Polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) share similar toxicities and thermal origins, e.g., municipal solid waste incinerator (MSWI). Recently, PBDD/Fs from MSWI attracted rising concern because their important precursors, i.e., brominated flame retardants (BFRs), were frequently found in various wastes for landfill or MSWI feedstock. So far, however, little is known about PBDD/Fs and their associated risks in the vicinal environments of MSWI. Here we analyzed PBDD/Fs and PCDD/Fs in 29 soil samples collected around a multiyear large-scale MSWI, and compared their spatial distributions, sources and risks. PBDD/Fs demonstrated comparable concentrations and toxic equivalent quantities (TEQs) to PCDD/Fs in these samples. Spatially, both the concentrations of PBDD/Fs and PCDD/Fs decreased outwards from the MSWI, and exhibited significant linear correlations with the distances from the MSWI in the southeast downwind soil, suggesting the influence of the MSWI on its vicinal soil environment. However, the existence of other dioxin sources concealed its influence beyond 6 km. PBDD/Fs in the soils were characterized by highly-brominated PBDFs, especially Octa-BDF, and their sources were diagnosed as the MSWI and diesel exhaust; PCDD/Fs, however, were dominated by highly-chlorinated PCDDs, particularly Octa-CDD, and were contributed individually or jointly by the MSWI, automobile exhaust and pentachlorophenol (PCP)/Na-PCP. The non-carcinogenic risks of dioxins in all the soil samples were acceptable, but their carcinogenic risks in 17% of the samples were unacceptable. These samples were all located close to the MSWI and highways, therefore, the land use of these two high-risk zones should be cautiously planed.

The installation rate of denitrification devices is accelerating in Chinese urban boilers. Previous studies on pulverized coal-fired boilers without denitrification devices showed that combustion products containing mainly oxidized mercury (Hg) preferably enriched lighter Hg isotopes than feed coals. However, the magnitude of this enrichment becomes less pronounced if denitrification devices are installed. The underlying Hg isotope fractionation mechanisms are still unclear. In this study, three types of urban boilers (two pulverized coal-fired boilers, one circulating fluidized bed boiler and one municipal waste incinerator boiler) all installed with denitrification devices were measured for Hg isotope compositions of their feed fuels and corresponding combustion products. We observed little mass independent fractionation but very significant mass dependent fractionation (MDF) between feed fuels and combustion products. The fly ash and desulfurization products both enriched heavier Hg isotopes than feed coals in three coal-fired boilers, and the enrichment of heavy Hg isotopes increased with sequential removal of combustion products in all boilers. Different from previously suggested kinetic MDF for gaseous Hg⁰(g)→Hgᴵᴵ(g) and gaseous Hgᴵᴵ(g)→particulate Hgᴵᴵ(p) in coal combustion flue gases, we propose an equilibrium MDF for Hg⁰(g)↔Hgᴵᴵ(g) followed by a kinetic MDF for Hgᴵᴵ(g)→Hgᴵᴵ(p). This equilibrium MDF most likely occurs during Hg⁰(g) oxidation in denitrification devices, which enriches heavy Hg isotopes in oxidized products (Hgᴵᴵ(g) and Hgᴵᴵ(p)) that are then sequestrated in fly ash and desulfurization products. The paradigm shift of MDF in boilers with denitrification devices was further verified by parallel Hg isotope measurement in urban atmosphere particulates. Our study clearly demonstrates that modern coal-fired boilers with denitrification devices have a quite different MDF compared to traditional boilers without denitrification devices. This has important implications for estimating isotope signatures of urban boiler Hg emissions, and for isotope tracing of anthropogenic Hg emissions.

