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.     

Reducing Sb-leaching from municipal solid waste incinerator bottom ash by addition of sorbent minerals

This paper investigates the mechanisms controlling Sb-leaching from fresh Municipal Solid Waste Incinerator (MSWI) bottom ash, as well as the possibilities of controlling the extent of Sb-leaching by the addition of sorbent minerals to the bottom ash. In alkaline MSWI bottom ash Sb is possibly incorporated in ettringite-like minerals. When weathering/carbonation continues the ettringite dissolves resulting in a mobilisation of Sb. At neutral pH values the leaching of Sb is likely to be controlled by sorption to amorphous Fe/Al-(hydr)oxides. It has been shown that Sb can effectively be removed from solution if salts of Fe(III) or Al(III) are added to the bottom ash. This addition of Fe(III)/Al(III)-salts leads to (1) the in-situ precipitation of Fe/Al-hydroxides and sorption/coprecipitation of contaminants such as Sb, and (2) a lower bottom ash pH and thus an increased affinity of oxyanions for sorption to Fe/Al-(hydr)oxides.     

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.     

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.     

Speciation of Cu in MSWI bottom ash and its relation to Cu leaching

In Flanders, recycling of bottom ash is mainly inhibited by the high leaching of Cu. Although it has been proved that dissolved organic C plays a major role in the Cu leaching, the possible role of inorganic Cu mineral speciation has never been experimentally examined. In this study the speciation of Cu is investigated using a combination of optical microscopy and electron microprobe –WDX/EDX. Several Cu species were determined. Metallic Cu (with or without an oxide shell), CuO and Cu₂O were the most abundant. These particles were most likely present in wire-like structures. Copper also occurred as alloy (brass, bronze, zamak), and was found frequently together with typical elements such as Ca, Cl and S. Finally, small metallic Cu particles seemed to be trapped in or precipitated on oxides and silicates. Based on this Cu speciation study, pure Cu minerals were selected and leached as a function of time. The solubility after equilibrium of all studied Cu minerals never exceeded 20 μg/L (which equals 10% of the total Cu leaching).The effect of heating (2 h at 400 °C) on the speciation of Cu was investigated using the same combination of techniques. Results show that metallic Cu seemed to be converted to Cu oxide (mostly CuO) and that the particles were more porous after heating. These conclusions were verified by XRD analysis of the heated pure Cu minerals. After heating, the Cu minerals were also leached as a function of time, to study the impact on Cu leaching. Results indicate that their leaching had slightly increased in comparison with the non-heated Cu minerals. However, the major decrease in Cu leaching in heated bottom ash, more than neutralizes this effect and thus can be attributed to the destruction of organic matter and not to the (small) change in Cu speciation.     

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.     

Hydromorphic dispersion of Cu and Mo over mineralized granodiorite in a high rainfall peaty area in Ireland: geochemical interpretation and case study

Dispersion of Cu and Mo in mainly ombrotrophic-type peat and till on mineralized Galway Granodiorite, Ireland, is controlled by high rainfall (leaching of surface peat), organic content of till, limonite/bog iron, Eh and pH. Sampling surface blanket peat should be avoided in mineral exploration due to downward leaching. Copper accumulates more effectively than Mo in slightly reduced basal peat, organic-rich till, and organic-rich drain and stream beds. Molybdenum, being more mobile, occurs in a much broader range of organic-rich till, and limonite-stained till and lakeshore sediments. Hence, Mo is a useful pathfinder for Cu. Mobility of Cu and Mo is low due to complexation and/or adsorption, hence overburden anomalies make reasonable drill targets.     

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.     

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.     

Surface complexation of Cu on birnessite (δ-MnO2): Controls on Cu in the deep ocean

Hexagonal birnessite (δ-MnO₂) is a close analogue to the dominant phase in hydrogenetic marine ferromanganese crusts and nodules. These deposits contain ∼0.25 wt.% Cu which is believed to be scavenged from the overlying water column where Cu concentrations are near 0.1 μg/L. Here, we measured the sorption of Cu on δ-MnO₂ as a function of pH and surface loading. We characterized the nature of the Cu sorption complex at pH 4 and 8 using EXAFS spectroscopy and find that, at pH 4, Cu sorbs to birnessite by inner-sphere complexation on the {0 0 1} surface at sites above Mn vacancies to give a three to fourfold coordinated complex with 6 Mn neighbors at ∼3.4 Å. At pH 8, however, we find that some Cu has become structurally incorporated into the MnO₂ layer by occupying the vacancy sites to give 6 Mn neighbors at ∼2.91 Å. Density functional calculations on and clusters predict a threefold coordinated surface complex and show that the change from surface complexation to structural incorporation is a response to protonation of oxygens surrounding the vacancy site. Consequently, we propose that the transformation between sorption via surface complex and vacancy site occupancy should be reversible. By fitting the Cu sorption as a function of surface loading and pH to the formation of the observed and predicted surface complex, we developed a surface complexation model (in the basic Stern approximation) for the sorption of Cu onto birnessite. Using this model, we demonstrate that the concentration of inorganic Cu in the deep ocean should be several orders of magnitude lower than the observed total dissolved Cu. We propose that the observed total dissolved Cu concentration in the oceans reflects solubilization of Cu by microbially generated ligands.     

Seasonal variations of Zn, Cu, As and Mo in arsenic-rich stream at the Mokrsko gold deposit, Czech Republic

Monthly sampling of slightly alkaline arsenic-rich stream in the Mokrsko gold deposit revealed seasonal variations in dissolved Zn, Cu, As and Mo. Concentrations of trace metal cations (Zn, Cu) increased as much as 330 and 178%, respectively, from minimum mean values at autumn to maximum mean values at spring. In contrast, concentrations of trace element oxyanions (As, Mo) revealed opposite seasonal pattern with increase to 189% (As) and 123% (Mo) during summer–autumn, indicating that in-stream biogeochemical process(es) played the main role in controlling the seasonal variations of these trace elements. The trace elements were mainly scavenged by low crystalline Mn oxyhydroxide and Fe oxyhydroxide (ferrihydrite). Results are consistent with sorption and coprecipitation processes controlling seasonal variations of dissolved Zn and Cu, while As and Mo dynamics appear linked to Mn redox reactions. The sorption processes and Mn redox processes are attributed to the changes of pH and oxic/anoxic conditions on the surface of oxyhydroxides, respectively, which are themselves controlled by the balance between photosynthesis and respiration. Under the geochemical conditions of the stream, inferred Mn redox reactions can only be explained by microbial activity.     

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.     

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.     

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.     

Adsorption of molybdenum on to anatase from dilute aqueous solutions

Adsorption of Mo on to hydrous TiO₂ (anatase) particles was investigated. Batch experiments were conducted at 19 and 90 °C over a pH range of 2 to 12 and Mo concentrations ranging from approximately 10⁻⁶ to 10⁻⁴ M. The extent of sorption was strongly dependent on pH and surface loading. Maximum sorption was observed in the acidic pH range at low surface loading. Adsorption behavior was described using the empirical Langmuir adsorption model. A constant capacitance surface complexation model was also used to fit the adsorption isotherms using a ligand exchange reaction for a hydroxyl surface site on anatase. Comparison of experimental data at two different temperatures (19 and 90 °C) indicates that Mo sorption in the acidic pH range decreases with increasing temperature.     

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.