基于污泥掺烧的某生活垃圾焚烧厂烟道气、飞灰及炉渣中的二噁英特征

以我国南方某生活垃圾焚烧厂掺烧10%市政污泥的生活垃圾为研究对象,对前/后口废气、飞灰、炉渣及用于掺烧的污泥中17种二噁英的含量进行了测定,并分析了其指纹分布特征.结合焚烧工况及处理设施,从生成机理角度探讨了二噁英的排放特征、毒性当量浓度主成分特征及主要单体的排放因子线性关系.结果表明:掺烧10%的市政污泥后,废气中二噁英的去除率为99.4%,低于国家排放标准;固体废物中二噁英含量为飞灰炉渣污泥.这说明采用高温焚烧和"活性炭喷射+布袋除尘"装置不会影响掺烧10%污泥的达标排放.指纹分布特征表明,前口废气以1,2,3,4,6,7,8-Hp CDF和OCDD为主,后口废气以OCDD和OCDF为主;飞灰、炉渣及污泥中的主要单体为OCDD、1,2,3,4,6,7,8-Hp CDD、OCDF、1,2,3,4,6,7,8-Hp CDF.主成分分析显示,前口废气和飞灰中的二噁英毒性分布特征相似;炉渣和污泥的毒性分布特征相似;后口废气有自身的特征.这说明在相同工况条件下,经同一设施处理的废物中二噁英排放特征相似.排放因子分析表明,2,3,4,7,8-Pe CDF和1,2,3,6,7,8-Hx CDF、1,2,3,6,7,8-Hx CDD和1,2,3,7,8,9-Hx CDD与总毒性排放因子具有较强的线性关系,且呋喃类(PCDFs)强于二噁英类(PCDDs).     

医疗废物焚烧烟气中二(口恶)英排放特征研究

医疗废物焚烧是二(口恶)英排放的重点源,但缺乏对其系统、全面的研究,为进一步明确其二(口恶)英排放水平和分布特征,获得二(口恶)英排放监控的重要基础数据,以3处医疗废物焚烧炉为研究对象,采用高分辨气相色谱/高分辨质谱联用仪对烟气中二(口恶)英进行测定和分析。结果表明,烟气中二(口恶)英质量浓度均值为2.379 ng/Nm~3,毒性当量浓度均值为0.249 ng/I-TEQ Nm~3,达到国家排放标准;同系物指纹特征分布以PCDFs为主,质量浓度和毒性当量浓度贡献率最大的单体分别为1,2,3,4,6,7,8-HpCDF和2,3,4,7,8-PeCDF;2,3,4,7,8-PeCDF对I-TEQ相关性最好,相关系数R~2达0.959,可作为指示单体;排放因子均值为6.087μg I-TEQ/t,明显高于生活垃圾焚烧炉,需引起更多关注。     

二(口哑)(口英)类化合物在生活垃圾焚烧飞灰中的分布

通过对上海市某生活垃圾焚烧发电厂飞灰中二(口哑)(口英)类化合物的长期监测,分析了它们的含量分布和毒性当量浓度贡献率,以探讨飞灰中二(口哑)(口英)类化合物的污染特征.结果表明,飞灰中多氯代二苯并呋喃(PCDFs)中1,2,3,4,6,7,8-HpCDF和1,2,3,7,8-PeCDF百分含量之和为36%～39%,2,3,4,7,8-PeCDF对PCDFs毒性当量浓度贡献率最大(>50%);多氯代二苯并-对-二(口哑)(口英)(PCDDs)中OCDD百分含量为46%～ 58%,1,2,3,4,6,7,8-HpCDD百分含量为28%～32%,而对PCDDs毒性当量浓度贡献最大的是1,2,3,7,8-PeCDD(55%～61%);多氯联苯(PCBs)中以3,3',4,4'-TeCB和3,3',4,4',5-PeCB百分含量较高,而且3,3',4,4',5-PeCB对毒性当量浓度贡献率占PCBs的94%以上.尽管不同取样时间的飞灰中二(口哑)(口英)毒性当量浓度变化较大,但二(口哑)(口英)类化合物却具有相似的分布规律,对毒性当量浓度贡献率最大的是2,3,4,7,8-PeCDF (29%～33%),其次是1,2,3,7,8-PeCDD(21%～26%).     

