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Natural Organic Matter and Humic Substances Interactions

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[10]. In this study, DAS is applied to the exploration of the complexation behaviour of<br />

st<strong>and</strong>ard Suwannee River fulvic acid.<br />

It is also desirable to have a means to model <strong>and</strong> predict the metal complexation behaviour of<br />

fulvic acids. While many models have been developed <strong>and</strong> utilized, the NICA-Donnan model<br />

has emerged as a very useful means for fitting <strong>and</strong> predicting complexation behavior of fulvic<br />

acids [11, 12]. This model uses a continuous distribution of binding site affinities to model the<br />

direct complexation of metal cations to NOM binding sites, <strong>and</strong> models the indirect<br />

electrostatic interactions between NOM <strong>and</strong> metal cations through distribution of potential<br />

throughout a uniform Donnan gel phase. This study uses the NICA-Donnan model for metal<br />

complexation to fulvic acids to fit the differential absorbance spectra generated during<br />

complexation of SRFA with metals.<br />

2. Methods<br />

A Suwannee River fulvic acid (SRFA) sample was obtained from the International <strong>Humic</strong><br />

<strong>Substances</strong> Society (Sample # 1S101F). SRFA solutions were prepared at DOC<br />

concentrations of 5 mg/L, <strong>and</strong> background ionic strength was established by including 0.01 M<br />

NaClO4. The pH of NOM solutions during titrations was controlled through addition of<br />

appropriate amounts of HClO4 or NaOH, <strong>and</strong> the volume changes associated with these<br />

additions of acid <strong>and</strong> base were corrected for in the final data analysis. Metal concentrations<br />

were adjusted between 0 – 1000 μg/L Cu 2+ or Pb 2+ through addition of small volumes of<br />

dilute CuSO4 <strong>and</strong> PbClO4 solutions. Absorbance spectra were recorded in a 5 cm quartz cell<br />

on a Perkin-Elmer Lambda 18 UV/Vis Spectrophotometer. Differential absorbance data<br />

fitting to model calculations was done using visual MINTEQA.<br />

3. Results <strong>and</strong> Discussion<br />

15th IHSS Meeting- Vol. 3<br />

Absorbance spectra for SRFA at varying metal concentrations retain the same broad <strong>and</strong><br />

featureless shape throughout the entire range of the titrations. However, the differential<br />

spectra for these titrations show the emergence of clear features, as illustrated by Figure 1.<br />

They indicate that subtle changes of the absorbance of SRFA can be detected even at copper<br />

concentrations as low as 5 µg/L. At higher CuTOT values, the presence of several b<strong>and</strong>s<br />

becomes notable, the most prominent of which have maxima at 245 <strong>and</strong> 390 nm.<br />

Correlations between the amount of copper bound by SRFA <strong>and</strong> changes in absorbance were<br />

calculated using by examining the relative change of the ratio of absorbances at 350 <strong>and</strong> 390<br />

nm (denoted as (ΔRA/RA), The selection of the wavelength of 390 nm is due to the presence of<br />

Vol. 3 Page - 406 -

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