Removal of Transition Metals from Contaminated Aquifers by PRB Technology: Performance Comparison among Reactive Materials.

The most common reactive material used for the construction of a permeable reactive barrier (PRB) is zero valent iron (ZVI), however, its processing can generate corrosive effects that reduce the efficiency of the barrier. The present study makes a major contribution to understanding new reactive materials as natural and synthetic, easy to obtain, economical and environmentally friendly as possible substitutes for the traditional ZHV to be used as filters in the removal of three transition metals (Zn, Cu, Cd). To assess the ability to remove these pollutants, a series of batch and column tests were carried out at laboratory scale with these materials. Through BACH tests, four of seven substances with a removal percentage higher than 99% were prioritized (cabuya, natural clinoptilolite zeolites, sodium mordenite and mordenite). From this group of substances, column tests were performed where it is evidenced that cabuya fiber presents the lowest absorption time (≈189 h) while natural zeolite mordenite shows the highest time (≈833 h). The latter being the best option for the PRB design. The experimental values were also reproduced by the RETRASO code; through this program, the trend between the observed and simulated values with respect to the best reactive substance was corroborated.

Porous Carbon Materials Obtained by the Hydrothermal Carbonization of Orange Juice.

Porous carbon materials are currently subjected to strong research efforts mainly due to their excellent performances in energy storage devices. A sustainable process to obtain them is hydrothermal carbonization (HTC), in which the decomposition of biomass precursors generates solid products called hydrochars, together with liquid and gaseous products. Hydrochars have a high C content and are rich with oxygen-containing functional groups, which is important for subsequent activation. Orange pomace and orange peels are considered wastes and then have been investigated as possible feedstocks for hydrochars production. On the contrary, orange juice was treated by HTC only to obtain carbon quantum dots. In the present study, pure orange juice was hydrothermally carbonized and the resulting hydrochar was filtered and washed, and graphitized/activated by KOH in nitrogen atmosphere at 800 °C. The resulting material was studied by transmission and scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and nitrogen sorption isotherms. We found porous microspheres with some degree of graphitization and high nitrogen content, a specific surface of 1725 m2/g, and a pore size distribution that make them good candidates for supercapacitor electrodes.

Anticancer activity modulation of an innovative solid formulation of extra virgin olive oil by cultured zeolite scaffolds.

This paper deals with the design and manufacture of pure and hybrid synthetic (Mixed Matrix Membranes, MMMs) zeolite scaffolds (containing various amount of zeolite crystals dispersed in a polymeric matrix) to obtain new biomaterials. These scaffolds can potentially be used in the field of translational medicine to obtain innovative results to address tumorigenesis mechanisms with the promotion of an effort to deal with technical methods and information. Since olive oil has beneficial effects in healthy human cells and slows down and/or inhibits cell growth, the aim of this work was to monitor the protective and beneficial antitumor effects of olive oil in a new solid formulation (Spread Bio-Oil) on cancer cell cultured on zeolite scaffolds. In order to investigate the cytotoxicity of the new bio-oil spread and to test antiproliferative activity on the cancer cells we used two phenotypically different human breast cancer cell lines (MCF-7 and MDA-MB-231) seeded on various morphologies of zeolite membranes. We report the fabrication and characterization of pure and hybrid (MMMs) zeolite membranes and evaluated the intensively cell adhesion, spreading and cell growth by adhesion test, MTT, optical microscopy analyses and Scanning Electronic Microscopy (SEM) microphotography analyses. Our results demonstrate that both cell lines adhered and grow on all zeolite surfaces and that both show better viability after Spread Bio-Oil treatments. All cell adhesions are a specific membrane-type and, in particular, MCF-7 cells interact and adhere preferentially on pure zeolite membranes. Cancer cells seem to recognize and prefer the characteristics of the supports according to the following trend: Co-ZSM-5 > Co-S-1 > 13X. Moreover, Co-ZSM-5 zeolite membranes were the best scaffolds and MDA-MB-231 cells after administration of Spread Bio-Oil showed less viability with respect to MCF-7 responding better to all concentrations of the innovative food. Our data indicate that Spread Bio-Oil decreases at very low concentration values (5, 10, 25, 50, 100, 200 and 300 µg/mL) cell proliferation in a dose- and time-dependent manner. The work confirms both the superiority of pure zeolite scaffolds for cultures of human normal and cancer cells and Spread Bio-Oil as an innovative food preserving all the beneficial and healthy properties of the extra virgin olive oil from which it derives.

Adsorption Performance Analysis of Alternative Reactive Media for Remediation of Aquifers Affected by Heavy Metal Contamination.

A series of experimental batch tests has been carried out with the aim of improving the knowledge of fundamental processes related to the fate and behavior of heavy metals that can be of environmental concern in groundwater. The analysis of contaminants (i.e., Cu, Zn, Cd and Pb) dynamics in different environmental compartments is specifically addressed by comparing the removal efficiencies of different types of reactive materials, three natural (i.e., vegetal fibers, natural limestone and natural zeolite) and one synthetic (i.e., synthetic zeolite). Results stemming from these reactive media has been compared with the outcomes related to the same test performed using zero valent iron which is the reactant usually employed for heavy metals remediation. All tested reactants exhibited important removal percentages, even larger than 90% in most cases, achieved in a contact time ranging between about 12 h and slightly longer than a day (i.e., 30 h). Maximum adsorption percentages are observed for pH ranging between 4 and 8 for all tested materials and contaminants. Our findings provided relevant evidence, to both researchers and technicians, on the competitiveness of the explored alternative mediums with respect to the classical reactants usually employed for heavy metals remediation.

