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.     

Neutralization of an extremely acidic sludge and stabilization of heavy metals in flyash aggregates

An extremely acidic, heavy metal-rich sludge (pH=-1.2) was scrubbed with a Class-F fly ash in order to simultaneously neutralize the acidity and stabilize the heavy metals contained in both wastes. This paper outlines the leaching behavior of the aggregate material generated by scrubbing. For proper fly ash/sludge ratios, the fly ash acted as an outstanding neutralizer for the acidic waste. Leaching of heavy metals from the aggregate samples was below the environmental limits within a pH range between 3 and 9. Subsequent washing of the leached aggregate with acidic CALWET solutions did not result in an additional release of heavy metals. It is proposed that coordinative bonding of the metal cations onto neutral surface sites and electrostatic adsorption led to stabilization of the heavy metals within the aggregate structure below hydrolysis pHs.     

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

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

Application of large volume injection GC-MS to analysis of organic compounds in the extracts and leachates of municipal solid waste incineration fly ash

Organic solvent and water extracts of fly ash from a Milan (Italy) municipal solid waste incinerator (MSWI) were analyzed by large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) with programmable temperature vaporizer (PTV). Using injection volumes of 10-100 microl, typically over a hundred compounds were detected in organic solvent extracts and ca. 35% of them could be tentatively identified from their electron impact ionization mass spectra. A protocol for the determination of the maximum amount of a potential environmental pollutant available for leaching (availability test) was developed for four selected target compounds: pentachlorobenzene (PeCB), hexachlorobenzene (HxCB), o-terphenyl (o-TPH) and m-terphenyl (m-TPH). Key parameters, extraction time and liquid-to-solid ratio (L/S), were studied in more detail. Recoveries of PeCB, HxCB and o-TPH spiked into the fly ash samples at two concentration levels ranged from 38% to 53% for freshly spiked and from 14% to 40% for 40-day aged fly ash. Recoveries of m-TPH were 8% to 11% from freshly spiked and less than 3% from aged spiked fly ash. The native amounts in Milan MSWI fly ash, determined in an interlaboratory exercise using the developed protocol, were 31 ng/g PeCB, 34 ng/g HxCB, 72 ng/g o-TPH and 4.4 ng/g m-TPH. A separate methodology was developed for the determination of compounds extracted from fly ash by water (leaching test). Following 8-h sonication at L/S 20, the leached amounts of PeCB, HxCB and o-TPH were 1.1, 3.1 and 6.0 ng/g fly ash, respectively.     

Removal techniques for heavy metals from fly ash

This study reviews different technologies for extraction of heavy metals from fly ash. With this perspective processes like bioleaching using microbes, carrier in pulp method, chemical extraction via acids, alkaline leachates and chelating agents, chloride evaporation process, electrodialytic and thermal treatments were studied thoroughly. A comprehensive comparison of all the techniques is also done by studying in detail their reaction conditions, metals leached and percentage extraction achieved. The study concluded that depending on the type of fly ash and metal under consideration determines the suitability of the process adopted for detoxification of fly ash. In addition to these, factors like cost, time and energy also define the final selection process.     

Leaching behavior of polychlorinated dibenzo-p-dioxins and furans from the fly ash and bottom ash of a municipal solid waste incinerator

The leaching behavior of dioxins from landfill containing bottom ash and fly ash from municipal solid waste incineration has been investigated by leaching tests with pure water, non-ionic surfactant solutions, ethanol solutions, or acetic acid solutions as elution solvents for a large-scale cylindrical column packed with ash. Larger amounts of dioxins were eluted from both bottom ash and fly ash with ethanol solution and acetic acid solution than with pure water. Large quantities of dioxins were leached from fly ash but not bottom ash by non-ionic surfactant solutions. The patterns of distribution of the dioxin congeners in the leachates were very similar to those in the bottom ash or fly ash from which they were derived.     

Enhancing performance and durability of slag made from incinerator bottom ash and fly ash

This work presents a method capable of melting the incinerator bottom ash and fly ash in a plasma furnace. The performance of slag and the strategies for recycling of bottom ash and fly ash are improved by adjusting chemical components of bottom ash and fly ash. Ashes are separated by a magnetic process to improve the performance of slag. Analytical results indicate that the air-cooled slag (ACS) and magnetic-separated slag (MSS) have hardness levels below 590 MPa, indicating fragility. Additionally, the hardness of crystallized slag (RTS) is between 655 and 686 MPa, indicating toughness. The leached concentrations of heavy metals for these three slags are all below the regulatory limits. ACS appears to have better chemical stability than MSS, and is not significantly different from RTS. In the potential alkali-silica reactivity of slag, MSS falls on the border between the harmless zone and the potentially harmful zone. ACS and RTS fall in the harmless zone. Hence, the magnetic separation procedure of ashes does not significantly improve the quality of slag. However, RTS appears to improve its quality.     