几种可能来源对广东某地空气中二(口恶)英的影响

采用高分辨气相色谱法/高分辨质谱法（HRGC/HRMS）对广东某地生活垃圾焚烧厂烟道气及周边环境空气和可能来源的环境空气中17种二英进行了分析.讨论了所有样品中同系物、主要毒性贡献体的特性.并运用主成分和聚类分析法,探究了焚烧厂周边监测点位与焚烧厂排放烟气及可能来源的关系.结果表明周边空气中二英浓度低于焚烧厂烟道气,且不受主导风向的影响.在调查基础上,推断轮胎厂及露天焚烧为可能污染源.轮胎厂二英浓度均低于上风向监测点,露天焚烧空气中二英高于厂界外监测点.对各同类物百分比分析可知,烟道气和所有空气中主要同类物为OCDD、1,2,3,4,6,7,8-HpCDD及1,2,3,4,6,7,8-HpCDF,但空气中同类物还包括OCDF;焚烧厂周边监测点与轮胎厂空气中二英单体百分浓度相似,烟气与露天焚烧中二英单体分布相似.进一步研究表明所有空气样品中单体1,2,3,7,8-PeCDD和2,3,4,6,7,8-HxCDF与总毒性当量浓度的线性相关系数分别为0.95和0.75,相关性较强.主成分分析及聚类分析表明垃圾焚烧厂对周边空气产生影响,轮胎厂对上风向产生影响,露天焚烧对厂界影响较小.     

医疗废物焚烧厂周边环境空气中二英浓度分布及其健康风险评估

于2015-2018年冬季（12月-2月）对广东省某医疗废物焚烧厂排放烟气及焚烧设施周边2.5 km范围内6个采样点分别进行了4次烟气和环境空气样品采集,应用高分辨气相色谱/高分辨质谱（HRGC-HRMS）联用技术对二（口恶）英（PCDD/Fs）浓度水平进行监测并对其组成特征进行了分析,运用主成分分析法（PCA）对周边环境空气中二（口恶）英来源进行了初步解析,同时采用VLIER-HUMAAN模型评估其对人体的健康风险.结果表明该医疗废物焚烧厂烟气二（口恶）英毒性当量浓度为0.542~21.300 ng·Nm^-3（以I-TEQ计）,排放水平较高;周边环境空气中PCDD/Fs质量浓度和毒性当量浓度变化范围分别为0.682~196.000 pg·m^-3和0.036~17.700 pg·m^-3（以I-TEQ计）,周边环境空气中PCDD/Fs浓度明显受到排放源烟气落地点的影响.空气样品中二（口恶）英同族体及异构体分布指纹谱图与该焚烧设施排放烟气类似,空气质量浓度主要贡献单体以OCDD、1,2,3,4,6,7,8-HpCDF、OCDF以及1,2,3,4,6,7,8-HpCDD为主,主要毒性贡献单体为2,3,4,7,8-PeCDF.PCA源解析结论与指纹谱图特征分析结论基本一致,该研究区域中环境空气二（口恶）英主要来源于医疗废物焚烧烟气排放.健康风险评估结果表明,该区域人群呼吸暴露风险总体处于较为安全的水平（0.0032~0.141 pg TEQ·kg^-1·d^-1）,部分个体的呼吸暴露贡献率超过了评价限值,应引起重视.     

垃圾焚烧飞灰或炉渣中二

分别采集了3种生活垃圾焚烧炉产生的飞灰或熔融炉渣样品,分析了其中的二(口恶)(口英)含量及其毒性当量,并讨论了17种2,3,7,8位氯取代的二(口恶)(口英)分布特征及其对总毒性当量的贡献.结果表明,机械炉排焚烧炉产生的飞灰中二(口恶)(口英)最多,总浓度为319ng/g,毒性当量为6.7ng I-TEQ/g;其次为流化床焚烧炉,产生的飞灰中二(口恶)(口英)总浓度为38.7ng/g,毒性当量为0.8ng I-TEQ/g;气化熔融焚烧炉产生的熔融炉渣中二(口恶)(口英)很少,总浓度为38.7pg/g,毒性当量仅为1.1pg I-TEQ/g;所有的2,3,7,8位氯取代的13C同位素标记内标化合物回收率在39%～156%之间.尽管不同的垃圾焚烧炉在二(口恶)(口英)的生成量上有明显的差别,但是产生的二(口恶)(口英)同类物的归一化浓度以及对毒性当量贡献的归一化结果分布特征十分相似,表明3种垃圾焚烧炉在垃圾焚烧过程产生二(口恶)(口英)可能具有相似的反应机理.     

