Evaluation of carbonization as a thermal pretreatment method for landfilling by column leaching tests

To evaluate carbonization as a thermal pretreatment method for landfilling, the releasing characteristics of organic and inorganic constituents from carbonization residue derived from shredded residue of bulky waste was investigated by means of batch and column leaching tests. Shredded residue of bulky waste itself and its incineration ash were tested together to compare pretreatment methods. In batch leaching tests at a liquid/solid ratio of 10, the release of organic carbon from carbonization residue was at a remarkably low level. Besides, carbonization contributed to immobilize heavy metals such as chromium, cadmium, and lead within its residue. In column tests, the discharges of organic constituents were lowest from carbonization residue under aerobic conditions due to microbial activity. The leaching of Cd, Cr, Pb, and Cu from carbonization residue was suppressed under anaerobic conditions; however, this suppression effect tended to be weaker under aerobic conditions. From the results showing that the total releasing amounts of organic and inorganic constituents from carbonization residue are so low as to be comparable to that of incineration ash, carbonization can be considered as one of the thermal pretreatment methods of organic wastes.     

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.     

Demobilisation of critical contaminants in four typical waste-to-energy ashes by carbonation

Two bottom ashes, one air pollution control (APC) residue and one fly ash from three different Swedish municipal solid waste incineration (MSWI) plants were characterised regarding the leaching of environmentally relevant components. Characterisation was performed using a diffusion tank leaching test. The impact of carbonation on the release of eight critical components, i.e., Cl(-), Cr, Cu, Mo, Pb, Sb, Se, SO(4)(2-) and Zn, was assessed at a lab-scale and showed carbonation to have a more pronounced demobilising effect on critical components in bottom ashes than in APC residue and fly ash. From grate type incinerator bottom ash, the release of Cr decreased by 97%, by 63% for Cu and by 45% for Sb. In the investigated APC residue, the releases of Cr, Se and Pb were defined as critical, although they either remained unaffected or increased after carbonation. Cl(-) and SO(4)(2-) remained mobile after carbonation in all investigated residues.     

Chemical properties of heavy metals in typical hospital waste incinerator ashes in China

Incineration has become the main mechanism for hospital waste (HW) disposal in China after the outbreak of Severe Acute Respiratory Syndrome (SARS) in 2003. However, little information is available on the chemical properties of the resulting ashes. In the present study, 22HW ash samples, including 14 samples of bottom ash and eight samples of fly ash, were collected from four typical HW incineration plants located across China. Chemical analysis indicated that the HW ashes contained large amounts of metal salts of Al, Ca, Fe, K, Mg, Na with a concentration range of 1.8-315gkg(-1). Furthermore, the ashes contained high concentrations of heavy metals such as Ag, As, Ba, Bi, Cd, Cr, Cu, Mn, Ni, Pb, Ti, Sb, Sn, Sr, Zn with a vast range of 1.1-121,411mgkg(-1), with higher concentrations found in the fly ash samples. Sequential extraction results showed that Ba, Cr, Ni and Sn are present in the residual fraction, while Cd existed in the exchangeable and carbonate fractions. As, Mn, Zn existed in the Fe-Mn oxide fraction, Pb was present in the Fe-Mn oxide and residual fractions, and Cu was present in the organic matter fraction. Furthermore, toxicity characteristic leaching procedure (TCLP) results indicated that leached amounts of Cd, Cu and Pb from almost all fly ash samples exceeded the USEPA regulated levels. A comparison between the HW ashes and municipal solid waste (MSW) ash showed that both HW bottom ash and fly ash contained higher concentrations of Ag, As, Bi, Cd, Cr, Cu, Pb, Ti, and Zn. This research provides critical information for appropriate HW incineration ash management plans.     

Metallic aluminum in MSWI fly ash: quantification and influence on the properties of cement-based products

This article focuses on the effects of metallic aluminum contained in municipal solid waste incineration (MSWI) fly ashes on cement-based materials in which they are added. The ash under study was treated by an industrial physicochemical process of neutralization. The paper also presents a method to quantify the metallic aluminum content of ash: it consists in measuring the amount of hydrogen gas produced by the oxidation reaction of metallic aluminum. This method is simple and fast. Results show that studied ash contains an appreciable amount of metallic aluminum. Investigations were carried out to study the incorporation of the ash in concrete: in this case, the presence of metallic aluminum is worrying because it could be responsible for disorders in concrete. In fact, swellings are observed on cement pastes and mortars containing ash during the first 24 h of hydration. A test based on hydrostatic weighing permits to quantify the swelling of fresh cement paste and to study the evolution of this swelling. Causes of swelling are analyzed. Results show that ettringite formation occurs after the end of the expansion reaction. So it can be concluded that metallic aluminum is the sole responsible for the observed swelling. Consequences of swelling are also analyzed by measuring compressive strength of ash-containing mortars: this swelling leads to cracks in the mortars and significant decrease of their compressive strength.     

