参数对脉冲电晕等离子体同时去除汞和三氯苯的影响

医疗垃圾焚烧排放烟气中含有汞和二恶英污染物,这两者均具有高毒性和较强的环境危害性。通常使用活性炭喷射法同时去除汞和二恶英,但该方法耗材高、成本大、存在着二次污染。为了解决上述问题,采用脉冲电晕低温等离子体技术处理汞和三氯苯(二恶英的模拟物),通过等离子体放电实现汞的氧化和三氯苯的降解,研究了电压、频率、脉宽、上升沿(即上升时间)对脉冲电晕等离子体同时去除汞和三氯苯的影响。结果表明:电压、频率对等离子体去除Hg~0和TCB有重要影响,在电压为17 kV时,最高可实现约65%的Hg~0氧化去除率,约70%的TCB去除率;脉宽、上升沿变化对二者的去除无明显影响;检测产物的主要物质为产生酮类、苯衍生物。综合上述结果,脉冲电晕等离子去除Hg~0和TCB的去除机制包括能量竞争和自由基反应,在能量竞争中,TCB具有明显优势。研究结果可为低温等离子体技术同时去除汞和二恶英的工业化应用提供参考。     

医疗废物回转窑焚烧线中二恶英的生成

通过采集医疗废物回转窑焚烧生产线不同部位的烟气的二恶英样品,研究了医废焚烧过程二恶英在焚烧线200～600℃区间不同烟道断面烟气中分布变化情况。研究结果表明,医疗废物焚烧后烟气中二恶英的发生浓度要高于一般的生活垃圾焚烧烟气的浓度,大致在5～23.3 ng TEQ/m3的范围,锅炉出口到脱酸塔入口段的管道和设备为烟气中二恶英重新合成的高发区域,医废焚烧烟气中二恶英(TEQ)主要是以气态污染物的形态存在。     

2种活性炭协同布袋除尘对垃圾焚烧厂烟气中二恶英的去除

考察了2种活性炭(活性炭A和活性碳B)对垃圾焚烧厂烟气中二恶英去除率的影响。通过采集与分析垃圾焚烧厂"活性炭喷射+布袋除尘"协同处置工艺前口和后口的烟气样品,得到前后口2,3,7,8-PCDD/Fs的浓度,并计算去除率。结果表明:2种活性炭对2,3,7,8-PCDFs的去除率相当,均为99%左右;而对2,3,7,8-PCDDs的去除率略低,分布在83.3%~99.9%之间,并且活性炭A的去除率高于活性炭B。通过对2种活性炭性能指标测试结果的比较,具备更丰富的中孔以及更大的微孔、中孔平均孔径可能是活性炭A去除率更高的原因。此外,比较了活性炭在不同投加速率(5、10和15 kg·h~(-1))下对二恶英的去除率,发现低投加速率时二恶英去除率随投加速率的增加而增加,而当投加速率从10 kg·h~(-1)增加到15 kg·h~(-1)时二恶英去除率无明显变化。     

荧光素酶报告基因法测定飞灰中二噁英类物质

荧光素酶报告基因法(CALUX)相比高分辨气相色谱/质谱法(HRGC/HRMS)测定二噁英浓度时,具有分析周期短、检测成本低、灵敏度高(皮克水平)、能反映样品的毒性总量且可进行高通量检测等优点。实际应用时,可先用CALUX对样品作初步筛选检测,再将筛选出的阳性样品用化学分析法作进一步定性定量检测。通过对42个垃圾焚烧飞灰样品同时进行HRGC/HRMS和CALUX分析,得到两者的换算系数,从而可以利用快速检测的结果和换算系数来推算HRGC/HRMS的结果。实验表明,CALUX结果与HRGC/HRMS结果具有很好的线性相关性(R=0.96),换算系数为0.332。该换算系数与日本得到的结果不同,表明中国飞灰性质有别于日本飞灰。而且,不同环境介质之间换算系数也不一致。为增加该方法在中国的适用性,必须通过实验方法找出符合中国样品的换算系数。     

火电厂协同资源化处理城市污泥二次污染控制

控制循环流化床锅炉掺烧城市污泥二次污染物的排放,实现污泥的减量化、无害化处置和资源化利用。方法:利用循环流化床锅炉烟气余热干燥污泥,干化污泥与燃煤掺配燃烧,污泥干燥系统与锅炉DCS控制系统对接,依据机组负荷自动化控制锅炉耗煤量、床温和污泥给入量等运行参数,有效抑制二恶英的形成。结果表明,污泥自动化掺烧系统投运后,烟气中二恶英的排放浓度小时均值不高于0.011 0 ng TEQ·(Nm)-3,飞灰中二恶英含量不高于2.802 2 ng TEQ·kg-1、底渣中二恶英含量不高于0.659 6 ng TEQ·kg-1,符合国家污染控制标准要求。火电厂协同资源化处理城市污泥过程中,污泥自动化掺烧系统投运能够有效控制二次污染物的排放,实现了城市污泥的减量化、无害化处置和资源化利用。     

