High Barium Research Articles

Endocrine disrupting activities of surface water associated with a West Virginia oil and gas industry wastewater disposal site

Currently, >95% of end disposal of hydraulic fracturing wastewater from unconventional oil and gas operations in the US occurs via injection wells. Key data gaps exist in understanding the potential impact of underground injection on surface water quality and environmental health. The goal of this study was to assess endocrine disrupting activity in surface water at a West Virginia injection well disposal site. Water samples were collected from a background site in the area and upstream, on, and downstream of the disposal facility. Samples were solid-phase extracted, and extracts assessed for agonist and antagonist hormonal activities for five hormone receptors in mammalian and yeast reporter gene assays. Compared to reference water extracts upstream and distal to the disposal well, samples collected adjacent and downstream exhibited considerably higher antagonist activity for the estrogen, androgen, progesterone, glucocorticoid and thyroid hormone receptors. In contrast, low levels of agonist activity were measured in upstream/distal sites, and were inhibited or absent at downstream sites with significant antagonism. Concurrent analyses by partner laboratories (published separately) describe the analytical and geochemical profiling of the water; elevated conductivity as well as high sodium, chloride, strontium, and barium concentrations indicate impacts due to handling of unconventional oil and gas wastewater. Notably, antagonist activities in downstream samples were at equivalent authentic standard concentrations known to disrupt reproduction and/or development in aquatic animals. Given the widespread use of injection wells for end-disposal of hydraulic fracturing wastewater, these data raise concerns for human and animal health nearby.

Mineralogy and geochemistry of laterites developed on chlorite schists in Tchollire region, North Cameroon

Laterites developed from the weathering of chlorite schists have been studied in Tchollire region, North Cameroon. They include two profiles: a 5.5 m depth profile in Doudja site and a 12.3 m profile in Fimbe site.The chlorite schists have a lepidoblastic to lepidogranoblastic texture and are mainly composed of chlorite, muscovite, biotite, feldspars and quartz but that of Fimbe is marked by the presence of amphibole. It is felsic with a high SiO2 content (67%) and low Fe2O3 (5.8%) and MgO (2.4%) contents in Doudja site but has a lower content of SiO2 (46%) in the Fimbe site where it is mafic with higher contents in Fe2O3 (12.4%) and MgO (6.3%). The chlorite schists of Doudja show high contents in Zr, Sr, Ta, with moderate contents in Cr, V, U and Zn. That of Fimbe is particularly rich in Cr, V, Ni, Sr and Zn with a moderate Zr content. All chlorite schists have high barium contents (270–393 ppm) with LREE-enrichment.The soils are yellowish and, from bottom to top, are composed of a coarse saprolite, fine saprolite, loose clayey horizon and an organo mineral horizon. The main minerals are chlorite, muscovite, biotite, feldspars, quartz, smectites, vermiculite, kaolinite, hematite and goethite. In Doudja, SiO2 mainly decreases from the bottom to the top of the profile while, Al2O3 and Fe2O3 generally increase; in Fimbe, SiO2 and Al2O3 increase up the profile but Fe2O3 decreases; the general high Fe and corresponding decrease in Mg contents in the soils show that the smectite formed is nontronite. Chromium, V, Cu, Ba and Sr show high contents in the two studied profiles but Zr, U and Ta is higher in Doudja than in Fimbe. Copper generally has high contents in the loose clayey and organo mineral horizons. Nickel is higher in the Fimbe profile and probably issued from the Ni-rich mafic protolith. SiO2 has positive correlations with K2O, Zr, Li and Rb. Correlations of SiO2 with CaO, TiO2 and Cr are negative. Al2O3 and Fe2O3 have a positive correlation with Pb. Doudja soil samples mostly show positive Ce and Eu anomalies. The (La/Yb)N ratio is low in Tchollire soils and indicative of the low degree of lanthanide fractionation.Mass balance assessment reveals that most of the elements in Doudja have accumulated while those from Fimbe have been mostly leached. Calcium in particular has accumulated in both profiles indicating that the smectites formed may have incorporated the Ca primarily on the exchange sites.

Radioactive Barium Ion Trap Based on Metal-Organic Framework for Efficient and Irreversible Removal of Barium from Nuclear Wastewater.

