Speciation of trace metals in leachate from a MSWI bottom ash landfill

Trace metal concentrations and speciation were determined in leachate from a municipal solid waste incinerator bottom ash landfill both experimentally and by thermodynamic model calculations. Total dissolved Cr, Sb and W concentrations determined directly by ICP-MS were up to two orders of magnitude higher than that determined upon preconcentration by anin-situ solid phase extraction technique based on 8-HQ cation exchanger which indicates oxyanion complex formation of these metals in the leachates. Speciation modeling suggests that a similar difference for Cu is caused by organic complexation. Lead and Zn concentrations determined by both methods were fairly comparable but very low, in the range 4–60 nmol l⁻¹. The low mobility of both metals can be modeled by assuming adsorption onto Fe-oxyhydroxides oxycoprecipitation with Ca-silicate hydrate phases. The resulting high retardation coefficients between 500 and 800 indicate that scavenging by these secondary weathering products in the MSWI bottom ash deposit can cause an efficient immobilization of both Pb and Zn.     

The leaching of major and trace elements from MSWI bottom ash as a function of pH and time

In this paper, the leaching behaviour of major components (Al, Ca, SO₄, Mg, Si, Fe, Na and DOC) and trace elements (Ni, Zn, Cd, Cu, Pb, Mo and Sb) from MSWI bottom ash is studied as a function of time over a wide range of pH, under pH-controlled conditions. Equilibrium geochemical modelling using the modelling framework ORCHESTRA is used to enable a process-based interpretation of the results and to investigate whether ‘equilibrium’ is attained during the time scale of the experiments. Depending on the element and setpoint-pH value, net concentration increases or decreases of up to one order of magnitude were observed. Different concentration–time trends (increase or decrease) are observed in different pH ranges. The direction of the concentration–time trends depends on: (1) the shape of the ‘equilibrium’ solubility curve, and (2) the position of the setpoint-pH in the leaching test relative to the natural pH of the sample. Although the majority of the elements do not reach steady state, leached concentrations over a wide pH range have been shown to closely approach ‘equilibrium’ model curves within an equilibration time of 168 h. The different effects that leaching kinetics may have on the pH dependent leaching patterns have been identified for a wide range of elements, and can generally be explained in a mechanistic way. The results are in support of the currently prescribed equilibration time of 48 h in the European standard for the pH-static leaching test (TS14997). Finally, this study demonstrates that pH-static leaching experiments such as described in the European standards (TS14497 and TS14429), in combination with selective chemical extractions and a mechanistically based modelling approach, constitute a powerful set of tools for the characterization of leaching processes in waste materials over a wide range of conditions.     

Stable isotope evidence for the atmospheric origin of CO2 involved in carbonation of MSWI bottom ash

Stable isotopes were used to constrain the origin of CO₂ involved in the ageing process of municipal solid waste incineration (MSWI) bottom ash under open-air conditions. The δ¹³C and δ¹⁸O values of CaCO₃ occurring in MSWI bottom ash samples of variable age and the δ¹³C of the residual organic matter content were measured, and laboratory assessments made of the isotopic fractionation accompanying CaCO₃ neo-formation during accelerated carbonation experiments of bottom ash or pure lime with atmospheric or industrial CO₂. The results indicate that stable isotopic compositions exhibited by fresh and aged bottom ash samples reflect non-equilibrium processes resembling those described in the carbonation of concrete and mortar. They also lead to conclusions on the prevalent involvement of atmospheric CO₂ in the open-air carbonation of MSWI bottom ash.     

