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Dissolved organic matter (DOM) in landfill leachate impacts the toxicity, bioavailability, and migration of heavy metals. The present study investigated the complexation of heavy metals (Cu2+ and Pb2+) with DOM from two landfill leachate samples, representing an old landfill site containing incineration residues and incombustible waste. The logarithms of the stability constant (log KM) and percentage of complexed fluorophores were calculated using both the Ryan-Weber non-linear model and the modified Stern-Volmer model, yielding good agreement. The log KM values (at pH = 6.0 ± 0.1) calculated using both methods for the two sampling points were 5.02-5.13 and 4.85-5.11 for Cu2+-DOM complexation, and 5.01-5.13 and 4.46-4.87 for Pb2+-DOM complexation, respectively. Log KM was slightly higher for binding of DOM with Cu2+ than Pb2+, and the quenching degree was stronger for complexation with Cu2+ (28.5-30.6% and 38.0-45.9%) than Pb2+ (6.5-7.1% and 10.0-15.4%) in both leachate samples. While log KM values were similar, differences in the contributions of functional groups and molecular composition led to varying degrees of quenching. This study reveals the potential for heavy metal binding by DOM in landfill leachate with a unique solid waste composition and emphasizes variations in fluorescence quenching between Cu2+ and Pb2+ despite similar log KM levels. These findings may be useful for assessing heavy metal behavior in landfill leachate and its impacts on the surrounding environment.
Assuntos
Metais Pesados , Instalações de Eliminação de Resíduos , Poluentes Químicos da Água , Cobre/química , Monitoramento Ambiental/métodos , Fluorescência , Japão , Chumbo/química , Metais Pesados/química , Poluentes Químicos da Água/químicaRESUMO
Factors associated with chronic elevation of the blood lactate levels in patients undergoing chronic maintenance hemodialysis (hereinafter, hemodialysis patients) have not yet been thoroughly investigated. The purpose of the present study was to clarify factors associated with elevated blood lactate levels in hemodialysis patients. We divided the hemodialysis patients into two groups according the blood lactate levels (the high blood lactate group [> 2 mmol/L] and normal blood lactate group), and conducted a retrospective comparison of the following items between the two groups: (1) the creatinine generation rate (%CGR) and the geriatric nutrition risk index (GNRI) as indices of the nutritional status; (2) the left ventricular ejection fraction (LVEF) and E/A, an indicator of diastolic function; (3) the ankle-brachial index (ABI) and transcutaneous partial pressure of oxygen as indices of the adequacy of circulation in the peripheral blood vessels of the lower extremities; (4) the white blood cell count and serum level of C-reactive protein (CRP) before dialysis as markers of an inflammatory state. The mean age and serum CRP level were significantly higher in the high blood lactate group than in the normal blood lactate group. There were no significant differences in the markers of the nutritional status, cardiac function, or adequacy of circulation in the peripheral blood vessels of the lower extremities between the two groups. Advanced age and a state of chronic inflammation appear to be associated with elevated blood lactate levels in patients undergoing chronic maintenance hemodialysis.
Assuntos
Falência Renal Crônica , Humanos , Idoso , Volume Sistólico , Estudos Retrospectivos , Função Ventricular Esquerda , Diálise Renal , Estado Nutricional , Fatores de RiscoRESUMO
The effects of sewage sludge phosphorus (P) content on heavy metal behavior during co-incineration of sewage sludge and municipal solid waste (MSW) were evaluated. Thermogravimetric differential thermal analysis revealed that MSW incineration was mainly caused by organic matter and fixed carbon, while sewage sludge incineration was caused by volatile matter. During co-incineration, the peak weight loss at 460 °C shifted to slightly higher temperatures and the sludge ratio increased, indicating that interaction effects during co-incineration delayed pyrolysis and polymer/fixed carbon incineration. The residual heavy metal ratios after mono-incineration of sewage sludge were higher than those after MSW mono-incineration. The Cl content of MSW (0.757%) was much higher than that of sewage sludge (0.068%), which resulted in the conversion of heavy metals into metal chlorides and then volatilized during MSW mono-incineration. A synergistic effect of co-incineration was evident for Cu, but not for lead (Pb) or cadmium (Cd). X-ray absorption fine structure (XAFS) measurement revealed that Cu in MSW ash was in the form of CuO(s), but was Cu3(PO4)2 in sewage sludge and co-incineration ashes. CuO(s) is relatively unstable and may be transformed to CuO(g) or CuCl(s) before volatilizing at high temperature or in the presence of Cl. Phosphorus has the effect of stabilizing Cu in sewage sludge during co-incineration.
