Occurrence and impact of polychlorinated dibenzo-p-dioxins/dibenzofurans in the air and soil around a municipal solid waste incinerator

To assess the influence of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans(PCDD/Fs) on the environment in the vicinity of municipal solid waste incinerators(MSWIs), we determined the levels of PCDD/Fs in air and soil samples collected around a MSWI, which is the largest in China. The International Toxicity Equivalency Quantity(I-TEQ) concentrations of PCDD/Fs in air samples were from 0.0300 to 1.03 pg I-TEQ/m~3(0.445–13.6 pg/m~3), with an average of 0.237 pg I-TEQ/m~3, while in soil samples they ranged from 0.520 to 3.40 pg I-TEQ/g(2.41–88.7 pg/g) with an average of1.49 pg I-TEQ/g. The concentrations of PCDD/Fs in air and soil samples were comparable to other areas, and Pe CDFs were the dominant contributors, which was different from stack gas homologue patterns. Multivariate statistical analysis showed that PCDD/Fs emission from the MSWI did not directly affect the profiles of PCDD/Fs in air and soils, so that vehicles and unidentified emission sources should be considered. The daily inhalation levels of PCDD/Fs for children(0.0110 to 0.392 pg I-TEQ/(kg·day) and adults(0.00600 to 0.221 pg I-TEQ/(kg·day) near the MSWI were lower than the tolerable daily intake of 1.00 to 4.00 pg WHO-TEQ/(kg·day), but in winter the values were higher than in summer. These results can be used as basic data for assessing the risk of PCDD/Fs exposure in residents living around this MSWI, and more monitoring programs and studies should be carried out around MSWIs.     

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.     

垃圾填埋场抽气竖井周边气体运移规律研究

通过建立填埋场抽气竖井周边气体轴对称稳态运移模型,分析了单层和分层垃圾体中气压力分布,并提出“降压百分比”的概念用于判定抽气影响范围,研究了垃圾产气率、气体渗透率、覆盖层厚度、覆盖层气体渗透率、抽气井深度和抽气负压对抽气影响范围和抽气量的影响,获得了竖井深度和井间距的确定方法.分析结果表明,抽气井的降压作用明显,抽气井深度和抽气负压越大,则抽气影响范围和抽气量越大.覆盖层厚度增加或其渗透率降低有助于扩大抽气影响范围和提高抽气量.抽气影响范围随气体渗透率的增加而增大,但随垃圾产气率的增加而减少;抽气量则随气体渗透率和产气率的增大而增加.抽气井深度是控制抽气影响范围的关键参数,建议竖井深度取垃圾填埋厚度的65％～75％,井间距取1.5～2.5倍竖井深度.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans and polychlorinated biphenyls in surface soil from the Tibetan Plateau

Concentrations of Polychlorinated dibenzo-p-dioxins and dibenzofurans（PCDD/Fs） and polychlorinated biphenyls（PCBs） in soil samples from Tibetan Plateau were determined. The average concentration of total 2,3,7,8-PCDD/Fs was（2.30 ± 1.02） pg/g, and World Health Organization Toxicity Equivalency（WHO-TEQ） average concentration was（0.013 ± 0.010）pg WHO-TEQ/g. The average concentration of ∑PCBs（7 indicator PCB and 12 dioxin like-PCB congeners） was（16.2 ± 9.25） pg/g, and WHO-TEQ average concentration was 0.043 ±0.049 pg WHO-TEQ/g. Comparing to previous studies in similar environmental conditions,PCDD/Fs and PCBs in this study showed a relatively lower concentration. The altitude dependences of PCDD/Fs and PCBs were also studied. Total organic carbon（TOC） normalized concentrations presented a quadratic relation with the altitudes, and an inflection could be found on the parabola of the total concentrations and some congeners of high concentration.The concentrations decreased with altitudes below about 4500 m above sea level（a.s.l.）, while they increased with altitudes above it. These phenomena indicate that cold condensation of PCDD/Fs and PCBs would happen above 4500 m a.s.l, on the Tibetan Plateau.     

