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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



Nafion\\/mordenite hybrid membrane for high-temperature operation of polymer electrolyte membrane fuel cell  

Microsoft Academic Search

Nafion\\/mordenite hybrid membranes for the operation of polymer electrolyte membrane fuel cells (PEMFCs) above 100 °C were prepared by mixing of H+-form mordenite powder and perfluorosulfonylfluoride copolymer resin. PEMFC operation above 100 °C reduces CO poisoning as well as passivation of the Pt anode electrocatalyst by other condensable species. The physico-chemical properties of hybrid membranes were investigated by tensile strength

Sang-Hee Kwak; Tae-Hyun Yang; Chang-Soo Kim; Ki Hyun Yoon



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



Organic iodine removal from simulated dissolver off-gas systems utilizing silver-exchanged mordenite  

SciTech Connect

The removal of methyl iodide by adsorption onto silver mordenite was studied using a simulated off-gas from the fuel dissolution step of a nuclear fuel reprocessing plant. The adsorption of methyl iodide on silver mordenite was examined for the effect of NO/sub x/, humidity, iodine concentration, filter temperature, silver loadings and filter pretreatment. The highest iodine loading achieved in these tests was 142 mg CH/sub 3/I per g of substrate on fully exchanged zeolite, approximately the same as elemental iodine loadings. A filter using fully exchanged silver mordenite operating at 200/sup 0/C obtained higher iodine loadings than a similar filter operating at 150/sup 0/C. Pretreatment of the sorbent bed with hydrogen rather than dry air, at a temperature of 200/sup 0/C, also improved the loading. Variations in the methyl iodide concentration had minimal effects on the overall loading. Filters exposed to moist air streams attained higher loadings than those in contact with dry air. Partially exchanged silver mordenite achieved higher silver utilizations than the fully exchanged material. The partially exchanged mordenite also achieved higher loadings at 200/sup 0/C than at 250/sup 0/C. The iodine loaded onto these beds was not stripped at 500/sup 0/C by either 4.5% hydrogen or 100% hydrogen; however, the iodine could be removed by air at 500/sup 0/C, and the bed could be reloaded. A study of the regeneration characteristics of fully exchanged silver mordenite indicates limited adsorbent capacity after complete removal of the iodine with 4.5% hydrogen in the regeneration gas stream at 500/sup 0/C. The loss of adsorbent capacity is much higher for silver mordenite regenerated in a stainless steel filter housing than in a glass filter housing.

Jubin, R.T.



Spectroscopy and redox chemistry of copper in mordenite.  


Copper-containing zeolites, such as mordenite (MOR), have recently gained increased attention as a consequence of their catalytic potential. While the preferred copper loadings in these catalytic studies are generally high, the literature lacks appropriate spectroscopic and structural information on such Cu-rich zeolite samples. Higher copper loadings increase the complexity of the copper identity and their location in the zeolite host, but they also provide the opportunity to create novel Cu sites, which are perhaps energetically less favorable, but possibly more reactive and more suitable for catalysis. In order to address the different role of each Cu site in catalysis, we here report a combined electron paramagnetic resonance (EPR), UV/Vis-NIR and temperature-programmed reduction (TPR) study on highly copper-loaded MOR. Highly resolved diffuse reflectance (DR) spectra of the CuMOR samples were obtained due to the increased copper loading, allowing the differentiation of two isolated mononuclear Cu(2+) sites and the unambiguous correlation with extensively reported features in the EPR spectrum. Ligand field theory is applied together with earlier suggested theoretical calculations to determine their coordination chemistry and location within the zeolite matrix, and the theoretical analysis further allowed us to define factors governing their redox behavior. In addition to monomeric species, an EPR-silent, possibly dimeric, copper site is present in accordance with its charge transfer absorption feature at 22200 cm(-1), and quantified with TPR. Its full description and true location in MOR is currently being investigated. PMID:24399800

Vanelderen, Pieter; Vancauwenbergh, Julie; Tsai, Ming-Li; Hadt, Ryan G; Solomon, Edward I; Schoonheydt, Robert A; Sels, Bert F



Comparison of the ion exchange uptake of ammonium ion onto New Zealand clinoptilolite and mordenite.  


In this study the uptake performances of the naturally occurring zeolite, clinoptilolite, and of New Zealand mordenite are compared. The uptake of fully ionised ammonium ion from aqueous solutions in the concentration range 0-200 mg/l on to these two materials was compared. The influence of other cations present in water upon the ammonia uptake was also determined. The cations studied were potassium, calcium and magnesium. In all cases the anionic counterion present was chloride. The results showed that the mordenite exhibited higher overall uptake concentrations at equilibrium compared with clinoptilolite at solution concentrations greater than 80 mg/l. Beyond this value, the difference in solid-phase equilibrium concentrations on the mordenite became greater at higher solution-phase ammonium ion concentrations. The effect of the other cations upon uptake of ammonium ion was relatively small. In all cases, the ammonium ion showed the highest uptake on to both the mordenite and the clinoptilolite. In the case of clinoptilolite this was rather an unexpected result since the majority of other work shows clinoptilolite exhibiting a higher affinity for potassium ion compared with ammonium ion. This may be explained by the fact that the clinoptilolite came from volcanic deposits in New Zealand. This is the first such study on this material. At solution-phase equilibrium concentrations of greater than 80 mg/l, the mordenite showed smaller reductions in ammonium ion uptake in the presence of the other cations when compared with clinoptilolite. PMID:15556205

Weatherley, L R; Miladinovic, N D



Adsorption and energetics of xenon in mordenite: A Monte Carlo simulation study  

NASA Astrophysics Data System (ADS)

Grand canonical Monte Carlo (GCMC) simulations were used to calculate energy contour maps, isodensity surfaces and adsorption isotherms of xenon in purely siliceous mordenite at 300 K using previously published potential parameters. Then, in order to understand the effect of aluminum content, Al-containing mordenites were modeled by adding the appropriate negative charge to each of the oxygen atoms in the mordenite framework and by inserting Na+ ions at fixed extra-framework positions previously identified from x-ray crystallographic data. GCMC simulations were again performed using these structure models. Both main channel and sidepocket xenon adsorption were observed in all mordenite structures. The sidepockets were found to be only singly occupied whereas the main channel allowed multiple occupancy. Sidepocket xenon adsorption became more favorable when cations (and aluminum) were introduced. In the main channel, xenon adsorbed into localized sites that were distributed in an octahedral arrangement within each unit cell with two apices in front of opposing sidepockets. These sites remained at the same location over the entire range of loading (0-16 Xe/unit cell) and cation (and aluminum) content.

Nivarthi, Sriram S.; Van Tassel, Paul R.; Davis, H. Ted; McCormick, Alon V.



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



Transesterification of ethyl butyrate with methanol over 1-butyl-3-methylimidazolium exchanged mordenite  

Microsoft Academic Search

Transesterification of ethyl butyrate with methanol on the organic cation-exchanged mordenite ([bmim]M20) was studied in order to examine the reactivity of the methoxide ions that were generated on [bmim]M20 by the dissociation of methanol. Since transesterification occurred by addition of NaCl, the methoxide ions on [bmim]M20 were demonstrated to be utilizable in the reaction. The activity improved with a concentration

Eisuke Yoda



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)



Optimization of sintered AgI-Mordenite composites for {sup 129}I storage  

SciTech Connect

The thermal processing of a proposed durable waste form for {sup 129}I was investigated. The waste form is a composite with a matrix of low-temperature sintering glass that encapsulates particles of AgI-mordenite. Ag-mordenite, an ion-exchanged zeolite, is being considered as a capture medium for gaseous {sup 129}I{sub 2} as part of a spent nuclear fuel reprocessing scheme under development by the US Department of Energy/Nuclear Energy (NE). The thermal processing of the waste form is necessary to increase the density of the glass matrix by viscous sintering so that the final waste form does not have any open porosity. Other processes that can also occur during the thermal treatment include desorption of chemisorbed I{sub 2}, volatilization of AgI and crystallization of the glass matrix. We have optimized the thermal processing to achieve the desired high density with higher AgI-mordenite loading levels and with minimal loss of iodine. Using these conditions, 625 C. degrees for 20 minutes, the matrix crystallizes to form a eulytite phase. Results of durability tests indicate that the matrix crystallization does not significantly decrease the durability in aqueous environments. (authors)

Garino, T.J.; Nenoff, T.M.; Rodriguez, M.A.; Mowry, C.D.; Rademacher, D.X. [Sandia National Laboratories, P.O. Box 5800, Albuquerque, NM 87185-1411 (United States)



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))



Adsorption and vibrational spectroscopy of CO on mordenite: Ab initio density-functional study.  


We present a periodic density-functional investigation of the adsorption and the vibrational spectroscopy of CO in mordenite. Our results highlight a pronounced sensitivity of the strength of the hydrogen bond between the acidic hydroxyl groups and the adsorbed molecule, and hence of the induced red shift of the OH, and the blue shift of the CO stretching mode on the choice of the exchange-correlation functional. The popular Perdew-Wang (PW) gradient-corrected functional strongly overestimates the frequency shifts and the interaction energies. We demonstrate that the revised Perdew-Burke-Ernzerhof (RPBE) functional leads to an improved description of hydrogen bonding. For bridging OH groups, terminal silanol groups and for Lewis sites formed by tricoordinated Al atoms, we predict adsorption energies and frequency shifts in good agreement with experiment. The calculated difference in the binding energies of CO in purely siliceous mordenite and at Brønsted acid sites in the main channel agrees very well with microcalorimetry data. We find that Brønsted acid sites in the small channels (the side-pockets) of mordenite do not adsorb CO, which is adsorbed only in the main channel via the C atom. For these adsorption complexes we find reasonable (though not perfect) agreement of the predicted blue shift of the CO-mode and of the red shift of the OH-mode with experiment. Our prediction that the side-pockets are inaccessible to CO correlates well with the microcalorimetric studies and with experimental observation of the adsorption of O(2), N(2) and H(2) molecules but contradicts the current interpretation of experimental adsorption studies for CO. PMID:16851841

Bucko, T; Hafner, J; Benco, L



Interaction of mordenite with an aromatic hydrocarbon: An embedded ONIOM study  

Microsoft Academic Search

The structure of mordenite (MOR) and its interaction with benzene has been investigated within the framework of our-own-N-layered integrated molecular orbital+molecular mechanics (ONIOM) approach utilizing the two-layer ONIOM scheme (B3LYP\\/6-31G(d,p):UFF). The effect of the long range interactions is also included via optimized point charges added to the ONIOM2(B3LYP\\/6-31G(d,p):UFF), embedded ONIOM. Inclusion of the extended zeolitic framework covering the nanocavity has

Bavornpon Jansang; Tanin Nanok; Jumras Limtrakul



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))



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)



Alkylations of benzene, alkylbenzenes, and halobenzenes catalyzed by protonated mordenite pretreated with chlorofluorocarbons  

SciTech Connect

The chlorofluorocarbon (CFC) treatment of protonated mordenite (HM) was carried out in a flow reactor under ordinary pressure, usually at 600C for 10 min using CCIF{sub 3} as a treatment agent. The mordenite structure was almost completely retained during the CFC treatment. Evidence for dealumination and surface fluorination was observed by XPS examination. Decrease of surface acidity, as seen by NH{sub 3-}TPD, accompanied the treatment. The function of HM as a catalyst for alkylations of benzene and alkylated or halobenzenes with methanol was greatly enhanced by the CFC treatment. In particular, the activity maintenance was remarkably improved. Thus, in the alkylations at 300C under the molar ratios of CH{sub 3}OH/Aromatic compound = 1 and W/F = 81.2 (for toluene) or 97.5 (for 1,2,4-trimethylbenzene (TBM)) g h/mol, the conversions at the initial stage of the run were increased from 27 to 65% (for toluene) and from 12 to 47% (for TMB) by CFC treatment of the Hm catalyst. In addition, the conversions of benzene and TMB were well maintained at about 60 and 40%, respectively, throughout the running time of 3 h in the reactions catalyzed by the treated HM, while the conversions of benzene and TMB rapidly decreased and became almost zero within 90 min in the reaction catalyzed by untreated HM.

Kodama, Hiroto; Okazaki, Susumu (Ibaraki Univ. (Japan))



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



Siting of B, Al, Ga or Zn and bridging hydroxyl groups in mordenite: an ab initio study  

Microsoft Academic Search

The siting of B, Al, Ga or Zn and bridging OH groups in the framework of mordenite was studied by ab initio Hartree–Fock MO methods. The basis set effect on the calculation results was investigated in details. It was shown that heteroatoms including B, Al, Ga and Zn prefer the same T sites, T3 and T4, when replacing Si in

Shuping Yuan; Jianguo Wang; Yongwang Li; Shaoyi Peng



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

NASA Astrophysics Data System (ADS)

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.

Arletti, Rossella; Martucci, Annalisa; Alberti, Alberto; Pasti, Luisa; Nassi, Marianna; Bagatin, Roberto



A study involving mordenite, titanate nanotubes, perfluoroalkoxy polymers, and ammonia borane  

NASA Astrophysics Data System (ADS)

Zeolites and molecular sieves are finding applications in many areas of catalysis due to appreciable acid activity, shape selectivity, and ion-exchange capacity, as they possess an unbalanced framework charge. For catalytic applications, zeolites become more valuable as the ratio of SiO2/Al2O 3 increases. Acid resistance and thermal stability of zeolite are both improved with increasing SiO2/Al2O3. This part of the thesis deals with the control of morphology focused on decreasing the crystal diameter of mordenite zeolite and to increase the SiO2/Al 2O3 ratio by changing synthesis conditions. A high SiO 2/Al2O3 ratio (SAR15) of mordenite was prepared in a very short reaction time. We studied the role of hydroxide in the crystallization of the mordenite as a structure director, nucleation time modifier, and crystallite aggregate enhancer. The formation of nano-aggregates of mordenites was greatly enhanced using a combination of alcohol additives and conventional heating. Mordenite nucleation was also increased without using alcohols when microwave heating was employed, but the alcohols further accelerated the nucleation process. The different heating techniques affected the morphology; microwave heating produced crystallites of ˜40 nm, while the conventional hydrothermal method formed larger size crystallites of ˜88 nm. We controlled the size and shape of the mordenite crystals because they have important implications in hydrocarbon conversion and separation processes. Mordenite synthesized showed jellyfish, acicular, flower, and wheat grain like structures. In the second part of this thesis, a phase transition was successfully achieved from TiO2 particles to titanate nanotubes by the breakage of Ti-O bonds and the creation of oxygen vacancies without using expensive precursors, high temperatures, high chemical concentrations of alkaline solutions, and long synthesis times. A combination of anatase nano-particles/titanate nano-tubes was synthesized using TiO2 (anatase) and a temperature of only 100°C. When TiO2 (P-25) was used with the same concentration of alkaline solution (1 molar NaOH), the same processing time of 12 hours, and a higher temperature at 110°C, only titanate nano-tubes were observed. The linkages of 'Ti-O' play a very important role in the structural features of different phases. Two crystalline phases (tetragonal and monoclinic) were synthesized as products in the case of TiO 2 (anatase) and one crystalline phase (monoclinic) for products of TiO 2 (P-25). The third part of the thesis concerns surface modification of hydrophobic fluoropolymers that have low surface energies and are very difficult to metallize. Surface modification was done to enhance surface roughness and hence to boost surface energy for metallization processes. We used low impact, environmentally friendly non-thermal plasmas at atmospheric pressure to strip off F - ions and replace them with reactive unsaturated hydrocarbon functionalities such as CH=CH2 on the surface of a polymer. As these hydrocarbon functionalities are reactive with metals, they form composites that have good adhesion between layers of polymer. Due to surface modification, polymeric chains were broken by the loss of fluorine atoms (F/C = 0.33) and the gain of oxygen atoms (O/C = 0.17) using methane/argon plasmas. Methane/hydrogen/argon plasmas on the other hand produced extensive loss of fluorine atoms (F/C = 0.07-0.33) and gain of oxygen atoms (O/C = 0.08-0.16) that was far better than pristine PFA. The surface of PFA was modified by defluorination and oxidation. Further enhancement of COF and COO groups revealed that the surface was modified to a hydrophilic membrane that can further be easily hydrolyzed to COOH in the presence of atmospheric humidity. The last part of the thesis deals with ammonia borane which was studied as a potential source of hydrogen for fuel cells. We analyzed the viability of ammonia borane as a hydrogen carrier compound for fuel cell applications using a thermolysis method. Ammonia borane is an attractive source for hydrogen productio

Nosheen, Shaneela


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.