环境污染与防治网络版论文摘要

Pb与1,2,4-三氯苯单一及复合污染对蚯蚓毒性机制的研究胡艳祝飞王艳吴石金(浙江工业大学生物与环境工程学院,浙江杭州310014)以赤子爱胜蚓(Eisenia Foetida)作为受试生物,研究了土壤中Pb2+与1,2,4-三氯苯单一及复合污染对蚯蚓的毒性机制。通过滤纸接触法研究Pb2+与1,2,4-三氯苯的单一急性毒性效应,结果表明,两者对赤子爱胜蚓均有毒性。染毒48 h时,Pb2+的半数致死浓     

在线固相萃取液质联用法测定饮用水源中的痕量联苯胺

建立了在线固相萃取液相色谱串联质谱法测定水中痕量联苯胺的方法。样品经自动进样器注入在线固相萃取小柱后,用富集泵流动相实现对样品的富集洗脱,然后用分析泵流动相将样品从富集柱冲洗至色谱柱后用串联质谱仪进行检测。该方法可在11 min内自动完成对样品的富集、净化、进样和检测过程。当进样量为5 m L时,联苯胺在0.010~2.0μg·L~(-1)范围内具有良好的线性关系,相关系数R为0.999,检出限为0.8 ng·L~(-1),实际水样的回收率为85%~104%。该方法具有简单、快速、重现性好、灵敏高等特点,可用于环境水体中痕量联苯胺的检测。     

某焦化厂PM_(2.5)中多环芳烃的排放特征及其对周边环境影响

为了解焦化厂在装煤过程中产生的PM_(2.5)及其周边区域空气环境PM_(2.5)中多环芳烃(PAHs)的含量,采用微纤维石英滤膜对PM_(2.5)采样,并通过气相色谱-质谱仪分析PM_(2.5)上负载的16种毒性较大PAHs。结果表明:焦炉装煤除尘烟气PM_(2.5)中PAHs的成分主要受到炼焦配煤的影响;布袋除尘器对装煤除尘烟气中高环PAHs的处理效果显著;焦化厂周边空气环境中PM_(2.5)中的PAHs浓度呈明显空间递减趋势。采用特征比值法分析得到该区域空气环境中PAHs主要来源于煤炭燃烧,用毒性当量法分析得到焦化厂区域PM_(2.5)中PAHs的毒性为其他区域的9~90倍,高环PAHs的毒性贡献较大。     

Ag@SiO_2核壳粒子SERS快速检测辛基酚

以Ag@SiO_2核壳粒子为基底,利用表面增强拉曼光谱(SERS)技术实现酚类内分泌干扰物的快速检测。采用柠檬酸钠还原硝酸银制得银纳米粒子,以正硅酸乙酯为硅源,在银纳米颗粒表面包裹不同厚度的SiO_2得到Ag@SiO_2核壳粒子。通过透射电镜、紫外光谱、X射线衍射等表征手段对Ag@SiO_2核壳粒子进行了表征和分析。以辛基酚为探针研究Ag@SiO_2粒子表面增强拉曼效应与SiO_2厚度、核壳粒子浓度的关系及辛基酚的检测限,并以此法检测实际环境样品中辛基酚的含量。结果表明,辛基酚的表面增强拉曼效应随着Ag@SiO_2壳厚的增加而减弱,随着辛基酚浓度的增大而增强,且在1 390 cm~(-1)处的峰强信息与浓度有着良好的线性关系,辛基酚最低检测限浓度为1μg·L~(-1),可以实现辛基酚的SERS检     

流化床垃圾焚烧炉产生的有毒二(口恶)英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2,3,7,8位氯取代二(口恶)英同类物的含量及其毒性当量.结果表明,产生的二(口恶)英主要存在于飞灰中,烟气中的含量很少.飞灰中二(口恶)英总浓度和毒性当量分别为8.44ng/g和0.80ng/g,经过布袋除尘器后的烟尘和烟气中二(口恶)英的浓度之和与毒性当量之和分别为0.34 ng/m3和0.02 ng/m3,而布袋除尘器前的烟尘和烟气中二(口恶)英的浓度之和与毒性当量之和分别为40.78 ng/m3和3.01ng/m3.飞灰和烟尘中2,3,7,8位氯取代二(口恶)英同类物的分布相似,但是与烟气中2,3,7,8位氯取代二(口恶)英同类物的分布差别较大.通过了解有毒二(口恶)英同类物的分布,可以进一步优化流化床垃圾焚烧炉的焚烧条件,降低二(口恶)英的排放量,减少垃圾焚烧对环境的污染.     

