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Sample records for dimeric fe ii

  1. Solid State Collapse of a High-Spin Square-Planar Fe(II) Complex, Solution Phase Dynamics, and Electronic Structure Characterization of an Fe(II)2 Dimer.

    Science.gov (United States)

    Pascualini, Matias E; Stoian, Sebastian A; Ozarowski, Andrew; Abboud, Khalil A; Veige, Adam S

    2016-06-06

    Square-planar high-spin Fe(II) molecular compounds are rare, and until recently, the only four examples of non-macrocyclic or sterically driven molecular compounds of this kind shared a common FeO4 core. The trianionic pincer-type ligand [CF3-ONO]H3 (1) supports the high-spin square-planar Fe(II) complex {[CF3-ONO]FeCl}{Li(Sv)2}2 (2). In the solid state, 2 forms the dimer complex {[CF3-ONO]Fe}2{(μ-Cl)2(μ-LiTHF)4} (3) in 96% yield by simply applying a vacuum or stirring it with pentane for 2 h. A detailed high-frequency electron paramagnetic resonance and field-dependent (57)Fe Mössbauer investigation of 3 revealed a weak antiferromagnetic exchange interaction between the local iron spins which exhibit a zero-field splitting tensor characterized by negative D parameter. In solution, 2 is in equilibrium with the solvento complex {[CF3-ONO]FeCl(THF)}{Li2(Sv)4} (2·Sv) and the dimer 3. A combination of frozen solution (57)Fe Mössbauer spectroscopy and single crystal X-ray crystallography helped elucidate the solvent dependent equilibrium between these three species. The oxidation chemistry of 2·Sv was investigated. Complex 2 reacts readily with the one-electron oxidizing agent CuCl2 to give the Fe(III) complex {[CF3-ONO]FeCl2}{Li(THF)2}2 (4). Also, 2·Sv reacts with 2 equiv of TlPF6 to form the Fe(III) complex [CF3-ONO]Fe(THF)3 (5).

  2. Dimeric Fe (II, III) complex of quinoneoxime as functional model of PAP enzyme: Moessbauer, magneto-structural and DNA cleavage studies

    Energy Technology Data Exchange (ETDEWEB)

    Salunke-Gawali, Sunita; Ahmed, Khursheed [University of Pune, Department of Chemistry (India); Varret, Francois; Linares, Jorge [Universite de Versailles, Laboratoire de Magnetisme et d' Optique, CNRS, UMR 8634 (France); Zaware, Santosh [University of Pune, Department of Chemistry (India); Date, Sadgopal [University of Pune, Department of Physics (India); Rane, Sandhya, E-mail: syrane@chem.unipune.ernet.in [University of Pune, Department of Chemistry (India)

    2008-07-15

    Purple acid phosphatase, (PAP), is known to contain dinuclear Fe{sub 2}{sup +2,+3} site with characteristic Fe{sup +3} <- Tyr ligand to metal charge transfer in coordination. Phthiocoloxime (3-methyl-2-hydroxy-1,4-naphthoquinone-1-oxime) ligand L, mimics (His/Tyr) ligation with controlled and unique charge transfers resulting in valence tautomeric coordination with mixed valent diiron site in model compound Fe-1: [{mu}-OH-Fe{sub 2}{sup +2,+3} (o-NQ{sub CH3ox}) (o-NSQ{sub CH3ox}){sub 2} (CAT) H{sub 2}O]. Fe-2: [Fe{sup +3}(o-NQ{sub CH3ox}) (p-NQ{sub CH3ox}){sub 2}]{sub 2} a molecularly associated dimer of phthiocoloxime synthesized for comparison of charge transfer. {sup 57}Fe Moessbauer studies was used to quantitize unusual valences due to ligand in dimeric Fe-1 and Fe-2 complexes which are supported by EPR and SQUID studies. {sup 57}Fe Moessbauer spectra for Fe-1 at 300 K indicates the presence of two quadrupole split asymmetric doublets due to the differences in local coordination geometries of [Fe{sup +3}]{sub A} and [Fe{sup +2}]{sub B} sites. The hyperfine interaction parameters are {delta}{sub A} = 0.152, ({Delta}E{sub Q}){sub A} 0.598 mm/s with overlapping doublet at {delta}{sub B} = 0.410 and ({Delta}E{sub Q}){sub B} 0.468 mm/s. Due to molecular association tendency of ligand, dimer Fe-2 possesses 100% Fe{sup +3}(h.s.) hexacoordinated configuration with isomer shift {delta} = 0.408 mm/s. Slightly distorted octahedral symmetry created by NQ{sub CH3ox} ligand surrounding Fe{sup +3}(h.s.) state generates small field gradient indicated by quadrupole split {Delta}E{sub Q} = 0.213 mm/s. Decrease of isomer shifts together with variation of quadrupole splits with temperature in Fe-1 dimer compared to Fe-2 is result of charge transfers in [Fe{sub 2}{sup +2,+3} SQ] complexes. EPR spectrum of Fe-1 shows two strong signals at g{sub 1} = 4.17 and g{sub 2} = 2.01 indicative of S = 3/2 spin state with an intermediate spin of Fe{sup +3}(h.s.) configuration. SQUID data of

  3. Calix[4]arene supported clusters: a dimer of [Mn(III)Mn(II)] dimers

    DEFF Research Database (Denmark)

    Taylor, Stephanie M; McIntosh, Ruaraidh D; Beavers, Christine M;

    2011-01-01

    Phosphinate ligands allow for the transformation of a calix[4]arene supported [Mn(III)(2)Mn(II)(2)] tetramer cluster motif into an unusual [Mn(III)Mn(II)](2) dimer of dimers; the clusters self-assemble in the crystal to form bi-layer arrays reminiscent of the typical packing of calixarene solvates....

  4. A [4Fe-4S] cluster dimer bridged by bis(2,2 ' : 6 ',2 ''-terpyridine-4 '-thiolato)iron(II)

    NARCIS (Netherlands)

    van der Geer, Erwin P. L.; van Koten, Gerard; Gebbink, Robertus J. M. Klein; Hessen, Bart

    2008-01-01

    The use of 2,2':6',2"-terpyridine-4'-thiol (tpySH) was explored as a bridging ligand for the formation of stable. assemblies containing both [4Fe-4S] clusters and single metal ions. Reaction of tpySH (2 equiv) with (NH4)(2)Fe(SO4)(2)center dot 6H(2)O generated the homoleptic complex

  5. Magnetic properties of transition metal Mn, Fe and Co dimers on monolayer phosphorene

    Science.gov (United States)

    Khan, Imran; Hong, Jisang

    2016-09-01

    We studied the geometries, electronic structure and magnetic properties of substitutional doping and adsorption of transition metal (Mn, Fe and Co) dimers on phosphorene monolayer in the framework of the generalized gradient approximation (GGA) and GGA + U. Electronic band structures and magnetic properties were dependent on the doping type and dopant materials. For Mn and Fe substitutional and adsorption dimers, we obtained semiconducting band structures with spin polarization. However, we found a half-metallic feature in Co substitutional dimer while the Co adsorption dimer showed a semiconducting behavior without any spin polarization. With GGA + U, all the systems showed spin polarized semiconducting band structures except Co adsorption dimer which remained unaffected. The hybridization between transition metal (TM) and phosphorene sheet contributed to suppressing the magnetic moment of TM dimers. For instance, the total magnetic moments of -2.0, 4.24 and 1.28 μ B/cell for Mn, Fe and Co substitutional dimers were obtained while the Mn and Fe adsorption dimers showed magnetic moments of -1.69 and 0.46 μ B/cell. These magnetic moments were enhanced with GGA + U. The same magnetic ground states were obtained both from GGA and GGA + U approaches except for the Mn dimers. We observed that the Mn and Fe substitutional dimers showed an out-of-plane magnetization while an in-plane magnetization was observed in Co substitutional dimer. The Mn adsorption dimer still displayed a perpendicular magnetization whereas the Fe adsorption dimer had an in-plane magnetization. We found that the both GGA and GGA + U showed the same magnetization direction in all the systems.

  6. Disturbing the dimers: Electron and hole doping in the intermetallic insulator FeGa3

    Science.gov (United States)

    Botana, Antia S.; Quan, Yundi; Pickett, Warren E.

    2015-10-01

    Insulating FeGa3 poses peculiar puzzles beyond the occurrence of an electronic gap in an intermetallic compound. This Fe-based material has a very distinctive structural characteristic with the Fe atoms occurring in dimers. The insulating gap can be described comparably well in either the weakly correlated limit or the strongly correlated limit within density functional theory viewpoints, where the latter corresponds to singlet formation on the Fe2 dimers. Though most of the calculated occupied Wannier functions are an admixture of Fe 3 d and Ga 4 s or 4 p states, there is a single bonding-type Wannier function per spin centered on each Fe2 dimer. Density functional theory methods have been applied to follow the evolution of the magnetic properties and electronic spectrum with doping, where unusual behavior is observed experimentally. Both electron and hole doping are considered, by Ge and Zn on the Ga site, and by Co and Mn on the Fe site, the latter introducing direct disturbance of the Fe2 dimer. Results from weakly and strongly correlated pictures are compared. Regardless of the method, magnetism including itinerant phases appears readily with doping. The correlated picture suggests that in the low doping limit Mn (for Fe) produces an in-gap hole state, while Co (for Fe) introduces a localized electronic gap state.

  7. Fe II emission in AGN

    Directory of Open Access Journals (Sweden)

    M. Joly

    2008-01-01

    Full Text Available El espectro óptico de las galaxias Seyfert 1 muestra una gran variedad de líneas de emisión producidas por FeII. Damos tres ejemplos e investigamos la formación de estas líneas con el fin de determinar las condiciones físicas de las regiones en donde se emiten.

  8. Acoustic Type-II Weyl Nodes from Stacking Dimerized Chains

    Science.gov (United States)

    Yang, Zhaoju; Zhang, Baile

    2016-11-01

    Lorentz-violating type-II Weyl fermions, which were missed in Weyl's prediction of nowadays classified type-I Weyl fermions in quantum field theory, have recently been proposed in condensed matter systems. The semimetals hosting type-II Weyl fermions offer a rare platform for realizing many exotic physical phenomena that are different from type-I Weyl systems. Here we construct the acoustic version of a type-II Weyl Hamiltonian by stacking one-dimensional dimerized chains of acoustic resonators. This acoustic type-II Weyl system exhibits distinct features in a finite density of states and unique transport properties of Fermi-arc-like surface states. In a certain momentum space direction, the velocity of these surface states is determined by the tilting direction of the type-II Weyl nodes rather than the chirality dictated by the Chern number. Our study also provides an approach of constructing acoustic topological phases at different dimensions with the same building blocks.

  9. The spectrum of Fe II

    CERN Document Server

    Nave, Gillian

    2012-01-01

    The spectrum of singly-ionized iron (Fe II) has been recorded using high-resolution Fourier transform and grating spectroscopy over the wavelength range 900 {\\AA} to 5.5 {\\mu}m. The spectra were observed in high-current continuous and pulsed hollow cathode discharges using Fourier transform (FT) spectrometers at the Kitt Peak National Observatory, Tucson, AZ and Imperial College, London and with the 10.7 m Normal Incidence Spectrograph at the National Institute of Standards and Technology. Roughly 12 900 lines were classified using 1027 energy levels of Fe II that were optimized to measured wavenumbers. The wavenumber uncertainties of lines in the FT spectra range from 10-4 cm-1 for strong lines around 4 {\\mu}m to 0.05 cm-1 for weaker lines around 1500 {\\AA}. The wavelength uncertainty of lines in the grating spectra is 0.005 {\\AA}. The ionization energy of (130 655.4+-0.4) cm-1 was estimated from the 3d6(5D)5g and 3d6(5D)6h levels.

  10. THE SPECTRUM OF Fe II

    Energy Technology Data Exchange (ETDEWEB)

    Nave, Gillian [National Institute of Standards and Technology, Gaithersburg, MD 20899-8422 (United States); Johansson, Sveneric, E-mail: gillian.nave@nist.gov [Lund Observatory, University of Lund, Box 43, SE-22100 Lund (Sweden)

    2013-01-15

    The spectrum of singly ionized iron (Fe II) has been recorded using high-resolution Fourier transform (FT) and grating spectroscopy over the wavelength range 900 A to 5.5 {mu}m. The spectra were observed in high-current continuous and pulsed hollow cathode discharges using FT spectrometers at the Kitt Peak National Observatory, Tucson, AZ and Imperial College, London and with the 10.7 m Normal Incidence Spectrograph at the National Institute of Standards and Technology. Roughly 12,900 lines were classified using 1027 energy levels of Fe II that were optimized to measured wavenumbers. The wavenumber uncertainties of lines in the FT spectra range from 10{sup -4} cm{sup -1} for strong lines around 4 {mu}m to 0.05 cm{sup -1} for weaker lines around 1500 A. The wavelength uncertainty of lines in the grating spectra is 0.005 A. The ionization energy of (130,655.4 {+-} 0.4) cm{sup -1} was estimated from the 3d{sup 6}({sup 5}D)5g and 3d{sup 6}({sup 5}D)6h levels.

  11. Fe ii fluorescence in symbiotic stars

    Directory of Open Access Journals (Sweden)

    M. Eriksson

    2004-01-01

    Full Text Available Se ha investigado la uorescencia por PAR del ion Fe II en ocho estrellas simbi oticas con muy diversos valores de la temperatura de la componente caliente y del per odo orbital. Los datos empleados son espectros de archivo del IUE. Todas las l neas de bombeo estudiadas se encuentran en la regi on (1200-2000 A del IUE, excepto He II 1084.942 y O VI 1032.041. Las l neas de uorescencia del Fe II est an principalmente en la regi on Fe II, pero algunas caen en la regi on de las l neas de bombeo. Nuestro objetivo es entender las condiciones optimas para la formaci on de l neas de uorescencia por PAR del Fe II. Tres de los sistemas estudiados, RR Tel, AG Peg and V1016 Cyg, presentan 10-30 canales activos del Fe II. Dos condiciones relacionan a estos sistemas. La componente caliente es una enana blanca de temperatura extrema (80 103-150 103 K, y los tres sistemas son novas simbi oticas, que han tenido erupciones en los ultimos 150 a~nos. Los sistemas AG Dra, RW Hya and R Aqr tienen s olo 2-3 canales activos del Fe II. Los dos sistemas restantes, CI Cyg and T CrB, no mostraron l neas de uorescencia del Fe II. Estos sistemas tienen en com un que la intensidad de emisi on de los elementos altamente ionizados es menor que en la mayor a de los sistemas simbi oticos, y que la componente caliente puede ser una estrella de secuencia principal con acreci on, en vez de una enana blanca.

  12. Unusually large spin polarization and magnetoresistance in a FeMg8-FeMg8 superatomic dimer

    Science.gov (United States)

    Zhu, Lin; Qian, Meichun; Khanna, Shiv N.

    2013-08-01

    Electronic transport across a FeMg8 magnetic superatom and its dimer has been investigated using a density functional theory combined with Keldysh nonequilibrium Green's-function formalism. For a single cluster, our studies for the cluster supported in various orientations on a Au(100) surface show that the transport is sensitive to the contact geometry. Investigations covering the cases where the axes of Mg square antiprism are 45°, perpendicular, and parallel to the transport direction, show that the equilibrium conductance, transferred charge, and current polarizations can all change significantly with orientation. Our studies on the transport across a magnetic superatom dimer FeMg8-FeMg8 focus on the effect of electrode contact distance and the support. The calculated I-V curves show negative differential resistance behavior at larger electrode-cluster contact distances. Further, the equilibrium conductance in ferromagnetic state shows an unusually high spin polarization that is about 81.48% for specific contact distance, and a large magnetoresistance ratio exceeding 500% is also found. The results show that the superatom assemblies can provide unusual transport characteristics, and that the spin polarization and magnetoresistance can be controlled via the contact geometry.

  13. Dimers on surface graphs and spin structures. II

    DEFF Research Database (Denmark)

    Cimasoni, David; Reshetikhin, Nicolai

    2009-01-01

    In a previous paper [3], we showed how certain orientations of the edges of a graph Γ embedded in a closed oriented surface Σ can be understood as discrete spin structures on Σ. We then used this correspondence to give a geometric proof of the Pfaffian formula for the partition function of the di......In a previous paper [3], we showed how certain orientations of the edges of a graph Γ embedded in a closed oriented surface Σ can be understood as discrete spin structures on Σ. We then used this correspondence to give a geometric proof of the Pfaffian formula for the partition function...... of the dimer model on Γ. In the present article, we generalize these results to the case of compact oriented surfaces with boundary. We also show how the operations of cutting and gluing act on discrete spin structures and how they change the partition function. These operations allow to reformulate the dimer...

  14. FeII/MgII, [Fe/Mg] Ratios and High-z Quasars

    CERN Document Server

    Korista, K; Corbin, M R; Freudling, W; Korista, Kirk; Kodituwakku, Nalaka; Corbin, Michael; Freudling, Wolfram

    2003-01-01

    It has been suggested in the literature that the (Fe/alpha) abundance ratio may be used as a chronometer, due to a delay in this ratio reaching its solar value as predicted by galactic chemical evolution models. Using grids of photoionization models along a sequence of the (Fe/Mg) abundance ratio vs.\\ metallicity with time in a giant elliptical starburst scenario, we investigate the relationship between the (Fe/Mg) abundance ratio and the FeII/MgII emission line flux ratio under the assumption that these lines originate in photoionized clouds within the broad emission line regions of quasars.

  15. Oxidation of Fe(II)-EDTA by nitrite and by two nitrate-reducing Fe(II)-oxidizing Acidovorax strains.

    Science.gov (United States)

    Klueglein, N; Picardal, F; Zedda, M; Zwiener, C; Kappler, A

    2015-03-01

    The enzymatic oxidation of Fe(II) by nitrate-reducing bacteria was first suggested about two decades ago. It has since been found that most strains are mixotrophic and need an additional organic co-substrate for complete and prolonged Fe(II) oxidation. Research during the last few years has tried to determine to what extent the observed Fe(II) oxidation is driven enzymatically, or abiotically by nitrite produced during heterotrophic denitrification. A recent study reported that nitrite was not able to oxidize Fe(II)-EDTA abiotically, but the addition of the mixotrophic nitrate-reducing Fe(II)-oxidizer, Acidovorax sp. strain 2AN, led to Fe(II) oxidation (Chakraborty & Picardal, 2013). This, along with other results of that study, was used to argue that Fe(II) oxidation in strain 2AN was enzymatically catalyzed. However, the absence of abiotic Fe(II)-EDTA oxidation by nitrite reported in that study contrasts with previously published data. We have repeated the abiotic and biotic experiments and observed rapid abiotic oxidation of Fe(II)-EDTA by nitrite, resulting in the formation of Fe(III)-EDTA and the green Fe(II)-EDTA-NO complex. Additionally, we found that cultivating the Acidovorax strains BoFeN1 and 2AN with 10 mM nitrate, 5 mm acetate, and approximately 10 mM Fe(II)-EDTA resulted only in incomplete Fe(II)-EDTA oxidation of 47-71%. Cultures of strain BoFeN1 turned green (due to the presence of Fe(II)-EDTA-NO) and the green color persisted over the course of the experiments, whereas strain 2AN was able to further oxidize the Fe(II)-EDTA-NO complex. Our work shows that the two used Acidovorax strains behave very differently in their ability to deal with toxic effects of Fe-EDTA species and the further reduction of the Fe(II)-EDTA-NO nitrosyl complex. Although the enzymatic oxidation of Fe(II) cannot be ruled out, this study underlines the importance of nitrite in nitrate-reducing Fe(II)- and Fe(II)-EDTA-oxidizing cultures and demonstrates that Fe(II)-EDTA cannot

  16. Dimeric (isoquinoline)(N-salicylidene-D,L-glutamato)copper(II) ethanol solvate.

    Science.gov (United States)

    Langer, Vratislav; Gyepesová, Dalma; Kohútová, Mária; Valent, Aladár

    2009-05-01

    The title racemic complex, bis[mu-N-(2-oxidobenzylidene)-D,L-glutamato(2-)]bis[(isoquinoline)copper(II)] ethanol disolvate, [Cu(2)(C(12)H(11)NO(5))(2)(C(9)H(7)N)(2)].2C(2)H(6)O, adopts a square-pyramidal Cu(II) coordination mode with a tridentate N-salicylideneglutamato Schiff base dianion and an isoquinoline ligand bound in the basal plane. The apex of the pyramid is occupied by a phenolic O atom from the adjacent chelate molecule at an apical distance of 2.487 (3) A, building a dimer located on the crystallographic inversion center. The Cu...Cu spacing within the dimers is 3.3264 (12) A. The ethanol solvent molecules are hydrogen bonded to the dimeric complex molecules, forming infinite chains in the a direction. The biological activity of the title complex has been studied.

  17. Structural, magnetic and optical properties of an Fe(III) dimer bridged by the meridional planar divergent N,N'-bis(salicyl)hydrazide and its photo- and electro-chemistry in solution.

    Science.gov (United States)

    Cheaib, Khaled; Martel, David; Clément, Nicolas; Eckes, Fabrice; Kouaho, Stéphanie; Rogez, Guillaume; Dagorne, Samuel; Kurmoo, Mohamedally; Choua, Sylvie; Welter, Richard

    2013-02-07

    {Fe(III)Cl(DMF)(2)}(2)(L) where L is N,N'-bis(salicyl)hydrazide has been synthesized as red crystals and characterized using single-crystal diffraction, infrared and UV-vis spectroscopies, and its magnetic properties studied. The dimeric unit in the structure is formed through the two meridional sets of divergent O, N, O coordinating atoms of the hexacoordinated and quadruply charged ligand. With the presence of the inversion symmetry the Fe atoms are strictly planar with the ligand. The magnetic exchange interaction is found to be antiferromagnetic with a J = -5.98(3) cm(-1) through the rare Fe-N-N-Fe pathway. Irradiation of the FeCl(3)/H(4)L red DMF solution in the visible region of the spectrum resulted in its complete discoloration and from which the unknown colorless salt [Fe(II)(DMF)(6)][Fe(II)Cl(4)] and the neutral ligand have been identified by single crystal diffraction. The UV-visible spectra of FeCl(3), H(4)L and their mixture in DMF solution indicate that the iron complex is the absorbing species and the presence of the free ligand in the irradiated solution suggests that the ligand is potentially acting as a catalyst to the photoreduction of Fe(III) to Fe(II), while electrochemistry points to a mixed-valent (Fe(II)-Fe(III)) intermediate in the process.

  18. Infrared [Fe II] Emission Lines from Radiative Atomic Shocks

    CERN Document Server

    Koo, Bon-Chul; Kim, Hyun-Jeong

    2016-01-01

    [Fe II] emission lines are prominent in the infrared (IR), and they are important diagnostic tools for radiative atomic shocks. We investigate the emission characteristics of [Fe II] lines using a shock code developed by Raymond (1979) with updated atomic parameters. We first review general characteristics of IR [Fe II] emission lines from shocked gas, and derive [Fe II] line fluxes as a function of shock speed and ambient density. We have compiled the available IR [Fe II] line observations of interstellar shocks and compare them to the ratios predicted from our model. The sample includes both young and old supernova remnants in the Galaxy and the Large Magellanic Cloud and several Herbig-Haro objects. We find that the observed ratios of IR [Fe II] lines generally fall on our grid of shock models, but the ratios of some mid-infrared lines, e.g., [Fe II] 35.35 um/[Fe II] 25.99 um, [Fe II] 5.340 um/[Fe II] 25.99 um, and [Fe II] 5.340 um/[Fe II] 17.94 um, are significantly offset from our model grid. We discuss ...

  19. Abiotic oxidation of Fe(II) by reactive nitrogen species in cultures of the nitrate-reducing Fe(II) oxidizer Acidovorax sp. BoFeN1 - questioning the existence of enzymatic Fe(II) oxidation.

    Science.gov (United States)

    Klueglein, N; Kappler, A

    2013-03-01

    Nitrate-reducing, Fe(II)-oxidizing bacteria were suggested to couple with enzymatic Fe(II) oxidation to nitrate reduction. Denitrification proceeds via intermediates (NO2 -, NO) that can oxidize Fe(II) abiotically at neutral and particularly at acidic pH. Here, we present a revised Fe(II) quantification protocol preventing artifacts during acidic Fe extraction and evaluate the contribution of abiotic vs. enzymatic Fe(II) oxidation in cultures of the nitrate-reducing, Fe(II) oxidizer Acidovorax sp. BoFeN1. Sulfamic acid used instead of HCl reacts with nitrite and prevents abiotic Fe(II) oxidation during Fe extraction. Abiotic experiments without sulfamic acid showed that acidification of oxic Fe(II) nitrite samples leads to 5.6-fold more Fe(II) oxidation than in anoxic samples because the formed NO becomes rapidly reoxidized by O(2) , therefore leading to abiotic oxidation and underestimation of Fe(II). With our revised protocol using sulfamic acid, we quantified oxidation of approximately 7 mm of Fe(II) by BoFeN1 within 4 days. Without addition of sulfamic acid, the same oxidation was detected within only 2 days. Additionally, abiotic incubation of Fe(II) with nitrite in the presence of goethite as surface catalyst led to similar abiotic Fe(II) oxidation rates as observed in growing BoFeN1 cultures. BoFeN1 growth was observed on acetate with N(2) O as electron acceptor. When adding Fe(II), no Fe(II) oxidation was observed, suggesting that the absence of reactive N intermediates (NO2 -, NO) precludes Fe(II) oxidation. The addition of ferrihydrite [Fe(OH)(3) ] to acetate/nitrate BoFeN1 cultures led to growth stimulation equivalent to previously described effects on growth by adding Fe(II). This suggests that elevated iron concentrations might provide a nutritional effect rather than energy-yielding Fe(II) oxidation. Our findings therefore suggest that although enzymatic Fe(II) oxidation by denitrifiers cannot be fully ruled out, its contribution to the observed Fe(II

  20. Fe(II)EDTA-NO reduction coupled with Fe(II)EDTA oxidation by a nitrate- and Fe(III)-reducing bacterium.

    Science.gov (United States)

    Dong, Xiyang; Zhang, Yu; Zhou, Jiti; Chen, Mingxiang; Wang, Xiaojun; Shi, Zhuang

    2013-06-01

    The nitrate- and Fe(III)-reducing bacterium Paracoccus versutus LYM was characterized in terms of its ability to perform Fe(II)EDTA-NO reduction coupled with Fe(II)EDTA oxidation (NO-dependent Fe(II)EDTA oxidation, NDFO). It experienced a single anaerobic FeEDTA redox cycling through NDFO and dissimilatory Fe(III)EDTA reduction in FeEDTA culture. The increase in the Fe(II)EDTA concentration contributed to the ascending Fe(II)EDTA-NO reduction rate. The amount of glucose controlled the rate and extent of Fe(II) oxidation during NDFO. Without glucose addition, Fe(II)EDTA-NO reduction rate was at a rather slow rate even in presence of relatively sufficient Fe(II)EDTA. Unlike aqueous Fe(2+) and solid-phase Fe(II), Fe(II)EDTA could prevent cells from encrustations. These findings suggested the occurrence of NDFO preferred being beneficial via a mixotrophic physiology in the presence of an organic cosubstrate to being out of consideration for metabolic strategy.

  1. Fractionation of Fe isotopes during Fe(II) oxidation by a marine photoferrotroph is controlled by the formation of organic Fe-complexes and colloidal Fe fractions

    Science.gov (United States)

    Swanner, Elizabeth D.; Wu, Wenfang; Schoenberg, Ronny; Byrne, James; Michel, F. Marc; Pan, Yongxin; Kappler, Andreas

    2015-09-01

    Much interest exists in finding mineralogical, organic, morphological, or isotopic biosignatures for Fe(II)-oxidizing bacteria (FeOB) that are retained in Fe-rich sediments, which could indicate the activity of these organisms in Fe-rich seawater, more common in the Precambrian Era. To date, the effort to establish a clear Fe isotopic signature in Fe minerals produced by Fe(II)-oxidizing metabolisms has been thwarted by the large kinetic fractionation incurred as freshly oxidized aqueous Fe(III) rapidly precipitates as Fe(III) (oxyhydr)oxide minerals at near neutral pH. The Fe(III) (oxyhydr)oxide minerals resulting from abiotic Fe(II) oxidation are isotopically heavy compared to the Fe(II) precursor and are not clearly distinguishable from minerals formed by FeOB isotopically. However, in marine hydrothermal systems and Fe(II)-rich springs the minerals formed are often isotopically lighter than expected considering the fraction of Fe(II) that has been oxidized and experimentally-determined fractionation factors. We measured the Fe isotopic composition of aqueous Fe (Feaq) and the final Fe mineral (Feppt) produced in batch experiment using the marine Fe(II)-oxidizing phototroph Rhodovulum iodosum. The δ56Feaq data are best described by a kinetic fractionation model, while the evolution of δ56Feppt appears to be controlled by a separate fractionation process. We propose that soluble Fe(III), and Fe(II) and Fe(III) extracted from the Feppt may act as intermediates between Fe(II) oxidation and Fe(III) precipitation. Based on 57Fe Mössbauer spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray total scattering, we suggests these Fe phases, collectively Fe(II/III)interm, may consist of organic-ligand bound, sorbed, and/or colloidal Fe(II) and Fe(III) mineral phases that are isotopically lighter than the final Fe(III) mineral product. Similar intermediate phases, formed in response to organic carbon produced by FeOB and inorganic

  2. Synthesis and Structural Study of the (N,N,N′,N′-TetraethylethylenediamineCdFe(CO4 Dimer

    Directory of Open Access Journals (Sweden)

    Torsten Kolb

    2014-01-01

    Full Text Available The new [(teedaCdFe(CO4]2 complex has been isolated from the reaction of [(NH32CdFe(CO4]n with tetraethylethylenediamine. Unlike previous structural reports of ligand adducts of [L2CdFe(CO4]x complexes, which have all been trimeric species composed of six-membered Cd3Fe3 rings, the teeda complex crystallized as a dimer, analogous to [(2,2-bpyZnFe(CO4]2. As in the zinc dimer, significant distortion arises from steric interactions between the axial carbonyl ligands on opposing iron centers. The complex sits on an inversion center, leading to two independent Cd–Fe distances, 2.7244(6 and 2.7433(6 Å, and crystallizes in the monoclinic space group P21/a with a = 14.8546(2 Å, b = 15.1647(3 Å, c = 15.5252(3 Å, β = 90.9517(12°, and Dcalc = 1.719 g/cm3 at 150(1 K.

  3. Effects of excited state mixing on transient absorption spectra in dimers Application to photosynthetic light-harvesting complex II

    CERN Document Server

    Valkunas, L; Trinkunas, G; Müller, M G; Holzwarth, A R

    1999-01-01

    The excited state mixing effect is taken into account considering the difference spectra of dimers. Both the degenerate (homo) dimer as well as the nondegenerate (hetero) dimer are considered. Due to the higher excited state mixing with the two-exciton states in the homodimer, the excited state absorption (or the difference spectrum) can be strongly affected in comparison with the results obtained in the Heitler-London approximation. The difference spectrum of the heterodimer is influenced by two resonance effects (i) mixing of the ground state optical transitions of both monomers in the dimer and (ii) mixing of the excited state absorption of the excited monomer with the ground state optical transition in the nonexcited monomer. These effects have been tested by simulating the difference absorption spectra of the light-harvesting complex of photosystem II (LHC II) experimentally obtained with the 60 fs excitation pulses at zero delay times and various excitation wavelengths. The pairs of coupled chlorophylls...

  4. Fe II Diagnostic Tools for Quasars

    CERN Document Server

    Verner, E; Verner, D; Johansson, S; Kallman, T; Gull, T R

    2004-01-01

    The enrichment of Fe, relative to alpha-elements such as O and Mg, represents a potential means to determine the age of quasars and probe the galaxy formation epoch. To explore how \\ion{Fe}{2} emission in quasars is linked to physical conditions and abundance, we have constructed a 830-level \\ion{Fe}{2} model atom and investigated through photoionization calculations how \\ion{Fe}{2} emission strengths depend on non-abundance factors. We have split \\ion{Fe}{2} emission into three major wavelength bands, \\ion{Fe}{2} (UV), \\ion{Fe}{2}(Opt1), and \\ion{Fe}{2}(Opt2), and explore how the \\ion{Fe}{2}(UV)/\\ion{Mg}{2}, \\ion{Fe}{2}(UV)/\\ion{Fe}{2}(Opt1) and \\ion{Fe}{2}(UV)/\\ion{Fe}{2}(Opt2) emission ratios depend upon hydrogen density and ionizing flux in broad-line regions (BLR's) of quasars. Our calculations show that: 1) similar \\ion{Fe}{2}(UV)/\\ion{Mg}{2} ratios can exist over a wide range of physical conditions; 2) the \\ion{Fe}{2}(UV)/\\ion{Fe}{2}(Opt1) and \\ion{Fe}{2}(UV)/\\ion{Fe}{2}(Opt2) ratios serve to constrain...

  5. Fe(II)-catalyzed recrystallization of goethite revisited.

    Science.gov (United States)

    Handler, Robert M; Frierdich, Andrew J; Johnson, Clark M; Rosso, Kevin M; Beard, Brian L; Wang, Chongmin; Latta, Drew E; Neumann, Anke; Pasakarnis, Timothy; Premaratne, W A P J; Scherer, Michelle M

    2014-10-01

    Results from enriched (57)Fe isotope tracer experiments have shown that atom exchange can occur between structural Fe in Fe(III) oxides and aqueous Fe(II) with no formation of secondary minerals or change in particle size or shape. Here we derive a mass balance model to quantify the extent of Fe atom exchange between goethite and aqueous Fe(II) that accounts for different Fe pool sizes. We use this model to reinterpret our previous work and to quantify the influence of particle size and pH on extent of goethite exchange with aqueous Fe(II). Consistent with our previous interpretation, substantial exchange of goethite occurred at pH 7.5 (≈ 90%) and we observed little effect of particle size between nanogoethite (average size of 81 × 11 nm; ≈ 110 m(2)/g) and microgoethite (average size of 590 × 42 nm; ≈ 40 m(2)/g). Despite ≈ 90% of the bulk goethite exchanging at pH 7.5, we found no change in mineral phase, average particle size, crystallinity, or reactivity after reaction with aqueous Fe(II). At a lower pH of 5.0, no net sorption of Fe(II) was observed and significantly less exchange occurred accounting for less than the estimated proportion of surface Fe atoms in the particles. Particle size appears to influence the amount of exchange at pH 5.0 and we suggest that aggregation and surface area may play a role. Results from sequential chemical extractions indicate that (57)Fe accumulates in extracted Fe(III) goethite components. Isotopic compositions of the extracts indicate that a gradient of (57)Fe develops within the goethite with more accumulation of (57)Fe occurring in the more easily extracted Fe(III) that may be nearer to the surface.

  6. Photochemical Formation of Fe(II) in the Aqueous Solutions of Fe(III)- Dicarboxylates

    Science.gov (United States)

    Okada, K.; Arakaki, T.

    2007-12-01

    Although there have been many studies reporting the photochemical formation of Fe(II) in various aqueous-phase such as rain, cloud waters, seawater and aerosols, the detailed formation mechanisms are not well understood. To better understand the mechanisms of Fe(II) formation, we attempted to determine the molar absorptivity and the quantum yield of Fe(II) photoformation for individual Fe(III)-dicarboxylate species. The concentrations of Fe(II) and total dissolved Fe were measured by a Ferrozine-HPLC method. The Visual MINTEQ computer program was used to calculate the equilibrium concentrations of chemical species in the solutions of Fe(III)-dicarboxylate complexes. The molar absorptivity and the product of the quantum yield and the molar absorptivity of Fe(III)- dicarboxylate complex can be analysed by UV-VIS spectrophotometer and photochemical experiments, and these experimental data were combined with the calculated equilibrium Fe(III) speciation to determine individual molar absorptivity and quantum yield of Fe(II) photoformation for a specific Fe(III)-dicarboxylate complex. Preliminary results, using an oxalate whose quantum yield has been previously reported, indicate that this approach gives lower quantum yield values in air saturated solutions than previously reported.

  7. Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

    Science.gov (United States)

    Neumann, Anke; Wu, Lingling; Li, Weiqiang; Beard, Brian L; Johnson, Clark M; Rosso, Kevin M; Frierdich, Andrew J; Scherer, Michelle M

    2015-03-03

    Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

  8. Revisited abundance diagnostics in quasars: Fe II/Mg II ratios

    CERN Document Server

    Verner, E M; Verner, D A; Johansson, S; Gull, T R

    2003-01-01

    Both the Fe II UV emission in the 2000- 3000 A region [Fe II (UV)] and resonance emission line complex of Mg II at 2800 A are prominent features in quasar spectra. The observed Fe II UV/ Mg II emission ratios have been proposed as means to measure the buildup of the Fe abundance relative to that of the alpha-elements C, N, O, Ne and Mg as a function of redshift. The current observed ratios show large scatter and no obvious dependence on redshift. Thus, it remains unresolved whether a dependence on redshift exists and whether the observed Fe II UV/ Mg II ratios represent a real nucleosynthesis diagnostic. We have used our new 830-level model atom for Fe+ in photoionization calculations, reproducing the physical conditions in the broad line regions of quasars. This modeling reveals that interpretations of high values of Fe II UV/ Mg II are sensitive not only to Fe and Mg abundance, but also to other factors such as microturbulence, density, and properties of the radiation field. We find that the Fe II UV/ Mg II...

  9. Effect of oxidation rate and Fe(II) state on microbial nitrate-dependent Fe(III) mineral formation.

    Science.gov (United States)

    Senko, John M; Dewers, Thomas A; Krumholz, Lee R

    2005-11-01

    A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems.

  10. Formation of a new copper(II) dimer through heterocyclic ligand ring opening reaction: Supramolecular features and magnetic properties

    Science.gov (United States)

    Gonçalves, Bruna Lisboa; Gervini, Vanessa Carratu; Flores, Alex Fabiani Claro; Junior, Jorge Luiz Pimentel; Bortoluzzi, Adailton João; Burrow, Robert Alan; Duarte, Rafael; da Silva, Robson Ricardo; Vicenti, Juliano Rosa de Menezes

    2017-01-01

    Two new compounds were synthesized and characterized in this work: the heterocycle (Z)-1-(4-(hydroxyimino)-3,5-dimethyl-1-(methylcarbamothioyl)-4,5-dihydro-1H-pyrazol-5-yl)-4-methylthiosemicarbazide and a copper(II) thiosemicarbazonato dimeric complex. Green prismatic single crystals of the dimer were obtained by the reaction of the heterocycle with copper(II) chloride dihydrate. Both compounds were essentially characterized by spectroscopic methods and X-ray diffraction crystallography. The crystal structures revealed molecules connected through supramolecular hydrogen bond interactions and copper(II) centers in a slightly distorted square-pyramidal environment. SQUID magnetometry performed for the dimer revealed both ferromagnetic and antiferromagnetic interactions in the studied complex, presenting a critical temperature of 19 K.

  11. Ligand-induced type II interleukin-4 receptor dimers are sustained by rapid re-association within plasma membrane microcompartments

    Science.gov (United States)

    Richter, David; Moraga, Ignacio; Winkelmann, Hauke; Birkholz, Oliver; Wilmes, Stephan; Schulte, Markos; Kraich, Michael; Kenneweg, Hella; Beutel, Oliver; Selenschik, Philipp; Paterok, Dirk; Gavutis, Martynas; Schmidt, Thomas; Garcia, K. Christopher; Müller, Thomas D.; Piehler, Jacob

    2017-07-01

    The spatiotemporal organization of cytokine receptors in the plasma membrane is still debated with models ranging from ligand-independent receptor pre-dimerization to ligand-induced receptor dimerization occurring only after receptor uptake into endosomes. Here, we explore the molecular and cellular determinants governing the assembly of the type II interleukin-4 receptor, taking advantage of various agonists binding the receptor subunits with different affinities and rate constants. Quantitative kinetic studies using artificial membranes confirm that receptor dimerization is governed by the two-dimensional ligand-receptor interactions and identify a critical role of the transmembrane domain in receptor dimerization. Single molecule localization microscopy at physiological cell surface expression levels, however, reveals efficient ligand-induced receptor dimerization by all ligands, largely independent of receptor binding affinities, in line with the similar STAT6 activation potencies observed for all IL-4 variants. Detailed spatiotemporal analyses suggest that kinetic trapping of receptor dimers in actin-dependent microcompartments sustains robust receptor dimerization and signalling.

  12. Fe hydroxyphosphate precipitation and Fe(II) oxidation kinetics upon aeration of Fe(II) and phosphate-containing synthetic and natural solutions

    Science.gov (United States)

    van der Grift, B.; Behrends, T.; Osté, L. A.; Schot, P. P.; Wassen, M. J.; Griffioen, J.

    2016-08-01

    Exfiltration of anoxic Fe-rich groundwater into surface water and the concomitant oxidative precipitation of Fe are important processes controlling the transport of phosphate (PO4) from agricultural areas to aquatic systems. Here, we explored the relationship between solution composition, reaction kinetics, and the characteristics of the produced Fe hydroxyphosphate precipitates in a series of aeration experiments with anoxic synthetic water and natural groundwater. A pH stat device was used to maintain constant pH and to record the H+ production during Fe(II) oxidation in the aeration experiments in which the initial aqueous P/Fe ratios ((P/Fe)ini), oxygen concentration and pH were varied. In general, Fe(II) oxidation proceeded slower in the presence of PO4 but the decrease of the PO4 concentration during Fe(II) oxidation due to the formation of Fe hydroxyphosphates caused additional deceleration of the reaction rate. The progress of the reaction could be described using a pseudo-second-order rate law with first-order dependencies on PO4 and Fe(II) concentrations. After PO4 depletion, the Fe(II) oxidation rates increased again and the kinetics followed a pseudo-first-order rate law. The first-order rate constants after PO4 depletion, however, were lower compared to the Fe(II) oxidation in a PO4-free solution. Hence, the initially formed Fe hydroxyphosphates also affect the kinetics of continuing Fe(II) oxidation after PO4 depletion. Presence of aqueous PO4 during oxidation of Fe(II) led to the formation of Fe hydroxyphosphates. The P/Fe ratios of the precipitates ((P/Fe)ppt) and the recorded ratio of H+ production over decrease in dissolved Fe(II) did not change detectably throughout the reaction despite a changing P/Fe ratio in the solution. When (P/Fe)ini was 0.9, precipitates with a (P/Fe)ppt ratio of about 0.6 were formed. In experiments with (P/Fe)ini ratios below 0.6, the (P/Fe)ppt decreased with decreasing (P/Fe)ini and pH value. Aeration experiments with

  13. The Fe II problem in NLS1s

    CERN Document Server

    Collin, S

    2000-01-01

    For more than twenty years, strong Fe II emission lines have been observed in Active Galactic Nuclei and in particular in Narrow Line Seyfert 1 galaxies. A quick overview of the observations and of the models proposed to interpret the Fe II spectrum is given. The influence of atomic data and of physical parameters are discussed, and it is shown that the strengths of the Fe II lines cannot be explained in the framework of photoionization models. A non-radiative heating, for instance due to shocks, with an overabundance of iron, can help to solve the problem. A comparison with other objects emitting intense Fe II lines favors also the presence of strong outflows and shocks. We suggest some issues in the context of AGN evolution.

  14. Doubly chloro bridged dimeric copper(II) complex: magneto-structural correlation and anticancer activity.

    Science.gov (United States)

    Sikdar, Yeasin; Modak, Ritwik; Bose, Dipayan; Banerjee, Saswati; Bieńko, Dariusz; Zierkiewicz, Wiktor; Bieńko, Alina; Das Saha, Krishna; Goswami, Sanchita

    2015-05-21

    We have synthesized and structurally characterized a new doubly chloro bridged dimeric copper(II) complex, [Cu2(μ-Cl)2(HL)2Cl2] (1) based on a Schiff base ligand, 5-[(pyridin-2-ylmethylene)-amino]-pentan-1-ol). Single crystal X-ray diffraction shows the presence of dinuclear copper(II) centres in a square pyramidal geometry linked by obtuse double chloro bridge. The magnetic study illustrated that weak antiferromagnetic interactions (J = -0.47 cm(-1)) prevail in complex 1 which is well supported by magneto-structural correlation. This compound adds to the library of doubly chloro bridged copper(ii) complexes in the regime of spin state cross over. DFT calculations have been conducted within a broken-symmetry (BS) framework to investigate the exchange interaction further which depicts that the approximate spin projection technique yields the best corroboration of the experimental J value. Spin density plots show the presence of an ∼0.52e charge residing on the copper atom along with a substantial charge on bridging and peripheral chlorine atoms. The potential of complex1 to act as an anticancer agent is thoroughly examined on a series of liver cancer cell lines and screening shows the HepG2 cell line exhibits maximum cytotoxicity by phosphatidyl serine exposure in the outer cell membrane associated with ROS generation and mitochondrial depolarization with increasing time in the in vitro model system.

  15. Redox cycling of Fe(II) and Fe(III) in magnetite by Fe-metabolizing bacteria

    Science.gov (United States)

    Byrne, James M.; Klueglein, Nicole; Pearce, Carolyn; Rosso, Kevin M.; Appel, Erwin; Kappler, Andreas

    2015-03-01

    Microorganisms are a primary control on the redox-induced cycling of iron in the environment. Despite the ability of bacteria to grow using both Fe(II) and Fe(III) bound in solid-phase iron minerals, it is currently unknown whether changing environmental conditions enable the sharing of electrons in mixed-valent iron oxides between bacteria with different metabolisms. We show through magnetic and spectroscopic measurements that the phototrophic Fe(II)-oxidizing bacterium Rhodopseudomonas palustris TIE-1 oxidizes magnetite (Fe3O4) nanoparticles using light energy. This process is reversible in co-cultures by the anaerobic Fe(III)-reducing bacterium Geobacter sulfurreducens. These results demonstrate that Fe ions bound in the highly crystalline mineral magnetite are bioavailable as electron sinks and electron sources under varying environmental conditions, effectively rendering magnetite a naturally occurring battery.

  16. Online spectrophotometric determination of Fe(II) and Fe(III) by flow injection combined with low pressure ion chromatography

    Science.gov (United States)

    Chen, Shujuan; Li, Nan; Zhang, Xinshen; Yang, Dongjing; Jiang, Heimei

    2015-03-01

    A simple and new low pressure ion chromatography combined with flow injection spectrophotometric procedure for determining Fe(II) and Fe(III) was established. It is based on the selective adsorption of low pressure ion chromatography column to Fe(II) and Fe(III), the online reduction reaction of Fe(III) and the reaction of Fe(II) in sodium acetate with phenanthroline, resulting in an intense orange complex with a suitable absorption at 515 nm. Various chemical (such as the concentration of colour reagent, eluant and reductive agent) and instrumental parameters (reaction coil length, reductive coil length and wavelength) were studied and were optimized. Under the optimum conditions calibration graph of Fe(II)/Fe(III) was linear in the Fe(II)/Fe(III) range of 0.040-1.0 mg/L. The detection limit of Fe(III) and Fe(II) was respectively 3.09 and 1.55 μg/L, the relative standard deviation (n = 10) of Fe(II) and Fe(III) 1.89% and 1.90% for 0.5 mg/L of Fe(II) and Fe(III) respectively. About 2.5 samples in 1 h can be analyzed. The interfering effects of various chemical species were studied. The method was successfully applied in the determination of water samples.

  17. Sorption and catalytic oxidation of Fe(II) at the surface of calcite

    NARCIS (Netherlands)

    Mettler, S.; Wolthers, M.; Charlet, L.; Von Gunten, U.

    2009-01-01

    The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a

  18. Light-induced activation of class II cyclobutane pyrimidine dimer photolyases.

    Science.gov (United States)

    Okafuji, Asako; Biskup, Till; Hitomi, Kenichi; Getzoff, Elizabeth D; Kaiser, Gebhard; Batschauer, Alfred; Bacher, Adelbert; Hidema, Jun; Teranishi, Mika; Yamamoto, Kazuo; Schleicher, Erik; Weber, Stefan

    2010-05-04

    Light-induced activation of class II cyclobutane pyrimidine dimer (CPD) photolyases of Arabidopsis thaliana and Oryza sativa has been examined by UV/Vis and pulsed Davies-type electron-nuclear double resonance (ENDOR) spectroscopy, and the results compared with structure-known class I enzymes, CPD photolyase and (6-4) photolyase. By ENDOR spectroscopy, the local environment of the flavin adenine dinucleotide (FAD) cofactor is probed by virtue of proton hyperfine couplings that report on the electron-spin density at the positions of magnetic nuclei. Despite the amino-acid sequence dissimilarity as compared to class I enzymes, the results indicate similar binding motifs for FAD in the class II photolyases. Furthermore, the photoreduction kinetics starting from the FAD cofactor in the fully oxidized redox state, FAD(ox), have been probed by UV/Vis spectroscopy. In Escherichia coli (class I) CPD photolyase, light-induced generation of FADH from FAD(ox), and subsequently FADH(-) from FADH, proceeds in a step-wise fashion via a chain of tryptophan residues. These tryptophans are well conserved among the sequences and within all known structures of class I photolyases, but completely lacking from the equivalent positions of class II photolyase sequences. Nevertheless, class II photolyases show photoreduction kinetics similar to those of the class I enzymes. We propose that a different, but also effective, electron-transfer cascade is conserved among the class II photolyases. The existence of such electron transfer pathways is supported by the observation that the catalytically active fully reduced flavin state obtained by photoreduction is maintained even under oxidative conditions in all three classes of enzymes studied in this contribution.

  19. [Fe II] jets from intermediate-mass protostars in Carina

    CERN Document Server

    Reiter, Megan; Bally, John

    2016-01-01

    We present new HST/WFC3-IR narrowband [Fe II] images of protostellar jets in the Carina Nebula. Combined with 5 previously published sources, we have a sample of 18 jets and 2 HH objects. All of the jets we targeted with WFC3 show bright infrared [Fe II] emission, and a few H$\\alpha$ candidate jets are confirmed as collimated outflows based on the morphology of their [Fe II] emission. Continuum-subtracted images clearly separate jet emission from the adjacent ionization front, providing a better tracer of the collimated jet than H$\\alpha$ and allowing us to connect these jets with their embedded driving sources. The [Fe II] 1.64 $\\mu$m/H$\\alpha$ flux ratio measured in the jets is $\\gtrsim 5$ times larger than in the adjacent ionization fronts. The low-ionization jet core requires high densities to shield Fe$^+$ against further ionization by the FUV radiation from O-type stars in the H II region. High jet densities imply high mass-loss rates, consistent with the intermediate-mass driving sources we identify fo...

  20. [Fe(II)LSCo(III)LS]2 ⇔ [Fe(III)LSCo(II)HS]2 photoinduced conversion in a cyanide-bridged heterobimetallic molecular square.

    Science.gov (United States)

    Mercurol, Julie; Li, Yanling; Pardo, Emilio; Risset, Olivia; Seuleiman, Mannan; Rousselière, Hélène; Lescouëzec, Rodrigue; Julve, Miguel

    2010-12-21

    The self-assembly of [Fe(III){B(pz)(4)}(CN)(3)](-) and [Co(II)(bik)(2)(S)(2)](2+) affords the diamagnetic cyanide-bridged [Fe(II)(LS)Co(III)(LS)](2) molecular square which is converted into the corresponding magnetic [Fe(III)(LS)Co(II)(HS)](2) species under light irradiation at relatively low temperatures.

  1. Condutividade da Polianilina e Poliacrilonitrila Dopadas com Fe(II e Fe(III

    Directory of Open Access Journals (Sweden)

    Yonis Fornazier Filho

    2015-01-01

    Full Text Available In this work we report O estudo da interação de íons Fe(II com a polianilina foi feito através da obtenção deste polímero na forma de salthe studies on Polyaniline Emeraldine (PANI-ES and Polyacrilonitrile (PAN doped with salt of Fe (II and Fe(III. We used the techniques of conductivity measurements with aplicação de pressão.application of pressure.  The results showed that conductivity of PANI-ES increase with pressure of range of 1.73 MPa until 20.0 MPa and PAN also increase with maximum of 6.0 mPa except to samples PAN-2-TT-FeIII and PAN-2-TTAA-FeIII.

  2. Efficiency of Chitosan for the Removal of Pb (II), Fe (II) and Cu (II) Ions from Aqueous Solutions

    OpenAIRE

    Soheil Sobhanardakani; Raziyeh Zandipak; Hassan Parvizimosaed; Arash Javanshir Khoei; Mehran Moslemi; Mahsa Tahergorabi; Seyed Mehdi Hosseini; Parisa Delfieh

    2014-01-01

    Background: Heavy metals have been recognized as harmful environmental pollutant known to produce highly toxic effects on different organs and systems of both humans and animals. The aim of this paper is to evaluate the adsorption potential of chitosan for the removal of Pb(II), Fe(II) and Cu(II) ions from aqueous solutions. Methods: This study was conducted in laboratory scale. In this paper chitosan has been used as an adsorbent for the removal of Pb(II), Fe(II) and Cu(II) from aqueous s...

  3. Hydrothermal Synthesis and Properties of Open-Framework Mixed-valence Iron Phosphates FeIII2FeII1.5(PO4)3 with Three-dimensional Structure

    Institute of Scientific and Technical Information of China (English)

    DUAN,Li-Ying(段丽颖); LIU,Fu-Chen(刘福臣); WANG,En-Bo(王恩波); LI,Yang-Guang(李阳光); HU,Chang-Wen(胡长文); XU,Lin(许林)

    2004-01-01

    The open-framework iron phosphate FeIII2FeII1.5(PO4)3 was hydrothermally synthesized and characterized by elemental analysis, IR, EPR, XPS and single crystal X-ray diffraction analysis. The title compound crystallized in the triclinic, space group P1 with a=0.64724(4) nm, b=0.79651(6) nm, c=0.94229(5) nm, α=104.447(2)°, β=108.919(4)°, γ=101.741(4)°, V=0.42302(5) nm3, Z=1 and R1 (wR2)=0.0307 (0.0793). Crystal data were collected on a Rigaku R-AXIS RAPID IP diffractometer with Mo Kα (λ=0.071073 nm) at 293(2) K in the range of 2.43°<θ<27.46°. The structure of 1 consists of 19 non-hydrogen atoms including three and a half crystallographically independent Fe and three P atoms. Fe(1) connects its symmetrical Fe(1A) through bridging oxygen forming a dimer and the dimers are connected by Fe(4) forming an infinite staircase-like chain. Fe(2) and Fe(3) connect the infinite chains into a layer with bridging oxygen. Layers are interconnected via Fe(4) forming the six-membered and eight-membered channel systems.

  4. Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

    Science.gov (United States)

    Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

    2013-05-01

    Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

  5. Biologically active new Fe(II, Co(II, Ni(II, Cu(II, Zn(II and Cd(II complexes of N-(2-thienylmethylenemethanamine

    Directory of Open Access Journals (Sweden)

    C. SPÎNU

    2008-04-01

    Full Text Available Iron(II, cobalt(II, nickel (II, copper (II, zinc(II and cadmium(II complexes of the type ML2Cl2, where M is a metal and L is the Schiff base N-(2-thienylmethylenemethanamine (TNAM formed by the condensation of 2-thiophenecarboxaldehyde and methylamine, were prepared and characterized by elemental analysis as well as magnetic and spectroscopic measurements. The elemental analyses suggest the stoichiometry to be 1:2 (metal:ligand. Magnetic susceptibility data coupled with electronic, ESR and Mössbauer spectra suggest a distorted octahedral structure for the Fe(II, Co(II and Ni(II complexes, a square-planar geometry for the Cu(II compound and a tetrahedral geometry for the Zn(II and Cd(II complexes. The infrared and NMR spectra of the complexes agree with co-ordination to the central metal atom through nitrogen and sulphur atoms. Conductance measurements suggest the non-electrolytic nature of the complexes, except for the Cu(II, Zn(II and Cd(II complexes, which are 1:2 electrolytes. The Schiff base and its metal chelates were screened for their biological activity against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa and the metal chelates were found to possess better antibacterial activity than that of the uncomplexed Schiff base.

  6. Bio-inspired cofacial Fe porphyrin dimers for efficient electrocatalytic CO2 to CO conversion: Overpotential tuning by substituents at the porphyrin rings

    Science.gov (United States)

    Zahran, Zaki N.; Mohamed, Eman A.; Naruta, Yoshinori

    2016-04-01

    Efficient reduction of CO2 into useful carbon resources particularly CO is an essential reaction for developing alternate sources of fuels and for reducing the greenhouse effect of CO2. The binuclear Ni, Fe-containing carbon monoxide dehydrogenase (CODHs) efficiently catalyzes the reduction of CO2 to CO. The location of Ni and Fe at proper positions allows their cooperation for CO2 to CO conversion through a push-pull mechanism. Bio-inspired from CODHs, we used several cofacial porphyrin dimers with different substituents as suitable ligands for holding two Fe ions with suitable Fe-Fe separation distance to efficiently and selectively promote CO2 to CO conversion with high turnover frequencies, TOFs. The substituents on the porphyrin rings greatly affect the catalysis process. By introducing electron-withdrawing/-donating groups, e.g. electron-withdrawing perfluorophenyl, at all meso positions of the porphyrin rings, the catalysis overpotential, η was minimized by ≈0.3 V compared to that obtained by introducing electron-donating mesityl groups. The Fe porphyrin dimers among reported catalysts are the most efficient ones for CO2 to CO conversion. Control experiments indicate that the high performance of the current CO2 to CO conversion catalysts is due to the presence of binuclear Fe centers at suitable Fe-Fe separation distance.

  7. Sulfate-bridged dimeric trinuclear copper(II)-pyrazolate complex with three different terminal ligands.

    Science.gov (United States)

    Mezei, Gellert

    2016-08-01

    The reaction of CuSO4·5H2O, 4-chloro-pyrazole (4-Cl-pzH) and tri-ethyl-amine (Et3N) in di-methyl-formamide (DMF) produced crystals of di-aqua-hexa-kis-(μ-4-chloro-pyrazolato-κ(2) N:N')bis-(N,N-di-methyl-formamide)di-μ3-hydroxido-bis-(μ4-sulfato-κ(4) O:O':O'':O'')hexa-copper(II) N,N-di-methyl-formamide tetra-solvate dihydrate, [Cu3(OH)(SO4)(C3H2ClN2)3(C3H7NO)(H2O)]2·4C3H7NO·2H2O. The centrosymmetric dimeric molecule consists of two trinuclear copper-pyrazolate units bridged by two sulfate ions. The title compound provides the first example of a trinuclear copper-pyrazolate complex with three different terminal ligands on the Cu atoms, and also the first example of such complex with a strongly binding basal sulfate ion. Within each trinuclear unit, the Cu(II) atoms are bridged by μ-pyrazolate groups and a central μ3-OH group, and are coordinated by terminal sulfate, H2O and DMF ligands, respectively. Moreover, the sulfate O atoms coordinate at the apical position to the Cu atoms of the symmetry-related unit, providing square-pyramidal coordination geometry around each copper cation. The metal complex and solvent mol-ecules are involved in O-H⋯O hydrogen bonds, leading to a two-dimensional network parallel to (10-1).

  8. Spectroscopic evidence for Fe(II)-Fe(III) electron transfer at clay mineral edge and basal sites.

    Science.gov (United States)

    Neumann, Anke; Olson, Tyler L; Scherer, Michelle M

    2013-07-02

    Despite the importance of Fe redox cycling in clay minerals, the mechanism and location of electron transfer remain unclear. More specifically, there is some controversy whether electron transfer can occur through both basal and edge surfaces. Here we used Mössbauer spectroscopy combined with selective chemical extractions to study electron transfer from Fe(II) sorbed to basal planes and edge OH-groups of clay mineral NAu-1. Fe(II) sorbed predominantly to basal planes at pH values below 6.0 and to edge OH-groups at pH value 7.5. Significant electron transfer occurred from edge OH-group bound Fe(II) at pH 7.5, whereas electron transfer from basal plane-sorbed Fe(II) to structural Fe(III) in clay mineral NAu-1 at pH 4.0 and 6.0 occurred but to a much lower extent than from edge-bound Fe(II). Mössbauer hyperfine parameters for Fe(II)-reacted NAu-1 at pH 7.5 were consistent with structural Fe(II), whereas values found at pH 4.0 and 6.0 were indicative of binding environments similar to basal plane-sorbed Fe(II). Reference experiments with Fe-free synthetic montmorillonite SYn-1 provided supporting evidence for the assignment of the hyperfine parameters to Fe(II) bound to basal planes and edge OH-groups. Our findings demonstrate that electron transfer to structural Fe in clay minerals can occur from Fe(II) sorbed to both basal planes and edge OH-groups. These findings require us to reassess the mechanisms of abiotic and microbial Fe reduction in clay minerals as well as the importance of Fe-bearing clay minerals as a renewable source of redox equivalents in subsurface environments.

  9. Tetrachloroethene degradation by reducing-agent enhanced Fe(II)/Fe(III) catalyzed percarbonate

    Science.gov (United States)

    Miao, Z.; Brusseau, M. L.; Lu, S.; Gu, X.; Yan, N.; Qiu, Z.; Sui, Q.

    2015-12-01

    This project investigated the effect of reducing agents on the degradation of tetrachloroethene(PCE) by Fe(II)/Fe(III) catalyzed sodium percarbonate (SPC). SPC possesses similar function as liquid H2O2, such that free H2O2 is released into solution when percarbonate is mixed with water. The addition of reducing agents, including hydroxylamine hydrochloride, sodium sulfite, ascorbic acid and sodium ascorbate, accelerated the Fe(III)/Fe(II) redoxcycle, leading to a relatively steady Fe(II) concentration and higher production of free radicals. This, in turn, resulted in enhanced PCE oxidation by SPC, with almost complete PCE removal obtained for appropriate Fe and SPC concentrations.The results of chemical probe tests, using nitrobenzene and carbon tetrachloride, demonstrated that HO● was the predominant radical in the system and that O2●-played a minor role. This was further confirmed by the results of electron paramagnetic resonance measurements and salicylic acid hydroxylationanalysis by high performance liquid chromatography(HPLC). PCE degradation decreased significantly with the addition of isopropanol, a strong HO● scavenger, supporting the hypothesis that HO● was primarily responsible for PCE degradation. It should be noted that the release of Cl- was slightly delayed in the first 20 mins, indicating that intermediate products were produced. However, gas chromatography mass spectrometry (GC/MS) analysis did not detect any chlorinated organic compound except PCE, indicating these intermediates were quickly degraded, which resulted in the complete conversion of PCE to CO2. In conclusion, the use of reducing agents to enhance Fe(II)/Fe(III) catalyzed SPC oxidation appears to be a promising approach for the rapid degradation of organic contaminants in groundwater.

  10. Spin relaxation in antiferromagnetic Fe–Fe dimers slowed down by anisotropic DyIII ions

    Directory of Open Access Journals (Sweden)

    Valeriu Mereacre

    2013-11-01

    Full Text Available By using Mössbauer spectroscopy in combination with susceptibility measurements it was possible to identify the supertransferred hyperfine field through the oxygen bridges between DyIII and FeIII in a {Fe4Dy2} coordination cluster. The presence of the dysprosium ions provides enough magnetic anisotropy to “block” the hyperfine field that is experienced by the iron nuclei. This has resulted in magnetic spectra with internal hyperfine fields of the iron nuclei of about 23 T. The set of data permitted us to conclude that the direction of the anisotropy in lanthanide nanosize molecular clusters is associated with the single ion and crystal field contributions and 57Fe Mössbauer spectroscopy may be informative with regard to the the anisotropy not only of the studied isotope, but also of elements interacting with this isotope.

  11. Efficiency of Chitosan for the Removal of Pb (II, Fe (II and Cu (II Ions from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Soheil Sobhanardakani

    2014-09-01

    Full Text Available Background: Heavy metals have been recognized as harmful environmental pollutant known to produce highly toxic effects on different organs and systems of both humans and animals. The aim of this paper is to evaluate the adsorption potential of chitosan for the removal of Pb(II, Fe(II and Cu(II ions from aqueous solutions. Methods: This study was conducted in laboratory scale. In this paper chitosan has been used as an adsorbent for the removal of Pb(II, Fe(II and Cu(II from aqueous solution. In batch tests, the effects of parameters like pH solution (1.0-8.0, initial metal concentrations (100-1000 mgL-1, contact time (5.0-150 min and adsorbent dose (1.0-7.0 g on the adsorption process were studied. Results: The results showed that the adsorption of Pb(II, Fe(II and Cu(II ions on chitosan strongly depends on pH. The experimental isothermal data were analyzed using the Langmuir and Freundlich equations and it was found that the removal process followed the Langmuir isotherm and maximum adsorption capacity for the adsorption of Pb(II, Fe(II and Cu(II ions by the chitosan were 55.5mg g−1, 71.4 mg g−1 and 59 mg g−1, respectively, under equilibrium conditions at 25±1 ºC. The adsorption process was found to be well described by the pseudo-second-order rate model. Conclusion: The obtained results showed that chitosan is a readily, available, economic adsorbent and was found suitable for removing Pb(II, Fe(II and Cu(II ions from aqueous solution.

  12. Cationic zinc (II) dimers and one dimensional coordination polymer from ionic carboxylic acid

    Indian Academy of Sciences (India)

    Paladugu Suresh; Ganesan Prabusankar

    2014-09-01

    A rare example of chelating two tetra cationic paddle-wheel zinc dimers were synthesized from the reaction between flexible imidazolium carboxylate (LH2Br2) and corresponding zinc precursors. A zinc coordination polymer was synthesised by treating in situ generation of 2 in the presence of 4,4′-bipyridine. These new molecules, dimers and polymer, were characterized by FT-IR, NMR, UV-vis, fluorescent and single crystal X-ray diffraction techniques. Zinc polymer is the first example of 1D coordination polymer constructed by tetra cationic zinc dimer as a secondary building unit in coordination polymer.

  13. Biosorption of Fe (II) and Cd (II) ions from aqueous solution using a ...

    African Journals Online (AJOL)

    ADOWIE PERE

    low cost adsorbent to adsorb Cd(II) and Fe(II) metal ions. ... the removal of heavy metals includes high efficiency in metal recovery, readily available, highly ..... sites and also by the decrease in positive surface charge on the adsorbents, which ...

  14. Fe biomineralization mirrors individual metabolic activity in a nitrate-dependent Fe(II-oxidizer

    Directory of Open Access Journals (Sweden)

    Jennyfer eMIOT

    2015-09-01

    Full Text Available Microbial biomineralization sometimes leads to periplasmic encrustation, which is predicted to enhance microorganism preservation in the fossil record. Mineral precipitation within the periplasm is however thought to induce death, as a result of permeability loss preventing nutrient and waste transit across the cell wall. This hypothesis had however never been investigated down to the single cell level. Here, we cultured the nitrate reducing Fe(II oxidizing bacteria Acidovorax sp. strain BoFeN1 that have been previously shown to promote the precipitation of a diversity of Fe minerals (lepidocrocite, goethite, Fe phosphate encrusting the periplasm. We investigated the connection of Fe biomineralization with carbon assimilation at the single cell level, using a combination of electron microscopy and Nano-Secondary Ion Mass Spectrometry (NanoSIMS. Our analyses revealed strong individual heterogeneities of Fe biomineralization. Noteworthy, a small proportion of cells remaining free of any precipitate persisted even at advanced stages of biomineralization. Using pulse chase experiments with 13C-acetate, we provide evidences of individual phenotypic heterogeneities of carbon assimilation, correlated with the level of Fe biomineralization. Whereas non- and moderately encrusted cells were able to assimilate acetate, higher levels of periplasm encrustation prevented any carbon incorporation. Carbon assimilation only depended on the level of Fe encrustation and not on the nature of Fe minerals precipitated in the cell wall. Carbon assimilation decreased exponentially with increasing cell-associated Fe content. Persistence of a small proportion of non-mineralized and metabolically active cells might constitute a strategy of survival in highly ferruginous environments. Eventually, our results suggest that periplasmic Fe biomineralization may provide a signature of individual metabolic status, which could be looked for in the fossil record and in modern

  15. Fe biomineralization mirrors individual metabolic activity in a nitrate-dependent Fe(II)-oxidizer

    Science.gov (United States)

    Miot, Jennyfer; Remusat, Laurent; Duprat, Elodie; Gonzalez, Adriana; Pont, Sylvain; Poinsot, Mélanie

    2015-01-01

    Microbial biomineralization sometimes leads to periplasmic encrustation, which is predicted to enhance microorganism preservation in the fossil record. Mineral precipitation within the periplasm is, however, thought to induce death, as a result of permeability loss preventing nutrient and waste transit across the cell wall. This hypothesis had, however, never been investigated down to the single cell level. Here, we cultured the nitrate reducing Fe(II) oxidizing bacteria Acidovorax sp. strain BoFeN1 that have been previously shown to promote the precipitation of a diversity of Fe minerals (lepidocrocite, goethite, Fe phosphate) encrusting the periplasm. We investigated the connection of Fe biomineralization with carbon assimilation at the single cell level, using a combination of electron microscopy and Nano-Secondary Ion Mass Spectrometry. Our analyses revealed strong individual heterogeneities of Fe biomineralization. Noteworthy, a small proportion of cells remaining free of any precipitate persisted even at advanced stages of biomineralization. Using pulse chase experiments with 13C-acetate, we provide evidence of individual phenotypic heterogeneities of carbon assimilation, correlated with the level of Fe biomineralization. Whereas non- and moderately encrusted cells were able to assimilate acetate, higher levels of periplasmic encrustation prevented any carbon incorporation. Carbon assimilation only depended on the level of Fe encrustation and not on the nature of Fe minerals precipitated in the cell wall. Carbon assimilation decreased exponentially with increasing cell-associated Fe content. Persistence of a small proportion of non-mineralized and metabolically active cells might constitute a survival strategy in highly ferruginous environments. Eventually, our results suggest that periplasmic Fe biomineralization may provide a signature of individual metabolic status, which could be looked for in the fossil record and in modern environmental samples. PMID

  16. Spin dimer and classical spin analyses of the ordered magnetic structures of alkali iron pyrophosphates NaFeP(2)O(7) and LiFeP(2)O(7).

    Science.gov (United States)

    Whangbo, Myung-Hwan; Dai, Dadi; Koo, Hyun-Joo

    2004-10-07

    The magnetic oxides NaFeP(2)O(7) and LiFeP(2)O(7), made up of FeO(6) octahedra containing high-spin Fe(3+)(d(5)) ions, undergo a three-dimensional antiferromagnetic ordering at low temperatures. The strengths of various Fe-O...O-Fe super-superexchange interactions of NaFeP(2)O(7) and LiFeP(2)O(7) were estimated on the basis of spin dimer analysis to probe the nature of their ordered magnetic structures. It is found that the critical factor governing the strength of a Fe-O...O-Fe super-superexchange interaction is not the Fe...Fe distance but the O...O distance. Using the spin exchange parameters thus obtained, the total spin exchange interaction energies were calculated for various ordered spin arrangements of NaFeP(2)O(7) and LiFeP(2)O(7) on the basis of classical spin analysis to confirm that the observed magnetic structures are the magnetic ground states.

  17. THE CONNECTIONS BETWEEN THE UV AND OPTICAL Fe ii EMISSION LINES IN TYPE 1 AGNs

    Energy Technology Data Exchange (ETDEWEB)

    Kovacević-Dojcinović, Jelena; Popović, Luka Č., E-mail: jkovacevic@aob.bg.ac.rs, E-mail: lpopovic@aob.bg.ac.rs [Astronomical Observatory, Volgina 7, 11060 Belgrade (Serbia)

    2015-12-15

    We investigate the spectral properties of the UV (λλ2650–3050 Å) and optical (λλ4000–5500 Å) Fe ii emission features in a sample of 293 Type 1 active galactic nuclei (AGNs) from the Sloan Digital Sky Survey database. We explore different correlations between their emission line properties, as well as the correlations with other emission lines from the spectral range. We find several interesting correlations and outline the most interesting results as follows. (i) There is a kinematical connection between the UV and optical Fe ii lines, indicating that the UV and optical Fe ii lines originate from the outer part of the broad line region, the so-called intermediate line region. (ii) The unexplained anticorrelations of the optical Fe ii equivalent width (EW Fe ii{sub opt}) versus EW [O iii] 5007 Å and EW Fe ii{sub opt} versus FWHM Hβ have not been detected for the UV Fe ii lines. (iii) The significant averaged redshift in the UV Fe ii lines, which is not present in optical Fe ii, indicates an inflow in the UV Fe ii emitting clouds, and probably their asymmetric distribution. (iv) Also, we confirm the anticorrelation between the intensity ratio of the optical and UV Fe ii lines and the FWHM of Hβ, and we find the anticorrelations of this ratio with the widths of Mg ii 2800 Å, optical Fe ii, and UV Fe ii. This indicates a very important role for the column density and microturbulence in the emitting gas. We discuss the starburst activity in high-density regions of young AGNs as a possible explanation of the detected optical Fe ii correlations and intensity line ratios of the UV and optical Fe ii lines.

  18. Physiology, Fe(II oxidation, and Fe mineral formation by a marine planktonic cyanobacterium grown under ferruginous conditions

    Directory of Open Access Journals (Sweden)

    Elizabeth D. Swanner

    2015-10-01

    Full Text Available Evidence for Fe(II oxidation and deposition of Fe(III-bearing minerals from anoxic or redox-stratified Precambrian oceans has received support from decades of sedimentological and geochemical investigation of Banded Iron Formations (BIF. While the exact mechanisms of Fe(II oxidation remains equivocal, reaction with O2 in the marine water column, produced by cyanobacteria or early oxygenic phototrophs, was likely. In order to understand the role of cyanobacteria in the deposition of Fe(III minerals to BIF, we must first know how planktonic marine cyanobacteria respond to ferruginous (anoxic and Fe(II-rich waters in terms of growth, Fe uptake and homeostasis, and Fe mineral formation. We therefore grew the common marine cyanobacterium Synechococcus PCC 7002 in closed bottles that began anoxic, and contained Fe(II concentrations that span the range of possible concentrations in Precambrian seawater. These results, along with cell suspension experiments, indicate that Fe(II is likely oxidized by this strain via chemical oxidation with oxygen produced during photosynthesis, and not via any direct enzymatic or photosynthetic pathway. Imaging of the cell-mineral aggregates with scanning electron microscopy (SEM and confocal laser scanning microscopy (CLSM are consistent with extracellular precipitation of Fe(III (oxyhydroxide minerals, but that >10% of Fe(III sorbs to cell surfaces rather than precipitating. Proteomic experiments support the role of reactive oxygen species (ROS in Fe(II toxicity to Synechococcus PCC 7002. The proteome expressed under low Fe conditions included multiple siderophore biosynthesis and siderophore and Fe transporter proteins, but most siderophores are not expressed during growth with Fe(II. These results provide a mechanistic and quantitative framework for evaluating the geochemical consequences of perhaps life’s greatest metabolic innovation, i.e. the evolution and activity of oxygenic photosynthesis, in ferruginous

  19. Physiology, Fe(II) oxidation, and Fe mineral formation by a marine planktonic cyanobacterium grown under ferruginous conditions

    Science.gov (United States)

    Swanner, Elizabeth; Wu, Wenfang; Hao, Likai; Wuestner, Marina; Obst, Martin; Moran, Dawn; McIlvin, Matthew; Saito, Mak; Kappler, Andreas

    2015-10-01

    Evidence for Fe(II) oxidation and deposition of Fe(III)-bearing minerals from anoxic or redox-stratified Precambrian oceans has received support from decades of sedimentological and geochemical investigation of Banded Iron Formations (BIF). While the exact mechanisms of Fe(II) oxidation remains equivocal, reaction with O2 in the marine water column, produced by cyanobacteria or early oxygenic phototrophs, was likely. In order to understand the role of cyanobacteria in the deposition of Fe(III) minerals to BIF, we must first know how planktonic marine cyanobacteria respond to ferruginous (anoxic and Fe(II)-rich) waters in terms of growth, Fe uptake and homeostasis, and Fe mineral formation. We therefore grew the common marine cyanobacterium Synechococcus PCC 7002 in closed bottles that began anoxic, and contained Fe(II) concentrations that span the range of possible concentrations in Precambrian seawater. These results, along with cell suspension experiments, indicate that Fe(II) is likely oxidized by this strain via chemical oxidation with oxygen produced during photosynthesis, and not via any direct enzymatic or photosynthetic pathway. Imaging of the cell-mineral aggregates with scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM) are consistent with extracellular precipitation of Fe(III) (oxyhydr)oxide minerals, but that >10% of Fe(III) sorbs to cell surfaces rather than precipitating. Proteomic experiments support the role of reactive oxygen species (ROS) in Fe(II) toxicity to Synechococcus PCC 7002. The proteome expressed under low Fe conditions included multiple siderophore biosynthesis and siderophore and Fe transporter proteins, but most siderophores are not expressed during growth with Fe(II). These results provide a mechanistic and quantitative framework for evaluating the geochemical consequences of perhaps life’s greatest metabolic innovation, i.e. the evolution and activity of oxygenic photosynthesis, in ferruginous

  20. Fe(III)EDTA and Fe(II)EDTA-NO reduction by a sulfate reducing bacterium in NO and SO₂ scrubbing liquor.

    Science.gov (United States)

    Chen, Mingxiang; Zhou, Jiti; Zhang, Yu; Wang, Xiaojun; Shi, Zhuang; Wang, Xiaowei

    2015-03-01

    A viable process concept, based on NO and SO2 absorption into an alkaline Fe(II)EDTA (EDTA: ethylenediaminetetraacetic acid) solution in a scrubber combined with biological reduction of the absorbed SO2 utilizing sulfate reducing bacteria (SRB) and regeneration of the scrubbing liquor in a single bioreactor, was developed. The SRB, Desulfovibrio sp. CMX, was used and its sulfate reduction performances in FeEDTA solutions and Fe(II)EDTA-NO had been investigated. In this study, the detailed regeneration process of Fe(II)EDTA solution, which contained Fe(III)EDTA and Fe(II)EDTA-NO reduction processes in presence of D. sp. CMX and sulfate, was evaluated. Fe(III)EDTA and Fe(II)EDTA-NO reduction processes were primarily biological, even if Fe(III)EDTA and Fe(II)EDTA-NO could also be chemically convert to Fe(II)EDTA by biogenic sulfide. Regardless presence or absence of sulfate, more than 87 % Fe(III)EDTA and 98 % Fe(II)EDTA-NO were reduced in 46 h, respectively. Sulfate and Fe(III)EDTA had no affection on Fe(II)EDTA-NO reduction. Sulfate enhanced final Fe(III)EDTA reduction. Effect of Fe(III)EDTA on Fe(II)EDTA-NO reduction rate was more obvious than effect of sulfate on Fe(II)EDTA-NO reduction rate before 8 h. To overcome toxicity of Fe(II)EDTA-NO on SRB, Fe(II)EDTA-NO was reduced first and the reduction of Fe(III)EDTA and sulfate occurred after 2 h. First-order Fe(II)EDTA-NO reduction rate and zero-order Fe(III)EDTA reduction rate were detected respectively before 8 h.

  1. Chelation of Cu(II, Zn(II, and Fe(II by Tannin Constituents of Selected Edible Nuts

    Directory of Open Access Journals (Sweden)

    Magdalena Karamać

    2009-12-01

    Full Text Available The tannin fractions isolated from hazelnuts, walnuts and almonds were characterised by colorimetric assays and by an SE-HPLC technique. The complexation of Cu(II and Zn(II was determined by the reaction with tetramethylmurexide, whereas for Fe(II, ferrozine was employed. The walnut tannins exhibited a significantly weaker reaction with the vanillin/HCl reagent than hazelnut and almond tannins, but the protein precipitation capacity of the walnut fraction was high. The SE-HPLC chromatogram of the tannin fraction from hazelnuts revealed the presence of oligomers with higher molecular weights compared to that of almonds. Copper ions were most effectively chelated by the constituents of the tannin fractions of hazelnuts, walnuts and almonds. At a 0.2 mg/assay addition level, the walnut tannins complexed almost 100% Cu(II. The Fe(II complexation capacities of the tannin fractions of walnuts and hazelnuts were weaker in comparison to that of the almond tannin fraction, which at a 2.5 mg/assay addition level, bound Fe(II by ~90%. The capacity to chelate Zn(II was quite varied for the different nut tannin fractions: almond tannins bound as much as 84% Zn(II, whereas the value for walnut tannins was only 8.7%; and for hazelnut tannins, no Zn(II chelation took place at the levels tested.

