[Tartrate-resistant acid phosphatase in free-living Amoeba proteus].

PubMed

Sopina, V A

2002-01-01

Tartrate-resistant acid phosphatase (TRAP) of Amoeba proteus (strain B) was represented by 3 of 6 bands (= electromorphs) revealed after disc-electrophoresis in polyacrylamide gels with the use of 2-naphthyl phosphate as a substrate at pH 4.0. The presence of MgCl2, CaCl2 or ZnCl2 (50 mM) in the incubation mixture used for gel staining stimulated activities of all 3 TRAP electromorphs or of two of them (in the case of ZnCl2). When gels were treated with MgCl2, CaCl2 or ZnCl2 (10 and 100 mM, 30 min) before their staining activity of TRAP electromorphs also increased. But unlike 1 M MgCl2 or 1 M CaCl2, 1 M ZnCl2 partly inactivated two of the three TRAP electromorphs. EDTA and EGTA (5 mM), and H2O2 (10 mM) completely inhibited TRAP electromorphs after gel treatment for 10, 20 and 30 min, resp. Of 5 tested ions (Mg2+, Ca2+, Fe2+, Fe3+ and Zn2+), only the latter reactivated the TRAP electromorphs previously inactivated by EDTA or EGTA treatment. In addition, after EDTA inactivation, TRAP electromorphs were reactivated better than after EGTA. The resistance of TRAP electromorphs to okadaic acid and phosphatase inhibitor cocktail 1 used in different concentrations is indicative of the absence of PP1 and PP2A among these electromorphs. Mg2+, Ca2+ and Zn2+ dependence of TRAP activity, and the resistance of its electromorphs to vanadate and phosphatase inhibitor cocktail 2 prevents these electromorphs from being classified as PTP. It is suggested that the active center of A. proteus TRAP contains zinc ion, which is essential for catalytic activity of the enzyme. Thus, TRAP of these amoebae is metallophosphatase showing phosphomonoesterase activity in acidic medium. This metalloenzyme differs from both mammalian tartrate-resistant PAPs and tartrate-resistant metallophosphatase of Rana esculenta.

Inorganic profile of some Brazilian medicinal plants obtained from ethanolic extract and ''in natura'' samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferreira, M.O.M.; de Sousa, P.T.; Salvador, V.L.R.

The Anadenathera macrocarpa, Schinus molle, Hymenaea courbaril, Cariniana legalis, Solidago microglossa and Stryphnodendron barbatiman, were collected ''in natura'' samples (leaves, flowers, barks and seeds) from different commercial suppliers. The pharmaco-active compounds in ethanolic extracts had been made by the Mato Grosso Federal University (UFMT). The energy-dispersive x-ray fluorescence (ED-XRF) spectrometry was used for the elemental analysis in different parts of the plants and respective ethanolic extracts. The Ca, Cl, Cu, Fe, K, Mg, Mn, Na, Ni, P, Rb, S, Sr and Zn concentrations were determined by the fundamental parameters method. Some specimens showed a similar inorganic profile for ''in natura''more » and ethanolic extract samples and some ones showed a distinct inorganic profile. For example, the Anadenathera macrocarpa showed a similar concentration in Mg, P, Cu, Zn and Rb elements in ''in natura'' and ethanolic extract samples; however very different concentration in Na, S, Cl, K , Ca, Mn, Fe and Sr was observed in distinctive samples. The Solidago microglossa showed the K, Ca, Cl, S, Mg, P and Fe elements as major constituents in both samples, suggesting that the extraction process did not affect in a considerable way the ''in natura'' inorganic composition. The elemental composition of the different parts of the plants (leaves, flowers, barks and seeds) has been also determined. For example, the Schinus molle specimen showed P, K, Cl and Ca elements as major constituents in the seeds, Mg, K and Sr in the barks and Mg, S, Cl and Mn in the leaves, demonstrating a differentiated elementary distribution. These inorganic profiles will contribute to evaluate the quality control of the Brazilian herbaceous trade and also will assist to identify which parts of the medicinal plants has greater therapeutic effect.« less

Synthesis and crystal structure of Fe[(Te1.5Se0.5)O5]Cl, the first iron compound with selenate(IV) and tellurate(IV) groups

NASA Astrophysics Data System (ADS)

Akhrorov, Akhmad Yu; Kuznetsova, Elena S.; Aksenov, Sergey M.; Berdonosov, Peter S.; Kuznetsov, Alexey N.; Dolgikh, Valery A.

2017-12-01

During the search for selenium analogues of FeTe2O5Cl, the new iron (III) tellurate(IV) selenate(IV) chloride with the composition Fe[(Te1.5Se0.5)O5]Cl was synthesized by chemical vapor transport (CVT) reaction and characterized by TGA-, EDX-,SCXRD-analysis, as well as IR and Raman spectroscopy. It was found that Fe[(Te1.5Se0.5)O5]Cl crystallizes in the monoclinic space group P21/c with unitcell parameters a = 5.183(3) Å, b = 15.521(9) Å, c = 7.128(5) Å and β = 107.16(1)°. The crystal structure of Fe[(Te1.5Se0.5)O5]Cl represents a new structure type and contains electroneutral heteropolyhedral layers formed by dimers of the [FeO5Cl]8- octahedra, linked via common O-O edges, and mixed [Te3SeO10]4- tetramers. Adjacent layers are stacked along the b axis and linked by weak residual bonds. The new compound is stable up to 420 °C. DFT calculations predict Fe[(Te1.5Se0.5)O5]Cl to be a wide-gap semiconductor with the band gap of ca. 2.7 eV.

Rates of cuticular penetration of chelated Fe(III): role of humidity, concentration, adjuvants, temperature, and type of chelate.

PubMed

Schönherr, Jörg; Fernández, Victoria; Schreiber, Lukas

2005-06-01

Time courses of cuticular penetration of FeCl3 and Fe(III) complexes of citric acid, EDTA, EDDHA (Sequestrene 138Fe), imidodisuccinic acid (IDHA), and ligninsulfonic acid (Natrel) were studied using astomatous cuticular membranes (CMs) isolated from Populus x canescens leaves. At 100% relative humidity, the Fe(III) chelates disappeared exponentially with time from the surface of the CMs; that is, penetration was a first-order process that can be described using rate constants or half-times of penetration (t(1/2)). Half-times ranged from 20 to 30 h. At 90% humidity, penetration rates were insignificant with the exception of Natrel, for which t(1/2) amounted to 58 h. Rate constants were independent of temperature (15, 25, and 35 degrees C). Permeability decreased with increasing Fe chelate concentration (IDHA and EDTA). At 100% humidity, half-times measured with FeIDHA were 11 h (2 mmol L(-1)), 17 h (10 mmol L(-1)) and 36 h (20 mmol L(-1)), respectively. In the presence of FeEDTA, penetration of CaCl2 was slowed greatly. Half-times for penetration of CaCl2, which were 1.9 h in the absence of FeEDTA, rose to 3.12 h in the presence of an equimolar concentration of EDTA and 13.3 h when the FeEDTA concentration was doubled. Hence, Fe chelates reduced permeability of CMs to CaCl2 and to the Fe chelates themselves. It is suggested that Fe chelates reduced the size of aqueous pores. This view is supported by the fact that rate constants for calcium salts were about 5 times higher than for Fe chelates with the same molecular weights. Adding Tween 20 (5 g L(-1)) as a humectant did not increase permeability to FeIDHA at 90% humidity and below, while addition of glycine betaine did. Penetration of FeCl3 applied at 5 g L(-1) (pH 1.5) was not a first order process as rate constants decreased rapidly with time. Only 2% of the dose penetrated during the first 2 h and less than that in the subsequent 8 h. Recovery was only 70%. This was attributed to the formation of insoluble Fe hydroxide precipitates on CMs. These results explain why in the past foliar application of Fe compounds had limited success. Inorganic Fe salts are instable and phytotoxic because of low pH, while Fe chelates penetrate slowly and 100% humidity is required for significant penetration rates. Concentrations as low as reasonably possible should be used. These physical facts are expected to apply to stomatous leaf surfaces as well, but absolute rates probably depend on leaf age and plant species. High humidity in stagnant air layers may favor penetration rates across stomatous leaf surfaces when humidity in bulk air is below 100%.

Arbuscular mycorrhizas enhance nutrient uptake in different wheat genotypes at high salinity levels under field and greenhouse conditions.

PubMed

Mardukhi, Baran; Rejali, Farhad; Daei, Gudarz; Ardakani, Mohammad Reza; Malakouti, Mohammad Javad; Miransari, Mohammad

2011-07-01

Since most experiments regarding the symbiosis between arbuscular mycorrhizal (AM) fungi and their host plants under salinity stress have been performed only under greenhouse conditions, this research work was also conducted under field conditions. The effects of three AM species including Glomus mosseae, G. etunicatum and G. intraradices on the nutrient uptake of different wheat cultivars (including Roshan, Kavir and Tabasi) under field and greenhouse (including Chamran and Line 9) conditions were determined. At field harvest, the concentrations of N, Ca, Mg, Fe, Cu, and Mn, and at greenhouse harvest, plant growth, root colonization and concentrations of different nutrients including N, K, P, Ca, Mg, Mn, Cu, Fe, Zn, Na and Cl were determined. The effects of wheat cultivars on the concentrations of N, Ca, and Mn, and of all nutrients were significant at field and greenhouse conditions, respectively. In both experiments, AM fungi significantly enhanced the concentrations of all nutrients including N, K, P, Ca, Mg, Mn, Cu, Fe, Zn, Na and Cl. The synergistic and enhancing effects of co-inoculation of AM species on plant growth and the inhibiting effect of AM species on Na(+) rather than on Cl(-) uptake under salinity are also among the important findings of this research work. Copyright © 2011 Académie des sciences. Published by Elsevier SAS. All rights reserved.

Determination of suitable chemical extraction methods for the available iron content of brown forest soils in Turkey

NASA Astrophysics Data System (ADS)

Adiloglu, Aydin

2006-09-01

The aim of this research was to determine the available iron (Fe) content of brown forest soils of Edirne Province and the most suitable chemical extraction method. Eight chemical extraction methods (the 0.005 M DTPA + 0.01 M CaCl2 + 0.1 MTEA, 0.05 M HCl + 0.012 M H2SO4, 1 M NH4OAc (pH: 4.8), 0.01 M EDTA + 1 M NH4OAc, 1 M MgCl2, 0.01 M EDTA + 1 M (NH4)2CO3, 0.005 M DTPA + 1 M NH4HCO3, and 0.001 M EDDHA methods) and six biological indices (the dry matter yield, Fe concentration, Fe uptake, relative dry matter yield, relative Fe concentration, and relative Fe uptake) were compared. The biological indices were determined with barley (Hordeum vulgare L.) grown under greenhouse conditions. At the end of the experiment, the highest correlation coefficients (r) were determined to be between the 0.005 M DTPA + 0.01 M CaCl2 + 0.1 M TEA method and the biological indices and between the 0.005 M DTPA + 1 M NH4HCO3 method and the biological indices. The corresponding correlation coefficients (r) for the 0.005 M DTPA + 0.01 M CaCl2 + 0.1 M TEA method and the six biological indices were 0.621**, 0.823**, 0.810** 0.433**, 0.558**, and 0.640**, respectively. For the 0.005 M DTPA + 1 M NH4HCO3 method, these coefficients were equal to 0.618**, 0.520**, 0.679**, 0.521**, 0.492**, and 0.641**, respectively (** indicate the validity of the relationships at p < 0.01) These extraction methods, out of all the methods tested, were suggested for the determination of the available Fe content of the brown forest soils.

Cathodoluminescence microscopy and spectroscopy of forsterite from Kaba meteorite: An application to the study of hydrothermal alteration of parent body

NASA Astrophysics Data System (ADS)

Gucsik, Arnold; Endo, Taro; Nishido, Hirotsugu; Ninagawa, Kiyotaka; Kayama, Masahiro; Bérczi, Szaniszló; Nagy, Szabolcs; Ábrahám, Péter; Kimura, Yuki; Miura, Hitoshi; Gyollai, Ildikó; Simonia, Irakli; Rózsa, Péter; Posta, József; Apai, Dániel; Mihályi, Krisztián; Nagy, Mihály; Ott, Ulrich

2013-12-01

Highly forsteritic olivine (Fo: 99.2-99.7) in the Kaba meteorite emits bright cathodoluminescence (CL). CL spectra of red luminescent forsterite grains have two broad emission bands at approximately 630 nm (impurity center of divalent Mn ions) in the red region and above 700 nm (trivalent Cr ions) in the red-IR region. The cores of the grains show CL blue luminescence giving a characteristic broad band emission at 400 nm, also associated with minor red emissions related to Mn and Cr ions. CL color variation of Kaba forsterite is attributed to structural defects. Electron probe microanalyzer (EPMA) analysis shows concentrations of Ca, Al, and Ti in the center of the forsterite grain. The migration of diffusible ions of Mn, Cr, and Fe to the rim of the Kaba meteoritic forsterite was controlled by the hydrothermal alteration at relatively low temperature (estimated at about 250 °C), while Ca and Al ions might still lie in the core. A very unusual phase of FeO (wüstite) was also observed, which may be a terrestrial alteration product of FeNi-metal.

Elemental concentration analysis in brain structures from young, adult and old Wistar rats by total reflection X-ray fluorescence with synchrotron radiation

NASA Astrophysics Data System (ADS)

Serpa, R. F. B.; de Jesus, E. F. O.; Anjos, M. J.; do Carmo, M. G. T.; Moreira, S.; Rocha, M. S.; Martinez, A. M. B.; Lopes, R. T.

2006-11-01

The knowledge of the spatial distribution and the local concentration of trace elements in tissues are of great importance since trace elements are involved in a number of metabolic and physiological processes in the human body, and their deficiency and excess may lead to different metabolic disorders. In this way, the main goal of this work is to compare the elemental concentration in different brain structures, namely temporal cortex, entorhinal cortex, visual cortex and hippocampus, from Wistar female rats ( n = 15) with different ages: 2, 8 and 48 weeks. The measurements were performed at the Synchrotron Light Brazilian Laboratory, Campinas, São Paulo, Brazil. In the entorhinal cortex, the following elements decreased with age: Zn, S, Cl, K, Ca and Br. In the temporal cortex, Ca, Fe and Br levels increased with aging and on the other hand, P, S, Cl, K and Rb levels decreased with aging. In the visual cortex almost all the elements decreased with aging: Cl, Ca, Fe, Ni and Zn. In the hippocampus, in turn, most of the elements identified, increased with aging: Al, P, S, K, Fe, Cu, Zn and Rb. The increase of Fe with aging in the hippocampus is an important fact that will be studied, since it is involved in oxidative stress. It is believed that oxidative stress is the one of the main causes responsible for neuronal death in Parkinson's disease.

Metal ion-oxytetracycline pharmacokinetic interactions after oral co-administration in broiler chickens.

PubMed

Ziółkowski, H; Jasiecka, A; Zuśka-Prot, M; Przybysz, J; Grabowski, T; Jaroszewski, J J

2016-08-01

The influence of the composition of calcium (Ca(2+)), magnesium (Mg(2+)), and iron (Fe(3+)) ions in two concentration levels (low-500 mg/L of CaCl2, 125 mg/L of MgCl2, and 10 mg/L of FeCl3 and high-2,500 mg/L of CaCl2, 625 mg/L of MgCl2, and 50 mg/L of FeCl3) contained in water on the pharmacokinetics (PK) of oxytetracycline (OTC) was determined. OTC hydrochloride was administered at a dose of 25 mg/kg of body weight to broiler chickens divided into four groups of nine birds each, including 3 oral groups (in deionized water -control, in water with low ion concentration, and in water with high ion concentration) and 1 intravenous group. OTC concentrations in plasma were determined using liquid chromatography-tandem mass spectrometry, after which non-compartmental pharmacokinetic analysis was conducted.The absolute bioavailability of OTC in the group of birds exposed to higher ions concentration was reduced (8.68% ± 2.56) as compared to the control (13.71% ± 2.60). Additionally, in this group, decrease in PK parameters such as: area under the concentration-time curve from 0 to infinity (15.36 μg × h/mL ± 4.36), from 0 to t (14.78 μg × h/mL ± 4.37), area under the first moment of curve from 0 to t (107.54 μg × h/mL ± 36.48), and maximum plasma concentration (2.13 μg/mL ± 0.32) were also observed. It is noteworthy, all mentioned parameters demonstrated a downward trend with high correlation coefficient (P = 0.004, P = 0.002, P = 0.005, P = 0.004, P = 0.011, respectively), reflecting the influence of increasing concentrations of Ca(2+), Mg(2+), and Fe(3+) ions on the decreasing absorption rate of OTC.Based on the current research results, it can be assumed that high concentrations of several ions applied concomitantly are able to decrease the absorption of OTC from gastrointestinal tract in broiler chickens. This occurrence might impair the drug's clinical efficacy toward some pathogenic microorganisms. It implies that using OTC on a farm may require administration of higher doses than the routine one when infections are caused by less sensitive pathogens. © 2016 Poultry Science Association Inc.

One pot synthesis of exchange coupled Nd2Fe14B/alpha-Fe by pechini type sol-gel method.

PubMed

Hussain, Abid; Jadhav, Abhijit P; Baek, Yeon Kyung; Choi, Hul Jin; Lee, Jaeho; Kang, Young Soo

2013-11-01

In this work, a combination of nanoparticles of Nd2Fe14B hard magnetic phase and alpha-Fe soft magnetic phase were synthesized by one pot chemical synthesis technique using sol-gel method. A gel of Nd-Fe-B was prepared using NdCl3 x 6H2O, FeCl3 x 6H2O, H3BO3, citric acid, and ethylene glycol by pechini type sol-gel method. The gel was subsequently calcined and annealed to obtain the mixed oxide powders. The produced metal oxide particles were identified with XRD, SEM, TEM to obtain the crystal structure, shape and domain structure of them. The nanoparticles of mixed phase of Nd2Fe14B/alpha-Fe were obtained from these oxides by a process of reduction-diffusion in vacuum by employing CaH2 as reducing agent. During this process it was optimized by controlling temperature, reaction time and concentration of the reducing agent (CaH2). The phase formation of Nd2Fe14B was resulted by the direct diffusion of NdH2, Fe and B. The magnetic property of produced hard and soft phases was successfully identified with vibrating sample magnetometer (VSM). The mixed domains of the hard and soft phases were identified with selected area electron diffraction method (SAED) patterns.

The effect of metal salts on the decomposition of sweet sorghum bagasse in flow-through liquid hot water.

PubMed

Yu, Qiang; Zhuang, Xinshu; Yuan, Zhenhong; Qi, Wei; Wang, Qiong; Tan, Xuesong

2011-02-01

The impact of the metal salts NaCl, KCl, CaCl(2), MgCl(2), FeCl(3), FeCl(2), and CuCl(2), particularly the latter, on the decomposition of hemicellulose and lignin from sweet sorghum bagasse in liquid hot water pretreatment processing was studied in an attempt to enhance the recovery of sugars. Transition metal chlorides significantly enhanced the hemicellulose removal compared to the alkaline earth metal chlorides and alkaline metal chlorides, contributing to the formation of a saccharide-metal cation intermediate complex. FeCl(2) greatly increased xylose degradation and about 60% xylan was converted into non-saccharide products. In contrast, an excellent total and monomeric xylose recovery was obtained after the CuCl(2) pretreatment. Most of the lignin was deposited on the surface of the residual solid with droplet morphologies after this pretreatment, and about 20% was degraded into monomeric products. The total recovery of sugars from sweet sorghum bagasse with 0.1% CuCl(2) solution pretreatment and 48 h enzymatic digestibility, reached 90.4%, which is superior to the recovery using hot water pretreatment only. Copyright © 2010 Elsevier Ltd. All rights reserved.

40 CFR 796.3100 - Aerobic aquatic biodegradation.

Code of Federal Regulations, 2011 CFR

2011-07-01

... reservoir. The reservoir access port is easily sealed during incubation with a serum bottle stopper. Two... II 2 KCl 10 MgSO4 20 FeSO4·7H2O 1 III CaCl2 5 ZnCl2 0.05 MnCl2·4H2O 0.5 CuCl2 0.05 CoCl2 0.001 H3 BO3... wool, and supplemented with 25 mg/L each of Difco vitamin-free casamino acids and yeast extract...

40 CFR 796.3100 - Aerobic aquatic biodegradation.

Code of Federal Regulations, 2010 CFR

2010-07-01

... reservoir. The reservoir access port is easily sealed during incubation with a serum bottle stopper. Two... II 2 KCl 10 MgSO4 20 FeSO4·7H2O 1 III CaCl2 5 ZnCl2 0.05 MnCl2·4H2O 0.5 CuCl2 0.05 CoCl2 0.001 H3 BO3... wool, and supplemented with 25 mg/L each of Difco vitamin-free casamino acids and yeast extract...

Trace element composition and cathodoluminescence of kyanite and its petrogenetic implications

NASA Astrophysics Data System (ADS)

Müller, Axel; van den Kerkhof, Alfons M.; Selbekk, Rune S.; Broekmans, Maarten A. T. M.

2016-09-01

Kyanite crystals from fourteen localities worldwide were analysed for their abundances of the trace elements Na, Mg, K, Ca, Ti, V, Cr, Mn, and Fe and cathodoluminescence (CL) properties. Based on protolith type, metamorphic setting, and distinctive trace element fingerprints, a genetic classification of kyanite-bearing rocks is suggested: (A) Al-rich metasediments which commonly contain coarse-grained quartz-kyanite segregations; (B) metamorphosed granitic rocks, specifically granulites; (C) metamorphosed argillic alteration zones hosted originally in felsic igneous rocks; (D) metamorphosed argillic alteration zones hosted originally in mafic igneous rocks; and (E) metamorphosed mafic to ultramafic rocks, specifically eclogites. Vanadium and Cr concentrations reflect both protolith and host rock compositions and therefore may provide a geochemical fingerprint for the nature of the protolith. The incorporation of Fe into kyanite is largely controlled by oxygen fugacity during kyanite formation, and therefore, in most cases, its concentration cannot be related to that of the protolith. From our results, Ti concentration appears to be related to metamorphic grade, particularly formation temperature. If proven by further studies, Ti-in-kyanite may provide a useful geothermometer. Correlation of trace element abundances with CL spectra confirms that common red CL, which is composed of the spectral bands centred at 1.69 eV (734 nm), 1.75 eV (708 nm), and 1.80 eV (689 nm), is related to Cr3+ defects. CL spectra of most kyanites show in addition a low-intensity blue emission centred at 2.56 eV (485 nm). Correlation of the intensity of the blue emission with Ti suggests that it is related to or sensitized by Ti4+ or Ti3+ defects. Kyanites with >3200 µgg-1 Fe show generally no detectable CL due to the CL-quenching effect of Fe2+. Our findings provide new criteria in the exploration for and quality assessment of new kyanite deposits. The Ti content, one of the critical contaminants of kyanite products, besides Fe, Ca, and Mg, appears predictable from the observed correlation of Ti with formation temperature. Iron will be hard to predict because its incorporation is mainly controlled by the oxidizing conditions during kyanite formation and the estimation of these conditions requires advanced analytical methods. Magnesium and Ca are consistently low in all investigated samples. From a regional exploration viewpoint, group C and D kyanites have the lowest Ti and relative low Fe and, therefore, will be most refractory. Due to their attractive blue colour, kyanite-bearing rocks of group C have potential as ornamental or dimension stone.

Geochemical behaviour of PM10 aerosol constituents under the influence of succeeding anticyclonic/cyclonic situations: case of Sfax City, southern Tunisia.

PubMed

Bahloul, Moez; Chabbi, Iness; Dammak, Rim; Amdouni, Ridha; Medhioub, Khaled; Azri, Chafai

2015-12-01

The present study investigates the geochemical behaviour of PM10 aerosol constituents (Cl, Na, Si, Al, Ca, Fe, Mg, Mn, Pb, Zn, S) at Sfax City (Tunisia) under succeeding meteorological conditions, including short-lived anticyclonic, cyclonic and prolonged anticyclonic situations. The results revealed daily total concentrations fluctuating between 4.07 and 88.51 μg/m(3). The highest level recorded was noted to occur under the effect of the short-lived anticyclonic situation characterized by low wind speeds. It was 1.5 times higher than those recorded during cyclonic and long-lived anticyclonic situations characterized by moderate to high wind speeds. During the cyclonic situation, the marked increase of (Na and Cl) concentrations is associated with relatively high sea wind speeds (6 to 9 m/s), which are in turn responsible for a slight increase of crustal elements such as Al, Ca, Si, Fe and Mg, by the entrainment in the air of dust from roads and undeveloped areas. During the two anticyclonic situations, the simultaneous increase (due to communal transport) of crustal (Ca, Si, Al, Fe, Mg) and man-made (Mn, S, Pb, Zn) elements was noted to be associated with the dominance of terrigenious wind flows with speeds varying between 1.5 and 4 m/s. However, the significant contribution rates observed for Cl under the prevalence of such winds as compared to other crustal elements such as Fe suggested the influence of the sebkhas of Southern Tunisia.

Spectroscopic, Elemental and Thermal Analysis, and Positron Annihilation Studies on Ca(II), Sr(II), Ba(II), Pb(II), and Fe(III) Penicillin G Potassium Complexes

NASA Astrophysics Data System (ADS)

Refat, M. S.; Sharshara, T.

2015-11-01

The [Pb(Pin)2] · 3H2O, [M(Pin)(H2O)2(Cl)] · nH2O (M = SrII, CaII or BaII; n = 0-1), and [Fe(Pin)2(Cl)(H2O)] · H2O penicillin G potassium (Pin) complexes were synthesized and characterized using elemental analyses, molar conductivity, thermal analysis and electronic spectroscopy techniques. The positron annihilation lifetime (PAL) and Doppler broadening (DB) techniques have been employed to probe the defects and structural changes of Pin ligand and its complexes. The PAL and DB line-shape parameters were discussed in terms of the structure, molecular weight, ligand-metal molar ratio, and other properties of the Pin complexes.

Determination of Elemental Composition of Malabar spinach, Lettuce, Spinach, Hyacinth Bean, and Cauliflower Vegetables Using Proton Induced X-Ray Emission Technique at Savar Subdistrict in Bangladesh

PubMed Central

Fahad, S. M.; Islam, A. F. M. Mahmudul; Ahmed, Mahiuddin; Alam, Md. Rezaul; Alam, Md. Ferdous; Khalik, Md. Farhan; Hossain, Md. Lokman; Abedin, Md. Joynal

2015-01-01

The concentrations of 18 different elements (K, Ca, Fe, Cl, P, Zn, S, Mn, Ti, Cr, Rb, Co, Br, Sr, Ru, Si, Ni, and Cu) were analyzed in five selected vegetables through Proton Induced X-ray Emission (PIXE) technique. The objective of this study was to provide updated information on concentrations of elements in vegetables available in the local markets at Savar subdistrict in Bangladesh. These elements were found in varying concentrations in the studied vegetables. The results also indicated that P, Cl, K, Ca, Mn, Fe, and Zn were found in all vegetables. Overall, K and Ca exhibited the highest concentrations. Cu and Ni exhibited the lowest concentrations in vegetables. The necessity of these elements was also evaluated, based on the established limits of regulatory standards. The findings of this study suggest that the consumption of these vegetables is not completely free of health risks. PMID:26229953

Inhibition of hydrogen sulfide generation from disposed gypsum drywall using chemical inhibitors.

PubMed

Xu, Qiyong; Townsend, Timothy; Bitton, Gabriel

2011-07-15

Disposal of gypsum drywall in landfills has been demonstrated to elevate hydrogen sulfide (H(2)S) concentrations in landfill gas, a problem with respect to odor, worker safety, and deleterious effect on gas-to-energy systems. Since H(2)S production in landfills results from biological activity, the concept of inhibiting H(2)S production through the application of chemical agents to drywall during disposal was studied. Three possible inhibition agents - sodium molybdate (Na(2)MoO(4)), ferric chloride (FeCl(3)), and hydrated lime (Ca(OH)(2)) - were evaluated using flask and column experiments. All three agents inhibited H(2)S generation, with Na(2)MoO(4) reducing H(2)S generation by interrupting the biological sulfate reduction process and Ca(OH)(2) providing an unfavorable pH for biological growth. Although FeCl(3) was intended to provide an electron acceptor for a competing group of bacteria, the mechanism found responsible for inhibiting H(2)S production in the column experiment was a reduction in pH. Application of both Na(2)MoO(4) and FeCl(3) inhibited H(2)S generation over a long period (over 180 days), but the impact of Ca(OH)(2) decreased with time as the alkalinity it contributed was neutralized by the generated H(2)S. Practical application and potential environmental implications need additional exploration. Copyright © 2011 Elsevier B.V. All rights reserved.

Water pollution in relation to mineral exploration: a case study from Alayi-Ovim area of southeastern Nigeria.

PubMed

Ibe, Kalu K; Akaolisa, Casmir C Zanders

2012-05-01

Water samples from rivers, streams, springs, and shallow wells in Alayi-Ovim area of southeast Nigeria have been analyzed for Pb, Ca, Mg, Fe, Mg, PO(4), NO(3), CO(3), SO(4), Cl, and pH. The analyses were carried out using atomic absorption spectrometer and Hach Direct Reading Equipment. Results of the analyses from the area conform to the WHO (1995) standards for drinking water. However, the results show relative enrichment of Ca, pH, Mg, CO(3), and Cl. Low values were obtained for Fe, SO(4), and NO(3). While the Cl and Pb enrichment in the area north of Alayi-Ovim axis is attributed to proximity to the lead-zinc and chloride-rich formations of the Turonian Eze-Aku and the Albian Asu River; the Ca, Mg, SO(4), and CO(3) enrichment in Southern part of Alayi-Ovim is due to the limestone-bearing Late Maastrichtian Nsukka Formation. Furthermore, the very low values of less than 5 ppm for these characters in water in the central region correlate well with the relatively clean Maastrichtian quartz arenite Ajali Sandstone Formation. The Pb-Zn and Cl incursions into the water system from the Older Albian Asu River/Turonian Eze-Aku Formations in the northern part of Alayi-Ovim area and the leaching of Mg, and Ca into the water system in the Maastrichtian limestone area in the south thus constitute geochemical indices for chemical pollution and mineral exploration for brine and dolomitic limestone in the area.

``Amarna blue'' painted on ancient Egyptian pottery

NASA Astrophysics Data System (ADS)

Uda, M.; Nakamura, M.; Yoshimura, S.; Kondo, J.; Saito, M.; Shirai, Y.; Hasegawa, S.; Baba, Y.; Ikeda, K.; Ban, Y.; Matsuo, A.; Tamada, M.; Sunaga, H.; Oshio, H.; Yamashita, D.; Nakajima, Y.; Utaka, T.

2002-04-01

"Amarna blue" pigments (18 Dynasty, c. 1400 BC) painted on pottery fragments were investigated using the PIXE, XRF and XRD methods in laboratories and also using a portable type of X-ray spectrometer at the sites of excavation. On the blue-colored part enrichment of Na, Al, S, Cl, Ca, Mn, Co, Ni and Zn was found using X-ray spectroscopy, and CaSO 4, NaCl and Co(M)Al 2O 4, M denoting Mn, Fe, Ni and Zn, were found by the help of X-ray diffraction. This means that Amarna blue is a mixture of CaSO 4 and Co(M)Al 2O 4, at least in part.

Impact of chemical leaching on permeability and cadmium removal from fine-grained soils.

PubMed

Lin, Zhongbing; Zhang, Renduo; Huang, Shuang; Wang, Kang

2017-08-01

The aim of this study was to investigate the influence of chemical leaching on permeability and Cd removal from fine-grained polluted soils. Column leaching experiments were conducted using two types of soils (i.e., artificially Cd-polluted loam and historically polluted silty loam). Chemical agents of CaCl 2 , FeCl 3 , citric acid, EDTA, rhamnolipid, and deionized water were used to leach Cd from the soils. Results showed that organic agents reduced permeability of both soils, and FeCl 3 reduced permeability of loam soil, compared with inorganic agents and deionized water. Entrapment and deposition of colloids generated from the organic agents and FeCl 3 treatments reduced the soil permeability. The peak Cd effluence from the artificially polluted loam columns was retarded. For the artificially polluted soils treated with EDTA and the historically polluted soils with FeCl 3 , Cd precipitates were observed at the bottom after chemical leaching. When Cd was associated with large colloid particles, the reduction of soil permeability caused Cd accumulation in deeper soil. In addition, the slow process of disintegration of soil clay during chemical leaching might result in the retardation of peak Cd effluence. These results suggest the need for caution when using chemical-leaching agents for Cd removal in fine-grained soils.

Petrographic and spectroscopic characterization of phosphate-stabilized mine tailings from Leadville, Colorado.

PubMed

Eusden, J D; Gallagher, L; Eighmy, T T; Crannell, B S; Krzanowski, J R; Butler, L G; Cartledge, F K; Emery, E F; Shaw, E L; Francis, C A

2002-01-01

The use of soluble PO4(3-) and lime as a heavy metal chemical stabilization agent was evaluated for mine tailings from Leadville, Colorado. The tailings are from piles associated with the Wolftone and Maid of Erin mines; ore material that was originally mined around 1900, reprocessed in the 1940s, and now requires stabilization. The dominant minerals in the tailings are galena (PbS), cerrusite (PbCO3), pyromorphite (Pb5(PO4)3Cl), plumbojarosite (Pb0.5Fe3(SO4)2(OH)6), and chalcophanites ((Pb,Fe,Zn,Mn)Mn2O5 x 2H2O). The tailings were treated with soluble PO4(3-) and lime to convert soluble heavy metals (principally Pb, Zn, Cu, Cd) into insoluble metal phosphate precipitates. The treatment process caused bulk mineralogical transformations as well as the formation of a reaction rind around the particles dominated by Ca and P. Within the mineral grains, Fe-Pb phosphosulfates, Fe-Pb sulfates (plumbojarosite), and galena convert to Fe-Ca-Pb hydroxides. The Mn-Pb hydroxides and Mn-(+/-Fe)-Pb hydroxides (chalcophanites) undergo chemical alteration throughout the grains during treatment. Bulk and surface spectroscopies showed that the insoluble reaction products in the rind are tertiary metal phosphate (e.g. (Cu,Ca2)(PO4)2) and apatite (e.g. Pb5(PO4)3Cl) family minerals. pH-dependent leaching (pH 4,6,8) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 150 for many metals; particularly Pb2+, Zn2+, Cd2+, and Cu2+. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca2+, PO4(3-) Pb2+, Zn2+, Cd2+, and Cu2+ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids.

Ultrasonically-enhanced preparation, characterization of CaFe-layered double hydroxides with various interlayer halide, azide and oxo anions (CO32-, NO3-, ClO4-).

PubMed

Szabados, Márton; Varga, Gábor; Kónya, Zoltán; Kukovecz, Ákos; Carlson, Stefan; Sipos, Pál; Pálinkó, István

2018-01-01

An ultrasonically-enhanced mechanochemical method was developed to synthesize CaFe-layered double hydroxides (LDHs) with various interlayer anions (CO 3 2- , NO 3 - , ClO 4 - , N 3 - , F - , Cl - , Br - and I - ). The duration of pre-milling and ultrasonic irradiation and the variation of synthesis temperature in the wet chemical step were investigated to obtain the optimal parameters of preparation. The main method to characterize the products was X-ray diffractometry, but infrared and synchrotron-based X-ray absorption spectroscopies as well as thermogravimetric measurements were also used to learn about fine structural details. The synthesis method afforded successful intercalation of the anions, among others the azide anion, a rarely used counter ion providing a system, which enables safe handling the otherwise highly reactive anion. The X-ray absorption spectroscopic measurements revealed that the quality of the interlayered anions could modulate the spatial arrangement of the calcium ions around the iron(III) ions, but only in the second coordination sphere. Copyright © 2017 Elsevier B.V. All rights reserved.

Long conducting polymer nanonecklaces with a `beads-on-a-string' morphology: DNA nanotube-template synthesis and electrical properties

NASA Astrophysics Data System (ADS)

Chen, Guofang; Mao, Chengde

2016-05-01

Complex and functional nanostructures are always desired. Herein, we present the synthesis of novel long conducting polymer nanonecklaces with a `beads-on-a-string' morphology by the DNA nanotube-template approach and in situ oxidative polymerization of the 3-methylthiophene monomer with FeCl3 as the oxidant/catalyst. The length of the nanonecklaces is up to 60 μm, and the polymer beads of around 20-25 nm in diameter are closely packed along the axis of the DNA nanotube template with a density of ca. 45 particles per μm. The formation of porous DNA nanotubes impregnated with FeCl3 was also demonstrated as intermediate nanostructures. The mechanisms for the formation of both the porous DNA nanotubes and the conducting polymer nanonecklaces are discussed in detail. The as-synthesized polymer/DNA nanonecklaces exhibit good electrical properties.Complex and functional nanostructures are always desired. Herein, we present the synthesis of novel long conducting polymer nanonecklaces with a `beads-on-a-string' morphology by the DNA nanotube-template approach and in situ oxidative polymerization of the 3-methylthiophene monomer with FeCl3 as the oxidant/catalyst. The length of the nanonecklaces is up to 60 μm, and the polymer beads of around 20-25 nm in diameter are closely packed along the axis of the DNA nanotube template with a density of ca. 45 particles per μm. The formation of porous DNA nanotubes impregnated with FeCl3 was also demonstrated as intermediate nanostructures. The mechanisms for the formation of both the porous DNA nanotubes and the conducting polymer nanonecklaces are discussed in detail. The as-synthesized polymer/DNA nanonecklaces exhibit good electrical properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01603k

Arsenic release from Fe/Mn oxide-rich (model) soils/sediments - A comparison of single extraction procedures

NASA Astrophysics Data System (ADS)

Vanek, A.; Komarek, M.; Galuskova, I.

2012-04-01

Arsenic extractability in As-modified Fe(III) and Mn(III,IV) oxide-coated sands was tested using five widely used 2-h single extraction procedures: deionised water, 0.01 M CaCl2, 1 M NH4NO3, 0.1 M Na2HPO4 and 0.005 DTPA. In general, the highest As recoveries reaching 39-50% of total As concentration were observed for all extracting media in the birnessite (delta-MnO2) system, indicating relatively weak adsorption of As onto the Mn oxides. The Na2HPO4 extracts from the Fe oxide systems (i.e., associated with ferrihydrite and goethite) were highest in As, accounting for up to 34% of total As amount. Surprisingly, comparable recoveries of As (14-20%) yielded deionised water, CaCl2, NH4NO3, DTPA as extracting media for both ferrihydrite and goethite coatings. Deionised water and Na2HPO4 extractions are suggested for quick estimation of easily soluble, exchangeable and/or specifically adsorbed As in real soil/sediment samples.

Hourly elemental concentrations in PM2.5 aerosols sampled simultaneously at urban background and road site

NASA Astrophysics Data System (ADS)

Dall'Osto, M.; Querol, X.; Amato, F.; Karanasiou, A.; Lucarelli, F.; Nava, S.; Calzolai, G.; Chiari, M.

2012-08-01

Hourly-resolved aerosol chemical speciation data can be a highly powerful tool to determine the source origin of atmospheric pollutants in urban Environments. Aerosol mass concentrations of seventeen elements (Na, Mg, Al, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Sr and Pb) were obtained by time (1 h) and size (PM2.5 particulate matter <2.5 μm) resolved Particle Induced X-ray Emission (PIXE) measurements. In the Marie Curie FP7-EU framework of SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies), the unique approach used is the simultaneous PIXE measurements at two monitoring sites: urban background (UB) and a street canyon traffic road site (RS). Elements related to primary non exhaust traffic emission (Fe, Cu), dust resuspension (Ca) and anthropogenic Cl were found enhanced at the RS, whereas industrial related trace metals (Zn, Pb, Mn) were found at higher concentrations at the more ventilated UB site. When receptor modelling was performed with positive matrix factorization (PMF), nine different aerosol sources were identified at both sites: three types of regional aerosols (secondary sulphate (S) - 27%, biomass burning (K) - 5%, sea salt (Na-Mg) - 17%), three types of dust aerosols (soil dust (Al-Ti) - 17%, urban crustal dust (Ca) - 6%, and primary traffic non exhaust brake dust (Fe-Cu) - 7%), and three types industrial aerosol plumes-like events (shipping oil combustion (V-Ni) - 17%, industrial smelters (Zn-Mn) - 3%, and industrial combustion (Pb-Cl) - 5%). The validity of the PMF solution of the PIXE data is supported by strong correlations with external single particle mass spectrometry measurements. Beside apportioning the aerosol sources, some important air quality related conclusions can be drawn about the PM2.5 fraction simultaneously measured at the UB and RS sites: (1) the regional aerosol sources impact both monitoring sites at similar concentrations regardless their different ventilation conditions; (2) by contrast, local industrial aerosol plumes associated with shipping oil combustion and smelters activities have a higher impact on the more ventilated UB site; (3) a unique source of Pb-Cl (associated with industrial combustion emissions) is found a to be the major (82%) source of Cl in the urban agglomerate; (4) PM2.5 traffic brake dust (Fe-Cu) is mainly primarily emitted and not resuspended, whereas PM2.5 urban crustal dust (Ca) is found mainly resuspended by both traffic vortex and sea breeze; (5) urban dust (Ca) is found the aerosol source most affected by land wetness, reduced by a factor of eight during rainy days and suggesting that wet roads may be a solution for reducing dust concentrations in road sites, far more effective than street sweeping activities.

Ca-Fe and Alkali-Halide Alteration of an Allende Type B CAI: Aqueous Alteration in Nebular or Asteroidal Settings

NASA Technical Reports Server (NTRS)

Ross, D. K.; Simon, J. I.; Simon, S. B.; Grossman, L.

2012-01-01

Ca-Fe and alkali-halide alteration of CAIs is often attributed to aqueous alteration by fluids circulating on asteroidal parent bodies after the various chondritic components have been assembled, although debate continues about the roles of asteroidal vs. nebular modification processes [1-7]. Here we report de-tailed observations of alteration products in a large Type B2 CAI, TS4 from Allende, one of the oxidized subgroup of CV3s, and propose a speculative model for aqueous alteration of CAIs in a nebular setting. Ca-Fe alteration in this CAI consists predominantly of end-member hedenbergite, end-member andradite, and compositionally variable, magnesian high-Ca pyroxene. These phases are strongly concentrated in an unusual "nodule" enclosed within the interior of the CAI (Fig. 1). The Ca, Fe-rich nodule superficially resembles a clast that pre-dated and was engulfed by the CAI, but closer inspection shows that relic spinel grains are enclosed in the nodule, and corroded CAI primary phases interfinger with the Fe-rich phases at the nodule s margins. This CAI also contains abundant sodalite and nepheline (alkali-halide) alteration that occurs around the rims of the CAI, but also penetrates more deeply into the CAI. The two types of alteration (Ca-Fe and alkali-halide) are adjacent, and very fine-grained Fe-rich phases are associated with sodalite-rich regions. Both types of alteration appear to be replacive; if that is true, it would require substantial introduction of Fe, and transport of elements (Ti, Al and Mg) out of the nodule, and introduction of Na and Cl into alkali-halide rich zones. Parts of the CAI have been extensively metasomatized.

Effects of Chloride and Sulfate Salts on the Inhibition or Promotion of Sucrose Crystallization in Initially Amorphous Sucrose-Salt Blends.

PubMed

Thorat, Alpana A; Forny, Laurent; Meunier, Vincent; Taylor, Lynne S; Mauer, Lisa J

2017-12-27

The effects of salts on the stability of amorphous sucrose and its crystallization in different environments were investigated. Chloride (LiCl, NaCl, KCl, MgCl 2 , CaCl 2 , CuCl 2 , FeCl 2 , FeCl 3 , and AlCl 3 ) and sulfate salts with the same cations (Na 2 SO 4 , K 2 SO 4 , MgSO 4 , CuSO 4 , Fe(II)SO 4 , and Fe(III)SO 4 ) were studied. Samples (sucrose controls and sucrose:salt 1:0.1 molar ratios) were lyophilized, stored in controlled temperature and relative humidity (RH) conditions, and monitored for one month using X-ray diffraction. Samples were also analyzed by differential scanning calorimetry, microscopy, and moisture sorption techniques. All lyophiles were initially amorphous, but during storage the presence of a salt had a variable impact on sucrose crystallization. While all samples remained amorphous when stored at 11 and 23% RH at 25 °C, increasing the RH to 33 and 40% RH resulted in variations in crystallization onset times. The recrystallization time generally followed the order monovalent cations < sucrose < divalent cations < trivalent cations. The presence of a salt typically increased water sorption as compared to sucrose alone when stored at the same RH; however, anticrystallization effects were observed for sucrose combined with salts containing di- and trivalent cations in spite of the increased water content. The cation valency and hydration number played a major role in dictating the impact of the added salt on sucrose crystallization.

Formation of 3-MCPD Fatty Acid Esters from Monostearoyl Glycerol and the Thermal Stability of 3-MCPD Monoesters.

PubMed

Zhao, Yue; Zhang, Yaqiong; Zhang, Zhongfei; Liu, Jie; Wang, Yi-Lin; Gao, Boyan; Niu, Yuge; Sun, Xiangjun; Yu, Liangli

2016-11-23

Formation of 3-monochloropropanediol (3-MCPD) esters from monostearoyl glycerol (MSG) was investigated under high temperature and low moisture conditions. Different organic and inorganic chlorides, including lindane, KCl, CaCl 2 , NaCl, MgCl 2 , AlCl 3 , CuCl 2 , MnCl 2 , SnCl 2 , ZnCl 2 , and FeCl 3 , were evaluated for their potential to react with MSG to form 3-MCPD and glycidyl esters at 120 and 240 °C using a UPLC-Q-TOF MS analysis. The results indicated that different chlorine compounds differed in their capacity to react with MSG and formed different products including 3-MCPD mono- and diesters, distearoylglycerol, and glycidyl esters. According to electron spin resonance (ESR) and Fourier transform infrared (FT-IR) spectroscopies, free radical mediated formation mechanisms involving either five-membered or six-membered cyclic acyloxonium free radicals (CAFR) from monoacylglycerol (MAG) were proposed. Tandem quadrupole-time-of-flight (Q-TOF) MS and MS/MS analyses confirmed the free radical mechanisms. In addition, the results from the present study showed that 3-MCPD monoester could be degraded upon thermal treatment and suggested a possible catalytic role of Fe 3+ under the experimental conditions.

Synthesis of Fe nanoparticles on polyaniline covered carbon nanotubes for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Hu, Tian-Hang; Yin, Zhong-Shu; Guo, Jian-Wei; Wang, Cheng

2014-12-01

Fe nanoparticles immobilized on polyaniline-covered carbon nanotube (CNT) surfaces (Fe NPs-PANI/CNT) are prepared by reducing FeCl3 in the mixing solution of aniline and CNT. Significantly, the structure of such composites can be effectively optimized by pretreating FeCl3 with sodium citrate (CA). In the absence of CNTs, we found these two routes have large differences in reduction behaviors and different PANI states with varied conductivities. Therefore, the self-assembly mechanism in the preparation is proposed and the controlled self-assembly manner in the pretreating route is disclosed. Under acid condition, both catalysts demonstrate high oxygen reduction reaction (ORR) activity with four-electron pathway, and high electrochemical durability, revealing a promising application in the proton exchange membrane fuel cells. However, the high Tafel slopes relating to the surface red-ox couple and porous conductivity are still the main obstacles to improve their ORR dynamic, and more efforts on these aspects are needed to drive non-noble catalyst application in future.

Chemistry of impact events on Mercury

NASA Astrophysics Data System (ADS)

Berezhnoy, Alexey A.

2018-01-01

Based on the equilibrium thermochemical approach and quenching theory, formation of molecules and dust grains in impact-produced clouds formed after collisions between meteoroids and Mercury is considered. Based on observations of Al, Fe, and Mn atoms in the exosphere of Mercury and new results of studies of the elemental composition of the surface of Mercury, quenching temperatures and pressures of main chemical reactions and condensation of dust particles were estimated. The behavior of the main Na-, K-, Ca-, Fe-, Al-, Mn-, Mg-, Si-, Ti, Ni-, Cr-, Co, Zn-, O-, H-, S-, C-, Cl-, N-, and P-containing species delivered to the Hermean exosphere during meteoroid impacts was studied. The importance of meteoroid bombardment as a source of Na, K, Ca, Fe, Al, Mn, Mg, and O atoms in the exosphere of Mercury is discussed.

Carbonate, Halide, and Other New Mineral Inclusions in Diamond and Deep-Seated Carbonatitic Magma

NASA Astrophysics Data System (ADS)

Kaminsky, F.; Wirth, R.; Matsyuk, S.

2009-05-01

A series of uncommon micro- and nano-inclusions was identified in diamonds from the Juina area: carbonates, halides, and others. Carbonates are represented by calcite (with Sr and Ba), K-rich nyerereite (K2O = 10.0-13.78 wt. %), and nahcolite. Halides are NaCl, KCl, CaCl2 and PbCl2. Minerals of the periclase- wüstite series belong to two separate groups: wüstite and Mg-wüstite with Mg# = 1.9-15.3, and Fe-periclase and periclase with Mg# = 84.9-92.1. Wollastonite-II (high, Ca: Si = 0.992) has a triclinic structure. Ca-rich garnet has a noticeable admixture of Zr; it belongs to the andradite - kimzeyite - schorlomite group. Two types of spinel were distinguished among mineral inclusions in diamond: zoned magnesioferrite (with Mg# varying from 13.5 in a core to 90.8 in a rim) and Fe-spinel (magnetite). Olivine (Mg# = 93.6), intergrown with nyerereite, forms elongated, lath-shaped crystal and, probably, is a retrograde transformation of ringwoodite or wadsleyite. Some apatite grains are enriched in La, Ce and Nd. Among other minerals, there are anhydrite, cuspidine, phlogopite, TiO2 with an α-PbO2 structure, native Fe. All inclusions are polymineralic solid inclusions. These minerals form a carbonatitic-type mineral association in diamond which may have been originated in lower mantle and/or transition zone. Wüstite inclusions with Mg# = 1.9-3.4, according to the experimental data, may have been formed in the lowermost mantle. The source for the observed carbonatitic-type mineral association in diamond is deep-seated carbonatitic, most likely natrocarbonatitic magma.

Strain selection and medium optimization for glucoamylase production from industrial potato waste by Aspergillus niger.

PubMed

Izmirlioglu, Gulten; Demirci, Ali

2016-06-01

Glucoamylase is one of the most common enzymes used in the food industry to break down starch into its monomers. Glucoamylase production and its activity are highly dependent on medium composition. Starch is well known as a glucoamylase inducer, and utilization of industrial starchy potato waste is an inexpensive way of improving glucoamylase production. Since glucoamylase production is highly dependent on medium composition, in this study medium optimization for glucoamylase production was considered to enhance glucoamylase activity. Among the evaluated microbial species, Aspergillus niger van Tieghem was found to be the best glucoamylase-producing fungus. The Plackett-Burman design was used to screen various medium ingredients, and malt extract, FeSO4 .7H2 O and CaCl2 ·2H2 O were found to have significant effects on glucoamylase production. Finally, malt extract, FeSO4 .7H2 O and CaCl2 .2H2 O were optimized by using a central composite design of response surface methodology. The results showed that the optimal medium composition for A. niger van Tieghem was 50 g L(-1) industrial waste potato mash supplemented with 51.82 g L(-1) malt extract, 9.27 g L(-1) CaCl2 ·2H2 O and 0.50 g L(-1) FeSO4 .7H2 O. At the end of optimization, glucoamylase activity and glucose production were improved 126% and 98% compared to only industrial waste potato mash basal medium; 274.4 U mL(-1) glucoamylase activity and 41.7 g L(-1) glucose levels were achieved, respectively. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

Assessment of groundwater quality in Kashipur Block, Purulia district, West Bengal

NASA Astrophysics Data System (ADS)

Kundu, Anindita; Nag, S. K.

2018-03-01

Hydrogeochemical investigation of groundwater resources of Kashipur Block, Purulia district, West Bengal has been carried out to assess the water quality for domestic and irrigation uses. Twenty groundwater samples were collected and analyzed for pH, electrical conductivity, total dissolved solids, hardness, major anions (CO3 2-, HCO3 -, Cl-, SO4 2-, F-) and cations (Ca2+, Mg2+, Fe2+, Na+, K+). Study results reveal that the groundwater of the area is mostly acidic in nature. The trend amongst average ionic concentrations of cations and anions is Mg2+ > Ca2+ > Na+ > Fe2+ > K+ and Cl- > HCO3 - > CO3 2- > SO4 2- > F- respectively during the post monsoon whereas the trend for cations and anions are Mg2+ > Ca2+> Na+ > K+ > Fe and Cl- > HCO3 - > SO4 2- > F- > CO3 - in pre monsoon session, respectively. To explore the ionic toxicity of the study area, the derived parameters like sodium adsorption ratio, soluble sodium percentage, residual sodium carbonate, magnesium adsorption ratio, Kelly's ratio and permeability index were calculated. The hydro geochemical data suggest that weathering of rock forming minerals along with secondary contributions from agricultural and anthropogenic sources are mainly controlling the groundwater composition of Kashipur Block, Purulia District. According to piper diagram, water samples of most of the area of the block are fresh water and in some areas sulphate rich throughout the year. All samples are distributed to central rock dominance category. Groundwater chemistry of this block is mainly controlled by the interaction existing between the litho units and the percolating water into the subsurface domain. However, the groundwater quality and suitability of this study area can be termed as good to moderate with a few exceptions which have been encountered on a local scale.

Metal-rich fluid inclusions provide new insights into unconformity-related U deposits (Athabasca Basin and Basement, Canada)

NASA Astrophysics Data System (ADS)

Richard, Antonin; Cathelineau, Michel; Boiron, Marie-Christine; Mercadier, Julien; Banks, David A.; Cuney, Michel

2016-02-01

The Paleoproterozoic Athabasca Basin (Canada) hosts numerous giant unconformity-related uranium deposits. The scope of this study is to establish the pressure, temperature, and composition (P-T-X conditions) of the brines that circulated at the base of the Athabasca Basin and in its crystalline basement before, during and after UO2 deposition. These brines are commonly sampled as fluid inclusions in quartz- and dolomite-cementing veins and breccias associated with alteration and U mineralization. Microthermometry and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data from five deposits (Rabbit Lake, P-Patch, Eagle Point, Millennium, and Shea Creek) complement previously published data for the McArthur River deposit. In all of the deposits investigated, fluid inclusion salinity is between 25 and 40 wt.% NaCl equiv., with compositions displaying a continuum between a "NaCl-rich brine" end-member (Cl > Na > Ca > Mg > K) and a "CaCl2-rich brine" end-member (Cl > Ca ≈ Mg > Na > K). The CaCl2-rich brine has the highest salinity and shows evidence for halite saturation at the time of trapping. The continuum of compositions between the NaCl-rich brine and the CaCl2-rich brine end-members combined with P-T reconstructions suggest anisothermal mixing of the two brines (NaCl-rich brine, 180 ± 30 °C and 800 ± 400 bars; CaCl2-rich brine, 120 ± 30 °C and 600 ± 300 bars) that occurred under fluctuating pressure conditions (hydrostatic to supra-hydrostatic). However, because the two brines were U bearing and therefore oxidized, brine mixing was probably not the driving force for UO2 deposition. Several scenarios are put forward to account for the Cl-Na-Ca-Mg-K composition of the brines, involving combinations of seawater evaporation, halite dissolution, mixing with a halite-dissolution brine, Mg/Ca exchange by dolomitization, Na/Ca exchange by albitization of plagioclase, Na/K exchange by albitization of K-feldspar, and Mg loss by Mg-rich alteration. Finally, the metal concentrations in the NaCl-rich and CaCl2-rich brines are among the highest recorded compared to present-day sedimentary formation waters and fluid inclusions from basin-hosted base metal deposits (up to 600 ppm U, 3000 ppm Mn, 4000 ppm Zn, 6000 ppm Cu, 8000 ppm Pb, and 10,000 ppm Fe). The CaCl2-rich brine carries up to one order of magnitude more metal than the NaCl-rich brine. Though the exact origin of major cations and metals of the two brines remains uncertain, their contrasting compositions indicate that the two brines had distinct flow paths and fluid-rock interactions. Large-scale circulation of the brines in the Athabasca Basin and Basement was therefore a key parameter for metal mobility (including U) and formation of unconformity-related U deposits.

Siudaite, Na8(Mn2+ 2Na)Ca6Fe3+ 3Zr3NbSi25O74(OH)2Cl·5H2O: a new eudialyte-group mineral from the Khibiny alkaline massif, Kola Peninsula

NASA Astrophysics Data System (ADS)

Chukanov, Nikita V.; Rastsvetaeva, Ramiza K.; Kruszewski, Łukasz; Aksenov, Sergey M.; Rusakov, Vyacheslav S.; Britvin, Sergey N.; Vozchikova, Svetlana A.

2018-03-01

The new eudialyte-group mineral siudaite, ideally Na8(Mn2+ 2Na)Ca6Fe3+ 3Zr3NbSi25O74(OH)2Cl·5H2O, was discovered in a peralkaline pegmatite situated at the Eveslogchorr Mt., Khibiny alkaline massif, Kola Peninsula, Russia. The associated minerals are aegirine, albite, microcline, nepheline, astrophyllite, and loparite-(Ce). Siudaite forms yellow to brownish-yellow equant anhedral grains up to 1.5 cm across. Its lustre is vitreous, and the streak is white. Cleavage is none observed. The Mohs' hardness is 4½. Density measured by hydrostatic weighing is 2.96(1) g/cm3. Density calculated using the empirical formula is equal to 2.973 g/cm3. Siudaite is nonpleochroic, optically uniaxial, negative, with ω = 1.635(1) and ɛ = 1.626(1) (λ = 589 nm). The IR spectrum is given. The chemical composition of siudaite is (wt%; electron microprobe, H2O determined by HCN analysis): Na2O 8.40, K2O 0.62, CaO 9.81, La2O3 1.03, Ce2O3 1.62, Pr2O3 0.21, Nd2O3 0.29, MnO 6.45, Fe2O3 4.51. TiO2 0.54, ZrO2 11.67, HfO2 0.29, Nb2O5 2.76, SiO2 47.20, Cl 0.54, H2O 3.5, -O = Cl - 0.12, total 99.32. According to Mössbauer spectroscopy data, all iron is trivalent. The empirical formula (based on 24.5 Si atoms pfu, in accordance with structural data) is [Na7.57(H2O)1.43]Σ9(Mn1.11Na0.88Ce0.31La0.20Nd0.05Pr0.04K0.41)Σ3(H2O)1.8(Ca5.46Mn0.54)Σ6(Fe3+ 1.76Mn2+ 1.19)Σ2.95Nb0.65(Ti0.20Si0.50)Σ0.71(Zr2.95Hf0.04Ti0.01)Σ3Si24.00Cl0.47O70(OH)2Cl0.47·1.82H2O. The crystal structure was determined using single-crystal X-ray diffraction data. The new mineral is trigonal, space group R3m, with a = 14.1885(26) Å, c = 29.831(7) Å, V = 5200.8(23) Å3 and Z = 3. Siudaite is chemically related to georgbarsanovite and is its analogue with Fe3+-dominant M2 site. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 6.38 (60) (-114), 4.29 (55) (-225), 3.389 (47) (131), 3.191 (63) (-228). 2.963 (100) (4-15), 2.843 (99) (-444), 2.577 (49) (3-39). Siudaite is named after the Polish mineralogist and geochemist Rafał Siuda (b. 1975).

A novel method for vanadium slag comprehensive utilization to synthesize Zn-Mn ferrite and Fe-V-Cr alloy.

PubMed

Liu, Shi-Yuan; Li, Shu-Jin; Wu, Shun; Wang, Li-Jun; Chou, Kuo-Chih

2018-07-15

Vanadium slag is a by-product from steelmaking process of vanadium-titanium magnetite, which mainly contains FeO, MnO, V 2 O 3 , and Cr 2 O 3 , The elements Fe and Mn are major components of Mn-Zn ferrite. The elements V and Cr are major components of V-Cr alloy. In view of the potential application in these study, a Mn 0.8 Zn 0.2 Fe 2 O 4 of high saturation magnetization (Ms = 68.6 emu/g) and low coercivity (Hc = 3.3 Oe) was successfully synthesized from the leaching solutions of vanadium slag by adding appropriate chemical reagents, ZnCl 2 and MnCl 2 ·4H 2 O, via roasting at 1300 °C for 1 h. The minor components (CaO and SiO 2 ) in the leaching solution of vanadium slag segregated to the grain boundaries resulting in increasing the resistivity of ferrite. The value of DC resistivity of Mn 0.8 Zn 0.2 Fe 2 O 4 at 25 °C reached 1230.7Ω m. The residue containing Fe, V and Cr was chlorinated by AlCl 3 and the Fe 3+ , V 3+ , and Cr 3+ ions were released into the NaCl-KCl eutectic. The current-time curve for the electrolysis of molten salt was investigated. Alloy (Fe, V, and Cr) of granular shape was obtained. The residue can be used to produce the mulite. This process provided a new approach to utilize slag from steelmaking. Copyright © 2018 Elsevier B.V. All rights reserved.

The effect of DEB powder processing on thermal cell performance

NASA Astrophysics Data System (ADS)

Szwarc, R.; Walton, R. D.

During the last twenty years, the system Ca/LiCl-KCl-CaCrO4/Fe has provided the basis for thermal batteries designed for military applications. In connection with greater performance demands, investigations are being conducted concerning the effect of catholyte processing on thermal cell performance. The catholyte layer is composed of three components including the depolarizer (D), CaCrO4, the electrolyte (E), LiCl-KCl eutectic, and the binder (B), finely divided SiO2. The catholyte layer or DEB pellets are produced by blending these components, fusing, pulverizing the cake, and hydrostatically pressing the powder into pellets. A description is given of ten powders which were prepared for the reported study. It was found that the procedure used in powder processing affects the capacity, but not its voltage. Increasing the prebake temperature for CaCrO4 from 400 to 600 C resulted in an increase in capacity.

Electrochemical Synthesis of Core–Shell-Structured NbC–Fe Composite Powder for Enforcement in Low-Carbon Steel

PubMed Central

Song, Qiushi; Xu, Qian; Chen, Ying; Xu, Liang; Man, Tiannan

2017-01-01

An NbC–Fe composite powder was synthesized from an Nb2O5/Fe/C mixture by electrochemical reduction and subsequent carbonization in molten CaCl2–NaCl. The composite has a core–shell structure, in which NbC acts as the cores distributing in the Fe matrix. A strong bonding between NbC and Fe is benefit from the core–shell structure. The sintering and electrochemical reduction processes were investigated to probe the mechanism for the reactions. The results show that NbC particles about several nanometers were embraced by the Fe shell to form a composite about 100 nm in size. This featured structure can feasibly improve the wettability and sinterability of NbC as well as the uniform distribution of the carbide in the cast steel. By adding the composite into steel in the casting process, the grain size of the casted steel was markedly deceased from 1 mm to 500 μm on average, favoring the hardening of the casted steel. PMID:29104266

Origin of CaCl2 brines by basalt-seawater interaction: Insights provided by some simple mass balance calculations

NASA Astrophysics Data System (ADS)

Hardie, Lawrence A.

1983-06-01

Modern rift zone hydrothermal brines are typically CaCl2-bearing brines, an unusual chemical signature they share with certain oil field brines, fluid inclusions in ore minerals and a few uncommon saline lakes. Many origins have been suggested for such CaCl2 brines but in the Reykjanes, Iceland, geothermal system a strong empirical case can be made for a basalt-seawater interaction origin. To examine this mechanism of CaCl2 brine evolution some simple mass balance calculations were carried out. Average Reykjanes olivine tholeiite was “reacted” with average North Atlantic seawater to make an albite-chlorite-epidotesphene rock using Al2O3 as the conservative rock component and Cl as the conservative fluid component. The excess components released by the basalt to the fluid were “precipitated” at 275° C as quartz, calcite, anhydrite, magnetite and pyrite to complete the conversion to greenstone. The resulting fluid was a CaCl2 brine of seawater chlorinity with a composition remarkably similar to the actual Reykjanes brine at 1750 m depth. Thus, the calculations strongly support the idea that the Reykjanes CaCl2 brines result from “closed system” oceanic basalt-seawater interaction (albitization — chloritization mechanism) at greenschist facies temperatures. The calculation gives a seawater: basalt mass ratio of 3∶1 to 4∶1 (vol. ratio of 9∶1 to 12∶1), in keeping with experimental results, submarine vent data and with ocean crust cooling calculations. The brine becomes anoxic because there is insufficient dissolved or combined oxygen to balance all the Fe released from the basalt during alteration. Large excesses of Ca are released to the fluid and precipitate out in the form of anhydrite which essentially sweeps the brine free of sulfate leaving an elevated Ca concentration. The calculated rock-water interaction basically involves Na + Mg + SO4 ⇌ Ca + K, simulating chemical differences observed between oceanic basalts and greenstones from many mid-ocean ridges.

A comparison of the techniques of PIXE, PIGE and INAA by reference to the elemental analysis of porcine brain samples

NASA Astrophysics Data System (ADS)

Stedman, J. D.; Spyrou, N. M.

1994-12-01

The trace element concentrations in porcine brain samples as determined by particle-induced X-ray emission (PIXE) analysis, instrumental neutron activation analysis (INAA) and particle-induced gamma-ray emission (PIGE) analysis are compared. The matrix composition was determined by Rutherford backscattering (RBS). Al, Si, P, S, Cl, K, Ca, Mn, Fe and Cd were determined by PIXE analysis Na, K, Sc, Fe, Co, Zn, As, Br, Rb, and Cs by INAA and Na, Mg and Fe by PIGE analysis. The bulk elements C, N, O, Na Cl and S were found by RBS analysis. Elemental concentrations are obtained using the comparator method of analysis rather than an absolute method, the validity which is examined by comparing the elemental concentrations obtained in porcine brain using two separate certified reference materials.

Hourly elemental concentrations in PM2.5 aerosols sampled simultaneously at urban background and road site during SAPUSS - diurnal variations and PMF receptor modelling

NASA Astrophysics Data System (ADS)

Dall'Osto, M.; Querol, X.; Amato, F.; Karanasiou, A.; Lucarelli, F.; Nava, S.; Calzolai, G.; Chiari, M.

2013-04-01

Hourly-resolved aerosol chemical speciation data can be a highly powerful tool to determine the source origin of atmospheric pollutants in urban environments. Aerosol mass concentrations of seventeen elements (Na, Mg, Al, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Sr and Pb) were obtained by time (1 h) and size (PM2.5 particulate matter < 2.5 μm) resolved aerosol samples analysed by Particle Induced X-ray Emission (PIXE) measurements. In the Marie Curie European Union framework of SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies), the approach used is the simultaneous sampling at two monitoring sites in Barcelona (Spain) during September-October 2010: an urban background site (UB) and a street canyon traffic road site (RS). Elements related to primary non-exhaust traffic emission (Fe, Cu), dust resuspension (Ca) and anthropogenic Cl were found enhanced at the RS, whereas industrial related trace metals (Zn, Pb, Mn) were found at higher concentrations at the more ventilated UB site. When receptor modelling was performed with positive matrix factorization (PMF), nine different aerosol sources were identified at both sites: three types of regional aerosols (regional sulphate (S) - 27%, biomass burning (K) - 5%, sea salt (Na-Mg) - 17%), three types of dust aerosols (soil dust (Al-Ti) - 17%, urban crustal dust (Ca) - 6%, and primary traffic non-exhaust brake dust (Fe-Cu) - 7%), and three types of industrial aerosol plumes-like events (shipping oil combustion (V-Ni) - 17%, industrial smelters (Zn-Mn) - 3%, and industrial combustion (Pb-Cl) - 5%, percentages presented are average source contributions to the total elemental mass measured). The validity of the PMF solution of the PIXE data is supported by very good correlations with external single particle mass spectrometry measurements. Some important conclusions can be drawn about the PM2.5 mass fraction simultaneously measured at the UB and RS sites: (1) the regional aerosol sources impact both monitoring sites at similar concentrations regardless their different ventilation conditions; (2) by contrast, local industrial aerosol plumes associated with shipping oil combustion and smelters activities have a higher impact on the more ventilated UB site; (3) a unique source of Pb-Cl (associated with combustion emissions) is found to be the major (82%) source of fine Cl in the urban agglomerate; (4) the mean diurnal variation of PM2.5 primary traffic non-exhaust brake dust (Fe-Cu) suggests that this source is mainly emitted and not resuspended, whereas PM2.5 urban dust (Ca) is found mainly resuspended by both traffic vortex and sea breeze; (5) urban dust (Ca) is found the aerosol source most affected by land wetness, reduced by a factor of eight during rainy days and suggesting that wet roads may be a solution for reducing urban dust concentrations.

10 CFR Appendix E to Part 835 - Values for Establishing Sealed Radioactive Source Accountability and Radioactive Material Posting...

Code of Federal Regulations, 2012 CFR

2012-01-01

...+05 C-14 4.6E+06 Na-22 1.9E+01 Al-26 1.5E+01 Si-32 4.9E+04 S-35 2.4E+06 Cl-36 5.2E+05 K-40 2.7E+02 Ca-41 9.3E+06 Ca-45 1.1E+06 Sc-46 6.2E+01 Ti-44 1.5E+02 V-49 1.0E+08 Mn-53 7.5E+07 Mn-54 6.5E+01 Fe-55 2.9E+06 Fe-59 1.9E+02 Fe-60 8.1E+03 Co-56 3.9E+01 Co-57 2.3E+02 Co-58 1.3E+02 Co-60 1.7E+01 Ni-59 3.2E...

10 CFR Appendix E to Part 835 - Values for Establishing Sealed Radioactive Source Accountability and Radioactive Material Posting...

Code of Federal Regulations, 2013 CFR

2013-01-01

...+05 C-14 4.6E+06 Na-22 1.9E+01 Al-26 1.5E+01 Si-32 4.9E+04 S-35 2.4E+06 Cl-36 5.2E+05 K-40 2.7E+02 Ca-41 9.3E+06 Ca-45 1.1E+06 Sc-46 6.2E+01 Ti-44 1.5E+02 V-49 1.0E+08 Mn-53 7.5E+07 Mn-54 6.5E+01 Fe-55 2.9E+06 Fe-59 1.9E+02 Fe-60 8.1E+03 Co-56 3.9E+01 Co-57 2.3E+02 Co-58 1.3E+02 Co-60 1.7E+01 Ni-59 3.2E...

10 CFR Appendix E to Part 835 - Values for Establishing Sealed Radioactive Source Accountability and Radioactive Material Posting...

Code of Federal Regulations, 2014 CFR

2014-01-01

...+05 C-14 4.6E+06 Na-22 1.9E+01 Al-26 1.5E+01 Si-32 4.9E+04 S-35 2.4E+06 Cl-36 5.2E+05 K-40 2.7E+02 Ca-41 9.3E+06 Ca-45 1.1E+06 Sc-46 6.2E+01 Ti-44 1.5E+02 V-49 1.0E+08 Mn-53 7.5E+07 Mn-54 6.5E+01 Fe-55 2.9E+06 Fe-59 1.9E+02 Fe-60 8.1E+03 Co-56 3.9E+01 Co-57 2.3E+02 Co-58 1.3E+02 Co-60 1.7E+01 Ni-59 3.2E...

A spin-crossover complex based on a 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) ligand functionalized with a carboxylate group.

PubMed

Abhervé, Alexandre; Clemente-León, Miguel; Coronado, Eugenio; Gómez-García, Carlos J; López-Jordà, Maurici

2014-07-07

Combining Fe(ii) with the carboxylate-functionalized 2,6-bis(pyrazol-1-yl)pyridine (bppCOOH) ligand results in the spin-crossover compound [Fe(bppCOOH)2](ClO4)2 which shows an abrupt spin transition with a T1/2 of ca. 380 K and a TLIESST of 60 K due to the presence of a hydrogen-bonded linear network of complexes.

Interfacing carbon nanotubes (CNT) with plants: enhancement of growth, water and ionic nutrient uptake in maize ( Zea mays) and implications for nanoagriculture

NASA Astrophysics Data System (ADS)

Tiwari, D. K.; Dasgupta-Schubert, N.; Villaseñor Cendejas, L. M.; Villegas, J.; Carreto Montoya, L.; Borjas García, S. E.

2014-06-01

The application of nano-biotechnology to crop-science/agriculture (`nanoagriculture') is a recent development. While carbon nanotubes (CNTs) have been shown to dramatically improve germination of some comestible plants, deficiencies in consistency of behavior and reproducibility arise, partially from the variability of the CNTs used. In this work, factory-synthesized multi-walled-CNTs (MWCNTs) of quality-controlled specifications were seen to enhance the germinative growth of maize seedlings at low concentrations but depress it at higher concentrations. Growth enhancement principally arose through improved water delivery by the MWCNT. Polarized EDXRF spectrometry showed that MWCNTs affect mineral nutrient supply to the seedling through the action of the mutually opposing forces of inflow with water and retention in the medium by the ion-CNT transient-dipole interaction. The effect varied with ion type and MWCNT concentration. The differences of the Fe tissue concentrations when relatively high equimolar Fe2+ or Fe3+ was introduced, implied that the ion-CNT interaction might induce redox changes to the ion. The tissue Ca2+ concentration manifested as the antipode of the Fe2+ concentration indicating a possible cationic exchange in the cell wall matrix. SEM images showed that MWCNTs perforated the black-layer seed-coat that could explain the enhanced water delivery. The absence of perforations with the introduction of FeCl2/FeCl3 reinforces the idea of the modification of MWCNT functionality by the ion-CNT interaction. Overall, in normal media, low dose MWCNTs were seen to be beneficial, improving water absorption, plant biomass and the concentrations of the essential Ca, Fe nutrients, opening a potential for possible future commercial agricultural applications.

A simple biofuel cell cathode with human red blood cells as electrocatalysts for oxygen reduction reaction.

PubMed

Ayato, Yusuke; Sakurai, Kenichiro; Fukunaga, Saori; Suganuma, Takuya; Yamagiwa, Kiyofumi; Shiroishi, Hidenobu; Kuwano, Jun

2014-05-15

A red blood cell (RBC) from human exhibited direct electron transfer (DET) activity on a bare indium tin oxide (ITO) electrode. A formal potential of -0.152 V vs. a silver-silver chloride saturated potassium chloride (Ag|AgCl|KCl(satd.)) was estimated for the human RBC (type AB) from a pair of redox peaks at around 0.089 and -0.215 V (vs. Ag|AgCl|KCl(satd.)) on cyclic voltammetric (CV) measurements in a phosphate buffered saline (PBS; 39 mM; pH 7.4) solution. The results agreed well with those of a redox couple for iron-bearing heme groups in hemoglobin molecules (HbFe(II)/HbFe(III)) on the bare ITO electrodes, indicated that DET active species were hemoglobin (Hb) molecules encapsulated by a phospholipid bilayer membrane of the human RBC. The quantity of electrochemically active Hb in the human RBC was estimated to be 30 pmol cm(-2). In addition, the human RBC exhibited oxygen reduction reaction (ORR) activity in the dioxygen (O2) saturated PBS solution at the negative potential from ca. -0.15 V (vs. Ag|AgCl|KCl(satd.)). A single cell test proved that a biofuel cell (BFC) with an O2|RBC|ITO cathode showed the open-circuit voltage (OCV) of ca. 0.43 V and the maximum power density of ca. 0.68 μW cm(-2). © 2013 Published by Elsevier B.V.

Fabrication and electrocatalytic properties of chitosan and keplerate-type polyoxometalate {Mo72Fe30} hybrid films.

PubMed

Fan, Dawei; Hao, Jingcheng

2009-05-28

Hybrid films composed of chitosan and Keplerate-type polyoxometalate, {Mo72Fe30} (Mo72VIFe30IIIO252L102.ca.180H2O, L=H2O/CH3COO-/Mo2O8/9n-), were fabricated on quartz, silicon, and ITO substrates by layer-by-layer (LbL) method. The LbL films were characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and cyclic voltammetry (CV). UV-vis spectra show that the absorbance values at characteristic wavelengths of the multilayer films increase almost linearly with the number of chitosan/{Mo72Fe30} bilayers. XPS spectra confirm the incorporation of chitosan and {Mo72Fe30} into the films. The electrocatalytic reduction of ClO3-, BrO3-, and IO3- by chitosan/{Mo72Fe30} hybrid films in an acidic aqueous solution shows an electrocatalytic reduction activity of IO3->BrO3->ClO3-. In particular, the modified electrodes exhibited high electrocatalytic activity for reduction of IO3-.

Complete series of chiral paramagnetic molecular conductors based on tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) and Chloranilate-bridged heterobimetallic honeycomb layers.

PubMed

Atzori, Matteo; Pop, Flavia; Auban-Senzier, Pascale; Clérac, Rodolphe; Canadell, Enric; Mercuri, Maria Laura; Avarvari, Narcis

2015-04-06

Electrocrystallization of enantiopure (S,S,S,S)- and (R,R,R,R)-tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) donors, as well as the racemic mixture, in the presence of potassium cations and the tris(chloranilato)ferrate(III) [Fe(Cl2An)3](3-) paramagnetic anion afforded a complete series of chiral magnetic molecular conductors formulated as β-[(S,S,S,S)-TM-BEDT-TTF]3PPh4[K(I)Fe(III)(Cl2An)3]·3H2O (1), β-[(R,R,R,R)-TM-BEDT-TTF]3PPh4[K(I)Fe(III)(Cl2An)3]·3H2O (2), and β-[(rac)-TM-BEDT-TTF]3PPh4[K(I)Fe(III)(Cl2An)3]·3H2O (3). Compounds 1-3 are isostructural and crystallize in triclinic space groups (P1 for 1 and 2, P-1 for 3) showing a segregated organic-inorganic crystal structure, where anionic honeycomb layers obtained by self-assembling of the Λ and Δ enantiomers of the paramagnetic complex with potassium cations alternate with organic layers where the chiral donors are arranged in the β packing motif. Compounds 1-3 show a molecular packing strongly influenced by the topology of the inorganic layers and behave as molecular semiconductors with room-temperature conductivity values of ca. 3 × 10(-4) S cm(-1). The magnetic properties are dominated by the paramagnetic S = 5/2 [Fe(Cl2An)3](3-) anions whose high-spin character is confirmed by magnetic susceptibility measurements. The correlation between crystal structure and conducting behavior has been studied by means of tight-binding band structure calculations which support the observed conducting properties.

Overexpression of afsR and Optimization of Metal Chloride to Improve Lomofungin Production in Streptomyces lomondensis S015.

PubMed

Wang, Wei; Wang, Huasheng; Hu, Hongbo; Peng, Huasong; Zhang, Xuehong

2015-05-01

As a global regulatory gene in Streptomyces, afsR can activate the biosynthesis of many secondary metabolites. The effect of afsR on the biosynthesis of a phenazine metabolite, lomofungin, was studied in Streptomyces lomondensis S015. There was a 2.5-fold increase of lomofungin production in the afsR-overexpressing strain of S. lomondensis S015 N1 compared with the wild-type strain. Meanwhile, the transcription levels of afsR and two important genes involved in the biosynthesis of lomofungin (i.e., phzC and phzE) were significantly upregulated in S. lomondensis S015 N1. The optimization of metal chlorides was investigated to further increase the production of lomofungin in the afsR-overexpressing strain. The addition of different metal chlorides to S. lomondensis S015 N1 cultivations showed that CaCl2, FeCl2, and MnCl2 led to an increase in lomofungin biosynthesis. The optimum concentrations of these metal chlorides were obtained using response surface methodology. CaCl2 (0.04 mM), FeCl2 (0.33 mM), and MnCl2 (0.38 mM) gave a maximum lomofungin production titer of 318.0 ± 10.7 mg/l, which was a 4.1-fold increase compared with that of S. lomondensis S015 N1 without the addition of a metal chloride. This work demonstrates that the biosynthesis of phenazine metabolites can be induced by afsR. The results also indicate that metal chlorides addition might be a simple and useful strategy for improving the production of other phenazine metabolites in Streptomyces.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Huan; Zhang, Weiguo; Qian, Yu

This study investigates the distributions of Br, Ca, Cl, Cr, Cu, K, Fe, Mn, Pb, Ti, V and Zn inPhragmites australisroot system and the function of Fe nanoparticles in scavenging metals in the root epidermis using synchrotron X-ray microfluorescence, synchrotron transmission X-ray microscope measurement and synchrotron X-ray absorption near-edge structure techniques. The purpose of this study is to understand the mobility of metals in wetland plant root systems after their uptake from rhizosphere soils.Phragmites australissamples were collected in the Yangtze River intertidal zone in July 2013. The results indicate that Fe nanoparticles are present in the root epidermis and thatmore » other metals correlate significantly with Fe, suggesting that Fe nanoparticles play an important role in metal scavenging in the epidermis.« less

Heterogeneous nano-Fe/Ca/CaO catalytic ozonation for selective surface hydrophilization of plastics containing brominated and chlorinated flame retardants (B/CFRs): separation from automobile shredder residue by froth flotation.

PubMed

Mallampati, Srinivasa Reddy; Lee, Byoung Ho; Mitoma, Yoshiharu; Simion, Cristian

2017-02-01

One method of weakening the inherently hydrophobic surface of plastics relevant to flotation separation is heterogeneous nano-Fe/Ca/CaO catalytic ozonation. Nano-Fe/Ca/CaO-catalyzed ozonation for 15 min efficiently decreases the surface hydrophobicity of brominated and chlorinated flame retardant (B/CFR)-containing plastics (such as acrylonitrile-butadienestyrene (ABS), high-impact polystyrene (HIPS), and polyvinyl chloride (PVC)) in automobile shredder residue (ASR) to such an extent that their flotation ability is entirely depressed. Such a hydrophilization treatment also stimulates the ABS, HIPS, and PVC surface roughness, wetting of the surface, and the thermodynamic equilibrium conditions at the surface and ultimately changes surface polarity. SEM-EDS, AFM, and XPS analyses of the PVC and ABS surfaces demonstrated a marked decrease in [Cl/Br] and a significant increase in the number of hydrophilic groups, such as C-O, C=O, and (C=O)-O. Under froth flotation conditions at 50 rpm, about 99.5 % of ABS and 99.5 % of HIPS in ASR samples settled out, resulting in a purity of 98 and 98.5 % for ABS and HIPS in ASR samples, respectively. Furthermore, at 150 rpm, we also obtained 100 % PVC separation in the settled fraction, with 98 % purity in ASR. Total recovery of non-B/CFR-containing plastics reached nearly 100 % in the floating fraction. The amount of nano-Fe/Ca/CaO reagent employed during ozonation is very small, and additional removal of surface contaminants from the recycled ASR plastic surfaces by ozonation makes the developed process simpler, greener, and more effective.

Thermodynamic modeling of non-ideal mineral-fluid equilibria in the system Si-Al-Fe-Mg-Ca-Na-K-H-O-Cl at elevated temperatures and pressures: Implications for hydrothermal mass transfer in granitic rocks

NASA Astrophysics Data System (ADS)

Dolejš, David; Wagner, Thomas

2008-01-01

We present the results of thermodynamic modeling of fluid-rock interaction in the system Si-Al-Fe-Mg-Ca-Na-H-O-Cl using the GEM-Selektor Gibbs free energy minimization code. Combination of non-ideal mixing properties in solids with multicomponent aqueous fluids represents a substantial improvement and it provides increased accuracy over existing modeling strategies. Application to the 10-component system allows us to link fluid composition and speciation with whole-rock mineralogy, mass and volume changes. We have simulated granite-fluid interaction over a wide range of conditions (200-600 °C, 100 MPa, 0-5 m Cl and fluid/rock ratios of 10-2-104) in order to explore composition of magmatic fluids of variable salinity, temperature effects on fluid composition and speciation and to simulate several paths of alteration zoning. At low fluid/rock ratios (f/r) the fluid composition is buffered by the silicate-oxide assemblage and remains close to invariant. This behavior extends to a f/r of 0.1 which exceeds the amount of exsolved magmatic fluids controlled by water solubility in silicate melts. With increasing peraluminosity of the parental granite, the Na-, K- and Fe-bearing fluids become more acidic and the oxidation state increases as a consequence of hydrogen and ferrous iron transfer to the fluid. With decreasing temperature, saline fluids become more Ca- and Na-rich, change from weakly acidic to alkaline, and become significantly more oxidizing. Large variations in Ca/Fe and Ca/Mg ratios in the fluid are a potential geothermometer. The mineral assemblage changes from cordierite-biotite granites through two-mica granites to chlorite-, epidote- and zeolite-bearing rocks. We have carried out three rock-titration simulations: (1) reaction with the 2 m NaCl fluid leads to albitization, chloritization and desilication, reproducing essential features observed in episyenites, (2) infiltration of a high-temperature fluid into the granite at 400 °C leads to hydrolytic alteration commencing with alkali-feldspar breakdown and leading to potassic, phyllic and argillic assemblages; this is associated with reduction and iron metasomatism as observed in nature and (3) interaction with a multicomponent fluid at 600 °C produces sodic-calcic metasomatism. Na, Ca and Fe are the most mobile elements whereas immobility of Al is limited by f/r ∼ 400. All simulations predict a volume decrease by 3.4-5.4%, i.e., porosity formation at f/r < 30. At higher fluid/rock ratios simulation (2) produces a substantial volume increase (59%) due to mineral precipitation, whereas simulation (3) predicts a volume decrease by 49% at the advanced albitization-desilication stage. Volume changes closely correlate with mass changes of SiO2 and are related to silica solubility in fluids. The combined effects of oxygen fugacity, fluid acidity and pH for breakdown of aqueous metal complexes and precipitation of ore minerals were evaluated by means of reduced activity products. Sharp increases in saturation indexes for oxidative breakdown occur at each alteration zone whereas reductive breakdown or involvement of other chloride complexes favor precipitation at high fluid/rock ratios only. Calculations of multicomponent aqueous-solid equilibria at high temperatures and pressures are able to accurately predict rock mineralogy and fluid chemistry and are applicable to diverse reactive flow processes in the Earth's crust.

A Comparative Cathodoluminescence Emission Study of Feldspathic Glasses in SNC Meteorites and Quenched Melts of These Glasses

NASA Astrophysics Data System (ADS)

Kubny, A.; Jagoutz, E.

2001-12-01

In this study the cathodoluminescence (electron-excited luminescence) emission spectra were measured in the range 200 to 900 nm of individual feldspathic glass grains in the SNC meteorites Shergotty 101, Shergotty 232, ALHA 84001, EETA 79001-47, EETA 79001-276, and Dar al Gani 476 and those of quenched melts of the feldspathic glass grains. The quenching experiments of the original feldspathic glasses were conducted at 1500° C and atmospheric pressure. The aim of this CL emission study was the characterization of feldspathic glasses of SNC meteorites by comparison of the diagnostic spectral features of the feldspathic glasses of SNC meteorites with those of their quenched melts. In the CL emission spectra of the studied feldspathic glasses generally broad bands in the blue (ca. 460 nm), green (ca. 560 nm), and red (ca. 700 nm) can appear. These emission bands are assigned to structural defects (Al-O--Al centers), and the structural incorporation of Mn2+ and Fe3+ , respectively. The blue emission band at about 460 nm attributed to Al-O--Al centers is observed in the spectra of the original feldspathic glasses whereas it is not present (or only in low relative intensity) in the spectra of the quenched melts. The green emission band at 550 to 575 nm assigned to electronic transitions of Mn2+ in M sites is observed in the spectra of the original feldspathic glasses. It is shifted to longer wavelengths of 590 to 605 nm in the spectra of the quenched melts. The occurrence of the red emission band at about 700 nm attributed to electronic transition of Fe3+ in the spectra of the quenched melts of the feldspathic glasses indicates the presence of structural units which allow the occupancy of Fe3+ on tetrahedral sites. The results obtained by CL emission spectroscopy confirm results of Raman spectroscopic studies that the stuctures of feldspathic glasses of the studied SNC meteorites are modified by melting and quenching at atmospheric pressure. Additionally, comparison with published work on CL emission of shocked oligoclases shows that the feldspathic glasses of the studied SNC meteorites are not diaplectic but melt glasses.

Degradation of trichloroethylene in aqueous solution by calcium peroxide activated with ferrous ion.

PubMed

Zhang, Xiang; Gu, Xiaogang; Lu, Shuguang; Miao, Zhouwei; Xu, Minhui; Fu, Xiaori; Qiu, Zhaofu; Sui, Qian

2015-03-02

The application of calcium peroxide (CaO2) activated with ferrous ion to stimulate the degradation of trichloroethylene (TCE) was investigated. The experimental results showed that TCE could be completely degraded in 5 min at a CaO2/Fe(II)/TCE molar ratio of 4/8/1. Probe compound tests demonstrated the presence of reactive oxygen species HO· and O2(-·) in CaO2/Fe(II) system, while scavenging tests indicated that HO· was the dominant active species responsible for TCE removal, and O2(-·) could promote TCE degradation in CaO2/Fe(II) system. In addition, the influences of initial solution pH and solution matrix were evaluated. It suggested that the elevation of initial solution pH suppressed TCE degradation. Cl(-) had significant scavenging effect on TCE removal, whereas HCO3(-) of high concentration showed favorable function. The influences of NO3(-) and SO4(2-) could be negligible, while natural organic matter (NOM) had a negative effect on TCE removal at a relatively high concentration. The results demonstrated that the technique of CaO2 activated with ferrous ion is a highly promising technique in in situ chemical oxidation (ISCO) remediation in TCE contaminated sites. Copyright © 2014. Published by Elsevier B.V.

Evaluation of elemental enrichments in surface sediments off southwestern Taiwan

NASA Astrophysics Data System (ADS)

Chen, Chen-Tung; Kandasamy, Selvaraj

2008-05-01

Surface slices of 20 sediment cores, off southwestern Taiwan, and bed sediment of River Kaoping were measured for major and trace elements (Al, As, Ca, Cd, Cl, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Si, Ti, V, and Zn) to evaluate the geochemical processes responsible for their distribution, including elemental contamination. Major element/Al ratio and mean grain size indicate quartz-dominated, coarse grained sediments that likely derived from sedimentary rocks of Taiwan and upper crust of Yangtze Craton. Bi-plot of SiO2 versus Fe2O{3/T} suggests the possible iron enrichment in sediments of slag dumping sites. Highest concentrations of Cr, Mn, P, S, and Zn found in sediments of dumping sites support this. Correlation analysis shows dual associations, detrital and organic carbon, for Cr, P, S, and V with the latter association typical for sediments in dumping sites. Normalization of trace elements to Al indicates high enrichment factors (>2) for As, Cd, Pb, and Zn, revealing contamination. Factor analysis extracted four geochemical associations with the principal factor accounted for 25.1% of the total variance and identifies the combined effects of dumped iron and steel slag-induced C-S-Fe relationship owing to authigenic precipitation of Fe-Mn oxyhydroxides and/or metal sulfides, and organic matter complexation of Fe, Mn, Ca, Cr, P, and V. Factors 2, 3, and 4 reveal detrital association (Ti, Al, Ni, Pb, Cu, and V), effect of sea salt (Cl, Mg, Na, and K) and anthropogenic component (As and Zn)-carbonate link, respectively, in the investigated sediments.

Effects of sustained-release composite on the oxygen levels and sediment phosphorus fractions of an urban river in Shanghai.

PubMed

Li, Yang; Zhou, Yanbo; Zhou, Zhenhua; Wang, Ningsheng; Zhou, Qiang; Wang, Fuchen

2014-01-01

The eutrophication of many rivers and lakes is attributed to the anoxia and the increasing internal loading of nutrients from sediment. A novel sustained-release composite (SRC) synthesis of stearic acid and calcium peroxide (CaO2) was applied to supply a water body with oxygen endured in this study. The influences of SRC on the dissolved oxygen (DO) level, pH and total phosphorus (TP) of an urban river in Shanghai were studied. The results show that SRC has a longer oxygen-releasing cycle and a more tender effect on pH with the comparison of CaO2 powder. Reduction of 79.6% in the concentration of TP was observed in the water column. After 35 days of SRC addition, there was a significant positive correlation between TP and DO. As a consequence, the phosphorus fractions in sediment, including loosely sorbed P (NH4Cl-P), redox-sensitive P (Fe-P), calcium bound P (Ca-P), aluminium bound P (Al-P) and residual P (organic and refractory P) were affected by the addition of SRC. The NH4Cl-P and Fe-P fractions in the sediment that could release P easily were well constrained under the positive effect of SRC.

Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

NASA Astrophysics Data System (ADS)

Lange, R. A.; Waters, L.

2014-12-01

The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ΔNNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels in these 14 rhyolitic magmas, no effect is detected. Therefore, it can be robustly concluded that degassing of substantial amounts of the H2O component (≤ 6.5 wt%), by itself, does not induce oxidation in erupted magmas, particularly those more iron-rich than rhyolites (e.g., arc basalts).

Mass and number size distributions of particulate matter components: comparison of an industrial site and an urban background site.

PubMed

Taiwo, Adewale M; Beddows, David C S; Shi, Zongbo; Harrison, Roy M

2014-03-15

Size-resolved composition of particulate matter (PM) sampled in the industrial town of Port Talbot (PT), UK was determined in comparison to a typical urban background site in Birmingham (EROS). A Micro-Orifice Uniform Deposit Impactor (MOUDI) sampler was deployed for two separate sampling campaigns with the addition of a Grimm optical spectrometer at the PT site. MOUDI samples were analysed for water-soluble anions (Cl(-), NO₃(-) and SO₄(2-)) and cations (Na(+), NH4(+), K(+), Mg(2+) and Ca(2+)) and trace metals (Al, V, Cr, Mn, Fe, Cu, Zn, Sb, Ba and Pb). The PM mass distribution showed a predominance of fine particle (PM₂.₅) mass at EROS whereas the PT samples were dominated by the coarse fraction (PM₂.₅₋₁₀). SO₄(2-), Cl(-), NH4(+), Na(+), NO₃(-), and Ca(2+) were the predominant ionic species at both sites while Al and Fe were the metals with highest concentrations at both sites. Mean concentrations of Cl(-), Na(+), K(+), Ca(2+), Mg(2+), Cr, Mn, Fe and Zn were higher at PT than EROS due to industrial and marine influences. The contribution of regional pollution by sulphate, ammonium and nitrate was greater at EROS relative to PT. The traffic signatures of Cu, Sb, Ba and Pb were particularly prominent at EROS. Overall, PM at EROS was dominated by secondary aerosol and traffic-related particles while PT was heavily influenced by industrial activities and marine aerosol. Profound influences of wind direction are seen in the 72-hour data, especially in relation to the PT local sources. Measurements of particle number in 14 separate size bins plotted as a function of wind direction and speed are highly indicative of contributing sources, with local traffic dominant below 0.5 μm, steelworks emissions from 0.5 to 15 μm, and marine aerosol above 15 μm. Copyright © 2013 Elsevier B.V. All rights reserved.

The application of Westcott Formalism k0 NAA method to estimate short and medium lived elements in some Ghanaian herbal medicines complemented by AAS

NASA Astrophysics Data System (ADS)

Ayivor, J. E.; Okine, L. K. N.; Dampare, S. B.; Nyarko, B. J. B.; Debrah, S. K.

