Occurrence and impact of polychlorinated dibenzo-p-dioxins/dibenzofurans in the air and soil around a municipal solid waste incinerator

To assess the influence of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans(PCDD/Fs) on the environment in the vicinity of municipal solid waste incinerators(MSWIs), we determined the levels of PCDD/Fs in air and soil samples collected around a MSWI, which is the largest in China. The International Toxicity Equivalency Quantity(I-TEQ) concentrations of PCDD/Fs in air samples were from 0.0300 to 1.03 pg I-TEQ/m~3(0.445–13.6 pg/m~3), with an average of 0.237 pg I-TEQ/m~3, while in soil samples they ranged from 0.520 to 3.40 pg I-TEQ/g(2.41–88.7 pg/g) with an average of1.49 pg I-TEQ/g. The concentrations of PCDD/Fs in air and soil samples were comparable to other areas, and Pe CDFs were the dominant contributors, which was different from stack gas homologue patterns. Multivariate statistical analysis showed that PCDD/Fs emission from the MSWI did not directly affect the profiles of PCDD/Fs in air and soils, so that vehicles and unidentified emission sources should be considered. The daily inhalation levels of PCDD/Fs for children(0.0110 to 0.392 pg I-TEQ/(kg·day) and adults(0.00600 to 0.221 pg I-TEQ/(kg·day) near the MSWI were lower than the tolerable daily intake of 1.00 to 4.00 pg WHO-TEQ/(kg·day), but in winter the values were higher than in summer. These results can be used as basic data for assessing the risk of PCDD/Fs exposure in residents living around this MSWI, and more monitoring programs and studies should be carried out around MSWIs.     

Laboratory-scale study of the suppression of PCDD/F emission during coal and MSW co-incineration

The experimental test of co-incinerating Chinese raw municipal solid waste （MSW） and coal in a laboratory-scale tubular reactor was first reported in present study, and the emission of normal gas components and the effects of the S/Cl molar ratio or coal mixing percentages on polychlorinated dibenzo-p-dioxins and dibenzofurans （PCDDs/Fs） emission were investigated and discussed. The results indicated that OCDD was the only PCDD homologues since others like TCDD-HpCDD was hardly detected, while as the categories of PCDF homologues were comparatively much more general. The amount of PCDD was much larger than that of PCDF in all operating conditions. Since ZPCDF/∑PCDD〈〈1, the dominant role of the precursor formation was proven in our experimental conductions. With increasing the coal addition to MSW （from 0 to 16%）, PCDD and PCDF were reduced considerably. Coal and MSW may suppress the PCDD/F emissions efficiently （over 95%） during the MSW incineration process. The PCDD/F suppression results of the present study could be helpful guidance to the industrial application of Chinese MSW and auxiliary coal co-incineration processes. The PCDD/F stack emission data of two industrial incinerators using co-incineration technology in China seem to have a great positive reduction of PCDDs/Fs.     

Experimental and modeling study of de novo formation of PCDD/PCDF on MSW fly ash

The effect of sulfur dioxide （SO2） on the formation of polychlorinated dibenzo-p-dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） has been studied in an entrained-flow reactor （EFR） under simulated waste combustion conditions. A chlorination model based on conditional probability was employed to evaluate the homologue patterns of PCDDs and PCDFs. Results revealed that the presence of SO2 did not alter the formation pathway although SO2 suppressed PCDD/F formation. The prediction model of PCDF showed good agreement with the experimental data （R--0.95）, whereas the prediction for PCDDs did not correlate well with the experimental data. This may be explained because potential chlorination pathways play a significant role in PCDF formation, whereas PCDDs are mainly formed through condensation reactions. Furthermore, the result indicated that the steric hindrance during formation has more effects on PCDD than on PCDF due to the symmetric molecular structures of PCDDs.     