Direct synthesis of ethanol from dimethyl ether and syngas over combined H-Mordenite and Cu/ZnO catalysts.  


Ethanol was directly synthesized from dimethyl ether (DME) and syngas with the combined H-Mordenite and Cu/ZnO catalysts that were separately loaded in a dual-catalyst bed reactor. Methyl acetate (MA) was formed by DME carbonylation over the H-Mordenite catalyst. Thereafter, ethanol and methanol were produced by MA hydrogenation over the Cu/ZnO catalyst. With the reactant gas containing 1.0% DME, the optimized temperature for the reaction was at 493 K to reach 100% conversion. In the products, the yield of methanol and ethanol could reach 46.3% and 42.2%, respectively, with a small amount of MA, ethyl acetate, and CO(2). This process is environmentally friendly as the main byproduct methanol can be recycled to DME by a dehydration reaction. In contrast, for the physically mixed catalysts, the low conversion of DME and high selectivity of methanol were observed. PMID:20715046

Li, Xingang; San, Xiaoguang; Zhang, Yi; Ichii, Takashi; Meng, Ming; Tan, Yisheng; Tsubaki, Noritatsu




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



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



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)



Adsorption and vibrational spectroscopy of ammonia at mordenite: ab initio study.  


The adsorption of ammonia at various active centers at the outer and inner surfaces of mordenite, involving Brønsted acid (BA) sites, terminal silanol groups, and Lewis sites has been investigated using periodic ab initio density-functional theory. It is shown that ammonia forms an ammonium ion when adsorbed at strong BA sites. The calculated adsorption energies for different BA sites vary in the interval from 111.5 to 174.7 kJ/mol depending on the local environment of the adduct. The lowest adsorption energy is found for a monodentate complex in the main channel, the highest for a tetradentate configuration in the side pocket. At weak BA sites such as terminal silanol groups or a defect with a BA site in a two-membered ring ammonia is H bonded via the N atom. Additional weak H bonds are formed between H atoms of ammonia and O atoms of neighboring terminal silanol groups. The calculated adsorption energies for such adducts range between 61.7 and 70.9 kJ/mol. The interaction of ammonia with different Lewis sites is shown to range between weak (DeltaE(ads)=17.8 kJ/mol) and very strong (DeltaE(ads)=161.7 kJ/mol), the strongest Lewis site being a tricoordinated Al atom at the outer surface. Our results are in very good agreement with the distribution of desorption energies estimated from temperature-programmed desorption (TPD) and microcalorimetry experiments, the multipeaked structure of the TPD spectra is shown to arise from strong and weak Brønsted and Lewis sites. The vibrational properties of the adsorption complexes are investigated using a force-constant approach. The stretching and bending modes of NH(4) (+) adsorbed to the zeolite are strongly influenced by the local environment. The strongest redshift is calculated for the asymmetric stretching mode involving the NH group hydrogen bonded to the bridging O atom of the BA site, the shift is largest for a monodentate and smallest for a tetradentate adsorption complex. The reduced symmetry of the adsorbate also leads to a substantial splitting of the stretching and bending modes. In agreement with experiment we show that the main vibrational feature which differentiates coordinatively bonded ammonia from a hydrogen-bonded ammonium ion is the absence of bending modes above 1630 cm(-1) and in the region between 1260 and 1600 cm(-1), and a low-frequency bending band in the range from 1130 to 1260 cm(-1). The calculated distribution of vibrational frequencies agrees very well with the measured infrared adsorption spectra. From the comparison of the adsorption data and the vibrational spectra we conclude that due to the complex adsorption geometry the redshift of the asymmetric stretching is a better measure of the acidity of an active sites than the adsorption energy. PMID:15268051

Bucko, T; Hafner, J; Benco, L



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



A density functional theory study of molecular and dissociative adsorption of H2 on active sites in mordenite.  


Adsorption and chemisorption of H2 in mordenite is studied using ab initio density functional theory (DFT) calculations. The geometries of the adsorption complex, the adsorption energies, stretching frequencies, and the capacity to dissociate the adsorbed molecule are compared for different active sites. The active centers include a Brønsted acid site, a three-coordinated surface Al site, and Lewis sites formed by extraframework cations: Na+, Cu+, Ag+, Zn2+, Cu2+, Ga3+, and Al3+. Adsorption properties of cations are compared for a location of the cation in the five-membered ring. This location differs from the location in the six-membered ring observed for hydrated cations. The five-membered ring, however, represents a stable location of the bare cation. In this position any cation exhibits higher reactivity compared with the location in the six-membered ring and is well accessible by molecules adsorbed in the main channel of the zeolite. Calculated adsorption energies range from 4 to 87 kJ/mol, depending on electronegativity and ionic radius of the cation and the stability of the cation-zeolite complex. The largest adsorption energy is observed for Cu+ and the lowest for Al3+ integrated into the interstitial site of the zeolite framework. A linear dependence is observed between the stretching frequency and the bond length of the adsorbed H2 molecule. The capacity of the metal-exchanged zeolite to dissociate the H2 molecule does not correlate with the adsorption energy. Dissociation is not possible on single Cu+ cation. The best performance is observed for the Ga3+, Zn2+, and Al3+ extraframework cations, in good agreement with experimental data. PMID:16853930

Benco, L; Bucko, T; Hafner, J; Toulhoat, H



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.



Effects of Zeolite Structure And Composition on the Synthesis of Dimethyl Carbonate By Oxidative Carbonylation of Methanol on Cu-Exchanged Y, ZSM-5, And Mordenite  

SciTech Connect

The aim of this work was to establish the effects of zeolite structure/chemical composition on the activity and selectivity of Cu-exchanged Y (Si/Al = 2.5), ZSM-5 (Si/Al = 12), and Mordenite (Si/Al = 10) for the oxidative carbonylation of methanol to DMC. Catalysts were prepared by solid-state ion-exchange of the H-form of each zeolite with CuCl and were then characterized by FTIR and X-ray absorption spectroscopy (XAS). The XANES portion of the XAS data showed that all of the copper was present as Cu{sup +} cations, and analysis of the EXAFS portion of the data shows the Cu{sup +} cations had a CuO coordination number of 2.1 on Cu-Y and 2.7 on Cu-ZSM-5 and Cu-MOR. Dimethyl carbonate (DMC) was observed as the primary product when a mixture of CH{sub 3}OH/CO/O{sub 2} was passed over Cu-Y, whereas dimethoxy methane was the primary product over Cu-ZSM-5 and Cu-MOR. The higher activity and selectivity of Cu-Y for the oxidative carbonylation of methanol can be attributed to the weaker adsorption of CO on the Cu{sup +} cations exchanged into Y zeolite. In situ IR observations revealed that under reaction conditions, adsorbed CO was displaced by methoxide groups bound to the Cu{sup +} cations. The kinetics of DMC synthesis suggests that the rate-limiting step in the formation of this product was the insertion of CO into CuOCH{sub 3} bonds. The yield of DMC decreased with methanol conversion, likely due to the hydrolysis of DMC to methanol and carbon dioxide.

Zhang, Y.; Briggs, D.N.; Smit,; Bell, A.T.



Molecular adsorption and metal-support interaction for transition-metal clusters in zeolites: NO adsorption on Pd(n) (n=1-6) clusters in mordenite.  


The adsorption of NO molecules on Pd(n) clusters of varying size (n=1-6) located in the main channel of mordenite and the interaction of the metallic clusters with the zeolitic framework were investigated using ab initio density-functional calculations under periodic boundary conditions. The supported clusters are created by binding Pd(n) (2+) cations to the inner cavity of a deprotonated Al-exchanged zeolite with an Al/Si ratio of 1/11, such that a charge-neutral system is created. Compared to the highly symmetric structures of the gas-phase clusters, the clusters bound to the zeolitic framework undergo appreciable geometric distortions lowering their symmetry. The distortions are induced by strong interactions with "activated" framework oxygens located close to the charge-compensating Al/Si substitution sites, but the cluster forms also weaker bonds to "nonactivated" oxygen atoms. The interaction with the framework also affects the electronic and magnetic properties of the clusters. While in the gas phase all clusters (except the isolated Pd atom with a closed d(10) ground state) have a paramagnetic moment of 2mu(B), in the zeolite clusters with two to four atoms have zero magnetic moment, while the Pd(5) cluster has a magnetic moment of 2mu(B) and for the Pd(6) cluster, it is even enhanced to 4 mu(B) (but the magnetic energy differences relative to low-spin configurations are modest). Analysis of the magnetization densities shows that in all clusters with zero total moment (singlet ground state), there are sites with excess spin densities of opposite sign. The influence of the cluster-support interaction on the chemical properties of the clusters has been tested by the adsorption of NO molecules. The results demonstrate the interplay between the molecule-cluster and cluster-framework interactions, which can lead to an increase or decrease in the adsorption energy compared to NO on a gas-phase cluster. While on the gas-phase cluster adsorption in low-coordination sites (vertex or bridge) is preferred, for the cluster in the zeolite adsorption in threefold coordinated hollow or twofold bridge sites is preferred. The magnetic properties of the clusters and of the paramagnetic NO molecule play an important role. For the supported clusters with zero magnetic moment, upon adsorption the spin of the molecule is transferred to the cluster (and induces also a modest polarization of the framework). For magnetic clusters, spin pairing induces a reduced magnetic moment of the NO-Pd(n) complex. The redshift of the NO stretching frequencies is reduced compared to the free clusters by the cluster-support interaction for the smaller clusters, while it remains essentially unchanged for the larger clusters. A detailed electronic analysis of the cluster-support interactions and of the adsorption properties is presented. PMID:19292537

Grybos, Robert; Benco, Lubomir; Bucko, Tomas; Hafner, Jürgen



Periodic DFT calculations of the stability of Al/Si substitutions and extraframework Zn2+ cations in mordenite and reaction pathway for the dissociation of H2 and CH4.  


The local stability of Al atoms replacing Si in the zeolite framework is compared for all inequivalent tetrahedral (T) sites in mordenite. For Al/Si substitutions in two T sites the stable location of the compensating extraframework Zn(2+) cation forming a Lewis acid site is determined. In the most stable Zn-MOR structures Zn(2+) is located in a small ring (5MR, 6MR) containing two Al/Si substitutions. In less stable structures the Al atoms are placed at larger distances from each other and Zn(2+) interacts with only one Al site. The simulated adsorption of H(2) and CH(4) shows that adsorption strength decreases with increasing stability of the Zn(2+) Lewis site. A higher adsorption strength is observed for Zn(2+) deposited in the 5MR than for the 6MR. The reactivity of a series of stable Zn(2+) Lewis sites is tested via the dissociative adsorption of H(2) and CH(4). The heterolytic dissociation of the adsorbed molecule on the extraframework Zn(2+) cation produces a proton and an anion. The anion binds to Zn(2+) and proton goes to the zeolite framework, restoring a Brønsted acid site. Because bonding of the anion to Zn(2+) is almost energetically equivalent for Zn(2+) in any of the extraframework positions the dissociation is governed by stabilizing bonding of the proton to the framework. Those structures which can exothermically accommodate the proton represent reaction pathways. Due to the repulsion between the proton and Zn(2+) the most favorable proton-accepting O sites are not those of the ring where Zn(2+) is deposited, but O sites close to the ring. Large differences are observed for neighboring positions in a- and b-directions and those oriented along the c-vector. Finally, among the stable Zn(2+) Lewis sites not all represent reaction pathways for dehydrogenation. For all of them the dissociation of H(2) is an exothermic process. In structures exhibiting the highest reactivity the Al/Si substitutions are placed at a large distance and the Zn(2+) cation interacts with O-atoms next to Al in the T4 site of the 5MR. This Lewis site is strong enough to break the C-H bond in the CH(4) molecule. PMID:16853635

Benco, L; Bucko, T; Hafner, J; Toulhoat, H



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.



Matrix-assisted laser desorption ionization using lithium-substituted mordenite surface  

NASA Astrophysics Data System (ADS)

An efficient matrix for matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) has been developed. The use of 2,4,6-trihydroxyacetophenone (THAP) on lithium-substituted zeolite has enabled ionization of low-molecular-weight compounds that are not detectable by conventional MALDI-MS. IR measurements and quantum-chemical calculations have also been carried out to understand the adsorption structure of THAP on zeolite. The mechanism of Li+ adduction from zeolite to THAP is also discussed. The important role of the water molecules adsorbed on the zeolite surface for the Li+ adduction from zeolite to THAP has been clarified.

Suzuki, Junya; Sato, Asami; Yamamoto, Ryo; Asano, Takashi; Shimosato, Taku; Shima, Hisashi; Kondo, Junko N.; Yamashita, Ken-ichi; Hashimoto, Kenro; Fujino, Tatsuya



The effect of iron on the biological activities of erionite and mordenite Estelle Facha  

E-print Network

University, 2074 Graves Hall, 333 W. 10th Avenue, Columbus, OH 43210, USA Received 8 August 2002; accepted 4 years, numerous studies have been performed to determine the mechanisms by which asbestos causes disease

Dutta, Prabir K.


Selective oxidation of methane by the bis(mu-oxo)dicopper core stabilized on ZSM-5 and mordenite zeolites.  


This work reports on the capability of the O2-activated Cu-ZSM-5 and Cu-MOR zeolites to selectively convert methane into methanol at a temperature of 398 K. A strong correlation between (i) the activity and (ii) the intensity of the 22 700 cm-1 UV-vis band, assigned to the bis(mu-oxo)dicopper core, is found (i) as a function of the reaction temperature, (ii) as a function of the Cu loading of the zeolite, and (iii) in comparison to other Cu materials. These three lines of evidence firmly support the key role of the bis(mu-oxo)dicopper core in this selective, low-temperature hydroxylation of methane. PMID:15686370

Groothaert, Marijke H; Smeets, Pieter J; Sels, Bert F; Jacobs, Pierre A; Schoonheydt, Robert A



Cyclohexanol conversion as a test reaction for acid properties of solids investigation of faujasites, mordenites and MCM-41  

Microsoft Academic Search

The goal of this study was to find an universal test reaction for the properties of both weak and strong acid sites. Cyclohexanol conversion was found to be such test reaction. It has been found that in the presence of weak Bronsted sites (such as Si-OHB in HBoralites or (AlO)3 Si-OH-Al (SiO)3 in NaHX) only dehydration occured. More acidic sites

J. Datka; B. Gil; O. Vog; J. Rakoczy



Fenton Chemistry of FeIII Zeolitic Minerals Treated with  

E-print Network

mesothelioma, pulmonary fibrosis, and bronchial carcinoma, often years after exposure. Erionite and mordenite. Introduction The development of pulmonary fibrosis, bronchogenic carcinoma, and malignant mesothelioma has been

Dutta, Prabir K.


Predicting adsorption in one-dimensional zeolite pores with the exact theory of one-dimensional hard rods  

NASA Astrophysics Data System (ADS)

The exact statistical mechanical theory of a one-dimensional hard-rod fluid in an arbitrary external field is applied to the adsorption of simple molecules into nearly one-dimensional zeolitic pores, using a zeolite-sorbent interaction potential based on the system of xenon in mordenite. The effect is explored of changing the zeolite-sorbent interaction on adsorption. By optimizing one parameter in the model, the results of this theory compare well with experimental isotherms of xenon in mordenite.