2012-04-01

The epithermal neutron shape factor, α of the inner and outer irradiation sites of the Ghana Research Reactor-1 (GHARR-1) was determined obtaining results of 0.105 for the inner (Channel 1) Irradiation site and 0.020 for the outer (channel 6) irradiation site. The neutron temperatures for the inner and outer irradiation sites were 27 °C and 20 °C, respectively. The α values used in Westcott Formalism k0 INAA was applied to determine multi elements in 13 Ghanaian herbal medicines used by the Centre for Scientific Research into Plant Medicine (CSRPM) for the management of various diseases complemented by Atomic Absorption Spectrometry. They are namely Mist. Antiaris, Mist. Enterica, Mist. Morazia, Mist. Nibima, Mist. Modium, Mist. Ninger, Mist Sodenia, Mist. Tonica, Chardicca Powder, Fefe Powder, Olax Powder, Sirrapac powder and Lippia Tea. Concentrations of Al, As, Br, K, Cl, Cu, Mg, Mn, Na and V were determined by short and medium irradiations at a thermal neutron flux of 5×1011 ncm-2 s-1. Fe, Cr, Pb, Co, Ni, Sn, Ca, Ba, Li and Sb were determined using Atomic Absorption Spectrometry (AAS). Ba, Cu, Li and V were present at trace levels whereas Al, Cl, Na, Ca were present at major levels. K, Br, Mg, Mn, Co, Ni, Fe and Sb were also present at minor levels. Arsenic was not detected in all samples. Standard Reference material, IAEA-V-10 Hay Powder was simultaneously analysed with samples. The precision and accuracy of the method using real samples and standard reference materials were evaluated and within ±10% of the reported value. Multivariate analytical techniques, such as cluster analysis (Q-mode and R-mode CA) and principal component analysis (PCA)/factor analysis (FA), have been applied to evaluate the chemical variations in the herbal medicine dataset. All the 13 samples may be grouped into 2 statistically significant clusters (liquid based and powdered herbal medicines), reflecting the different chemical compositions. R-mode CA and PCA suggest common sources for Co, Mg, Fe, Ca, Cr, Ni, Sn, Li and Sb and Na, V, Cl, Mn, Al, Br and K. The PCA/FA identified 3 dominant factors as responsible for the data structure, explaining 84.5% of the total variance in the dataset.

Ionic liquids and solids with paramagnetic anions.

PubMed

Krieger, Brenna M; Lee, Heather Y; Emge, Thomas J; Wishart, James F; Castner, Edward W

2010-08-21

Four paramagnetic ionic compounds have been prepared and their magnetic, structural and thermal properties have been investigated. The four compounds are methylbutylpyrrolidinium tetrachloroferrate(III) ([Pyrr(14)](+)/[FeCl(4)](-)), methyltributylammonium tetrachloroferrate(III) ([N(1444)](+)/[FeCl(4)](-)), butylmethylimidazolium tetrachloroferrate(III) ([bmim](+)/[FeCl(4)](-)) and tetrabutylammonium bromotrichloroferrate(III) ([N(4444)](+)/[FeBrCl(3)](-)). Temperature-dependent studies of their magnetic behaviors show that all four compounds are paramagnetic at ambient temperatures. Glass transitions are observed for only two of the four compounds, [Pyrr(14)](+)/[FeCl(4)](-) and [bmim](+)/[FeCl(4)](-). Crystal structures for [Pyrr(14)](+)/[FeCl(4)](-) and [N(1444)](+)/[FeCl(4)](-) are compared with the previously reported [N(4444)](+)/[FeBrCl(3)](-).

Role of solution chemistry in the retention and release of ...

EPA Pesticide Factsheets

Upon increasing production and use of graphene oxide nanoparticles (GONPs), concerns agitate over their potential impacts and risks to the environment, ecosystem, and human health. An improved understanding of the fate and transport including remobilization of GONPs in the subsurface environment enables us to better expedite the benign use of GONPs in a sustainable fashion but also evaluate their environmental impacts and health risks. In this study, the deposition and release of GONPs were systematically examined in water-saturated columns packed with either uncoated sand or iron oxide-coated sand (U-S and Fe-S, respectively) at environmentally relevant solution chemistry conditions (1–100 mM KCl and 0.1–10 mM CaCl2 at pH 7.0). Our results indicate that, in line with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, increasing influent ionic strength (IS) resulted in the reduced mobility of GONPs; and the impact of monovalent K+ was less than divalent Ca2+ in weakening the mobility of GONPs in both U-S and Fe-S. The positively charged iron oxide coating on the sand surface strongly immobilized the negatively charged GONPs at pH 7.0, producing the hyperexponential retention profiles for GONPs particularly in the presence of CaCl2 due primarily to the synergistic effects between iron oxide coating and Ca2+ (e.g., aggravate physical straining). A stepwise decreasing in pore-water transient IS initiated detachment of GONPs that were previously retained in the

Tularosa Basin Play Fairway Analysis: Water Chemistry

DOE Data Explorer

Adam Brandt

2015-12-15

This shapefile contains 409 well data points on Tularosa Basin Water Chemistry, each of which have a location (UTM), temperature, quartz and Potassium/Magnesium geothermometer; as well as concentrations of chemicals like Mn, Fe, Ba, Sr, Cs, Rb, As, NH4, HCO3, SO4, F, Cl, B, SiO2, Mg, Ca, K, Na, and Li.

Sources of variability in livestock water quality over 5 years in the Northern Great Plains

USDA-ARS?s Scientific Manuscript database

Mineral content of livestock water grazing rangelands can be a source of minerals affecting health and drinkability. To estimate yearly variation in water mineral concentrations, 11 indicators of quality were measured (Ca, Cl, Fe, Fl, Mg, Mn, Na, NO3-N, pH, SO4, total dissolved solids (TDS) and temp...

One-step electrolytic preparation of Si-Fe alloys as anodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Hailong; Sun, Diankun; Song, Qiqi; Xie, Wenqi; Jiang, Xu; Zhang, Bo

2016-06-01

One-step electrolytic formation of uniform crystalline Si-Fe alloy particles was successfully demonstrated in direct electro-reduction of solid mixed oxides of SiO2 and Fe2O3 in molten CaCl2 at 900∘C. Upon constant voltage electrolysis of solid mixed oxides at 2.8V between solid oxide cathode and graphite anode for 5h, electrolytic Si-Fe with the same Si/Fe stoichimetry of the precursory oxides was generated. The firstly generated Fe could function as depolarizers to enhance reduction rate of SiO2, resulting in the enhanced reduction kinetics to the electrolysis of individual SiO2. When evaluated as anode for lithium ion batteries, the prepared SiFe electrode showed a reversible lithium storage capacity as high as 470mAh g-1 after 100 cycles at 200mA g-1, promising application in high-performance lithium ion batteries.

Identifying and Quantifying Chemical Forms of Sediment-Bound Ferrous Iron.

NASA Astrophysics Data System (ADS)

Kohler, M.; Kent, D. B.; Bekins, B. A.; Cozzarelli, I.; Ng, G. H. C.

2015-12-01

Aqueous Fe(II) produced by dissimilatory iron reduction comprises only a small fraction of total biogenic Fe(II) within an aquifer. Most biogenic Fe(II) is bound to sediments on ion exchange sites; as surface complexes and, possibly, surface precipitates; or incorporated into solid phases (e.g., siderite, magnetite). Different chemical forms of sediment-bound Fe(II) have different reactivities (e.g., with dissolved oxygen) and their formation or destruction by sorption/desorption and precipitation/dissolution is coupled to different solutes (e.g., major cations, H+, carbonate). We are quantifying chemical forms of sediment-bound Fe(II) using previously published extractions, novel extractions, and experimental studies (e.g., Fe isotopic exchange). Sediments are from Bemidji, Minnesota, where biodegradation of hydrocarbons from a burst oil pipeline has driven extensive dissimilatory Fe(III) reduction, and sites potentially impacted by unconventional oil and gas development. Generally, minimal Fe(II) was mobilized from ion exchange sites (batch desorption with MgCl2 and repeated desorption with NH4Cl). A < 2mm sediment fraction from the iron-reducing zone at Bemidji had 1.8umol/g Fe(II) as surface complexes or carbonate phases (sodium acetate at pH 5) of which ca. 13% was present as surface complexes (FerroZine extractions). Total bioavailable Fe(III) and biogenic Fe(II) (HCl extractions) was 40-50 umole/g on both background and iron-reducing zone sediments . Approximately half of the HCl-extractable Fe from Fe-reducing zone sediments was Fe(II) whereas 12 - 15% of Fe extracted from background sediments was present as Fe(II). One-third to one-half of the total biogenic Fe(II) extracted from sediments collected from a Montana prairie pothole located downgradient from a produced-water disposal pit was present as surface-complexed Fe(II).

Leaf elemental analysis in mycorrhizal post oak seedlings

NASA Astrophysics Data System (ADS)

Boling, B. C.; Naab, F. U.; Smith, D.; Duggan, J. L.; McDaniel, F. D.

2006-09-01

Growth and element assimilation was investigated in the leaves of post oak seedlings exposed to four different treatment combinations of fertilization and ectomycorrhizal inoculation. Element concentration was analyzed via particle-induced X-ray emission spectrometry (PIXE). PIXE detected 10 of the 13 essential macro and micronutrients: P, S, Mg, Ca, K, Cu, Zn, Mn, Fe and Cl. Mean growth and dry weight was significantly different across the treatment groups as well as the mean concentration of Mg, Al, S, K, Ca, Fe, Cu and Zn. The data suggest that fertilization rather than mycorrhizal inoculation had a stronger influence on nutrient uptake. This study is the first to analyze element concentration in post oak and to investigate the potential benefits of mycorrhizal symbiosis in post oak seedlings in terms of nutrient uptake.

Volatilization, transport and sublimation of metallic and non-metallic elements in high temperature gases at Merapi Volcano, Indonesia

USGS Publications Warehouse

Symonds, R.B.; Rose, William I.; Reed, M.H.; Lichte, F.E.; Finnegan, David L.

1987-01-01

Condensates, silica tube sublimates and incrustations were sampled from 500-800??C fumaroles and lava samples were collected at Merapi Volcano, Indonesia in Jan.-Feb., 1984. With respect to the magma, Merapi gases are enriched by factors greater than 105 in Se, Re, Bi and Cd; 104-105 in Au, Br, In, Pb and W; 103-104 in Mo, Cl, Cs, S, Sn and Ag; 102-103 in As, Zn, F and Rb; and 1-102 in Cu, K, Na, Sb, Ni, Ga, V, Fe, Mn and Li. The fumaroles are transporting more than 106 grams/day ( g d) of S, Cl and F; 104-106 g/d of Al, Br, Zn, Fe, K and Mg; 103-104 g d of Pb, As, Mo, Mn, V, W and Sr; and less than 103 g d of Ni, Cu, Cr, Ga, Sb, Bi, Cd, Li, Co and U. With decreasing temperature (800-500??C) there were five sublimate zones found in silica tubes: 1) cristobalite and magnetite (first deposition of Si, Fe and Al); 2) K-Ca sulfate, acmite, halite, sylvite and pyrite (maximum deposition of Cl, Na, K, Si, S, Fe, Mo, Br, Al, Rb, Cs, Mn, W, P, Ca, Re, Ag, Au and Co); 3) aphthitalite (K-Na sulfate), sphalerite, galena and Cs-K. sulfate (maximum deposition of Zn, Bi, Cd, Se and In; higher deposition of Pb and Sn); 4) Pb-K chloride and Na-K-Fe sulfate (maximum deposition of Pb, Sn and Cu); and 5) Zn, Cu and K-Pb sulfates (maximum deposition of Pb, Sn, Ti, As and Sb). The incrustations surrounding the fumaroles are also chemically zoned. Bi, Cd, Pb, W, Mo, Zn, Cu, K, Na, V, Fe and Mn are concentrated most in or very close to the vent as expected with cooling, atmospheric contamination and dispersion. The highly volatile elements Br, Cl, As and Sb are transported primarily away from high temperature vents. Ba, Si, P, Al, Ca and Cr are derived from wall rock reactions. Incomplete degassing of shallow magma at 915??C is the origin of most of the elements in the Merapi volcanic gas, although it is partly contaminated by particles or wall rock reactions. The metals are transported predominantly as chloride species. As the gas cools in the fumarolic environment, it becomes saturated with sublimate phases that fractionate from the gas in the order of their equilibrium saturation temperatures. Devolatilization of a cooling batholith could transport enough acids and metals to a hydrothermal system to play a significant role in forming an ore deposit. However, sublimation from a high temperature, high velocity carrier gas is not efficient enough to form a large ore deposit. Re, Se, Cd and Bi could be used as supporting evidence for magmatic fluid transport in an ore deposit. ?? 1987.

Influence of marine, terrestrial and anthropogenic sources on ionic and metallic composition of rainwater at a suburban site (northwest coast of Spain)

NASA Astrophysics Data System (ADS)

Moreda-Piñeiro, Jorge; Alonso-Rodríguez, Elia; Moscoso-Pérez, Carmen; Blanco-Heras, Gustavo; Turnes-Carou, Isabel; López-Mahía, Purificación; Muniategui-Lorenzo, Soledad; Prada-Rodríguez, Darío

2014-05-01

In the present research, the rainwater chemistry of soluble (SF) and non-soluble (NSF) fractions is studied over a one a half year period (from March 2011 to August 2012) at a suburban site (Oleiros, A Coruña, Spain). The monthly rainfall in this region during the studied period ranged from 10 to 137 mm, while the NSF ranged from 0.9 to 54 mg L-1. More rainfall occurs within October-January. Eighteen samples, which provide information pertaining to the monthly variation in chemistry, were analyzed. Trace metals (Al, As, Ba, Co, Cu, Cr, Fe, Mn, Ni, Pb, Sr, V, Zn) were enclosed in the study of both fractions of the rainwater. Major inorganic ions (Cl-, NO3-, SO42-, Na+, K+, Ca2+, Mg2+ and NH4+) were also enclosed in the study of the SF of the rainwater. After partition coefficients analysis, univariate and principal components analysis (PCA) and air mass back trajectories analysis, three sources were found for the ionic and metal composition of the SF of rainwater; terrestrial (Ca2+, non sea salt SO42-, Al and Fe), marine (Mg2+, Na+, Cl-) and anthropogenic (K+, NH4+, NO3-, Fe, Mn, Pb, Sr, V and Zn). Results also suggest ubiquitous sources for Ba, Co, Cu, Cr and Ni. One source (terrestrial) was found for NSF of rainwater.

Documentation of the appearance of a caviar-type deposit in Oven 1 following a large scale experiment for heating oil with Upper Silesian coal (in German)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rank

1942-03-26

When the oven was disassembled after the test, small kernels of porous material were found in both the upper and lower portion of the oven to a depth of about 2 m. The kernels were of various sizes up to 4 mm. From 1,300 metric ..cap alpha..ons of dry coal, there were 330 kg or the residue of 0.025% of the coal input. These kernels brought to mind deposits of spheroidal material termed ''caviar'', since they had rounded tops. However, they were irregularly long. After multiaxis micrography, no growth rings were found as in Leuna's lignite caviar. So, it wasmore » a question of small particles consisting almost totally of ash. The majority of the composition was Al, Fe, Na, silicic acid, S and Cl. The sulfur was found to be in sulfide form and Cl in a volatile form. The remains did not turn to caviar form since the CaO content was slight. The Al, Fe, Na, silicic acid, S and Cl were concentrated in comparison to coal ash and originate apparently from the catalysts (FeSO/sub 4/, Bayermasse, and Na/sub 2/S). It was notable that the Cl content was so high. 2 graphs, 1 table« less

Calculation of phase diagrams for the FeCl2, PbCl2, and ZnCl2 binary systems by using molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Seo, Won-Gap; Matsuura, Hiroyuki; Tsukihashi, Fumitaka

2006-04-01

Recently, molecular dynamics (MD) simulation has been widely employed as a very useful method for the calculation of various physicochemical properties in the molten slags and fluxes. In this study, MD simulation has been applied to calculate the structural, transport, and thermodynamic properties for the FeCl2, PbCl2, and ZnCl2 systems using the Born—Mayer—Huggins type pairwise potential with partial ionic charges. The interatomic potential parameters were determined by fitting the physicochemical properties of iron chloride, lead chloride, and zinc chloride systems with experimentally measured results. The calculated structural, transport, and thermodynamic properties of pure FeCl2, PbCl2, and ZnCl2 showed the same tendency with observed results. Especially, the calculated structural properties of molten ZnCl2 and FeCl2 show the possibility of formation of polymeric network structures based on the ionic complexes of ZnCl{4/2-}, ZnCl{3/-}, FeCl{4/2-}, and FeCl{3/-}, and these calculations have successfully reproduced the measured results. The enthalpy, entropy, and Gibbs energy of mixing for the PbCl2-ZnCl2, FeCl2-PbCl2, and FeCl2-ZnCl2 systems were calculated based on the thermodynamic and structural parameters of each binary system obtained from MD simulation. The phase diagrams of the PbCl2-ZnCl2, FeCl2-PbCl2, and FeCl2-ZnCl2 systems estimated by using the calculated Gibbs energy of mixing reproduced the experimentally measured ones reasonably well.

Understanding the evolution of S- and I-type granitic plutons through analysis of apatite.

NASA Astrophysics Data System (ADS)

Hess, B. L.; Fiege, A.; Tailby, N.

2017-12-01

The major and trace element composition of apatites from the Lachlan fold belt (LFB) S- and I-type granitoids (Australia) and the Central French Massif (CFM) S-type leucogranites (France) were analyzed to investigate their compositional and redox variation. Apatite is a common accessory mineral in magmatic systems that can incorporate a variety of trace elements, including the polyvalent elements sulfur (S), iron (Fe), and manganese (Mn). It was recently discovered that apatite can incorporate three oxidation states of S (S6+, S4+, S2-) into its structure as a function of oxygen fugacity [1]. However, the oxidation states of Mn and Fe in apatite are essentially unknown (2+ and/or 3+). In this study, we collected many electron probe line transects across apatites in several different host phases from a variety of S- and I-type plutons. The F-H-Cl contents of the S- and I-type LFB samples were similar ( 2.9 wt% F, 0.4 wt% Cl, 0.5 wt% OH). The CFM S-types contained virtually no Cl and ranged from near-endmember OH-apatite to near-endmember F-apatite. The apatites of all studied the S- and I-type plutons are characterized by similar ranges of Fe content (<1.5 wt% Fe), while Mn reaches much higher concentrations in the S-type when compared to I-type apatites (<6.5 wt% Mn). The S content of the apatites varies significantly, from <50 ppm S in the LFB S-types, up to 2,000 ppm S in the LFB I-types, and reaching 1,650 ppm S in the CFM S-types. The elevated S contents in the LFB I-type and CFM S-type apatites allowed us to measure the S oxidation states by using X-ray absorption near-edge structure (XANES) spectroscopy. The spectra show variability in S oxidation states ranging from mostly sulfate down to nearly equal S6+/S2- ratios, indicating redox variations during apatite formation. The S-type Mn + Fe content plots in a 1:1 ratio against calcium (Ca) in atoms per formula unit, while the I-type apatites have too low Mn and Fe to show a clear trend. Thus, divalent Mn and Fe probably replace Ca2+ in the S-types' apatite structure, while the incorporation of trivalent Mn or Fe in apatite is rather unlikely. We suggest that Mn and Fe contents in apatite may become a useful tracer of melt evolution once the distributions coefficients are experimentally calibrated. [1] Konecke et al. (2017), Am Mineral

Orosensory responsiveness to and preference for hydroxide-containing salts in mice.

PubMed

St John, Steven J; Boughter, John D

2009-07-01

Historically, taste researchers have considered the possibility that the gustatory system detects basic compounds, such as those containing the hydroxide ion, but evidence for an "alkaline taste" has not been strong. We found that, in 48 h, 2-bottle preference tests, C3HeB/FeJ (C3) mice showed a preference for Ca(OH)(2), whereas SWR/J (SW) mice showed avoidance. Strain differences were also apparent to NaOH but not CaCl(2). Follow-up studies showed that the strain difference for Ca(OH)(2) was stable over time (Experiment 2) but that C3 and SW mice did not differ in their responses to Ca(OH)(2) or NaOH in brief-access tests, where both mice avoided high concentrations of these compounds (Experiment 3). In order to assess the perceived quality of Ca(OH)(2), mice were tested in 2 taste aversion generalization experiments (Experiments 4 and 5). Aversions to Ca(OH)(2) generalized to NaOH but not CaCl(2) in both strains, suggesting that the generalization was based on the hydroxide ion. Both strains also generalized aversions to quinine, suggesting the possibility that the hydroxide ion has a bitter taste quality to these mice, despite the preference shown by C3 mice to middle concentrations in long-term tests.

Ionic Liquids and Solids with Paramagnetic Anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Castner, Jr., E.W.; Wishart, J.; Krieger, B.M.

2010-06-18

Four paramagnetic ionic compounds have been prepared and their magnetic, structural and thermal properties have been investigated. The four compounds are methylbutylpyrrolidinium tetrachloroferrate(III) ([Pyrr{sub 14}]{sup +}/[FeCl{sub 4}]{sup -}), methyltributylammonium tetrachloroferrate(III) ([N{sub 1444}]{sup +}/[FeCl{sub 4}]{sup -}), butylmethylimidazolium tetrachloroferrate(III) ([bmim]{sup +}/[FeCl{sub 4}]{sup -}) and tetrabutylammonium bromotrichloroferrate(III) ([N{sub 4444}]{sup +}/[FeBrCl{sub 3}]{sup -}). Temperature-dependent studies of their magnetic behaviors show that all four compounds are paramagnetic at ambient temperatures. Glass transitions are observed for only two of the four compounds, [Pyrr{sub 14}]{sup +}/[FeCl{sub 4}]{sup -} and [bmim]{sup +}/[FeCl{sub 4}]{sup -}. Crystal structures for [Pyrr{sub 14}]{sup +}/[FeCl{sub 4}]{sup -} and [N{sub 1444}]{sup +}/[FeCl{sub 4}]{sup -}more » are compared with the previously reported [N{sub 4444}]{sup +}/[FeBrCl{sub 3}]{sup -}.« less

Synchrotron X-ray microfluorescence measurement of metal distributions in Phragmites australis root system in the Yangtze River intertidal zone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Huan; Zhang, Weiguo; Qian, Yu

2016-06-15

This study investigates the distributions of Br, Ca, Cl, Cr, Cu, K, Fe, Mn, Pb, Ti, V and Zn inPhragmites australisroot system and the function of Fe nanoparticles in scavenging metals in the root epidermis using synchrotron X-ray microfluorescence, synchrotron transmission X-ray microscope measurement and synchrotron X-ray absorption near-edge structure techniques. The purpose of this study is to understand the mobility of metals in wetland plant root systems after their uptake from rhizosphere soils.Phragmites australissamples were collected in the Yangtze River intertidal zone in July 2013. The results indicate that Fe nanoparticles are present in the root epidermis and thatmore » other metals correlate significantly with Fe, suggesting that Fe nanoparticles play an important role in metal scavenging in the epidermis.« less

The size distribution and origin of elements bound to ambient particles: a case study of a Polish urban area.

PubMed

Rogula-Kozłowska, Wioletta; Majewski, Grzegorz; Czechowski, Piotr Oskar

2015-05-01

Ambient particulate matter (PM) was sampled in Zabrze (southern Poland) in the heating period of 2009. It was investigated for distribution of its mass and of the masses of its 18 component elements (S, Cl, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Ge, As, Br, Sr, Cd, Sb, Ba, and Pb) among 13 PM size fractions. In the paper, the distribution modality of and the correlations between the ambient concentrations of these elements are discussed and interpreted in terms of the source apportionment of PM emissions. By weight, S, Cl, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Ge, As, Br, Sr, Cd, Sb, Ba, and Pb were 10% of coarse and 9% of ultrafine particles. The collective mass of these elements was no more than 3.5 % of the mass of the particles with the aerodynamic diameter D p between 0.4 and 1.0 μm (PM₀.₄₋₁), whose ambient mass concentration was the highest. The PM mass size distribution for the sampling period is bimodal; it has the accumulation and coarse modes. The coarse particles were probably of the mineral/soil origin (characteristic elements: Ca, Fe, Sr, and Ba), being re-suspended polluted soil or road dust (characteristic elements: Ca, Fe, Sr, Ba, S, K, Cr, Cu, Zn, Br, Sb, Pb). The maxima of the density functions (modes) of the concentration distributions with respect to particle size of PM-bound S, Cl, K, Cu, Zn, Ge, Br, Cd, Sb, and Pb within the D p interval from 0.108 to 1.6 μm (accumulation PM particles) indicate the emissions from furnaces and road traffic. The distributions of PM-bound As, Mn, Ba, and Sr concentrations have their modes within D p ≤ 0.108 μm (nucleation PM particles), indicating the emissions from high-temperature processes (industrial sources or car engines). In this work, principal component analysis (PCA) is applied separately to each of the 13 fraction-related sets of the concentrations of the 18 PM-bound elements, and further, the fractions are grouped by their origin using cluster analysis (CA) applied to the 13 fraction-related first principal components (PC1). Four distinct groups of the PM fractions are identified: (PM₁.₆₋₂.₅, PM₂.₅₋₄.₄,), (PM₀.₀₃₋₀.₀₆, PM₀.₁₀₈₋₀.₁₇), (PM₀.₀₆₋₀.₁₀₈, PM₀.₁₇₋₀.₂₆, PM₀.₂₆₋₀.₄, PM₀.₄₋₀.₆₅, PM₀.₆₅₋₁, PM₁₋₁.₆), and (PM₄.₄₋₆.₈, PM₆.₈₋₁₀, PM>₁₀). The PM sources attributed to these groups by using PCA followed by CA are roughly the same as the sources from the apportionment done by analyzing the modality of the mass size distributions.

Source identification of particulate matter in a semi-urban area of Malaysia using multivariate techniques.

PubMed

Wahid, N B A; Latif, M T; Suan, L S; Dominick, D; Sahani, M; Jaafar, S A; Mohd Tahir, N

2014-03-01

This study aims to determine the composition and sources of particulate matter with an aerodynamic diameter of 10 μm or less (PM10) in a semi-urban area. PM10 samples were collected using a high volume sampler. Heavy metals (Fe, Zn, Pb, Mn, Cu, Cd and Ni) and cations (Na(+), K(+), Ca(2+) and Mg(2+)) were detected using inductively coupled plasma mass spectrometry, while anions (SO4 (2-), NO3 (-), Cl(-) and F(-)) were analysed using Ion Chromatography. Principle component analysis and multiple linear regressions were used to identify the source apportionment of PM10. Results showed the average concentration of PM10 was 29.5 ± 5.1 μg/m(3). The heavy metals found were dominated by Fe, followed by Zn, Pb, Cu, Mn, Cd and Ni. Na(+) was the dominant cation, followed by Ca(2+), K(+) and Mg(2+), whereas SO4 (2-) was the dominant anion, followed by NO3 (-), Cl(-) and F(-). The main sources of PM10 were the Earth's crust/road dust, followed by vehicle emissions, industrial emissions/road activity, and construction/biomass burning.

Trace elemental analysis in cancer-afflicted tissues of penis and testis by PIXE technique

NASA Astrophysics Data System (ADS)

Naga Raju, G. J.; John Charles, M.; Bhuloka Reddy, S.; Sarita, P.; Seetharami Reddy, B.; Rama Lakshmi, P. V. B.; Vijayan, V.

2005-04-01

PIXE technique was employed to estimate the trace elemental concentrations in the biological samples of cancerous penis and testis. A 3 MeV proton beam was employed to excite the samples. From the present results it can be seen that the concentrations of Cl, Fe and Co are lower in the cancerous tissue of the penis when compared with those in normal tissue while the concentrations of Cu, Zn and As are relatively higher. The concentrations of K, Ca, Ti, Cr, Mn, Br, Sr and Pb are in agreement within standard deviations in both cancerous and normal tissues. In the cancerous tissue of testis, the concentrations of K, Cr and Cu are higher while the concentrations of Fe, Co and Zn are lower when compared to those in normal tissue of testis. The concentrations of Cl, Ca, Ti and Mn are in agreement in both cancerous and normal tissues of testis. The higher levels of Cu lead to the development of tumor. Our results also support the underlying hypothesis of an anticopper, antiangiogenic approach to cancer therapy. The Cu/Zn ratios of both penis and testis were higher in cancer tissues compared to that of normal.

Improving La0.6Sr0.4Co0.8Fe0.2O3-δ infiltrated solid oxide fuel cell cathode performance through precursor solution desiccation

NASA Astrophysics Data System (ADS)

Burye, Theodore E.; Nicholas, Jason D.

2015-02-01

Here, for the first time, the average size of solid oxide fuel cell (SOFC) electrode nano-particles was reduced through the chemical desiccation of infiltrated precursor nitrate solutions. Specifically, after firing at 700 °C, CaCl2-desiccated La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF) - Ce0.9Gd0.1O1.95 (GDC) cathodes contained LSCF infiltrate particles with an average size of 22 nm. This is in contrast to comparable, undesiccated LSCF-GDC cathodes which contained LSCF infiltrate particles with an average size of 48 nm. X-ray diffraction, scanning electron microscopy, and controlled atmosphere electrochemical impedance spectroscopy revealed that desiccation reduced the average infiltrate particle size without altering the infiltrate phase purity, the cathode concentration polarization resistance, or the cathode electronic resistance. Compared to undesiccated LSCF-GDC cathodes achieving polarization resistances of 0.10 Ωcm2 at 640 °C, comparable CaCl2-dessicated LSCF-GDC cathodes achieved 0.10 Ωcm2 at 575 °C. Mathematical modeling suggested that these performance improvements resulted solely from average infiltrate particle size reductions.

μPIXE for a μBrain: The vinegar fly's brain, antenna, sensilla hairs and eye ion concentrations

NASA Astrophysics Data System (ADS)

Reinert, Anja; Barapatre, Nirav; Sachse, Silke; Reinert, Tilo

2011-10-01

The vinegar fly Drosophila melanogaster is used as model organism to study a variety of different scientific purposes. Thus, our laboratory studies the olfactory system by neurobiological experiments. These techniques are often disruptive and need to compensate or exchange the body fluid, the lymph, with an artificial Ringer's solution in defined compartments of the fly. The solution mainly contains Na, Cl, K and Ca and is to keep physiological conditions. Therefore, the knowledge about the ion concentrations in the respective Drosophila lymph is required for a correct mixture of the ions. This paper presents the spatially resolved concentrations of P, S, Cl, K, Ca, Fe, Cu and Zn in lyophilised head cryosections of Drosophila by using quantitative μPIXE at the ion beam facility LIPSION in Leipzig. The PIXE maps enable a detailed analysis of particular regions of interest down to a spatial resolution of 0.5 μm. We quantified the ion concentrations especially in the brain, the antenna and its sensilla hairs acting as the olfactory organ of the fly, in the compound eye and in the mouthparts. The averaged element concentrations of these main compartments are (in descending order): P: 90 mM, K: 81 mM, S: 38 mM, Cl: 18 mM, Ca: 4.9 mM, Fe: 1.4 mM, Zn: 1.2 mM, Cu: 0.06 mM. Certain structures or cavities possess a remarkably high concentration of particular elements and might reflect the different functions of the compartments. An example presented in more detail is the composition of the compound eye. Conclusively, our findings on the ion concentrations might be useful for the mixture of the Drosophila Ringer's solution to ensure physiological conditions in experiments.

Use of ferric chloride to identify salicylate-containing poisons.

PubMed

Hoffman, Robert J; Nelson, Lewis S; Hoffman, Robert S

2002-01-01

Ferric chloride (FeCl3) is used to qualitatively test the urine of patients with presumed salicylate exposure. FeCl3 testing of an unidentified poison might provide evidence of salicylate exposure in situations where FeCl3 urine testing cannot be used. Such situations include the absence of a urine sample, immediately after ingestion before urine contains a detectable quantity of salicylate, or for patients chronically using salicylatesfor which FeCl3 testing is unhelpful. This study seeks to determine if FeCl3 can be used to identify salicylate-containing products. We assessed the reactivity of FeCl3 with commercially available salicylate-containing products. We applied 0.1 mL of 10% FeCl3 solution to each of 15 various salicylate-containing products including: regular and buffered acetylsalicylic acid, bismuth subsalicylate, methylsalicylate, physostigmine salicylate, salicylic acid, trolamine salicylate, and herbal tablets with salicin-containing white willow bark (Salix sp.). These products tested were: regular and enteric-coatedpills (n = 4), powder (n = 1), topical creams (n = 5), topical liquids (n = 4), and intravenous solution (n = 1). FeCl3 was applied to crushed tablets and added directly to liquids and creams. Fifteen salicylate-free controls including liquids, pills, and creams similar in appearance to experimental samples were also tested. Three blinded physiciansfamiliar with FeCl3 testing independently observed the addition of FeCl3 to each sample and rated a positive or negative result. All salicylate-containing products were interpreted to be clearly FeCl3 positive and all control samples were interpreted to be clearly FeCl3 negative. Salicylate-containing products may be identified using FeCl33. When using FeCl3

Crystal structures of two new low-symmetry calcium-deficient analogs of eudialyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rastsvetaeva, R. K.; Rozenberg, K. A.; Pekov, I. V.

2006-03-15

The crystal structures of two new low-symmetry (sp. gr. R3) representatives of the eudialyte group from Mont Saint-Hilaire (Quebec, Canada) and the Lovozero massif (Kola Peninsula, Russia) were studied by single-crystal X-ray diffraction analysis and refined to R = 0.068 and 0.054 using 2899 reflections with F > 5{sigma}(F) and 2927 reflections with F > 3{sigma}(F), respectively. The idealized formulas of these representatives are Na{sub 13}(Ca{sub 3}Mn{sub 3})Zr{sub 3}(Fe, Mn){sub 3}({open_square})(Si)[Si{sub 3}O{sub 9}]{sub 2}[Si{sub 9}O{sub 27}]{sub 2}(O, OH, Cl){sub 3} . 2H{sub 2}O and Na{sub 15}(Ca{sub 3}Mn{sub 3})Zr{sub 3}(Fe, Zr){sub 3}(Si)(Si) . [Si{sub 3}O{sub 9}]{sub 2}[Si{sub 9}O{sub 27}]{sub 2}O{sub 2}(OH,more » F, Cl){sub 2} . 2H{sub 2}O. Both minerals are analogs of oneillite and are characterized by a low Ca content. The distinguishing features of the mineral from Quebec are that the M(4) site is essentially vacant (>50%) and Ca atoms occupy one independent site in the six-membered ring, whereas another site is occupied by Mn along with a small impurity of Na. In the mineral from the Lovozero massif, both the M(3) and M(4) sites are occupied predominantly by silicon, while Ca atoms are distributed between both octahedral sites of the six-membered ring, one of these sites being occupied predominantly by Mn.« less

Comparison between PGAA and ID-AMS analysis for determining chlorine content in whole rock basalt

NASA Astrophysics Data System (ADS)

di Nicola, L.; Schnabel, C.; Wilcken, K. M.; Gméling, K.

2009-04-01

Accurate determination of chlorine concentrations in terrestrial rocks is of importance for the interpretation of terrestrial in-situ cosmogenic 36Cl. Neutron capture by 35Cl, together with production from Ca and K, is one of the three major production pathways of 36Cl in rocks. Here, we present an inter-comparison of chlorine determinations by two procedures. The first approach is an independent Cl determination by prompt gamma (neutron) activation analysis (PGAA). The second method is isotope dilution based on isotopically-enriched stable chlorine carrier added during chemical sample preparation for accelerator mass spectrometry (ID-AMS). Twenty six (26) whole rock samples have been processed for PGAA and ID-AMS analyses. Elemental analysis by PGAA provides concentrations of major, minor and trace elements including the target elements for 36Cl production (K, Ca, Ti, and Fe), as well as of neutron absorbers and neutron moderators (H, B, Cl, Sm and Gd). The Cl concentrations determined during this study constitute the first inter-comparison for concentrations below 100 μCl/g. Our results show no significant difference in Cl concentrations between methods, and comparable uncertainties. This agreement guarantees that during the procedure we employ for whole rock sample no significant loss of stable chlorine from either the spike or the sample occurs before isotopic equilibration, prior to AgCl precipitation. Furthermore, we show that the elemental analysis by PGAA offers anadvance for the interpretation of 36Cl measurements. It allows simultaneous measurement of major and most trace element concentrations with a precision necessary for calculating the relative contributions to 36Cl production rates of the different mechanisms. Finally, the Cl concentration can be used to optimize the amount of isotopically-enriched spike for AMS-ID sample preparation for 36Cl.

The effect of age and gender on 38 chemical element contents in human iliac crest investigated by instrumental neutron activation analysis.

PubMed

Zaichick, Sofia; Zaichick, Vladimir

2010-01-01

To understand the role of major, minor, and trace elements in the etiology of bone diseases including osteoporosis, it is necessary to determine the normal levels and age-related changes of bone chemical elements. The effect of age and gender on 38 chemical element contents in intact iliac crest of 84 apparently healthy 15-55 years old women (n=38) and men (n=46) was investigated by neutron activation analysis. Mean values (M+/-SEM) for mass fraction (on dry weight basis) of Ca, Cl, Co, Fe, K, Mg, Mn, Na, P, Rb, Sr, and Zn for both female and male taken together were Ca - 169+/-3g/kg, Cl - 1490+/-43 mg/kg, Co - 0.0073+/-0.0024 mg/kg, Fe - 177+/-24 mg/kg, K - 1820+/-79 mg/kg, Mg - 1840+/-48 mg/kg, Mn - 0.316+/-0.013 mg/kg, Na - 4970+/-87 mg/kg, P - 79.7+/-1.5 g/kg, Rb - 1.89+/-0.22 mg/kg, Sr - 312+/-15 mg/kg, and Zn - 65.9+/-3.4 mg/kg, respectively. The upper limit of mean contents of Cs, Eu, Hg, Sb, Sc, and Se were Cs < or = 0.09 mg/kg, Eu < or = 0.005 mg/kg, Hg < or = 0.005 mg/kg, Sb < or = 0.004 mg/kg, Sc < or = 0.001 mg/kg, and Se < or = 0.1mg/kg, respectively. In all bone samples the contents of Ag, As, Au, Ba, Br, Cd, Ce, Cr, Gd, Hf, La, Lu, Nd, Sm, Ta, Tb, Th, U, Yb, and Zr were under detection limits. The Ca, Mg, and P contents decrease with age, regardless of gender. Higher Ca, Mg, P, and Sr mass fractions as well as lower Fe content are typical of female iliac crest as compared to those in male bone. Copyright 2009 Elsevier GmbH. All rights reserved.

Groundwater chemistry and occurrence of arsenic in the Meghna floodplain aquifer, southeastern Bangladesh

USGS Publications Warehouse

Zahid, A.; Hassan, M.Q.; Balke, K.-D.; Flegr, M.; Clark, D.W.

2008-01-01

Dissolved major ions and important heavy metals including total arsenic and iron were measured in groundwater from shallow (25-33 m) and deep (191-318 m) tube-wells in southeastern Bangladesh. These analyses are intended to help describe geochemical processes active in the aquifers and the source and release mechanism of arsenic in sediments for the Meghna Floodplain aquifer. The elevated Cl- and higher proportions of Na+ relative to Ca2+, Mg2+, and K+ in groundwater suggest the influence by a source of Na+ and Cl-. Use of chemical fertilizers may cause higher concentrations of NH 4+ and PO 43- in shallow well samples. In general, most ions are positively correlated with Cl-, with Na+ showing an especially strong correlation with Cl-, indicating that these ions are derived from the same source of saline waters. The relationship between Cl-/HCO 3- ratios and Cl- also shows mixing of fresh groundwater and seawater. Concentrations of dissolved HCO 3- reflect the degree of water-rock interaction in groundwater systems and integrated microbial degradation of organic matter. Mn and Fe-oxyhydroxides are prominent in the clayey subsurface sediment and well known to be strong adsorbents of heavy metals including arsenic. All five shallow well samples had high arsenic concentration that exceeded WHO recommended limit for drinking water. Very low concentrations of SO 42- and NO 3- and high concentrations of dissolved Fe and PO 43- and NH 4+ ions support the reducing condition of subsurface aquifer. Arsenic concentrations demonstrate negative co-relation with the concentrations of SO 42- and NO 3- but correlate weakly with Mo, Fe concentrations and positively with those of P, PO 43- and NH 4+ ions. ?? 2007 Springer-Verlag.

The Interfacial Behavior between Biochar and Soil Minerals and Its Effect on Biochar Stability.

PubMed

Yang, Fan; Zhao, Ling; Gao, Bin; Xu, Xiaoyun; Cao, Xinde

2016-03-01

In this study, FeCl3, AlCl3, CaCl2, and kaolinite were selected as model soil minerals and incubated with walnut shell derived biochar for 3 months and the incubated biochar was then separated for the investigation of biochar-mineral interfacial behavior using XRD and SEM-EDS. The XPS, TGA, and H2O2 oxidation were applied to evaluate effects of the interaction on the stability of biochar. Fe8O8(OH)8Cl1.35 and AlCl3·6H2O were newly formed on the biochar surface or inside of the biochar pores. At the biochar-mineral interface, organometallic complexes such as Fe-O-C were generated. All the 4 minerals enhanced the oxidation resistance of biochar surface by decreasing the relative contents of C-O, C═O, and COOH from 36.3% to 16.6-26.5%. Oxidation resistance of entire biochar particles was greatly increased with C losses in H2O2 oxidation decreasing by 13.4-79.6%, and the C recalcitrance index (R50,bicohar) in TGA analysis increasing from 44.6% to 45.9-49.6%. Enhanced oxidation resistance of biochar surface was likely due to the physical isolation from newly formed minerals, while organometallic complex formation was probably responsible for the increase in oxidation resistance of entire biochar particles. Results indicated that mineral-rich soils seemed to be a beneficial environment for biochar since soil minerals could increase biochar stability, which displays an important environmental significance of biochar for long-term carbon sequestration.

On the understanding and control of the spontaneous heating of dried tannery wastewater sludge.

PubMed

Biasin, A; Della Zassa, M; Zerlottin, M; Refosco, D; Bertani, R; Canu, P

2014-04-01

We studied the spontaneous heating of dried sludge produced by treating wastewater mainly originating from tanneries. Heating up to burning has been observed in the presence of air and moisture, starting at ambient temperature. To understand and prevent the process we combined chemical and morphological analyses (ESEM) with thermal activity monitoring in insulated vessels. Selective additions of chemicals, either to amplify or depress the reactivity, have been used to investigate and identify both the chemical mechanism causing the sludge self-heating, and a prevention or a mitigation strategy. FeS additions accelerate the onset of reactivity, while S sustains it over time. On the contrary, Ca(OH)2, Na2CO3, NaHCO3, FeCl2, EDTA, NaClO can limit, up to completely preventing, the exothermic activity. All the experimental evidences show that the reactions supporting the dried sludge self-heating involve the Fe/S/O system. The total suppression of the reactivity requires amounts of additives that are industrially incompatible with waste reduction and economics. The best prevention requires reduction or removal of S and Fe from the dried solid matrix. Copyright © 2014 Elsevier Ltd. All rights reserved.

Influence of humic acid on the removal of arsenate and arsenic by ferric chloride: effects of pH, As/Fe ratio, initial As concentration, and co-existing solutes.

PubMed

Kong, Yanli; Kang, Jing; Shen, Jimin; Chen, Zhonglin; Fan, Leitao

2017-01-01

The influence of humic acid (HA) on the removal of arsenic by FeCl 3 was systematically studied in this paper. Jar tests were performed to investigate the influence on arsenic during FeCl 3 coagulation of the pH adjusting method, the initial As/Fe ratio, the equilibrium As concentration, and co-occurring anions and cations. Compared with results in HA-free systems, the removal trends of arsenic in HA solutions were quite different. It was found that As(V) removal was higher at low equilibrium concentration, yet the opposite was true for As(III) removal. The presence of HA influenced the effective number of active sites for arsenic removal by FeCl 3 flocculation. In addition, in the presence of HA, the impacts of co-existing solutions on arsenic removal were also different from that of an HA-free system. This study examined the influence of co-occurring anions, such as phosphate, sulfate, and silicate on arsenic removal, depending on their ability to compete for sorption sites and to hinder or facilitate the aggregation of ferric hydroxide flocs. The presence of Ca 2+ or Cd 2+ significantly increased arsenic removal at higher pH. Low concentrations of dissolved HA and high concentrations of colloid affected the adsorption of arsenic onto iron oxide. The influence of HA on the adsorption of arsenic onto iron oxide primarily depended on the relative content of the dissolved and mineral combination states of HA and the interface combination forms.

Rational synthesis of high nuclearity Mo/Fe/S clusters: the reductive coupling approach in the convenient synthesis of (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et, (n)Pr, (n)Bu] and the new [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl]-1/2(Fe(PEt(3))(2)(MeCN)(4)) and (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) clusters.

PubMed

Han, J; Koutmos, M; Ahmad, S A; Coucouvanis, D

2001-11-05

A general method for the synthesis of high nuclearity Mo/Fe/S clusters is presented and involves the reductive coupling of the (Et(4)N)(2)[(Cl(4)-cat)MoOFeS(2)Cl(2)] (I) and (Et(4)N)(2)[Fe(2)S(2)Cl(4)] (II) clusters. The reaction of I and II with Fe(PR(3))(2)Cl(2) or sodium salts of noncoordinating anions such as NaPF(6) or NaBPh(4) in the presence of PR(3) (R = Et, (n)Pr, or (n)Bu) affords (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et (IIIa), (n)Pr (IIIb), (n)Bu (IIIc)], Fe(6)S(6)(PEt(3))(4)Cl(2) (IV) and (PF(6))[Fe(6)S(8)(P(n)Pr(3))(6)] (V) as byproducts. The isolation of (Et(4)N)[Fe(PEt(3))Cl(3)] (VI), NaCl, and SPEt(3) supports a reductive coupling mechanism. Cluster IV and V also have been synthesized by the reductive self-coupling of compound II. The reductive coupling reaction between I and II by PEt(3) and NaPF(6) in a 1:1 ratio produces the (Et(4)N)(2)[(Cl(4)-cat)Mo(L)Fe(3)S(4)Cl(3)] clusters [L = MeCN (VIIa), THF (VIIb)]. The hitherto unknown [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl](+) cluster (VIII) has been isolated as the 2:1 salt of the (Fe(PEt(3))(2)(MeCN)(4))(2+) cation after the reductive self-coupling reaction of I in the presence of Fe(PEt(3))(2)Cl(2). Cluster VIII crystallizes in the monoclinic space group P2(1)/c with a = 11.098(3) A, b = 22.827(6) A, c = 25.855(6) A, beta = 91.680(4) degrees, and Z = 4. The formal oxidation states of metal atoms in VIII have been assigned as Mo(III), Mo(IV), Fe(II), and Fe(III) on the basis of zero-field Mössbauer spectra. The Fe(PEt(3))(2)(MeCN)(4) cation of VIII is also synthesized independently, isolated as the BPh(4)(-) salt (IX), and has been structurally characterized. The reductive coupling of compound I also affords in low yield the new (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) cluster (X) as a byproduct. Cluster X crystallizes in the monoclinic space group P2(1)/n with a = 14.811(3) A, b = 22.188(4) A, c = 21.864(4) A, beta = 100.124(3) degrees, and Z = 4 and the structure shows very short Mo-Fe, Fe-Fe, Mo-S, Fe-S bonds. The oxidation states of the metal atoms in this neutral cluster (X) have been assigned as Mo(IV)Mo(III)Fe(II)Fe(II)Fe(III) based on zero-field Mössbauer and magnetic measurement. All Fe atoms are high spin and two of the three Fe-Fe distances are found at 2.4683(9) A and 2.4721(9) A.

Chemical composition of Martian fines

NASA Technical Reports Server (NTRS)

Clark, B. C.; Baird, A. K.; Weldon, R. J.; Tsusaki, D. M.; Schnabel, L.; Candelaria, M. P.

1982-01-01

Of the 21 samples acquired for the Viking X-ray fluorescence spectrometer, 17 were analyzed to high precision. Compared to typical terrestrial continental soils and lunar mare fines, the Martian fines are lower in Al, higher in Fe, and much higher in S and Cl concentrations. Protected fines at the two lander sites are almost indistinguishable, but concentration of the element S is somewhat higher at Utopia. Duricrust fragments, successfully acquired only at the Chryse site, invariably contained about 50% higher S than fines. No elements correlate positively with S, except Cl and possibly Mg. A sympathetic variation is found among the triad Si, Al, Ca; positive correlation occurs between Ti and Fe. Sample variabilities are as great within a few meters as between lander locations (4500 km apart), implying the existence of a universal Martian regolith component of constant average composition. The nature of the source materials for the regolith fines must be mafic to ultramafic.

X-ray Fluorescence Core Scanning of Oman Drilling Project Holes BT1B and GT3A Cores on D/V CHIKYU

NASA Astrophysics Data System (ADS)

Johnson, K. T. M.; Kelemen, P. B.; Michibayashi, K.; Greenberger, R. N.; Koepke, J.; Beinlich, A.; Morishita, T.; Jesus, A. P. M.; Lefay, R.

2017-12-01

The JEOL JSX-3600CA1 energy dispersive X-ray fluorescence core logger (XRF-CL) on the D/V Chikyu provides quantitative element concentrations of scanned cores. Scans of selected intervals are made on an x-y grid with point spacing of 5 mm. Element concentrations for Si, Al, Ti, Ca, Mg, Mn, Fe, Na, K, Cr, Ni, S and Zn are collected for each point on the grid. Accuracy of element concentrations provided by the instrument software is improved by applying empirical correction algorithms. Element concentrations were collected for 9,289 points from twenty-seven core intervals in Hole BT1B (basal thrust) and for 6,389 points from forty core intervals in Hole GT3A (sheeted dike-gabbro transition) of the Oman Drilling Project on the D/V Chikyu XRF-CL during Leg 2 of the Oman Drilling Project in August-September, 2017. The geochemical data are used for evaluating downhole compositional details associated with lithological changes, unit contacts and mineralogical variations and are particularly informative when plotted as concentration contour maps or downhole concentration diagrams. On Leg 2 additional core scans were made with X-ray Computed Tomography (X-ray CT) and infrared images from the visible-shortwave infrared imaging spectroscopy (IR) systems on board. XRF-CL, X-ray CT and IR imaging plots used together provide detailed information on rock compositions, textures and mineralogy that assist naked eye visual observations. Examples of some uses of XRF-CL geochemical maps and downhole data are shown. XRF-CL and IR scans of listvenite clearly show zones of magnesite, dolomite and the Cr-rich mica, fuchsite that are subdued in visual observation, and these scans can be used to calculate variations in proportions of these minerals in Hole BT1B cores. In Hole GT3A XRF-CL data can be used to distinguish compositional changes in different generations of sheeted dikes and gabbros and when combined with visual observations of intrusive relationships the detailed geochemical information can be used to infer temporal changes in parental magma compositions. Secondary sulfide mineralization and epidote-rich hydrothermal alteration zones in sheeted dikes and gabbros are clearly highlighted on element maps of S, Fe, Ca, Al, and Zn.

Phase relations of aluminous silica to 120 GPa and lowermost mantle dynamics

NASA Astrophysics Data System (ADS)

Tronnes, R. G.; Andrault, D.; Konopkova, Z.; Morgenroth, W.; Liermann, H.-P.

2012-04-01

Basalts have 3-10 times higher concentrations of Al, Ti, Ca and Na and more than 5 times lower concentration of Mg than peridotite. The resulting lower mantle basaltic mineralogy has no ferropericlase and low proportion of Mg-perovskite and post-perovskite with high Fe/Mg-ratio. Oversaturation of silica and alumina produces separate silica-dominated phases and Al-rich phases (NAL and Ca-ferrite phases). At pressures of 60-100 GPa common basalts crystallize 15-20% CaCl2-structured silica, 15-25% Ca-ferrite, 35-40% Mg-perovskite and 20-30% Ca-perovskite. The Fe-rich Mg-perovskite makes basaltic material denser than peridotite throughout the lower mantle below 720 km depth, with important implications for mantle dynamics. Partial separation of subducted basaltic crust from depleted lithosphere may occur within the strongly heterogeneous D" zone. The silica-dominated phases have considerable solubility of alumina [1]. At 3500-4000 K the transition from the CaCl2-phase to seifertite (a-PbO2-structure) of pure SiO2 occurs at 130-140 GPa, with a dp/dT-slope of about 10 MPa/K [2]. The transition pressure is reduced with Al-saturation. We investigated silica with 4 and 6 wt% alumina to 120 GPa, using LH-DAC at the Extreme Conditions Beamline (P02.2) at PETRA-III, DESY. Powdered glass mixed with 10-15 wt% Pt-powder was compressed and heated in NaCl pressure media in Re-gaskets. To delineate the phase transition, the samples were compressed incrementally with intermittent laser heating. Slow reaction rates required 20-40 min heating at 3500-4000 K for each heating step. The XRD data and pressure estimates were acquired repeatedly during heating and after quenching to room temperature. The first crystallization of seifertite at 3500-4000 K was recorded at about 118 and 108 GPa in samples with 4 and 6 wt% AlO1.5, respectively. The CaCl2-structured silica phase crystallized along with seifertite, consistent with a binary phase loop trending towards lower pressure with increasing Al-content. Due to the presence of the Al-rich Ca-ferrite phase (near the MgAl2O4-NaAlSiO4-join) in natural basaltic compositions, the Al-solubility limits for the silica-dominated phases in basaltic lithologies may be similar to those in the binary system SiO2-AlO1.5. Phase transitions in response to increasing pressure are generally associated with densification. Because of the strong partitioning of light and voluminous AlO1.5 into seifertite, however, the densification effect is more than offset by the lighter alumina component. The unit cell data of ref. [1] indicate a volume increase of about 3.8% associated with the transition. The associated density reduction would be strongly dependent on the substitution mechanism. O-vacancy and cation (3Si4+ → 4Al3+) substitutions yield density reductions of 5.4% and 1.9%, respectively [1]. The large density reduction accompanying the seifertite transition may limit the role of gravitational accretion of evolved MORB to the LLSVPs. Segregation of Fe-rich picritic, komatiitic or peridotitic rocks with no separate silica phase may be more likely. Deep-mantle cumulates and solidified melts of peridotitic to komatiitic composition were mostly produced in the Hadean and early Archean, indicating that the antipodal and near-equatorial LLSVPs, stabilized by Earth's rotation, could also represent ancient structures.

Synchrotron X-ray microfluorescence measurement of metal distributions in Phragmites australis root system in the Yangtze River intertidal zone

DOE PAGES

Feng, Huan; Zhang, Weiguo; Qian, Yu; ...

2016-06-15

This paper investigates the distributions of Br, Ca, Cl, Cr, Cu, K, Fe, Mn, Pb, Ti, V and Zn in Phragmites australis root system and the function of Fe nanoparticles in scavenging metals in the root epidermis using synchrotron X-ray microfluorescence, synchrotron transmission X-ray microscope measurement and synchrotron X-ray absorption near-edge structure techniques. The purpose of this study is to understand the mobility of metals in wetland plant root systems after their uptake from rhizosphere soils. Phragmites australis samples were collected in the Yangtze River intertidal zone in July 2013. The results indicate that Fe nanoparticles are present in themore » root epidermis and that other metals correlate significantly with Fe, suggesting that Fe nanoparticles play an important role in metal scavenging in the epidermis.« less

Synchrotron X-ray microfluorescence measurement of metal distributions in Phragmites australis root system in the Yangtze River intertidal zone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Huan; Zhang, Weiguo; Qian, Yu

This paper investigates the distributions of Br, Ca, Cl, Cr, Cu, K, Fe, Mn, Pb, Ti, V and Zn in Phragmites australis root system and the function of Fe nanoparticles in scavenging metals in the root epidermis using synchrotron X-ray microfluorescence, synchrotron transmission X-ray microscope measurement and synchrotron X-ray absorption near-edge structure techniques. The purpose of this study is to understand the mobility of metals in wetland plant root systems after their uptake from rhizosphere soils. Phragmites australis samples were collected in the Yangtze River intertidal zone in July 2013. The results indicate that Fe nanoparticles are present in themore » root epidermis and that other metals correlate significantly with Fe, suggesting that Fe nanoparticles play an important role in metal scavenging in the epidermis.« less

Thermodynamic description of Tc(iv) solubility and hydrolysis in dilute to concentrated NaCl, MgCl2 and CaCl2 solutions.

PubMed

Yalçıntaş, Ezgi; Gaona, Xavier; Altmaier, Marcus; Dardenne, Kathy; Polly, Robert; Geckeis, Horst

2016-06-07

We present the first systematic investigation of Tc(iv) solubility, hydrolysis and speciation in dilute to concentrated NaCl, MgCl2 and CaCl2 systems, and comprehensive thermodynamic and activity models for the system Tc(4+)-H(+)-Na(+)-Mg(2+)-Ca(2+)-OH(-)-Cl(-)-H2O using both SIT and Pitzer approaches. The results are advancing the fundamental scientific understanding of Tc(iv) solution chemistry and are highly relevant in the applied context of nuclear waste disposal. The solubility of Tc(iv) was investigated in carbonate-free NaCl-NaOH (0.1-5.0 M), MgCl2 (0.25-4.5 M) and CaCl2 (0.25-4.5 M) solutions within 2 ≤ pHm≤ 14.5. Undersaturation solubility experiments were performed under an Ar atmosphere at T = 22 ± 2 °C. Strongly reducing conditions (pe + pHm≤ 2) were imposed with Na2S2O4, SnCl2 and Fe powder to stabilize technetium in the +IV redox state. The predominance of Tc(iv) in the aqueous phase was confirmed by solvent extraction and XANES/EXAFS spectroscopy. Solid phase characterization was accomplished after attaining thermodynamic equilibrium using XRD, SEM-EDS, XANES/EXAFS, TG-DTA and quantitative chemical analysis, and indicated that TcO2·0.6H2O(s) exerts solubility-control in all evaluated systems. The definition of the polyatomic Tc3O5(2+) species instead of TcO(2+) is favoured under acidic conditions, consistently with slope analysis (mTcvs. pHm) of the solubility data gained in this work and spectroscopic evidence previously reported in the literature. The additional formation of Tc(iv)-OH/O-Cl aqueous species in concentrated chloride media ([Cl(-)] = 9 M) and pHm≤ 4 is suggested by solubility and EXAFS data. The pH-independent behaviour of the solubility observed under weakly acidic to weakly alkaline pHm conditions can be explained with the equilibrium reaction TcO2·0.6H2O(s) + 0.4H2O(l) ⇔ TcO(OH)2(aq). Solubility data determined in dilute NaCl systems with pHm≥ 11 follow a well-defined slope of +1, consistent with the predominance of TcO(OH)3(-) previously selected by NEA-TDB. In concentrated MgCl2 and CaCl2 solutions with pHm≥ 8, the formation of the ternary Mg3[TcO(OH)5](3+) and Ca3[TcO(OH)5](3+) species is proposed based on the slope analysis of the solubility data, model calculations and previous observations for analogous An(iv) and Zr(iv) systems. The formation and stability of these hitherto unknown Tc(iv) species are supported by DFT calculations. Based on the newly generated experimental data and previous spectroscopic observations, new comprehensive chemical, thermodynamic and activity models (SIT, Pitzer) for these systems are derived.

Orosensory Responsiveness to and Preference for Hydroxide-Containing Salts in Mice

PubMed Central

St. John, Steven J.; Boughter, John D.

2009-01-01

Historically, taste researchers have considered the possibility that the gustatory system detects basic compounds, such as those containing the hydroxide ion, but evidence for an “alkaline taste” has not been strong. We found that, in 48 h, 2-bottle preference tests, C3HeB/FeJ (C3) mice showed a preference for Ca(OH)2, whereas SWR/J (SW) mice showed avoidance. Strain differences were also apparent to NaOH but not CaCl2. Follow-up studies showed that the strain difference for Ca(OH)2 was stable over time (Experiment 2) but that C3 and SW mice did not differ in their responses to Ca(OH)2 or NaOH in brief-access tests, where both mice avoided high concentrations of these compounds (Experiment 3). In order to assess the perceived quality of Ca(OH)2, mice were tested in 2 taste aversion generalization experiments (Experiments 4 and 5). Aversions to Ca(OH)2 generalized to NaOH but not CaCl2 in both strains, suggesting that the generalization was based on the hydroxide ion. Both strains also generalized aversions to quinine, suggesting the possibility that the hydroxide ion has a bitter taste quality to these mice, despite the preference shown by C3 mice to middle concentrations in long-term tests. PMID:19423656

Oxidative desulfurization of fuels catalyzed by Fenton-like ionic liquids at room temperature.

PubMed

Jiang, Yunqing; Zhu, Wenshuai; Li, Huaming; Yin, Sheng; Liu, Hua; Xie, Qingjie

2011-03-21

Oxidation of the sulfur-containing compounds benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been studied in a desulfurization system composed of model oil, hydrogen peroxide, and different types of ionic liquids [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3), [(C(8)H(17))(3)CH(3)N]Cl/CuCl(2), [(C(8)H(17))(3)CH(3)N]Cl/ZnCl(2), [(C(8)H(17))(3)CH(3)N]Cl/SnCl(2), [(C(4)H(9))(3)CH(3)N]Cl/FeCl(3), [C(10)H(21)(CH(3))(3)N]Cl/FeCl(3), [(C(10)H(21))(2)(CH(3))(2)N]Cl/FeCl(3). Deep desulfurization is achieved in the Fenton-like ionic liquid [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) at 25 °C for 1 h. The desulfurization of DBT reaches 97.9%, in consuming very low amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) (only 0.702 mmol). The reaction conditions, for example, the amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) or H(2)O(2), the temperature, and the molar ratio of FeCl(3) to [(C(8)H(17))(3)CH(3)N]Cl, are investigated for this system. The oxidation reactivity of the different sulfur-containing compounds is found to decrease in the order of DBT>BT>4,6-DMDBT. The desulfurization system can be recycled six times without significant decrease in activity. The sulfur level of FCC gasoline could be reduced from 360 ppm to 110 ppm. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solubility of Anhydrite (CaSO4) in NaCl-H2O Fluids at High T and P

NASA Astrophysics Data System (ADS)

Newton, R. C.; Manning, C. E.

2003-12-01

Weight losses of single crystals of a very pure natural anhydrite exposed to NaCl solutions of 0-0.3 mol fraction were measured at 600-800 \\deg C and 6-14 kbar. Experimental charges were contained in welded Pt capsules in 1.91 cm-diameter piston-cylinder apparatus with NaCl pressure medium for 5-72 hr. Measurements in initially pure H2O were made with HM, NNO, and MnO2 buffers, as well as without buffering. At 800 \\deg C and 10 kbar, CaSO4 molalities are: MnO2, 0.014 mol/kg H2O; HM, 0.017; NNO, 0.148; and unbuffered, 0.026. Variation in oxygen fugacity thus has a large effect on CaSO4 solubility, increasing with H2S/SO2 in the fluid. Unbuffered (self-buffered) charges gave solubilities much closer to HM than NNO. Melting occurred in the NNO experiment at this P and T. NaCl increases CaSO4 solubility enormously, with m(CaSO4) reaching 5.4, or 23.5 wt. %, at 800 \\deg C, 10 kbar and X(NaCl)=0.3. There is also a very large increase with temperature. Regression of all the data give: log(m-mo) = -1.533 + 0.00291T + (1.441 + 0.00016T)logX(NaCl) + 0.0413(P-10) where mo is molality in pure H2O, P is in kbar, and T is in Kelvins. The very large carrying capacity for sulfate in even mildly saline fluids at high P and T, together with the high oxygen potential generated when these solutions react with FeO in rocks to yield pyrrhotite, indicates that such fluids should be considered as principal agents in S-rich, highly oxidizing processes such as Pinatubo-type volcanic eruptions, certain deep-crustal granulite facies metamorphism, as in Bamble, Norway and Shevaroy Hills, S. India, and the anhydrite-related, oxidized Au ore deposits like Abitibi, Ontario, and Kalgoorlie, Australia.

Chemical profile of size-fractionated soils collected in a semiarid industrial area of Argentina

NASA Astrophysics Data System (ADS)

Morales Del Mastro, Anabella; Pereyra, Marcelo; Londonio, Agustín; Pereyra, Victoria; Rebagliati, Raúl Jiménez; Dawidowski, Laura; Gómez, Darío; Smichowski, Patricia

2014-12-01

A study was undertaken to assess the chemical profile of soil collected in Bahía Blanca (Argentina). In this industrial city, semiarid soils are affected by different industrial and agricultural activities, the presence of a saltpeter extraction facility, traffic and increasing urbanization. Sixteen soil samples (superficial and sub-superficial) were collected. Samples were sieved in two fractions (A < 37 μm, and 37 < B < 50 μm) before elemental analysis. Major, minor and trace elements namely, Al, As, Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sb, Ti, V and Zn were determined by inductively coupled plasma optical emission spectrometry (ICP OES). Anions (Cl-, F-, SO42-) and cations (K+, Na+ and NH4+) were determined by high performance liquid chromatography (HPLC) after an aqueous extraction. As expected, crustal elements namely, Al, Ca, Fe, Mg and Ti exhibited the highest concentrations. Mean elemental concentration ranged from <0.3 μg g-1 (Sb) to 14.6 ± 0.6% (Ca). Ions concentrations in the soluble fraction measured at mg g-1 levels were in the order Cl- > Na+ ≅ SO42- > K+ > NO3-. Three indicators, namely, (i) coefficient of variation, (ii) coefficient of divergence and (iii) ratio of elemental concentration with respect to Ca were used to assess chemical, spatial and inter-profile variability. Chloride > Ca > Na+ > Mo > SO42-, dominated the variability indicating that these are key chemical markers for future assessment of crustal contribution to airborne particles in the area. The ratios Xi/Ca allowed discriminating the soil of the semi-arid region surrounding Bahía Blanca. The chemical profiles obtained in this study, particularly those of topsoil, will be a key input to characterize soil resuspension and its contribution to airborne particulate matter in a forthcoming receptor model analysis.

Magnetic properties and magnetization reversal mechanism of Nd-Fe-B nanoparticles synthesized by a sol-gel method

NASA Astrophysics Data System (ADS)

Rahimi, Hamed; Ghasemi, Ali; Mozaffarinia, Reza; Tavoosi, Majid

2017-12-01

Nd-Fe-B oxide powders with various pH were prepared using chloride and nitrate precursors including NdCl3·6H2O, FeCl3·6H2O, H3BO3, Nd2O3, Fe(NO3)3·9H2O, HNO3, citric acid (CA), ethylene glycol (EG) by Pechini type sol-gel method. The pH of chloride and nitrate base sols were 0 and 2.2, respectively. Mixed oxide powders were obtained by calcination and annealing the gels. These oxides by using a reduction-diffusion process under high vacuum and employing CaH2 as reducing agent at 800 °C were hated to prepare Nd2Fe14B nanoparticles. The role of pH on phase, morphologies, microstructure, and magnetic properties of the powders were investigated. The results show that with a decrease in pH, the average particle size and coercivity of Nd-Fe-B oxide powders were decreased and increased, respectively. Nd2Fe14B nanoparticles were formed successfully after reduction process. The average particle size of reduction treated products were 30 and 65 nm for powders which made of chloride and nitrate base metal salts, respectively. Final powders which made of chloride and nitrate base metal salts had a saturation magnetization of 127.7 emu/g and 122.8 emu/g while the coercivity of samples were 3.32 kOe and 1.82 kOe, respectively. The experimental results in the angular dependence of coercivity indicated that the normalized coercivity of the permanent magnets Hc(θ)/Hc(0) obeys the 1/cosθ law and intermediate between the 1/cosθ law and Stoner-Wohlfarth formula for different Nd2Fe14B magnets which made of nitrate and chloride base metal salts, respectively. Also, the results show that different Nd2Fe14B magnets which made of nitrate and chloride base metal salts had the maximum energy product of 5 and 16 MGOe, respectively. The Henkel plot showed that magnetic phases in synthesized NdFeB magnets which made of chloride and nitrate base metal salts were coupled by exchange and dipolar interactions, respectively. Different average particle size, morphology and microstructure were the reasons for variation of magnetic properties.

THE INFLUENCE OF THE CHEMICAL NATURE OF SOLID PARTICLES ON THEIR CATAPHORETIC P.D. IN AQUEOUS SOLUTIONS

PubMed Central

Loeb, Jacques

1923-01-01

1. The effect of eight salts, NaCl, Na2SO4, Na4Fe(CN)6, CaCl2, LaCl3, ThCl4, and basic and acid fuchsin on the cataphoretic P.D. between solid particles and aqueous solutions was measured near the point of neutrality of water (pH 5.8). It was found that without the addition of electrolyte the cataphoretic P.D. between particles and water is very minute near the point of neutrality (pH 5.8), often less than 10 millivolts, if care is taken that the solutions are free from impurities. Particles which in the absence of salts have a positive charge in water near the point of neutrality (pH 5.8) are termed positive colloids and particles which have a negative charge under these conditions are termed negative colloids. 2. If care is taken that the addition of the salt does not change the hydrogen ion concentration of the solution (which in these experiments was generally pH 5.8) it can be said in general, that as long as the concentration of salts is not too high, the anions of the salt have the tendency to make the particles more negative (or less positive) and that cations have the opposite effect; and that both effects increase with the increasing valency of the ions. As soon as a maximal P.D. is reached, which varies for each salt and for each type of particles, a further addition of salt depresses the P.D. again. Aside from this general tendency the effects of salts on the P.D. are typically different for positive and negative colloids. 3. Negative colloids (collodion, mastic, Acheson's graphite, gold, and metal proteinates) are rendered more negative by low concentrations of salts with monovalent cation (e.g. Na) the higher the valency of the anion, though the difference in the maximal P.D. is slight for the monovalent Cl and the tetravalent Fe(CN)6 ions. Low concentrations of CaCl2 also make negative colloids more negative but the maximal P.D. is less than for NaCl; even LaCl3 increases the P.D. of negative particles slightly in low concentrations. ThCl4 and basic fuchsin, however, seem to make the negative particles positive even in very low concentrations. 4. Positive colloids (ferric hydroxide, calcium oxalate, casein chloride—the latter at pH 4.0) are practically not affected by NaCl, are rendered slightly negative by high concentrations of Na2SO4, and are rendered more negative by Na4Fe(CN)6 and acid dyes. Low concentrations of CaCl2 and LaCl3 increase the positive charge of the particles until a maximum is reached after which the addition of more salt depresses the P.D. again. 5. It is shown that alkalies (NaOH) act on the cataphoretic P.D. of both negative and positive particles as Na4Fe(CN)6 does at the point of neutrality. 6. Low concentrations of HCl raise the cataphoretic P.D. of particles of collodion, mastic, graphite, and gold until a maximum is reached, after which the P.D. is depressed by a further increase in the concentration of the acid. No reversal in the sign of charge of the particle occurs in the case of collodion, while if a reversal occurs in the case of mastic, gold, and graphite, the P.D. is never more than a few millivolts. When HCl changes the chemical nature of the colloid, e.g. when HCl is added to particles of amphoteric electrolytes like sodium gelatinate, a marked reversal will occur, on account of the transformation of the metal proteinate into a protein-acid salt. 7. A real reversal in the sign of charge of positive particles occurs, however, at neutrality if Na4Fe(CN)6 or an acid dye is added; and in the case of negative colloids when low concentrations of basic dyes or minute traces of ThCl4 are added. 8. Flocculation of the suspensions by salts occurs when the cataphoretic P.D. reaches a critical value which is about 14 millivolts for particles of graphite, gold, or mastic or denatured egg albumin; while for collodion particles it was about 16 millivolts. A critical P.D. of about 15 millivolts was also observed by Northrop and De Kruif for the flocculation of certain bacteria. PMID:19872064

Davinciite, Na12K3Ca6Fe{3/2+}Zr3(Si26O73OH)Cl2, a New K,Na-Ordered mineral of the eudialyte group from the Khibiny Alkaline Pluton, Kola Peninsula, Russia

NASA Astrophysics Data System (ADS)

Khomyakov, A. P.; Nechelyustov, G. N.; Rastsvetaeva, R. K.; Rozenberg, K. A.

2013-12-01

This paper presents a description of a new zirconosilicate of the eudialyte group, which was named davinciite in honor of Leonardo da Vinci (1452-1519), a famous Italian scientist, painter, sculptor and architect. The new mineral has been found in hyperagpaitic pegmatite at the Rasvumchorr Mountain, Khibiny Pluton, Kola Peninsula, as relict inclusions, up to 1-2 mm in size in a rastsvetaevite matrix. It is associated with nepheline, sodalite, potassium feldspar, delhayelite, aegirine, shcherbakovite, villiaumite, nitrite, nacaphite, rasvumite, and djerfisherite. Davinciite is dark lavender and transparent, with a vitreous luster and white streak. The new mineral is brittle, with conchoidal fracture; the Mohs' hardness is 5. No indications of cleavage or parting were observed. The measured density is 2.82(2) g/cm3 (volumetric method); the calculated density is 2.848 g/cm3. Davinciite is optically uniaxial, positive; ω = 1.603(2), ɛ = 1.605(2). It is nonpleochroic and nonfluorescent in UV light. The new mineral slowly breaks down and gelates in 50% HCl and HNO3. It is trigonal, space group R3m. The unit-cell dimensions are a = 14.2956(2), c = 30.0228(5) Å, V=5313.6(2) Å3. The strongest reflections in the X-ray powder diffraction pattern [ d, Å ( I, %) ( hkl)] are as follows: 2.981(100)(315), 2.860(96)(404), 4.309(66)(205), 3.207(63)(208), 6.415(54)(104), 3.162(43)(217). The chemical composition (electron microprobe, H2O calculated from X-ray diffraction data) is as follows, wt %: 12.69 Na2O, 3.53 K2O, 11.02 CaO, 0.98 SrO, 0.15 BaO, 5.33 FeO, 0.37 MnO, 0.07 Al2O3, 51.20 SiO2, 0.39 TiO2, 11.33 ZrO2, 0.21HfO2, 0.09 Nb2O5, 1.89 Cl, 0.93H2O, -O = Cl2 0.43; total is 99.75. The empirical formula calculated on the basis of Si + Al + Zr + Hf + Ti + Nb = 29 ( Z = 3) is (Na1l.75Sr0.29Ba0.03)Σ12.07(K2.28Na0.72)Σ3Ca5.99(Fe2.26Mn0.16)Σ2.42(Zr2.80Ti0.15Hf0.03Nb0.02) Σ3(Si1.96Al0.04)Σ2[Si3O9]2 [Si9O27]2[(OH)1.42O0.58]Σ2[Cl1.62(H2O)0.38]Σ2 · 0.48H2O. The simplified formula is Na12K3Ca6Fe{3/2+}Zr3(Si26O73OH)Cl2. The IR-spectrum is given and the crystal structure is described. The position of davinciite in the crystal chemical taxonomy of the eudialyte group is shown, and its relationships with the other eudialyte-group minerals (acentric eudialyte, andrianovite, and kentbrooksite) are characterized. The type material of davinciite is deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.

Mineral concentrations in diets, water, and milk and their value in estimating on-farm excretion of manure minerals in lactating dairy cows.

PubMed

Castillo, A R; St-Pierre, N R; Silva del Rio, N; Weiss, W P

2013-05-01

Thirty-nine commercial dairies in Merced County, California were enrolled in the present study to (1) compare lactating cow mineral intakes (via drinking water and total mixed ration) to the National Research Council (NRC) requirements, (2) evaluate the association between dietary concentrations of minerals with and without drinking water and adjusted for mineral concentrations in milk, and (3) compare 4 different methods to estimate excretion of minerals using either assays or estimations of milk mineral outputs and total daily mineral intake per cow with or without minerals coming from drinking water. Dairies were selected to represent a range of herd milk yields and a range of water mineral contents. Samples of total mixed ration, drinking water, and bulk tank milk were taken on 2 different days, 3 to 7d apart in each farm. Across-farm medians and percentile distributions were used to analyze results. The herd median milk yield interquartile ranged (10th to 90th percentile) from less than 25 to more than 39 kg/d and the concentration of total solids in water interquartile ranged from less than 200 to more than 1,490 mg/L. Including drinking water minerals in the diets increased dietary concentrations by <4% for all minerals except for Na and Cl, which increased by 9.3 and 6.5%, respectively. Concentrations of P and K in milk were essentially the same as the NRC value to estimate lactation requirements. However, NRC milk values of Ca, Cl, and Zn were 10 to 20% greater than dairy farm values; and Na, Cu, Fe, and Mn were no less than 36% below NRC values. Estimated excretion of minerals via manure varied substantially across farms. Farms in the 10th percentile did have 2 to 3 times less estimated mineral excretions than those in the 90th percentile (depending on the mineral). Although including water minerals increased excretion of most minerals, the actual median effect of Ca, Mg, S, Cu, Fe, and Mn was less than 5%, and about 8% for Na and Cl. Replacing assayed concentrations of minerals in milk with NRC constants resulted in reduced estimated excretion of Ca, Na, Cu, Fe, and Zn, but median differences were <5% except for Na which was 7.5%. Results indicate that not including mineral intake via drinking water and not using assayed concentrations of milk minerals lead to errors in estimation manure excretion of minerals (e.g., Ca, Na, Cl, and S). Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Effect of environmental factor and microstructure on morphology of corrosion products in CO{sub 2} environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ueda, Masakatsu; Takabe, Hideki

The effect of environmental factors such as HCO{sup 3+} ion, CH{sub 3}COO{minus} ion, and Ca{sup 2+} ion, and microstructure on morphology of corrosion products was investigated in CO{sub 2} environments with 0.3MPa CO{sub 2} at 80 C. Steel J55 with ferritic-pearlitic microstructure and Steel N80 with martensitic microstructure were used as testing materials. Steel J55 showed good localized-corrosion resistance compared with Steel N80. A linear relationship between pH and corrosion rate was obtained in Steel J55 with homogeneous corrosion, but the relationship was not so good in Steel N80 with heterogeneous corrosion. The good localized-corrosion of Steel J55 can bemore » explained from the morphology of corrosion products. Namely, as Steel J55 corrodes away, there is lamellar cementite left behind. An increase in the local concentration of Fe{sup 2+} ions arises in the cavities between lamellar cementites and leads to FeCO{sub 3} formation between those. Then, the lamellar cementite helps to anchor the corrosion product. In Steel N80 with the homogeneous dispersed-cementite to act as cathodic site, the corrosion product peels off partially because not having the anchor effect in Steel J55. Therefore, Steel N80 suffered from severe corrosion on locations without the corrosion product. In CaCl{sub 2} solution, FeCO{sub 3} and CaCO{sub 3} were identified as corrosion product of Steel J55 by X-ray analysis. In this case, FeCO{sub 3} forms in the cavities between lamellar cementites due to a local flow stagnation and higher local Fe{sup 2+} ion concentration, but in former ferrite phase, the higher local Fe{sup 2+} concentration does not arise and CaCO{sub 3} crystallizes.« less

Volatile Contents in Mafic Magmas from two Aleutian volcanoes: Augustine and Makushin

NASA Astrophysics Data System (ADS)

Zimmer, M. M.; Plank, T.; Hauri, E. H.; Nye, C.; Faust Larsen, J.; Kelemen, P. B.

2004-12-01

There are several competing theories for the origin of tholeiitic (TH) vs. calc-alkaline (CA) fractionation trends in arc magmas. One relates to water (TH-dry magma, CA-wet magma), another to pressure (TH-low pressure crystallization, CA-high pressure), and a third to primary magma composition (TH-low Si/Fe#, CA-hi Si/Fe#) These theories have been difficult to test without quantitative measures of the water contents and pressures of crystallization of arc magmas. We are in the process of studying several Aleutian arc tephra suites (phenocrysts and melt inclusions) with the aim of obtaining volatile element concentrations (by SIMS), major and trace element concentrations and thermobarometric data (by EMP and laser-ICPMS). We report preliminary results on olivine-hosted melt inclusions from Augustine and Makushin volcanoes that support the role of water in calc-alkaline fractionation. Basaltic melt inclusions from Augustine, a low-K2O, calc-alkaline volcano, are hosted in Fo80-82 olivine. The inclusions yield high water contents, up to 5 wt%, and contain 60-90 ppm CO2, 3000-4500 ppm S, and 3000-6000 ppm Cl. Inclusions record vapor-saturation pressures near 2 kbar. Cl/K2O ratios in Augustine inclusions (ave. 1.9) are among the highest documented in an arc setting, and likely record a Cl- and H2O- rich fluid from the subducting plate. High water contents in Augustine primary melts may have contributed to the strong calc-alkaline trend observed at this volcano. Basaltic melt inclusions from Pakushin, a medium-K2O, tholeiitic cone on the flanks of Makushin volcano, are hosted in Fo80-86 olivine. These inclusions have low water contents (<0.15 wt%) and low CO2 contents (<125 ppm), and record shallow vapor saturation pressures (<300 bars). The high sulfur (2000-4000 ppm) and Cl (>2000 ppm) in Pakushin melt inclusions, however, indicate that degassing was minimal. The low water contents and low vapor saturation pressures recorded in Pakushin melt inclusions are consistent with development of its tholeiitic trend, but we cannot distinguish whether the low water contents at Pakushin reflect a difference in the primary magma, or in crustal stresses that favor low pressure fractionation and degassing. These questions will be addressed with further work on the trace element contents of the melt inclusions and on phenocryst-melt geobarometers.

Discovery of a hexagonal ultradense hydrous phase in (Fe,Al)OOH

NASA Astrophysics Data System (ADS)

Zhang, Li; Yuan, Hongsheng; Meng, Yue; Mao, Ho-kwang

2018-03-01

A deep lower-mantle (DLM) water reservoir depends on availability of hydrous minerals which can store and transport water into the DLM without dehydration. Recent discoveries found hydrous phases AlOOH (Z = 2) with a CaCl2-type structure and FeOOH (Z = 4) with a cubic pyrite-type structure stable under the high-pressure–temperature (P-T) conditions of the DLM. Our experiments at 107–136 GPa and 2,400 K have further demonstrated that (Fe,Al)OOH is stabilized in a hexagonal lattice. By combining powder X-ray-diffraction techniques with multigrain indexation, we are able to determine this hexagonal hydrous phase with a = 10.5803(6) Å and c = 2.5897(3) Å at 110 GPa. Hexagonal (Fe,Al)OOH can transform to the cubic pyrite structure at low T with the same density. The hexagonal phase can be formed when δ-AlOOH incorporates FeOOH produced by reaction between water and Fe, which may store a substantial quantity of water in the DLM.

Electrochemical Synthesis of Core-Shell-Structured NbC-Fe Composite Powder for Enforcement in Low-Carbon Steel.

PubMed

Li, Hongmei; Song, Qiushi; Xu, Qian; Chen, Ying; Xu, Liang; Man, Tiannan

2017-11-01

An NbC-Fe composite powder was synthesized from an Nb₂O₅/Fe/C mixture by electrochemical reduction and subsequent carbonization in molten CaCl₂-NaCl. The composite has a core-shell structure, in which NbC acts as the cores distributing in the Fe matrix. A strong bonding between NbC and Fe is benefit from the core-shell structure. The sintering and electrochemical reduction processes were investigated to probe the mechanism for the reactions. The results show that NbC particles about several nanometers were embraced by the Fe shell to form a composite about 100 nm in size. This featured structure can feasibly improve the wettability and sinterability of NbC as well as the uniform distribution of the carbide in the cast steel. By adding the composite into steel in the casting process, the grain size of the casted steel was markedly deceased from 1 mm to 500 μm on average, favoring the hardening of the casted steel.

Synthesis of brominated acenaphthylenes and their flame-retardant effects on ethylene-propylene-diene terpolymer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morita, Y.; Hagiwara, M.

1982-09-01

Bromoacenaphthylenes and their condensates as flame-retardant reagents were synthesized by bromination of acenaphthylene using ZnCl/sub 2/ - CF/sub 3/COOH or FeCl/sub 3/ as catalysts and subsequent dehydrobromination. The chief components were identified as bromoacenaphthylene monomers when ZnCl/sub 2/ - CF/sub 3/COOH were used, and as their condensates (mostly trimers) in the case of FeCl/sub 3/. Their performance as flame-retardant reagents for ethylene-propylene-diene terpolymer (EPDM) was evaluated by measuring the oxygen index of finished compounds, and flammability by a vertical flammability test based on UL-94-VO. Both the monomers and the condensates demonstrated high flame-retardant effectiveness. The high efficiency was attributed tomore » their excellent dispersity in the base polymer and their characteristic thermal decomposition behavior. In thermal gravimetric analysis (TGA), they decomposed in a very wide range of temperature (ca.200-560/sup 0/C), which covers the decomposition range of EPDM. This was attributed to the existence of bromines of different thermal stabilities in one molecule. This paper is a part of a series of studies to develop new flame retardants which can give high flame retardancy as well as stabilty against ionizing radiation to EPDM.« less

Geochemical Characterization Of Cherts From The 3.46Ga Apex Basalt To Assess The Origins Of Possible Biosignatures

NASA Astrophysics Data System (ADS)

Bower, D. M.; Steele, A.; Ackerson, M. R.; Bullock, E. S.; Green, O. R.; Fries, M.; Conrad, P. G.

2017-12-01

Many terrestrial cherts contain compelling microtextures and mineral phases that are indicative of ancient life in hydrothermal systems on early Earth. In volcanically-derived hydrothermal deposits, cherts have undergone multiple alteration events often resulting in separate generations of quartz veins that are much younger than the host rocks. In some cases, multiple episodes of hydrothermal alteration obscure otherwise syngenetic biosignatures and likewise create false signatures in the form of secondary carbon emplacement or diagenetic phase changes. To better identify possible biosignatures in hydrothermal deposits and understand their origins, we used confocal micro Raman spectroscopy, electron probe microanalysis, and cathodoluminescence (CL) imaging to characterize the quartz fabrics, mineral phases, trace elements, and macromolecular carbon (MMC) in quartz veins from the 3.46 Ga Apex Basalt chert samples. MMC, anatase (TiO2), pyrite (Fe2S), jarosite-alunite (KFe3(SO4)2(OH)6 - Kal3(SO4)2(OH)6), chamosite-phyllosilicates, and Fe-oxides all occur in close association in multiple generations of quartz veins throughout the sample suite. Mineral phases xenotime (YPO4), scorodite (FeAsO4 . H2O), apatite (CaPO4), pentlandite ((Fe,Ni)9S8), barite (BaSO4), sphalerite ((Zn,Fe)S), dolomite ((CaMg(CO3)2) and halides occur in specific generations of quartz. Trace elements (Cr, Mn, Mo, Cu, Sc, Va, Sb, and Co) are heterogeneously distributed within individual samples and likely occur due to fluid scavenging of the host basalts. CL imaging of quartz demonstrates that the majority of silicate material in the Apex cherts underwent recrystallization. This could result in the alteration of MMC and associated mineral assemblages. The biogencity and true origins of morphological features and chemical signatures in the Apex cherts are hotly debated, yet discovering the causes and nature of these puzzling attributes will be key for determining the usefulness of interrogating hydrothermal silica-rich deposits on other planetary environments.

Origin of the magnetoelectric effect in the Cs2FeCl5.D2O compound

NASA Astrophysics Data System (ADS)

Fabelo, Oscar; Rodríguez-Velamazán, J. Alberto; Canadillas-Delgado, Laura; Mazzuca, Lidia; Campo, Javier; Millán, Ángel; Chapon, Laurent C.; Rodríguez-Carvajal, Juan

2017-09-01

Cs2FeCl5.D2O has been identified as a linear magnetoelectric material, although the correlation of this property with the magnetic structures of this compound has not been adequately studied. We have used single-crystal and powder neutron diffraction to obtain detailed information about its nuclear and magnetic structures. From the nuclear structure analysis, we describe the occurrence of a phase transition related to the reorganization of the [FeCl5.D2O] -2 ions and the Cs+ counterion. The magnetic structure was determined at zero magnetic field at 1.8 K using single-crystal diffraction and its temperature evolution was recorded using powder diffraction. The symmetry analysis of the magnetic structure is compatible with the occurrence of the magnetoelectric effect. Moreover, the evolution of the magnetic structure as a function of the external magnetic field has also been studied. The reorientation of the magnetic moments under applied external field along the easy axis (b axis at low temperature) is compatible with the occurrence of a spin-flop transition. The application of a magnetic field below TN compels the magnetic moments to flip from the b axis to the a c plane (with a small induced component along the b axis), for a critical magnetic field of ca. 1.2 T.

Molecular emission in laser-induced breakdown spectroscopy: An investigation of its suitability for chlorine quantification on Mars

NASA Astrophysics Data System (ADS)

Vogt, D. S.; Rammelkamp, K.; Schröder, S.; Hübers, H. W.

2018-03-01

The intensity of the molecular CaCl emission in LIBS spectra is examined in order to evaluate its suitability for the detection of chlorine in a Martian environment. Various mixtures resembling Martian targets with varying Cl content are investigated under simulated Martian conditions. The reactions leading to the formation of CaCl are modeled based on reaction kinetics and are used to fit the measured CaCl band intensities. MgCl bands are also investigated as potential alternatives to CaCl, but no MgCl bands can be identified in samples containing both Mg and Cl. The study confirms that CaCl is well suited for the indirect detection of chlorine, but finds a strong dependence on the concentrations of Ca and Cl in the sample. Spectra from samples with a high chlorine concentration can have low-intensity CaCl emission due to a deficiency of Ca. A qualitative estimate of the sample composition is possible based on the ratio of the band intensity of CaCl to the intensity of Ca emission lines. Time-resolved measurements show that the CaCl concentration in the plasma is highest after about 1 μs.

Induction of apoptosis by Fe(salen)Cl through caspase-dependent pathway specifically in tumor cells.

PubMed

Pradhan, Nitika; Pratheek, B M; Garai, Antara; Kumar, Ashutosh; Meena, Vikram S; Ghosh, Shyamasree; Singh, Sujay; Kumari, Shikha; Chandrashekar, T K; Goswami, Chandan; Chattopadhyay, Subhasis; Kar, Sanjib; Maiti, Prasanta K

2014-10-01

Iron-based compounds possess the capability of inducing cell death due to their reactivity with oxidant molecules, but their specificity towards cancer cells and the mechanism of action are hitherto less investigated. A Fe(salen)Cl derivative has been synthesized that remains active in monomer form. The efficacy of this compound as an anti-tumor agent has been investigated in mouse and human leukemia cell lines. Fe(salen)Cl induces cell death specifically in tumor cells and not in primary cells. Mouse and human T-cell leukemia cell lines, EL4 and Jurkat cells are found to be susceptible to Fe(salen)Cl and undergo apoptosis, but normal mouse spleen cells and human peripheral blood mononuclear cells (PBMC) remain largely unaffected by Fe(salen)Cl. Fe(salen)Cl treated tumor cells show significantly higher expression level of cytochrome c that might have triggered the cascade of reactions leading to apoptosis in cancer cells. A significant loss of mitochondrial membrane potential upon Fe(salen)Cl treatment suggests that Fe(salen)Cl induces apoptosis by disrupting mitochondrial membrane potential and homeostasis, leading to cytotoxity. We also established that apoptosis in the Fe(salen)Cl-treated tumor cells is mediated through caspase-dependent pathway. This is the first report demonstrating that Fe(salen)Cl can specifically target the tumor cells, leaving the primary cells least affected, indicating an excellent potential for this compound to emerge as a next-generation anti-tumor drug. © 2014 International Federation for Cell Biology.

X-ray absorption studies of chlorine valence and local environments in borosilicate waste glasses

NASA Astrophysics Data System (ADS)

McKeown, David A.; Gan, Hao; Pegg, Ian L.; Stolte, W. C.; Demchenko, I. N.

2011-01-01

Chlorine (Cl) is a constituent of certain types of nuclear wastes and its presence can affect the physical and chemical properties of silicate melts and glasses developed for the immobilization of such wastes. Cl K-edge X-ray absorption spectra (XAS) were collected and analyzed to characterize the unknown Cl environments in borosilicate waste glass formulations, ranging in Cl-content from 0.23 to 0.94 wt.%. Both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data for the glasses show trends dependent on calcium (Ca) content. Near-edge data for the Ca-rich glasses are most similar to the Cl XANES of CaCl 2, where Cl - is coordinated to three Ca atoms, while the XANES for the Ca-poor glasses are more similar to the mineral davyne, where Cl is most commonly coordinated to two Ca in one site, as well as Cl and oxygen nearest-neighbors in other sites. With increasing Ca content in the glass, Cl XANES for the glasses approach that for CaCl 2, indicating more Ca nearest-neighbors around Cl. Reliable structural information obtained from the EXAFS data for the glasses is limited, however, to Cl sbnd Cl, Cl sbnd O, and Cl sbnd Na distances; Cl sbnd Ca contributions could not be fit to the glass data, due to the narrow k-space range available for analysis. Structural models that best fit the glass EXAFS data include Cl sbnd Cl, Cl sbnd O, and Cl sbnd Na correlations, where Cl sbnd O and Cl sbnd Na distances decrease by approximately 0.16 Å as glass Ca content increases. XAS for the glasses indicates Cl - is found in multiple sites where most Cl-sites have Ca neighbors, with oxygen, and possibly, Na second-nearest neighbors. EXAFS analyses suggest that Cl sbnd Cl environments may also exist in the glasses in minor amounts. These results are generally consistent with earlier findings for silicate glasses, where Cl - was associated with Ca 2+ and Na + in network modifier sites.

Physical conditions in CaFe interstellar clouds

NASA Astrophysics Data System (ADS)

Gnaciński, P.; Krogulec, M.

2008-01-01

Interstellar clouds that exhibit strong Ca I and Fe I lines are called CaFe clouds. Ionisation equilibrium equations were used to model the column densities of Ca II, Ca I, K I, Na I, Fe I and Ti II in CaFe clouds. We find that the chemical composition of CaFe clouds is solar and that there is no depletion into dust grains. CaFe clouds have high electron densities, n_e≈1 cm-3, that lead to high column densities of neutral Ca and Fe.

Long-range volcanic ash transport and fallout during the 2008 eruption of Chaiten volcano, Chile

NASA Astrophysics Data System (ADS)

Durant, A. J.; Prata, A. J.; Villarosa, G.; Rose, W. I.; Delmelle, P.; Viramonte, J.

2012-04-01

The May 2008 eruption of Chaitén volcano, Chile, provided a rare opportunity to measure the long-range transport of volcanic emissions and characteristics of a widely-dispersed terrestrial ash deposit. Airborne ash mass, quantified using thermal infrared satellite remote sensing, ranged between 0.2-0.4 Tg during the period 3-7 May 2008. A high level of spatiotemporal correspondence was observed between cloud trajectories and changes in surface reflectivity, which was inferred to indicate ash deposition. The evolution of the deposit was mapped for the first time using satellite-based observations of surface reflectivity. The distal (>80 km) ash deposit was poorly sorted and fine grained, and mean particle size varied very little beyond a distance >300 km. There were 3 consistent particle size subpopulations in fallout at distances >300 km which suggests that aggregation influenced particle settling. Discrete temporal sampling and characterisation of fallout demonstrated contributions from specific eruptive phases. Some evidence for winnowing was identified through comparison of samples collected at the time of deposition to bulk samples collected months after deposition. X-Ray Photoelectron Spectroscopy (XPS) analyses revealed surface enrichments in Ca, Na and Fe and the presence of coatings of mixed Ca-, Na- and Fe-rich salts on ash particles prior to deposition. XPS analyses revealed strong surface Fe enrichments (in contrast to the results from bulk leachate analyses), which indicates that surface analysis techniques should be applied to investigate potential influences on ocean productivity in response to volcanic ash fallout over oceans. Low S:Cl ratios in leachates indicate that the eruption had a low S content, and high Cl:F ratios imply gas-ash interaction within a Cl-rich environment. We estimate that ash fallout had potential to scavenge ~42 % of total S released into the atmosphere prior to deposition.

Coatings on Atacama Desert Basalt: A Possible Analog for Coatings on Gusev Plains Basalt

NASA Technical Reports Server (NTRS)

Sutter, B.; Golden, D. C.; Amundson, R.; Chong-Diaz, G.; Ming, D. W.

2007-01-01

Surface coatings on Gusev Plains basalt have been observed and may contain hematite and nanophase Fe-oxides along with enrichments in P, S, Cl, and K relative to the underlying rock. The Gusev coatings may be derived from the dissolution of adhering soil and/or parent rock along with the addition of S and Cl from outside sources. Transient water for dissolution could be sourced from melting snow during periods of high obliquity, acid fog, and/or ground water (Haskin et al., 2005). Coatings on basalt in the hyper-arid (less than 2mm y(sup -1)) Atacama Desert may assist in understanding the chemistry, mineralogy and formation mechanisms of the Gusev basalt coatings. The Atacama Desert climate is proposed to be analogous to a paleo-Mars climate that was characterized by limited aqueous activity when the Gusev coatings could have formed. The objectives of this work are to (i) determine the chemical nature and extent of surface coatings on Atacama Desert basalt, and (ii) assess coating formation mechanisms in the Atacama Desert. Preliminary backscattered electron imaging of Atacama basalt thin-sections indicated that the coatings are as thick as 20 m. The boundary between the coating and the basalt labradorite, ilmenite, and augite grains was abrupt indicating that the basalt minerals underwent no chemical dissolution. The Atacama coatings have been added to the basalt instead of being derived from basalt chemical weathering. Semi-quantitative energy dispersive spectroscopy shows the coatings to be chemically homogeneous. The coating is depleted in Ca (0.9 wt% CaO) and enriched in K (1.3 wt.% K2O) and Si (69.1 wt.% SiO2) relative to the augite and labradorite grains. A dust source enriched in Si (e.g., poorly crystalline silica) and K and depleted in Ca appears to have been added to the basalt surface. Unlike the Gusev coatings, no P, S, and Cl enrichment was observed. However, Fe (3.2 wt.% FeO) was present in the Atacama coatings suggesting the present of Fe-oxides. While the chemistry of Atacama coating does not mirror the Gusev coating, the coating formation mechanism may be similar. The Atacama coatings of surface basalt are derived completely from exogenous sources. If surface Mars rocks have experienced limited wetting conditions as in the Atacama, then Mars coatings may be derived only from dissolution of material adhering to rock.

