Enhanced Dye Adsorption on Cold Plasma-Oxidized Multi-Walled Carbon Nanotubes: A Comparative Study.

The oxidation of multi-walled carbon nanotubes (MWCNTs) using cold plasma was investigated for their subsequent use as adsorbents for the removal of dyes from aqueous solutions. The properties of MWCNTs after plasma modification and their adsorption capacities were compared with pristine and chemically oxidized nanotubes. The modification process employed a reactor where plasma was generated through dielectric barrier discharges (DBD) powered by high-voltage nanosecond pulses. Various modification conditions were examined, such as processing time and pulse voltage amplitude. The degree of oxidation and the impact on the chemistry and structure of the nanotubes was investigated through various physicochemical and morphological characterization techniques (XPS, BET, TEM, etc.). Maximum oxidation (O/C = 0.09 from O/C = 0.02 for pristine MWCNTs) was achieved after 60 min of nanopulsed-DBD plasma treatment. Subsequently, the modified nanotubes were used as adsorbents for the removal of the dye methylene blue (MB) from water. The adsorption experiments examined the effects of contact time between the adsorbent and MB, as well as the initial dye concentration in water. The plasma-modified nanotubes exhibited high MB removal efficiency, with adsorption capacity proportional to the degree of oxidation. Notably, their adsorption capacity significantly increased compared to both pristine and chemically oxidized MWCNTs (~54% and ~9%, respectively). Finally, the kinetics and mechanism of the adsorption process were studied, with experimental data fitting well to the pseudo-second-order kinetic model and the Langmuir isotherm model. This study underscores the potential of plasma technology as a low-cost and environmentally friendly approach for material modification and water purification.

Exploring the Synergistic Mechanisms of Nanopulsed Plasma Bubbles and Photocatalysts for Trimethoprim Degradation and Mineralization in Water.

In this study, the synergetic action of nanopulsed plasma bubbles (PBs) and photocatalysts for the degradation/mineralization of trimethoprim (TMP) in water was investigated. The effects of ZnO or TiO2 loading, plasma gas, and initial TMP concentration were evaluated. The physicochemical characterization of plasma-treated water, the quantification of plasma species, and the use of appropriate plasma species scavengers shed light on the plasma-catalytic mechanism. ZnO proved to be a superior catalyst compared to TiO2 when combined with plasma bubbles, mainly due to the increased production of ⋅OH and oxygen species resulting from the decomposition of O3. The air-PBs + ZnO system resulted in higher TMP degradation (i.e., 95% after 5 min of treatment) compared to the air-PBs + TiO2 system (i.e., 87%) and the PBs-alone process (83%). The plasma gas strongly influenced the process, with O2 resulting in the best performance and Ar being insufficient to drive the process. The synergy between air-PBs and ZnO was more profound (SF = 1.7), while ZnO also promoted the already high O2-plasma bubbles' performance, resulting in a high TOC removal rate (i.e., 71%). The electrical energy per order in the PBs + ZnO system was very low, ranging from 0.23 to 0.46 kWh/m3, depending on the plasma gas and initial TMP concentration. The study provides valuable insights into the rapid and cost-effective degradation of emerging contaminants like TMP and the plasma-catalytic mechanism of antibiotics.

Phenanthrene sorption studies on coffee waste- and diatomaceous earth-based adsorbents, and adsorbent regeneration with cold atmospheric plasma.