Assuntos
Metais Pesados , Esgotos , Carbono/química , Cinza de Carvão/química , Metais Pesados/análise , Fósforo , Esgotos/química , Resíduos SólidosRESUMO
Manganese (Mn) is considered an important, energy-critical metal due to its leading role in the production of electrochemical energy storage devices. One valuable source of Mn is hyperaccumulator plants used for the phytoremediation of contaminated soil. In this study, stems and leaves of ginger (Zingiber officinale), which accumulate Mn at moderate levels (â¼0.2 wt %) and potassium (K) at high levels (>5 wt %), were analyzed to assess the potential of recovering metals from this plant. The extraction behaviors of Mn and K were studied using raw and ash samples (100-600 °C). It was crucial to set an appropriate incineration temperature (300 °C) to selectively extract K (â¼96%) and Mn (â¼90%) using water and nitric acid over two consecutive steps. Additionally, citric acid, a cost-effective and environmentally friendly solvent, was just as effective (â¼85%) as nitric acid in extracting Mn. X-ray absorbance near-edge spectroscopy and X-ray diffraction analysis of the ash before and after extractions were applied to elucidate the extraction mechanism. The results revealed that selective extraction of both compounds was possible due to the change in the oxidative state of Mn(II) (soluble in water) into Mn(III) and Mn(IV) (insoluble in water) during sample incineration. Simultaneously, there were complex reactions associated with the changes within potassium carbonate compounds; however, these did not affect the K extraction efficiency.
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We evaluated mercury (Hg) behavior in a full-scale sewage sludge torrefaction plant with a capacity of 150 wet tons/day, which operates under a nitrogen atmosphere at a temperature range of 250-350 °C. Thermodynamic calculations and monitoring results show that elemental Hg (Hg0) was the dominant species in both the pyrolysis gas during the torrefaction stage and in the flue gas from downstream air pollution control devices. A wet scrubber (WS) effectively removed oxidized Hg from the flue gas and moved Hg to wastewater, and an electrostatic precipitator (ESP) removed significant particulate-bound Hg but showed a limited capacity for overall Hg removal. Hg bound to total suspended solids had a much higher concentration than that of dissolved Hg in wastewater. Total suspended solid removal from wastewater is therefore recommended to reduce Hg discharge. Existing air pollution control devices, which consist of a cyclone, WS, and ESP, are not sufficient for Hg removal due to the poor Hg0 removal performance of the WS and ESP; a further Hg0 removal unit is necessary. A commercial packed tower with sorbent polymer catalyst composite material was effective in removing Hg (83.3%) during sludge torrefaction.
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Poluentes Atmosféricos , Mercúrio , Poluentes Atmosféricos/análise , Carvão Mineral/análise , Mercúrio/análise , Polímeros , EsgotosRESUMO
Biodiesel produced from microalgae is a potential alternative due to the high growth rate of microalgae, the possibility of using nonarable land, and high lipid accumulation rate. Microalgae cultivation, cell harvesting and disruption are the important steps before lipid extraction for the biodiesel. In the co-submission article, the details of the whole process cannot be clearly explained. In this regard, we present the details of methods on parameter of photo-bioreactor for cultivating microalgae, flocculation tests to determine optimal flocculant dosage in harvesting, parameter of Dimethyl ether (DME) subcritical extraction device and full-factorial design for investigating the influence of extraction time, initial water content and DME dosage on the extraction performance. It will allow researchers to reproduce these experiments. ⢠The method shows a cell disruption assisted lipid extraction by subcritical dimethyl ether. ⢠Model is built from full-factorial design to investigate multi-factor influence. ⢠Differential scanning calorimetry can be applicable to measure free water content.
