Ecotoxicological characterisation of 12 incineration ashes using 6 laboratory tests

In the European Waste List (2000/532/EC as amended) the ash of municipal waste incineration is defined as a so called mirror entry. This waste can be classified as hazardous or non-hazardous depending on the content of hazardous substances and other risk properties. For the assignment of waste in mirror entries, 14 criteria are defined. One of the criteria is H14 “ecotoxic”. In the presented study, the ecotoxicological potential of 12 ashes from different incineration plants has been assessed using biological test systems. The test battery included aquatic tests with eluates (algae, daphnids, and luminescent bacteria) and terrestrial tests with solid waste (plants, earthworms and bacteria). The test results revealed a clear ecotoxicological hazard potential for some of the MWI ashes. Despite the fact that fresh ashes were several times more toxic than aged ashes both groups did not differ consistently in terms of toxicity. The results show also that there is no correlation between the biological effects and the analyzed chemical compounds of the ash samples.     

Controlled combustion tests and bottom ash analysis using household waste with varying composition

The influence of the co-combustion of household waste with either sewage sludge, shredder fluff, electronic and electrical waste (WEEE) or PVC on the bottom ash quality and content was investigated under controlled laboratory conditions using a pot furnace. This laboratory approach avoids the interpretation problems related to large variations in input waste composition and combustion conditions that are observed in large scale MSW incinerators. The data for metals content, transfer coefficients and leaching values are presented relative to data for a base household waste composition that did not contain any of the added special wastes. The small WEEE invited direct measurement of precious metals content in the ashes, where measurement accuracy is facilitated by using only mobile phone scrap for small WEEE. The analyses were carried out for different particle size ranges that are of relevance to the recyclability of metals and minerals in the ashes. Positive correlations were found between elements content of the input waste and the bottom ashes, and also between increased levels of Cl, Mo and Cu in the input waste and their leaching in the bottom ashes. These correlations indicate that addition of PVC, small WEEE and shredder fluff in input waste can have a negative influence on the quality of the bottom ashes. Enrichment of Au and Ag occurred in the fractions between 0.15 and 6 mm. The precious metals content represents an economically interesting intrinsic value, even when the observed peak values are properly averaged over a larger volume of ashes. Overall, it has been shown that changes in quality and content of bottom ashes may be traced back to the varied input waste composition.     

Metal leachability, heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in fly and bottom ashes of a medical waste incineration facility

Medical waste from hospitals and other healthcare institutions has become an imperative environmental and public safety problem. Medical waste in Greece has become one of the most urgent environmental problems, because there are 14,000 tons produced annually, of which only a small proportion is incinerated. In the prefecture of Attica there is only one modern municipal medical waste incinerator (started 2004) burning selected infectious hospital waste (5-6 tons day(-1)). Fly and bottom residues (ashes) are collected and stored temporarily in barrels. High values of metal leachability prohibit the landfilling of these ashes, as imposed by EU directives. In the present study we determined quantitatively the heavy metals and other elements in the fly and bottom ashes of the medical waste incinerator, by inductively coupled plasma emission spectrometry (ICP) and by energy dispersive X-ray analysis (EDAX). Heavy metals, which are very toxic, such as Pb, Cd, Ni, Cr, Cu and Zn were found in high concentrations in both fly and bottom ashes. Metal leachability of fly and bottom ashes by water and kerosene was measured by ICP and the results showed that toxic metals in both ashes, such as Pb, Cr, Cd, Cu and Zn, have high leaching values. These values indicate that metals can become soluble and mobile if ash is deposited in landfills, thus restricting their burial according to EU regulations. Analysis of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in fly and bottom ashes showed that their concentrations were very low. This is the first known study in Greece and the results showed that incineration of medical waste can be very effective in minimizing the most hazardous and infectious health-care waste. The presence of toxic metals with high leachability values remains an important draw back of incineration of medical waste and various methods of treating these residues to diminish leaching are been considered at present to overcome this serious technical problem.     

