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Krypton retention on solid adsorbents. [Activated alumina; hydrogen mordenite, silver mordenite, sodium mordenite, cerium mordenite-H, cerium mordenite-Na, potassium mordenite-H, potassium mordenite-Na  

SciTech Connect

An experimental laboratory program was conducted to develop economical solid adsorbents for the retention of krypton from a dissolver off-gas stream. The study indicates that a solid adsorbent system is feasible and competitive with other developing systems which utilize fluorocarbon absorption nd cryogenic distillation. This technology may have potential applications not only in nuclear fuel reprocessing plants, but also in nuclear reactors and in environmental monitoring. Of the 13 prospective adsorbents evaluated with respect to adsorption capacity and cost, the commercially available hydrogen mordenite was the most cost-effective material at subambient temperatures (-40/sup 0/ to -80/sup 0/C). Silver mordenite has a higher capacity for krypton retention, but is 50 times more expensive than hydrogen mordenite.

Monson, P.R. Jr.



NQRS Data for Mordenite (Subst. No. 2511)  

NASA Astrophysics Data System (ADS)

This document is part of Subvolume B 'Substances Containing C10H16 … Zn' of Volume 48 'Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III 'Condensed Matter'. It contains an extract of Section '3.2 Data tables' of the Chapter '3 Nuclear quadrupole resonance data' providing the NQRS data for Mordenite (Subst. No. 2511)

Chihara, H.; Nakamura, N.


Direct synthesis of high-silica mordenite using seed crystals  

Microsoft Academic Search

The direct hydrothermal synthesis of high-silica mordenite (MOR) zeolite in the presence of tetraethylammonium hydroxide using various seed crystals was investigated. When seed crystals with the Si\\/Al ratio of 15 synthesized without NaF were employed, the highly crystalline MOR zeolite with the Si\\/Al ratio of approximately 30 and the crystal length of ?8?m was successfully prepared.

Baowang Lu; Tomohiro Tsuda; Yasunori Oumi; Keiji Itabashi; Tsuneji Sano



Iodine Loading of NO Aged Silver Exchanged Mordenite  

SciTech Connect

In an off-gas treatment system for used nuclear fuel processing, a solid sorbent will typically be exposed to a gas stream for months at a time. This gas stream may be at elevated temperature and could contain water vapor, gaseous nitrogen oxides (NO{sub x}), nitric acid vapors, and a variety of other constituents. For this reason, it is important to evaluate the effects of long-term exposure, or aging, on proposed sorbents. Silver exchanged mordenite (AgZ) is being studied at Oak Ridge National Laboratory (ORNL) to determine its iodine sorption capacity after long term exposure to increasingly more complex chemical environments. Studies previously conducted at ORNL investigated the effects of aging reduced silver exchanged mordenite (Ag{sup 0}Z) in dry air, moist air, and NO2. This study investigated the effects of extended exposure to nitric oxide (NO) gas on the iodine capture performance of Ag{sup 0}Z. A deep bed of Ag{sup 0}Z was aged in a 1% nitric oxide (NO) air stream, and portions of the bed were removed at pre-determined intervals. After being removed from the NO stream, each sample was loaded with iodine in a thin bed configuration. These samples were analyzed by neutron activation analysis (NAA) to quantify the iodine content in the sample. Samples were removed at one week and one month. A 78% decrease in sample capacity was seen after one week of exposure, with no further decrease observed after 1 month of aging. The observed loss in capacity is larger in magnitude than previous studies exposing Ag{sup 0}Z to dry air, moist air, or NO2 gas. The aging study was terminated after one month and repeated; this successfully demonstrated the reproducibility of the results.

Patton, K. K. [ORNL; Bruffey, S. H. [ORNL; Jubin, J. T. [ORNL; Walker, Jr., J. F. [ORNL



Mineralogy, geochemistry and uses of the mordenite–bentonite ash-tuff beds of Los Escullos, Almer??a, Spain  

Microsoft Academic Search

The mordenite ore deposit of Los Escullos has a surface area of 106 m2 with an average thickness of 5 m and estimated reserves of 7,500,000 tons of mordenite–bentonite. It is made up of horizontal layers of interbedded epiclastic tuffs with volcanic bentonitised materials which have been subjected to hydromagmatic activity. The layers are essentially composed of bentonite and mordenite

Raul Benito; Javier Garcia-Guinea; Francisco J Valle-Fuentes; Paloma Recio



Aging of Iodine-Loaded Silver Mordenite in NO2  

SciTech Connect

Used nuclear fuel facilities need to control and minimize radioactive emissions. Off-gas systems are designed to remove radioactive contaminants, such as 85Kr, 14C, 3H, and 129I. In an off-gas system, any capture material will be exposed to a gas stream for months at a time. This gas stream may be at elevated temperature and could contain water, NOx gas, or a variety of other constituents comprising the dissolver off-gas stream in a nuclear fuel reprocessing plant. For this reason, it is important to evaluate the effects of long-term exposure, or aging, on proposed capture materials. One material under consideration is reduced silver mordenite (Ag0Z), which is recognized for its efficient iodine capture properties. Iodine is immobilized on Ag0Z as AgI, a solid with low volatility (m.p. ? 500°C). The aim of this study was to determine whether extended aging at elevated temperature in a nominally 2% NO2 environment would result in a loss of immobilized iodine from this material due to either physical or chemical changes that might occur during aging. Charges of iodine-loaded reduced silver mordenite (I2-Ag0Z) were exposed to a 2% NO2 environment for 1, 2, 3, and 4 months at 150°C, then analyzed for iodine losses The aging study was completed successfully. The material did not visibly change color or form. The results demonstrate that no significant iodine loss was observed over the course of 4 months of 2% NO2 aging of I2-Ag0Z at elevated temperature within the margin of error and the variability (~10%) in the loading along the beds. This provides assurance that iodine will remain immobilized on Ag0Z during extended online use in an off-gas capture treatment system. Future tests should expose I2-Ag0Z to progressively more complex feed gases in an effort to accurately replicate the conditions expected in a reprocessing facility.

Bruffey, Stephanie H. [ORNL; Jubin, Robert Thomas [ORNL; Patton, Kaara K. [ORNL; Walker Jr, Joseph Franklin [ORNL



Hydrothermally synthesized high silica mordenite as an efficient catalyst in alkylation reaction under liquid phase condition  

Microsoft Academic Search

High silica mordenite (HSM) samples have been synthesized hydrothermally by using low aluminum contents (Si\\/Al molar ratios 40 and 60) with the synthesis gel in the presence of orthophosphoric acid as promoter at 443K. Sodium silicate and aluminum sulfate were used as Si and Al precursors, respectively. Solid yield and particle size of these materials have been improved considerably over

Sujit Samanta; Nawal Kishor Mal; Prashant Kumar; Asim Bhaumik



Optimization of lead adsorption of mordenite by response surface methodology: characterization and modification  

PubMed Central

Background In order to remove heavy metals, water treatment by adsorption of zeolite is gaining momentum due to low cost and good performance. In this research, the natural mordenite was used as an adsorbent to remove lead ions in an aqueous solution. Methods The effects of adsorption temperature, time and initial concentration of lead on the adsorption yield were investigated. Response surface methodology based on Box-Behnken design was applied for optimization. Adsorption data were analyzed by isotherm models. The process was investigated by batch experiments; kinetic and thermodynamic studies were carried out. Adsorption yields of natural and hexadecyltrimethylammonium-bromide-modified mordenite were compared. Results The optimum conditions of maximum adsorption (nearly 84 percent) were found as follows: adsorption time of 85-90 min, adsorption temperature of 50°C, and initial lead concentration of 10 mg/L. At the same optimum conditions, modification of mordenite produced 97 percent adsorption yield. The most appropriate isotherm for the process was the Freundlich. Adsorption rate was found as 4.4. Thermodynamic calculations showed that the adsorption was a spontaneous and an exothermic process. Conclusions Quadratic model and reduced cubic model were developed to correlate the variables with the adsorption yield of mordenite. From the analysis of variance, the most influential factor was identified as initial lead concentration. At the optimum conditions modification increased the adsorption yield up to nearly 100 percent. Mordenite was found an applicable adsorbent for lead ions especially in dilute solutions and may also be applicable in more concentrated ones with lower yields. PMID:24393442



Kinetic study and modelization of n-butenes oligomerization over H-mordenite  

SciTech Connect

n-Butenes have been oligomerized at temperatures lower than 450 K in the liquid phase over H-mordenite in a continuously stirred tank reactor. The composition and molecular weight of the products are very dependent on reaction temperature. Products are essentially dimers, trimers, and tetramers. The complex reactions were modeled by taking into account only the type of carbonium ion; the initial rates showed that the oligomerization reactions followed a Rideal mechanism. The dimerization rate constants of butenes and oligomers decrease with increasing number of carbon atoms of the olefins, while the adsorption constants increase with the hydrocarbon chain length. A model for the conversion of butenes to liquid products over H-Mordenite is proposed. This model fits the experimental data rather well, although some simplifying approximations were made to describe these complex reactions.

Ngandjui, L.M.T.; Thyrion, F.C. [Louvain Univ., Louvain-la-Neuve (Belgium). Chemical Engineering Inst.



Crystallization and morphology of mordenite zeolite influenced by various parameters in organic-free synthesis  

SciTech Connect

Research highlights: {yields} Seed, gel composition and silicon source affect the crystallization process of MOR. {yields} Seed, gel composition and silicon source influence the morphology of MOR. {yields} Low silica concentration results in MOR with high c/b aspect ratio. {yields} Novel nano fiber-like MOR with c/b aspect ratio of 89 was organic-free synthesized. {yields} The morphology of MOR influences its mesopore property and thermal stability. -- Abstract: A series of mordenite zeolites with different morphologies were synthesized via a facile organic-free hydrothermal route, and characterized by X-ray diffraction, scanning electron microscopy, X-ray fluorescence spectrometer and N{sub 2} adsorption-desorption techniques. Influences of synthetic parameters, including seed crystal, silicon precursor, SiO{sub 2}/Al{sub 2}O{sub 3}, Na{sub 2}O/SiO{sub 2} and H{sub 2}O/SiO{sub 2}, on mordenite crystallization were investigated systematically. It was found that mordenite zeolites with various morphologies, such as fiber-like, rod-like, prism-like and needle-like ones could be synthesized in control. Especially, novel nano fiber-like MOR crystals with high c/b aspect ratio were prepared from low silica concentration system, which was manipulated by using small initial SiO{sub 2}/Al{sub 2}O{sub 3} ratio, large H{sub 2}O/SiO{sub 2} and silicon source with slow dissolution rate. Moreover, mordenite samples with various morphologies exhibited different mesopore property and thermal stability.

Zhang, Ling [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian P.O. Box 110, 116023 (China) [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian P.O. Box 110, 116023 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Xie, Sujuan; Xin, Wenjie; Li, Xiujie; Liu, Shenglin [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian P.O. Box 110, 116023 (China)] [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian P.O. Box 110, 116023 (China); Xu, Longya, E-mail: [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian P.O. Box 110, 116023 (China)] [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian P.O. Box 110, 116023 (China)



Quantitative characterisation of H-Mordenite zeolite structure by infrared spectroscopy using benzene adsorption  

Microsoft Academic Search

Infrared spectroscopy has been used to characterise the Brönsted acidity, the hydroxyls of H-Mordenite (HM) zeolite and the interaction of hydroxyls with benzene molecules. After pre-treatment under dry oxygen and then under vacuum at 723 K, three hydroxyl groups at 3749, 3660 and 3608 cm?1, assigned to terminal silanol, extraframework Al–OH and framework bridged Si–OH–Al species, respectively, have been detected.

Bao-Lian Su; Valérie Norberg



Studies on the acidity of mordenite and ZSM-5. 1. Determination of Broensted acid site concentrations in mordenite and ZSM-5 by conductometric titration  

SciTech Connect

The Broensted acidity of H-mordenite and H-ZSM-5 samples of varying proton concentration has been studied using aqueous conductometric titration, IR spectroscopy, and aqueous potentiometric titration. Good agreement is observed between Broensted acid site concentrations determined by conductometric titration and IR measurements, while indirect potentiometric titration affords acid site concentrations consistently lower than those measured using the conductometric technique. This finding is rationalized on the basis that, in a conductometric titration, all the accessible Broensted acid sites are direct;y titrated, whereas in the potentiometric procedure utilized, only those protons which can be ion-exchanged out of the zeolite are titrated. After allowing for the presence of extraframework aluminum in the zeolites (determined by [sup 27]Al NMR), the measured acidity for H-mordenite is found to increase linearly with increasing Al content within the range 0-1.5 mmol Al/g but appears to reach a limiting value at higher Al concentrations. For H-ZSM-5, the experimentally determined number of Broensted acid sites is also found to be linearly dependent on the Al molar fraction within the range measured (0-1.20 mmol Al/g). For both series of zeolite samples, the measured acidity is generally found to be less than the theoretical maximum calculated on the basis of an H[sup +]/Al ratio of 1. 43 refs., 10 figs., 4 tabs.

Crocker, M.; Herold, R.H.M.; Sonnemans, M.H.W.; Emeis, C.A.; Wilson, A.E.; Moolen, J.N. van der (Koninklijke/Shell-Laboratorium, Amsterdam (Netherlands))



Location of MTBE and toluene in the channel system of the zeolite mordenite: Adsorption and host-guest interactions  

SciTech Connect

This paper reports a study of the location of Methyl Tertiary Butyl Ether (MTBE) and toluene molecules adsorbed in the pores of the organophylic zeolite mordenite from an aqueous solution. The presence of these organic molecules in the zeolite channels was revealed by structure refinement performed by the Rietveld method. About 3 molecules of MTBE and 3.6 molecules of toluene per unit cell were incorporated into the cavities of mordenite, representing 75% and 80% of the total absorption capacity of this zeolite. In both cases a water molecule was localized inside the side pocket of mordenite. The saturation capacity determined by the adsorption isotherms, obtained by batch experiments, and the weight loss given by thermogravimetric (TG) analyses were in very good agreement with these values. The interatomic distances obtained after the structural refinements suggest MTBE could be connected to the framework through a water molecule, while toluene could be bonded to framework oxygen atoms. The rapid and high adsorption of these hydrocarbons into the organophylic mordenite zeolite makes this cheap and environmental friendly material a suitable candidate for the removal of these pollutants from water. - graphical abstract: Location of MTBE (a) and toluene (b) in mordenite channels (projection along the [001] direction). Highlights: Black-Right-Pointing-Pointer We investigated the MTBE and toluene adsorption process into an organophilic zeolite mordenite. Black-Right-Pointing-Pointer The presence of MTBE and toluene in mordenite was determined by X-ray diffraction studies. Black-Right-Pointing-Pointer About 3 molecules of MTBE and 3.6 molecules of toluene per unit cell were incorporated into the zeolite cavities. Black-Right-Pointing-Pointer MTBE is connected to the framework through a water molecule. Black-Right-Pointing-Pointer Toluene is directly bonded to framework oxygen atoms.

Arletti, Rossella, E-mail: [Department of Earth Sciences, University of Torino Via Valperga Caluso 35, I-10125, Torino (Italy)] [Department of Earth Sciences, University of Torino Via Valperga Caluso 35, I-10125, Torino (Italy); Martucci, Annalisa; Alberti, Alberto [Department of Earth Sciences, University of Ferrara, Via G. Saragat 1, I-44100, Ferrara (Italy)] [Department of Earth Sciences, University of Ferrara, Via G. Saragat 1, I-44100, Ferrara (Italy); Pasti, Luisa; Nassi, Marianna [Department of Chemistry, University of Ferrara, Via L. Borsari 26, I-44100 Ferrara (Italy)] [Department of Chemistry, University of Ferrara, Via L. Borsari 26, I-44100 Ferrara (Italy); Bagatin, Roberto [Research Centre for Non-Conventional Energy-Istituto ENI Donegani, Environmental Technologies, Via Fauser 4, I-28100 Novara (Italy)] [Research Centre for Non-Conventional Energy-Istituto ENI Donegani, Environmental Technologies, Via Fauser 4, I-28100 Novara (Italy)



Reaction of butanes on Na, H-Y zeolites and H-mordenites  

SciTech Connect

The reaction chemistry for the conversion of isobutane and n-butane on H-mordenites was compared with that on Na,H-Y zeolites in continuous flow experiments. The close resemblance of the product distribution as a function of conversion suggests that identical mechanism for conversion is effective on both types of zeolites. Hydrogen and methane from isobutane and in addition ethane and ethylene from n-butane were expected to be formed in chain initiation processes, while propene and butenes were expected to be formed in chain termination processes. The major products, alkanes, are produced in chain carrying hydride and methyl transfer. A rate of initiation approximately 10-fold higher than with mordenites having stronger Bronsted acid sites is required to reach identical conversion with Y-zeolites. The yield of individual products on zeolites with identical structure and at identical temperature was almost independent of the Si/Al ratio or the Na{sup +} content of zeolites but depended on the conversion; at identical conversion the chain length on zeolites with different activity was similar. 28 refs., 9 figs., 6 tabs.

Engelhardt, J. [Central Research Inst. for Chemistry of the Hungarian Academy of Sciences, Budapest (Hungary)] [Central Research Inst. for Chemistry of the Hungarian Academy of Sciences, Budapest (Hungary)



Mordenite and montmorillonite alteration of glass structures in a rhyolite pipe, northern Black Hills, South Dakota  

SciTech Connect

Green structures, 0.5 to 1.5 in. across, occur in a Tertiary rhyolite pipe in the northern Black Hills, South Dakota. The structures are of two types: angular to ellipsoidal masses and stretched or smeared structures. Thin section analysis revealed that those of the first type are massive, with no internal structure, and those of the second type are cellular and have classic flame structure characteristics. XRD indicated the composition to be a mixture of secondary mordenite (a zeolite) and montmorillonite. The first type is interpreted to be deuterically altered vitrophyre clasts and the second type to be altered vesicular structures produced by degassing of the magma in the pipe. Chemical analysis of the alteration material indicates a loss of alkalies and silica, with an increase in water, CaO, MgO and ferric iron when compared to the composition of fresh vitrophyre from the same pipe. The changes are in agreement with experimental work on the alteration of rhyolitic glass by a number of researchers. This is the first occurrence of mordenite reported for the Black Hills.

Kirchner, J.G. (Illinois State Univ., Normal (United States))



Kinetic and equilibrium studies of the removal of ammonium ions from aqueous solution by rice husk ash-synthesized zeolite Y and powdered and granulated forms of mordenite.  


The removal of ammonium from aqueous solutions using zeolite NaY prepared from a local agricultural waste, rice husk ash waste was investigated and a naturally occurring zeolite mordenite in powdered and granulated forms was used as comparison. Zeolite NaY and mordenite were well characterized by powder X-ray diffraction (XRD), energy dispersive X-ray (EDX) analysis and the total cation exchange capacity (CEC). CEC of the zeolites were measured as 3.15, 1.46 and 1.34 meq g(-1) for zeolite Y, powdered mordenite and granular mordenite, respectively. Adsorption kinetics and equilibrium data for the removal of NH(4)(+) ions were examined by fitting the experimental data to various models. Kinetic studies showed that the adsorption followed a pseudo-second-order reaction. The equilibrium pattern fits well with the Langmuir isotherm compared to the other isotherms. The monolayer adsorption capacity for zeolite Y (42.37 mg/g) was found to be higher than that powdered mordenite (15.13 mg/g) and granular mordenite (14.56 mg/g). Thus, it can be concluded that the low cost and economical rice husk ash-synthesized zeolite NaY could be a better sorbent for ammonium removal due to its rapid adsorption rate and higher adsorption capacity compared to natural mordenite. PMID:19879040

Yusof, Alias Mohd; Keat, Lee Kian; Ibrahim, Zaharah; Majid, Zaiton Abdul; Nizam, Nik Ahmad



Synthesis and characterization of nanocrystalline mordenite, high silica zeolite RHO, and copper faujasite  

NASA Astrophysics Data System (ADS)

Mordenite is a zeolite that has been used as a selective adsorbent and as a catalyst. In reactions where the diffusion of reagents into the pore system is the rate-determining step, nanoparticles of the catalyst improve the reaction rate. Mordenite with a crystal diameter smaller than 100 nm has been prepared by the modification of different synthetic parameters such as the source of aluminum, the presence of seeds, the use of low temperatures (150°C vs. 170°C), longer crystallization times (24 h vs. 96 h), and different silica to alumina ratios (10--30). The decrease in the crystal diameter of the prepared mordenite was monitored by the application of the Scherrer equation that relates the broadness of the X-ray diffraction peaks to crystal sizes. Zeolite RHO with an initial silica to alumina ratio (SAR) higher than 20 has been prepared. EDTA, citric acid, and tartaric acid have been used as complexing agents in the synthesis of zeolite RHO. Crystallization time increases (from 48 h to 900 h) with increasing the silica to alumina ratios (SAR) of the initial gel (SAR: 10.8 to 30) and by adding complexing agents. Complexing agents favor the formation of small crystals (0.8 mum) with increased silica to alumina ratio (final SAR: 4.5 vs. 4.0 without complexing agents). The products were characterized by XRD, FESEM, EDX, FTIR, and in-situ XRD. Copper containing faujasite has been successfully prepared for the first time using a direct synthesis method. Ammonium hydroxide was used to form a copper complex that was later mixed with the reacting gel. Crystallization took place at 85°C for 11 days. The copper containing faujasite obtained was characterized by XRD, FESEM, EDX, EPR, FTIR, TPR, and BET. According to the XRD pattern only FAU type zeolite was obtained. According to TPR experiments, the reduction temperature for Cu2+ ions present in Cu-FAU prepared by direct synthesis was 70 K higher than for Cu-FAU prepared by ion-exchange. This difference can be due to the different location of the copper ions in the supercages or in the sodalite cages of the faujasite.

Hincapie Palacio, Beatriz Omaira


K/AR dating of clinoptilolite, mordenite, and associated clays from Yucca Mountains, Nevada  

SciTech Connect

Zeolites are abundant in the geologic record in both continental and marine environments. The purpose of the present study is to evaluate the utility of K-bearing zeolites for dating by the K/Ar method to determine the time of zeolite diagenesis at Yucca Mountain, Nevada (Fig. 1). At Yucca Mountain, K-rich clinoptilolite and possibly mordenite are the only potentially K/Ar dateable secondary minerals present in the zeolite-rich tuffs except for some illite/smectites ({ge}10% illite layers) associated with these minerals. Direct dating of K-rich clinoptilolite, the most abundant zeolite in the altered tuffs, is important to delineate zeolite chronology as part of the site characterization of Yucca Mountain.

WoldeGabriel, G.