Highly efficient and irreversible capture of radioactive barium from aqueous media remains a serious task for nuclear waste disposal and environmental protection. To address this task, here we propose a concept of barium ion trap based on metal-organic framework (MOF) with a strong barium-chelating group (sulfate and sulfonic acid group) in the pore structures of MOFs. The functionalized MOF-based ion traps can remove >90% of the barium within the first 5 min, and the removal efficiency reaches 99% after equilibrium. Remarkably, the sulfate-group-functionalized ion trap demonstrates a high barium uptake capacity of 131.1 mg g(-1), which surpasses most of the reported sorbents and can selectively capture barium from nuclear wastewater, whereas the sulfonic-acid-group-functionalized ion trap exhibits ultrafast kinetics with a kinetic rate constant k2 of 27.77 g mg(-1) min(-1), which is 1-3 orders of magnitude higher than existing sorbents. Both of the two MOF-based ion traps can capture barium irreversibly. Our work proposes a new strategy to design barium adsorbent materials and provides a new perspective for removing radioactive barium and other radionuclides from nuclear wastewater for environment remediation. Besides, the concrete mechanisms of barium-sorbent interactions are also demonstrated in this contribution.

Origins of elements building travertine and tufa: New perspectives provided by isotopic and geochemical tracers

Fluid/rock interaction represents a major process in the formation of calcitic or aragonitic travertine and tufa (CATT). In most cases, CATT is associated to limestone dissolution somewhere along the hydrogeological pathway. However, a wide array of other substratum (basalts, rhyolites, carbonatites, ultramafics, granites, dolomites, evaporites) can act as potential source of elements involved in the formation of CATT. This study reports on the evaluation of potential geochemical tracers linking CATT to their substratum, and unravelling the origin of elements. A large database was established from available literature data as well as new data acquired in the frame of this study for a set of Modern to Recent CATT (Ligurian ophiolites, Italy; the Chaine des Puys, Limagne graben and Paris Basin, France; Reunion Island, Indian Ocean; Jebel Oust, Tunisia). Four most reliable tracing methods are identified (1) δ13C and δ18O cross-plot allows distinguishing epigean (minδ13C=−27.2‰, maxδ13C=0.9‰, meanδ13C=−12.3‰ for N=314) from hypogean systems (minδ13C=−4‰, maxδ13C=11.7‰, meanδ13C=−2.87‰ for N=198). Very low δ13C values (<−12‰) and δ18O>−4‰ associated to negative δ13C values are specifically indicative of an ultramafic source rock. (2) Barium and strontium cross-plot helps to discriminate different groups of source rocks amongst the hypogean CATT: (i) source rocks composed of mixed limestones, evaporites, and dolomites are characterised by low barium (<100ppm) and high strontium (>400ppm) contents, (ii) mafic and granitic source rocks are undifferentiated and display similar barium (from 15 to 930ppm) and high strontium (>200ppm) contents, (iii) the carbonatite group is characterised by its exceptional high barium and strontium values. In epigean CATT, a pure limestone source rock usually relates to very low barium and strontium contents (<50ppm and <70ppm respectively), whereas mixed limestone, evaporite and dolomite source rocks generally display low strontium content (<580ppm) with higher barium content (>50ppm). (3) Relatively high beryllium content (>30ppm) in CATT seems to indicate a pure granitoid source. (4) High chromium concentrations (>20ppm) are systematically documented in Modern CATT located on an ultramafic substratum. The definition of diagnostic compositional fields for actively forming or recently formed CATT is influenced by many factors including water composition, water temperature, dissolved gas composition and concentration, biological activity, position in the sedimentary body and early diagenesis, in addition to substratum lithology. However, the results of this study illustrate that, despite these many factors, the combined use of Ba, Sr, Be, Cr, δ13C, and δ18O may be valuable to discriminate the rock lithology prevailing in the hydrogeological or palaeo-hydrogeological reservoir of CATT.

