Investigation of Potential Drivers of Elevated Uranium Prevalence in Indian Groundwaters with a Unified Speciation Model.

Elevated uranium (U) (>WHO limit of 30 µg L-1) in Indian groundwaters is primarily considered geogenic, but the specific mineralogical sources and mechanisms for U mobilization are poorly understood. In this contribution, statistical and geochemical analyses of well-constrained metadata of Indian groundwater quality (n = 342 of 8543) were performed to identify key parameters and processes that influence U concentrations. For geochemical predictions, a unified speciation model was developed from a carefully compiled and updated thermodynamic database of inorganic, organic (Stockholm Humic model), and surface complexation reactions and associated constants. Critical U contamination was found at shallow depths (<100 m) within the Indo-Gangetic plain, as determined by bivariate nonparametric Kendall's Taub and probability-based association tests. Analysis of aquifer redox states, multivariate hierarchical clusters, and principal components indicated that U contamination was predominant not just in oxic but mixed (oxic-anoxic) aquifers under high Fe, Mn, and SO4 concentrations, presumably due to U release from dissolution of Fe/Mn oxides or Fe sulfides and silicate weathering. Most groundwaters were undersaturated with respect to relevant U-bearing solids despite being supersaturated with respect to atmospheric CO2 (average pCO2 of reported dissolved inorganic carbonate (DIC) data = 10-1.57 atm). Yet, dissolved U did not appear to be mass limited, as predicted solubilities from reported sediment concentrations of U were ∼3 orders of magnitude higher. Integration of surface complexation models of U on typical aquifer adsorbents, ferrihydrite, goethite, and manganese dioxide, was necessary to explain dissolved U concentrations. Uranium contamination probabilities with increasing dissolved Ca and Mn exhibited minima at equilibrium solubilities of calcite [∼50 mg L-1] and rhodochrosite [∼0.14 mg L-1], respectively, at an average groundwater pH of ∼7.5. A potential indirect control of such U-free carbonate solids on U mobilization was suggested. For locations (n = 37) where dissolved organic carbon was also reported, organic complexes of U contributed negligibly to dominant U speciation at the groundwater pH. Overall, the unified model suggested competitive dissolution-precipitation and adsorption-desorption controls on U speciation. The model provides a quantitative framework that can be extended to understand dominant mobilization mechanisms of geogenic U in aquifers worldwide after suitable modifications to the relevant aquifer parameters.

Heat and Bleach: A Cost-Efficient Method for Extracting Microplastics from Return Activated Sludge.

The extraction of plastic microparticles, so-called microplastics, from sludge is a challenging task due to the complex, highly organic material often interspersed with other benign microparticles. The current procedures for microplastic extraction from sludge are time consuming and require expensive reagents for density separation as well as large volumes of oxidizing agents for organic removal, often resulting in tiny sample sizes and thus a disproportional risk of sample bias. In this work, we present an improved extraction method tested on return activated sludge (RAS). The treatment of 100 ml of RAS requires only 6% hydrogen peroxide (H2O2) for bleaching at 70 °C, followed by density separation with sodium nitrate/sodium thiosulfate (SNT) solution, and is completed within 24 h. Extracted particles of all sizes were chemically analyzed with confocal Raman microscopy. An extraction efficiency of 78 ± 8% for plastic particle sizes 20 µm and up was confirmed in a recovery experiment. However, glass shards with a diameter of less than 20 µm remained in the sample despite the density of glass exceeding the density of the separating SNT solution by 1.1 g/cm3. This indicates that density separation may be unreliable for particle sizes in the lower micrometer range.