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)     

Effect of leachate recirculation on the migration of copper and zinc in municipal solid waste and municipal solid waste incineration bottom ash co-disposed landfill

Municipal solid waste incinerator (MSWI) bottom ash was allowed to be disposed of with municipal solid waste (MSW) in landfill sites in the recently enacted standard of China. In this study, three sets of simulated landfill reactors, namely, conventional MSW landfill (CL), conventional MSWI bottom ash and MSW co-disposed landfill (CCL), and leachate recirculated MSWI bottom ash and MSW co-disposed landfill (RCL), were operated to investigate the environmental impact of the co-disposal. The effect of leachate recirculation on the migration of Cu and Zn in the co-disposed landfill was also presented. The results showed that the co-disposal of MSWI bottom ash with MSW would not enhance the leaching of Cu and Zn from landfill. However, the co-disposal increased the Cu and Zn contents of the refuse in the bottom layer of the landfill from 56.7 to 65.3 mg/kg and from 210 to 236 mg/kg, respectively. The recirculation of the leachate could further increase the Cu and Zn contents of the refuse in the bottom layer of the landfill to 72.9 and 441 mg/kg, respectively. Besides these observations, the results also showed that the co-disposed landfill with leachate recirculation could facilitate the stabilization of the landfill.     

The weathering of municipal solid waste incineration bottom ash evaluated by some weathering indices for natural rock

The weathering of municipal solid waste incineration (MSWI) residues consists of complicated phenomena. This makes it difficult to describe leaching behaviors of major and trace elements in fresh/weathered MSWI bottom ash, which was relevant interactively to pH neutralization and formation of secondary minerals. In this study, mineralogical weathering indices for natural rock profiles were applied to fresh/landfilled MSWI bottom ash to investigate the relation of these weathering indices to landfill time and leaching concentrations of component elements. Tested mineralogical weathering indices were Weathering Potential Index (WPI), Ruxton ratio (R), Weathering Index of Parker (WIP), Vogt’s Residual Index (V), Chemical Index of Alternation (CIA), Chemical Index of Weathering (CIW), Plagioclase Index of Alternation (PIA), Silica–Titania Index (STI), Weathering Index of Miura (Wm), and Weatherability index of Hodder (Ks). Welch’s t-test accepted at 0.2% of significance level that all weathering indices could distinguish fresh and landfilled MSWI bottom ash. However, R and STI showed contrasted results for landfilled bottom ash to theoretical expectation. WPI, WIP, Wm, and Ks had good linearity with reclamation time of landfilled MSWI bottom ash. Therefore, these four indices might be applicable as an indicator to indentify fresh/weathered MSWI bottom ash and to estimate weathering time. Although WPI had weak correlation with leachate pH, other weathering indices had no significant correlation. In addition, all weathering indices could not explain leaching concentration of Al, Ca, Cu, and Zn quantitatively. Large difficulty to modify weathering indices correctly suggests that geochemical simulation including surface sorption, complexation with DOM, and other mechanisms seems to be the only way to describe leaching behaviors of major and trace elements in fresh/weathered 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.     

Leaching from land disposed municipal composts: 3. Inorganic ions

The leachates from 17 lysimeters containing compost of varying origin, age (3 and 12 months)., and packing depths (15–50 cm) were monitored for a 2.5-year period. This paper reports on the results on Na, K, Ca, Mg, Mn, Fe, Cl, SO₄ and to a lesser extent specific conductivity, total dissolved solids, F, B and P. High initial leachate concentrations exceeding the drinking water standards several-fold were observed for all constituents except B and F. Sulphate and K were identified as the most serious pollutants of the ions studied but they were found to be less critical than N compounds and organic matter previously reported in the leachate. The leaching of most constitutents increased with increasing amounts of compost per square metre. The origin of the compost affected the leaching of K, Mn, Fe, Cl, Mg and SO₄. The first year of leaching released significant parts of the Na, K, Mg, Cl and SO₄ but only minor parts of the Mn, Fe, F and P present in the compost.     

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.     

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.     

Leachability of municipal solid waste ashes in simulated landfill conditions

In Japan the volume of municipal solid waste is reduced by incineration, with fly ash and bottom ash disposed in controlled landfills. The leachability of anions and heavy metal cations, Zn, Cu and Pb, from MSW fly ash and bottom ash at different pHs was examined using batch- and column-leaching tests. The MSW ashes had a high capacity for neutralizing acids. Behaviour during leaching depended on the pH of the solution. For the volumes applied, the leachabilities of MSW fly ash were very similar at pHs from 3 to 6. Due to its amphoteric nature, Pb is leachable at pHs of approximately 10 or more, with leachate concentrations of about 3 and 3-10mg/L for the fly ash and bottom ash, respectively, much higher than for Zn and Cu. Pb concentrations for most leaching solutions were 1 and 3mg/L for the fly ash and bottom ash, respectively. Zn, and Cu leached at low concentrations for solutions of pH 3-6. Na and K ions leached at high concentrations of approximately 5000 mg/L in the first batch leaching test, decreasing to 10mg/L by the fourth leach. Ca and Mg ions leached more gradually than Na and K. Cl(-) and SO(4)(2+) ions were the major anions in the MSW ash. The high pH and cation leaching are expected to have negative impacts on the performance of clay liners.     

