Zinc speciation in fly ash from MSWI using XAS - novel insights and implications.

The chemical forms of zinc in fly ash from municipal solid waste incineration (MSWI) crucially affect ash management, influencing both material recovery options and the risk of unwanted leaching into ecosystems. The zinc speciation was investigated in fly ash samples sourced from full-scale MSWI plants, including four grate fired boilers (GB) and one fluidized bed boiler (FB). We applied X-ray Absorption Spectroscopy (XAS), and the spectra were analyzed against a unique library of over 30 relevant compounds, tailored to the nuances of zinc chemistry of fly ash. Nano-XANES and sequential leaching were employed as complementary analytical methods. Multiple chemical forms of zinc were found in the ash, whereof potassium zinc chloride salts (K2ZnCl4) emerged as the predominant form in GB fly ash representing 41-64 % of the zinc content, while less for FB fly ash (19 %). The mere exposure to humidity in the air during storage resulted in hydroxylation of the alkali zinc chlorides into Zn5(OH)8Cl2·H2O. Other forms of zinc in the ash were Zn4Si2O7(OH)2·H2O, ZnFe2O4, ZnAl2O4, surface adsorbed zinc, and Zn5(CO3)2(OH)6. Notably, the proportion of zinc in spinel forms (ZnFe2O4 and ZnAl2O4) increased threefold in FB ash compared to GB ash, representing ∼60 % and ∼10-20 % of the zinc, respectively.

Removal and release of microplastics and other environmental pollutants during the start-up of bioretention filters treating stormwater.

Untreated stormwater is a major source of microplastics, organic pollutants, metals, and nutrients in urban water courses. The aim of this study was to improve the knowledge about the start-up periods of bioretention filters. A rain garden pilot facility with 13 bioretention filters was constructed and stormwater from a highway and adjacent impervious surfaces was used for irrigation for ∼12 weeks. Selected plants (Armeria maritima, Hippophae rhamnoides, Juncus effusus, and Festuca rubra) was planted in ten filters. Stormwater percolated through the filters containing waste-to-energy bottom ash, biochar, or Sphagnum peat, mixed with sandy loam. Influent and effluent samples were taken to evaluate removal of the above-mentioned pollutants. All filters efficiently removed microplastics >10 µm, organic pollutants, and most metals. Copper leached from all filters initially but was significantly reduced in the biochar filters at the end of the period, while the other filters showed a declining trend. All filters leached nutrients initially, but concentrations decreased over time, and the biochar filters had efficiently reduced nitrogen after a few weeks. To conclude, all the filters effectively removed pollutants during the start-up period. Before being recommended for full-scale applications, the functionality of the filters after a longer period of operation should be evaluated.

Enhanced soil washing with copper recovery using chemical precipitation.

Worldwide, the number of contaminated sites is large, and remediation methods including recovery of metals have potential to be key aspects of a sustainable and circular economy. Soil washing, followed by chemical precipitation is a possible method for recovery of metals. The purpose of this study is to propose a complete recovery method, where Cu is efficiently leached from samples with contaminated bark ash and soil. Thereafter the Cu is precipitated as metal hydroxide. The results show that pH is the most important parameter that controls the leaching of Cu. The leaching process was independent of the liquid to solid ratio (L/S) for the soil, while the leaching increased with the L/S ratio for the bark ash. The shaking method used for leaching affected the results, as a low leaching efficiency was achieved with the turn-over-end technique used. The final Cu precipitation product from the bark ash contained ≥40 wt % Cu, whereas the corresponding soil precipitation product contained ≤15 wt % Cu. The conclusion is that the bark ash precipitation product is of interest for further refining within the metal industry. Due to inefficient leaching and washing, the soil and bark ash residues left after leaching are classified as hazardous waste.

Leaching for recovery of copper from municipal solid waste incineration fly ash: influence of ash properties and metal speciation.

