The 14th International Congress on Combustion By-Products and Their Health Effects was held in Umeå, Sweden from June 14th to 17th, 2015. The Congress, mainly sponsored by the National Institute of Environmental Health Sciences Superfund Research Program and the Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning, focused on the “Origin, fate and health effects of combustion-related air pollutants in the coming era of bio-based energy sources”. The international delegates included academic and government researchers, engineers, scientists, policymakers and representatives of industrial partners. The Congress provided a unique forum for the discussion of scientific advances in this research area since it addressed in combination the health-related issues and the environmental implications of combustion by-products. The scientific outcomes of the Congress included the consensus opinions that: (a) there is a correlation between human exposure to particulate matter and increased cardiac and respiratory morbidity and mortality; (b) because currently available data does not support the assessment of differences in health outcomes between biomass smoke and other particulates in outdoor air, the potential human health and environmental impacts of emerging air-pollution sources must be addressed. Assessment will require the development of new approaches to characterize combustion emissions through advanced sampling and analytical methods. The Congress also concluded the need for better and more sustainable e-waste management and improved policies, usage and disposal methods for materials containing flame retardants.

This case study investigated PCDF and PCDD emissions from a 65 MW waste-to-energy plant to identify why an air pollution control system remodeling to accommodate increased production resulted in increased TEQ concentrations. Pre- and post-filter gases were collected simultaneously in four sample sets with varying filter temperatures and with/without activated carbon injection. Samples were analyzed to determine total PCDF and PCDD concentrations, as well as homologue profiles, and concentrations of individual congeners (some remained co-eluted). The total post filter PCDD concentrations where found to increase while the concentrations of PCDF and 2,3,7,8-substituted congeners declined. An investigation of the individual congener concentrations revealed that the increase of PCDD concentrations were due to a few congeners, suggesting a single formation route. The study also concludes that vital information about the formation could be obtained by not restricting the analysis to just the 2,3,7,8-substituted congeners.

Open burning tests of municipal waste from two countries, Mexico and China, showed composition-related differences in emissions of polychlorinated dibenzodioxins and dibenzofurans (PCDDs/PCDFs). Twenty-six burn tests were conducted, comparing results from two laboratory combustion facilities. Waste was shredded to isolate composition-specific effects from those due to random waste orientation. Emissions ranged from 5 to 780 ng toxic equivalent/kg carbon burned (ng TEQ (kg C-b)(-1)) with an average of 140 ng TEQ (kg C-b)(-1) (stdev = 170). The waste from Mexico (17 ng TEQ (kg C-b)(-1)) had a statistically lower average emission factor than waste from China (240 ng TEQ (kg C-b)(-1). This difference was attributed primarily to waste composition differences, although one time-integrated combustion quality measure, Delta CO/Delta CO2, showed statistical significance between laboratories. However, waste composition differences were far more determinant than which laboratory conducted the tests, illustrated using both statistical techniques and comparison of cross-over samples (wastes tested at both facilities). Comparison of emissions from previous waste combustion tests in Sweden and the U.S.A, showed emission factors within the range of those determined for Mexico and China waste. For laboratory-scale combustion, existing emission factors and test methodologies are generally applicable to both developed and developing countries. Published by Elsevier Ltd.

The relationship between the properties of fly ash generated during waste incineration and the thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs ...

Two artificial wastes (A and B) whose contents reflect regional differences in municipal solid waste composition, were used to investigate the thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) during incineration. Flue gas samples were simultaneously collected at three ports in the post-combustion zone corresponding to flue gas temperatures of 400, 300, and 200 °C. The combustion of Waste B, which had a higher chlorine and metal content than Waste A, produced greater levels of highly-chlorinated homologues, as demonstrated by a higher degree of chlorination. The total concentrations of PCDDs, PCDFs, PCBs, and PCNs formed in the combustion of both wastes increased as temperature decreased along the convector. There were no significant differences in total concentrations between Waste A and Waste B combustion at specific temperatures, with exception of PCDFs at 400 °C. Orthogonal Projections to Latent Structures Discriminant Analysis (OPLS-DA) modeling, used to evaluate the data for all compound groups, suggest that during flue gas quenching at temperatures of 400 °C low-chlorinated homologues are preferentially formed in the presence of copper, which is known to be a very active catalyst for this process. At 300 and 200 °C, the formation of highly-chlorinated homologues is favored.

