Quasi-dynamic leaching characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans from raw and solidified waste incineration residues

Quasi-dynamic leaching characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from raw and solidified air pollution control (APC) residues were examined via a nine-time multiple leaching test. The effect of injected activated carbon in the APC residues on the PCDD/F leachability was also evaluated. When humic acid solution was used as a leachant, the leaching concentrations of PCDD/Fs fluctuated between the first and the fifth leaching, followed by a gradual increase and then suddenly reached maximum values at the leaching sequences around seventh and eighth. This significant enhancement in PCDD/F leachability was mainly due to an increase in the release of highly chlorinated PCDD/Fs. Leaching of PCDD/Fs with n-hexane was, in contrast, primarily caused by the partitioning of hydrophobic PCDD/Fs between the APC residue surface and the liquid phase of n-hexane. Consequently, the largest leaching concentrations for n-hexane tests achieved at the first leaching, followed by a decrease and reached plateaus. Solidification/stabilization (S/S) decreased the PCDD/F leachability up to the fifth leaching by the use of humic acid solution. However, S/S increased the PCDD/F leaching concentrations and rates with n-hexane. The activated carbon in APC residues significantly inhibited the release of PCDD/F with n-hexane. The inhibiting effect provided by activated carbon was, however, less significant by the use of humic acid solution.     

Influence of start-up on PCDD/F emission of incinerators

This study aims to evaluate the influence of start-up on polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) concentration in the stack flue gas of incinerators and its contributing PCDD/F emission. The PCDD/F emission of the first sample among three consecutive stack flue gas samples of five intermittent incinerators, which sampled at a stable combustion condition after start-up, is 2-3 times higher than the mean of the others. For verifying the PCDD/F characteristics of incinerators during start-up, one continuous MSWI was investigated for two years. The elevated PCDD/F emissions of the MSWI during start-up could reach 96.9 ng I-TEQN m(-3) and still maintained a high PCDD/F emission (40 times higher than the Taiwan emission limit) even 18 h after the injection of activated carbon, indicating the memory effect. Taking the MSWI for example, which consists of four incinerators, the estimated annual PCDD/F emission from normal operational conditions was 0.112 g I-TEQ. However, one start-up procedure can generate approximately 60% of the PCDD/F emissions for one whole year of normal operations. And the PCDD/F emission, which is the result of the start-ups of four incinerators, was at least two times larger than that of a whole year's normal operations, without consideration for the PCDD/F emission contributed by the long lasting memory effect.     

Effects of experimental parameters on NF(3) decomposition fraction in an oxygen-based RF plasma environment

Clean procedure is one of the major emitters of perfluorinated compounds (PFCs) in semiconductor manufacturing. Nitrogen trifluoride (NF(3)) is increasingly the process gas of choice for eliminating PFC emissions. However, its toxic to human and similar global warming potential compared to most other PFCs made NF(3) warranted much more investigation. This study demonstrated a radio-frequency plasma system for decomposing NF(3). The effects of experimental parameters: input power, O(2)/NF(3) ratio, operational pressure and NF(3) feeding concentration on NF(3) decomposition fraction (eta(NF3)) and energy efficiency E(NF3) were examined in detail. The analytical results demonstrated that the NF(3) was almost completely decomposed (>99%) at input power=30W, [NF(3)](in)=1.0% and eta(NF3) increased with input power. However, adding O(2) to the system inhibited NF(3) decomposition and decreased E(NF3). Moreover, eta(NF3) and E(NF3), decreased with gradually increasing operational pressure. Notably, increasing the NF(3) feeding concentration increased molecule density, reducing eta(NF3), but increasing E(NF3). Furthermore, the products detected in the NF(3)/O(2)/Ar plasma system were NO(2), NO, N(2)O, SiF(4), N(2) and F(2). Potential reaction pathways in the oxygen-based NF(3) plasma environment were built-up and elucidated.     

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.     

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).     

