Impact of Changes in Redox Conditions on Leaching of Some Elements from MSW Fly Ash

Abstract. Oxidation and reduction processes can influence extent of leaching of elements from solid waste. Three samples of municipal solid waste combustion fly ash were subjected to oxidizing and reducing conditions in order to evaluate leaching of elements in the Milli-Q water and fly ash (liquid to solid ratio, 100) mixtures. Although the oxidizing and reducing conditions were applied for 6 hours only, elements like Cs, Li, Mg, Sb, Tl and V leached more under oxidizing condition than under reducing condition in the case of all three ash samples. Cadmium, Pb and Zn leached more from all samples under reducing condition than under oxidizing condition. Leaching of other elements like Al, Ba, Cr, Cu, Ni and Rb was inconsistent with oxidizing or reducing conditions and varied from sample to sample, suggesting that factors other than redox may be more important in controlling leaching of these elements. Strong acid neutralization capacity of the fly ash samples let the pH vary within a narrow range, and thus severely limited the extent of leaching during the course of the experiment. Lead and Zn were the most sensitive while K and Na were the least sensitive to changes in redox conditions.     

Changes in mobility and speciation of heavy metals in clay-amended incinerator fly ash

The generation of municipal solid waste incinerator fly ash (MSWIF) has been increasing significantly over the recent past, and its disposal is problematic and costly due to high concentration of leachable heavy metals present in the material. This study explored a potential stabilization of MSWIF by blending with a natural sorbent material with low permeability, clay, and assessed the potential release of heavy metals from the stabilized mixtures under various simulated subsurface environments. The leachability of heavy metals such as Pb, Cd, Cr, Zn and Cu in the MSWIF-clay mixtures cured for 1 to 360 days was investigated by performing leaching tests and sequential chemical extractions (SCE). Leaching tests were performed at acidic, neutral and alkaline pH values. The leaching test results suggested that the natural clay could turn the MSWIF into non-hazardous material. All the MSWIF-clay mixtures demonstrated leaching behavior different from that of the original MSWIF. SCE results revealed that the acidic and reducing conditions were the most unfavorable to the immobilization of the heavy metals in the stabilized MSWIF-clay matrix. Conversely, the oxidizing and alkaline conditions were not critical to the stabilized MSWIF-clay mixtures. Apparently, clay in the mixtures could function as an adsorptive micro-barrier to retain the heavy metals within the MSWIF-clay matrices.     

Leaching characteristics of fly ash

The disposal of fly ash as a byproduct of thermic power stations, results in significant environmental problems. The leaching of coal fly ash during disposal is of concern for possible contamination, especially for the aquatic environment when ash is in contact with water. The aim of this study was to investigate the leaching behaviour of fly ashes currently disposed in Kemerkoy Power Plant (Turkey) fly-ash-holding pond. The studies were conducted with fly ashes from the electrostatic precipitators (fresh fly ash) and from the fly ash pond (pre-leached fly ash). The fly ashes has alkaline in nature and pH ranges between 11.9 to 12.2. The pre-leached fly ash exhibited lower EC values (7,400 µS) than the fresh fly ash (10,300 µS). In contrast to Fe and Pb, the elements such as Cr, Cd, Cu and Co did not leach from the fly ash. The Ca and Mn concentrations decreased with increasing temperature whereas, Na and K concentrations increased. The results showed that the most important effects of fly ash leaching were pH, Na, Ca, K, Fe, Mg, Mn and Pb.     

Leachability of trace elements from two stabilized low lime Indian fly ashes

Fly ash is a waste by-product obtained from the burning of coal by thermal power plants for generating electricity. When bulk quantities are involved, in order to arrest the fugitive dust, it is stored wet rather than dry. Fly ash contains trace concentrations of heavy metals and other substances in sufficient quantities to be able to leach out over a period of time. In this study an attempt was made to study the leachabilities of a few selected trace metals: Cd, Cu, Cr, Mn, Pb and Zn from two different types of class F fly ashes. Emphasis is also laid on developing an alternative in order to arrest the relative leachabilities of heavy metals after amending them with suitable additives. A standard laboratory leaching test for combustion residues has been employed to study the leachabilities of these trace elements as a function of liquid to solid ratio and pH. The leachability tests were conducted on powdered fly ash samples before and after amending them suitably with the matrices lime and gypsum; they were compacted to their respective proctor densities and cured for periods of 28 and 180 days. A marked reduction in the relative leachabilities of the trace elements was observed to be present at the end of 28 days. These relative leachability values further reduced marginally when tests were performed at the end of 180 days.     

