Abstract

Environmental context Reliable interpretation of metal levels measured by diffusive gradients in thin film (DGT) requires a sound understanding of the diffusion properties of dissolved organic matter (DOM), the main ligand of metals in natural waters. The present study determined that the molecular weight of DOM and conductivity are the main factors controlling the diffusion of freshly collected estuarine DOM across the DGT diffusive gel. Abstract Diffusion coefficients (D) and the molecular weight distribution (MW) of 18 dissolved organic matter (DOM) samples collected in the Churchill River estuary system (Manitoba, Canada) were determined using a diffusive cell apparatus. NaN3 addition has been shown to preserve the DOM MW distribution within 5 weeks of collection whereas the diffusive properties (i.e. D) were strongly influenced by storage conditions, suggesting D must be determined on freshly collected material. Aquatic DOM from the river and estuarine sites was capable of diffusing across a polyacrylamide diffusive gel membrane with mean D values ranging from 2.74×10–6 to 6.98×10–6cm2s–1 and from 2.42×10–6 to 10.7×10–6cm2s–1 respectively, congruent with previous studies using humic substances and natural DOM. The molecular weight of the river and estuary DOM samples (~400–830Da) measured using asymmetrical flow-field flow fractionation (AF4) strongly influenced D, with larger MW DOM having lower D values. Conductivity had a significant negative correlation with D in estuarine samples collected at high and low tides (R2=0.82 and 0.46 respectively). These results suggest that MW and conductivity can significantly influence D of DOM in river and marine-dominated sites respectively.

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