Mitchell, Martha C.; McCormick, Alon V.; Davis, H. Ted


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



Design of a new counting cell for monitoring ⁸⁵Kr in environmental air samples  

Microsoft Academic Search

A sample counting cell for monitoring ultralow-level ⁸⁵Kr in environmental air samples has been designed. The cell consists of approx. =10g of hydrogen mordenite covered with 0.075-mm aluminum foil. The ⁸⁵Kr is adsorbed by the hydrogen mordenite inside the counting cell. The radioactivity of ⁸⁵Kr in the cell is measured by a modified external gas flow proportional counter. A refined

J. G. Lo; D. Y. Chen; J. Z. Wang



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)



Pulmonary Toxicity of Manufactured Nanoparticles from the Perspective of Industrial Hygiene  

E-print Network

Pulmonary Toxicity of Manufactured Nanoparticles from the Perspective of Industrial Hygiene Mean samples were tested. Samples marked "trtd" went through a heat treatment process, 800C for 8 hours under minerals, were tested after ion exchange with iron. Erionite is a potent human carcinogen; mordenite is not

Dutta, Prabir K.


Conversion of methane to methanol on copper-containing small-pore zeolites and zeotypes.  


This communication reports the discovery of several small-pore Cu-zeolites and zeotypes that produce methanol from methane and water vapor, and produce more methanol per copper atom than Cu-ZSM-5 and Cu-mordenite. The new materials include Cu-SSZ-13, Cu-SSZ-16, Cu-SSZ-39, and Cu-SAPO-34. PMID:25679753

Wulfers, M J; Teketel, S; Ipek, B; Lobo, R F



Distribution and chemistry of fracture-lining zeolites 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 are possible sources of information on past transport within the tuffs, and they may act as natural barriers to radionuclide migration along the fractures. Cores from several drill holes were examined to determine the distribution and chemistry of zeolite minerals in fractures. Fracture-lining minerals in the Paintbrush Tuff are highly variable in distribution, both vertically and laterally across the mountain, with mordenite, heulandite, and stellerite widespread in fractures even though the tuff matrix is generally devitrified and not zeolitic. 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. In contrast to the Paintbrush Tuff, fractures in the Calico Hills Formation and the Crater Flat Tuff generally contain abundant clinoptilolite and mordenite only where the matrix is zeolitic, although mordenite does occur as fracture linings in some devitrified intervals of the Crater Flat Tuff as well. The fracture-lining zeolites correlate with the degree of alteration of the zeolitic tuffs, with clinoptilolite plus mordenite in tuffs containing clinoptilolite, and analcime in fractures limited to tuff intervals containing analcime. These data suggest that fracture-lining zeolite formation may have been coincident with the original alteration of the tuffs.

Carlos, B.; Chipera, S.; Bish, D.; Raymond, R.



Characterization and environmental application of a Chilean natural zeolite  

Microsoft Academic Search

The use of natural zeolites for environmental applications is gaining new research interests mainly due to their properties and significant worldwide occurrence. The present work describes the characterization of a natural Chilean zeolite and the results as adsorbent for ammonia from aqueous solutions. The zeolitic-rich tuff sample, mainly composed of clinoptilolite and mordenite, consisted of 13 ?m mean volumetric particle

A. H. Englert; J. Rubio



Association of indigo with zeolites for improved colour stabilization , Martinetto P.a,*  

E-print Network

Association of indigo with zeolites for improved colour stabilization Dejoie C.a , Martinetto P on the association of indigo #12;blue with several zeolitic matrices (LTA zeolite, mordenite, MFI zeolite of the MFI zeolite matrix, we show that matching the pore size with the dimensions of the guest indigo

Paris-Sud XI, Université de


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



Alternative alkali resistant deNO x catalysts  

Microsoft Academic Search

Alternative alkali resistant deNOx catalysts were prepared using three different supports ZrO2, TiO2 and Mordenite zeolite. The majority of the catalysts were prepared by incipient wetness impregnation of a commercial support, with vanadium, copper or iron precursor, one catalyst was prepared by onepot sol–gel method. All catalysts were characterized by BET, XRPD and NH3-TPD. Initial SCR activities of 8 out

Siva Sankar Reddy Putluru; Steffen Buus Kristensen; Johannes Due-Hansen; Anders Riisager; Rasmus Fehrmann


Deactivation of solid acid catalysts during isobutane alkylation with C4 olefins  

Microsoft Academic Search

Coke formation on solid acid catalysts during isobutane alkylation with C4 olefins was studied. Y-zeolite, mordenite and L-zeolite were investigated, as well as sulfated zirconia catalysts. Zeolites were used in protonic form or after ion exchange with lanthanum nitrate. Studies were carried out in liquid phase in a fixed-bed reactor. It was found that Y-zeolite exchanged with lanthanum, being the

C. A. Querini; E. Roa



Addadi, L. and C. R. Safinya, "Biomaterials, Current Opinion in Solid State and Materials Science, Vol. 2, pg. 325 (1997) (editorial overview)  

E-print Network

-ray diffraction and ESR study of Cu-ferrierite", J. of Catalysis, Vol. 172, pg. 274 (1997) Bates, F.S., W Studies in Surface Science and Catalysis, Vol 105, pg. 471, Elsevier Science B. V., H. Chon, S-K. IhmNOx catalyst: Cu-mordenite," J. of Catalysis, Vol. 170, pg. 227 (1997) Attfield, M.P., S.J. Weigel and A

Bigelow, Stephen


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



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.



Catalytic removal of perchloroethylene (PCE) over supported chromium oxide catalysts  

Microsoft Academic Search

The oxidation of perchloroethylene (PCE) was investigated over chromium oxide catalysts supported on SiO2, SiO2–Al2O3, activated carbon, mordenite type zeolites, MgO, TiO2 and Al2O3. Supported chromium oxide catalysts were more active than any other metal oxide catalysts including noble metal examined in the present study. PCE removal activity of chromium oxide catalysts mainly depended on the type of supports and

Sung Dae Yim; Kwang-Hyun Chang; Dong Jun Koh; In-Sik Nam; Young Gul Kim



Polymerization of methylacetylene in hydrogen zeolites  

Microsoft Academic Search

Acid zeolites as media for the alignment and packaging of included conjugated polymers were investigated with the goal of producing materials with enhanced nonlinear optical properties. Methylacetylene gas was absorbed onto acid forms of Mordenite, Omega, L, Y, Beta ZSM-5, and SAPO-5 at room temperature. The resulting yellow to red-brown powders were characterized by mass uptake, powder XRD, TPD-TGA, ¹³C

Sherman D. Cox; Galen D. Stucky



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



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, Improved, Solid-Acid Catalyzed Process for Generating Linear Alkylbenzenes (LABs)  

Microsoft Academic Search

Linear alkylbenzenes (LABs) comprising >80% 2-phenyl isomer content, have been prepared in high yields from detergent-range linear olefins via regioselective benzene alkylation. HF-treated mordenites, acidic Beta-zeolites, and fluorided montmorillonite clays, each provide enhanced shape-selective alkylation performance when employed as heterogeneous catalysts in the subject syntheses. Both individual C8–C12 a-olefins, as well as mixed, commercial plant-derived, C10 through C14 paraffin dehydrogenate

John F. Knifton; Prakasa Rao Anantaneni; P. Eugene Dai; Melvin E. Stockton



Reactive distillation for sustainable, high 2-phenyl LAB production  

Microsoft Academic Search

Linear alkylbenzenes (LABs) comprising >80% 2-phenyl isomer content, have been prepared in sustainable high yields from detergent-range linear olefins via regioselective benzene alkylation using reactive distillation technology. Hydrofluoric acid (HF)-treated mordenites provide enhanced, shape-selective, alkylation performance when employed as heterogeneous catalysts in the subject syntheses. Both individual C10–C12 ?-olefins, as well as mixed, commercial plant-derived, C10–C14 paraffin dehydrogenate feedstocks containing

John F. Knifton; Prakasa Rao Anantaneni; P. Eugene Dai; Melvin E. Stockton



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



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.



Summary of FY 2010 Iodine Capture Studies at the INL  

SciTech Connect

Three breakthrough runs using silver mordenite sorbents were conducted and a dynamic sorption capacity estimated based on MeI analysis from a 2" bed. However, it is now believed the data for the first 2 runs is incomplete because the contributions from elemental iodine were not included. Although the only source of iodine was MeI, elemental iodine was generated within the sorbent bed, presumably from a recombination reaction likely catalyzed by silver mordenite. On-line effluent analysis with a GC was only capable of analyzing MeI, not I2. Scrub samples drawn during Run #3, which are specific for I2, show significant levels of I2 being emitted from a partially spent Ag-mordenite bed. By combining MeI and I2 analyses, a well defined total iodine breakthrough curve can be generated for Run #3. At the conclusion of Run #3 (IONEX Ag-900 was the sorbent) the effluent level from Bed 2 was approaching 70% of the feed concentration. The leading bed (Bed 1) had an estimated average loading of 66 mg I/g sorbent, Bed 2's was 52 mg I/g. The corresponding silver utilizations (assuming formation of AgI) were about 59% and 46%, respectively. The spent sorbents are being sent to Sandia National Laboratories for confirmatory analysis of iodine and silver utilization as well as source material for waste form development.

Daryl R. Haefner; Tony L. Watson; Michael G. Jones



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 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.



Molecular sieve effect in the hydration of olefins on zeolites  

SciTech Connect

Olefin reactivity for synthetic mordenites varies in the series ethylene, propylene, isobutylene. S study of the hydration of these alkenes on high-silicon zeolite ZHM displayed an unusual reactivity order: ethylen = propylene is greater than isobutylene oligomers zation of the catalyst and the formation of isobutylene oligomers increased at higher temperature; the yield of tert-butyl alcohol did not increase. These results may be explained by a molecular sieve effect for olefin hydration and not by sample deactivation and side reactions since even a partially carbonized catalyst did not display reduced activity in olefin hydration.

Tolkacheva, L.N.; Dmitriev, R.V.; Minachev, K.M.; Novikova, L.A.; Taits, S.Z.



Effective catalysts for decomposition of aqueous ozone  

Microsoft Academic Search

Activities of a series of oxide supports and dozens of supported metal catalysts toward the decomposition of aqueous ozone have been investigated. Under reaction conditions, active carbon (AC) showed comparatively high activity, while zeolite (HY and mordenite), Al2O3, SiO2, SiO2·Al2O3 and TiO2 showed no or negligible activity. Noble metals showed high activity. Among four kinds (Al2O3, SiO2, SiO2·Al2O3 and TiO2)

Jianjun Lin; Akimasa Kawai; Tsuyoshi Nakajima



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.



Influence of solid–acid catalysts on steam reforming and hydrolysis of dimethyl ether for hydrogen production  

Microsoft Academic Search

Influences of solid–acid catalyst on dimethyl ether steam reforming (DME SR) and DME hydrolysis for hydrogen production were investigated. Series of zeolite (JRC-ZHM20(5), JRC-ZHM90(1) as H-mordenite type and JRC-Z5-90H(1) as ZSM-5 type) and of alumina (ALO8, TA1301, TA3301, DK503, NKHD24, NKHO24 and NK324) were used as acidic catalysts for DME hydrolysis. The composite catalysts of the acidic catalyst and CuFe2O4

Kajornsak Faungnawakij; Yohei Tanaka; Naohiro Shimoda; Tetsuya Fukunaga; Shunichiro Kawashima; Ryuji Kikuchi; Koichi Eguchi



Polymerization of methylacetylene in hydrogen zeolites  

SciTech Connect

Acid zeolites as media for the alignment and packaging of included conjugated polymers were investigated with the goal of producing materials with enhanced nonlinear optical properties. Methylacetylene gas was absorbed onto acid forms of Mordenite, Omega, L, Y, Beta ZSM-5, and SAPO-5 at room temperature. The resulting yellow to red-brown powders were characterized by mass uptake, powder XRD, TPD-TGA, {sup 13}C CP/MAS NMR, {sup 1}H MAS NMR, UV-vis, ESR, FTIR, heptane absorption, ammonia bleaching, and chemical extraction techniques. The data show that large, conjugated, oligomeric species are formed within the internal void spaces of the zeolites.

Cox, S.D.; Stucky, G.D. (Univ. of California, Santa Barbara (USA))



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.



Peculiarities observed in H-D exchange between perdeuterioisobutane and H-zeolites  

SciTech Connect

H-D exchange between perdeuterioisobutane and NaH-Y-zeolites and H-mordenite (H-M) was studied using the pulse technique. Nine of the ten D atoms in the isobutane molecule were exchanged for H on the most acidic Y-zeolites at the lowest temperature (200{degrees}C) where H-D exchange was observed, while other transformations of isobutane were not. The reaction is thought to be initiated by protonation of the tertiary C-D bond on the Bronsted acid sites of the catalyst and the exchange to proceed via the t-butyl carbenium ion intermediate. Release of the ion from the surface occurs via hydride transfer conserving the identity of the tertary position. At higher temperatures and over the more acidic H-mordenite at even lower temperature (125{degrees}C) an extensive intermolecular H-D exchange occurs between perdeuterioisobutane and its exchanged products. A more detailed understanding of this reaction chemistry is developed herein. 16 refs., 9 figs., 4 tabs.

Engelhardt, J.; Hall, W.K. [Univ. of Pittsburgh, PA (United States)] [Univ. of Pittsburgh, PA (United States)



The selective adsorption of tellurium in the aluminosilicate regions of AFI- and MOR-type microporous crystals.  


Attempts have been made to load tellurium (Te) atoms into the one-dimensional nano-channels of microporous crystals of aluminophosphate AlPO4-5 and of aluminosilicate mordenites of the Na(+) form (Na-MOR) and the H(+)-form (H-MOR) at 673 K. The density of the atoms adsorbed was in the sequence 0 ? AlPO4-5 ? H-MOR < Na-MOR. AlPO4-5 provides a shallow potential of periodical charge fluctuation for Te atoms, from the alternate ordering of Al and P atoms through O atoms. Mordenite offers a sufficiently strong potential for Te adsorption, but the magnitude varies with the type of cation. Dipoles between framework AlO2(-) anion sites and their Na(+) counter-ions in Na-MOR provide a stronger potential than the Brønsted acid points in H-MOR. The adsorption of Te atoms in the silico-aluminophosphate SAPO-5 was between that of AlPO4-5 and H-MOR, leading us to suspect that Te atoms are selectively adsorbed in the aluminosilicate regions accompanying the Brønsted acid points distributed in the major aluminophosphate network. The aluminosilicate regions in SAPO-5 are below 500 nm in size and are distributed throughout a single crystal. PMID:25117797

Kodaira, Tetsuya; Ikeda, Takuji



Calibration analysis of zeolites by laser induced breakdown spectroscopy  

NASA Astrophysics Data System (ADS)

Laser induced breakdown spectroscopy was used for calibration analysis of different types of microporous crystalline aluminosilicates with exactly ordered structure — zeolites. The LIBS plasma was generated using a Q-switched Nd:YAG laser operating at the wavelength of 532 nm and providing laser pulses of 4 ns duration. Plasma emission was analysed by echelle type emission spectrometer, providing wide spectral range 200-950 nm. The spectrometer was equipped with intensified CCD camera providing rapid spectral acquisition (gating time from 5 ns). The optimum experimental conditions (time delay, gate width and laser pulse energy) have been determined for reliable use of LIBS for quantitative analysis. Samples of different molar ratios of Si/Al were used to create the calibration curves. Calibration curves for different types of zeolites (mordenite, type Y and ZSM-5) were constructed. Molar ratios of Si/Al for samples used for calibration were determined by classical wet chemical analysis and were in the range 5.3-51.8 for mordenite, 2.3-12.8 for type Y and 14-600 for ZSM-5. Zeolites with these molar ratios of Si/Al are usually used as catalysts in alkylation reactions. Laser induced breakdown spectroscopy is a suitable method for analysis of molar ratio Si/Al in zeolites, because it is simple, fast, and does not require sample preparation compared with classical wet chemical analysis which are time consuming, require difficult sample preparation and manipulation with strong acids and bases.