Leaching capabilities of iodine monochloride (ICl) and diethylenetriamine pentaacetic acid (DPTA) at different concentrations and pH for some major and trace metals from coal and coal fly ash

In the present study, coal from Chakwal (Pakistan) was leached with an aqueous solutions of iodine monochloride (ICl) and diethylenetriamine pentaacetic acid (DPTA) of different concentrations. The effect of stirring time, concentration and pH was studied on the leaching of different metals from coal. The physicochemical parameters indicated that the coal was of reasonably good quality. The results indicated that with increase in time duration, the extraction of metals increased. In most of the cases, metal concentration increased in the leachate with increasing the concentration of the leaching agents. DPTA was found to be the best leaching agent for most of the metals. Higher extraction of metals from coal fly ash indicated that coal organic matter has a pronounced effect on the leaching. Higher concentration of metals was extracted from virgin coal and coal fly ash at low pH (p?>?0.00) as compared to high pH. DPTA extracted metals in higher concentration from virgin coal and coal fly ash at low pH as compared to ICl. Based on the present study, the most leached metals were Fe, Cu, Mn and the least were Pb, Ni, Cd and Cr.     

Stability and leaching of cobalt smelter fly ash

The leaching behaviour of fly ash from a Co smelter situated in the Zambian Copperbelt was studied as a function of pH (5–12) using the pH-static leaching test (CEN/TS 14997). Various experimental time intervals (48 h and 168 h) were evaluated. The leaching results were combined with the ORCHESTRA modelling framework and a detailed mineralogical investigation was performed on the original FA and leached solid residues. The largest amounts of Co, Cu, Pb and Zn were leached at pH 5, generally with the lowest concentrations between pH 9 and 11 and slightly increased concentrations at pH 12. For most elements, the released concentrations were very similar after 48 h and 168 h, indicating near-equilibrium conditions in the system. Calcite, clinopyroxenes, quartz and amorphous phases predominated in the fly ash. Various metallic sulfides, alloys and the presence of Cu, Co and Zn in silicates and glass were detected using SEM/EDS and/or TEM/EDS. The leaching of metals was mainly attributed to the dissolution of metallic particles. Partial dissolution of silicate and glass fractions was assumed to significantly influence the release of Ca, Mg, Fe, K, Al and Si as well as Cu, Co and Zn. The formation of illite was suggested by the ORCHESTRA modelling to be one of the main solubility-controlling phases for major elements, whereas Co and Zn were controlled by CoO and zincite, respectively. Sorption of metals on hydrous ferric oxides was assumed to be an important attenuation mechanism, especially for the release of Pb and Cu. However, there is a high risk of Co, Cu, Pb and Zn mobility in the acidic soils around the smelter facility. Therefore, potential local options for “stabilisation” of the fly ash were evaluated on the basis of the modelling results using the PHREEQC code.     

Leaching characteristics of a high-calcium fly ash as a function of pH: a potential source of selenium toxicity

Using a modified extraction procedure, the effect of pH on the leaching of selected elements from Ca-rich (Type C) power plant fly ash was studied. Continuous additions of acetic acid were used to maintain pH values of fly ash slurries at 4.0, 6.0 and 8.0 for 24 h and an additional set was leached at its natural pH (average 11.8) value. Analyses for Se, As, Ca, Cd, Cr, Fe, Na and Pb showed that the highest concentrations occur in the leachate at pH 4.0 and decline with increasing pH. Concentrations of Cr and Fe increased slightly between neutral and high pH. Arsenic, Cd, Cr, Pb and Se concentrations exceeded the Environmental Protection Agency's toxicity criteria at pH 4.0. Selenium was above its toxicity level at pH values near 7 but the other elements were below their respective toxicity levels near neutral pH. Because recent studies show adverse effects of Se on aquatic life at far lower concentrations than the current Environmental Protection Agency's standard, high-Ca, power plant fly ashes represent a potentially hazardous pollutant to surface and subsurface waters.     