The emission of polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) from full-scale municipal solid waste incinerators (MSWI) is harmful to human and environmental health. This study analyzes the effect of different units of an air pollution control devices (APCDs), i.e. the semi-dry scrubber, fabric filter (FF), selective catalytic reduction (SCR), and wet scrubber (WS), on the removal characteristics and gas- and solid-phase distributions of PCDD/F in MSWI flue gas. APCDs reduce PCDD/F concentrations from 24.9 ng Nm⁻³ to 0.979 ng Nm⁻³ (2.16 ng I-TEQ Nm⁻³ to 0.0607 ng I-TEQ Nm⁻³), with a total removal efficiency (RE) of 96.1% (97.2% I-TEQ). Specifically, APCDs remove more than 95% of both gas- and solid-phase PCDD/F. The FF coupled with active carbon injection (FF + ACI) substantially reduces both gas- and solid-phase PCDD/F concentrations with an RE of 97.2% (98.7% I-TEQ). Additionally, FF + ACI exhibits a better RE of PCDF (98.9%) than PCDD (94.6%) and leads to PCDD congeners dominating the gas-phase. Both desorption and destruction of PCDD/F occur in the SCR, which favors removal of gas-phase PCDD/F but increases solid-phase PCDD/F. Therefore, SCR only decreases PCDD/F with a low RE of 27.6% (16.9% I-TEQ). However, SCR reduces NOₓ with a high RE of 82.3%, which could inhibit the RE of PCDD/F because of their different reaction mechanisms. WS increases PCDD/F in both the gas and solid-phase by 1.95 times (2.57 times for I-TEQ) due to the memory effect, which typically increases the total mass concentration of PCDD/F and the proportions of lower-chlorinated gas-phase PCDD/F. Migration of gas- and solid-phase PCDD/F are also analyzed according to temperature. The results of this study can contribute to the optimized design of industrial APCDs for controlling PCDD/F emissions from MSWI.

Apportioning sources of environmental pollutants is key to controlling pollution. In this study, the sources of heavy metals to 234 agricultural soils from the Jianghan Plain (JHP) (∼22454 km2) in central China were discriminated between using Cd and Pb isotope compositions and multivariate statistical analyses. Concentrations of some metals in JHP soils (0.48 ± 0.2, 48.2 ± 15.9, 0.12 ± 0.23, 48.8 ± 16.4, 36.5 ± 9.8, and 96.8 ± 42.2 mg kg−1 for Cd, Cu, Hg, Ni, Pb, and Zn, respectively) were higher than background concentrations in Chinese soil. The Cd isotope compositions for the JHP soils (δ114/110Cd values −0.76‰ to −0.25‰) were similar to Cd isotope compositions found for smelter dust and incinerator fly ash, indicating Cd was supplied to the JHP soils by ore smelting and/or refining processes. The Pb isotope compositions for the JHP soils (206Pb/207Pb 1.182–1.195 and 208Pb/206Pb 2.078–2.124) were between the Pb isotope compositions found for Chinese coal and natural sources, which a binary isotope mixing model indicated contributed 52% and 48%, respectively, of the Pb in JHP soils. Cluster analysis and positive matrix factorization indicated that the sources of heavy metals in JHP soils may consist of smelting and/or refining activities, coal combustion, agricultural activities, and natural sources (including Han River sediment and soil parent materials). The isotope fingerprints and multivariate statistical analyses together indicated that coal combustion and smelting and/or refining activities were the main anthropogenic sources of heavy metals polluting JHP soils.

