ABSTRACT
This study describes the development of hydrogel formulations with ionic crosslinking capacity and photocatalytic characteristics. The objective of this research is to provide an effective, accessible, "green", and facile route for the decontamination of chemical warfare agents (CWAs, namely the blistering agent-mustard gas/sulfur mustard (HD)) from contaminated surfaces, by decomposition and entrapment of CWAs and their degradation products inside the hydrogel films generated "on-site". The decontamination of the notorious warfare agent HD was successfully achieved through a dual hydrolytic-photocatalytic degradation process. Subsequently, the post-decontamination residues were encapsulated within a hydrogel membrane film produced via an ionic crosslinking mechanism. Polyvinyl alcohol (PVA) and sodium alginate (ALG) are the primary constituents of the decontaminating formulations. These polymeric components were chosen for this application due to their cost-effectiveness, versatility, and their ability to form hydrogen bonds, facilitating hydrogel formation. In the presence of divalent metallic ions, ALG undergoes ionic crosslinking, resulting in rapid gelation. This facilitated prompt PVA-ALG film curing and allowed for immediate decontamination of targeted surfaces. Additionally, bentonite nanoclay, titanium nanoparticles, and a tetrasulfonated nickel phthalocyanine (NiPc) derivative were incorporated into the formulations to enhance absorption capacity, improve mechanical properties, and confer photocatalytic activity to the hydrogels obtained via Zn2+-mediated ionic crosslinking. The resulting hydrogels underwent characterization using a variety of analytical techniques, including scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), viscometry, and mechanical analysis (shear, tensile, and compression tests), as well as swelling investigations, to establish the optimal formulations for CWA decontamination applications. The introduction of the fillers led to an increase in the maximum strain up to 0.14 MPa (maximum tensile resistance) and 0.39 MPa (maximum compressive stress). The UV-Vis characterization of the hydrogels allowed the determination of the band-gap value and absorption domain. A gas chromatography-mass spectrometry assay was employed to evaluate the decontamination efficacy for a chemical warfare agent (sulfur mustard-HD) and confirmed that the ionic crosslinked hydrogel films achieved decontamination efficiencies of up to 92.3%. Furthermore, the presence of the photocatalytic species can facilitate the degradation of up to 90% of the HD removed from the surface and entrapped inside the hydrogel matrix, which renders the post-decontamination residue significantly less dangerous.
ABSTRACT
This study presents the synthesis and characterization of alginate-based nanocomposite peelable films, reinforced by carbon nanofibers (CNFs) decorated with nanoparticles that possess remarkable antimicrobial properties. These materials are suitable for immediate decontamination applications, being designed as fluid formulations that can be applied on contaminated surfaces, and subsequently, they can rapidly form a peelable film via divalent ion crosslinking and can be easily peeled and disposed of. Silver, copper, and zinc oxide nanoparticles (NPs) were synthesized using superficial oxidized carbon nanofibers (CNF-ox) as support. To obtain the decontaminating formulations, sodium alginate (ALG) was further incorporated into the colloidal solutions containing the antimicrobial nanoparticles. The properties of the initial CNF-ox-NP-ALG solutions and the resulting peelable nanocomposite hydrogels (obtained by crosslinking with zinc acetate) were assessed by rheological measurements, and mechanical investigations, respectively. The evaluation of Minimal Inhibitory Concentration (MIC) and Minimal Bactericidal Concentration (MBC) for the synthesized nanoparticles (silver, copper, and zinc oxide) was performed. The best values for MIC and MBC were obtained for CNF-ox decorated with AgNPs for both types of bacterial strains: Gram-negative (MIC and MBC values (mg/L): E. coli-3 and 108; P. aeruginosa-3 and 54) and Gram-positive (MIC and MBC values (mg/L): S. aureus-13 and 27). The film-forming decontaminating formulations were also subjected to a microbiology assay consisting of the time-kill test, MIC and MBC estimations, and evaluation of the efficacity of peelable coatings in removing the biological agents from the contaminated surfaces. The best decontamination efficiencies against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa varied between 97.40% and 99.95% when employing silver-decorated CNF-ox in the decontaminating formulations. These results reveal an enhanced antimicrobial activity brought about by the synergistic effect of silver and CNF-ox, coupled with an efficient incorporation of the contaminants inside the peelable films.
