Ioannis Pashalidis

Activated biochar derived from cactus fibres – Preparation, characterization and application on Cu(II) removal from aqueous solutions

The adsorption efficiency of activated biochar prepared from cactus fibres regarding the removal of Cu(II) from aqueous solutions has been investigated as a function of various physicochemical parameters (e.g. pH, initial metal concentration, ionic strength, temperature and contact time). Activation of the biochar took place using nitric acid oxidation and characterisation was performed by SEM analysis, FTIR spectroscopy, N2 adsorption and acid-base titrations. The results show that laminar structures constitute the material and carboxylic moieties are the predominant binding sites. The experimental data were analyzed by the Langmuir, Freundlich and Dubinin-Radushkevich adsorption models and the monolayer adsorption capacity was found to be 3.5 mol kg(-1). The effect of ionic strength and temperature on the adsorption efficiency indicates that at low pH outer-sphere and at near neutral pH inner-sphere complexes are the predominant surface species and the kinetic data obtained were fitted very well by the Lagergren rate expression.

Radon levels in Cyprus

Radon levels in atmospheric and aquatic systems in Cyprus have recently been measured using the radon monitor Alpha Guard. Indoor and outdoor radon levels were obtained in situ, whereas analysis of radon concentrations in water was performed using tap and ground water samples collected from several areas of the island. The average value for outdoor and indoor radon concentration is 11+/-10 and 7+/-6 Bq m(-3), respectively, and for tap and ground water 0.4 Bq l(-1) and 1.4 Bq l(-1), respectively. From these data the annual dose equivalent of airborne radon to the Cypriot population is about 0.19 mSv y(-1), which is quite low compared to the total dose equivalent of natural and man-made ionising radiation in Cyprus. Radon levels in aquatic systems are relatively low due to an exhaustive utilisation of ground water resources and also to the increased input of desalinated sea water in the water distribution network and eventually into the ground water reservoirs.

Uranium adsorption by non-treated and chemically modified cactus fibres in aqueous solutions

The adsorption efficiency of Opuntia ficus indica fibres regarding the removal of hexavalent uranium [U(VI)] from aqueous solutions has been investigated prior and after the chemical treatment (e.g. phosphorylation and MnO2-coating) of the biomass. The separation/removal efficiency has been studied as a function of pH, uranium concentration, adsorbent mass, ionic strength, temperature and contact time. Evaluation of the experimental data shows that biosorption is strongly pH-depended and that the MnO2-coated product presents the highest adsorption capacity followed by the phosphorylated and non-treated material. Experiments with varying ionic strength/salinity don’t show any significant effect on the adsorption efficiency, indicating the formation of inner-sphere surface complexes. The adsorption reactions are in all cases exothermic and relatively fast, particularly regarding the adsorption on the MnO2-coated product. The results of the present study indicate that adsorption of uranium from waters is very effective by cactus fibres and particularly the modified treated fibres. The increased adsorption efficiency of the cactus fibres is attributed to their primary and secondary fibrillar structure, which result in a relative relative high specific surface available for sorption.

Effective complex formation in the interaction of 1,2-dimethyl-3-hydroxypyrid-4-one (Deferiprone or L1) with uranium(VI)

In an effort to develop new chelating agents for the decorporation of uranium and other actinides, the interaction of the clinically used 1,2-dimethyl-3-hydroxypyrid-4-one (Deferiprone or L1) with hexavalent uranium was investigated by using UV-VIS spectroscopy and solubility measurements. The complex stoichiometry estimation carried out by the Job plot method indicated that under normal conditions up to pH 8.0 a 1[U(VI)]∶1[L1] complex is formed. The stability constant of the UO2L1+ complex was determined by spectroscopic and solubility experiments and found to be log β11=9.1±0.3. The molar extinction coefficient at pH 7.6 for the complex at 500 nm was estimated to be 650 l·mol−1·cm−1. At ligand concentrations higher than 6·10−4 mol·l−1 the formation of a precipitate was observed. The stoichiometry UO2(L1)2 was identified following FTIR measurements of the red precipitate and UV/VIS spectroscopy after dissolution.

Adsorption of hexavalent chromium on dunite

The paper presents and discusses the effect of various physicochemical parameters (e.g. pH, ionic strength, Cr(VI) initial concentration, amount of the adsorbent, temperature and contact time between metal ion and adsorbent) on the adsorption efficiency of Cr(VI) on dunite in aqueous solutions under atmospheric conditions. Evaluation of the experimental data shows that dunite presents increased affinity for Cr(VI) over a wide pH range and Cr(VI) concentration, and the experimental data are well fitted by the K(d) adsorption model. The relative adsorption is pH dependent and decreases slightly (about 10%) with increasing pH, because of changes in the surface charge of the solid. The effect of the ionic strength is significant (particularly at low pH), indicating the predominance of outer-sphere complexes. Moreover, adsorption experiments at various temperatures, two different pH values (pH 3 and pH 8) and three different ionic strengths (0.0, 0.1 and 1.0 M NaClO(4)), indicate an endothermic but spontaneous entropy-driven processes.

Experimental and theoretical studies on physico-chemical parameters affecting the solubility of phosphogypsum.