垃圾焚烧飞灰或炉渣中二(口恶)(口英)的分布特征

分别采集了3种生活垃圾焚烧炉产生的飞灰或熔融炉渣样品,分析了其中的二(口恶)(口英)含量及其毒性当量,并讨论了17种2,3,7,8位氯取代的二(口恶)(口英)分布特征及其对总毒性当量的贡献.结果表明,机械炉排焚烧炉产生的飞灰中二(口恶)(口英)最多,总浓度为319ng/g,毒性当量为6.7ng I-TEQ/g;其次为流化床焚烧炉,产生的飞灰中二(口恶)(口英)总浓度为38.7ng/g,毒性当量为0.8ng I-TEQ/g;气化熔融焚烧炉产生的熔融炉渣中二(口恶)(口英)很少,总浓度为38.7pg/g,毒性当量仅为1.1pg I-TEQ/g;所有的2,3,7,8位氯取代的13C同位素标记内标化合物回收率在39%～156%之间.尽管不同的垃圾焚烧炉在二(口恶)(口英)的生成量上有明显的差别,但是产生的二(口恶)(口英)同类物的归一化浓度以及对毒性当量贡献的归一化结果分布特征十分相似,表明3种垃圾焚烧炉在垃圾焚烧过程产生二(口恶)(口英)可能具有相似的反应机理.     

垃圾焚烧飞灰或炉渣中二噁的分布特征

分别采集了3种生活垃圾焚烧炉产生的飞灰或熔融炉渣样品,分析了其中的二口恶口英含量及其毒性当量,并讨论了17种2,3,7,8位氯取代的二口恶口英分布特征及其对总毒性当量的贡献.结果表明,机械炉排焚烧炉产生的飞灰中二口恶口英最多,总浓度为319ng/g,毒性当量为6.7ngI-TEQ/g;其次为流化床焚烧炉,产生的飞灰中二口恶口英总浓度为38.7ng/g,毒性当量为0.8ngI-TEQ/g;气化熔融焚烧炉产生的熔融炉渣中二口恶口英很少,总浓度为38.7pg/g,毒性当量仅为1.1pgI-TEQ/g;所有的2,3,7,8位氯取代的13C同位素标记内标化合物回收率在39%~156%之间.尽管不同的垃圾焚烧炉在二口恶口英的生成量上有明显的差别,但是产生的二口恶口英同类物的归一化浓度以及对毒性当量贡献的归一化结果分布特征十分相似,表明3种垃圾焚烧炉在垃圾焚烧过程产生二口恶口英可能具有相似的反应机理.     

中国危险废物和医疗废物焚烧处置行业二（口恶）排放水平研究

通过调研全国危险废物和医疗废物焚烧处置设施,对包含二噁英排放水平的设施按处置对象、炉型和处理量分类,并作系统分析和研究.结果表明现有危险废物焚烧设施烟气中二噁英的浓度比医疗废物低,达标率为74.19%;危险废物选用回转窑处置效果较好,达标率为66.67%;而医疗废物选用回转窑或热解炉,要综合考虑处置规模、生产成本和二英排放总量等因素;危险废物介于10~30 t·d-1和医疗废物介于10~20 t·d-1的处置设施要尤其注意二噁英的排放问题;医疗废物焚烧飞灰中二噁英的均值浓度为危险废物6倍以上,仅有16.67%满足填埋要求.二者烟气中二英的浓度分布以1,2,3,4,6,7,8-HpCDF、2,3,7,8-TCDF和OCDD为主.     

二噁类化合物在生活垃圾焚烧飞灰中的分布

通过对上海市某生活垃圾焚烧发电厂飞灰中二噁类化合物的长期监测,分析了它们的含量分布和毒性当量浓度贡献率,以探讨飞灰中二噁类化合物的污染特征.结果表明,飞灰中多氯代二苯并呋喃(PCDFs)中1,2,3,4,6,7,8-HpCDF和1,2,3,7,8-PeCDF百分含量之和为36%~39%,2,3,4,7,8-PeCDF对PCDFs毒性当量浓度贡献率最大(>50%);多氯代二苯并-对-二噁(PCDDs)中OCDD百分含量为46%~ 58%,1,2,3,4,6,7,8-HpCDD百分含量为28%~32%,而对PCDDs毒性当量浓度贡献最大的是1,2,3,7,8-PeCDD(55%~61%);多氯联苯(PCBs)中以3,3’,4,4’-TeCB和3,3’,4,4’,5-PeCB百分含量较高,而且3,3’,4,4’,5-PeCB对毒性当量浓度贡献率占PCBs的94%以上.尽管不同取样时间的飞灰中二噁毒性当量浓度变化较大,但二噁类化合物却具有相似的分布规律,对毒性当量浓度贡献率最大的是2,3,4,7,8-PeCDF (29%~33%),其次是1,2,3,7,8-PeCDD(21%~26%).     

