Zeolitic Volcanic Tuff Research Articles

Low-Cost Carbon Paste Cu(II)-Exchanged Zeolite Amperometric Sensor for Hydrogen Peroxide Detection

The aim of this work was to explore the possibility of using a Cu-exchanged zeolitic volcanic tuff (which is natural and easy to prepare and apply) for the preparation of a new low-cost carbon paste amperometric sensor for H2O2 detection. The properties of the zeolitic volcanic tuff were determined using chemical analysis, energy-dispersive X-ray spectroscopy, the specific surface area, electron microscopy, X-ray diffraction spectroscopy, and Fourier-transform infrared spectroscopy. The sensor was successfully built and operates at pH 7, at an applied potential of −150 mV Ag/AgCl/KClsat, presenting a sensitivity of 0.87 mA M−1, a detection limit of 10 µM and a linear domain up to 30 mM H2O2. These good electroanalytic parameters for H2O2 detection (a low detection limit and high sensitivity) support the possibility of using these sensors for the detection of many analytes in environmental, food and medical applications.

Simultaneous Removal of Heavy Metals (Cu, Cd, Cr, Ni, Zn and Pb) from Aqueous Solutions Using Thermally Treated Romanian Zeolitic Volcanic Tuff.

Increased concentrations of heavy metals in the environment are of public health concern, their removal from waters receiving considerable interest. The aim of this paper was to study the simultaneous adsorption of heavy metals (Cu, Cd, Cr, Ni, Zn and Pb) from aqueous solutions using the zeolitic volcanic tuffs as adsorbents. The effect of thermal treatment temperature, particle size and initial metal concentrations on the metal ions sorption was investigated. The selectivity of used zeolite for the adsorption of studied heavy metals followed the order: Pb > Cr > Cu > Zn > Cd > Ni. The removal efficiency of the heavy metals was strongly influenced by the particle sizes, the samples with smaller particle size (0–0.05 mm) being more efficient in heavy metals removal than those with larger particle size (1–3 mm). Generally, no relevant changes were observed in heavy metals removal efficiency for the treatment temperatures of 200 °C and 350 °C. Moreover, at a higher temperature (550 °C), a decrease in the removal efficiencies was observed. The Cd, Zn, Cu, Cr, Zn and Ni sorption was best described by Langmuir model according to the high values of correlation coefficient. The pseudo-first-order kinetic model presented the best correlation of the experimental data.

Characteristics of Volcanic Tuff from Macicasu (Romania) and Its Capacity to Remove Ammonia from Contaminated Air.

In the present work, the capability of the volcanic tuff from Macicasu (Romania) to remove ammonia (NH3) from air with different contamination levels during 24 h of adsorption experiments was investigated. The natural zeolitic volcanic tuff was characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), the Brunauer–Emmett–Teller (BET) method, inductively coupled plasma optical emission spectrometry (ICP-OES), and thermogravimetric analysis (TGA). The adsorption capacities varied between 0.022 mg NH3 g−1 zeolite and 0.282 mg NH3 g−1 zeolite, depending on the NH3 concentrations in the air and at the contact time. The nonlinear forms of the Langmuir and Freundlich isotherm models were used to fit the experimental data. Additionally, the adsorption of NH3 was studied using nonlinear pseudo-first-order (PFO), pseudo-second-order (PSO), and Elovich kinetic model. Based on the total volume of pores of used volcanic tuff, the NH3 was removed from the air both due to the physical adsorption of NH3 gas and the ion exchange of NH4+ (resulted from a reaction between NH3 and H2O adsorbed by the zeolite). Depending on the initial NH3 concentration and the amount of volcanic tuff, the NH3 concentrations can be reduced below the threshold of this contaminant in the air. The adsorption capacity of NH3 per unit of zeolite (1 g) varied in the range of 0.022–0.282 mg NH3 g−1 depending on the NH3 concentration in the air.

Exploring the Properties of Micronized Natural Zeolitic Volcanic Tuff as Cosmetic Ingredient.

