Wen-Jhy Lee

PAH emission from various industrial stacks

Abstract The emission of polycyclic aromatic hydrocarbons (PAHs) from various industrial stacks (blast furnace, basic oxygen furnace, coke oven, electric arc furnace, heavy oil plant, power plant and cement plant) in southern Taiwan were investigated. PAH concentrations ( μ g/N m 3 ) and PAH emission factors ( μ g/kg feedstock) were determined. In addition to these eight stationary industrial stacks, an industrial waste incinerator, a diesel engine and a gasoline-powered engine were selected and combined for the identification of source indicatory-PAHs in this study. The qualitative contribution of PAHs to the ambient air by various sources was estimated by factor analysis. Combustion of heavy oil produced considerably higher 4, 5 and 6+7-ring PAH concentration than other stacks. In addition, the HMW (higher molecular weight) PAH concentrations were significantly higher for the coke oven, the electric arc furnace and heavy oil combustion. Measured total-PAHs emission factors of eight stationary sources were between 77.0 and 3970 μ g/kg feedstock, while BaP (the most carcinogenic PAH) emission factors were between 1.87 and 15.5 μ g/kg feedstock. Among these eight emission sources, the heavy oil plant had both the highest total-PAH and the highest BaP emission factor. Indicatory PAHs of the cement plant were AcPy, Acp and Ant, which are all 3-ringed PAHs. However, the indicatory PAHs of the industrial waste incinerator were IND and CHR. For mobile sources (diesel- and gasoline-powered vehicles), the indicatory PAHs were mainly lower molecular weight PAHs (AcPy, FL and Flu). By using factor analysis, the cursorily qualitative analysis of PAH emission was found to be practicable.

PAH characteristics in the ambient air of traffic-source

Twenty-seven PAH (polycyclic aromatic hydrocarbon) samples in the ambient air of a traffic-source were investigated for their concentration, particle-bound PAH composition, phase distribution, time variation, and distance variation. In addition, 18 and 12 PAH samples in the ambient air of an urban site and a rural site, respectively, were determined and compared with those of the traffic-source. The total-PAH concentrations (gas + particle phases) in the ambient air of the traffic-source averaged approximately 5.3 and 8.3 times higher than mean values in the urban and rural atmosphere, respectively. The particle phase distribution of total-PAHs averaged 46.1, 18.7, and 20.6% measured at the traffic-source, urban site, and rural site, respectively. The condensation process prevailed in the ambient air of the traffic-source. Even though the TSP concentration near the traffic-source averaged only two times higher than the mean value measured on the urban or rural site, the particle-bound composition of 12 potentially carcinogenic PAHs, namely CYC, BaA, Chr, BbF, BkF, BeP, BaP, PER, IND, DBA, BbC, and BghiP, in the ambient air at the traffic-source averaged approximately 7.8 and 16.5 times higher than those measured at the urban and rural site, respectively. High concentrations of carcinogenic PAHs in the air near traffic sources is a strong factor in inducing a high rate of lung cancer in Taiwan. The results of both time-variation and distance-variation investigations show that traffic sources have a very significant impact on urban air quality. The results of PAH analyses of five commercial vehicle fuels showed that diesel had the highest total-PAH concentration (7341 mg/l). Lower molecular weight PAHs such as Nap, AcPy, and Acp were dominant in all vehicle fuels (concentration > 100 mg/l). Comparison of individual-PAH patterns in the vehicle fuels with those in the ambient air of traffic-source showed that a significant fraction of PAHs was formed during incomplete combustion with thermal synthesis.

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.

