Surface catalyzed halogenation-dehalogenation reactions of aromatic bromine compounds adsorbed on fly ash

Brominated aromatic compounds like brominated benzenes, diphenylethers and dibenzodioxins adsorbed on the surface of fly ash from a municipal waste incininerator give mixed brominated/chlorinated und completely chlorinated aromatic compounds. These consecutive halogenation-dehalogenation reactions proceed by a nucleophilic mechanism, which is favoured by a high concentration of chloride on the fly ash. Results of kinetic and stereoselective behavior of these reactions will be discussed. The relevance of these results for PCDD/PCDF formation from bromine precursors in municipal waste incinerators will be discussed.     

Polycyclic aromatic hydrocarbons in weathered bottom ash from incineration of municipal solid waste

Polycyclic aromatic hydrocarbons (PAHs) were analysed in weathered bottom ash from different municipal solid waste incinerators. The sum of the 16 "USEPA" PAHs was found to vary from 480 to 3590 microg/kg. The amounts of carcinogenic PAHs were between 89 and 438 microg/kg ash. The maximum levels of carcinogenic PAHs exceed the Swedish generic guidelines for sensitive land use. The results showed that the amount of PAHs in fresh and weathered bottom ash are similar, indicating that the PAHs are strongly bound to the ash and only limited amounts are released to the surroundings.     

Comparison of 2,4,6-trichlorophenol conversion to PCDD/ PCDF on a MSWI-fly ash and a model fly ash

We performed experiments on two different matrices with 2,4,6-trichlorophenol as precursor to Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD)/F. A municipal solid waste incinerators (MSWI) and a model fly ash were spiked in two different ways. The experiments demonstrated a three times higher formation potential of the trichlorophenol to PCDD on MSWI fly ash compared with the model fly ash used. For both fly ashes the PCDD yield was higher when gaseous trichlorophenol was fed continuously compared to mixing the fly ashes prior to the experiments with the total amount of the precursor. Despite dilution of the fly ashes tenfold with an inactive matrix the conversion of the chlorophenol was very high.     

Use of Bioassay Methods to Evaluate Mutagenicity of Ambient Air Collected Near a Municipal Waste Combustor

An ambient air sampling study was conducted around a municipal waste combustor; a primary goal was to develop procedures and methods to evaluate the emissions of organic mutagens resulting from incomplete combustion of municipal waste. The products of Incomplete combustion from incineration include complex mixtures of organics, particularly polycycllc aromatic compounds, which are present after atmospheric dilution and cooling In emissions as semi-volatile or particle bound organic compounds. Combustion emissions are generally recognized as a potential cancer risk since they contain many carcinogenic and mutagenlc polycyclic aromatic hydrocarbons. Analyzing such a complex mixture for the presence of even a few selected chemicals is difficult and provides risk information on only a fraction of the chemicals present. Bioassay methods, however, may be directly applied to evaluate the mutagenic and potential carcinogenic activity of the complex organics from combustion emissions. The Salmonella (Ames) assay was used to determine the mutagenicity associated with particles from ambient air collected near a municipal waste combustor. Dose-response data was generated, and mutagenicity concentrations were calculated to demonstrate the utility of bioassay In assessing the potential Impact of emissions from municipal waste combustion. This phase of study quantified mutagenicity concentrations In ambient air but did not detect organic mutagens that could be attributed to Incinerator emissions.     

Size distribution and leaching characteristics of poly brominated diphenyl ethers (PBDEs) in the bottom ashes of municipal solid waste incinerators

The particle size distributions and leaching characteristics of polybrominated diphenyl ethers (PBDEs) in the bottom ashes of two Taiwanese municipal solid waste incinerators (MSWIs A and B) were investigated to evaluate PBDE leaching into the environment through reutilization of bottom ashes. The PBDE contents in the bottom ashes of the MSWIs (29.0–243 ng/g) could be two orders higher than those in rural and urban soils. The PBDE fraction of the bottom ashes was more distributed in larger particles (> 0.25 mm). Similar trends were found for the PBDE contents in the bottom ashes and their PBDE leaching concentrations, revealing that the elevated PBDE contents in the bottom ashes may lead to a higher PBDE leaching mass. The leaching of PBDEs is attributed to diffusion driven by the concentration gradient and effective surface area. The normalized leaching ratios (NLRs) of PBDEs for the bottom ashes of the MSWIs are about four orders greater than those of PBDE-related raw materials and products, and this may be due to their porous structures having much greater effective surface area. The elevated NLRs of PBDEs thus deserve more attention when bottom ashes are recycled and reutilized as construction materials.     

