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.     

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.     

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)     

Leaching toxicity and heavy metal bioavailability of medical waste incineration fly ash

The aim of this study was to provide a comprehensive risk assessment for medical waste incineration fly ash from another aspect through various leaching methods. The differences and connections between leaching concentrations achieved via the toxicity characteristic leaching procedure (TCLP), the physiologically based extraction test (PBET) and the sequential extraction procedure were also described. Heavy metal contents of the used medical waste incineration fly ash were 1.7–31 times higher than that from Japan, indicating poor medical waste management in China. The fly ash leaching concentration in the TCLP test exceeded the regulation value and can be characterized as hazardous waste under current regulations. However, the PBET concentrations were only 1/10 of the TCLP value or even lower, and the calculated ingested contents of all heavy metals were lower than tolerable daily intake, demonstrating that TCLP might have overestimated the environment risk to some degree. The leaching metal content of TCLP ranged from exchangeable to residual forms, and the leaching percentage varied from 7.75 to 92.55 %, while the content for PBET was equal to or lower than the exchangeable form.     

气化炉渣的重金属浸出特性及化学形态分析

分别采用硫酸硝酸法、水平振荡法和醋酸缓冲溶液法制取气化炉渣的浸出液，考察了不同提取方式对浸出液中重金属质量浓度的影响。采用改进BCR连续提取法对气化炉渣中的重金属Cr，Zn，Cu，Pb，Ni，As，Cd的化学形态进行了分析。实验结果表明：煤气化工艺中的气化炉渣属第Ⅰ类一般工业固体废物;在3种提取方式中，醋酸缓冲溶液法的重金属浸出种类最多，且浸出量最大;Cd和Cr对环境具有较高的潜在危害性，Cu次之，Zn，Pb，Ni，As主要以残渣态形式存在，对环境的直接危害性较低。     

Heavy metals removal/stabilization from municipal solid waste incineration fly ash: a review and recent trends

Waste treatment using thermal technologies, such as incineration, leads to the production of pollutants and wastes, including fly ash (FA). Fly ash contains heavy metals (HMs) and other contaminants and can potentially pose high risks to the environment and negatively impact health and safety. Consequently, stabilizing fly ash prior to either use or landfilling is crucial. The toxicity of fly ash through heavy metal leaching can be assessed using leaching tests. The leaching rates of heavy metals primarily depend on the surrounding conditions as well as fly ash properties and metal speciation. Physical separation, leaching or extraction, thermal treatment and solidification/chemical stabilization are proposed as suitable approaches for fly ash treatment. Economic considerations, environmental concerns, energy consumption and processing times can define the efficiency and selection of the treatment approach. This review considers the latest findings and compares the advantages and shortcomings of different fly ash treatment methods with the aim of highlighting the recent advances in the field. The review concludes that the simultaneous implementation of various methods can lead to highly efficient heavy metals removal/stabilization while simultaneously taking economic and environmental considerations into account.

     

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.     

Stabilization/solidification of MSW incineration residues from facilities with different air pollution control systems. Durability of matrices versus carbonation

This paper discusses the stabilisation/solidification process with Portland cement applied to municipal solid waste incineration residues. Two types of residues were considered: fly ash (FA) produced in an electrostatic precipitator, and air pollution control (APC) residues from a semi-dry scrubber process. Cement pastes with different percentages of FA and APC residues were characterised according to their physical properties, the effect of the hydration products and their leaching behaviour. Portland pastes prepared with APC residues showed a rapid setting velocity in comparison with setting time for those pastes substituted with FA residues. Portland cement hydration was retarded in FA pastes. Leaching test results showed that heavy metals (such as Zn, Pb and Cd) and sulphates are immobilised within the paste, whereas chlorides are only partially retained. The carbonation process increases the leachability of S04(2-) and heavy metals such as Zn and Cr.     

Metal distribution in incineration residues of municipal solid waste (MSW) in Japan

This study aimed to identify distribution of metals and the influential factors on metal concentrations in incineration residues. Bottom ash and fly ash were sampled from 19 stoker and seven fluidized bed incinerators, which were selected to have a variety of furnace capacity, furnace temperature, and input waste. In the results, shredded bulky waste in input waste increased the concentration of some metals, such as Cd and Pb, and the effect was confirmed by analysis of shredded bulky waste. During MSW incineration, lithophilic metals such as Fe, Cu, Cr, and Al remained mainly in the bottom ash while Cd volatilized from the furnace and condensed to the fly ash. About two thirds of Pb and Zn was found in the bottom ash despite their high volatility. Finally, based on the results obtained in this study, the amount of metal in incineration residues of MSW was calculated and the loss of metal was estimated in terms of mass and money. A considerable amount of metal was found to be lost as waste material by landfilling of incineration residues.     

