A. Godelitsas

Thorium and uranium uptake by natural zeolitic materials

Abstract The thorium and uranium uptake from their aqueous solutions by unpretreated and NaCl-pretreated zeolite-bearing volcanoclastic rock samples from Metaxades (Thrace, Greece) has been studied using a batch-type method. The concentration of the solutions varied between 50 and 20 000 mg/l. The NaCl pretreatment of the materials improved the thorium but not the uranium uptake. The absolute thorium uptake by the pretreated material, determined using neutron activation and X-ray fluorescence techniques, reached 12.41 mg/g, whereas the uranium uptake by the raw material was 8.70 mg/g. The uptake distribution coefficients ( K d ) indicated that the relative thorium and uranium uptake is higher for initial concentrations below 250 mg/l. The zeolitic materials showed exceptional resistance to the initial low pH of the solutions used. The pH in was significantly increased due to the simultaneous hydrogen-ion uptake. The thorium and uranium uptake is a rather complicated phenomenon related to the aqueous chemistry of the elements, the nature of the constituent minerals and the properties of the zeoliferous rock specimens. The various metal species are bound through different uptake processes such as ion-exchange, adsorption and surface precipitation. Microporous minerals (zeolites, phyllosilicates) are mainly responsible for the considerable uptake ability of the rock samples studied.

The chemical behavior of natural zeolites in aqueous environments: Interactions between low-silica zeolites and 1 M NaCl solutions of different initial pH-values

A natural zeolitic material composed of microscale intergrowths of the low-silica zeolites natrolite and thomsonite (NAT/THO) was found to be more reactive in distilled water compared to the high-silica zeolites heulandite and stilbite. Relevant experiments using 1 M NaCl solutions of different initial pH-values revealed a pH increase in the acidic region and an analogous decrease in the basic region, indicating that the NAT/THO material shows a tendency to neutralize the solutions behaving either as a proton acceptor or as a proton donor. This amphoteric character is related to the H+ uptake, as well as to the OH− attack to surface reactions sites of the crystals. However, phase transformations to analcime in the base-treated low-silica zeolites were also noted. The interaction of the hydrogen ions with the aluminosilicate framework of the zeolites caused in a small extent, degradation-dissolution phenomena, resulting in surface-eroded crystals.

Characterisation of Zeolitic Materials with a HEU‐Type Structure Modified by Transition Metal Elements: Definition of Acid Sites in Nickel‐Loaded Crystals in the Light of Experimental and Quantum‐Chemical Results

Nickel-loaded HEU-type zeolite crystals have been obtained by well-known synthetic procedures and characterised by X-ray fluorescence (XRF), scanning-electron microscopy/ energy-dispersive spectroscopy (SEM-EDS), FT-IR, diffuse reflectance UV/ Vis spectroscopy (DR(UV/Vis)S) and X-ray photoelectron spectroscopy (XPS) measurements as non-homoionic and non-stoichiometric substances containing exchangeable hydrated Ni2+ ions in the micropores and nickel hydroxide phases supported on the surface. Thermogravimetric analysis/differential gravimetry (TGA/DTG) and differential thermal analysis (DTA) demonstrated that full dehydration below approximately 400 degrees C follows a clearly endothermic process, whereas at higher temperatures the zeolite is amorphised and finally partially recrystallised to Ni(Al,Si) oxides, detected by powder X-ray powder diffraction (XRD). The solid acidity of NiHEU, initially determined by temperature-programmed desorption (TPD) of ammonia to be 8.93 mgg(-1) NH3, is attributed to the weak acid sites (fundamentally Lewis sites) resolved at approximately 183 degrees C, and to the strong acid sites (essentially Brønsted sites) resolved at approximately 461 degrees C in the TPD pattern. A more sophisticated study based on in situ/ex situ FT-IR with in situ/ex situ 27Al MAS NMR and pyridine (Py) as a probe molecule, revealed that the Lewis acid sites can be attributed primarily to Ni2+ ions, whereas the Brønsted ones can probably be associated with the surface-supported nickel hydroxide phases. The spectroscopic measurements in conjunction with powder XRD and 29Si MAS NMR data strongly suggest that distorted Al tetrahedra are formed during the dehydration process and Py chemisorption/complexation (NiHEU-Py), whereas the crystal structure is remarkably well preserved in the rehydrated material (NiHEU-Py/R). The structural, electronic, energetic and spectroscopic properties of all possible nickel(II) aqua and dihydroxy complexes absorbed in the zeolite micropores or supported on the zeolite surface were studied theoretically by density functional theory (DFT). The computed proton affinity, found to be in the range 182.0-210.0 kcalmol(-1), increases with increasing coordination number of the aqua and dihydroxy nickel(II) complexes.

