Lirong Gao

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.

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.

Long-term persistence of polychlorinated dibenzo-p-dioxins and dibenzofurans in air, soil and sediment around an abandoned pentachlorophenol factory in China

Air, soils and sediments surrounding an abandoned pentachlorophenol (PCP) factory were sampled to determine the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), unintentionally formed during PCP production. The mean concentration of PCDD/Fs in ambient air was one order of magnitude higher than that of the reference site. A trend of decreasing concentrations with increasing distance from the factory was observed, suggesting this site has a significant influence on the regional ambient air. As for soil samples collected within 3 km from the factory and sediment samples from the adjacent rivers, high levels of contamination were found with WHO-TEQ concentrations of 193 ± 211 pg/g and 667 ± 978 pg/g, respectively. The PCDD/F homologue profiles of all samples were consistent with those found in the technical product of PCP, with OCDD as the dominant congener. These results indicate PCDD/Fs in the historical contaminated site pose a long-term impact on surrounding environment.

Background air levels of polychlorinated biphenyls in China.

Measurements of the atmospheric concentrations of polychlorinated biphenyls (PCBs) were taken in 11 background sites geographically distributed throughout China. Active high-volume samplers were employed during two deployment periods between November 2007 and November 2008. 12 dioxin-like and 7 indicator PCBs were identified and measured. To keep the consistency, the two sampling periods were set in the same seasons (autumn and winter) and there were few variations between the results at all sites. The congener profile of indicator PCBs was dominated by CB28 and CB52. The most abundant mono-ortho congener was CB118, and the most abundant non-ortho congener was CB77. This study is the first systematic investigation into background atmospheric PCB levels in China. The background indicator ∑(7)PCB levels in China are similar to those obtained at other background areas around the world.

Distribution and assessment of heavy metals in the surface sediment of Yellow River, China

Large amounts of heavy metals discharged by industrial cities that are located along the middle reach of Yellow River, China have detrimental impacts on both the ecological environment and human health. In this study, fourteen surface sediment samples were taken in the middle reach of the Yellow River. Contents of Zn, Pb, Ni, Cu, Cr, Cd, As were measured, and the pollution status was assessed using three widely used pollution assessment methods, including the single factor index method, Nemerow pollution index method and potential ecological risk index. The concentrations of the studied heavy metals followed the order: Zn>Cr>Cu>Ni>Pb>As>Cd. Nearly 50% of sites had Cu and Cr accumulation. The concentration of Cu at the Yiluo River exceeded the secondary standard value of the Environmental quality standard for soils. Comparison of heavy metal concentrations between this study and other selected rivers indicated that Cu and Cr may be the major pollutants in our case. The single factor index indicated that many samples were at high levels of pollution for Cu and Cd; the Nemerow pollution index indicated that the Yihe River, Luohe River, Yiluo River and Huayuankou were polluted. According to the results of potential ecological risk assessment, Cd in the tributaries of Luo River, Yihe River, and Yiluo River showed high risk toward the ecosystem and human health, Cd in Huanyuankou and Cu in Yiluo River showed a middle level of risk and other samples were at a low level of risk.

A Novel Method for Profiling and Quantifying Short- and Medium-Chain Chlorinated Paraffins in Environmental Samples Using Comprehensive Two-Dimensional Gas Chromatography–Electron Capture Negative Ionization High-Resolution Time-of-Flight Mass Spectrometry

Chlorinated paraffins (CPs) are complex technical mixtures containing thousands of isomers. Analyzing CPs in environmental matrices is extremely challenging. CPs have broad, unresolved profiles when analyzed by one-dimensional gas chromatography (GC). Comprehensive two-dimensional GC (GC×GC) can separate CPs with a high degree of orthogonality. A novel method for simultaneously profiling and quantifying short- and medium-chain CPs, using GC×GC coupled with electron capture negative ionization high-resolution time-of-flight mass spectrometry, was developed. The method allowed 48 CP formula congener groups to be analyzed highly selectively in one injection through accurate mass measurements of the [M - Cl](-) ions in full scan mode. The correlation coefficients (R(2)) for the linear calibration curves for different chlorine contents were 0.982 for short-chain CPs and 0.945 for medium-chain CPs. The method was successfully used to determine CPs in sediment and fish samples. By using this method, with enhanced chromatographic separation and high mass resolution, interferences between CP congeners and other organohalogen compounds, such as toxaphene, are minimized. New compounds, with the formulas C9H14Cl6 and C9H13Cl7, were found in sediment and biological samples for the first time. The method was shown to be a powerful tool for the analysis of CPs in environmental samples.

