Guo-Ping Chang-Chien

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.

Distribution of polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in municipal solid waste incinerators.

The stack flue gases and the ashes in different units of two municipal solid waste incinerators (MSWIs) are sampled to investigate the characteristics of polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Bottom ashes (BA) exhibited much higher PBDD/F (8.11-52.2 pg TEQ/g) and PBDE contents (20.4-186 ng/g) than those of fly ashes (0.0932-2.02 pg TEQ/g and 0.332-25.5 ng/g), revealing that the PBDD/Fs and PBDEs in the feeding waste may not be completely destroyed. The PBDE concentrations/contents in the stack flue gases (26.1-109 ng/Nm(3)) and in the BA (20.4-186 ng/g) of the MSWIs could reach three orders higher than those in the atmosphere and reference soils. PBDE contributions to the environment from the stack flue gases or the reutilization of BA of MSWIs should not be ignored from the developing PBDE inventory.

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.

Characterizing the emissions of polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) from metallurgical processes.

This study investigated the characteristics of polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in the stack flue gases of the metallurgical processes. An examination of the PBDEs existing in the stack flue gases of sinter plants revealed that PBDEs can form during the combustion processes through the similar formation conditions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The PBDD/F and PBDE emission rates of the metallurgical facilities were 0.446-3.19 microg TEQ/h and 4470-27000 microg/h, correspondingly. Both emission rates could reach several orders higher than those of the reported sources, revealing that the metallurgical facilities are not only important PCDD/F but also significant PBDD/F and PBDE emission sources to the environment. BDE-209 is the most abundant PBDE congener in the emissions of metallurgical facilities and is found to be dominant in the atmosphere and soils. However, few studies have considered metallurgical facilities as potential PBDE contributors to the environment. Because PBDEs could form or not be completely destroyed in the feeding materials in the combustion system, PBDE contributions from combustion emission sources to the atmosphere should not be ignored and need further investigation.

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).

Multivariate analysis of heavy metal contaminations in seawater and sediments from a heavily industrialized harbor in Southern Taiwan

Heavy metal pollution, including chromium, zinc, arsenic, cadmium, mercury, copper, lead, and aluminum, in the largest industrial harbor in southern Taiwan was investigated. Increasing metal contamination was observed by monitoring heavy metal concentrations in seawater and sediments and estimating the enrichment factors, particularly those inside the harbor. Compared to other metal-polluted harbors worldwide, the presence of chromium in the sediments was relatively high. Excluding the background contribution, the harbor area was polluted by outflows from river mouths, wastewater discharging pipes, and point sources near industrial activities within the harbor. It is shown by principal component and cluster analyses that metal contamination was affected by a wide range of different and complex contamination mechanisms inside and outside the harbor, suggesting managing the pollution using straightforward strategies, i.e., solutions that only consider a single source or single pathway of metal emissions, is problematic.

Polycyclic aromatic hydrocarbon-induced oxidative stress and lipid peroxidation in relation to immunological alteration

Objectives We evaluated the association between exposure to polycyclic aromatic hydrocarbons (PAHs) and immunological measurements using blood samples from coke oven workers exposed to high and low PAH levels. Methods A population-based cross-sectional study was conducted from 2008–2009 with coke oven workers and steel-rolling workers as the exposed and control groups, respectively. Questionnaires on basic demographic information were administered. Personal breathing zone and urine samples were collected to quantify personal PAH intake and biological response doses. Immunological and cytokine parameters in serum were analysed. Urinary malondialdehyde (MDA) and 8-hydroxydeoxyguanosine (8-OHdG) were analysed to determine oxidative stress induced by PAHs in relation to altered humoural immunological status. Results Mean levels of serum immunoglobulin A (IgA) and TNF-α were significantly increased in coke oven workers compared to steel-rolling workers who had no or minimal PAH exposure (p=0.0033 and p<0.0001, respectively). There were no significant differences in mean levels of IL-4 and IL-10 between coke oven workers and steel-rolling workers. Moderate activation of lipid peroxidation and oxidative damage as determined by plasma MDA and 8-OHdG levels were detected simultaneously with significant alterations in IgA and IgE levels. Multiple regression analyses demonstrated that PAHs with high molecular weights >252 (dibenzo(a,h)anthracene, benzo(a)pyrene, benzo(a)anthracene and/or indeno(1,2,3-cd)pyrene) correlated with IgA and IgE levels. Conclusions This study showed that coke oven workers with chronic exposure to PAHs may develop immunological alteration. Oxidative stress and lipid peroxidation induced by PAHs may partly explain the alteration in immunological parameters.

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.

Determination of levels of persistent organic pollutants (PCDD/Fs, PBDD/Fs, PBDEs, PCBs, and PBBs) in atmosphere near a municipal solid waste incinerator.

This work develops a comprehensive approach for quantitatively analyzing polychlorinated and polybrominated dibenzo-p-dioxins (PCDDs/PBDDs), dibenzofurans (PCDFs/PBDFs), biphenyls (PCBs/PBBs) and diphenyl ethers (PBDEs). This technique, based on multiple (silica, alumina, and active carbon) columns, can be applied to prepare samples for determining the five group compounds based on high-resolution gas chromatography/high-resolution mass spectrometry. The method was also validated by analyses of blank and spiked samples. In the sampled air, the mean PCDD/F, PCB, PBDD/F, PBDE, and PBB concentrations were 59.6 fg WHO-TEQ Nm(-3), 6.74 fg WHO-TEQ Nm(-3), 12.2 fg WHO-TEQ Nm(-3), 52100 fg Nm(-3), and 341 fg Nm(-3), respectively. The WHO-TEQ of dioxin-like PCB and PBDD/Fs counted for 8.9% and 16% of total TEQ (summed over PCDD/Fs, PBDD/Fs, and dioxin-like PCBs), respectively, suggesting that the atmospheric concentrations of dioxin and dioxin-like compounds should be regulated together because of the persistence and toxicity of PBDD/Fs and dioxin-like PCBs.