Seasonal trend of ambient PCDD/Fs in Tianjin City, northern China using active sampling strategy

The spatial concentrations, seasonal trends, profiles and congener pairs of ambient polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were investigated within a seasonally active sampling scheme during Jun 2008 and Jan 2009 in Tianjin City, northern China. The PCDD/F concentrations ranged 14.2-172 fg I-TEQ/m³ (average 69.3 fg I-TEQ/m³) in summer and (89.8-1.01) × 10³ fg I-TEQ/m³ (average 509 fg I-TEQ/m³) in winter, respectively, except for the E-waste dismantling site where much higher values were observed (1.04 × 10³ fg I-TEQ/m³ in summer and 7.123 × 10³ fg I-TEQ/m³ in winter). The results indicated a significantly seasonal trend with higher TEQ values in winter as compared with summer, which could be related to increased emission sources and seasonal variations of the atmospheric boundary layer height. 2,3,4,7,8-PeCDF was the dominant contributor to the total PCDD/F toxic equivalents, and 2,3,7,8-TCDD was detected at almost all the sampling sites in winter. Most of the similarly substituted PCDD/F congener pairs exhibited high correlations, suggesting that they might have similar environmental fate or sources. But different seasonal and spatial distributions of PCDD/F concentrations indicated that the emission sources might be intermittent.     

Atmospheric emission characterization of a novel sludge drying and co-combustion system

A novel system combining sludge drying and co-combustion with coal was applied in disposing sludge and its atmospheric emission characteristics were tested. The system was composed of a hollow blade paddle dryer, a thermal drying exhaust gas control system, a 75 tons/hr circulating fluidized bed and a flue gas cleaning system. The emissions of NH3, SO2, CH4 and some other pollutants released from thermal drying, and pollutants such as NOx, SO2 etc. discharged by the incinerator, were all tested. Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans （PCDD/Fs） in the flue gas from the incinerator were investigated as well. The results indicated that the concentrations of NOx and SO2 in the flue gas from the incinerator were 145 and 16 mg/m^3, respectively, and the I-TEQ concentration of 2,3,7,8-substitued PCDD/Fs was 0.023 ng I-TEQ/Nm^3. All these values were greatly lower than the emission standards of China. In addition, there was no obvious odor in the air around the sludge dryer. The results demonstrated that this drying and co-combustion system is efficient in controlling pollutants and is a feasible way for large-scale treatment of industrial sludge and sewage sludge.     

Effect of ammonium sulfate and urea on PCDD/F formation from active carbon and possible mechanism of inhibition

The effect of ammonium sulfate （（NH4）2SO4） and urea （CO（NH2）2） on polychlorinated dibenzo-p-dioxin and dibenzofuran （PCDD/F） formation from active carbon was investigated in this study. Both additives could significantly inhibit PCDD/F formation, and PCDD/F （TEQ） generation was reduced to 98.5% （98%） or 64.5% （77.2%） after 5% （NH4）2S04 or CO（NH2）2 was added into model ash, respectively. The inhibition efficiency of PCDDs was higher than the value of PCDFs, however, the reduction of PCDD/F yield was mainly from PCDFs decreasing. In addition, the solid-phase products were reduced more than the gas-phase compounds by inhibitors. By the measurement of chlorine emission in the phase of ion （Cl[Cl^-]） and molecule gas （Cl[Cl2]）, it was observed that both Cl[Cl^-] and Cl[Cl2] were reduced after inhibitors were added into ash. Cl[Cl2] was reduced to 51.0% by urea addition, which was supposed as one possible mechanism of PCDD/F inhibition.     

Removal of PCDD/Fs and PCBs from flue gas using a pilot gas cleaning system

A 100 Nm3 /hr capacity pilot scale dual bag filter (DBF) system was tested on the flue gas from an actual hazardous waste incinerator (HWI), the removal efficiency of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) was also studied. The first filter collected most of the fly ash and associated chlorinated organic; then activated carbon (AC) was injected and used to collect phase chlorinated organic from the gas. Concentrations of PCDD/Fs and PCBs after the DBF system were 0.07 and 0.01 ng TEQ/Nm3 , respectively, which were both far below the national emission standard. Comparing with the original single bag filter system, the PCDD/Fs concentration dropped a lot from 0.36 to 0.07 ng TEQ/Nm3 . Increasing AC feeding rate enhanced their collection efficiency, yet reduced the AC utilization efficiency, and it still needs further study to select an appropriate feeding rate in the system. These results will be useful for industrial application and assist in controlling emissions of PCDD/Fs and other persistent organic pollutions from stationary sources in China.     