Cluster Analysis for Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans Concentrations in Southern Taiwan

Abstract

This study investigates the characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the ambient air of two municipal solid waste incinerators (MSWIs: GS and RW) and a coal-fired power plant (PW) in the Kaohsiung County (KC) area in Taiwan. The results show that the toxic equivalency (TEQ) concentration in the flue gas of GS and RW averaged 0.090 and 0.044 ng international toxic equivalents (I-TEQ)/N·m³, respectively. The TEQ concentration in the flue gas of PW averaged 0.050 ng I-TEQ/N·m³. All PCDD/Fs concentrations from the stack flue gas are lower than the Taiwan Environmental Protection Administration emission standard. Furthermore, the mean I-TEQ concentration in the ambient atmosphere ranged from approximately 0.019 to 0.165 pg I-TEQ/N·m³, much lower than the environmental quality standards for dioxins in Japan (0.6 pg TEQ/N·m³). This work classified all sampling sites into three clusters according to k-means cluster analysis. The result shows a probable direct correlation between the GS incinerator and site C. Although the concentration from the PW plant did not exceed the emission standard, it was much higher than that in Fernández-Martínez’s study. For proper environmental management of dioxins, establishing a complete emission inventory of PCDD/Fs is necessary. The government of Taiwan should particularly pay more attention to power plants to address the information shortage.     

Identification of surrogate compounds for the emission of PCdd/F (I-TEQ value) and evaluation of their on-line real-time detectability in flue gases of waste incineration plants by REMPI-TOFMS mass spectrometry

Correlations between products of incomplete combustion (PIC), e.g., chloroaromatic compounds, can be used to characterise the emissions from combustion processes, like municipal or hazardous waste incineration. A possible application of such relationships may be the on-line real-time monitoring of a characteristic surrogate, e.g., with Resonance-Enhanced Multiphoton Ionization-Time-of-Flight Mass Spectrometry (REMPI-TOFMS). In this paper, we report the relationships of homologues and individual congeners of chlorinated benzenes (PCBz), dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and phenols (PCPh) to the International Toxicity Equivalent (I-TEQ) of the PCDD/F (I-TEQ value) in the flue gas and stack gas of a 22 MW hazardous waste incinerator (HWI). As the REMPI detection sensitivity is decreasing with the increase of the degree of chlorination, this study focuses on the lower chlorinated species of the compounds mentioned above. Lower chlorinated species, e.g., chlorobenzene (MCBz), 1,4-dichlorobenzene, 2,4,6-trichlorodibenzofuran or 2,4-dichlorophenol, were identified as I-TEQ surrogates in the flue gas. In contrast to the higher chlorinated phenols, the lower chlorinated phenols (degree of chlorination <4) were not reliable as surrogates in the stack gas. The identified surrogates are evaluated in terms of their detectability by REMPI-TOFMS laser mass spectrometry. The outcome is that MCBz is the best suited surrogate for (indirect) on-line measuring of the I-TEQ value in the flue gas by REMPI-TOFMS. The correlation coefficient r of the MCBz concentration to the I-TEQ in the flue gas was 0.85.     

Online measurements of low-volatile organic chlorine for dioxin monitoring at municipal waste incinerators

In this study, an automatic sampling device and an analysis device have been developed for the measurement of low-volatile organic chlorine (LVOCl) in flue gas. The concentrations of dioxins (polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls) have been estimated by online measurements of LVOCl at a municipal solid waste incinerator (MSWI) using these devices. The LVOCl concentration at the outlet of the selective catalyst reactor (SCR) of the MSWI increased momentarily up to 95 μg Cl m⁻³ during the startup period of the MSWI; subsequently, it gradually decreased to less than 1.0 μg Cl m⁻³ after 50 h from the start of waste feeding. The concentration of toxic equivalent quantity (TEQ)-Dioxins at the SCR outlet had a linear positive relationship with the LVOCl concentrations. Moreover, the level of TEQ-Dioxins concentration can be estimated by using this relationship with LVOCl. From our results, since the LVOCl concentrations in a flue gas can thus be automatically analyzed every hour by online measurements, the operators of an MSWI would be able to monitor approximate TEQ-Dioxin emissions on a daily basis.     