Carbonation processes in municipal solid waste incinerator bottom ash and their effect on the leaching of copper and molybdenum

The interaction of CO₂ with municipal solid waste incinerator (MSWI) bottom ash was studied in order to investigate the resulting changes in pH and bottom ash mineralogy and the impact that these changes have on the mobility of Cu and Mo. Carefully controlled carbonation experiments were performed on bottom ash suspensions and on filtered bottom ash leachates. Changes in leachate composition were interpreted with the geochemical model MINTEQA2, and neoformed minerals were investigated by means of chemical and spectroscopic analysis. The leaching of Cu and Mo during artificial carbonation is compared to the leachability of Cu and Mo from a sample of naturally carbonated bottom ash from the same incinerator. During carbonation in the laboratory, a precipitate was formed that consisted mainly of Al-rich amorphous material, calcite, and possibly gibbsite. Carbonation to pH ≈8.3 resulted in a reduction of more than 50% in Cu leaching, and a reduction of less than 3% in Mo leaching. The reduction in Cu leaching is attributed to sorption to the neoformed amorphous Al-minerals. During natural weathering/carbonation of bottom ash, additional sorption sites are formed which further reduce the leaching of Cu and Mo on a time scale of months to years.     

Mineralogical study of secondary mineral phases from weathered MSWI bottom ash: implications for the modelling and trapping of heavy metals

A mineralogical study of 3 samples of municipal solid waste incineration bottom ash collected from different storage sites and with storage times varying from 3 weeks to 2 years, has enabled identification of the main secondary mineral species formed during weathering. The frequencies of the secondary phases were determined and a diagram is proposed for the relative distribution of the newly formed mineral phases: calcite ≫ Fe oxides quartz ⩾ sulphates and/or ettringite (depending on the amount of reactive Al present in the bottom ash). This approach, involving careful sampling, sample preparation and the combined use of various analytical techniques, also showed the high frequency of Al hydroxides and amorphous phases and helped to identify more than 30 sulphates s.l. (sulphates, chromates, vanadates, etc.). Most of the secondary minerals (carbonates and sulphates s.l.) have broad metal trapping capacities for heavy element uptake (Pb, Zn, Cd, As, V, Cr, etc.) due to their crystal-chemistry characteristics. Ca-oxalates were also identified. Mineralogical data from the study provide new input for thermochemical models. The relative stability of metal uptake and the extent of associated neogenesis occurring during bottom-ash decomposition is discussed. Sulphate minerals (and certain heavy metal oxides (zincite)), which are extremely sensitive to environmental conditions, can trap metals only temporarily, as opposed to Fe oxyhydroxides (As, etc.) and carbonates (Pb, Zn, Cd), which are more stable under atmospheric conditions and constitute more sustainable trapping media with higher liquid/solid (L/S) ratios. Finally, a composite predictive diagram is proposed for the mineralogical evolution of bottom ash that accounts for variations in L/S ratios.     

The leaching of trace elements from municipal solid waste incinerator bottom ash at different stages of weathering

For a proper assessment of the environmental impact of the utilisation and disposal of Municipal Solid Waste Incinerator (MSWI) bottom ash it is necessary to understand weathering processes and their effects on (trace) element leaching. The authors have investigated the processes that control the leaching of Cd, Pb, Zn, Cu, and Mo from 3 categories of bottom ash: (A) unweathered bottom ash (grate siftings and unquenched samples), (B) quenched/non-carbonated bottom ash (freshly quenched and 6-week-old samples), and (C) weathered bottom ash (1.5- and 12-year-old samples). Leaching experiments were performed in a pH-stat at a large range of pH values. The speciation code MINTEQA2 was used for subsequent modelling of precipitation/dissolution processes. The speciation of trace elements in weathered bottom ash was also investigated by microanalytical techniques. In A- and B-type bottom ash the general controlling processes are thought to be precipitation/dissolution of relatively soluble minerals or, in the case of Cu in particular, extensive complexation with dissolved organic C. At the “natural” pH of the samples, the leaching of Cd, Pb, Cu, Zn and Mo is generally significantly lower from C-type bottom ash than from less weathered types of bottom ash. This reduction in leaching is due to the neutralisation of bottom ash pH and the formation of less soluble species of these elements as weathering continues. In the more weathered (C-type) bottom ash trace element leaching does not seem to be solubility-controlled; although slow precipitation reactions cannot be totally excluded, it is hypothesised that the controlling mechanism in those samples is sorption to neoformed minerals.     

