Identification and quantification of Cr, Cu, and As incidental nanomaterials derived from CCA-treated wood in wildland-urban interface fire ashes

Abstract

In addition to the combustion of vegetation, fires at the wildland-urban interface (WUI) burn structural materials, including chromated copper arsenate (CCA)-treated wood. This study identifies, quantifies, and characterizes Cr-, Cu-, and As-bearing incidental nanomaterials (INMs) in WUI fire ashes collected from three residential structures suspected to have originated from the combustion of CCA-treated wood. The total elemental concentrations were determined by inductively coupled plasma-time of flight-mass spectrometry (ICP-TOF-MS) following acid digestion. The crystalline phases were determined using transmission electron microscopy (TEM), specifically using electron diffraction and high-resolution imaging. The multi-element single particle composition and size distribution were determined by single particle (SP)-ICP-TOF-MS coupled with agglomerative hierarchical clustering analysis. Chromium, Cu, and As are the dominant elements in the ashes and together account for 93%, 83%, and 24% of the total mass of measured elements in the ash samples. Chromium, Cu, and As phases, analyzed by TEM, most closely match CrO3, CrO2, eskolaite (Cr2O3), CuCrO2, CuCr2O4, CrAs2O6, As2O5, AsO2, claudetite (As2O3, monoclinic), or arsenolite (As2O3, cubic), although a bona fide phase identification for each particle was not always possible. These phases occur predominantly as heteroaggregates. Multi-element single particle analyses demonstrate that Cr occurs as a pure phase (i.e., Cr oxides) as well as in association with other elements (e.g., Cu and As); Cu occurs predominantly in association with Cr and As; and As occurs as As oxides and in association with Cu and Cr. Several Cr, Cu, and As clusters were identified and the molar ratios of Cr/Cu and Cr/As within these clusters are consistent with the crystalline phases identified by TEM as well as their heteroaggregates. These results indicate that WUI fires can lead to significant release of CCA constituents and their combustion-transformed by-products into the surrounding environment. This study also provides a method to identify and track CCA constituents in environmental systems based on multi-element analysis using SP-ICP-TOF-MS.