Assessment of the PCDD/F fate from MSWI residue used in road construction in France

MSWI fly ash is susceptible to contain high amount of polychlorinated dibenzo-dioxins and polychlorinated dibenzo-furans. However, the use of MSWI residue for road construction started in France at a period when MSWI Bottom Ash and MSWI fly ash were not separated. From four old road sites, MSWI residue, road soils, reference soils and geo-textiles were sampled and their PCDD/F contents were analyzed. MSWI residue show a great heterogeneity but also high amounts of PCDD/F (14-2960 ng I-TEQ kg(-1)dm). Soils underlying the road show less heterogeneity and PCDD/F contents between 0.57 and 7.23 ng I-TEQ kg(-1)dm, lower than ordinary soils. Moreover, the specific analysis of the 17 toxic PCDD/F congeners (notably the 2,3,7,8-TetraCDD) indicates the very low harmfulness of road soils. The study also allows to assert the relation between the MSWI residue particle size and the PCDD/F content.     

Influence of start-up on PCDD/F emission of incinerators

This study aims to evaluate the influence of start-up on polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) concentration in the stack flue gas of incinerators and its contributing PCDD/F emission. The PCDD/F emission of the first sample among three consecutive stack flue gas samples of five intermittent incinerators, which sampled at a stable combustion condition after start-up, is 2-3 times higher than the mean of the others. For verifying the PCDD/F characteristics of incinerators during start-up, one continuous MSWI was investigated for two years. The elevated PCDD/F emissions of the MSWI during start-up could reach 96.9 ng I-TEQN m(-3) and still maintained a high PCDD/F emission (40 times higher than the Taiwan emission limit) even 18 h after the injection of activated carbon, indicating the memory effect. Taking the MSWI for example, which consists of four incinerators, the estimated annual PCDD/F emission from normal operational conditions was 0.112 g I-TEQ. However, one start-up procedure can generate approximately 60% of the PCDD/F emissions for one whole year of normal operations. And the PCDD/F emission, which is the result of the start-ups of four incinerators, was at least two times larger than that of a whole year's normal operations, without consideration for the PCDD/F emission contributed by the long lasting memory effect.     

Polypropylene as regenerable absorber for PCDD/F emission control

A new method for the PCDD/F reduction in exhaust gases of incineration plants is based on the property of polypropylene (PP) of interacting with PCDD/F to a variable degree depending on the temperature. After having been loaded with PCDD/F at approx. 80 degrees C, the PP absorber material can be regenerated by a temperature increase of about 50 degrees C. Hence, PP can be applied in a closed cycle as a thermally regenerable PCDD/F separator without an additional waste flow being generated. The setup of the pilot plant and the first results achieved shall be described.     

On-line real-time measurements at incineration plants: PAHs and a PCDD/F surrogate compound at stationary combustion conditions and during transient emission puffs

Laser mass spectrometry has been applied for on-line monitoring of traces of aromatic compounds from flue gas of incineration plants. The experiments have been carried out at two sampling sites in an industrial hazardous-waste incinerator. With laser mass spectrometry resonance-enhanced multiphoton ionization (REMPI) with time-of-flight mass spectrometry (TOFMS) (REMPI-TOFMS), using the group selective multi-component monitoring approach, aromatic compounds are selectively ionized from the complex flue-gas matrix. In this case, the result of an REMPI-TOFMS on-line measurement is a distinct pattern of aromatic compounds. These patterns are dependent on: (i) the point of measurement, (ii) the incineration plant, (iii) the temperature, and (iv) the fuel. This contribution focuses on the fuel dependence of the pattern. The most transient behavior can be observed when containers filled with hazardous waste are burnt, leading to puffs. Real-time monitoring results of puffs are given. Furthermore, as an approach towards on-line monitoring of the TEQ (PCDD/F toxicity equivalent), REMPI-TOFMS on-line analysis results of chlorobenzene are presented.     

