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TECHNICAL REPORTS

Organic Compounds in the Environment

Phenanthrene Sorption to Structurally Modified Humic Acids

^a Department of Chemistry, Ohio State University, 100 W. 18th Avenue, Columbus, OH 43210
^b Department of Soil and Water Sciences, Faculty of Agricultural, Food and Environmental Sciences, The Hebrew University of Jerusalem, P.O. Box 12, Rehovot, 76100, Israel
^c Department of Physical and Environmental Sciences, University of Toronto, Scarborough Campus, 1265 Military Trail, Toronto, ON, Canada M1C 1A4

^* Corresponding authors (myrna.simpson{at}utoronto.ca, hatcher{at}chemistry.ohio-state.edu).

Received for publication November 25, 2002. Several studies emphasize the importance of soil organic matter characteristics in hydrophobic contaminant sorption and outline the strong dependence of sorption on organic matter aromaticity. In this study, the role of organic matter aromaticity in phenanthrene sorption was investigated using humic acids (HAs) from compost, peat, and soil that were structurally modified by bleaching, hydrolysis, oximation, and subcritical water extraction. The HAs were characterized with cross polarization magic angle spinning carbon-13 nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopy and used in batch equilibrations with phenanthrene. Bleaching substantially reduced the aromaticity of the samples whereas the other treatments increased the relative aromaticity. Phenanthrene sorption increased, even though there was a substantial reduction in sorbent aromaticity with some samples. The HAs that exhibited comparable CPMAS ¹³C NMR spectra and aromaticity did not behave similarly with respect to phenanthrene sorption. When the sorption data (K_oc values) were correlated to sample aromaticity, the correlation coefficients (r²) did not exceed 0.39. Comparisons with the atomic H to C ratio provided slightly better r² values (up to 0.54). This study demonstrates that macroscopic sorbent characteristics could not explain the observed phenanthrene sorption coefficients, aliphatic structural components of HAs can contribute appreciably to phenanthrene sorption, and organic matter physical conformation may regulate access to organic matter structures. Therefore, the use of only macroscopic sorbent properties, such as aromaticity, to predict and rationalize sorption values cannot solely be used to explain the behavior of organic contaminants in soil environments.

Abbreviations: CPMAS, cross polarization magic angle spinning • HA, humic acid • NMR, nuclear magnetic resonance

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This Issue in Journal of Environmental Quality

JEQ 2003 32: 1577-1582. [Full Text]  

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