Ecotoxicological assessment of leachates from MSWI bottom ashes

In this paper, chemical and ecotoxicological data of leachates from bottom ashes collected in different Municipal Solid Waste Incinerators (MSWI) are shown. The bottom ashes were collected in Belgium (three incinerators--samples B1 to B3), France, Germany, Italy and United Kingdom (one incinerator in each country--samples F1, D1, I1 and UK1, respectively). Both chemical and ecotoxicological characterizations of leachates were done on the framework of the European Directive 91/689/EEC and the European Council Decision 94/904/EC. This work was carried out under the European project called Valomat, which was supported by the European Commission through Brite-Euram III program. Twenty-one inorganic parameters were analyzed. The ecotoxicological assays were done under standard laboratory conditions, using the bacterium Photobacterium phosphoreum, the freshwater alga Pseudokirchneriella subcapitata, the crustacean Daphnia magna and the vegetable Lactuca sativa. Chemical data varied from sample to sample. Similar results were obtained in biological assays. The samples can be classified as ecotoxic/hazardous according to the French proposal for a Criterion and Evaluation Methods of Waste Ecotoxicity (CEMWE) and the German regulation on Hazardous Waste Classification (HWC). However, samples B1, B2, B3 and D1 comply the maximum limits for direct valorization category defined in the French Classification of Bottom Ashes based on their Polluting Potential (CBAPP). Sample B1 presented the lowest level of ecotoxicity, being considered as the most interesting to be used in the development of new materials for civil engineering works.     

Belgian MSWI fly ashes and APC residues: a characterisation study

Municipal Solid Waste Incineration (MSWI) produces different sorts of residues, bottom ash, fly ashes and Air Pollution Control (APC) residues. Generally, fly ashes and APC residues are mixed at the MSWI plant and manage as a sole residue. In this study, fly ashes and APC residues have been sampled separately at different Belgian MSWI plant and analysed by X-ray fluorescence in order to highlight the composition differences that may appear between the solids. Ca and Cl are found to be the major elements in most of the samples. Lithophilic elements, such as Al and Si, are richer in furnace and boiler ashes, as can be expected. Leaching tests also show differences between the residues; leachates from furnace and boiler ashes are alkaline while those from bag filter residues present a pH value of 6, which impacts the leaching of heavy metals (Pb and Zn). The results suggest that it could be advantageous to manage fly ashes and APC residues separately by adjusting the treatment to their specificities.     

MSWI boiler fly ashes: magnetic separation for material recovery

Nowadays, ferrous materials are usually recovered from Municipal Solid Waste Incineration (MSWI) bottom ash by magnetic separation. To our knowledge, such a physical technique has not been applied so far to other MSWI residues. This study focuses thus on the applicability of magnetic separation on boiler fly ashes (BFA). Different types of magnet are used to extract the magnetic particles. We investigate the magnetic particle composition, as well as their leaching behaviour (EN 12457-1 leaching test). The magnetic particles present higher Cr, Fe, Mn and Ni concentration than the non-magnetic (NM) fraction. Magnetic separation does not improve the leachability of the NM fraction. To approximate industrial conditions, magnetic separation is also applied to BFA mixed with water by using a pilot. BFA magnetic separation is economically evaluated. This study globally shows that it is possible to extract some magnetic particles from MSWI boiler fly ashes. However, the magnetic particles only represent from 23 to 120 g/kg of the BFA and, though they are enriched in Fe, are composed of similar elements to the raw ashes. The industrial application of magnetic separation would only be profitable if large amounts of ashes were treated (more than 15 kt/y), and the process should be ideally completed by other recovery methods or advanced treatments.     

