New light on a dark subject: comment |
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| Authors: | Matthew P Miller Bailey E Simone Diane M McKnight Rose M Cory Mark W Williams Elizabeth W Boyer |
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| Institution: | (1) School of Forest Resources, 312 Forest Resources Building, Pennsylvania State University, University Park, Pennsylvania, PA 16802, USA;(2) Department of Civil, Environmental, and Architectural Engineering, Institute of Arctic and Alpine Research, University of Colorado, Boulder, CO 80309, USA;(3) Department of Environmental Sciences and Engineering, University of North Carolina, Chapel Hill, NC 27599, USA;(4) Department of Geography, Institute of Arctic and Alpine Research, University of Colorado, Boulder, CO 80309, USA |
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| Abstract: | In their article, “New light on a dark subject: On the use of fluorescence data to deduce redox states of natural organic
matter,” Macalady and Walton-Day (2009) subjected natural organic matter (NOM) samples to oxidation, reduction, and photochemical transformation. Fluorescence spectra
were obtained on samples, which were diluted “to bring maximum uvvisible absorbance values below 1.0.” The spectra were fit
to the Cory and McKnight (2005) parallel factor analysis (PARAFAC) model, and consistent variation in the redox state of quinone-like moieties was not detected.
Based on these results they concluded that fitting fluorescence spectra to the Cory and McKnight (2005) PARAFAC model to obtain information about the redox state of quinone-like moieties in NOM is problematic. Recognizing that
collection and correction of fluorescence spectra requires consideration of many factors, we investigated the potential for
inner-filter effects to obscure the ability of fluorescence spectroscopy to quantify the redox state of quinone-like moieties.
We collected fluorescence spectra on Pony Lake and Suwannee River fulvic acid standards that were diluted to cover a range
of absorbance wavelengths, and fit these spectra to the Cory and McKnight (2005) PARAFAC model. Our results suggest that, in order for the commonly used inner-filter correction to effectively remove inner-filter
effects, samples should be diluted such that the absorbance at 254 nm is less than 0.3 prior to the collection of fluorescence
spectra. This finding indicates that inner-filter effects may have obscured changes in the redox signature of fluorescence
spectra of the highly absorbing samples studied by Macalady and Walton-Day (2009). |
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