城市生活垃圾焚烧炉周边环境空气及土壤中二噁英来源研究

系统研究了某城市生活垃圾焚烧炉周边地区6个焚烧炉废气样品、14个环境空气样品和3个表层土壤样品中二噁英的组成及其含量,并对其来源进行了解析.结果表明,焚烧炉排放废气中二噁英含量较高,周边地区环境空气及主导风向下风向污染物最大落地点附近土壤中的二噁英含量均处于较低水平,且主导风向下游环境空气中二噁英含量与其它地点采集的样品中二噁英含量差别不明显,但最大落地点表层土壤样品与背景点表层土壤样品中二噁英的组成及含量均有一定的变化.主成分分析结果表明,最大落地点附近表层土壤样品中的二噁英可能受到了污染源废气排放的影响,但环境空气中二英类污染物来源较为复杂,具体原因还需进一步的深入研究.     

珠三角某垃圾焚烧厂周边环境空气重金属分布特征研究

以华南某垃圾焚烧厂为研究对象,根据研究区域主导风向特点,以焚烧炉为中心进行布点,累积采集环境空气样98个,焚烧炉烟气9个,分析了焚烧炉周围环境空气中重金属的空间分布特征.同时,采用相关分析和主成分分析法,分析了焚烧炉周围环境空气TSP中重金属含量与焚烧炉烟气中重金属含量的关系.结果表明,焚烧炉周围环境空气中各重金属的含量(μg·m-3)排序为:Fe(0.766～19.551)＞Zn(0.791-1.833)＞ Mn(0.431～1.014)＞ Pb(0.263～0.626)＞ Cu(0.054～0.578)＞ Cr(0.057～0.180)＞ Ni(0.030～0.106) ＞ Cd (0.017～0.044) ＞ As(0.009～0.014)＞Tl(0.002～0.004).焚烧炉烟气各重金属含量(μg·m-3)排序为:Zn(90～4570)＞Ni(4～3510) ＞ Cr(2～650)＞Cu(5～1380)＞ Pb(25 ～430)＞ Cd(2 ～53)＞ T1 (0.1-3).分析各元素空间分布特征发现,除与距焚烧炉距离远近有关外,其他人为活动(如农业活动)对焚烧炉周围环境空气中重金属含量也有一定的贡献.对各采样点金属含量进行相关性分析,发现焚烧炉烟气与其他采样点的重金属间有显著相关性(r＞0.81,p ＜0.05),对各采样点元素含量进行主成分分析也得到了相似结论,说明焚烧炉对周围环境空气重金属含量有直接影响.     

Chemical speciation and mobility of heavy metals in municipal solid waste incinerator fly ash

Chemical speciation is a significant factor that govems the toxicity and mobility of heavy metals in municipal solid waste incinerator fly ash. Sequential extraction procedure is applied to fractionate heavy metals( Pb, Zn, Cd, Cu, and Cr) into five defined groups: exchangeable, carbonate, Fe-Mn oxide, organic, and residual fractions. The mobility of heavy metals is also investigated with the aid of toxicity characteristic leaching procedure. In the fly ash sample, Pb is primarily presented in the carbonate (51%) and exchangeable(20% ) fractions; Cd and Zn mainly exist as the exchangeable(83% and 49% respectively) ; Cu is mostly contained in the last three fractions(totally 87% ) ; and Cr is mainly contained in the residual fraction(62% ). Pb, Zn and Cd showed the high mobility in the investigation, thus might be of risk to the natural environment when municipal solid waste incinerator fly ash is landfilled or reutilized.     

垃圾焚烧炉渣对电镀废水中Cu的吸附特性

以垃圾焚烧炉渣作吸附剂,对电镀废水中Cu的吸附特性进行了研究,包括吸附速率、解吸速率、吸附等温线和连续柱吸附实验等。结果表明,炉渣对电镀废水中Cu的吸附平衡时间和解吸平衡时间均为8 h。炉渣对Cu的吸附等温线为直线型,可用Henry型方程进行拟合。连续柱吸附实验结果表明,炉渣对电镀废水在连续吸附55 h后吸附能力逐渐丧失,累计最大吸附量为921μg/g,而炉渣对人工配水在连续吸附80 h后吸附能力完全丧失,累计最大吸附量为2 687μg/g。     

Experimental investigation of ash deposits on convection heating surfaces of a circulating fluidized bed municipal solid waste incinerator