O2(a1Δg) + Mg, Fe, and Ca: Experimental kinetics and formulation of a weak collision, multiwell master equation with spin-hopping

NASA Astrophysics Data System (ADS)

Plane, J. M. C.; Whalley, C. L.; Frances-Soriano, L.; Goddard, A.; Harvey, J. N.; Glowacki, D. R.; Viggiano, A. A.

2012-07-01

The first excited electronic state of molecular oxygen, O2(a1Δg), is formed in the upper atmosphere by the photolysis of O3. Its lifetime is over 70 min above 75 km, so that during the day its concentration is about 30 times greater than that of O3. In order to explore its potential reactivity with atmospheric constituents produced by meteoric ablation, the reactions of Mg, Fe, and Ca with O2(a) were studied in a fast flow tube, where the metal atoms were produced either by thermal evaporation (Ca and Mg) or by pulsed laser ablation of a metal target (Fe), and detected by laser induced fluorescence spectroscopy. O2(a) was produced by bubbling a flow of Cl2 through chilled alkaline H2O2, and its absolute concentration determined from its optical emission at 1270 nm (O2(a1Δg - X3Σg-). The following results were obtained at 296 K: k(Mg + O2(a) + N2 → MgO2 + N2) = (1.8 ± 0.2) × 10-30 cm6 molecule-2 s-1; k(Fe + O2(a) → FeO + O) = (1.1 ± 0.1) × 10-13 cm3 molecule-1 s-1; k(Ca + O2(a) + N2 → CaO2 + N2) = (2.9 ± 0.2) × 10-28 cm6 molecule-2 s-1; and k(Ca + O2(a) → CaO + O) = (2.7 ± 1.0) × 10-12 cm3 molecule-1 s-1. The total uncertainty in these rate coefficients, which mostly arises from the systematic uncertainty in the O2(a) concentration, is estimated to be ±40%. Mg + O2(a) occurs exclusively by association on the singlet surface, producing MgO2(1A1), with a pressure dependent rate coefficient. Fe + O2(a), on the other hand, shows pressure independent kinetics. FeO + O is produced with a probability of only ˜0.1%. There is no evidence for an association complex, suggesting that this reaction proceeds mostly by near-resonant electronic energy transfer to Fe(a5F) + O2(X). The reaction of Ca + O2(a) occurs in an intermediate regime with two competing pressure dependent channels: (1) a recombination to produce CaO2(1A1), and (2) a singlet/triplet non-adiabatic hopping channel leading to CaO + O(3P). In order to interpret the Ca + O2(a) results, we utilized density functional theory along with multireference and explicitly correlated CCSD(T)-F12 electronic structure calculations to examine the lowest lying singlet and triplet surfaces. In addition to mapping stationary points, we used a genetic algorithm to locate minimum energy crossing points between the two surfaces. Simulations of the Ca + O2(a) kinetics were then carried out using a combination of both standard and non-adiabatic Rice-Ramsperger-Kassel-Marcus (RRKM) theory implemented within a weak collision, multiwell master equation model. In terms of atmospheric significance, only in the case of Ca does reaction with O2(a) compete with O3 during the daytime between 85 and 110 km.

Recurring Slope Lineae (RSL) and Chloride Hydrates within Mars Subsurface

NASA Astrophysics Data System (ADS)

Lu, Y.; Wang, A.

2012-12-01

RSL is an important phenomenon revealed by HiRISE-MRO observations on Mars (McEwen et al., 2011). The RSL form and grow on some equator-facing slopes during warm seasons on Mars when temperature (T in afternoon) is in the range of ~250-300K. We hypothesize that chloride hydrates may exist in some areas within the subsurface of southern hemisphere on Mars, and the deliquescence of these chloride hydrates at elevated temperature may have produced large quantity of brine that caused the RSL observed by HiRISE team. This hypothesis is based on three lines of reasoning: (1) chlorine (Cl) is found to be broadly distributed on Mars (GRS-ODY) and has been detected in the chemistry of every surface samples during all Mars surface exploration missions (Vikings, Pathfinder, Spirit, Opportunity, and Phoenix). In addition, the existence of chlorides in martian southern hemisphere was suggested by a set of THEMIS-ODY data analyses (Osterloo et al., 2008, 2010). In terrestrial saline playas, large amounts of chlorides invariably appears in the precipitates from salty brines (Zheng et al., 2009, Wang et al., 2009), although the precipitation sequence of chlorides on Mars might be different from that on Earth (Tosca et al., 2008, McLennan et al., 2012). (2) A subsurface layer when enriched with ice, or hydrous sulfates or chloride hydrates (all have high thermal inertia) and covered by a dry layer of surface soils (very low thermal inertia) will be able to maintain a lower Tmax and a much smaller delta-T that are not affected by the large temperature variations at Mars surface during diurnal and seasonal cycles (Mellon, 2004). (3) Chloride hydrates (such as MgCl2.12H2O, FeCl2.6H2O, CaCL2.6H2O, etc) would form from Cl-bearing brine at low T; they would be stable in a large T range (beyond room T in lab) and their deliquescence would occur abruptly at elevated temperatures (Baumgartner & Bakker 2009, and many others). We have started a systematic laboratory investigation on the thermodynamics and kinetics properties of chloride hydrates. The goals are to determine (1) the stability fields of Mg-, Fe2+-, Fe3+-, Ca-, Al-, Na-chloride hydrates in RH-T space, especially the phase boundaries of hydrates-deliquescence; (2) the rate of their dehydration, and especially the rate of their deliquescence as function of T, P, and PH2O; (3) the RH level that each chloride hydrate can maintain in an enclosure at T relevant to those within Mars subsurface. We will report the experimental results from (3), and will compare them with a similar set of data from hydrous sulfates (Mg, Fe, Ca, Al). The criticality of learning the property (3) is that the deliquescence of a hydrous salt at a T only occurs when RH is higher than a threshold. For example, deliquescence of ferricopiapite would happen when RH > 75% at 0°C. If the environmental RH is lower, the dehydration of hydrous salt will go through solid-solid phase transition, instead of deliquescence, such that water would be released to the atmosphere and brine would not form. It is possible that deliquescence of both hydrous sulfates and chlorides (as well as the melting of Cl-enriched brines) contributed the RSL. Our working hypothesis favors chloride hydrates because dry chloride (after releasing water) in RSL would not be visible by Vis-NIR spectroscopy, which is consistent with the mission observations.

Development of weathering profile of a forest hillslope in clay-rich sedimentary system

NASA Astrophysics Data System (ADS)

Nicklas, R. W.; Kim, H.; Bishop, J. K.; Rempe, D. M.

2012-12-01

Hillslopes are an essential element to the understanding of landscape evolution, storm flow generation and biogeochemical processes. Since 2008, extensive studies of climate variables, vegetation, soil moisture, subsurface hydrology, and water chemistry have taken place at a small forested hillslope, "Rivendell", at the Angelo Coast Range Reserve located at the headwaters of the Eel River, California. Here we report on the signature of weathering processes through analysis of core and soil samples collected during well drilling campaigns. Core samples from multiple depths at four wells (at creek edge, mid-slope, up-slope, and ridge-top) were selected and include 1) soil; 2) unsaturated fractured/ weathered zone; 3) zone of seasonal water table fluctuation within weathered bedrock; and 4) chronically saturated fresh bedrock zone. We also include soil samples from a groundwater seep located at the toe of the slope. The mineralogy of these samples was identified using X-ray diffraction. Samples were analyzed for salt and Ca(Mg)CO3 concentrations, and cation exchange capacity using Milli-Q water and acetic acid extraction and BaCl2-NH4Cl treatments, respectively. To further quantify the mineral dissolution and secondary mineral precipitation, a sequential extraction of trace metals were conducted - 1) exchangeable using MgCl2; 2) bound to carbonates using NaOAc; 3) bound to Fe-Mn oxides using NH2OH HCl; and 4) bound to organic matters using H2O2 and HNO3. The total elemental contents were determined using HF-HNO3-HClO4 dissolution. The mineralogy of the fresh bedrock zone showed similar patterns throughout the site -for clay minerals, chlorite, illite, interstratified illite/smectite were dominant; K-feldspar dominated the primary minerals. Shallow (<30 cm) soils had kaolinite, and chlorite was absent in some samples. CaCO3 was also predominantly found in the fresh bedrock zone and progressively increased with depth. The depletion profile of major cations (Ca, Na, Mg, K, and Si) and trace metals (Fe, Mn and Al) show the mineral dissolution fronts. K-feldspar, chlorite and CaCO3 dissolution and secondary mineral precipitation are thus the major processes that are critical to the interpretation of groundwater chemistry.

Direct effects of soil amendments on field emergence and growth of the invasive annual grass Bromus tectorum L. and the native perennial grass Hilaria jamesii (Torr.) Benth

USGS Publications Warehouse

Newingham, B.A.; Belnap, J.

2006-01-01

Bromus tectorum L. is a non-native, annual grass that has invaded western North America. In SE Utah, B. tectorum generally occurs in grasslands dominated by the native perennial grass, Hilaria jamesii (Torr.) Benth. and rarely where the natives Stipa hymenoides Roem. and Schult. and S. comata Trin. & Rupr. are dominant. This patchy invasion is likely due to differences in soil chemistry. Previous laboratory experiments investigated using soil amendments that would allow B. tectorum to germinate but would reduce B. tectorum emergence without affecting H. jamesii. For this study we selected the most successful treatments (CaCl2, MgCl2, NaCl and zeolite) from a previous laboratory study and applied them in the field in two different years at B. tectorum-dominated field sites. All amendments except the lowest level of CaCl2 and zeolite negatively affected B. tectorum emergence and/or biomass. No amendments negatively affected the biomass of H. jamesii but NaCl reduced emergence. Amendment effectiveness depended on year of application and the length of time since application. The medium concentration of zeolite had the strongest negative effect on B. tectorum with little effect on H. jamesii. We conducted a laboratory experiment to determine why zeolite was effective and found it released large amounts of Na+, adsorbed Ca2+, and increased Zn2+, Fe2+, Mn2+, Cu2+, exchangeable Mg2+, exchangeable K, and NH 4+ in the soil. Our results suggest several possible amendments to control B. tectorum. However, variability in effectiveness due to abiotic factors such as precipitation and soil type must be accounted for when establishing management plans. ?? Springer 2006.

Synthesis and characterization of sulfur-voided cubanes. Structural analogues for the MoFe(3)S(3) subunit in the nitrogenase cofactor.

PubMed

Coucouvanis, Dimitri; Han, Jaehong; Moon, Namdoo

2002-01-16

A new class of Mo/Fe/S clusters with the MoFe(3)S(3) core has been synthesized in attempts to model the FeMo-cofactor in nitrogenase. These clusters are obtained in reactions of the (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et (I), (n)Pr (II)] clusters with CO. The new clusters include those preliminarily reported: (Cl(4)-cat)MoFe(3)S(3)(PEt(3))(2)(CO)(6) (III), (Cl(4)-cat)(O)MoFe(3)S(3)(PEt(3))(3)(CO)(5) (IV), (Cl(4)-cat)(Pyr)MoFe(3)S(3)(PEt(3))(2)(CO)(6) (VI), and (Cl(4)-cat)(Pyr)MoFe(3)S(3)(P(n)Pr(3))(3)(CO)(4) (VIII). In addition the new (Cl(4)-cat)(O)MoFe(3)S(3)(P(n)Pr(3))(3)(CO)(5) cluster (IVa), the (Cl(4)-cat)(O)MoFe(3)S(3)(PEt(3))(2)(CO)(6)cluster (V), the (Cl(4)-cat)(O)MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (Va), the (Cl(4)-cat)(Pyr)MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (VIa), and the (Cl(4)-cat)(P(n)Pr(3))MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (VII) also are reported. Clusters III-VIII have been structurally and spectroscopically characterized. EPR, zero-field (57)Fe-Mössbauer spectroscopic characterizations, and magnetic susceptibility measurements have been used for a tentative assignment of the electronic and oxidation states of the MoFe(3)S(3) sulfur-voided cuboidal clusters. A structural comparison of the clusters with the MoFe(3)S(3) subunit of the FeMo-cofactor has led to the suggestion that the storage of reducing equivalents into M-M bonds, and their use in the reduction of substrates, may occur with the FeMo-cofactor, which also appears to have M-M bonding. On the basis of this argument, a possible N(2)-binding and reduction mechanism on the FeMoco-cofactor is proposed.

Probing Intracellular Element Concentration Changes during Neutrophil Extracellular Trap Formation Using Synchrotron Radiation Based X-Ray Fluorescence

PubMed Central

Niemiec, Maria J.; Laforce, Brecht; Garrevoet, Jan; Vergucht, Eva; De Rycke, Riet; Cloetens, Peter; Urban, Constantin F.; Vincze, Laszlo

2016-01-01

High pressure frozen (HPF), cryo-substituted microtome sections of 2 μm thickness containing human neutrophils (white blood cells) were analyzed using synchrotron radiation based X-ray fluorescence (SR nano-XRF) at a spatial resolution of 50 nm. Besides neutrophils from a control culture, we also analyzed neutrophils stimulated for 1–2 h with phorbol myristate acetate (PMA), a substance inducing the formation of so-called Neutrophil Extracellular Traps (or NETs), a defense system again pathogens possibly involving proteins with metal chelating properties. In order to gain insight in metal transport during this process, precise local evaluation of elemental content was performed reaching limits of detection (LODs) of 1 ppb. Mean weight fractions within entire neutrophils, their nuclei and cytoplasms were determined for the three main elements P, S and Cl, but also for the 12 following trace elements: K, Ca, Mn, Fe, Co, Ni, Cu, Zn, Se, Br, Sr and Pb. Statistical analysis, including linear regression provided objective analysis and a measure for concentration changes. The nearly linear Ca and Cl concentration changes in neutrophils could be explained by already known phenomena such as the induction of Ca channels and the uptake of Cl under activation of NET forming neutrophils. Linear concentration changes were also found for P, S, K, Mn, Fe, Co and Se. The observed linear concentration increase for Mn could be related to scavenging of this metal from the pathogen by means of the neutrophil protein calprotectin, whereas the concentration increase of Se may be related to its antioxidant function protecting neutrophils from the reactive oxygen species they produce against pathogens. We emphasize synchrotron radiation based nanoscopic X-ray fluorescence as an enabling analytical technique to study changing (trace) element concentrations throughout cellular processes, provided accurate sample preparation and data-analysis. PMID:27812122

Determination of some enzymes and macro- and microelements in stallion seminal plasma and their correlations to semen quality.

PubMed

Pesch, Sandra; Bergmann, Martin; Bostedt, Hartwig

2006-07-15

Seminal plasma is very important for sperm metabolism as well as sperm function and survival and transport in the female genital tract. Analysis of enzyme activities and concentrations of elements can estimate integrity and function of sperm cell membranes. In man much data are available about biochemical analyses of seminal plasma. However, not many studies have been conducted in horses yet. We collected ejaculates from 72 stallions, measured the volume, obtained seminal plasma by centrifugation and examined spermatozoa with light microscopy for motility, concentration, for dead sperm and morphology. Of seminal plasma fluid, we measured activities of aspartate-amino-transferase (AST), gamma-glutamyl-transferase (GGT), alkaline phosphatase (AlP), acid phosphatase (AcP) and lactate-dehydrogenase (LDH) as well as concentrations of sodium (Na(+)), potassium (K(+)), total and ionised calcium (Ca(TOTAL)/Ca(2+)), magnesium (Mg(2+)), phosphate (P), chloride (Cl), copper (Cu), iron (Fe) and zinc (Zn). In addition, correlations among different parameters in light microscopy and seminal plasma were statistically examined by using the Spearman rank correlation coefficient. Median enzyme activities for AST, GGT, AlP, AcP and LDH were 80.0, 7,500, 30,200, 20.0, 81.0 IU/L, respectively. Concentrations of Na(+), K(+), Ca(TOTAL), Ca(2+), Mg(2+), P, Cl were 110.5, 22.1, 2.9, 1.7, 3.1, 1.1 and 114.5 mmol/L, and of microelements Cu, Fe and Zn were 17.8, 1.9 and 13.2 micromol/L, respectively. Furthermore, we found significant correlations between semen volume as well as sperm concentration and AST, GGT, AlP, AcP and LDH as well as Fe and Zn. This made us propose a primary testicular and epididymal origin of these parameters. Significant correlation between GGT and motility may be a sign for its function for cell protection against free radicals. LDH activity significantly correlates with motility and progressive motility, live:dead-ratio and pathomorphology. In our study, LDH seems to be the most predictive enzyme for semen quality. This is the first report about GGT, AcP and LDH activities as well as iron in equine seminal plasma.

Low-temperature carbonization and more effective degradation of carbohydrates induced by ferric trichloride.

PubMed

Xia, Juan; Song, Le Xin; Dang, Zheng

2012-07-05

The present work is devoted to an attempt to understand the effect of an inorganic salt such as ferric trichloride (FeCl(3)) on the carbonization and degradation of carbohydrates such as β-cyclodextrin (CD), amylose, and cellulose. Our data revealed two important observations. First, the presence of FeCl(3) led to the occurrence of a low carbonization temperature of 373 K. This is a rare phenomenon, in which carbonization improvement is present even if a small amount of FeCl(3) was added. Experimental results had provided evidence for the fact that a redox process was started during the low-temperature carbonization of β-CD, causing the reduction of FeCl(3) to ferrous chloride (FeCl(2)) by carbon materials formed in the carbonization process in air. However, the reduction process of FeCl(3) produced the in situ composite nanomaterial of Fe-FeCl(2) combination in nitrogen. Second, a molecule-ion interaction emerged between FeCl(3) and the carbohydrates in aqueous solution, resulting in a more effective degradation of the carbohydrates. Moreover, our results demonstrated that FeCl(3) played the role of a catalyst during the degradation of the carbohydrates in solution. We believe that the current work not only has a significant potential application in disposal of waste carbohydrates but also could be helpful in many fields such as environmental protection, biomass energy development, and inorganic composite nanomaterials.

Metamorphosed Plio-Pleistocene evaporites and the origins of hypersaline brines in the Salton Sea geothermal system, California: Fluid inclusion evidence

NASA Astrophysics Data System (ADS)

McKibben, Michael A.; Williams, Alan E.; Okubo, Susumu

1988-05-01

The Salton Sea geothermal system (SSGS) occurs in Plio-Pleistocene deltaic-lacustrine-evaporite sediments deposited in the Salton Trough, an active continental rift zone. Temperatures up to 365°C and hypersaline brines with up to 26 wt.% TDS are encountered at 1-3 km depth in the sediments, which are undergoing active greenschist facies hydrothermal metamorphism. Previous models for the origins of the Na-Ca-K-Cl brines have assumed that the high salinities were derived mainly from the downward percolation of cold, dense brines formed by low-temperature dissolution of shallow non-marine evaporites. New drillcores from the central part of the geothermal field contain metamorphosed, bedded evaporites at 1 km depth consisting largely of hornfelsic anhydrite interbedded with anhydrite-cemented solution-collapse shale breccias. Fluid inclusions trapped within the bedded and breccia-cementing anhydrite homogenize at 300°C (identical to the measured downhole temperature) and contain saline Na-Ca-K-Cl brines. Some of the inclusions contain up to 50 vol.% halite, sylvite and carbonate crystals at room temperature, and some halite crystals persist to above 300°C upon laboratory heating. The data are consistent with the trapping of halite-saturated Na-Ca-K-Cl fluids during hydrothermal metamorphism of the evaporites and accompanying solution collapse of interbedded shales. We conclude that many of the salt crystals in inclusions are the residuum of bedded evaporitic salt that was dissolved during metamorphism by heated connate fluids. Therefore, the high salinities of the Salton Sea geothermal brines are derived in part from the in situ hydrothermal metamorphism and dissolution of halides and CaSO 4 from relatively deeply-buried lacustrine evaporites. This fact places important constraints on modeling fluid-flow in the SSGS, as brines need not have migrated over great distances. The brines have been further modified to their present complex Na-Ca-K-Fe-Mn-Cl compositions by on-going sediment metamorphism and water-rock interaction.

Experimental study of the solubilities of pyrite in NaCl-bearing aqueous solutions at 250-350°C

NASA Astrophysics Data System (ADS)

Ohmoto, Hiroshi; Hayashi, Ken-Ichiro; Kajisa, Yukari

1994-05-01

A total of sixty-three silica capsule experiments were performed to determine the solubilities of pyrite in NaCl-bearing aqueous solutions (0, 0.1, 0.5, 1, 2, 3, and 4 m) at 250, 300, and 350°C at pressures of vapor/liquid coexistence. The starting materials in the capsules were H2O(1) + FeS2( s) + S ° ( s) ± NaCl ( s). After reaction times up to ~ 60 days, the quenched solutions were analyzed for ΣFe, σH2S, ΣSO42-, and pH; the ΣFe content, ranging 5-1,300 ppm, generally increased with increasing temperature and ΣCl content of solution. The calculated solution compositions at the experimental P-T conditions fall mostly in the following ranges: pH = 2.0 to 3.2, logaH2s = -1.9 to -1.0, logaHSO4- = -3.8 to -2.0, and logaH2( aq) = -7.0 to -5.0. Evaluation of the experimental data suggests that the various redox equilibria between solution and mineral were attained in most of the experimental solutions. The pH, aH2S( aq) , and aH2( aq) of the solutions were controlled by the sulfur hydrolysis reaction (48° + 4 H2O( l) = 3 H2S( aq) + HSO4- + H+) and the sulfide/sulfate reaction ( H2S( aq) + 4 H2O( l) = 4 H2( aq) + H+ + HSO4-). The pyrite solubility is controlled by a general reaction: FeS2( s) + nCl- + 2 H+ + H2( aq) = FeCln2- n + 2 H2S( aq). The equilibrium constants for this reaction, as well as those for association of ferrous chloride complexes ( Fe2+ + nCl- = FeCln2- n), were obtained at 250, 300, and 350°C; they were used also to compute the equilibrium constants for the reactions controlling the solubilities of pyrrhotite, magnetite, and hematite: FeS( s) + 2 H+ + nCl- = FeCln2- n + H2S( aq); Fe3O4( s) + 6 H+ + 3 nCl- + H2( aq) = 3 FeCln2- n + H2O( aq); Fe2O3( s) + 4 H+ + 2 nCl- + H2( aq) = 2 FeCln2- n + 3 H2O( aq). Our experimental data suggest that the dominant Fe-Cl complex is FeCl + in solutions of ΣCl ≤ 0.5 m at 250°C and ΣCl ≤ 0.1 m at 300 and 350°C; FeCl 20 is dominant in solutions of the higher ΣCl contents at each temperature. The association constants for FeCl + and FeCl 2 estimated from this study are in good agreement with those estimated recently by HEINRICH and SEWARD (1990), DING and SEYFRIED (1992), Fein et al. (1992), and Palmer and Hyde (1992). Our solubility constants for pyrite are in good agreement with those obtained by CRERAR et al. (1978) and WOOD et al. (1987) for 3 m ΣCl solution at 350°C, but are 0.5-2 orders of magnitude higher than those obtained by them at lower temperatures and/or at lower ΣCl values. Our data suggest that natural hydrothermal fluids that are in equilibrium with pyrite, the most abundant sulfide mineral in the upper crust, are able to transport sufficient amounts (> 10 -m) of both Fe and H 2S to produce pyrite-rich ore deposits at temperatures above 250°C, and possibly at lower temperatures. The solubility of pyrite (and of other Fe-bearing minerals) is affected very little by a change of temperature, provided the pH, aH2( aq), aH2S( aq), and ΣCl values remain constant.

Vertical nutrient and trace element migration in cambisoils after application of residues from anaerobic digestion of pig manure

NASA Astrophysics Data System (ADS)

Sager, Manfred; Unterfrauner, Hans

2013-04-01

Cambisols sampled in alpine pastures were packed into soil columns in order to monitor downward migration of nutrient and trace elements, applied within the residue from anaerobic digestion of a pig manure. 2 rain events per week were simulated. The manure added substantial amounts of K, ammonium, Na, Ca, P, S, Cl, B, Zn and Cu to the soil, whereas Mg, Mn, Ni, Cr, Pb, Cd and V were at the same level. In the eluates, total elemental composition as well as nitrate and ammonium were monitored. Addition of soluble Fe (at 1000 mg/l as FeCl3) decreased the release of soluble sulphate, but had no significant effect on the release of Fe and P. During subsequent rain events, exchangeable K remained enriched in the topsoil, wheras total sulfur moved to deeper layers. After 8 weeks, the columns were dismantled and analyzed for quasi-total and mobile fractions. Both in topsoils and subsoils, manure addition finally increased soil pH in case of low P soils, but decreased soil pH in case of high pH soils. Effects of manure applications on groundwater formation processes will be discussed.

Cosmogenic Cl-36 production rates in meteorites and the lunar surface

NASA Technical Reports Server (NTRS)

Nishiizumi, K.; Arnold, J. R.; Kubik, P. W.; Elmore, D.; Reedy, R. C.

1989-01-01

Activity vs. depth profiles of cosmic ray produced Cl-36 were measured in metal from two cores each in the St. Severin and Jilin chondrites and in lunar core 15008. Production of Cl-36 in these samples range from high-energy reactions with Fe and Ni to low-energy reactions with Ca and K and possibly neutron-capture reactions with Cl-36. The cross sections used in the Reedy-Arnold model for neutron-induced reactions were adjusted to get production rates that fit the measured Cl-36 activities in St. Severin metal and in the lunar soil of core 15008. The Cl-36 in metal from St. Severin has a fairly flat activity-vs-depth profile, unlike most other cosmogenic nuclides in bulk samples from St. Severin, which increase in concentration with depth. In metal from Jilin, a decrease in Cl-36 was observed near its center. The length of Jilin's most recent cosmic-ray exposure was approximately 0.5 My. Lunar core 15008 has an excess in Cl-36 of about 4 dpm/kg near its surface that was produced by solar-proton-induced reactions. The calculated production rates are consistent with these measured trends in 15008.

Characterization of homoionic Fe 2+-type montmorillonite: Potential chemical species of iron contaminant

NASA Astrophysics Data System (ADS)

Kozai, Naofumi; Inada, Koichi; Adachi, Yoshifusa; Kawamura, Sachi; Kashimoto, Yusuke; Kozaki, Tamotsu; Sato, Seichi; Ohnuki, Toshihiko; Sakai, Takuro; Sato, Takahiro; Oikawa, Masakazu; Esaka, Fumitaka; Mitamura, Hisayoshi

2007-08-01

Fe 2+-montmorillonite with Fe 2+ ions occupying cation exchange sites is an ideal transformation product in bentonite buffer material. In our previous study on preparation and characterization of Fe 2+-montmorillonite, the montmorillonite sample that adsorbed Fe 2+ ions on almost all of the cation exchange sites was prepared using a FeCl 2 solution under an inert gas condition [N. Kozai, Y. Adachi, S. Kawamura, K. Inada, T. Kozaki, S. Sato, H. Ohashi, T. Ohnuki, T. Banba, J. Nucl. Sci. Technol. 38 (2001) 1141]. In view of the unstable nature of iron(II) chemical species, this study attempted to determine the potential contaminant iron chemical species in the sample. Nondestructive elemental analysis revealed that a small amount of chloride ions remained dispersed throughout the clay particles. The chloride ion retention may be due to the adsorption of FeCl + ion pairs in the initial FeCl 2 solution and the subsequent containment of the Cl - ions that are dissociated from the FeCl + ion pairs during excess salt removal treatment. Two explanations are advanced for the second process: the slow release of the remaining Cl - ions from the collapsed interlayer of the montmorillonite, and the transformation of a minor fraction of the remaining FeCl + ion pairs to iron(III) hydroxide chloride complexes having low solubility.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Comar, C.L.; Lengemann, F.W.; Wasserman, R.H. et al

Research activities during the past 6 years are reviewed. Results are reported for recent studies on adaptation to increased dietary Ca by dairy cows as a factor in the reduction of Sr/sup 90/ content of milk; the testing of a theoretical model of alkaline earth absorption in rats by a comparison of biological discrimination among Ca/sup 47/, Sr/sup 85/, and Ba/sup 133/ in the presence of glucose, lactose, and lysine; the effects of lactose on the intestinal absorption of Ca in rats; a comparison of the ileal absorption of Ca/ sup 47/ and Sr/sup 85/ by rats from solutions withmore » high and low concentrations of stable Ca; determinatione of the Ca, Mg, and total alkaline earth content in mucosal tissue and plasma of normally fed rats, fasted rats, and rats fed a lactose solution; an investigation of non-exchangeable Ca compartments in the plasma of sheep; the effect of lactose and vitamin D on calcification in the rachitic chick; the metabolism and milk content of I/sup 131/ of dairy cows after long-term daily administration of I/sup 131/; the absorption of Fe/sup 59/ in sheep; the development of a method for the estimation of parasitic blood loss in sheep by whole-body counting of Fe/sup 59/ retention; the development of a method for the simultaneous measurement of erythrocyte and plasma volume in sheep using Fe/sup 59/ as a tracer; the concentration of Na/sup 22/, Cl/sup 36/, and C/sup 14/ inulin in rat kidney and counter-current mechanisms for the production of concentrated urine in mammals; the effects of diuretics on the distribution of Na/ sup 22/, Fe/sup 59/-labeled erythrocytes, and I/sup 131/labeled albumin in rat kidneys; the effects of thiamine on nervous response to ultraviolet radiation in frogs and lobsters; the effects of gamma radiation on reproductive capabilities of young male rabbits; and an evaluation of the contamination of the food chain by fallout fission products, with emphasis on Sr/sup 90/, Cs/sup 137/, and I/sup 131/ intake from total diet and individual food items. A list is included of publications resulting from research conducted under this contract. (C.H.)« less

PURIFICATION OF URANIUM FUELS

DOEpatents

Niedrach, L.W.; Glamm, A.C.

1959-09-01

An electrolytic process of refining or decontaminating uranium is presented. The impure uranium is made the anode of an electrolytic cell. The molten salt electrolyte of this cell comprises a uranium halide such as UF/sub 4/ or UCl/sub 3/ and an alkaline earth metal halide such as CaCl/sub 2/, BaF/sub 2/, or BaCl/sub 2/. The cathode of the cell is a metal such as Mn, Cr, Co, Fe, or Ni which forms a low melting eutectic with U. The cell is operated at a temperature below the melting point of U. In operation the electrodeposited uranium becomes alloyed with the metal of the cathode, and the low melting alloy thus formed drips from the cathode.

Matrix isolation infrared spectra, assignment and DFT investigation on reactions of iron and manganese monoxides with CH3Cl.

PubMed

Zhao, Yanying; Fan, Kexue; Huang, Yongfei; Zheng, Xuming

2013-12-01

The reactions of iron and manganese monoxide molecules (FeO, and MnO) with monochloromethane in solid argon have been studied by matrix isolation infrared spectroscopy and quantum chemistry calculations. When annealing, the reactions of FeO and MnO with CH3Cl first form the OM-(η(Cl)-CH3Cl) (MMn, Fe) complexes, which can isomerize to CH3MOCl (MMn, Fe) upon 300<λ<580 nm irradiation. The products were characterized by isotopic IR studies with CD3Cl and (13)CH3Cl and density functional calculations. Based on theoretical calculations, the OFe-(η(Cl)-CH3Cl) and OMn-(η(Cl)-CH3Cl) complexes have (5)A' and (6)A' ground state with Cs symmetry, respectively. The accurate CCSD(T) single point calculations illustrate the CH3MOCl isomerism are 13.8 and 3.1 kcal/mol lower in energy than the OM-(η(Cl)-CH3Cl) (MMn, Fe) complexes. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Carbonate Mineral Assemblages as Inclusions in Yakutian Diamonds: TEM Verifications

NASA Astrophysics Data System (ADS)

Logvinova, A. M.; Wirth, R.; Sobolev, N. V.; Taylor, L. A.

2014-12-01

Carbonate mineral inclusions are quite rare in diamonds from the upper mantle, but are evidence for a carbonate abundance in the mantle. It is believed that such carbonatitic inclusions originated from high-density fluids (HDFs) that were enclosed in diamond during its growth. Using TEM and EPMA, several kinds of carbonate inclusions have been identified in Yakutian diamonds : aragonite, dolomite, magnesite, Ba-, Sr-, and Fe-rich carbonates. Most of them are represented by multi-phase inclusions of various chemically distinct carbonates, rich in Ca, Mg, and K and associated with minor amounts of silicate, oxide, saline, and volatile phases. Volatiles, leaving some porosity, played a significant role in the diamond growth. A single crystal of aragonite (60μm) is herein reported for the first time. This inclusion is located in the center of a diamond from the Komsomolskaya pipe. Careful CL imaging reveals the total absence of cracks around the aragonite inclusion - i.e., closed system. This inclusion has been identified by X-ray diffraction and microprobe analysis. At temperatures above 1000 0C, aragonite is only stable at high pressures of 5-6 GPa. Inside this aragonite, we observed nanocrystalline inclusions of titanite, Ni-rich sulfide, magnetite, water-bearing Mg-silicate, and fluid bubbles. Dolomite is common in carbonate multi-phase inclusions in diamonds from the Internatsionalnaya, Yubileinaya, and Udachnaya kimberlite pipes. Alluvial diamonds of the northeastern Siberian Platform are divided into two groups based on the composition of HDFs: 1) Mg-rich multi-phase inclusions (60% magnesite + dolomite + Fe-spinel + Ti-silicate + fluid bubbles); and 2) Ca-rich multi-phase inclusions (Ca,Ba-, Ca,Sr-, Ca,Fe-carbonates + Ti-silicate + Ba-apatite + fluid bubbles). High-density fluids also contain K. Volatiles in the fluid bubbles are represented by water, Cl, F, S, CO2, CH4, and heavy hydrocarbons. Origin of the second group of HDFs may be related to the non-silicate carbonatitic melt. We consider the primary hydrous, Сa-rich and Mg-poor carbonate melts as having formed in subducted oceanic crust. Variations of carbonate-inclusion compositions among diamonds indicate the variability in the source media during the formation of diamond and may be the result of metasomatic interaction with host rocks.

Time-resolved interaction of seawater with gabbro: An experimental study of rare-earth element behavior up to 475 °C, 100 MPa

NASA Astrophysics Data System (ADS)

Beermann, Oliver; Garbe-Schönberg, Dieter; Bach, Wolfgang; Holzheid, Astrid

2017-01-01

High metal and rare-earth element (REE) concentrations with unusual ('atypical') normalized REE patterns are documented in fluids from active hydrothermal vent fields on the Mid-Atlantic Ridge, 5°S and the East Scotia Ridge. Those fluids show relative enrichment of middle heavy REEs and almost no Eu anomalies in chondrite-normalized patterns. To understand the processes that produce such atypical REE patterns we ran a series of experiments, in which natural bottom seawater or aqueous solutions (NaCl, NaCl-MgCl2, or NaCl-CaCl2) were reacted with gabbro and gabbro mineral assemblages from 300 to 475 °C and 40 and 100 MPa. These P-T conditions are representative for water-rock interactions in hydrothermal root and discharge zones. Fluid flux variability and kinetics were addressed in the experiments by varying the water-to-rock mass ratio (w/r) from 0.5-10 and using different run durations from 3-720 h. Only seawater and synthetic MgCl2-bearing fluid mobilized significant amounts of REEs, Si, Ca, Fe, and Mn from gabbro, from clinopyroxene, and from plagioclase. At 425 °C and 40 MPa, fluids were initially acidic with pH (25 °C) of ∼2 increasing to values between ∼4 and 7 upon progressing reactions. Rare earth element and Fe contents peaked within 3-6 h after interaction with gabbroic mineral grains (125-500 μm) at w/r of 5 (REEs) and 2-5 (Fe) but decreased with continuing reaction without strong REE fractionation. Most of the REEs that were leached from primary minerals and dissolved in the fluids early became redeposited into solid reaction products after 720 h. Contents of dissolved SiO2 were pressure-dependent, being about twofold higher at 100 MPa than at 40 MPa (425 °C) and were below quartz saturation with gabbro and clinopyroxene as solid starting material and close to quartz saturation with plagioclase reactant. However, Si in fluids from the rock-dominated experiments at 100 MPa with gabbro (w/r 0.5-1) dropped to very low contents. A concomitant decrease in chlorinity suggests that these changes may be due to the breakdown of olivine and the formation of serpentine and Fe-hydroxy chlorides. Regardless of the starting solid reactants, fluid REE patterns were dominantly controlled by w/r. Atypical fluid REE patterns and high fluid REE contents were obtained at high w/r (⩾5). Whereas typical REE patterns known from many mid-ocean ridge vent fluids, showing relative enrichments of light REEs and a positive Eu anomaly, were obtained at low w/r of 0.5-1. Our results hence clearly show that REE contents and patterns of vent fluids are sensitive to variations in the w/r.

Chemical Composition by the APXS along the Downhill Traverse of the Mars Exploration Rover Spirit at Gusev Crater

NASA Technical Reports Server (NTRS)

Bruckner, J.; Dreibus, G.; Gellert, R.; Clark, B.C.; Cohen, B.; McCoy, T.; Ming, D.W.; Mittlefehldt, D.W.; Yen, A.; Athena Science Team

2006-01-01

The Alpha Particle X-ray Spectrometer (APXS) onboard the Mars Exploration Rover Spirit continues to determine the elemental composition of samples at Gusev Crater. Starting around sol 600 the rover descended Husband Hill, which is part of the Columbia Hills, visited the inner basin with a large dune field, called 'El Dorado', and parked at Low Ridge to conserve energy during the martian winter. Many unique samples were discovered by the instruments onboard Spirit during her downhill traverse. Here, we report only on the chemical data obtained by the APXS. The compositions of some of the soil samples are comparable to the mean soil determined along the earlier traverse. However, a light-toned subsurface sample (disturbed by the rover wheels), called Dead Sea Samra , showed the highest sulfur content of all soil samples, the lowest Na, Mg, Al, Cl, K, Ca, Ti, Mn, and Zn, among the lowest Si and P, and among the highest Cr, Fe and Ni. Assuming ferric sulfate as a major mineral, large amounts of a pure silica phase must be present. Color and quantity of Dead Sea Samra resemble somewhat an earlier soil called Paso Robles , though the latter is a mixture of sulfates with phosphate-rich soil. Manganese in Dead Sea Samra is so low that the Fe/Mn ratio exceeds 300, a value that has never been found previously on Mars (Fe/Mn ratio of 46 for Gusev basalts), indicating that only Fe(3+) occurs. The dune field El Dorado contained granulated material that exhibited the highest Mg and Ni concentrations and the lowest S and Cl compared to all other soils implying an enrichment of olivine-rich sands. Two outcrops, called Algonquin and Comanche , revealed compositions that differ significantly from those of earlier outcrops as they have the highest concentrations of Mg, Fe, and Ni (except for Ni in Independence) and the lowest of Al, K (detection limit), Ca, and Ti of all brushed and almost all abraded rocks. Normative estimates assign them the highest olivine contents ever found for martian rocks and a very mafic nature based on their high Mg/(Mg+Fe) and low Al, Ca and Na. Their significantly high Ni contents point to a different source than the Gusev plains basalts. The elemental compositions of samples encountered during the downhill traverse revealed a larger chemical diversity of the Columbia Hills than the uphill trek already published.

Effects of Sodium Chloride, Potassium Chloride and Calcium Chloride on the Formation of α-Dicarbonyl Compounds, Furfurals and Development of Browning in Cookies during Baking.

PubMed

Kocadağlı, Tolgahan; Gökmen, Vural

2016-10-02

Effect of NaCl, KCl, CaCl2, NaHCO3, and NH4HCO3 on the formation of glucosone, 1-deoxyglucosone, 3-deoxyglucosone, glyoxal, methylglyoxal, diacetyl, 5-hydroxymethyl-2-furfural, 2-furfural and browning were investigated in cookies. Presence of 1.5% NaCl, 1% KCl, and 1% CaCl2 on flour basis had no effect on α-dicarbonyl compounds, except 1-deoxyglucosone increased in the presence of KCl and CaCl2. The increase in 5-hydroxymethyl-2-furfural formation in the presence of NaCl, KCl, and CaCl2 did not relate to 3-deoxyglucosone formation and pH changes. NaCl, KCl, and CaCl2 increased browning in cookies. Model reaction systems indicated that NaCl, KCl, and CaCl2 enhance browning by increasing furfurals in caramelization. NaCl, KCl, and CaCl2 decreased browning intensity in heated glucose-glycine system. Usage of CaCl2 in cookies may considerably increase furfurals but not α-dicarbonyl compounds. Sodium reduction can be obtained by replacement with potassium without sacrificing the desired consequences of caramelization in sugar rich bakeries.

Molecular and electronic structure of thin films of protoporphyrin(IX)Fe(III)Cl

NASA Astrophysics Data System (ADS)

Snyder, Shelly R.; White, Henry S.

1991-11-01

Electrochemical, scanning tunneling microscopy (STM), and tunneling spectroscopy studies of the molecular and electronic properties of thin films of protoporphyrin(IX)Fe(III)Cl (abbreviated as PP(IX)Fe(III)Cl) on highly oriented pyrolytic graphite (HOPG) electrodes are reported. PP(IX)Fe(III)Cl films are prepared by two different methods: (1) adsorption, yielding an electrochemically-active film, and (2) irreversible electrooxidative polymerization, yielding an electrochemically-inactive film. STM images, in conjunction with electro-chemical results, indicate that adsorption of PP(IX)Fe(III)Cl from aqueous solutions onto freshly cleaved HOPG results in a film comprised of molecular aggregates. In contrast, films prepared by irreversible electrooxidative polymerization of PP(IX)Fe(III)Cl have a denser, highly structured morphology, including what appear to be small pinholes (approx. 50A diameter) in an otherwise continuous film.

A New Green Chemical Synthesis Strategy for Synthesis of L10 FePt Nanoparticles from Layered Precursor Fe(H2O)6PtCl6

NASA Astrophysics Data System (ADS)

Hadjipanayis, George; Hu, Xiaocao; Capobianchi, Aldo; Gallagher, Ryan

2014-03-01

In this work, a new green chemical strategy for the synthesis of L10 FePt nanoparticles is reported. The starting material is a polycrystalline molecular complex (Fe(H2O)6PtCl6) , in which Fe and Pt atoms are arranged on alternating planes. The starting compound was milled with crystalline NaCl and then annealed under forming gas (5 % H2 and 95 % Ar) at 450 °C for 2h. Finally, the mixture was washed with water to remove the NaCl and L10 FePt nanoparticles were obtained. Transmission electron microscopy (TEM) images revealed that this method is able to produce L10 nanoparticles with different average size varying from 13.9 nm to 5.4 nm depending on the (Fe(H2O)6PtCl6) /NaCl ratio. With smaller (Fe(H2O)6PtCl6) /NaCl ratio(10mg/20g) and longer milling time(15h), FePt nanoparticles had a smaller size and narrower size distribution. The X-Ray Diffraction (XRD) pattern showed the presence of the characteristic peaks of the fct phase. The hysteresis loop, measured both at room temperature and 50 K, shows a high coercivity of 7.6 kOe and 11.2 kOe, respectively as expected for the high anisotropy L10 phase. Larger precursor/NaCl ratio and shorter ball milling time led to larger coercivity.

Collision-induced dissociation of [4Fe-4S] cubane cluster complexes: [Fe4S4Cl4 - x(SC2H5)x]2-/1- (x = 0-4)

NASA Astrophysics Data System (ADS)

Fu, You-Jun; Laskin, Julia; Wang, Lai-Sheng

2006-09-01

Collision-induced dissociation (CID) experiments on a series of [4Fe-4S] cluster ions, [Fe4S4Cl4 - x(SC2H5)x]2-/1- (x = 0-4), revealed that their fragmentation channels change with the coordination environment. Among the three Coulomb repulsion related channels for the doubly charged species, the collision induced electron detachment channel was found to become more significant from x = 0 to 4 due to the decreasing electron binding energies and the magnitude of repulsion Coulomb barrier, while both the ligand detachment of Cl- and the fission of the [Fe4S4]2+ core became more and more significant with the increase of the Cl- coordination, and eventually became the dominant channel at x = 0. From the parents containing the SC2H5 ligand, neutral losses of HSC2H5 (62 u) and/or HSCHCH2 (60 u) were observed. It was proposed that inter- and intra-ligand proton transfer could happen during the CID process, resulting in hydrogen coordination to the [4Fe-4S] cluster. In the presence of O2, [Fe4S4Cl3(SC2H5)]2- and [Fe4S4Cl4]2- can form the O2-substituted products [Fe4S4Cl2(SC2H5)O2]- and [Fe4S4Cl3O2]-, respectively. It was shown that the O2 complexation occurs by coordination to the empty iron site of the [4Fe-4S] cubane core after dissociation of one Cl- ligand.

Solubility relations in the system potassium chloride-ferrous chloride-water between 25 and 75.degree.C at 1 atm

USGS Publications Warehouse

Chou, I.-Ming; Phan, L.D.

1986-01-01

Solubility relations in the ternary system KCl-FeCl2-H2O have been determined by means of the visual polythermal method at 1 atm from 18 to 75??C along 10 composition lines. Solubilities of sylvite were measured along five composition lines defined by mixing KCl with five aqueous FeCl2 solutions containing 10, 20, 30, 38, and 45 wt % of FeCl2, respectively. Solubilities of FeCl2??4H2O were also determined along five composition lines defined by mixing FeCl2??4H2O with five aqueous KCl solutions containing 5, 10, 14.98, 19.97, and 24.99 wt % KCl, respectively. The maximum uncertainties in these measurements are ??0.02 wt % in KCl, ??0.15 wt % in FeCl2, and ??0.15??C. The data along each composition line were regressed to a smooth curve. The maximum deviations of the measured solubilities from the smoothed curves are 0.22 wt % in KCl and 0.12 wt % in FeCl2. Isothermal solubilities of sylvite and FeCl2??4H2O were calculated from these smoothed curves at 25, 40, 50, 60, 70, and 75??C.

Synthesis of the new compound CaFe(CO 3) 2 and experimental constraints on the (Ca,Fe)CO 3 join

NASA Astrophysics Data System (ADS)

Davidson, Paula M.; Symmes, Gregory H.; Cohen, Barbara A.; Reeder, Richard J.; Lindsley, Donald H.

1993-12-01

Synthesis of the new (disordered) compound CaFe(CO 3) 2 has been achieved with the use of Fe-substituted CaCO 3(Cc ss) + Ca-substituted FeCO 3(Sid ss) as starting materials, and high CO 2 pressures. High pressure (20-30 kbar) is needed to stabilize FeCO 3 to sufficiently high temperatures for disordered CaFe(CO 3) 2 to form. Experiments provide reversed compositions of coexisting disordered phases in the CaFe join and locate the solvus temperature for CaFe(C) 3) 2 between 815 and 845°C at 30 kbars. Calculated phase relations predict that the stability of ordered CaFe(CO 3) 2 is limited to T < ˜450°C by the breakdown to Cc ss + Sid ss. A comparison of the unit-cell volume measured for disordered CaFe(CO 3) 2 vs. that estimated for ordered CaFe(CO 3) 2 suggests that increasing pressure stabilizes the disordered phase.

Thermal Behavior of d-Ribose Adsorbed on Silica: Effect of Inorganic Salt Coadsorption and Significance for Prebiotic Chemistry.

PubMed

Akouche, Mariame; Jaber, Maguy; Zins, Emilie-Laure; Maurel, Marie-Christine; Lambert, Jean-Francois; Georgelin, Thomas

2016-10-24

Understanding ribose reactivity is a crucial step in the "RNA world" scenario because this molecule is a component of all extant nucleotides that make up RNA. In solution, ribose is unstable and susceptible to thermal destruction. We examined how ribose behaves upon thermal activation when adsorbed on silica, either alone or with the coadsorption of inorganic salts (MgCl 2 , CaCl 2 , SrCl 2 , CuCl 2 , FeCl 2 , FeCl 3 , ZnCl 2 ). A combination of 13 C NMR, in situ IR, and TGA analyses revealed a variety of phenomena. When adsorbed alone, ribose remains stable up to 150 °C, at which point ring opening is observed, together with minor oxidation to a lactone. All the metal salts studied showed specific interactions with ribose after dehydration, resulting in the formation of polydentate metal ion complexes. Anomeric equilibria were affected, generally favoring ribofuranoses. Zn 2+ stabilized ribose up to higher temperatures than bare silica (180 to 200 °C). Most other cations had an adverse effect on ribose stability, with ring opening already upon drying at 70 °C. In addition, alkaline earth cations catalyzed the dehydration of ribose to furfural and, to variable degrees, its further decarbonylation to furan. Transition-metal ions with open d-shells took part in redox reactions with ribose, either as reagents or as catalysts. These results allow the likelihood of prebiotic chemistry scenarios to be evaluated, and may also be of interest for the valorization of biomass-derived carbohydrates by heterogeneous catalysis. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Installation and Implementation of a Comprehensive Groundwater Monitoring Program for the Indian Wells Valley, California

DTIC Science & Technology

2010-04-01

isotopes. Laboratory analysis for general chemistry included Na, Ca, Mg, K, Fe, Cl, HCO3, CO3 , SO4, F, B, NO3, arsenic (As), hardness, alkalinity...used for interpretations within the project. Prior to this effort, a single -location repository for isotopic data related to IWV investigations...canyons of importance to this study (Indian Wells Canyon, Freeman Canyon, and the upgradient canyons of Cow Haven, Sage, and Horse). Single samples

Development of (177)Lu-DOTA-Dendrimer and Determination of Its Effect on Metal and Ion Levels in Tumor Tissue.

PubMed

Kovacs, Luciana; Tassano, Marcos; Cabrera, Mirel; Zamboni, Cibele B; Fernández, Marcelo; Anjos, Roberto M; Cabral, Pablo

2015-12-01

Dendrimers are synthetic nanomolecules with well-defined chemical structures. Different strategies have been used for radiolabeling dendrimers with different radioisotopes. In this study, the aim was to conjugate dendrimers with (177)Lu, to observe the in vivo behavior of the labeled compound and to measure the elementary changes in tumor tissue that could be caused by ionizing radiation. PAMAM G4 dendrimers conjugated with DOTA were labeled with (177)Lu. The radiolabeled compound was characterized and its stability was evaluated by reverse phase high performance liquid chromatography. Radiolabeling yield was >98% and stable for 24 hours. Biodistribution studies of (177)Lu-DOTA-dendrimers in C57BL/6 melanoma-bearing mice showed blood clearance with hepatic and renal depuration and tumor uptake. The concentrations of Br, Ca, Cl, Fe, K, Mg, Na, Rb, S, and Zn were determined in tumor tissues of C57BL/6 mice treated with (177)Lu-DOTA-dendrimers and in untreated mice. The results showed decreased concentrations of Br (62%), Ca (24%), Cl (51%), K (12%) and Na (60%) and increased concentrations of Fe (8%), Mg (28%), Rb (100%), S (6%) and Zn (4%) in tumor tissues of mice treated with (177)Lu-DOTA-dendrimers. These data may be useful to evaluate changes in tumor tissues as indicators of damage that could be caused by ionizing radiation.

Elemental analysis of size-fractionated particulate matter sampled in Göteborg, Sweden

NASA Astrophysics Data System (ADS)

Wagner, Annemarie; Boman, Johan; Gatari, Michael J.

2008-12-01

The aim of the study was to investigate the mass distribution of trace elements in aerosol samples collected in the urban area of Göteborg, Sweden, with special focus on the impact of different air masses and anthropogenic activities. Three measurement campaigns were conducted during December 2006 and January 2007. A PIXE cascade impactor was used to collect particulate matter in 9 size fractions ranging from 16 to 0.06 µm aerodynamic diameter. Polished quartz carriers were chosen as collection substrates for the subsequent direct analysis by TXRF. To investigate the sources of the analyzed air masses, backward trajectories were calculated. Our results showed that diurnal sampling was sufficient to investigate the mass distribution for Br, Ca, Cl, Cu, Fe, K, Sr and Zn, whereas a 5-day sampling period resulted in additional information on mass distribution for Cr and S. Unimodal mass distributions were found in the study area for the elements Ca, Cl, Fe and Zn, whereas the distributions for Br, Cu, Cr, K, Ni and S were bimodal, indicating high temperature processes as source of the submicron particle components. The measurement period including the New Year firework activities showed both an extensive increase in concentrations as well as a shift to the submicron range for K and Sr, elements that are typically found in fireworks. Further research is required to validate the quantification of trace elements directly collected on sample carriers.

[Physico-chemical characteristics of ambient particles settling upon leaf surface of six conifers in Beijing].

PubMed

Wang, Lei; Hasi, Eerdun; Liu, Lian-You; Gao, Shang-Yu

2007-03-01

The study on the density of ambient particles settling upon the leaf surface of six conifers in Beijing, the micro-configurations of the leaf surface, and the mineral and element compositions of the particles showed that at the same sites and for the same tree species, the density of the particles settling upon leaf surface increased with increasing ambient pollution, but for various tree species, it differed significantly, with the sequence of Sabina chinensis and Platycladus orientalis > Cedrus deodara and Pinus bungeana > P. tabulaeformis and Picea koraiensis. Due to the effects of road dust, low height leaf had a larger density of particles. The density of the particles was smaller in summer than in winter because of the rainfall and new leaf growth. The larger the roughness of leaf surface, the larger density of the particles was. In the particles, the overall content of SiO2, CaCO3, CaMg(CO3,), NaCl, 2CaSO4 . H2O, CaSO4 . 2H2O and Fe2O3 was about 10%-30%, and the main minerals were montmorillonite, illite, kaolinite and feldspar. The total content of 21 test elements in the particles reached 16%-37%, among which, Ca, Al, Fe, Mg, K, Na and S occupied 97% or more, while the others were very few and less affected by sampling sites and tree species.

Retention Mechanisms of Citric Acid in Ternary Kaolinite-Fe(III)-Citrate Acid Systems Using Fe K-edge EXAFS and L3,2-edge XANES Spectroscopy

PubMed Central

Yang, Jianjun; Wang, Jian; Pan, Weinan; Regier, Tom; Hu, Yongfeng; Rumpel, Cornelia; Bolan, Nanthi; Sparks, Donald

2016-01-01

Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. These findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils. PMID:27212680

Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L 3,2-edge XANES spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Jianjun; Wang, Jian; Pan, Weinan

Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L- 3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorptionmore » and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.« less

Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L 3,2-edge XANES spectroscopy

DOE PAGES

Yang, Jianjun; Wang, Jian; Pan, Weinan; ...

2016-05-23

Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L- 3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorptionmore » and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.« less

High chloride content calcium silicate glasses.

PubMed

Chen, Xiaojing; Karpukhina, Natalia; Brauer, Delia S; Hill, Robert G

2017-03-08

Chloride is known to volatilize from silicate glass melts and until now, only a limited number of studies on oxychloride silicate glasses have been reported. In this paper we have synthesized silicate glasses that retain large amounts of CaCl 2 . The CaCl 2 has been added to the calcium metasilicate composition (CaO·SiO 2 ). Glasses were produced via a melt quench route and an average of 70% of the chloride was retained after melting. Up to 31.6 mol% CaCl 2 has been successfully incorporated into these silicate glasses without the occurrence of crystallization. 29 Si MAS-NMR spectra showed the silicon being present mainly as a Q 2 silicate species. This suggests that chloride formed Cl-Ca(n) species, rather than Si-Cl bonds. Upon increasing the CaCl 2 content, the T g reduced markedly from 782 °C to 370 °C. Glass density and glass crystallization temperature decreased linearly with an increase in the CaCl 2 content. However, both linear regressions revealed a breakpoint at a CaCl 2 content just below 20 mol%. This might be attributed to a significant change in the structure and is also correlated with the nature of the crystallizing phases formed upon heat treatment. The glasses with less than 19.2 mol% CaCl 2 crystallized to wollastonite, whilst the compositions with CaCl 2 content equal to or greater than 19.2 mol% are thought to crystallize to CaCl 2 . In practice, the crystallization of CaCl 2 could not occur until the crystallization temperature fell below the melting point of CaCl 2 . The implications of the results along with the high chloride retention are discussed.

Effective removal of contaminants in landfill leachate membrane concentrates by coagulation.

PubMed

Long, Yuyang; Xu, Jing; Shen, Dongsheng; Du, Yao; Feng, Huajun

2017-01-01

Leachate membrane concentrates containing high concentrations of organics and trace toxic compounds pose a major threat to the environment, and their treatment is an urgent issue. In this work, various coagulants were used to treat leachate membrane concentrates. Appropriate pH values for treatments with FeCl 2 , FeSO 4 , polyaluminum chloride, and FeCl 3 were 3, 5, 5, and 4, respectively. FeCl 3 achieved the highest total organic carbon (TOC) removal efficiency. The effect of the various anions in ferric coagulants [FeCl 3 , Fe 2 (SO 4 ) 3 , and Fe(NO 3 ) 3 ] on the TOC removal efficiency was negligible. The main organics remaining in the leachate membrane concentrates after coagulation were humic and fulvic acids. The conditions for coagulation with FeCl 3 were optimized using the response surface method (RSM). The highest TOC, chemical oxygen demand (COD), and chromaticity reduction efficiencies, 81%, 82%, and 97%, respectively, were achieved at pH 4 using FeCl 3 (5 g L -1 ) and polyacrylamide (PAM; 0.07 g L -1 ). The COD of leachate membrane concentrates was reduced from 4000 to 718 mg L -1 . The mole ratio of removed COD and Fe(III) (2.4 mol) at 5 g L -1 FeCl 3 (pH 4, PAM 0.07 g L -1 ) was lower than that (3.8 mol) at 3 g L -1 FeCl 3 (pH 4, PAM 0.07 g L -1 ); based on the cost and COD removal efficiency, the latter conditions were the best choice. Our work provides guidelines for the treatment of leachate membrane concentrates in engineering. Copyright © 2016 Elsevier Ltd. All rights reserved.

Separate Cl^- Conductances Activated by cAMP and Ca2+ in Cl^--Secreting Epithelial Cells

NASA Astrophysics Data System (ADS)

Cliff, William H.; Frizzell, Raymond A.

1990-07-01

We studied the cAMP- and Ca2+-activated secretory Cl^- conductances in the Cl^--secreting colonic epithelial cell line T84 using the whole-cell patch-clamp technique. Cl^- and K^+ currents were measured under voltage clamp. Forskolin or cAMP increased Cl^- current 2-15 times with no change in K^+ current. The current-voltage relation for cAMP-activated Cl^- current was linear from -100 to +100 mV and showed no time-dependent changes in current during voltage pulses. Ca2+ ionophores or increased pipette Ca2+ increased both Cl^- and K^+ currents 2-30 times. The Ca2+-activated Cl^- current was outwardly rectified, activated during depolarizing voltage pulses, and inactivated during hyperpolarizing voltage pulses. Addition of ionophore after forskolin further increased Cl^- conductance 1.5-5 times, and the current took on the time-dependent characteristics of that stimulated by Ca2+. Thus, cAMP and Ca2+ activate Cl^- conductances with different properties, implying that these second messengers activate different Cl^- channels or that they induce different conductive and kinetic states in the same Cl^- channel.

The occurrence of chlorine in serpentine minerals

USGS Publications Warehouse

Miura, Y.; Rucklidge, J.; Nord, G.L.

1981-01-01

Partially serpentinized dunites containing small amounts of Chlorine (< 0.5%) from Dumont, Quebec, and Horoman, Hokkaido, Japan, and one containing less than 0.05% Chlorine from Higashi-Akaishi-Yama, Ehime, Japan have been examined using the electron probe microanalyzer and scanning transmission electron microscope with X-ray analytical capabilities. Chlorine was found together with Si, Mg, Ca and Fe in the serpentine minerals of the Dumont and Hokkaido dunites but not in the Ehime dunite. Chlorine is found associated only with the most finely crystalline facies of the serpentine (grain size less than 10 nm). The Ehime dunite contained no such fine grained serpentine, and was thus effectively chlorine-free, as are the coarser grained serpentines of the other samples. The finegrained chlorine-bearing serpentine also has a much higher concentration of Fe, and can contain smaller amounts of Ca, Ni and Mn than the coarse-grained variety as well as minute awaruite (FeNi3) grains. This fine-grained serpentine probably represents an early stage in the transformation of olivine to serpentine, with chlorine from hydrothermal solutions assisting the necessary chemical changes. The Cl increases the reaction rate by lowering the activation barrier to reaction by the introduction of reaction steps. ?? 1981 Springer-Verlag.

Method for treating rare earth-transition metal scrap

DOEpatents

Schmidt, Frederick A.; Peterson, David T.; Wheelock, John T.; Jones, Lawrence L.

1992-12-29

Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a prefused, rare earth fluoride-bearing flux of CaF.sub.2, CaCl.sub.2 or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy.

Method for treating rare earth-transition metal scrap

DOEpatents

Schmidt, F.A.; Peterson, D.T.; Wheelock, J.T.; Jones, L.L.

1992-12-29

Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a rare earth fluoride-bearing flux of CaF[sub 2], CaCl[sub 2] or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy. 3 figs.

Single and combined effects of phosphate, silicate, and natural organic matter on arsenic removal from soft and hard groundwater using ferric chloride

NASA Astrophysics Data System (ADS)

Chanpiwat, Penradee; Hanh, Hoang Thi; Bang, Sunbaek; Kim, Kyoung-Woong

2017-06-01

In order to assess the effects of phosphate, silicate and natural organic matter (NOM) on arsenic removal by ferric chloride, batch coprecipitation experiments were conducted over a wide pH range using synthetic hard and soft groundwaters, similar to those found in northern Vietnam. The efficiency of arsenic removal from synthetic groundwater by coprecipitation with FeCl3 was remarkably decreased by the effects of PO4 3-, SiO4 4- and NOM. The negative effects of SiO4 4- and NOM on arsenic removal were not as strong as that of PO4 3-. Combining PO4 3- and SiO4 4- increased the negative effects on both arsenite (As3+) and arsenate (As5+) removal. The introduction of NOM into the synthetic groundwater containing both PO4 3- and SiO4 4- markedly magnified the negative effects on arsenic removal. In contrast, both Ca2+ and Mg2+ substantially increased the removal of As3+ at pH 8-12 and the removal of As5+ over the entire pH range. In the presence of Ca2+ and Mg2+, the interaction of NOM with Fe was either removed or the arsenic binding to Fe-NOM colloidal associations and/or dissolved complexes were flocculated. Removal of arsenic using coprecipitation by FeCl3 could not sufficiently reduce arsenic contents in the groundwater (350 μg/L) to meet the WHO guideline for drinking water (10 μg/L), especially when the arsenic-rich groundwater also contains co-occurring solutes such as PO4 3-, SiO4 4- and NOM; therefore, other remediation processes, such as membrane technology, should be introduced or additionally applied after this coprecipitation process, to ensure the safety of drinking water.

Mineral Systems, Their Types, and Distribution in Nature: 2. Products of Contemporary Fumarole Activity at Tolbachik Volcano (Russia) and Vulcano (Italy)

NASA Astrophysics Data System (ADS)

Krivovichev, V. G.; Charykova, M. V.

2017-12-01

The number of mineral species in which a certain chemical element is species-defining (according to statistical data up to 2015) has been specified. Seventy chemical elements are species-defining for 5044 minerals. The following chemical elements lead in the composition of minerals (number of mineral species in parentheses): oxygen (4115), hydrogen (2800), silicon (1471), calcium (1167), sulfur (1056), aluminium (985), sodium (949), iron (945), copper (636), phosphorus (597), arsenic (594), and magnesium (571). The distribution of mineral species by various systems in the products of contemporary fumarole activity at two volcanoes, Tolbachik in Kamchatka, Russia, and Vulcano in Sicily, Italy, has been compared. These locations were also compared for the distribution of species-defining elements. Thus, it has been determined that in fumaroles of both volcanoes, Tl, S, Cl, F and Na are "excessive," present in minerals in elevated amounts, whereas H, Ca, Fe, and Mn are "deficient." The abundance of Cu, Se, V, Mg, Zn, As, and F in minerals at Tolbachik is higher than the global mean values of these elements in the Earth's crust, whereas the abundance is significantly lower at Vulcano. Sn, I, Br, K, Pb, Al, Fe, and Bi demonstrate the opposite behavior. Comparison of the Yadovitaya and Arsenatnaya fumaroles at the Tolbachik volcano showed that the products of the former are richer in H, Cl, Cu, S, K, O, Al, Fe, and Pb, and poorer in As, Ca, Mg, and Na as species-defining elements. In addition, V-and Mo-bearing minerals are found only at Yadovitaya, whereas minerals containing F, Ti, B, Te, and Zn are known only at Arsenatnaya.

Consumer Acceptability of Cucumber Pickles Produced by Fermentation in Calcium Chloride Brine for Reduced Environmental Impact.

PubMed

Wilson, Emily M; Johanningsmeier, Suzanne D; Osborne, Jason A

2015-06-01

Fermentation of cucumbers in calcium chloride (CaCl2 ) brine has been proposed as an alternative process to reduce the environmental impact of traditional, high salt fermentations. The objective of this research was to determine whether consumer acceptability of pickle products would be impacted by fermentation and storage of cucumbers in CaCl2 brine. Cucumbers were fermented and stored with 0.1M CaCl2 or 1M sodium chloride (NaCl) in open-air, 3000 gal tanks at a commercial facility and processed into hamburger dill chips containing 0.38M NaCl. Cucumbers fermented in CaCl2 required additional desalting to reduce CaCl2 concentrations to that of current products. Consumers (n = 101) showed no significant preference for pickles from different fermentation treatments, whether stored for 2 mo (P = 0.75) or 8 mo (P = 0.68) prior to processing. In contrast, NaCl fermented pickles were preferred over CaCl2 fermented pickles stored for 10 mo and desalted only once (P < 0.01). A series of preference tests indicated that the taste of CaCl2 was not the factor affecting consumer preference, and the 50% detection threshold of CaCl2 in dill pickle chips was found to be 61.8 ± 7.6 mM, indicating that processors could potentially use CaCl2 fermentations with a single desalting step. Consumer liking of flavor (n = 73) was not influenced by fermentation in CaCl2 or by 23 or 35 mM CaCl2 in finished products (P > 0.05), but variability in texture decreased consumer liking (P < 0.05). Although promising, individual fermentation variability and texture quality of CaCl2 fermented products should be further evaluated prior to broad implementation of this process. Published 2015. This article is a U.S. Government work and is in the public domain in the USA.

Polymethylated [Fe(η6-arene)2]2+ dications: methyl-group rearrangements and application of the EINS mechanism.

PubMed

Štíbr, Bohumil; Bakardjiev, Mario; Hájková, Zuzana; Holub, Josef; Padělková, Zdenka; Růžička, Aleš; Kennedy, John D

2011-06-14

Reactions between the methylated arenes ArMe(n) [where ArMe(n) = C(6)Me(n)H((6-n)), and n = 1-6] and FeCl(2) in heptane at 90 °C in the presence of anhydrous AlCl(3) give, for the arenes with n = 1-5, extensive isomerisations and disproportionations involving the methyl groups on the arene rings, and the formation of mixtures of [Fe(ArMe(n))(2)](2+) dications that defy separation into pure species. GC-MS studies of AlCl(3)/mesitylene and AlCl(3)/durene reactions in the absence of FeCl(2) (90 °C, 2 h) allow quantitative assessments of the rearrangements, and the EINS mechanism (electrophile-induced nucleophilic substitution) is applied to rationalise the phenomena. By contrast, ArMe(n) / FeCl(2) /AlCl(3) reactions in heptane for 24-36 h at room-temperature proceed with no rearrangements, allowing the synthesis of the complete series of pure [Fe(ArMen)](2+) cations in yields of 48-71%. The pure compounds are characterised by (1)H NMR spectroscopy and electrospray-ionization mass-spectrometry (ESI-MS), and the structures of [Fe(m-xylene)(2)][PF(6)](2) and [Fe(durene)(2)][PF(6)](2) are established by single-crystal X-ray diffraction analyses.

Synthesis of Mg-Fe-Cl hydrotalcite-like nanoplatelets as an oral phosphate binder: evaluations of phosphorus intercalation activity and cellular cytotoxicity

NASA Astrophysics Data System (ADS)

Lung, Yung-Feng; Sun, Ying-Sui; Lin, Chun-Kai; Uan, Jun-Yen; Huang, Her-Hsiung

2016-09-01

The patients with end-stage of renal disease (ESRD) need to take oral phosphate binder. Traditional phosphate binders may leave the disadvantage of aluminum intoxication or cardiac calcification. Herein, Mg-Fe-Cl hydrotalcite-like nanoplatelet (HTln) is for the first time characterized as potential oral phosphate binder, with respect to its phosphorus uptake capacity in cow milk and cellular cytotoxicity. A novel method was developed for synthesizing the Mg-Fe-Cl HTln powder in different Mg2+: Fe3+ ratios where the optimization was 2.8:1. Addition of 0.5 g Mg-Fe-Cl HTln in cow milk could reduce its phosphorus content by 40% in 30 min and by 65% in 90 min. In low pH environment, the Mg-Fe-Cl HTln could exhibit relatively high performance for uptaking phosphorus. During a 90 min reaction of the HTln in milk, no phosphorus restoration occurred. In-vitro cytotoxicity assay of Mg-Fe-Cl HTln revealed no potential cellular cytotoxicity. The cells that were cultured in the HTln extract-containing media were even more viable than cells that were cultured in extract-free media (blank control). The Mg-Fe-Cl HTln extract led to hundred ppm of Mg ion and some ppm of Fe ion in the media, should be a positive effect on the good cell viability.

Hybrid coagulation-UF processes for spent filter backwash water treatment: a comparison studies for PAFCl and FeCl3 as a pre-treatment.

PubMed

Ebrahimi, Afshin; Amin, Mohammad Mehdi; Pourzamani, Hamidreza; Hajizadeh, Yaghoub; Mahvi, Amir Hossein; Mahdavi, Mokhtar; Rad, Mohammad Hassan Rabie

2017-08-01

In this study, the reclamation of clean water from spent filter backwash water (SFBW) was investigated through pilot-scale experiments. The pilot plant consisted of pre-sedimentation, coagulation, flocculation, clarification, and ultrafiltration (UF). Two coagulants of PAFCl and FeCl 3 were investigated with respect to their performance on treated SFBW quality and UF membrane fouling. At the optimum dose of PAFCl and FeCl 3 turbidity removal of 99.6 and 99.4% was attained, respectively. PAFCl resulted in an optimum UV 254 , TOC, and DOC removal of 80, 83.6, and 72.7%, respectively, and FeCl 3 caused the removal of those parameters by 76.7, 80.9, and 65.9%, respectively. PAFCl removed hydrophilic and transphilic constituent better than FeCl 3 , but FeCl 3 had, to some extent, higher affinities to a hydrophobic fraction. It was concluded that PAFCl showed a better coagulation performance in most cases and caused a lower membrane fouling rate compared to FeCl 3 . Finally, the treated SFBW with both coagulant-UF systems met the drinking water standards.

Trace elements in hydrothermal quartz: Relationships to cathodoluminescent textures and insights into vein formation

USGS Publications Warehouse

Rusk, B.G.; Lowers, H.A.; Reed, M.H.

2008-01-01

High-resolution electron microprobe maps show the distribution of Ti, Al, Ca, K, and Fe among quartz growth zones revealed by scanning electron microscope-cathodoluminescence (SEM-CL) from 12 hydrothermal ore deposits formed between ???100 and e1750 ??C. The maps clearly show the relationships between trace elements and CL intensity in quartz. Among all samples, no single trace element consistently correlates with variations in CL intensity. However in vein quartz from five porphyry-Cu (Mo-Au) deposits, CL intensity always correlates positively with Ti concentrations, suggesting that Ti is a CL activator in quartz formed at >400 ??C. Ti concentrations in most rutile-bearing vein quartz from porphyry copper deposits indicate reasonable formation temperatures of 2000 ppm, but in high-temperature quartz, Al concentrations are consistently in the range of several hundred ppm. Aluminum concentrations in quartz refl ect the Al solubility in hydrothermal fluids, which is strongly dependent on pH. Aluminum concentrations in quartz therefore reflect fluctuations in pH that may drive metal-sulfide precipitation in hydrothermal systems. ?? 2008 The Geological Society of America.

Inhibitory actions of synthesised polyamine spider toxins and their analogues on Ca2+-activated Cl- currents recorded from cultured DRG neurones from neonatal rats.

PubMed

Sutton, K G; Stapleton, S R; Scott, R H

1998-07-24

The whole cell variant of the patch clamp technique was used to investigate the actions of polyamine spider toxins and their analogues on high voltage-activated Ca2+ currents and Ca2+-activated Cl- currents (I(Cl(Ca))). The actions of synthesised FTX (putative natural toxin from the American funnel web spider), sFTX-3.3, Orn-FTX-3.3, Lys-FTX-3.3, and argiotoxin-636 on cultured dorsal root ganglion neurones from neonatal rats were investigated. Synthesised FTX (1 microM) inhibited I(Cl(Ca)) but did not inhibit high voltage-activated Ca2+ currents. In contrast, sFTX-3.3 (10 microM) inhibited both high voltage-activated Ca2+ currents and the associated I(Cl(Ca)) in near equal proportions. Argiotoxin-636 (1-10 microM) inhibited I(Cl(Ca)) evoked by Ca2+ entry through voltage-activated channels and by intracellular photorelease of Ca2+ from a caged precursor DM-nitrophen. This data indicates that synthesised FTX and argiotoxin-636 directly inhibit Ca2+-activated Cl- channels. In conclusion, the potency of polyamines as non-selective inhibitors of Ca2+ channels and Ca2+-activated Cl- channels is in part determined by the presence of a terminal arginine and this may involve an interaction between terminal guanidino groups and Ca2+ binding sites.

Sustainable treatment of different high-strength cheese whey wastewaters: an innovative approach for atmospheric CO2 mitigation and fertilizer production.

PubMed

Prazeres, Ana R; Rivas, Javier; Paulo, Úrsula; Ruas, Filipa; Carvalho, Fátima

2016-07-01

Raw cheese whey wastewater (CWW) has been treated by means of FeCl3 coagulation-flocculation, NaOH precipitation, and Ca(OH)2 precipitation. Three different types of CWW were considered: without cheese whey recovery (CWW0), 60 % cheese whey recovery (CWW60), and 80 % cheese whey recovery (CWW80). Cheese whey recovery significantly influenced the characteristics of the wastewater to be treated: organic matter, solids, turbidity, conductivity, sodium, chloride, calcium, nitrogen, potassium, and phosphorus. Initial organic load was reduced to values in the interval of 60-70 %. Application of FeCl3, NaOH, or Ca(OH)2 involved additional chemical oxygen demand (COD) depletions regardless of the CWW used. Under optimum conditions, the combination of 80 % cheese whey recovery and lime application led to 90 % reduction in COD. Turbidity (99.8%), total suspended solids (TSS) (98-99 %), oils and fats (82-96 %), phosphorus (98-99 %), potassium (96-97 %), and total coliforms (100 %) were also reduced. Sludge generated in the latter process showed excellent settling properties. This solid after filtration and natural evaporation can be used as fertilizer with limitations due to its saline nature. In an innovative, low-cost, and environmentally friendly technology, supernatant coming from the Ca(OH)2 addition was naturally neutralized in 4-6 days by atmospheric CO2 absorption without reagent addition. Consequently, a final aerobic biodegradation step can be applied for effluent polishing. This technology also allows for some atmospheric CO2 mitigation. Time requirement for the natural carbonation depends on the effluent characteristics. A precipitate rich in organic matter and nutrients and depletions of solids, sodium, phosphorus, magnesium, Kjeldahl, and ammoniacal nitrogen were also achieved during the natural carbonation.

Energy dispersive X-ray fluorescence spectrometry for the direct multi-element analysis of dried blood spots

NASA Astrophysics Data System (ADS)

Marguí, E.; Queralt, I.; García-Ruiz, E.; García-González, E.; Rello, L.; Resano, M.

2018-01-01

Home-based collection protocols for clinical specimens are actively pursued as a means of improving life quality of patients. In this sense, dried blood spots (DBS) are proposed as a non-invasive and even self-administered alternative to sampling whole venous blood. This contribution explores the potential of energy dispersive X-ray fluorescence spectrometry for the simultaneous and direct determination of some major (S, Cl, K, Na), minor (P, Fe) and trace (Ca, Cu, Zn) elements in blood, after its deposition onto clinical filter papers, thus giving rise to DBS. For quantification purposes the best strategy was to use matrix-matched blood samples of known analyte concentrations. The accuracy and precision of the method were evaluated by analysis of a blood reference material (Seronorm™ trace elements whole blood L3). Quantitative results were obtained for the determination of P, S, Cl, K and Fe, and limits of detection for these elements were adequate, taking into account their typical concentrations in real blood samples. Determination of Na, Ca, Cu and Zn was hampered by the occurrence of high sample support (Na, Ca) and instrumental blanks (Cu, Zn). Therefore, the quantitative determination of these elements at the levels expected in blood samples was not feasible. The methodology developed was applied to the analysis of several blood samples and the results obtained were compared with those reported by standard techniques. Overall, the performance of the method developed is promising and it could be used to determine the aforementioned elements in blood samples in a simple, fast and economic way. Furthermore, its non-destructive nature enables further analyses by means of complementary techniques to be carried out.

Studies on transport phenomena in electrothermal vaporization sample introduction applied to inductively coupled plasma for optical emission and mass spectrometry

NASA Astrophysics Data System (ADS)

Kántor, T.; Maestre, S.; de Loos-Vollebregt, M. T. C.

2005-10-01

In the present work electrothermal vaporization (ETV) was used in both inductively coupled plasma mass spectrometry (ICP-MS) and optical emission spectrometry (OES) for sample introduction of solution samples. The effect of (Pd + Mg)-nitrate modifier and CaCl 2 matrix/modifier of variable amounts were studied on ETV-ICP-MS signals of Cr, Cu, Fe, Mn and Pb and on ETV-ICP-OES signals of Ag, Cd, Co, Cu, Fe, Ga, Mn and Zn. With the use of matrix-free standard solutions the analytical curves were bent to the signal axes (as expected from earlier studies), which was observed in the 20-800 pg mass range by ICP-MS and in the 1-50 ng mass range by ICP-OES detection. The degree of curvature was, however, different with the use of single element and multi-element standards. When applying the noted chemical modifiers (aerosol carriers) in microgram amounts, linear analytical curves were found in the nearly two orders of magnitude mass ranges. Changes of the CaCl 2 matrix concentration (loaded amount of 2-10 μg Ca) resulted in less than 5% changes in MS signals of 5 elements (each below 1 ng) and OES signals of 22 analytes (each below 15 ng). Exceptions were Pb (ICP-MS) and Cd (ICP-OES), where the sensitivity increase by Pd + Mg modifier was much larger compared to other elements studied. The general conclusions suggest that quantitative analysis with the use of ETV sample introduction requires matrix matching or matrix replacement by appropriate chemical modifier to the specific concentration ranges of analytes. This is a similar requirement to that claimed also by the most commonly used pneumatic nebulization of solutions, if samples with high matrix concentration are concerned.

Effect of Ca sup 2+ on Cl sup minus transport in thin ascending limb of Henle's loop

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kondo, Yoshiaki; Yoshitomi, Koji; Imai, Masashi

1988-02-01

Effects of ambient Ca{sup 2+} concentration on Cl{sup {minus}} transport across the thin ascending limb of Henle's loop (TAL) were examined by the in vitro microperfusion technique. When Ca{sup 2+} concentration in the bathing fluid was decreased from 1.5 mM to nominally 0 mM at 37{degree}C, the relative permeability of Cl{sup {minus}} to Na{sup +} (P{sub Cl}/P{sub Na}) estimated from the NaCl diffusion voltage changed from 2.44 to 1.27. When Ca{sup 2+} concentration of the luminal fluid was reduced, P{sub Cl}/P{sub Na} was unchanged. When Ca{sup 2+} concentration in the bathing fluid was change from 4.5 to nominally 0 mM,more » the lumen-to-bath flux coefficient for {sup 36}Cl (K{sub 1{yields}b}{sup 36Cl}) was decreased, whereas the value of {sup 22}Na was unchanged, indicating that the reduction of Ca{sup 2+} concentration in the bathing fluid selectively inhibits Cl{sup {minus}} transport without affecting Na{sup +} transport. The pH titration curves of relative Cl{sup {minus}} permeability examined at three different Ca{sup 2+} concentrations at 37{degree}C revealed that the interaction between proton and Ca{sup +} was noncompetitive. Addition of quin 2-AM, which reduced intracellular Ca{sup 2+} concentration, to the bath caused an irreversible suppression of Cl{sup {minus}} permeability, suggesting that the decrease in intracellular Ca{sup 2+} concentration also inhibits the Cl{sup {minus}} transport across the TAL. From these observations the authors suggest: (1) Cl{sup {minus}} transport across the TAL is regulated by Ca{sup 2+} preferentially on the basolateral membrane; (2) this regulation depends on temperature; and (3) there is a noncompetitive interaction between Ca{sup 2+} and proton in the regulation of the conductive Cl{sup {minus}} pathway.« less

Iron and chlorine as guides to stratiform Cu-Co-Au deposits, Idaho Cobalt Belt, USA

USGS Publications Warehouse

Nash, J.T.; Connor, J.J.

1993-01-01

The Cu-Co-Au deposits of the Idaho Cobalt Belt are in lithostratigraphic zones of the Middle Proterozoic Yellowjacket Formation characterized by distinctive chemical and mineralogical compositions including high concentrations of Fe (15- > 30 wt. percent Fe2O3), Cl (0.1-1.10 wt. percent), and magnetite or biotite (> 50 vol. percent). The Cu-Co-Au deposits of the Blackbird mine are stratabound in Fe-silicate facies rocks that are rich in biotite, Fe, and Cl, but stratigraphically equivalent rocks farther than 10 km from ore deposits have similar compositions. A lower lithostratigraphic zone containing magnetite and small Cu-Co-Au deposits extends for more than 40 km. The Fe-rich strata are probably exhalative units related to mafic volcanism and submarine hot springs, but the origin of the high Cl concentrations is less clear. Former chlorine-rich pore fluids are suggested by the presence of supersaline fluid inclusions, by Cl-rich biotite and scapolite (as much as 1.87 percent Cl in Fe-rich biotite), and by high Cl concentrations in rock samples. Chlorine is enriched in specific strata and in zones characterized by soft-sediment deformation, thus probably was introduced during sedimentation or diagenesis. Unlike some metasedimentary rocks containing scapolite and high Cl, the Yellowjacket Formation lacks evidence for evaporitic strata that could have been a source of Cl. More likely, the Cl reflects a submarine brine that carried Fe, K, and base metals. Strata containing anomalous Fe-K-Cl are considered to be a guide to sub-basins favorable for the occurrence of stratiform base-metal deposits. ?? 1993 Springer-Verlag.

Luminescence and energy transfer properties of Ca2Ba3(PO4)3Cl and Ca2Ba3(PO4)3Cl:A (A = Eu2+/Ce3+/Dy3+/Tb3+) under UV and low-voltage electron beam excitation.

PubMed

Shang, Mengmeng; Geng, Dongling; Yang, Dongmei; Kang, Xiaojiao; Zhang, Yang; Lin, Jun

2013-03-18

Pure Ca2Ba3(PO4)3Cl and rare earth ion (Eu(2+)/Ce(3+)/Dy(3+)/Tb(3+)) doped Ca2Ba3(PO4)3Cl phosphors with the apatite structure have been prepared via a Pechini-type sol-gel process. X-ray diffraction (XRD) and structure refinement, photoluminescence (PL) spectra, cathodoluminescence (CL) spectra, absolute quantum yield, as well as lifetimes were utilized to characterize samples. Under UV light excitation, the undoped Ca2Ba3(PO4)3Cl sample shows broad band photoluminescence centered near 480 nm after being reduced due to the defect structure. Eu(2+) and Ce(3+) ion doped Ca2Ba3(PO4)3Cl samples also show broad 5d → 4f transitions with cyan and blue colors and higher quantum yields (72% for Ca2Ba3(PO4)3Cl:0.04Eu(2+); 67% for Ca2Ba3(PO4)3Cl:0.016Ce(3+)). For Dy(3+) and Tb(3+) doped Ca2Ba3(PO4)3Cl samples, they give strong line emissions coming from 4f → 4f transitions. Moreover, the Ce(3+) ion can transfer its energy to the Tb(3+) ion in the Ca2Ba3(PO4)3Cl host, and the energy transfer mechanism has been demonstrated to be a resonant type, via a dipole-quadrupole interaction. However, under the low voltage electron beam excitation, Tb(3+) ion doped Ca2Ba3(PO4)3Cl samples present different luminescence properties compared with their PL spectra, which is ascribed to the different excitation mechanism. On the basis of the good PL and CL properties of the Ca2Ba3(PO4)3Cl:A (A = Ce(3+)/Eu(2+)/Tb(3+)/Dy(3+)), Ca2Ba3(PO4)3Cl might be promising for application in solid state lighting and field-emission displays.

Physicochemical characteristics of ambient particles settling upon leaf surfaces of urban plants in Beijing.

PubMed

Wang, Lei; Liu, Lian-you; Gao, Shang-yu; Hasi, Eerdun; Wang, Zhi

2006-01-01

Particulate pollution is a serious health problem throughout the world, exacerbating a wide range of respiratory and vascular illnesses in urban areas. Urban plants play an important role in reducing particulate pollution. Physicochemical characteristics of ambient particles settling upon leaf surfaces of eleven roadside plants at four sites of Beijing were studies. Results showed that density of particles on the leaf surfaces greatly varied with plant species and traffic condition. Fraxinus chinensis, Sophora japonica, A ilanthus altissima, Syringa oblata and Prunus persica had larger densities of particles among the tall species. Due to resuspension of road dust, the densities of particles of Euonymus japonicus and Parthenocissus quinquefolia with low sampling height were 2-35 times to other taller tree species. For test plant species, micro-roughness of leaf surfaces and density of particles showed a close correlation. In general, the larger micro-roughness of leaf surfaces is, the larger density of particles is. Particles settling upon leaf surfaces were dominantly PM, (particulate matter less than 10 microm in aerodynamic diameter; 98.4%) and PM25 (particulate matter less than 2.5 microm in aerodynamic diameter; 64.2%) which were closely relative to human health. Constant elements of particles were C, O, K, Ca, Si, Al, Mg, Na, Fe, S, Cl and minerals with higher content were SiO2, CaCO3, CaMg(CO3)2, NaCI and 2CaSO4 x H20, SiO2. CaCO3 and CaMg(CO3)2 mainly came from resuspension of road dust. 2CaSO4 x H20 was produced by the reaction between CaCO3 derived from earth dust or industrial emission and SO2, H2SO4 or sulfate. NaCl was derived from sea salt.

SODIUM CHLORIDE AND SELECTIVE DIFFUSION IN LIVING ORGANISMS.

PubMed

Loeb, J

1922-11-20

1. It is shown that NaCl acts like CaCl(2) or LaCl(3) in preventing the diffusion of strong acids through the membrane of the egg of Fundulus with this difference only that a M/8 solution of NaCl acts like a M/1,000 solution of CaCl(2) and like a M/30,000 solution of LaCl(3). 2. It is shown that these salts inhibit the diffusion of non-dissociated weak acid through the membrane of the Fundulus egg but slightly if at all. 3. Both NaCl and CaCl(2) accelerate the diffusion of dissociated strong alkali through the egg membrane of Fundulus and CaCl(2) is more efficient in this respect than NaCl. 4. It is shown that in moderate concentrations NaCl accelerates the rate of diffusion of KCl through the membrane of the egg of Fundulus while CaCl(2) does not.

Batteries: An Advanced Na-FeCl2 ZEBRA Battery for Stationary Energy Storage Application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Guosheng; Lu, Xiaochuan; Kim, Jin Yong

2015-06-17

Sodium-metal chloride batteries, ZEBRA, are considered as one of the most important electrochemical devices for stationary energy storage applications because of its advantages of good cycle life, safety, and reliability. However, sodium-nickel chloride (Na-NiCl2) batteries, the most promising redox chemistry in ZEBRA batteries, still face great challenges for the practical application due to its inevitable feature of using Ni cathode (high materials cost). In this work, a novel intermediate-temperature sodium-iron chloride (Na-FeCl2) battery using a molten sodium anode and Fe cathode is proposed and demonstrated. The first use of unique sulfur-based additives in Fe cathode enables Na-FeCl2 batteries can bemore » assembled in the discharged state and operated at intermediate-temperature (<200°C). The results in this work demonstrate that intermediate-temperature Na-FeCl2 battery technology could be a propitious solution for ZEBRA battery technologies by replacing the traditional Na-NiCl2 chemistry.« less

Solubility relations in the system sodium chloride-ferrous chloride-water between 25 and 70.degree.C at 1 atm

USGS Publications Warehouse

Chou, I.-Ming; Phan, L.D.

1985-01-01

Solubility relations in the ternary system NaCl-FeCl2-H2O have been determined by the visual polythermal method at 1 atm from 20 to 85??C along six composition lines. These she composition lines are defined by mixing FeCl2??4H2O with six aqueous NaCl solutions containing 5, 10, 11, 15, 20, and 25 wt % of NaCl, respectively. The solid phases encountered in these experiments were NaCl and FeCl2??4H2O. The maximum uncertainties in these measurements are ??0.02 wt % NaCl and ??0.15??C. The data along each composition line were regressed to a smooth curve when only one solid phase was stable. When two solids were stable along a composition line, the data were regressed to two smooth curves, the intersection of which indicated the point where the two solids coexisted. The maximum deviation of the measured solubilities from the smoothed curves is 0.14 wt % FeCl2. Isothermal solubilities of halite and FeCl2??4H2O were calculated from these smoothed curves at 25, 50, and 70 ??C.

High-Order Ca(II)-Chloro Complexes in Mixed CaCl2-LiCl Aqueous Solution: Insights from Density Functional Theory and Molecular Dynamics Simulations.

PubMed

Wang, Yu-Lin; Wang, Ying; Yi, Hai-Bo

2016-07-21

In this study, the structural characteristics of high-coordinated Ca-Cl complexes present in mixed CaCl2-LiCl aqueous solution were investigated using density functional theory (DFT) and molecular dynamics (MD) simulations. The DFT results show that [CaClx](2-x) (x = 4-6) clusters are quite unstable in the gas phase, but these clusters become metastable when hydration is considered. The MD simulations show that high-coordinated Ca-chloro complexes are possible transient species that exist for up to nanoseconds in concentrated (11.10 mol·kg(-1)) Cl(-) solution at 273 and 298 K. As the temperature increases to 423 K, these high-coordinated structures tend to disassociate and convert into smaller clusters and single free ions. The presence of high-order Ca-Cl species in concentrated LiCl solution can be attributed to their enhanced hydration shell and the inadequate hydration of ions. The probability of the [CaClx](2-x)aq (x = 4-6) species being present in concentrated LiCl solution decreases greatly with increasing temperature, which also indicates that the formation of the high-coordinated Ca-Cl structure is related to its hydration characteristics.

Hydrogeochemistry and water quality of the Kordkandi-Duzduzan plain, NW Iran: application of multivariate statistical analysis and PoS index.

PubMed

Soltani, Shahla; Asghari Moghaddam, Asghar; Barzegar, Rahim; Kazemian, Naeimeh; Tziritis, Evangelos

2017-08-18

Kordkandi-Duzduzan plain is one of the fertile plains of East Azarbaijan Province, NW of Iran. Groundwater is an important resource for drinking and agricultural purposes due to the lack of surface water resources in the region. The main objectives of the present study are to identify the hydrogeochemical processes and the potential sources of major, minor, and trace metals and metalloids such as Cr, Mn, Cd, Fe, Al, and As by using joint hydrogeochemical techniques and multivariate statistical analysis and to evaluate groundwater quality deterioration with the use of PoS environmental index. To achieve these objectives, 23 groundwater samples were collected in September 2015. Piper diagram shows that the mixed Ca-Mg-Cl is the dominant groundwater type, and some of the samples have Ca-HCO 3 , Ca-Cl, and Na-Cl types. Multivariate statistical analyses indicate that weathering and dissolution of different rocks and minerals, e.g., silicates, gypsum, and halite, ion exchange, and agricultural activities influence the hydrogeochemistry of the study area. The cluster analysis divides the samples into two distinct clusters which are completely different in EC (and its dependent variables such as Na + , K + , Ca 2+ , Mg 2+ , SO 4 2- , and Cl - ), Cd, and Cr variables according to the ANOVA statistical test. Based on the median values, the concentrations of pH, NO 3 - , SiO 2 , and As in cluster 1 are elevated compared with those of cluster 2, while their maximum values occur in cluster 2. According to the PoS index, the dominant parameter that controls quality deterioration is As, with 60% of contribution. Samples of lowest PoS values are located in the southern and northern parts (recharge area) while samples of the highest values are located in the discharge area and the eastern part.

Effect of Halide Flux on Physicochemical Properties of MgCl2-Based Molten Salts for Accelerating Zirconium Production: Thermodynamic Assessment

NASA Astrophysics Data System (ADS)

Shin, Jae Hong; Park, Joo Hyun

2016-09-01

The effective halide flux additive for increasing the density of MgCl2 mixture and for decreasing the activity of MgCl2 was investigated in order to improve the reaction efficiency between gaseous ZrCl4 and fresh Mg melt to produce zirconium sponge. Thermochemical computation using FactSageTM software was primarily carried out, followed by the experimental confirmation. The addition of CaCl2, BaCl2, MgF2, and CaF2 to the molten MgCl2 increases the density of the melts, indicating that these halide additives can be a candidate to increase the density of the MgCl2-based molten salts. Among them, BaCl2, MgF2, and CaF2 are the useful additives. The activity of MgCl2 can be reduced by the addition of BaCl2, KCl, NaCl, MgF2, and CaF2, among which the CaF2 is the most effective additive to reduce the activity of MgCl2 with the strongest negative deviation from an ideality. Thus, the addition of CaF2 to the MgCl2, forming the MgCl2-CaF2 binary melt, is the most effective way not only to increase the density of the melt but also to decrease the activity of MgCl2, which was experimentally confirmed. Consequently, the production rate of zirconium sponge by magnesiothermic reduction process can be accelerated by the addition of CaF2.

Sorption, desorption, and speciation of Cd, Ni, and Fe by four calcareous soils as affected by pH.

PubMed

Tahervand, Samaneh; Jalali, Mohsen

2016-06-01

The sorption, desorption, and speciation of cadmium (Cd), nickel (Ni), and iron (Fe) in four calcareous soils were investigated at the pH range of 2-9. The results indicated that sorption of Fe by four soils was higher than 80 % at pH 2, while in the case of Cd and Ni was less than 30 %. The most common sequence of metal sorption at pH 2-9 for four soils was in the order of Fe ≫ Ni > Cd. Cadmium and Ni sorption as a function of pH showed the predictable trend of increasing metal sorption with increase in equilibrium pH, while the Fe sorption trend was different and characterized by three phases. With regard to the order of Cd, Ni, and Fe sorption on soils, Cd and Ni showed high affinity for organic matter (OM), whereas Fe had high tendency for calcium carbonate (CaCO3). Results of metal desorption using 0.01 M NaCl demonstrated that metal sorption on soils containing high amounts of CaCO3 was less reversible in comparison to soils containing high OM. In general, Cd and Ni desorption curves were characterized by three phases; (1) the greatest desorption at pH 2, (2) the low desorption at pH 3-7, and (3) the least desorption at pH > 7. The MINTEQ speciation solubility program showed that the percentage of free metals declined markedly with increase of pH, while the percentage of carbonate and hydroxyl species increased. Furthermore, MINTEQ predicted that saturation index (SI) of metals increased with increasing pH.