铜矿采矿废石重金属环境污染的淋溶实验研究——以安徽铜陵凤凰山矿田药园山铜矿床为例

本文基于凤凰山铜矿田药园山矿床采矿废石的淋溶实验研究,着重探索表生环境下影响重金属淋滤迁移的因素,分析重金属在采矿废石中迁移转化的机制。动态淋滤实验考查了重金属从两种采矿废石中淋出的浓度与淋溶液的pH值、淋滤时间以及淋出液酸度的关系。结果表明,采矿废石中重金属淋滤强度随酸度的增加而逐渐增强,而淋滤出的重金属浓度并不总是随时间的延长而递减,同时实验研究也表明,淋溶采矿废石的排放水不一定都是酸性的。因此,在评价矿山环境污染以及治理过程中要对当地雨水的平均pH值、所排放采矿废石的岩性以及废石的堆放时间进行综合考虑。     

Sorption of As and Se on mineral components of fly ash: Relevance for leaching processes

To improve our understanding of As and Se leaching from fly ash it is necessary to know the underlying geochemical processes. It has been previously suggested that sorption processes may control the partitioning of these trace elements during leaching of fly ash. In natural systems, such as soils and sediments, As and Se have been shown to interact with iron oxides at acidic pH, with CaCO₃ at alkaline pH and with clay-minerals at neutral pH. By analogy, we compared the leaching of As and Se from fly ash with the sorption of arsenate and selenite on hematite, portlandite and mullite. It was possible to describe the leaching of As and Se from acidic fly ash with a simplified model of surface complexation with iron oxides. The apparent adsorption constants calculated from the leaching experiments resembled those calculated from our sorption experiments with hematite and values published for amorphous iron oxide. The leaching of As and Se from alkaline fly ash was compared with the sorption of arsenate and selenite on portlandite. A Ca-phase was shown to control the leaching process. Portlandite was shown to be an important sorbent for arsenate and to a lesser extent for selenite, at pH > 12.4. The affinity of arsenate and selenite for mullite was low. Maximum sorption was reached in the neutral pH ranges, similar to the interactions of oxyanions with kaolinite. Sorption reversibility of arsenate on all three minerals considered in this study was less, or at least slower, than that of selenite. This feature may partly explain that the fraction of As available for leaching from fly ash is generally lower.     

Leaching mechanisms of oxyanionic metalloid and metal species in alkaline solid wastes: A review

An overview is presented on possible mechanisms that control the leaching behaviour of the oxyanion forming elements As, Cr, Mo, Sb, Se, V and W in cementituous systems and alkaline solid wastes, such as municipal solid waste incinerator bottom ash, fly ash and air pollution control residues, coal fly ash and metallurgical slags. Although the leachability of these elements generally depends on their redox state, speciation measurements are not common. Therefore, experimental observations available in the literature are combined with a summary of the thermal behaviour of these elements to assess possible redox states in freshly produced alkaline wastes, given their origin at high temperature. Possible redox reactions occurring at room temperature, on the other hand, are reviewed because these may alter the initial redox state in alkaline wastes and their leachates. In many cases, precipitation of oxyanions as a pure metalate cannot provide a satisfactory explanation for their leaching behaviour. It is therefore highly likely that adsorption and solid solution formation with common minerals in alkaline waste and cement reduce the leachate concentration of oxyanions below pure-phase solubility.     