Emission characteristic of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) from 12 medical waste incinerators (MWIs) which have a total yearly capacity of 523 440 ton medical waste and accounted for 8.1% of total yearly capacity of 246 MWIs in China were studied. The congeners profile, emissions and toxic equivalent concentrations (TEQ) indicators of PCDD/Fs in stack gas from two groups of MWIs were researched, and the possible formation mechanisms of PCDD/Fs from MWIs were preliminarily discussed. The results of present study were summarized as follows. (1) The total concentrations and TEQ of PCDD/Fs in stack gas from MWIs were 0.516–122.803 ng Nm−3 and 0.031–3.463 ng I-TEQ Nm−3, respectively. (2) 1,2,3,4,6,7,8-H7CDF, O8CDD, O8CDF and 1,2,3,4,6,7,8-H7CDD were the indicatory PCDD/Fs of MWI source, which could be used to apportion the sources of PCDD/Fs in environmental medium in China. (3) The emission factors of PCDD/Fs from MWIs ranged from 32.7 to 4900.0 ng I-TEQ ton−1 with a mean of 1923.6 ng I-TEQ ton−1. (4) The gas emissions of PCDD/Fs from researched 12 MWIs and all of MWIs in China in 2016 were 37.742 and 465.951 mg I-TEQ year−1, respectively. (5) 1,2,3,7,8,9-H6CDF and 1,2,3,4,7,8-H6CDF were effective TEQ indicators for the real-time monitoring of the PCDD/Fs emission. (6) The congeners profile and factor composition of PCDD/Fs in stack gas from two groups of MWIs were researched based on positive matrix factorization (PMF) model, and the possible formation mechanisms of PCDD/Fs from MWIs were preliminarily discussed.

We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and brominated polycyclic aromatic hydrocarbons (Br-PAHs) in e-waste open burning soils (EOBS). In this study, concentrations of 15 PAHs, 26 Cl-PAHs and 14 Br-PAHs were analyzed in EOBS samples. We found that e-waste open burning is an important emission source of Cl-PAHs and Br-PAHs as well as PAHs. Concentrations of total Cl-PAHs and Br-PAHs in e-waste open burning soil samples ranged from 21 to 2800 ng/g and from 5.8 to 520 ng/g, respectively. Compared with previous studies, the mean of total Cl-PAH concentrations of the EOBS samples in this study was higher than that of electronic shredder waste, that of bottom ash, and comparable to fly ash from waste incinerators in Korea and Japan. The mean of total Br-PAH concentrations of the EOBS samples was generally three to four orders of magnitude higher than those in incinerator bottom ash and comparable to incinerator fly ash, although the number of Br-PAH congeners measured differed among studies. We also found that the Cl-PAH and Br-PAH profiles were similar among all e-waste open burning soil samples but differed from those in waste incinerator fly ash. The profiles and principal component analysis results suggested a unique mechanism of Cl-PAH and Br-PAH formation in EOBS. In addition, the Cl-PAHs and Br-PAHs showed high toxicities equivalent to PCDD/Fs measured in same EOBS samples when calculated based on their relative potencies to benzo[a]pyrene. Along with chlorinated and brominated dioxins and PAHs, Cl-PAHs and Br-PAHs are important environmental pollutants to investigate in EOBS.

The waste-to-energy (WTE) incinerator plant located in the Turin area (Italy) started to recover energy from the combustion of municipal solid waste in 2013. A health surveillance program was implemented to evaluate the potential health effects on the population living near the plant. This program included a longitudinal biomonitoring to evaluate temporal changes of some environmental pollutants, including polycyclic aromatic hydrocarbons (PAHs), in residents living in areas near the Turin incinerator (exposed group, E) compared to those observed in subjects living far from the plant (not exposed group, NE). Ten monohydroxy-PAHs (OH-PAHs), consisting in the principal metabolites of naphthalene, fluorine, phenanthrene, and pyrene, were analyzed in urines collected from the E and NE subjects after one (T₁) and three years (T₂) of plant activity and compared with those determined in the same cohort established before the plant start-up (T₀). Spearman correlation analysis was undertaken to explore possible associations between OH-PAHs and personal characteristics, lifestyle variables, and dietary habits. A linear mixed model (LMM) approach was applied to determine temporal trends of OH-PAHs observed in the E and NE subjects and to evaluate possible differences in trend between the two groups. Temporal trends of OH-PAHs determined by LMM analysis demonstrated that, at all times, the E group had concentrations lower than those assessed in the NE group, all other conditions being equal. Moreover, no increase in OH-PAH concentrations was observed at T₁ and T₂ either in E or in NE group. Significant positive correlations were found between all OH-PAHs and smoking habits. Regarding variables associated to outdoor PAH exposure, residence near high traffic roads and daily time in traffic road was positively correlated with 1-hydroxynaphthalene and 1-hydroxypyrene, respectively. In conclusion, no impact of the WTE plant on exposure to PAHs was observed on the population living near the plant.