A study of Cr(VI) in ashes from fluidized bed combustion of municipal solid waste: leaching, secondary reactions and the applicability of some speciation methods

The use of the fluidized bed technique for the combustion of municipal solid waste is a rather new concept. This type of combustor produces ash residues with somewhat different properties than the residues generated from the traditional mass burn techniques. Therefore, chemical characterization and the investigation of toxic metals behavior during ash water reactions are necessary for the safe disposal of these residues. In the present work, the total elemental composition, mineralogy and leaching behavior of ashes from the combustion of municipal solid waste in a fluidized bed combustion boiler have been investigated. The cyclone ash and, in particular, the filter ash contained considerable amounts of soluble substances, thus giving leachates with high levels of Cl-, Na+, K+, Ca2 + and Al(IIl). On the other hand, the two ash fractions taken in the boiler, the bottom and hopper ashes, were much more stable with respect to the release of salts and heavy metals. Since Cr(VI) is mobile and toxic its release from combustion residues can pose environmental problem. Even though the total Cr contents were similar in all ashes studied, the bottom ash gave about a thousand times higher levels of Cr(VI) in test leachates than the hopper, cyclone and filter ashes. However, it was found that the leached amount of Cr(VI) from the bottom ash decreased significantly when bottom ash was mixed with the hopper ash. The most probable cause for this decrease is the coupled oxidation of Al(0) to Al(III) and reduction of dissolved Cr(VI) to Cr(III). This finding that the mixing of two ash streams from the same boiler could result in the immobilization of Cr may point at a simple stabilization method. Selective extraction of water soluble, exchangeable and sparingly soluble forms of Cr(VI) was also investigated. Extraction methods were evaluated for their suitability for ash matrixes. It was found that interferences due to the presence of reducing substances in some ash materials may occur.     

Characterization of MSWI bottom ashes towards utilization as glass raw material

The characterization of the bottom ashes produced by two Portuguese municipal solid waste incinerators (MSWI) was performed with the aim of assessing the feasibility of using this waste as raw material in the production of glass that can be further processed as glass-ceramics for application in construction. Density and particle size distribution measurements were carried out for physical characterization. Chemical characterization revealed that SiO(2), a network glass former oxide, was present in a relatively high content (52-58wt%), indicating the suitability for this waste to be employed in the development of vitreous materials. CaO, Na(2)O and K(2)O, which act as fluxing agents, were present in various amounts (2-17wt%) together with several other oxides normally present in ceramic and glass raw materials. Mineralogical characterization revealed that the main crystalline phases were quartz (SiO(2)) and calcite (CaCO(3)) and that minor amounts of different alkaline and alkaline-earth aluminosilicate phases were also present. Thermal characterization showed that the decomposition of the different compounds occurred up to 1100 degrees C and that total weight loss was <10wt%. Heating both bottom ashes at 1400 degrees C for 2h resulted in a melt with suitable viscosity to be poured into a mould, and homogeneous black-coloured glasses with a smooth shiny surface were obtained after cooling. The vitrified bottom ashes were totally amorphous as confirmed by X-ray diffraction. The results from the present experimental work indicate that the examined bottom ashes can be a potential material to melt and to obtain a glass that can be further processed as glass-ceramics to be applied in construction.     

Management of incinerator residues in Flanders (Belgium) and in neighbouring countries. A comparison

This paper covers the Flemish legislative tools concerning the management of bottom ash, fly ash and APC residue from municipal waste incinerators, with respect to their contamination with heavy metals. The situation in Flanders is compared to the one in the Walloon region, The Netherlands, Germany and France. Waste management in the countries considered differs on the level of available management options, of leaching tests and of limit values. To make an indicative comparison of leaching tests and limit values in the different countries, leaching tests were carried out on bottom ash and fly ash, and the results are compared to the relevant limit values for recycling and landfilling of the different countries. The comparison of legislations as well as the leaching results show that discrepancies in waste management between the different regions and countries exist. Recently, European limit values for landfilling became available. European legislation on recycling, however, has not been developed and urgently needs to be considered and drafted as the market for recycling can be expanding rapidly.     