Dioxin-like potencies and extractable organohalogens (EOX) in medical, municipal and domestic waste incinerator ashes in Japan

Ash samples collected from medical, municipal and small-scale domestic incinerators in Japan were tested for dioxin-like activity using bioassay technique (ethoxyresorufin-O-deethylase: EROD assay) and for extractable organohalogens (EOX) using instrumental neutron activation analysis in order to estimate potential toxicity and responsible chemicals in those samples. Crude extracts and fractions cleaned-up for dioxin analysis from the samples were used for the analysis. The ranges of dioxins in the ashes were between 2.23 and 12.29 ng TEQ/g (dry weight). Relative potency ranges estimated by EROD assay in the medical incinerator ashes were 3.8-17.6 times higher than the results of conventional chemical analysis. EOX analysis suggested that ash samples contained plenty of organochlorine compounds apart from chlorinated dioxins. In addition, medical waste incinerator ashes were considered to have relatively higher amount of organoiodine compounds. In the cleaned-up fractions, bioassay potency ranges were lower than those in the crude extracts. However, some samples still exhibited higher potency than expected from chemical analysis. Though some polycyclic aromatic hydrocarbons were found in the fractions, the amounts were relatively low (0.39-10.56 ng/g). The results imply that some bioactive organohalogens that cannot be detected in the conventional chemical analysis might have potential for dioxin-like toxicity, and contribute to higher bioassay activities. The combination of the chemical analysis with the bioassay and EOX provides rough figure of dioxin-like toxicity and suggests types of organohalogen compounds that should be identified as a part of dioxin analysis for control emission from an incineration plant.     

Determination of polychlorinated dibenzo-p-dioxins and dibenzo-furans in solid residues from wood combustion by HRGC/HRMS

PCDD/PCDF were determined in solid samples from wood combustion. The samples included grate ashes, bottom ashes, furnace ashes as well as fly and cyclone ashes. The solid waste samples were classified into bottom and fly ash from native wood and bottom and fly ash from waste wood. For each of the four classes concentration distribution patterns from individual congeners, the sums of PCDD/PCDF and the international toxicity equivalents (I-TEQ) values are given. The I-TEQ levels of fly ash from waste wood burning can be approximately up to two thousand times higher than the values from fly ashes of natural wood. The I-TEQ levels in bottom ashes from waste wood combustion systems are as low as the corresponding ashes from the combustion of native wood. Grate ash samples from waste wood combustion systems with low carbon burnout show high levels of PCDD/PCDF.     

Screening of heavy metal containing waste types for use as raw material in Arctic clay-based bricks

In the vulnerable Arctic environment, the impact of especially hazardous wastes can have severe consequences and the reduction and safe handling of these waste types are therefore an important issue. In this study, two groups of heavy metal containing particulate waste materials, municipal solid waste incineration (MSWI) fly and bottom ashes and mine tailings (i.e., residues from the mineral resource industry) from Greenland were screened in order to determine their suitability as secondary resources in clay-based brick production. Small clay discs, containing 20 or 40% of the different particulate waste materials, were fired and material properties and heavy metal leaching tests were conducted before and after firing. Remediation techniques (washing in distilled water and electrodialytical treatment) applied to the fly ash reduced leaching before firing. The mine tailings and bottom ash brick discs obtained satisfactory densities (1669–2007 kg/m³) and open porosities (27.9–39.9%). In contrast, the fly ash brick discs had low densities (1313–1578 kg/m³) and high open porosities (42.1–51. %). However, leaching tests on crushed brick discs revealed that heavy metals generally became more available after firing for all the investigated materials and that further optimisation is therefore necessary prior to incorporation in bricks.     

