Wei-Shan Lee

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from stack flue gases of sinter plants

This study investigated four sinter plants, classified into two categories--with selective catalytic reduction (SCR) (S1, S2 and S3) and without SCR (S4) as its air pollution control device. Polychlorinated dibenzofurans (PCDFs) are dominant in the stack flue gases of sinter plants with and without SCR. The polychlorinated dibenzofurans/polychlorinated dibenzo-p-dioxins (PCDFs/PCDDs) ratio exceeds 1 extremely. The degree of chlorination of the sinter plant without SCR is towards hepta and hexa congeners while that of the sinter plant with SCR is towards penta and hexa congeners. PCDD/Fs are indeed decomposed (75.5% and 69% on ng and ng TEQ bases, respectively) and not only reduced in degree of chlorination. The overall concentration in the stack flue gas of sinter plants with SCR (7.97-14.1 ng/Nm(3); 0.995-2.06 ng TEQ/Nm(3)) is lower than that of the sinter plant without SCR (28.9 ng/Nm(3); 3.10 ng TEQ/Nm(3)). In Taiwan, based on the emission factors of 0.970 microg TEQ/ton-feedstock (sinter plants with SCR) and 3.13 microg TEQ/ton-feedstock (sinter plant without SCR), the annual PCDD/F emission of 44.7 g TEQ/year from sinter plants is 60 and 121 times higher than those from municipal solid waste incinerators (0.750 g TEQ/year) and MWIs (0.369 g TEQ/year). These results show that sinter plants have become the dominating PCDD/F emission source since tighter emission limits have been applied to incinerators.

Effect of chlorine content in feeding wastes of incineration on the emission of polychlorinated dibenzo-p-dioxins/dibenzofurans

This study attempts to clarify the effects of chlorine content in waste on the formation mechanisms of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in full scale incinerators by proposing and using the principal component analysis (PCA) to compare the congener profiles of PCDD/Fs in the stack flue gases of 17 emission sources, including incinerators and vehicles. Four incinerators, among these 17 emission sources, were sampled and analyzed in this study, and the data for the other 13 emission sources were selected from previous studies. These 17 emission sources can be classified into four categories, including medical waste incinerators (MWIs, H1-H5), municipal solid waste incinerators (MSWIs, M1-M8), vehicle fuel combustion (unleaded gas-fueled vehicles, UGFV; diesel-fueled vehicles, DFV, n = 2) and polyvinylchloride (PVC) facility vent combustors (PVC1 and PVC2, n = 2). PCA was conducted for these emission sources with the fractions of 17 2,3,7,8-congeners in the stack flue gases as variables to clarify the effect of chlorine content in feeding wastes on the emission of PCDD/Fs. From the results of PCA, we extrapolated that the threshold value of the chlorine content was at 0.8-1.1%, and the formation mechanisms of PCDD/Fs are influenced first by whether the chlorine content in the feeding waste is over or below the threshold value then by other factors, which furnaces or APCDs represent. When the chlorine level in the waste is below the threshold value at 0.8-1.1%, the formation of PCDDs dominates, probably because the chlorine is used to chlorinate the non-substituted phenol to produce chlorophenols, which are important precursors for PCDDs. rather than chlorinate the dibenzofuran. While the chlorine level in the waste exceeds this threshold (0.8-1.1%), the rates of formation of PCDFs increase faster than those of PCDDs, probably because the chlorine content in the waste contributes to the deterioration of combustion conditions, and many products of incomplete combustion (PICs) like PAHs, will grow to a substantial level. When PCDD/Fs are formed from PAHs, the formation rates of PCDFs are higher than those of PCDDs.

Emission estimation and congener-specific characterization of polybrominated diphenyl ethers from various stationary and mobile sources

Here we show that combustion sources, including waste incinerators, metallurgical processes, power-heating systems and so on, are also important emitters of polybrominated diphenyl ethers (PBDEs) to the atmosphere. Geometric mean PBDE concentrations in the stack flue gases of the combustion sources ranged from 8.07 to 469 ng/Nm3. The sinter plants (24.7 mg/h), electric arc furnaces (EAFs) (11.3 mg/h) and power plants (50.8 mg/h) possessed the largest PBDE emission rates, which were several orders higher than those of the other reported sources. The occurrences of the PBDEs in the flue gases of the power plants and vehicles, as well as their PBDE concentrations statistically highly correlated with combustion-originated PCDD/Fs, revealing that PBDEs should be the products of combustion. The ranking of major PBDE emission sources in Taiwanese PBDE inventory for combustion sources was power plants (30.85 kg/year), vehicles (14.9 kg/year) and metallurgical processes (5.88 kg/year).