流化床垃圾焚烧炉产生的有毒二噁英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2，3，7，8位氯取代二噁英同类物的含量及其毒性当量。结果表明，产生的二噁英主要存在于飞灰中，烟气中的含量很少。飞灰中二噁英总浓度和毒性当量分别为8.44ng／g和0．80ng／g，经过布袋除尘器后的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为0．34ng／m^3和0．02ng／m^3，而布袋除尘器前的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为40．78ng／m^3和3．0ng／m^3。飞灰和烟尘中2，3，7，8位氯取代二噁英同类物的分布相似，但是与烟气中2，3，7，8位氯取代二噁英同类物的分布差别较大。通过了解有毒二噁英同类物的分布，可以进一步优化流化床垃圾焚烧炉的焚烧条件，降低二噁英的排放量，减少垃圾焚烧对环境的污染。     

Assessment of PCDD/F risk after implementation of emission reduction at a MSWI

Municipal solid waste incinerators (MSWIs) have been shown to be important sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The emission of PCDD/Fs by MSWIs is a controversial subject in human health risk assessment. In this study the effect of a MSWI on a residential area was assessed before and after the installation of an additional treatment system for flue gas. This additional treatment system resulted in a dramatic decrease in PCDD/F concentrations in stack flue gas samples by 99.98%, while the concentrations in air decreased by approximately 50% (36,500 and 0.75 pg I-TEQ m(-3) for air in 1999; 3.5 and 0.38 pg I-TEQ m(-3) in 2002; 1.6 and 0.076 pg I-TEQ m(-3) in 2005 for stack gas and air, respectively). Considering the congener distributions of PCDD/Fs between stack flue gas and air samples, the study area seemed to have been contaminated by other urban sources as well as the MSWI. ISC3 model results support the conclusion that this incinerator became only a minor contributor to the study area after installation of the supplementary systems. This resulted from both proper MSWI operation using modern technology and additional sources of contaminants in this region. Finally, PCDD/F uptake by humans through inhalation of contaminated air was estimated. Assuming that inhalation exposure contributes 10% of total exposure, total exposure was lower than WHO guidelines. These results confirm that proper operation and maintenance of the incinerator led to a reduction in emissions and potential health impacts of PCDD/Fs.     

Long-term monitoring and modeling of polychlorinated dibenzo-p-dioxins and dibenzofurans from municipal solid waste incinerators and surrounding area in northern Taiwan

Municipal solid waste incinerators (MSWIs) have long been the major contributors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to ambient air in Taiwan. After stringent MSWI emission standards were introduced in 2001, the long-term continuous monitoring of flue gas and ambient air quality became necessary to ensure the effectiveness of the related control strategies. Three MSWIs and the surrounding ambient air were investigated in the current study for PCDD/F characteristics during 2006 to 2011. The average concentrations in the flue gas ranged from 0.008?~?0.0488 ng I-TEQ/Nm³, which is much less than the emission standard in Taiwan (0.1 ng I-TEQ/Nm³) (I-TEQ is the abbreviation of International Toxic Equivalent). This led to extremely low levels in the ambient air, 0.0255 pg I-TEQ/Nm³, much less than the levels seen in most urban areas around the world. Additionally, the results obtained using the Industrial Source Complex Short-Term Dispersion Model (ISCST3) indicate that the PCDD/F contributions from the three MSWIs to the ambient air were only in the range from 0.164?~?0.723 %. Principal component analysis (PCA) showed that the PCDD/Fs in the air samples had very similar characteristics to those from mobile sources. The results thus show that stringent regulations have been an effective control strategy, especially for urban areas, such as Taipei City.     

Study of PCDD/Fs distribution in fly ash,ash deposits,and bottom ash from a medical waste incinerator in China

Over the past decades in China, the number of medical waste incinerators (MWIs) has been rising rapidly, causing emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). In this study, samples of fly ash, ash deposits, and bottom ash from typical MWIs were analyzed for PCDD/Fs and their distribution characteristics. Results showed international toxic equivalent (I-TEQ) values in the range of 6.9–67 ng I-TEQ/g in fly ash and ash deposits, whereas the concentration in bottom ash was extremely low (only 1.33 pg I-TEQ/g), yet the generation of PCDD/Fs was mostly de novo synthesis in fly ash and ash deposits according to the ratio of PCDFs to PCDDs; the major distribution differences of PCDD/Fs in fly ash was manifested by the content of toxic furan 2,3,7,8-TCDF, but other toxic PCDD/Fs showed similar distribution. Other findings are that 2,3,4,7,8-PeCDF had the most contribution to TEQ concentration, and that the most abundant toxic furan congener is 1,2,3,4,6,7,8-HpCDF. Correlation analysis showed that there was no significant correlation between PCDD/Fs concentration and several other physical and chemical parameters.

