Carbon speciation in municipal solid waste incinerator (MSWI) bottom ash in relation to facilitated metal leaching

The release of inorganic and organic contaminants from municipal solid waste incinerator (MSWI) bottom ash is controlled to a large extent by the release of dissolved organic carbon (DOC), and in particular by the reactive humic (HA) and fulvic acids (FA) subfractions of DOC. The properties of organic matter contributing to the release of DOC, HA and FA are, therefore, important for environmental risk assessment. In this study we have quantitatively measured the carbon speciation, and its relation with the leaching of Cu, in three fresh and carbonated MSWI bottom ash samples. Results show that up to only 25% of loss on ignition (LOI) consists of organic carbon (OC), while about 17% of OC in the three samples consists of HA and FA. Up to 50% of DOC in MSWI bottom ash leachates was identified as fulvic acid (FA). This value is substantially higher than previously estimated for these MSWI bottom ash samples and is consistent with the higher recovery of the new method that was applied. The results of this study imply that methods focusing on specific carbon fractions are more appropriate for assessment of environmentally relevant organic carbon species than the measurement of LOI.     

Hydrothermal treatment of MSWI bottom ash forming acid-resistant material

To recycle municipal solid waste incinerator (MSWI) bottom ash, synthesis of hydrothermal minerals from bottom ash was performed to stabilize heavy metals. MSWI bottom ash was mixed with SiO(2), Al(OH)(3), and Mg(OH)(2) so its chemical composition was similar to that of hydrothermal clay minerals. These solid specimens were mixed with water at a liquid/solid ratio of 5. The reaction temperature was 200 degrees C, and reactions were performed for 24-240h. Generation of kaolinite/smectite mixed-layer clay mineral was found in the samples after the reaction of the mixture of bottom ash, SiO(2), and Mg(OH)(2). Calcium silicate hydrate minerals such as tobermorite and xonotlite were also generated. X-ray powder diffraction suggested the presence of amorphous materials. Leaching tests at various pHs revealed that the concentration of heavy metals in the leachates from MSWI bottom ash hydrothermally treated with SiO(2) and Mg(OH)(2) was lower than that in leachates from non-treated bottom ash, especially under acid conditions. Hydrothermal treatment with modification of chemical composition may have potential for the recycling of MSWI bottom ash.     

Road soil retention of Pb leached from MSWI bottom ash

Municipal solid waste incinerator (MSWI) bottom ash may be used as a road construction material; it potentially contains however a sizable quantity of heavy metals, which under the effect of rainfall infiltration through the road structure can be leached out from the material and infiltrate into the underlying soil. An eco-compatibility assessment of MSWI bottom ash reuse in road construction applications necessitates examining the solubility and retention of heavy metals in road soils. This study is dedicated to Pb transfer, sorption and desorption (NEN 7341 standard test) within various soils. These experiments yield results relative to the interaction between road soils and an MSWI bottom ash leachate representative of a "fresh" product, with a high leaching potential. For the soils investigated, the sorption of lead varies between 90% and 99%. For an extraction at pH 7, Pb release is very low (<2%) for all soils, while at pH 4 leaching varies between 4% and 47%. This work shows that Pb may be fixed by some types of road soil in mostly stable forms.     

Strength, leachability and microstructure characterisation of Na2SiO3-activated ground granulated blast-furnace slag solidified MSWI fly ash.

The chemical composition and the leachability of heavy metals in municipal solid waste incinerator (MSWI) fly ash were measured and analysed. For the leachability of unstabilized MSWI fly ash it was found that the concentrations of Pb and Cr exceeded the leaching toxicity standard. Cementitious solidification of the MSWI fly ash by Na2SiO3-activated ground granulated blast-furnace slag (NS) was investigated. Results show that all solidified MSWI fly ash can meet the landfill standards after 28 days of curing. The heavy metals were immobilized within the hydration products such as C-S-H gel and ettringite through physical encapsulation, substitution, precipitation or adsorption mechanisms.     

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.     

Copper leaching of MSWI bottom ash co-disposed with refuse: Effect of short-term accelerated weathering

Co-disposal of refuse with municipal solid waste incinerator (MSWI) bottom ash (IBA) either multi-layered as landfill cover or mixed with refuse could pose additional risk to the environment because of enhanced leaching of heavy metals, especially Cu. This study applied short-term accelerated weathering to IBA, and monitored the mineralogical and chemical properties of IBA during the weathering process. Cu extractability of the weathered IBA was then evaluated using standard leaching protocols (i.e. SPLP and TCLP) and co-disposal leaching procedure. The results showed that weathering had little or no beneficial effect on Cu leaching in SPLP and TCLP, which can be explained by the adsorption and complexation of Cu with DOM. However, the Cu leaching of weathered IBA was reduced significantly when situated in fresh simulated landfill leachate. This was attributed to weakening Cu complexation with fulvic acid or hydrophilic fractions and/or intensifying Cu absorption to neoformed hydr(oxide) minerals in weathered IBA. The amount of total leaching Cu and Cu in free or labile complex fraction (the fraction with the highest mobility and bio-toxicity) of the 408-h weathered IBA were remarkably decreased by 86.3% and 97.6% in the 15-day co-disposal leaching test. Accelerated weathering of IBA may be an effective pretreatment method to decrease Cu leaching prior to its co-disposal with refuse.     