Zeolite inorganic supports for BSA immobilization: comparative study of several zeolite crystals and composite membranes.

Zeolites due to their low toxicity and high compatibility are considered new biomaterials for medical applications. The surface adsorption behaviour of zeolite crystals and composite membranes was discussed in this research. The zeolite materials were synthesized by hydrothermal syntheses using different reaction gels to modulate the Brönsted acidity of the microporous structures. Spectrophotometric analyses were used to evaluate protein adsorption on these surfaces. This study revealed that zeolite chemical composition and structure influenced the kinetics of protein adsorption. Zeolite Y surface adsorbed greater amount of BSA than the other structures. The percentage of adsorption increases with temperature and depends on the pH of the solution, being highest at the pI of the protein. The influence of the membrane configuration on the protein adsorption was studied using different zeolite structures and crystallization types. It seems that the observed differences could depend on the type of hydrothermal crystallization inside the inorganic support.

Use of Vegetable Fibers for PRB to Remove Heavy Metals from Contaminated Aquifers-Comparisons among Cabuya Fibers, Broom Fibers and ZVI.

The Zero Valent Iron (ZVI) is the material most commonly used for permeable reactive barriers (PRB). For technical and economic reasons, hoter reactive substances usable in alternative to ZVI are investigated. The present study takes into account a vegetable fibers, the cabuya, investigating its capacity to retain heavy metals. The capacity of the cabuya fibers to adsorb heavy metals was verified in laboratory, by batch and column tests. The batch tests were carried out with cabuya and ZVI, using copper (Cu), zinc (Zn), cadmium (Cd) and lead (Pb). The results obtained by the cabuya fibers showed a very high adsorption capacity of heavy metals and resulted very similar to those obtained for the broom fibers in a previous study. The high value of the absorption capacity of the cabuya fibers was also confirmed by the analogous comparison made with the results of the batch tests carried out with ZVI. Column tests, using copper, zinc and cadmium, allowed to determine for the cabuya fibers the maximum removal percentage of the heavy metals considered, the corresponding times and the time ranges of the release phase. For each metal considered, for a given length and three different times, the constant of degradation of cabuya fibers was determined, obtaining values very close to those reported for broom fibers. The scalar behavior of heavy metal removal percentage was verified. An electron microscope analysis allowed to compare, by SEM images, the characteristics of the cabuya and broom fibers. Finally, to investigate the chemical structure of cabuya and broom fibers, the FTIR technique was used, obtaining their respective infrared spectra.

Fabrication and evaluation of novel zeolite membranes to control the neoplastic activity and anti-tumoral drug treatments in human breast cancer cells. Part 1: Synthesis and characterization of Pure Zeolite Membranes and Mixed Matrix Membranes for adhesion and growth of cancer cells.

Novel pure and hybrid zeolite membranes were prepared with appropriate different physicochemical characteristics such as frameworks, hydrophilicity, crystal size, chemical composition, acid-base properties (Point of Zero Charge, PZC) and surface morphology and used in inorganic cell/scaffold constructs. Because the control of cell interactions, as the adhesion, proliferation, remodelling and mobility, is important for differentiation and progression of tumors, this work focused on response of cancer cells adhered and grown on synthesized zeolite surfaces in order to study the influence of these scaffolds in controlled conditions. We have selected the MCF-7 and MDA-MB-231 human breast cancer cell line as model tumor cell lines. This study showed that all the zeolite membranes synthesized are excellent scaffolds because they are very selective materials to support the adhesion and growth of neoplastic cells. All zeolite scaffolds were characterized by FESEM, FTIR ATR, XRD, AFM, PZC and contact angle analyses. Cell adhesion, viability and morphology were measured by count, MTT assay and FESEM microphotography analysis, at various incubation times.

Zeolite scaffolds for cultures of human breast cancer cells. Part II: Effect of pure and hybrid zeolite membranes on neoplastic and metastatic activity control.

This work is focused on the response of two invasive phenotypes of human breast cancer cells, MCF-7 and MDA-MB-231, grown on synthesized zeolite scaffolds in order to study the influence of those biomaterials in controlled conditions with and without anti-tumoral drug treatments. Our research was directed to the use of doxorubicin (DOX) and bergapten (5-MOP). The former is broadly considered the most active single agent available for the treatment of breast cancer, the second is a natural psoralen with an apoptotic effect. The results indicate that both drugs inhibit the cell viability of all cell lines grown on all zeolite scaffolds and that all Pure Zeolite Membranes are more responsive with respect to all Mixed Matrix Membranes. Moreover, the results after treatment with DOX at a concentration of 7.4µM for 24h, show that the expression of the matrix metalloproteinases (MMP-2 and MMP-9) is greatly reduced in both cell lines, especially in those adherent on Pure Zeolite Scaffolds.

Influence of zeolite PZC and pH on the immobilization of cytochrome c: a preliminary study regarding the preparation of new biomaterials.

The adsorption of cytochrome c on to zeolite crystals and membranes with different chemical composition and structure was studied. The structure and texture of zeolite materials were identified by X-ray diffraction (XRD) and scanning electron microscopy (FESEM), while the variation of protein conformation was studied by Fourier transform infrared attenuated total reflectance (FTIR-ATR) analysis. In order to separate the influence of zeolite structures from the effect of composite membranes, a through analysis of the cytochrome c adsorption was performed on different crystals by varying several experimental parameters such as: pH value, protein amount, zeolite structures and chemical compositions. It is shown that the electrostatic type of interaction seems to be of the utmost importance to govern the immobilization, while the zeolite Brönsted acidity of the support is the subordinate parameter which differentiates the adsorption performances of different zeolite structures (that distinct for chemical composition of the framework).