Formation of mixed Al-Fe colloidal sorbent and dissolved-colloidal partitioning of Cu and Zn in the Cement Creek - Animas River Confluence, Silverton, Colorado

Abstract

Transport and chemical transformations of dissolved and colloidal Al, Fe, Cu and Zn were studied by detailed sampling in the mixing zone downstream from the confluence of Cement Creek (pH 4.1) with the Animas River (pH 7.6). Complete mixing resulted in circumneutral pH in the downstream reach of the 1300 m study area. All four metals were transported through this mixing zone without significant losses to the streambed, and they exhibited transformations from dissolved to colloidal forms to varying degrees during the mixing process. Nearly all of the Al formed colloidal hydrous Al oxides (HAO) as pH increased (4.8–6.5), whereas colloidal hydrous Fe oxides (HFO) were supplied by Cement Creek as well as formed in the mixing zone primarily at higher pH (>6.5). The short travel time through the mixing zone (approx. 40 min) and pH limited the formation of HFO from dissolved Fe 2+ supplied by Cement Creek. Although the proportions of HAO and HFO varied as the streams mixed, the colloidal sorbent typically was enriched in HAO relative to HFO by a factor of 1.5–2.1 (by mole) in the pH range where dissolved-to-colloidal partitioning of Cu and Zn was observed. Model simulations of sorption by HFO (alone) greatly underestimated the dissolved-to-colloidal partitioning of Zn. Previous studies have shown that HAO–HFO mixtures can sorb greater amounts of Zn than HFO alone, but the high Zn-to-sorbent ratio in this mixing zone could also account for greater partitioning. In contrast to Zn, comparisons with model simulations did not show that Cu sorption was greater than that for HFO alone, and also indicated that sorption was possibly less than what would be expected for a non-interactive mixture of these two sorbents. These field results for Cu, however, might be influenced by (organic) complexation or other factors in this natural system. Laboratory mixing experiments using natural source waters (upstream of the confluence) showed that the presence of HFO in the mixed sorbent resulted in greater Cu partitioning than for HAO alone, and that the effect was greater with increasing (mole fraction) HFO. This was consistent with field results that showed greater Cu sorption when additional HFO was formed in the downstream reach of the mixing zone. Further research is needed to identify the significance of surface-related mechanisms specific to HAO–HFO mixtures that could affect the partitioning of Cu in natural systems.