The control of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from the flue gas in hazardous waste incinerators (HWIs) is an intractable problem. To figure out the formation mechanism of PCDD/Fs and reduce the emission, a field study was carried out in a full-scale HWI. Ca(OH)₂ & (NH₄)H₂PO₄ or CH₄N₂S & (NH₄)H₂PO₄ were injected into the quench tower, and the detailed inhibition effect on PCDD/Fs formation by the inhibitors coupled with quench tower was studied. Gas and ash samples were collected to analyze PCDD/Fs. XPS, EDS characterization and Principal component analysis were adopted to further analyze the de novo and precursors synthesis. The PCDD/Fs emissions reduced from 0.135 ng I-TEQ/Nm³ to 0.062 or 0.025 ng I-TEQ/Nm³ after the injection of Ca(OH)₂ & (NH₄)H₂PO₄ or CH₄N₂S & (NH₄)H₂PO₄, respectively. The quench tower was found mainly hindering de novo synthesis by reducing reaction time. CP-route was the dominant formation pathway of PCDD/Fs in quench tower ash. Ca(OH)₂ & (NH₄)H₂PO₄ effectively inhibit precursors synthesis and reduce proportions of organic chlorine from 4.11% to 2.86%. CH₄N₂S & (NH₄)H₂PO₄ show good control effects on both de novo and precursors synthesis by reducing chlorine content and inhibiting metal-catalysts. Sulfur-containing inhibitors can cooperate well with the quench tower to inhibit PCDD/Fs formation and will be effective to reduce dioxins formation in high chlorine flue gas. The results pave the way for further industrial application of inhibition to reduce PCDD/Fs emissions in the HWIs flue gas.

Incineration has gradually become the most effective way to deal with MSW due to its obvious volume reduction and weight reduction effects. However, since heavy metals and organic pollutants carried by municipal solid waste incinerator fly ash (MSWI FA) pose a serious threat to the ecological environment and human health, they need to be handled carefully. In this study, the current status of MSWI FA disposal was first reviewed, and the harmless and resourceful disposal technologies of heavy metals and organic pollutants in MSWI FA are summarized as well. A summary of the advantages and disadvantages of each technology, including sintering, melting/vitrification, hydrothermal treatment, mechanochemistry, solidification/stabilization of MSWI FA, is compared. Finally, the research work that needs to be strengthened in the future (such as codisposal of multiple wastes, long-term stability research of disposal products, etc.) was proposed. Through comprehensive analysis, some reasonable and feasible suggestions were provided for the effective and safe disposal of MSWI FA in the future.

Organobromine compounds comprise between 3 and 8% by weight of WEEE and mainly converted to HBr and Br₂ in the incinerator. However, these compounds, during the cooling of the flue gases, can form the PBDD/Fs in the post-combustion area of the furnace. Due to the many benefits of Oxy-combustion process, our group has developed a fluidised bed incinerator for burning the WEEE and plan to maximise HBr/Br₂ in the flue gas. Experimental results presented in the recent papers show that the combustion of the WEEE particles attains quickly to thermodynamic equilibrium. Thermodynamic modelling can, therefore, predict the concentration of brominated pollutants, particularly HBr, Br₂, HgBr₂, and Br˙ in the flue gas. In this paper, the effect of various parameters for increasing the HBr/Br₂ ratio in the flue gas has been investigated. The model shows that the addition of very small amounts of hydrogen in the post-combustion area can convert Br₂ and Br˙ into HBr.