Impact of emission control on regional air quality: An observational study of air pollutants before, during and after the Beijing Olympic Games

An observational study on trace gases and PM2.5 was conducted at three sites in and around Beijing, during the Olympic season from 2007 to 2009. Air quality improved significantly during the Olympic Games due to the special emission control measures. However, concentrations of the primary pollutants and PM were found to have risen significantly after the Games. Although the major O3 precursors （NOx and VOCs） were well controlled during the Olympic season, O3 was still found to be the highest in 2008, based on the data of ground-based observation. All this information suggests that while control of regional emissions for the Beijing Olympic Games did improved the air quality in Beijing, more efforts will be needed for the continuous improvement of regional air quality, especially for significant reductions of O3 and fine particulate pollution, and not only in Beijing, but also in the B eijing-Tianjin-Hebei region.     

Combination of biodiesel-ethanol-diesel fuel blend and SCR catalyst assembly to reduce emissions from a heavy-duty diesel engine

In this study, the efforts to reduce NOx and particulate matter （PM） emissions from a diesel engine using both ethanol-selective catalytic reduction （SCR） of NOx over an Ag/Al2O3 catalyst and a biodiesel-ethanol-diesel fuel blend （BE-diesel） on an engine bench test are discussed. Compared with diesel fuel, use of BE-diesel increased PM emissions by 14% due to the increase in the soluble organic fraction （SOF） of PM, but it greatly reduced the Bosch smoke number by 60%-80% according to the results from 13-mode test of European Stationary Cycle （ESC） test. The SCR catalyst was effective in NOx reduction by ethanol, and the NOx conversion was approximately 73%. Total hydrocarbons （THC） and CO emissions increased significantly during the SCR of NOx process. Two diesel oxidation catalyst （DOC） assemblies were used after Ag/Al2O3 converter to remove CO and HC. Different oxidation catalyst showed opposite effect on PM emission. The PM composition analysis revealed that the net effect of oxidation catalyst on total PM was an integrative effect on SOF reduction and sulfate formation of PM. The engine bench test results indicated that the combination of BE-diesel and a SCR catalyst assembly could provide benefits for NOx and PM emissions control even without using diesel particle filters （DPFs）.     

Evaluation of PCDD/Fs and metals emission from a circulating fluidized bed incinerator co-combusting sewage sludge with coal

The emission characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and heavy metals were evaluated during co-combustion of sewage sludge with coal from a circulating fluidized bed incinerator. The stack gas, slag and fly ash samples were sampled and analyzed. The gas-cleaning system consisted of electrostatic precipitators and a semi-dry scrubber. Results showed that the stack gas and fly ash exhibited mean dioxin levels of 9.4 pg I-TEQ/Nm 3 and 11.65 pg I-TEQ/g, respectively, and showed great similarities in congener profiles. By contrast, the slag presented a mean dioxin level of 0.15 pg I-TEQ/g and a remarkable difference in congener profiles compared with those of the stack gas and fly ash. Co-combusting sewage sludge with coal was able to reduce PCDD/Fs emissions significantly in comparison with sewage sludge mono-combustion. The leaching levels of Hg, Pb, Cd, Ni, Cr, Cu, and As in the fly ash and slag were much lower than the limits of the environmental protection standard in China. These suggest that the co-combustion of sewage sludge and coal is an advisable treatment method from an environmental perspective.     