Characterization of multiple airborne particulate metals in the surroundings of a municipal waste incinerator in Taiwan

Abstract Heavy metals are one of the concerned pollutants emitted by the municipal waste incineration system (MWIs). The objective of this study was to evaluate the potential impact on local airborne metals from the emissions of an MWI. Aerosol samples were simultaneously collected at eight different sites around the municipal waste incinerator using PS-1 sampler. The concentrations of 16 elements (Mg, Al, Fe, Cu, Zn, Pb, Ti, V, Cr, Mn, Co, Ni, As, Cd, Ba and Hg) were quantified by inductively coupled plasma-mass spectrometry (ICP–MS) and atomic absorption spectrometer (AA). The profiles of the 16 metals in the surroundings of a municipal incinerator in central Taiwan were compared with those of the emission sources. The results showed that the profiles of multiple metals obtained at all sampling sites were similar to those emitted from the MWI stack. These findings suggested that the local airborne metal pollutants might probably derive from the stack emission of the MWI. Using cadmium as an index metal, it was found that the metals like Mg, Ti, V, Cr, Mn, Co, Ni, As, and Hg are highly influenced by the stack emission from the municipal incinerator. Moreover, the ratio of other metals to Cd that were increased with the distance from the incinerator. This might be due to the additional sources contributed to airborne metals following the emission from the incinerator and a difference in particle size of each particle-bound metal.

Emissions of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans from Stack Gases of Electric Arc Furnaces and Secondary Aluminum Smelters

Abstract This study investigates the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from four electric arc furnaces (EAFs) and eight secondary aluminum smelters (secondary ALSs) in Taiwan. The mean PCDD/F International-Toxicity Equivalents (I-TEQ) concentrations in the stack gases of these EAFs and secondary ALSs are 0.28 ng I-TEQ/Nm3 (relative standard deviation [RSD = 100%) and 3.3 ng I-TEQ/Nm3 (RSD = 260%), respectively. The high RSDs, especially for those obtained from secondary ALSs, could be caused by the intrinsic differences in their involved feeding materials, furnace operating conditions, and air pollution control devices. The mean I-TEQ emission factor of PCDD/Fs for EAFs (1.8 μg I-TEQ/tonne-feedstock) is lower than that for secondary ALSs (37 μm g I-TEQ/tonne-feedstock). This result might be because the involved furnace temperatures for secondary ALSs (650–750 °C) are lower than those for EAFs (1600–1700 °C), resulting in the deterioration of the combustion condition, leading to the formation of PCDD/Fs during the industrial process. This study found that the total PCDD/F emissions from EAFs (20 g I-TEQ/yr) and secondary ALSs (18 g I-TEQ/yr) are ∼27, 53, and ∼24, 49 times higher than those from municipal solid waste incinerators (MSWIs; 0.74 g ITEQ/yr) and medical waste incinerators (MWIs; 0.37 g I-TEQ/yr), respectively; while those are 44 and 40% of total PCDD/F emission from sinter plants (45 g I-TEQ/yr), respectively. Considering a more stringent emission limit has been applied to waste incinerators (0.1 ng I-TEQ/Nm3) in Taiwan lately, the results suggest that the control of the emissions from metallurgical processes has become the most important issue for reducing the total PCDD/F emission from industrial sectors to the ambient environment.

Polybrominated diphenyl ethers in various atmospheric environments of Taiwan: Their levels, source identification and influence of combustion sources

In this study, ambient air samples from different atmospheric environments were examined for both PBDE and PCDD/F characteristics to verify that combustion is a significant PBDE emission source. The mean ± SD atmospheric PBDE concentrations were 165 ± 65.0 pg Nm(-3) in the heavy steel complex area and 93.9 ± 24.5 pg Nm(-3) in the metals complex areas, 4.7 and 2.7 times higher than that (35.3 ± 15.5 pg Nm(-3)) in the urban areas, respectively. The statistically high correlation (r=0.871, p<0.001) found between the atmospheric PBDE and PCDD/F concentrations reveals that the combustion sources are the most likely PBDE emission sources. Correspondence analysis shows the atmospheric PBDEs of the heavy steel and metals complex areas are associated with BDE-209, -203, -207, -208, indicative of combustion source contributions. Furthermore, the PBDEs in urban ambient air experience the influence of the evaporative releases of the commercial penta- and octa-BDE mixtures, as well as combustion source emissions. By comparing the PBDE homologues of indoor air, urban ambient air, and stack flue gases of combustion sources, we found that the lighter brominated PBDEs in urban ambient air were contributed by the indoor air, while their highly brominated ones were from the combustion sources, such as vehicles. The developed source identification measure can be used to clarify possible PBDE sources not only for Taiwanese atmosphere but also for other environmental media in other countries associated with various emission sources in the future.

Validation of the CALUX bioassay as a screening and semi-quantitative method for PCDD/F levels in cow's milk.

