Amirhomayoun Saffarzadeh

Mineralogical characterization of municipal solid waste incineration bottom ash with an emphasis on heavy metal-bearing phases.

Municipal solid waste incineration (MSWI) bottom ash contains a considerable amount of heavy metals. The occurrence and uneven distribution of these heavy metals in bottom ash can increase the complexity of such residues in terms of long-term behavior upon landfilling or recycling. Bottom ashes sampled from three stoker-type incinerators in Japan were analyzed in this paper. This study presents detailed information on the mineralogical characterization of bottom ash constituents and the weathering behavior of these constituents by means of optical microscopy and scanning electron microscopy. It was revealed that bottom ash mainly consists of assorted silicate-based glass phases (48-54 wt% of ash) and mineral phases including melilites, pseudowollastonite, spinels, and metallic inclusions (Fe-P, Fe-S, Fe-Cu, Cu-Sn, Cu-Zn, Cu-S, and Cu-Pb dominated phases), as melt products formed during the incineration process. The compounds embedded in the glass matrix, e.g. spinels and metallic inclusions, played the most important role in concentration of heavy metals (Pb, Zn, Cu, Cr, Mn, Ni, etc.). Other phases such as refractory minerals and ceramics, frequently found in ash, were of less significance in terms of their influence on the involvement of heavy metals. Analysis of lab-scale artificially weathered and 10-year landfilled bottom ash samples revealed that secondary mineralization/alteration of the bottom ash constituents principally carbonation and glass evolution substantially decreased the potential risk of the heavy metals to the surrounding environment.

Impacts of natural weathering on the transformation/neoformation processes in landfilled MSWI bottom ash: A geoenvironmental perspective

UNLABELLED Natural weathering processes are significant mechanisms that noticeably affect the fundamental nature of incineration ash residues. To provide a greater understanding of these processes, a MSWI (mono)landfill site in the north east of the US was selected as the target for systematic investigation of the natural weathering of bottom ash residues. Samples of various ages were collected from locations A (1 yr), B (10 yrs), C (13-14 yrs) and D (20 yrs) of the landfill in 2009. We investigated the phase transformation of the collected bottom ash particles, neoformation processes as well as the behavior and distribution of certain heavy metals (Cu, Pb, Zn, Ni, and Cr) in the neoformed phases using optical microscopy, SEM-EDX, and bulk examinations. KEY FINDINGS at the preliminary stage, the waste metallic particles (Al, Fe, and Cu) and unstable minerals such as lime, portlandite, ettringite and hydrocalumite convert to oxide and hydroxide (hydrate) phases, calcite, alumina gel and gypsum. At the intermediate stage, the decomposition of melt products including magnetite spinels and metallic inclusions is triggered due to the partial dissolution of the melt glass. At the longer time horizon it is possible to track the breakdown of the glass phase, the extensive formation of calcite and anhydrite, Al-hydrates and more stable Fe-hydrates all through the older ash deposits. Among the dominant secondary phases, we propose the following order based on their direct metal uptake capacity: Fe-hydrates>Al-hydrates>>calcite. Calcite was found to be the least effective phase for the direct sorption of heavy metals. Based on overall findings, a model is proposed that demonstrates the general trend of ash weathering in the landfill.

Existence of Cl in municipal solid waste incineration bottom ash and dechlorination effect of thermal treatment

Municipal solid waste incineration (MSWI) is widely used in Japan, through which large amount of incineration residues are produced. The recycle/reuse of the incineration residues is troubled by many factors. This paper studied the MSWI bottom ash with the principal focus on Cl. Both bulk analysis and microanalysis methods have been carried out. The bulk analysis disclosed a particle-size dependent pattern of the Cl content in the bottom ash and the insoluble Cl is essentially in the form of Friedels salt (3CaO·Al(2)O(3)·CaCl(2)·10H(2)O). The microanalysis revealed that Cl preferentially exists in the quench phase of the individual bottom ash particle. Since Friedels salt and the other quench products are thermally unstable, a series of thermal treatments were carried out to decompose such Cl-bearing phases. The experimental results showed the total Cl content in the MSWI bottom ash was reduced by 55.46% after a 4-h heating process at 1000°C. The removal of the soluble Cl (originally as alkali salts) by the thermal process was found to be more effective. However, the insoluble Cl content in the heated sample was barely lowered owing to the formation of calcium chlorocalumite (11CaO·7Al(2)O(3)·CaCl(2)) in the course of heating.