Evaluation of PCDD/Fs and metals emission from a circulating fluidized bed incinerator co-combusting sewage sludge with coal

The emission characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and heavy metals were evaluated during co-combustion of sewage sludge with coal from a circulating fluidized bed incinerator. The stack gas, slag and fly ash samples were sampled and analyzed. The gas-cleaning system consisted of electrostatic precipitators and a semi-dry scrubber. Results showed that the stack gas and fly ash exhibited mean dioxin levels of 9.4 pg I-TEQ/Nm 3 and 11.65 pg I-TEQ/g, respectively, and showed great similarities in congener profiles. By contrast, the slag presented a mean dioxin level of 0.15 pg I-TEQ/g and a remarkable difference in congener profiles compared with those of the stack gas and fly ash. Co-combusting sewage sludge with coal was able to reduce PCDD/Fs emissions significantly in comparison with sewage sludge mono-combustion. The leaching levels of Hg, Pb, Cd, Ni, Cr, Cu, and As in the fly ash and slag were much lower than the limits of the environmental protection standard in China. These suggest that the co-combustion of sewage sludge and coal is an advisable treatment method from an environmental perspective.     

Characteristics of air pollution by polychlorinated dibenzo-p-dioxins and dibenzofurans in the typical industrial areas of Tangshan City, China

The ambient air in vicinity of different industrial sources for PCDD/PCDFs was sampled by TSP/PM10 active samplers and passive PUF disk samplers in Tangshan City, a metropolis containing clusters of various industrial plants. The TEQ concentrations of PCDD/PCDFs ranged from 44.2 to 394.1 fg I-TEQ/m3 with an average of 169.9 fg I-TEQ/m3. 2,3,4,7,8-PeCDF was the dominant contributor to PTEQ, contributing 41% (12% to 55%), while 1,2,3,4,6,7,8-HpCDF, OCDD and OCDF were the major congeners for the total concentrations. The ratios of PPCDF/PPCDD reached 2.54 on average, suggesting that de novo synthesis in thermal processes played an important role to the airborne pollution of PCDD/PCDFs. The similarities congener profiles indicated that TSP and PM10 active sampling methods are comparable for the determination of the PCDD/PCDFs in ambient air, and the ratios of concentrations determined by the two methods suggested that the PCDD/PCDFs tended to stay in fine particles. It was found that 2,3,7,8-TCDF and OCDD were the dominating congeners in the passive PUF disks samples. Through principal components analysis, the coke industry was suggested to be a relatively high potential emission source for PCDD/PCDFs in the ambient air of Tangshan, which was possibly formed by de novo synthesis mechanism. In this study, the atmospheric impacts to the environment from di erent industrial sources could be ranked as follows (from high to low): coking, iron sintering, steel making, power generation and chlorinate alkali chemical production industries.     

珠三角大气中二英污染水平与区域迁移

采用高分辨气相色谱/高分辨质谱法对珠三角地区2019年11月冬季期间和2020年8月夏季期间大气环境中17种氯取代二■英的现状水平进行了测定,并在此基础上对其空间分布、指纹特征、指示性单体和区域迁移特征也进行了分析.结果表明,夏季和冬季二■英的浓度平均值分别为1.40 pg·m^-3和5.14 pg·m^-3,而毒性当量（以I-TEQ计）平均值分别为0.087 pg·m^-3和0.076 pg·m^-3.同时,9个城市夏季和冬季二■英的空间分布不一致,这可能由各地区采样期间的气象条件和排放源的影响导致. OCDD、 1,2,3,4,6,7,8-HpCDD、 OCDF和1,2,3,4,6,7,8-HpCDF是夏季和冬季的主要指纹特征单体;而2,3,4,7,8-PeCDF和1,2,3,4,7,8-HxCDF是主要的毒性贡献单体,且贡献率越大,其与总毒性当量的线性相关性越强.由后向轨迹模拟结果发现,夏季受东南偏南季风影响,气团由海上迁移至陆地,导致夏季二■英浓度较低,且高浓度区域主要受本地排放源影响;而冬季受东北...     