Incineration of municipal solid waste(MSW) is a waste treatment method which can be sustainable in terms of waste volume reduction, as well as a source of renewable energy.During MSW combustion, increased formation of deposits on convection heating exchanger surfaces can pose severe operational problems, such as fouling, slagging and corrosion.These problems can cause lower heat transfer efficiency from the hot flue gas to the working fluid inside the tubes. A study was performed where experiments were carried out to examine the ash deposition characteristics in a full-scale MSW circulating fluidized bed(CFB) incinerator, using a newly designed deposit probe that was fitted with six thermocouples and four removable half rings. The influence of probe exposure time and probe surface temperature(500, 560, and 700℃) on ash deposit formation rate was investigated. The results indicate that the deposition mass and collection efficiency achieve a minimum at the probe surface temperature of 560℃. Ash particles are deposited on both the windward and leeward sides of the probe by impacting and thermophoretic/condensation behavior. The major inorganic elements present in the ash deposits are Ca,Al and Si. Compared to ash deposits formed on the leeward side of the probe,windward-side ash deposits contain relatively higher Ca and S concentrations, but lower levels of Al and Si. Among all cases at different surface temperatures, the differences in elemental composition of the ash deposits from the leeward side are insignificant.However, as the surface temperature increases, the concentrations of Al, Si, K and Na in the windward-side ash deposits increase, but the Ca concentration is reduced. Finally,governing mechanisms are proposed on the basis of the experimental data, such as deposit morphology, elemental composition and thermodynamic calculations.     

全烧垃圾流化床炉飞灰制备免烧砖的性能研究

开展了水泥固化全烧垃圾循环流化床焚烧炉飞灰特性及其制备免烧砖的研究.同时,分析了飞灰的特性,研究了水泥用量对砖体抗压强度和重金属浸出毒性的影响,并对固化前后飞灰在不同p H值溶液环境下的重金属渗滤特性和基于改进RCR连续提取法的重金属形态分布进行了对比研究.结果表明:飞灰中Cd、Cu、Pb、Ni的浸出浓度分别达到1.76、60.29、5.36、1.48 mg·L-1,远超出生活垃圾填埋标准的规定,Cd、Zn、Cu的酸可交换态部分很高,分别为48%、21.26%、20.72%.水泥基材具有良好的稳定效果,添加量达到30%时,免烧砖中重金属的浸出毒性已远低于标准值.随着水泥掺量的提高,免烧砖的抗压强度呈上升趋势,当水泥比例为30%时,强度可达到12.8 MPa,35%水泥比例的砖体,其抗压强度则达到国标建筑用砖的MU15级.与原始飞灰相比,砖体中重金属在不同渗滤液p H下的浸出趋势并未改变,浸出量却显著下降,p H的适应范围变宽.另外,重金属中酸可交换态部分降至低于1%,主要转变成了可还原态,对环境的污染风险大幅降低.     

生活垃圾循环流化床焚烧锅炉飞灰中二噁英热解析特性研究

实际垃圾焚烧系统中飞灰会在尾部烟道堆积并在受热后发生二噁英的再生成、热降解及向烟气解析等协同作用.本文研究了半干法脱硫塔前生活垃圾焚烧飞灰在受热过程中二噁英的质量变化及其气固相分布情况,重点研究了反应温度、含氧量及硫胺基复合阻滞剂的添加等对飞灰中二噁英热解析特性的影响.试验结果表明,250℃时飞灰析出的气相二噁英很少,而450℃时气相二噁英的比例高达99.7%;氧含量对飞灰中二噁英的热解析特性影响较大,当氧含量为6%时,气相二噁英的析出量最大,达到2.87 ng·g-1;350℃时添加硫胺基复合阻滞剂后二噁英总量明显下降,表明阻滞剂能够抑制二噁英再合成,但气相中二噁英的比例从47.69%上升到87.50%.     

PCDD/Fs in soil around a hospital waste incinerator: comparison after three years of operation

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) can be formed during the cooling of flue gases in waste incinerator. These pollutants are either in the gas phase or attached to the fine particles, escaping dust collection. After stack emission, they are slowly oxidized photochemically (gas phase), or eventually are deposited (dry and wet deposition of particulate) in earth surface. In 2007 and 2010, 11 soil samples were collected in the vicinity of a hospital waste incinerator (HWI), prior and after its startup. In order to find out any variation of PCDD/Fs in soil, in brief dioxins, their concentrations were analyzed by high-resolution gas chromatography with high-resolution mass spectrometry (HRGC/HRMS). Compared to the baseline survey (2007), PCDD/Fs in soil significantly increased, by average, +81.6% in total PCDD/Fs and +132.7% in international toxic equivalency (I-TEQ) unit. By principal component analysis (PCA), both the PCDD/Fs homologue and the HxCDF isomer profile in soil were found to become more similar with fly ash. Generally, this incinerator influences the soil only in a limited area. More comprehensive supervision, stricter management and more advanced technology should be implemented in this plant to reduce pollutants emission, even though the level of PCDD/Fs in soil is quite low at present.     

