Biocatalyst developed with recovered iron-rich minerals enhances the biotransformation of SARS-CoV-2 antiviral drugs in anaerobic bioreactors.

The biotransformation of the SARS-CoV-2 antiviral drugs, ribavirin and tenofovir, was studied in methanogenic bioreactors. The role of iron-rich minerals, recovered from a metallurgic effluent, on the biotransformation process was also assessed. Enrichment of anaerobic sludge with recovered minerals promoted superior removal efficiency for both antivirals (97.4 % and 94.7 % for ribavirin and tenofovir, respectively) as compared to the control bioreactor lacking minerals, which achieved 58.5 % and 37.9 % removal for the same drugs, respectively. Further analysis conducted by liquid chromatography coupled to mass spectroscopy revealed several metabolites derived from the biotransformation of both antivirals. Interestingly, tracer analysis with 13CH4 revealed that anaerobic methane oxidation coupled to Fe(III) reduction occurred in the enriched bioreactor, which was reflected in a lower content of methane in the biogas produced from this system, as compared to the control bioreactor. This treatment proposal is suitable within the circular economy concept, in which recovered metals from an industrial wastewater are applied in bioreactors to create a biocatalyst for promoting the biotransformation of emerging pollutants. This strategy may be appropriate for the anaerobic treatment of wastewaters originated from hospitals, as well as from the pharmaceutical and chemical sectors.

New bimetallic adsorbent material based on cerium-iron nanoparticles highly selective and affine for arsenic(V).

Bimetallic oxy(hydroxides) have gain great interest in water treatment systems based on adsorption processes. Their high OH groups density, in addition to inheriting the oxides properties make them highly promising adsorbents of anions. In this work, highly affine and selective bimetallic oxyhydroxides of cerium and iron (Ce:Fe-P's) for arsenic(V) were synthesized by implementing an assisted microwave methodology. The Ce:Fe-P's were characterized by various techniques (SEM, FTIR, XRD and XPS) and the As(V) adsorption capacity and kinetics as well as the effect of pH and the presence of coexisting anions were determined. The results showed that Ce:Fe-P's have an outstanding As(V) adsorption capacity (179.8 mg g-1 at Ce = 3 mg L-1) even at low concentrations (120 mg g-1 at Ce = 37 µg L-1). Moreover, the adsorption equilibrium was reached very fast, just in 3 min, with an adsorption rate of 0.123 mg min-1, that is, 80% of the initial As(V) concentration of 5 mg L-1 was removed in the first 3 min. The arsenic adsorption capacity decreased only up to 20% at pH above 7, attributed to electrostatic repulsions due to the adsorbent's pHPZC, which was 6.8. On the other hand, the arsenic adsorption capacity of Ce:Fe-P's decreased just 21% in the presence of 10 mg L-1 of each of the following competing anions: F-, Cl-, SO42-, NO3-, PO43- and CO32-, which usually coincide in contaminated water with As(V). Ce:Fe-P's has proven to be one of the most promising As(V) adsorbent materials reported so far in the literature, because it presented an outstanding adsorption capacity and at the same time a very fast adsorption speed. Furthermore, the pH and the concentration of coexisting anions caused little interference in the adsorption processes. Due to the above, the Ce:Fe-P's is already in the process of intellectual protection.

Synthesis of Bamboo-like Multiwall Carbon Nanotube-Poly(Acrylic Acid-co-Itaconic Acid)/NaOH Composite Hydrogel and its Potential Application for Electrochemical Detection of Cadmium(II).

A poly(acrylic acid-co-itaconic acid) (PAA-co-IA)/NaOH hydrogel containing bamboo-type multiwall carbon nanotubes (B-MWCNTs) doped with nitrogen (PAA-co-IA/NaOH/B-MWCNTs) was synthesized and characterized by SEM, absorption of water, point of zero charges, infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The possible use of the PAA-co-IA/NaOH/B-MWCNT hydrogel as an electrode modifier and pre-concentrator agent for Cd(II) sensing purposes was then evaluated using carbon paste electrodes via differential pulse voltammetry. The presence of the B-MWCNTs in the hydrogel matrix decreased its degree of swelling, stabilized the structure of the swollen gel, and favored the detection of 3 ppb Cd(II), which is comparable to the World Health Organization's allowable maximum value in drinking water. A calibration curve was obtained in the concentration range of 2.67 × 10-8 to 6.23 × 10-7 M (i.e., 3 and 70 ppb) to determine a limit of detection (LOD) of 19.24 µgL-1 and a sensitivity of 0.15 µC ppb-1. Also, the Zn(II), Hg(II), Pb(II) and Cu(II) ions interfered moderately on the determination of Cd(II).

Effects of surface-engineered nanoparticle-based dispersants for marine oil spills on the model organism Artemia franciscana.

Fine particles are under active consideration as alternatives to chemical dispersants for large-scale petroleum spills. Fine carbon particles with engineered surface chemistry have been shown to stabilize oil-in-water emulsions, but the environmental impacts of large-scale particle introduction to the marine environment are unknown. Here we study the impact of surface-engineered carbon-black materials on brine shrimp (Artemia franciscana) as a model marine microcrustacean. Mortality was characterized at 50-1000 mg/L, and levels of heat shock protein 70 (hsp70) were characterized at sublethal particle concentrations (25-50 mg/L). Functionalized carbon black (CB) nanoparticles were found to be nontoxic at all concentrations, while hydrophobic (annealed) and as-produced CB induced adverse effects at high concentrations. CB was also shown to adsorb benzene, a model hydrocarbon representing the more soluble and toxic low-molecular weight aromatic fraction of petroleum, but the extent of adsorption was insufficient to mitigate benzene toxicity to Artemia in coexposure experiments. At lower benzene concentrations (25-75 mg/L), coexposure with annealed and as-produced CB increased hsp70 protein levels. This study suggests that surface functionalization for increased hydrophilicity can not only improve the performance of CB-based dispersants but also reduce their adverse environmental impacts on marine organisms.

Reactive adsorption of SO2 on activated carbons with deposited iron nanoparticles.

The effect of iron particle size anchored on the surface of commercial activated carbon on the removal of SO(2) from a gas phase was studied. Nanosize iron particles were deposited using forced hydrolysis of FeCl(3) with or without H(3)PO(4) as a capping agent. Dynamic adsorption experiments were carried out on either dry or pre-humidified materials and the adsorption capacities were calculated. The surface of the initial and exhausted materials was extensively characterized by microscopic, porosity, thermogravimetric and surface chemistry. The results indicate that the SO(2) adsorption capacity increased two and half times after the prehumidification process owing to the formation of H(2)SO(4) in the porous system. Iron species enhance the SO(2) adsorption capacity only when very small nanoparticles are deposited on the pore walls as a thin layer. Large iron nanoparticles block the ultramicropores decreasing the accessibility of the active sites and consuming oxygen that rest adsorption centers for SO(2) molecules. Iron nanoparticles of about 3-4 nm provide highly dispersed adsorption sites for SO(2) molecules and thus increase the adsorption capacity of about 80%. Fe(2)(SO(4))(3) was detected on the surface of exhausted samples.