High Glass Transition Temperature Barium Silicophosphate Glasses Designed with Topological Constraint Theory

Alkali‐free glasses have attracted tremendous attentions for their high glass transition temperature (Tg). Such a feature broadens their potential applications, especially in the area of high‐density and high‐power laser glasses. BaO–P2O5 glasses, as one of the major matrix materials due to its high‐Tg, can be applied in high‐power laser glasses. Introducing SiO2 is an effective method to improve the thermal, refractive index, and mechanical properties of phosphate glasses. Herein, we studied the barium silicophosphate glasses with MAS NMR and the Tg was successfully calculated by the topological constraint theory. The designed glass (20BaO–26.7SiO2–53.3P2O5, mol%) with a high Tg (789K) was prepared and it also exhibited high refractive index and high Vickers hardness, suggesting the barium silicophosphate glasses have widespread applications in high‐power laser glasses and optical fibers.

STRUSKY PO TAVBĚ POLYMETALICKÝCH RUD Z LOKALITY ČEJKOV-TRSOV (PELHŘIMOVSKÝ RUDNÍ REVÍR)

Slags after smelting of polymetallic ores occur at the locality Čejkov-Trsov which represents medieval smelting site and lies approximately 1 030 m SE from the center of the Čejkov village. Samples collected during archaeological excavation were obtained from the Museum Vysočiny Jihlava. Bulk chemical analyses show that studied slags are dominated by SiO2-FeO-Al2O3 oxides (sum of these three components is 75.27–88.81 wt. %). Unusual are high barium (up to 9.2 wt. % of Ba) and lead contents (up to 15.0 wt. % of Pb) as well as low zinc contents (230–3780 ppm). All samples except one are generally CaO poor (an exception is sample CT4 containing 6.03 wt. % CaO) which probably refl ect lack of CaO – based additives. Light microscopy and EDS analyses on an electron microprobe proved following phases: spinelides, olivine, feldspars, pyroxene, glass and quartz. Spinelides are the most variable in their composition ranging from almost pure magnetite (92 mol. % of magnetite, 5 mol. % of spinel and 3 mol. % of galaxite) to spinel-rich hercynite (50 mol. % of hercynite, 45 mol. % of spinel and 5 mol. % of magnetite). Olivine is represented by fayalite (89–90 mol. % Fa, 5–7 mol. % Te, 4–5 mol. % Fo). Newly formed feldspars are present in all studied samples and contain up to 22.8 wt. % of BaO (44–50 mol. % of orthoclase, 40–47 mol. % of celsiane and 9–11 mol. % of albite). Ca-Fe pyroxene (Fs52Wo38En11–Fs51Wo37En13) was formed probably due to high enough temperature and a sufficient CaO content. Cracked quartz grains are present within all samples. They were more or less corroded by a slag melt.

High capacitive amorphous barium nickel phosphate nanofibers for electrochemical energy storage

BaxNi3−x(PO4)2(0 &lt;x&lt; 3) amorphous nanofibers with excellent supercapacitive performance were synthesized through a facile cation-exchange method.

On the solid-state formation of BaTiO3 nanocrystals from mechanically activated BaCO3 and TiO2 powders: innovative mechanochemical processing, the mechanism involved, and phase and nanostructure evolutions

It still remains a challenge for the scientific community to obtain high quality barium titanate nanocrystals using high-energy ball mills while avoiding unwanted (carbonate) by-products. The current work addresses this challenge by developing a new solid-state methodology.

Optical properties of high density barium borate glass for gamma ray shielding applications

Study of optical and gamma rays shielding properties were performed in glassy system of xBaO–5MgO–8Na2O–(87 − x)B2O3, previously prepared by melt-quenching technique. The optical properties of the glass samples have been obtained using UV–Vis measurements. The WinXCom computer program (version 3.1) and Auto Zeff program (version 1.7) were used to calculate the mass attenuation coefficients and effective atomic numbers, respectively, of γ-photon energies from 1 keV up to 1 GeV. The results reflected that, an addition of BaO improves the studied properties of the glass samples; hence the reported glassy system can find applications in the areas of nuclear radiation-shielding.