Hor?á?ková, M.; Grolmusová, Z.; Hor?á?ek, M.; Rakovský, J.; Hudec, P.; Veis, P.



NO decomposition in non-reducing atmospheres. Technical progress report, December 1995--February 1996  

SciTech Connect

The preparation of Co(II) ion exchanged zeolites was described in the previous quarterly progress report, and NO adsorption/desorption studies with these zeolites have now been carried out, especially with ZSM-5 and erionite zeolites. Diffuse reflectance spectroscopy was utilized to monitor the spectral changes that occurred during adsorption of NO on the Co(II) cations, which was observed to occur after dehydration treatments at 350{degrees}C and 525{degrees}C. Absorption bands in the charge transfer spectral region of NO-Co intrazeolitic complexes depended mainly on Co siting in the zeolites. Catalytic testing of NO decomposition and NO reduction by methane was carried out. It was observed that Co-mordenite and Co-A zeolite exhibited low, but stable, activity in NO decomposition. For NO reduction by methane in the presence of excess oxygen, Co-mordenite and Co-ferrierite exhibited the highest %NO converted to products and selectivity toward N{sub 2} formation, but Co-A zeolite and Co-erionite yielded the highest selectivities to NO{sub 2} formation. Co-ZSM-5 zeolite exhibited an intermediate behavior.

Klier, K.; Herman, R.G.; Dedecek, J.



Clay mineral assemblages and analcime formation in a Palaeogene fluvial lacustrine sequence (Maíz Gordo Formation Palaeogen) from northwestern Argentina  

NASA Astrophysics Data System (ADS)

The Palaeogene Maíz Gordo Formation is one of the main lacustrine events recorded in northwestern Argentina. It consists of sandstone, mudstone, and limestone beds 200 m thick, deposited in a brackish-alkaline lake and braided alluvial systems. The Maíz Gordo Lake evolved mainly as a closed system, with brief periods as an open one. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to study samples from seven sites, corresponding respectively to proximal, intermediate, and transitional positions of the fluvial environment and marginal and inner-lake environment, focusing on the clay mineralogy and analcime formation. The basinward zonation of diagenetic minerals identified in the Maíz Gordo Lake was: mordenite ? analcime ? K-feldspar. Although not a typical zonation of saline-alkaline lakes, it does indicate an increase in salinity and alkalinity towards the centre. In proximal fluvial settings, smectite predominates at the base of the sequence, with scarce kaolinite. Towards the top, a striking increase in kaolinite content suggests a change from a relatively arid climate with alternating humid and dry seasons, towards a warm and humid climate. Kaolinite content clearly decreases in a basinward direction. Such a variation is attributable to changes in hydro-geochemistry, denoting the progressive influence of the brackish and alkaline lake water on interstitial pores. SEM images of intermediate fluvial samples reveal authigenesis of illite at the expense of kaolinite booklets. In littoral and inner-lake settings the clay fraction is composed of muscovite, sometimes with subordinate smectite. Analcime occurs in variable amounts in all sedimentary facies, in rock pores or filling veins. It forms subhedral square to hexagonal, or anhedral rounded crystals, denoting that they coarsened at low to moderate degrees of supersaturation. Although the mordenite identified in a fluvial level would have been the precursor of analcime in the Maíz Gordo Basin, no textural evidence of analcime formation through replacement of mordenite or other precursor zeolite was found. Hence it is more probable that analcime formation took place by direct authigenic precipitation or through the reaction between interstitial brines and clay minerals or plagioclase.

Do Campo, M.; del Papa, C.; Jiménez-Millán, J.; Nieto, F.



Radioactive iodine separations and waste forms development.  

SciTech Connect

Reprocessing nuclear fuel releases gaseous radio-iodine containing compounds which must be captured and stored for prolonged periods. Ag-loaded mordenites are the leading candidate for scavenging both organic and inorganic radioiodine containing compounds directly from reprocessing off gases. Alternately, the principal off-gas contaminant, I2, and I-containing acids HI, HIO3, etc. may be scavenged using caustic soda solutions, which are then treated with bismuth to put the iodine into an insoluble form. Our program is focused on using state-of-the-art materials science technologies to develop materials with high loadings of iodine, plus high long-term mechanical and thermal stability. In particular, we present results from research into two materials areas: (1) zeolite-based separations and glass encapsulation, and (2) in-situ precipitation of Bi-I-O waste forms. Ag-loaded mordenite is either commercially available or can be prepared via a simple Ag+ ion exchange process. Research using an Ag+-loaded Mordenite zeolite (MOR, LZM-5 supplied by UOP Corp.) has revealed that I2 is scavenged in one of three forms, as micron-sized AgI particles, as molecular (AgI)x clusters in the zeolite pores and as elemental I2 vapor. It was found that only a portion of the sorbed iodine is retained after heating at 95o C for three months. Furthermore, we show that even when the Ag-MOR is saturated with I2 vapor only roughly half of the silver reacted to form stable AgI compounds. However, the Iodine can be further retained if the AgI-MOR is then encapsulated into a low temperature glass binder. Follow-on studies are now focused on the sorption and waste form development of Iodine from more complex streams including organo-iodine compounds (CH3I). Bismuth-Iodate layered phases have been prepared from caustic waste stream simulant solutions. They serve as a low cost alternative to ceramics waste forms. Novel compounds have been synthesized and solubility studies have been completed using competing groundwater anions (HCO3-, Cl- and SO42-). Distinct variations in solubility were found that related to the structures of the materials.

Krumhansl, James Lee; Nenoff, Tina Maria; Garino, Terry J.; Rademacher, David



Removal of free fatty acid in waste frying oil by esterification with methanol on zeolite catalysts.  


The removal of free fatty acid (FFA) in waste frying oil by esterification with methanol was conducted using various zeolite catalysts. The ZSM-5 (MFI), mordenite (MOR), faujasite (FAU), beta (BEA) zeolites, and silicalite were employed with different Si/Al molar ratio in the reaction. The effects of acidic properties and pore structure of the zeolite catalysts were discussed relating to the conversion of the FFA. The MFI zeolite induced an improvement of the removal efficiency of FFA by cracking to the FFA in its pore structure due to its narrow pore mouth. The catalytic activity for FFA removal was lowered with decreasing of acid strength of the zeolites. The strong acid sites of zeolites induced the high conversion of FFA comparatively. The acid strength and pore structure of acidic zeolites affected the catalytic activity in FFA removal. PMID:18387298

Chung, Kyong-Hwan; Chang, Duck-Rye; Park, Byung-Geon



Adsorption properties of Cs{sup +} for composite adsorbents and their irradiation stabilities  

SciTech Connect

Novel composite adsorbents using impregnation-precipitation methods have been developed; these fine crystals are loaded in the macro-pores of porous silica gels and zeolites. The 2 following composite adsorbents: KCoFC-NM (NM: natural mordenite, 0.4-1.0 mm), KCoFC-SG (SG: porous silica gel, NH and Q-10)) were prepared by impregnation-precipitation methods. This article presents the results of tests about their characterization, their selective adsorption ability of Cs{sup 137} and their irradiation stability. It is shown that the KCoFC-SG and KCoFC-NM composites are thus efficient for the selective separation of Cs{sup 137} in low-level radioactive waste (LLW) containing highly concentrated sodium nitrate.

Susa, Shunsuke; Mimura, Hitoshi [Tohoku University, Aramaki-Aza-Aoba 6-6, Aoba-ku, Sendai, Miyagi 980-8579 (Japan); Ito, Yoshiyuki; Saito, Yasuo [Japan Atomic Energy Agency, Muramatsu 4-33, Tokai-mura, Naka-gun, Ibaraki 319-1194 (Japan)



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.



Supercritical fluid removal of hydrocarbons adsorbed on wide pore zeolite catalysts  

SciTech Connect

The effect of zeolite pore structure on coke removal by supercritical fluid regeneration (SFR) was studied on a series of wide pore zeolite catalysts, which included acidic Y, beta, L, and mordenite zeolites. Catalyst samples were deactivated under liquid phase isobutane/butene alkylation reaction conditions and treated under flowing supercritical isobutane for 60 min. The chemical nature of the species remaining on the catalyst surface before and after SFR was analyzed by temperature-programmed oxidation (TPO), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and ultraviolet-visible (UV-Vis) spectroscopy. Zeolite pore structure played an important role not only in hydrocarbon deposition during alkylation but also in hydrocarbon transformation and removal during SFR. During SFR, the formation of unsaturated cyclic or polycyclic compounds, which likely affects catalyst long-term activity after cyclic alkylation/SFR treatments, was hindered on beta zeolites and favored on catalysts containing periodic expansions or cages, such as Y and L zeolites.

Lucia M. Petkovic; Daniel M. Ginosar; Kyle C. Burch



Manufacture of naphthenic type lubricating oils  

SciTech Connect

A process for making naphthenic type lubricating oils from a low viscosity waxy crude which comprises distilling said low viscosity waxy crude to 500 to 650/sup 0/F. At atmospheric pressure to separate distillable fractions therefrom, subjecting the residue to a vacuum distillation at about 25 to about 125 mm Hg absolute pressure to obtain one or more gas oil fractions, optionally hydrotreating said gas oil fractions in the presence of a Ni/Mo catalyst at 550 to 650/sup 0/F, 0.25 to 1.0 lhsv, and 700-1500 psig, and catalytically dewaxing said distillates in the presence of a H+ form mordenite catalyst containing a group VI or group VIII metal at 550 to 750/sup 0/F, 500 to 1500 psig and 0.25 to 5.0 lhsv, to obtain said naphthenic type oils having pour points of from about -60 to +20/sup 0/F.

Reynolds, R.W.



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



Experimental and simulated propene isotherms on porous solids  

NASA Astrophysics Data System (ADS)

The lack of treatment capacity of hydrocarbons by three-way catalysts during the "cold start" period creates an important environmental problem. During this period, the temperature of the three-way catalyst is too low for effective operation and cannot convert the hydrocarbons in the exhaust. 50-80% of the total hydrocarbon emissions are produced in this phase that accomplishes the first 60-120 s of the engine operation. In this study, the technology chosen to treat these emissions is the use of HC-traps, and molecular simulations are tested as a tool to reproduce the experimental adsorption behaviour of porous solids. Therefore, experimental and simulated adsorption isotherms of propene (model hydrocarbon) have been obtained for four different crystalline materials with distinctive framework structures (3D and 1D) and a variety of Si/Al ratios and cations (three zeolites: ZSM-5, BETA and Mordenite; and a silicoaluminophosphate molecular sieve: SAPO-5).

Navarro, M. V.; Puértolas, B.; García, T.; Murillo, R.; Mastral, A. M.; Varela-Gandía, F. J.; Lozano-Castelló, D.; Cazorla-Amorós, D.; Bueno-López, A.



Multiple zeolite structures from one ionic liquid template.  


This study reports the use of 1-butyl-3-methyl imidazolium methanesulfonate ionic liquid as a template in the synthesis of zeolites. It is found that the silicon source determines the formation of beta (BEA), mordenite framework inverted (MFI), or analcime (ANA) zeolites. Depending on this source, different preorganized complexes are obtained that drive the formation of the different zeolite structures. In the presence of ethanol, the ionic liquid form preorganized complexes that drive the formation of MFI. In its absence, BEA is obtained. Whereas, the large amount of sodium present when using sodium metasilicate leads to ANA formation. A molecular simulation study of the relative stability of the template-framework system and location of the template provides further insight into the mechanism of synthesis. PMID:23255393

Martínez Blanes, José María; Szyja, Bart?omiej M; Romero-Sarria, Francisca; Centeno, Miguel Ángel; Hensen, Emiel J M; Odriozola, José Antonio; Ivanova, Svetlana



Water mobility in Calico Hills tuff measured by quasielastic neutron scattering  

NASA Astrophysics Data System (ADS)

Quasielastic neutron scattering (QNS) was used to measure the mobility of water in tuff at low saturation. The tuff sample is from a surface outcrop of the Calico Hills formation, which lies below the proposed location for a high-level nuclear waste repository, at Yucca Mountain, NV. The sample is a devitrified tuff composed mainly of zeolites and having clinoptilolite (approximately 70%), mordenite, and opal-CT as major constituents. The sample is an air dry, intact core sample. QNS measurements were made in the range 200 K to 423 K. Rotational motion of adsorbed water is easily observable and translational motion is observable at higher temperatures. The tuff data are analyzed to determine the rotational diffusion coefficient and the translational diffusion coefficient. The results yield a translational diffusion coefficient in the tuff that is significantly lower than that of bulk water but higher than for water in montmorillonite or vermiculite clays.

Maddox, S. A.; Gomez, P.; McCall, K. R.; Eckert, J.



Effect of aluminum on the local structure of silicon in zeolites as studied by Si K edge X-ray absorption near-edge fine structure: spectra simulation with a non-muffin tin atomic background.  


Experimental Si K edge X-ray absorption near-edge fine structure (XANES) of zeolite faujasite, mordenite, and beta are interpreted by means of the FEFF8 code, replacing the theoretical atomic background mu(0) by a background that was extracted from an experimental spectrum. To some extent, this diminished the effect of the inaccuracy introduced by the MT potential and accounted for the intrinsic loss of photoelectrons. The agreement of the theoretical and experimental spectra at energies above the white lines enabled us to identify structural distortion around silicon, which occurs with increasing aluminum content. The Si K edge XANES spectra are very sensitive to slight distortions in the silicon coordination. Placing an aluminum atom on a nearest neighboring T site causes a distortion in the silicon tetrahedron, shortening one of the silicon-oxygen bonds relative to the other three. PMID:19281202

Bugaev, Lusegen A; Bokhoven, Jeroen A van; Khrapko, Valerii V



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.



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.



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



Analysis of the biological and chemical reactivity of zeolite-based aluminosilicate fibers and particulates.  

PubMed Central

Environmental and/or occupational exposure to minerals, metals, and fibers can cause lung diseases that may develop years after exposure to the agents. The presence of toxic fibers such as asbestos in the environment plus the continuing development of new mineral or vitreous fibers requires a better understanding of the specific physical and chemical features of fibers/particles responsible for bioactivity. Toward that goal, we have tested aluminosilicate zeolites to establish biological and chemical structure-function correlations. Zeolites have known crystal structure, are subject to experimental manipulation, and can be synthesized and controlled to produce particles of selected size and shape. Naturally occurring zeolites include forms whose biological activity is reported to range from highly pathogenic (erionite) to essentially benign (mordenite). Thus, we used naturally occurring erionite and mordenite as well as an extensively studied synthetic zeolite based on faujasite (zeolite Y). Bioactivity was evaluated using lung macrophages of rat origin (cell line NR8383). Our objective was to quantitatively determine the biological response upon interaction of the test particulates/fibers with lung macrophages and to evaluate the efficacy of surface iron on the zeolites to promote the Fenton reaction. The biological assessment included measurement of the reactive oxygen species by flow cytometry and chemiluminescence techniques upon phagocytosis of the minerals. The chemical assessment included measuring the hydroxyl radicals generated from hydrogen peroxide by iron bound to the zeolite particles and fibers (Fenton reaction). Chromatography as well as absorption spectroscopy were used to quantitate the hydroxyl radicals. We found that upon exposure to the same mass of a specific type of particulate, the oxidative burst increased with decreasing particle size, but remained relatively independent of zeolite composition. On the other hand, the Fenton reaction depended on the type of zeolite, suggesting that the surface structure of the zeolite plays an important role. PMID:12417479

Fach, Estelle; Waldman, W James; Williams, Marshall; Long, John; Meister, Richard K; Dutta, Prabir K



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.