Leachability of automotive shredder residues burned in a fluidized bed system

This paper presents the results of the study of a combustible fraction of automotive shredder residues (CASRs) and the corresponding ashes generated by combustion on a fluidized bed pilot with the aim to understand the influence of thermal treatment regarding properties for final disposal, such as landfilling. The chemical composition was evaluated and the leachability behaviour of ashes and CASR was investigated using the three more commonly used tests: the European Standard EN 12457, the US TCLP-EPA 1311 and the Dutch availability test EA NEN 7371. Different results were obtained depending on the specific conditions of the methods employed. It was found that both the CASR and the ashes contained large amounts of toxic metals and other undesirable elements, such as Cl and S. For the CASR, in addition to the leachability of organic matter above the limit set for hazardous materials, the release of heavy metals, either under alkaline and acidic conditions was significant, revealing the serious risks associated to the landfilling practices still being undertaken worldwide. Release of organic matter from ashes was insignificant, but solubility of sulphates increased and chlorides exceed the hazardous limits in the case of fly ashes. Toxic metals were found to leach from the ashes only under acidic conditions, except Pb and Cu which also leached from finer ashes at alkaline pH. Cr also leached from ashes at alkaline pH values. Both the Dutch availability and TCLP revealed much higher leaching intensities than the European Standard due to the acidity of leachants. However, it was found that ashes may be more resistant to acidification because they exhibit much higher acid neutralization capacity (ANC) than the untreated CASR. The study undertaken shows that thermal valorisation of the combustible fraction of ASR may avoid the risks associated with their landfilling; however, care has to be taken with the ashes because they also behave as hazardous residues. Although, the mass reduction provided by thermal treatment may make landfilling less expensive, a more profitable reutilization of the ashes should be developed.     

An investigation on the potential of metal recovery from the municipal waste incinerator in Taiwan

This study aimed to identify distribution of metals and to estimate the amount of these metals that can be potentially recovered from incineration residues. First, the partitioning behavior of Cr, Cu, Fe, Cd, Al, Zn, and Pb in bottom ash and fly ash was investigated in one large municipal waste incinerator in Taiwan. In addition, the material flow analysis (MFA) method was used to estimate the material flux of metals within incinerator plant, and to calculate the amount of metal recovery. According to the findings of this study, six metals (Fe, Al, Cu, Zn, Cr, and Pb) concentrated in bottom ash mostly, while Cd existed primarily in fly ash. The weight percentages of Fe (4.49%), Al (5.24%), Cu (1.29%), Zn (2.21%), and Pb (0.58%) in incinerator ash are high, and even higher than the compositions of natural minerals. Finally, the amount of Cr, Cu, Fe, Cd, Al, Zn and Pb that can be potentially recovered from incineration residues will reach 2.69 x 10(2), 1.46 x 10(4), 4.91 x 10(4), 6.92 x 10(1), 5.10 x 10(4), 1.85 x 10(4) and 4.66 x 10(3) ton/yr, respectively.     

Leaching characteristics of rare metal elements and chlorine in fly ash from ash melting plants for metal recovery

In terms of resource recovery and environmental impact, melting furnace fly ash (MFA) is attracting much attention in Japan due to its high metal content. The study aims to obtain fundamental information on using a water extraction method not only to concentrate valuable rare metals but also to remove undesirable substances such as chlorine for their recovery from MFA. The composition and leaching characteristics of MFA was investigated. The results revealed that the metal content in MFA is nearly equal to raw ore quality. The content of Ag, In, Pd, Pb, and Zn is, in fact, higher than the content of raw ore. As for leaching behavior, Ag, Bi, In, Ga, Ge, Sb, Sn, and Te showed the lowest release at a neutral pH range. Pd was leached constantly regardless of pH, but its concentration was quite low. On the other hand, most of the Tl was easily leached, revealing that water extraction is not appropriate for Tl recovery from MFA. Major elements Cl, Ca, Na, and K, occupying about 70% of MFA, were mostly leached regardless of pH. Base metal elements Cu, Pb, and Zn showed minimum solubility at a neutral pH. The leaching ratio of target rare metal elements and base metal elements suggests that the optimal pH for water extraction is 8-10, at which the leaching concentration is minimized. The water extraction process removed most of the Cl, Ca, Na, and K, and the concentration of rare metals and base metals increased by four or five times.     