Behavior of TiO2 nanoparticles during incineration of solid paint waste: A lab-scale test

In order to assess the potential impacts posed by products containing engineered nanoparticles, it is essential to generate more data about the release of these particles from products’ life cycle. Although first studies were performed to investigate the release of nanoparticles from use phase, very few data are available on the potential release from recycling or disposal of nano-enhanced products.In this work, we investigated the behavior of TiO₂ nanoparticles from incineration of solid paint waste containing these particles. Solid paint debris with and without TiO₂ nanoparticles were treated in a lab scale incineration plant at 950 °C (combustion temperature) and in oxidizing atmosphere. The obtained ashes were also vitrified with additives and the release of Ti was finally evaluated by leaching test. From our incineration lab-scale experiment, we did not observe a release of TiO₂ nanoparticles into the atmosphere, and Ti was attached to the surface of obtained solid residues (i.e. ashes). The characterization of ashes showed that TiO₂ nanoparticles reacted during the incineration to give calcium titanate. Finally, a very low release of Ti was measured, less 1 mg/kg, during the leaching test of ashes vitrified with glass cullet and feldspathic inert. Our work suggests that TiO₂ nanoparticles added in paints may undergo to physicochemical transformation during the incineration, and that Ti found in ashes may be strongly immobilized in glass matrix. Since this conclusion is based on lab-scale experiment, further research is required to identify which nanoparticles will be emitted to the environment from a real-word-incineration system of household hazardous waste.     

Leaching behaviour of elements and evaluation of pre-treatment methods for municipal solid waste incinerator residues in column leaching tests.

Two new pre-treatment methods (water-washing/carbonation and carbonation/phosphate stabilization) of municipal solid waste (MSW) incinerator residues were evaluated by column leaching tests under aerobic conditions and anaerobic conditions (which were changed to aerobic conditions after 10 months). A mixture of bottom ash and fly ash (5:1 ratio) was pre-treated using each method. Shredded incombustible residues (SIR) were added to each ash preparation in proportions similar to the ratios present in landfills. For comparison, landfill wastes typical of Japan, namely, a mixture of bottom ash, chelating-pre-treated fly ash, and SIR, were also examined. Leachate samples were collected periodically and analysed over a 15-month period. When compared with chelating pretreatment, both water-washing/carbonation and carbonation/ phosphate stabilization reduced the leaching of Pb, Al, and Cu by about one to two orders of magnitude. Moreover, the initial concentrations of Ca and Pb in leachates from column of water-washing/carbonation were 56-57% and 84-96% less than those from the column of carbonation/phosphate stabilization. Therefore, water-washing/carbonation was considered to be a promising approach to obtain early waste stabilization and to reduce the release of heavy metals to near-negligible levels. The leaching behaviour of elements was also discussed.     

High temperature co-treatment of bottom ash and stabilized fly ashes from waste incineration

Bottom ashes from two Danish municipal solid waste incineration plants were heated at 900 degrees C with iron oxide stabilized air pollution control residues at actual mass flow ratios (9:1), simulating a treating method for the residues. The two residues were co-treated, producing one combined stream that may be utilized as a secondary road construction material. Scanning electron microscope analysis and grain size distribution analysis indicated that sintering of the particles did not occur. Batch leaching tests at liquid/solid 10 l/kg at a range of pH-values (6-10) quantified with respect to Cd, Cr and Pb revealed significant positive effects of co-heating the ashes, although Pb showed slightly increased leaching. At a liquid/solid ratio of 10 l/kg the leachate concentrations were still low at pH 7-10 and the release of Pb was, thus, not expected to limit the utilization of the mixed ashes. The process, thus, fixates the metals in the solid residues without altering the leaching properties of the bottom ash too significantly.     

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.     

Influence of test conditions on solubility controlled leaching predictions from air-pollution-control residues.

Leaching of Al, Ca, Mg, Si, S, Ba, Sr, Mo, Zn, Cd, Pb, and Cu from waste incineration air-pollution-control (APC) residues was investigated. Real-life conditions, i.e. removal of readily soluble compounds and longer equilibration time, were considered. Three different pH-static leaching experiments evaluating the importance of salt level and equilibration time were performed: (i) 48-h test on untreated APC residue samples, (ii) 48-h test on washed residue samples, and finally (iii) a 172-h test on washed residue samples. Experimental data were evaluated by geochemical modelling to identify potential solubility controlling minerals. For some elements (Al, Ca, Mg, Si, S, Mo, Zn, Cd, and Cu) the same controlling minerals were suggested regardless of the equilibration period or untreated/washed character of the tested material, whereas leaching of other elements (Ba, Sr) was far better described by considering a longer equilibration time, thereby pointing out the kinetic effects. Finally, a significant fraction of total lead (57%) was found to be rather mobile in the initial stage of leaching. Both pre-washing of the residues and longer equilibration times were shown to be simple yet useful methods to identify mineral phases that could control the release of constituents after the removal of readily soluble compounds in the initial stage of leaching.     