Multivariate statistical analysis of the hydrogeochemical and isotopic composition of the groundwater resources in northeastern Peloponnesus (Greece).

The present study involves an integration of the hydrogeological, hydrochemical and isotopic (both stable and radiogenic) data of the groundwater samples taken from aquifers occurring in the region of northeastern Peloponnesus. Special emphasis has been given to health-related ions and isotopes in relation to the WHO and USEPA guidelines, to highlight the concentrations of compounds (e.g., As and Ba) exceeding the drinking water thresholds. Multivariate statistical analyses, i.e. two principal component analyses (PCA) and one discriminant analysis (DA), combined with conventional hydrochemical methodologies, were applied, with the aim to interpret the spatial variations in the groundwater quality and to identify the main hydrogeochemical factors and human activities responsible for the high ion concentrations and isotopic content in the groundwater analysed. The first PCA resulted in a three component model, which explained approximately 82% of the total variance of the data sets and enabled the identification of the hydrogeological processes responsible for the isotopic content i.e., δ(18)Ο, tritium and (222)Rn. The second PCA, involving the trace element presence in the water samples, revealed a four component model, which explained approximately 89% of the total variance of the data sets, giving more insight into the geochemical and anthropogenic controls on the groundwater composition (e.g., water-rock interaction, hydrothermal activity and agricultural activities). Using discriminant analysis, a four parameter (δ(18)O, (Ca+Mg)/(HCO3+SO4), EC and Cl) discriminant function concerning the (222)Rn content was derived, which favoured a classification of the samples according to the concentration of (222)Rn as (222)Rn-safe (<11 Bq·L(-1)) and (222)Rn-contaminated (>11 Bq·L(-1)). The selection of radon builds on the fact that this radiogenic isotope has been generally related to increased health risk when consumed.

Uranium sorption from aqueous solutions on sodium-form of HEU-type zeolite crystals

The uranium sorption from aqueous solutions (concentration range 50–20.000 mg/l) by the sodium-form (Na-form) of HEU-type zeolite crystals (particle-size <20 μm) has been investigated by means of a batch-type method. The INAA, RI-XRF, powder-XRF, SEM-EDS and FT-IR techniques were used for the study of the experimental products. The absolute uranium uptake by the material reached the value of 11.68 mg/g in the case of initial concentraton 20,000 mg/l. On the other hand theKd-values indicated that the relative uranium uptake, and consequently the percentage of removal, is higher for concentrations below 100 mg/l. The uranium uptake by the zeolite is attributed to different sorption processes such as ion-exchange, adsorption and surface precipitation, taking place both to the interior and the surface of the crystals and strongly depending on the pH of the solutions. The investigated zeolitic material was sufficiently resistant at the low initial pH of the solutions with dealumination phaenomena only observed in the case of the most acidic solution used.

Characterisation and management of ash produced in the hospital waste incinerator of Athens, Greece

Bottom and fly ash samples (BASH and FASH) from the APOTEFROTIRAS S.A. medical waste incinerator (Athens, Greece) were investigated. Powder-XRD data and geochemical diagrams showed BASH to be an amorphous material, analogous to basaltic glass, and FASH consisting of crystalline compounds (mainly CaClOH). Bulk analyses by ICP-MS and point analyses by SEM-EDS indicated a high content of heavy metals, such as Fe, Cu and Cr, in both samples. However, BASH was highly enriched in Ni while FASH was additionally enriched in Zn and Pb. Gamma-ray measurements showed that the radioactivity of both ash samples, due to natural and artificial radionuclides ((137)Cs, (57)Co), was within the permissible levels recommended by IAEA. According to EN-type leaching tests, BASH was practically inert with regard to the mobility of the hazardous elements in aqueous media. FASH, however, showed a relatively high EN (and TCLP) leachability with regard to Pb and Zn. Finally, the stabilisation method, suggested for the treatment of FASH, included compression of the powder into briquettes using an appropriate machine and embedding the briquettes into pozzolanic cement blocks. After this treatment, TCLP and EN-type tests showed minimal release of Pb and Zn, thereby demonstrating a reliable management of ash waste.