Risk assessment of bottom ash from fuel oil power plant of Italy: mineralogical,chemical and leaching characterization

The main aim of the present study is to contribute to the field of environmental research by providing new data on bottom ash samples derived from an oil power plant located in Southern Italy. To achieve this purpose, the mineralogical and chemical properties of representative bottom ash samples were investigated through the integrated employment of different analytical techniques, i.e., X-ray powder diffraction, scanning electron microscopy, X-ray fluorescence and atomic absorption spectrometry. The obtained experimental results show that quartz, alunogen, rhomboclase and potassium hydrogen silicate are the major crystalline phases of all the analyzed samples. Furthermore, the revealed main ash constituents are SiO₂ and SO₃, with low contents of Fe₂O₃ and Al₂O₃, and little amounts of CaO, Na₂O, K₂O, MgO, P₂O₅ and TiO₂. Among the trace elements, very high amounts of heavy metals, i.e., V, Cr, Ni, La, Pb and Mo, were detected. The comparison of the obtained heavy metal abundance data with those reported in the literature highlights significant differences. Leaching test evidenced V, Ni and Cr values that make these ashes a potential contamination source for groundwater quality and for soil, nearby the ash disposal landfills area. All the obtained findings show that these materials are highly harmful for the human health, with a greater extent for the heavy metal concentrations.     

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.     

Petrogenesis of municipal solid waste combustion bottom ash

A petrographic study was conducted on a suite of bottom ash particles from 3 different modern municipal solid waste combustors. The object of the study was to evaluate the mineralogical characteristics and formation process of the bottom ash by using standard geological techniques of light microscopy, electron microscopy, and X-ray microanalysis. This information was subsequently used to model the bottom ash petrogenesis based upon an examination of the mineralogy, melt structure, and composition of the ash.Bottom ash can be divided into two major groups: 1) refractory waste products and 2) melt products. The refractory waste products consist largely of rock and mineral fragments, various waste metals, and unmelted glass shards. The melt products consist of two distinct glasses: 1) isotropic glass, and 2) opaque glass. Complex silicate minerals are precipitated from and are abundant in the isotropic glass whereas both metal oxide and silicate minerals are precipitated from the opaque glass.The isotropic and opaque glasses formed simultaneously in different locations on the combustor grate. The contrast in melting (liquidus) temperatures shown by these glasses suggests that the isotropic melts were produced at localized hot spots (1500°C to 1650°C) and the opaque melts formed at cold spots (1150°C to 1400°C) on the grate. This could be the result of heterogeneous distribution of combustible municipal solid waste on the grate or from localized hot spots where air is introduced through the grates. In some instances the two glasses then had the opportunity to variably mix with each other. Fe-oxides represent waste metal fragments that were assimilated by melting and later recrystallized.Bottom ash is produced via a co-mingled two melt system that forms melilite-bearing, alkaline, volcanic-like rocks. The great similarity of the bottom ash residues between these 3 different MSW combustors suggests that, despite variable combustor designs and heterogeneous waste feed, high temperature combustion of MSW produces bottom ash of fairly uniform composition and structure that formed via the petrogenetic process described above. Alterations to the combustion process or implementations of secondary treatment technologies may render the bottom ash residue into a more environmentally stable material better suited for aggregate or long term secure disposal in landfills.     

Morphological and strength analysis of PCC bottom ash amended with bentonite

Within the last few years several studies have been completed to evaluate strength, stiffness, and durability properties of pulverized coal combustion (PCC) bottom ash mixed with various admixtures. Studies have shown that strength and stiffness of PCC bottom ash mixed with sodium bentonite changes with the increase in the curing period. Researchers have concluded that this change is due to the chemical composition of the bottom ash and bentonite. In order to understand the reasons for the change in characteristics of bottom ash-bentonite mixtures with time, the strength and structural characteristics of bottom ash-bentonite mixtures cured for various periods was evaluated. Results of the strength testing showed increase in strength and stiffness of the mixtures with curing period. The results of structural analysis using environmental scanning electron microscopy show development of fibrous elements which may cause increase in the unconfined compressive strength and stiffness of the mixtures with the curing period. Selected results from this study are presented herein.     