Influence of assumptions about household waste composition in waste management LCAs

This article takes a detailed look at an uncertainty factor in waste management LCA that has not been widely discussed previously, namely the uncertainty in waste composition. Waste composition is influenced by many factors; it can vary from year to year, seasonally, and with location, for example. The data publicly available at a municipal level can be highly aggregated and sometimes incomplete, and performing composition analysis is technically challenging. Uncertainty is therefore always present in waste composition. This article performs uncertainty analysis on a systematically modified waste composition using a constructed waste management system. In addition the environmental impacts of several waste management strategies are compared when applied to five different cities. We thus discuss the effect of uncertainty in both accounting LCA and comparative LCA. We found the waste composition to be important for the total environmental impact of the system, especially for the global warming, nutrient enrichment and human toxicity via water impact categories.     

Enrichment of elements in industrial waste incineration bottom ashes obtained from three different types of incinerators,as studied by ICP-AES and ICP-MS

The elemental composition of the industrial waste incineration bottom ash (IWIBA) samples collected from three different types of incinerator with different kinds of wastes were compared. The major-to-ultratrace elements in the IWIBA samples were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). As a result, ca. 40 elements in the concentration range from milligrams per gram to submicrograms per gram could be determined with relative standard deviations of less than 5%. The IWIBA sample from petrochemical wastes contained lower concentrations of the elements, because fewer mineral constituents were contained in the input waste materials. On the contrary, the elemental concentrations in the IWIBA sample from industrial solid wastes provided the highest values for most elements, while the elemental compositions of the IWIBA sample from food wastes were similar to those of municipal solid waste incineration bottom ash. In addition, it was found from the analytical results that the levels of various heavy metals such as Cr, Mn, Fe, Ni, Cu, As, Zr, Mo, Sb, Ba, and Pb were higher in the IWIBA samples than in municipal solid waste incineration bottom ash. The enrichment factors of the elements in the IWIBA samples were estimated from the analytical results to compare the elemental distributions in incineration bottom ashes in relation to their mining influence factors, which are the indices for human use of the elements.     

Use of vitrified MSWI bottom ashes for concrete production

Bottom ashes from a north Italian municipal solid waste incinerator (MSWI) were vitrified at 1450 degrees C without adding any vitrifying agent, then ground and sieved to different granulometry (ranging from 50 microm to 20mm), and used as filler, sand, or aggregate for concrete. Samples were characterized via slump tests (UNI 9418), alkali-silica reactivity (UNI 8520/22 and ASTM C 298), and compression strength tests (UNI 6132, 6132/72, 6686/72), and compared to reference samples obtained without vitrified bottom ashes (VBA). Our results show that vitrified bottom ashes are unsuitable as a sand substitute; however, concrete containing up to 20 wt.% of VBA filler used as a substitute for cement and up to 75 vol.% of VBA as a substitute for natural aggregate retains the same mechanical properties as reference samples. Alkali-silica or other detrimental reactions were not observed in VBA-containing concrete samples after a period of two years. The results of this work demonstrate that vitrified bottom ashes from MSWI can be used instead of natural aggregates in mortar and concrete production.     

Cement-based materials as containment systems for ash from hospital waste incineration

Waste generation has increased considerably worldwide in the last decades. As a consequence, incineration became an alternative for reducing waste volume, leading to the generation of ash as a new type of waste. The new cement-ash composite systems have been tested for future applications in building materials. Having in mind the previous data and scientific reports, the objective of the present study is oriented to evaluate the additions of hospital waste ash in cement matrices to be potentially used as construction elements. This involved the assessment of the effect of the additions (different proportions of ash and metal-spiked ash) on the physico-mechanical properties of the building materials and the leachability of metals. The experiences show the feasibility of including hospital waste ashes in masonry blocks or other similar products.     