This study explores the characteristics of a micronized natural zeolitic volcanic tuff (MZ) as ingredient in cosmetic formulations. In particular, the purpose was to prepare and investigate the organoleptic and physicochemical properties of two representative cosmetic formulations containing MZ. The MZ samples were characterized using X-ray fluorescence (XRF), X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. pH, cation exchange capacity (CEC), apparent density, chemical composition and particle size distribution of MZ samples were also determined. The micronization treatment applied did not produce significant structural and physicochemical changes with respect to the raw zeolitic volcanic tuff. The prepared formulations containing 5% MZ with different particle sizes (100–125 µm and 125–250 µm) were subjected to preliminary and accelerated stability tests, and the pH and organoleptic properties were also evaluated. The cosmetic formulations presented a pH of 4.3, a pleasant touch, good spreadability, easy application on skin, no color alteration and a good stability after 15, 30 and 60 days of storage at room temperature, low temperature and freezer during the accelerated stability tests. The obtained results endorse the MZ as suitable for the development of formulations exploiting the clinoptilolite properties as a cosmetic ingredient.

Na+ - NH4+ cation exchange study on treated zeolitic volcanic tuff in fixed bed column

Na+ - NH4+ cation exchange study on treated zeolitic volcanic tuff in fixed bed column

The usage of a zeolitic composite for quality improvement of copper contaminated mining wastewaters

In this paper, a new material based on zeolite has been investigated in an attempt to explore the possibility of using it as an efficient adsorbent of copper(II) from industrial wastewater. This composite material is composed of volcanic tuff (containing 83 % zeolite) and cellulose in a 4 to 1 ratio. The performances of the new adsorbent composite have been examined against those of a common adsorbent, the zeolitic volcanic tuff. The adsorption studies were carried out in a batch process at room temperature, and the effect of various parameters (i.e., initial concentration, contact time, adsorbent dosage and pH) was tested. The experimental data have been modeled with Langmuir, Freundlich and Temkin isotherms. The results correspond to Langmuir model showing a monolayer adsorption with a maximum adsorption capacity of 12.74 mg g−1 at 25 °C. The copper adsorption onto zeolitic composite was well described by a pseudo-second order kinetic model. The experimental results indicate a superior adsorption of copper(II) onto the new adsorbent when compared against the common zeolite.

Physical-chemical and electrochemical characterization of Fe-exchanged natural zeolite applied for obtaining of hydrogen peroxide amperometric sensors

This work demonstrates that a Fe-exchanged zeolitic volcanic tuff from Cepari (Fe/CV) (Bistrita-Nasaud County, Romania) is suitable for the amperometric detection of H2O2, using new modified carbon paste electrodes based on this material (Fe/CV-CPEs). The physical-chemical characterization of natural (CV) and modified (Fe/CV) forms was realized using chemical analysis, optical microscopy, scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), energy dispersive X-ray spectroscopy (EDX) and Fourier transformed infrared (FTIR) spectroscopy. The resulting electrodes (Fe/CV-CPEs) were investigated using cyclic voltammetry and chronoamperometry measurements. The new electrodes showed good electrocatalytic activity toward H2O2 reduction. The calibration curve for H2O2 determination was linear up to 0.1mM, with a detection limit (signal to noise ratio of 3) of 20μM.

Valorification of Volcanic Tuff in Constructions and Materials Manufacturing Industry

Abstract Zeolitic volcanic tuffs are important local reserve, which can be exploited in building materials industry both as rocks and the preparation of mortar for masonry, lightweight concrete or autoclaved aerated concrete. This study presents the results of the tests performed on different mortar recipes that are based on zeolitic volcanic tuff (from Macicas quarry situated in the north-western part of Cluj-Napoca area) used as a substitute for cement or aggregate. The aim of the study is to obtain new building materialmade from local resources that can be used to realize new masonry works and to rehabilitate the old ones.