SciTech Connect

A novel new sorbent for the separation of krypton from off-gas streams resulting from the reprocessing of used nuclear fuel has been developed and evaluated. A hydrogen mordenite powder was successfully incorporated into a macroporous polymer binder and formed into spherical beads. The engineered form sorbent retained the characteristic surface area and microporosity indicative of mordenite powder. The sorbent was evaluated for krypton adsorption capacities utilizing thermal swing operations achieving capacities of 100 mmol of krypton per kilogram of sorbent at a temperature of 191 K. A krypton adsorption isotherm was also obtained at 191 K with varying krypton feed gas concentrations. Adsorption/desorption cycling effects were also evaluated with results indicating that the sorbent experienced no decrease in krypton capacity throughout testing.

Mitchell Greenhalgh; Troy G. Garn; Jack D. Law



Growth and characterization of NiS and NiCoS nanoparticles in mordenite zeolite host  

Microsoft Academic Search

We report the optical and structural properties of NiS and the ternary NiCoS nanoparticles in mordenite zeolite. The samples were obtained by sulfidation of the Ni2+ and Co2+ ion-exchange zeolite in a Na2S solution at room temperature. The optical properties of the samples were studied by UV–visible spectroscopy. Their crystalline structure and morphology were studied by XRD and scanning electron

Sh. Sohrabnezhad; A. Pourahmad; M. S. Sadjadi; M. A. Zanjanchi



ZSM-5, Y, and Mordenite Zeolites as Sensing Materials for Ethanol Vapor  

NASA Astrophysics Data System (ADS)

The effects of the framework type, the charge balancing cation type, and the Si/Al ratio of ZSM-5, Y, and Mordenite zeolites on the electrical conductivity responses towards ethanol vapor have been investigated. All zeolites were characterized using XRD, FT-IR, SEM, TGA, BET, and NH3-TPD techniques. For the effect of the framework type, H^+Y has a higher electrical conductivity sensitivity value than that of H^+MOR because of a greater pore volume and available surface area. For the effect of the charge balancing cation, all NH4^+ZSM-5 zeolites (Si/Al = 23, 50, 80, 280) show negative responses, whereas the H^+Y zeolites (Si/Al = 30, 60, 80) and the H^+MOR zeolites (Si/Al = 30, 200) show positive responses. These differing behaviors can be traced to the interactions between ethanol molecules and the reactive sites of the zeolites. For the effect of Si/Al ratio, the electrical conductivity sensitivity towards the ethanol decreases with increasing Si/Al ratio or decreasing Al content, and there is a lesser degree of interaction between ethanol molecules and the active sites of the zeolites. The interactions between the ethanol molecules and the zeolites were investigated through infrared spectroscopy.

Sirivat, Anuvat; Yimlamai, Intira



Expanded Analysis of Hot Isostatic Pressed Iodine-Loaded Silver-Exchanged Mordenite  

SciTech Connect

Reduced silver-exchanged mordenite (Ag0Z) is being evaluated as a potential material to control the release of radioactive iodine that is released during the reprocessing of used nuclear fuel into the plant off-gas streams. The purpose of this study was to determine if hot pressing could directly convert this iodine loaded sorbent into a waste form suitable for long-term disposition. The minimal pretreatment required for production of pressed pellets makes hot pressing a technically and economically desirable process. Initial scoping studies utilized hot uniaxial pressing (HUPing) to prepare samples of non-iodine-loaded reduced silver exchanged mordenite (Ag0Z). The resulting samples were very fragile due to the low pressure (~ 28 MPa) used. It was recommended that hot isostatic pressing (HIPing), performed at higher temperatures and pressures, be investigated. HIPing was carried out in two phases, with a third and final phase currently underway. Phase I evaluated the effects of pressure and temperature conditions on the manufacture of a pressed sample. The base material was an engineered form of silver zeolite. Six samples of Ag0Z and two samples of I-Ag0Z were pressed. It was found that HIPing produced a pressed pellet of high density. Analysis of each pressed pellet by scanning electron microscopy-energy dispersive spectrophotometry (SEM-EDS) and X-ray diffraction (XRD) demonstrated that under the conditions used for pressing, the majority of the material transforms into an amorphous structure. The only crystalline phase observed in the pressed Ag0Z material was SiO2. For the samples loaded with iodine (I-Ag0Z) iodine was present as AgI clusters at low temperatures, and transformed into AgIO4 at high temperatures. Surface mapping and EDS demonstrate segregation between silver iodide phases and silicon dioxide phases. Based on the results of the Phase I study, an expanded test matrix was developed to examine the effects of multiple source materials, compositional variations, and an expanded temperature range. Each sample was analyzed with the approach used in Phase I. In all cases, there is nothing in the SEM or XRD analyses that indicates creation of any AgI-containing silicon phase, with the samples being found to be largely amorphous. Phase III of this study has been initiated and is the final phase of scoping tests. It will expand upon the test matrix completed in Phase II and will examine the durability of the pressed pellets through product consistency testing (PCT) studies. Transformation of the component material into a well-characterized iodine-containing mineral phase would be desirable. This would limit the additional experimental testing and modeling required to determine the long-term stability of the pressed pellet, as much of that information has already been learned for several common iodine-containing minerals. However, this is not an absolute requirement, especially if pellets produced by hot isostatic pressing can be demonstrated through initial PCT studies to retain iodine well despite their amorphous composition.

Jubin, R. T. [ORNL; Bruffey, S. H. [ORNL; Patton, K. K. [ORNL



Methanol conversion on acidic ZSM-5, offretite, and mordenite zeolites: a comparative study of the formation and stability of coke deposits  

Microsoft Academic Search

The deposition of carbonaceous residues, leading to aging and modifications in the acidic properties of three zeolite samples differing by the size and shape of their interconnecting channel networks (ZSM-5, offretite, and mordenite), has been investigated during the conversion reaction of methanol to hydrocarbons. Catalytic tests, thermogravimetry, and microcalorimetry are used as complementary techniques. For zeolite ZSM-5, it is observed

P. Dejaifve; A. Auroux; P. C. Gravelle; J. C. Vedrine; Z. Gabelica; E. G. Derouane



Impact of Pretreatment and Aging on the Iodine Capture Performance of Silver-Exchanged Mordenite - 12314  

SciTech Connect

Volatile gas emissions from a nuclear fuel recycle facility in the United States are governed by several key regulations, including 10 CFR 20, 40 CFR 61, and 40 CFR 190. Under 40 CFR 190, the total quantity of iodine that may be released to the environment from the entire fuel cycle is limited to 5 millicuries of I-129 per gigawatt-year of electrical energy produced by the fuel cycle. With a reasonable engineering margin, an iodine decontamination factor (DF) of approximately 1000 will be required for the complete fuel cycle. Off-gas treatment in a fuel reprocessing plant must address several gas streams containing iodine, among a number of volatile radionuclides. Past research and developmental activities identified silver-exchanged mordenite (AgZ) as a very promising sorbent based on its acid resistance, relatively high iodine and methyl iodide capacity, and high achievable DF. Recent studies at ORNL have focused on the impacts of long-term exposure to simulated off-gas streams (aging) and pretreatment on the iodine adsorption performance of hydrogen-reduced silver-exchanged mordenite (Ag{sup 0}Z). Experiments were conducted to determine the effects of long-term exposure to both dry and moist air on the iodine sorption capacity of Ag{sup 0}Z. The data indicates that aging reduces the capacity of Ag{sup 0}Z, which must be accounted for to prevent degradation of DF. Because of its high acid resistance, a AgZ sorbent has been selected specifically for application in treating off-gas streams containing iodine. While extensive tests have been conducted in the United States on a form of this sorbent, the specific material previously tested is no longer commercially available and similar materials are currently being evaluated. As part of this evaluation, tests were conducted to determine the iodine sorption properties of this replacement media and the effects of long-term (up to 6 months) exposure to simulated off-gas streams. The ultimate goal is to develop an understanding of the fundamental phenomena that controls aging for this material and other zeolites that could be considered for use in off-gas treatment in the future. The trends in the study results indicate that the amount of elemental silver observed by XRD increases from 0.3 wt% in vendor-supplied AgZ to approximately 5 wt% by reducing the material with hydrogen. The study also concluded that aging decreases the quantity of elemental silver in the material. After 2 months of aging, the Ag{sup 0} content of an experimental sample was reduced from 5 wt% to about 1.3 wt%. The form into which the elemental silver is converted during aging was not determined. Experimental tests have been initiated to study how aging of Ag{sup 0}Z impacts iodine loading on the zeolite. Loading tests with un-aged Ag{sup 0}Z resulted in an 81% silver utilization. The loading capacity of iodine on Ag{sup 0}Z was reduced with aging in dry air. Material aged for 6 months in dry air had a 40% reduction in iodine loading capacity. Under moist-air aging conditions, a significant decrease in the rate and total loading (?45% of theoretical) of iodine uptake can be observed beginning with the shortest aging period (i.e., after 1 month) when compared with the loading curve using Ag{sup 0}Z with no aging. Increasing exposure time to the humid air used to age the Ag{sup 0}Z beyond 1 month resulted in a slight additional reduction in capacity to about 35% of theoretical at 2 months. Virtually identical capacity was observed with 4 months of aging. Compared to the non-aged material, the 1 month dry-air aged Ag{sup 0}Z shows about a 35% reduction (approximate) in iodine loading capacity and the 6 month dry-air aged Ag{sup 0}Z shows about a 50% reduction. These studies generated several questions that will be addressed in future tests. They include the following: Is there indeed degradation over time (in storage) in the iodine adsorption performance of Ag{sup 0}Z? Once reduced, how should the Ag{sup 0}Z be stored- under a hydrogen atmosphere, an inert atmosphere, a desiccant, or some other method or c

Jubin, R.T.; Ramey, D.W.; Spencer, B.B.; Anderson, K.K.; Robinson, S.M. [Oak Ridge National Laboratory (United States)



FT-IR spectroscopic and catalytic study of de-aluminated H-mordenites as environmental friendly catalysts in the hydroxymethylation of 2-methoxyphenol with formaldehyde in aqueous medium  

Microsoft Academic Search

Several de-aluminated H-mordenites, prepared by treating a commercial H-mordenite (HM-16, Engelhard) with aqueous HCl solutions, were characterized and tested as catalysts in the liquid-phase hydroxymethylation of guaiacol with aqueous solutions of formalin, for the production of p-vanillic alcohol (3-methoxy-4-hydroxybenzyl alcohol), the intermediate in vanillin synthesis.Samples were obtained with Si\\/Al atomic ratios from 10 to 36; their acidic and hydrophilic properties

M. Armandi; B. Bonelli; E. Garrone; M. Ardizzi; F. Cavani; L. Dal Pozzo; L. Maselli; R. Mezzogori; G. Calestani



Calorimetric study of the acidity of decationized mordenite according to the adsorption of ammonia at 30 and 300°C  

Microsoft Academic Search

The heats of adsorption of NHâ at 30 and 300°C on decationized mordenites have been studied by the method of adsorption calorimetry. It has been found that the heat of adsorption on the strong acid sites increases with increasing temperature, the highest initial heat of adsorption of NHâ, 170 kJ\\/mole, being discovered on the dehydroxylated zeolite. Acidity spectra obtained at

G. I. Kapustin; T. R. Brueva; A. L. Klyachko; A. D. Rukhadze; A. M. Rubinshtein



Silver-Mordenite for Radiologic Gas Capture from Complex Streams: Dual Catalytic CH3I Decomposition and I Confinement  

SciTech Connect

The effective capture and storage of radiological iodine (129I) remains a strong concern for safe nuclear waste storage and safe nuclear energy. Silver-containing mordenite (MOR) is a longstanding benchmark for iodine capture. In nuclear fuel reprocessing scenarios, complex gas streams will be present and the need for high selectivity of all iodine containing compounds is of the utmost importance for safety and the environment. In particular, a molecular level understanding of the sorption of organic iodine compounds is not well understood. Here we probe the structure and distribution of methyl iodide sorbed by silver-containing MOR using a combination of crystallographic and materials characterization techniques including: infrared spectroscopy, thermogravimetric analysis with mass spectrometry, Micro-X-ray Fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. The iodine is captured inside the MOR pore in the form of AgI nanoparticles, that is consistent with the pores sizes of the MOR, indicating that the molecule is both physically and chemically captured in the Ag-MOR. The organic component is surface catalyzed by the zeolite via the formation of Surface Methoxy Species (SMS) that result in downstream organics of dimethyl ether and methanol formation.

Tina M. Nenoff; Mark Rodriguez; Nick Soelberg; Karena W. Chapman



Structural investigations of zeolites ERS-7, mordenite, and sodalite using a combination of powder diffraction and computer simulation techniques  

NASA Astrophysics Data System (ADS)

The framework structure of dehydrated template-free ERS-7 was determined by a combination of synchrotron X-ray powder diffraction and the simulated annealing approach of Deem and Newsam. The orthorhombic unit cell ( a = 9.79976(4) A, b = 12.41163(6) A, c = 22.86063(11) A) contains 6 tetrahedral framework atoms (Si/Al = 8.4), all on general positions, and 14 bridging oxygens. It can be constructed as a network of purely face-sharing 17-sided (465 46582) "picnic-basket"-shaped cages that are stacked so as to form a 1D 8-ring channel system (3.5 A x 4.7 A) that runs through the handles of the baskets. Three Bronsted acid sites were then identified via a multi-dataset Rietveld refinement against both PXD and PND data. Previous reports of correlations between diffracted intensities and aluminum content in as-synthesized Na mordenites (Si/Al = 5 to 10) are shown to be explained as a selective suppression of the (h, k,? = 2n + 1) reflections caused by linear faulting along the main channel axis. Computer generated structures with up to 500,000 atoms were used to simulate the diffuse scattering patterns for several different correlated defect models, which were then compared to previously reported experimental results. The regions of faulted material are shown to consist of c-axis chains of shifted framework 4-rings, such that neighboring pairs of chains along the a-axis shift together. The intensity of odd-? reflections is suppressed by a factor of (1 - 2po) 2 where po is the fraction of fault-shifted material, the intensity of the diffusely scattered sheets in the odd-? planes perpendicular to c* increases in proportion to po(1 - po), and the in-plane modulations of these sheets are shown to have the form sin 2(pih/2). Variable-temperature synchrotron PXD data from dehydrated sodium sodalite, Na6[Al6Si6O24], reveals a structural phase transition at 500 K that involves both a commensurate ordering of the extra-framework Na cations and a one-dimensional incommensurate modulation of the framework. Peak splittings and superlattice reflections implicate an orthorhombically distorted supercell which is related to the original 9.1 A cubic cell by a 45° rotation about a 4-fold axis and a doubling of the volume (?2 a x ?2a x a). The incommensurate modulation vector is then shown to be [211]/8.9 on the commensurate supercell basis. The 88 unique orderings of the 12 Na cations of the supercell among its 16 available sites were enumerated, and each configuration was subjected to lattice energy minimization using an empirical interatomic potential. A unique solution was identified that minimizes the structural energy and also matches the experimental diffraction data. The high-temperature phase (Pm3¯n) is well described by dynamical disorder among the cation sites and also between opposite framework "partial collapse" angles.

Campbell, Branton J.


Rationalizing Inter- and Intracrystal Heterogeneities in Dealuminated Acid Mordenite Zeolites by Stimulated Raman Scattering Microscopy Correlated with Super-resolution Fluorescence Microscopy  

PubMed Central

Dealuminated zeolites are widely used acid catalysts in research and the chemical industry. Bulk-level studies have revealed that the improved catalytic performance results from an enhanced molecular transport as well as from changes in the active sites. However, fully exploiting this information in rational catalyst design still requires insight in the intricate interplay between both. Here we introduce fluorescence and stimulated Raman scattering microscopy to quantify subcrystal reactivity as well as acid site distribution and to probe site accessibility in the set of individual mordenite zeolites. Dealumination effectively introduces significant heterogeneities between different particles and even within individual crystals. Besides enabling direct rationalization of the nanoscale catalytic performance, these observations reveal valuable information on the industrial dealumination process itself. PMID:25402756



Rationalizing Inter- and Intracrystal Heterogeneities in Dealuminated Acid Mordenite Zeolites by Stimulated Raman Scattering Microscopy Correlated with Super-resolution Fluorescence Microscopy.  


Dealuminated zeolites are widely used acid catalysts in research and the chemical industry. Bulk-level studies have revealed that the improved catalytic performance results from an enhanced molecular transport as well as from changes in the active sites. However, fully exploiting this information in rational catalyst design still requires insight in the intricate interplay between both. Here we introduce fluorescence and stimulated Raman scattering microscopy to quantify subcrystal reactivity as well as acid site distribution and to probe site accessibility in the set of individual mordenite zeolites. Dealumination effectively introduces significant heterogeneities between different particles and even within individual crystals. Besides enabling direct rationalization of the nanoscale catalytic performance, these observations reveal valuable information on the industrial dealumination process itself. PMID:25402756

Liu, Kuan-Lin; Kubarev, Alexey V; Van Loon, Jordi; Uji-I, Hiroshi; De Vos, Dirk E; Hofkens, Johan; Roeffaers, Maarten B J



Review of the thermal stability and cation exchange properties of the zeolite minerals clinoptilolite, mordenite, and analcime; applications to radioactive waste isolation in silicic tuff  

SciTech Connect

Silicic tuffs of the southern Great Basin and basalts of the Columbia River Plateau are under investigation as potential host rocks for high- and intermediate-level radioactive wastes. Nonwelded and partially welded tuffs may contain major amounts (> 50%) of the zeolite minerals clinoptilolite, mordenite, and analcime. Densely welded tuffs and some basalt flows may contain clinoptilolite as fracture filling that limits the permeability of these rocks. The cation exchange properties of these zeolite minerals allow them to pose a formidable natural barrier to the migration of cationic species of various radionuclides in aqueous solutions. However, these minerals are unstable at elevated temperatures and at low water-vapor pressures and may break down either by reversible dehydration or by irreversible mineralogical reactions. All the breakdown reactions occurring at increased temperature involve a net volume reduction and evolution of fluids. Thus, they may provide a pathway (shrinkage fractures) and a driving force (fluid pressure) for release of radionuclides to the biosphere. These reactions may be avoided by keeping zeolite-bearing horizons saturated with water and below about 85{sup 0}C. This may restrict allowable gross thermal loadings in waste repositories in volcanic rocks.

Smyth, J.R.; Caporuscio, F.A.



The growth of zeolites A, X and mordenite in space  

NASA Technical Reports Server (NTRS)

Zeolites are a class of crystalline aluminosilicate materials that form the backbone of the chemical process industry worldwide. They are used primarily as adsorbents and catalysts and support to a significant extent the positive balance of trade realized by the chemical industry in the United States (around $19 billion in 1991). The magnitude of their efforts can be appreciated when one realizes that since their introduction as 'cracking catalysts' in the early 1960's, they have saved the equivalent of 60 percent of the total oil production from Alaska's North Slope. Thus the performance of zeolite catalysts can have a profound effect on the U.S. economy. It is estimated that a 1 percent increase in yield of the gasoline fraction per barrel of oil would represent a savings of 22 million barrels of crude oil per year, representing a reduction of $400 million in the United States' balance of payments. Thus any activity that results in improvement in zeolite catalyst performance is of significant scientific and industrial interest. In addition, due to their 'stability,' uniformity, and, within limits, their 'engineerable' structures, zeolites are being tested as potential adsorbents to purify gases and liquids at the parts-per-billion levels needed in today's electronic, biomedical, and biotechnology industries and for the environment. Other exotic applications, such as host materials for quantum-confined semiconductor atomic arrays, are also being investigated. Because of the importance of this class of material, extensive efforts have been made to characterize their structures and to understand their nucleation and growth mechanisms, so as to be able to custom-make zeolites for a desired application. To date, both the nucleation mechanics and chemistry (such as what are the 'key' nutrients) are, as yet, still unknown for many, if not all, systems. The problem is compounded because there is usually a 'gel' phase present that is assumed to control the degree of supersaturation, and this gel undergoes a continuous 'polymerization' type reaction during nucleation and growth. Generally, for structure characterization and diffusion studies, which are useful in evaluating zeolites for improving yield in petroleum refining as well as for many of the proposed new applications (e.g., catalytic membranes, molecular electronics, chemical sensors) large zeolites (greater than 100 to 1000 times normal size) with minimum lattice defects are desired. Presently, the lack of understanding of zeolite nucleation and growth precludes the custom design of zeolites for these or other uses. It was hypothesized that the microgravity levels achieved in an orbiting spacecraft could help to isolate the possible effects of natural convection (which affects defect formation) and minimize sedimentation, which occurs since zeolites are twice as dense as the solution from which they are formed. This was expected to promote larger crystals by allowing growing crystals a longer residence time in a high-concentration nutrient field. Thus it was hypothesized that the microgravity environment of Earth orbit would allow the growth of large, more defect-free zeolite crystals in high yield.

Sacco, Albert, Jr.; Bac, N.; Coker, E. N.; Dixon, A. G.; Warzywoda, J.; Thompson, R. W.



Determination of Ni(II) Uptake Mechanisms on Mordenite Surfaces:1 A Combined Macroscopic and Microscopic Approach2  

E-print Network

at the water-mineral31 interface.32 33 1. Introduction34 The frequency and severity of heavy metal pollutants adverse43 health effects such as anemia, encephalopathy, diarrhea, hepatitis, nephritic syndrome,44 in2p3 at mineral-water interfaces are closely48 related with the accumulation, migration, transformation

Paris-Sud XI, Université de


Hydroisomerization of a refinery naphtha stream over platinum zeolite-based catalysts  

Microsoft Academic Search

In this paper, the hydroisomerization of a C7–C8 stream obtained by distillation of a refinery naphtha stream using platinum zeolites (mordenite, beta and ZSM-5) agglomerated with a binder was performed. Catalysts based on beta and ZSM-5 zeolites were more active than that based on mordenite one. With this catalyst, the catalyst activity was likely controlled by the accessibility to the

María Jesús Ramos; Juan Pedro Gómez; Fernando Dorado; Paula Sánchez; José Luis Valverde



Method for treating a nuclear process off-gas stream  


Disclosed is a method for selectively removing and recovering the noble gas and other gaseous components typically emitted during nuclear process operations. The method is adaptable and useful for treating dissolver off-gas effluents released during reprocessing of spent nuclear fuels whereby to permit radioactive contaminant recovery prior to releasing the remaining off-gases to the atmosphere. Briefly, the method sequentially comprises treating the off-gas stream to preliminarily remove NO.sub.x, hydrogen and carbon-containing organic compounds, and semivolatile fission product metal oxide components therefrom; adsorbing iodine components on silver-exchanged mordenite; removing water vapor carried by said stream by means of a molecular sieve; selectively removing the carbon dioxide components of said off-gas stream by means of a molecular sieve; selectively removing xenon in gas phase by passing said stream through a molecular sieve comprising silver-exchanged mordenite; selectively separating krypton from oxygen by means of a molecular sieve comprising silver-exchanged mordenite; selectively separating krypton from the bulk nitrogen stream using a molecular sieve comprising silver-exchanged mordenite cooled to about to C.; concentrating the desorbed krypton upon a molecular sieve comprising silver-exchange mordenite cooled to about to C.; and further cryogenically concentrating, and the recovering for storage, the desorbed krypton.