  2. Abiotic reduction of nitroaromatic compounds by Fe(II) associated with iron oxides and humic acid.

    Science.gov (United States)

    Luan, Fubo; Xie, Li; Li, Jun; Zhou, Qi

    2013-05-01

    Experiments were conducted to examine the reduction of nitroaromatic compounds (NACs) by Fe(II) associated with iron oxides (goethite, hematite and magnetite) and humic acid. The reduction rate of nitrobenzene decreased in the order of Fe(II) associated with magnetite>Fe(II) associated with goethite>Fe(II) associated with hematite. We proposed a four-step model (adsorption, electron transfer to conduction band, electron transfer to nitrobenzene and electron transfer to crystal lattice) for nitrobenzene reduction by Fe(II) associated with iron oxides. Fe(II)-humic acid complexes did not present reduction capability of nitrobenzene. Furthermore, Humic acid significantly inhibited nitrobenzene reduction by Fe(II) associated with iron oxides. The inhibitory effect of humic acid toward the reduction of nitrobenzene decreased in the order of magnetite>goethite>hematite. Copyright © 2013 Elsevier Ltd. All rights reserved.

  3. Spectral studies of dimeric copper(II) complexes of acid amide derivatives as models for type III copper enzymes

    Science.gov (United States)

    Garg, Bhagwan S.; Nandan Kumar, Deo; Sarbhai, Meenu; Reddy, Malladi J.

    2003-10-01

    Dimeric (hydrated and anhydrated) complexes of Cu(II) with N, N'-bis(3-carboxy-1-oxo-2-prop-2-enyl)ethylenediamine(BCOPENH 2, A) and N, N'-bis(2-carboxy-1-oxo-phenylenyl)ethylenediamine(BCOPHENH 2, B) have been prepared and characterised by elemental analysis, magnetic susceptibility measurements, EPR, thermal and spectral (IR, UV/Vis) studies. EPR parameters and magnetic behaviour indicates that the complexes are antiferromagnetic in nature and most likely adopt the typical carboxylate cage structure. Interesting amide bonding patterns have been observed and various EPR parameters have been evaluated on the basis of these studies, tentative probable structures of the complexes have been proposed.

  4. FeII/MgII Emission Line Ratio in High Redshift Quasars

    DEFF Research Database (Denmark)

    Dietrich, M.; Hamann, F.; Appenzeller, I.

    2003-01-01

    We present results of the analysis of near infrared spectroscopic observations of 6 high-redshift quasars (z > 4), emphasizing the measurement of the ultraviolet FeII/MgII emission line strength in order to estimate the beginning of intense star formation in the early universe. To investigate...... the evolution of the FeII/MgII ratio over a wider range in cosmic time, we measured this ratio for composite quasar spectra which cover a redshift range of 0 4 quasars must have started already at an epoch corresponding to z_f = 6 to 9, when the age of the universe was ~0.5 Gyr (H_o = 72 km/s/Mpc, Omega_M = 0...

  5. Thermodynamics of Fe(II)Fe(III) oxide systems I. Hydrothermal Fe3O4

    Science.gov (United States)

    Bartel, J.J.; Westrum, E.F.; Haas, J.L.

    1976-01-01

    The heat capacity of a hydrothermally-prepared polycrystalline sample of Fe3O4 was measured from 53 to 350 K, primarily to study the thermophysics of the Verwey transitions. Although the bifurcation of the transition was confirmed, the sample was found to contain traces of manganese. The observed transition temperatures of 117.0 and 123.0 K are 3.7 and 4.2 K higher respectively than those found in pure Fe3O4. Ancillary analytical results are consistent and indicate a stoichiometry of Mn0.008Fe2.992O4 for this material. Characteristics in the transition region are ascribed to dopant effects. ?? 1976.

  6. Oxygen isotope indicators of selenate reaction with Fe(II) and Fe(III) hydroxides.

    Science.gov (United States)

    Schellenger, Alexandra E P; Larese-Casanova, Philip

    2013-06-18

    Selenate (SeO(4)(2-)) reduction to elemental selenium is an important Se immobilization process in subsurface environments that could be mediated by Fe(II)-rich minerals or selenate-respiring microorganisms. We report the kinetic isotope effects for (18)O within selenate during abiotic reactions with iron-bearing hydroxides within laboratory experiments. Selenate was reduced to Se(0) by a green rust (chloride interlayer type) and ferrous hydroxide, the two known environmentally relevant mineral reductants for selenate. Reaction kinetics are described by a rapid, low-fractionating uptake step caused by diffusive exchange between selenate and chloride followed by a slower, high-fractionating reduction step caused by electron transfer from structural Fe(II). The dual-phase kinetics cannot be described with the traditional Rayleigh fractionation model; however, well after the initial uptake step, the extent of selenate reaction is well correlated with δ(18)O values in accordance with the Rayleigh model. Selenate-(18)O enrichment (εO) was nearly identical for reaction with chloride green rust (22.7 ± 2.2‰) and ferrous hydroxide (22.1 ± 1.1‰) which suggests a common reduction mechanism by structural Fe(II). The minor enrichment due to anion exchange alone (1.4 ± 0.2‰) was confirmed using iowaite, a nonredox active Mg(II)-Fe(III) layered double hydroxide. Our εO results may contribute to Se isotope forensics to identify selenate reduction within field sites and to possibly distinguish between abiotic and biotic reduction processes.

  7. Atomic Data and Spectral Models for FeII

    CERN Document Server

    Bautista, Manuel A; Ballance, Connor; Quinet, Pascal; Ferland, Gary; Mendoza, Claudio; Kallman, Timothy R

    2015-01-01

    We present extensive calculations of radiative transition rates and electron impact collision strengths for Fe II. The data sets involve 52 levels from the $3d\\,^7$, $3d\\,^64s$, and $3d\\,^54s^2$ configurations. Computations of $A$-values are carried out with a combination of state-of-the-art multiconfiguration approaches, namely the relativistic Hartree--Fock, Thomas--Fermi--Dirac potential, and Dirac--Fock methods; while the $R$-matrix plus intermediate coupling frame transformation, Breit--Pauli $R$-matrix and Dirac $R$-matrix packages are used to obtain collision strengths. We examine the advantages and shortcomings of each of these methods, and estimate rate uncertainties from the resulting data dispersion. We proceed to construct excitation balance spectral models, and compare the predictions from each data set with observed spectra from various astronomical objects. We are thus able to establish benchmarks in the spectral modeling of [Fe II] emission in the IR and optical regions as well as in the UV Fe...

  8. Discoloration and mineralization of Orange II using different heterogeneous catalysts containing Fe: a comparative study.

    Science.gov (United States)

    Feng, Jiyun; Hu, Xijun; Yue, Po Lock

    2004-11-01

    Four heterogeneous catalysts containing Fe including a bentonite-clay-based Fe nanocomposite (Fe-B), hematite (alpha-Fe2O3), amorphous FeOOH, and calcined FeOOH (denoted as FeOOH-M) were employed for the photo-Fenton discoloration and mineralization of 0.2 mM Orange II in the presence of 10 mM H2O2 and 8 W UVC at two different initial solution pH values (3.0 and 6.6). It was found that, at an initial solution pH of 3.0, their photocatalytic activities follow the order Fe-B > FeOOH, FeOOH-M > alpha-Fe2O3. When the Fe-B nanocomposite, FeOOH, and FeOOH-M were used as heterogeneous catalysts, both heterogeneous and homogeneous photo-Fenton reactions were responsible for the discoloration and mineralization of 0.2 mM Orange II because homogeneous photo-Fenton reaction occurred due to the presence of Fe ions leached from the catalysts. At an initial solution pH of 6.6, their photocatalytic activities still follow the order Fe-B > FeOOH, FeOOH-M > alpha-Fe2O3. However, only heterogeneous photo-Fenton reaction accounted for the discoloration and mineralization of 0.2 mM Orange II because Fe leaching from the catalysts was significantly depressed. In the case of alpha-Fe2O3 as a catalyst, whether at an initial solution pH of 3.0 or 6.6, only heterogeneous photo-Fenton reaction happened for the discoloration and mineralization of 0.2 mM Orange II because Fe leaching from the catalyst is negligible. The apparent discoloration kinetics of Orange II with the four catalysts at two different initial solution pH values was also investigated.

  9. Endogenous type II cGMP-dependent protein kinase exists as a dimer in membranes and can Be functionally distinguished from the type I isoforms

    NARCIS (Netherlands)

    A.B. Vaandrager (Arie); M.J. Edixhoven (Marcel); A.G. Bot (Alice); M.A. Kroos (Marian); T. Jarchau; S. Lohmann; H.G. Genieser; H.R. de Jonge (Hugo)

    1997-01-01

    textabstractIn mammalian tissues two types of cGMP-dependent protein kinase (cGK) have been identified. In contrast to the dimeric cGK I, cGK II purified from pig intestine was shown previously to behave as a monomer. However, recombinant rat cGK II was found to have hy

  10. Incorporation of oxidized uranium into Fe (hydr)oxides during Fe(II) catalyzed remineralization

    Energy Technology Data Exchange (ETDEWEB)

    Nico, Peter S.; Stewart, Brandy D.; Fendorf, Scott

    2009-07-01

    The form of solid phase U after Fe(II) induced anaerobic remineralization of ferrihydrite in the presence of aqueous and absorbed U(VI) was investigated under both abiotic batch and biotic flow conditions. Experiments were conducted with synthetic ground waters containing 0.168 mM U(VI), 3.8 mM carbonate, and 3.0 mM Ca{sup 2+}. In spite of the high solubility of U(VI) under these conditions, appreciable removal of U(VI) from solution was observed in both the abiotic and biotic systems. The majority of the removed U was determined to be substituted as oxidized U (U(VI) or U(V)) into the octahedral position of the goethite and magnetite formed during ferrihydrite remineralization. It is estimated that between 3% and 6% of octahedral Fe(III) centers in the new Fe minerals were occupied by U(VI). This site specific substitution is distinct from the non-specific U co-precipitation processes in which uranyl compounds, e.g. uranyl hydroxide or carbonate, are entrapped with newly formed Fe oxides. The prevalence of site specific U incorporation under both abiotic and biotic conditions and the fact that the produced solids were shown to be resistant to both extraction (30 mM KHCO{sub 3}) and oxidation (air for 5 days) suggest the potential importance of sequestration in Fe oxides as a stable and immobile form of U in the environment.

  11. Incorporation of oxidized uranium into Fe (hydr)oxides during Fe(II) catalyzed remineralization

    Energy Technology Data Exchange (ETDEWEB)

    Nico, Peter S.; Stewart, Brandy D.; Fendorf, Scott

    2009-07-01

    The form of solid phase U after Fe(II) induced anaerobic remineralization of ferrihydrite in the presence of aqueous and absorbed U(VI) was investigated under both abiotic batch and biotic flow conditions. Experiments were conducted with synthetic ground waters containing 0.168 mM U(VI), 3.8 mM carbonate, and 3.0 mM Ca{sup 2+}. In spite of the high solubility of U(VI) under these conditions, appreciable removal of U(VI) from solution was observed in both the abiotic and biotic systems. The majority of the removed U was determined to be substituted as oxidized U (U(VI) or U(V)) into the octahedral position of the goethite and magnetite formed during ferrihydrite remineralization. It is estimated that between 3% and 6% of octahedral Fe(III) centers in the new Fe minerals were occupied by U(VI). This site specific substitution is distinct from the non-specific U co-precipitation processes in which uranyl compounds, e.g. uranyl hydroxide or carbonate, are entrapped with newly formed Fe oxides. The prevalence of site specific U incorporation under both abiotic and biotic conditions and the fact that the produced solids were shown to be resistant to both extraction (30 mM KHCO{sub 3}) and oxidation (air for 5 days) suggest the potential importance of sequestration in Fe oxides as a stable and immobile form of U in the environment.

  12. Peculiarities of MCD C-term saturation behavior of the exchange coupled Co(II) dimers

    Energy Technology Data Exchange (ETDEWEB)

    Ostrovsky, S.M., E-mail: sm_ostrovsky@yahoo.com [Institute of Applied Physics, Academy of Sciences of Moldova, Academiei Str. 5, MD 2028, Chisinau, Republic of Moldova (Moldova, Republic of)

    2011-07-28

    Graphical abstract: The change of sign of the MCD signal with temperature and magnetic field increase can take place. The origin of this peculiarity is explained by the strong orbital contribution. Highlights: {yields} MCD C-term saturation behavior of the exchange coupled cobalt dimer. {yields} Strong orbital contribution to the magneto-optical behavior. {yields} Change of sign of the MCD signal with temperature and magnetic field increase. - Abstract: The MCD C-term saturation behavior of the exchange coupled octahedrally coordinated cobalt dimers is studied for different types of distortion of the local surrounding of each interacting ion. It was found that in the case of antiferromagnetic exchange interaction the change of sign of the MCD signal with temperature and magnetic field increase can take place. This signal behavior is not the result of overlapping of different electronic transitions and it is characteristic of an individual MCD line. The origin of this magneto-optical behavior is explained by the strong contribution coming from the unquenched orbital angular momenta of interacting cobalt ions. The found peculiarity is inherent to complexes composed of nonequivalent cobalt ions as well as to the dimeric complexes with the equivalent Co ions with nonparallel local axes.

  13. Electron transfer and atom exchange between aqueous Fe(II) and structural Fe(III) in clays. Role in U and Hg(II) transformations

    Energy Technology Data Exchange (ETDEWEB)

    Scherer, Michelle [Univ. of Iowa, Iowa City, IA (United States)

    2016-08-31

    During this project, we investigated Fe electron transfer and atom exchange between aqueous Fe(II) and structural Fe(III) in clay minerals. We used selective chemical extractions, enriched Fe isotope tracer experiments, computational molecular modeling, and Mössbauer spectroscopy. Our findings indicate that structural Fe(III) in clay minerals is reduced by aqueous Fe(II) and that electron transfer occurs when Fe(II) is sorbed to either basal planes and edge OH-groups of clay mineral. Findings from highly enriched isotope experiments suggest that up to 30 % of the Fe atoms in the structure of some clay minerals exhanges with aqueous Fe(II). First principles calculations using a small polaron hopping approach suggest surprisingly fast electron mobility at room temperature in a nontronite clay mineral and are consistent with temperature dependent Mössbauer data Fast electron mobility suggests that electrons may be able to conduct through the mineral fast enough to enable exchange of Fe between the aqueous phase and clay mineral structure. over the time periods we observed. Our findings suggest that Fe in clay minerals is not as stable as previously thought.

  14. Environments of strong/ultrastrong, ultraviolet Fe II emitting quasars

    Science.gov (United States)

    Clowes, Roger G.; Raghunathan, Srinivasan; Söchting, Ilona K.; Graham, Matthew J.; Campusano, Luis E.

    2013-08-01

    We have investigated the strength of ultraviolet (UV) Fe II emission from quasars within the environments of large quasar groups (LQGs) in comparison with quasars elsewhere, for 1.1 ≤ zLQG ≤ 1.7, using the DR7QSO catalogue of the Sloan Digital Sky Survey. We use the Weymann et al. W2400 equivalent width, defined between the rest-frame continuum windows 2240-2255 and 2665-2695 Å, as the measure of the UV Fe II emission. We find a significant shift of the W2400 distribution to higher values for quasars within LQGs, predominantly for those LQGs with 1.1 ≤ zLQG ≤ 1.5. There is a tentative indication that the shift to higher values increases with the quasar i magnitude. We find evidence that within LQGs the ultrastrong emitters with W2400 ≥ 45 Å (more precisely, ultrastrong plus with W2400 ≥ 44 Å) have preferred nearest-neighbour separations of ˜30-50 Mpc to the adjacent quasar of any W2400 strength. No such effect is seen for the ultrastrong emitters that are not in LQGs. The possibilities for increasing the strength of the Fe II emission appear to be iron abundance, Lyα fluorescence and microturbulence, and probably all of these operate. The dense environment of the LQGs may have led to an increased rate of star formation and an enhanced abundance of iron in the nuclei of galaxies. Similarly, the dense environment may have led to more active blackholes and increased Lyα fluorescence. The preferred nearest-neighbour separation for the stronger emitters would appear to suggest a dynamical component, such as microturbulence. In one particular LQG, the Huge-LQG (the largest structure known in the early Universe), six of the seven strongest emitters very obviously form three pairings within the total of 73 members.

  15. THE Fe II EMISSION IN ACTIVE GALACTIC NUCLEI: EXCITATION MECHANISMS AND LOCATION OF THE EMITTING REGION

    Energy Technology Data Exchange (ETDEWEB)

    Marinello, M. [Universidade Federal de Itajubá, Rua Doutor Pereira Cabral 1303, 37500-903, Itajubá, MG (Brazil); Rodríguez-Ardila, A.; Garcia-Rissmann, A. [Laboratório Nacional de Astrofísica, Rua Estados Unidos 154, Itajubá, MG, 37504-364 (Brazil); Sigut, T. A. A. [The University of Western Ontario, London, ON N6A 3K7 (Canada); Pradhan, A. K., E-mail: murilo.marinello@gmail.com [McPherson Laboratory, The Ohio State University, 140 W. 18th Ave., Columbus, OH 43210-1173 (United States)

    2016-04-01

    We present a study of Fe ii emission in the near-infrared region (NIR) for 25 active galactic nuclei (AGNs) to obtain information about the excitation mechanisms that power it and the location where it is formed. We employ an NIR Fe ii template derived in the literature and find that it successfully reproduces the observed Fe ii spectrum. The Fe ii bump at 9200 Å detected in all objects studied confirms that Lyα fluorescence is always present in AGNs. The correlation found between the flux of the 9200 Å bump, the 1 μm lines, and the optical Fe ii implies that Lyα fluorescence plays an important role in Fe ii production. We determined that at least 18% of the optical Fe ii is due to this process, while collisional excitation dominates the production of the observed Fe ii. The line profiles of Fe ii λ10502, O i λ11287, Ca ii λ8664, and Paβ were compared to gather information about the most likely location where they are emitted. We found that Fe ii, O i and Ca ii have similar widths and are, on average, 30% narrower than Paβ. Assuming that the clouds emitting the lines are virialized, we show that the Fe ii is emitted in a region twice as far from the central source than Paβ. The distance, though, strongly varies: from 8.5 light-days for NGC 4051 to 198.2 light-days for Mrk 509. Our results reinforce the importance of the Fe ii in the NIR to constrain critical parameters that drive its physics and the underlying AGN kinematics, as well as more accurate models aimed at reproducing this complex emission.

  16. Characterization of the physiology and cell-mineral interactions of the marine anoxygenic phototrophic Fe(II) oxidizer Rhodovulum iodosum--implications for Precambrian Fe(II) oxidation.

    Science.gov (United States)

    Wu, Wenfang; Swanner, Elizabeth D; Hao, Likai; Zeitvogel, Fabian; Obst, Martin; Pan, Yongxin; Kappler, Andreas

    2014-06-01

    Anoxygenic phototrophic Fe(II)-oxidizing bacteria (photoferrotrophs) are suggested to have contributed to the deposition of banded iron formations (BIFs) from oxygen-poor seawater. However, most studies evaluating the contribution of photoferrotrophs to Precambrian Fe(II) oxidation have used freshwater and not marine strains. Therefore, we investigated the physiology and mineral products of Fe(II) oxidation by the marine photoferrotroph Rhodovulum iodosum. Poorly crystalline Fe(III) minerals formed initially and transformed to more crystalline goethite over time. During Fe(II) oxidation, cell surfaces were largely free of minerals. Instead, the minerals were co-localized with EPS suggesting that EPS plays a critical role in preventing cell encrustation, likely by binding Fe(III) and directing precipitation away from cell surfaces. Fe(II) oxidation rates increased with increasing initial Fe(II) concentration (0.43-4.07 mM) under a light intensity of 12 μmol quanta m(-2) s(-1). Rates also increased as light intensity increased (from 3 to 20 μmol quanta m(-2) s(-1)), while the addition of Si did not significantly change Fe(II) oxidation rates. These results elaborate on how the physical and chemical conditions present in the Precambrian ocean controlled the activity of marine photoferrotrophs and confirm the possibility that such microorganisms could have oxidized Fe(II), generating the primary Fe(III) minerals that were then deposited to some Precambrian BIFs. © 2014 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

  17. Role of (NO)2 dimer in reactions of Fe+ with NO and NO2 studied by ICP-SIFT mass spectrometry.

    Science.gov (United States)

    Blagojevic, Voislav; Jarvis, Michael J Y; Koyanagi, Gregory K; Bohme, Diethard K

    2013-05-09

    In a recent publication by J. J. Melko et al. (J. Phys. Chem. A2012, 116, 11500-11508) on the reactions of Fe(+) cations with NO and NO2, these authors made a number of assertions regarding the work previously published in our laboratory. Melko et al. assert that our previously reported data was erroneously analyzed, resulting in our misreporting of the Fe(+) + NO2 reaction branching ratio for NO(+). Also, they proposed that this alleged misreporting made it likely for the second-order chemistry observed in our Fe(+) + NO experiments to be a product of an impurity of NO2 in our NO reagent and, furthermore, that our reported rate coefficient for the effective second-order chemistry was unreasonably high on the basis of their model calculations. Despite extensive private communications in which we presented detailed data supporting our original data analysis to Melko et al., these authors proceeded to publish their critique without any reference to this data. Here, we present the data communicated by us to Melko et al. and show that our result reported earlier for the Fe(+) + NO2 reaction branching ratio to form NO(+) is accurate and, furthermore, that there is no evidence for a sufficient NO2 impurity in any of our NO experiments. We suggest that the discrepancy in the results observed by us and Melko et al. may be attributed to a reaction with the dimer (NO)2. This possibility was dismissed in our earlier work as the dimer concentration under the flow tube conditions was calculated to be below 10(-5)% of the monomer, but the new results of J. J. Melko et al. raise the dimer reaction as a real possibility. Finally, J. J. Melko et al. appear to have misunderstood the mechanism of the second-order NO chemistry that we had proposed.

  18. Controls on Fe(II)-Activated Trace Element Release from Goethite and Hematite

    Energy Technology Data Exchange (ETDEWEB)

    Frierdich, Andrew J.; Catalano, Jeffrey G. (WU)

    2012-03-26

    Electron transfer and atom exchange (ETAE) between aqueous Fe(II) and Fe(III) oxides induces surface growth and dissolution that affects trace element fate and transport. We have recently demonstrated Ni(II) cycling through goethite and hematite (adsorbed Ni incorporates into the mineral structure and preincorporated Ni releases to solution) during Fe(II)-Fe(III) ETAE. However, the chemical parameters affecting net trace element release remain unknown. Here, we examine the chemical controls on Ni(II) and Zn(II) release from Ni- and Zn-substituted goethite and hematite during reaction with Fe(II). Release follows a rate law consistent with surface reaction limited mineral dissolution and suggests that release occurs near sites of Fe(III) reductive dissolution during Fe(II)-Fe(III) ETAE. Metal substituent type affects reactivity; Zn release is more pronounced from hematite than goethite, whereas the opposite trend occurs for Ni. Buildup of Ni or Zn in solution inhibits further release but this resumes upon fluid exchange, suggesting that sustained release is possible under flow conditions. Mineral and aqueous Fe(II) concentrations as well as pH strongly affect sorbed Fe(II) concentrations, which directly control the reaction rates and final metal concentrations. Our results demonstrate that structurally incorporated trace elements are mobilized from iron oxides into fluids without abiotic or microbial net iron reduction. Such release may affect micronutrient availability, contaminant transport, and the distribution of redox-inactive trace elements in natural and engineered systems.

  19. Heterogeneous reduction of PuO₂ with Fe(II): importance of the Fe(III) reaction product.

    Science.gov (United States)

    Felmy, Andrew R; Moore, Dean A; Rosso, Kevin M; Qafoku, Odeta; Rai, Dhanpat; Buck, Edgar C; Ilton, Eugene S

    2011-05-01

    Heterogeneous reduction of actinides in higher, more soluble oxidation states to lower, more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied, even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO₂(am) by Fe(II). We present the first experimental evidence that reduction of PuO₂(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) {[Pu(III) + Pu(IV)] - Pu(IV)} by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II).

  20. $Ly \\alpha$ Fluorescent Excitation of FeII in Active Galactic Nuclei

    CERN Document Server

    Sigut, T A A; Pradhan, Anil K.

    1998-01-01

    We have calculated FeII emission line strengths for Active Galactic Nuclei Broad-Line Regions using precise radiative transfer and Iron Project atomic data. We improve the treatment of all previously considered excitation mechanisms for the FeII emission, continuum fluorescence, collisional excitation, fluorescence by self-overlap among the iron lines, and fluorescent excitation by Lyman-alpha. We demonstrate that Lyman-alpha fluorescence is of fundamental importance in determining the strength of the FeII emission. In addition to enhancing the ultraviolet and optical FeII flux, Lyman-alpha fluorescence also results in significant near-infrared FeII emission in the 8500-9500 Angstrom wavelength range. New observations are suggested to probe this effect in strong FeII emitting quasars.

  1. Environments of Strong / Ultrastrong, Ultraviolet Fe II Emitting Quasars

    CERN Document Server

    Clowes, Roger G; Soechting, Ilona K; Graham, Matthew J; Campusano, Luis E

    2013-01-01

    We have investigated the strength of ultraviolet Fe II emission from quasars within the dense environments of Large Quasar Groups (LQGs) in comparison with quasars elsewhere, for 1.1 = 45 Ang. (more precisely, ultrastrong-plus with W2400 >= 44 Ang.) have preferred nearest-neighbour separations of ~ 30-50 Mpc to the adjacent quasar of any W2400 strength. No such effect is seen for the ultrastrong emitters that are not in LQGs. The possibilities for increasing the strength of the Fe II emission appear to be iron abundance, Ly-alpha fluorescence, and microturbulence, and probably all of these operate. The dense environment of the LQGs may have led to an increased rate of star formation and an enhanced abundance of iron in the nuclei of galaxies. Similarly the dense environment may have led to more active blackholes and increased Ly-alpha fluorescence. The preferred nearest-neighbour separation for the stronger emitters would appear to suggest a dynamical component, such as microturbulence. In one particular LQ...

  2. Selection of Chelated Fe (III)/Fe (II) Catalytic Oxidation Agents for Desulfurization Based on Iron Complexation Method

    Institute of Scientific and Technical Information of China (English)

    Luo Ying; Liu Youzhi; Qi Guisheng; Guo Huidong; Zhu Zhengfeng

    2014-01-01

    Optimization of factors inlfuencing the experiments on reactions involving 8 different chelating agents and sol-uble Fe (III)/Fe (II) salts was carried out to yield chelated iron complexes. A combination of optimized inlfuencing factors has resulted in a Fe chelating capacity of the iron-based desulfurization solution to be equal to 6.83-13.56 g/L at a redox potential of 0.185-0.3. The desulfurization performance of Fe (III)/Fe (II) chelating agents was investigated on a simulated sulfur-containing industrial gas composed of H2S and N2 in a cross-lfow rotating packed bed. Test results have revealed that the proposed iron-based desulfurization solution showed a sulfur removal efifciency of over 99%along with a Fe chelating capacity exceeding 1.35 g/L. This desulfurization technology which has practical application prospect is currently in the phase of commercial scale-up study.

  3. MOF catalysis of Fe(II)-to-Fe(III) reaction for an ultrafast and one-step generation of the Fe2O3@MOF composite and uranium(vi) reduction by iron(ii) under ambient conditions.

    Science.gov (United States)

    Xiong, Yang Yang; Li, Jian Qiang; Yan, Chang Sheng; Gao, Heng Ya; Zhou, Jian Ping; Gong, Le Le; Luo, Ming Biao; Zhang, Le; Meng, Pan Pan; Luo, Feng

    2016-08-07

    Herein, we demonstrate that Zn-MOF-74 enables the ultrafast and one-step generation of the Fe2O3@MOF composite once Zn-MOF-74 contacts with FeSO4 solution. This unique reaction can be further applied in catalysis of U(vi) reduction by Fe(ii) under ambient conditions. The results provide a highly renovated strategy for U(vi) reduction by Fe(ii) just under ambient conditions, which completely subvert all established methods about U(vi) reduction by Fe(ii) in which O2- and CO2-free conditions are absolutely required.

  4. Cr(III,Mn(II,Fe(III,Co(II,Ni(II,Cu(II and Zn(II Complexes with Diisobutyldithiocarbamato Ligand

    Directory of Open Access Journals (Sweden)

    Mohammad Tarique

    2011-01-01

    Full Text Available The synthesis of sulphur and nitrogen containing dithiocarbamato ligand derived from diisobutylamine as well as its coordination compounds with 3d series transition metals is presented. These synthesized compounds were characterized on the basis of elemental analysis, conductometric measurements and IR spectral studies. The analytical data showed the stoichiometry 1:2 and 1:3 for the compounds of the types ML2 {M=Mn(II, Co(II, Ni(II, Cu(II and Zn(II} and M'L3{M'=Cr(III and Fe(III} respectively. The conductometric measurements proved the non-electrolytic behaviour of all the compounds. The bidentate nature of dithiocarbamato moiety was confirmed on the basis of IR spectral data.

  5. Abiotic and microbial interactions during anaerobic transformations of Fe(II and NOx-

    Directory of Open Access Journals (Sweden)

    Flynn ePicardal

    2012-03-01

    Full Text Available Microbial Fe(II oxidation using NO3- as the terminal electron acceptor (nitrate-dependent Fe(II oxidation; NDFO has been studied for over 15 years. Although there are reports of autotrophic isolates and stable enrichments, many of the bacteria capable of NDFO are known organotrophic NO3- -reducers that require the presence of an organic, primary substrate, e.g., acetate, for significant amounts of Fe(II oxidation. Although the thermodynamics of Fe(II oxidation are favorable when coupled to either NO3- or NO2- reduction, the kinetics of abiotic Fe(II oxidation by NO3- are relatively slow except under special conditions. NDFO is typically studied in batch cultures containing millimolar concentrations of Fe(II, NO3-, and the primary substrate. In such systems, NO2- is often observed to accumulate in culture media during Fe(II oxidation. Compared to NO3-, abiotic reactions of biogenic NO2- and Fe(II are relatively rapid. The kinetics and reaction pathways of Fe(II oxidation by NO2- are strongly affected by medium composition and pH, reactant concentration, and the presence of Fe(II-sorptive surfaces, e.g., Fe(III oxyhydroxides and cellular surfaces. In batch cultures, the combination of abiotic and microbial Fe(II oxidation can alter product distribution and, more importantly, results in the formation of intracellular precipitates and extracellular Fe(III oxyhydroxide encrustations that apparently limit further cell growth and Fe(II oxidation. Unless steps are taken to minimize or account for potential abiotic reactions, results of microbial NDFO studies can be obfuscated by artifacts of the chosen experimental conditions, the use of inappropriate analytical methods, and the resulting uncertainties about the relative importance of abiotic and microbial reactions.In this manuscript, abiotic reactions of NO3- and NO2- with aqueous Fe2+, chelated Fe(II, and solid-phase Fe(II are reviewed along with factors that can influence overall NDFO reac

  6. Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides

    Science.gov (United States)

    White, A.F.; Peterson, M.L.

    1996-01-01

    Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25??C. For an aqueous transition metal m, such reactions are 3[Fe2+Fe3+2]O4(magnetite) + 2/nmz ??? 4[Fe3+2]O3(maghemite) + Fe2+ + 2/nmz-n and 3[Fe2+Ti]O3(ilmenite) + 2/nmz ??? Fe3+2Ti3O9(pseudorutile) + Fe2+ + 2/nmz-n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] ??? [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 ?? 10-10 mol m-2 s-1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe2+ is oxidized homogeneously in solution to Fe3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental

  7. One-step green synthesis of bimetallic Fe/Pd nanoparticles used to degrade Orange II

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Fang; Yang, Die; Chen, Zuliang, E-mail: zuliang.chen@newcastle.edu.au; Megharaj, Mallavarapu; Naidu, Ravendra

    2016-02-13

    Highlights: • Green synthesis of bimetallic Fe/Pd NPs was firstly reported using the one-step method. • 98.0% of Orange II was removed by Fe/Pd NPs, but only 16.0% by Fe NPs. • Fe/Pd NPs with a diameter ranging from 10 to 100 nm were observed. • Removing Orange II using Fe/Pd NPs involved both adsorption and catalytic degradation. - Abstract: To reduce cost and enhance reactivity, bimetallic Fe/Pd nanoparticles (NPs) were firstly synthesized using grape leaf aqueous extract to remove Orange II. Green synthesized bimetallic Fe/Pd NPs (98.0%) demonstrated a far higher ability to remove Orange II in 12 h compared to Fe NPs (16.0%). Meanwhile, all precursors, e.g., grape leaf extract, Fe{sup 2+} and Pd{sup 2+}, had no obvious effect on removing Orange II since less than 2.0% was removed. Kinetics study revealed that the removal rate fitted well to the pseudo-first-order reduction and pseudo-second-order adsorption model, meaning that removing Orange II via Fe/Pd NPs involved both adsorption and catalytic reduction. The remarkable stability of Fe/Pd NPs showed the potential application for removing azo dyes. Furthermore, Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) confirmed the changes in Fe/Pd NPs before and after reaction with Orange II. High Performance Liquid Chromatography–Mass Spectrum (HPLC–MS) identified the degraded products in the removal of Orange II, and finally a removal mechanism was proposed. This one-step strategy using grape leaf aqueous extract to synthesize Fe/Pd NPs is simple, cost-effective and environmentally benign, making possible the large-scale production of Fe/Pd NPs for field remediation.

  8. An extreme Fe II emitter the narrow line quasar PHL 1092

    CERN Document Server

    Bergeron, J

    1980-01-01

    A search for Fe II emission in a sample of radio-quiet quasars has revealed the outstanding properties of PHL 1092. Intense Fe II lines dominate the entire spectrum, and the Fe II UV multiplets are nearly as strong as the optical ones. In contrast the extreme weakness of the Balmer and Mg II lines is striking. For the first time, Fe I lines are identified in an extra-galactic object. The lines are narrow, with a FWHM of 1300 km s/sup -1/. The presence of Fe II UV lines and Fe I lines from the ground state requires moderate column densities. However Fe/sup 0/ can exist only in a region completely shielded from the UV continuum. The weakness of Mg II and H beta relative to Fe II lines is best explained by their thermalization. The emitting region is of high electron density n/sub e/ approximately=10/sup 12/ cm/sup -3/, low temperature T approximately=10000K, and has an optical depth in the Fe II UV lines tau /sub UV/ approximately=10/sup 3/-10/sup 4/. It is speculated that for higher densities all the lines wou...

  9. Fine-Structure FeII* Emission and Resonant MgII Emission in z = 1 Star-Forming Galaxies

    CERN Document Server

    Kornei, K A; Martin, C L; Coil, A L; Lotz, J M; Weiner, B J

    2013-01-01

    We present a study of the prevalence, strength, and kinematics of ultraviolet FeII and MgII emission lines in 212 star-forming galaxies at z = 1 selected from the DEEP2 survey. We find FeII* emission in composite spectra assembled on the basis of different galaxy properties, indicating that FeII* emission is prevalent at z = 1. In these composites, FeII* emission is observed at roughly the systemic velocity. At z = 1, we find that the strength of FeII* emission is most strongly modulated by dust attenuation, and is additionally correlated with redshift, star-formation rate, and [OII] equivalent width, such that systems at higher redshifts with lower dust levels, lower star-formation rates, and larger [OII] equivalent widths show stronger FeII* emission. We detect MgII emission in at least 15% of the individual spectra and we find that objects showing stronger MgII emission have higher specific star-formation rates, smaller [OII] linewidths, larger [OII] equivalent widths, lower dust attenuations, and lower st...

  10. A Crystal Structure of a Dimer of the Antibiotic Ramoplanin Illustrates Membrane Positioning and a Potential Lipid II Docking Interface

    Energy Technology Data Exchange (ETDEWEB)

    Hamburger, J.; Hoertz, A; Lee, A; Senturia, R; McCafferty, D; Loll, P

    2009-01-01

    The glycodepsipeptide antibiotic ramoplanin A2 is in late stage clinical development for the treatment of infections from Gram-positive pathogens, especially those that are resistant to first line antibiotics such as vancomycin. Ramoplanin A2 achieves its antibacterial effects by interfering with production of the bacterial cell wall; it indirectly inhibits the transglycosylases responsible for peptidoglycan biosynthesis by sequestering their Lipid II substrate. Lipid II recognition and sequestration occur at the interface between the extracellular environment and the bacterial membrane. Therefore, we determined the structure of ramoplanin A2 in an amphipathic environment, using detergents as membrane mimetics, to provide the most physiologically relevant structural context for mechanistic and pharmacological studies. We report here the X-ray crystal structure of ramoplanin A2 at a resolution of 1.4 {angstrom}. This structure reveals that ramoplanin A2 forms an intimate and highly amphipathic dimer and illustrates the potential means by which it interacts with bacterial target membranes. The structure also suggests a mechanism by which ramoplanin A2 recognizes its Lipid II ligand.

  11. Redox cycling of Fe(II) and Fe(III) in magnetite by Fe-metabolizing bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Byrne, James; Klueglein, Nicole; Pearce, Carolyn I.; Rosso, Kevin M.; Appel, Erwin; Kappler, Andreas

    2015-03-26

    Despite the regular occurrence of both magnetite and iron-metabolizing bacteria in the same environments, it is currently unknown whether the iron(II) and iron(III) in magnetite can be cycled between different bacteria and whether or how magnetic properties are affected by this metabolic activity. We show through magnetic and spectroscopic measurements that the phototrophic Fe(II)-oxidizer Rhodopseudomonas palustris TIE-1 can oxidize solid-phase magnetite nanoparticles using light energy, leading to a decrease in the measured magnetic susceptibility (MS). This process likely occurs at the surface and is reversible in the dark by the Fe(III)-reducer Geobacter sulfurreducens resulting in an increase in MS. These results show that iron ions bound in highly crystalline mineral magnetite are bioavailable as electron stores and electron sinks under varying environmental conditions, making magnetite a potential “biogeobattery” during day/night cycles. These findings are relevant for environmental studies and reinforce the impact of microbial redox processes on the global iron cycle.

  12. Fe II Emission in 14 Low-Redshift Quasars. I. Observations

    Science.gov (United States)

    Tsuzuki, Yumihiko; Kawara, Kimiaki; Yoshii, Yuzuru; Oyabu, Shinki; Tanabé, Toshihiko; Matsuoka, Yoshiki

    2006-10-01

    We present the spectra of 14 quasars with a wide coverage of rest wavelengths from 1000 to 7300 Å. The redshift ranges from z=0.061 to 0.555 and the luminosity from MB=-22.69 to -26.32. These spectra of high quality result from combining Hubble Space Telescope spectra with those taken from ground-based telescopes. We describe the procedure of generating the template spectrum of Fe II line emission from the spectrum of a narrow-line Seyfert 1 galaxy, I Zw 1, that covers two wavelength regions of 2200-3500 and 4200-5600 Å. Our template Fe II spectrum is semiempirical in the sense that the synthetic spectrum calculated with the CLOUDY photoionization code is used to separate the Fe II emission from the Mg II λ2798 line. The procedure of measuring the strengths of Fe II emission lines is twofold: (1) subtracting the continuum components by fitting models of the power-law and Balmer continua in the continuum windows, which are relatively free from line emissions, and (2) fitting models of the Fe II emission based on the Fe II template to the continuum-subtracted spectra. From 14 quasars including I Zw 1, we obtained the Fe II fluxes in five wavelength bands (U1 [2200-2660 Å], U2 [2660-3000 Å], U3 [3000-3500 Å], O1 [4400-4700 Å], and O2 [5100-5600 Å]), the total flux of Balmer continuum, and the fluxes of Mg II λ2798, Hα, and other emission lines, together with the full widths at half-maximum (FWHMs) of these lines. Regression analysis was performed by assuming a linear relation between any two of these quantities. Eight correlations were found with a confidence level higher than 99%: (1) larger Mg II FWHM for larger Hα FWHM, (2) larger Γ for fainter MB, (3) smaller Mg II FWHM for larger Γ, (4) larger Mg II FWHM for smaller Fe II(O1)/Mg II, (5) larger MBH for smaller Γ, (6) larger MBH for smaller Fe II(O1)/Mg II, (7) larger [O III]/Hβ for larger Mg II FWHM, and (8) larger Fe II(O1)/Mg II for larger Fe II(O1)/Fe II(U1). The fact that six of these eight are

  13. Anaerobic, Nitrate-Dependent Fe(II) Oxidation Under Advective Flow

    Science.gov (United States)

    Weber, K. A.; Coates, J. D.

    2005-12-01

    Microbially-catalyzed nitrate-dependent Fe(II) oxidation has been identified as a ubiquitous biogeochemical process contributing to anaerobic iron redox cycling in sedimentary environments. Most probable number enumeration revealed nitrate-dependent Fe(II) oxidizing microbial communities in groundwater and subsurface sediments in the order of 0 - 2.04 x 103 cells mL-1 and 2.39 x 102 - 1.17 x 103 cells (g wet sediment)-1, respectively. The efficacy of nitrate-dependent Fe(II) oxidation under advective flow was evaluated in a meso-scale column reactor packed with sterile low iron sand amended with subsurface sediments collected from the NABIR FRC background field site (10% mass/mass). Continuous flow of minimal medium mimicked the natural groundwater. Periodic FeCl2 and nitrate injections over a period of 49 days resulted in the retention of 95% of the iron (290 mmol). Extraction of solid-phase Fe revealed a net increase in Fe(III) of 160 mmol above background Fe(III) content indicating that 55% of the injected Fe(II) was oxidized. Differential solubility analysis of 0.5M HCl-extractable Fe and 3M HCl-extractable Fe indicated that the oxidation product was crystalline in nature as only 20% was soluble in 0.5M HCl. This formation of crystalline biogenic Fe(III) oxides is consistent with previous studies. Periodic injections of nitrate and acetate did not result in significant changes in Fe(II) or Fe(III) throughout a control column. Together these results demonstrate that native subsurface sediments harbor microbial communities capable of nitrate-dependent Fe(II) oxidation under advective flow. The biogenic formation of reactive Fe(III) oxide minerals capable of immobilizing heavy metals and radionuclides presents a plausible bioremediative strategy for contaminated subsurface environments.

  14. Clinical study on the influence of phloroglucinol on plasma angiotensin II and D-Dimer index in patients with severe pregnancy-induced hypertension.

    Science.gov (United States)

    Ai, Liang; Lan, Xinzhi; Wang, Limin; Xu, Yanjie; Zhang, Bin

    2016-07-01

    To observe the effect of phloroglucinol on plasma angiotensin II and D-dimer index when it was applied to patients with severe pregnancy-induced hypertension. 212 cases of severe pregnancy-induced hypertension patients diagnosed clinically were selected to be randomly divided into the research group and the control group. The research groups were given phloroglucinol, while the control groups were given magnesium sulfate. The plasma angiotensin II and D-dimer index in patients were detected before treatment and after 7 days respectively with statistical analysis of results. The diffidence after treatment was statistically significant (P0.05). It showed that the research group could reduce the plasma D-dimer and angiotensin II index in severe pregnancy-induced hypertension patients, and its effect was significantly better than the control group according to the plasma D-dimer and angiotensin II index changes in patients, it indicated that it was effective of phloroglucinol treatment for patients with pregnancy-induced hypertension disease and superior to the western medicine conventional treatment, worth clinical promotion.

  15. The Ca II triplet in red giant spectra: [Fe/H] determinations and the role of [Ca/Fe

    CERN Document Server

    Da Costa, G S

    2015-01-01

    Measurements are presented and analyzed of the strength of the Ca II triplet lines in red giants in Galactic globular and open clusters, and in a sample of red giants in the LMC disk that have significantly different [Ca/Fe] abundance ratios to the Galactic objects. The Galactic objects are used to generate a calibration between Ca II triplet line strength and [Fe/H], which is then used to estimate [Fe/H]_CaT for the LMC stars. The values are then compared with the [Fe/H]_spec determinations from high dispersion spectroscopy. After allowance for a small systematic offset the two abundance determinations are in excellent agreement. Further, as found in earlier studies, e.g., Battaglia et al. (2008), the difference is only a very weak function of the [Ca/Fe] ratio. For example, changing [Ca/Fe] from +0.3 to -0.2 causes the Ca II based abundance to underestimate [Fe/H]_spec by only ~0.15 dex, assuming a Galactic calibration. Consequently, the Ca II triplet approach to metallicity determinations can be used witho...

  16. Tuning through-bond Fe(III)/Fe(II) coupling by solvent manipulation of a central ruthenium redox couple.

    Science.gov (United States)

    Lin, Yu-Chen; Chen, Wei-Tin; Tai, Joe; Su, Denny; Huang, Sheng-Yi; Lin, Ingrid; Lin, Ju-Ling; Lee, Mandy M; Chiou, Mong Feng; Liu, Yen-Hsiang; Kwan, Ken-Shin; Chen, Yuan-Jang; Chen, Hsing-Yin

    2009-03-02

    The relationships between the intervalence energy (E(IT)) and the free energy difference (DeltaG) that exists between the minima of redox isomers (Fe(II)-Ru(III)/Fe(III)-Ru(II)) for various heterobimetallic complexes [(R-Fcpy)Ru(NH(3))(5)](2+/3+) (R = H, ethyl, Br, actyl; Fcpy = (4-pyridyl)ferrocenyl; Ru(NH(3))(5) = pentaam(m)ineruthenium) were examined. The changes in DeltaG for the complexes in various solvents were due to the effects of both solvent donicity and the substituents. The intervalence energy versus DeltaG, DeltaG approximately FDeltaE(1/2) (DeltaE(1/2) = E(1/2)(Fe(III/II)) - E(1/2)(Ru(III/II))), plots for the complexes in various solvents suggest a nuclear reorganization energy (lambda) of approximately 6000 cm(-1) (Chen et al. Inorg. Chem. 2000, 39, 189). For [(R-Fcpy)Ru(NH(3))(5)](2+) and [(et-Fcpy)Ru(NH(3))(4)(py)](2+) (Ru(NH(3))(4) = trans-tetraam(m)ineruthenium; py = pyridine) in various solvents, the E(1/2)(Ru(III/II)) of rutheniumam(m)ine typically was less than the E(1/2)(Fe(III/II)) of the ferrocenyl moiety. However, the low-donicity solvents resulted in relatively large values of E(1/2)(Ru(III/II)) for [(et-Fcpy)Ru(NH(3))(4)(py)](2+/3+/4+). Under our unique solvent conditions, a dramatic end-to-end interaction was observed for the trimetal cation, [(et-Fcpy)(2)Ru(NH(3))(4)](4+), in which the [(et-Fcpy)(2)Ru(NH(3))(4)](4+) included a central trans-tetraam(m)ineruthenium(III) and a terminal Fe(II)/Fe(III) pair. In general, results of electrochemical studies of [(et-Fcpy)(2)Ru(NH(3))(4)](2+) indicated both solvent-tunable E(1/2)(Ru(III/II)) (1 e(-)) and solvent-insensitive E(1/2)(Fe(III/II)) (2 e(-)) redox centers. However, in nitriles, two E(1/2)(Fe(III/II)) peaks were found with DeltaE(1/2)(Fe(III/II) - Fe(III/II)) ranging between 83 and 108 mV at a terminal metal-to-metal distance of up to 15.6 A. Furthermore, the bridging dpi orbital of the ruthenium center mediated efficient end-to-end interaction between the combinations of the terminal

  17. Speciative Determination of Dissolved Inorganic Fe(II, Fe(III and Total Fe in Natural Waters by Coupling Cloud Point Extraction with FAAS

    Directory of Open Access Journals (Sweden)

    Ramazan GÜRKAN

    2013-12-01

    Full Text Available A new cloud point extraction (CPE method for the preconcentration of trace iron speciation in natural waters prior to determination by flame atomic absorption spectrometry (FAAS was developed in the present study. In this method, Fe(II sensitively and selectively reacts with Calcon carboxylic acid (CCA in presence of cetylpyridinium chloride (CPC yielding a hydrophobic complex at pH 10.5, which is then entrapped in surfactant-rich phase. Total Fe was accurately and reliably determined after the reduction of Fe(III to Fe(II with sulfite. The amount of Fe(III in samples was determined from the difference between total Fe and Fe(II. CPC was used not only as an auxiliary ligand in CPE, but also as sensitivity enhancement agent in FAAS. The nonionic surfactant, polyethylene glycol tert-octylphenyl ether (Triton X-114 was used as an extracting agent. The analytical variables affecting CPE efficiency were investigated in detail. The preconcentration/enhancement factors of 50 and 82 respectively, were obtained for the preconcentration of Fe(II with 50 mL solution. Under the optimized conditions, the detection limit of Fe(II in linear range of 0.2-60 μg L-1 was 0.06 μg L-1. The relative standard deviation was 2.7 % (20 μg L-1, N: 5, recoveries for Fe(II were in range of 99.0-102.0% for all water samples including certified reference materials (CRMs. In order to verify its accuracy, two CRMs were analyzed and the results obtained were statistically in good agreement with the certified values.

  18. Synthesis, investigation and spectroscopic characterization of piroxicam ternary complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with glycine and DL-phenylalanine

    Science.gov (United States)

    Mohamed, Gehad G.; El-Gamel, Nadia E. A.

    2004-11-01

    The ternary piroxicam (Pir; 4-hydroxy-2-methyl- N-(2-pyridyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with various amino acids (AA) such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized by elemental analyses, molar conductance, IR, UV-Vis, magnetic moment, diffuse reflectance and X-ray powder diffraction. The UV-Vis spectra of Pir and the effect of metal chelation on the different interligand transitions are discussed in detailed manner. IR and UV-Vis spectra confirm that Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine- N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its carboxylic group, in addition PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its carboxylic and amino groups. All the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. The molar conductance data reveal that most of these chelates are non electrolytes, while Fe(III)-Pir-Gly, Co(II)-, Ni(II)-, Cu(II)- and Zn(II)-Pir-PhA cheletes were 1:1 electrolytes. X-ray powder diffraction is used as a new tool to estimate the crystallinity of chelates as well as to elucidate their geometrical structures.

  19. Role of Natural Organic Matter in Regulating the Partitioning of Fe(II, III) in Seawater

    Science.gov (United States)

    Guo, L.; Chen, M.; Roberts, K.; Santschi, P. H.

    2008-12-01

    Iron (Fe) is an essential micronutrient and plays an important role in controlling ocean productivity and carbon cycling. Fe has been shown to be mostly complexed with dissolved organic matter in seawater. However, the interaction of Fe with natural organic matter and how the quality and quantity of organic matter affect the chemical speciation of Fe in seawater remain poorly understood. Controlled laboratory experiments have been conducted to examine the partitioning of Fe(II, III) between dissolved, colloidal and particulate phases using radiotracers, model organic compounds, and ultrafiltration. In natural seawater, Fe is mostly partitioned in the colloidal and particulate phases, resulting in a logKd value of 7.3 and a logKc of 6.1, respectively. On average, about 25% of dissolved Fe-55 was found in the complexation of Fe with DOM could depress the bioavailability of Fe in seawater, the resultant Fe reduction may significantly enhance its solubility and bioavailability to marine organisms.

  20. Acid-tolerant microaerophilic Fe(II)-oxidizing bacteria promote Fe(III)-accumulation in a fen.

    Science.gov (United States)

    Lüdecke, Claudia; Reiche, Marco; Eusterhues, Karin; Nietzsche, Sandor; Küsel, Kirsten

    2010-10-01

    The ecological importance of Fe(II)-oxidizing bacteria (FeOB) at circumneutral pH is often masked in the presence of O(2) where rapid chemical oxidation of Fe(II) predominates. This study addresses the abundance, diversity and activity of microaerophilic FeOB in an acidic fen (pH ∼ 5) located in northern Bavaria, Germany. Mean O(2) penetration depth reached 16 cm where the highest dissolved Fe(II) concentrations (up to 140 µM) were present in soil water. Acid-tolerant FeOB cultivated in gradient tubes were most abundant (10(6) cells g(-1) peat) at the 10-20 cm depth interval. A stable enrichment culture was active at up to 29% O(2) saturation and Fe(III) accumulated 1.6 times faster than in abiotic controls. An acid-tolerant, microaerophilic isolate (strain CL21) was obtained which was closely related to the neutrophilic, lithoautotrophic FeOB Sideroxydans lithotrophicus strain LD-1. CL21 oxidized Fe(II) between pH 4 and 6.0, and produced nanoscale-goethites with a clearly lower mean coherence length (7 nm) perpendicular to the (110) plane than those formed abiotically (10 nm). Our results suggest that an acid-tolerant population of FeOB is thriving at redox interfaces formed by diffusion-limited O(2) transport in acidic peatlands. Furthermore, this well-adapted population is successfully competing with chemical oxidation and thereby playing an important role in the microbial iron cycle.

  1. Spiral Dinuclear Complexes of Tetradentate N(4) Diazine Ligands with Mn(II), Fe(II), Fe(III), Co(III), and Ni(II) Salts.

    Science.gov (United States)

    Xu, Zhiqiang; Thompson, Laurence K.; Miller, David O.; Clase, Howard J.; Howard, Judith A. K.; Goeta, Andrés E.

    1998-07-13

    A series of dinuclear complexes of the tetradentate dipyridyl-diazine ligand PAHAP with Mn(II), Fe(II), Fe(III), Co(III), and Ni(II) salts is reported in which three ligands wrap themselves around the six-coordinate metal centers in a rare spiral-like fashion. A similar Fe(II) complex is found for the dipyrazinyl-diazine ligand PZHPZ. The ligands are severely twisted with dihedral angles between the metal chelate ring mean planes on each ligand in the range 50-70 degrees, values close to the expected twist angle for orthogonality between the bridging nitrogen atom p orbitals. Full structures are reported for the dinuclear complexes [Mn(2)(PAHAP)(3)](ClO(4))(4).5H(2)O (1), [Fe(2)(PAHAP)(3)](NO(3))(4).3H(2)O (2), [Fe(2)(PZHPZ)(3)](NO(3))(4).5H(2)O (5), [Co(2)(PAHAP)(3)](NO(3))(6).5H(2)O (6), and [Ni(2)(PAHAP)(3)][Ni(H(2)O)(6)](NO(3))(6).4.5H(2)O (7). Other derivatives [Fe(2)(PAHAP)(3)](ClO(4))(4).4H(2)O (3), [Fe(2)(PAHAP)(3)](ClO(4))(6).4.5H(2)O (4), [Ni(2)(PAHAP)(3)](ClO(4))(4).5H(2)O (8), and [Fe(PHAAP-H)(H(2)O)(2)(NO(3))](NO(3))(2) (9) are also reported. Complex 1 crystallized in the monoclinic system, space group C2/c, with a = 13.4086(2) Å, b = 32.0249(1) Å, c = 14.3132(2) Å, alpha = 90 degrees, beta = 115.635(1) degrees, gamma = 90 degrees, and Z = 4. Complex 2 crystallized in the cubic system, space group Pa&thremacr;, with a = b = c = 21.0024(1) Å, alpha = beta = gamma = 90 degrees, and Z = 8. Complex 5 crystallized in the monoclinic system, space group P2/n, with a = 14.039(3) Å, b = 11.335(6) Å, c = 14.6517(15) Å, beta = 96.852(11) degrees, and Z = 1. Complex 6 crystallized in the trigonal system, space group R&thremacr;c(h), with a = b = 17.386(2) Å, c = 32.15(2) Å, alpha = beta = 90 degrees, gamma = 120 degrees, and Z = 4. Complex 7 crystallized in the trigonal system, space group R&thremacr;c, with a = b = 17.3737(3) Å, c = 33.235(6) Å, alpha = beta = 90 degrees, gamma = 120 degrees, and Z = 27. Weak ferromagnetic coupling was observed for 1

  2. Density functional perturbational orbital theory of spin polarization in electronic systems. II. Transition metal dimer complexes.

    Science.gov (United States)

    Seo, Dong-Kyun

    2007-11-14

    We present a theoretical scheme for a semiquantitative analysis of electronic structures of magnetic transition metal dimer complexes within spin density functional theory (DFT). Based on the spin polarization perturbational orbital theory [D.-K. Seo, J. Chem. Phys. 125, 154105 (2006)], explicit spin-dependent expressions of the spin orbital energies and coefficients are derived, which allows to understand how spin orbitals form and change their energies and shapes when two magnetic sites are coupled either ferromagnetically or antiferromagnetically. Upon employment of the concept of magnetic orbitals in the active-electron approximation, a general mathematical formula is obtained for the magnetic coupling constant J from the analytical expression for the electronic energy difference between low-spin broken-symmetry and high-spin states. The origin of the potential exchange and kinetic exchange terms based on the one-electron picture is also elucidated. In addition, we provide a general account of the DFT analysis of the magnetic exchange interactions in compounds for which the active-electron approximation is not appropriate.

  3. Oxygen dependency of neutrophilic Fe(II) oxidation by Leptothrix differs from abiotic reaction

    NARCIS (Netherlands)

    Vollrath, S.; Behrends, T.; Van Cappellen, P.

    2012-01-01

    Neutrophilic Fe(II) oxidizing microorganisms are found in many natural environments. It has been hypothesized that, at low oxygen concentrations, microbial iron oxidation is favored over abiotic oxidation. Here, we compare the kinetics of abiotic Fe(II) oxidation to oxidation in the presence of

  4. Adsorption and surface oxidation of Fe(II) on metal (hydr)oxides.

    NARCIS (Netherlands)

    Hiemstra, T.; Riemsdijk, van W.H.

    2007-01-01

    The Fe(II) adsorption by non-ferric and ferric (hydr)oxides has been analyzed with surface complexation modeling. The CD model has been used to derive the interfacial distribution of charge. The fitted CD coefficients have been linked to the mechanism of adsorption. The Fe(II) adsorption is

  5. Is optical Fe II emission related to the soft X-ray properties of quasars?

    Science.gov (United States)

    Wilkes, Belinda J.; Elvis, Martin; Mchardy, Ian

    1987-01-01

    Radio-quiet quasars generally show broad, blended multiplets of Fe II emission in their optical and UV spectra. Radio-loud quasars also show UV Fe II emission, but their optical Fe II emission is generally weaker. No satisfactory theory connecting the generation of Fe II and radio emission has been found to explain this effect. A second, well-established distinction between the two clases of quasar is in their X-ray properties: radio-loud quasars are more X-ray luminous, and recent results have shown that they also have systematically flatter soft X-ray slopes. Here it is proposed that the second effect causes the first; i.e., that the primary factor controlling the optical Fe II emission is the soft X-ray spectrum. This proposition is supported by X-ray and optical data for nine quasars, which shows a correlation between the soft X-ray slope and the strength of the optical Fe II emission. One of these quasars (1803+676) is radio-quiet, and yet its optical spectrum shows no evidence for Fe II emission. This quasar is also unusual in that it has a flat X-ray spectrum. This further supports the proposal that the X-ray spectrum is important in determining the relative strengths of UV and optical Fe II emission.

  6. Uptake and Release of Cerium During Fe-Oxide Formation and Transformation in Fe(II) Solutions

    DEFF Research Database (Denmark)

    Nedel, Sorin; Dideriksen, Knud; Christiansen, Bo C.

    2010-01-01

    microscopy revealed that it formed discrete nanocrystals of CeO2(s). These results demonstrate that Fe-oxide interaction with radionuclides is likely to depend strongly on the local redox conditions. By analogy with Ce, the trivalent actinides are not expected to be sequestered by preformed GR in anoxic......Fe-oxides are ubiquitous in soils and sediments and form during Fe(0) corrosion. Depending on redox conditions and solution composition, Fe-oxides such as ferrihydrite, goethite, magnetite, and green rust (GR) may form. These phases typically have high surface area and large affinity for adsorption...... of trace components. Further, Fe(II)-Fe(III) (hydr)oxides are redox active. Cerium, a member of the lanthanide family, can be used as an analogue for the tri- and tetra-valent actinides found in radioactive waste, expected to be stored in subsurface repositories. In experiments with ferrihydrite, Ce...

  7. Removal of Fe(II) from tap water by electrocoagulation technique

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, D.; Solanki, H. [Department of Chemical Engineering, Indian Institute of Technology, Guwahati 781039 (India); Purkait, M.K. [Department of Chemical Engineering, Indian Institute of Technology, Guwahati 781039 (India)], E-mail: mihir@iitg.ernet.in

    2008-06-30

    Electrocoagulation (EC) is a promising electrochemical technique for water treatment. In this work electrocoagulation (with aluminum as electrodes) was studied for iron Fe(II) removal from aqueous medium. Different concentration of Fe(II) solution in tap water was considered for the experiment. During EC process, various amorphous aluminum hydroxides complexes with high sorption capacity were formed. The removal of Fe(II) was consisted of two principal steps; (a) oxidation of Fe(II) to Fe(III) and (b) subsequent removal of Fe(III) by the freshly formed aluminum hydroxides complexes by adsorption/surface complexation followed by precipitation. Experiments were carried out with different current densities ranging from 0.01 to 0.04 A/m{sup 2}. It was observed that the removal of Fe(II) increases with current densities. Inter electrode distance was varied from 0.005 to 0.02 m and was found that least inter electrode distance is suitable in order to achieve higher Fe(II) removal. Other parameters such as conductivity, pH and salt concentration were kept constant as per tap water quality. Satisfactory iron removal of around 99.2% was obtained at the end of 35 min of operation from the initial concentration of 25 mg/L Fe(II). Iron concentration in the solution was determined using Atomic absorption spectrophotometer. By products obtained from the electrocoagulation bath were analyzed by SEM image and corresponding elemental analysis (EDAX). Cost estimation for the electrocoagulation was adopted and explained well. Up to 15 mg/L of initial Fe(II) concentration, the optimum total cost was 6.05 US$/m{sup 3}. The EC process for removing Fe(II) from tap water is expected to be adaptable for household use.

  8. Influences of Alkyl and Aryl Substituents on Iminopyridine Fe(II- and Co(II-Catalyzed Isoprene Polymerization

    Directory of Open Access Journals (Sweden)

    Lihua Guo

    2016-11-01

    Full Text Available A series of alkyl- and aryl-substituted iminopyridine Fe(II complexes 1a–7a and Co(II complexes 2b, 3b, 5b, and 6b were synthesized. The activator effect, influence of temperature, and, particularly, the alkyl and aryl substituents’ effect on catalytic activity, polymer molecular weight, and regio-/stereoselectivity were investigated when these complexes were applied in isoprene polymerization. All of the Fe(II complexes afforded polyisoprene with high molecular weight and moderate cis-1,4 selectivity. In contrast, the Co(II complexes produced polymers with low molecular weight and relatively high cis-1,4 selectivity. In the iminopyridine Fe(II system, the alkyl and aryl substituents’ effect exhibits significant variation on the isoprene polymerization. In the iminopyridine Co(II system, there is little influence observed on isoprene polymerization by alkyl and aryl substituents.

  9. Fe(II) sorption on a synthetic montmorillonite. A combined macroscopic and spectroscopic study.

    Science.gov (United States)

    Soltermann, Daniela; Fernandes, Maria Marques; Baeyens, Bart; Dähn, Rainer; Miehé-Brendlé, Jocelyne; Wehrli, Bernhard; Bradbury, Michael H

    2013-07-02

    Extended X-ray absorption fine structure (EXAFS) and Mössbauer spectroscopy combined with macroscopic sorption experiments were employed to investigate the sorption mechanism of Fe(II) on an iron-free synthetic montmorillonite (Na-IFM). Batch sorption experiments were performed to measure the Fe(II) uptake on Na-IFM at trace concentrations as a function of pH and as a function of sorbate concentration at pH 6.2 and 6.7 under anoxic conditions (O2 < 0.1 ppm). A two-site protolysis nonelectrostatic surface complexation and cation exchange sorption model was used to quantitatively describe the uptake of Fe(II) on Na-IFM. Two types of clay surface binding sites were required to model the Fe(II) sorption, the so-called strong (≡S(S)OH) and weak (≡S(W)OH) sites. EXAFS data show spectroscopic differences between Fe sorbed at low and medium absorber concentrations that were chosen to be characteristic for sorption on strong and weak sites, respectively. Data analysis indicates that Fe is located in the continuity of the octahedral sheet at trans-symmetric sites. Mössbauer spectroscopy measurements confirmed that iron sorbed on the weak edge sites is predominantly present as Fe(II), whereas a significant part of surface-bound Fe(III) was produced on the strong sites (∼12% vs ∼37% Fe(III) species to total sorbed Fe).

  10. Synthesis, spectral, electrochemical, crystal structure studies of two novel di-μ-halo-bis[halo(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)cadmium(II)] dimer complexes and their thermolysis to nanometal oxides

    Science.gov (United States)

    Warad, Ismail; Abdoh, Muneer; Shivalingegowda, Naveen; Lokanath, Neartur Krishnappagowda; Salghi, Rachid; Al-Nuri, Mohammed; Jodeh, Shehdeh; Radi, Smaail; Hammouti, Belkheir

    2015-11-01

    Two new neutral dimer Cadmium(II) complexes, [Cd2(dmdphphen)2X4] and where X = Cl (complex 1), Br (complex 2), and dmdphphen = 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, were synthesized and characterized by an elemental analysis, UV-Vis, IR, TG/DTA, CV and single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic system with the space group P-1 with unit cell parameters a = 10.1124(8) Å, b = 10.8875(8) Å, c = 11.5730(9) Å, α = 108.323(3)°, β = 107.010(3)°, γ = 91.260(3)° V = 1147.51(15) Å3 and Z = 1. The Cd(II) ions are located in a slightly distorted square-pyramidal geometry. The complexes exhibit a quasi-reversible one electron response at -570 mV vs. Cp2Fe/Cp2Fe+, which has been assigned Cd(II)/Cd(III) couples. TG/DTA result shows that these complexes are very stable and decomposed through one step reaction. Calcination of Complex 1, revealed the formation of Cubic nanoparticle CdO.

  11. One-step green synthesis of bimetallic Fe/Pd nanoparticles used to degrade Orange II.

    Science.gov (United States)

    Luo, Fang; Yang, Die; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

    2016-02-13

    To reduce cost and enhance reactivity, bimetallic Fe/Pd nanoparticles (NPs) were firstly synthesized using grape leaf aqueous extract to remove Orange II. Green synthesized bimetallic Fe/Pd NPs (98.0%) demonstrated a far higher ability to remove Orange II in 12h compared to Fe NPs (16.0%). Meanwhile, all precursors, e.g., grape leaf extract, Fe(2+) and Pd(2+), had no obvious effect on removing Orange II since less than 2.0% was removed. Kinetics study revealed that the removal rate fitted well to the pseudo-first-order reduction and pseudo-second-order adsorption model, meaning that removing Orange II via Fe/Pd NPs involved both adsorption and catalytic reduction. The remarkable stability of Fe/Pd NPs showed the potential application for removing azo dyes. Furthermore, Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) confirmed the changes in Fe/Pd NPs before and after reaction with Orange II. High Performance Liquid Chromatography-Mass Spectrum (HPLC-MS) identified the degraded products in the removal of Orange II, and finally a removal mechanism was proposed. This one-step strategy using grape leaf aqueous extract to synthesize Fe/Pd NPs is simple, cost-effective and environmentally benign, making possible the large-scale production of Fe/Pd NPs for field remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Molar Absorptivity and Concentration-Dependent Quantum Yield of Fe(II) Photo-Formation for the Aqueous Solutions of Fe(III)-Dicarboxylate Complexes

    Science.gov (United States)

    Hitomi, Y.; Arakaki, T.

    2009-12-01

    Redox cycles of iron in the aquatic environment affect formation of reactive oxygen species such as hydrogen peroxide and hydroxyl radicals, which in turn determines lifetimes of many organic compounds. Although aqueous Fe(III)-dicarboxylate complexes are considered to be important sources of photo-formed Fe(II), molar absorptivity and quantum yield of Fe(II) formation for individual species are not well understood. We initiated a study to characterize Fe(II) photo-formation from Fe(III)-dicarboxylates with the concentration ranges that are relevant to the natural aquatic environment. The Visual MINTEQ computer program was used to calculate the equilibrium concentrations of individual Fe(III)-dicarboxylate species. The molar absorptivity of Fe(III)-dicarboxylate species was obtained by UV-VIS spectrophotometer, and the product of the quantum yield and the molar absorptivity of Fe(III)-dicarboxylate species were obtained from photochemical experiments. These experimental data were combined with the calculated equilibrium Fe(III)-dicarboxylate concentrations to determine individual molar absorptivity and quantum yield of Fe(II) photo-formation for a specific Fe(III)-dicarboxylate species. We used initial concentrations of less than 10 micromolar Fe(III) to study the photochemical formation of Fe(II). Dicarboxylate compounds studied include oxalate, malonate, succinate, malate, and phthalate. We report molar absorptivity and concentration-dependent quantum yields of Fe(II) photo-formation of individual Fe(III)-dicarboxylates.

  13. Fe(II) sorption on pyrophyllite: Effect of structural Fe(III) (impurity) in pyrophyllite on nature of layered double hydroxide (LDH) secondary mineral formation

    Energy Technology Data Exchange (ETDEWEB)

    Starcher, Autumn N.; Li, Wei; Kukkadapu, Ravi K.; Elzinga, Evert J.; Sparks, Donald L.

    2016-11-01

    Fe(II)-Al(III)-LDH (layered double hydroxide) phases have been shown to form from reactions of aqueous Fe(II) with Fe-free Al-bearing minerals (phyllosilicate/clays and Al-oxides). To our knowledge, the effect of small amounts of structural Fe(III) impurities in “neutral” clays on such reactions, however, were not studied. In this study to understand the role of structural Fe(III) impurity in clays, laboratory batch studies with pyrophyllite (10 g/L), an Al-bearing phyllosilicate, containing small amounts of structural Fe(III) impurities and 0.8 mM and 3 mM Fe(II) (both natural and enriched in 57Fe) were carried out at pH 7.5 under anaerobic conditions (4% H2 – 96% N2 atmosphere). Samples were taken up to 4 weeks for analysis by Fe-X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy. In addition to the precipitation of Fe(II)-Al(III)-LDH phases as observed in earlier studies with pure minerals (no Fe(III) impurities in the minerals), the analyses indicated formation of small amounts of Fe(III) containing solid(s), most probably hybrid a Fe(II)-Al(III)/Fe(III)-LDH phase. The mechanism of Fe(II) oxidation was not apparent but most likely was due to interfacial electron transfer from the sorbed Fe(II) to the structural Fe(III) and/or surface-sorption-induced electron-transfer from the sorbed Fe(II) to the clay lattice. Increase in the Fe(II)/Al ratio of the LDH with reaction time further indicated the complex nature of the samples. This research provides evidence for the formation of both Fe(II)-Al(III)-LDH and Fe(II)-Fe(III)/Al(III)-LDH-like phases during reactions of Fe(II) in systems that mimic the natural environments. Better understanding Fe phase formation in complex laboratory studies will improve models of natural redox systems.

  14. Fe isotope fractionation during Fe(II) oxidation by the marine photoferrotroph Rhodovulum iodosum in the presence of Si - Implications for Precambrian iron formation deposition

    Science.gov (United States)

    Wu, Wenfang; Swanner, Elizabeth D.; Kleinhanns, Ilka C.; Schoenberg, Ronny; Pan, Yongxin; Kappler, Andreas

    2017-08-01

    The iron (Fe) isotopic composition of Precambrian iron formations (IFs), besides providing geological context through its mineralogical properties, was suggested to function as a biosignature that can be used to infer a potential microbial role in the formation of the deposited Fe minerals. Anoxygenic phototrophic Fe(II)-oxidizing bacteria (photoferrotrophs), capable of oxidizing Fe(II) anoxically using light energy, were potentially involved in Fe(II) oxidation in anoxic or suboxic Precambrian oceans. The effect of Si on Fe isotopic fractionation between aqueous Fe(II) and Fe-Si-co-precipitates has been investigated before. However, it is currently unknown how stable Fe isotopes are fractionated during enzymatic Fe(II) oxidation under marine hydrogeochemical conditions, and particularly how the presence of Si affects the Fe isotope composition and the isotopic exchange among different Fe phases. We therefore studied Fe isotope fractionation during Fe(II) oxidation by the marine photoferrotroph Rhodovulum iodosum in simulated Precambrian seawater amended with 1 mM dissolved Si. Our results show that the change in the Fe isotope compositions over time for both the initial aqueous Fe(II) (Feaq) and the Fe(III) precipitates (Feppt) follow a Rayleigh distillation model. Moreover, the fractionation (ε56Feppt-aq) determined independently from either δ56Feaq or δ56Feppt data resulted in a value of 2.3 ± 0.3 (2SD, N = 6). This value differs from the fractionation factor determined previously for Fe(II) oxidation by R. iodosum in the absence of Si, where the fractionation calculated from δ56Feaq (i.e. 0.96-1.18) was different from that calculated from δ56Feppt (1.96-1.98). This difference was attributed to isotopic exchange processes with soluble and sorbed Fe species. The present study suggests that Si present in Precambrian oceans retards Fe isotopic exchange, likely through combined effects of complexation of dissolved Fe species by Si and sorption of Si to Fe

  15. Enhancement effects of reducing agents on the degradation of tetrachloroethene in the Fe(II)/Fe(III) catalyzed percarbonate system

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Zhouwei [State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai 200237 (China); Soil, Water and Environmental Science Department, School of Earth and Environmental Sciences, The University of Arizona, 429 Shantz Building, Tucson, AZ 85721 (United States); Gu, Xiaogang [State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai 200237 (China); Lu, Shuguang, E-mail: lvshuguang@ecust.edu.cn [State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai 200237 (China); Brusseau, Mark L. [Soil, Water and Environmental Science Department, School of Earth and Environmental Sciences, The University of Arizona, 429 Shantz Building, Tucson, AZ 85721 (United States); Yan, Ni [Hydrology and Water Resources Department, School of Earth and Environmental Sciences, University of Arizona, 429 Shantz Building, Tucson, AZ 85721 (United States); Qiu, Zhaofu; Sui, Qian [State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai 200237 (China)

    2015-12-30

    Highlights: • PCE degradation by reducing-agent modified Fe-catalyzed percarbonate was studied. • The addition of reducing agents significantly increased PCE degradation. • Hydroxylamine hydrochloride showed the best effect on enhancing PCE degradation. • The primary PCE degradation mechanism was oxidation by hydroxyl radical. • O{sub 2}·{sup −} participated in the degradation of PCE in reducing-agent modified system. - Abstract: In this study, the effects of reducing agents on the degradation of tetrachloroethene (PCE) were investigated in the Fe(II)/Fe(III) catalyzed sodium percarbonate (SPC) system. The addition of reducing agents, including hydroxylamine hydrochloride, sodium sulfite, ascorbic acid and sodium ascorbate, accelerated the Fe(III)/Fe(II) redox cycle, leading to a relatively steady Fe(II) concentration and higher production of free radicals. This, in turn, resulted in enhanced PCE oxidation by SPC, with almost complete PCE removal obtained for appropriate Fe and SPC concentrations. The chemical probe tests, using nitrobenzene and carbon tetrachloride, demonstrated that HO· was the predominant radical in the system and that O{sub 2}·{sup −} played a minor role, which was further confirmed by the results of electron spin resonance measurements. PCE degradation decreased significantly with the addition of isopropanol, a HO· scavenger, supporting the hypothesis that HO· was primarily responsible for PCE degradation. It is noteworthy that Cl{sup −} release was slightly delayed in the first 20 min, indicating that intermediate products were produced. However, these intermediates were further degraded, resulting in the complete conversion of PCE to CO{sub 2}. In conclusion, the use of reducing agents to enhance Fe(II)/Fe(III) catalyzed SPC oxidation appears to be a promising approach for the rapid degradation of organic contaminants in groundwater.

  16. Heterogeneous Reduction of PuO2 with Fe(II): Importance of the Fe(III) Reaction Product

    Energy Technology Data Exchange (ETDEWEB)

    Felmy, Andrew R.; Moore, Dean A.; Rosso, Kevin M.; Qafoku, Odeta; Rai, Dhanpat; Buck, Edgar C.; Ilton, Eugene S.

    2011-05-01

    Abstract Heterogeneous reduction of actinides in higher and more soluble oxidation states to lower more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO2(am) by Fe(II). We present the first experimental evidence that reduction of PuO2(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time-dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) [(Pu(III) + Pu(IV)) - Pu(IV)] by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II).

  17. What controls the FeII strength in active galactic nuclei?

    CERN Document Server

    Dong, Xiaobo; Wang, Tinggui; Wang, Huiyuan; Fan, Xiaohui; Zhou, Hongyan; Yuan, Weimin

    2009-01-01

    We have investigated the correlations of the equivalent widths (EWs) of narrow and broad FeII emission lines and the FeII/MgII intensity ratio with fundamental physical parameters of active galactic nuclei (AGNs), luminosity (L), black hole mass (M_{BH}) and Eddington ratio (L/Ledd), using a homogenous sample of z<0.8 Seyfert 1 galaxies and QSOs in the spectroscopic data set of Sloan Digital Sky Survey Fourth Data Release (SDSS DR4). The sample comprises 4178 spectra that are selected to suffer little from the host-galaxy starlight contamination. We find that the strongest correlations of almost all the emission-line intensity ratios and EWs are with L/Ledd, either positively (e.g. FeII EW) or negatively (e.g. MgII EW), rather than with L or M_{BH}; In particular, the intensity ratios of both the ultraviolet and optical FeII emissions to MgII 2800 correlate quite tightly with L/Ledd (e.g., Spearman r_s = 0.74 for the [narrow FeII]/MgII -- L/Ledd correlation). We have also investigated the FeII emission in ...

  18. TRANSFORMATION OF NITROSOBENZENES AND HYDROXYLANILINES BY FE II SPECIES: ELUCIDATION OF MECHANISM, EFFECT OF FERRIC OXIDES AND PH

    Science.gov (United States)

    Nitrosobenzenes, the first intermediates in the reduction of nitrobenzenes, were reduced by Fe(II) solutions as well as by Fe(II)-treated goethite suspensions (Fe(II)/G). Results indicate a reactivity trend in which electron-withdrawing groups in the para position increased the ...

  19. Physiology and Mechanism of Phototrophic Fe(II) Oxidation by Rhodopseudomonas palustris TIE-1

    Science.gov (United States)

    Jiao, Y.; Newman, D.

    2007-12-01

    Phototrophic Fe(II)-oxidizing bacteria use electrons from ferrous iron [Fe(II)] and energy from light to drive reductive CO2 fixation. This metabolism is thought to be ancient in origin, and plays an important role in environmental iron cycling. It has been implicated in the deposition of Banded Iron Formations, a class of ancient sedimentary iron deposits. Consistent with this hypothesis, we discovered that hydrogen gas, a thermodynamically favorable electron donor to Fe(II), in an Archean atmosphere would not have inhibited phototrophic Fe(II) oxidation. To understand this physiology and the connection to BIF formation at the molecular level, the mechanisms of phototrophic Fe(II) oxidation were examined in a model organism Rhodopseudomonas palustris TIE-1. Increased expression of a putative decaheme c-type cytochrome, encoded by pioA, was observed when cells were grown under Fe(II)-oxidizing conditions. Two genes located immediately downstream of pioA in the same operon, pioB and pioC, encode a putative outer membrane beta-barrel protein and a putative high potential iron-sulfur protein, respectively. Deletion studies demonstrated that all three genes are involved in phototrophic Fe(II) oxidation. This study provides our first insight into the molecular mechanisms of this metabolism, which will be further characterized by in vitro biochemical studies.

  20. Peptide-based FeS4 complexes: the zinc ribbon fold is unsurpassed to stabilize both the FeII and FeIII states.

    Science.gov (United States)

    Jacques, Aurélie; Latour, Jean-Marc; Sénèque, Olivier

    2014-03-14

    Whereas Zn(Cys)4 zinc fingers exist with different protein folds, only the zinc ribbon fold is found in rubredoxin Fe(Cys)4 sites. To assess the significance of this observation, we have investigated the binding and stability of Fe(2+) and Fe(3+) ions by a set of four peptides designed to model Zn(Cys)4 zinc fingers with various folds, i.e. zinc ribbon, treble clef and a loosened zinc ribbon fold. All peptides were shown by means of UV-Vis and CD spectroscopies to form stable 1 : 1 Fe(II)/peptide complexes with binding constants higher than 10(7) M(-1) at pH 7. Their oxidation into Fe(III) complexes and the stability of the latter were compared. The UV-Vis absorption and CD spectroscopic properties of the Fe(II) and Fe(III) complexes were analysed with respect to the structures of the zinc analogues in order to get insight into the local arrangement of the Fe(Cys)4 core around the metal ion. The chemical stability of these complexes was rationalized according to the shielding from the solvent provided by the various peptide folds to the FeS4 core. In addition, we showed that whereas UV-visible spectra inform only on the FeS4, the information derived from the corresponding CD spectra extend to the Cβ orientation and the peptide fold. The results presented here demonstrate that while the zinc ribbon fold is not strictly required to obtain a Fe(Cys)4 site, it affords a drastically superior protection of the site toward external redox agents. This finding brings new clues to engineer stable and redox-active Fe(Cys)4 sites in de novo proteins.