Phosphogypsum is a waste by-product of the phosphate fertilizer industry, which is usually disposed in the environment because of its restricted use in industrial applications. Physico-chemical conditions existing in stack fluids and leachates are of major importance and determine solubility and redox stability of phosphogypsum, as well as radionuclide release from stacks to terrestrial environments. The aim of this study is to assess the effect of key parameters (e.g. ionic strength, temperature, pH) on the solubility of phosphogypsum. Phosphogypsum sampling and in-situ measurements were carried out at a coastal stack in Cyprus, solubility experiments were performed in simulated laboratory systems and thermodynamic calculations by means of MINTEQA2, an equilibrium speciation model. Generally, increasing ionic strength and temperature leads to increased phosphogypsum solubility, with the former being much more effective. The increased solubility of phosphogypsum in saline solutions is attributed solely to ionic strength effects on the activity of ionic species in solution and no solid phase transformations could be observed. The effect of pH on phosphogypsum solubility seems to be insignificant at least in a pH range between 4 and 8. Regarding uranium levels, there is a strong correlation between salinity and uranium concentration and linear correlation between phosphogypsum solubility and uranium levels in stack solutions, indicating the incorporation of uranium into the gypsum lattice and the formation of a solid solution.

Hydrophilic olive cake extracts: Characterization by physicochemical properties and Cu(II) complexation

Disposed olive cake generates hydrophilic components that can be mobilized in the aquatic environment. This paper deals with the characterization of such components, isolated by alkaline extraction. It is shown that these substances possess properties very much resembling humic acid, including a substantial inventory of proton exchanging groups. Extraction and purification of the hydrophilic components from the disposed olive cake was performed by the standard approach for isolation of humic acids from solid sources, i.e. alternating alkaline dissolution and acid flocculation, leaving the purified extract in the protonated form. The purified sample was characterized by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), Fourier Transform Infra Red Spectroscopy (FTIR), UV-vis, Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) and Asymmetrical Flow Field-Flow Fractionation (AFFFF). The complex formation properties were investigated by potentiometry using Cu(II) ion selective electrode under atmospheric conditions at I=0.1M NaClO(4) (aqueous solution) and pH 6. The formation constant for the CuHA complex is found to be logbeta=5.3+/-0.4 which is close to the corresponding value (logbeta=5.2+/-0.4) obtained from similar investigations with the commercially available Aldrich humic acid (this study) and corresponding published values for various humic acids. Both, structural properties and complex formation data show that the olive cake extract has considerable similarities with humic acids from different sources, pointing towards potential similarities in environmental behavior and impact.

Removal of trivalent samarium from aqueous solutions by activated biochar derived from cactus fibres

Abstract The efficiency of activated biochar fibres obtained from Opuntia Ficus Indica regarding the sorption of trivalent samarium (Sm(III)) from aqueous solutions was investigated by batch experiments. The effect of various physicochemical parameters (e.g. pH, initial metal concentration, ionic strength, temperature and contact time) on the Sm(III) adsorption was studied and the surface species were characterized by FTIR spectroscopy prior to and after the lanthanide sorption. The experimental results showed that the activated biochar fibres possessed extraordinary sorption capacity for Sm(III) in acidic solutions ( q max =90 g/kg, pH 3.0) and near neutral solutions ( q max =350 g/kg, pH 6.5). This was attributed to the formation of samarium complexes with the surface carboxylic moieties, available in high density on the lamellar structures of the bio-sorbent.

Adsorption of boron on iron-oxide in aqueous solutions

Abstract The adsorption of boron on iron-oxide (FeO(OH)) has been investigated in aqueous solutions as a function of pH, ionic strength, temperature, boron concentration and amount of the adsorbent. Analysis of the experimental data indicates that boron adsorption on iron-oxide is based on the replacement of a water molecule by a boric acid molecule. Evaluation of the experimental data reveals that boron adsorption on iron-oxide is an exothermic process, which is not significantly affected by the ionic strength, indicating the formation of inner-sphere complexes. Furthermore, the maximum adsorption capacity of iron-oxide for boron has been determined using the Langmuir isotherm and is equal to 0.03 mol/kg. The conditional formation constant of the surface complexes under optimum conditions has been found to be logβ∗ = 4.5, indicating the relative high affinity of iron-oxide for boron.

Uranium levels in Cypriot groundwater samples determined by ICP-MS and α-spectroscopy

The uranium concentration and the isotopic ratio (238)U/(234)U have been determined in Cypriot groundwater samples by ICP-MS after ultrafiltration and acidification of the samples and α-spectroscopy after pre-concentration and separation of uranium by cation-exchange (Chelex 100 resin) and electro-deposition on stainless steel discs. The uranium concentration in the groundwater samples varies strongly between 0.1 and 40 μg l(-1). The highest uranium concentrations are found in groundwater samples associated with sedimentary rock formations and the obtained isotopic ratio (238)U/(234)U varies between 0.95 and 1.2 indicating basically the presence of natural uranium in the studied samples. The pH of the groundwater samples is neutral to weak alkaline (7 < pH < 8) and this is attributed to the carbonaceous content of the sedimentary rocks and the ophiolitic origin of the igneous rocks, which form the background geology in Cyprus. Generally, in groundwaters uranium concentration in solution increases with decreasing pH (7 < pH < 8) and this is attributed to the fact that at lower pH dissolution of soil minerals occurs, and uranium, which is adsorbed or forms solid solution with the geological matrix enters the aqueous phase. This is also corroborated by the strong correlation between the uranium concentration and the electrical conductivity (e.g. dissolved solids) measured in the groundwaters under investigation.