Spatial and seasonal distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans and polychlorinated biphenyls around a municipal solid waste incinerator, determined using polyurethane foam passive air samplers

Twenty-six ambient air samples were collected around a municipal solid waste incinerator (MSWI) in the summer and winter using polyurethane foam passive air samplers, and analyzed to assess the spatial and seasonal distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). Three stack gas samples were also collected and analyzed to determine PCDD/F (971 pg m(-3) in average) and PCB (2,671 pg m(-3) in average) emissions from the MSWI and to help identify the sources of the pollutants in the ambient air. The total PCDD/F concentrations in the ambient air samples were lower in the summer (472-1,223 fg m(-3)) than the winter (561-3913 fg m(-3)). In contrast, the atmospheric total PCB concentrations were higher in the summer (716-4,902 fg m(-3)) than the winter (489-2,298 fg m(-3)). Principal component analysis showed that, besides emissions from the MSWI, the domestic burning of coal and wood also contributed to the presence of PCDD/Fs and PCBs in the ambient air. The PCDD/F and PCB spatial distributions were analyzed using ordinary Kriging Interpolation and limited effect was found to be caused by emissions from the MSWI. Higher PCDD/F and PCB concentrations were observed downwind of the MSWI than in the other directions, but the highest concentrations were not to be found in the direction with the greatest wind frequency which might be caused by emissions from domestic coal and wood burning. We used a systemic method including sampling and data analysis method which can provide pioneering information for characterizing risks and assessing uncertainty of PCDD/Fs and PCBs in the ambient air around MSWIs in China.

Characteristics of air pollution by polychlorinated dibenzo-p-dioxins and dibenzofurans in the typical industrial areas of Tangshan City, China

The ambient air in vicinity of different industrial sources for PCDD/PCDFs was sampled by TSP/PM10 active samplers and passive PUF disk samplers in Tangshan City, a metropolis containing clusters of various industrial plants. The TEQ concentrations of PCDD/PCDFs ranged from 44.2 to 394.1 fg I-TEQ/m3 with an average of 169.9 fg I-TEQ/m3. 2,3,4,7,8-PeCDF was the dominant contributor to sigma TEQ, contributing 41% (12% to 55%), while 1,2,3,4,6,7,8-HpCDF, OCDD and OCDF were the major congeners for the total concentrations. The ratios of sigma PCDF/ sigma PCDD reached 2.54 on average, suggesting that de novo synthesis in thermal processes played an important role to the airborne pollution of PCDD/PCDFs. The similarities congener profiles indicated that TSP and PM10 active sampling methods are comparable for the determination of the PCDD/PCDFs in ambient air, and the ratios of concentrations determined by the two methods suggested that the PCDD/PCDFs tended to stay in fine particles. It was found that 2,3,7,8-TCDF and OCDD were the dominating congeners in the passive PUF disks samples. Through principal components analysis, the coke industry was suggested to be a relatively high potential emission source for PCDD/PCDFs in the ambient air of Tangshan, which was possibly formed by de novo synthesis mechanism. In this study, the atmospheric impacts to the environment from different industrial sources could be ranked as follows (from high to low): coking, iron sintering, steel making, power generation and chlorinate alkali chemical production industries.

Synergetic effect of alkaline earth metal oxides and iron oxides on the degradation of hexachlorobenzene and its degradation pathway.

The degradation of hexachlorobenzene (HCB) was carried out over physical mixtures of a series of alkaline earth metal oxides (MO: M=Mg, Ca, Sr, Ba) and iron oxides with different crystal types (Fe(x)O(y):Fe(2)O(3) or Fe(3)O(4)) at 300°C. These physical mixtures all showed a synergetic effect toward the degradation of HCB. A range of degradation products were identified by various methods, including tri- to penta-chlorobenzenes by gas chromatography/mass spectrometry (GC-MS), tri- to penta-chlorophenols, tetrachlorocatechol (TCC) and tetrachlorohydroquinone (TCHQ) by GC-MS after derivatization, and formic and acetic acids by ion chromatography. Two degradation pathways, hydrodechlorination and oxidative degradation, appear to occur competitively. However, more sequential chlorinated benzene and phenol congeners were formed over mixed MO/Fe(3)O(4) than over mixed MO/Fe(2)O(3) under the same conditions. The oxidative reaction dominated over mixed MO/Fe(2)O(3) and was promoted as the major reaction by the synergetic effect, while both the oxidative and hydrodechlorination reactions were important over mixed MO/Fe(3)O(4), and both pathways are remarkably promoted by the synergetic effect. The enhanced hydrodechlorination may be attributed to free electrons generated by the transformation of Fe(3)O(4) into Fe(2)O(3), and hydrogen provided by water adsorbed on the MO.

Profiles, sources and potential exposures of parent, chlorinated and brominated polycyclic aromatic hydrocarbons in haze associated atmosphere

Profiles, sources and potential exposures of chlorinated and brominated polycyclic aromatic hydrocarbons (ClPAHs and BrPAHs) in haze associated atmosphere remain unclear. Haze events happened frequently during heating period in Beijing provided a typical urban context to investigate the concentrations, profiles, sources and potential exposures of ClPAHs, BrPAHs and their non-halogenated parent compounds (PAHs) in air samples. Average concentrations of PAHs, ClPAHs and BrPAHs during heating periods (with more frequent haze events) were about 3-9 times higher than during non-heating periods. Concentrations of particulate matter (PM)-associated ClPAHs and BrPAHs were higher in heating period than in non-heating period, while for gas-associated ClPAHs and BrPAHs, this distinction was not significant. Congener patterns and congener profiles indicated that with increasing coal combustion during the heating period, concentrations of PAHs and ClPAHs in air were elevated in comparison to the non-heating period. Inhalation of PM-associated PAHs, ClPAHs and BrPAHs accounted for higher exposure than inhalation of gas phase and dermal contact of both gas phase and particulate phase. In this study we found that the particulate phase is the dominant exposure pathway of atmospheric PAHs, ClPAHs and BrPAHs during haze days, which is different from previous studies.