  1. Uptake and Release of Cerium During Fe-Oxide Formation and Transformation in Fe(II) Solutions

    DEFF Research Database (Denmark)

    Nedel, Sorin; Dideriksen, Knud; Christiansen, Bo C.

    2010-01-01

    Fe-oxides are ubiquitous in soils and sediments and form during Fe(0) corrosion. Depending on redox conditions and solution composition, Fe-oxides such as ferrihydrite, goethite, magnetite, and green rust (GR) may form. These phases typically have high surface area and large affinity for adsorption...... of trace components. Further, Fe(II)-Fe(III) (hydr)oxides are redox active. Cerium, a member of the lanthanide family, can be used as an analogue for the tri- and tetra-valent actinides found in radioactive waste, expected to be stored in subsurface repositories. In experiments with ferrihydrite, Ce......(III) release. X-ray photoelectron spectroscopy revealed Ce(III) adsorbed on magnetite. When Fe-oxides were synthesized by air oxidation of Fe(II) solutions at pH 7, GR(Na,SO4) played a catalytic role in the oxidation of Ce(III) to Ce(IV) by O-2, removing more than 90% of the dissolved Ce. Transmission electron...

  2. Variability of Fe II in Two NLS1s, PG 1700+815 and NGC 4051

    Indian Academy of Sciences (India)

    Weihao Bian; Zhen Yang

    2011-03-01

    We analyze the spectral variability for two narrow line Seyfert 1 galaxies, PG 1700+518 and NGC 4051 using the spectral decomposition method. We focus on their optical Fe II variability to investigate the origin of Fe II in AGNs. For PG 1700+518, we find that the Fe II size is about 200 light-days, which is consistent with the H size derived from the empirical R–L relation. For NGC 4051, the [O III] 5007 Å flux is strongly correlated with continuum flux, suggesting that we should recalibrate the spectral flux on a scale defined by [O III] flux. The corrected light curves of Fe II, H, He II, (5100 Å) are given here. A detailed analysis will be given in the near future.

  3. Stable iron isotope fractionation between aqueous Fe(II) and model Archean ocean Fe-Si coprecipitates and implications for iron isotope variations in the ancient rock record

    Science.gov (United States)

    Wu, Lingling; Percak-Dennett, Elizabeth M.; Beard, Brian L.; Roden, Eric E.; Johnson, Clark M.

    2012-05-01

    Iron isotope fractionation between aqueous Fe(II) (Fe(II)aq) and two amorphous Fe(III) oxide-Si coprecipitates was investigated in an aqueous medium that simulated Archean marine conditions, including saturated amorphous silica, low sulfate, and zero dissolved oxygen. The equilibrium isotope fractionation (in 56Fe/54Fe) between Fe(II)aq and Fe(III)-Si coprecipitates at circum-neutral pH, as inferred by the three-isotope method, was -3.51 ± 0.20 (2σ)‰ and -3.99 ± 0.17 (2σ)‰ for coprecipitates that had Fe:Si molar ratios of 1:2 and 1:3, respectively. These results, when combined with earlier work, indicate that the equilibrium isotope fractionation factor between Fe(II)aq and Fe(III)-Si coprecipitates changes as a function of Fe:Si ratio of the solid. Isotopic fractionation was least negative when Fe:Si = 1:1 and most negative when Fe:Si = 1:3. This change corresponds with changes in the local structure of iron, as revealed by prior spectroscopic studies. The kinetics of isotopic exchange was controlled by movement of Fe(II) and Si, where sorption of Fe(II) from aqueous to solid phase facilitated atom exchange, but sorption of Si hindered isotopic exchange through blockage of reactive surface sites. Although Fe(II)-Fe(III) isotopic exchange rates were a function of solid and solution compositions in the current study, in all cases they were much higher than that determined in previous studies of aqueous Fe(III) and ferrihydrite interaction, highlighting the importance of electron exchange in promoting Fe atom exchange. When compared to analogous microbial reduction experiments of overlapping Fe(II) to Fe(III) ratios, isotopic exchange rates were faster in the biological experiments, likely due to promotion of atom exchange by the solid-phase Fe(II) produced in the biological experiments. These results provide constraints for interpreting the relatively large range of Fe isotope compositions in Precambrian marine sedimentary rocks, and highlight important

  4. Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(III)/Fe(II) cycle with hydroxylamine.

    Science.gov (United States)

    Zou, Jing; Ma, Jun; Chen, Liwei; Li, Xuchun; Guan, Yinghong; Xie, Pengchao; Pan, Chao

    2013-10-15

    The reaction between ferrous iron (Fe(II)) with peroxymonosulfate (PMS) generates reactive oxidants capable of degrading refractory organic contaminants. However, the slow transformation from ferric iron (Fe(III)) back to Fe(II) limits its widespread application. Here, we added hydroxylamine (HA), a common reducing agent, into Fe(II)/PMS process to accelerate the transformation from Fe(III) to Fe(II). With benzoic acid (BA) as probe compound, the addition of HA into Fe(II)/PMS process accelerated the degradation of BA rapidly in the pH range of 2.0-6.0 by accelerating the key reactions, including the redox cycle of Fe(III)/Fe(II) and the generation of reactive oxidants. Both sulfate radicals and hydroxyl radicals were considered as the primary reactive oxidants for the degradation of BA in HA/Fe(II)/PMS process with the experiments of electron spin resonance and alcohols quenching. Moreover, HA was gradually degraded to N2, N2O, NO2 (−), and NO3 (−), while the environmentally friendly gas of N2 was considered as its major end product in the process. The present study might provide a promising idea based on Fe(II)/PMS process for the rapid degradation of refractory organic contaminants in water treatment.

  5. Evidence for Fluorescent Fe II Emission from Extended Low Ionization Outflows in Obscured Quasars

    Science.gov (United States)

    Wang, Tinggui; Ferland, Gary J.; Yang, Chenwei; Wang, Huiyuan; Zhang, Shaohua

    2016-06-01

    Recent studies have shown that outflows in at least some broad absorption line (BAL) quasars are extended well beyond the putative dusty torus. Such outflows should be detectable in obscured quasars. We present four WISE selected infrared red quasars with very strong and peculiar ultraviolet Fe ii emission lines: strong UV Fe ii UV arising from transitions to ground/low excitation levels, and very weak Fe ii at wavelengths longer than 2800 Å. The spectra of these quasars display strong resonant emission lines, such as C iv, Al iii and Mg ii but sometimes, a lack of non-resonant lines such as C iii], S iii and He ii. We interpret the Fe ii lines as resonantly scattered light from the extended outflows that are viewed nearly edge-on, so that the accretion disk and broad line region are obscured by the dusty torus, while the extended outflows are not. We show that dust free gas exposed to strong radiation longward of 912 Å produces Fe ii emission very similar to that observed. The gas is too cool to collisionally excite Fe ii lines, accounting for the lack of optical emission. The spectral energy distribution from the UV to the mid-infrared can be modeled as emission from a clumpy dusty torus, with UV emission being reflected/scattered light either by the dusty torus or the outflow. Within this scenario, we estimate a minimum covering factor of the outflows from a few to 20% for the Fe ii scattering region, suggesting that Fe ii BAL quasars are at a special stage of quasar evolution.

  6. Characterization of β-FeSi II films as a novel solar cell semiconductor

    Science.gov (United States)

    Fukuzawa, Yasuhiro; Ootsuka, Teruhisa; Otogawa, Naotaka; Abe, Hironori; Nakayama, Yasuhiko; Makita, Yunosuke

    2006-04-01

    β-FeSi II is an attractive semiconductor owing to its extremely high optical absorption coefficient (α>10 5 cm -1), and is expected to be an ideal semiconductor as a thin film solar cell. For solar cell use, to prepare high quality β-FeSi II films holding a desired Fe/Si ratio, we chose two methods; one is a molecular beam epitaxy (MBE) method in which Fe and Si were evaporated by using normal Knudsen cells, and occasionally by e-gun for Si. Another one is the facing-target sputtering (FTS) method in which deposition of β-FeSi II films is made on Si substrate that is placed out of gas plasma cloud. In both methods to obtain β-FeSi II films with a tuned Fe/Si ratio, Fe/Si super lattice was fabricated by varying Fe and Si deposition thickness. Results showed significant in- and out-diffusion of host Fe and Si atoms at the interface of Si substrates into β-FeSi II layers. It was experimentally demonstrated that this diffusion can be suppressed by the formation of template layer between the epitaxial β-FeSi II layer and the substrate. The template layer was prepared by reactive deposition epitaxy (RDE) method. By fixing the Fe/Si ratio as precisely as possible at 1/2, systematic doping experiments of acceptor (Ga and B) and donor (As) impurities into β-FeSi II were carried out. Systematical changes of electron and hole carrier concentration in these samples along variation of incorporated impurities were observed through Hall effect measurements. Residual carrier concentrations can be ascribed to not only the remaining undesired impurities contained in source materials but also to a variety of point defects mainly produced by the uncontrolled stoichiometry. A preliminary structure of n-β-FeSi II/p-Si used as a solar cell indicated a conversion efficiency of 3.7%.

  7. Evidence for the Existence of Autotrophic Nitrate-Reducing Fe(II)-Oxidizing Bacteria in Marine Coastal Sediment.

    Science.gov (United States)

    Laufer, Katja; Røy, Hans; Jørgensen, Bo Barker; Kappler, Andreas

    2016-10-15

    Nitrate-reducing Fe(II)-oxidizing microorganisms were described for the first time ca. 20 years ago. Most pure cultures of nitrate-reducing Fe(II) oxidizers can oxidize Fe(II) only under mixotrophic conditions, i.e., when an organic cosubstrate is provided. A small number of nitrate-reducing Fe(II)-oxidizing cultures have been proposed to grow autotrophically, but unambiguous evidence for autotrophy has not always been provided. Thus, it is still unclear whether or to what extent Fe(II) oxidation coupled to nitrate reduction is an enzymatically catalyzed and energy-yielding autotrophic process or whether Fe(II) is abiotically oxidized by nitrite from heterotrophic nitrate reduction. The aim of the present study was to find evidence for the existence of autotrophic nitrate-reducing Fe(II) oxidizers in coastal marine sediments. Microcosm incubations showed that with increasing incubation times, the stoichiometric ratio of reduced nitrate/oxidized Fe(II) [NO3(-)reduced/Fe(II)oxidized] decreased, indicating a decreasing contribution of heterotrophic denitrification and/or an increasing contribution of autotrophic nitrate-reducing Fe(II) oxidation over time. After incubations of sediment slurries for >10 weeks, nitrate-reducing activity ceased, although nitrate was still present. This suggests that heterotrophic nitrate reduction had ceased due to the depletion of readily available organic carbon. However, after the addition of Fe(II) to these batch incubation mixtures, the nitrate-reducing activity resumed, and Fe(II) was oxidized, indicating the activity of autotrophic nitrate-reducing Fe(II) oxidizers. The concurrent reduction of (14)C-labeled bicarbonate concentrations unambiguously proved that autotrophic C fixation occurred during Fe(II) oxidation and nitrate reduction. Our results clearly demonstrated that autotrophic nitrate-reducing Fe(II)-oxidizing bacteria were present in the investigated coastal marine sediments.

  8. Effect of Iron Fe (II and Fe (III in a Binary System Evaluated Bioluminescent Method

    Directory of Open Access Journals (Sweden)

    Elena Sorokina

    2013-01-01

    Full Text Available The effect of iron ions Fe2+ and Fe3+ on the bioluminescent recombinant strain of Escherichia coli in a single-component and binary system. Found that for the bacteria E. coli Fe3+ ions are more toxic than Fe2+. Under the combined effect of iron toxicity increases, the percentage of luminescence quenching increases, but the value is much less than the sum of the indicator for the Fe2+ and Fe3+. The biological effect of insertion of iron is not proportional to their content in the mixture.

  9. Phototrophic Fe(II-oxidation in the chemocline of a ferruginous meromictic lake

    Directory of Open Access Journals (Sweden)

    Xavier Alexis eWalter

    2014-12-01

    Full Text Available Precambrian Banded Iron Formation (BIF deposition was conventionally attributed to the precipitation of iron-oxides resulting from the abiotic reaction of ferrous iron (Fe(II with photosynthetically-produced oxygen. Earliest traces of oxygen date from 2.7 Ga, thus raising questions as to what may have caused BIF precipitation before oxygenic photosynthesis evolved. The discovery of anoxygenic phototrophic bacteria thriving through the oxidation of Fe(II has provided support for a biological origin for some BIFs, but despite reports suggesting that anoxygenic phototrophs may oxidize Fe(II in the environment, a model ecosystem of an ancient ocean where they are demonstrably active was lacking. Here we show that anoxygenic phototrophic bacteria contribute to Fe(II oxidation in the water column of the ferruginous sulfate-poor, meromictic lake La Cruz (Spain. We observed in-situ photoferrotrophic activity through stimulation of phototrophic carbon uptake in the presence of Fe(II, and determined light-dependent Fe(II-oxidation by the natural chemocline microbiota. Moreover, a photoferrotrophic bacterium most closely related to Chlorobium ferrooxidans was enriched from the ferruginous water column. Our study for the first time demonstrates a direct link between anoxygenic photoferrotrophy and the anoxic precipitation of Fe(III-oxides in a ferruginous water column, providing a plausible mechanism for the bacterial origin of BIF’s before the advent of free oxygen.

  10. Mtr Extracellular Electron Transfer Pathways in Fe(III)-reducing or Fe(II)-oxidizing Bacteria: A Genomic Perspective

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Liang; Rosso, Kevin M.; Zachara, John M.; Fredrickson, Jim K.

    2012-12-01

    Originally discovered in the dissimilatory metal-reducing bacterium Shewanella oneidensis MR-1 (MR-1), the Mtr (i.e., metal-reducing) pathway exists in all characterized strains of metal-reducing Shewanella. The protein components identified to date for the Mtr pathway of MR-1 include four multi-heme c-type cytochromes (c-Cyts), CymA, MtrA, MtrC and OmcA, and a porin-like, outer membrane protein MtrB. They are strategically positioned along the width of the MR-1 cell envelope to mediate electron transfer from the quinone/quinol pool in the inner-membrane to the Fe(III)-containing minerals external to the bacterial cells. A survey of microbial genomes revealed homologues of the Mtr pathway in other dissimilatory Fe(III)-reducing bacteria, including Aeromonas hydrophila, Ferrimonas balearica and Rhodoferax ferrireducens, and in the Fe(II)-oxidizing bacteria Dechloromonas aromatica RCB, Gallionella capsiferriformans ES-2 and Sideroxydans lithotrophicus ES-1. The widespread distribution of Mtr pathways in Fe(III)-reducing or Fe(II)-oxidizing bacteria emphasizes the importance of this type of extracellular electron transfer pathway in microbial redox transformation of Fe. Their distribution in these two different functional groups of bacteria also emphasizes the bi-directional nature of electron transfer reactions carried out by the Mtr pathways. The characteristics of the Mtr pathways may be shared by other pathways used by microorganisms for exchanging electrons with their extracellular environments.

  11. Selection of Chelated Fe (III)/Fe (II) Catalytic Oxidation Agents for Desulfurization Based on Iron Complexation Method

    Institute of Scientific and Technical Information of China (English)

    Luo Ying; Liu Youzhi; Qi Guisheng; Guo Huidong; Zhu Zhengfeng

    2014-01-01

    Optimization of factors inlfuencing the experiments on reactions involving 8 different chelating agents and sol-uble Fe (III)/Fe (II) salts was carried out to yield chelated iron complexes. A combination of optimized inlfuencing factors has resulted in a Fe chelating capacity of the iron-based desulfurization solution to be equal to 6.83—13.56 g/L at a redox potential of 0.185—0.3. The desulfurization performance of Fe (III)/Fe (II) chelating agents was investigated on a simulated sulfur-containing industrial gas composed of H2S and N2 in a cross-lfow rotating packed bed. Test results have revealed that the proposed iron-based desulfurization solution showed a sulfur removal efifciency of over 99%along with a Fe chelating capacity exceeding 1.35 g/L. This desulfurization technology which has practical application prospect is currently in the phase of commercial scale-up study.

  12. Experimental study on NO oxidation by K2S2O8 + Fe(II)EDTA

    Science.gov (United States)

    Hu, Hui; Huang, Hao; Tao, Gong-Kai; Xie, Jing; Yang, Cheng; Huang, Ting

    2017-06-01

    NO absorption and oxidation by K2S2O8 + Fe(II)EDTA system was studied in a lab-scale bubble reactor. The effects of different additives, reaction temperatures, pH values, K2S2O8 and Fe(II)EDTA concentrations on NO conversion were systematic investigated. Results indicated that NO conversion rate of K2S2O8 + Fe(II)EDTA system increased to 91.6% when concentrations of K2S2O8 and Fe(II)EDTA were both 30 mmol/L at 80 °C. NO conversion rate was positively correlated with the SO42- concentration in absorption solution, and it kept around 80% in a wide pH range, which made this technology to be a promising method for the denitrification of coal-fired flue gas.

  13. Heterotrimetallic coordination polymers: {Cu(II)Ln(III)Fe(III)} chains and {Ni(II)Ln(III)Fe(III)} layers: synthesis, crystal structures, and magnetic properties.

    Science.gov (United States)

    Alexandru, Maria-Gabriela; Visinescu, Diana; Andruh, Marius; Marino, Nadia; Armentano, Donatella; Cano, Joan; Lloret, Francesc; Julve, Miguel

    2015-03-27

    The use of the [Fe(III) (AA)(CN)4](-) complex anion as metalloligand towards the preformed [Cu(II) (valpn)Ln(III)](3+) or [Ni(II) (valpn)Ln(III) ](3+) heterometallic complex cations (AA=2,2'-bipyridine (bipy) and 1,10-phenathroline (phen); H2 valpn=1,3-propanediyl-bis(2-iminomethylene-6-methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[Cu(II) (valpn)Ln(III) (H2O)3 (μ-NC)2 Fe(III) (phen)(CN)2 {(μ-NC)Fe(III) (phen)(CN)3}]NO3 ⋅7 H2O}n (Ln=Gd (1), Tb (2), and Dy (3)) and the trinuclear complex [Cu(II) (valpn)La(III) (OH2 )3 (O2 NO)(μ-NC)Fe(III) (phen)(CN)3 ]⋅NO3 ⋅H2O⋅CH3 CN (4) were obtained with the [Cu(II) (valpn)Ln(III)](3+) assembling unit, whereas three isostructural heterotrimetallic 2D networks, {[Ni(II) (valpn)Ln(III) (ONO2 )2 (H2 O)(μ-NC)3 Fe(III) (bipy)(CN)]⋅2 H2 O⋅2 CH3 CN}n (Ln=Gd (5), Tb (6), and Dy (7)) resulted with the related [Ni(II) (valpn)Ln(III) ](3+) precursor. The crystal structure of compound 4 consists of discrete heterotrimetallic complex cations, [Cu(II) (valpn)La(III) (OH2)3 (O2 NO)(μ-NC)Fe(III) (phen)(CN)3 ](+), nitrate counterions, and non-coordinate water and acetonitrile molecules. The heteroleptic {Fe(III) (bipy)(CN)4} moiety in 5-7 acts as a tris-monodentate ligand towards three {Ni(II) (valpn)Ln(III)} binuclear nodes leading to heterotrimetallic 2D networks. The ferromagnetic interaction through the diphenoxo bridge in the Cu(II)-Ln(III) (1-3) and Ni(II)-Ln(III) (5-7) units, as well as through the single cyanide bridge between the Fe(III) and either Ni(II) (5-7) or Cu(II) (4) account for the overall ferromagnetic behavior observed in 1-7. DFT-type calculations were performed to substantiate the magnetic interactions in 1, 4, and 5. Interestingly, compound 6 exhibits slow relaxation of the magnetization with maxima of the out-of-phase ac signals below 4.0 K in the lack of a dc field, the values of the pre

  14. Determination of Total Iron as Fe(II) in Multivitamins, Haematinics ...

    African Journals Online (AJOL)

    The determination of total iron in pharmaceutical products and natural waters as Fe(II) ... as a [Fe(phen)32+] complex at 515 nm with a UV/Vis spectrophotometer. The linear range of the system is between 1 and 60 mg/l with a detection limit of ...

  15. NO and O2 absorption in FeII(EDTA) solutions

    NARCIS (Netherlands)

    Gambardella, Francesca

    2005-01-01

    BiodeNOx is an industrial process for the removal of nitrogen monoxide from waste gases. The process consist in a chemical absorption in Fe(EDTA) solutions coupled with a biological regeneration. In order to optimize this process, the absorptions of nitrogen monoxide and oxygen in FeII(EDTA) solutio

  16. TEMPERATURE DEPENDENCE OF 57Fe-MÖSSBAUER SPECTRA FOR A 〖〖Fe〗_Fc^II-Fe〗_tpy^II-〖Fe〗_Fc^II TRINUCLEAR SYSTEM

    Directory of Open Access Journals (Sweden)

    Dumitru Sirbu

    2015-06-01

    Full Text Available 57Fe Mӧssbauer spectra were recorded for 1'-terpyridine ferrocenecarboxylic acid and [bis(1'-terpyridine ferrocenecarboxylic acid Fe(II]2+ in the temperature range 7 – 293 K. The temperature dependence of the Quadrupole Splitting, Isomer Shift and Debye-Waller factor are discussed. The Debye temperature for the iron nuclei in the investigated compounds was determined.

  17. Celdas galvánicas. Montaje y comprobación de la celda constituida por los pares Fe(III)/Fe(II)y Cu(II)/Cu.

    OpenAIRE

    Milla González, Miguel

    2013-01-01

    Se dispone de disoluciones de sulfato de cobre(II), sulfato de hierro(II) y nitrato de Fe(III), de un potenciómetro, un puente salino y electrodos de Cu y de grafito. Con las disoluciones citadas, montar una celda galvánica y medir su potencial. Son posibles todas las combinaciones tanto en el compartimento anódico como en el catódico.

  18. Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

    Science.gov (United States)

    Bassez, Marie-Paule

    2017-03-01

    In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as

  19. Evidence for Fluorescent Fe II Emission from Extended Low Ionization Outflows in Obscured Quasars

    CERN Document Server

    Wang, Tinggui; Yang, Chenwei; Wang, Huiyuan; Zhang, Shaohua

    2016-01-01

    Recent studies have shown that outflows in at least some broad absorption line (BAL) quasars are extended well beyond the putative dusty torus. Such outflows should be detectable in obscured quasars. We present four WISE selected infrared red quasars with very strong and peculiar ultraviolet Fe ii emission lines: strong UV Fe II UV arising from transitions to ground/low excitation levels, and very weak Fe II at wavelengths longer than 2800 {\\AA}. The spectra of these quasars display strong resonant emission lines, such as C IV, Al III and Mg II but sometimes, a lack of non-resonant lines such as C III], S III and He II. We interpret the Fe II lines as resonantly scattered light from the extended outflows that are viewed nearly edge-on, so that the accretion disk and broad line region are obscured by the dusty torus, while the extended outflows are not. We show that dust free gas exposed to strong radiation longward of 912 {\\AA} produces Fe II emission very similar to that observed. The gas is too cool to coll...

  20. Investigation of Co, Ni and Fe Doped II-VI Chalcogenides

    Science.gov (United States)

    2013-01-04

    72 70 Luminescence spectra of Fe:ZnSe samples at T = 14K having the following iron concentrations: (i) CFe = 112×1018 cm-3 and (ii... CFe = 5×1018 cm-3; and an Fe:ZnS sample at T = 14K having an iron concentration of: (iii) CFe = 5×1018 cm-3 ................................72 71...Luminescence lifetime versus temperature for Fe:ZnSe (+ - CFe = 0.1×1018 cm-3) and for Fe:ZnS crystals (×- CFe = 3×1018 cm-3, - CFe = 73×1018 cm-3

  1. Green rust formation during Fe(II) oxidation by the nitrate-reducing Acidovorax sp. strain BoFeN1.

    Science.gov (United States)

    Pantke, Claudia; Obst, Martin; Benzerara, Karim; Morin, Guillaume; Ona-Nguema, Georges; Dippon, Urs; Kappler, Andreas

    2012-02-07

    Green rust (GR) as highly reactive iron mineral potentially plays a key role for the fate of (in)organic contaminants, such as chromium or arsenic, and nitroaromatic compounds functioning both as sorbent and reductant. GR forms as corrosion product of steel but is also naturally present in hydromorphic soils and sediments forming as metastable intermediate during microbial Fe(III) reduction. Although already suggested to form during microbial Fe(II) oxidation, clear evidence for GR formation during microbial Fe(II) oxidation was lacking. In the present study, powder XRD, synchrotron-based XAS, Mössbauer spectroscopy, and TEM demonstrated unambiguously the formation of GR as an intermediate product during Fe(II) oxidation by the nitrate-reducing Fe(II)-oxidizer Acidovorax sp. strain BoFeN1. The spatial distribution and Fe redox-state of the precipitates associated with the cells were visualized by STXM. It showed the presence of extracellular Fe(III), which can be explained by Fe(III) export from the cells or extracellular Fe(II) oxidation by an oxidant diffusing from the cells. Moreover, GR can be oxidized by nitrate/nitrite and is known as a catalyst for oxidation of dissolved Fe(II) by nitrite/nitrate and may thus contribute to the production of extracellular Fe(III). As a result, strain BoFeN1 may contribute to Fe(II) oxidation and nitrate reduction both by an direct enzymatic pathway and an indirect GR-mediated process.

  2. Study of the reaction between ammonium thiocyanate and Fe (II or Fe (III using infrared spectroscopy: an experiment of prebiotic chemistry

    Directory of Open Access Journals (Sweden)

    Dimas Augusto Morozin Zaia

    2010-09-01

    Full Text Available The prebiotic chemistry studies the reactions that could be played an important role on origins of life on Earth. However, these reactions should be carried out under conditions that existed on the prebiotic Earth. The laboratory experiments of heating substances in solid state could be corresponding to the following prebiotic environments: cooling lava from volcanoes on the ground and impact of meteorites or comets on the earth. The present study examined the reaction in solid state between ammonium thiocyanate and Fe (II or Fe (III. The samples were heated at 220 ºC in several different times (6 hours, 24 hours, 7 days. The most important finding of this work is that a reaction of oxidation-reduction is occurring between Fe (II and ammonium thiocyanate, the infrared spectrum of the reaction product ammonium thiocyanate/Fe (II showed a band that it is characteristic of ferricyanate. The infrared spectra also showed bands that they are characteristics of guanidine thiocyanate. Thus, the heating of ammonium thiocyanate with Fe (II in solid state is synthesizing guanidine thiocyanate and at the same time oxidizing Fe (II to Fe (III. The product of reaction between Fe (III and ammonium thiocyanate is guanidine thiocyanate. Fe (II and Fe (III are reacting with ammonium thiocyanate in different way.

  3. The Role of Anisotropic Exchange in Single Molecule Magnets: A CASSCF/NEVPT2 Study of the Fe4 SMM Building Block [Fe2(OCH32(dbm4] Dimer

    Directory of Open Access Journals (Sweden)

    Alessandro Lunghi

    2016-09-01

    Full Text Available The rationalisation of single molecule magnets’ (SMMs magnetic properties by quantum mechanical approaches represents a major task in the field of the Molecular Magnetism. The fundamental interpretative key of molecular magnetism is the phenomenological Spin Hamiltonian and the understanding of the role of its different terms by electronic structure calculations is expected to steer the rational design of new and more performing SMMs. This paper deals with the ab initio calculation of isotropic and anisotropic exchange contributions in the Fe(III dimer [Fe 2 (OCH 3 2 (dbm 4 ]. This system represents the building block of one of the most studied Single Molecule Magnets ([Fe 4 RC(CH 2 O 3 2 (dpm 6 ] where R can be an aliphatic chain or a phenyl group just to name the most common functionalization groups and its relatively reduced size allows the use of a high computational level of theory. Calculations were performed using CASSCF and NEVPT2 approaches on the X-ray geometry as assessment of the computational protocol, which has then be used to evinced the importance of the outer coordination shell nature through organic ligand modelization. Magneto-structural correlations as function of internal degrees of freedom for isotropic and anisotropic exchange contributions are also presented, outlining, for the first time, the extremely rapidly changing nature of the anisotropic exchange coupling.

  4. Rate law of Fe(II) oxidation under low O2 conditions

    Science.gov (United States)

    Kanzaki, Yoshiki; Murakami, Takashi

    2013-12-01

    Despite intensive studies on Fe(II) oxidation kinetics, the oxidation rate law has not been established under low O2 conditions. The importance of Fe(II) oxidation under low O2 conditions has been recently recognized; for instance, the Fe(II)/Fe(III) compositions of paleosols, ancient soils formed by weathering, can produce a quantitative pattern of the atmospheric oxygen increase during the Paleoproterozoic. The effects of partial pressure of atmospheric oxygen (PO2) on the Fe(II) oxidation rate were investigated to establish the Fe(II) oxidation rate - PO2 relationships under low O2 conditions. All oxidation experiments were carried out in a glove box by introducing Ar gas at ∼10-5-∼10-4 atm of PO2, pH 7.57-8.09 and 22 °C. Luminol chemiluminescence was adopted to measure low Fe(II) concentrations (down to ∼2 nM). Combining previous data under higher PO2 conditions (10-3-0.2 atm) with the present data, the rate law for Fe(II) oxidation over a wide range of PO2 (10-5-0.2 atm) was found to be written as: d[Fe(II)]/dt=-k[Fe(II)][[]2 where the exponent of [O2], x, and the rate constant, k, change from x = 0.98 (±0.04) and log k = 15.46 (±0.06) at ∼6 × 10-3-0.2 atm of PO2 to x = 0.58 (±0.02) and log k = 13.41 (±0.03) at 10-5-∼6 × 10-3 atm of PO2. The most plausible mechanism that explains the change in x under low O2 conditions is that, instead of O2, oxygen-derived oxidants, H2O2 and to some extent, O2rad -, dominate the oxidation reactions at oxygen in the Precambrian.

  5. Coordination chemistry and solution structure of Fe(II)-peplomycin. Two possible coordination geometries.

    Science.gov (United States)

    Li, Yang; Lehmann, Teresa

    2012-06-01

    The solution structure of Fe(II)-peplomycin was determined from NMR data collected for this molecule. As found previously for Fe(II)- and Co(II)-bound bleomycin; the coordination sphere of the metal is composed of the primary and secondary amines in β-aminoalanine, the pyrimidine and imidazole rings in the pyrimidinylpropionamide, and β-hydroxyhistidine moieties, respectively, the amine nitrogen in β-hydroxyhistidine, and either the carbamoyl group in mannose or a solvent molecule. The two most discussed coordination geometries for the aforementioned ligands in metallo-bleomycins have been tested against the NMR data generated for Fe(II)-peplomycin. The interpretation of the experimental evidence obtained through molecular dynamics indicates that both geometries are equally likely in solution for this compound in the absence of DNA, but arguments are offered to explain why one of these geometries is preferred in the presence of DNA.

  6. Fe(II)-mediated reduction and repartitioning of structurally incorporated Cu, Co, and Mn in iron oxides.

    Science.gov (United States)

    Frierdich, Andrew J; Catalano, Jeffrey G

    2012-10-16

    The reduction of trace elements and contaminants by Fe(II) at Fe(III) oxide surfaces is well documented. However, the effect of aqueous Fe(II) on the fate of redox-active trace elements structurally incorporated into iron oxides is unknown. Here, we investigate the fate of redox-active elements during Fe(II)-activated recrystallization of Cu-, Co-, and Mn-substituted goethite and hematite. Enhanced release of Cu, Co, and Mn to solution occurs upon exposure of all materials to aqueous Fe(II) relative to reactions in Fe(II)-free fluids. The quantity of trace element release increases with pH when Fe(II) is present but decreases with increasing pH in the absence of Fe(II). Co and Mn release from goethite is predicted well using a second-order kinetic model, consistent with the release of redox-inactive elements such as Ni and Zn. However, Cu release and Co and Mn release from hematite require the sum of two rates to adequately model the kinetic data. Greater uptake of Fe(II) by Cu-, Co-, and Mn-substituted iron oxides relative to analogues containing only redox-inactive elements suggests that net Fe(II) oxidation occurs. Reduction of Cu, Co, and Mn in all materials following reaction with Fe(II) at pHs 7.0-7.5 is confirmed by X-ray absorption near-edge structure spectroscopy. This work shows that redox-sensitive elements structurally incorporated within iron oxides are reduced and repartitioned into fluids during Fe(II)-mediated recrystallization. Such abiotic reactions likely operate in tandem with partial microbial and abiotic iron reduction or during the migration of Fe(II)-containing fluids, mobilizing structurally bound contaminants and micronutrients in aquatic systems.

  7. Thermal decomposition of solid solutions in systems of Fe(II), Co(II), and Ni(II) hydrogen maleates with the formation of bimetallic nanoparticles

    Science.gov (United States)

    Yudanova, L. I.; Logvinenko, V. A.; Sheludyakova, L. A.; Ishchenko, A. V.; Rudina, N. A.

    2017-01-01

    XRD phase analysis and thermal analysis are used to confirm the formation of a continuous series of solid solutions in which one cation is substituted for another in the systems Co(II) hydrogen maleate-Ni(II) hydrogen maleate; Fe(II) hydrogen maleate-Co(II) hydrogen maleate; and Fe(II) hydrogen maleate-Ni(II) hydrogen maleate. The unit cell volume of these solid solutions is shown to depend linearly on their composition. The linear character of changes in the initial temperatures of dehydration and thermal decomposition is established. Using the example of the first of these systems, it is shown that when heated, bimetallic nanoparticles embedded in the polymeric matrix of composites obtained via the thermal decomposition of solid solutions of hydrogen maleates undergo a second-order phase transition, resulting in decomposition of the solid solutions of metals at the Curie temperature.

  8. As(III) removal and speciation of Fe (Oxyhydr)oxides during simultaneous oxidation of As(III) and Fe(II).

    Science.gov (United States)

    Han, Xu; Song, Jia; Li, Yi-Liang; Jia, Shao-Yi; Wang, Wen-Hui; Huang, Fu-Gen; Wu, Song-Hai

    2016-03-01

    Abiotic oxidation of Fe(II) is an important pathway in the formation of Fe (oxyhydr)oxides. However, how can As(III) affect the oxidation rate of Fe(II) and the speciation of Fe (oxyhydr)oxides, and what's the extent of the newly formed Fe (oxyhydr)oxides on the removal of aqueous arsenic are still poorly understood. Oxidation of Fe(II) under neutral pH conditions was therefore investigated under different molar ratios of As:Fe. Our results suggest that co-existence of aqueous As(III) significantly slows down the oxidation rate of Fe(II). Speciation of Fe (oxyhydr)oxides is dependent on pH and As:Fe ratios. At pH 6.0, formation of lepidocrocite and goethite is apparently inhibited at low As:Fe ratios, and ferric arsenate is favored at high As:Fe ratios. At pH 7.0, lepidocrocite gradually degenerates with the increasing As:Fe ratios. At pH 8.0, arsenite significantly inhibits the development of magnetite and favors a formation of lepidocrocite. XPS analysis further reveals that more than half of As(III) is oxidized to As(V) at pH 6.0 and 7.0, whereas at pH 8.0, the rapid oxidation of Fe(II) as well as the rapid formation of Fe (oxyhydr)oxides facilitate a rapid removal of dissolved As(III) before its further oxidation to As(V). Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Molar Absorptivity and Quantum Yield of Fe(II) Photo-formation for the Aqueous Solutions of Fe(III)-Dicarboxylate Comlexes

    Science.gov (United States)

    Hitomi, Y.; Arakaki, T.

    2009-04-01

    Fe(III)/Fe(II) cycle in the environment affects formation of active oxygen species such as hydrogen peroxide and hydroxyl radicals, which in turn determines lifetimes of many organic compounds. Although aqueous Fe(III)-dicarboxylate complexes are considered to be an important source of photo-chemically formed Fe(II), molar absorptivity and quantum yield of Fe(II) formation for individual species are not well understood. The Visual MINTEQ computer program was used to calculate the equilibrium concentrations of individual Fe(III)-dicarboxylate species in the aqueous solutions of Fe(III)-dicarboxylate complexes. The molar absorptivity and the product of the quantum yield and the molar absorptivity of Fe(III)-dicarboxylate species were obtained by UV-VIS spectrophotometer and photochemical experiments, and these experimental data were combined with the calculated equilibrium Fe(III)-dicarboxylate concentrations to determine individual molar absorptivity and quantum yield of Fe(II) photo-formation for a specific Fe(III)-dicarboxylate species. Dicarboxylate compounds studied were oxalate, malonate, succinate, malate, and phthalate.

  10. Kinetics of Fe(II)-catalyzed transformation of 6-line ferrihydrite under anaerobic flow conditions

    Energy Technology Data Exchange (ETDEWEB)

    Yang, L.; Steefel, C.I.; Marcus, M.A.; Bargar, J.R.

    2010-04-01

    The readsorption of ferrous ions produced by the abiotic and microbially-mediated reductive dissolution of iron oxy-hydroxides drives a series of transformations of the host minerals. To further understand the mechanisms by which these transformations occur and their kinetics within a microporous flow environment, flow-through experiments were conducted in which capillary tubes packed with ferrihydrite-coated glass spheres were injected with inorganic Fe(II) solutions under circumneutral pH conditions at 25 C. Synchrotron X-ray diffraction was used to identify the secondary phase(s) formed and to provide data for quantitative kinetic analysis. At concentrations at and above 1.8 mM Fe(II) in the injection solution, magnetite was the only secondary phase formed (no intermediates were detected), with complete transformation following a nonlinear rate law requiring 28 hours and 150 hours of reaction at 18 and 1.8 mM Fe(II), respectively. However, when the injection solution consisted of 0.36 mM Fe(II), goethite was the predominant reaction product and formed much more slowly according to a linear rate law, while only minor magnetite was formed. When the rates are normalized based on the time to react half of the ferrihydrite on a reduced time plot, it is apparent that the 1.8 mM and 18 mM input Fe(II) experiments can be described by the same reaction mechanism, while the 0.36 input Fe(II) experiment is distinct. The analysis of the transformation kinetics suggest that the transformations involved an electron transfer reaction between the aqueous as well as sorbed Fe(II) and ferrihydrite acting as a semiconductor, rather than a simple dissolution and recrystallization mechanism. A transformation mechanism involving sorbed inner sphere Fe(II) alone is not supported, since the essentially equal coverage of sorption sites in the 18 mM and 1.8 mM Fe(II) injections cannot explain the difference in the transformation rates observed.

  11. Kinetics of Fe(II)-catalyzed transformation of 6-line ferrihydrite under anaerobic flow conditions

    Energy Technology Data Exchange (ETDEWEB)

    Yang, L.; Steefel, C.I.; Marcus, M.A.; Bargar, J.R.

    2010-04-01

    The readsorption of ferrous ions produced by the abiotic and microbially-mediated reductive dissolution of iron oxy-hydroxides drives a series of transformations of the host minerals. To further understand the mechanisms by which these transformations occur and their kinetics within a microporous flow environment, flow-through experiments were conducted in which capillary tubes packed with ferrihydrite-coated glass spheres were injected with inorganic Fe(II) solutions under circumneutral pH conditions at 25 C. Synchrotron X-ray diffraction was used to identify the secondary phase(s) formed and to provide data for quantitative kinetic analysis. At concentrations at and above 1.8 mM Fe(II) in the injection solution, magnetite was the only secondary phase formed (no intermediates were detected), with complete transformation following a nonlinear rate law requiring 28 hours and 150 hours of reaction at 18 and 1.8 mM Fe(II), respectively. However, when the injection solution consisted of 0.36 mM Fe(II), goethite was the predominant reaction product and formed much more slowly according to a linear rate law, while only minor magnetite was formed. When the rates are normalized based on the time to react half of the ferrihydrite on a reduced time plot, it is apparent that the 1.8 mM and 18 mM input Fe(II) experiments can be described by the same reaction mechanism, while the 0.36 input Fe(II) experiment is distinct. The analysis of the transformation kinetics suggest that the transformations involved an electron transfer reaction between the aqueous as well as sorbed Fe(II) and ferrihydrite acting as a semiconductor, rather than a simple dissolution and recrystallization mechanism. A transformation mechanism involving sorbed inner sphere Fe(II) alone is not supported, since the essentially equal coverage of sorption sites in the 18 mM and 1.8 mM Fe(II) injections cannot explain the difference in the transformation rates observed.

  12. Phototrophic Fe(II)-oxidation in the chemocline of a ferruginous meromictic lake

    Science.gov (United States)

    Walter, Xavier A.; Picazo, Antonio; Miracle, Maria R.; Vicente, Eduardo; Camacho, Antonio; Aragno, Michel; Zopfi, Jakob

    2014-01-01

    Precambrian Banded Iron Formation (BIF) deposition was conventionally attributed to the precipitation of iron-oxides resulting from the abiotic reaction of ferrous iron (Fe(II)) with photosynthetically produced oxygen. Earliest traces of oxygen date from 2.7 Ga, thus raising questions as to what may have caused BIF precipitation before oxygenic photosynthesis evolved. The discovery of anoxygenic phototrophic bacteria thriving through the oxidation of Fe(II) has provided support for a biological origin for some BIFs, but despite reports suggesting that anoxygenic phototrophs may oxidize Fe(II) in the environment, a model ecosystem of an ancient ocean where they are demonstrably active was lacking. Here we show that anoxygenic phototrophic bacteria contribute to Fe(II) oxidation in the water column of the ferruginous sulfate-poor, meromictic lake La Cruz (Spain). We observed in-situ photoferrotrophic activity through stimulation of phototrophic carbon uptake in the presence of Fe(II), and determined light-dependent Fe(II)-oxidation by the natural chemocline microbiota. Moreover, a photoferrotrophic bacterium most closely related to Chlorobium ferrooxidans was enriched from the ferruginous water column. Our study for the first time demonstrates a direct link between anoxygenic photoferrotrophy and the anoxic precipitation of Fe(III)-oxides in a ferruginous water column, providing a plausible mechanism for the bacterial origin of BIFs before the advent of free oxygen. However, photoferrotrophs represent only a minor fraction of the anoxygenic phototrophic community with the majority apparently thriving by sulfur cycling, despite the very low sulfur content in the ferruginous chemocline of Lake La Cruz. PMID:25538702

  13. Nanosheets of Two-Dimensional Magnetic and Conducting Fe(II)/Fe(III) Mixed-Valence Metal-Organic Frameworks.

    Science.gov (United States)

    Benmansour, Samia; Abhervé, Alexandre; Gómez-Claramunt, Patricia; Vallés-García, Cristina; Gómez-García, Carlos J

    2017-08-09

    We report the synthesis, magnetic properties, electrical conductivity, and delamination into thin nanosheets of two anilato-based Fe(II)/Fe(III) mixed-valence two-dimensional metal-organic frameworks (MOFs). Compounds [(H3O)(H2O)(phenazine)3][Fe(II)Fe(III)(C6O4X2)3]·12H2O [X = Cl (1) and Br (2)] present a honeycomb layered structure with an eclipsed packing that generates hexagonal channels containing the water molecules. Both compounds show ferrimagnetic ordering at ca. 2 K coexisting with electrical conductivity (with room temperature conductivities of 0.03 and 0.003 S/cm). Changing the X group from Cl to Br leads to a decrease in the ordering temperature and room temperature conductivity that is correlated with the decrease of the electronegativity of X. Despite the ionic charge of the anilato-based layers, these MOFs can be easily delaminated in thin nanosheets with the thickness of a few monolayers.

  14. Implications of infalling Fe II - emitting clouds in AGN: anisotropic properties

    CERN Document Server

    Ferland, Gary J; Wang, Jian-Min; Baldwin, Jack A; Porter, Ryan L; van Hoof, Peter A M; Williams, R J R

    2009-01-01

    We investigate consequences of the discovery that Fe II emission in quasars, one of the spectroscopic signatures of "Eigenvector 1", may originate in infalling clouds. Eigenvector 1 correlates with the Eddington ratio L/L_Edd so that Fe II/Hbeta increases as L/L_Edd increases. We show that the "force multiplier", the ratio of gas opacity to electron scattering opacity, is ~ 10^3 - 10^4 in Fe II emitting gas. Such gas would be accelerated away from the central object if the radiation force is able to act on the entire cloud. Infall requires that the clouds have large column densities so that a substantial amount of shielded gas is present. The critical column density required for infall to occur depends on L/L_Edd, establishing a link between Eigenvector 1 and the Fe II/Hbeta ratio. We see predominantly the shielded face of the infalling clouds rather than the symmetric distribution of emitters that has been assumed. The Fe II spectrum emitted by the shielded face is in good agreement with observations thus so...

  15. Electron transfer and hydrogen generation from a molecular dyad: platinum(II) alkynyl complex anchored to [FeFe] hydrogenase subsite mimic.

    Science.gov (United States)

    Wang, Wen-Guang; Wang, Feng; Wang, Hong-Yan; Tung, Chen-Ho; Wu, Li-Zhu

    2012-02-28

    A PS-Fe(2)S(2) molecular dyad 1a directly anchoring a platinum(II) alkynyl complex to a Fe(2)S(2) active site of a [FeFe] H(2)ase mimic, and an intermolecular system of its reference complexes 1b and 2, have been successfully constructed. Time-dependence of H(2) evolution shows that PS-Fe(2)S(2)1a as well as complex 2 with 1b can produce H(2) in the presence of a proton source and sacrificial donor under visible light irradiation. Spectroscopic and electrochemical studies on the electron transfer event reveal that the reduced Fe(I)Fe(0) species generated by the first electron transfer from the excited platinum(II) complex to the Fe(2)S(2) active site in PS-Fe(2)S(2)1a and complex 2 with 1b is essential for photochemical H(2) evolution, while the second electron transfer from the excited platinum(II) complex to the protonated Fe(I)Fe(0) species is thermodynamically unfeasible, which might be an obstacle for the relatively small amount of H(2) obtained by PS-Fe(2)S(2) molecular dyads reported so far.

  16. Synthesis and photoelectric properties of new Dawson-type polyoxometalate-based dimeric and oligomeric Pt(II)-acetylide inorganic-organic hybrids.

    Science.gov (United States)

    Liu, Li; Hu, Lei; Liu, Qian; Du, Zu-Liang; Li, Fa-Bao; Li, Guang-Hua; Zhu, Xun-Jin; Wong, Wai-Yeung; Wang, Lei; Li, Hua

    2015-01-07

    A new synthesis route for preparing Dawson-type polyoxometalate (POM) based inorganic-organic hybrid materials is presented. Two new heteropolytungstate-based dimeric and oligomeric Pt(II) acetylide inorganic-organic hybrid compounds (2PtOD and PPtOD) were prepared by Hagihara's dehydrohalogenating coupling of a terminal diacetylene POM hybrid containing diphosphoryl functionality and an appropriate platinum(II) halide precursor. This method provides a rigid covalent linkage between the POM and the organometallic Pt(II) acetylide moiety. The redox potential of the polyanion can be tuned by grafting the organic and organometallic groups on it. The photoelectric properties of hybrid LB films derived from these inorganic-organic composites were studied.

  17. Data on Fe (II biosorption onto Sargassum hystrix algae obtained from the Persian Gulf in Bushehr Port, Iran

    Directory of Open Access Journals (Sweden)

    Fatemeh Faraji Ghasemi

    2016-12-01

    Full Text Available In this article, we used Sargassum hystrix algae as biosorbent for removal of Fe (II from aqueous solutions that was collected along the Persian Gulf coastline, Bushehr, Iran. The concentration level of remaining Fe (II in the samples was measured by using flame atomic absorption spectrometry (FAAS, Varian AA240, Australia. The isotherms, kinetics and modeling data of Fe (II biosorption onto Sargassum hystrix were also presented.

  18. Easy and quantitative access to Fe(II) and Fe(III) di(aryl)alkynylphosphine oxides featuring [Fe(dppe)Cp*] endgroups: terminal P=O functionality blocks the dimerisation of the Fe(III) derivatives.

    Science.gov (United States)

    Tohmé, Ayham; Hagen, Charles T; Essafi, Stéphanie; Bondon, Arnaud; Roisnel, Thierry; Carmichael, Duncan; Paul, Frédéric

    2015-01-25

    A series of paramagnetic di(aryl)alkynylphosphine oxides [PF6] featuring an open-shell [Fe(κ(2)-dppe)(η(5)-C5Me5)](+) endgroup were obtained by oxidation of their neutral Fe(II) parents 3a-c, themselves obtained in a simple and nearly quantitative fashion from the corresponding Fe(II) metallophosphines 1a-c. The new organometallic radicals were characterised by NMR and ESR and were shown to be perfectly stable in solution, in contrast to species such as 1a-b[PF6] which readily dimerise.

  19. Effects of waterborne Fe(II) on juvenile turbot Scophthalmus maximus: analysis of respiratory rate, hematology and gill histology

    Science.gov (United States)

    Wu, Zhihao; You, Feng; Liu, Hongjun; Liu, Mengxia; Li, Jun; Zhang, Peijun

    2012-03-01

    The concentration of Fe(II) is high in some groundwater supplies used in turbot culture, and the toxicity of waterborne Fe(II) is unknown. We investigated the stress responses of juvenile turbot, Scophthalmus maximus, exposed to Fe(II) of different concentrations (0.01, 0.05, 0.1, 0.5, 1, and 2 mg/L) for 1, 7, 14, and 28 d, under the same ambient conditions of other parameters. Changes in respiratory rate, hematological parameters, and gill structure were determined. The results show that waterborne Fe(II) did not cause severe hematological perturbation to turbot. A low-medium Fe(II) concentration (lower than 0.1 mg/L) could boost the respiratory rate, and caused no or very limited damage to fish. A high Fe(II) concentration (0.1 mg/L or higher), however, caused gill damage, such as vacuoles in branchial lamellae, epithelial necrosis, and hypertrophy of epithelial cells, and even death after extended exposure time. Therefore, excess waterborne Fe(II) and long-term exposure to Fe(II) could be responsible for poor growth and high mortality of turbot in culture. The concentration of waterborne Fe(II) in turbot culture should be kept below 0.1 mg/L.

  20. Persistence of Fe(II) in Seawater Due to the Effect of Organic Exudates from D. tertiolecta

    Science.gov (United States)

    Gonzalez, A.; Santana-Casiano, M.; González-Dávila, M.; Rico-Santos, M.; Lopez, A.; Perez-Almeida, N.; Suarez de Tangil, M. A.; Martel-Quintana, A.

    2016-02-01

    The chemistry of iron is highly affected by the presence of organic ligands in solution, where the exudates produced by microorganisms play a key role. In this sense, the Fe(II) oxidation was studied in the presence of exudates produced by Dunaliella tertiolecta. The Fe(II) oxidation rate was studied at different stages of growth, where the Dissolved Organic Carbon (DOC) increased from 2.1 to 7.1 mg L-1. The oxidation of Fe(II) was also studied as a function of pH (7.2 - 8.2), temperature (5-35 °C) and salinity (10-37). The presence of exudates invoked a decrease in Fe(II) rate constant with respect to the control seawater. On the other hand, the phenolic profile of the exudates and extracts of D. tertiolecta were studied in the stationary phase (8 days of culture) and compared with the control seawater. The phenolic profile revealed an enrichment in phenolic compounds that are able to reduce Fe(III) to Fe(II) acting as a source of Fe(II) in the surface waters. The two phenolic compounds, catechin and sinapic acid, were selected to study the reduction of Fe(III) in seawater from pH 8.0 to 6.0. The reduction of Fe(III) by these two phenolic compounds was a pH-dependent process. The organic exudates of D. tertiolecta favoured the persistence of Fe(II) in surface waters. This must be factored under ocean acidification conditions due to the key role played by them on the Fe(II) oxidation rate at lower pH values. As they are responsible for decreasing the Fe(II) oxidation rate, these experiments indicated that the exudates of D. tertiolecta can act as an important Fe(II) supplier to other marine organisms.

  1. A 2D [Fe-II-bistetrazole] coordination polymer exhibiting spin-crossover properties

    NARCIS (Netherlands)

    Quesada, Manuel; Prins, Ferry; Roubeau, Olivier; Gamez, Patrick; Teat, Simon J.; van Koningsbruggen, Petra J.; Haasnoot, Jaap G.; Reedijk, Jan

    2007-01-01

    The reaction of 1,3-bis(tetrazol-1-yl)-2-propanol (btzpol) with Fe(BF4)(2) center dot 6H(2)O in acetonitrile yields the remarkable 2D coordination polymer [Fe-II(btzpol)(1.8)(btzpol-OBF3)(1.2)](BF4)(0.8) center dot (H2O)(0.8)(CH3CN) (1). This compound has been structurally characterized using an X-r

  2. Crystal structure of a chloride-bridged copper(II dimer: piperazine-1,4-dium bis(di-μ-chlorido-bis[(4-carboxypyridine-2-carboxylato-κ2N,O2chloridocuprate(II

    Directory of Open Access Journals (Sweden)

    Bassey Enyi Inah

    2017-02-01

    Full Text Available Crystals of a new dimeric chloride-bridged cuprate(II derived from pyridine-2,4-dicarboxylic acid were obtained solvothermally in the presence of piperazine and hydrochloric acid. The crystal structure determination of the title salt, (C4H12N2[Cu2(C7H4NO42Cl4], revealed one of the carboxyl groups of the original pyridine-2,4-dicarboxylic acid ligand to be protonated, whereas the other is deprotonated and binds together with the pyridine N atom to the CuII atom. The coordination environment of the CuII atom is distorted square-pyramidal. One of the chloride ligands bridges two metal cations to form a centrosymmetric dimer with two different Cu—Cl distances of 2.2632 (8 and 2.7853 (8 Å, whereby the longer distance is associated with the apical ligand. The remaining chloride ligand is terminal at one of the basal positions, with a distance of 2.2272 (9 Å. In the crystal, the dimers are linked by intermolecular O—H...O hydrogen bonds, together with N—H...O and N—H...Cl interactions involving the centrosymmetric organic cation, into a three-dimensional supramolecular network. Further but weaker C—H...O and C—H...Cl interactions consolidate the packing.

  3. Crystal structure of a chloride-bridged copper(II) dimer: piperazine-1,4-dium bis-(di-μ-chlorido-bis[(4-carboxypyridine-2-carboxyl-ato-κ(2)N,O(2))chlorido-cuprate(II)].

    Science.gov (United States)

    Inah, Bassey Enyi; Ayi, Ayi Anyama; Adhikary, Amit

    2017-02-01

    Crystals of a new dimeric chloride-bridged cuprate(II) derived from pyridine-2,4-di-carb-oxy-lic acid were obtained solvothermally in the presence of piperazine and hydro-chloric acid. The crystal structure determination of the title salt, (C4H12N2)[Cu2(C7H4NO4)2Cl4], revealed one of the carboxyl groups of the original pyridine-2,4-di-carb-oxy-lic acid ligand to be protonated, whereas the other is deprotonated and binds together with the pyridine N atom to the Cu(II) atom. The coordination environment of the Cu(II) atom is distorted square-pyramidal. One of the chloride ligands bridges two metal cations to form a centrosymmetric dimer with two different Cu-Cl distances of 2.2632 (8) and 2.7853 (8) Å, whereby the longer distance is associated with the apical ligand. The remaining chloride ligand is terminal at one of the basal positions, with a distance of 2.2272 (9) Å. In the crystal, the dimers are linked by inter-molecular O-H⋯O hydrogen bonds, together with N-H⋯O and N-H⋯Cl inter-actions involving the centrosymmetric organic cation, into a three-dimensional supra-molecular network. Further but weaker C-H⋯O and C-H⋯Cl inter-actions consolidate the packing.

  4. Effect of aqueous Fe(II) on Sb(V) sorption on soil and goethite.

    Science.gov (United States)

    Fan, Jian-Xin; Wang, Yu-Jun; Fan, Ting-Ting; Dang, Fei; Zhou, Dong-Mei

    2016-03-01

    The effects of Fe(II) on the sorption and precipitation of Sb(V) on soils and goethite were investigated using batch experiments and X-ray photoelectron spectroscopy (XPS) in this study. The sorption capacity of Sb(V) were much higher in anoxic soil than oxic soil. Typically, dissolved Fe(II) concentration in anoxic soils decreased significantly with increasing Sb(V), which may be suggestive of Fe-Sb precipitation. The elevated concentrations of Fe(II) (1 mM) enhanced the sorption capacity of Sb(V) on goethite significantly. However, synchrotron radiation X-ray diffraction showed no new characteristic peak, indicating that this Fe-Sb precipitate might be poor crystallinity or amorphous. Moreover, Sb(III) was detected in anoxic soil, and the reduction of Sb(V) to Sb (III) improved the sorption capacity of Sb in anoxic soil because of the low solubility and migration of Sb(III). Nevertheless, Fe-Sb co-precipitation and Sb(V) reduction to Sb(III) might contribute simultaneously to the increased sorption capacity of Sb(V) on anoxic soils. This research could improve our current understanding of soil Sb chemistry in paddy and wetland soils.

  5. Ferritin ion channel disorder inhibits Fe(II)/O2 reactivity at distant sites.

    Science.gov (United States)

    Tosha, Takehiko; Behera, Rabindra K; Theil, Elizabeth C

    2012-11-05

    Ferritins, a complex, mineralized, protein nanocage family essential for life, provide iron concentrates and oxidant protection. Protein-based ion channels and Fe(II)/O(2) catalysis initiate conversion of thousands of Fe atoms to caged, ferritin Fe(2)O(3)·H(2)O minerals. The ion channels consist of six helical segments, contributed by 3 of 12 or 24 polypeptide subunits, around the 3-fold cage axes. The channel structure guides entering Fe(II) ions toward multiple, catalytic, diiron sites buried inside ferritin protein helices, ~20 Å away from channel internal exits. The catalytic product, Fe(III)-O(H)-Fe(III), is a mineral precursor; mineral nucleation begins inside the protein cage with mineral growth in the central protein cavity (5-8 nm diameter). Amino acid substitutions that changed ionic or hydrophobic channel interactions R72D, D122R, and L134P increased ion channel structural disorder (protein crystallographic analyses) and increased Fe(II) exit [chelated Fe(II) after ferric mineral reduction/dissolution]. Since substitutions of some channel carboxylate residues diminished ferritin catalysis with no effect on Fe(II) exit, such as E130A and D127A, we investigated catalysis in ferritins with altered Fe(II) exit, R72D, D122R and L134P. The results indicate that simply changing the ionic properties of the channels, as in the R72D variant, need not change the forward catalytic rate. However, both D122R and L134P, which had dramatic effects on ferritin catalysis, also caused larger effects on channel structure and order, contrasting with R72D. All three amino acid substitutions, however, decreased the stability of the catalytic intermediate, diferric peroxo, even though overall ferritin cage structure is very stable, resisting 80 °C and 6 M urea. The localized structural changes in ferritin subdomains that affect ferritin function over long distances illustrate new properties of the protein cage in natural ferritin function and for applied ferritin uses.

  6. Role of Fe(II) and phosphate in arsenic uptake by coprecipitation

    Energy Technology Data Exchange (ETDEWEB)

    Sahai, N.; Lee, Y.J.; Xu, H.; Ciardelli, M.; Gaillard, J.-F. (NWU); (UW)

    2008-07-08

    Natural attenuation of arsenic by simple adsorption on oxyhydroxides may be limited due to competing oxyanions, but uptake by coprecipitation may locally sequester arsenic. We have systematically investigated the mechanism and mode (adsorption versus coprecipitation) of arsenic uptake in the presence of carbonate and phosphate, from solutions of inorganic composition similar to many groundwaters. Efficient arsenic removal, >95% As(V) and {approx}55% in initial As(III) systems, occurred over 24 h at pHs 5.5-6.5 when Fe(II) and hydroxylapatite (Ca{sub 5}(PO{sub 4}){sub 3}OH, HAP) 'seed' crystals were added to solutions that had been previously reacted with HAP, atmospheric CO{sub 2(g)} and O{sub 2(g)}. Arsenic adsorption was insignificant (<10%) on HAP without Fe(II). Greater uptake in the As(III) system in the presence of Fe(II) was interpreted as due to faster As(III) to As(V) oxidation by molecular oxygen in a putative pathway involving Fe(IV) and As(IV) intermediate species. HAP acts as a pH buffer that allows faster Fe(II) oxidation. Solution analyses coupled with high-resolution transmission electron microscopy (HRTEM), X-ray Energy-Dispersive Spectroscopy (EDS), and X-Ray Absorption Spectroscopy (XAS) indicated the precipitation of sub-spherical particles of an amorphous, chemically-mixed, nanophase, Fe{sup III}[(OH){sub 3}(PO{sub 4})(As{sup V}O{sub 4})] {center_dot} nH{sub 2}O or Fe{sup III}[(OH){sub 3}(PO{sub 4})(As{sup V}O{sub 4})(As{sup III}O{sub 3}){sub minor}] {center_dot} nH{sub 2}O, where As{sup III}O{sub 3} is a minor component. The mode of As uptake was further investigated in binary coprecipitation (Fe(II) + As(III) or P), and ternary coprecipitation and adsorption experiments (Fe(II) + As(III) + P) at variable As/Fe, P/Fe and As/P/Fe ratios. Foil-like, poorly crystalline, nanoparticles of Fe{sup III}(OH){sub 3} and sub-spherical, amorphous, chemically-mixed, metastable nanoparticles of Fe{sup III}[(OH){sub 3}, PO{sub 4}] {center_dot} n

  7. Preparation and surface photoelectric properties of Fe(II/III) complexes

    Science.gov (United States)

    Jin, Jing; Xu, Xiao-Ting; Li, Dan; Han, Xiao; Li, Lei; Chi, Yu-Xian; Niu, Shu-Yun; Zhang, Guang-Ning

    2013-05-01

    Four Fe(II/III) supramolecules, {[Fe(Hpdc)2(H2O)2]·2H2O} (1), [Fe(HImbc)2(H2O)2] (2), [Fe(phen)2(CN)2]·CH3CH2OH·2H2O (3), K[Fe(tp)2]·SO4 (4) (H2pdc = 2,5-Pyridinedicarboxylic acid, H2Imbc = 4,5-Imidazoledicarboxylic acid, phen = 1,10-phenanthroline, tp- = poly(pyrazolyl)borate), were synthesized by hydrothermal and room temperature stirring methods. They were characterized by single crystal X-ray diffraction, surface photovoltage spectroscopy (SPS), field-induced surface photovoltage spectroscopy (FISPS), electron paramagnetic resonance (EPR), UV-Vis absorption spectra (UV-Vis), infrared spectra (IR) and element analysis. The structural analyses indicate that complex (1) is a supramolecule with 2D structure connected by hydrogen bonds. Complex (2) is a supramolecule with hydrogen-bonded 3D structure. Complexes (3) and (4) are both 1D supramolecules connected by hydrogen bonds. The electronic state of central metal Fe(II) ions in complexes (1) and (2) is d6 with FeN2O4 coordination mode, lying in weaker distorted octahedral field. The electronic state of Fe(II) ion in complex (3) is d6 with Fe(CN)2N4 mode in the strong distorted octahedral field. The electronic state of Fe(III) ion in complex (4) is d5 with FeN6 mode, lying in the strong octahedral field. The micro-environment of Fe(II/III) ions in the four complexes is further investigated by EPR. The SPS of four complexes all exhibit photovoltage responses in the range of 300-700 nm. This indicates that they all possess certain photoelectric conversion capability. The effects of component, structure, type of ligands of the complexes, valence state and coordination micro-environment of the central metal ions on the SPS were discussed. Furthermore, the SPS and UV-Vis absorption spectra were interrelated.

  8. SYNTHESIS AND CRYSTAL STRUCTURE OF A NEW Fe(II α-DIOXIMATE WITH TRIAZINE

    Directory of Open Access Journals (Sweden)

    О. Ciobanica

    2013-06-01

    Full Text Available The interaction of [Fe(DfgH2Py2] (where DfgH=monodeprotonated diphenylglyioxime, Py-pyridune and 1,3,5-triazine (Trz in chloroform resulted in a new coordination compound with the composition [Fe(DfgH2(Trz2]·2CHCl3 (1. The crystal structure of 1, determined by single crystal X-ray diffraction, revealed that Fe(II atom is coordinated by four oximic nitrogen atoms of two DfgH and two nitrogen atoms of two Trz ligands resulting in octahedral surrounding.

  9. Reactive Transport Modeling of Microbe-mediated Fe (II) Oxidation for Enhanced Oil Recovery

    Science.gov (United States)

    Surasani, V.; Li, L.

    2011-12-01

    Microbially Enhanced Oil Recovery (MEOR) aims to improve the recovery of entrapped heavy oil in depleted reservoirs using microbe-based technology. Reservoir ecosystems often contain diverse microbial communities those can interact with subsurface fluids and minerals through a network of nutrients and energy fluxes. Microbe-mediated reactions products include gases, biosurfactants, biopolymers those can alter the properties of oil and interfacial interactions between oil, brine, and rocks. In addition, the produced biomass and mineral precipitates can change the reservoir permeability profile and increase sweeping efficiency. Under subsurface conditions, the injection of nitrate and Fe (II) as the electron acceptor and donor allows bacteria to grow. The reaction products include minerals such as Fe(OH)3 and nitrogen containing gases. These reaction products can have large impact on oil and reservoir properties and can enhance the recovery of trapped oil. This work aims to understand the Fe(II) oxidation by nitrate under conditions relevant to MEOR. Reactive transport modeling is used to simulate the fluid flow, transport, and reactions involved in this process. Here we developed a complex reactive network for microbial mediated nitrate-dependent Fe (II) oxidation that involves both thermodynamic controlled aqueous reactions and kinetic controlled Fe (II) mineral reaction. Reactive transport modeling is used to understand and quantify the coupling between flow, transport, and reaction processes. Our results identify key parameter controls those are important for the alteration of permeability profile under field conditions.

  10. Sorption of As(V) on aluminosilicates treated with Fe(II) nanoparticles.

    Science.gov (United States)

    Dousová, Barbora; Grygar, Tomás; Martaus, Alexandr; Fuitová, Lucie; Kolousek, David; Machovic, Vladimír

    2006-10-15

    Adsorption of arsenic on clay surfaces is important for the natural and simulated removal of arsenic species from aqueous environments. In this investigation, three samples of clay minerals (natural metakaoline, natural clinoptilolite-rich tuff, and synthetic zeolite) in both untreated and Fe-treated forms were used for the sorption of arsenate from model aqueous solution. The treatment of minerals consisted of exposing them to concentrated solution of Fe(II). Within this process the mineral surface has been laden with Fe(III) oxi(hydroxides) whose high affinity for the As(V) adsorption is well known. In all investigated systems the sorption capacity of Fe(II)-treated sorbents increased significantly in comparison to the untreated material (from about 0.5 to >20.0 mg/g, which represented more than 95% of the total As removal). The changes of Fe-bearing particles in the course of treating process and subsequent As sorption were investigated by the diffuse reflectance spectroscopy and the voltammetry of microparticles. IR spectra of treated and As(V)-saturated solids showed characteristic bands caused by Fe(III)SO(4), Fe(III)O, and AsO vibrations. In untreated As(V)-saturated solids no significant AsO vibrations were observed due to the negligible content of sorbed arsenate.

  11. Near-IR [Fe II] emission diagnostics applied to cold disk winds in young stars

    CERN Document Server

    Pesenti, N; Cabrit, S; O'Brien, D; García, P; Ferreira, J

    2003-01-01

    We investigate the emissivity properties of the main near-IR transitions of the Fe+ ion in the conditions prevailing in the inner regions of jets from young stars, based on a simplified 16-level atom model. We present new diagnostic diagrams involving prominent near-IR line ratios that allow us to constrain the electronic density, temperature, and Fe gas phase abundance ratio, independently of the heating process. Comparison with recent near-IR observations of a sample of HH objects indicates gas phase Fe abundances ranging from 15-50 % up to 100 % of the solar value in agreement with the moderate depletions previously derived from optical line ratios or shock models. Hence, it appears that Fe-bearing dust is efficiently destroyed in stellar jets. We then use our Fe+ emissivity model to predict near-IR [Fe II] emission maps for self-similar, cold MHD disk wind models. We show that observations in [Fe II] with AMBER on the VLTI could severely constrain the MHD solution and the inner launch radius of the jet. W...

  12. Mixed-valence, layered, cation radical salts of the ethane-bridged dimeric tetrathiafulvalene [(EDT-TTF-CH2-)2#centre dot#+] [X-][THF]0.5, X-=FeCl4-, GaCl4-

    DEFF Research Database (Denmark)

    Mézière, C.; Fourmigué, M.; Canadell, E.

    2000-01-01

    The synthesis and X-ray crystal structure of the ethane-linked dimeric tetrathiafulvalene [(EDT-TTF-CH2)(2)], 1,2-bis(ethylenedithiotetrathiafulvalenyl)ethane (1), is reported. It oxidizes reversibly at 0.45 and 0.90 V vs SCE. Electrocrystallization in the presence of [n-Bu4N][FeCl4] or [n-Bu4N...

  13. A Comparison between Four Analytical Methods for the Measurement of Fe(II at Nanomolar Concentrations in Coastal Seawater

    Directory of Open Access Journals (Sweden)

    Mark J. Hopwood

    2017-06-01

    Full Text Available Dissolved Fe(II in seawater is deemed an important micronutrient for microbial organisms, but its analysis is challenging due to its transient nature. We conducted a series of Fe(II method comparison experiments, where spikes of 5 to 31 nM Fe(II were added to manipulated seawaters with varying dissolved oxygen (37 to 156 μM concentrations. The observed Fe(II concentrations from four analytical methods were compared: spectrophotometry with ferrozine, stripping voltammetry, and flow injection analysis using luminol (with, and without, a pre-concentration column. Direct comparisons between the different methods were undertaken from the derived apparent Fe(II oxidation rate constant (k1. Whilst the two luminol based methods produced the most similar concentrations throughout the experiments, k1 was still subject to a 20–30% discrepancy between them. Contributing factors may have included uncertainty in the calibration curves, and different responses to interferences from Co(II and humic/fulvic organic material. The difference in measured Fe(II concentrations between the luminol and ferrozine methods, from 10 min–2 h after the Fe(II spikes were added, was always relatively large in absolute terms (>4 nM and relative to the spike added (>20% of the initial Fe(II concentration. k1 derived from ferrozine observed Fe(II concentrations was 3–80%, and 4–16%, of that derived from luminol observed Fe(II with, and without, pre-concentration respectively. The poorest comparability of k1 was found after humic/fulvic material was added to raise dissolved organic carbon to 120 μM. A luminol method without pre-concentration then observed Fe(II to fall below the detection limit (<0.49 nM within 10 min of a 17 nM Fe(II spike addition, yet other methods still observed Fe(II concentrations of 2.7 to 3.7 nM 30 min later. k1 also diverged accordingly with the ferrozine derived value 4% of that derived from luminol without pre-concentration. These apparent

  14. Universality in bosonic dimer-dimer scattering

    Energy Technology Data Exchange (ETDEWEB)

    Deltuva, A. [Centro de Fisica Nuclear, Universidade de Lisboa, P-1649-003 Lisboa (Portugal)

    2011-08-15

    Bosonic dimer-dimer scattering is studied near the unitary limit using momentum-space equations for the four-particle transition operators. The impact of the Efimov effect on the dimer-dimer scattering observables is explored, and a number of universal relations is established with high accuracy. The rate for the creation of Efimov trimers via dimer-dimer collisions is calculated.

  15. Electrochemical studies of DNA interaction and antimicrobial activities of MnII, FeIII, CoII and NiII Schiff base tetraazamacrocyclic complexes

    Science.gov (United States)

    Kumar, Anuj; Vashistha, Vinod Kumar; Tevatia, Prashant; Singh, Randhir

    2017-04-01

    Tetraazamacrocyclic complexes of MnII, FeIII, CoII and NiII have been synthesized by template method. These tetraazamacrocycles have been analyzed with various techniques like molar conductance, IR, UV-vis, mass spectral and cyclic voltammetric studies. On the basis of all these studies, octahedral geometry has been assigned to these tetraazamacrocyclic complexes. The DNA binding properties of these macrocyclic complexes have been investigated by electronic absorption spectra, fluorescence spectra, cyclic voltammetric and differential pulse voltammetric studies. The cyclic voltammetric data showed that ipc and ipa were effectively decreased in the presence of calf thymus DNA, which is a strong evidence for the interaction of these macrocyclic complexes with the calf thymus DNA (ct-DNA). The heterogeneous electron transfer rate constant found in the order: KCoII > KNiII > KMnII which indicates that CoII macrocyclic complex has formed a strong intercalated intermediate. The Stern-Volmer quenching constant (KSV) and voltammetric binding constant were found in the order KSV(CoII) > KSV(NiII) > KSV(MnII) and K+(CoII) > K+(NiII) > K+(MnII) which shows that CoII macrocyclic complex exhibits the high interaction affinity towards ct-DNA by the intercalation binding. Biological studies of the macrocyclic complexes compared with the standard drug like Gentamycin, have shown antibacterial activities against E. coli, P. aeruginosa, B. cereus, S. aureus and antifungal activity against C. albicans.

  16. Preparation and reactivity of a tetranuclear Fe(II) core in the metallothionein α-domain.

    Science.gov (United States)

    Sano, Yohei; Onoda, Akira; Sakurai, Rie; Kitagishi, Hiroaki; Hayashi, Takashi

    2011-05-01

    Metallothioneins (MTs) are small cysteine-rich proteins which exhibit high affinities for various metal ions and play roles in storage of essential metals and detoxification of toxic metals. Studies on the redox properties of MTs have been quite limited. Recently, we focused on the α-domain of MT (MTα) as a protein matrix and incorporated a tetranuclear metal cluster as a reductant. UV-visible, CD and MS data indicate the formation of the stable tetranuclear metal-cysteine cluster in the MTα matrix with Fe(II)(4)-MTα and Co(II)(4)-MTα species existing in water. Furthermore, the Fe(II)(4)-MTα species was found to promote the reduction of met-myoglobin and azobenzene derivatives under mild conditions. Particularly, the stoichiometric reduction of methyl red with Fe(II)(4)-MTα (1:1) was found to proceed with a conversion of 98% over a period of 6h at 25°C. This indicates that all of the four Fe(II) cores contribute to the reduction. In this paper, we describe the preparation and reactivity of the tetranuclear iron cluster in the protein matrix.

  17. Transformation impacts of dissolved and solid phase Fe(II) on trichloroethylene (TCE) reduction in an iron-reducing bacteria (IRB) mixed column system: a mathematical model.

    Science.gov (United States)

    Bae, Yeunook; Kim, Dooil; Cho, Hyun-Hee; Singhal, Naresh; Park, Jae-Woo

    2012-12-01

    In this research, we conducted trichloroethylene (TCE) reduction in a column filled with iron and iron-reducing bacteria (IRB) and developed a mathematical model to investigate the critical reactions between active species in iron/IRB/contaminant systems. The formation of ferrous iron (Fe(II)) in this system with IRB and zero-valent iron (ZVI, Fe(0)) coated with a ferric iron (Fe(III)) crust significantly affected TCE reduction and IRB respiration in various ways. This study presents a new framework for transformation property and reducing ability of both dissolved (Fe(II)(dissolved)) and solid form ferrous iron (Fe(II)(solid)). Results showed that TCE reduction was strongly depressed by Fe(II)(solid) rather than by other inhibitors (e.g., Fe(III) and lactate), suggesting that Fe(II)(solid) might reduce IRB activation due to attachment to IRB cells. Newly exposed Fe(0) from the released Fe(II)(dissolved) was a strong contributor to TCE reduction compared to Fe(II)(solid). In addition, our research confirmed that less Fe(II)(solid) production strongly supported long-term TCE reduction because it may create an easier TCE approach to Fe(0) or increase IRB growth. Our findings will aid the understanding of the contributions of iron media (e.g., Fe(II)(solid), Fe(II)(dissolved), Fe(III), and Fe(0)) to IRB for decontamination in natural groundwater systems.

  18. Influence of cyclic dimer formation on the phase behavior of carboxylic acids. II. Cross-associating systems.

    Science.gov (United States)

    Janeček, Jiří; Paricaud, Patrice

    2013-08-15

    The doubly bonded dimer association scheme (DBD) proposed by Sear and Jackson is extended to mixtures exhibiting both self- and cross-associations. The PC-SAFT equation of state is combined with the new DBD association contribution to describe the vapor-liquid equilibria of binary mixtures of carboxylic acids + associating compounds (water, alcohols, and carboxylic acids). The effect of doubly bonded dimers on the phase behavior in such systems is less important than in mixtures of carboxylic acids with nonassociating compounds, due to the cross-associations that compete with the formation of DBDs. Nevertheless, a clear improvement in the description of vapor-liquid coexistence curves is achieved over the classical 2B association model, particularly for the dew point curves.

  19. Degradation of nitrates with the participation of Fe(II) and Fe(0) in groundwater: A review

    Science.gov (United States)

    Vodyanitskii, Yu. N.; Mineev, V. G.

    2015-02-01

    Nitrates from soil and nitrogen fertilizers unused by plants become hazardous pollutants and contaminate surface and ground waters. In the water-saturated layers, into which nitrates are leached, the content of organic matter (i.e., electron donors necessary for nitrification) can be insufficient. The deficiency of electrons in the groundwater can be eliminated by Fe(II) minerals that remained in the heavy rocks and are available to microorganisms due to dispersion. However, when the groundwater table is shallow (less than at 10 m), the natural denitrification develops poorly; therefore, remediation is needed to enrich the contaminated water with electron donors. Zerovalent iron is most frequently used for this purpose. The efficiency of the Fe0 barriers for the purification of groundwater from nitrates increases due to the activation of anaerobic denitrifying bacteria. In addition, the geochemical conditions and the composition of the bacterial community change in the Fe0 barrier zone, which favors the development of a wide range of anaerobic hydrogenotrophic bacteria (primarily Fe(III) reductants).

  20. Mechanical milling of Fe3O4/SiO2: Formation of an amorphous Fe(II)-Si-O-containing phase

    DEFF Research Database (Denmark)

    Koch, C.B.; Jiang, Jianzhong; Mørup, Steen

    1999-01-01

    of Fe(III). The material constitutes a mixture of ultrafine Fe-rich spinel particles (magnetite/maghemite) and ail amorphous Fe(II)-containing silicate with a magnetic transition temperature of approximately 25 K. The amorphous phase has a rather high Fe content and is distinctly differenct from......The product of ball milling of magnetite and amorphous silica (40 mole% Fe3O4 in SiO2) for an extended period of time (800 h) in a closed vial, has been investigated by Mossbauer spectroscopy, X-ray diffraction and infrared spectroscopy. It is found that the milling induces extensive reduction...... the initial amorphous silica....

  1. Mechanical milling of Fe3O4/SiO2: Formation of an amorphous Fe(II)-Si-O-containing phase

    DEFF Research Database (Denmark)

    Koch, C.B.; Jiang, Jianzhong; Mørup, Steen

    1999-01-01

    The product of ball milling of magnetite and amorphous silica (40 mole% Fe3O4 in SiO2) for an extended period of time (800 h) in a closed vial, has been investigated by Mossbauer spectroscopy, X-ray diffraction and infrared spectroscopy. It is found that the milling induces extensive reduction...... of Fe(III). The material constitutes a mixture of ultrafine Fe-rich spinel particles (magnetite/maghemite) and ail amorphous Fe(II)-containing silicate with a magnetic transition temperature of approximately 25 K. The amorphous phase has a rather high Fe content and is distinctly differenct from...

