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Discovery and potential ramifications of reduced iron-bearing nanoparticles — Magnetite, wüstite, and zero-valent iron — In wildland–urban interface fire ashes

The increase in fires at the wildland–urban interface has raised concerns about the potential environmental impact of ash remaining after burning. Here, we examined the concentrations and speciation of iron-bearing nanoparticles in wildland–urban interface ash. Total iron concentrations in ash varied between 4 and 66 mg g −1 . Synchrotron X-ray absorption near-edge structure (XANES) spectroscopy of bulk ash samples was used to quantify the relative abundance of major Fe phases, which were corroborated by transmission electron microscopy measurements. Maghemite (γ-(Fe 3+ ) 2 O 3 ) and magnetite (γ-Fe 2+ (Fe 3+ ) 2 O 4 ) were detected in most ashes and accounted for 0–90 and 0–81% of the spectral weight, respectively. Ferrihydrite (amorphous Fe( III )–hydroxide, (Fe 3+ ) 5 HO 8 ·4H 2 O), goethite (α-Fe 3+ OOH), and hematite (α-Fe 3+ 2 O 3 ) were identified less frequently in ashes than maghemite and magnetite and accounted for 0–65, 0–54, and 0–50% of spectral weight, respectively. Other iron phases identified in ashes include wüstite (Fe 2+ O), zerovalent iron, FeS, FeCl 2 , FeCl 3 , FeSO 4 , Fe 2 (SO 4 ) 3 , and Fe(NO 3 ) 3 . Our findings demonstrate the impact of fires at the wildland–urban interface on iron speciation; that is, fires can convert iron oxides ( e.g. , maghemite, hematite, and goethite) to reduced iron phases such as magnetite, wüstite, and zerovalent iron. Magnetite concentrations ( e.g. , up to 25 mg g −1 ) decreased from black to gray to white ashes. Based on transmission electron microscopy (TEM) analyses, most of the magnetite nanoparticles were less than 500 nm in size, although larger particles were identified. Magnetite nanoparticles have been linked to neurodegenerative diseases as well as climate change. This study provides important information for understanding the potential environmental impacts of fires at the wildland–urban interface, which are currently poorly understood.

Environmental Science Nano↗

Comparative study of the elemental composition of metal(loid)-bearing nanomaterials in wildland-urban interface fire ashes using icp-TOF-MS

This study investigates the abundance and elemental composition of metal(loid) incidental nanomaterials (INMs) in wildland–urban interface (WUI) fire ashes from different sources, including vegetation, structures, and vehicles, collected following the 2020 LNU (the Sonoma-Lake-Napa unit) Lightning Complex Fire in California. Particle number concentrations, elemental compositions and ratios, and size distributions were determined by single particle inductively coupled plasma-time of flight-mass spectrometry (SP-ICP-TOF-MS) coupled with automated two-stage hierarchical clustering analysis. Iron- and Mn-bearing INMs accounted for >80% of INMs detected in vegetation and atmospheric deposition ashes but they represented <50% of all INMs in structural and vehicle ashes. Together, Al, Ba, Cr, Cu, Ti, Pb, and Zn-bearing INMs accounted for 45 to 75% of all INMs in structural and vehicle ashes and 7 to 13% in vegetation and atmospheric deposition ashes. The sizes of INMs varied between a few tens to a few hundreds of nanometers with larger Ba, Cr, Fe, Ti, Pb, and Zn-bearing INMs in structural and vehicles ashes than in vegetation ashes. Several types of multi-element INMs were identified by SP-ICP-TOF-MS including chromated-copper-arsenate-related NMs ( e.g. , CuCrO 2 , CuCr 2 O 4 , CrAsO 4 ); CuSn and CuPb alloys; SnPb, SbPb, and SnSb alloys; and CoAl alloys. Overall, this study demonstrates the abundance and elemental makeup of various metal(loid) INMs in WUI fire ashes. This study highlights the research opportunities into the discovery, transformation, reactivity, fate, and effects of INMs during and following WUI fires.

Environmental Science: Nano↗