Quantification of the resource recovery potential of municipal solid waste incineration bottom ashes

Municipal solid waste incineration (MSWI) plays an important role in many European waste management systems. However, increasing focus on resource criticality has raised concern regarding the possible loss of critical resources through MSWI. The primary form of solid output from waste incinerators is bottom ashes (BAs), which also have important resource potential. Based on a full-scale Danish recovery facility, detailed material and substance flow analyses (MFA and SFA) were carried out, in order to characterise the resource recovery potential of Danish BA: (i) based on historical and experimental data, all individual flows (representing different grain size fractions) within the recovery facility were quantified, (ii) the resource potential of ferrous (Fe) and non-ferrous (NFe) metals as well as rare earth elements (REE) was determined, (iii) recovery efficiencies were quantified for scrap metal and (iv) resource potential variability and recovery efficiencies were quantified based on a range of ashes from different incinerators. Recovery efficiencies for Fe and NFe reached 85% and 61%, respectively, with the resource potential of metals in BA before recovery being 7.2%ww for Fe and 2.2%ww for NFe. Considerable non-recovered resource potential was found in fine fraction (below 2 mm), where approximately 12% of the total NFe potential in the BA were left. REEs were detected in the ashes, but the levels were two or three orders of magnitude lower than typical ore concentrations. The lack of REE enrichment in BAs indicated that the post-incineration recovery of these resources may not be a likely option with current technology. Based on these results, it is recommended to focus on limiting REE-containing products in waste for incineration and improving pre-incineration sorting initiatives for these elements.     

Waste management from pulp and paper production in the European Union

Eleven million tonnes of waste are produced yearly by the European pulp and paper industry, of which 70% originates from the production of deinked recycled paper. Wastes are very diverse in composition and consist of rejects, different types of sludges and ashes in mills having on-site incineration treatment. The production of pulp and paper from virgin pulp generates less waste but the waste has similar properties to waste from the production of deinked pulp, although with less inorganics. Due to legislation and increased taxes, landfills are quickly being eliminated as a final destination for wastes in Europe, and incineration with energy recovery is becoming the main waste recovery method. Other options such as pyrolysis, gasification, land spreading, composting and reuse as building material are being applied, although research is still needed for optimization of the processes. Due to the large volumes of waste generated, the high moisture content of the waste and the changing waste composition as a result of process conditions, recovery methods are usually expensive and their environmental impact is still uncertain. For this reason, it is necessary to continue research on different applications of wastes, while taking into account the environmental and economic factors of these waste treatments.     

Release of salts from municipal solid waste combustion residues

Residues from fluidized bed combustion of municipal solid waste were investigated with respect to their leaching behavior and possible extraction of salts. The total water extractable amounts of Na, K, Ca, Cl(-), Br(-), F(-) and SO(4)(2-) along with the total dissolved solids of bottom, hopper, cyclone and bag house filter ashes were determined. A simple multistage washing process (using water as the extraction medium) was tested in lab scale experiments. The effect of variations in parameters, such as water to ash weight ratio, contact time, temperature and number of extraction steps was investigated. The leaching behavior of untreated and washed cyclone and bag house filter ashes was evaluated by a two-step batch-leaching test, i.e. the CEN test. The ashes investigated in this study can be arranged according to their decreasing water extractable contents and total dissolved solids as follows: filter ash > cyclone ash > hopper ash > bottom ash. A triple extraction with water at liquid to solid ratio 2 and extraction time 5 min gave the best results for the extraction of Ca, Na, K, Cl(-) and SO(4)(2-) from the cyclone as well as from the filter ashes. The leached amounts of salts in the CEN test performed on the washed cyclone ash were considerably lower than the corresponding amounts released from the unwashed ash. Thus, the washed cyclone ash was made more stable with respect to salt leachability. On the other hand, large amounts of salts were leached from the washed filter ashes as well as from unwashed filter ashes. Therefore, it can be concluded that three stage water extraction is not a suitable stabilization method for this type of filter ashes.     

