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Sample records for lanthanideiii nitrate complexes

  1. Studies of Some Lanthanide(III Nitrate Complexes of Schiff Base Ligands

    Directory of Open Access Journals (Sweden)

    Kishor Arora Mukesh Sharma

    2009-01-01

    Full Text Available The studies of 16 new lanthanide(III nitrate complexes of Schiff base ligands are discussed. Schiff bases were obtained by the condensation of 2–methyl–4–N,N–bis–2' –cyanoethyl aminobenzaldehyde with aniline and 3 different substituted anilines. Lanthanide(III nitrates, viz. gadolinium(III nitrate, lanthanum(III nitrate, samarium(III nitrate and cerium(III nitrate were chosen to synthesize new complexes. The complexes were characterized on the basis of physicochemical studies viz. elemental analysis, spectral, viz. IR and electronic spectral and magnetic studies. TGA studies of some of the representative complexes were also done. Some of the representative complexes were also screened for the anti microbial studies.

  2. Synthesis and Characterization of Lanthanide(III Nitrate Complexes with Terdentate ONO Donor Hydrazone Derived from 2-Benzimidazolyl Mercaptoaceto Hydrazide and o-Hydroxy Aromatic Aldehyde

    Directory of Open Access Journals (Sweden)

    Vinayak M. Naik

    2011-01-01

    Full Text Available A few eight coordinated complexes of lanthanide(III nitrate with 2-benzimidazolyl mercaptoaceto hydrazone ligand (LH2 with the general formula [Ln(LH2NO2]H2O (where Ln = La, Pr, Nd, Sm and Gd have been synthesized and characterized by elemental analysis, magnetic susceptibility, molar conductance, UV-Visible, IR and 1H NMR spectral studies. The experimental data sustain stoichiometry of 1:2 (metal/ligand for the complexes. The spectral data shows that the ligand reacts in keto form and behaves as monobasic terdentate in nature. The nitrate appears to coordinate in the bidentate fashion to the metal ion. The thermal stabilities of the complexes have been studied by TGA and their kinetic parameters were calculated using Coats-Redfern and MKN methods. The antimicrobial activity studies have been under taken and results are discussed.

  3. Synthesis and spectroscopic characterization of some lanthanide(III nitrate complexes of ethyl 2-[2-(1-acetyl-2-oxopropylazo]-4,5-dimethyl-3-thiophenecarboxyate

    Directory of Open Access Journals (Sweden)

    CHEMPAKAM JANARDHANAN ATHIRA

    2011-02-01

    Full Text Available Ethyl 2-[2-(1-acetyl-2-oxopropylazo]-4,5-dimethyl-3-thiophenecarboxyate was synthesized by coupling diazotized ethyl 2-amino-4,5-dimethylthiophene-3-carboxylate with acetylacetone. Based on various spectral studies and elemental analysis, an intramolecularly hydrogen-bonded azo-enol structural form was assigned for the ligand. This ligand is versatile in forming a series of lanthanide(III complexes, viz., lanthanum(III, cerium(III, praseodymium(III, neodymium(III, samarium(III and gadolinium(III, which were characterized through various spectral studies, elemental analysis, magnetic susceptibility measurements, molar conductance and thermal analysis. The spectral data revealed that the ligand acted as a neutral tridentate, coordinating to the metal ion through one of the azo nitrogen atoms, the ester carbonyl and the enolic oxygen of the acetylacetone moiety, without deprotonation. Molar conductance values adequately supported their non-electrolytic nature. The ligand and lanthanum(III complex were subjected to X-ray diffraction studies. In addition, the lanthanum(III complex underwent a facile transesterification reaction on refluxing with methanol for a long period. The thermal behaviour of the lanthanum(III complex was also examined

  4. Lanthanide(III) complexation with an amide derived pyridinophane.

    Science.gov (United States)

    Castro, Goretti; Bastida, Rufina; Macías, Alejandro; Pérez-Lourido, Paulo; Platas-Iglesias, Carlos; Valencia, Laura

    2015-02-16

    Herein we report a detailed investigation of the solid state and solution structures of lanthanide(III) complexes with the 18-membered pyridinophane ligand containing acetamide pendant arms TPPTAM (TPPTAM = 2,2',2″-(3,7,11-triaza-1,5,9(2,6)-tripyridinacyclododecaphane-3,7,11-triyl)triacetamide). The ligand crystallizes in the form of a clathrated hydrate, where the clathrated water molecule establishes hydrogen-bonding interactions with the amide NH groups and two N atoms of the macrocycle. The X-ray structures of 13 different Ln(3+) complexes obtained as the nitrate salts (Ln(3+) = La(3+)-Yb(3+), except Pm(3+)) have been determined. Additionally, the X-ray structure of the La(3+) complex obtained as the triflate salt was also obtained. In all cases the ligand provides 9-fold coordination to the Ln(3+) ion, ten coordination being completed by an oxygen atom of a coordinated water molecule or a nitrate or triflate anion. The bond distances of the metal coordination environment show a quadratic change along the lanthanide series, as expected for isostructural series of Ln(3+) complexes. Luminescence lifetime measurements obtained from solutions of the Eu(3+) and Tb(3+) complexes in H2O and D2O point to the presence of a water molecule coordinated to the metal ion in aqueous solutions. The analysis of the Ln(3+)-induced paramagnetic shifts indicates that the complexes are ten-coordinated throughout the lanthanide series from Ce(3+) to Yb(3+), and that the solution structure is very similar to the structures observed in the solid state. The complexes of the light Ln(3+) ions are fluxional due to a fast Δ(λλλλλλ) ↔ Λ(δδδδδδ) interconversion that involves the inversion of the macrocyclic ligand and the rotation of the acetamide pendant arms. The complexes of the small Ln(3+) ions are considerably more rigid, the activation free energy determined from VT (1)H NMR for the Lu(3+) complex being ΔG(⧧)298 = 72.4 ± 5.1 kJ mol(-1).

  5. Extraction and coordination studies of a carbonyl-phosphine oxide scorpionate ligand with uranyl and lanthanide(III) nitrates: structural, spectroscopic and DFT characterization of the complexes.

    Science.gov (United States)

    Matveeva, Anna G; Vologzhanina, Anna V; Goryunov, Evgenii I; Aysin, Rinat R; Pasechnik, Margarita P; Matveev, Sergey V; Godovikov, Ivan A; Safiulina, Alfiya M; Brel, Valery K

    2016-03-28

    Hybrid scorpionate ligand (OPPh2)2CHCH2C(O)Me (L) was synthesized and characterized by spectroscopic methods and X-ray diffraction. The selected coordination chemistry of L with UO2(NO3)2 and Ln(NO3)3 (Ln = La, Nd, Lu) has been evaluated. The isolated mono- and binuclear complexes, namely, [UO2(NO3)2L] (1), [{UO2(NO3)L}2(μ2-O2)]·EtOH (2), [La(NO3)3L2]·2.33MeCN (3), [Nd(NO3)3L2]·3MeCN (4), [Nd(NO3)2L2]+·(NO3)−·EtOH (5) and [Lu(NO3)3L2] (6) have been characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray structures have been determined for complexes 1-5. Intramolecular intraligand π-stacking interactions between two phenyl fragments of the coordinated ligand(s) were observed in all complexes 1-5. The π-stacking interaction energy was estimated from Bader's AIM theory calculations performed at the DFT level. Solution properties have been examined using IR and multinuclear ((1)H, (13)C, and (31)P) NMR spectroscopy in CD3CN and CDCl3. Coordination modes of L vary with the coordination polyhedron of the metal and solvent nature showing many coordination modes: P(O),P(O), P(O),P(O),C(O), P(O),C(O), and P(O). Preliminary extraction studies of U(VI) and Ln(III) (Ln = La, Nd, Ho, Yb) from 3.75 M HNO3 into CHCl3 show that scorpionate L extracts f-block elements (especially uranium) better than its unmodified prototype (OPPh2)2CH2.

  6. Lanthanide(III and Yttrium(III Complexes of Benzimidazole-2-Acetic Acid: Synthesis, Characterisation and Effect of La(III Complex on Germination of Wheat

    Directory of Open Access Journals (Sweden)

    2006-01-01

    Full Text Available The synthesis and characterisation of lanthanide(III and yttrium(III nitrate complexes of benzimidazole-2-acetic acid (HBIA are reported. The complexes have been characterised by elemental analysis, molar conductance, magnetic studies, IR, 1 H NMR, UV-visible, EPR, and TG/DTA studies. They have the stoichiometry [ Ln 3 ( BIA 2 ( NO 3 7 ( H 2 O 4 ]⋅3 H 2 O where Ln=La(III, Pr(III, Nd(II, Sm(III, Eu(III, Gd(III, Tb(III, Dy(III, and Y(III. The effect of La(III complex on germination, coleoptile, and root length of two local varieties of wheat DWR-195 and GW-349 for different treatment periods has been investigated. The complex was found to exhibit enhanced activity, compared to HBIA or metal salt alone at lower treatment periods.

  7. Enantiomeric self-recognition in homo- and heterodinuclear macrocyclic lanthanide(III) complexes.

    Science.gov (United States)

    Lisowski, Jerzy

    2011-06-20

    The controlled formation of lanthanide(III) dinuclear μ-hydroxo-bridged [Ln(2)L(2)(μ-OH)(2)X(2)](n+) complexes (where X = H(2)O, NO(3)(-), or Cl(-)) of the enantiopure chiral macrocycle L is reported. The (1)H and (13)C NMR resonances of these complexes have been assigned on the basis of COSY, NOESY, TOCSY, and HMQC spectra. The observed NOE connectivities confirm that the dimeric solid-state structure is retained in solution. The enantiomeric nature of the obtained chiral complexes and binding of hydroxide anions are reflected in their CD spectra. The formation of the dimeric complexes is accompanied by a complete enantiomeric self-recognition of the chiral macrocyclic units. The reaction of NaOH with a mixture of two different mononuclear lanthanide(III) complexes, [Ln(1)L](3+) and [Ln(2)L](3+), results in formation of the heterodinuclear [Ln(1)Ln(2)L(2)(μ-OH)(2)X(2)](n+) complexes as well as the corresponding homodinuclear complexes. The formation of the heterodinuclear complex is directly confirmed by the NOESY spectra of [EuLuL(2)(μ-OH)(2)(H(2)O)(2)](4+), which reveal close contacts between the macrocyclic unit containing the Eu(III) ion and the macrocyclic unit containing the Lu(III) ion. While the relative amounts of homo- and heterodinuclear complexes are statistical for the two lanthanide(III) ions of similar radii, a clear preference for the formation of heterodinuclear species is observed when the two mononuclear complexes contain lanthanide(III) ions of markedly different sizes, e.g., La(III) and Yb(III). The formation of heterodinuclear complexes is accompanied by the self-sorting of the chiral macrocyclic units based on their chirality. The reactions of NaOH with a pair of homochiral or racemic mononuclear complexes, [Ln(1)L(RRRR)](3+)/[Ln(2)L(RRRR)](3+), [Ln(1)L(SSSS)](3+)/[Ln(2)L(SSSS)](3+), or [Ln(1)L(rac)](3+)/[Ln(2)L(rac)](3+), results in mixtures of homochiral, homodinuclear and homochiral, heterodinuclear complexes. On the contrary, no

  8. Design of efficient electroluminescent lanthanide(III) complexes

    CERN Document Server

    You, B R; Park, N G; Kim, Y S

    2001-01-01

    The lanthanide complexes have been anticipated to exhibit high efficiency along with a narrow emission spectrum. Photoluminescence for the lanthanide complex is characterized by a high efficiency since both single and triplet excitons are involved in the luminescence process. However, the maximum external electroluminescence quantum efficiencies have exhibited values around 1% due to triplet-triplet annihilation at high current. Here, we proposed a new energy transfer mechanism to overcome triplet-triplet annihilation by the Eu complex doped into phosphorescent materials with triplet levels that were higher than single levels of the Eu complex. In order to show the feasibility of the proposed energy transfer mechanism and to obtain the optimal ligands and host material, we have calculated the effect depending on ligands as a factor that controls emission intensity in lanthanide complexes. The calculation shows that triplet state as well as singlet state of anion ligand affects on absorption efficiency indirec...

  9. Lanthanide(III) Complexes with Tridentate Schiff Base Ligand ...

    African Journals Online (AJOL)

    The cell parameters of the Nd complex are a = 11.0927(8) Å, b = 17.9926 (13) Å, c = 11.9395(9) Å and ... lanthanide ions and to study their physicochemical proper- ...... 5 R.W. Wen, S.D. Han, G.J. Ren, Z. Chang, Y.W. Li and X.H. Bu, A flexible.

  10. Synthesis, spectral characterization, thermal and biological studies of lanthanide(III) complexes of oxyphenbutazone

    Institute of Scientific and Technical Information of China (English)

    PS Binil; MR Anoop; KR Jisha; S Suma; MR Sudarsanakumar

    2014-01-01

    Lanthanide(III) complexes of 4-butyl-1-(4-hydroxyphenyl)-2-phenyl-3,5-pyrazolidinedione (OPB) were prepared by ho-mogeneous precipitation. The solid complexes were characterized by elemental analysis, magnetic susceptibility data, molar conduc-tivity measurements and IR, UV-Vis, mass, 1H NMR and 13C NMR spectral methods. The thermal decomposition of the complexes under static air atmosphere was investigated by simultaneous TG/DTG at a heating rate of 10 °C/min. The final decomposition prod-ucts were found to be metal oxides. The spectroscopic data suggested that OPB acted as a bidentate, mono-ionic ligand coordinating through two carbonyl oxygens of the pyrazolidinedione ring. The kinetic and thermodynamic parameters such as activation energy, pre-exponential factor and entropy of activation for each step of the decomposition reactions were evaluated using Coats-Redfern and MacCallum-Tanner equations. The negative entropy values of the complexes indicated that the activated complexes had a more or-dered structure than the reactant and that the reactions were slower than normal. Investigations of antimicrobial activity of the com-pounds were carried out by the disk diffusion technique.

  11. Evidence of Different Stoichiometries for the Limiting Carbonate Complexes across the Lanthanide(III) Series

    Energy Technology Data Exchange (ETDEWEB)

    Philippini, V.; Vercouter, T.; Vitorge, P. [CEA Saclay, DEN DPC SECR Lab Speciat Radionucleides and Mol, F-91191 Gif Sur Yvette (France); Vitorge, P. [Univ Evry Val Essonne, CNRS, Lab Anal and Modelisat Biol and Environm, UMR 8587, F-91025 Evry (France)

    2010-07-01

    The stoichiometries of limiting carbonate complexes of lanthanide(III) ions were investigated by solubility measurements of hydrated NaLn(CO{sub 3}){sub 2} solid compounds (Ln = La, Nd, Eu and Dy) at room temperature in aqueous solutions of high ionic strength (3. 5 mol. kg{sup -1}) NaClO{sub 4}) and high CO{sub 3}{sup 2-} concentrations (0. 1 to 1. 5 mol. kg{sup -1}). The results were interpreted by considering the stability of carbonate complexes, with limiting species found to be La(CO{sub 3}){sub 4}{sup 5-}, Nd(CO{sub 3}){sub 4}{sup 5-}, Eu(CO{sub 3}){sub 3}{sup 3-} and Dy(CO{sub 3}){sub 3}{sup 3-}. TRLFS measurements on the Eu and Dy solutions confirmed the predominance of a single aqueous complex in all the samples. Equilibrium constants were determined for the reaction Ln(CO{sub 3}){sub 3}{sup 3-} + CO{sub 3}{sup 2-} reversible arrow Ln(CO{sub 3}){sub 4}{sup 5-}: log(10) K{sub 4,} {sub L}a{sup 3}. 5{sup m} {sup N}a{sup C}l{sup O}{sub 4} = 0. 7 {+-} 0. 3, log(10) K{sub 4,} {sub N}d{sup 3}. 5{sup m} {sup N}a{sup C}l{sup O}{sub 4} = 1. 3 {+-} 0. 3, and for Ln = Eu and Dy, log(10) K{sub 4,} {sub L}n{sup 3}. 5{sup m} {sup N}a{sup C}l{sup O}{sub 4}) {<=} -0. 4. These results suggest that tetra-carbonato complexes are stable only for the light lanthanide ions in up to 1. 5 molal CO{sub 3}{sup 2-} aqueous solutions, in agreement with our recent capillary electrophoresis study. Comparison with literature results indicates that analogies between actinide(III) and lanthanide(III) ions of similar ionic radii do not hold in concentrated carbonate solutions. Am(CO{sub 3}){sub 3}{sup 3-} was previously evidenced by solubility measurements, whereas we have observed that Nd(CO{sub 3}){sub 4}{sup 5-} predominates in similar conditions. We may speculate that small chemical differences between Ln(III) and An(III) could result in macroscopic differences when their coordination sphere is complete. (authors)

  12. Synthesis, X-ray crystal structure, DNA binding and Nuclease activity of lanthanide(III) complexes of 2-benzoylpyridine acetylhydrazone

    Indian Academy of Sciences (India)

    KARREDDULA RAJA; AKKILI SUSEELAMMA; KATREDDI HUSSAIN REDDY

    2016-08-01

    Lanthanide(III) complexes of general formula [La(BPAH)₂(NO₃)₃] and [Ce(BPAH)₂(NO₃)(H₂O)₂] 2NO₃.H₂O (where, BPAH = 2-benzoylpyridine acetyl hydrazone), were synthesized and characterized by elemental analysis, molar conductance, IR spectroscopy and single crystal X-ray diffraction and Hirschfeld studies. The central metal ion is 12-coordinate in lanthanum complex and 10-coordinated in the cerium complex. The coordination polyhedra around the lanthanum and cerium were found to have distorted icosahedron and distorted bicapped square antiprism respectively. DNA binding and nuclease activity of these complexes were also investigated in the present work.

  13. Microwave assisted synthesis, spectroscopic, electrochemical and DNA cleavage studies of lanthanide(III) complexes with coumarin based imines.

    Science.gov (United States)

    Kapoor, Puja; Fahmi, Nighat; Singh, R V

    2011-12-01

    The present work stems from our interest in the synthesis, characterization and biological evaluation of lanthanide(III) complexes of a class of coumarin based imines which have been prepared by the interaction of hydrated lanthanide(III) chloride with the sodium salts of 3-acetylcoumarin thiosemicarbazone (ACTSZH) and 3-acetylcoumarin semicarbazone (ACSZH) in 1:3 molar ratio using thermal as well as microwave method. Characterization of the ligands as well as the metal complexes have been carried out by elemental analysis, melting point determinations, molecular weight determinations, magnetic moment, molar conductance, IR, (1)H NMR, (13)C NMR, electronic, EPR, X-ray powder diffraction and mass spectral studies. Spectral studies confirm ligands to be monofunctional bidentate and octahedral environment around metal ions. The redox behavior of one of the synthesized metal complex was investigated by cyclic voltammetry. Further, free ligands and their metal complexes have been screened for their antimicrobial as well as DNA cleavage activity. The results of these findings have been presented and discussed.

  14. Configuration-averaged open shell ab initio method for crystal field levels and magnetic properties of lanthanide(III) complexes

    CERN Document Server

    Heuvel, Willem Van den; Soncini, Alessandro

    2015-01-01

    We present an ab initio methodology dedicated to the determination of the electronic structure and magnetic properties of ground and low-lying excited states, i.e., the crystal field levels, in lanthanide(III) complexes. Currently, the most popular and successful ab initio approach is the CASSCF/RASSI-SO method, consisting of the optimization of multiple complete active space self-consistent field (CASSCF) spin eigenfunctions, followed by full diagonalization of the spin--orbit coupling (SOC) Hamiltonian in the basis of the CASSCF spin states featuring spin-dependent orbitals. Based on two simple observations valid for Ln(III) complexes, namely: (i) CASSCF 4f atomic orbitals are expected to change very little when optimized for different multiconfigurational states belonging to the 4f-electronic configuration, (ii) due to strong SOC the total spin is not a good quantum number, we propose here an efficient ab initio strategy which completely avoids any multiconfigurational calculation, by optimizing a unique s...

  15. Photo-induced DNA cleavage activity and remarkable photocytotoxicity of lanthanide(III) complexes of a polypyridyl ligand.

    Science.gov (United States)

    Hussain, Akhtar; Gadadhar, Sudarshan; Goswami, Tridib K; Karande, Anjali A; Chakravarty, Akhil R

    2012-01-21

    Lanthanide(III) complexes [Ln(pyphen)(acac)(2)(NO(3))] (1, 2), [Ln(pydppz)(acac)(2)(NO(3))] (3, 4) and [La(pydppz)(anacac)(2)(NO(3))] (5), where Ln is La(III) (in 1, 3, 5) and Gd(III) (in 2, 4), pyphen is 6-(2-pyridyl)-1,10-phenanthroline, pydppz is 6-(2-pyridyl)-dipyrido[3,2-a:2',3'-c]phenazine, anacac is anthracenylacetylacetonate and acac is acetylacetonate, were prepared, characterized and their DNA photocleavage activity and photocytotoxicity studied. The crystal structure of complex 2 displays a GdO(6)N(3) coordination. The pydppz complexes 3-5 show an electronic spectral band at ~390 nm in DMF. The La(III) complexes are diamagnetic, while the Gd(III) complexes are paramagnetic with seven unpaired electrons. The molar conductivity data suggest 1 : 1 electrolytic nature of the complexes in aqueous DMF. They are avid binders to calf thymus DNA giving K(b) in the range of 5.4 × 10(4)-1.2 × 10(6) M(-1). Complexes 3-5 efficiently cleave supercoiled DNA to its nicked circular form in UV-A light of 365 nm via formation of singlet oxygen ((1)O(2)) and hydroxyl radical (HO˙) species. Complexes 3-5 also exhibit significant photocytotoxic effect in HeLa cancer cells giving respective IC(50) value of 0.16(±0.01), 0.15(±0.01) and 0.26±(0.02) μM in UV-A light of 365 nm, while they are less toxic in dark with an IC(50) value of >3 μM. The presence of an additional pyridyl group makes the pydppz complexes more photocytotoxic than their dppz analogues. FACS analysis of the HeLa cells treated with complex 4 shows apoptosis as the major pathway of cell death. Nuclear localization of complex 5 having an anthracenyl moiety as a fluorophore is evidenced from the confocal microscopic studies.

  16. Aqueous Binary Lanthanide(III) Nitrate Ln(NO3)3 Electrolytes Revisited: Extended Pitzer and Bromley Treatments

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, Sayandev; Campbell, Emily L.; Neiner, Doinita; Pence, Natasha; Robinson, Troy; Levitskaia, Tatiana G.

    2015-09-11

    To date, only limited thermodynamic models describing activity coefficients of the aqueous solutions of lanthanide ions are available. This work expands the existing experimental osmotic coefficient data obtained by classical isopiestic technique for the aqueous binary trivalent lanthanide nitrate Ln(NO3)3 solutions using a combination of water activity and vapor pressure osmometry measurements. The combined osmotic coefficient database for each aqueous lanthanide nitrate at 25°C, consisting of literature available data as well as data obtained in this work, was used to test the validity of Pitzer and Bromley thermodynamic models for the accurate prediction of mean molal activity coefficients of the Ln(NO3)3 solutions in wide concentration ranges. The new and improved Pitzer and Bromley parameters were calculated. It was established that the Ln(NO3)3 activity coefficients in the solutions with ionic strength up to 12 mol kg-1 can be estimated by both Pitzer and single-parameter Bromley models, even though the latter provides for more accurate prediction, particularly in the lower ionic strength regime (up to 6 mol kg-1). On the other hand for the concentrated solutions, the extended three-parameter Bromley model can be employed to predict the Ln(NO3)3 activity coefficients with remarkable accuracy. The accuracy of the extended Bromley model in predicting the activity coefficients was greater than ~95% and ~90% for all solutions with the ionic strength up to 12 mol kg-1 and and 20 mol kg-1, respectively. This is the first time that the activity coefficients for concentrated lanthanide solutions have been predicted with such a remarkable accuracy.

  17. Controlled Synthesis of a Novel Heteropolymetallic Complex with Selectively Incorporated Lanthanide(III) Ions

    OpenAIRE

    Debroye, Elke; Ceulemans, Matthias; Vander Elst, Luce; Laurent, Sophie; Muller, Robert N.; Parac-Vogt, Tatjana

    2014-01-01

    A novel synthetic strategy toward a heteropolymetallic lanthanide complex with selectively incorporated gadolinium and europium ions is outlined. Luminescence and relaxometric measurements suggest possible applications in bimodal (magnetic resonance/optical) imaging.

  18. H4octapa: highly stable complexation of lanthanide(III) ions and copper(II).

    Science.gov (United States)

    Kálmán, Ferenc Krisztián; Végh, Andrea; Regueiro-Figueroa, Martín; Tóth, Éva; Platas-Iglesias, Carlos; Tircsó, Gyula

    2015-03-02

    The acyclic ligand octapa(4-) (H4octapa = 6,6'-((ethane-1,2-diylbis((carboxymethyl)azanediyl))bis(methylene))dipicolinic acid) forms stable complexes with the Ln(3+) ions in aqueous solution. The stability constants determined for the complexes with La(3+), Gd(3+), and Lu(3+) using relaxometric methods are log KLaL = 20.13(7), log KGdL = 20.23(4), and log KLuL = 20.49(5) (I = 0.15 M NaCl). High stability constants were also determined for the complexes formed with divalent metal ions such as Zn(2+) and Cu(2+) (log KZnL = 18.91(3) and log KCuL = 22.08(2)). UV-visible and NMR spectroscopic studies and density functional theory (DFT) calculations point to hexadentate binding of the ligand to Zn(2+) and Cu(2+), the donor atoms of the acetate groups of the ligand remaining uncoordinated. The complexes formed with the Ln(3+) ions are nine-coordinated thanks to the octadentate binding of the ligand and the presence of a coordinated water molecule. The stability constants of the complexes formed with the Ln(3+) ions do not change significantly across the lanthanide series. A DFT investigation shows that this is the result of a subtle balance between the increased binding energies across the 4f period, which contribute to an increasing complex stability, and the parallel increase of the absolute values of the hydration free energies of the Ln(3+) ions. In the case of the [Ln(octapa)(H2O)](-) complexes the interaction between the amine nitrogen atoms of the ligand and the Ln(3+) ions is weakened along the lanthanide series, and therefore the increased electrostatic interaction does not overcome the increasing hydration energies. A detailed kinetic study of the dissociation of the [Gd(octapa)(H2O)](-) complex in the presence of Cu(2+) shows that the metal-assisted pathway is the main responsible for complex dissociation at pH 7.4 and physiological [Cu(2+)] concentration (1 μM).

  19. Exploring the ability of the nalidixate to sensitize visible and near-infrared emitting lanthanide(III) cations

    Science.gov (United States)

    Eliseeva, Svetlana V.; Liasotkyi, Valerii S.; Golovach, Iurii P.; Doga, Pavel G.; Antonovich, Valery P.; Petoud, Stéphane; Meshkova, Svetlana B.

    2017-03-01

    Recently, a strong interest has been directed towards near-infrared (NIR) emitting lanthanide(III) compounds as they do possess complementary advantages in respect to organic molecules and semi-conductor nanocrystals, especially in the fields of biological analysis and imaging. To benefit from their emission, a key requirement to fulfill is the sensitization of lanthanide(III) cations with an appropriate chromophore. This condition is especially challenging to address for the lanthanide(III) cations emitting in the NIR. The quest for new chromophores well adapted to the NIR-emitting lanthanide(III) ions is an important direction of research in order to broaden the rationalization of the parameters that control the sensitization process. In this work, we have investigated the ability of a readily available chromophoric ligand, the nalidixic acid, to sensitize lanthanide(III) cations with a specific interest for those emitting in the NIR. We have therefore performed an extensive study of the luminescence properties of lanthanide(III) complexes emitting in the visible and in the NIR ranges formed in situ upon mixing the corresponding Ln(III) nitrates (Ln(III)  =  Pr, Nd, Sm, Eu, Tb, Dy, Ho, Tm, Yb) with nalidixic acid (HNA) in a 1:3 molar ratio in the presence of a base. Luminescence spectra, quantum yields and luminescence lifetimes have been measured and discussed. The red emission of Eu with a quantum yield value of 5.90(3)%, red and NIR of Pr (7(1) · 10-4 and 5.6(1) · 10-4%) and Ho (9.3(2) · 10-4 and 2.8(1) · 10-4%), green of Tb (5.21(5)%), yellow and NIR of Dy (0.51(2) and 0.065(4)%), orange and NIR of Sm (0.147(5) and 0.037(2)%), as well as NIR of Nd (0.0321(2)%) and Yb (0.021(1)%) were observed. These results and analysis show that the nalidixate is a versatile chromophoric ligand that is suitable for the sensitization of nine different lanthanide(III) cations, five of them emitting in the NIR.

  20. Temperature-dependent luminescence properties of lanthanide(III) β-diketonate complex-doped LAPONITE®.

    Science.gov (United States)

    Xu, Qianqian; Li, Zhiqiang; Wang, Yige; Li, Huanrong

    2016-03-01

    In this work, by doping the lanthanide(III)-hexafluoroacetylacetone complex into LAPONITE®, we obtained a lanthanide-based organic-inorganic hybrid material. The resulting hybrid materials were fully characterized with elementary analysis, scanning electron microscopy (SEM) and powder X-ray diffraction (PXRD) techniques. The Ln(3+) and HFA loadings were experimentally determined to be roughly 0.3 per u.c. and 0.72 per u.c. by analyzing the supernatant (titration against EDTA) and elemental analysis, respectively. XRD patterns suggest that at least partial complexes are intercalated within the interlayers of the LAPONITE®. The in situ formation of luminescent Ln(3+) complexes is confirmed by the luminescence data. Furthermore, the emission intensity ratio of the (5)D4→(7)F5 transition (Tb(3+)) to the (5)D0→(7)F2 transition (Eu(3+)) of the hybrid material containing both Eu(3+) and Tb(3+) can be linearly related to temperature in the range from 197 K to 287 K (temperature sensitivity: 1.107% per K), which will be an appealing alternative for in situ and real time detection of temperature in many special areas. This strategy presents new opportunities for the development of highly sensitive and stable thermo sensors.

  1. Increasing the luminescence of lanthanide(III) macrocyclic complexes by the use of polymers and lanthanide enhanced luminescence

    Science.gov (United States)

    Leif, Robert C.; Becker, Margie C.; Bromm, Alfred J., Jr.; Vallarino, Lidia M.; Williams, Steven A.; Yang, Sean

    2001-05-01

    A Eu (III)-macrocycle-isothiocyanate, Quantum DyeTM, has been reacted with lysine homo- and hetero-peptides to give polymers with multiple luminescent side chains. Contrary to the concentration quenching that occurs with conventional organic fluorophores, the attachment of multiple Quantum Dyes to a polymer results in a concomitant increase in luminescence. The emission intensity of the peptide-bound Quantum Dye units is approximately linearly related to their number. The attachment of peptides containing multiple lanthanide (III) macrocycles to analyte-binding species is facilitated by employing solid-phase technology. Bead-bound peptides are first labeled with multiple Quantum Dye units, then conjugated to an antibody, and finally released from the bead by specific cleavage with Proteinase K unedr physiological conditions. Since the luminescence of lanthanide(III) macrocycles is enhanced by the presence of GD(III) or Y(III) ions in a micellar system, a significant increase in signal can be achieved by attaching a polymer labeled with multiple Quantum Dye units to an analyte- binding species, such as a monoclonal antibody, or by taking advantage of the luminescence enhancing effects of Gd(III) or Y(III), or by both approaches concomitantly. A comparison between the integrated intensity and lifetime measurements of the Eu(III)-macrocycle under a variety of conditions show that the signal increase caused by Gd(III) can not be explained solely by the increase in lifetime, and must result in significant part from an energy transfer process invloving donors not directly bound to the Eu(III).

  2. A general method for preparing lanthanide oxide nanoparticles via thermal decomposition of lanthanide(III) complexes with 1-hydroxy-2-naphthoic acid and hydrazine ligands

    Science.gov (United States)

    Parimalagandhi, Karuppannan; Premkumar, Thathan; Vairam, Sundararajan

    2016-09-01

    Six new lanthanide(III) complexes (i.e., [Ln(L)2(NA)1.5]·3H2O, where Ln=La(III), Pr(III), Nd(III), Sm(III), Gd(III), and Ce(III) and L and NA indicate N2H4 and C10H6(1-O)(2-COO), respectively) with 1-hydroxy-2-naphthoic acid [C10H6(1-O)(2-COOH)] and hydrazine (N2H4) as co-ligands were characterized by elemental, FTIR, UV-visible, and XRD techniques. In the FT-IR spectra, the N-N stretching frequency in the range of 981-949 cm-1 demonstrates evidence of the presence of coordinated N2H4, indicating the bidentate bridging nature of hydrazine in the complexes. These complexes show symmetric and asymmetric COO- stretching from 1444 to 1441 cm-1 and 1582 to 1557 cm-1, respectively, indicating bidentate coordination. TG-DTA studies revealed that the compounds underwent endothermic dehydration from 98 to 110 °C. This was followed by the exothermic decomposition of oxalate intermediates to yield the respective metal oxides as the end products. From SEM images, the average size of the metal oxide particles prepared by thermal decomposition of the complexes was determined to be 39-42 nm. The powder X-ray and SEM coupled with energy dispersive X-ray (EDX) studies revealed the presence of the respective nano-sized metal oxides. The kinetic parameters of the decomposition of the complexes were calculated using the Coats-Redfern equation.

  3. 21 CFR 176.320 - Sodium nitrate-urea complex.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium nitrate-urea complex. 176.320 Section 176... Substances for Use Only as Components of Paper and Paperboard § 176.320 Sodium nitrate-urea complex. Sodium nitrate-urea complex may be safely used as a component of articles intended for use in...

  4. Hydrolytic synthesis of novel lanthanide(III) complexes with pyridine-2,6-dicarboxylic acid: Characterization of the structure and the physical properties

    Science.gov (United States)

    Hojnik, Nuša; Kristl, Matjaž; Golobič, Amalija; Jagličić, Zvonko; Drofenik, Miha

    2015-01-01

    The coordination compounds of pyridine-2,6-dicarboxylic acid and two lanthanide(III) ions, Ho3+ and Dy3+, were hydrolytically synthesized in aqueous solutions at a slightly basic pH, and then characterized by thermogravimetric analysis, IR spectroscopy, magnetic measurements as well as X-ray powder and single-crystal diffraction analysis. The elemental analyses were performed to check the purity of the compounds. The formula for these compounds is identified as Na3[Ln(Pydc)3]ṡ14H2O (Ln = Ho, 1; Ln = Dy, 2) in agreement with the X-ray structural analysis and all the other experimental data. The absence of the 1709 cm-1 band corresponding to ν(C dbnd O) in the IR spectra of the compounds evidences the deprotonating of the carboxyl group. The very strong inductive effect of the metal ion that is readily coordinated by the carboxylate group of the zwitterionic ligand is responsible for the formation of the product. The single-crystal X-ray structural analysis revealed that compounds 1 and 2 are isostructural. Their structure can be described as interchanging layers of complex anions [Ln(Pydc)3]3 (Ln = Ho and Dy for 1 and 2, respectively) and layers of hydrated sodium cations. In complex anions the holmium and dysprosium atoms are coordinated by three crystallographically independent pyridinedicarboxylate ligands in tridentate-chelate mode, via one O atom of both carboxylate groups and the ring N atom. The coordination number is nine and the coordination polyhedron is a tricapped trigonal prism with O atoms at the corners.

  5. Synthesis and luminescent properties of novel lanthanide(III) beta-diketone complexes with nitrogen p,p'-disubstituted aromatic ligands.

    Science.gov (United States)

    Bellusci, Anna; Barberio, Giovanna; Crispini, Alessandra; Ghedini, Mauro; La Deda, Massimo; Pucci, Daniela

    2005-03-21

    Tris-beta-diketonate lanthanide(III) complexes (Ln = Eu, Er, Yb, Tb), of general formula [Ln(acac)3 L(m)], with chelating ligands such as 4,7-disubstituted-1,10-phenanthrolines and 4,4'-disubstituted-2,2'-bipyridines, have been synthesized and fully characterized. The inductive effects of the para-substituents on the aromatic N-donor ligands have been investigated both in the solid and in the solution states. Single-crystal X-ray structures have been determined for the diethyl 1,10-phenanthroline-4,7-dicarboxylate europium and 4,4'-dimethoxy-2,2'-bipyridine erbium derivatives, revealing a distorted square antiprismatic geometry around the lanthanide atom in both cases. The influence exerted by the p,p'-substituents with respect to the nitrogen coordinating atoms on the Ln-N bond distances is discussed comparing the geometrical parameters with those found for the crystal structures containing the fragments [Ln(III)(phen)] and [Ln(III)(bipy)] obtained from the Cambridge Structural Database. The influence exerted by the electron-attracting groups on the coordination ability of the ligands, that in some cases becomes lack of coordination of the lanthanide ions, has been also detected in solution where the loss of the ligand has been followed by UV-vis spectroscopy. Moreover, the use of relatively long alkoxy chains as substituents on the 1,10-phenanthroline ligand led to the formation of a promesogenic lanthanide complex, whose thermal behavior is encouraging for the synthesis of new lanthanide liquid-crystalline species.

  6. Synthesis, spectroscopic characterization, DNA cleavage and antibacterial studies of a novel tridentate Schiff base and some lanthanide(III) complexes

    Institute of Scientific and Technical Information of China (English)

    K. Mohanan; R. Aswathy; L.P. Nitha; Niecy Elsa Mathews; B. Sindhu Kumari

    2014-01-01

    A novel potential tridentate Schiff base was prepared by condensing equimolar quantities of 2-hydroxyacetophenone and 2-aminopyrimidine in methanol. This ligand was versatile in forming a series of complexes with lanthanide ions such as La(III), Pr(III), Nd(III), Sm(III), Gd(III), Dy(III) and Yb(III). The ligand and the metal complexes were characterized through elemental analysis, molar conductance, UV-Visible, IR, 1H NMR, and mass spectral studies. The spectral studies indicated that the ligand was coordinated to the metal ion in neutral tridentate fashion through the azomethine nitrogen, one of the nitrogen atoms in the pyrimidine ring and the phenolic oxygen without deprotonation. Thermal decomposition and luminescence property of lanthanum(III) complex were also examined. The X-ray diffraction patterns showed the crystalline nature of the ligand and its lanthanum(III) complex. The DNA cleavage studies of the ligand and the metal complexes were carried out and it was observed that the lanthanum(III) and neo-dymium(III) complexes cleaved the pUC19 DNA effectively. The ligand and the metal complexes were screened for their antibacte-rial activities. The metal complexes were found to be more potent bactericides than the ligand.

  7. Dual Emissive-Reflective Display Materials with Large Emission Switching Using Highly Luminescent Lanthanide(III) Complex and Electrochromic Material

    Science.gov (United States)

    Kanazawa, Kenji; Nakamura, Kazuki; Kobayashi, Norihisa

    2013-05-01

    Electroswitching of emission and coloration was achieved by a combination of a luminescent Eu(III) complex and an electrochromic molecule of diheptyl viologen (HV2+), in order to utilize them as novel display devices with dual emissive-reflective modes. The coloration was associated with the HV2+ electrochromism. Emission control was also achieved by the HV2+ electrochromism via intermolecular energy transfer from the excited state of the Eu(III) ion to the HV+. In order to improve ON-OFF contrast in emission, the emission quantum yield of Eu(III) complex were considerably improved using low vibrational phosphine oxide ligands, resulting in the large control of emission switching.

  8. Sensitization of visible and NIR emitting lanthanide(III) ions in noncentrosymmetric complexes of hexafluoroacetylacetone and unsubstituted monodentate pyrazole.