Pence, Dallas T. (San Diego, CA); Chou, Chun-Chao (San Diego, CA)



Chromatographic properties of zeolites modified for analysis of atmospheric pollutants  

Microsoft Academic Search

Chromatographic properties of different types of synthetic zeolites and samples of natural mordenite, modified by ion-exchange have been studied. The influence of degree of replacement and character of cations of alkali and alkaline-earth metals and also of silver and copper on chromatographic retainment of constant components of air and its most spread pollutants have been shown. Recommendations are made of

T. G. Andronikashvili; O. S. Banakh; V. I. Rogovik



Removal of Heavy Metals and Other Cations from Wastewater Using Zeolites  

Microsoft Academic Search

Zeolites from abundant natural deposits were investigated by the Bureau of Mines for efficiently cleaning up mining industry wastewaters. Twenty-two zeolites were analyzed by X-ray diffraction and inductively coupled plasma analysis (ICP). These included clinoptilolite, mordenite, chabazite, erionite, and phillipsite. The zeolites were primarily in the sodium or calcium form, but potassium and magnesium counter ions were also present. Bulk

M. J. Zamzow; B. R. Eichbaum; K. R. Sandgren; D. E. Shanks



Zeolites in Antarctic soils: Examples from Coombs Hills and Marble Point  

Microsoft Academic Search

The distribution of zeolites in rocks and soils of the McMurdo Sound region is reviewed and two new occurrences are described, One of these is in the Coombs Hills where mordenite derived from hyaloclastic rocks is found in soils formed from till. The other is of phillipsite, found at Marble Point in a bedded formation which appears to have been

G. G. C. Claridge; I. B. Campbell



Mass transport in vitric tuffs of Rainier Mesa, Nye County, Nevada  

Microsoft Academic Search

Chemical and physical analyses of reactant and product phases found in subaerially-exposed vitric tuffs of Rainier Mesa, Nevada, indicate that diagenetic alteration is occurring today. Variations in the composition of the fluid phase with depth suggest a predominantly vertical transport process whereby the dissolution of metastable glass drives the sequential precipitation of montmorillonite, clinoptilolite and possibly analcime. Mordenite was found



Ring opening of methylcyclohexane over platinum-loaded zeolites.  


The activity of different platinum-loaded zeolites (Mordenite, ZSM-12, ZSM-5, ZSM-23) was investigated in the hydroconversion of methylcyclohexane (MCH), in the context of upgrading highly aromatic distillates for fuel blending. In all cases, conversion of MCH proceeds according to a pathway where the primary products are a mixture of dimethylcyclopentanes and ethylcyclopentane formed by isomerization and ring contraction of MCH. The primary products undergo consecutive ring-opening reactions with formation of n- and isoheptanes. The latter further react to form lower-molecular-weight n- and isoalkanes. The selectivity and distribution of products deriving from ring-contraction and ring-opening reactions are strongly affected by the pore size and topology of the zeolites. ZSM-5 exhibits a strong reactant shape-selectivity effect on ring-opening products. The evaluated zeolites show the following order of activity in the conversion of methylcyclohexane: Mordenite>ZSM-12>ZSM-5>ZSM-23. PMID:18702154

Calemma, Vincenzo; Carati, Angela; Flego, Cristina; Giardino, Roberto; Gagliardi, Federica; Millini, Roberto; Bellussi, Giuseppe



Siting and Distribution of the Co Ions in Beta Zeolite: A UV–Vis–NIR and FTIR Study  

Microsoft Academic Search

The Co(II) ion sites in dehydrated beta zeolites, consisting of polymorphs A, B, and C, were identified using an approach based on a similarity between visible spectra of the Co(II) ions in mordenite, ferrierite ZSM-5, and beta zeolites, and similarity in local framework structures accommodating the Co(II) ions in these zeolites. The results were supported by FTIR spectra in the

J. D?de?ek; L. ?apek; D. Kaucký; Z. Sobal??k; B. Wichterlová



Zeolites in Pre-Caldera Pyroclastic Rocks of the Santorini Volcano, Aegean Sea, Greece  

Microsoft Academic Search

The vitric matrix of pre-caldera acid tuff and tuff breccia of the Santorini volcano, Aegean Sea, Greece has been generally replaced by one or more of the following authigenic minerals: K-rich and (K,Ca)-rich clinoptilolite, mordenite, opal-CT, and clay minerals. Halite is also present in some samples. Initial compositional inhomogeneities between the dacitic blocks in tuff breccia and tuff seem to

Panayota Tsolis-Katagas; CHRISTOS KATAGAS



An electron paramagnetic resonance spectroscopy investigation of the retention mechanisms of Mn and Cu in the nanopore channels of three zeolite minerals  

SciTech Connect

The adsorption mechanisms of divalent cations in zeolite nanopore channels can vary as a function of their pore dimensions. The nanopore inner-sphere enhancement (NISE) theory predicts that ions may dehydrate inside small nanopore channels in order to adsorb more closely to the mineral surface if the nanopore channel is sufficiently small. The results of an electron paramagnetic resonance (EPR) spectroscopy study of Mn and Cu adsorption on the zeolite minerals zeolite Y (large nanopores), ZSM-5 (intermediate nanopores), and mordenite (small nanopores) are presented. The Cu and Mn cations both adsorbed via an outer-sphere mechanism on zeolite Y based on the similarity between the adsorbed spectra and the aqueous spectra. Conversely, Mn and Cu adsorbed via an inner-sphere mechanism on mordenite based on spectrum asymmetry and peak broadening of the adsorbed spectra. However, Mn adsorbed via an outer-sphere mechanism on ZSM-5, whereas Cu adsorbed on ZSM-5 shows a high degree of surface interaction that indicates that it is adsorbed closer to the mineral surface. Evidence of dehydration and immobility was more readily evident in the spectrum of mordenite than ZSM-5, indicating that Cu was not as close to the surface on ZSM-5 as it was when adsorbed on mordenite. Divalent Mn cations are strongly hydrated and are held strongly only in zeolites with small nanopore channels. Divalent Cu cations are also strongly hydrated, but can dehydrate more easily, presumably due to the Jahn-Teller effect, and are held strongly in zeolites with medium sized nanopore channels or smaller.

Ferreira, Daniel R.; Schulthess, Cristian P.; Amonette, James E.; Walter, Eric D.



Characterisation and environmental application of an Australian natural zeolite for basic dye removal from aqueous solution  

Microsoft Academic Search

An Australian natural zeolite was collected, characterised and employed for basic dye adsorption in aqueous solution. The natural zeolite is mainly composed of clinoptiloite, quartz and mordenite and has cation-exchange capacity of 120meq\\/100g. The natural zeolite presents higher adsorption capacity for methylene blue than rhodamine B with the maximal adsorption capacity of 2.8×10?5 and 7.9×10?5mol\\/g at 50°C for rhodamine B

Shaobin Wang; Z. H. Zhu



Environmental Applications of Natural Zeolitic Materials Based on Their Ion Exchange Properties  

Microsoft Academic Search

\\u000a Present and potential use of natural zeolites as cation exchangers in environmental protection is reviewed. Siliceous zeolites,\\u000a such as chabazite, clinoptilolite, mordenite and phillipsite, exhibit good selectivities for cations with low charge density,\\u000a e.g., Cs+ and NH4\\u000a +, and for cations with low hydration energy, such as Pb2+. Zeolitised tuffs, containing the mentioned zeolites, may therefore be utilised for removing

C. Colella; Piazza Ie; V. Tecchio


A new synthesis procedure for titanium-containing zeolites under strong alkaline conditions and the catalytic activity for partial oxidation and photocatalytic decomposition  

Microsoft Academic Search

A new synthesis procedure for titanium-containing aluminosilicate zeolites has been obtained using a clear colloidal dispersion (sol) which was prepared with titanium isopropoxide, water, hydrochloric acid and colloidal silica, Ludox. When NaY, KL, offretite, mordenite and ZSM-5 zeolites were crystallized from the sol following conventional hydrothermal crystallization procedures, all the aluminosilicate zeolites showed the same X-ray absorption fine structure at

Ja Hun Kwak; Sung June Cho; Ryong Ryoo



Removal of Metal Cations from Water Using Zeolites  

Microsoft Academic Search

Zeolites from abundant natural deposits were investigated by the Bureau of Mines for efficiently cleaning up mining industry wastewaters. Twenty-four zeolite samples were analyzed by x-ray diffraction and inductively coupled plasma. These included clinoptilolite, mordenite, chabazite, erionite, and phillipsite. Bulk densities of a sized fraction (-40, +65 mesh) varied from 0.48 to 0.93 g\\/mL. Attrition losses ranged from 1 to

M. J. Zamzow; J. E. Murphy



Oxygen and hydrogen isotope geochemistry of zeolites  

NASA Technical Reports Server (NTRS)

Oxygen and hydrogen isotope ratios for natural samples of the zeolites analcime, chabazite, clinoptilolite, laumontite, mordenite, and natrolite have been obtained. The zeolite samples were classified into sedimentary, hydrothermal, and igneous groups. The ratios for each species of zeolite are reported. The results are used to discuss the origin of channel water, the role of zeolites in water-rock interaction, and the possibility that a calibrated zeolite could be used as a low-temperature geothermometer.

Karlsson, Haraldur R.; Clayton, Robert N.



Characterization of acidic properties of microporous and mesoporous zeolite catalysts using TGA and DSC  

SciTech Connect

Thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) were applied for characterizing the acidic properties of microporous and mesoporous zeolite catalysts through temperature-programmed desorption (TPD) of n-butylamine (n-BA). A flow system was designed with heating and evacuation capability for preparing the n-BA adsorbed sample. The sample was then transferred to TGA (or DSC) apparatus. n-BA desorption conducted on TGA at different temperatures represents the interaction with surface acidic sites of different strength. BAse desorption at 100-240{degrees}C, 240-340{degrees}C, and 340-500{degrees}C, was classified as weak, intramediate, and strong acid sites, respectively. DSC indicates the endothermic nature of the differential thermogravimetric peaks (observed from TGA) in the above temperature regimes, confirming the TPD data. The microporous zeolites examined include three proton-form mordenites, three proton-form and metal-ion exchanged Y-zeolites, and four noble metal catalysts supported on mordenite and Y-zeolite. Four mesoporous zeolites were synthesized and examined by the same TPD method. Both the total acidity (mmol/g) and acid strength distribution depend on the zeolite type. Si/Al ratio, and metal loading. Ni and La ion-exchange decreased the strong acid sites. Pt and Pd loading on an HY decreased the strong acid sites but their loading on an H-mordenite had little effect on its strong acid sites. Mesoporous zeolites showed lower acidity and lower fraction of strong acid sites compared to HY and H-mordenites. However, the acidity of mesoporous zeolites strongly depends on the aluminum source compounds used in the hydrothermal synthesis of the zeolites.

Song, Chunshan; Lai, Wei-Chuan; Schmitz, A.D.; Reddy, K.M. [Pennsylvania State Univ., University Park, PA (United States)] [and others



Characterization of acidic properties of microporous and mesoporous zeolite catalysts using TGA and DSC  

SciTech Connect

Thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) were applied for characterizing the acidic properties of microporous and mesoporous zeolite catalysts through temperature-programmed desorption (TPD) of n-butylamine (n-BA) as a base probe molecule. A flow system was designed with heating and evacuation capability for preparing the n-BA adsorbed sample. In the TGA, n-BA desorption at different temperatures represents the interaction with surface acidic sites of different strength. The acid sites corresponding to base desorption at 100-240{degrees}C, 240-340{degrees}C, and 340-500{degrees}C, were classified as weak, intermediate, and strong acid sites, respectively. DSC indicates the endothermic nature of the differential thermogravimetric peaks (observed from TGA) in the above temperature regimes, consuming the TPD data. The microporous zeolites examined include three proton-form mordenites, three proton-form and metal-ion exchanged Y-zeolites, and four noble metal catalysts supported on mordenite and Y-zeolite. Four mesoporous zeolites were synthesized and examined by the same TPD method. Both the total acidity (mmol/g) and acid strength distribution depend on the zeolite VAX, Si/Al ratio, and metal loading. Ni and La ion-exchange decreased the strong acid sites. Pt and Pd loading on an HY decreased the strong acid sites but their loading on an H-mordenite had little effect on its strong acid sites. Mesoporous zeolites showed lower acidity and lower fraction of strong acid sites compared to HY and H-mordenites. However, the acidity of mesoporous zeolites strongly depends on the aluminum source compounds used in the hydrothermal synthesis of the zeolites.

Song, Chunshan; Lai, Wei-Chuan; Schmitz, A.D. [Pennsylvania State Univ., University Park, PA (United States)] [and others



New catalysts for the indirect liquefaction of coal. Second annual technical report, August 1, 1981-July 31, 1982  

SciTech Connect

Series of zeolite-supported iron-containing catalysts with weight percent iron (% Fe) varying from approx. 1 to approx. 17% Fe have been prepared from Fe/sub 3/(CO)/sub 12/ and the synthetic zeolites ZSM-5, mordenite and 13X by an extraction technique. The zeolites ZSM-5 and mordenite were used in the acid form, 13X in the sodium form. The catalysts were characterized by a variety of techniques including infrared spectroscopy, X-ray powder diffractometry, X-ray photoelectron spectroscopy, ion-scattering spectrometry and Mossbauer spectroscopy. All catalysts contain highly dispersed, small particle-sized ..gamma..-Fe/sub 2/O/sub 3/ with a small amount of the iron (0.6 to 1.5% Fe depending on the support) located in the pores of the support. Evaluation of the catalytic ability of some of these materials for synthesis gas conversion was conducted at 280/sup 0/C and 300/sup 0/C by using a fixed-bed continuous flow microreactor. All catalysts evaluated produce significant quantities of hydrocarbons. The distribution of hydrocarbons varies, depending upon the support used, for catalysts with similar weight percent iron. For the liquid hydrocarbons, Fe/ZSM-5 produces the highest percentage of aromatics, Fe/mordenite produces the highest percentage of olefins, and Fe/13X produces the highest percentage of saturates. The effect of support acidity and pore structure on hydrocarbon product distribution is discussed.

Melson, G.A.



Distribution of potentially hazardous phases in the subsurface at Yucca Mountain, Nevada  

SciTech Connect

Drilling, trenching, excavation of the Exploratory Studies Facility, and other surface and underground-distributing activities have the potential to release minerals into the environment from tuffs at Yucca Mountain, Nevada. Some of these minerals may be potential respiratory health hazards. Therefore, an understanding of the distribution of the minerals that may potentially be liberated during site-characterization and operation of the potential repository is crucial to ensuring worker and public safety. Analysis of previously reported mineralogy of Yucca Mountain tuffs using data and criteria from the International Agency for Research on Cancer (IARC) suggests that the following minerals are of potential concern: quartz, cristobalite, tridymite, opal-CT, erionite, mordenite, and palygorskite. The authors have re-evaluated the three-dimensional mineral distribution at Yucca Mountain above the static water level both in bulk-rock samples and in fractures, using quantitative X-ray powder diffraction analysis. Erionite, mordenite, and palygorskite occur primarily in fractures; the crystalline-silica minerals, quartz, cristobalite, and tridymite are major bulk-rock phases. Erionite occurs in the altered zone just above the lower Topopah Spring Member vitrophyre, and an occurrence below the vitrophyre but above the Calico Hills has recently been identified. In this latter occurrence, erionite is present in the matrix at levels up to 35 wt%. Mordenite and palygorskite occur throughout the vadose zone nearly to the surface. Opal-CT is limited to zeolitic horizons.

Guthrie, G.D. Jr.; Bish, D.L.; Chipera, S.J.; Raymond, R. Jr.



Aluminum-Phosphate Binder Formation in Zeolites as Probed with X-ray Absorption Microscopy.  


In this work, three industrially relevant zeolites with framework topologies of MOR, FAU and FER have been explored on their ability to form an AlPO4 phase by reaction of a phosphate precursor with expelled framework aluminum. A detailed study was performed on zeolite H-mordenite, using in situ STXM and soft X-ray absorption tomography, complemented with (27)Al and (31)P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, XRD, FT-IR spectroscopy, and N2 physisorption. Extraframework aluminum was extracted from steam-dealuminated H-mordenite and shown to dominantly consist of amorphous AlO(OH). It was found that phosphoric acid readily reacts with the AlO(OH) phase in dealuminated H-mordenite and forms an extraframework amorphous AlPO4 phase. It was found that while AlPO4 crystallizes outside of the zeolitic channel system forming AlPO4 islands, AlPO4 that remains inside tends to stay more amorphous. In the case of ultrastable zeolite Y the FAU framework collapsed during phosphatation, due to extraction of framework aluminum from the lattice. However, using milder phosphatation conditions an extraframework AlPO4 ?-cristobalite/tridymite phase could also be produced within the FAU framework. Finally, in steamed zeolite ferrierite with FER topology the extraframework aluminum species were trapped and therefore not accessible for phosphoric acid; hence, no AlPO4 phase could be formed within the structure. Therefore, the parameters to be taken into account in AlPO4 synthesis are the framework Si/Al ratio, stability of framework aluminum, pore dimensionality and accessibility of extraframework aluminum species. PMID:25415849

van der Bij, Hendrik E; Cicmil, Dimitrije; Wang, Jian; Meirer, Florian; de Groot, Frank M F; Weckhuysen, Bert M



Zeolite crystal growth in space - What has been learned  

NASA Technical Reports Server (NTRS)

Three zeolite crystal growth experiments developed at WPI have been performed in space in last twelve months. One experiment, GAS-1, illustrated that to grow large, crystallographically uniform crystals in space, the precursor solutions should be mixed in microgravity. Another experiment evaluated the optimum mixing protocol for solutions that chemically interact ('gel') on contact. These results were utilized in setting the protocol for mixing nineteen zeolite solutions that were then processed and yielded zeolites A, X and mordenite. All solutions in which the nucleation event was influenced produced larger, more 'uniform' crystals than did identical solutions processed on earth.

Sacco, A., Jr.; Thompson, R. W.; Dixon, A. G.



Zeolite catalysis: technology  

SciTech Connect

Zeolites have been used as catalysts in industry since the early nineteen sixties. The great majority of commercial applications employ one of three zeolite types: zeolite Y; Mordenite; ZSM-5. By far the largest use of zeolites is in catalytic cracking, and to a lesser extent in hydrocracking. This paper reviews the rapid development of zeolite catalysis and its application in industries such as: the production of gasoline by catalytic cracking of petroleum; isomerization of C/sub 5/ and C/sub 6/ paraffin hydrocarbons; alkylation of aromatics with olefins; xylene isomerization; and conversion of methanol to gasoline.

Heinemann, H.



Catalytic Reduction of Nitrogen Oxides by Propene in the Presence of Oxygen over Cerium Ion-Exchanged Zeolites  

Microsoft Academic Search

The mechanism of catalytic reduction of NOxby propene in the presence of oxygen, NO (or NO2)+C3H6+O2reaction, over Ce-supported catalysts was studied, focusing on the relative activities of catalysts and carriers for several relevant reactions. The rate of N2formation in the NO+C3H6+O2reaction was very much dependent on the kinds of carriers, the rate being in the order of Ce-ZSM-5>Ce-mordenite?Ce-Y zeolite>Ce\\/SiO2. This

Chikafumi Yokoyama; Makoto Misono



Catalytic transformations of olefins on HZSM5 observed by radiolysis/EPR  

SciTech Connect

A new method for elucidating elementary reaction steps in zeolite catalysis was demonstrated for reactions of isobutene and other monoolefins on HZSM5. Radiolysis was used to `spin label` reaction products, and EPR was used for product analysis. The evolution of products was revealed by quenching the reactions cryogenically in a series of equilibrium experiments. Isobutene dimerization and isomerization occur on HZSM5 even at 77 K, and cracking occurs below room temperature. The radiolysis/EPR results allow a consistent interpretation of the literature on EPR signals that arise spontaneously upon interaction of acyclic olefins with air-activated H-Mordenite and HZSM5. 55 refs., 10 figs., 2 tabs.

Piocos, E.A.; Han, P.; Werst, D.W. [Argonne National Lab., IL (United States)] [Argonne National Lab., IL (United States)



Paramagnetic complexes of 9,10-anthraquinone on zeolite surfaces and their thermal transformations  

NASA Astrophysics Data System (ADS)

The concentration of one-electron transfer sites on the surface of H-ZSM-5, H-Y, H-mordenite, and H-? zeolites was measured by EPR using 9,10-antrhraquinone as a probe. It has been found that the hyperfine structure from four protons typical for one-centered complexes of anthraquinone with one acidic site was observed in the EPR spectra after anthraquinone interaction with a zeolite surface in the temperature range of 373 to 423 K. It has been established that an elevated temperature of 473 K promoted the decomposition of the adsorbed anthraquinone and the disappearance of the hyperfine structure. It has been shown that the thermal instability of anthraquinone adsorbed on zeolites changed in the series H-? > H-Y > H-ZSM-5 ˜ H-mordenite; the coke-forming ability of zeolites with regard to n-decane at 443 K changed in a similar manner. It has been established that the presence of air promoted coke-forming processes upon interaction between n-decane and zeolites.

Fionov, A. V.; Nekhaev, A. I.; Shchapin, I. Yu.; Maksimov, A. L.; Lunin, V. V.



Equilibrium modeling of the formation of zeolites in fractures at Yucca Mountain, Nevada  

SciTech Connect

Yucca Mountain, in southern Nevada, is currently being investigated to determine its suitability to host the first US high-level nuclear waste repository. One of the reasons that Yucca Mountain was chosen for study is the presence of thick sequences of zeolite-rich horizons. In as much as fractures may serve as potential pathways for aqueous transport, the minerals that line fractures are of particular interest. Zeolites are common in fractures at Yucca Mountain and consist mainly of clinoptilolite/heulandite and mordenite although sporadic occurrences of chabazite, erionite, phillipsite, and stellrite have been identified using X-ray powder diffraction. To understand better the conditions under which the observed zeolite species were formed, thermodynamic data were estimated and calculations of log a((K{sup +}){sup 2}/Ca{sup ++}) versus log a((Na{sup +}){sup 2}/Ca{sup ++}) were conducted at various temperatures and silica activities. Using present-day Yucca Mountain water chemistries as a lower constraint on silica activity, clinoptilolite/heulandite and mordenite are still the zeolite species that would form under present conditions.

