Chemical characteristics of wildfire ash across the globe and their environmental and socio-economic implications.

The mobilisation of potentially harmful chemical constituents in wildfire ash can be a major consequence of wildfires, posing widespread societal risks. Knowledge of wildfire ash chemical composition is crucial to anticipate and mitigate these risks. Here we present a comprehensive dataset on the chemical characteristics of a wide range of wildfire ashes (42 types and a total of 148 samples) from wildfires across the globe and examine their potential societal and environmental implications. An extensive review of studies analysing chemical composition in ash was also performed to complement and compare our ash dataset. Most ashes in our dataset had an alkaline reaction (mean pH 8.8, ranging between 6 and 11.2). Important constituents of wildfire ash were organic carbon (mean: 204 g kg-1), calcium, aluminium, and iron (mean: 47.9, 17.9 and 17.1 g kg-1). Mean nitrogen and phosphorus ranged between 1 and 25 g kg-1, and between 0.2 and 9.9 g kg-1, respectively. The largest concentrations of metals of concern for human and ecosystem health were observed for manganese (mean: 1488 mg kg-1; three ecosystems > 1000 mg kg-1), zinc (mean: 181 mg kg-1; two ecosystems > 500 mg kg-1) and lead (mean: 66.9 mg kg-1; two ecosystems > 200 mg kg-1). Burn severity and sampling timing were key factors influencing ash chemical characteristics like pH, carbon and nitrogen concentrations. The highest readily dissolvable fractions (as a % of ash dry weight) in water were observed for sodium (18 %) and magnesium (11.4 %). Although concentrations of elements of concern were very close to, or exceeded international contamination standards in some ashes, the actual effect of ash will depend on factors like ash loads and the dilution into environmental matrices such as water, soil and sediment. Our approach can serve as an initial methodological standardisation of wildfire ash sampling and chemical analysis protocols.

Organic matter identifies the nano-mechanical properties of native soil aggregates.

Localized variations at the nanoscale in soil aggregates and in the spatial organisation of soil organic matter (SOM) are critical to understanding the factors involved in soil composition and turnover. However soil nanoscience has been hampered by the lack of suitable methods to determine soil biophysical properties at nanometre spatial resolution with minimal sample preparation. Here we introduce for the first time an Atomic Force Microscopy (AFM)-based Quantitative Nano-Mechanical mapping (QNM) approach that allows the characterisation of the role of SOM in controlling surface nano-mechanical properties of soil aggregates. SOM coverage resulted in an increased roughness and surface variability of soil, as well as in decreased stiffness and adhesive properties. The latter also correlates with nano- to macro-wettability features as determined by contact angle measurements and Water Drop Penetration Time (WDPT) testing. AFM thus represents an ideal quantitative tool to complement existing techniques within the emerging field of soil nanoscience.

Application of atomic force microscopy to the study of natural and model soil particles.

The structure and surface chemistry of soil particles has extensive impact on many bulk scale properties and processes of soil systems and consequently the environments that they support. There are a number of physiochemical mechanisms that operate at the nanoscale which affect the soil's capability to maintain native vegetation and crops; this includes soil hydrophobicity and the soil's capacity to hold water and nutrients. The present study used atomic force microscopy in a novel approach to provide unique insight into the nanoscale properties of natural soil particles that control the physiochemical interaction of material within the soil column. There have been few atomic force microscopy studies of soil, perhaps a reflection of the heterogeneous nature of the system. The present study adopted an imaging and force measurement research strategy that accounted for the heterogeneity and used model systems to aid interpretation. The surface roughness of natural soil particles increased with depth in the soil column a consequence of the attachment of organic material within the crevices of the soil particles. The roughness root mean square calculated from ten 25 microm(2) images for five different soil particles from a Netherlands soil was 53.0 nm, 68.0 nm, 92.2 nm and 106.4 nm for the respective soil depths of 0-10 cm, 10-20 cm, 20-30 cm and 30-40 cm. A novel analysis method of atomic force microscopy phase images based on phase angle distribution across a surface was used to interpret the nanoscale distribution of organic material attached to natural and model soil particles. Phase angle distributions obtained from phase images of model surfaces were found to be bimodal, indicating multiple layers of material, which changed with the concentration of adsorbed humic acid. Phase angle distributions obtained from phase images of natural soil particles indicated a trend of decreasing surface coverage with increasing depth in the soil column. This was consistent with previous macroscopic determination of the proportions of organic material chemically extracted from bulk samples of the soils from which specimen particles were drawn. Interaction forces were measured between atomic force microscopy cantilever tips (Si(3)N(4)) and natural soil and model surfaces. Adhesion forces at humic acid free specimen surfaces (Av. 20.0 nN), which are primarily hydrophilic and whose interactions are subject to a significant contribution from the capillary forces, were found to be larger than those of specimen surfaces with adsorbed humic acid (Av. 6.5 nN). This suggests that adsorbed humic acid increased surface hydrophobicity. The magnitude and distribution of adhesion forces between atomic force microscopy tips and the natural particle surfaces was affected by both local surface roughness and the presence of adsorbed organic material. The present study has correlated nanoscale measurements with established macroscale methods of soil study. Thus, the research demonstrates that atomic force microscopy is an important addition to soil science that permits a multiscale analysis of the multifactorial phenomena of soil hydrophobicity and wetting.