Synthetic fluid inclusions in natural quartz I. Compositional types synthesized and applications to experimental geochemistry

NASA Astrophysics Data System (ADS)

Sterner, S. Michael; Bodnar, Robert J.

1984-12-01

Synthetic fluid inclusions having a wide range of geologically applicable compositions in the C-O-H-S-Na-K-Ca-Cl-Cu-Fe system have been formed by healing fractures in inclusion-free natural quartz and by precipitating new quartz overgrowths on an original "seed" crystal. Inclusion types synthesized include: (1) liquid-rich, pure H 2O inclusions of primary and secondary origin, (2) pure H 2O inclusions with the critical density, (3) liquid-rich inclusions containing undersaturated aqueous solutions of NaCl or KCl or CaCl 2, or mixtures of the three salts, (4) H 2O-NaCl inclusions containing halite daughter minerals, (5) H 2O-NaCl-KCl inclusions containing halite and sylvite daughter minerals, (6) H 2O-CO 2 inclusions of various compositions containing liquid H 2O and either CO 2 vapor or CO 2 liquid, or both, at 25°C, (7) H 2O-CO 2-NaCl inclusions containing an aqueous phase, liquid and vapor CO 2, and halite at 25°C, (8) C-O-H inclusions containing liquid H 2O, a CO 2-CH 4 liquid phase and graphite daughter minerals at 25°C, (9) H 2O-NaCl inclusions that contain a chalcopyrite daughter mineral, and (10)inclusions representing trapping of the coexisting, immiscible fluids in the H 2O-NaCl, H 2O-CO 2-NaCl, and Na-C-O-H systems. The inclusions exhibit uniform phase ratios at room temperature, and the temperatures of various phase changes within individual inclusions agree with those predicted from experimental and theoretical data, indicating that the inclusion fluid has the same composition and density as the parent solution. These 'miniature autoclaves' thus may be used to study various problems related to fluid inclusion research, to calibrate analytical equipment used to study natural inclusions, and to study phase equilibria, solubility and PVT relations of a variety of chemical systems.

Effects of Fe-Enrichment on the Equation of State and Stability of (Mg,Fe)SiO3 Perovskite and Post-Perovskite

NASA Astrophysics Data System (ADS)

Dorfman, S. M.; Holl, C. M.; Meng, Y.; Prakapenka, V.; Duffy, T. S.

2010-12-01

Fe-enrichment in the deep lower mantle has been proposed as an explanation for seismic anomalies such as large low shear velocity provinces (LLSVPs) and ultralow velocity zones (ULVZs). In order to resolve the effect of Fe on the stability and equation of state of the lower mantle’s dominant constituent, (Mg,Fe)SiO3 perovskite, we have studied Fe-rich natural orthopyroxenes, (Mg0.61Fe0.37Ca0.02)SiO3 and (Mg0.25Fe0.70Ca0.05)SiO3 (compositions determined by microprobe analysis), at lower mantle P-T conditions. Pyroxene starting materials were mixed with Au (pressure calibrant and laser absorber) and loaded with NaCl or Ne (pressure medium and thermal insulator) in a symmetric diamond anvil cell. X-ray diffraction experiments at pressures up to 122 GPa with in-situ laser heating were performed at the GSECARS (13-ID-D) and HPCAT (16-ID-B) sectors of the Advanced Photon Source. Heating samples to 2000 K produced single-phase orthorhombic GdFeO3-type perovskite at 63 GPa for the Mg# 61 composition and at 72 GPa for the Mg# 25 composition. At lower pressures (56 GPa for Mg# 61, 67 GPa for Mg# 25), heating both compositions resulted in a mixture of perovskite, SiO2 and (Mg,Fe)O. These measurements provide new constraints on the dependence of (Mg,Fe)SiO3 perovskite stability on pressure and composition. Upon further compression to 93 GPa and higher pressures with laser heating, Mg# 25 perovskite transformed to a two-phase mixture of perovskite and post-perovskite. This is consistent with previous findings that Fe substitution destabilizes (Mg,Fe)SiO3 perovskite relative to (Mg,Fe)SiO3 post-perovskite (Mao et al. 2004, Caracas and Cohen 2005). The bulk modulus at 80 GPa (K80) is ~550 GPa for both Fe-rich perovskites, comparable to values measured for MgSiO3 perovskite (Lundin et al. 2008). However, the volume of Fe-rich perovskites increases linearly with Fe-content. The (Mg0.25Fe0.70Ca0.05)SiO3 perovskite is 3% greater at 80 GPa than V80 for the Mg end-member, corresponding to a 20% density difference. This volume difference arises from variations in the a (2% larger than Fe-free perovskite) and c (1% larger) lattice parameters. Volumes under compression show no evidence of a discontinuity in the range measured; any magnetic spin transition in the Fe is either gradual or has too weak an effect on volume to be observed.

Synchrotron micro-scale study of trace metal transport and distribution in Spartina alterniflora root system in Yangtze River intertidal zone

DOE PAGES

Feng, Huan; Tappero, Ryan; Zhang, Weiguo; ...

2015-07-26

This study is focused on micro-scale measurement of metal (Ca, Cl, Fe, K, Mn, Cu, Pb, and Zn) distributions in Spartina alterniflora root system. The root samples were collected in the Yangtze River intertidal zone in July 2013. Synchrotron X-ray fluorescence (XRF), computed microtomography (CMT), and X-ray absorption near-edge structure (XANES) techniques, which provide micro-meter scale analytical resolution, were applied to this study. Although it was found that the metals of interest were distributed in both epidermis and vascular tissue with the varying concentrations, the results showed that Fe plaque was mainly distributed in the root epidermis. Other metals (e.g.,more » Cu, Mn, Pb, and Zn) were correlated with Fe in the epidermis possibly due to scavenge by Fe plaque. Relatively high metal concentrations were observed in the root hair tip. As a result, this micro-scale investigation provides insights of understanding the metal uptake and spatial distribution as well as the function of Fe plaque governing metal transport in the root system.« less

The role of counter ions in nano-hematite synthesis: Implications for surface area and selenium adsorption capacity.

PubMed

Lounsbury, Amanda W; Yamani, Jamila S; Johnston, Chad P; Larese-Casanova, Philip; Zimmerman, Julie B

2016-06-05

Nano metal oxides are of interest for aqueous selenium (Se) remediation, and as such, nano-hematite (nα-Fe2O3) was examined for use as a Se adsorbent. The effect of surface area on adsorption was also studied. nα-Fe2O3 particles were synthesized from Fe(NO3)3 and FeCl3 via forced hydrolysis. The resulting particles have similar sizes, morphologies, aggregate size, pore size, and PZC. The nα-Fe2O3 from FeCl3 (nα-Fe2O3-C) differs from the nα-Fe2O3 from Fe(NO3)3 (nα-Fe2O3-N) with a ∼25±2m(2)/g greater surface area. Selenite Se(IV) adsorption capacity on nα-Fe2O3 has a qmax ∼17mg/g for the freeze-dried and re-suspended nα-Fe2O3. The Δqmax for nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension was 4.6mg/g. For selenate Se(VI), the freeze-dried and re-suspended particles realize a Δqmax= 1.5mg/g for nα-Fe2O3 from Fe(NO3)3 and FeCl3. The nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension demonstrated Se(VI) Δqmax=5.4mg/g. In situ ATR-FTIR isotherm measurements completed for Se(VI) at a pH 6 suggest that Se(VI) forms primarily outer-sphere complexes with nα-Fe2O3 synthesized from both salts. Copyright © 2016 Elsevier B.V. All rights reserved.

Heterobimetallic Nitrido Complexes of Group 8 Metalloporphyrins.

PubMed

Cheung, Wai-Man; Chiu, Wai-Hang; de Vere-Tucker, Matthew; Sung, Herman H-Y; Williams, Ian D; Leung, Wa-Hung

2017-05-15

Heterobimetallic nitrido porphyrin complexes with the [(L)(por)M-N-M'(L OEt )Cl 2 ] formula {por 2- = 5,10,15,20-tetraphenylporphyrin (TPP 2- ) or 5,10,15,20-tetra(p-tolyl)porphyrin (TTP 2- ) dianion; L OEt - = [Co(η 5 -C 5 H 5 ){P(O)(OEt) 2 } 3 ] - ; M = Fe, Ru, or Os; M' = Ru or Os; L = H 2 O or pyridine} have been synthesized, and their electrochemistry has been studied. Treatment of trans-[Fe(TPP)(py) 2 ] (py = pyridine) with Ru(VI) nitride [Ru(L OEt )(N)Cl 2 ] (1) afforded Fe/Ru μ-nitrido complex [(py)(TPP)Fe(μ-N)Ru(L OEt )Cl 2 ] (2). Similarly, Fe/Os analogue [(py)(TPP)Fe(μ-N)Os(L OEt )Cl 2 ] (3) was obtained from trans-[Fe(TPP)(py) 2 ] and [Os(L OEt )(N)Cl 2 ]. However, no reaction was found between trans-[Fe(TPP)(py) 2 ] and [Re(L OEt )(N)Cl(PPh 3 )]. Treatment of trans-[M(TPP)(CO)(EtOH)] with 1 afforded μ-nitrido complexes [(H 2 O)(TPP)M(μ-N)Ru(L OEt )Cl 2 ] [M = Ru (4a) or Os (5)]. TTP analogue [(H 2 O)(TTP)Ru(μ-N)Ru(L OEt )Cl 2 ] (4b) was prepared similarly from trans-[Ru(TTP)(CO)(EtOH)] and 1. Reaction of [(H 2 O)(por)M(μ-N)M(L OEt )Cl 2 ] with pyridine gave adducts [(py)(por)M(μ-N)Ru(L OEt )Cl 2 ] [por = TTP, and M = Ru (6); por = TPP, and M = Os (7)]. The diamagnetism and short (por)M-N(nitride) distances in 2 [Fe-N, 1.683(3) Å] and 4b [Ru-N, 1.743(3) Å] are indicative of the M IV ═N═M' IV bonding description. The cyclic voltammograms of the Fe/Ru (2) and Ru/Ru (4b) complexes in CH 2 Cl 2 displayed oxidation couples at approximately +0.29 and +0.35 V versus Fc +/0 (Fc = ferrocene) that are tentatively ascribed to the oxidation of the {L OEt Ru} and {Ru(TTP)} moieties, respectively, whereas the Fe/Os (3) and Os/Ru (5) complexes exhibited Os-centered oxidation at approximately -0.06 and +0.05 V versus Fc +/0 , respectively. The crystal structures of 2 and 4b have been determined.

Elemental analysis of different varieties of rice samples using XRF technique

NASA Astrophysics Data System (ADS)

Kaur, Jaspreet; Kumar, Anil

2016-05-01

Rice is most consumed staple food in the world providing over 21% of the calorie intake of world's population having high yielding capacity. Elements detected in rice are Al, As, Br, Cd, Cl, Co, Cs, Cu, Fe, Hg, K, Mg, Mn, Mo, Rb, Se and Zn by using Instrumental Neutron Activation with k0 standardization (R. Jayasekera etal,2004). Some of these trace elements are C, H, O, N, S, Ca, P, K, Na, Cl, Mn, Ti, Mg, Cu, Fe, Ni, Si and Zn are essential for growth of human physique The deficiency or excess of these elements in food is known to cause a variety of malnutrition or health disorders in the world. Every year, various varieties of rice are launched by Punjab Agriculture University, Ludhiana. The main purpose of which is to increases the yield to attain the maximum profit. But this leads to changing the elemental concentration in them, which may affect the human health according to variation in the nutrition values. The main objective is to study the presence of elemental concentration in various varieties of rice using EDXRF technique.

Surface complexation of carboxylate adheres Cryptosporidium parvum öocysts to the hematite-water interface

USGS Publications Warehouse

Gao, X.; Metge, D.W.; Ray, C.; Harvey, R.W.; Chorover, J.

2009-01-01

The interaction of viable Cryptosporidium parvum öocysts at the hematite (α-Fe2O3)−water interface was examined over a wide range in solution chemistry using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Spectra for hematite-sorbed öocysts showed distinct changes in carboxylate group vibrations relative to spectra obtained in the absence of hematite, indicative of direct chemical bonding between carboxylate groups and Fe metal centers of the hematite surface. The data also indicate that complexation modes vary with solution chemistry. In NaCl solution, öocysts are bound to hematite via monodentate and binuclear bidentate complexes. The former predominates at low pH, whereas the latter becomes increasingly prevalent with increasing pH. In a CaCl2 solution, only binuclear bidentate complexes are observed. When solution pH is above the point of zero net proton charge (PZNPC) of hematite, öocyst surface carboxylate groups are bound to the mineral surface via outer-sphere complexes in both electrolyte solutions.

"JCE" Classroom Activity Connections: NaCl or CaCl[subscript 2], Smart Polymer Gel Tells More

ERIC Educational Resources Information Center

Chen, Yueh-Huey; Lin, Jia-Ying; Wang, Yu-Chen; Yaung, Jing-Fun

2010-01-01

This classroom activity connection demonstrates the differences between the effects of NaCl (a salt of monovalent metal ions) and CaCl[subscript 2] (a salt of polyvalent metal ions) on swollen superabsorbent polymer gels. Being ionic compounds, NaCl and CaCl[subscript 2] both collapse the swollen polymer gels. The gel contracted by NaCl reswells…

Reducing toughness of beef from Bos indicus draught steers by injection of calcium chloride: Effect of concentration and time postmortem.

PubMed

Jaturasitha, S; Thirawong, P; Leangwunta, V; Kreuzer, M

2004-09-01

Calcium chloride (CaCl(2)) solution in concentrations of 0, 0.2, 0.3 and 0.4 M was injected at 10% (wt/wt) either 45 min or 24 h postmortem into longissimus dorsi muscles of eight draught steers discharged from work and >4 years of age. Shear force, after 7 days of aging, declined by CaCl(2) injection by up to 50% of control, depending on CaCl(2) concentration. Prerigor treatment was twice as efficient as postrigor injection. Collagen content and solubility were less clearly affected. Sensory tenderness scores were higher by 50% with all CaCl(2) concentrations, but only with prerigor treatment. A bitter taste was noted only with the highest concentration of CaCl(2), but overall acceptance did not increase with CaCl(2) concentration. CaCl(2) enhanced electrical conductivity, reduced redness and luminosity, and increased drip and thawing loss, but not boiling loss, of longissiumus dorsi. Results indicate a high potential of CaCl(2) treatment in extraordinarily tough meat.

Molecular dynamics simulation, ab initio calculation, and size-selected anion photoelectron spectroscopy study of initial hydration processes of calcium chloride.

PubMed

He, Zhili; Feng, Gang; Yang, Bin; Yang, Lijiang; Liu, Cheng-Wen; Xu, Hong-Guang; Xu, Xi-Ling; Zheng, Wei-Jun; Gao, Yi Qin

2018-06-14

To understand the initial hydration processes of CaCl 2 , we performed molecular simulations employing the force field based on the theory of electronic continuum correction with rescaling. Integrated tempering sampling molecular dynamics were combined with ab initio calculations to overcome the sampling challenge in cluster structure search and refinement. The calculated vertical detachment energies of CaCl 2 (H 2 O) n - (n = 0-8) were compared with the values obtained from photoelectron spectra, and consistency was found between the experiment and computation. Separation of the Cl-Ca ion pair is investigated in CaCl 2 (H 2 O) n - anions, where the first Ca-Cl ionic bond required 4 water molecules, and both Ca-Cl bonds are broken when the number of water molecules is larger than 7. For neutral CaCl 2 (H 2 O) n clusters, breaking of the first Ca-Cl bond starts at n = 5, and 8 water molecules are not enough to separate the two ion pairs. Comparing with the observations on magnesium chloride, it shows that separating one ion pair in CaCl 2 (H 2 O) n requires fewer water molecules than those for MgCl 2 (H 2 O) n . Coincidentally, the solubility of calcium chloride is higher than that of magnesium chloride in bulk solutions.

Igneous and Sedimentary Compositions from Four Landing Sites on Mars from the Alpha Particle X-Ray Spectrometer (APXS)

NASA Technical Reports Server (NTRS)

Gellert, R.; Arvidson, R. E.; Clark, B. C.; Ming, D. W.; Mittlefehldt, D. W.; Morris, R. W.; Squyres, S. W.; VanBommel, S.; Yen, A. S.

2016-01-01

The APXS - supported and promoted strongly by Heinrich Waenke - on all four Mars Rovers has returned compositional data from about 1000 rocks and soil targets along the combined traverses of over 60 kilometers. Providing precise and accurate bulk chemistry with typically 16 quantified elements, the APXS is a powerful and versatile tool that when combined with the ability to traverse to key rocks and soils has provided critical information needed to understand the geologic evolution of Mars. APXS data allow comparisons among landing sites, provide ground truth for orbiters and connections back to SNC meteorites. The soils and dust are basaltic in character and represent the average Mars composition similar to Adirondack basalts from Gusev crater but with unambiguous elevated and correlated S, Cl and Zn contents. At all four landing sites the APXS found several rocks with a felsic composition. The similarity is best assessed in a logarithmic ratio plot of rock normalized to the average soil composition (Fig.1). High alkaline, Al, and low Mg, Fe, low S, Cl and Ni, Zn as well as an Fe/Mn ratio of approximately 50 indicate a likely unaltered and igneous origin. Sediments, e.g. the Burns formation, with approximately 25 wt% SO3 at Meridiani Planum have been documented over 10s of kilometers (Fig. 2). This formation is compositionally homogeneous, but showing the removal of MgSO4 and a threefold increase in Cl downhill in 2 craters. The degraded rim of the Noachian crater Endeavour resembles average Mars crust, with local Ca, Mg and Fe sulfate alteration and elevated Mn, some felsic rocks, and high Al, Si and low Fe rocks, possibly indicating clays. Unusual soils at Gusev crater in the area surrounding Home Plate include some very rich in ferric sulfate salts (up to 35 wt% SO3) and some with 90% wt% SiO2, possibly indicating fumerolic activities. Rocks in the Columbia Hills show significant signs of alteration including elevated S, Cl and Br in the abraded interior. At Gale Crater, mudstones with approximately 20% clay, less than 1% SO3 and overall average Mars composition indicate a former habitable environment with low acidity. A remarkable diversity of compositions was found during Curiosity's traverses, which likely stems from material influx from the northern Gale rim. At Pahrump, the base of Mount Sharp, a homogeneous mudstone with lower Mg and Ca was encountered. The composition of this Murray unit can be traced over several kilometers with smooth trends of higher Fe/Mn and lower soluble trace elements Ni and Zn at higher elevation. The likely aeolian Stimson formation with average Mars crustal composition intersects in several places in sharp contact with the Murray formation. Both units show local alteration halos with highly elevated SiO2 of up to 75%, usually correlated with increase in Ti and often P.

High-temperature corrosion of iron-aluminum and iron-aluminum-yttrium alloys

NASA Astrophysics Data System (ADS)

Insoo, Kim

The high-temperature corrosion behavior of Fe3Al alloy has been investigated by conducting two studies: (1) corrosion of Fe 3Al and Fe3Al-Y alloys in oxidizing atmosphere and (2) corrosion of Fe3Al in mixed chlorine/oxygen environments. In the first study, oxidation of the two alloys, Fe-14.3 wt% Al and Fe-14.1 wt% Al-0.3 wt% Y, was carried out in the temperature range of 800 to 1100°C to investigate the general oxidation behavior of Fe3Al and the effect of yttrium on the oxidation of Fe3Al in terms of oxidation kinetics, oxide scale adhesion and microstructure. At lower temperatures (<1000°C), the oxidation rate of the two alloys was nearly identical, and the parabolic rate constant obtained as a function of temperature was Kp = 5128 exp[--39500 (cal/mol)/RT] mg2/cm4 h. At higher temperatures, however, yttrium-added Fe3Al alloy exhibited lower oxidation rate and much more improved oxide adhesion. The lower oxidation rate observed in Fe3Al-Y alloy seems to be due to the followings: (1) a decrease in aluminum diffusion through alumina scale and (2) modification of the scale growth mechanism from simultaneous countercurrent diffusion of aluminum and oxygen to predominant inward diffusion of oxygen, which generates less growth stress and thus prevents the formation of fast diffusion paths such as microcracks. The adhesion improvement of alumina scale formed on the Fe3Al-Y was attributed to the modification of alumina growth mechanism by the addition of Y to the Fe3Al alloy. The change of growth mechanism leads to the formation of pegs, decrease of the oxide growth stress, and decrease of voids formation, which enhances the adhesion of alumina scale to the Fe3Al alloy. The second study has focused on the corrosion of Fe3Al in the temperature range of 600--800°C in Cl2-Ar gas mixtures containing traces of oxygen as an impurity. Weight gain was observed during the corrosion of Fe3Al at 600°C in 0.25% Cl2-Ar, which is due to the formation of Fe2O3, while continuous weight loss of the specimen in 5% Cl2-Ar at 800°C was observed because of the formation of volatile metal chlorides, FeCl2, FeCl 3, and AlCl3. Meanwhile, three distinct stages of weight change during the corrosion of Fe3Al at 700°C in 1% Cl 2-Ar were observed: (1) weight gain, (2) linear weight loss, and (3) gradual decrease of weight loss. Initial weight gain is due to the formation of Fe2O3, and the weight loss in the subsequent two stages is due to the formation of volatile metal chlorides, FeCl 2, FeCl3, and AlCl3. Based on the kinetic and microstructural analyses, a reaction mechanism is proposed for each stage.

Preserving elemental content in adherent mammalian cells for analysis by synchrotron-based x-ray fluorescence microscopy

DOE PAGES

Jin, Qiaoling; Paunesku, Tatjana; Lai, Barry; ...

2016-08-31

Trace metals play important roles in biological function, and x-ray fluorescence microscopy (XFM) provides a way to quantitatively image their distribution within cells. The faithfulness of these measurements is dependent on proper sample preparation. Using mouse embryonic fibroblast NIH/3T3 cells as an example, we compare various approaches to the preparation of adherent mammalian cells for XFM imaging under ambient temperature. Direct side-by-side comparison shows that plunge-freezing-based cryoimmobilization provides more faithful preservation than conventional chemical fixation for most biologically important elements including P, S, Cl, K, Fe, Cu, Zn and possibly Ca in adherent mammalian cells. Although cells rinsed with freshmore » media had a great deal of extracellular background signal for Cl and Ca, this approach maintained cells at the best possible physiological status before rapid freezing and it does not interfere with XFM analysis of other elements. If chemical fixation has to be chosen, the combination of 3% paraformaldehyde and 1.5 % glutaraldehyde preserves S, Fe, Cu and Zn better than either fixative alone. Lastly, when chemically fixed cells were subjected to a variety of dehydration processes, air drying was proved to be more suitable than other drying methods such as graded ethanol dehydration and freeze drying. This first detailed comparison for x-ray fluorescence microscopy shows how detailed quantitative conclusions can be affected by the choice of cell preparation method.« less

Preserving elemental content in adherent mammalian cells for analysis by synchrotron-based x-ray fluorescence microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Qiaoling; Paunesku, Tatjana; Lai, Barry

Trace metals play important roles in biological function, and x-ray fluorescence microscopy (XFM) provides a way to quantitatively image their distribution within cells. The faithfulness of these measurements is dependent on proper sample preparation. Using mouse embryonic fibroblast NIH/3T3 cells as an example, we compare various approaches to the preparation of adherent mammalian cells for XFM imaging under ambient temperature. Direct side-by-side comparison shows that plunge-freezing-based cryoimmobilization provides more faithful preservation than conventional chemical fixation for most biologically important elements including P, S, Cl, K, Fe, Cu, Zn and possibly Ca in adherent mammalian cells. Although cells rinsed with freshmore » media had a great deal of extracellular background signal for Cl and Ca, this approach maintained cells at the best possible physiological status before rapid freezing and it does not interfere with XFM analysis of other elements. If chemical fixation has to be chosen, the combination of 3% paraformaldehyde and 1.5 % glutaraldehyde preserves S, Fe, Cu and Zn better than either fixative alone. Lastly, when chemically fixed cells were subjected to a variety of dehydration processes, air drying was proved to be more suitable than other drying methods such as graded ethanol dehydration and freeze drying. This first detailed comparison for x-ray fluorescence microscopy shows how detailed quantitative conclusions can be affected by the choice of cell preparation method.« less

Site specific ligand substitution in cubane-type Mo3FeS(4)(4+) clusters: kinetics and mechanism of reaction and isolation of mixed ligand Cl/SPh complexes.

PubMed

Algarra, Andrés G; Basallote, Manuel G; Fernandez-Trujillo, M J; Llusar, Rosa; Pino-Chamorro, Jose A; Sorribes, Ivan; Vicent, Cristian

2010-04-21

The synthesis, crystal structure and solution characterization of the cubane-type [Mo(3)(FeCl)S(4)(dmpe)(3)Cl(3)] (1) (dmpe = 1,2-bis(dimethylphophane-ethane)) cluster are reported and the ligand substitution processes of chloride by thiophenolate investigated. The kinetics and the intimate mechanism of these substitutions reveal that compound 1 undergoes a number of Fe and Mo site specific ligand substitution reactions in acetonitrile solutions. In particular, PhS(-) coordination at the tetrahedral Fe site proceeds in a single resolved kinetic step whereas such substitutions at the Mo sites proceed more slowly. The effect of the presence of acids in the reaction media is also investigated and reveals that an acid excess hinders substitution reactions both at the Fe and Mo sites; however, an acid-promoted solvolysis of the Fe-Cl bonds is observed. Electrospray ionization (ESI) and tandem (ESI-MS/MS) mass spectrometry allow the identification of all the reaction intermediates proposed on the basis of stopped-flow measurements. The distinctive site specific reactivity made it possible to isolate two new clusters of the Mo(3)FeS(4)(4+) family featuring mixed chlorine/thiophenolate ligands, namely Mo(3)S(4)(FeSPh)(dmpe)(3)Cl(3) (2) and [Mo(3)S(4)(FeSPh)(dmpe)(3)(SPh)(3)] (3). A detailed computational study has also been carried out to understand the details of the mechanism of substitution at the M-Cl (M = Mo and Fe) bonds as well as the solvolysis at the Fe-Cl sites, with particular emphasis on the role of acids on the substitution process. The results of the calculations are in agreement with the experimental observations, thus justifying the non-existence of an accelerating effect of acids on the thiophenolate substitution reaction, which differs from previous proposals for the Fe(4)S(4) and MoFe(3)S(4) clusters and some related compounds.

Reduction of Mn-oxides by ferrous iron in a flow system: column experiment and reactive transport modeling

NASA Astrophysics Data System (ADS)

Postma, D.; Appelo, C. A. J.

2000-04-01

The reduction of Mn-oxide by Fe2+ was studied in column experiments, using a column filled with natural Mn-oxide coated sand. Analysis of the Mn-oxide indicated the presence of both Mn(III) and Mn(IV) in the Mn-oxide. The initial exchange capacity of the column was determined by displacement of adsorbed Ca2+ with Mg2+. Subsequently a FeCl2 solution was injected into the column causing the reduction of the Mn-oxide and the precipitation of Fe(OH)3. Finally the exchange capacity of the column containing newly formed Fe(OH)3 was determined by injection of a KBr solution. During injection of the FeCl2 solution into the column, an ion distribution pattern was observed in the effluent that suggests the formation of separate reaction fronts for Mn(III)-oxide and Mn(IV)-oxide travelling at different velocities through the column. At the proximal reaction front, Fe2+ reacts with MnO2 producing Fe(OH)3, Mn2+ and H+. The protons are transported downstream and cause the disproportionation of MnOOH at a separate reaction front. Between the two Mn reaction fronts, the dissolution and precipitation of Fe(OH)3 and Al(OH)3 act as proton buffers. Reactive transport modeling, using the code PHREEQC 2.0, was done to quantify and analyze the reaction controls and the coupling between transport and chemical processes. A model containing only mineral equilibria constraints for birnessite, manganite, gibbsite, and ferrihydrite, was able to explain the overall reaction pattern with the sequential appearance of Mn2+, Al3+, Fe3+, and Fe2+ in the column outlet solution. However, the initial breakthrough of a peak of Ca2+ and the observed pH buffering indicated that exchange processes were of importance as well. The amount of potential exchangers, such as birnessite and ferrihydrite, did vary in the course of the experiment. A model containing surface complexation coupled to varying concentrations of birnessite and ferrihydrite and a constant charge exchanger in addition to mineral equilibria provided a satisfactory description of the distribution of all solutes in time and space. However, the observed concentration profiles are more gradual than indicated by the equilibrium model. Reaction kinetics for the dissolution of MnO2 and MnOOH and dissolution of Al(OH)3 were incorporated in the model, which explained the shape of the breakthrough curves satisfactorily. The results of this study emphasize the importance of understanding the interplay between chemical reactions and transport in addition to interactions between redox, proton buffering, and adsorption processes when dealing with natural sediments. Reactive transport modeling is a powerful tool to analyze and quantify such interactions.

Iron Sulfide Attenuates the Methanogenic Toxicity of Elemental Copper and Zinc Oxide Nanoparticles and their Soluble Metal Ion Analogs

PubMed Central

Gonzalez-Estrella, Jorge; Gallagher, Sara; Sierra-Alvarez, Reyes; Field, Jim A.

2016-01-01

Elemental copper (Cu0) and zinc oxide (ZnO) nanoparticle (NP) toxicity to methanogens has been attributed to the release of soluble metal ions. Iron sulfide (FeS) partially controls the soluble concentration of heavy metals and their toxicity in aquatic environments. Heavy metals displace the Fe from FeS forming poorly soluble metal sulfides in the FeS matrix. Therefore, FeS may be expected to attenuate the NP toxicity. This work assessed FeS as an attenuator of the methanogenic toxicity of Cu0 and ZnO NPs and their soluble salt analogs. The toxicity attenuation capacity of fine (25–75 µm) and coarse (500 to 1200 µm) preparations of FeS (FeS-f and FeS-c respectively) was tested in the presence of highly inhibitory concentrations of CuCl2, ZnCl2 Cu0 and ZnO NPs. FeS-f attenuated methanogenic toxicity better than FeS-c. The results revealed that 2.5× less FeS-f than FeS-c was required to recover the methanogenic activity to 50% (activity normalized to uninhibited controls). The results also indicated that a molar FeS-f/Cu0 NP, FeS-f/ZnO NP, FeS-f/ZnCl2, and FeS-f/CuCl2 ratio of 2.14, 2.14, 4.28, and 8.56 respectively, was necessary to recover the methanogenic activity to >75%. Displacement experiments demonstrated that CuCl2 and ZnCl2 partially displaced Fe from FeS. As a whole, the results indicate that not all the sulfide in FeS was readily available to react with the soluble Cu and Zn ions which may explain the need for a large stoichiometric excesses of FeS to highly attenuate Cu and Zn toxicity. Overall, this study provides evidence that FeS attenuates the toxicity caused by Cu0 and ZnO NPs and their soluble ion analogs to methanogens. PMID:26803736

Formation of 3-monochloro-1,2-propanediol (3-MCPD) di- and monoesters from tristearoylglycerol (TSG) and the potential catalytic effect of Fe²⁺ and Fe³⁺.

PubMed

Zhang, Zhongfei; Gao, Boyan; Zhang, Xiaowei; Jiang, Yuanrong; Xu, Xuebing; Yu, Liangli Lucy

2015-02-18

This study investigated whether and how triacylglycerol (TAG) may serve as a precursor for 3-monochloro-1,2-propanediol (3-MCPD) fatty acid ester formation using tristearoylglycerol (TSG). TSG was reacted with inorganic chloride compounds including NaCl, KCl, FeCl2, CuCl2, ZnCl2, FeCl3 and dry HCl, or organic chlorine compound lindane at different temperatures. Only FeCl2 and FeCl3 were able to form 3-MCPD esters from TSG. Further electron spin resonance (ESR) determination of TSG, Fe2(SO4)3 and 5,5-dimethylpyrroline-N-oxide (DMPO) reactions revealed potential of Fe ion in promoting free radical generations under the experimental conditions. To further confirm the effect of Fe ion, chelating agent (EDTA-2Na) was added to the model reactions. The results showed for the first time that EDTA-2Na was able to reduce the generation of 3-MCPD esters. In addition, FT-IR examination indicated a possible involvement of a carbonyl group during the reaction. Taking all the observations together, the possible mechanisms, involving the formation of either a cyclic acyloxonium or a glycidol ester radical intermediate, were proposed for generating 3-MCPD fatty acid di- and mono- esters from TAG under a high temperature and low moisture condition, as well as the coformation of glycidol esters. The results from this study may be useful for reducing the level of 3-MCPD esters and related toxicants in the refined edible oils and food products.

Uranium Reduction by Fe(II) in the Presence of Montmorillonite and Nontronite.

PubMed

Tsarev, Sergey; Waite, T David; Collins, Richard N

2016-08-02

Uranium(VI) interactions with three smectites (one montmorillonite and two nontronites - NAu1 and NAu2) were examined with 0, 1, and 2 mM aqueous concentrations of Fe(II) over the pH range of 3-9.5 in a background electrolyte of 100 mM NaCl and 1 mM CaCl2 in equilibration with 400 ppmv CO2(g) ([U(VI)] = 4 μM and 0.5 g smectite/L). In the absence of Fe(II), no differences were observed in the U(VI) sorption curves for the three clay minerals. In the presence of 1 or 2 mM Fe(II), under anoxic conditions, U(VI) uptake by the smectites changed slightly between ∼pH 3 and 6; however, uranium uptake increased significantly above ∼pH 6 and was proportional to the concentration of Fe(II) added to the system, particularly at pH values >8. The uptake of Fe(II) showed a sharp edge starting from ∼pH 6.5 with 95%-100% uptake occurring at pH values >7.5, with no difference observed between the iron-rich nontronites and montmorillonite. After 3 days of reaction at pH 7.6 (i.e., above the Fe(II) "sorption" edge), U(VI) was transformed to a mixture of U(IV) and U(VI) sorption complexes, and after 14 days of reaction, 100% of the U was found to be reduced to U(IV) in the form of nanocrystalline uraninite. In contrast, U remained as sorbed species until 14 days of reaction at pH 6.5. Ferrihydrite (NAu1), lepidocrocite, and magnetite (NAu2) were detected as secondary mineralization products upon reaction of the nontronites with Fe(II) but appeared to have no effect on the partitioning or speciation of uranium.

A Volcanic Environment for Bedrock Diagenesis at Meridiani Planum, Mars

NASA Astrophysics Data System (ADS)

Hynek, B. M.; McCollom, T. M.

2005-12-01

Exposed bedrocks at Meridiani Planum on Mars display chemical and mineralogical evidence suggesting interaction with liquid water. Based on the observed bedding morphology, crystal vugs, varying Br:Cl ratios, as well as high abundances of hematite and sulfate minerals, the rocks have been interpreted by the Mars Exploration Rover (MER) team as sedimentary/evaporite deposits. However, the composition of the Meridiani bedrocks indicates that the formation model advocated by the MER team is not plausible. If the sulfates were attributable to precipitation of salts from an evaporating brine the rocks would be enriched in a balancing cation (e.g., Ca, Mg, or Fe) but this is not observed. Ratios of cations including Fe, Mg, Ca, and Na to (Si + Al) in the rocks are nearly identical to the basaltic martian meteorite Shergotty, and also very similar to unweathered basaltic rocks at Meridiani and Gusev Crater. The compositional data strongly suggest that the Meridiani rocks represent typical martian basalt with a sulfur component added. Here, we propose an alternative model for diagenesis of Meridiani bedrock that involves deposition of volcanic ash followed by reaction with condensed SO2- and H2O-bearing vapors in a solfatara-like setting. We suggest that volcanic deposition may account for the textures observed in Meridiani rocks since morphologic bedding features including sorted grains, planar bedding, low-angle cross-stratification, festoon bedding, and ripple lamination are common in base surge deposits of ash on Earth. The lath-shaped vugs may be the remains of ferrous sulfates (or mixed Fe-Mg-Ca sulfates) formed in the early stages of alteration that became unstable during oxidation. Widely varying Br:Cl ratios are also common in solfatara environments on Earth. In this scenario, most of the alteration of the rocks likely occurred at high temperatures (~100° C or higher), possibly soon after the volcaniclastic deposits were emplaced and still retained their original heat. Extended periods of time, a standing body of water, and clement conditions would not have been required for completion of the hypothesized diagenetic sequence.

Coupled extremely light Ca and Fe isotopes in peridotites

NASA Astrophysics Data System (ADS)

Zhao, Xinmiao; Zhang, Zhaofeng; Huang, Shichun; Liu, Yufei; Li, Xin; Zhang, Hongfu

2017-07-01

Large metal stable isotopic variations have been observed in both extraterrestrial and terrestrial samples. For example, Ca exhibits large mass-dependent isotopic variation in terrestrial igneous rocks and mantle minerals (on the order of ∼2‰ variation in 44Ca/40Ca). A thorough assessment and understanding of such isotopic variations in peridotites provides important constraints on the evolution and compositon of the Earth's mantle. In order to better understand the Ca and Fe isotopic variations in terrestrial silicate rocks, we report Ca isotopic compositions in a set of peridotitic xenoliths from North China Craton (NCC), which have been studied for Fe isotopes. These NCC peridotites have large Ca and Fe isotopic variations, with δ44/40Ca ranging from -0.08 to 0.92 (delta value relative to SRM915a) and δ57/54Fe (delta value relative to IRMM-014) ranging from -0.61 to 0.16, and these isotopic variations are correlated with large Mg# (100 × Mg/(Mg + Fe) molar ratio) variation, ranging from 80 to 90. Importantly, NCC Fe-rich peridotites have the lowest 44Ca/40Ca and 57Fe/54Fe ratios in all terrestrial silicate rocks. In contrast, although ureilites, mantle rocks from a now broken differentiated asteroid(s), have large Mg# variation, from 70 to 92, they have very limited δ57Fe/54Fe variation (0.03-0.21, delta value relative to IRMM-014). Our model calculations show that the coupled extremely light Ca-Fe isotopic signatures in NCC Fe-rich peridotites most likely reflect kinetic isotopic fractionation during melt-peridotite reaction on a timescale of several to 104 years. In addition, our new data and compiled literature data show a possible compositional effect on the inter-mineral Ca isotopic fractionation between co-existing clinopyroxene and orthopyroxene pairs.

Combined effects of simulated acid rain and lanthanum chloride on chloroplast structure and functional elements in rice.

PubMed

Hu, Huiqing; Wang, Lihong; Zhou, Qing; Huang, Xiaohua

2016-05-01

Acid rain and rare earth element (REE) pollution exist simultaneously in many agricultural regions. However, how REE pollution and acid rain affect plant growth in combination remains largely unknown. In this study, the combined effects of simulated acid rain and lanthanum chloride (LaCl3) on chloroplast morphology, chloroplast ultrastructure, functional element contents, chlorophyll content, and the net photosynthetic rate (P n) in rice (Oryza sativa) were investigated by simulating acid rain and rare earth pollution. Under the combined treatment of simulated acid rain at pH 4.5 and 0.08 mM LaCl3, the chloroplast membrane was smooth, proteins on this membrane were uniform, chloroplast structure was integrated, and the thylakoids were orderly arranged, and simulated acid rain and LaCl3 exhibited a mild antagonistic effect; the Mg, Ca, Mn contents, the chlorophyll content, and the P n increased under this combined treatment, with a synergistic effect of simulated acid rain and LaCl3. Under other combined treatments of simulated acid rain and LaCl3, the chloroplast membrane surface was uneven, a clear "hole" was observed on the surface of chloroplasts, and the thylakoids were dissolved and loose; and the P n and contents of functional elements (P, Mg, K, Ca, Mn, Fe, Ni, Cu, Zn and Mo) and chlorophyll decreased. Under these combined treatments, simulated acid rain and LaCl3 exhibited a synergistic effect. Based on the above results, a model of the combined effects of simulated acid rain and LaCl3 on plant photosynthesis was established in order to reveal the combined effects on plant photosynthesis, especially on the photosynthetic organelle-chloroplast. Our results would provide some references for further understanding the mechanism of the combined effects of simulated acid rain and LaCl3 on plant photosynthesis.

1D and 2D assembly structures by imidazole···chloride hydrogen bonds of iron(II) complexes [Fe(II)(HL(n-Pr))3]Cl·Y (HL(n-Pr) = 2-methylimidazol-4-yl-methylideneamino-n-propyl; Y = AsF6, BF4) and their spin states.

PubMed

Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Iijima, Seiichiro; Halcrow, Malcolm A; Sunatsuki, Yukinari; Kojima, Masaaki

2011-12-07

Two Fe(II) complexes fac-[Fe(II)(HL(n-Pr))(3)]Cl·Y (Y = AsF(6) (1) and BF(4) (2)) were synthesized, where HL(n-Pr) is 2-methylimidazole-4-yl-methylideneamino-n-propyl. Each complex-cation has the same octahedral N(6) geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[Fe(II)(HL(n-Pr))(3)](2+) with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) are hydrogen-bonded to three Cl(-) ions or, from the viewpoint of the Cl(-) ion, one Cl(-) ion is hydrogen-bonded to three neighbouring fac-[Fe(II)(HL(n-Pr))(3)](2+) cations. The 3 : 3 NH···Cl(-) hydrogen bonds between Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) and Cl(-) generate two kinds of assembly structures. The directions of the 3 : 3 NH···Cl(-) hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) enantiomorphs are bridged by two NH···Cl(-) hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[Fe(II)(HL(n-Pr))(3)](2+)···Cl(-)}(3) giving a smaller cavity, in which Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) species with the same chirality are linked by NH···Cl(-) hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and Mössbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T(c↓) = 125.5 K and T(c↑) = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range.

Comparative Effects of Biochar, Slag and Ferrous-Mn Ore on Lead and Cadmium Immobilization in Soil.

PubMed

Mehmood, Sajid; Rizwan, Muhammad; Bashir, Saqib; Ditta, Allah; Aziz, Omar; Yong, Li Zhe; Dai, Zhihua; Akmal, Muhammad; Ahmed, Waqas; Adeel, Muhammad; Imtiaz, Muhammad; Tu, Shuxin

2018-02-01

A variety of remediation approaches have been applied to the heavy metals-contaminated soils, however, the immobilization of metals in co-contaminated soils still not cleared. Therefore, an incubation study was conducted to evaluate the instantaneous effects of different concentrations of biochar (BC), slag (SL) and Fe-Mn ore (FMO) on immobilization of Pb and Cd through the Toxicity Characteristic Leaching Procedure (TCLP) by following the the European Community Bureau of Reference (BCR), CaCl 2 and NH 4 NO 3 . The sequential extraction of BCR showed decrease in acid soluble fractions, while the residual proportions of Pb and Cd were enhanced with increasing concentrations of SL and BC. Addition of BC significantly lowered the extractable fractions of both metals by TCLP, NH 4 NO 3 and CaCl 2 as compared to SL and FMO. Among all amendments, BC incorporation into co-contaminated soil offered promising results for Pb and Cd immobilization. Overall, all amendments showed positive and long-term impact on the reclamation of co-contaminated soil with heavy metals and could deserve advance monitoring studies on a field scale.

Trace Element Studies on Tinospora cordifolia (Menispermaceae), Ocimum sanctum (Lamiaceae), Moringa oleifera (Moringaceae), and Phyllanthus niruri (Euphorbiaceae) Using PIXE.

PubMed

Gowrishankar, Ramadurai; Kumar, Manish; Menon, Vinay; Divi, Sai Mangala; Saravanan, M; Magudapathy, P; Panigrahi, B K; Nair, K G M; Venkataramaniah, K

2010-03-01

Traditionally, Tinospora cordifolia (Willd.) Hook. F. & Thomson (Menispermaceae), Ocimum sanctum L. (Lamiaceae), Moringa oleifera Lam. (Moringaceae), and Phyllanthus niruri L. (Euphorbiaceae) are some of the commonly used medicinal plants in India for curing ailments ranging from common cold, skin diseases, and dental infections to major disorders like diabetes, hypertension, jaundice, rheumatism, etc. To understand and correlate their medicinal use, trace element studies on the aqueous extract of these medicinal plants have been carried out using particle-induced X-ray emission technique. A 2-MeV proton beam was used to identify and characterize major and minor elements namely Cl, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Br, and Sr in them. Results have revealed that these elements are present in varying concentrations in the selected plants. Notable results include very high concentrations of Cl, K, and Ca in all the leaf samples, appreciable levels of Mn in all plants, high Zn content in T. cordifolia, and the aqueous extract of Moringa leaves compared to others and relative higher concentrations of Cr in all the plants.

Effect of oxidation agent on wood biomass in ethylene vinyl acetate conductive polymer: tensile properties, tensile fracture surface and electrical properties

NASA Astrophysics Data System (ADS)

Hanif, M. P. M.; Supri, A. G.; Rozyanty, A. R.; Tan, S. J.

2017-10-01

The wood fiber (WF) type of Pulverised Wood Filler obtained by combustion process at temperature under 700 °C for 3 hours was characterized and coated with ferric chloride (FeCl3) by ethanol solution. Both carbonized wood fiber (CWF) and carbonized wood fiber-ferric chloride (CWF-FeCl3) were used as filler in ethylene vinyl acetate (EVA) conductive polymer. The filler was coated with FeCl3 to enhance the properties of the CWF to achieve progressive mechanical and electrical properties. The CWF and CWF-FeCl3 loading were varied from 2.5 to 10.0 wt%. EVA/CWF and EVA/CWF-FeCl3 conductive polymer were processed by using Brabender Plasticoder at 160 °C with 50 rpm rotor speed for 10 min. The mechanical properties were investigated by tensile testing and the tensile fractured surface of conductive polymers was analyzed by scanning electron microscopy (SEM) analysis. Then, the electrical conductivity of conductive polymer was determined by four-point probe I-V measurement system. The EVA/CWF-FeCl3 conductive polymer showed greater electrical conductivity and tensile strength but lower elongation at break than EVA/CWF conductive polymer. SEM morphology displayed rougher surface between CWF-FeCl3 and EVA phases compared to EVA/CWF conductive polymer.

cis-2,2'-Bipyrimidine-bridged polynuclear complex: a stairway-like mixed-valent {Fe(4)} cluster.

PubMed

Alborés, Pablo; Rentschler, Eva

2010-10-04

We report the first example of a polynuclear discrete coordination compound exhibiting only bpym bridges and containing a first-row d transition metal. A smooth self-assembly one-pot synthetic route, starting from simply FeCl(2) and FeCl(3) hydrates, allowed us to prepare a tetranuclear Fe(4) cluster with a stairway-like structure and the formula cis-{[(H(2)O)Cl(3)Fe(III)-μ(bpym)Fe(II)Cl(2)]}(2)-μ(bpym) (1) . All spectroscopic data suggest that complex 1 is a valence-localized mixed-valent Fe(II)-Fe(III) cluster with typical Mössbauer lines for both sites, which do not change with temperature. Reflectance spectroscopy did not allow one to distinguish an intervalence charge-transfer band. However, time-dependent density functional theory (DFT) calculations predict a weak high-energy Fe(II) → Fe(III) transition. Regarding the magnetic properties, the high-spin Fe(II) and Fe(III) ions interact in a weakly antiferromagnetic way with isotropic J constants of only a few wavenumbers as derived from direct-current susceptibility and magnetization data. Broken-symmetry DFT calculations support these observations.

Intestinal absorption of calcium from calcium ascorbate in rats.

PubMed

Tsugawa, N; Yamabe, T; Takeuchi, A; Kamao, M; Nakagawa, K; Nishijima, K; Okano, T

1999-01-01

The intestinal absorption of calcium (Ca) from Ca ascorbate (Ca-AsA) was investigated in normal rats. Each animal was perorally administered either 5mg (low dose) or 10mg (high dose) of Ca in 1ml of distilled water as Ca-AsA, Ca carbonate (CaCO3), or Ca chloride (CaCl2), which were intrinsically labeled with 45Ca using 45CaCl2. The amount of radioactivity in plasma was measured periodically up to 34h after dosing, and pharmacokinetic parameters were calculated from the radioactivity in plasma. The time taken to reach the maximum 45Ca level (Tmax) did not differ among the three groups. The area under the plasma 45Ca level/time curve (AUCinfinity) value for the Ca-AsA group was significantly higher than those for the CaCO3 and the CaCl2 groups. The radioactivity at Tmax (Cmax) for the Ca-AsA group was significantly higher than those for the CaCO3 and the CaCl2 groups for the low dose, and comparable with or significantly higher than those for the CaCl2 and CaCO3 groups for the high dose. Similar results were observed for whole-body 45Ca retention. Radioactivity in the femur 34h after dosing was the highest in the Ca-AsA group and the lowest in the CaCO3 group. The rank order of solubility in water, the first fluid (pH 1.2, JP-1) of JPXIII disintegration medium, acetate buffer solution (pH 4.0), triethanolamine-malate buffer solution (pH 7.0) and ammonium chloride buffer solution (pH 10.0) at 37 degrees C was CaCl2 > Ca-AsA > CaCO3. In contrast, the rank order of the solubility in the second fluid (pH 6.8, JP-2) of JPXIII disintegration medium at 37 degrees C was Ca-AsA > CaCl2 > CaCO3. These results indicate that the absorbability of Ca from Ca-AsA is almost comparable with, or higher than, that from CaCl2 and significantly higher than that from CaCO3 because of its high degree of solubility in the intestine. Therefore, Ca-AsA would be useful as a Ca supplement with relatively high absorption from intestine.

Textural improvement of salt-reduced Alaska pollack (Theragra chalcogramma) roe product by CaCl2.

PubMed

Chen, Chaoping; Okazaki, Emiko; Osako, Kazufumi

2016-12-15

Salt-reduced Alaska pollack roe benefits public health by decreasing NaCl intake; however, it has a poor texture with low breaking strength. This study addresses the feasibility of NaCl reduction in salted roe products, with focusing on the improvement of breaking strength using CaCl2. Salted roe products were prepared by immersing Alaska pollack roe in either NaCl solutions (3.5, 7.0, 15.0, 20.0, and 25.0%) or 7.0% NaCl solutions with added CaCl2 (0.0, 0.5, 1.0, 2.0, and 3.0%). Breaking strength, moisture and salt contents, eggshell protein composition of the salted roe products, as well as total endogenous transglutaminase (TGase) activity in various NaCl and CaCl2 concentrations were analyzed. CaCl2 addition enhanced eggshell protein crosslinking and breaking strength of the salt-reduced roe products. An acyl transfer reaction catalyzed by calcium-dependent TGase may be responsible for the eggshell protein crosslinking and improved texture. Thus, we successfully developed a salt-reduced Alaska roe product using CaCl2. Copyright © 2016 Elsevier Ltd. All rights reserved.

Inhibition and Promotion of Heat-Induced Gelation of Whey Proteins in the Presence of Calcium by Addition of Sodium Caseinate.

PubMed

Nguyen, Bach T; Balakrishnan, Gireeshkumar; Jacquette, Boris; Nicolai, Taco; Chassenieux, Christophe; Schmitt, Christophe; Bovetto, Lionel

2016-11-14

Heat-induced aggregation and gelation of aqueous solutions of whey protein isolate (WPI) in the presence of sodium caseinate (SC) and CaCl 2 was studied at pH 6.6. The effect of adding SC (0-100 g/L) on the structure of the aggregates and the gels was investigated by light scattering and confocal laser scanning microscopy at different CaCl 2 concentration ([CaCl 2 ] = 0-30 mM). The gelation process was studied by oscillatory shear rheology. At the whey protein concentrations studied here (34 and 60 g/L), no gels were formed in the absence of CaCl 2 and SC. However, WPI solutions gelled above a critical CaCl 2 concentration that increased with increasing SC concentration. In the absence of CaCl 2 , WPI gels were formed only above a critical SC concentration. The critical SC concentration needed to induce WPI gelation decreased weakly when CaCl 2 was added. In an intermediate range of CaCl 2 concentrations, gels were formed both at low and high SC concentrations, but not at intermediate SC concentrations. Finally, at high CaCl 2 concentrations gels were formed at all SC concentrations. The gelation rate and the gel structure of the gels formed at low and high casein concentrations were very different. The effect of SC on the thermal gelation of WPI was interpreted by competition for Ca 2+ , a chaperon effect, and microphase separation.

Effect of chloride channel inhibitors on cytosolic Ca2+ levels and Ca2+-activated K+ (Gardos) channel activity in human red blood cells.

PubMed

Kucherenko, Yuliya V; Wagner-Britz, Lisa; Bernhardt, Ingolf; Lang, Florian

2013-04-01

DIDS, NPPB, tannic acid (TA) and AO1 are widely used inhibitors of Cl(-) channels. Some Cl(-) channel inhibitors (NPPB, DIDS, niflumic acid) were shown to affect phosphatidylserine (PS) scrambling and, thus, the life span of human red blood cells (hRBCs). Since a number of publications suggest Ca(2+) dependence of PS scrambling, we explored whether inhibitors of Cl(-) channels (DIDS, NPPB) or of Ca(2+)-activated Cl(-) channels (DIDS, NPPB, TA, AO1) modified intracellular free Ca(2+) concentration ([Ca(2+)]i) and activity of Ca(2+)-activated K(+) (Gardos) channel in hRBCs. According to Fluo-3 fluorescence in flow cytometry, a short treatment (15 min, +37 °C) with Cl(-) channels inhibitors decreased [Ca(2+)]i in the following order: TA > AO1 > DIDS > NPPB. According to forward scatter, the decrease of [Ca(2+)]i was accompanied by a slight but significant increase in cell volume following DIDS, NPPB and AO1 treatments. TA treatment resulted in cell shrinkage. According to whole-cell patch-clamp experiments, TA activated and NPPB and AO1 inhibited Gardos channels. The Cl(-) channel blockers further modified the alterations of [Ca(2+)]i following ATP depletion (glucose deprivation, iodoacetic acid, 6-inosine), oxidative stress (1 mM t-BHP) and treatment with Ca(2+) ionophore ionomycin (1 μM). The ability of the Cl(-) channel inhibitors to modulate PS scrambling did not correlate with their influence on [Ca(2+)]i as TA and AO1 had a particularly strong decreasing effect on [Ca(2+)]i but at the same time enhanced PS exposure. In conclusion, Cl(-) channel inhibitors affect Gardos channels, influence Ca(2+) homeostasis and induce PS exposure of hRBCs by Ca(2+)-independent mechanisms.

Pb{sub 5}Fe{sub 3}TiO{sub 11}Cl: A rare example of Ti(IV) in a square pyramidal oxygen coordination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Batuk, Maria, E-mail: Maria.Batuk@uantwerpen.be; Batuk, Dmitry; Abakumov, Artem M.

A new oxychloride Pb{sub 5}Fe{sub 3}TiO{sub 11}Cl has been synthesized using the solid state method. Its crystal and magnetic structure was investigated in the 1.5–550 K temperature range using electron diffraction, high angle annular dark field scanning transmission electron microscopy, atomic resolution energy dispersive X-ray spectroscopy, neutron and X-ray powder diffraction. At room temperature Pb{sub 5}Fe{sub 3}TiO{sub 11}Cl crystallizes in the P4/mmm space group with the unit cell parameters a=3.91803(3) Å and c=19.3345(2) Å. Pb{sub 5}Fe{sub 3}TiO{sub 11}Cl is a new n=4 member of the oxychloride perovskite-based homologous series A{sub n+1}B{sub n}O{sub 3n−1}Cl. The structure is built of truncated Pb{submore » 3}Fe{sub 3}TiO{sub 11} quadruple perovskite blocks separated by CsCl-type Pb{sub 2}Cl slabs. The perovskite blocks consist of two layers of (Fe,Ti)O{sub 6} octahedra sandwiched between two layers of (Fe,Ti)O{sub 5} square pyramids. The Ti{sup 4+} cations are preferentially located in the octahedral layers, however, the presence of a noticeable amount of Ti{sup 4+} in a five-fold coordination environment has been undoubtedly proven using neutron powder diffraction and atomic resolution compositional mapping. Pb{sub 5}Fe{sub 3}TiO{sub 11}Cl is antiferromagnetically ordered below 450(10) K. The ordered Fe magnetic moments at 1.5 K are 4.06(4) μ{sub B} and 3.86(5) μ{sub B} on the octahedral and square-pyramidal sites, respectively. - Highlights: • Pb{sub 5}Fe{sub 3}TiO{sub 11}Cl has been synthesized using the solid state method. • The structure has been refined using neutron powder diffraction data at 1.5–550 K. • It is a new n=4 member of the perovskite-related homologous series A{sub n+1}B{sub n}O{sub 3n−1}Cl. • Ti{sup 4+} cations have both octahedral and square-pyramidal coordination environment. • Pb{sub 5}Fe{sub 3}TiO{sub 11}Cl is antiferromagnetically ordered below T{sub N}≈450 K.« less

Report: antioxidant and nutraceutical value of wild medicinal Rubus berries.

PubMed

Ahmad, Mushtaq; Masood, Saima; Sultana, Shazia; Hadda, Taibi Ben; Bader, Ammar; Zafar, Muhammad

2015-01-01

Nutritional quality and antioxidant capacity of three edible wild berries (Rubus ellipticus Smith, Rubus niveus Thunb, Rubus ulmifolius L.) from Lesser Himalayan Range (LHR) were evaluated. Their edible portion was assayed for moisture, fats, ash, carbohydrates, proteins, fibers, essential minerals (Ca, P, Mg, K, Na, Cl, S, Mn, Zn, Fe, Cu, Se, Co, Ni) and DPPH free radical scavenging activity was applied to determine the antioxidant potential. The fruit of Rubus ulmifolius L. (blackberry) possessed the highest values of energy (403.29 Kcal), total protein (6.56g/100 g), Nitrogen (N) content (1500mg/100g), K (860.17mg/100g), Ca (620.56mg/100g), Zn (17.509mg/100g) and the strongest antioxidant activity (98.89% inhibition). While the raspberries (Rubus ellipticus Smith, Rubus niveus Thunb.) exhibited more significant contents of dietary fiber (5.90g/100g), carbohydrates (86.4 g/100 g) and Fe (4.249mg/100g). Significant variation was observed among the tested samples in all the investigated features. The combination of bio elements and active antioxidants clearly showed the applicability of these berries as a nutraceutical supplement.

Physicochemical and thermal characteristics of the sludge produced after thermochemical treatment of petrochemical wastewater.

PubMed

Verma, Shilpi; Prasad, Basheshwar; Mishra, I M

2012-01-01

The present work describes the physicochemical and thermal characteristics of the sludge generated after thermochemical treatment of wastewater from a petrochemical plant manufacturing purified terephthalic acid (PTA). Although FeCl3 was found to be more effective than CuSO4 in removing COD from wastewater, the settling and filtration characteristics of FeCl3 sludge were poorer. Addition of cationic polyacrylamide (CPAA; 0.050kg/m3) to the FeCl3 wastewater system greatly improved the values of the filter characteristics of specific cake resistance (1.2 x 10(8) m/kg) and resistance of filter medium (9.9 x 10(8) m(-1)) from the earlier values of 1.9 x 10(9) m/kg and 1.7 x 10(8) m(-1), respectively. SEM-EDAX and FTIR studies were undertaken, to understand the sludge structure and composition, respectively. The moisture distribution in the CuSO4 sludge, FeCl3 sludge and FeCl3 + CPAA sludge showed that the amount of bound water content in the CuSO4 and FeCl3 + CPAA sludges is less than that of the FeCl3 sludge and there was a significant reduction in the solid-water bond strength of FeCl3 + CPAA sludge, which was responsible for better settling and filtration characteristics. Due to the hazardous nature of the sludge, land application is not a possible route of disposal. The thermal degradation behaviour of the sludge was studied for its possible use as a co-fuel. The studies showed that degradation behaviour of the sludge was exothermic in nature. Because of the exothermic nature of the sludge, it can be used in making fuel briquettes or it can be disposed of via wet air oxidation.

Structure of Fe(III) precipitates generated by Fe(0) electrocoagulation in the presence of groundwater ions

NASA Astrophysics Data System (ADS)

van Genuchten, C. M.; Pena, J.; Addy, S. E.; Gadgil, A. J.

2012-12-01

Electrocoagulation (EC) using Fe(0) electrodes is an inexpensive and efficient technology capable of removing a variety of contaminants from water supplies. Because of its ease of use and modest electricity and Fe(0) requirements, EC has potential as an arsenic-removal technology for rural South Asia, where millions drink groundwater contaminated by arsenic. In EC, a small external voltage applied to a sacrificial Fe(0) anode in contact with an electrolyte (e.g. pumped groundwater containing arsenic) promotes the oxidative dissolution of Fe ions, which polymerize and create reactive hydrous ferric oxides (HFO) in-situ with a high affinity for binding contaminants. The chemical composition of the electrolyte influences EC performance. For example, major inorganic ions present in groundwater (e.g. Ca, Mg, P, As(V), Si) alter the pathway by which FeO6 oligomers polymerize to form crystalline Fe (oxyhydr)oxide minerals. Because the precipitate structure largely determines properties that govern the efficiency of EC systems (e.g. precipitate reactivity and colloidal stability), it is essential to understand the individual and interdependent structural effects of common groundwater ions. In this work, we integrate Fe K-edge EXAFS spectroscopy with the Pair Distribution Function (PDF) technique to create a detailed description of EC precipitate structure as a function of electrolyte chemistry. EC precipitate samples were generated in a range of individual and combined concentrations of Ca, Mg, P, As(V), and Si, encompassing most of the typical levels found in natural groundwater. Combining complementary EXAFS and PDF techniques with batch uptake experiments and general chemical reasoning, we obtain structural representations of EC precipitates that are inaccessible with any single characterization technique. Our results indicate that the presence of As(V), P, and Si oxyanions promote the formation of nanoscale material bearing similar, but not identical, intermediate-ranged atomic pair correlations as 2-line ferrihydrite (2LFH), rather than lepidocrocite (Lp) which is generated in an NaCl electrolyte. However, when Ca or Mg is added to oxyanion electrolytes, Fe-Fe polymerization and particle size both tend to increase and a Lp-like material with characteristic Fe-O and Fe-Fe pair correlations is once again favored. The presence of either Ca or Mg also enhances the removal P, As(V), and to a lesser extent, Si per mass of Fe. The analysis from EXAFS and PDF spectra provide new insights into the polyhedral connectivity of nanoscale oxyanion-bearing HFO formed under a wide range of chemical conditions, improving predictions of EC performance in the field and allowing for knowledge-based improvements in the design of future EC systems. Our PDF data also show that the most disordered EC precipitate samples (formed at high oxyanion/Fe ratios) all share a similar "backbone" of 3-4 peaks beyond the first 4 Å, regardless of the oxyanion present during synthesis. Using 2LFH as a reference, we index all atomic pair correlations throughout the coherently scattering structure of our disordered samples.

Modeling the Reaction of Fe Atoms with CCl4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camaioni, Donald M.; Ginovska, Bojana; Dupuis, Michel

2009-01-05

The reaction of zero-valent iron with carbon tetrachloride (CCl4) in gas phase was studied using density functional theory. Temperature programmed desorption experiments over a range of Fe and CCl4 coverages on a FeO(111) surface, demonstrate a rich surface chemistry with several reaction products (C2Cl4, C2Cl6, OCCl2, CO, FeCl2, FeCl3) observed. The reactivity of Fe and CCl4 was studied under three stoichiometries, one Fe with one CCl4, one Fe with two CCl4 molecules and two Fe with one CCl4, modeling the environment of the experimental work. The electronic structure calculations give insight into the reactions leading to the experimentally observed productsmore » and suggest that novel Fe-C-Cl containing species are important intermediates in these reactions. The intermediate complexes are formed in highly exothermic reactions, in agreement with the experimentally observed reactivity with the surface at low temperature (30 K). This initial survey of the reactivity of Fe with CCl4 identifies some potential reaction pathways that are important in the effort to use Fe nano-particles to differentiate harmful pathways that lead to the formation of contaminants like chloroform (CHCl3) from harmless pathways that lead to products such as formate (HCO2-) or carbon oxides in water and soil. The Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Roles of Nano- and Micro-Scale Subsurface Geochemical Reactions on Environmentally Sustainable Geologic Carbon Dioxide Sequestration

NASA Astrophysics Data System (ADS)

Hu, Yandi

Geologic CO2 sequestration (GCS) is a promising approach to reduce anthropogenic CO2 emissions into the atmosphere. At GCS sites, injected CO2 is kept in formation rock by an overlying low permeability caprock. During and after CO2 injection, geochemical reactions can affect the porosity, permeability, and pollutant transport in aquifers. Despite their importance, nano- and micro-scale subsurface geochemical reactions are far from well-understood. Clay mobilization has been reported to decrease aquifer permeability during water flooding, and clay minerals are abundant in caprock. Thus, we studied CO2-brine-clay interactions under varied conditions relevant to different GCS sites (at 35-95°C and under 35-120 atm CO2, in water, NaCl, MgCl2, or CaCl2 solutions). Biotite, Fe-bearing mica, was used as a model clay mineral. We observed numerous fibrous illite precipitates on mica after reaction for only 3 h, which had not been previously reported. A few hours later, the mica surface cracked and fibrous illite detached. The mobilization of fibrous illite can decrease the aquifer's permeability greatly and affect the safety and efficiency of GCS. Mechanisms related to ion exchange, mica swelling, and CO2 intercalation were explored. Oriented aggregation of illite nanoparticles forming the fibrous illite was directly observed, suggesting a new mechanism for fibrous illite formation. Interestingly, besides the pH effect, aqueous CO2 enhances mica cracking over N2. These findings can help to achieve safer subsurface operations. At GCS field sites, Fe concentration increased near the injection sites and originally adsorbed pollutants were released. As the brine flows, Fe re-precipitated because of pH increase. To better predict the fate and transport of aqueous pollutants, the nucleation and growth of Fe(III) (hydr)oxides were studied. New information about sizes and volumes of the Fe(III) (hydr)oxide nanoparticles precipitated in solution and on quartz, mica, and sapphire were provided using small angle X-ray scattering, in the presence of different ions (Al 3+, Cl-, NO3-, and SO 42-). Using complementary techniques, the controlling mechanisms related to surface charge, bond formation, and interfacial energies were explored. These new findings can help better predict pollutant transport in aquifers not only at GCS sites, but also in managed aquifer recharge and acid mine drainage sites.

Homoleptic versus Heteroleptic Formation of Mononuclear Fe(II) Complexes with Tris-Imine Ligands

DOE PAGES

Barrios, Leoni A.; Bartual-Murgui, Carlos; Peyrecave-Lleixa, Eugenia; ...

2016-04-13

In this paper, we show a marked tendency of Fe(II) to form heteroleptic [Fe(L)(L')](ClO 4) 2 complexes from pairs of chelating tris-imine 3bpp, tpy, or 2bbp ligands. New synthetic avenues for spin crossover research become thus available, here illustrated with three new heteroleptic compounds with differing magnetic behaviors: [Fe(H 4L1)(Cl-tpy)](ClO 4) 2 ·C 3H 6O (1), [Fe(H 2L3)(Me3bpp)](ClO 4) 2 ·C 3H 6O (2), [Fe(H 4L1)(2bbp)](ClO 4) 2 ·3C 3H 6O (3). Structural studies demonstrate that 1 is in the low-spin (LS) state up to 350 K, while complexes 2 and 3 are, by contrast, in the high-spin (HS) statemore » down to 2 K, as corroborated through magnetic susceptibility measurements. Upon exposure to the atmosphere, the latter exhibits the release of three molecules of acetone per complex, turning into the solvent-free analogue [Fe(H 4L1)(2bbp)](ClO 4) 2 (3a), through a single-crystal-to-single-crystal transformation. Lastly, this guest extrusion process is accompanied by a spin switch, from HS to LS.« less

Apatite-Melt Partitioning of Volatiles in Basaltic Systems: Implications for Determining Volatile Abundances in Planetary Bodies from Apatite

NASA Technical Reports Server (NTRS)

McCubbin, F. M.

2017-01-01

Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials, and due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources [i.e., 1]. Experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in basaltic systems [e.g., 2- 3], reporting that apatite-melt partitioning of volatiles is best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, exchange coefficients may vary as a function of temperature, pressure, melt composition, and/or oxygen fugacity. Furthermore, exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite [3]. In these regions of ternary space, we anticipate that crystal chemistry could influence partitioning behavior. Consequently, we conducted experiments to investigate the effect of apatite crystal chemistry on apatite-melt partitioning of F, Cl, and OH.

Mechanisms of intracellular calcium homeostasis in developing and mature bovine corpora lutea.

PubMed

Wright, Marietta F; Bowdridge, Elizabeth; McDermott, Erica L; Richardson, Samuel; Scheidler, James; Syed, Qaisar; Bush, Taylor; Inskeep, E Keith; Flores, Jorge A

2014-03-01

Although calcium (Ca(2+)) is accepted as an intracellular mediator of prostaglandin F2 alpha (PGF2alpha) actions on luteal cells, studies defining mechanisms of Ca(2+) homeostasis in bovine corpora lutea (CL) are lacking. The increase in intracellular Ca(2+) concentration ([Ca(2+)]i) induced by PGF2alpha in steroidogenic cells from mature CL is greater than in those isolated from developing CL. Our hypothesis is that differences in signal transduction associated with developing and mature CL contribute to the increased efficacy of PGF2alpha to induce a Ca(2+) signal capable of inducing regression in mature CL. To test this hypothesis, major genes participating in Ca(2+) homeostasis in the bovine CL were identified, and expression of mRNA, protein, or activity, in the case of phospholipase Cbeta (PLCbeta), in developing and mature bovine CL was compared. In addition, we examined the contribution of external and internal Ca(2+) to the PGF2alpha stimulated rise in [Ca(2+)]i in LLCs isolated from developing and mature bovine CL. Three differences were identified in mechanisms of calcium homeostasis between developing and mature CL, which could account for the lesser increase in [Ca(2+)]i in response to PGF2alpha in developing than in mature CL. First, there were lower concentrations of inositol 1,4,5-trisphosphate (IP3) after similar PGF2alpha challenge, indicating reduced phospholipase C beta (PLCbeta) activity, in developing than mature CL. Second, there was an increased expression of sorcin (SRI) in developing than in mature CL. This cytoplasmic Ca(2+) binding protein modulates the endoplasmic reticulum (ER) Ca(2+) release channel, ryanodine receptor (RyR), to be in the closed configuration. Third, there was greater expression of ATP2A2 or SERCA, which causes calcium reuptake into the ER, in developing than in mature CL. Developmental differences in expression detected in whole CL were confirmed by Western blots using protein samples from steroidogenic cells isolated from developing and mature CL. Localization of these genes in steroidogenic luteal cells was confirmed by immunohistochemistry. Therefore, it is concluded that the cellular mechanisms that allow PGF2alpha to induce a calcium signal of greater magnitude in mature than in developing CL involve 1) greater PLCbeta activity with enhanced generation of IP3, 2) an enhanced Ca(2+) release from the ER via unrestrained RYR2 due to a decrease in SRI expression, and 3) a reduction in calcium reuptake to the ER due to lower expression of ATP2A2. Accordingly, the increase in [Ca(2+)]i induced by PGF2alpha in mature large steroidogenic cells had less dependency from extracellular calcium than in those isolated from immature CL.

A view on elemental distribution alterations of coronary artery walls in atherogenesis

NASA Astrophysics Data System (ADS)

Pallon, J.; Homman, P.; Pinheiro, T.; Halpern, M. J.; Malmqvist, K.

1995-09-01

In this study, the Nuclear Microprobe technique was employed to investigate the elemental concentration alterations of minor and trace elements at the different cellular layers and structures of freeze-dried cryosections of human coronary arteries. Nuclear microprobe analyses enable to determine 7 elements, i.e., P, S, Cl, K, Ca, Fe and Zn in the artery walls. Furthermore, it was possible to identify early modifications of the artery due to the atherosclerosis progression that cannot be detected with specific staining or conventional histological methods. These modifications are shown to be related to abnormal Fe and Zn depositions in the surroundings of the elastic laminae. Later on, the calcifications of these regions occur, contributing to the elastic laminae damage and leading to the atheroma growing and maturation.

Naturally occurring levels of elements in fishes as determined by PIXE and XRF methods

NASA Astrophysics Data System (ADS)

Tallandini, L.; Giacobini, F.; Turchetto, M.; Galassini, S.; Liu, Q. X.; Shao, H. R.; Moschini, G.; Moro, R.; Gialanella, G.; Ghermandi, G.; Cecchi, R.; Injuk, J.; Valković, V.

1989-04-01

Naturally occurring levels of S, Cl, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, Sb, Sr and Pb were measured in the gills, liver and muscles of fishes ( Zosterisessor ophiocephalus Pall) in the northwestern region of the Adriatic Sea. The overall performance of PIXE and XRF methods was tested by the analysis of standard reference materials. The mean concentration values for elements were calculated from the distribution of experimentally determined concentration values. The obtained data are discussed in the framework of metal metabolism and toxicology.

Evidence from an Ice Core of a Large Impact Circa 1443 A.D.

NASA Astrophysics Data System (ADS)

Abbott, D.; Biscaye, P.; Cole-Dai, J.; Breger, D.

2005-12-01

Published data on melt water from the Siple Dome ice core show distinct anomalies at 1443.16 A.D. The Ca value is 111 ppb, over 9 times the next highest Ca value between 850-1760 A.D. The K value is 20 ppb, about 1.4 times the next highest K value. The Ca anomaly may be due to partial dissolution of CaCO3 microfossils from the 24 km Mahuika bolide impact crater on the southern New Zealand shelf. Deep-sea samples of the Mahuika ejecta layer contain >98% carbonate microfossils. The Mahuika impact may have produced tsunami runups of 130 meters in Jervis Bay, Australia. The Australian megatsunami deposits date to 1450±50 A.D. We analyzed the melt water from 8 ice-core samples from the West Antarctic Siple Dome ice core that date from 1440-1448 A.D. The 1443 A.D. level contained a peak in K of 53 ppb as compared to a background of ~6-7 ppb. Ca was high at 26 ppb but this is not as pronounced as reported earlier. We extracted solid material from the melt water. Except for the 1443 A.D. horizon and one fractured grain at the 1442 A.D. level, most samples were barren except for typical dust. At the 1443 A.D. level, we found 5 carbonate microfossils (coccoliths?) from 5 to 20 microns across. Two were round and solid. One microfossil appeared either caught during mitosis or broken during deformation and elongation. Another carbonate microfossil was unbroken, but appeared deformed into a square. We found a Cu grain with a small amount of oxygen. It is most likely a grain of native copper with an oxidized surface. Deformed microfossils and native minerals are both characteristic of bolide impacts. We also found many microcrystalline magnetite cubes, with an average crystal size of 0.3 microns or less. The high magnetic susceptibility of impact ejacta layers is caused by microcrystalline magnetite. We found a grain of conchoidally fractured feldspar ~15 microns long. A semi-quantitive EDAX analysis found 21% Si, 55% O, 9% Al, 5% Na, 3% K, 2% Fe, and 1% Ca (atomic %), well within the range of K-feldspar compositions. Because Fe does not fit into the feldspar structure, its occurrence implies either that the Fe-bearing feldspar is a glass, or that the Fe is in microcracks within the grain. As ice is not Fe-rich, the former is more likely. Because conchoidal fracture is characteristic of glass, this suggests that the feldspar is a glass (maskelynite) derived from an impact onto continental crust. We also found Al Fe oxide, Ti Al oxide, and amphibole. A semi-quantitative EDAX analysis of the latter found 53% O, 20% Si, 5% Na, 4% Al, Mg, and Fe, 3% Ca, and 0.5% K (atomic %) with trace Ti, S and Cl, close to the composition of the alkali amphibole richterite, which forms in contact metamorphosed limestones (skarns). The Al Fe oxide is most likely hercynite, a spinel that forms in contact metamorphic aureoles in silica-poor environments. All mineral grains had distinct edges. We also found radiating, fibrous crystals of a Ca Na silicate. An EDAX analysis of the mineral found 59% O, 13% Ca, 8% Si, 3% Na, and 1% Mg (atomic %). The Ca Na silicate is most likely pectolite (NaCa2Si3O8), which has radiating, fibrous crystals and forms in skarns. The presence of minerals characteristic of contact metamorphism is important as we have found abundant skarn facies minerals in the Mahuika ejecta layer within deep sea sediment. Thus, our data taken together are most consistent with an impact ejecta layer within the Siple Dome ice core that comes from the Mahuika impact event about 4044 kilometers away; providing a well-constrained date for the event around 1443 A.D.

Performance Optimization of Metallic Iron and Iron Oxide Nanomaterials for Treatment of Impaired Water Supplies

NASA Astrophysics Data System (ADS)

Xie, Yang

Iron nanomaterials including nanoscale zero valent iron (NZVI), NZVI-based bimetallic reductants (e.g., Pd/NZVI) and naturally occurring nanoscale iron mineral phases represent promising treatment tools for impaired water supplies. However, questions pertaining to fundamental and practical aspects of their reactivity may limit their performance during applications. For NZVI treatment of pollutant source zones, a major hurdle is its limited reactive lifetime. In Chapter 2, we report the longevity of NZVI towards 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA) and hexavalent chromium [Cr(VI)] in oxygen-free systems with various anionic co-solutes (e.g., Cl-, SO4 2-, ClO4-, HCO3 -, NO3-). Trends in longevity provide evidence that surface-associated Fe(II) species are responsible for Cr(VI) reduction, whereas 1,1,1,2-TeCA reduction depends on the accessibility of Fe(0) at the NZVI particle surface. In Chapter 3, we show that dithionite, previously utilized for in situ redox manipulation, can restore the reducing capacity of passivated NZVI treatment systems. Air oxidation of NZVI at pH ≥ 8 quickly exhausted reactivity despite a significant fraction of Fe(0) persisting in the particle core. Reduction of this passive layer by low dithionite concentrations restored suspension reactivity to levels of unaged NZVI, with multiple dithionite additions further improving pollutant removal. In Chapter 4, measurements of solvent kinetic isotope effects reveals that optimal Pd/NZVI reactivity results from accumulation of atomic hydrogen, which only occurs in NZVI-based systems due to their higher rates of corrosion. However, atomic hydrogen formation only occurs in aged Pd/NZVI suspensions for ˜2 weeks, after which any reactivity enhancement likely results from galvanic corrosion of Fe(0). Finally, the activity of hybrid nanostructures consisting of multi-walled carbon nanotubes decorated with of hematite nanoparticles (alphaFe 2O3/MWCNT) is explored in Chapter 5. Sorption of Cu(II) and Cr(VI) is enhanced in hybrid nanostructure systems beyond what would be expected from simple additive sorption capacities of their building blocks. The enhanced sorption capacity is in part derived from the greater surface area of hematite nanoparticles immobilized on MWCNTs relative to aggregated hematite suspensions. The hybrid alphaFe2O3/MWCNT may also exhibit unique surface chemistry, as supported by the tunable values of zeta potential measured as a function of the mass of alphaFe2O 3 deposited on the MWCNTs.

[Bio-oil production from biomass pyrolysis in molten salt].

PubMed

Ji, Dengxiang; Cai, Tengyue; Ai, Ning; Yu, Fengwen; Jiang, Hongtao; Ji, Jianbing

2011-03-01

In order to investigate the effects of pyrolysis conditions on bio-oil production from biomass in molten salt, experiments of biomass pyrolysis were carried out in a self-designed reactor in which the molten salt ZnCl2-KCl (with mole ratio 7/6) was selected as heat carrier, catalyst and dispersion agent. The effects of metal salt added into ZnCl2-KCl and biomass material on biomass pyrolysis were discussed, and the main compositions of bio-oil were determined by GC-MS. Metal salt added into molten salt could affect pyrolysis production yields remarkably. Lanthanon salt could enhance bio-oil yield and decrease water content in bio-oil, when mole fraction of 5.0% LaCl3 was added, bio-oil yield could reach up to 32.0%, and water content of bio-oil could reduce to 61.5%. The bio-oil and char yields were higher when rice straw was pyrolysed, while gas yield was higher when rice husk was used. Metal salts showed great selectivity on compositions of bio-oil. LiCl and FeCl2 promoted biomass to pyrolyse into smaller molecular weight compounds. CrCl3, CaCl2 and LaCl3 could restrain second pyrolysis of bio-oil. The research provided a scientific reference for production of bio-oil from biomass pyrolysis in molten salt.

Chloride channels are necessary for full platelet phosphatidylserine exposure and procoagulant activity.

PubMed

Harper, M T; Poole, A W

2013-12-19

Platelets enhance thrombin generation at sites of vascular injury by exposing phosphatidylserine during necrosis-like cell death. Anoctamin 6 (Ano6) is required for Ca(2+)-dependent phosphatidylserine exposure and is defective in patients with Scott syndrome, a rare bleeding disorder. Ano6 may also form Cl(-) channels, though the role of Cl(-) fluxes in platelet procoagulant activity has not been explored. We found that Cl(-) channel blockers or removal of extracellular Cl(-) inhibited agonist-induced phosphatidylserine exposure. However, this was not due to direct inhibition of Ca(2+)-dependent scrambling since Ca(2+) ionophore-induced phosphatidylserine exposure was normal. This implies that the role of Ano6 in Ca(2+-)dependent PS exposure is likely to differ from any putative function of Ano6 as a Cl(-) channel. Instead, Cl(-) channel blockade inhibited agonist-induced Ca(2+) entry. Importantly, Cl(-) channel blockers also prevented agonist-induced membrane hyperpolarization, resulting in depolarization. We propose that Cl(-) entry through Cl(-) channels is required for this hyperpolarization, maintaining the driving force for Ca(2+) entry and triggering full phosphatidylserine exposure. This demonstrates a novel role for Cl(-) channels in controlling platelet death and procoagulant activity.

Preparation of Ferrotitanium Alloys by Electrolysis-Assisted Calciothermic Reduction of Ilmenite in Equimolar CaCl2-NaCl Electrolyte: Effect of Calcium Oxide

NASA Astrophysics Data System (ADS)

Zhou, Zhongren; Zhang, Yingjie; Hua, Yixin; Xu, Cunying; Dong, Peng; Zhang, Qibo; Wang, Ding

2018-04-01

The effect of CaO content on the preparation of ferrotitanium alloys from ilmenite with the method of the electrolysis-assisted calciothermic reduction has been investigated by use of ilmenite powders as raw materials that positions them next to the cathodic molybdenum plate, equimolar CaCl2-NaCl molten salt with 2-7 mol.% CaO as electrolyte and graphite as anode at 700°C with cell voltage of 2.8 V under argon atmosphere. It is demonstrated that increasing the reactant CaO content is beneficial to the calciothermic reduction of ilmenite and the intermediate CaTiO3. Experimental results also show that after 14 h of calciothermic reduction process, the products are ferrotitanium alloys and the specific energy consumption is only about 10.21 kWh kg-1 when adding 5 mol.% CaO into equimolar CaCl2-NaCl molten salt and approximately 14.40 kWh kg-1 when CaO content is increased to 7 mol.%.

Important role of calcium chloride in preventing carbon monoxide generation during desflurane degradation with alkali hydroxide-free carbon dioxide absorbents.

PubMed

Ando, Takahiro; Mori, Atsushi; Ito, Rie; Nishiwaki, Kimitoshi

2017-12-01

We investigated whether calcium chloride (CaCl 2 ), a supplementary additive in carbon dioxide (CO 2 ) absorbents, could affect carbon monoxide (CO) production caused by desflurane degradation, using a Japanese alkali-free CO 2 absorbent Yabashi Lime ® -f (YL-f), its CaCl 2 -free and 1% CaCl 2 -added derivatives, and other commercially available alkali-free absorbents with or without CaCl 2 . The reaction between 1 L of desflurane gas (3-10%) and 20 g of desiccated specimen was performed in an artificial closed-circuit anesthesia system for 3 min at 20 or 40 °C. The CO concentration was measured using a gas chromatograph equipped with a semiconductor sensor detector. The systems were validated by detecting dose-dependent CO production with an alkali hydroxide-containing CO 2 absorbent, Sodasorb ® . Compared with YL-f, the CaCl 2 -free derivative caused the production of significantly more CO, while the 1% CaCl 2 -added derivative caused the production of a comparable amount of CO. These phenomena were confirmed using commercially available absorbents AMSORB ® PLUS, an alkali-free absorbent with CaCl 2 , and LoFloSorb™, an alkali-free absorbent without CaCl 2 . These results suggest that CaCl 2 plays an important role in preventing CO generation caused by desflurane degradation with alkali hydroxide-free CO 2 absorbents like YL-f.

The influence of manganese treatment on the distribution of metal elements in rats and the protection by sodium para-amino salicylic acid.

PubMed

Yuan, Zong-Xiang; Chen, Hai-Bin; Li, Shao-Jun; Huang, Xiao-Wei; Mo, Yu-Huan; Luo, Yi-Ni; He, Sheng-Nan; Deng, Xiang-Fa; Lu, Guo-Dong; Jiang, Yue-Ming

2016-07-01

Manganese (Mn) overexposure induced neurological damages, which could be potentially protected by sodium para-aminosalicylic acid (PAS-Na). In this study, we systematically detected the changes of divalent metal elements in most of the organs and analyzed the distribution of the metals in Mn-exposed rats and the protection by PAS-Na. Sprague Dawley (SD) rats received intraperitoneal injections of 15mg/kg MnCl2·4H2O (5d/week for 3 weeks), followed by subcutaneous (back) injections of PAS-Na (100 and 200mg/kg, everyday for 5 weeks). The concentrations of Mn and other metal elements [Iron (Fe), Copper (Cu), Zinc (Zn), Magnesium (Mg), Calcium (Ca)] in major organs (liver, spleen, kidney, thighbone and iliac bone, cerebral cortex, hippocampus and testes) and blood by Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES). The results showed that Mn overexposure significantly increased Mn in most organs, Fe and Zn in liver, Fe and Mg in blood; however decreased Fe, Cu, Zn, Mg and Ca in cortex, Cu and Zn in kidney, Cu and Mg in iliac bone, and Zn in blood. In contrast, PAS-Na treatment restored most changes particularly in cortex. In conclusion, excessive Mn exposure disturbed the balance of other metal elements but PAS-Na post-treatments could restore these alterations. Copyright © 2016 Elsevier GmbH. All rights reserved.

Scan Rate Dependent Spin Crossover Iron(II) Complex with Two Different Relaxations and Thermal Hysteresis fac-[Fe(II)(HL(n-Pr))3]Cl·PF6 (HL(n-Pr) = 2-Methylimidazol-4-yl-methylideneamino-n-propyl).

PubMed

Fujinami, Takeshi; Nishi, Koshiro; Hamada, Daisuke; Murakami, Keishiro; Matsumoto, Naohide; Iijima, Seiichiro; Kojima, Masaaki; Sunatsuki, Yukinari

2015-08-03

Solvent-free spin crossover Fe(II) complex fac-[Fe(II)(HL(n-Pr))3]Cl·PF6 was prepared, where HL(n-Pr) denotes 2-methylimidazol-4-yl-methylideneamino-n-propyl. The magnetic susceptibility measurements at scan rate of 0.5 K min(-1) showed two successive spin transition processes consisting of the first spin transition T1 centered at 122 K (T1↑ = 127.1 K, T1↓ = 115.8 K) and the second spin transition T2 centered at ca. 105 K (T2↑ = 115.8 K, T2↓ = 97.2 K). The magnetic susceptibility measurements at the scan rate of 2.0, 1.0, 0.5, 0.25, and 0.1 K min(-1) showed two scan speed dependent spin transitions, while the Mössbauer spectra detected only the first spin transition T1. The crystal structures were determined at 160, 143, 120, 110, 95 K in the cooling mode, and 110, 120, and 130 K in the warming mode so as to follow the spin transition process of high-spin HS → HS(T1) → HS(T2) → low-spin LS → LS(T2) → LS(T1) → HS. The crystal structures at all temperatures have a triclinic space group P1̅ with Z = 2. The complex-cation has an octahedral N6 coordination geometry with three bidentate ligands and assume a facial-isomer with Δ- and Λ-enantimorphs. Three imidazole groups of fac-[Fe(II)(HL(n-Pr))3](2+) are hydrogen-bonded to three Cl(-) ions. The 3:3 NH(imidazole)···Cl(-) hydrogen-bonds form a stepwise ladder assembly structure, which is maintained during the spin transition process. The spin transition process is related to the structural changes of the FeN6 coordination environment, the order-disorder of PF6(-) anion, and the conformation change of n-propyl groups. The Fe-N bond distance in the HS state is longer by 0.2 Å than that in the LS state. Disorder of PF6(-) anion is not observed in the LS state but in the HS state. The conformational changes of n-propyl groups are found in the spin transition processes except for HS → HS(T1) → HS(T2).

Effect of CoCl(2) treatment on major and trace elements metabolism and protein concentration in mice.

PubMed

Zaksas, Nataliya; Gluhcheva, Yordanka; Sedykh, Sergey; Madzharova, Maria; Atanassova, Nina; Nevinsky, Georgy

2013-01-01

Cobalt (Co) is a transition metal and an essential trace element, required for vitamin B(12) biosynthesis, enzyme activation and other biological processes, but toxic in high concentrations. There is lack of data for the effect of long-term Co(II) treatment on the concentrations of other trace elements. We estimate the influence of cobalt chloride (CoCl(2)) on the relative content of different metals in mouse plasma using two-jet arc plasmatron atomic emission and on the total protein content. On average, the content of different elements in the plasma of 2-month-old balb/c mice (control group) decreased in the order: Ca>Mg>Si>Fe>Zn>Cu≥Al≥B. The treatment of mice for 60 days with CoCl(2) (daily dose 125 mg/kg) did not appreciably change the relative content of Ca, Cu, and Zn, while a 2.4-fold statistically significant decrease in the content of B and significant increase in the content of Mg (1.4-fold), Al and Fe (2.0-fold) and Si (3.2-fold) was found. A detectable amount of Mo was observed only for two control mice, while the plasma of 9 out of 16 mice of the treated group contained this metal. The administration of Co made its concentration detectable in the plasma of all mice of the treated group, but the relative content varied significantly. The treatment led to a 2.2-fold decrease in the concentration of the total plasma protein. Chronic exposure to CoCl(2) affects homeostasis as well as the concentrations and metabolism of other essential elements, probably due to competition of Co ions for similar binding sites within cells, altered signal transduction and protein biosynthesis. Long-term treatment also leads to significant weight changes and reduces the total protein concentration. The data may be useful for an understanding of Co toxicity, its effect on the concentration of other metal ions and different physiological processes. Copyright © 2012 Elsevier GmbH. All rights reserved.

Effect of groundwater geochemistry on pentachlorophenol remediation by smectite-templated nanosized Pd0/Fe0.

PubMed

Jia, Hanzhong; Gu, Cheng; Li, Hui; Fan, Xiaoyun; Li, Shouzhu; Wang, Chuanyi

2012-09-01

Zero-valent iron holds great promise in treating groundwater, and its reactivity and efficacy depend on many surrounding factors. In the present work, the effects of solution chemistry such as pH, humic acid (HA), and inorganic ions on pentachlorophenol (PCP) dechlorination by smectite-templated Pd(0)/Fe(0) were systematically studied. Smectite-templated Pd(0)/Fe(0) was prepared by saturating the negatively charged sites of smectite clay with Fe(III) and a small amount of Pd(II), followed by borohydride reduction to convert Fe(III) and Pd(II) into zero-valent metal clusters. Batch experiments were conducted to investigate the effects of water chemistry on PCP remediation. The PCP dechlorination rate critically depends on the reaction pH over the range 6.0~10.0; the rate constant (k (obs)) increases with decreasing the reaction pH value. Also, the PCP remediation is inhibited by HA, which can be attributed to the electron competition of HA with H(+). In addition, the reduction of PCP can be accelerated by various anions, following the order: Cl(-) > HCO (3) (-) > SO (4) (2-) ~no anion. In the case of cations, Ca(2+) and Mg(2+) (10 mM) decrease the dechlorination rate to 0.7959 and 0.7798 from 1.315 h(-1), respectively. After introducing HA into the reaction systems with cations or/and anions, the dechlorination rates are similar to that containing HA alone. This study reveals that low pH and the presence of some anions such as Cl(-) facilitate the PCP dechlorination and induce the rapid consumption of nanosized zero-valent iron simultaneously. However, the dechlorination rate is no longer correlated to the inhibitory or accelerating effects by cations and anions in the presence of 10 mg/L HA.

Enhanced magnetism of perovskite oxides, Sr(Sn,Fe)O3- δ , by substitution of nonmagnetic Ca and Ti ions

NASA Astrophysics Data System (ADS)

Nomura, Kiyoshi; Suzuki, Shigeyo; Mizunuma, Tomoya; Koike, Yuya; Okazawa, Atsushi

2017-11-01

Magnetic properties of perovskite oxides, SrSn1- x Fe x O3- δ ( x ≤ 0.15), substituted with nonmagnetic Ca and Ti ions were studied. XRD patterns showed the orthorhombic structure (close to tetragonal) of (Sr1- y Ca y )(Sn1- x Fe x )O3- δ and Sr(Sn1- x- y Fe x Ti y )O3- δ . The cell volumes decreased with the increase of Ca and Ti doping rates. Although Ti-substituted Sr(Sn, Fe)O3- δ showed small saturation magnetizations as compared with non-Ti substituted one, the magnetization increased a little with Ti doping rates up to 15%. On the other hand, all Ca-substituted Sr(Sn, Fe)O3- δ showed larger saturation magnetization than non-Ca substituted one. Two doublets of Fe3+ and a doublet of Fe4+ were observed in Mössbauer spectra of Ca-substituted Sr(Sn, Fe)O3- δ with weak ferromagnetism, and two sextets of high spin Fe3+ were additionally observed in Mössbauer spectra of Ca-doped Sr(Sn, Fe)O3- δ with relatively strong ferromagnetism. When Sr(Sn, Fe)O3- δ were further codoped with Ca and Ti ions, they showed the stable and enhanced ferromagnetic properties. It is considered that magnetic polarons among high spin Fe3+ species are overlapped by shrinking or deforming the crystal structure of perovskite oxides. That is the magnetism induced by a chemical pressure of perovskite oxides.

Ferromagnetic and photocatalytic behaviors observed in Ca-doped BiFeO3 nanofibres

NASA Astrophysics Data System (ADS)

Feng, Yan-Nan; Wang, Huan-Chun; Luo, Yi-Dong; Shen, Yang; Lin, Yuan-Hua

2013-04-01

Ca-doped BiFeO3 nanofibres have been fabricated by electrospinning method. Our results indicate that phase transition from space group R3c to C222 can be observed by the Ca doping. These BiFeO3 nanofibres show obvious room temperature ferromagnetic behaviors, and saturation magnetization can be enhanced with the Ca-doping concentration increasing, which could be correlated with the variation of the ratio of Fe2+/Fe3+ valence state. The BiFeO3 nanofibres show obvious photocatalytic performance and can be improved by the Ca-doping.

Mechanical properties and leaching modeling of activated incinerator bottom ash in Portland cement blends

DOE Office of Scientific and Technical Information (OSTI.GOV)

Onori, Roberta, E-mail: Roberta.onori@uniroma1.it; Polettini, Alessandra; Pomi, Raffaella

2011-02-15

In the present study the evolution of mechanical strength and the leaching behavior of major and trace elements from activated incinerator bottom ash/Portland cement mixtures were investigated. Chemical and mechanical activation were applied with the purpose of improving the reactivity of bottom ash in cement blends. Chemical activation made use of NaOH, KOH, CaCl{sub 2} or CaSO{sub 4}, which were selected for the experimental campaign on the basis of the results from previous studies. The results indicated that CaCl{sub 2} exhibited by far the best effects on the evolution of the hydration process in the mixtures; a positive effect onmore » mechanical strength was also observed when CaSO{sub 4} was used as the activator, while the gain in strength produced by KOH and NaOH was irrelevant. Geochemical modeling of the leaching solutions provided information on the mineral phases responsible for the release of major elements from the hardened materials and also indicated the important role played by surface sorption onto amorphous Fe and Al minerals in dictating the leaching of Pb. The leaching of the other trace metal cations investigated (Cu, Ni and Zn) could not be explained by any pure mineral included in the thermodynamic database used, suggesting they were present in the materials in the form of complex minerals or phase assemblages for which no consistent thermodynamic data are presently available in the literature.« less

Mechanical properties and leaching modeling of activated incinerator bottom ash in Portland cement blends.