Tailpipe emission characterizations of diesel-fueled forklifts under real-world operations using a portable emission measurement system

Non-road equipment is one of the key contributing sources to air pollution. Thus, an accurate development of emission inventory from non-road equipment is imperative for air quality management, especially for equipment with a large population such as diesel-fueled forklifts. The objective of this paper is to characterize duty-cycle based emissions from diesel-fueled forklifts using a portable emission measurement system (PEMS). Three duty-cycles were defined in this study, including idling, moving, and working (active duty operation) and used to characterize in-use emissions for diesel-fueled forklifts. A total of twelve diesel-fueled forklifts were selected for real-world emission measurements. Results showed that fuel-based emission factors appear to have smaller variability compared to time-based ones. For example, the time-based emission factors for CO, HC, NO, and PM_2.5 for forklifts were estimated to be 16.6–43.9, 5.3–15.1, 26.2–49.9, 5.5–11.1 g/hr with the fuel-based emission factors being 12.1–20.3, 4.1–8.3, 19.1–32.4, 3.5–6.5 g/kg-fuel, respectively. NO emissions appear to be the biggest concern for emissions control. Furthermore, most of the emissions factors estimated from this study are significantly different from those in both National Guideline for Emission Inventory Development for Non-Road Equipment in China and well-developed emission factor models such as NONROAD by US EPA. This implies that localized, preferably fuel-based emission factors should be adjusted based on real-world emission measurements in order to develop a representative emission inventory for non-road equipment.     

Effectiveness of national air pollution control policies on the air quality in metropolitan areas of China

Understanding the effectiveness of national air pollution controls is important for control policy design to improve the future air quality in China. This study evaluated the effectiveness of major national control policies implemented recently in China through a modeling analysis. The sulfur dioxide （SO2） control policy during the llth Five Year Plan period （2006-2010） had succeeded in reducing the national SO2 emission in 2010 by 14% from its 2005 level, which correspondingly reduced ambient SO2 and sulfate （SO42-） concentrations by 13%-15% and 8%-10% respectively over east China. The nitrogen oxides （NOx） control policy during the 12th Five Year Plan period （2011-2015） targets the reduction of the national NOx emission in 2015 by 10% on the basis of 2010. The simulation results suggest that such a reduction in NOx emission will reduce the ambient nitrogen dioxide （NO2）, nitrate （NO3-）, 1-hr maxima ozone （03） concentrations and total nitrogen deposition by 8%, 3%-14%, 2% and 2%--4%, respectively over east China. The application of new emission standards for power plants will further reduce the NO2, NO3-, 1-hr maxima 03 concentrations and total nitrogen deposition by 2%-4%, 1%-%, 0-2% and 1%-2%, respectively. Sensitivity analysis was conducted to evaluate the inter-provincial impacts of emission reduction in Beijing-Tianjin-Hebei and the Yangtze River Delta, which indicated the need to implement joint regional air pollution control.     

Operating condition influences on PCDD/Fs emissions from sinter pot tests with hot flue gas recycling

This study was designed to clarify the influence of operating conditions on the formation and emissions of polychlorinated-pdibenzodioxins and dibenzofurans (PCDD/Fs) from a sintering process with hot flue gas recycling. A pilot scale sinter pot with simulated flue gas recycling was developed, and four key operational parameters, including temperature, oxygen content of the simulated waste flue gas, the coke rate of the sintering mixture, and the quicklime quality, were selected for exploring PCDD/Fs formation. The results showed that the temperature of the recycled flue gas had a major affect on PCDD/Fs formation, and a high temperature could significantly increase their formation during sintering. A clear linear correlation between the temperature of recycling flue gas and PCDD/Fs emission (r = 0.93) was found. PCDD/Fs could be reduced to a certain extent by decreasing the level of oxygen in the recycled flue gas, while sintering quality was unchanged. The coke rate had no significant influence on the formation of PCDD/Fs, but the quality of quicklime used in the sintering mixture could affect not only the amount of PCDD/Fs emissions but also the sintering productivity. Compared with a benchmark sinter pot test, PCDD/Fs emissions markedly decreased with improvements to quicklime quality. However, the reduction in PCDD/Fs emissions realized by using high-quality quicklime was limited by the temperature of the inlet gas. The highest reduction achieved was 51% compared with conventional quicklime when the temperature of the inlet gas was 150°C.     