Comparison of leaching characteristics of heavy metals in APC residue from an MSW incinerator using various extraction methods

This study investigates four extraction methods (water extraction, toxicity characteristics leaching procedure (TCLP), modified TCLP with pH control, and sequential chemical extraction (SCE)), each representing different liquid-to-solid (L/S) ratios, pH controls, and types of leachant, and their effects on the leaching concentration of heavy metals in municipal solid waste (MSW) incinerator air pollution control (APC) residue. The results indicated that for extraction with distilled water, the heavy metal leaching concentration (mg/l) decreased with L/S ratio, but the amount of heavy metal released (AHMR), defined as the leached amount of heavy metals to the weight of the tested sample (mg/kg), increased with an increase in L/S ratio, in the range of 2-100. The results also showed that both the leaching concentration and the amount of released metals were strongly pH-dependent in the TCLP and modified TCLP tests. In the case of pHs lower than 6.5, the leaching concentrations of Cd, Pb, Cu, Zn, and Cr decreased with an increase in pH. As pH increased higher than 6.5, Cr and Zn were almost insoluble. Meanwhile, Cd and Cu also showed a similar trend but at pHs of 8.5 and 7.5, respectively. Due to the nature of amphoteric elements, in the case of pHs higher than 7, the Pb leaching concentration increased with increasing pH. In modified TCLP tests with the pH value controlled at the same level as in the SCE test, the heavy metal speciation approached the extractable carbonate bound fraction by the SCE. Both amounts of targeted metals leached from the SCE and modified TCLP tests were much higher than those for the regular TCLP and water extraction tests.     

Metal toxicity assessment of mobile phone parts using Milli Q water

Environmentally safe disposal of end-of-life (EoL) or discarded mobile phone is a serious problem on account of their ever increasing number and toxic metals contents. In the present work, metal toxicity of mobile phone plastics, printed wire boards (PWBs) and batteries were assessed through dynamic batch leaching using Milli Q (MQ) water. Phone plastics failed Toxicity Characterization Leaching Procedure (TCLP) and Waste Extraction Test (WET) for Pb as the cumulative amount of Pb leached from plastics (5.33 mg/l) exceeded the regulatory limits (5.0 mg/l) used in characterizing a waste as hazardous. Similarly, the average cumulative amount (21.83 mg/l) of Ni leached from PWBs exceeded the regulatory limit of 20 mg/l and thus PWBs failed WET. Metals leached from batteries in small amounts (Cr: 0.40 mg/l and Ni: 0.15 mg/l). The presence of Fe in the batteries and its precipitation as oxides/hydroxides in the leaching solution hindered the leaching of other metals in MQ water. Both plastics and PWBs should be treated as hazardous waste and should not be disposed in open landfills. Further, MQ water leaching could provide good simulation of metals leaching from the mobile phones disposed at landfill sites.     

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.     

The adsorption characteristics of heavy metals by various particle sizes of MSWI bottom ash

The incineration rate of municipal solid waste (MSW) has been increased because of difficulty in securing a proper disposal site for MSW in Korea. The advantage of incineration is reduction of the volume of waste; however, significant amounts of bottom ash and fly ash were generated in the incineration process. Their treatment has attracted growing interest because of the potential toxicity of hazardous heavy metals. Generally, heavy metals are less released from bottom ash than from fly ash. In this study the adsorption characteristics of heavy metals were investigated using various particle sizes of MSWI bottom ash. Since bottom ash has a broad particle size distribution, it was sieved to size classes of +20, -20, -48, -80, -100 mesh. Cation exchange capacity (CEC) was analyzed by the ammonium acetate method to evaluate the potential as an adsorbent. The CEC values and surface areas increase as the range of particle size becomes finer. The adsorption experiment was conducted using synthetic (Cu and Ni) and plating rinse water as a function of reaction time (10-180 min), liquid/solid ratio (2-100) and particle size (+20 to -100 mesh), respectively. The adsorption rate increased with decreasing particle size and with increasing liquid/solid ratio; however, the removal efficiency of Cu was higher than that of Ni. In the case of plating rinse water, the adsorption rate decreased sharply at high liquid/solid ratio, and it showed over 80% of adsorption rates for Cu and Ni at an initial pH of 3.     