  2. A new perspective on vanadyl tartrate dimers. Part II. Structure and spectroscopic properties of calcium vanadyl tartrate tetrahydrate

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Jaca, J.; Rojo, T.; Pizarro, J.L.; Goni, A.; Arriortua, M.I. [Universidad del Pais Vasco, Bilbao (Spain)

    1993-12-31

    The calcium vanadyl tartrate complex [Ca(VO)(d,l-C{sub 4}H{sub 2}O{sub 6})(H{sub 2}O){sub 4}] has been synthesized and characterized by spectroscopic methods. Its crystal structure was solved by X-ray metods. The compound is monoclinic, space group P2{sub 1/c}, with a = 8.0282(5), b = 17.1568(8), c = 7.6113(3) {angstrom}, {beta} = 94.269(4){degrees} and Z = 4. The structure consists of centrosymmetric vanadyl tartrate dimers, [(VO)(d,l-C{sub 4}H{sub 2}O{sub 6})]{sup 4{minus}}{sub 2}, and calcium cations placed between them. As a result, dimers form chains in the [101] direction. Neighbouring chains are linked by the coordination of the calcium ion to the oxygen atom of a vanadyl group of a different chain, thus forming a two-dimensional structure. Different layers are linked by hydrogen bonds. Spectroscopic studies show the existence of intra-dimeric interactions between vanadium atoms. 23 refs., 4 figs., 5 tabs.

  3. Heterogeneous reduction of {sup 239}PuO{sub 2} by aqueous Fe(II) in the presence of hematite

    Energy Technology Data Exchange (ETDEWEB)

    Felmy, A.R.; Moore, D.A.; Qafoku, O.; Buck, E.; Ilton, E.S. [Pacific Northwest National Laboratory, Richland, WA (United States); Conradson, S.D. [Los Alamos National Laboratory, NM (United States)

    2013-07-01

    The reduction of PuO{sub 2}(am) by Fe(II) in the presence and absence of hematite was studied over a range of pH values and oxidation/reduction potentials. In contrast to thermodynamic predictions, the presence of hematite did not have a major effect on the overall reduction of PuO{sub 2}(am) to aqueous Pu(III). Instead the aqueous Pu(III) concentrations at longer time frames were accurately predicted using the measured Fe(II) concentration and existing thermodynamic data for the reaction: H{sub 2}O + H{sup +} + Fe{sup 2+} + PuO{sub 2}(am) {r_reversible} Pu{sup 3+} + Fe(OH){sub 3}(am) with log K = -0.6. The accuracy of this approach in all solutions containing aqueous Fe(II), coupled with the apparent lack of oxidation of Fe(II) by O{sub 2}(g), suggests that the Fe(OH){sub 3}(am) is formed by the oxidation of Fe(II) to Fe(III) by radiolysis. The continued generation of reactive amorphous iron hydroxide by radiolysis prevents thermodynamic equilibrium from being reached with more stable ferric oxide compounds, except possibly under acidic conditions where amorphous ferric hydroxide is soluble. The use of measured pe values, instead of aqueous Fe(II) measurements, also yields reasonable predictions of the final Pu(III) concentrations although the predictions are more uncertain. (orig.)

  4. Fe(II) oxidation during acid mine drainage neutralization in a pilot-scale sequencing batch reactor

    CSIR Research Space (South Africa)

    Zvimba, JN

    2013-10-01

    Full Text Available the suspended solids impacted more positively on Fe(II) oxidation during pilot scale AMD neutralization in a SBR, a phenomenon ascribed to generation of acidity by hydrolysis of Fe(II) as shown in equation 2. Figure 3 shows the chemical behavior... to the acidity generation resulting from hydrolysis of Fe(III) (Reaction 2) that would require further neutralization by CaCO3 (Reaction 3), and as such promotes further CaCO3 dissolution with AMD pH increasing to above 6.8 following complete Fe(II) oxidation...

  5. A search for supernova remnants in NGC 6946 using the [Fe II] 1.64 μm line

    Energy Technology Data Exchange (ETDEWEB)

    Bruursema, Justice; Meixner, Margaret [Department of Physics and Astronomy, The Johns Hopkins University, 3400 North Charles Street, Baltimore, MD 21218 (United States); Long, Knox S.; Otsuka, Masaaki, E-mail: justiceb@pha.jhu.edu [Space Telescope Science Institute, 3700 San Martin Drive, Baltimore, MD 21218 (United States)

    2014-09-01

    Shock models indicate and observations show that in the infrared (IR), supernova remnants (SNRs) emit strongly in [Fe II] at 1.64 μm. Here, we report the results of a search for SNRs in NGC 6946 relying on [Fe II] 1.64 μm line emission, where we employed an adjacent [Fe II]{sub Off} filter to accurately assess the local continuum levels. For this study, we used the WIYN High Resolution Infrared Camera on the WIYN 3.5 m telescope to image NGC 6946 in broadbands J and H and narrowbands [Fe II], [Fe II]{sub Off}, Paβ, and Paβ{sub Off}. From our search, we have identified 48 SNR candidates (SNRcs), 6 of which are coincident with sources found in prior radio, optical, and/or X-ray studies. The measured [Fe II] fluxes of our SNRcs range from 1.5 × 10{sup –16} to 4.2 × 10{sup –15} erg s{sup –1} cm{sup –2} and are among the highest of previously published extragalactic SNR [Fe II] fluxes. All of the candidates now need to be confirmed spectroscopically. However, the fact that we detect as many objects as we did suggests that [Fe II] can be used as an effective search tool to find extragalactic SNRs.

  6. Multi-reverse flow injection analysis integrated with multi-optical sensor for simultaneous determination of Mn(II), Fe(II), Cu(II) and Fe(III) in natural waters.

    Science.gov (United States)

    Youngvises, Napaporn; Suwannasaroj, Kittigan; Jakmunee, Jaroon; AlSuhaimi, Awadh

    2017-05-01

    Multi-reverse flow injection analysis (Mr-FIA) integrated with multi-optical sensor was developed and optimized for the simultaneous determination of multi ions; Mn(II), Fe(II), Cu(II) and Fe(III) in water samples. The sample/standard solutions were propelled making use of a four channels peristaltic pump whereas 4 colorimetric reagents specific for the metal ions were separately injected in sample streams using multi-syringe pump. The color zones that formed in the individual mixing coils were then streamed into multi-channels spectrometer, which comprised of four flows through cell and four pairs of light emitting diode and photodiode, whereby signals were measured concurrently. The linearity range (along with detection limit, µgL(-1)) was 0.050-3.0(16), 0.30-2.0 (11), 0.050-1.0(12) and 0.10-1.0(50)mgL(-1), for Mn(II), Fe(II), Cu(II) and Fe(III), respectively. In the interim, the correlation coefficients were 0.9924-0.9942. The percentages relative standard deviation was less than 3. The proposed system was applied successfully to determine targeted metal ions simultaneously in natural water with high sample throughput and low reagent consumption, thus it satisfies the criteria of Green Analytical Chemistry (GAC) and its goals.

  7. [Fe II] 1.64 um Imaging Observations of the Outflow Features around Ultracompact H II Regions in the 1st Galactic Quadrant

    CERN Document Server

    Shinn, Jong-Ho; Lee, Jae-Joon; Lee, Yong-Hyun; Kim, Hyun-Jeong; Pyo, Tae-Soo; Koo, Bon-Chul; Kyeong, Jaemann; Hwang, Narae; Park, Byeong-Gon

    2014-01-01

    We present [Fe II] 1.644 um features around ultracompact H II regions (UCHIIs) found on a quest for the "footprint" outflow features of UCHIIs---the feature produced by the outflowing materials ejected during the earlier, active accretion phase of massive young stellar objects (MYSOs). We surveyed 237 UCHIIs in the 1st Galactic quadrant, employing the CORNISH UCHII catalog and UWIFE data which is an imaging survey in [Fe II] 1.644 um performed with UKIRT-WFCAM under ~ 0.8" seeing condition. The [Fe II] features were found around five UCHIIs, one of which is of low plausibility. We interpret that the [Fe II] features are shock-excited by outflows from YSOs, and estimate the outflow mass loss rates from the [Fe II] flux, which are ~ 1 x 10^-6 - 4 x 10^-5 Ms yr^-1. We propose that the [Fe II] features might be the "footprint" outflow features, but more studies are required to clarify it. This is based on the morphological relation between the [Fe II] and 5 GHz radio features, the outflow mass loss rate, the trav...

  8. Four-site cooperative spin crossover in a mononuclear FeII complex

    DEFF Research Database (Denmark)

    Lennartson, Anders; Bond, Andrew; Piligkos, Stergios;

    2012-01-01

    Round and round: A mononuclear Fe(II) complex (see picture) with an N(4)S(2) coordination set has been characterized in four polymorphic forms. Two of the polymorphs display four-site cooperative spin crossover (SCO), shown conclusively by the crystal structure of a fully ordered 1:3 high-spin/lo...

  9. Dual-nanomaterial based electrode for voltammetric stripping of trace Fe(II) in coastal waters.

    Science.gov (United States)

    Lin, Mingyue; Pan, Dawei; Zhu, Yun; Hu, Xueping; Han, Haitao; Wang, ChenChen

    2016-07-01

    In this work, a dual-nanomaterial based electrode was established for selective and sensitive detection of trace Fe(II) in the presence of complexing agent (2,2'-bipyridyl). Titanium carbide nanoparticles (TiCNPs) were used as the growth-template for the formation of three-dimensional platinum nanoflowers (PtNFs) due to their unique cubic structures. Nafion was employed as the conducting matrix to help TiCNPs better attached onto the surface of the electrode and slow down the crystal rate of PtNFs during electrodeposition, which resulted in flower structure and more active surface of PtNFs. Taking advantage of synergistic effects of TiCNPs and Nafion as well as the catalytic amplifying effect of PtNFs, the excellent anodic signal responses for the voltammetric stripping determination of Fe(II) were obtained. The linear range of Fe(II) on this dual-nanomaterial based electrode was from 1nmolL(-1) to 6μmolL(-1) with the lowest detectable concentration of 0.1nmolL(-1) and a detection limit of 0.03nmolL(-1). Additionally, the effect of several experimental parameters, such as concentration and pH value of buffer solution, concentration of modifier and ligand, deposition potential and time of electrochemical determination, and scan rate were studied for analytical applications. The fabricated sensor had been successfully applied for the sensitive determination of trace Fe(II) in coastal waters.

  10. Variability of Fe II Emission Features in the Seyfert 1 Galaxy NGC 5548

    DEFF Research Database (Denmark)

    Vestergaard, Marianne; Peterson, B. M.

    2005-01-01

    We study the low-contrast Fe II emission blends in the ultraviolet (1250--2200A) and optical (4000--6000A) spectra of the Seyfert 1 galaxy NGC 5548 and show that these features vary in flux and that these variations are correlated with those of the optical continuum. The amplitude of variability ...

  11. Study on the spin crossover transition and glass transition for Fe(II) complex film, [Fe(II)(H-triazole){sub 3}]-Nafion, by means of Moessbauer spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nakamoto, Akio; Kamebuchi, Hajime, E-mail: cc106909@mail.ecc.u-tokyo.ac.jp [University of Tokyo, Graduate School of Arts and Sciences (Japan); Enomoto, Masaya [Tokyo University of Science, Department of Chemistry, Faculty of Science Division I (Japan); Kojima, Norimichi [University of Tokyo, Graduate School of Arts and Sciences (Japan)

    2012-03-15

    [Fe(II)(H-trz){sub 3}]-Nafion (trz = triazole) is a transparent spin crossover complex film, where the spin crossover transition between the low-spin (S = 0) and the high-spin (S = 2) states takes place between 225 K and 300 K. In this film, two doublets corresponding to the low-spin and high-spin states were observed in the {sup 57}Fe Moessbauer spectra, reflecting the spin crossover transition. From the analysis of {sup 57}Fe Moessbauer spectra, the Debye temperatures of the low-spin and high-spin sites were estimated at 185 K and 176 K, respectively, in the temperature range between 10 K and 150 K. In this film, the total intensity of the Moessbauer spectra corresponding to the low-spin and high-spin sites drastically decreases above 200 K, reflecting the glass transition of Nafion, where the lattice vibration of [Fe(H-trz){sub 3}]{sub n}{sup 2n+} is softened just as in solution due to micro-Brown motion of the segment of Nafion polymer membrane.

  12. [Reduction of nitrobenzene by iron oxides bound Fe(II) system at different pH values].

    Science.gov (United States)

    Luan, Fu-Bo; Xie, Li; Li, Jun; Zhou, Qi

    2009-07-15

    Batch tests were conducted to investigate the reductive transformation of nitrobenzene by goethite, hematite, magnetite and steel converter slag bound Fe(II) system. And the reduction mechanism was explored at different pH values. Experimental results showed that hematite, magnetite and steel converter slag could adsorb Fe(II) on surfaces and form iron oxides bound Fe(II) system at pH from 6.5 to 7.0. The systems had strong reductive capacity and could reduce nitrobenzene to aniline. The reduction efficiency of nitrobenzene in surface bound Fe(II) system followed the sequence of magnetite, hematite and steel converter slag from high to low. The reduction efficiency of hematite and magnetite system increased with pH increasing. While it was almost pH independent in steel converter slag system. Although goethite adsorbed most of Fe(II) in solution, the adsorbed Fe(II) had no reductive activity for nitrobenzene. At pH 6.0, small amount of Fe(II) was adsorbed on magnetite and hematite and the systems did not show reductive activity for nitrobenzene. However, steel converter slag could adsorb Fe(II) at pH 6.0 and reduction efficiency almost equaled to the value at pH 7.0. When pH was above 7.5, dissolved Fe(II) could be converted to Fe(OH)2 and the newly formed Fe(OH)2 became the main redactor in the system. Under alkali condition, the presence of iron oxides inhibited the reduction capacity of system.

  13. Syntheses, crystal structures, and magnetic properties of the oxalato-bridged mixed-valence complexes (FeII(bpm)3]2[FeIII2(ox)5].8H2O and FeII(bpm)3Na(H2O)2Fe(ox)(3).4H2O (bpm = 2,2'-bipyrimidine).

    Science.gov (United States)

    Armentano, D; De Munno, G; Faus, J; Lloret, F; Julve, M

    2001-02-12

    The preparation and crystal structures of two oxalato-bridged FeII-FeIII mixed-valence compounds, [FeII(bpm)3]2[FeIII2(ox)5].8H2O (1) and FeII(bpm)3Na(H2O)2FeIII(ox)(3).4H2O (2) (bpm = 2,2'-bipyrimidine; ox = oxalate dianion) are reported here. Complex 1 crystallizes in the triclinic system, space group P1, with a = 10.998(2) A, b = 13.073(3) A, c = 13.308(3) A, alpha = 101.95(2) degrees, beta = 109.20(2) degrees, gamma = 99.89(2) degrees, and Z = 1. Complex 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 12.609(2) A, b = 19.670(5) A, c = 15.843(3) A, beta = 99.46(1) degrees, and Z = 4. The structure of complex 1 consists of centrosymmetric oxalato-bridged dinuclear high-spin iron(III) [Fe2(ox)5]2- anions, tris-chelated low-spin iron(II) [Fe(bpm)3]2+ cations, and lattice water molecules. The iron atoms are hexacoordinated: six oxygen atoms (iron(III)) from two bidentate and one bisbidentate oxalato ligands and six nitrogen atoms (iron(II)) from three bidentate bpm groups. The Fe(III)-O(ox) and Fe(II)-N(bpm) bond distances vary in the ranges 1.967(3)-2.099(3) and 1.967(4)-1.995(3) A, respectively. The iron(III)-iron(III) separation across the bridging oxalato is 5.449(2) A, whereas the shortest intermolecular iron(III)-iron(II) distance is 6.841(2) A. The structure of complex 2 consists of neutral heterotrinuclear Fe(bpm)2Na(H2O)2Fe(ox)3 units and water molecules of crystallization. The tris-chelated low-spin iron(II) ([Fe(bpm)3]2+) and high-spin iron(III) ([Fe(ox)3]3-) entities act as bidentate ligands (through two bpm-nitrogen and two oxalato-oxygen atoms, respectively) toward the univalent sodium cation, yielding the trinuclear (bpm)2Fe(II)-bpm-Na(I)-ox-Fe(III)(ox)2 complex. Two cis-coordinated water molecules complete the distorted octahedral surrounding of the sodium atom. The ranges of the Fe(II)-N(bpm) and Fe(III)-O(ox) bond distances [1.968(6)-1.993(5) and 1.992(6)-2.024(6) A, respectively] compare well with those observed in 1. The Na

  14. Application of Fe(VI) in the treatment of Zn(II)-NTA complexes in aqueous solutions.

    Science.gov (United States)

    Yang, J; Tiwari, D; Yu, M; Pachuau, L; Kim, W; Lee, S

    2010-06-01

    The higher oxidation state of iron, i.e. Fe(VI), was exploited to treat the synthetic wastewater containing Zn(II)-NTA. The decomposition of Zn(II)-NTA by Fe(VI) was investigated with the help of analytical data obtained for the change in Fe(VI) concentration, dissolved organic carbon (DOC) and total soluble Zn(II) concentration as a function of time at various concentrations of Zn(II)-NTA and at constant Fe(VI) concentration. The UV-Visible data was used to explain the reaction kinetics for redox reactions between Fe(VI) and Zn(II)-NTA. The pseudo-first-order rate constant was calculated keeping the Zn(II)-NTA concentration in excess and hence the overall second-order-rate constant was obtained. Fe(VI) reduction was almost unaffected with the 1000 times increase in ionic strength (NaNO3), as well as in the presence of completely oxidized background electrolytes. However, Fe(VI) reduction was greatly affected in the presence of both SO3(2-) and NO2(-) especially at higher concentrations, indicating a competitive reduction took place between Zn(II)-NTA and Na2SO3 or NaNO2 in the Fe(VI) treatment. These results were again supported by the dissolved organic carbon observations since relatively very low removal of the dissolved organic carbon occurred in the presence of Na2SO3 and NaNO2.

  15. On the ortho-positronium quenching reactions promoted by Fe(II), Fe(III), Co(III), Ni(II), Zn(II) and Cd(II) cyanocomplexes

    Science.gov (United States)

    Fantola Lazzarini, Anna L.; Lazzarini, Ennio

    The o-Ps quenching reactions promoted in aqueous solutions by the following six cyanocomplexes: [Fe(CN) 6] 4-; [Co(CN) 6] 3-; [Zn(CN) 4] 2-; [Cd(CN) 6] 2-; [Fe(CN) 6] 3-; [Ni(CN) 4] 2- were investigated. The first four reactions probably consist in o-Ps addition across the CN bond, their rate constants at room temperature, Tr, being ⩽(0.04±0.02) × 10 9 M -1 s -1, i.e. almost at the limit of experimental errors. The rate constant of the fifth reaction, in o-Ps oxydation, at Tr is (20.3±0.4) × 10 9 M -1 s -1. The [Ni(CN) 4] 2-k value at Tr, is (0.27±0.01) × 10 9 M -1 s -1, i.e. 100 times less than the rate constants of o-Ps oxydation, but 10 times larger than those of the o-Ps addition across the CN bond. The [Ni(CN) 4] 2- reaction probably results in formation of the following positronido complex: [Ni(CN) 4Ps] 2-. However, it is worth noting that the existence of such a complex is only indirectly deduced. In fact it arises from comparison of the [Ni(CN) 4] 2- rate constant with those of the Fe(II), Zn(II), Cd(II), and Co(III) cyanocomplexes, which, like the Ni(II) cyanocomplex, do not promote o-Ps oxydation or spin exchange reactions.

  16. High-resolution mid-infrared spectra of Co II, Ni I, and Fe II in SN 1987A

    Science.gov (United States)

    Jennings, D. E.; Boyle, R. J.; Wiedemann, G. R.; Moseley, S. H.

    1993-01-01

    Ground-based infrared observations of SN 1987A on day 612 after the explosion have yielded resolved line profiles of Co II, Ni I, Fe II at 10.52, 11.31, and 17.94 micron, respectively. The spectra were taken at a resolving power of about 1000 with an array grating spectrometer on the 4 m telescope of Cerro Tololo Inter-American Observatory. Based on the observed line intensities we have estimated the minimum mass of each ion: M(Co II) = (6.0 +/- 1.8) x 10 exp -5 solar mass; M(Ni I) = (1.1 +/- 0.1) x 10 exp -3 solar mass; and M(Fe II) = (8.0 +/- 1.5) x 10 exp -3 solar mass. From these we infer total masses for cobalt, nickel, and iron in the ejecta. The nickel and iron line profiles are markedly asymmetric. We interpret these as arising from two components, one centered on the stellar rest velocity with an approximately 3250 km/s full width, and the second at about +1200 km/s with an approximately 1100 km/s full width. The asymmetry may represent a large-scale fracturing of the ejecta by Rayleigh-Taylor instabilities.

  17. Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

    Energy Technology Data Exchange (ETDEWEB)

    Frierdich, Andrew J. [Univ. of Wisconsin, Madison, WI (United States); Univ. of Iowa, Iowa City, IA (United States); Beard, Brian L. [Univ. of Wisconsin, Madison, WI (United States); Rosso, Kevin M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Scherer, Michelle M. [Univ. of Iowa, Iowa City, IA (United States); Spicuzza, Michael J. [Univ. of Wisconsin, Madison, WI (United States); Valley, John W. [Univ. of Wisconsin, Madison, WI (United States); Johnson, Clark M. [Univ. of Wisconsin, Madison, WI (United States)

    2015-07-01

    The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Fe isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II)aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II)aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II)aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous

  18. Formation of iron (hydr)oxides during the abiotic oxidation of Fe(II) in the presence of arsenate.

    Science.gov (United States)

    Song, Jia; Jia, Shao-Yi; Yu, Bo; Wu, Song-Hai; Han, Xu

    2015-08-30

    Abiotic oxidation of Fe(II) is a common pathway in the formation of Fe (hydr)oxides under natural conditions, however, little is known regarding the presence of arsenate on this process. In hence, the effect of arsenate on the precipitation of Fe (hydr)oxides during the oxidation of Fe(II) is investigated. Formation of arsenic-containing Fe (hydr)oxides is constrained by pH and molar ratios of As:Fe during the oxidation Fe(II). At pH 6.0, arsenate inhibits the formation of lepidocrocite and goethite, while favors the formation of ferric arsenate with the increasing As:Fe ratio. At pH 7.0, arsenate promotes the formation of hollow-structured Fe (hydr)oxides containing arsenate, as the As:Fe ratio reaches 0.07. Arsenate effectively inhibits the formation of magnetite at pH 8.0 even at As:Fe ratio of 0.01, while favors the formation of lepidocrocite and green rust, which can be latterly degenerated and replaced by ferric arsenate with the increasing As:Fe ratio. This study indicates that arsenate and low pH value favor the slow growth of dense-structured Fe (hydr)oxides like spherical ferric arsenate. With the rapid oxidation rate of Fe(II) at high pH, ferric (hydr)oxides prefer to precipitate in the formation of loose-structured Fe (hydr)oxides like lepidocrocite and green rust. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Fe(II)-Polypyridines as Chromophores in Dye-Sensitized Solar Cells: A Computational Perspective.

    Science.gov (United States)

    Jakubikova, Elena; Bowman, David N

    2015-05-19

    Over the past two decades, dye-sensitized solar cells (DSSCs) have become a viable and relatively cheap alternative to conventional crystalline silicon-based systems. At the heart of a DSSC is a wide band gap semiconductor, typically a TiO2 nanoparticle network, sensitized with a visible light absorbing chromophore. Ru(II)-polypyridines are often utilized as chromophores thanks to their chemical stability, long-lived metal-to-ligand charge transfer (MLCT) excited states, tunable redox potentials, and near perfect quantum efficiency of interfacial electron transfer (IET) into TiO2. More recently, coordination compounds based on first row transition metals, such as Fe(II)-polypyridines, gained some attention as potential sensitizers in DSSCs due to their low cost and abundance. While such complexes can in principle sensitize TiO2, they do so very inefficiently since their photoactive MLCT states undergo intersystem crossing (ISC) into low-lying metal-centered states on a subpicosecond time scale. Competition between the ultrafast ISC events and IET upon initial excitation of Fe(II)-polypyridines is the main obstacle to their utilization in DSSCs. Suitability of Fe(II)-polypyridines to serve as sensitizers could therefore be improved by adjusting relative rates of the ISC and IET processes, with the goal of making the IET more competitive with ISC. Our research program in computational inorganic chemistry utilizes a variety of tools based on density functional theory (DFT), time-dependent density functional theory (TD-DFT) and quantum dynamics to investigate structure-property relationships in Fe(II)-polypyridines, specifically focusing on their function as chromophores. One of the difficult problems is the accurate determination of energy differences between electronic states with various spin multiplicities (i.e., (1)A, (1,3)MLCT, (3)T, (5)T) in the ISC cascade. We have shown that DFT is capable of predicting the trends in the energy ordering of these electronic

  20. Fe(III) oxides protect fermenter-methanogen syntrophy against interruption by elemental sulfur via stiffening of Fe(II) sulfides produced by sulfur respiration.

    Science.gov (United States)

    Igarashi, Kensuke; Kuwabara, Tomohiko

    2014-03-01

    Thermosipho globiformans (rod-shaped thermophilic fermenter) and Methanocaldococcus jannaschii (coccal hyperthermophilic hydrogenotrophic methanogen) established H2-mediated syntrophy at 68 °C, forming exopolysaccharide-based aggregates. Electron microscopy showed that the syntrophic partners connected to each other directly or via intercellular bridges made from flagella, which facilitated transfer of H2. Elemental sulfur (S(0)) interrupted syntrophy; polysulfides abiotically formed from S(0) intercepted electrons that were otherwise transferred to H(+) to produce H2, resulting in the generation of sulfide (sulfur respiration). However, Fe(III) oxides significantly reduced the interruption by S(0), accompanied by stiffening of Fe(II) sulfides produced by the reduction of Fe(III) oxides with the sulfur respiration-generated sulfide. Sea sand replacing Fe(III) oxides failed to generate stiffening or protect the syntrophy. Several experimental results indicated that the stiffening of Fe(II) sulfides shielded the liquid from S(0), resulting in methane production in the liquid. Field-emission scanning electron microscopy showed that the stiffened Fe(II) sulfides formed a network of spiny structures in which the microorganisms were buried. The individual fermenter rods likely produced Fe(II) sulfides on their surface and became local centers of a core of spiny structures, and the connection of these cores formed the network, which was macroscopically recognized as stiffening.

  1. Uranium Immobilization through Fe(II) bio-oxidation: A Column study

    Energy Technology Data Exchange (ETDEWEB)

    Coates, John D.

    2009-09-14

    Current research on the bioremediation of heavy metals and radionuclides is focused on the ability of reducing organisms to use these metals as alternative electron acceptors in the absence of oxygen and thus precipitate them out of solution. However, many aspects of this proposed scheme need to be resolved, not the least of which is the time frame of the treatment process. Once treatment is complete and the electron donor addition is halted, the system will ultimately revert back to an oxic state and potentially result in the abiotic reoxidation and remobilization of the immobilized metals. In addition, the possibility exists that the presence of more electropositive electron acceptors such as nitrate or oxygen will also stimulate the biological oxidation and remobilization of these contaminants. The selective nitrate-dependent biooxidation of added Fe(II) may offer an effective means of “capping off” and completing the attenuation of these contaminants in a reducing environment making the contaminants less accessible to abiotic and biotic reactions and allowing the system to naturally revert to an oxic state. Our previous DOE-NABIR funded studies demonstrated that radionuclides such as uranium and cobalt are rapidly removed from solution during the biogenic formation of Fe(III)-oxides. In the case of uranium, X-ray spectroscopy analysis indicated that the uranium was in the hexavalent form (normally soluble) and was bound to the precipitated Fe(III)-oxides thus demonstrating the bioremediative potential of this process. We also demonstrated that nitrate-dependent Fe(II)- oxidizing bacteria are prevalent in the sediment and groundwater samples collected from sites 1 and 2 and the background site of the NABIR FRC in Oakridge, TN. However, all of these studies were performed in batch experiments in the laboratory with pure cultures and although a significant amount was learned about the microbiology of nitrate-dependent bio-oxidation of Fe(II), the effects of

  2. A first principles investigation of electron transfer between Fe(II) and U(VI) on insulating Al- vs. semiconducting Fe-oxide surfaces via the proximity effect

    Science.gov (United States)

    Taylor, S. D.; Marcano, M. C.; Becker, U.

    2017-01-01

    This study investigates how the intrinsic chemical and electronic properties of mineral surfaces and their associated electron transfer (ET) pathways influence the reduction of U(VI) by surface-associated Fe(II). Density functional theory (DFT), including the Hubbard U correction to the exchange-correlation functional, was used to investigate sorption/redox reactions and ET mechanisms between Fe(II) and U(VI) coadsorbed on isostructural, periodic (0 0 1) surfaces of the insulator corundum (α-Al2O3) vs. the semiconductor hematite (α-Fe2O3). Furthermore, the coadsorbed Fe(II) and U(VI) ions are spatially separated from one another on the surfaces (⩾5.9 Å) to observe whether electronic-coupling through the semiconducting hematite surface facilitates ET between the adsorbates, a phenomenon known as the proximity effect. The calculations show that the different chemical and electronic properties between the isostructural corundum and hematite (0 0 1) surfaces lead to considerably different ET mechanisms between Fe(II) and U(VI). ET on the insulating corundum (0 0 1) surface is limited by the adsorbates' structural configuration. When Fe(II) and U(VI) are spatially separated and do not directly interact with one another (e.g. via an inner-sphere complex), U(VI) reduction by Fe(II) cannot occur as there is no physical pathway enabling ET between the adsorbates. In contrast to the insulating corundum (0 0 1) surface, the hematite (0 0 1) surface can potentially participate in ET reactions due to the high number of electron acceptor sites from the Fe d-states near the Fermi level at the hematite surface. The adsorption of Fe(II) also introduces d-states near the Fermi level as well as shifts unoccupied d-states of the Fe cations at the hematite surface to lower energies, making the surface more conductive. In turn, electronic coupling through the surface can link the spatially separated adsorbates to one another and provide distinct ET pathways for an electron from Fe(II

  3. Self-assembly of a Co(II) dimer through H-bonding of water molecules to a 3D open-framework structure

    Indian Academy of Sciences (India)

    Sujit K Ghosh; Parimal K Bharadwaj

    2005-01-01

    Reaction of pyridine-2,4,6-tricarboxylic acid (ptcH3) with Co(NO3)2.6H2O in presence of 4,4'-bipyridine (4,4'-bpy) in water at room temperature results in the formation of {[Co2(ptcH)2(4,4'-bpy)(H2O)4].2H2O}, (1). The solid-state structure reveals that the compound is a dimeric Co(II) complex assembled to a 3D architecture via an intricate intra- and inter-molecular hydrogen-bonding interactions involving water molecules and carboxylate oxygens of the ligand ptcH2-. Crystal data: monoclinic, space group 21/, = 11.441(5) Å, = 20.212(2) Å, = 7.020(5) Å, = 103.77(5)°, = 1576.7(1) Å3, = 2, 1 = 0.0363, 2 = 0.0856, = 1.000.

  4. Microbial Fe(II) oxidation at circumneutral pH: Reaction kinetics, mineral products, and distribution of neutrophilic iron oxidizers in wetland soils

    NARCIS (Netherlands)

    Vollrath, S.

    2012-01-01

    Multiple studies have shown that neutrophilic Fe(II) oxidizers can conserve energy from Fe(II) oxidation, however, it is still unclear how they can compete against the fast abiotic reaction at neutral pH, or to which extent these bacteria increase the overall Fe(II) oxidation rate. Similar to

  5. Optimized Gen-II FeCrAl cladding production in large quantity for campaign testing

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Yukinori [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Sun, Zhiqian [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Pint, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Terrani, Kurt A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-06-03

    There are two major objectives in this report; (1) to optimize microstructure control of ATF FeCrAl alloys during tube drawing processes, and (2) to provide an update on the progress of ATF FeCrAl tube production via commercial manufacturers. Experimental efforts have been made to optimize the process parameters balancing the tube fabricability, especially for tube drawing processes, and microstructure control of the final tube products. Lab-scale sheet materials of Gen II FeCrAl alloys (Mo-containing and Nb-containing FeCrAl alloys) were used in the study, combined with a stepwise warm-rolling process and intermediate annealing, aiming to simulate the tube drawing process in a commercial tube manufacturer. The intermediate annealing at 650ºC for 1h was suggested for the tube-drawing process of Mo-containing FeCrAl alloys because it successfully softened the material by recovering the work hardening introduced through the rolling step, without inducing grain coarsening due to recrystallization. The final tube product is expected to have stabilized deformed microstructure providing the improved tensile properties with sufficient ductility. Optimization efforts on Nb-containing FeCrAl alloys focused on the effect of alloying additions and annealing conditions on the stability of deformed microstructure. Relationships between the second-phase precipitates (Fe2Nb-Laves phase) and microstructure stability are discussed. FeCrAl tube production through commercial tube manufacturers is currently in progress. Three different manufacturers, Century Tubes, Inc. (CTI), Rhenium Alloys, Inc. (RAI), and Superior Tube Company, Inc. (STC), are providing capabilities for cold-drawing, warm-drawing, and HPTR cold-pilgering, respectively. The first two companies are currently working on large quantity tube production (expected 250 ft length) of Gen I model FeCrAl alloy (B136Y3, at CTI) and Gen II (C35M4, at RAI), with the process parameters obtained from the experimental

  6. Chitosan film loaded with silver nanoparticles-sorbent for solid phase extraction of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II).

    Science.gov (United States)

    Djerahov, Lubomir; Vasileva, Penka; Karadjova, Irina; Kurakalva, Rama Mohan; Aradhi, Keshav Krishna

    2016-08-20

    The present study describes the ecofriendly method for the preparation of chitosan film loaded with silver nanoparticles (CS-AgNPs) and application of this film as efficient sorbent for separation and enrichment of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II). The stable CS-AgNPs colloid was prepared by dispersing the AgNPs sol in chitosan solution at appropriate ratio and further used to obtain a cast film with very good stability under storage and good mechanical strength for easy handling in aqueous medium. The incorporation of AgNPs in the structure of CS film and interaction between the polymer matrix and nanoparticles were confirmed by UV-vis and FTIR spectroscopy. The homogeneously embedded AgNPs (average diameter 29nm, TEM analysis) were clearly observed throughout the film by SEM. The CS-AgNPs nanocomposite film shows high sorption activity toward trace metals under optimized chemical conditions. The results suggest that the CS-AgNPs nanocomposite film can be feasibly used as a novel sorbent material for solid-phase extraction of metal pollutants from surface waters.

  7. Incidence of HI 21-cm absorption in strong FeII systems at $0.5

    CERN Document Server

    Dutta, R; Gupta, N; Joshi, R; Petitjean, P; Noterdaeme, P; Ge, J; Krogager, J -K

    2016-01-01

    We present the results from our search for HI 21-cm absorption in a sample of 16 strong FeII systems ($W_{\\rm r}$(MgII $\\lambda2796$) $\\ge1.0$ \\AA\\ and $W_{\\rm r}$(FeII $\\lambda2600$) or $W_{\\rm FeII}$ $\\ge1$ \\AA) at $0.5II systems at this redshift range by $\\sim50$%. Combining our measurements with those in the literature, we find that the detection rate of HI 21-cm absorption increases with $W_{\\rm FeII}$, being four times higher in systems with $W_{\\rm FeII}$ $\\ge1$ \\AA\\ compared to systems with $W_{\\rm FeII}$ $<1$ \\AA. The $N$(HI) associated with the HI 21-cm absorbers would be $\\ge 2 \\times 10^{20}$ cm$^{-2}$, assuming a spin temperature of $\\sim500$ K (based on HI 21-cm absorption measurements of damped Lyman-$\\alpha$ systems at this redshift range) and unit covering factor. We find that ...

  8. Influence of organics and silica on Fe(II) oxidation rates and cell-mineral aggregate formation by the green-sulfur Fe(II)-oxidizing bacterium Chlorobium ferrooxidans KoFox - Implications for Fe(II) oxidation in ancient oceans

    Science.gov (United States)

    Gauger, Tina; Byrne, James M.; Konhauser, Kurt O.; Obst, Martin; Crowe, Sean; Kappler, Andreas

    2016-06-01

    Most studies on microbial phototrophic Fe(II) oxidation (photoferrotrophy) have focused on purple bacteria, but recent evidence points to the importance of green-sulfur bacteria (GSB). Their recovery from modern ferruginous environments suggests that these photoferrotrophs can offer insights into how their ancient counterparts grew in Archean oceans at the time of banded iron formation (BIF) deposition. It is unknown, however, how Fe(II) oxidation rates, cell-mineral aggregate formation, and Fe-mineralogy vary under environmental conditions reminiscent of the geological past. To address this, we studied the Fe(II)-oxidizer Chlorobium ferrooxidans KoFox, a GSB living in co-culture with the heterotrophic Geospirillum strain KoFum. We investigated the mineralogy of Fe(III) metabolic products at low/high light intensity, and in the presence of dissolved silica and/or fumarate. Silica and fumarate influenced the crystallinity and particle size of the produced Fe(III) minerals. The presence of silica also enhanced Fe(II) oxidation rates, especially at high light intensities, potentially by lowering Fe(II)-toxicity to the cells. Electron microscopic imaging showed no encrustation of either KoFox or KoFum cells with Fe(III)-minerals, though weak associations were observed suggesting co-sedimentation of Fe(III) with at least some biomass via these aggregates, which could support diagenetic Fe(III)-reduction. Given that GSB are presumably one of the most ancient photosynthetic organisms, and pre-date cyanobacteria, our findings, on the one hand, strengthen arguments for photoferrotrophic activity as a likely mechanism for BIF deposition on a predominantly anoxic early Earth, but, on the other hand, also suggest that preservation of remnants of Fe(II)-oxidizing GSB as microfossils in the rock record is unlikely.

  9. Numerical Simulations Reveal Randomness of Cu(II) Induced Aβ Peptide Dimerization under Conditions Present in Glutamatergic Synapses

    Science.gov (United States)

    Goch, Wojciech; Bal, Wojciech

    2017-01-01

    The interactions between the Aβ1–40 molecules species and the copper ions (Cu(II)) were intensively investigated due to their potential role in the development of the Alzheimer Disease (AD). The rate and the mechanism of the Cu(II)—Aβ complexes formation determines the aggregation pathway of the Aβ species, starting from smaller but more cytotoxic oligomers and ending up in large Aβ plaques, being the main hallmark of the AD. In our study we exploit the existing knowledge on the Cu(II)—Aβ interactions and create the theoretical model of the initial phase of the copper- driven Aβ aggregation mechanism. The model is based on the direct solution of the Chemical Master Equations, which capture the inherent stochastics of the considered system. In our work we argue that due to a strong Cu(II) affinity to Aβ and temporal accessibility of the Cu(II) ions during normal synaptic activity the aggregation driven by Cu(II) dominates the pure Aβ aggregation. We also demonstrate the dependence of the formation of different Cu(II)—Aβ complexes on the concentrations of reagents and the synaptic activity. Our findings correspond to recent experimental results and give a sound hypothesis on the AD development mechanisms. PMID:28125716

  10. [Nitrate removal by a strain of nitrate-dependent Fe (II) -oxidizing bacteria].

    Science.gov (United States)

    Wang, Hong-Yu; Yang, Kai; Zhang, Qian; Ji, Bin; Chen, Dan; Sun, Yu-Chong; Tian, Jun

    2014-04-01

    A nitrate-dependent Fe(II)-oxidizing bacterial strain, named W5, was isolated from the sediment of the East Lake in Wuhan. Strain W5 was studied for its characteristics of denitrification and nitrogen removal. According to its physiological and biochemical characteristics and the analysis of its 16S rRNA gene sequence, strain W5 was identified as Microbacterium sp. The optimal denitrification performance can be obtained under conditions of NO3(-) -N 40 mg x L(-1), Fe2+ 500 mg x L(-1) and pH 6.8-7.0. After one week of cultivation under optimal conditions, nitrate removal percentage reached 87.0%. During the process of the culture, the nitrite nitrogen concentration was no more than 0.31 mg x L(-1) and there was no ammonia nitrogen production. It was indicated that the nitrate was mostly converted into N2. The consumption rate of Fe2+ was 95.2%.

  11. Spectroscopic and thermal degradation behavior of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes with thiopental sodium anesthesia drug

    Science.gov (United States)

    Refat, Moamen S.

    2013-04-01

    A new series of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized with thiopental sodium anesthesia drug. The elemental analyses of the complexes are confined to stoichiometry of the formulas [M(TPL)3]ṡnH2O (M = Cr(III) or Fe(III); n = 6 or 5), [M(TPL)2(H2O)2]ṡnH2O (M = Mn(II), Co(II) or Ni(II); n = 0 or 4), and [M(TPL)2] (M = Cu(II) or Zn(II); n = 2 or 0) respectively, where TPL is thiopental chelating agent. Structures have been discussed and suggested upon elemental analyses, infrared, Raman, electronic, electron spin resonance, 1H NMR spectral data and magnetic studies. The X-ray powder diffraction (XRD) was performed of metal complexes. The XRD patterns indicate crystalline nature for the complexes. The measured low molar conductance values in dimethylsulfoxide indicate that the complexes are non-electrolyte nature. Spectroscopic discussion refer that coordination take place through three types: Cdbnd N (pyrimidine moiety) nitrogen and C2sbnd S (2-thiolate group) for Cr(III), Mn(II) and Fe(III), C6dbnd O (amido group) oxygen and C2sbnd S (2-thiolate group) for Co(II) and Ni(II), and Cu(II) and Zn(II) ions coordinated via Cdbnd N (pyrimidine moiety) nitrogen, C2dbnd S (2-thiolate group) and C6dbnd O (amido group) oxygen, respectively. The thermal behavior (TG/DTG/DTA) of the complexes was studied and kinetic parameters were determined by Horowitz-Metzger and Coats-Redfern methods. The thiopental and its complexes have been screened for their antimicrobial (G+ and G-) bacteria (Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa) and fungi (Aspergillus flavus and Candida albicans) activities by minimum inhibitory concentration (MIC) method.

  12. The Reduction of Aqueous Metal Species on the Surfaces of Fe(II)-Containing Oxides: The Role of Surface Passivation

    Science.gov (United States)

    White, A.F.; Peterson, M.L.

    1998-01-01

    The reduction of aqueous transition metal species at the surfaces of Fe(II)- containing oxides has important ramifications in predicting the transport behavior in ground water aquifers. Experimental studies using mineral suspensions and electrodes demonstrate that structural Fe(II) heterogeneously reduces aqueous ferric, cupric, vanadate and chromate ions on magnetite and ilmenite surfaces. The rates of metal reduction on natural oxides is strongly dependent on the extent of surface passivation and redox conditions in the weathering environment. Synchrotron studies show that surface oxidation of Fe(II)-containing oxide minerals decreases their capacity for Cr(VI) reduction at hazardous waste disposal sites.

  13. The effect of biogenic Fe(II) on the stability and sorption of Co(II)EDTA 2- to goethite and a subsurface sediment

    Science.gov (United States)

    Zachara, John M.; Smith, Steven C.; Fredrickson, James K.

    2000-04-01

    Laboratory experiments were conducted with suspensions of goethite (α-FeOOH) and a subsurface sediment to assess the influence of bacterial iron reduction on the fate of Co(II)EDTA 2-, a representative metal-ligand complex of intermediate stability (log K Co(II)EDTA = 17.97). The goethite was synthetic (ca. 55 m 2/g) and the sediment was a Pleistocene age, Fe(III) oxide-containing material from the Atlantic coastal plain (Milford). Shewanella alga strain BrY, a dissimilatory iron reducing bacterium (DIRB), was used to promote Fe(III) oxide reduction. Sorption isotherms and pH adsorption edges were measured for Co 2+, Fe 2+, Co(II)EDTA 2-, and Fe(II)EDTA 2- on the two sorbents in 0.001 mol/L Ca(ClO 4) 2 to aid in experiment interpretation. Anoxic suspensions of the sorbents in PIPES buffer at pH 6.5-7.0 were spiked with Co(II)EDTA 2- (10 -5 mol/L, 60Co and 14EDTA labeled), inoculated with BrY (1-6 × 10 8 organisms/mL), and the headspace filled with a N 2/H 2 gas mix. The experiments were conducted under non-growth conditions. The medium did not contain PO 43- (with one exception), trace elements, or vitamins. The tubes were incubated under anoxic conditions at 25°C for time periods in excess of 100 d. Replicate tubes were sacrificed and analyzed at desired time periods for pH, Fe(II) TOT, Fe (aq)2+, 60Co, and 14EDTA. Abiotic analogue experiments were conducted where Fe (aq)2+ was added in increasing concentration to Co(II)EDTA 2-/mineral suspensions to simulate the influence of bacterial Fe(II) evolution. The DIRB generated Fe(II) from both goethite and the Milford sediment that was strongly sorbed by mineral surfaces. Aqueous Fe 2+ increased during the experiment as surfaces became saturated; Fe (aq)2+ induced the dissociation of Co(II)EDTA 2- into a mixture of Co 2+, Co(II)EDTA 2-, and Fe(II)EDTA 2- (log K Fe(II)EDTA = 15.98). The extent of dissociation of Co(II)EDTA 2- was greater in the subsurface sediment because it sorbed Fe(II) less strongly than did

  14. Regulatory Fe(II/III) heme: the reconstruction of a molecule's biography.

    Science.gov (United States)

    Kühl, Toni; Imhof, Diana

    2014-09-22

    More than 20 years of research on heme as a temporary effector molecule of proteins have revealed its widespread impact on virtually all primary functions in the human organism. As our understanding of this influence is still growing, a comprehensive overview of compiled data will give fresh impetus for creativity and developing new strategies in heme-related research. From known data concerning heme-regulated proteins and their involvement in the development of diseases, we provide concise information of Fe(II/III) heme as a regulator and the availability of "regulatory heme". The latter is dependent on the balance between free and bound Fe(II/III) heme, here termed "hemeostasis". Imbalance of this system can lead to the development of diseases that were not always attributed to this small molecule. Diseases such as cancer or Alzheimer's disease highlight the reawakened interest in heme, whose function was previously believed to be completely understood.

  15. Optical Waveguiding Organic Nanorods Coated with Reversibly Switchable Fe(II Spin Transition Nanoparticles

    Directory of Open Access Journals (Sweden)

    Supratim Basak

    2013-01-01

    Full Text Available A dual functional nanohybrid object combining photonic and magnetic properties was successfully prepared through a “bottom-up” self-assembly approach. In this method, spin transition Fe(II coordination nanoparticles and optical wave guiding organic nanorods were generated in situ and successfully integrated together in a single pot through self-assembly. The Fe(II nanoparticles coated on organic nanorods (nanohybrids display temperature dependent reversible spin transition (Paramagnetic; diamagnetic; behavior. The nano-hybrids show efficient optical wave guiding behavior, which demonstrates the future possibility to perform light induced excited spin state trapping (LIESST experiments on a single spin transition nanoparticle level. These photonic and magnetic “nanohybrids” offer promising option to externally manipulate spin state of the spin transition nanoparticles using temperature as well as remote laser light.

  16. Fe K alpha and hydrodynamic loop model diagnostics for a large flare on II Peg

    CERN Document Server

    Ercolano, Barbara; Reale, Fabio; Testa, Paola; Miller, Jon M

    2008-01-01

    The observation by the Swift X-ray Telescope of the Fe K alpha_1, alpha_2 doublet during a large flare on the RS CVn binary system II Peg represents one of only two firm detections to date of photospheric Fe K alpha from a star other than our Sun. We present models of the Fe K alpha equivalent widths reported in the literature for the II Peg observations and show that they are most probably due to fluorescence following inner shell photoionisation of quasi-neutral Fe by the flare X-rays. Our models constrain the maximum height of flare the to 0.15 R_* assuming solar abundances for the photospheric material, and 0.1 R_* and 0.06 R_* assuming depleted photospheric abundances ([M/H]=-0.2 and [M/H]=-0.4, respectively). Accounting for an extended loop geometry has the effect of increasing the estimated flare heights by a factor of ~3. These predictions are consistent with those derived using results of flaring loop models, which are also used to estimate the flaring loop properties and energetics. From loop models...

  17. Role of adsorbed arsenic and structural aluminum on Fe(II) retention and transformation of ferrihydrite (Invited)

    Science.gov (United States)

    Sharma, R.; Masue-Slowey, Y.; Fendorf, S. E.

    2009-12-01

    Arsenic is a wide-spread toxin contaminating water from both natural (as in the case of South and Southeast Asia) and anthropogenic sources. Its high affinity for soil solids helps to regulate the deleterious impacts of this toxic element on ecosystem and human health. Iron (hydr)oxides are of particular importance in controlling dissolved concentrations of arsenic, making the behavior of these substrates crucial to understanding the transport and ultimate fate of arsenic. Ferrihydrite is one of the most active forms of Fe (hydr)oxides, and aluminum-substituted ferrihydrite is a common form of this phase in soils and sediment. Sorption of Fe(II) catalyzes the transformation of the thermodynamically unstable ferrihydrite to more thermodynamically stable Fe (hydr)oxides. Although the process of ferrihydrite transformation has been extensively studied, the role of structural aluminum and adsorbed arsenic on the Fe(II)-catalyzed transformation of ferrihydrite is unknown. Hence, the objective of this study was to compare how ferrihydrite and aluminum-substituted ferrihydrite differ in their retention of Fe(II) and the resulting transformation rates and products in the presence and absence of arsenic. Sand coated with ferrihydrite and aluminum-ferrihydrite (with and without adsorbed arsenic) was packed into columns and flow of circumneutral groundwater solution containing 0.2 to 4 mM Fe(II) was initiated. Breakthrough of Fe(II) was monitored using the ferrozine colorimetric assay to determine Fe(II) retention in the solid phase. The solid phase was characterized using Fe K-edge X-ray absorption spectroscopy and scanning electron microscopy. Structural aluminum limits Fe(II) sorption, and, as a consequence, the extent of the aluminum-substituted ferrihydrite transformation is much less than that of ferrihydrite. Adsorbed As further decreases Fe(II) retention on aluminum-ferrihydrite. In contrast, Fe(II) retention on ferrihydrite is enhanced in the presence of arsenic due

  18. The reaction of hydrogen peroxide with Fe(II) ions at elevated temperatures

    DEFF Research Database (Denmark)

    Christensen, H.; Sehested, K.; Løgager, T.

    1993-01-01

    The rate constant for the reaction between Fe(II) ions and H2O2 has been determined at pH 0.4-2 as a function of temperature in the range 5-300-degrees-C. H2O2 was produced by irradiating the aqueous solution with a pulse of electrons. The rate constants at 20 and 300-degrees-C were determined to...

  19. Stability of continuously produced Fe(II)/Fe(III)/As(V) co-precipitates under periodic exposure to reducing agents.

    Science.gov (United States)

    Doerfelt, Christoph; Feldmann, Thomas; Daenzer, Renaud; Demopoulos, George P

    2015-11-01

    Arsenic mobilized during ore processing necessitates its effective removal from process effluents and disposal in environmentally stable tailings. The most common method to accomplish this involves co-precipitation with excess ferric iron during lime neutralization. The precipitates produced are stable under oxic conditions. This may not be true, however, under sub-oxic or anoxic conditions. In this context, the potential stabilizing role of ferrous iron on arsenic removal/retention becomes important. As such, this work investigates the removal and redox stability of arsenic with ferrous, ferric and mixtures of both. The stability of produced solids is monitored in terms of arsenic release over time. It was found that ferrous was very effective for arsenic (V) removal with Fe(II)/As(V)=4, reducing its concentration down to reducing agent exposure. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Dinuclear Metallacycles with Single M-X-M Bridges (X = Cl(-), Br(-); M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)): Strong Antiferromagnetic Superexchange Interactions.

    Science.gov (United States)

    Reger, Daniel L; Pascui, Andrea E; Foley, Elizabeth A; Smith, Mark D; Jezierska, Julia; Wojciechowska, Agnieszka; Stoian, Sebastian A; Ozarowski, Andrew

    2017-03-06

    A series of monochloride-bridged, dinuclear metallacycles of the general formula [M2(μ-Cl)(μ-L)2](ClO4)3 have been prepared using the third-generation, ditopic bis(pyrazolyl)methane ligands L = m-bis[bis(1-pyrazolyl)methyl]benzene (Lm), M = Cu(II), Zn(II), and L = m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (Lm*), M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II). These complexes were synthesized from the direct reactions of M(ClO4)2·6H2O, MCl2, and the ligand, Lm or Lm*, in the appropriate stoichiometric amounts. Three analogous complexes of the formula [M2(μ-Cl)(μ-L)2](BF4)3, L = Lm, M = Cu(II), and L = Lm*, M = Co(II), Cu(II), were prepared from the reaction of [M2(μ-F)(μ-L)2](BF4)3 and (CH3)3SiCl. The bromide-bridged complex [Cu2(μ-Br)(μ-Lm*)2](ClO4)3 was prepared by the first method. Three acyclic complexes, [Co2(μ-Lm)μ-Cl4], [Co2(μ-Lm*)Cl4], and [Co2(μ-Lm*)Br4], were also prepared. The structures of all [M2(μ-X)(μ-L)2](3+) (X = Cl(-), Br(-)) complexes have two ditopic bis(pyrazolyl)methane ligands bridging two metals in a metallacyclic arrangement. The fifth coordination site of the distorted trigonal bipyramidal metal centers is filled by a bridging halide ligand that has an unusual linear or nearly linear M-X-M angle. The NMR spectra of [Zn2(μ-Cl)(μ-Lm*)2](ClO4)3 and especially [Cd2(μ-Cl)(μ-Lm*)2](ClO4)3 demonstrate that the metallacycle structure is maintained in solution. Solid state magnetic susceptibility data for the copper(II) compounds show very strong antiferromagnetic exchange interactions, with -J values of 536 cm(-1) for [Cu2(μ-Cl)(μ-Lm)2](ClO4)3·xCH3CN, 720 cm(-1) for [Cu2(μ-Cl)(μ-Lm*)2](ClO4)3, and 945 cm(-1) for [Cu2(μ-Br)(μ-Lm*)2](ClO4)3·2CH3CN. Smaller but still substantial antiferromagnetic interactions are observed with other first row transition metals, with -J values of 98 cm(-1) for [Ni2(μ-Cl)(μ-Lm*)2](ClO4)3, 55 cm(-1) for [Co2(μ-Cl)(μ-Lm*)2](ClO4)3, and 34 cm(-1) for [Fe2(μ-Cl)(μ-Lm*)2](ClO4

  1. Interfacial charge separation and photovoltaic efficiency in Fe(ii)-carbene sensitized solar cells.

    Science.gov (United States)

    Pastore, Mariachiara; Duchanois, Thibaut; Liu, Li; Monari, Antonio; Assfeld, Xavier; Haacke, Stefan; Gros, Philippe C

    2016-10-12

    The first combined theoretical and photovoltaic characterization of both homoleptic and heteroleptic Fe(ii)-carbene sensitized photoanodes in working dye sensitized solar cells (DSSCs) has been performed. Three new heteroleptic Fe(ii)-NHC dye sensitizers have been synthesized, characterized and tested. Despite an improved interfacial charge separation in comparison to the homoleptic compounds, the heteroleptic complexes did not show boosted photovoltaic performances. The ab initio quantitative analysis of the interfacial electron and hole transfers and the measured photovoltaic data clearly evidenced fast recombination reactions for heteroleptics, even associated with un unfavorable directional electron flow, and hence slower injection rates, in the case of homoleptics. Notably, quantum mechanics calculations revealed that deprotonation of the not anchored carboxylic function in the homoleptic complex can effectively accelerate the electron injection rate and completely suppress the electron recombination to the oxidized dye. This result suggests that introduction of strong electron-donating substituents on the not-anchored carbene ligand in heteroleptic complexes, in such a way of mimicking the electronic effects of the carboxylate functionality, should yield markedly improved interfacial charge generation properties. The present results, providing for the first time a detailed understanding of the interfacial electron transfers and photovoltaic characterization in Fe(ii)-carbene sensitized solar cells, open the way to a rational molecular engineering of efficient iron-based dyes for photoelectrochemical applications.

  2. [Fe II] emissions associated with the young interacting binary UY Aurige

    CERN Document Server

    Pyo, Tae-Soo; Beck, Tracy; Davis, Christopher J; Takami, Michihiro

    2014-01-01

    We present high resolution 1.06 -- 1.28 micron spectra toward the interacting binary UY Aur obtained with GEMINI/NIFS and the AO system Altair. We have detected [FeII] $\\lambda$~1.257 micron and [He I] $\\lambda$~1.083 micron lines from both UY Aur A (the primary source) and UY Aur B (the secondary). In [Fe II] UY Aur A drives fast and widely opening outflows with an opening angle of ~ 90 degree along a position angle of ~40 degree, while UY Aur B is associated with a redshifted knot. The blueshifted and redshifted emissions show complicated structure between the primary and secondary. The radial velocities of the [Fe II] emission features are similar for UY Aur A and B: ~ -100 km/s for the blueshifted emission and ~ +130 km/s for the red-shifted component. The [He I] line profile observed toward UY Aur A comprises a central emission feature with deep absorptions at both blueshifted and redshifted velocities. These absorption features may be explained by stellar wind models. The [He I] line profile of UY Aur B...

  3. [Fe II] emissions associated with the young interacting binary UY Aurigae

    Energy Technology Data Exchange (ETDEWEB)

    Pyo, Tae-Soo [Subaru Telescope, National Astronomical Observatory of Japan, 650 North A' ohoku Place, Hilo, HI 96720 (United States); Hayashi, Masahiko [National Astronomical Observatory of Japan, 2-21-1 Osawa, Mitaka, Tokyo 181-8588 (Japan); Beck, Tracy L. [Space Telescope Science Institute, 3700 San Martin Drive, Baltimore, MD 21218 (United States); Davis, Christopher J. [Astrophysics Research Institute, Liverpool John Moores University, Liverpool Science Park, 146 Brownlow Hill, Liverpool L3 5RF (United Kingdom); Takami, Michihiro, E-mail: pyo@subaru.naoj.org [Institute of Astronomy and Astrophysics, Academia Sinica, P.O. Box 23-141, Taipei 10617, Taiwan (China)

    2014-05-01

    We present high-resolution 1.06-1.28 μm spectra toward the interacting binary UY Aur obtained with GEMINI/NIFS and the adaptive optics system Altair. We have detected [Fe II] λ1.257 μm and He I λ1.083 μm lines from both UY Aur A (the primary source) and UY Aur B (the secondary). In [Fe II] UY Aur A drives fast and widely opening outflows with an opening angle of ∼90° along a position angle of ∼40°, while UY Aur B is associated with a redshifted knot. The blueshifted and redshifted emissions show a complicated structure between the primary and secondary. The radial velocities of the [Fe II] emission features are similar for UY Aur A and B: ∼ –100 km s{sup –1} for the blueshifted emission and ∼ +130 km s{sup –1} for the redshifted component. The He I line profile observed toward UY Aur A comprises a central emission feature with deep absorptions at both blueshifted and redshifted velocities. These absorption features may be explained by stellar wind models. The He I line profile of UY Aur B shows only an emission feature.

  4. Crystal structure of K0.75[FeII3.75FeIII1.25(HPO36]·0.5H2O, an open-framework iron phosphite with mixed-valent FeII/FeIII ions

    Directory of Open Access Journals (Sweden)

    Edurne S. Larrea

    2016-01-01

    Full Text Available Single crystals of the title compound, potassium hexaphosphitopentaferrate(II,III hemihydrate, K0.75[FeII3.75FeIII1.25(HPO36]·0.5H2O, were grown under mild hydrothermal conditions. The crystal structure is isotypic with Li1.43[FeII4.43FeIII0.57(HPO36]·1.5H2O and (NH42[FeII5(HPO36] and exhibits a [FeII3.75FeIII1.25(HPO36]0.75− open framework with disordered K+ (occupancy 3/4 as counter-cations. The anionic framework is based on (001 sheets of two [FeO6] octahedra (one with point group symmetry 3.. and one with point group symmetry .2. linked along [001] through [HPO3]2− oxoanions. Each sheet is constructed from 12-membered rings of edge-sharing [FeO6] octahedra, giving rise to channels with a radius of ca 3.1 Å where the K+ cations and likewise disordered water molecules (occupancy 1/4 are located. O...O contacts between the water molecule and framework O atoms of 2.864 (5 Å indicate hydrogen-bonding interactions of medium strength. The infrared spectrum of the compound shows vibrational bands typical for phosphite and water groups. The Mössbauer spectrum is in accordance with the presence of FeII and FeIII ions.

  5. The reduction of chromate ions by Fe(II layered hydroxides

    Directory of Open Access Journals (Sweden)

    S. Loyaux-Lawniczak

    1999-01-01

    Full Text Available The reduction of chromate ions by Fe(OH2 and the iron (II-iron (III hydroxysulphate green rust, GR(SO42-, was studied to evaluate whether such synthetic layered hydroxides and the corresponding natural green rust mineral could be involved in the natural attenuation of contaminated environments. The resulting Cr (III bearing phases, which would govern the subsequent behaviour of chromium, were clearly characterised. Both compounds proved to be very reactive and oxidised instantaneously while chromate ions were reduced to Cr (III as evidenced by X-ray photoelectron spectroscopy. Mass balance (ICP-AES demonstrated that the Fe/Cr ratio inside the solid end product was equal to the initial Fe/Cr ratio. The solid phases, analysed by X-ray diffraction, Raman and Mossbauer spectroscopies were identified as Cr-substituted poorly crystallised iron (III oxyhydroxides in both cases, more precisely δ-FeOOH when starting with Fe(OH2 and ferrihydrite when starting with GR(SO42-.

  6. Autotrophic denitrification by nitrate-dependent Fe(II) oxidation in a continuous up-flow biofilter.

    Science.gov (United States)

    Zhou, Jun; Wang, Hongyu; Yang, Kai; Ji, Bin; Chen, Dan; Zhang, Huining; Sun, Yuchong; Tian, Jun

    2016-02-01

    A continuous-upflow biofilter packed with sponge iron was constructed for nitrate removal under an anaerobic atmosphere. Microbacterium sp. W5, a nitrate reducing and Fe(II) oxidizing strain, was added to the biofilter as an inoculum. The best results were achieved when NO3 (-)-N concentration was 30 mg/L and Fe(2+) was 800 mg/L. Nitrite in influent would inhibit nitrate removal and aqueous Fe(2+) resulted in encrustation. Fe(II)EDTA would prevent cells from encrustation and the maximum nitrogen removal efficiency was about 90 % with Fe(II)EDTA level of 1100 mg/L. Nitrate reduction followed first-order reaction kinetics. Characteristics of biofilms were analyzed by X-ray fluorescence spectroscopy.

  7. Incidence of H I 21-cm absorption in strong Fe II systems at 0.5 < z < 1.5

    Science.gov (United States)

    Dutta, R.; Srianand, R.; Gupta, N.; Joshi, R.; Petitjean, P.; Noterdaeme, P.; Ge, J.; Krogager, J.-K.

    2017-03-01

    We present the results from our search for H I 21-cm absorption in a sample of 16 strong Fe II systems [Wr(Mg II λ2796) ≥ 1.0 Å and Wr(Fe II λ2600) or W_{Fe II} ≥ 1 Å] at 0.5 measurements with those in the literature, we find that the detection rate of H I 21-cm absorption increases with W_{Fe II}, being four times higher in systems with W_{Fe II} ≥ 1 Å compared to systems with W_{Fe II} measurements of damped Lyman α systems at this redshift range) and unit covering factor. We find that H I 21-cm absorption arises on an average in systems with stronger metal absorption. We also find that quasars with H I 21-cm absorption detected towards them have systematically higher E(B - V) values than those which do not. Further, by comparing the velocity widths of H I 21-cm absorption lines detected in absorption- and galaxy-selected samples, we find that they show an increasing trend (significant at 3.8σ) with redshift at z < 3.5, which could imply that the absorption originates from more massive galaxy haloes at high z. Increasing the number of H I 21-cm absorption detections at these redshifts is important to confirm various trends noted here with higher statistical significance.

  8. Adsorption of Ni(II, Cu(II and Fe(III from Aqueous Solutions Using Activated Carbon

    Directory of Open Access Journals (Sweden)

    A. Edwin Vasu

    2008-01-01

    Full Text Available An activated carbon was tested for its ability to remove transition metal ions from aqueous solutions. Physical, Chemical and liquid-phase adsorption characterizations of the carbon were done following standard procedures. Studies on the removal of Ni(II, Cu(II and Fe(III ions were attempted by varying adsorbate dose, pH of the metal ion solution and time in batch mode. The equilibrium adsorption data were fitted with Freundlich, Langmuir and Redlich-Peterson isotherms and the isotherm constants were evaluated. Time variation studies indicate that adsorptions follow pseudo-second order kinetics. pH was found to have a significant role to play in the adsorption. The processes were endothermic and the thermodynamic parameters were evaluated. Desorption studies indicate that ion-exchange mechanism is operating.

  9. Preparation and XPS studies of macromolecule mixed-valent Cu(I, II) and Fe(II, III) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Wang Bo [Institute of Energy Chemistry, College of Chemistry and Materials Science, Shaanxi Normal University, Xi' An 710062 (China)]. E-mail: wangbo@snnu.edu.cn; Gao Fengqin [Institute of Energy Chemistry, College of Chemistry and Materials Science, Shaanxi Normal University, Xi' An 710062 (China); Department of Chemistry, Xianyang Normal University, Xianyang (China); Ma Hongzhu [Institute of Energy Chemistry, College of Chemistry and Materials Science, Shaanxi Normal University, Xi' An 710062 (China)

    2007-06-01

    A new macromolecule ligand and its mixed-valent Cu(I, II) and Fe(II, III) complexes have been prepared by using ethylenediamine as core and maleic anhydride as branched units and characterized by UV-vis, FT-IR, thermal analysis and X-ray photoelectron spectroscopy (XPS). The data obtained from these studies suggested that the coordinate bonds of N {sup {yields}} M, Cl {sup {yields}} M, Ph-OH {sup {yields}} M and H{sub 2}O {sup {yields}} M have been formed and possible binding models are proposed for these complexes. The thermal analysis (TG-DTG) reveals that these complexes possess thermal stable property below 800 deg. C.

  10. Identification and Characterization of MtoA: a Decaheme c-Type Cytochrome of the Neutrophilic Fe(II-oxidizing Bacterium Sideroxydans lithotrophicus ES-1

    Directory of Open Access Journals (Sweden)

    Juan eLiu

    2012-02-01

    Full Text Available The Gram-negative bacterium Sideroxydans lithotrophicus ES-1 (ES-1 grows on FeCO3 or FeS at oxic-anoxic interfaces at circumneutral pH, and the ES-1-mediated Fe(II oxidation occurs extracellularly. However, the molecular mechanisms underlying ES-1’s ability to oxidize Fe(II remain unknown. Survey of the ES-1 genome for candidate genes for microbial extracellular Fe(II oxidation revealed that it contained a three-gene cluster encoding homologues of MtrA, MtrB and CymA of Shewanella oneidensis MR-1 (MR-1 that are involved in extracellular Fe(III reduction. Homologues of MtrA and MtrB were also involved in extracellular Fe(II oxidation by Rhodopseudomonas palustris TIE-1. To distinguish them from those found in MR-1, the identified homologues were named MtoAB and CymAES-1. Cloned mtoA partially complemented an MR-1 mutant without MtrA with regards to ferrihydrite reduction. Characterization of purified MtoA showed that it was a decaheme c-type cytochrome and oxidized soluble Fe(II. Oxidation of Fe(II by MtoA was pH- and Fe(II-complexing ligand-dependent. Under conditions tested, MtoA oxidized Fe(II from pH 7-9 with the optimal rate at pH 9. MtoA oxidized Fe(II complexed with different ligands at different rates. The reaction rates followed the order Fe(IICl2 > Fe(II-citrate > Fe(II-NTA > Fe(II-EDTA with the second-order rate constants ranging from 6.3 × 10-3 μM-1s-1 for oxidation of Fe(IICl2 to 1.0 × 10-3 μM-1s-1 for oxidation of Fe(II-EDTA. Thermodynamic modeling shows that redox reaction rates for the different Fe(II-complexes correlated with their respective estimated reaction-free energies. Collectively, these results demonstrate that MtoA is a functional Fe(II-oxidizing protein and, by working in concert with MtoB and CymAES 1, may oxidize Fe(II at the bacterial surface and transfer released electrons across the bacterial cell envelope to the quinone pool in the inner membrane during extracellular Fe(II oxidation by ES-1.

  11. Biochemistry and Ecology of Novel Cytochromes Catalyzing Fe(II) Oxidation by an Acidophilic Microbial Community

    Science.gov (United States)

    Singer, S. W.; Jeans, C. J.; Thelen, M. P.; Verberkmoes, N. C.; Hettich, R. C.; Chan, C. S.; Banfield, J. F.

    2007-12-01

    An acidophilic microbial community found in the Richmond Mine at Iron Mountain, CA forms abundant biofilms in extremely acidic (pHcytochromes with unique properties. Sulfuric acid extraction of biofilm samples liberated one of these proteins, a 16 kDa cytochrome with an unusual alpha-band absorption at 579 (Cyt579). Genomic sequencing of multiple biofilms indicated that several variants of Cyt579 were present in Leptospirillum strains. Intact protein MS analysis identified the dominant variants in each biofilm and documented multiple N-terminal cleavage sites for Cyt579. By combining biochemical, geochemical and microbiological data, we established that the sequence variation and N-terminal processing of Cyt579 are selected by ecological conditions. In addition to the soluble Cyt579, the second cytochrome appears as a much larger protein complex of ~210 kDa predominant in the biofilm membrane fraction, and has an alpha-band absorption at 572 nm. The 60 kDa cytochrome subunit, Cyt572, resides in the outer membrane of LeptoII, and readily oxidizes Fe(II) at low pH (0.95 - 3.0). Several genes encoding Cyt572 were localized within a recombination hotspot between two strains of LeptoII, causing a large range of variation in the sequences. Genomic sequencing and MS proteomic studies established that the variants were also selected by ecological conditions. A general mechanistic model for Fe(II) oxidation has been developed from these studies. Initial Fe(II) oxidation by Cyt572 occurs at the outer membrane. Cyt572 then transfers electrons to Cyt579, perhaps representing an initial step in energy flow to the biofilm community. Amino acid variations and post-translational modifications of these unique cytochromes may represent fine-tuning of function in response to local environmental conditions.

  12. Adsorption antagonism and synergy of arsenate(V) and cadmium(II) onto Fe-modified rice straw biochars.

    Science.gov (United States)

    Zhang, Youchi; Fan, Jiajun; Fu, Minglai; Ok, Yong Sik; Hou, Yanwei; Cai, Chao

    2017-05-26

    Arsenic-containing water poses a serious threat to human health. In this study, two types of Fe-modified rice straw biochars [(Fe-impregnated biochar (FeIm char) and pre-modified rice straw biochar (PMRS char)] were prepared, in which three ratios [1, 5, and 10% (w/w)] of Fe modification were evaluated, resulting in six different Fe-modified biochars. Then, a series of adsorption experiments, using single- and binary-metal solutions of As(V) and Cd(II), were conducted to investigate the performances of modified biochars on metal adsorption compared to pristine rice straw biochar (RS char). Results indicated Fe modification improved the As(V) adsorption capacity of biochar. PMRS char showed higher adsorption of As(V) than FeIm char. At the 5% Fe modification ratio (FMR), the As(V) removal by PMRS char (at 10 g/L dosage) from 100 mg/L As(V) solution was approximately 69.6%, which was higher than 46.1% of FeIm char or 22.6% of RS char. In contrast, the adsorption of Cd(II) was decreased after modified at 5 or 10% FMR. Interestingly, for treating solution containing As(V) and Cd(II) together, the adsorption of As(V) onto FeIm char or PMRS char prepared at 5 or 10% FMR remained higher than that onto RS char, while the simultaneous removal of Cd(II) ion by either modified biochar was kept over 50%. Thus, the finding of this study suggested Fe-modified biochars, especially prepared via the pyrolysis of FeCl3 pre-soaking rice straw, could be a promising adsorbent for the remediation of complex As(V)-containing wastewater.

  13. Distribution of manganese species in an oxidative dimerization reaction of a bis-terpyridine mononuclear manganese (II) complex and their heterogeneous water oxidation activities.

    Science.gov (United States)

    Takahashi, Kosuke; Sato, Taisei; Yamazaki, Hirosato; Yagi, Masayuki

    2015-11-01

    Heterogeneous water oxidation catalyses were studied as a synthetic model of oxygen evolving complex (OEC) in photosynthesis using mica adsorbing various manganese species. Distribution of manganese species formed in the oxidative dimerization reaction of [Mn(II)(terpy)2](2+) (terpy=2,2':6',2″-terpyridine) (1') with various oxidants in water was revealed. 1' was stoichiometrically oxidized to form di-μ-oxo dinuclear manganese complex, [(OH2)(terpy)Mn(III)(μ-O)2Mn(IV)(terpy)(OH2)](3+) (1) by KMnO4 as an oxidant. When Oxone and Ce(IV) oxidants were used, the further oxidation of 1 to [(OH2)(terpy)Mn(IV)(μ-O)2Mn(IV)(terpy)(OH2)](4+) (2) was observed after the oxidative dimerization reaction of 1'. The mica adsorbates with various composition of 1', 1 and 2 were prepared by adding mica suspension to the various oxidant-treated solutions followed by filtration. The heterogeneous water oxidation catalysis by the mica adsorbates was examined using a Ce(IV) oxidant. The observed catalytic activity of the mica adsorbates corresponded to a content of 1 (1ads) adsorbed on mica for KMnO4- and Oxone-treated systems, indicating that 1' (1'ads) and 2 (2ads) adsorbed on mica do not work for the catalysis. The kinetic analysis suggested that 1ads works for the catalysis through cooperation with adjacent 1ads or 2ads, meaning that 2ads assists the cooperative catalysis by 1ads though 2ads is not able to work for the catalysis alone. For the Ce(IV)-treated system, O2 evolution was hardly observed although the sufficient amount of 1ads was contained in the mica adsorbates. This was explained by the impeded penetration of Ce(IV) ions (as an oxidant for water oxidation) into mica by Ce(3+) cations (generated in oxidative dimerization of 1') co-adsorbed with 1ads.

  14. Direct and simultaneous spectrophotometric determination of Fe (III and Ni (II using salicylaldehyde acetoacetic acid hydrazone – Applications

    Directory of Open Access Journals (Sweden)

    V Srilalitha

    2010-12-01

    Full Text Available A rapid, simple and sensitive spectrophotometric method has been developed for determination of Fe (III and Ni (II using salicylaldehyde acetoacetic acid hydrazone (SAAH as a chromophoric reagent. The linear calibration ranges were obtained in each case. The proposed method is applied for the simultaneous determination of Fe (III and Ni (II utilizing their first order spectra. The method is based on the zero crossing measurement of first derivative amplitudes. The first derivative amplitudes at 525 nm and 395 nm obey Beer's law in the concentration range 0.054-0.270 μg/mL and 0.112-0.561 μg/mL for Fe (III and Ni (II respectively. A large number of foreign ions do not interfere in the present method. The method is used for the determination of micro amounts of Fe (III and Ni (II in alloy steels and in synthetic mixtures.

  15. Multifunctional nanocomposites Fe3O4@SiO2-EDTA for Pb(II) and Cu(II) removal from aqueous solutions

    Science.gov (United States)

    Liu, Yu; Fu, Ruiqi; Sun, Yue; Zhou, Xiaoxin; Baig, Shams Ali; Xu, Xinhua

    2016-04-01

    In this study, EDTA-functionalized Fe3O4 (Fe3O4@SiO2-EDTA) was prepared by silanization reaction between N-(trimethoxysilylpropyl) ethylenediamine triacetic acid (EDTA-silane) and hydroxyl groups for Pb(II) and Cu(II) removal from aqueous solutions. Fe3O4@SiO2-EDTA composites were characterized using SEM, TEM, EDX, FTIR, XPS, TGA and saturated magnetization techniques. Maximum Pb(II) adsorption capacity was found to be 114.94 mg g-1 with SiO2/EDTA molar ratio of 2.5:1. The adsorption rate was significantly fast and the equilibrium was reached within 10 min. The optimum pH was recorded to be 5.0. The maximum adsorption capacity of the studied heavy metal ions calculated by Langmuir model followed the order: Cu(II) (0.58 mmol g-1) > Pb(II) (0.55 mmol g-1) ≈ Ni(II) (0.55 mmol g-1) > Cd(II) (0.45 mmol g-1). Moreover, Pb(II) and Cu(II) adsorption capacities were not significantly affected by co-existing cations and NOM. These results suggested that this adsorbent can be considered as a promising adsorbent to remove Pb(II) and Cu(II) from wastewaters.

  16. Free energy of formation for green rust sodium sulphate (NaFe II6Fe III3(OH) 18(SO 4) 2(s))

    Science.gov (United States)

    Davesne, E.; Dideriksen, K.; Christiansen, B. C.; Sonne, M.; Ayala-Luis, K. B.; Koch, C. Bender; Hansen, H. C. B.; Stipp, S. L. S.

    2010-11-01

    In a recent study, sulphate-bearing green rust (GR) was shown to incorporate Na + in its structure (NaFe II6Fe III3(OH) 18(SO 4) 2(s); GR). The compound was synthesised by aerial oxidation of Fe(OH) 2(s) in the presence of NaOH. This paper reports on its free energy of formation (ΔGf0). Freshly synthesised GR was titrated with 0.5 M H 2SO 4 in an inert atmosphere at 25 °C, producing dissolved Fe 2+ and magnetite or goethite. Solution concentrations, PHREEQC and the MINTEQ database were used to calculate reaction constants for the reactions: 2NaFeII6 FeIII3 (OH)18(SO)+12H+(aq) ⇆9Fe2+(aq) +2Na+(aq) +4SO42-(aq) +3FeFeIII2 O+24HO,K=10 and NaFeII6 FeIII3 (OH)18(SO)+9H(aq)+⇆6Fe2+(aq) +Na+(aq) +2SO42-(aq) +3α-FeOOH+12HO,K=10. From the determined equilibrium constants and published ΔGf0 values for the other compounds, we derived ΔGf0 = -6366 ± 18 kJ/mol for anhydrous GR. The solubility product at 25 °C and atmospheric pressure is K = 10 -210.5±3.2. It is not yet known if the extent of Na + incorporation in GR depends on formation pathway; it cannot be excluded that both Na-free GR and GR exist. If so, uncertainty in ΔGf0 determined from acid titration is such that the EH-pH stability fields of the two phases are statistically indistinguishable for Na + concentrations as low as ˜30 μM (2 SD level; 0.036 M SO 42- concentration). In sea water, where Na + and SO 42- concentrations are high, but soluble Fe 2+ is low, GR is expected to form where local conditions increase concentration gradients, such as for corrosion of metallic iron and steel. Another example of an environment that would provide GR-favourable conditions is a degrading concrete and steel radioactive waste storage facility, where groundwater is saline. Green rust is a well-known sink for redox-active trace components, making it a compound that should be considered in risk assessment modelling of groundwater quality. Phase stability is critical in such simulations.

  17. Treatment of groundwater containing Mn(II), Fe(II), As(III) and Sb(III) by bioaugmented quartz-sand filters.

    Science.gov (United States)

    Bai, Yaohui; Chang, Yangyang; Liang, Jinsong; Chen, Chen; Qu, Jiuhui

    2016-12-01

    High concentrations of iron (Fe(II)) and manganese (Mn(II)) often occur simultaneously in groundwater. Previously, we demonstrated that Fe(II) and Mn(II) could be oxidized to biogenic Fe-Mn oxides (BFMO) via aeration and microbial oxidation, and the formed BFMO could further oxidize and adsorb other pollutants (e.g., arsenic (As(III)) and antimony (Sb(III))). To apply this finding to groundwater remediation, we established four quartz-sand columns for treating groundwater containing Fe(II), Mn(II), As(III), and Sb(III). A Mn-oxidizing bacterium (Pseudomonas sp. QJX-1) was inoculated into two parallel bioaugmented columns. Long-term treatment (120 d) showed that bioaugmentation accelerated the formation of Fe-Mn oxides, resulting in an increase in As and Sb removal. The bioaugmented columns also exhibited higher overall treatment effect and anti-shock load capacity than that of the non-bioaugmented columns. To clarify the causal relationship between the microbial community and treatment effect, we compared the biomass of active bacteria (reverse-transcribed real-time PCR), bacterial community composition (Miseq 16S rRNA sequencing) and community function (metagenomic sequencing) between the bioaugmented and non-bioaugmented columns. Results indicated that the QJX1 strain grew steadily and attached onto the filter material surface in the bioaugmented columns. In general, the inoculated strain did not significantly alter the composition of the indigenous bacterial community, but did improve the relative abundances of xenobiotic metabolism genes and Mn oxidation gene. Thus, bioaugmentation intensified microbial degradation/utilization for the direct removal of pollutants and increased the formation of Fe-Mn oxides for the indirect removal of pollutants. Our study provides an alternative method for the treatment of groundwater containing high Fe(II), Mn(II) and As/Sb. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Biological Oxidation of Fe(II) in Reduced Nontronite Coupled with Nitrate Reduction by Pseudogulbenkiania sp. Strain 2002

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.; Agrawal, A.; Liu, Deng; Zhang, Jing; Edelmann, Richard E.