Assessment of current serum levels of PCDD/Fs, dl-PCBs and PBDEs in a Dutch cohort with known perinatal PCDD/F exposure

As part of a longitudinal cohort study, now in its second decade, we determined PCDDs/Fs dl-PCBs and PBDEs in serum of adolescents with known perinatal PCDD/F exposure. Of the original cohort, 33 adolescents aged 14-19 years, who had been studied previously during their neonatal (n=60), toddler and pre-pubertal period (n=41) agreed to participate in the current follow-up. PCDD/F-, dl-PCB- and PBDE congeners were measured using GC/MS. Current serum levels of PCDD/Fs determined in our cohort were relatively low (mean of 2.2pg/g) compared to the perinatal exposure. No correlation between perinatal exposure and current serum PCDD/F was found. Planar PCB TEQ levels were 2.2pg/g. Current summation operatorPBDE levels were 8.7ng/g lipid. There was one outlier with a summation operatorPBDE of 74ng/g lipid. The presence of this high value indicates that the exposure pathway is different from PCDD/F and PCB, most likely by dust and food contaminated with dust. Concluding we can say that current PCDD/F levels are quite low compared to the perinatal PCDD/F exposure of the cohort. PBDE levels however are relatively high compared to other European countries, more research on possible health effects of these levels, especially for subjects with outlier concentrations, should be performed.     

PCDD/F reduction in incinerator flue gas by adding urea to RDF feedstock

The effect of urea on PCDD/F formation in a pilot incinerator was studied by incinerating urea with refuse-derived fuel (RDF) at three concentrations (0.1%, 0.5% and 1.0%, of the fuel feed). A distinct reduction in both PCDD/F and chlorophenol concentrations could be noticed when urea was introduced into the system. Partial-least-square (PLS) analysis of the data showed the importance of certain chlorophenol isomers as PCDD/F precursors, pointing to the possibility that the impact point of the urea inhibitor could be before the precursor molecules, i.e. chlorophenols, have been formed.     

Kinetics of carbon degradation and PCDD/PCDF formation on MSWI fly ash

The native carbon oxidation and PolyChloroDibenzo-p-Dioxins and PolyChloroDibenzoFurans, PCDD/F, formation were simultaneously studied at different temperatures (230-350 degrees C) and times (0-1440 min) in order to establish a direct correlation between the disappearance of the reagent and the formation of the products. The kinetic runs were conducted in an experimental set up where conditions were chosen to gain information on the role of fly ash deposits in cold zones of municipal solid waste incinerators in PCDD/F formation reaction. The carbon oxidation measured as the decrease of total organic carbon of fly ash was in agreement with the carbon evolved as sum of CO and CO(2). The carbon mass balance indicated an increase in the efficiency of carbon conversion in CO and CO(2) with temperature. The CO and CO(2) formation was the result of two parallel pseudo first order reactions thus giving significant information about the reaction mechanism. PCDD/F formation as a function of temperature showed that the maximum formation was achieved in a narrow range around 280 degrees C; the time effect at 280 degrees C was a progressive formation increase at least up to 900 min. The PCDF:PCDD molar ratio increased with temperature and time, and the most abundant homologues were HxCDD, HpCDD, OCDD for PCDD, and HxCDF, HpCDF within PCDF. These experimental results supported the hypothesis that the formation mechanism was the de novo synthesis.     

Formation and destruction of PCDD/F inside a grate furnace

Formation and destruction of polychlorinated dibenzo-p-dioxins and dibenzofurans PCDD/F during the combustion process was investigated experimentally in a pilot plant. All important process steps like the burnout of the fuel bed on the grate, the burnout of the flue gas inside the combustion chamber, the heat recovery in a boiler as well as influences of the fuel composition are described in detail.

High concentrations especially of PCDF are formed during the burnout of the fuel bed. The formation reaction is mainly influenced by the fuel composition and the burnout characteristic of the fuel bed. Fuels with low chlorine and low metal content (Cu) result only in negligible concentrations of PCDD/F.

Under stable combustion conditions characterized by an excellent flue gas burnout PCDD/F will almost be completely destroyed already inside the combustion chamber. “Cold strands” of unburned flue gas (high CO concentrations) caused by disturbed combustion conditions will result in high concentrations of PCDD and especially of PCDF in the raw gas.

A second place of PCDD/F formation is the well-known boiler section. Here fly ash deposits containing residual carbon (mainly soot particles) are the source for the formation reaction. Under stationary effective combustion conditions, they are dominant for PCDD/F concentrations in the raw gas over a very long period of time.

Stationary efficient flue gas burnout (especially soot) together with effective boiler cleaning will guaranty low concentrations of PCDD/F in the flue gas in front of the flue gas cleaning system.     

Myeloperoxidase-catalyzed formation of PCDD/F from chlorophenols

Chlorophenols (CP) are transformed in vitro to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) by a biochemical-catalyzed oxidation. This is shown for 2,4,5-tri-, 2,3,4,6-tetra-and pentachlorophenol with myeloperoxidase recovered from human leucocytes in the presence of hydrogen peroxide. The yield, the reaction, and the PCDD/F-pattern found depend on the CP. The formation rates are in the micromol-per-mol range for all substrates. The experiments confirm the suspicion that a biochemical formation of PCDD/F from precursors such as CPs can take place in the human body and that this metabolic pathway may lead to a higher inner exposure with PCDD/F than is now assumed.     