Haneş and Valea Vinului (Romania) closed mines Acid Mine Drainages (AMDs) – Actual condition and passive treatment remediation proposal

Acid Mine Drainages (AMDs) from Haneş and Valea Vinului (Romania) closed mines were considered for characterization and treatment using a local zeolitic volcanic tuff, ZVT, (Măcicaş, Cluj County, Romania). Water samples were collected from two locations, before and after discharging point in case of Haneş mine, and on three horizons in case of Valea Vinului mine. Physico-chemical (pH, total solid, heavy metal ions concentration) analyses showed that the environment is strongly affected by these AMD discharges even if the mines were closed years ago. Iron, manganese and zinc were the main pollutants identified in Haneş mine AMD, while zinc is the one mainly present in case of Valea Vinului AMD. A batch technique (no stirring) in which the ZVT was put in contact with the AMD sample was proposed as a passive remediation technique. ZVT successfully remove heavy metal ion from AMD. According to heavy metal ion concentrations, removal efficiencies are reaching 100%, varying as follows, Fe2+>Zn2+>Mn2+. When the ZVT was compared with two cationic resins (strong, SAR and weak acid, WAR) the following series was depicted, SAR>ZVT>WAR.

Phenol removal from wastewater by adsorption on zeolitic composite

It is well known that adsorption is an efficient method of removal of various pollutants from wastewater. The present study examines the phenol removal from water by adsorption on a new material, based on zeolitic volcanic tuff. This compound contains zeolitic tuff and cellulose, another known adsorbent, in a mass ratio of 4 to 1. The performances of the new adsorbent composite were compared with those of a widely used adsorbent material, zeolitic volcanic tuff. The adsorbent properties were tested on batch synthetic solutions containing 1-10mgL(-1) (1-10ppm) phenol, at room temperature without pH adjustment. The influence of the adsorbent dose, pH and contact time on the removal degree of phenol from water was investigated. The experimental data were modeled using the Langmuir, Freundlich, and Temkin adsorption isotherms. The Langmuir model was found to best represent our data revealing a monolayer adsorption with a maximum adsorption capacity between 0.12 and 0.53mgg(-1) at 25°C, for 2.00g of adsorbent, depending on the initial phenol concentration. The adsorption kinetic study was performed using a pseudo-first- and pseudo-second-order kinetic models illustrating that phenol adsorption on zeolite composite is well described by pseudo-first kinetic equations. Our results indicated that phenol adsorption on the new adsorbent composite is superior to that on the classic zeolite.

Application of linear regression analysis for iron and copper removal process using natural zeolites

Natural zeolites (zeolitic volcanic tuffs) cropped out from three regions of Transilvania, Vultureni (V), Pâglisa (P) and Măcicas (M), were evaluated in the process of iron (V, P, M) and copper (M) removal from wastewaters. Iron and copper removal process was studied using a fixed bed column, when equilibrium and kinetic data were acquired. Four isotherms, Langmuir, Freundlich, Langmuir–Freundlich and Redlich–Peterson, were used to fit the experimental data obtained for each natural zeolite sample. Parameters of the adsorption isotherms were estimated from the experimental equilibrium data using MATLAB. Using these data the best fit with one of the chosen isotherm can be found. Isotherm constants were determined by linear regression analysis of the experimental data. We concluded that the mathematical model based on Freundlich isotherm is the most appropriate to describe the iron and copper exchange on our natural zeolite samples.

Removal of Pb(II) from water by natural zeolitic tuff: Kinetics and thermodynamics

The present study was aimed at examining the ability of a natural zeolitic volcanic tuff to remove Pb(II) ions from aqueous solutions under various conditions. The effects of various parameters such as optimum adsorbent mass, contact time, pH of the medium, Pb(II) concentration, and temperature were investigated. In addition, different adsorption isotherms were obtained using concentrations of Pb(II) ions ranging from 1 mg/L to 200 mg/L. The adsorption process follows second-order reaction kinetics and follows the Langmuir adsorption isotherm. The thermodynamic parameters are discussed in this article, including changes in Gibbs free energy, entropy, and enthalpy, for the adsorption of Pb(II) on tuff, and it is revealed that the adsorption process was spontaneous and exothermic under natural conditions. The maximum removal efficiency of 92% was obtained at a pH of 5 with a 25-min contact time for a 10 g/L solid-to-liquid ratio and an initial heavy metal concentration of 100 mg/L.

