Guorui Liu

Atmospheric Emission of PCDD/Fs, PCBs, Hexachlorobenzene, and Pentachlorobenzene from the Coking Industry

The coking process is considered to be a potential source of unintentionally produced persistent organic pollutants (UP-POPs). However, intensive studies on the emission of UP-POPs from the coking industry are still very scarce. Emission of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), hexachlorobenzene (HxCBz), and pentachlorobenzene (PeCBz) covered under the Stockholm Convention were investigated for the coking process in this study. Stack gases from some typical coke plants in China were collected and analyzed to estimate the emission of UP-POPs from the coking industry. Emission factors of 28.9 ng WHO-TEQ tonne(-1) for PCDD/Fs, 1.7 ng WHO-TEQ tonne(-1) for dl-PCBs, 596 ng tonne(-1) for HxCBz, and 680 ng tonne(-1) for PeCBz were derived based on the investigated data. The annual emissions from the global coking industry were estimated to be 15.8 g WHO-TEQ for PCDD/Fs, 0.93 g WHO-TEQ for dl-PCBs, 333 g for HxCBz, and 379 g for PeCBz, respectively (reference year 2007). According to the distribution of PCDD/Fs, we argued for the de novo synthesis to be the major pathway of PCDD/F formation. With regard to the characteristics of dl-PCBs, the most abundant congener was CB-118, and the most dominant contributor to the total WHO-TEQ of dl-PCBs was CB-126.

Estimation and Characterization of Polychlorinated Naphthalene Emission from Coking Industries

Occurrence of polycyclic aromatic hydrocarbons (PAHs) during the coking process has been widely recognized. The formation of polychlorinated naphthalenes (PCNs) from PAHs during some thermal related processes has been confirmed in many studies. Thus, the coking process is assumed to be a potential source of PCNs. However, intensive investigations on PCN emissions during the coking process are lacking. In order to evaluate PCN emissions from the coking process, an intensive study comprising 11 typical coke plants was undertaken. PCNs were qualified and quantified by isotope dilution HRGC/HRMS techniques. The concentrations of PCNs in stack gas samples collected from the investigated coke plants were in the range of 1.6-91.8 ng Nm(-3) (0.08-4.23 pg TEQ Nm(-3)). The emission factors of PCNs were found to be in the range of 0.77-1.24 ng TEQ per ton of coke production. The estimated annual toxic emissions of PCNs from the global coking industry vary from 430 to 692 mg TEQs. Characteristics of the PCN profiles were dominated by the lower chlorinated homologues, with mono-CN being the most abundant homologue. According to the PCN distribution and correlations of PCN homologues, it was speculated that chlorination is possibly the dominant pathway of PCN formation during the coking process.

Estimation and Congener-Specific Characterization of Polychlorinated Naphthalene Emissions from Secondary Nonferrous Metallurgical Facilities in China

Secondary nonferrous production is addressed as one of the potential sources of the unintentionally produced persistent organic pollutants (UP-POPs) due to the impurity of raw material. Although there are inventories of dioxin emissions from secondary nonferrous metallurgical facilities, release inventories of polychlorinated naphthalenes (PCNs) are scarce. This study selected typical secondary copper, aluminum, zinc, and lead plants to investigate the emissions of PCNs in secondary nonferrous production in China. The toxic equivalency (TEQ) emission factor for PCNs released to the environment is highest for secondary copper production, at 428.4 ng TEQ t(-1), followed by secondary aluminum, zinc, and lead production, at 142.8, 125.7, and 20.1 ng TEQ t(-1), respectively. PCNs released in secondary copper, aluminum, lead, and zinc production in China are estimated to be 0.86, 0.39, 0.009, and 0.01 g TEQ a(-1), respectively. Analysis of stack gas emission from secondary nonferrous production revealed that less-chlorinated PCNs are the dominant homologues, with mono- to tri-CNs making the most important contributions to the concentration. However, for fly ash, the more highly chlorinated PCNs such as octa-CN are the dominant homologues.