Chipera, S.J.; Bish, D.L.; Carlos, B.A.



Hydrolysis of cellulose by amorphous carbon bearing SO3H, COOH, and OH groups.  


The hydrolysis of cellulose into saccharides using a range of solid catalysts is investigated for potential application in the environmentally benign saccharification of cellulose. Crystalline pure cellulose is not hydrolyzed by conventional strong solid Brønsted acid catalysts such as niobic acid, H-mordenite, Nafion and Amberlyst-15, whereas amorphous carbon bearing SO 3H, COOH, and OH function as an efficient catalyst for the reaction. The apparent activation energy for the hydrolysis of cellulose into glucose using the carbon catalyst is estimated to be 110 kJ mol (-1), smaller than that for sulfuric acid under optimal conditions (170 kJ mol (-1)). The carbon catalyst can be readily separated from the saccharide solution after reaction for reuse in the reaction without loss of activity. The catalytic performance of the carbon catalyst is attributed to the ability of the material to adsorb beta-1,4 glucan, which does not adsorb to other solid acids. PMID:18759399

Suganuma, Satoshi; Nakajima, Kiyotaka; Kitano, Masaaki; Yamaguchi, Daizo; Kato, Hideki; Hayashi, Shigenobu; Hara, Michikazu



Optical spectra of noble metal nanoparticles supported on zeolites  

NASA Astrophysics Data System (ADS)

Optical spectra of noble metal nano-particles supported on different types of zeolites are studied and compared. The absorbance spectra of Cu, Ag and Au nanoparticles supported on mordenite, ?-zeolite, Na/Y and H/Y zeolites respectively are reported. Spectra for pre-exchanged Au-Cu/Na/Y, Au-Ni/Na/Y and Au-Fe/Na/Y are also studied. A simple effective medium approach (Maxwell-Garnett) is used to obtain a theoretical complex effective dielectric function of the composite and to asses the sensibility of the plasmon resonance to the sample characteristics. The knowledge of these properties can hopefully be applied to the development of optical tools to monitor the synthetic path.

López Bastidas, Catalina; Smolentseva, Elena; Machorro, Roberto; Petranovskii, Vitalii



Gas phase synthesis of MTBE from methanol and isobutene over dealuminated zeolites  

SciTech Connect

Gas phase synthesis of MTBE from methanol and isobutene has been investigated over different zeolites. It is shown that bulk Si/Al ratio has a marked influence on the formation of MTBE. H-beta zeolite was found to be as active as acid Amberlyst-15 (reference catalyst), and noticeably superior to non- and dealuminated forms of H-Y, H-ZSM-5, zeolite omega, and H-mordenites. Screening test results obtained over other catalysts (SAPOs and pillared clays) are briefly commented. The contribution of the external surface of the zeolites to the reaction is discussed. In the case of H-Y zeolites, it is shown that extra framework Al species ({sup 27}Al NMR signal at 30 ppm) have a detrimental effect on the reaction. 64 refs., 12 figs., 3 tabs.

Collignon, F.; Mariani, M.; Moreno, S.; Remy, M.; Poncelet, G. [Universite Catholique de Louvain (Belgium)] [Universite Catholique de Louvain (Belgium)



The zeolite deposits of Greece  

USGS Publications Warehouse

Zeolites are present in altered pyroclastic rocks at many localities in Greece, and large deposits of potential economic interest are present in three areas: (1) the Evros region of the province of Thrace in the north-eastern part of the Greek mainland; (2) the islands of Kimolos and Poliegos in the western Aegean; and (3) the island of Samos in the eastern Aegean Sea. The deposits in Thrace are of Eocene-Oligocene age and are rich in heulandite and/or clinoptilolite. Those of Kimolos and Poliegos are mainly Quaternary and are rich in mordenite. Those of Samos are Miocene, and are rich in clinoptilolite and/or analcime. The deposits in Thrace are believed to have formed in an open hydrological system by the action of meteoric water, and those of the western Aegean islands in a similar way but under conditions of high heat flow, whereas the deposits in Samos were formed in a saline-alkaline lake.

Stamatakis, M.G.; Hall, A.; Hein, J.R.



Slow release of NO by microporous titanosilicate ETS-4.  


A novel approach to designing nitric oxide (NO) storage and releasing microporous agents based on very stable, zeolite-type silicates possessing framework unsaturated transition-metal centers has been proposed. This idea has been illustrated with ETS-4 [Na(9)Si(12)Ti(5)O(38)(OH)·xH(2)O], a titanosilicate that displays excellent NO adsorption capacity and a slow releasing kinetics. The performance of these materials has been compared to the performance of titanosilicate ETS-10, [(Na,K)(2)Si(5)TiO(13)·xH(2)O], of benchmark zeolites mordenite and CaA, and of natural and pillared clays. DFT periodic calculations have shown that the presence of water in the pores of ETS-4 promotes the NO adsorption at the unsaturated (pentacoordinated) Ti(4+) framework ions. PMID:21449590

Pinto, Moisés L; Rocha, João; Gomes, José R B; Pires, João



Fracture-lining minerals in the lower Topopah Spring Tuff at Yucca Mountain  

SciTech Connect

Fracture-lining minerals in the lower Topopah Spring Member of the Paintbrush Tuff at Yucca Mountain, Nevada, are being examined to characterize potential flow paths within and away from the candidate repository horizon. Fracture coatings within this interval can be divided into five categories based on rock matrix and type of fracture. Fracture coatings in the densely welded tuff above the basal vitrophyre, near the candidate repository horizon, include (1) those related to lithophysal cavities; (2) mordenite and manganese oxides on nearly planar fractures; (3) later fracture coatings consisting of zeolites, smectite, and calcite. Fracture-coating minerals in the vitrophyre are fine-grained and consist of smectite and a variety of zeolites. The non- to partially-welded vitric and/or zeolitic stuff below the vitrophyre contains fractures mostly lined by cristobalite and clinoptilolite. 13 refs., 2 figs., 1 tab.

Carlos, B.A.; Bish, D.L.; Chipera, S.J.



Hydrothermal interactions of cement or mortar with zeolites or montmorillonites  

SciTech Connect

Concretes, grouts, clays and/or zeolites are candidate borehole, shaft or tunnel plugging materials for any nuclear waste repository. Interactions between these plugging materials may take place under mild hydrothermal conditions during the life of a repository. Class H cement or motar (PSU/WES mixture) was reacted with one of two montmorillonites, clinoptilolite or mordenite at 100/sup 0/ and 200/sup 0/C for different periods under a confining pressure of 30 MPa. The solid reaction products were characterized by x-ray powder diffraction and scanning electron microscopy after the hydrothermal treatments. When zeolites were in contact (not intimate mixture) with class H cement, they did not seem to alter but clinoptilolite altered to analcime, and mordenite became poorly crystalline in the presence of mortar (containing NaCl) at both 100/sup 0/ and 200/sup 0/C. When cement or mortar was intimately mixed with zeolites or montmorillonites and reacted hydrothermally, the reaction resulted in the formation of Al substituted tobermorite (11A type) in all cases (this type of reaction is expected at the interface) at both 100/sup 0/ and 200/sup 0/C. The mechanism of tobermorite formation includes the decomposition of zeolites or montmorillonites in the presence of alkaline (pH approx. = 12) cement or mortar and recrystallization to form Al substituted tobermorite. Cesium sorption measurements in 0.01N CaCl/sub 2/ on the reaction products revealed that selective Cs sorption increased in most cases, even though little or none of the original zeolites and montmorillonites remained in the products. For example, Cs sorption K/sub d/ (mL/g) increased from 80 in the untreated mortar + Ca montmorillonite mixture to 1700 in the interaction product which is Al substituted tobermorite. Thus, we discover here that Al substituted tobermorite has good selectivity for Cs.

Komarneni, S.; Roy, D.M.



Preparation for kinetic measurements on the silicates of the Yucca Mountain potential repository. [Final report], June 15, 1993--September 30, 1993  

SciTech Connect

Part 1, ``The Preparation of Clinoptilolite, Mordenite and Analcime,`` summarized progress made during the contract period on preparing Na-end member clinoptilolite, mordenite, and analcime. The objective is to use the prepared zeolites to determine rates of dissolution and precipitation in laboratory flow-through systems in both this lab to 350 C and by the geochemists at Yale University to about 80 C. Because clinoptilolite represents the most complicated phase of these three zeolites and it is most abundant at Yucca Mountain, the authors have concentrated most of their efforts on its preparation. They have collected, high-concentration natural clinoptilolite samples. A hindered settling technique that takes advantage of the relatively low specific gravity of clinoptilolite coupled with ultrasonic cleaning in deionized water has been employed. This material is now a mixed Na-K zeolite which must then be converted to the pure Na-end member composition. In Part 2, ``Draft Manuscript on the Heterogeneous Kinetics of Cristobalite,`` experiments on the rates of reactions of dissolution and precipitation of cristobalite were carried at 150--300 C. Results show that cristobalite may precipitate from hydrothermal solution if the concentration of Si(OH){sub 4} exceeds that at quartz saturation and is less than that of amorphous silica saturation and if there are cristobalite nuclei present. Such nuclei may occur where there has been devitrification of volcanic glasses, for example. Cristobalite has refused to crystallize in the absence of such nuclei. Steady state concentrations were reached experimentally after starting at 150 {degree} with initially supersaturated solutions and at 200 C starting with either supersaturated or undersaturated solutions. From the steady state conditions, equilibrium constants can be derived.




Studies of anions sorption on natural zeolites.  


This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method. PMID:25002191

Barczyk, K; Mozgawa, W; Król, M



Changes in the Vibrational Spectra of Zeolites Due to Sorption of Heavy Metal Cations  

NASA Astrophysics Data System (ADS)

This work presents the results of spectroscopic (MIR and Raman) studies of zeolite structures after immobilization of heavy metal cations from aqueous solutions. The sorption of Ag+, Cu2+, Cd2+, Pb2+, Zn2+, and Cr3+ ions has been conducted on zeolites belonging to different structural groups, i.e., sodium forms of natural chabazite, mordenite, ferrierite, and clinoptilolite, as well as on synthetic zeolite Y. Systematic changes in intensities and positions of the bands corresponding to the characteristic ring vibrations have been observed in the measured spectra. The most visible changes are observed in the FT-IR spectra of the samples in the range of 850-450 cm-1, and in the Raman spectra in the range of 600-250 cm-1. Depending on the zeolite structure, the bands, which can be regarded as a kind of indicator of ion exchange, were indentifi ed. For example, in the case of IR spectra, these bands are at 766, 703, 648, 578, and 506 cm-1 for zeolite Y, at 733 and 560 cm-1 for mordenite, at 675 cm-1 for clinoptilolite, etc. The degree of changes depends on both the type of cation and its concentration in the initial solution. This is connected with the way of binding of metal ions to the zeolite aluminosilicate framework, i.e., a proportion of the ion exchange and chemisorption in the process. Cations mainly undergoing ion exchange, such as Cd2+ or Pb2+, have the greatest impact on the character of the spectra. On the other hand, Cr3+ ions practically do not modify the spectra of zeolites. Results of IR and Raman spectroscopic studies have been compared with those obtained by atomic absorption spectroscopy (AAS), from which the proportion of ion exchange to chemisorption in the process and the effective cation exchange capacity of the individual samples have been estimated.

Król, M.; Mozgawa, W.; Barczyk, K.; Bajda, T.; Kozanecki, M.



Environmental effect and genetic influence: a regional cancer predisposition survey in the Zonguldak region of Northwest Turkey  

NASA Astrophysics Data System (ADS)

The Cretaceous-Eocene volcano-sedimentary units of the Zonguldak region of the western Black Sea consist of subalkaline andesite and tuff, and sandstone dominated by smectite, kaolinite, accessory chlorite, illite, mordenite, and analcime associated with feldspar, quartz, opal-CT, amphibole, and calcite. Kaolinization, chloritization, sericitization, albitization, Fe-Ti-oxidation, and the presence of zeolite, epidote, and illite in andesitic rocks and tuffaceous materials developed as a result of the degradation of a glass shards matrix, enclosed feldspar, and clinopyroxene-type phenocrysts, due to alteration processes. The association of feldspar and glass with smectite and kaolinite, and the suborientation of feldspar-edged, subparallel kaolinite plates to fracture axes may exhibit an authigenic smectite or kaolinite. Increased alteration degree upward in which Al, Fe, and Ti are gained, and Si, Na, K, and Ca are depleted, is due to the alteration following possible diagenesis and hydrothermal activities. Micromorphologically, fibrous mordenite in the altered units and the presence of needle-type chrysotile in the residential buildings in which cancer cases lived were detected. In addition, the segregation pattern of cancer susceptibility in the region strongly suggested an environmental effect and a genetic influence on the increased cancer incidence in the region. The most likely diagnosis was Li-Fraumeni syndrome, which is one of the hereditary cancer predisposition syndromes; however, no mutations were observed in the p53 gene, which is the major cause of Li-Fraumeni syndrome. The micromorphology observed in the altered units in which cancer cases were detected may have a role in the expression of an unidentified gene, but does not explain alone the occurrence of cancer as a primary cause in the region.

Kadir, Selahattin; Önen-Hall, A. Piril; Aydin, S. Nihal; Yakicier, Cengiz; Akarsu, Nurten; Tuncer, Murat



Hydrothermal alteration in research drill hole Y-3, Lower Geyser Basin, Yellowstone National Park, Wyoming  

USGS Publications Warehouse

Y-3, a U.S. Geological Survey research diamond-drill hole in Lower Geyser Basin, Yellowstone National Park, Wyoming, reached a depth of 156.7 m. The recovered drill core consists of 42.2 m of surficial (mostly glacial) sediments and two rhyolite flows (Nez Perce Creek flow and an older, unnamed rhyolite flow) of the Central Plateau Member of the Pleistocene Plateau Rhyolite. Hydrothermal alteration is fairly extensive in most of the drill core. The surficial deposits are largely cemented by silica and zeolite minerals; and the two rhyolite flows are, in part, bleached by thermal water that deposited numerous hydrothermal minerals in cavities and fractures. Hydrothermal minerals containing sodium as a dominant cation (analcime, clinoptilolite, mordenite, Na-smectite, and aegirine) are more abundant than calcium-bearing minerals (calcite, fluorite, Ca-smectite, and pectolite) in the sedimentary section of the drill core. In the volcanic section of drill core Y-3, calcium-rich minerals (dachiardite, laumontite, yugawaralite, calcite, fluorite, Ca-smectite, pectolite, and truscottite) are predominant over sodium-bearing minerals (aegirine, mordenite, and Na-smectite). Hydrothermal minerals that contain significant amounts of potassium (alunite and lepidolite in the sediments and illitesmectite in the rhyolite flows) are found in the two drill-core intervals. Drill core y:.3 also contains hydrothermal silica minerals (opal, [3-cristobalite, chalcedony, and quartz), other clay minerals (allophane, halloysite, kaolinite, and chlorite), gypsum, pyrite, and hematite. The dominance of calcium-bearing hydrothermal minerals in the lower rhyolitic section of the y:.3 drill core appears to be due to loss of calcium, along with potassium, during adiabatic cooling of an ascending boiling water.

Bargar, Keith E.; Beeson, Melvin H.



Summary of the mineralogy-petrology of tuffs of Yucca Mountain and the secondary-phase thermal stability in tuffs  

SciTech Connect

Yucca Mountain is composed of a thick sequence of silicic tuffs that are quite variable in degree of welding, alteration, and zeolitization. Tuff units above the water table are commonly devitrified or still vitric, with the exception of the zeolitized Pah Canyon Member in USW-G2. The devitrified tuffs above the water table commonly contain alkali feldspar, quartz, tridymite, and cristobalite, with minor smectite. The vitric tuffs are partly to wholly altered to sodium-calcium-saturated smectite. Below the water table are generally densely welded nonzeolitized tuffs and less densely welded zeolite-containing tuffs. The specific mineral assemblage present in Yucca Mountain tuffs has important implications in choosing a repository. The secondary phases clinoptilolite, mordenite, and smectite are very important because of their large cation sorption capacities. However, whereas densely welded tuffs containing no zeolite or glass are resistant to heating and do not dehydrate significantly, zeolitized, vitric, and smectite-containing horizons are very sensitive to minor increases in temperature. Smectites are particularly sensitive to changes in water vapor pressure and temperature, and temperature increases can lead to water evolution and large volume reductions. Similarly, clinoptilolite and mordenite begin to dehydrate below 100{sup 0}C, resulting in volume decreases. The exact effect of temperature on vitric tuffs is unclear. Under hydrothermal conditions the smectites gradually transform to nonexpanding, low sorption capacity illites, and there is evidence that this reaction has occurred in the deeper portions of USW-G2. Clinoptilolite transforms under hydrothermal conditions to analcime plus quartz with a concomitant volume decrease and water evolution. Again, there is evidence of this reaction occurring in Yucca Mountain tuffs at 80 to 100{sup 0}C.

Bish, D.L.; Vaniman, D.T.; Byers, F.M. Jr.; Broxton, D.E.



Zeolite-clay mineral zonation of volcaniclastic sediments within the McDermitt caldera complex of Nevada and Oregon  

USGS Publications Warehouse

Volcaniclastic sediments deposited in the moat of the collapsed McDermitt caldera complex have been altered chiefly to zeolites and potassium feldspar. The original rhyolitic and peralkaline ash-flow tuffs are included in conglomerates at the caldera rims and grade into a lacustrine series near the center of the collapse. The tuffs show a lateral zeolitic alteration from almost fresh glass to clinoptilolite, clinoptilolite-mordenite, and erionite; to analcime-potassium feldspar; and finally to potassium feldspar. Vertical zonation is in approximately the same order. Clay minerals in associated mudstones, on the other hand, show little lateral variation but a distinct vertical zonation, having a basal dioctahedral smectite, a medial trioctahedral smectite, and an upper dioctahedral smectite. The medial trioctahedral smectite is enriched in lithium (as much as 6,800 ppm Li). Hydrothermal alteration of the volcaniclastic sediments, forming both mercury and uranium deposits, caused a distinct zeolite and clay-mineral zonation within the general lateral zonation. The center of alteration is generally potassium feldspar, commonly associated with alunite. Potassium feldspar grades laterally and vertically to either clinoptilolite or clinoptilolite-mordenite, generally associated with gypsum. This zone then grades vertically and laterally into fresh glass. The clay minerals are a dioctahedral smectite, a mixed-layer clay mineral, and a 7-A clay mineral. The mixed-layer and 7-A clay minerals are associated with the potassium feldspar-alunite zone of alteration, and the dioctahedral smectite is associated with clinoptilolite. This mineralogical zonation may be an exploration guide for mercury and uranium mineralization in the caldera complex environment.

Glanzman, Richard K.; Rytuba, James J.



Revised mineralogic summary of Yucca Mountain, Nevada  

SciTech Connect

We have evaluated three-dimensional mineral distribution at Yucca Mountain, Nevada, using quantitative x-ray powder diffraction analysis. All data were obtained on core cuttings, or sidewall samples obtained from drill holes at and around Yucca Mountain. Previously published data are included with corrections, together with new data for several drill holes. The new data presented in this report used the internal standard method of quantitative analysis, which yields results of high precision for the phases commonly found in Yucca Mountain tuffs including opal-CT and glass. Mineralogical trends with depth previously noted are clearly shown by these new data. Glass occurrence is restricted almost without exception to above the present-day static water level (SWL), although glass has been identified below the SWL in partially zeolitized tuffs. Silica phases undergo well-defined transitions with depth, with tridymite and cristobalite occurring only above the SWL, opal-CT occurring with clinoptilolite-mordenite tuffs, and quartz most abundant below the SWL. Smectite occurs in small amounts in most samples but is enriched in two distinct zones. These zones are at the top of the vitric nonwelded base of the Tiva Canyon Member and at the top of the basal vitrophyre of the Topopah Spring Member. Our data support the presence of several zones of mordenite and clinoptilolite-heulandite as shown previously. New data on several deep clinoptililite-heulandite samples coexisting with analcime show that they are heulandite. Phillipsite has not been found in any Yucca Mountain samples, but erionite and chabazite have been found once in fractures. 21 refs., 17 figs.

Bish, D.L.; Chipera, S.J.



Hydrothermal alteration and evolution of the Ohakuri hydrothermal system, Taupo volcanic zone, New Zealand  

NASA Astrophysics Data System (ADS)

Erosion and excavations at Ohakuri in the Taupo Volcanic zone have exposed the upper portion (100-150 m) of a hydrothermal system that was active sometime between 700,000 and 160,000 years ago. Extensive hydrothermal alteration occurred within a host sequence of young, relatively undeformed, chemically and lithologically similar unwelded rhyolitic ignimbrite and air-fall tuffs. Mapping and petrologic work have identified six distinct alteration types. An early event formed a concentrically zoned suite of alteration through the pervasive movement of alkaline chloride type water. In the innermost zone, primary rock components were almost entirely converted to quartz + adularia ± illite ± hematite ± leucoxene. Mineralized veins and breccias of quartz ± pyrite ± adularia ± chlorite formed here in response to episodic hydraulic fracturing. This zone grades outward and upward into a zone of less intense, lower rank alteration with a mordenite + clinoptilolite + smectite + opal ± hematite assemblage, then a zone of weak clay alteration and into fresh rock. Calcite is conspicuously absent from the entire suite. Acid-sulphate type water, formed from steam-condensate, dominated the shallow activity in a second stage of alteration that followed local erosion. Widespread but discontinuous alteration converted the ignimbrite to kaolinite + opal ± hematite, with alunite occurring in the more intense zones. This alteration locally overprints the early alkali-chloride produced suite, but the focus of the second-stage activity was north of the focus of the older event. Scattered opaline sinters and silicified surficial deposits are products of either still later activity or the waning part of the second stage. Chemical analysis shows that the various alteration types have characteristic patterns of major element addition and removal; these reflect the key hydrothermal mineral reactions that formed the new assemblages. Quartz-adularia alteration involved mainly silicification, dehydration and cation exchange (K + for Na 2+, H +, Ca 2+, Mg 2+), whereas alteration in the mordenite zone was mostly a moderate hydration process. Kaolinite alteration involved strong hydration, hydrolysis and redistribution of silica. Trace elements show varying degrees of mobility and correlation with major elements. Alteration features identify the important upflow zones, zones of mixing between hydrothermal and shallow groundwater, and changes in alkali chloride water level. They also reflect a transition from diffuse to channel flow as sealing eliminated original rock porosity, and led to hydraulic fracturing which maintained fracture permeability in the system. Mineralogy and fluid inclusion studies indicate that the primary fluid at now-exposed levels was a high-pH (7-8), low-CO 2 and low-H 2S water cooler than 200°C, probably modified by boiling at depth.

