In this work, three silica pillared clays (Si-PILC) were synthetized, characterized, and evaluated as possible adsorbents of ciprofloxacin (CPX) and tetracycline (TC) form alkaline aqueous media. The pillared clays obtained showed significant increases in their specific surface areas (SBET) and micropore volumes (Vμp) regarding the raw material, resulting in microporosity percentages higher than 57% in all materials. The studies of CPX and TC removal using pillared clays were compared with the natural clay and showed that the Si-PILC adsorption capacities have a strong relationship with their porous structures. The highest adsorption capacities were obtained for CPX on Si-PILC due to the lower molecular size of CPX respect to the TC molecule, favoring the interaction between the CPX− and the pillars adsorption sites. Tetracycline adsorption on silica pillared clays evidenced that for this molecule the porous structure limits the interaction between the TCH− and the pillars, decreasing their adsorption capacities. However, the results obtained for both antibiotics suggested that their negative species interact with adsorption sites on the pillared structure by adsorption mechanisms that involve inner-sphere complex formation as well as van der Waals interactions. The adsorption mechanism proposed for the anionic species on Si-PILC could be considered mainly as negative cooperative phenomena where firstly there is a hydrophobic effect followed by other interactions, such as der Waals or inner-sphere complex formation.
This study evaluated non-fibrous Mg-clays as potential adsorbents of emerging contaminants (ECs) from water. The materials were characterized, and their textural and structural properties were related to their ability to remove two model EC molecules: ciprofloxacin (CPX) and lidocaine (LID). The results showed that Ad-6 and Ad-7 are mixed-layer kerolite/stevensite, while Ad-5 and Ad-8 are mainly composed of smectite minerals like stevensite and saponite, respectively. Ad-8 exhibited the highest CPX-adsorption capacity (0.91 mmol·g−1 clay), likely due to its saponite content. Mixed-layer materials also performed well, with Ad-6 and Ad-7 achieving an adsorption capacity of 0.8 and 0.55 mmol·g−1 clay, respectively. Adsorption studies suggested that CPX is adsorbed through ion exchange in materials with high smectite content (Ad-8 and Ad-5), while interstratified materials showed enhanced retention due to kerolite presence, which improves their porous structures. Similar findings were observed for LID, indicating a cationic-exchange mechanism for LID adsorption in all the materials and suggesting that the molecular size of the EC could regulate the removal capacity of these materials. This work showed that the studied Mg-clays could be effectively used for the removal of pharmaceutical pollutants, expanding their commercial possibilities.
Copahue Thermal Center is characterized by the presence of mineromedicinal acidic waters with high temperatures, therapeutic peloids, and relevant consortia of extremophiles species, distributed in small natural pools which cannot be disinfected. The objective of this research was to investigate the survival of SARS-CoV-2 in Copahue’s waters and its remaining infective capacity. In a first assay, a decrease of more than 50% of the initially viral load compared to the initially inoculated positive sample was detected for all the water samples analyzed. After that, two of the Copahue springs, which are used as an immersion bath in closed environments without going through any disinfection treatment, was selected to determine the viral viability. VERO cell infections were performed, with no cytopathic effect detected, but a strikingly high resistance of the virus, detecting its genome by real time PCR, during the seven days of study under laboratory conditions. SARS-CoV-2 survival in acid media was reaffirmed, which is a peculiarity for a covered virus. A decrease in the detectable viral load of the positive sample was found as the infection time passed, becoming completely negative in the subsequent blind passages. More research is needed to further study the feasibility of SARS-CoV-2 in mineromedicinal waters, especially natural acidic waters that cannot disinfected, in order to expand information about the risk to populations that are exposed to them.