Experimental and numerical analysis of metal leaching from fly ash-amended highway bases

A study was conducted to evaluate the leaching potential of unpaved road materials (URM) mixed with lime activated high carbon fly ashes and to evaluate groundwater impacts of barium, boron, copper, and zinc leaching. This objective was met by a combination of batch water leach tests, column leach tests, and computer modeling. The laboratory tests were conducted on soil alone, fly ash alone, and URM-fly ash-lime kiln dust mixtures. The results indicated that an increase in fly ash and lime content has significant effects on leaching behavior of heavy metals from URM-fly ash mixture. An increase in fly ash content and a decrease in lime content promoted leaching of Ba, B and Cu whereas Zn leaching was primarily affected by the fly ash content. Numerically predicted field metal concentrations were significantly lower than the peak metal concentrations obtained in laboratory column leach tests, and field concentrations decreased with time and distance due to dispersion in soil vadose zone.     

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.     

Optimum Dose Of Lime And Fly Ash For Treatment Of Hexavalent Chromium–Contaminated Soil

The presence of hexavalent chromium, Cr(VI), in soil is an environmental concern due to its effect on human health. The concern arises from the leaching and the seepage of Cr(VI) from soil to groundwater. In this paper, a stabilization technology to prevent this problem was simulated on an artificial soil contaminated with hexavalent chromium. The process is a physico-chemical treatment in which the toxic pollutant is physically entrapped within a solid matrix formed by the pozzolanic reactions of lime and fly ash to reduce its leachability and, therefore, its toxicity. This paper presents the optimum ratio of fly ash and lime in order to stabilize artificial soils contaminated with 0.4 wt.% of Cr (VI) in a brief term process. The degree of chromium released from the soil was evaluated using a modified Toxicity Characteristic Leaching Procedure (TCLP) by US Environmental Protection Agency (EPA). Overall, experimental results showed reduced leachability of total and hexavalent chromium from soils treated with both fly ash and quicklime, and that leachability reduction was more effective with increasing amount of fly ash and quicklime. Stabilization percentages between 97.3% and 99.7% of the initial chromium content were achieved, with Cr(VI) concentration in the TCLP leachates below the US EPA limit for chromium of 5 mg/l. Adequate treatment was obtained after 1 day of curing with just 25% fly ash and 10% quicklime.     

Re-cycling of remediated soil - Evaluation of leaching tests as tools for characterization

In Sweden, leaching tests with deionized water (D.W.) are utilized in risk assessment of materials entering landfills, but implementation of these results to evaluate the risk of spreading of pollutants in the environment is difficult. One problem is that most leaching procedures only consider heavy metals release, whereas organic pollutants are left out. The aim of the present study was to assess the possible pollutant mitigation in four remediated soils, three with heavy metals and one with polycyclic aromatic hydrocarbons (PAH) contamination. The mitigation was evaluated by standardized batch and column leaching tests utilizing three different leaching solutions: D.W., a weak ionic solution (0.001 M CaCl₂) and an artificially made soil water (ASW). In general, batch leaching tests implied larger contaminant removal than column leaching test, possibly due to the more rough treatment of the soil particles, and guidelines would at times be exceeded by the batch leaching test but not by column leaching tests. Utilization of CaCl₂ was found to release less heavy metal than D.W., whereas the metals mobilized by ASW were removed from solution by the filtration of soil leachates. Low molecular weight PAH was most efficiently mobilized by CaCl₂, while D.W. worked better for high molecular weight PAH. Despite very low initial PAH-concentrations, tap- and groundwater criteria were exceeded by all leaching solutions.     

Manufacture of artificial aggregate using MSWI bottom ash

This paper reports the results of an investigation on material recovery by stabilization/solidification of bottom ash coming from a municipal solid waste incineration plant. Stabilization/solidification was carried out to produce artificial aggregate in a rotary plate granulator by adding hydraulic binders based on cement, lime and coal fly ash. Different mixes were tested in which the bottom ash content ranged between 60% and 90%. To avoid undesirable swelling in hardened products, the ash was previously milled and then granulated at room temperature. The granules were tested to assess their suitability to be used as artificial aggregate through the measurement of the following properties: density, water absorption capacity, compressive strength and heavy metals release upon leaching. It was demonstrated that the granules can be classified as lightweight aggregate with mechanical strength strongly dependent on the type of binder. Concrete mixes were prepared with the granulated artificial aggregate and tested for in-service performance, proving to be suitable for the manufacture of standard concrete blocks in all the cases investigated.     