    2013-10-15

    Nitrate contamination in soils, sediments, and water bodies is a significant issue. Although much is known about nitrate degradation in these environments, especially via microbial pathways, a complete understanding of all degradation processes, especially in clay mineral-rich soils, is still lacking. The objective of this study was to study the potential of removing nitrate contaminant using structural Fe(II) in clay mineral nontronite. Specifically, the coupled processes of microbial oxidation of Fe(II) in microbially reduced nontronite (NAu-2) and nitrate reduction by Pseudogulbenkiania species strain 2002 was investigated. Bio-oxidation experiments were conducted in bicarbonate-buffered medium under both growth and nongrowth conditions. The extents of Fe(II) oxidation and nitrate reduction were measured by wet chemical methods. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and 57Fe-Mössbauer spectroscopy were used to observe mineralogical changes associated with Fe(III) reduction and Fe(II) oxidation in nontronite. The bio-oxidation extent under growth and nongrowth conditions reached 93% and 57%, respectively. Over the same time period, nitrate was completely reduced under both conditions to nitrogen gas (N2), via an intermediate product nitrite. Magnetite was a mineral product of nitrate-dependent Fe(II) oxidation, as evidenced by XRD data and TEM diffraction patterns. The results of this study highlight the importance of iron-bearing clay minerals in the global nitrogen cycle with potential applications in nitrate removal in soils.

  19. EMPIRICAL DETERMINATION OF EINSTEIN A-COEFFICIENT RATIOS OF BRIGHT [Fe II] LINES

    Energy Technology Data Exchange (ETDEWEB)

    Giannini, T.; Antoniucci, S.; Nisini, B.; Lorenzetti, D. [INAF-Osservatorio Astronomico di Roma, Via Frascati 33, I-00040 Monte Porzio Catone (Italy); Alcalá, J. M. [INAF-Osservatorio Astronomico di Capodimonte, Via Moiariello 16, I-80131 Napoli (Italy); Bacciotti, F.; Podio, L. [INAF-Osservatorio Astrofisico di Arcetri, Largo E. Fermi 5, I-50125 Firenze (Italy); Bonito, R.; Stelzer, B., E-mail: teresa.giannini@oa-roma.inaf.it [INAF-Osservatorio Astronomico di Palermo, Piazza del Parlamento 1, I-90134 Palermo (Italy)

    2015-01-01

    The Einstein spontaneous rates (A-coefficients) of Fe{sup +} lines have been computed by several authors with results that differ from each other by up to 40%. Consequently, models for line emissivities suffer from uncertainties that in turn affect the determination of the physical conditions at the base of line excitation. We provide an empirical determination of the A-coefficient ratios of bright [Fe II] lines that would represent both a valid benchmark for theoretical computations and a reference for the physical interpretation of the observed lines. With the ESO-Very Large Telescope X-shooter instrument between 3000 Å and 24700 Å, we obtained a spectrum of the bright Herbig-Haro object HH 1. We detect around 100 [Fe II] lines, some of which with a signal-to-noise ratios ≥100. Among these latter lines, we selected those emitted by the same level, whose dereddened intensity ratios are direct functions of the Einstein A-coefficient ratios. From the same X-shooter spectrum, we got an accurate estimate of the extinction toward HH 1 through intensity ratios of atomic species, H I  recombination lines and H{sub 2} ro-vibrational transitions. We provide seven reliable A-coefficient ratios between bright [Fe II] lines, which are compared with the literature determinations. In particular, the A-coefficient ratios involving the brightest near-infrared lines (λ12570/λ16440 and λ13209/λ16440) are in better agreement with the predictions by the Quinet et al. relativistic Hartree-Fock model. However, none of the theoretical models predict A-coefficient ratios in agreement with all of our determinations. We also show that literature data of near-infrared intensity ratios better agree with our determinations than with theoretical expectations.

  20. Nano-sized magnetic iron oxides as catalysts for heterogeneous Fenton-like reactions-Influence of Fe(II)/Fe(III) ratio on catalytic performance.

    Science.gov (United States)

    Rusevova, Klara; Kopinke, Frank-Dieter; Georgi, Anett

    2012-11-30

    Nano-sized Fe(II, III) oxides with various Fe(II)/Fe(III) ratios were characterized and tested as catalysts for the oxidative degradation of phenol via Fenton-like reactions at neutral pH. Under conditions typically applied for wet peroxide oxidation, Fe(II) in magnetite is oxidized to Fe(III), successively converting the mineral into maghemite. The residual Fe(II) content in the catalyst core is of only minor benefit for the catalytic activity in phenol oxidation, i.e. magnetite is not superior to maghemite. Achievable reaction rates for phenol degradation appeared to be rather low, e.g. phenol half-life of about 12 h when 3 g L(-1) magnetite and 5 g L(-1) H(2)O(2) were applied. Preceding surface-reduction of maghemite by NaBH(4), leading to an over-stoichiometric Fe(II) content compared to magnetite, only enhanced the non-productive decomposition of H(2)O(2) rather than the rate of phenol degradation. Reaction rates were shown to be relatively insensitive to catalyst concentration in the range of 1-10 g L(-1), probably resulting from a scavenging of reactive species by the catalyst surface, whereby particle agglomeration seems to play a key role. Degradation experiments with various structurally distinct compounds were carried out, indicating a similar selectivity of the heterogeneous Fenton-like system to that known for oxidation with ·OH. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Speciation of Fe(II) and Fe(III) by the modified ferrozine method, FIA-spectrophotometry, and flame AAS after cloud-point extraction

    Energy Technology Data Exchange (ETDEWEB)

    Giokas, Dimosthenis L.; Paleologos, Evangelos K.; Karayannis, Miltiades I. [Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina (Greece)

    2002-07-01

    A method has been developed for the simultaneous determination of traces of Fe(III) and Fe(II) in water by on-line coupling of spectrophotometry with flame atomic absorption spectrometry (FAAS). The method involves cloud-point extraction (CPE) of both species with ammonium pyrrolidinecarbodithioate (APDC) under standard conditions, which facilitates the in situ complexation and extraction of both species. Differentiation of the oxidation states of iron is achieved by using mathematical equations to overcome the interference of Fe(III) in the spectrophotometric determination of Fe(II) when they are both present in the same solution. In this manner the time-consuming and labor-intensive steps of preoxidation of Fe(II) or reduction of Fe(III) are eliminated. By preconcentrating a 10-mL sample solution detection limits as low as 7 {mu}g L{sup -1}, were obtained after a single-step extraction procedure. The relative standard deviation (n=4, 30 {mu}g L{sup -1}) was 2.6 % and 1.8 % for spectrophotometry and FAAS, respectively. Recoveries in the range of 96-105 % were obtained by analysis of spiked real samples. The method was further verified by analyzing a certified reference material (IMEP-9); for this the recovery was 98.5 %. (orig.)

  2. Synthesis, structure determination, and spectroscopic/computational characterization of a series of Fe(II)-thiolate model complexes: implications for Fe-S bonding in superoxide reductases.

    Science.gov (United States)

    Fiedler, Adam T; Halfen, Heather L; Halfen, Jason A; Brunold, Thomas C

    2005-02-16

    A combined synthetic/spectroscopic/computational approach has been employed to prepare and characterize a series of Fe(II)-thiolate complexes that model the square-pyramidal [Fe(II)(N(His))(4)(S(Cys))] structure of the reduced active site of superoxide reductases (SORs), a class of enzymes that detoxify superoxide in air-sensitive organisms. The high-spin (S = 2) Fe(II) complexes [(Me(4)cyclam)Fe(SC(6)H(4)-p-OMe)]OTf (2) and [FeL]PF(6) (3) (where Me(4)cyclam = 1,4,8,11-tetramethylcyclam and L is the pentadentate monoanion of 1-thioethyl-4,8,11-trimethylcyclam) were synthesized and subjected to structural, magnetic, and electrochemical characterization. X-ray crystallographic studies confirm that 2 and 3 possess an N(4)S donor set similar to that found for the SOR active site and reveal molecular geometries intermediate between square pyramidal and trigonal bipyramidal for both complexes. Electronic absorption, magnetic circular dichroism (MCD), and variable-temperature variable-field MCD (VTVH-MCD) spectroscopies were utilized, in conjunction with density functional theory (DFT) and semiemperical INDO/S-CI calculations, to probe the ground and excited states of complexes 2 and 3, as well as the previously reported Fe(II) SOR model [(L(8)py(2))Fe(SC(6)H(4)-p-Me)]BF(4) (1) (where L(8)py(2) is a tetradentate pyridyl-appended diazacyclooctane macrocycle). These studies allow for a detailed interpretation of the S-->Fe(II) charge transfer transitions observed in the absorption and MCD spectra of complexes 1-3 and provide significant insights into the nature of Fe(II)-S bonding in complexes with axial thiolate ligation. Of the three models investigated, complex 3 exhibits an absorption spectrum that is particularly similar to the one reported for the reduced SOR enzyme (SOR(red)), suggesting that this model accurately mimics key elements of the electronic structure of the enzyme active site; namely, highly covalent Fe-S pi- and sigma-interactions. These spectral

  3. Advanced oxidation removal of hypophosphite by O3/H2O2 combined with sequential Fe(II) catalytic process.

    Science.gov (United States)

    Zhao, Zilong; Dong, Wenyi; Wang, Hongjie; Chen, Guanhan; Wang, Wei; Liu, Zekun; Gao, Yaguang; Zhou, Beili

    2017-08-01

    Elimination of hypophosphite (HP) was studied as an example of nickel plating effluents treatment by O3/H2O2 and sequential Fe(II) catalytic oxidation process. Performance assessment performed with artificial HP solution by varying initial pH and employing various oxidation processes clearly showed that the O3/H2O2─Fe(II) two-step oxidation process possessed the highest removal efficiency when operating under the same conditions. The effects of O3 dosing, H2O2 concentration, Fe(II) addition and Fe(II) feeding time on the removal efficiency of HP were further evaluated in terms of apparent kinetic rate constant. Under improved conditions (initial HP concentration of 50 mg L(-1), 75 mg L(-1) O3, 1 mL L(-1) H2O2, 150 mg L(-1) Fe(II) and pH 7.0), standard discharge (oxidation treatment favored the improvement of phosphorus removal due to the formation of more metal hydroxides. Moreover, as a comparison with lab-scale Fenton approach, the O3/H2O2─Fe(II) oxidation process had more competitive advantages with respect to applicable pH range, removal efficiency, sludge production as well as economic costs. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides - II. Effects of chloride and sulfate

    Science.gov (United States)

    Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

    2004-01-01

    Common complexing ligands such as chloride and sulfate can significantly impact the sorption of Hg(II) to particle surfaces in aqueous environmental systems. To examine the effects of these ligands on Hg(II) sorption to mineral sorbents, macroscopic Hg(II) uptake measurements were conducted at pH 6 and [Hg]i=0.5 mM on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) in the presence of chloride or sulfate, and the sorption products were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. The presence of chloride resulted in reduced uptake of Hg(II) on all three substrates over the Cl- concentration ([Cl-]) range 10-5 to 10-2 M, lowering Hg surface coverages on goethite, ??-alumina, and bayerite from 0.42 to 0.07 ??mol/m2, 0.06 to 0.006 ??mol/m2, and 0.55 to 0.39 ??mol/m2 ([Cl -]=10-5 to 10-3 M only), respectively. This reduction in Hg(II) uptake is primarily a result of the formation of stable, nonsorbing aqueous HgCl2 complexes in solution, limiting the amount of free Hg(II) available to sorb. At higher [Cl-] beam reduction of Hg(II) to Hg(I) was observed, resulting in the possible formation of aqueous Hg2Cl2 species and the precipitation of calomel, Hg 2Cl2(s). The presence of sulfate caused enhanced Hg(II) uptake over the sulfate concentration ([SO42-]) range 10-5 to 0.9 M, increasing Hg surface coverages on goethite, ??-alumina, and bayerite from 0.39 to 0.45 ??mol/m2, 0.11 to 0.38 ??mol/m2, and 0.36 to 3.33 ??mol/m2, respectively. This effect is likely due to the direct sorption or accumulation of sulfate ions at the substrate interface, effectively reducing the positive surface charge that electrostatically inhibits Hg(II) sorption. Spectroscopic evidence for ternary surface complexation was observed in isolated cases, specifically in the Hg-goethite-sulfate system at high [SO42-] and in the Hg-goethite-chloride system. ?? 2003 Elsevier Inc. All rights reserved.

  5. Empirical determination of Einstein A-coefficient ratios of bright [Fe II] lines

    CERN Document Server

    Giannini, T; Nisini, B; Lorenzetti, D; Alcala', J M; Bacciotti, F; Bonito, R; Podio, L; Stelzer, B

    2014-01-01

    The Einstein spontaneous rates (A-coefficients) of Fe^+ lines have been computed by several authors, with results that differ from each other up to 40%. Consequently, models for line emissivities suffer from uncertainties which in turn affect the determination of the physical conditions at the base of line excitation. We provide an empirical determination of the A-coefficient ratios of bright [Fe II] lines, which would represent both a valid benchmark for theoretical computations and a reference for the physical interpretation of the observed lines. With the ESO-VLT X-shooter instrument between 3,000 A, and 24,700 A, we obtained a spectrum of the bright Herbig-Haro object HH1. We detect around 100 [Fe II] lines, some of which with a signal-to-noise ratio > 100. Among these latter, we selected those emitted by the same level, whose de-reddened intensity ratio is a direct function of the Einstein A-coefficient ratios. From the same X-shooter spectrum, we got an accurate estimate of the extinction toward HH1 thr...

  6. Arsenic Uptake by Hydroxyapatite in the Presence of Fe(II)

    Science.gov (United States)

    Sahai, N.; Lee, Y. J.; Xu, H.; Ciardelli, M.

    2005-12-01

    We have examined As(III) and As(V) uptake by hydroxyapatite (HAP) in the absence and presence of the commonly occurring geochemical species, Fe(II), in a system open to the atmosphere and at near-neutral pH. The immediate goal of our project is to develop an inexpensive, efficient remediation method for the acute As contamination problem in well-waters of Bangladesh and Eastern India. Our study also provide a conceptual model system for understanding cation, neutral species and anion uptake by a class of minerals (apatites) capable of multiple substitutions, the effect of co-ions on metal(loid) uptake and the geochemically ubiquitous, but relatively poorly-understood, process of coprecipitation. Batch experiments on HAP suspensions, equilibrated for 24 hours, indicate that As(III) and As(V) uptake is slightly greater in the presence of HAP compared to the control experiment. The addition of Fe(II) significantly improves As(III) and As(V) uptake from solutions, both, without and with HAP suspensions. Analyses of equilibrated solutions and High Resolution Transmission Electron Microscopy of solids formed suggest that precipitation of amorphous FePO4.nH2O nanoparticles (10-20 nm) is mainly responsible for As removal with additional uptake by HAP. The efficiency of the process suggests the potential for an effective remediation strategy of As-contaminated drinking water after it has been withdrawn from the affected well.

  7. Crystal structure of the coordination polymer [FeIII2{PtII(CN4}3

    Directory of Open Access Journals (Sweden)

    Maksym Seredyuk

    2015-01-01

    Full Text Available The title complex, poly[dodeca-μ-cyanido-diiron(IIItriplatinum(II], [FeIII2{PtII(CN4}3], has a three-dimensional polymeric structure. It is built-up from square-planar [PtII(CN4]2− anions (point group symmetry 2/m bridging cationic [FeIIIPtII(CN4]+∞ layers extending in the bc plane. The FeII atoms of the layers are located on inversion centres and exhibit an octahedral coordination sphere defined by six N atoms of cyanide ligands, while the PtII atoms are located on twofold rotation axes and are surrounded by four C atoms of the cyanide ligands in a square-planar coordination. The geometrical preferences of the two cations for octahedral and square-planar coordination, respectively, lead to a corrugated organisation of the layers. The distance between neighbouring [FeIIIPtII(CN4]+∞ layers corresponds to the length a/2 = 8.0070 (3 Å, and the separation between two neighbouring PtII atoms of the bridging [PtII(CN4]2− groups corresponds to the length of the c axis [7.5720 (2 Å]. The structure is porous with accessible voids of 390 Å3 per unit cell.

  8. Applicability of anaerobic nitrate-dependent Fe(II) oxidation to microbial enhanced oil recovery (MEOR).

    Science.gov (United States)

    Zhu, Hongbo; Carlson, Han K; Coates, John D

    2013-08-06

    Microbial processes that produce solid-phase minerals could be judiciously applied to modify rock porosity with subsequent alteration and improvement of floodwater sweep in petroleum reservoirs. However, there has been little investigation of the application of this to enhanced oil recovery (EOR). Here, we investigate a unique approach of altering reservoir petrology through the biogenesis of authigenic rock minerals. This process is mediated by anaerobic chemolithotrophic nitrate-dependent Fe(II)-oxidizing microorganisms that precipitate iron minerals from the metabolism of soluble ferrous iron (Fe(2+)) coupled to the reduction of nitrate. This mineral biogenesis can result in pore restriction and reduced pore throat diameter. Advantageously and unlike biomass plugs, these biominerals are not susceptible to pressure or thermal degradation. Furthermore, they do not require continual substrate addition for maintenance. Our studies demonstrate that the biogenesis of insoluble iron minerals in packed-bed columns results in effective hydrology alteration and homogenization of heterogeneous flowpaths upon stimulated microbial Fe(2+) biooxidation. We also demonstrate almost 100% improvement in oil recovery from hydrocarbon-saturated packed-bed columns as a result of this metabolism. These studies represent a novel departure from traditional microbial EOR approaches and indicate the potential for nitrate-dependent Fe(2+) biooxidation to improve volumetric sweep efficiency and enhance both the quality and quantity of oil recovered.

  9. GalICS II: the [alpha/Fe]-mass relation in elliptical galaxies

    CERN Document Server

    Pipino, A; Thomas, D; Silk, J; Kaviraj, S

    2008-01-01

    We aim at reproducing the mass- and sigma-[alpha/Fe] relations in the stellar populations of early-type galaxies by means of a cosmologically motivated assembly history for the spheroids. We implement a detailed treatment for the chemical evolution of H, He, O and Fe in GalICS, a semi-analytical model for galaxy formation which successfully reproduces basic low- and high-redshift galaxy properties. The contribution of supernovae (both type Ia and II) as well as low- and intermediate-mass stars to chemical feedback are taken into account. We find that this chemically improved GalICS does not produce the observed mass- and sigma-[alpha/Fe] relations. The slope is too shallow and scatter too large, in particular in the low and intermediate mass range. The model shows significant improvement at the highest masses and velocity dispersions, where the predicted [alpha/Fe] ratios are now marginally consistent with observed values. We show that this result comes from the implementation of AGN (plus halo) quenching of ...

  10. A combined experimental and theoretical study of the supramolecular self-assembly of Cu(II) malonate complex assisted by various weak forces and water dimer

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Prankrishna [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India); Ray Choudhury, Somnath [Central Chemical Laboratory, Geological Survey of India, 15 A and B Kyd Street, Kolkata 700 016 (India); Mitra, Monojit [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India); Kumar Seth, Saikat [Department of Physics, M. G. Mahavidyalaya, Bhupatinagar, Purba Medinipur, West Bengal 721 425 (India); Helliwell, Madeleine [School of Chemistry, The University of Manchester, Brunswick Street, Manchester M13 9PL (United Kingdom); Bauzá, Antonio [Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma (Baleares) (Spain); Frontera, Antonio, E-mail: toni.frontera@uib.es [Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma (Baleares) (Spain); Mukhopadhyay, Subrata, E-mail: smukhopadhyay@chemistry.jdvu.ac.in [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India)

    2014-12-15

    A Cu(II) malonate complex with formula [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)]{sub 2}·4H{sub 2}O (1) [C{sub 6}H{sub 8}N{sub 2}=2-picolylamine, C{sub 3}H{sub 2}O{sub 4}{sup 2−}=malonate dianion] has been synthesized by mixing the reactants in their stoichiometric proportion and its crystal structure has been determined by single-crystal X-ray diffraction. In 1, monomeric neutral metal malonate units [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)] are interlinked with each other through hydrogen bonds, weak lone pair⋯π and cuprophilic interactions to generate supramolecular dimers, which in turn further associated through hydrogen bonding to form infinite 1D chains. Water dimers, through series of hydrogen bonds and weak π–stacking forces are found to be responsible for interconnection of 1D chains, which resulted in a 3D network. A density functional (DFT) study of the energetic features of several noncovalent interactions observed in the solid state have been analyzed and characterized using Bader's theory of “atoms-in-molecules”. We also present here Hirshfeld surface analysis to investigate the close intermolecular contacts. - Graphical Abstract: Interplay of weak forces like hydrogen bonding, lone pair⋯π, Cu⋯Cu and π–stacking interactions leading to the formation of supramolecular network in [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)]{sub 2}·4H{sub 2}O complex. - Highlights: • A complex of Cu(II) with malonate and 2-picolylamine is synthesized and X-ray characterized. • We report a density functional study of the energetic features of several noncovalent interactions • We perform Hirshfeld surface analysis to investigate the close intermolecular contacts.

  11. Determination of the Fe(II)aq-magnetite equilibrium iron isotope fractionation factor using the three-isotope method and a multi-direction approach to equilibrium

    Science.gov (United States)

    Frierdich, Andrew J.; Beard, Brian L.; Scherer, Michelle M.; Johnson, Clark M.

    2014-04-01

    Magnetite is ubiquitous in the Earth's crust and its presence in modern marine sediments has been taken as an indicator of biogeochemical Fe cycling. Magnetite is also the most abundant Fe oxide in banded iron formations (BIFs) that have not been subjected to ore-forming alteration. Magnetite is therefore an important target of stable Fe isotope studies, and yet interpretations are currently difficult because of large uncertainties in the equilibrium stable Fe isotope fractionation factors for magnetite relative to fluids and other minerals. In this study, we utilized the three-isotope method (57Fe-56Fe-54Fe) to explore isotopic exchange via an enriched-57Fe tracer, and natural mass-dependent fractionation using 56Fe/54Fe variations, during reaction of aqueous Fe(II) (Fe(II)aq) with magnetite. Importantly, we employed a multi-direction approach to equilibrium by reacting four 57Fe-enriched Fe(II) solutions that had distinct 56Fe/54Fe ratios, which identifies changes in the instantaneous Fe isotope fractionation factor and hence identifies kinetic isotope effects. We find that isotopic exchange can be described by two 56Fe/54Fe fractionations, where an initial rapid exchange (∼66% isotopic mixing within 1 day) involved a relatively small Fe(II)aq-magnetite 56Fe/54Fe fractionation, followed by slower exchange (∼25% isotopic mixing over 50 days) that was associated with a larger Fe(II)aq-magnetite 56Fe/54Fe fractionation; this later fractionation is interpreted to approach isotopic equilibrium between Fe(II)aq and the total magnetite. All four Fe(II) solutions extrapolate to the same final equilibrium 56Fe/54Fe fractionation for Fe(II)aq-magnetite of -1.56±0.20‰ (2σ) at 22 °C. Additional experiments that synthesized magnetite via conversion of ferrihydrite by reaction with aqueous Fe(II) yield final 56Fe/54Fe fractionations that are identical to those of the exchange experiments. Our experimental results agree well with calculated fractionation factors using

  12. Composition and anion ordering in some Fe II-III hydroxysalt green rusts (carbonate, oxalate, methanoate): The fougerite mineral

    Science.gov (United States)

    Génin, Jean-Marie R.; Ruby, Christian

    2008-03-01

    Main features of Fe II-III hydroxysalts (green rusts) are obtained from XRD. Moreover, Mössbauer spectroscopy revealed that several Fe II sites exist. The structure is classified in green rusts one and two (GR1 and GR2) according to the stacking sequence of Fe(OH) 2 brucite-like layers depending on the shape and type of anions inserted within interlayers. Long range order as determined for hydroxysulphate GR2(SO 42-) is extended to distributions of cations and anions within GR1s even though these are not observed by XRD. Abundances of Fe II and Fe III environments within GR1s that intercalate carbonate, oxalate and methanoate (formate) are found for compositions [Fe 6IIFe 2III(OH) 16] 2+·[CO 32-·5H 2O] 2-, [Fe 4IIFe 2III(OH) 12] 2+·[CO 32-·3H 2O] 2-, [Fe 6IIFe 2III(OH) 16] 2+·[C 2O 42-·4H 2O] 2- and [Fe 5IIFe 2III(OH) 14] 2+·[2HCOO -·3H 2O] 2-, which correspond to orders α, β and γ where the cation distances are (2 × a0), (√3 × a0) or a mixture of both, with a ferric molar ratio x = {[Fe III]/[Fe total]} = 1/4, 1/3 and 2/7, respectively. Anion distributions within interlayers are devised and long range orders in other layered double hydroxides could questionably be extended from these models. The formula [Fe 6II(1- x) Fe 6 xIIIO 12H 2(7-3 x) ] 2+·[CO 32-·3H 2O] 2- for the fougerite mineral, which is the oxyhydroxycarbonate obtained by deprotonation of Fe II-III hydroxycarbonate [Fe 4IIFe 2III(OH) 12] 2+·[CO 32-·3H 2O] 2- where x ∈ [1/3,2/3] is confirmed.

  13. Spectral and thermodynamic properties of Ag(I), Au(III), Cd(II), Co(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(IV), and Zn(II) binding by methanobactin from Methylosinus trichosporium OB3b.

    Science.gov (United States)

    Choi, Dong W; Do, Young S; Zea, Corbin J; McEllistrem, Marcus T; Lee, Sung-W; Semrau, Jeremy D; Pohl, Nicola L; Kisting, Clint J; Scardino, Lori L; Hartsel, Scott C; Boyd, Eric S; Geesey, Gill G; Riedel, Theran P; Shafe, Peter H; Kranski, Kim A; Tritsch, John R; Antholine, William E; DiSpirito, Alan A

    2006-12-01

    Methanobactin (mb) is a novel chromopeptide that appears to function as the extracellular component of a copper acquisition system in methanotrophic bacteria. To examine this potential physiological role, and to distinguish it from iron binding siderophores, the spectral (UV-visible absorption, circular dichroism, fluorescence, and X-ray photoelectron) and thermodynamic properties of metal binding by mb were examined. In the absence of Cu(II) or Cu(I), mb will bind Ag(I), Au(III), Co(II), Cd(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(VI), or Zn(II), but not Ba(II), Ca(II), La(II), Mg(II), and Sr(II). The results suggest metals such as Ag(I), Au(III), Hg(II), Pb(II) and possibly U(VI) are bound by a mechanism similar to Cu, whereas the coordination of Co(II), Cd(II), Fe(III), Mn(II), Ni(II) and Zn(II) by mb differs from Cu(II). Consistent with its role as a copper-binding compound or chalkophore, the binding constants of all the metals examined were less than those observed with Cu(II) and copper displaced other metals except Ag(I) and Au(III) bound to mb. However, the binding of different metals by mb suggests that methanotrophic activity also may play a role in either the solubilization or immobilization of many metals in situ.

  14. Biphenolate Iron (II) Complexes with Intramolecularly Coordinating Nitrogen Lewis Bases

    NARCIS (Netherlands)

    Koten, G. van; Brandts, J.A.M.; Janssen, M.D.; Hogerheide, M.P.; Boersma, J.; Spek, A.L.

    1999-01-01

    The synthesis and characterisation of a novel Fe(II) bisphenolate complex [Fe(OC{6}H{4}CH{2}NMe{2}-2){2}]{2} (1) from [Na(OC{6}H{4}CH{2}NMe{2}-2)] and anhydrous FeCl{2} is reported. The solid state structure has been elucidated by single crystal X-ray analysis and shows a dimeric structure with two

  15. Biphenolate Iron (II) Complexes with Intramolecularly Coordinating Nitrogen Lewis Bases

    NARCIS (Netherlands)

    Koten, G. van; Brandts, J.A.M.; Janssen, M.D.; Hogerheide, M.P.; Boersma, J.; Spek, A.L.

    1999-01-01

    The synthesis and characterisation of a novel Fe(II) bisphenolate complex [Fe(OC{6}H{4}CH{2}NMe{2}-2){2}]{2} (1) from [Na(OC{6}H{4}CH{2}NMe{2}-2)] and anhydrous FeCl{2} is reported. The solid state structure has been elucidated by single crystal X-ray analysis and shows a dimeric structure with two

  16. Complexation facilitated reduction of aromatic N-oxides by aqueous Fe(II)-tiron complex: reaction kinetics and mechanisms.

    Science.gov (United States)

    Chen, Yiling; Zhang, Huichun

    2013-10-01

    Rapid reduction of carbadox (CDX), olaquindox and several other aromatic N-oxides were investigated in aqueous solution containing Fe(II) and tiron. Consistent with previous work, the 1:2 Fe(II)-tiron complex, FeL2(6-), is the dominant reactive species as its concentration linearly correlates with the observed rate constant kobs under various conditions. The N-oxides without any side chains were much less reactive, suggesting direct reduction of the N-oxides is slow. UV-vis spectra suggest FeL2(6-) likely forms 5- or 7-membered rings with CDX and olaquindox through the N and O atoms on the side chain. The formed inner-sphere complexes significantly facilitated electron transfer from FeL2(6-) to the N-oxides. Reduction products of the N-oxides were identified by HPLC/QToF-MS to be the deoxygenated analogs. QSAR analysis indicated neither the first electron transfer nor N-O bond cleavage is the rate-limiting step. Calculations of the atomic spin densities of the anionic N-oxides confirmed the extensive delocalization between the aromatic ring and the side chain, suggesting complex formation can significantly affect the reduction kinetics. Our results suggest the complexation facilitated N-oxide reduction by Fe(II)-tiron involves a free radical mechanism, and the subsequent deoxygenation might also benefit from the weak complexation of Fe(II) with the N-oxide O atom.

  17. Potentiometric and electrokinetic signatures of iron(II) interactions with (a,y)-Fe2O3

    Energy Technology Data Exchange (ETDEWEB)

    Toczydlowska, Diana; Kedra-Krolik, Karolina; Nejbert, Krzysztof; Preocanin, Tajana; Rosso, Kevin M.; Zarzycki, Piotr P.

    2015-05-29

    The role of surface electrostatics on the reductive dissolution of iron (III) oxides is poorly understood, despite its importance in controlling the amount of mobilized iron. We report the potentiometric titration of the a; y -Fe2O3 oxides exposed to reductants and complexing ligands (Fe(II), ascorbate, oxalate, malonate). We monitored in situ surface and potentials, the ratio of mobilized ferric to ferrous ions, and periodically analyzed nanoparticle crystal structure using X-ray diffraction. We found that addition of Fe2+ ions produces a response consistent with the iron solubilityactivity curve, whereas the presence of ascorbate significantly decreases the amount of mobilized Fe(III) due to reduction to Fe(II). In addition, XRD analysis proved that y-Fe2O3 particles remain structurally unchanged along the titration pathway despite iron cycling between aqueous and solid reservoirs. Our studies, suggest that the surface redoxactivity of iron oxides is primarily governed by the balance between Fe(III) and Fe(II) ions in aqueous phase, which may be easily altered by complexing and reducing agents.

  18. Fluorinated Dodecaphenylporphyrins: Synthetic and Electrochemical Studies Including the First Evidence of Intramolecular Electron Transfer Between an Fe(II) Porphyrin -Anion Radical and an Fe(I) Porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    D' Souza, F.; Forsyth, T.P.; Fukuzumi, S.; Kadish, K.M.; Krattinger, B.; Lin, M.; Medforth, C.J.; Nakanishi, I.; Nurco, D.J.; Shelnutt, J.A.; Smith, K.M.; Van Caemelbecke, E.

    1998-10-19

    Dodecaphenylporphyrins with varying degrees of fluorination of the peripheral phenyl rings (FXDPPS) were synthesized as model compounds for studying electronic effects in nonplan~ porphyrins, and detailed electrochemical studies of the chloroiron(HI) complexes of these compounds were undertaken. The series of porphyrins, represented as FeDPPCl and as FeFXDPPCl where x = 4, 8 (two isomers), 12, 20,28 or 36, could be reversibly oxidized by two electrons in dichloromethane to give n-cation radicals and n-dications. All of the compounds investigated could also be reduced by three electrons in benzonitrile or pyridine. In benzonitrile, three reversible reductions were observed for the unfluorinated compound FeDPPC1, whereas the FeFXDPPCl complexes generally exhibited irreversible first and second reductions which were coupled to chemical reactions. The chemical reaction associated with the first reduction involved a loss of the chloride ion after generation of Fe FXDPPC1. The second chemical reaction involved a novel intramolecular electron transfer between the initially generated Fe(H) porphyrin n-anion radical and the final Fe(I) porphyrin reduction product. In pyridine, three reversible one electron reductions were observed with the second reduction affording stable Fe(II) porphyrin o - anion radicals for ail of the complexes investigated.

  19. Iron Isotope Fractionation during Fe(II) Oxidation Mediated by the Oxygen-Producing Marine Cyanobacterium Synechococcus PCC 7002

    Energy Technology Data Exchange (ETDEWEB)

    Swanner, E. D.; Bayer, T.; Wu, W.; Hao, L.; Obst, M.; Sundman, A.; Byrne, J. M.; Michel, F. M.; Kleinhanns, I. C.; Kappler, A.; Schoenberg, R.

    2017-04-11

    In this study, we couple iron isotope analysis to microscopic and mineralogical investigation of iron speciation during circumneutral Fe(II) oxidation and Fe(III) precipitation with photosynthetically produced oxygen. In the presence of the cyanobacterium Synechococcus PCC 7002, aqueous Fe(II) (Fe(II)aq) is oxidized and precipitated as amorphous Fe(III) oxyhydroxide minerals (iron precipitates, Feppt), with distinct isotopic fractionation (ε56Fe) values determined from fitting the δ56Fe(II)aq (1.79‰ and 2.15‰) and the δ56Feppt (2.44‰ and 2.98‰) data trends from two replicate experiments. Additional Fe(II) and Fe(III) phases were detected using microscopy and chemical extractions and likely represent Fe(II) and Fe(III) sorbed to minerals and cells. The iron desorbed with sodium acetate (FeNaAc) yielded heavier δ56Fe compositions than Fe(II)aq. Modeling of the fractionation during Fe(III) sorption to cells and Fe(II) sorption to Feppt, combined with equilibration of sorbed iron and with Fe(II)aq using published fractionation factors, is consistent with our resulting δ56FeNaAc. The δ56Feppt data trend is inconsistent with complete equilibrium exchange with Fe(II)aq. Because of this and our detection of microbially excreted organics (e.g., exopolysaccharides) coating Feppt in our microscopic analysis, we suggest that electron and atom exchange is partially suppressed in this system by biologically produced organics. These results indicate that cyanobacteria influence the fate and composition of iron in sunlit environments via their role in Fe(II) oxidation through O2 production, the capacity of their cell surfaces to sorb iron, and the interaction of secreted organics with Fe(III) minerals.

  20. Removal of trace mercury(II) from aqueous solution by in situ formed Mn–Fe (hydr)oxides

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Xixin, E-mail: luxixin@outlook.com; Huangfu, Xiaoliu, E-mail: hfxl-hit@163.com; Ma, Jun, E-mail: majun@hit.edu.cn

    2014-09-15

    Highlights: • Trace mercury removal from solution was performed using in situ Mn–Fe. • In situ Mn–Fe have better removal efficiency of trace mercury than PAC and FeCl{sub 3}. • Mercury removal mechanism by in situ Mn–Fe is adsorption–flocculation–precipitation. - Abstract: The efficiency and mechanism of trace mercury (Hg(II)) removal by in situ formed manganese–ferric (hydr)oxides (in situ Mn–Fe) were investigated by reacting KMnO{sub 4} with Fe(II) in simulated solutions and natural water. In the simulated solutions, the impact of coagulant dosage, pH, and temperature on mercury removal was studied. Experimental results showed that in situ Mn–Fe more effectively removed mercury compared with polyaluminum chloride (PAC) and iron(III) chloride (FeCl{sub 3}), and that mercury existed in the form of uncharged species, namely Hg(OH){sub 2}, HgClOH(aq), and HgCl{sub 2}(aq). Fourier transform infrared spectroscopy demonstrated that in situ Mn–Fe contained hydroxyl groups as the surface active sites, while X-ray photoelectron spectroscopy (XPS) measurements revealed that MnO{sub 2} or MnOOH and FeOOH were the dominant species in the precipitates. XPS analysis indicated that an Hg–Mn–Fe mixture was formed in the precipitates, suggesting that mercury was removed from solutions via transfer from the liquid phase to solid phase. These results indicated that the primary mercury removal mechanisms in in situ Mn–Fe were surface complexation and flocculation–precipitation processes. Satisfactory removal efficiency of mercury was also observed following in situ Mn–Fe in natural waters.

  1. [Fe II] 1.64 um Features of Jets and Outflows from Young Stellar Objects in the Carina Nebula

    CERN Document Server

    Shinn, Jong-Ho; Lee, Jae-Joon; Lee, Ho-Gyu; Kim, Hyun-Jeong; Koo, Bon-Chul; Sung, Hwankyung; Chun, Moo Young; Lyo, A -Ran; Moon, Dae-Sik; Kyeong, Jaemann; Park, Byeong-Gon; Hur, Hyeonoh; Lee, Yong-Hyun

    2013-01-01

    We present [Fe II] 1.64 {\\mu}m imaging observations for jets and outflows from young stellar objects (YSOs) over the northern part (~ 24'x45') of the Carina Nebula, a massive star forming region. The observations were performed with IRIS2 of Anglo-Australian Telescope and the seeing was ~1.5"+-0.5". Eleven jet and outflow features are detected at eight different regions, and are named as Ionized Fe Objects (IFOs). One Herbig-Haro object candidate missed in Hubble Space Telescope H{\\alpha} observations is newly identified as HHc-16, referring our [Fe II] images. IFOs have knotty or longish shapes, and the detection rate of IFOs against previously identified YSOs is 1.4 %, which should be treated as a lower limit. Four IFOs show an anti-correlated peak intensities in [Fe II] and H{\\alpha}, where the ratio I([Fe II])/I(H{\\alpha}) is higher for longish IFOs than for knotty IFOs. We estimate the outflow mass loss rate from the [Fe II] flux, using two different methods. The jet-driving objects are identified for th...

  2. Combined analysis of chemical bonding in a Cu(II) dimer using QTAIM, Voronoi tessellation and Hirshfeld surface approaches.

    Science.gov (United States)

    Vologzhanina, Anna V; Kats, Svitlana V; Penkova, Larisa V; Pavlenko, Vadim A; Efimov, Nikolay N; Minin, Vadim V; Eremenko, Igor L

    2015-10-01

    Interaction of 1-(1H-pyrazol-5-yl)ethanone oxime (H2PzOx) with copper(II) chloride in the presence of pyridine afforded a binuclear discrete [Cu2(HPzOx)2Cl2py2] complex, which was characterized by Fourier transform-IR and electron paramagnetic resonance (EPR) spectra, magnetochemistry and high-resolution X-ray diffraction experiments. Multipole refinement of X-ray diffraction data and density-functional theory (DFT) calculations of an isolated molecule allowed charge and spin distributions to be obtained for this compound. Magnetochemistry data, EPR spectra and DFT calculations of an isolated molecule show antiferromagnetic coupling between copper(II) ions. The spin distribution suggests an exchange pathway via the bridging pyrazole ring in the equatorial plane of the CuN4Cl coordination polyhedron, thus providing support for the classical superexchange mechanism; the calculated value of the magnetic coupling constant -2J is equal to 220 cm(-1), which compares well with the experimental value of 203 ± 2 cm(-1). Chemical connectivity was derived by Bader's 'quantum theory of atoms in molecules' and compared with Voronoi tessellation and Hirshfeld surface representations of crystal space. All methodologies gave a similar qualitative and semi-quantitative description of intra- and intermolecular connectivity.

  3. Effect of metal oxides on the reactivity of persulfate/Fe(II) in the remediation of diesel-contaminated soil and sand.

    Science.gov (United States)

    Do, Si-Hyun; Kwon, Yong-Jae; Kong, Sung-Ho

    2010-10-15

    The effect of metal oxides on the ability of persulfate (PS) with Fe(II) to remediate diesel-contaminated soil was investigated. In both natural soil and purchased sand, the highest diesel degradation occurred at pH 3 and the optimum molar ratio of PS/Fe(II) was 100:1 (i.e. 500 mM PS to 5 mM Fe(II)). Moreover, adding Fe(II) increased PS reactivity more in soil than it did in sand, indicating the involvement of metal oxides in the soil matrix. Evaluating the effects of metal oxides (i.e. goethite, hematite, magnetite, and manganese oxide) on the reactivity of PS with/without Fe(II) in a system containing diesel-contaminated sand revealed that manganese oxide increased PS activity the most and that the highest diesel degradation by PS occurred when both manganese oxide and Fe(II) were used as activators. XRD did not show the transformation of manganese oxide in the presence of Fe(II). SEM-EDS showed the association of Fe(II) on the surface of manganese oxide, and ICP analysis revealed that almost all the added Fe(II) adsorbed to manganese oxide but almost none adsorbed to iron oxides under acidic conditions. Therefore, the high reactivity of PS could be due to the high density of Fe(II) over the surface of manganese oxide. 2010 Elsevier B.V. All rights reserved.

  4. Removal of trace mercury(II) from aqueous solution by in situ formed Mn-Fe (hydr)oxides.

    Science.gov (United States)

    Lu, Xixin; Huangfu, Xiaoliu; Ma, Jun

    2014-09-15

    The efficiency and mechanism of trace mercury (Hg(II)) removal by in situ formed manganese-ferric (hydr)oxides (in situ Mn-Fe) were investigated by reacting KMnO4 with Fe(II) in simulated solutions and natural water. In the simulated solutions, the impact of coagulant dosage, pH, and temperature on mercury removal was studied. Experimental results showed that in situ Mn-Fe more effectively removed mercury compared with polyaluminum chloride (PAC) and iron(III) chloride (FeCl3), and that mercury existed in the form of uncharged species, namely Hg(OH)2, HgClOH(aq), and HgCl2(aq). Fourier transform infrared spectroscopy demonstrated that in situ Mn-Fe contained hydroxyl groups as the surface active sites, while X-ray photoelectron spectroscopy (XPS) measurements revealed that MnO2 or MnOOH and FeOOH were the dominant species in the precipitates. XPS analysis indicated that an Hg-Mn-Fe mixture was formed in the precipitates, suggesting that mercury was removed from solutions via transfer from the liquid phase to solid phase. These results indicated that the primary mercury removal mechanisms in in situ Mn-Fe were surface complexation and flocculation-precipitation processes. Satisfactory removal efficiency of mercury was also observed following in situ Mn-Fe in natural waters. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. TRANSFORMATION OF NITROSOBENZENES AND HYDROXYLANILINES BY FE (II) SPECIES: ELUCIDATION OF MECHANISM, EFFECT OF FERRIC OXIDES AND PH

    Science.gov (United States)

    The purpose of this work was to (i) study the effect of structure composition on the reactivity of a series of N-hydroxylaniline and nitrosobenzene compounds toward their reduction by Fe(II) species, (ii) evaluate the usefulness of several chemical parameters for predicting the r...

  6. Sol-gel based optical sensor for determination of Fe (II): a novel probe for iron speciation.

    Science.gov (United States)

    Samadi-Maybodi, Abdolraouf; Rezaei, Vida; Rastegarzadeh, Saadat

    2015-02-05

    A highly selective optical sensor for Fe (II) ions was developed based on entrapment of a sensitive reagent, 2,4,6-tri(2-pyridyl)-s-triazine (TPTZ), in a silica sol-gel thin film coated on a glass substrate. The thin films fabricated based on tetraethoxysilane (TEOS) as precursor, sol-gel pH∼3, water:alkoxyde ratio of 4:1 and TPTZ concentration of 0.112 mol L(-1). The influence of sol-gel parameters on sensing behavior of the fabricated sensor was also investigated. The fabricated sensor can be used for determination of Fe (II) ion with an outstanding high selectivity over a dynamic range of 5-115 ng mL(-1) and a detection limit of 1.68 ng mL(-1). It also showed reproducible results with relative standard deviation of 3.5% and 1.27% for 10 and 90 ng mL(-1) of Fe (II), respectively, along with a fast response time of ∼120 s. Total iron also was determined after reduction of Fe (III) to Fe (II) using ascorbic acid as reducing agent. Then, the concentration of Fe (III) was calculated by subtracting the concentration of Fe (II) from the total iron concentration. Interference studies showed a good selectivity for Fe (II) with trapping TPTZ into sol-gel matrix and appropriately adjusting the structure of doped sol-gel. The sensor was compared with other sensors and was applied to determine iron in different water samples with good results.

  7. A Near-Infrared Template Derived from I Zw 1 for the FeII Emission in Active Galaxies

    CERN Document Server

    Garcia-Rissmann, A; Sigut, T A A; Pradhan, A K

    2012-01-01

    In AGN spectra, a series of FeII multiplets form a pseudo-continuum that extends from the ultraviolet to the near-infrared (NIR). This emission is believed to originate in the Broad Line Region (BLR), and it has been known for a long time that pure photoionization fails to reproduce it in the most extreme cases, as does the collisional-excitation alone. The most recent models by Sigut & Pradhan (2003) include details of the FeII ion microphysics and cover a wide range in ionization parameter log U_ion= (-3.0 -> -1.3) and density log n_H = (9.6 -> 12.6). With the aid of such models and a spectral synthesis approach, we study for the first time in detail the NIR emission of I Zw 1. The main goals are to confirm the role played by Ly\\alpha-fluorescence mechanisms in the production of the FeII spectrum and to construct the first semi-empirical NIR FeII template that best represents this emission and can be used to subtract it in other sources. A good overall match between the observed FeII+MgII features with ...

  8. Complexation and coordination selectivities of the tetradentate ligand 7-[(2-hydroxy-5-sulfophenyl) azo]-8-hydroxyquinoline-5-sulfonic acid with Fe(II), Ni(II), Zn(II), Cd(II) and VO(IV)

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Hu; Kai, Fumiaki; Hirohata, Masaaki; Nakamura, Masaaki; Matsuzaki, Susumu; Komori, Kenji; Tsunematsu, Yuriko [Kumamoto Univ. (Japan)

    1993-12-31

    The new title tetradentate ligand (SPAHQS), containing both phenylazo and 8-quinolinol fragments, was prepared. Proton-dissociation processes of the ligand and complexing equilibria with Fe(II), Ni(II), Zn(II), Cd(II), and VO(IV) were analyzed spectrophotometrically. Coordination modes of SPAHQS with these metal ions have been investigated by means of polarography and Raman spectroscopy in aqueous solution. It was established that the coordination selectivity of SPAHQS for such metal ions is mainly dependent on steric factors in the chelate ring formed, not on HSAB properties. 18 refs., 6 figs., 2 tabs.

  9. Building-up novel coordination polymer with Zn(II) porphyrin dimer: Synthesis, structures, surface morphology and effect of axial ligands

    Indian Academy of Sciences (India)

    Sk Asif Ikbal; Sanfaori Brahma; Avinash Dhamija; Sankar Prasad Rath

    2014-09-01

    Highly flexible Zn(II)1,2-bis(meso-octaethylporphyrin)ethane (1) has been used as host in which two porphyrin rings are found to be face-to-face in non-coordinating solvents. Upon addition of one relatively smaller 4,4′-dipyridine (L1) and one extended N,N′-bispyridine-4-yl-methylene ethylenediamine (L2) guest ligands, the syn conformation of 1 is switched to the anti complexes 1·(L1)2 and 1·L2, respectively. Single crystal X-ray structures of all the complexes are reported in which a stable one-dimensional coordination polymer is produced only in 1·L2 that is, to the best of our knowledge, the first structural report of 1D-coordination polymer with porphyrin dimer. Solution structures of the complexes along with binding studies in solution between 1 and L have also been investigated. The morphology of the polymeric complex 1·L2 on silicon wafer surface was examined by Atomic Force Microscopy (AFM) in which the crystalline islands of well defined facets of size ranging from 200-550 nm perimeter and a height of 20-40 nm have been observed.

  10. Dimerization of pentanuclear clusters [Fe3Q(AsMe)(CO)9] (Q = Se, Te) as a conversion pathway to novel cubane-like aggregates.

    Science.gov (United States)

    Pushkarevsky, Nikolay A; Konchenko, Sergey N; Zabel, Manfred; Bodensteiner, Michael; Scheer, Manfred

    2011-03-07

    The first examples of carbonyl heterocubane-type clusters, [Fe(4)(μ(3)-Q)(2)(μ(3)-AsMe)(2)(CO)(12)] (2, Q = Se (a), Te (b)), which simultaneously contain elements of group 15 and 16, were obtained by thermolysis of [Fe(3)(μ(3)-Q)(μ(3)-AsMe)(CO)(9)] (1) in acetonitrile. The clusters 2 possess a cubic Fe(4)Q(2)As(2) core with alternating Fe and Q/As atoms. The coordination environment of the Fe atoms is close to octahedral, and those of Q or As atoms are tetrahedral, which determines the distorted cubic cluster core geometry. The second main products of thermolysis are the clusters [Fe(6)(μ(3)-Q)(μ(4)-Q)(μ(4)-AsMe)(2)(CO)(12)] (3a,b), whose core contains double the elemental composition of the initial cluster 1. In the case of the Se-containing cluster two other minor products [Fe(4)(μ(4)-Se)(μ(4)-SeAsMe)(CO)(12)] (4) and [Fe(3)(μ(3)-AsMe)(2)(CO)(9)] (5) are formed. Based on the structures and properties of the products, a reaction route for the conversion of 1 into 2 is proposed, which includes the associative formation of the clusters 3 as intermediates, unlike the dissociative pathways previously known for the transformations of similar clusters of the type [Fe(3)Q(2)(CO)(9)].

  11. The [Fe/H] Dependence on the Ca {\\sc ii}-$M_V$ Relationship

    CERN Document Server

    Gomez, Thomas; Pancino, Elena

    2012-01-01

    We examined the Wilson-Bappu effect, a relationship between the absolute magnitude of the star, $M_V$, and the logarithm of the Ca {\\sc ii} emission width, $W_0$, over the largest $M_V$ range to date, +13 to -5, covering M-dwarfs to type Ia supergiants. We used an extensive literature, the latest Hipparcos reduction, data from two globular clusters, and new observations from Apache Point Observatory to compile a sample that allowed us to study the effect of [Fe/H] on the Wilson-Bappu relationship. Our results include reporting the deviations from linearity and demonstrating that the Wilson-Bappu relationship is insensitive to metallicity.

  12. Formation of Fe(0-Nanoparticles via Reduction of Fe(II Compounds by Amino Acids and Their Subsequent Oxidation to Iron Oxides

    Directory of Open Access Journals (Sweden)

    K. Klačanová

    2013-01-01

    Full Text Available Iron nanoparticles were prepared by the reduction of central Fe(II ion in the coordination compounds with amino acid ligands. The anion of the amino acid used as a ligand acted as the reducing agent. Conditions for the reduction were very mild; the temperature did not exceed 52°C, and the optimum pH was between 9.5 and 9.7. The metal iron precipitated as a mirror on the flask or as a colloid in water. Identification of the product was carried out by measuring UV/VIS spectra of the iron nanoparticles in water. The iron nanoparticles were oxidized by oxygen yielding a mixture of iron oxides. Oxidation of Fe(0 to Fe(II took several seconds under air. The size and properties of iron oxide nanoparticles were studied by UV/VIS, TEM investigation, RTG diffractometry, Mössbauer spectroscopy, magnetometry, thermogravimetry, and GC/MS.

  13. The metallomics approach: use of Fe(II) and Cu(II) footprinting to examine metal binding sites on serum albumins.

    Science.gov (United States)

    Duff, Michael R; Kumar, Challa V

    2009-11-01

    Metal binding to serum albumins is examined by oxidative protein-cleavage chemistry, and relative affinities of multiple metal ions to particular sites on these proteins were identified using a fast and reliable chemical footprinting approach. Fe(ii) and Cu(ii), for example, mediate protein cleavage at their respective binding sites on serum albumins, in the presence of hydrogen peroxide and ascorbate. This metal-mediated protein-cleavge reaction is used to evaluate the binding of metal ions, Na(+), Mg(2+), Ca(2+), Al(3+), Cr(3+), Mn(2+), Co(2+), Ni(2+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), and Ce(3+) to albumins, and the relative affinities (selectivities) of the metal ions are rapidly evaluated by examining the extent of inhibition of protein cleavage. Four distinct systems Fe(II)/BSA, Cu(II)/BSA, Fe(II)/HSA and Cu(II)/HSA are examined using the above strategy. This metallomics approach is novel, even though the cleavage of serum albumins by Fe(II)/Cu(II) has been reported previously by this laboratory and many others. The protein cleavage products were analyzed by SDS PAGE, and the intensities of the product bands quantified to evaluate the extent of inhibition of the cleavage and thereby evaluate the relative binding affinities of specific metal ions to particular sites on albumins. The data show that Co(II) and Cr(III) showed the highest degree of inhibition, across the table, followed by Mn(II) and Ce(III). Alakali metal ions and alkaline earth metal ions showed very poor affinity for these metal sites on albumins. Thus, metal binding profiles for particular sites on proteins can be obtained quickly and accurately, using the metallomics approach.

  14. Oxalate enhanced mechanism of hydroxyl-Fe-pillared bentonite during the degradation of Orange II by UV-Fenton process.

    Science.gov (United States)

    Chen, Jianxin; Zhu, Lizhong

    2011-01-30

    An enhanced method of hydroxyl-Fe-pillared bentonite (H-Fe-P-B) during the degradation of Orange II was studied to provide novel insight to interactions of degradation intermediates with heterogeneous catalyst in UV-Fenton system. Based on the degradation mechanism of Orange II, oxalate enhanced mechanism of H-Fe-P-B in heterogeneous UV-Fenton system was developed. The results showed that additional oxalate could increase the Fe leaching of H-Fe-P-B during heterogeneous UV-Fenton process, which led to higher mineralization efficiency of Orange II and lower energy consumption of treatment. When the concentrations of additional sodium oxalate increased up to 0.1 mmol L(-1), 0.2 mmol L(-1) and 0.4 mmol L(-1), the rate of Orange II degradation could increase 30%, 46% and 63%, respectively. The iron ions leached from catalyst could be adsorbed back to the catalyst again after the organic intermediates were mineralized completely. Then the catalyst of H-Fe-P-B could be reused and additional pollution caused by iron ions could be avoided.

  15. Periodic trends within a series of five-coordinate thiolate-ligated [MII(SMe2N4(tren))]+ (M = Mn, Fe, Co, Ni, Cu, Zn) complexes, including a rare example of a stable CuII-thiolate.

    Science.gov (United States)

    Brines, Lisa M; Shearer, Jason; Fender, Jessica K; Schweitzer, Dirk; Shoner, Steven C; Barnhart, David; Kaminsky, Werner; Lovell, Scott; Kovacs, Julie A

    2007-10-29

    A series of five-coordinate thiolate-ligated complexes [M(II)(tren)N4S(Me2)]+ (M = Mn, Fe, Co, Ni, Cu, Zn; tren = tris(2-aminoethyl)amine) are reported, and their structural, electronic, and magnetic properties are compared. Isolation of dimeric [Ni(II)(SN4(tren)-RS(dang))]2 ("dang"= dangling, uncoordinated thiolate supported by H bonds), using the less bulky [(tren)N4S](1-) ligand, pointed to the need for gem-dimethyls adjacent to the sulfur to sterically prevent dimerization. All of the gem-dimethyl derivatized complexes are monomeric and, with the exception of [Ni(II)(S(Me2)N4(tren)]+, are isostructural and adopt a tetragonally distorted trigonal bipyramidal geometry favored by ligand constraints. The nickel complex uniquely adopts an approximately ideal square pyramidal geometry and resembles the active site of Ni-superoxide dismutase (Ni-SOD). Even in coordinating solvents such as MeCN, only five-coordinate structures are observed. The MII-S thiolate bonds systematically decrease in length across the series (Mn-S > Fe-S > Co-S > Ni-S approximately Cu-S tren)]+, represents a rare example of a stable CuII-thiolate, and models the perturbed "green" copper site of nitrite reductase. In contrast to the intensely colored, low-spin Fe(III)-thiolates, the M(II)-thiolates described herein are colorless to moderately colored and high-spin (in cases where more than one spin-state is possible), reflecting the poorer energy match between the metal d- and sulfur orbitals upon reduction of the metal ion. As the d-orbitals drop in energy proceeding across the across the series M(2+) (M= Mn, Fe, Co, Ni, Cu), the sulfur-to-metal charge-transfer transition moves into the visible region, and the redox potentials cathodically shift. The reduced M(+1) oxidation state is only accessible with copper, and the more oxidized M(+4) oxidation state is only accessible for manganese.

  16. Mechanochemical synthesis and intercalation of Ca(II)Fe(III)-layered double hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Ferencz, Zs.; Szabados, M.; Varga, G.; Csendes, Z. [Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged H-6720 (Hungary); Materials and Solution Structure Research Group, Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged H-6720 (Hungary); Kukovecz, Á. [Department of Applied and Environmental Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged H-6720 (Hungary); MTA-SZTE “Lendület” Porous Nanocomposites Research Group, Rerrich Béla tér 1, Szeged H-6720 (Hungary); Kónya, Z. [Department of Applied and Environmental Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged H-6720 (Hungary); MTA-SZTE Reaction Kinetics and Surface Chemistry Research Group, Rerrich Béla tér 1, Szeged H-6720 (Hungary); Carlson, S. [MAX IV Laboratory, Ole Römers väg 1, Lund SE-223 63 (Sweden); Sipos, P. [Materials and Solution Structure Research Group, Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged H-6720 (Hungary); Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, Szeged H-6720 (Hungary); and others

    2016-01-15

    A mechanochemical method (grinding the components without added water – dry grinding, followed by further grinding in the presence of minute amount of water or NaOH solution – wet grinding) was used in this work for the preparation and intercalation of CaFe-layered double hydroxides (LDHs). Both the pristine LDHs and the amino acid anion (cystinate and tyrosinate) intercalated varieties were prepared by the two-step grinding procedure in a mixer mill. By systematically changing the conditions of the preparation method, a set of parameters could be determined, which led to the formation of close to phase-pure LDH. The optimisation procedure was also applied for the intercalation processes of the amino acid anions. The resulting materials were structurally characterised by a range of methods (X-ray diffractometry, scanning electron microscopy, energy dispersive analysis, thermogravimetry, X-ray absorption and infra-red spectroscopies). It was proven that this simple mechanochemical procedure was able to produce complex organic–inorganic nanocomposites: LDHs intercalated with amino acid anions. - Graphical abstract: Amino acid anion-Ca(II)Fe(III)-LDHs were successfully prepared by a two-step milling procedure. - Highlights: • Synthesis of pristine and amino acid intercalated CaFe-LDHs by two-step milling. • Identifying the optimum synthesis and intercalation parameters. • Characterisation of the samples with a range of instrumental methods.

  17. Synthesis, characterization, DFT calculations and biological studies of Mn(II), Fe(II), Co(II) and Cd(II) complexes based on a tetradentate ONNO donor Schiff base ligand

    Science.gov (United States)

    Abdel-Rahman, Laila H.; Ismail, Nabawia M.; Ismael, Mohamed; Abu-Dief, Ahmed M.; Ahmed, Ebtehal Abdel-Hameed

    2017-04-01

    This study highlights synthesis and characterization of a tetradentate ONNO Schiff base ligand namely (1, 1‧- (pyridine-2, 3-dimethyliminomethyl) naphthalene-2, 2‧-diol) and hereafter denotes as "HNDAP″ and selected metal complexes including Mn(II), Fe(II), Co(II) and Cd(II) as a central metal. HNDAP was synthesized from 1:2 M ratio condensation of 2, 3-diaminopyridine and 2- hydroxy-1-naphthaldhyde, respectively. The stoichiometric ratios of the prepared complexes were estimated using complementary techniques such as; elemental analyses (-C, H, N), FT-IR, magnetic measurements and molar conductivity. Furthermore, their physicochemical studies were carried out using thermal TGA, DTA and kinetic-thermodynamic studies along with DFT calculations. The results of elemental analyses showed that these complexes are present in a 1:1 metal-to- ligand molar ratio. Moreover, the magnetic susceptibilities values at room temperature revealed that Mn(II), Fe(II) and Co(II) complexes are paramagnetic in nature and have an octahedral (Oh) geometry. In contrast, Cd(II) is diamagnetic and stabilizes in square planar sites. The molar conductivity measurements indicated that all complexes are nonelectrolytes in dimethyl formamide. Spectral data suggested that the ligand is as tetradentate and coordinated with Co(II) ion through two phenolic OH and two azomethine nitrogen. However, for Mn(II), Fe(II) and Cd(II) complexes, the coordination occurred through two phenolic oxygen and two azomethine nitrogen with deprotonation of OH groups. The proposed chemical structures have been validated by quantum mechanics calculations. Antimicrobial activities of both the HNDAP Schiff base ligand and its metal complexes were tested against strains of Gram (-ve) E. coli and Gram (+ve) B. subtilis and S. aureus bacteria and C. albicans, A. flavus and T. rubrum fungi. All the prepared compounds showed good results of inhibition against the selected pathogenic microorganisms. The investigated

  18. Physiological characterization of a halotolerant anoxygenic phototrophic Fe(II)-oxidizing green-sulfur bacterium isolated from a marine sediment.

    Science.gov (United States)

    Laufer, Katja; Niemeyer, Annika; Nikeleit, Verena; Halama, Maximilian; Byrne, James M; Kappler, Andreas

    2017-05-01

    Anoxygenic photoautotrophic bacteria which use light energy and electrons from Fe(II) for growth, so-called photoferrotrophs, are suggested to have been amongst the first phototrophic microorganisms on Earth and to have contributed to the deposition of sedimentary iron mineral deposits, i.e. banded iron formations. To date only two isolates of marine photoferrotrophic bacteria exist, both of which are closely related purple non-sulfur bacteria. Here we present a novel green-sulfur photoautotrophic Fe(II) oxidizer isolated from a marine coastal sediment, Chlorobium sp. strain N1, which is closely related to the freshwater green-sulfur bacterium Chlorobium luteolum DSM273 that is incapable of Fe(II) oxidation. Besides Fe(II), our isolated strain grew phototrophically with other inorganic and organic substrates such as sulfide, hydrogen, lactate or yeast extract. Highest Fe(II) oxidation rates were measured at pH 7.0-7.3, the temperature optimum was 25°C. Mössbauer spectroscopy identified ferrihydrite as the main Fe(III) mineral and fluorescence and helium-ion microscopy revealed cell-mineral aggregates without obvious cell encrustation. In summary, our study showed that the new isolate is physiologically adapted to the conditions of its natural habitat but also to conditions as proposed for early Earth and is thus a suitable model organism for further studies addressing phototrophic Fe(II) oxidation on early Earth. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  19. Removal of Fe(II) from the wastewater of a galvanized pipe manufacturing industry by adsorption onto bentonite clay.

    Science.gov (United States)

    Tahir, S S; Rauf, Naseem

    2004-12-01

    Bentonite clay has been used for the adsorption of Fe(II) from aqueous solutions over a concentration range of 80-200 mg/l, shaking time of 1-60 min, adsorbent dosage from 0.02 to 2 g and pH of 3. The process of uptake follows both the Langmuir and Freundlich isotherm models and also the first-order kinetics. The maximum removal (>98%) was observed at pH of 3 with initial concentration of 100 mg/l and 0.5 g of bentonite. The efficiency of Fe(II) removal was also tested using wastewater from a galvanized pipe manufacturing industry. More than 90% of Fe(II) can be effectively removed from the wastewater by using 2.0 g of the bentonite. The effect of cations (i.e. zinc, manganese, lead, cadmium, nickel, cobalt, chromium and copper) on the removal of Fe(II) was studied in the concentration range of 10-500 mg/l. All the added cations reduced the adsorption of Fe(II) at high concentrations except Zn. Column studies have also been carried out using a certain concentration of wastewater. More than 99% recovery has been achieved by using 5 g of the bentonite with 3M nitric acid solution.

  20. The HH34 outflow as seen in [FeII]1.64um by LBT-LUCI

    CERN Document Server

    Antoniucci, S; Nisini, B; Giannini, T; Lorenzetti, D; Paris, D; Sani, E

    2014-01-01

    Dense atomic jets from young stars copiously emit in [FeII] IR lines, which can, therefore, be used to trace the immediate environments of embedded protostars. We want to investigate the morphology of the bright [FeII] 1.64um line in the jet of the source HH34 IRS and compare it with the most commonly used optical tracer [SII]. We analyse a 1.64um narrow-band filter image obtained with the Large Binocular Telescope (LBT) LUCI instrument, which covers the HH34 jet and counterjet. A Point Spread Function (PSF) deconvolution algorithm was applied to enhance spatial resolution and make the IR image directly comparable to a [SII] HST image of the same source. The [FeII] emission is detected from both the jet, the (weak) counter-jet, and from the HH34-S and HH34-N bow shocks. The deconvolved image allows us to resolve jet knots close to about 1\\arcsec from the central source. The morphology of the [FeII] emission is remarkably similar to that of the [SII] emission, and the relative positions of [FeII] and [SII] pea...

  1. Adsorption of Pb(II) and Cu(II) from aqueous solution on magnetic porous ferrospinel MnFe2O4.

    Science.gov (United States)

    Ren, Yueming; Li, Nan; Feng, Jing; Luan, Tianzhu; Wen, Qing; Li, Zhanshuang; Zhang, Milin

    2012-02-01

    The adsorption of Pb(II) and Cu(II) from aqueous solution on magnetic porous ferrospinel MnFe(2)O(4) prepared by a sol-gel process was investigated. Single batch experiment was employed to test pH effect, sorption kinetics, and isotherm. The interaction mechanism and the regeneration were also explored. The results showed that Pb(II) and Cu(II) removal was strongly pH-dependent with an optimum pH value of 6.0, and the equilibrium time was 3.0 h. The adsorption process could be described by a pseudo-second-order model, and the initial sorption rates were 526.3 and 2631.5 μmol g(-1)min(-1) for Pb(II) and Cu(II) ions, respectively. The equilibrium data were corresponded well with Langmuir isotherm, and the maximum adsorption capacities were 333.3 and 952.4 μmol g(-1) for Pb(II) and Cu(II) ions, respectively. The adsorbed Pb(II) and Cu(II) ions were in the form of the complex with oxygen in carboxyl and hydroxyl groups binding on the surface of magnetic porous MnFe(2)O(4). The sorbent could be reused for five times with high removal efficiency.

  2. Immobilization of 99-Technetium (VII) by Fe(II)-Goethite and Limited Reoxidation

    Energy Technology Data Exchange (ETDEWEB)

    W Um; H Chang; J Icenhower; W Lukens; R Serne; N Qafoku; J Westsik Jr.; E Buck; S Smith

    2011-12-31

    During the nuclear waste vitrification process volatilized {sup 99}Tc will be trapped by melter off-gas scrubbers and then washed out into caustic solutions, and plans are currently being contemplated for the disposal of such secondary waste. Solutions containing pertechnetate [{sup 99}Tc(VII)O{sub 4}{sup -}] were mixed with precipitating goethite and dissolved Fe(II) to determine if an iron (oxy)hydroxide-based waste form can reduce Tc(VII) and isolate Tc(IV) from oxygen. The results of these experiments demonstrate that Fe(II) with goethite efficiently catalyzes the reduction of technetium in deionized water and complex solutions that mimic the chemical composition of caustic waste scrubber media. Identification of the phases, goethite + magnetite, was performed using XRD, SEM and TEM methods. Analyses of the Tc-bearing solid products by XAFS indicate that all of the Tc(VII) was reduced to Tc(IV) and that the latter is incorporated into goethite or magnetite as octahedral Tc(IV). Batch dissolution experiments, conducted under ambient oxidizing conditions for more than 180 days, demonstrated a very limited release of Tc to solution (2-7 {micro}g Tc/g solid). Incorporation of Tc(IV) into the goethite lattice thus provides significant advantages for limiting reoxidation and curtailing release of Tc disposed in nuclear waste repositories.

  3. Enhanced reductive degradation of carbon tetrachloride by biogenic vivianite and Fe(II)

    Science.gov (United States)

    Bae, Sungjun; Lee, Woojin

    2012-05-01

    We demonstrated that reductive dechlorination of carbon tetrachloride (CT) can be enhanced by iron-bearing soil minerals (IBSMs) in the presence of Shewanella putrefaciens CN32 (CN32) due to the formation of biogenic vivianite and Fe(II). The bioreduction efficiency of magnetite was the highest (51.1%), followed by lepidocrocite (25.7%), goethite (3.6%), and hematite (1.8%). The dechlorination kinetic of CT by lepidocrocite (0.043 d-1) in the presence of CN32 was three times faster than that by microbial transformation with CN32 (0.014 d-1). Chloroform (16.1-29.4%), carbon monoxide (2.4-23.8%), and formate (0-58.0%) were measured as main products for the degradation of CT by magnetite and lepidocrocite in the presence of CN32. X-ray diffraction and electron microscope analyses revealed that the biogenic vivianite can form during the CT degradation in magnetite and lepidocrocite suspensions with CN32. The dechlorination kinetics of CT by chemogenic vivianite was much faster than that by magnetite and lepidocrocite with CN32. The highest formate production (84.2%) was observed during a full degradation of CT by the chemogenic vivianite. The experimental results showed that biogenic vivianite and sorbed Fe(II) formed during the bioreduction of IBSMs played a pivotal role for the reductive dechlorination of CT.

  4. Experimental diagenesis of organo-mineral structures formed by microaerophilic Fe(II)-oxidizing bacteria.

    Science.gov (United States)

    Picard, Aude; Kappler, Andreas; Schmid, Gregor; Quaroni, Luca; Obst, Martin

    2015-02-18

    Twisted stalks are organo-mineral structures produced by some microaerophilic Fe(II)-oxidizing bacteria at O2 concentrations as low as 3 μM. The presence of these structures in rocks having experienced a diagenetic history could indicate microbial Fe(II)-oxidizing activity as well as localized abundance of oxygen at the time of sediment deposition. Here we use spectroscopy and analytical microscopy to evaluate if--and what kind of--transformations occur in twisted stalks through experimental diagenesis. Unique mineral textures appear on stalks as temperature and pressure conditions increase. Haematite and magnetite form from ferrihydrite at 170 °C-120 MPa. Yet the twisted morphology of the stalks, and the organic matrix, mainly composed of long-chain saturated aliphatic compounds, are preserved at 250 °C-140 MPa. Our results suggest that iron minerals might play a role in maintaining the structural and chemical integrity of stalks under diagenetic conditions and provide spectroscopic signatures for the search of ancient life in the rock record.

  5. Energetic Chromophores: Low-Energy Laser Initiation in Explosive Fe(II) Tetrazine Complexes.

    Science.gov (United States)

    Myers, Thomas W; Bjorgaard, Josiah A; Brown, Kathryn E; Chavez, David E; Hanson, Susan K; Scharff, R Jason; Tretiak, Sergei; Veauthier, Jacqueline M

    2016-04-01

    The synthesis and characterization of air stable Fe(II) coordination complexes with tetrazine and triazolo-tetrazine ligands and perchlorate counteranions have been achieved. Time-dependent density functional theory (TD-DFT) was used to model the structural, electrochemical, and optical properties of these materials. These compounds are secondary explosives that can be initiated with Nd:YAG laser light at lower energy thresholds than those of PETN. Furthermore, these Fe(II) tetrazine complexes have significantly lower sensitivity than PETN toward mechanical stimuli such as impact and friction. The lower threshold for laser initiation was achieved by altering the electronic properties of the ligand scaffold to tune the metal ligand charge transfer (MLCT) bands of these materials from the visible into the near-infrared region of the electromagnetic spectrum. Unprecedented decrease in both the laser initiation threshold and the mechanical sensitivity makes these materials the first explosives that are both safer to handle and easier to initiate than PETN with NIR lasers.

  6. Mariprofundus ferrooxydans PV-1 the first genome of a marine Fe(II oxidizing Zetaproteobacterium.

    Directory of Open Access Journals (Sweden)

    Esther Singer

    Full Text Available Mariprofundus ferrooxydans PV-1 has provided the first genome of the recently discovered Zetaproteobacteria subdivision. Genome analysis reveals a complete TCA cycle, the ability to fix CO(2, carbon-storage proteins and a sugar phosphotransferase system (PTS. The latter could facilitate the transport of carbohydrates across the cell membrane and possibly aid in stalk formation, a matrix composed of exopolymers and/or exopolysaccharides, which is used to store oxidized iron minerals outside the cell. Two-component signal transduction system genes, including histidine kinases, GGDEF domain genes, and response regulators containing CheY-like receivers, are abundant and widely distributed across the genome. Most of these are located in close proximity to genes required for cell division, phosphate uptake and transport, exopolymer and heavy metal secretion, flagellar biosynthesis and pilus assembly suggesting that these functions are highly regulated. Similar to many other motile, microaerophilic bacteria, genes encoding aerotaxis as well as antioxidant functionality (e.g., superoxide dismutases and peroxidases are predicted to sense and respond to oxygen gradients, as would be required to maintain cellular redox balance in the specialized habitat where M. ferrooxydans resides. Comparative genomics with other Fe(II oxidizing bacteria residing in freshwater and marine environments revealed similar content, synteny, and amino acid similarity of coding sequences potentially involved in Fe(II oxidation, signal transduction and response regulation, oxygen sensation and detoxification, and heavy metal resistance. This study has provided novel insights into the molecular nature of Zetaproteobacteria.

  7. Astrophysical Lasers Operating in optical Fe II Lines Lines in Stellar Ejecta of Eta Carinae

    CERN Document Server

    Johansson, S

    2004-01-01

    After the discovery of space masers based on OH radicals (Weaver et al, 1965) and H2O (Cheung et al, 1969) such microwave lasers have been found to work in more than 100 molecular species (Elitzur, 1992; Townes, 1997), as well as in highly excited H atoms (Strelnitski et al,1996). In the IR region (10 microns), the effect of stimulated emission of radiation in the CO2 molecule has been discovered in the Martian and Venus' atmospheres (Betz et al, 1976; Mumma et al, 1981). We report here on the discovery of laser action in the range 0.9-2 micr. in several spectral lines of Fe II, which are associated with transitions from "pseudo-metastable" states populated by spontaneous transitions from Ly-alpha pumped Fe II levels. The intense Ly-alpha radiation is formed in the HII region of gas condensations close to the star Eta Carinae. The laser transitions form together with spontaneous transitions closed radiative cycles, one of which includes the extremely bright 2507/09 A lines. Closed radiative cycles, together w...

  8. Molecular Hydrogen and [Fe II] in Active Galactic Nuclei III: LINERS and Star Forming Galaxies

    CERN Document Server

    Riffel, R; Aleman, I; Brotherton, M S; Pastoriza, M G; Bonatto, C J; Dors, O L

    2013-01-01

    We study the kinematics and excitation mechanisms of H2 and [Fe II] lines in a sample of 67 emission-line galaxies with Infrared Telescope Facility SpeX near-infrared (NIR, 0.8-2.4 micrometers) spectroscopy together with new photoionisation models. H2 emission lines are systematically narrower than narrow-line region (NLR) lines, suggesting that the two are, very likely, kinematically disconnected. The new models and emission-line ratios show that the thermal excitation plays an important role not only in active galactic nuclei but also in star forming galaxies. The importance of the thermal excitation in star forming galaxies may be associated with the presence of supernova remnants close to the region emitting H2 lines. This hypothesis is further supported by the similarity between the vibrational and rotational temperatures of H2. We confirm that the diagram involving the line ratios H2 2.121/Br_gamma and [Fe II] 1.257/Pa_beta is an efficient tool for separating emission-line objects according to their dom...

  9. Fe(II)EDTA-NO reduction by a newly isolated thermophilic Anoxybacillus sp. HA from a rotating drum biofilter for NOx removal.

    Science.gov (United States)

    Chen, Jun; Li, Yan; Hao, Hong-hong; Zheng, Ji; Chen, Jian-meng

    2015-02-01

    The reduction of Fe(II)EDTA-NO is one of the core processes in BioDeNOx, an integrated physicochemical and biological technique for NOx removal from industrial flue gases. A newly isolated thermophilic Anoxybacillus sp. HA, identified by 16S rRNA sequence analysis, could simultaneously reduce Fe(II)EDTA-NO and Fe(III)EDTA. A maximum NO removal efficiency of 98.7% was achieved when 3mM Fe(II)EDTA-NO was used in the nutrient solution at 55°C. Results of this study strongly indicated that the biological oxidation of Fe(II)EDTA played an important role in the formation of Fe(III)EDTA in the anaerobic system. Fe(II)EDTA-NO was more competitive than Fe(III)EDTA as an electron acceptor, and the presence of Fe(III)EDTA slightly affected the reduction rate of Fe(II)EDTA-NO. At 55°C, the maximum microbial specific growth rate μmax reached the peak value of 0.022h(-1). The maximum NO removal efficiency was also measured (95.4%) under this temperature. Anoxybacillus sp. HA, which grew well at 50°C-60°C, is a potential microbial resource for Fe(II)EDTA-NO reduction at thermophilic temperatures.

  10. HH 666: different kinematics from H α and [Fe II] emission provide a missing link between jets and outflows

    Science.gov (United States)

    Reiter, Megan; Smith, Nathan; Kiminki, Megan M.; Bally, John

    2015-06-01

    HH 666 is an externally irradiated protostellar outflow in the Carina nebula for which we present new near-IR [Fe II] spectra obtained with the Folded-Port Infrared Echellette spectrograph at Magellan Observatory. Earlier H α and near-IR [Fe II] imaging revealed that the two emission lines trace substantially different morphologies in the inner ˜40 arcsec of the outflow. H α traces a broad cocoon that surrounds the collimated [Fe II] jet that extends throughout the parent dust pillar. New spectra show that this discrepancy extends to their kinematics. Near-IR [Fe II] emission traces steady, fast velocities of ±200 km s-1 from the eastern and western limbs of the jet. We compare this to a previously published H α spectrum that reveals a Hubble-flow velocity structure near the jet-driving source. New, second-epoch Hubble Space Telescope (HST)/Advanced Camera for Surveys (ACS) H α images reveal the lateral spreading of the H α outflow lobe away from the jet axis. H α proper motions also indicate a sudden increase in the mass-loss rate ˜1000 yr ago, while steady [Fe II] emission throughout the inner jet suggest that the burst is ongoing. An accretion burst sustained for ˜1000 yr is an order of magnitude longer than expected for FU Orionis outbursts, but represents only a small fraction of the total age of the HH 666 outflow. Altogether, available data suggests that [Fe II] traces the highly collimated protostellar jet while H α traces the entrained and irradiated outflow. HH 666 appears to be a missing link between bare jets seen in H II regions and entrained molecular outflows seen from embedded protostars in more quiescent regions.

  11. Crystal structure of (NH42[FeII5(HPO36], a new open-framework phosphite

    Directory of Open Access Journals (Sweden)

    Teresa Berrocal

    2014-11-01

    Full Text Available Diammonium hexaphosphitopentaferrate(II, (NH42[Fe5(HPO36], was synthesized under mild hydrothermal conditions and autogeneous pressure, yielding twinned crystals. The crystal structure exhibits an [FeII5(HPO36]2− open framework with NH4+ groups as counter-cations. The anionic skeleton is based on (001 sheets of [FeO6] octahedra (one with point-group symmetry 3.. and one with .2. linked along [001] through [HPO3]2− oxoanions. Each sheet is constructed from 12-membered rings of edge-sharing [FeO6] octahedra, giving rise to channels with a radius of ca 3.1 Å in which the disordered NH4+ cations are located. The IR spectrum shows vibrational bands typical for phosphite and ammonium groups.

  12. Dimerization of Human Growth Hormone by Zinc

    Science.gov (United States)

    Cunningham, Brian C.; Mulkerrin, Michael G.; Wells, James A.