Assessment of MSWI bottom ash organic carbon behavior: a biophysicochemical approach

In order to understand the influence of organic components on the behavior of municipal solid waste incinerator bottom ash, samples from five French incinerators have been analyzed and compared. Biological and physico-chemical experiments were coupled with a view to developing a new rapid assessment method of bottom ash quality. Bottom ash had different total organic carbon contents ranging from 8.8 g kg(-1) to 37.4 g kg(-1). A part of this organic carbon can be leached into the environment or provide a substrate for microbial activity. Samples showed really different behaviors regarding these processes. Comparative results of leaching tests and biodegradation experiments showed a positive correlation between dissolved organic carbon and microbial activity. However, quantities of biodegraded or leached carbon are not representative of the samples' total organic carbon content. Thermal analyses in oxidizing conditions have revealed the presence of two fractions of organic components, showing different thermal behaviors. The associated mass losses were measured and compared to dissolved organic carbon. One of the two fractions can be directly linked to the leachable and easily biodegradable organic matter fraction. Calorimetric test is then presented as a novel analysis method that allows to provide rapid and global information concerning the characteristics of organic matter in bottom ash and its possible short and long-term evolution.     

Melting and incineration plants of municipal waste. Chemical and biochemical diagnosis of thermal processing samples (emission,residues)

Control of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in emissions and thermal residues from incinerators has been a cause of public concern for more than one decade. Recently, several studies showed that other persistent organic pollutants (POPs) such as coplanar polychlorinated biphenyls (co-PCBs) also have dioxin-like activity and are released from incinerators. Therefore, the present study was aimed at making a risk assessment about dioxin-like activity in extracts of thermal waste residues (e.g. combustion gas; fly ash, slag) from incineration and melting processes in Germany and Japan. For this purpose, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (co-PCBs), polychlorinated naphthalenes (PCNs) and polyaromatic hydrocarbons (PAHs) were analyzed by chemical analysis. Additionally, 2, 3, 7, 8-TCDD equivalents (EROD-TEQs) were determined by in vitro Micro-EROD bioassay using rat H4IIE hepatoma cells. EROD-TEQs could be correlated to I-TEQ values (from PCDD/Fs/co-PCBs) analyzed by chemical analysis resulting in a maximal sixfold higher estimate. Our study indicates minor influences of co-PCBs, PAHs and PCNs to the sum of dioxin-like toxicity in the extracts of thermal waste residues as determined here. Furthermore, we showed that the levels of dioxins and co-PCBs contained in slag from melting processes and bottom ashes from incineration processes were lower by 1-2 orders of magnitude than that in fly ash.     

Investigation of 1,4-dioxane originating from incineration residues produced by incineration of municipal solid waste

As a groundwater contaminant, 1,4-dioxane is of considerable concern because of its toxicity, refractory nature to degradation, and rapid migration within an aquifer. Although landfill leachate has been reported to contain significant levels of 1,4-dioxane, the origin of 1,4-dioxane in leachate has not been clarified until now. In this study, the origins of 1,4-dioxane in landfill leachate were investigated at 38 landfill sites and three incineration plants in Japan. Extremely high levels of 1,4-dioxane 89 and 340 microg l(-1), were detected in leachate from two of the landfill sites sampled. Assessments of leachate and measurement of 1,4-dioxane in incineration residues revealed the most likely source of 1,4-dioxane in the leachate to be the fly ash produced by municipal solid waste incinerators. Effective removal of 1,4-dioxane in leachate from fly ash was achieved using heating dechlorination systems. Rapid leaching of 1,4-dioxane observed from fly ash in a sequential batch extraction indicated that the incorporation of a waste washing process could also be effective for the removal of 1,4-dioxane in fly ash.     

Element immobilization in refuse incinerator ashes by solidification in glass, ceramic or cement

Incineration of municipal refuse results in the production of massive quantities of fly ash and bottom ash. Toxic elements in the original refuse may be concentrated up to 40-fold in the resultant ash. There is concern that burial of such ash in landfills could result in leaching of these elements downward into groundwater. In this study, refuse ashes were incorporated into glass, ceramic and cement composites to immobilize such toxic elements. The EP Toxicity Test (1986) was used to show that extraction of such elements by simulated acid rain is effectively blocked in these new solid materials.     

Evaluation of Canisters for Measuring Emissions of Volatile Organic Air Pollutants from Hazardous Waste Incineration

Regulation to control air emissions of toxic organic compounds require the collection and analysis of effluent gas from low level sources such as hazardous waste incinerators. The standard SW- 846 Method specifies the use of Tenax and Tenax/charcoal adsorbent traps for collection of volatile organics from incinerators. This study evaluates passivated stainless steel canisters as an alternative to adsorbent traps to eliminate some of the problems associated with adsorbent sampling. Initially the stability of 18 nonpolar, volatile organic compounds was determined in Summa-treated stainless steel canisters with greater than 100 ppmv HCI and saturated with water vapor. All 18 components were stable for a twoweek period; however, an Interference caused a 10-fold increase In the FID response of trlchloroethylene, toluene, and chlorobenzene. No Interference of the ECD response was found for any of the 11 compounds detected with the ECD including trlchloroethylene. A pilot scale incinerator was sampled using canisters, and the destruction efficiency of 1,1,1-trichloroethane was determined at a concentration of less than 0.5 ppbv while determining 1,1-dichloroethylene, the major product of Incomplete combustion, at a concentration of 8000 ppbv from the same sample.     