    Science.gov (United States)

    Ahmed, Zubair; Iftikhar, K

    2013-11-07

    A series of highly volatile eight-coordinate air and moisture stable lanthanide complexes of the type [Ln(hfaa)3(L)2] (Ln = Pr (1), Nd (2), Eu (3), Gd (4), Tb (5), Dy (6), Ho (7), Er (8), Tm (9), and Yb (10); hfaa = anion of hexafluoroacetylacetone and L = pyrazole) have been synthesized and characterized by elemental analysis, IR, ESI-MS(+), and NMR studies. Single-crystal X-ray structures have been determined for the Eu(III) and Dy(III) complexes. These complexes crystallize in the monoclinic space group P2(1)/c. The lanthanide ion in each of these complexes is eight-coordinate with six oxygen atoms from three hfaa and two N-atoms from two pyrazole units, forming a coordination polyhedron best describable as a distorted square antiprism. The NMR spectra reveal that both the pyrazole units remain attached to the metal in solution and the β-diketonate and pyrazole protons are shifted in opposite directions in the case of paramagnetic complexes. The lanthanide-induced chemical shifts are dipolar in nature. The hypersensitive transitions of Nd(III), Ho(III), and Er(III) are sensitive to the environment (solvent), which is reflected by the oscillator strength and band shape of these transitions. The band shape due to the hypersensitive transition of Nd(III) in noncoordinating chloroform and dichloromethane is similar to those of the typical eight-coordinate Nd(III) β-diketonate complexes. The quantum yield and lifetime of Pr(III), Eu(III), Tb(III), Dy(III), and Tm(III) in visible and Pr(III), Nd(III), Dy(III), Ho(III), Er(III) Tm(III), and Yb(III) in the NIR region are sizable. The environment around these metal ions is asymmetric, which leads to increased radiative rates and luminescence efficiencies. The quantum yield of the complexes reveal that ligand-to-metal energy transfer follows the order Eu(III) > Tb(III) ≫ Pr(III) > Dy(III) > Tm(III). Both ligands (hfaa and pyrazole) are good sensitizers for all the visible and NIR emitters effectively, except for Tb

  9. Efficient formation of luminescent lanthanide(III) complexes by solid-phase synthesis and on-resin screening.

    Science.gov (United States)

    Nakamura, Tatsuya; Mizukami, Shin; Tanaka, Miho; Kikuchi, Kazuya

    2013-11-01

    Time-resolved luminescence measurements of luminescent lanthanide complexes have advantages in biological assays and high-throughput screening, owing to their high sensitivity. In spite of the recent advances in their energy-transfer mechanism and molecular-orbital-based computational molecular design, it is still difficult to estimate the quantum yields of new luminescent lanthanide complexes. Herein, solid-phase libraries of luminescent lanthanide complexes were prepared through amide-condensation and Pd-catalyzed coupling reactions and their luminescent properties were screened with a microplate reader. Good correlation was observed between the time-resolved luminescence intensities of the solid-phase libraries and those of the corresponding complexes that were synthesized by using liquid-phase chemistry. This method enabled the rapid and efficient development of new sensitizers for Sm(III), Eu(III), and Tb(III) luminescence. Thus, solid-phase combinatorial synthesis combined with on-resin screening led to the discovery of a wide variety of luminescent sensitizers.

  10. Lanthanide(III) di- and tetra-nuclear complexes supported by a chelating tripodal tris(amidate) ligand.

    Science.gov (United States)

    Brown, Jessie L; Jones, Matthew B; Gaunt, Andrew J; Scott, Brian L; MacBeth, Cora E; Gordon, John C

    2015-04-20

    Syntheses, structural, and spectroscopic characterization of multinuclear tris(amidate) lanthanide complexes is described. Addition of K3[N(o-PhNC(O)(t)Bu)3] to LnX3 (LnX3 = LaBr3, CeI3, and NdCl3) in N,N-dimethylformamide (DMF) results in the generation of dinuclear complexes, [Ln(N(o-PhNC(O)(t)Bu)3)(DMF)]2(μ-DMF) (Ln = La (1), Ce (2), Nd(3)), in good yields. Syntheses of tetranuclear complexes, [Ln(N(o-PhNC(O)(t)Bu)3)]4 (Ln = Ce (4), Nd(5)), resulted from protonolysis of Ln[N(SiMe3)2]3 (Ln = Ce, Nd) with N(o-PhNCH(O)(t)Bu)3. In the solid-state, complexes 1-5 exhibit coordination modes of the tripodal tris(amidate) ligand that are unique to the 4f elements and have not been previously observed in transition metal systems.

  11. Organic Nitrates: A Complex Family of Atmospheric Trace Constituents

    Science.gov (United States)

    Ballschmiter, K.; Fischer, R. G.; Grünert, A.; Kastler, J.; Schneider, M.; Woidich, S.

    2003-04-01

    Biogenic and geogenic hydrocarbons are the precursors of organic nitrates that are formed as tropospheric photo-oxidation products in the presence of NOx. Air chemistry leads to a very complex pattern of nitric acid esters: alkyl nitrates, aryl-alkyl nitrates, and bifunctional nitrates like alkyl dinitrates, hydroxy alkyl nitrates and carbonyl alkyl nitrates. We have analyzed the pattern of organic nitrates in air samples after adsorption/thermal desorption (low volume sampling-LVS) or adsorption/solvent desorption (high volume sampling-HVS) by capillary gas chromatography with electron capture (ECD) and mass spectrometric detection (MSD) using air aliquotes of 100 up to 3000 liters on column. The complexity of the organic nitrates found in air requires a group pre-separation by normal phase liquid chromatography. A detection limit per compound of 0.005 ppt(v) is achieved by our approach. We have synthesized a broad spectrum of organic nitrates as reference compounds. Air samples were taken from central Europe, the US West (Utah, Nevada, California), and the North- and South Atlantic including Antarctica. Levels and patterns of the regional and global occurrence of the various groups of C1-C12 organic nitrates including dinitrates and hydroxy nitrates and nitrates of isoprene (2-methylbutadiene) are presented. Werner G., J. Kastler, R. Looser, K. Ballschmiter: "Organic nitrates of isoprene as atmospheric trace compounds" Angewandte Chemie - International Edition (1999) 38: 1634-1637. Woidich S., O. Froescheis, O. Luxenhofer, K. Ballschmiter: "EI- and NCI-mass spectrometry of arylalkyl nitrates and their occurrence in urban air" Fresenius J. Anal. Chem. (1999) 364 : 91-99. Kastler, J; Jarman, W; Ballschmiter, K.: "Multifunctional organic nitrates as constituents in European and US urban photo-smog" Fresenius J. Anal. Chem. (2000) 368:244-249. Schneider M., K. Ballschmiter: "C3-C14 alkyl nitrates in remote South Atlantic air" Chemosphere (1999) 38: 233-244. Fischer

  12. A [Cyclentetrakis(methylene)]tetrakis[2-hydroxybenzamide]Ligand That Complexes and Sensitizes Lanthanide(III) Ions

    Energy Technology Data Exchange (ETDEWEB)

    D' Aleo, Anthony; Xu, Jide; Do, King; Muller, Gilles; Raymond, Kenneth N.

    2009-04-30

    The synthesis of a cyclen derivative containing four isophthalamide groups (L{sup 1}) is described. The spectroscopic properties of the Ln(III) complexes of L{sup 1} (Ln = Gd, Tb, Yb, Eu) reveal changes of the UV/visible absorption, circular dichroism absorption, luminescence and circularly polarized luminescence properties. It is shown that at least two metal complex species are present in solution, whose relative amounts are pH dependent. When at pH > 8.0, an intense long lived emission is observed (for [L{sup 1}Tb] and [L{sup 1}Yb]) while at pH < 8.0, a weaker, shorter-lived species predominates. Unconventional Ln(III) emitters (Pr, Nd, Sm, Dy and Tm) were sensitized in basic solution, both in the visible and in the near infra-red, to measure the emission of these ions.

  13. Solid-state and solution-state coordination chemistry of lanthanide(III) complexes with α-hydroxyisobutyric acid.

    Science.gov (United States)

    Chen, Xiao-Yan; Goff, George S; Ewing, William C; Scott, Brian L; Runde, Wolfgang

    2012-12-17

    Despite the wide range of applications of α-hydroxyisobutyric acid (HIBA) in biochemical processes, pharmaceutical formulations, and group and elemental separations of lanthanides and actinides, the structures and geometries of lanthanide-HIBA complexes are still not well understood. We reacted HIBA with lanthanides in aqueous solution at pH = 5 and synthesized 14 lanthanide-HIBA complexes of the formula [Ln(HIBA)(2)(H(2)O)(2)](NO(3))·H(2)O (Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13), Lu (14)), isolating single crystals (1-7, 10, and 11) and powders (8, 9, and 12-14). Both single-crystal and powder X-ray diffraction studies reveal a two-dimensional extended structure across the entire lanthanide series. The environment around the eight-coordinated Ln(III) atom is best described as a distorted dodecahedron, where HIBA acts as a monoanionic tridentate ligand with one carboxylato oxygen atom and one hydroxyl oxygen atom chelating to one Ln(III) center. The carboxylato oxygen atom from a second HIBA ligand bridges to a neighboring Ln(III) atom to form a two-dimensional extended structure. While the coordination mode for HIBA is identical across the lanthanide series, three different structure types are found for La, Ce-Ho, and Er-Lu. Solution characterization using (13)C NMR further confirmed a single solution complex under the crystallization conditions. Raman and UV-vis-NIR absorbance and diffuse reflectance spectra of HIBA-Ln(III) complexes were also measured.

  14. Self-aggregated dinuclear lanthanide(III) complexes as potential bimodal probes for magnetic resonance and optical imaging.

    Science.gov (United States)

    Regueiro-Figueroa, Martín; Nonat, Aline; Rolla, Gabriele A; Esteban-Gómez, David; de Blas, Andrés; Rodríguez-Blas, Teresa; Charbonnière, Loïc J; Botta, Mauro; Platas-Iglesias, Carlos

    2013-08-26

    Homodinuclear lanthanide complexes (Ln = La, Eu, Gd, Tb, Yb and Lu) derived from a bis-macrocyclic ligand featuring two 2,2',2''-(1,4,7,10-tetraazacyclododecane-1,4,7-triyl)triacetic acid chelating sites linked by a 2,6-bis(pyrazol-1-yl)pyridine spacer (H2L(3)) were prepared and characterized. Luminescence lifetime measurements recorded on solutions of the Eu(III) and Tb(III) complexes indicate the presence of one inner-sphere water molecule coordinated to each metal ion in these complexes. The overall luminescence quantum yields were determined (ϕ H2O = 0.01 for [Eu2(L(3))] and 0.50 for [Tb2(L(3))] in 0.01 M TRIS/HCl, pH 7.4; TRIS = tris(hydroxymethyl)aminomethane), pointing to an effective sensitization of the metal ion by the bispyrazolylpyridyl unit of the ligand, especially with Tb. The nuclear magnetic relaxation dispersion (NMRD) profiles recorded for [Gd2(L(3))] are characteristic of slowly tumbling systems, showing a low-field plateau and a broad maximum around 30 MHz. This suggests the occurrence of aggregation of the complexes giving rise to slowly rotating species. A similar behavior is observed for the analogous Gd(III) complex containing a 4,4'-dimethyl-2,2'-bipyridyl spacer ([Gd2(L(1))]). The relaxivity of [Gd2(L(3))] recorded at 0.5 T and 298 K (pH 6.9) amounts to 13.7 mM(-1)  s(-1). The formation of aggregates has been confirmed by dynamic light scattering (DLS) experiments, which provided mean particle sizes of 114 and 38 nm for [Gd2(L(1))] and [Gd2(L(3))], respectively. TEM images of [Gd2(L(3))] indicate the formation of nearly spherical nanosized aggregates with a mean diameter of about 41 nm, together with some nonspherical particles with larger size.

  15. Two new complexes of Lanthanide(III) ion with the N3O2-donor Schiff base ligand: Synthesis, crystal structure, and magnetic properties

    Science.gov (United States)

    Gao, Xu-Sheng; Jiang, Xia; Yao, Cheng

    2016-12-01

    Two rare earth coordination complexes, [Dy(DAPBH)NO3(H2O)2]ṡ(NO3)2 (1), La(DAPBH)(NO3)3 (2) (where DAPBH = 2, 6-diacetylpyridine benzoyhydrazone), have been synthesized and characterized. Single crystal structural analysis revealed that the Dy3+ ion is nine-coordinated with three N-atoms and two O-atoms from pentadentate DAPBH ligand, two O-atoms from one nitrate and other two O-atoms from two water molecules, and the coordination sphere features as a capped tetragonal antiprism in 1, while the La3+ ion is bound to six O atoms from three nitrate counter ions, three N-atoms and two O-atoms from a pentadentate DAPBH ligand to form a tricapped tetragonal antiprism coordination geometry in 2. Variable-temperature magnetic susceptibility measurements showed the existence of weak antiferromagnetic interaction in 1.

  16. Tri- and tetra-substituted cyclen based lanthanide(III) ion complexes as ribonuclease mimics: a study into the effect of log Ka, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP).

    Science.gov (United States)

    Fanning, Ann-Marie; Plush, Sally E; Gunnlaugsson, Thorfinnur

    2015-05-28

    A series of tetra-substituted 'pseudo' dipeptide ligands of cyclen (1,4,7,10,-tetraazacyclododecane) and a tri-substituted 3'-pyridine ligand of cyclen, and the corresponding lanthanide(III) complexes were synthesised and characterised as metallo-ribonuclease mimics. All complexes were shown to promote hydrolysis of the phosphodiester bond of 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP, τ1/2 = 5.87 × 10(3) h), a well known RNA mimic. The La(III) and Eu(III) tri-substituted 3'-pyridine lanthanide(III) complexes being the most efficient in promoting such hydrolysis at pH 7.4 and at 37 °C; with τ1/2 = 1.67 h for La(III) and 1.74 h for Eu(III). The series was developed to provide the opportunity to investigate the consequences of altering the lanthanide(III) ion, coordination ability and hydrophobicity of a metallo-cavity on the rate of hydrolysis using the model phosphodiester, HPNP, at 37 °C. To further provide information on the role that the log Ka of the metal bound water plays in phosphodiester hydrolysis the protonation constants and the metal ion stability constants of both a tri and tetra-substituted 3'pyridine complex were determined. Our results highlighted several key features for the design of lanthanide(III) ribonucelase mimics; the presence of two metal bound water molecules are vital for pH dependent rate constants for Eu(III) complexes, optimal pH activity approximating physiological pH (∼7.4) may be achieved if the log Ka values for both MLOH and ML(OH)2 species occur in this region, small changes to hydrophobicity within the metallo cavity influence the rate of hydrolysis greatly and an amide adjacent to the metal ion capable of forming hydrogen bonds with the substrate is required for achieving fast hydrolysis.

  17. Prototypes of Lanthanide(III) Agents Responsive to Enzymatic Activities in Three Complementary Imaging Modalities: Visible/Near-Infrared Luminescence, PARACEST-, and T1-MRI.

    Science.gov (United States)

    He, Jiefang; Bonnet, Célia S; Eliseeva, Svetlana V; Lacerda, Sara; Chauvin, Thomas; Retailleau, Pascal; Szeremeta, Frederic; Badet, Bernard; Petoud, Stéphane; Tóth, Éva; Durand, Philippe

    2016-03-09

    We report first prototypes of responsive lanthanide(III) complexes that can be monitored independently in three complementary imaging modalities. Through the appropriate choice of lanthanide(III) cations, the same reactive ligand can be used to form complexes providing detection by (i) visible (Tb(3+)) and near-infrared (Yb(3+)) luminescence, (ii) PARACEST- (Tb(3+), Yb(3+)), or (iii) T1-weighted (Gd(3+)) MRI. The use of lanthanide(III) ions of different natures for these imaging modalities induces only a minor change in the structure of complexes that are therefore expected to have a single biodistribution and cytotoxicity.

  18. Lanthanide(III) complexes of 4,10-bis(phosphonomethyl)-1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (trans-H6do2a2p) in solution and in the solid state: structural studies along the series.

    Science.gov (United States)

    Campello, M Paula C; Lacerda, Sara; Santos, Isabel C; Pereira, Giovannia A; Geraldes, Carlos F G C; Kotek, Jan; Hermann, Petr; Vanek, Jakub; Lubal, Premysl; Kubícek, Vojtech; Tóth, Eva; Santos, Isabel

    2010-07-26

    Complexes of 4,10-bis(phosphonomethyl)-1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (trans-H(6)do2a2p, H(6)L) with transition metal and lanthanide(III) ions were investigated. The stability constant values of the divalent and trivalent metal-ion complexes are between the corresponding values of H(4)dota and H(8)dotp complexes, as a consequence of the ligand basicity. The solid-state structures of the ligand and of nine lanthanide(III) complexes were determined by X-ray diffraction. All the complexes are present as twisted-square-antiprismatic isomers and their structures can be divided into two series. The first one involves nona-coordinated complexes of the large lanthanide(III) ions (Ce, Nd, Sm) with a coordinated water molecule. In the series of Sm, Eu, Tb, Dy, Er, Yb, the complexes are octa-coordinated only by the ligand donor atoms and their coordination cages are more irregular. The formation kinetics and the acid-assisted dissociation of several Ln(III)-H(6)L complexes were investigated at different temperatures and compared with analogous data for complexes of other dota-like ligands. The [Ce(L)(H(2)O)](3-) complex is the most kinetically inert among complexes of the investigated lanthanide(III) ions (Ce, Eu, Gd, Yb). Among mixed phosphonate-acetate dota analogues, kinetic inertness of the cerium(III) complexes is increased with a higher number of phosphonate arms in the ligand, whereas the opposite is true for europium(III) complexes. According to the (1)H NMR spectroscopic pseudo-contact shifts for the Ce-Eu and Tb-Yb series, the solution structures of the complexes reflect the structures of the [Ce(HL)(H(2)O)](2-) and [Yb(HL)](2-) anions, respectively, found in the solid state. However, these solution NMR spectroscopic studies showed that there is no unambiguous relation between (31)P/(1)H lanthanide-induced shift (LIS) values and coordination of water in the complexes; the values rather express a relative position of the central ions between the N(4

  19. Cyclopentadienyl complexes of hafnium and zirconium containing nitrate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Minacheva, M.Kh.; Brajnina, Eh.M.; Klemenkova, Z.S.; Lokshin, B.V.; Nikolaeva, T.D.; Zhdanov, S.I.; Petrovskij, P.V. (AN SSSR, Moscow. Inst. Ehlementoorganicheskikh Soedinenij)

    1983-06-01

    New types of monocyclopentadienyl nitrate complexes of zirconium and hafnium CpHf(DBM)(NO/sub 3/)/sub 2/ and CpHfCl/sub 2/(NO/sub 3/)x4H/sub 2/O (DBM = dibenzoylmethane residue) are synthesized. CpMCl/sub 2/(NO/sub 3/) dichlorides are formed during the reaction of CpM(chel)/sub 2/Cl and HNO/sub 3/ as a result of the interaction of the extracted HCl with the CpM(chel)/sub 2/(NO/sub 3/) exchange product. A supposition is made about the non-ionic character of the metal-nitrate bonds and the bidentate character of the nitrate ligands in Cp/sub 2/M(NO/sub 3/)Cl on the base of studying the electric conductivity, IR- and Raman spectra.

  20. Synthesis, spectral properties and DNA binding and nuclease activity of lanthanide (III) complexes of 2-benzoylpyridine benzhydrazone: X-ray crystal structure, Hirshfeld studies and nitrate- interactions of cerium(III) complex

    Indian Academy of Sciences (India)

    Karreddula Raja; Akkili Suseelamma; Katreddi Hussain Reddy

    2016-01-01

    The lanthanide(III) complexes of general formula of [Ln(BPBH)2(NO3)3] (where, Ln = La, Ce, Pr, Nd and BPBH = 2-benzoylpyridine benzhydrazone) have been synthesized and characterized by elemental analysis, molar conductance, spectroscopic (UV, IR), electrochemical and single crystal X-ray diffraction studies. The coordination mode of the ligand and the geometry of [Ce(BPBH)2(NO3)3] are confirmed by single crystal X-ray studies. The crystals are monoclinic with C2/c crystallographic symmetry. The central metal is 12 coordinated and the coordination polyhedron around the cerium atom can be described as a distorted icosahedron. The existence of nitrate. . . and CH. . . stacking interactions in the [Ce(BPBH)2(NO3)3] leads to a supramolecular arrangement in its network. The binding properties of these complexes with calf-thymus DNA have been investigated by viscosity measurements. The complexes show more nuclease activity in the presences of H2O2.

  1. Fixation of carbon dioxide by macrocyclic lanthanide(III) complexes under neutral conditions producing self-assembled trimeric carbonato-bridged compounds with μ3-η2:η2:η2 bonding.

    Science.gov (United States)

    Bag, Pradip; Dutta, Supriya; Biswas, Papu; Maji, Swarup Kumar; Flörke, Ulrich; Nag, Kamalaksha

    2012-03-28

    A series of mononuclear lanthanide(III) complexes [Ln(LH(2))(H(2)O)(3)Cl](ClO(4))(2) (Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate macrocyclic ligand (LH(2)) in 95 : 5 (v/v) methanol-water solution fix atmospheric carbon dioxide to produce the carbonato-bridged trinuclear complexes [{Ln(LH(2))(H(2)O)Cl}(3)(μ(3)-CO(3))](ClO(4))(4)·nH(2)O. Under similar conditions, the mononuclear Y(III) complex forms the dimeric compound [{Y(LH(2))(H(2)O)Cl}(μ(2)-CO(3)){Y(LH(2))(H(2)O)(2)}](ClO(4))(3)·4H(2)O. These complexes have been characterized by their IR and NMR ((1)H, (13)C) spectra. The X-ray crystal structures have been determined for the trinuclear carbonato-bridged compounds of Nd(III), Gd(III) and Tb(III) and the dinuclear compound of Y(III). In all cases, each of the metal centers are 8-coordinate involving two imine nitrogens and two phenolate oxygens of the macrocyclic ligand (LH(2)) whose two other imines are protonated and intramolecularly hydrogen-bonded with the phenolate oxygens. The oxygen atoms of the carbonate anion in the trinuclear complexes are bonded to the metal ions in tris-bidentate μ(3)-η(2):η(2):η(2) fashion, while they are in bis-bidentate μ(2)-η(2):η(2) mode in the Y(III) complex. The magnetic properties of the Gd(III) complex have been studied over the temperature range 2 to 300 K and the magnetic susceptibility data indicate a very weak antiferromagnetic exchange interaction (J = -0.042 cm(-1)) between the Gd(III) centers (S = 7/2) in the metal triangle through the carbonate bridge. The luminescence spectral behaviors of the complexes of Sm(III), Eu(III), and Tb(III) have been studied. The ligand LH(2) acts as a sensitizer for the metal ions in an acetonitrile-toluene glassy matrix (at 77 K) and luminescence intensities of the complexes decrease in the order Eu(3+) > Sm(3+) > Tb(3+).

  2. Nitrates

    Science.gov (United States)

    ... Blockers Angiotensin-Converting Enzyme (ACE) Inhibitors Antiarrhythmics Anticoagulants Antiplatelet Therapy Aspirin Beta-Blockers Blood Thinners Calcium Channel Blockers Digitalis Medicines Diuretics Inotropic Agents Statins, Cholesterol-Lowering Medicines Nitrates Disclaimer The information ...

  3. Synthesis and Characterization of Heteronuclear Copper(II-Lanthanide(III Complexes of N,N′-1,3-Propylenebis(Salicylaldiminato Where Lanthanide(III = Gd or Eu

    Directory of Open Access Journals (Sweden)

    Longjam Jaideva Singh

    2013-01-01

    Full Text Available Three complexes, namely, [Cu(salbn] (1, [Cu(salbnGd(NO33·H2O] (2, and [Cu(salbnEu(NO33·H2O] (3 where salbn = N,N′-1,3-propylenebis (salicylaldiminato have been synthesized and characterized by elemental analyses, ICP-AES, IR, UV, NMR, MS, EDX, powder XRD, and EPR spectroscopies. The EDX results suggest the presence of two different metal ions in heteronuclear complexes (2 and (3. The ligand(salbn, complex (1, and complex (3 crystallize in triclinic system while complex (2 crystallizes in monoclinic system. The EPR studies suggest that [Cu(salbn] complex is tetragonally coordinated monomeric copper(II complex with unpaired electron in the dx2-y2 orbital and spectral features that are the characteristics of axial symmetry while complex (2 in DMF solution at liquid nitrogen temperature exhibits an anisotropic broad signal around g ~ 2.03 which may suggest a weak magnetic spin-exchange interaction between Gd(III and Cu(II ions. The fluorescence intensity of Eu(III decreased markedly in the complex (3.

  4. Synthesis, spectroscopic characterization, solid state d.c. electrical conductivity and biological studies of some lanthanide(III chloride complexes with a heterocyclic Schiff base ligand

    Directory of Open Access Journals (Sweden)

    K. Mohanan

    2016-07-01

    Full Text Available Condensation of 2-hydroxy-1-naphthaldehyde with 2-amino-3-carboxyethyl-4,5-dimethylthiophene in 1:1 molar ratio, yielded a potentially tridentate Schiff base viz. 2-[N-(2′-hydroxy-1-naphthylideneamino]-3-carboxyethyl-4,5-dimethylthiophene (HNAT. This ligand formed complexes with lanthanum(III, cerium(III, praseodymium(III, neodymium(III, samarium(III, europium(III and gadolinium(III chloride under well defined conditions. These complexes were characterized through elemental analysis, molar conductance, magnetic moment measurements, IR, UV–Vis, FAB mass and 1H NMR spectral studies. Analytical data showed that all the metal complexes exhibited 1:1 metal–ligand ratio. Molar conductance values adequately confirmed the non-electrolytic nature of the metal complexes. The proton NMR spectral observations supplement the IR spectral assignments. The spectral data revealed that the ligand acted as neutral tridentate, coordinating to the metal ion through azomethine nitrogen, ester carbonyl and naphtholate oxygen without deprotonation. The ligand and its lanthanum(III chloride complex were subjected to XRD studies. The lanthanum(III chloride complex has undergone a facile transesterification reaction. The solid state d.c. electrical conductivity of some selected complexes were measured as a function of temperature, indicating the semiconducting nature of the metal complexes. The antimicrobial activities were examined by disk diffusion method against some pathogenic bacterial and fungal species.

  5. Highly Efficient Visible-to-NIR Luminescence of Lanthanide(III) Complexes with Zwitterionic Ligands Bearing Charge-Transfer Character: Beyond Triplet Sensitization.

    Science.gov (United States)

    Pan, Mei; Du, Bin-Bin; Zhu, Yi-Xuan; Yue, Mei-Qin; Wei, Zhang-Wen; Su, Cheng-Yong

    2016-02-12

    Two zwitterionic-type ligands featuring π-π* and intraligand charge-transfer (ILCT) excited states, namely 1,1'-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)dipyridinium-4-olate (TMPBPO) and 1-dodecylpyridin-4(1 H)-one (DOPO), have been prepared and applied to the assembly of lanthanide coordination complexes in an effort to understand the ligand-direction effect on the structure of the Ln complexes and the ligand sensitization effect on the luminescence of the Ln complexes. Due to the wide-band triplet states plus additional ILCT excitation states extending into lower energy levels, broadly and strongly sensitized photoluminescence of f→f transitions from various Ln(3+) ions were observed to cover the visible to near-infrared (NIR) regions. Among which, the Pr, Sm, Dy, and Tm complexes simultaneously display both strong visible and NIR emissions. Based on the isostructural feature of the Ln complexes, color tuning and single-component white light was achieved by preparation of solid solutions of the ternary systems Gd-Eu-Tb (for TMPBPO) and La-Eu-Tb and La-Dy-Sm (for DOPO). Moreover, the visible and NIR luminescence lifetimes of the Ln complexes with the TMPBPO ligand were investigated from 77 to 298 K, revealing a strong temperature dependence of the Tm(3+) ((3) H4 ) and Yb(3+) ((2) F5/2 ) decay dynamics, which has not been explored before for their coordination complexes.

  6. Lanthanide(III) complexes of aminoethyl-DO3A as PARACEST contrast agents based on decoordination of the weakly bound amino group.

    Science.gov (United States)

    Krchová, Tereza; Kotek, Jan; Jirák, Daniel; Havlíčková, Jana; Císařová, Ivana; Hermann, Petr

    2013-11-28

    2-Aminoethyl DOTA analogues with unsubstituted (H3L1), monomethylated (H3L2) and dimethylated (H3L3) amino groups were prepared by improved synthetic procedures. Their solid-state structures exhibit an extensive system of intramolecular hydrogen bonds, which is probably present in solution and leads to the rather high value of the last dissociation constant. The protonation sequence of H3L1 in solution corresponds to that found in the solid state. The stability constants of the H3L1 complexes with La(3+) and Gd(3+) (20.02 and 22.23, respectively) are similar to those of DO3A and the reduction of the pK(A) value of the pendant amino group from 10.51 in the free ligand to 6.06 and 5.83 in the La(3+) and Gd(3+) complexes, respectively, points to coordination of the amino group. It was confirmed in the solid state structure of the [Yb(L1)] complex, where disorder between the SA' and TSA' isomers was found. A similar situation is expected in solution, where a fast equilibration among the isomers hampers the unambiguous determination of the isomer ratio in solution. The PARACEST effect was observed in Eu(III)-H3L1/H3L2 and Yb(III)-H3L1/H3L2 complexes, being dependent on pH in the region of 4.5-7.5 and pH-independent in more alkaline solutions. The decrease of the PARACEST effect parallels with the increasing abundance of the complex protonated species, where the pendant amino group is not coordinating. Surprisingly, a small PARACEST effect was also observed in solutions of Eu(III)/Yb(III)-H3L3 complexes, where the pendant amino group is dimethylated. The effect is detectable in a narrow pH region, where both protonated and deprotonated complex species are present in equilibrium. The data points to the new mechanism of the PARACEST effect, where the slow coordination-decoordination of the pendant amine is coupled with the fast proton exchange between the free amino group and bulk water mediates the magnetization transfer. The pH-dependence of the effect was proved to be

  7. Antioxidation and DNA-binding properties of binuclear lanthanide(III) complexes with a Schiff base ligand derived from 8-hydroxyquinoline-7-carboxaldehyde and benzoylhydrazine.

    Science.gov (United States)

    Liu, Yongchun; Zhang, Kejun; Wu, Yun; Zhao, Junying; Liu, Jianning

    2012-08-01

    8-Hydroxyquinoline-7-carboxaldehyde (8-HQ-7-CA), Schiff-base ligand 8-hydroxyquinoline-7-carboxaldehyde benzoylhydrazone, and binuclear complexes [LnL(NO(3))(H(2)O)(2)](2) were prepared from the ligand and equivalent molar amounts of Ln(NO(3))·6H(2)O (Ln=La(3+), Nd(3+), Sm(3+), Eu(3+), Gd(3+), Dy(3+), Ho(3+), Er(3+), Yb(3+), resp.). Ligand acts as dibasic tetradentates, binding to Ln(III) through the phenolate O-atom, N-atom of quinolinato unit, and C=N and -O-C=N- groups of the benzoylhydrazine side chain. Dimerization of this monomeric unit occurs through the phenolate O-atoms leading to a central four-membered (LnO)(2) ring. Ligand and all of the Ln(III) complexes can strongly bind to CT-DNA through intercalation with the binding constants at 10(5)-10(6) M(-1). Moreover, ligand and all of the Ln(III) complexes have strong abilities of scavenging effects for hydroxyl (HO·) radicals. Both the antioxidation and DNA-binding properties of Ln(III) complexes are much better than that of ligand.

  8. Lanthanide(III) complexes of bis-semicarbazone and bis-imine-substituted phenanthroline ligands: solid-state structures, photophysical properties, and anion sensing.

    Science.gov (United States)

    Nadella, Sandeep; Selvakumar, Paulraj M; Suresh, Eringathodi; Subramanian, Palani S; Albrecht, Markus; Giese, Michael; Fröhlich, Roland

    2012-12-21

    Phenanthroline-based hexadentate ligands L(1) and L(2) bearing two achiral semicarbazone or two chiral imine moieties as well as the respective mononuclear complexes incorporating various lanthanide ions, such as La(III), Eu(III), Tb(III), Lu(III), and Y(III) metal ions, were synthesized, and the crystal structures of [ML(1)Cl(3)] (M=La(III), Eu(III), Tb(III), Lu(III), or Y(III)) complexes were determined. Solvent or water molecules act as coligands for the rare-earth metals in addition to halide anions. The big Ln(III) ion exhibits a coordination number (CN) of 10, whereas the corresponding Eu(III), Tb(III), Lu(III), and Y(III) centers with smaller ionic radii show CN=9. Complexes of L(2), namely [ML(2)Cl(3)] (M=Eu(III), Tb(III), Lu(III), or Y(III)) ions could also be prepared. Only the complex of Eu(III) showed red luminescence, whereas all the others were nonluminescent. The emission properties of the Eu derivative can be applied as a photophysical signal for sensing various anions. The addition of phosphate anions leads to a unique change in the luminescence behavior. As a case study, the quenching behavior of adenosine-5'-triphosphate (ATP) was investigated at physiological pH value in an aqueous solvent. A specificity of the sensor for ATP relative to adenosine-5'-diphosphate (ADP) and adenosine-5'-monophosphate (AMP) was found. (31)P NMR spectroscopic studies revealed the formation of a [EuL(2)(ATP)] coordination species.

  9. Evidence of different stoichiometries for the limiting carbonate complexes across the lanthanide(III) series: A capillary electrophoresis-mass spectrometry study

    Energy Technology Data Exchange (ETDEWEB)

    Philippini, V.; Vercouter, T.; Vitorge, P. [CEA, Dept Physicochem, Lab Speciat Radionucleides et Mol, F-91191 Gif Sur Yvette, (France); Aupiais, J.; Topin, S.; Ambard, C. [CEA, Serv Radioanalyse Chim et Environm, Bruyeres Le Chatel, (France); Chausse, A.; Vitorge, P. [Lab Analyse et Modelisat Biol et Environm, Evry, (France)

    2008-07-01

    The electrophoretic mobilities ({mu}{sub ep,Ln}) of twelve lanthanides (not Ce, Pr and Yb) were measured by CE-ICP-MS in 0.15 and 0.5 mol L{sup -1} Alk{sub 2}CO{sub 3} aqueous solutions for Alk{sup +} = Li{sup +}, Na{sup +}, K{sup +} and Cs{sup +}. In 0.5 mol L{sup -1} solutions, two different {mu}{sub ep,Ln} values were found for the light (La to Nd) and the heavy (Dy to Tm) lanthanides, which suggests two different stoichiometries for the carbonate limiting complexes. These results are consistent with a solubility study that attests the Ln(CO{sub 3}){sub 3}{sup 3-} and Ln(CO{sub 3}){sub 4}{sup 5-} stoichiometries for the heavy (small) and the light (big) lanthanides, respectively. The Alk{sup +} counter-ions influence the {mu}{sub ep,Ln}{sup Alk2CO3} values, but not the overall shape of the {mu}{sub ep,Ln}{sup Alk2CO3} plots as a function of the lanthanide atomic numbers: the counter-ions do not modify the stoichiometries of the inner sphere complexes. The influence of the Alk{sup +} counter-ions decreases in the Li{sup +} {>=} Na{sup +} {>=}{>=} K{sup +} {>=} Cs{sup +} series. The K{sub 3,Ln} stepwise formation constants of the Ln(CO{sub 3}){sub 3}{sup 3-} complexes slightly increase with the atomic numbers of the lanthanides while K{sub 4,Ln}, the stepwise formation constants of Ln(CO{sub 3}){sub 4}{sup 5-} complexes, slightly decrease from La to Th, and is no longer measurable for heavier lanthanides. (authors)

  10. Solid-state and solution-state coordination chemistry of lanthanide(III) complexes with (pyrazol-1-yl)acetic acid.

    Science.gov (United States)

    Chen, Xiao-Yan; Goff, George S; Scott, Brian L; Janicke, Michael T; Runde, Wolfgang

    2013-03-18

    As a precursor of carboxyl-functionalized task-specific ionic liquids (TSILs) for f-element separations, (pyrazol-1-yl)acetic acid (L) can be deprotonated as a functionalized pyrazolate anion to coordinate with hard metal cations. However, the coordination chemistry of L with f-elements remains unexplored. We reacted L with lanthanides in aqueous solution at pH = 5 and synthesized four lanthanide complexes of general formula [Ln(L)3(H2O)2]·nH2O (1, Ln = La, n = 2; 2, Ln = Ce, n = 2; 3, Ln = Pr, n = 2; 4, Ln = Nd, n = 1). All complexes were characterized by single crystal X-ray diffraction analysis revealing one-dimensional chain formations. Two distinct crystallographic structures are governed by the different coordination modes of carboxylate groups in L: terminal bidentate and bridging tridentate (1-3); terminal bidentate, bridging bidentate, and tridentate coordination in 4. Comparison of the solid state UV-vis-NIR diffuse reflectance spectra with solution state UV-vis-NIR spectra suggests a different species in solution and solid state. The different coordination in solid state and solution was verified by distinctive (13)C NMR signals of the carboxylate groups in the solid state NMR.

  11. Spectrophotometric study of neptunium (VI) complexation by nitrate ions; Etude par spectrophotometrie de la complexation du neptunium au degre d'oxydation (VI) par les ions nitrates

    Energy Technology Data Exchange (ETDEWEB)

    Pochon, P. [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification (DRRV), 30 - Marcoule (France)]|[Conservatoire National des Arts et Metiers (CNAM), 75 - Paris (France)]|[Centre Regional Associe de Lyon, 69 (France)

    2000-07-01

    Neptunium(VI) complexation by nitrate ions was investigated by visible and near-infrared spectrophotometry, a technique suitable for observing the appearance and evolution of the species in solution. In the absence of reference spectra for Np(VI) nitrate- complexes, mathematical (factor analysis) tools were used to interpret the spectra. These chemo-metric techniques were first tested and validated on a simpler chemical system: Np(VI)complexation by the SiW{sub 11}O{sub 39}{sup 8-} anion. The test media used to investigate Np(VI) nitrate- complexes generally contain nitrate and perchlorate salts at high concentrations (high ionic strength). Media effects arising from the presence of cations, acidity or the perchlorate ion concentration are therefore significant, and no doubt account for the scattered values of the complexation constants published in the literature. The evolution of the neptunium spectra according to the parameters of the reaction medium illustrated these effects and allowed them to be quantified by a global 'perturbation constant'. In order to minimize the spectrum modifications due to media effects, the neptunium nitrate-complexes were studied at constant ionic strength in weak acidic media (2 mol.kg{sup -1}{sub H2O}) in the presence of sodium salts. The bulk formation constants and the spectrum of the NpO{sub 2}(NO{sub 3}){sup +} complex were determined for ionic strength values of 2.2, 4, 6 and 8 mol.kg{sup -1}{sub H2O}. The constants remained on the same order of magnitude regardless of the ionic strength; the thermodynamic constant {beta}{sub 1}{sup 0} determined from them according to specific interaction theory is thus probably of little significance. Conversely, the bulk constants can be corrected for the effects of the perchlorate ions by taking the global 'perturbation constant' into account. (author)

  12. SPECTROSCOPIC STUDIES OF SOME LANTHANIDE(III) NITRATE ...

    African Journals Online (AJOL)

    a

    involving the formation of imines groups is well known. ... This phenol-based macroacyclic ligand have two similar metal-binding sites sharing the .... position of phenol moiety promote the reaction of the Schiff base as monoanionic ligand and ...