    1991-08-01

    Size-exclusion chromatography and sedimentation equilibrium studies demonstrated that zinc ion (Zn2+) induced the dimerization of human growth hormone (hGH). Scatchard analysis of 65Zn2+ binding to hGH showed that two Zn2+ ions associate per dimer of hGH in a cooperative fashion. Cobalt (II) can substitute for Zn2+ in the hormone dimer and gives a visible spectrum characteristic of cobalt coordinated in a tetrahedral fashion by oxygen- and nitrogen-containing ligands. Replacement of potential Zn2+ ligands (His18, His21, and Glu174) in hGH with alanine weakened both Zn2+ binding and hGH dimer formation. The Zn2+-hGH dimer was more stable than monomeric hGH to denaturation in guanidine-HCl. Formation of a Zn2+-hGH dimeric complex may be important for storage of hGH in secretory granules.

  13. Synthesis, characterization and biological activities of Cu(II), Co(II), Mn(II), Fe(II), and UO2(VI) complexes with a new Schiff Base hydrazone: O-hydroxyacetophenone-7-chloro-4-quinoline hydrazone.

    Science.gov (United States)

    Al-Shaalan, Nora H

    2011-10-13

    The Schiff base hydrazone ligand HL was prepared by the condensation reaction of 7-chloro-4-quinoline with o-hydroxyacetophenone. The ligand behaves either as monobasic bidentate or dibasic tridentate and contain ONN coordination sites. This was accounted for be the presence in the ligand of a phenolic azomethine and imine groups. It reacts with Cu(II), Ni(II), Co(II), Mn(II), UO(2) (VI) and Fe(II) to form either mono- or binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, NMR, Mass, and UV-Visible spectra. The magnetic moments and electrical conductance of the complexes were also determined. The Co(II), Ni(II) and UO(2) (VI) complexes are mononuclear and coordinated to NO sites of two ligand molecules. The Cu(II) complex has a square-planar geometry distorted towards tetrahedral, the Ni(II) complex is octahedral while the UO(2) (VI) complex has its favoured heptacoordination. The Co(II), Mn(II) complexes and also other Ni(II) and Fe(III) complexes, which were obtained in the presence of Li(OH) as deprotonating agent, are binuclear and coordinated via the NNNO sites of two ligand molecules. All the binuclear complexes have octahedral geometries and their magnetic moments are quite low compared to the calculated value for two metal ions complexes and thus antiferromagnetic interactions between the two adjacent metal ions. The ligand HL and metal complexes were tested against a strain of Gram +ve bacteria (Staphylococcus aureus), Gram -ve bacteria (Escherichia coli), and fungi (Candida albicans). The tested compounds exhibited high antibacterial activities.

  14. Synthesis, Characterization and Biological Activities of Cu(II, Co(II, Mn(II, Fe(II, and UO2(VI Complexes with a New Schiff Base Hydrazone: O-Hydroxyacetophenone-7-chloro-4-quinoline Hydrazone

    Directory of Open Access Journals (Sweden)

    Nora H. Al-Shaalan

    2011-10-01

    Full Text Available The Schiff base hydrazone ligand HL was prepared by the condensation reaction of 7-chloro-4-quinoline with o-hydroxyacetophenone. The ligand behaves either as monobasic bidentate or dibasic tridentate and contain ONN coordination sites. This was accounted for be the presence in the ligand of a phenolic azomethine and imine groups. It reacts with Cu(II, Ni(II, Co(II, Mn(II, UO2 (VI and Fe(II to form either mono- or binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, NMR, Mass, and UV-Visible spectra. The magnetic moments and electrical conductance of the complexes were also determined. The Co(II, Ni(II and UO2 (VI complexes are mononuclear and coordinated to NO sites of two ligand molecules. The Cu(II complex has a square-planar geometry distorted towards tetrahedral, the Ni(II complex is octahedral while the UO2 (VI complex has its favoured heptacoordination. The Co(II, Mn(II complexes and also other Ni(II and Fe(III complexes, which were obtained in the presence of Li(OH as deprotonating agent, are binuclear and coordinated via the NNNO sites of two ligand molecules. All the binuclear complexes have octahedral geometries and their magnetic moments are quite low compared to the calculated value for two metal ions complexes and thus antiferromagnetic interactions between the two adjacent metal ions. The ligand HL and metal complexes were tested against a strain of Gram +ve bacteria (Staphylococcus aureus, Gram −ve bacteria (Escherichia coli, and fungi (Candida albicans. The tested compounds exhibited high antibacterial activities.

  15. Comparative and competitive adsorption of Pb(II) and Cu(II) using tetraethylenepentamine modified chitosan/CoFe2O4 particles.

    Science.gov (United States)

    Fan, Chunzhen; Li, Kan; Li, Juexiu; Ying, Diwen; Wang, Yalin; Jia, Jinping

    2017-03-15

    In this paper, tetraethylenepentamine (TEPA) modified chitosan/CoFe2O4 particles were prepared for comparative and competitive adsorption of Cu(II) and Pb(II) in single and bi-component aqueous solutions. The characteristics results of SEM, FTIR and XRD indicated that the adsorbent was successfully fabricated. The magnetic property results manifested that the particles with saturation magnetization value of 63.83emug(-1) would have a fast magnetic response. The effects of experimental parameters including contact time, pH value, initial metal ions concentration and coexisting ions on single and bi-component adsorption were investigated. The results revealed that the adsorption kinetic was followed pseudo-second-order kinetic model, indicating that chemical adsorption was the rate-limiting step. Sorption isotherms were also determined in single and bi-component solutions with different mass ratio of Cu(II) to Pb(II) (Cu(II)/Pb(II)) and fitted using Langmuir and Freundlich isotherm models. A better fit for Cu(II) and Pb(II) adsorption were obtained with Langmuir model, with a maximum sorption capacity of 168.067 and 228.311mgg(-1) for Cu(II) and Pb(II) in single component solution, 139.860 and 160.256mgg(-1) in bi-component solution (Cu(II)/Pb(II)=1:1), respectively. The present results suggest that TEPA modified chitosan/CoFe2O4 particles are feasible and satisfactory adsorbent for efficient removal of Cu(II) and Pb(II) ions.

  16. Incorporation of Pyrazine and Bipyridine Linkers with High-Spin Fe(II) and Co(II) in a Metal–Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Kawamura, Airi; Greenwood, Arin R.; Filatov, Alexander S.; Gallagher, Audrey T.; Galli, Giulia; Anderson, John S.

    2017-02-27

    A series of isoreticular metal organic frameworks (MOFs) of the formula M(BDC)(L) (M = Fe(II) or Co(II), BDC = 1,4-benzenedicarboxylate, L = pyrazine (pyz) or 4,4'-bipyridine (bipy)) has been synthesized and characterized by N-2 gas uptake Measurements, single crystal and powder X-ray diffraction, magnetometry, X-ray absorption spectroscopy, and Mossbauer spectroscopy. These studies indicate the formation of a permanently porous solid with high-spin Fe(II) and Co(II) centers that are weakly coupled, consistent with first-principles density functional theory calculations. This family of materials represents unusual examples of paramagnetic metal centers coordinated by linkers capable of mediating magnetic or electronic coupling in a porous framework. While only weak interactions are observed, the rigid 3D framework of the MOF dramatically impacts the properties of these materials when compared with close structural analogues.

  17. Characteristics and biotechnology applications of aliphatic amino acid hydroxylases belonging to the Fe(II)/α-ketoglutarate-dependent dioxygenase superfamily.

    Science.gov (United States)

    Hibi, Makoto; Ogawa, Jun

    2014-05-01

    The asymmetric hydroxylation of inactive carbon atoms is still an important reaction in the industrial synthesis of valuable chiral compounds such as pharmaceuticals and fine chemicals. Applications of monooxygenation enzymes, like cytochrome P450 monooxygenases, flavin-containing monooxygenases, and Fe(II)/α-ketoglutarate-dependent dioxygenases (Fe/αKG-DOs), are strongly desired as hydroxylation biocatalysts because they have great advantages in regio- and stereoselectivity of the reactions. Recently, several novel Fe/αKG-DOs have been found to catalyze the asymmetric hydroxylation of aliphatic amino acids. Depending on their amino acid sequences, these Fe/αKG-DOs catalyze different types of regioselective hydroxylations, or C3-, C4-, and C5-hydroxylation. Additionally, most also have stereoselective sulfoxidation activities. Here, we have reviewed the characterization and process development of this novel functioning group of Fe/αKG-DOs.

  18. Tunable Excited-State Properties and Dynamics as a Function of Pt–Pt Distance in Pyrazolate-Bridged Pt(II) Dimers

    Energy Technology Data Exchange (ETDEWEB)

    Brown-Xu, Samantha E.; Kelley, Matthew S. J.; Fransted, Kelly A.; Chakraborty, Arnab; Schatz, George C.; Castellano, Felix N.; Chen, Lin X.

    2016-02-04

    The influence of molecular structure on excited state properties and dynamics of a series of cyclometalated platinum dimers was investigated through a combined experimental and theoretical approach using femtosecond transient absorption (fs TA) spectroscopy and density functional theory (DFT) calculations. The molecules have the general formula [Pt(ppy)(µ-R2pz)]2 where ppy = 2-phenylpyridine, pz = pyrazolate and R = H, Me, Ph, or tBu, and are strongly photoluminescent at room temperature. The distance between the platinum centers in this A frame geometry can be varied depending on the steric bulk of the bridging pyrazolate ligands that exert structural constraints and compress the Pt-Pt distance. At large Pt-Pt distances there is little interaction between the subunits and the chromophore behaves similar to a monomer with excited states described as mixtures of ligand-centered and metal-to-ligand charge transfer (LC/MLCT) transitions. When the Pt(II) centers are brought closer together with bulky bridging ligands, they interact through their orbitals and the S1 and T1 states are best characterized as metal metal to ligand charge transfer (MMLCT) in character. The results of the fs TA experiments reveal that intersystem crossing (ISC) occurs on ultrafast timescales (τS1 < 200 fs) while there are two relaxation processes occurring within the triplet manifold, τ1 = 0.5 – 3.2 ps and τ2 = 20 – 70 ps; the longer time constants correspond to the presence of bulkier bridging ligands. DFT calculations illustrate that the Pt-Pt distances further contract in the T1 3MMLCT states, therefore slower relaxation may be related to a larger structural reorganization. Subsequent investigations using faster time resolution are planned to measure the ISC process as well as to identify any potential coherent interaction(s) between the platinum centers that may occur.

  19. A synthetic model of the putative Fe(II)-iminobenzosemiquinonate intermediate in the catalytic cycle of o-aminophenol dioxygenases.

    Science.gov (United States)

    Bittner, Michael M; Lindeman, Sergey V; Fiedler, Adam T

    2012-03-28

    The oxidative ring cleavage of aromatic substrates by nonheme Fe dioxygenases is thought to involve formation of a ferrous-(substrate radical) intermediate. Here we describe the synthesis of the trigonal-bipyramdial complex Fe((Ph2)Tp)(ISQ(tBu)) (2), the first synthetic example of an iron(II) center bound to an iminobenzosemiquinonate (ISQ) radical. The unique electronic structure of this S = 3/2 complex and its one-electron oxidized derivative ([3](+)) have been established on the basis of crystallographic, spectroscopic, and computational analyses. These findings further demonstrate the viability of Fe(2+)-ISQ intermediates in the catalytic cycles of o-aminophenol dioxygenases.

  20. Synthesis of Magnetically Modified Fe-Al Pillared Bentonite and Heterogeneous Fenton-like Degradation of Orange II

    Institute of Scientific and Technical Information of China (English)

    CHEN Kun; WANG Guanghua; LI Wenbing; WAN Dong; HU Qin; LU Lulu; WEI Xiaobi; CHENG Zhengzai

    2015-01-01

    Magnetically modified Fe-Al pillared bentonite (Fe3O4/ Fe-Al-Bent) was prepared via chemical co-precipitation method and characterized by powder X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). A series of experiments were carried out to investigate the degradation of Orange II by the obtained heterogeneous catalysts in the presence of H2O2. The experimental result indicated that the synthetic materials had a high catalytic activity and good reusability.

  1. Effects of temperature on rates and mineral products of microbial Fe(II) oxidation by Leptothrix cholodnii at microaerobic conditions

    Science.gov (United States)

    Vollrath, Susann; Behrends, Thilo; Koch, Christian Bender; Cappellen, Philippe Van

    2013-05-01

    Oxygen concentrations are important in constraining the geochemical niche of neutrophilic iron oxidizers. However, other factors like temperature may affect the competition between microbial and abiotic Fe(II) oxidation and may cause community changes. Here, rates and mineral products of Fe(II) oxidation (initial concentration 150 μmol Fe(II)/l) by the Fe(II) oxidizing bacterial strain Leptothrix cholodnii Appels were compared to those of abiotic oxidation in the temperature range 11-37 °C. Experiments were carried out in a batch reactor at 12-13 μmol O2/l (0.92-1% O2 saturation), pH 7 and, for the microbial experiments, a cell density of around 108 cells/ml. The iron precipitates formed at the different temperatures were characterized by SEM, XRD, FTIR and Mössbauer spectroscopy. Abiotic and microbial Fe(II) oxidation proceeded in two stages. During the initial stage, rates of microbial oxidation exhibited a temperature optimum curve. In contrast, the temperature dependency of abiotic Fe(II) oxidation rate followed the Arrhenius equation. As a consequence, microbial oxidation rates were about 10 times higher compared to the abiotic oxidation at 30 °C. During the second stage, microbial and abiotic rates and their temperature dependencies were similar. Independent of temperature or presence of bacteria, lepidocrocite and ferrihydrite were identified as reaction products, but the characteristics of the precipitates differed. At 37 °C, less lepidocrocite was precipitated in microbial and abiotic experiments due to high oxidation rates. Abiotic oxidation produced larger lepidocrocite crystals mixed with smaller, less crystalline oxides. Large crystals were absent in the microbial products, possibly due to growth inhibition of the minerals by EPS substances. Nevertheless, Mössbauer spectra revealed a better crystal structure of the smaller, microbial precipitates compared to the abiotically formed oxides.

  2. Abiotic process for Fe(II) oxidation and green rust mineralization driven by a heterotrophic nitrate reducing bacteria (Klebsiella mobilis).

    Science.gov (United States)

    Etique, Marjorie; Jorand, Frédéric P A; Zegeye, Asfaw; Grégoire, Brian; Despas, Christelle; Ruby, Christian

    2014-04-01

    Green rusts (GRs) are mixed Fe(II)-Fe(III) hydroxides with a high reactivity toward organic and inorganic pollutants. GRs can be produced from ferric reducing or ferrous oxidizing bacterial activities. In this study, we investigated the capability of Klebsiella mobilis to produce iron minerals in the presence of nitrate and ferrous iron. This bacterium is well-known to reduce nitrate using an organic carbon source as electron donor but is unable to enzymatically oxidize Fe(II) species. During incubation, GR formation occurred as a secondary iron mineral precipitating on cell surfaces, resulting from Fe(II) oxidation by nitrite produced via bacterial respiration of nitrate. For the first time, we demonstrate GR formation by indirect microbial oxidation of Fe(II) (i.e., a combination of biotic/abiotic processes). These results therefore suggest that nitrate-reducing bacteria can potentially contribute to the formation of GR in natural environments. In addition, the chemical reduction of nitrite to ammonium by GR is observed, which gradually turns the GR into the end-product goethite. The nitrogen mass-balance clearly demonstrates that the total amount of ammonium produced corresponds to the quantity of bioreduced nitrate. These findings demonstrate how the activity of nitrate-reducing bacteria in ferrous environments may provide a direct link between the biogeochemical cycles of nitrogen and iron.

  3. Bioalteration of synthetic Fe(III)-, Fe(II)-bearing basaltic glasses and Fe-free glass in the presence of the heterotrophic bacteria strain Pseudomonas aeruginosa: Impact of siderophores

    Science.gov (United States)

    Perez, Anne; Rossano, Stéphanie; Trcera, Nicolas; Huguenot, David; Fourdrin, Chloé; Verney-Carron, Aurélie; van Hullebusch, Eric D.; Guyot, François

    2016-09-01

    This study aims to evaluate the role of micro-organisms and their siderophores in the first steps of the alteration processes of basaltic glasses in aqueous media. In this regard, three different types of glasses - with or without iron, in the reduced Fe(II) or oxidized Fe(III) states - were prepared on the basis of a simplified basaltic glass composition. Control and Pseudomonas aeruginosa inoculated experiments were performed in a buffered (pH 6.5) nutrient depleted medium to stimulate the production of the pyoverdine siderophore. Results show that the presence of P. aeruginosa has an effect on the dissolution kinetics of all glasses as most of the calculated elemental release rates are increased compared to sterile conditions. Reciprocally, the composition of the glass in contact with P. aeruginosa has an impact on the bacterial growth and siderophore production. As an essential nutrient for this microbial strain, Fe notably appears to play a central role during biotic experiments. Its presence in the glass stimulates the bacterial growth and minimizes the synthesis of pyoverdine. Moreover the initial Fe2+/Fe3+ ratio in the glasses modulates this synthesis, as pyoverdine is not detected at all in the system in contact with Fe(III)-bearing glass. Finally, the dissolution rates appear to be correlated to siderophore concentrations as they increase with respect to sterile experiments in the order Fe(III)-bearing glass < Fe(II)-bearing glass < Fe-free glass. This increase is attributed to complexation reactions between siderophores and Fe or Al for Fe(II)-bearing glass or Fe-free glass, respectively. The dissolution of an Fe-free glass is significantly improved in the presence of bacteria, as initial dissolution rates are increased by a factor of 3. This study attests to the essential role of siderophores in the P. aeruginosa-promoted dissolution processes of basaltic glasses as well as to the complex relationships between the nutritional potential of the glass and

  4. Nitric oxide as a non-innocent ligand in (bio-)inorganic complexes: spin and electron transfer in Fe(II)-NO bond.

    Science.gov (United States)

    Broclawik, Ewa; Stępniewski, Adam; Radoń, Mariusz

    2014-07-01

    The nature of electron density transfer upon bond formation between NO ligand and Fe(II) center is analyzed on the basis of DFT calculation for two {Fe-NO}(7) complexes with entirely diverse geometric and electronic structures: Fe(II)P(NH3)NO (with bent Fe-N-O unit) and [Fe(II)(H2O)5(NO)](2+) (with linear Fe-N-O structure). Proper identification of an electronic status of the fragments, "prepared" to make a bond, was found necessary to get meaningful resolution of charge and spin transfer processes from a spin-resolved analysis of natural orbitals for chemical valence. The Fe(II)P(NH3)NO adduct (built of NO(0) (S=1/2) and Fe(II)P(NH3) (S=0) fragments) showed a strong π*-backdonation competing with spin transfer via a σ-donation, yielding significant red-shift of the NO stretching frequency. [Fe(II)(H2O)5(NO)](2+) (built of NO(0) (S=1/2) antiferromagnetically coupled to Fe(II)(H2O)5 (S=2) fragment) gave no noticeable charge or spin transfer between fragments; a slight blue-shift of the NO stretching frequency could be related to a residual π-donation due to weak π-bonding.

  5. Sorption of Pb(II and Cu(II by low-cost magnetic eggshells-Fe3O4 powder

    Directory of Open Access Journals (Sweden)

    Ren Jianwei

    2012-01-01

    Full Text Available This study explored the feasibility of using magnetic eggshell-Fe3O4 powder as adsorbent for the removal of Pb(II and Cu(II ions from aqueous solution. The metal ionsadsorption media interaction was characterized using XRD and FTIR. The effects of contact time, initial concentrations, temperature, solution pH and reusability of the adsorption media were investigated. The metal ions adsorption was fast and the amount of metal ions adsorbed increased with an increase in temperature, suggesting an endothermic adsorption. The kinetic data showed that the adsorption process followed the pseudo-second-order kinetic model. The optimal adsorption pH value was around 5.5 at which condition the equilibrium capacity was 263.2 mg/g for Pb(II and 250.0 for Cu(II. The adsorption equilibrium data fitted very well to the Langmuir and Freundlich adsorption isotherm models. The thermodynamics of Pb(II and Cu(II adsorption onto the magnetic eggshell-Fe3O4 powder indicated that the adsorption was spontaneous. The reusability study has proven that magnetic eggshell-Fe3O4 powder can be employed as a low-cost and easy to separate adsorbent.

  6. Intramolecular Oxidative O-Demethylation of an Oxoferryl Porphyrin Complexed with a Per-O-methylated β-Cyclodextrin Dimer.

    Science.gov (United States)

    Kitagishi, Hiroaki; Kurosawa, Shun; Kano, Koji

    2016-11-22

    The intramolecular oxidation of ROCH3 to ROCH2 OH, where the latter compound spontaneously decomposed to ROH and HCHO, was observed during the reaction of the supramolecular complex (met-hemoCD3) with cumene hydroperoxide in aqueous solution. Met-hemoCD3 is composed of meso-tetrakis(4-sulfonatophenyl)porphinatoiron(III) (Fe(III) TPPS) and a per-O-methylated β-cyclodextrin dimer having an -OCH2 PyCH2 O- linker (Py=pyridine-3,5-diyl). The O=Fe(IV) TPPS complex was formed by the reaction of met-hemoCD3 with cumene hydroperoxide, and isolated by gel-filtration chromatography. Although the isolated O=Fe(IV) TPPS complex in the cyclodextrin cage was stable in aqueous solution at 25 °C, it was gradually converted to Fe(II) TPPS (t1/2 =7.6 h). This conversion was accompanied by oxidative O-demethylation of an OCH3 group in the cyclodextrin dimer. The results indicated that hydrogen abstraction by O=Fe(IV) TPPS from ROCH3 yields HO-Fe(III) TPPS and ROCH2(.) . This was followed by radical coupling to afford Fe(II) TPPS and ROCH2 OH. The hemiacetal (ROCH2 OH) immediately decomposed to ROH and HCHO. This study revealed the ability of oxoferryl porphyrin to induce two-electron oxidation.

  7. Spin crossover in Fe(II) complexes with N4S2 coordination

    DEFF Research Database (Denmark)

    Arroyave, Alejandra; Lennartson, Anders; Dragulescu-Andrasi, Alina;

    2016-01-01

    A systematic study of a series of Fe(II) complexes with the tetradentate N2S2-binding ligand and NCX− coligands (X = S, Se, BH3) conclusively demonstrates the occurrence of temperature-driven spin crossover (SCO), which is rarely observed for the Fe(II) ion in the N4S2 coordination environment....... The SCO is confirmed by crystallography, magnetic measurements, and Mössbauer spectroscopy. The last two methods also reveal a light-induced excited spin state trapping (LIESST) effect at low temperatures....

  8. Cu(II), Fe(III) and Mn(II) combinations as environmental stress factors have distinguishing effects on Enterococcus hirae.

    Science.gov (United States)

    Vardanyan, Zaruhi; Trchounian, Armen

    2015-02-01

    Pollution by various heavy metals as environmental stress factors might affect bacteria. It was established that iron (Fe(III)), manganese (Mn(II)) and copper (Cu(II)) ion combinations caused effects on Enterococcus hirae that differed from the sum of the effects when the metals were added separately. It was shown that the Cu2+-Fe3+ combination decreased the growth and ATPase activity of membrane vesicles of wild-type E. hirae ATCC9790 and atpD mutant (with defective FoF1-ATPase) MS116. Addition of Mn2+-Fe3+ combinations within the same concentration range had no effects on growth compared to control (without heavy metals). ATPase activity was increased in the presence of Mn2+-Fe3+, while together with 0.2 mmol/L N,N'-dicyclohexylcarbodiimide (DCCD), ATPase activity was decreased compared to control (when only 0.2 mmol/L DCCD was present). These results indicate that heavy metals ion combinations probably affect the FOF1-ATPase, leading to conformational changes. Moreover the action may be direct or be mediated by environment redox potential. The effects observed when Fe3+ was added separately disappeared in both cases, which might be a result of competing processes between Fe3+ and other heavy metals. These findings are novel and improve the understanding of heavy metals ions effects on bacteria, and could be applied for regulation of stress response patterns in the environment.

  9. Fe(III) and Fe(II) ions different effects on Enterococcus hirae cell growth and membrane-associated ATPase activity

    Energy Technology Data Exchange (ETDEWEB)

    Vardanyan, Zaruhi [Department of Biophysics of the Biology Faculty, Yerevan State University, 1 A. Manoukian Str., 0025 Yerevan (Armenia); Trchounian, Armen, E-mail: trchounian@ysu.am [Department of Biophysics of the Biology Faculty, Yerevan State University, 1 A. Manoukian Str., 0025 Yerevan (Armenia)

    2012-01-06

    Highlights: Black-Right-Pointing-Pointer Fe{sup 3+} stimulates but Fe{sup 2+} suppresses Enterococcus hirae wild-type and atpD mutant growth. Black-Right-Pointing-Pointer Fe ions change oxidation-reduction potential drop during cell growth. Black-Right-Pointing-Pointer Fe{sup 3+} and Fe{sup 2+} have opposite effects on a membrane-associated ATPase activity. Black-Right-Pointing-Pointer These effects are either in the presence of F{sub 0}F{sub 1} inhibitor or non-functional F{sub 0}F{sub 1}. Black-Right-Pointing-Pointer Fe ions decrease protons and coupled potassium ions fluxes across the membrane. -- Abstract: Enterococcus hirae is able to grow under anaerobic conditions during glucose fermentation (pH 8.0) which is accompanied by acidification of the medium and drop in its oxidation-reduction potential (E{sub h}) from positive values to negative ones (down to {approx}-200 mV). In this study, iron (III) ions (Fe{sup 3+}) have been shown to affect bacterial growth in a concentration-dependent manner (within the range of 0.05-2 mM) by decreasing lag phase duration and increasing specific growth rate. While iron(II) ions (Fe{sup 2+}) had opposite effects which were reflected by suppressing bacterial growth. These ions also affected the changes in E{sub h} values during bacterial growth. It was revealed that ATPase activity with and without N,N Prime -dicyclohexylcarbodiimide (DCCD), an inhibitor of the F{sub 0}F{sub 1}-ATPase, increased in the presence of even low Fe{sup 3+} concentration (0.05 mM) but decreased in the presence of Fe{sup 2+}. It was established that Fe{sup 3+} and Fe{sup 2+} both significantly inhibited the proton-potassium exchange of bacteria, but stronger effects were in the case of Fe{sup 2+} with DCCD. Such results were observed with both wild-type ATCC9790 and atpD mutant (with defective F{sub 0}F{sub 1}) MS116 strains but they were different with Fe{sup 3+} and Fe{sup 2+}. It is suggested that the effects of Fe{sup 3+} might be due to

  10. Coupling of Fe(II) oxidation in illite with nitrate reduction and its role in clay mineral transformation

    Science.gov (United States)

    Zhao, Linduo; Dong, Hailiang; Edelmann, Richard E.; Zeng, Qiang; Agrawal, Abinash

    2017-03-01

    In pedogenic and diagenetic processes, clay minerals transform from pre-existing phases to other clay minerals via intermediate interstratified clays. Temperature, pressure, chemical composition of fluids, and time are traditionally considered to be the important geological variables for clay mineral transformations. Nearly ten years ago, the role of microbes was recognized for the first time, where microbial reduction of structural Fe(III) in smectite resulted in formation of illite under ambient conditions within two weeks. However, the opposite process, the oxidation of structural Fe(II) in illite has not been studied and it remains unclear whether or not this process would result in the back reaction, e.g., from illite to smectite. The overall objective of this study was to investigate biological oxidation of structural Fe(II) in illite coupled with nitrate reduction and the effect of this process on clay mineral transformation. Laboratory incubations were set up, where structural Fe(II) in illite served as electron donor, nitrate as electron acceptor, and Pseudogulbenkiania sp. strain 2002 as mediator. Solution chemistry and gas composition were monitored over time. Mineralogical transformation resulting from bio-oxidation was characterized with X-ray diffraction and scanning and transmission electron microscopy. Our results demonstrated that strain 2002 was able to couple oxidation of structural Fe(II) in illite with reduction of nitrate to N2 with nitrite as a transient intermediate. This oxidation reaction resulted in transformation of illite to smectite and ultimately to kaolinite (illite → smectite → kaolinite transformations). This study illustrates the importance of Fe redox process in mediating the smectite-illite mineral cycle with important implications for Fe redox cycling and mineral evolution in surficial earth environments.

  11. Study of Stability Constants of Fe (Iii And Mn (Ii with Chloramphenicol by Paper Electrophoretic Technique

    Directory of Open Access Journals (Sweden)

    Arvind Singh

    2014-12-01

    Full Text Available Stabilty constant of binary complexes of Fe(III and Mn(II with medicinally important ligand chloramphenicol antibiotics in solution were determined by paper electrophoretic technique. Stability constant of the complexes were determined at 25°C temperature and 0.1M (HClO4 ionic strength. Our study is based upon the migration of a spot of metal ions on a paper strip at different pH against mobility gives information about the binary complexes and permits to calculate their stability constant. The stability constant data revealed that chloramphenicol may be used as chelating agent in chelation for medical treatment of metal overload or poisoning.

  12. Stark width measurements of Fe II lines with wavelengths in the range 260-300 nm

    Energy Technology Data Exchange (ETDEWEB)

    Aragon, C; Aguilera, J A [Departamento de Fisica, Universidad Publica de Navarra, Campus de ArrosadIa, E-31006 Pamplona (Spain); Vega, P, E-mail: carlos.aragon@unavarra.es [Departamento de Fisica, Facultad de Ciencias, Universidad de Oviedo, C/Calvo Sotelo s/n, E-33007 Oviedo (Spain)

    2011-03-14

    The Stark widths of 21 Fe II lines with wavelengths in the range 260-300 nm have been measured using laser-induced plasmas as spectroscopic sources. A set of Fe-Cu samples has been employed to generate the plasmas. To reduce self-absorption, each line has been measured using a different sample, with an iron concentration determined by means of the curve-of-growth methodology. The remaining error due to self-absorption has been estimated to be lower than 10%. Different instants of the plasma evolution, from 0.84 to 2.5 {mu}s, are included in the measurements. The electron density, in the range (1.6-7.3) x 10{sup 17} cm{sup -3}, is determined by the Stark broadening of the H{sub {alpha}} line. Within this range, the Stark widths are found to be proportional to the electron density. The Boltzmann plot method is used to obtain the plasma temperature, which is in the range 12 900-15 200 K. The Stark widths obtained have been compared with available experimental and theoretical data.

  13. A novel endogenous antimalarial: Fe(II)-protoporphyrin IX alpha (heme) inhibits hematin polymerization to beta-hematin (malaria pigment) and kills malaria parasites.

    Science.gov (United States)

    Monti, D; Vodopivec, B; Basilico, N; Olliaro, P; Taramelli, D

    1999-07-13

    The polymerization of hemoglobin-derived ferric-protoporphyrin IX [Fe(III)PPIX] to inert hemozoin (malaria pigment) is a crucial and unique process for intraerythrocytic plasmodia to prevent heme toxicity and thus a good target for new antimalarials. Quinoline drugs, i.e., chloroquine, and non-iron porphyrins have been shown to block polymerization by forming electronic pi-pi interactions with heme monomers. Here, we report the identification of ferrous-protoporphyrin IX [Fe(II)PPIX] as a novel endogenous anti-malarial. Fe(II)PPIX molecules, released from the proteolysis of hemoglobin, are first oxidized and then polymerized to hemozoin. We obtained Fe(II)PPIX on preparative scale by electrochemical reduction of Fe(III)PPIX, and the reaction was monitored by cyclic voltammetry. Polymerization assays at acidic pH were conducted with the resulting Fe(II)PPIX using a spectrophotometric microassay of heme polymerization adapted to anaerobic conditions and the products characterized by infrared spectroscopy. Fe(II)PPIX (a) did not polymerize and (b) produced a dose-dependent inhibition of Fe(III)PPIX polymerization (IC(50) = 0.4 molar equiv). Moreover, Fe(II)PPIX produced by chemical reduction with thiol-containing compounds gave similar results: a dose-dependent inhibition of heme polymerization was observed using either L-cysteine, N-acetylcysteine, or DL-homocysteine, but not with L-cystine. Cyclic voltammetry confirmed that the inhibition of heme polymerization was due to the Fe(II)PPIX molecules generated by the thiol-mediated reduction of Fe(III)PPIX. These results point to Fe(II)PPIX as a potential endogenous antimalarial and to Fe(III)PPIX reduction as a potential new pharmacological target.

  14. Enhanced ion anisotropy by nonconventional coordination geometry: single-chain magnet behavior for a [{Fe(II)L}2{Nb(IV)(CN)8}] helical chain compound designed with heptacoordinate Fe(II).

    Science.gov (United States)

    Venkatakrishnan, Thengarai S; Sahoo, Shaon; Bréfuel, Nicolas; Duhayon, Carine; Paulsen, Carley; Barra, Anne-Laure; Ramasesha, S; Sutter, Jean-Pascal

    2010-05-05

    Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {Fe(II)Nb(IV)} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb(IV), Mo(IV), W(IV)). X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H(2)O)Fe(L(1))}{M(CN)(8)}{Fe(L(1))}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L(1))}(2+) and {M(CN)(8)}(4-) units (L(1) stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L(1))} unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L(1))(H(2)O)(2)]Cl(2) a negative zero field splitting parameter of D approximately = -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L(1))(H(2)O)(2)]Cl(2) are also reported.

  15. Galactic winds with MUSE: A direct detection of Fe II* emission from a z = 1.29 galaxy

    Science.gov (United States)

    Finley, Hayley; Bouché, Nicolas; Contini, Thierry; Epinat, Benoît; Bacon, Roland; Brinchmann, Jarle; Cantalupo, Sebastiano; Erroz-Ferrer, Santiago; Marino, Raffaella Anna; Maseda, Michael; Richard, Johan; Schroetter, Ilane; Verhamme, Anne; Weilbacher, Peter M.; Wendt, Martin; Wisotzki, Lutz

    2017-09-01

    Emission signatures from galactic winds provide an opportunity to directly map the outflowing gas, but this is traditionally challenging because of the low surface brightness. Using very deep observations (27 h) of the Hubble Deep Field South with the Multi Unit Spectroscopic Explorer (MUSE) instrument, we identify signatures of an outflow in both emission and absorption from a spatially resolved galaxy at z = 1.29 with a stellar mass M⋆ = 8 × 109M⊙, star formation rate SFR = 77+40-25 M⊙ yr-1, and star formation rate surface brightness ΣSFR = 1.6M⊙ kpc-2 within the [Oii] λλ3727,3729 half-light radius R1/2, [OII] = 2.76 ± 0.17 kpc. From a component of the strong resonant Mg II and Fe II absorptions at -350 km s-1, we infer a mass outflow rate that is comparable to the star formation rate. We detect non-resonant Fe II* emission, at λ2365, λ2396, λ2612, and λ2626, at 1.2-2.4-1.5-2.7 × 10-18 erg s-1 cm-2 respectively. The flux ratios are consistent with the expectations for optically thick gas. By combining the four non-resonant Fe II* emission lines, we spatially map the Fe II* emission from an individual galaxy for the first time. The Fe II* emission has an elliptical morphology that is roughly aligned with the galaxy minor kinematic axis, and its integrated half-light radius, R1/2, Fe II ∗ =4.1 ± 0.4 kpc, is 70% larger than the stellar continuum (R1/2,⋆ ≃2.34 ± 0.17) or the [Oii] nebular line. Moreover, the Fe II* emission shows a blue wing extending up to -400 km s-1, which is more pronounced along the galaxy minor kinematic axis and reveals a C-shaped pattern in a p-v diagram along that axis. These features are consistent with a bi-conical outflow. Based on observations of the Hubble Deep Field South made with ESO telescopes at the La Silla Paranal Observatory under program ID 60.A-9100(C). Advanced data products are available at http://muse-vlt.eu/ science

  16. Insights into Nitrate-Reducing Fe(II) Oxidation Mechanisms through Analysis of Cell-Mineral Associations, Cell Encrustation, and Mineralogy in the Chemolithoautotrophic Enrichment Culture KS.

    Science.gov (United States)

    Nordhoff, M; Tominski, C; Halama, M; Byrne, J M; Obst, M; Kleindienst, S; Behrens, S; Kappler, A

    2017-07-01

    Most described nitrate-reducing Fe(II)-oxidizing bacteria (NRFeOB) are mixotrophic and depend on organic cosubstrates for growth. Encrustation of cells in Fe(III) minerals has been observed for mixotrophic NRFeOB but not for autotrophic phototrophic and microaerophilic Fe(II) oxidizers. So far, little is known about cell-mineral associations in the few existing autotrophic NRFeOB. Here, we investigate whether the designated autotrophic Fe(II)-oxidizing strain (closely related to Gallionella and Sideroxydans) or the heterotrophic nitrate reducers that are present in the autotrophic nitrate-reducing Fe(II)-oxidizing enrichment culture KS form mineral crusts during Fe(II) oxidation under autotrophic and mixotrophic conditions. In the mixed culture, we found no significant encrustation of any of the cells both during autotrophic oxidation of 8 to 10 mM Fe(II) coupled to nitrate reduction and during cultivation under mixotrophic conditions with 8 to 10 mM Fe(II), 5 mM acetate, and 4 mM nitrate, where higher numbers of heterotrophic nitrate reducers were present. Two pure cultures of heterotrophic nitrate reducers (Nocardioides and Rhodanobacter) isolated from culture KS were analyzed under mixotrophic growth conditions. We found green rust formation, no cell encrustation, and only a few mineral particles on some cell surfaces with 5 mM Fe(II) and some encrustation with 10 mM Fe(II). Our findings suggest that enzymatic, autotrophic Fe(II) oxidation coupled to nitrate reduction forms poorly crystalline Fe(III) oxyhydroxides and proceeds without cellular encrustation while indirect Fe(II) oxidation via heterotrophic nitrate-reduction-derived nitrite can lead to green rust as an intermediate mineral and significant cell encrustation. The extent of encrustation caused by indirect Fe(II) oxidation by reactive nitrogen species depends on Fe(II) concentrations and is probably negligible under environmental conditions in most habitats.IMPORTANCE Most described nitrate

  17. Preparation of graphene oxide/chitosan/FeOOH nanocomposite for the removal of Pb(II) from aqueous solution.

    Science.gov (United States)

    Sheshmani, Shabnam; Akhundi Nematzadeh, Mehrnaz; Shokrollahzadeh, Soheila; Ashori, Alireza

    2015-09-01

    In the present study, a graphene oxide/chitosan/FeOOH (GO/Ch/FeOOH) nanostructured composite was prepared and used as an adsorbent for the removal of Pb(II) ions from aqueous solution. The nanocomposite was characterized by FT-IR, XRD, and SEM techniques. Several important parameters influencing the adsorption of Pb(II) ions such as pH (3-7), temperature (25-80 °C), shaking speed (150-800 rpm), contact time (10-70 min), and sorbent mass (10-100 mg) were studied. The results showed that, benefiting from the surface property of graphene oxide, the abundant amino and hydroxyl functional groups of chitosan, the adsorbent provides adequate and versatile adsorption for the Pb(II) ions under investigation. The batch adsorption experiments showed that the adsorption of the Pb(II) is considerably dependent on pH of milieu, amount of adsorbent, and contact time. The Freundlich and Langmuir adsorption models were used for the mathematical description of adsorption equilibrium and isotherm constants. Both models were applicable for the description of Pb(II) adsorption isotherm in the concentration range studied. However, Langmuir model showed higher correlation coefficient (R(2)) than Freundlich model. The study suggests that the GO/Ch/FeOOH is a promising nano adsorbent for the removal of Pb(II) ions from aqueous solution.

  18. The performance of nonhybrid density functionals for calculating the structures and spin states of Fe(II) and Fe(III) complexes.

    Science.gov (United States)

    Deeth, Robert J; Fey, Natalie

    2004-11-30

    The local density approximation and a range of nonhybrid gradient corrected density functionals (PW91, BLYP, PBE, revPBE, RPBE) have been assessed with respect to the prediction of geometries and spin-state energy preferences for a range of homoleptic Fe(II)L6 and Fe(III)L6 complexes, where L = Cl-, CN-, NH3, pyridine, imidazole, H2O, O=CH2 and tetrahydrofuran. While the qualitative spin-state energies from in vacuo structure optimizations are reasonable the geometries are relatively poorly treated, especially for [FeCl6]3-/4-. Structural results for all the complexes are significantly improved by including environmental effects. The best compromise between structural and spin-state predictive accuracy was obtained for the RPBE functional in combination with the COSMO solvation approach. This approach systematically overestimates the energetic preference for a low spin state, which is partly due to the well-known effect of the lack of exact exchange in nonhybrid functionals and partly due to the larger solvation stabilization of low-spin complexes that have shorter bond lengths and thus smaller molecular volumes than their high-spin partners. Calculations on low spin [Fe(bipy)3]2+ and [Fe(phen)3]2+ and their ortho methyl substituted analogs, which are high spin at room temperature but cross over to low spin at low temperature, suggest the RPBE/COSMO combination generates low spin states which are too stable by approximately 13 kcal mol(-1).

  19. A dual nitrite isotopic investigation of chemodenitrification by mineral-associated Fe(II) and its production of nitrous oxide

    Science.gov (United States)

    Grabb, Kalina C.; Buchwald, Carolyn; Hansel, Colleen M.; Wankel, Scott D.

    2017-01-01

    Under anaerobic conditions, the environmental reduction of nitrate (NO3-) and nitrite (NO2-) to more reduced forms is widely regarded as being microbially catalyzed. However, the chemical reduction of oxidized nitrogen species by reduced iron (Fe(II)), whether mineral-bound or surface-associated, may also occur under environmentally relevant conditions. Here we examine the nitrogen (N) and oxygen (O) stable isotope dynamics of the chemical reduction of NO2- by mineral associated Fe(II) (chemodenitrification) and its production of the potent greenhouse gas nitrous oxide (N2O). By shedding light on factors controlling kinetics of the reaction and its corresponding dual isotopic expression in the reactant NO2- and product N2O, this work contributes to a growing body of work aiming to improve our ability to identify chemodenitrification in the environment. Consistent with previous studies, we find that while homogenous reactions between aqueous NO2- and Fe(II) were kinetically slow, heterogeneous reactions involving Fe(II)-containing minerals often catalyzed considerable nitrite loss. In particular, rapid reduction of NO2- was catalyzed by the Fe-rich smectite clay mineral nontronite as well as the mixed Fe(II)-Fe(III) oxyhydroxide phase green rust. These minerals serve as both a source of reduced iron within the mineral structure as well as a surface for promoting the reactivity of Fe(II). However, even in the presence of aqueous Fe(II), experiments with low-Fe and non-Fe containing minerals showed little to no NO2- loss, perhaps suggesting a more dominant role for structural iron during chemodenitrification. When catalyzed by nontronite and green rust, N and O isotope effects for chemodenitrification (15εcDNF and 18εcDNF) ranged from 2 to 11‰ and 4 to 10‰, respectively, with lower values generally observed at higher reaction rates. Higher reaction rates were also linked to higher molar yields of N2O (up to 31%), highlighting a strong potential for

  20. HH 666: Different kinematics from H{\\alpha} and [Fe II] emission provide a missing link between jets and outflows

    CERN Document Server

    Reiter, Megan; Kiminki, Megan M; Bally, John

    2015-01-01

    HH 666 is an externally irradiated protostellar outflow in the Carina Nebula for which we present new near-IR [Fe II] spectra obtained with the FIRE spectrograph at Magellan Observatory. Earlier H{\\alpha} and near-IR [Fe II] imaging revealed that the two emission lines trace substantially different morphologies in the inner ~40" of the outflow. H{\\alpha} traces a broad cocoon that surrounds the collimated [Fe II] jet that extends throughout the parent dust pillar. New spectra show that this discrepancy extends to their kinematics. Near-IR [Fe II] emission traces steady, fast velocities of +/- 200 km/s from the eastern and western limbs of the jet. We compare this to a previously published H{\\alpha} spectrum that reveals a Hubble-flow velocity structure near the jet-driving source. New, second-epoch HST/ACS H{\\alpha} images reveal the lateral spreading of the H{\\alpha} outflow lobe away from the jet axis. H{\\alpha} proper motions also indicate a sudden increase in the mass-loss rate ~1000 yr ago, while steady ...

  1. Effect of sulfur compounds on biological reduction of nitric oxide in aqueous Fe(II)EDTA2- solutions

    NARCIS (Netherlands)

    Manconi, I.; Maas, van der P.M.F.; Lens, P.N.L.

    2006-01-01

    Biological reduction of nitric oxide (NO) in aqueous solutions of EDTA chelated Fe(II) is one of the main steps in the BioDeNOx process, a novel bioprocess for the removal of nitrogen oxides (NOx) from polluted gas streams. Since NOx contaminated gases usually also contain sulfurous pollutants, the

  2. A comparative study for the ion exchange of Fe(III) and Zn(II) on zeolite NaY.

    Science.gov (United States)

    Ostroski, Indianara C; Barros, Maria A S D; Silva, Edson A; Dantas, João H; Arroyo, Pedro A; Lima, Oswaldo C M

    2009-01-30

    The uptake capacity of Fe(III) and Zn(II) ions in NaY zeolite was investigated. Experiments were carried out in a fixed bed column at 30 degrees C, pH 3.5 and 4.5 for Fe(III) and Zn(II), respectively, and an average particle size of 0.180 mm. In order to minimize the diffusional resistances the influence of flow rate on the breakthrough curves at feed concentrations of 1.56 meq/L for Fe(III) and 0.844 meq/L for Zn(II) was investigated. Flow rate of the minimal resistance in the bed according to mass transfer parameter were 2.0 mL/min for iron and 8.0 mL/min for zinc ions. Freundlich and Langmuir isotherm models have been used to represent the column equilibrium data. The iron dynamic isotherm was successfully modeled by the Langmuir equation and this mathematical model described well the experimental breakthrough curves for feed concentrations from 0.1 up to 3.5 meq/L. The zinc dynamic isotherm was successfully modeled by the Freundlich equation. This equilibrium model was applied to mathematical model. Experimental breakthrough curves could be predicted. Experiments were also carried out in a batch reactor to investigate the kinetics adsorption of the ions Fe(III) and Zn(II). Langmuir kinetic model fit well both experimental data.

  3. Synthesis and characterization of dinuclear complexes containing the Fe(III)-F...(H2O)M(II) motif

    DEFF Research Database (Denmark)

    Ghiladi, M; Jensen, K.B.; Jiang, Jianzhong;

    1999-01-01

    The dinucleating phenolate-hinged ligand 4-tert-butyl-2,6-bis[bis(2-pyridylmethyl)aminomethyl]phenolate(bpb p) has been used to prepare a series of Fe(III)M(II) complexes containing independent species at the exogenous binding sites. These sites are occupied by fluoride and water ligands and show...

  4. The opposite effects of Cu(II) and Fe(III) on the assembly of glucagon amyloid fibrils

    NARCIS (Netherlands)

    Zhou, Xingfei; Tan, Juhua; Zheng, Lifei; Pillai, Saju; Li, Bin; Xu, Peng; Zhang, Bobo; Zhang, Yi

    2012-01-01

    A few transition metal ions are strongly implicated as co-factors in modulating the aggregation of amyloid peptides, which is believed to be a key factor in regulating the cytotoxicity of peptides. In this paper, we explored the effects of Cu(II) and Fe(III) on the aggregation/fibrillation of

  5. NO Removal in Continuous BioDeNOx Reactors: Fe(II)EDTA2- Regeneration, Biomass Growth, and EDTA Degradation

    NARCIS (Netherlands)

    Maas, van der P.M.F.; Brink, van den P.; Utomo, S.; Klapwijk, A.; Lens, P.N.L.

    2006-01-01

    BioDeNOx is a novel technique for NOx removal from industrial flue gases. In principle, BioDeNOx is based on NO absorption into an aqueous Fe(II)EDTA2- solution combined with biological regeneration of that scrubber liquor in a bioreactor. The technical and economical feasibility of the BioDeNOx

  6. On Spin Hamiltonian fits to Moessbauer spectra of high-spin Fe(II) porphyrinate systems

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, Charles E., E-mail: cschulz@knox.edu [Knox College, Department of Physics (United States); Hu Chuanjiang, E-mail: scheidt.1@nd.edu; Scheidt, W. Robert [University of Notre Dame, Department of Chemistry and Biochemistry (United States)

    2006-06-15

    Fits to Moessbauer spectra of high-spin iron(II) porphyrinates have been applied to the Fe(II) model compounds octaethylporphyrin(1,2-dimethylimidazole) and tetra-paramethoxyporphyrin(1,2-dimethylimidazole). Moessbauer spectra have been measured on these compounds at 4.2 K in large applied fields. Spin Hamiltonians were used for fitting both the electronic and nuclear interactions. The fits are done by adjusting the Hamiltonian parameters to simultaneously minimize the total {chi}{sup 2} for three different applied fields. In order to get best fits, the EFG tensor need to be rotated relative to the ZFS tensor. A comparative sensitivity analysis of their Spin Hamiltonian parameters has also been done on the ZFS parameters D, and the EFG asymmetry parameter {eta}. The best fits suggest that both systems definitely have a negative quadrupole splitting, and that largest EFG component is tilted far from the z-axis of the ZFS tensor, which is likely to be near the heme normal.

  7. Preparation and estimation of thermodynamic properties of Fe(II)-, Co(II)-, Ni(II)- and Zr(IV)-containing layered double hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Rozov, Konstantin; Curtius, Hilde; Bosbach, Dirk [Forschungszentrum Juelich GmbH (Germany). Inst. for Nuclear Waste Management and Reactor Safety (IEK-6)

    2015-07-01

    The investigation of layered double hydroxides (LDHs) was performed because they and similar 'green rust' phases were identified as specific secondary phases forming during the evolution of the disposed research reactor fuel elements under nuclear repository relevant conditions. LDHs or 'hydrotalcite-like' solids are of interest in environmental geochemistry because they can substitute various cations and especially due to the anion-exchange properties and, therefore, can be considered as buffer materials for retention of mobile and hazardous radionuclides (like, {sup 14}C, {sup 129}I, {sup 36}Cl, {sup 79}Se etc.). In our study Fe{sup 2+}-, Co{sup 2+}-, Ni{sup 2+}- and Zr{sup 4+}-containing LDHs have been synthesized by co-precipitation method and characterized (PXRD, FT-IR, SEM-EDX, TGA-DSC) in order to investigate the effect of substitution of 2- and 4-valent cations on the stability of LDHs. PXRD measurements demonstrated that: (1) pure Mg-Al-Fe(II) LDHs are existing in the range of the mole fraction of iron x{sub Fe} = Fe/(Mg+Fe) between 0 and 0.13. Unit-cell parameters (a{sub o}=b{sub o}) as a function of x{sub Fe} follow Vegard's law corroborating the existence of a solid solution when x{sub Fe} = 0 - 0.13. Products of syntheses with x{sub Fe} ≥ 0.13 contain detectable amounts (≥1-2 wt%) of additional phases (like, magnetite, maghemite, lepidocrocite); (2) pure Ni{sup 2+}- and Co{sup 2+}-containing LDHs (mole fractions of Ni and Co were equal to 0.1) have been synthesized successfully; (3) Mg-Al-Zr(IV) precipitates with mole fraction of zirconium x{sub Zr} = Zr/(Zr+Al) = 0.0 - 0.5 show PXRD patterns attributed to pure LDHs and the variation of lattice parameters a{sub o}=b{sub o} as a function of x{sub Zr} is in agreement with Vegard's law demonstrating the presence of solid solution. In contrast, PXRD analyses of precipitates with x{sub Zr} ≥ 0.5 have shown the presence of additional X-ray reflexes typical for brucite. The

  8. The acrylonitrile dimer ion

    Science.gov (United States)

    Ervasti, Henri K.; Jobst, Karl J.; Burgers, Peter C.; Ruttink, Paul J. Ae; Terlouw, Johan K.

    2007-04-01

    Large energy barriers prohibit the rearrangement of solitary acrylonitrile ions, CH2CHCN+, into their more stable hydrogen-shift isomers CH2CCNH+ or CHCH-CNH+. This prompted us to examine if these isomerizations occur by self-catalysis in acrylonitrile dimer ions. Such ions, generated by chemical ionization experiments of acrylonitrile with an excess of carbon dioxide, undergo five dissociations in the [mu]s time frame, as witnessed by peaks at m/z 53, 54, 79, 80 and 105 in their metastable ion mass spectrum. Collision experiments on these product ions, deuterium labeling, and a detailed computational analysis using the CBS-QB3 model chemistry lead to the following conclusions: (i) the m/z 54 ions are ions CH2CHCNH+ generated by self-protonation in ion-dipole stabilized hydrogen-bridged dimer ions [CH2CHCN...H-C(CN)CH2]+ and [CH2CHCN...H-C(H)C(H)CN]+; the proton shifts in these ions are associated with a small reverse barrier; (ii) dissociation of the H-bridged ions into CH2CCNH+ or CHCH-CNH+ by self-catalysis is energetically feasible but kinetically improbable: experiment shows that the m/z 53 ions are CH2CHCN+ ions, generated by back dissociation; (iii) the peaks at m/z 79, 80 and 105 correspond with the losses of HCN, C2H2 and H, respectively. The calculations indicate that these ions are generated from dimer ions that have adopted the (much more stable) covalently bound "head-to-tail" structure [CH2CHCN-C(H2)C(H)CN]+; experiments indicate that the m/z 79 (C5H5N) and m/z 105 (C6H6N2) ions have linear structures but the m/z 80 (C4H4N2) ions consist of ionized pyrimidine in admixture with its stable pyrimidine-2-ylidene isomer. Acrylonitrile is a confirmed species in interstellar space and our study provides experimental and computational evidence that its dimer radical cation yields the ionized prebiotic pyrimidine molecule.

  9. SERS and DFT investigation of 1-(2-pyridylazo)-2-naphthol and its metal complexes with Al(III), Mn(II), Fe(III), Cu(II), Zn(II) and Pb(II)

    Science.gov (United States)

    Szabó, László; Herman, Krisztian; Mircescu, Nicoleta E.; Fălămaş, Alexandra; Leopold, Loredana F.; Leopold, Nicolae; Buzumurgă, Claudia; Chiş, Vasile

    The development of surface-enhanced Raman scattering (SERS) as a prospective analytical methodology for detection of metal ions was shown in recent years by several studies on metal complexes. In this work, 1-(2-pyridylazo)-2-naphthol (PAN) and its Al(III), Mn(II), Fe(III), Cu(II), Zn(II) and Pb(II) complexes were studied by FTIR, FT-Raman and surface enhanced Raman spectroscopies. Molecular geometry optimization, molecular electrostatic potential (MEP) distribution and vibrational frequencies calculations were performed using the hybrid B3LYP exchange-correlation functional for the PAN molecule and its bidentate complexes. The calculated MEP distributions indicated the atoms with highest electronegativity, the adsorption to the silver surface occurring through these atoms. Based on experimental and theoretical data we were able to identify unique and representative features, useful for the identification of each PAN-metal complex.

  10. Influence of Exciplex formation on the electroluminescent properties of dimeric Zn (II) bis-2-(2'-hydroxyphenyl) benzoxazole complex and monomeric Zn (II) 2-(1'-hydroxynaphthyl) benzothiazole complex

    Science.gov (United States)

    Prakash, Sattey; Anand, R. S.; Manoharan, S. Sundar

    2011-10-01

    In this paper we present the factors affecting electroluminescent properties of Zinc complexes of oxazole & thiazole derivatives. Electroluminescent spectra of the Zinc (II) complex of bis-[2-(2'-hydroxyphenyl) benzoxazole], [Zn (HPBO)2]2 and 2-(1'-hydroxynaphthyl) benzothiazole [Zn (HNBT)2] show unusual broadening and shows structural and photophysical similarity with [Zn (HPBT)2]2, a dimeric complex. The [Zn (HPBO)2]2 complex as an emissive layer in the device structure ITO /PEDOT:PSS /TPD (30nm) /[Zn (HPBO)2]2 (60nm) /BCP (6nm) /Ca (3nm) /Al (200nm) shows a broad bluish green emission, with a full width at half maxima (FWHM1˜70nm). The EL spectra is much broader compared to the PL spectra because of exciplex formation at the interfacial region between the emissive layer (EML) & hole transport layer (HTL). We also show the device performance of Zinc 2-(1'-hydroxynaphthyl) benzothiazole [Zn (HNBT)2] complex as emissive layer. Distinctly this device shows a broad greenish yellow emission with a peak maxima at 535nm and 690nm, owing to the exciplex formation between electron transport layer (ETL) and emissive layer (EML), which is in sharp contrast to the exciplex formation across the HTL-EML interface observed for the [Zn (HPBO)2]2 complex.

  11. Importance of reduced sulfur for the equilibrium chemistry and kinetics of Fe(II), Co(II) and Ni(II) supplemented to semi-continuous stirred tank biogas reactors fed with stillage

    Energy Technology Data Exchange (ETDEWEB)

    Shakeri Yekta, Sepehr, E-mail: sepehr.shakeri.yekta@liu.se [Department of Thematic Studies – Water and Environmental Studies, Linköping University, SE-581 83 Linköping (Sweden); Lindmark, Amanda [Department of Thematic Studies – Water and Environmental Studies, Linköping University, SE-581 83 Linköping (Sweden); Skyllberg, Ulf [Department of Forest Ecology and Management, Swedish University of Agricultural Sciences, SE-901 83 Umeå (Sweden); Danielsson, Åsa; Svensson, Bo H. [Department of Thematic Studies – Water and Environmental Studies, Linköping University, SE-581 83 Linköping (Sweden)

    2014-03-01

    Highlights: • Thermodynamics and kinetics of Fe, Co and Ni added to biogas reactors were studied. • Formation of Fe-sulfide and Fe-thiol aqueous complexes controlled the Fe solubility. • Cobalt solubility was controlled by processes independent of Co-sulfide interaction. • Iron added to the biogas reactors effected the Ni speciation and solubility. - Abstract: The objective of the present study was to assess major chemical reactions and chemical forms contributing to solubility and speciation of Fe(II), Co(II), and Ni(II) during anaerobic digestion of sulfur (S)-rich stillage in semi-continuous stirred tank biogas reactors (SCSTR). These metals are essential supplements for efficient and stable performance of stillage-fed SCSTR. In particular, the influence of reduced inorganic and organic S species on kinetics and thermodynamics of the metals and their partitioning between aqueous and solid phases were investigated. Solid phase S speciation was determined by use of S K-edge X-ray absorption near-edge spectroscopy. Results demonstrated that the solubility and speciation of supplemented Fe were controlled by precipitation of FeS(s) and formation of the aqueous complexes of Fe-sulfide and Fe-thiol. The relatively high solubility of Co (∼20% of total Co content) was attributed to the formation of compounds other than Co-sulfide and Co-thiol, presumably of microbial origin. Nickel had lower solubility than Co and its speciation was regulated by interactions with FeS(s) (e.g. co-precipitation, adsorption, and ion substitution) in addition to precipitation/dissolution of discrete NiS(s) phase and formation of aqueous Ni-sulfide complexes.

  12. Comportamento do ácido fítico na presença de Fe(II e Fe(III Behaviour of phytic acid in the presence of iron(II and iron(III

    Directory of Open Access Journals (Sweden)

    Hanna Raquel Quirrenbach

    2009-03-01

    Full Text Available O ácido fítico, dependendo do valor de pH, apresenta alto potencial quelante, complexando íons metálicos, inibindo, assim, a produção de espécies reativas de oxigênio, responsáveis pela destruição oxidativa em sistemas biológicos. Esse potencial quelante tem fundamentado diversos estudos aplicados à ação antioxidante em produtos alimentícios. O objetivo deste trabalho foi estudar o grau de interação do ácido fítico com os íons metálicos Fe(II e Fe(III, de importância biológica, em condições próximas às fisiológicas, e a estabilidade destes complexos. Titulações potenciométricas foram conduzidas para determinar as constantes de formação dos complexos ácido fítico-Fe(II e ácido fítico-Fe(III em solução aquosa, atmosfera inerte, força iônica 0,100 mol.L-1 de cloreto de potássio e à temperatura de 36 ± 0,1 ºC. Estudos espectroscópicos na região do UV-Vis foram realizados para acompanhar a formação dos complexos em solução. Os complexos ácido fítico-Fe(II e ácido fítico-Fe(III foram sintetizados e caracterizados por espectroscopia de absorção na região do infravermelho e por estudos termoanalíticos. Os resultados do conjunto de técnicas utilizadas evidenciaram, tanto em solução como no estado sólido, a presença dos íons metálicos coordenados ao ácido fítico.Depending on the pH value, phytic acid presents high chelating potential bonding metallic ions thus inhibiting the production of reactivated oxygen species, which are responsible for the oxidative destruction in biological systems. Such chelating potential has been the basis of several studies on the antioxidant action in food products. The objective of this work was to study the degree of interaction of the phytic acid with the metallic ions Fe(II and Fe(III, of biological importance, in near-physiological conditions and the stability of these complexes. Potentiometric titrations were applied to determine the constants of

  13. 4-nitrocatechol as a probe of a Mn(II)-dependent extradiol-cleaving catechol dioxygenase (MndD): comparison with relevant Fe(II) and Mn(II) model complexes.

    Science.gov (United States)

    Reynolds, Mark F; Costas, Miquel; Ito, Masami; Jo, Du-Hwan; Tipton, A Alex; Whiting, Adam K; Que, Lawrence

    2003-02-01

    Mn(II)-dependent 3,4-dihydroxyphenylacetate 2,3-dioxygenase (MndD) is an extradiol-cleaving catechol dioxygenase from Arthrobacter globiformis that has 82% sequence identity to and cleaves the same substrate (3,4-dihydroxyphenylacetic acid) as Fe(II)-dependent 3,4-dihydroxyphenylacetate 2,3-dioxygenase (HPCD) from Brevibacterium fuscum. We have observed that MndD binds the chromophoric 4-nitrocatechol (4-NCH(2)) substrate as a dianion and cleaves it extremely slowly, in contrast to the Fe(II)-dependent enzymes which bind 4-NCH(2) mostly as a monoanion and cleave 4-NCH(2) 4-5 orders of magnitude faster. These results suggest that the monoanionic binding state of 4-NC is essential for extradiol cleavage. In order to address the differences in 4-NCH(2) binding to these enzymes, we synthesized and characterized the first mononuclear monoanionic and dianionic Mn(II)-(4-NC) model complexes as well as their Fe(II)-(4-NC) analogs. The structures of [(6-Me(2)-bpmcn)Fe(II)(4-NCH)](+), [(6-Me(3)-TPA)Mn(II)(DBCH)](+), and [(6-Me(2)-bpmcn)Mn(II)(4-NCH)](+) reveal that the monoanionic catecholate is bound in an asymmetric fashion (Delta r(metal-O(catecholate))=0.25-0.35 A), as found in the crystal structures of the E(.)S complexes of extradiol-cleaving catechol dioxygenases. Acid-base titrations of [(L)M(II)(4-NCH)](+) complexes in aprotic solvents show that the p K(a) of the second catecholate proton of 4-NCH bound to the metal center is half a p K(a) unit higher for the Mn(II) complexes than for the Fe(II) complexes. These results are in line with the Lewis acidities of the two divalent metal ions but are the opposite of the trend observed for 4-NCH(2) binding to the Mn(II)- and Fe(II)-catechol dioxygenases. These results suggest that the MndD active site decreases the second p K(a) of the bound 4-NCH(2) relative to the HPCD active site.

  14. Neutron scattering in dimers

    DEFF Research Database (Denmark)

    Gudel, H. U.; Furrer, A.; Kjems, Jørgen

    1986-01-01

    Insulating compounds containing dimers of transition metal and rare earth ions have been studied by inelastic neutron scattering (INS). Energy splittings can be directly determined, and the corresponding parameters are easily extracted from the experimental data. The intensities of dimer excitati......Insulating compounds containing dimers of transition metal and rare earth ions have been studied by inelastic neutron scattering (INS). Energy splittings can be directly determined, and the corresponding parameters are easily extracted from the experimental data. The intensities of dimer...

  15. Ultraviolet photodissociation of the van der Waals dimer (CH3I)(2) revisited. II. Pathways giving rise to neutral molecular iodine

    NARCIS (Netherlands)

    Vidma, K.V.; Baklanov, A.V.; Zhang, Y.W.; Parker, D.H.

    2006-01-01

    The formation of neutral I-2 by the photodissociation of the methyl iodide dimer, (CH3I)(2), excited within the A band at 249.5 nm is evaluated using velocity map imaging. In previous work [J. Chem. Phys. 122, 204301 (2005)], we showed that the formation of I-2(+) from photodissociation of the

  16. Novel bentonite clay-based Fe-nanocomposite as a heterogeneous catalyst for photo-Fenton discoloration and mineralization of Orange II.

    Science.gov (United States)

    Feng, Jiyun; Hu, Xijun; Yue, Po Lock

    2004-01-01

    A novel bentonite clay-based Fe-nanocomposite (Fe-B) was successfully developed as a heterogeneous catalyst for photo-Fenton discoloration and mineralization of an azo-dye Orange II. X-ray diffraction (XRD) analysis clearly reveals that the Fe-B nanocomposite catalyst mainly consists of Fe2O3 (hematite) and SiO2 (quartz) crystallites, and the Fe concentration of the Fe-B catalyst determined by X-reflective fluorescence (XRF) is 31.8 wt %. The catalytic activity of the Fe-B was evaluated in the discoloration and mineralization of Orange II in the presence of H2O2 and UVC light (254 nm). It was found that the optimal Fe-B catalyst dosage is around 1.0 g/L, and the efficiency of discoloration and mineralization of Orange II increases as initial Orange II concentration decreases or reaction temperature increases. In addition, at optimal conditions (10 mM H2O2, 1.0 g of Fe-B/L, 1 x 8W UVC, and pH = 3.0), complete discoloration and mineralization of 0.2 mM Orange II can be achieved in less than 60 and 120 min, respectively. The result strongly indicates that the Fe-B nanocomposite catalyst exhibits a high catalytic activity not only in the photo-Fenton discoloration of Orange II but also in the mineralization of Orange II. The reaction kinetics analysis illustrates that the photo-Fenton discoloration of Orange II in the first 15 min obeys the pseudo-first-order kinetics. The reaction activation energy calculated was 9.94 kJ/mol, indicating that the photo-Fenton discoloration of Orange II is not very sensitive to reaction temperature.

  17. Dissolved Fe(II) in the Pacific Ocean: Measurements from the P16N CLIVAR/CO2 Repeat Hydrography Cruise

    Science.gov (United States)

    Hansard, S. P.; Landing, W. M.; Measures, C. I.

    2006-12-01

    Vertical profiles of seawater Fe(II) concentration were obtained for 37 stations sampled in early 2006, in conjunction with the CLIVAR Repeat Hydrography P16N transect (152° W, Tahiti to Alaska). At each station, seawater samples were collected from 12 target depths (0-1000 m) using trace-metal clean Go-Flo bottles. Upon recovery, Go-Flo bottles were immediately transferred to a Class 100 clean van and sub-sampled for Fe(II) by passing sample water through a 0.2 μm Supor (polyethersulfone) cartridge filter into 125 mL containers, pre-loaded with 25 μL of 6M quartz-distilled HCl (final pH ~~ 6) to slow oxidation. Samples were immediately analyzed for Fe(II) using a luminol-based chemiluminescence method. Total dissolved iron was also determined shipboard by spectrophotometric flow injection analysis. The data collected from this cruise will be presented, along with corroborating data from another North Pacific cruise (PO2). Concentrations of Fe(II) ranged from below detection (meters. Photoreduction of Fe(III) has been cited as a source of Fe(II) in surface waters, and the pattern of attenuation with depth is consistent with this mechanism. Many samples collected at or near the bottom of the profile (500-1000 m) exhibited elevated Fe(II) relative to the mid-depths of the profile. Due to the higher total dissolved iron at depth, the percentage of Fe(II) was low in these samples. Recent studies support the presence of Fe(II) at depth, in association with low or suboxic conditions. In situ processes such as the remineralization of sinking biogenic particles may provide a source for this Fe(II).

  18. Selective NO trapping in the pores of chain-type complex assemblies based on electronically activated paddlewheel-type [Ru2(II,II)]/[Rh2(II,II)] dimers.

    Science.gov (United States)

    Kosaka, Wataru; Yamagishi, Kayo; Hori, Akihiro; Sato, Hiroshi; Matsuda, Ryotaro; Kitagawa, Susumu; Takata, Masaki; Miyasaka, Hitoshi

    2013-12-11

    The design of porous materials that undergo selective adsorption of a specific molecule is a critical issue in research on porous coordination polymers or metal-organic frameworks. For the purpose of the selective capture of molecules possessing an electron-acceptor character such as nitric oxide (NO), one-dimensional chain compounds possessing a high donor character have been synthesized using 4-chloroanisate-bridged paddlewheel-type dimetal(II, II) complexes with M = Ru and Rh and phenazine (phz) as the chain linker: [M2(4-Cl-2-OMePhCO2)4(phz)]·n(CH2Cl2) (M = Ru, 1; Rh, 2). These compounds are isostructural and are composed of chains with a [-{M2}-phz-] repeating unit and CH2Cl2 occupying the void space between the chains. Compounds 1 and 2 change to a new phase (1-dry and 2-dry) upon evacuating the crystallization solvent (CH2Cl2) and almost lose their pores in the drying process: no void space in 1-dry and 31.8 Å(3), corresponding to 2.9% of the cell volume, in 2-dry. Nevertheless, the compounds show a unique gas accommodation ability. Accompanied by a structural transformation (i.e., the first gate-opening) at low pressures of molecules per [M2] unit. In addition, the adsorption isotherm for NO (121 K) involves the first gate-opening followed by a second gate-opening anomaly at NO pressures of ≈52 kPa for 1-dry and ≈21 kPa for 2-dry. At the first gate-opening, the absorbed amount of NO is ca. 4 molecules per [M2] unit, and then it reaches 8.4 and 6.3 for 1-dry and 2-dry, respectively, at 95 kPa. Only the isotherm for NO exhibits hysteresis in the desorption process, and some of the NO molecules are trapped in pores even after evacuating at 121 K, although it recovers to the original dried sample on heating to room temperature. The adsorbed NO molecules accrue a significant electron donation from the host framework even in the [Rh2] derivative, indicating that such simple porous compounds with electron-donor characteristics are useful for the selective

  19. ADSORPSI ION CU(II MENGGUNAKAN PASIR LAUT TERAKTIVASI H2SO4 DAN TERSALUT Fe2O3

    Directory of Open Access Journals (Sweden)

    DS Pambudi

    2014-11-01

    Full Text Available Pasir laut merupakan bahan alam yang melimpah. Selain digunakan sebagai bahan bangunan, pasir dapat dimanfaatkan sebagai penjerap ion logam berat mengingat 30% lebih dari volumenya adalah pori-pori. Tujuan penelitian adalah untuk mengetahui kapasitas adsorpsi ion logam Cu(II menggunakan pasir laut kontrol, pasir laut teraktivasi H2SO4, pasir laut tersalut Fe2O3, serta pasir laut teraktivasi H2SO4 dan tersalut Fe2O3. Ada dua macam pasir laut yang digunakan, yaitu pasir hitam dan pasir putih. Kajian yang dilakukan meliputi optimasi adsorben pada variasi pH, konsentrasi ion logam, dan waktu kontak. Optimasi pH diperoleh pada pH 7, optimasi konsentasi ion logam diperoleh 250 ppm untuk pasir hitam dan 200 ppm untuk pasir putih, dan optimasi waktu diperoleh 60 menit untuk pasir hitam dan 90 menit untuk pasir putih. Kapasitas adsorpsi pasir laut teraktivasi H2SO4 dan tersalut Fe2O3 dalam menyerap ion logam tembaga sebesar 24,8634 mg/g untuk pasir hitam dan 19,8854 mg/g untuk pasir putih. Sebanyak 6,5 g pasir hitam teraktivasi H2SO4 dan tersalut Fe2O3 digunakan untuk menyerap limbah pada konsentrasi Cu(II sebesar 2960,32 ppm dengan persentase teradsorpsi sebesar 94,70%. Sedangkan pada pasir putih teraktivasi H2SO4 dan tersalut Fe2O3, sebanyak 8 g pasir digunakan untuk menyerap limbah dengan konsentrasi Cu(II sebesar 2984,13 ppm, hasilnya menunjukkan 92,56% ion logam Cu(II teradsorp. Sea sand is abundant natural materials. In addition to be used as a building material, sand can be utilized as heavy metal ion adsorbent, because it has quite a lot of pores, i.e 30% more than its volume. The purpose of this study was to determine the adsorption capacity of Cu(II ions using sea sand alone as control, H2SO4-activated sea sand, Fe2O3-coated sea sand, as well as H2SO4-activated and Fe2O3-coated sea sand. Two kinds of sea sand have been used in the research, i.e the black sand and the white sand. Studies were performed to examine the optimization of the

  20. Effects of Fe(II) and hydrogen peroxide interaction upon dissolving UO2 under geologic repository conditions.

    Science.gov (United States)

    Amme, M; Bors, W; Michel, C; Stettmaier, K; Rasmussen, G; Betti, M

    2005-01-01

    Iron redox cycling is supposed to be one of the major mechanisms that control the geochemical boundary conditions in the near field of a geologic repository for UO2 spent nuclear fuel. This work investigates the impact of reactions between hydrogen peroxide (H2O2) and iron (Fe2+/Fe3+) on UO2 dissolution. The reaction partners were contacted with UO2 in oxygen-free batch reactor tests. The interaction in absence of UO2 gives a stoichiometric redox reaction of Fe2+ and H2O2 when the reactants are present in equal concentration. Predomination of H202 results in its delayed catalytic decomposition. With UO2 present, its dissolution is controlled by either a slow mechanism (as typical for anoxic environments) or uranium peroxide precipitation, depending strongly on the reactant ratio. Uranium peroxide (UO4 x nH2O, m-studtite), detected on UO2 surfaces after exposure to H2O2, was not found on the surfaces exposed to solutions with stoichometric Fe(II)/ H2O2 ratios. This suggests that H2O2 was deactivated in redox reactions before a formation of UO4 took place. ESR measurements employing the spin trapping technique revealed only the DMPO-OH adduct within the first minutes after the reaction start (high initial concentrations of the OH radical); however, in the case of Fe(II) and H2O2 reacting at 10(-4) mol/L with UO2, dissolved oxygen and Fe2+ concentrations indicate the participation of further Fe intermediates and, therefore, Fenton redox activities.

  1. Production of hydroxyl radicals from Fe(II) oxygenation induced by groundwater table fluctuations in a sand column.

    Science.gov (United States)

    Jia, Mengqi; Bian, Xiao; Yuan, Songhu

    2017-04-15

    Natural and artificial processes often cause the fluctuation of groundwater table, inducing the interaction of O2 from the unsaturated zone with reduced components such as Fe(II) from the saturated zone. In light of previous findings that hydroxyl radicals (OH) can be produced from Fe(II) oxygenation, we hypothesize that OH could be produced during groundwater table fluctuations. Therefore, this study aims to measure the production of OH during water table fluctuations in a simulated sand column. Deoxygenated water in the absence and presence of 20mg/L Fe(2+) (pH6.5) was fed into the sand column. Water table fluctuations were manipulated to observe O2 entrapment, Fe(2+)oxygenation and OH production. Results showed that O2 in the pore air was efficiently entrapped by the rise of water table at the tested rates of 0.16-0.34cm/min (or 0.10-0.20m/h), and the dissolution of entrapped O2 into the pore water led to the oxygenation of Fe(2+). Production of OH was presumably attributed to oxygenation of the Fe(2+) adsorbed on Fe(III) oxyhydroxides generated in situ. In a total of 4cycles of fluctuations, the cumulative OH at all the elevations increased progressively, attaining 2.7μM in the zone near the water table in the 4th cycle. We suggest that OH produced from water table fluctuations could induce an overlooked pathway for contaminant transformation in the fluctuation zone. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Effect of phosphate, silicate, and Ca on the morphology, structure and elemental composition of Fe(III)-precipitates formed in aerated Fe(II) and As(III) containing water

    Science.gov (United States)

    Kaegi, Ralf; Voegelin, Andreas; Folini, Doris; Hug, Stephan J.

    2010-10-01

    We investigated Fe(III)-precipitates formed from Fe(II) oxidation in water at pH 7 as a function of dissolved Fe(II), As(III), phosphate, and silicate in the absence and presence of Ca. We used transmission electron microscopy (TEM), including selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDX) to characterize the morphology, structure and elemental composition of the precipitates. Results from our companion X-ray absorption spectroscopy (XAS) study suggested that the oxidation of Fe(II) leads to the sequential formation of distinct polymeric units in the following order: Fe(III)-phosphate oligomers in the presence of phosphate, silicate-rich hydrous ferric oxide (HFO-Si) at high Si/Fe (>0.5) or 2-line ferrihydrite (2L-Fh) at lower Si/Fe (˜0.1-0.5), and lepidocrocite (Lp) in the absence of phosphate at low Si/Fe (arrangement of the different polymeric units within Fe(III)-precipitates. The resulting structural and compositional heterogeneity of short-range-ordered Fe(III)-precipitates likely affects their colloidal stability and their chemical reactivity and needs to be considered when addressing the fate of co-transformed trace elements such as arsenic.

  3. Importance of reduced sulfur for the equilibrium chemistry and kinetics of Fe(II), Co(II) and Ni(II) supplemented to semi-continuous stirred tank biogas reactors fed with stillage.

    Science.gov (United States)

    Shakeri Yekta, Sepehr; Lindmark, Amanda; Skyllberg, Ulf; Danielsson, Asa; Svensson, Bo H

    2014-03-30

    The objective of the present study was to assess major chemical reactions and chemical forms contributing to solubility and speciation of Fe(II), Co(II), and Ni(II) during anaerobic digestion of sulfur (S)-rich stillage in semi-continuous stirred tank biogas reactors (SCSTR). These metals are essential supplements for efficient and stable performance of stillage-fed SCSTR. In particular, the influence of reduced inorganic and organic S species on kinetics and thermodynamics of the metals and their partitioning between aqueous and solid phases were investigated. Solid phase S speciation was determined by use of S K-edge X-ray absorption near-edge spectroscopy. Results demonstrated that the solubility and speciation of supplemented Fe were controlled by precipitation of FeS(s) and formation of the aqueous complexes of Fe-sulfide and Fe-thiol. The relatively high solubility of Co (∼ 20% of total Co content) was attributed to the formation of compounds other than Co-sulfide and Co-thiol, presumably of microbial origin. Nickel had lower solubility than Co and its speciation was regulated by interactions with FeS(s) (e.g. co-precipitation, adsorption, and ion substitution) in addition to precipitation/dissolution of discrete NiS(s) phase and formation of aqueous Ni-sulfide complexes. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. C-C bond formation and related reactions at the CNC backbone in (smif)FeX (smif = 1,3-di-(2-pyridyl)-2-azaallyl): dimerizations, 3 + 2 cyclization, and nucleophilic attack; transfer hydrogenations and alkyne trimerization (X = N(TMS)2, dpma = (di-(2-pyridyl-methyl)-amide)).

    Science.gov (United States)

    Frazier, Brenda A; Williams, Valerie A; Wolczanski, Peter T; Bart, Suzanne C; Meyer, Karsten; Cundari, Thomas R; Lobkovsky, Emil B

    2013-03-18

    Molecular orbital analysis depicts the CNC(nb) backbone of the smif (1,3-di-(2-pyridyl)-2-azaallyl) ligand as having singlet diradical and/or ionic character where electrophilic or nucleophilic attack is plausible. Reversible dimerization of (smif)Fe{N(SiMe3)2} (1) to [{(Me3Si)2N}Fe]2(μ-κ(3),κ(3)-N,py2-smif,smif) (2) may be construed as diradical coupling. A proton transfer within the backbone-methylated, and o-pyridine-methylated smif of putative ((b)Me2(o)Me2smif)FeN(SiMe3)2 (8) provides a route to [{(Me3Si)2N}Fe]2(μ-κ(4),κ(4)-N,py2,C-((b)Me,(b)CH2,(o)Me2(smif)H))2 (9). A 3 + 2 cyclization of ditolyl-acetylene occurs with 1, leading to the dimer [{2,5-di(pyridin-2-yl)-3,4-di-(p-tolyl-2,5-dihydropyrrol-1-ide)}FeN(SiMe3)2]2 (11), and the collateral discovery of alkyne cyclotrimerization led to a brief study that identified Fe(N(SiMe3)2(THF) as an effective catalyst. Nucleophilic attack by (smif)2Fe (13) on (t)BuNCO and (2,6-(i)Pr2C6H3)NCO afforded (RNHCO-smif)2Fe (14a, R = (t)Bu; 14b, 2,6-(i)PrC6H3). Calculations suggested that (dpma)2Fe (15) would favorably lose dihydrogen to afford (smif)2Fe (13). H2-transfer to alkynes, olefins, imines, PhN═NPh, and ketones was explored, but only stoichiometric reactions were affected. Some physical properties of the compounds were examined, and X-ray structural studies on several dinuclear species were conducted.