Dechlorination and destruction of PCDDs/PCDFs in fly ashes from municipal solid waste incinerators by low temperature thermal treatment

Dechlorination and destruction characteristics of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in fly ashes from commercial-scale municipal solid waste incinerators by low temperature thermal treatment using a laboratory-scale heating system were investigated. Experiments were carried out in reducing atmosphere at temperatures of 300 degrees C, 450 degrees C and 600 degrees C respectively, for the treatment time of 1h and 3h. Concentrations of PCDDs/PCDFs in raw fly ashes ranged from 35.5 to 107.3 microg kg(-1) (1.5-3.4 microg TEQ kg(-1)) and treated fly ashes ranged from 0.34 to 45.3 microg kg(-1) (0.012-1.63 microg TEQ kg(-1)). Concentrations of PCDDs/PCDFs in fly ashes treated at the different temperatures and times were observed to decrease with increase of treatment temperature and time by dechlorination or destruction. The distribution of octa- and hepta-chlorinated congeners were decreased and tetra-, penta- and hexa-chlorinated congeners were increased at 300 degrees C and 450 degrees C, but the distribution of octa- and hepta-chlorinated congeners were increased and tetra-, penta- and hexa-chlorinated congeners were again decreased at 600 degrees C. Total destruction efficiencies of PCDDs/PCDFs in fly ashes showed above 95% at the treatment temperature of 450 degrees C for 3h. However, removal efficiency of each congener in fly ashes varied, especially, 2,3,7,8-TeCDD and 1,2,3,7,8-PeCDD in fly ash A increased. And the dechlorination and destruction characteristics of PCDDs/PCDFs in fly ash A and B was different due to difference in contents of Ca-compounds and metal oxides such as CuO and PbO in fly ashes.     

The behavior of PCDD and PCDF during thermal treatment of waste incineration ash

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.     

Extraction of heavy metals from MSW incinerator fly ash using saponins

An extraction process with saponins was evaluated for removing heavy metals from MSW (municipal solid waste) incinerator fly ashes. Two different fly ashes, A and B, were treated on a laboratory scale with three triterpene-glycoside type of saponins, M, Q, and T, in the pH range 4-9. The results were compared with those of the HCI and EDTA treatment. The treatment with saponins extracted 20-45% of Cr from the fly ashes. Saponins were also effective in extracting Cu from fly ash A attaining 50-60% extraction. Saponin T extracted 100% of Pb from fly ash A at pH around 4. The extraction of Zn with the saponin treatment was similar to that of the HCl treatment. Further, Cr, Cu, Pb, and Zn were fractionated by sequential extraction to investigate the effect of saponins on each fraction. Extraction behavior of other elements during the saponin treatment was also studied. The leaching test on the residues received after the saponin treatment showed that the fly ashes were successfully detoxified to meet the landfilling guideline.     

Influence of organic matter on municipal solid waste incinerator bottom ash carbonation

The biodegradation of organic matter in municipal solid waste incinerator (MSWI) bottom ash was studied in order to investigate the interaction between the CO(2) produced by microbial respiration and bottom ash. Respiration tests were performed on bottom ash at different moisture contents in an incubator at 30 degrees C. O(2) consumption and CO(2) production were monitored and quantified. Leaching tests were carried out at the end of the experiments. Total organic carbon (TOC) leaching had decreased. Over a period of three weeks, pH decreased from 10.7 to 8.2 and bottom ash was considered to be fully carbonated. This showed that the organic matter found in bottom ash can provide a substrate for microbial activity. The CO(2) produced by microbial respiration was directly dissolved in bottom ash pore water in order to be mineralized in carbonate form. The origin of the carbon dioxide which induces maturation of bottom ash on weathering areas has never been really discussed and is often presumed to be atmospheric CO(2). However, biodegradation of organic matter could contribute for a large part to this phenomenon, depending on field-scale physico-chemical weathering conditions.     

