Phosphate adsorption by riverborne clay sediments in a southern-Italy Mediterranean reservoir: Insights from a "natural geo-engineering" experiment.

This paper reports data from a southern-Italy reservoir (Lake Occhito) characterized by a strong riverborne sediment transport. Main hydrochemical, trophic, and nutrient variables were measured (over a twelve-month period) in both lake and tributaries. Lacustrine sediments were subjected to mineralogical characterization and to phosphorus fractioning, while a 6-day long batch experiment was carried out to evaluate the lake sediment orthophosphate adsorption capacity. A set of algal growth potential tests was also undertaken on the lake and its tributaries. Results highlight the presence of a strong gradient in nutrient availability among the inflows. Most of the nutrient loads were from the main tributary (20.3 t P a-1, ~83 %), that showed the highest trophic potential (average: 56.8 mg L-1) and was nitrogen/phosphorus co-limited. The other inflows were phosphorus limited and characterized by a higher sediment transport. The lake showed the lowest nutrient concentrations (average total phosphorus: 21 µg P L-1) and was strongly phosphorus limited. Clays were the principal minerals in the lake sediments (~51 %), while the main phosphorus fraction was apatite (~78 %). The batch experiment demonstrated the capability of the lake sediments to reduce orthophosphate concentrations in phosphorus-rich waters (initial orthophosphate: 320 µg P L-1; ~80 % reduction). The lake sediment orthophosphate kinetics of abatement was similar to that of a commercially available phosphorus sorbent (lanthanum modified bentonite), although the stability of phosphorus binding was higher for the commercial product. Theoretical average in-lake total phosphorus, chlorophyll-a, and transparency values, estimated through Vollenweider models, were approximately double of the average values measured in the lake. Therefore, the massive presence of riverborne clay sediments seems to markedly reduce the in-lake orthophosphate concentrations (and light penetration), inducing an overall lowering of the lake trophic state, as if the lake ecosystem were permanently subjected to a geo-engineering phosphorus sorbent treatment.

Integrated Exposure and Algal Ecotoxicological Assessments of Effluents from Secondary and Advanced-Tertiary Wastewater-Treatment Plants.

The great concern over the environmental impact of wastewaters has led to the designing of advanced treatment processes to upgrade conventional treatment plants and achieve a significant reduction of contaminants in receiving waters. In the present study we combined chemical and ecotoxicological analyses, aiming to evaluate the reduction of toxicity effects associated with the removal of micropollutants and to define the contribution of the detected compounds to the overall toxicity of the mixtures in a series of wastewater effluents collected from a secondary treatment (OUT 2) and from a tertiary activated carbon treatment (OUT 3) plant. The target compounds were selected after a screening procedure among pharmaceuticals, musk fragrances, and trace metals. The classical algal growth inhibition test was conducted on the original effluent samples and on different fractions obtained by solid-phase extraction (SPE) treatment. A good accordance was found between the removal of toxicity (30%-80%) and organic compounds (70%-80%) after the tertiary treatment, suggesting its high efficiency to improve the wastewater quality. The discrepancy between the contribution to the overall toxicity of the nonadsorbable compounds (i.e., inorganic or very polar organic compounds) as experimentally measured by the SPE bioassays (18%-76%) and calculated by the concentration addition approach (>97%) could be mitigated by including the bioavailability correction in metal-toxicity modeling of wastewater mixtures. For the organic compounds, the toxic equivalency method enabled us to quantify the portion of toxicity explained by the detected chemicals in both OUT 2 (82%-104%) and OUT 3 (5%-57%), validating the selection of the target molecules. The applied integrating approach could be implemented by the inclusion of both additional target chemicals and toxicity endpoints. Environ Toxicol Chem 2022;41:2404-2419. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Suspect screening of wastewaters to trace anti-COVID-19 drugs: Potential adverse effects on aquatic environment.

During the first period of the SARS-CoV-2 pandemic, the lack of specific therapeutic treatments led to the provisional use of a number of drugs, with a continuous review of health protocols when new scientific evidence emerged. The management of this emergency sanitary situation could not take care of the possible indirect adverse effects on the environment, such as the release of a large amount of pharmaceuticals from wastewater treatment plants. The massive use of drugs, which were never used so widely until then, implied new risks for the aquatic environment. In this study, a suspect screening approach using Liquid Chromatography-High Resolution Mass Spectrometry techniques, allowed us to survey the presence of pharmaceuticals used for COVID-19 treatment in three WWTPs of Lombardy region, where the first European cluster of SARS-CoV-2 cases was detected. Starting from a list of sixty-three suspect compounds used against COVID-19 (including some metabolites and transformation products), six compounds were fully identified and monitored together with other target analytes, mainly pharmaceuticals of common use. A monthly monitoring campaign was conducted in a WWTP from April to December 2020 and the temporal trends of some anti-COVID-19 drugs were positively correlated with those of COVID-19 cases and deaths. The comparison of the average emission loads among the three WWTPs evidenced that the highest loads of hydroxychloroquine, azithromycin and ciprofloxacin were measured in the WWTP which received the sewages from a hospital specializing in the treatment of COVID-19 patients. The monitoring of the receiving water bodies evidenced the presence of eight compounds of high ecological concern, whose risk was assessed in terms of toxicity and the possibility of inducing antibiotic and viral resistance. The results clearly showed that the enhanced, but not completely justified, use of ciprofloxacin and azithromycin represented a risk for antibiotic resistance in the aquatic ecosystems.

Bioelectrochemical approach for reductive and oxidative dechlorination of chlorinated aliphatic hydrocarbons (CAHs).

A sequential reductive-oxidative treatment was developed in this study in a continuous-flow bioelectrochemical reactor to address bioremediation of groundwater contaminated by trichloroethene (TCE) and less-chlorinated but still harmful intermediates, such as vinyl chloride. In order to optimize the anodic compartment, whereby the oxygen-driven microbial oxidation of TCE-daughter products occurs, abiotic batch experiments were performed with various anode materials poised at +1.20 V vs. SHE (i.e., graphite rods and titanium mesh anode coated with mixed metal oxides (MMO)) and setups (i.e., electrodes embedded within a bed of silica beads or graphite granule). The MMO anode displayed higher efficiency (>90%) for oxygen generation compared to the graphite electrodes. Additionally, the graphite bed presence adversely affects oxygen generation, likely due to the oxygen scavenging. This effect was completely eliminated by replacing the graphite granules with silica beads. The anodic setups were thereafter verified in a mentioned reactor at an applied TCE loading rate of approximately 20 µM d-1 and a hydraulic retention time of 1.4 d in each compartment. The cathode consisted of a bed of graphite granules and was potentiostatically controlled at -0.65 V vs. SHE. The best reactor performance in terms of removal efficiency (i.e., >97%), removal rate (i.e., 121.8 ± 2.7 µeq L-1 d-1), and the residual concentration (i.e., 5.03 ± 0.63 µeq L-1) of chlorinated contaminants was achieved with the MMO anode placed in a silica bed. Ecotoxicity tests performed with algae confirmed these results by showing progressive toxicity reduction from inlet to cathodic and anodic effluent using this reactor configuration.