土壤中持久性有机污染物的提取技术研究

文章介绍了持久性有机污染物的分析检测方法,指明了研究土壤中持久性有机污染物的必要性.将国内最常用的两种提取方法--索式提取和超声波提取进行比较,结果表明了索式提取的方法更适合从土壤中提取多种持久性有机污染物,提取剂和洗脱剂可选比例1:1的丙酮和石油醚,回收率可在70%～90%之间;而超声波提取的方法比较适合从土壤中提取个别的持久性有机污染物,如op′-DDT 和pp′-DDT,节省实验时间,试剂使用量少,回收率也可在50%以上.     

Effects of 5-year application of municipal solid waste compost on the distribution and mobility of heavy metals in a Tunisian calcareous soil

It is obvious that the application of solid waste compost improves the soil fertility. These wastes, however, may also have some negative effects on the agricultural environment due to their metal content. This research aimed at evaluating the influence of Tunisian municipal solid waste compost and farmyard manure on some chemical properties and the distribution of heavy metals in a calcareous Tunisian soil (clayey–loamy soil). A field plot experiment, without vegetation, was installed since 1999 at the experimental farm of the Agronomic National Institute of Tunis (INAT) in the region of Mornag (20 km south of Tunis, Tunisia). During 5 years, the field received yearly the following treatments: 0, 40, 80 and 120 t/ha of municipal solid waste compost and 0, 40 and 120 t/ha of manure. The fractionation of heavy metals in the soil was evaluated after 5 years using a sequential extraction procedure. The application of the two amendments was found to increase the content of organic matter, the total nitrogen content and the electrical conductivity, whereas it slightly decreased the soil pH. The addition of manure did not have a significant effect on the accumulation of heavy metals in the soil, whereas compost application increased the total concentration of heavy metals in the soil. The distribution of heavy metals between the different fractions in untreated and treated soils showed the residual fraction to be dominant, followed by the fraction bound to Fe and Mn oxides. The amount of Cu bound to the organic fraction increased with the application rate, which is probably caused by the formation of organic complexes. For the other metals, the increase of the association with organic matter is very limited. The application of compost moreover increases the amount of Zn associated with Fe and Mn oxides. The “Mobility Factor (MF)” was quite low and did not change after the 5-year application of the two organic amendments. It always remained lower than 10%, although for Cd it amounted to 17%.     

城市污泥对通菜-水稻土中有机污染物的累积效应

在水稻土上施用城市污泥及化肥盆栽通菜,应用GC/MS对通菜植株和土壤中的邻苯二甲酸酯(PAEs)和多环芳烃(PAHs)等7类43有机污染物进行系统分析,探讨通菜植株和土壤中其累积效应.结果表明,通菜植株中检出邻苯二甲酸酯、多环芳烃、氯苯类、硝基苯类、醚类和卤代烃类共6类28种化合物(胺类未检出),土壤中检出上述7类33种化合物,均以PAEs和PAHs为主,其总含量是其他类污染物的几倍或数十倍.不同处理的通菜和土壤中各类有机污染物的含量差别较大,均以个别或少数污染物为主.施用城市污泥增加了植株和土壤中PAEs和PAHs等污染物的含量.强致癌性化合物苯并(a)芘在通菜中被检出,在部分土壤中的含量超过加拿大土壤质量控制标准(1.0mg/kg).除佛山污泥处理的通菜对氯苯类和醚类的生物浓缩系数(BCF)大于1外,其余均小于1.0.     