Evaluation of Ammonium Removal Performances of Some Zeolitic Volcanic Tuffs from Transylvania, Romania

In this study, zeolitic volcanic tuffs (ZVT) originated from Transylvania, Romania were used, to remove ammonium ions from model solution. The zeolitic volcanic tuff samples used as ionic exchangers were characterized by means of chemical analysis, optical microscopy, SEM, XRD, FTIR, and BET analysis. The main zeolite species identified in the volcanic tuffs from mentioned areas is clinoptilolite. All samples were subjected to chemical treatment with HCl and NaCl, followed by the ionic exchange process. The ionic exchange process was realized in batch and fixed bed column conditions. We found that ionic exchange efficiency varies according to their zeolite content, therefore P (Pâglişa) and M (Măcicaş) samples, which have the highest clinoptilolite content, proved to be more efficient.

Investigations on some zeolitic volcanic tuffs from Cluj County (Romania), used for zinc ions removal from aqueous solution

Representative samples of zeolitic tuffs from M a cica s , Aluni s , and Apahida occurrences (Cluj County, Romania) were investigated using optical microscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD) and wet chemical analyses. The studied tuff samples are represented mainly by vitric and vitric crystal varieties. The mineral assemblage suggests a rhyodacitic volcanic tuff. Diagenetic alteration led to the formation of zeolites, mainly clinoptilolite. Zn 2+ removal was performed on some bulk samples: Alunis (labelled A1), Apahida (Ap), and Macicas (M2) grain size of 0.2-0.4 mm. Each sample was chemically modified with HCl 1M (Z-H form) and NaCl + NaOH 1M pH = 10 (Z-Na form). The ionic exchange experiments were performed in a batch reactor (immobile phases) and in a fixed bed column. Ionic exchange efficiencies for the samples considered are presented for static and dynamic regimes. Removal efficiencies higher than 53.97% and exchanged Zn 2+ quantities higher than 1.05 mg/g were obtained. Therefore, the zeolitic tuffs under investigation are considered to be active in the ionic exchange process and can be used in wastewaters treatment to remove Zn 2+ ions. The results for all the samples considered in batch and fixed bed

Iron-enriched natural zeolite modified carbon paste electrode for H2O2 detection

This work demonstrates that iron-enriched natural zeolitic volcanic tuff (Paglisa deposit, Cluj county, Transilvania, Romania) resulting from a previous use as adsorbent in wastewater treatment can be recycled into effective electrode modifier applied to the electrocatalytic detection of hydrogen peroxide. After physico-chemical characterization of tuff samples using various techniques such as chemical analysis, X-ray diffraction, scanning electron microscopy, infrared spectroscopy, BET analysis and X-ray photoelectron spectroscopy, the electrochemical response of the iron-enriched zeolites was studied on the basis of solid carbon paste electrodes modified with these samples. The results indicate that iron centers in the zeolite are electroactive and that they act as electrocatalysts in the voltammetric and amperometric detection of H2O2. Best performance was achieved in phosphate buffer at pH 7, showing a sensitivity of 0.57 mA M−1 cm−2, a detection limit down to 60 μM, and a linear domain up to 100 mM H2O2.

Detection and Isolation of Antiatherogenic and Antioxidant Substances Present in Olive Mill Wastes by a Novel Filtration System

Olive mill waste water (OMWW) is a major environmental issue in the Mediterranean. We address this problem by investigating the wastes for the presence of biologically active compounds already detected in both olive oil and pomace. Two initial OMWW samples were filtered using two microporous filtering media: (a) clayey diatomite and (b) zeolitic volcanic tuffs, obtaining three filtered samples from each. All initial and filtrated samples were tested for their activity on platelet activating factor (PAF)-induced aggregation. The results showed that the initial samples contain biologically active compounds (PAF inhibitors) and that in their respective last-eluted filtered samples these compounds are purified. These eluted samples, along with their corresponding initial OMWW, were further separated with HPLC and the purified fractions responsible for the aforementioned biological activity, were further studied using chemical determinations and MS analysis. It was confirmed that the PAF inhibitor present in these fractions resembles the one isolated from olive oil. These results offer a new approach on the OMWW handling by offering an alternative use of this waste as starting material for nutritional and/or pharmaceutical purposes in the future.