Evaluation of procedures for 226Ra determination in samples with high barium concentration by α-particle spectrometry

The γ emitter 133Ba is the most often used tracer in determination of 226Ra by α-particle spectrometry. If the source for α-particle spectrometry is prepared by microcoprecipitation, a high Ba concentration causes a thicker source layer which results in reduced counting efficiency due to self-absorption on the α spectrometer and consequently lower result for 226Ra, while not effecting the measurement of 133Ba in γ-ray spectrometry. If the electrodeposition is used, recoveries of deposited Ra and Ba are not necessarily the same and impurities of other α emitters may interfere with the α spectrum.

Design of Light Multi-layered Shields for Use in Diagnostic Radiology and Nuclear Medicine via MCNP5 Monte Carlo Code

Introduction Lead-based shields are the most widely used attenuators in X-ray and gamma ray fields. The heavy weight, toxicity and corrosion of lead have led researchers towards the development of non-lead shields. Materials and Methods The purpose of this study was to design multi-layered shields for protection against X-rays and gamma rays in diagnostic radiology and nuclear medicine. In this study, cubic slabs composed of several materials with high atomic numbers, i.e., lead, barium, bismuth, gadolinium, tin and tungsten, were simulated, using MCNP5 Monte Carlo code. Cubic slabs (30×30×0.05 cm3) were simulated at a 50 cm distance from the point photon source. The X-ray spectra of 80 kVp and 120 kVp were obtained, using IPEM Report 78. The photon flux following the use of each shield was obtained inside cubic tally cells (1×1×0.5 cm3) at a 5 cm distance from the shields. The photon attenuation properties of multi-layered shields (i.e., two, three, four and five layers), composed of non-lead radiation materials, were also obtained via Monte Carlo simulations. Results Among different shield designs proposed in this study, the three-layered shield, composed of tungsten, bismuth and gadolinium, showed the most significant attenuation properties in radiology, with acceptable shielding at 140 keV energy in nuclear medicine. Conclusion According to the results, materials with k-edges equal to energies common to diagnostic radiology can be proper substitutes for lead shields.

High quality barium titanate nanofibers for flexible piezoelectric device applications

Piezoelectric and ferroelectric nanostructures and devices have attracted extensive attention because they can realize the conversion between mechanical and electrical energies for sensors and energy harvesting applications. In the present work high quality lead-free BaTiO3 nanofibers were obtained by a sol-gel based electrospinning technique. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and piezoresponse force microscopy (PFM) were utilized to characterize the morphologies, phase and domain structures along with the nanoscale electromechanical response. Well-crystallized BaTiO3 fibers were obtained with good local piezoelectric response (d33,eff of ∼40pm/V using PFM). Further, a flexible piezoelectric device was fabricated by combining aligned BaTiO3 nanofibers and a PDMS polymer matrix. An inter-digital electrode on a flexible substrate was incorporated to enhance the output signal. The proposed device displayed an output peak–peak voltage of ∼0.45V at a load resistance of 1MΩ under a periodic bending excitation of ∼45Hz. It has the advantages of small-size, ease of processing, high flexibility and strain tolerance, and high-sensitivity to external vibration at low-frequency which may open up a range of new applications.

Highly aligned arrays of high aspect ratio barium titanate nanowires via hydrothermal synthesis

We report on the development of a hydrothermal synthesis procedure that results in the growth of highly aligned arrays of high aspect ratio barium titanate nanowires. Using a multiple step, scalable hydrothermal reaction, a textured titanium dioxide film is deposited on titanium foil upon which highly aligned nanowires are grown via homoepitaxy and converted to barium titanate. Scanning electron microscope images clearly illustrate the effect the textured film has on the degree of orientation of the nanowires. The alignment of nanowires is quantified by calculating the Herman's Orientation Factor, which reveals a 58% improvement in orientation as compared to growth in the absence of the textured film. The ferroelectric properties of barium titanate combined with the development of this scalable growth procedure provide a powerful route towards increasing the efficiency and performance of nanowire-based devices in future real-world applications such as sensing and power harvesting.

Analytical Method for Measuring Cosmogenic (35)S in Natural Waters.

