The availability of dissolved silicon (DSi) exerts an important control on phytoplankton communities in freshwater environments: DSi limitation can shift species dominance to non-siliceous algae and increase the likelihood of harmful algal blooms. The availability of DSi in the water column in turn depends on the dissolution kinetics of amorphous silica (ASi), including diatoms frustules and phytoliths. Here, batch dissolution experiments conducted with diatom frustules from three diatom species and synthetic Aerosil OX 50 confirmed the previously reported non-linear dependence of ASi dissolution rate on the degree of undersaturation of the aqueous solution. At least two first-order dissolution rate constants are therefore required to describe the dissolution kinetics at high (typically, ≥0.55) and low (typically, <0.55) degrees of undersaturation. Our results further showed aqueous ferrous ion (Fe2+), which is ubiquitous in anoxic waters, strongly inhibited ASi dissolution. The inhibition is attributed to the preferential binding of Fe2+ to Q2 groups (i.e., surface silicate groups bonded to the silica lattice via two bridging oxygen) which stabilizes the silica surface. However, further increasing the aqueous Fe2+ concentration likely catalyzes the detachment of Q3 groups (i.e., silicate groups bonded to the silica lattice via three bridging oxygen) from the surface. Overall, our study illustrates the manyfold effects the aqueous solution composition, notably the inhibition effect of Fe2+ under anoxic conditions, has on ASi dissolution. The results help to explain the controversial redox dependence of DSi internal loading from sediments, which is vital to quantitatively understanding silicon (Si) cycling in freshwater systems.

Most pharmaceuticals are found at trace concentrations in aquatic systems, but their continuous release and potential accumulation can lead to adverse health effects in exposed organisms. Concentrations can vary temporally, driven by variations in discharges of receiving waters, sorption to sediments, and other biotic and abiotic exchange processes. The principal aim of this research was to better understand the occurrence, trends, and dynamics of pharmaceuticals in a cold-climate, riverine environment. To this end, a suite of seven representative antipsychotic pharmaceuticals was measured upstream and downstream of two wastewater treatment plants (WWTPs) in Saskatchewan, Canada, located in the South Saskatchewan River and Wascana Creek, respectively, across three seasons. Concentrations of analytes were in the ng/L range and generally greater downstream of both WWTPs compared to upstream. Some compounds, including the tricyclic antidepressant amitriptyline, which was the most abundant analyte in water and sediment from both sites and across seasons, reached low μg/L concentrations. Data collected from this research effort indicate contamination with antipsychotic pharmaceuticals, with the potential to adversely impact exposed organisms.