Metal leaching from MSWI bottom ash as affected by salt or dissolved organic matter

In order to manage municipal solid waste incineration (MSWI) bottom ash safely, risk assessments, including the prediction of leaching under different field conditions, are necessary. In this study, the influence of salt or dissolved organic matter (DOM) in the influent on metal leaching from MSWI bottom ash was investigated in a column experiment. The presence of salt (0.1M NaCl) resulted in a small increase of As leaching, whereas no impact on leachate concentration was found when lakewater DOM (35.1mg/l dissolved organic carbon) was added. Most of the added DOM was retained within the material. Further, X-ray spectroscopy revealed that Cu(II) was the dominating form of Cu and that it probably occurred as a CuO-type mineral. The Cu(2+) activity in the MSWI bottom ash leachate was most likely determined by the dissolution of CuO together with the formation of Cu-DOM complexes and possibly also by adsorption to (hydr)oxide minerals. The addition of lake DOM in the influent resulted in lower saturation indices for CuO in the leachates, which may be due to slow CuO dissolution kinetics in combination with strong Cu-DOM complexation.     

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.     

Life cycle assessment of disposal of residues from municipal solid waste incineration: recycling of bottom ash in road construction or landfilling in Denmark evaluated in the ROAD-RES model

Two disposal methods for MSWI bottom ash were assessed in a new life cycle assessment (LCA) model for road construction and disposal of residues. The two scenarios evaluated in the model were: (i) landfilling of bottom ash in a coastal landfill in Denmark and (ii) recycling of bottom ash as subbase layer in an asphalted secondary road. The LCA included resource and energy consumption, and emissions associated with upgrading of bottom ash, transport, landfilling processes, incorporation of bottom ash in road, substitution of natural gravel as road construction material and leaching of heavy metals and salts from bottom ash in road as well as in landfill. Environmental impacts associated with emissions to air, fresh surface water, marine surface water, groundwater and soil were aggregated into 12 environmental impact categories: Global Warming, Photochemical Ozone Formation, Nutrient Enrichment, Acidification, Stratospheric Ozone Depletion, Human Toxicity via air/water/soil, Ecotoxicity in water/soil, and a new impact category, Stored Ecotoxicity to water/soil that accounts for the presence of heavy metals and very persistent organic compounds that in the long-term might leach. Leaching of heavy metals and salts from bottom ash was estimated from a series of laboratory leaching tests. For both scenarios, Ecotoxicity(water) was, when evaluated for the first 100 yr, the most important among the twelve impact categories involved in the assessment. Human Toxicity(soil) was also important, especially for the Road scenario. When the long-term leaching of heavy metals from bottom ash was evaluated, based on the total content of heavy metals in bottom ash, all impact categories became negligible compared to the potential Stored Ecotoxicity, which was two orders of magnitudes greater than Ecotoxicity(water). Copper was the constituent that gave the strongest contributions to the ecotoxicities. The most important resources consumed were clay as liner in landfill and the groundwater resource which was potentially spoiled due to leaching of salts from bottom ash in road. The difference in environmental impacts between landfilling and utilization of bottom ash in road was marginal when these alternatives were assessed in a life cycle perspective.     

Distribution of remaining Cd in MSWI fly ash washed with nitric acid

Municipal solid waste incineration (MSWI) fly ash is by-product and hazardous waste produced from MSWI plant. In the MSWI fly ash there are high contents heavy metals, among which cadmium (Cd) is more active and toxic. Although inorganic acid leaching is an effective way to remove heavy metals out from the MSWI fly ash and nitric acid has great efficiency for Cd removal, little literature reported the redistribution of remaining Cd in the MSWI fly ash. This investigation focused on the change of different factions (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter and residual) of Cd in treated (i.e. washed with nitric acid) MSWI fly ash. Sequence extraction procedures (SEP) have been used to derive different fractions of Cd, results indicated that fractions of Cd have changed significantly after nitric acid washing procedures. Due to the changes of main compounds and microstructures stable Cd (bound to organic matter and residual) had opportunity to leach out, which resulted in a higher potential risk (or higher bioavailability index) for living creatures, although the total amount of Cd decreased. X-ray diffraction (XRD) and images of scanning electron microscope (SEM) proved these changes in washed MSWI fly ash.     