  5. Heterogeneous dimer peptide-conjugated polylysine dendrimer-Fe3O4 composite as a novel nanoscale molecular probe for early diagnosis and therapy in hepatocellular carcinoma

    Science.gov (United States)

    Shen, Jian-Min; Li, Xin-Xin; Fan, Lin-Lan; Zhou, Xing; Han, Ji-Min; Jia, Ming-Kang; Wu, Liang-Fan; Zhang, Xiao-Xue; Chen, Jing

    2017-01-01

    A novel nanoscale molecular probe is formulated in order to reduce toxicity and side effects of antitumor drug doxorubicin (DOX) in normal tissues and to enhance the detection sensitivity during early imaging diagnosis. The mechanism involves a specific targeting of Arg-Gly-Asp peptide (RGD)-GX1 heterogeneous dimer peptide-conjugated dendrigraft poly-l-lysine (DGL)–magnetic nanoparticle (MNP) composite by αvβ3-integrin/vasculature endothelium receptor-mediated synergetic effect. The physicochemical properties of the nanoprobe were characterized by using transmission electron microscope, Fourier transform infrared spectroscopy, X-ray diffraction, dynamic light scattering (DLS), and vibrating sample magnetometer. The average diameter of the resulting MNP–DGL–RGD-GX1–DOX nanoparticles (NPs) was ~150−160 nm by DLS under simulate physiological medium. In the present experimental system, the loading amount of DOX on NPs accounted for 414.4 mg/g for MNP–DGL–RGD-GX1–DOX. The results of cytotoxicity, flow cytometry, and cellular uptake consistently indicated that the MNP–DGL–RGD-GX1–DOX NPs were inclined to target HepG2 cells in selected three kinds of cells. In vitro exploration of molecular mechanism revealed that cell apoptosis was associated with the overexpression of Fas protein and the significant activation of caspase-3. In vivo magnetic resonance imaging and biodistribution study showed that the MNP–DGL–RGD-GX1–DOX formulation had high affinity to the tumor tissue, leading to more aggregation of NPs in the tumor. In vivo antitumor efficacy research verified that MNP–DGL–RGD-GX1–DOX NPs possessed significant antitumor activity and the tumor inhibitory rate reached 78.5%. These results suggested that NPs could be promising in application to early diagnosis and therapy in hepatocellular carcinoma as a specific nanoprobe. PMID:28243083

  6. Novel FeII and CoII Complexes of Natural Product Tryptanthrin: Synthesis and Binding with G-Quadruplex DNA

    Science.gov (United States)

    Zhong, Yi-ning; Zhang, Yan; Gu, Yun-qiong; Wu, Shi-yun; Shen, Wen-ying

    2016-01-01

    Tryptanthrin is one of the most important members of indoloquinoline alkaloids. We obtained this alkaloid from Isatis. Two novel FeII and CoII complexes of tryptanthrin were first synthesized. Single-crystal X-ray diffraction analyses show that these complexes display distorted four-coordinated tetrahedron geometry via two heterocyclic nitrogen and oxygen atoms from tryptanthrin ligand. Binding with G-quadruplex DNA properties revealed that both complexes were found to exhibit significant interaction with G-quadruplex DNA. This study may potentially serve as the basis of future rational design of metal-based drugs from natural products that target the G-quadruplex DNA. PMID:27698647

  7. Synthesis, crystal structures and magnetic properties of cyanide- and phenolate-bridged [M(III)NiII]2 tetranuclear complexes (M=Fe and Cr).

    Science.gov (United States)

    Toma, Liviu; Toma, Luminita Marilena; Lescouëzec, Rodrigue; Armentano, Donatella; De Munno, Giovanni; Andruh, Marius; Cano, Joan; Lloret, Francesc; Julve, Miguel

    2005-04-21

    The binuclear complex NiII2L(H2O)2(ClO4)2(1) and the neutral tetranuclear bimetallic compounds [{M(III)(phen)(CN)4}2{NiII2L(H2O)2}].2CH3CN with M=Fe (2) and Cr (3)[H2L=11,23-dimethyl-3,7,15,19-tetraazatricyclo[19.3.1.1(9,13)]hexacosa-2,7,9,11,13(26),14,19,21(25),22,24-decaene-25,26-diol] have been synthesized and the structures of and determined by single crystal X-ray diffraction. and are isostructural compounds whose structure is made up of centrosymmetric binuclear cations [Ni2(L)(H2O)2]2+ and two peripheral [M(phen)(CN)4]- anions [M=Fe (2) and Cr (3)] acting as monodentate ligands towards the nickel atoms through one of their four cyanide nitrogen atoms. The environment of the metal atoms in 2 and 3 is six-coordinated: two phen-nitrogen and four cyanide-carbon atoms at the iron and chromium atoms and a water molecule, one cyanide-nitrogen and two phenolate-oxygens and two imine-nitrogens from the binucleating ligand L2- at the nickel atom build distorted octahedral surroundings. The values of the FeNi and CrNi separations through the single cyanide bridge are 5.058(1) and 5.174(2)A respectively, whereas the Ni-Ni distances across the double phenolate bridge are 3.098(2)(2) and 3.101(1) A (3). The magnetic properties of have been investigated in the temperature range 1.9-290 K. The magnetic behaviour of corresponds to that of an antiferromagnetically coupled nickel(II) dimer with J=-61.0(1) cm-1, the Hamiltonian being defined as H=-J S(A).S(B). An overall antiferromagnetic behaviour is observed for and with a low-lying singlet spin state. The values of the intramolecular magnetic couplings are J(Fe-Ni)=+17.4(1) cm-1 and J(Ni-Ni(a))=-44.4(1) cm-1 for and J(Cr-Ni)=+11.8(1) cm-1 and J(Ni-Ni(a))=-44.6(1) cm-1 for [H=-J(M-Ni)(S(M).S(Ni)+S(Ma).S(Nia))-J(Ni-Nia)S(Ni)S(Nia)]. Theoretical calculations using methods based on density functional theory (DFT) have been employed on in order to analyze the efficiency of the exchange pathways involved and also to substantiate

  8. Strongly Variable z=1.48 MgII and FeII Absorption in the Spectra of z=4.05 GRB 060206

    CERN Document Server

    Hao, H; Dobrzycki, A; Matheson, T; Bentz, M C; Kuraszkiewicz, J; Garnavich, P M; Howk, J C; Calkins, M L; Worthey, G; Modjaz, M; Serven, J

    2006-01-01

    We report on the discovery of strongly variable MgII and FeII absorption lines seen at z=1.48 in the spectra of the z=4.05 GRB 060206 obtained between 4.13 to 7.63 hours after the burst. In particular, the FeII line equivalent width (EW) decayed rapidly from 1.72+-0.25 AA to 0.28+-0.21 AA, only to increase to 0.96+-0.21 AA in a later date spectrum. The MgII doublet shows even more complicated evolution: the weaker line of the doublet drops from 2.05+-0.25 AA to 0.92+-0.32 AA, but then more than doubles to 2.47+-0.41 AA in later data. The ratio of the EWs for the MgII doublet is also variable, being closer to 1:1 (saturated regime) when the lines are stronger and becoming closer to 2:1 (unsaturated regime) when the lines are weaker, consistent with expectations based on atomic physics. We have investigated and rejected the possibility of any instrumental or atmospheric effects causing the observed strong variations. The possibility of variable intervening absorption in GRB spectra was recently predicted by Fra...

  9. Self-assembled 3D heterometallic Cu(II)/Fe(II) coordination polymers with octahedral net skeletons: structural features, molecular magnetism, thermal and oxidation catalytic properties.

    Science.gov (United States)

    Karabach, Yauhen Y; Guedes da Silva, M Fátima C; Kopylovich, Maximilian N; Gil-Hernández, Beatriz; Sanchiz, Joaquin; Kirillov, Alexander M; Pombeiro, Armando J L

    2010-12-06

    The new three-dimensional (3D) heterometallic Cu(II)/Fe(II) coordination polymers [Cu(6)(H(2)tea)(6)Fe(CN)(6)](n)(NO(3))(2n)·6nH(2)O (1) and [Cu(6)(Hmdea)(6)Fe(CN)(6)](n)(NO(3))(2n)·7nH(2)O (2) have been easily generated by aqueous-medium self-assembly reactions of copper(II) nitrate with triethanolamine or N-methyldiethanolamine (H(3)tea or H(2)mdea, respectively), in the presence of potassium ferricyanide and sodium hydroxide. They have been isolated as air-stable crystalline solids and fully characterized including by single-crystal X-ray diffraction analyses. The latter reveal the formation of 3D metal-organic frameworks that are constructed from the [Cu(2)(μ-H(2)tea)(2)](2+) or [Cu(2)(μ-Hmdea)(2)](2+) nodes and the octahedral [Fe(CN)(6)](4-) linkers, featuring regular (1) or distorted (2) octahedral net skeletons. Upon dehydration, both compounds show reversible escape and binding processes toward water or methanol molecules. Magnetic susceptibility measurements of 1 and 2 reveal strong antiferromagnetic [J = -199(1) cm(-1)] or strong ferromagnetic [J = +153(1) cm(-1)] couplings between the copper(II) ions through the μ-O-alkoxo atoms in 1 or 2, respectively. The differences in magnetic behavior are explained in terms of the dependence of the magnetic coupling constant on the Cu-O-Cu bridging angle. Compounds 1 and 2 also act as efficient catalyst precursors for the mild oxidation of cyclohexane by aqueous hydrogen peroxide to cyclohexanol and cyclohexanone (homogeneous catalytic system), leading to maximum total yields (based on cyclohexane) and turnover numbers (TONs) up to about 22% and 470, respectively.

  10. [Molecular techniques for cyanobacteria detection at Riogrande II and La Fe water reservoirs, Colombia].

    Science.gov (United States)

    Hurtado-Alarcón, Julio César; Polanía-Vorenberg, Jaime

    2014-03-01

    In lentic water bodies as reservoirs occur eutrophication processes, originated mainly from human activities (i.e. agriculture, animal exploitation). This influx of nutrients in aquatic ecosystems could promote blooms of potentially toxic cyanobacteria. The purpose of this work is to detect the presence of cyanobacteria strains in water samples, using molecular techniques to help in preventive management of reservoirs dedicated to water purification. We used two molecular techniques to detect genes implied with the synthesis of hepatotoxic microcystins from potentially toxic cyanobacteria strains, and to evaluate the molecular diversity of cyanobacteria in water samples from two high-mountain reservoirs used for purification of drinking water for the metropolitan area of Medellin, Colombia. Between 2010-2011 collections of 12 water samples were taken and DNA extraction together with PCR and DGGE analyses where carried out. We amplified 22 sequences between 250-300bp of the genes mcyA and mcyE, and these sequences were related with several strains and cyanobacteria genera accessions from NCBI-GenBank databases. Moreover, sequence amplifications of the 16S small ribosomal RNA subunit - 16S rRNA- between 400-800bp were also performed in order to use them for the DGGE technique. The amplification products of DGGE were set in polyacrilamide gel with posterior denaturing electrophoresis, and the scanned images of the gel bands were analysed with the software GelCompar II. For Riogrande II and La Fe reservoirs we found 35 and 30 different DGGE bands, respectively, as a measurement of molecular diversity in these artificial ecosystems. Here, we demonstrated the utility of two molecular techniques for the detection of genes associated with toxicity and molecular diversity of cyanobacteria in reservoirs destined for drinking water in urban centers. We recommend strongly following with periodically molecular biology studies in these ecosystems combined with limnological and

  11. Experimental and Computational Evidence for the Reduction Mechanisms of Aromatic N-oxides by Aqueous Fe(II)-Tiron Complex.

    Science.gov (United States)

    Chen, Yiling; Dong, Hao; Zhang, Huichun

    2016-01-05

    A combined experimental-theoretical approach was taken to elucidate the reduction mechanisms of five representative aromatic N-oxides (ANOs) by Fe(II)-tiron complex and to identify the rate-limiting step. Based on the possible types of complexes formed with the reductant, three groups of ANOs were studied: type I refers to those forming 5-membered ring complexes through the N and O atoms on the side chain; type II refers to those forming 6-membered ring complexes through the N-oxide O atom and the O atom on the side chain; and type III refers to complexation through the N-oxide O atom only. Density functional theory calculations suggested that the elementary reactions, including protonation, N-O bond cleavage, and the second electron transfer processes, are barrierless, indicating that the first electron transfer is rate-limiting. Consistent with the theoretical results, the experimental solvent isotope effect, KIEH, for the reduction of quinoline N-oxide (a type III ANO) was obtained to be 1.072 ± 0.025, suggesting protonation was not involved in the rate-limiting step. The measured nitrogen kinetic isotope effect, KIEN, for the reduction of pyridine N-oxide (a type III ANO) (1.022 ± 0.006) is in good agreement with the calculated KIEN for its first electron transfer (1.011-1.028), confirming that the first electron transfer is rate-limiting. Electrochemical cell experiments demonstrated that the electron transfer process can be facilitated significantly by type I complexation with FeL2(6-) (1:2 Fe(II)-tiron complex), to some extent by type II complexation with free Fe(II), but not by weak type III complexation.

  12. Self-Assembly of Two Chiral Supramolecules with Three-Dimensional Porous Host Frameworks: (Delta){[Fe(II)(phen)(3)][Fe(III)Na(C(2)O(4))(3)]}(n)() and Its Enantiomer.

    Science.gov (United States)

    Li, Pei-zhou; Lu, Xiao-ming; Liu, Bo; Wang, Shuo; Wang, Xiao-jun

    2007-07-23

    Two chiral supramolecules with enantiomeric three-dimensional porous host frameworks, (Delta){[Fe(II)(phen)(3)][Fe(III)Na(C(2)O(4))(3)]}(n) (1) and (Lambda){[Fe(II)(phen)(3)][Fe(III)Na(C(2)O(4))(3)]}(n) (2) (phen = 1,10-phenanthroline), have been synthesized, and their crystal structures have been determined. The structural analysis shows that compounds 1 and 2 are a pair of enantiomers, both consisting of a three-dimensional porous skeleton formed by (Delta)/(Lambda){[Fe(III)Na(C(2)O(4))(3)](2-)}(n) and guest (Delta)/(Lambda)[Fe(phen)(3)](2+) units. The circular dichroism spectrum measurements confirmed the optical activity and the enantiomeric nature of complexes 1 and 2.

  13. Synthesis and magnetic properties of Co1-xZnxFe2O4 (x=0÷1) nanopowders by thermal decomposition of Co(II), Zn(II) and Fe(III) carboxylates

    Science.gov (United States)

    Stefanescu, Mircea; Bozdog, Marius; Muntean, Cornelia; Stefanescu, Oana; Vlase, Titus

    2015-11-01

    Nanoparticles of cobalt-zinc ferrite Co1-xZnxFe2O4 with x varying from 0 to 1.0 were prepared by a new method, the thermal decomposition of carboxylates of Fe(III), Co(II) and Zn(II). The obtained carboxylate precursor was characterized by thermal analysis and FT-IR spectroscopy. The precursor was annealed at 350, 600 and 1000 °C. It was found that the spinel cobalt-zinc ferrite was formed starting at 350 °C, but in mixture with simple oxides γ-Fe2O3, Co3O4 and ZnO. At 1000 °C Co1-xZnxFe2O4 was formed quantitatively as a single, well-crystallized phase. The saturation magnetization of the samples annealed at 1000 °C decreased significantly with increasing Zn2+ content from 83.93 emu/g (x=0) to 4.92 emu/g (x=1.0). At 350 and 600 °C the saturation magnetization had the same trend, even if there were contributions of other magnetic phases. Obtaining of spinel ferrite was evidenced by X-ray diffractometry and FT-IR spectrometry. Powder morphology was determined by scanning electron microscopy. Magnetic properties of the synthesized ferrites were investigated employing a conventional induction method.

  14. Schwertmannite and Fe oxides formed by biological low-pH Fe(II) oxidation versus abiotic neutralization: Impact on trace metal sequestration

    Science.gov (United States)

    Burgos, William D.; Borch, Thomas; Troyer, Lyndsay D.; Luan, Fubo; Larson, Lance N.; Brown, Juliana F.; Lambson, Janna; Shimizu, Masayuki

    2012-01-01

    Three low-pH coal mine drainage (CMD) sites in central Pennsylvania were studied to determine similarities in sediment composition, mineralogy, and morphology. Water from one site was used in discontinuous titration/neutralization experiments to produce Fe(III) minerals by abiotic oxidative hydrolysis for comparison with the field precipitates that were produced by biological low-pH Fe(II) oxidation. Even though the hydrology and concentration of dissolved metals of the CMD varied considerably between the three field sites, the mineralogy of the three iron mounds was very similar. Schwertmannite was the predominant mineral precipitated at low-pH (2.5-4.0) along with lesser amounts of goethite. Trace metals such as Zn, Ni and Co were only detected at μmol/g concentrations in the field sediments, and no metals (other than Fe) were removed from the CMD at any of the field sites. Metal cations were not lost from solution in the field because of unfavorable electrostatic attraction to the iron mound minerals. Ferrihydrite was the predominant mineral formed by abiotic neutralization (pH 4.4-8.4, 4 d aging) with lesser amounts of schwertmannite and goethite. In contrast to low-pH precipitation, substantial metal removal occurred in the neutralized CMD. Al was likely removed as hydrobasaluminite and Al(OH) 3, and as a co-precipitate into schwertmannite or ferrihydrite. Zn, Ni and Co were likely removed via adsorption onto and co-precipitation into the freshly formed Fe and Al solids. Mn was likely removed by co-precipitation and, at the highest final pH values, as a Mn oxide. Biological low-pH Fe(II) oxidation can be cost-effectively used to pre-treat CMD and remove Fe and acidity prior to conventional neutralization techniques. A further benefit is that solids formed under these conditions may be of industrial value because they do not contain trace metal or metalloid contaminants.

  15. Inhibition of trace element release during Fe(II)-activated recrystallization of Al-, Cr-, and Sn-substituted goethite and hematite.

    Science.gov (United States)

    Frierdich, Andrew J; Scherer, Michelle M; Bachman, Jonathan E; Engelhard, Mark H; Rapponotti, Brett W; Catalano, Jeffrey G

    2012-09-18

    Aqueous Fe(II) reacts with Fe(III) oxides by coupled electron transfer and atom exchange (ETAE) resulting in mineral recrystallization, contaminant reduction, and trace element cycling. Previous studies of Fe(II)-Fe(III) ETAE have explored the reactivity of either pure iron oxide phases or those containing small quantities of soluble trace elements. Naturally occurring iron oxides, however, contain substantial quantities of insoluble impurities (e.g., Al) which are known to affect the chemical properties of such minerals. Here we explore the effect of Al(III), Cr(III), and Sn(IV) substitution (1-8 mol %) on trace element release from Ni(II)-substituted goethite and Zn(II)-substituted hematite during reaction with aqueous Fe(II). Fe(II)-activated trace element release is substantially inhibited from both minerals when an insoluble element is cosubstituted into the structure, and the total amount of release decreases exponentially with increasing cosubstituent. The limited changes in surface composition that occur following reaction with Fe(II) indicate that Al, Cr, and Sn do not exsolve from the structure and that Ni and Zn released to solution originate primarily from the bulk rather than the particle exterior (upper ~3 nm). Incorporation of Al into goethite substantially decreases the amount of iron atom exchange with aqueous Fe(II) and, consequently, the amount of Ni release from the structure. This implies that trace element release inhibition caused by substituting insoluble elements results from a decrease in the amount of mineral recrystallization. These results suggest that naturally occurring iron oxides containing insoluble elements are less susceptible to Fe(II)-activated recrystallization and exhibit a greater retention of trace elements and contaminants than pure mineral phases.

  16. Inhibition of trace element release during Fe(II)-activated recrystallization of Al-, Cr-, and Sn-substituted goethite and hematite

    Energy Technology Data Exchange (ETDEWEB)

    Frierdich, Andrew J.; Scherer, M.; Bachman, Jonathan E.; Engelhard, Mark H.; Rapponotti, Brett W.; Catalano, Jeffrey G.

    2012-09-18

    Aqueous Fe(II) reacts with Fe(III) oxides by coupled electron transfer and atom exchange (ETAE) resulting in mineral recrystallization, contaminant reduction, and trace element cycling. Previous studies of Fe(II)-Fe(III) ETAE have explored the reactivity of either pure iron oxide phases or those containing small quantities of soluble trace elements. Naturally occurring iron oxides, however, contain substantial quantities of insoluble impurities (e.g., Al) which are known to affect the chemical properties of such minerals. Here we explore the effect of Al(III), Cr(III), and Sn(IV) substitution on trace element release from Ni(II)-substituted goethite and Zn(II)-substituted hematite during reaction with aqueous Fe(II). Fe(II)-activated trace element release is substantially inhibited from both minerals when an insoluble element is co-substituted into the structure, and the total amount of release decreases exponentially with increasing co substituent. The limited changes in surface composition that occur following reaction with Fe(II) indicate that Al, Cr, and Sn do not exsolve from the structure and that Ni and Zn released to solution originate primarily from the bulk rather than the particle exterior (upper ~3 nm). Incorporation of Al into goethite substantially decreases the amount of iron atom exchange with aqueous Fe(II) and, consequently, the amount of Ni release from the structure. This implies that trace element release inhibition caused by substituting insoluble elements results from a decrease in the amount of mineral recrystallization. These results suggest that naturally occurring iron oxides containing insoluble elements are less susceptible to Fe(II)-activated recrystallization and exhibit a greater retention of trace elements and contaminants than pure mineral phases.

  17. A new combined process for efficient removal of Cu(II) organic complexes from wastewater: Fe(III) displacement/UV degradation/alkaline precipitation.

    Science.gov (United States)

    Xu, Zhe; Gao, Guandao; Pan, Bingcai; Zhang, Weiming; Lv, Lu

    2015-12-15

    Efficient removal of heavy metals complexed with organic ligands from water is still an important but challenging task now. Herein, a novel combined process, i.e., Fe(III)-displacement/UV degradation/alkaline precipitation (abbreviated as Fe(III)/UV/OH) was developed to remove copper-organic complexes from synthetic solution and real electroplating effluent, and other processes including alkaline precipitation, Fe(III)/OH, UV/OH were employed for comparison. By using the Fe(III)/UV/OH process, some typical Cu(II) complexes, such as Cu(II)-ethylenediaminetetraacetic acid (EDTA), Cu(II)-nitrilotriacetic acid (NTA), Cu(II)-citrate, Cu(II)-tartrate, and Cu(II)-sorbate, each at 19.2 mg Cu/L initially, were efficiently removed from synthetic solution with the residual Cu below 1 mg/L. Simultaneously, 30-48% of total organic carbon was eliminated with exception of Cu(II)-sorbate. Comparatively, the efficiency of other processes was much lower than the Fe(III)/UV/OH process. With Cu(II)-citrate as the model complex, the optimal conditions for the combined process were obtained as: initial pH for Fe(III) displacement, 1.8-5.4; molar ratio of [Fe]/[Cu], 4:1; UV irradiation, 10 min; precipitation pH, 6.6-13. The mechanism responsible for the process involved the liberation of Cu(II) ions from organic complexes as a result of Fe(III) displacement, decarboxylation of Fe(III)-ligand complexes subjected to UV irradiation, and final coprecipitation of Cu(II) and Fe(II)/Fe(III) ions. Up to 338.1 mg/L of Cu(II) in the electroplating effluent could be efficiently removed by the process with the residual Cu(II) below 1 mg/L and the removal efficiency of ∼99.8%, whereas direct precipitation by using NaOH could only result in total Cu(II) removal of ∼8.6%. In addition, sunlight could take the place of UV to achieve similar removal efficiency with longer irradiation time (90 min).

  18. Six-coordinate high-spin iron(ii) complexes with bidentate PN ligands based on 2-aminopyridine - new Fe(ii) spin crossover systems.

    Science.gov (United States)

    Holzhacker, Christian; Calhorda, Maria José; Gil, Adrià; Carvalho, Maria Deus; Ferreira, Liliana P; Stöger, Berthold; Mereiter, Kurt; Weil, Matthias; Müller, Danny; Weinberger, Peter; Pittenauer, Ernst; Allmaier, Günter; Kirchner, Karl

    2014-08-01

    Several new octahedral iron(ii) complexes of the type [Fe(PN(R)-Ph)2X2] (X = Cl, Br; R = H, Me) containing bidentate PN(R)-Ph (R = H, Me) (1a,b) ligands based on 2-aminopyridine were prepared. (57)Fe Mössbauer spectroscopy and magnetization studies confirmed in all cases their high spin nature at room temperature with magnetic moments very close to 4.9μB reflecting the expected four unpaired d-electrons in all these compounds. While in the case of the PN(H)-Ph ligand an S = 2 to S = 0 spin crossover was observed at low temperatures, complexes with the N-methylated analog PN(Me)-Ph retain an S = 2 spin state also at low temperatures. Thus, [Fe(PN(H)-Ph)2X2] (2a,3a) and [Fe(PN(Me)-Ph)2X2] (2b,3b) adopt different geometries. In the first case a cis-Cl,P,N-arrangement seems to be most likely, as supported by various experimental data derived from (57)Fe Mössbauer spectroscopy, SQUID magnetometry, UV/Vis, Raman, and ESI-MS as well as DFT and TDDFT calculations, while in the case of the PN(Me)-Ph ligand a trans-Cl,P,N-configuration is adopted. The latter is also confirmed by X-ray crystallography. In contrast to [Fe(PN(Me)-Ph)2X2] (2b,3b), [Fe(PN(H)-Ph)2X2] (2a,3a) is labile and undergoes rearrangement reactions. In CH3OH, the diamagnetic dicationic complex [Fe(PN(H)-Ph)3](2+) (5) is formed via the intermediacy of cis-P,N-[Fe(κ(2)-P,N-PN(H)-Ph)2(κ(1)-P-PN(H)-Ph)(X)](+) (4a,b) where one PN ligand is coordinated in a κ(1)-P-fashion. In CH3CN the diamagnetic dicationic complex cis-N,P,N-[Fe(PN(H)-Ph)2(CH3CN)2](2+) (6) is formed as a major isomer where the two halide ligands are replaced by CH3CN.

  19. Potential function of added minerals as nucleation sites and effect of humic substances on mineral formation by the nitrate-reducing Fe(II)-oxidizer Acidovorax sp. BoFeN1.

    Science.gov (United States)

    Dippon, Urs; Pantke, Claudia; Porsch, Katharina; Larese-Casanova, Phil; Kappler, Andreas

    2012-06-19

    The mobility of toxic metals and the transformation of organic pollutants in the environment are influenced and in many cases even controlled by iron minerals. Therefore knowing the factors influencing iron mineral formation and transformation by Fe(II)-oxidizing and Fe(III)-reducing bacteria is crucial for understanding the fate of contaminants and for the development of remediation technologies. In this study we followed mineral formation by the nitrate-reducing Fe(II)-oxidizing strain Acidovorax sp. BoFeN1 in the presence of the crystalline Fe(III) (oxyhydr)oxides goethite, magnetite and hematite added as potential nucleation sites. Mössbauer spectroscopy analysis of minerals precipitated by BoFeN1 in (57)Fe(II)-spiked microbial growth medium showed that goethite was formed in the absence of mineral additions as well as in the presence of goethite or hematite. The presence of magnetite minerals during Fe(II) oxidation induced the formation of magnetite in addition to goethite, while the addition of humic substances along with magnetite also led to goethite but no magnetite. This study showed that mineral formation not only depends on the aqueous geochemical conditions but can also be affected by the presence of mineral nucleation sites that initiate precipitation of the same underlying mineral phases.

  20. U(VI) Uptake and Reduction by Fe(II)-Bearing Secondary Mineralization Products of the Bioreduction of Fe(III) Oxides by Dissimilatory Fe(III)-Reducing Bacteria

    Science.gov (United States)

    O'Loughlin, E. J.; Kelly, S. D.; Kemner, K. M.

    2008-12-01

    Biogenic Fe(II) phases (magnetite, green rust, siderite, vivianite, etc.) provide a reservoir of reducing capacity in the subsurface that may contribute to the reduction of contaminants such as U(VI). In this study we examined the potential for the uptake and reduction of U(VI) in the presence of biogenic green rust, (BioGR) biogenic magnetite (BioMAG), and biogenic siderite (BioSID) resulting from the reduction of Fe(III) oxides by Shewanella putrefaciens CN32. Suspensions of biogenic Fe(II) phases were pasteurized (70 °C for 1 h) to eliminate the potential for microbial reduction of U(VI) and washed repeatedly to remove any soluble reductants. The suspensions were then spiked with uranyl chloride solution. Within 48 h, the total solution-phase U(VI) concentrations decreased from 500 μM to 1.5 μM in the U-BioGR system, to 392 μM in the U-BioMAG system, and to 472 μM in the U-BioSID system, as determined by ICP- OES. Analysis of the samples by U LIII extended X-ray absorption fine structure spectroscopy (EXAFS) indicated that despite a stoichiometric excess of Fe(II), no more than 6% of U(VI) was reduced in the U- BioSID system, and no more than 22% of U(VI) was reduced in the U-BioMAG system. For comparison, in the U-BioGR system, no less than 80% of U(VI) was reduced to U(IV). Uptake of U(VI) by BioGR and BioMAG was accompanied by the formation of nanoparticulate uraninite. The U EXAFS data from the U-BioSID system was consistent with partial U(VI)/U(IV) substitution for Fe(II) in the surface layer of siderite particles and adsorption of U(IV). Our results clearly demonstrate that there are significant differences in reactivity among biogenic Fe(II) phases with respect to the uptake and reduction of U(VI).

  1. Intervalence charge transfer transition in mixed valence complexes synthesised from RuIII(edta)- and FeII(CN)5-cores

    Indian Academy of Sciences (India)

    H C Bajaj; Atindra D Shukla; Amitava Das

    2002-08-01

    Intervalence charge transfer properties were studied for a set of mixed valence complexes incorporating Ru(III) and Fe(II)-centres linked by various saturated and unsaturated bridging ligands (BL). Studies reveal that degree of ground state electronic interaction and coupling between Ru(III) and Fe(II)-centres can be attenuated by changing the nature of the bridging ligand. Further, inclusion of the bridging ligand with interrupted -electron system in a -CD cavity initiate an optical electron transfer from Fe(II) to Ru(III) which is otherwise not observed.

  2. How to overcome inter-electrode variability and instability to quantify dissolved oxygen, Fe(II, mn(II, and S(−II in undisturbed soils and sediments using voltammetry

    Directory of Open Access Journals (Sweden)

    Slowey Aaron J

    2012-06-01

    Full Text Available Abstract Background Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indirectly calibrated electrodes has been developed, but the protocol for and accuracy of this approach—the pilot ion method—has not been documented in detail. Results A detailed procedure for testing electrode quality is provided, and the application and limitations of the pilot ion method have been documented. To quantify Fe(II and Mn(II, subtraction of non-linear baseline functions from voltammetric signals produced better calibration curves than did linear baselines, enabled lower detection limits and reliable deconvolution of overlapping signals, and was successfully applied to sediment pore water signals. We observed that electrode sensitivities often vary by tens of percent, and that the sensitivity declines over time. The ratio of calibration slopes of Mn(II to Fe(II varied by no more than 11% from one Hg/Au electrode to another and Fe(II concentrations predicted by the Mn(II pilot ion were, on average, 13% different from their actual values. However, concentration predictions by the pilot ion method were worse for less than 15 μM Fe(II (46% different on average. The ratio of calibration slopes of Mn(II to S(−II varied by almost 20% from one Hg/Au electrode to another, and S(−II predicted concentrations were as much as 58% different from their actual values. These predictions of Fe(II and S(−II concentrations indicate that the accuracy of the pilot ion method depends on how independent calibration slope ratios are from the electrode used. At

  3. The pectic polysaccharide rhamnogalacturonan II is present as a dimer in pectic populations of bilberries and black currants in muro and in juice

    NARCIS (Netherlands)

    Hilz, H.; Williams, P.; Doco, T.; Schols, H.A.; Voragen, A.G.J.

    2006-01-01

    Rhamnogalacturonan II (RG II) can play an important role during processing of berries due to its enzyme resistance and its possible role as a pectic cross-linker. This article describes the presence of RG II in cell walls, in juice and in press cake of bilberries and black currants. RG II was

  4. Spectroscopic and magnetic studies of wild-type and mutant forms of the Fe(II)- and 2-oxoglutarate-dependent decarboxylase ALKBH4.

    Science.gov (United States)

    Bjørnstad, Linn G; Zoppellaro, Giorgio; Tomter, Ane B; Falnes, Pål Ø; Andersson, K Kristoffer

    2011-03-15

    The Fe(II)/2OG (2-oxoglutarate)-dependent dioxygenase superfamily comprises proteins that couple substrate oxidation to decarboxylation of 2OG to succinate. A member of this class of mononuclear non-haem Fe proteins is the Escherichia coli DNA/RNA repair enzyme AlkB. In the present work, we describe the magnetic and optical properties of the yet uncharacterized human ALKBH4 (AlkB homologue). Through EPR and UV-visible spectroscopy studies, we address the Fe-binding environment of the proposed catalytic centre of wild-type ALKBH4 and an Fe(II)-binding mutant. We could observe a novel unusual Fe(III) high-spin EPR-active species in the presence of sulfide with a g(max) of 8.2. The Fe(II) site was probed with NO. An intact histidine-carboxylate site is necessary for productive Fe binding. We also report the presence of a unique cysteine-rich motif conserved in the N-terminus of ALKBH4 orthologues, and investigate its possible Fe-binding ability. Furthermore, we show that recombinant ALKBH4 mediates decarboxylation of 2OG in absence of primary substrate. This activity is dependent on Fe as well as on residues predicted to be involved in Fe(II) co-ordination. The present results demonstrate that ALKBH4 represents an active Fe(II)/2OG-dependent decarboxylase and suggest that the cysteine cluster is involved in processes other than Fe co-ordination.

  5. Direct Detection of Fe(II) in Extracellular Polymeric Substances (EPS) at the Mineral-Microbe Interface in Bacterial Pyrite Leaching.

    Science.gov (United States)

    Mitsunobu, Satoshi; Zhu, Ming; Takeichi, Yasuo; Ohigashi, Takuji; Suga, Hiroki; Jinno, Muneaki; Makita, Hiroko; Sakata, Masahiro; Ono, Kanta; Mase, Kazuhiko; Takahashi, Yoshio

    2016-01-01

    We herein investigated the mechanisms underlying the contact leaching process in pyrite bioleaching by Acidithiobacillus ferrooxidans using scanning transmission X-ray microscopy (STXM)-based C and Fe near edge X-ray absorption fine structure (NEXAFS) analyses. The C NEXAFS analysis directly showed that attached A. ferrooxidans produces polysaccharide-abundant extracellular polymeric substances (EPS) at the cell-pyrite interface. Furthermore, by combining the C and Fe NEXAFS results, we detected significant amounts of Fe(II), in addition to Fe(III), in the interfacial EPS at the cell-pyrite interface. A probable explanation for the Fe(II) in detected EPS is the leaching of Fe(II) from the pyrite. The detection of Fe(II) also indicates that Fe(III) resulting from pyrite oxidation may effectively function as an oxidizing agent for pyrite at the cell-pyrite interface. Thus, our results imply that a key role of Fe(III) in EPS, in addition to its previously described role in the electrostatic attachment of the cell to pyrite, is enhancing pyrite dissolution.

  6. Direct Detection of Fe(II) in Extracellular Polymeric Substances (EPS) at the Mineral-Microbe Interface in Bacterial Pyrite Leaching

    Science.gov (United States)

    Mitsunobu, Satoshi; Zhu, Ming; Takeichi, Yasuo; Ohigashi, Takuji; Suga, Hiroki; Jinno, Muneaki; Makita, Hiroko; Sakata, Masahiro; Ono, Kanta; Mase, Kazuhiko; Takahashi, Yoshio

    2016-01-01

    We herein investigated the mechanisms underlying the contact leaching process in pyrite bioleaching by Acidithiobacillus ferrooxidans using scanning transmission X-ray microscopy (STXM)-based C and Fe near edge X-ray absorption fine structure (NEXAFS) analyses. The C NEXAFS analysis directly showed that attached A. ferrooxidans produces polysaccharide-abundant extracellular polymeric substances (EPS) at the cell-pyrite interface. Furthermore, by combining the C and Fe NEXAFS results, we detected significant amounts of Fe(II), in addition to Fe(III), in the interfacial EPS at the cell-pyrite interface. A probable explanation for the Fe(II) in detected EPS is the leaching of Fe(II) from the pyrite. The detection of Fe(II) also indicates that Fe(III) resulting from pyrite oxidation may effectively function as an oxidizing agent for pyrite at the cell-pyrite interface. Thus, our results imply that a key role of Fe(III) in EPS, in addition to its previously described role in the electrostatic attachment of the cell to pyrite, is enhancing pyrite dissolution. PMID:26947441

  7. Final Report: Molecular mechanisms and kinetics of microbial anaerobic nitrate-dependent U(IV) and Fe(II) oxidation

    Energy Technology Data Exchange (ETDEWEB)

    O' Day, Peggy A. [Univ. of California, Merced, CA (United States); Asta, Maria P. [Univ. of California, Merced, CA (United States); Kanematsu, Masakazu [Univ. of California, Merced, CA (United States); Beller, Harry [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zhou, Peng [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Steefel, Carl [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2015-02-27

    In this project, we combined molecular genetic, spectroscopic, and microscopic techniques with kinetic and reactive transport studies to describe and quantify biotic and abiotic mechanisms underlying anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation, which influences the long-term efficacy of in situ reductive immobilization of uranium at DOE sites. In these studies, Thiobacillus denitrificans, an autotrophic bacterium that catalyzes anaerobic U(IV) and Fe(II) oxidation, was used to examine coupled oxidation-reduction processes under either biotic (enzymatic) or abiotic conditions in batch and column experiments with biogenically produced UIVO2(s). Synthesis and quantitative analysis of coupled chemical and transport processes were done with the reactive transport modeling code Crunchflow. Research focused on identifying the primary redox proteins that catalyze metal oxidation, environmental factors that influence protein expression, and molecular-scale geochemical factors that control the rates of biotic and abiotic oxidation.

  8. Two-step spin-switchable tetranuclear Fe(II) molecular solid: Ab initio theory and predictions

    Science.gov (United States)

    Maldonado, Pablo; Kanungo, Sudipta; Saha-Dasgupta, Tanusri; Oppeneer, Peter M.

    2013-07-01

    Using density functional theory supplemented with on-site Coulomb U interaction in combination with ab initio molecular dynamics simulations, we investigate the spin-crossover (SCO) properties of a Fe(II) based cyanide-bridged square molecular system, [FeII4(μ-CN)4(bpy)4(tpa)2](PF6)4 (where bpy = 2,2'-bipyridine and tpa = tris(2-pyridylmethyl)amine], exhibiting a two-step SCO transition. The ab initio calculated SCO temperatures are found to show remarkably good agreement with experimentally measured spin conversion temperatures [M. Nihei , Angew. Chem., Int. Ed.1433-785110.1002/anie.200502216 44, 6484 (2005)]. Our theoretical study predicts further chemo switching of the spin state by introduction of guest molecules such as CO2, CS2, and H2O into the porous topology of the system, which would add another dimensionality to this interesting material.

  9. Discoloration and mineralization of Orange II by using a bentonite clay-based Fe nanocomposite film as a heterogeneous photo-Fenton catalyst.

    Science.gov (United States)

    Feng, Jiyun; Hu, Xijun; Yue, Po Lock

    2005-01-01

    Discoloration and mineralization of an azo dye Orange II was conducted by using a bentonite clay-based Fe nanocomposite (Fe-B) film as a heterogeneous photo-Fenton catalyst in the presence of UVC light and H(2)O(2). Under optimal conditions (pH=3.0, 10 mM H(2)O(2), and 1 x 8W UVC), 100% discoloration and 50-60% TOC removal of 0.2 mM Orange II can be achieved in 90 and 120 min, respectively. The mineralization kinetics of 0.2 mM Orange II is much slower than the corresponding discoloration kinetics. Under the same conditions, the Fe leaching from the Fe-B-coated catalyst film is very low. The Fe-B-coated catalyst film could be used in the pre-treatment of wastewater for an integrated system consisting of a photochemical reactor and a biological reactor. Multi-run experimental results reveal that the Fe-B-coated catalyst film could have a long-term stability for the discoloration and mineralization of Orange II. A comparison between the performance of the Fe-B-coated catalyst film and a suspended Fe-B catalyst in the discoloration and mineralization of Orange II was also discussed.

  10. Nitrite to nitric oxide interconversion by heme FeII complex assisted by [CuI(tmpa)]+

    KAUST Repository

    Turias, Francesc

    2015-09-09

    The present computational study complements the recent experimental efforts by Karlin and coworkers to describe the interconversion of nitrite to nitric oxide by means of an iron porphyrin complex together with a Cu chemical system, i.e., the iron(II) complex (F8TPP)FeII [F8TPP = tetrakis(2,6-difluorophenyl)porphyrinate(2−)] and a preformed copper(II)–nitrito complex [(tmpa)CuII(NO2)][B(C6F5)4] [tmpa = tris(2-pyridylmethyl)amine], being the latter an oxidized species of [(tmpa)CuI(MeCN)]+. By DFT calculations, we unravel how the reduction of nitrite to nitric oxide takes place through a μ-oxo heme-FeIII–O–CuII complex, following a mimetic path as in the cytochrome c oxidase. Mayer bond order (MBO) and energy decomposition analyses are used to analyze the bonding strength of such nitro derivatives to either copper or iron. © 2015 Springer Science+Business Media New York

  11. Synthesis, spectroscopic, thermal and anticancer studies of metal-antibiotic chelations: Ca(II), Fe(III), Pd(II) and Au(III) chloramphenicol complexes

    Science.gov (United States)

    Al-Khodir, Fatima A. I.; Refat, Moamen S.

    2016-09-01

    Four Ca(II), Fe(III), Pd(II) and Au(III) complexes of chloramphenicol drug have been synthesized and well characterized using elemental analyses, (infrared, electronic, and 1H-NMR) spectra, magnetic susceptibility measurement, and thermal analyses. Infrared spectral data show that the chloramphenicol drug coordinated to Ca(II), Pd(II) and Au(III) metal ions through two hydroxyl groups with 1:1 or 1:2 M ratios, but Fe(III) ions chelated towards chloramphenicol drug via the oxygen and nitrogen atoms of amide group with 1:2 ratio based on presence of keto↔enol form. The X-ray powder diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) techniques were used to identify the nano-size particles of both iron(III) and gold(III) chloramphenicol complexes. The antimicrobial assessments of the chloramphenicol complexes were scanned and collected the results against of some kind of bacteria and fungi. The cytotoxic activity of the gold(III) complex was tested against the human colon carcinoma (HCT-116) and human hepatocellular carcinoma (HepG-2) tumor cell lines.

  12. Reactions of H2O3 in the pulse-irradiated Fe(II)-O2 system

    DEFF Research Database (Denmark)

    Sehested, Knud; Bjergbakke, Erling; Lang Rasmussen, O.;

    1969-01-01

    G(Fe(III)] is measured in pulse-irradiated O2-saturated solutions of 20 to 160 μMFe(II), at the p H's 0.46, 1.51, and 2.74 H2SO4 and HClO4 and with dose rates between 1 and 8 krad/1 μsec pulse. Based on homogeneous kinetics, the results are interpreted by a system of 18 reactions. The formation...

  13. Comparative adsorption of Fe(III) and Cd(II) ions on glutaraldehyde crosslinked chitosan–coated cristobalite

    OpenAIRE

    Rahmi; Fathurrahmi; Irwansyah; Arie Purnaratrie

    2015-01-01

    In this study, chitosan was crosslinked with glutaraldehyde and coated on the surface of cristobalite through a dip and phase inversion process. The adsorbent was used in batch experiments to evaluate the adsorption of Fe(III) and Cd(II) ions. A maximum adsorption capacity was observed at a glutaraldehyde concentration in sorbent preparation of 1% (w/w). The equilibrium adsorption quantity was determined to be a function of the solution pH, initial concentration and agitation period. Langmuir...

  14. Structural fold, conservation and Fe(II) binding of the intracellular domain of prokaryote FeoB

    Energy Technology Data Exchange (ETDEWEB)

    Hung, Kuo-Wei; Chang, Yi-Wei; Eng, Edward T.; Chen, Jai-Hui; Chen, Yi-Chung; Sun, Yuh-Ju; Hsiao, Chwan-Deng; Dong, Gang; Spasov, Krasimir A.; Unger, Vinzenz M.; Huang, Tai-huang (Yale-MED); (Perutz Lab); (AS); (NTHU-Taiwan)

    2010-09-17

    FeoB is a G-protein coupled membrane protein essential for Fe(II) uptake in prokaryotes. Here, we report the crystal structures of the intracellular domain of FeoB (NFeoB) from Klebsiella pneumoniae (KpNFeoB) and Pyrococcus furiosus (PfNFeoB) with and without bound ligands. In the structures, a canonical G-protein domain (G domain) is followed by a helical bundle domain (S-domain), which despite its lack of sequence similarity between species is structurally conserved. In the nucleotide-free state, the G-domain's two switch regions point away from the binding site. This gives rise to an open binding pocket whose shallowness is likely to be responsible for the low nucleotide-binding affinity. Nucleotide binding induced significant conformational changes in the G5 motif which in the case of GMPPNP binding was accompanied by destabilization of the switch I region. In addition to the structural data, we demonstrate that Fe(II)-induced foot printing cleaves the protein close to a putative Fe(II)-binding site at the tip of switch I, and we identify functionally important regions within the S-domain. Moreover, we show that NFeoB exists as a monomer in solution, and that its two constituent domains can undergo large conformational changes. The data show that the S-domain plays important roles in FeoB function.

  15. Importance of out-of-state spin-orbit coupling for slow magnetic relaxation in mononuclear Fe(II) complexes.

    Science.gov (United States)

    Lin, Po-Heng; Smythe, Nathan C; Gorelsky, Serge I; Maguire, Steven; Henson, Neil J; Korobkov, Ilia; Scott, Brian L; Gordon, John C; Baker, R Tom; Murugesu, Muralee

    2011-10-12

    Two mononuclear high-spin Fe(II) complexes with trigonal planar ([Fe(II)(N(TMS)(2))(2)(PCy(3))] (1) and distorted tetrahedral ([Fe(II)(N(TMS)(2))(2)(depe)] (2) geometries are reported (TMS = SiMe(3), Cy = cyclohexyl, depe = 1,2-bis(diethylphosphino)ethane). The magnetic properties of 1 and 2 reveal the profound effect of out-of-state spin-orbit coupling (SOC) on slow magnetic relaxation. Complex 1 exhibits slow relaxation of the magnetization under an applied optimal dc field of 600 Oe due to the presence of low-lying electronic excited states that mix with the ground electronic state. This mixing re-introduces orbital angular momentum into the electronic ground state via SOC, and 1 thus behaves as a field-induced single-molecule magnet. In complex 2, the lowest-energy excited states have higher energy due to the ligand field of the distorted tetrahedral geometry. This higher energy gap minimizes out-of-state SOC mixing and zero-field splitting, thus precluding slow relaxation of the magnetization for 2.

  16. Synthesis, characterization and performance in arsenic removal of iron-doped activated carbons prepared by impregnation with Fe(III) and Fe(II).

    Science.gov (United States)

    Muñiz, G; Fierro, V; Celzard, A; Furdin, G; Gonzalez-Sánchez, G; Ballinas, M L

    2009-06-15

    Arsenic removal from natural well water from the state of Chihuahua (Mexico) is investigated by adsorption using a commercial activated carbon (AC). The latter is used as such, or after oxidation by several chemicals in aqueous solution: nitric acid, hydrogen peroxide, and ammonium persulphate. Raw and oxidised activated carbons are fully characterised (elementary analysis, surface chemistry, pore texture parameters, pH(ZC), and TEM observation). Adsorption of As is measured in the aforementioned water, containing ca. 300 ppb of arsenic: removal of As is poor with the raw AC, and only the most oxidised carbons exhibit higher performances. By contrast, iron-doped ACs are much more efficient for that purpose, though their As uptake strongly depends on their preparation conditions: a number of samples were synthesised by impregnation of raw and oxidised ACs with HCl aqueous solutions of either FeCl(3) or FeCl(2) at various concentrations and various pH. It is shown that iron(II) chloride is better for obtaining high iron contents in the resultant ACs (up to 8.34 wt.%), leading to high As uptake, close to 0.036 mg As/g C. In these conditions, 100% of the As initially present in the natural well water is removed, as soon as the Fe content of the adsorbent is higher than 2 wt.%.

  17. Synthesis, characterization and performance in arsenic removal of iron-doped activated carbons prepared by impregnation with Fe(III) and Fe(II)

    Energy Technology Data Exchange (ETDEWEB)

    Muniz, G. [Laboratoire de Chimie du Solide Mineral, Nancy-Universite, UMR CNRS 7555, BP 239, 54506 Vandoeuvre-les Nancy (France); Facultad de Ciencias Quimicas, Universidad Autonoma de Chihuahua, Circuito Universitario S/N, Chihuahua (Mexico); Fierro, V., E-mail: Vanessa.Fierro@lcsm-uhp.nancy.fr [Laboratoire de Chimie du Solide Mineral, Nancy-Universite, UMR CNRS 7555, BP 239, 54506 Vandoeuvre-les Nancy (France); Celzard, A. [Laboratoire de Chimie du Solide Mineral, UMR CNRS 7555, Nancy-Universite, ENSTIB, 27 rue du Merle Blanc, BP 1041, 88051 Epinal Cedex 9 (France); Furdin, G. [Laboratoire de Chimie du Solide Mineral, Nancy-Universite, UMR CNRS 7555, BP 239, 54506 Vandoeuvre-les Nancy (France); Gonzalez-Sanchez, G. [Centro de Investigacion en Materiales Avanzados (CIMAV) Miguel de Cervantes 120, Compl. Ind. Chih., 31109 Chihuahua (Mexico); Ballinas, M.L. [Facultad de Ciencias Quimicas, Universidad Autonoma de Chihuahua, Circuito Universitario S/N, Chihuahua (Mexico)

    2009-06-15

    Arsenic removal from natural well water from the state of Chihuahua (Mexico) is investigated by adsorption using a commercial activated carbon (AC). The latter is used as such, or after oxidation by several chemicals in aqueous solution: nitric acid, hydrogen peroxide, and ammonium persulphate. Raw and oxidised activated carbons are fully characterised (elementary analysis, surface chemistry, pore texture parameters, pH{sub ZC}, and TEM observation). Adsorption of As is measured in the aforementioned water, containing ca. 300 ppb of arsenic: removal of As is poor with the raw AC, and only the most oxidised carbons exhibit higher performances. By contrast, iron-doped ACs are much more efficient for that purpose, though their As uptake strongly depends on their preparation conditions: a number of samples were synthesised by impregnation of raw and oxidised ACs with HCl aqueous solutions of either FeCl{sub 3} or FeCl{sub 2} at various concentrations and various pH. It is shown that iron(II) chloride is better for obtaining high iron contents in the resultant ACs (up to 8.34 wt.%), leading to high As uptake, close to 0.036 mg As/g C. In these conditions, 100% of the As initially present in the natural well water is removed, as soon as the Fe content of the adsorbent is higher than 2 wt.%.

  18. One- and two-step spin-crossover behavior of [Fe(II)(isoxazole)(6)](2+) and the structure and magnetic properties of triangular [Fe(III)(3)O(OAc)(6)(isoxazole)(3)][ClO(4)].

    Science.gov (United States)

    Hibbs, Wendy; van Koningsbruggen, Petra J; Arif, Atta M; Shum, William W; Miller, Joel S

    2003-09-08

    The structure and spin-crossover magnetic behavior of [Fe(II)1(6)][BF(4)](2) (1 = isoxazole) and [Fe(II)1(6)][ClO(4)](2) have been studied. [Fe(II)1(6)][BF(4)](2) undergoes two reversible spin-crossover transitions at 91 and 192 K, and is the first two-step spin transition to undergo a simultaneous crystallographic phase transition, but does not exhibit thermal hysteresis. The single-crystal structure determinations at 260 [space group P3, a = 17.4387(4) A, c = 7.6847(2) A] and at 130 K [space group P1, a = 17.0901(2) A, b = 16.7481(2) A, c = 7.5413(1) A, alpha = 90.5309(6) degrees, beta = 91.5231(6) degrees, gamma = 117.8195(8) degrees ] reveal two different iron sites, Fe1 and Fe2, in a 1:2 ratio. The room-temperature magnetic moment of 5.0 mu(B) is consistent with high-spin Fe(II). A plateau in mu(T) having a moment of 3.3 mu(B) centered at 130 K suggests a mixed spin system of some high-spin and some low-spin Fe(II) molecules. On the basis of the Fe-N bond distances at the two temperatures, and the molar fraction of high-spin molecules at the transition plateau, Fe1 and Fe2 can be assigned to the 91 and 192 K transitions, respectively. [Fe(II)1(6)][ClO(4)](2) [space group P3, a = 17.5829(3) A, c = 7.8043(2) A, beta = 109.820 (3) degrees, T = 295 K] also possesses Fe1:Fe2 in a 1:2 ratio, and magnetic measurements show a single spin transition at 213 K, indicating that both Fe1 and Fe2 undergo a simultaneous spin transition. [Fe(II)1(6)][ClO(4)](2) slowly decomposes in solutions containing acetic anhydride to form [Fe(III)(3)O(OAc)(6)1(3)][ClO(4)] [space group I2, a = 10.1547(7) A, b = 16.5497(11) A, c = 10.3205(9) A, beta = 109.820 (3) degrees, T = 200 K]. The isosceles Fe(3) unit contains two Fe.Fe distances of 3.2844(1) A and a third Fe.Fe distance of 3.2857(1) A. The magnetic data can be fit to a trinuclear model with H = -2J(S(1)xS(2) + S(2)xS(3)) - 2J(13)(S(1)xS(3)), where J = -27.1 and J(13) = -32.5 cm(-1).

  19. Liquid crystal dimers

    CERN Document Server

    Kumar Pal, Santanu

    2017-01-01

    This book covers in-depth discussion of design principles, synthesis and thermal behavior of all types of liquid crystal (LC) dimers. The text presents recent advances in the field of LC dimers consisting of different mesogenic units such as calamitic, discotic and bent-core molecules. It starts with a chapter on the introduction of liquid crystal dimers, including their odd-even behavior, basic classification of dimers and common mesophases in dimers. The text shows how the molecular architectures are being used to develop new materials to study a range of interesting phenomena such as the biaxial nematic phase containing rod-like and disc-like mesogenic units. Finally, the text presents perspectives related to technological relevance of these dimers such as dopants in LC display mixtures exhibiting faster relaxation time, strong flexoelectric coupling and others to effect control over the properties of these materials.

  20. SOFIA-EXES Mid-IR Observations of [Fe II] Emission from the Extended Atmosphere of Betelgeuse

    Science.gov (United States)

    Harper, G. M.; DeWitt, C.; Richter, M. J.; Greathouse, T. K.; Ryde, N.; Guinan, E. F.; O’Gorman, E.; Vacca, W. D.

    2017-02-01

    We present a NASA-DLR SOFIA-Echelon Cross Echelle Spectrograph (EXES) and NASA Infrared Telescope Facility-Texas Echelon Cross Echelle Spectrograph (TEXES) mid-IR R≃ {{50,000}} spectral study of forbidden Fe ii transitions in the early-type M supergiants, Betelgeuse (α Ori: M2 Iab) and Antares (α Sco: M1 Iab + B3 V). With EXES, we spectrally resolve the ground term [Fe ii] 25.99 μm (a{}6{D}J=7/2{--9/2}: {E}{up}=540 K) emission from Betelgeuse. We find a small centroid blueshift of 1.9 ± 0.4 {km} {{{s}}}-1 that is a significant fraction (20%) of the current epoch wind speed, with a FWHM of 14.3 ± 0.1 {km} {{{s}}}-1. The TEXES observations of [Fe ii] 17.94 μm (a{}4{F}J=7/2-9/2: {E}{up}={{3400}} K) show a broader FWHM of 19.1 ± 0.2 {km} {{{s}}}-1, consistent with previous observations, and a small redshift of 1.6 ± 0.6 {km} {{{s}}}-1 with respect to the adopted stellar center-of-mass velocity of {V}{CoM}=20.9+/- 0.3 {km} {{{s}}}-1. To produce [Fe ii] 25.99 μm blueshifts of 20% wind speed requires that the emission arises closer to the star than existing thermal models for α Ori’s circumstellar envelope predict. This implies a more rapid wind cooling to below 500 K within 10{R}* ({θ }* =44 mas, dist = 200 pc) of the star, where the wind has also reached a significant fraction of the maximum wind speed. The line width is consistent with the turbulence in the outflow being close to the hydrogen sound speed. EXES observations of [Fe ii] 22.90 μm (a{}4{D}J=5/2{--7/2}: {E}{up}={{11,700}} K) reveal no emission from either star. These findings confirm the dominance of cool plasma in the mixed region where hot chromospheric plasma emits copiously in the UV, and they also constrain the wind heating produced by the poorly understood mechanisms that drive stellar outflows from these low variability and weak-dust signature stars.

  1. A [4Fe−4S] cluster dimer bridged by Bis(2,2′:6′,2″-terpyridine-4′-thiolato)iron(II)

    NARCIS (Netherlands)

    van der Geer, E.P.L.; van Koten, G.; Klein Gebbink, R.J.M.; Hessen, B.

    2008-01-01

    The use of 2,2′:6′,2″-terpyridine-4′-thiol (tpySH) was explored as a bridging ligand for the formation of stable assemblies containing both [4Fe−4S] clusters and single metal ions. Reaction of tpySH (2 equiv) with (NH4)2Fe(SO4)2·6H2O generated the homoleptic complex [Fe(tpySH)2]2+, which was

  2. Thermal- and light-induced spin crossover in novel 2D Fe(II) metalorganic frameworks {Fe(4-PhPy)(2)[M(II)(CN)(x)](y)}.sH(2)O: spectroscopic, structural, and magnetic studies.

    Science.gov (United States)

    Seredyuk, M; Gaspar, A B; Ksenofontov, V; Verdaguer, M; Villain, F; Gütlich, P

    2009-07-06

    Five novel two-dimensional coordination polymers {Fe(4PhPy)(2)[M(II)(CN)(4)]}.sH(2)O (4PhyPy = 4-phenylpyridine; 1: M(II) = Pd, s = 0; 2: M(II) = Ni, s = 0; 3: M(II) = Pt, s = 1) and {Fe(4PhPy)(2)[M(I)(CN)(2)](2)}.sH(2)O (4: M(I) = Ag, s = 1; 5: M(I) = Au, s = 0.5) exhibiting spin-crossover properties have been synthesized. They were characterized at various temperatures using X-ray absorption spectroscopy (XAS), powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), and magnetic susceptibility measurements. The occurrence of a cooperative thermal spin transition detected by the magnetic method is located at critical temperatures T(c)( downward arrow)/T(c)( upward arrow) = 163 K/203 K (1), 135 K/158 K (2), and 172 K/221 K (3), and a less cooperative one is located at T(c) = 188 K (4) and 225 K (5). Compounds 1-5 show an abrupt color change from yellow (high-spin (HS) state) to red (low-spin (LS) state) upon spin-state conversion. The dehydration of the compounds changes the type of the spin transition, making it more abrupt and shifting the critical temperature to higher temperatures. For 1 and 2, XAS provides local structural information on the contraction of the FeN(6) coordination sphere upon the HS-to-LS transition, in line with the magnetic results. Variable-temperature characterization of 1 by X-ray diffraction evidences the very abrupt phase transition with a large hysteresis. A light-induced spin conversion (LIESST effect) is detected by magnetic measurements in 1-5 below 70 K.

  3. Speciation of Fe(II) and Fe(III) in Contaminated Aquifer Sediments Using Chemical Extraction Techniques

    DEFF Research Database (Denmark)

    Heron, Gorm; Crouzet, Catherine.; Bourg, Alain C. M.;

    1994-01-01

    The iron mineralogy of aquifer sediments was described by chemical extraction techniques. Single-step extractions including 1 M CaC12, NaAc, oxalate, dithionite, Ti(II1)- EDTA, 0.5 M HC1,5 M HC1, hot 6 M HC1, and a sequential extraction by HI and CrIIHC1 were tested on standard iron minerals...

  4. Effect of initial solution pH on the degradation of Orange II using clay-based Fe nanocomposites as heterogeneous photo-Fenton catalyst.

    Science.gov (United States)

    Feng, Jiyun; Hu, Xijun; Yue, Po Lock

    2006-02-01

    Effect of initial solution pH on the discoloration and mineralization of 0.2 mM Orange II by using two clay-based Fe nanocomposites (Fe-B (Fe supported on bentonite clay) and Fe-Lap-RD (Fe supported on laponite clay)) as catalysts was studied in detail. It was found that the initial solution pH not only influences the photo-catalytic activity of Fe-B and Fe-Lap-RD but also the Fe leaching from the two catalysts. Both catalysts show the best photo-catalytic activity at an initial solution pH of 3.0, and the activity of the catalysts decreases as the initial solution pH increases. At optimal conditions, 100% discoloration and mineralization of 0.2 mM Orange II are achieved in 60 and 120 min reaction in the presence of 10 mM H2O2, 1.0 g/L Fe-B, and 1 x 8 W UVC at initial solution pH of 3.0. 100% discoloration and 90% mineralization of 0.2 mM Orange II are achieved when Fe-Lap-RD is used as catalyst under the same conditions. Both catalysts also display a reasonable good photo-catalytic activity and negligible Fe leaching at an initial solution pH of 6.6 that is very close to neutral pH. This characteristic makes it possible for the Fe-B and Fe-Lap-RD to have a long-term stability. It also becomes feasible for the photo-Fenton process to treat the original wastewater without the need to pre-adjust the solution pH.

  5. The reactivity of Fe(II) associated with goethite formed during short redox cycles toward Cr(VI) reduction under oxic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Tomaszewski, Elizabeth J.; Lee, Seungyeol; Rudolph, Jared; Xu, Huifang; Ginder-Vogel, Matthew (UW)

    2017-08-01

    Chromium (Cr) is a toxic metal that causes a myriad of health problems and enters the environment as a result of anthropogenic activities and/or natural processes. The toxicity and solubility of chromium is linked to its oxidation state; Cr(III) is poorly soluble and relatively nontoxic, while Cr(VI) is soluble and a known carcinogen. Solid Fe(II) in iron-bearing minerals, such as pyrite, magnetite, and green rusts, reduce the oxidation state of chromium, reducing its toxicity and mobility. However, these minerals are not the only potential sources of solid-associated Fe(II) available for Cr(VI) reduction. For example, ferric (Fe(III)) (hydr)oxides, such as goethite or hematite, can have Fe(II) in the solid without phase transformation; however, the reactivity of Fe(II) within Fe(III) (hydr)oxides with contaminants, has not been previously investigated. Here, we cyclically react goethite with dissolved Fe(II) followed by dissolved O2, leading to the formation of reactive Fe(II) associated with goethite. In separate reactors, the reactivity of this Fe(II) is probed under oxic conditions, by exposure to chromate (CrO42 -) after either one, two, three or four redox cycles. Cr is not present during redox cycling; rather, it is introduced to a subset of the solid after each oxidation half-cycle. Analysis of X-ray absorption near edge structure (XANES) spectra reveals that the extent of Cr(VI) reduction to Cr(III) depends not only on solid Fe(II) content but also surface area and mean size of ordered crystalline domains, determined by BET surface area analysis and X-ray diffraction (XRD), respectively. Shell-by-shell fitting of the extended X-ray absorption fine structure (EXAFS) spectra demonstrates chromium forms both single and double corner sharing complexes on the surface of goethite, in addition to sorbed Cr(III) species. Finally, transmission electron microscope (TEM) imaging and X-ray energy-dispersive spectroscopy (EDS) illustrate that Cr preferentially

  6. Copper(II) complex as a precursor for formation of cyano-bridged pentanuclear FeIII-CuII bimetallic assembly: Synthesis, characterization, crystal structure and antibacterial activity

    Indian Academy of Sciences (India)

    SURACHAI KONGCHOO; KITTIPONG CHAINOK; ANOB KANTACHA; SUMPUN WONGNAWA

    2017-04-01

    [CuL(ClO ₄) ₂] (1) (L = 3,10-diisobutyl-1,3,5,8,10,12-hexaazacyclotetradecane) was synthesized by condensation reaction of ethylenediamine, formaldehyde and iso-butylamine in absolute ethanol. Characterization of 1 utilized various spectroscopic techniques, viz. elemental analysis, electrospray ionization-mass spectrometry (ESI-MS), Fourier-transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-Vis), diffuse reflectance spectroscopy (DRS) and thermogravimetric analysis (TGA). Based on these techniques, the structure of 1 was proposed as Cu(II) ion occupying octahedral geometry with four secondary amine nitrogens of the hexaazamacrocyclic ligand and two perchlorato anions. 1 was used as a precursor in the preparation of cyano-bridged bimetallic compound, [CuL] ₃ [Fe(CN) ₆] ₂•5H ₂O (2), by reaction with K ₃ [Fe(CN) ₆] in aqueous solution. Single-crystal X-ray analysis indicated that 2 crystallized in the monoclinic system with space group P21/n. The structure of 2 consisted of cyano-bridged FeIII-CuII pentanuclear molecules having two [Fe(CN) ₆] ³⁻ anions connected to three cis-[CuL] ²⁺ cations via two cis-cyanide ligands from each ferrate unit. In each of pentanuclear unit, the central [CuL] ²⁺ cation exhibited a distorted octahedral geometry while the other two units exhibited a distorted square pyramidal geometry. The room temperature magnetic moments of both complexes were measured to be 1.92 B.M. for 1 and 5.61 B.M. for 2. The in vitro antibacterial activity of 1 against Staphylococcus aureus ATCC 25923, Escherichia coli ATCC 25922, and Pseudomonas aeruginosa ATCC 27853 strains were studied and compared with standard drugs, which showed moderate antibacterial activity compared with Penicillin and Gentamicin.

  7. In Situ Structural Characterization of Ferric Iron Dimers in Aqueous Solutions

    DEFF Research Database (Denmark)

    Zhu, Mengqiang; Puls, Brendan W.; Frandsen, Cathrine

    2013-01-01

    The structure of ferric iron (Fe3+) dimers in aqueous solutions has long been debated. In this work, we have determined the dimer structure in situ in aqueous solutions using extended X-ray absorption fine structure (EXAFS) spectroscopy. An Fe K-edge EXAFS analysis of 0.2 M ferric nitrate solutio...

  8. mer-[Fe(pcq)(CN)3]-: a novel cyanide-containing building block and its application to assembling cyanide-bridged trinuclear FeIII2MnII complexes [pcq- = 8-(pyridine-2-carboxamido)quinoline anion].

    Science.gov (United States)

    Ni, Zhong-Hai; Kou, Hui-Zhong; Zhang, Li-Fang; Ni, Wei-Wei; Jiang, Yun-Bo; Cui, Ai-Li; Ribas, Joan; Sato, Osamu

    2005-12-26

    A new cyanide-containing building block K[Fe(pcq)(CN)(3)] [1; pcq(-) = 8-(pyridine-2-carboxamido)quinoline anion] containing a low-spin Fe(III) center with three cyanide groups in a meridional arrangement has been successfully designed and synthesized. Three cyanide-bridged trinuclear Fe(III)(2)Mn(II) complexes, [Fe(pcq)(CN)(3)](2)[Mn(CH(3)OH)(2)(H(2)O)(2)].2H(2)O (2), [Fe(pcq)(CN)(3)](2)[Mn(bipy)(2)].CH(3)OH.2H(2)O (3), and [Fe(pcq)(CN)(3)](2)[Mn(phen)(2)].CH(3)OH.2H(2)O (4), have been synthesized and structurally characterized. The magnetic susceptibilities of the three heterometallic complexes have been investigated.

  9. Synthesis, characterization and antimicrobial activity of Fe(II), Zn(II), Cd(II) and Hg(II) complexes with 2,6-bis(benzimidazol-2-yl) pyridine ligand.

    Science.gov (United States)

    Aghatabay, Naz M; Neshat, A; Karabiyik, T; Somer, M; Haciu, D; Dülger, B

    2007-02-01

    2,6-Bis(benzimidazol-2-yl)pyridine (L) ligand and complexes [M(L)Cl(2)] and [Fe(L)(2)](ClO(4))(2) (M=Zn, Cd, Hg) have been synthesized. The geometries of the [M(L)Cl(2)] complexes were derived from theoretical calculation in DGauss/DFT level (DZVP basis set) on CACHE. The central M(II) ion is penta-coordinated and surrounded by N(3)Cl(2) environment, adopting a distorted trigonal bipyramidal geometry. The ligand is tridentate, via three nitrogen atoms to metal centre and two chloride ions lie on each side of the distorted benzimidazole ring. In the [Fe(L)(2)](ClO(4))(2) complex, the central Fe(II) ion is surrounded by two (3N) units, adopting a octahedral geometry. The elemental analysis, molecular conductivity, FT-Raman, FT-IR (mid-, far-IR), (1)H, and (13)C NMR were reported. The antimicrobial activities of the free ligand, its hydrochloride salt, and the complexes were evaluated using the disk diffusion method in dimethyl sulfoxide (DMSO) as well as the minimal inhibitory concentration (MIC) dilution method, against 10 bacteria and the results compared with that for gentamycin. Antifungal activities were reported for Candida albicans, Kluyveromyces fragilis, Rhodotorula rubra, Debaryomyces hansenii, Hanseniaspora guilliermondii, and the results were referenced against nystatin, ketaconazole, and clotrimazole antifungal agents. In most cases, the compounds tested showed broad-spectrum (Gram positive and Gram negative bacteria) activities that were either more effective than or as potent as the references. The binding of two most biologically effective compounds of zinc and mercury to calf thymus DNA has also been investigated by absorption spectra.

  10. Cryogenic Field Measurement of Pr2Fe14B Undulator and Performance Enhancement Options at the NSLS-II

    Energy Technology Data Exchange (ETDEWEB)

    Tanabe, T.; Chubar, O.; Harder, David A.; Lehecka, Michael; Rank, James; Rakowsky, George; Spataro, Charles

    2009-09-27

    Short period (14.5mm) hybrid undulator arrays composed of Praseodymium Iron Boron (Pr{sub 2}Fe{sub 14}B) magnets (CR53, NEOMAX, Inc.) and vanadium permendur poles have been fabricated at Brookhaven National Laboratory. Unlike Neodymium Iron Boron (Nd{sub 2}Fe{sub 14}B) magnets which exhibit spin reorientation at temperatures below 150K, PrFeB arrays monotonically increase performance with lower operating temperature. It opens up the posibility for use in operating a cryo-permanent magnet undulator (CPMU) in the range of 40K to 60K where very efficient cryocoolers are available. Magnetic flux density profiles were measured at various temperature ranges from room temperature down to liquid helium (LHe) using the Vertical Testing Facility (VTF) at the National Snchrotron Light Source-II (NSLS-II). Temperature variations of phase error have been characterized. In addition, we examined the use of textured Dysprosium (Dy) poles to replace permendur poles to obtain further improvement in performance.

  11. HST/WFC3 Imaging of Protostellar Jets in Carina: [Fe II] Emission Tracing Massive Jets from Intermediate Mass Protostars

    CERN Document Server

    Reiter, Megan

    2013-01-01

    We present narrowband WFC3-UVIS and -IR images of four externally irradiated protostellar jets in the Carina nebula: HH666, HH901, HH902, and HH1066. These massive jets are unusual because they are bathed in UV radiation from dozens of nearby O stars, but despite the strong incident ionizing radiation, portions of the jet remain neutral. Near-IR [Fe II] images reveal dense, neutral gas that was not seen in previous studies of H-alpha emission. We show that near-IR [Fe II] emitting gas must be self-shielded from Lyman continuum photons, regardless of its excitation mechanism (shocks, FUV radiation, or both). High densities are required for the survival of Fe+ amid the strong Lyman continuum from Tr14, raising estimates of the mass-loss rates by an order of magnitude. Higher jet mass-loss rates require higher accretion rates onto their driving protostars, implying that these jets are driven by intermediate-mass (IM; ~2-8 Msun) stars. Indeed, the IR driving sources of two of these outflows have luminosities that...

  12. Submicron-Scale Heterogeneities in Nickel Sorption of Various Cell-Mineral Aggregates Formed by Fe(II)-Oxidizing Bacteria.

    Science.gov (United States)

    Schmid, Gregor; Zeitvogel, Fabian; Hao, Likai; Ingino, Pablo; Adaktylou, Irini; Eickhoff, Merle; Obst, Martin

    2016-01-01

    Fe(II)-oxidizing bacteria form biogenic cell-mineral aggregates (CMAs) composed of microbial cells, extracellular organic compounds, and ferric iron minerals. CMAs are capable of immobilizing large quantities of heavy metals, such as nickel, via sorption processes. CMAs play an important role for the fate of heavy metals in the environment, particularly in systems characterized by elevated concentrations of dissolved metals, such as mine drainage or contaminated sediments. We applied scanning transmission (soft) X-ray microscopy (STXM) spectrotomography for detailed 3D chemical mapping of nickel sorbed to CMAs on the submicron scale. We analyzed different CMAs produced by phototrophic or nitrate-reducing microbial Fe(II) oxidation and, in addition, a twisted stalk structure obtained from an environmental biofilm. Nickel showed a heterogeneous distribution and was found to be preferentially sorbed to biogenically precipitated iron minerals such as Fe(III)-(oxyhydr)oxides and, to a minor extent, associated with organic compounds. Some distinct nickel accumulations were identified on the surfaces of CMAs. Additional information obtained from scatter plots and angular distance maps, showing variations in the nickel-iron and nickel-organic carbon ratios, also revealed a general correlation between nickel and iron. Although a high correlation between nickel and iron was observed in 2D maps, 3D maps revealed this to be partly due to projection artifacts. In summary, by combining different approaches for data analysis, we unambiguously showed the heterogeneous sorption behavior of nickel to CMAs.

  13. A novel reusable nanocomposite adsorbent, xanthated Fe{sub 3}O{sub 4}-chitosan grafted onto graphene oxide, for removing Cu(II) from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jinshui, E-mail: jsliu@sina.com; Liu, Wenxiu; Wang, Yiru; Xu, Meijiao; Wang, Bin

    2016-03-30

    Graphical abstract: - Highlights: • Xanthated Fe{sub 3}O{sub 4}-chitosan grafted onto graphene oxide (xanthated Fe{sub 3}O{sub 4}-CS-GO) was synthesized. • Xanthated Fe{sub 3}O{sub 4}-CS-GO demonstrates the high affinity to Cu(II) ions. • The adsorbent can be effectively reused to remove Cu(II) ions. - Abstract: Novel nanocomposites of xanthated Fe{sub 3}O{sub 4}-chitosan grafted onto graphene oxide (xanthated Fe{sub 3}O{sub 4}-CS-GO) were successfully synthesized for the first time using an amidation reaction. The xanthated Fe{sub 3}O{sub 4}-CS-GO was used to remove Cu(II) from aqueous solutions. The xanthated Fe{sub 3}O{sub 4}-CS-GO was characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffractometry, and energy dispersive X-ray spectroscopy. The Cu(II) adsorption isotherms for the xanthated Fe{sub 3}O{sub 4}-CS-GO fitted the Langmuir isotherm model. The maximum Cu(II) adsorption capacity of the xanthated Fe{sub 3}O{sub 4}-CS-GO was 426.8 mg g{sup −1}, which is much higher than the maximum adsorption capacities of other adsorbents that have been described in the literature. This was attributed to xanthated Fe{sub 3}O{sub 4}-CS-GO having abundant functional groups. The xanthated Fe{sub 3}O{sub 4}-CS-GO could be regenerated using ethylene diamine tetraacetic acid, and could easily be removed from a liquid using an external magnetic field. These features would allow secondary pollution of the environment to be avoided more easily than is the case for other adsorbents. Cu(II) was adsorbed from aqueous solutions quickly and efficiently by the xanthated Fe{sub 3}O{sub 4}-CS-GO complex, suggesting that xanthated Fe{sub 3}O{sub 4}-CS-GO may be an ideal candidate for removing Cu(II) from wastewater.

  14. A two-fold interpenetrated flexible bi-pillared-layer framework of Fe(II) with interesting solvent adsorption property

    Indian Academy of Sciences (India)

    Ritesh Haldar; Tapas Kumar Majia

    2011-11-01

    A two-fold interpenetrated microporous bi-pillared-layer framework of Fe(II), {[Fe(2,6-napdc)(4,4'-bipy)](EtOH)(H2O)} (1) (2,6-napdc =2,6-naphthalenedicarboxylate; 4,4'-bipy=4,4'-bipyridine) composed of mixed ligand system has been synthesized and structurally characterized. The 2,6-napdc linkers form a 2D corrugated sheet of {Fe(2,6-napdc)} by linking the secondary building unit of Fe2(CO2)2 in the plane, which are further connected by double 4,4'-bipy pillars resulting in a bi-pillared-layer type 3D framework. The 3D framework is two-fold interpenetrated and exhibits a 3D channel structure (4.0 × 3.5, 1.5 × 0.5 and 2.2 × 2.1 Å2) occupied by the guest water and ethanol molecules. Framework 1 shows high thermal stability, and the desolvated framework (1′) renders permanent porosity realized by N2 adsorption profile at 77K (BET surface area of ∼ 52 m2 g-1). Moreover, the framework 1′ also uptakes different solvent vapours (water, methanol and ethanol) and their type-I profile suggest strong interaction with pore surfaces and overall hydrophilic nature of the framework. Temperature dependent magnetic measurements suggest overall antiferromagnetic behaviour in compound 1.

  15. One-step synthesis of water-dispersible cysteine functionalized magnetic Fe{sub 3}O{sub 4} nanoparticles for mercury(II) removal from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Xiaofang, E-mail: xfshen@jiangnan.edu.cn [State Key Laboratory of Dairy Biotechnology, Technology Center, Bright Dairy and Food Co. Ltd., Shanghai 200436 (China); State Key Laboratory of Food Science and Technology, School of Food Science and Technology, Jiangnan University, Wuxi 214122 (China); Wang, Qin; Chen, WenLing; Pang, Yuehong [State Key Laboratory of Food Science and Technology, School of Food Science and Technology, Jiangnan University, Wuxi 214122 (China)

    2014-10-30

    Graphical abstract: Using Fe{sup 2+} as precursors, air as oxidant and cysteine as protectant, this novel cysteine functionalized Fe{sub 3}O{sub 4} magnetic nanoparticles (Cys-Fe{sub 3}O{sub 4} MNPs) was facilely one-pot synthesized at room temperature by oxidation–precipitation method with the assistance of sonication. Then the Cys-Fe{sub 3}O{sub 4} MNPs were demonstrated as an inexpensive and quite efficient magnetic nano-adsorbent for as high as 95% Hg(II) removal efficiency. These results indicated that Cys-Fe{sub 3}O{sub 4} MNPs is a potentially attractive material for the removal of Hg(II) from water. - Highlights: • A simplified one-step synthesis method of superparamagnetic Cys-Fe{sub 3}O{sub 4} MNPs was developed. • It was synthesized at room temperature by oxidation-precipitation method with the assistance of sonication. • It was demonstrated as an inexpensive and quite efficient magnetic nano-adsorbent for Hg(II) removal. - Abstract: Cysteine functionalized Fe{sub 3}O{sub 4} magnetic nanoparticles (Cys-Fe{sub 3}O{sub 4} MNPs) were prepared facilely for Hg(II) removal from aqueous solutions. Using Fe{sup 2+} as precursors, air as oxidant and Cys as protectant, this novel material was one-pot synthesis at room temperature by oxidation–precipitation method with the assistance of sonication. The MNPs were characterized by TEM, VSM, FTIR, X-ray powder diffraction analysis (XRD) and TGA methods. Under the optimum experimental conditions, the removal efficiency was as high as 95% and the maximum sorption capacity is found to be 380 mg/mol for Hg(II). Study on adsorption kinetics shows that adsorption of Hg(II) onto Cys-Fe{sub 3}O{sub 4} MNPs follows pseudo-first-order kinetic model and the adsorption rate constant was 0.22 min{sup −1}. Additionally, the Hg(II)-loaded Cys-Fe{sub 3}O{sub 4} MNPs could be easily regenerated up to 95% using 1.0 M acetic acid. These results indicated that Cys-Fe{sub 3}O{sub 4} MNPs is a potentially attractive material

  16. An insight into the magnetoelectric coupling effect in the MOF of [NH2(CH3)2]n[FeIIIFeII(HCOO)6]n

    Science.gov (United States)

    Guo, Jiangbin; Chen, Lihong; Li, Dong; Zhao, Haixia; Dong, Xinwei; Long, Lasheng; Huang, Rongbin; Zheng, Lansun

    2017-05-01

    Understanding the microscopic mechanism of magnetoelectric coupling is of fundamental importance for the rational design of multiferroics. Herein, the magnetoelectric coupling effect in the metal-organic frameworks of [NH2(CH3)2]n[FeIIIFeII(HCOO)6]n (1) was investigated, respectively, through measuring the dielectric properties and ferroelectric polarization of single-crystal 1 along different crystal axes under external magnetic fields. Analysis on the magnetic structure of 1 reveals that the defect in the FeII-FeIII sublattices plays a key contribution to the magnetoelectric coupling of 1, providing a unique insight into the magnetoelectric coupling effect of MOFs-based multiferroics.