Concentration changes for 5 PCDD/F congeners after administration in beef cattle

Ten cattle were treated with daily doses of five PCDD/F congeners, over a 4 week period. Four control animals were not treated. They were subsequently slaughtered as three groups, at 5, 18 and 31 weeks after the first dose. All congeners showed an increase in concentration within animal tissues when sampled at 5 weeks post-dosing. Concentrations had reduced after 18 weeks and there was a further small reduction after 31 weeks. Halflives for each congener were calculated at 13-21 weeks (93-148 days). Concentrations of congeners were different in the various tissues analysed. At 5 weeks after dosing commenced, concentrations in sub-cutaneous fat and in perirenal fat were close to 40 ng/kg (a predicted level based on 50% absorption of the dosed compounds). Concentrations on a fat basis in muscle tissue and liver were, however, about 5 and 10 times higher, respectively. The concentrations found in muscle tissue and liver samples taken at 18 and 31 weeks were approximately twice that found in fat deposits, thus the differences were still apparent, but at a reduced level. It is possible that the distribution phase was incomplete and that PCDD/Fs remained predominantly in association with circulating blood lipids rather than in equilibrium with depot fat. It follows that if livestock were recently exposed to PCDD/Fs (for example, through the consumption of contaminated feed), the analysis of depot fats would not necessarily provide a reliable indicator of the concentrations of PCDD/Fs in edible tissues.     

A proposal for a diet-based local PCDD/F deposition limit

This study proposes a method to estimate the maximal tolerable value for the atmospheric deposition of dioxins (PCDD/Fs) to soil. The case study for the application of this methodology is an Alpine valley where a steel production plant is present. In order to estimate the limit value for the PCDD/F deposition, consolidated food chain models were applied, but were adapted to be run backwards with respect to their original formulation, by starting from the diet of people living in the region and from the PCDD/F Tolerable Daily Intake value proposed by the World Health Organization. For this case study, the estimated limit value was 2.30 pg WHO-TEQ m⁻² d⁻¹ when only local diary products were taken into account and 1.91 pg WHO-TEQ m⁻² d⁻¹ when also the role of local cereals and vegetables was considered. The average PCDD/F deposition measured in the same region during a monitoring campaign was lower than the above limit values (1.40 pg WHO-TEQ m⁻² d⁻¹). Indications on how to consider the contribution of meat and fish are provided too. The approach proposed in this paper represents a useful tool to assess the acceptable overall deposition for a specific region.     

The emission inventory of PCDD/PCDF in Taiwan

Establishment of a country or region-based dioxin inventory was considered a crucial step toward elimination of worldwide dioxins/POPs contaminations, although no harmonized method for the preparation of an inventory is available at present. In this study, we used limited data and information to generate an inventory of dioxin emissions from some major sources in Taiwan. A total of 67.25 g I-TEQ of dioxins released annually was estimated. Unlike most of the industrialized countries, municipal waste incineration is not the highest contributor for dioxins released into the atmosphere. In contrast, secondary copper smelting accounts for more than 39% of the total dioxin emissions, and is higher than those from all waste incinerators combined (23.7%). Cement kilns and electric arc furnaces for steels also produced significant portion (both >10%) of dioxins into the environment, followed by secondary aluminum smelting (6.53%), industrial oil combustion (5.02%) and power plants fueled by coal (5.01%). Other known sources are either insignificant with respect to their dioxin emissions or not included in this inventory due to lack of information or uncertainty of the results. Data presented in this report provide a general picture of dioxin emissions in Taiwan, but were mostly based on less reliable or representative information, especially with respect to emission factors from different emission sources. It is necessary to establish background information relative to our own environment at present. Upon available, the inventory should be updated accordingly for proper environmental management on dioxins.     

