Shujun Dong

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.

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.

Occupational Exposure to Polychlorinated Dibenzo-p-dioxins and Dibenzofurans, Dioxin-like Polychlorinated Biphenyls, and Polychlorinated Naphthalenes in Workplaces of Secondary Nonferrous Metallurgical Facilities in China

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), and polychlorinated naphthalenes (PCNs) were determined in workplace air from eight secondary nonferrous metal processing plants to investigate occupational exposure to these toxic compounds. The total estimated daily intakes of PCDD/Fs and dl-PCBs for workers by inhalation in the workplace were in the range of 0.15-9.91 and 0.13-8.59 pg of WHO-TEQ/kg of body weight (bw) for moderate and light activities, respectively. The daily inhalation doses for workers in the workplaces of three investigated plants exceeded the tolerable daily intake recommended by the World Health Organization. These results indicate that the risk of occupational exposure to dioxins by inhalation in the workplace of plants investigated was considerably high. For PCNs, the daily inhalation doses for workers in the workplace were in the range of 0.005-4.46 and 0.004-3.87 pg of TEQ/kg of bw for moderate and light activities, respectively, which were lower than those of dioxins. To identify the source of PCDD/Fs, PCBs, and PCNs in workplace air, their homologue profiles were compared with those in stack gas from the plants investigated. It was found that significant dioxin contamination in workplace air was mainly attributed to the emission of fugitive gas from smelting furnaces during reclamation processes.

Cooking Process: A New Source of Unintentionally Produced Dioxins?

To improve understanding of human background exposure to dioxins, the influence of cooking on dioxin concentrations in food has received much attention. Studies have focused on changes in the distribution of dioxins that originate from raw foods. However, the possibility of dioxin formation during cooking has been neglected. In this study, cooking experiments were designed to investigate the generation of dioxins during cooking at high temperature and with flavorings containing organic chlorine. Solid, liquid, and gas phase samples were collected during cooking. The results indicate that dioxins can be generated during some cooking processes, such as burning, or when cooking with reactive organic chlorides, and the dioxins are more likely to be present in the smoke (gas phase) than the edible portion (solid and liquid phases). Thus, more attention should be given to cooking of raw foods and organic chlorine-containing flavorings at high temperature. Maintaining good ventilation during cooking is also necessary to reduce human exposure risk to dioxins.

Polychlorinated naphthalene concentrations and profiles in cheese and butter, and comparisons with polychlorinated dibenzo-p-dioxin, polychlorinated dibenzofuran and polychlorinated biphenyl concentrations

Polychlorinated naphthalenes (PCNs) are candidates for inclusion in the Stockholm Convention on persistent organic pollutants. PCNs are structurally and toxicologically similar to 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) and its analogues. Intake in food is considered to be an important human exposure pathway for PCNs. In this preliminary study, cheese and butter samples were analysed for PCNs, polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) using an isotope dilution gas chromatography high-resolution mass spectrometry method. The aim of this study was to evaluate the PCN concentrations in the cheese and butter samples and to compare them with the PCDD, PCDF and PCB concentrations. The PCN concentrations were 5.6–103 pg g−1 of wet weight in the seven cheese samples tested and 5.0–199 pg g−1 of wet weight in the seven butter samples tested. The mass concentrations of lower chlorinated congeners were greater than those of the higher chlorinated congeners. Congeners of CN45/36, CN27/30 and CN33/34/37 were much more abundant than other congeners found in tetrachlorinated PCNs. Congeners of CN51, CN66/67 and CN73 were determined to be the predominant congeners in penta-, hexa- and heptachlorinated homologs, respectively. The PCNs contributed around 5% of the total PCN, PCDD, PCDF and PCB toxic equivalence (TEQ) values. CN73 was found to be the dominant PCN congener and contributed more than 40% to the PCN TEQ value. Congeners CN66/67, CN69 and CN63 were also found at relatively high levels. The PCB congener CB118 was the predominant congener (by mass-based concentration) of the 12 dioxin-like PCBs (dl-PCBs). The PCBs contributed 53.8% of the total TEQ, and congener CB126 contributed more than any other compound that was analysed to the total TEQ. The PCDDs and PCDFs contributed 11.6% and 29.7% of the total TEQ values, respectively.

Polychlorinated dibenzo-p-dioxins and dibenzofurans formed from sucralose at high temperatures

Sucralose is a widely-used artificial high-intensity sweetener. Although doubts have been raised about the safety of sucralose by several researchers, it can still be found in a broad range of foods and beverages worldwide, including in baked goods. Sucralose may decompose at high temperatures, and participate in chlorination reactions, generating highly toxic compounds. Here, we demonstrate that heating sucralose at high temperatures in stainless steel or other metal utensils in the presence of rust (Al2O3, Fe2O3, and CuO) produces polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). PCDD/Fs were found in smoke generated during the heating of sucralose and in the residues after heating. CuO enhanced the PCDD/F yield in comparison with Al2O3 and Fe2O3.

Determination of Ultratrace Polychlorinated Dibenzo-p-dioxins and Dibenzofurans by Gas Chromatography-Triple Quadrupole Mass Spectrometry

In this study a gas chromatography-tandem mass spectrometry (GC/MS/MS) method with a triple quadrupole mass spectrometer was developed for ultratrace analysis of seventeen 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The GC and MS/MS parameters were optimized to improve the separation and resolution of the target compounds. In multiple reaction monitoring mode, two pairs of precursor ions and product ions were selected for each target compound for qualitative and quantitative analysis. The average relative response factors were calculated from five-point calibration (0.5-2000 μg L−1) curves for the 17 PCDD/F congeners. The relative standard deviations of all the congeners were <11%. The lower limit of detection ranged from 0.05 to 0.34 μg L−1. The method was applied to analysis of certified reference materials, including one solution sample and four sediment samples. The sediment samples were extracted by accelerated solvent extraction, and then purified using a Power-Prep(tm) automatic cleanup system. The precision of the PCDD/Fs quantitation in the solution sample was determined, and the relative standard deviations were <4%. The results for the solution and sediment samples agreed with their certified values. Consequently, this GC/MS/MS method can be proposed as an alternative to the relatively expensive high-resolution MS method for monitoring PCDD/Fs.