Development of Stable Solidification Method for Insoluble Ferrocyanides-13170  

SciTech Connect

The development of stable solidification method of insoluble ferrocyanides sludge is an important subject for the safety decontamination in Fukushima NPP-1. By using the excellent immobilizing properties of zeolites such as gas trapping ability and self-sintering properties, the stable solidification of insoluble ferrocyanides was accomplished. The immobilization ratio of Cs for K{sub 2}[CoFe(CN){sub 6}].nH{sub 2}O saturated with Cs{sup +} ions (Cs{sub 2}[CoFe(CN){sub 6}].nH{sub 2}O) was estimated to be less than 0.1% above 1,000 deg. C; the adsorbed Cs{sup +} ions are completely volatilized. In contrast, the novel stable solid form was produced by the press-sintering of the mixture of Cs{sub 2}[CoFe(CN){sub 6}].nH{sub 2}O and zeolites at higher temperature of 1,000 deg. C and 1,100 deg. C; Cs volatilization and cyanide release were completely depressed. The immobilization ratio of Cs, under the mixing conditions of Cs{sub 2}[CoFe(CN){sub 6}].nH{sub 2}O:CP= 1:1 and calcining temperature: 1,000 deg. C, was estimated to be nearly 100%. As for the kinds of zeolites, natural mordenite (NM), clinoptilolite (CP) and Chabazite tended to have higher immobilization ratio compared to zeolite A. This may be due to the difference in the phase transformation between natural zeolites and synthetic zeolite A. In the case of the composites (K{sub 2-X}Ni{sub X/2}[NiFe(CN){sub 6}].nH{sub 2}O loaded natural mordenite), relatively high immobilization ratio of Cs was also obtained. This method using zeolite matrices can be applied to the stable solidification of the solid wastes of insoluble ferrocyanides sludge. (authors)

Ikarashi, Yuki; Masud, Rana Syed; Mimura, Hitoshi [Dept. of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University, Aramaki-Aza-Aoba6-6-01-2, Sendai, 980-8579 (Japan)] [Dept. of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University, Aramaki-Aza-Aoba6-6-01-2, Sendai, 980-8579 (Japan); Ishizaki, Eiji; Matsukura, Minoru [UNION SHOWA K.K. 17-20, Mita 2-chome, Minato-ku, Tokyo 108-0073 (Japan)] [UNION SHOWA K.K. 17-20, Mita 2-chome, Minato-ku, Tokyo 108-0073 (Japan)



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



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.



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.



Shape-selective hydrogenation of naphthalene over zeolite-supported Pt and Pd catalysts  

SciTech Connect

Per-hydrogenation of naphthalene produces two decalin isomers: cis and trans. High selectivity for one isomer can be achieved using the appropriate combination of noble metal and zeolite (Y or mordenite) support, and the appropriate choice or reaction conditions. For example, over 80% selectivity for cis-decalin has been obtained at 200{degrees}C, with 100% naphthalene conversion to decalins. cis-Decalin has potential industrial applications in polymers and specialty chemicals. An example is in the production of sebacic acid, which can be used for manufacturing Nylon 6,10 and softeners. On the other hand, catalysts that promote the thermodynamically favored cis- to trans-decalin isomerization can give nearly 95% selectivity to trans-decalin. This technology can be used in fuel processing, to reduce the content of aromatics in the fuel, and to increase fuel thermal stability-especially for high-performance jet aircraft fuels. It is significant that Pt catalyzes both hydrogenation and isomerization on some zeolite supports, but on another type of support, only hydrogenation is catalyzed. Regardless of the type of zeolite used. Pd catalyzes both reactions.

Schmitz, A.D.; Bowers, G.; Song, C. [Pennsylvania State Univ., University Park, PA (United States)



Evaluation of dust-related health hazards associated with air coring at G-Tunnel, Nevada Test Site  

SciTech Connect

The Yucca Mountain Project was established to evaluate the potential for storing high-level radioactive wastes in geologic formations. Hydrologists recommended that drilling or coring in support of characterization tests be performed dry. Dry drilling, or air coring, presents a concern about health protection for the drilling personnel. The rock generally has a high silica content, and natural zeolites are abundant. Some zeolites are fibrous, leading to concerns that inhalation may result in asbestos-like lung diseases. An industrial hygiene study (IH) was conducted as part of an air coring technical feasibility test. The IH study found the potential for exposures to airborne silica and nuisance dusts to be within regulatory requirements and determined the commercial dust control equipment monitored to be effective when used in conjunction with a good area ventilation system and sound IH practices. Fibrous zeolites were not detected. Recommendations for the Yucca Mountain studies are (1) dust collection and control equipment equivalent or superior to that monitored must be used for any dry drilling activity and must be used with good general dilution ventilation and local exhaust ventilation provided on major emission sources; (2) good industrial hygiene work practices must be implemented, including monitoring any area where zeolitic fibers are suspect; and (3) a study should be conducted to determine the biological effects of the fibrous zeolite, mordenite. 25 refs., 17 figs., 14 tabs.

Skaggs, B.J.; Ortiz, L.W.; Burton, D.J.; Isom, B.L.; Vigil, E.A.



Xylose isomerization with zeolites in a two-step alcohol-water process.  


Isomerization of xylose to xylulose was efficiently catalyzed by large-pore zeolites in a two-step methanol-water process that enhanced the product yield significantly. The reaction pathway involves xylose isomerization to xylulose, which, in part, subsequently reacts with methanol to form methyl xyluloside (step?1) followed by hydrolysis after water addition to form additional xylulose (step?2). NMR spectroscopy studies performed with (13) C-labeled xylose confirmed the proposed reaction pathway. The most active catalyst examined was zeolite?Y, which proved more active than zeolite beta, ZSM-5, and mordenite. The yield of xylulose obtained over H-USY (Si/Al=6) after 1?h of reaction at 100?°C was 39?%. After water hydrolysis in the second reaction step, the yield increased to 47?%. Results obtained from pyridine adsorption studies confirm that H-USY (6) is a catalyst that combines Brønsted and Lewis acid sites, and isomerizes xylose in alcohol media to form xylulose at low temperature. The applied zeolites are commercially available; do not contain any auxiliary tetravalent metals, for example, tin, titanium, or zirconium; isomerize xylose efficiently; are easy to regenerate; and are prone to recycling. PMID:25703506

Paniagua, Marta; Saravanamurugan, Shunmugavel; Melian-Rodriguez, Mayra; Melero, Juan A; Riisager, Anders



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.



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



Determination of Si/Al molar ratios in microporous zeolites using calibration-free laser induced breakdown spectroscopy  

NASA Astrophysics Data System (ADS)

In this paper, the potential application of a calibration-free laser-induced breakdown spectroscopy (CF-LIBS) method for the determination of the silicon-to-aluminum molar ratio in microporous zeolites (with both intermediate and high silica contents) is discussed. Three different zeolite types, i.e., mordenite and zeolites type Y and ZSM-5, were analyzed in this study and were shown to have Si/Al molar ratios in the range between 2.3 and 51.8. Many ionic and neutral atomic spectral lines of silicon and aluminum were detected in the measured LIBS spectra in the spectral range 200-1000 nm, but not all of the observed spectral lines are convenient for a CF-LIBS analysis. To increase the accuracy of the results, only lines with no or low self-absorption probability were selected. A systematic method is proposed to select spectral lines based on three main parameters: the transition probability (Einstein coefficient), the lower level energy of the observed transition and the number density ratio between singly ionized and neutral species (as calculated for Si and Al for the measured electron density and electron temperature). The calculated Si/Al molar ratios were close to that determined by wet chemical analysis with an average relative standard deviation of approximately 5% (maximum less than 15%). Our results point to the possibility of using CF-LIBS for analysis of these types of materials and for determination of Si/Al molar ratios.

Hor?á?ková, M.; Hor?á?ek, M.; Rakovský, J.; Hudec, P.; Veis, P.



Binding and catalytic reduction of NO by transition metal aluminosilicates  

SciTech Connect

The objective of this research is to provide the scientific understanding of processes that actively and selectively reduce NO in dilute exhaust streams, as well as in concentrated streams, to N{sub 2}. Experimental studies of NO chemistry in transition metal-containing aluminosilicate catalysts are being carried out with the aim of determining the chemical rules for NO reduction on non-precious metals. The catalyst supports chosen for this investigation are A and Y zeolites, mordenite, and monoliths based on cordierite. The supported transition metal cations that were examined are principally the first row redox metals, e.g. Cr(2), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Cu(I). The reactions of interest are the reductions of NO by H{sub 2}, CO, and CH{sub 4}, as well as the disproportionation of NO. Rare earth cations that possess redox properties were placed in the more shielded sites, e.g. Site I in Y zeolite, prior to or simultaneously with the exchange procedure with the transition metal cations. Theoretical calculations of the electronic structure of the transition metal cations in zeolitic sites were carried out by ab initio methods. The aim of this part of the research is to find the best match between the metal-based antibonding orbitals and the antibonding orbitals of the NO molecule such that the N-O bond is weakened and is readily broken. 9 refs., 4 figs., 3 tabs.

Klier, K.; Herman, R.G.; Hou, Shaolie.



Hydrothermal fabrication of ZSM-5 zeolites: biocompatibility, drug delivery property, and bactericidal property.  


The bone graft-associated infection is widely considered in orthopedic surgery, which may lead to implant failure, extensive bone debridement, and increased patient morbidity. In this study, we fabricated ZSM-5 zeolites for drug delivery systems by hydrothermal method. The structure, morphology, biocompatibility, drug delivery property, and bactericidal property of the ZSM-5 zeolites were investigated. The ZSM-5 zeolites have mordenite framework inverted-type structure and exhibit the disk-like shape with the diameter of ?350 nm and thickness of ?165 nm. The biocompatibility tests indicate that human bone marrow stromal cells spread out well on the surfaces of the ZSM-5 zeolites and proliferate significantly with increasing culture time. As compared with the conventional hydroxyapatite particles, the ZSM-5 zeolites possess greater drug loading efficiency and drug sustained release property because of the ordered micropores, large Brunauer-Emmett-Teller (BET) surface areas, and functional groups. For the gentamicin-loaded ZSM-5 zeolites, the sustained release of gentamicin minimizes significantly bacterial adhesion and prevents biofilm formation against Staphylococcus epidermidis. The excellent biocompatibility, drug delivery property, and bactericidal property of the ZSM-5 zeolites suggest that they have great application potentials for treating implant-associated infections. PMID:24123971

Guo, Ya-Ping; Long, Teng; Song, Zhen-Fu; Zhu, Zhen-An



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



Reaction-path calculations of groundwater chemistry and mineral formation at Rainier Mesa, Nevada  

SciTech Connect

Reaction-patch calculations of groundwater chemistry and mineral formation at Rainier Mesa, Nevada, have been done using a model of volcanic-glass dissolution by water that is initially saturated with CO{sub 2}. In the reaction-path calculation, rate processes control the availability of species through dissolution of volcanic glass, and equilibrium processes distribute the species between the aqueous phase and mineral phases in equilibrium at each step in the reaction path. The EQ3/6 chemical-equilibrium programs were used for the calculation. Formation constants were estimated for three zeolites (clinoptilolite, mordenite, and heulandite), so they could be considered as possible mineral precipitates. The first stage of mineral evolution, from volcanic glass to a cristobalite, smectite clay, and zeolite mixture, was modeled quite well. Predicted aqueous-phase compositions and precipitates agree with observations at Rainier Mesa and other Nevada Test Site areas. Further mineral evolution, to quartz, clay, analcime, and albite mixtures, was also modeled. Decreasing aqueous silica activity from the first stage, where cristobalite precipitates, to later stages, where quartz is present, was the controlling variable in the mineral evolution. 30 references, 20 figures, 4 tables.

Kerrisk, J F



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.



Adsorption tests of water vapor on synthetic zeolites for an atmospheric detritiation dryer  

NASA Astrophysics Data System (ADS)

Tritiated hydrogen and hydrocarbon are usually oxidized to a tritiated water vapor to make the tritium adsorbable and easy to treat. The adsorption system as a subsequent process plays an important role in a tritium recovery and its performance affects the overall detritiation efficiency significantly. In order to quantify an adsorbent's utilization and its dynamic capacity against an inlet humidity and a flow rate, a series of quantitative tests based on the breakthrough behavior were carried out in an isothermal fixed bed of synthetic zeolites such as molecular sieve 4A, 5A, 13X and mordenite. The amount of water vapor breaking during the adsorption was estimated to provide a breakthrough capacity at the various inlet flow rates and humidity conditions. The molecular sieve 13X exhibited a better adsorption performance at a given bed height. The existence of CO 2 in a humid atmosphere had a minor effect on the net adsorption capacity and the hydrogen isotopic water (HDO) in the elution stream showed a delayed behavior during a thermal desorption.

Kim, K. R.; Lee, M. S.; Paek, S.; Yim, S. P.; Ahn, D. H.; Chung, H.



AGATE as an indicator of impact structures: an example from Saaksjarvi, Finland  

NASA Astrophysics Data System (ADS)

Mineralogical, petrographical and chemical determinations were made for 743 agate (banded variety of chalcedonic quartz) nodules (diameters from 5 mm to 5 cm) formed during post-impact, low-temperature hydrothermal activity as vesicle fillings in the melt rocks of the Saaksjarvi meteorite impact structure (diameter 5 km) in SW-Finland. Other hydrothermal vesicle fillings in the impact melt rocks include chlorite, mordenite, smectite and kaolinite. The agates were classified into two types, whose mineralogical properties and chemical compositions fall within the range of volcanic agates (basaltic and rhyolitic host rocks). The relatively high age (about 510 Ma) of the Saaksjarvi impact melt rocks, however, is reflected by the presence of recrystallization textures, which are rare in younger volcanic agates. The Saaksjarvi structure was initially located after following the fortuitous discovery of agate "path-finders" in the glacial overburden. It is recommended that wherever volcanic type agates are found as float in Precambrian shield areas devoid of younger volcanic rocks, the possible presence of impact (or volcanic) craters in the vicinity should be considered.

Kinnunen, Kari A.; Lindqvist, Kristian



Novel Sorbent Development and Evaluation for the Capture of Krypton and Xenon from Nuclear Fuel Reprocessing Off-Gas Streams  

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, INL 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.

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



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)



Novel Sorbent Development and Evaluation for the Capture of Krypton and Xenon from Nuclear Fuel Reprocessing Off-Gas Streams  

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, INL 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.

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



Low sintering temperature glass waste forms for sequestering radioactive iodine  


Materials and methods of making low-sintering-temperature glass waste forms that sequester radioactive iodine in a strong and durable structure. First, the iodine is captured by an adsorbant, which forms an iodine-loaded material, e.g., AgI, AgI-zeolite, AgI-mordenite, Ag-silica aerogel, ZnI.sub.2, CuI, or Bi.sub.5O.sub.7I. Next, particles of the iodine-loaded material are mixed with powdered frits of low-sintering-temperature glasses (comprising various oxides of Si, B, Bi, Pb, and Zn), and then sintered at a relatively low temperature, ranging from C. to C. The sintering converts the mixed powders into a solid block of a glassy waste form, having low iodine leaching rates. The vitrified glassy waste form can contain as much as 60 wt % AgI. A preferred glass, having a sintering temperature of C. (below the silver iodide sublimation temperature of C.) was identified that contains oxides of boron, bismuth, and zinc, while containing essentially no lead or silicon.

Nenoff, Tina M.; Krumhansl, James L.; Garino, Terry J.; Ockwig, Nathan W.



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)



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)




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



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.

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



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



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

NASA Astrophysics Data System (ADS)

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.

French, Samuel A.; Coates, Rosie; Lewis, Dewi W.; Catlow, C. Richard A.