Characterization and Leaching of Coal Fly Ash

Physical characteristics, chemical composition and leaching behaviour of a waste fly ash from a coal-fired power station are reported. Particle size distribution was studied by the following techniques: sedimentation in a liquid medium; sedimentation in an air flow; and Fraunhofer diffraction of a laser beam. Results obtained by the different methods are in good agreement. Mineralogical content and chemical composition were determined by X-ray diffraction, electronic microprobe and X-ray fluorescence. Acid leaching of the samples was investigated, using the following strong acids in sequence: HCl+ HNO₃, H₂F₂, HClO₄. Analysis of leachates by atomic absorption shows trace metals In, Tl, Ge, Cu, Ga, Pb, Ni, Co, Mn, Cd, Zn, Cr.In this work fly ashes from a Spanish power plant are characterized according to the type of particles, size distribution and chemical composition by means of physical methods. Three particle size fractions are leached by acids and analysis of trace elements in the leaching liquor is carried out. The concentration of trace metals is somewhat higher in the particles of smallest size.     

Chemical stability of geopolymers containing municipal solid waste incinerator fly ash

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

Leaching of heavy metals from chromated copper arsenate (CCA) treated wood after disposal

Wood treated by preservatives is commonly found in solid waste. Among the different types of preserved wood, chromated copper arsenate (CCA) treated wood recently has received much attention due to the scale of usage and its significant role in soil and water contamination. As the ash of CCA treated wood would be hazardous if the wood were to be incinerated, this is not a good alternative, and the best available disposal method is thus landfilling in the US, Canada and Australia. Leaching of the metals from preserved wood that is disposed in unlined landfills for construction debris pollutes the soil and water environments. Several factors affecting leaching of the metals from wood, including pH of the leachant, temperature, the duration of leaching and the type of leachant, were investigated. These factors affect each of the metals, chromium, copper and arsenic, differently. A comparison of these effects on each metal was performed. The results of the experiments showed that the pH of the leachants has a significant effect on the leaching process, and sulfuric acid (pH 3) is the most effective leachant compared to nitric and acetic acid (pH 3-4-5). The amounts of leached chromium, copper and arsenic by sulfuric acid (pH 3) during 15 days were, respectively, 0.2, 0.14 and 0.15 mg more than leachates by nitric acid (pH 5) on the basis of 1g of wood (initial contents of 1.03 mg, 0.42 g and 0.8 mg per g of wood). Most of the leaching occurs in the first 5 days, and the rate of leaching decreases significantly after 5 days. Increasing temperature increases the amount of leached metals, and arsenic is the least resistant metal to the leaching when the temperature increases. Increasing the temperature from 15 degrees C to 35 degrees C during 15 days increases the amount of leached chromium, copper and arsenic by acetic acid at pH 5 by about 0.1, 0.4 and 1.2mg per g of wood, respectively.     

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.     

Evaluation of the use of a sequential extraction procedure for the characterization and treatment of metal containing solid waste

Metal containing wastes like MSWI fly ashes and blast furnace sludge form a major environmental problem as they are polluted with heavy metals. The ash has to be landfilled or can be used as a construction material, but a pretreatment is in general necessary. Washing of the ashes with water in order to dissolve soluble salts or extracting the heavy metals with chemicals are possibilities. Blast furnace sludge contains large quantities of iron and carbon and could be recycled in the blast furnace, if the zinc content were not that high. Using a hydrometallurgical process the zinc can be removed from the sludge particles. In order to evaluate such treatment methods knowledge of the leaching behaviour of the studied material is very important. One of the factors influencing the leaching behaviour is the composition and mineralogy of the solids. A sequential extraction procedure, whereby the material is sequentially leached with different leaching solutions, can be used as an aid to characterize the material and to determine which chemical conditions are needed to obtain a sufficient extraction efficiency. To verify the accuracy of the sequential extraction procedure, a method is tested on MSWI fly ash and evaluated by comparing the results with those of leaching experiments whereby the final pH of the leaching solutions is varied over a wide range. Based upon this evaluation some suggestions for the use of the sequential extraction procedure are made and an adapted procedure is suggested, and applied to a blast furnace sludge.     

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.