Metal toxin threat in wildland fires determined by geology and fire severity.

Accentuated by climate change, catastrophic wildfires are a growing, distributed global public health risk from inhalation of smoke and dust. Underrecognized, however, are the health threats arising from fire-altered toxic metals natural to soils and plants. Here, we demonstrate that high temperatures during California wildfires catalyzed widespread transformation of chromium to its carcinogenic form in soil and ash, as hexavalent chromium, particularly in areas with metal-rich geologies (e.g., serpentinite). In wildfire ash, we observed dangerous levels (327-13,100 µg kg-1) of reactive hexavalent chromium in wind-dispersible particulates. Relatively dry post-fire weather contributed to the persistence of elevated hexavalent chromium in surficial soil layers for up to ten months post-fire. The geographic distribution of metal-rich soils and fire incidents illustrate the broad global threat of wildfire smoke- and dust-born metals to populations. Our findings provide new insights into why wildfire smoke exposure appears to be more hazardous to humans than pollution from other sources.

Advancing Chelation Chemistry for Actinium and Other +3 f-Elements, Am, Cm, and La.

A major chemical challenge facing implementation of 225Ac in targeted alpha therapy-an emerging technology that has potential for treatment of disease-is identifying an 225Ac chelator that is compatible with in vivo applications. It is unclear how to tailor a chelator for Ac binding because Ac coordination chemistry is poorly defined. Most Ac chemistry is inferred from radiochemical experiments carried out on microscopic scales. Of the few Ac compounds that have been characterized spectroscopically, success has only been reported for simple inorganic ligands. Toward advancing understanding in Ac chelation chemistry, we have developed a method for characterizing Ac complexes that contain highly complex chelating agents using small quantities (µg) of 227Ac. We successfully characterized the chelation of Ac3+ by DOTP8- using EXAFS, NMR, and DFT techniques. To develop confidence and credibility in the Ac results, comparisons with +3 cations (Am, Cm, and La) that could be handled on the mg scale were carried out. We discovered that all M3+ cations (M = Ac, Am, Cm, La) were completely encapsulated within the binding pocket of the DOTP8- macrocycle. The computational results highlighted the stability of the M(DOTP)5- complexes.

Antimonite Binding to Natural Organic Matter: Spectroscopic Evidence from a Mine Water Impacted Peatland.

Peatlands and other wetlands are sinks for antimony (Sb), and solid natural organic matter (NOM) may play an important role in controlling Sb binding. However, direct evidence of Sb sequestration in natural peat samples is lacking. Here, we analyzed solid phase Sb, iron (Fe), and sulfur (S) as well as aqueous Sb speciation in three profiles up to a depth of 80 cm in a mine water impacted peatland in northern Finland. Linear combination fittings of extended X-ray absorption fine structure spectra showed that Sb binding to Fe phases was of minor importance and observed only in the uppermost layers of the peatland. Instead, the dominant (to almost exclusive) sequestration mechanism was Sb(III) binding to oxygen-containing functional groups, and at greater depths, increasingly Sb(III) binding to thiol groups of NOM. Aqueous Sb speciation was dominated by antimonate, while antimonite concentrations were low, further supporting our findings of much higher reactivity of Sb(III) than Sb(V) toward peat surfaces. Insufficient residence time for efficient reduction of antimonate to antimonite currently hinders higher Sb removal in the studied peatland. Overall, our findings imply that Sb(III) binding to solid NOM acts as an important sequestration mechanism under reducing conditions in peatlands and other high-organic matter environments.