Raman Spectroscopic Characteristics of Zeolite Group Minerals

In this work, Raman spectroscopic experiments are conducted on zeolites, including a total of 33 varieties and seven groups with different secondary structural frameworks, for which characteristic vibration modes are studied. Most of the zeolites show prominent Raman peaks in the spectral range between 200–1200 cm−1. Different groups of zeolites can be recognized by differences in the wavenumbers of the T-O-T (T = Si and Al, O = oxygen) modes in the range 379–538 cm−1, the M-O (M = metal,) modes in the range 250–360 cm−1 and the T-O bending modes in the range 530–575 cm−1. All zeolites show characteristic Raman peaks in the range 379–529 cm−1, except for natrolite group (fibrous) zeolites, which are characterized by T-O-T modes in the 433–447 cm−1 range and T-O bending modes in the 528–538 cm−1 range. The analcime group (with singly connected four-ring chains) zeolites show T-O-T modes in the 379–392 cm−1 and 475–497 cm−1 ranges. The gismondine group (with doubly connected four-ring chains) zeolites have T-O-T modes in the 391–432 cm−1 and 463–497 cm−1 ranges. The chabazite group (with a six-cyclic ring) zeolites are characterized by M-O modes in the 320–340 cm−1 range and T-O-T modes in the 477–509 cm−1 range. The Raman modes of mordenite group zeolites (397–410 cm−1 and 470–529 cm−1) overlap with those of heulandite group zeolites (402–416 cm−1 and 480–500 cm−1). Moreover, the mordenite group has a characteristic peak in the 502–529 cm−1 range, and an additional peak in the 800–965 cm−1 range. Another recognizable peak for the heulandite group is in the 612–620 cm−1 range. The unknown zeolites (cowlesite) have unique characteristic peaks at 534 cm−1, which can aid in the verification of their identity.

Real-Time Observation of Fibrous Zeolites Reactivity in Contact with Simulated Lung Fluids (SLFs) Obtained by Atomic Force Microscope (AFM)

Inhalation of fibrous erionite particles has been linked to malignant mesothelioma. Accordingly, erionite is considered the most carcinogenic mineral. The reactivity and the nature of erionite biotoxicity has been the subject of intensive research. Despite very close chemical and structural relationships between erionite and offretite, the reactivity of offretite in lung fluids remains unknown. In this paper, the interaction of erionite and offretite surfaces with simulated lung fluids was investigated by means of in situ atomic force microscope (AFM). To simulate different environments in the lungs, artificial lysosomal fluid (ALF) and Gamble’s solution were used. In ALF (4.15 < pH < 4.31) the dissolution of erionite and offretite surfaces was detected, as well as an evident removal of particles (mainly attributed to impurities) from the crystal faces. Instead, the growth of a layer of a yet unknown phase on the surface of both zeolites was observed during the interaction with Gamble’s solution (7.4 < pH < 8.48). The thickness of this layer reached a few tens of nanometers and covered all the observed areas. The understanding of the observed processes is of paramount importance, since they could be potentially involved in the mechanisms triggering the toxicological effects of erionite fibres.

Mineralogical characterization of fibrous zeolites from the Kahrizak volcanic suite, south Tehran, Iran

Selected samples of large cavity filling and vein-type fibrous zeolites from Eocene volcanic rocks in the Kahrizak region, northern Iran, have been studied for their mineralogical and chemical characteristics. X-ray powder diffraction and electron microprobe analyses confirmed the presence of natrolite, mesolite and scolecite with compositions of [Na14.922Ca0.202K0.015Ba0.002] [Al15.697Si24.267O80]·nH2O, [Ca15.714Na14.224][Al46.431Si73.398O240]·nH2O and [Ca7.804Na0.142K0.024Ba0.012Mg0.006][Al15.320Si24.437O80]·nH2O, respectively. In addition, examination of textural relationships in thin sections and back-scattered electron images reveals a paragenetic order in which the Ca-rich zeolites crystallized first. It is most probable that the fibrous zeolites of Kahrizak were formed during two pulses of hydrothermal activity in the area. Scolecite and mesolite were precipitated from Ca-rich solution, whereas the second stage Na-rich, low-temperature fluid crystallized natrolite and reacted with Ca-species.

Structural disorder of a new zeolite-like lithosilicate, K2.6Li5.4[Li4Si16O38]·4.3H2O

The framework structure of the synthetic microporous lithosilicate RUB-30 (K2.6Li5.4[Li4Si16O38]·4.3H2O) is similar to that of the fibrous zeolites such as natrolite, edingtonite and thomsonite, since all their frameworks include the same secondary structural building unit, the so-called 4–1 T 5O10 cluster of tetrahedra. Unique to the structure of RUB-30, each 4–1 unit consists of a LiSi4O10 moiety within which the single [LiO4] tetrahedron is strictly segregated from the other four [SiO4] tetrahedra. The connection of neighboring 4–1 units through edge-sharing [LiO4] tetrahedra results in a new framework topology. The present work reports an `average' structure of RUB-30 solved by synchrotron X-ray single-crystal diffraction data collected at a second-generation source. A superstructure with a × 2b × c (relative to the subcell quoted above) could be seen in X-ray diffraction data collected with better resolution and higher brightness at a third generation source. Diffuse streaks along k with l = odd and unusual superstructure hkl reflections, with k = odd and l = odd only, indicate a more complicated real structure of the material. To explain this observation we propose two different structure types which are statistically, but coherently, intergrown in RUB-30.