RESUMO
Subcritical dimethyl ether, a green solvent, was used to extract lipids from microalgae. The effect of the water content on the process was firstly investigated. Secondly, microalgal samples were subjected to five cell disruptions, and the effects on raw lipid and fatty acid methyl ester, and its profile were evaluated. Among them, heating, microwave, and ultrasonic treatments greatly improved extraction. Mechanism analysis revealed the improvements by the three treatments were due to increased cell wall permeability rather than to complete cell disruption. After the extraction, microalgal cells with lipid being well-extracted were shriveled with extensive surface folds, indicating a loss of intracellular substances, but the cell structure was undamaged. As for dewatering performance, extraction process removed almost all of the free water but left bound water. Finally, the potential of the residues after lipid extraction to serve as solid fuel was evaluated by combustion characteristics and heating value calculation.
Assuntos
Microalgas , Biocombustíveis , Biomassa , Lipídeos , Éteres Metílicos , ÁguaRESUMO
Polycarbonate (PC) is an engineering thermoplastic that is widely used in electrical and electronic equipment. This plastic often contains tetrabromobisphenol A (TBBA), the most common brominated flame retardant. Thermal degradation of the PC-TBBA leads to generation of numerous bromo-organic products in the pyrolytic oil, hindering its appropriate utilization, as well as corrosive hydrogen bromide gas. The purpose of this study was to experimentally investigate and compare the pyrolysis products of PC-TBBA and PC-TBBA + Cu2O at various temperatures, with an emphasis on the yield and distribution of brominated compounds. In pyrolysis of PC-TBBA + Cu2O, at the maximum degradation temperature (600 °C), as much as 86% of total Br was trapped in the residue, while 3% and 11% were distributed in the condensate and gas fractions, respectively. In contrast, the distribution of Br from non-catalytic pyrolysis of PC-TBBA (600 °C) was 0.5% residue, 40% condensate, and 60% gas. The results of this study revealed that in the presence of Cu2O, organo-bromine products were most likely involved in Ullman-type coupling reactions, leading to early cross-linking of the polymer network that efficiently hinders their vaporization. HBr in the gas fraction was suppressed due to effective fixation of bromine in residue in the form of CuBr.
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The elemental composition of 120 dewatered sludge samples from 32 wastewater treatment plants in Japan was analyzed, and the influential factors determining sludge elemental composition were clarified. Through Hayashi's quantification method I, the relationship and influence of each element to the dominant categories were confirmed, and the correlation between the elements was also analyzed. The Van Krevelen diagram was used to determine the similarity in organic contents between sludge and biomass/fossil fuels. Principal component and cluster analyses were used to verify the identification of influential factors. Finally, a standard composition of dewatered sludge in Japan was defined based on different sewage collection systems and digestion processes, shown to have the greatest influence on sludge composition. The potential of sludge for agricultural and cement industrial recycling was also assessed.
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Open burning of PVC-coated cables is a major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F). In the present study, the formation characteristics of PCDD/F from burning of PVC-based samples with and without metallic copper were evaluated over the dioxin formation temperature window (200-500 °C). This temperature range also inevitably occurs under open burning conditions. The PCDD/F yield from PVC added with Cu increased by factors of 1390 (300 °C), 65 (400 °C) and 17 (500 °C) compared with that from PVC alone, confirming the stimulatory effect of metallic Cu on PCDD/F production. For the first time, a relatively complete isomer-specific analysis is established for PVC acting as source of PCDD/F. Formation pathways of PCDD/F and the reaction mechanisms were investigated using a combined analysis of PCDD/F isomer signatures, thermogravimetric results and Cl K-edge X-ray absorption spectra. De novo synthesis is the major pathway leading to massive production of PCDD/F. Copper extends the temperature range for the concurrence of de(hydro)chlorination of PVC with cross-linking and aromatisation of polyenes and then stimulates cracking of the chlorine-embedded carbon network. Together, these processes contribute to the strongly enhanced formation of PCDD/F via de novo synthesis.