Speciation of some heavy metals in bottom sediments of the Ob and Yenisei estuarine zones

The speciation of Fe, Mn, Zn, Cu, Co, Ni, Cr, Pb, and Cd was studied in 52 samples of bottom sediments collected during Cruise 49 of the R/V Dmitrii Mendeleev in estuaries of the Ob and Yenisei rivers in the southwestern Kara Sea. Immediately after sampling, the samples were subjected to on-board consecutive extraction to separate metal species according to their modes of occurrence in the sediments: (1) adsorbed, (2) amorphous Fe-Mn hydroxides and related metals, (3) organic + sulfide, and (4) residual, or lithogenic. The atomic absorption spectroscopy of the extracts was carried out at a stationary laboratory. The distribution of Fe, Zn, Cu, Co, Ni, Cr, Pb, and Cd species is characterized by the predominance of lithogenic or geochemically inert modes (70–95% of the bulk content), in which the metals are bound in terrigenous and clastic mineral particles and organic detritus. About half of the total Mn amount and 15–30% Zn and Cu is contained in geochemically mobile modes. The spatiotemporal variations in the proportions of metal species in the surface layer of sediments along the nearly meridional sections and through the vertical sections of bottom sediments cores testify that Mn and, to a lesser extent, Cu are the most sensitive to changes in the sedimentation environment. The role of their geochemically mobile species notably increases under reducing conditions.     

江西城门山铜多金属矿岩浆侵位机制与成矿关系探讨

城门山铜矿自二十世纪50年代发现以来,经过多年工作已被证实为一个大型的"三位一体"的铜多金属矿床,成矿与区内花岗闪长斑岩、石英斑岩有关。文章通过以往资料和实地工作成果研究,认为矿区内花岗闪长斑岩和石英斑岩二者存在演化关系,且两种岩浆的侵位机制的不同导致了其成岩时代、成矿专属性的不同。在没有经过演化分异之前的原始岩浆可能首先被九瑞地区的基底隆起运动抬升,后期花岗闪长斑岩岩浆从原始岩浆中分异出来并继续被抬升,形成被动侵位,并发生了中低温成矿元素和中高温成矿元素的运移和富集,形成与花岗闪长斑岩有关的铜、锌、金矿床;随后的构造运动叠加作用,使矿区断裂构造与剩余的石英斑岩岩浆联通,造成了其主动侵位,从而形成与石英斑岩有关的钼矿床。     

Chemical composition and leaching characteristics of granules made of wood ash and dolomite

 In 1995, the central heating plant Draken in Kalmar, Sweden, started manufacturing a granular ash product for nutrient recycling to forest soil, instead of dumping the ash in landfills. Chemical composition, leaching and dissolution characteristics were determined for the Draken wood ash, the dolomite used in granule manufacturing and the final granule product. The heavy metal concentrations in fly ash were within the limit values recommended by the Swedish National Board of Forestry for ash recycling, except for Cd and As levels which occasionally exceeded the limit values. The Ca, Mn and P levels were too low for nutrient recycling at the time. Adding dolomite insures that the levels of the important nutrients Ca and Mg are sufficient in the granules. After 7 months in the field, about 60 % of Na and K was leached out from granules. Between 20 and 60% of trace elements Mo, Sc, V, Y and Zr were leached out after 7 months. The release of Ca and Mg was low, 1–5% during 7 months. Received: 12 July 1999 · Accepted: 31 August 1999     

Microbial mutualism in leaching of Cu−Ni sulfide concentrate

With tightening legislations on air pollution and decreasing grades of Cu and Ni ores, the mineral processing industry will have to find an alternative to smelting. One such hydrometallurgical alternative is bacterial leaching; it utilizes the action of Thiobacillus ferrooxidans on sulfide minerals converting them to metal sulfates which can be leached by acid produced by the bacteria. The metal is recovered by cementation, solvent extraction or electrowinning. In the present paper, the authors report their test work with a Cu-Ni sulfide concentrate and show that the mutualistic association of T. ferrooxidans with nitrogen-fixing bacteria Beijerinckia lacticogenes helps leach more metal faster in a leaching medium devoid of any added carbon or nitrogen source. Use of intentionally mixed bacterial culture in ore leaching has not been previously reported.     