In a laboratory-scale combustion reactor, flue-gas samples were collected at two temperatures in the post-combustion zone, 700°C and 400°C, using two different water-cooled sampling probes. The probes were the cooled probe described in the European Standard method EN-1948:1, referred to as the original probe, and a modified probe that contained a salt/ice mixture to assist the cooling, referred to as the sub-zero probe. To determine the efficiency of the cooling probes, internal temperature measurements were recorded at 5cm intervals inside the probes. Flue-gas samples were analyzed for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs). Samples collected at 700°C using the original cooling probe showed higher concentrations of PCDD/Fs compared to samples collected using the sub-zero probe. No significant differences were observed between samples collected at 400°C. The results indicated that artifact formation of PCDD/Fs readily occurs during flue-gas sampling at high temperatures if the cooling within the probe is insufficient, as found for the original probe at 700°C. It was also shown that this problem could be alleviated by using probes with an enhanced cooling capacity, such as the sub-zero probe. Although this may not affect samples collected for regulatory purposes in exit gases, it is of great importance for research conducted in the high-temperature region of the post-combustion zone.

The polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) content of three fly ash samples with different elemental compositions from different municipal waste incinerators were analyzed before and after thermal treatment at 300°C or 500°C. Gas phase emissions during the treatments were also collected and analyzed. Substantial reductions in the total PCCD/F content of the ashes were observed after treatment at 500°C, seemingly due to degradation rather than dechlorination. Treatment at 300°C resulted in an increase in the PCDD/F content of the three ashes. Initial concentration of PCDD/F in the untreated ashes did not reflect the outcome of the treatment at the different temperatures. In addition, the composition of the ash was found to influence the rate of decomposition and formation of PCDD and PCDF during thermal treatment; the results showed that Cu, Fe, Ca and S play important roles in these processes.

Open burning of waste is the most significant source of polychlorinated dibenzo-para-dioxins and dibenzofurans (PCDD/PCDF) in many national inventories prepared pursuant to the Stockholm Convention on Persistent Organic Pollutants. This is particularly true for developing countries. Emission factors for POPs such as PCDD/PCDF, dioxin-like polychlorinated biphenyls (dl-PCB) and penta- and hexachlorobenzenes (PeCBz/HCB) from open burning of municipal solid waste in China and Mexico are reported herein. Six different waste sources were studied varying from urban-industrial to semi-urban to rural. For PCDD/PCDF, the emission factors to air ranged from 3.0 to 650 ng TEQ kg(-1)waste and for dl-PCB from 0.092 to 54 ng TEQ kg(-1)waste. Emission factors for PeCBz (17-1200 ng kg(-1)waste) and HCB (24-1300 ng kg(-1)waste) spanned a wide but similar range. Within the datasets there is no indication of significant waste composition effect on emission factor with the exception of significantly higher Mexico rural samples.

This study investigated the effects of transient combustion conditions on formation of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) along the postcombustion zone. Polychlorinated benzenes (PCBz) and polycyclic aromatic hydrocarbons (PAH) were also studied. The study was conducted in a laboratory fluidized-bed reactor fed with an artificial municipal solid waste (MSW) under controllable but realistic combustion conditions. PCDD/Fs, PCBz, and PAHs were monitored under normal, transient, and posttransient combustion conditions and simultaneously sampled at three different sampling points/temperatures (400 degrees C, 300 degrees C, and 200 degrees C). Substantially higher PCDD/F, PCBz, and PAH concentrations were found during transient combustion than during normal combustion. Elevated concentrations were found to decrease with time. PCDD/F concentrations were similar at all points during normal and transient combustion conditions, but were found in higher concentrations at 200 degrees C than 400 degrees C under the posttransient combustion periods. Higher concentrations of the sum PAH and PCBz were also found at 200 degrees C than 400 degrees C in the posttransient combustion periods. Transient combustion conditions induced changes in both PCDD/F homologue profile and PCDD/F congener patterns compared to normal combustion. PCDD/PCDF ratios indicated an increase of the de novo synthesis during transient combustion conditions. Although, the PCDD/F congeners found to be most strongly affected by the transient combustion conditions indicated different reactions pathways active for formation of PCDF and PCDD, de novo synthesis and precursors, respectively. The most strongly affected PCDD/F congeners of transient combustion were identified and are presented.