PubMed

Onori, Roberta; Polettini, Alessandra; Pomi, Raffaella

2011-02-01

In the present study the evolution of mechanical strength and the leaching behavior of major and trace elements from activated incinerator bottom ash/Portland cement mixtures were investigated. Chemical and mechanical activation were applied with the purpose of improving the reactivity of bottom ash in cement blends. Chemical activation made use of NaOH, KOH, CaCl(2) or CaSO(4), which were selected for the experimental campaign on the basis of the results from previous studies. The results indicated that CaCl(2) exhibited by far the best effects on the evolution of the hydration process in the mixtures; a positive effect on mechanical strength was also observed when CaSO(4) was used as the activator, while the gain in strength produced by KOH and NaOH was irrelevant. Geochemical modeling of the leaching solutions provided information on the mineral phases responsible for the release of major elements from the hardened materials and also indicated the important role played by surface sorption onto amorphous Fe and Al minerals in dictating the leaching of Pb. The leaching of the other trace metal cations investigated (Cu, Ni and Zn) could not be explained by any pure mineral included in the thermodynamic database used, suggesting they were present in the materials in the form of complex minerals or phase assemblages for which no consistent thermodynamic data are presently available in the literature. Copyright © 2010 Elsevier Ltd. All rights reserved.

Hexanuclear Fe(III) wheels functionalized by amino-acetonitrile derivatives

NASA Astrophysics Data System (ADS)

Kravtsov, Victor Ch.; Malaestean, Iurie; Stingach, Eugenia P.; Duca, Gheorghe G.; Macaev, Fliur Z.; van Leusen, Jan; Kögerler, Paul; Hauser, Jürg; Krämer, Karl; Decurtins, Silvio; Liu, Shi-Xia; Ghosh, Ashta C.; Garcia, Yann; Baca, Svetlana G.

2018-04-01

Three new hexanuclear Fe(III) coordination wheels [Fe6Cl6(L1)6]·5(MeCN) (1), [Na0.5Fe6Cl6(L1)6](N3)0.5·4.5(MeCN) (2), and [Fe6Cl6(L2)6]·2(MeCN) (3) have been synthesized with new prepared amino-acetonitrile derivatives 2-[bis(2-hydroxyethyl)amino]acetonitrile hydrochloride (H2L1) and 3-[bis(2-hydroxyethyl)amino]propanenitrile hydrochloride (H2L2). They were structurally characterized by single-crystal X-ray diffraction. Mößbauer spectroscopy and magnetic susceptibility measurements indicate dominant antiferromagnetic behavior between the Fe(III) centers.

Novel Flaxseed Gum Nanocomposites Are Slow Release Iron Supplements.

PubMed

Liang, Shan; Huang, Yu; Shim, Youn Young; Ma, Xiang; Reaney, Martin J T; Wang, Yong

2018-05-23

Nanocomposites, based on iron salts and soluble flaxseed gum (FG), were prepared as potential treatments of iron deficiency anemia (IDA). FG was extracted, characterized, and formulated into iron-loading nanocomposites via ion-exchange against FeCl 3 , Fe 2 (SO 4 ) 3 , FeCl 2 , and FeSO 4 ·7H 2 O. FG-iron nanocomposites preparation condition was optimized, and physicochemical properties of the nanocomposites were investigated. In vitro release kinetics of iron in simulated gastric fluid (SGF) was also evaluated. FG heteropolysaccharide, consisting of rhamnose (33.73%), arabinose (24.35%), xylose (14.23%), glucose (4.54%), and galactose (23.15%) monosaccharides, linked together via varieties of glycosidic bonds, was a good recipient for both ferric and ferrous irons under screened conditions (i.e., 80 °C, 2 h, I/G = 1:2). Iron loaded contents in the nanocomposites prepared from FG-FeCl 3 , FG-Fe 2 (SO 4 ) 3 , FG-FeCl 2 , and FG-FeSO 4 ·7H 2 O were 25.51%, 10.36%, 5.83%, and 22.83%, respectively. Iron in these nanocomposites was mostly in a bound state, especially in FG-FeCl 3 , due to chelation forming bonds between iron and polysaccharide hydroxyl or carboxyl groups and formed stable polysaccharide-iron crystal network structures. Free iron ions were effectively removed by ethanol treatments. Because of chelation, the nanocomposites delayed iron release in SGF and the release kinetics were consistent with Korsmeyer-Peppas model. This indicates that such complexes might reduce side effects of free iron in human stomach. Altogether, this study indicates that these synthetic FG-iron nanocomposites might be developed as novel iron supplements for iron deficiency, in which FG-FeCl 3 is considered as the best option.

Potential Precursor Compounds for Chlorohydrocarbons Detected in Gale Crater, Mars, by the SAM Instrument Suite on the Curiosity Rover

NASA Technical Reports Server (NTRS)

Miller, Kristen E.; Eigenbrode, Jennifer L.; Freissinet, Caroline; Glavin, Daniel P.; Kotrc, Benjamin; Francois, Pascaline; Summons, Roger E.

2016-01-01

The detection of chlorinated organic compounds in near-surface sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite aboard the Mars Science Laboratory Curiosity rover represents an important step toward characterizing habitable environments on Mars. However, this discovery also raises questions about the identity and source of their precursor compounds and the processes by which they become chlorinated. Here we present the results of analog experiments, conducted under conditions similar to SAM gas chromatography-mass spectrometry analyses, in which we pyrolyzed potential precursor compounds in the presence of various Cl salts and Fe oxides that have been identified in Martian sediments. While chloromethanes could not be unambiguously identified, 1,2-dichloropropane (1,2-DCP), which is one of the chlorinated compounds identified in SAM data, is formed from the chlorination of aliphatic precursors. Additionally, propanol produced more 1,2-DCP than nonfunctionalized aliphatics such as propane or hexanes. Chlorinated benzenes ranging from chlorobenzene to hexachlorobenzene were identified in experiments with benzene carboxylic acids but not with benzene or toluene. Lastly, the distribution of chlorinated benzenes depended on both the substrate species and the nature and concentration of the Cl salt. Ca and Mg perchlorate, both of which release O2 in addition to Cl2 and HCl upon pyrolysis, formed less chlorobenzene relative to the sum of all chlorinated benzenes than in experiments with ferric chloride. FeCl3, a Lewis acid, catalyzes chlorination but does not aid combustion. Accordingly, both the precursor chemistry and sample mineralogy exert important controls on the distribution of chlorinated organics.

Petrographic, fluid inclusion and isotopic study of the Dikulushi Cu-Ag deposit, Katanga (D.R.C.): implications for exploration

NASA Astrophysics Data System (ADS)

Haest, Maarten; Muchez, Philippe; Dewaele, Stijn; Boyce, Adrian J.; von Quadt, Albrecht; Schneider, Jens

2009-07-01

The Dikulushi Cu-Ag vein-type deposit is located on the Kundelungu Plateau, in the southeastern part of the Democratic Republic of Congo (D.R.C.). The Kundelungu Plateau is situated to the north of the Lufilian Arc that hosts the world-class stratiform Cu-Co deposits of the Central African Copperbelt. A combined petrographic, fluid inclusion and stable isotope study revealed that the mineralisation at Dikulushi developed during two spatially and temporally distinct mineralising episodes. An early Cu-Pb-Zn-Fe mineralisation took place during the Lufilian Orogeny in a zone of crosscutting EW- and NE-oriented faults and consists of a sequence of sulphides that precipitated from moderate-temperature, saline H2O-NaCl-CaCl2-rich fluids. These fluids interacted extensively with the country rocks. Sulphur was probably derived from thermochemical reduction of Neoproterozoic seawater sulphate. Undeformed, post-orogenic Cu-Ag mineralisation remobilised the upper part of the Cu-Pb-Zn-Fe mineralisation in an oxidising environment along reactivated and newly formed NE-oriented faults in the eastern part of the deposit. This mineralisation is dominated by massive Ag-rich chalcocite that precipitated from low-temperature H2O-NaCl-KCl fluids, generated by mixing of moderate- and low-saline fluids. The same evolution in mineralisation assemblages and types of mineralising fluids is observed in three other Cu deposits on the Kundelungu Plateau. Therefore, the recognition of two distinct types of (vein-type) mineralisation in the study area has a profound impact on the exploration in the Kundelungu Plateau region. The identification of a Cu-Ag type mineralisation at the surface could imply the presence of a Cu-Pb-Zn-Fe mineralisation at depth.

Cardiolipin modulates allosterically peroxynitrite detoxification by horse heart cytochrome c

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ascenzi, Paolo, E-mail: ascenzi@uniroma3.it; Ciaccio, Chiara; Interuniversity Consortium for the Research on the Chemistry of Metals in Biological Systems, I-70126 Bari

2011-01-07

Research highlights: {yields} Cardiolipin binding to cytochrome c. {yields} Cardiolipin-dependent peroxynitrite isomerization by cytochrome c. {yields} Cardiolipin-cytochrome c complex plays pro-apoptotic effects. {yields} Cardiolipin-cytochrome c complex plays anti-apoptotic effects. -- Abstract: Upon interaction with bovine heart cardiolipin (CL), horse heart cytochrome c (cytc) changes its tertiary structure disrupting the heme-Fe-Met80 distal bond, reduces drastically the midpoint potential out of the range required for its physiological role, binds CO and NO with high affinity, and displays peroxidase activity. Here, the effect of CL on peroxynitrite isomerization by ferric cytc (cytc-Fe(III)) is reported. In the absence of CL, hexa-coordinated cytc does notmore » catalyze peroxynitrite isomerization. In contrast, CL facilitates cytc-Fe(III)-mediated isomerization of peroxynitrite in a dose-dependent fashion inducing the penta-coordination of the heme-Fe(III)-atom. The value of the second order rate constant for CL-cytc-Fe(III)-mediated isomerization of peroxynitrite (k{sub on}) is (3.2 {+-} 0.4) x 10{sup 5} M{sup -1} s{sup -1}. The apparent dissociation equilibrium constant for CL binding to cytc-Fe(III) is (5.1 {+-} 0.8) x 10{sup -5} M. These results suggest that CL-cytc could play either pro-apoptotic or anti-apoptotic effects facilitating lipid peroxidation and scavenging of reactive nitrogen species, such as peroxynitrite, respectively.« less

Color improvement by irradiation of Curcuma aromatica extract for industrial application

NASA Astrophysics Data System (ADS)

Kim, Jae Kyung; Jo, Cheorun; Hwang, Han Joon; Park, Hyun Jin; Kim, Young Ji; Byun, Myung Woo

2006-03-01

Curcuma species are medicinal herbs with various pharmacological activities. They have a characteristic yellow color and contain curcuminoids which are natural antioxidants. In this study, Curcuma aromatica (CA) and Curcuma longa (CL) extracts were gamma-irradiated for improving the color, and the irradiation effects on the curcuminoids contents in CA and CL extracts were determined in order to evaluate if CA can replace CL on the market, where the price of CA is 70% lower than the price of CL. The Hunter color L*-values were increased significantly in all the samples with increasing dose, while the a*-values and b*-values decreased, which implies that the color of the CA and CL extracts changed from dark yellow to brighter yellow. Curcuminoids contents of all the samples were evaluated, and CA contains more curcuminoids than CL. These results indicated that irradiation improved the properties of CA for possible industrial use in manufacturing food and cosmetic industrial products.

Effect of immersion time of restorative glass ionomer cements and immersion duration in calcium chloride solution on surface hardness.

PubMed

Shiozawa, Maho; Takahashi, Hidekazu; Iwasaki, Naohiko; Wada, Takahiro; Uo, Motohiro

2014-12-01

The objective of this study was to evaluate the effect of immersion time of restorative glass ionomer cements (GICs) and immersion duration in calcium chloride (CaCl2) solution on the surface hardness. Two high-viscosity GICs, Fuji IX GP and GlasIonomer FX-II, were selected. Forty-eight specimens were randomly divided into two groups. Sixty minutes after being mixed, half of them were immersed in a 42.7wt% CaCl2 solution for 10, 30, or 60min (Group 1); the remaining specimens were immersed after an additional 1-week of storage (Group 2). The surface hardness of the specimens was measured and analyzed with two-way ANOVA and the Tukey HSD test (α=0.05). The surface compositions were examined using energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The surface hardness of Group 1 significantly increased as the immersion duration in CaCl2 increased; that of Group 2 significantly increased only after 60-minute CaCl2 immersion. After CaCl2 immersion, the amounts of Ca increased as the immersion duration increased. The surface hardness after CaCl2 immersion significantly correlated with the amount of Ca in Group 1, but not in Group 2. The binding energy of the Ca2p peak was similar to that of calcium polyalkenoate. These findings indicated that the Ca ions from the CaCl2 solution created chemical bonds with the carboxylic acid groups in the cement matrix. Immersion of GICs in CaCl2 solution at the early stage of setting was considered to enhance the formation of the polyacid salt matrix; as a result, the surface hardness increased. Copyright © 2014. Published by Elsevier Ltd.

Magnetism and electronic structures of novel layered CaFeAs{sub 2} and Ca{sub 0.75}(Pr/La){sub 0.25}FeAs{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Yi-Na; Zou, Liang-Jian, E-mail: zou@theory.issp.ac.cn; University of Science and Technology of China, Hefei, Anhui 230026

2015-05-07

The magnetic and electronic properties of the parent material CaFeAs{sub 2} of new superconductors are investigated using first-principles calculations. We predict that the ground state of CaFeAs{sub 2} is a spin-density-wave (SDW)-type striped antiferromagnet driven by Fermi surface nesting. The magnetic moment around each Fe atom is about 2.1 μ{sub B}. We also present electronic and magnetic structures of electron-doped phase Ca{sub 0.75}(Pr/La){sub 0.25}FeAs{sub 2}, the SDW order was suppressed by La/Pr substitution. The As in arsenic layers is negative monovalent and acts as blocking layers enhancing two-dimensional character by increasing the spacing distance between the FeAs layers. This favorsmore » strong antiferromagnetic fluctuations mediated pairing, implying higher T{sub c} in Ca{sub 0.75}(Pr/La){sub 0.25}FeAs{sub 2} than Ca{sub 0.75}(Pr/La){sub 0.25}Fe{sub 2}As{sub 2}.« less

The Influence of Calcium Chloride Deicing Salt on Phase Changes and Damage Development in Cementitious Materials.

PubMed

Farnam, Yaghoob; Dick, Sarah; Wiese, Andrew; Davis, Jeffrey; Bentz, Dale; Weiss, Jason

2015-11-01

The conventional CaCl 2 -H 2 O phase diagram is often used to describe how calcium chloride behaves when it is used on a concrete pavement undergoing freeze-thaw damage. However, the chemistry of the concrete can alter the appropriateness of using the CaCl 2 -H 2 O phase diagram. This study shows that the Ca(OH) 2 present in a hydrated portland cement can interact with CaCl 2 solution creating a behavior that is similar to that observed in isoplethal sections of a ternary phase diagram for a Ca(OH) 2 -CaCl 2 -H 2 O system. As such, it is suggested that such isoplethal sections provide a reasonable model that can be used to describe the behavior of concrete exposed to CaCl 2 solution as the temperature changes. Specifically, the Ca(OH) 2 can react with CaCl 2 and H 2 O resulting in the formation of calcium oxychloride. The formation of the calcium oxychloride is expansive and can produce damage in concrete at temperatures above freezing. Its formation can also cause a significant decrease in fluid ingress into concrete. For solutions with CaCl 2 concentrations greater than about 11.3 % (by mass), it is found that calcium oxychloride forms rapidly and is stable at room temperature (23 °C).

The Influence of Calcium Chloride Deicing Salt on Phase Changes and Damage Development in Cementitious Materials

PubMed Central

Farnam, Yaghoob; Dick, Sarah; Wiese, Andrew; Davis, Jeffrey; Bentz, Dale; Weiss, Jason

2015-01-01

The conventional CaCl2-H2O phase diagram is often used to describe how calcium chloride behaves when it is used on a concrete pavement undergoing freeze-thaw damage. However, the chemistry of the concrete can alter the appropriateness of using the CaCl2-H2O phase diagram. This study shows that the Ca(OH)2 present in a hydrated portland cement can interact with CaCl2 solution creating a behavior that is similar to that observed in isoplethal sections of a ternary phase diagram for a Ca(OH)2-CaCl2-H2O system. As such, it is suggested that such isoplethal sections provide a reasonable model that can be used to describe the behavior of concrete exposed to CaCl2 solution as the temperature changes. Specifically, the Ca(OH)2 can react with CaCl2 and H2O resulting in the formation of calcium oxychloride. The formation of the calcium oxychloride is expansive and can produce damage in concrete at temperatures above freezing. Its formation can also cause a significant decrease in fluid ingress into concrete. For solutions with CaCl2 concentrations greater than about 11.3 % (by mass), it is found that calcium oxychloride forms rapidly and is stable at room temperature (23 °C). PMID:26692655

Cofortification of ferric pyrophosphate and citric acid/trisodium citrate into extruded rice grains doubles iron bioavailability through in situ generation of soluble ferric pyrophosphate citrate complexes.

PubMed

Hackl, Laura; Cercamondi, Colin I; Zeder, Christophe; Wild, Daniela; Adelmann, Horst; Zimmermann, Michael B; Moretti, Diego

2016-05-01

Iron fortification of rice is a promising strategy for improving iron nutrition. However, it is technically challenging because rice is consumed as intact grains, and ferric pyrophosphate (FePP), which is usually used for rice fortification, has low bioavailability. We investigated whether the addition of a citric acid/trisodium citrate (CA/TSC) mixture before extrusion increases iron absorption in humans from FePP-fortified extruded rice grains. We conducted an iron absorption study in iron-sufficient young women (n = 20), in which each participant consumed 4 different meals (4 mg Fe/meal): 1) extruded FePP-fortified rice (No CA/TSC); 2) extruded FePP-fortified rice with CA/TSC added before extrusion (CA/TSC extruded); 3) extruded FePP-fortified rice with CA/TSC solution added after cooking and before consumption (CA/TSC solution); and 4) nonextruded rice fortified with a FeSO4 solution added after cooking and before consumption (reference). Iron absorption was calculated from erythrocyte incorporation of stable iron isotopes 14 d after administration. In in vitro experiments, we assessed the soluble and dialyzable iron from rice meals in which CA/TSC was added at different preparation stages and from meals with different iron:CA:TSC ratios. Fractional iron absorption was significantly higher from CA/TSC-extruded meals (3.2%) than from No CA/TSC (1.7%) and CA/TSC solution (1.7%; all P < 0.05) and was not different from the FeSO4 reference meal (3.4%). In vitro solubility and dialyzability were higher in CA/TSC-extruded rice than in rice with No CA/TSC and CA/TSC solution, and solubility increased with higher amounts of added CA and TSC in extruded rice. Iron bioavailability nearly doubled when CA/TSC was extruded with FePP into fortified rice, resulting in iron bioavailability comparable to that of FeSO4 We attribute this effect to an in situ generation of soluble FePP citrate moieties during extrusion and/or cooking because of the close physical proximity of FePP and CA/TSC in the extruded rice matrix. This trial was registered at clinicaltrials.gov as NCT02176759. © 2016 American Society for Nutrition.

Speciation in the Fe(III)-Cl(I)-H2O System at 298.15 K, 313.15 K, and 333.15 K (25 °C, 40 °C, and 60 °C)

NASA Astrophysics Data System (ADS)

Jamett, Nathalie E.; Hernández, Pía C.; Casas, Jesús M.; Taboada, María E.

2018-02-01

This article presents the results on speciation of ferric iron generated by the dissolution of chemical reagent hydromolysite (ferric chloride hexahydrate, FeCl3:6H2O) in water at 298.15 K, 313.15 K, and 333.15 K (25 °C, 40 °C, and 60 °C). Experiments were performed with a thermoregulated system up to the equilibrium point, as manifested by solution pH. Solution samples were analyzed in terms of concentration, pH, and electrical conductivity. Measurements of density and refractive index were obtained at different temperatures and iron concentrations. A decrease of pH was observed with the increase in the amount of dissolved iron, indicating that ferric chloride is a strong electrolyte that reacts readily with water. Experimental results were modeled using the hydrogeochemical code PHREEQC in order to obtain solution speciation. Cations and neutral and anion complexes were simultaneously present in the system at the studied conditions according to model simulations, where dominant species included Cl-, FeCl2+, FeCl2 +, FeOHCl 2 0 , and H+. A decrease in the concentration of Cl- and Fe3+ ions took place with increasing temperature due to the association of Fe-Cl species. Standard equilibrium constants for the formation of FeOHCl 2 0 obtained in this study were log Kf0 = -0.8 ± 0.01 at 298.15 K (25 °C), -0.94 ± 0.02 at 313.15 K (40 °C), and -1.03 ± 0.01 at 333.15 K (60 °C).

A chemically activated graphene-encapsulated LiFePO4 composite for high-performance lithium ion batteries.

PubMed

Ha, Jeonghyun; Park, Seung-Keun; Yu, Seung-Ho; Jin, Aihua; Jang, Byungchul; Bong, Sungyool; Kim, In; Sung, Yung-Eun; Piao, Yuanzhe

2013-09-21

A composite of modified graphene and LiFePO4 has been developed to improve the speed of charging-discharging and the cycling stability of lithium ion batteries using LiFePO4 as a cathode material. Chemically activated graphene (CA-graphene) has been successfully synthesized via activation by KOH. The as-prepared CA-graphene was mixed with LiFePO4 to prepare the composite. Microscopic observation and nitrogen sorption analysis have revealed the surface morphologies of CA-graphene and the CA-graphene/LiFePO4 composite. Electrochemical properties have also been investigated after assembling coin cells with the CA-graphene/LiFePO4 composite as a cathode active material. Interestingly, the CA-graphene/LiFePO4 composite has exhibited better electrochemical properties than the conventional graphene/LiFePO4 composite as well as bare LiFePO4, including exceptional speed of charging-discharging and excellent cycle stability. That is because the CA-graphene in the composite provides abundant porous channels for the diffusion of lithium ions. Moreover, it acts as a conducting network for easy charge transfer and as a divider, preventing the aggregation of LiFePO4 particles. Owing to these properties of CA-graphene, LiFePO4 could demonstrate enhanced and stably long-lasting electrochemical performance.

A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron

DOE PAGES

Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.

2016-05-23

We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py) 4FeCl 2. Furthermore, we prepared a series of monoalkylated salts of the type (py) 2FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py) 4FeCl 2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane thatmore » readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py) 2FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe) 2FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe) 2FeCl 2 gave the reduced Fe(0) nitrogen complex (dmpe) 2Fe(N 2). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.« less

[FeIII(SR)4]1− Complexes Can Be Synthesized By the Direct Reaction of Thiolates With FeCl3**

PubMed Central

Chang, Sechin; Koch, Stephen A.

2007-01-01

It is shown that the previously characterized [FeIII(SR)4]1− (R= Et, i-Pr, Ph) complexes can be synthesized by the direct reaction of 4 equiv of LiSR with FeCl3 in DMF solution. [FeIII(SR)4]1− complexes are synthetic analogs for the [FeIII(S-Cys)4] center in rubredoxin proteins. PMID:17723243

Assessment of groundwater quality from Bankura I and II Blocks, Bankura District, West Bengal, India

NASA Astrophysics Data System (ADS)

Nag, S. K.; Das, Shreya

2017-10-01

Hydrochemical evaluation of groundwater has been conducted in Bankura I and II Blocks to analyze and determining groundwater quality in the area. Thirty-six groundwater samples were analyzed for their physical and chemical properties using standard laboratory methods. The constituents have the following ranges in the water: pH 6.4-8.6, electrical conductivity 80-1900 μS/cm, total hardness 30-730 mg/l, TDS 48-1001 mg/l, Ca2+ 4.2-222.6 mg/l, Na+ 2.33-103.33 mg/l, Mg2+ 1.56-115.36 mg/l, K+ 0.67-14 mg/l and Fe BDL-2.53 mg/l, {HCO}3^{ - } 48.8-1000.4 mg/l, Cl- 5.6-459.86 mg/l and {SO}4^{ = } BDL-99.03 mg/l. Results also show that bicarbonate ions ( {HCO}3^{ - } ) dominate the other anions (Cl- and {SO}4^{2 - } ). Sodium adsorption ratio (SAR), soluble sodium percentage (SSP), residual sodium carbonate (RSC), magnesium adsorption ratio (MAR), total hardness (TH), and permeability index (PI) were calculated as derived parameters, to investigate the ionic toxicity. Concerned chemical parameters when plotted in the U.S. Salinity diagram indicate that waters are of C1-S1, C2-S1 and C3-S1 types, i.e., low salinity and low sodium which is good for irrigation. The values of Sodium Adsorption Ratio indicate that the groundwater of the area falls under the category of low sodium hazard. So, there is neither salinity nor toxicity problem of irrigation water, and hence the ground water can safely be used for long-term irrigation. The chemical parameters when plotted in Piper's trilinear diagram are found to concentrate in the central and west central part of the diamond-shaped field. Based on the analytical results, groundwater in the area is found to be generally fresh and hard to very hard. The abundance of the major ions is as follows: HCO3 > Cl > SO4 and Ca > Na > Mg > K > Fe. Results also show that bicarbonate ions ( {HCO}3^{ - } ) dominate the other anions (Cl- and {SO}4^{2 - } ). According to Gibbs diagrams samples fall in the rock dominance field and the chemical quality of groundwater is related to the lithology of the area. The alkaline earth elements (Ca and Mg) occur in greater abundance than alkaline elements (Na and K). A comparative study of our analytical results with the WHO standards of drinking water indicate that the present waters are also good for drinking purposes.

Binder-jetting 3D printing and alloy development of new biodegradable Fe-Mn-Ca/Mg alloys.

PubMed

Hong, Daeho; Chou, Da-Tren; Velikokhatnyi, Oleg I; Roy, Abhijit; Lee, Boeun; Swink, Isaac; Issaev, Ilona; Kuhn, Howard A; Kumta, Prashant N

2016-11-01

3D printing of various biomaterials including titanium and stainless steel has been studied for treating patients with cranio-maxillofacial bone defect. The potential long term complications with use of inert biometals have opened the opportunities for use of biodegradable metals in the clinical arena. The authors previously reported that binder-jet 3D printing technique enhanced the degradation rates of biodegradable Fe-Mn alloy by creating engineered micropores rendering the system attractive as biodegradable implantable devices. In the present study, the authors employed CALPHAD modeling to systematically study and modify the Fe-Mn alloy composition to achieve enhanced degradation rates. Accordingly, Ca and Mg addition to Fe-35wt% Mn solid solution predicted increase in degradation rates. In order to validate the CALPHAD results, Fe - (35-y)wt% Mn - ywt% X (X=Ca, Mg, and y=0, 1, 2) were synthesized by using high energy mechanical alloying (HEMA). Sintered pellets of Fe-Mn-Ca and Fe-Mn-Mg were then subjected to potentiodynamic polarization (PDP) and live/dead cell viability tests. Sintered pellets of Fe-Mn, Fe-Mn-Ca, and Fe-Mn-Mg also exhibited MC3T3 murine pre-osteoblast cells viability in the live/dead assay results. Fe-Mn and Fe-Mn-1Ca were thus accordingly selected for 3D printing and the results further confirmed enhanced degradation of Ca addition to 3D printed constructs validating the theoretical and alloy development studies. Live/dead and MTT cell viability results also confirmed good cytocompatibility of the 3D-printed Fe-Mn and Fe-Mn-1Ca constructs. Bone grafting is widely used for the treatment of cranio-maxillofacial bone injuries. 3D printing of biodegradable Fe alloy is anticipated to be advantageous over current bone grafting techniques. 3D printing offers the fabrication of precise and tailored bone grafts to fit the patient specific bone defect needs. Biodegradable Fe alloy is a good candidate for 3D printing synthetic grafts to regenerate bone tissue without eliciting complications. CALPHAD theoretical models were used to develop new Fe-Mn-Ca/Mg alloys to enhance the degradation rates of traditional Fe-Mn alloys. In vitro experimental results also showed enhanced degradation rates and good cytocompatibility of sintered Fe-Mn-Ca/Mg compacts. 3D printing of Fe-Mn and Fe-Mn-1Ca alloys further demonstrated their feasibility as potentially viable bone grafts for the future. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Essential and toxic elements in seaweeds for human consumption.

PubMed

Desideri, D; Cantaluppi, C; Ceccotto, F; Meli, M A; Roselli, C; Feduzi, L

2016-01-01

Essential elements (K, Ca, P, S, Cl, Mn, Fe, Cu, Zn, Ni, Br, and I) and nonessential or toxic elements (Al, Ti, Si, Rb, Sr, As, Cd, Sn, and Pb) were determined by energy-dispersive polarized x-ray fluorescence spectrometry in 14 seaweeds purchased in local specialty stores in Italy and consumed by humans. The differences in elements between the algae species reached up to 2-4 orders of magnitude. Lithothamnium calcareum showed the highest levels of Ca, Al, Si, Fe, and Ti. Palmaria palmata showed the highest concentrations of K, Rb, and Cl. The highest content of S was in Chondrus crispus. Laminaria digitata contained the highest concentrations of total As, Cd, Sn, Br, and I. The highest concentration of Zn was in Chlorella pyrenoidosa. Ulva lactuca displayed the highest levels of Cu, Ni, Mn, and Pb. Iodine levels ranged from 3.4 in Chlorella pyrenoidosa to 7316 mg/kg(dry) in Laminaria digitata. The nutrimental importance of essential elements was assessed using nutritional requirements. The results showed that the consumption of algae might serve as an important source of the essential elements. Health risk due to the toxic elements present in seaweed was estimated using risk estimators. Total As, Cd, and Pb concentrations ranged from <1 to 67.6, to 7.2 and to 6.7 mg/kg(dry) respectively; therefore, their contribution to total elemental intake does not appear to pose any threat to the consumers, but the concentrations of these elements should be controlled to protect the consumer against potential adverse health risks.

Compositional variability of the aerosols collected on Kerkennah Islands (central Tunisia)

NASA Astrophysics Data System (ADS)

Trabelsi, A.; Masmoudi, M.; Quisefit, J. P.; Alfaro, S. C.

2016-03-01

The aim of the present study is to investigate the seasonal variability of the aerosol concentrations and origins in central Tunisia. Four field campaigns were carried out in 2010/2011 to collect air-suspended particles on the Kerkennah Islands. The elemental composition (Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Cu, Zn, Pb, Ni, V, and As) of the particles collected in summer (June and July), autumn (September and November), winter (February and March), and spring (April and May) is determined by X-ray fluorescence analysis. Examination of the enrichment factors (EF) of all elements indicate that Al, Fe, Si, Ca, Ti, Mn, and Cr are mainly derived from soil sources, whereas Na and Cl are mostly of marine origin. Other elements such as K and Mg or S and P have multiple origins (Marine/crustal and crustal/anthropogenic, respectively). Finally, V, Cu, Ni, As, and Pb appear to be produced by anthropogenic activities. Based on the inter-elemental correlations, the mass concentrations of mineral dust (MD), sea-salt (SS) and anthropogenic (non-crustal and non-marine) sulfates (NSS) are quantified. MD, SS and NSS display significant inter-seasonal differences: on the one hand, MD and SS are the highest in spring and the lowest in winter, probably because of the seasonal change in meteorological conditions. On the other hand, NSS and Cu concentrations are above their autumn and winter values in spring and summer, which suggests the existence of a common source of the combustion type for these two pollutants.

Synthesis and characterization of Fe3O4-SiO2-AgCl photocatalyst

NASA Astrophysics Data System (ADS)

Husni, H. N.; Mahmed, N.; Ngee, H. L.

2016-07-01

Magnetite-silica-silver chloride (Fe3O4-SiO2-AgCl) coreshell particles with AgCl crystallite size of 117 nm was prepared by a wet chemistry method at ambient temperature. The magnetite-core was synthesized by using iron (II) sulfate heptahydrate (FeSO4•7H2O) and iron (III) sulfate hydrate (Fe2(SO4)3) with ammonium hydroxide (NH4OH) as the precipitating agent. The silica-shell was synthesized by using a modified Stöber process. The silver ions (Ag+) was adsorbed onto the silica surface after Söber process, followed by the addition of Cl- and polyvinylpyrrolidone (PVP) for the formation of Fe3O4-SiO2-AgCl coreshell particles. The effectiveness of the synthesized photocatalyst was investigated by monitoring the degradation of the methylene blue (MB) under sunlight for five cycles. About 90 % of the MB solution can be degraded after 2 hours. The degradation of MB solution by the Fe3O4-SiO2-AgCl particles is highly efficient for first three cycles according to the MB concentration recorded by the UV-Visible spectroscopy (UV-Vis). Nevertheless, the synthesized particles could be a promising material for photocatalytic applications.

STM/STS study of superconducting properties in Ca10(Pt4As8)(Fe2As2)5

NASA Astrophysics Data System (ADS)

Kim, Jisun; Nam, Hyoungdo; Li, Guorong; Karki, Amar; Shih, Chih-Kang; Zhang, Jiandi; Jin, Rongying; Plummer, E. W.

2014-03-01

Newly discovered iron-based superconductor, Ca10(Pt4As8)(Fe2As2)5 (Tc = 34 K) is studied using scanning tunneling microscopy/spectroscopy (STM/S). Given the symmetry of the crystal structure, several surface terminations are expected with roughly same probability: 1) Ca or partial Ca layer on top Fe2As2; 2) Ca or partial Ca layer on top Pt4As8 layer; 3) A Fe2As2 layer, and; 4) A Pt4As8layer.Surprisingly,Fe2As2 related layers (1 & 3) are rarely observed (less than 1%). Instead, we observe Pt4As8 layers separated by unit-cell-high (~ 1 nm) steps accompanied with Ca or partial Ca layer on top Pt4As8 layer (1 - 2 Å step height). Scanning tunneling spectroscopy reveals different spectra for each surface, with superconducting coherence peaks seen only on Ca layers. We argue that intermediary layers are proximity-coupled to superconducting Fe2As2 layers. The results from Ca10(Pt4As8)(Fe2As2)5 are discussed with the properties observed in other iron-based superconductors. Funded by NSF

Spectral and stratigraphic mapping of hydrated minerals associated with interior layered deposits near the southern wall of Melas Chasma, Mars

NASA Astrophysics Data System (ADS)

Liu, Yang; Goudge, Timothy A.; Catalano, Jeffrey G.; Wang, Alian

2018-03-01

Orbital remote sensing data acquired from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) onboard Mars Reconnaissance Orbiter (MRO), in conjunction with other datasets, are used to perform detailed spectral and stratigraphic analyses over a portion of south Melas Chasma, Mars. The Discrete Ordinate Radiative Transfer (DISORT) model is used to retrieve atmospherically corrected single scattering albedos from CRISM I/F data for mineral identification. A sequence of interbedded poly- and monohydrated sulfates associated with interior layered deposits (ILDs) is identified and mapped. Analyses from laboratory experiments and spectral unmixing of CRISM hyperspectral data support the hypothesis of precipitation and dehydration of multiple inputs of complex Mg-Ca-Fe-SO4-Cl brines. In this scenario, the early precipitated Mg sulfates could dehydrate into monohydrated sulfate due to catalytic effects, and the later-precipitated Mg sulfates from the late-stage "clean" brine could terminate their dehydration at mid-degree of hydration to form a polyhydrated sulfate layer due to depletion of the catalytic species (e.g., Ca, Fe, and Cl). Distinct jarosite-bearing units are identified stratigraphically above the hydrated sulfate deposits. These are hypothesized to have formed either by oxidation of a fluid containing Fe(II) and SO4, or by leaching of soluble phases from precursor intermixed jarosite-Mg sulfate units that may have formed during the later stages of deposition of the hydrated sulfate sequence. Results from stratigraphic analysis of the ILDs show that the layers have a consistent northward dip towards the interior of the Melas Chasma basin, a mean dip angle of ∼6°, and neighboring strata that are approximately parallel. These strata are interpreted as initially sub-horizontal layers of a subaqueous, sedimentary evaporite deposits that underwent post-depositional tilting from slumping into the Melas Chasma basin. The interbedded hydrated sulfate units and jarosite-bearing units, which have distinct stratigraphic relationships, are indicative of a complex sedimentary and aqueous history in south Melas Chasma.

A new method of calculating electrical conductivity with applications to natural waters

USGS Publications Warehouse

McCleskey, R. Blaine; Nordstrom, D. Kirk; Ryan, Joseph N.; Ball, James W.

2012-01-01

A new method is presented for calculating the electrical conductivity of natural waters that is accurate over a large range of effective ionic strength (0.0004–0.7 mol kg-1), temperature (0–95 °C), pH (1–10), and conductivity (30–70,000 μS cm-1). The method incorporates a reliable set of equations to calculate the ionic molal conductivities of cations and anions (H+, Li+, Na+, K+, Cs+, NH4+, Mg2+, Ca2+, Sr2+, Ba2+, F-, Cl-, Br-, SO42-, HCO3-, CO32-, NO3-, and OH-), environmentally important trace metals (Al3+, Cu2+, Fe2+, Fe3+, Mn2+, and Zn2+), and ion pairs (HSO4-, NaSO4-, NaCO3-, and KSO4-). These equations are based on new electrical conductivity measurements for electrolytes found in a wide range of natural waters. In addition, the method is coupled to a geochemical speciation model that is used to calculate the speciated concentrations required for accurate conductivity calculations. The method was thoroughly tested by calculating the conductivities of 1593 natural water samples and the mean difference between the calculated and measured conductivities was -0.7 ± 5%. Many of the samples tested were selected to determine the limits of the method and include acid mine waters, geothermal waters, seawater, dilute mountain waters, and river water impacted by municipal waste water. Transport numbers were calculated and H+, Na+, Ca2+, Mg2+, NH4+, K+, Cl-, SO42-, HCO3-, CO32-, F-, Al3+, Fe2+, NO3-, and HSO4- substantially contributed (>10%) to the conductivity of at least one of the samples. Conductivity imbalance in conjunction with charge imbalance can be used to identify whether a cation or an anion measurement is likely in error, thereby providing an additional quality assurance/quality control constraint on water analyses.

A new method of calculating electrical conductivity with applications to natural waters

NASA Astrophysics Data System (ADS)

McCleskey, R. Blaine; Nordstrom, D. Kirk; Ryan, Joseph N.; Ball, James W.

2012-01-01

A new method is presented for calculating the electrical conductivity of natural waters that is accurate over a large range of effective ionic strength (0.0004-0.7 mol kg-1), temperature (0-95 °C), pH (1-10), and conductivity (30-70,000 μS cm-1). The method incorporates a reliable set of equations to calculate the ionic molal conductivities of cations and anions (H+, Li+, Na+, K+, Cs+, NH4+, Mg2+, Ca2+, Sr2+, Ba2+, F-, Cl-, Br-, SO42-, HCO3-, CO32-, NO3-, and OH-), environmentally important trace metals (Al3+, Cu2+, Fe2+, Fe3+, Mn2+, and Zn2+), and ion pairs (HSO4-, NaSO4-, NaCO3-, and KSO4-). These equations are based on new electrical conductivity measurements for electrolytes found in a wide range of natural waters. In addition, the method is coupled to a geochemical speciation model that is used to calculate the speciated concentrations required for accurate conductivity calculations. The method was thoroughly tested by calculating the conductivities of 1593 natural water samples and the mean difference between the calculated and measured conductivities was -0.7 ± 5%. Many of the samples tested were selected to determine the limits of the method and include acid mine waters, geothermal waters, seawater, dilute mountain waters, and river water impacted by municipal waste water. Transport numbers were calculated and H+, Na+, Ca2+, Mg2+, NH4+, K+, Cl-, SO42-, HCO3-, CO32-, F-, Al3+, Fe2+, NO3-, and HSO4-substantially contributed (>10%) to the conductivity of at least one of the samples. Conductivity imbalance in conjunction with charge imbalance can be used to identify whether a cation or an anion measurement is likely in error, thereby providing an additional quality assurance/quality control constraint on water analyses.

Pre-treatment processes of Azolla filiculoides to remove Pb(II), Cd(II), Ni(II) and Zn(II) from aqueous solution in the batch and fixed-bed reactors.

PubMed

Khosravi, Morteza; Rakhshaee, Roohan; Ganji, Masuod Taghi

2005-12-09

Intact and treated biomass can remove heavy metals from water and wastewater. This study examined the ability of the activated, semi-intact and inactivated Azolla filiculoides (a small water fern) to remove Pb(2+), Cd(2+), Ni(2+) and Zn(2+) from the aqueous solution. The maximum uptake capacities of these metal ions using the activated Azolla filiculoides by NaOH at pH 10.5 +/- 0.2 and then CaCl(2)/MgCl(2)/NaCl with total concentration of 2 M (2:1:1 mole ratio) in the separate batch reactors were obtained about 271, 111, 71 and 60 mg/g (dry Azolla), respectively. The obtained capacities of maximum adsorption for these kinds of the pre-treated Azolla in the fixed-bed reactors (N(o)) were also very close to the values obtained for the batch reactors (Q(max)). On the other hand, it was shown that HCl, CH(3)OH, C(2)H(5)OH, FeCl(2), SrCl(2), BaCl(2) and AlCl(3) in the pre-treatment processes decreased the ability of Azolla to remove the heavy metals in comparison to the semi-intact Azolla, considerably. The kinetic studies showed that the heavy metals uptake by the activated Azolla was done more rapid than those for the semi-intact Azolla.

Comparative Study of Electronic Structure and Magnetic Properties of Osmate Double Perovskites: Ca2FeOsO6 versus Ca2Co(Ni)OsO6

NASA Astrophysics Data System (ADS)

Samanta, Kartik; Saha-Dasgupta, Tanusri

2018-04-01

Employing density functional theory, we study the trend in the electronic and magnetic properties of 3d-5d double perovskites, upon varying the 3d element for a fixed choice of 5d element, namely Ca2BOsO6 (B = Fe/Co/Ni). While all three compounds are reported to be ferrimagnets, the magnetic transition temperature of Ca2FeOsO6 is reported to be 2-2.4 times larger than that of Ca2CoOsO6 or Ca2NiOsO6. Our first-principles study provides microscopic insight into this trend. This trend is found to be caused by the downward shift in the position of d level energies of the B site element with respect to that of the Os t2g level upon moving across the 3d series from Fe to Co and Ni. This in turn changes the nominal valence of the Os ion from 5+ in Ca2FeOsO6 to 6+ in Ca2CoOsO6 and Ca2NiOsO6, resulting in differing superexchange paths between Ca2FeOsO6 and Ca2Co(Ni)OsO6, and additionally enabling the hybridization-mechanism-driven magnetism in Ca2FeOsO6. These together significantly enhance the magnetic transition temperature in Ca2FeOsO6 compared with that in Ca2Co(Ni)OsO6.

Elemental analysis of different varieties of rice samples using XRF technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaur, Jaspreet, E-mail: gillpreet05051812@gmail.com; Kumar, Anil, E-mail: gilljaspreet06@gmail.com

Rice is most consumed staple food in the world providing over 21% of the calorie intake of world’s population having high yielding capacity. Elements detected in rice are Al, As, Br, Cd, Cl, Co, Cs, Cu, Fe, Hg, K, Mg, Mn, Mo, Rb, Se and Zn by using Instrumental Neutron Activation with k0 standardization (R. Jayasekera etal,2004). Some of these trace elements are C, H, O, N, S, Ca, P, K, Na, Cl, Mn, Ti, Mg, Cu, Fe, Ni, Si and Zn are essential for growth of human physique The deficiency or excess of these elements in food is knownmore » to cause a variety of malnutrition or health disorders in the world. Every year, various varieties of rice are launched by Punjab Agriculture University, Ludhiana. The main purpose of which is to increases the yield to attain the maximum profit. But this leads to changing the elemental concentration in them, which may affect the human health according to variation in the nutrition values. The main objective is to study the presence of elemental concentration in various varieties of rice using EDXRF technique.« less

Efficacy of chlorine dioxide against Listeria monocytogenes in brine chilling solutions.

PubMed

Valderrama, W B; Mills, E W; Cutter, C N

2009-11-01

Chilled brine solutions are used by the food industry to rapidly cool ready-to-eat meat products after cooking and before packaging. Chlorine dioxide (ClO(2)) was investigated as an antimicrobial additive to eliminate Listeria monocytogenes. Several experiments were performed using brine solutions made of sodium chloride (NaCl) and calcium chloride (CaCl(2)) inoculated with L. monocytogenes and/or treated with 3 ppm of ClO(2). First, 10 and 20% CaCl(2) and NaCl solutions (pH 7.0) were inoculated with a five-strain cocktail of L. monocytogenes to obtain approximately 7 log CFU/ml and incubated 8 h at 0 degrees C. The results demonstrated that L. monocytogenes survived in 10% CaCl(2), 10 and 20% NaCl, and pure water. L. monocytogenes levels were reduced approximately 1.2 log CFU/ml in 20% CaCl(2). Second, inoculated ( approximately 7 log CFU/ml) brine solutions (10 and 20% NaCl and 10% CaCl(2)) treated with 3 ppm of ClO(2) resulted in a approximately 4-log reduction of the pathogen within 90 s. The same was not observed in a solution of 20% CaCl(2); further investigation demonstrated that high levels of divalent cations interfere with the disinfectant. Spent brine solutions from hot dog and ham chilling were treated with ClO(2) at concentrations of 3 or 30 ppm. At these concentrations, ClO(2) did not reduce L. monocytogenes. Removal of divalent cations and organic material in brine solutions prior to disinfection with ClO(2) should be investigated to improve the efficacy of the compound against L. monocytogenes. The information from this study may be useful to processing establishments and researchers who are investigating antimicrobials in chilling brine solutions.

Mechanism of chloride-dependent release of Ca2+ in the sarcoplasmic reticulum of rabbit skeletal muscle.

PubMed Central

Sukhareva, M; Morrissette, J; Coronado, R

1994-01-01

We investigated the effect of Cl- on the Ca2+ permeability of rabbit skeletal muscle junctional sarcoplasmic reticulum (SR) using 45Ca2+ fluxes and single channel recordings. In 45Ca2+ efflux experiments, the lumen of the SR was passively loaded with solutions of 150 mM univalent salt containing 5 mM 45Ca2+. Release of 45Ca2+ was measured by rapid filtration in the presence of extravesicular 0.4-0.8 microM free Ca2+ and 150 mM of the same univalent salt loaded into the SR lumen. The rate of release was 5-10 times higher when the univalent salt equilibrated across the SR-contained Cl- (Tris-Cl, choline-Cl, KCl) instead of an organic anion or other halides (gluconate-, methanesulfonate-, acetate-, HEPES-, Br-, I-). Cations (K+, Tris+) could be interchanged without a significant effect on the release rate. To determine whether Cl- stimulated ryanodine receptors, we measured the stimulation of release by ATP (5 mM total) and caffeine (20 mM total) and the inhibition by Mg2+ (0.8 mM estimated free) in Cl(-)-free and Cl(-)-containing solutions. The effects of ATP, caffeine, and Mg2+ were the largest in K-gluconate and Tris-gluconate, intermediate in KCl, and notably poor or absent in choline-Cl and Tris-Cl. Procaine (10 mM) inhibited the caffeine-stimulated release measured in K-gluconate, whereas the Cl- channel blocker clofibric acid (10 mM) but not procaine inhibited the caffeine-insensitive release measured in choline-Cl. Ruthenium red (20 microM) inhibited release in all solutions. In SR fused to planar bilayers we identified a nonselective Cl- channel (PCl: PTris: PCa = 1:0.5:0.3) blocked by ruthenium red and clofibric acid but not by procaine. These conductive and pharmacological properties suggested the channel was likely to mediate Cl(-)-dependent SR Ca2+ release. The absence of a contribution of ryanodine receptors to the Cl(-)-dependent release were indicated by the lack of an effect of Cl- on the open probability of this channel, a complete block by procaine, and a stimulation rather than inhibition by clofibric acid. A plug model of Cl(-)-dependent release, whereby Cl- removed the inhibition of the nonselective channel by large anions, was formulated under the assumption that nonselective channels and ryanodine receptor channels operated separately from each other in the terminal cisternae. The remarkably large contribution of Cl- to the SR Ca2+ permeability suggested that nonselective Cl- channels may control the Ca2+ permeability of the SR in the resting muscle cell. Images FIGURE 8 FIGURE 13 PMID:7948689

Association between domestic water hardness, chlorine, and atopic dermatitis risk in early life: A population-based cross-sectional study.

PubMed

Perkin, Michael R; Craven, Joanna; Logan, Kirsty; Strachan, David; Marrs, Tom; Radulovic, Suzana; Campbell, Linda E; MacCallum, Stephanie F; McLean, W H Irwin; Lack, Gideon; Flohr, Carsten

2016-08-01

Domestic water hardness and chlorine have been suggested as important risk factors for atopic dermatitis (AD). We sought to examine the link between domestic water calcium carbonate (CaCO3) and chlorine concentrations, skin barrier dysfunction (increased transepidermal water loss), and AD in infancy. We recruited 1303 three-month-old infants from the general population and gathered data on domestic water CaCO3 (in milligrams per liter) and chlorine (Cl2; in milligrams per liter) concentrations from local water suppliers. At enrollment, infants were examined for AD and screened for filaggrin (FLG) skin barrier gene mutation status. Transepidermal water loss was measured on unaffected forearm skin. CaCO3 and chlorine levels were strongly correlated. A hybrid variable of greater than and less than median levels of CaCO3 and total chlorine was constructed: a baseline group of low CaCO3/low total chlorine (CaL/ClL), high CaCO3/low total chlorine (CaH/ClL), low CaCO3/high total chlorine (CaL/ClH) and high CaCO3/high total chlorine (CaH/ClH). Visible AD was more common in all 3 groups versus the baseline group: adjusted odds ratio (AOR) of 1.87 (95% CI, 1.25-2.80; P = .002) for the CaH/ClL group, AOR of 1.46 (95% CI, 0.97-2.21; P = .07) for the CaL/ClH, and AOR of 1.61 (95% CI, 1.09-2.38; P = .02) for the CaH/ClH group. The effect estimates were greater in children carrying FLG mutations, but formal interaction testing between water quality groups and filaggrin status was not statistically significant. High domestic water CaCO3 levels are associated with an increased risk of AD in infancy. The influence of increased total chlorine levels remains uncertain. An intervention trial is required to see whether installation of a domestic device to decrease CaCO3 levels around the time of birth can reduce this risk. Copyright © 2016 American Academy of Allergy, Asthma & Immunology. Published by Elsevier Inc. All rights reserved.

Short term effects of increasing dietary salt concentrations on urine composition in healthy cats.

PubMed

Paßlack, N; Burmeier, H; Brenten, T; Neumann, K; Zentek, J

2014-09-01

High dietary salt (NaCl) concentrations are assumed to be beneficial in preventing the formation of calcium oxalate (CaOx) uroliths in cats, since increased water intake and urine volume have been observed subsequent to intake. In human beings, dietary NaCl restriction is recommended for the prevention of CaOx urolith formation, since high NaCl intake is associated with increased urinary Ca excretion. The aim of the present study was to clarify the role of dietary NaCl in the formation of CaOx uroliths in cats. Eight cats received four diets that differed in Na and Cl concentrations (0.38-1.43% Na and 0.56-2.52% Cl dry matter, DM). Each feeding period consisted of a 21 day adaptation period, followed by a 7 day sampling period for urine collection. Higher dietary NaCl concentrations were associated with increased urine volume and renal Na excretion. Urinary Ca concentration was constant, but renal Ca excretion increased from 0.62 to 1.05 mg/kg bodyweight (BW)/day with higher dietary NaCl concentrations (P ≤ 0.05). Urinary oxalate (Ox), citrate, P and K concentrations decreased when NaCl intake was high (P ≤ 0.05), and urinary pH was low in all groups (6.33-6.45; P > 0.05). Relative supersaturation of CaOx in the urine was unaffected by dietary NaCl concentrations. In conclusion, the present study demonstrated several beneficial effects of high dietary NaCl intake over a relatively short time period. In particular, urinary Ca concentration remained unchanged because of increased urine volume. Decreased urinary Ox concentrations might help to prevent the formation of CaOx uroliths, but this should be verified in future studies in diseased or predisposed cats. Copyright © 2014 Elsevier Ltd. All rights reserved.

Activation of chloride channels in normal and cystic fibrosis airway epithelial cells by multifunctional calcium/calmodulin-dependent protein kinase

NASA Astrophysics Data System (ADS)

Wagner, John A.; Cozens, Alison L.; Schulman, Howard; Gruenert, Dieter C.; Stryer, Lubert; Gardner, Phyllis

1991-02-01

CYSTIC fibrosis is associated with defective regulation of apical membrane chloride channels in airway epithelial cells. These channels in normal cells are activated by cyclic AMP-dependent protein kinase1,2 and protein kinase C3,4. In cystic fibrosis these kinases fail to activate otherwise normal Cl- channels1-4. But Cl- flux in cystic fibrosis cells, as in normal cells, can be activated by raising intracellular Ca2+ (refs 5-10). We report here whole-cell patch clamp studies of normal and cystic fibrosis-derived airway epithelial cells showing that Cl- channel activation by Ca2+ is mediated by multifunctional Ca2+/calmodulin-dependent protein kinase. We find that intracellular application of activated kinase and ATP activates a Cl- current similar to that activated by a Ca2+ ionophore, that peptide inhibitors of either the kinase or calmodulin block Ca2+-dependent activation of Cl- channels, and that a peptide inhibitor of protein kinase C does not block Ca2+-dependent activation. Ca2+/calmodulin activation of Cl- channels presents a pathway with therapeutic potential for circumventing defective regulation of Cl- channels in cystic fibrosis.

Restaurant consumer acceptance of beef loin strip steaks tenderized with calcium chloride.

PubMed

Hoover, L C; Cook, K D; Miller, M F; Huffman, K L; Wu, C K; Lansdell, J L; Ramsey, C B

1995-12-01

Beef strip loins from either the right or left side of 22 carcasses of Bos indicus-type steers were injected with 200 mM calcium chloride (CaCl2) solution at 5% (wt/wt) to determine its effect on tenderness and other selected quality traits of steaks. Loins from opposite sides of the carcasses were untreated and served as the control. The steaks were evaluated for tenderness, juiciness, flavor intensity, tenderness acceptability, and overall acceptability by 62 restaurant consumers over a 6-wk period. The CaCl2 injection improved (P < .05) tenderness and flavor intensity ratings by the restaurant consumers. Tenderness acceptability and overall acceptability were improved 23 and 17%, respectively, by the CaCl2 injection. Flavor was not compromised by the CaCl2 injection. The CaCl2-treated steaks were rated superior(P < .05) for flavor compared to the control steaks. Restaurant consumers preferred the beef loin strip steaks injected with 200 mM CaCl2 at 5% (wt/wt). The results of this study are interpreted to indicate that, from a restaurant consumer perspective, CaCl2 injection is an acceptable means of making beef a more consistently tender product.

Characterizing the Fate and Mobility of Phosphorus in Utah Lake Sediments

NASA Astrophysics Data System (ADS)

Carling, G. T.; Randall, M.; Nelson, S.; Rey, K.; Hansen, N.; Bickmore, B.; Miller, T.

2017-12-01

An increasing number of lakes worldwide are impacted by eutrophication and harmful algal blooms due to anthropogenic nutrient inputs. Utah Lake is a unique eutrophic freshwater lake that is naturally shallow, turbid, and alkaline with high dissolved oxygen levels that has experienced severe algal blooms in recent years. Recently, the Utah Division of Water Quality has proposed a new limitation of phosphorus (P) loading to Utah Lake from wastewater treatment plants in an effort to mitigate eutrophication. However, reducing external P loads may not lead to immediate improvements in water quality due to the legacy pool of nutrients in lake sediments. The purpose of this study was to characterize the fate and mobility of P in Utah Lake sediments to better understand P cycling in this unique system. We analyzed P speciation, mineralogy, and binding capacity in lake sediment samples collected from 15 locations across Utah Lake. P concentrations in sediment ranged from 615 to 1894 ppm, with highest concentrations in Provo Bay near the major metropolitan area. Sequential leach tests indicate that 25-50% of P is associated with Ca (CaCO₃/ Ca10(PO4)6(OH,F,Cl)2 ≈ P) and 40-60% is associated with Fe (Fe(OOH) ≈ P). Ca-associated P was confirmed by SEM images, which showed the highest P concentrations correlating with Ca (carbonate minerals/apatite). The Ca-associated P fraction is likely immobile, but the Fe-bound P is potentially bioavailable under changing redox conditions. Batch sorption results indicate that lake sediments have a high capacity to absorb and remove P from the water column, with an average uptake of 70-96% removal over the range of 1-10 mg/L P. Mineral precipitation and sorption to bottom sediments is an efficient removal mechanism of P in Utah Lake, but a significant portion of P may be temporarily available for resuspension and cycling in surface waters. Mitigating lake eutrophication is a complex problem that goes beyond decreasing external nutrient loads to the water body and requires a better understanding in-lake P cycling.

Mass closure and source apportionment of PM2.5 by Positive Matrix Factorization analysis in urban Mediterranean environment

NASA Astrophysics Data System (ADS)

Mantas, E.; Remoundaki, E.; Halari, I.; Kassomenos, P.; Theodosi, C.; Hatzikioseyian, A.; Mihalopoulos, N.

2014-09-01

A systematic monitoring of PM2.5 was carried out during a period of three years (from February 2010 to April 2013) at an urban site, at the National Technical University of Athens campus. Two types of 24-h PM2.5 samples have been collected: 271 samples on PTFE and 116 samples on quartz filters. Daily PM2.5 concentrations were determined for both types of samples. Total sulfur, crustal origin elements and elements of a major crustal component (Al, Si, Fe, Ca, K, Mg, Ti) trace elements (Zn, Pb, Cu, Ni, P, V, Cr, Mn) and water soluble ions (Cl-, NO3-, SO42-, Na+, K+, NH4+, Ca2+, Mg2+) were determined on the PTFE samples. Organic carbon (OC), elemental carbon (EC) and water soluble ions were determined on the quartz samples. For the mass closure six components were considered: Secondary Inorganic Aerosol (SIA), Organic Matter (OM), Elemental Carbon (EC), Dust, Mineral anthropogenic component (MIN) and Sea Salt (SS). SIA and OM contributed in the mass of PM2.5 almost equally: 30-36% and 30% respectively. EC, SS and MIN accounted for 5, 4 and 3% respectively of the total PM2.5 mass. Dust accounted for about 3-5% in absence of dust transport event and reached a much higher percentage in case of dust transport event. These contributions justify at least 80% of the PM2.5 mass. Source apportionment analysis has been performed by Positive Matrix Factorization. The combination of the PMF results obtained by both data sets lead to the definition of six factors: 1. SO42-, NH4+, OC (industrial/regional sources, secondary aerosol) 2. EC, OC, K and trace metals (traffic and heating by biomass burning, locally emitted aerosol). 3. Ca, EC, OC and trace metals (urban-resuspended road dust reflecting exhaust emissions), 4. Secondary nitrates 5. Na, Cl (marine source) 6. Si, Al, Ti, Ca, Fe (Dust transported from Sahara). These factors reflect not only main sources contributions but also underline the key role of atmospheric dynamics and aerosol ageing processes in this Mediterranean environment.

Signers and co-speech gesturers adopt similar strategies for portraying viewpoint in narratives.

PubMed

Quinto-Pozos, David; Parrill, Fey

2015-01-01

Gestural viewpoint research suggests that several dimensions determine which perspective a narrator takes, including properties of the event described. Events can evoke gestures from the point of view of a character (CVPT), an observer (OVPT), or both perspectives. CVPT and OVPT gestures have been compared to constructed action (CA) and classifiers (CL) in signed languages. We ask how CA and CL, as represented in ASL productions, compare to previous results for CVPT and OVPT from English-speaking co-speech gesturers. Ten ASL signers described cartoon stimuli from Parrill (2010). Events shown by Parrill to elicit a particular gestural strategy (CVPT, OVPT, both) were coded for signers' instances of CA and CL. CA was divided into three categories: CA-torso, CA-affect, and CA-handling. Signers used CA-handling the most when gesturers used CVPT exclusively. Additionally, signers used CL the most when gesturers used OVPT exclusively and CL the least when gesturers used CVPT exclusively. Copyright © 2014 Cognitive Science Society, Inc.

Dissolution of nontronite in chloride brines and implications for the aqueous history of Mars

NASA Astrophysics Data System (ADS)

Steiner, M. H.; Hausrath, E. M.; Elwood Madden, M. E.; Tschauner, O.; Ehlmann, B. L.; Olsen, A. A.; Gainey, S. R.; Smith, J. S.

2016-12-01

Increasing evidence suggests the presence of recent liquid water, including brines, on Mars. Brines have therefore likely impacted clay minerals such as the Fe-rich mineral nontronite found in martian ancient terrains. To interpret these interactions, we conducted batch experiments to measure the apparent dissolution rate constant of nontronite at 25.0 °C at activities of water (aH2O) of 1.00 (0.01 M CaCl2 or NaCl), 0.75 (saturated NaCl or 3.00 mol kg-1 CaCl2), and 0.50 (5.00 mol kg-1 CaCl2). Experiments at aH2O = 1.00 (0.01 M CaCl2) were also conducted at 4.0 °C, 25.0 °C, and 45.0 °C to measure an apparent activation energy for the dissolution of nontronite. Apparent dissolution rate constants at 25.0 °C in CaCl2-containing solutions decrease with decreasing activity of water as follows: 1.18 × 10-12 ± 9 × 10-14 mol mineral m-2 s-1 (aH2O = 1.00) > 2.36 × 10-13 ± 3.1 × 10-14 mol mineral m-2 s-1 (aH2O = 0.75) > 2.05 × 10-14 ± 2.9 × 10-15 mol mineral m-2 s-1 (aH2O = 0.50). Similar results were observed at 25.0 °C in NaCl-containing solutions: 1.89 × 10-12 ± 1 × 10-13 mol mineral m-2 s-1 (aH2O = 1.00) > 1.98 × 10-13 ± 2.3 × 10-14 mol mineral m-2 s-1 (aH2O = 0.75). This decrease in apparent dissolution rate constants with decreasing activity of water follows a relationship of the form: log kdiss = 3.70 ± 0.20 × aH2O - 15.49, where kdiss is the apparent dissolution rate constant, and aH2O is the activity of water. The slope of this relationship (3.70 ± 0.20) is within uncertainty of that of other minerals where the relationship between dissolution rates and activity of water has been tested, including forsteritic olivine (log R = 3.27 ± 0.91 × aH2O - 11.00) (Olsen et al., 2015) and jarosite (log R = 3.85 ± 0.43 × aH2O - 12.84) (Dixon et al., 2015), where R is the mineral dissolution rate. This result allows prediction of mineral dissolution as a function of activity of water and suggests that with decreasing activity of water, mineral dissolution will decrease due to the role of water as a ligand in the reaction. Apparent dissolution rate constants in the dilute NaCl solution (1.89 × 10-12 ± 1 × 10-13 mol mineral m-2 s-1) are slightly greater than those in the dilute CaCl2 solutions (1.18 × 10-12 ± 9 × 10-14 mol mineral m-2 s-1). We attribute this effect to the exchange of Na with Ca in the nontronite interlayer. An apparent activation energy of 54.6 ± 1.0 kJ/mol was calculated from apparent dissolution rate constants in dilute CaCl2-containing solutions at temperatures of 4.0 °C, 25.0 °C, and 45.0 °C: 2.33 × 10-13 ± 1.3 × 10-14 mol mineral m-2 s-1 (4.0 °C), 1.18 × 10-12 ± 9 × 10-14 mol mineral m-2 s-1 (25.0 °C), and 4.98 × 10-12 ± 3.8 × 10-13 mol mineral m-2 s-1 (45.0 °C). The greatly decreased dissolution of nontronite in brines and at low temperatures suggests that any martian nontronite found to be perceptibly weathered may have experienced very long periods of water-rock interaction with brines at the low temperatures prevalent on Mars, with important implications for the paleoclimate and long-term potential habitability of Mars.

Creation of a 3Mn/1Fe cluster in the oxygen-evolving complex of photosystem II and investigation of its functional activity.

PubMed

Semin, B К; Davletshina, L N; Seibert, M; Rubin, A B

2018-01-01

Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H 2 Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH5.7) than at neutral pH (3Mn/RC are extracted at pH6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extract only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster. Also we found that the presence of Fe cations in a heteronuclear cluster (2Mn/2Fe) increases the resistance of the remaining Mn cations to H 2 Q action, since H 2 Q can extract Mn cations from homonuclear Mn clusters of PSII(-Ca,4Mn) and PSII(-Ca,2Mn) membranes but not from the heteronuclear cluster in PSII(-Ca,2Mn,2Fe) membranes. H 2 Q also cannot extract Mn from PSII membranes obtained by incubation of PSII(-Ca,4Mn) membranes with Fe(II) cations at pH5.7, which suggests the formation of a heteronuclear 3Mn/1Fe cluster in the OEC. Functional activity of PSII with a 3Mn/1Fe cluster was investigated. PSII preparations with a 3Mn/1Fe cluster in the OEC are able to photoreduce the exogenous electron acceptor 2,6-dichlorophenolindophenol, possibly due to incomplete oxidation of water molecules as is the case with PSII(-Ca,2Mn,2Fe) samples. However, in the contrast to PSII(-Ca,2Mn,2Fe) samples PSII(-Ca,3Mn,1Fe) membranes can evolve O 2 at a low rate in the presence of exogenous Ca 2+ (at about 27% of the rate of O 2 evolution in native PSII membranes). The explanation for this phenomenon (either water splitting and production of molecular O 2 by the 3Mn/1Fe cluster or apparent O 2 evolution due to minor contamination of PSII(3Mn,1Fe) samples with PSII(-Ca,4Mn) membranes) is discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Calcium interacts with antifreeze proteins and chitinase from cold-acclimated winter rye.

PubMed

Stressmann, Maja; Kitao, Satoshi; Griffith, Marilyn; Moresoli, Christine; Bravo, León A; Marangoni, Alejandro G

2004-05-01

During cold acclimation, winter rye (Secale cereale) plants accumulate pathogenesis-related proteins that are also antifreeze proteins (AFPs) because they adsorb onto ice and inhibit its growth. Although they promote winter survival in planta, these dual-function AFPs proteins lose activity when stored at subzero temperatures in vitro, so we examined their stability in solutions containing CaCl2, MgCl2, or NaCl. Antifreeze activity was unaffected by salts before freezing, but decreased after freezing and thawing in CaCl2 and was recovered by adding a chelator. Ca2+ enhanced chitinase activity 3- to 5-fold in unfrozen samples, although hydrolytic activity also decreased after freezing and thawing in CaCl2. Native PAGE, circular dichroism, and Trp fluorescence experiments showed that the AFPs partially unfold after freezing and thawing, but they fold more compactly or aggregate in CaCl2. Ruthenium red, which binds to Ca(2+)-binding sites, readily stained AFPs in the absence of Ca2+, but less stain was visible after freezing and thawing AFPs in CaCl2. We conclude that the structure of AFPs changes during freezing and thawing, creating new Ca(2+)-binding sites. Once Ca2+ binds to those sites, antifreeze activity, chitinase activity and ruthenium red binding are all inhibited. Because free Ca2+ concentrations are typically low in the apoplast, antifreeze activity is probably stable to freezing and thawing in planta. Ca2+ may regulate chitinase activity if concentrations are increased locally by release from pectin or interaction with Ca(2+)-binding proteins. Furthermore, antifreeze activity can be easily maintained in vitro by including a chelator during frozen storage.

Determination of hyperin in seed of Cuscuta chinensis Lam. by enhanced chemiluminescence of CdTe quantum dots on calcein/K3Fe(CN)6 system.

PubMed

Kang, Jing; Li, Xuwen; Geng, Jiayang; Han, Lu; Tang, Jieli; Jin, Yongri; Zhang, Yihua

2012-10-15

In this paper, 3-mercaptocarboxylic acid (MPA) modified CdTe quantum dots (QDs) were used as sensitizers, to enhance the chemiluminescence (CL) of the calcein/K(3)Fe(CN)(6) system. A new CL system of CdTe/calcein/K(3)Fe(CN)(6) was developed. The effects of reactant concentrations and the particle sizes of CdTe QDs on the CL emission were investigated in detail. The possible enhancement mechanism of the CL was also further investigated based on the photoluminescence (PL) and CL spectra. Polyphenols such as chlorogenic acid, quercetin, hyperin, catechin and kaempferol, were observed to inhibit the CL signal of the CdTe/calcein/K(3)Fe(CN)(6) system and determined by the proposed method. The proposed method was applied to the determination of hyperin in seed of Cuscuta chinensis Lam. and the results obtained were satisfactory. Copyright © 2012 Elsevier Ltd. All rights reserved.

Crystalline and Electronic Structures and Magnetic and Electrical Properties of La-Doped Ca2Fe2O5 Compounds

NASA Astrophysics Data System (ADS)

Phan, T. L.; Tho, P. T.; Tran, N.; Kim, D. H.; Lee, B. W.; Yang, D. S.; Thiet, D. V.; Cho, S. L.

2018-01-01

Brownmillerite Ca2Fe2O5 has been observed to exhibit many outstanding properties that are applicable to ecotechnology. However, very little work on doped Ca2Fe2O5 compounds has been carried out to widen their application scope. We present herein a detailed study of the crystalline/geometric and electronic structures and magnetic and electrical properties of Ca2- x La x Fe2O5 ( x = 0 to 1) prepared by conventional solid-state reaction. X-ray diffraction patterns indicated that the compounds with x = 0 to 0.05 exhibited brownmillerite-type single phase. La doping with higher content ( x ≥ 0.1) stimulated additive formation of Grenier- (LaCa2Fe3O8) and perovskite-type (LaFeO3) phases. Extended x-ray absorption fine structure spectroscopy at the Fe K-edge and electron spin resonance spectroscopy revealed presence of Fe3+ in the parent Ca2Fe2O5 ( x = 0) and both Fe3+ and Fe4+ in the doped compounds ( x ≥ 0.05). The Fe4+ content tended to increase with increasing x. This stimulates ferromagnetic exchange interactions between Fe3+ and Fe4+ ions and directly influences the magnetic properties of Ca2- x La x Fe2O5. Electrical resistivity ( ρ) measurements in the temperature range of T = 20 K to 400 K revealed that all the compounds exhibit insulator behavior; the ρ( T) data for x ≥ 0.1 could be described based on the adiabatic small polaron hopping model.

Transport of carboxyl-functionalized carbon black nanoparticles in saturated porous media: Column experiments and model analyses

NASA Astrophysics Data System (ADS)

Kang, Jin-Kyu; Yi, In-Geol; Park, Jeong-Ann; Kim, Song-Bae; Kim, Hyunjung; Han, Yosep; Kim, Pil-Je; Eom, Ig-Chun; Jo, Eunhye

2015-06-01

The aim of this study was to investigate the transport behavior of carboxyl-functionalized carbon black nanoparticles (CBNPs) in porous media including quartz sand, iron oxide-coated sand (IOCS), and aluminum oxide-coated sand (AOCS). Two sets of column experiments were performed under saturated flow conditions for potassium chloride (KCl), a conservative tracer, and CBNPs. Breakthrough curves were analyzed to obtain mass recovery and one-dimensional transport model parameters. The first set of experiments was conducted to examine the effects of metal (Fe, Al) oxides and flow rate (0.25 and 0.5 mL min- 1) on the transport of CBNPs suspended in deionized water. The results showed that the mass recovery of CBNPs in quartz sand (flow rate = 0.5 mL min- 1) was 83.1%, whereas no breakthrough of CBNPs (mass recovery = 0%) was observed in IOCS and AOCS at the same flow rate, indicating that metal (Fe, Al) oxides can play a significant role in the attachment of CBNPs to porous media. In addition, the mass recovery of CBNPs in quartz sand decreased to 76.1% as the flow rate decreased to 0.25 mL min- 1. Interaction energy profiles for CBNP-porous media were calculated using DLVO theory for sphere-plate geometry, demonstrating that the interaction energy for CBNP-quartz sand was repulsive, whereas the interaction energies for CBNP-IOCS and CBNP-AOCS were attractive with no energy barriers. The second set of experiments was conducted in quartz sand to observe the effect of ionic strength (NaCl = 0.1 and 1.0 mM; CaCl2 = 0.01 and 0.1 mM) and pH (pH = 4.5 and 5.4) on the transport of CBNPs suspended in electrolyte. The results showed that the mass recoveries of CBNPs in NaCl = 0.1 and 1.0 mM were 65.3 and 6.4%, respectively. The mass recoveries of CBNPs in CaCl2 = 0.01 and 0.1 mM were 81.6 and 6.3%, respectively. These results demonstrated that CBNP attachment to quartz sand can be enhanced by increasing the electrolyte concentration. Interaction energy profiles demonstrated that the interaction energy profile for CBNP-quartz sand was compressed and that the energy barrier decreased as the electrolyte concentration increased. Furthermore, the mass recovery of CBNPs in the presence of divalent ions (CaCl2 = 0.1 mM) was far lower than that in the presence of monovalent ions (NaCl = 0.1 mM), demonstrating a much stronger effect of Ca2 + than Na+ on CBNP transport. Mass recovery of CBNPs at pH 4.5 was 55.6%, which was lower than that (83.1%) at pH 5.4, indicating that CBNP attachment to quartz sand can be enhanced by decreasing the pH. The sticking efficiencies (α) calculated from the mass recovery by colloid filtration theory were in the range from 2.1 × 10- 2 to 4.5 × 10- 1, which were far greater than the values (2.56 × 10- 6-3.33 × 10- 2) of theoretical sticking efficiencies (αtheory) calculated from the DLVO energy by the Maxwell model.

A bicarbonate- and weak acid-permeable chloride conductance controlled by cytosolic Ca2+ and ATP in rat submandibular acinar cells.

PubMed

Ishikawa, T

1996-09-01

A Ca(2+)-activated Cl- conductance in rat submandibular acinar cells was identified and characterized using whole-cell patch-clamp technique. When the cells were dialyzed with Cs-glutamate-rich pipette solutions containing 2 mM ATP and 1 microM free Ca2+ and bathed in N-methyl-D-glucamine chloride (NMDG-Cl) or Choline-Cl-rich solutions, they mainly exhibited slowly activating currents. Dialysis of the cells with pipette solutions containing 300 nM or less than 1 nM free Ca2+ strongly reduced the Cl- currents, indicating the currents were Ca(2+)-dependent. Relaxation analysis of the "on" currents of slowly activating currents suggested that the channels were voltage-dependent. The anion permeability sequence of the Cl- channels was: NO3- (2.00) > I- (1.85) > or = Br- (1.69) > Cl- (1.00) > bicarbonate (0.77) > or = acetate (0.70) > propionate (0.41) > > glutamate (0.09). When the ATP concentration in the pipette solutions was increased from 0 to 10 mM, the Ca(2+)-dependency of the Cl- current amplitude shifted to lower free Ca2+ concentrations by about two orders of magnitude. Cells dialyzed with a pipette solution (pCa = 6) containing ATP-gamma S (2 mM) exhibited currents of similar magnitude to those observed with the solution containing ATP (2 mM). The addition of the calmodulin inhibitors trifluoperazine (100 microM) or calmidazolium (25 microM) to the bath solution and the inclusion of KN-62 (1 microM), a specific inhibitor of calmodulin kinase, or staurosporin (10 nM), an inhibitor of protein kinase C to the pipette solution had little, if any, effect on the Ca(2+)-activated Cl- currents. This suggests that Ca2+/Calmodulin or calmodulin kinase II and protein kinase C are not involved in Ca(2+)-activated Cl- currents. The outward Cl- currents at +69 mV were inhibited by NPPB (100 microM), IAA-94 (100 microM), DIDS (0.03-1 mM), 9-AC (300 microM and 1 mM) and DPC (1 mM), whereas the inward currents at -101 mV were not. These results demonstrate the presence of a bicarbonate- and weak acid-permeable Cl- conductance controlled by cytosolic Ca2+ and ATP levels in rat submandibular acinar cells.

Enhanced degradation of trichloroethene by calcium peroxide activated with Fe(III) in the presence of citric acid

PubMed Central

ZHANG, Xiang; GU, Xiaogang; LU, Shuguang; MIAO, Zhouwei; XU, Minhui; FU, Xiaori; DANISH, Muhammad; Brusseau, Mark L.; QIU, Zhaofu; SUI, Qian

2017-01-01

Trichloroethene (TCE) degradation by Fe(III)-activated calcium peroxide (CP) in the presence of citric acid (CA) in aqueous solution was investigated. The results demonstrated that the presence of CA enhanced TCE degradation significantly by increasing the concentration of soluble Fe(III) and promoting H2O2 generation. The generation of HO• and O2−• in both the CP/Fe(III) and CP/Fe(III)/CA systems was confirmed with chemical probes. The results of radical scavenging tests showed that TCE degradation was due predominantly o direct oxidation by HO•, while O2−• strengthened the generation of HO• by promoting Fe(III) transformation in the CP/Fe(III)/CA system. Acidic pH conditions were favorable for TCE degradation, and the TCE degradation rate decreased with increasing pH. The presence of Cl−, HCO3−, and humic acid (HA) inhibited TCE degradation to different extents for the CP/Fe(III)/CA system. Analysis of Cl− production suggested that TCE degradation in the CP/Fe(III)/CA system occurred through a dechlorination process. In summary, this study provided detailed information for the application of CA-enhanced Fe(III)-activated calcium peroxide for treating TCE contaminated groundwater. PMID:28959499

Geochemical signatures of groundwater in the coastal aquifers of Thiruvallur district, south India

NASA Astrophysics Data System (ADS)

Senthilkumar, S.; Balasubramanian, N.; Gowtham, B.; Lawrence, J. F.

2017-03-01

An attempt has been made to identify the chemical processes that control the hydrochemistry of groundwater in the coastal aquifers of Thiruvallur coastal village of Thiruvallur district, Tamil Nadu, south India. The parameters such as pH, EC, TDS and major ion concentrations of Na, K, Ca, Mg, Cl, HCO3, SO4 and NO3 of the groundwater were analyzed. Abundances of these ions are in the following order Na > Ca > Mg > K and HCO3 > Cl > SO4 > NO3. The dominant water types are in the order of NaCl> mixed CaMgCl > CaHCO3 > CaNaHCO3. Water types (mixed CaHCO3, mixed CaMgCl and NaCl) suggest that the mixing of high salinity water caused from surface contamination sources such as irrigation return flow, domestic wastewater and septic tank effluents with existing water followed by ion exchange reaction processes, silicate weathering and evaporation are responsible for the groundwater chemistry of the study area. The above statement is further supported by Gibbs plot where most of the samples fall within the evaporation zone.

Influence of solution acidity and CaCl2 concentration on the removal of heavy metals from metal-contaminated rice soils.

PubMed

Kuo, S; Lai, M S; Lin, C W

2006-12-01

Soil washing is considered a useful technique for remediating metal-contaminated soils. This study examined the release edges of Cd, Zn, Ni, Cr, Cu or Pb in two contaminated rice soils from central Taiwan. The concentrations exceeding the trigger levels established by the regulatory agency of Taiwan were Cu, Zn, Ni and Cr for the Ho-Mei soil and Pb for the Nan-Tou soil. Successive extractions with HCl ranging from 0 to 0.2 M showed increased release of the heavy metals with declining pH, and the threshold pH value below which a sharp increase in the releases of the heavy metals was highest for Cd, Zn, and Ni (pH 4.6 to 4.9), intermediate for Pb and Cu (3.1 to 3.8) and lowest for Fe (2.1), Al (2.2) and Cr (1.7) for the soils. The low response slope of Ni and Cr particularly for the rice soils make soil washing with the acid up to the highest concentration used ineffective to reduce their concentrations to below trigger levels. Although soil washing with 0.1 M HCl was moderately effective in reducing Cu, Pb, Zn and Cd, which brought pH of the soils to 1.1+/-0.1 (S.D.), the concurrent release of large quantities of Fe and Al make this remediation technique undesirable for the rice soils containing high clay. Successive washings with 0.01 M HCl could be considered an alternative as the dissolution of Fe and Al was minimal, and between 46 to 64% of Cd, Zn, and Cu for the Ho-Mei soil and 45% of Pb in the Na-Tou soil were extracted after four successive extractions with this dilute acid solution. The efficacy of Cd extraction improved if CaCl2 was added to the acid solution. The correlation analysis revealed that Cr extracted was highly correlated (P < 0.001) with Fe extracted, whereas the Cu, Ni, Zn, Cd or Pb extracted was better correlated (P < 0.001) with Al than with Fe extracted. It is possible that the past seasonal soil flooding and drainage in the soils for rice production was conducive to incorporating Cr within the structure of Fe oxide, thereby making them extremely insoluble even in 0.2 M HCl solution. The formation of solid solution of Ni with Al oxide was also possible, making it far less extractable than Cd, Zn, Cu, or Pb with the acid concentrations used.

Calcium deprivation increases the palatability of calcium solutions in rats.

PubMed

McCaughey, Stuart A; Forestell, Catherine A; Tordoff, Michael G

2005-02-15

Calcium-deprived rats have elevated intakes of CaCl2, other calcium salts, and some non-calcium compounds. We used taste reactivity to examine the effects of calcium deprivation on the palatability of CaCl2 and other solutions. Nine male Sprague-Dawley rats were calcium-deprived by maintenance on a low-calcium diet, and eight replete rats were used as controls. All rats were videotaped during intraoral infusion of the following solutions: 30 and 300 mM CaCl2, 30 mM calcium lactate, 100 and 600 mM NaCl, 30 mM MgCl2, 1 mM quinine.HCl, 2.5 mM sodium saccharin, and deionized water. We counted individual orofacial and somatic movements elicited by the infusions and used them to calculate total ingestive and aversive scores. Relative to controls, calcium-deprived rats gave a significantly larger number of tongue protrusions and had higher total ingestive scores for CaCl2, calcium lactate, NaCl, and MgCl2. Our results suggest that CaCl2, calcium lactate, NaCl, and MgCl2 taste more palatable to rats when they are calcium-deprived than replete, and this may be responsible for the increased intake of these solutions following calcium deprivation.

Effect of Initial FeO Content and CaO:SiO2 Ratio on the Reduction Smelting Kinetics of the CaO-SiO2-MgOsatd.-FeO Slag System

NASA Astrophysics Data System (ADS)

Kim, Jong Bae; Sohn, Il

2018-02-01

The effect of the initial FeO content and CaO:SiO2 ratio (CaO mass pct/SiO2 mass pct) on the reduction smelting of FeO with carbon flake addition is investigated in the CaO-MgOsatd.-SiO2-FeO slag system at 1823 K (1550 °C). Carbon rapidly reacted with FeO in the molten slag, causing both foaming and compositional changes in the slag. As FeO is reduced, the MgO saturation is modified, and solid precipitants, including MgO and other complex oxides, were observed, which significantly affected the slag properties, including the viscosity and foaming behavior. The solid-phase fraction and viscosity were estimated from changes in the measured FeO content over time using the thermochemical software FactSage. The iron recovery, which is distinguished from the amount of reduced Fe droplets, showed opposite behavior to the measured maximum foaming height and modified foaming index. According to the FeO mass transfer coefficient considering slag foaming at various initial FeO contents and CaO:SiO2 ratios, the reduction rate was optimal at higher initial FeO contents and a CaO:SiO2 ratio of 2.0, which did not correspond to the optimal iron recovery at an initial FeO content of 44 mass pct and above and a CaO:SiO2 ratio of 1.2. The results showed that slag foaming may increase the reduction kinetics, but the slag composition needs to be optimized for greater iron recovery.

Direct Conversion of Greenhouse Gas CO2 into Graphene via Molten Salts Electrolysis.

PubMed

Hu, Liwen; Song, Yang; Jiao, Shuqiang; Liu, Yingjun; Ge, Jianbang; Jiao, Handong; Zhu, Jun; Wang, Junxiang; Zhu, Hongmin; Fray, Derek J

2016-03-21

Producing graphene through the electrochemical reduction of CO2 remains a great challenge, which requires precise control of the reaction kinetics, such as diffusivities of multiple ions, solubility of various gases, and the nucleation/growth of carbon on a surface. Here, graphene was successfully created from the greenhouse gas CO2 using molten salts. The results showed that CO2 could be effectively fixed by oxygen ions in CaCl2-NaCl-CaO melts to form carbonate ions, and subsequently electrochemically split into graphene on a stainless steel cathode; O2 gas was produced at the RuO2-TiO2 inert anode. The formation of graphene in this manner can be ascribed to the catalysis of active Fe, Ni, and Cu atoms at the surface of the cathode and the microexplosion effect through evolution of CO in between graphite layers. This finding may lead to a new generation of proceedures for the synthesis of high value-added products from CO2, which may also contribute to the establishment of a low-carbon and sustainable world. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Micro-spatial variation of elemental distribution in estuarine sediment and their accumulation in mangroves of Indian Sundarban.

PubMed

Bakshi, Madhurima; Ram, S S; Ghosh, Somdeep; Chakraborty, Anindita; Sudarshan, M; Chaudhuri, Punarbasu

2017-05-01

This work describes the micro-spatial variation of elemental distribution in estuarine sediment and bioaccumulation of those elements in different mangrove species of the Indian Sundarbans. The potential ecological risk due to such elemental load on this mangrove-dominated habitat is also discussed. The concentrations of elements in mangrove leaves and sediments were determined using energy-dispersive X-ray fluorescence spectroscopy. Sediment quality and potential ecological risks were assessed from the calculated indices. Our data reflects higher concentration of elements, e.g., Al, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, and Pb, in the sediment, as compared to that reported by earlier workers. Biological concentration factors for K, Ca, Mn, Fe, Cu, and Zn in different mangroves indicated gradual elemental bioaccumulation in leaf tissues (0.002-1.442). Significant variation was observed for elements, e.g., Ni, Mn, and Ca, in the sediments of all the sites, whereas in the plants, significant variation was found for P, S, Cl, K, Ca, Mn, Fe, Cu, and Zn. This was mostly due to the differences in uptake and accumulation potential of the plants. Various sediment quality indices suggested the surface sediments to be moderately contaminated and suffering from progressive deterioration. Cu, Cr, Zn, Mn, and Ni showed higher enrichment factors (0.658-1.469), contamination factors (1.02-2.7), and geo-accumulation index (0.043-0.846) values. The potential ecological risk index values considering Cu, Cr, Pb, and Zn were found to be within "low ecological risk" category (20.04-24.01). However, Cr and Ni in the Sundarban mangroves exceeded the effect range low and probable effect level limits. Strong correlation of Zn with Fe and K was observed, reflecting their similar transportation and accumulation process in both sediment and plant systems. The plant-sediment elemental correlation was found to be highly non-linear, suggesting role of some physiological and edaphic factors in the accumulation process. Overall, the study of micro-spatial distribution of elements can act as a useful tool for determining health of estuarine ecosystem.

Electron paramagnetic resonance g-tensors from state interaction spin-orbit coupling density matrix renormalization group

NASA Astrophysics Data System (ADS)

Sayfutyarova, Elvira R.; Chan, Garnet Kin-Lic

2018-05-01

We present a state interaction spin-orbit coupling method to calculate electron paramagnetic resonance g-tensors from density matrix renormalization group wavefunctions. We apply the technique to compute g-tensors for the TiF3 and CuCl42 - complexes, a [2Fe-2S] model of the active center of ferredoxins, and a Mn4CaO5 model of the S2 state of the oxygen evolving complex. These calculations raise the prospects of determining g-tensors in multireference calculations with a large number of open shells.

Handbook of Isotopes in the Cosmos

NASA Astrophysics Data System (ADS)

Clayton, Donald

2007-08-01

List of illustrations; Preface; Introduction; 1. Hydrogen (H); 2. Helium (He); 3. Lithium (Li); 4. Beryllium (Be); 5. Boron (B); 6. Carbon (C); 7. Nitrogen (N); 8. Oxygen (O); 9. Fluorine (F); 10. Neon (Ne); 11. Sodium (Na); 12. Magnesium (Mg); 13. Aluminium (Al); 14. Silicon (Si); 15. Phosphorous (P); 16. Sulphur (S); 17. Chlorine (Cl); 18. Argon (Ar); 19. Potassium (K); 20. Calcium (Ca); 21. Scandium (Sc); 22. Titanium (Ti); 23. Vanadium (V); 24. Chromium (Cr); 25. Manganese (Mn); 26. Iron (Fe); 27. Cobalt (Co); 28. Nickel (Ni); 29. Copper (Cu); 30. Zinc (Zn); 31. Gallium (Ga); Glossary.

Handbook of Isotopes in the Cosmos

NASA Astrophysics Data System (ADS)

Clayton, Donald

2003-09-01

List of illustrations; Preface; Introduction; 1. Hydrogen (H); 2. Helium (He); 3. Lithium (Li); 4. Beryllium (Be); 5. Boron (B); 6. Carbon (C); 7. Nitrogen (N); 8. Oxygen (O); 9. Fluorine (F); 10. Neon (Ne); 11. Sodium (Na); 12. Magnesium (Mg); 13. Aluminium (Al); 14. Silicon (Si); 15. Phosphorous (P); 16. Sulphur (S); 17. Chlorine (Cl); 18. Argon (Ar); 19. Potassium (K); 20. Calcium (Ca); 21. Scandium (Sc); 22. Titanium (Ti); 23. Vanadium (V); 24. Chromium (Cr); 25. Manganese (Mn); 26. Iron (Fe); 27. Cobalt (Co); 28. Nickel (Ni); 29. Copper (Cu); 30. Zinc (Zn); 31. Gallium (Ga); Glossary.

Analysis of Lung Tissue Using Ion Beams

NASA Astrophysics Data System (ADS)

Alvarez, J. L.; Barrera, R.; Miranda, J.

2002-08-01

In this work a comparative study is presented of the contents of metals in lung tissue from healthy patients and with lung cancer, by means of two analytical techniques: Particle Induced X-ray Emission (PIXE) and Rutherford Backscattering Spectrometry (RBS). The samples of cancerous tissue were taken from 26 autopsies made to individuals died in the National Institute of Respiratory Disease (INER), 22 of cancer and 4 of other non-cancer biopsies. When analyzing the entirety of the samples, in the cancerous tissues, there were increments in the concentrations of S (4%), K (635%), Co (85%) and Cu (13%). Likewise, there were deficiencies in the concentrations of Cl (59%), Ca (6%), Fe (26%) and Zn (7%). Only in the cancerous tissues there were appearances of P, Ca, Ti, V, Cr, Mn, Ni, Br and Sr. The tissue samples were classified according to cancer types (adenocarcinomas, epidermoides and of small cell carcinoma), personal habits (smokers and alcoholic), genetic predisposition and residence place. There was a remarkable decrease in the concentration of Ca and a marked increment in the Cu in the epidermoide tissue samples with regard to those of adenocarcinoma or of small cells cancer. Also, decrements were detected in K and increments of Fe, Co and Cu in the sample belonging to people that resided in Mexico City with regard to those that resided in the State of Mexico.

Organic-Silica Interactions in Saline: Elucidating the Structural Influence of Calcium in Low-Salinity Enhanced Oil Recovery.

PubMed

Desmond, J L; Juhl, K; Hassenkam, T; Stipp, S L S; Walsh, T R; Rodger, P M

2017-09-08

Enhanced oil recovery using low-salinity solutions to sweep sandstone reservoirs is a widely-practiced strategy. The mechanisms governing this remain unresolved. Here, we elucidate the role of Ca 2+ by combining chemical force microscopy (CFM) and molecular dynamics (MD) simulations. We probe the influence of electrolyte composition and concentration on the adsorption of a representative molecule, positively-charged alkylammonium, at the aqueous electrolyte/silica interface, for four electrolytes: NaCl, KCl, MgCl 2 , and CaCl 2 . CFM reveals stronger adhesion on silica in CaCl 2 compared with the other electrolytes, and shows a concentration-dependent adhesion not observed for the other electrolytes. Using MD simulations, we model the electrolytes at a negatively-charged amorphous silica substrate and predict the adsorption of methylammonium. Our simulations reveal four classes of surface adsorption site, where the prevalence of these sites depends only on CaCl 2 concentration. The sites relevant to strong adhesion feature the O - silica site and Ca 2+ in the presence of associated Cl - , which gain prevalence at higher CaCl 2 concentration. Our simulations also predict the adhesion force profile to be distinct for CaCl 2 compared with the other electrolytes. Together, these analyses explain our experimental data. Our findings indicate in general how silica wettability may be manipulated by electrolyte concentration.

Pressure-induced phase transition in titanium alloys

NASA Astrophysics Data System (ADS)

Murugeswari, R.; Rajeswarapalanichamy, R.; Benial, A. Milton Franklin

2018-05-01

The structural, elastic, magnetic and electronic properties of titanium-based ferromagnetic (FM) TiX (X = Fe, Co, Ni) alloys are investigated by the first principles calculations based on density functional theory using the Vienna ab initio simulation code. At ambient pressure, all the three alloys TiFe, TiCo and TiNi are highly stable in CsCl structure. The calculated lattice parameters and ground state properties are in good agreement with the available theoretical and experimental results. The density of states explains that these alloys possess the metallic nature at normal and high pressures. A pressure-induced structural phase transitions from CsCl to NaCl phase at 46 GPa and NaCl to ZB phase at 49 GPa in TiFe, CsCl to ZB phase in TiCo at 52 GPa, CsCl to hexagonal phase at 22 GPa and hexagonal to ZB phase at 66 GPa in TiNi are observed. The calculated Debye temperatures of TiX (X = Fe, Co, Ni) alloys are in good agreement with earlier reports. Binding energy shows that the TiCo is the most stable alloy. The magnetic property of TiX (X = Fe, Co, Ni) alloys reveals that TiFe is stable in nonmagnetic phase and the other two alloys, TiCo and TiNi, are stable in FM phase at normal pressure.

Resolving the multifaceted mechanisms of the ferric chloride thrombosis model using an interdisciplinary microfluidic approach

PubMed Central

Ciciliano, Jordan C.; Sakurai, Yumiko; Myers, David R.; Fay, Meredith E.; Hechler, Beatrice; Meeks, Shannon; Li, Renhao; Dixon, J. Brandon; Lyon, L. Andrew; Gachet, Christian

2015-01-01

The mechanism of action of the widely used in vivo ferric chloride (FeCl3) thrombosis model remains poorly understood; although endothelial cell denudation is historically cited, a recent study refutes this and implicates a role for erythrocytes. Given the complexity of the in vivo environment, an in vitro reductionist approach is required to systematically isolate and analyze the biochemical, mass transfer, and biological phenomena that govern the system. To this end, we designed an “endothelial-ized” microfluidic device to introduce controlled FeCl3 concentrations to the molecular and cellular components of blood and vasculature. FeCl3 induces aggregation of all plasma proteins and blood cells, independent of endothelial cells, by colloidal chemistry principles: initial aggregation is due to binding of negatively charged blood components to positively charged iron, independent of biological receptor/ligand interactions. Full occlusion of the microchannel proceeds by conventional pathways, and can be attenuated by antithrombotic agents and loss-of-function proteins (as in IL4-R/Iba mice). As elevated FeCl3 concentrations overcome protective effects, the overlap between charge-based aggregation and clotting is a function of mass transfer. Our physiologically relevant in vitro system allows us to discern the multifaceted mechanism of FeCl3-induced thrombosis, thereby reconciling literature findings and cautioning researchers in using the FeCl3 model. PMID:25931587

Potential Anticancer Heterometallic Fe-Au and Fe-Pd Agents: Initial Mechanistic Insights

PubMed Central

Lease, Nicholas; Vasilevski, Vadim; Carreira, Monica; de Almeida, Andreia; Sanaú, Mercedes; Hirva, Pipsa; Casini, Angela; Contel, Maria

2013-01-01

A series of gold(III) and palladium(II) heterometallic complexes with new iminophosphorane ligands derived from ferrocenyl-phosphanes [{Cp-P(Ph2)=N-Ph}2Fe] (1), [{Cp-P(Ph2)=N-CH2-2-NC5H4}2Fe] (2) and [{Cp-P(Ph2)=N-CH2-2-NC5H4}Fe(Cp)] (3) have been synthesized and structurally characterized. Ligands 2 and 3 afford stable coordination complexes [AuCl2(3)]ClO4, [{AuCl2}2(2)](ClO4)2, [PdCl2(3)] and [{PdCl2}2(2)]. The complexes have been evaluated for their antripoliferative properties in human ovarian cancer cells sensitive and resistant to cisplatin (A2780S/R), in human breast cancer cells (MCF7) and in a non-tumorigenic human embryonic kidney cell line (HEK-293T). The highly cytotoxic trimetallic derivatives M2Fe (M = Au, Pd) are more cytotoxic to cancer cells than their corresponding monometallic fragments. Moreover, these complexes were significantly more cytotoxic than cisplatin in the resistant A2780R and the MCF7 cell lines. Studies of the interactions of the trimetallic compounds with DNA and the zinc-finger protein PARP-1 indicate that they exert anticancer effects in vitro based on different mechanisms of actions with respect to cisplatin. PMID:23786413

Scanning Electron Microscope-Cathodoluminescence Analysis of Rare-Earth Elements in Magnets.