Level and characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans in feed and feed additives

Feed security is a prerequisite for safe animal food products. In this study, 13 groups of feed and feed ingredients, totaling 2067 samples, were collected in the period of 2011 to 2014 from China. The highest mean level of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) was found in fish meals and shell powders, with a concentration of 60.35 ng/kg, followed by mineral origin materials. In terms of the toxicity equivalent concentration, the fish oil group showed the highest PCDD/F levels because of their bio-accumulation through the aquatic food chain, with an average concentration of 1.26 ng WHO-TEQ/kg, while the lowest level was observed in compound feed for chickens and pigs, with an average value of 0.16 ng WHO-TEQ/kg. OCDD and OCDF were the predominant congeners in all groups except fish oils, in which the primary congeners were 2,3,4,7,8-PeCDF and 2,3,7,8-TCDF. For zinc chloride samples, different from other zinc-based compound samples, the main congeners were 1,2,3,4,6,7,8-HpCDF (17%), 1,2,3,4,7,8,9-HpCDF (15%), 1,2,3,4,7,8-HxCDF (12%) and OCDF (30%). Considering toxicity equivalency factors, the dominant congeners were 2,3,4,7,8-PeCDF, 1, 2,3,4,7,8-HxCDF, 2,3,7,8-TCDF and 1,2,3,7,8-PeCDD, and the contribution to the total TEQ was 29%, 16%, 14% and 12%, respectively. Overall, 2.1% (43 out of 2067) of all the analyzed samples exceeded the different individual ''European Union maximum limited levels for PCDD/Fs. This study is beneficial for the determination of the status of contamination levels of feed and feed ingredients.     

生活垃圾焚烧厂周边环境空气中PCDD/Fs含量及分布特征

对我国某工业区生活垃圾焚烧厂周边5km范围内14个采样点环境空气中四氯~八氯代二 英(2,3,7,8-PCDD/Fs)含量及其组成特征进行了分析.结果表明该垃圾焚烧厂周边环境空气PCDD/Fs浓度的变化范围为1.74~15.2pg/m3(0.156~1.44pg I-TEQ/m3),均值为4.60pg/m3(0.426pg I-TEQ/m3),其中3个点位接近或超出日本环境空气质量标准限值(0.6pg I-TEQ/m3),表明某些区域处于一个较高的污染水平;最大浓度点位于焚烧设施下风方向1.3km处,与AERMOD预测的最大落地浓度位置一致.1,2,3,4,6,7,8-HpCDF和OCDD是空气中二 英质量浓度主要贡献因子,而2,3,4,7,8-PeCDF是毒性当量浓度的主要贡献因子.样品中二 英同族物分布的指纹特征显示出可能受MSWI源影响点位与非MSWI影响(或受此源影响较小)点位的区别.主成分分析(PCA)源解析结论与空间分布以及指纹特征分析结论基本一致,且更具体地判断MSWI的影响点位,在一定程度上说明了此方法的可靠性.二 英呼吸暴露剂量估算结果表明该区域人群二 英呼吸暴露风险总体处于较为安全的水平.     

等离子体技术在处理垃圾焚烧飞灰中的应用研究

对飞灰进行TCLP重金属浸出试验,发现重金属Cd的浸出浓度达到0.322 5 mg/L,高出国家规定的毒性浸出标准(Cd:0.3mg/L),采用美国EPA规定的1613方法分析飞灰中的二(噁)英含量,其毒性当量I-TEQ为0.45 ng/g.利用直流双阳极等离子体电弧对飞灰进行熔融处理,对得到的熔渣进行分析,结果表明,飞灰经过熔融处理后,重金属的浸出浓度得到很好的控制,远低于毒性浸出标准,飞灰中的二(噁)英毒性当量I-TEQ接近91.6%被降解消除,得到的熔渣呈非结晶质的玻璃质结构,具有非常致密的微观结构.     

Atmospheric emission characterization of a novel sludge drying and co-combustion system

A novel system combining sludge drying and co-combustion with coal was applied in disposing sludge and its atmospheric emission characteristics were tested. The system was composed of a hollow blade paddle dryer, a thermal drying exhaust gas control system, a 75 tons/hr circulating fluidized bed and a flue gas cleaning system. The emissions of NH3, SO2, CH4 and some other pollutants released from thermal drying, and pollutants such as NOx, SO2 etc. discharged by the incinerator, were all tested. Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans （PCDD/Fs） in the flue gas from the incinerator were investigated as well. The results indicated that the concentrations of NOx and SO2 in the flue gas from the incinerator were 145 and 16 mg/m^3, respectively, and the I-TEQ concentration of 2,3,7,8-substitued PCDD/Fs was 0.023 ng I-TEQ/Nm^3. All these values were greatly lower than the emission standards of China. In addition, there was no obvious odor in the air around the sludge dryer. The results demonstrated that this drying and co-combustion system is efficient in controlling pollutants and is a feasible way for large-scale treatment of industrial sludge and sewage sludge.