Alteration of municipal solid waste incineration bottom ash focusing on the evolution of iron-rich constituents

Municipal solid waste incineration (MSWI) bottom ash contains a considerable amount of Fe-rich constituents. The behaviors of these constituents, such as dissolution and precipitation, are quite important as they regulate the distribution of a series of ions between the liquid (percolated fluid) and solid (ash deposit) phases. This paper studied both fresh and weathered MSWI bottom ash from the mineralogical and geochemical viewpoint by utilizing optical microscopy, scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), and powder X-ray diffraction. The analysis results revealed that for the fresh bottom ash, iron preferentially existed in the chemical forms of spinel group (mainly Fe(3)O(4), and a series of Al- or Ti- substituted varieties), metallic inclusions (including Fe-P, Fe-S, Fe-Cu-Pb), hematite (Fe(2)O(3)) and unburned iron pieces. In the 1-20 years weathered bottom ash collected from a landfill site, interconversions among these Fe-rich constituents were identified. Consequently, numerous secondary products were developed, including goethite (α-FeOOH), lepidocrocite (γ-FeOOH), hematite, magnetite, wustite (FeO), Fe-Si-rich gel phase. Of all these transformation products, hydrous iron oxides were the most common secondary minerals. Quantitative chemical analysis of these secondary products by SEM/EDX disclosed a strong association between the newly formed hydrous iron oxides and heavy metals (e.g. Pb, Zn, Ni, and Cu). The results of this study suggest that the processes of natural weathering and secondary mineralization contribute to reduction of the potential risks of heavy metals to the surrounding environments.

Modeling the formation of the quench product in municipal solid waste incineration (MSWI) bottom ash

This study investigated changes in bottom ash morphology and mineralogy under lab-scale quenching conditions. The main purpose was to clarify the mechanisms behind the formation of the quench product/layer around bottom ash particles. In the experiments, the unquenched bottom ashes were heated to 300°C for 1h, and were quenched by warm water (65°C) with different simulated conditions. After having filtered and dried, the ashes were analyzed by a combination of methodologies namely, particle size distribution analysis, intact particle and thin-section observation, X-ray diffractometry, and scanning electron microscope with energy dispersive X-ray spectroscopy. The results indicated that after quenching, the morphology and mineralogy of the bottom ash changed significantly. The freshly quenched bottom ash was dominated by a quench product that was characterized by amorphous and microcrystalline calcium-silicate-hydrate (CSH) phases. This product also enclosed tiny minerals, glasses, ceramics, metals, and organic materials. The dominant mineral phases produced by quenching process and detected by XRD were calcite, Friedels salt, hydrocalumite and portlandite. The formation of quench product was controlled by the fine fraction of the bottom ash (particle size <0.425mm). From the observations, a conceptual model of the ash-water reactions and formation of the quench product in the bottom ash was proposed.

Influence of ignition process on mineral phase transformation in municipal solid waste incineration (MSWI) fly ash: Implications for estimating loss-on-ignition (LOI)

This research focused on the mineral phase transformation under varied ignition conditions with the objective of estimating loss-on-ignition (LOI) parameter in municipal solid waste incineration (MSWI) fly ash residues. LOI is commonly used to measure the volatile species, unburned carbon and moisture in the solid materials. There are criteria for LOI measurement in some research fields, while there is no standard protocol for LOI measurement in MSWI fly ash. Using thermogravimetry technique, the ignition condition candidates were proposed at 440/700/900°C for 1 and 2h. Based on X-ray diffractometry results, obvious mineral phase transformation occurred as a function of ignition temperature variation rather than ignition time. Until 440°C, only some minor phases disappeared comparing with the original state. Significant mineral phase transformations of major phases (Ca- and Cl-based minerals) occurred between 440 and 700°C. The mineral phase transformation and the occurrence of newly-formed phases were determined not only by the ignition condition but also by the content of the co-existing components. Mineral phase components rarely changed when ignition temperature rose from 700 to 900°C. Consequently, in order to prevent critical damages to the original mineralogical composition of fly ash, the lowest ignition temperature (440°C) for 2h was suggested as an ideal measurement condition of LOI in MSWI fly ash.

Geoenvironmental weathering/deterioration of landfilled MSWI-BA glass

Municipal solid waste incineration bottom ash (MSWI-BA) glass serves as a matrix of assorted bottom ash (BA) compounds. Deterioration of the BA glass phases is quite important as they regulate the distribution of a series of toxic elements. This paper studied landfilled MSWI-BA samples from the mineralogical and geochemical viewpoint to understand the deterioration behavior of the BA glass phases as well as mechanisms involved. Bulk analysis by PXRD as well as micro-scale analysis by optical microscopy and SEM/EDX was conducted for such purposes. The results revealed that dissolution of the BA glass phases has resulted in a deterioration layer of 10(0)-10(2)μm thickness after years of disposal. This rapid weathering process is highly relevant to the specific glass characteristics and solution pH. The BA glass phases with more embedded compounds and cracks/fissures tend to be more vulnerable. Moreover, the generally alkaline pH in ash deposit favors a rapid disruption of the glass phase. The weathering products are mainly gel phases (including Al-Si gel, Ca-Al-Si gel, Fe-Al-Si gel etc.) with iron oxide/hydroxide as accessory products. Breakdown of the BA glass phases triggers chemical evolution of the embedded compounds. Based on all the findings above, a model is proposed to illustrate a general evolution trend for the landfilled MSWI-BA glass phases.