PubMed

Imashuku, Susumu; Wagatsuma, Kazuaki; Kawai, Jun

2016-02-01

Scanning electron microscope-cathodoluminescence (SEM-CL) analysis was performed for neodymium-iron-boron (NdFeB) and samarium-cobalt (Sm-Co) magnets to analyze the rare-earth elements present in the magnets. We examined the advantages of SEM-CL analysis over conventional analytical methods such as SEM-energy-dispersive X-ray (EDX) spectroscopy and SEM-wavelength-dispersive X-ray (WDX) spectroscopy for elemental analysis of rare-earth elements in NdFeB magnets. Luminescence spectra of chloride compounds of elements in the magnets were measured by the SEM-CL method. Chloride compounds were obtained by the dropwise addition of hydrochloric acid on the magnets followed by drying in vacuum. Neodymium, praseodymium, terbium, and dysprosium were separately detected in the NdFeB magnets, and samarium was detected in the Sm-Co magnet by the SEM-CL method. In contrast, it was difficult to distinguish terbium and dysprosium in the NdFeB magnet with a dysprosium concentration of 1.05 wt% by conventional SEM-EDX analysis. Terbium with a concentration of 0.02 wt% in an NdFeB magnet was detected by SEM-CL analysis, but not by conventional SEM-WDX analysis. SEM-CL analysis is advantageous over conventional SEM-EDX and SEM-WDX analyses for detecting trace rare-earth elements in NdFeB magnets, particularly dysprosium and terbium.

Solid-State Reaction Between Fe-Al-Ca Alloy and Al2O3-CaO-FeO Oxide During Heat Treatment at 1473 K (1200 °C)

NASA Astrophysics Data System (ADS)

Liu, Chengsong; Yang, Shufeng; Li, Jingshe; Ni, Hongwei; Zhang, Xueliang

2017-04-01

The aim of this study was to control the physicochemical characteristics of inclusions in steel through appropriate heat treatment. Using a confocal scanning laser microscope (CSLM) and pipe furnace, the solid-state reactions between Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide during heat treatment at 1473 K (1200 °C) and the influence of these reactions on the compositions of and phases in the alloy and oxide were investigated by the diffusion couple method. Suitable pretreatment of the oxide using a CSLM and production of the diffusion couple of Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide gave good contact between the alloy and oxide. The diffusion couple was then sealed in a quartz tube with a piece of Ti foil to lower oxygen partial pressure and a block of Fe-Al-Ca alloy was introduced to conduct heat treatment experiments. Solid-state reactions between the alloy and oxide during heat treatment at 1473 K (1200 °C) were analyzed and discussed. A dynamic model to calculate the width of the particle precipitation zone based on the Wagner model of internal oxidation of metal was proposed. This model was helpful to understand the solid-state reaction mechanism between Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide.

Purification and partial biochemical-genetic characterization of trehalose 6-phosphate synthase from muscles of adult female Ascaris suum.

PubMed

Dmitryjuk, M; Dopieralska, M; Łopieńska-Biernat, E; Frączek, R J

2013-06-01

Trehalose 6-phosphate (T6P) synthase (TPS; EC 2.4.1.15) was isolated from muscles of Ascaris suum by ammonium sulphate fractionation, ion-exchange DEAE SEPHACEL(TM) anion exchanger column chromatography and Sepharose 6B gel filtration. On sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE), 265-fold purified TPS exhibited a molecular weight of 66 kDa. The optimum pH and temperature of the purified enzyme were 3.8-4.2 and 35°C, respectively. The isoelectric point (pI) of TPS was pH 5.4. The studied TPS was not absolutely substrate specific. Besides glucose 6-phosphate, the enzyme was able to use fructose 6-phosphate as an acceptor of glucose. TPS was activated by 10 mM MgCl2, 10 mM CaCl2 and 10 mM NaCl. In addition, it was inhibited by ethylenediaminetetra-acetic acid (EDTA), KCl, FeCl3 and ZnCl2. Two genes encoding TPS were isolated and sequenced from muscles of the parasite. Complete coding sequences for tps1 (JF412033.2) and tps2 (JF412034.2) were 3917 bp and 3976 bp, respectively. Translation products (AEX60788.1 and AEX60787.1) showed expression to the glucosyltransferase-GTB-type superfamily.

Singular value decomposition approach to the yttrium occurrence in mineral maps of rare earth element ores using laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Romppanen, Sari; Häkkänen, Heikki; Kaski, Saara

2017-08-01

Laser-induced breakdown spectroscopy (LIBS) has been used in analysis of rare earth element (REE) ores from the geological formation of Norra Kärr Alkaline Complex in southern Sweden. Yttrium has been detected in eudialyte (Na15 Ca6(Fe,Mn)3 Zr3Si(Si25O73)(O,OH,H2O)3 (OH,Cl)2) and catapleiite (Ca/Na2ZrSi3O9·2H2O). Singular value decomposition (SVD) has been employed in classification of the minerals in the rock samples and maps representing the mineralogy in the sampled area have been constructed. Based on the SVD classification the percentage of the yttrium-bearing ore minerals can be calculated even in fine-grained rock samples.

Groundwater arsenic and fluoride in Rajnandgaon District, Chhattisgarh, northeastern India

NASA Astrophysics Data System (ADS)

Patel, Khageshwar Singh; Sahu, Bharat Lal; Dahariya, Nohar Singh; Bhatia, Amarpreet; Patel, Raj Kishore; Matini, Laurent; Sracek, Ondra; Bhattacharya, Prosun

2017-07-01

The groundwater of Ambagarh Chouki, Rajnandgaon, India, shows elevated levels of As and F-, frequently above the WHO guidelines. In this work, the concentrations of As, F-, Na+, Mg2+, Ca2+, Cl-, SO4 2-, HCO3 -, Fe, dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) in the groundwater of Ambagarh Chouki are described. The sources of dissolved components in the groundwater are investigated using the cluster and factor analysis. Five factors have been identified and linked to processes responsible for the formation of groundwater chemistry. High concentrations of dissolved As seems to be linked to high concentrations of DOC, suggesting reductive dissolution of ferric oxyhydroxides as arsenic mobilization process. Fluoride is found in shallow depth water, presumably as a consequence of evaporation of water and removal of Ca2+ by precipitation of carbonates.

Inhibitory effects of HgCl2 on excitation-secretion coupling at the motor nerve terminal and excitation-contraction coupling in the muscle cell.

PubMed

Røed, A; Herlofson, B B

1994-12-01

1. Indirect and direct twitch (0.1-Hz) stimulation of the rat phrenic nerve-diaphragm disclosed that the inhibitory effect of HgCl2, 3.7 x 10(-5) M, on the neuromuscular transmission and in the muscle cell, was accelerated by 10-sec periods of 50-Hz tetanic stimulation every 10 min. This activity-dependent enhancement suggested an inhibitory mechanism of HgCl2 related to the development of fatigue, like membrane depolarization or decreased excitability, decreased availability of transmitter, or interference with the factors controlling excitation-secretion coupling of the nerve terminal, i.e. (Ca2+)0 or (Ca2+)i, and excitation-contraction coupling in the muscle cell, i.e., (Ca2+)i. 2. During both indirect and direct stimulation, HgCl2-induced inhibition was enhanced markedly by pretreatment with caffeine, which releases Ca2+ from endoplasmic and sarcoplasmic reticulum in the nerve terminal and muscle cell, respectively. This caffeine-induced enhancement was completely antagonized by dantrolene, which inhibits the caffeine-induced release. However, dantrolene alone did not antagonize the HgCl2-induced inhibition. 3. Since caffeine depletes the intracellular Ca2+ stores of the smooth endoplasmic reticulum, HgCl2 probably inhibits by binding to SH groups of transport proteins conveying the messenger function of (Ca2+)i. In the muscle cell this leads to inhibition of contraction. In the nerve terminal, an additional enhancement of the HgCl2-induced inhibition, by inhibiting reuptake of choline by TEA and tetanic stimulation, suggested that HgCl2 inhibited a (Ca2+)i signal necessary for this limiting factor in resynthesis of acetylcholine. 4. The (Ca2+)0 signal necessary for stimulus-induced release of acetylcholine was not affected by HgCl2. Hyperpolarization in K(+)-free solution antagonized the inhibitory effect of HgCl2 at indirect stimulation, and Ca(2+)-free solution enhanced the inhibitory effect at direct stimulation. K+ depolarization, membrane electric field increase with high Ca2+, membrane stabilization with lidocaine, and half-threshold stimulation, did not change the inhibitory effect of HgCl CH3HgCl. 1.85 x 10(-5) M, disclosed a synergistic interaction with caffeine during direct, but not during indirect, stimulation.

Effect of an annealing on magnetic properties of Fe-Ni films electroplated in citric-acid-based plating baths

NASA Astrophysics Data System (ADS)

Yanai, T.; Koda, K.; Eguchi, K.; Morimura, T.; Takashima, K.; Nakano, M.; Fukunaga, H.

2018-04-01

We have already reported Fe-Ni films with good soft magnetic properties prepared by using an electroplating method. In the present study, we employed an annealing for further improvement in soft magnetic properties of the electroplated Fe-Ni films. The annealing reduces the coercivity of the films, and the reduction rate of the coercivity depended on the Cl- ion concentration in the bath. The Fe22Ni78 films prepared in the plating bath with high Cl- ion concentration showed large reduction rate of the coercivity, and we found that the annealing is more effective for high Cl- ion concentration bath since much lower coercivity value can be obtained compared with that for low Cl- ion concentration one.

[Effects of different salt and alkali stresses on ion distribution in Red globe/Beta grapevines].

PubMed

Du, Yuan-peng; Jin, Xue-juan; Guo, Shu-hua; Fu, Qing-qing; Zhai, Heng

2015-06-01

The potted Red globe/Beta grapevines were selected to irrigated with NaCl, Na2SO4, NaHCO3, NH4Cl, (NH4)2SO4. Hence, the ions which induced leaf etiolation were screened and the impacts of different salt and alkali on ion distribution in different organs of grapevines were investigated. It was found that NaHCO3 exerted the greatest effects on grapevines, leaf etiolation at 14 days after treatment. By contrast, NaCl and NH4Cl treatments induced leaf etiolation at 28 days after treatment. The Na+ content in all the detected organs were significantly increased under NaHCO3 and NaCl treatment, and Na+ content in root under NaHCO3 treatment was 6.4 times as that in control root. NaHCO3 and NaCl treatments significantly decreased K+ content in the organs with the exception of leaf. NaHCO3 treatment significantly decreased K/Na in different organs, which declined to 0.1 in root. By contrast, NaCl treatment significantly decreased K/Na in the detected organs with exception of stem. Besides, the transport of Ca2+, Mg2+, Fe2+ to aboveground organs was significantly decreased by NaHCO3 and NaCl treatments. K/Na ratio in the detected organs were decreased under NH4Cl, (NH4) 2SO4 and Na2SO4 treatments, especially under NH4 Cl treatment. Taken together, NaHCO3 was the primary factor resulting in leaf etiolation, followed by NaCl and NH4Cl, while (NH4) 2SO4 and Na2SO4 produced impacts.

Characteristics of Catalytic Gasification of Natural Coke with H2O in a Fluidized Bed

NASA Astrophysics Data System (ADS)

Lin, L. S.; Zhao, C. S.; Wang, S.; Zhu, G.; Xiang, W. G.

The experimental investigation on gasification characteristics of natural coke from Peicheng, Jiangsu with steam were conducted in a fluidized bed gasifier setup. The effects of several parameters, in terms of the catalyst type, the catalyst mixed manner and the dosage of catalyst over coke on the yield, the components, the heating value of fuel gas and the carbon conversion rate were examined. Results indicate that the fluidized bed gasification technology could overcome the shortcomings of natural coke. Ca-, Fe- and Cu-based nitrates could improve the gasification reaction effectively with a little difference, they could be listed in a descending sequence as follows: Cu-based>Fe-based>Ca-based according to their catalytic effect. The influences of Fe/Ca ratio and Cu/Ca ratio on gasification are similar, gas yield, carbon conversion rate and gas heating value per hour increase as Fe/Ca ratio or Cu/Ca ratio increases, but all of them go up first and then drop with decrease in Fe/Cu ratio. When the dosage of Ca-, Fe- and Cu-based nitrates mixed with the ratio of Ca/Fe/Cu= 10/35/55 is 3%, the best catalytic effect is achieved.

Fabrication of CaFe2O4 nanofibers via electrospinning method with enhanced visible light photocatalytic activity

NASA Astrophysics Data System (ADS)

Wang, Jianmin; Wang, Yunan; Liu, Yinglei; Li, Song; Cao, Feng; Qin, Gaowu

CaFe2O4 nanofibers with diameters of about 130nm have been fabricated via a facile electrospinning method. The structures, morphologies and optical properties of the obtained CaF2O4 nanofibers have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-Visible UV-Vis diffuse reflectance spectrum. The photocatalytic activities of the CaFe2O4 nanofibers are evaluated by the photo-degradation of Methyl orange (MO). The results show that the CaFe2O4 nanofibers (72%) exhibit much higher photocatalytic performance than the CaFe2O4 powders (27%) prepared by conventional method under visible light irradiation. The enhanced photocatalytic performance of CaFe2O4 nanofibers could be attributed to the large surface area, high photogenerated charge carriers density and low charge transfer resistance, as revealed by photoelectrochemical measurement. And fundamentally, it could be attributed to the decreased particle size and the fibrous nanostructure. This work not only provides an efficient way to improve the photocatalytic activity of CaFe2O4, but also provides a new method for preparing materials with nanofibrous structure.

Molecular dynamics simulation, ab initio calculation, and size-selected anion photoelectron spectroscopy study of initial hydration processes of calcium chloride

NASA Astrophysics Data System (ADS)

He, Zhili; Feng, Gang; Yang, Bin; Yang, Lijiang; Liu, Cheng-Wen; Xu, Hong-Guang; Xu, Xi-Ling; Zheng, Wei-Jun; Gao, Yi Qin

2018-06-01

To understand the initial hydration processes of CaCl2, we performed molecular simulations employing the force field based on the theory of electronic continuum correction with rescaling. Integrated tempering sampling molecular dynamics were combined with ab initio calculations to overcome the sampling challenge in cluster structure search and refinement. The calculated vertical detachment energies of CaCl2(H2O)n- (n = 0-8) were compared with the values obtained from photoelectron spectra, and consistency was found between the experiment and computation. Separation of the Cl—Ca ion pair is investigated in CaCl2(H2O)n- anions, where the first Ca—Cl ionic bond required 4 water molecules, and both Ca—Cl bonds are broken when the number of water molecules is larger than 7. For neutral CaCl2(H2O)n clusters, breaking of the first Ca—Cl bond starts at n = 5, and 8 water molecules are not enough to separate the two ion pairs. Comparing with the observations on magnesium chloride, it shows that separating one ion pair in CaCl2(H2O)n requires fewer water molecules than those for MgCl2(H2O)n. Coincidentally, the solubility of calcium chloride is higher than that of magnesium chloride in bulk solutions.

2:1 Charge disproportionation in perovskite-structure oxide La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Haichuan; Hosaka, Yoshiteru; Seki, Hayato

La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+} was synthesized at a high pressure and high temperature. The compound crystallizes in a √2a×2a×√2a perovskite cell in which the La and Ca ions at the A site are disordered. At 217 K the Fe{sup 3.67+} shows charge disproportionation to Fe{sup 3+} and Fe{sup 5+} in a ratio of 2:1, and this disproportionation is accompanied by transitions in magnetic and transport properties. The charge-disproportionated Fe{sup 3+} and Fe{sup 5+} are arranged along the <111> direction of the cubic perovskite cell. The local electronic and magnetic environments of Fe in La{sub 1/3}Ca{sub 2/3}FeO{submore » 3} are quite similar to those of Fe in La{sub 1/3}Sr{sub 2/3}FeO{sub 3}, and the 2:1 charge disproportionation pattern of Fe{sup 3+} and Fe{sup 5+} in La{sub 1/3}Ca{sub 2/3}FeO{sub 3} is also the same as that in La{sub 1/3}Sr{sub 2/3}FeO{sub 3}. - Graphical abstract: The perovskite-structure oxide La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+} shows charge disproportionation to Fe{sup 3+} and Fe{sup 5+} in a ratio of 2:1, and the charge-disproportionated Fe{sup 3+} and Fe{sup 5+} are arranged along the <111> direction of the cubic perovskite cell. - Highlights: • La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+} was synthesized at a high pressure and high temperature. • At 217 K the Fe{sup 3.67+} shows charge disproportionation (CD) to Fe{sup 3+} and Fe{sup 5+} in a ratio of 2:1. • The charge-disproportionated Fe{sup 3+} and Fe{sup 5+} are arranged along the <111> direction of the cubic perovskite cell. • The disproportionation is accompanied by transitions in magnetic and transport properties.« less

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

DOE PAGES

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.; ...

2017-10-06

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Isolation and characterization of a novel lectin from the mushroom Armillaria luteo-virens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, K.; College of Food Science, Heilongjiang August First Land Reclamation University, Daqing 163319; Liu, Q.H.

2006-07-14

From the dried fruiting bodies of the mushroom Armillaria luteo-virens, a dimeric lectin with a molecular mass of 29.4 kDa has been isolated. The purification procedure involved (NH{sub 4}){sub 2}SO{sub 4} precipitation, ion exchange chromatography on DEAE-cellulose, CM-cellulose, and Q-Sepharose, and gel filtration by fast protein liquid chromatography on Superdex 75. The hemagglutinating activity of the lectin could not be inhibited by simple sugars but was inhibited by the polysaccharide inulin. The activity was stable up to 70 {sup o}C but was acid- and alkali-labile. Salts including FeCl{sub 3}, AlCl{sub 3}, and ZnCl{sub 2} inhibited the activity whereas MgCl{sub 2},more » MnCl{sub 2}, and CaCl{sub 2} did not. The lectin stimulated mitogenic response of mouse splenocytes with the maximal response achieved by 1 {mu}M lectin. Proliferation of tumor cells including MBL2 cells, HeLa cells, and L1210 cells was inhibited by the lectin with an IC{sub 5} of 2.5, 5, and 10 {mu}M, respectively. However, proliferation of HepG2 cells was not affected. The novel aspects of the isolated lectin include a novel N-terminal sequence, fair thermostability, acid stability, and alkali stability, together with potent mitogenic activity toward spleen cells and antiproliferative activity toward tumor cells.« less

First-principles calculations for XAS of infinite-layer iron oxides

NASA Astrophysics Data System (ADS)

Kodera, Mitsuru; Shishidou, Tatsuya; Oguchi, Tamio

2011-03-01

The oxygen defect perovskite SrFe O3 - x shows various properties such as the giant magnetoresistance effect and the thermoelectric effect. It had been believed that the oxygen content in SrFe O3 - x changes up to x = 0.5 . Recently, Tsujimoto et al . have succeeded in synthesizing the infinite-layer iron oxide SrFe O2 . SrFe O2 has a square-planar oxygen coordination, while the iron oxides usually have the tetrahedral and octahedral coordination. CaFe O2 has also infinite layer structure and the same magnetic ordering as SrFe O2 . However, it is suggested that the oxygen coordination of CaFe O2 is different from that of SrFe O2 . In order to investigate the electronic structure of iron in (Ca, Sr) Fe O2 , the x-ray absorption spectroscopy (XAS) spectrum has been measured. In this work, we perform the calculation for XAS spectrum near the Fe-K edge of (Ca, Sr) Fe O2 using the first-principles calculations. We compare the results with the experiment and discuss the electronic structure of iron in (Ca, Sr) Fe O2 .

Mineral Content and Biochemical Variables of Aloe vera L. under Salt Stress

PubMed Central

Murillo-Amador, Bernardo; Córdoba-Matson, Miguel Víctor; Villegas-Espinoza, Jorge Arnoldo; Hernández-Montiel, Luis Guillermo; Troyo-Diéguez, Enrique; García-Hernández, José Luis

2014-01-01

Despite the proven economic importance of Aloe vera, studies of saline stress and its effects on the biochemistry and mineral content in tissues of this plant are scarce. The objective of this study was to grow Aloe under NaCl stress of 0, 30, 60, 90 and 120 mM and compare: (1) proline, total protein, and enzyme phosphoenolpyruvate carboxylase (PEP-case) in chlorenchyma and parenchyma tissues, and (2) ion content (Na, K, Ca, Mg, Cl, Fe, P. N, Zn, B, Mn, and Cu) in roots, stems, leaves and sprouts. Proline and PEP-case increased as salinity increased in both parenchyma and chlorenchyma, while total protein increased in parenchyma and decreased in chlorenchyma, although at similar salt concentrations total protein was always higher in chlorenchyma. As salinity increased Na and Cl ions increased in roots, stems, leaves, while K decreased only significantly in sprouts. Salinity increases typically caused mineral content in tissue to decrease, or not change significantly. In roots, as salinity increased Mg decreased, while all other minerals failed to show a specific trend. In stems, the mineral concentrations that changed were Fe and P which increased with salinity while Cu decreased. In leaves, Mg, Mn, N, and B decreased with salinity, while Cu increased. In sprouts, the minerals that decreased with increasing salinity were Mg, Mn, and Cu. Zinc did not exhibit a trend in any of the tissues. The increase in protein, proline and PEP-case activity, as well as the absorption and accumulation of cations under moderate NaCl stress caused osmotic adjustment which kept the plant healthy. These results suggest that Aloe may be a viable crop for soil irrigated with hard water or affected by salinity at least at concentrations used in the present study. PMID:24736276

Osmotic Stress Induces Expression of Choline Monooxygenase in Sugar Beet and Amaranth1

PubMed Central

Russell, Brenda L.; Rathinasabapathi, Bala; Hanson, Andrew D.

1998-01-01

Choline monooxygenase (CMO) catalyzes the committing step in the synthesis of glycine betaine, an osmoprotectant accumulated by many plants in response to salinity and drought. To investigate how these stresses affect CMO expression, a spinach (Spinacia oleracea L., Chenopodiaceae) probe was used to isolate CMO cDNAs from sugar beet (Beta vulgaris L., Chenopodiaceae), a salt- and drought-tolerant crop. The deduced beet CMO amino acid sequence comprised a transit peptide and a 381-residue mature peptide that was 84% identical (97% similar) to that of spinach and that showed the same consensus motif for coordinating a Rieske-type [2Fe-2S] cluster. A mononuclear Fe-binding motif was also present. When water was withheld, leaf relative water content declined to 59% and the levels of CMO mRNA, protein, and enzyme activity rose 3- to 5-fold; rewatering reversed these changes. After gradual salinization (NaCl:CaCl2 = 5.7:1, mol/mol), CMO mRNA, protein, and enzyme levels in leaves increased 3- to 7-fold at 400 mm salt, and returned to uninduced levels when salt was removed. Beet roots also expressed CMO, most strongly when salinized. Salt-inducible CMO mRNA, protein, and enzyme activity were readily detected in leaves of Amaranthus caudatus L. (Amaranthaceae). These data show that CMO most probably has a mononuclear Fe center, is inducibly expressed in roots as well as in leaves of Chenopodiaceae, and is not unique to this family. PMID:9489025

Photocatalytic activity of Fe-doped CaTiO₃ under UV-visible light.

PubMed

Yang, He; Han, Chong; Xue, Xiangxin

2014-07-01

The photocatalytic degradation of methylene blue (MB) over Fe-doped CaTiO₃ under UV-visible light was investigated. The as-prepared samples were characterized using X-ray diffraction (XRD), scanning electron microscope (SEM) equipped with an energy dispersive spectrometer (EDS) system, Fourier transform infrared spectra (FT-IR), and UV-visible diffuse reflectance spectroscopy (DRS). The results show that the doping with Fe significantly promoted the light absorption ability of CaTiO₃ in the visible light region. The Fe-doped CaTiO₃ exhibited higher photocatalytic activity than CaTiO₃ for the degradation of MB. However, the photocatalytic activity of the Fe-doped CaTiO₃ was greatly influenced by the calcination temperature during the preparation process. The Fe-doped CaTiO₃ prepared at 500°C exhibited the best photocatalytic activity, with degradation of almost 100% MB (10ppm) under UV-visible light for 180 min. Copyright © 2014. Published by Elsevier B.V.

Kinetics and mechanism of diclofenac removal using ferrate(VI): roles of Fe3+, Fe2+, and Mn2.

PubMed

Zhao, Junfeng; Wang, Qun; Fu, Yongsheng; Peng, Bo; Zhou, Gaofeng

2018-06-01

In this study, the effect of Fe 3+ , Fe 2+ , and Mn 2+ dose, solution pH, reaction temperature, background water matrix (i.e., inorganic anions, cations, and natural organic matters (NOM)), and the kinetics and mechanism for the reaction system of Fe(VI)/Fe 3+ , Fe(VI)/Fe 2+ , and Fe(VI)/Mn 2+ were investigated systematically. Traces of Fe 3+ , Fe 2+ , and Mn 2+ promoted the DCF removal by Fe(VI) significantly. The pseudo-first-order rate constant (k obs ) of DCF increased with decreasing pH (9-6) and increasing temperature (10-30 °C) due to the gradually reduced stability and enhanced reactivity of Fe(VI). Cu 2+ and Zn 2+ ions evidently improved the DCF removal, while CO 3 2- restrained it. Besides, SO 4 2- , Cl - , NO 3 - , Mg 2+ , and Ca 2+ almost had no influence on the degradation of DCF by Fe(VI)/Fe 3+ , Fe(VI)/Fe 2+ , and Fe(VI)/Mn 2+ within the tested concentration. The addition of 5 or 20 mg L -1 NOM decreased the removal efficiency of DCF. Moreover, Fe 2 O 3 and Fe(OH) 3 , the by-products of Fe(VI), slightly inhibited the DCF removal, while α-FeOOH, another by-product of Fe(VI), showed no influence at pH 7. In addition, MnO 2 and MnO 4 - , the by-products of Mn 2+ , enhanced the DCF degradation due to catalysis and superposition of oxidation capacity, respectively. This study indicates that Fe 3+ and Fe 2+ promoted the DCF removal mainly via the self-catalysis for Fe(VI), and meanwhile, the catalysis of Mn 2+ and the effect of its by-products (i.e., MnO 2 and MnO 4 - ) contributed synchronously for DCF degradation. Graphical abstract ᅟ.

Cadmium is acutely toxic for murine hepatocytes: effects on intracellular free Ca(2+) homeostasis.

PubMed

Wang, S S; Chen, L; Xia, S K

2007-01-01

We studied cadmium toxicity in murine hepatocytes in vitro. Cadmium effects on intracellular free Ca(2+) concentration ([Ca(2+)](i)) were assayed, using a laser scanning confocal microscope with a fluorescent probe, Fluo-3/AM. The results showed that administration of cadmium chloride (CdCl(2), 5, 10, 25 microM) resulted in a dose-dependent decrease of hepatocyte viability and an elevated aspartate aminotransferase (AST) activity in the culture medium (p<0.05 for 25 microM CdCl(2) vs. control). Significant increases of lactate dehydrogenase (LDH) activities in 10 and 25 microM CdC1(2)-exposed groups were observed (p<0.05 and p<0.01, respectively). A greatly decreased albumin content and a more malondialdehyde (MDA) formation also occurred after CdC1(2) treatment. The Ca(2+) concentrations in the culture medium of CdCl(2)-exposed hepatocytes were significantly decreased, while [Ca(2+)](i) appeared to be significantly elevated (p<0.05 or p<0.01 vs. control). We found that in Ca(2+)-containing hydroxyethyl piperazine ethanesulfonic acid-buffered salt solution (HBSS) only, CdCl(2) elicited [Ca(2+)](i) increases, which comprised an initially slow ascent and a strong elevated phase. However, in Ca(2+)-containing HBSS with addition of 2-aminoethoxydiphenyl borane (2-APB), CdCl(2) caused a mild [Ca(2+)](i) elevation in the absence of an initial rise phase. Removal of extracellular Ca(2+) showed that CdCl(2) induced an initially slow [Ca(2+)](i) rise alone without being followed by a markedly elevated phase, but in a Ca(2+)-free HBSS with addition of 2-APB, CdCl(2) failed to elicit the [Ca(2+)](i) elevation. These results suggest that abnormal Ca(2+) homeostasis due to cadmium may be an important mechanism of the development of the toxic effect in murine hepatocytes. [Ca(2+)](i) elevation in acutely cadmium-exposed hepatocytes is closely related to the extracellular Ca(2+) entry and an excessive release of Ca(2+) from intracellular stores.

Combustion synthesis and luminescence properties of yellow-emitting phosphors Ca{sub 2}BO{sub 3}Cl:Eu{sup 2+}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia, Zhiguo, E-mail: xiazg426@yahoo.com.cn; Liao, Libing, E-mail: lbliao@cugb.edu.cn; Zhang, Zepeng

2012-02-15

Graphical abstract: A yellow-emitting phosphor Ca{sub 2}BO{sub 3}Cl:Eu{sup 2+} was firstly synthesized by the solution-combustion method. The photoluminescence excitation and emission spectra, temperature dependence of luminescence intensity, and luminescence lifetime of the phosphor were investigated. Highlights: Black-Right-Pointing-Pointer Ca{sub 2}BO{sub 3}Cl:Eu{sup 2+} phosphor was synthesized by a solution-combustion method. Black-Right-Pointing-Pointer Ca{sub 2}BO{sub 3}Cl:Eu{sup 2+} showed an intense yellow emission band centered at 569 nm with the CIE coordinate of (0.453, 0.526). Black-Right-Pointing-Pointer The temperature dependent luminescence property and mechanism of Ca{sub 2}BO{sub 3}Cl:Eu{sup 2+} were studied. -- Abstract: Yellow-emitting phosphor Ca{sub 2}BO{sub 3}Cl:Eu{sup 2+} was synthesized by a solution-combustion method. Themore » phase structure and microstructure were determined by the X-ray diffraction (XRD) and scanning electron microscope (SEM) analysis, respectively. The as-prepared Ca{sub 2}BO{sub 3}Cl:Eu{sup 2+} phosphor absorbed near ultraviolet and blue light of 320-500 nm, and showed an intense yellow emission band centered at 569 nm with the CIE coordinate of (0.453, 0.526). The lifetime of Eu{sup 2+} ions in Ca{sub 2}BO{sub 3}Cl:Eu{sup 2+} phosphor was measured, furthermore the temperature dependent luminescence property and mechanism were studied, which also testified that the present phosphor had a promising potential for white light-emitting diodes.« less

New Evidence for the Origin of White Matrix in Tieschitz

NASA Astrophysics Data System (ADS)

Hutchison, R.

1992-07-01

In Tieschitz, an unequilibrated ordinary chondrite, chondrules, and inclusions have rims of fine-grained, opaque matrix. Between the larger objects, channels <~20 micrometers wide may be filled with Na- and Al-rich, nepheline-normative white matrix. Christophe Michel-Levy (1976) suggested that white matrix was formed by the partial solution and redeposition of chondrule mesostases, but this was disputed by Hutchison et al. (1979), because silica undersaturated white matrix commonly abuts low-Ca pyroxene, with no sign of reaction. Such materials should be incompatible at low pressure and elevated temperature. Alexander et al. (1989) found material resembling white matrix in two Sharps chondrules, but did not find it elsewhere. Furthermore, the major minerals of white matrix are still unidentified. In a thick polished section, the analytical scanning electron microscope revealed several porphyritic chondrules with mesostases composed of two types of material with different electron back-scattering properties. One type lacks internal boundaries and appears brighter than the other, which is blocky on a 5-micrometer scale; the latter resembles white matrix. Bright mesostasis has higher SiO2, TiO2, FeO, MgO, and CaO compared with the dark, blocky material, which is richer in Al2O3 and the alkalis (Table 1, cf nos. 3 and 5). A porphyritic olivine (PO) chondrule 1 mm in diameter has zoned phenocrysts of Fo(sub)90-75 (Table 1 ) and mesostasis containing Ca-pyroxene dendrites of uniform composition close to Wo(sub)38En(sub)42 and with a high MnO/FeO ratio of ~0.07. Both types of mesostasis are present and in contact. Pyroxene dendrites extend across contacts without structural or compositional change. Furthermore, at its contact with a 0.6-mm barred pyroxene chondrule, the PO chondrule is slightly indented and needles of Ca-pyroxene radiate from the point of contact into bright mesostasis. The evidence indicates that in the PO chondrule a single generation of dendritic Ca pyroxene crystallized from bright mesostasis. The pyroxene resisted later alteration (H2O, Cl?) that transformed some of the bright mesostasis into white matrix material. It is concluded that white matrix formed from chondrule mesostases by secondary metasomatism that caused depletion in Si, Ti, Fe, Mg, and Ca and enrichment in Al, Na, K (and Cl?), possibly from opaque matrix, which in Tieschitz is not enriched in these elements over bulk meteorite (Alexander et al., 1989). Christophe Michel-Levy (1976) was largely correct. The metasomatism probably occurred on the parent body, which is compatible with the textural observations that many chondrules aggregated when hot and plastic. TABLE 1: EDS analyses, 15 kV, 1 x 10^-9Amp 1 2 3 4 5 6 SiO2 41.1 38.3 63.3 53.7 53.3 50.8 TiO2 -- -- 0.44 0.41 -- 0 51 Al2O3 -- -- 10.1 1.80 21.1 2.06 Cr2O3 0.10 -- 0.09 0-94 0.15 1.31 FeO 9.6 22.2 8.8 10.5 1.90 10.5 MnO 0.33 0.65 0.20 0.68 -- 0.87 MgO 49.7 38.7 4.8 13.5 1.08 13.1 CaO 0.09 0.12 2.80 16.4 0.80 16.4 Na2O -- -- 7.8 0.95 10 0 1 62 SUM 100.9 100.0 98.2 98.9 *89.3 97.2 Comp. Fo90 Fo75 Wo37En43 Wo38En42 *Includes 0.63%K(sub)2O and 0.28%Cl. 1,2 Olivine core and rim. 3 Bright mesostasis. 4 Px in 3. 5 Blocky mesostasis. 6 Px in 5. REFERENCES: Alexander, C. M. O'D., Hutchison, R. and Barber, D.J. (1989) Earth Planet. Sci. Lett. 95 1, 87-207. Christophe Michel-Levy, M. (1976) Earth Planet. Sci. Lett. 30, 143-150. Hutchison, R., Bevan, A.W.R., Agrell, S.O. and Ashworth, J.R. (1979) Nature 280, 116-119.

Simultaneous X-ray and neutron diffraction Rietveld refinements of nanophase iron substituted hydroxyapatite

NASA Astrophysics Data System (ADS)

Kyriacou, Andreas

The effect of Fe substitution on the crystal structure of hydroxyapatite (HAp) is studied by applying simultaneous Rietveld refinements of powder x-ray and neutron diffraction patterns. Fe is one of the trace elements replacing Ca in HAp, which is the major mineral phase in bones and teeth. The morphology and magnetic properties of the Fe-HAp system are also studied by transmission electron microscopy and magnetization measurements. Samples of Ca(5-x)Fex(PO4)3OH with 0 ≤ x ≤ 0.3 were prepared. Single phase HAp was identified in x-ray diffraction patterns (XRD) of samples with x < 0.1 inferring that the solubility limits are less than 0.1. Hematite (alpha-Fe2O3) is identified as a secondary phase for higher Fe content. The refined parameters show that Fe is incorporated in the HAp structure by replacing Ca in the two crystallographic sites with a preference at the Ca2 site. This preference explains the small effect of the Fe substitution on the lattice constants of HAp. The overall decrease of the lattice constants is explained by the ionic size difference of Ca and Fe. The increasing trend of the a-lattice constant with x in the Fe substituted samples is attributed to a lattice relaxation caused by the substitution of the 4- and 6-fold Fe at the 7- and 9-fold Ca1 and Ca2 sites. This Ca local geometry reduction is indicated by a slight increase of the Ca1-O3 and Ca2-O1 bond lengths. Above the solubility limit x = 0.05, the Fe is partitioned in and out of the HAp structure with increasing nominal Fe content x. The excess Fe is oxidized to hematite. The TEM analysis and magnetic measurements support the results of the simultaneous Rietveld refinements. The TEM images show no significant effect on the morphology and size of the HAp particles upon Fe incorporation. The particles are either spheres or short rods of dimensions 20--60 nm. Hematite particles are imaged in the samples with x exceeding the solubility limit. These particles are spheres, about 15 nm in diameter and are more resistant to electron beam damage. Magnetic measurements reveal a transition of the diamagnetic pure HAp to paramagnetic Fe substituted HAp.

The role of calcium and calmodulin in freezing-induced freezing resistance of Populus tomentosa cuttings.

PubMed

Lin, Shan-Zhi; Zhang, Zhi-Yi; Lin, Yuan-Zhen; Zhang, Qian; Guo, Huan

2004-02-01

To explore the role of calcium-calmodulin messenger system in the transduction of low temperature signal in woody plants, Populus tomentosa cuttings after being treated with CaCl(2) (10 mmol/L), Ca(2+) chelator EGTA (3 mmol/L), Ca(2+) channel inhibitor LaCl(3) (100 mmol/L) or CaM antagonist CPZ (50 mmol/L) were used for freezing acclimation at -3 degrees C. The changes in the calmodulin (CaM) and malonaldehyde (MDA) contents, the activities of superoxide dismutase (SOD), peroxidase (POD) and Ca(2+)-dependent adenosinetriphosphatase (Ca(2+)-ATPase) of mitochondrial membrane as well as freezing resistance (expressed as LT(50)) of cuttings were investigated to elucidate the physiological mechanisms by which trees adapt to freezing. The results showed that freezing acclimation increased the CaM content, the activities of SOD, POD and Ca(2+)-ATPase of mitochondrial membrane as well as freezing resistance of cuttings, and decreased the MDA content as compared with control cuttings. Treatment with CaCl(2) at the time of freezing acclimation enhanced the effect of freezing acclimation on the above-mentioned indexes, but this enhancement was abolished by Ca(2+)chelator EGTA, Ca(2+) channel inhibitor LaCl(3) or CaM antagonist CPZ, indicating that the calcium-calmodulin messenger system was involved in the course of freezing resistance development. The presence of CaCl(2) at the same time of freezing acclimation also reduced the degree of decline in CaM content, and in SOD, POD and Ca(2+)-ATPase activities caused by freezing stress at -14 degrees C, and enhanced the level of increase in CaM content, and in SOD, POD and Ca(2+)-ATPase activity in the recovery periods at 25 degrees C . The change in CaM content was found to be closely correlated to the levels of SOD, POD and Ca(2+)-ATPase, and to the degree of freezing resistance of cuttings during freezing acclimation either with or without CaCl(2) treatment. It was suggested that the increase of CaM content induced by CaCl(2) treatment promote the formation of Ca(2+)-CaM complexes, which effectively activates the activities of SOD, POD and mitochondrial Ca(2+)-ATPase and then further result in the adaptive changes associated with the development and enhancement of freezing resistance. Thus, It could be concluded that Ca(2+)-calmodulin may be involved in the regulation of the increase in SOD, POD and Ca(2+)-ATPase activities, and the induction of freezing resistance of cuttings.

Co-adsorption of Trichloroethylene and Arsenate by Iron-Impregnated Granular Activated Carbon.

PubMed

Deng, Baolin; Kim, Eun-Sik

2016-05-01

Co-adsorption of trichloroethylene (TCE) and arsenate [As(V)] was investigated using modified granular activated carbons (GAC): untreated, sodium hypochlorite-treated (NaClO-GAC), and NaClO with iron-treated GAC (NaClO/Fe-GAC). Batch experiments of single- [TCE or As(V)] and binary- [TCE and As(V)] components solutions are evaluated through Langmuir and Freundlich isotherm models and adsorption kinetic tests. In the single-component system, the adsorption capacity of As(V) was increased by the NaClO-GAC and the NaClO/Fe-GAC. The untreated GAC showed a low adsorption capacity for As(V). Adsorption of TCE by the NaClO/Fe-GAC was maximized, with an increased Freundlich constant. Removal of TCE in the binary-component system was decreased 15% by the untreated GAC, and NaClO- and NaClO/Fe-GAC showed similar efficiency to the single-component system because of the different chemical status of the GAC surfaces. Results of the adsorption isotherms of As(V) in the binary-component system were similar to adsorption isotherms of the single-component system. The adsorption affinities of single- and binary-component systems corresponded with electron transfer, competitive adsorption, and physicochemical properties.

Comparison of real waste (MSW and MPW) pyrolysis in batch reactor over different catalysts. Part II: contaminants, char and pyrolysis oil properties.

PubMed

Miskolczi, Norbert; Ateş, Funda; Borsodi, Nikolett

2013-09-01

Pyrolysis of real wastes (MPW and MSW) has been investigated at 500°C, 550°C and 600°C using Y-zeolite, β-zeolite, equilibrium FCC, MoO3, Ni-Mo-catalyst, HZSM-5 and Al(OH)3 as catalysts. The viscosity of pyrolysis oils could be decreased by the using of catalysts, especially by β-zeolite and MoO3. Both carbon frame and double bound isomerization was found in case of thermo-catalytic pyrolysis. Char morphology and texture analysis showed more coke deposits on the catalyst surface using MSW raw material. Pyrolysis oils had K, S, P Cl, Ca, Zn, Fe, Cr, Br and Sb as contaminants; and the concentrations of K, S, P, Cl and Br could be decreased by the using of catalysts. Copyright © 2013 Elsevier Ltd. All rights reserved.

Microwave-assisted inorganic salt pretreatment of sugarcane leaf waste: Effect on physiochemical structure and enzymatic saccharification.

PubMed

Moodley, Preshanthan; Kana, E B Gueguim

2017-07-01

This paper presents a method to pretreat sugarcane leaf waste using microwave-assisted (MA) inorganic salt to enhance enzymatic saccharification. The effects of process parameters of salt concentration, microwave power intensity and pretreatment time on reducing sugar yield from sugarcane leaf waste were investigated. Pretreatment models based on MA-NaCl, MA-ZnCl 2 and MA-FeCl 3 were developed with high coefficients of determination (R 2 >0.8) and optimized. Maximum reducing sugar yield of 0.406g/g was obtained with 2M FeCl 3 at 700W for 3.5min. Scanning electron microscopy (SEM), Fourier Transform Infrared analysis (FTIR) and X-ray diffraction (XRD) showed major changes in lignocellulosic structure after MA-FeCl 3 pretreatment with 71.5% hemicellulose solubilization. This regime was further assessed on sorghum leaves and Napier grass under optimal MA-FeCl 3 conditions. A 2-fold and 3.1-fold increase in sugar yield respectively were observed compared to previous reports. This pretreatment was highly effective for enhancing enzymatic saccharification of lignocellulosic biomass. Copyright © 2017. Published by Elsevier Ltd.

Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars

USGS Publications Warehouse

Marion, G.M.; Catling, D.C.; Kargel, J.S.

2003-01-01

Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 ??C to 25 ??C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars. Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl2??4H2O, FeCl2??6H2O, FeSO4??H2O, FeSO4??7H2O, FeCO3, and Fe(OH)3] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO4, Fe-HCO3, H-Fe-Cl, and H-Fe-SO4. We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO3), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification. What began as a dilute Mg-Fe-HCO3 dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO4-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O2(g)], but later caused oxidation of iron [high O2(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses. ?? 2003 Elsevier Ltd.

Relaxation-phenomena in LiAl/FeS-cells

NASA Astrophysics Data System (ADS)

Borger, W.; Kappus, W.; Panesar, H. S.

A theoretical model of the capacity of strongly relaxing electrochemical systems is applied to the LiAl/FeS system. Relaxation phenomena in LiAl and FeS electrodes can be described by this model. Experimental relaxation data indicate that lithium transport through the alpha-LiAl layer to the particle surface is the capacity limiting process at high discharge current density in the LiAl electrode in LiCl-KCl and LiF-LiCl-LiBr mixtures. Strong relaxation is observed in the FeS electrode with LiCl-KCl electrolyte caused by lithium concentration gradients and precipitation of KCl in the pores.

RECOVERY OF URANIUM FROM LOW GRADE URANIUM BEARING ORES

DOEpatents

Rhodes, H.B.; Pesold, W.F.; Hirshon, J.M.

1959-06-01

Recovery of U, Fe, and Al from Chattanooga shale is described. Ground shale (-4 to +325 mesh) is roasted to remove organic and volatile matter. The heated shale is then reacted with a chlorinating agent (CCl/sub 4/, COCl/sub 2/, Cl, and SCl) at 600 to 1000 C. The metal chloride vapor is separated from entrained solids and then contacted with a liquid alkali metal chloride which removes U. The U is reeovered by cooling and dissolving the bath followed by acidification and solvent extraction. A condensed phase of Al, Fe, and K chlorides is treated to separate Al as alumina by passing through a Fe/sub 2/O/ sub 3/ bed. The remaining FeCl/sub 3/ is oxidized by O/sub 2/ at 1000 C to form Fe/sub 2/O/sub 3/ and Cl/sub 2/. Alternatively, vapor from the U separation step may be passed to a liquid KCl bath at 500 to 650 C. The resulting mixture is oxidized to form Cl/sub 2/ and Fe/sub 2/O/sub 3/ + Al/sub 2/O/sub 3/. The Al and Fe are separated by reaction with NaOH at high temperatures and pressures. (T.R.H.)

Magnetic Fe-Co films electroplated in a deep-eutectic-solvent-based plating bath

NASA Astrophysics Data System (ADS)

Yanai, T.; Shiraishi, K.; Watanabe, Y.; Ohgai, T.; Nakano, M.; Suzuki, K.; Fukunaga, H.

2015-05-01

We fabricated Fe-Co films from a deep eutectic solvent (DES)-based plating bath and investigated magnetic properties of the plated films. The plating baths were obtained by stirring the mixture of choline chloride, ethylene glycol, FeCl2.4H2O, and CoCl2.6H2O. The composition of the plated films depended on the amount of FeCl2.4H2O in the plating bath, and Fe content of the films was varied from 0 to 100 at. %. Depending on the Fe content, the saturation magnetization and the coercivity of the films varied. The Fe76Co24 film shows high saturation magnetization and smooth surface, and the change in the saturation magnetization shows good agreement with the expected change by the Slater-Pauling curve. High current efficiency (>90%) could be obtained in the wide film composition. From these results, we concluded that the DES-based plating bath is one of effective baths for the Fe-Co films with high current efficiency.

Theoretical investigation of the interaction between aromatic sulfur compounds and [BMIM](+)[FeCl4](-) ionic liquid in desulfurization: A novel charge transfer mechanism.

PubMed

Li, Hongping; Zhu, Wenshuai; Chang, Yonghui; Jiang, Wei; Zhang, Ming; Yin, Sheng; Xia, Jiexiang; Li, Huaming

2015-06-01

In this work, interaction nature between a group of aromatic sulfur compounds and [BMIM](+)[FeCl4](-) have been investigated by density functional theory (DFT). A coordination structure is found to be critical to the mechanism of extractive desulfurization. Interaction energy and extractive selectivity follow the order: thiophene (TH)

A newly developed Fe-doped calcium sulfide nanoparticles with magnetic property for cancer hyperthermia

NASA Astrophysics Data System (ADS)

Wu, Steven Yueh-Hsiu; Tseng, Ching-Li; Lin, Feng-Huei

2010-05-01

In this study, a magnetic iron-doped calcium sulfide (Fe-CaS) nanoparticle was newly developed and studied for the purpose of hyperthermia due to its promising magnetic property, adequate biodegradation rate, and relatively good biocompatibility. Fe-CaS nanoparticles were synthesized by a wet chemical co-precipitation process with heat treatment in a N2 atmosphere, and were subsequently cooled in N2 and exposed to air at a low temperature. The crystal structure of the Fe-CaS nanoparticles was similar to that of the CaS, which was identified by an X-ray diffractometer (XRD). The particle size was less than 40 nm based on a Debye-Scherrer equation and transmission electron microscope (TEM) examination. Magnetic properties obtained from the SQUID magnetometer demonstrated that the synthesized CaS was a diamagnetic property. Once the Fe ions were doped, the synthesized Fe-CaS converted into paramagnetism which showed no hysteresis loop. Having been heated above 600 °C in N2, the Fe-CaS showed a promising magnetic property to produce enough energy to increase the temperature for hyperthermia. 10 mg/ml of the Fe-CaS was able to generate heat to elevate the media temperature over 42.5 °C within 6 min. The area of the hysteresis loop increased with the increasing of the treated temperature, especially at 800 °C for 1 h. This is because more Fe ions replaced Ca ions in the lattice at the higher heat treatment temperature. The heat production was also increasing with the increasing of heat treatment temperature, which resulted in an adequate specific absorption ratio (SAR) value, which was found to be 45.47 W/g at 37 °C under an alternative magnetic field of f = 750 KHz , H = 10 Oe. The in vitro biocompatibility test of the synthesized Fe-CaS nanoparticles examined by the LDH assay showed no cytotoxicity to 3T3 fibroblast. The result of in vitro cell hyperthermia shows that under magnetic field the Fe-CaS nanoparticles were able to generate heat and kill the CT-26 cancer cells significantly. We believe that the developed Fe-CaS nanoparticles have great potential as thermo-seeds for cancer hyperthermia in the near future.

The generation of HCl in the system CaCl2-H2O: Vapor-liquid relations from 380-500°C

USGS Publications Warehouse

Bischoff, James L.; Rosenbauer, Robert J.; Fournier, Robert O.

1996-01-01

We determined vapor-liquid relations (P-T-x) and derived critical parameters for the system CaCl2-H2O from 380-500??C. Results show that the two-phase region of this system is extremely large and occupies a significant portion of the P-T space to which circulation of fluids in the Earth's crust is constrained. Results also show the system generates significant amounts of HCl (as much as 0.1 mol/kg) in the vapor phase buffered by the liquid at surprisingly high pressures (???230 bars at 380??C, <580 bars at 500??C), presumably by hydrolysis of CaCl2: CaCl2 + 2H2O = Ca(OH)2 + 2HCl. We interpret the abundance of HCl in the vapor as due to its preference for the vapor phase, and by the preference of Ca(OH)2 for either the liquid phase or solid. The recent recognition of the abundance of CaCl2 in deep brines of the Earth's crust and their hydrothermal mobilization makes the hydrolysis of CaCl2 geologically important. The boiling of Ca-rich brines produces abundant HCl buffered by the presence of the liquid at moderate pressures. The resultant Ca(OH)2 generated by this process reacts with silicates to form a variety of alteration products, such as epidote, whereas the vapor produces acid-alteration of rocks through which it ascends.

Rapamycin inhibits CaCl2-induced thoracic aortic aneurysm formation in rats through mTOR-mediated suppression of proinflammatory mediators.

PubMed

Cao, Jiumei; Wu, Qihong; Geng, Liang; Chen, Xiaonan; Shen, Weifeng; Wu, Fang; Chen, Ying

2017-08-01

The aim of the present study was to investigate the effect of the mammalian target of rapamycin (mTOR) signaling pathway on thoracic aortic aneurysm (TAA) development. The study used a calcium chloride (CaCl2)‑induced rat TAA model to explore the potential role of mTOR signaling pathway in the disease development. Adult male Sprague‑Dawley rats underwent the periarterial exposure of thoracic aorta to either 0.5 M CaCl2 or normal saline, and a subgroup of CaCl2‑treated rats received rapamycin 1 day prior to surgery. Without pre‑administering rapamycin, significantly enhanced phosphorylation of mTOR and expression of proinflammatory cytokines [i.e., tumor necrosis factor α (TNF‑α), interleukin 6 (IL‑6), and interleukin (IL)‑1β] were observed in the CaCl2‑treated aortic segments 2 days post‑treatment compared with the NaCl‑treated segments. At 2 weeks post‑treatment, hematoxylin and eosin and Verhoeff‑Van Gieson staining revealed aneurysmal alteration and disappearance of normal wavy elastic structures in the aortic segments exposed to CaCl2. In contrast, the CaCl2‑induced TAA formation was inhibited by pre‑administering rapamycin to CaCl2‑treated rats, which demonstrated attenuated mTOR phosphorylation and downregulation of the proinflammatory mediators (i.e., TNF‑α, IL‑6, IL‑1β, matrix metallopeptidases 2 and 9) to the control level. Further in vitro cell culture experiments using aortic smooth muscle cell (SMC) suggested that the inhibition of the mTOR signaling pathway by rapamycin could promote the differentiation of SMCs, as reflected by the reduced expression of S100A4 and osteopontin. The present study indicated that the early enhanced mTOR signaling pathway in the TAA development and mTOR inhibitor rapamycin may inhibit CaCl2‑induced TAA formation.

Is there a potential consumer market for low-sodium fermented sausages?

PubMed

Dos Santos, Bibiana A; Campagnol, Paulo C B; da Cruz, Adriano G; Morgano, Marcelo A; Wagner, Roger; Pollonio, Marise A R

2015-05-01

The NaCl levels in dry fermented sausages were reduced by 50% or were substituted with KCl, CaCl2 , or a blend of KCl and CaCl2 (1:1). The quality, safety, and the potential consumer market of dry fermented sausages were assessed. Neither 50% reduction of the NaCl content nor the substitution of 50% of the NaCl with KCl influenced the fermentation and maturation process. However, when CaCl2 was used as the substitute salt (50%), there was a significant decrease in pH, an increase in the water activity, and a decrease in lactic acid and micrococcus bacterial counts. Overall, the sensory acceptance decreased in dry fermented sausages with reduced sodium content. However, cluster analysis and internal preference mapping revealed potential for commercialization of samples with 50% of the NaCl content substituted with KCl or with a mixture of KCl and CaCl2 (1:1). © 2015 Institute of Food Technologists®

The stability of Cl-CO3-scapolite relative to plagioclase + CaCO3 + CaSO4 in the presence of NaCl brines as a function of P-T-XNaCl

NASA Astrophysics Data System (ADS)

Harlov, D. E.; Budzyn, B.

2008-12-01

Cl-CO3-scapolite [(Na,Ca)4[Al3 (Al,Si) 3 Si3 O24](Cl, CO3 , SO4 )] occurs as a common partial to total alteration of plagioclase in deep-crustal xenoliths, skarns, marbles, gabbros, metabasites, calc-silicate gneisses, as well as in quartzofeldspathic granulite-facies rocks in general (Moecher and Essene, 1990, J Petrol 31, 997). Alteration of plagioclase to Cl-CO3-scapolite is presumed due to metasomatism by CO2-NaCl-H2O fluids (Satish-Kumar and Santosh, 1998, Geol Mag 135, 27). Previous experimental work on CO3-scapolite has focused on reversing the equilibrium 3 CaAl2 Si2 O8 + CaCO3 = Ca4 Al6 Si6 O24 CO3 in either pure CO2 (Goldschmidt and Newton, 1977, Am Mineral 62, 1063) or in CO2-H2O (Huckenholz and Seiberl, 1989 Abs IGC 28, 2.79). These experiments have determined that the anorthite- calcite-scapolite equilibrium is nearly pressure-invariant in P-T space (200 to 1500 MPa) occurring at approximately 790 to 820 °C (Huckenholz and Seiberl, 1989). In this study, a series of experiments, involving the equilibrium 3 Plagioclase(An60) + 0.5 CaCO3 + 0.5 CaSO4 = [(Na,Ca)4[Al3 (Al,Si)3 Si3 O24](Cl, CO3, SO4 )] plus an NaCl brine (10/90, 20/80, 30/70, and 50/50 molar NaCl/H2O) have been done at 500, 1000, and 1500 MPa and 600 to 900 °C. Natural plagioclase and scapolite, along with synthetic calcite and anhydrite, were lightly ground together in equi-molar amounts in ethanol. The mineral mix (10 mg) + NaCl brine (5 mg), or pure H2O (1.5 mg), were loaded into 3 mm diameter/1.3 mm long Pt capsules which were arc-welded shut, folded, and placed horizontally in a CaF2 setup (with graphite oven), such that the thermocouple tip touched the Pt capsule, or placed in a hydrothermal autoclave (600 and 700 °C; 500 MPa) with an internal thermocouple. A series of duplicate experiments for the same mineral mix, at the same P-T conditions, were done utilizing pure H2O as the flux. The H2O-only experiments duplicated the P-T reversals of Huckenholz and Seiberl (1989). In contrast, the NaCl/H2 O experiments indicate that the stability field of Cl-CO3-scapolite (SiO2 =52.1, Al2O3=24.9, CaO=11.9, Na2O=7.60, Cl=1.86, CO3=2.00, SO4=0.45), relative to plagioclase, greatly expands in the presence of NaCl brines at NaCl concentrations above 10 percent NaCl such that Cl-CO2-scapolite is stable over 600 to 900 °C and 500 to 1500 MPa. This result further strengthens the proposition that NaCl brines, coupled with CO2-bearing fluids, can be and probably are involved during high-grade scapolitization of plagioclase-bearing rocks in the mid to lower crust and upper mantle.

Size distribution of chemical elements and their source apportionment in ambient coarse, fine, and ultrafine particles in Shanghai urban summer atmosphere.

PubMed

Lü, Senlin; Zhang, Rui; Yao, Zhenkun; Yi, Fei; Ren, Jingjing; Wu, Minghong; Feng, Man; Wang, Qingyue

2012-01-01

Ambient coarse particles (diameter 1.8-10 microm), fine particles (diameter 0.1-1.8 microm), and ultrafine particles (diameter < 0.1 microm) in the atmosphere of the city of Shanghai were sampled during the summer of 2008 (from Aug 27 to Sep 08). Microscopic characterization of the particles was investigated by scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM/EDX). Mass concentrations of Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, Rb, Sr, and Pb in the size-resolved particles were quantified by using synchrotron radiation X-ray fluorescence (SRXRF). Source apportionment of the chemical elements was analyzed by means of an enrichment factor method. Our results showed that the average mass concentrations of coarse particles, fine particles and ultrafine particles in the summer air were 9.38 +/- 2.18, 8.82 +/- 3.52, and 2.02 +/- 0.41 microg/m3, respectively. The mass percentage of the fine particles accounted for 51.47% in the total mass of PM10, indicating that fine particles are the major component in the Shanghai ambient particles. SEM/EDX results showed that the coarse particles were dominated by minerals, fine particles by soot aggregates and fly ashes, and ultrafine particles by soot particles and unidentified particles. SRXRF results demonstrated that crustal elements were mainly distributed in the coarse particles, while heavy metals were in higher proportions in the fine particles. Source apportionment revealed that Si, K, Ca, Fe, Mn, Rb, and Sr were from crustal sources, and S, Cl, Cu, Zn, As, Se, Br, and Pb from anthropogenic sources. Levels of P, V, Cr, and Ni in particles might be contributed from multi-sources, and need further investigation.

Source apportionment revisited for long-term measurements of fine aerosol trace elements at two locations in southern Norway

NASA Astrophysics Data System (ADS)

Maenhaut, Willy

2018-02-01

Five-year-long (1991-1996) aerosol trace element data sets for the fine (PM2) size fraction from the sites of Birkenes and Skreådalen in southern Norway were reanalysed by US EPA positive matrix factorization PMF5 in order to assess the sources and their contribution to the PM2 aerosol. The data sets contained the concentrations of the particulate mass (PM), black carbon (BC) and 21 elements in over 700 samples for each of the two sites. The PM was obtained from weighing with a microbalance and BC was determined with a light reflectance technique. The data for the elements were obtained by a combination of particle-induced X-ray emission and instrumental neutron activation analysis. Eight source factors were retained for each site, i.e., (i) secondary sulfate, which accounted for around 40% of the average measured PM2 mass, (ii) wood burning, with BC, K, Zn and As, which accounted for about 17%, (iii) an iodine factor (with also Br and Se), which is probably related to a marine biogenic source and was responsible for about 6.5%, (iv) aged sea salt with Na, Mg, Cl and Ca, but heavily depleted in Cl; (v) a crustal factor containing Al, Si, Ca, Ti and Fe; (vi) a heavy oil burning factor with V and Ni in a ratio of 3-4; (vii) a general pollution factor (with Cu, Zn, As, Se, Sb and Pb), and (viii) an almost pure manganese factor, which is attributed to Mn and FeMn industries in southern Norway. The results were substantially different from those of an earlier PMF analysis, in which use was made of PMF2.

Evaluation of Populus and Salix continuously irrigated with landfill leachate I. Genotype-specific elemental phytoremediation.

PubMed

Zalesny, Ronald S; Bauer, Edmund O

2007-01-01

There is a need for the identification and selection of specific tree genotypes that can sequester elements from contaminated soils, with elevated rates of uptake. We irrigated Populus (DN17, DN182, DN34, NM2, NM6) and Salix (94003, 94012, S287, S566, SX61) genotypes planted in large soil-filled containers with landfill leachate or municipal water and tested for differences in inorganic element concentrations (P, K, Ca, Mg, S, Zn, B, Mn, Fe, Cu, Al, Na, and Cl) in the leaves, stems, and roots. Trees were irrigated with leachate or water during the final 12 wk of the 18-wk study. Genotype-specific uptake existed. For genera, tissue concentrations exhibited four responses. First, Populus had the greatest uptake of P, K, S, Cu, and Cl. Second, Salix exhibited the greatest uptake of Zn, B, Fe, and Al. Third, Salix had greater concentrations of Ca and Mg in leaves, while Populus had greater concentrations in stems and roots. Fourth, Populus had greater concentrations of Mn and Na in leaves and stems, while Salix had greater concentrations in roots. Populus deltoides x P. nigra clones exhibited better overall phytoremediation than the P. nigra x P. maximowiczii genotypes tested. Phytoremediation for S. purpurea clones 94003 and 94012 was generally less than for other Salix genotypes. Overall, concentrations of elements in the leaves, stems, and roots corroborated those in the plant-sciences literature. Uptake was dependent upon the specific genotype for most elements. Our results corroborated the need for further testing and selecting of specific clones for various phytoremediation needs, while providing a baseline for future researchers developing additional studies and resource managers conducting on-site remediation.

Detection of Labile Low-Molecular-Mass Transition Metal Complexes in Mitochondria

PubMed Central

McCormick, Sean P.; Moore, Michael J.; Lindahl, Paul A.

2015-01-01

Liquid chromatography was used with an on-line inductively coupled plasma mass spectrometer to detect low-molecular-mass (LMM) transition metal complexes in mitochondria isolated from fermenting yeast cells, human Jurkat cells, and mouse brain and liver. These complexes constituted 20 – 40% of total mitochondrial Mn, Fe, Zn, and Cu ions. The major LMM Mn complex in yeast mitochondria had a mass of ca. 1100 Da and a concentration of ~ 2 μM. Mammalian mitochondria contained a second Mn species with a mass of ca. 2000 Da at a comparable concentration. The major Fe complex in mitochondria isolated from exponentially growing yeast cells had a mass of ca. 580 Da; the concentration of Fe580 in mitochondria was ca. 100 μM. When mitochondria were isolated from fermenting cells in post-exponential phase, the mass of the dominant LMM Fe complex was ca. 1100 Da. Upon incubation, the intensity of Fe1100 declined and Fe580 increased, suggesting that the two are interrelated. Mammalian mitochondria contained Fe580 and 2 other Fe species (Fe2000 and Fe1100) at concentrations of ca. 50 μM each. The dominant LMM Zn species in mitochondria had a mass of ca. 1200 Da and a concentration of ca. 110 μM. Mammalian mitochondria contained a second major LMM Zn species at 1500 Da. The dominant LMM Cu species in yeast mitochondria had a mass of ca. 5000 Da and a concentration in yeast mitochondria of ca. 16 μM; Cu5000 was not observed in mammalian mitochondria. The dominant Co species in mitochondria, Co1200, had a concentration of 20 nM and was probably a cobalamin. Mammalian but not yeast mitochondria contained a LMM Mo species, Mo730, at ca. 1 μM concentration. Increasing Mn, Fe, Cu, and Zn concentrations 10 fold in the medium increased the concentration of the same element in the corresponding isolated mitochondria. Treatment with metal chelators confirmed that these LMM species were labile. The dominant S species at 1100 Da was not free GSH or GSSG. PMID:26018429

The Interface Structure of FeSe Thin Film on CaF2 Substrate and its Influence on the Superconducting Performance.

PubMed

Qiu, Wenbin; Ma, Zongqing; Patel, Dipak; Sang, Lina; Cai, Chuanbing; Shahriar Al Hossain, Mohammed; Cheng, Zhenxiang; Wang, Xiaolin; Dou, Shi Xue

2017-10-25

The investigations into the interfaces in iron selenide (FeSe) thin films on various substrates have manifested the great potential of showing high-temperature-superconductivity in this unique system. In present work, we obtain FeSe thin films with a series of thicknesses on calcium fluoride (CaF 2 ) (100) substrates and glean the detailed information from the FeSe/CaF 2 interface by using scanning transmission electron microscopy (STEM). Intriguingly, we have found the universal existence of a calcium selenide (CaSe) interlayer with a thickness of approximate 3 nm between FeSe and CaF 2 in all the samples, which is irrelevant to the thickness of FeSe layers. A slight Se deficiency occurs in the FeSe layer due to the formation of CaSe interlayer. This Se deficiency is generally negligible except for the case of the ultrathin FeSe film (8 nm in thickness), in which the stoichiometric deviation from FeSe is big enough to suppress the superconductivity. Meanwhile, in the overly thick FeSe layer (160 nm in thickness), vast precipitates are found and recognized as Fe-rich phases, which brings about degradation in superconductivity. Consequently, the thickness dependence of superconducting transition temperature (T c ) of FeSe thin films is investigated and one of our atmosphere-stable FeSe thin film (127 nm) possesses the highest T c onset /T c zero as 15.1 K/13.4 K on record to date in the class of FeSe thin film with practical thickness. Our results provide a new perspective for exploring the mechanism of superconductivity in FeSe thin film via high-resolution STEM. Moreover, approaches that might improve the quality of FeSe/CaF 2 interfaces are also proposed for further enhancing the superconducting performance in this system.

Selective Extraction and Recovery of Nd and Dy from Nd-Fe-B Magnet Scrap by Utilizing Molten MgCl2

NASA Astrophysics Data System (ADS)

Shirayama, Sakae; Okabe, Toru H.

2018-06-01

Fundamental experiments are conducted with the aim of developing an efficient recycling process for rare earth elements (REEs) from neodymium-iron-boron (Nd-Fe-B) permanent magnet scrap. Molten magnesium dichloride (MgCl2) was chosen as an extraction medium, which can selectively chlorinate and extract REEs in magnet alloys. Dysprosium-containing Nd-Fe-B magnet alloy was immersed in molten MgCl2 at 1273 K (1000 °C) for 3 to 12 hours. The results of the experiments clearly show that the REEs in the magnetic alloy were successfully extracted into the molten salt, while the Fe-B alloy remained in a solid form. The extraction ratios of Nd and Dy were at most 87 and 78 mass pct, respectively. After the extraction experiment, excess MgCl2 and Mg were removed by vacuum distillation and the rare earth chlorides were recovered. Thus, the feasibility of this method for efficient recovery of rare earths using molten MgCl2 is demonstrated.

Selective Extraction and Recovery of Nd and Dy from Nd-Fe-B Magnet Scrap by Utilizing Molten MgCl2

NASA Astrophysics Data System (ADS)

Shirayama, Sakae; Okabe, Toru H.

2018-02-01

Fundamental experiments are conducted with the aim of developing an efficient recycling process for rare earth elements (REEs) from neodymium-iron-boron (Nd-Fe-B) permanent magnet scrap. Molten magnesium dichloride (MgCl2) was chosen as an extraction medium, which can selectively chlorinate and extract REEs in magnet alloys. Dysprosium-containing Nd-Fe-B magnet alloy was immersed in molten MgCl2 at 1273 K (1000 °C) for 3 to 12 hours. The results of the experiments clearly show that the REEs in the magnetic alloy were successfully extracted into the molten salt, while the Fe-B alloy remained in a solid form. The extraction ratios of Nd and Dy were at most 87 and 78 mass pct, respectively. After the extraction experiment, excess MgCl2 and Mg were removed by vacuum distillation and the rare earth chlorides were recovered. Thus, the feasibility of this method for efficient recovery of rare earths using molten MgCl2 is demonstrated.

CLC-mediated anion transport in plant cells

PubMed Central

De Angeli, Alexis; Monachello, Dario; Ephritikhine, Geneviève; Frachisse, Jean-Marie; Thomine, Sébastien; Gambale, Franco; Barbier-Brygoo, Hélène

2008-01-01

Plants need nitrate for growth and store the major part of it in the central vacuole of cells from root and shoot tissues. Based on few studies on the two model plants Arabidopsis thaliana and rice, members of the large ChLoride Channel (CLC) family have been proposed to encode anion channels/transporters involved in nitrate homeostasis. Proteins from the Arabidopsis CLC family (AtClC, comprising seven members) are present in various membrane compartments including the vacuolar membrane (AtClCa), Golgi vesicles (AtClCd and AtClCf) or chloroplast membranes (AtClCe). Through a combination of electrophysiological and genetic approaches, AtClCa was shown to function as a 2NO3−/1H+ exchanger that is able to accumulate specifically nitrate into the vacuole, in agreement with the main phenotypic trait of knockout mutant plants that accumulate 50 per cent less nitrate than their wild-type counterparts. The set-up of a functional complementation assay relying on transient expression of AtClCa cDNA in the mutant background opens the way for studies on structure–function relationships of the AtClCa nitrate transporter. Such studies will reveal whether important structural determinants identified in bacterial or mammalian CLCs are also crucial for AtClCa transport activity and regulation. PMID:18957376

Kinetics Study on the Effect of NaCl on the CaSO4 Dissolution Behavior

NASA Astrophysics Data System (ADS)

Song, Jingyao; Shi, Peiyang; Wang, Yeguang; Jiang, Maofa

2018-01-01

The study of the dissolution kinetics of CaSO4 is essential for the control of the dissolution and recrystallization behavior of CaSO4. In this work, the kinetic behavior of CaSO4 dissolved in NaCl solution was investigated by means of conductivity meter. The results show that with the increase of concentration of NaCl, the temperature rise and the time prolonged, the dissolution rate of dihydrate CaSO4 gradually increases, and the dissolved apparent activation energy is gradually decreased. When the NaCl concentration is 1.8%, the dissolution kinetic equation is 1-(1-α) 1/3=5.46*10-4exp (-9147/RT) t; When the NaCl concentration is 3.0%, the dissolution kinetic equation is 1-(1-α) 1/3=2.81×10-4 exp (-6753/RT)t; When the NaCl concentration is 3.6%, the dissolution kinetic equation is 1-(1-α) 1/3=3.07×l0-4exp(-6103/RT)t.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.

We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py) 4FeCl 2. Furthermore, we prepared a series of monoalkylated salts of the type (py) 2FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py) 4FeCl 2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane thatmore » readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py) 2FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe) 2FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe) 2FeCl 2 gave the reduced Fe(0) nitrogen complex (dmpe) 2Fe(N 2). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.« less

Contribution of an ancient evaporitic-type reservoir to lake vostok chemistry

NASA Astrophysics Data System (ADS)

de Angelis, M.; Thiemens, M. H.; Savarino, J.; Petit, J. R.

2003-04-01

Accretion ice 1 (3538 to 3608 m) contents visible sediment inclusions likely incorporated into ice in a shallow bay upstream Vostok where glacier moves against a relief rise. Ion chromatography measurements indicate that elemental concentrations are linked to inclusions abundances. More than 80% of SO_42- is present as CaSO_4 or MgSO_4. While SO_42- concentrations and the relative proportion of CaSO_4 and MgSO_4 varies in a wide range in accreted ice, concentration profiles of Na and Cl, present as NaCl, are much more regular even along individual crystals. Question rises about the presence of such salts in lake water: The 17O anomaly of sulphate in one samples taken at 3570 m suggests that less than 10% of total sulphate comes from DMS oxidation, ruling out any significant contribution of glacer melt water. Fe concentrations are low (10 ppb) excluding sulphate production from the pyrite oxidation by biogenic in-situ activity. This conclusion is supported by the isotopic signature of 34S. Taken all together, these observations strongly suggest the contribution of an evaporitic-type basin to the lake salinity. Assuming that sediments accumulated in an isolated reservoir prior the lake formation, seismotectonic activated hydrothermal circulation may pulse NaCl rich water with sulphate salts through faults up to their vents in a shallow bay upstream Vostok, where they could be incorporated in the accreted ice and also contribute to lake salinity.

Electrolyte induced rheological modulation of graphene oxide suspensions and its applications in adsorption

NASA Astrophysics Data System (ADS)

Ojha, Abhijeet; Thareja, Prachi

2018-03-01

In this study, we report the microstructure, rheology and adsorption characteristics of aqueous suspensions of Graphene Oxide (GO) at a volume fraction (ϕGO) = 0.018, which can be transformed into gels by cation induced charge shielding and cross-linking between GO nanosheets. GO nanosheets of average thickness ∼1.5 nm and a lateral dimension of ∼750 nm are synthesized by Hummer's process. At ϕGO= 0.018, cations of varying size and valence are systematically introduced with electrolytes NH4Cl, LiCl, NaCl, KCl, MgCl2 and FeCl3 at concentrations ranging from 10-5-10-1 M to investigate their effect on the rheology of GO suspensions. Our results suggest that depending on the electrolyte concentration, size and the valence of the cation: low viscosity suspensions, fragile gels and solid-like GO-electrolyte gels are formed. The storage modulus (G') of all GO-electrolyte gels increases with the increase in electrolyte concentration and G' follows the order GO-FeCl3 > GO-MgCl2> GO-KCl > GO-NaCl > GO-LiCl > GO-NH4Cl. FESEM analysis shows that lyophilized GO-electrolyte gels with 10-1 M electrolytes have a porous morphology resulting from the aggregation of GO nanosheets. The GO-electrolyte gels are shown to adsorb high quantities of oils, with GO-FeCl3 gels showing a higher adsorption capacity. The GO-NaCl and GO-FeCl3 lyophilized gels are also shown to adsorb methylene blue dye and follow the pseudo-second-order kinetics of adsorption. Along with higher oil and dye adsorption efficiency, GO-electrolyte gels are easy to recollect after the adsorption, thus avoiding the potential toxicity for bio-organisms in water caused by GO nanosheets.

Spatial Associations and Chemical Composition of Organic Carbon Sequestered in Fe, Ca, and Organic Carbon Ternary Systems.

PubMed

Sowers, Tyler D; Adhikari, Dinesh; Wang, Jian; Yang, Yu; Sparks, Donald L

2018-05-25

Organo-mineral associations of organic carbon (OC) with iron (Fe) oxides play a major role in environmental OC sequestration, a process crucial to mitigating climate change. Calcium has been found to have high coassociation with OC in soils containing high Fe content, increase OC sorption extent to poorly crystalline Fe oxides, and has long been suspected to form bridging complexes with Fe and OC. Due to the growing realization that Ca may be an important component of C cycling, we launched a scanning transmission X-ray microscopy (STXM) investigation, paired with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, in order to spatially resolve Fe, Ca, and OC relationships and probe the effect of Ca on sorbed OC speciation. We performed STXM-NEXAFS analysis on 2-line ferrihydrite reacted with leaf litter-extractable dissolved OC and citric acid in the absence and presence of Ca. Organic carbon was found to highly associate with Ca ( R 2 = 0.91). Carboxylic acid moieties were dominantly sequestered; however, Ca facilitated the additional sequestration of aromatic and phenolic moieties. Also, C NEXAFS revealed polyvalent metal ion complexation. Our results provide evidence for the presence of Fe-Ca-OC ternary complexation, which has the potential to significantly impact how organo-mineral associations are modeled.

Experimental study of iron-chloride complexing in hydrothermal fluids

USGS Publications Warehouse

Fein, J.B.; Hemley, J.J.; d'Angelo, W. M.; Komninou, A.; Sverjensky, D.A.

1992-01-01

Mineral assemblage solubilities were measured in cold-seal pressure vessels as a function of pressure, temperature, and potassium chloride concentration in order to determine the nature and thermodynamic properties of iron-chloride complexes under hydrothermal conditions. The assemblage pyritepyrrhotite-magnetite was used to buffer f{hook}S2 and f{hook}O2, and K+ H+ ratios were buffered at reasonable geologic values using the assemblage potassium feldspar-muscovite (or andalusite)-quartz. The pressure-temperature ranges were 0.5-2.0 kbar and 300-600??C, and initial fluid compositions ranged from 0.01-2.0 molal KCl. With all other factors constant, the concentration of iron in solution increases with increasing temperature, with decreasing pressure, and with increasing total potassium chloride concentration. Changes in iron concentrations as a function of KCl concentration, in conjunction with charge balance, mass action, and mass balance constraints on the system, place constraints on the stoichiometry of the important iron-chloride complexes under each of the experimental conditions. Using least-squared linear regression fits to determine these slopes, the calculations yield values for the average ligand numbers that are in the range 1.2-1.9, with uncertainties ranging from ??0.1-0.6 at the several PT conditions considered. The slopes of the regressed fits to the data suggest that both FeCl+ and FeCl20 are important in the experimental fluids, with FeCl20 becoming dominant at the higher temperatures. Theoretical calculations, however, indicate that FeCl+ does not contribute significantly to the solubility. Because of the large uncertainties associated with some of the calculated average ligand numbers, we base our data analysis on the theoretical calculations. A statistical analysis is applied to the solubility data in order to determine the values and uncertainties of the dissociation constant for FeCl20 that best fit the data at each of the experimental pressures and temperatures. The calculated stability of FeCl20 increases with increasing temperature and total chloride concentration, and with decreasing pressure. The values of the dissociation constant of FeCl20that are calculated in this study are in moderately good agreement with FeCl20dissociation constants from other studies of iron-chloride complexing in supercritical fluids. Differences are likely due to different assumptions made concerning activity coefficients of aqueous species. Log kd values for full dissociation of FeCl20 at 0.5 kbar-300??C-and at 1 kbar-400, 500, and 600??C, respectively-are -3.75 ?? 0.40, -6.25 ?? 0.10, -9.19 ?? 0.44, and -13.29 ?? 0.09. ?? 1992.

Fermentation in nutrient salt mixtures affects green Spanish-style Manzanilla table olive characteristics.

PubMed

López-López, Antonio; Bautista-Gallego, Joaquín; Moreno-Baquero, José María; Garrido-Fernández, Antonio

2016-11-15

This work studies the effects of the substitution of NaCl with KCl and CaCl2 on the physicochemical, mineral and sensory profile of fermented green Spanish-style Manzanilla olives, using an enlarged centroid mixture design. An increasing presence of CaCl2 in the initial brines improved the colour index, L(∗), b(∗) values, and firmness. The Na in the olives decreased (linearly) while the levels of K and Ca increased (quadratic) as a function of the KCl and CaCl2 concentrations in the initial brines. CaCl2 also improved the retention of Zn and P in the flesh. PLS showed a strong relationship between Ca and bitterness, hardness, fibrousness, crunchiness and saltiness (negative) and allowed for the prediction of sensory attributes (except acid) from the mineral contents in the flesh. Most of the treatments could lead to new green Spanish-style Manzanilla olive presentations with reduced Na and healthier characteristics. Copyright © 2016 Elsevier Ltd. All rights reserved.

Formation of unusual Cr5+ charge state in CaCr0.5Fe0.5O3 perovskite

NASA Astrophysics Data System (ADS)

Dai, Jian-Hong; Zhao, Qing; Sun, Qian; Zhang, Shuo; Wang, Xiao; Shen, Xu-Dong; Liu, Zhe-Hong; Shen, Xi; Yu, Ri-Cheng; Chan, Ting-Shan; Li, Lun-Xiong; Zhou, Guang-Hui; Yang, Yi-feng; Jin, Chang-Qing; Long, You-Wen

2018-03-01

A new oxide CaCr0.5Fe0.5O3 was prepared under high pressure and temperature conditions. It crystallizes in a B-site disordered Pbnm perovskite structure. The charge combination is determined to be Cr5+/Fe3+ with the presence of unusual Cr5+ state in octahedral coordination, although Cr4+ and Fe4+ occur in the related perovskites CaCrO3 and CaFeO3. The randomly distributed Cr5+ and Fe3+ spins lead to short-range ferromagnetic coupling, whereas an antiferromagnetic phase transition takes place near 50 K due to the Fe3+–O–Fe3+ interaction. In spite of the B-site Cr5+/Fe3+ disorder, the compound exhibits electrical insulating behavior. First-principles calculations further demonstrate the formation of {CaCr}}0.55+{Fe}}0.53+{{{O}}}3 charge combination, and the electron correlation effect of Fe3+ plays an important role for the insulting ground state. CaCr0.5Fe0.5O3 provides the first Cr5+ perovskite system with octahedral coordination, opening a new avenue to explore novel transition-metal oxides with exotic charge states. Project supported by the National Natural Science Foundation of China (Grant Nos. 11574378, 51772324, and 61404052),the National Basic Research Program of China (Grant No. 2014CB921500), and the Chinese Academy of Sciences (Grant Nos. YZ201555, QYZDB-SSW-SLH013, GJHZ1773, and XDB07030300).

Osteogenic differentiation of equine adipose tissue derived mesenchymal stem cells using CaCl2.

PubMed

Elashry, Mohamed I; Baulig, Nadine; Heimann, Manuela; Bernhardt, Caroline; Wenisch, Sabine; Arnhold, Stefan

2018-04-01

Adipose tissue derived mesenchymal stem cells (ASCs) may be used to cure bone defects after osteogenic differentiation. In this study we tried to optimize osteogenic differentiation for equine ASCs using various concentrations of CaCl 2 in comparison to the standard osteogenic protocol. ASCs were isolated from subcutaneous adipose tissue from mixed breed horses. The osteogenic induction protocols were (1) the standard osteogenic medium (OM) composed of dexamethasone, ascorbic acid and β-glycerol phosphate; (2) CaCl 2 based protocol composed of 3, 5 and 7.5mM CaCl 2 . Differentiation and proliferation were evaluated at 7, 10, 14 and 21days post-differentiation induction using the alizarin red staining (ARS) detecting matrix calcification. Semi-quantification of cell protein content, ARS and alkaline phosphatase activity (ALP) were performed using an ELISA reader. Quantification of the transcription level for the common osteogenic markers alkaline phosphatase (ALP) and Osteopontin (OP) was performed using RT-qPCR. In the presence of CaCl 2 , a concentration dependent effect on the osteogenic differentiation capacity was evident by the ARS evaluation and OP gene expression. We provide evidence that 5 and 7mM CaCl 2 enhance the osteogenic differentiation compared to the OM protocol. Although, there was a clear commitment of ASCs to the osteogenic fate in the presence of 5 and 7mM CaCl 2 , cell proliferation was increased compared to OM. We report that an optimized CaCl 2 protocol reliably influences ASCs osteogenesis while conserving the proliferation capacity. Thus, using these protocols provide a platform for using ASCs as a cell source in bone tissue engineering. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Calcium-Sensing Receptor Increases Activity of the Renal NCC through the WNK4-SPAK Pathway.

PubMed

Bazúa-Valenti, Silvana; Rojas-Vega, Lorena; Castañeda-Bueno, María; Barrera-Chimal, Jonatan; Bautista, Rocío; Cervantes-Pérez, Luz G; Vázquez, Norma; Plata, Consuelo; Murillo-de-Ozores, Adrián R; González-Mariscal, Lorenza; Ellison, David H; Riccardi, Daniela; Bobadilla, Norma A; Gamba, Gerardo

2018-05-30

Background Hypercalciuria can result from activation of the basolateral calcium-sensing receptor (CaSR), which in the thick ascending limb of Henle's loop controls Ca 2+ excretion and NaCl reabsorption in response to extracellular Ca 2+ However, the function of CaSR in the regulation of NaCl reabsorption in the distal convoluted tubule (DCT) is unknown. We hypothesized that CaSR in this location is involved in activating the thiazide-sensitive NaCl cotransporter (NCC) to prevent NaCl loss. Methods We used a combination of in vitro and in vivo models to examine the effects of CaSR on NCC activity. Because the KLHL3-WNK4-SPAK pathway is involved in regulating NaCl reabsorption in the DCT, we assessed the involvement of this pathway as well. Results Thiazide-sensitive 22 Na + uptake assays in Xenopus laevis oocytes revealed that NCC activity increased in a WNK4-dependent manner upon activation of CaSR with Gd 3+ In HEK293 cells, treatment with the calcimimetic R-568 stimulated SPAK phosphorylation only in the presence of WNK4. The WNK4 inhibitor WNK463 also prevented this effect. Furthermore, CaSR activation in HEK293 cells led to phosphorylation of KLHL3 and WNK4 and increased WNK4 abundance and activity. Finally, acute oral administration of R-568 in mice led to the phosphorylation of NCC. Conclusions Activation of CaSR can increase NCC activity via the WNK4-SPAK pathway. It is possible that activation of CaSR by Ca 2+ in the apical membrane of the DCT increases NaCl reabsorption by NCC, with the consequent, well known decrease of Ca 2+ reabsorption, further promoting hypercalciuria. Copyright © 2018 by the American Society of Nephrology.

Modeling the Onset of Phase Separation in CaO-SiO2-CaCl2 Chlorine-Containing Silicate Glasses.

PubMed

Swansbury, Laura A; Mountjoy, Gavin; Chen, Xiaojing; Karpukhina, Natalia; Hill, Robert

2017-06-08

The addition of chlorine into a bioactive glass composition is expected to reduce its abrasiveness and increase its bioactivity, which is important for dental applications such as toothpastes. There is a lack of information and understanding regarding the structural role of chlorine in chlorine-containing bioactive silicate glasses. This has prompted classical core-shell model molecular dynamics simulations of (50 - x/2)CaO-(50 - x/2)SiO 2 -xCaCl 2 glasses to be performed, where x ranges from x = 0.0 to 43.1 mol % CaCl 2 . These ternary glasses are advantageous for a fundamental study because they do not have additional network formers (e.g., phosphorus pentoxide) or modifiers (e.g., sodium) typically found in bioactive glass compositions. The (50 - x/2)CaO-(50 - x/2)SiO 2 -xCaCl 2 glasses were seen to become phase-separated around the x = 16.1 mol % CaCl 2 composition, and chlorine predominantly coordinated with calcium. These findings provide a solid foundation for further computational modeling work on more complex chlorine-containing bioactive glass compositions.

CO2 sensing of La0.875Ca0.125FeO3 in wet vapor: a comparison of experimental results and first-principles calculations.

PubMed

Wang, Xiaofeng; Chen, Yanping; Qin, Hongwei; Li, Ling; Shi, Changmin; Liu, Liang; Hu, Jifan

2015-05-28

Experimental results show that with an increase of relative humidity, the resistance of La0.875Ca0.125FeO3 decreases at room temperature but increases at higher temperatures (140-360 °C). The humid effect at room temperature is due to the movement of H(+) or H3O(+) inside of the condensed water layer on the surface of La0.875Ca0.125FeO3. Regarding the humid effect at high temperatures, the density functional theory (DFT) calculations show that H2O can be adsorbed onto the La0.875Ca0.125FeO3 surface in the molecular and dissociative adsorption configurations, where the La0.875Ca0.125FeO3 surface gains some electrons from H2O or its dissociative products, consistent with our observation. Experimental results also show that CO2 sensing response at high temperatures decreases with an increase of room-temperature relative humidity. DFT calculations indicate that CO2 adsorbed onto the La0.875Ca0.125FeO3(010) surface, where high concentration oxygen adsorption occurs without water adsorption nearby, releases some electrons into the semiconductor surface, playing the role of a donor. The interaction between CO2 and the local La0.875Ca0.125FeO3(010) surface with pre-adsorption of H2O nearby results in some electron transfer from the La0.875Ca0.125FeO3 surface to CO2, which is responsible for the weakening of CO2 response at high temperatures for La0.875Ca0.125FeO3 with an increase of room-temperature relative humidity.

Analysis of X-ray adsorption edges: L 2,3 edge of FeCl 4 -

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bagus, Paul S.; Nelin, Connie J.; Ilton, Eugene S.

We describe a detailed analysis of the features of the X-ray adsorption spectra at the Fe L 2,3 edge of FeCl 4. The objective of this analysis is to explain the origin of the complex features in relation to properties of the wavefunctions, especially for the excited states. These properties include spin-orbit and ligand field splittings where a novel aspect of the dipole selection rules is applied to understand the influence of these splittings on the spectra. We also explicitly take account of the intermediate coupling of the open core and valence shell electrons. Our analysis also includes comparison ofmore » theory and experiment for the Fe L 2,3 edge and comparison of theoretical predictions for the Fe 3+ cation and FeCl 4-. The electronic structure is obtained from theoretical wavefunctions for the ground and excited states.« less

Magnetic solid base catalyst CaO/CoFe2O4 for biodiesel production: Influence of basicity and wettability of the catalyst in catalytic performance

NASA Astrophysics Data System (ADS)

Zhang, Pingbo; Han, Qiuju; Fan, Mingming; Jiang, Pingping

2014-10-01

A novel magnetic solid base catalyst CaO/CoFe2O4 was successfully prepared with CoFe2O4 synthesized by hydrothermal method as the magnetic core and applied to the transesterification of soybean oil for the production of biodiesel. The magnetic solid base catalysts were characterized by a series of techniques including CO2-TPD, powder XRD, TGA, TEM and the contact angle measurement of the water droplet. It was demonstrated that CaO/CoFe2O4 has stronger magnetic strength indicating perfect utility for repeated use and better basic strength. Compared with CaO/ZnFe2O4 and CaO/MnFe2O4, solid base catalyst CaO/CoFe2O4 has better catalytic performance, weaker hydroscopicity and stronger wettability, demonstrating that catalytic performance was relative to both basicity of catalyst and the full contact between the catalyst and the reactants, but the latter was a main factor in the catalytic system.

Near-infrared spectroscopic investigation of water in supercritical CO2 and the effect of CaCl2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zheming; Felmy, Andrew R.; Thompson, Christopher J.

2013-01-01

Near-infrared (NIR) spectroscopy was applied to investigate the dissolution and chemical interaction of water dissolved into supercritical carbon dioxide (scCO2) and the influence of CaCl2 in the co-existing aqueous phase at fo empe e : 40 50 75 nd 100 C at 90 atm. Consistent with the trend of the vapor pressure of water, the solubility of pure water in scCO2 inc e ed f om 40 °C (0.32 mole%) o 100 °C (1.61 mole%). The presence of CaCl2 negatively affects the solubility of water in scCO2: at a given temperature and pressure the solubility of water decreased as themore » concentration of CaCl2 in the aqueous phase increased, following the trend of the activity of water. A 40 °C, the water concentration in scCO2 in contact with saturated CaCl2 aqueous solution was only 0.16 mole%, a drop of more than 50% as compared to pure water while that a 100 °C was 1.12 mole%, a drop of over 30% as compared to pure water, under otherwise the same conditions. Analysis of the spectral profiles suggested that water dissolved into scCO2 exists in the monomeric form under the evaluated temperature and pressure conditions, for both neat water and CaCl2 solutions. However, its rotational degrees of freedom decrease at lower temperatures due to higher fluid densities, leading to formation of weak H2O:CO2 Lewis acid-base complexes. Similarly, the nearly invariant spectral profiles of dissolved water in the presence and absence of saturated CaCl2 under the same experimental conditions was taken as evidence that CaCl2 dissolution in scCO2 was limited as the dissolved Ca2+/CaCl2 would likely be highly hydrated and would alter the overall spectra of waters in the scCO2 phase.« less

Fe²⁺ block and permeation of CaV3.1 (α1G) T-type calcium channels: candidate mechanism for non-transferrin-mediated Fe²⁺ influx.

PubMed

Lopin, Kyle V; Gray, I Patrick; Obejero-Paz, Carlos A; Thévenod, Frank; Jones, Stephen W

2012-12-01

Iron is a biologically essential metal, but excess iron can cause damage to the cardiovascular and nervous systems. We examined the effects of extracellular Fe²⁺ on permeation and gating of Ca(V)3.1 channels stably transfected in HEK293 cells, by using whole-cell recording. Precautions were taken to maintain iron in the Fe²⁺ state (e.g., use of extracellular ascorbate). With the use of instantaneous I-V currents (measured after strong depolarization) to isolate the effects on permeation, extracellular Fe²⁺ rapidly blocked currents with 2 mM extracellular Ca²⁺ in a voltage-dependent manner, as described by a Woodhull model with K(D) = 2.5 mM at 0 mV and apparent electrical distance δ = 0.17. Extracellular Fe²⁺ also shifted activation to more-depolarized voltages (by ∼10 mV with 1.8 mM extracellular Fe²⁺) somewhat more strongly than did extracellular Ca²⁺ or Mg²⁺, which is consistent with a Gouy-Chapman-Stern model with surface charge density σ = 1 e(-)/98 Ų and K(Fe) = 4.5 M⁻¹ for extracellular Fe²⁺. In the absence of extracellular Ca²⁺ (and with extracellular Na⁺ replaced by TEA), Fe²⁺ carried detectable, whole-cell, inward currents at millimolar concentrations (73 ± 7 pA at -60 mV with 10 mM extracellular Fe²⁺). With a two-site/three-barrier Eyring model for permeation of Ca(V)3.1 channels, we estimated a transport rate for Fe²⁺ of ∼20 ions/s for each open channel at -60 mV and pH 7.2, with 1 μM extracellular Fe²⁺ (with 2 mM extracellular Ca²⁺). Because Ca(V)3.1 channels exhibit a significant "window current" at that voltage (open probability, ∼1%), Ca(V)3.1 channels represent a likely pathway for Fe²⁺ entry into cells with clinically relevant concentrations of extracellular Fe²⁺.

Pressure-induced quantum phase transition in the quantum antiferromagnet CsFeCl3

NASA Astrophysics Data System (ADS)

Hayashida, Shohei; Zaharko, Oksana; Kurita, Nobuyuki; Tanaka, Hidekazu; Hagihala, Masato; Soda, Minoru; Itoh, Shinichi; Uwatoko, Yoshiya; Masuda, Takatsugu

2018-04-01

We have studied the pressure-induced quantum phase transition in the singlet-ground-state antiferromagnet CsFeCl3. Neutron diffraction experiments under pressure evidence the magnetic long-range order at low temperatures. Magnetic structure analysis reveals a 120∘ structure with a propagation vector of kmag=(1 /3 ,1 /3 ,0 ) . The estimated critical exponent of the order parameter suggests that CsFeCl3 belongs to the universality class of U (1 ) ×Z2 symmetry which is expected to realize the chiral liquid state.

Ferric chloride-graphite intercalation compounds as anode materials for Li-ion batteries.

PubMed

Wang, Lili; Zhu, Yongchun; Guo, Cong; Zhu, Xiaobo; Liang, Jianwen; Qian, Yitai

2014-01-01

Ferric chloride-graphite intercalation compounds (FeCl3 -GICs) with stage 1 and stage 2 structures were synthesized by reacting FeCl3 and expanded graphite (EG) in air in a stainless-steel autoclave. As rechargeable Li-ion batteries, these FeCl3 -GICs exhibit high capacity, excellent cycling stability, and superior rate capability, which could be attributed to their unique intercalation features. This work may enable new possibilities for the fabrication of Li-ion batteries. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The influence of Ca substitution on LaFeO3 nanoparticles in terms of structural and magnetic properties.