SciTech Connect

Several classes of molecular sieves were investigated as methanol dehydration catalysts for the LPDME{trademark} (liquid-phase dimethyl ether) process. Molecular sieves offer a number of attractive features as potential catalysts for the conversion of methanol to DME. These include (1) a wide range of acid strengths, (2) diverse architectures and channel connectivities that provide latitude for steric control, (3) high active site density, (4) well-investigated syntheses and characterization, and (5) commercial availability in some cases. We directed our work in two areas: (1) a general exploration of the catalytic behavior of various classes of molecular sieves in the LPDME{trademark} system and (2) a focused effort to prepare and test zeolites with predominantly Lewis acidity. In our general exploration, we looked at such diverse materials as chabazites, mordenites, pentasils, SAPOs, and ALPOs. Our work with Lewis acidity sought to exploit the structural advantages of zeolites without the interfering effects of deleterious Broensted sites. We used zeolite Ultrastable Y (USY) as our base material because it possesses a high proportion of Lewis acid sites. This work was extended by modifying the USY through ion exchange to try to neutralize residual Broensted acidity.

Andrew W. Wang



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



Radionuclide Leaching from Organic Ion Exchange Resin  

SciTech Connect

Laboratory tests were performed to examine the efficacy of leach treatments for decontaminating organic ion exchange resins (OIER), which have been found in a number of samples retrieved from K East Basin sludge. Based on process records, the OIER found in the K Basins is a mixed-bet strong acid/strong base material marketed as Purolite{trademark} NRW-037. Radionuclides sorbed or associated with the OIER can restrict its disposal to the Environmental Restoration Disposal Facility (ERDF). The need for testing to support development of a treatment process for K Basin sludge has been described in Section 4.2 of ''Testing Strategy to Support the Development of K Basins Sludge Treatment Process'' (Flament 1998). To help understand the effects of anticipated OIER elutriation and washing, tests were performed with well-rinsed OIER material from K East Basin floor sludge (sample H-08 BEAD G) and with well-rinsed OIER having approximately 5% added K East canister composite sludge (sample KECOMP). The rinsed resin-bearing material also contained the inorganic ion exchanger Zeolon-900{trademark}, a zeolite primarily composed of the mineral mordenite. The zeolite was estimated to comprise 27 weight percent of the dry H-08 BEAD G material.

Delegard, C.H.; Rinehart, D.E.



Petrology, sedimentology, and diagenesis of hemipelagic limestone and tuffaceous turbidities in the Aksitero Formation, central Luzon, Philippines  

USGS Publications Warehouse

The Aksitero Formation of central Luzon is an upper Eocene and lower Oligocene sequence of evenly bedded hemipelagic limestone with a few thin interlayers of tuffaceous turbidites. The limestone consists chiefly of planktonic foraminifers and calcareous nannofossils, with up to 30 percent of noncarbonate components, chiefly volcaniclastic debris. The tuff layers are graded beds. Composed mainly of glass shards, pumice fragments, crystals, and fine-grained volcanic rock fragments. Hydrocarbons migrated into the pores of the tuffaceous layers early during diagenesis but they were subsequently flushed out and only bitumen remains, chiefly as thin coatings on grains and wthin pumice vesicles. Later during diagenesis, zeolites (mordenite and c1inoptilolite) and secondary calcite preferentially replaced glass shards and pumice fragments. Deposition of the Aksitero Formation probably occurred at depths of at least 1,000 meters within a subsiding basin adjacent to an active island arc system. Submarine ash eruptions of silicic composition caused volcaniclastic turbidity currents that occasionally reached the basin floor. The more proximal facies of these volcaniclastic deposits may be prospective for hydrocarbons.

Garrison, Robert E.; Espiritu, E.; Horan, L.J.; Mack, L.E.



Incredible antibacterial activity of noble metal functionalized magnetic core-zeolitic shell nanostructures.  


Functionalized magnetic core-zeolitic shell nanostructures were prepared by hydrothermal and coprecipitation methods. The products were characterized by Vibrating Sample Magnetometer (VSM), X-ray powder diffraction (XRD), Fourier Transform Infrared (FTIR) spectra, nitrogen adsorption-desorption isotherms, and Transmission Electron Microscopy (TEM). The growth of mordenite nanoparticles on the surface of silica coated nickel ferrite nanoparticles in the presence of organic templates was also confirmed. Antibacterial activity of the prepared nanostructures was investigated by the inactivation of Escherichia coli as a gram negative bacterium. A new mechanism was proposed for inactivation of E. coli over the prepared samples. In addition, the Minimum Inhibitory Concentration (MIC) and reuse ability were studied. TEM images of the destroyed cell wall after the treatment time were performed to illustrate the inactivation mechanism. According to the experimental results, the core-shell nanostructures which were modified by organic agents and then functionalized with noble metal nanoparticles were the most active. The interaction of the noble metals with the organic components on the surface of nanostructures was studied theoretically and the obtained results were used to interpret the experimental results. PMID:24411359

Padervand, M; Janatrostami, S; Karanji, A Kiani; Gholami, M R



Evaluation of factors affecting performance of a zeolitic rock barrier to remove zinc from water.  


This study examined the factors affecting the performance of zeolitic rocks as reactive media in a permeable reactive barrier (PRB) used to remediate groundwater contaminated with Zn. Serial batch kinetic and sorption tests were conducted on zeolitic rock samples under a variety of conditions (i.e., reaction time, pH, initial Zn concentration, and particle size) using Zn(NO(3))(2).6H(2)O solutions. Serial column tests were also conducted on zeolitic rock samples at various flow rates. The removal of Zn increased approximately from 20-60 to 70-100% with increasing pH from 2 to 4 and decreasing initial Zn concentration from 434 to 5mg/L. Zn removal was not affected by the particle size, regardless of the zeolitic rock samples used in this study. The Zn removal increased approximately from 20-70 to 60-100% with increasing the cation exchange capacity (CEC) from 124.9 to 178.5meq/100g and increasing zeolite (i.e., clinoptilonite and mordenite) and montmorillonite contents from 53.7 to 73.2%. The results from the column and batch tests were comparable. Increasing the flow rate caused the earlier breakthrough of Zn (sorbing cation) and a rapid decrease in the concentration of Na, Ca, and Mg (desorbing cations). The hydraulic conductivities of the samples were unaffected by the particle size and mineral components. PMID:19880248

Lee, Se-Hoon; Jo, Ho Young; Yun, Seong-Taek; Lee, Young Jae



Association of Indigo with Zeolites for Improved Color Stabilization  

NASA Astrophysics Data System (ADS)

The durability of an organic colour and its resistance against external chemical agents and exposure to light can be significantly enhanced by hybridizing the natural dye with a mineral. In search for stable natural pigments, the present work focuses on the association of indigo blue with several zeolitic matrices (LTA zeolite, mordenite, MFI zeolite). The manufacturing of the hybrid pigment is tested under varying oxidising conditions, using Raman and UV-visible spectrometric techniques. Blending indigo with MFI is shown to yield the most stable composite in all of our artificial indigo pigments. In absence of defects and substituted cations such as aluminum in the framework of the MFI zeolite matrix, we show that matching the pore size with the dimensions of the guest indigo molecule is the key factor. The evidence for the high colour stability of indigo@MFI opens a new path for modeling the stability of indigo in various alumino-silicate substrates such as in the historical Maya Blue pigment.

Dejoie, Catherine; Martinetto, Pauline; Dooryhée, Eric; van Elslande, Elsa; Blanc, Sylvie; Bordat, Patrice; Brown, Ross; Porcher, Florence; Anne, Michel



Characterization of Binary Ag-Cu Ion Mixtures in Zeolites: Their Reduction Products and Stability to Air Oxidation  

SciTech Connect

A series of Ag+-Cu2+ binary mixtures with different Ag/Cu ratios were supported on mordenite with different Si/Al ratios and were subsequently reduced under hydrogen in the temperature range 323K - 473K. Ag and Cu K-edge X-ray Absorption Spectroscopy (XAS) was conducted on these systems in-situ to monitor the reduction species formed and the kinetics of their reduction. In-situ XANES clearly demonstrates that the formation of silver particles is severely impeded by the addition of copper and that the copper is converted from Cu(II) to Cu(I) during reduction and completely reverts back to Cu(II) during cooling. There are no indications at any stage of the formation of bimetallic Ag-Cu clusters. Interestingly, the Ag/Cu ratio appears to have no influence of the reduction kinetics and reduction products formed with only the highest Si/Al ratio (MR = 128) investigated during this study having an influence on the reduction and stability to air oxidation.

Fiddy, Steven [CCLRC Daresbury Laboratory, Daresbury, Warrington, UK, WA4 4AD (United Kingdom); Petranovskii, Vitalii [CCMC-UNAM, Apdo Postal 2681, 22800 Ensenada. B.C., (Mexico); Ogden, Steve [Department of Chemistry, University of Southampton, Southampton (United Kingdom); Iznaga, Inocente Rodriguez [Laboratorio Ingenieria de Zeolitas, Instituto de Materiales y Reactivos (IMRE) - Universidad de la Habana. Zapata y G. s/n. Havana0400 (Cuba)



Bis(?-oxo) versus mono(?-oxo)dicopper cores in a zeolite for converting methane to methanol: an in situ XAS and DFT investigation.  


Dicopper species have been identified as the active sites in converting methane to methanol in Cu-zeolites. To understand the formation of these copper cores in mordenite, we used in situ time-resolved X-ray absorption spectroscopy during heat treatment. Significant dehydration enabled the reduction of the copper cores, after which molecular oxygen was cleaved. The activated oxygen bridged two copper atoms to make the reactive precursor for the activation of methane. Even though the active bridging oxygen was detected, the XAS data were unable to distinguish a bis(?-oxo)dicopper core from a mono(?-oxo)dicopper core since XAS measures the average structure of the total copper population and the sample contains a mixture of copper species. We therefore used DFT calculations to understand the energetics of the formation of the active copper species and found that if a copper dimer exists in a zeolite, the mono(?-oxo)dicopper species is an energetically plausible structure. This is in contrast to molecular dicopper cores where the bis(?-oxo)dicopper core is preferentially formed. PMID:25732559

Alayon, Evalyn Mae C; Nachtegaal, Maarten; Bodi, Andras; Ranocchiari, Marco; van Bokhoven, Jeroen A



Fixed-bed adsorption of toluene on high silica zeolites: experiments and mathematical modelling using LDF approximation and a multisite model.  


The adsorption of toluene (TOL) as a target volatile organic compound has been studied experimentally and modelled on various hydrophobic zeolites: Faujasite (FAU), ZSM-5 (Z) and Mordenite (MOR). The influence of the nature of the compensating cation (H(+) or Na(+)) has also been investigated for ZSM-5 zeolite, which is known to possess three kinds of adsorption sites (sinusoidal channels, straight channels and intersections). Type I isotherms observed on FAU, Na-Z and MOR fitted well with the Langmuir model. A deviation from a type I isotherm was observed for H-Z, because of the structure of this zeolite. The Successive Langmuir Model was more successful to fit the 'bump' of the experimental curve than the Double Langmuir. Classical shapes were found for MOR, FAU and Na-Z breakthrough curves that were fitted with good accuracy using the Linear Driving Force (LDF) approximation. In the case of H-Z, a change of profile was observed during the dynamic adsorption and the differences seen between the Na-Z and H-Z behaviours were explained by the strong interactions between Na(+) and adsorbed TOL at the intersection sites. The Na(+) cations prevented reorientation of TOL molecules at the intersection and thereby avoided the filling of the sinusoidal channel segments. Thus, a specific model was developed for fitting the breakthrough curve of H-Z. The model developed took into account these two types of adsorption sites with the overall uptake for each site being given by an LDF approximation. PMID:25624172

Brodu, Nicolas; Sochard, Sabine; Andriantsiferana, Caroline; Pic, Jean-Stéphane; Manero, Marie-Hélène



NO decomposition in non-reducing atmospheres. Final report, September 1993--February 1997  

SciTech Connect

Co(II)NH{sub 4}-erionite zeolites with cobalt contents varying from 0.002 to 8.2 wt% of Co(II) were prepared, and the samples were studied via diffuse reflectance spectroscopy in the UV-VIS-NIR region and measurement of magnetic moments of the Co ions. Samples of Co(II)-ZSM-5 zeolites were also prepared and studied via diffuse reflectance spectroscopy after being dehydrated at 350 and 525 C and after adsorption of carbon monoxide, water, and ethylene. NO adsorption/desorption studies were carried out, and diffuse reflectance spectroscopy was utilized to monitor the spectral changes that occurred during adsorption of NO on the Co(II) cations, which was observed to occur after dehydration treatments at 350 C and 525 C. In selective catalytic reduction of NO by methane, it was observed that Co-mordenite and Co-ferrierite exhibited the highest % NO converted to products and selectivity toward N{sub 2} formation, but Co-A zeolite and Co-erionite yielded the highest selectivities to NO{sub 2} formation. Co-ZSM-5 zeolite exhibited an intermediate behavior.




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.



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.



Zeolite-supported Metal Complexes of Rhodium and of Ruthenium: a General Synthesis Method Influenced by Molecular Sieving Effects  

SciTech Connect

A general method for synthesis of supported metal complexes having a high degree of uniformity is presented, whereby organometallic precursors incorporating acetylacetonate (C{sub 5}H{sub 7}O{sub 2}{sup -}, acac) ligands react with zeolites incorporating OHgroups near Al sites. The method is illustrated by the reactions of Rh(acac)(CO){sub 2} and of cis-Ru(acac){sub 2}({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2} with zeolites slurried in n-pentane at room temperature. The zeolites were H-Beta, H-SSZ-42, H-Mordenite, and HZSM-5. Infrared (IR) and extended X-ray absorption fine structure spectra of the zeolites incorporating rhodium complexes indicate the formation of Rh(CO){sub 2}{sup +} bonded near Al sites; similar results have been reported for the formation of zeolite-supported Rh({eta}{sup 2}-C{sub 2}H{sub 4}){sup 2+} from Rh(acac)({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2}. IR spectra of the supported rhodiumgem-dicarbonyls include sharp, well-resolved {nu}{sub CO} bands, demonstrating that the sites surrounding each metal complex are nearly equivalent. The frequencies of the {nu}{sub CO} bands show how the composition of the zeolite influences the bonding of the supported species, demonstrating subtle differences in the roles of the zeolite as ligands. When the zeolite has pore openings larger than the critical diameter of the precursor organometallic compound, the latter undergoes facile transport into the interior of the zeolite, so that a uniform distribution of the supported species results, but when the precursors barely fit through the zeolite apertures, the mass transport resistance is significant and the supported metal complexes are concentrated near the pore mouths.

Ogino, I.; Chen, C; Gates , B



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.



Hydrothermal alteration in research drill hole Y-2, Lower Geyser Basin, Yellowstone National Park, Wyoming  

SciTech Connect

Y-2, a US Geological Survey research diamond-drill hole in Lower Geyser Basin, Yellowstone National Park, was drilled to a depth of 157.4 meters. The hole penetrated interbedded siliceous sinter and travertine to 10.2 m, glacial sediments of the Pinedale Glaciation interlayered with pumiceous tuff from 10.2 to 31.7 m, and rhyolitic lavas of the Elephant Back flow of the Central Plateau Member and the Mallard Lake Member of the Pleistocene Plateau Rhyolite from 31.7 to 157.4 m. Hydrothermal alteration is pervasive in most of the nearly continuous drill core. Rhyolitic glass has been extensively altered to clay and zeolite minerals (intermediate heulandite, clinoptilolite, mordenite, montmorillonite, mixed-layer illite-montmorillonite, and illite) in addition to quartz and adularia. Numerous veins, vugs, and fractures in the core contain these and other minerals: silica minerals (opal, ..beta..-cristobalite, ..cap alpha..-cristobalite, and chalcedony), zeolites (analcime, wairakite, dachiardite, laumontite, and yugawaralite), carbonates (calcite and siderite), clay (kaolinite and chlorite), oxides (hematite, goethite, manganite, cryptomelane, pyrolusite, and groutite), and sulfides (pyrhotite and pyrite) along with minor aegirine, fluorite, truscottite, and portlandite. Interbedded travertine and siliceous sinter in the upper part of the drill core indicate that two distinct types of thermal water are responsible for precipitation of the surficial deposits, and further that the water regime has alternated between the two thermal waters more than once since the end of the Pinedale Glaciation (approx. 10,000 years B.P.). Alternation of zones of calcium-rich and sodium- and potassium-rich hydrothermal minerals also suggests that the calcium-rich and sodium- and potassium-rich hydrothermal minerals also suggests that the water chemistry in this drill hole varies with depth.