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.     

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.

     

Heavy metal speciation in various types of fly ash from municipal solid waste incinerator

Fly ash (FA) from municipal solid waste incinerators has been known as hazardous waste, which is mostly because of the high content of heavy metal and dioxins. Besides the content, the form of the heavy metals in fly ash is also very important, because it is tightly related with the leaching behavior of fly ash in diverse circumstances. To evaluate the environment potential risk of fly ash, the Tessier chemical extraction method was adopted. In this study, four kinds of fly ash were examined, one sample from China (CFA) and the other three from Japan (RFA, CaFA and NaFA). Five metal elements were detected and they were Ni, Cr, Cd, Pb, and Cu. The result of total heavy metals’ concentration showed CFA has the lowest content. As to the Tessier chemical extraction experiments, the results show that Cd, Pb, and Cu have higher leaching risk in the environment than other heavy metals. The result of leaching test experiment showed that the more exchangeable speciation of Cd, Cr and Pb in FA, the more it could leach out in natural environment.     

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.     

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.     

Influence of treatment techniques on Cu leaching and different organic fractions in MSWI bottom ash leachate

The leaching of heavy metals, such as copper, from municipal solid waste incinerator (MSWI) bottom ash is of concern in many countries and may inhibit the beneficial reuse of this secondary material. Previous studies have focused on the role of dissolved organic carbon (DOC) on the leaching of copper. Recently, a study of the Energy Research Centre of The Netherlands (ECN) showed fulvic acid-type components to exist in the MSWI bottom ash leachates and to be likely responsible for the generally observed enhanced copper leaching. These findings were verified for a MSWI bottom ash (slashed circle 0.1-2 mm) fraction from an incinerator in Flanders. The filtered leachates were subjected to the IHSS fractionation procedure to identify and quantify the fractions of humic acid (HA), fulvic acid (FA) and hydrophilic organic carbon (Hi). The possible complexation of fulvic acid with other heavy metals (e.g., lead) was also investigated. The identified role of fulvic acids in the leaching of copper and other heavy metals can be used in the development of techniques to improve the environmental quality of MSWI bottom ash. Thermal treatment and extraction with a 0.2 M ammonium-citrate solution were optimized to reduce the leaching of copper and other heavy metals. The effect of these techniques on the different fractions of organic matter (HA, FA, Hi) was studied. However, due to the obvious drawbacks of the two techniques, research is focused on finding other (new) techniques to treat MSWI bottom ash. In view of this, particle size-based separation was performed to evaluate its effect on heavy metal leaching and on HA, FA and Hi in MSWI bottom ash leachates.     

Road soil retention of Pb leached from MSWI bottom ash

Municipal solid waste incinerator (MSWI) bottom ash may be used as a road construction material; it potentially contains however a sizable quantity of heavy metals, which under the effect of rainfall infiltration through the road structure can be leached out from the material and infiltrate into the underlying soil. An eco-compatibility assessment of MSWI bottom ash reuse in road construction applications necessitates examining the solubility and retention of heavy metals in road soils. This study is dedicated to Pb transfer, sorption and desorption (NEN 7341 standard test) within various soils. These experiments yield results relative to the interaction between road soils and an MSWI bottom ash leachate representative of a "fresh" product, with a high leaching potential. For the soils investigated, the sorption of lead varies between 90% and 99%. For an extraction at pH 7, Pb release is very low (<2%) for all soils, while at pH 4 leaching varies between 4% and 47%. This work shows that Pb may be fixed by some types of road soil in mostly stable forms.     

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.     

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.     

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.     

Distribution of remaining Cd in MSWI fly ash washed with nitric acid

Municipal solid waste incineration (MSWI) fly ash is by-product and hazardous waste produced from MSWI plant. In the MSWI fly ash there are high contents heavy metals, among which cadmium (Cd) is more active and toxic. Although inorganic acid leaching is an effective way to remove heavy metals out from the MSWI fly ash and nitric acid has great efficiency for Cd removal, little literature reported the redistribution of remaining Cd in the MSWI fly ash. This investigation focused on the change of different factions (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter and residual) of Cd in treated (i.e. washed with nitric acid) MSWI fly ash. Sequence extraction procedures (SEP) have been used to derive different fractions of Cd, results indicated that fractions of Cd have changed significantly after nitric acid washing procedures. Due to the changes of main compounds and microstructures stable Cd (bound to organic matter and residual) had opportunity to leach out, which resulted in a higher potential risk (or higher bioavailability index) for living creatures, although the total amount of Cd decreased. X-ray diffraction (XRD) and images of scanning electron microscope (SEM) proved these changes in washed MSWI fly ash.     