Voltammetric Detection of Urea on an Ag-Modified Zeolite-Expanded Graphite-Epoxy Composite Electrode.

In this paper, a modified expanded graphite composite electrode based on natural zeolitic volcanic tuff modified with silver (EG-Ag-Z-Epoxy) was developed. Cyclic voltammetry measurements revealed a reasonably fast electron transfer and a good stability of the electrode in 0.1 M NaOH supporting electrolyte. This modified electrode exhibited moderate electrocatalytic effect towards urea oxidation, allowing its determination in aqueous solution. The linear dependence of the current versus urea concentration was reached using square-wave voltammetry in the concentrations range of urea between 0.2 to 1.4 mM, with a relatively low limit of detection of 0.05 mM. A moderate enhancement of electroanalytical sensitivity for the determination of urea at EG-Ag-Z-Epoxy electrode was reached by applying a chemical preconcentration step prior to voltammetric/amperometric quantification.

Electrochemical behavior of carbon paste electrodes modified with methylene green immobilized on two different X type zeolites

Two new modified carbon paste electrodes (CPEs) based on two different X type zeolites, a natural zeolitic volcanic tuff (NZ) and a NaX type synthetic zeolite (SZ), modified with methylene green (MG) were developed. Cyclic voltammetry measurements revealed a reasonably fast electron transfer rate and a good stability for both investigated electrodes. The observed differences between the electrochemical behavior of MG-NZ-CPEs and MG-SZ-CPEs (the effect of pH on the formal standard potential, the magnitude of the rate constants for heterogeneous electron transfer and electrode response decay) were explained in terms of zeolites structure. The modified electrodes showed moderate electrocatalytic effect towards H2O2 reduction and a relatively low limit of detection (0.5 mM for MG-NZ-CPEs).

Kinetic and thermodynamic aspects of U(VI) and Th(IV) sorption on a zeolitic volcanic tuff

The sorption behavior of U(VI) and Th(IV) from simulated waste solutions on a zeolitic volcanic tuff from Nereju (Vrancea, Romania) has been studied in the absence of the ionic competition as a function of contact time, radioactive ions concentration, temperature and pH using a batch mode technique. The effect of the above-mentioned parameters on the sorption efficiency was discussed. The apparent thermodynamic parameters of the sorption of uranium and thorium onto the considered volcanic tuff were calculated, showing that the process is endothermic and higher temperatures favor the sorption process.

Zeolitic volcanic tuffs from Măcicaş (Cluj County), natural raw materials used for NH4+ removal from wastewaters

Volcanic tuffs out cropping in Măcicaş area (Cluj County) have been investigated and tested for their ammonium removal capacity. The zeolitic volcanic tuffs from Măcicaş are mainly represented by vitric and vitric crystal tuffs. In this region, significant amounts of volcanic glass in the pyroclastic sequence have been replaced by zeolites (between 50-80 %). The main zeolite species identified in volcanic tuffs from Măcicaş is clinoptilolite and subordinately mordenite. The zeolitic tuff samples considered in zeolitic sodium form (labeled M1-Na and M2-Na) are tested in ammonium removal experiments. The ammonium ions were completely removed from 0.0716g/dm3 NH4+ solution onto 10g of zeolitic material in static regime. In dynamic regime, the ammonium ions were completely removed after 250 ml and 500 ml solution passed on M1-Na and M2-Na sample respectively. Also the zeolite exhaustion takes place after more than 1500 ml solution is processed in both cases. The ionic exchange properties suggest that the zeolitic tuff of the Măcicaş region can be used as a final stage (following the biological process) in wastewater treatment plants in order to assure compliance with environmental standards.