Henneberger, R. C.; Browne, P. R. L.



Complete Phase I Tests As Described in the Multi-lab Test Plan for the Evaluation of CH3I Adsorption on AgZ  

SciTech Connect

Silver-exchanged mordenite (AgZ) has been identified as a potential sorbent for iodine present in the off-gas streams of a used nuclear fuel reprocessing facility. In such a facility, both elemental and organic forms of iodine are released from the dissolver in gaseous form. These species of iodine must be captured with high efficiency for a facility to avoid radioactive iodine release above regulatory limits in the gaseous effluent of the plant. Studies completed at Idaho National Laboratory (INL) examined the adsorption of organic iodine in the form of CH3I by AgZ. Upon breakthrough of the feed gas through the sorbent bed, elemental iodine was observed in the effluent stream, despite the fact that the only source of iodine in the system was the CH3I in the feed gas.1 This behavior does not appear to have been reported previously nor has it been independently confirmed. Thus, as a result of these prior studies, multiple knowledge gaps relating to the adsorption of CH3I by AgZ were identified, and a multi-lab test plan, including Oak Ridge National Laboratory (ORNL), INL, Pacific Northwest National Laboratory (PNNL), and Sandia National Laboratories, was formulated to address each in a systematic way.2 For this report, the scope of work for ORNL was further narrowed to three thin-bed experiments that would characterize CH3I adsorption onto AgZ in the presence of water, NO, and NO2. Completion of these three-thin bed experiments demonstrated that organic iodine in the form of CH3I was adsorbed by reduced silver mordenite (Ag0Z) to a 50% higher loading than that of I2 when adsorbed from a dry air stream. Adsorption curves suggest different adsorption mechanisms for I2 and CH3I. In the presence of NO and NO2 gas, the loading of CH3I onto Ag0Z is suppressed and may be reversible. Further, the presence of NO and NO2 gas appears to oxidize CH3I to I2; this is indicated by an adsorption curve similar to that of I2 on Ag0Z. Finally, the loss of organic iodine loading capacity by Ag0Z in the presence of NOx is unaffected by the addition of water vapor to the gas stream; no marked additional loss in capacity or retention was observed.

Bruffey, S. H. [ORNL; Jubin, R. T. [ORNL



Preliminary Results of Voloxidation Processing of Kilogram Quantities of Used Nuclear Fuel  

SciTech Connect

Advanced nuclear fuel processing methodologies are being studied as part of the Advanced Fuel Cycle Initiative (AFCI) program at ORNL. To support this initiative, processes and equipment were deployed at ORNL to perform all steps in the recycle process on actual used nuclear fuels, ranging from used fuel receipt to production of products and waste forms at the kilogram-scale (with capacity to process 20 kg of used fuel per year in up to four campaigns). In the first campaign, approximately 4 kg of used fuel was processed. As previously reported, the head-end processing was completed using saw-segmented Dresden fuel in lab-scale equipment in multiple batches. The second processing campaign used a new single pin shear and a new bench-scale voloxidizer to perform the dry head-end treatment prior to fuel dissolution. Approximately ~5 kg of used fuel (heavy metal basis) was processed in the second campaign. Two different fuels were oxidized in three separate batches to provide a range of processing conditions. The material used for each batch and general processing conditions are summarized in Table 1. Progress of the oxidation reaction was monitored continuously by two primary measurements; the concentration of oxygen in the effluent stream which was depressed as the oxygen was consumed, and the concentration of krypton-85 in the effluent stream as measured by a gamma counter on the off-gas pipeline. Table 1. Voloxidation test conditions for second campaign. Batch Fuel Source Burnup (GWd/MT)Batch size (kg*)/(kg**)Segment Length (in) Oxidation GasOperation Temperature ( C) 1Surry-2361.223/1.7041.0Air500 2North Anna63 702.071/2.8850.88Air600 3North Anna63 702.012/2.8030.88Oxygen600 * Heavy metal basis. ** Total fuel (oxide + cladding) basis. Fission product gases evolved from the fuel during the oxidation process were trapped for subsequent chemical and radiochemical analysis. The series of traps included a bed of molecular sieves to recover tritium (as HTO), silver-substituted zeolite to capture iodine (e.g. as AgI), a caustic scrubber to collect carbon dioxide (including 14CO2), a hydrogen-substituted mordenite to capture krypton (e.g. 85Kr) by cryogenic temperature swing adsorption, and a silver-substituted mordenite to capture xenon by cryogenic temperature swing absorption. The quantities of these volatile gases collected were compared to ORIGEN calculations to estimate the effectiveness of the voloxidation process to separate the volatiles from the used fuel. This paper will describe the voloxidation system and present preliminary results from the second processing campaign.

Spencer, Barry B [ORNL] [ORNL; DelCul, Guillermo D [ORNL] [ORNL; Jubin, Robert Thomas [ORNL] [ORNL; Owens, R Steven [ORNL] [ORNL; Ramey, Dan W [ORNL] [ORNL; Collins, Emory D [ORNL] [ORNL



Novel sorbent development and evaluation for the capture of krypton and xenon from nuclear fuel reprocessing off-gas stream  

SciTech Connect

The release of volatile radionuclides generated during Used Nuclear Fuel reprocessing in the US will most certainly need to be controlled to meet US regulatory emission limits. A US DOE sponsored Off-Gas Sigma Team has been tasked with a multi-lab collaborative research and development effort to investigate and evaluate emissions and immobilization control technologies for the volatile radioactive species generated from commercial Used Nuclear Fuel (UNF) Reprocessing. Physical Adsorption technology is a simpler and potential economical alternative to cryogenic distillation processes that can be used for the capture of krypton and xenon and has resulted in a novel composite sorbent development procedure using synthesized mordenite as the active material. Utilizing the sorbent development procedure, Idaho National Laboratory sigma team members have developed two composite sorbents that have been evaluated for krypton and xenon capacities at ambient and 191 K temperature using numerous test gas compositions. Adsorption isotherms have been generated to predict equilibration and maximum capacities enabling modeling to support process equipment scale-up. (authors)

Garn, T.G.; Greenhalgh, M.R.; Law, J.D. [Idaho National Laboratory, 1625 N. Fremont Ave., Idaho Falls, ID 83415 (United States)



Determine Minimum Silver Flake Addition to GCM for Iodine Loaded AgZ  

SciTech Connect

The minimum amount of silver flake required to prevent loss of I{sub 2} during sintering in air for a SNL Glass Composite Material (GCM) Waste Form containing AgI-MOR (ORNL, 8.7 wt%) was determined to be 1.1 wt% Ag. The final GCM composition prior to sintering was 20 wt% AgI-MOR, 1.1 wt% Ag, and 80 wt% Bi-Si oxide glass. The amount of silver flake needed to suppress iodine loss was determined using thermo gravimetric analysis with mass spectroscopic off-gas analysis. These studies found that the ratio of silver to AgI-MOR required is lower in the presence of the glass than without it. Therefore an additional benefit of the GCM is that it serves to inhibit some iodine loss during processing. Alternatively, heating the AgI-MOR in inert atmosphere instead of air allowed for densified GCM formation without I{sub 2} loss, and no necessity for the addition of Ag. The cause of this behavior is found to be related to the oxidation of the metallic Ag to Ag{sup +} when heated to above ~300{degrees}C in air. Heating rate, iodine loading levels and atmosphere are the important variables that determine AgI migration and results suggest that AgI may be completely incorporated into the mordenite structure by the 550{degrees}C sintering temperature.

Terry J. Garino; Tina M. Nenoff; Mark A. Rodriguez



Removal of water and iodine by solid sorbents: adsorption isotherms and kinetics  

SciTech Connect

Tritium and iodine-129 are two major radioactive elements that are present in off-gases from spent fuel reprocessing plants. Adsorption by solid sorbents is the state-of-the-art technique for removal of these species from off-gases. Modeling and simulating adsorption processes require accurate adsorption equilibrium and kinetic data to permit reasonable estimates of process parameters. We have developed a continuous flow single-pellet adsorption system to gather accurate adsorption equilibrium and kinetic data for adsorption of water by molecular sieve 3A and for adsorption of iodine by silver exchanged mordenite. In this paper, the design of the water and iodine adsorption experimental systems are briefly described and results of water adsorption experiments are presented and discussed. Water uptake curves are fitted with the linear-driving force (LDF) model and the shrinking-core model to determine kinetic parameters. It is shown that the kinetics of water adsorption on zeolite 3A under current experimental conditions is controlled by both the external film resistance and the macro-pore diffusion and can be predicted by both the LDF model and the shrinking-core model with the former one performing slightly better. Preliminary results from iodine adsorption experiments will be presented in the conference.

Lin, R.; Tavlarides, L.L. [Syracuse University, 121 Link Hall, Syracuse, NY 13244 (United States)



Gold nanoparticles as efficient antimicrobial agents for Escherichia coli and Salmonella typhi  

PubMed Central

Background It is imperative to eliminate bacteria present in water in order to avoid problems in healthy. Escherichia coli and Salmonella typhi bacteria are two common pollutants and they are developing resistance to some of the most used bactericide. Therefore new biocide materials are being tested. Thus, gold nanoparticles are proposed to inhibit the growth of these two microorganisms. Results Gold nanoparticles were supported onto clinoptilolite, mordenite and faujasite zeolites. Content of gold in materials varied between 2.3 and 2.8 wt%. The size, dispersion and roughness of gold nanoparticles were highly dependent of the zeolite support. The faujasite support was the support where the 5 nm nanoparticles were highly dispersed. The efficiency of gold-zeolites as bactericides of Escherichia coli and Salmonella typhi was determined by the zeolite support. Conclusions Gold nanoparticles dispersed on zeolites eliminate Escherichia coli and Salmonella typhi at short times. The biocidal properties of gold nanoparticles are influenced by the type of support which, indeed, drives key parameters as the size and roughness of nanoparticles. The more actives materials were pointed out Au-faujasite. These materials contained particles sized 5 nm at surface and eliminate 90–95% of Escherichia coli and Salmonella typhi colonies. PMID:23331621



The high temperature synthesis of CsAlSiO 4-ANA, a new polymorph in the system Cs 2O?Al 2O 3?SiO 2. I. The end member of ANA type of zeolite framework  

NASA Astrophysics Data System (ADS)

High temperature phase transformations of Cs + exchanged zeolites were investigated. Above 1000°C, Cs?X, Cs?Y (FAU), and Cs, ZK-4 (LTA) frameworks recrystallized in a pollucite phase. A Cs + loaded mordenite recrystallized at 1300°C in the orthorhombic CsAlSi 5O 12 phase. A Cs + exchanged zeolite A at 960°C recrystallized in a mixture of two polymorphic CsAlSiO 4 phases having different (Al,Si)O 4 frameworks. The unstable orthorhombic CsAlSiO 4?ABW phase has a topotactic transition at 1150°C into an ordered low CsAlSiO 4-ANA framework. Further calcination produces, at 1200°C, transformation of the low CsAlSiO 4-ANA phase to the more stable high CsAlSiO 4-ANA polymorph having cubic ( a 0 = 13.6595 (5) Å) symmetry and an ordered Si?Al distribution. The crystal structure of high CsAlSiO 4?ANA, a new polymorph in the system Cs 2O?Al 2O 3?SiO 2, was determined using X-ray Rietveld analyses and 29Si MAS NMR spectroscopy.

Dimitrijevic, R.; Dondur, V.; Petranovic, N.



Proton Adsorption Selectivity of Zeolites in Aqueous Media: Effect of Si/Al Ratio of Zeolites.  


In addition to their well-known uses as catalysts, zeolites are utilized to adsorb and remove various cations from aqueous system. The adsorption of the cations is ascribed to the negative charge of zeolites derived from isomorphous substitution of Si by Al. The amount of Na+ adsorption on 4A, X, Y, Na-P1 and mordenite type zeolites were determined in aqueous media, in a two-cation (Na+ and H+) system. Although each zeolite has a constant amount of negative charge, the amount of Na+ adsorption of each zeolite decreased drastically at low pH-pNa values, where pH-pNa is equal to log{(Na+)/(H+)}. By using the plot of the amount of Na+ adsorption versus pH-pNa, an index of the H+ selectivity, which is similar to the pKa of acids, of each zeolite was estimated, and the index tended to increase with decreasing Si/Al ratio of zeolites. These indicate that zeolites with lower Si/Al and higher negative charge density have higher H+ adsorption selectivity, and in fact, such a zeolite species (4A and X) adsorbed considerable amount of H+ even at weakly alkaline pH region. The adsorption of H+ results in the decrease of cation adsorption ability, and may lead to the dissolution of zeolites in aqueous media. PMID:25493632

Munthali, Moses Wazingwa; Elsheikh, Mohammed Abdalla; Johan, Erni; Matsue, Naoto




SciTech Connect

Engineered silver-functionalized silica aerogels are being investigated for their application in off-gas treatment at a used nuclear fuel reprocessing facility. Reprocessing will release several key volatile radionuclides, including iodine-129. To achieve regulatory compliance, iodine-129 must be removed from any off-gas stream prior to environmental discharge. Silver-functionalized aerogels have been demonstrated to have high iodine capture capacity, high porosity and potential for conversion into a waste form. Capture materials used in off-gas treatment may be exposed to a heated, high humidity, acidic gas stream for months. Extended exposure to this stream could affect sorbent performance. It was the aim of this study to evaluate what impacts might be observed when Ag0-functionalized aerogels prepared at Pacific Northwest National Laboratory were contacted with a dry air stream for up to 6 months and then used to adsorb iodine from a synthetic off-gas stream. Results demonstrate that there is some loss of iodine capture capacity caused by aging, but that this loss is not as marked as for aging of more traditional iodine sorbents, such as silver-impregnated mordenite. Specifically, aging silver-functionalized aerogel under a dry air stream for up to 6 months can decrease its iodine capacity from 41wt% to 32wt%.

Bruffey, Stephanie H [ORNL; Jubin, Robert Thomas [ORNL; Anderson, Kaara K [ORNL; Walker Jr, Joseph Franklin [ORNL



Aging and iodine loading of silver-functionalized aerogels  

SciTech Connect

Engineered silver-functionalized silica aerogels are being investigated for their potential application in off-gas treatment at a used nuclear fuel reprocessing facility. Reprocessing will release several key volatile radionuclides, including iodine-129. To achieve regulatory compliance, iodine-129 must be removed from any off-gas stream prior to environmental discharge. Ag{sup 0}-functionalized aerogels have been demonstrated to have high iodine-capture capacity, high porosity, and potential for conversion into a waste form. Capture materials used in off-gas treatment may be exposed to a heated, high-humidity, acidic gas stream for months. Extended exposure to this stream could affect sorbent performance. It was the aim of this study to evaluate what impacts might be observed when Ag{sup 0}-functionalized aerogels prepared at Pacific Northwest National Laboratory were contacted with a dry air stream for up to 6 months and then used to adsorb iodine from a synthetic off-gas stream. Results demonstrate that there is some loss of iodine-capture capacity caused by aging, but that this loss is not as marked as for aging of more traditional iodine sorbents, such as silver-impregnated mordenite. Specifically, aging silver-functionalized aerogel under a dry air stream for up to 6 months can decrease its iodine capacity from 41 wt% to 32 wt%. (authors)

Bruffey, S.H.; Jubin, R.T.; Anderson, K.K.; Walker, J.F. [Oak Ridge National Laboratory, P.O. Box 2008, MS-6223, Oak Ridge, TN 37831 (United States)



Petrology and hydrothermal mineralogy of U. S. Geological Survey Newberry 2 drill core from Newberry caldera, Oregon  

SciTech Connect

U.S. Geological Survey Newberry 2 was drilled to a depth of 932 m within Newberry caldera. The bottom-hole temperature of 265/sup 0/C is the highest reported temperature of any drill hole in the Cascades region of the United States. The upper part of the stratigraphic section pentrated by Newberry 2 consists of caldera fill below which are increasingly more mafic lavas ranging from rhyodacite at 501 m to basalt at 932 m. Measured temperatures shallower than 300 m are less than 35/sup 0/C, and rock alteration consists of hydration of glass and local palagonitization of basaltic tuffs. Incipient zeolitization and partial smectite replacement of ash and pumice occurred throughout the pumiceous lithic tuffs from 300 to 500 m. Higher-temperature alteration of the tuffs to chlorite and mordenite occurs adjacent to a rhyodacite sill at 460--470 m; alteration minerals within the sill consist of pyrrhotite, pyrite, quartz, calcite, and siderite. Below 697 m the rocks are progressively more altered with depth mainly because of increased temperature along a conductive gradient from 100/sup 0/C at 697 m to 265/sup 0/C at 930 m. Fluid inclusions in quartz and calcite indicate that temperature in the past have been higher than at present, most likely due to local confining pressures between impermeable lava flows.

Keith, T.E.C.; Bargar, K.E.



Characterisation and environmental application of an Australian natural zeolite for basic dye removal from aqueous solution.  


An Australian natural zeolite was collected, characterised and employed for basic dye adsorption in aqueous solution. The natural zeolite is mainly composed of clinoptiloite, quartz and mordenite and has cation-exchange capacity of 120 meq/100g. The natural zeolite presents higher adsorption capacity for methylene blue than rhodamine B with the maximal adsorption capacity of 2.8 x 10(-5) and 7.9 x 10(-5)mol/g at 50 degrees C for rhodamine B and methylene blue, respectively. Kinetic studies indicated that the adsorption followed the pseudo second-order kinetics and could be described as two-stage diffusion process. The adsorption isotherm could be fitted by the Langmuir and Freundlich models. Thermodynamic calculations showed that the adsorption is endothermic process with Delta H(0) at 2.0 and 8.7 kJ/mol for rhodamine B and methylene blue. It has also found that the regenerated zeolites by high-temperature calcination and Fenton oxidation showed similar adsorption capacity but lower than the fresh sample. Only 60% capacity could be recovered by the two regeneration techniques. PMID:16504394

Wang, Shaobin; Zhu, Z H



Lithology, mineralogy, and paleontology of Quaternary lake deposits in Long Valley Caldera, California  

USGS Publications Warehouse

Drill cores and cuttings from two drill holes, about 3 km apart, in Long Valley caldera, Mono County, California, were studied using x-ray diffraction and optical methods. A thick sequence of tuffs and lake sediments was encountered in LVCH-1 (1,000 ft deep) and Republic well 66-29 (6,920 ft deep), drilled in the southeast part of the Long Valley caldera. Ostracods, diatoms, and isotopic data indicate that the sediments and tuffs were deposited in a shallow caldera lake which changed in salinity over time. Conditions ranged from very saline in the older lake to fresh in the youngest. The sequence of secondary minerals from top to bottom is: clinoptilolite, mordenite, analcime, K-feldspar (and albite). In some geothermal systems, this sequence of secondary minerals is a function of temperature; however, the paleontological and isotopic data indicate that the change in secondary minerals with increasing depth is due to the older strata being deposited in a more saline environment. No mineralogical evidence of hydrothermal alteration is present, although the high lithium content of some clays and feldspars and the isotopic composition of some sulfate (gypsum) seems to require a hydrothermal source. (Lantz-PTT)

Fournier, R.B.



Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: the influence of zeolite chemical surface characteristics.  


In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity. PMID:24794812

Alejandro, Serguei; Valdés, Héctor; Manéro, Marie-Hélène; Zaror, Claudio A



Probing the structure of complex solids using a distributed computing approach-Applications in zeolite science  

SciTech Connect

We demonstrate the viability of distributed computing techniques employing idle desktop computers in investigating complex structural problems in solids. Through the use of a combined Monte Carlo and energy minimisation method, we show how a large parameter space can be effectively scanned. By controlling the generation and running of different configurations through a database engine, we are able to not only analyse the data 'on the fly' but also direct the running of jobs and the algorithms for generating further structures. As an exemplar case, we probe the distribution of Al and extra-framework cations in the structure of the zeolite Mordenite. We compare our computed unit cells with experiment and find that whilst there is excellent correlation between computed and experimentally derived unit cell volumes, cation positioning and short-range Al ordering (i.e. near neighbour environment), there remains some discrepancy in the distribution of Al throughout the framework. We also show that stability-structure correlations only become apparent once a sufficiently large sample is used. - Graphical Abstract: Aluminium distributions in zeolites are determined using e-science methods. Highlights: > Use of e-science methods to search configurationally space. > Automated control of space searching. > Identify key structural features conveying stability. > Improved correlation of computed structures with experimental data.

French, Samuel A.; Coates, Rosie [Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ (United Kingdom); Lewis, Dewi W., E-mail: [Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ (United Kingdom); Catlow, C. Richard A. [Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ (United Kingdom)



Comparison between leached metakaolin and leached diatomaceous earth as raw materials for the synthesis of ZSM-5.  


Inexpensive raw materials have been used to prepare ZSM-5 zeolites with SiO2/Al2O3 molar ratios in the range 20 - 40. Kaolin or Bolivian diatomaceous earth was used as aluminosilicate raw materials and sodium hydroxide and n-butylamine were used as mineralizing agents and template. Dealumination of the raw materials by acid leaching made it possible to reach appropriate SiO2/Al2O3 ratios and to reduce the amount of iron and other impurities. After mixing the components and aging, hydrothermal treatment was carried out and the products were recovered The results clearly show for the first time that well-crystallized ZSM-5 can be directly prepared from leached metakaolin or leached diatomaceous earth using sodium hydroxide and n-butylamine as mineralizing agents and template under appropriate synthesis conditions. A longer induction time prior to crystallization was observed for reaction mixtures prepared from leached diatomaceous earth, probably due to slower digestion of the fossilized diatom skeletons as compared with that for microporous leached metakaolin. The use of leached diatomaceous earth allowed higher yield of ZSM-5 crystals within comparable synthesis times. However, low amounts of Mordenite formed, which was related to the high calcium content of diatomaceous earth. Another considerable advantage of diatomaceous earth over kaolin is that diatomaceous earth does not require heat treatment at high temperature for metakaolinization. PMID:25019042

Aguilar-Mamani, Wilson; García, Gustavo; Hedlund, Jonas; Mouzon, Johanne



Prospects for the direct electron crystallographic determination of zeolite structures.  