The objectives of this study were first to set up and validate the quality criteria of the Xenobiotic Detection Systems-chemical activated luciferase gene expression (CALUX) bioassay for the analysis of cows milk samples spiked with polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). The application of this bioassay was then tested by analyzing 28 commercially available pasteurized milk samples and comparing the data with the reference method for PCDD/F analysis. The CALUX criteria from the U.S. EPA and the European Union (EU) were calculated from 16 replaced spiked milk (SM) samples and 8 performance evaluation (PE) samples to validate the CALUX bioassay system. The CALUX bioassay criteria included control chart for quality control (QC) standards, recovery efficiency, and data comparability. The control chart for QC standards were both within the micro+/-2sigma range. The recovery efficiencies ranged from 60.4% to 106% with an average of 79.9% (relative standard deviation (RSD): 20.7%). The mean of data comparability (i.e., relative percent difference, RPD) between CALUX bioassay and high-resolution gas chromatography and high-resolution mass spectrometry (HRGC/HRMS) was 19.0% for SM samples. For the PE samples, Pearsons correlation coefficient between CALUX and the HRGC/HRMS method was 0.953. The high correlation shows that the CALUX system is suitable as a screening method and a semi-quantitative method to analyze the PCDD/F concentration in milk samples. Next, the validated CALUX bioassay was applied to measure 28 commercially available pasteurized milk samples. These milk samples were also analyzed with the HRGC/HRMS method to compare the analysis data from two different methods. There is no false negative sample when applying the bioassay to pasteurized milk and PE samples as a screening method and a semi-quantitative method. The present study indicates that CALUX is a powerful bioassay method for screening a large number of milk samples.

Liquid crystalline polysiloxane polymer as stationary phase in gas chromatography capillary column for the separation of dioxin/furan compounds

A side-chain liquid crystalline polysiloxane polymer (PS3DBDE1) with high purity and high isotropic transition temperature served as a stationary phase in an attempt to chromatographize the dioxin/furan compounds. The polymer was coated on the inner surface of a 0.25 mm I.D. capillary column by using the static coating method, forming a film with a thickness of df approximately 0.25 microm. A commercial standard solution (US EPA 1613 standard solution 1613CS4) containing polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was used to test the chromatographic behavior of the laboratory-made capillary column. Two commercial capillary columns HP-5MS (Hewlett-Packard) and RTX-5MS (RTX) were chosen to compare their chromatographic behavior. The results show that by the use of PS3DBDE1 the isomeric pair compounds 1,2,3,4-TeCDD vs. 2,3,7,8-TeCDD and 1,2,3,4,7,8-HxCDD vs. 1,2,3,6,7,8-HxCDD and the same substituted-chlorine number compounds 1,2,3,4,6,7,8-HpCDF vs. 1,2.3,4,6,7,8-HpCDD and 1,2,3,4,6,7,8,9-OCDD vs. 1,2,3,4,6,7,8,9-OCDF had higher resolution than HP-5MS and RTX-5MS as suggested by the column makers.

All-hydrocarbon liquid crystalline polysiloxane polymer as stationary phase in gas chromatography capillary column for separation of isomeric compounds of polynuclear aromatic hydrocarbons.

Two new and high-purity all-hydrocarbon side-chain liquid crystalline polysiloxane polymers were synthesized by grafting all-hydrocarbon liquid crystal monomers onto a polymethylhydrosiloxane backbone. The two polysiloxane polymers show both smectic B and E mesophases which were characterized by (differential scanning calorimetry and X-ray analysis. As stationary phases, these liquid crystalline polysiloxane polymers were coated on the inner surface of a capillary column (i.d. = 0.32 mm, film thickness d(f) ≈ 0.25 μm) using the static coating method. The capillary column was installed on a GC/MS instrument. We used a standard commercial mixture of 21 species of polynuclear aromatic hydrocarbons (purchased from Supelco Co. and Merck Co.) to test the chromatographic behavior of the coated stationary phase. Test results of the isomeric pair compounds show a better separation resolution than identical tests using the commercial HP-5 capillary column, which is a standard and state-of-the-art analytical tool for the chromatographic resolution of PAHs.

Establishment of a fluorescence resonance energy transfer-based bioassay for detecting dioxin-like compounds

Dioxins comprise a group of compounds which contain a double aromatic ring-like structure. They are among the most prevalent and toxic environmental pollutants. Accumulation of dioxins in human tissues poses a potential threat to human health. Currently, analytical chemical procedures dominate dioxin-detection protocols. In this study, we established a fluorescence resonance energy transfer (FRET)-based dioxin-detection bioassay. Aryl hydrocarbon receptor (AHR) and AHR nuclear translocator (ARNT) fused-cyan fluorescent protein (CFP) and -yellow fluorescent protein (YFP) constructed were transiently co-transfected into rat hepatoma cell line, H4IIEC3 cells. Our results showed that no FRET signals were detected in AHR-CFP- and ARNT-YFP-transfected H4IIEC3 cells. However, dioxin treatments upregulated FRET signals in these transfected cells in a dose-dependent manner. This work highlighted the potential of FRET technique in the detection of dioxin-like compounds.