  13. Synthesis, Characterization and Properties of Lanthanide Nitrate Complexes with Isonicotinoyl Hydrazone

    Institute of Scientific and Technical Information of China (English)

    卜显和; 高育新; 陈巍; 刘河; 张若桦

    2001-01-01

    Some light-lanthanide nitrate complexes were obtained by the reaction of lanthanide nitrate with isonicotinoyl hydrazone (HL=N,N′-diisonicotinoyl-2-hydroxy-5-methyl-isophthalaldehyde dihydrazone) in methanol. The general formula of the complexes is Ln(L)(NO3)2*nH2O(Ln=La, Ce, Pr, Nd and Sm; n=0, 1). The complexes were characterized by elemental analyses, conductance, thermal analyses, UV and IR spectra. The results show that the lanthanide ion in each complex is coordinated by oxygen and nitrogen atoms of the ligand (L) and the oxygen atoms of the nitrate. The amide-oxygen atoms of L coordinate to the Ln ions in its keto-form. The magnetic susceptibility of the neodymium complex shows that the magnetic data obey Curie-Weiss law in the range of 75K<T<300K.

  14. Nitrate adsorption from aqueous solution using granular chitosan-Fe{sup 3+} complex

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Qili [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing, 100083 (China); Key Laboratory of Groundwater Cycle and Environment Evolution,China University of Geosciences (Beijing), Ministry of Education, Beijing, 100083 (China); Chen, Nan, E-mail: chennan@cugb.edu.cn [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing, 100083 (China); Key Laboratory of Groundwater Cycle and Environment Evolution, China University of Geosciences (Beijing), Ministry of Education, Beijing, 100083 (China); Feng, Chuanping [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing, 100083 (China); Key Laboratory of Groundwater Cycle and Environment Evolution, China University of Geosciences (Beijing), Ministry of Education, Beijing, 100083 (China); Hu, WeiWu [The Journal Center, China University of Geosciences (Beijing), Beijing, 100083 (China)

    2015-08-30

    Highlights: • Granular chitosan-Fe{sup 3+} complex had high performance for nitrate adsorption. • Granular chitosan-Fe{sup 3+} complex had shorter equilibrium time (1.5 h). • Nitrate adsorption was ascribed to ion exchange and electrostatic attraction. • Granular chitosan-Fe{sup 3+} complex could be regenerated using NaCl solution. - Abstract: In the present study, In order to efficiently remove nitrate, granular chitosan-Fe{sup 3+} complex with high chemical stability and good environmental adaptation was synthesized through precipitation method and characterized using SEM, XRD, BET and FTIR. The nitrate adsorption performance was evaluated by batch experiments. The results indicated that granular chitosan-Fe{sup 3+} complex was an amorphous and mesoporous material. The BET specific surface area and average pore size were 8.98 m{sup 2} g{sup −1} and 56.94 Å, respectively. The point of zero charge was obtained at pH 5. The maximum adsorption capacity reached 8.35 mg NO{sub 3}{sup −}-N g{sup −1} based on Langmuir–Freundlich model. Moreover, no significant change in the nitrate removal efficiency was observed in the pH range of 3.0–10.0. The adverse influence of sulphate on nitrate removal was the most significant, followed by bicarbonate and fluoride, whereas chloride had slightly adverse effect. Adsorption process followed the pseudo-second-order kinetic model, and the experimental equilibrium data were fitted well with the Langmuir–Freundlich and D–R isotherm models. Thermodynamic parameters revealed that nitrate adsorption was a spontaneous and exothermic process. Granular chitosan-Fe{sup 3+} complex could be effectively regenerated by NaCl solution.

  15. Kinetic studies of nitrate removal from aqueous solution using granular chitosan-Fe(III) complex.

    Science.gov (United States)

    Hu, Qili; Chen, Nan; Feng, Chuanping; Zhang, Jing; Hu, Weiwu; Lv, Long

    2016-01-01

    In the present study, a granular chitosan-Fe(III) complex was prepared as a feasible adsorbent for the removal of nitrate from an aqueous solution. There was no significant change in terms of nitrate removal efficiency over a wide pH range of 3-11. Nitrate adsorption on the chitosan-Fe(III) complex followed the Langmuir-Freundlich isotherm model. In order to more accurately reflect adsorption and desorption behaviors at the solid/solution interface, kinetic model I and kinetic model II were proposed to simulate the interfacial process in a batch system. Nitrate adsorption on the chitosan-Fe(III) complex followed the pseudo-first-order kinetic model and kinetic model I. The proposed half-time could provide useful information for optimizing process design. Adsorption and desorption rate constants obtained from kinetic model I and kinetic model II were beneficial to understanding the interfacial process and the extent of adsorption reaction. Kinetic model I and kinetic model II implied that nitrate uptake exponentially approaches a limiting value.

  16. Complexes of uranyl nitrate with 2,6-pyridinedicarboxamides: synthesis, crystal structure, and DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Alyapyshev, Mikhail; Babain, Vasiliy [ITMO University, 49, Kronverksky pr., 197101, St. Petersburg (Russian Federation); ThreeArc Mining Ltd., 5, Stary Tolmachevskiy per., 115184, Moscow (Russian Federation); Tkachenko, Lyudmila; Lumpov, Alexander [Khlopin Radium Institute, 28, 2nd Murinskiy pr., 194021, St. Petersburg (Russian Federation); Gurzhiy, Vladislav; Zolotarev, Andrey; Dar' in, Dmitriy [St. Petersburg State University, 7-9, Universitetskaya nab., 199034, St. Petersburg (Russian Federation); Ustynyuk, Yuriy; Gloriozov, Igor [M.V. Lomonosov Moscow State University, 119991, Moscow (Russian Federation); Paulenova, Alena [Department of Nuclear Engineering, Oregon State University, Corvallis, OR (United States)

    2017-05-04

    Two complexes of uranyl nitrate with N,N,N',N'-tetrabutyl-2,6-pyridinedicarboxamide (TBuDPA) and N,N'-diethyl-N,N'-diphenyl-2,6-pyridinedicarboxamide (EtPhDPA) were synthesized and studied. The complex of tetraalkyl-2,6-pyridinedicarboxamide with metal nitrate was synthesized for the first time. XRD analysis revealed the different type of complexation: a 1:1 metal:ligand complex for EtPhDPA and complex with polymeric structure for TBuDPA. The quantum chemical calculations (DFT) confirm that both ligands form the most stable complexes that match the minimal values pre-organization energy of the ligands. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Coordination mode of nitrate in uranyl(VI) complexes: a first-principles molecular dynamics study.

    Science.gov (United States)

    Bühl, Michael; Diss, Romain; Wipff, Georges

    2007-06-25

    According to Car-Parrinello molecular dynamics simulations for [UO(2)(NO(3))(3)](-), [UO(2)(NO(3))(4)](2-), and [UO(2)(OH(2))(4-)(NO(3))](+) complexes in the gas phase and in aqueous solution, the nitrate coordination mode to uranyl depends on the interplay between ligand-metal attractions, interligand repulsions, and solvation. In the trinitrate, the eta(2)-coordination is clearly favored in water and in the gas phase, leading to a coordination number (CN) of 6. According to pointwise thermodynamic integration involving constrained molecular dynamics simulations, a change in free energy of +6 kcal/mol is predicted for eta(2)- to eta(1)-transition of one of the three nitrate ligands in the gas phase. In the gas phase, the mononitrate-hydrate complex also prefers a eta(2)-binding mode but with a CN of 5, one H(2)O molecule being in the second shell. This contrasts with the aqueous solution where the nitrate binds in a eta(1)-fashion and uranyl coordinates to four H2O ligands. A driving force of ca. -3 kcal/mol is predicted for the eta(2)- to eta(1)- transition in water. This structural preference is interpreted in terms of steric arguments and differential solvation of terminal vs uranyl-coordinated O atoms of the nitrate ligands. The [UO(2)(NO(3))(4)](2-) complex with two eta(2)- and two eta(1)- coordinated nitrates, observed in the solid state, is stable for 1-2 ps in the gas phase and in solution. In the studied series, the modulation of uranyl-ligand distances upon immersion of the complex in water is found to depend on the nature of the ligand and the composition of the complex.

  18. Interaction between hydrogen sulfide-induced sulfhydration and tyrosine nitration in the KATP channel complex.

    Science.gov (United States)

    Kang, Minho; Hashimoto, Atsushi; Gade, Aravind; Akbarali, Hamid I

    2015-03-15

    Hydrogen sulfide (H₂S) is an endogenous gaseous mediator affecting many physiological and pathophysiological conditions. Enhanced expression of H2S and reactive nitrogen/oxygen species (RNS/ROS) during inflammation alters cellular excitability via modulation of ion channel function. Sulfhydration of cysteine residues and tyrosine nitration are the posttranslational modifications induced by H₂S and RNS, respectively. The objective of this study was to define the interaction between tyrosine nitration and cysteine sulfhydration within the ATP-sensitive K(+) (KATP) channel complex, a significant target in experimental colitis. A modified biotin switch assay was performed to determine sulfhydration of the KATP channel subunits, Kir6.1, sulphonylurea 2B (SUR2B), and nitrotyrosine measured by immunoblot. NaHS (a donor of H₂S) significantly enhanced sulfhydration of SUR2B but not Kir6.1 subunit. 3-Morpholinosydnonimine (SIN-1) (a donor of peroxynitrite) induced nitration of Kir6.1 subunit but not SUR2B. Pretreatment with NaHS reduced the nitration of Kir6.1 by SIN-1 in Chinese hamster ovary cells cotransfected with the two subunits, as well as in enteric glia. Two specific mutations within SUR2B, C24S, and C1455S prevented sulfhydration by NaHS, and these mutations prevented NaHS-induced reduction in tyrosine nitration of Kir6.1. NaHS also reversed peroxynitrite-induced inhibition of smooth muscle contraction. These studies suggest that posttranslational modifications of the two subunits of the KATP channel interact to alter channel function. The studies described herein demonstrate a unique mechanism by which sulfhydration of one subunit modifies tyrosine nitration of another subunit within the same channel complex. This interaction provides a mechanistic insight on the protective effects of H₂S in inflammation. Copyright © 2015 the American Physiological Society.

  19. Energetic Ionic Liquids Based on Lanthanide Nitrate Complex Anions (Postprint)

    Science.gov (United States)

    2008-01-01

    xH2O (x=27–44) [5a] and lanthanide complexes of the pseudohalide SCN in the hydrolytically unstable [ bmim ]4Ln ACHTUNGTRENNUNG(SCN)7·H2O ( bmim =1-butyl-3...Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim These are not the final page numbers! &1& FULL PAPER cal ionic liquids. The instability of [ bmim ]4Ln... bmim ]4Ln ACHTUNGTRENNUNG(SCN)7·H2O ionic liquids by displacing the isothiocyanate ligand.[5b] In our syntheses, guanidinium ni- trate and lanthanum or

  20. Terminal group effects on the fluorescence spectra of Eu(III) nitrate complexes with a family of amide-based 1,10-phenanthroline derivatives

    Science.gov (United States)

    Chen, Su-Wen; Zhang, Yu-Liang; Dou, Wei; Wang, Ya-Wen; Liu, Wei-Sheng

    2005-12-01

    Four ligands 1,10-phenanthroline-5,6-bis( N, N-dibenzyl-1'-oxopropylamide) (L a) 1,10-phenanthroline-5,6-bis( N-methyl-N-benzyl-1'-oxopropylamide) (L b) 1,10-phenanthroline-5,6-bis(N-benzyl-1'-oxopropylamide) (L c) and 1,10-phenanthroline-5,6-bis( N, N-diethyl-1'-oxopropylamide) (L d), and their lanthanide(III) (La and Eu) complexes were synthesized. The complexes were characterized by elemental analysis, IR, fluorescence spectroscopy and conductivity. The lanthanide atoms are coordinated by O atoms from C=O, Ar-O -C and N atoms from phen With the difference of the ligands, the fluorescent intensities of the Eu(III) complexes vary regularly in the THF solution. Some factors that influence the fluorescent intensity were discussed.

  1. Influence of nitrate ions on the physicochemical behavior of neptunium; Etude de la complexation du neptunium+6 par les ions nitrate: approche chimiometrique

    Energy Technology Data Exchange (ETDEWEB)

    Pochon, P.; Moisy, Ph.; Blanc, P. [CEA Valrho, (DCC/DRRV/SEMP), 30 - Marcoule (France)

    2000-07-01

    The aim of this work was to acquire data on Np(VI) nitrate-complexes, particularly concerning their stability in nitric acid media, to gain a closer understanding of neptunium behavior in the PUREX process used for spent nuclear fuel reprocessing. Due to their very poor stability and the importance of physico-chemical mechanisms in concentrated solutions (media effects), the published data concerning these complexes are subject to considerable debate. A visible and near-infrared spectrophotometric study of Np(VI) nitrate-complexes was therefore undertaken to observe and quantify the influence of nitrate ions on the physicochemical behavior of neptunium, and to estimate the magnitude of the media effects in order to propose a constant of complexation by nitrate ions that is independent of the composition of the reaction medium (i.e. a thermodynamic constant). In the absence of reliable spectra for neptunium in nitric acid media, the spectrophotometric data were processed by principal components analysis and factor analysis mathematical method. The ionic strength of the solutions was adjusted by adding perchlorate salts (perchlorate ions were considered to have little or no complexing properties). The influence of the type of cation (H{sup +}, Li{sup +}, Na{sup +}, Ba{sup 2+}, Mg{sup 2+}) and the perchlorate ion concentration was observed on the neptunium(VI) spectra in nitric and perchloric media. In the presence of nitrate ions, the spectrum modifications in case of substitution of one cation by another were comparable to those observed for major nitrate ion concentration variations. Similarly, the extent of the spectrum modifications for the same nitrate ion concentration variation depended on the proton concentration. Weak spectrum modifications were also observed when the perchlorate ion concentration varied. They were quantified by a 'perturbation constant' {beta}* calculated in the same way as a complexation constant ({beta}* = 0.023 in the molal

  2. Coordinatively Unsaturated Lanthanide(III) Helicates: Luminescence Sensors for Adenosine Monophosphate in Aqueous Media.

    Science.gov (United States)

    Sahoo, Jashobanta; Arunachalam, Rajendran; Subramanian, Palani S; Suresh, Eringathodi; Valkonen, Arto; Rissanen, Kari; Albrecht, Markus

    2016-08-08

    Coordinatively unsaturated double-stranded helicates [(H2 L)2 Eu2 (NO3 )2 (H2 O)4 ](NO3 )4 , [(H2 L)2 Tb2 (H2 O)6 ](NO3 )6 , and [(H2 L)2 Tb2 (H2 O)6 ]Cl6 (H2 L=butanedioicacid-1,4-bis[2-(2-pyridinylmethylene)hydrazide]) are easily obtained by self-assembly from the ligand and the corresponding lanthanide(III) salts. The complexes are characterized by X-ray crystallography showing the helical arrangement of the ligands. Co-ligands at the metal ions can be easily substituted by appropriate anions. A specific luminescence response of AMP in presence of ADP, ATP, and other anions is observed. Specificity is assigned to the perfect size match of AMP to bridge the two metal centers and to replace quenching co-ligands in the coordination sphere.

  3. Standard Enthalpies of Formation of Solid Complexes of Lanthanide Nitrates with Alanine

    Institute of Scientific and Technical Information of China (English)

    杨旭武; 陈三平; 高胜利; 刘晓华; 史启祯

    2002-01-01

    The combustion energies of fourteen solid complexes of lanthanide nitrate with alanine were determined. The standard enthalpies of combustion, Δc,coor(s)H°, and standard enthalpies of formation, Δf,coor(s)H°, were calculated for these complexes. The relationship of Δc,coor(s)H° and Δf,coor(s)H° with the atomic numbers of the elements in the lanthanide series were examined. The results show that a certain amount of covalence is present in the chemical bond between the lanthanide cations and alanine.

  4. Synthesis, Characterization and Fluorescence of Phenylcarboxymethyl Sulfoxide Complexes with Lanthanide Nitrates

    Institute of Scientific and Technical Information of China (English)

    李文先; 张东凤

    2002-01-01

    Phenylcarboxymethyl Sulfoxide, PhSOCH2COOH(LH), complexes of six lanthanide nitrates: Ln2L2(NO3)4*2LH*nH2O(where Ln=La, Ce, Pr, Nd, Sm, Eu) were synthesized. Elemental analyses, molar conductivities, IR, 1HNMR and TG-DTA measurements were used to characterize the complexes. The results show that the ligand(L) is coordinated to metal ions through two oxygen atoms of the carboxyl group and one oxygen atom of the sulfoxide moieties. Neutral ligang (LH)is coordinated to two metal ions through two oxygen atoms of carboxyl group as an asymmetrical bridging bidentate. The fluorescence spectra of Eu3+ complex indicates that there is no inversion symmetry at the site of Eu3+ ion, but the emission intensity of fluorescence is quite good.The solubility of the complexes is very good in water.

  5. Electronic structure and spectral properties of terbium(III) nitrate complex with hexamethylphosphoramide

    Science.gov (United States)

    Kharchenko, Valerii I.; Kurbatov, Ilya A.; Cherednichenko, Alexander I.; Mirochnik, Anatoly G.; Zhikhareva, Polina A.

    2017-03-01

    Spectral properties of terbium(III) nitrate complex with hexamethylphosphoramide have been studied by quantum-chemical methods within the density functional theory and methods of luminescent and X-ray photoelectron spectroscopy. Analysis of the luminescence excitation spectrum of the complex has indicated the absence of intramolecular transfer of electronic excitation energy from the ligand levels to the resonance levels of the rare earth central ion, so luminescence of the complex is associated with the electronic f-f-transitions of Tb3 + ion (transitions 5D4 → 7FJ, J = 3-6). According to quantum-chemical modeling of the excited singlet and triplet levels of the complex, the excitation energy transfer from the ligands onto the central ion does not occur because of the significant difference of energies of their excited states.

  6. Synthesis, characterization and thermolysis of lanthanide metal nitrate complexes with 1, 10-phenanthroline, Part-95

    Institute of Scientific and Technical Information of China (English)

    Nibha; BP Baranwal; Gurdip Singh; Constantin G. Daniliuc

    2014-01-01

    The nitrate complexes of cerium, praseodymium and neodymium with 1,10-phenanthroline (phen) of general formula [Ln(phen)2(NO3)2(H2O)2]·NO3 (where, Ln=Ce, Pr and Nd) were prepared and characterized by X-ray crystallography. Thermolysis of these complexes was investigated by simultaneous thermogravimetry (TG) and differential thermal analysis (DTA). Isothermal TG was taken to evaluate the kinetic parameters using model fitting as well as model free isoconversional methods. The thermolytic pathways were also suggested, which involves decomposition followed by ignition. All the three complexes had coordination number ten and showed multistep decompositions. In order to evaluate the response of rapid heating, ignition delay (Di) measurements were undertaken. The activation energies for ignition were found to decrease in the order: Nd>Pr>Ce.

  7. Crystal structures of bis- and hexakis[(6,6′-dihydroxybipyridinecopper(II] nitrate coordination complexes

    Directory of Open Access Journals (Sweden)

    Deidra L. Gerlach

    2015-12-01

    Full Text Available Two multinuclear complexes synthesized from Cu(NO32 and 6,6′-dihydroxybipyridine (dhbp exhibit bridging nitrate and hydroxide ligands. The dinuclear complex (6,6′-dihydroxybipyridine-2κ2N,N′[μ-6-(6-hydroxypyridin-2-ylpyridin-2-olato-1:2κ3N,N′:O2](μ-hydroxido-1:2κ2O:O′(μ-nitrato-1:2κ2O:O′(nitrato-1κOdicopper(II, [Cu2(C10H7N2O2(OH(NO32(C10H8N2O2] or [Cu(6-OH-6′-O-bpy(NO3(μ-OH(μ-NO3Cu(6,6′-dhbp], (I, with a 2:1 ratio of nitrate to hydroxide anions and one partially deprotonated dhbp ligand, forms from a water–ethanol mixture at neutral pH. The hexanuclear complex bis(μ3-bipyridine-2,2′-diolato-κ3O:N,N′:O′tetrakis(6,6′-dihydroxybipyridine-κ2N,N′tetrakis(μ-hydroxido-κ2O:O′bis(methanol-κOtetrakis(μ-nitrato-κ2O:O′hexacopper(II, [Cu6(C10H6N2O22(CH4O2(OH4(NO34(C10H8N2O24] or [Cu(6,6′-dhbp(μ-NO32(μ-OHCu(6,6′-O-bpy(μ-OHCu(6,6′dhbp(CH3OH]2, (II, with a 1:1 NO3–OH ratio and two fully protonated and fully deprotonated dhbp ligands, was obtained by methanol recrystallization of material obtained at pH 3. Complex (II lies across an inversion center. Complexes (I and (II both display intramolecular O—H...O hydrogen bonding. Intermolecular O—H...O hydrogen bonding links symmetry-related molecules forming chains along [100] for complex (I with π-stacking along [010] and [001]. Complex (II forms intermolecular O—H...O hydrogen-bonded chains along [010] with π-stacking along [100] and [001].

  8. Complex phylogeny and gene expression patterns of members of the NITRATE TRANSPORTER 1/PEPTIDE TRANSPORTER family (NPF) in wheat.

    Science.gov (United States)

    Buchner, Peter; Hawkesford, Malcolm J

    2014-10-01

    NPF (formerly referred to as low-affinity NRT1) and 'high-affinity' NRT2 nitrate transporter genes are involved in nitrate uptake by the root, and transport and distribution of nitrate within the plant. The NPF gene family consists of 53 members in Arabidopsis thaliana, however only 11 of these have been functionally characterized. Although homologous genes have been identified in genomes of different plant species including some cereals, there is little information available for wheat (Triticum aestivum). Sixteen genes were identified in wheat homologous to characterized Arabidopsis low-affinity nitrate transporter NPF genes, suggesting a complex wheat NPF gene family. The regulation of wheat NFP genes by plant N-status indicated involvement of these transporters in substrate transport in relation to N-metabolism. The complex expression pattern in relation to tissue specificity, nitrate availability and senescence may be associated with the complex growth patterns of wheat depending on sink/source demands, as well as remobilization during grain filling.

  9. Complexation of Sn{sub 2}Se{sub 6} with lanthanide(III) centers influenced by ethylene polyamines: Solvothermal syntheses, crystal structures, and optical properties of lanthanide selenidostannates

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Chunying; Wang, Fang; Chen, Ruihong; Jiang, Wenqing; Zhang, Yong; Jia, Dingxian, E-mail: jiadingxian@suda.edu.cn

    2013-08-15

    Lanthanide selenidostannates (H{sub 3}O){sub n}[Ce(tepa)(μ-1κ{sup 2}:2κ{sup 2}-Sn{sub 2}Se{sub 6})]{sub n} (1), [(Yb(tepa)(μ-OH)){sub 2}(μ-1κ:2κ-Sn{sub 2}Se{sub 6})]{sub n}·nH{sub 2}O (2), [Htrien]{sub 2}[(Ln(trien)(tren)){sub 2}(μ-1κ:2κ-Sn{sub 2}Se{sub 6})][Sn{sub 2}Se{sub 6}] (Ln=Ce(3), Nd(4)) and [(Yb(dien){sub 2}){sub 2}(μ-OH){sub 2}]Sn{sub 2}Se{sub 6} (5) were solvothermally prepared in different ethylene polyamines. The Sn{sub 2}Se{sub 6} unit connects [Ce(tepa)]{sup 3+} and [(Yb(tepa)(μ-OH)){sub 2}]{sup 4+} fragments with tetradentate μ-1κ{sup 2}Se{sup 1},Se{sup 2}:2κ{sup 2}Se{sup 5},Se{sup 6} and bidentate μ-1κSe{sup 1}:2κSe{sup 5} bridging coordination modes in tepa, to form polymers 1 and 2, respectively. It joins two [Ln(trien)(tren)]{sup 3+} fragments as a μ-1κSe{sup 1}:2κSe{sup 5} ligand to form binuclear complexes 3 and 4 in trien. Unlike the Sn{sub 2}Se{sub 6} units in 1–4 that bind with Ln(III) centers as Se-donor ligands, the Sn{sub 2}Se{sub 6} unit in 5 exists as a discrete ion. The syntheses of 1–5 show that the ethylene polyamines play an important role in the complexation of Sn{sub 2}Se{sub 6} ligand with Ln(III) centers. Compounds 1–5 exhibit optical band gaps in the range of 2.09–2.42 eV, which are influenced by the complexation of Sn{sub 2}Se{sub 6} with Ln(III) centers. - Graphical abstract: New lanthanide complexes concerning the Sn{sub 2}Se{sub 6} ligand were solvothermally prepared, and the effect of ethylene polyamines on the complexation of Sn{sub 2}Se{sub 6} with Ln(III) centers are observed. Highlights: • Lanthanide complexes concerning the selenidostannates have been solvothermally prepared in different ethylene polyamines. • A tetradentate μ-1κ{sup 2}Se{sup 1},Se{sup 2}:2κ{sup 2}Se{sup 5},Se{sup 6} and a bidentate μ-1κSe{sup 1}:2κSe{sup 5} bridging coordination modes for the Sn{sub 2}Se{sub 6} ligand is obtained. • The complexation of the Sn{sub 2}Se{sub 6} ligand with Ln(III) centers are

  10. Reaction of a copper(II)-nitrosyl complex with hydrogen peroxide: phenol ring nitration through a putative peroxynitrite intermediate.

    Science.gov (United States)

    Kalita, Apurba; Deka, Ramesh C; Mondal, Biplab

    2013-10-07

    Copper(II) complex, 1, with the histidine-derived ligand L (L = methyl 2-(2-hydroxybenzylamino)-3-(1H-imidazol-5-yl)propanoate) has been synthesized and characterized. Single-crystal structure determination reveals a diphenolato-bridged dicopper(II) core in 1. Addition of (•)NO to an acetonitrile solution of 1 affords the corresponding mononuclear copper(II)-nitrosyl complex, 2. In the presence of H2O2, 2 results in formation of the corresponding copper(I)-peroxynitrite. Formation of peroxynitrite ((-)OONO) intermediate is evident from its characteristic phenol ring nitration reaction which resembles the tyrosine nitration in biological systems. Further, isolation of nitrate (NO3(-)) as the decomposition product from 2 at room temperature also supports the involvement of (-)OONO intermediate.

  11. Lanthanide(III) complexes with μ-SnSe{sub 4} and μ-Sn{sub 2}Se{sub 6} linkers. Solvothermal syntheses and properties of new Ln(III) selenidostannates decorated with linear polyamine

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shuzhen; Sun, Peipei; Shen, Yali; Han, Jingyu; Sun, Hui; Jia, Dingxian [Soochow Univ., Suzhou (China). College of Chemistry, Chemical Engineering and Materials Science

    2017-06-01

    New lanthanide-selenidostannate complexes [{La(peha)(Cl)}{La(peha)(NO_3)}(μ-1κ{sup 2}:2κ{sup 2}-SnSe{sub 4})] (1), [H{sub 2}trien][{La(trien)_2}{sub 2}(μ-1-κ:2κ-Sn{sub 2}Se{sub 6})][Sn{sub 2}Se{sub 6}].H{sub 2}O (2) and [{Ln(tepa)(μ-OH)}{sub 2}(μ-1κ:2κ-Sn{sub 2}Se{sub 6})]{sub n}.nH{sub 2}O (Ln=Sm(3), Eu(4)) were prepared by solvothermal methods in pentaethylenehexamine (peha), triethylenetetramine (trien) and tetraethylenepentamine (tepa), respectively. Acting as a tetradentate chelating and bridging ligand, μ-1κ{sup 2}:2κ{sup 2}-SnSe{sub 4}, the tetrahedral SnSe{sub 4} unit joins {La(peha)(Cl)}{sup 2+} and {La(peha)(NO_3)}{sup 2+} complex fragments to generate the neutral coordination compound 1. The tetradentate μ-1κ{sup 2}:2κ{sup 2} bridge in 1 represents a new coordination mode for the SnSe{sub 4} tetrahedron. In 2, dinuclear [Sn{sub 2}Se{sub 6}]{sup 4-} anions are formed of SnSe{sub 4} tetrahedra via edge-sharing. One [Sn{sub 2}Se{sub 6}]{sup 4-} anion acts as a bidentate bridging ligand in a μ-1κ:2κ coordination mode to join two {La(trien)_2}{sup 3+} units, and the other [Sn{sub 2}Se{sub 6}]{sup 4-} anion exists as a free charge compensating ion. In 3 and 4, the [Sn{sub 2}Se{sub 6}]{sup 4-} anion connects binuclear [{Ln(tepa)(μ-OH)}{sub 2}]{sup 2+}(Ln=Sm, Eu) units with a bidentate μ-1κ:2κ mode, giving neutral coordination polymers [{Ln(tepa)(μ-OH)}{sub 2}(μ-1κ:2κ-Sn{sub 2}Se{sub 6})]{sub n}. The La(2){sup 3+} ion in 1 is in a 10-fold coordination environment of LaN{sub 6}O{sub 2}Se{sub 2}, whereas the La(1){sup 3+} ions in 1 and 2 are in 9-fold coordinated environments forming polyhedra LaN{sub 6}ClSe{sub 2} and LaN{sub 8}Se, respectively. The Sm{sup 3+} and Eu{sup 3+} ions in 3 and 4 are both in an 8-fold coordination environment of LnN{sub 5}O{sub 2}Se. Compounds 1-4 exhibit optical band gaps between 2.21 and 2.42 eV. Their thermal stabilities were investigated by thermogravimetric analyses.

  12. Density functional theory study of model complexes for the revised nitrate reductase active site in Desulfovibrio desulfuricans NapA.

    Science.gov (United States)

    Hofmann, Matthias

    2009-09-01

    [Mo(SSCH3)(S2C2(CH3)2)2](x) complexes with charges x between -3 and +3 were investigated by density functional theory computations as minimal nitrate reductase active-site models. The strongly reduced species (x = -2, -3) exist preferentially as pentacoordinate sulfo complexes separated from a thiolate anion. The oxidized extremes (x > 0) clearly prefer hexacoordinate complexes with an eta(2)-MeSS ligand. Among the neutral and especially for the singly negatively charged species structures with eta(2)-MeSS and eta(1)-MeSS ligands are energetically close to the sulfo methyl sulfide complex without SS bonding. For x = -1 the three isomers lie in a 1.5 kcal mol(-1) energy range. Putative mechanistic pathways for nitrate reduction from the literature were investigated computationally: (1) reduction at a pentacoordinate sulfo complex, (2) reduction at the ligand, and (3) reduction at the molybdenum center with an R-S-S ligand. All three pathways could be traced at least for some overall charges but no definite conclusion can be drawn about the mechanism. Complexes with larger dithiolato ligands were also computed in order to model the tricyclic metallopterin framework more accurately: the first heterocyclus (5,6-dihydro-2H-pyran) stabilizes the nitrate complex and the molybdenum oxo product complex by approximately 10 kcal mol(-1) and also reduces the activation barrier (by approximately 5 kcal mol(-1)). The effect of the second (1,2,3,4-tetrahydropyrazin) and third heterocyclus (2-amino-3H-pyrimidin-4-one) on the relative energies is relatively small. For bigger models derived from an experimental protein structure, nitrate reduction at a persulfo molybdenum(IV) complex fragment (mechanism 3) is clearly favored over the oxidation of a molybdenum-bound sulfur atom (mechanism 2). Mechanism 1 could not be investigated for the big models but seems the least favorable on the basis of the results from smaller models.

  13. Critical Parameters of Complex Geometry Intersecting Cylinders Containing Uranyl Nitrate Solution

    Energy Technology Data Exchange (ETDEWEB)

    Rothe, Robert Emil; Briggs, Joseph Blair

    1999-06-01

    About three dozen previously unreported critical configurations are presented for very complex geometries filled with high concentration enriched uranyl nitrate solution. These geometries resemble a tall, thin Central Column (or trunk of a "tree") having long, thin arms (or "branches") extending up to four directions off the column. Arms are equally spaced from one another in vertical planes; and that spacing ranges from arms in contact to quite wide spacings. Both the Central Column and the many different arms are critically safe by themselves when each, alone, is filled with fissile solution; but, in combination, criticality occurs due to the interactions between arms and the column. Such neutronic interactions formed the principal focus of this study. While these results are fresh to the nuclear criticality safety industry and to those seeking novel experiments against which to validate computer codes, the experiments, themselves, are not recent. Over 100 experiments were performed at the Rocky Flats Critical Mass Laboratory between September, 1967, and February of the following year.

  14. Critical Parameters of Complex Geometries of Intersecting Cylinders Containing Uranyl Nitrate Solution

    Energy Technology Data Exchange (ETDEWEB)

    J. B. Briggs (INEEL POC); R. E. Rothe

    1999-06-14

    About three dozen previously unreported critical configurations are presented for very complex geometries filled with high concentration enriched uranyl nitrate solution. These geometries resemble a tall, thin Central Column (or trunk of a ''tree'') having long, thin arms (or ''branches'') extending up to four directions off the column. Arms are equally spaced from one another in vertical planes, and that spacing ranges from arms in contact to quite wide spacings. Both the Central Column and the many different arms are critically safe by themselves with each, alone, is filled with fissile solution; but, in combination, criticality occurs due to the interactions between arms and the column. Such neutronic interactions formed the principal focus of this study. While these results are fresh to the nuclear criticality safety industry and to those seeking novel experiments against which to validate computer codes, the experiments, themselves, are not recent. Over 100 experiments were performed at the Rocky Flats Critical Mass Laboratory between September, 1967, and February of the following year.

  15. Characterization of a periplasmic nitrate reductase in complex with its biosynthetic chaperone

    OpenAIRE

    Dow, J. M.; Grahl, S.; Ward, R; Evans, R.; Byron, O; Norman, D. G.; Palmer, T; Sargent, F

    2013-01-01

    Escherichia coli is a Gram‐negative bacterium that can use nitrate during anaerobic respiration. The catalytic subunit of the periplasmic nitrate reductase NapA contains two types of redox cofactor and is exported across the cytoplasmic membrane by the twin‐arginine protein transport pathway. NapD is a small cytoplasmic protein that is essential for the activity of the periplasmic nitrate reductase and binds tightly to the twin‐arginine signal peptide of NapA. Here we show, using spin labelli...

  16. Complex Controls on Groundwater Quality in Growing Mid-sized Cities: A Case Study Focused on Nitrate and Emerging Contaminants

    Science.gov (United States)

    Ohr, C. A.; Godsey, S.; Welhan, J. A.; Larson, D. M.; Lohse, K. A.; Finney, B.; Derryberry, D.

    2015-12-01

    Many regions rely on quality groundwater to support urban growth. Groundwater quality often responds in a complex manner to stressors such as land use change, climate change, or policy decisions. Urban growth patterns in mid-sized cities, especially ones that are growing urban centers in water-limited regions in the western US, control and are controlled by water availability and its quality. We present a case study from southeastern Idaho where urban growth over the past 20 years has included significant ex-urban expansion of houses that rely on septic systems rather than city sewer lines for their wastewater treatment. Septic systems are designed to mitigate some contaminants, but not others. In particular, nitrates and emerging contaminants, such as pharmaceuticals, are not removed by most septic systems. Thus, even well-maintained septic systems at sufficiently high densities can impact down gradient water quality. Here we present patterns of nitrate concentrations over the period from 1985-2015 from the Lower Portneuf River Valley in southeastern Idaho. Concentrations vary from 0.03 to 27.09 nitrate-nitrogen mg/L, with average values increasing significantly over the 30 year time period from 3.15 +/- 0.065 to 3.57 +/- 0.43 mg/L. We examine temporal changes in locations of nitrate hotspots, and present pilot data on emerging contaminants of concern. Initial results suggest that high nitrate levels are generally associated with higher septic densities, but that this pattern is influenced by legacy agricultural uses and strongly controlled by underlying aquifer properties. Future work will include more detailed hydrological modeling to predict changes in hotspot locations under potential climate change scenarios.

  17. Electric Hindrance and Precursor Complexes in the Regiochemistry of Some Nitrations

    Science.gov (United States)

    Sanchez-Viesca, Francisco; Gomez, Maria Reina Gomez; Berros, Martha

    2011-01-01

    There are still gaps in the theory of supposedly well-known chemical reactions. For example, there is no explanation why there is a notorious preponderance of one of the expected isomers in some electrophilic aromatic substitutions. The preferred ortho orientation of acetyl nitrate has been used widely to obtain ortho nitro compounds; however,…

  18. Electric Hindrance and Precursor Complexes in the Regiochemistry of Some Nitrations

    Science.gov (United States)

    Sanchez-Viesca, Francisco; Gomez, Maria Reina Gomez; Berros, Martha

    2011-01-01

    There are still gaps in the theory of supposedly well-known chemical reactions. For example, there is no explanation why there is a notorious preponderance of one of the expected isomers in some electrophilic aromatic substitutions. The preferred ortho orientation of acetyl nitrate has been used widely to obtain ortho nitro compounds; however,…

  19. One-dimensional Copper(Ⅱ) Complex Constructed with Nitrate Counter-anion as Bitopic Connector

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    Coordination polymer {[Cu(NPPCA)3(NO3)(H2O)]·NO3·H2O}n 1 ( NPPCA = N-(4′-nitrophenyl)-4-pyridinecarboxamide) has been synthesized by the reaction of NPPCA with copper(Ⅱ) nitrate in ethanol-water solution and characterized by X-ray diffraction. 1 crystallizes in the monoclinic space, group P21/n, a = 17.341(6)A, b = 6.744(2) (A), c = 34.555(12)(A), β =100.493(6)°, V = 3974(2) (A)3, Z = 4. Each copper(Ⅱ) ion has a distorted octahedral coordination geometry. Nitrate anion adopts the unusual coordination mode linking two adjacent copper(Ⅱ)ions to form a one-dimensional coordination polymer and these chains are further linked by noncovalent interactions.

  20. Incorporation of trinuclear lanthanide(III) hydroxo bridged clusters in macrocyclic frameworks.

    Science.gov (United States)

    Kobyłka, Michał J; Ślepokura, Katarzyna; Acebrón Rodicio, Maria; Paluch, Marta; Lisowski, Jerzy

    2013-11-18

    A cluster of lanthanide(III) or yttrium(III) ions, Ln3(μ3-OH)2, (Ln(III) = Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Yb(III), or Y(III)) can be bound in the center of a chiral macrocyclic amines H3L1(R), H3L1(S), and H3L2(S) obtained in a reduction of a 3 + 3 condensation product of (1R,2R)- or (1S,2S)-1,2-diaminocyclohexane and 2,6-diformyl-4-methylphenol or 2,6-diformyl-4-tertbutylphenol. X-ray crystal structures of the Nd(III), Sm(III), Gd(III), Dy(III), and Y(III) complexes reveal trinuclear complexes with Ln(III) ions bridged by the phenolate oxygen atoms of the macrocycle as well as by μ3-hydroxo bridges. In the case of the Nd(III) ion, another complex form can be obtained, whose X-ray crystal structure reveals two trinuclear macrocyclic units additionally bridged by hydroxide anions, corresponding to a [Ln3(μ3-OH)]2(μ2-OH)2 cluster encapsulated by two macrocycles. The formation of trinuclear complexes is confirmed additionally by (1)H NMR, electrospray ionization mass spectrometry (ESI MS), and elemental analyses. Titrations of free macrocycles with Sm(III) or Y(III) salts and KOH also indicate that a trinuclear complex is formed in solution. On the other hand, analogous titrations with La(III) salt indicate that this kind of complex is not formed even with the excess of La(III) salt. The magnetic data for the trinuclear Gd(III) indicate weak antiferromagnetic coupling (J = -0.17 cm(-1)) between the Gd(III) ions. For the trinuclear Dy(III) and Tb(III) complexes the χ(M)T vs T plots indicate a more complicated dependence, resulting from the combination of thermal depopulation of mJ sublevels, magnetic anisotropy, and possibly weak antiferromagnetic and ferromagnetic interactions.

