Organic Functional Group Chemistry in Mineralized Deposits Containing U(IV) and U(VI) from the Jackpile Mine in New Mexico

We investigated the functional group chemistry of natural organic matter (NOM) associated with both U­(IV) and U­(VI) in solids from mineralized deposits exposed to oxidizing conditions from the Jackpile Mine, Laguna Pueblo, NM. The uranium (U) content in unreacted samples was 0.44–2.6% by weight determined by X-ray fluorescence. In spite of prolonged exposure to ambient oxidizing conditions, ≈49% of U­(IV) and ≈51% of U­(VI) were identified on U LIII edge extended X-ray absorption fine structure spectra. Loss on ignition and thermogravimetric analyses identified from 13% to 44% of NOM in the samples. Carbonyl, phenolic, and carboxylic functional groups in the unreacted samples were identified by fitting of high-resolution X-ray photoelectron spectroscopy (XPS) C 1s and O 1s spectra. Peaks corresponding to phenolic and carbonyl functional groups had intensities higher than those corresponding to carboxylic groups in samples from the supernatant from batch extractions conducted at pH 13, 7, and 2. U­(IV) and U­(VI) species were detected in the supernatant after batch extractions conducted under oxidizing conditions by fitting of high-resolution XPS U 4f spectra. The outcomes from this study highlight the importance of the influence of pH on the organic functional group chemistry and U speciation in mineralized deposits.