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Wildland-urban interface (WUI) fires consume fuels, such as vegetation and structural materials, leaving behind ash composed primarily of pyrogenic carbon and metal oxides. However, there is currently limited understanding of the role of WUI fire ash from different sources as a source of paramagnetic species such as environmentally persistent free radicals (EPFRs) and transition metals in the environment. Electron paramagnetic resonance (EPR) was used to detect and quantify paramagnetic species, including organic persistent free radicals and transition metal spins, in fifty-three fire ash and soil samples collected following the North Complex Fire and the Sonoma-Lake-Napa Unit (LNU) Lightning Complex Fire, California, 2020. High concentrations of organic EPFRs (e.g., 1.4 × 1014 to 1.9 × 1017 spins g−1) were detected in the studied WUI fire ash along with other paramagnetic species such as iron and manganese oxides, as well as Fe3+ and Mn2+ ions. The mean concentrations of EPFRs in various ash types decreased following the order: vegetation ash (1.1 × 1017 ± 1.1 × 1017 spins g−1) > structural ash (1.6 × 1016 ± 3.7 × 1016 spins g−1) > vehicle ash (6.4 × 1015 ± 8.6 × 1015 spins g−1) > soil (3.2 × 1015 ± 3.7 × 1015 spins g−1). The mean concentrations of EPFRs decreased with increased combustion completeness indicated by ash color; black (1.1 × 1017 ± 1.1 × 1017 spins g−1) > white (2.5 × 1016 ± 4.4 × 1016 spins g−1) > gray (1.8 × 1016 ± 2.4 × 1016 spins g−1). In contrast, the relative amounts of reduced Mn2+ ions increased with increased combustion completeness. Thus, WUI fire ash is an important global source of EPFRs and reduced metal species (e.g., Mn2+). Further research is needed to underpin the formation, transformation, and environmental and human health impacts of these paramagnetic species in light of the projected increased frequency, size, and severity of WUI fires.
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Iron dissolution and speciation from combustion particles under environmentally relevant conditions
Environmental contextIron-containing combustion particles are likely to contribute to environmental iron deposition, while atmospheric acidic processing of such particles can promote their dissolution. Here we report the surface-mediated dissolution of iron from ashes generated by biomass burning power plants and kilns. Examination of the dissolution process at several environmentally relevant pHs, suggests that pH has little impact on the fraction of bioavailable Fe(II) that dissolves into the aqueous phase, although Fe(III) is heavily pH dependent. RationaleAnthropogenic combustion particles, such as ash produced in power plants or kilns, are byproducts with limited use that accumulate in large deposits and become materials of environmental concern. While stored, these particles can be carried by winds into the atmosphere or into soil or near water bodies. Recent studies suggest that a fraction of metals present in the environment come from combustion particles. MethodologyIn this study, we carry out a comparative study of iron dissolution and speciation from two different combustion particles: bottom ash from a biomass-fired power plant (BA) and lime kiln dust (LKD). Samples were fully characterised and their iron leaching was investigated in aqueous suspensions under environmentally relevant acidic conditions. Iron analysis and speciation was carried out calorimetrically. ResultsFor the combustion particles examined, the fraction of bioavailable Fe2+ is lower than Fe3+. The solubility of Fe3+ is highly dependent on pH, dropping significantly at pHs higher than 3. On the other hand, the solubility of Fe2+ from both BA and LKD was found to be relatively constant over the range of pH investigated. DiscussionIron availability from combustion particles with similar mineralogy is driven by the particle’s surface properties. While iron from LKD dissolves faster than that from BA, the initial rate of dissolution of iron remains statistically constant at pHs relevant for the atmospheric aerosol deliquescent layer, decreasing at pHs above 3. This work provides insight into the ability of combustion particles to provide iron micronutrients under different environmentally relevant acidic conditions.
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- PAR ID:
- 10643914
- Publisher / Repository:
- DOI PREFIX: 10.1071
- Date Published:
- Journal Name:
- Environmental Chemistry
- Volume:
- 20
- Issue:
- 4
- ISSN:
- 1448-2517
- Format(s):
- Medium: X Size: p. 171-182
- Size(s):
- p. 171-182
- Sponsoring Org:
- National Science Foundation
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