Phenanthrene (PHE) is a polycyclic aromatic hydrocarbon categorized as a high priority organic pollutant being toxic for the ecosystem and human health, and its sorption on natural organic or inorganic substances seems a well-promising method for its removal from water streams. The goals of the present work are (i) to assess the capacity of low-cost adsorbents fabricated by treating coffee wastes and diatomaceous earth to remove PHE from water; (ii) to elucidate the role of the pore structure on PHE sorption dynamics; and (iii) to assess the potential to regenerate adsorbents loaded with PHE, by using the novel technology of cold atmospheric plasma (CAP). Diatomaceous earth (DE) and DE pre-treated with sodium hydroxide (NaOH) or phosphoric acid (H3PO4) were chosen as inorganic adsorbents. Coffee waste (CW) and activated carbons (AC) produced from its pyrolysis at 800 °C (CWAC), either untreated (CWAC-800) or pre-treated with NaOH (CWAC-NaOH-800) and H3PO4 (CWAC-H3PO4-800), were chosen as organic adsorbents. The adsorbents were characterized with nitrogen adsorption-desorption isotherms, attenuated total reflectance-Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, and mercury intrusion porosimetry. Based on the PHE sorption capacity and pore structure/surface characteristics, the CWAC-NaOH-800 was chosen as the most efficient adsorbent for further equilibrium and kinetic sorption studies. The multi-compartment model was used to describe the PHE sorption dynamics in CWAC-NaOH-800 by accounting for the pore/surface diffusion and instantaneous sorption. The CWAC-NaOH-800 exhibited remarkable values for (i) the specific surface area (SBET = 676.5 m2/g) and meso- and micro-pore volume determined by nitrogen sorption (VLN2 = 0.415 cm3/g); (ii) the macro- and meso-pore volume determined by mercury intrusion porosimetry (VMIP = 3.134 cm3/g); and (iii) the maximum PHE sorption capacity (qmax = 142 mg/g). The percentage of adsorbent recovery after its regeneration with CAP was found to be ~ 35%. From the simulation of sorption dynamics, it was found that at early times, the sorption kinetics is governed by the film diffusion towards the external surface of grains, but at late times, most of the adsorbed mass is transferred primarily to meso-/macro-pores via diffusion, and secondarily to micro-porosity via surface diffusion. Based on the adsorbent characteristics, effect of pH on sorption efficiency, and numerical analysis of sorption dynamics, it was concluded that probably the dominant adsorption mechanism is the π-π interactions between hydrophobic PHE aromatic rings and CWAC-NaOH-800 graphene layers. The high PHE removal efficiency of CWAC-NaOH-800, the successful interpretation of sorption dynamics with the multi-compartment model, and the potential to regenerate PHE-loaded adsorbents with the green and economic technology of CAP motivate a strategy for testing CWACs towards the adsorption of other PAHs, application of adsorbents to real wastewaters, and scaling-up to pilot units.

Nanostructured Materials and Advanced Processes for Application in Water Purification.

Water pollution is a major environmental problem that has a significant impact on human and animal health and the ecosystem [...].

Mechanisms of Individual and Simultaneous Adsorption of Antibiotics and Dyes onto Halloysite Nanoclay and Regeneration of Saturated Adsorbent via Cold Plasma Bubbling.

Halloysite nanoclay (HNC) was examined as an adsorbent for the individual and simultaneous removal of antibiotic enrofloxacin (ENRO) and methylene blue (MB) from aqueous solutions, alongside its regeneration via cold atmospheric plasma (CAP) bubbling. Initially, batch kinetics and isotherm studies were carried out, while the effect of several parameters was evaluated. Both ENRO and MB adsorption onto HNC was better described by Langmuir model, with its maximum adsorption capacity being 34.80 and 27.66 mg/g, respectively. A Pseudo-second order model fitted the experimental data satisfactorily, suggesting chemisorption (through electrostatic interactions) as the prevailing adsorption mechanism, whereas adsorption was also controlled by film diffusion. In the binary system, the presence of MB seemed to act antagonistically to the adsorption of ENRO. The saturated adsorbent was regenerated inside a CAP microbubble reactor and its adsorption capacity was re-tested by applying new adsorption cycles. CAP bubbling was able to efficiently regenerate saturated HNC with low energy requirements (16.67 Wh/g-adsorbent) in contrast to Fenton oxidation. Most importantly, the enhanced adsorption capacity of the CAP-regenerated HNC (compared to raw HNC), when applied in new adsorption cycles, indicated its activation during the regeneration process. The present study provides a green, sustainable and highly effective alternative for water remediation where pharmaceutical and dyes co-exist.

Cold Atmospheric Plasma Attenuates Breast Cancer Cell Growth Through Regulation of Cell Microenvironment Effectors.

Breast cancer exists in multiple subtypes some of which still lack a targeted and effective therapy. Cold atmospheric plasma (CAP) has been proposed as an emerging anti-cancer treatment modality. In this study, we investigated the effects of direct and indirect CAP treatment driven by the advantageous nanosecond pulsed discharge on breast cancer cells of different malignant phenotypes and estrogen receptor (ER) status, a major factor in the prognosis and therapeutic management of breast cancer. The main CAP reactive species in liquid (i.e. H2O2, NO 2 - /NO 3 - ) and gas phase were determined as a function of plasma operational parameters (i.e. treatment time, pulse voltage and frequency), while pre-treatment with the ROS scavenger NAC revealed the impact of ROS in the treatment. CAP treatment induced intense phenotypic changes and apoptosis in both ER+ and ER- cells, which is associated with the mitochondrial pathway as evidenced by the increased Bax/Bcl-2 ratio and cleavage of PARP-1. Interestingly, CAP significantly reduced CD44 protein expression (a major cancer stem cell marker and matrix receptor), while differentially affected the expression of proteases and inflammatory mediators. Collectively, the findings of the present study suggest that CAP suppresses breast cancer cell growth and regulates several effectors of the tumor microenvironment and thus it could represent an efficient therapeutic approach for distinct breast cancer subtypes.