Acid leaching of ash and coal: Time dependence and trace element occurrences

The leaching of coal and coal/asphaltite/wood-ashes in sulfuric acid (pH 1.0, 25 °C, S/L, 1:10) was studied as a function of time; acid consumption and extracted metal concentrations are presented. Whole coals consumed acid rapidly during the first few minutes, followed by slow acid consumption. Wood-, lignite-, and asphaltite-ashes consumed acid in two stages, the rapid phase extending < 30 min and the slow phase extended up to 10 days. The rapid phase was dominated by the dissolution of Ca, K and Mg ions for wood-ash, by Ca, Al and Mg ions for lignite-ash and Ca and Mg ions for asphaltite-ash. The sulfur concentration in solution and the concentrations of Ca, Fe, K, Mg, Na, P, Al and Mn in the aqueous phase verified the neutralizing capacity of the untreated ashes as well as the formation of insoluble sulfates in the residues. The slow phase kinetics differed for different fuels and exhibited leaching of several abundant elements—Fe, Al, K, Na and Mn. Trace elements (Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Th, U, V, Zn) sometimes required up to 32 h for maximal extraction from ashes. Suggestions are presented regarding the chemical nature of trace elements in the untreated coals and ashes and suitable residence times for economical industrial processes. We think it possible to combine bacteriological oxidation of sulfidic concentrates of acid leaching from ash of various qualities or even whole coals.     

Utilization of leonardite and coal bottom ash for production of ceramic floor tiles

The aim of this research was to exploit leonardite and coal bottom ash (CBA), which are waste products from coal power plants, for investigating their potential as raw materials in the production of ceramic floor tiles. The developments of ceramic body were mixed with traditional raw materials. Different proportions of ceramic materials were studied in order to explore the proper composition with a variety of wastes containing leonardite and coal bottom ash from 20% up to 80%. Unglazed tiles were produced by shaping through dry pressing and single firing. The physical, chemical, and mechanical properties of the samples were investigated. The total waste (CBA and leonardite) contained in the production was close to 42.8%, and it presented properties that are adequate for it to be classified in groups within the ISO 13006 standard, and yielded the highest flexural strength which enabled the obtained ceramic floor tile bodies to satisfy the requirement to be classified in group BIIa. The chemical resistances of the products were classified in the category UA group which passed the minimum requirement for classification as chemical attack, set by standard EN 14411.     

Bearing capacity of soft soil model treated with end-bearing bottom ash columns

Granular column technique is a soil improvement method used to increase the bearing capacity of a soft soil area by replacing the soil with a group of granular column materials. The by-product utilisation is a worldwide interest for sustainable infrastructure development. Bottom ash, which is a combustion deposit derived from coal burning, is a potential by-product that could be used alternatively to sand or aggregate as a green granular column material. This research is to study the potential use of the bottom ash column-improved soft clay by conducting a series of small-scale physical modelling test. The bearing capacity behaviour and failure mode of soft clay improved with end-bearing group of bottom ash columns with and without geotextile encasement are investigated. The bearing capacity of soft clay is significantly enhanced by the inclusion of bottom ash columns; that is, 239% of bearing capacity improvement is observed with only 13% of improvement area. The bulging of the bottom ash column is transferred to buckling failure with higher bearing capacity when the bottom ash column is encased by geotextile. The outcome of this research leads to the usage of bottom ash by-product as a granular column material in sustainable soil improvement technique.     

准格尔地区粉煤灰中镓的浸出率影响因素研究

为了粉煤灰的高附加值综合利用,采用酸浸法对准格尔地区循环流化床粉煤灰进行了镓的浸出实验研究,考察了多种因素对镓的浸出率的影响,包括粉煤灰粒度,酸的种类与浓度、酸浸温度与时间、固液比等。结果表明,提高镓的浸出率的适宜条件为:粉煤灰粒度200目,盐酸的浓度6 mol/L,酸浸温度应大于160℃,酸浸时间6 h,液固比在5∶1~6∶1之间为宜。在优选的工艺条件下,镓的浸出率可达80%以上。从粉煤灰中提取镓,使其作为一种资源加以利用,是提高粉煤灰综合利用价值的有效途径。