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Optical Properties of Humic Substances and CDOM: Effects of Borohydride Reduction
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    Optical Properties of Humic Substances and CDOM: Effects of Borohydride Reduction
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    Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, and Earth System Science Interdisciplinary Center (ESSIC), University of Maryland, College Park, Maryland 20740
    * Address correspondence to either author. E-mail: [email protected] (N.V.B.); [email protected] (R.D.V.).
    †Department of Chemistry and Biochemistry.
    ‡Earth System Science Interdisciplinary Center.
    §Current Address: College of Chemistry and Chemical Engineering, Graduate University of Chinese Academy of Sciences, Beijing 100049 (China).
    ⊥Current Address: Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53711.
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    Environmental Science & Technology

    Cite this: Environ. Sci. Technol. 2010, 44, 14, 5395–5402
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    https://doi.org/10.1021/es100880q
    Published June 17, 2010
    Copyright © 2010 American Chemical Society

    Abstract

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    Treatment of Suwanee River humic (SRHA) and fulvic (SRFA) acids, a commercial lignin (LAC), and a series of solid phase extracts (C18) from the Middle Atlantic Bight (MAB extracts) with sodium borohydride (NaBH4), a selective reductant of carbonyl-containing compounds including quinones and aromatic ketones, produces a preferential loss of visible absorption (≥50% for SRFA) and substantially enhanced, blue-shifted fluorescence emission (2- to 3-fold increase). Comparison of the results with those obtained from a series of model quinones and hydroquinones demonstrates that these spectral changes cannot be assigned directly to the absorption and emission of visible light by quinones/hydroquinones. Instead, these results are consistent with a charge transfer model in which the visible absorption is due primarily to charge transfer transitions arising among hydroxy- (methoxy-) aromatic donors and carbonyl-containing acceptors. Unlike most of the model hydroquinones, the changes in optical properties of the natural samples following NaBH4 reduction were largely irreversible in the presence of air and following addition of a Cu2+ catalyst, providing tentative evidence that aromatic ketones (or other similar carbonyl-containing structures) may play a more important role than quinones in the optical properties of these materials.

    Copyright © 2010 American Chemical Society

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    Effect of pH alone on absorption and emission spectra (Figures S1, S2), kinetics of reduction (Figure S3), absorption spectra of reduced HS after introduction of air (pH 10) (Figure S4), absorption spectra of reduced HS over long times at neutral pH in the presence of air (Figure S5), absorption spectra of reduced HS following addition of a Cu2+ catalyst in the presence of air (Figure S6), effects of borohydride reduction on the complete absorption and emission spectra of SRHA, LAC, and the MAB extracts (Figures S7−S11), complete absorption and emission spectra of the model quinones and hydroquinones (Figures S12−S18), and the reversibility of model hydroquinone oxidation under air (Figures S19, S20). This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cite this: Environ. Sci. Technol. 2010, 44, 14, 5395–5402
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    https://doi.org/10.1021/es100880q
    Published June 17, 2010
    Copyright © 2010 American Chemical Society

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