Effect of carbonation on the leaching of organic carbon and of copper from MSWI bottom ash

In Flanders, the northern part of Belgium, about 31% of the produced amount of MSWI bottom ash is recycled as secondary raw material. In view of recycling a higher percentage of bottom ash, a particular bottom ash fraction (Ø 0.1–2 mm) was studied. As the leaching of this bottom ash fraction exceeds some of the Flemish limit values for heavy metals (with Cu being the most critical), treatment is required.Natural weathering and accelerated carbonation resulted in a significant decrease of the Cu leaching. Natural weathering during 3 months caused a decrease of Cu leaching to <50% of its original value, whereas accelerated carbonation resulted in an even larger decrease (to ca. 13% of its initial value) after 2 weeks, with the main decrease taking place within the first 48 h.Total organic carbon decreased to ca. 70% and 55% of the initial concentration in the solid phase, and to 40% and 25% in the leachate after natural weathering and after accelerated carbonation, respectively. In the solid material the decrease of the Hy fraction was the largest, the FA concentration remained essentially constant. The decrease of FA in the leachate can be attributed partly to an enhanced adsorption of FA to Fe/Al (hydr)oxides, due to the combined effect of a pH decrease and the neoformation of Al (hydr)oxides (both due to carbonation). A detailed study of adsorption of FA to Fe/Al (hydr)oxides showed that significant adsorption of FA occurs, that it increases with decreasing pH and started above pH 12 for Fe (hydr)oxides and around 10 for Al (hydr)oxides. Depending whether FA or Hy are considered the controlling factor in enhanced Cu leaching, the decreasing FA or Hy in the leachate explains the decrease in the Cu leaching during carbonation.     

Reducing volatilization of heavy metals in phosphate-pretreated municipal solid waste incineration fly ash by forming pyromorphite-like minerals

This research investigated the feasibility of reducing volatilization of heavy metals (lead, zinc and cadmium) in municipal solid waste incineration (MSWI) fly ash by forming pyromorphite-like minerals via phosphate pre-treatment. To evaluate the evaporation characteristics of three heavy metals from phosphate-pretreated MSWI fly ash, volatilization tests have been performed by means of a dedicated apparatus in the 100-1000 °C range. The toxicity characteristic leaching procedure (TCLP) test and BCR sequential extraction procedure were applied to assess phosphate stabilization process. The results showed that the volatilization behavior in phosphate-pretreated MSWI fly ash could be reduced effectively. Pyromorphite-like minerals formed in phosphate-pretreated MSWI fly ash were mainly responsible for the volatilization reduction of heavy metals in MSWI fly ash at higher temperature, due to their chemical fixation and thermal stabilization for heavy metals. The stabilization effects were encouraging for the potential reuse of MSWI fly ash.     

Leaching behavior of heavy metals from municipal solid waste incineration bottom ash and its geochemical modeling

With the increase in the number of municipal solid waste incineration (MSWI) plants constructed in China recently, great attention has been paid to the heavy metal leaching toxicity of MSWI residues. In this study, the effects of various parameters, including extractant, leaching time, liquid-to-solid ratio, leachate pH, and heavy metal content, on the release properties of Cd, Cr, Cu, Ni, Pb, and Zn from MSWI bottom ash were investigated. Partial least-squares analysis was employed to highlight the interrelationships between the factors and response variables. Both experimental research and geochemical modeling using Visual MINTEQ software were conducted to study the pH-dependent leaching behavior of these metals in fresh and weathered bottom ash, considering precipitation/dissolution and surface complexation reactions (adsorption by hydrous ferric oxide and amorphous aluminum oxide/hydroxide). The results showed that leachate pH was the predominant factor influencing heavy metal leachability. The leaching of Cu, Pb, and Zn was mainly controlled by precipitation/dissolution reactions, whereas surface complexation had some effect on the leaching of Cr, Cd, and Ni for certain pH ranges. The modeling results aggreed well with the experimental results. Part of this work was presented at the Fourth International Conference on Combustion, Incineration/Pyrolysis and Emission Control (i-CIPEC)     

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.     

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.     

Short-term natural weathering of MSWI bottom ash as a function of particle size

The chemical and material composition of MSWI bottom ash depends on the particle size; this suggests that the mechanisms and kinetics of natural weathering are also a function of particle size. This paper reports the effects of short-term natural weathering on the leaching of heavy metals (mainly Pb, Cu and Zn) from MSWI bottom ash. Initial concentrations of heavy metals were higher for the smallest particle size fractions, but these levels fell dramatically during the first 50 days of weathering before levelling off. The main differences between size fractions were in the pH and the solubility of calcium and aluminium. For the initial stages of weathering and small size fractions, portlandite solubility seemed to control the pH. In contrast, for fractions bigger than 6 mm, the formation of ettringite was the reaction controlling the pH and the solubility of sulphates, aluminium and calcium.     

