This study presents the effect of thermal treatment (450, 500, 600, 750, and 800 °C) on a Romanian clinoptilolite-rich natural zeolite, along with the interaction of raw and thermally treated zeolites with simulated gastric fluid (SGF, pH = 1.20) at different zeolite to SGF ratios and exposure times. The zeolites were characterized using gravimetric analysis, X-ray fluorescence, powder X-ray diffraction (pXRD), and Fourier transform infrared (FT-IR) spectroscopy. The chemical composition of the zeolite subjected to thermal treatment did not change significantly with the increase of temperature. Structural changes were not detectable by pXRD and FT-IR analyses in the zeolites thermally treated up to 500 °C, while above 600 °C a gradual structural breakdown of zeolite was noticed. At high temperatures, the broad, low-intensity peaks in pXRD patterns indicated the partial amorphization of the crystalline structure. The pXRD and FT-IR analyses showed that the crystalline structure of zeolites remains unaffected after their exposure to SGF. The results revealed that the amounts of Fe, Na, Mg, K, Ca, Al, and Si released depends mainly on the zeolite to SGF ratio, and to a lower extent on the thermal treatment temperature, while the exposure time of 1 to 7 days does not have a significant impact on the elements released in SGF.

Natural zeolites are hydrated aluminosilicate minerals that, due to their remarkable physical-chemical properties of being molecular sieves and cation exchangers, have applications in different areas such as environmental protection, catalysis, animal feed, and dietary supplements. Since natural zeolites may contain traces of undesirable compounds such as toxic metals, the accurate quantification of these elements is necessary. In this study, a direct method for Hg determination in zeolite samples based on the thermal desorption atomic absorption spectrometry (TD-AAS) technique is fully validated, taking into account the legislative requirements in the field. The chosen quantification limit was 0.9 µg kg−1, which is satisfactory for intended use. Trueness was evaluated by recovery rate using certified reference materials containing mercury, with satisfactory results. Other figures of merit, such as repeatability and measurement uncertainty, also fulfill the legislative requirements related to the analysis of dietary supplements. This paper presents, for the first time, a fully validated method for mercury determination in zeolite samples, and the obtained results reveal that the method can be applied successfully for the intended purpose.

The clarity of the beer is essential to its marketability and good consumer approval. Moreover, the beer filtration aims to remove the unwanted constituents that cause beer haze formation. Natural zeolite, an inexpensive and widespread material, was tested as a substitute filter media for diatomaceous earth in removing the haze constituents in beer. The zeolitic tuff samples were collected from two quarries in Northern Romania: Chilioara, in which the zeolitic tuff has a clinoptilolite content of about 65%, and the Valea Pomilor quarry, containing zeolitic tuff with a clinoptilolite content of about 40%. Two-grain sizes, <40 and <100 µm, from each quarry were prepared and thermally treated at 450 °C in order to improve their adsorption properties and remove organic compounds and for physico-chemical characterization. The prepared zeolites were used for beer filtration in different mixtures with commercial filter aids (DIF BO and CBL3) in laboratory-scale experiments, and the filtered beer was characterized in terms of pH, turbidity, color, taste, flavor, and concentrations of the major and trace elements. The results showed that the taste, flavor, and pH of the filtered beer were generally not affected by filtration, while turbidity and color decreased with an increase in the zeolite content used in the filtration. The concentrations of Na and Mg in the beer were not significantly altered by filtration; Ca and K slowly increased, while Cd and Co were below the limits of quantification. Our results show that natural zeolites are promising aids for beer filtration and can be readily substituted for diatomaceous earth without significant changes in brewery industry process equipment and protocols for preparation.

An analytical method based on microwave-assisted acid digestion and atomic absorption spectrometry with graphite furnace as atomization source was developed and validated for determining trace elements (Cd and Pb) in zeolites used as dietary supplements, for their characterization and safety evaluation. The method was checked for the main performance parameters according to the legislation requirements in the field of dietary supplements. In all cases, the obtained performance parameters were satisfactory. The selectivity study showed no significant non-spectral matrix effect. The linearity study was conducted for the calibration curves in the range of 0–10 ng mL−1 for Cd and 0–30 ng mL−1 for Pb. The obtained limits of detection (LoDs) and the limits of quantification (LoQs) were sufficiently low in order to allow Pb and Cd determination in dietary supplements. For the internal quality control, certified reference materials were analysed and good recoveries were obtained. The precision study was performed in terms of repeatability and reproducibility, considering the requirements imposed by the Commission Decision (2007/333/EC) and the method fulfilled these performance parameters. Expanded measurement uncertainties were estimated to 11% for Cd and 10% for Pb. Cd and Pb content were measured in real zeolite samples and, using these data, a safety evaluation was carried out.