Cosmogenic sulfur-35 in water as dissolved sulfate ((35)SO4) has successfully been used as an intrinsic hydrologic tracer in low-SO4, high-elevation basins. Its application in environmental waters containing high SO4 concentrations has been limited because only small amounts of SO4 can be analyzed using current liquid scintillation counting (LSC) techniques. We present a new analytical method for analyzing large amounts of BaSO4 for (35)S. We quantify efficiency gains when suspending BaSO4 precipitate in Inta-Gel Plus cocktail, purify BaSO4 precipitate to remove dissolved organic matter, mitigate interference of radium-226 and its daughter products by selection of high purity barium chloride, and optimize LSC counting parameters for (35)S determination in larger masses of BaSO4. Using this improved procedure, we achieved counting efficiencies that are comparable to published LSC techniques despite a 10-fold increase in the SO4 sample load. (35)SO4 was successfully measured in high SO4 surface waters and groundwaters containing low ratios of (35)S activity to SO4 mass demonstrating that this new analytical method expands the analytical range of (35)SO4 and broadens the utility of (35)SO4 as an intrinsic tracer in hydrologic settings.

Ba-RICH K-FELDSPAR FROM MAFIC XENOLITHS WITHIN MESOARCHEAN GRANITIC ROCKS, BEARTOOTH MOUNTAINS, MONTANA, USA: INDICATORS FOR BARIUM METASOMATISM

A mafic xenolith included within 2.8 Ga granitic rocks from the eastern Beartooth Mountains of Montana, USA shows evidence of significant Ba metasomatism related to an influx of hydrous fluids under lower amphibolite-facies conditions, and is indicated by the development of “hyalophane”. The volumetrically dominant Mesoarchean host rocks include granodioritic-granitic-tonalitic gneisses that have variable and high barium (Ba) contents, with some rocks exceeding 3500 ppm Ba. The mafic xenolith retains some textural features inherited from its igneous tonalitic protolith, but it was affected by multi-stage metamorphic overprints. An initial amphibolite-facies overprint generated a distinctive texture, mineral assemblage, and mineral chemistry, but these features are locally replaced by mineral assemblages and chemistry that result from infiltration of lower-temperature Ba-rich hydrous fluids. The original amphibolite facies assemblage is magnesio-hornblende + plagioclase (An 35 ) + biotite + quartz + titanite + allanite + zircon. Thermobarometry indicates peak conditions of ~660 °C and ~7 kbar partially overprinted by a later, fluid-rich metamorphism at ~550 °C. Submillimeter-scale regions modified by the invasive fluid are characterized by a change in texture denoted by vermicular epidote, epidote overgrowths on allanite cores, myrmekitic plagioclase (~An 20 ), and complexly zoned hyalophane. Hyalophane grains locally have interior regions with a low celsian component (Cn,BaAl 2 Si 2 O 8 ) of ~Cn 7 flanked by more enriched zones of up to Cn 27 . Very fine exsolution lamellae of albite-hair perthite are observed in the central zone of the low-Cn “hyalophane”. The Ba-rich hydrous fluid is considered to have been derived from the surrounding granitic rocks. Ultimately, the most likely source of the Ba is subducted sediments in a Mesoarchean subduction zone where fluids generated from Ba-enriched sediments were incorporated into fluids associated with formation of the 2.8 Ga granitic rocks. Upon crystallization of the granitic rocks, a Ba-enriched metasomatic fluid was released to develop “hyalophane” in the mafic xenolith.

Effects of Fabrication Conditions on the Crystallinity, Barium Deficiency, and Conductivity of BaZr0.8Y0.2O3–δ Films Grown by Pulsed Laser Deposition

AbstractYttrium‐doped barium zirconate (BZY) thin films were deposited on MgO and sapphire substrates using a pulsed‐laser deposition (PLD) method with varying deposition rates. The films deposited with a low deposition rate exhibited highly oriented microstructures with little grain boundaries. The electrical conductivities of these films were higher than those of the films, deposited with high deposition rates, which showed little‐oriented polycrystalline microstructure. While the films deposited on the MgO substrates had a stoichiometric composition, those deposited on the sapphire substrates had a high barium deficiency, which was possibly due to the differences in the crystal structure and large lattice mismatch between the sapphire substrate and the BZY film. The electrical conductivity of the highly oriented BZY film, grown on MgO substrate with a low deposition rate, showed little barium deficiency and the highest conductivity value that is higher than the typical conductivity of sintered pellets.