Self-sealing isolation and immobilization: a geochemical approach to solve the environmental problem of waste acidic jarosite

Mimicking geochemical processes to solve environmental problems was implemented in dealing with waste acidic jarosite and alkaline coal fly ash. By placing these two chemically different materials adjacent to one another, a self-sealing layer was formed at the interface between both wastes, isolating and immobilizing chemical constituents in the process. A series of leaching experiments were performed on each material separately to study the release behavior of the principal constituents. Radiotracer experiments were conducted to explore diffusion and reaction of constituents such as Fe³⁺ in a combined jarosite/fly ash system. A model has been developed to simulate the coupled processes of diffusion and precipitation taking into account porosity change due to pore filling by precipitates. The formation of a self-sealing isolation layer in a hypothetical jarosite/fly ash disposal site was modelled. Leaching results indicate that the release of elements from jarosite is much larger than that from fly ash, and that the highly pH dependent release of Fe, Al, and Zn was controlled by the solubility of their hydroxides. Leaching results also suggest that precipitation reactions can be expected to occur at the interface between jarosite and alkaline coal fly ash where a large pH gradient exists. Radiotracer experiments showed that accumulation of constituents occurred at the interface. Modeled Fe³⁺ profiles in layered jarosite/fly ash were well validated by experiments. Modeling results also showed that with the accumulation of constituents at the interface, a new layer with low porosity was formed. Application of this model suggests that there is a potential use to form a self-sealing layer in jarosite/fly ash co-disposal sites.     

Leaching behaviour of slag and fly ash from laterite nickel ore smelting (Niquelândia,Brazil)

The laterite nickel (Ni) ore smelting operation in Niquelândia (Goiás state, Brazil) produced large amounts of smelting wastes, stockpiled on dumps (slags) and in settling ponds (fly ash). In this study we present data on the chemistry, mineralogy and pH-dependent leaching behaviours of these two waste materials.Bulk chemical analyses indicated that both wastes contained significant amounts of potentially toxic elements (PTEs), with substantially higher concentrations in the case of the fly ash (up to 2.51 wt% Ni, 1870 mg/kg Cr and 488 mg/kg Co). The mineralogical investigations carried out using X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and electron microprobe (EPMA) indicated that the slag was mainly composed of silicate glass, olivine and pyroxene. In contrast, the fly ash was composed of Ni-bearing serpentine-like phases (originating from the furnace feed), Ni-bearing glass, olivine, pyroxene and spinel. The pH-dependent leaching behaviour was performed according the EU standard experimental protocol (CEN/TS 14997) in the pH range of 3–12. The leaching was highly pH-dependent for both materials, and the highest releases of PTEs occurred at pH 3. The slag generally exhibited an U-shaped leaching behaviour of the PTEs as a function of pH, and was found to release up to 48.0 mg/kg Ni, 25.6 mg/kg Cr, and 1.42 mg/kg Co. The fly ash was significantly more reactive, and exhibited its highest leaching level of PTEs between pH 3 and 7. The maximum observed release corresponded to 5750 mg/kg Ni, 4.35 mg/kg Cr, and 112 mg/kg Co. The leached Ni concentrations after 24 h of leaching in deionized water exceeded the limit for hazardous waste by more than 100x according to the EU legislation (40 mg/kg Ni). X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structures (EXAFS) spectra indicated that Ni in the fly ash is predominantly bound in a serpentine-like phase, and during the fly ash experimental alteration it was mainly released from the second shell (corresponding to the atomic distances between Ni and Si, Mg, Fe in high-temperature silicates, glass, and partially dissolved serpentine). This study shows that disposal sites for the fly ash can represent a significant source of local pollution, and direct recycling of the fly ash in the smelting technology (as currently adopted at the Barro Alto new smelter and since few years also at the Niquelândia smelter) is the best environment-friendly option for handling of fly ash in the future.     

Distribution of heavy metals in an incineration system of solid wastes in the Three-Gorges region of the Yangtze River

On the basis of investigations on the composition and contents of heavy metals in the domestic refuse in the Three-Gorges region of the Yangtze River, in combination with the experimental results, this paper deals with the distribution rule of heavy metals in the various compartments of an incineration system： leachate pool, fly ash and residue. It is concluded that in the leachate pool heavy metals should not be neglectable since about 30% of Pb and 10% of Cr are leached here; in the incineration system, above 74% of Cr, As and Pb exists in residue; above 96% of Hg exists in fly ash and the contents of Cd in fly ash are close to those of residue. It is also concluded that the physical conditions of incineration have a significant influence on the distribution of heavy metals in the incineration system.     