Particle-bound PAH content in ambient air

Ambient air samples from a traffic intersection, an urban site and a petrochemical-industrial site (PCI) were collected by using several dry deposition plates, two Microorifice uniform deposited impactors (MOUDIs), one Noll Rotary Impactor (NRI) and several PS-1 (General Metal Work) samplers from March 1994 to June 1995 in southern Taiwan, to characterize the atmospheric particle-bound PAH content of these three areas. Twenty-one individual polycyclic aromatic hydrocarbons (PAHs) were analyzed primarily by using a gas chromatograph/mass spectrometer (GC/MS). In general, the sub-micron particles have a higher PAH content. This is due to the fact that soot from combustion sources consists primarily of fine particles and has a high PAH content. In addition, a smaller particle has a higher specific surface area and therefore may contain more organic carbon, which allows for more PAH adsorption. For a particle size range between 0.31 and 3.2 microm, both Urban/Traffic and PCI/Traffic ratios of particle-bound total-PAH content have the lowest values, ranging from 0.25 to 0.28 (mean = 0.26) and from 0.07 to 0.13 (mean = 0.10), respectively. This indicates that, during the accumulation process, the PAH mass shifted from a particle phase to a gas phase, or the particles aggregated with lower PAH-content particles, resulting in a reduction in particle-bound PAH content. By using the particle size distribution data, the dry deposition model in this study can provide a good prediction for the PAH content of dry deposition materials. In general, lower molecular weight PAHs had a larger fraction of dry deposition flux contributed by the gas phase; for 2-ring PAH (50.4, 46.3 and 28.4%), 3-ring PAHs (15.2, 15.4 and 11.7%) and 4-ring PAHs (13.0, 3.60 and 5.01%) for the traffic intersection, urban and PCI sites, respectively. For higher molecular weight PAHs-5-ring, 6-ring and 7-ring PAHs-their cumulation fraction (F%) of dry deposition flux contributed by the gas phase was lower than 3.26%. At the traffic intersection, urban and PCI sites, the mass median diameter of dry deposition materials (MMD(F)) of individual PAHs was between 25.3 and 49.6 microm, between 27.6 and 43.9 microm, and between 19.1 and 41.9 microm, respectively. This is due to the fact that PAH dry-deposition primarily resulted from gravitational settling of the coarse particulates (> 10 microm).

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.

Characterization of PAHs in the atmosphere of carbon black manufacturing workplaces.

The objective of this study was set out to characterize the polycyclic aromatic hydrocarbon (PAH) content in the atmosphere of an oil furnace carbon black manufacturing plant located in southern Taiwan. A standard semi-volatile sampling train, the PS-1 sampler, was used to collect samples from eight areas, including the feedstock oil unloading, furnace, filtering/micro-pulverization, pelletizing, packaging, office/outside, office/inside, and boundary area, respectively. For each area, side-by-side static samples were collected simultaneously and a total of 16 samples were obtained. For each collected sample, the adsorbent-retained PAH content and the filter-retained PAH content were used directly to determine the concentrations of gaseous-phase PAHs and particle-bound PAHs, respectively. The gas chromatograph/mass spectrometer (GC/MS) technique was used for PAH analyses, and a total of 21 PAH species were determined. Results show the gaseous-phase PAHs accounted for only 69.2% of the total PAH content for samples collected from the packaging area, which was significantly lower than those samples collected from the rest of seven areas (ranging from 96.3 to 99.7%). The result is not so surprising since the packaging area had the highest dust concentration due to the releasing of carbon black dusts during the packaging process. In this study, we further examine the contribution of gaseous-phase PAHs to the total benzo[a]pyrene equivalent (BaP(eq)) content from the health-risk assessment view of point. It can be found the contribution of gaseous-phase PAHs to the total BaP(eq) content (63.1%) was quite comparable to the corresponding contribution to the total PAH content for samples collected from the packaging area. However, a different trend can be found for samples collected from the other seven areas, where the contributions of gaseous-phase PAHs to the total BaP(eq) content (ranging from 67.7 to 93.4%) were lower than the corresponding contributions to the total PAH content. The above results can be explained by PAH homologues that contained in both gaseous-phase and particle-bound PAHs. It was found the gaseous-phase PAHs contained higher fractions of less carcinogenic low molecular weight PAH homologues, whereas particle-bound PAHs contained higher fractions of more carcinogenic high molecular weight PAH homologues. Considering the contributions of gaseous-phase PAHs to both total PAH content and total BaP(eq) content were well above 50% for the eight studied areas, it is concluded that both particle-bound and gaseous-phase PAHs should be included for assessing the exposures of carbon black workers.