Petrogenetic characteristics of molten slag from the pyrolysis/melting treatment of MSW

MSW slag materials derived from four pyrolysis melting plants in Japan were studied from the viewpoint of petrology in order to discriminate the glass and mineral phases and to propose a petrogenetic model for the formation process of molten slag. Slag material is composed of two major components: melt and refractory products. The melt products that formed during the melting process comprise silicate glass, and a suite of minerals as major constituents. The silicate glass is essentially composed of low and high silica glass members (typically 30% and 50% of SiO(2), respectively), from which minerals such as spinels, melilite, pseudowollastonite, and metallic inclusions have been precipitated. The refractory products consist mainly of pieces of metals, minerals and lithic fragments that survived through the melting process. Investigations demonstrated that the low silica melts (higher Ca and Al contents) were produced at upper levels of high temperature combustion chamber HTCC, at narrower temperature ranges (1250-1350 degrees C), while the high silica melts formed at broader temperature ranges (1250-1450 degrees C), at the lower levels of HTCC. The recent temperature ranges were estimated by using CaOAl(2)O(3)SiO(2) (CAS) ternary liquidus diagram that are reasonably consistent with those reported for a typical combustor. It was also understood that the samples with a higher CaO/SiO(2) ratio (>0.74-0.75) have undergone improved melting, incipient crystallization of minerals, and extensive homogenization. The combined mineralogical and geochemical examinations provided evidence to accept the concept of stepwise generation of different melt phases within the HTCC. The petrogenesis of the melt products may therefore be described as a two-phase melt system with immiscible characteristics that have been successively generated during the melting process of MSW.

The impact of thermal treatment and cooling methods on municipal solid waste incineration bottom ash with an emphasis on Cl

ABSTRACT Municipal solid waste incineration (MSWI) bottom-ash products possess qualifications to be utilized in cement production. However, the instant use of bottom ash is inhibited by a number of factors, among which the chlorine (Cl) content is always strictly restricted. In this paper, the unquenched MSWI bottom ash was used as the experimental substance, and the influences of thermal treatment and cooling methods on the content and existence of Cl in the ash residues were investigated. The characterization of the MSWI bottom-ash samples examined by utilizing X-ray diffraction, optical microscopy, scanning electron microscopy/energy dispersive X-ray spectroscopy. The experimental results show that as a function of thermal treatment, the reduction rate of Cl is slight below 15.0%, which is relatively low compared with water washing process. Different cooling methods had impacts on the existing forms of Cl. It was understood that most of Cl existed in the glass phase if the bottom ash was air cooled. Contrarily in case of water-quenched bottom ash, Cl could also be accumulated in the newly-formed quench products as chloride salts or hydrate substances such as Friedels salt.

Occurrence and Significance of Secondary Iron-rich Products in Landfilled MSWI Bottom Ash

Incineration is one of the most effective techniques for the treatment of both municipal and hazardous wastes. Via this technique, the majority of toxic substances are expected to be stabilized in the durable matrix of the end-ofprocess bottom ash products. These products consist of a variety of glassy/crystalline components including primary Fe-rich phases that may undergo alterations when exposed to natural environment. In the present research, the impact of natural weathering on the behavior of primary Fe-rich phases, their alteration, and the formation of the relevant secondary products in the weathered bottom ash samples of a (mono) landfill site was systematically investigated. Samples of various ages (1-20 yrs) were collected from four locations of the landfill in 2009. Optical microscopy, SEM-EDX, XRD and XRF examinations were applied in order to document the footprints of weathering processes. Using these techniques, we understood that several secondary (newly-formed) products (amorphous or crystalline) have been developed, including goethite (α-FeOOH), lepidocrocite (γ-FeOOH), hematite (Fe2O3), magnetite (Fe3O4), iron oxide (FeO), and Fe-rich Ca-Si and Ca-Al-Si gel phases. They occurred under variable environmental conditions as the weathering products of the primary iron-rich phases. The strong affinity of these secondary phases with heavy metals of environmental significance such as Zn, Cu, Pb, and Ni was also identified. This suggests that the development of secondary Fe-rich products can partially contribute to the reduction of heavy metals release to the surrounding environments. However such phenomena may have inhibitory effect on the utilization of bottom ash as recycled aggregates.