Environmental impact of fly ash utilization in roadway embankments

The leaching potential of heavy metals from a roadway embankment constructed of fly ash and soil mixture was studied. Leaching of eight environmentally concerned metals Ag, As, Ba, Cd, Cr, Hg, Pb, and Se from the fly ash–soil mixtures was examined through batch leaching test and column leaching test. The batch leaching test results showed that the fly ash meets the local regulatory standards for beneficial use of nonhazardous wastes. The column leach test revealed that only Ba, Cr, and Se were detectable in the effluents. The peak concentration of Ba in the effluents was much lower than the US EPA Primary Drinking Water Regulations’ maximum contaminant level (MCL). The peak concentrations of Cr and Se exceeded the MCLs only in the initial flush stage and quickly decreased to below the MCLs. Results of this study suggest a great potential for fly ash to be used in roadway embankments to enhance their mechanical properties, reduce the use of soil, and avoid the disposal of fly ash as waste.     

Metal leachability, heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in fly and bottom ashes of a medical waste incineration facility

Medical waste from hospitals and other healthcare institutions has become an imperative environmental and public safety problem. Medical waste in Greece has become one of the most urgent environmental problems, because there are 14,000 tons produced annually, of which only a small proportion is incinerated. In the prefecture of Attica there is only one modern municipal medical waste incinerator (started 2004) burning selected infectious hospital waste (5-6 tons day(-1)). Fly and bottom residues (ashes) are collected and stored temporarily in barrels. High values of metal leachability prohibit the landfilling of these ashes, as imposed by EU directives. In the present study we determined quantitatively the heavy metals and other elements in the fly and bottom ashes of the medical waste incinerator, by inductively coupled plasma emission spectrometry (ICP) and by energy dispersive X-ray analysis (EDAX). Heavy metals, which are very toxic, such as Pb, Cd, Ni, Cr, Cu and Zn were found in high concentrations in both fly and bottom ashes. Metal leachability of fly and bottom ashes by water and kerosene was measured by ICP and the results showed that toxic metals in both ashes, such as Pb, Cr, Cd, Cu and Zn, have high leaching values. These values indicate that metals can become soluble and mobile if ash is deposited in landfills, thus restricting their burial according to EU regulations. Analysis of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in fly and bottom ashes showed that their concentrations were very low. This is the first known study in Greece and the results showed that incineration of medical waste can be very effective in minimizing the most hazardous and infectious health-care waste. The presence of toxic metals with high leachability values remains an important draw back of incineration of medical waste and various methods of treating these residues to diminish leaching are been considered at present to overcome this serious technical problem.     

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.     

Characteristics of ashes from different locations at the MSW incinerator equipped with various air pollution control devices

The characteristics of ashes from different locations at a municipal solid waste incinerator (MSWI) equipped with a water spray tower (WST) as a cooling system, and a spray dryer adsorber (SDA), a bag filter (BF) and a selective catalytic reactor (SCR) as air pollution control devices (APCD) was investigated to provide the basic data for further treatment of ashes. A commercial MSWI with a capacity of 100 tons per day was selected. Ash was sampled from different locations during the normal operation of the MSWI and was analyzed to obtain chemical composition, basicity, metal contents and leaching behavior of heavy metals. Basicity and pH of ash showed a broad range between 0.08-9.07 and 3.5-12.3, respectively. Some major inorganics in ash were identified and could affect the basicity. This could be one of the factors to determine further treatment means. Partitioning of hazardous heavy metals such as Pb, Cu, Cr, Hg and Cd was investigated. Large portions of Hg and Cd were emitted from the furnace while over 90% of Pb, Cu and Cr remained in bottom ash. However 54% of Hg was captured by WST and 41% by SDA/BF and 3.6% was emitted through the stack, while 81.5% of Cd was captured by SDA/BF. From the analysis data of various metal contents in ash and leach analysis, such capturing of metal was confirmed and some heavy metals found to be easily released from ash. Based on the overall characteristics of ash in different locations at the MSWI during the investigation, some considerations and suggestions for determining the appropriate treatment methods of ash were made as conclusions.     

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.     