  17. Spin crossover iron(II) coordination polymer chains: syntheses, structures, and magnetic characterizations of [Fe(aqin)2(μ2-M(CN)4)] (M = Ni(II), Pt(II), aqin = quinolin-8-amine).

    Science.gov (United States)

    Setifi, Fatima; Milin, Eric; Charles, Catherine; Thétiot, Franck; Triki, Smail; Gómez-García, Carlos J

    2014-01-06

    New Fe(II) coordination polymeric neutral chains of formula [Fe(aqin)2(μ2-M(CN)4)] (M = Ni(II) (1) and Pt(II) (2)) (aqin = Quinolin-8-amine) have been synthesized and characterized by infrared spectroscopy, X-ray diffraction, and magnetic measurements. The crystal structure determinations of 1-2 reveal in both cases a one-dimensional structure in which the planar [M(CN)4](2-) (M = Ni(II) (1) and Pt(II) (2)) anion acts as a μ2-bridging ligand, and the two aqin molecules as chelating coligands. Examination of the intermolecular contacts in the two compounds reveals that the main contacts are ascribed to hydrogen bonding interactions involving the amine groups of the aqin chelating ligands and the nitrogen atoms of the two non bridging CN groups of the [M(CN)4](2-) (M = Ni(II) (1) and Pt(II) (2)) anion. The average values of the six Fe-N distances observed respectively at room temperature (293 K) and low temperature (120 K), that is, 2.142(3) and 2.035(2) Å for 1, and 2.178(3) and 1.990(2) Å for 2, and the thermal variation of the cell parameters (performed on 2) are indicative of the presence of an abrupt HS-LS spin crossover (SCO) transition in both compounds. The thermal dependence of the product of the molar magnetic susceptibility times the temperature (χmT), in cooling and warming modes, confirms the SCO behavior at about 145 and 133 K in 1 and 2, respectively, and reveals the presence of a small thermal hysteresis of about 2 K for each compound.

  18. Adsorption of Cd(II) and Pb(II) by in situ oxidized Fe3O4 membrane grafted on 316L porous stainless steel filter tube and its potential application for drinking water treatment.

    Science.gov (United States)

    Zhu, Mengfei; Zhu, Li; Wang, Jianlong; Yue, Tianli; Li, Ronghua; Li, Zhonghong

    2017-03-08

    Removing heavy metal ions from aqueous solutions is one of the most challenging separations. In situ oxidized Fe3O4 membranes using 316L porous stainless steel filter tube have shown great potential for removing anion Cr(VI). Here we report the performances of the in situ oxidized Fe3O4 membranes for removing two toxic cations Cd(II) and Pb(II) commonly existing in water and their potential applications for drinking water purification. The membranes exhibited high removal efficiency: 97% at pH 9.0 for Cd(II) of 1.0 mg/L initial concentration and 100% at pH 5.0-6.0 for Pb(II) of 5.0 mg/L initial concentration. The maximum adsorption capabilities were estimated at 0.800 mg/g and 2.251 mg/g respectively for Cd(II) and Pb(II) at 318 K by the Langmuir model. Results of batch tests revealed the existence of electrostatic attraction and chemisorption. XRD and FT-IR analyses indicated that the chemisorption might be the insertion of Cd(II) and Pb(II) into the Fe3O4 crystal faces of 311 and 511 to form mononuclear or binuclear coordination with O atoms of Fe-O6 groups. Competitive adsorption of Cd(II) and Pb(II) in binary solutions revealed a preferential adsorption for Pb(II). Na2EDTA solution was used to regenerate the membranes, and the maximum desorption ratio was 90.29% and 99.75% respectively for Cd(II) and Pb(II). The membranes were able to efficiently lower Cd(II) and Pb(II) concentrations to meet the drinking water standards recommended by the World Health Organization and are promising for engineering applications aimed at drinking water purification.

  19. Sub-picosecond time resolved infrared spectroscopy of high-spin state formation in Fe(II) spin crossover complexes

    DEFF Research Database (Denmark)

    Døssing, Anders Rørbæk; Wolf, Matthias M. N.; Gross, Ruth

    2008-01-01

      The photoinduced low-spin (S = 0) to high-spin (S = 2) transition of the iron(II) spin-crossover systems [Fe(btpa)](PF6)2 and [Fe(b(bdpa))](PF6)2 in solution have been studied for the first time by means of ultrafast transient infrared spectroscopy at room temperature. Negative and positive...... absorption cross sections. The simulated infrared difference spectra are dominated by an increase of the absorption cross section upon high-spin state formation in accordance with the experimental infrared spectra....... infrared difference bands between 1000 and 1065 cm-1 that appear within the instrumental system response time of 350 fs after excitation at 387 nm display the formation of the vibrationally unrelaxed and hot high-spin 5T2 state. Vibrational relaxation is observed and characterized by the time constants 9...

  20. Electro-assisted heterogeneous activation of persulfate by Fe/SBA-15 for the degradation of Orange II.

    Science.gov (United States)

    Cai, Chun; Zhang, Zhuoyue; Zhang, Hui

    2016-08-05

    The removal of Orange II by activation of persulfate (S2O8(2-), PS) using synthesized Fe/SBA-15 in the electrochemical (EC) enhanced process was reported in this study. The reaction rate constants, degradation mechanism, catalyst stability, and evolution of mineralization and toxicity were detailed investigated. On the basis of radical scavenger results, both the sulfate radicals (SO4(-)) and hydroxyl radicals (OH) were responsible for the degradation of Orange II. A possible pathway is suggested to describe the degradation of Orange II according to the degradation intermediates identified. The results showed that the Fe/SBA-15 catalyst maintained strong reusability and stability with a low level of iron leaching. In addition, favorable mineralization efficiency in terms of COD removal efficiency (75.4%) and TOC removal efficiency (46.3%) was obtained when the reaction time was prolonged to 24h. The toxicity experiments implied that the toxicity of the treated solution ascended at the first 30min but then dropped to almost zero eventually. This study provides a proof-of-concept that can be applied widely for the PS remediation of contaminated water.

  1. Nanosized yolk-shell Fe3O4@Zr(OH)x spheres for efficient removal of Pb(II) from aqueous solution.

    Science.gov (United States)

    Pan, Shunlong; Li, Jiansheng; Wan, Gaojie; Liu, Chao; Fan, Wenhong; Wang, Lianjun

    2016-05-15

    In this work, Fe3O4@Zr(OH)x yolk-shell nanospheres (YSNs) were synthesized via a two-step process and further examined as adsorbents for the removal of Pb(II). To understand the hollow structure on the adsorption properties of Pb(II), another adsorbent without hollow cavities, i.e., Fe3O4@SiO2@Zr(OH)x core-shell nanospheres (CSNs), was also prepared for comparison. The adsorption results showed that Fe3O4@Zr(OH)x YSNs exhibited 41.6% higher Pb(II) adsorption capacity as compared to that of Fe3O4@SiO2@Zr(OH)x CSNs. The isotherm was well fitted to Langmuir adsorption model with qmax value of 310.8 mg/g after normalized by the weight of Zr in Fe3O4@Zr(OH)x YSNs. Scanning transmission electron microscopy (STEM) mapping results revealed that the existence of cavities between Fe3O4 cores and Zr(OH)x shells is responsible for the improved adsorption performance. XPS analysis indicated the surface hydroxyl groups played a key role in the Pb(II) adsorption. The removal efficiency of Pb(II) was maintained above 90% in five consecutive adsorption-desorption cycles.

  2. Metagenomic insights into the dominant Fe(II oxidizing Zetaproteobacteria from an iron mat at Lōi’hi, Hawai’I

    Directory of Open Access Journals (Sweden)

    Esther eSinger

    2013-03-01

    Full Text Available Zetaproteobacteria are among the most prevalent Fe(II oxidizing bacteria at deep-sea hydrothermal vents; however, knowledge about their environmental significance is limited. We provide metagenomic insights into an iron mat at the Lōʻihi Seamount, Hawai’I, revealing novel genomic information of locally dominant Zetaproteobacteria lineages. These lineages were previously estimated to account for ~13% of all local Zetaproteobacteria based on 16S clone library data. Biogeochemically relevant genes include nitrite reductases, which were previously not identified in Zetaproteobacteria, sulfide:quinone oxidases, and ribulose-1,5-bisphosphate carboxylase (RuBisCo. Genes assumed to be involved in Fe(II oxidation correlate in synteny and share 70% AASim with those previously identified in the related Zetaproteobacterium Mariprofundus ferrooxydans PV-1. Overall, Zetaproteobacteria genes appear to originate primarily from within the Proteobacteria and the Fe(II oxidizing Leptospirillum spp. and are predicted to facilitate adaptation to a deep-sea hydrothermal vent environment in addition to microaerophilic Fe(II and H2S oxidation. This dataset represents the first metagenomic study of Fe(II oxidizing bacteria (FeOB from an iron oxide mat at a deep-sea hydrothermal habitat.

  3. Heteroleptic Fe(II) complexes of 2,2'-biimidazole and its alkylated derivatives: spin-crossover and photomagnetic behavior.

    Science.gov (United States)

    Phan, Hoa V; Chakraborty, Pradip; Chen, Meimei; Calm, Yitzi M; Kovnir, Kirill; Keniley, Lawrence K; Hoyt, Jordan M; Knowles, Elisabeth S; Besnard, Céline; Meisel, Mark W; Hauser, Andreas; Achim, Catalina; Shatruk, Michael

    2012-12-03

    Three iron(II) complexes, [Fe(TPMA)(BIM)](ClO(4))(2)⋅0.5H(2)O (1), [Fe(TPMA)(XBIM)](ClO(4))(2) (2), and [Fe(TPMA)(XBBIM)](ClO(4))(2)⋅0.75CH(3)OH (3), were prepared by reactions of Fe(II) perchlorate and the corresponding ligands (TPMA=tris(2-pyridylmethyl)amine, BIM=2,2'-biimidazole, XBIM=1,1'-(α,α'-o-xylyl)-2,2'-biimidazole, XBBIM=1,1'-(α,α'-o-xylyl)-2,2'-bibenzimidazole). The compounds were investigated by a combination of X-ray crystallography, magnetic and photomagnetic measurements, and Mössbauer and optical absorption spectroscopy. Complex 1 exhibits a gradual spin crossover (SCO) with T(1/2) =190 K, whereas 2 exhibits an abrupt SCO with approximately 7 K thermal hysteresis (T(1/2) =196 K on cooling and 203 K on heating). Complex 3 is in the high-spin state in the 2-300 K range. The difference in the magnetic behavior was traced to differences between the inter- and intramolecular interactions in 1 and 2. The crystal packing of 2 features a hierarchy of intermolecular interactions that result in increased cooperativity and abruptness of the spin transition. In 3, steric repulsion between H atoms of one of the pyridyl substituents of TPMA and one of the benzene rings of XBBIM results in a strong distortion of the Fe(II) coordination environment, which stabilizes the high-spin state of the complex. Both 1 and 2 exhibit a photoinduced low-spin to high-spin transition (LIESST effect) at 5 K. The difference in the character of intermolecular interactions of 1 and 2 also manifests in the kinetics of the decay of the photoinduced high-spin state. For 1, the decay rate constant follows the single-exponential law, whereas for 2 it is a stretched exponential, reflecting the hierarchical nature of intermolecular contacts. The structural parameters of the photoinduced high-spin state at 50 K are similar to those determined for the high-spin state at 295 K. This study shows that N-alkylation of BIM has a negligible effect on the ligand field strength. Therefore

  4. Orientation towards asymmetric transfer hydrogenation of ketones catalyzed by (pyrazolyl)ethyl)pyridine Fe(II) and Ni(II) complexes

    Science.gov (United States)

    Magubane, Makhosazane N.; Alam, Mohd Gulfam; Ojwach, Stephen O.; Munro, Orde Q.

    2017-05-01

    Compounds 2-[1-(3,5-dimethylpyrazol-1-yl)ethyl]pyridine (L1) and 2-[1-(3,5-diphenylpyrazol-1-yl)ethyl]pyridine (L2) were obtained in a three-step procedure which involved the reduction of acetylpyridine using NaBH4, chlorination of the alcohol intermediate using SOCl2 and subsequent reaction with appropriate pyrazoles. Reactions of L1 and L2 with Ni(II) and Fe(II) halides produced the respective complexes Ni(L1)Br2 (1), Ni(L1)Cl2 (2), Fe(L1)Cl2 (3) and Ni(L2)Br2 (4) as racemic mixtures in moderate yields. The molecular structures of complexes 1 and 4 are dinuclear and mononuclear respectively. All the complexes (1-4) formed active catalysts for the transfer hydrogenation of ketones (THK) in 2-propanol at 82 °C affording conversions of 58%-84% within 48 h. The influence of catalyst structure, reaction conditions and identity of ketone substrates in the TH reactions have been successfully established.

  5. Synthesis and Structural Studies of Cr(III, Mn(II and Fe(III Complexes of N(2-Benzimidazolylacetylacetohydrazone

    Directory of Open Access Journals (Sweden)

    G. H. Anuradha

    2011-01-01

    Full Text Available The ligand N(2-benzimidazolylacetylacetohydrazone (BAAH have been synthesized and characterized. Coordination complexes of Cr(III, Mn(II and Fe(III have been synthesized with the ligand BAAH. These complexes were characterized on the basis of analytical, conductance, thermal, magnetic data and infrared and electronic spectral data. The ligand BAAH is behaving as a neutral tridentate NNO donar employing two azomethine nitrogens (ring and side chain and carbonyl oxygen. The ligand and it's metal complexes were tested for anti microbial activity on the gram positive S. Aureus, E. coli and Proteus.

  6. Comparative adsorption of Fe(III and Cd(II ions on glutaraldehyde crosslinked chitosan–coated cristobalite

    Directory of Open Access Journals (Sweden)

    Rahmi

    2015-12-01

    Full Text Available In this study, chitosan was crosslinked with glutaraldehyde and coated on the surface of cristobalite through a dip and phase inversion process. The adsorbent was used in batch experiments to evaluate the adsorption of Fe(III and Cd(II ions. A maximum adsorption capacity was observed at a glutaraldehyde concentration in sorbent preparation of 1% (w/w. The equilibrium adsorption quantity was determined to be a function of the solution pH, initial concentration and agitation period. Langmuir and Freundlich adsorption models were used to describe adsorption isotherms.

  7. Plausible mechanisms of the fenton-like reactions, M = Fe(II) and Co(II), in the presence of RCO2(-) substrates: are OH(•) radicals formed in the process?

    Science.gov (United States)

    Kornweitz, Haya; Burg, Ariela; Meyerstein, Dan

    2015-05-01

    DFT calculations concerning the plausible mechanism of Fenton-like reactions catalyzed by Fe(II) and Co(II) cations in the presence of carboxylate ligands suggest that hydroxyl radicals are not formed in these reactions. This conclusion suggests that the commonly accepted mechanisms of Fenton-like reactions induced oxidative stress and advanced oxidation processes have to be reconsidered.

  8. Characterizing the production and retention of dissolved iron as Fe(II) across a natural gradient in chlorophyll concentrations in the Southern Drake Passage - Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Katherine Barbeau

    2007-04-10

    Recent mesoscale iron fertilization studies in the Southern Ocean (e.g. SOIREE, EisenEx, SOFeX) have demonstrated the importance of iron as a limiting factor for phytoplankton growth in these high nutrient, low-chlorophyll (HNLC) waters. Results of these experiments have demonstrated that factors which influence the biological availability of the iron supplied to phytoplankton are crucial in bloom development, longevity, and generation of carbon export flux. These findings have important implications for the future development of iron fertilization protocols to enhance carbon sequestration in high-latitude oceans. In particular, processes which lead to the mobilization and retention of iron in dissolved form in the upper ocean are important in promoting continued biological availability of iron. Such processes can include photochemical redox cycling, which leads to the formation of soluble reduced iron, Fe(II), within iron-enriched waters. Creation of effective fertilization schemes will thus require more information about Fe(II) photoproduction in Southern Ocean waters as a means to retain new iron within the euphotic zone. To contribute to our knowledge base in this area, this project was funded by DOE with a goal of characterizing the production and retention of dissolved Fe as Fe(II) in an area of the southern Drake Passage near the Shackleton Transverse Ridge, a region with a strong recurrent chlorophyll gradient which is believed to be a site of natural iron enrichment in the Southern Ocean. This area was the focus of a multidisciplinary NSF/OPP-funded investigation in February 2004 (OPP02-30443, lead PI Greg Mitchell, SIO/UCSD) to determine the influence of mesoscale circulation and iron transport with regard to the observed patterns in sea surface chlorophyll in the region near the Shackleton Transverse Ridge. A number of parameters were assessed across this gradient in order to reveal interactions between plankton community structure and iron distributions

  9. Protein dimerization. Inside job.

    Science.gov (United States)

    Metzger, H

    1994-04-01

    In a sophisticated combination of genetic engineering and organic synthesis, a general method for dimerizing recombinant intracellular proteins has been devised; the usefulness of the method should now be testable.

  10. Marinobacter subterrani, a genetically tractable neutrophilic Fe(II-oxidizing strain isolated from the Soudan Iron Mine

    Directory of Open Access Journals (Sweden)

    Benjamin Michael Bonis

    2015-07-01

    Full Text Available We report the isolation, characterization, and development of a robust genetic system for a halophilic, Fe(II-oxidizing bacterium isolated from a vertical borehole originating 714 m below the surface located in the Soudan Iron Mine in northern Minnesota, USA. Sequence analysis of the 16S rRNA gene places the isolate in the genus Marinobacter of the Gammaproteobacteria. The genome of the isolate was sequenced using a combination of short- and long-read technologies resulting in 2 contigs representing a 4.4 Mbp genome. Using genomic information, we used a suicide vector for targeted deletion of specific flagellin genes, resulting in a motility-deficient mutant. The motility mutant was successfully complemented by expression of the deleted genes in trans. Random mutagenesis using a transposon was also achieved. Capable of heterotrophic growth, this isolate represents a microaerophilic Fe(II-oxidizing species for which a system for both directed and random mutagenesis has been established. Analysis of 16S rDNA suggests Marinobacter represents a major taxon in the mine, and genetic interrogation of this genus may offer insight into the structure of deep subsurface communities as well as an additional tool for analyzing nutrient and element cycling in the subsurface ecosystem.

  11. Innovative combination of electrolysis and Fe(II)-activated persulfate oxidation for improving the dewaterability of waste activated sludge.

    Science.gov (United States)

    Zhen, Guang-Yin; Lu, Xue-Qin; Li, Yu-You; Zhao, You-Cai

    2013-05-01

    The feasibility of electrolysis integrated with Fe(II)-activated persulfate (S2O8(2-)) oxidation to improve waste activated sludge (WAS) dewaterability was evaluated. The physicochemical properties (sludge volume (SV), total suspended solids (TSS) and volatile suspended solids (VSS)) and extracellular polymeric substances (EPS), including slime EPS, loosely bound EPS (LB-EPS) and tightly bound EPS (TB-EPS) were characterized to identify their exact roles in sludge dewatering. While dewaterability negatively corresponded to LB-EPS, TB-EPS, protein (PN) and polysaccharide (PS) in LB-EPS and TB-EPS, it was independent of SV, TSS, VSS, slime EPS and PN/PS. Further study through scanning electron microscope (SEM) verified the entrapment of bacterial cells by TB-EPS, protecting them against electrolysis disruption. Comparatively, electrolysis integrated with S2O8(2-)/Fe(II) oxidation was able to effectively disrupt the protective barrier and crack the entrapped cells, releasing the water inside EPS and cells. Therefore, the destruction of both TB-EPS and cells is the fundamental reason for the enhanced dewaterability.

  12. Confinement of a bioinspired nonheme Fe(II) complex in 2D hexagonal mesoporous silica with metal site isolation.

    Science.gov (United States)

    Jollet, Véronique; Albela, Belén; Sénéchal-David, Katell; Jégou, Pascale; Kolodziej, Emilie; Sainton, Joëlle; Bonneviot, Laurent; Banse, Frédéric

    2013-08-28

    A mixed amine pyridine polydentate Fe(II) complex was covalently tethered in hexagonal mesoporous silica of the MCM-41 type. Metal site isolation was generated using adsorbed tetramethylammonium cations acting as a patterned silanol protecting mask and trimethylsilylazane as a capping agent. Then, the amine/pyridine ligand bearing a tethering triethoxysilane group was either grafted to such a pretreated silica surface prior to or after complexation to Fe(II). These two synthetic routes, denoted as two-step and one-step, respectively, were also applied to fumed silica for comparison, except that the silanol groups were capped after tethering the metal unit. The coordination of the targeted complex was monitored using UV-visible spectrophotometry and, according to XPS, the best control was achieved inside the channels of the mesoporous silica for the two-step route. For the solid prepared according to the one-step route, tethering of the complex occurred mainly at the entrance of the channel.

  13. The phosphatidylserine receptor from Hydra is a nuclear protein with potential Fe(II dependent oxygenase activity

    Directory of Open Access Journals (Sweden)

    Stiening Beate

    2004-06-01

    Full Text Available Abstract Background Apoptotic cell death plays an essential part in embryogenesis, development and maintenance of tissue homeostasis in metazoan animals. The culmination of apoptosis in vivo is the phagocytosis of cellular corpses. One morphological characteristic of cells undergoing apoptosis is loss of plasma membrane phospholipid asymmetry and exposure of phosphatidylserine on the outer leaflet. Surface exposure of phosphatidylserine is recognised by a specific receptor (phosphatidylserine receptor, PSR and is required for phagocytosis of apoptotic cells by macrophages and fibroblasts. Results We have cloned the PSR receptor from Hydra in order to investigate its function in this early metazoan. Bioinformatic analysis of the Hydra PSR protein structure revealed the presence of three nuclear localisation signals, an AT-hook like DNA binding motif and a putative 2-oxoglutarate (2OG-and Fe(II-dependent oxygenase activity. All of these features are conserved from human PSR to Hydra PSR. Expression of GFP tagged Hydra PSR in hydra cells revealed clear nuclear localisation. Deletion of one of the three NLS sequences strongly diminished nuclear localisation of the protein. Membrane localisation was never detected. Conclusions Our results suggest that Hydra PSR is a nuclear 2-oxoglutarate (2OG-and Fe(II-dependent oxygenase. This is in contrast with the proposed function of Hydra PSR as a cell surface receptor involved in the recognition of apoptotic cells displaying phosphatidylserine on their surface. The conservation of the protein from Hydra to human infers that our results also apply to PSR from higher animals.

  14. Spin crossover properties of the [Fe(PM-BiA) sub 2 (NCS) sub 2] complex - phases I and II

    CERN Document Server

    Letard, J F; Nguyen, O; Marcen, S; Marchivie, M; Guionneau, P; Chasseau, D; Guetlich, P

    2003-01-01

    In the present review, we reexamine the photomagnetic properties of the [Fe (PM-BiA) sub 2 (NCS) sub 2], cis-bis(thiocyanato)-bis[(N-2'-pyridylmethylene)-4-(aminobiphenyl)] iron(II), compound which exhibits, depending on the synthetic method, an exceptionally abrupt spin transition (phase 1) with a very narrow hysteresis (T sub 1 sub / sub 2 arrow down = 168 K and T sub 1 sub / sub 2 arrow up = 173 K) or a gradual spin conversion (phase II) occurring at 190 K. In both cases, light irradiation in the tail of the sup 1 MLCT-LS absorption band, at 830 nm, results in the population of the high-spin state according to the light-induced excited spin-state trapping (LIESST) effect. The capacity of a compound to retain the light-induced HS information, estimated through the T(LIESST) experiment, is determined for both phases. Interestingly, the shape of the T(LIESST) curve is more gradual for the phase II than for the phase I and the T(LIESST) value is found considerably lower in the case of the phase II. The kinetic...

  15. Crystal structure of a chloride-bridged copper(II) dimer: piperazine-1,4-dium bis­(di-μ-chlorido-bis[(4-carboxypyridine-2-carboxyl­ato-κ2 N,O 2)chlorido­cuprate(II)

    Science.gov (United States)

    Inah, Bassey Enyi; Adhikary, Amit

    2017-01-01

    Crystals of a new dimeric chloride-bridged cuprate(II) derived from pyridine-2,4-di­carb­oxy­lic acid were obtained solvothermally in the presence of piperazine and hydro­chloric acid. The crystal structure determination of the title salt, (C4H12N2)[Cu2(C7H4NO4)2Cl4], revealed one of the carboxyl groups of the original pyridine-2,4-di­carb­oxy­lic acid ligand to be protonated, whereas the other is deprotonated and binds together with the pyridine N atom to the CuII atom. The coordination environment of the CuII atom is distorted square-pyramidal. One of the chloride ligands bridges two metal cations to form a centrosymmetric dimer with two different Cu—Cl distances of 2.2632 (8) and 2.7853 (8) Å, whereby the longer distance is associated with the apical ligand. The remaining chloride ligand is terminal at one of the basal positions, with a distance of 2.2272 (9) Å. In the crystal, the dimers are linked by inter­molecular O—H⋯O hydrogen bonds, together with N—H⋯O and N—H⋯Cl inter­actions involving the centrosymmetric organic cation, into a three-dimensional supra­molecular network. Further but weaker C—H⋯O and C—H⋯Cl inter­actions consolidate the packing. PMID:28217352

  16. Importance of Fe(II)-Hydroxide Complexes For the In-Situ Bioremediation of ARD Sites

    Science.gov (United States)

    Bilgin, A.; Silverstein, J.; Nordstrom, D. K.

    2003-12-01

    Enhancing the growth of heterotrophic bacteria such as Acidiphilium cryptum that are indigenous to acid rock drainage (ARD) sources is a potential strategy for in-situ inhibition of pyrite oxidation and acid formation. When biodegradable organic carbon was supplied to A. cryptum, oxygen was consumed by rapidly growing heterotrophs, and bacterial iron reduction observed, accompanied by increasing solution pH. A. cryptum (ATCC 33463) cells were incubated in well-aerated liquid media containing Fe2(SO4)3 and glucose at varying initial pH values from 1.5 to 3.5. No more than 1% of the added ferric iron was detected as soluble Fe3+ for any of the media, indicating that the A. cryptum cells were able to reduce precipitated ferric iron. No organic carbon consumption or iron reduction was observed in flasks incubated at pH 1.5 indicating that A. cryptum may not be able to grow at this low pH. In reactors where the initial pH was 3.5, the pH increased to approximately 5.5 during the experiment accompanied by a 0.4 gl-1 decrease in Fe(III) species after aeration stopped. In reactors where the initial pH was 2.5, final pH values were inconsistent between replicate experiments: pH decreased to 2.3 in one experiment and increased to 2.8 in the second. Dissociation of Fe(OH)2+ complexes at pH values near 2.5 could have acted as a buffer, minimizing pH change during iron respiration. The existence of Fe(OH)2+ complexes was investigated using O-square wave voltametry, a pulse polarography technique which allows for identification of metal complexes and estimation of complex stability constants. The presence of ferric hydroxide complexes at pH near 2.5 was confirmed by pulse polarography. When the initial pH was 3.5, the base neutralizing capacity of the solution decreased due to the replacement of Fe(OH)2+ by Fe(OH)3 resulting in the pH increase of over 2 units.

  17. Adsorption and separation of CO{sub 2} on Fe(II)-MOF-74: Effect of the open metal coordination site

    Energy Technology Data Exchange (ETDEWEB)

    Lou, Wolong; Yang, Jiangfeng; Li, Libo; Li, Jinping, E-mail: Jpli211@hotmail.com

    2014-05-01

    We describe the successful synthesis of Fe{sub 2}(dobdc) (dobdc{sup 4−}=2, 5-dioxido-1, 4-benzenedicarboxylate), which has an open metal coordination site Fe(II), and investigate the adsorption properties of three important molecules CO{sub 2}, CH{sub 4} and N{sub 2} on Fe{sub 2}(dobdc) and an oxidized analog, Fe{sub 2}(O{sub 2})(dobdc). We found that CO{sub 2} adsorption isotherm of Fe{sub 2}(dobdc) at 10 bar was very different from Fe{sub 2}(O{sub 2})(dobdc), with the capacities of 144.5 cm{sup 3} g{sup −1} and 98.1 cm{sup 3} g{sup −1}, respectively. The adsorption capacities for CH{sub 4} were 75.8 cm{sup 3} g{sup −1} and 36.8 cm{sup 3} g{sup −1}, respectively, at 10 bar in these materials. Using ideal adsorbed solution theory (IAST), we obtain the adsorption selectivity for CO{sub 2} using equimolar mixtures of CO{sub 2}/CH{sub 4} and CO{sub 2}/N{sub 2} with Fe{sub 2}(dobdc) and Fe{sub 2}(O{sub 2})(dobdc) as a function of pressure. Fe{sub 2}(dobdc) has a higher, more stable separation factor. - Graphical abstract: The selectivity of CO{sub 2}/CH{sub 4} mixture (50%/50%) on Fe{sub 2}(dobdc) and Fe{sub 2}(O{sub 2})(dobdc). - Highlights: • We explored the contrastive adsorption of CO{sub 2}, CH{sub 4}, and N{sub 2} in Fe{sub 2}(dobdc) and Fe{sub 2}(O{sub 2})(dobdc) for the first time. • Through IAST, we obtain the adsorption selectivity for CO{sub 2} from the equimolar mixture of CO{sub 2}/CH{sub 4} and CO{sub 2}/N{sub 2} for Fe{sub 2}(dobdc) and Fe{sub 2}(O{sub 2})(dobdc). • We determined that the open coordination site of Fe(II) is the main reason for different adsorption performances.

  18. Sequential extraction method for determination of Fe(II/III) and U(IV/VI) in suspensions of iron-bearing phyllosilicates and uranium.

    Science.gov (United States)

    Luan, Fubo; Burgos, William D

    2012-11-06

    Iron-bearing phyllosilicates strongly influence the redox state and mobility of uranium because of their limited hydraulic conductivity, high specific surface area, and redox reactivity. Standard extraction procedures cannot be accurately applied for the determination of clay-Fe(II/III) and U(IV/VI) in clay mineral-U suspensions such that advanced spectroscopic techniques are required. Instead, we developed and validated a sequential extraction method for determination of clay-Fe(II/III) and U(IV/VI) in clay-U suspensions. In our so-called "H(3)PO(4)-HF-H(2)SO(4) sequential extraction" method, H(3)PO(4)-H(2)SO(4) is used first to solubilize and remove U, and the remaining clay pellet is subject to HF-H(2)SO(4) digestion. Physical separation of U and clay eliminates valence cycling between U(IV/VI) and clay-Fe(II/III) that otherwise occurred in the extraction solutions and caused analytical discrepancies. We further developed an "automated anoxic KPA" method to measure soluble U(VI) and total U (calculate U(IV) by difference) and modified the conventional HF-H(2)SO(4) digestion method to eliminate a series of time-consuming weighing steps. We measured the kinetics of uraninite oxidation by nontronite using this sequential extraction method and anoxic KPA method and measured a stoichiometric ratio of 2.19 ± 0.05 mol clay-Fe(II) produced per mol U(VI) produced (theoretical value of 2.0). We found that we were able to recover 98.0-98.5% of the clay Fe and 98.1-98.5% of the U through the sequential extractions. Compared to the theoretical stoichiometric ratio of 2.0, the parallel extractions of 0.5 M HCl for clay-Fe(II) and 1 M NaHCO(3) for U(VI) leached two-times more Fe(II) than U(VI). The parallel extractions of HF-H(2)SO(4) for clay Fe(II) and 1 M NaHCO(3) for U(VI) leached six-times more Fe(II) than U(VI).

  19. Genome-wide profiling of PPARgamma:RXR and RNA polymerase II occupancy reveals temporal activation of distinct metabolic pathways and changes in RXR dimer composition during adipogenesis

    DEFF Research Database (Denmark)

    Nielsen, Ronni; Pedersen, Thomas Askov; Hagenbeek, Dik;

    2008-01-01

    with deep sequencing to generate genome-wide maps of PPARgamma and retinoid X receptor (RXR)-binding sites, and RNA polymerase II (RNAPII) occupancy at very high resolution throughout adipocyte differentiation of 3T3-L1 cells. We identify >5000 high-confidence shared PPARgamma:RXR-binding sites...

  20. Synthetic, structural, spectroscopic and theoretical study of a Mn(III)-Cu(II) dimer containing a Jahn-Teller compressed Mn ion

    DEFF Research Database (Denmark)

    Berg, Nelly; Hooper, Thomas N.; Liu, Junjie;

    2013-01-01

    The heterobimetallic complex [Cu(II)Mn(III)(L)(2)(py)(4)](ClO(4))·EtOH (1) built using the pro-ligand 2,2'-biphenol (LH(2)), contains a rare example of a Jahn-Teller compressed Mn(III) centre. Dc magnetic susceptibility measurements on 1 reveal a strong antiferromagnetic exchange between the Cu(I...

  1. Mononuclear diastereopure non-heme Fe(II) complexes of pentadentate ligands with pyrrolidinyl moieties: structural studies, and alkene and sulfide oxidation

    NARCIS (Netherlands)

    Gosiewska, S.; Lutz, M.; Spek, A.L.; Klein Gebbink, R.J.M.

    2007-01-01

    Mononuclear iron(II) complexes of enantiopure Py(ProOH)2 (2) and Py(ProPh2OH)2(3) ligands have been prepared with FeCl2 and Fe(OTf)2 . 2MeCN. Both ligands coordinate to the metal in a pentadentate fashion. Next to the meridional N,N',N-coordination of the ligand, additional coordination of the

  2. N2O production in the Fe(II)(EDTA)-NO reduction process: the effects of carbon source and pH.

    Science.gov (United States)

    Chen, Jun; Wang, Lei; Zheng, Ji; Chen, Jianmeng

    2015-07-01

    Chemical absorption-biological reduction (BioDeNOx), which uses Fe(II)(EDTA) as a complexing agent for promoting the mass transfer efficiency of NO from gas to water, is a promising technology for removing nitric oxide (NO) from flue gases. The carbon source and pH are important parameters for Fe(II)(EDTA)-NO (the production of absorption) reduction and N2O emissions from BioDeNOx systems. Batch tests were performed to evaluate the effects of four different carbon sources (i.e., methanol, ethanol, sodium acetate, and glucose) on Fe(II)(EDTA)-NO reduction and N2O emissions at an initial pH of 7.2 ± 0.2. The removal efficiency of Fe(II)(EDTA)-NO was 93.9%, with a theoretical rate of 0.77 mmol L(-1) h(-1) after 24 h of operation. The highest N2O production was 0.025 mmol L(-1) after 3 h when glucose was used as the carbon source. The capacities of the carbon sources to enhance the activity of the Fe(II)(EDTA)-NO reductase enzyme decreased in the following order based on the C/N ratio: glucose > ethanol > sodium acetate > methanol. Over the investigated pH range of 5.5-8.5, the Fe(II)(EDTA)-NO removal efficiency was highest at a pH of 7.5, with a theoretical rate of 0.88 mmol L(-1) h(-1). However, the N2O production was lowest at a pH of 8.5. The primary effect of pH on denitrification resulted from the inhibition of nosZ in acidic conditions.

  3. Comparing the effects of Fe(III) and Cu(II) on the binding affinity of erlotinib to bovine serum albumin using spectroscopic methods

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yan [The State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Chen, Mingmao [Institute of Biomedical and Pharmaceutical Technology, Fuzhou University, Fuzhou, Fujian 350002 (China); Song, Ling, E-mail: songling@fjirsm.ac.cn [The State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)

    2013-02-15

    The interactions between erlotinib (ET) and bovine serum albumin (BSA) in the absence and presence of Cu(II) and Fe(III) in aqueous solution were investigated by using fluorescence, circular dichroism and three-dimensional (3D) fluorescence spectroscopic methods under simulative physiological conditions. Erlotinib effectively quenched the intrinsic fluorescence of BSA with slight redshifts in the absence and presence of Cu(II) and Fe(III). Cu(II) decreased the binding affinity and reduced the binding sites of erlotinib to BSA, while Fe(III) increased the binding affinity and binding sites of erlotinib to BSA. The negative values of {Delta}H and {Delta}S illustrate that the binding is mainly driven by the hydrogen bond and van der Waals force. The conformation of BSA was changed through ET binding in the presence of Cu(II) and Fe(III), which was revealed by circular dichroism, synchronous fluorescence and 3D fluorescence spectroscopic methods. The results indicate that the binding capability of erlotinib to BSA is affected by the types of metal ions. Highlights: Black-Right-Pointing-Pointer Interaction of erlotinib (ET) with BSA in the presence of Cu(II) and Fe(III) was studied. Black-Right-Pointing-Pointer Using various spectroscopic methods such as UV, CD, fluorescence and three-dimensional (3D) fluorescence. Black-Right-Pointing-Pointer Effects of metal ions on the binding activity of ET to BSA have not been reported. Black-Right-Pointing-Pointer Ternary system Cu(II)/Fe(III)-ET-BSA induced the conformational change of BSA.

  4. Highly sensitive amperometric sensor for micromolar detection of trichloroacetic acid based on multiwalled carbon nanotubes and Fe(II)–phtalocyanine modified glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Kurd, Masoumeh [Department of Chemistry, University of Kurdistan, P. O. Box 416, Sanandaj (Iran, Islamic Republic of); Salimi, Abdollah, E-mail: absalimi@uok.ac.ir [Department of Chemistry, University of Kurdistan, P. O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P. O. Box 416, Sanandaj (Iran, Islamic Republic of); Hallaj, Rahman [Department of Chemistry, University of Kurdistan, P. O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2013-04-01

    A highly sensitive electrochemical sensor for the detection of trichloroacetic acid (TCA) is developed by subsequent immobilization of phthalocyanine (Pc) and Fe(II) onto multiwalled carbon nanotubes (MWCNTs) modified glassy carbon (GC) electrode. The GC/MWCNTs/Pc/Fe(II) electrode showed a pair of well-defined and nearly reversible redox couple correspondent to (Fe(III)Pc/Fe(II)Pc) with surface-confined characteristics. The surface coverage (Γ) and heterogeneous electron transfer rate constant (k{sub s}) of immobilized Fe(II)–Pc were calculated as 1.26 × 10{sup −10} mol cm{sup −2} and 28.13 s{sup −1}, respectively. Excellent electrocatalytic activity of the proposed GC/MWCNTs/Pc/Fe(II) system toward TCA reduction has been indicated and the three consequent irreversible peaks for electroreduction of CCl{sub 3}COOH to CH{sub 3}COOH have been clearly seen. The observed chronoamperometric currents are linearly increased with the concentration of TCA at concentration range up to 20 mM. Detection limit and sensitivity of the modified electrode were 2.0 μM and 0.10 μA μM{sup −1} cm{sup −2}, respectively. The applicability of the sensor for TCA detection in real samples was tested. The obtained results suggest that the proposed system can serve as a promising electrochemical platform for TCA detection. Highlights: ► Phthalocyanine (PC) and Fe(II) immobilized onto MWCNTs modified GC electrode. ► A pair of well-defined redox couple correspondent to (Fe(III)Pc/Fe(II)Pc) observed. ► Modified electrode shows excellent catalytic activity to electroreduction of CCl{sub 3}COOH. ► Amperometry and cyclic voltammetry techniques were used for detection of CCl{sub 3}COOH. ► Detection limit and sensitivity were 2.0 μM and 0.10 μA μM{sup −1} cm{sup −2}, respectively.

  5. Synthesis, characterization and magnetic properties of carbon nanotubes decorated with magnetic M{sup II}Fe{sub 2}O{sub 4} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ali, Syed Danish [National Centre for Physics, Quaid-e-Azam University Campus, Islamabad (Pakistan); Department of Chemistry, University of Engineering and Technology, Lahore (Pakistan); Hussain, Syed Tajammul, E-mail: dr_tajammul@yahoo.ca [National Centre for Physics, Quaid-e-Azam University Campus, Islamabad (Pakistan); Gilani, Syeda Rubina [Department of Chemistry, University of Engineering and Technology, Lahore (Pakistan)

    2013-04-15

    In this study, a simple, efficient and reproducible microemulsion method was applied for the successful decoration of carbon nanotubes (CNTs) with magnetic M{sup II}Fe{sub 2}O{sub 4} (M = Co, Ni, Cu, Zn) nanoparticles. The structure, composition and morphology of the prepared nanocomposite materials were characterized using X-ray diffraction (XRD), Rutherford backscattering spectroscopy (RBS), Fourier transform infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM). The magnetic properties were investigated by the vibrating sample magnetometer (VSM). The SEM results illustrated that large quantity of M{sup II}Fe{sub 2}O{sub 4} nanoparticles were uniformly decorated around the circumference of CNTs and the sizes of the nanoparticles ranged from 15 to 20 nm. Magnetic hysteresis loop measurements revealed that all the M{sup II}Fe{sub 2}O{sub 4}/CNTs nanocomposites displayed ferromagnetic behavior at 300 K and can be manipulated using an external magnetic field. The CoFe{sub 2}O{sub 4}/CNTs nanocomposite showed maximum value of saturation magnetization which was 37.47 emu g{sup −1}. The as prepared M{sup II}Fe{sub 2}O{sub 4}/CNTs nanocomposites have many potential application in magnetically guided targeted drug delivery, clinical diagnosis, electrochemical biosensing, magnetic data storage and magnetic resonance imaging.

  6. Speciation analysis of Mn(II)/Mn(VII) using Fe3O4@ionic liquids-β-cyclodextrin polymer magnetic solid phase extraction coupled with ICP-OES.

    Science.gov (United States)

    Chen, Songqing; Qin, Xingxiu; Gu, Weixi; Zhu, Xiashi

    2016-12-01

    Ionic liquids-β-cyclodextrin polymer (ILs-β-CDCP) was attached on Fe3O4 nanoparticles to prepare magnetic solid phase extraction agent (Fe3O4@ILs-β-CDCP). The properties and morphology of Fe3O4@ILs-β-CDCP were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction(XRD), size distribution and magnetic analysis. A new method of magnetic solid phase extraction (MSPE) coupled to ICP-OES for the speciation of Mn(II)/Mn(VII) in water samples was established. The results showed that Mn(VII) and total manganese [Mn(II)+Mn(VII)] were quantitatively extracted after adjusting aqueous sample solution to pH 6.0 and 10.0, respectively. Mn(II) was calculated by subtraction of Mn(VII) from total manganese. Fe3O4@ILs-β-CDCP showed a higher adsorption capacity toward Mn(II) and Mn(VII). Several factors, such as the pH value, extraction temperature and sample volume, were optimized to achieve the best extraction efficiency. Moreover, the adsorption ability of Fe3O4@ILs-β-CDCP would not be significantly lower after reusing of 10 times. The accuracy of the developed method was confirmed by analyzing certified reference materials (GSB 07-1189-2000), and by spiking spring water, city water and lake water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Sub-micron-sized polyethylenimine-modified polystyrene/Fe3O4/chitosan magnetic composites for the efficient and recyclable adsorption of Cu(II) ions

    Science.gov (United States)

    Xiao, Changwei; Liu, Xijian; Mao, Shimin; Zhang, Lijuan; Lu, Jie

    2017-02-01

    A sub-micron-sized polyethylenimine(PEI)-modified polystyrene/Fe3O4/chitosan magnetic composite (PS/Fe3O4/CS-PEI) was developed as a novel adsorbent for the removal of Cu(II) ions from aqueous solutions. The PS/Fe3O4/CS-PEI microspheres with a diameter of ∼300 nm can be highly monodisperse and conveniently separated from suspensions by a magnet due to their excellent magnetism. When the PS/Fe3O4/CS-PEI microspheres were used as an absorbent for the absorption of Cu(II) ions, the adsorption isotherms and adsorption kinetics well fitted the Langmuir model and the pseudo-second-order model, respectively. The maximum adsorption capacity was about 204.6 mg g-1, which was higher than those of other chitosan adsorbents reported recently. The adsorption was considerably fast, reaching the equilibrium within 15 min. In addition, the adsorbed Cu(II) ions could be effectively desorbed using 0.1 mol L-1 NaOH solution, and the regeneration study proved that the composite microspheres could be repeatedly utilized without significant capacity loss after six cycles. All the results demonstrated that the synthesized sub-micron-sized magnetic PS/Fe3O4/CS-PEI composites can be used as an ideal adsorbent of Cu(II) ions for environmental cleanup applications.

  8. Anoxygenic growth of cyanobacteria on Fe(II) and their associated biosignatures: Implications for biotic contributions to Precambrian Banded Iron Formations

    Science.gov (United States)

    Parenteau, M.; Jahnke, L. L.; Cady, S. L.; Pierson, B.

    2011-12-01

    Banded Iron Formations (BIFs) are widespread Precambrian sedimentary deposits that accumulated in deep ocean basins or shallow platformal areas with inputs of reduced iron (Fe(II)) and silica from deep ocean hydrothermal activity. There is debate as to whether abiotic or biotic mechanisms were responsible for the oxidation of aqueous Fe(II) and the subsequent accumulation of ferric iron (Fe(III)) mineral assemblages in BIFs. Biotic Fe(II) oxidation could have occurred indirectly as a result of the photosynthetic production of oxygen by cyanobacteria, or could have been directly mediated by anoxygenic phototrophs or chemolithotrophs. The anoxygenic use of Fe(II) as an electron donor for photosynthesis has also been hypothesized in cyanobacteria, representing another biotic mechanism by which Fe(II) could be oxidized in BIFs. This type of photoferrotrophic metabolism may also represent a key step in the evolution of oxygenic photosynthesis. Members of our group have speculated that an intermediate reductant such as Fe(II) could have acted as a transitional electron donor before water. The widespread abundance of Fe(II) in Archean and Neoproterozoic ferruginous oceans would have made it particularly suitable as an electron donor for photosynthesis. We have been searching for modern descendants of such an ancestral "missing link" cyanobacterium in the phototrophic mats at Chocolate Pots, a hot spring in Yellowstone National Park with a constant outflow of anoxic Fe(II)-rich thermal water. Our physiological ecology study of the Synechococcus-Chloroflexi mat using C-14 bicarbonate uptake and autoradiography experiments revealed that the cyanobacteria grow anoxygenically using Fe(II) as an electron donor for photosynthesis in situ. An initial set of similar experiments substituting C-13 bicarbonate as the tracer was used to characterize labeling of the community lipid biomarker signature and confirm the C-14 results. Under light conditions with and without Fe(II), the C

  9. Electronic spectra and photophysics of platinum(II) complexes with alpha-diimine ligands - Solid-state effects. I - Monomers and ligand pi dimers

    Science.gov (United States)

    Miskowski, Vincent M.; Houlding, Virginia H.

    1989-01-01

    Two types of emission behavior for Pt(II) complexes containing alpha-diimine ligands have been observed in dilute solution. If the complex also has weak field ligands such as chloride, ligand field (d-d) excited states become the lowest energy excited states. If only strong field ligands are present, a diimine 3(pi-pi/asterisk/) state becomes the lowest. In none of the cases studied did metal-to-ligand charge transfer excited state lie lowest.

  10. Nickel incorporation in Fe(II, III hydroxysulfate Green Rust: effect on crystal lattice spacing and oxidation products Incorporação de níquel em Fe (II-III Grenn Rust hidroxisulfato: efeito sobre a estrutura cristalina e produtos de oxidação

    Directory of Open Access Journals (Sweden)

    Lucia Helena Garófalo Chaves

    2009-10-01

    Full Text Available Ni(II-Fe(II-Fe(III layered double hydroxides (LDH or Ni-containing sulfate green rust (GR2 samples were prepared from Ni(II, Fe(II and Fe(III sulfate salts and analyzed with X ray diffraction. Nickel is readily incorporated in the GR2 structure and forms a solid solution between GR2 and a Ni(II-Fe(III LDH. There is a correlation between the unit cell a-value and the fraction of Ni(II incorporated into the Ni(II-GR2 structure. Since there is strong evidence that the divalent/trivalent cation ratio in GR2 is fixed at 2, it is possible in principle to determine the extent of divalent cation substitution for Fe(II in GR2 from the unit cell a-value. Oxidation forms a mixture of minerals but the LDH structure is retained if at least 20 % of the divalent cations in the initial solution are Ni(II. It appears that Ni(II is incorporated in a stable LDH structure. This may be important for two reasons, first for understanding the formation of LDHs, which are anion exchangers, in the natural environment. Secondly, this is important for understanding the fate of transition metals in the environment, particularly in the presence of reduced Fe compounds.Amostras de hidróxidos de dupla camada (HDC, ou "sulfate green rust" (GR2, contendo Ni foram preparadas utilizando-se sulfatos de Ni(II, Fe(II e Fe(III e analisadas por difração de raios X. O Ni está incorporado na estrutura do GR2 e forma um sólido entre GR2 e um HDC contendo Ni(II-Fe(III. Há correlação entre os valores de "a" da célula unitária e os da fração de Ni(II incorporado na estrutura do Ni(II-GR2. Desde que haja forte evidência de que a razão entre os cátions divalente/trivalente no GR2 seja igual a 2, é possível, a princípio, determinar a extensão da substituição do cátion divalente por Fe(II no GR2 a partir dos valores de "a" da célula unitária do cristal. Sob o efeito da oxidação, é formada uma mistura de minerais, porém a estrutura do HDC não é alterada se pelo menos

  11. Tri-μ-ethanethiolato-bis{[η5-1,2,3,4-tetramethyl-5-(trimethylsilylcyclopentadienyl]iron(II,III}(FeII–FeIII

    Directory of Open Access Journals (Sweden)

    Jing Li

    2009-12-01

    Full Text Available The title complex, [Fe2(C2H5S3(C12H21Si2], has an unusual Fe2S3 core. The two 1,2,3,4-tetramethyl-5-(trimethylsilylcyclopentadienyl (Cp′ ligands coordinate to the Fe atoms with their C5 planes perpendicular [dihedral angles = 88.23 (7 and 88.55 (7°] to the Fe—Fe vector, building two Cp′Fe subunits. These two subunits are bridged by three thiolate ligands. There are no significant differences in the coordination geometries between the two Fe atoms. The short Fe—Fe distance of 2.7842 (5 Å is clear evidence of an intermetallic bond. Such a diiron–sulfur structure might act as a model of active sites in some metalloproteins.

  12. Cadmium (II) and lead (II) transport in a polymer inclusion membrane using tributyl phosphate as mobile carrier and CuFeO(2) as a polarized photo electrode.

    Science.gov (United States)

    Arous, Omar; Amara, Mourad; Trari, Mohamed; Bouguelia, Aissa; Kerdjoudj, Hacène

    2010-08-15

    In this work, a development of polymeric inclusion membranes for the cations separation is reported. The membrane was made up of cellulose triacetate (CTA) with a tributyl phosphate (TBP) incorporated into the polymer as metal ions carrier. The transport of lead (II) and cadmium (II) ions in two membrane systems polymer inclusion membrane (PIM), PIM coupled with photo-chemical electrode using TBP as carrier and 2-nitro phenyl octyl ether (NPOE) or tris ethylhexyl phosphate (TEHP) as plasticizer have been investigated. The membranes: polymer+plasticizer+carrier were synthesized and characterized by FTIR, X-ray diffraction and scanning electron microscopy (SEM). Transports of lead and cadmium have been studied using these systems and the results were compared to commercial cation exchange membrane (CRA). The obtained results showed that for Pb(2+) ion, the concentrations of the strip phase increases using synthesized membranes. The conduction band of the delafossite CuFeO(2) (-1.25 V(SCE)) yields a thermodynamically M(2+) (=Pb(2+), Cd(2+)) photo electrodeposition and speeds up the diffusion process. In all the cases, the potential of the electrode M/M(2+) in the feed compartment increases until a maximum value, reached at approximately 100 min above which it undergoes a diminution.

  13. Synthesis, thermogravimetric analysis, infrared, electronic and mass spectra of Mn(II), Co(II) and Fe(III) norfloxacin complexes

    Science.gov (United States)

    Sadeek, Sadeek A.

    2005-10-01

    The interactions of manganese acetate, ferric chloride and cobalt sulphate with norfloxacin (NOR) in acetone or methanol were studied. The isolated solid complexes were characterized by elemental analysis, infrared, electronic, mass spectra and thermal analysis. The results support the formation of complexes of the formula [Fe(NOR) 3]Cl 3·12H 2O and [M(NOR) 2]X 2·8H 2O (M=Mn(II) or Co(II) and X=(CH 3COO -) or SO4-2). The infrared spectra of the isolated solid complexes suggested, indicated that NOR act as bidentate ligands through one of the oxygen atoms of the carboxylic group and the ring carbonyl oxygen atom. The interpretation, mathematical analysis and evaluation of kinetic parameters of thermogravimetric (TGA) and its differential (DTG), such as entropy of activation, pre-exponential factors, activation energy evaluated by using Coats-Redfern and Horowitz-Metzger equations for two complexes are carried out. General mechanisms describing the decomposition of the solid complexes are suggested.

  14. Superbackscattering nanoparticle dimers.

    Science.gov (United States)

    Liberal, Iñigo; Ederra, Iñigo; Gonzalo, Ramón; Ziolkowski, Richard W

    2015-07-10

    The theory and design of superbackscattering nanoparticle dimers are presented. We analytically derive the optimal configurations and the upper bound of their backscattering cross-sections. In particular, it is demonstrated that electrically small nanoparticle dimers can enhance the backscattering by a factor of 6.25 with respect to single dipolar particles. We demonstrate that optimal designs approaching this theoretical limit can be found by using a simple circuit model. The study of practical implementations based on plasmonic and high-permittivity particles has been also addressed. Moreover, the numerical examples reveal that the dimers can attain close to a fourfold enhancement of the single nanoparticle response even in the presence of high losses.

  15. Monitoring, field experiments, and geochemical modeling of Fe(II) oxidation kinetics in a stream dominated by net-alkaline coal-mine drainage, Pennsylvania, USA

    Science.gov (United States)

    Cravotta, Charles A.

    2015-01-01

    Watershed-scale monitoring, field aeration experiments, and geochemical equilibrium and kinetic modeling were conducted to evaluate interdependent changes in pH, dissolved CO2, O2, and Fe(II) concentrations that typically take place downstream of net-alkaline, circumneutral coal-mine drainage (CMD) outfalls and during aerobic treatment of such CMD. The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO2 outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law −d[Fe(II)]/dt = k1·[O2]·[H+]−2·[Fe(II)] that indicates an increase in pH by 1 unit at pH 5–8 and at constant dissolved O2 (DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant (k1′) of 0.5–1.7 times the reference value of k1 = 3 × 10−12 mol/L/min (for pH 5–8 and 20 °C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO2 outgassing and O2ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the

  16. Pretreatment of furfural industrial wastewater by Fenton, electro-Fenton and Fe(II)-activated peroxydisulfate processes: a comparative study.

    Science.gov (United States)

    Yang, C W; Wang, D; Tang, Q

    2014-01-01

    The Fenton, electro-Fenton and Fe(II)-activated peroxydisulfate (PDS) processes have been applied for the treatment of actual furfural industrial wastewater in this paper. Through the comparative study of the three processes, a suitable pretreatment technology for actual furfural wastewater treatment was obtained, and the mechanism and dynamics process of this technology is discussed. The experimental results show that Fenton technology has a good and stable effect without adjusting pH of furfural wastewater. At optimal conditions, which were 40 mmol/L H₂O₂ initial concentration and 10 mmol/L Fe²⁺ initial concentration, the chemical oxygen demand (COD) removal rate can reach 81.2% after 90 min reaction at 80 °C temperature. The PDS process also has a good performance. The COD removal rate could attain 80.3% when Na₂S₂O₈ initial concentration was 4.2 mmol/L, Fe²⁺ initial concentration was 0.1 mol/L, the temperature remained at 70 °C, and pH value remained at 2.0. The electro-Fenton process was not competent to deal with the high-temperature furfural industrial wastewater and only 10.2% COD was degraded at 80 °C temperature in the optimal conditions (2.25 mA/cm² current density, 4 mg/L Na₂SO₄, 0.3 m³/h aeration rate). For the Fenton, electro-Fenton and PDS processes in pretreatment of furfural wastewater, their kinetic processes follow the pseudo first order kinetics law. The pretreatment pathways of furfural wastewater degradation are also investigated in this study. The results show that furfural and furan formic acid in furfural wastewater were preferentially degraded by Fenton technology. Furfural can be degraded into low-toxicity or nontoxic compounds by Fenton pretreatment technology, which could make furfural wastewater harmless and even reusable.

  17. Emissão de hidrogênio molecular e [FeII] em núcleos Seyfert

    Science.gov (United States)

    Rodríguez-Ardila, A.; Pastoriza, M. G.; Viegas, S.

    2003-08-01

    Um dos problemas fundamentais em núcleos ativos de galáxias (AGN) é determinar os mecanismos de excitação dominantes do gás emissor de linhas estreitas, seja este excitado por mecanismos não-estelares (fotoionização por uma fonte central ou choques produzidos por um jato rádio no gás circumnuclear) ou estelares (fotoionização por estrelas OB ou choques originados por um remanescente de supernova em expansão). Essa ambiguedade se faz mais evidente ao intepretar o espectro de espécies tais como H2 e [FeII]. Na primeira, fluorescência UV, processos térmicos (choques e/ou aquecimento por fótons) ou illuminação por raios-x, podem ser responsáveis pelo espectro observado enquanto que na segunda, os dois últimos mechanismos seriam relevantes. Neste trabalho, utilizando espectroscópia JHK de média resolução para uma amostra de AGN encontramos que o H2 observado é gerado principalmente por processos térmicos associados à presença de episódios de formação estelar circumnuclear. No entanto, em galáxias tais como NGC4151 as observações mostram que o hidrogênio molecular origina-se, principalmente, da interação entre o jato radio e o gás da NLR. Esses resultados baseiam-se nos valores das razões de linhas H2 2.24/2.12 mm e H2 2.03/2.22 mm. H2 2.24/2.12 separa claramente processos não-térmicos dos térmicos enquanto H2 2.03/2.22 serve como indicador de temperatura da componente térmica, e portanto, discrimina entre choques e associações OB. Já para o [FeII], as observações são compatíveis com excitação produzida diretamente pela fonte central ou choques associados com o jato rádio. A comparação da largura dos perfis de linhas observados permite concluir que não há correlação entre a emissão de H2 e [FeII]. Em praticamente todos os casos analisados, os perfis das linhas de H2 são não-resolvidos, enquanto que os perfis de [FeII] indicam, em alguns casos, velocidades de até 600 km/s.

  18. Superbackscattering Nanoparticle Dimers

    CERN Document Server

    Liberal, Iñigo; Gonzalo, Ramón; Ziolkoski, Richard W

    2015-01-01

    The theory and design of superbackscattering nanoparticle dimers are presented. We analytically derive the optimal configurations and the upper bound of their backscattering cross-sections. In particular, it is demonstrated that electrically small nanoparticle dimers can enhance the backscattering by a factor of 6.25 with respect to single dipolar particles. We demonstrate that optimal designs approaching this theoretical limit can be found by using a simple circuit model. The study of practical implementations based on plasmonic and high-permittivity particles reveal that fourfold enhancement factors might be attainable even with realistic losses.

  19. Synthesis, characterization, fluorescence and biological studies of Mn(II, Fe(III and Zn(II complexes of Schiff bases derived from Isatin and 3-substituted-4-amino-5-mercapto-1,2,4-triazoles

    Directory of Open Access Journals (Sweden)

    Sangamesh A. Patil

    2014-12-01

    Full Text Available A series of Mn(II, Fe(III and Zn(II complexes have been synthesized with Schiff bases derived from isatin and 3-substituted-4-amino-5-mercapto-1,2,4-triazole. The elemental, spectroscopic (Infrared, nuclear magnetic resonance, ultraviolet-visible, fast atom bombardment-mass, fluorescence and electrochemistry and magnetic studies suggested that the metal complexes possess octahedral geometry. The Schiff bases and their metal complexes exhibit fluorescent properties. The antimicrobial studies of Schiff bases and their metal complexes against various bacterial (Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Bacillus subtilis and fungal (Aspergillus niger, and Penicillium chrysogenum species by the minimum inhibitory concentration method revealed that the metal complexes possess more healing antibacterial activities than the Schiff bases. DNA cleavage property of Mn(II, Fe(III and Zn(II complexes revealed the important role of metal ion in the biological system.

  20. Metal membrane with dimer slots as a universal polarizer

    DEFF Research Database (Denmark)

    Zhukovsky, Sergei; Zalkovskij, Maksim; Malureanu, Radu

    2014-01-01

    In this work, we show theoretically and confirm experimentally that thin metal membranes patterned with an array of slot dimers (or their Babinet analogue with metal rods) can function as a versatile spectral and polarization filter. We present a detailed covariant multipole theory...... for the electromagnetic response of an arbitrary dimer based on the Green functions approach. The theory confirms that a great variety of polarization properties, such as birefringence, chirality and elliptical dichroism, can be achieved in a metal layer with such slot-dimer patterning (i.e. in a metasurface). Optical...... properties of the metasurface can be extensively tuned by varying the geometry (shape and dimensions) of the dimer, for example, by adjusting the sizes and mutual placement of the slots (e.g. inter-slot distance and alignment angle). Three basic shapes of dimers are analyzed: II-shaped (parallel slots), V...

  1. Alkane dimers interaction

    DEFF Research Database (Denmark)

    Ferrighi, Lara; Madsen, Georg Kent Hellerup; Hammer, Bjørk

    2010-01-01

    The interaction energies of a series of n-alkane dimers, from methane to decane, have been investigated with Density Functional Theory (DFT), using the MGGA-M06-L density functional. The results are compared both to the available wavefunction-based values as well as to dispersion corrected DFT...

  2. Bis(imino)pyridine (BIMP) Fe(II) catalyses one-pot green condensation of resorcinol, malononitrile, aromatic aldehydes and cyclohexanone

    Indian Academy of Sciences (India)

    Saman Damavandi; Reza Sandaroos

    2012-03-01

    A novel, efficient and green approach for the synthesis of pyranopyridine derivatives through one-pot, four-component reaction of resorcinol, malononitrile, aromatic aldehydes and cyclohexanone using bis(imino)pyridine (BIMP) Fe(II) catalyst under solvent-free and ultrasonic irradiation is described.

  3. c2d Spitzer IRS Spectra of Disks around T Tauri Stars. III. [Ne II], [Fe I], and H_2 gas-phase lines

    CERN Document Server

    Lahuis, Fred; Blake, Geoffrey A; Evans, Neal J; Kessler-Silacci, Jacqueline E; Pontoppidan, Klaus M

    2007-01-01

    We present a survey of mid-infrared gas-phase lines toward a sample of 76 circumstellar disks around low mass pre-main sequence stars from the Spitzer "Cores to Disks" legacy program. We report the first detections of [Ne II] and [Fe I] toward classical T Tauri stars in ~20% respectively ~9% of our sources. The observed [Ne II] line fluxes and upper limits are consistent with [Ne II] excitation in an X-ray irradiated disk around stars with X-ray luminosities L_X=10^{29}-10^{31} erg s^{-1}. [Fe I] is detected at ~10^-5-10^-4 L_Sun, but no [S I] or [Fe II] is detected down to ~10^{-6} L_Sun. The [Fe I] detections indicate the presence of gas-rich disks with masses of >~0.1 M_J. No H_2 0-0 S(0) and S(1) disk emission is detected, except for S(1) toward one source. These data give upper limits on the warm (T~100-200K) gas mass of a few Jovian masses, consistent with recent T Tauri disk models which include gas heating by stellar radiation. Compact disk emission of hot (T>~500K) gas is observed through the H_2 0-0...

  4. Simultaneous determination of Mn(II), Cu(II) and Fe(III) as 2-(5'-bromo-2'-pyridylazo)-5-diethylaminophenol complexes by adsorptive cathodic stripping voltammetry at a carbon paste electrode.

    Science.gov (United States)

    Ghoneim, Enass M

    2010-07-15

    A simple and precise square-wave adsorptive cathodic stripping voltammetry (SW-AdCSV) method has been described for simultaneous determination of Mn(II), Cu(II) and Fe(III) in water samples using a carbon paste electrode. In 0.1 mol L(-1) acetate buffer (pH 5) containing 50 micromol L(-1) of 2-(5'-bromo-2'-pyridylazo)-5-diethylaminophenol (5-Br-PADAP), Mn(II), Cu(II) and Fe(III) were simultaneously determined as metal-complexes with 5-Br-PADAP following preconcentration onto the carbon paste electrode by adsorptive accumulation at +1.0V (vs. Ag/AgCl/3M KCl). Insignificant interference from various cations (K(+), Na(+), Mg(2+), Ca(2+), Al(3+), Bi(3+), Sb(3+), Se(4+), Zn(2+), Ni(2+), Co(2+), Cd(2+), Pb(2+), V(5+), Ti(4+) and NH(4)(+)), anions (HCO(3)(-), Cl(-), NO(3-), SO(4)(2-) and PO(4)(3-)) and ascorbic acid was noticed. Limits of detection of 0.066, 0.108 and 0.093 microg L(-1) and limits of quantitation of 0.22, 0.36 and 0.31 microg L(-1) Mn(II), Cu(II) and Fe(III), respectively, were achieved by the described method. The described stripping voltammetry method was successfully applied for simultaneous determination of Mn(II), Cu(II) and Fe(III) in ground, tap and bottled natural water samples. Copyright 2010 Elsevier B.V. All rights reserved.

  5. Simultaneous surface-adsorbed organic matter desorption and cell integrity maintenance by moderate prechlorination to enhance Microcystis aeruginosa removal in KMnO4Fe(II) process.

    Science.gov (United States)

    Qi, Jing; Lan, Huachun; Liu, Huijuan; Liu, Ruiping; Miao, Shiyu; Qu, Jiuhui

    2016-11-15

    The KMnO4Fe(II) process was proved to have good application potential in Microcystis aeruginosa removal, although at relatively high doses. This study aims to improve the algae removal in KMnO4Fe(II) process by moderate prechlorination, which can realize the desorption of surface-adsorbed organic matter (S-AOM) from algae cells without damaging cell integrity. S-AOM was proved to not only inhibit algae removal but also maintain cell integrity, using various dilution methods for algal suspension preparation. The dilution after filtration method mainly removed the dissolved organics in cultured M. aeruginosa, while the dilution after centrifugal cleaning method could also remove the S-AOM on algae cells. Compared with the S-AOM-removed algal suspension, the lower algae removal in KMnO4Fe(II) process and the reduced proportion of damaged cells during prechlorination of algal suspension without S-AOM removed indicated the inhibitory role of S-AOM in algae removal and the protective function of S-AOM toward cell integrity, respectively. Moderate prechlorination of directly diluted M. aeruginosa could be realized at chlorine doses of below 0.5 mg/L, and the damaged cell ratios were below 4% after 5-min prechlorination. The ability of the KMnO4Fe(II) process to remove algae was dramatically enhanced by the elevation of chlorine dose from 0 to 0.5 mg/L, as more S-AOM was desorbed during prechlorination. Additionally, algae cells were easily captured by flocs after moderate prechlorination, which benefited the floc aggregation for formation of tightly bounded algae flocs. Therefore, the desorption of S-AOM without damaging cell integrity is the key feature of moderate prechlorination, which can be applied in improving the algae removal of KMnO4Fe(II) process. Copyright © 2016. Published by Elsevier Ltd.

  6. Development of carbon nanotubes/CoFe{sub 2}O{sub 4} magnetic hybrid material for removal of tetrabromobisphenol A and Pb(II)

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Lincheng, E-mail: zhoulc@lzu.edu.cn [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Institute of Biochemical Engineering and Environmental Technology, Lanzhou University, Lanzhou 730000 (China); Ji, Liqin [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Institute of Biochemical Engineering and Environmental Technology, Lanzhou University, Lanzhou 730000 (China); Ma, Peng-Cheng [The Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi 830011 (China); Shao, Yanming; Zhang, He; Gao, Weijie; Li, Yanfeng [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Institute of Biochemical Engineering and Environmental Technology, Lanzhou University, Lanzhou 730000 (China)

    2014-01-30

    Highlights: • Amino-functionalized CoFe{sub 2}O{sub 4} nanoparticles were deposited on MWCNTs in one-pot. • Novel chitosan modified MWCNTs/CoFe{sub 2}O{sub 4} hybrid material were successfully synthesized. • The hybrid material had high specific surface area and abundant functional groups. • The hybrid material exhibited high adsorption properties for TBBPA and Pb(II). • The hybrid material was an efficient, eco-friendly and reusable adsorbent. -- Abstract: Multi-walled carbon nanotubes (MWCNTs) coated with magnetic amino-modified CoFe{sub 2}O{sub 4} (CoFe{sub 2}O{sub 4}–NH{sub 2}) nanoparticles (denoted as MNP) were prepared via a simple one-pot polyol method. The MNP composite was further modified with chitosan (CTS) to obtain a chitosan-functionalized MWCNT/CoFe{sub 2}O{sub 4}–NH{sub 2} hybrid material (MNP–CTS). The obtained hybrid materials were characterized by Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectrogram (FT-IR) Analysis and X-ray Photoelectron Spectroscopy (XPS) Analysis, Vibrating Sample Magnetometer (VSM) Analysis and the Brunauer–Emmett–Teller (BET) surface area method, respectively. The composites were tested as adsorbents for tetrabromobisphenol A (TBBPA) and Pb(II), and were investigated using a pseudo-second-order model. The adsorption of TBBPA was well represented by the Freundlich isotherm; the Langmuir model better described Pb(II) absorption. MNP–CTS adsorbed both TBBPA and Pb(II) (maximum adsorption capacities of 42.48 and 140.1 mg g{sup −1}, respectively) better than did MNP without CTS. Magnetic composite particles with adsorbed TBBPA and Pb(II) could be regenerated using 0.2 M NaOH solution and were separable from liquid media using a magnetic field.

  7. The Resistance of Electron Transport Chain Fe-S Clusters to Oxidative Damage during the Reaction of Peroxynitrite with Mitochondrial Complex II and Rat Heart Pericardium

    Science.gov (United States)

    Pearce, Linda L.; Martinez-Bosch, Sandra; Manzano, Elisenda Lopez; Winnica, Daniel E.; Epperly, Michael W.; Peterson, Jim

    2009-01-01

    The effects of peroxynitrite and nitric oxide on the iron-sulfur clusters in complex II (succinate dehydrogenase) isolated from bovine heart have been studied primarily by EPR spectroscopy and no measurable damage to the constitutive 2Fe-2S, 3Fe-4S, or 4Fe-4S clusters was observed. The enzyme can be repeatedly oxidized with a slight excess of peroxynitrite and then quantitatively re-reduced with succinate. When added in large excess, peroxynitrite reacted with at least one tyrosine in each subunit of complex II to form 3-nitrotyrosines, but activity was barely compromised. Examination of rat-heart pericardium subjected to conditions leading to peroxynitrite production showed a small inhibition of complex II (16%) and a greater inhibition of aconitase (77%). In addition, experiments performed with excesses of sodium citrate and sodium succinate on rat-heart pericardium indicated that the “g ~2.01” EPR signal observed immediately following the beginning of conditions modeling oxidative/nitrosative stress, could be a consequence of both reversible oxidation of the constitutive 3Fe-4S cluster in complex II and degradation of the 4Fe-4S cluster in aconitase. However, the net signal envelope, which becomes apparent in less than one minute following the start of oxidative/nitrosative conditions, is dominated by the component arising from complex II. Taking into account the findings of a previous study concerning complexes I and III [L.L. Pearce, A.J. Kanai, M.W. Epperly, J. Peterson (2005) Nitric Oxide 13, 254-63] it is now apparent that, with the exception of the cofactor in aconitase, mammalian (mitochondrial) iron-sulfur clusters are surprisingly resistant to degradation stemming from oxidative/nitrosative stress. PMID:19118636

  8. On the Oxidation of α-Fe and ε-Fe2N1-z : II. Residual Strains and Blisters in the Oxide Layer

    NARCIS (Netherlands)

    Kooi, Bart J.; Somers, Marcel A.J.; Jutte, Robin H.; Mittemeijer, Eric J.

    1997-01-01

    The development of residual strains in the iron-oxide layers growing on α-Fe and ε-Fe2N1-z at 673 K in O2 at 1 atm was investigated by X-ray diffraction at room temperature. After correction for thermal-strain development due to cooling after oxidation, it was found that tensile growth strains occur

  9. Structures of Fe(II) spin-crossover complexes from synchrotron powder-diffraction data.

    Science.gov (United States)

    Dova, Eva; Peschar, René; Sakata, Makoto; Kato, Kenichi; Stassen, Arno F; Schenk, Henk; Haasnoot, Jaap G

    2004-10-01

    Crystal structure determination and analysis have been carried out for the two spin-crossover compounds [Fe(teeX)(6)](BF(4))(2) (teeX is haloethyltetrazole; X = I: teei; X = Br: teeb), in both their high-spin (near 300 K) and their low-spin states (T = 90 K), using high-resolution powder-diffraction data collected at the ESRF (Grenoble, France) and SPring8 (Japan) synchrotron radiation facilities. The structures of teei have been solved using various direct-space structure determination techniques (grid search, genetic algorithm and parallel tempering) and refined with the Rietveld method using geometrical restraints. In the case of teeb, a structural model was found but a full refinement was not successful because of the presence of a significant amount of an amorphous component. Analysis of the structures (space group P2(1)/c, Z = 2) and diffraction data, and the absence of phase transitions, show the overall structural similarity of these compounds and lead to the conclusion that the gradual spin-crossovers are likely to be accompanied by small structural changes only.

  10. Mechanochemical synthesis and intercalation of Ca(II)Fe(III)-layered double hydroxides

    Science.gov (United States)

    Ferencz, Zs.; Szabados, M.; Varga, G.; Csendes, Z.; Kukovecz, Á.; Kónya, Z.; Carlson, S.; Sipos, P.; Pálinkó, I.

    2016-01-01

    A mechanochemical method (grinding the components without added water - dry grinding, followed by further grinding in the presence of minute amount of water or NaOH solution - wet grinding) was used in this work for the preparation and intercalation of CaFe-layered double hydroxides (LDHs). Both the pristine LDHs and the amino acid anion (cystinate and tyrosinate) intercalated varieties were prepared by the two-step grinding procedure in a mixer mill. By systematically changing the conditions of the preparation method, a set of parameters could be determined, which led to the formation of close to phase-pure LDH. The optimisation procedure was also applied for the intercalation processes of the amino acid anions. The resulting materials were structurally characterised by a range of methods (X-ray diffractometry, scanning electron microscopy, energy dispersive analysis, thermogravimetry, X-ray absorption and infra-red spectroscopies). It was proven that this simple mechanochemical procedure was able to produce complex organic-inorganic nanocomposites: LDHs intercalated with amino acid anions.

  11. Luminous and Variable Stars in M31 and M33. II. Luminous Blue Variables, Candidate LBVs, Fe II Emission Line Stars, and Other Supergiants

    CERN Document Server

    Humphreys, Roberta M; Davidson, Kris; Bomans, D J; Burggraf, Birgitta

    2014-01-01

    An increasing number of non-terminal eruptions are being found in the numerous surveys for optical transients. Very little is known about these giant eruptions, their progenitors and their evolutionary state. A greatly improved census of the likely progenitor class, including the most luminous evolved stars, the Luminous Blue Varaibles (LBVs), and the warm and cool hypergiants is now needed for a complete picture of the final pre-SN stages of very massive stars. We have begun a survey of the evolved and un stable luminous star populations in several nearby resolved galaxies. In this second paper on M31 and M33, we review the spectral characteristics, spectral energy distributions, circumstellar ejecta, and evidence for mass loss for 82 luminous and variable stars.We show that many of these stars have warm circumstellar dust including several of the Fe II emission line stars, but conclude that the confirmed LBVs in M31 and M33 do not. The confirmed LBVs have relatively low wind speeds even in their hot, quiesc...

  12. The Integrated Calcium II Triplet as a Metallicity Indicator: Comparisons with High Resolution [Fe/H] in M31 Globular Clusters

    CERN Document Server

    Sakari, Charli M

    2015-01-01

    Medium resolution (R=4,000 to 9,000) spectra of the near infrared Ca II lines (at 8498, 8542, and 8662 A) in M31 globular cluster integrated light spectra are presented. In individual stars the Ca II triplet (CaT) traces stellar metallicity; this paper compares integrated CaT strengths to well determined, high precision [Fe/H] values from high resolution integrated light spectra. The target globular clusters cover a wide range in metallicity (from [Fe/H] = -2.1 to -0.2). While most are older than 10 Gyr, some may be of intermediate age (2-6 Gyr). A handful (3-6) have detailed abundances (e.g. low [Ca/Fe]) that indicate they may have been accreted from dwarf galaxies. Using various measurements and definitions of CaT strength, it is confirmed that for GCs with [Fe/H] < -0.4 and older than 2 Gyr the integrated CaT traces cluster [Fe/H] to within about 0.2 dex, independent of age. CaT lines in metal rich GCs are very sensitive to nearby atomic lines (and TiO molecular lines in the most metal rich GCs), largel...

  13. Core-Shell Ferromagnetic Nanorod Based on Amine Polymer Composite (Fe3O4@DAPF) for Fast Removal of Pb(II) from Aqueous Solutions.

    Science.gov (United States)

    Venkateswarlu, Sada; Yoon, Minyoung

    2015-11-18

    Heavy metal ion removal from wastewater constitutes an important issue in the water treatment industry. Although a variety of nanomaterials have been developed for heavy metal removal via adsorption, the adsorption capacity, removal efficiency, and material recyclability still remain a challenge. Here, we present novel Fe3O4@DAPF core-shell ferromagnetic nanorods (CSFMNRs) for the removal of Pb(II) from aqueous solutions; they were prepared by the facile surface modification of twin-like ferromagnetic Fe3O4 nanorods using a 2,3-diaminophenol and formaldehyde (DAPF)-based polymer. The crystallinity and structure of the Fe3O4 nanorods were confirmed via X-ray diffraction (XRD). Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) revealed the core-shell morphology and composition of the materials. Pb(II) removal using the prepared Fe3O4@DAPF CSFMNRs was assessed, and comparable adsorption capacities (83.3 mg g(-1)) to the largest value were demonstrated. A thermodynamic study of the adsorption clearly indicated that the adsorption was exothermic and spontaneous. Due to the ferromagnetic properties with a high saturation magnetization value (56.1 emu g(-1)) of the nanorods, the nanorods exhibited excellent reusability with one of the fastest recovery times (25 s) among reported materials. Therefore, the Fe3O4@DAPF CSFMNRs can serve as recyclable adsorbent materials and as an alternative to commonly used sorbent materials for the rapid removal of heavy metals from aqueous solutions.

  14. Nanoparticulas basadas en complejos de Fe(II) con transicion de espin: sintesis, caracterizacion y aplicaciones en electronica molecular

    Science.gov (United States)

    Monrabal Capilla, Maria

    Esta tesis doctoral esta organizada en 5 capitulos y esta destinada al estudio de sistemas de Fe (II) que presentan el fenomeno de la transicion de espin a escala nanometrica. El capitulo 1 contiene una introduccion general sobre materiales moleculares multifuncionales, destacando aquellos ejemplos mas importantes. Por otro lado, se explicara el fenomeno de la transicion de espin, tratando aspectos conceptuales, los antecedentes mas importantes y la situacion actual. En el capitulo 2 se describen los diferentes procesos existentes para la obtencion de diferentes tipos de nanoparticulas. Ademas, se presenta la sintesis y caracterizacion de nanoparticulas del polimero de coordinacion unidimensional [Fe(Htrz)2(trz)]BF4, obtenidas mediant