  1. Studies on some lanthanide(Ⅲ)complexes with 4-hydroxyantipyrine

    Institute of Scientific and Technical Information of China (English)

    G. Rijulal; P. Indrasenan

    2008-01-01

    Seven new lanthanide(III) complexes with 4-hydroxyantipyrine were synthesized. These complexes were characterized by elemental analysis, molar conductance, magnetic moment measurements, FT-IR, electronic and 1HNMR spectra, X-ray powder diffraction, and thermogravimetric studies. The ligand, 4-hydroxyantipyrine (hap), contained carbonyl oxygen and hydroxyl oxygen as potential donor sites. On coordination, deprotonation occurred and as a result, hap acted as a monobasic bidentate ligand. A coordination number 6 was assigned to the lanthanide(III) ions in these complexes with orthorhombic structure. All the complexes were thermally stable~150℃ and underwent decomposition in three stages with the formation of Ln2O3 as the final residues.

  2. The Influence of Nitrate Salts and Complex Metal Ion to Regio-Selective Synthesis of 2-Nitro-5,10,15,20-Tetra-(4-Methoxyphenyl)Porphyrinato Metal

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A series of 2-nitro-5,10,15,20-tetra(4-methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2-substituted porphyrin. The influence of nitrate salts and complex metal ion to the reaction were investigated. The extent of 2-nitration increased with the electronegativity of the central metal. When Cu(NO3)2·3H2O was used as nitrating reagent, almost quantitative yields of 2 nitro porphyrin were obtained in the case of Cu(Ⅱ) or Ni(Ⅱ) chelates, while Zn(Ⅱ) or Mn(Ⅲ) chelates gave 50% and 30% yields respectively. If Zn(NO3)2·10H2O was used as nitrating agent, no product was found for Cu(Ⅱ) or Ni(Ⅱ) chelates, 12% was found for Zn(Ⅱ) chelates. The other metal ion and nitrate salts were also found in quite different influence.

  3. Sponge-like silver obtained by decomposition of silver nitrate hexamethylenetetramine complex

    Science.gov (United States)

    Afanasiev, Pavel

    2016-07-01

    Silver nitrate hexamethylenetetramine [Ag(NO3)·N4(CH2)6] coordination compound has been prepared via aqueous route and characterized by chemical analysis, XRD and electron microscopy. Decomposition of [Ag(NO3)·N4(CH2)6] under hydrogen and under inert has been studied by thermal analysis and mass spectrometry. Thermal decomposition of [Ag(NO3)·N4(CH2)6] proceeds in the range 200-250 °C as a self-propagating rapid redox process accompanied with the release of multiple gases. The decomposition leads to formation of sponge-like silver having hierarchical open pore system with pore size spanning from 10 μm to 10 nm. The as-obtained silver sponges exhibited favorable activity toward H2O2 electrochemical reduction, making them potentially interesting as non-enzyme hydrogen peroxide sensors.

  4. Sponge-like silver obtained by decomposition of silver nitrate hexamethylenetetramine complex

    Energy Technology Data Exchange (ETDEWEB)

    Afanasiev, Pavel, E-mail: pavel.afanasiev@ircelyon.univ-lyon.fr

    2016-07-15

    Silver nitrate hexamethylenetetramine [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] coordination compound has been prepared via aqueous route and characterized by chemical analysis, XRD and electron microscopy. Decomposition of [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] under hydrogen and under inert has been studied by thermal analysis and mass spectrometry. Thermal decomposition of [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] proceeds in the range 200–250 °C as a self-propagating rapid redox process accompanied with the release of multiple gases. The decomposition leads to formation of sponge-like silver having hierarchical open pore system with pore size spanning from 10 µm to 10 nm. The as-obtained silver sponges exhibited favorable activity toward H{sub 2}O{sub 2} electrochemical reduction, making them potentially interesting as non-enzyme hydrogen peroxide sensors. - Graphical abstract: Thermal decomposition of silver nitrate hexamethylenetetramine coordination compound [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] leads to sponge like silver that possesses open porous structure and demonstrates interesting properties as an electrochemical hydrogen peroxide sensor. Display Omitted - Highlights: • [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] orthorhombic phase prepared and characterized. • Decomposition of [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] leads to metallic silver sponge with opened porosity. • Ag sponge showed promising properties as a material for hydrogen peroxide sensors.

  5. Thermodynamics of complexation in an aqueous solution of Tb(III) nitrate at 298 K

    Science.gov (United States)

    Lobacheva, O. L.; Berlinskii, I. V.; Dzhevaga, N. V.

    2017-01-01

    The pH of the formation of hydroxo complexes and hydrates in an aqueous solution of terbium Tb(III) is determined using combined means of potentiometric and conductometric titration. The stability constants of the hydroxo complexes, the products of hydroxide solubility, and the Gibbs energy of terbium hydroxo complex formation are calculated.

  6. Crystal structures of bis- and hexakis[(6,6'-di-hydroxy-bipyridine)copper(II)] nitrate coordination complexes.

    Science.gov (United States)

    Gerlach, Deidra L; Nieto, Ismael; Herbst-Gervasoni, Corey J; Ferrence, Gregory M; Zeller, Matthias; Papish, Elizabeth T

    2015-12-01

    Two multinuclear complexes synthesized from Cu(NO3)2 and 6,6'-di-hydroxy-bipyridine (dhbp) exhibit bridging nitrate and hydroxide ligands. The dinuclear complex (6,6'-di-hydroxy-bipyridine-2κ(2) N,N')[μ-6-(6-hy-droxy-pyridin-2-yl)pyridin-2-olato-1:2κ(3) N,N':O (2)](μ-hydroxido-1:2κ(2) O:O')(μ-nitrato-1:2κ(2) O:O')(nitrato-1κO)dicopper(II), [Cu2(C10H7N2O2)(OH)(NO3)2(C10H8N2O2)] or [Cu(6-OH-6'-O-bpy)(NO3)(μ-OH)(μ-NO3)Cu(6,6'-dhbp)], (I), with a 2:1 ratio of nitrate to hydroxide anions and one partially deprotonated dhbp ligand, forms from a water-ethanol mixture at neutral pH. The hexa-nuclear complex bis-(μ3-bi-pyridine-2,2'-diolato-κ(3) O:N,N':O')tetra-kis-(6,6'-di-hydroxy-bipyridine-κ(2) N,N')tetra-kis-(μ-hydroxido-κ(2) O:O')bis-(methanol-κO)tetra-kis-(μ-nitrato-κ(2) O:O')hexa-copper(II), [Cu6(C10H6N2O2)2(CH4O)2(OH)4(NO3)4(C10H8N2O2)4] or [Cu(6,6'-dhbp)(μ-NO3)2(μ-OH)Cu(6,6'-O-bpy)(μ-OH)Cu(6,6'dhbp)(CH3OH)]2, (II), with a 1:1 NO3-OH ratio and two fully protonated and fully deprotonated dhbp ligands, was obtained by methanol recrystallization of material obtained at pH 3. Complex (II) lies across an inversion center. Complexes (I) and (II) both display intra-molecular O-H⋯O hydrogen bonding. Inter-molecular O-H⋯O hydrogen bonding links symmetry-related mol-ecules forming chains along [100] for complex (I) with π-stacking along [010] and [001]. Complex (II) forms inter-molecular O-H⋯O hydrogen-bonded chains along [010] with π-stacking along [100] and [001].

  7. Synthesis, spectroscopic characterization and thermal studies of some lanthanide(Ⅲ) nitrate complexes with a hydrazo derivative of 4-aminoantipyrine

    Institute of Scientific and Technical Information of China (English)

    K. Mohanan; C.J. Athira; Y. Sindhu; M.S. Sujamol

    2009-01-01

    A heterocyclic ligand synthesized by the coupling of diazotized 4-aminoantipyrine with acetylacetone reacted with lanthanide(Ⅲ) nitrate to form complexes of the type [Ln(HAAP)2(NO3)3] where, Ln=La(Ⅲ), Ce(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sm(Ⅲ), or Gd(Ⅲ) and HAAP=3-{[2-(N-1-pheny1-2,3-dimethylpyrazol-3-in-5-on-4-yl)]hydrazone}pent-2,3,4-trione. The ligand and metal complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, UV-Visible, infrared, far infrared and proton NMR spectral data. The spectral data revealed that the ligand existed in the hydrazo form and coordinated to the metal ion without deproto-nation in a neutral tridentate manner, through carbonyl oxygen of pyrazolone ring, hydrazo nitrogen and carbonyl oxygen of the acetylace-tone moiety. The molar conductance values adequately supported their non-electrolytic nature. The ligand and the praseodymium(Ⅲ) com-plex were subjected to X-ray diffraction studies. Thermal decomposition behavior of the lanthanum(Ⅲ) complex was also examined.moiety.

  8. Nickel(II) Complexation with Nitrate in Dry [C4mim][Tf2N] Ionic Liquid: A Spectroscopic, Microcalorimetric, and Molecular Dynamics Study.

    Science.gov (United States)

    Melchior, Andrea; Gaillard, Clotilde; Gràcia Lanas, Sara; Tolazzi, Marilena; Billard, Isabelle; Georg, Sylvia; Sarrasin, Lola; Boltoeva, Maria

    2016-04-04

    The complex formation of nitrate ions with nickel(II) in dry [C4mim][Tf2N] ionic liquid (IL) was investigated by means of UV-visible spectrophotometry, isothermal titration calorimetry (ITC), extended X-ray absorption fine structure spectroscopy (EXAFS), and molecular dynamics (MD) simulations. EXAFS spectroscopy and MD simulations show that the solvated Ni(II) cation is initially coordinated by the oxygens of the [Tf2N](-) anion of IL, which can behave either as mono- or bidentate. Spectroscopic and thermodynamic data show that Ni(II) is able to form up to three stable mononuclear complexes with nitrate in this solvent. The stability constants for Ni(NO3)j complexes (j = 1-3) calculated from spectrophotometry and ITC experiments decrease in the order log K1 > log K2 > log K3. The formation of the first two species is enthalpy-driven, while the third species is entropy-stabilized. The UV-vis spectra of solutions containing different nitrate/Ni(II) ratios show that the metal ion retains the six-coordinate geometry. Furthermore, the EXAFS evidences that nitrate is always bidentate. Molecular dynamics simulations show that the [Tf2N](-) anions bind Ni(II) through the sulfonyl oxygen atoms and can coordinate either as monodentate or chelate. The analysis of the MD data shows that introduction of nitrates in the first coordination sphere of the metal ion results in remarkable structural rearrangement of the ionic liquid.

  9. Synthesis, Characterization and Luminescent Properties of Complexes of Rare Earth Nitrates with 2,2′:4′,4″:2″,2-Quaterpyridine

    Institute of Scientific and Technical Information of China (English)

    唐瑜; 张正华; 谭民裕; 王锐

    2002-01-01

    The rare earth nitrate complexes with 2,2′:4′,4″:2″,2-quaterpyridine (L) were prepared in ethylacetate. These new complexes with the general formula [RE(NO3)3L]*H2O (RE = La, Pr, Eu, Tb, Er, Y) were characterized by elemental analysis, IR spectra, thermal analysis and molar conductance measurements. The luminescence properties of these complexes were also studied.

  10. Synthesis, Characterization and Fluorescence of Rare earth Nitrate Complexes with Triaza-crown Ether Derivative

    Institute of Scientific and Technical Information of China (English)

    胡晓黎; 崔书亚; 闫兰; 杨汝栋

    2003-01-01

    Four new complexes of rare earths with a triaza-crown ether (L) derived from N3O2-macro cycle 1,12,15-triaza-3, 4: 9,10-dibenzo-5, 8-dioxacycloheptadecane were synthesized and characterized by elemental analysis, IR, molar conductance, TG-DTA analysis and fluorescence spectra. The composition of the complexes determined as [RE(NO3)3L*3H2O]*H2O (RE=Sm, Eu, Tb and Dy). It is found that Sm3+, Eu3+, Tb3+ and Dy3+ complexes all show strong fluorescence emission in the solid state. Among these complexes, Tb3+ complex has the strongest luminescence intensity. It shows that the ligand L triplet state energy matches 5D4 energy level of Tb3+. In the Eu3+ complex, η(5D0→7F2/5D0→7F1) is 2.6, which indicates that Eu3+ locates at the asymmetric coordination field.

  11. Triheterometallic Lanthanide Complexes Prepared from Kinetically Inert Lanthanide Building Blocks

    DEFF Research Database (Denmark)

    Sørensen, Thomas Just; Tropiano, Manuel; Kenwright, Alan M.

    2017-01-01

    . The photophysical properties of these heterotrimetallic complexes were investigated and are discussed by comparison with simpler, but related, heterodimetallic compounds. It was found that an aminonaphthalene unit inhibits the sensitisation of terbium, and that the spatial arrangement of the chromophores......Three molecular structures, each containing three different lanthanide(III) centres, have been prepared by coupling three kinetically inert lanthanide(III) complexes in an Ugi reaction. These 2 kDa molecules were purified by dialysis and characterised by NMR and luminescence techniques...

  12. Enthalpies of Solution of Complexes of Rare Earth Nitrate with L-α-Histidine in Water

    Institute of Scientific and Technical Information of China (English)

    刘洋; 房艳; 高胜利; 陈三平; 史启祯

    2002-01-01

    The enthalpies of solution in water of complexes of RE(NO3)3 (RE=La~Nd, Sm~Lu, Y) with L-α-Histidine (His) were measured at 298.15 K. The standard enthalpies of formation of RE(His)3+(aq) were calculated. The "tetrad effect" regularity was observed from the curve, which is the enthalpies of solution plotted against the atomic numbers of the elements in lanthanide series.

  13. Biological Role of Anions (Sulfate, Nitrate , Oxalate and Acetate) on the Antibacterial Properties of Cobalt (II) and Nickel(II) Complexes With Pyrazinedicarboxaimide Derived, Furanyl and Thienyl Compounds

    OpenAIRE

    Chohan, Zahid H.; Praveen, M.

    1999-01-01

    A number of biologically active complexes of cobalt(II) and nickel(II) with pyrazinedicarboxaimido derived thienyl and furanyl compounds having the same metal ion but different anions such as sulphate, nitrate, oxalate and acetate have been synthesized and characterized on the basis of their physical, spectral and analytical data. In order to evaluate the role of anions on their antibacterial properties, these ligands and their synthesized metal complexes with various anions have been screene...

  14. NPY binds with heme to form a NPY-heme complex: enhancing peroxidase activity in free heme and promoting NPY nitration and inactivation.

    Science.gov (United States)

    Ye, Huixian; Yang, Zhen; Li, Hailing; Gao, Zhonghong

    2017-08-08

    Neuropeptide Y (NPY) is a member of the pancreatic peptide family of neuropeptides that play a crucial role in numerous central and peripheral nervous system responses. Recently, it has been shown that NPY protects cells against neurotoxic damage from β-amyloid peptides (Aβ) in Alzheimer's disease (AD). Heme is a common factor linking several metabolic perturbations in AD and altered heme metabolism has been shown to be related to the pathologies of AD. Thus, heme may have a chance to act on NPY and potentially counteract its function. To explore this, UV-visible spectroscopy, fluorescence spectroscopy and differential pulse voltammetry (DPV) were used to demonstrate that NPY can bind with heme to form a NPY-heme complex and the binding enhances the peroxidase activity of heme. Dot blotting results indicate that NPY is easily nitrated upon binding with heme when H2O2 and NO2(-) are present. Furthermore, LC-MS/MS results confirm that tyrosine36 (Tyr36), an important amino acid residue of NPY in binding and activating neuropeptide receptors, can be nitrated during the nitration process. Thereafter, we used mutant peptide NPY(3N) (Tyr36 replaced by 3-nitrotyrosine) to investigate the impact of nitration on the structure and bioactivity of the peptide. Our results show that Tyr36 nitration destabilizes the α-helix conformation of the peptide, and counteracts NPY-induced inhibition of cAMP accumulation in SK-N-MC cells. Collectively, these data imply that the self-association of NPY with heme potentially induces tyrosine nitration, destroys the active monomeric conformation of the peptide and thereby counteracts its bioactivity.

  15. Synthesis and luminescent spectroscopy of lanthanide complexes with dimethylpyridine-2,6-dicarboxylate (dmpc)

    Energy Technology Data Exchange (ETDEWEB)

    Taha, Ziyad A., E-mail: tahaz33@just.edu.jo [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Ajlouni, Abdulaziz M.; Hijazi, Ahmed K. [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Al-Rawashdeh, Nathir A. [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Department of Chemistry, United Arab Emirates University, Al Ain 15551 (United Arab Emirates); Al-Hassan, Khader A.; Al-Haj, Yaser A. [Department of Chemistry, Faculty of Science, Yarmouk University, 1163 Irbid (Jordan); Ebqa' ai, Mohammad A. [Al-Qunfudah Center For Scientific Research, Umm Al-Qura University, College in Al-Qunfudah, Makkah (Saudi Arabia); Altalafha, Ammar Y. [Department of Chemistry, Faculty of Science, Yarmouk University, 1163 Irbid (Jordan)

    2015-05-15

    A series of lanthanide complexes with the general formulae [Ln(dmpc)(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}]NO{sub 3} (Ln=Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Er) and [La(dmpc)(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}]NO{sub 3} were prepared by direct reaction between hydrated lanthanide(III) nitrate and dimethylpyridine-2,6-dicarboxylate (dmpc) in a 1:1 M ratio in ethylacetate–chloroform mixture. The luminescence properties of the dmpc and its Ln(III) complexes were investigated in solid state and in methanol, DMF and DMSO solutions. The Tb–dmpc, Eu–dmpc, Sm–dmpc and Dy–dmpc complexes exhibit characteristic luminescence of Tb(III), Eu(III), Sm(III) and Dy(III) ions indicating energy transfer from the dmpc to the Ln(III) ions. Scavenging activities of the dmpc and its Ln(III) complexes on DPPH{sup •} free radical were investigated in DMSO solution at a different concentrations ranges. - Highlights: • Nine new lanthanide complexes with dmpc ligand are prepared and characterized. • Ln–dmpc {Ln=Eu, Tb, Sm, Dy} complexes exhibit characteristic emissions of Ln ions. • The solvent effect on the luminescence intensity is investigated. • The antioxidant activity of the dmpc is enhanced upon complexation with lanthanide.

  16. Synthesis, characterization and biological activities of copper(II) complex of 2-Benzimidazolyl-urea and the nitrate salt of 2-Benzimidazolyl-urea

    Science.gov (United States)

    Poyraz, Mehmet; Sari, Musa; Banti, Christina N.; Hadjikakou, Sotiris K.

    2017-10-01

    The synthesis of the complex {[Cu(BZIMU)2](NO3)2} (1) (BZIMU = 2-Benzimidazolyl-urea) is reported here. The complex 1 was characterized by elemental analysis, FT-IR, magnetic susceptibility and molar conductance measurements. The crystal structures of 1 and of the nitrate salt of [(BZIMUH+)(NO3)-] (2) were determined by X-ray diffraction analysis. The copper complex 1 and [(BZIMUH+)(NO3)-] (2) were evaluated for their in vitro cytotoxic activity (cell viability) against human cervix adenocarcinoma (HeLa) and human breast adenocarcinoma (MCF-7) cell line and normal human fetal lung fibroblast cells (MRC-5) with SRB assay.

  17. Ga(3+)/Ln(3+) Metallacrowns: A Promising Family of Highly Luminescent Lanthanide Complexes That Covers Visible and Near-Infrared Domains.

    Science.gov (United States)

    Chow, Chun Y; Eliseeva, Svetlana V; Trivedi, Evan R; Nguyen, Tu N; Kampf, Jeff W; Petoud, Stéphane; Pecoraro, Vincent L

    2016-04-20

    Luminescent lanthanide(III)-based molecular scaffolds hold great promises for materials science and for biological applications. Their fascinating photophysical properties enable spectral discrimination of emission bands that range from the visible to the near-infrared (NIR) regions. In addition, their strong resistance to photobleaching makes them suitable for long duration or repeated biological experiments using a broad range of sources of excitation including intense and focalized systems such as lasers (e.g., confocal microscopy). A main challenge in the creation of luminescent lanthanide(III) complexes lies in the design of a ligand framework that combines two main features: (i) it must include a chromophoric moiety that possesses a large molar absorptivity and is able to sensitize several different lanthanide(III) ions emitting in the visible and/or in the near-infrared, and (ii) it must protect the Ln(3+) cation by minimizing nonradiative deactivation pathways due to the presence of -OH, -NH and -CH vibrations. Herein, a new family of luminescent Ga(3+)/Ln(3+) metallacrown (MC) complexes is reported. The MCs with the general composition [LnGa4(shi)4(C6H5CO2)4(C5H5N) (CH3OH)] (Ln-1, Ln = Sm(3+)-Yb(3+)) were synthesized in a one pot reaction using salicylhydroxamic acid (H3shi) with Ga(3+) and Ln(3+) nitrates as reagents. The molecular structure of [DyGa4(shi)4(C6H5CO2)4(C5H5N) (CH3OH)] was obtained by X-ray analysis of single crystals and shows that the complex is formed as a [12-MCGa(III)shi-4] core with four benzoate molecules bridging the central Dy(3+) ion to the Ga(3+) ring metals. The powder X-ray diffraction analysis demonstrates that all other isolated complexes are isostructural. The extended analysis of the luminescence properties of these complexes, excited by the electronic states of the chromophoric ligands, showed the presence of characteristic, sharp f-f transitions that can be generated not only in the NIR (Sm, Dy, Ho, Er, Yb) but also in the

  18. spectral characterization and dna binding properties of lanthanide(iii)

    African Journals Online (AJOL)

    The complexes undergo quasi-reversible one electron reduction. The binding interaction ... cleavage activities of transition metal complex, herein we report synthesis, spectral ... instruments 660C Electrochemical analyzer and a conventional three electrode, Ag/AgCl reference ..... F.19-106/2013(BSR)] for financial support.

  19. Synthesis, characterization and DNA interaction studies of complexes of lanthanide nitrates with tris{2-[(3,4-dihydroxybenzylidene)imino]ethyl}amine

    Science.gov (United States)

    Liu, Min; Yuan, Wen-bing; Zhang, Qi; Yan, Lan; Yang, Ru-dong

    2008-10-01

    A new tripodal, hydroxyl-rich ligand, tris{2-[(3,4-dihydroxybenzylidene)imino]ethyl}amine (L), and its complexes with lanthanide nitrates were synthesized. These complexes which are stable in air with the general formula of [LnL(NO 3) 2]NO 3·H 2O (Ln = La, Sm, Eu, Gd, Y) were characterized by molar conductivity, elemental analysis, IR spectra and thermal analysis. The NO 3- groups coordinated to lanthanide mono-dentately, and the coordination number in these complexes may be 8. The interaction of complexes with DNA were investigated by ultraviolet and fluorescent spectra, which showed that the binding mode of complexes with DNA was intercalation, and the binding affinity with DNA were La(III) complex > Sm(III) complex > Eu(III) complex > Gd(III) complex > Y(III) complex. Based on these results, it can be shown that the La(III)complex is promising candidate for therapeutic reagents and DNA probes.

  20. Crystal structures of two mononuclear complexes of terbium(III) nitrate with the tripodal alcohol 1,1,1-tris-(hy-droxy-meth-yl)propane.

    Science.gov (United States)

    Gregório, Thaiane; Giese, Siddhartha O K; Nunes, Giovana G; Soares, Jaísa F; Hughes, David L

    2017-02-01

    Two new mononuclear cationic complexes in which the Tb(III) ion is bis-chelated by the tripodal alcohol 1,1,1-tris-(hy-droxy-meth-yl)propane (H3L(Et), C6H14O3) were prepared from Tb(NO3)3·5H2O and had their crystal and mol-ecular structures solved by single-crystal X-ray diffraction analysis after data collection at 100 K. Both products were isolated in reasonable yields from the same reaction mixture by using different crystallization conditions. The higher-symmetry complex dinitratobis[1,1,1-tris-(hy-droxy-meth-yl)propane]-terbium(III) nitrate di-meth-oxy-ethane hemisolvate, [Tb(NO3)2(H3L(Et))2]NO3·0.5C4H10O2, 1, in which the lanthanide ion is 10-coordinate and adopts an s-bicapped square-anti-prismatic coordination geometry, contains two bidentate nitrate ions bound to the metal atom; another nitrate ion functions as a counter-ion and a half-mol-ecule of di-meth-oxy-ethane (completed by a crystallographic twofold rotation axis) is also present. In product aqua-nitratobis[1,1,1-tris-(hy-droxy-meth-yl)propane]-terbium(III) dinitrate, [Tb(NO3)(H3L(Et))2(H2O)](NO3)2, 2, one bidentate nitrate ion and one water mol-ecule are bound to the nine-coordinate terbium(III) centre, while two free nitrate ions contribute to charge balance outside the tricapped trigonal-prismatic coordination polyhedron. No free water mol-ecule was found in either of the crystal structures and, only in the case of 1, di-meth-oxy-ethane acts as a crystallizing solvent. In both mol-ecular structures, the two tripodal ligands are bent to one side of the coordination sphere, leaving room for the anionic and water ligands. In complex 2, the methyl group of one of the H3L(Et) ligands is disordered over two alternative orientations. Strong hydrogen bonds, both intra- and inter-molecular, are found in the crystal structures due to the number of different donor and acceptor groups present.

  1. Structure of a dinuclear cadmium complex with 2,2′-bipyridine, monodentate nitrate and 3-carboxy-6-methylpyridine-2-carboxylate ligands: intramolecular carbonyl(lone pair...π(ring and nitrate(π...π(ring interactions

    Directory of Open Access Journals (Sweden)

    Juan Granifo

    2015-08-01

    Full Text Available The centrosymmetric dinuclear complex bis(μ-3-carboxy-6-methylpyridine-2-carboxylato-κ3N,O2:O2;κ3O2:N,O2-bis[(2,2′-bipyridine-κ2N,N′(nitrato-κOcadmium] methanol monosolvate, [Cd2(C8H6NO42(NO32(C10H8N22]·CH3OH, was isolated as colourless crystals from the reaction of Cd(NO32·4H2O, 6-methylpyridine-2,3-dicarboxylic acid (mepydcH2 and 2,2′-bipyridine in methanol. The asymmetric unit consists of a CdII cation bound to a μ-κ3N,O2:O2-mepydcH− anion, an N,N′-bidentate 2,2′-bipyridine group and an O-monodentate nitrate anion, and is completed with a methanol solvent molecule at half-occupancy. The Cd complex unit is linked to its centrosymmetric image through a bridging mepydcH− carboxylate O atom to complete the dinuclear complex molecule. Despite a significant variation in the coordination angles, indicating a considerable departure from octahedral coordination geometry about the CdII atom, the Cd—O and Cd—N distances in this complex are surprisingly similar. The crystal structure consists of O—H...O hydrogen-bonded chains parallel to a, further bound by C—H...O contacts along b to form planar two-dimensional arrays parallel to (001. The juxtaposed planes form interstitial columnar voids that are filled by the methanol solvent molecules. These in turn interact with the complex molecules to further stabilize the structure. A search in the literature showed that complexes with the mepydcH− ligand are rare and complexes reported previously with this ligand do not adopt the μ-κ3 coordination mode found in the title compound.

  2. Unusual self-assembled 1D tape of tetramers and water-nitrate clusters trapped in a zinc(II) complex: Synthesis, characterization, luminescence and catalytic properties

    Science.gov (United States)

    Ma, De-Yun; Guo, Hai-Fu; Dong, Ji; Xu, Jun

    2013-12-01

    Unusual tetramers and water-nitrate clusters have been observed in a mononuclear zinc(II) complex of [Zn(4-cpa)(phen)2(H2O)]·(H2O)·(NO3)] (1), (4-Hcpa = 4-chlorophenoxyacetic acid, phen = 1,10-phenanthroline), which was synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction, UV-vis absorption spectra and single-crystal X-ray diffraction. The crystal structure analysis of 1, reveals that the nitrate anions, water molecules and carboxylate oxygen atoms (O3) pack to form a one-dimensional infinite tape parallel to the c-axis. The uncoordinated carboxylate oxygen atoms (O3) of 4-cpa ligands, water molecules and nitrate anions interact via hydrogen bonds and extend 1 into a water-anion-cation tape, which are finally connected into a 3D supramolecular structure via π⋯π stacking interactions. Excitation (λex = 310 nm) and luminescence data observed at room temperature show that 1 emits bright blue fluorescence. Moreover, 1 has a remarkable activity for degradation of methyl orange in a photo-assisted Fenton-like process.

  3. Differential nitrate accumulation, nitrate reduction, nitrate reductase ...

    African Journals Online (AJOL)

    use

    2011-12-07

    Dec 7, 2011 ... storage in the leaf vacuole cells to be released later and reduced in the cytosol ... pathway dependent on nitrate ion concentration, and (2) potassium and ..... converted to starch in storage organs (Li et al., 2009;. Amtmann and ...

  4. Terminal group effects on the fluorescence spectra of europium(III) nitrate complexes with a family of amide-based 2,3-dihydroxynaphthalene derivatives

    Science.gov (United States)

    Lei, Ke-Wei; Liu, Wei-Sheng

    2006-09-01

    Three ligands 2,2'-[2,3-naphthylenebis(oxy)]-bis( N, N-diethyl(acetamide)) (L a), 2,2'-[2,3-naphthylenebis(oxy)]-bis( N, N-diisopropyl(acetamide)) (L b) and 2,2'-[2,3-naphthylenebis(oxy)]-bis( N, N-dibutyl(acetamide)) (L c) and their europium(III) nitrate complexes were synthesized. The complexes were characterized by elemental analysis, IR, fluorescence spectroscopy and conductivity. The europium atoms are coordinated by O-atoms from C dbnd O, Ar-O-C. With the difference of the ligands, the solid fluorescent intensities of the Eu complexes vary regularly. Some factors that influencing the fluorescent intensity were discussed.

  5. Copper(II) bromide, nitrate and perchlorate complexes with sterically demanding N-(6-methylpyridin-2-yl)acetamide ligands.

    Science.gov (United States)

    Smolentsev, Anton I

    2017-08-01

    Functionalized acid amides are widely used in biology, medicine, environmental chemistry and many other areas. Among them, pyridine-substituted amides, in particular N-(pyridin-2-yl)acetamide and its derivatives, play an important role due to their excellent chelating properties. The donor properties of these ligands can be effectively modified by introducing electron-donating substituents (e.g. alkyl groups) into the heterocycle. On the other hand, substituents in the α-position of the pyridine ring can create steric hindrance, which significantly influences the coordination number and geometry. To achieve a better understanding of these effects, copper(II) complexes with sterically demanding N-(6-methylpyridin-2-yl)acetamide ligands (L) and monoanions of different size, shape and coordination ability have been chosen as model compounds. The crystal structures of three new compounds, bromidobis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) bromide, [CuBr(C8H10N2O)]Br, (I), aquabis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) dinitrate, [Cu(C8H10N2O)(H2O)](NO3)2, (II), and aquabis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) bis(perchlorate), [Cu(C8H10N2O)(H2O)](ClO4)2, (III), have been determined by single-crystal X-ray diffraction analysis. It has been shown that the presence of the 6-methyl group results in either a distorted square-pyramidal or a distorted trigonal-bipyramidal coordination geometry around the Cu(II) centres instead of the typical octahedral geometry observed when the methyl substituent is absent or occupies any other position on the pyridine ring. Moreover, due to the steric hindrance provided by the L ligands, only the bromide ligand, the smallest of the series, enters into the first coordination sphere of the Cu(II) ion in (I). In (II) and (III), the vacant coordination site of the Cu(II) ion is occupied by a water molecule, while the nitrate and perchlorate anions are not involved in coordination to the metal centre

  6. Formation of colloidal silver nanoparticles stabilized by Na+-poly(gamma-glutamic acid)-silver nitrate complex via chemical reduction process.

    Science.gov (United States)

    Yu, Da-Guang

    2007-10-01

    Macromolecular and polyanionic Na(+)-poly(gamma-glutamic acid) (PGA) silver nitrate complex acted as both a metal ion provider and a particle protector to fabricate nanosized silver colloids under chemical reduction by dextrose. The formation and size of particles have been characterized from transmission electron microscopy (TEM), dynamic light scattering analysis and UV-vis spectrophotometer. The results showed that the average particle size was 17.2+/-3.4 to 37.3+/-5.5 nm, apparently depending on the complex concentration. It was found that the rate constant and conversion of silver nanoparticles were proportional to the concentration of PGA. The growth mechanism of nanosized silver colloid was fully discussed. In addition, the in vitro cytotoxicity evaluated by L929 fibroblasts proliferation and antibacterial activity against Gram-positive strain (methicillin-resistant S. aureus (MRSA)) and Gram-negative strain (P. aeruginosa) bacteria have been assessed.

  7. Synthesis, Characterization and Luminescent Properties of Complexes of Rare Earth Nitrates with Tris {2-[N-(pyridine-methanoyl)amino]ethyl} amine

    Institute of Scientific and Technical Information of China (English)

    台夕市; 唐瑜; 刘伟生; 谭民裕

    2003-01-01

    A tripodal ligand, tris{2-[N-(pyridine-methanoyl)amino]ethyl}amine(L), and its complexes with rare earth nitrates were synthesized. These new complexes with the general formula of Ln(NO3)3*L*6H2O(where Ln=La, Nd, Eu, Tb, Y) were characterized by elemental analysis, IR spectra, thermal analysis, 1 H NMR spectra, molar conductivity and luminescent spectra. All the complexes are stable in air and their conductances in acetonitrile solution lie in the range of 142~150 S*cm2*mol-1, indicating 1∶1 type electrolytes. The IR and 1H NMR spectra of the ligand and its complexes show that all the C=O groups take part in coordination to the metal ions. The thermal behaviour of Eu complex shows that the weight losses at 75~120 ℃ and 120~210 ℃ correspond to the loss of four lattice water molecules and that of two coordinated water molecules, respectively. The luminescent spectra of the complexes of Eu(Ⅲ) and Tb(Ⅲ) were investigated in methanol.

  8. Cytotoxic and genotoxic potential of Cr(VI), Cr(III)-nitrate and Cr(III)-EDTA complex in human hepatoma (HepG2) cells.

    Science.gov (United States)

    Novotnik, Breda; Ščančar, Janez; Milačič, Radmila; Filipič, Metka; Žegura, Bojana

    2016-07-01

    Chromium (Cr) and ethylenediaminetetraacetate (EDTA) are common environmental pollutants and can be present in high concentrations in surface waters at the same time. Therefore, chelation of Cr with EDTA can occur and thereby stable Cr(III)-EDTA complex is formed. Since there are no literature data on Cr(III)-EDTA toxicity, the aim of our work was to evaluate and compare Cr(III)-EDTA cytotoxic and genotoxic activity with those of Cr(VI) and Cr(III)-nitrate in human hepatoma (HepG2) cell line. First the effect of Cr(VI), Cr(III)-nitrate and Cr(III)-EDTA on cell viability was studied in the concentration range from 0.04 μg mL(-1) to 25 μg mL(-1) after 24 h exposure. Further the influence of non-cytotoxic concentrations of Cr(VI), Cr(III)-nitrate and Cr(III)-EDTA on DNA damage and genomic stability was determined with the comet assay and cytokinesis block micronucleus cytome assay, respectively. Cell viability was decreased only by Cr(VI) at concentrations above 1.0 μg mL(-1). Cr(VI) at ≥0.2 μg mL(-1) and Cr(III) at ≥1.0 μg mL(-1) induced DNA damage, while after Cr(III)-EDTA exposure no formation DNA strand breaks was determined. Statistically significant formation of micronuclei was induced only by Cr(VI) at ≥0.2 μg mL(-1), while no influence on the frequency of nuclear buds nor nucleoplasmic bridges was observed at any exposure. This study provides the first evidence that Cr(III)-EDTA did not induce DNA damage and had no influence on the genomic stability of HepG2 cells.

  9. Normal coordinate analysis and DFT calculations of the vibrational spectra for lanthanide(III) complexes with 3-bromo-4-methoxy-2,6-lutidine N-oxide: LnCl 3(3Br4CH 3OC 7H 7NO) 3 (Ln=Pr, Nd, Sm, Eu, Gd, Dy)

    Science.gov (United States)

    Godlewska, P.; Ban-Oganowska, H.; Macalik, L.; Hanuza, J.; Oganowski, W.; Roszak, S.; Lipkowski, P.

    2006-01-01

    The results of the FT-Raman and FT-IR studies of the LnCl 3(LNO) 3 type complexes (where Ln=Pr, Nd, Sm, Eu, Gd, Dy and LNO=3-Br-4-CH 3OC 7H 7NO) are presented. The spectral contours observed in the regions of the lanthanide-oxygen, lanthanide-chlorine and nitrogen-oxygen vibrations are employed in the discussion of the molecular structure of the complex ions and the local symmetry of the LnCl 3(ON) 3 polyhedron. The discussion of the vibrational spectra is based on the classical normal coordinate analysis and its results are compared to the results of DFT quantum chemical calculations performed for complete molecule. The normal coordinate analysis has been performed for PrCl 3(ON) 3 and DyCl 3(ON) 3 molecular systems, which have been treated as a different 'isotopic units'. Basing on the predominant PED contributions of the respective internal coordinates the assignment of the normal vibrations has been proposed.

  10. Crystal structure of a pyrazine-2,3-dicarboxamide ligand and of its silver(I nitrate complex, a three-dimensional coordination polymer

    Directory of Open Access Journals (Sweden)

    Dilovan S. Cati

    2017-06-01

    Full Text Available The title ligand, C18H16N6O2·2H2O (L1 [N2,N3-bis(pyridin-4-ylmethylpyrazine-2,3-dicarboxamide], crystallized as a dihydrate. The molecule is U-shaped with the carboxamide groups being cis to one another, making a dihedral angle of 81.6 (5°. The terminal pyridine rings are inclined to one another by 58.5 (4°. There is an intramolecular N—H...Npyrazine hydrogen bond present, forming an S(5 ring motif. In the crystal, adjacent molecules are linked by N—H...Ocarboxamide hydrogen bonds, forming a chain along [001]. A chain of hydrogen-bonded water molecules is linked to the chain of (L1 molecules by O—H...N hydrogen bonds, forming columns propagating along the c axis. The columns are linked by C—H...O and C—H...N hydrogen bonds, forming a three-dimensional supramolecular structure. The reaction of ligand (L1 with silver(I nitrate led to the formation of a new three-dimensional coordination polymer, {[Ag(C18H16N6O2]NO3}n, poly[[[μ4-N2,N3-bis(pyridin-4-ylmethylpyrazine-2,3-dicarboxamide]silver(I] nitrate] (I. The asymmetric unit is composed of half of one silver ion, located on a twofold rotation axis, half a ligand molecule and half a positionally disordered nitrate anion located about a twofold rotation axis. The full molecule of the ligand is generated by twofold rotational symmetry, with this twofold axis bisecting the Car—Car bonds of the pyrazine ring and the Ag—Ag bond. The carboxamide groups are now trans to one another, making a dihedral angle of 65.8 (4°. The two terminal pyridine rings are inclined to one another by 6.6 (3°. Two ligands wrap around an Ag—Ag bond of 3.1638 (11 Å, forming a figure-of-eight-shaped complex molecule. Each silver ion is coordinated by two pyridine N atoms and by two carboxamide O atoms of neighbouring molecules, hence forming a three-dimensional framework. The nitrate anion is linked to the framework by N—H...O and C—H...O hydrogen bonds.

  11. Nitrate storage and dissimilatory nitrate reduction by eukaryotic microbes

    DEFF Research Database (Denmark)

    Kamp, Anja; Høgslund, Signe; Risgaard-Petersen, Nils;

    2015-01-01

    The microbial nitrogen cycle is one of the most complex and environmentally important element cycles on Earth and has long been thought to be mediated exclusively by prokaryotic microbes. Rather recently, it was discovered that certain eukaryotic microbes are able to store nitrate intracellularly...... and use it for dissimilatory nitrate reduction in the absence of oxygen. The paradigm shift that this entailed is ecologically significant because the eukaryotes in question comprise global players like diatoms, foraminifers, and fungi. This review article provides an unprecedented overview of nitrate...... storage and dissimilatory nitrate reduction by diverse marine eukaryotes placed into an eco-physiological context. The advantage of intracellular nitrate storage for anaerobic energy conservation in oxygen-depleted habitats is explained and the life style enabled by this metabolic trait is described...

