Photooxidation of wetland and riverine dissolved organic matter: altered copper complexation and organic composition |
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Authors: | Marjorie L Brooks Joseph S Meyer Diane M McKnight |
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Institution: | (1) Department of Zoology and Physiology, University of Wyoming, Laramie, WY 82071, USA;(2) National Center for Ecological Analysis and Synthesis, University of California, Santa Barbara, 735 State Street, Suite 300, Santa Barbara, CA 93101, USA;(3) Institute of Artic and Alpine Research, University of Colorado, Boulder, CO 80309, USA |
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Abstract: | In natural waters, the uptake of transition metals such as copper (Cu) by aquatic biota depends on the activity of the free
cupric ion ({Cu2+}) rather than on total Cu concentration. Thus, an important ecological function of dissolved organic matter (DOM) in aquatic
ecosystems is Cu–DOM complexation, which greatly decreases the {Cu2+}. However, Cu bioavailability is greatly modified by source and environmental history of DOM because DOM affinity for Cu
varies by orders of magnitude among DOM sources; moreover, DOM is photochemically unstable. During 72-h irradiation experiments
at intensities approximating sunlight with DOM from a palustrine wetland and a third-order river, we investigated photooxidative
effects on DOM complexation of Cu as well as spectral and chemical changes in DOM that might explain altered Cu complexation.
Irradiation decreased Cu complexation by riverine DOM, but unexpectedly increased Cu complexation by wetland DOM, resulting
in 150% greater {Cu2+} in riverine DOM at the same dissolved organic carbon concentrations. The specific ultraviolet absorption (SUVa) and humic substances tracked photochemical changes in the conditional stability constants of Cu–DOM complexes, suggesting
that the aromaticity of DOM influences its affinity for Cu. Carbonyl concentration in 13C nuclear magnetic resonance spectra (13C-NMR) covaried directly with Cu binding-site densities in DOM. However, no aspect of Cu–DOM complexation consistently covaried
with fluorophores (i.e., the fluorescence index) or low molecular weight organic acids. Our results suggest that global increases
in UV radiation will affect Cu–DOM complexation and subsequent Cu toxicity depending on light regime as well as DOM source.
Handling editor: K. Martens |
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Keywords: | Dissolved organic matter DOC Cu Bioavailability Photooxidation Biotic ligand model |
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