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Parallel Factor Analysis of Excitation–Emission Matrix Fluorescence Spectra of Water Soluble Soil Organic Matter as Basis for the Determination of Conditional Metal Binding Parameters

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journal contribution
posted on 01.01.2008, 00:00 by Tsutomu Ohno, Aria Amirbahman, Rasmus Bro
Organic matter−metal complexes in soil solution and aquatic systems are involved in important environmental and ecological processes such as plant nutrient availability and the solubilization and transport of metals. Our work presented here extends the use of fluorescence spectrometry for determining conditional stability constants for such complexes. We combine the use of excitation–emission matrix (EEM) fluorescence spectrometry and parallel factor analysis (PARAFAC) to determine the stability constants of the chemically meaningful components modeled by PARAFAC. Water-soluble organic matter (WSOM) from O-horizon soils of deciduous and coniferous forest stands were extracted and titrated at pH = 4.7 with iron(III) (Fe) and aluminum (Al) which are important metals in acid soil systems. The EEM spectra were then recorded and PARAFAC analysis showed that the WSOM contained three humic-substance-like components. Fe titration led to fluorescence quenching of the three components, while Al titration enhanced fluorescence for two components and quenched one of the components. The average Ryan−Weber stability constants at pH 4.7 ranged from log K of 4.28 to 4.91 for Fe and 4.84 to 5.96 for Al. The conditional stability constants were similar for Fe binding for deciduous and coniferous stand-derived WSOM, while they were stronger for Al binding with coniferous stand-derived WSOM. This difference in binding strengths for Al may affect the chemical behavior of Al in soil and aquatic systems. Determining the individual binding parameters of organic matter components with metals represents a significant advance over current approaches that utilize fluorescence quenching at a single excitation–emission wavelength pair to characterize organic matter−metal interactions.

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