  12. Insensitive Ammonium Nitrate.

    Science.gov (United States)

    is reduced by replacing the ammonium nitrate with a solid solution of potassium nitrate in form III ammonium nitrate wherein the potassium nitrate...constitutes from more than zero to less than 50 weight percent of the solid solution . (Author)

  13. Synthesis and Molecular Structure of A Bimetallic Salen Complex Containing Zn and La: A Disordered Nitrate Group Dancing between Two Metal Centers

    Institute of Scientific and Technical Information of China (English)

    Leon Dyers Jr; Donald Van Derveer; Xiu R Bu

    2005-01-01

    A new bimetallic complex containing Zn and La was prepared from a salen ligand possessing methoxyl groups at the 3, 3'-positions. The structural feature is that one of nitrate groups is disordered and displaced between two metal centers. Crystal system: Triclinic space group:P-1, Z=2. a=0.82714(17) nm, b=1.3484(3) (1) nm, and c=1.3898(3) (1) nm, α=79.89(3)°, β=76.67(3)°, and γ=72.43(3)°. V=1.428.6(5) nm3, Dx=1.812 g·cm-3. (Δρ)max=1.510×10-3 enm3, (Δρ)min=-1.503×10-3 enm3. Accordingly, two water molecules occupy the metal centers in the apical positions via the syn-geometry.

  14. Nitrate Reductase: Properties and Regulation

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Nitrate Reductase (NR) is a rating-limit and key enzyme of nitrate assimilation in plants ,so ,NR activity is important for growth,development and the dry matter accumulation of plants. The regulation of NR activity appears to be rather complex and many studies have been devoted to the description of regulation and properties,but in this paper we focus on the properties and regulation of NR in higher plants.

  15. Synthesis and Crystal Structure of a Dinuclear Complex: Bis[aqua(phen)(4-aba)copper(Ⅱ)nitrate(4-abaH)dihydrate

    Institute of Scientific and Technical Information of China (English)

    LI Yan-Guo; CHEN Hong-Ji

    2007-01-01

    The title complex has been obtained by the reaction of copper nitrate trihydrate with 4-abaH (4-abaH = 4-aminobenzonic acid) and phenanthroline in ethanol solution,and its structure was determined by X-ray crystallography with the following data: monoclinic,space group C2/c, Mr = 1266.13, Cu2C52H54N10O20, a = 25.884(5), b = 10.205(2), c = 20.849(4)(A), β= 106.34(3)°, Z = 4, V= 5284.7(18) (A)3, F(000) = 2616, Dc = 1.591 g/cm3, μ = 0.896 mm-1,the final R = 0.0441 and wR = 0.1148 for 4200 observed reflections (I > 2σ(I)). In the molecule of the title complex, the asymmetric unit contains one half molecule. The Cu(Ⅱ) atom is five-coordinated by a terminal water molecule, a bidentate phenanthroline and two monodentate 4-aminobenzoate ligands forming a square pyramidal coordination environment. The two bridging 4-aminobenzoate ligands result in a dinuclear copper(Ⅱ) cluster with a short Cu-Cu distance (3.048 (A)) and a π-πstacking between the adjacent phenanthroline rings (2.96 (A)).

  16. Nuclear magnetic resonance study of charge transfer complex formation between Silver Nitrate and Benzylcyanide in Solvent Ethylene Glycol

    CERN Document Server

    Modarress, H

    2003-01-01

    The formation constant for charge transfer complexes between electron acceptor (AgNo sub 3) and electron donor benzylcyanide (C sub 6 H sub 5 -CH sub 2 -C ident to N) in solvent ethyleneglycol [(CH sub 2 OH) sub 2] has been evaluated by using the nuclear magnetic resonance chemical shifts of aromatic group of benzylcyanide measured against external references, tetramethylsilane, hexamethyldisilane and cyclohexane at 20 sup d ig sup C. The external referencing procedure eliminated the interference of internal reference in the course of complexation. The necessary bulk magnetic susceptibility corrections on the measured chemical shifts have been made. The solution nationalised and their effects on the formation constant have been considered and a new equation has been suggested to obtain the main ionic activity coefficient of AgNO sub 3 from nuclear magnetic resonance results. The mean ionic activity coefficient has been taken into account in the formation constant calculations. The results indicated that the a...

  17. Nitrate metabolism in the gromiid microbial universe

    DEFF Research Database (Denmark)

    Høgslund, Signe; Risgaard-Petersen, Nils; Cedhagen, Tomas

    Eukaryotic nitrate respiration supported by intracellular nitrate storages contributes substantially to the nitrogen cycle. Research focus is currently directed towards two phyla: Foraminifera and diatoms, but the widespread Gromia in the Rhizaria may be another key organism. These giant protists...... enclose and regulate a small biogeochemical universe within their cell. Their transparent proteinaceous cell wall surrounds a complex matrix consisting of sediment, bacteria and nitrate which is concentrated to hundreds of mM in the gromiid cell. The nitrate is respired to dinitrogen, but in contrast...... to the findings of eukaryotic mediated nitrate reduction in some foraminifera and diatoms, nitrate respiration in gromiids seems to be mediated by bacterial endosymbionts. The role of endobionts in nitrate accumulating eukaryotes is of fundamental importance for understanding the evolutionary path...

  18. A Triple-Probe Channel NO{sub 2}S{sub 2}-Macrocycle: Synthesis, Sensing Characteristics and Crystal Structure of Mercury(II) Nitrate Complex

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ji Eun; Seo, Moo Lyong; Lee, Shim Sung [Gyeongsang National University, Jinju (Korea, Republic of); Choi, Kyu Seong [Kyungnam University, Masan (Korea, Republic of)

    2010-07-15

    A triple-probe channel type chemosensor based on an NO{sub 2}S{sub 2}-macrocycle functionalized with phenyltricyanovinyl group was synthesized and its sensing characteristics were examined. The pink-red solution of L changed selectively to pale yellow upon addition of Hg{sup 2+}. The selective fluorometric response of L to all the tested metal ions was studied. The results showed that a large enhancement of the fluorescence of L was observed only in the case of Hg{sup 2+}. In addition, L showed large anodic shift ({approx} 0.3 V) for the addition of excess Hg{sup 2+}. Through above three observed results by the different techniques, we confirmed that the proposed chemosensor acts as the multiple-probe channel sensing material. The crystal structure of mercury(II) nitrate complexes of L which shows a 1-D polymer network with a formula [Hg{sub 2}(L){sub 2}(NO{sub 3}){sub 2}({mu}-NO{sub 3}){sub 2}]{sub n} was also reported.

  19. Synthesis and magnetic properties of a new family of macrocyclic M(II)3Ln(III) complexes: insights into the effect of subtle chemical modification on single-molecule magnet behavior.

    Science.gov (United States)

    Feltham, Humphrey L C; Clérac, Rodolphe; Ungur, Liviu; Vieru, Veacheslav; Chibotaru, Liviu F; Powell, Annie K; Brooker, Sally

    2012-10-15

    Thirteen tetranuclear mixed-metal complexes of the hexaimine macrocycle (L(Pr))(6-) have been prepared in a one-pot 3:1:3:3 reaction of copper(II) acetate hydrate, the appropriate lanthanide(III) nitrate hydrate, 1,4-diformyl-2,3-dihydroxybenzene (1), and 1,3-diaminopropane. The resulting family of copper(II)-lanthanide(III) macrocyclic complexes has the general formula Cu(II)(3)Ln(III)(L(Pr))(NO(3))(3)·solvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Tb, Ho, Er, Tm, or Yb). X-ray crystal structure determinations carried out on [Cu(3)Ce(L(Pr))(NO(3))(3)(MeOH)(3)] and [Cu(3)Dy(L(Pr))(NO(3))(3)(MeOH)(3)] confirmed that the large Ln(III) ion is bound in the central O(6) site and the three square pyramidal Cu(II) ions in the outer N(2)O(2) sites (apical donor either nitrate anion or methanol molecule) of the Schiff base macrocycle. Only the structurally characterized Cu(3)Tb complex, reported earlier, is a single-molecule magnet (SMM): the other 12 complexes do not exhibit an out-of-phase ac susceptibility signal or hysteresis of magnetization in a dc field. Ab initio calculations allowed us to rationalize the observed magnetic properties, including the significant impact of subtle chemical modification on SMM behavior. Broken-symmetry density functional theory (BS-DFT) calculations show there is a subtle structural balance as to whether the Cu···Cu exchange coupling is ferro- or antiferromagnetic. Of the family of 13 magnetically characterized tetranuclear Cu(II)(3)Ln(III) macrocyclic complexes prepared, only the Tb(III) complex is an SMM: the theoretical reasons for this are discussed.

  20. Sterically congested uranyl complexes with seven-coordination of the UO{sub 2} unit: the peculiar ligation mode of nitrate in [UO{sub 2}(NO{sub 3}){sub 2}(Rbtp)] complexes

    Energy Technology Data Exchange (ETDEWEB)

    Berthet, J. C.; Thuery, P.; Dognon, J. P.; Ephritikhine, M. [CEA Saclay, DSM, Serv Chim Mol, CNRS, URA 331, F-91191 Gif Sur Yvette, (France); Guillaneux, D. [CEA VALRHO, DEN/VRH/DRCP/SCPS/LCAM, F-30207 Bagnols Sur Ceze, (France)

    2008-07-01

    Addition of 1 or 2 molar equiv of Rbtp [Rbtp 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine; R = Me, Pr{sup n} to UO{sub 2}(OTf){sub 2} in anhydrous acetonitrile gave the neutral compounds [UO{sub 2}(OTf){sub 2}(Rbtp)] [RMe (1), {sup n}Pr (2)] and the cationic complexes [UO{sub 2}(Rbtp){sub 2}][OTf]{sub 2} [R = Me (3), Pr{sup n} (4)], respectively. No equilibrium between the mono and bis(Rbtp) complexes or between [UO{sub 2}(Rbtp){sub 2}][OTf]{sub 2} and free Rbtp in acetonitrile was detected by NMR spectroscopy. The crystal structures of 1 and 3 resemble those of their ter-pyridine analogues, and 3 is another example of a uranyl complex with the uranium atom in the unusual rhombohedral environment. In the presence of 1 molar equiv of Rbtp in acetonitrile, UO{sub 2}(NO{sub 3}){sub 2} was in equilibrium with [UO{sub 2}(NO{sub 3}){sub 2}(Rbtp)] and the formation of the bis adduct was not observed, even with an excess of Rbtp. The X-ray crystal structures of [UO{sub 2}(NO{sub 3}){sub 2}(Rbtp)] [R = Me (5), Pr{sup n} (6)] reveal a particular coordination geometry with seven coordinating atoms around the UO{sub 2} fragment. The large steric crowding in the equatorial girdle forces the bidentate nitrate ligands to be almost perpendicular to the mean equatorial plane, inducing bending of the UO{sub 2} fragment. The dinuclear oxo compound [U(CyMe{sub 4}btbp){sub 2}({mu}-O)UO{sub 2}(NO{sub 3}){sub 3}][OTf] (7), which was obtained fortuitously from a 1:21 mixture of U(OTf){sub 4}, CyMe{sub 4}btbp, and UO{sub 2}(NO{sub 3}){sub 2} [CyMe{sub 4}btbp6,6'-bis-(3,3,6,6-tetramethyl-cyclohexane-1,2,4-triazin-3-yl)-2,2 = '-bipyridine] is a very rare example of a mixed valence complex involving covalently bound U(IV) and U(VI) ions; its crystal structure also exhibits a seven coordinate uranyl moiety, with one bidentate nitrate group almost parallel to the UO{sub 2} fragment. The distinct structural features of [UO{sub 2}(k{sup 2}-NO{sub 3}){sub 2}(Mebtp)], with its high

  1. Silver(I nitrate complexes of three tetrakis-thioether-substituted pyrazine ligands: metal–organic chain, network and framework structures

    Directory of Open Access Journals (Sweden)

    Tokouré Assoumatine

    2017-03-01

    Full Text Available The reaction of the ligand 2,3,5,6-tetrakis[(methylsulfanylmethyl]pyrazine (L1 with silver(I nitrate led to {[Ag(C12H20N2S4](NO3}n, (I, catena-poly[[silver(I-μ-2,3,5,6-tetrakis[(methylsulfanylmethyl]pyrazine] nitrate], a compound with a metal–organic chain structure. The asymmetric unit is composed of two half ligands, located about inversion centres, with one ligand coordinating to the silver atoms in a bis-tridentate manner and the other in a bis-bidentate manner. The charge on the metal atom is compensated for by a free nitrate anion. Hence, the silver atom has a fivefold S3N2 coordination sphere. The reaction of the ligand 2,3,5,6-tetrakis[(phenylsulfanylmethyl]pyrazine (L2 with silver(I nitrate, led to [Ag2(NO32(C32H28N2S4]n, (II, poly[di-μ-nitrato-bis{μ-2,3,5,6-tetrakis[(phenylsulfanylmethyl]pyrazine}disilver], a compound with a metal–organic network structure. The asymmetric unit is composed of half a ligand, located about an inversion centre, that coordinates to the silver atoms in a bis-tridentate manner. The nitrate anion coordinates to the silver atom in a bidentate/monodentate manner, bridging the silver atoms, which therefore have a sixfold S2NO3 coordination sphere. The reaction of the ligand 2,3,5,6-tetrakis[(pyridin-2-ylsulfanylmethyl]pyrazine (L3 with silver(I nitrate led to [Ag3(NO33(C28H24N6S4]n, (III, poly[trinitrato{μ6-2,3,5,6-tetrakis[(pyridin-2-ylsulfanylmethyl]pyrazine}trisilver(I], a compound with a metal–organic framework structure. The asymmetric unit is composed of half a ligand, located about an inversion centre, that coordinates to the silver atoms in a bis-tridentate manner. One pyridine N atom bridges the monomeric units, so forming a chain structure. Two nitrate O atoms also coordinate to this silver atom, hence it has a sixfold S2N2O2 coordination sphere. The chains are linked via a second silver atom, located on a twofold rotation axis, coordinated by the second pyridine N atom. A second nitrate anion

  2. Modeled Wet Nitrate Deposition

    Data.gov (United States)

    U.S. Environmental Protection Agency — Modeled data on nitrate wet deposition was obtained from Dr. Jeff Grimm at Penn State Univ. Nitrate wet depostion causes acidification and eutrophication of surface...

  3. Crystal structures of two mononuclear complexes of terbium(III) nitrate with the tripodal alcohol 1,1,1-tris­(hy­droxy­meth­yl)propane

    Science.gov (United States)

    Gregório, Thaiane; Giese, Siddhartha O. K.; Nunes, Giovana G.; Soares, Jaísa F.; Hughes, David L.

    2017-01-01

    Two new mononuclear cationic complexes in which the TbIII ion is bis-chelated by the tripodal alcohol 1,1,1-tris­(hy­droxy­meth­yl)propane (H3 L Et, C6H14O3) were prepared from Tb(NO3)3·5H2O and had their crystal and mol­ecular structures solved by single-crystal X-ray diffraction analysis after data collection at 100 K. Both products were isolated in reasonable yields from the same reaction mixture by using different crystallization conditions. The higher-symmetry complex dinitratobis[1,1,1-tris­(hy­droxy­meth­yl)propane]­terbium(III) nitrate di­meth­oxy­ethane hemisolvate, [Tb(NO3)2(H3 L Et)2]NO3·0.5C4H10O2, 1, in which the lanthanide ion is 10-coordinate and adopts an s-bicapped square-anti­prismatic coordination geometry, contains two bidentate nitrate ions bound to the metal atom; another nitrate ion functions as a counter-ion and a half-mol­ecule of di­meth­oxy­ethane (completed by a crystallographic twofold rotation axis) is also present. In product aqua­nitratobis[1,1,1-tris­(hy­droxy­meth­yl)propane]­terbium(III) dinitrate, [Tb(NO3)(H3 L Et)2(H2O)](NO3)2, 2, one bidentate nitrate ion and one water mol­ecule are bound to the nine-coordinate terbium(III) centre, while two free nitrate ions contribute to charge balance outside the tricapped trigonal-prismatic coordination polyhedron. No free water mol­ecule was found in either of the crystal structures and, only in the case of 1, di­meth­oxy­ethane acts as a crystallizing solvent. In both mol­ecular structures, the two tripodal ligands are bent to one side of the coordination sphere, leaving room for the anionic and water ligands. In complex 2, the methyl group of one of the H3 L Et ligands is disordered over two alternative orientations. Strong hydrogen bonds, both intra- and inter­molecular, are found in the crystal structures due to the number of different donor and acceptor groups present. PMID:28217359

  4. Micromachined Amperometric Nitrate Sensor

    OpenAIRE

    Dohyun Kim; Ira Goldberg; Jack Judy

    2003-01-01

    A nitrate-sensing system that consists of a micromachined sensor substrate, nitrate-permeable membrane, integrated microfluidic channels, and standard fluidic connectors has been designed, fabricated, assembled, and tested. Our microsensor was designed for in-situ monitoring of nitrate concentrations in ground water. A silver electrode was patterned for amperometric nitrate detection. An electrochemically oxidized silver electrode was used as a reference electrode. Microfluidic channels were ...

  5. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium nitrate and potassium nitrate. 181.33...-Sanctioned Food Ingredients § 181.33 Sodium nitrate and potassium nitrate. Sodium nitrate and potassium nitrate are subject to prior sanctions issued by the U.S. Department of Agriculture for use as sources...

  6. Molecular dynamics simulations of ter-pyridine and bis-triazinyl-pyridine complexes with lanthanide cations; Etude de dynamique moleculaire de complexes de la bis-triazinyl-pyridine (BTP) et de la terpyridine avec des lanthanides(3)

    Energy Technology Data Exchange (ETDEWEB)

    Guilbaud, Ph. [CEA Valrho, (DCC/DRRV/SEMP), 30 - Marcoule (France)

    2000-07-01

    The search for ligands which specifically separate actinides(III) from lanthanides(III) by liquid-liquid extraction has prompted considerable research in the Process Design and Modeling Department ('Service d'Etude et de Modelisation des Procedes'- SEMP). Ligands with soft donor atoms AS) that are able to perform this separation have already been investigated and research is currently under way to improve their performance for high acidic feeds. Theoretical chemistry research is conducted in the Theoretical and Structural Chemistry Laboratory ('Laboratoire de Chimie Theorique et Structurale') to improve our understanding of the complexation and extraction of these cations with such ligands. Theoretical studies were first carried out for the ter-pyridine (TPY) and bis-triazinyl-pyridine (BTP) ligands that display fairly good ability to separate and extract actinide(III) from lanthanide(III) ions. Molecular dynamics simulations were performed on ter-pyridine and bis-triazinyl-pyridine complexes with three lanthanide cations (La{sup 3+}, Eu{sup 3+} and Lu{sup 3+}) for vacuum and for water solutions. These calculations were carried out without counter-ions, with three nitrate (NO{sub 3}{sup -}) ions, and, in the case of ter-pyridine, with three {alpha}-bromo-caprate anions that are likely to be used experimentally as synergistic agents for the separation and extraction of An(III) from Ln(III). Molecular dynamics simulations were first performed for vacuum to evaluate the distances between nitrogen and lanthanide atoms (Ln{sup 3+},N) and intrinsic interaction energies to poly-nitrogenous ligands with or without NO{sub 3} ions, and for both ligands. The (Ln{sup 3+},N) distances decrease and the cation/ligand interaction energies increase along the La{sup 3+}, Eu{sup 3+}, Lu{sup 3+} series, with decreasing Ln(III) ion radii. The introduction of nitrate counter-ions makes the (Ln{sup 3+},N) distances slightly higher, and the TPY/Ln{sup 3+} and BTP

  7. Ammonium nitrate explosion hazards

    Directory of Open Access Journals (Sweden)

    Negovanović Milanka

    2015-01-01

    Full Text Available Ammonium nitrate (AN primarily is used as a fertilizer but it is also very important compound in the production of industrial explosives. The application of ammonium nitrate in the production of industrial explosives was related with the early era of Nobel dynamite and widely increased with the appearance of blasting agents such as ANFO and Slurry, in the middle of the last Century. Throughout the world millions of tons of ammonium nitrate are produced annually and handled without incident. Although ammonium nitrate generally is used safely, accidental explosions involving AN have high impact resulting in loss of lives and destruction of property. The paper presents the basic properties of ammonium nitrate as well as hazards in handling of ammonium nitrate in order to prevent accidents. Several accidents with explosions of ammonium nitrate resulted in catastrophic consequences are listed in the paper as examples of non-compliance with prescribed procedures.

  8. The silver(I nitrate complex of the ligand N-(pyridin-2-ylmethylpyrazine-2-carboxamide: a metal–organic framework (MOF structure

    Directory of Open Access Journals (Sweden)

    Dilovan S. Cati

    2017-04-01

    Full Text Available The reaction of silver(I nitrate with the mono-substituted pyrazine carboxamide ligand, N-(pyridin-2-ylmethylpyrazine-2-carboxamide (L, led to the formation of the title compound with a metal–organic framework (MOF structure, [Ag(C11H10N4O(NO3]n, poly[μ-nitrato-[μ-N-(pyridin-2-ylmethyl-κNpyrazine-2-carboxamide-κN4]silver(I]. The silver(I atom is coordinated by a pyrazine N atom, a pyridine N atom, and two O atoms of two symmetry-related nitrate anions. It has a fourfold N2O2 coordination sphere, which can be described as distorted trigonal–pyramidal. The ligands are bridged by the silver atoms forming –Ag–L–Ag–L– zigzag chains along the a-axis direction. The chains are arranged in pairs related by a twofold screw axis. They are linked via the nitrate anions, which bridge the silver(I atoms in a μ2 fashion, forming the MOF structure. Within the framework there are N—H...O and C—H...O hydrogen bonds present.

  9. Synthesis and spectral studies of macrocyclic Pb(Ⅱ), Zn(Ⅱ), Cd(II)and La(Ⅲ) complexes derived from 1,4-bis(3-aminopropoxy)butane with metal nitrate and salicylaldehyde derivatives

    Institute of Scientific and Technical Information of China (English)

    Salih Ilhan; Hamdi Temel; Salih Pasa

    2009-01-01

    Eight new macrocyclic complexes were synthesized by template reaction of 1,4-bis(3-aminopropoxy)butane with metal nitrate and 1,3-bis(2-forrnylphenyl)propane or 1,4-bis(2-formylphenyl)butane and their structures were proposed on the basis of elemental analysis, FTIR, UV-vis, molar conductivity measurements, 1H NMR and mass spectra. The metals to ligand molar ratios of the complexes were found to be 1:1. The complexes are 1:2 electrolytes for Pb(II), Zn(II) and Cd(II) complexes and 1:3 electrolytes for La(lIl) as shown by their molar conductivities (Am) in DMSO at 10-3 tool L-l. Due to the existence of free ions in these complexes,such complexes are electrically conductive. The configurations of La(Ⅲ) and Pb(U) were proposed to probably octahedral and Zn(II) and Cd(II) complexes were proposed to probably tetrahedral.

  10. Nitrate-Bridged One-Dimension Coordination Polymer Self-Assembled from a N4O2-Tetraiminodiphenolate Dicopper(II Macrocyclic Complex

    Directory of Open Access Journals (Sweden)

    Julio Cesar da Rocha

    2015-01-01

    Full Text Available Herein we report on the synthesis and single crystal X-ray structure characterization of [{Cu2(tidf(μ-NO3}∞]ClO4 (tidf = a Robson type macrocyclic ligand obtained upon condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane. The coordination geometry around the copper(II is square-pyramidal and has [Cu2(tidf]2+ units connected to each other through nitrate bridges extending as a one-dimension coordination polymer. The compound exhibits an extensive supramolecular structure supported by nonclassic hydrogen bonding between C-H⋯Operchlorate and C-H⋯Onitrate.

  11. Structural and thermodynamic study of rare earth(III) complexation by poly-hydroxylated carboxylic acids: synthesis of new extractants and outlook for the extraction of these cations; Etude structurale et thermodynamique de la complexation de lanthanides (III) par des acides carboxyliques polyhydroxyles: synthese de nouveaux extractants et perspectives pour l'extraction de ces cations

    Energy Technology Data Exchange (ETDEWEB)

    Aury, S

    2002-12-15

    The aim of this work is: to improve the knowledge on the binding sites of the poly-hydroxylated carboxylic acids with the trivalent lanthanide(III) ions by comparing them to gluconic acid (previously studied) and to molecules with different configuration and with a variable number of OH functions (threonic acid, glyceric acid, 2-hydroxy-butanoic acid, 3-hydroxy-butanoic acid). To find the best complexing agent among different acids (aldonic acids, aldaric acids, di-hydroxybenzoic acids) (determination of the set of complexes and their stability constants by potentiometry, NMR and UV-Visible spectroscopy). To synthesize hydrophobic monoamides from one lactone form of saccharic acid, to study their complexing power and their capacity to extract the trivalent lanthanide(III) ions. (author)

  12. Agricultural nitrate pollution

    DEFF Research Database (Denmark)

    Anker, Helle Tegner

    2015-01-01

    Despite the passing of almost 25 years since the adoption of the EU Nitrates Directive, agricultural nitrate pollution remains a major concern in most EU Member States. This is also the case in Denmark, although a fairly strict regulatory regime has resulted in almost a 50 per cent reduction...

  13. Nitrate Leaching Index

    Science.gov (United States)

    The Nitrate Leaching Index is a rapid assessment tool that evaluates nitrate (NO3) leaching potential based on basic soil and climate information. It is the basis for many nutrient management planning efforts, but it has considerable limitations because of : 1) an oversimplification of the processes...

  14. Factors influencing protein tyrosine nitration--structure-based predictive models.

    Science.gov (United States)

    Bayden, Alexander S; Yakovlev, Vasily A; Graves, Paul R; Mikkelsen, Ross B; Kellogg, Glen E

    2011-03-15

    Models for exploring tyrosine nitration in proteins have been created based on 3D structural features of 20 proteins for which high-resolution X-ray crystallographic or NMR data are available and for which nitration of 35 total tyrosines has been experimentally proven under oxidative stress. Factors suggested in previous work to enhance nitration were examined with quantitative structural descriptors. The role of neighboring acidic and basic residues is complex: for the majority of tyrosines that are nitrated the distance to the heteroatom of the closest charged side chain corresponds to the distance needed for suspected nitrating species to form hydrogen bond bridges between the tyrosine and that charged amino acid. This suggests that such bridges play a very important role in tyrosine nitration. Nitration is generally hindered for tyrosines that are buried and for those tyrosines for which there is insufficient space for the nitro group. For in vitro nitration, closed environments with nearby heteroatoms or unsaturated centers that can stabilize radicals are somewhat favored. Four quantitative structure-based models, depending on the conditions of nitration, have been developed for predicting site-specific tyrosine nitration. The best model, relevant for both in vitro and in vivo cases, predicts 30 of 35 tyrosine nitrations (positive predictive value) and has a sensitivity of 60/71 (11 false positives). Copyright © 2010 Elsevier Inc. All rights reserved.

  15. Covalent lanthanide(III) macrocyclic complexes: the bonding nature and optical properties of a promising single antenna molecule.

    Science.gov (United States)

    Rabanal-León, Walter A; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

    2014-12-21

    The present work is focused on the elucidation of the electronic structure, bonding nature and optical properties of a series of low symmetry (C2) coordination compounds of type [Ln(III)HAM](3+), where "Ln(III)" are the trivalent lanthanide ions: La(3+), Ce(3+), Eu(3+) and Lu(3+), while "HAM" is the neutral six-nitrogen donor macrocyclic ligand [C22N6H26]. This systematic study has been performed in the framework of the Relativistic Density Functional Theory (R-DFT) and also using a multi-reference approach via the Complete Active Space (CAS) wavefunction treatment with the aim of analyzing their ground state and excited state electronic structures as well as electronic correlation. Furthermore, the use of the energy decomposition scheme proposed by Morokuma-Ziegler and the electron localization function (ELF) allows us to characterize the bonding between the lanthanide ions and the macrocyclic ligand, obtaining as a result a dative-covalent interaction. Due to a great deal of lanthanide optical properties and their technological applications, the absorption spectra of this set of coordination compounds were calculated using the time-dependent density functional theory (TD-DFT), where the presence of the intense Ligand to Metal Charge Transfer (LMCT) bands in the ultraviolet and visible region and the inherent f-f electronic transitions in the Near-Infra Red (NIR) region for some lanthanide ions allow us to propose these systems as "single antenna molecules" with potential applications in NIR technologies.

  16. Bioactivation of organic nitrates and the mechanism of nitrate tolerance.

    Science.gov (United States)

    Klemenska, Emila; Beresewicz, Andrzej

    2009-01-01

    Organic nitrates, such as nitroglycerin, are commonly used in the therapy of cardiovascular disease. Long-term therapy with these drugs, however, results in the rapid development of nitrate tolerance, limiting their hemodynamic and anti-ischemic efficacy. In addition, nitrate tolerance is associated with the expression of potentially deleterious modifications such as increased oxidative stress, endothelial dysfunction, and sympathetic activation. In this review we discuss current concepts regarding the mechanisms of organic nitrate bioactivation, nitrate tolerance, and nitrate-mediated oxidative stress and endothelial dysfunction. We also examine how hydralazine may prevent nitrate tolerance and related endothelial dysfunction.

  17. Experimental and Theoretical Studies on Biologically Active Lanthanide (III) Complexes

    Science.gov (United States)

    Kostova, I.; Trendafilova, N.; Georgieva, I.; Rastogi, V. K.; Kiefer, W.

    2008-11-01

    The complexation ability and the binding mode of the ligand coumarin-3-carboxylic acid (HCCA) to La(III), Ce(III), Nd(III), Sm(III), Gd(III) and Dy(III) lanthanide ions (Ln(III)) are elucidated at experimental and theoretical level. The complexes were characterized using elemental analysis, DTA and TGA data as well as 1H NMR and 13C NMR spectra. FTIR and Raman spectroscopic techniques as well as DFT quantum chemical calculations were used for characterization of the binding mode and the structures of lanthanide(III) complexes of HCCA. The metal—ligand binding mode is predicted through molecular modeling and energy estimation of different Ln—CCA structures using B3LYP/6-31G(d) method combined with a large quasi-relativistic effective core potential for lanthanide ion. The energies obtained predict bidentate coordination of CCA- to Ln(III) ions through the carbonylic oxygen and the carboxylic oxygen. Detailed vibrational analysis of HCCA, CCA- and Ln(III) complexes based on both calculated and experimental frequencies confirms the suggested metal—ligand binding mode. The natural bonding analysis predicts strongly ionic character of the Ln(III)-CCA bonding in the- complexes studied. With the relatively resistant tumor cell line K-562 we obtained very interesting in-vitro results which are in accordance with our previously published data concerning the activity of lanthanide(III) complexes with other coumarin derivatives.

  18. VT Nitrate Leaching Index

    Data.gov (United States)

    Vermont Center for Geographic Information — (Link to Metadata) Nitrate Leaching Index data for the state of Vermont. This is a derivative product based on the SSURGO soils data for all counties except Essex...

  19. Agricultural nitrate pollution

    DEFF Research Database (Denmark)

    Anker, Helle Tegner

    2015-01-01

    Despite the passing of almost 25 years since the adoption of the EU Nitrates Directive, agricultural nitrate pollution remains a major concern in most EU Member States. This is also the case in Denmark, although a fairly strict regulatory regime has resulted in almost a 50 per cent reduction...... in nitrogen leaching since the mid-80s. Nevertheless, further effort is needed, particularly in ecologically sensitive areas. This article discusses different regulatory approaches – and in particular the need for a differentiated nitrate regulation tailored to meet site-specific ecological demands – from...... of the mandatory specification standards of the Nitrates Directive combined with additional instruments to address the need for severe restrictions on fertiliser use or cultivation practices in the most ecologically vulnerable areas....

  20. Nitrate storage and dissimilatory nitrate reduction by eukaryotic microbes

    DEFF Research Database (Denmark)

    Kamp, Anja; Høgslund, Signe; Risgaard-Petersen, Nils

    2015-01-01

    and use it for dissimilatory nitrate reduction in the absence of oxygen. The paradigm shift that this entailed is ecologically significant because the eukaryotes in question comprise global players like diatoms, foraminifers, and fungi. This review article provides an unprecedented overview of nitrate....... A first compilation of intracellular nitrate inventories in various marine sediments is presented, indicating that intracellular nitrate pools vastly exceed porewater nitrate pools. The relative contribution by foraminifers to total sedimentary denitrification is estimated for different marine settings...

  1. Protein tyrosine nitration

    Science.gov (United States)

    Chaki, Mounira; Leterrier, Marina; Barroso, Juan B

    2009-01-01

    Nitric oxide metabolism in plant cells has a relative short history. Nitration is a chemical process which consists of introducing a nitro group (-NO2) into a chemical compound. in biological systems, this process has been found in different molecules such as proteins, lipids and nucleic acids that can affect its function. This mini-review offers an overview of this process with special emphasis on protein tyrosine nitration in plants and its involvement in the process of nitrosative stress. PMID:19826215

  2. Synthesis and Characterization of New Macrocyclic Cu(Ⅱ)Complexes from Various Diamines, Copper(Ⅱ) Nitrate and 1,4-Bis(2-formylphenoxy)butane

    Institute of Scientific and Technical Information of China (English)

    ILHAN, Salih; TEMEL, Hamdi; KILIC, Ahmet

    2007-01-01

    Six new macrocyclic complexes were synthesized by a template reaction of 1,4-bis(2-formylphenoxy)butane with diamines and Cu(NO3)2·3H2O and their structures were proposed on the basis of elemental analysis, FT-IR,UV-Vis, magnetic susceptibility measurements, molar conductivity measurements and mass spectra. The metal to ligand molar ratios of the Cu(Ⅱ) complexes were found to be 1∶1. The Cu(Ⅱ) complexes are 1∶2 electrolytes as shown by their molar conductivities (Λm) in DMF at 10-3 mol·L-1. Due to the existence of free ions the Cu(Ⅱ)complexes are electrically conductive. Their configurations were proposed to be probably distorted octahedral.

  3. Structure of a dinuclear cadmium complex with 2,2'-bi-pyridine, monodentate nitrate and 3-carb-oxy-6-methyl-pyridine-2-carboxyl-ate ligands: intra-molecular carbon-yl(lone pair)⋯π(ring) and nitrate(π)⋯π(ring) inter-actions.

    Science.gov (United States)

    Granifo, Juan; Suarez, Sebastián; Baggio, Ricardo

    2015-08-01

    The centrosymmetric dinuclear complex bis-(μ-3-carb-oxy-6-methyl-pyridine-2-carboxyl-ato)-κ(3) N,O (2):O (2);κ(3) O (2):N,O (2)-bis-[(2,2'-bi-pyridine-κ(2) N,N')(nitrato-κO)cadmium] methanol monosolvate, [Cd2(C8H6NO4)2(NO3)2(C10H8N2)2]·CH3OH, was isolated as colourless crystals from the reaction of Cd(NO3)2·4H2O, 6-methyl-pyridine-2,3-di-carb-oxy-lic acid (mepydcH2) and 2,2'-bi-pyridine in methanol. The asymmetric unit consists of a Cd(II) cation bound to a μ-κ(3) N,O (2):O (2)-mepydcH(-) anion, an N,N'-bidentate 2,2'-bi-pyridine group and an O-mono-dentate nitrate anion, and is completed with a methanol solvent mol-ecule at half-occupancy. The Cd complex unit is linked to its centrosymmetric image through a bridging mepydcH(-) carboxyl-ate O atom to complete the dinuclear complex mol-ecule. Despite a significant variation in the coordination angles, indicating a considerable departure from octa-hedral coordination geometry about the Cd(II) atom, the Cd-O and Cd-N distances in this complex are surprisingly similar. The crystal structure consists of O-H⋯O hydrogen-bonded chains parallel to a, further bound by C-H⋯O contacts along b to form planar two-dimensional arrays parallel to (001). The juxtaposed planes form inter-stitial columnar voids that are filled by the methanol solvent mol-ecules. These in turn inter-act with the complex mol-ecules to further stabilize the structure. A search in the literature showed that complexes with the mepydcH(-) ligand are rare and complexes reported previously with this ligand do not adopt the μ-κ(3) coordination mode found in the title compound.

  4. Synthesis, characterization, and activity of yttrium(III) nitrate complexes bearing tripodal phosphine oxide and mixed phosphine-phosphine oxide ligands.

    Science.gov (United States)

    Sues, Peter E; Lough, Alan J; Morris, Robert H

    2012-09-03

    A series of four tripodal phosphine oxide ligands, (OPR(2))(2)CHCH(2)POR(2) (1a-1d), and four mixed phosphine-phosphine oxide ligands, (OPR(2))(2)CHCH(2)PR(2) (3a-3d), were synthesized and coordinated to yttrium to produce Y(NO(3))(3)[(OPR(2))(2)CHCH(2)POR(2)] (2a-2d) and Y(NO(3))(3)[(OPR(2))(2)CHCH(2)PR(2)](OPPh(3)) (4a-4d) complexes. The previously reported ligand 1a and unknown phosphine oxide ligands 1b-1d were generated in an unprecedented trisubstitution reaction of bromoacetaldehyde diethyl acetal, while the novel partially reduced ligands 3a-3d were synthesized from 1a-1d according to a known literature protocol for the selective monoreduction of bisphosphine oxides. The neutral yttrium complexes 2a-2d are nine-coordinate and display a tricapped trigonal-prismatic geometry. Complexes 4a-4d are also neutral, nine-coordinate species and have a pendant phosphine functionality, which provides the potential to form bimetallic early-late transition-metal complexes. Additionally, yttrium complexes 2a-2d were activated with base and tested for the ring-opening polymerization of ε-caprolactone, but the results showed that base by itself was significantly more effective than the yttrium species investigated.

  5. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660{plus_minus}0.092 at 25 C, and extraction enthalpy is -5. 46{plus_minus}0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 {times} 10{sup 6}{plus_minus}3.56 {times} 10{sup 4} at 25 C; reaction enthalpy was -9.610{plus_minus}0.594 kcal/mol. Nitration complexation constant is 8.412{plus_minus}0.579, with an enthalpy of -10.72{plus_minus}1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured.

  6. Determination of Constant-Volume Combustion Energy for the Complexes of Zinc Nitrate with Four Amino Acids%硝酸锌与四种α-氨基酸配合物的恒容燃烧能测定

    Institute of Scientific and Technical Information of China (English)

    谢钢; 杨旭武; 陈三平; 高胜利; 史启祯

    2003-01-01

    Ten solid complexes of zinc nitrate with L-α-leucine(Leu), L-α-valine(Val), L-α-tryptophan(Try) andL-α-threonine(Thr) were prepared in water. The compositions of these complexes are determined by chemicalanalysis and elemental analysis, which are identified as Zn (Leu) (NO3) 2 @ 2H2O (A), Zn (Leu)2 (NO3)2 @ H2O (B),Zn(Val) (NO3)2 @ 2H2O(C), Zn(Val) 2(NO3)2 @ H2O(D), Zn(Val) 3(NO3) 2 @ H2O(E), Zn(Try) (NO3)2 @ 2H2O(F), Zn(Try)2(NO3)2 @ H2O(G), Zn(Thr) (NO3)2 @ 2H2O(H), Zn(Thr) 2(NO3)2 @ H2O(I) and Zn(Thr) 3(NO3)@ H2O(J) . The constant-volume combustion energies of the complexes, Δc U(complex), were determined by aprecise rotating bomb calorimeter at 298.15K. Standard enthalpies of combustion, ΔcH-m(complex, s, 298. 15K),and standard enthalpies of formation, ΔfH-m (complex, s, 298. 15K) for these complexes were calculated as(4523.22 ± 2.08), (7208.86 ± 4.28), (3442.21 ± 1.85), (5971.21 ±3.32), (9007.26 ± 4.24),(5802.35±2.14), (10891.58±3.01), (2147.40±1.28), (4120.83±0.99), (6444.68±3.85)kJ@mol-1and (615.67±2.27), (1863.16±4.60), (1017.34±2.00), (1742.93±3.61), (2245.70±4.73),(1161.18±2.61), (1829.71±4.20), (1632.82±1.43), (1885.55±1.50), (2770. 25 ± 4. 21) kJ @ mol-1,respectively.