Urea as a PCDD/F Inhibitor in Municipal Waste Incineration

ABSTRACT

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from municipal waste incineration have been widely studied because of their extensive toxicity, and many efforts have been made to restrict their emissions. Although a number of chemical compounds have been shown in laboratory-scale tests to inhibit the formation of PCDD/Fs, few have been tested in pilot- or full-scale plants. This work evaluates the effect of urea as a PCDD/F inhibitor in a pilot-scale incinerator that uses refuse-derived fuel (RDF). The decomposition of urea under the test conditions was also studied using detailed kinetic modeling. An aqueous solution of urea was injected into the flue gas stream after the furnace at ~730 °C, with varied urea concentrations and flue gas residence times used between the furnace and the sampling point. The results demonstrate that urea can successfully inhibit PCDD/F formation in waste incineration if concentrations and injection points are properly adjusted. The kinetic model showed that urea can be rapidly decomposed under appropriate flue gas conditions, indicating that in addition to the urea molecule itself, decomposition products of urea can also be responsible for the reduction of PCDD/F production during incineration.     

Urea as a PCDD/F inhibitor in municipal waste incineration

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from municipal waste incineration have been widely studied because of their extensive toxicity, and many efforts have been made to restrict their emissions. Although a number of chemical compounds have been shown in laboratory-scale tests to inhibit the formation of PCDD/Fs, few have been tested in pilot- or full-scale plants. This work evaluates the effect of urea as a PCDD/F inhibitor in a pilot-scale incinerator that uses refuse-derived fuel (RDF). The decomposition of urea under the test conditions was also studied using detailed kinetic modeling. An aqueous solution of urea was injected into the flue gas stream after the furnace at approximately 730 degrees C, with varied urea concentrations and flue gas residence times used between the furnace and the sampling point. The results demonstrate that urea can successfully inhibit PCDD/F formation in waste incineration if concentrations and injection points are properly adjusted. The kinetic model showed that urea can be rapidly decomposed under appropriate flue gas conditions, indicating that in addition to the urea molecule itself, decomposition products of urea can also be responsible for the reduction of PCDD/F production during incineration.     

PCDD/PCDF reduction by the co-combustion process

A novel process, termed the co-combustion process, has been developed and designed to utilise the thermal treatment of municipal solid waste (MSW) in cement clinker production and reduce PCDD/PCDF emissions. To test the conceptual design; detailed engineering design of the process and equipment was performed and a pilot plant was constructed to treat up to 40 tonnes MSW per day. The novel process features included several units external to the main traditional cement rotary kiln: an external calcinations unit in which the hot gas calcined the limestone thus making significant energy savings for this chemical reaction; the lime generated was used in a second chamber to act as a giant acid gas scrubber to remove SOx and particularly HCl (a source of chloride); an external rotary kiln and secondary combustion unit capable of producing a hot gas at 1200 degrees C; a gas cooler to simulate a boiler turbogenerator set for electricity generation; the incorporation of some of the bottom ash, calcined lime and dust collector solids into the cement clinker. A PCDD/PCDF inventory has been completed for the entire process and measured PCDD/PCDF emissions were 0.001 ng I-TEQ/Nm(3) on average which is 1% of the best practical means [Hong Kong Environmental Protection Department, 2001. A guidance note on the best practicable means for incinerators (municipal waste incineration), BPM12/1] MSW incineration emission limit values.     

Improvements to the UK PCDD/F and PCB atmospheric emission inventory following an emissions measurement programme

PCDD/F data are presented from 75 samples of primary emissions sampled between 1995-97 as part of the compliance monitoring survey undertaken by the UK Environment Agency. Municipal solid waste (MSW), chemical waste and clinical waste incinerators, cement kilns, sinter plants and sewage sludge incinerators were the source categories monitored and reported here. Based on this monitoring programme, the previous national UK emission estimates by Eduljee and Dyke (1) of 560-1100 g I-TEQ a(-1) for 1993 have been revised downwards to 220-660 g I-TEQ a(-1). Despite source reduction measures, MSW incinerators remain a significant source of PCDD/Fs to the atmosphere, contributing between 30-50% of the EPCDD/F I-TEQ emission, rather than the approximately 80% they were estimated to contribute in 1993. 2,3,7,8-substituted PCDD/F congener profile data are presented for some of the source categories and generally support the view that differences in the mixtures ('fingerprints') of PCDD/Fs emitted from different sources are observed. New data on the dioxin-like PCB emissions are presented for cement kilns and sinter plants. These show that TEQ-rated PCBs can make an important contribution to the I-TEQ emitted from certain combustion sources. High concentrations of a full range of PCB congeners/homologues have been measured in the atmosphere close to sintering strands, although the precise source of PCBs from this process remains unclear.     

