In meeting rapidly growing demands for energy and clean water, engineered systems such as unconventional oil and gas recovery and desalination processes produce large amounts of briny water. In the environment, these highly concentrated halides can be oxidized and transformed to reactive halogen radicals, whose roles in the degradation and transformation of organic pollutants have been studied. However, redox reactions between halogen radicals and heavy metal ions are still poorly understood. In this work, we found that aqueous manganese ions (Mn2+) could be oxidized to Mn oxide solids by reactive halogen radicals generated from reactions between halide ions and hydroxyl radicals or between halide ions and triplet state dissolved organic matter. In particular, more Mn2+ was oxidized by Br radicals generated from bromide ion (Br−) than by Cl radicals generated from chloride ion (Cl−), even though the concentrations of Br− in surface waters are much lower than Cl− concentrations. In addition, the highly concentrated halides greatly increased the ionic strength of the solution, affecting Mn2+ oxidation kinetics and the crystallinity and oxidation state of the newly formed Mn oxides. These newly discovered pathways involving Mn2+(aq) and reactive halogen radicals aid in understanding the generation of abiotic Mn oxide solids and forecasting their redox activities. Moreover, this work emphasizes the critical need for a better knowledge of the roles of reactive halogen radicals in inorganic redox reactions.
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Environmentally persistent free radicals and other paramagnetic species in wildland-urban interface fire ashes
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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- Award ID(s):
- 2101983
- PAR ID:
- 10559288
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Chemosphere
- Volume:
- 363
- Issue:
- C
- ISSN:
- 0045-6535
- Page Range / eLocation ID:
- 142950
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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