Effects of injected activated carbon and solidification treatment on the leachability of polychlorinated dibenzo-p-dioxins and dibenzofurans from air pollution control residues of municipal waste incineration

To assess the effectiveness of the injected activated carbon, cement, and sulfur-containing chelating agent in controlling polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) release from the surface of air pollution control (APC) residues, this study examined the leachability of PCDD/Fs from APC residues generated by municipal solid waste incinerators. Results showed that PCDD/Fs were stably retained in the APC residues when the samples were leached with acetic acid solution. Highly chlorinated PCDD/F homologues (i.e., hepta- and octa-CDDs and CDFs) were relatively easy to leach. The leaching percentages of PCDD/Fs from raw APC residue samples containing activated carbon were smaller than those from samples without activated carbon, especially when n-hexane was used as the leachant. These results indicate that the flue gas injected activated carbon not only controls PCDD/F emissions, but also suppresses the leachability of PCDD/Fs from the APC residues. Solidification/stabilization (S/S) processes with 30wt% cement and 5wt% sulfur-containing agent can additionally decrease the leachability of PCDD/Fs with humic acid. Using n-hexane as the leachant, S/S processes increased the leachability of PCDD/Fs. Various low chlorinated PCDD/F congeners were moreover leached out of the APC residue samples, markedly increasing the leachate toxicity. The enhancement of leachability and toxicity owing to S/S processes may negatively impact the environment when APC residues are exposed to nonpolar organic solvents.     

An integrated approach for identification of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) pollutant sources based on human blood contents

Background, aim, and scope  

This study developed an integrated approach to identify pollutant sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) of workers based on their blood contents.     

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.     

Size distribution and leaching characteristics of poly brominated diphenyl ethers (PBDEs) in the bottom ashes of municipal solid waste incinerators

The particle size distributions and leaching characteristics of polybrominated diphenyl ethers (PBDEs) in the bottom ashes of two Taiwanese municipal solid waste incinerators (MSWIs A and B) were investigated to evaluate PBDE leaching into the environment through reutilization of bottom ashes. The PBDE contents in the bottom ashes of the MSWIs (29.0–243 ng/g) could be two orders higher than those in rural and urban soils. The PBDE fraction of the bottom ashes was more distributed in larger particles (> 0.25 mm). Similar trends were found for the PBDE contents in the bottom ashes and their PBDE leaching concentrations, revealing that the elevated PBDE contents in the bottom ashes may lead to a higher PBDE leaching mass. The leaching of PBDEs is attributed to diffusion driven by the concentration gradient and effective surface area. The normalized leaching ratios (NLRs) of PBDEs for the bottom ashes of the MSWIs are about four orders greater than those of PBDE-related raw materials and products, and this may be due to their porous structures having much greater effective surface area. The elevated NLRs of PBDEs thus deserve more attention when bottom ashes are recycled and reutilized as construction materials.     

Particle size distributions and health-related exposures of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) of sinter plant workers

This study measured particle size distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in two workplace atmospheres of the sintering grate and rough roll shredder in a sintering plant, and to assess their workers’ health-related exposures. We found that the PCDD/F concentration of the sintering grate (site A = 14.47 pg m⁻³) was lower than that of the rough roll shredder (site B = 17.20 pg m⁻³). Particle size distributions of PCDD/Fs were in the form of the unimodal with the mass median aerodynamic diameter (MMAD) of 4.74 μm and 5.23 μm, and geometric standard deviation (σ_g) of 3.15 and 2.15 for the site A and B, respectively. The above results suggest that the workplace of the site A had a less fraction of coarse particles than that of the site B. The estimated PCDD/F concentrations of the inhalable fraction (11.0 pg m⁻³) and thoracic fraction (8.89 pg m⁻³) of the site A were lower than those of the site B (12.4 and 9.39 pg m⁻³, respectively). But to the contrary the estimated respirable fraction of the site A (5.05 pg m⁻³) was slightly higher than that of the site B (4.93 pg m⁻³). Our results clearly indicate the importance to conduct particle size segregating samplings for assessing human PCDD/F exposures.