Reuse of municipal solid wastes incineration fly ashes in concrete mixtures

This study is aimed at assessing the feasibility of concrete production using stabilized m.s.w. (municipal solid waste) incineration fly ashes in addition to natural aggregates. The tested fly ashes were washed and milled, then stabilized by a cement-lime process and finally were reused as a "recycled aggregate" for cement mixture production, in substitution of a natural aggregate (with dosage of 200-400 kg m(-3)). These mixtures, after curing, were characterized with conventional physical-mechanical tests (compression, traction, flexure, modulus of elasticity, shrinkage). In samples containing 200 kg(waste) m(-3)(concrete), a good compressive strength was achieved after 28 days of curing. Furthermore, concrete leaching behavior was evaluated by means of different leaching tests, both on milled and on monolithic samples. Experimental results showed a remarkable reduction of metal leaching in comparison with raw waste. In some cases, similar behavior was observed in "natural" concrete (produced with natural aggregates) and in "waste containing" concrete.     

Metal mobilization from municipal solid waste incineration bottom ash through metal complexation with organic and inorganic ligands

As a first step in the development of ligand-assisted removal of heavy metals from municipal solid waste incineration bottom ash under alkaline conditions, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, urea, and mixtures of ammonium salts and urea were examined to find which ligands could promote the leachability of elements, including heavy metals, and which elements could be mobilized through complexation. Ammonium citrate promoted the mobilization of Cr, Cu, Mn, P, Sb, and especially Fe. Ammonium nitrate accelerated Mg leachability significantly. Under the conditions used in this study, counter anions seemed to contribute mainly to the complexation. When a mixture of ammonium citrate and urea was utilized, a coexistence effect appeared on Fe mobilization. Although the correlation analysis of leaching test results showed a strong correlation among Cr, Cu, Fe, Mn, and P, X-ray diffraction analysis partially supported the correlation between Fe and Mn only.     

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.     

Changes in carbon and nitrogen pool during in-situ aeration of old landfills under varying conditions

Emissions from old landfills via leachate and the gas phase are influenced by state and stability of the organic matter in the solid waste and by environmental conditions within the landfill. Remediation of landfills by means of in-situ aeration is one possibility to reduce these emissions. By establishing aerobic conditions, biological processes in the landfill are accelerated. To investigate the effects of this remediation technology, lab-scale experiments with column tests have been carried out. The main goal of the present work is to characterize the changes of the carbon and nitrogen compounds in the aerated solid waste, the leachate and the gas phase under varying conditions. The results demonstrate a clear reduction of emissions and a stabilization of the organic matter. Furthermore, it is shown that both the intensity of aeration and the amount of water affect biological processes to a certain extent. Even when columns were operated under anaerobic conditions after a long running period of aeration, the emissions remained low.     

Chemical stability of geopolymers containing municipal solid waste incinerator fly ash

Municipal solid waste incinerators every year produce tons of fly ashes which, differently from coal fly ashes, contain large amounts of toxic substances (heavy metals, dioxins, furans). The stabilization/solidification (S/S) technology known as geopolymerization is proposed with the purpose to bond physically and chemically incinerator fly ashes (IFA) in a solid matrix, in order to reduce pollutant mobility. The chemical stability of geopolymers with Si/Al ratio of 1.8–1.9 and Na/Al ratio of 1.0, synthesized by alkali activation of metakaolin and the addition of 20 wt% of two different kinds of IFA, is presented. The concentration of the alkaline solution, water to solid ratio and curing process have been optimized. The room temperature consolidation of IFA containing geopolymers has been tested for leachability in water for 1 day, accordingly to EN 12457 regulation and extended to 7 days to increase the water attack on solid granules. Leachable metals in the test solution, determined by ICP_AES, fall within limit values set by regulation for non-dangerous waste landfill disposal. Geopolymeric matrix evolution with leaching time has been also evaluated in terms of pH and electrical conductivity increase in solution.     