PubMed

Lin, Qing; Xu, Jianmei; Yang, Fang; Yang, Xingxing; He, Yun

2018-01-01

The nanocrystalline structure of La 1 -x Ca x FeO 3 was prepared by a sol-gel method involving an auto-combustion process. The incorporation of rare-earths in LaFeO 3 induces strain in magnetic properties, especially in terms of the following parameters: replacement amount, oxygen partial pressure, and calcination temperature. To determine the effects of the amount of Ca 2+ ion doping agent and the calcination temperature on the microstructure, particle morphology, and magnetic properties of LaFeO 3 crystal, we performed the following respective analytical methods: X-ray powder diffraction, Fourier-transform infrared (FT-IR) spectroscopy, scanning electron microscopy, and vibrating sample magnetometer tests. The orthorhombic structure of LaFeO 3 perovskite did not change even when it was doped with Ca 2+ ions, and its space group continued to be Pnma (No.62). FT-IR spectra confirmed that the main band appearing at 568 cm -1 is due to the antisymmetric stretching vibration of Fe-O-Fe bonds in FeO 6 . The introduction of Ca inhibits the growth of grains but the morphology of particles is improved. With an increasing concentration of Ca 2+ ions, magnetic behavior of the samples also witnessed an increasing trend in a proportionate manner. With an increase in calcination temperature, the enclosed area of the magnetic hysteresis curve of the sample reduced remarkably. The growth of nanoparticles can be restrained with an increase of Ca content that is used as doping agent. The magnetic behavior of La 1 -x Ca x FeO 3 tilts towards G-type antiferromagnetism; the magnetic orientation is achieved from the super exchange interaction of Fe 3+ ions with oxygen ions.

A high performance hybrid battery based on aluminum anode and LiFePO4 cathode.

PubMed

Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; Fang, Youxing; Bridges, Craig A; Paranthaman, M Parans; Dai, Sheng; Brown, Gilbert M

2016-01-28

A novel hybrid battery utilizing an aluminum anode, a LiFePO4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl3) (EMImCl-AlCl3, 1-1.1 in molar ratio) with or without LiAlCl4 is proposed. The hybrid ion battery delivers an initial high capacity of 160 mA h g(-1) at a current rate of C/5. It also shows good rate capability and cycling performance.

A high performance hybrid battery based on aluminum anode and LiFePO 4 cathode

DOE PAGES

Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; ...

2015-12-07

A unique battery hybrid utilizes an aluminum anode, a LiFePO 4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl 3) (EMImCl-AlCl 3, 1-1.1 in molar ratio) with or without LiAlCl 4 is proposed. This hybrid ion battery delivers an initial high capacity of 160 mAh g -1 at a current rate of C/5. It also shows good rate capability and cycling performance.

Elemental composition of commercial sea cucumbers (holothurians).

PubMed

Wen, J; Hu, C

2010-01-01

Toxic and essential elements in 11 different sea cucumber species were determined and compared with daily intake recommendations and maximum allowed levels. The contents of macro-elements contents in dried sea cucumber samples were found to be 25,000-152,000 mg kg(-1) for Na, 4000-8600 mg kg(-1) for Mg, 1100-5200 mg kg(-1) for K, 15,000-68,000 mg kg(-1) and 36,300-251,000 mg kg(-1) for Cl. Trace element concentrations in dried sea cucumber samples were found to be 11-100 mg kg(-1) for Zn, 41-660 mg kg(-1) for Fe, 3-74 mg kg(-1) for Cu, 1.1-16 mg kg(-1) for Mn, 1.4-3.7 mg kg(-1) for Se, 1.1-9.6 mg kg(-1) for Cr, and 0.3-5.1 mg kg(-1) for Ni. All sea cucumber species were rich sources of Na, Cl, Mg, Ca, Fe, Cu, Se and Cr for human consumption. Regarding contaminants, As, Cd and Pb concentrations in dried sea cucumbers were in the ranges of 1.1-6.1, 0.03-0.06 and 0.11-0.69 mg kg(-1), respectively. Moreover, Hg values of 11 sea cucumbers were below the detection limit (0.01 mg kg(-1)).

57Fe Mössbauer study of stoichiometric iron-based superconductor CaKFe 4As 4: a comparison to KFe 2As 2 and CaFe 2As 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bud’ko, Sergey L.; Kong, Tai; Meier, William R.

57Fe Mössbauer spectra at different temperatures between ~5 and ~300 K were measured on an oriented mosaic of single crystals of CaKFe 4 As 4. The data indicate that is a well formed compound with narrow spectral lines, no traces of other, Fe – containing, secondary phases in the spectra and no static magnetic order. There is no discernible feature at the superconducting transition temperature in any of the hyperfine parameters. The temperature dependence of the quadrupole splitting approximately follows the empirical ‘ T 3/2 law’. Furthermore, the hyperfine parameters of CaKFe 4 As 4 are compared with those formore » measured in this work, and the literature data for CaFe 2 As 2, and were found to be in between those for these two, ordered, 122 compounds, in agreement with the gross view of CaKFe 4 As 4 as a structural analog of KFe 2 As 2 and CaFe 2 As 2 that has alternating Ca- and K-layers in the structure.« less

57Fe Mössbauer study of stoichiometric iron-based superconductor CaKFe 4As 4: a comparison to KFe 2As 2 and CaFe 2As 2

DOE PAGES

Bud’ko, Sergey L.; Kong, Tai; Meier, William R.; ...

2017-07-06

57Fe Mössbauer spectra at different temperatures between ~5 and ~300 K were measured on an oriented mosaic of single crystals of CaKFe 4 As 4. The data indicate that is a well formed compound with narrow spectral lines, no traces of other, Fe – containing, secondary phases in the spectra and no static magnetic order. There is no discernible feature at the superconducting transition temperature in any of the hyperfine parameters. The temperature dependence of the quadrupole splitting approximately follows the empirical ‘ T 3/2 law’. Furthermore, the hyperfine parameters of CaKFe 4 As 4 are compared with those formore » measured in this work, and the literature data for CaFe 2 As 2, and were found to be in between those for these two, ordered, 122 compounds, in agreement with the gross view of CaKFe 4 As 4 as a structural analog of KFe 2 As 2 and CaFe 2 As 2 that has alternating Ca- and K-layers in the structure.« less

Studies of structure of calcium-iron phosphate glasses by infrared, Raman and UV-Vis spectroscopies

NASA Astrophysics Data System (ADS)

Li, H. J.; Liang, X. F.; Yu, H. J.; Yang, D. Q.; Yang, S. Y.

2016-06-01

Glasses in the ternary CaO-Fe2O3-P2O5 system were prepared and studied by means of density, differential scanning calorimetry, infrared, Raman and UV-Vis spectroscopies. The results showed that density and molar volume in the glass system decreased with increasing substitution of CaO for Fe2O3. The variation of glass transition temperature and thermal stability was strictly related to the nature of bonding in the vitreous network. Spectroscopic analysis showed that substitution of CaO for Fe2O3 induced an evolution of structural units from pyrophosphate to metaphosphate species indicating the polymerization of phosphate chains and the decrease of non-bridging oxygen concentrations. With increasing substitution of CaO for Fe2O3 The P-O-Ca linkage and (P-O- Ca2+ -O-P) chains participated in the glass network by replacing P-O-Fe bonds. The absorption band of the P-O-Ca stretching mode in the glasses with high CaO content (≥32 mol%) was assigned at around 1084 cm-1. The absorption edge would fall in the region between 332 and 420 nm which are the absorption bands of Fe3+ ions.

Eu(2+)-Activated Alkaline-Earth Halophosphates, M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) for NUV-LEDs: Site-Selective Crystal Field Effect.

PubMed

Kim, Donghyeon; Kim, Sung-Chul; Bae, Jong-Seong; Kim, Sungyun; Kim, Seung-Joo; Park, Jung-Chul

2016-09-06

Eu(2+)-activated M5(PO4)3X (M = Ca, Sr, Ba; X = F, Cl, Br) compounds providing different alkaline-earth metal and halide ions were successfully synthesized and characterized. The emission peak maxima of the M5(PO4)3Cl:Eu(2+) (M = Ca, Sr, Ba) compounds were blue-shifted from Ca to Ba (454 nm for Ca, 444 nm for Sr, and 434 nm for Ba), and those of the Sr5(PO4)3X:Eu(2+) (X = F, Cl, Br) compounds were red-shifted along the series of halides, F → Cl → Br (437 nm for F, 444 nm for Cl, and 448 nm for Br). The site selectivity and occupancy of the activator ions (Eu(2+)) in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) crystal lattices were estimated based on theoretical calculation of the 5d → 4f transition energies of Eu(2+) using LCAO. In combination with the photoluminescence measurements and theoretical calculation, it was elucidated that the Eu(2+) ions preferably enter the fully oxygen-coordinated sites in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) compounds. This trend can be well explained by "Pauling's rules". These compounds may provide a platform for modeling a new phosphor and application in the solid-state lighting field.

Electrodeposition of amorphous Ni P coatings onto Nd Fe B permanent magnet substrates

NASA Astrophysics Data System (ADS)

Ma, C. B.; Cao, F. H.; Zhang, Z.; Zhang, J. Q.

2006-12-01

Decorative and protective Ni-P amorphous coatings were electroplated onto NdFeB permanent magnet from an ortho-phosphorous acid contained bath. The influences of the main electroplating technological parameters including current density, bath pH, bath temperature and H3PO3 on the structure and chemical composition of Ni-P coatings were investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques in conjunction with X-ray diffraction (XRD), scanning transmission electron microscopy (SEM) and X-ray energy-dispersive spectrometry (EDX). The optimized amorphous Ni-P coated NdFeB can stand for ca. 180 h against neutral 3.0 wt.% NaCl salt spray without any pitting corrosion. Meanwhile, the results also showed that large phosphorous content is the precondition for Ni-P coatings to possess the amorphous structure, but too much high phosphorous content can damage the amorphous structure due to the separation of superfluous P from Ni2P/Ni3P and the resultant formation of multi-phase coatings (such as Ni2P-P).

The in vitro photodynamic effect of laser activated gallium, indium and iron phthalocyanine chlorides on human lung adenocarcinoma cells.

PubMed

Maduray, K; Odhav, B

2013-11-05

Metal-based phthalocyanines currently are utilized as a colorant for industrial applications but their unique properties also make them prospective photosensitizers. Photosensitizers are non-toxic drugs, which are commonly used in photodynamic therapy (PDT), for the treatment of various cancers. PDT is based on the principle that, exposure to light shortly after photosensitizer administration predominately leads to the production of reactive oxygen species for the eradication of cancerous cells and tissue. This in vitro study investigated the photodynamic effect of gallium (GaPcCl), indium (InPcCl) and iron (FePcCl) phthalocyanine chlorides on human lung adenocarcinoma cells (A549). Experimentally, 2 × 10(4)cells/ml were seeded in 24-well tissue culture plates and allowed to attach overnight, after which cells were treated with different concentrations of GaPcCl, InPcCl and FePcCl ranging from 2 μg/ml to 100 μg/ml. After 2h, cells were irradiated with constant light doses of 2.5 J/cm(2), 4.5 J/cm(2) and 8.5 J/cm(2) delivered from a diode laser (λ = 661 nm). Post-irradiated cells were incubated for 24h before cell viability was measured using the MTT Assay. At 24h after PDT, irradiation with a light dose of 2.5 J/cm(2) for each photosensitizing concentration of GaPcCl, InPcCl and FePcCl produced a significant decrease in cell viability, but when the treatment light dose was further increased to 4.5 J/cm(2) and 8.5 J/cm(2) the cell survival was less than 40%. Results also showed that photoactivated FePcCl decreased cell survival of A549 cells to 0% with photosensitizing concentrations of 40 μg/ml and treatment light dose of 2.5 J/cm(2). A 20 μg/ml photosensitizing concentration of FePcCl in combination with an increased treatment light dose of either 4.5 J/cm(2) or 8.5 J/cm(2) also resulted in 0% cell survival. This PDT study concludes that low concentrations on GaPcCl, InPcCl and FePcCl activated with low level light doses can be used for the effective in vitro killing of lung cancer cells. Copyright © 2013 Elsevier B.V. All rights reserved.

Immobilization of hexavalent chromium in contaminated soils using biochar supported nanoscale iron sulfide composite.

PubMed

Lyu, Honghong; Zhao, Hang; Tang, Jingchun; Gong, Yanyan; Huang, Yao; Wu, Qihang; Gao, Bin

2018-03-01

Biochar supported carboxymethyl cellulose (CMC)-stabilized nanoscale iron sulfide (FeS) composite (CMC-FeS@biochar) was prepared and tested for immobilization of hexavalent chromium Cr(VI) in soil. Results of UV-vis and transmission electron microscopy (TEM) showed that the backbone of biochar suppressed the aggregation of FeS, resulting in smaller particle size and more sorption sites than bare FeS. The composite at a dosage of 2.5 mg per gram soil displayed an enhanced Cr(VI) immobilization efficiency (a 94.7% reduction in the toxicity characteristic leaching procedure (TCLP) based leachability and a 95.6% reduction in the CaCl 2 extraction) compared to plain biochar and bare FeS. Sequential extraction procedure (SEP) and X-ray photoelectron spectroscopy (XPS) analysis suggested that CMC-FeS@biochar promoted the conversion of more accessible Cr (exchangeable and carbonate-bound fractions) into the less accessible forms (iron-manganese oxides-bound, organic material-bound, and residual fractions) to reduce the toxicity of Cr(VI) and that surface sorption and reduction were dominant mechanisms for Cr(VI) immobilization. CMC-FeS@biochar greatly reduced the bioavailability of Cr(VI) to wheat and earthworms (Eisenia fetida). Moreover, the application of CMC-FeS@biochar enhanced soil organic matter content and microbial activity. This work highlighted the potential of CMC-FeS@biochar composite as a low-cost, "green", and effective amendment for immobilizing Cr(VI) in contaminated soils and improving soil properties. Copyright © 2017 Elsevier Ltd. All rights reserved.

Protective effects of fucoxanthin against ferric nitrilotriacetate-induced oxidative stress in murine hepatic BNL CL.2 cells.

PubMed

Liu, Cheng-Ling; Liang, Ai-Ling; Hu, Miao-Lin

2011-10-01

Fucoxanthin is a carotenoid that is rich in some seaweed. Although fucoxanthin has been reported to possess radical-scavenging activities in vitro, little is known whether it may protect against iron-induced oxidative stress in cultured cells. In this study, we examined the protection of fucoxanthin against oxidative damage in BNL CL.2 cells induced by ferric nitrilotriacetate (Fe-NTA). The data show that incubation of BNL CL.2 cells with Fe-NTA for 30 min significantly decreased cell proliferation, whereas pretreatment with fucoxanthin (1-20 μΜ) for 24h significantly recovered cell proliferation in a dose-dependent manner. In addition, fucoxanthin pretreatment significantly decreased intracellular reactive oxygen species (ROS) and DNA damage in BNL CL.2 cells incubated with Fe-NTA for 30 min. Moreover, fucoxanthin markedly decreased the level of thiobarbituric acid-reactive substances (TBARS) and protein carbonyl contents in BNL CL.2 cells induced by Fe-NTA. By contrast, fucoxanthin significantly increased the levels of GSH in a concentration-dependent manner. These results demonstrate that fucoxanthin at 1-20μΜ effectively prevents cytotoxicity in BNL CL.2 cells treated with Fe-NTA, and that the protective effect is likely associated with decreased intracellular ROS, TBARS, protein carbonyl contents and increased GSH levels. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

Some mineral stability relations in the system CaOMgOSiO2H2OHCl

USGS Publications Warehouse

Luce, R.W.; Cygan, G.L.; Hemley, J.J.; d'Angelo, W. M.

1985-01-01

Mineral-aqueous solution equilibria for the assemblages talc-quartz, tremolite-talc-quartz, diopside-tremolite-quartz, wollastonite-diopside-quartz and wollastonite-quartz have been studied at 2 kb total pressure, 500?? to 700??C and chloride concentrations from 0.03 to 6.0 molal. Most work was at 1 m chloride. Both buffered and unbuffered data were obtained and a recalibration of the Ag-AgCl buffer is presented. Log equilibrium quotients at 500??, 600?? and 700??C are respectively: Ta-Qz ( mMgCl2 mHCl2) 2.57, 1.71, 0.73; Tr-Ta-Qz and Di-Tr-Qz ( mCaCl2 mMgCl2mHCl2) 4.98, 3.99, 2.21 and 7.29, 5.30, 3.56; WoDi-Qz ( mCaCl2 mMgCl2) 3.30, 3.00, 2.79: Wo-Qz ( mCaCl2 mHCl2) 5.15, 3.95, 2.68. Mineral stability fields plotted in terms of these concentration data more tangibly represent the compositional character of real systems and the mass transfer capabilities of their fluids than do the analogous theoretical activity diagrams. Overall dissociation constants of MgCl2 and CaCl2 were calculated from the experimental data using the calculated ionic activity constants for the reactions and the established dissociation constants of HCl. The negative log values are respectively: 3.88. 6.63, 9.20 for CaCl2 and 4.60, 7.54, 10.37 for MgCl2 at 500??, 600?? and 700??C, 2 kb. The Ca values are about an order of magnitude more positive than the conductance-derived values by Frantz and Marshall (1982). The phase relations developed in this study have application to the genesis of talc, tremolite, and diopside-bearing assemblages in some regional metamorphic rocks, but more specifically to the calcsilicate skarn assemblages of many metasomatic aureoles. The equilibrium fluids are characterized by high concentrations of Ca relative to Mg and increasing Ca Mg ratios with decreasing temperatures. The stability fields of talc, tremolite, and quartz expand relative to those of diopside and wollastonite with decreasing temperature, hence their more common appearance as retrograde products in skarn systems. ?? 1985.

Enhanced phosphate removal from wastewater by using in situ generated fresh trivalent Fe composition through the interaction of Fe(II) on CaCO3.

PubMed

Li, Yujie; He, Xiaoman; Hu, Huimin; Zhang, Tingting; Qu, Jun; Zhang, Qiwu

2018-05-21

Excessive existences of nutrients such as phosphate in the aqueous environment remain as a heavy concern although many researches have been reported for dealing with their removal. Based on the understanding toward the interactions of Fe compounds with phosphate and carbonate from many available researches, we designed a very simple and efficient approach for phosphate removal by using in situ generated fresh trivalent Fe composition through the interaction of Fe(II) as FeSO 4 on CaCO 3 . Addition and agitation of Fe(II) and CaCO 3 simultaneously to phosphate solution allowed an amorphous Fe(III)-P or Ca-Fe(III)-P precipitation, with a phosphate removal rate close to 100%, to reduce the residual phosphorus concentration less than 0.03 mg/L from 100 mg/L, reaching the discharge limit, even with the addition amounts of CaCO 3 as low as a stoichiometric ratio of CaCO 3 /PO 4 3- at 0.9 and ratio of Fe(II)/PO 4 3- at 1.5, and the percent of P 2 O 5 in the precipitate was as high as 19.4% enough as phosphate source for fertilizer production. Different from the alkaline process with enough OH - group, the slow hydrolysis of CaCO 3 resulting in low concentration of OH - group for the formation of Fe(OH) 2 , which was oxidized soon by air into trivalent Fe, achieved a continuous generation of fresh ferric composition for phosphate precipitation and could avoid its rapid formation and subsequent transformation into stable FeOOH of large particle size to lose the activity. These results based on the synergistic effect of using CaCO 3 and Fe(II) together may have applications in the treatment of eutrophic wastewater through a process with many advantages of easy operation and low-cost besides the high removal efficiency with phosphate percentage inside the precipitate high enough to serve for fertilizer production. Copyright © 2018 Elsevier Ltd. All rights reserved.

PIXE and ICP-MS Analysis of Andrographis Paniculata Medicinal Plant

NASA Astrophysics Data System (ADS)

Chandrasekhar Rao, J.; Naidu, B. G.; Sarita, P.; Srikanth, S.; Naga Raju, G. J.

2017-08-01

The concentrations of elements Li, Be, Al, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Ag, Cd, Ba, Pb and U in Andrographis Paniculata medicinal plant used in the treatment of Diabetes Mellitus were determined by using Particle Induced X-ray Emission (PIXE) and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) techniques. This plant was collected from four different geographical locations in Andhra Pradesh, India in order to assess the regional variation of elemental concentrations. Appreciable levels of K, Ca, Cr, Mn, Cu and Zn determined in this plant can be correlated to the antidiabetic property of Andrographis Paniculata since these elements are known to regulate and potentiate insulin action. Presence of toxic elements As, Cd and Pb necessitates the adoption of precautionary measures while prescribing dosage of the herbal medicine prepared from this plant for the treatment diabetes mellitus.

Casein phosphopeptides and CaCl2 increase penicillin production and cause an increment in microbody/peroxisome proteins in Penicillium chrysogenum.

PubMed

Domínguez-Santos, Rebeca; Kosalková, Katarina; García-Estrada, Carlos; Barreiro, Carlos; Ibáñez, Ana; Morales, Alejandro; Martín, Juan-Francisco

2017-03-06

Transport of penicillin intermediates and penicillin secretion are still poorly characterized in Penicillium chrysogenum (re-identified as Penicillium rubens). Calcium (Ca 2+ ) plays an important role in the metabolism of filamentous fungi, and casein phosphopeptides (CPP) are involved in Ca 2+ internalization. In this study we observe that the effect of CaCl 2 and CPP is additive and promotes an increase in penicillin production of up to 10-12 fold. Combination of CaCl 2 and CPP greatly promotes expression of the three penicillin biosynthetic genes. Comparative proteomic analysis by 2D-DIGE, identified 39 proteins differentially represented in P. chrysogenum Wisconsin 54-1255 after CPP/CaCl 2 addition. The most interesting group of overrepresented proteins were a peroxisomal catalase, three proteins of the methylcitrate cycle, two aminotransferases and cystationine β-synthase, which are directly or indirectly related to the formation of penicillin amino acid precursors. Importantly, two of the enzymes of the penicillin pathway (isopenicillin N synthase and isopenicillin N acyltransferase) are clearly induced after CPP/CaCl 2 addition. Most of these overrepresented proteins are either authentic peroxisomal proteins or microbody-associated proteins. This evidence suggests that addition of CPP/CaCl 2 promotes the formation of penicillin precursors and the penicillin biosynthetic enzymes in peroxisomes and vesicles, which may be involved in transport and secretion of penicillin. Penicillin biosynthesis in Penicillium chrysogenum is one of the best characterized secondary metabolism processes. However, the mechanism by which penicillin is secreted still remains to be elucidated. Taking into account the role played by Ca 2+ and CPP in the secretory pathway and considering the positive effect that Ca 2+ exerts on penicillin production, the analysis of global protein changes produced after CPP/CaCl 2 addition is very helpful to decipher the processes related to the biosynthesis and secretion of penicillin. Copyright © 2017 Elsevier B.V. All rights reserved.

Temporal Variability of Groundwater Chemistry in Shallow and Deep Aquifers of Araihazar, Bangladesh

PubMed Central

Dhar, R. K.; Zheng, Y.; Stute, M.; van Geen, A.; Cheng, Z.; Shanewaz, M.; Shamsudduha, M.; Hoque, M. A.; Rahman, M. W.; Ahmed, K. M.

2008-01-01

Samples were collected every 2–4 weeks from a set of 37 monitoring wells over a period of 2–3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5–91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to ± 90%. In wells tapping the deeper aquifers > 30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by 3H/3He and 14C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged < 5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 µg/L (range: < 5 to 648 µg/L; n=118) and 272 µg/L (range: 10 to 485 µg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with > 5 yr 3H/3He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanism of mobilization. PMID:18467001

Influence of ball milling and annealing conditions on the properties of L10 FePt nanoparticles fabricated by a new green chemical synthesis method

NASA Astrophysics Data System (ADS)

Hu, X. C.; Capobianchi, A.; Gallagher, R.; Hadjipanayis, G. C.

2014-05-01

In this work, a new green chemical strategy for the synthesis of L10 FePt alloy nanoparticles is reported. The precursor is a polycrystalline molecular complex (Fe(H2O)6PtCl6), in which Fe and Pt atoms are arranged on alternating planes and milled with NaCl to form nanocrystals. Then the mixture was annealed under reducing atmosphere (5% H2 and 95% Ar) at temperatures varying from 350 °C to 500 °C for 2 h with a heating rate of 5 °C/min. After the reduction, the mixture was washed with water to remove the NaCl and L10 FePt nanoparticles were obtained. The X-Ray Diffraction pattern showed the presence of the characteristic peaks of the fct phase of FePt nanoparticles. Influence of precursor/NaCl ratio and ball milling time on particle size was investigated. Transmission electron microscopy images revealed that smaller precursor/NaCl ratio (10 mg/20 g) and longer milling time (15 h) lead to smaller particle size and narrower size distribution. Milling time does not influence the coercivity much but the decrease of the amount of precursor leads to a decrease of coercivity from 10.8 kOe to 4.8 kOe.

Medium-resolution Spectroscopy of Red Giant Branch Stars in ω Centauri

NASA Astrophysics Data System (ADS)

An, Deokkeun; Lee, Young Sun; In Jung, Jae; Rey, Soo-Chang; Rhee, Jaehyon; Lee, Jae-Woo; Lee, Young-Wook; Joe, Young Hoon

2017-10-01

We present [Fe/H] and [Ca/Fe] of ˜600 red giant branch (RGB) members of the globular cluster Omega Centauri (ω {Cen}). We collect medium-resolution (R˜ 2000) spectra using the Blanco 4 m telescope at the Cerro Tololo Inter-American Observatory equipped with Hydra, the fiber-fed multi-object spectrograph. We demonstrate that blending of stellar light in optical fibers severely limits the accuracy of spectroscopic parameters in the crowded central region of the cluster. When photometric temperatures are taken in the spectroscopic analysis, our kinematically selected cluster members, excluding those that are strongly affected by flux from neighboring stars, include relatively fewer stars at intermediate metallicity ([{Fe}/{{H}}]˜ -1.5) than seen in the previous high-resolution survey for brighter giants in Johnson & Pilachowski. As opposed to the trend of increasing [Ca/Fe] with [Fe/H] found by those authors, our [Ca/Fe] estimates, based on Ca II H & K measurements, show essentially the same mean [Ca/Fe] for most of the metal-poor and metal-intermediate populations in this cluster, suggesting that mass- or metallicity-dependent SN II yields may not be necessary in their proposed chemical evolution scenario. Metal-rich cluster members in our sample show a large spread in [Ca/Fe], and do not exhibit a clear bimodal distribution in [Ca/Fe]. We also do not find convincing evidence for a radial metallicity gradient among RGB stars in ω {Cen}.

Effects of FeCl3 additives on optical parameters of PVA

NASA Astrophysics Data System (ADS)

Latif, Duha M. A.; Chiad, Sami S.; Erhayief, Muhssen S.; Abass, Khalid H.; Habubi, Nadir F.; Hussin, Hadi A.

2018-05-01

PVA doped FeCl3 have been deposited utilizing casting technique. Absorption spectrum was registered in the wavelengths (300-900 nm) utilizing UV-Visible spectrophotometer. Optical constants behavior such as, absorbance, absorption coefficient, and skin depth were studied. It was found these parameters were increased as Fe content increase. While the extinction coefficient and optical conductivity was decreased. The energy gap of PVA-Fe films were decreased from 4 eV for the PVA film to 3.5 eV for the PVA: 4 % Fe film.

Variations in iron and calcium abundances during solar flares

NASA Astrophysics Data System (ADS)

Antonucci, E.; Martin, R.

1995-07-01

Evidence for variations in iron and calcium abundances during the impulsive phase of solar flares has been obtained by analyzing the Ca XIX and Fe XXV spectra, detected with the Bent Crystal Spectrometer of the Solar Maximum Mission. The plasma thermal conditions have been investigated by considering different temperature indicators: namely, the temperatures TCa and TFe, derived from the intensity ratios of the dielectronic recombination satellites to the resonance line, and the temperature TCaFe, calculated from the ratio of the resonance lines of Ca XIX and Fe XXV, which is also depending on the Fe/Ca abundance ratio. The observed values of TCa and TFe can be ascribed to the specific characteristics of the plasma therma distribution, the corresponding values of TCaFe can be explained by allowing also for variations in the Fe/Ca abundance ratio relative to the photospheric ratio by a factor within 0.2 and 2.4. According to the observed abundance variations, the events analyzed can be divided in Ca-rich and Fe-rich flares.

A rice tonoplastic calcium exchanger, OsCCX2 mediates Ca2+/cation transport in yeast

PubMed Central

Yadav, Akhilesh K.; Shankar, Alka; Jha, Saroj K.; Kanwar, Poonam; Pandey, Amita; Pandey, Girdhar K.

2015-01-01

In plant cell, cations gradient in cellular compartments is maintained by synergistic action of various exchangers, pumps and channels. The Arabidopsis exchanger family members (AtCCX3 and AtCCX5) were previously studied and belong to CaCA (calcium cation exchangers) superfamily while none of the rice CCXs has been functionally characterized for their cation transport activities till date. Rice genome encode four CCXs and only OsCCX2 transcript showed differential expression under abiotic stresses and Ca2+ starvation conditions. The OsCCX2 localized to tonoplast and suppresses the Ca2+ sensitivity of K667 (low affinity Ca2+ uptake deficient) yeast mutant under excess CaCl2 conditions. In contrast to AtCCXs, OsCCX2 expressing K667 yeast cells show tolerance towards excess Na+, Li+, Fe2+, Zn2+ and Co2+ and suggest its ability to transport both mono as well as divalent cations in yeast. Additionally, in contrast to previously characterized AtCCXs, OsCCX2 is unable to complement yeast trk1trk2 double mutant suggesting inability to transport K+ in yeast system. These finding suggest that OsCCX2 having distinct metal transport properties than previously characterized plant CCXs. OsCCX2 can be used as potential candidate for enhancing the abiotic stress tolerance in plants as well as for phytoremediation of heavy metal polluted soil. PMID:26607171

New molecular assemblies of redox isomers, [CrIII(X4SQ)3-n(X4Cat)n]-n (X = Cl and Br; n = 0, 1, and 2), with metallocenium cations, [MIIICp2]+ (M = Co and Fe): X-ray crystal structures and physical properties.

PubMed

Chang, H C; Miyasaka, H; Kitagawa, S

2001-01-01

A series of redox isomers of [CrIII(X4SQ)(X4Cat)2]2-, [CrIII(X4SQ)2(X4Cat)]-, and [CrIII(X4SQ)3]0 (X = Cl and Br, SQ = semiquinonate, and Cat = catecholate) have been synthesized and characterized as charge-transfer (CT) compounds with metallocenium cations: (CoIIICp2)2[CrIII(Cl4SQ)(Cl4Cat)2] (1), (CoIIICp2)2[CrIII(Br4SQ)(Br4Cat)2] (2), (FeIIICp2)[CrIII(Cl4SQ)2(Cl4Cat)].C6H6 (4), (FeIIICp2)[CrIII(Br4SQ)2(Br4Cat)].CS2 (5), and (FeIIICp2)[CrIII(Cl4SQ)2(Cl4Cat)][CrIII(Cl4SQ)3] (6). First, the oxidation states of the chromium complexes are strongly dependent on the redox potentials of the metallocenes used. The CoIICp2, exhibiting stronger reduction power than FeIICp2, is useful for two-electron reduction of the [CrIII(X4SQ)3]0, affording [CrIII(X4SQ)(X4Cat)2]2- (1 and 2), which are first isolated and crystallographically characterized in the solid state. In contrast the reaction with FeIICp2 affords only [CrIII(X4SQ)2(X4Cat)]- (4 and 5). Second, solvents influence crystal structures of these compounds. The solvent set of C6H6/CS2 gives 1:1:C6H6 compound 4 with unique charged anions, [CrIII(Cl4SQ)2(Cl4Cat)]-, while the other set, n-C6H12/CS2, affords 1:2 compound 6 including the two redox isomers, [CrIII(Cl4SQ)2(Cl4Cat)]- and [CrIII(Cl4SQ)3]0. The [CrIII(X4SQ)(X4Cat)2]2- anions in 1 and 2 show no significant interconnection between them (discrete type), while the [CrIII(X4SQ)2(X4Cat)]- anions in 4-6 show one-dimensional column-type structures with the aid of intermolecular stacking interactions of the ligand moieties. The anions in 4 show additional stacking interaction with the [FeIIICp2]+ to form one-dimensional ...[D][A][S][D][A]... (D = [FeIIICp2]+, A = [CrIII(Cl4SQ)2(Cl4Cat)]-, and S = C6H6) type mixed-stack arrangements similar to that of previously reported (CoIIICp2)[CrIII(Cl4SQ)2(Cl4Cat)].C6H6 (3). Compound 6 forms a two-dimensional sheet structure where the two redox isomers, [CrIII(Cl4SQ)2(Cl4Cat)]- and [CrIII(Cl4SQ)3]0, are included. The sheet is regarded as a mixed-valence molecular assembly. Two types of the anions, [CrIII(X4SQ)(X4Cat)2]2- (1 and 2) and [CrIII(X4SQ)2(X4Cat)]- (4-6), exhibiting an intramolecular mixed-valence state, show intramolecular intervalence CT transition (IVCT) from the Cat to the SQ at near 5800 and 4300 cm-1, respectively, both in the solution and in the solid states. The intermolecular mixed-valence state of 6 was characterized by absorption spectroscopy, electric conductivity, and SQUID magnetometry. Interestingly, this mixed-valence state of the chromium module is dependent on the redox active nature of the coordinated ligands.

Anthropogenically driven changes in chloride complicate interpretation of base cation trends in lakes recovering from acidic deposition.

PubMed

Rosfjord, Catherine H; Webster, Katherine E; Kahl, Jeffrey S; Norton, Stephen A; Fernandez, Ivan J; Herlihy, Alan T

2007-11-15

Declines in Ca and Mg in low ANC lakes recovering from acidic deposition are widespread across the northern hemisphere. We report overall increases between 1984 and 2004 in the concentrations of Ca + Mg and Cl in lakes representing the statistical population of nearly 4000 low ANC lakes in the northeast U.S. Increases in Cl occurred in nearly all lakes in urbanized southern New England, but only 18% of lakes in more remote Maine had Cl increases. This spatial pattern implicates road salt application as the major source of the increased Cl salts. Among the 48% of the lake population classified as salt-affected, the median changes in Cl (+133 microeq/L) and Ca + Mg (+47 microeq/ L) were large and positive in direction over the 20 years. However, in the unaffected lakes, Cl remained stable and Ca + Mg decreased (-3 microeq/L), consistent with reported long-term trends in base cations of acid-sensitive lakes. This discrepancy between the Cl groups suggests that changes in ion exchange processes in salt-affected watersheds have altered the geochemical cycling of Ca and Mg. One policy-relevant implication is that waters influenced by Cl salts complicate regional assessments of surface water recovery from "acid rain" related to the passage of the Clean Air Act.

A thermodynamic model for the prediction of phase equilibria and speciation in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to halite saturation

NASA Astrophysics Data System (ADS)

Li, Jun; Duan, Zhenhao

2011-08-01

A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H+,Na+,Ca, CaHCO3+,Ca(OH)+,OH-,Cl-, HCO3-,HSO4-,SO42-, CO32-,CO,CaCO and CaSO 4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results. Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO 2 in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model.

Crystal structure of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2} and luminescence properties of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2}:Eu{sup 2+}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iwata, Tomoyuki; Haniuda, Masahide; Fukuda, Koichiro

2008-01-15

The crystal structure of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2} was determined from laboratory X-ray powder diffraction data (CuK{alpha}{sub 1}) using the Rietveld method, with the anisotropic displacement parameters being assigned for all atoms. The crystal structure is cubic (space group I4-bar 3d, Z=2) with lattice dimensions a=1.200950(5) nm and V=1.73211(1) nm{sup 3}. The reliability indices calculated from the Rietveld method were R{sub wp}=8.48% (S=1.21), R{sub p}=6.05%, R{sub B}=1.27% and R{sub F}=1.01%. The validity of the structural model was verified by the three-dimensional electron density distribution, the structural bias of which was reduced as much as possible using the maximum-entropy methods-basedmore » pattern fitting (MPF). The reliability indices calculated from the MPF were R{sub B}=0.75% and R{sub F}=0.56%. In the structural model there are one Ca site, two Al sites, two O sites and one Cl site. This compound is isomorphous with Ca{sub 12}Al{sub 10.6}Si{sub 3.4}O{sub 32}Cl{sub 5.4}. Europium-doped sample Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2}:Eu{sup 2+} was prepared and the photoluminescence properties were presented. The excitation spectrum consisted of two wide bands, which were located at about 268 and 324 nm. The emission spectrum, when excited at 324 nm, resulted in indigo light with a peak at about 442 nm. - Graphical abstract: A portion of the crystal structure of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2} showing eight-membered AlO{sub 4} rings and Ca-Cl-Ca unit.« less

Ca2+-activated Cl- currents in the murine vomeronasal organ enhance neuronal spiking but are dispensable for male-male aggression.

PubMed

Münch, Jonas; Billig, Gwendolyn; Huebner, Christian A; Leinders-Zufall, Trese; Zufall, Frank; Jentsch, Thomas J

2018-05-16

Ca2+-activated Cl- currents have been observed in many physiological processes, including sensory transduction in mammalian olfaction. The olfactory vomeronasal (or Jacobson's) organ (VNO) detects molecular cues originating from animals of the same species or from predators. It then triggers innate behaviors such as aggression, mating, or flight. In the VNO, Ca2+-activated Cl- channels (CaCCs) are thought to amplify the initial pheromone-evoked receptor potential by mediating a depolarizing Cl- efflux. Here, we confirmed the co-localization of the Ca2+-activated Cl- channels anoctamin 1 (Ano1, also called TMEM16A) and Ano2 (TMEM16B) in microvilli of apically and basally located vomeronasal sensory neurons (VSNs) and their absence in supporting cells of the VNO. Both channels were expressed as functional isoforms capable of giving rise to Ca2+-activated Cl- currents. While these currents persisted in the VNOs of mice lacking Ano2, they were undetectable in olfactory neuron-specific Ano1 knock-out mice irrespective of the presence of Ano2. The loss of Ca2+-activated Cl- currents resulted in diminished spontaneous and drastically reduced pheromone-evoked spiking of VSNs. Although this indicated an important role of anoctamin channels in VNO signal amplification, the lack of this amplification did not alter VNO-dependent male-male territorial aggression in olfactory Ano1/Ano2 double knock-out mice. We conclude that Ano1 mediates the bulk of Ca2+-activated Cl- currents in the VNO and that Ano2 plays only a minor role. Furthermore, vomeronasal signal amplification by CaCCs appears to be dispensable for the detection of male-specific pheromones and for near-normal aggressive behavior in mice. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

Changes in taste receptor cell [Ca2+]i modulate chorda tympani responses to salty and sour taste stimuli

PubMed Central

DeSimone, John A.; Ren, ZuoJun; Phan, Tam-Hao T.; Heck, Gerard L.; Mummalaneni, Shobha

2012-01-01

The relationship between taste receptor cell (TRC) Ca2+ concentration ([Ca2+]i) and rat chorda tympani (CT) nerve responses to salty [NaCl and NaCl+benzamil (Bz)] and sour (HCl, CO2, and acetic acid) taste stimuli was investigated before and after lingual application of ionomycin+Ca2+, 1,2-bis(2-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid acetoxymethyl ester (BAPTA-AM), U73122 (phospholipase C blocker), and thapsigargin (Ca2+-ATPase inhibitor) under open-circuit or lingual voltage-clamp conditions. An increase in TRC [Ca2+]i attenuated the tonic Bz-sensitive NaCl CT response and the apical membrane Na+ conductance. A decrease in TRC [Ca2+]i enhanced the tonic Bz-sensitive and Bz-insensitive NaCl CT responses and apical membrane Na+ conductance but did not affect CT responses to KCl or NH4Cl. An increase in TRC [Ca2+]i did not alter the phasic response but attenuated the tonic CT response to acidic stimuli. A decrease in [Ca2+]i did not alter the phasic response but attenuated the tonic CT response to acidic stimuli. In a subset of TRCs, a positive relationship between [H+]i and [Ca2+]i was obtained using in vitro imaging techniques. U73122 inhibited the tonic CT responses to NaCl, and thapsigargin inhibited the tonic CT responses to salty and sour stimuli. The results suggest that salty and sour taste qualities are transduced by [Ca2+]i-dependent and [Ca2+]i-independent mechanisms. Changes in TRC [Ca2+]i in a BAPTA-sensitive cytosolic compartment regulate ion channels and cotransporters involved in the salty and sour taste transduction mechanisms and in neural adaptation. Changes in TRC [Ca2+]i in a separate subcompartment, sensitive to inositol trisphosphate and thapsigargin but inaccessible to BAPTA, are associated with neurotransmitter release. PMID:22956787

pH and external Ca(2+) regulation of a small conductance Cl(-) channel in kidney distal tubule.

PubMed

Sauvé, R; Cai, S; Garneau, L; Klein, H; Parent, L

2000-12-20

A single channel characterization of the Cl(-) channels in distal nephron was undertaken using vesicles prepared from plasma membranes of isolated rabbit distal tubules. The presence in this vesicle preparation of ClC-K type Cl(-) channels was first established by immunodetection using an antibody raised against ClC-K isoforms. A ClC-K1 based functional characterization was next performed by investigating the pH and external Ca(2+) regulation of a small conductance Cl(-) channel which we identified previously by channel incorporation experiments. Acidification of the cis (external) solution from pH 7.4 to 6.5 led to a dose-dependent inhibition of the channel open probability P(O). Similarly, changing the trans pH from 7.4 to 6.8 resulted in a 4-fold decrease of the channel P(O) with no effect on the channel conductance. Channel activity also appeared to be regulated by cis (external) Ca(2+) concentration, with a dose-dependent increase in channel activity as a function of the cis Ca(2+) concentration. It is concluded on the basis of these results that the small conductance Cl(-) channel present in rabbit distal tubules is functionally equivalent to the ClC-K1 channel in the rat. In addition, the present work constitutes the first single channel evidence for a chloride channel regulated by external Ca(2+).

An ultrasensitive chemiluminescence aptasensor for thrombin detection based on iron porphyrin catalyzing luminescence desorbed from chitosan modified magnetic oxide graphene composite.

PubMed

Sun, Yuanling; Wang, Yanhui; Li, Jianbo; Ding, Chaofan; Lin, Yanna; Sun, Weiyan; Luo, Chuannan

2017-11-01

In this work, an ultrasensitive chemiluminescence (CL) aptasensor was prepared for thrombin detection based on iron porphyrin catalyzing luminol - hydrogen peroxide luminescence under alkaline conditions, and iron porphyrin was desorbed from chitosan modified magnetic oxide graphene composite (CS@Fe 3 O 4 @GO). Firstly, CS@Fe 3 O 4 @GO was prepared. CS@Fe 3 O 4 @GO has advantages of the good biocompatibility and positively charged on its surface of CS, the large specific surface area of GO and the easy separation characteristics of Fe 3 O 4 . GO, Fe 3 O 4 and CS@Fe 3 O 4 @GO were confirmed by transmission electron microscopy (TEM), scanning electron microscope (SEM), fourier transform infrared (FTIR) and X-ray powder diffraction (XRD). Then, thrombin aptamer (T-Apt) and hemin (HM, an iron porphyrin) were sequentially modified on the surface of CS@Fe 3 O 4 @GO to form CS@Fe 3 O 4 @GO@T-Apt@HM. The immobilization properties of CS@Fe 3 O 4 @GO to T-Apt and adsorption properties of CS@Fe 3 O 4 @GO@T-Apt to HM were sequentially researched through the curves of kinetics and the curves of thermodynamics. When thrombin existed in solutions, HM was desorbed from the surface of CS@Fe 3 O 4 @GO@T-Apt@HM owing to the strong specific recognition ability between thrombin and T-Apt, causing the changes of CL signal. Under optimized CL conditions, thrombin could be measured with the linear concentration range of 5.0×10 -15 -2.5×10 -10 mol/L. The detection limit was 1.5×10 -15 mol/L (3δ) while the relative standard deviation (RSD) was 3.2%. Finally, the CS@Fe 3 O 4 @GO@T-Apt@HM-CL aptasensor was used for the determination of thrombin in practical serum samples and recoveries ranged from 95% to 103%. Those satisfactory results revealed potential application of the CS@Fe 3 O 4 @GO@T-Apt@HM-CL aptasensor for thrombin detection in monitoring and diagnosis of human blood diseases. Copyright © 2017 Elsevier B.V. All rights reserved.

A first principles study on newly proposed (Ca/Sr/Ba)Fe2Bi2 compounds with their parent compounds

NASA Astrophysics Data System (ADS)

Sundareswari, M.; Jayalakshmi, D. S.; Viswanathan, E.

2016-02-01

The structural, electronic, bonding and magnetic properties of newly proposed iron-based compounds viz., CaFe2Bi2, SrFe2Bi2, BaFe2Bi2 with their Fermi surface topology are reported here for the first time by means of first principles calculation. All these properties of newly proposed compounds are compared and analysed along with their respective parent compounds namely (Ca,Sr,Ba)Fe2As2.

Fermentation of cucumbers brined with calcium chloride instead of sodium chloride.

PubMed

McFeeters, Roger F; Pérez-Díaz, Ilenys

2010-04-01

Waste water containing high levels of NaCl from cucumber fermentation tank yards is a continuing problem for the pickled vegetable industry. A major reduction in waste salt could be achieved if NaCl were eliminated from the cucumber fermentation process. The objectives of this project were to ferment cucumbers in brine containing CaCl(2) as the only salt, to determine the course of fermentation metabolism in the absence of NaCl, and to compare firmness retention of cucumbers fermented in CaCl(2) brine during subsequent storage compared to cucumbers fermented in brines containing both NaCl and CaCl(2) at concentrations typically used in commercial fermentations. The major metabolite changes during fermentation without NaCl were conversion of sugars in the fresh cucumbers primarily to lactic acid which caused pH to decrease to less than 3.5. This is the same pattern that occurs when cucumbers are fermented with NaCl as the major brining salt. Lactic acid concentration and pH were stable during storage and there was no detectable production of propionic acid or butyric acid that would indicate growth of spoilage bacteria. Firmness retention in cucumbers fermented with 100 to 300 mM CaCl(2) during storage at a high temperature (45 degrees C) was not significantly different from that obtained in fermented cucumbers with 1.03 M NaCl and 40 mM CaCl(2). In closed jars, cucumber fermentations with and without NaCl in the fermentation brine were similar both in the chemical changes caused by the fermentative microorganisms and in the retention of firmness in the fermented cucumbers.

Crystal Phases Formed in a CaO-Fe2O3 System Under a High Cooling Rate in Air

NASA Astrophysics Data System (ADS)

Kashiwaya, Yoshiaki

2017-12-01

A CaO-Fe2O3 system is a fundamental binary system for the iron ore sintering process. Although the basic reactions have been investigated since the 1960s, melting and solidification caused by the combustion of coke results in an unstable state owing to extreme temperature variations. In this study, using a hot thermocouple method, samples of 10 pct CaO-90 pct Fe2O3 and 20 pct CaO-80 pct Fe2O3 were melted on a thermocouple and quenched with several techniques. The obtained samples were precisely examined by XRD. It was found that the sample containing 10 pct CaO-90 pct Fe2O3 changed to 10 pct CaO-13 pct FeO-77 pct Fe2O3 under an oxygen partial pressure ( P_{{{O}2 }} ) of 0.21 during melting. For the 10 pct CaO sample, the crystal phases found at a low cooling rate (509 K/s) were WFss, C4WF8 (C: CaO, W: FeO, F: Fe2O3), and C2W4F9. When the sample composition was 20 pct CaO, the precipitated crystal phases were C4WF4, C4F7, and C4WF8. On the other hand, the crystal phases for high cooling rates (1590 and 7900 K/s) with 10 pct CaO were WFss (solid solution of WF and F), F, and C2W4F9. The formation of the equilibrium phases WFss, F, C4WF4, and C4WF8 can be understood by examining the isothermal section of the phase diagrams, while the unstable phases C2W4F9 and C4F7 are discussed on the basis of the reactions under an equilibrium state.

Metal-based phthalocyanines as a potential photosensitizing agent in photodynamic therapy for the treatment of melanoma skin cancer

NASA Astrophysics Data System (ADS)

Maduray, Kaminee; Odhav, B.

2014-03-01

Photodynamic therapy (PDT) is an emerging medical treatment that uses photosensitizers (drug) which are activated by laser light for the generation of cytotoxic free radicals and singlet oxygen molecules that cause tumor cell death. In the recent years, there has been a focus on using and improving an industrial colorant termed phthalocyanines as a prospective photosensitizer because of its unique properties. This in vitro study investigated the photodynamic effect of indium (InPcCl) and iron (FePcCl) phthalocyanine chlorides on human skin cancer cells (melanoma). Experimentally, 2 x 104 cells/ml were seeded in 24-well tissue culture plates and allowed to attach overnight, after which cells were treated with different concentrations (2 μg/ml - 100 μg/ml) of InPcCl and FePcCl. After 2 h, cells were irradiated with constant light doses of 2.5 J/cm2, 4.5 J/cm2 and 8.5 J/cm2 delivered from a diode laser. Post-irradiated cells were incubated for 24 h before cell viability was measured using the MTT Assay. At 24 h after PDT, irradiation with a light dose of 2.5 J/cm2 for each photosensitizing concentration of InPcCl and FePcCl produced a significant decrease in cell viability, but when the treatment light dose was further increased to 4.5 J/cm2 and 8.5 J/cm2 the cell survival was less than 55% for photosensitizing concentrations of InPcCl and FePcCl from 4 μg/ml to 100 μg/ml. This PDT study concludes that low concentrations on InPcCl and FePcCl activated with low level light doses can be used for the effective in vitro killing of melanoma cancer cells.

Fabrication of Iron-Containing Carbon Materials From Graphite Fluoride

NASA Technical Reports Server (NTRS)

Hung, Ching-cheh

1996-01-01

Carbon materials containing iron alloy, iron metal, iron oxide or iron halide were fabricated. Typical samples of these metals were estimated to contain 1 iron atom per 3.5 to 5 carbon atoms. Those carbon materials containing iron alloy, iron metal, and/or Fe3O4 were magnetic. The kinetics of the fabrication process were studied by exposing graphite fluoride (CF(0.68)) to FeCl3 over a 280 to 420 C temperature range. Between 280 and 295 C, FeCl3 quickly entered the structure of CF(0.68), broke the carbon-fluorine bonds, and within 10 to 30 min, completely converted it to carbon made up of graphite planes between which particles of crystalline FeF3 and noncrystalline FeCl3 were located. Longer reaction times (e.g., 28 hr) or higher reaction temperatures (e.g., 420 C) produced materials containing graphite, a FeCl3-graphite intercalation compound, FeCl2(center dot)4H2O, and FeCl2(center dot)2H2O. These products were further heat treated to produce iron-containing carbon materials. When the heating temperature was kept in the 750 to 850 C range, and the oxygen supply was kept at the optimum level, the iron halides in the carbon structure were converted to iron oxides. Raising the heat to temperatures higher than 900 C reduced such iron oxides to iron metal. The kinetics of these reactions were used to suggest processes for fabricating carbon materials containing iron alloy. Such processes were then tested experimentally. In one of the successful trial runs, commercially purchased CF(0.7) powder was used as the reactant, and NiO was added during the final heating to 1200 C as a source of both nickel and oxygen. The product thus obtained was magnetic and was confirmed to be a nickel-iron alloy in carbon.

Activation Thermodynamics and H/D Kinetic Isotope Effect of the Hox to HredH+ Transition in [FeFe] Hydrogenase.

PubMed

Ratzloff, Michael W; Wilker, Molly B; Mulder, David W; Lubner, Carolyn E; Hamby, Hayden; Brown, Katherine A; Dukovic, Gordana; King, Paul W

2017-09-20

Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here we address the route of electron transfer from CdSe→CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The H ox →H red H + reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol -1 and a ∼2.5-fold kinetic isotope effect. Overall, these results support electron injection from CdSe into CaI involving F-clusters, and that the H ox →H red H + step of catalytic proton reduction in CaI proceeds by a proton-dependent process.

MICRURGICAL STUDIES IN CELL PHYSIOLOGY

PubMed Central

Chambers, Robert; Reznikoff, Paul

1926-01-01

By means of micro-dissection and injection Amœba proteus was treated with the chlorides of Na, K, Ca, and Mg alone, in combination, and with variations of pH. I. The Plasmalemma. 1. NaCl weakens and disrupts the surface membrane of the ameba. Tearing the membrane accelerates the disruption which spreads rapidly from the site of the tear. KCl has no disruptive effect on the membrane but renders it adhesive. 2. MgCl2 and CaCl2 have no appreciable effect on the integrity of the surface membrane of the ameba when applied on the outside. No spread of disruption occurs when the membrane is torn in these salts. When these salts are introduced into the ameba they render the pellicle of the involved region rigid. II. The Internal Protoplasm. 3. Injected water either diffuses through the protoplasm or becomes localized in a hyaline blister. Large amounts when rapidly injected produce a "rushing effect". 4. HCl at pH 1.8 solidifies the internal protoplasm and at pH 2.2 causes solidification only after several successive injections. The effect of the subsequent injections may be due to the neutralization of the cell-buffers by the first injection. 5. NaCl and KCl increase the fluidity of the internal protoplasm and induce quiescence. 6. CaCl2 and MgCl2 to a lesser extent solidify the internal protoplasm. With CaCl2 the solidification tends to be localized. With MgCl2 it tends to spread. The injection of CaCl2 accelerates movement in the regions not solidified whereas the injection of MgCl2 induces quiescence. III. Pinching-Off Reaction. 7. A hyaline blister produced by the injection of water may be pinched off. The pinched-off blister is a liquid sphere surrounded by a pellicle. 8. Pinching off always takes place with injections of HCl when the injected region is solidified. 9. The injection of CaCl2 usually results in the pinching off of the portion solidified. The rate of pinching off varies with the concentration of the salt. The injection of MgCl2 does not cause pinching off. IV. Reparability of Torn Surfaces. 10. The repair of a torn surface takes place readily in distilled water. In the different salt solutions, reparability varies specifically with each salt, with the concentration of the salt, and with the extent of the tear. In NaCl and in KCl repair occurs less readily than in water. In MgCl2 repair takes place with great difficulty. In CaCl2 a proper estimate of the process of repair is complicated by the pinching-off phenomenon. However, CaCl2 is the only salt found to increase the mobility of the plasmalemma, and this presumably enhances its reparability. 11. The repair of the surface is probably a function of the internal protoplasm and depends upon an interaction of the protoplasm with the surrounding medium. V. Permeability. 12. NaCl and KCl readily penetrate the ameba from the exterior. CaCl2 and MgCl2 do not. 13. All four salts when injected into an ameba readily diffuse through the internal protoplasm. In the case of CaCl2 the diffusion may be arrested by the pinching-off process. VI. Toxicity. 14. NaCl and KCl are more toxic to the exterior of the cell than to the interior, and the reverse is true for CaCl2 and MgCl2. 15. The relative non-toxicity of injected NaCl to the interior of the ameba is not necessarily due to its diffusion outward from the cell. 16. HCl is much more toxic to the exterior of a cell than to the interior; at pH 5.5 it is toxic to the surface whereas at pH 2.5 it is not toxic to the interior. NaOH to pH 9.8 is not toxic either to the surface or to the interior. VII. Antagonism. 17. The toxic effects of NaCl and of KCl on the exterior of the cell can be antagonized by CaCl2 and this antagonism occurs at the surface. Although the lethal effect of NaCl is thus antagonized, NaCl still penetrates but at a slower rate than if the ameba were immersed in a solution of this salt alone. 18. NaCl and HCl are mutually antagonistic in the interior of the ameba. No antagonism between the salts and HCl was found on the exterior of the ameba. No antagonism between the salts and NaOH was found on the interior or exterior of the ameba. 19. The pinching-off phenomenon can be antagonized by NaCl or by KCl, and the rate of the retardation of the pinching-off process varies with the concentration of the antagonizing salt. 20. The prevention of repair of a torn membrane by toxic solutions of NaCl or KCl can be antagonized by CaCl2. These experiments show directly the marked difference between the interior and the exterior of the cell in their behavior toward the chlorides of Na, K, Ca, and Mg. PMID:19872206

Bhasmas: unique ayurvedic metallic-herbal preparations, chemical characterization.

PubMed

Kumar, A; Nair, A G C; Reddy, A V R; Garg, A N

2006-03-01

Bhasmas are unique Ayurvedic metallic preparations with herbal juices/fruits, known in the Indian subcontinent since the seventh century BC and widely recommended for treatment of a variety of chronic ailments. Twenty bhasmas based on calcium, iron, zinc, mercury, silver, potassium, arsenic, copper, tin, and gemstones were analyzed for up to 18 elements by instrumental neutron activation analysis, including their C, H, N, and S contents. In addition to the major constituent element found at % level, several other essential elements such as Na, K, Ca, Mg, V, Mn, Fe, Cu, and Zn have also been found in microg/g amounts and ultratrace (ng/g) amounts of Au and Co. These seem to remain chelated with organic ligands derived from medicinal herbs. The bhasmas are biologically produced nanoparticles and are taken along with milk, butter, honey, or ghee (a preparation from milk); thus, this makes these elements easily assimilable, eliminating their harmful effects and enhancing their biocompatibility. Siddha Makaradhwaja, a mercury preparation is found to be stoichiometrically HgS without any traces of any other element. Similarly, Swet Parpati is stoichiometrically KNO3 but is found to have Mn, Cu, Zn, Na, P, and Cl as well. An attempt has been made to correlate the metallic contents with their medicinal importance. Na and K, the two electrolytic elements, seem to be well correlated, although K/Na varies in a wide range from 0.06 to 95, with specifically low values for Ca-, Fe-, and Zn-based bhasmas. K/P also varies in a wide range from 0.23 to 12, although for most bhasmas (n = 12), it is 2.3 +/- 1.2. Further, Fe/Mn is linearly correlated (r = 0.96) with Fe in nine noniron bhasmas.

Investigations on FCAM-III (Ca2.38Mg2.09Fe3+10.61Fe2+1.59Al9.33O36): A new homologue of the aenigmatite structure-type in the system CaO-MgO-Fe2O3-Al2O3

NASA Astrophysics Data System (ADS)

Zöll, Klaus; Kahlenberg, Volker; Krüger, Hannes; Tropper, Peter

2018-02-01

In the course of a systematic study of a part of the quaternary system Fe2O3-CaO-Al2O3-MgO (FCAM) the previously unknown compound Ca2.38Mg2.09Fe3+10.61Fe2+1.59Al9.33O36 (FCAM-III) has been synthesized. By analogy with the so-called SFCA series [1-5], our investigation in the system of FCAM shows the existence of a stoichiometric homologous series M14+6nO20+8n, where M = Fe, Ca, Al, Mg and n = 1 or 2. In air, we can prove the formation of coexisting FCAM-III and FCAM-I solid solutions at 1400 °C. By increasing the temperature up to 1425 °C FCAM-I disappears completely and FCAM-III co-exists with magnesiumferrite and a variety of calcium iron oxides. At 1450 °C FCAM-III breaks down to a mixture of FCAM-I again as well as magnesioferrite and melt. Small single-crystals of FCAM-III up to 35 μm in size could be retrieved from the 1425 °C experiment and were subsequently characterized using electron microprobe analysis and synchroton X-ray single-crystal diffraction. Finally the Fe2+/Fetot ratio was calculated from the total iron content based on the crystal-chemical formula obtained from EMPA measurements and charge balance considerations. FCAM-III or Ca2.38Mg2.09Fe3+10.61Fe2+1.59Al9.33O36 has a triclinic crystal structure (space group P 1 ̅). The basic crystallographic data are: a = 10.223(22) Å, b = 10.316(21) Å, c = 14.203(15) Å, α = 93.473(50)°, β = 107.418(67)°, γ = 109.646(60)°, V = 1323.85(2) ų, Z = 1. Using Schreinemaker's technique to analyze the phase relations in the system Fe2O3-CaO-Al2O3-MgO it was possible to obtain the semi-quantitative stability relations between the participating phases and construct a topologically correct phase sequence as a function of T and fO2. The analysis shows that Ca2Al0.5Fe1.5O5 (C2A0.25F0.75) and CaAl1.5Fe2.5O7 (CA0.75F1.25) with higher calculated Fe2+ contents are preferably formed at lower oxygen fugacity and react to CaAl0.5Fe1.5O4 (CA0.25F0.75) by increasing fO2. Spinel-type magnesium-aluminium-ferrite (Mg,Fe2+)Fe3+1.25Al0.75O4 or (MA0.375F0.625) is the typical phase which occurs at high temperature (1400 °C).

Crystal structures of Ca(ClO4)2·4H2O and Ca(ClO4)2·6H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, calcium perchlorate tetra­hydrate and calcium perchlorate hexa­hydrate, were crystallized at low temperatures according to the solid–liquid phase diagram. The structure of the tetra­hydrate consists of one Ca2+ cation eightfold coordinated in a square-anti­prismatic fashion by four water mol­ecules and four O atoms of four perchlorate tetra­hedra, forming chains parallel to [01-1] by sharing corners of the ClO4 tetra­hedra. The structure of the hexa­hydrate contains two different Ca2+ cations, each coordinated by six water mol­ecules and two O atoms of two perchlorate tetra­hedra, forming [Ca(H2O)6(ClO4)]2 dimers by sharing two ClO4 tetra­hedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4 tetra­hedra. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO4)2·6H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures. PMID:25552974

Guanosine 5′-monophosphate-chelated calcium and iron feed additives maintains egg production and prevents Salmonella Gallinarum in experimentally infected layers

PubMed Central

Noh, Hye-Ji; Kim, HeeKyong; Heo, Su Jeong; Cho, Hyang Hyun

2017-01-01

We evaluated the effects of guanosine 5′-monophosphate (GMP)-chelated calcium and iron (CaFe-GMP) on health and egg quality in layers experimentally infected with Salmonella Gallinarum. In this study, a CaFe-GMP feed additive was added to a commercial layer feed and fed to layers over a four-week period. All were inoculated with Salmonella Gallinarum. Body weight, mortality, clinical symptoms, and poultry production including feed intake, egg production, egg loss, and feed conversion rate were observed, and Salmonella Gallinarum was re-isolated from the liver, spleen, and cecum of the layers. All tested internal organs for the CaFe-GMP additive group exhibited significantly lower re-isolation numbers of Salmonella Gallinarum and less severe pathological changes than those in the control group, indicating that the CaFe-GMP feed supplement induced bacterial clearance and increased resistance to Salmonella Gallinarum. Additionally, due to the inhibitory action of CaFe-GMP on the growth of Salmonella Gallinarum, the CaFe-GMP additive group exhibited better egg production, including a higher laying rate and fewer broken eggs. The results suggest that a 0.16% CaFe-GMP additive may help prevent salmonellosis in the poultry industry. PMID:28057911

1,2,3-triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M=FeIII, CrIII and VIII/IV) and related compounds: ground-state spins ranging from S=0 to S=25 and spin-enhanced magnetocaloric effect.

PubMed

Shaw, Rachel; Laye, Rebecca H; Jones, Leigh F; Low, David M; Talbot-Eeckelaers, Caytie; Wei, Qiang; Milios, Constantinos J; Teat, Simon; Helliwell, Madeleine; Raftery, James; Evangelisti, Marco; Affronte, Marco; Collison, David; Brechin, Euan K; McInnes, Eric J L

2007-06-11

We report the synthesis, by solvothermal methods, of the tetradecametallic cluster complexes [M14(L)6O6(OMe)18Cl6] (M=FeIII, CrIII) and [V14(L)6O6(OMe)18Cl6-xOx] (L=anion of 1,2,3-triazole or derivative). Crystal structure data are reported for the {M14} complexes [Fe14(C2H2N3)6O6(OMe)18Cl6], [Cr14(bta)6O6(OMe)18Cl6] (btaH=benzotriazole), [V14O6(Me2bta)6(OMe)18Cl6-xOx] [Me2btaH=5,6-Me2-benzotriazole; eight metal sites are VIII, the remainder are disordered between {VIII-Cl}2+ and {VIV=O}2+] and for the distorted [FeIII14O9(OH)(OMe)8(bta)7(MeOH)5(H2O)Cl8] structure that results from non-solvothermal synthetic methods, highlighting the importance of temperature regime in cluster synthesis. Magnetic studies reveal the {Fe14} complexes to have ground state electronic spins of S

Coarse particle (PM10-2.5) source profiles for emissions from domestic cooking and industrial process in Central India.

PubMed

Bano, Shahina; Pervez, Shamsh; Chow, Judith C; Matawle, Jeevan Lal; Watson, John G; Sahu, Rakesh Kumar; Srivastava, Anjali; Tiwari, Suresh; Pervez, Yasmeen Fatima; Deb, Manas Kanti

2018-06-15

To develop coarse particle (PM 10-2.5 , 2.5 to 10μm) chemical source profiles, real-world source sampling from four domestic cooking and seven industrial processing facilities were carried out in "Raipur-Bhilai" of Central India. Collected samples were analysed for 32 chemical species including 21 elements (Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, S, Sb, Se, V, and Zn) by atomic absorption spectrophotometry (AAS), 8 water-soluble ions (Na + , K + , Mg 2+ , Ca 2+ , Cl - , F - , NO 3 - , and SO 4 2- ) by ion chromatography, ammonium (NH 4 + ) by spectrophotometry, and carbonaceous fractions (OC and EC) by thermal/optical transmittance. The carbonaceous fractions were most abundant fraction in household fuel and municipal solid waste combustion emissions while elemental species were more abundant in industrial emissions. Most of the elemental species were enriched in PM 2.5 (<2.5μm) size fraction as compared to the PM 10-2.5 fraction. Abundant Ca (13-28%) was found in steel-rolling mill (SRM) and cement production industry (CPI) emissions, with abundant Fe (14-32%) in ferro-manganese (FEMNI), steel production industry (SPI), and electric-arc welding emissions. High coefficients of divergence (COD) values (0.46 to 0.88) among the profiles indicate their differences. These region-specific source profiles are more relevant to source apportionment studies in India than profiles measured elsewhere. Copyright © 2018. Published by Elsevier B.V.

Sampling and major element chemistry of the recent (A.D. 1631-1944) Vesuvius activity

USGS Publications Warehouse

Belkin, H.E.; Kilburn, C.R.J.; de Vivo, B.

1993-01-01

Detailed sampling of the Vesuvius lavas erupted in the period A.D. 1631-1944 provides a suite of samples for comprehensive chemical analyses and related studies. Major elements (Si, Ti, Al, Fetotal, Mn, Mg, Ca, Na, K and P), volatile species (Cl, F, S, H2O+, H2O- and CO2), and ferrous iron (Fe2+) were determined for one hundred and forty-nine lavas and five tephra from the A.D. 1631-1944 Vesuvius activity. The lavas represent a relatively homogeneous suite with respect to SiO2, TiO2, FeOtotal, MnO and P2O5, but show systematic variations among MgO, K2O, Na2O, Al2O3 and CaO. The average SiO2 content is 48.0 wt.% and the rocks are classified as tephriphonolites according to their content of alkalis. All of the lavas are silica-undersaturated and are nepheline, leucite, and olivine normative. There is no systematic variation in major-element composition with time, over the period A.D. 1631-1944. The inter-eruption and intra-eruption compositional differences are the same magnitude. The lavas are highly porphyritic with clinopyroxene and leucite as the major phases. Fractionation effects are not reflected in the silica content of the lavas. The variability of MgO, K2O, Na2O, and CaO can be modelled as a relative depletion or accumulation of clinopyroxene. ?? 1993.

Phase stability and large in-plane resistivity anisotropy in the 112-type iron-based superconductor Ca 1 - x La x FeAs 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Chang-Jong; Birol, Turan; Kotliar, Gabriel

The recently discovered high-T c superconductor Ca 1-xLa xFeAs 2 is a unique compound not just because of its low-symmetry crystal structure but also because of its electronic structure, which hosts Dirac-like metallic bands resulting from (spacer) zigzag As chains. We present a comprehensive first-principles theoretical study of the electronic and crystal structures of Ca 1-xLa xFeAs 2. After discussing the connection between the crystal structure of the 112 family, which Ca 1-xLa xFeAs 2 is a member of, with the other known structures of Fe pnictide superconductors, we check the thermodynamic phase stability of CaFeAs 2, and similar hyphotheticalmore » compounds SrFeAs 2 and BaFeAs 2 which, we find, are slightly higher in energy. We calculate the optical conductivity of Ca 1-xLa xFeAs 2 using the DFT+DMFT method and predict a large in-plane resistivity anisotropy in the normal phase, which does not originate from electronic nematicity, but is enhanced by the electronic correlations. In particular, we predict a 0.34 eV peak in the yy component of the optical conductivity of the 30% La-doped compound, which corresponds to coherent interband transitions within a fast-dispersing band arising from the zigzag As chains, which are unique to this compound. We also study the Landau free energy for Ca 1-xLa xFeAs 2 including the order parameter relevant for the nematic transition and find that the free energy does not have any extra terms that could induce ferro-orbital order. This explains why the presence of As chains does not broaden the nematic transition in Ca 1-xLa xFeAs 2.« less

Phase stability and large in-plane resistivity anisotropy in the 112-type iron-based superconductor Ca 1 - x La x FeAs 2

DOE PAGES

Kang, Chang-Jong; Birol, Turan; Kotliar, Gabriel

2017-01-17

The recently discovered high-T c superconductor Ca 1-xLa xFeAs 2 is a unique compound not just because of its low-symmetry crystal structure but also because of its electronic structure, which hosts Dirac-like metallic bands resulting from (spacer) zigzag As chains. We present a comprehensive first-principles theoretical study of the electronic and crystal structures of Ca 1-xLa xFeAs 2. After discussing the connection between the crystal structure of the 112 family, which Ca 1-xLa xFeAs 2 is a member of, with the other known structures of Fe pnictide superconductors, we check the thermodynamic phase stability of CaFeAs 2, and similar hyphotheticalmore » compounds SrFeAs 2 and BaFeAs 2 which, we find, are slightly higher in energy. We calculate the optical conductivity of Ca 1-xLa xFeAs 2 using the DFT+DMFT method and predict a large in-plane resistivity anisotropy in the normal phase, which does not originate from electronic nematicity, but is enhanced by the electronic correlations. In particular, we predict a 0.34 eV peak in the yy component of the optical conductivity of the 30% La-doped compound, which corresponds to coherent interband transitions within a fast-dispersing band arising from the zigzag As chains, which are unique to this compound. We also study the Landau free energy for Ca 1-xLa xFeAs 2 including the order parameter relevant for the nematic transition and find that the free energy does not have any extra terms that could induce ferro-orbital order. This explains why the presence of As chains does not broaden the nematic transition in Ca 1-xLa xFeAs 2.« less

Photochemical organic oxidations and dechlorinations with a mu-oxo bridged heme/non-heme diiron complex.

PubMed

Wasser, Ian M; Fry, H Christopher; Hoertz, Paul G; Meyer, Gerald J; Karlin, Kenneth D

2004-12-27

Steady state and laser flash photolysis studies of the heme/non-heme mu-oxo diiron complex [((6)L)Fe(III)-O-Fe(III)-Cl](+) (1) have been undertaken. The anaerobic photolysis of benzene solutions of 1 did not result in the buildup of any photoproduct. However, the addition of excess triphenylphosphine resulted in the quantitative photoreduction of 1 to [((6)L)Fe(II)...Fe(II)-Cl](+) (2), with concomitant production by oxo-transfer of 1 equiv of triphenylphosphine oxide. Under aerobic conditions and excess triphenylphosphine, the reaction produces multiple turnovers (approximately 28) before the diiron complex is degraded. The anaerobic photolysis of tetrahydrofuran (THF) or toluene solutions of 1 likewise results in the buildup of 2. The oxidation products from these reactions included gamma-butyrolactone (approximately 15%) for the reaction in THF and benzaldehyde (approximately 23%) from the reaction in toluene. In either case, the O-atom which is incorporated into the carbonyl product is derived from dioxygen present under workup or under aerobic photolysis conditions. Transient absorption measurements of low-temperature THF solutions of 1 revealed the presence of an (P)Fe(II)-like [P = tetraaryl porphyrinate dianion] species suggesting that the reactive species is a formal (heme)Fe(II)/Fe(IV)=O(non-heme) pair. The non-heme Fe(IV)=O is thus most likely responsible for C-H bond cleavage and subsequent radical chemistry. The photolysis of 1 in chlorobenzene or 1,2-dichlorobenzene resulted in C-Cl cleavage reactions and the formation of [[((6)L)Fe(III)-Cl...Fe(III)-Cl](2)O](2+) (3), with chloride ligands that are derived from solvent dehalogenation chemistry. The resulting organic products are biphenyl trichlorides or biphenyl monochlorides, derived from dichlorobenzene and chlorobenzene, respectively. Similarly, product 3 is obtained by the photolysis of benzene-benzyl chloride solutions of 1; the organic product is benzaldehyde (approximately 70%). A brief discussion of the dehalogenation chemistry, along with relevant environmental perspectives, is included.

Raman study of CaDNA films as a function of water content and excess CaCl2 concentration: Stability of the B conformation.

NASA Astrophysics Data System (ADS)

Schwenker, Megan; Marlowe, Robert; Lee, Scott; Rupprecht, Allan

2006-03-01

Highly oriented, wet-spun films of CaDNA expand in the direction perpendicular to the helical axis as the hydration of the film is increased. CaDNA films with a high CaCl2 content show an unexpected shrinkage at a relative humidity of about 93%. We have performed Raman experiments on CaDNA films as a function of both water content and excess CaCl2 concentration in order to determine if this unexpected shrinkage might be related to a conformational transition of the DNA molecules. We find that the DNA molecules remain in the B conformation for all salt contents down to a relative humidity of 59%.

Effect of the CaO/SiO2 mass ratio and FeO content on the viscosity of CaO-SiO2-"FeO"-12wt%ZnO-3wt%Al2O3 slags

NASA Astrophysics Data System (ADS)

Lü, Jian-fang; Jin, Zhe-nan; Yang, Hong-ying; Tong, Lin-lin; Chen, Guo-bao; Xiao, Fa-xin

2017-07-01

An effective process for recycling lead from hazardous waste cathode ray tubes (CRTs) funnel glass through traditional lead smelting has been presented previously. The viscous behavior of the molten high lead slag, which is affected by the addition of funnel glass, plays a critical role in determining the production efficiency. Therefore, the viscosities of the CaO-SiO2-"FeO"-12wt%ZnO-3wt%Al2O3 slags were measured in the current study using the rotating spindle method. The slag viscosity decreases as the CaO/SiO2 mass ratio is increased from 0.8 to 1.2 and also as the FeO content is increased from 8wt% to 20wt%. The breaking temperature of the slag is lowered substantially by the addition of FeO, whereas the influence of the CaO/SiO2 mass ratio on the breaking temperature is complex. The structural analysis of quenched slags using Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy reveals that the silicate network structure is depolymerized with increasing CaO/SiO2 mass ratio or increasing FeO content. The [FeO6]-octahedra in the slag melt increase as the CaO/SiO2 mass ratio or the FeO content increases. This increase can further decrease the degree of polymerization (DOP) of the slag. Furthermore, the activation energy for viscous flow decreases both with increasing CaO/SiO2 mass ratio and increasing FeO content.

Surface reactivity of mercury on the oxygen-terminated hematite(0001) surface: a first-principle study

NASA Astrophysics Data System (ADS)

Jung, J. E.; Wilcox, J.

2016-12-01

Hematite (α-Fe2O3) is a common mineral found in Earth's near-surface environment. Due to its nontoxicity, corrosion-resistance, and high thermal stability, α-Fe2O3 has attracted attentions as materials for various applications such as photocatalysts, gas sensors, as well as for the removal of heavy metals. In this study, α-Fe2O3 is chosen for potential mercury (Hg) sorbent in order to remove Hg from coal-fired power plants. Specifically, theoretical approaches using density functional theory (DFT) is used to understand surface reactivity of Hg on oxygen (O) terminated α-Fe2O3(0001) surface. The most probable adsorption sites of Hg, chlorine (Cl), and mercury chloride (HgCl) on the α-Fe2O3 surface are found based on adsorption energy calculations, and the oxidation states of the adsorbates are determined by Bader charge analysis. Additionally, projected density of states (PDOS) analysis characterizes the surface-adsorbate bonding mechanism. The results of adsorption energy calculation proposes that Hg physisorbs to the α-Fe2O3(0001) surface with adsorption energy of -0.278 eV, and the subsequent Bader charge analysis confirms that Hg is slightly oxidized. In addition, Cl introduced to the Hg-adsorbed surface strengthens Hg stability on the α-Fe2O3(0001) surface as evidenced by a shortened Hg-surface equilibrium distance. The PDOS analysis also suggests that Cl enhances the chemical bonding between the surface and the adsorbate, thereby increasing adsorption strength. In summary, α-Fe2O3 has ability to adsorb and oxidize Hg, and this reactivity is enhanced in the presence of Cl.

Effects of electron acceptors on soluble reactive phosphorus in the overlying water during algal decomposition.

PubMed

Wang, Jinzhi; Jiang, Xia; Zheng, Binghui; Niu, Yuan; Wang, Kun; Wang, Wenwen; Kardol, Paul

2015-12-01

Endogenous phosphorus (P) release from sediments is an important factor to cause eutrophication and, hence, algal bloom in lakes in China. Algal decomposition depletes dissolved oxygen (DO) and causes anaerobic conditions and therefore increases P release from sediments. As sediment P release is dependent on the iron (Fe) cycle, electron acceptors (e.g., NO3 (-), SO4 (2-), and Mn(4+)) can be utilized to suppress the reduction of Fe(3+) under anaerobic conditions and, as such, have the potential to impair the release of sediment P. Here, we used a laboratory experiment to test the effects of FeCl3, MnO2, and KNO3 on soluble reactive phosphorus (SRP) concentration and related chemical variables in the overlying water column during algal decomposition at different algal densities. Results showed that algal decomposition significantly depleted DO and thereby increased sediment Fe-bound P release. Compared with the control, addition of FeCl3 significantly decreased water SRP concentration through inhibiting sediment P release. Compared with FeCl3, addition of MnO2 has less potential to suppress sediment P release during algal decomposition. Algal decomposition has the potential for NO3 (-) removal from aquatic ecosystem through denitrification and by that alleviates the suppressing role of NO3 (-) on sediment P release. Our results indicated that FeCl3 and MnO2 could be efficient in reducing sediment P release during algal decomposition, with the strongest effect found for FeCl3; large amounts of NO3 (-) were removed from the aquatic ecosystem through denitrification during algal decomposition. Moreover, the amounts of NO3 (-) removal increased with increasing algal density.

High time-resolved elemental components in fine and coarse particles in the Pearl River Delta region of Southern China: Dynamic variations and effects of meteorology.

PubMed

Zhou, Shengzhen; Davy, Perry K; Wang, Xuemei; Cohen, Jason Blake; Liang, Jiaquan; Huang, Minjuan; Fan, Qi; Chen, Weihua; Chang, Ming; Ancelet, Travis; Trompetter, William J

2016-12-01

Hourly-resolved PM 2.5 and PM 10-2.5 samples were collected in the industrial city Foshan in the Pearl River Delta region, China. The samples were subsequently analyzed for elemental components and black carbon (BC). A key purpose of the study was to understand the composition of particulate matter (PM) at high-time resolution in a polluted urban atmosphere to identify key components contributing to extreme PM concentration events and examine the diurnal chemical concentration patterns for air quality management purposes. It was found that BC and S concentrations dominated in the fine mode, while elements with mostly crustal and oceanic origins such as Si, Ca, Al and Cl were found in the coarse size fraction. Most of the elements showed strong diurnal variations. S did not show clear diurnal variations, suggesting regional rather than local origin. Based on empirical orthogonal functions (EOF) method, 3 forcing factors were identified contributing to the extreme events of PM 2.5 and selected elements, i.e., urban direct emissions, wet deposition and a combination of coarse mode sources. Conditional probability functions (CPF) were performed using wind profiles and elemental concentrations. The CPF results showed that BC and elemental Cl, K, Fe, Cu and Zn in the fine mode were mostly from the northwest, indicating that industrial emissions and combustion were the main sources. For elements in the coarse mode, Si, Al, K, Ca, Fe and Ti showed similar patterns, suggesting same sources such as local soil dust/construction activities. Coarse elemental Cl was mostly from the south and southeast, implying the influence of marine aerosol sources. For other trace elements, we found vanadium (V) in fine PM was mainly from the sources located to the southeast of the measuring site. Combined with CPF results of S and V in fine PM, we concluded shipping emissions were likely an important elemental emission source. Copyright © 2016. Published by Elsevier B.V.

Steady-state equation of water vapor sorption for CaCl2-based chemical sorbents and its application

PubMed Central

Zhang, Haiquan; Yuan, Yanping; Sun, Qingrong; Cao, Xiaoling; Sun, Liangliang

2016-01-01

Green CaCl2-based chemical sorbent has been widely used in sorption refrigeration, air purification and air desiccation. Methods to improve the sorption rate have been extensively investigated, but the corresponding theoretical formulations have not been reported. In this paper, a sorption system of solid-liquid coexistence is established based on the hypothesis of steady-state sorption. The combination of theoretical analysis and experimental results indicates that the system can be described by steady-state sorption process. The steady-state sorption equation, μ = (η − γT) , was obtained in consideration of humidity, temperature and the surface area. Based on engineering applications and this equation, two methods including an increase of specific surface area and adjustment of the critical relative humidity (γ) for chemical sorbents, have been proposed to increase the sorption rate. The results indicate that the CaCl2/CNTs composite with a large specific surface area can be obtained by coating CaCl2 powder on the surface of carbon nanotubes (CNTs). The composite reached sorption equilibrium within only 4 h, and the sorption capacity was improved by 75% compared with pure CaCl2 powder. Furthermore, the addition of NaCl powder to saturated CaCl2 solution could significantly lower the solution’s γ. The sorption rate was improved by 30% under the same environment. PMID:27682811

Steady-state equation of water vapor sorption for CaCl2-based chemical sorbents and its application

NASA Astrophysics Data System (ADS)

Zhang, Haiquan; Yuan, Yanping; Sun, Qingrong; Cao, Xiaoling; Sun, Liangliang

2016-09-01

Green CaCl2-based chemical sorbent has been widely used in sorption refrigeration, air purification and air desiccation. Methods to improve the sorption rate have been extensively investigated, but the corresponding theoretical formulations have not been reported. In this paper, a sorption system of solid-liquid coexistence is established based on the hypothesis of steady-state sorption. The combination of theoretical analysis and experimental results indicates that the system can be described by steady-state sorption process. The steady-state sorption equation, μ = (η - γT) , was obtained in consideration of humidity, temperature and the surface area. Based on engineering applications and this equation, two methods including an increase of specific surface area and adjustment of the critical relative humidity (γ) for chemical sorbents, have been proposed to increase the sorption rate. The results indicate that the CaCl2/CNTs composite with a large specific surface area can be obtained by coating CaCl2 powder on the surface of carbon nanotubes (CNTs). The composite reached sorption equilibrium within only 4 h, and the sorption capacity was improved by 75% compared with pure CaCl2 powder. Furthermore, the addition of NaCl powder to saturated CaCl2 solution could significantly lower the solution’s γ. The sorption rate was improved by 30% under the same environment.

Effects of aging and oxidation of palladized iron embedded in activated carbon on the dechlorination of 2-chlorobiphenyl

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hyeok Choi; Souhail R. Al-Abed; Shirish Agarwal

2009-06-15

Reactive activated carbon (RAC) impregnated with palladized iron has been developed to effectively treat polychlorinated biphenyls (PCBs) in the environment by coupling adsorption and dechlorination of PCBs. In this study, we addressed the dechlorination reactivity and capacity of RAC toward aqueous 2-chlorobiphenyl (2-ClBP), and its aging and longevity under various oxidizing environments. RAC containing 14.4% Fe and 0.68% Pd used in this study could adsorb 122.6 mg 2-ClBP/g RAC, and dechlorinate 56.5 mg 2-ClBP/g RAC which corresponds to 12% (yield) of its estimated dechlorination capacity. Due to Fe0 oxidation to form oxide passivating layers, Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} (oxide-watermore » interface) and FeOOH/FeO (oxide-metal interface), RAC reactivity decreased progressively over aging under N{sub 2} < H{sub 2}O + N{sub 2} < H{sub 2}O + O{sub 2} conditions. Considering nanoscale Fe/Pd corrosion chemistry, the decline was quite slow at only 5.6%, 19.5%, and 32.5% over one year, respectively. Dissolved oxygen played a crucial role in enhancing 2-ClBP adsorption but inhibiting its dechlorination. The reactivity change could be explained with the properties of the aged RAC including surface area, Fe0 content, and Fe species. During the aging and oxidation, the RAC showed limited dissolution of Fe and Pd. Finally, implementation issues regarding application of RAC system to contaminated sites are discussed. 25 refs., 6 figs., 1 tab.« less

CaCl 2 -Accelerated Hydration of Tricalcium Silicate: A STXM Study Combined with 29 Si MAS NMR

DOE PAGES

Li, Qinfei; Ge, Yong; Geng, Guoqing; ...

2015-01-01

Tmore » he effect of calcium chloride (CaCl 2 ) on tricalcium silicate (C 3 S) hydration was investigated by scanning transmission X-ray microscopy (SXM) with Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra and 29 Si MAS NMR. SXM is demonstrated to be a powerful tool for studying the chemical composition of a cement-based hydration system. he Ca L 3,2 -edge NEXAFS spectra obtained by examining C 3 S hydration in the presence of CaCl 2 showed that this accelerator does not change the coordination of calcium in the calcium silicate hydrate (C-S-H), which is the primary hydration product. O K-edge NEXAFS is also very useful in distinguishing the chemical components in hydrated C 3 S. Based on the Ca L 3,2 -edge spectra and chemical component mapping, we concluded that CaCl 2 prefers to coexist with unhydrated C 3 S instead of C-S-H. In Si K-edge NEXAFS analysis, CaCl 2 increases the degree of silicate polymerization of C-S-H in agreement with the 29 Si CP/MAS NMR results, which show that the presence of CaCl 2 in hydrated C 3 S considerably accelerates the formation of middle groups ( Q 2 ) and branch sites ( Q 3 ) in the silicate chains of C-S-H gel at 1-day hydration.« less

Experimental Determination of Solubilities of Tri-calcium Di-Citrate Tetrahydrate [Ca 3[C 3H 5O(COO) 3] 2•4H 2O] Earlandite in NaCl and MgCl 2 Solutions to High Ionic Strengths and Its Pitzer Model: Applications to Nuclear Waste Isolation and Other Low Temperature Environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiong, Yongliang; Kirkes, Leslie Dawn; Westfall, Terry

In this study, solubility measurements on tri-calcium di-citrate tetrahydrate [Ca 3[C 3H 5O(COO) 3]2•4H 2O, abbreviated as Ca 3[Citrate] 2•4H 2O] as a function of ionic strength are conducted in NaCl solutions up to I = 5.0 mol•kg –1 and in MgCl 2 solutions up to I = 7.5 mol•kg –1, at room temperature (22.5 ± 0.5°C). The solubility constant (log Kmore » $$0\\atop{sp}$$) for Ca 3[Citrate] 2•4H 2O and formation constant (logβ$$0\\atop{1}$$) for Ca[C 3H 5O(COO) 3] –Ca 3[C 3H 5O(COO) 3] 2•4H 2O (earlandite) = 3Ca 2+ + 2[C 3H 5O(COO) 3] 3– + 4H 2O (1) Ca 2+ + [C 3H 5O(COO) 3] 3– = Ca[C 3H 5O(COO) 3] – (2) are determined as –18.11 ± 0.05 and 4.97 ± 0.05, respectively, based on the Pitzer model with a set of Pitzer parameters describing the specific interactions in NaCl and M gCl 2 media.« less

Composition and source of salinity of ore-bearing fluids in Cu-Au systems of the Carajás Mineral Province, Brazil

USGS Publications Warehouse

Xavier, Roberto; Rusk, Brian; Emsbo, Poul; Monteiro, Lena

2009-01-01

The composition and Cl/Br – NaCl ratios of highly saline aqueous inclusions from large tonnage (> 100 t) IOCG deposits (Sossego, Alvo 118, and Igarapé Bahia) and a Paleoproterozoic intrusion-related Cu-Au-(Mo-W-Bi-Sn) deposit (Breves; < 50 Mt)) in the Carajás Mineral Province have been analysed by LA-ICP-MS and ion chromatography. In both Cu-Au systems, brine inclusions are Ca-dominated (5 to 10 times more than in porphyry Cu-Au fluids), and contain percent level concentrations of Na and K. IOCG inclusion fluids, however, contain higher Sr, Ba, Pb, and Zn concentrations, but significantly less Bi, than the intrusion-related Breves inclusion fluids. Cu is consistently below detection limits in brine inclusions from the IOCG and intrusion-related systems and Fe was not detected in the latter. Cl/Br and Na/Cl ratios of the IOCG inclusion fluids range from entirely evaporative brines (bittern fluids; e.g. Igarapé Bahia and Alvo 118) to values that indicate mixing with magma-derived brines. Cl/Br and Na/Cl ratios of the Breves inclusion fluids strongly suggest the involvement of magmatic brines, but that possibly also incorporated bittern fluids. Collectively, these data demonstrate that residual evaporative and magmatic brines were important components of the fluid regime involved in the formation of Cu-Au systems in the Carajás Mineral Province.

Characterization of the enhancement effect of Na2CO3 on the sulfur capture capacity of limestones.

PubMed

Laursen, Karin; Kern, Arnt A; Grace, John R; Lim, C Jim

2003-08-15

It has been known for a long time that certain additives (e.g., NaCl, CaCl2, Na2CO3, Fe2O3) can increase the sulfur dioxide capture-capacity of limestones. In a recent study we demonstrated that very small amounts of Na2CO3 can be very beneficial for producing sorbents of very high sorption capacities. This paper explores what contributes to these significant increases. Mercury porosimetry measurements of calcined limestone samples reveal a change in the pore-size from 0.04-0.2 microm in untreated samples to 2-10 microm in samples treated with Na2CO3--a pore-size more favorable for penetration of sulfur into the particles. The change in pore-size facilitates reaction with lime grains throughout the whole particle without rapid plugging of pores, avoiding premature change from a fast chemical reaction to a slow solid-state diffusion controlled process, as seen for untreated samples. Calcination in a thermogravimetric reactor showed that Na2CO3 increased the rate of calcination of CaCO3 to CaO, an effect which was slightly larger at 825 degrees C than at 900 degrees C. Peak broadening analysis of powder X-ray diffraction data of the raw, calcined, and sulfated samples revealed an unaffected calcite size (approximately 125-170 nm) but a significant increase in the crystallite size for lime (approximately 60-90 nm to approximately 250-300 nm) and less for anhydrite (approximately 125-150 nm to approximately 225-250 nm). The increase in the crystallite and pore-size of the treated limestones is attributed to an increase in ionic mobility in the crystal lattice due to formation of vacancies in the crystals when Ca is partly replaced by Na.

Experimental Determination of the Cosmogenic Ar Production Rate From Ca

NASA Astrophysics Data System (ADS)

Niedermann, S.; Schäfer, J. M.; Wieler, R.; Naumann, R.

2005-12-01

Cosmogenic 38Ar is produced in terrestrial surface rocks by spallation of target nuclides, in particular K and Ca. Though the presence of cosmogenic Ar in Ca-rich minerals has been demonstrated earlier [1], is has proven difficult to establish its production rate. To circumvent problems connected to 36Ar production by 35Cl neutron capture and different production rates from K and Ca, we have analyzed the noble gases in seven pyroxene separates (px) from the Antarctic Dry Valleys which are essentially free of Cl and K. The px were obtained from dolerite rocks, for which 3He and 21Ne exposure ages from 1.5 to 6.5 Ma have been reported [2]. The noble gases were extracted in two or three heating steps at GFZ Potsdam, yielding 38Ar/36Ar ratios up to 0.2283 ± 0.0008 (air: 0.1880). Ca (3.7-11.2 wt. %) is expected to be the only relevant target element for Ar production in the five pure px (<0.05% K); the production rate from Fe is at least two orders of magnitude lower than that from Ca [e.g. 3]. Assuming an 38Ar/36Ar production ratio of 1.5 ± 0.2, we obtain cosmogenic 38Ar concentrations between 130 and 530x106 atoms/g. The 38Ar production rate was calculated based on 21Ne exposure ages [2], corrected for elevated nuclide production in Antarctica due to prevailing low air pressure and for the revised 21Ne production rate from Si. We obtain values between 188 ± 17 and 243 +110/-24 atoms (g Ca)-1 a-1 at sea level and high (northern) latitudes for four out of the five pure px, while one yields a very high value of 348 ± 70 atoms (g Ca)-1 a-1. Values above 250 atoms (g Ca)-1 a-1 are also obtained from two less pure px containing 0.3 and 0.9% K and from one feldspar/quartz accumulate, indicating that the production rate from K may be higher than that from Ca. The weighted mean (excluding the outlier) of ~200 atoms (g Ca)-1 a-1 is in excellent agreement with Lal's [3] theoretical estimate. [1] Renne et al., EPSL 188 (2001) 435. [2] Schäfer et al., EPSL 167 (1999) 215. [3] Lal, EPSL 104 (1991) 424.

Uptake of divalent ions (Mn+2 and Ca+2) by heat-set whey protein gels.

PubMed

Oztop, Mecit H; McCarthy, Kathryn L; McCarthy, Michael J; Rosenberg, Moshe

2012-02-01

Divalent salts are used commonly for gelation of polymer molecules. Calcium, Ca(+2), is one of the most common divalent ions that is used in whey protein gels. Manganese, Mn(+2), is also divalent, but paramagnetic, enhancing relaxation decay rates in magnetic resonance imaging (MRI) and can be used as a probe to understand the behavior of Ca(+2) in whey protein gels. The objective of this study was to investigate the diffusion of Ca(+2) and Mn(+2) ions in heat-set whey protein gels by using MRI and nuclear magnetic resonance (NMR) relaxometry. Whey protein gels were immersed in solutions containing MnCl(2) and CaCl(2) at neutral pH. Images obtained with gels immersed in MnCl(2) solution revealed a relaxation sink region in the gel's surface and the thickness of the region increased with time. These "no signal" regions in the MR images were attributed to uptake of Mn(+2) by the gel. Results obtained with CaCl(2) solution indicated that since Ca(+2) did not have the paramagnetic effect, the regions where Ca(+2) diffused into the gel exhibited a slight decrease in signal intensity. The relaxation spectrums exhibited 3 populations of protons, for gels immersed in MnCl(2) solution, and 2 populations for gels in CaCl(2) solution. No significant change in T(2) distributions was observed for the gels immersed in CaCl(2) solution. The results demonstrated that MRI and NMR relaxometry can be used to understand the diffusion of ions into the whey protein gel, which is useful for designing gels of different physical properties for controlled release applications. Design of food systems for delivery of bioactive compounds requires knowledge of diffusion rates and structure. Utilizing magnetic resonance imaging the diffusion rates of ions can be measured. Relaxation spectra could yield information concerning molecular interactions. © 2012 Institute of Food Technologists®

Optimization of the crystal growth of the superconductor CaKFe4As4 from solution in the FeAs -CaFe2As2-KFe2As2 system

NASA Astrophysics Data System (ADS)

Meier, W. R.; Kong, T.; Bud'ko, S. L.; Canfield, P. C.

2017-06-01

Measurements of the anisotropic properties of single crystals play a crucial role in probing the physics of new materials. Determining a growth protocol that yields suitable high-quality single crystals can be particularly challenging for multicomponent compounds. Here we present a case study of how we refined a procedure to grow single crystals of CaKFe4As4 from a high temperature, quaternary liquid solution rich in iron and arsenic ("FeAs self-flux"). Temperature dependent resistance and magnetization measurements are emphasized, in addition to the x-ray diffraction, to detect intergrown CaKFe4As4 , CaFe2As2 , and KFe2As2 within what appear to be single crystals. Guided by the rules of phase equilibria and these data, we adjusted growth parameters to suppress formation of the impurity phases. The resulting optimized procedure yielded phase-pure single crystals of CaKFe4As4 . This optimization process offers insight into the growth of quaternary compounds and a glimpse of the four-component phase diagram in the pseudoternary FeAs -CaFe2As2-KFe2As2 system.