Implications: This paper is of interest because it presents the emission performances of PCDD/Fs in ash from medical waste incineration in China. PCDD/F contents in fly ash and ash deposits vary between 6.9 and 67.3 ng I-TEQ/g. However, the concentration in bottom ash was extremely low (only 1.33?×?10^?3 ng I-TEQ/g). The fingerprints of PCDD/Fs in fly ash are almost similar, except for 2,3,7,8-TCDF. There is no marked correlation between PCDD/Fs and other physicochemical properties.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

PCDD/PCDF emissions from small firing systems in households

This report presents results of emission measurements of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in the flue gas of seven oil, nine gas, and two wood firing systems under laboratory conditions. The burn rate of the combustion was in the range of the rated useful heat output. Two additional test series varied the amount of combustion air and thus the heat output. The PCDD/PCDF emissions for oil- and gas-fired boilers are in the range of 0.0020-0.0142 ng I-TEQ/m3 (referring to 3% O2 in the dry flue gas). No correlation between the combustion technique and the PCDD/PCDF emissions could be established. In the tests with the wood-fired furnaces PCDD/PCDF concentrations in the flue gas ranging from 0.014 to 0.076 ng I-TEQ/m3 (referring to 13% O2 in the dry flue gas) were found. A significant correlation between the firing rate of the heating insert and the measured PCDD/PCDF concentrations was found. On examination of three typical 2,3,7,8-CDD/CDF congener profiles, a comparable pattern could be observed with natural gas and light fuel oil. The congener distribution for wood combustion is considerably different.     

Characteristics of dioxin emissions at startup and shutdown of MSW incinerators

Dioxin concentrations from municipal waste incinerators in Japan and elsewhere often show low concentrations that comply with legal limits (in this paper, the term "dioxin" designates WHO-TEQ: PCDD/Fs+dioxin-like PCB). However, such data is usually generated under normal steady state operational conditions, and there has been little investigation of releases occurring during startup and shutdown. It is important, therefore, to ascertain quantitatively emissions in an unsteady state (startup and shutdown) in order to correctly evaluate the relationship between emissions from a facility and the surrounding environment. The present study aimed to examine dioxin emissions of a continuously operated incinerator at startup and shutdown, and estimating the time period of greatest emission, and the processes causing dioxin generation. The startup process was divided into five stages and the shutdown into two; at each stage, dioxins in the flue gas were measured at the boiler outlet and the stack. From the concentration of dioxins and the flue gas volume at each stage, the amount of dioxins at startup and shutdown were calculated, and these were compared with that under steady state conditions. Dioxin concentration at the stack under steady state conditions was a very low level, while those at startup and shutdown were higher. In the case where dioxin concentration under a steady state is a low level like in this study, it is indicated that the total annual dioxin emission from a facility could be attributed to the startup periods.     

Air and soil dioxin levels at three sites in Italy in proximity to MSW incineration plants

Levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in both air and soil samples were measured at three different sites in Italy, in proximity to three municipal solid waste incinerators (MSWIs) to determine baseline contamination and the contributory role of incinerator emissions. At the first site, located in an agricultural, cattle-breeding, typically flattish area of the Po Valley, the dioxin concentrations had already been measured before the start-up of the new MSWI. These dioxin concentrations were then again measured after two years of continual operation of the incinerator. Despite the presence of the plant, the PCDD/Fs concentrations appear not to have been affected and were found to be in a range of 22-125 fg I-TEQ m(-3) in the air samples and 0.7-1.5 pg I-TEQ g(-1) in the soil samples. The second site is located in an industrial district of the Veneto Region, in the surroundings of an old MSWI that is not equipped with Best Available Technology (BAT) dioxin removal system. The PCDD/Fs concentrations in the air samples were between 144 and 337 fg I-TEQ m(-3). This is a typical range of values for industrial areas, while the soil samples showed contamination levels between 1.1 and 1.4 pg I-TEQ g(-1). The third site lies in the Adige Valley, near a MSWI that has been equipped with BAT for flue gas cleaning. The observed values ranged from 10 to 67 fg I-TEQ m(-3) for the air samples and 0.08-1.2 pg I-TEQ g(-1) for the soil samples. The contributory factors of the varying characteristics of the different areas together with the types of technology adopted at each MSWI plant are discussed. The PCDD/Fs levels are subsequently compared with established values from previous studies.