ABSTRACT
Radioactive materials are potentially harmful due to the radiation emitted by radionuclides and the risk of radioactive contamination. Despite strict compliance with safety protocols, contamination with radioactive materials is still possible. This paper describes innovative and inexpensive formulations that can be employed as 'eco-friendly' tools for the safe decontamination of radiopharmaceuticals spills or other accidental radioactive contamination of the surfaces arising from general-purpose radioisotope handling facilities (radiopharmaceutical laboratories, hospitals, research laboratories, etc.). These new peelable nanocomposite coatings are obtained from water-based, non-toxic, polymeric blends containing readily biodegradable components, which do not damage the substrate on which they are applied while also displaying efficient binding and removal of the contaminants from the targeted surfaces. The properties of the film-forming decontamination solutions were assessed using rheological measurements and evaporation rate tests, while the resulting strippable coatings were subjected to Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and tensile tests. Radionuclide decontamination tests were performed on various types of surfaces encountered in radioisotope workspaces (concrete, painted metal, ceramic tiles, linoleum, epoxy resin cover). Thus, it was shown that they possess remarkable properties (thermal and mechanical resistance which permits facile removal through peeling) and that their capacity to entrap and remove beta and alpha particle emitters depends on the constituents of the decontaminating formulation, but more importantly, on the type of surface tested. Except for the cement surface (which was particularly porous), at which the decontamination level ranged between approximately 44% and 89%, for all the other investigated surfaces, a decontamination efficiency ranging from 80.6% to 96.5% was achieved.
ABSTRACT
The issue of heavy metal and radionuclide contamination is still causing a great deal of concern worldwide for environmental protection and industrial sites remediation. Various techniques have been developed for surface decontamination aiming for high decontamination factors (DF) and minimal environmental impact, but strippable polymeric nanocomposite coatings are some of the best candidates in this area. In this study, novel strippable coatings for heavy metal and radionuclides decontamination were developed based on the film-forming ability of polyvinyl alcohol, with the remarkable metal retention capacity of bentonite nanoclay, together with the chelating ability of sodium alginate and with "new-generation" "green" complexing agents: iminodisuccinic acid (IDS) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC). These environmentally friendly water-based decontamination solutions are capable of generating strippable polymeric films with optimized mechanical and thermal properties while exhibiting high decontamination efficiency (DF ≈ 95-98% for heavy metals tested on glass surface and DF ≈ 91-97% for radionuclides 241Am, 90Sr-Y and 137Cs on metal, painted metal, plastic, and glass surfaces).
ABSTRACT
In the context of imminent threats concerning biological and chemical warfare agents, the aim of this study was the development of a new method for biological and chemical decontamination, employing non-toxic, film-forming, water-based biodegradable solutions, using a nano sized reagent together with bentonite as trapping agents for the biological and chemical contaminants. Bentonite-supported nanoparticles of Cu, TiO2, and Ag were successfully synthesized and dispersed in a polyvinyl alcohol (PVA)/glycerol (GLY) aqueous solution. The decontamination effectiveness of the proposed solutions was evaluated by qualitative and quantitative analytical techniques on various micro-organisms, with sulfur mustard (HD) and dimethyl methylphosphonate (DMMP) as contaminants. The results indicate that the peelable active nanocomposite films can be successfully used on contaminated surfaces to neutralize and entrap the hazardous materials and their degradation products. Mechanical and thermal characterization of the polymeric films was also performed to validate the decontamination solution's potential as peelable-film generating materials. The removal efficacy from the contaminated surfaces for the tested micro-organisms varied between 93% and 97%, while for the chemical agent HD, the highest decontamination factor obtained was 90.89%. DMMP was almost completely removed from the contaminated surfaces, and a decontamination factor of 99.97% was obtained.
ABSTRACT
Eight different types of complexing agents were employed for the development of new biodegradable decontamination solutions that are able to form strippable coatings after they are dispersed and allowed to dry on a variety of surfaces contaminated with 60Co, 133Ba, 137Cs and 241Am radioactive isotopes. The new generation of eco-friendly chelators with superior biodegradability, utilized for the first time in such applications, can easily replace the non-biodegradable and carcinogenic complexing agents that are still in use today, due to their decontamination performances. Furthermore, besides the complexing action over the radionuclides, the solutions contain two types of clays, Bentonite (BT) and Saponite (SP), which have the capacity to adsorb specific ions, improving the decontamination efficiency of the solutions. Our research revealed that it is preferable to replace BT with SP, due to its better dispersibility, thermal stability, next to superior ability to gel and better thermal stability (Miles, 2011). The solutions showed a decontamination factor superior to 95% for 137Cs (on all surfaces), over 90% for 60Co and 133Ba, and more than 72% 241Am (on all surfaces), except for galvanized metal plates, where lower decontamination factors were obtained: over 70% for 133Ba, maximum 41.87% for 241Am and 43.19% for 60Co.