PCDD/F concentrations in soil and vegetation in the vicinity of a municipal waste incinerator after a pronounced decrease in the emissions of PCDD/Fs from the facility

Emission of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) by municipal solid waste incinerators (MSWI) is an issue of great concern. In 1997, an adaptation to the EU legislation on pollutant emissions from the stack was carried out in an MSWI from Tarragona (Catalonia, Spain). As a result, PCDD/F emissions were significantly reduced. The aim of this study was to determine the current levels of PCDD/Fs in soil and vegetation samples collected near the facility and to compare these levels with those obtained in previous surveys (1996 and 1997). In the period 1997-1999, PCDD/F concentrations in vegetation samples were significantly decreased (60%). By contrast, the levels of PCDD/Fs in soil samples increased slightly (14%, P > 0.05) during the same period. An exhaustive analysis of the present data indicates that other emission sources of PCDD/Fs have also a notable environmental impact on the area under direct influence of the MSWI.     

Assessment of PCDD/F and PBDD/F emissions from coal-fired power plants during injection of brominated activated carbon for mercury control

The effect of the injection of brominated powdered activated carbon (Br-PAC) on the emission of brominated and chlorinated dioxins and furans in coal combustion flue gas has been evaluated. The sampling campaigns were performed at two U.S. Department of Energy (DOE) demonstration sites where brominated PAC was being injected for control of mercury emissions. The results of the sampling campaigns showed that injection of the brominated PAC upstream of the electrostatic precipitator (ESP) did not increase the emissions of total and Toxic EQuivalent (TEQ) chlorinated and brominated dioxin compounds. Rather, the data suggested the sorbent may capture these compounds and reduce their concentration in the flue gas stream. This effect, when seen, was small, and independent of the type of plant emission controls, temperature at the point of injection, or fuel-chlorine content. The addition of the brominated PAC sorbent resulted in slight increases the total content of chlorinated dioxins and furan in the particulate matter (ash) collected in the ESP, but did not increase its overall toxicity.     

PCDD/F levels in plasma of a belgian population before and after the 1999 belgian PCB/DIOXIN incident

We evaluated the impact of the 1999 Belgian dioxin incident on the blood plasma polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) levels among 232 Belgian blood donors (74% men, mean age 47 years). The Red Cross made plasma samples from before the incident of these donors available. A second plasma sample was collected during the second half of 2000. The sum of the 17 PCDD/F congeners was significantly lower in 2000 compared to 1998 (417 pg/g fat versus 445 pg/g fat, respectively). This could be completely attributed to the significant decrease of OctaCDD (301 pg/g fat in 2000 versus 277 pg/g fat in 1998). Moreover a slight but significant decrease was observed for 2,3,7,8-TetraCDF and for 1,2,3,4,6,7,8-HeptaCDF. 1,2,3,7,8-PentaCDF and 2,3,4,7,8-PentaCDF however showed a slight but significant increase (respective levels in 1998 were 0.004 and 14.5 pg/g fat compared to 0.006 and 17.9 pg/g fat in 2000). Given their significantly higher presence in incident related food samples this increase can be attributed to the food contamination episode. However, the total toxicity remained unchanged (22.9 in 1998 versus 23.1 pg WHO-TEQ/g fat, p>0.05). Moreover the observed congener profiles and the total PCDD/F levels were similar to those of other European non-occupationally exposed populations. In conclusion, the 1999 PCB/dioxin incident was traceable in the plasma profiles (rise of the two specific PCDF congeners), but comparison of the results for both years indicates that the changes were too small to cause an adverse public health effect.     

Modelling of PCDD/F release from MSW bio-drying

In the present work, an experimentation was carried out to study the behaviour of PCDD/F during the process of municipal solid waste (MSW) bio-drying. This process belongs to the biological mechanical treatment (BMT) options and is aimed to the dewatering of MSW thanks to the biological exothermal reactions (thermal drying, on the contrary, needs an external heat source as methane). The result is a decrease of waste weight and an increase of lower heating value (as the energy content refers to a lower amount of waste). Of course, the overall energy availability does not increase, but the characteristics of bio-drying are interesting as a way for refuse derived fuel generation: glass, metals and inert removals are easier after bio-drying. The literature of the sector shows only few data on PCDD/F emission to air from BMT. Anyway, in the present work an original theory has been put forward in order to explain the enrichment of PCDD/F in the air exiting the biological processes. The role of the initial PCDD/F concentration in the ambient air entering the plant is obviously taken into account. The results of the developed experimentation and the following elaborations point out that PCDD/F could be freed from the volatile solids consumed during the process. The different amount of PCDD/F in the waste and the different consumption of volatile solids depending on the biological process can explain the different PCDD/F emission factors available in the literature.