Meral Dogan

BASELINE STUDIES OF THE CLAY MINERALS SOCIETY SOURCE CLAYS: SPECIFIC SURFACE AREA BY THE BRUNAUER EMMETT TELLER (BET) METHOD

Specific surface area measurements of The Clay Minerals Society source clays were made by the Brunauer, Emmett and Teller (BET) method of adsorption of nitrogen gas. Two replicate measurements of specific surface area were performed for each source clay. All pair values were within 3%, which is very good agreement for this type of measurement.

Crystal structure and iron topochemistry of erionite-K from Rome, Oregon, U.S.A.

Abstract A complete crystal-chemical characterization of erionite-K from Rome, Oregon, was obtained by combining field emission scanning electron microscopy, laboratory parallel-beam transmission powder diffraction, and 57Fe Mössbauer spectroscopy. Rietveld refinement results evidenced that the most striking difference in comparison with the structure of erionite-Ca is significant K at a K2 site (½, 0, 0), which is empty in erionite-Ca. In addition, site Ca1 shows low occupancy and Ca3 is vacant. The oxidation and coordination state of Fe, whose occurrence was revealed by chemical analysis, have been clarified by exploiting room- and low-temperature 57Fe Mössbauer spectroscopy. The majority of Fe (95%) was attributed to Fe3+-bearing, superparamagnetic, oxide-like nanoparticles with dimensions between 1 and 9 nm, and the remaining 5% was attributed to hematite particles with size ≥10 nm, both located on the crystal surface.

Re-evaluation and re-classification of erionite series minerals.

Governments and industries have introduced regulatory measures requiring safety controls to limit asbestos exposure of the general public and asbestos workers. Although erionite is a more potent health hazard mineral than asbestos, it has received far less attention. Precise definition of erionite, types of these fibrous minerals, and most importantly, characterization requirements still raise questions and often lead to arguments and even legal disputes. Many bulk erionite samples used in animal and cell experiments for carcinogenicity are not mineralogically pure. To test this hypothesis, we characterized two erionite standards from Rome, Oregon, and Pine Valley, Nevada, USA. These standards were characterized quantitatively using modern analytical techniques, and one of them, the erionite standard from Rome, Oregon, passed the required tests for positive identification, but the other, the erionite standard from Pine Valley, Nevada, did not. Furthermore, we observed ambiguous definitions, incorrect identifications, and inaccurate reporting of clinical investigations. To address this problem, we established characterization guidelines for positive identification of erionite using a modified balance error formula, and we re-evaluated and re-classified published erionite data from the literature as erionite-Ca, erionite-Na, and erionite-K. If data did not pass either the E% or Mg-content test, then we propose that reference to them in the literature be disregarded. Erionite requires special attention from the mineralogical community to help establish its true carcinogenetic properties. We believe that the characterization guidelines established in this paper will contribute to setting up rules and regulations for evaluation of erionite by regulatory agencies.

Morpho-chemical characterization and surface properties of carcinogenic zeolite fibers.

Erionite belonging to the zeolite family is a human health-hazard, since it was demonstrated to be carcinogenic. Conversely, offretite family zeolites were suspected carcinogenic. Mineralogical, morphological, chemical, and surface characterizations were performed on two erionites (GF1, MD8) and one offretite (BV12) fibrous samples and, for comparison, one scolecite (SC1) sample. The specific surface area analysis indicated a larger availability of surface sites for the adsorption onto GF1, while SC1 shows the lowest one and the presence of large pores in the poorly fibrous zeolite aggregates. Selected spin probes revealed a high adsorption capacity of GF1 compared to the other zeolites, but the polar/charged interacting sites were well distributed, intercalated by less polar sites (Si-O-Si). MD8 surface is less homogeneous and the polar/charged sites are more interacting and closer to each other compared to GF1. The interacting ability of BV12 surface is much lower than that found for GF1 and MD8 and the probes are trapped in small pores into the fibrous aggregates. In comparison with the other zeolites, the non-carcinogenic SC1 shows a poor interacting ability and a lower surface polarity. These results helped to clarify the chemical properties and the surface interacting ability of these zeolite fibers which may be related to their carcinogenicity.

Quantitative characterization of the mesothelioma-inducing erionite series minerals by transmission electron microscopy and energy dispersive spectroscopy

Air-collected erionite series minerals from Cappadocia region of Turkey were characterized quantitatively by using transmission electron microscopy (TEM) equipped with energy dispersive spectroscopy (EDS). Field emission scanning electron microscopy aided identification of fibrous minerals. Quantitative characterization guidelines for positive identification of erionites proposed by Dogan and Dogan (2008) was applied and the modified balance error formula (E%<10) and Mg-content test <0.80 were performed for each analysis. Erionite species computation showed that the mineral is erionite-K and a mean chemical formula is proposed based upon the TEM-EDS results. Among the 60 analyses, 11 passed E% test (18.3%), 33 passed Mg-content test (55.0%), and only 3 passed both E% and Mg-content tests (5.0%). This shows difficulty of quantitative characterization of the erionite series minerals. However, as erionite is the most carcinogenic mineral known and is classified by IARC as a Group-I (human) carcinogen, it requires special attention from the mineralogical community to help establish its true mineralogical properties. Quantitatively characterized erionite data are very scarce in literature. Correctly identified erionite mineral types will be useful to medical researchers in their search to find a possible cure for the deadly disease of mesothelioma.