Effects of postcombustion zone temperatures and flue gas residence times on monochlorinated to octachlorinated dibenzo-p-dioxins and -furans (PCDD/F) in a laboratory-scale reactor combusting municipal solid waste were investigated. Four different quench time profiles were investigated, falling from 400 degrees C to 200 degrees C, 300 degrees C to 100 degrees C, 450 degrees C to 200 degrees C and 460 degrees C to 260 degrees C, with corresponding residence times of 1.4 to 4.4 sec, 1.4 to 5.4 sec, 1.3 to 4.3 sec, and 1.3 to 4.0 sec, respectively. Flue gas samples were collected simultaneously at three fixed sampling points, with an additional sampling of flue gas entering the postcombustion zone (640 degrees C). The quench time profiles resulted in different total PCDD/F yields, as well as differences in homologue profiles and congener patterns. Thus, the formation pathways seem to be dependent on sufficient residence time within a specific temperature region. Formation of PCDD/F was shown to be rapid and mainly located to the 640 degrees C to 400 degrees C temperature region, with non-detectable levels at 640 degrees C and concentrations at 400 degrees C that did not increase or decrease significantly downstream. Furthermore, a prolonged residence time at and above 450 degrees C/460 degrees C showed low yields even downstream the postcombustion zone compared to the 400 degrees C to 200 degrees C and 300 degrees C to 100 degrees C profiles. The 460 degrees C to 260 degrees C profile resulted in increased abundance at the last two sampling points of PCDD congeners known to correlate with 2,4,6-trichlorophenols, suggesting that chlorophenol condensation reactions were promoted by this quench time profile.

SO2 levels in the flue gas from a laboratory-scale fluidized bed reactor combusting artificial municipal solid waste (MSW) were varied (resulting in four different SO2:HCl ratios 0, 0.2, 0.7 and 2.7 (by mass)) to study the effects of sulfur on the formation of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzothiophenes (PCDTs). Sampling was performed simultaneously at three fixed points in the post-combustion zone with temperatures of 400, 300 and 200°C, under normal combustion conditions and both during and after transient combustion conditions. The findings indicate that sulfur has a greater inhibitory effect on PCDF formation than on PCDD formation and that the PCDD/PCDF ratio in the flue gas depends on both the SO2:HCl ratio in the flue gas and memory effects arising from transient combustion conditions. The results also indicate that the relative importance of different pathways shifts in the post-combustion zone; condensation products increasing with reductions in temperature and increases in residence time. However, these changes appear to depend on the SO2:HCl ratio in the flue gas and combustion conditions. Sulfur seems to inhibit the chlorination of PCDFs. A tendency for increased SO2 levels in the flue gas to increase levels of PCDTs was also detected, but the increases were much less significant than the reductions in PCDF levels.

The isomer distribution patterns of mono- to hepta-chlorinated dibenzo-p-dioxins (PC1-7DD) and dibenzofurans (PC1-7DF) in postcombustion zone flue gas during incineration of an artificial municipal solid waste in a laboratory-scale fluidized-bed reactor were evaluated. Bidirectional orthogonal projections to latent structures (O2PLS) was used to correlate a set of physicochemical properties and chlorine substitution descriptors with the objective to identify parameters correlated with postcombustion zone PCDD and PCDF formation. The most influential variable for the distribution of PCDD congeners was chlorine substitution in positions 1 and 3 (Cl1+3), and overall the chlorine substitution descriptors exerted a larger impact on PCDDs than on PCDFs. For the PCDF, chlorination of the 9-position was the most influential X-variable. Distinct clustering was observed and was most pronounced for PCDFs, dividing mostof the homologues into two or three subgroups of congeners. These subgroups seemed to correspond to the probability of formation by chlorophenol condensation. The sterically crowded dibenzofuran bay-sites (1- and 9-positions) were found to negatively influence PCDF formation, with chlorination of the 9-position having the greatest impact. Since PCDD/F toxicity is related to the lateral positions, elucidating the factors governing chlorination may be of great importance for detoxification of incineration byproducts.