Mercury flows in large-scale gold production and implications for Hg pollution control

Large-scale gold production(LSGP) is one of the five convention-related atmospheric mercury(Hg) emission sources in the Minamata Convention on Mercury. However, field experiments on Hg flows of the whole process of LSGP are limited. To identify the atmospheric Hg emission points and understand Hg emission characteristics of LSGP, Hg flows in two gold smelters were studied. Overall atmospheric Hg emissions accounted for 10%–17% of total Hg outputs and the Hg emission factors for all processes were 7.6–9.6 kg/ton. There were three dominant atmospheric Hg emission points in the studied gold smelters, including the exhaust gas of the roasting process, exhaust gas from the environmental fog collection stack and exhaust gas from the converter of the refining process. Atmospheric Hg emissions from the roasting process only accounted for 16%–29% of total emissions and the rest were emitted from the refining process. The overall Hg speciation profile(gaseous elemental Hg/gaseous oxidized Hg/particulate-bound Hg) for LSGP was 34.1/57.1/8.8. The dominant Hg output byproducts included waste acid, sulfuric acid and cyanide leaching residue. Total Hg outputs from these three byproducts were 80% in smelter A and 84% in smelter B. Our study indicated that previous atmospheric Hg emissions from large-scale gold production might have been overestimated.Hg emission control in LSGP is not especially urgent in China compared to other significant emission sources(e.g., cement plants). Instead, LSGP is a potential Hg release source due to the high Hg output proportions to acid and sludge.     

Destruction of PCDD/Fs by gliding arc discharges

PCDD/Fs have been become a serious issue because of their toxicological effects and associated adverse health implications.In this study,the gliding arc plasma was tested for treatment of polychlorinated dibenzo-p-dioxins(PCDDs)and polychlorinated dibenzofurans (PCDFs),which was synthesized from pentachiorophenol in atmospheric condition at 35℃with or without the catalysis of CuCl_2. From the experiment,we found that the destruction efficiency of PCDD/F homologues after gliding was discharge ranged from 25% to 79%.This result demonstrates that gliding arc plasma is an effective technology to decompose PCDDs/Fs in flue gas.A plausible degradation mechanism for PCDD/Fs by gliding arc was discussed.Finally,a multistage reactor structure of gliding arc was proposed to upgrade removal efficiency for PCDD/Fs.     

Effect of temperature and oxygen on the formation of chlorobenzene as the indicator of PCDD/Fs

Sampling and analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs) are both time-consuming and expensive. In principle,real-time monitoring of chlorobenzene(CBz) as an indicator for PCDD/Fs could be useful to control and optimize incinerator operating conditions.To test this strategy,CBz was analyzed together with PCDD/Fs in flue gas samples collected from a hospital waste incinerator.Moreover,lab experiments were conducted to investigate the eect of temperature and oxygen on CBz formation from fly ash from the same incinerator.The experimental results demonstrate that chlorobenzene(in particular PeCBz) correlate well with PCDD/Fs,in line with previous research.The optimum temperature of CBz formation is in a range of 350 to 400°C and CBz yield increases significantly with oxygen,in line with PCDD/Fs formation.This study is useful for confirming the de novo mechanism and defining correlations between CBz and PCDD/Fs.     

Brominated dioxins and furans in a cement kiln co-processing municipal solid waste

