rearing and nearby dumping sites were discharged into the river, and the lower reaches of the river where metal recovery activities including open burning of waste electrical wire/scrap occurred. Sediment samples collected near the burning site show 2,3,7,8-TCDD toxicity equivalents (TEQ) ranging from 0.014 to 14.2 ng g^-1 by PCDD/DFs and from 0.015 to 1.03 ng g^-1 by coplanar PCBs (Co-PCBs). the fish samples show TEQ ranging from 0.029 to 0.615 ng g^-1 by PCDD/DFs and from 0.012 to 0.12 ng g^-1 by Co-PCBs. Possible PCDD/DFs sources are discharged PCBs, open burning of waste wire/scrap, and pentachlorophenol. the consumption of these fish will cause an average intake of 54 pg kg^-1 d^-1 TEQ. the prevention of direct discharge of livestock and the dumping of waste effuents into River Er-Jen as well as the control of metal recovery activities appears to be the first step toward the restoration of River Er-Jen.     

PBDEs and PCDD/Fs in surface soil taken from the Taizhou e-waste recycling area,China

The emerging issue of electronic wastes (e-waste) and the associated environmental problems has gained considerable attention from the scientific community in recent decades. In the present study, the levels of polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the surface soil obtained from the Taizhou e-waste recycling area of China were investigated. Also the correlation among these chemicals and previously published data of heavy metals, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls was analysed. We determined that the pollution levels of eight PBDEs congeners were serious, ranging from 27.9 to 3128.4 μg/kg. The concentration of PCDD/Fs was in the range of 218.3–3122.2 pg/g with a mean value of 659.5 pg/g. The PBDEs were not well-correlated with organic pollutants (PAHs and PCBs) in soil, whereas PCDD/Fs exhibited a significant positive correlation with the PCBs. The higher levels of persistent organic pollutants may pose potential adverse effects to soil quality and human beings and needs to be properly managed and remediated.