Effects of magnetic pre-alignment of nano-powders on formation of high textured barium hexa-ferrite quasi-single crystals via a magnetic forming and liquid participation sintering route

Highly textured barium hexa-ferrite quasi-single crystal with narrow ferromagnetic resonance line-width is believed to be a potential gyromagnetic material for self-biased microwave devices. To fabricate barium hexa-ferrite quasi-single crystal with a high grain orientation degree, a magnetic forming and liquid participation sintering route has been developed. In this paper, the effects of the pre-alignment of the starting nano-powders on the formation of barium quasi-single crystal structures have been investigated. The results indicated that: the crystallites with large sizes and small specific surfaces were easily aligned for they got higher driving forces and lower resistances during magnetic forming. The average restricting magnetic field was about 4.647kOe to overcome the average friction barrier between crystallites. The pre-aligned crystallites in magnetic forming acted as the “crystal seeds” for oriented growth of the un-aligned crystallites during liquid participation sintering to achieve a high grain orientation. To effectively promote the grain orientation degrees of the sintered pellets, the grain orientation degrees of the green compacts must be higher than a limited value of 15.0%. Barium hexa-ferrite quasi-single crystal with a high grain orientation degree of 98.6% was successfully fabricated after sintering the green compact with its grain orientation degree of 51.1%.

The Selene Obsidian Source (Formerly Sonora Unknown B) of the Upper Río Bavispe Basin, Sonora, Mexico

An energy-dispersive X-ray fluorescence (EDXRF) analysis of nineteen obsidian source rocks from a mid-Tertiary rhyolite/perlite flow in the upper Río Bavispe basin of northeastern Sonora, Mexico solves the location of “Sonora Unknown B” as reported by ) for recent archaeological projects in northeastern Sonora and southeastern Arizona. This newly discovered source, called Selene, is a relatively large marekanite source consisting of a very high-silica rhyolite with regionally distinct high barium (Ba) and strontium (Sr) values, and low zirconium (Zr) elemental concentrations. The Selene nodules are relatively large compared to nodules from other northern Sonoran and Chihuahuan obsidian sources, and have excellent knapping qualities. We believe these attributes contributed to the transport, trade, and use of Selene obsidian hundreds of kilometers from the source. This is in contrast to marekanites from some other sources in northwestern Mexico, which were at most transported and used a few tens of kilometers from their sources (; :77).

High barium content lead and alkaline-free glasses

Four glass compositions of the system BaO-Al2O3-SiO2 with high content of BaO>50% mol and with B2O3 addition (3–10wt%) were melted at 1400°C. The effect of alkaline earth BaO oxide on the glass phase separation and on refraction index n is investigated. IR and MAS-NMR spectroscopy are used for structural characterization. Finally stable alkaline free glasses with a content of BaO ranging from 47.4Mol.% to 54.5Mol.% and with a n=1.62±0.01at 468.1nm have been obtained.

Synthesis and properties of single domain sphere-shaped barium hexa-ferrite nano powders via an ultrasonic-assisted co-precipitation route

To synthesize high quality barium hexa-ferrite nano powders, an ultrasonic-assisted co-precipitation method has been used and the influences of the ultrasonic technique on the particle morphologies and magnetic properties of the synthesized barium hexa-ferrite nano powders have been investigated. The results indicated that the introduction of ultrasonic energy into the co-precipitation process promoted the composition homogeneities of the co-precipitated precursors, minished their particle sizes, and exerted the additional surface barriers between the particles, which influenced both the phase formation and particle growth-up processes during the subsequent heating treatment and altered the particle sizes, size distributions and particle shapes of the final synthesized powders. The average particle sizes of the synthesized nano powders dramatically decreased from 210nm to about 100nm as the inputting ultrasonic power increased, while the size distribution became increasingly uniform except for a few of large particles existed as the inputting power approached to a high value. The magnetization at 1.4 T of the as-synthesized barium hexa-ferrite dramatically increased and approached to the highest value of 57.9emu/g due to the elimination of multi-domain particles, the alleviation of particle adhesion and the evolution of particle shape from flake to quasi-sphere as well as the uniform particle size distribution as the ultrasonic assistance was employed, and slightly decreased because of the coarsening in particle sizes.