Recently two successful zeolite structures based on experimental electron crystallographic data have been published. Diffraction and image data based on the silicate portion of the zeolite, mordenite, which are perturbed by dynamical (as well as secondary) scattering, have been simulated by a multiple-beam dynamical scattering program. Structure analyses with these data show that the above claims are not unreasonable, given a high enough accelerating voltage for the electron beam. If, for example, 2.9 A resolution micrographs are taken from a 120 A thick crystal in a 200 or 400 kV electron microscope, the crystallographic phases found by image analysis (Fourier filtration) are accurate enough to be extended by the Sayre equation to the (atomic) resolution limit of the electron diffraction pattern (for example from a 105 A thick crystal illuminated by a 1,200 kV electron source). The resultant potential map can be interpreted to find most of the atomic positions and the remaining ones will appear during the progress of a Fourier refinement. PMID:9080411

Dorset, D L; McCourt, M P



ESCA studies of the surface chemistry of zeolites  

SciTech Connect

It has been demonstrated that the constituents on the surfaces of various pure zeolites, clays, silicas, and aluminas yield reproducible ESCA peaks with unique binding energies. The collective patterns realized by these different binding energies strongly suggest the registration of selective group rather than elemental chemical shifts. The two primary chemical groups identified in many of the zeolites seem to be a unit that resembles SiO/sub 2/ and another that mimics N/sup + +/-Al/sub 2/O/sub 4//sup 2 -/ (where N symbolizes the cations, usually alkali or alkaline earth species that balance the aluminate charge), a feature supported by quantum calculations, relatively narrow line widths, and reproducible valence band and loss data. These results have been employed to determine the relative purity of the surface region of different conventionally prepared zeolite systems. High-resolution ESCA studies of mordenite, ZSM-5, a silicate surfaces always seem to exhibit Al(2p) spectra that are significantly broadened into patterns that suggest several Al-containing species. The nonzeolites present at the surface of these systems generally constitute more than 50% of the total aluminum. The primary impurity species have been identified as metal aluminates and aluminas in differing ratios apparently depending upon the cation (e.g., sodium) concentrations. The possible presence of silica on the surface of some freshly prepared zeolite systems is suggested, but unconfirmed.

Barr, T.L.; Lishka, M.A.



Computational differentiation of Brønsted acidity induced by alkaline earth or rare earth cations in zeolites.  


For bi- and trivalent Me(q+) (Me = metal) cations of alkaline earth (AE) and rare earth (RE) metals, respectively, the formation of the nonacid MeOH((q-1)+) species and acid H-Ozeo group, where Ozeo is the framework atom, from water adsorbed at the multivalent Me(q+)(H2O) cation in cationic form zeolites was checked at both isolated cluster (8R or 6R + 4R) and periodic (the mordenite framework) levels. Both approaches demonstrate qualitative differences for the stability of the dissociated water between the two classes of industrial cationic forms if two Al atoms are closely located. The RE forms split water while the AE ones do not, that can be a basis of different proton transfer in the RE zeolites (thermodynamic control) than in the AE forms (kinetic control). The cluster models allow quantitatively explaining nearly equal intensities IHF ? ILF of the high frequency (HF) and low frequency (LF) OH vibrations in the RE forms and lowered IHF ? ILF in the AE forms, where HF bands are assigned to the Me-OH groups in the RE and AE forms, respectively, while LF bands are assigned to the Si-O(H)-Al groups. The role of electrostatic terms for water dissociation in the RE and AE forms is discussed. PMID:23131140

Rybakov, Andrey A; Larin, Alexander V; Zhidomirov, Georgy M



Status of radioiodine control for nuclear fuel reprocessing plants  

SciTech Connect

This report summarizes the status of radioiodine control in a nuclear fuel reprocessing plant with respect to capture, fixation, and disposal. Where possible, we refer the reader to a number of survey documents which have been published in the last four years. We provide updates where necessary. Also discussed are factors which must be considered in developing criteria for iodine control. For capture from gas streams, silver mordenite and a silver nitrate impregnated silica (AC-6120) are considered state-of-the-art and are recommended. Three aqueous scrubbing processes have been demonstrated: Caustic scrubbing is simple but probably will not give an adequate iodine retention by itself. Mercurex (mercuric nitrate-nitric acid scrubbing) has a number of disadvantages including the use of toxic mercury. Iodox (hyperazeotropic nitric acid scrubbing) is effective but employs a very corrosive and hazardous material. Other technologies have been tested but require extensive development. The waste forms recommended for long-term storage or disposal are silver iodide, the iodates of barium, strontium, or calcium, and silver loaded sorbents, all fixed in cement. Copper iodide in bitumen (asphalt) is a possibility but requires testing. The selection of a specific form will be influenced by the capture process used.

Burger, L.L.; Scheele, R.D.



Alteration history studies in the Exploratory Studies Facility, Yucca Mountain, Nevada, USA  

SciTech Connect

By mid-1995, the Exploratory Studies Facility (ESF) extended about 1. 1 km from Exile Hill westward toward Yucca Mountain, mostly within densely welded, devitrfied Tiva Canyon Tuff. Secondary mineral occurrences in this unit include breccia cements of mordenite, a fibrous zeolite, and vapor-phase deposits of silica, alkali feldspar, apatite, hollandite, amphibole, and zircon. Calcite is also a common secondary mineral in faults and fractures. Studies of water and gas contents in fluid inclusions in calcites from a fault in nonwelded tuff and a fracture in densely welded tuff suggest mineral deposition under transient locally saturated conditions. Calcite in the nonwelded tuff incorporated air from the unsaturated tuff adjacent to the fault. A highly altered interval within pre-Pah Canyon tuffs just above the top of the Topopah Spring Tuff may be a fossil fumarole or other hydrothermal feature associated with cooling pyroclastic deposits, overprinted by later zeolitic alteration. The observed quartz, cristobalite, opal-CT, and fluorite have been widely identified as products of syngenetic devitrification and vapor-phase alteration in and above the Topopah Spring Tuff. Smectite, also an abundant secondary mineral at the ESF site, has been observed elsewhere at this stratigraphic level. Zeolitic alteration of nonwelded tuffs above the Topopah Spring Tuff, as seen in the ESF, has also been noted in drill core and outcrop at northeastern Yucca Mountain. The hydrologic and geochemical conditions that favored zeolitization only in certain areas of this stratigraphic interval have yet to be determined.

Levy, S.S; Chipera, S.J. [Los Alamos National Lab., NM (United States); Norman, D.I. [New Mexico Inst. of Mining and Technology, Socorro, NM (United States). Dept. of Geoscience



Thermodynamic modeling of natural zeolite stability  

SciTech Connect

Zeolites occur in a variety of geologic environments and are used in numerous agricultural, commercial, and environmental applications. It is desirable to understand their stability both to predict future stability and to evaluate the geochemical conditions resulting in their formation. The use of estimated thermodynamic data for measured zeolite compositions allows thermodynamic modeling of stability relationships among zeolites in different geologic environments (diagenetic, saline and alkaline lakes, acid rock hydrothermal, basic rock, deep sea sediments). This modeling shows that the relative cation abundances in both the aqueous and solid phases, the aqueous silica activity, and temperature are important factors in determining the stable zeolite species. Siliceous zeolites (e.g., clinoptilolite, mordenite, erionite) present in saline and alkaline lakes or diagenetic deposits formed at elevated silica activities. Aluminous zeolites (e.g., natrolite, mesolite/scolecite, thomsonite) formed in basic rocks in association with reduced silica activities. Likewise, phillipsite formation is favored by reduced aqueous silica activities. The presence of erionite, chabazite, and phillipsite are indicative of environments with elevated potassium concentrations. Elevated temperature, calcic water conditions, and reduced silica activity help to enhance the laumontite and wairakite stability fields. Analcime stability increases with increased temperature and aqueous Na concentration, and/or with decreased silica activity.

Chipera, S.J.; Bish, D.L.



Kinetics of silica-phase transitions  

SciTech Connect

In addition to the stable silica polymorph quartz, several metastable silica phases are present in Yucca Mountain. The conversion of these phases to quartz is accompanied by volume reduction and a decrease in the aqueous silica activity, which may destabilize clinoptilolite and mordenite. The primary reaction sequence for the silica phases is from opal or glass to disordered opal-CT, followed by ordering of the opal-CT and finally by the crystallization of quartz. The ordering of opal-CT takes place in the solid state, whereas the conversion of opal-CT takes place through dissolution-reprecipitation involving the aqueous phase. It is proposed that the rate of conversion of opal-CT to quartz is controlled by diffusion of defects out of a disordered surface layer formed on the crystallizing quartz. The reaction rates are observed to be dependent on temperature, pressure, degree of supersaturation, and pH. Rate equations selected from the literature appear to be consistent with observations at Yucca Mountain.

Duffy, C.J.



Removal efficiency of water purifier and adsorbent for iodine, cesium, strontium, barium and zirconium in drinking water.  


The severe incident of Fukushima Daiichi Nuclear Power Station has caused radioactive contamination of environment including drinking water. Radioactive iodine, cesium, strontium, barium and zirconium are hazardous fission products because of the high yield and/or relatively long half-life. In the present study, 4 pot-type water purifiers and several adsorbents were examined for the removal effects on these elements from drinking water. Iodide, iodate, cesium and barium were removed by all water purifiers with efficiencies about 85%, 40%, 75-90% and higher than 85%, respectively. These efficiencies lasted for 200 l, which is near the recommended limits for use of filter cartridges, without decay. Strontium was removed with initial efficiencies from 70% to 100%, but the efficiencies were slightly decreased by use. Zirconium was removed by two models, but hardly removed by the other models. Synthetic zeolite A4 efficiently removed cesium, strontium and barium, but had no effect on iodine and zirconium. Natural zeolite, mordenite, removed cesium with an efficiency as high as zeolite A4, but the removal efficiencies for strontium and barium were far less than those of zeolite A4. Activated carbon had little removal effects on these elements. In case of radioactive contamination of tap water, water purifiers may be available for convenient decontamination of drinking water in the home. PMID:22129747

Sato, Itaru; Kudo, Hiroaki; Tsuda, Shuji



Growth of Megaspherulites In a Rhyolitic Vitrophyre  

NASA Technical Reports Server (NTRS)

Megaspherulites occur in the middle zone of a thick sequence of rhyolitic vitrophyre that occupies a small, late Eocene to early Oligocene volcanic-tectonic basin near Silver Cliff, Custer County, Colorado. Diameters of the megaspherulites range from 0.3 m to over 3.66 m, including a clay envelope. The megaspherulites are compound spherulites. consisting of an extremely large number (3.8 x 10(exp 9) to 9.9 x 10(exp 9)) of individual growth cones averaging 3 mm long by 1.25 mm wide at their termination. They are holocrystalline, very fine- to fine-grained, composed of disordered to ordered sanidine (orthoclase) and quartz, and surrounded by a thin K-feldspar, quartz rich rind, an inner clay layer with mordenite, and an outer clay layer composed wholly of 15 A montmorillonite. Whole rock analyses of the megaspherulites show a restricted composition from their core to their outer edge, with an average analyses of 76.3% SiO2, 0.34% CaO, 2.17% Na2O, 6.92% K2O, 0.83% H2O+ compared to the rhyolitic vitrophyre from which they crystallize with 71.07% SiO2, 0.57% CaO, 4.06% Na2O,4.l0% K2O, and 6.40% H2O+. The remaining oxides of Fe2O3 (total Fe), A12O3, MnO,MgO, TiO2, P2O5, Cr2O3, and trace elements show uniform distribution between the megaspherulites and the rhyolitic vitrophyre. Megaspherulite crystallization began soon after the rhyolitic lava ceased to flow as the result of sparse heterogeneous nucleation, under nonequilibrium conditions, due to a high degree of undercooling, delta T. The crystals grow with a fibrous habit which is favored by a large delta T ranging between 245 C and 295 C, despite lowered viscosity, and enhanced diffusion due to the high H2O content, ranging between 5% and 7%. Therefore, megaspherulite growth proceeded in a diffusion controlled manner, where the diffusion, rate lags behind the crystal growth rate at the crystal-liquid interface, restricting fibril lengths and diameters to the 10 micron to 15 micron and 3 micron and 8 micron ranges respectively. Once diffusion reestablishes itself at the crystallization front, a new nucleation event occurs at the terminated tips of the fibril cones and a new cone begins to develop with a similar orientation (small angle branching) to the earlier cones. During crystallization, these fibril cones impinge upon each other, resulting in fibril cone-free areas. These cone-free areas consist of coarser, fine-grained phases, dominated by quartz, which crystallized from the melt as it accumulated between the crystallizing K-feldspar fibrils of the cones. The anhydrous nature of the disordered to ordered sanidine (orthoclase) and quartz, suggests that water in the vitrophyre moved ahead of the crystallization front, resulting in a water rich fluid being enriched in Si, K, Na, Mg, Ca, Sr, Ba, and Y. The clay layers associated with the megaspherulites are therefore, the result of the deuteric alteration between the fractionated water and the vitrophyre, as indicated by the presence of the minerals mordenite and montmorillonite. This silica rich fluid also resulted in the total silicification of the megaspherulites within the upper 3 m of the vitrophyre.

Smith, Robert K.; Tremallo, Robin L.; Lofgren, Gary E.



Assessment of Methods to Consolidate Iodine-Loaded Silver-Functionalized Silica Aerogel  

SciTech Connect

The U.S. Department of Energy is currently investigating alternative sorbents for the removal and immobilization of radioiodine from the gas streams in a nuclear fuel reprocessing plant. One of these new sorbents, Ag0-functionalized silica aerogels, shows great promise as a potential replacement for Ag-bearing mordenites because of its high selectivity and sorption capacity for iodine. Moreover, a feasible consolidation of iodine-loaded Ag0-functionalized silica aerogels to a durable SiO2-based waste form makes this aerogel an attractive choice for sequestering radioiodine. This report provides a preliminary assessment of the methods that can be used to consolidate iodine-loaded Ag0-functionalized silica aerogels into a final waste form. In particular, it focuses on experimental investigation of densification of as prepared Ag0-functionalized silica aerogels powders, with or without organic moiety and with or without sintering additive (colloidal silica), with three commercially available techniques: 1) hot uniaxial pressing (HUP), 2) hot isostatic pressing (HIP), and 3) spark plasma sintering (SPS). The densified products were evaluated with helium gas pycnometer for apparent density, with the Archimedes method for apparent density and open porosity, and with high-resolution scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS) for the extent of densification and distribution of individual elements. The preliminary investigation of HUP, HIP, and SPS showed that these sintering methods can effectively consolidate powders of Ag0-functionalized silica aerogel into products of near-theoretical density. Also, removal of organic moiety and adding 5.6 mass% of colloidal silica to Ag0-functionalized silica aerogel powders before processing provided denser products. Furthermore, the ram travel data for SPS indicated that rapid consolidation of powders can be performed at temperatures below 950°C.

Matyas, Josef; Engler, Robert K.



Continuous chemoselective methylation of functionalized amines and diols with supercritical methanol over solid acid and acid-base bifunctional catalysts.  


The selective N-methylation of bifunctionalized amines with supercritical methanol (scCH(3)OH) promoted by the conventional solid acids (H-mordenite, beta-zeolite, amorphous silica-alumina) and acid-base bifunctional catalysts (Cs-P-Si mixed oxide and gamma-alumina) was investigated in a continuous-flow, fixed-bed reactor. The use of scCH(3)OH in the reaction of 2-aminoethanol with methanol (amine/CH(3)OH = 1/10.8) over the solid catalysts led to a significant improvement in the chemoselectivity of the N-methylation. Among the catalysts examined, the Cs-P-Si mixed oxide provided the most efficient catalyst performance in terms of selectivity and reactivity at 300 degrees C and 8.2 MPa; the N-methylation selectivity in the products reaching up to 94% at 86% conversion. The present selective methylation was successfully applied to the synthesis of N-methylated amino alcohols and diamines as well as O-methylated ethylene glycol. Noticeably, ethoxyethylamine was less reactive, suggesting that the hydroxy group of the amino alcohols is a crucial structural factor in determining high reactivity and selectivity, possibly because of the tethering effect of another terminus, a hydroxo group, to the catalyst surface. The magic-angle-spinning NMR spectroscopy and X-ray diffraction analysis of the Cs-P-Si mixed oxide catalyst revealed that the acidic and basic sites originate from P(2)O(5)/SiO(2) and Cs/SiO(2), respectively, and the weak acid-base paired sites are attributed to three kinds of cesium phosphates on SiO(2). The weak acid-base sites on the catalyst surface might be responsible for the selective dehydrative methylation. PMID:15186176

Oku, Tomoharu; Arita, Yoshitaka; Tsuneki, Hideaki; Ikariya, Takao



Adsorption Model for Off-Gas Separation  

SciTech Connect

The absence of industrial scale nuclear fuel reprocessing in the U.S. has precluded the necessary driver for developing the advanced simulation capability now prevalent in so many other countries. Thus, it is essential to model complex series of unit operations to simulate, understand, and predict inherent transient behavior and feedback loops. A capability of accurately simulating the dynamic behavior of advanced fuel cycle separation processes will provide substantial cost savings and many technical benefits. The specific fuel cycle separation process discussed in this report is the off-gas treatment system. The off-gas separation consists of a series of scrubbers and adsorption beds to capture constituents of interest. Dynamic models are being developed to simulate each unit operation involved so each unit operation can be used as a stand-alone model and in series with multiple others. Currently, an adsorption model has been developed in gPROMS software. Inputs include gas stream constituents, sorbent, and column properties, equilibrium and kinetic data, and inlet conditions. It models dispersed plug flow in a packed bed under non-isothermal and non-isobaric conditions for a multiple component gas stream. The simulation outputs component concentrations along the column length as a function of time from which the breakthrough data is obtained. It also outputs temperature along the column length as a function of time and pressure drop along the column length. Experimental data will be input into the adsorption model to develop a model specific for iodine adsorption on silver mordenite as well as model(s) specific for krypton and xenon adsorption. The model will be validated with experimental breakthrough curves. Another future off-gas modeling goal is to develop a model for the unit operation absorption. The off-gas models will be made available via the server or web for evaluation by customers.

Veronica J. Rutledge



Further description of the petrology of the Topopah Spring member of the paintbrush tuff in drill holes UE25A-1 and USW-G1 and of the lithic-rich tuff in USW-G1, Yucca Mountain, Nevada  

SciTech Connect

The Topopah Spring Member of the Paintbrush Tuff and the Lithic-rich tuff and two Tertiary volcanic units that occur in cores from drill holes UE25a-1 and USW-G1 at Yucca Mountain, Nevada. Recently they have been suggested as possibly suitable for the permanent storage of high-level radioactive waste. Earlier petrologic characterization of these units is augmented here. The Topopah Spring Member (approximately 350 m thick) has two compound cooling units. The upper, thinner unit is densely welded to vitrophyric. The lower unit ranges from nonwelded to vitrophyric, and its nonwelded base is extensively zeolitized to clinoptilolite and mordenite. Heulandite occurs as fracture fill in the overlying vitrophyric part, but zeolites are absent above that vitrophyre. Here primary devitrification plus vapor-phase crystallization dominate the mineralogy. Vapor-phase effects are especially prominent between the two vitrophyres in both cores and include numerous large lithophysal cavities throughout most of this moderately to densely welded tuff. The Lithic-rich tuff extends from 1203 to 1506 m in the USW-G1 drill core. It is nonwelded to partly welded but is well indurated due to pervasive intergrowths of authigenic minerals. These phases are analcime, albite, alkali feldspar, sericite, chlorite and quartz. The transition from analcime to secondary albite corresponds to Iijima`s zeolite Zone IV boundary, and this boundary appears in USW-G1 at 1326 m. However, analcime remains as a prominent phase through most of the Lithic-rich tuff. Further work is necessary to assess the suitability of either of these horizons for a waste repository. In the Topopah Spring Member, both mechanical and hydrologic properties of thick lithophysal zone must be studied, as well as the complete sequence of fracture fill. For both units, zeolite and clay mineral stabilities need to be investigated.

Carroll, P.I.; Caporuscio, F.A.; Bish, D.L.



Adsorption properties of nitrogen monoxide on silver ion-exchanged zeolites  

SciTech Connect

The removal of nitrogen oxides (NO{sub x}) which cause acid rain and air pollution is an important global environmental problem which needs to be solved soon. The adsorption properties of nitrogen monoxide (NO) on various silver ion-exchanged zeolites were examined by adsorption-desorption measurements in a fixed bed flow apparatus. Both reversible (q{sub rev}) and irreversible (q{sub irr}) adsorption of NO is dependent on the aluminum content in the zeolites and the zeolite structure. The amounts of reversible and irreversible adsorption of NO per silver ion increased with decreasing aluminum content of the zeolites and were constant, independent of the ion exchange level for ZSM-5 zeolites, but increased with the ion exchange level for mordenite zeolites (MOR). It was also found that the adsorption properties are dependent on the temperature and pressure of adsorption: q{sub irr} and q{sub rev} of Ag-MOR increased with decreasing absorption temperature and increasing adsorption pressure. Furthermore, the influence of preadsorbed gases on the Ag-MOR zeolite was investigated, and an enhancement of q{sub rev} was observed when NO{sub 2} was preadsorbed. The NO species adsorbed on the Ag-MOR zeolite were characterized by infrared (IR). Most of the reversibly adsorbed NO species are NO{sup {delta}+} and some N{sub 2}O adsorbed on Ag{sup +}, and the irreversibly adsorbed NO species are some N{sub 2}O, NO{sup {delta}+}, and a small amount of NO{sup {delta}{minus}}, NO{sub 2}{sup {delta}+}.

Zhang, W.; Jia, M.; Yu, J.; Wu, T. [Jilin Univ., Changchun (China). Dept. of Chemistry] [Jilin Univ., Changchun (China). Dept. of Chemistry; Yahiro, Hidenori; Iwamoto, Masakazu [Hokkaido Univ., Sapporo (Japan). Catalysis Research Center] [Hokkaido Univ., Sapporo (Japan). Catalysis Research Center



Stratigraphy, structure, and some petrographic features of Tertiary volcanic rocks at the USW G-2 drill hole, Yucca Mountain, Nye County, Nevada  

SciTech Connect

A continuously cored drill hole penetrated 1830.6 m of Tertiary volcanic strata comprised of the following in descending order: Paintbrush Tuff, tuffaceous beds of Calico Hills, Crater Flat Tuff, lava and flow breccia (rhyodacitic), tuff of Lithic Ridge, bedded and ash-flow tuff, lava and flow breccia bedded tuff, conglomerate and ash-flow tuff, and older tuffs of USW G-2. Comparison of unit thicknesses at USW G-2 to unit thicknesses at previously drilled holes at Yucca Mountain indicate: (1) thickening of the Paintbrush Tuff members and tuffaceous beds of Calico Hills toward the northern part of Yucca Mountain; (2) thickening of the Prow Pass Member but thinning of the Bullfrog Member and Tram unit; (3) thinning of the tuff of Lithic Ridge; (4) presence of about 280 m of lava and flow breccia not previously penetrated by any drill hole; and (5) presence of an ash-flow tuff unit at the bottom of the drill hole not previously intersected, apparently the oldest unit penetrated at Yucca Mountain to date. Petrographic features of some of the units include: (1) decrease in quartz and K-feldspar and increases in biotite and plagioclase with depth in the tuffaceous beds of Calico Hills; (2) an increase in quartz phenocrysts from the top to the bottom members of the Crater Flat Tuff; (3) a low quartz content in the tuff of Lithic Ridge, suggesting tapping of the magma chamber at quartz-poor levels; (4) a change in zeolitic alteration from heulandite to clinoptilolite to mordenite with increasing depth; (5) lavas characterized by a rhyolitic top and dacitic base, suggesting reverse compositional zoning; and (6) presence of hydrothermal mineralization in the lavas that could be related to an itrusive under Yucca Mountain or to volcanism associated with the Timber Mountain-Claim Canyon caldera complex. A fracture analysis of the core resulted in tabulation of 7848 fractures, predominately open and high angle.