Characteristic of heavy metals in biochar derived from sewage sludge

This study investigates the characteristic of heavy metals (Pb, Zn, Cu, Cd, Cr, Ni and As) in biochar derived from sewage sludge at different pyrolysis temperatures (300, 400, 500, 600 and 700 °C). The heavy metal concentrations, chemical speciation distribution, leaching toxicity, and bio-available contents were investigated using ICP-OES after microwave digestion, a sequential extraction procedure recommended by the Community Bureau of Reference (BCR), an improved nitric acid–sulphuric acid method, and diethylenetriamine pentaacetic acid (DTPA) extraction method, respectively. The results showed that a great percentage of the heavy metals remained in biochar, the concentrations of heavy metals in biochar (except Cd in B7) were higher than that in sludge, and the enrichment of the heavy metals in biochar enhanced with the pyrolysis temperature. Although the effect of pyrolysis temperature on the chemical speciation distribution, the leaching toxicity and the bio-available contents of heavy metals in biochar was inconsistent, the potential risk of biochar on soil and groundwater contamination was lower than sewage sludge.     

Flow analysis of metals in a municipal solid waste management system

This study aimed to identify the metal flow in a municipal solid waste (MSW) management system. Outputs of a resource recovery facility, refuse derived fuel (RDF) production facility, carbonization facility, plastics liquefaction facility, composting facility, and bio-gasification facility were analyzed for metal content and leaching concentration. In terms of metal content, bulky and incombustible waste had the highest values. Char from a carbonization facility, which treats household waste, had a higher metal content than MSW incinerator bottom ash. A leaching test revealed that Cd and Pb in char and Pb in RDF production residue exceeded the Japanese regulatory criteria for landfilling, so special attention should be paid to final disposal of these substances. By multiplying metal content and the generation rate of outputs, the metal content of input waste to each facility was estimated. For most metals except Cr, the total contribution ratio of paper/textile/plastics, bulky waste, and incombustible waste was over 80%. Approximately 30% of Cr originated from plastic packaging. Finally, several MSW management scenarios showed that most metals are transferred to landfills and the leaching potential of metals to the environment is quite small.     

脱硫用电石渣的重金属浸出特性及其对环境的影响

针对电厂用脱硫剂电石渣,分析了其基本组成及重金属浸出特性,为电厂脱硫设施的参数设计和环境影响评价提供依据和参考。研究结果表明,脱硫用电石渣主要成分为Ca（OH）2,含量在40%～50%之间;在8种重金属的含量中,只有Cd的含量超出土壤质量三级标准的要求,基本不会对土壤造成污染。浸出毒性试验表明,电石渣及其脱硫产物属于非危险废物,其各种重金属的浸出浓度主要受其本身重金属含量和最终pH的影响,这种影响在Pb、Cu和Cd上表现得较为突出,酸性环境下更有利于他们的浸出;碱性环境下有利于Pb和Ni的浸出。     

重金属污染土壤生物毒性的发光菌法测定及评价

向土壤中人为投加重金属污染物,制备了重金属含量不同的一系列污染土壤,对土壤重金属浸提条件进行了探究,并应用明亮发光杆菌T3（Photobacterium phosphoreum T3）对单一Cu、Cd和Pb污染及Cu-Cd和Cu-Pb复合重金属污染土壤的生物毒性进行了测定。实验结果表明,土壤重金属的最佳浸提剂为0.1 mol/L HCl溶液,最佳浸提时间为2.0 h。在单一重金属污染条件下：Cu表现出低浓度促进生长、高浓度抑制生长的双重生物效应,而Cd和Pb则表现出浓度与生物毒性的正相关性;3种重金属污染土壤的毒性强弱顺序为Cd>Pb>Cu。在复合重金属污染条件下,由于重金属之间的相互作用,污染土壤的生物毒性增强。     

Fate and behavior of selected heavy metals with mercury mass distribution in a fluidized bed sewage sludge incinerator

In this paper, emission and distribution behavior of six heavy metals (As, Cd, Cr, Ni, Pb, and Hg), particulate matter and mass distribution of mercury within the different streams of a fluidized bed sewage sludge incinerator are presented. At the inlet of air pollution control devices (APCDs); Cd, Cr, Ni and Pb were mainly enriched in coarse particles; comparatively As content was higher in fine particles (<PM_2.5). The concentration of heavy metals in total particulate matter and PM_2.5, at the inlet of APCDs, were in the order of Cr > Ni > Pb > As > Cd. Mercury was almost always distributed in flue gas. Metals, other than mercury, were efficiently removed in APCDs and their concentrations in bottom ash, with fly ash being higher, whereas for that in wastewater, then waste sand was lesser. Overall mercury removal efficiency of APCDs was 98.6 %. More than 83.3 % of mercury was speciated into oxidized form at the inlet of APCDs, attributed by higher chlorine content in sludge. Mercury was mainly distributed in wastewater (78.4 %), wastewater from a spray dry reactor (16.8 %), fly ash in a hopper (3.4 %) and flue gas (1.4 %). This result is one of the first for data to be obtained; more experiments are required to control emission from such sources.     

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

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