Interaction of natrolite and thomsonite intergrowths with aqueous solutions of different initial pH values at 25°C in the presence of KCl : Reaction mechanisms

Natural zeolitic material composed of natrolite and thomsonite intergrowths (NAT/THO) was treated in solutions of different initial pH values at 25°C under N2 atmosphere and in 1M KCl as ionic modulator, until pH equilibration. The solid experimental products were studied by means of powder X-ray diffraction (XRD), scanning electron microscopy-energy dispersive system (SEM-EDS), Fourier-transformed infra-red (FTIR) and thermogravimetric analysis/differential thermal analysis (TGA/DTA). The liquid experimental products were analysed using atomic absorption spectroscopy (AAS) and atomic emission spectroscopy (AES). The NAT/THO material exhibited an amphoteric character with a tendency to neutralise the reacting solutions. The pH equilibration was faster for the acidic region than for the basic one. The H+ ions are chemisorbed on the bulk material, whereas the OH− ions promote a proton detachment from the exchangable cation-water complexes. No Brœnsted acidity, possibly responsible for the neutralisation in the basic region, was found by temperature-programmed desorption (TPD) measurements. Reaction mechanisms involving hydrolysis and degradation-dissolution are proposed. Zeolite crystals remaining at the end of the experiments showed no loss of crystallinity, phase transformation nor even framework dealumination. The insertion of K+ into the zeolites is suggested here as the reason as to why no collapse of their crystal structure occurred in the most acidic solutions causing the zeolites to be more resistant to chemical weathering.

Heavy metal uptake by zeoliferous rocks from Metaxades, Thrace, Greece : an exploratory study

The uptake of mercury, cadmium and silver from aqueous solutions by unpretreated and NaCl-pretreated clinoptilolite-bearing volcaniclastic rocks from Metaxades (Thrace, Greece) has been studied using a batch method with radioactive tracers (197Hg,115Cd and110mAg). The concentration of the solutions used varied between approximately 1000 and 17000 ppm. An improvement of the uptake ability was observed in the case of NaCl-pretreated material for all the investigated metals and especially for mercury at the upper part of the concentration range studied. The heavy metal uptake is attributed to different mechanisms taking place both at the rock grains and their individual mineral components.

Investigation of chemical processes at mineral surfaces using accelerator-based and surface analytical techniques: heavy metal sorption on zeolite crystals

Abstract Natural HEU-type zeolite crystals were exposed to copper, mercury, lead and uranium aqueous solutions. The reacted zeolite samples obtained were examined using SEM-EDS and further investigated by means of 12 C-RBS and XPS. The 12 C-RBS study proved an inhomogeneous depth distribution of sorbed metals on the mineral surface and particularly an intense metal accumulation in the near-surface layers of the material, which can be attributed to an anomalous diffusion of metal cations into the micropores due to ion-exchange reactions. This phenomenon strongly depends on the size of the zeolite crystals, the treatment time and the type of the exchangeable cations. In addition in the case of mercury and uranium, metal-rich “layers” supported on the surface could also be identified. The XPS results showed that these “layers” consist of metal oxides and hydroxides adsorbed and precipitated during the interaction of the zeolite with the heavy metal-containing aqueous solutions. The surface morphology and microtopography seem to play an important role to the chemical processes taking place at the zeolite surface.

Extra-framework cation release from heulandite-type rich tuffs on exchange with NH4+

The outgoing cations of Greek heulandite-rich tuff samples (heulandite type-III, 91wt.%, mica 4wt.%, feldspar 5wt. %, CEC 2.22meq/g) were analysed upon exchange with ammonium acetate using atomic absorption spectrometry (AAS). The kinetic curves of each cation were investigated over a total time of contact of 720h with sampling at frequent intervals. The materials were examined by powder X-ray diffraction, SEM-EDS, and AAS. The sorption ability was measured using the ammonium acetate saturation method. It was found that Ca(2+) presents an unexpected extra-framework release and a surprisingly high degree of exchange (90%). The exchange of Mg (57%) is also worthy of note whereas the behavior of K(+) showed an expected rapid initial release. The behavior of Na(+) must be similar. However, its lower concentration in the zeolitic material minimizes its overall significance somewhat. On the other hand, Ca(2+) and Mg(2+) release is kinetically much slower, compared to that of alkali metal ions, and this phenomenon indicates that different exchange energies are needed till final equilibrium.