Estimation and characterization of PCDD/Fs, dl-PCBs, PCNs, HxCBz and PeCBz emissions from magnesium metallurgy facilities in China

Magnesium production is considered to be one potential source of unintentional persistent organic pollutants (unintentional POPs). However, studies on the emissions of unintentional POPs from magnesium metallurgy are still lacking. Emissions of unintentional POPs, such as polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), polychlorinated naphthalenes (PCNs), hexachlorobenzene (HxCBz) and pentachlorobenzene (PeCBz) are covered under the Stockholm Convention. In this study, these emissions were investigated through a magnesium smelting process. Stack gas and fly ash samples from a typical magnesium plant in China were collected and analyzed to estimate the emissions of unintentional POPs from magnesium metallurgy. Emissions factors of 412 ng TEQ t(-1) for PCDD/Fs, 18.6 ng TEQ t(-1) for dl-PCBs, 3329 μg t(-1) for PCNs, 820 μg t(-1) for HxCBz, and 1326 μg t(-1) for PeCBz were obtained in 2009. Annual emissions from magnesium metallurgy in China were estimated to be 0.46 g WHO-TEQ for PCDD/Fs and dl-PCBs, 1651 g for PCNs, 403 g for HxCBz and 653 g for PeCBz, respectively.

Sources of unintentionally produced polychlorinated naphthalenes.

The European Union has proposed that polychlorinated naphthalenes (PCNs) should be included in the annexes of the Stockholm Convention on Persistent Organic Pollutants, signifying that there will be an increase in activities aimed at reducing PCN emissions. It has been speculated that the unintentional formation and emission of PCNs from industrial activities are the main current sources, because they have ceased to be manufactured as industrial chemicals in many countries. In this review, we provide a brief overview of recent progress in research into the unintentional formation and emission of PCNs from various industries that use thermal processes. The sampling and analysis of PCNs, and their formation mechanisms during thermal processes, are reviewed and discussed. The emission levels, emission profiles, and emission factors of PCNs from a number of industries that use thermal processes are summarized and compared, and this will provide helpful information for planning PCN source control measures and studying the source-receptor relationships of PCNs.

Atmospheric emission of polychlorinated biphenyls from multiple industrial thermal processes

In this study, field measurements were conducted to estimate and characterize the atmospheric emission levels and profiles of polychlorinated biphenyls (PCBs) from multiple industrial thermal processes. The emission levels and profiles of PCBs from five types of thermal processes at twenty-three plants were studied and compared with eight processes reported in our previous studies. Correlation analysis was preformed to identify a marker congener for emission of ΣPCB. A significant correlation was observed between congener CB-118 and ΣPCB (R(2)=0.65 and p<0.01), which suggests that CB-118 is a good marker congener for emission of ΣPCB. The profiles of PCBs emitted from the thirteen thermal processes were compared, and this information could be used for studying source-receptor relationships and identifying the specific sources of PCBs. To prioritize the sources for control, the concentrations of PCBs from thirteen industrial thermal sources were compared. The PCB concentrations from secondary zinc smelting and thermal wire reclamation were about one to three order magnitude higher than those of other sources, which suggests that these two sources be given priority in PCB source control. Finally, the atmospheric emission factors of PCBs from the thirteen industrial sources were summarized, and these data will be useful for developing an integrated emission inventory of PCBs.

Atmospheric emission of polychlorinated naphthalenes from iron ore sintering processes

Iron ore sintering processes constitute significant sources of dioxins, and studies have confirmed a close correlation between polychlorinated naphthalenes (PCNs) and dioxin formation. Thus, iron ore sintering processes are thought to be a potential source of PCNs, although intensive investigations on PCN emissions from sintering processes have not been carried out. Therefore, the aim of the present study was to qualify and quantify PCN emissions from nine sintering plants operating on different industrial scales. PCN concentrations ranged from 3 to 983 ng m(-3) (0.4-23.3 pg TEQ(PCN) m(-3)) and emission factors ranged from 14 to 1749 μg t(-1) (0.5-41.5 ng TEQ(PCN) t(-1)), with a geometric mean of 84 μg t(-1) (2.1 ng TEQ(PCN) t(-1)). The estimated annual emission of PCNs from sintering processes in China was 1390 mg TEQ(PCN). These figures will assist in the development of a PCN emissions inventory. Regarding emission characteristics, PCNs mainly comprised low-chlorinated homologs. The ratios of several characteristic PCN congeners were also measured and compared with those from other sources. Taken together, these results may provide useful information for identifying the sources of PCNs produced by iron ore sintering processes.