Assuntos
Benzofuranos , Dibenzodioxinas Policloradas , Dibenzofuranos , Dibenzofuranos Policlorados , Incineração , Cloreto de PolivinilaRESUMO
Brominated aromatic compounds are unintentionally generated during various thermal processes, including municipal solid waste incineration, electric-waste open burning, and secondary copper smelting. Copper (Cu) plays an important role in the formation of brominated aromatic compounds. In the present study, the thermochemical behaviors of Cu and Br in model samples, including copper bromide (CuBr2) and activated carbon, were studied using in situ X-ray absorption near-edge structure (XANES) and thermogravimetry. Quantification of polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) was also conducted by gas chromatograph-high resolution mass spectrometer. Three key reactions were identified: (i) the reduction of CuBr2 to CuBr (room temperature to 300 °C), (ii) the generation of Br bonded with aromatic carbon (150-350 °C), and (iii) the oxidation of copper (>350 °C). Maximum amounts of PBDD/Fs were found in residual solid phase after heating at 300 °C. The analytical results indicated the direct bromination of aromatic carbon by the debromination of copper bromides (I, II) and that CuBr and CuO acted as catalysts in the oxidation of the carbon matrix. The bromination mechanisms revealed in this study are essential to the de novo formation of PBDD/Fs and other brominated aromatic compounds.
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We investigated the distribution of 18 elements including non-volatiles (Al, P, Ca, Fe, Mg, K, Mn, Cu, Na, Cr, and Ni), semi-volatiles (Zn, Pb, Ag, As, and Cd), and volatiles (Hg and S) and compared their behaviors in two types of full-scale sewage sludge mono-incinerators, namely, a step-grate stoker (GS) and two fluidized bed incinerators (F-types), with the same feed sludge. Most of the non-volatile elements were enriched five-fold in all incinerated sewage sludge ash (ISSA), while the volatile S and Hg were barely enriched in ash due to the combustion components generated in the gas phase. While the semi-volatile elements were also enriched five-fold in the F-types, a different enrichment behavior was observed in the GS. Boiler and multi-cyclone dust in the GS showed higher enrichments of Pb and Cd compared to ash due to the combined effects of lower temperature and smaller particle size. Compared to the F-types, the GS generated ashes with lower toxicity as the major component (99.7%) and hazardous dust as the minor component. In the future, more attention should be paid to grate stokers in terms of recycling ISSA.
Assuntos
Metais Pesados , Esgotos , Cinza de Carvão , IncineraçãoRESUMO
Chromium is commonly found in the flue gases and ashes of Municipal Solid Waste Incineration. It has been reported as an active catalyst for the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) during de novo tests, yet its specific mode of action has remained unclear. This study aims to identify the effects of chromium chloride on the formation of PCDD/F and other chloro-aromatics and to elucidate the underlying reaction mechanisms. A series of de novo tests, conducted over a wide range of temperature (from 250 to 550⯰C) and for four different oxygen contents (0, 5, 10, 20 %), confirmed the promoting effect of CrCl3 on the PCDD/F formation. In situ X-ray Absorption Fine Structure (XAFS) spectroscopy was applied to investigate the behavior of CrCl3 during heating, describing the entire picture of CrCl3-promoted formation pathways of dioxins. The effect of oxygen was studied by measuring XAFS spectra on samples heated at different oxygen concentrations. According to these spectra, chromium compounds play two key roles during dioxins formation: (a) chlorinating carbon, using chlorine derived from conversion of CrCl3 into Cr2O3, and further oxidation to Cr(VI), and (b) facilitating oxidative destruction of the carbon matrix, while reducing Cr(VI) to Cr2O3.
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Lead is a hazardous heavy metal that can be stabilized by incorporation into the matrix of aluminosilicate bearing phases as they solidify. The actual mechanism by which lead is stabilized, however, continues to be unclear because the individual mechanisms of Pb incorporation into crystalline and amorphous aluminosilicate phases have not yet been studied separately. A detailed investigation of the incorporation of Pb into the amorphous phase of aluminosilicate solids was therefore performed. Amorphous aluminosilicate solids were synthesized with 0.7, 1.5, and 3.7 wt.% of Pb from aluminosilicate gel produced from chemical reagents. Based on Raman spectroscopy, the SiO stretching vibration bond shifted to lower wavenumbers with increasing Pb concentration. This shift suggested that covalent bonding between Pb and O in the matrix of the aluminosilicate solids increased. In addition, sequential extraction revealed that most of the Pb (75-90%) in the aluminosilicate solids was in a poorly soluble form (i.e., reducible, oxidizable, and residual fractions). These findings indicate that most of Pb is bonded covalently to the amorphous phase in aluminosilicate solids.