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。     

Leaching behaviour of elements and evaluation of pre-treatment methods for municipal solid waste incinerator residues in column leaching tests.

Two new pre-treatment methods (water-washing/carbonation and carbonation/phosphate stabilization) of municipal solid waste (MSW) incinerator residues were evaluated by column leaching tests under aerobic conditions and anaerobic conditions (which were changed to aerobic conditions after 10 months). A mixture of bottom ash and fly ash (5:1 ratio) was pre-treated using each method. Shredded incombustible residues (SIR) were added to each ash preparation in proportions similar to the ratios present in landfills. For comparison, landfill wastes typical of Japan, namely, a mixture of bottom ash, chelating-pre-treated fly ash, and SIR, were also examined. Leachate samples were collected periodically and analysed over a 15-month period. When compared with chelating pretreatment, both water-washing/carbonation and carbonation/ phosphate stabilization reduced the leaching of Pb, Al, and Cu by about one to two orders of magnitude. Moreover, the initial concentrations of Ca and Pb in leachates from column of water-washing/carbonation were 56-57% and 84-96% less than those from the column of carbonation/phosphate stabilization. Therefore, water-washing/carbonation was considered to be a promising approach to obtain early waste stabilization and to reduce the release of heavy metals to near-negligible levels. The leaching behaviour of elements was also discussed.     

Concentrations of heavy metals in fly ash from a coal-fired power plant with respect to the new Finnish limit values

In Finland, the new limit values for heavy metals in fertilizers used in agriculture and in forestry came into force in March 2007, and for materials used as earth construction agents, in June 2006. From the utilization point of view, it was notable that the total heavy metal concentrations (Cd, Cu, Pb, Cr, Mo, Zn, As, Ni, Ba, and Hg) in fly ash from a coal-fired power plant were lower than those limit values. The concentrations of the easily soluble elements Ca, Mg, Na, P, and Zn in the fly ash were between 3.5 and 35 times higher than those found in the coarse mineral soils of Finland. Fly ash is a potential agent for soil remediation and for improving soil fertility. If inorganic materials and by-products are utilized in earthworks, the content of harmful compounds must be low and the harmful components must be tightly bound to the matrix. Therefore, a five-stage sequential extraction procedure was used to evaluate the extractability of different elements in fly ash into the following fractions: (1) the water-soluble fraction, (2) the exchangeable fraction (CH₃COOH), (3) the easily reduced fraction (NH₂OH-HCl), (4) the oxidizable fraction (H₂O₂ + CH₃COONH₄), and (5) the residual fraction (HF + HNO₃ + HCl).     

Solubility and Potential Mobility of Heavy Metals in Two Contaminated Urban Soils from Stockholm,Sweden

The solubility and potential mobility of heavy metals (Cd, Cu,Hg, Pb and Zn) in two urban soils were studied by sequential andleaching extractions (rainwater). Compared to rural (arable) soils on similar parent material, the urban soils were highlycontaminated with Hg and Pb and to a lesser extent also with Cd,Cu and Zn. Metal concentrations in rainwater leachates were related to sequential extractions and metal levels reported fromStockholm groundwater. Cadmium and Zn in the soils were mainly recovered in easily extractable fractions, whereas Cu and Pb were complex bound. Concentrations of Pb in the residual fractionwere between two- and eightfold those in arable soils, indicatingthat the sequential extraction scheme did not reflect the solidphases affected by anthropogenic inputs. Cadmium and Zn conc. inthe rainwater leachates were within the range detected in Stockholm groundwater, while Cu and Pb conc. were higher, whichsuggests that Cu and Pb released from the surface soil were immobilised in deeper soil layers. In a soil highly contaminatedwith Hg, the Hg conc. in the leachate was above the median concentration, but still 50 times lower than the max concentration found in groundwater, indicating the possibilityof other sources. In conclusion, it proved difficult to quantitatively predict the mobility of metals in soils by sequential extractions.