A field study and theoretical calculations were performed to clarify the levels, profiles, and distributions of polybrominated dibenzo-p-dioxins and dibenzofurans(PBDD/Fs) in a cement kiln co-processing solid waste, with a focus on the PBDF formation mechanism.The raw materials contributed greatly to input of PBDD/Fs into the cement kiln. The PBDD/F concentrations in the raw materials were much higher than those in particle samples from different process stages in the cement kiln. The PBDD/F concentrations in the clinkers were1.40% of the concentrations in the raw materials, which indicated that the high destruction efficiencies for PBDD/Fs by cement kiln. PBDD/F distribution patterns in particle samples collected from different process stages indicated the cement kiln backend was a major site for PBDD/F formation. PBDFs with high levels of halogenation, such as heptabrominated furans(Hp BDF), were the dominant contributors to the total PBDD/F concentrations and accounted for 42%–73% of the total PBDD/F concentrations in the particle samples. Our results showed that co-processing of municipal solid waste in a cement kiln may influence the congener profile of PBDD/Fs, especially for the higher halogenated PBDD fraction. In addition, there were significant correlations between the decabromodiphenyl ether and heptabrominated furan concentrations, which is an indicator of transformation from polybrominated diphenyl ethers to PBDD/Fs. Theoretical calculations were performed and demonstrated that elimination of HBr and Br_2 from polybrominated diphenyl ethers were the dominant formation pathways for PBDD/Fs. These pathways differed from that for polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs).     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in different tissues of the cormorants (Phalacrocorax carbo) from Dongting Lake, China

Tissue distribution provides important information regarding the pharmacokinetic behavior of pollutants and is invaluable when analyzing the risk posed to avian species by the exposure to such kind of pollutants. In this study, concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in muscle, liver, spleen, kidney, stomach, gall bladder, skin, heart, pancreas, intestine and lung tissue extracts of cormorants collected from Dongting Lake, China. Tissue distribution results showed preferential accumulation of PCDD/Fs in both liver and skin. The total concentration of PCDD/Fs ranged from 421 to 5696 pg/g lipid weight. Octachlorinated dibenzo-p-dioxin (OCDD) was the predominant congener in all tissues and contributed between 31% and 82% to all 17 PCDD/Fs in different tissues. The liver/muscle ratios progressively increased with the degree of chlorination of PCDDs, except for OCDD. The relative toxic potential of PCDDs and PCDFs in tissues were calculated using the World Health Organization (WHO) Toxic Equivalency Factors (TEFs) for birds. The concentrations of WHO-toxic equivalent in different tissues ranged between 14.8 and 2021 pg/g lipid weight. These results indicated PCDD/Fs may have been bio-accumulated in cormorant via food-web. Furthermore, when compared with studies reported in the literatures, the PCDD/Fs levels in the cormorant collected from Dongting Lake were still relatively high.     

Development of database of real-world diesel vehicle emission factors for China

A database of real-world diesel vehicle emission factors, based on type and technology, has been developed following tests on more than 300 diesel vehicles in China using a portable emission measurement system. The database provides better understanding of diesel vehicle emissions under actual driving conditions. We found that although new regulations have reduced real-world emission levels of diesel trucks and buses significantly for most pollutants in China,NO_x emissions have been inadequately controlled by the current standards, especially for diesel buses, because of bad driving conditions in the real world. We also compared the emission factors in the database with those calculated by emission factor models and used in inventory studies. The emission factors derived from COPERT (Computer Programmer to calculate Emissions from Road Transport) and MOBILE may both underestimate real emission factors, whereas the updated COPERT and PART5 (Highway Vehicle Particulate Emission Modeling Software) models may overestimate emission factors in China. Real-world measurement results and emission factors used in recent emission inventory studies are inconsistent, which has led to inaccurate estimates of emissions from diesel trucks and buses over recent years. This suggests that emission factors derived from European or US-basedmodels will not truly represent real-world emissions in China. Therefore, it is useful and necessary to conduct systematic real-world measurements of vehicle emissions in China in order to obtain the optimum inputs for emission inventory models.     

Estimation of OCDD degradation rate in soil

The current concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans （PCDD/Fs） were determined in soils contaminated with Chinese technical product sodium pentachlorophenate （ Na- PCP）. The estimated half-life of octachlorodioxin （OCDD） was about 14 years in contaminated soils based on the local historical record and mass balance calculation during the past 43 years（ 1960-2003）. The isomer profiles remained the same regardless of paddy field soil or riverbank soil. The results indicated that the congenerspecific information was efficient in estimating the PCDD/Fs fate in contaminated soils.