Enhancing the adhesion of graphene to polymer substrates by controlled defect formation.

The mechanical integrity of composite materials depends primarily on the interface strength and the defect density of the reinforcement which is the provider of enhanced strength and stiffness. In the case of graphene/polymer nanocomposites which are characterized by an extremely large interface region, any defects in the inclusion (such as folds, cracks, holes, etc) will have a detrimental effect to the internal strain distribution and the resulting mechanical performance. This conventional wisdom, however, can be challenged if the defect size is reduced beyond the critical size for crack formation to the level of atomic vacancies. In that case, there should be no practical effect on crack propagation and depending on the nature of the vacancies the interface strength may in fact increase. In this work we employed argon ion (Ar+) bombardment and subsequent exposure to hydrogen (H2) to induce (as revealed by x-ray and ultraviolet photoelectron spectroscopy and Raman spectroscopy) passivated atomic single vacancies to CVD graphene. The modified graphene was subsequently transferred to PMMA bars and the morphology, wettability and the interface adhesion of the CVD graphene/PMMA system were investigated with atomic force microscopy technique and Raman analysis. The results obtained showed clearly an overall improved mechanical behavior of graphene/polymer interface, since an increase as well as a more uniform shift distribution with strain is observed. This paves the way for interface engineering in graphene/polymer systems which, in pristine condition, suffer from premature graphene slippage and subsequent failure.

Effects of carbon dioxide on the mobilization of metals from aquifers.

Potential leakages of CO2 from storage sites to shallow aquifers could have adverse impacts on the quality of potable groundwater. The mineralogy of well-sorted silica sand is modified by the pH-controlled precipitation of eight metals (Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd). Continuous flow tests are performed in two fixed-bed columns packed with the modified sand by coinjecting gas CO2/distilled water (2-phase column) and distilled water (1-phase column/control test) at constant influx rates for a period of two months. The concentration of dissolved metals is measured in the effluents of columns with atomic absorption spectroscopy (AAS). Mineralogical analysis of the surface of sand grains is done before and after the flow tests with scanning electron microscopy-X-ray energy dispersive spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS), whereas the precise quantitative measurement of the metal content in the sand is done with AAS. A dynamic numerical model that couples the flow and mass-transfer processes in porous media with the equilibrium and kinetically driven metal desorption processes is developed. Inverse modeling of the continuous flow test enables us to quantify and rank the selectivity of metal mobility in terms of equilibrium and kinetic desorption parameters. The continuous CO2 dissolution and water acidification causes significant mobilization and dissolution of several metals (Mn, Ni, Cu, Zn, Co), moderate mobilization of Cr, acceleration of Cd dissolution, whereas Fe remains strongly bonded on the sand grains as goethite. The parameters estimated from lab-scale column tests might be helpful for interpreting field-scale CO2 leakage scenarios and installing relevant early warning monitoring systems.

Complex hydrogel systems composed of polymers, liposomes, and cyclodextrins: implications of composition on rheological properties and aging.

Rheological properties of complex hydrogels containing different amounts of liposomes and/or cyclodextrin (CD) were evaluated. Sonicated unilamellar vesicles (SUV) were loaded in a hydrogel composed of Carbopol 974 NF and hydroxyethylcellulose (Natrosol 250 HX). Phosphatidylcholine (PC) and hydrogenated-PC (HPC) liposomes, both mixed with cholesterol in a 2:1 lipid/chol mol ratio, were used. In some cases, hydroxypropyl-beta-cyclodextrin was also added (100 or 400 mg/mL). Gels were incubated at 40 degrees C/75% humidity for 7 days or 1 month to evaluate the effect of aging on their rheological properties. FTIR and DSC studies were performed to investigate possible interactions between the polymers and CD molecules at different CD concentrations. Static and dynamic rheological measurements were carried out. All gels had shear-thinning behavior (fitted well by the Cross model) with the exception of gels containing high concentrations of CD that were transformed into nonflowing elastic sticky solids, especially after aging. The more pronounced elastic behavior of gels containing 400 mg/mL CD is reflected by the higher values of relaxation strengths over all relaxation times. Complete interaction between polymers and CD, in the high-CD-content gels, as proven by FTIR and DSC studies, explains the dominating contribution of CD on gel characteristics. The addition of liposomes to such CD-containing gels has a substantial effect on their rheological properties, which are dependent on the liposome type (HPC/chol liposomes > PC/chol) and the lipid/CD ratio. This is explained by the "neutralization" of some CD molecules that prefer to interact with chol molecules that they extract from the lipid membranes. Gels with a high CD concentration (400 mg/mL) are almost insensitive to aging, whereas all other gels become slightly more elastic and less viscous as aging proceeds.