Municipal solid waste composition determination supporting the integrated solid waste management system in the island of Crete

A one-year survey was conducted in the greater region of Crete (located at the lower region of the Aegean Sea) for the purpose of identifying waste composition (including chemical and physical characterization), as well as any seasonal variation. The investigation was carried out repeatedly at seven landfills and one transfer station in Crete, in four phases. Each sampling phase corresponded to a season (autumn, winter, spring, summer). ASTM D5231-92(2003) standard method and RCRA Waste Sampling Draft Technical Guidance were used. Hand sorting was used for classifying the collected wastes into the following categories: plastics, paper, metals, aluminium, leather-wood-textiles-rubbers, organic wastes, non-combustibles and miscellaneous. Further analysis included proximate and ultimate analysis of combustible materials. Metals such as lead, cadmium and mercury were also investigated. The results show that there has been a significant decrease of organic wastes during the last decade due to the increase of packaging materials, as a result of a change in consumption patterns. Three main waste categories were determined: organic wastes, paper and plastics, which combined represent 76% of the total waste in Crete. Furthermore, a high fraction of glass and a seasonal variation of aluminium indicate a strong correlation of waste composition with certain human activities, such as tourism. There is also a variation between the municipal solid waste (MSW) composition in the region of Crete (2003-2004) and MSW composition suggested in the National Solid Waste Planning (2000) [National Solid Waste Planning, 2000. Completion and particularization of Common Ministerial Act 113944//1944/1997: National Solid Waste Planning, June 2000]. The results of this survey are to be utilized by the regional solid waste authorities in order to establish an integrated waste treatment site, capable of fulfilling the regional waste management demands.     

Characteristics of ashes from different locations at the MSW incinerator equipped with various air pollution control devices

The characteristics of ashes from different locations at a municipal solid waste incinerator (MSWI) equipped with a water spray tower (WST) as a cooling system, and a spray dryer adsorber (SDA), a bag filter (BF) and a selective catalytic reactor (SCR) as air pollution control devices (APCD) was investigated to provide the basic data for further treatment of ashes. A commercial MSWI with a capacity of 100 tons per day was selected. Ash was sampled from different locations during the normal operation of the MSWI and was analyzed to obtain chemical composition, basicity, metal contents and leaching behavior of heavy metals. Basicity and pH of ash showed a broad range between 0.08-9.07 and 3.5-12.3, respectively. Some major inorganics in ash were identified and could affect the basicity. This could be one of the factors to determine further treatment means. Partitioning of hazardous heavy metals such as Pb, Cu, Cr, Hg and Cd was investigated. Large portions of Hg and Cd were emitted from the furnace while over 90% of Pb, Cu and Cr remained in bottom ash. However 54% of Hg was captured by WST and 41% by SDA/BF and 3.6% was emitted through the stack, while 81.5% of Cd was captured by SDA/BF. From the analysis data of various metal contents in ash and leach analysis, such capturing of metal was confirmed and some heavy metals found to be easily released from ash. Based on the overall characteristics of ash in different locations at the MSWI during the investigation, some considerations and suggestions for determining the appropriate treatment methods of ash were made as conclusions.     

Sequestration of metals in carbonated municipal solid waste incineration (MSWI) fly ash

Waste management is in need of a reliable and economical treatment method for metals in fly ashes from municipal solid waste incineration (MSWI). However, no state-of-the-art technique has gained wide acceptance yet. This paper is a synthesis of five elsewhere published investigations covering a project which aimed to assess the possibilities and limitations of adding carbon dioxide (CO2) to fly ash as a stabilization method. Carbonation factors that were studied are the partial pressure of carbon dioxide (CO2), the addition of water, the temperature, and the reaction time. Laboratory experiments were performed applying methods such as factorial experimental design, thermal analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD), and leaching assays including pHstat titration and sequential extraction. Leaching data were verified and complemented using chemical equilibrium calculations. Data evaluation was performed by means of multivariate statistics such as multiple linear regression, principal component analysis (PCA), and partial least squares (PLS) modeling. It was found that carbonation is a good prospect for a stabilization technique especially with respect to the major pollutants lead (Pb) and zinc (Zn). Their mobility decreased with increasing factor levels. Dominating factors were the partial pressure of CO2 and the reaction time, while temperature and the addition of water were of minor influence. However, the treatment caused a mobilization of cadmium (Cd), requiring further research on possible countermeasures such as metal demobilization through enhanced silicate formation.