  7. Hot Spots and Persistence of Nitrate in Aquifers Across Scales

    Directory of Open Access Journals (Sweden)

    Dipankar Dwivedi

    2016-01-01

    Full Text Available Nitrate-N (NO3 -- N is one of the most pervasive contaminants in groundwater. Nitrate in groundwater exhibits long-term behavior due to complex interactions at multiple scales among various geophysical factors, such as sources of nitrate-N, characteristics of the vadose zone and aquifer attributes. To minimize contamination of nitrate-N in groundwater, it is important to estimate hot spots (>10 mg/L of NO3 -- N, trends and persistence of nitrate-N in groundwater. To analyze the trends and persistence of nitrate-N in groundwater at multiple spatio-temporal scales, we developed and used an entropy-based method along with the Hurst exponent in two different hydrogeologic settings: the Trinity and Ogallala Aquifers in Texas at fine (2 km × 2 km, intermediate (10 km × 10 km and coarse (100 km × 100 km scales. Results show that nitrate-N exhibits long-term persistence at the intermediate and coarse scales. In the Trinity Aquifer, overall mean nitrate-N has declined with a slight increase in normalized marginal entropy (NME over each decade from 1940 to 2008; however, the number of hot spots has increased over time. In the Ogallala Aquifer, overall mean nitrate-N has increased with slight moderation in NME since 1940; however, the number of hot spots has significantly decreased for the same period at all scales.

  8. Interaction of neodymium nitrate with rubidium and cesium nitrates

    Energy Technology Data Exchange (ETDEWEB)

    Molodkin, A.K.; Odinets, Z.K.; S' ' edina, T.V.; Ivanova, T.N. (Universitet Druzhby Narodov, Moscow (USSR))

    1982-12-01

    The Rb/sub 2/Nd(NO/sub 3/)/sub 5/xH/sub 2/O (1) and Cs/sub 2/Nd(NO/sub 3/)/sub 5/xH/sub 2/O (2) new complexes are prepared. The crystals 1 are isotropic, of cubic crystal system, Ng=1.570+-0.002; 2 - Ng=1.582+-0.002; Csub(Np)=0-9 degrees, of low crystal system (syngony). The bands of coordinated nitrate group, the ..delta nu..=..nu../sub 4/(B/sub 2/)-..nu../sub 1/(A/sub 1/) splitting value is respectively equal to 225 and 230 cm/sup -1/ are present in the infrared absorption spectra of the compounds. The interplane distances and corresponding intensities for the 1, 2 and hexahydrate of neodymium nitrate are determined. Derivatograms of the compounds are recorded, the final products of the thermolysis are correspondingly RbNdO/sub 2/ and Nd/sub 2/O/sub 3/.

  9. Nitrate absorption through hydrotalcite reformation.

    Science.gov (United States)

    Frost, Ray L; Musumeci, Anthony W

    2006-10-01

    Thermally activated hydrotalcite based upon a Zn/Al hydrotalcite with carbonate in the interlayer has been used to remove nitrate anions from an aqueous solution resulting in the reformation of a hydrotalcite with a mixture of nitrate and carbonate in the interlayer. X-ray diffraction of the reformed hydrotalcites with a d(003) spacing of 7.60 A shows that the nitrate anion is removed within a 30 min period. Raman spectroscopy shows that two types of nitrate anions exist in the reformed hydrotalcite (a) nitrate bonded to the 'brucite-like' hydrotalcite surface and (b) aquated nitrate anion in the interlayer. Kinetically the nitrate is replaced by the carbonate anion over a 21 h period. Two types of carbonate anions are observed. This research shows that the reformation of a thermally activated hydrotalcite can be used to remove anions such as nitrate from aqueous systems.

  10. Nitrate Leaching Management

    Science.gov (United States)

    Nitrate (NO3) leaching is a significant nitrogen (N) loss process for agriculture that must be managed to minimize NO3 enrichment of groundwater and surface waters. Managing NO3 leaching should involve the application of basic principles of understanding the site’s hydrologic cycle, avoiding excess ...

  11. Complexation of actinides(III) and lanthanides(III) cations by tridentate nitrogen ligands; Complexation des cations actinides(III) et lanthanides(III) par des ligands azotes tridentates

    Energy Technology Data Exchange (ETDEWEB)

    Cordier, P.Y.; Francois, N.; Guillaneux, D.; Hill, C.; Madic, Ch. [CEA Valrho, (DCC/DRRV/SEMP), 30 - Marcoule (France); Illemassene, M. [Paris-11 Univ., 91 - Orsay (France). Inst. de Physique Nucleaire

    2000-07-01

    constants were then evaluated by mathematical processing of the whole spectrum. The following conclusions were drawn: - the protonation constants for MeBtp are far lower than for Tptz or Toy. This can be correlated to the fact that MeBtp can extract M(III) nitrates from solutions up to 2 molar nitric acid, whereas Tpy and Tptz are limited to acidities below 0,1 mol/l and require the use of a lipophilic anion; - all three ligands behave differently towards lanthanides(III) and americium(III): they all are quite stable AmL{sub 2}{sup 3+} complexes, and MeBtp forms a very stable Am(MeBtp){sub 3}{sup 3+} complex. This is consistent with the fact that both types of ligand selectively extract Am(III) cation, extractants of the Btp family demonstrating singular behavior. The number, stoichiometries and stability constants of the complexes formed in aqueous homogeneous conditions between lanthanide(III) and americium(III) cations and poly-hetero-aromatic nitrogen-containing ligands were determined through the combined use of Time-Resolved Laser Induced Fluorimetry and UV-visible spectrophotometry. Data obtained in homogeneous conditions confirmed the ability of nitrogen-containing ligands to discriminate between 4f and 5f cations, an ability already observed in solvent extraction studies. Evidence for the very high selectivity of 2,6-bis-(1,2,4-triazine-3-yl)-pyridine derivatives (Btp's) for americium(III) vs lanthanide(III) cations could also be obtained. This constitutes the first clue for a correlation, at least qualitative, between homogeneous and solvent extraction results. (authors)

  12. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Science.gov (United States)

    2010-07-01

    ... 33 Navigation and Navigable Waters 2 2010-07-01 2010-07-01 false Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. 126.28 Section 126...) WATERFRONT FACILITIES HANDLING OF DANGEROUS CARGO AT WATERFRONT FACILITIES § 126.28 Ammonium...

  13. Nitrate in drinking water

    DEFF Research Database (Denmark)

    Schullehner, Jörg; Hansen, Birgitte; Sigsgaard, Torben

    Annual nationwide exposure maps for nitrate in drinking water in Denmark from the 1970s until today will be presented based on the findings in Schullehner & Hansen (2014) and additional work on addressing the issue of private well users and estimating missing data. Drinking water supply in Denmark...... is highly decentralized and fully relying on simple treated groundwater. At the same time, Denmark has an intensive agriculture, making groundwater resources prone to nitrate pollution. Drinking water quality data covering the entire country for over 35 years are registered in the public database Jupiter....... In order to create annual maps of drinking water quality, these data had to be linked to 2,852 water supply areas, which were for the first time digitized, collected in one dataset and connected to the Jupiter database. Analyses of the drinking water quality maps showed that public water supplies...

  14. A structural and theoretical study of the alkylammonium nitrates forefather: Liquid methylammonium nitrate

    Science.gov (United States)

    Gontrani, Lorenzo; Caminiti, Ruggero; Salma, Umme; Campetella, Marco

    2017-09-01

    We present here a structural and vibrational analysis of melted methylammonium nitrate, the simplest compound of the family of alkylammonium nitrates. The static and dynamical features calculated were endorsed by comparing the experimental X-ray data with the theoretical ones. A reliable description cannot be obtained with classical molecular dynamics owing to polarization effects. Contrariwise, the structure factor and the vibrational frequencies obtained from ab initio molecular dynamics trajectories are in very good agreement with the experiment. A careful analysis has provided additional information on the complex hydrogen bonding network that exists in this liquid.

  15. Assimilation of nitrate by yeasts.

    Science.gov (United States)

    Siverio, José M

    2002-08-01

    Nitrate assimilation has received much attention in filamentous fungi and plants but not so much in yeasts. Recently the availability of classical genetic and molecular biology tools for the yeast Hansenula polymorpha has allowed the advance of the study of this metabolic pathway in yeasts. The genes YNT1, YNR1 and YNI1, encoding respectively nitrate transport, nitrate reductase and nitrite reductase, have been cloned, as well as two other genes encoding transcriptional regulatory factors. All these genes lie closely together in a cluster. Transcriptional regulation is the main regulatory mechanism that controls the levels of the enzymes involved in nitrate metabolism although other mechanisms may also be operative. The process involved in the sensing and signalling of the presence of nitrate in the medium is not well understood. In this article the current state of the studies of nitrate assimilation in yeasts as well as possible venues for future research are reviewed.

  16. Nitrate sensing by the maize root apex transition zone: a merged transcriptomic and proteomic survey.

    Science.gov (United States)

    Trevisan, Sara; Manoli, Alessandro; Ravazzolo, Laura; Botton, Alessandro; Pivato, Micaela; Masi, Antonio; Quaggiotti, Silvia

    2015-07-01

    Nitrate is an essential nutrient for plants, and crops depend on its availability for growth and development, but its presence in agricultural soils is far from stable. In order to overcome nitrate fluctuations in soil, plants have developed adaptive mechanisms allowing them to grow despite changes in external nitrate availability. Nitrate can act as both nutrient and signal, regulating global gene expression in plants, and the root tip has been proposed as the sensory organ. A set of genome-wide studies has demonstrated several nitrate-regulated genes in the roots of many plants, although only a few studies have been carried out on distinct root zones. To unravel new details of the transcriptomic and proteomic responses to nitrate availability in a major food crop, a double untargeted approach was conducted on a transition zone-enriched root portion of maize seedlings subjected to differing nitrate supplies. The results highlighted a complex transcriptomic and proteomic reprogramming that occurs in response to nitrate, emphasizing the role of this root zone in sensing and transducing nitrate signal. Our findings indicated a relationship of nitrate with biosynthesis and signalling of several phytohormones, such as auxin, strigolactones, and brassinosteroids. Moreover, the already hypothesized involvement of nitric oxide in the early response to nitrate was confirmed with the use of nitric oxide inhibitors. Our results also suggested that cytoskeleton activation and cell wall modification occurred in response to nitrate provision in the transition zone.

  17. Amyloid beta modulated the selectivity of heme-catalyzed protein tyrosine nitration: an alternative mechanism for selective protein nitration.

    Science.gov (United States)

    Yuan, Can; Li, Hailing; Gao, Zhonghong

    2012-10-01

    Protein tyrosine nitration is a post-translational modification associated with numerous pathological conditions. The biological consequences of this modification strongly depend on the site selectivity. Unfortunately, to date there is still no reliable model for predicting the selectivity of protein tyrosine nitration. Previously, we found that amyloid beta (Aβ) changed the selectivity of enolase tyrosine nitration upon binding to heme. It seemed that there was a link between the hydrophilicity of Aβ and the site-specific tyrosine nitration. We further investigated the role of the hydrophilicity of the molecules that bind to heme in the selectivity of protein tyrosine nitration. We found that Aβ(1-16), Aβ(1-20), and Aβ(1-40), upon binding to heme and interacting with glyceraldehyde-3-phosphate dehydrogenase (GAPDH) in a site-specific manner, differently modulated the site selectivity of heme-catalyzed GAPDH tyrosine nitration. The modulation is associated with the hydrophilicity of the Aβ peptides, which changed the surrounding environment of the heme. At the same time, the Aβ-heme complexes were found to be more effective at inactivating GAPDH than heme alone, and the selective tyrosine nitration that was catalyzed by Aβ-heme played an important role. These findings suggest an alternative mechanism for the selectivity of protein tyrosine nitration, which may lead to a better understanding of the factors that influence protein tyrosine nitration selectivity and the important roles of Aβ and heme in the pathogenesis of Alzheimer's disease, where Aβ accumulation and Aβ-dependent protein nitration play central roles.

  18. Bifunctional alkyl nitrates - trace constituents of the atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Kastler, J. [Department of Analytical and Environmental Chemistry, University of Ulm (Germany); Ballschmiter, K. [Center of Technology Assessment in Baden-Wuerttemberg, Stuttgart (Germany)

    1998-04-01

    Mono- and multifunctional esters of nitric acid (alkyl nitrates or organonitrates) form very complex mixtures of organic trace constituents in air. An analytical method was developed which combines selectivity in separation and detection in order to simplify this complexity in analytical terms. Mononitrates, dinitrates, keto nitrates, hydroxy nitrates of alkanes and alkenes, respecitvely, and bifunctional terpene nitrates were synthesized as reference substances. A specially developed new HPLC stationary phase (organonitrate phase) allows a group separation of mono-, di-, and hydroxy nitrates. After the HPLC preseparation the single components were finally separated by capillary HRGC-ECD and HRGC-MSD on polar and non-polar stationary phases. Mass spectrometric detection in the selected-ion-mode using the highly selective NO{sub 2}{sup +} fragment (m/z = 46 amu) led to very good selectivities for the nitric acid ester moiety. The analysis of a 100 m{sup 3} ambient air sample using this new analytical protocol allowed the identification of seven hydroxy nitrates and 24 dinitrates ranging from C2 to C7, 22 of them for the first time ever. (orig.) With 3 figs., 3 tabs., 20 refs.

  19. Waterproofing Materials for Ammonium Nitrate

    Directory of Open Access Journals (Sweden)

    R.S. Damse

    2004-10-01

    Full Text Available This study explores the possibility of overcoming the problem of hygroscopicity of ammonium nitrate by coating the particles with selected waterproofing materials. Gravimetric analysis ofthe samples of ammonium nitrate coated with eight different waterproofing materials, vis-a-vis, uncoated ammonium nitrate, were conducted at different relative humidity and exposuretime. The results indicate that mineral jelly is the promising waterproofing material for ammonium nitrate among the materials tested, viz, calcium stearate, dioctyl phthalate, kaoline, diethylphthalate, dinitrotoluene, shelac varnish, and beeswax. Attempts were made to confirm the waterproofing ability of mineral jelly to ammonium nitrate using differential thermal analysisand x-ray diffraction patterns as an experimental tool. Suitability of mineral jelly as an additive for the gun propellant was also assessed on the basis of theoretical calculations using THERMprogram.

  20. Factors influencing protein tyrosine nitration – structure-based predictive models

    Science.gov (United States)

    Bayden, Alexander S.; Yakovlev, Vasily A.; Graves, Paul R.; Mikkelsen, Ross B.; Kellogg, Glen E.

    2010-01-01

    Models for exploring tyrosine nitration in proteins have been created based on 3D structural features of 20 proteins for which high resolution X-ray crystallographic or NMR data are available and for which nitration of 35 total tyrosines has been experimentally proven under oxidative stress. Factors suggested in previous work to enhance nitration were examined with quantitative structural descriptors. The role of neighboring acidic and basic residues is complex: for the majority of tyrosines that are nitrated the distance to the heteroatom of the closest charged sidechain corresponds to the distance needed for suspected nitrating species to form hydrogen bond bridges between the tyrosine and that charged amino acid. This suggests that such bridges play a very important role in tyrosine nitration. Nitration is generally hindered for tyrosines that are buried and for those tyrosines where there is insufficient space for the nitro group. For in vitro nitration, closed environments with nearby heteroatoms or unsaturated centers that can stabilize radicals are somewhat favored. Four quantitative structure-based models, depending on the conditions of nitration, have been developed for predicting site-specific tyrosine nitration. The best model, relevant for both in vitro and in vivo cases predicts 30 of 35 tyrosine nitrations (positive predictive value) and has a sensitivity of 60/71 (11 false positives). PMID:21172423

  1. Nitration of Polystyrene-Part II Effect of Nitrating Medium on Nitration

    Directory of Open Access Journals (Sweden)

    I. Bajaj

    1968-04-01

    Full Text Available Polystyrene has been nitrated in mixtures of anhydrous nitric and sulphuric acid (70 : 30 and 80 : 20 by volume. Degree of substitution of nitro group per benzene ring varies from 1 to 2 depending on the time, temperature and composition of the nitrating media. Effect of polar and non polar solvents on nitration has been studied by nitrating the polymer in (i fuming nitric acid and (iimixture of nitric and sulphuric acid in presence of dimethyl formamide (DMF and carbon tetrachloride (CCI/Sub4. MF increase the rate of nitration in fuming nitric acid whereas the rate of nitration is lowered in the presence of DMF in the nitrating mixtures. In the case of CCI/Sub4, however, the effect is just the opposite to that observed in DMF. The results have been explained from the mechanism of the formation of 'nitroniumion,NO/Sub2+ in various nitrating media. Degradation of the polymer has been found to be comparatively less in the presence of the organic solvents used in the study.

  2. Complexity

    CERN Document Server

    Gershenson, Carlos

    2011-01-01

    The term complexity derives etymologically from the Latin plexus, which means interwoven. Intuitively, this implies that something complex is composed by elements that are difficult to separate. This difficulty arises from the relevant interactions that take place between components. This lack of separability is at odds with the classical scientific method - which has been used since the times of Galileo, Newton, Descartes, and Laplace - and has also influenced philosophy and engineering. In recent decades, the scientific study of complexity and complex systems has proposed a paradigm shift in science and philosophy, proposing novel methods that take into account relevant interactions.

  3. Variability of nitrate and phosphate

    Digital Repository Service at National Institute of Oceanography (India)

    Sardessai, S.; Sundar, D.

    Nitrate and phosphate are important elements of the biogeochemical system of an estuary. Observations carried out during the dry season April-May 2002, and March 2003 and wet season September 2002, show temporal and spatial variability of these two...

  4. Complex

    African Journals Online (AJOL)

    CLEMENT O BEWAJI

    Schiff bases and their complex compounds have been studied for their .... establishing coordination of the N–(2 – hydroxybenzyl) - L - α - valine Schiff base ..... (1967); “Spectrophotometric Identification of Organic Compounds”, Willey, New.

  5. Headspace Analysis of Ammonium Nitrate

    Science.gov (United States)

    2017-01-25

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6110--17-9709 Headspace Analysis of Ammonium Nitrate January 25, 2017 Approved for public...TELEPHONE NUMBER (include area code) b. ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Headspace Analysis of Ammonium Nitrate G...isobutane reagent ion from analysis of ammonia desorbed from packed tungsten oxide sampling tube .................. 18 E-1 Executive Summary The

  6. 21 CFR 172.170 - Sodium nitrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium nitrate. 172.170 Section 172.170 Food and... Preservatives § 172.170 Sodium nitrate. The food additive sodium nitrate may be safely used in or on specified... sablefish, smoked, cured salmon, and smoked, cured shad, so that the level of sodium nitrate does not...

  7. Characterizing sources of nitrate leaching from an irrigated dairy farm in Merced County, California

    NARCIS (Netherlands)

    Schans, van der M.L.; Harter, T.; Leijnse, A.; Mathews, M.C.; Meyer, R.D.

    2009-01-01

    Dairy farms comprise a complex landscape of groundwater pollution sources. The objective of our work is to develop a method to quantify nitrate leaching to shallow groundwater from different management units at dairy farms. Total nitrate loads are determined by the sequential calibration of a sub-re

  8. Nitrate transport and signalling.

    Science.gov (United States)

    Miller, Anthony J; Fan, Xiaorong; Orsel, Mathilde; Smith, Susan J; Wells, Darren M

    2007-01-01

    Physiological measurements of nitrate (NO(3)(-)) uptake by roots have defined two systems of high and low affinity uptake. In Arabidopsis, genes encoding both of these two uptake systems have been identified. Most is known about the high affinity transport system (HATS) and its regulation and yet measurements of soil NO(3)(-) show that it is more often available in the low affinity range above 1 mM concentration. Several different regulatory mechanisms have been identified for AtNRT2.1, one of the membrane transporters encoding HATS; these include feedback regulation of expression, a second component protein requirement for membrane targeting and phosphorylation, possibly leading to degradation of the protein. These various changes in the protein may be important for a second function in sensing NO(3)(-) availability at the surface of the root. Another transporter protein, AtNRT1.1 also has a role in NO(3)(-) sensing that, like AtNRT2.1, is independent of their transport function. From the range of concentrations present in the soil it is proposed that the NO(3)(-)-inducible part of HATS functions chiefly as a sensor for root NO(3)(-) availability. Two other key NO(3)(-) transport steps for efficient nitrogen use by crops, efflux across membranes and vacuolar storage and remobilization, are discussed. Genes encoding vacuolar transporters have been isolated and these are important for manipulating storage pools in crops, but the efflux system is yet to be identified. Consideration is given to how well our molecular and physiological knowledge can be integrated as well to some key questions and opportunities for the future.

  9. Water rotational jump driven large amplitude molecular motions of nitrate ions in aqueous potassium nitrate solution

    CERN Document Server

    Banerjee, Puja; Bagchi, Biman

    2016-01-01

    Molecular dynamics simulations of aqueous potassium nitrate solution reveal a highly complex rotational dynamics of nitrate ions where, superimposed on the expected continuous Brownian motion, are large amplitude angular jumps that are coupled to and at least partly driven by similar large amplitude jump motions in water molecules which are associated with change in the hydrogen bonded water molecule. These jumps contribute significantly to rotational and translational motions of these ions. We explore the detailed mechanism of these correlated (or, coupled) jumps and introduce a new time correlation function to decompose the coupled orientational- jump dynamics of solvent and solute in the aqueous electrolytic solution. Time correlation function provides for the unequivocal determination of the time constant involved in orientational dynamics originating from making and breaking of hydrogen bonds. We discover two distinct mechanisms-both are coupled to density fluctuation but are of different types.

  10. Thermodynamic and Spectroscopic Studies of Lanthanides(III) Complexation with Polyamines in Dimethyl Sulfoxide

    Energy Technology Data Exchange (ETDEWEB)

    Di Bernardo, Plinio [Univ. of Padova (Italy); Zanonato, Pier Luigi [Univ. of Padova (Italy); Melchior, Andrea [Univ. of Udine (Italy); Portanova, Roberto [Univ. of Udine (Italy); Tolazzi, Marilena [Univ. of Udine (Italy); Choppin, Gregory R. [Florida State Univ., Tallahassee, FL (United States); Wang, Zheming [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2008-01-01

    The thermodynamic parameters of complexation of Ln(III) cations with tris(2-aminoethyl)amine (tren) and tetraethylenepentamine (tetren) were determined in dimethyl sulfoxide (DMSO) by potentiometry and calorimetry. The excitation and emission spectra and luminescence decay constants of Eu3+ and Tb3+ complexed by tren and tetren, as well as those of the same lanthanides(III) complexed with diethylenetriamine (dien) and triethylenetetramine (trien), were also obtained in the same solvent. The combination of thermodynamic and spectroscopic data showed that, in the 1:1 complexes, all nitrogens of the ligands bound to the lanthanides except in the case of tren, in which only pendant N bound. For the larger ligands (trien, tren, tetren) in the higher complexes (ML2), there was less complete binding by available donors, presumably due to steric crowding. FT-IR studies were carried out in an acetonitrile/DMSO mixture, suitably chosen in order to follow the changes in the primary solvation sphere of lanthanide(III) due to complexation of amine ligands. Results show that the mean number of molecules of DMSO removed from the inner coordination sphere of lanthanides(III) is lower than ligand denticity and that the coordination number of the metal ions increases with amine complexation from ~8 to ~10. Independently of the number and structure of the amines, linear trends, similar for all lanthanides, were obtained by plotting the values of ΔGj°, ΔHj° and TΔSj° for the complexation of ethylenediamine (en), dien, trien, tren and tetren as a function of the number of amine metal-coordinated nitrogen atoms. The main factors on which the thermodynamic functions of lanthanide(III) complexation reactions in DMSO depend are discussed.

  11. Assessment of changes in riverine nitrate in the Sesan, Srepok and Sekong tributaries of the Lower Mekong River Basin

    Directory of Open Access Journals (Sweden)

    Chantha Oeurng

    2016-12-01

    Full Text Available Changes in nitrates are of particular concern in tropical regions undergoing rapid development, as these changes may affect local and downstream riverine ecosystems. This study assessed the spatial and temporal differences in nitrate loads within the Sesan, Srepok, and Sekong (3S Rivers, the largest tributaries of the Mekong River. Simulation results from a flow and nitrate calibrated SWAT model show large differences in year-to-year nitrate loads, a strong seasonality, and clear variability patterns in monthly nitrate loads in the 3S outlet during the wet season. The annual total nitrate loading from the 3S Rivers account for approximately 30% of the total nitrate load of the Mekong River at Pakse. Nitrate loads during the rainy season accounts for 79% of the total annual load into the Mekong River. The Sesan, Sekong, and Srepok basins have average nitrate yields of 400, 330, and 290 kg N/km2, respectively, which is comparable with other forested catchments, but much lower than agriculture dominated catchments in the tropics. Simulations of three future climate scenarios show little variability in annual nitrate loadings under current land use/land cover (LULC, but seasonal difference in nitrate loading during rainy months was observed. Further research is needed to estimate nitrate loads in the 3S basin as influenced by LULC change and dam development, which may potentially result in complex changes to local and downstream riverine ecosystems.

  12. Revealing and tuning the core, structure, properties and function of polymer micelles with lanthanide-coordination complexes.

    Science.gov (United States)

    Wang, Junyou; Groeneveld, Andrea; Oikonomou, Maria; Prusova, Alena; Van As, Henk; van Lent, Jan W M; Velders, Aldrik H

    2016-01-07

    Controlling self-assembly processes is of great interest in various fields where multifunctional and tunable materials are designed. We here present the versatility of lanthanide-complex-based micelles (Ln-C3Ms) with tunable coordination structures and corresponding functions (e.g. luminescence and magnetic relaxation enhancement). Micelles are prepared by charge-driven self-assembly of a polycationic-neutral diblock copolymer and anionic coordination complexes formed by Ln(III) ions and the bis-ligand L2EO4, which contains two dipicolinic acid (DPA) ligand groups (L) connected by a tetra-ethylene oxide spacer (EO4). By varying the DPA/Ln ratio, micelles are obtained with similar size but with different stability, different aggregation numbers and different oligomeric and polymeric lanthanide(III) coordination structures in the core. Electron microscopy, light scattering, luminescence spectroscopy and magnetic resonance relaxation experiments provide an unprecedented detailed insight into the core structures of such micelles. Concomitantly, the self-assembly is controlled such that tunable luminescence or magnetic relaxation with Eu-C3Ms, respectively, Gd-C3Ms is achieved, showing potential for applications, e.g. as contrast agents in (pre)clinical imaging. Considering the various lanthanide(III) ions have unique electron configurations with specific physical chemical properties, yet very similar coordination chemistry, the generality of the current coordination-structure based micellar design shows great promise for development of new materials such as, e.g., hypermodal agents.

  13. Iron(III) complexes of 2-(1H-benzo[d]imidazol-2-yl)phenol and acetate or nitrate as catalysts for epoxidation of olefins with hydrogen peroxide

    Science.gov (United States)

    Dutta, Amit Kumar; Samanta, Suvendu; Dutta, Supriya; Lucas, C. Robert; Dawe, Louise N.; Biswas, Papu; Adhikary, Bibhutosh

    2016-07-01

    Cheap and environmentally friendly Fe(III) catalysts [Fe(L)2(CH3COO)] (1) and [Fe(L)2(NO3)]·2CH3OH (2) where HL = 2-(1H-benzo[d]imidazol-2-yl)phenol for epoxidation of olefins have been developed. The catalysts have been characterized by elemental analyses, IR, UV-Vis spectroscopy and by X-ray crystallography. The X-ray structures reveal mononuclear compounds having a bidentate acetate or nitrate in 1 and 2, respectively. Catalytic epoxidations of styrene and cyclohexene have been carried out homogeneously by using 30% aqueous hydrogen peroxide in acetonitrile in the presence of catalytic amounts of 1 or 2. Yields of the respective epoxides were fair (1) to good (2) and selectivities were good in all cases although 2 produced two to three times the yield, depending on the substrate, than 1 and higher selectivity as well. A hypothesis for these differences in catalytic efficacy between 1 and 2 that is consistent with mechanistic details of related enzymatic and biomimetic model systems is proposed. Herein we report [Fe(L)2(NO3)]·2CH3OH (2) as the first structurally characterized non-heme iron epoxidation catalyst with a bidentate nitrate ligand.

  14. Quantification of naphazoline nitrate by UV-spectrophoto-metry

    Directory of Open Access Journals (Sweden)

    O. I. Panasenko

    2013-12-01

    Full Text Available One of the main tasks of pharmaceutical chemistry – medical drugs study. Spectrophotometry is widely used in studying of the structure and composition (complexes, dyes, analytical reagents, etc. of various compounds. It widely used for qualitative and quantitative determination of substances (determination of elements traces in metals, alloys, technical facilities. The dependence between substance structure and its electronic spectrum is being studied by many researchers till nowadays. The aim of this work was to highlight the issues of naphazoline quantify definition techniques by the UV-spectrophotometry. According to the existing methods of quality control (MQC, naphazoline nitrate is a substance quantitatively determined by acid-base titration among a mixture of anhydrous acetic acid and acetic anhydride. Titration is carried out with a solution of 0,1 M perchloric acid (indicator - crystal violet. To check the quality of nasal drops nafazoline nitrate MQC is recommended UV-spectrophotometry: drug is dissolved in boric acid solution (20 g/l as the reference solution used solution pharmacopoeia standard sample substance nafazoline nitrate. The character of UV-spectra of the nafazoline nitrate in solvents of different polarity (water, 95% ethanol, 0,1 M NaOH, 0,1 M HCl, 5M H2SO4, was defined and studied. Standard sample of nafazoline nitrate was obtained from the State Enterprise "Scientific and Expert Pharmacopoeia Centre Ukraine". In order to study UV-spectra nafazoline nitrate spectrophotometer SPECORD 200-222U214 (Germany was used. UV-spectrum of nafazoline nitrate in water and 95% ethanol are characterized by two maxima at 270 and 280 nm. Absorption band of nafazoline nitrate in 0, 1 M sodium hydroxide has two maxima at 271 and 280 nm, and in 0, 1 M solution of hydrochloric acid and 5 M solution of sulfuric acid maxima coincide with the maxima spectrum of the drug in water, 95% ethanol. In order to avoid errors associated with

  15. Selectivity of the highly preorganized tetradentate ligand 2,9-di(pyrid-2-yl)-1,10-phenanthroline for metal ions in aqueous solution, including lanthanide(III) ions and the uranyl(VI) cation.

    Science.gov (United States)

    Carolan, Ashley N; Cockrell, Gregory M; Williams, Neil J; Zhang, Gang; VanDerveer, Donald G; Lee, Hee-Seung; Thummel, Randolph P; Hancock, Robert D

    2013-01-01

    Some metal ion complexing properties of DPP (2,9-Di(pyrid-2-yl)-1,10-phenanthroline) are reported with a variety of Ln(III) (Lanthanide(III)) ions and alkali earth metal ions, as well as the uranyl(VI) cation. The intense π-π* transitions in the absorption spectra of aqueous solutions of 10(-5) M DPP were monitored as a function of pH and metal ion concentration to determine formation constants of the alkali-earth metal ions and Ln(III) (Ln = lanthanide) ions. It was found that log K(1)(DPP) for the Ln(III) ions has a peak at Ln(III) = Sm(III) in a plot of log K(1) versus 1/r(+) (r(+) = ionic radius for 8-coordination). For Ln(III) ions larger than Sm(III), there is a steady rise in log K(1) from La(III) to Sm(III), while for Ln(III) ions smaller than Sm(III), log K(1) decreases slightly to the smallest Ln(III) ion, Lu(III). This pattern of variation of log K(1) with varying size of Ln(III) ion was analyzed using MM (molecular mechanics) and DFT (density functional theory) calculations. Values of strain energy (∑U) were calculated for the [Ln(DPP)(H(2)O)(5)](3+) and [Ln(qpy)(H(2)O)(5)](3+) (qpy = quaterpyrdine) complexes of all the Ln(III) ions. The ideal M-N bond lengths used for the Ln(III) ions were the average of those found in the CSD (Cambridge Structural Database) for the complexes of each of the Ln(III) ions with polypyridyl ligands. Similarly, the ideal M-O bond lengths were those for complexes of the Ln(III) ions with coordinated aqua ligands in the CSD. The MM calculations suggested that in a plot of ∑U versus ideal M-N length, a minimum in ∑U occurred at Pm(III), adjacent in the series to Sm(III). The significance of this result is that (1) MM calculations suggest that a similar metal ion size preference will occur for all polypyridyl-type ligands, including those containing triazine groups, that are being developed as solvent extractants in the separation of Am(III) and Ln(III) ions in the treatment of nuclear waste, and (2) Am(III) is very

  16. Lanthanide-isophthalate cavity frameworks encapsulated copper(I) complexes

    Science.gov (United States)

    Zhou, Youfu; Yuan, Daqiang; Jiang, Feilong; Xu, Yanqing; Hong, Maochun

    2006-08-01

    The hydrothermal reactions of Ln 2O 3, [Cu(2,2'-bpy) 2](ClO 4) and isophthalic acid (H 2ip) yielded a series of heterometallic coordination frameworks with the empirical formula [{Ln 4(ip) 7(H 2O) 2}{Cu(bpy) 2} 2] n [Ln=Nd ( 1), Sm ( 2), Eu ( 3)]. Single-crystal X-ray diffraction analyses reveal that they are isostructural and possess a 3D cavity framework with two complex cations [Cu(2,2'-bpy) 2] + encapsulated in each cavity. TGA curve shows that they are highly thermally stable. Magnetic studies illustrate weakly antiferromagnetic exchange interactions between lanthanide(III) ions at room temperature in 1- 3. Compound 2 has interesting photoluminescent property owing to the coexistence of host and guest photoluminescent units.

  17. Evaluation of the nitrate content in leaf vegetables produced through different agricultural systems.

    Science.gov (United States)

    Guadagnin, S G; Rath, S; Reyes, F G R

    2005-12-01

    The nitrate content of leafy vegetables (watercress, lettuce and arugula) produced by different agricultural systems (conventional, organic and hydroponic) was determined. The daily nitrate intake from the consumption of these crop species by the average Brazilian consumer was also estimated. Sampling was carried out between June 2001 to February 2003 in Campinas, São Paulo State, Brazil. Nitrate was extracted from the samples using the procedure recommended by the AOAC. Flow injection analysis with spectrophotometric detection at 460 nm was used for nitrate determination through the ternary complex FeSCNNO+. For lettuce and arugula, the average nitrate content varied (p < 0.05) between the three agricultural systems with the nitrate level in the crops produced by the organic system being lower than in the conventional system that, in turn, was lower than in the hydroponic system. For watercress, no difference (p < 0.05) was found between the organic and hydroponic samples, both having higher nitrate contents (p < 0.05) than conventionally cultivated samples. The nitrate content for each crop species varied among producers, between different parts of the plant and in relation to the season. The estimated daily nitrate intake, calculated from the consumption of the crops produced by the hydroponic system, represented 29% of the acceptable daily intake established for this ion.

  18. Sensitive Immunoassays of Nitrated Fibrinogen in Human Biofluids

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Zhiwen; Wu, Hong; Du, Dan; Wang, Jun; Wang, Hua; Qian, Weijun; Bigelow, Diana J.; Pounds, Joel G.; Smith, Richard D.; Lin, Yuehe

    2010-05-05

    Three new sandwich immunoassays for detection of nitrated biomarker have been established with potential applications in biomedical studies and clinical practice. In this study, nitrated human fibrinogen, a potential oxidative stress biomarker for several pathologies, was chosen as the target. To improve the sensitivity and overcome the interference caused by the complexity of human biofluids, we developed three sandwich strategies using various combinations of primary antibody and secondary antibody. All three strategies demonstrated high sensitivity and selectivity towards nitrated forms of fibrinogen in buffer, but their performances were dramatically reduced when tested with human plasma and serum samples. Systematically optimizations were carried out to investigate the effects of numerous factors, including sampling, coating, blocking, and immunoreactions. Our final optimization results indicate that two of these strategies retain sufficient sensitivity and selectivity for use as assays in human physiological samples. Specifically, detection limits reached the pM level and the linear response ranges were up to nM level with a correlation coefficient > 0.99. To our best knowledge, this is the first example of using an electrochemical immunoassay for a nitrated biomarker in a physiological fluid. This novel approach provides a rapid, sensitive, selective, cost efficient and robust bioassay for detection of oxidative stress in pathology and for clinical applications. Moreover, the sandwich strategies developed in this paper can be readily used to establish effective methods targeting other nitration biomarkers.

  19. Intracellular Nitrate of Marine Diatoms as a Driver of Anaerobic Nitrogen Cycling in Sinking Aggregates

    Directory of Open Access Journals (Sweden)

    Anja Kamp

    2016-11-01

    Full Text Available Diatom-bacteria aggregates are key for the vertical transport of organic carbon in the ocean. Sinking aggregates also represent pelagic microniches with intensified microbial activity, oxygen depletion in the center, and anaerobic nitrogen cycling. Since some of the aggregate-forming diatom species store nitrate intracellularly, we explored the fate of intracellular nitrate and its availability for microbial metabolism within anoxic diatom-bacteria aggregates. The ubiquitous nitrate-storing diatom Skeletonema marinoi was studied as both axenic cultures and laboratory-produced diatom-bacteria aggregates. Stable 15N isotope incubations under dark and anoxic conditions revealed that axenic S. marinoi is able to reduce intracellular nitrate to ammonium that is immediately excreted by the cells. When exposed to a light:dark cycle and oxic conditions, S. marinoi stored nitrate intracellularly in concentrations > 60 mmol L-1 both as free-living cells and associated to aggregates. Intracellular nitrate concentrations exceeded extracellular concentrations by three orders of magnitude. Intracellular nitrate was used up within 2-3 days after shifting diatom-bacteria aggregates to dark and anoxic conditions. Thirty-one percent of the diatom-derived nitrate was converted to nitrogen gas, indicating that a substantial fraction of the intracellular nitrate pool of S. marinoi becomes available to the aggregate-associated bacterial community. Only 5% of the intracellular nitrate was reduced to ammonium, while 59% was recovered as nitrite. Hence, aggregate-associated diatoms accumulate nitrate from the surrounding water and sustain complex nitrogen transformations, including loss of fixed nitrogen, in anoxic, pelagic microniches. Additionally, it may be expected that intracellular nitrate not converted before the aggregates have settled onto the seafloor could fuel benthic nitrogen transformations.

  20. Short-term effects of a high nitrate diet on nitrate metabolism in healthy individuals.

    Science.gov (United States)

    Bondonno, Catherine P; Liu, Alex H; Croft, Kevin D; Ward, Natalie C; Puddey, Ian B; Woodman, Richard J; Hodgson, Jonathan M

    2015-03-12

    Dietary nitrate, through the enterosalivary nitrate-nitrite-NO pathway, can improve blood pressure and arterial stiffness. How long systemic nitrate and nitrite remain elevated following cessation of high nitrate intake is unknown. In 19 healthy men and women, the time for salivary and plasma nitrate and nitrite to return to baseline after 7 days increased nitrate intake from green leafy vegetables was determined. Salivary and plasma nitrate and nitrite was measured at baseline [D0], end of high nitrate diet [D7], day 9 [+2D], day 14 [+7D] and day 21 [+14D]. Urinary nitrite and nitrate was assessed at D7 and +14D. Increased dietary nitrate for 7 days resulted in a more than fourfold increase in saliva and plasma nitrate and nitrite (p nitrate had returned to baseline while saliva nitrate and nitrite were more than 1.5 times higher than at baseline levels. By [+7D] all metabolites had returned to baseline levels. The pattern of response was similar between men and women. Urinary nitrate and nitrate was sevenfold higher at D7 compared to +14D. These results suggest that daily ingestion of nitrate may be required to maintain the physiological changes associated with high nitrate intake.