Environmental assessment of incinerator residue utilisation

Incineration ashes may be treated either as a waste to be dumped in landfill, or as a resource that is suitable for re-use. In order to choose the best management scenario, knowledge is needed on the potential environmental impact that may be expected, including not only local, but also regional and global impact. In this study, A life cycle assessment (LCA) based approach was outlined for environmental assessment of incinerator residue utilisation, in which leaching of trace elements as well as other emissions to air and water and the use of resources were regarded as constituting the potential environmental impact from the system studied. Case studies were performed for two selected ash types, bottom ash from municipal solid waste incineration (MSWI) and wood fly ash. The MSWI bottom ash was assumed to be suitable for road construction or as drainage material in landfill, whereas the wood fly ash was assumed to be suitable for road construction or as a nutrient resource to be recycled on forest land after biofuel harvesting. Different types of potential environmental impact predominated in the activities of the system and the use of natural resources and the trace element leaching were identified as being relatively important for the scenarios compared. The scenarios differed in use of resources and energy, whereas there is a potential for trace element leaching regardless of how the material is managed. Utilising MSWI bottom ash in road construction and recycling of wood ash on forest land saved more natural resources and energy than when these materials were managed according to the other scenarios investigated, including dumping in landfill.     

Leaching behavior of heavy metals and PAHs from MSWI bottom ash in a long-term static immersing experiment

Bottom ash is the main solid residue (in weight) which is produced by municipal solid waste incineration (MSWI) facilities. This material is composed of a mineral matrix and may be used as secondary raw material for construction purpose. However, for this specific application the leaching behavior of the environmentally relevant elements under field conditions is different from the predicted behavior based on results obtained from the standardized leaching test. Therefore, a 70-day simulative experiment has been carried out in this study to investigate the release of major heavy metals (Cu and Pb) and polycyclic aromatic hydrocarbons (PAHs) from several particle fractions of bottom ash under a static leaching condition, where bottom ash was immersed in water at different initial pH values. Results showed that: (1) the leaching behavior of Cu and Pb was much similar with that depicted by the standardized leaching tests, and fit well with the solubility-controlling mechanism; (2) the sorption mechanism on the neoformed phases may control the solubility of Pb, whereas the dissolved organic carbon (DOC) may play an important role in the solubility of Cu; and (3) the leached PAHs were degraded during the later period of leaching process.     

Assessment of mobility and bioavailability of contaminants in MSW incineration ash with aquatic and terrestrial bioassays

Incineration of municipal solid waste (MSW) is a waste treatment method which can be sustainable in terms of waste volume reduction as well as a source of renewable energy. In the process fly and bottom ash is generated as a waste material. The ash residue may vary greatly in composition depending on the type of waste incinerated and it can contain elevated levels of harmful contaminants such as heavy metals. In this study, the ecotoxicity of a weathered, untreated incineration bottom ash was characterized as defined by the H14 criterion of the EU Waste Framework Directive by means of an elemental analysis, leaching tests followed by a chemical analysis and a combination of aquatic and solid-phase bioassays. The experiments were conducted to assess the mobility and bioavailability of ash contaminants. A combination of aquatic and terrestrial bioassays was used to determine potentially adverse acute effects of exposure to the solid ash and aqueous ash leachates. The results from the study showed that the bottom ash from a municipal waste incineration plant in mid-Sweden contained levels of metals such as Cu, Pb and Zn, which exceeded the Swedish EPA limit values for inert wastes. The chemical analysis of the ash leachates showed high concentrations of particularly Cr. The leachate concentration of Cr exceeded the limit value for L/S 10 leaching for inert wastes. Filtration of leachates prior to analysis may have underestimated the leachability of complex-forming metals such as Cu and Pb. The germination test of solid ash and ash leachates using T. repens showed a higher inhibition of seedling emergence of seeds exposed to the solid ash than the seeds exposed to ash leachates. This indicated a relatively low mobility of toxicants from the solid ash into the leachates, although some metals exceeded the L/S 10 leaching limit values for inert wastes. The Microtox® toxicity test showed only a very low toxic response to the ash leachate exposure, while the D. magna immobility test showed a moderately high toxic effect of the ash leachates. Overall, the results from this study showed an ecotoxic effect of the solid MSW bottom ash and the corresponding ash leachates. The material may therefore pose an environmental risk if used in construction applications. However, as the testing of the solid ash was rather limited and the ash leachate showed an unusually high leaching of Cr, further assessments are required in order to conclusively characterize the bottom ash studied herein as hazardous according to the H14 criterion.