Bargar, K.E.; Beeson, M.H.



Further studies of effects of sodium aluminosilicate on egg shell quality.  


Five experiments were conducted using 36 dietary treatments to compare chloride salts and HCl as chemical sources of Cl for the adjustment of dietary Cl when using sodium aluminosilicate (SAS), to compare SAS to natural zeolites (clinoptilolite and mordenite), and to determine the appropriate level of dietary SAS for optimum egg specific gravity. The methods of Na and Cl correction used in the various treatments included altering the levels of NaCl, calcium chloride (CaCl2), potassium chloride (KCl), magnesium chloride (MgCl2), iron chloride (FeCl3), or hydrochloric acid (HCl). Experimental diets were fed for 6 to 8 wk. Results of all experiments (except Experiment 2) indicated that the addition of SAS to layer diets improved egg specific gravity and that correction for Na by removal of NaCl and the addition of HCl was not necessary for SAS to be effective. No beneficial effects of dietary SAS on egg specific gravity were observed when Na and Cl corrections were made using CaCl2, KCl, MgCl2, or FeCl3. The feeding of SAS has no influence on egg production in Experiments 1 and 3 but significantly improved egg production in Experiment 4, when it was added to diets containing 2.75% Ca. An adverse effect on production of feeding SAS was observed, especially at the higher levels of SAS in Experiments 2 and 5. In general, SAS tended to reduce feed consumption, with no effect on egg weight. It was concluded that .75% SAS will improve egg specific gravity approximately 1 to 3 units and that correction for Na was not necessary for SAS to be effective. PMID:2841658

Roland, D A



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



Preliminary stratigraphic and petrologic characterization of core samples from USW-G1, Yucca Mountain, Nevada  

SciTech Connect

Tuffs of the Nevada Test Site are currently under investigation to determine their potential for long-term storage of radioactive waste. As part of this program, hole USW-G1 was drilled to a depth of 6000 ft below the surface, in the central part of the Yucca Mountain area, Nevada Test Site, Nevada. Petrographic study of the USW-G1 core is presented in this report and shows the tuffs (which generally were variably welded ash flows) are partly recrystallized to a variety of secondary minerals. The important alteration products are zeolites (heulandite, clinoptilolite, mordenite and analcime), smectite clays with minor interstratified illite, albite, micas, potassium feldspar, and various forms of silica. Iijima`s zeolite zones I through IV of burial metamorphism can be recognized in the core. Zeolites are first observed at about the 1300-ft depth, and the high-temperature boundary of zeolite stability in this core occurs at about 4350 ft. Analcime persists, either metastably or as a retrograde mineral, deeper in the core. The oxidation state of Fe-Ti oxide minerals, through most of the core, increases as the degree of welding decreases, but towards the bottom of the hole, reducing conditions generally prevail. Four stratigraphic units transected by the core may be potentially favorable sites for a waste repository. These four units, in order of increasing depth in the core, are (1) the lower cooling unit of the Topopah Spring Member, (2) cooling unit II of the Bullfrog Member, (3) the upper part of the Tram tuff, and (4) the Lithic-rich tuff.

Waters, A.C.; Carroll, P.R. (eds.)



Distribution of Components in Ion Exchange Materials Taken from the K East Basin and Leaching of Ion Exchange Materials by Nitric/Hydrofluoric Acid and Nitric/Oxalic Acid  

SciTech Connect

Laboratory tests were performed to examine the efficacy of mixed nitric/hydrofluoric acid followed by mixed nitric/oxalic acid leach treatments to decontaminate ion exchange materials that have been found in a number of samples retrieved from K East (KE)Basin sludge. The ion exchange materials contain organic ion exchange resins and zeolite inorganic ion exchange material. Based on process records, the ion exchange resins found in the K Basins is a mixed-bed, strong acid/strong base material marketed as Purolite NRW-037. The zeolite material is Zeolon-900, a granular material composed of the mineral mordenite. Radionuclides sorbed or associated with the ion exchange material can restrict its disposal to the Environmental Restoration Disposal Facility (ERDF). The need for testing to support development of a treatment process for K Basin sludge has been described in Section 4.2 of ''Testing Strategy to Support the Development of K Basins Sludge Treatment Process'' (Flament 1998). Elutriation and washing steps are designed to remove the organic resins from the K Basin sludge. To help understand the effects of the anticipated separation steps, tests were performed with well-rinsed ion exchange (IX) material from KE Basin floor sludge (sample H-08 BEAD G) and with well-rinsed IX having small quantities of added KE canister composite sludge (sample KECOMP). Tests also were performed to determine the relative quantities of organic and inorganic IX materials present in the H-08 K Basin sludge material. Based on chemical analyses of the separated fractions, the rinsed and dry IX material H-08 BEAD G was found to contain 36 weight percent inorganic material (primarily zeolite). The as-received (unrinsed) and dried H-08 material was estimated to contain 45 weight percent inorganic material.

Delegard, C.H.; Rinehart, D.E.; Hoopes, F.V.



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.



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



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.



NO decomposition in non-reducing atmospheres. Technical progress report, December 1994--February 1995  

SciTech Connect

The overall goal of this research is to establish the fundamental science needed to develop catalysts that will exhibit high activity and selectivity in the decomposition of NO into N{sub 2} and O{sub 2}. This project is centered on the preparation, characterization, and testing of transition metal exchanged catalysts, especially Co(III) zeolites. Additional Co(II) exchanged A zeolite samples have been prepared in aqueous solution at pH = 5.0-6.1 that contain different exchange levels of Co(II). Some of these have been analyzed for Na and Co contents by chemical methods and by X-ray photoelectron spectroscopy. It was shown that preparation of the samples by ion exchange between pH {approx}6 and 7 tended to give stoichiometric ion exchange of Co(II) for Na{sup +}. However, ion exchange at lower pH tended to lead to exchange with H{sup +} while ion exchange at higher pH tended to lead to the presence of excess Co(H), probably by precipitation of a basic Co phase. Systematic analyses of Na A zeolite, CO(II) A zeolites, and Co(II)/Ce(III) A zeolites, as well as Na X zeolite, Na Y zeolite, and Na mordenite for comparison purposes, have been carried out by X-ray photoelectron spectroscopy and Auger spectroscopy methods. Complete data analysis has not yet been carried out, but trends in some parameters have been noted, e.g. the relative intensity of the O KL{sub 2,3}L{sub 2,3} line in the O ls spectral region increases as the Si Al ratio of the Na zeolites increases.

Klier, K.; Herman, R.G.; Jirka, I.



Thorium removal by different adsorbents.  


The removal of radiotoxic Th(4+) from aqueous solutions has been explored using two different groups of adsorptive materials (e.g. two activated carbons and four zeolites-two natural and two synthetic). The activated carbons were prepared from solvent extracted olive pulp (SEOP) and olive stone (OS) by a two-step physical activation method with steam. They were characterized by N(2) at 77K adsorption, Hg porosimetry and by determination of their iodine number. All carbons prepared are of the H-type (e.g. contain mainly basic surface oxides) confirmed by the results of the Boehm's method. The natural zeolites, clinoptilolite (NaCLI) and mordenite (NaMOR), were pretreated with Na(+) before the adsorption experiments, while the synthetic ones, NaX and NaA, were provided in their commercial sodium form. The natural zeolites, NaCLI and NaMOR, utilized 11.5 and 38.6% of the theoretical ion-exchange capacity, based on Al content, respectively, while NaX and NaA utilized 41.5 and 45.9%, respectively. The activated carbons showed better removal capability than NaCLI. NaMOR, showed comparable results to the carbon originated from OS, but lower removal capability than the carbon originated from SEOP. The synthetic zeolites showed the highest removal ability for thorium ions due to their increased ion-exchange capacity because of their cleaner and larger framework channels and their higher number of ion-exchange sites. The carbons adsorption capacity mainly depends on the content and nature of functional surface groups. The adsorption data were fitted to Langmuir and Freundlich models. The former achieved best fits and was further applied to obtain the respective Langmuir constant and maximum adsorption capacity for each system. PMID:12573830

Metaxas, Michail; Kasselouri-Rigopoulou, Vasilia; Galiatsatou, Polymnia; Konstantopoulou, Cathrine; Oikonomou, Dimitrios



Methane to Acetic Acid over Cu-Exchanged Zeolites: Mechanistic Insights from a Site-Specific Carbonylation Reaction.  


The selective low temperature oxidation of methane is an attractive yet challenging pathway to convert abundant natural gas into value added chemicals. Copper-exchanged ZSM-5 and mordenite (MOR) zeolites have received attention due to their ability to oxidize methane into methanol using molecular oxygen. In this work, the conversion of methane into acetic acid is demonstrated using Cu-MOR by coupling oxidation with carbonylation reactions. The carbonylation reaction, known to occur predominantly in the 8-membered ring (8MR) pockets of MOR, is used as a site-specific probe to gain insight into important mechanistic differences existing between Cu-MOR and Cu-ZSM-5 during methane oxidation. For the tandem reaction sequence, Cu-MOR generated drastically higher amounts of acetic acid when compared to Cu-ZSM-5 (22 vs 4 ?mol/g). Preferential titration with sodium showed a direct correlation between the number of acid sites in the 8MR pockets in MOR and acetic acid yield, indicating that methoxy species present in the MOR side pockets undergo carbonylation. Coupled spectroscopic and reactivity measurements were used to identify the genesis of the oxidation sites and to validate the migration of methoxy species from the oxidation site to the carbonylation site. Our results indicate that the Cu(II)-O-Cu(II) sites previously associated with methane oxidation in both Cu-MOR and Cu-ZSM-5 are oxidation active but carbonylation inactive. In turn, combined UV-vis and EPR spectroscopic studies showed that a novel Cu(2+) site is formed at Cu/Al <0.2 in MOR. These sites oxidize methane and promote the migration of the product to a Brønsted acid site in the 8MR to undergo carbonylation. PMID:25562431

Narsimhan, Karthik; Michaelis, Vladimir K; Mathies, Guinevere; Gunther, William R; Griffin, Robert G; Román-Leshkov, Yuriy



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.



Long-term product consistency test of simulated 90-19/Nd HLW glass  

NASA Astrophysics Data System (ADS)

Chemical durability of 90-19/Nd glass, a simulated high-level waste (HLW) glass in contact with the groundwater was investigated with a long-term product consistency test (PCT). Generally, it is difficult to observe the long term property of HLW glass due to the slow corrosion rate in a mild condition. In order to overcome this problem, increased contacting surface ( S/ V = 6000 m -1) and elevated temperature (150 °C) were employed to accelerate the glass corrosion evolution. The micro-morphological characteristics of the glass surface and the secondary minerals formed after the glass alteration were analyzed by SEM-EDS and XRD, and concentrations of elements in the leaching solution were determined by ICP-AES. In our experiments, two types of minerals, which have great impact on glass dissolution, were found to form on 90-19/Nd HLW glass surface when it was subjected to a long-term leaching in the groundwater. One is Mg-Fe-rich phyllosilicates with honeycomb structure; the other is aluminosilicates (zeolites). Mg and Fe in the leaching solution participated in the formation of phyllosilicates. The main components of phyllosilicates in alteration products of 90-19/Nd HLW glass are nontronite (Na 0.3Fe 2Si 4O 10(OH) 2·4H 2O) and montmorillonite (Ca 0.2(Al,Mg) 2Si 4O 10(OH) 2·4H 2O), and those of aluminosilicates are mordenite ((Na 2,K 2,Ca)Al 2Si 10O 24·7H 2O)) and clinoptilolite ((Na,K,Ca) 5Al 6Si 30O 72·18H 2O). Minerals like Ca(Mg)SO 4 and CaCO 3 with low solubility limits are prone to form precipitant on the glass surface. Appearance of the phyllosilicates and aluminosilicates result in the dissolution rate of 90-19/Nd HLW glass resumed, which is increased by several times over the stable rate. As further dissolution of the glass, both B and Na in the glass were found to leach out in borax form.

Gan, X. Y.; Zhang, Z. T.; Yuan, W. Y.; Wang, L.; Bai, Y.; Ma, H.



Neutron Scattering Studies of Fundamental Processes in Earth Materials, Final Report  

SciTech Connect

The aim of this work was to use neutron scattering techniques to explore the dynamics and structure of water in rock samples. The dynamics of water in rock at low (residual) saturation are directly related to the transport properties of fluids within the host rock. The structure of water in rock may be related to the elastic behavior of the rock, which in many cases is nonlinear and hysteretic. Neutron scattering techniques allow us to study water in intact rock samples at both the molecular and microstructural scales. Our samples were Berea sandstone, Calico Hills and Prow Pass tuffs from Yucca Mountain, NV, and pure samples of the tuff constituents, specifically mordenite and clinoptilolite. We chose Berea sandstone because its macroscopic elastic behavior is known to be highly unusual, and the microscopic mechanisms producing this behavior are not understood. We chose Yucca Mountain tuff, because the fluid transport properties of the geologic structure at Yucca Mountain, Nevada could be relevant to the performance of a high level nuclear waste repository at that site. Neutron scattering methods have a number of properties that are extremely useful for the study of earth materials. In contrast to X-rays, neutrons have very low absorption cross-sections for most elements so that entire bulk samples of considerable size can be 'illuminated' by the neutron beam. Similarly, samples that are optically opaque can be readily investigated by inelastic neutron scattering techniques. Neutrons are equally sensitive to light atoms as to heavy atoms, and can, for example, readily distinguish between Al and Si, neighboring atoms in the periodic table that are difficult to tell apart by X-ray diffraction. Finally, neutrons are particularly sensitive to hydrogen and thus can be used to study the motions, both vibrational and diffusive, of H-containing molecules in rocks, most notably of course, water. Our studies were primarily studies of guest molecules (in our case, water) in a host material (rock). We used three neutron scattering techniques: quasielastic neutron scattering (QNS), inelastic neutron scattering (INS), and neutron powder diffraction (NPD). We used QNS to measure the translational and rotational diffusional motion of water in rock; INS vibrational spectra allowed us to determine the nature of residual water in a sample (disassociated, chemisorbed, or physisorbed); and NPD measurements may allow us to determine the locations of residual water molecules (and the associated dynamic disorder), and thereby understand the binding of water molecules in our samples.

McCall, K. R.



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.