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Open burning of electronic waste (E-waste) produces numerous organochlorine compounds (OCs). Although the presence of unidentified OCs has been suggested, the mass balance of identified and unidentified OCs in E-waste open burning soils (EOBSs) still remains unknown. In this study, the concentrations of Cl bonded with aromatic carbon (aromatic-Cl) and aliphatic carbon (aliphatic-Cl), and inorganic Cl in EOBSs were determined by focusing on chlorine (Cl) in water-insoluble fractions (insoluble Cl) and applying Cl K-edge X-ray absorption spectroscopy in conjunction with combustion ion chromatography. The concentrations of identified Cl (Cl in five individual OCs: polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, chlorinated polycyclic aromatic hydrocarbons and chlorinated benzenes) were calculated from the concentrations previously reported for the same samples. The proportions of identified Cl were less than 1% to aromatic-Cl, indicating the abundance of unidentified OCs. The concentrations of both aromatic-Cl and identified Cl were highest in the sample collected from the site in Vietnam (VN), where wires and cables were mainly burned, suggesting that unidentified aromatic-Cl were produced through pathways similar to those of identified OCs, and the pathway could be related to burning of wires and cables. Further, insoluble Cu (II) compound, Cu2(OH)3Cl were assumed to be present in EOBSs and the concentration was highest in VN, implying that insoluble inorganic chlorides could be related to the formation of aromatic-Cl and identified Cl.
Assuntos
Cloretos/análise , Resíduo Eletrônico/análise , Hidrocarbonetos Clorados/análise , Incineração , Hidrocarbonetos Policíclicos Aromáticos/análise , Poluentes do Solo/análise , Incineração/métodos , Solo/química , VietnãRESUMO
We explored the effects of gas emission by mixtures undergoing alkali-activation of municipal solid waste incineration fly ash (MSWIFA) and pyrophyllite (the mixtures included dehydrated pyrophyllite, MSWIFA, 14â¯mol/L aqueous sodium hydroxide, and sodium silicate; curing proceed at 105⯰C for 24â¯h). We measured the compressive strengths of the derived solid composites. The causes of gas emission, and the physical and chemical properties of products created under controlled gas emission, were investigated. Hydrogen was emitted after mixing MSWIFA and alkali. The compressive strength of products prepared when gas emission was complete was 2-3.4-fold greater than that of products prepared when gas emission was incomplete. X-ray micro-tomography and mercury intrusion porosimetry showed that products formed during complete gas emission tended to have smaller pores. X-ray diffraction and nuclear magnetic resonance (27Al and 29Si) indicated that the aluminum substitution levels in tectosilicate differed under such conditions, although the minerals were identical. Thus, complete gas emission after mixing improved ultimate products.
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Silicatos de Alumínio/química , Cinza de Carvão/química , Incineração/métodos , Indústria de Petróleo e Gás/métodos , Resíduos Sólidos/análise , Carbono/químicaRESUMO
This study investigated core samples from a landfill site for incinerator residue. The landfill site is one of the first monofill sites for municipal solid waste incinerator residue in the world. The concentrations of the heavy metals Cd, Cr, Cu, Pb, Zn, and Ni in the landfilled incinerator residues were 1-108, 41-926, 40-5498, 35-9806, 103-11453, and 25-719â¯mg/kg, respectively. Based on comparisons of heavy metal contents between raw incinerator fly ash and bottom ash reported in the literature, our samples comprised a mixture of incinerator fly ash and bottom ash. Rainfall had removed the dissolvable salts from the incinerator residues. The compositions of incinerator residues from different locations varied markedly. The vertical distribution showed a high heavy metal content in the waste layers, suggesting no vertical movement of heavy metals in this landfill site. A comparison between the experimental data and data calculated from historic records of the original metal compositions of the incinerator residues suggested high mobility of Zn, Cu, and Pb and low mobility of Cr and Cd. This trend was supported by a leaching test of waste layer samples. Zn and Cu were leached more readily at pH 9.0-10.0 and 10.5-11.5, respectively.