Comparison of leaching characteristics of heavy metals from bottom and fly ashes in Korea and Japan

The objective of this research was to compare the leaching characteristics of heavy metals such as cadmium, chromium, copper, nickel, lead, etc., in Korean and Japanese municipal solid waste incineration (MSWI) ash. The rate of leaching of heavy metal was measured by KSLT and JTL-13, and the amount of heavy metals leached was compared with the metal content in each waste component. Finally, bio-availability testing was performed to assess the risks associated with heavy metals leached from bottom ash and fly ash. From the results, the value of neutralization ability in Japanese fly ash was four times higher than that in Korean fly ash. The reason was the difference in the content of Ca(OH)(2) in fly ash. The amount of lead leached exceeded the regulatory level in both Japanese and Korean fly ash. The rate of leaching was relatively low in ash with a pH in the range of 6-10. The bio-availability test in fly ash demonstrated that the amount of heavy metals leached was Pb>Cd>Cr, but the order was changed to Pb>Cr>Cd in the bottom ash. The leaching concentration of lead exceeded the Japanese risk level in all fly ashes from the two countries, but the leaching concentration of cadmium exceeded the regulatory level in Korean fly ash only.     

Comparative studies of waste incineration bottom ashes from various grate and firing systems,conducted with respect to mineralogical and geochemical methods of examination

Mineralogical and geochemical techniques can be used successfully to characterize and evaluate bottom ashes produced in waste incineration. At the present time, it is not quite clear to what extent the mineral phase compositions and the content of main elements and heavy metal concentrations of bottom ashes are influenced by the conditions of combustion. Once the location of heavy metals in or with specific minerals is known, it may be considered, in the light of technical possibilities, whether a change in temperature or in the residence time of waste in the combustion chamber could be sufficient to remove these components from their mineral phases.     

Leaching from solid waste incineration ashes used in cement-treated base layers for pavements

Waste incineration bottom ash and treated flue gas cleaning products mixed with 2.5% of cement (50 kg/m3) were tested in the laboratory in terms of compressive strength and tank leaching tests over a 64-day period. Although the material displayed lower mechanical strength than a reference concrete, the strength still was sufficient for use as a base layer for roads. The metal content in the incineration-residue-based specimens was up to 100 times higher than in the reference concrete, suggesting that the mixed waste incineration residue should be used only for dedicated purposes. The leaching of Cl and Na was increased by a factor of 20-100 from the incineration-residue-based specimens as compared to the reference, while the leaching of K, Ca and SO4 was increased by a factor of 2-10. The leaching of heavy metals was also higher from the incineration-residue-based specimens than from the reference with respect to Cu (50 times), Cd, Pb and Zn (5 times), but not with respect to Cr and Ni. The leaching curves did only allow for a closer evaluation of the leaching process in a few cases. The physical retention of the constituents seemed to be the same in the reference as in the incineration-residue-based specimens. Heavy metal leaching was limited by enhanced chemical retention in the incineration-residue-specimens as compared to the reference. Since no quality criteria in terms of leaching from a monolithic material are currently available, the leaching issue must be evaluated case by case.     

Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste

Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated the isotopic signatures of δ¹³C, δ²H and δ¹⁸O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25 year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration.We found significant differences in the δ¹³C-value of the dissolved inorganic carbon (δ¹³C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ¹³C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ¹³C-DIC of ?20‰ to ?25‰. The production of methane under anaerobic conditions caused an increase in δ¹³C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW. During aeration of a landfill the aerobic degradation of the remaining organic matter caused a decrease to a δ¹³C-DIC of about ?20‰. Therefore carbon isotope analysis in leachates and groundwater can be used for tracing the oxidation–reduction status of MSW landfills.Our results indicate that monitoring of stable isotopic signatures of landfill leachates over a longer time period (e.g. during in situ aeration) is a powerful and cost-effective tool for characterising the biodegradability and stability of the organic matter in landfilled municipal solid waste and can be used for monitoring the progress of in situ aeration.     

Metal releases from a municipal solid waste incineration air pollution control residue mixed with compost

The influence of 10 wt.% mature compost was tested on the heavy metal leachate emissions from a calcium-rich municipal solid waste incineration air pollution control residue (MSWI APC). Apart from elongated columns (500 and 1250 mm), an otherwise norm compliant European percolation test setup was used. More than 99% of the metals Al, As, Cd, Cr, Cu, Fe and Ni were left in the APC residue after leaching to a liquid-to-solid ratio (L/S) of 10. Apparent short-term effects of elevated leachate DOC concentrations on heavy metal releases were not detected. Zn and Pb leachate concentrations were one order of magnitude lower for L/S 5 and 10 from the pure APC residue column, which suggests a possible long-term effect of compost on the release of these elements. Prolonging the contact time between the pore water and the material resulted in elevated leachate concentrations at L/S 0.1 to L/S 1 by a factor of 2. Only Cr and Pb concentrations were at their maxima in the first leachates at L/S 0.1. Equilibrium speciation modelling with the PHREEQC code suggested portlandite (Ca(OH)2) to control Ca solubility and pH.