Emerging contaminants in the environment have caused enormous concern in the last few decades, and among them, antibiotics have received special attention. On the other hand, adsorption has shown to be a useful, low-cost, and eco-friendly method for the removal of this type of contaminants from water. This work is focused on the study of ciprofloxacin (CPX) removal from water by adsorption on pillared clays (PILC) under basic pH conditions, where CPX is in its anionic form (CPX⁻). Four different materials were synthetized, characterized, and studied as adsorbents of CPX (Al-, Fe-, Si-, and Zr-PILC). The highest CPX adsorption capacities of 100.6 and 122.1 mg g⁻¹ were obtained for the Si- and Fe-PILC (respectively), and can be related to the porous structure of the PILCs. The suggested adsorption mechanism involves inner-sphere complexes formation as well as van der Waals interactions between CPX⁻ and the available adsorption sites on the PILC surfaces.

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 (S_BET) and micropore volumes (V_μp) 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.

The Copahue Thermal Center, situated in Neuquén, Argentina, produces natural and matured peloids, which are employed in the prevention and treatment of various osteoarticular and dermatological disorders. The presence of sulfur as a constituent and its thermotherapeutic potential constitute the primary strengths of these peloids. Nevertheless, accessing Copahue is challenging due to its distance from densely populated centers and the snow cover during the winter months in the southern hemisphere. Therefore, in order to propose a material that can be utilized year-round in any location, a mudpack was obtained by combining medicinal paraffin with dehydrated Copahue peloids, with concentrations evaluated up to 10% w/w. This mudpack was analyzed through X-ray diffraction, which detected the presence of sulfur, the most important component of Copahue’s peloids. Through IR spectroscopy, the signals that identify medicinal paraffin were clearly observed, and for concentrations of 6% and 10% peloid in the material, it was possible to detect the presence of mineral clay components associated with Si-O stretching vibrations at around 1041 cm⁻¹. The low values of luminosity and grey tonality obtained for the mudpack contributed to patient acceptability and the absorption of electromagnetic radiation. The experimental cooling rate, calculated using the ratio of the temperature variation (∆T) with respect to the time variation (∆t) in each interval of the experimental curve, was determined to be 0.6 °C·min⁻¹ for both paraffin and the mudpack. However, for peloids, higher values ranging from 0.6 to 4.8 °C·min⁻¹ were obtained. This suggests that the mudpack mixtures have a slower heat release, which is a desirable property for their use as a thermotherapeutic agent. Considering the reusability of the mudpack, its stability was evaluated after 10 cycles of cooling and heating through XRD, DSC, and FTIR tests, resulting in a system that retains its properties. The formulation of the obtained mudpack is promising for the development of these materials on a larger scale.

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.

Adsorption studies of ciprofloxacine (CPX) and lidocaine (LID) emerging contaminants were performed on two fibrous Mg clays from the Madrid basin and Senegal. The samples were characterized by X-ray diffraction, ICP major element analysis, infrared spectroscopy, thermal analysis, optical petrography, scanning and transmission electron microscopy, cation exchange capacity (CEC), and N₂-BET analysis. Two mineral assemblages were established. Assemblage 1 mainly consists of sepiolite and minor trioctahedral smectite, while assemblage 2 is mostly composed of palygorskite, which is associated with dioctahedral smectite. The sorption was fast and reached equilibrium in 2 h. Fibrous Mg clays showed a higher adsorption capacity for CPX than for LID in the conditions studied. CPX adsorption on sepiolite and palygorskite can be the result of the combination of various mechanisms: ion exchange with permanently charged sites, electrostatic attractions with external surfaces, and an inner sphere complex with broken edges. LID adsorption mainly occurs by ion exchange and electrostatic interaction with the external surfaces of the clays. Dioctahedral smectite, as an associated phase, contributed to a higher removal percentage in palygorskite samples. By contrast, the trioctahedral smectite did not play a significant role in the adsorption of the samples with sepiolite. The mesoporous structure, high surface area, and moderate cation exchange of fibrous clays play a key role in the sorption process of CPX and LID.

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.