TiO2 nanoparticles for the remediation of eutrophic shallow freshwater systems: Efficiency and impacts on aquatic biota under a microcosm experiment.

The application of nanomaterials (NMs) in the remediation of eutrophic waters, particularly in the control of internal loading of nutrients, has been started, but limited investigations evaluated the effectiveness of these new treatment approaches and of their potential impacts on species from shallow freshwater lakes. The present work investigated, under a microcosm experiment, the application of a TiO2 nanomaterial both for reducing nutrient (mainly phosphorus and nitrogen forms) desorption and release from sediments (preventive treatment-PT) and for eliminating algal blooms (remediation treatment-RT). Furthermore, we also intended to assess the potential impacts of nano-TiO2 application on key freshwater species. The results showed the effectiveness of nano-TiO2 in controlling the release of phosphates from surface sediment and the subsequent reduction of total phosphorus in the water column. A reduction in total nitrogen was also observed. Such changes in nutrient dynamics contributed to a progressive inhibition of development of algae after the application of the NM in PT microcosms. Concerning the ability of nano-TiO2 to interact with algal cells, this interaction has likely occurred, mainly in RT, enhancing the formation of aggregates and their rapid settlement, thus reducing the algal bloom. Both treatments caused deleterious effects on freshwater species. In PT, Daphnia magna and Lemna minor showed a significant inhibition of several endpoints. Conversely, no inhibitory effect on the growth of Chironomus riparius was recorded. In opposite, C. riparius was the most affected species in RT microcosms. Such difference was probably caused by the formation of larger TiO2-algae aggregates in RT, under a high algal density, that rapidly settled in the sediment, becoming less available for pelagic species. In summary, despite the effectiveness of both treatments in controlling internal nutrient loading and in the mitigating algal bloom episodes, their negative effects on biota have to be seriously taken into account.

Phosphogypsum as a soil fertilizer: Ecotoxicity of amended soil and elutriates to bacteria, invertebrates, algae and plants.

Phosphogypsum (PG) is a metal and radionuclide rich-waste produced by the phosphate ore industry, which has been used as soil fertilizer in many parts of the world for several decades. The positive effects of PG in ameliorating some soil properties and increasing crop yields are well documented. More recently concerns are emerging related with the increase of metal/radionuclide residues on soils and crops. However, few studies have focused on the impact of PG applications on soil biota, as well as the contribution to soils with elements in mobile fractions of PG which may affect freshwater species as well. In this context the main aim of this study was to assess the ecotoxicity of soils amended with different percentages of Tunisian phosphogypsum (0.0, 4.9, 7.4, 11.1, 16.6 and 25%) and of elutriates obtained from PG - amended soil (0.0, 6.25, 12.5 and 25% of PG) to a battery of terrestrial (Eisenia andrei, Enchytraeus crypticus, Folsomia candida, Hypoaspis aculeifer, Zea mays, Lactuca sativa) and aquatic species (Vibrio fischeri, Daphnia magna, Raphidocelis subcapitata, Lemna minor). Both for amended soils and elutriates, invertebrates (especially D. magna and E. andrei) were the most sensitive species, displaying acute (immobilization) and chronic (reproduction inhibition) effects, respectively. Despite the presence of some concerning metals in PG and elutriates (e.g., zinc and cadmium), the extremely high levels of calcium found in both test mediums, suggest that this element was the mainly responsible for the ecotoxicological effects observed. Terrestrial and aquatic plants were the most tolerant species, which is in line with studies supporting the application of PG to increase crop yields. Nevertheless, no stimulatory effects on growth were observed for any of the species tested despite the high levels of phosphorus added to soils by PG. Given the importance of soil invertebrates for several soil functions and services, this study gives rise to new serious concerns about the consequences of PG applications on agricultural soils.