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There is an urgent need to dispose safely of the municipal solid waste incineration fly ash (MSWIFA) contaminated by cesium (Cs) released from the Fukushima Daiichi nuclear power plant accidents. This study investigated the relationship between quantitative Cs speciation and Cs immobilization in composite product from alkali-activated pyrophyllite and MSWIFA, with added stable cesium chloride and cesium carbonate. Cesium speciation was determined using X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS), while Cs immobilization was evaluated by a leaching method. Twenty-four composite products, with different Cs leaching properties, were prepared under various conditions. The XRD analysis of six composite products with different Cs leaching properties qualitatively identified a crystalline pollucite in the two products with the least Cs leaching. The quantitative speciation determined using XAFS revealed a strong negative correlation between the pollucite content in the 24 products and their Cs leaching ratio. Cesium species with a CsO bond were found in all products. These were at least two Cs species with different leaching properties. These results indicate that the change from a Cs species to pollucite in the product increased the Cs immobilization level in the system.
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Césio/química , Cinza de Carvão/química , Incineração/métodos , Resíduos Sólidos/análise , Álcalis , Césio/análise , Eliminação de Resíduos/métodos , Difração de Raios XRESUMO
We measured bioaccessible lead (Pb) in simulated gastrointestinal fluids containing Pb-contaminated soil or dust from electronic waste (e-waste) recycling sites to assess the risk of Pb ingestion. The physiologically based extraction test (PBET) was used as in vitro bioaccessibility assay. Pb speciation was determined using X-ray absorption spectroscopy. The total Pb concentrations in dusts (n=8) and soils (n=4) were in the range of 1630-131,000 and 239-7800mg/kg, respectively. Metallic Pb, a common component of e-waste, was ubiquitous in the samples. We also found Pb adsorbed onto goethite and as oxides and carbonate, implying soil mixing and weathering influences. Pb phosphate and organic species were only found in the soil samples, suggesting that formation was soil-specific. We identified other Pb compounds in several samples, including Pb silicate, Pb chromate, and Pb(II) hydrogen phosphate. A correlation analysis indicated that metallic Pb decreased bioaccessibility in the stomach, while a Pb speciation analysis revealed a low bioaccessibility for Pb phosphates and high bioaccessibility for organic Pb species. The health risk based on bioaccessible Pb was estimated to be much lower than that of total Pb due to the lower concentrations.
Assuntos
Suco Gástrico/química , Secreções Intestinais/química , Chumbo/química , Poluentes do Solo/química , Disponibilidade Biológica , Poeira/análise , Resíduo Eletrônico , Monitoramento Ambiental , Chumbo/análise , Reciclagem , Poluentes do Solo/análise , Espectroscopia por Absorção de Raios XRESUMO
Environmentally sound treatments are required to dispose of municipal solid waste incineration fly ash (MSWIFA) contaminated with radioactive cesium (Cs) from the Fukushima Daiichi nuclear power plant accident in Japan. This study focuses on the stabilization of Cs using an alkali-activated MSWIFA and pyophyllite-based system. Three composite solid products were synthesized after mixtures of raw materials (dehydrated pyrophyllite, MSWIFA, 14 mol/L aqueous sodium hydroxide, and sodium silicate solution) were cured at 105 °C for 24 h. Three types of MSWIFAs were prepared as raw fly ash, raw fly ash with 0.1% CsCl, and raw fly ash with 40% CsCl to understand the stabilization mechanism of Cs. Cs stabilization in two solid products was successful, with less than 6.9% leaching observed from two types tests, and was partly successful for the solid product with the highest concentration of Cs. X-ray diffraction showed that all of the solid products produced several crystalline phases, and that pollucite was formed in the highest Cs concentration product. The X-ray absorption fine structure and scanning electron microscopy with X-ray analysis suggested that most Cs species formed pollucite in the two solid products from MSWIFA with added CsCl. This system provides a technique for the direct stabilization of Cs in MSWIFA.