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



Adsorption of Amino Acids (Ala, Cys, His, Met) on Zeolites: Fourier Transform Infrared and Raman Spectroscopy Investigations  

NASA Astrophysics Data System (ADS)

Minerals adsorb more amino acids with charged R-groups than amino acids with uncharged R-groups. Thus, the peptides that form from the condensation of amino acids on the surface of minerals should be composed of amino acid residues that are more charged than uncharged. However, most of the amino acids (74%) in today's proteins have an uncharged R-group. One mechanism with which to solve this paradox is the use of organophilic minerals such as zeolites. Over the range of pH (pH 2.66-4.50) used in these experiments, the R-group of histidine (His) is positively charged and neutral for alanine (Ala), cysteine (Cys), and methionine (Met). In acidic hydrothermal environments, the pH could be even lower than those used in this study. For the pH range studied, the zeolites were negatively charged, and the overall charge of all amino acids was positive. The conditions used here approximate those of prebiotic Earth. The most important finding of this work is that the relative concentrations of each amino acid (X=His, Met, Cys) to alanine (X/Ala) are close to 1.00. This is an important result with regard to prebiotic chemistry because it could be a solution for the paradox stated above. Pore size did not affect the adsorption of Cys and Met on zeolites, and the Si/Al ratio did not affect the adsorption of Cys, His, and Met. ZSM-5 could be used for the purification of Cys from other amino acids (Student-Newman-Keuls test, p<0.05), and mordenite could be used for separation of amino acids from each other (Student-Newman-Keuls test, p<0.05). As shown by Fourier transform infrared (FT-IR) spectra, Ala interacts with zeolites through the group, and methionine-zeolite interactions involve the COO, , and CH3 groups. FT-IR spectra show that the interaction between the zeolites and His is weak. Cys showed higher adsorption on all zeolites; however, the hydrophobic Van der Waals interaction between zeolites and Cys is too weak to produce any structural changes in the Cys groups (amine, carboxylic, sulfhydryl, etc.); thus, the FT-IR and Raman spectra are the same as those of solid Cys.

Carneiro, Cristine E. A.; de Santana, Henrique; Casado, Clara; Coronas, Joaquin; Zaia, Dimas A. M.



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.



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.



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




SciTech Connect

The operational requirements for the River Protection Project - Waste Treatment Plant (RPP-WTP) Low Activity Waste (LAW) and High Level Waste (HLW) melter systems, together with the feed constituents, impose a number of challenges to the off-gas treatment system. The system must be robust from the standpoints of operational reliability and minimization of maintenance. The system must effectively control and remove a wide range of solid particulate matter, acid mists and gases, and organic constituents (including those arising from products of incomplete combustion of sugar and organics in the feed) to concentration levels below those imposed by regulatory requirements. The baseline design for the RPP-WTP LAW primary off-gas system includes a submerged bed scrubber (SBS), a wet electrostatic precipitator (WESP), and a high efficiency particulate air (HEPA) filter. The secondary off-gas system includes a sulfur-impregnated activated carbon bed (AC-S), a thermal catalytic oxidizer (TCO), a single-stage selective catalytic reduction NOx treatment system (SCR), and a packed-bed caustic scrubber (PBS). The baseline design for the RPP-WTP HLW primary off-gas system includes an SBS, a WESP, a high efficiency mist eliminator (HEME), and a HEPA filter. The HLW secondary off-gas system includes a sulfur-impregnated activated carbon bed, a silver mordenite bed, a TCO, and a single-stage SCR. The one-third scale HLW DM1200 Pilot Melter installed at the Vitreous State Laboratory (VSL) was equipped with a prototypical off-gas train to meet the needs for testing and confirmation of the performance of the baseline off-gas system design. Various modifications have been made to the DM1200 system as the details of the WTP design have evolved, including the installation of a silver mordenite column and an AC-S column for testing on a slipstream of the off-gas flow; the installation of a full-flow AC-S bed for the present tests was completed prior to initiation of testing. The DM1200 system was reconfigured to enable testing of the baseline HLW or LAW off-gas trains to perform off-gas emissions testing with both LAW and HLW simulants in the present work. During 2002 and 2003, many of these off-gas components were tested individually and in an integrated manner with the DM1200 Pilot Melter. Data from these tests are being used to support engineering design confirmation and to provide data to support air permitting activities. In fiscal year 2004, the WTP Project was directed by the Office of River Protection (ORP) to comply with Environmental Protection Agency (EPA) Maximum Achievable Control Technology (MACT) requirements for organics. This requires that the combined melter and off-gas system have destruction and removal efficiency (DRE) of >99.99% for principal organic dangerous constituents (PODCs). In order to provide confidence that the melter and off-gas system are able to achieve the required DRE, testing has been directed with both LAW and HLW feeds. The tests included both 'normal' and 'challenge' WTP melter conditions in order to obtain data for the potential range of operating conditions for the WTP melters and off-gas components. The WTP Project, Washington State Department of Ecology, and ORP have agreed that naphthalene will be used for testing to represent semi-volatile organics and allyl alcohol will be used to represent volatile organics. Testing was also performed to determine emissions of halides, metals, products of incomplete combustion (PICs), dioxins, furans, coplanar PCBs, total hydrocarbons, and COX and NOX, as well as the particle size distribution (PSD) of particulate matter discharged at the end of the off-gas train. A description of the melter test requirements and analytical methods used is provided in the Test Plan for this work. Test Exceptions were subsequently issued which changed the TCO catalyst, added total organic emissions (TOE) to exhaust sampling schedule, and allowing modification of the test conditions in response to attainable plenum temperatures as well as temperature increases in the sulfur impr




Megabreccias, Early Lakes, and Duration of Resurgence Recorded in Valles Caldera, New Mexico  

NASA Astrophysics Data System (ADS)

New 1:24,000 scale geologic mapping combined with previous and ongoing geoscientific studies are revealing significant new findings on intracaldera stratigraphy and structure, initial development of intracaldera lakes, and the duration of resurgence within the ca. 1.25 Myr Valles caldera. The caldera is about 22 km in diameter and contains a resurgent dome that is a northeast-trending oval roughly11 x 9 km in dimension. Maximum resurgence (uplift) was more than 1000 m, during which the dome split into three principal segments herein named the Redondo Peak, Redondo Border, and Valle San Luis segments. These segments are separated from each other by long, narrow grabens herein called the Redondo Creek, Jaramillo Creek, and San Luis Creek grabens. Differential uplift accompanied by intense faulting has exposed large, rootless megabreccia (Mbx) blocks composed of precaldera rocks submerged in densely welded, intracaldera upper Bandelier Tuff. The largest Mbx blocks are roughly 0.2 to 2.0 km long and consist primarily of Abo Fm (Permian), Gallisteo Fm (?) (Eocene), Santa Fe Group (Miocene), Paliza Canyon Fm (late Miocene) and lower Bandelier Tuff (ca. 1.62 Ma). Deep geothermal wells drilled within the Redondo Creek graben from 1970 to 1983 penetrate as much as 2032 m of intracaldera Bandelier Tuff and post-Bandelier rocks before intersecting caldera floor rocks (average = 1646 m, n = 23 wells). Evidence that a lake developed within the caldera depression is preserved in finely laminated lacustrine beds and rhyolitic, hydromagmatic tuffs that overlie intracaldera Bandelier Tuff on the resurgent dome. The lacustrine rocks contain organic remains and the hydromagmatic tuffs contain accretionary lapilli. In some locations, lacustrine and hydromagmatic rocks are interbedded. Earliest post-caldera rhyolite lavas (Deer Canyon Member) display occasional pepperite and pillow textures. Many lavas contain significant amounts of fine, opalized flow breccia indicating interaction with water. Associated Deer Canyon tuffs are altered to variable mixtures of silica, smectite, clinoptilolite, mordenite and other phases. Slightly younger rhyolite lava flows (Redondo Creek Member) occasionally display upper flow surfaces in which cracks are filled with zeolitized mud. The combined geologic evidence indicates that the initial Valles lake was widespread and relatively shallow, containing waters with neutral to alkaline pH and relatively high K/Na ratios. 40Ar/39Ar dating of sanidine separates from Deer Canyon and Redondo Creek rhyolites yields ages that are statistically indistinguishable from the age of underlying upper Bandelier Tuff. These results indicate that the intracaldera lake developed immediately after the caldera formed and that the resurgent dome rose out of a lake. Most resurgence occurred after Redondo Creek rhyolite was erupted because the unit is intensely faulted and associated lacustrine beds are now as much as 500 m above the undeformed caldera moat. In contrast, rhyolite lavas of the first post-caldera moat complex, Cerro del Medio (about 1.22 Ma) show no apparent deformation or uplift due to resurgence. Within the errors of the various 40Ar/39Ar dates, the apparent duration of resurgence was no longer than about 50,000 years yielding a minimum resurgence rate of about 2 cm/y.

Goff, F.; Goff, C. J.; Phillips, E. H.; Kyle, P. R.; McIntosh, W. C.; Chipera, S.; Gardner, J. N.



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.



Development of Composite Adsorbents for LLW Treatment and Their Adsorption Properties for Cs and Sr - 13127  

SciTech Connect

In this study, the composite adsorbents (KCoFC-NM (NM: natural mordenite), KCoFC-SG (SG: porous silica gel), AMP-SG and so on) were prepared by impregnation-precipitation methods. As for the distribution properties, the largest K{sub d,Cs} value of 3.8 x 10{sup 4} cm{sup 3}/g was obtained for KCoFC-SG (Davi.) composite. KCoFC-SG (NH, MB5D) and T-KCFC also had relatively large K{sub d,Cs} values above 1.0 x 10{sup 4} cm{sup 3}/g. The uptake rate of Cs{sup +} ions was examined by batch method. KCoFC-SG (NH, MB5D) and AMP-SG (Davi.) had relatively large uptake rate of Cs{sup +}, and the uptake attained equilibrium within 1 h. The maximum uptake capacity of Cs{sup +} ions was estimated to be above 0.5 mmol/g for KCoFC-NM and KCoFC-CP composites. KCoFC-X composite had a relatively large uptake capacity of Cs{sup +} ions (0.23 mmol/g > 0.17 mmol/g (T-KCFC)) and this composite also had a selectivity towards Sr{sup 2+} ions; KCoFC-X is effective adsorbent for both Cs{sup +} and Sr{sup 2+} ions. The largest value of K{sub d,Sr} was estimated to be 218 cm{sup 3}/g for titanic acid-PAN. Titanic acid-PAN had the largest uptake rate of Sr{sup 2+} ions, and the uptake attained equilibrium within 8 h. Adsorbability of other nuclides was further examined by batch method. All adsorbents had adsorbability for Rb{sup +} and RuNO{sup 3+} ions. KCoFC-SG (NH), KCoFC-CP and T-KCFC had higher selectivity towards Cs{sup +} than other adsorbents; these adsorbents had adsorbability to Cs{sup +} ions even in the presence of Ba{sup 2+}, Ca{sup 2+} and Mg{sup 2+} ions. The separation factor of K{sub d,Sr}/K{sub d,Ba} for titanic acid-PAN was about 1, indicating that the K{sub d,Sr} for titanic acid-PAN tends to decrease with Ba{sup 2+} concentration. As for the breakthrough properties, the largest 5 % breakpoint and 5 % breakthrough capacity of Cs{sup +} ions were estimated to be 47.1 cm{sup 3} and 0.07 mmol/g for the column of KCoFC-SG (NH), respectively. The order of 5 % breakthrough capacity of Cs{sup +} is as follows; KCoFC-SG (NH) > KCoFC-NM > KCoFC-SG (Q-10) > T-KCFC > KCoFC-X > KCoFC-CP. From the results of batch and column experiments, the composite adsorbent of KCoFC-SG (NH) was effective for the uptake of Cs{sup +} ions, and KCoFC-X composite was useful for the uptake of both Cs{sup +} and Sr{sup 2+} ions. The estimation of irradiation stability and the uptake properties using the actual wastes are further essential for the practical operation. (authors)

Susa, Shunsuke; Mimura, Hitoshi [Dept. of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University, Aramaki-Aza-Aoba 6-6-01-2, Sendai, 980-8579 (Japan)] [Dept. of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University, Aramaki-Aza-Aoba 6-6-01-2, Sendai, 980-8579 (Japan); Ito, Yoshiyuki; Saito, Yasuo [Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, 2-4 Shirakata Shirone, Naka-gun, Ibaraki, 319-1195 (Japan)] [Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, 2-4 Shirakata Shirone, Naka-gun, Ibaraki, 319-1195 (Japan)



Final report on the safety assessment of aluminum silicate, calcium silicate, magnesium aluminum silicate, magnesium silicate, magnesium trisilicate, sodium magnesium silicate, zirconium silicate, attapulgite, bentonite, Fuller's earth, hectorite, kaolin, lithium magnesium silicate, lithium magnesium sodium silicate, montmorillonite, pyrophyllite, and zeolite.  


This report reviews the safety of Aluminum, Calcium, Lithium Magnesium, Lithium Magnesium Sodium, Magnesium Aluminum, Magnesium, Sodium Magnesium, and Zirconium Silicates, Magnesium Trisilicate, Attapulgite, Bentonite, Fuller's Earth, Hectorite, Kaolin, Montmorillonite, Pyrophyllite, and Zeolite as used in cosmetic formulations. The common aspect of all these claylike ingredients is that they contain silicon, oxygen, and one or more metals. Many silicates occur naturally and are mined; yet others are produced synthetically. Typical cosmetic uses of silicates include abrasive, opacifying agent, viscosity-increasing agent, anticaking agent, emulsion stabilizer, binder, and suspending agent. Clay silicates (silicates containing water in their structure) primarily function as adsorbents, opacifiers, and viscosity-increasing agents. Pyrophyllite is also used as a colorant. The International Agency for Research on Cancer has ruled Attapulgite fibers >5 microm as possibly carcinogenic to humans, but fibers <5 microm were not classified as to their carcinogenicity to humans. Likewise, Clinoptilolite, Phillipsite, Mordenite, Nonfibrous Japanese Zeolite, and synthetic Zeolites were not classified as to their carcinogenicity to humans. These ingredients are not significantly toxic in oral acute or short-term oral or parenteral toxicity studies in animals. Inhalation toxicity, however, is readily demonstrated in animals. Particle size, fibrogenicity, concentration, and mineral composition had the greatest effect on toxicity. Larger particle size and longer and wider fibers cause more adverse effects. Magnesium Aluminum Silicate was a weak primary skin irritant in rabbits and had no cumulative skin irritation in guinea pigs. No gross effects were reported in any of these studies. Sodium Magnesium Silicate had no primary skin irritation in rabbits and had no cumulative skin irritation in guinea pigs. Hectorite was nonirritating to the skin of rabbits in a Draize primary skin irritation study. Magnesium Aluminum Silicate and Sodium Magnesium Silicate caused minimal eye irritation in a Draize eye irritation test. Bentonite caused severe iritis after injection into the anterior chamber of the eyes of rabbits and when injected intralamellarly, widespread corneal infiltrates and retrocorneal membranes were recorded. In a primary eye irritation study in rabbits, Hectorite was moderately irritating without washing and practically nonirritating to the eye with a washout. Rats tolerated a single dose of Zeolite A without any adverse reaction in the eye. Calcium Silicate had no discernible effect on nidation or on maternal or fetal survival in rabbits. Magnesium Aluminum Silicate had neither a teratogenic nor adverse effects on the mouse fetus. Female rats receiving a 20% Kaolin diet exhibited maternal anemia but no significant reduction in birth weight of the pups was recorded. Type A Zeolite produced no adverse effects on the dam, embryo, or fetus in either rats or rabbits at any dose level. Clinoptilolite had no effect on female rat reproductive performance. These ingredients were not genotoxic in the Ames bacterial test system. In primary hepatocyte cultures, the addition of Attapulgite had no significant unscheduled DNA synthesis. Attapulgite did cause significant increases in unscheduled DNA synthesis in rat pleural mesothelial cells, but no significant increase in sister chromosome exchanges were seen. Zeolite particles (<10 microm) produced statistically significant increase in the percentage of aberrant metaphases in human peripheral blood lymphocytes and cells collected by peritoneal lavage from exposed mice. Topical application of Magnesium Aluminum Silicate to human skin daily for 1 week produced no adverse effects. Occupational exposure to mineral dusts has been studied extensively. Fibrosis and pneumoconiosis have been documented in workers involved in the mining and processing of Aluminum Silicate, Calcium Silicate, Zirconium Silicate, Fuller's Earth, Kaolin, Montmorillonite, Pyrophyllite, and Zeolite. The Cosmetic Ingre

Elmore, Amy R



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.



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.