Observations and assessment of iron oxide and green rust nanoparticles in metal-polluted mine drainage within a steep redox gradient

In this study of iron- and silica-bearing nanoparticle and colloid aggregates in slightly acidic mine drainage, we combined bulk scale geochemistry techniques with detailed nanoscale analyses using high-resolution transmission electron microscopy (HR-TEM) to demonstrate the complexity of iron oxide formation and transformation at a steep redox gradient (groundwater outflow into a stream), and the resulting role in metal(loid) uptake. We also identified pseudohexagonal nanosheets of Zn-bearing green rust in outflowing groundwater using HR-TEM. This is only the second study where green rust was identified in groundwater, and the second to examine naturally occurring green rust with analytical TEM. In aerated downstream waters, we found aggregates of poorly crystalline iron oxide particles (20-200nm in diameter). Inductively coupled plasma-mass spectrometry (ICP-MS) analysis of water fractions shows that most elements such as Ni and Zn were found almost exclusively in the dissolved-nanoparticulate (<0.1m) fraction, whereas Cu and As were primarily associated with suspended particles. In the underlying sediments composed of deposited particles, goethite nanoneedles formed on the ferrihydrite surfaces of larger aggregated particles (100-1000nm), resulting in more reactive surface area for metal(loid) uptake. Sequential extraction of sediments showed that many metal(loid)s, particularly As and Zn, were associated with iron oxides identified as ferrihydrite, goethite and possibly schwertmannite. Amorphous silica co-precipitation with iron oxides was prevalent at all sampling sites, but its effect on metal(loid) sorption is unknown. Fine-grained iron oxide sediments are easily remobilised during turbulent flow events, adding to the mobility of the associated metals. © CSIRO 2014.