Quantitative mineralogical properties (morphology-chemistry-structure) of pharmaceutical grade kaolinites and recommendations to regulatory agencies.

The physical and chemical characteristics of kaolinite (kaolin) may be variable, and minor amounts of other clay minerals, nonclay minerals, and other impurities may affect the properties of kaolinites. Thus specific technical properties of pharmaceutical grade kaolinites become very important because these clays are used in medical applications, e.g., as pharmaceutical excipients, and will be consumed by humans. Seven pharmaceutical grade kaolinite specimens were used in this study: K1004, KA105, 2242-01, K2-500, Acros, Acros-mono, and KX0007-1. In addition, two kaolinites from the Clay Minerals Society Source Clays, KGa-1b and KGa-2, were used for comparison purposes. The Acros-mono and 2242-01 kaolinites contained minor amounts of illite, which was demonstrated both compositionally and structurally by using inductively coupled plasma spectroscopy and powder X-ray diffraction. The KX0007-1 kaolinite powder was found to be heavily contaminated with quartz, cristobalite, and alunite. Crystal structure computations also showed excess Si in its tetrahedral site, and the mineral no longer has the typical kaolinite crystal structure. These widely-used industrial standards should be quantitatively characterized morphologically, compositionally, and structurally. Results of the mineralogical characteristics should be clearly labeled on the pharmaceutical grade kaolinites and reported to the relevant regulatory agencies.

Potential carcinogenic erionite from Lessini Mounts, NE Italy: Morphological, mineralogical and chemical characterization

ABSTRACT Exposure of humans to erionite fibers of suitable morphology and dimension has been unambiguously linked to the occurrence of malignant mesothelioma. For this reason, a morphological, morphometrical, mineralogical, and chemical investigation was performed on two representative samples of potential carcinogenic, fibrous erionite from Lessini Mounts, northeastern (NE) Italy, which has not apparently been examined previously. The first sample is erionite-Ca with an extremely fibrous, hair-like and flexible appearance, and growth in intimate association with levyne. The second sample is erionite-Ca with prismatic to acicular crystals and rigid behavior, enriched in K+ and Ca2+ extra-framework cations. Although erionite is a nominally Fe-free phase, iron (Fe) was detected in low amounts in all the analyzed crystals. In both the investigated samples, erionite is present as individual fibers of respirable size. Considering that the toxicity and carcinogenic potential of erionite is associated with its size parameters, together with its in vivo durability and high surface area, most of the investigated fibers may also be potentially carcinogenic. The presence of erionite in extensively quarried and largely employed volcanic rocks, suggesting the need for detailed health-based studies in the region.

Classifications of hardgrounds based upon their strength properties

Rock samples from the Baglum-Kosrelik area, 30 km north of Ankara, Turkey have been studied petrographically in detail to differentiate between nodular limestones and hardgrounds. However, it is found that petrographic criteria alone may not always be used to differentiate between nodular limestones and true hardgrounds. Distinction between hardgrounds and other wellindurated carbonate rocks can be made based upon the strength properties of the rocks, including uniaxial compressive strengths, triaxial compressive strengths, modulus ratios, and elastic constant ratios. This study showed that rock petrophysical characteristics could be used to develop criteria for distinguishing hardgrounds. For example, strength tests using the International Society for Rock Mechanics result in very high strength and extreme hardness values, with a minimum uniaxial compressive strength value, of 130 MPa with 10% standard deviation, therefore the rock can be classified as “true” hardground. Classification of these carbonates in this manner would facilitate quantitative discussions between hardground carbonate petrographers and engineering geologists. Hardgrounds throughout the world then could be tested and classified accordingly.

Bassanite fromSalvadora persica: A new evaporitic biomineral

For centuries, stems ofSalvadora persica have been commonly used as a chewing stick or a natural toothbrush in many parts of the world, including Saudi Arabia, Africa, and India. We report, for the first time, the existence of a new biomineral, “bassanite”, extracted from the stems ofSalvadora persica. Detailed scanning electron microscopy and thin window energy dispersive spectroscopy were employed to document the crystal morphology and to determine the elemental composition of the bassanite. Comparison of the powder X-ray diffraction data of the biomineral found inSalvadora persica with that of a synthetic bassanite confirmed the identity of the biomineral as bassanite. The bassanite reported herein is quite different than the fibrous nature of the non-biogenic mineral bassanite.

Asbestos Mineralogy and Health Effects

Asbestos, characterized as a group A human carcinogen, is a generic name given to the fibrous variety of six naturally occurring minerals: chrysotile, actinolite, tremolite, anthophyllite, amosite, and crocidolite. The permissible exposure limits recommended by WHO is 1.0F/cc or below. The identification of asbestos fibers can be performed through morphologic, crystal structural, and compositional analyses. It is widely accepted that asbestos fibers can be associated with asbestosis, lung cancer, and mesothelioma. Despite extensive cancer studies in humans, certain controversies remain about asbestos exposure and cancer. Today, only chrysotile is used as an asbestos material because it is considered to be less potent. The key questions concern whether or not, and to what extent, exposure to chrysotile asbestos, including its natural contaminant tremolite, causes mesothelioma. Many companies ceased production of asbestos-containing insulations, plasters, ceiling tiles, and cement products because of liability issues. However, there is a continued demand for inexpensive and durable construction materials.