  1. Nitrations Conference Held at Menlo Park, California on 27-29 July 1983.

    Science.gov (United States)

    1983-09-01

    superacids can also be used in conjunction with fuming or concentrated nitric acids under conditions of azeotropic removal of water . When the Nafion-H...substrate selectivity of polyether complexed NO2BF4, a tenfold excess of a 1:1 mixture of benzene and toluene was nitrated with the soluble crown... mixtures at room temperature with these complexed nitronium ions nitrated toluene 2-44 times faster than benzene compared to 1.7 times with uncomplexed

  2. Efficiency of nitrate uptake in spinach : impact of external nitrate concentration and relative growth rate on nitrate influx and efflux

    NARCIS (Netherlands)

    Ter Steege, MW; Stulen, [No Value; Wiersema, PK; Posthumus, F; Vaalburg, W

    1999-01-01

    Regulation of nitrate influx and efflux in spinach (Spinacia oleracea L., cv. Subito), was studied in short-term label experiments with N-13- and N-15-nitrate. Nitrate fluxes were examined in relation to the N demand for growth, defined as relative growth rate (RGR) times plant N concentration. Plan

  3. Metal nitrate conversion method, patent application

    NARCIS (Netherlands)

    2008-01-01

    A method for converting a supported metal nitrate into the corresponding supported metal comprises heating the metal nitrate to effect its decomposition under a gas mixture that contains nitric oxide and has an oxygen content of

  4. 76 FR 62311 - Ammonium Nitrate Security Program

    Science.gov (United States)

    2011-10-07

    ... to best notify agents (AN Agents) when ammonium nitrate purchasers (AN Purchasers) submit those AN... directly to ammonium nitrate sellers (AN Sellers) when it is not possible for an AN Seller to verify the...

  5. {gamma}-radiolysis of uranous nitrate solutions

    Energy Technology Data Exchange (ETDEWEB)

    Bisel, Isabelle; Lebouille, Odile; Rossetti, Thomas [CEA ValRHo - BP 17171 - 30207 Bagnols sur Ceze (France)

    2008-07-01

    Full text of publication follows: The knowledge of uranous nitrate solutions stability under radiolysis effect is of interest for all the processes aiming its co-conversion into a solid form with other actinides. In the presence of hydrazine, the oxidation of U(IV) to U(VI) under {gamma}-radiolysis ({sup 137}Cs) is due to the reaction with water radiolysis products, mainly hydrogen peroxide. Its kinetic law is of order 0. In addition, the zero order hydrazine consumption reaction, leads to the accumulation of hydrazoic acid related to its oxidation by nitrous acid himself generated by the radiolysis of the nitric acid. Lastly, the increase of acidity of the solution with a stoichiometry of 1.5 compared to uranium indicates multiple reactions. In absence of hydrazine, uranous nitrate is very quickly oxidized by the nitric and solutions acidity increases according to a complex mechanism catalysed by the nitrous acid. Results are not found to be sensitive to dose rate between 10 and 300 Gy/min. (authors)

  6. Nitrate Removal from Ground Water: A Review

    OpenAIRE

    Archna *; Surinder K. Sharma; Ranbir Chander Sobti

    2012-01-01

    Nitrate contamination of ground water resources has increased in Asia, Europe, United States, and various other parts of the world. This trend has raised concern as nitrates cause methemoglobinemia and cancer. Several treatment processes can remove nitrates from water with varying degrees of efficiency, cost, and ease of operation. Available technical data, experience, and economics indicate that biological denitrification is more acceptable for nitrate removal than reverse osmosis and ion ex...

  7. FTIR spectroscopy combined with quantum chemical calculations to investigate adsorbed nitrate on aluminium oxide surfaces in the presence and absence of co-adsorbed water.

    Science.gov (United States)

    Baltrusaitis, Jonas; Schuttlefield, Jennifer; Jensen, Jan H; Grassian, Vicki H

    2007-09-28

    Surface reactions of nitrogen oxides with aluminium oxide particles result in the formation of adsorbed nitrate. Specifically, when alpha-Al(2)O(3) and gamma-Al(2)O(3) particles are exposed to gas-phase NO(2) and HNO(3) adsorbed nitrate forms on the surface. In this study, Fourier transform infrared (FTIR) spectroscopy is combined with quantum chemical calculations to further our understanding of the adsorbed nitrate product on aluminium oxide particle surfaces in the presence and absence of co-adsorbed water at 296 K. FTIR spectra of adsorbed nitrate on alpha-Al(2)O(3) and gamma-Al(2)O(3) particles are interpreted using calculated vibrational frequencies of nitrate coordinated to binuclear Al oxide cluster models. Comparison of the calculated and experimental vibrational frequencies of adsorbed nitrate establishes different modes of coordination (monodentate, bidentate and bridging) of the nitrate ion to the surface in the absence of adsorbed water. In the presence of co-adsorbed water, the nitrate ion becomes fully solvated, as shown by a comparison of the experimental nitrate infrared spectra as a function of relative humidity with the calculated nitrate vibrational frequencies for binuclear Al cluster compounds which contain both coordinated nitrate ions and water molecules. These calculations also suggest that adsorbed water can displace nitrate from direct coordination to the surface, leading to an outer-sphere nitrate adsorption complex as well as an inner-sphere complex. Furthermore, the relative humidity dependence of the spectra suggest that water does not evenly wet the surface even at high relative humidity, as there are open or bare surface sites where nitrate ions are not solvated. Besides adsorbed mondendate, bidendate, bridging and solvated nitrate, the presence of ion bound nitrate ion, partially solvated nitrate, molecular nitric acid, hydronium ion and H(3)O(+):NO(3)(-) ion pairs on the oxide surface are also discussed.

  8. 49 CFR 176.410 - Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures. 176.410 Section 176.410 Transportation Other Regulations Relating to... nitrate and ammonium nitrate mixtures. (a) This section prescribes requirements to be observed...

  9. Nitrate tolerance impairs nitric oxide-mediated vasodilation in vivo

    DEFF Research Database (Denmark)

    Laursen, Jørn Bech; Boesgaard, Søren; Poulsen, Henrik E.;

    1996-01-01

    Nitrates, Nitrate tolerence, Nitric oxide, acetylcholine, N-acetylcholine, N-acetylcysteine, L-NAME, Rat, Anesthetized......Nitrates, Nitrate tolerence, Nitric oxide, acetylcholine, N-acetylcholine, N-acetylcysteine, L-NAME, Rat, Anesthetized...

  10. Nitration of Naphthol: A Laboratory Experiment.

    Science.gov (United States)

    Mowery, Dwight F.

    1982-01-01

    Products of nitrations, upon distillation or steam distillation, may produce dermatitis in some students. A procedure for nitration of beta-naphthol producing a relatively non-volatile product not purified by steam distillation is described. Nitration of alpha-naphthol by the same procedure yields Martius Yellow dye which dyes wool yellow or…

  11. 76 FR 11273 - Ammonium Nitrate From Russia

    Science.gov (United States)

    2011-03-01

    ... COMMISSION Ammonium Nitrate From Russia AGENCY: United States International Trade Commission. ACTION: Institution of a five-year review concerning the suspended investigation on ammonium nitrate from Russia... investigation on ammonium nitrate from Russia would be likely to lead to continuation or recurrence of...

  12. 76 FR 47238 - Ammonium Nitrate From Russia

    Science.gov (United States)

    2011-08-04

    ... COMMISSION Ammonium Nitrate From Russia Determination On the basis of the record \\1\\ developed in the subject... order on ammonium nitrate from Russia would be likely to lead to continuation or recurrence of material... Commission are contained in USITC Publication 4249 (August 2011), entitled Ammonium Nitrate from...

  13. 21 CFR 172.160 - Potassium nitrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Potassium nitrate. 172.160 Section 172.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Preservatives § 172.160 Potassium nitrate. The food additive potassium nitrate may be safely used as a...

  14. Nitration of soluble proteins in organotypic culture models of Parkinson's disease

    DEFF Research Database (Denmark)

    Larsen, Trine R; Söderling, Ann-Sofi; Caidahl, Kenneth

    2008-01-01

    Protein nitration due to oxidative and nitrative stress has been linked to the pathogenesis of Parkinson's disease (PD), but its relationship to the loss of dopamine (DA) or tyrosine hydroxylase (TH) activity is not clear. Here we quantified protein-bound 3-nitrotyrosine (3-NT) by a novel gas...... toxin 1-methyl-4-phenylpyridinium (MPP(+)) or the lipophilic complex I inhibitor rotenone. Incubation with SIN-1 (24h) or MPP(+) treatments (48h) caused dose-dependent protein nitration reaching a maximum of eightfold increase by 10mM SIN-1 or twofold by 10muM MPP(+), but significant DA depletions...... occurred at much lower concentrations of MPP(+) (1muM). Chronic MPP(+) or rotenone treatments (3 weeks) caused maximum protein nitration by 1muM (twofold) or 10nM (fourfold), respectively. Co-treatment with the nitric oxide synthase inhibitor l-NAME (300muM) prevented protein nitration by MPP(+), but did...

  15. Negative feedback loops leading to nitrate homeostasis and oscillatory nitrate assimilation in plants and fungi.

    OpenAIRE

    Huang, Yongshun

    2011-01-01

    Nitrate is an important nutrient for plants and fungi. For plants it has been shown that cytosolic nitrate levels are under homeostatic control. Here we describe two networks that can obtain robust, i.e. perturbation independent, homeostatic behavior in cytosolic nitrate concentration. One of the networks, a member in the family of outflow controllers, is based on a negative feedback loop containing a nitrate-induced activation of a controller molecule which removes nitrate. In plants this co...

  16. Continuous flow nitration in miniaturized devices.

    Science.gov (United States)

    Kulkarni, Amol A

    2014-01-01

    This review highlights the state of the art in the field of continuous flow nitration with miniaturized devices. Although nitration has been one of the oldest and most important unit reactions, the advent of miniaturized devices has paved the way for new opportunities to reconsider the conventional approach for exothermic and selectivity sensitive nitration reactions. Four different approaches to flow nitration with microreactors are presented herein and discussed in view of their advantages, limitations and applicability of the information towards scale-up. Selected recent patents that disclose scale-up methodologies for continuous flow nitration are also briefly reviewed.

  17. Continuous flow nitration in miniaturized devices

    Directory of Open Access Journals (Sweden)

    Amol A. Kulkarni

    2014-02-01

    Full Text Available This review highlights the state of the art in the field of continuous flow nitration with miniaturized devices. Although nitration has been one of the oldest and most important unit reactions, the advent of miniaturized devices has paved the way for new opportunities to reconsider the conventional approach for exothermic and selectivity sensitive nitration reactions. Four different approaches to flow nitration with microreactors are presented herein and discussed in view of their advantages, limitations and applicability of the information towards scale-up. Selected recent patents that disclose scale-up methodologies for continuous flow nitration are also briefly reviewed.

  18. A novel targeted proteomics method for identification and relative quantitation of difference in nitration degree of OGDH between healthy and diabetic mouse.

    Science.gov (United States)

    Yu, Qing; Liu, Bin; Ruan, Dandan; Niu, Chao; Shen, Jiayi; Ni, Maowei; Cong, Weitao; Lu, Xianghong; Jin, Litai

    2014-11-01

    For analysis of nitration modification of α oxoglutarate dehydrogenase (α-OGDH) induced by diabetes, a targeted proteomics strategy was developed through the use of Skyline. All peptides containing Y and W of the target proteins were nitrated in silico and output to produce parallel reaction monitoring (PRM) or SRM method for nitration analysis. A nitrated casein mixture was used as standard protein to assess the feasibility of this method. The results demonstrated the availability of this strategy for nitration identification, and subsequently this method was used to analyze the nitration of α-OGDH from myocardial tissue extracts of diabetic mouse. The PRM method was primarily generated by Skyline for identification of the actual nitrated peptides from all possible nitrated peptides of α-OGDH due to the complexity of α-OGDH. The PRM-based data were analyzed by SEQUEST, and transitions of the identified nitrated peptides were used to develop an SRM method for relative quantitation of nitration degree. The nitration degree of α-OGDH for diabetic mouse is higher than that for control mouse, indicating that α-OGDH of the diabetic mouse suffered from more intense oxidative damage. We believe that this approach for obtaining information regarding nitration will facilitate the study of other PTMs in complex mixtures. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Transition Metal Carbohydrazide Nitrates: Burn-rate Modifiers for Propellants

    Directory of Open Access Journals (Sweden)

    S. H. Sonawane

    2006-07-01

    Full Text Available This paper discusses the synthesis and characterisation of cobalt (Co, nickel (Ni andcopper (Cu carbohydrazide nitrates. In differential scanning calorimetry (DSC, the complexesexhibited exothermic decomposition indicating their energetic nature. The commencement ofdecomposition was observed at 220 °C for Ni complex, and at 160 °C for Co complex whereasthat of Cu complex occurred at 75 °C. In view of the better thermal stability, Ni and Co complexeswere selected for further study. The activation energy of decomposition of Ni and Co complexeswere found to be 47 kcal/mol and 60 kcal/mol respectively. Impact and friction sensitivity testresults revealed relatively lower vulnerability of carbohydrazide cobalt nitrate. Its incorporationin an ammonium perchlorate (AP-based composite propellant led to 9-19 per cent enhancementwhereas that of carbohydrazide nickel nitrate resulted in 28-74 per cent enhancement in burningrates in the pressure range 1.9 MPa to 8.8 MPa. Exothermic decomposition of the coordinationcomplexes on propellant surface and involvement of metal at molecular level formed ondecomposition of the complexes in combustion environment of composite propellant may beattributed to the catalytic effect of this class of compounds on the lines of reported literature.

  20. Phase diagram of ammonium nitrate

    Science.gov (United States)

    Dunuwille, M.; Yoo, C. S.

    2014-05-01

    Ammonium Nitrate (AN) has often subjected to uses in improvised explosive devices, due to its wide availability as a fertilizer and its capability of becoming explosive with slight additions of organic and inorganic compounds. Yet, the origin of enhanced energetic properties of impure AN (or AN mixtures) is neither chemically unique nor well understood -resulting in rather catastrophic disasters in the past1 and thereby a significant burden on safety in using ammonium nitrates even today. To remedy this situation, we have carried out an extensive study to investigate the phase stability of AN at high pressure and temperature, using diamond anvil cells and micro-Raman spectroscopy. The present results confirm the recently proposed phase IV-to-IV' transition above 17 GPa2 and provide new constraints for the melting and phase diagram of AN to 40 GPa and 400 °C.

  1. 49 CFR 176.415 - Permit requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers.

    Science.gov (United States)

    2010-10-01

    ... nitrates, and certain ammonium nitrate fertilizers. 176.415 Section 176.415 Transportation Other... requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers. (a) Except as... Captain of the Port (COTP). (1) Ammonium nitrate UN1942, ammonium nitrate fertilizers containing more...

  2. Relationship Between Urinary Nitrate Excretion and Blood Pressure in the InChianti Cohort.

    Science.gov (United States)

    Smallwood, Miranda J; Ble, Alessandro; Melzer, David; Winyard, Paul G; Benjamin, Nigel; Shore, Angela C; Gilchrist, Mark

    2017-07-01

    Inorganic nitrate from the oxidation of endogenously synthesized nitric oxide (NO) or consumed in the diet can be reduced to NO via a complex enterosalivary circulation pathway. The relationship between total nitrate exposure by measured urinary nitrate excretion and blood pressure in a large population sample has not been assessed previously. For this cross-sectional study, 24-hour urinary nitrate excretion was measured by spectrophotometry in the 919 participants from the InChianti cohort at baseline and blood pressure measured with a mercury sphygmomanometer. After adjusting for age and sex only, diastolic blood pressure was 1.9 mm Hg lower in subjects with ≥2 mmol urinary nitrate excretion compared with those excreting <1 mmol nitrate in 24 hours: systolic blood pressure was 3.4 mm Hg (95% confidence interval (CI): -3.5 to -0.4) lower in subjects for the same comparison. Effect sizes in fully adjusted models (for age, sex, potassium intake, use of antihypertensive medications, diabetes, HS-CRP, or current smoking status) were marginally larger: systolic blood pressure in the ≥2 mmol urinary nitrate excretion group was 3.9 (CI: -7.1 to -0.7) mm Hg lower than in the comparison <1 mmol excretion group. Modest differences in total nitrate exposure are associated with lower blood pressure. These differences are at least equivalent to those seen from substantial (100 mmol) reductions in sodium intake.

  3. 2-Amino-5-chloropyridinium nitrate

    Directory of Open Access Journals (Sweden)

    Donia Zaouali Zgolli

    2009-11-01

    Full Text Available The title structure, C5H6ClN2+·NO3−, is held together by extensive hydrogen bonding between the NO3− ions and 2-amino-5-chloropyridinium H atoms. The cation–anion N—H...O hydrogen bonds link the ions into a zigzag- chain which develops parallel to the b axis. The structure may be compared with that of the related 2-amino-5-cyanopyridinium nitrate.

  4. Sensitivity of nitrate aerosols to ammonia emissions and to nitrate chemistry: implications for present and future nitrate optical depth

    Directory of Open Access Journals (Sweden)

    F. Paulot

    2015-09-01

    Full Text Available We update and evaluate the treatment of nitrate aerosols in the Geophysical Fluid Dynamics Laboratory (GFDL atmospheric model (AM3. Accounting for the radiative effects of nitrate aerosols generally improves the simulated aerosol optical depth, although nitrate concentrations at the surface are biased high. This bias can be reduced by increasing the deposition of nitrate to account for the near-surface volatilization of ammonium nitrate or by neglecting the heterogeneous production of nitric acid to account for the inhibition of N2O5 reactive uptake at high nitrate concentrations. Globally, uncertainties in these processes can impact the simulated nitrate optical depth by up to 25 %, much more than the impact of uncertainties in the seasonality of ammonia emissions (6 % or in the uptake of nitric acid on dust (13 %. Our best estimate for present-day fine nitrate optical depth at 550 nm is 0.006 (0.005–0.008. We only find a modest increase of nitrate optical depth (2 (−40 % and ammonia (+38 % from 2010 to 2050. Nitrate burden is projected to increase in the tropics and in the free troposphere, but to decrease at the surface in the midlatitudes because of lower nitric acid concentrations. Our results suggest that better constraints on the heterogeneous chemistry of nitric acid on dust, on tropical ammonia emissions, and on the transport of ammonia to the free troposphere are needed to improve projections of aerosol optical depth.

  5. Sensitivity of nitrate aerosols to ammonia emissions and to nitrate chemistry: implications for present and future nitrate optical depth

    Science.gov (United States)

    Paulot, F.; Ginoux, P.; Cooke, W. F.; Donner, L. J.; Fan, S.; Lin, M.-Y.; Mao, J.; Naik, V.; Horowitz, L. W.

    2016-02-01

    We update and evaluate the treatment of nitrate aerosols in the Geophysical Fluid Dynamics Laboratory (GFDL) atmospheric model (AM3). Accounting for the radiative effects of nitrate aerosols generally improves the simulated aerosol optical depth, although nitrate concentrations at the surface are biased high. This bias can be reduced by increasing the deposition of nitrate to account for the near-surface volatilization of ammonium nitrate or by neglecting the heterogeneous production of nitric acid to account for the inhibition of N2O5 reactive uptake at high nitrate concentrations. Globally, uncertainties in these processes can impact the simulated nitrate optical depth by up to 25 %, much more than the impact of uncertainties in the seasonality of ammonia emissions (6 %) or in the uptake of nitric acid on dust (13 %). Our best estimate for fine nitrate optical depth at 550 nm in 2010 is 0.006 (0.005-0.008). In wintertime, nitrate aerosols are simulated to account for over 30 % of the aerosol optical depth over western Europe and North America. Simulated nitrate optical depth increases by less than 30 % (0.0061-0.010) in response to projected changes in anthropogenic emissions from 2010 to 2050 (e.g., -40 % for SO2 and +38 % for ammonia). This increase is primarily driven by greater concentrations of nitrate in the free troposphere, while surface nitrate concentrations decrease in the midlatitudes following lower concentrations of nitric acid. With the projected increase of ammonia emissions, we show that better constraints on the vertical distribution of ammonia (e.g., convective transport and biomass burning injection) and on the sources and sinks of nitric acid (e.g., heterogeneous reaction on dust) are needed to improve estimates of future nitrate optical depth.

  6. New insights into nitrate dynamics in a karst groundwater system gained from in situ high-frequency optical sensor measurements

    Science.gov (United States)

    Opsahl, S. P.; Musgrove, M.; Slattery, R. N.

    2017-03-01

    urbanized area of the aquifer. Changes in specific conductance were observed at both sites during groundwater recharge, and a significant correlation between specific conductance and nitrate (correlation coefficient [R] = 0.455) was evident at the urban site where large (3-fold) changes in nitrate occurred. Nitrate concentrations and specific conductance measured during a depth profile indicated that the water column was generally homogeneous as expected for this karst environment, but changes were observed in the most productive zone of the aquifer that might indicate some heterogeneity within the complex network of flow paths. Resolving the timing and magnitude of changes and characterizing fine-scale vertical differences would not be possible using conventional sampling techniques. The patterns observed in situ provided new insight into the dynamic nature of nitrate in a karst groundwater system.

  7. Challenging lanthanide relaxation theory: erbium and thulium complexes that show NMR relaxation rates faster than dysprosium and terbium analogues.

    Science.gov (United States)

    Funk, Alexander M; Harvey, Peter; Finney, Katie-Louise N A; Fox, Mark A; Kenwright, Alan M; Rogers, Nicola J; Senanayake, P Kanthi; Parker, David

    2015-07-07

    Measurements of the proton NMR paramagnetic relaxation rates for several series of isostructural lanthanide(III) complexes have been performed in aqueous solution over the field range 1.0 to 16.5 Tesla. The field dependence has been modeled using Bloch-Redfield-Wangsness theory, allowing values for the electronic relaxation time, Tle and the magnetic susceptibility, μeff, to be estimated. Anomalous relaxation rate profiles were obtained, notably for erbium and thulium complexes of low symmetry 8-coordinate aza-phosphinate complexes. Such behaviour challenges accepted theory and can be interpreted in terms of changes in Tle values that are a function of the transient ligand field induced by solvent collision and vary considerably between Ln(3+) ions, along with magnetic susceptibilities that deviate significantly from free-ion values.

  8. Transport of nitrated albumin across continuous vascular endothelium

    OpenAIRE

    Predescu, Dan; Predescu, Sanda; Malik, Asrar B.

    2002-01-01

    Because modification of plasma albumin on tyrosine residues generates nitrated albumin (NOA) that may function as a mechanism of nitrogen monoxide clearance from microcirculation, we investigated biochemicaly and morphologically the cell surface binding and the transendothelial transport of NOA. An electron microscopic study was carried out with mouse lungs and hearts perfused in situ with NOA and NOA-Au complexes. The results indicate that NOA-Au can bind to the endothelial cell surface, and...

  9. Signalling cascades integrating light-enhanced nitrate metabolism.

    Science.gov (United States)

    Lillo, Cathrine

    2008-10-01

    In higher plants, light is crucial for regulation of nitrate uptake, translocation and assimilation into organic compounds. Part of this metabolism is tightly coupled to photosynthesis because the enzymes involved, nitrite reductase and glutamate synthase, are localized to the chloroplasts and receive reducing power from photosynthetic electron transport. However, important enzymes in nitrate acquisition and reduction are localized to cellular compartments other than chloroplasts and are also up-regulated by light, i.e. transporters in cell and organellar membranes and nitrate reductase in the cytosol. This review describes the different light-dependent signalling cascades regulating nitrate metabolism at the transcriptional as well as post-transcriptional level, and how reactions in different compartments of the cell are co-ordinated. Essential players in this network are phytochrome and HY5 (long hypocotyls 5)/HYH (HY5 homologue)-dependent signalling pathways, the energy-related AMPK (AMP-activated protein kinase) protein kinase homologue SNRK1 (sucrose non-fermenting kinase 1-related kinase), chloroplastic thioredoxins and the prokaryotically originated PII protein. A complex light-dependent network of regulation emerges, which appears to be necessary for optimal nitrogen assimilation and for avoiding the accumulation of toxic intermediates and side products, such as nitrite and reactive oxygen compounds.

  10. Identifying Efficient Nitrate Reduction Strategies in the Upper Danube

    Directory of Open Access Journals (Sweden)

    Angel Udias

    2016-08-01

    Full Text Available Nitrogen losses in the form of Nitrate (N-NO3 from point and diffuse sources of pollution are recognized to be the leading cause of water body impairment throughout Europe. Implementation of conservation programs is perceived as being crucial for restoring and protecting the good ecological status of freshwater bodies. The success of conservation programs depends on the efficient identification of management solutions with respect to the envisaged environmental and economic objectives. This is a complex task, especially considering that costs and effectiveness of conservation strategies depend on their locations. We applied a multi-objective, spatially explicit analysis tool, the R-SWAT-DM framework, to search for efficient, spatially-targeted solution of Nitrate abatement in the Upper Danube Basin. The Soil Water Assessment Tool (SWAT model served as the nonpoint source pollution estimator for current conditions as well as for scenarios with modified agricultural practices and waste water treatment upgrading. A spatially explicit optimization analysis that considered point and diffuse sources of Nitrate was performed to search for strategies that could achieve largest pollution abatement at minimum cost. The set of optimal spatial conservation strategies identified in the Basin indicated that it could be possible to reduce Nitrate loads by more than 50% while simultaneously provide a higher income.

  11. Workgroup report: Drinking-water nitrate and health - Recent findings and research needs

    Science.gov (United States)

    Ward, M.H.; deKok, T.M.; Levallois, P.; Brender, J.; Gulis, G.; Nolan, B.T.; VanDerslice, J.

    2005-01-01

    Human alteration of the nitrogen cycle has resulted in steadily accumulating nitrate in our water resources. The U.S. maximum contaminant level and World Health Organization guidelines for nitrate in drinking water were promulgated to protect infants from developing methemoglobinemia, an acute condition. Some scientists have recently suggested that the regulatory limit for nitrate is overly conservative; however, they have not thoroughly considered chronic health outcomes. In August 2004, a symposium on drinking-water nitrate and health was held at the International Society for Environmental Epidemiology meeting to evaluate nitrate exposures and associated health effects in relation to the current regulatory limit. The contribution of drinking-water nitrate toward endogenous formation of N-nitroso compounds was evaluated with a focus toward identifying subpopulations with increased rates of nitrosation. Adverse health effects may be the result of a complex interaction of the amount of nitrate ingested, the concomitant ingestion of nitrosation cofactors and precursors, and specific medical conditions that increase nitrosation. Workshop participants concluded that more experimental studies are needed and that a particularly fruitful approach may be to conduct epidemiologic studies among susceptible subgroups with increased endogenous nitrosation. The few epidemiologic studies that have evaluated intake of nitrosation precursors and/or nitrosation inhibitors have observed elevated risks for colon cancer and neural tube defects associated with drinking-water nitrate concentrations below the regulatory limit. The role of drinking-water nitrate exposure as a risk factor for specific cancers, reproductive outcomes, and other chronic health effects must be studied more thoroughly before changes to the regulatory level for nitrate in drinking water can be considered.

  12. Hydrological and environmental controls of the stream nitrate concentration and flux in a small agricultural watershed

    Science.gov (United States)

    Zhou, Y.; Xu, J. F.; Yin, W.; Ai, L.; Fang, N. F.; Tan, W. F.; Yan, F. L.; Shi, Z. H.

    2017-02-01

    Nitrate exports from diffuse sources constitute a major cause of eutrophication and episodic acidification in inland aquatic systems, and remedial action requires the identification of the influencing factors associated with these nitrate exports. This paper examines the combined effects of watershed complexity on nitrate concentration and flux in terms of the hydrological and environmental factors in heterogeneous nested subwatersheds in the Danjiangkou Reservoir Area (DRA), China. We established 15 sampling sites in the main stream and tributaries and conducted biweekly sampling in 2008-2012 to monitor the nitrate exports. The hydrological and environmental indices within the watershed were divided into subwatersheds and considered as potential influencing factors. In consideration of the high co-linearity of these influencing factors, we used partial least squares regression (PLSR) to determine the associations between the stream nitrate concentration or flux and 26 selected watershed characteristics. The number of components was unequal for the nitrate concentration and flux models. The optimal models explained 66.4%, 60.0% and 59.9% of the variability in nitrate concentration and 74.7%, 67.1% and 58.0% of the variability in nitrate flux annually, in the dry season, and in the wet season, respectively. According to the variable importance in the projection (VIP) values, the dominant first-order factors for the nitrate concentration were as follows: the areal percentages of agricultural, forest and residential areas; followed by the slope; the largest patch index (LPI); the flow path gradient (FPG); the slope gradient variance (SGV); and the splitting index (SPLIT). In addition to these factors, the runoff coefficient (RC), flashiness index (FI), and patch density (PD) affected the changes in the nitrate flux. This study illustrates the influence of hydrological and environmental factors on seasonal water quality and can serve as guidelines for better watershed

  13. Impacts of management and climate change on nitrate leaching in a forested karst area.

    Science.gov (United States)

    Thomas, Dirnböck; Johannes, Kobler; David, Kraus; Rüdiger, Grote; Ralf, Kiese

    2016-01-01

    Forest management and climate change, directly or indirectly, affect drinking water resources, both in terms of quality and quantity. In this study in the Northern Limestone Alps in Austria we have chosen model calculations (LandscapeDNDC) in order to resolve the complex long-term interactions of management and climate change and their effect on nitrogen dynamics, and the consequences for nitrate leaching from forest soils into the karst groundwater. Our study highlights the dominant role of forest management in controlling nitrate leaching. Both clear-cut and shelterwood-cut disrupt the nitrogen cycle to an extent that causes peak concentrations and high fluxes into the seepage water. While this effect is well known, our modelling approach has revealed additional positive as well as negative impacts of the expected climatic changes on nitrate leaching. First, we show that peak nitrate concentrations during post-cutting periods were elevated under all climate scenarios. The maximal effects of climatic changes on nitrate concentration peaks were 20-24 mg L(-1) in 2090 with shelterwood or clear-cut management. Second, climate change significantly decreased the cumulative nitrate losses over full forest rotation periods (by 10-20%). The stronger the expected temperature increase and precipitation decrease (in summer), the lesser were the observed nitrate losses. However, mean annual seepage water nitrate concentrations and cumulative nitrate leaching were higher under continuous forest cover management than with shelterwood-cut and clear-cut systems. Watershed management can thus be adapted to climate change by either reducing peak concentrations or long-term loads of nitrate in the karst groundwater.

  14. Workgroup Report: Drinking-Water Nitrate and Health—Recent Findings and Research Needs

    Science.gov (United States)

    Ward, Mary H.; deKok, Theo M.; Levallois, Patrick; Brender, Jean; Gulis, Gabriel; Nolan, Bernard T.; VanDerslice, James

    2005-01-01

    Human alteration of the nitrogen cycle has resulted in steadily accumulating nitrate in our water resources. The U.S. maximum contaminant level and World Health Organization guidelines for nitrate in drinking water were promulgated to protect infants from developing methemoglobinemia, an acute condition. Some scientists have recently suggested that the regulatory limit for nitrate is overly conservative; however, they have not thoroughly considered chronic health outcomes. In August 2004, a symposium on drinking-water nitrate and health was held at the International Society for Environmental Epidemiology meeting to evaluate nitrate exposures and associated health effects in relation to the current regulatory limit. The contribution of drinking-water nitrate toward endogenous formation of N-nitroso compounds was evaluated with a focus toward identifying subpopulations with increased rates of nitrosation. Adverse health effects may be the result of a complex interaction of the amount of nitrate ingested, the concomitant ingestion of nitrosation cofactors and precursors, and specific medical conditions that increase nitrosation. Workshop participants concluded that more experimental studies are needed and that a particularly fruitful approach may be to conduct epidemiologic studies among susceptible subgroups with increased endogenous nitrosation. The few epidemiologic studies that have evaluated intake of nitrosation precursors and/or nitrosation inhibitors have observed elevated risks for colon cancer and neural tube defects associated with drinking-water nitrate concentrations below the regulatory limit. The role of drinking-water nitrate exposure as a risk factor for specific cancers, reproductive outcomes, and other chronic health effects must be studied more thoroughly before changes to the regulatory level for nitrate in drinking water can be considered. PMID:16263519

  15. Nitrate contamination of groundwater and its countermeasures

    Energy Technology Data Exchange (ETDEWEB)

    Mitamura, Hisayoshi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    2003-03-01

    The inevitable increases of food production and energy consumption with an increase in world population become main causes of an increase of nitrate load to the environment. Although nitrogen is essential for the growth of animal and plant as a constituent element of protein, excessive nitrate load to the environment contaminates groundwater resources used as drinking water and leads to seriously adverse effects on the health of man and livestock. In order to clarify the problem of nitrate contamination of groundwater and search a new trend of technology development from the viewpoint of environment remediation and protection, the present paper has reviewed adverse effects of nitrate on human health, the actual state of nitrogen cycle, several kinds of nitrate sources, measures for reducing nitrate level, etc. (author)

  16. KINETICS STUDY ON NITRATION OF METHYL RICINOLEATE

    OpenAIRE

    Abdullah, Abdullah; Triyono, Triyono; Trisunaryanti, Wega; Haryadi, Winarto

    2012-01-01

    Kinetics parameter values of methyl ricinoleate nitration (rate constant, reaction order and the rate of reaction) have been determined. Nitration was carried out with both concentrations of HNO3 and acetic anhydride in excess to the concentration of methyl ricinoleate. Thus, the kinetics parameter value was only affected by the concentration of methyl ricinoleate. Based on kinetic study conducted, it could be concluded that the nitration follows pseudo first-order, and the reaction rate for ...

  17. Nitrate leaching from Silage Maize

    OpenAIRE

    Hansen, Elly Møller; Eriksen, Jørgen

    2009-01-01

    During the last 20 years the area with maize in Denmark has increased dramatically and reached 163,000 ha in 2008. Silage maize is easy to grow, is a suitable fodder for cows and goes well with grass-clover in the diet. This means that silage maize is often found in crop rotations with grass-clover on sandy soils in western Denmark. The ploughing in of grass-clover fields poses a serious risk of increased nitrate leaching on a coarse sandy soil, even when carried out in spring. With increased...

  18. Trend Analyses of Nitrate in Danish Groundwater

    Science.gov (United States)

    Hansen, B.; Thorling, L.; Dalgaard, T.; Erlandsen, M.

    2012-04-01

    This presentation assesses the long-term development in the oxic groundwater nitrate concentration and nitrogen (N) loss due to intensive farming in Denmark. Firstly, up to 20-year time-series from the national groundwater monitoring network enable a statistically systematic analysis of distribution, trends and trend reversals in the groundwater nitrate concentration. Secondly, knowledge about the N surplus in Danish agriculture since 1950 is used as an indicator of the potential loss of N. Thirdly, groundwater recharge CFC (Chlorofluorocarbon) age determination allows linking of the first two dataset. The development in the nitrate concentration of oxic groundwater clearly mirrors the development in the national agricultural N surplus, and a corresponding trend reversal is found in groundwater. Regulation and technical improvements in the intensive farming in Denmark have succeeded in decreasing the N surplus by 40% since the mid 1980s while at the same time maintaining crop yields and increasing the animal production of especially pigs. Trend analyses prove that the youngest (0-15 years old) oxic groundwater shows more pronounced significant downward nitrate trends (44%) than the oldest (25-50 years old) oxic groundwater (9%). This amounts to clear evidence of the effect of reduced nitrate leaching on groundwater nitrate concentrations in Denmark. Are the Danish groundwater monitoring strategy obtimal for detection of nitrate trends? Will the nitrate concentrations in Danish groundwater continue to decrease or are the Danish nitrate concentration levels now appropriate according to the Water Framework Directive?

  19. Measurement of isoprene nitrates by GCMS

    Science.gov (United States)

    Mills, Graham P.; Hiatt-Gipson, Glyn D.; Bew, Sean P.; Reeves, Claire E.

    2016-09-01

    According to atmospheric chemistry models, isoprene nitrates play an important role in determining the ozone production efficiency of isoprene; however this is very poorly constrained through observations as isoprene nitrates have not been widely measured. Measurements have been severely restricted largely due to a limited ability to measure individual isoprene nitrate isomers. An instrument based on gas chromatography/mass spectrometry (GCMS) and the associated calibration methods are described for the speciated measurements of individual isoprene nitrate isomers. Five of the primary isoprene nitrates which formed in the presence of NOx by reaction of isoprene with the hydroxyl radical (OH) in the Master Chemical Mechanism are identified using known isomers on two column phases and are fully separated on the Rtx-200 column. Three primary isoprene nitrates from the reaction of isoprene with the nitrate radical (NO3) are identified after synthesis from the already identified analogous hydroxy nitrate. A Tenax adsorbent-based trapping system allows the analysis of the majority of the known hydroxy and carbonyl primary isoprene nitrates, although not the (1,2)-IN isomer, under field-like levels of humidity and showed no impact from typical ambient concentrations of NOx and ozone.

  20. Nitration of Phenol Catalyzed by Horseradish Peroxidase

    Institute of Scientific and Technical Information of China (English)

    DAI Rong-ji; HUANG Hui; TONG Bin; XIAO Sheng-yuan

    2007-01-01

    Horseradish peroxidase, an acidic peroxidase from the horseradish, is one of the most important enzymes as analytical reagent.The enzymatic nitration of phenol by oxidation of nitrite was studied using horseradish peroxidase in the presence of H2O2.The results showed that nitration occur at 2- and 4- positions of phenol.There were also minor products of hydroquinone and catechol.The influence of various reaction parameters, including pH, organic solvent, and concentration of H2O2, on nitration products were discussed.The best nitration pH was 7.0, and H2O2 should be added to the reaction mixture slowly.

  1. Nitration of Y10 in Aβ1-40: is it a compensatory reaction against oxidative/nitrative stress and Aβ aggregation?

    Science.gov (United States)

    Zhao, Jie; Wang, Peipei; Li, Hailing; Gao, Zhonghong

    2015-03-16

    Amyloid β peptide (Aβ) aggregation is considered to be a crucial pathological biomarker of Alzheimer's disease (AD). It was found that Aβ and heme can form an Aβ-heme complex, which results in increased heme pseudoperoxidase activity. Recently, we found that increasing pseudoperoxidase activity induces elevated tyrosine nitration on Aβ in the presence of nitrite and hydrogen peroxide. However, the nature of tyrosine nitration of Aβ and its physiologic significance are still unknown. In this study, we revealed that Aβ1-40 can be nitrated in vitro by binding to heme in the presence of nitrite and hydrogen peroxide. Moreover, we found that tyrosine nitration had little effect on Aβ1-40's binding activity with heme. A TMB assay also revealed that the peroxidase activity of the heme-Aβ1-40Y10(3N)T (tyrosine 10 was replaced with 3-nitrtotyrosine in Aβ1-40) complex was moderately increased compared with that of the heme-Aβ1-40 complex. Furthermore, Thioflavin T fluorescence and transmission electron microscopic characterization indicated that tyrosine nitration significantly decreased the aggregation of Aβ1-40. In addition, a cytotoxicity test verified that wild-type Aβ1-40 was more cytotoxic than that of Aβ1-40Y10(3N)T. These results suggest that nitration of Aβ1-40 might be an Aβ detoxicant process and a compensatory reaction to nitrative stress. Our findings may lead to a detailed understanding of the function of Aβ1-40 and may be helpful in preventing and curing AD.