Maldonado, F.; Koether, S.L.



Electron transfer reactions in microporous solids. Progress report, June 1991--May 1992  

SciTech Connect

We have studied electron transfer quenching of the excited state of Ru(bpy){sub 3}{sup 2+} in aqueous suspensions of zeolites Y, L, and mordenite. The internal pore network of the zeolite is ion-exchanged with methylviologen cations, which quench the excited state of the surface-bound sensitizer. A detailed study of the quenching and charge recombination kinetics, using time-resolved luminescence quenching and transient diffuse reflectance spectroscopies, shows to remarkable effects: first, the excited state quenching is entirely dynamic is large-pore zeolites (L and Y), even when they are prepared as apparently ``dry`` powders (which still contain significant amounts of internally sited water). Second, a lower limit for the diffusion coefficient of the MV{sup 2+} ion in these zeolites, determined by this technique, is 10{sup {minus}7} cm{sup 2}sec, i.e., only about one order of magnitude slower than a typical ion in liquid water, and 2--3 orders of magnitude faster than charge transfer diffusion of cations in polyelectrolyte films or membranes such as Nafion. Surface sensitization of internally platinized layered oxide semiconductors such as K{sub 4-x}H{sub x}Nb{sub 6}O{sub 17}{center_dot}nH{sub 2}O (x {approx} 2.5) yields photocatalysts for the production of H{sub 2} and I{sub 3{minus}} in aqueous iodide solutions. Layered alkali niobates and titanates form a class of zeolitic wide-bandap semiconductors, and are the first examples of photocatalysts that evolve hydrogen from an electrochemically reversible (i.e., non-sacrificial) electron donor with visible light excitation.

Mallouk, T.E.



Electron transfer reactions in microporous solids  

SciTech Connect

We have studied electron transfer quenching of the excited state of Ru(bpy){sub 3}{sup 2+} in aqueous suspensions of zeolites Y, L, and mordenite. The internal pore network of the zeolite is ion-exchanged with methylviologen cations, which quench the excited state of the surface-bound sensitizer. A detailed study of the quenching and charge recombination kinetics, using time-resolved luminescence quenching and transient diffuse reflectance spectroscopies, shows to remarkable effects: first, the excited state quenching is entirely dynamic is large-pore zeolites (L and Y), even when they are prepared as apparently dry'' powders (which still contain significant amounts of internally sited water). Second, a lower limit for the diffusion coefficient of the MV{sup 2+} ion in these zeolites, determined by this technique, is 10{sup {minus}7} cm{sup 2}sec, i.e., only about one order of magnitude slower than a typical ion in liquid water, and 2--3 orders of magnitude faster than charge transfer diffusion of cations in polyelectrolyte films or membranes such as Nafion. Surface sensitization of internally platinized layered oxide semiconductors such as K{sub 4-x}H{sub x}Nb{sub 6}O{sub 17}{center dot}nH{sub 2}O (x {approx} 2.5) yields photocatalysts for the production of H{sub 2} and I{sub 3{minus}} in aqueous iodide solutions. Layered alkali niobates and titanates form a class of zeolitic wide-bandap semiconductors, and are the first examples of photocatalysts that evolve hydrogen from an electrochemically reversible (i.e., non-sacrificial) electron donor with visible light excitation.

Mallouk, T.E.



Distribution and chemistry of fracture-lining minerals at Yucca Mountain, Nevada  

SciTech Connect

Yucca Mountain, a >1.5-km-thick sequence of tuffs and subordinate lavas in southwest Nevada, is being investigated as a potential high-level nuclear waste repository site. Fracture-lining minerals have been studied because they may provide information on past fluid transport and because they may act as natural barriers to radionuclide migration within the fractures. Cores from seven drill holes have been studied to determine the distribution and chemistry of minerals lining fractures at Yucca Mountain. Fracture-lining minerals in tuffs of the Paintbrush Group, which is above the static water level at Yucca Mountain, are highly variable in distribution, both vertically and laterally across the mountain, with the zeolites mordenite, heulandite, and stellerite widespread in fractures even though the tuff matrix is generally devitrified and nonzeolitic. Where heulandite occurs as both tabular and prismatic crystals in the same fracture, the two morphologies have different compositions, suggesting multiple episodes of zeolite formation within the fractures. Manganese-oxide minerals within the Paintbrush Group are rancieite and lithiophorite. The silica polymorphs (quartz, tridymite, and cristobalite) generally exist in fractures where they exist in the matrix, suggesting that they formed in the fractures at the same time they formed in the matrix. Fluorite, calcite, and opal occur over tridymite in some lithophysal cavities. Calcite also occurs over zeolites in fractures unrelated to lithophysal cavities and is often the youngest mineral in a given fracture. The clays smectite, palygorskite, and sepiolite are common in fractures in the Paintbrush Group in drill core USW GU-3; smectite is an abundant fracture-coating mineral in all drill cores at Yucca Mountain.

Carlos, B.A.; Chipera, S.J.; Bish, D.L.



Zeolitization of intracaldera sediments and rhyolitic rocks in the 1.25 Ma lake of Valles caldera, New Mexico, USA  

NASA Astrophysics Data System (ADS)

Quantitative X-ray diffraction analysis of about 80 rhyolite and associated lacustrine rocks has characterized previously unrecognized zeolitic alteration throughout the Valles caldera resurgent dome. The alteration assemblage consists primarily of smectite-clinoptilolite-mordenite-silica, which replaces groundmass and fills voids, especially in the tuffs and lacustrine rocks. Original rock textures are routinely preserved. Mineralization typically extends to depths of only a few tens of meters and resembles shallow "caldera-type zeolitization" as defined by Utada et al. [Utada, M., Shimizu, M., Ito, T., Inoue, A., 1999. Alteration of caldera-forming rocks related to the Sanzugawa volcanotectonic depression, northeast Honshu, Japan — with special reference to "caldera-type zeolitization." Resource Geol. Spec. Issue No. 20, 129-140]. Geology and 40Ar/ 39Ar dates limit the period of extensive zeolite growth to roughly the first 30 kyr after the current caldera formed (ca. 1.25 to 1.22 Ma). Zeolitic alteration was promoted by saturation of shallow rocks with alkaline lake water (a mixture of meteoric waters and degassed hydrothermal fluids) and by high thermal gradients caused by cooling of the underlying magma body and earliest post-caldera rhyolite eruptions. Zeolitic alteration of this type is not found in the later volcanic and lacustrine rocks of the caldera moat (? 0.8 Ma) suggesting that later lake waters were cooler and less alkaline. The shallow zeolitic alteration does not have characteristics resembling classic, alkaline lake zeolite deposits (no analcime, erionite, or chabazite) nor does it contain zeolites common in high-temperature hydrothermal systems (laumontite or wairakite). Although aerially extensive, the early zeolitic alteration does not form laterally continuous beds and are consequently, not of economic significance.

Chipera, Steve J.; Goff, Fraser; Goff, Cathy J.; Fittipaldo, Melissa



Sorption of cesium and strontium from concentrated brines by backfill barrier materials  

SciTech Connect

The sorption of radionuclides from potentially intruding groundwater at a nuclear waste repository is a major chemical function of backfill barriers. In this study, various materials (including clays, zeolites and an inorganic ion exchanger) were screened for the sorption of the fission products cesium and strontium in concentrated brines. Representative brines A and B for the Waste Isolation Pilot Plant (WIPP), a proposed radioactive waste repository and test facility in bedded salt were used. Sorption properties were quantified using empirical distribution coefficients, k/sub d/. Of the materials examined, sodium titanate had the highest k/sub d/ for the sorption of Sr(II) in both brine A (k/sub d/ = 125 ml/g) and brine B(k/sub d/ = 500 to 600 ml/g). A mordenite-type zeolite was the most effective getter for Cs(I) in brine A (k/sub d = 27 ml/g), while illite yielded the highest k/sub d/ for Cs(I) in brine B (k/sub d/ = 115 ml/g). The relative merit of these k/sub d/ values is evaluated in terms of calculated estimates of breakthrough times for a backfill barrier containing the getter. Results show that a backfill mixture containing these getters is potentially an effective barrier to the migration of Sr(II) and Cs(I), although further study (especially for the sorption of cesium from brine A) is recommended. Initial mechanistic studies revealed competing ion effects which would support an ion exchange mechanism. K/sub d/'s were constant over a Sr(II) concentration range of 10/sup -11/ to 10/sup -5/ M and a Cs(I) concentration range of 10/sup -8/ to 10/sup -5/ M, supporting the choice of a linear sorption isotherm as a model for the results. Constant batch composition was shown to be attained within one week.

Winslow, C D



Mineral Resources of the Warm Springs Wilderness Study Area, Mohave County, Arizona  

USGS Publications Warehouse

At the request of the U.S. Bureau of Land Management, approximately 113,500 acres of the Warm Springs Wilderness Study Area (AZ-020-028/029) were evaluated for mineral resources and mineral resource potential. In this report, the area studied is referred to as the 'wilderness study area' or 'study area'; any reference to the Warm Springs Wilderness Study Area refers only to that part of the wilderness study area for which a mineral survey was requested. This study area is located in west-central Arizona. The U.S. Geological Survey and the U.S. Bureau of Mines conducted geological, geochemical, and geophysical surveys to appraise the identified mineral resources (known) and assess the mineral resource potential (undiscovered) of the study area. fieldwork for this report was carried out largely in 1986-1989. There is a 1-million short ton indicated subeconomic resource of clinoptilolite-mordenite zeolite and an additional inferred resource of 2 million short tons near McHeffy Butte, approximately 2 miles west of the study area. A perlite deposit in the southeast corner of the study area contains an inferred subeconomic resource totaling 13 million short tons. An inferred subeconomic resource of gold in 225 short tons of quartz having a grade of 0.01 8 troy ounces per short ton is present at the Cook mine, 0.5 miles west of the study area. The northwestern part of the Warm Springs Wilderness Study Area has high mineral resource potential for gold and silver. The south-central part of the study area has one area of moderate and one area north of this south-central part has low mineral resource potential for gold and silver in and near Warm Springs Canyon; the mineral resource potential for gold is also moderate in three small areas in the southern part and one area in the northeastern part of the study area. The mineral resource potential for zeolite is high for the area surrounding the McHeffy Butte prospect and for one area in the southern part of the study area. Two areas inside the south and southeast boundaries of the study area have high mineral resource potential for perlite. The potential for ka: olinite resources is moderate in two areas in the southern part of the study area. The southern part of the study area has low resource potential for perlite and zeolite. Geothermal energy resource potential of the study area is low. The study area has no resource potential for oil and gas.

Gray, Floyd; Jachens, Robert C.; Miller, Robert J.; Turner, Robert L.; Knepper, Daniel H.; Pitkin, James A.; Keith, William J.; Mariano, John; Jones, Stephanie L.; Korzeb, Stanley L.



Structure-property relationship of metal-organic frameworks (MOFs) and physisorbed off-gas radionuclides.  

SciTech Connect

We report on the host-guest interactions between metal-organic frameworks (MOFs) with various profiles and highly polarizable molecules (iodine), with emphasis on identifying preferential sorption sites in these systems. Radioactive iodine 129I, along with other volatile radionuclides (3H, 14C, Xe and Kr), represents a relevant component in the off-gas resulted during nuclear fuel reprocessing. Due to its very long half-life, 15.7 x 106 years, and potential health risks in humans, its efficient capture and long-term storage is of great importance. The leading iodine capture technology to date is based on trapping iodine in silver-exchanged mordenite. Our interests are directed towards improving existent capturing technologies, along with developing novel materials and alternative waste forms. Herein we report the first study that systematically monitors iodine loading onto MOFs, an emerging new class of porous solid-state materials. In this context, MOFs are of particular interest as: (i) they serve as ideal high capacity storage media, (ii) they hold potential for the selective adsorption from complex streams, due to their high versatility and tunability. This work highlights studies on both newly developed in our lab, and known highly porous MOFs that all possess distinct characteristics (specific surface area, pore volume, pore size, and dimension of the window access to the pore). The materials were loaded to saturation, where elemental iodine was introduced from solution, as well as from vapor phase. Uptakes in the range of {approx}125-150 wt% I2 sorbed were achieved, indicating that these materials outperform all other solid adsorbents to date in terms of overall capacity. Additionally, the loaded materials can be efficiently encapsulated in stable waste forms, including as low temperature sintering glasses. Ongoing studies are focused on gathering qualitative information with respect to localizing the physisorbed iodine molecules within the frameworks: X-ray single-crystal analyses, in conjunction with high pressure differential pair distribution function (d-PDF) studies aimed to identify preferential sites in the pores, and improve MOFs robustness. Furthermore, durability studies on the iodine loaded MOFs and subsequent waste forms include thermal analyses, SEM/EDS elemental mapping, and leach-durability testing. We anticipate for this in-depth analysis to further aid the design of advanced materials, capable to address major hallmarks: safe capture, stability and durability over extended timeframes.

Nenoff, Tina Maria; Chupas, Peter J. (Argonne National Laboratory); Garino, Terry J.; Rodriguez, Mark Andrew; Chapman, Karena W. (Argonne National Laboratory); Sava, Dorina Florentina



A call to expand regulation to all carcinogenic fibrous minerals  

NASA Astrophysics Data System (ADS)

The regulatory term "asbestos" groups only the six fibrous minerals that were commercially used among approximately 400. The carcinogenicity of these six regulated minerals has been largely demonstrated and is related to fiber structure, fiber length/diameter ratio, and bio-persistence. From a public perception, the generic term "asbestos" refers to the fibrous minerals that cause asbestosis, mesothelioma and other cancers. However, other non-regulated fibrous minerals are potentially as dangerous as the regulatory asbestos because they share similar physical and chemical properties, epidemiological studies have demonstrated their relationship with asbestos-related diseases, and both in vitro and in vivo experiments have established the toxicity of these minerals. For example, the non-regulated asbestiform winchite and richterite minerals that contaminated the vermiculite mined from Libby, Montana, (USA) were associated with mesothelioma, lung cancer and asbestosis observed among the area's residents and miners. Many other examples of non-regulated carcinogenic fibrous minerals include, but are not limited to, antigorite, arfvedsonite, balangeroite, carlosturanite, erionite, fluoro-edenite, hornblende, mordenite, palygorskite, and sepiolite. To propose a regulatory definition that would provide protection from all carcinogenic fibers, we have conducted an interdisciplinary literature review to compare the characteristics of "asbestos" and of non-regulated mineral fibers that relate to carcinogenicity. We specifically studied two non-regulated fibrous minerals that are associated with asbestos-related diseases: the serpentine antigorite and the zeolite erionite. Both examples underscore the problem of regulation based on commercial, rather than scientific principles: 1) the occurrence of fibrous antigorite in materials used to pave roads has been correlated with high mesothelioma rates in New Caledonia. Antigorite was also the cause of asbestosis in Poland, and in vitro and in vivo studies have shown its toxic and carcinogenic properties; 2) the carcinogenic properties of erionite have been demonstrated, and erionite has been associated with a mesothelioma epidemic in Anatolia, Turkey. Erionite is also widespread in areas of north central USA, where it is contained in gravel paving stone, and is cause for concern due to increased commercial traffic. Numerous studies have shown that non-regulated fibrous materials pose similar health hazards to regulated "asbestos". An increase in human activities in areas where these fibrous minerals are present, such as in surficial rock and soil, will result in the generation of airborne dust, exposing people to carcinogenic fibers. The current limited regulation leads people to believe that only the six mineral fibers referred to as "asbestos" are dangerous. We propose that fibrous minerals should be regulated as a single group, as they have similar deleterious effects on the human body. Regulations would be simplified and more effective if they embrace all carcinogenic fibrous minerals.

Baumann, F.; Steele, I.; Ambrosi, J.; Carbone, M.



Spectroscopic study of the dehydration and/or dehydroxylation of phyllosilicate and zeolite minerals  

NASA Astrophysics Data System (ADS)

Phyllosilicates on Mars mapped by infrared spectroscopic techniques could have been affected by dehydration and/or dehydroxylation associated with chemical weathering in hyperarid conditions, volcanism or shock heating associated with meteor impact. The effects of heat-induced dehydration and/or dehydroxylation on the infrared spectra of 14 phyllosilicates from four structural groups (kaolinite, smectite, sepiolite-palygorskite, and chlorite) and two natural zeolites are reported here. Pressed powders of size-separated phyllosilicate and natural zeolite samples were heated incrementally from 100°C to 900°C, cooled to room temperature, and measured using multiple spectroscopic techniques: midinfrared (400-4000 cm-1) attenuated total reflectance, midinfrared reflectance (400-1400 cm-1), and far-infrared reflectance (50-600 cm-1) spectroscopies. Correlated thermogravimetric analysis and X-ray diffraction data were also acquired in order to clarify the thermal transformation of each sample. For phyllosilicate samples, the OH stretching (˜3600 cm-1), OH bending (˜590-950 cm-1), and/or H2O bending (˜1630 cm-1) bands all become very weak or completely disappear upon heating to temperatures > 500°C. The spectral changes associated with SiO4 vibrations (˜1000 cm-1 and ˜500 cm-1) show large variations depending on the compositions and structures of phyllosilicates. The thermal behavior of phyllosilicate IR spectra is also affected by the type of octahedral cations. For example, spectral features of Al3+-rich smectites are more stable than those of Fe3+-rich smectites. The high-temperature (>800°C) spectral changes of trioctahedral Mg2+-rich phyllosilicates such as hectorite, saponite, and sepiolite result primarily from crystallization of enstatite. Phyllosilicates with moderate Mg2+ concentration (e.g., palygorskite, clinochlore) and dioctahedral montmorillonites (e.g., SAz-1 and SCa-3) with partial Mg2+-for-Al3+ substitution all have new spectral feature developed at ˜900 cm-1 upon heating to 800°C. Compared with phyllosilicates, spectral features of two natural zeolites, clinoptilolite and mordenite, are less affected by thermal treatments. Even after heating to 900°C, the IR spectral features attributed to Si (Al)-O stretching and bending vibration modes do not show significant differences from those of unheated zeolites.

Che, Congcong; Glotch, Timothy D.; Bish, David L.; Michalski, Joseph R.; Xu, Wenqian



Minerals produced during cooling and hydrothermal alteration of ash flow tuff from Yellowstone drill hole Y-5  

USGS Publications Warehouse

A rhyolitic ash-flow tuff in a hydrothermally active area within the Yellowstone caldera was drilled in 1967, and cores were studied to determine the nature and distribution of primary and secondary mineral phases. The rocks have undergone a complex history of crystallization and hydrothermal alteration since their emplacement 600,000 years ago. During cooling from magmatic temperatures, the glassy groundmass underwent either devitrification to alkali feldspar + ??-cristobalite ?? tridymite or granophyric crystallization to alkali feldspar + quartz. Associated with the zones of granophyric crystallization are prismatic quartz crystals in cavities similar to those termed miarolitic in plutonic rocks. Vapor-phase alkali feldspar, tridymite, magnetite, and sporadic ??-cristobalite were deposited in cavities and in void spaces of pumice fragments. Subsequently, some of the vapor-phase alkali feldspar crystals were replaced by microcrystalline quartz, and the vapor-phase minerals were frosted by a coating of saccharoidal quartz. Hydrothermal minerals occur primarily as linings and fillings of cavities and fractures and as altered mafic phenocrysts. Chalcedony is the dominant mineral related to the present hydrothermal regime and occurs as microcrystalline material mixed with various amounts of hematite and goethite. The chalcedony displays intricate layering and was apparently deposited as opal from silica-rich water. Hematite and goethite also replace both mafic phenocrysts and vapor-phase magnetite. Other conspicuous hydrothermal minerals include montmorillonite, pyrite, mordenite, calcite, and fluorite. Clinoptilolite, erionite, illite, kaolinite, and manganese oxides are sporadic. The hydrothermal minerals show little correlation with temperature, but bladed calcite is restricted to a zone of boiling in the tuff and clearly was deposited when CO2 was lost during boiling. Fractures and breccias filled with chalcedony are common throughout Y-5 and may have been produced by rapid disruption of rock caused by sudden decrease of fluid pressure in fractures, most likely a result of fracturing during resurgent doming in this part of the Yellowstone caldera. The chalcedony probably was deposited as opal or ??-cristobalite from a pre-existing silica floc that moved rapidly into the fractures and breccias immediately after the sudden pressure drop. ?? 1978.

Keith, T.E.C.; Muffler, L.J.P.



Mineralogy and chemistry of bentonite (?) deposits at Minjingu, Lake Manyara, North Tanzania  

NASA Astrophysics Data System (ADS)

Olive green clays likely to be bentonitic in composition have been mineralogically and chemically studied. They occur in association with other lacustrine sediments at Lake Manyara. Radiocarbon dates from four diatom horizons indicate ages ranging from 12 Ka to 135 Ka suggesting a Mid-Holocene age. Middle Pleistocene age have been assigned to the ridged oncolites of Lake Manyara. The olive green coloured clays in the Manyara basin are known to occur in association with other lake beds including phosphorite deposits, stromatolites, bioturbated silty clays, partly silicified marls, conglomerates and olive green coloured opal beds. The results presented herein are from the olive green coloured clays. The olive green clays (bentonite?) are a result of devitrification or alteration of volcanic ashes and/or pyroclasts. The green clays occur in different forms as they are separated from each other by other lacustrine sediments. The alteration might have taken place in slightly different environments in terms of salinity and alkalinity. One of the top layer is friable and shows conchoidal fractures when dry. The other beds below in the lacustrine sequence are cemented with calcite and some dolomite as well as zeolites. The lowermost layer in the sequence is friable and shows cracks filled with coarse crystalline calcite. Mineralogically the bentonite is composed of the clay minerals illite, illite-smectite mixed layer clays, and chlorite. Other authigenic minerals include various zeolites (analcime, clinoptilolite, erionite and some traces of mordenite), opal, and fluorapatite. The clays have magnesium contents varying from 3.01% to 7.43%. The calcium contents vary widely due to presence or absence of one of the two minerals calcite or apatite. Trace elements like Ba, Ce, Sr, Zr are equally attributed to the presence of calcite and apatite. The formation of the illite-smectite mixed layer clays in an alternating manner with other lake sediments depicts different episodes of volcanic eruptions in the area. The mineralogical composition of smectites, zeolites, and opal in the green clays suggests a deposition of pyroclasts and volcanic ashes in a closed lake system with fluctuating levels. Due to evaporation alkalinity and salinity levels were fluctuating. The clays might have been bentonite which have undergone illitisation, a phenomena noted in other neighbouring rift basins.