Experimental and statistical determination of indicator parameters for the evaluation of fly ash and boiler ash PCDD/PCDF concentration from municipal solid waste incinerators

On-line detectable indicator parameters in the flue gas of municipal solid waste incinerators (MSWI) such as chlorinated benzenes (PCBz) are well known surrogate compounds for gas-phase PCDD/PCDF concentration. In the here presented work derivation of indicators is broadened to the detection of fly and boiler ash fractions with increased PCDD/PCDF content. Subsequently these fractions could be subject to further treatment such as recirculation in the combustion chamber to destroy their PCDD/PCDF and other organic pollutants' content. Aim of this work was to detect suitable on-line detectable indicator parameters in the gas phase, which are well correlated to PCDD/PCDF concentration in the solid residues. For this, solid residues and gas-phase samples were taken at three MSWI plants in Bavaria. Analysis of the ash content from different plants yielded a broad variation range of PCDD/PCDF concentrations especially after disturbed combustion conditions. Even during normal operation conditions significantly increased PCDD/PCDF concentrations may occur after unanticipated disturbances. Statistical evaluation of gas phase and ash measurements was carried out by means of principal component analysis, uni- and multivariate correlation analysis. Surprisingly, well known indicators for gas-phase PCDD/PCDF concentration such as polychlorinated benzenes and phenols proved to be insufficiently correlated to PCDD/PCDF content of the solid residues. Moreover, no single parameter alone was found appropriate to describe the PCDD/PCDF content of fly and boiler ashes. On the other hand, multivariate fitting of three or four parameters yielded convenient correlation coefficients of at least r=0.8 for every investigated case. Thereby, comprehension of plant operation parameters such as temperatures and air flow alongside concentrations of inorganic compounds in the gas phase (HCl, CO, SO2, NOx) gave the best results. However, the suitable set of parameters suited best for estimation of PCDD/PCDF concentration in solid residues has to be derived anew for each individual plant and type of ash.     

Cytotoxicity of municipal solid waste incinerator ash wastes toward mammalian kidney cell lines

In this study, three municipal solid waste incinerator (MSWI) ash wastes-bottom ash, scrubber residue, and baghouse ash-were extracted using a toxicity characteristic leaching procedure (TCLP) extractant. These so-called final TCLP extracts were applied to African green monkey kidney cells (Vero), baby hamster kidney cells (BHK-21), and pig kidney cells (PK-15), multi-well absorption reader analysis was performed to test how the cytotoxicity of the incineration ashes would affect the digestive systems of animals. Ion-coupled plasma analyses indicated that the baghouse ash extract possessed the highest pH and heavy metal concentration, its cytotoxicity was also the highest. In contrast, the bottom ash and the scrubber residue exhibited very low cytotoxicities. The cytotoxicities of mixtures of baghouse ash and scrubber residue toward the three tested cell lines increased as the relative ratio of the baghouse ash increased, especially for the Vero cells. The slight cytotoxicity of the scrubber residue arose mainly from the presence of Cr species, whereas the high cytotoxicity of the baghouse ash resulted from its high content of heavy metals and alkali ions. In addition, it appears that the dissolved total organic carbon content of these ash wastes can reduce the cytotoxicity of ash wastes that collect in animal cells.     

Levels and characteristic homologue patterns of polychlorinated dibenzo-p-dioxins and dibenzofurans in various incinerator emissions and in air collected near an incinerator

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were monitored in stack gas and fly ash of various Korean incinerators and in air samples collected near the facilities. Concentrations of PCDD/Fs in emissions were investigated, and characteristic PCDD/F homologue patterns were classified using statistical analyses. The PCDD/F emission levels in stack gas and fly ash samples from small incinerators (SIs) were higher than those from municipal solid waste incinerators (MSWIs). The PCDD/F concentrations ranged between 0.38 and 1.16 pg I-TEQ/m3 (21.2-75.2 pg/m3) in ambient air samples. The lower-chlorinated furans were the dominant components in most of the stack gas and fly ash samples from SIs, although this was not the case for fly ash from MSWIs. This homologue pattern is consistent with other studies reporting a high fraction of lower-chlorinated furans in most environmental samples affected by incinerator emissions, and it can be used as an indicator to assess the impact of such facilities on the surrounding environment.