A preliminary investigation of unintentional POP emissions from thermal wire reclamation at industrial scrap metal recycling parks in China

Thermal wire reclamation is considered to be a potential source of unintentional persistent organic pollutants (unintentional POPs). In this study, unintentional POP concentrations, including PCDD/Fs, dioxin like PCBs (dl-PCBs), polychlorinated naphthalenes (PCNs), hexachlorobenzene (HxCBz) and pentachlorobenzene (PeCBz), were quantified in flue gas and residual ash emissions from thermal wire reclamation at scrap metal dismantling parks in Zhejiang Province, China. The total average TEQ emissions of the investigated unintentional POPs from flue gas and residual ash in two typical scrap metal recycling plants ranged from 13.1 to 48.3ngTEQNm(-3) and 0.08 to 2.8ngTEQg(-1), respectively. The dominant PCDD/F congeners were OCDD, 1,2,3,4,6,7,8-HpCDD, OCDF and 1,2,3,4,6,7,8-HpCDF, while PCB-126 and PCB-169 were the main contributors to the toxicity of the dl-PCBs. There were clear differences in the distribution dl-PCBs congeners contributing to the TEQ concentrations in the flue gas samples from the two plants. The PCN TEQs were dominated by PCN-66/67 and PCN-73. Although thermal wire reclamation in incinerators has been proposed as an alternative to open burning, there are still considerable environmental risks associated with regulated incinerators, and unintentional POP emissions from thermal wire reclamation sites need to be controlled by local government agencies.

Comparison of PCDD/F levels and profiles in fly ash samples from multiple industrial thermal sources

A comprehensive comparison of the levels and profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in fly ash samples from multiple industrial sources may help to prioritize sources and to understand discrepancies in profiles. In this study, PCDD/F data from 113 fly ash samples from 14 sources reported in previous studies were summarized and compared. The highest PCDD/F levels occurred in samples from secondary copper smelting (SCu). Although PCDD/F levels from secondary zinc smelting (SZn) were slightly lower than those of SCu, the PCDD/F profiles varied widely between the two sources. For SCu, more chlorinated homologs were dominant, with highest degrees of chlorination being 6.6 for PCDF and 7.2 for PCDD. For SZn, less chlorinated homologs were dominant, with lowest degrees of chlorination being 4.4 for PCDF and 4.8 for PCDD. We speculate that copper and zinc might promote PCDD/F formation by catalyzing different pathways of thermal reactions. Diagnostic ratios of specific PCDD/F congeners for different sources were suggested to identify potential sources of PCDD/Fs in the environment. Equations describing correlations between congeners and PCDD/F toxic equivalents were established, which may be useful for rapid and inexpensive screening of the toxic levels of PCDD/Fs in fly ash samples.

A preliminary investigation on emission of polychlorinated dibenzo-p-dioxins/dibenzofurans and dioxin-like polychlorinated biphenyls from coke plants in China.

Thermal related processes are widely recognized as the main sources of formation and emission of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It is well known that, carbonization of coal in coke production involves many thermal reactions at high-temperature. However, there are still no strong evidences to identify coking processes as source of PCDD/Fs and PCBs. In this study, coke production was qualified and quantified for emission of PCDD/Fs and dioxin-like PCBs (dl-PCBs) in some typical coke plants in China. In the preliminary investigation, stack gases from three typical coke plants were collected, and dl-PCBs and 2378-substituted PCDD/Fs were analyzed by isotope dilution HRGC/HRMS technique. The total toxic equivalents of dl-PCBs and PCDD/Fs were in the range of 1.6-1785.4pg WHO-TEQNm(-3). For dl-PCBs, the most abundant congener was CB-118, and the most dominant contributor to total WHO-TEQ of dl-PCBs was CB-126. With regard to PCDD/Fs, four congeners comprised of OCDD, 1234678-HpCDD, 1234678-HpCDF and OCDF were the predominant species in stack gases. Further investigation on the emission of dioxins from coking industry is still in process.