Method for production of hydrocarbons from hydrates

DOEpatents

McGuire, Patrick L.

1984-01-01

A method of recovering natural gas entrapped in frozen subsurface gas hydrate formations in arctic regions. A hot supersaturated solution of CaCl.sub.2 or CaBr.sub.2, or a mixture thereof, is pumped under pressure down a wellbore and into a subsurface hydrate formation so as to hydrostatically fracture the formation. The CaCl.sub.2 /CaBr.sub.2 solution dissolves the solid hydrates and thereby releases the gas entrapped therein. Additionally, the solution contains a polymeric viscosifier, which operates to maintain in suspension finely divided crystalline CaCl.sub.2 /CaBr.sub.2 that precipitates from the supersaturated solution as it is cooled during injection into the formation.

Differential Regulation of c-di-GMP Metabolic Enzymes by Environmental Signals Modulates Biofilm Formation in Yersinia pestis.

PubMed

Ren, Gai-Xian; Fan, Sai; Guo, Xiao-Peng; Chen, Shiyun; Sun, Yi-Cheng

2016-01-01

Cyclic diguanylate (c-di-GMP) is essential for Yersinia pestis biofilm formation, which is important for flea-borne blockage-dependent plague transmission. Two diguanylate cyclases (DGCs), HmsT and HmsD and one phosphodiesterase (PDE), HmsP are responsible for the synthesis and degradation of c-di-GMP in Y. pestis. Here, we systematically analyzed the effect of various environmental signals on regulation of the biofilm phenotype, the c-di-GMP levels, and expression of HmsT, HmsD, and HmsP in Y. pestis. Biofilm formation was higher in the presence of non-lethal high concentration of CaCl2, MgCl2, CuSO4, sucrose, sodium dodecyl sulfate, or dithiothreitol, and was lower in the presence of FeCl2 or NaCl. In addition, we found that HmsD plays a major role in biofilm formation in acidic or redox environments. These environmental signals differentially regulated expression of HmsT, HmsP and HmsD, resulting in changes in the intracellular levels of c-di-GMP in Y. pestis. Our results suggest that bacteria can sense various environmental signals, and differentially regulate activity of DGCs and PDEs to coordinately regulate and adapt metabolism of c-di-GMP and biofilm formation to changing environments.

Substituting Fe for two of the four Mn ions in photosystem II-effects on water-oxidation.

PubMed

Semin, Boris K; Seibert, Michael

2016-06-01

We have investigated the interaction of Fe(II) cations with Ca-depleted PSII membranes (PSII[-Ca,4Mn]) in the dark and found that Fe(II) incubation removes 2 of 4 Mn ions from the tetranuclear Mn cluster of the photosynthetic O2-evolving complex (OEC). The reduction of Mn ions in PSII(-Ca,4Mn) by Fe(II) and the concomitant release of two Mn(II) cations is accompanied by the binding of newly generated Fe(III) in at least one vacated Mn site. Flash-induced chlorophyll (Chl) fluorescence yield measurements of this new 2Mn/nFe cluster (PSII[-Ca,2Mn,nFe]) show that charge recombination in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) occurs between Qa (-) and the remaining Mn/Fe cluster (but not YZ (●)) in the OEC, and extraction of 2 Mn occurs uniformly in all PSII complexes. No O2 evolution is observed, but the heteronuclear metal cluster in PSII(-Ca,2Mn,nFe) samples is still able to supply electrons for reduction of the exogenous electron acceptor, 2,6-dichlorophrenolindophenol, by photooxidizing water and producing H2O2 in the absence of an exogenous donor as seen previously with PSII(-Ca,4Mn). Selective extraction of Mn or Fe cations from the 2Mn/nFe heteronuclear cluster demonstrates that the high-affinity Mn-binding site is occupied by one of the iron cations. It is notable that partial water-oxidation function still occurs when only two Mn cations are present in the PSII OEC.

Potential Interactions of Calcium-Sensitive Reagents with Zinc Ion in Different Cultured Cells

PubMed Central

Fujikawa, Koichi; Fukumori, Ryo; Nakamura, Saki; Kutsukake, Takaya; Takarada, Takeshi; Yoneda, Yukio

2015-01-01

Background Several chemicals have been widely used to evaluate the involvement of free Ca2+ in mechanisms underlying a variety of biological responses for decades. Here, we report high reactivity to zinc of well-known Ca2+-sensitive reagents in diverse cultured cells. Methodology/Principal Findings In rat astrocytic C6 glioma cells loaded with the fluorescent Ca2+ dye Fluo-3, the addition of ZnCl2 gradually increased the fluorescence intensity in a manner sensitive to the Ca2+ chelator EGTA irrespective of added CaCl2. The addition of the Ca2+ ionophore A23187 drastically increased Fluo-3 fluorescence in the absence of ZnCl2, while the addition of the Zn2+ ionophore pyrithione rapidly and additionally increased the fluorescence in the presence of ZnCl2, but not in its absence. In cells loaded with the zinc dye FluoZin-3 along with Fluo-3, a similarly gradual increase was seen in the fluorescence of Fluo-3, but not of FluoZin-3, in the presence of both CaCl2 and ZnCl2. Further addition of pyrithione drastically increased the fluorescence intensity of both dyes, while the addition of the Zn2+ chelator N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine (TPEN) rapidly and drastically decreased FluoZin-3 fluorescence. In cells loaded with FluoZin-3 alone, the addition of ZnCl2 induced a gradual increase in the fluorescence in a fashion independent of added CaCl2 but sensitive to EGTA. Significant inhibition was found in the vitality to reduce 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide in a manner sensitive to TPEN, EDTA and BAPTA in C6 glioma cells exposed to ZnCl2, with pyrithione accelerating the inhibition. Similar inhibition occurred in an EGTA-sensitive fashion after brief exposure to ZnCl2 in pluripotent P19 cells, neuronal Neuro2A cells and microglial BV2 cells, which all expressed mRNA for particular zinc transporters. Conclusions/Significance Taken together, comprehensive analysis is absolutely required for the demonstration of a variety of physiological and pathological responses mediated by Ca2+ in diverse cells enriched of Zn2+. PMID:26010609

The structural role and homogeneous redox equilibria of iron in peraluminous, metaluminous and peralkaline silicate melts

NASA Astrophysics Data System (ADS)

Dickenson, M. P.; Hess, P. C.

1986-02-01

The compositional dependence of the redox ratio (FeO/FeO1.5) has been experimentally determined in K2O-Al2O3-SiO2-Fe2O3-FeO (KASFF) and K2O-CaO-Al2O3-SiO2-Fe2O3-FeO (KCASFF) silicate melts. Compositions were equilibrated at 1,450° C in air, with 78 mol % SiO2. KASFF melts have from 1 to 5 mol % Fe2O3 and include both peraluminous (K2OAl2O3) compositions. KCASFF melts have 1 mol % Fe2O3 encompassing peraluminous, metaluminous (CaO+K2O>Al2O3) and peralkaline compositions. Peralkaline KASFF melts with 1 mol % Fe2O3 have low and constant values for the redox ratio, whereas in peraluminous melts the redox ratio increases with increasing (K2O/Al2O3). Increasing total iron concentration increases the redox ratio in peraluminous melts and slightly decreases the redox ratio in peralkaline melts. Substituting CaO for K2O at fixed total iron (1 mol %) increases the redox ratio in both peraluminous and metaluminous KCASFF melts; however, the redox ratio in peralkaline KCASFF melts is not affected by this exchange. These data indicate that Fe3+ is in four-fold coordination, with K+ or Ca2+ providing local charge balance. The tetrahedral ferric species is most stable in peralkaline melts and least stable in peraluminous melts, due to the competition between Al3+ and Fe3+ for charge balancing cations in the latter melt. Tetrahedral Fe3+ is also less stable when Ca2+ provides local charge balance. The data are consistent with a network modifying role for Fe2+ in the melt. The data are interpreted to reflect the effects of melt composition on the partitioning of K+ and Ca2+ and Fe3+ and Al3+ between various species in the melt. These relationships are discussed in terms of homogeneous equilibria between various iron-bearing and iron-free melt species. The results also reflect the effect of liquid composition on the exchange potentials μFe3+ Al-1 and μCa0.5K-1. The exchange potentials are relatively constant in peralkaline melts, but decrease in metaluminous and peraluminous melts as both (CaO+K2O)/(CaO+K2O+Al2O3) and K2O/CaO decrease. These qualitative observations imply that minerals exhibiting these exchanges will also be similarly affected as liquid composition changes.

The mechanism of potentiation of the glutamate-induced neurotoxicity by serum albumin. A possible role of nitric oxide.

PubMed

Sorokina, E G; Reutov, V P; Pinelis, V G; Vinskaya, N P; Vergun, O V; Khodorov, B I

2000-01-01

Potentiation of the delayed (Glu)-induced neurotoxicity by serum albumin (SA) was studied in experiments with cultured cerebellar granule cells. The delayed neuronal death (DND) was evaluated by counting neurons containing or excluding Trypan Blue 4 h after treatment with Glu. Cytoplasmic Ca2+ ([Ca2+]i) was measured in individual Fura-2-loaded neurons. It was shown that a 15-min application of bovine SA (4 mg/ml) together with Glu (100 microM, 10 microM glycine, Mg2+-free solution) enhanced DND in the culture 1.7 times (43.1+/-3.1%) with respect to the effect induced by Glu alone (24.6+/-0.6%). The bovine SA application did not change the dynamics of [Ca2+]i response during a short-term (1 min) and long-term (15 min) Glu-treatment. DND was prevented by simultaneous application of Glu and inhibitor of NO-synthase N omega-nitro-L-arginine methyl ester (L-NAME), 100 microM) (10.8+/-1.0%) as well as by the application of Glu with SA and L-NAME (9.8+/-1.2%). In order to evaluate the role of nitric oxide (NO) in the SA effect, the cells were incubated for 15 min with the NO-donors sodium nitroprusside (SNP, 10 and 100 microM) and sodium nitrite (NaNO2, 10 and 100 microM) together with SA and in its absence. SA also greatly enhanced the DND induced by SNP and NaNO2. Thus, the DND after simultaneous treatment with SA and SNP was 16.3+/-2.5% (10 microM) or 29.6+/-2.1% (100 microM), and 9.6+/-0.8% (10 microM) and 19.7+/-2.1% after treatment with SNP alone. Exposure to SA together with NaNO2 led to the DND increase up to 26.5+/-1.9% (10 microM) and 37.7+/-3.5% (100 microM) in comparison with 7.4+/-2.0% (10 microM) and 18.9+/-0.8% (100 microM) in experiments with NaNO2 alone. Taking into account the ability of NO and NO2 to oxidize unsaturated fatty acids and the ability of SA to bind them after their hydrolytic removal, we suggested that the SA-induced potentiation of Glu neurotoxicity resulted from exacerbation of the toxic effects of NO and other trace radicals on the neuronal membranes. This hypothesis was supported by the finding that SA also enhanced the neurotoxicity of the lipid prooxidant FeCl2. The simultaneous 15-min application of FeCl2 (10 microM) and SA caused a 51.5+/-4.0% increase in DND, which exceeded 2.4 times the effect produced by FeCl2 alone (21.3+/-2.3%).

The alteration of interelemental ratios in myocardium under the congenital heart disease (SRXRF)

NASA Astrophysics Data System (ADS)

Trunova, V. A.; Zvereva, V. V.; Okuneva, G. N.; Levicheva, E. N.

2007-05-01

It is the myocardium that bears the basic functional loading during heart working, including muscle contractility and enzyme activity. The elemental concentrations in myocardium tissue of heart were determined by SRXRF technique. Our investigation is systematical: the elemental content in each compartment (left and right ventricles, left and right auricles) of hearts of healthy and diseased children (congenital heart diseases, transposition of main vessels (TMV)) was analyzed. The elemental distribution in myocardium of four heart chambers of human fetuses was also analyzed. Following elements were determined: S, Cl, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, Rb, Sr. It was revealed that the elemental concentrations in myocardium of both ventricles are almost constant in heart of fetuses and healthy children. The transition from pre-natal study (fetus) to post-natal study is accompanied by the redistribution of chemical elements in myocardium. The higher concentrations of S, Fe, Ca, Sr and Cu in myocardium of children are observed, the content of K, Br, Rb and especially Se is lower than in heart of fetuses. The elemental distribution in myocardium of children TMV is considerably different in comparison with the healthy children: the higher levels of Cu are observed. The content of Se is lower.

Selective sequential separation of ABS/HIPS and PVC from automobile and electronic waste shredder residue by hybrid nano-Fe/Ca/CaO assisted ozonisation process.

PubMed

Mallampati, Srinivasa Reddy; Lee, Byoung Ho; Mitoma, Yoshiharu; Simion, Cristian

2017-02-01

The separation of plastics containing brominated flame retardants (BFR) like (acrylonitrile-butadiene-styrene (ABS), high-impact polystyrene (HIPS), and polyvinyl chloride (PVC)) from automobile and electronic waste shredder residue (ASR/ESR) are a major concern for thermal recycling. In laboratory scale tests using a hybrid nano-Fe/Ca/CaO assisted ozonation treatment has been found to selectively hydrophilize the surface of ABS/HIPS and PVC plastics, enhancing ABS wettability and thereby promoting its separation from ASR/ESR by means of froth flotation. The water contact angles, of ABS/HIPS and PVC decreased, about 18.7°, 18.3°, and 17.9° in ASR and about 21.2°, 20.7°, and 20.0° in ESR respectively. SEM-EDS, FT-IR, and XPS analyses demonstrated a marked decrease in [Cl] and a significant increase in the number of hydrophilic groups, such as CO, CO, and (CO)O, on the PVC or ABS surface. Under froth flotation conditions at 50rpm, about 99.1% of combined fraction of ABS/HIPS in ASR samples and 99.6% of ABS/HIPS in ESR samples were separated as settled fraction. After separation, the purity of the recovered combined ABS/HIPS fraction was 96.5% and 97.6% in ASR and ESR samples respectively. Furthermore, at 150rpm a 100% PVC separation in the settled fraction, with 98% and 99% purity in ASR and ESR plastics, respectively. Total recovery of non-ABS/HIPS and PVC plastics reached nearly 100% in the floating fraction. Further, this process improved the quality of recycled ASR/ESR plastics by removing surface contaminants or impurities. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fe-V redox flow batteries

DOEpatents

Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Xia, Guanguang

2014-07-08

A redox flow battery having a supporting solution that includes Cl.sup.- anions is characterized by an anolyte having V.sup.2+ and V.sup.3+ in the supporting solution, a catholyte having Fe.sup.2+ and Fe.sup.3+ in the supporting solution, and a membrane separating the anolyte and the catholyte. The anolyte and catholyte can have V cations and Fe cations, respectively, or the anolyte and catholyte can each contain both V and Fe cations in a mixture. Furthermore, the supporting solution can contain a mixture of SO.sub.4.sup.2- and Cl.sup.- anions.

Heterometal cubane-type MFe(3)S(4) clusters (M = Mo, V) trigonally symmetrized with hydrotris(pyrazolyl)borate(1-) and tris(pyrazolyl)methanesulfonate(1-) capping ligands.

PubMed

Fomitchev, Dmitry V; McLauchlan, Craig C; Holm, R H

2002-02-25

A series of heterometal cubane-type clusters containing [VFe(3)S(4)](2+) and [MoFe(3)S(4)](3+,2+) cores has been prepared. Ligand substitution of [(DMF)(3)VFe(3)S(4)Cl(3)](-) affords [(Tpms)VFe(3)S(4)L(3)](2)(-) (L = Cl(-) (8), EtS(-) (9), p-MeC(6)H(4)S(-), p-MeC(6)H(4)O(-)). A new procedure for the preparation of molybdenum single cubanes is introduced by the reaction of recently reported [(Tp)MoS(S(4))](-) with FeCl(2)/NaSEt to afford [(Tp)MoFe(3)S(4)Cl(3)](-) (1, 75% yield). This procedure is more efficient that the existing multistep synthesis of single cubanes, which generally affords clusters of mirror symmetry. Also prepared were [(Tp)MoFe(3)S(4)L(3)](-) (L = EtS(-) (2), p-MeC(6)H(4)S(-)). Reduction of 1 with borohydride gives [(Tp)MoFe(3)S(4)Cl(3)](2-) (5, 67%). Owing to the nature of the heterometal ligand, all clusters have idealized trigonal symmetry, reflected in their (1)H NMR spectra. Trigonal structures are demonstrated by crystallography of (Bu(4)N)[1,2], (Bu(4)N)(2)[5] x MeCN, and (Me(4)N)(2)[8,9]. The availability of 1 and 5 allows the first comparison of structures and (57)Fe isomer shifts of [MoFe(3)S(4)](3+,2+) in a constant ligand environment. Small increases in most bond distances indicate that an antibonding electron is added in the reduction of 1. Collective synthetic and electrochemical results from this and other studies demonstrate the existence of the series of oxidation states [VFe(3)S(4)](3+,2+,1+) and [MoFe(3)S(4)](4+,3+,2+) whose relative stabilities within a given series are strongly ligand dependent. Isomer shifts indicate that the reduction of 1 largely affects the Fe(3) subcluster and are consistent with the formal descriptions [MoFe(3+)(2)Fe(2+)S(4)](3+) (1) and [MoFe(3+)Fe(2+)(2)S(4)](2+) (5). Reaction of 1 with excess Li(2)S in acetonitrile affords the double cubane [[(Tp)MoFe(3)S(4)Cl(2)](2)(mu(2)(-)S)](2)(-), whose sulfide-bridged structure is supported by two sequential reductions separated by 290 mV, in analogy with previously reported double cubanes of higher charge. Trigonally symmetric single cubanes eliminate isomers in the formation of double cubanes and other cluster structures, and may be of considerable value in the preparation of new types of M-Fe-S clusters. (Tpms = tris(pyrazolyl)methanesulfonate(1-); Tp = hydrotris(pyrazolyl)borate(1-).)

Two dimensional Z-scheme AgCl/Ag/CaTiO3 nano-heterojunctions for photocatalytic hydrogen production enhancement

NASA Astrophysics Data System (ADS)

Jiang, Ziyuan; Pan, Jiaqi; Wang, Beibei; Li, Chaorong

2018-04-01

The two dimensional(2D) Z-scheme AgCl/Ag/Ca/TiO3 nano-heterojunction is synthesized via simple preparation of hydrothermal-chemical co-deposition method. The results of SEM, EDS, elemental mapping, XRD, TEM, XPS and Raman shift imply that the AgCl/Ag nanoparticles have deposited on the surfaces of CaTiO3 nanosheets successfully. Compared with the unmodified samples, the photocatalytic activity of the as-prepared 2D AgCl/Ag/CaTiO3 nano-heterojunction exhibits a remarkable enhancement by the hydrogen production. Further, the photocatalytic process has been studied and the mechanism of the photocatalytic hydrogen production enhancement has been provided, which could be ascribed to the Z-scheme heterojunction and 2D lamellar structure of the CaTiO3.

Reaction of iron with hydrogen chloride-oxygen mixtures at 550 C

NASA Technical Reports Server (NTRS)

Jacobson, N. S.

1986-01-01

The reaction of iron with 1 percent HCl/0-50 percent O2/Ar has been studied at 550 C with thermogravimetry to monitor kinetics and scanning electron microscopy to characterize product morphologies. In addition, the volatile species were identified with an atmospheric pressure sampling mass spectrometer. The reaction of 1 percent HCl/Ar produces FeCl2. The reactions of 1 percent HCl/1, 10, 50 percent O2/Ar produce Fe2O3, Fe3O4, FeCl2, and FeCl3. In each case condensed phase chlorides form at the oxide/metal interface where the oxygen potential is low. The 10 and 50 percent oxygen mixtures have kinetics in the first 3 hr similar to pure oxidation with some deviations due to iron-chloride formation. The 1 percent oxygen mixture shows enhanced reaction rates over oxidation, very likely due to the formation of a porous scale.

Multicomponent Pt-Based Zigzag Nanowires as Selectivity Controllers for Selective Hydrogenation Reactions.

PubMed

Bai, Shuxing; Bu, Lingzheng; Shao, Qi; Zhu, Xing; Huang, Xiaoqing

2018-06-22

The selective hydrogenation of α, β-unsaturated aldehyde is an extremely important transformation, while developing efficient catalysts with desirable selectivity to highly value-added products is challenging, mainly due to the coexistence of two conjugated unsaturated functional groups. Herein, we report that a series of Pt-based zigzag nanowires (ZNWs) can be adopted as selectivity controllers for α, β-unsaturated aldehyde hydrogenation, where the excellent unsaturated alcohol (UOL) selectivity (>95%) and high saturated aldehyde (SA) selectivity (>94%) are achieved on PtFe ZNWs and PtFeNi ZNWs+AlCl 3 , respectively. The excellent UOL selectivity of PtFe ZNWs is attributed to the lower electron density of the surface Pt atoms, while the high SA selectivity of PtFeNi ZNWs+AlCl 3 is due to synergy between PtFeNi ZNWs and AlCl 3 , highlighting the importance of Pt-based NWs with precisely controlled surface and composition for catalysis and beyond.

Major element compositions of fluid inclusions from hydrothermal vein-type deposits record eroded sedimentary units in the Schwarzwald district, SW Germany

NASA Astrophysics Data System (ADS)

Walter, Benjamin F.; Burisch, Mathias; Marks, Michael A. W.; Markl, Gregor

2017-12-01

Mixing of sedimentary formation fluids with basement-derived brines is an important mechanism for the formation of hydrothermal veins. We focus on the sources of the sediment-derived fluid component in ore-forming processes and present a comprehensive fluid inclusion study on 84 Jurassic hydrothermal veins from the Schwarzwald mining district (SW Germany). Our data derive from about 2300 fluid inclusions and reveal differences in the average fluid composition between the northern, central, and southern Schwarzwald. Fluids from the northern and southern Schwarzwald are characterised by high salinities (18-26 wt% NaCl+CaCl2), low Ca/(Ca+Na) mole ratios (0.1-0.4), and variable Cl/Br mass ratios (30-1140). In contrast, fluids from the central Schwarzwald show even higher salinities (23-27 wt% NaCl+CaCl2), higher Ca/(Ca+Na) mole ratios (0.2-0.9), and less variable Cl/Br mass ratios (40-130). These fluid compositions correlate with the nature and thickness of the now eroded sedimentary cover rocks. Compared to the northern and the southern Schwarzwald, where halite precipitation occurred during the Middle Triassic, the sedimentary basin in the central Schwarzwald was relatively shallow at this time and no halite was precipitated. Accordingly, Cl/Br ratios of fluids from the central Schwarzwald provide no evidence for the reaction of a sedimentary brine with halite, whereas those from the northern and southern Schwarzwald do. Instead, elevated Ca/(Ca+Na), high SO4 contents, and relatively low Cl/Br imply the presence of a gypsum dissolution brine during vein formation in the central Schwarzwald which agrees with the reconstructed regional Triassic geology. Hence, the information archived in fluid inclusions from hydrothermal veins in the crystalline basement has the potential for reconstructing sedimentary rocks in the former overburden.

Milk and dairy products: a unique micronutrient combination.

PubMed

Gaucheron, Frédéric

2011-10-01

Milk and dairy products contain micronutrients such as minerals and vitamins, which contribute to multiple and different vital functions in the organism. The mineral fraction is composed of macroelements (Ca, Mg, Na, K, P, and Cl) and oligoelements (Fe, Cu, Zn, and Se). From a physicochemical point of view, the chemical forms, the associations with other ions or organic molecules, and the location of macroelements such as Ca, Mg, Na, K, P, and Cl in milk are relatively well described and understood. Thus, it is admitted that these macroelements are differently distributed into aqueous and micellar phases of milk, depending on their nature. K, Na, and Cl ions are essentially in the aqueous phase, whereas Ca, P, and Mg are partly bound to the casein micelles. About one third of the Ca, half of the P, and two thirds of the Mg are located in the aqueous phase of milk. Dairy products are more or less rich in these different minerals. In cheeses, mineral content depends mainly on their processing. The Ca content is strongly related to the acidification step. Moreover, if acidification is associated with the draining step, the Ca content in the cheese will be reduced. Thus, the Ca content varies in the following increasing order: milks/fermented milks/fresh cheeses < soft cheeses < semi-hard cheeses < hard cheeses. The chemical forms and associations are less described than those present in milk. Concerning Ca, the formation of insoluble calcium phosphate, carbonate, and lactate is reported in some ripened cheeses. The NaCl content in cheeses depends on the salting of the curd. From a nutritional point of view, it is largely admitted that milk and dairy products are important sources of Ca, Mg, Zn, and Se. The vitamin fraction of milk and dairy products is composed of lipophilic (A, D, E, and K) and hydrophilic (B(1), B(2), B(3), B(5), B(6), B(8), B(9), B(12), and C) vitamins. Because of their hydrophobic properties, the lipophilic vitamins are mainly in the milk fat fraction (cream, butter). The hydrophilic vitamins are in the aqueous phase of milk. For one part of these vitamins, the concentrations described in the literature are not always homogenous and sometimes not in accordance between them; these discrepancies are due to the difficulty of the sample preparation and the use of appropriate methods for their quantification. However, there is no doubt of the significant contribution of milk and dairy products to the intake of vitamins. Milk and dairy are considered essential sources for vitamins. Key teaching points: Milk and dairy products are unique micronutrient combinations with recognized health benefits. The concentration, chemical forms, and location of different minerals are relatively well known and described. For example, Ca is present in dairy products in different forms: free, associated with citrate, inorganic and organic phosphates, and free fatty acids. Milk and dairy products are excellent sources of Ca, P, Mg, Zn, and Se. The concentration of vitamins in milk and dairy products is variable and depends on several factors such as biosynthesis, animal feeding, physicochemical conditions (heat, light, O(2), oxidant agents), and analytical methods for their determinations. Vitamins A, D, E, and K are mainly located in the lipid phase and vitamins of group B and C in the aqueous phase. Milk and dairy products are excellent sources of vitamins A, B(1), B(2), and B(12).

Quantum chemical calculations to determine partitioning coefficients for HgCl2 on iron-oxide aerosols.

PubMed

Tacey, Sean A; Xu, Lang; Szilvási, Tibor; Schauer, James J; Mavrikakis, Manos

2018-04-30

Gas-to-particle phase partitioning controls the pathways for oxidized mercury deposition from the atmosphere to the Earth's surface. The propensity of oxidized mercury species to transition between these two phases is described by the partitioning coefficient (K p ). Experimental measurements of K p values for HgCl 2 in the presence of atmospheric aerosols are difficult and time-consuming. Quantum chemical calculations, therefore, offer a promising opportunity to efficiently estimate partitioning coefficients for HgCl 2 on relevant aerosols. In this study, density functional theory (DFT) calculations are used to predict K p values for HgCl 2 on relevant iron-oxide surfaces. The model is first verified using a NaCl(100) surface, showing good agreement between the calculated (2.8) and experimental (29-43) dimensionless partitioning coefficients at room temperature. Then, the methodology is applied to six atmospherically relevant terminations of α-Fe 2 O 3 (0001): OH-Fe-R, (OH) 3 -Fe-R, (OH) 3 -R, O-Fe-R, Fe-O 3 -R, and O 3 -R (where R denotes bulk ordering). The OH-Fe-R termination is predicted to be the most stable under typical atmospheric conditions, and on this surface termination, a dimensionless HgCl 2 K p value of 5.2 × 10 3 at 295 K indicates a strong preference for the particle phase. This work demonstrates DFT as a promising approach to obtain partitioning coefficients, which can lead to improved models for the transport of mercury, as well as for other atmospheric pollutant species, through and between the anthroposphere and troposphere. Copyright © 2018 Elsevier B.V. All rights reserved.

Highly Efficient Extraction of Phenolic Compounds by Use of Magnetic Room Temperature Ionic Liquids for Environmental Remediation

PubMed Central

Deng, Ning; Li, Min; Zhao, Lijie; Lu, Chengfei; de Rooy, Sergio L.; Warner, Isiah M.

2011-01-01

A hydrophobic magnetic room temperature ionic liquid (MRTIL), trihexyltetradecylphosphonium tetrachloroferrate(III) ([3C6PC14][FeCl4]), was synthesized from trihexyltetradecylphosphonium chloride and FeCl3·6H2O. This MRTIL was investigated as a possible separation agent for solvent extraction of phenolic compounds from aqueous solution. Due to its strong paramagnetism, [3C6PC14][FeCl4] responds to an external neodymium magnet, which was employed in the design of a novel magnetic extraction technique. The conditions for extraction, including extraction time, volume ratio between MRTIL and aqueous phase, pH of aqueous solution, and structures of phenolic compounds were investigated and optimized. The magnetic extraction of phenols achieved equilibrium in 20 min and the phenolic compounds were found to have higher distribution ratios under acidic conditions. In addition, it was observed that phenols containing a greater number of chlorine or nitro substitutents exhibited higher distribution ratios. For example, the distribution ratio of phenol (DPh) was 107. In contrast, 3,5-dichlorophenol distribution ratio (D3,5-DCP) had a much higher value of 6372 under identical extraction conditions. When compared with four selected traditional non-magnetic room temperature ionic liquids, our [3C6PC14][FeCl4] exhibited significantly higher extraction efficiency under the same experimental conditions used in this work. Pentachlorophenol, a major component in the contaminated soil sample obtained from a superfund site, was successfully extracted and removed by use of [3C6PC14][FeCl4] with high extraction efficiency. Pentachlorophenol concentration was dramatically reduced from 7.8 μg.mL−1 to 0.2 μg.mL−1 after the magnetic extraction by use of [3C6PC14][FeCl4]. PMID:21783320

Partially hydrolyzed guar gum supplement reduces high-fat diet increased blood lipids and oxidative stress and ameliorates FeCl3-induced acute arterial injury in hamsters

PubMed Central

Kuo, Dar-Chih; Hsu, Shih-Ping; Chien, Chiang-Ting

2009-01-01

Increased reactive oxygen species (ROS) and hyperlipidemia can promote arterial thrombus. We evaluated the potential of a partially hydrolyzed guar gum (PHGG) as dietary fiber on lipid profiles and FeCl3-induced arterial thrombosis in the high fat-diet fed hamsters. Our in vitro results found that PHGG is efficient to scavenge O2-•, H2O2, and HOCl. High fat-diet increased plasma triglyceride, total cholesterol, LDL, VLDL, methylguanidine and dityrosine level and accelerated FeCl3-induced arterial thrombosis formation (from 463 ± 51 to 303 ± 45 sec). Low dose PHGG supplement significantly decreased the total cholesterol, LDL, methylguanidine and dityrosine level and delayed the time for arterial thrombosis formation (528 ± 75 sec). High dose PHGG supplement decreased the level in triglyceride, total cholesterol, LDL and VLDL and further delayed the time for arterial thrombus (671 ± 36 sec). The increased Bax protein and decreased Bcl-2 and HSP-70 protein expression was found in the carotid and femoral arteries of high fat-diet hamsters. Low and high dose of PHGG supplement decreased Bax expression and increased Bcl-2 and HSP-70 protein expression. We found that FeCl3 significantly enhanced intercellular adhesion molecule-1 and 4-hydroxynonenal expression in the endothelial site of damaged artery after 150-sec FeCl3 stimulation. PHGG supplement decreased the endothelial ICAM-1 and 4-hydroxynonenal expression after 150-sec FeCl3 stimulation. Based on these results, we conclude that PHGG supplement can increase antioxidant protein expression and thus decrease oxidative stress induced arterial injury. PMID:19272178

Synthesis, properties, and reactivity of a series of non-heme {FeNO}(7/8) complexes: implications for Fe-nitroxyl coordination.

PubMed

Sanders, Brian C; Patra, Ashis K; Harrop, Todd C

2013-01-01

The biochemical properties of nitroxyl (HNO/NO(-)) are distinct from nitric oxide (NO). Metal centers, particularly Fe, appear as suitable sites of HNO activity, both for generation and targeting. Furthermore, reduced Fe-NO(-)/Fe-HNO or {FeNO}(8) (Enemark-Feltham notation) species offer unique bonding profiles that are of fundamental importance. Given the unique chemical properties of {FeNO}(8) systems, we describe herein the synthesis and properties of {FeNO}(7) and {FeNO}(8) non-heme complexes containing pyrrole donors that display heme-like properties, namely [Fe(LN(4)(R))(NO)] (R = C(6)H(4) or Ph for 3; and R = 4,5-Cl(2)C(6)H(2) or PhCl for 4) and K[Fe(LN(4)(R))(NO)] (R = Ph for 5; R = PhCl for 6). X-ray crystallography establishes that the Fe-N-O angle is ~155° for 3, which is atypical for low-spin square-pyramidal {FeNO}(7) species. Both 3 and 4 display ν(NO) at ~1700 cm(-1) in the IR and reversible diffusion-controlled cyclic voltammograms (CVs) (E(1/2)=~-1.20 V vs. Fc/Fc(+) (ferrocene/ferrocenium redox couple) in MeCN) suggesting that the {FeNO}(8) compounds 5 and 6 are stable on the CV timescale. Reduction of 3 and 4 with stoichiometric KC(8) provided the {FeNO}(8) compounds 5 and 6 in near quantitative yield, which were characterized by the shift in ν(NO) to 1667 and ~1580 cm(-1), respectively. While the ν(NO) for 6 is consistent with FeNO reduction, the ν(NO) for 5 appears more indicative of ligand-based reduction. Additionally, 5 and 6 engage in HNO-like chemistry in their reactions with ferric porphyrins [Fe(III)(TPP)X] (TPP = tetraphenylporphyrin; X = Cl(-), OTf(-) (trifluoromethanesulfonate anion or CF(3)SO(3)(-))) to form [Fe(TPP)NO] in stoichiometric yield via reductive nitrosylation. Copyright © 2012 Elsevier Inc. All rights reserved.

(CaO)(FeSe): A layered wide-gap oxychalcogenide semiconductor

DOE PAGES

Han, Fei; Wang, Di; Malliakas, Christos D.; ...

2015-07-20

A new iron-oxychalcogenide (CaO)(FeSe) was obtained which crystallizes in the orthorhombic space group Pnma (No. 62) with a = 5.9175(12) Å, b = 3.8797(8) Å, c = 13.170(3) Å. The unique structure of (CaO)(FeSe) is built up of a quasi-two-dimensional network of corrugated infinite layers of corner-shared FeSe 2O 2 tetrahedra that extend in the ab-plane. The FeSe 2O 2 layers stack along the c-axis with Ca 2+ cations sandwiched between the layers. Optical spectroscopy and resistivity measurements reveal semiconducting behavior with an indirect optical band gap of around 1.8 eV and an activation energy of 0.19(1) eV. Furthermore, electronicmore » band structure calculations at the density function level predict a magnetic configuration as ground state and confirm the presence of an indirect wide gap in (CaO)(FeSe).« less

The Elemental Analysis of Biological and Environmental Materials Using a 2MEV Proton Beam

NASA Astrophysics Data System (ADS)

Arshed, Waheed

Available from UMI in association with The British Library. A programme has been developed to simulate the proton induced x-ray emission (PIXE) spectra and its uses have been described. The PIXE technique has been applied to the analysis of new biological reference materials which consist of IAEA human diet samples and NIST leaf samples. Homogeneity of these and two existing reference materials, IAEA soil -7 and Bowen's kale, has also been determined at the mug scale. A subsample representative of a material is ascertained by determination of sampling factors for the elements detected in the material. Proton induced gamma-ray emission (PIGE) analysis in conjunction with PIXE has been employed to investigate F and other elemental concentrations found in human teeth samples. The mean F concentration in enamel and dentine parts of teeth followed an age dependent model. Concentrations of Ca and P were found to be higher in the enamel than in the dentine. Analysis of blood and its components in the study of elemental models in sickle cell disease in Nigerians has been carried out. Comparisons revealed that Cl, Ca and Cu were at higher levels whereas K, Fe, Zn and Rb were at lower levels in the whole blood of the sicklers compared to controls. Similar results were obtained for the erythrocytes except that Br was found at higher concentration in erythrocytes of the sicklers. Higher concentrations of Cl, K, Fe and Cu were also observed in plasma of the sicklers compared to controls. PIXE and scanning electron microscopy (SEM) were used in the characterization of the Harmattan dust particulates collected at Kano and Ife. Most of the elements were found to be at higher concentrations as compared to those found in Recife (Brazil) and Toronto (Canada). The value of total suspended particulate was above the relevant national air quality standards. PIXE in conjunction with Rutherford backscattering spectrometry and instrumental neutron activation analysis was employed in the analysis of soil samples detecting 31 elements. The results have been discussed with reference to elemental concentrations and Ca/Si ratio. The latter was a valid indicator of soil pollution by the cement dust. (Abstract shortened by UMI.).

Cyclic-nucleotide–gated cation current and Ca2+-activated Cl current elicited by odorant in vertebrate olfactory receptor neurons

PubMed Central

Li, Rong-Chang; Ben-Chaim, Yair; Yau, King-Wai; Lin, Chih-Chun

2016-01-01

Olfactory transduction in vertebrate olfactory receptor neurons (ORNs) involves primarily a cAMP-signaling cascade that leads to the opening of cyclic-nucleotide–gated (CNG), nonselective cation channels. The consequent Ca2+ influx triggers adaptation but also signal amplification, the latter by opening a Ca2+-activated Cl channel (ANO2) to elicit, unusually, an inward Cl current. Hence the olfactory response has inward CNG and Cl components that are in rapid succession and not easily separable. We report here success in quantitatively separating these two currents with respect to amplitude and time course over a broad range of odorant strengths. Importantly, we found that the Cl current is the predominant component throughout the olfactory dose–response relation, down to the threshold of signaling to the brain. This observation is very surprising given a recent report by others that the olfactory-signal amplification effected by the Ca2+-activated Cl current does not influence the behavioral olfactory threshold in mice. PMID:27647918

Solubility of NaCl in aqueous electrolyte solutions from 10 to 100°C

USGS Publications Warehouse

Clynne, M.A.; Potter, R.W.; Haas, J.L.

1981-01-01

The solubilities of NaCl in aqueous KCl, MgCl2, CaCl2, and mixed CaCl2-KCl solutions have been determined from 10 to 100??C. The data were fit to an equation, and the equation was used to calculate values of the change in solubility of NaCl, ???[NaCl]/???T. These values are required for calculations of the rate of migration of fluids in a thermal gradient in rock salt. The data obtained here indicate that the values of ???[NaCl]/???T are 36-73% greater for solutions containing divalent ions than for the NaCl-H2O system.

Iron-mediated and -catalyzed metalative cyclization of electron-withdrawing-group-substituted alkynes and alkenes with Grignard reagents.

PubMed

Hata, Takeshi; Sujaku, Shiro; Hirone, Naoki; Nakano, Kirihiro; Imoto, Junsuke; Imade, Haduki; Urabe, Hirokazu

2011-12-16

Treatment of ethyl (E)-5,5-bis[(benzyloxy)methyl]-8-(N,N-diethylcarbamoyl)-2-octen-7-ynoate with an iron reagent generated from FeCl(2) and tBuMgCl in a ratio of 1:4 (abbreviated as FeCl(2)/4 tBuMgCl) afforded ethyl [4,4-bis[(benzyloxy)methyl]-2-[(E)-(N,N-diethylcarbamoyl)methylene]cyclopent-1-yl]acetate in good yield. Deuteriolysis of an identical reaction mixture afforded the bis-deuterated product ethyl [4,4-bis[(benzyloxy)methyl]-2-[(E)-(N,N-diethylcarbamoyl)deuteriomethylene]cyclopent-1-yl]deuterioacetate, thus confirming the existence of the corresponding dimetalated intermediate. The latter intermediate can react with halogens or aldehydes to facilitate further synthetic transformations. The amount of FeCl(2) was reduced to catalytic levels (10 mol % relative to enyne), and catalytic cyclizations of this sort proceeded with yields comparable to those of the aforementioned stoichiometric reactions. The cyclization of diethyl (E,E)-2,7-nonadienedioate with a stoichiometric amount of FeCl(2)/4 tBuMgCl, followed by the addition of sBuOH as a proton source, afforded a mixture of 2-(ethoxycarbonyl)-3-bicyclo[3.3.0]octanone and its enol form in good yield. The use of aldehyde or ketone in place of sBuOH afforded 2-(ethoxycarbonyl)-3-bicyclo[3.3.0]octanone, which has an additional hydroxyalkyl side chain. Additionally, the metalation of a carbon-carbon unsaturated bond in N,N-diethyl-5,5-bis[(benzyloxy)methyl]-7,8-epoxy-2-octynamide or (E)-3,3-dimethyl-6-(N,N-diethylcarbamoyl)-5-hexenyl p-toluenesulfonate with FeCl(2)/4 tBuMgCl or FeCl(2)/4 PhMgBr was followed by an intramolecular alkylation with an epoxide or alkyl p-toluenesulfonate to afford 5,5-bis[(benzyloxy)methyl]-3-[(E)-(N,N-diethylcarbamoyl)methylene]-1-cyclohexanol or N,N-diethyl(3,3-dimethylcyclopentyl)acetamide after hydrolysis. In both cases, the remaining metalated portion α to the amide group was confirmed by deuteriolysis and could be utilized for an alkylation with methyl iodide. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fermentation profiles of Manzanilla-Aloreña cracked green table olives in different chloride salt mixtures.

PubMed

Bautista-Gallego, J; Arroyo-López, F N; Durán-Quintana, M C; Garrido-Fernández, A

2010-05-01

NaCl plays an important role in table olive processing affecting the flavour and microbiological stability of the final product. However, consumers demand foods low in sodium, which makes necessary to decrease levels of this mineral in fruits. In this work, the effects of diverse mixtures of NaCl, CaCl(2) and KCl on the fermentation profiles of cracked directly brined Manzanilla-Aloreña olives, were studied by means of response surface methodology based in a simplex lattice mixture design with constrains. All salt combinations led to lactic acid processes. The growth of Enterobacteriaceae populations was always limited and partially inhibited by the presence of CaCl(2). Only time to reach half maximum populations and decline rates of yeasts, which were higher as concentrations of NaCl or KCl increased, were affected, and correspondingly modelled, as a function of salt mixtures. However, lactic acid bacteria growth parameters could not be related to initial environmental conditions. They had a longer lag phase, slower growth and higher population levels than yeasts. Overall, the presence of CaCl(2) led to a slower Enterobacteriaceae and lactic acid bacteria growth than the traditional NaCl brine but to higher yeast activity. The presence of CaCl(2) in the fermentation brines also led to higher water activity, lower pH and combined acidity as well as a faster acidification while NaCl and KCl had fairly similar behaviours. Apparently, NaCl may be substituted in diverse proportions with KCl or CaCl(2) without substantially disturbing water activity or the usual fermentation profiles while producing olives with lower salt content. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Activation Thermodynamics and H/D Kinetic Isotope Effect of the H ox to H red H + Transition in [FeFe] Hydrogenase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ratzloff, Michael W.; Wilker, Molly B.; Mulder, David W.

Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here in this paper we address the route of electron transfer from CdSe→CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The H ox→H redH + reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol -1 and a ~2.5-foldmore » kinetic isotope effect. Overall these results support electron injection from CdSe into CaI involving F-clusters, and that the H ox→H redH + step of catalytic proton reduction in CaI proceeds by a proton-dependent process.« less

Activation Thermodynamics and H/D Kinetic Isotope Effect of the H ox to H red H + Transition in [FeFe] Hydrogenase

DOE PAGES

Ratzloff, Michael W.; Wilker, Molly B.; Mulder, David W.; ...

2017-08-29

Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here in this paper we address the route of electron transfer from CdSe→CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The H ox→H redH + reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol -1 and a ~2.5-foldmore » kinetic isotope effect. Overall these results support electron injection from CdSe into CaI involving F-clusters, and that the H ox→H redH + step of catalytic proton reduction in CaI proceeds by a proton-dependent process.« less

High-temperature carbonates in the Stillwater Complex, Montana, USA

NASA Astrophysics Data System (ADS)

Aird, H. M.; Boudreau, A. E.

2012-12-01

The processes involved in the petrogenesis of the sulphide-hosted platinum-group-element (PGE) deposits of the Stillwater Complex are controversial, with theories ranging from the purely magmatic to those involving an aqueous fluid. To further constrain these models, we have been examining the trace phase assemblages in rocks away from the ore zones. High-temperature carbonates have been observed in association with sulphide minerals below the platiniferous J-M Reef of the Stillwater Complex. The carbonate assemblage consists of dolomite with exsolved calcite and is found in contact with sulphide minerals: chalcopyrite and pyrrhotite in the Peridotite Zone; and pyrrhotite with pentlandite, pyrite and chalcopyrite in Gabbronorite I of the Lower Banded Series. The minimal silicate alteration and the lack of greenschist minerals in association with the mineral assemblage are consistent with a high-temperature origin for the carbonates. The calcite-dolomite geothermometer [1] yields a minimum formation temperature of ~900°C for the unmixed assemblages. A reaction rim surrounds the carbonate-sulphide assemblages, showing an alteration of the host orthopyroxene to a more Ca-enriched, Fe-depleted composition. This is consistent with diffusive exchange between carbonates and pyroxenes at high temperatures, mediated by an aqueous fluid. The highly variable molar MnO/FeO ratios in both the high-temperature carbonates and their associated altered pyroxene rims also imply their interaction with a fluid. The carbonate assemblages are consistent with Stillwater fluid inclusion studies [2], showing that fluids comprising coexisting Cl-rich brine and carbonic fluid were trapped in pegmatitic quartz at 700-715°C, some of which also contained "accidental" calcite inclusions. The high Cl-content of apatite [3] found below the platiniferous J-M Reef is further evidence that a Cl-rich fluid was migrating through the rocks beneath the Reef. Carbonates have been shown to be stabilized by Cl-rich fluids [4]. The association of high-temperature carbonates with sulphides beneath the J-M reef supports the hydromagmatic theory which involves a late-stage chloride-carbonate fluid percolating upwards, dissolving PGE and sulphides and redepositing them at a higher stratigraphic level. [1] Anovitz, L.M., and Essene, E.J., 1987, Phase Equilibria in the System CaCO3-MgCO3-FeCO3: Journal of Petrology, v. 28, p. 389-414. [2] Hanley, J.J., Mungall, J.E., Pettke, T., Spooner, E.T.C., and Bray, C.J., 2008, Fluid and Halide Melt Inclusions of Magmatic Origin in the Ultramafic and Lower Banded Series, Stillwater Complex, Montana, USA: Journal of Petrology, v. 49, p. 1133-1160. [3] Boudreau, A.E., and McCallum, I.S., 1989, Investigations of the Stillwater Complex: Part V. Apatites as indicators of evolving fluid composition: Contributions to Mineralogy and Petrology, v. 102, p. 138-153. [4] Newton, R.C., and Manning, C.E., 2002, Experimental determination of calcite solubility in H2O-NaCl solutions at deep crust/upper mantle pressures and temperature: implications for metasomatic processes in shear zones: American Mineralogist, v. 87, p. 1401-1409.

Phase Diagram of the Al-Ca-Fe-Si System and Its Application for the Design of Aluminum Matrix Composites

NASA Astrophysics Data System (ADS)

Belov, Nikolay A.; Naumova, Evgeniya A.; Akopyan, Torgom K.; Doroshenko, Vitaliy V.

2018-05-01

The phase composition of aluminum alloys in the Al-Ca-Fe-Si system, including the distribution of phases in the solid state and solidification reactions, has been studied. It is shown that the addition of iron and silicon to Al-Ca alloys leads to the formation of ternary Al2CaSi2 and Al10CaFe2 compounds. The equilibrium between these compounds implies the occurrence of the quaternary L → Al + Al4Ca + Al2CaSi2 + Al10CaFe2 eutectic reaction. The alloys near this eutectic have the best structure, which is typical of aluminum matrix composites. It is shown that Al-Ca alloys can have high manufacturability during both shape casting and rolling. This is due to the combination of a narrow temperature range of solidification and a favorable morphology for the eutectic, which has a fine structure. The combination of the mechanical and physical properties of the Al-Ca eutectic-based alloys significantly exceed those of branded alloys based on aluminum-silicon eutectics.

Fluoride adsorption properties of three modified forms of activated alumina in drinking water.

PubMed

Duan, Ying; Wang, Chenchen; Li, Xuede; Xu, Wei

2014-12-01

The study describes the removal of fluoride from drinking water using activated alumina (AA). AA was modified with H2SO4, FeCl3 and a combination of the two to enhance fluoride adsorption. The AA adsorbents were characterized using Brunauer-Emmett-Teller surface area analysis and X-ray fluorescence. The maximum adsorption capacity of H2SO4- and FeCl3-modified AA adsorbents was 4.98 mg/g, which is 3.4 times higher compared with that of normal AA. The results showed that the surface area of AA increased when modified with H2SO4. AA modified with FeCl3 enhanced fluoride adsorption ability through ion-exchange between chlorine ions and fluoride ions. The fluoride adsorption properties of AA modified with both H2SO4 and FeCl3 were consistent with the Langmuir model. The fluoride adsorption kinetics of the adsorbents were well described by the pseudo-second-order kinetic model.

Enhanced cellulase hydrolysis of eucalyptus waste fibers from pulp mill by Tween80-assisted ferric chloride pretreatment.

PubMed

Chen, Liheng; Fu, Shiyu

2013-04-03

Pretreatment combining FeCl3 and Tween80 was performed for cellulose-to-ethanol conversion of eucalyptus alkaline peroxide mechanical pulping waste fibers (EAWFs). The FeCl3 pretreatment alone showed a good effect on the enzymatic hydrolysis of EAWFs, but inhibited enzyme activity to some extent. A surfactant, Tween80, added during FeCl3 pretreatment was shown to significantly enhance enzyme reaction by eluting enzymatic inhibitors such as iron(III) that are present at the surface of the pretreated biomass. Treatment temperature, liquid-solid ratio, treatment time, FeCl3 concentration, and Tween80 dosage for pretreatment were optimized as follows: 180 °C, 8:1, 30 min, 0.15 mol/L, and 1% (w/v). Pretreated EAWFs under such optimal conditions provided enzymatic glucose (based on 100 g of oven-dried feedstock) and substrate enzymatic digestibility of EAWFs of 34.8 g and 91.3% after 72 h of enzymatic hydrolysis, respectively, with an initial cellulase loading of 20 FPU/g substrate.

Synthesis and application of magnetic deep eutectic solvents: Novel solvents for ultrasound assisted liquid-liquid microextraction of thiophene.

PubMed

Khezeli, Tahere; Daneshfar, Ali

2017-09-01

Two novel magnetic deep eutectic solvents (MDESs), comprised of cheap and simple components named [choline chloride/phenol] [FeCl 4 ] and [choline chloride/ethylene glycol] [FeCl 4 ] were prepared and characterized by CHN elemental analysis, proton nuclear magnetic resonance ( 1 H NMR), vibrating sample magnetometery (VSM), Raman, Fourier transform-infrared (FT-IR) and UV-Vis spectrometery. The extraction efficiency of the prepared MDESs has been investigated in ultrasound assisted liquid-liquid microextraction based MDES (UALLME-MDES). Briefly, MDESs were added to n-heptan containing thiophene. Then, MDESs were dispersed in n-heptane by sonication. After that, microdroplets of MDESs were collected by a magnet and the remained concentration of thiophene in n-heptane phase was analyzed by GC-FID. The results indicated that [choline chloride/phenol] [FeCl 4 ] has higher extraction efficiency than [choline chloride/ethylene glycol] [FeCl 4 ]. This work opens a new way to the application of MDESs. Copyright © 2016 Elsevier B.V. All rights reserved.

Microbiological, physicochemical, and heavy metals assessment of groundwater quality in the Triffa plain (eastern Morocco)

NASA Astrophysics Data System (ADS)

Yahya, Hameed Saleh Ali; Jilali, Abdelhakim; Mostareh, Mohammed Mohammed Mohammed; Chafik, Zouheir; Chafi, Abdelhafid

2017-12-01

The focus of this study is the physicochemical and bacteriological characteristics of groundwater in the Triffa plain, Morocco. In total, 34 groundwater samples were analyzed for major elements (Tp, pH, EC, K+, Na+, Ca2+, Mg2+, Cl-, SO4 2-, NO3 -, NO2 -, NH4 +, H2PO4 -, CO3, and HCO3 -) and trace metal (Al, Cd, Cu, Fe, and Zn) content. The results show that the pH values range between 6.7 and 8.9, electrical conductivity ranges between 740 and 7340 µS/cm, and nitrate content ranges between 1.7 and 212 mg/l. Hydrochemical facies represented using a Piper diagram indicate an Na-K-Cl type water. All the trace metal concentrations are within the admissible standard range except for Cd. The bacteriological analysis showed that the majority of groundwater samples are contaminated. Generally, the content of total coliforms, fecal coliforms, and fecal streptococci ranged from 0 to 140, 0 to 125, and 0 to 108 CFU/100 ml, respectively. The samples are grouped according to three factors. Factor 1 shows strong positive loadings of EC, Mg, Cl, Na and K with 51.91% of total variance (TV); factor 2 shows strong negative loadings of NO3, SO4 and Ca with 17.98% of TV; and factor 3 shows strong negative loading of HCO3 with 15.56 of TV. We conclude that the quality of this groundwater is suitable for irrigation and domestic use (cleaning house, ect).

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy.

PubMed

Kumar, N; Andersson, M P; van den Ende, D; Mugele, F; Siretanu, I

2017-12-19

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl 2 concentration. Using DLVO theory with charge regulation, we determine from the measured force-distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl 2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl 2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca 2+ ion adsorption, while Cl - adsorption at higher CaCl 2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca 2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl - ions will co-adsorb, thereby changing the observed ordered surface structure.

Preparation and characterization of silk fibroin as a biomaterial with potential for drug delivery

PubMed Central

2012-01-01

Background Degummed silk fibroin from Bombyx mori (silkworm) has potential carrier capabilities for drug delivery in humans; however, the processing methods have yet to be comparatively analyzed to determine the differential effects on the silk protein properties, including crystalline structure and activity. Methods In this study, we treated degummed silk with four kinds of calcium-alcohol solutions, and performed secondary structure measurements and enzyme activity test to distinguish the differences between the regenerated fibroins and degummed silk fibroin. Results Gel electrophoresis analysis revealed that Ca(NO3)2-methanol, Ca(NO3)2-ethanol, or CaCl2-methanol treatments produced more lower molecular weights of silk fibroin than CaCl2-ethanol. X-ray diffraction and Fourier-transform infrared spectroscopy showed that CaCl2-ethanol produced a crystalline structure with more silk I (α-form, type II β-turn), while the other treatments produced more silk II (β-form, anti-parallel β-pleated sheet). Solid-State 13C cross polarization and magic angle spinning-nuclear magnetic resonance measurements suggested that regenerated fibroins from CaCl2-ethanol were nearly identical to degummed silk fibroin, while the other treatments produced fibroins with significantly different chemical shifts. Finally, enzyme activity test indicated that silk fibroins from CaCl2-ethanol had higher activity when linked to a known chemotherapeutic drug, L-asparaginase, than the fibroins from other treatments. Conclusions Collectively, these results suggest that the CaCl2-ethanol processing method produces silk fibroin with biomaterial properties that are appropriate for drug delivery. PMID:22676291

The evaluation of the statistical monomineral thermobarometric methods for the reconstruction of the lithospheric mantle structure

NASA Astrophysics Data System (ADS)

Ashchepkov, I.; Vishnyakova, E.

2009-04-01

The modified versions of the thermobarometers for the mantle assemblages were revised sing statistical calibrations on the results of Opx thermobarometry. The modifications suggest the calculation of the Fe# of coexisting olivine Fe#Ol according to the statistical approximations by the regressions obtained from the xenoliths from kimberlite data base including >700 associations. They allow reproduces the Opx based TP estimates and to receive the complete set of the TP values for mantle xenoliths and xenocrysts. For GARNET Three variants of barometer give similar results. The first is published (Ashchepkov, 2006). The second is calculating the Al2O3 from Garnet for Orthopyroxene according to procedure: xCrOpx=Cr2O3/CaO)/FeO/MgO/500 xAlOpx=1/(3875*(exp(Cr2O3^0.2/CaO)-0.3)*CaO/989+16)-XcrOpx Al2O3=xAlOp*24.64/Cr2O3^0.2*CaO/2.+FeO*(ToK-501)/1002 And then it suppose using of the Al2O3 in Opx barometer (McGregor, 1974). The third variant is transformation of the G. Grutter (2006) method by introducing of the influence of temperature. P=40+(Cr2O3)-4.5)*10/3-20/7*CaO+(ToC)*0.0000751*MgO)*CaO+2.45*Cr2O3*(7-xv(5,8)) -Fe*0.5 with the correction for P>55: P=55+(P-55)*55/(1+0.9*P) Average from this three methods give appropriate values comparable with determined with (McGregor,1974) barometer. Temperature are estimating according to transformed Krogh thermometer Fe#Ol_Gar=Fe#Gar/2+(T(K)-1420)*0.000112+0.01 For the deep seated associations P>55 kbar T=T-(0.25/(0.4-0.004*(20-P))-0.38/Ca)*275+51*Ca*Cr2-378*CaO-0.51)-Cr/Ca2*5+Mg/(Fe+0.0001)*17.4 ILMENITE P= ((TiO2-23.)*2.15-(T0-973)/20*MgO*Cr2O3 and next P=(60-P)/6.1+P ToK is determined according to (Taylor et al , 1998) Fe#Ol_Chr =(Fe/(Fe+Mg)ilm -0.35)/2.252-0.0000351*(T(K)-973) CHROMITE The equations for PT estimates with chromite compositions P=Cr/(Cr+Al)*T(K)/14.+Ti*0.10 with the next iteration P=-0.0053*P^2+1.1292*P+5.8059 +0.00135*T(K)*Ti*410-8.2 For P> 57 P=P+(P-57)*2.75 Temperature estimates are according to the O'Neill- Wall, 1987 The Fe#Ol values are estimated according to three iterations Fe#Ol_Chr=(Fe/Fe+Mg)/4.5-(P-32)*0.00115-0.03 Fe#Ol_Chr =( Fe#Ol -0.074)*0.45+0.086 Fe#Ol _Chr= Fe#Ol -( Fe#Ol -0.06)*(T(K)-1300)*0.000115+0.01 CLINOPYROXENE (Ash2009)=0.32 (1-0.2*Na/Al+0.012*Fe/Na)*Kd ^(3/4)*ToK/(1+Fe)-35*ln(1273/ToK)*(Al+Ti+2.5Na+1.5Fe3+)+(0.9-CaO)*10+Na20/Al2O3* ToK /200 with the second iteration P=(0.0000002* P4 +0.000002+P^3-0.0027*P^2+1.2241*P) The TP estimates were statistically tested wit the available experimental results in peridotite (315 runs) and eclogite (302 runs) system and show good agreement with the TP conditions of runs. The methods are joined together with the other 40 thermometers and 30 barometers for mantle associations in the FORTRAN program allowing simultaneous calculations of 10 pairs of T and P and write the matrix of calculated TPFO2 values together with the compositions of minerals or their formula coefficients. Grant RBRF 05-05-64718.

Experimental study of Fe-Mg- and Ca-distribution between coexisting ortho- and clinopyroxenes at P=294 MPa, T=750 and 800° C

NASA Astrophysics Data System (ADS)

Fonarev, V. I.; Graphchikov, A. A.

1982-07-01

The Fe-Mg-Ca-distribution was investigated in synthesis experiments and with the mineral assemblage orthopyroxene+clinopyroxene+quartz. The phase compositions were identified by X-ray diffraction and, where possible, by electron microprobe. The attainment of equilibrium in the run products was signalled by the compositions from control runs (different solutions) becoming closely similar, by recycling runs, by the attainment of equilibrium from different directions (depending on the composition of starting phases), and by special kinetic experiments. The study produced the following results: (1) the Ca content of the clinopyroxenes decreases with increasing Fe (mol%) from 48.4 at X {Cpx/Fe}=5 to 39.8 at X {Cpx/Fe}=45 (800° C); from 47.6 at X {Cpx/Fe}= 10 to 41.7 at X {Cpx/Fe}=45 (750° C); increasing temperature expands the stability field of the less calcic clinopyroxenes. (2) The Ca content of orthopyroxenes increases slightly with Fe content from 1.8 at X {Opx/Fe}=20.5 to 3.2 at X {Opx/Fe}=75; the temperature effect on the Ca content under the T, P conditions of the experiment was not large. (3) Fe and Mg distribution between the coexisting ortho-and clinopyroxenes is largely temperature-dependent, particularly in the compositional range X {Opx/Fe}=15 75 mol%; as T increases, Fe redistributes from the rhombic to monoclinic mineral. Preliminary estimates of rock formation temperatures using the obtained data show that most of the known two-pyroxene geothermometers overstate the actual values by 50 150° C.

Magnetic Fe3O4@V2O5/rGO nanocomposite as a recyclable photocatalyst for dye molecules degradation under direct sunlight irradiation.

PubMed

Boruah, Purna K; Szunerits, Sabine; Boukherroub, Rabah; Das, Manash R

2018-01-01

Reduced graphene oxide nanosheets decorated with Fe 3 O 4 and V 2 O 5 nanoparticles as a magnetically recoverable nanocomposite (Fe 3 O 4 @V 2 O 5 /rGO) was synthesized by a simple solution chemistry approach. The synthesized nanocomposite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometer (VSM), Fourier transform infrared (FTIR), fluorescence, and zeta potential measurements. The narrow band gap and different band gap energies of Fe 3 O 4 and V 2 O 5 proved to be suitable for the absorption of visible light in the solar spectrum. The Fe 3 O 4 @V 2 O 5 /rGO displayed indeed excellent photocatalytic activity towards the degradation of harmful cationic Bismarck Brown (BB) as well as anionic Acid Orange 7 (AO) dyes under direct sunlight irradiation. The photocatalytic activity of the Fe 3 O 4 @V 2 O 5 /rGO is influenced by solution pH, catalyst loading, initial dye concentration and the presence of different inorganic ions (NH 4 + , Na + , Mg 2+ , Ca 2+, SO 4 2- , Br - , NO 3 - , Cl - , HCO 3 - ). This study provides a new scientific knowledge on the sunlight driven photocatalytic degradation of dye molecules using novel mixed metal oxide/rGO nanocomposite photocatalyst. Copyright © 2017 Elsevier Ltd. All rights reserved.

A Nanoindentation Study of the Plastic Deformation and Fracture Mechanisms in Single-Crystalline CaFe2As2

NASA Astrophysics Data System (ADS)

Frawley, Keara G.; Bakst, Ian; Sypek, John T.; Vijayan, Sriram; Weinberger, Christopher R.; Canfield, Paul C.; Aindow, Mark; Lee, Seok-Woo

2018-04-01

The plastic deformation and fracture mechanisms in single-crystalline CaFe2As2 has been studied using nanoindentation and density functional theory simulations. CaFe2As2 single crystals were grown in a Sn-flux, resulting in homogeneous and nearly defect-free crystals. Nanoindentation along the [001] direction produces strain bursts, radial cracking, and lateral cracking. Ideal cleavage simulations along the [001] and [100] directions using density functional theory calculations revealed that cleavage along the [001] direction requires a much lower stress than cleavage along the [100] direction. This strong anisotropy of cleavage strength implies that CaFe2As2 has an atomic-scale layered structure, which typically exhibits lateral cracking during nanoindentation. This special layered structure results from weak atomic bonding between the (001) Ca and Fe2As2 layers.

Hydrogen and electricity production in a light-assisted microbial photoelectrochemical cell with CaFe2O4 photocathode

NASA Astrophysics Data System (ADS)

Chen, Qing-Yun; Zhang, Kai; Liu, Jian-Shan; Wang, Yun-Hai

2017-04-01

A microbial photoelectrochemical cell (MPEC) was designed with a p-type CaFe2O4 semiconductor as the photoelectrode for simultaneous hydrogen and electricity production under light illumination. The CaFe2O4 photoelectrode was synthesized by the sol-gel method and well characterized by x-ray diffraction, field emission scanning electron microscope, and UV-Vis-NIR spectrophotometer. The linear sweep voltammogram of the CaFe2O4 photoelectrode presented the cathodic photocurrent output. For the MPEC, with an external resistance of 2000 Ω, the maximum power density of 143 mW was obtained. Furthermore, with an external resistance of 100 Ω, the maximum hydrogen production rate of 6.7 μL·cm-2 could be achieved. The MPEC with CaFe2O4 photocathode was compared to MPEC with other photocathodes as well as photocatalytic water splitting technology.

A Nanoindentation Study of the Plastic Deformation and Fracture Mechanisms in Single-Crystalline CaFe 2As 2

DOE PAGES

Frawley, Keara G.; Bakst, Ian; Sypek, John T.; ...

2018-04-10

In this paper, the plastic deformation and fracture mechanisms in single-crystalline CaFe 2As 2 has been studied using nanoindentation and density functional theory simulations. CaFe 2As 2 single crystals were grown in a Sn-flux, resulting in homogeneous and nearly defect-free crystals. Nanoindentation along the [001] direction produces strain bursts, radial cracking, and lateral cracking. Ideal cleavage simulations along the [001] and [100] directions using density functional theory calculations revealed that cleavage along the [001] direction requires a much lower stress than cleavage along the [100] direction. This strong anisotropy of cleavage strength implies that CaFe 2As 2 has an atomic-scalemore » layered structure, which typically exhibits lateral cracking during nanoindentation. This special layered structure results from weak atomic bonding between the (001) Ca and Fe 2As 2 layers.« less

A Nanoindentation Study of the Plastic Deformation and Fracture Mechanisms in Single-Crystalline CaFe 2As 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frawley, Keara G.; Bakst, Ian; Sypek, John T.

In this paper, the plastic deformation and fracture mechanisms in single-crystalline CaFe 2As 2 has been studied using nanoindentation and density functional theory simulations. CaFe 2As 2 single crystals were grown in a Sn-flux, resulting in homogeneous and nearly defect-free crystals. Nanoindentation along the [001] direction produces strain bursts, radial cracking, and lateral cracking. Ideal cleavage simulations along the [001] and [100] directions using density functional theory calculations revealed that cleavage along the [001] direction requires a much lower stress than cleavage along the [100] direction. This strong anisotropy of cleavage strength implies that CaFe 2As 2 has an atomic-scalemore » layered structure, which typically exhibits lateral cracking during nanoindentation. This special layered structure results from weak atomic bonding between the (001) Ca and Fe 2As 2 layers.« less

Calcium cation enhanced cathode/electrolyte interface property of Li2FeSiO4/C cathode for lithium-ion batteries with long-cycling life

NASA Astrophysics Data System (ADS)

Qu, Long; Li, Mingtao; Tian, Xiaolu; Liu, Pei; Yi, Yikun; Yang, Bolun

2018-03-01

Currently, the cycle performance at low rate is one of the most critical factor for realizing practical applications of Li2FeSiO4/C as a cathode of the lithium-ion batteries. To meet this challenge, calcium (Ca)-doped Li2FeSiO4/C is prepared by using the sol-gel method with soluble Li, Fe, Si and Ca sources. X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy and X-ray photoelectron spectroscopy measurements are carried out to determine the crystal structures, morphologies, particle sizes and chemical valence states of the resulting products. Rietveld refinement confirms that Ca-doped Li2FeSiO4 has a monoclinic P21/n structure and that a Ca cation occupies the Fe site in the Li2FeSiO4 lattice. The grain size of Ca-doped Li2FeSiO4 is approximately 20 nm and the nanoparticles are interconnected tightly with amorphous carbon layer. As a cathode material for the lithium-ion batteries, Li2Fe0.97Ca0.03SiO4/C delivers a high discharge capacity of 186 mAh g-1 at a 0.5 C rate. Its capacity retention after the 100th cycle reaches 87%, which increases by 25 percentage points compared with Li2FeSiO4/C. The Li2Fe0.97Ca0.03SiO4/C cathode exhibits good rate performance, with corresponding discharge capacities of 170, 157, 144 and 117 mAh g-1 at 1 C, 2 C, 5 C and 10 C rates, respectively. In summary, the improvement of the electrochemical performance can be attributed to a coefficient of the strengthened crystal structure stability during Li+ deintercalation-intercalation and restrained side reactions between electrode and electrolyte.

Efficacy of magnesium chloride in the treatment of Hailey-Hailey disease: from serendipity to evidence of its effect on intracellular Ca(2+) homeostasis.

PubMed

Borghi, Alessandro; Rimessi, Alessandro; Minghetti, Sara; Corazza, Monica; Pinton, Paolo; Virgili, Annarosa

2015-01-01

Hailey-Hailey disease (HHD), also known as familial benign chronic pemphigus, is a rare autosomal dominant inherited intraepidermal blistering genodermatosis. Mutations in the ATP2C1 gene encoding for the Golgi secretory pathway Ca(2+) /Mn(2+) -ATPasi protein 1 (SPCA1) affect the processing of desmosomal components and the epidermal suprabasal cell-cell adhesion by deregulating the keratinocyte cytosolic Ca(2+) concentration. We report the unexpected, dramatic, and persistent clinical improvement of the skin lesions of a patient affected with longstanding HHD with daily intake of a solution containing magnesium chloride hexahydrate (MgCl2 ). We investigated the effect of MgCl2 on the intracellular Ca(2+) homeostasis and on the activity of particular Ca(2+) -effectors in HeLa cells transfected with chimeric aequorins (cytAEQ, mtAEQ, erAEQ and GoAEQ) targeted to different subcellular compartments (cytosol, mitochondria, endoplasmic reticulum, and Golgi, respectively). Experimental investigations on HeLa cells showed the effect of MgCl2 on the function of Ca(2+) -extrusor systems, resulting in increased cytosolic and mitochondrial Ca(2+) levels, without altering the mechanisms of intraluminal Ca(2+) -filling and Ca(2+) -release of stores. Based on our clinical observation and experimental results, it can be hypothesized that MgCl2 could act as an inhibitor of the Ca(2+) -extruding activity in keratinocytes favoring intracellular Ca(2+) -disponibility and Ca(2+) -dependent mechanisms in desmosome assembly. This may represent the molecular basis of the good response of the HHD clinical features with MgCl2 solution in the patient described. © 2014 The International Society of Dermatology.

Trichloroethylene decomposition and in-situ dry sorption of Cl-products by calcium oxides prepared from hydrated limes.

PubMed

Gotoh, Yoshimi; Iwata, Goichi; Choh, Kyaw; Kubota, Mitsuhiro; Matsuda, Hitoki

2011-10-01

A comparison of CaOs produced by calcining two types of hydrated lime and calcium carbonate was made for decomposition of trichloroethylene and in-situ dry sorption of the decomposed Cl-products using a lab-scale gas flow type tubular packed bed reactor. About 20 mg of CaO sample was mixed with about 2 g of Al2O3 particles and packed in the reactor and allowed to react with a flowing standard gas containing 500 ppm of C2HCl3 (N2 balance) at 673 and 873 K, under the condition that the reaction of CaO with C2HCl3 might be completed within a few hours. It was found that no thermal decomposition of C2HCl3 at or below 673 K was observed in a reactor packed only with Al2O3 particles. However, a considerable amount of decomposition of C2HCl3 was obtained in a reactor packed with CaO and Al2O3, even at 673 K. For 1 mol of CaO prepared by calcining highly reactive Ca(OH)2 at 673 K, decomposition of 0.42 mol of C2HCl3 and in-situ absorption product of 0.53 mol of CaCl2 were obtained. At 873 K, about 46% of C2HCl3 was thermally decomposed. The total amount of C2HCl3 decomposed in CaO-Al2O3 particle bed at 873 K became nearly twice larger than that at 673 K. For 1 mol of CaO prepared by calcining highly reactive Ca(OH)2 at 873 K, decomposition of 0.59 mol of C2HCl3 and in-situ absorption product of 0.67 mol of CaCl2 were obtained. Small amounts of C2Cl2, C2Cl4, CCl4, etc. were detected during decomposition of C2HCl3 at 673 and 873 K. It was recognized that the data on decomposition of C2HCl3 as well as in-situ dry sorption of Cl-products in CaO particle bed were correlated with specific surface area of the CaO employed. Copyright © 2011 Elsevier Ltd. All rights reserved.

Physical properties and biological effects of mineral trioxide aggregate mixed with methylcellulose and calcium chloride.

PubMed

Lee, Bin-Na; Chun, Soo-Ji; Chang, Hoon-Sang; Hwang, Yun-Chan; Hwang, In-Nam; Oh, Won-Mann

2017-01-01

Methylcellulose (MC) is a chemical compound derived from cellulose. MTA mixed with MC reduces setting time and increases plasticity. This study assessed the influence of MC as an anti-washout ingredient and CaCl2 as a setting time accelerator on the physical and biological properties of MTA. Test materials were divided into 3 groups; Group 1(control): distilled water; Group 2: 1% MC/CaCl2; Group 3: 2% MC/CaCl2. Compressive strength, pH, flowability and cell viability were tested. The gene expression of bone sialoprotein (BSP) was detected by RT-PCR and real- time PCR. The expression of alkaline phosphatase (ALP) and mineralization behavior were evaluated using an ALP staining and an alizarin red staining. Compressive strength, pH, and cell viability of MTA mixed with MC/CaCl2 were not significantly different compared to the control group. The flowability of MTA with MC/CaCI2 has decreased significantly when compared to the control (p<.05). The mRNA level of BSP has increased significantly in MTA with MC/CaCl2 compared to the control (p<.05). This study revealed higher expression of ALP and mineralization in cells exposed to MTA mixed with water and MTA mixed with MC/CaCl2 compared to the control (p<.05). MC decreased the flowability of MTA and did not interrupt the physical and biological effect of MTA. It suggests that these cements may be useful as a root-end filling material.

Optimization of the crystal growth of the superconductor CaKFe 4 As 4 from solution in the FeAs - CaFe 2 As 2 - KFe 2 As 2 system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meier, W. R.; Kong, T.; Bud'ko, S. L.

Measurements of the anisotropic properties of single crystals play a crucial role in probing the physics of new materials. Determining a growth protocol that yields suitable high-quality single crystals can be particularly challenging for multicomponent compounds. Here we present a case study of how we refined a procedure to grow single crystals of CaKFe 4As 4 from a high temperature, quaternary liquid solution rich in iron and arsenic (“FeAs self-flux”). Temperature dependent resistance and magnetization measurements are emphasized, in addition to the x-ray diffraction, to detect intergrown CaKFe 4As 4, CaFe 2As 2, and KFe 2As 2 within what appearmore » to be single crystals. Guided by the rules of phase equilibria and these data, we adjusted growth parameters to suppress formation of the impurity phases. The resulting optimized procedure yielded phase-pure single crystals of CaKFe 4As 4. In conclusion, this optimization process offers insight into the growth of quaternary compounds and a glimpse of the four-component phase diagram in the pseudoternary FeAs–CaFe 2As 2–KFe 2As 2 system.« less

Optimization of the crystal growth of the superconductor CaKFe 4 As 4 from solution in the FeAs - CaFe 2 As 2 - KFe 2 As 2 system

DOE PAGES

Meier, W. R.; Kong, T.; Bud'ko, S. L.; ...

2017-06-19

Measurements of the anisotropic properties of single crystals play a crucial role in probing the physics of new materials. Determining a growth protocol that yields suitable high-quality single crystals can be particularly challenging for multicomponent compounds. Here we present a case study of how we refined a procedure to grow single crystals of CaKFe 4As 4 from a high temperature, quaternary liquid solution rich in iron and arsenic (“FeAs self-flux”). Temperature dependent resistance and magnetization measurements are emphasized, in addition to the x-ray diffraction, to detect intergrown CaKFe 4As 4, CaFe 2As 2, and KFe 2As 2 within what appearmore » to be single crystals. Guided by the rules of phase equilibria and these data, we adjusted growth parameters to suppress formation of the impurity phases. The resulting optimized procedure yielded phase-pure single crystals of CaKFe 4As 4. In conclusion, this optimization process offers insight into the growth of quaternary compounds and a glimpse of the four-component phase diagram in the pseudoternary FeAs–CaFe 2As 2–KFe 2As 2 system.« less

Numerical analysis of moving contact line with contact angle hysteresis using feedback deceleration technique

NASA Astrophysics Data System (ADS)

Park, Jun Kwon; Kang, Kwan Hyoung

2012-04-01

Contact angle (CA) hysteresis is important in many natural and engineering wetting processes, but predicting it numerically is difficult. We developed an algorithm that considers CA hysteresis when analyzing the motion of the contact line (CL). This algorithm employs feedback control of CA which decelerates CL speed to make the CL stationary in the hysteretic range of CA, and one control coefficient should be heuristically determined depending on characteristic time of the simulated system. The algorithm requires embedding only a simple additional routine with little modification of a code which considers the dynamic CA. The method is non-iterative and explicit, and also has less computational load than other algorithms. For a drop hanging on a wire, the proposed algorithm accurately predicts the theoretical equilibrium CA. For the drop impacting on a dry surface, the results of the proposed algorithm agree well with experimental results including the intermittent occurrence of the pinning of CL. The proposed algorithm is as accurate as other algorithms, but faster.

Melt densities in the CaO-FeO-Fe 2O 3-SiO 2 system and the compositional dependence of the partial molar volume of ferric iron in silicate melts

NASA Astrophysics Data System (ADS)

Dingwell, Donald B.; Brearley, Mark

1988-12-01

The densities of 10 melts in the CaO-FeO-Fe 2O 3-SiO 2 system were determined in equilibrium with air, in the temperature range of 1200 to 1550°C, using the double-bob Archimedean technique. Melt compositions range from 6 to 58 wt% SiO 2, 14 to 76 wt% Fe 2O 3 and 10 to 46 wt% CaO. The ferric-ferrous ratios of glasses drop-quenched from loop fusion equilibration experiments were determined by 57Fe Mössbauer spectroscopy. Melt densities range from 2.689 to 3.618 gm/cm 3 with a mean standard deviation from replicate experiments of 0.15%. Least-squares regressions of molar volume versus molar composition have been performed and the root mean squared deviation shows that a linear combination of partial molar volumes for the oxide components (CaO, FeO, Fe 2O 3 and SiO 2) cannot describe the data set within experimental error. Instead, the inclusion of excess terms in CaFe 3+ and CaSi (product terms using the oxides) is required to yield a fit that describes the experimental data within error. The nonlinear compositional-dependence of the molar volumes of melts in this system can be explained by structural considerations of the roles of Ca and Fe 3+. The volume behavior of melts in this system is significantly different from that in the Na 2O-FeO-Fe 2O 3-SiO 2 system, consistent with the proposal that a proportion of Fe 3+ in melts in the CaO-FeO-Fe 2O 3-SiO 2 system is not tetrahedrally-coordinated by oxygen, which is supported by differences in 57Fe Mössbauer spectra of glasses. Specifically, this study confirms that the 57Fe Mössbauer spectra exhibit an area asymmetry and higher values of isomer shift of the ferric doublet that vary systematically with composition and temperature (this study; Dingwell and Virgo, 1987, 1988). These observations are consistent with a number of other lines of evidence ( e.g., homogeneous redox equilibria, Dickenson and Hess, 1986; viscosity, Dingwell and Virgo, 1987,1988). Two species of ferric iron, varying in proportions with temperature, composition and redox state, are sufficient to describe the above observations. The presence of more than one coordination geometry for Fe 3+ in low pressure silicate melts has several implications for igneous petrogenesis. The possible effects on compressibility, the pressure dependence of the redox ratio, and redox enthalpy are briefly noted.

Optimization of Performance of Arc Welding Using Fluxes in Welded Ship Structures from HY-100 and HY-130 KPSI.

DTIC Science & Technology

1981-09-01

production and formulation for several decades. NMgO + NCaO + NMnO + NFeO + NAI 20 3Basicity = NSiO 2 + NTi0 2 + NZr0 2 + NA1 203 This differs from the widely...20 3 100 (CaO-SiO, )(40) slag CaO/SiO 2 0.15 none 2600 NCaO /NSiO2 0.17 8% FeSi 1900 16% FeSi 1700 32% FeSi 1400 52 I Table 8 (continued). Islag Ca0...SiO~e .79 none 1200 NCaO /NSiOz .84 2% FeSi 1000 4% FeSi 900 16% FeSi 500 32% FeSi 500 Mechanical Property Tests Mechanical property weldments were

Spatial and temporal characterization of trace elements and nutrients in the Rawal Lake Reservoir, Pakistan using multivariate analysis techniques.

PubMed

Malik, Riffat Naseem; Nadeem, Muhammad

2011-12-01

Rawal Lake Reservoir is renowned for its ecological significance and is the sole source of drinking water of the third largest city of Pakistan. However, fish kill in recent years and anthropogenic impacts from human-related activities in its catchment area have resulted in deterioration of its surface water quality. This study aims to characterize spatial and temporal variations in surface water quality, identify contaminant sources, and compare their levels with quality guidelines. Surface water samples were collected from 10 sites and analyzed for 27 physicochemical parameters for a period of 2 years on a seasonal basis. Concentration of metals in surface water in pre-monsoon were in the order: Fe > Mg > Ca > Mn > Zn > Ni > Cr > Cu > Co > Pb, whereas in post-monsoon, the order of elemental concentrations was: Ca > Mg > Na > Fe > K > Zn > Cr > Li > Pb > Co > Ni > Cu > Mn > Cd. Metals (Ni, Fe, Zn, and Ca), pH, electrical conductivity (EC), dissolved oxygen (DO), chemical oxygen demand (COD), and nutrients (PO (4) (3-) , NO(3)-N, and SO (4) (2-) ) were measured higher in pre-monsoon, whereas concentration of Cu, Mn, Cr, Co, Pb, Cd, K, Na, Mg, Li, Cl(-), and NH(4)-N were recorded higher in post-monsoon. Results highlighted serious metal pollution of surface water. Mean concentration of Zn, Cd, Ni, Cu, Fe, Cr, and Pb in both seasons and Mn in post-monsoon were well above the permissible level of surface water quality criteria. Results stress the dire need to reduce heavy-metal input into the lake basin and suggest that heavy-metal contamination should be considered as an integral part of future planning and management strategies for restoration of water quality of the lake reservoir.

Heterobimetallic Complexes with MIII-(μ-OH)-MII Cores (MIII = Fe, Mn, Ga; MII = Ca, Sr, and Ba): Structural, Kinetic, and Redox Properties

PubMed Central

Park, Young Jun; Cook, Sarah A.; Sickerman, Nathaniel S.; Sano, Yohei; Ziller, Joseph W.

2013-01-01

The effects of redox-inactive metal ions on dioxygen activation were explored using a new FeII complex containing a tripodal ligand with 3 sulfonamido groups. This iron complex exhibited a faster initial rate for the reduction of O2 than its MnII analog. Increases in initial rates were also observed in the presence of group 2 metal ions for both the FeII and MnII complexes, which followed the trend NMe4+ < BaII < CaII = SrII. These studies led to the isolation of heterobimetallic complexes containing FeIII-(μ-OH)-MII cores (MII = Ca, Sr, and Ba) and one with a [SrII(OH)MnIII]+ motif. The analogous [CaII(OH)GaIII]+ complex was also prepared and its solid state molecular structure is nearly identical to that of the [CaII(OH)FeIII]+ system. Nuclear magnetic resonance studies indicated that the diamagnetic [CaII(OH)GaIII]+ complex retained its structure in solution. Electrochemical measurements on the heterobimetallic systems revealed similar one-electron reduction potentials for the [CaII(OH)FeIII]+ and [SrII(OH)FeIII]+ complexes, which were more positive than the potential observed for [BaII(OH)FeIII]+. Similar results were obtained for the heterobimetallic MnII complexes. These findings suggest that Lewis acidity is not the only factor to consider when evaluating the effects of group 2 ions on redox processes, including those within the oxygen-evolving complex of Photosystem II. PMID:24058726

Heterobimetallic Complexes with MIII-(μ-OH)-MII Cores (MIII = Fe, Mn, Ga; MII = Ca, Sr, and Ba): Structural, Kinetic, and Redox Properties.

PubMed

Park, Young Jun; Cook, Sarah A; Sickerman, Nathaniel S; Sano, Yohei; Ziller, Joseph W; Borovik, A S

2013-02-01

The effects of redox-inactive metal ions on dioxygen activation were explored using a new Fe II complex containing a tripodal ligand with 3 sulfonamido groups. This iron complex exhibited a faster initial rate for the reduction of O 2 than its Mn II analog. Increases in initial rates were also observed in the presence of group 2 metal ions for both the Fe II and Mn II complexes, which followed the trend NMe 4 + < Ba II < Ca II = Sr II . These studies led to the isolation of heterobimetallic complexes containing Fe III -( μ -OH)-M II cores (M II = Ca, Sr, and Ba) and one with a [Sr II (OH)Mn III ] + motif. The analogous [Ca II (OH)Ga III ] + complex was also prepared and its solid state molecular structure is nearly identical to that of the [Ca II (OH)Fe III ] + system. Nuclear magnetic resonance studies indicated that the diamagnetic [Ca II (OH)Ga III ] + complex retained its structure in solution. Electrochemical measurements on the heterobimetallic systems revealed similar one-electron reduction potentials for the [Ca II (OH)Fe III ] + and [Sr II (OH)Fe III ] + complexes, which were more positive than the potential observed for [Ba II (OH)Fe III ] + . Similar results were obtained for the heterobimetallic Mn II complexes. These findings suggest that Lewis acidity is not the only factor to consider when evaluating the effects of group 2 ions on redox processes, including those within the oxygen-evolving complex of Photosystem II.

Salt exclusion and mycorrhizal symbiosis increase tolerance to NaCl and CaCl2 salinity in ‘Siam Queen’ basil

USDA-ARS?s Scientific Manuscript database

A study was conducted to evaluate the effects of salinity on growth and nutrient uptake in basil (Ocimum basilicum L.). Plants were fertilized with a complete nutrient solution and exposed to no, low, or moderate levels of salinity from NaCl or CaCl2. Plants in the control and moderate salinity tre...

Phase diagram of pressure-induced superconductor β-(BDA-TTP)2MX4 (M=Fe, Ga and X=Cl, Br) with localized magnetic moments

NASA Astrophysics Data System (ADS)

Choi, E. S.; Graf, D.; Tokumoto, T.; Brooks, J. S.; Yamada, Jun-Ichi

2007-03-01

We have investigated transport and magnetization properties of β-(BDA-TTP)2MX4 (M=Fe, Ga and X=Cl, Br) as a function of pressure, temperature and magnetic field. The title material undergoes metal-insulator transitions above 100 K at ambient pressure. The insulating phase is suppressed with pressure and superconductivity eventually appears above Pc= 4.5 kbar (X=Cl) and 13 kbar (X=Br). The general temperature-pressure (TP) phase diagram is similar each other, while higher pressure is required for X=Br compounds to suppress the insulating state and induce the superconductivity. Pressure dependent DC magnetization studies on β-(BDA-TTP)2FeCl4 compound revealed that the AFM ordering persist well above Pc. In spite of similarity of phase diagram between M=Fe and M=Ga compounds, magnetoresistance results show distinct behaviors, which indicates the magnetic interaction with the conduction electrons are still effective. The comparison between X=Cl and X=Br compounds suggests the anion-size effect rather than the existence of localized magnetic moments plays more important role in determining the ground state.

Crystal structure of bis-(benzyl-amine-κN)[5,10,15,20-tetra-kis-(4-chloro-phen-yl)porphyrinato-κ(4) N]iron(II) n-hexane monosolvate.

PubMed

Dhifaoui, Selma; Harhouri, Wafa; Bujacz, Anna; Nasri, Habib

2016-01-01

In the title compound, [Fe(II)(C44H24Cl4N4)(C6H5CH2NH2)2]·C6H14 or [Fe(II)(TPP-Cl)(BzNH2)2]·n-hexane [where TPP-Cl and BzNH2 are 5,10,15,20-tetra-kis-(4-chloro-phen-yl)porphyrinate and benzyl-amine ligands, respectively], the Fe(II) cation lies on an inversion centre and is octa-hedrally coordinated by the four pyrrole N atoms of the porphyrin ligand in the equatorial plane and by two amine N atoms of the benzyl-amine ligand in the axial sites. The crystal structure also contains one inversion-symmetric n-hexane solvent mol-ecule per complex mol-ecule. The average Fe-Npyrrole bond length [1.994 (3) Å] indicates a low-spin complex. The crystal packing is sustained by N-H⋯Cl and C-H⋯Cl hydrogen-bonding inter-actions and by C-H⋯π inter-molecular inter-actions, leading to a three-dimensional network structure.

Bioethanol production from rice husk using different pretreatments and fermentation conditions.

PubMed

Madu, Joshua Osuigwe; Agboola, Bolade Oyeyinka

2018-01-01

Bioethanol is an environmentally friendly alternative to petroleum energy sources. This study evaluated the effects of H 2 O, HCl, NaOH and FeCl 3 pretreated rice husk feedstocks on the production of bioethanol. The pretreatments were carried out using water, 0.1 M HCl, NaOH and FeCl 3 at 121 °C for 15 min, followed by simultaneous saccharification and fermentation (SSF) as well as separate hydrolysis and fermentation (SHF). The raw and pretreated lignocellulosic feedstocks were analyzed using Fourier transform infrared spectroscopy. Saccharification and fermentation were accomplished using Trichoderma reesei cellulase and Saccharomyces cerevisiae , respectively. The products obtained after saccharification and fermentation were collected and analyzed for reducing sugars and ethanol contents using 3,5-dinitrosalicylic acid and high-performance liquid chromatography, respectively. Enzyme hydrolysis of the FeCl 3 and HCl treated samples resulted in hydrolysates containing 3.845 and 3.402 mg/ml glucose equivalent, respectively. In all pretreatments, SSF for each pretreatment produced more ethanol than the SHF method; the FeCl 3 pretreatment gave the highest ethanol yield of 3.011 ± 0.034 and 3.802 ± 0.041% in the SHF and SSF methods, respectively. Utilization of FeCl 3 pretreatment of rice husk is a potential option for bioethanol production in the future.

Apparently enhanced magnetization of Cu(I)-modified γ-Fe2O3 based nanoparticles

NASA Astrophysics Data System (ADS)

Qiu, Xiaoyan; He, Zhenghong; Mao, Hong; Zhang, Ting; Lin, Yueqiang; Liu, Xiaodong; Li, Decai; Meng, Xiangshen; Li, Jian

2017-11-01

Using a chemically induced transition method in FeCl2 solution, γ-Fe2O3 based magnetic nanoparticles, in which γ-Fe2O3 crystallites were coated with FeCl3ṡ6H2O, were prepared. During the synthesis of the γ-Fe2O3 nanoparticles Cu(I) modification of the particles was attempted. According to the results from both magnetization measurements and structural characterization, it was judged that a magnetic silent "dead layer", which can be attributed to spin disorder in the surface of the γ-Fe2O3 crystallites due to breaking of the crystal symmetry, existed in the unmodified particles. For the Cu(I)-modified sample, the CuCl thin layer on the γ-Fe2O3 crystallites incurred the crystal symmetry to reduce the spin disorder, which "awakened" the "dead layer" on the surface of the γ-Fe2O3 crystallites, enhancing the apparent magnetization of the Cu(I)-modified nanoparticles. It was determined that the surface spin disorder of the magnetic crystallite could be related to the coating layer on the crystallite, and can be modified by altering the coating layer to enhance the effective magnetization of the magnetic nanoparticles.

Photosynthesis is improved by exogenous calcium in heat-stressed tobacco plants.

PubMed

Tan, Wei; Meng, Qing wei; Brestic, Marian; Olsovska, Katarina; Yang, Xinghong

2011-11-15

Effects of exogenous calcium chloride (CaCl(2)) (20 mM) on photosynthetic gas exchange, photosystem II photochemistry, and the activities of antioxidant enzymes in tobacco plants under high temperature stress (43°C for 2 h) were investigated. Heat stress resulted in a decrease in net photosynthetic rate (P(n)), stomatal conductance as well as the apparent quantum yield (AQY) and carboxylation efficiency (CE) of photosynthesis. Heat stress also caused a decrease of the maximal photochemical efficiency of primary photochemistry (F(v)/F(m)). On the other hand, CaCl(2) application improved P(n), AQY, and CE as well as F(v)/F(m) under high temperature stress. Heat stress reduced the activities of superoxide dismutase (SOD), catalase (CAT), ascorbate peroxidase (APX), peroxidase (POD), whereas the activities of these enzymes either decreased less or increased in plants pretreated with CaCl(2); glutathione reductase (GR) activity increased under high temperature, and it increased more in plants pretreated with CaCl(2). There was an obvious accumulation of H(2)O(2) and O(2)(-) under high temperature, but CaCl(2) application decreased the contents of H(2)O(2) and O(2)(-) under heat stress conditions. Heat stress induced the level of heat shock protein 70 (HSP70), while CaCl(2) pretreatment enhanced it. These results suggested that photosynthesis was improved by CaCl(2) application in heat-stressed plants and such an improvement was associated with an improvement in stomatal conductance and the thermostability of oxygen-evolving complex (OEC), which might be due to less accumulation of reactive oxygen species. Copyright © 2011 Elsevier GmbH. All rights reserved.

Optimization of pH, temperature and CaCl2 concentrations for Ricotta cheese production from Buffalo cheese whey using Response Surface Methodology.

PubMed

Rashid, Abdul Ahid; Huma, Nuzhat; Zahoor, Tahir; Asgher, Muhammad

2017-02-01

The recovery of milk constituents from cheese whey is affected by various processing conditions followed during production of Ricotta cheese. The objective of the present investigation was to optimize the temperature (60-90 °C), pH (3-7) and CaCl2 concentration (2·0-6·0 mm) for maximum yield/recovery of milk constituents. The research work was carried out in two phases. In 1st phase, the influence of these processing conditions was evaluated through 20 experiments formulated by central composite design (CCD) keeping the yield as response factor. The results obtained from these experiments were used to optimize processing conditions for maximum yield using response surface methodology (RSM). The three best combinations of processing conditions (90 °C, pH 7, CaCl2 6 mm), (100 °C, pH 5, CaCl2 4 mm) and (75 °C, pH 8·4, CaCl2 4 mm) were exploited in the next phase for Ricotta cheese production from a mixture of Buffalo cheese whey and skim milk (9 : 1) to determine the influence of optimized conditions on the cheese composition. Ricotta cheeses were analyzed for various physicochemical (moisture, fat, protein, lactose, total solids, pH and acidity indicated) parameters during storage of 60 d at 4 ± 2 °C after every 15 d interval. Ricotta cheese prepared at 90 °C, pH 7 and CaCl2 6 mm exhibited the highest cheese yield, proteins and total solids, while high fat content was recorded for cheese processed at 100 °C, pH 5 and 4 mm CaCl2 concentration. A significant storage-related increase in acidity and NPN was recorded for all cheese samples.

Structure and reactivity of ferrihydrite-soil organic carbon-calcium ternary complexes

NASA Astrophysics Data System (ADS)

Yang, Y.; Adhikari, D.; Sowers, T.; Stuckey, J.; Poulson, S.; Sparks, D. L.

2017-12-01

Complete understanding about the interactions between soil organic carbon (SOC) and minerals is important for predicting the stability of SOC and its response to climate change. Recent studies have shown the importance of calcium (Ca)-bearing minerals and iron (Fe) oxide in associating with and stabilizing SOC. In this study, we have investigated the formation and reactivity of ferrihydrite-SOC-Ca ternary complexes. During the co-precipitation of ferrihydrite with SOC in the presence of Ca2+, 60% of SOC can be co-precipitated with ferrihydrite at a C/Fe (molar ratio) of up to 10, whereas the Ca/Fe ratio was saturated at 0.2. Increasing amount of Ca2+ did not affect the co-precipitation of SOC with ferrihydrite or the lability of ferrihydrite-bound SOC. In addition, microbial reduction of ferrihydrite and reductive release of ferrihydrite-bound SOC were not influenced by the presence of Ca, but the pathway for Fe mineral transformation during the reduction was affected by Ca. In the meantime, Fe reduction selectively released carboxylic-enriched SOC. As a comparison, the presence of SOC increased the incorporation of Ca into the structure of ferrihydrite. Our results indicate the formation of ferrihydrite-SOC-Ca complexes, with organic carbon bridging the ferrihydrite and Ca. Such ternary complexes potentially play an important role in regulating the interactions between SOC and mineral phases in soil.