Effect of fuel aromatic content on PAH emission from a heavy-duty diesel engine

Polycyclic aromatic hydrocarbons (PAHs) emission tests for a heavy-duty diesel engine fueled with blend base diesel fuel by adding batch fractions of poly-aromatic and mono-aromatic hydrocarbons, Fluorene and Toluene, respectively, were simulated to five steady-state modes by a DC-current dynamometer with fully automatic control system. The main objective of this study is to investigate the effect of total aromatic content and poly-aromatic content in diesel fuels on PAH emission from the HDD engine exhaust under these steady-state modes. The results of this study revealed that adding 3% and 5% (fuel vol%) Fluorene in the diesel fuel increases the amount of total-PAH emission by 2.6 and 5.7 times, respectively and increases the amount of Fluorene emission by 52.9 and 152 times, respectively, than no additives. However, there was no significant variation of PAH emission by adding 10% (vol%) of Toluene. To regulate the content of poly-aromatic content in diesel fuel, in contrast to the total aromatic content, will be more suitable for the management of PAH emission.

Emission of polycyclic aromatic hydrocarbons from medical waste incinerators

Abstract This study was conducted on two batch-type medical waste incinerators (MWIs), including the one with a mechanical grate (MG-MWI) and the other with a fixed grate (FG-MWI) for the disposal of general medical waste and special medical waste, respectively. Both incinerators shared the same air-pollution control devices which were installed in series, including one electrostatic precipitator (ESP) and one wet scrubber (WSB). In addition to the investigated emissions of polycyclic aromatic hydrocarbons (PAHs) from both types of MWIs, the PAH removal efficiencies of air-pollution control devices were also included. In this study, the GC/MS technique was used to analyze the concentrations of 21 PAH species contained in the stack flue gas, ESP fly ash, WSB effluent, and incinerating ash. Results show that total-PAHs (i.e., the sum of 21 PAH species) in stack flue gas were dominated by LM-PAHs (i.e., two- to three-ringed PAHs), but in incinerating ash, ESP fly ash and WSB effluent we found that they were dominated by MM-PAHs (i.e., four-ringed PAHs) and HM-PAHs (i.e., five- to seven-ringed PAHs) for both types of MWIs. The above results due to air-pollution control devices used in both types of MWIs had much higher removal efficiencies on both MM-PAHs and HM-PAHs (>78%) than on LM-PAHs (

PAH emission from the incineration of waste oily sludge and PE plastic mixtures

A batch-type, controlled-air incinerator was used for the treatment of oily sludge and polyethylene (PE) plastic mixtures. The concentration and composition of 21 individual PAHs (polycyclic aromatic hydrocarbons) in the raw wastes, flue gas (gas and particle phases) and ash were determined. Stack flue-gas samples were collected by a PAH stack-sampling system. Twenty one individual PAHs were analyzed primarily by a gas chromatograph and a gas chromatography/mass spectrometer. Due to incomplete combustion, PAH content in the feeding wastes have a strong influence on PAH emission in both stack flue gas and ash residue. With the oily sludge in the feeding waste mixtures, the input mass of lower molecular weight PAHs — Nap, AcPy, Acp, Flu, PA, Ant and FL — was contributed mainly by liquid diesel, while the input mass of higher molecular weight PAHs — Pyr, CYC, CHR, BbF, BkF, BeP, BaP, PER, IND, DBA, BbC, BghiP and COR — was primarily contributed by the oily sludge. For the distribution of individual PAH mean output mass, lower molecular weight PAHs — Nap, AcPy, Acp and Flu — have > 87% of their mass discharged by the stack flue gas. However, the higher molecular weight PAHs — Ant, FL, CHR, BbF, BeP, BaP, PER, IND, DBA, BbC, BghiP and COR — have significant mass fractions (>18%) discharged by the ash residue. The total-PAH output/input mass ratios were between 0.00103 and 0.00360 and averaged 0.00203. This result indicated that the depletion of PAH mass in the combustion process was very significant. The PAH content in the fuel during the combustion process is the control factor of PAH emission. The co-combustion of oily sludge with plastic is a potential method of reducing the PAH emission and of saving the consumption of auxiliary fuel.

Size distribution and dry deposition of road dust PAHs

Abstract The size distribution of polycyclic aromatic hydrocarbons (PAHs) for road dust and for the engine exhaust of both gasoline-powered cars and motorcycles was investigated. In addition, by using the measured size distribution data, monitoring and modeling the PAH dry deposition, the contribution fraction of road dust on the dry deposition materials was also studied. Twenty-one PAHs were analyzed primarily by using a gas chromatograph/mass spectrometer (GC/MS). The mass median diameters (MMDs) of 21 individual PAHs for resuspendable road dust (cut size