Mutakyahwa, M. K. D.



Carbon dioxide-krypton separation and radon removal from nuclear-fuel-reprocessing off-gas streams  

SciTech Connect

General Atomic Company (GA) is conducting pilot-plant-scale tests that simulate the treatment of radioactive and other noxious volatile and gaseous constituents of off-gas streams from nuclear reprocessing plants. This paper reports the results of engineering-scale tests performed on the CO/sub 2//krypton separation and radon holdup/decay subsystems of the GA integrated off-gas treatment system. Separation of CO/sub 2/ from krypton-containing gas streams is necessary to facilitate subsequent waste processing and krypton storage. Molecular sieve 5A achieved this separation in dissolver off-gas streams containing relatively low krypton and CO/sub 2/ concentrations and in krypton-rich product streams from processes such as the krypton absorption in liquid carbon dioxide (KALC) process. The CO/sub 2//krypton separation unit is a 30.5-cm-diameter x 1.8-m-long column containing molecular sieve 5A. The loading capacity for CO/sub 2/ was determined for gas mixtures containing 250 ppM to 2.2% CO/sub 2/ and 170 to 750 ppM krypton in either N/sub 2/ or air. Gas streams rich in CO/sub 2/ were diluted with N/sub 2/ to reduce the temperature rise from the heat of adsorption, which would otherwise affect loading capacity. The effluent CO/sub 2/ concentration prior to breakthrough was less than 10 ppM, and the adsorption capacity for krypton was negligible. Krypton was monitored on-line with a time-of-flight mass spectrometer and its concentration determined quantitatively by a method of continuous analysis, i.e., selected-ion monitoring. Radon-220 was treated by holdup and decay on a column of synthetic H-mordenite. The Rn-220 concentration was monitored on-line with flow-through diffused-junction alpha detectors. Single-channel analyzers were utilized to isolate the 6.287-MeV alpha energy band characteristic of Rn-220 decay from energy bands due to daughter products.

Hirsch, P.M.; Higuchi, K.Y.; Abraham, L.



Geological, mineralogical and geochemical characteristics of zeolite deposits associated with borates in the Bigadiç, Emet and Kirka Neogene lacustrine basins, western Turkey  

NASA Astrophysics Data System (ADS)

The Bigadiç, Emet and Kirka lacustrine basins of western Turkey may be considered as Tibet-type graben structures that were developed during the Miocene within the Izmir-Ankara suture zone complex. The volcanic-sedimentary successions of these basins are made up of mudstone, carbonate (limestone and dolomite) and detrital rocks, and also of crystal or vitric tuffs about 135 to 200 m thick. The Degirmenli (Bigadiç), Emirler (Bigadiç) Köpenez (Emet) and Karaören (Kirka) tuffs constituting the zeolite deposits are situated beneath four borate deposits (colemanite, ulexite, borax). The most abundant diagenetic silicate minerals are K- and Ca-clinoptilolites in the zeolite deposits, and Li-rich trioctahedral smectites (stevensite, saponite and hectorite) and K-feldspar in the borate deposits. In the Degirmenli, Emirler, Köpenez and Karaören deposits, the following diagenetic facies were developed from rhyolitic glasses rich in K and poor in Na: (glass+smectite), (K-clinoptilolite+opal-CT), (Ca-clinoptilolite+K-feldspar±analcime± quartz) and (K-feldspar+analcime+quartz). K-feldspar which is also rarely associated with phillipsite (Karaören) and heulandite (Degirmenli and Karaören), succeeds clinoptilolite and precedes analcime in these diagenetic facies where dioctahedral smectites, opal-CT and quartz are the latest minerals. No diagenetic transformations exist between clinoptilolite, K-feldspar and analcime that were formed directly from glass. The lateral facies distributions resulted from the differences in salinity and pH of pore water trapped during deposition of the tuffs, but vertical distributions in vitric tuffs seem to have been controlled by the glass/liquid ratio of the reacting system and the permeability or diffusion rate of alkali elements. The Bigadiç, Emet and Kirka zeolite deposits which were formed in saline basins rich in Ca and Mg ions, show similar chemical changes, i.e. loss of alkalis and gain in alkaline-earth elements that have taken place during the diagenetic transformation of rhyolitic glasses to dioctahedral smectites or clinoptilolite. The absence of sodic zeolites such as mordenite, erionite, chabazite and silica-rich phillipsite is mainly due to the very high K/Na ratio of the starting materials rather than initial alkaline conditions or high Na content in lake waters.

Gündogdu, M. N.; Yalçin, H.; Temel, A.; Clauer, N.



Tephra Deposits in Lake Mead Miocene Sediments: Characteristics, Chronology, and Sources  

NASA Astrophysics Data System (ADS)

The Lake Mead extensional domain, in the east central Basin and Range Province, contains Miocene basin sediments that have undergone complex faulting and deformation. A rich tephra record in the basin sediments provides a chronological and correlation framework that can help understand the depositional and deformational processes during Miocene and post-Miocene time. The tephra layers, up to 10s of cm thick, range from white deposits containing glassy shards to bright green layers in which all original glass has been altered to the zeolite mordenite. The tephra layers range from aphyric to extremely crystal rich. Many appear to be primary ashfall deposits based on depositional geometry, uniform crystal size, and good preservation of glass or relict glass shard structures. However, some layers show evidence of reworking as evidenced by variable crystal size, and the presence of plutonic feldspar and rock fragments. Electron microprobe analyses of preserved glass reveal that compositions of almost all of the tephra layers are high silica rhyolite, typically with FeO and CaO contents of 1wt% or lower. Where present, the glass in the tephra layers is invariably hydrated, consistent with their age, but although the alkali concentrations in the glass are likely to have been modified by the hydration process, other elements, particularly Fe, Ca, Ti, and Cl appear to yield robust concentrations. The compositions of individual layers with respect to these elements are very homogeneous, based on analysis of 20-30 glass shards per sample, and can be used to correlate individual tephra layers between different parts of the sedimentary basin, although a number of layers have very similar compositions. Some higher Fe rhyolites/dacites (up to 4 wt.% FeO) are also observed. Crystal-bearing tephra layers contain some combination of quartz, one or two feldspars (typically a chemically uniform sanidine and a range of plagioclase compositions), biotite, amphibole, and magnetite. Variation is observed in the crystal size (close to 1 mm down to 10 um) and content (close to 50% to aphyric) of different tephra layers. For correlation of tephra layers with no glass, precisely measured K content of sanidine, along with the range of Ba concentration has proved to be most useful, although this criteria is more robust when suggesting non-correlations, because there appear to be instances where different eruptions have identical sanidine composition. 40Ar/39Ar age determinations on sanidine crystals reveal a large age range in tephra layers from the Lake Mead sedimentary basin, with the oldest tephra erupted at 22.88×0.02 Ma and the youngest at 12.93×0.02. Other tephra have ages of 13.20×0.04, 13.43×0.02, 14.20×0.05, 14.62×0.01, 15.09×0.02, 15.35×0.06, 15.67×0.07, 16.29×0.11, and 18.41×0.04. The chronology, geochemistry and coarse grain size of many of the tephra layers suggest derivation from either the Southwest Nevada Volcanic Field or the Caliente Caldera area. The tephra erupted at 12.93×0.02 is chronologically and geochemically similar to the very large Topopah Tuff eruption, and the 18.41×0.04 tephra may be related to the Caliente Caldera Hiko Canyon/Racer Canyon events. However, a set of finer grained, Fe-rich and/or anorthoclase-bearing tephra layers may have been erupted further afield, likely being related to Miocene Yellowstone plume track volcanism.

Dunbar, N. W.; McIntosh, W. C.; Umhoefer, P. J.; Lamb, M. A.; Hickson, T.



Geothermometry, geochronology, and mass transfer associated with hydrothermal alteration of a rhyolitic hyaloclastite from Ponza Island, Italy  

USGS Publications Warehouse

A rhyolitic hyaloclastite from Ponza Island, Italy, was hydrothermally altered, producing four distinct alteration zones based on X-ray diffraction mineralogy and field textures: (1) nonpervasive argillic zone; (2) propylitic zone; (3) silicic zone; and (4) sericitic zone. The unaltered hyaloclastite is volcanic breccia with clasts of vesiculated obsidian in a matrix of predominantly pumice lapilli. Incomplete alteration of the hyaloclastite resulted in the nonpervasive argillic zone, characterized by smectite and disordered opal-CT. The other three zones exhibit more complete alteration of the hyaloclastite. The propylitic zone is characterized by mixed-layer illite-smectite (I-S) with 10 to 85% I, mordenite, opal-C, and authigenic K-feldspar (akspar). The silicic zone is characterized by I-S with ???90% I, pure illite, quartz, akspar, and occasional albite. The sericitic zone consists primarily of I-S with ???66% I, pure illite, quartz, and minor akspar and pyrite. K/Ar dates of I-S indicate hydrothermal alteration occurred at 3.38 ?? 0.08 Ma. Oxygen isotope compositions of I-S systematically decrease from zones 1 to 4. In the argillic zone, smectite has ??18 O values of 21.7 to 22.0??? and I-S from the propylitic, silicic, and sericitic zones ranges from 14.5 to 16.3???, 12.5 to 14.0???, and 8.6 to 11.9???, respectively. ??18 O values for quartz from the silicic and sericitic zones range from 12.6 to 15.9???. By use of isotope fractionation equations and data from authigenic quartz-hosted primary fluid inclusions, alteration temperatures ranged from 50 to 65 ??C for the argillic zone, 85 to 125 ??C for the propylitic zone, 110 to 210 ??C for the silicic zone, and 145 to 225 ??C for the sericitic zone. Fluid inclusion data and calculated ??18 O water values indicate that hydrothermal fluids were seawater dominated. Mass-transfer calculations indicate that hydrothermal alteration proceeded in a relatively open chemical system and alteration in the sericitic zone involved the most extensive loss of chemical species, especially Si. Systematic gains in Mg occur in all alteration zones as a result of I-S clay mineral formation, and systematic losses of Na, Ca, and K occur in most zones. With the exception of Ca, calculations of mass transfer associated with hydrothermal alteration on Ponza agree with chemical fluxes observed in laboratory experiments involving hydrothermal reactions of rhyolite and seawater. The anomalous Ca loss at Ponza may be due to hydrothermal formation of anhydrite and later low-temperature dissolution. On the basis of Mg enrichments derived from circulating seawater, we estimate the following minimum water/rock ratios: 9, 3, 6, and 9 for the argillic, propylitic, silicic, and sericitic zones, respectively. Hydrothermal fluid pH for the propylitic and silicic zones was neutral to slightly basic and relatively acidic for the sericitic zone as a result of condensation of carbonic and perhaps other acids. Copyright ?? 2003 Elsevier Science Ltd.

Altaner, S.P.; Ylagan, R.F.; Savin, S.M.; Aronson, J.L.; Belkin, H.E.; Pozzuoli, A.



Erionite and other fibrous zeolites in volcanic environments: the need for a risk assessment in Italy  

NASA Astrophysics Data System (ADS)

In many European countries in the '90s there was a significant increase in mortality linked to mesothelioma, a cancer of the lung, involving pleural, pericardial and peritoneal mesothelial cells, which unfortunately has no cure at present. Though most of these cases have been attributed to t asbestos, in Italy at least 17% of cases of mesothelioma is still not fully explained. In the years between 1990 and 2000, it was discovered that the inhalation of erionite fibers (a zeolite group mineral, that can be found in altered volcanic rocks) was the cause of a regional epidemic of mesothelioma in some villages of Cappadocia (Turkey). Erionite, in fact, was recently included in Class 1 (highly carcinogenic) by the World Health Organization, up to 800 times more carcinogenic than asbestos; on the other hand, little is known about the toxicity of other fibrous zeolites, commonly intergrown with erionite, such as offretite and mordenite. Erionite was reported in different regions of Italy; nevertheless, a systematic mapping of its distribution, the quantification of its presence in rocks and data about airborne fibers are still missing. We carried out first preliminary sampling in Veneto, in Tertiary volcanic rocks, mainly hydrothermally altered basalts. The first mineralogical investigations by means of XRPD, SEM-EDS and OM confirmed the presence of small amounts of erionite and abundant fibrous offretite, in vugs of basaltic rocks. Intergrowths and overgrowths with other fibrous minerals are quite common, and the morphological-chemical similarities among these zeolites pose a special analytical problem, with the need of combining different techniques. Our first findings, combined with the fact that zeolites are important industrial minerals, emphasize the need of a risk assessment in Italy and Europe, because there are no systematic studies on the distribution of erionite or similar fibrous zeolites in the environment. The knowledge of the epidemiology of mesothelioma linked to erionite in Italy is extremely scarce: INAIL, through its database of occupational diseases, can provide essential information for epidemiological research. An effective risk assessment in Italy will require coordinated actions from government agencies, local health authorities, Universities and research centers, in order to record the actual presence of fibrous zeolites, recognizing mineral species and quantifying their abundance in rock deposits. The different geological conditions through time of volcanic deposits will be compared with an updated "database" on the physical-chemical-geological conditions of formation of zeolites. In sites where the presence of fibrous zeolites has been validated by laboratory tests, we will proceed with accurate field surveys and sampling campaigns, in order to determine detailed geological-stratigraphic and structural features, and resolving precisely the thickness, areal extent and volume of lithostratigraphic units containing these minerals. These data will be entered into a GIS to produce a result that can be used immediately and in the long-period by research institutes, local authorities and regional agencies for environmental protection. In sites where the presence of hazardous fibrous minerals has been validated, we will plan airborne fibers sampling campaigns, and we will assess the extent of airborne dispersion produced by natural agents and by man activity. In the case that these sites host active mining or quarrying activities, we will quantify the airborne fibers contamination at workplaces and propose measures for environmental risk mitigation.

Cavallo, A.; Rimoldi, B.



A thermodynamic and structural study of atomistic, nano and bulk systems  

NASA Astrophysics Data System (ADS)

Atomistic and nanocrystalline materials exhibit significantly different properties than bulk materials. This work aims to compare thermodynamic and structural properties of atomistic, nanocrystalline and bulk materials using high temperature oxide melt drop solution calorimetry, high energy synchrotron X-ray diffraction and computational techniques using molecular mechanics modelling. Oxidative drop solution calorimetry is being developed as a general method for sulfide thermochemistry. Enthalpies of formation (kJ/mol) from the elements (DeltaH°f) are determined for sphalerite (ZnS) (-206.53 +/- 4.03 kJ/mol), galena (PbS) (-98.12 +/- 4.37 kJ/mol), greenockite (hexagonal CdS) (-148.79 +/- 4.13 kJ/mol) and hawleyite (cubic CdS) (-147.65 +/- 4.28 kJ/mol). The enthalpy of formation of hawleyite was determined for the first time. Oxide melt drop solution calorimetry was also developed for selenides. Enthalpies of formation (kJ/mol) from the elements (DeltaH°f) are determined for zinc selenide (ZnSe) (-160.13 +/- 2.91 kJ/mol), lead selenide (PbSe) (-100.83 +/- 4.39 kJ/mol), and cadmium selenide (CdSe) (-138.99 +/- 8.70 kJ/mol). The values for CdSe and PbSe match published data, the DeltaH°f value for CdSe from direct calorimetry is reported for the first time, and a more reliable value for ZnSe is proposed as available data for ZnSe are quite scattered. High-temperature oxide melt solution calorimetry was used to determine the dehydration enthalpy and the formation enthalpy of cationic variants of zeolite beta (Li-BEA, Na-BEA, K-BEA, Rb-BEA and Cs-BEA) from the constituent oxides. The dehydration enthalpy per mole of water decreases in the order Li-BEA > Na-BEA >Cs-BEA > K-BEA >Rb-BEA. Molecular mechanics was used to investigate location of the alkali cations and bonding of water molecules in BEA zeolites. The somewhat smaller dehydration enthalpy of K-BEA can be attributed to weaker cation-water interaction, weaker cation-framework interaction, and absence of framework-water interaction. The enthalpies of formation and dehydration of Li and Na ion exchanged zeolite beta are investigated by high temperature oxide melt solution calorimetry. For Li-BEA, the formation enthalpies of formation from oxides at 25°C are 25.6 +/- 1.7 kJ/mol TO2 for the dehydrated zeolite and -8.45 +/- 0.94 kJ/mol TO2 for the fully hydrated zeolite; for Na-BEA they are -2.4 +/- 0.6 kJ/mol TO2 for the dehydrated and -17.8 +/- 1.0 kJ/mol TO2 for the fully hydrated zeolite. The integral dehydration enthalpy at 25°C is 33.2 +/- 1.8 kJ/mol H2O for Li-BEA and 16.5 +/- 1.1 kJ/mol H2O for Na-BEA. Molecular mechanics simulations explore the cation and water molecule positions in the framework at several water contents. This study presents an analysis of the role of structural water in stabilization of bulk synthetic akaganeite (beta-FeOOH) and compare the structural behavior of bulk and nano akaganeite. Rietveld refinements using synchrotron X-ray powder diffraction data are presented. Akaganeite is, indeed, monoclinic with the Cl atoms located at the center of the tunnels and filling only ˜2.8% of the tunnel sites (0,0,0) in this sample. Structural water and vacancies occupy the remaining tunnel sites. There is no evidence of ordering of water molecules in the tunnels. In nanophase akaganeite, the diffraction pattern shows a mixture of akaganeite and a goethite-like phase. The destruction of the tunnel structure, because of the large fraction of tunnels exposed at the surface of the small particles, leads to the formation of this goethite-like phase, possibly a surface reconstruction on the akaganeite particles. As the particle size increases, the formation of the tunnel structure is complete and the goethite-like phase disappears. The closely balanced energetics of akaganeite and goethite permit this complex crossover in stability, with goethite or goethite-like phases present at small and large, but not intermediate, particle size. The localization and arrangement of thionin blue (C12H 10N3S+) dye molecules in the zeolite mordenite frame

Deore, Suraj Waman


Impact Materials of Takamatsu Crater in Japan  

NASA Astrophysics Data System (ADS)

Shocked quartz materials have been found in Japanese K.T boundary (Hokkaido) and mountains of middle main-islands of Japan, though there are few direct evidence of "natural circular structure" on the surface in Japan. However circular structure has been recently found as a buried crater(up to 150m deep) [1] which is ca. 4km in diameter with -10 mgal of Bouguer gravity anomaly from surrounding Rhyoke granitic region of the southern part of Takamatsu City, Kagawa Prefecture, northeast Shikoku, Japan [1,2,3]. Two boring cores of 300m deep near small mountains inside the crater could not reach the bottom of the crater so far. From model calculation of the negative gravity anomaly, the Takamatsu crater shows deep basin structure up to 1.4km. If the Takamatsu crater is considered to be only impact crater, it is difficult to discuss only surface materials on the crater. But anomalous minerals are found only around small volcanic intrusions inside the crater, which the mixed minerals are clearly different with those of other volcanic intrusions of the Yashima and Goshikidai outside the crater [1,2,3]. The small volcanic intrusions are not origin of large Takamatsu crater, because the small volcanic intrusions are found on whole areas of Kagawa Prefecture. Major different activity of the small intrusions inside the crater is to bring the brecciated materials of the interior (esp. crater sediments). The xenolith materials around only volcanic intrusion of andesite are divided into the following four major mineral materials:(a) round pebble fragments from the Rhyoke granitic basement (Sampling No.15), (b) rock fragments from intruded biotite andesites (Nos. 2,15), (c) impact-induced fragments of shocked Quartz grains (Nos. 2,3,6,15), diaplectic feldspars (Nos. 2,3,6,15), silica glasses (Nos. 2,15) and small Fe-Ni metallic grains (No.15), and (d) small sedimentary fragments of halite and mordenite, as listed in Table 1. Table I, showing the characterization of surface samples around small intrusions of the Takamatsu crater, appears here in the hard copy. The following anomalous mixed materials are considered to be impact-induced origin: 1) Fe-Ni grains: Black glassy rocks at Jissojiyama (No. 15) contain irregularly Fe-Ni grains of 10 to 100 micrometers in diameter. Chemical composition of the small Fe+Ni grains varies from ca. 18~90 atom. % mixed with the major granitic components. Atomic ratios of Fe/Ni are the same of kamacite as 3.4 to 68.7, but differ from those of awaruite (Fe/Ni<0.5) from the deep seated rock of the interior of the Earth [4]. The similar tiny Fe grains are found on the Wolf Creek and Ries impact craters. 2) Shocked quartz with high-density and shock lamellae: Anomalous quartz grains with undulatory anomalous extinction and shock lamellae are found at the Hiyama (Nos. 2,3,6 in whitish fine rocks) and Jissoiiyama (No. 15 in black glass) as brecciated xenolith from the interior of crater sediments. Typical shocked quartz grain shows with two sets of shock lamellae along pi (102) crystallographic planes [5]. The main X-ray diffraction peaks of each Miller plane show high Bragg angle and X-ray density (Delta rho=+0.9+/-0.3%) and lower values (ca.- 0.4%) of each plane-distance of all shock-generated Plane deformation features (PDFs). The structural data of high density are the same of shocked quartz grains in terrestrial impact craters [6,7]. 3) Diaplectic feldspars: Shock-generated diaplectic feldspars with compositions of albite plagioclases with undulatory extinction are observed with dark or partly dark (i.e. diaplectic) glassy materials under cross-polarized microscope (Nos. 2,3,6,15). Crushed plagioclases with circular or ellipsoidal shape are also found at Hiyama (No. 6) and Hiraike (No. ll). Diffuse and irregular textures of feldspar fragments are different with other localities outside the crater [2,3]. 4) G1asses of potassium feldspar compositions: Many glassy fragments with flow texture are observed from fine-grained sediments around Hiyama (Nos. 2,3,6), which have potassium feldspars compos

Miura, Y.; Okamoto, M.; Fukuchi, T.