Formation of polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF), benzenes (PCBz), and phenols (PCPh) was studied during combustion of an artificial municipal solid waste (MSW) in a laboratory-scale fluidized-bed reactor with simultaneous collection of flue gas samples at three different temperatures in the post-combustion zone (450 °C, 300 °C, and 200 °C). PCDF, PCBz, and PCPh were predominantly formed at or above the first sampling point (450 °C) with a dominance of the lower chlorinated homologues. PCDDs, on the other hand, were dominated by the intermediately chlorinated homologues with concentrations peaking at 300 °C. The dominating PCPh congeners clearly displayed the ortho–para directionality, which is indicative of electrophilic aromatic substitution, as did the PCBz isomer distribution patterns to some extent. Comparison of the observed PCBz isomer distribution patterns to prior work may indicate coupling of aliphatic species in chlorobenzene formation. The PCDDs seemed to be largely influenced by chlorophenol condensation reactions and to some extent chlorination reactions, while the PCDFs displayed a chlorination-oriented pattern for the mono- to tri-chlorinated homologues and a PCPh condensation pattern for the higher chlorinated homologues. Injection of non-chlorinated dibenzo-p-dioxin at 650 °C resulted in increased formation of Tri-HxCDD and a decrease in the dibenzofuran levels. The affected PCDD and PCDF congeners were not products expected to form from chlorine substitution, but instead are well known chlorophenol condensation products.

Process, combustion and fuel parameters were varied to elucidate factors that substantially affect the formation and emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) arising from municipal solid waste (MSW) incineration. The combustion conditions were varied by changing the: freeboard temperatures; quench time in the post-combustion zone; fuel load; chlorine and copper levels in the fuel; and the water, sulfur dioxide, carbon monoxide and oxygen levels in the combustion gases. The study was performed using a 5kW laboratory-scale fluidized-bed reactor and PCDD/Fs were sampled at a point at 300°C in the post-combustion zone. The results showed that increasing the SO2 level (from 0 to 130ppm) substantially reduced the PCDD/F emissions, by up to 60%. In contrast, increasing the CO levels (due to transient combustion conditions), raising the Cl level (from 0.7% to 1.7%) and reducing the freeboard temperature (from 800°C to 660°C) all substantially increased the emission levels (more than 3-fold). Changes in PCDD/F profiles associated with increases in Cl, SO2 or CO levels and increasing the freeboard temperature (from 800°C to 950°C) indicate that the PCDFs were mainly formed by chlorination. In addition, increasing the Cl level increased the chlorination activity in the formation of PCDDs. Increasing the SO2 level appeared to be less effective in reducing the amount of PCDDs formed via the precursor pathway. While increased CO levels induced PCDD formation via the precursor pathway, although this was found to depend on the O2 level in the flue gas.

We have estimated the concentration and distribution of the mono to octa-chlorinated congeners of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in fly ashes at various sampling points in a large-scale municipal solid waste incinerator at Umea, Sweden, as they cooled from 700 to 170 degrees C. Differences between the ashes were observed, the PCDD homologue profile was found to vary with temperature. The total amount of PCDD and PCDF increased as the temperature decreased in the postcombustion zone. The increase was due to both adsorption to the fly ash and formation of PCDD and PCDF. Mono- to trichlorinated PCDD predominated at high temperatures, whereas hepta- and octachlorinated PCDD predominated at temperatures below 400 degrees C. PCDF predominated over PCDD in the whole temperature range. However,the changes in homologue profile for PCDF were minor. The isomer distribution within the homologue groups was not changed as the temperature decreased in the postcombustion zone.