Investigating the chemical stabilization of hazardous waste material (fly ash) encapsulated in Portland cement

Portland cement has been suggested as an effective stabilization (physico-chemical) method for hazardous waste. This research explored the immobilization of metals in various mixtures of Portland cement and fly ash waste sampled from coal power plant in the province of Lodz, central Poland. The stabilization of fly ash in Portland cement was investigated under a wide range of pH conditions (3–12). Leachability tests were used to determine the efficiency of the encapsulation by studying the dissolution of alkaline metals (sodium, potassium) and alkaline earth metals (calcium, magnesium). The lowest value of leached metals was obtained for ratio of ash to cement of 1:10 in a case of sodium and calcium, while ratio 1.5 gave the lowest leached effects for potassium and magnesium. The high effectiveness of solidification/stabilization process was gained in high pH values (9–11).     

Long-term brine impacted fly ash,Part II: Mobility of major species in the ash residues

The leaching of major species from fly ash is a function of the pH of the solution in contact with the fly ash. The aim of this study was to determine the effect of the pH of the leachant on the leaching of species from the ash residues recovered after the long-term fly ash–brine interactions. Acid neutralization capacity (ANC) tests using solutions of different pH values ranging from the initial pH of the ash residues (11–12) to pH 4 were employed in the leaching experiments. The ANC tests revealed that the release of major species from the ash residues depended on the pH of the leachants except for Na and Cl, where the significant concentrations leached were independent of the solution pH. The concentrations of Al and Si in the ANC leachates were very high at pH below 6 while Ca, K, Sr, Mg and B were immediately mobilized from the brine impacted fly ash when in contact with de-ionized water, and leaching increased as the pH decreased. The concentration of SO₄ leached from the brine impacted ash residues at high pH was high, and the leaching increased with decrease in the pH of the leachant. This study shows that most of the major elements captured in the ash residues could be mobilized when in contact with aqueous solutions of various pH. This reveals that the co-disposal of fly ash and brine may not be the best practice as the major elements captured in the ash residues could leach over time.     

Coal fly ash interaction with environmental fluids: Geochemical and strontium isotope results from combined column and batch leaching experiments

The major element and Sr isotope systematics and geochemistry of coal fly ash and its interactions with environmental waters were investigated using laboratory flow-through column leaching experiments (sodium carbonate, acetic acid, nitric acid) and sequential batch leaching experiments (water, acetic acid, hydrochloric acid). Column leaching of Class F fly ash samples shows rapid release of most major elements early in the leaching procedure, suggesting an association of these elements with soluble and surface bound phases. Delayed release of certain elements (e.g., Al, Fe, Si) signals gradual dissolution of more resistant silicate or glass phases as leaching continues. Strontium isotope results from both column and batch leaching experiments show a marked increase in ⁸⁷Sr/⁸⁶Sr ratio with continued leaching, yielding a total range of values from 0.7107 to 0.7138. For comparison, the isotopic composition of fluid output from a fly ash impoundment in West Virginia falls in a narrow range around 0.7124. The experimental data suggest the presence of a more resistant, highly radiogenic silicate phase that survives the combustion process and is leached after the more soluble minerals are removed. Strontium isotopic homogenization of minerals in coal does not always occur during the combustion process, despite the high temperatures encountered in the boiler. Early-released Sr tends to be isotopically uniform; thus the Sr isotopic composition of fly ash could be distinguishable from other sources and is a useful tool for quantifying the possible contribution of fly ash leaching to the total dissolved load in natural surface and ground waters.     