Influence of SO2 in incineration flue gas on the sequestration of CO2 by municipal solid waste incinerator fly ash

The influence of CO2 content and presence of SO2 on the sequestration of CO2 by municipal solid waste incinerator(MSWI) fly ash was studied by investigating the carbonation reaction of MSWI fly ash with different combinations of simulated flue gas.The reaction between fly ash and 100% CO2 was relatively fast;the uptake of CO2 reached 87g CO2/kg ash,and the sequestered CO2 could be entirely released at high temperatures.When CO2 content was reduced to 12%,the reaction rate decreased;the uptake fell to 41g CO2/kg ash,and 70.7% of the sequestered CO2 could be released.With 12% CO2 in the presence of SO2,the reaction rate significantly decreased;the uptake was just 17g CO2/kg ash,and only 52.9% of the sequestered CO2 could be released.SO2 in the simulated gas restricted the ability of fly ash to sequester CO2 because it blocked the pores of the ash.     

生活废弃物焚烧处置烟气中二(口恶)英排放特性研究

研究了某市10座生活垃圾焚烧炉烟气中二噁英的排放特性,对比了焚烧炉炉型、焚烧处理量、烟气净化系统对二噁英排放特性的影响.结果表明:10座生活垃圾焚烧炉二噁英的排放浓度为0.016~0.104 ng·Nm~(-3)(以I-TEQ计),9座垃圾焚烧炉二噁英排放满足国家相应的排放标准(0.1 ng·Nm~(-3)(以I-TEQ计)).根据二噁英排放浓度排序对应的烟气净化系统分别为SNCR(Selective Non-Catalytic Reduction)+半干法+活性炭喷射+布袋湿法+活性炭喷射+布袋半干法+活性炭喷射+布袋,表明安装SNCR装置有利于二噁英的减排.另外,不同垃圾焚烧炉排放的二噁英指纹特性不仅与烟气净化系统和炉型有关,还与垃圾来源有一定关联.     

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.     

北京市城市生活垃圾处理温室气体排放特征及减排策略

根据《IPCC国家温室气体清单指南》和《省级温室气体清单编制指南》方法,建立北京市3种生活垃圾处理方式温室气体排放清单,测算2010—2019年不同生活垃圾处理方式下温室气体CH₄、CO₂、N₂O排放量,分析CO₂排放量随时间变化特征,并基于此提出碳减排策略。结果表明：1）2010—2019年北京市生活垃圾处理温室气体的排放量总体呈先增后减的趋势,且变动幅度减缓,2019年达到最低水平,这主要与近年来北京市生活垃圾处理方式从以卫生填埋为主转变为以焚烧为主有关。2）2018年北京市生活垃圾焚烧量已超过填埋量,而垃圾焚烧处理CO₂排放量远低于填埋处理,表明焚烧处理方式CO₂排放强度低于填埋处理。3）生活垃圾处理温室气体排放量与垃圾处理方式及处理量密切相关,随着生活垃圾产生量的日益增加,建议在生活垃圾管理全过程加强垃圾精细化分类,推进源头减量;合理开展垃圾处理设施的建设,优化垃圾收运系统,防止垃圾处理二次污染,探索适合我国城市生活垃圾处理低碳优化模式。

     

垃圾焚烧厂周边大气二噁英含量及变化特征——以北京某城市生活垃圾焚烧发电厂为例

2013年4月至2014年1月对北京市某生活垃圾焚烧厂周边4km范围内5个采样点环境空气中二噁英含量、组成特征及季节变化特征进行了分析.结果表明该垃圾焚烧厂周边环境空气中PCDD/Fs质量浓度的变化范围为8.3~115pg/m³,毒性当量(TEQ)变化范围为0.11~1.9pg I-TEQ/m³,其中秋季1个采样点和冬季全部采样点超出日本环境空气质量标准限值(0.6pg I-TEQ/m³).1,2,3,4,6,7,8-HpCDF和OCDF均是四季空气中PCDD/Fs质量浓度的主要贡献单体,而2,3,4,7,8-PeCDF是总TEQ贡献最大的单体.空间分布特征表现为近源点位(~400m)浓度水平较高而其他点位(>1000m)浓度水平与距污染源距离远近没有显著相关性;季节变化特征表现为冬季值显著高于其他季节,分析可能与冬季采暖及大气扩散条件差导致的大气整体污染较重有关.样品中二噁英同族体及异构体分布指纹谱图与焚烧设施排放烟气存在差别,主成分分析(PCA)源解析结论与指纹谱图特征分析结论一致,体现为多种污染源共同作用的影响.二噁英呼吸暴露剂量估算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(0.034~0.161pg I-TEQ/(kg·d)),但仍需关注大气重污染天气发生时的呼吸暴露风险.