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.     

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.     

Assessment of long-term leaching from waste incineration air-pollution-control residues

Assessment of long-term leaching from MSWI air-pollution-control (APC) residues is discussed with respect to use in environmental impact assessment, such as life-cycle assessment (LCA). A method was proposed for estimating leaching as a function of the liquid-to-solid (L/S) ratio in a long-term perspective (L/S 5000l/kg). Data for changes in residue pH as a function of L/S was used in combination with pH dependent leaching data to predict leachate concentrations of Al, Ca, Cd, Ba, Mg, Ni, Pb, S, Pb, V and Zn as a function of L/S. Mass balance calculations were used to determine the element fractions leached with respect to L/S. The estimated long-term leaching from a semi-dry residue and a fly ash was compared with short-term leaching determined by batch tests at L/S 10l/kg, both carbonated and non-carbonated versions of the residues were investigated. Generally, very high L/S ratios above 2000l/kg were required to leach 20-30% of the solid contents. However, Ca and S were depleted at L/S 200-900l/kg. The long-term leachate concentrations were found to either remain at the same level as the initial leaching determined by the L/S 10 batch test, or to significantly decrease compared with the initial leaching. Only Al and Zn were found to show higher leachate concentrations at L/S ratios above 3000-5000l/kg. Carbonation generally prolonged the time needed for depletion from the solid residues; however, Ca and S were depleted faster than in the case of non-carbonated residues. This study shows that uncritical use of batch leaching data for assessing the potential leaching is highly problematic, and evaluations of residue disposal should include scenario specific quantification of the long-term leaching.     

Mobility of organic carbon from incineration residues

Dissolved organic carbon (DOC) may affect the transport of pollutants from incineration residues when landfilled or used in geotechnical construction. The leaching of dissolved organic carbon (DOC) from municipal solid waste incineration (MSWI) bottom ash and air pollution control residue (APC) from the incineration of waste wood was investigated. Factors affecting the mobility of DOC were studied in a reduced 2(6-1) experimental design. Controlled factors were treatment with ultrasonic radiation, full carbonation (addition of CO2 until the pH was stable for 2.5h), liquid-to-solid (L/S) ratio, pH, leaching temperature and time. Full carbonation, pH and the L/S ratio were the main factors controlling the mobility of DOC in the bottom ash. Approximately 60 weight-% of the total organic carbon (TOC) in the bottom ash was available for leaching in aqueous solutions. The L/S ratio and pH mainly controlled the mobilization of DOC from the APC residue. About 93 weight-% of TOC in the APC residue was, however, not mobilized at all, which might be due to a high content of elemental carbon. Using the European standard EN 13 137 for determination of total organic carbon (TOC) in MSWI residues is inappropriate. The results might be biased due to elemental carbon. It is recommended to develop a TOC method distinguishing between organic and elemental carbon.     

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.     

Effect of sintering temperature on the properties and leaching of incinerator bottom ash.

The fine particle size fraction of municipal solid waste incinerator bottom ash is often problematic because reuse applications for this material are limited. In these experiments incinerator bottom ash with a particle size of less than 8 mm was processed using conventional ceramic production techniques involving wet milling, drying, compacting and sintering. The effect of sintering temperature on the sintered density, microstructure, acid neutralization capacity (ANC) and the release of metal ions as a function of leachate pH are reported. Sintering at 1080 degrees C produced samples with maximum density. This material contained diopside (CaMgSi2O6), clinoenstatite (Mg2Si2O6) and wollastonite (CaSiO3) as the major crystalline phases. The acid neutralization capacity of sintered samples is significantly lower than milled bottom ash, and further reduces as the sintering temperature increases. This is associated with reduced leaching of Ca from sintered ash samples under all leachate pH conditions. Heavy metals present in the incinerator bottom ash included Cr, Cu, Ni, Zn, Cd and Pb. Sintering under optimum conditions reduced the leachable fraction of these metals under aggressive acid conditions (leachate pH 3) by factors ranging from 90% for Ni to greater than 99% for Cr, Cd, Zn and Pb.     

Criteria selection for landfills: do we need a limitation on inorganic total content?

The chemistry of the landfill environment is complex and dissolution rates may be higher than in natural systems. As will be shown in this paper, there are often great uncertainties in terms of leaching kinetics and long-term emissions of landfills in general. Leaching tests used in the laboratory may reflect a leaching behaviour not consistent with real landfill scenarios. Geochemical calculations for model systems provide an impression of the possible long-term behaviour of buffered, inorganic landfills. For a buffered carbonate-containing system (this system may be a mono-landfill of slag and/or ash after a few decades and/or centuries), maximums for the solubility of the elements Zn, Cd, Pb and Cu can be calculated while taking into account the presence of gypsum, the complexation in water ("speciation") and other factors influencing solubility. We have made these calculations using the recent version of the geochemical code PHREEQC-2. Finally, we conclude that under most circumstances the total elemental content, or the so-called "total availability," is a valuable assessment tool when combined with other criteria, such as leachable amounts and leachate test results. Exceptions may be carbonate-buffered monofill scenarios (e.g. monofill or quasi-monofill of MSWI residues), where setting limits on some elemental contents (Cu, Zn, Fe and Mn) does not seem to be very useful.     

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.     

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.     

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.     

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.