Geochemical controls on leaching of lignite-fired combustion by-products from Greece

The mobility of inorganic pollutants is of key concern for a range of industrial and engineering applications of fly ash produced during the combustion of lignite in power generation. This paper investigates the role that the geochemical features of lignite, the ash composition and the partitioning of elements during combustion play in determining leaching properties of lignite fired by-products. The work is based on surveys on three lignite-fired power plants in Greece. Calcium-rich ashes show a high abatement potential for SO₂ and other gaseous pollutants. For most elements, the concentrations in the parent lignite and the ashes follow the same trend. Relative enrichments in Cd, Co, Cr, Cu, Mo, Ni, Pb, U, V, W, Zn fingerprint the regional and local geological settings of the lignite basins. The total and leachable concentrations of highly volatile elements are strongly influenced by the interaction with ubiquitous free lime. A broad array of elements is highly insoluble in alkaline ash, while a few oxyanionic-forming elements display substantial mobility. Their mode of occurrence in the parent lignite plays a primary role in the leaching of combustion ashes. The outcomes of this study may assist in addressing the impact of co-firing high ash or high Ca alternative fuels on the leaching properties of combustion by-products.     

高钙粉煤灰固化重金属污染土的工程性质试验研究

高钙粉煤灰是燃煤电厂排出的固体废物,其堆放不仅需占用大量土地,而且对周围环境存在严重威胁。通过系统的室内试验,着重研究了高钙粉煤灰固化铅与锌污染土的工程性质,揭示了其作用机制,探讨了利用高钙粉煤灰固化重金属污染土的可行性。试验结果表明,土体受到重金属离子污染后其无侧限抗压强度降低,掺入高钙粉煤灰可提高土体强度,并能抑制重金属离子的滤出;污染物浓度较低时,固化污染土中的Pb2+和Zn2+均能得到有效固化,污染物浓度较高时,Zn2+的固化效果优于Pb2+。干湿循环试验结果表明,高钙粉煤灰固化污染土的强度随干湿循环次数的增加,先增大后减小;固化土体中重金属离子浓度较低时,滤出液中金属离子浓度随干湿循环次数增加而增大;重金属离子浓度较高时,滤出液中金属离子浓度基本保持不变。     

粉煤灰污泥添加剂对地下水质影响的模拟研究

通过测定土柱和淋洗液中重金属的含量,研究石灰岩质土壤应用粉煤灰污泥添加剂改良后重金属在土壤剖面上的分布移动特征及对地下水质的影响.结果表明:仅试验层内除As和Ni外,Zn、Cd、Pb、Cu、Cr、Hg含量明显增加,未出现明显向下移动的趋势;同时重金属淋出量明显增加,但未超过地下水Ⅲ级标准.初步认为与添加剂自身、重金属的特性及石灰岩质土壤滤层的截固作用相关.粉煤灰污泥经过合理的配施和预处理应用于石灰岩质矿区退化土壤的改良,短期内不会对地下水的质量产生明显的影响.     

Feasibility of using fly ash,lime, and bentonite to neutralize acidity of pore fluids

Acidic groundwater resulting from the poorly planned use of acid sulfate soils has become a major environmental issue in coastal Australia over the last several years. Use of permeable reactive barriers (PRBs) designed to generate alkalinity by promoting sulfate reduction has recently become popular as an alternative solution to this problem. However, recent studies have also revealed that the long-term performance of such PRBs can be significantly undermined by chemical precipitation and clogging of pore space, which would decrease the buffer capacity and hydraulic conductivity of the reactive material. This study seeks to explore the feasibility of using bentonite in addition to lime and fly ash to form mixtures with a high buffer capacity and permeability that would enable groundwater flow through PRBs over a substantial period of time. A series of laboratory experiments, including buffer capacity and leaching tests, were performed on different mixtures of fly ash with lime and bentonite using acidic fluids of low pH. It was found that the ability of such mixtures to neutralize acidic fluids was mostly controlled by the content of lime. Laboratory data also showed that an addition of bentonite to lime—fly ash mixtures could decrease the buffer capacity of soil. Compaction tests indicated that the presence of bentonite would increase the dry density of mixtures at the optimum moisture content. A series of hydraulic conductivity tests were carried out to study changes in the coefficient of permeability of lime—fly ash mixtures with different contents of bentonite permeated with acidic liquids. The obtained results revealed that the coefficient of permeability of the specimens tended to increase over a period of time, likely due to the changes in the diffuse double layer of bentonite particles.