Recovery of metals occurring in significant amounts in municipal solid waste incineration fly ash, such as copper, could offer several advantages: a decreased amount of potentially mobile metal compounds going to landfill, saving of natural resources and a monetary value. A combination of leaching and solvent extraction may constitute a feasible recovery path for metals from municipal solid waste incineration fly ash. However, it has been shown that the initial dissolution and leaching is a limiting step in such a recovery process. The work described in this article was focused on elucidating physical and chemical differences between two ash samples with the aim of explaining the differences in copper release from these samples in two leaching methods. The results showed that the chemical speciation is an important factor affecting the release of copper. The occurrence of copper as phosphate or silicate will hinder leaching, while sulphate and chloride will facilitate leaching.

Remediation of metal polluted hotspot areas through enhanced soil washing--evaluation of leaching methods.

Soil washing offers a permanent remediation alternative for metal polluted sites. In addition, the washed out metals can be recovered from the leachate and re-introduced into the social material cycle instead of landfilled. In this paper, soil, bark and bark-ash washing was tested on four different metal polluted soil and bark samples from hotspots at former industrial sites. Six different leaching agents; HCl, NH4Cl, lactic acid, EDDS and two acidic process waters from solid waste incineration, were tested, discussed and evaluated. For the soil washing processes, the final pH in the leachate strongly influences the metal leachability. The results show that a pH < 2 is needed to achieve a high leaching yield, while <50 w% of most metals were leached when the pH was higher than 2 or below 10. The acidic process waste waters were generally the most efficient at leaching metals from all the samples studied, and as much as 90-100 w% of the Cu was released from some samples. Initial experiments show that from one of these un-purified leachates, Cu metal (>99% purity) could be recovered. After a single leaching step, the metal contents of the soil residues still exceed the maximum limits according to the Swedish guidelines. An additional washing step is needed to reduce the contents of easy soluble metal compounds in the soil residues. The overall results from this study show that soil and bark-ash washing followed by metal recovery is a promising on-site permanent alternative to remediate metal polluted soils and to utilize non-used metal resources.

Bioelectrochemical recovery of Cu, Pb, Cd, and Zn from dilute solutions.

In a microbial bioelectrochemical system (BES) living microorganisms catalyze the anodic oxidation of organic matter at a low anode potential. We used a BES with a biological anode to power the cathodic recovery of Cu, Pb, Cd, and Zn from a simulated municipal solid waste incineration ash leachate. By varying the control of the BES, the four metals could sequentially be recovered from a mixed solution by reduction on a titanium cathode. First, the cell voltage was controlled at zero, which allowed recovery of Cu from the solution without an electrical energy input. Second, the cathode potential was controlled at -0.51 V to recover Pb, which required an applied voltage of about 0.34 V. Third, the cathode potential was controlled at -0.66 V to recover Cd, which required an applied voltage of 0.51 V. Finally, Zn was the only metal remaining in solution and was recovered by controlling the anode at +0.2V to maximize the generated current. The study is the first to demonstrate that a BES can be used for cathodic recovery of metals from a mixed solution, which potentially could be used not only for ash leachates but also for e.g. metallurgical wastewaters and landfill leachates.

Removal of hazardous metals from MSW fly ash--an evaluation of ash leaching methods.

Incineration is a commonly applied management method for municipal solid waste (MSW). However, significant amounts of potentially hazardous metal species are present in the resulting ash, and these may be leached into the environment. A common idea for cleaning the ash is to use enhanced leaching with strong mineral acids. However, due to the alkalinity of the ash, large amounts of acid are needed and this is a drawback. Therefore, this work was undertaken in order to investigate some alternative leaching media (EDTA, ammonium nitrate, ammonium chloride and a number of organic acids) and to compare them with the usual mineral acids and water. All leaching methods gave a significant increase in ash specific surface area due to removal of soluble bulk (matrix) compounds, such as CaCO(3) and alkali metal chlorides. The use of mineral acids and EDTA mobilised many elements, especially Cu, Zn and Pb, whereas the organic acids generally were not very effective as leaching agents for metals. Leaching using NH(4)NO(3) was especially effective for the release of Cu. The results show that washing of MSW filter ash with alternative leaching agents is a possible way to remove hazardous metals from MSW fly ash.