  2. Yttrium Nitrate mediated Nitration of Phenols at room temperature in Glacial Acetic acid

    Indian Academy of Sciences (India)

    MOHABUL A MONDAL; DBASHIS MANDAL; KANCHAN MITRA

    2017-01-01

    Rapid nitration of electron rich phenols using Y(NO₃)₃.6H₂O in glacial acetic acid at room temperature was observed with good yield. The method allows nitration of phenols without oxidation, and isolation of nitration product in a rapid and simple way. The described method is selective for phenols.

  3. Arabidopsis Nitrate Transporter NRT1.9 Is Important in Phloem Nitrate Transport[W][OA

    Science.gov (United States)

    Wang, Ya-Yun; Tsay, Yi-Fang

    2011-01-01

    This study of the Arabidopsis thaliana nitrate transporter NRT1.9 reveals an important function for a NRT1 family member in phloem nitrate transport. Functional analysis in Xenopus laevis oocytes showed that NRT1.9 is a low-affinity nitrate transporter. Green fluorescent protein and β-glucuronidase reporter analyses indicated that NRT1.9 is a plasma membrane transporter expressed in the companion cells of root phloem. In nrt1.9 mutants, nitrate content in root phloem exudates was decreased, and downward nitrate transport was reduced, suggesting that NRT1.9 may facilitate loading of nitrate into the root phloem and enhance downward nitrate transport in roots. Under high nitrate conditions, the nrt1.9 mutant showed enhanced root-to-shoot nitrate transport and plant growth. We conclude that phloem nitrate transport is facilitated by expression of NRT1.9 in root companion cells. In addition, enhanced root-to-shoot xylem transport of nitrate in nrt1.9 mutants points to a negative correlation between xylem and phloem nitrate transport. PMID:21571952

  4. Arabidopsis nitrate transporter NRT1.9 is important in phloem nitrate transport.

    Science.gov (United States)

    Wang, Ya-Yun; Tsay, Yi-Fang

    2011-05-01

    This study of the Arabidopsis thaliana nitrate transporter NRT1.9 reveals an important function for a NRT1 family member in phloem nitrate transport. Functional analysis in Xenopus laevis oocytes showed that NRT1.9 is a low-affinity nitrate transporter. Green fluorescent protein and β-glucuronidase reporter analyses indicated that NRT1.9 is a plasma membrane transporter expressed in the companion cells of root phloem. In nrt1.9 mutants, nitrate content in root phloem exudates was decreased, and downward nitrate transport was reduced, suggesting that NRT1.9 may facilitate loading of nitrate into the root phloem and enhance downward nitrate transport in roots. Under high nitrate conditions, the nrt1.9 mutant showed enhanced root-to-shoot nitrate transport and plant growth. We conclude that phloem nitrate transport is facilitated by expression of NRT1.9 in root companion cells. In addition, enhanced root-to-shoot xylem transport of nitrate in nrt1.9 mutants points to a negative correlation between xylem and phloem nitrate transport.

  5. Challenges with nitrate therapy and nitrate tolerance: prevalence, prevention, and clinical relevance.

    Science.gov (United States)

    Thadani, Udho

    2014-08-01

    Nitrate therapy has been an effective treatment for ischemic heart disease for over 100 years. The anti-ischemic and exercise-promoting benefits of sublingually administered nitrates are well established. Nitroglycerin is indicated for the relief of an established attack of angina and for prophylactic use, but its effects are short lived. In an effort to increase the duration of beneficial effects, long-acting orally administered and topical applications of nitrates have been developed; however, following their continued or frequent daily use, patients soon develop tolerance to these long-acting nitrate preparations. Once tolerance develops, patients begin losing the protective effects of the long-acting nitrate therapy. By providing a nitrate-free interval, or declining nitrate levels at night, one can overcome or reduce the development of tolerance, but cannot provide 24-h anti-anginal and anti-ischemic protection. In addition, patients may be vulnerable to occurrence of rebound angina and myocardial ischemia during periods of absent nitrate levels at night and early hours of the morning, and worsening of exercise capacity prior to the morning dose of the medication. This has been a concern with nitroglycerin patches but not with oral formulations of isosorbide-5 mononitrates, and has not been adequately studied with isosorbide dinitrate. This paper describes problems associated with nitrate tolerance, reviews mechanisms by which nitrate tolerance and loss of efficacy develop, and presents strategies to avoid nitrate tolerance and maintain efficacy when using long-acting nitrate formulations.

  6. California GAMA Special Study: An isotopic and dissolved gas investigation of nitrate source and transport to a public supply well in California's Central Valley

    Energy Technology Data Exchange (ETDEWEB)

    Singleton, M J; Moran, J E; Esser, B K; Roberts, S K; Hillegonds, D J

    2010-04-14

    study provides two new pieces of evidence that the Ripon Farm Services Plant is the source of elevated nitrate in Ripon City Well 12. (1) Chemical mass balance calculations using nitrate concentration, nitrate isotopic composition, and initial tritium activity all indicate that that the source water for elevated nitrate to Ripon City Well 12 is a very small component of the water produced by City Well 12 and thus must have extremely high nitrate concentration. The high source water nitrate concentration ({approx}1500 mg/L as nitrate) required by these mass balance calculations precludes common sources of nitrate such as irrigated agriculture, dairy wastewater, and septic discharge. Shallow groundwater under the Ripon Farm Services RFS plant does contain extremely high concentrations of nitrate (>1700 mg/L as nitrate). (2) Nitrogen and oxygen isotope compositions of nitrate indicate that the additional anthropogenic nitrate source to Ripon City Well 12 is significantly enriched in {delta}{sup 18}O-NO{sub 3}, an isotopic signature consistent with synthetic nitrate fertilizer, and not with human or animal wastewater discharge (i.e. dairy operations, septic system discharge, or municipal wastewater discharge), or with organic fertilizer. Monitoring wells on and near the RFS plant also have high {delta}{sup 18}O-NO{sub 3}, and the plant has handled and stored synthetic nitrate fertilizer that will have this isotopic signature. The results described here highlight the complexity of attributing nitrate found in long screened, high capacity wells to specific sources. In this case, the presence of a very high concentration source near the well site combined with sampling using multiple isotopic tracer techniques and specialized depth-specific techniques allowed fingerprinting of the source in the mixed-age samples drawn from the production well.

  7. Synthesis, spectroscopic characterization, and thermal decomposition kinetics of some lanthanide(Ⅲ) nitrate complexes of 2-(N-o-hydroxyacetophenone) amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene

    Institute of Scientific and Technical Information of China (English)

    K.Mohanan; M.Thankamony; B.Sindhu Kumari

    2008-01-01

    Complexes of La(Ⅲ), Ce(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), Dy(Ⅲ), Yb(Ⅲ), and Lu(Ⅲ) with 2-(N-o- hydroxyacetophenone)amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene (HAAT) formed by the condensation of o-hydroxyacetophenone and 2-amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene were synthesized and characterized on the basis of elemental analyses, molar conductance measurements, magnetic susceptibility data, UV-Visible, IR, and NMR spectral studies. The spectral data revealed that the ligand acted as a neutral tridentate coordinating to the metal ion through ONO donor sequence. A coordination number nine was proposed for the complexes. Thermal decomposition studies of the ligand and lanthanum(Ⅲ) complex were carried out and kinetic parameters were calculated using Coats-Redfern equation. The decomposition reactions followed random nucleation mechanism with one nucleus on each particle.

  8. Evaluation of nitrates in albanian wines

    Directory of Open Access Journals (Sweden)

    Ariola Morina

    2013-05-01

    Full Text Available Nitrates are important compounds in nature but not desirable if they are present in wine at increased amount. The high level of nitrate is attributed to the use of nitrogen fertilizers in the vineyards. Method of the reactive Gries I and Gries II was used for the determination of nitrates in wine. There were analyzed 45 white wines and 55 red wines produced in 2008 – 2010, as well as wines produced from Albanian grape varieties Shesh i Bardhë and Shesh i Zi in 2009 and 2010, as an authentic wines evidence with denominated origin. From the results of analyses was observed that, in 51 % of white wines was found that the content of nitrates were less than 5 mg/l, in 46% of them the nitrates level goes up to 10 mg/l and only in 3 % of them the amount of nitrates is up to 12 mg/l. None of white wine samples have the content of nitrates over 20 mg/l. In this case there is no doubt for water addition during wine preparation. In regards of red wines, in 34% of them the amount of nitrates is up to 5 mg/l, in 30% of them up to 10 mg/l, while in 26% of them the amount of nitrates is 20 mg/l. Only 10 % of red wines have nitrates content over 20 mg/l which raise dubiety for falsified wines where water and sugar is added in the red marc. The level of nitrates in wines with denominated origin was under 20 mg/L.

  9. Regulation of nitrate assimilation in cyanobacteria.

    Science.gov (United States)

    Ohashi, Yoshitake; Shi, Wei; Takatani, Nobuyuki; Aichi, Makiko; Maeda, Shin-ichi; Watanabe, Satoru; Yoshikawa, Hirofumi; Omata, Tatsuo

    2011-02-01

    Nitrate assimilation by cyanobacteria is inhibited by the presence of ammonium in the growth medium. Both nitrate uptake and transcription of the nitrate assimilatory genes are regulated. The major intracellular signal for the regulation is, however, not ammonium or glutamine, but 2-oxoglutarate (2-OG), whose concentration changes according to the change in cellular C/N balance. When nitrogen is limiting growth, accumulation of 2-OG activates the transcription factor NtcA to induce transcription of the nitrate assimilation genes. Ammonium inhibits transcription by quickly depleting the 2-OG pool through its metabolism via the glutamine synthetase/glutamate synthase cycle. The P(II) protein inhibits the ABC-type nitrate transporter, and also nitrate reductase in some strains, by an unknown mechanism(s) when the cellular 2-OG level is low. Upon nitrogen limitation, 2-OG binds to P(II) to prevent the protein from inhibiting nitrate assimilation. A pathway-specific transcriptional regulator NtcB activates the nitrate assimilation genes in response to nitrite, either added to the medium or generated intracellularly by nitrate reduction. It plays an important role in selective activation of the nitrate assimilation pathway during growth under a limited supply of nitrate. P(II) was recently shown to regulate the activity of NtcA negatively by binding to PipX, a small coactivator protein of NtcA. On the basis of accumulating genome information from a variety of cyanobacteria and the molecular genetic data obtained from the representative strains, common features and group- or species-specific characteristics of the response of cyanobacteria to nitrogen is summarized and discussed in terms of ecophysiological significance.

  10. Nitrate reduction functional genes and nitrate reduction potentials persist in deeper estuarine sediments. Why?

    Directory of Open Access Journals (Sweden)

    Sokratis Papaspyrou

    Full Text Available Denitrification and dissimilatory nitrate reduction to ammonium (DNRA are processes occurring simultaneously under oxygen-limited or anaerobic conditions, where both compete for nitrate and organic carbon. Despite their ecological importance, there has been little investigation of how denitrification and DNRA potentials and related functional genes vary vertically with sediment depth. Nitrate reduction potentials measured in sediment depth profiles along the Colne estuary were in the upper range of nitrate reduction rates reported from other sediments and showed the existence of strong decreasing trends both with increasing depth and along the estuary. Denitrification potential decreased along the estuary, decreasing more rapidly with depth towards the estuary mouth. In contrast, DNRA potential increased along the estuary. Significant decreases in copy numbers of 16S rRNA and nitrate reducing genes were observed along the estuary and from surface to deeper sediments. Both metabolic potentials and functional genes persisted at sediment depths where porewater nitrate was absent. Transport of nitrate by bioturbation, based on macrofauna distributions, could only account for the upper 10 cm depth of sediment. A several fold higher combined freeze-lysable KCl-extractable nitrate pool compared to porewater nitrate was detected. We hypothesised that his could be attributed to intracellular nitrate pools from nitrate accumulating microorganisms like Thioploca or Beggiatoa. However, pyrosequencing analysis did not detect any such organisms, leaving other bacteria, microbenthic algae, or foraminiferans which have also been shown to accumulate nitrate, as possible candidates. The importance and bioavailability of a KCl-extractable nitrate sediment pool remains to be tested. The significant variation in the vertical pattern and abundance of the various nitrate reducing genes phylotypes reasonably suggests differences in their activity throughout the

  11. Nitrate Reduction Functional Genes and Nitrate Reduction Potentials Persist in Deeper Estuarine Sediments. Why?

    Science.gov (United States)

    Papaspyrou, Sokratis; Smith, Cindy J.; Dong, Liang F.; Whitby, Corinne; Dumbrell, Alex J.; Nedwell, David B.

    2014-01-01

    Denitrification and dissimilatory nitrate reduction to ammonium (DNRA) are processes occurring simultaneously under oxygen-limited or anaerobic conditions, where both compete for nitrate and organic carbon. Despite their ecological importance, there has been little investigation of how denitrification and DNRA potentials and related functional genes vary vertically with sediment depth. Nitrate reduction potentials measured in sediment depth profiles along the Colne estuary were in the upper range of nitrate reduction rates reported from other sediments and showed the existence of strong decreasing trends both with increasing depth and along the estuary. Denitrification potential decreased along the estuary, decreasing more rapidly with depth towards the estuary mouth. In contrast, DNRA potential increased along the estuary. Significant decreases in copy numbers of 16S rRNA and nitrate reducing genes were observed along the estuary and from surface to deeper sediments. Both metabolic potentials and functional genes persisted at sediment depths where porewater nitrate was absent. Transport of nitrate by bioturbation, based on macrofauna distributions, could only account for the upper 10 cm depth of sediment. A several fold higher combined freeze-lysable KCl-extractable nitrate pool compared to porewater nitrate was detected. We hypothesised that his could be attributed to intracellular nitrate pools from nitrate accumulating microorganisms like Thioploca or Beggiatoa. However, pyrosequencing analysis did not detect any such organisms, leaving other bacteria, microbenthic algae, or foraminiferans which have also been shown to accumulate nitrate, as possible candidates. The importance and bioavailability of a KCl-extractable nitrate sediment pool remains to be tested. The significant variation in the vertical pattern and abundance of the various nitrate reducing genes phylotypes reasonably suggests differences in their activity throughout the sediment column. This

  12. Computational insight into nitration of human myoglobin.

    Science.gov (United States)

    Lin, Ying-Wu; Shu, Xiao-Gang; Du, Ke-Jie; Nie, Chang-Ming; Wen, Ge-Bo

    2014-10-01

    Protein nitration is an important post-translational modification regulating protein structure and function, especially for heme proteins. Myoglobin (Mb) is an ideal protein model for investigating the structure and function relationship of heme proteins. With limited structural information available for nitrated heme proteins from experiments, we herein performed a molecular dynamics study of human Mb with successive nitration of Tyr103, Tyr146, Trp7 and Trp14. We made a detailed comparison of protein motions, intramolecular contacts and internal cavities of nitrated Mbs with that of native Mb. It showed that although nitration of both Tyr103 and Tyr146 slightly alters the local conformation of heme active site, further nitration of both Trp7 and Trp14 shifts helix A apart from the rest of protein, which results in altered internal cavities and forms a water channel, representing an initial stage of Mb unfolding. The computational study provides an insight into the nitration of heme proteins at an atomic level, which is valuable for understanding the structure and function relationship of heme proteins in non-native states by nitration. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Bacterial nitrate assimilation: gene distribution and regulation.

    Science.gov (United States)

    Luque-Almagro, Víctor M; Gates, Andrew J; Moreno-Vivián, Conrado; Ferguson, Stuart J; Richardson, David J; Roldán, M Dolores

    2011-12-01

    In the context of the global nitrogen cycle, the importance of inorganic nitrate for the nutrition and growth of marine and freshwater autotrophic phytoplankton has long been recognized. In contrast, the utilization of nitrate by heterotrophic bacteria has historically received less attention because the primary role of these organisms has classically been considered to be the decomposition and mineralization of dissolved and particulate organic nitrogen. In the pre-genome sequence era, it was known that some, but not all, heterotrophic bacteria were capable of growth on nitrate as a sole nitrogen source. However, examination of currently available prokaryotic genome sequences suggests that assimilatory nitrate reductase (Nas) systems are widespread phylogenetically in bacterial and archaeal heterotrophs. Until now, regulation of nitrate assimilation has been mainly studied in cyanobacteria. In contrast, in heterotrophic bacterial strains, the study of nitrate assimilation regulation has been limited to Rhodobacter capsulatus, Klebsiella oxytoca, Azotobacter vinelandii and Bacillus subtilis. In Gram-negative bacteria, the nas genes are subjected to dual control: ammonia repression by the general nitrogen regulatory (Ntr) system and specific nitrate or nitrite induction. The Ntr system is widely distributed in bacteria, whereas the nitrate/nitrite-specific control is variable depending on the organism.

  14. Dietary Nitrate, Nitric Oxide, and Cardiovascular Health.

    Science.gov (United States)

    Bondonno, Catherine P; Croft, Kevin D; Hodgson, Jonathan M

    2016-09-09

    Emerging evidence strongly suggests that dietary nitrate, derived in the diet primarily from vegetables, could contribute to cardiovascular health via effects on nitric oxide (NO) status. NO plays an essential role in cardiovascular health. It is produced via the classical L-arginine-NO-synthase pathway and the recently discovered enterosalivary nitrate-nitrite-NO pathway. The discovery of this alternate pathway has highlighted dietary nitrate as a candidate for the cardioprotective effect of a diet rich in fruit and vegetables. Clinical trials with dietary nitrate have observed improvements in blood pressure, endothelial function, ischemia-reperfusion injury, arterial stiffness, platelet function, and exercise performance with a concomitant augmentation of markers of NO status. While these results are indicative of cardiovascular benefits with dietary nitrate intake, there is still a lingering concern about nitrate in relation to methemoglobinemia, cancer, and cardiovascular disease. It is the purpose of this review to present an overview of NO and its critical role in cardiovascular health; to detail the observed vascular benefits of dietary nitrate intake through effects on NO status as well as to discuss the controversy surrounding the possible toxic effects of nitrate.

  15. 4-Methoxy-N,N′-diphenylbenzamidinium nitrate

    Directory of Open Access Journals (Sweden)

    Renata S. Silva

    2016-09-01

    Full Text Available The asymmetric unit of the title salt N,N′-diphenyl-4-methoxybenzamidinium nitrate, C20H19N2O+·NO3−, comprises two independent N,N′-diphenyl-4-methoxybenzamidinium cations and two nitrate anions. The crystal structure features N—H...O hydrogen bonds and C—H...O contacts responsible for the packing.

  16. Can nitrate contaminated groundwater be remediated by optimizing flood irrigation rate with high nitrate water in a desert oasis using the WHCNS model?

    Science.gov (United States)

    Liang, Hao; Qi, Zhiming; Hu, Kelin; Prasher, Shiv O; Zhang, Yuanpei

    2016-10-01

    Nitrate contamination of groundwater is an environmental concern in intensively cultivated desert oases where this polluted groundwater is in turn used as a major irrigation water resource. However, nitrate fluxes from root zone to groundwater are difficult to monitor in this complex system. The objectives of this study were to validate and apply the WHCNS (soil Water Heat Carbon Nitrogen Simulator) model to simulate water drainage and nitrate leaching under different irrigation and nitrogen (N) management practices, and to assess the utilization of groundwater nitrate as an approach to remediate nitrate contaminated groundwater while maintain crop yield. A two-year field experiment was conducted in a corn field irrigated with high nitrate groundwater (20 mg N L(-1)) in Alxa, Inner Mongolia, China. The experiment consisted of two irrigation treatments (Istd, standard, 750 mm per season; Icsv, conservation, 570 mm per season) factorially combined with two N fertilization treatments (Nstd, standard, 138 kg ha(-1); Ncsv, conservation, 92 kg ha(-1)). The validated results showed that the WHCNS model simulated values of crop dry matter, yield, soil water content and soil N concentration in soil profile all agreed well with the observed values. Compared to the standard water management (Istd), the simulated drainage and nitrate leaching decreased about 65% and 59%, respectively, under the conservation water management (Icsv). Nearly 55% of input N was lost by leaching under the IstdNstd and IstdNcsv treatments, compared to only 26% under the IcsvNstd and IcsvNcsv treatments. Simulations with more than 240 scenarios combing different levels of irrigation and fertilization indicated that irrigation was the main reason leading to the high risk of nitrate leaching, and the nitrate in irrigation groundwater can be best utilized without corn yield loss when the total irrigation was reduced from the current 750 mm to 491 mm. This reduced irrigation rate facilitated

  17. Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants; Cinetique d`extraction liquide-liquide du nitrate d`uranyle et des nitrates d`actinides (III) et de lanthanides (III) par des extractants a fonction amide

    Energy Technology Data Exchange (ETDEWEB)

    Toulemonde, V. [CEA Centre d`Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France)]|[CEA Centre d`Etudes de la Vallee du Rhone, 30 -Marcoule (France). Dept. d`Exploitation du Retraitement et de Demantelement

    1995-12-20

    The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author). 89 refs.

  18. Nitrate reduction in an unconfined sandy aquifer

    DEFF Research Database (Denmark)

    Postma, Diederik Jan; Boesen, Carsten; Kristiansen, Henning;

    1991-01-01

    Nitrate distribution and reduction processes were investigated in an unconfined sandy aquifer of Quaternary age. Groundwater chemistry was studied in a series of eight multilevel samplers along a flow line, deriving water from both arable and forested land. Results show that plumes of nitrate...... processes of O2 and NO3- occur at rates that are fast compared to the rate of downward water transport. Nitrate-contaminated groundwater contains total contents of dissolved ions that are two to four times higher than in groundwater derived from the forested area. The persistence of the high content...... of total dissolved ions in the NO3- free anoxic zone indicates the downward migration of contaminants and that active nitrate reduction is taking place. Nitrate is apparently reduced to N2 because both nitrite and ammonia are absent or found at very low concentrations. Possible electron donors...

  19. Sedimentary nitrate reduction and its effect on the N-isotopic composition of oceanic nitrate

    Science.gov (United States)

    Lehmann, M. F.; Sigman, D. M.; McCorkle, D. C.

    2005-12-01

    A prerequisite for assessing denitrification fluxes in a specific environment using water column nitrate N isotope ratios is the knowledge of the expressed N isotope effects of water column and/or benthic denitrification in this environment. Here, we aim at assessing the effects of benthic nitrogen cycling on the N isotopic composition of the oceanic nitrate pool in deep-sea sediments, which are believed to harbour a large portion of the global benthic denitrification. We report 15N/14N ratios of pore water nitrate in pelagic sediments from the deep Bering Sea, where benthic nitrate reduction has previously been identified as a significant sink of fixed nitrogen. Porewater profiles from multicores indicate strong 15N enrichment in porewater nitrate at all stations, as one goes deeper in the sediments and nitrate concentrations decrease (δ15N generally reached 25-35‰). Our data are consistent with variable biological isotope effect (ɛ) for dissimilatory nitrate reduction ranging between 13 to 30 ‰. A one-dimensional diffusion-reaction model including organic matter degradation, nitrification, and denitrification indicates that, although denitrification leads to a pore water nitrate pool that is enriched in 15N, N isotope fractionation is poorly expressed at the scale of sediment-water nitrate exchange, independent of whether sediments are a net sink or a net source of nitrate. The apparent nitrate isotope effect of sedimentary denitrification on nitrate in overlying waters is generally below 2‰, as a result of diffusive transport limitation into, and within, the sediments and/or the production of light nitrate during nitrification. Thus, our data suggest that the low expressed isotope effect of benthic denitrification observed previously in reactive shelf sediments also applies to deep-sea sediments. However, where ammonium fluxes out of the sediments, it is enriched in 15-N, and may ultimately lead to an N-isotopic enrichment of the water-column nitrate

  20. Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

    Science.gov (United States)

    Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J.K.

    2017-01-01

    weeks. Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation–reduction reaction.

  1. Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

    Science.gov (United States)

    Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J. K.

    2017-01-01

    . Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation-reduction reaction.

  2. Reaction of lanthanide nitrates with macrocyclic amidoacylhydrazones

    Energy Technology Data Exchange (ETDEWEB)

    Malinka, E.V.; Bondarev, M.L.; Bel' tyukova, S.V.; Poleuktov, N.S.; Nazarenko, N.A.

    1987-09-01

    This paper deals with a study of the reaction of neodymium and europium nitrates with 3,5,14,16-tetraazasubstituted dibenzo (d,j) (1,2,6,9,13,14) hexaazahexadeca-2,4,10,12-tetraene-7,8,15,16-tetraones. The authors carried out the investigations by means of conductimetry, UV luminescence, IR spectroscopy, and mass spectroscopy. Conductimetric titrations of the neodymium complexes were carried out on an OK-102/1 conductimeter. The luminescence spectra of the europium ion in the region of the /sup 5/D/sub 0/ ..-->.. /sup 7/F/sub 1/ and /sup 5/D/sub 0/ ..-->.. /sup 7/F/sub 2/ transitions (550-620 nm) were recorded on an ISP-51 spectrograph with an FEP-1 photoelectric attachment, using excitation by an SVD-120A mercury quartz lamp. The UV spectra of solutions of the compounds and the IR spectra of the solid substances in KBr disks were recorded on SpecordUViS and UR-20 spectrophotometers, respectively, and the mass spectra on a Varian Mat-112 spectrometer.

  3. Selective nitration and bromination of surprisingly ruffled phosphorus corroles.

    Science.gov (United States)

    Pomarico, Giuseppe; Tortora, Luca; Fronczek, Frank R; Smith, Kevin M; Paolesse, Roberto

    2016-05-01

    Phosphorus complexes of corrole have recently attracted increasing interest since these compounds can be easily prepared in good yields, are stable, and show unusual optical properties. For these reasons, phosphorus corroles represent a class of interesting compounds to be exploited in the field of material science or for biomedical investigations and the definition of synthetic pathways for their functionalization is an important step to optimize their properties for various applications. We report here the reactivity of the phosphorus complex of 5,10,15-tritolylcorrole in the nitration or bromination reaction. Both these attempts were successful, allowing the preparation of substituted phosphorus corroles, which can be used as intermediates of more complex architectures endowed with useful properties. Furthermore, the crystallographic characterization of both complexes shows that they have an unusual ruffled geometry of the corrole core, a conformation that has not been considered possible for such a macrocycle.

  4. Modeling nitrate removal in a denitrification bed.

    Science.gov (United States)

    Ghane, Ehsan; Fausey, Norman R; Brown, Larry C

    2015-03-15

    Denitrification beds are promoted to reduce nitrate load in agricultural subsurface drainage water to alleviate the adverse environmental effects associated with nitrate pollution of surface water. In this system, drainage water flows through a trench filled with a carbon media where nitrate is transformed into nitrogen gas under anaerobic conditions. The main objectives of this study were to model a denitrification bed treating drainage water and evaluate its adverse greenhouse gas emissions. Field experiments were conducted at an existing denitrification bed. Evaluations showed very low greenhouse gas emissions (mean N2O emission of 0.12 μg N m(-2) min(-1)) from the denitrification bed surface. Field experiments indicated that nitrate removal rate was described by Michaelis-Menten kinetics with the Michaelis-Menten constant of 7.2 mg N L(-1). We developed a novel denitrification bed model based on the governing equations for water flow and nitrate removal kinetics. The model evaluation statistics showed satisfactory prediction of bed outflow nitrate concentration during subsurface drainage flow. The model can be used to design denitrification beds with efficient nitrate removal which in turn leads to enhanced drainage water quality.

  5. Catalytic wet peroxide oxidation of azo dye (Direct Blue 15) using solvothermally synthesized copper hydroxide nitrate as catalyst.

    Science.gov (United States)

    Zhan, Yuzhong; Zhou, Xiang; Fu, Bei; Chen, Yiliang

    2011-03-15

    Copper hydroxide nitrate (Cu(2)(OH)(3)NO(3)) was synthesized solvothermally in anhydrous ethanol and characterized by XRD, FTIR, TG-DTA and SEM. The peroxide degradation of an azo dye (Direct Blue 15) on this material was evaluated by examining catalyst loading, initial pH, hydrogen peroxide dosage, initial dye concentration and temperature. The leaching of Cu from the copper hydroxide nitrate during the reaction was also measured. The copper hydroxide nitrate synthesized solvothermally, which was of a novel spherical morphology with complex secondary structures and contained high-dispersed Cu(2)O impurity, showed good performance for oxidation degradation of the azo dye, especially high catalytic activity, high utilization of hydrogen peroxide and a wide pH range, whereas the copper hydroxide nitrate synthesized by the direct reaction of copper nitrate and sodium hydroxide showed low catalytic activity. Copyright © 2011 Elsevier B.V. All rights reserved.

  6. Photodegradation of Paracetamol in Nitrate Solution

    Science.gov (United States)

    Meng, Cui; Qu, Ruijuan; Liang, Jinyan; Yang, Xi

    2010-11-01

    The photodegradation of paracetamol in nitrate solution under simulated solar irradiation has been investigated. The degradation rates were compared by varying environmental parameters including concentrations of nitrate ion, humic substance and pH values. The quantifications of paracetamol were conducted by HPLC method. The results demonstrate that the photodegradation of paracetamol followed first-order kinetics. The photoproducts and intermediates of paracetamol in the presence of nitrate ions were identified by extensive GC-MS method. The photodegradation pathways involving. OH radicals as reactive species were proposed.

  7. Nitration of Tyrosine Residue Y10 of Aβ1-42 Significantly Inhibits Its Aggregation and Cytotoxicity.

    Science.gov (United States)

    Zhao, Jie; Wu, Jinming; Yang, Zhen; Li, Hailing; Gao, Zhonghong

    2017-04-17

    Amyloid-β plaques and oxidative stress are the major hallmarks of Alzheimer's disease. Our previous study found that the heme-Aβ complex enhanced the catalytic effect of free heme on protein tyrosine nitration in the presence of hydrogen peroxide (H2O2) and nitrite (NO2(-)). Y10 in Aβ could be the first target to be nitrated. We also found that nitration of Aβ1-40 significantly decreased its aggregation. However, a contrary report showed that nitration of Aβ1-42 by peroxynitrite enhanced its aggregation. To rule out the interference of peroxynitrite caused Aβ oxidation, we used synthetic Y10 nitrated Aβ1-42 to study the influence of Y10 nitration on Aβ1-42's aggregation and cytotoxicity in this study. We confirmed that Aβ1-42 could be nitrated in the presence of H2O2, NO2(-), and heme by dot blotting. CD spectroscopy showed an increase of β-sheet structure of Aβ1-42 and its mutants. The thioflavin T (ThT) flourescence assay revealed that both nitration and chlorination significantly inhibited Aβ1-42 fibril formation. TEM and AFM observations of Aβ peptide aggregates further confirmed that Y10 modification inhibited Aβ1-42 fibril formation. The cytotoxicity study of native and modified Aβ peptides on SH-SY5Y cells revealed that nitration of Aβ1-42 remarkably decreased the neurotoxicity of Aβ1-42. On the basis of these results, we hypothesized that nitration of Y10 may block the π-π stacking interactions of Aβ1-42 so that it inhibit its aggregation and neurotoxicity. More importantly, considerable evidence suggested that the levels of nitrite plus nitrate significantly decreased in the brain of AD patients. Thus, we believe that these findings would be helpful for further understanding the function of Aβ in AD.

  8. 77 FR 65532 - Solid Fertilizer Grade Ammonium Nitrate From the Russian Federation: Notice of Rescission of...

    Science.gov (United States)

    2012-10-29

    ... International Trade Administration Solid Fertilizer Grade Ammonium Nitrate From the Russian Federation: Notice... the antidumping duty order on solid fertilizer grade ammonium nitrate (ammonium nitrate) from the... Administrative Review: Solid Fertilizer Grade Ammonium Nitrate (Ammonium Nitrate) from the Russian...

  9. Analytical Chemistry and Materials Characterization Results for Debris Recovered from Nitrate Salt Waste Drum S855793

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Patrick Thomas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Chamberlin, Rebecca M. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Schwartz, Daniel S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Worley, Christopher Gordon [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Garduno, Katherine [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lujan, Elmer J. W. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Borrego, Andres Patricio [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Castro, Alonso [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Colletti, Lisa Michelle [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Fulwyler, James Brent [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Holland, Charlotte S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Keller, Russell C. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Klundt, Dylan James [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Martinez, Alexander [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Martin, Frances Louise [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Montoya, Dennis Patrick [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Myers, Steven Charles [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Porterfield, Donivan R. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Schake, Ann Rene [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Schappert, Michael Francis [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Soderberg, Constance B. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Spencer, Khalil J. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Stanley, Floyd E. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Thomas, Mariam R. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Townsend, Lisa Ellen [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Xu, Ning [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2015-09-16

    Solid debris was recovered from the previously-emptied nitrate salt waste drum S855793. The bulk sample was nondestructively assayed for radionuclides in its as-received condition. Three monoliths were selected for further characterization. Two of the monoliths, designated Specimen 1 and 3, consisted primarily of sodium nitrate and lead nitrate, with smaller amounts of lead nitrate oxalate and lead oxide by powder x-ray diffraction. The third monolith, Specimen 2, had a complex composition; lead carbonate was identified as the predominant component, and smaller amounts of nitrate, nitrite and carbonate salts of lead, magnesium and sodium were also identified. Microfocused x-ray fluorescence (MXRF) mapping showed that lead was ubiquitous throughout the cross-sections of Specimens 1 and 2, while heteroelements such as potassium, calcium, chromium, iron, and nickel were found in localized deposits. MXRF examination and destructive analysis of fragments of Specimen 3 showed elevated concentrations of iron, which were broadly distributed through the sample. With the exception of its high iron content and low carbon content, the chemical composition of Specimen 3 was within the ranges of values previously observed in four other nitrate salt samples recovered from emptied waste drums.

  10. Denitrification of nitrate waste solutions

    Energy Technology Data Exchange (ETDEWEB)

    Bertolami, R.J.; Chao, E.I.; Choi, W.M.; Johnson, B.R.; Varlet, J.L.P.

    1976-04-26

    Growth rates for the denitrifying bacteria Pseudomonas Stutzeri were studied to minimize the time necessary to start up a bacterial denitrification reactor. Batch experiments were performed in nine 250-ml Erlenmeyer flasks, a 7-liter fermentor, and a 67-liter fermentor. All reactors maintained an anaerobic environment. Initial microorganism inoculum concentration was varied over four orders of magnitude. Initial nitrate and substrate carbon concentrations were varied from 200 to 6000 ppm and from 56 to 1596 ppm, respectively, with a carbon-to-nitrogen weight ratio of 1.18. In all experiments, except those with the highest initial substrate-to-bacteria ratio, no growth was observed due to substrate depletion during the lag period. In those experiments which did exhibit an increase in bacterial population, growth also stopped due to substrate depletion. A model simulating microbe growth during the induction period was developed, but insufficient data were available to properly adjust the model constants. Because of this, the model does not accurately predict microbe growth. The metabolism of Pseudomonas Stutzeri was studied in detail. This resulted in a prediction of the denitrification stoichiometry during steady state reactor operation. Iron was found to be an important component for bacterial anabolism.

  11. Removal of Nitrate from Groundwater by Cyanobacteria: Quantitative Assessment of Factors Influencing Nitrate Uptake

    OpenAIRE

    Hu, Qiang; Westerhoff, Paul; Vermaas, Wim

    2000-01-01

    The feasibility of biologically removing nitrate from groundwater was tested by using cyanobacterial cultures in batch mode under laboratory conditions. Results demonstrated that nitrate-contaminated groundwater, when supplemented with phosphate and some trace elements, can be used as growth medium supporting vigorous growth of several strains of cyanobacteria. As cyanobacteria grew, nitrate was removed from the water. Of three species tested, Synechococcus sp. strain PCC 7942 displayed the h...

  12. ROE Wet Nitrate Deposition 1989-1991

    Data.gov (United States)

    U.S. Environmental Protection Agency — The raster data represent the amount of wet nitrate deposition in kilograms per hectare from 1989 to 1991. Summary data in this indicator were provided by EPA’s...

  13. ROE Wet Nitrate Deposition 2011-2013

    Data.gov (United States)

    U.S. Environmental Protection Agency — The raster data represent the amount of wet nitrate deposition in kilograms per hectare from 2011 to 2013. Summary data in this indicator were provided by EPA’s...

  14. Spectrophotometric Determination of Nitrate and Phosphate Levels ...

    African Journals Online (AJOL)

    MBI

    2013-04-09

    Apr 9, 2013 ... Drinking Water Samples in The Vicinity of Irrigated Farmlands of Kura ... of Kura irrigated farmlands using polythene plastic containers and were analysed for the nitrate and ... polythene bottles, the bottles were covered with.

  15. Nitrate reduction in geologically heterogeneous catchments

    DEFF Research Database (Denmark)

    Refsgaard, Jens Christian; Auken, Esben; Bamberg, C.A.

    2014-01-01

    In order to fulfil the requirements of the EU Water Framework Directive nitrate load from agricultural areas to surface water in Denmark needs to be reduced by about 40%. The regulations imposed until now have been uniform, i.e. the same restrictions for all areas independent of the subsurface...... conditions. Studies have shown that on a national basis about 2/3 of the nitrate leaching from the root zone is reduced naturally, through denitrification, in the subsurface before reaching the streams. Therefore, it is more cost-effective to identify robust areas, where nitrate leaching through the root...... the entire catchment. However, as distributed models often do not include local scale hydrogeological heterogeneities, they are typically not able to make accurate predictions at scales smaller than they are calibrated. We present a framework for assessing nitrate reduction in the subsurface...

  16. Nitrate Waste Treatment Sampling and Analysis Plan

    Energy Technology Data Exchange (ETDEWEB)

    Vigil-Holterman, Luciana R. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Martinez, Patrick Thomas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Garcia, Terrence Kerwin [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-07-05

    This plan is designed to outline the collection and analysis of nitrate salt-bearing waste samples required by the New Mexico Environment Department- Hazardous Waste Bureau in the Los Alamos National Laboratory (LANL) Hazardous Waste Facility Permit (Permit).

  17. Qualitative Determination of Nitrate with Triphenylbenzylphosphonium Chloride.

    Science.gov (United States)

    Berry, Donna A.; Cole, Jerry J.

    1984-01-01

    Discusses two procedures for the identification of nitrate, the standard test ("Brown Ring" test) and a new procedure using triphenylbenzylphosphonium chloride (TPBPC). Effectiveness of both procedures is compared, with the TPBPC test proving to be more sensitive and accurate. (JM)

  18. 76 FR 70366 - Ammonium Nitrate Security Program

    Science.gov (United States)

    2011-11-14

    ...- accessible Internet access could obtain the access necessary to register online. 3. How to best notify... ammonium nitrate sellers (AN Sellers) when it is not possible for an AN Seller to verify the identity of...

  19. The Arabidopsis ATNRT2.7 nitrate transporter controls nitrate content in seeds.

    Science.gov (United States)

    Chopin, Franck; Orsel, Mathilde; Dorbe, Marie-France; Chardon, Fabien; Truong, Hoai-Nam; Miller, Anthony J; Krapp, Anne; Daniel-Vedele, Françoise

    2007-05-01

    In higher plants, nitrate is taken up by root cells where Arabidopsis thaliana NITRATE TRANSPORTER2.1 (ATNRT2.1) chiefly acts as the high-affinity nitrate uptake system. Nitrate taken up by the roots can then be translocated from the root to the leaves and the seeds. In this work, the function of the ATNRT2.7 gene, one of the seven members of the NRT2 family in Arabidopsis, was investigated. High expression of the gene was detected in reproductive organs and peaked in dry seeds. beta-Glucuronidase or green fluorescent protein reporter gene expression driven by the ATNRT2.7 promoter confirmed this organ specificity. We assessed the capacity of ATNRT2.7 to transport nitrate in Xenopus laevis oocytes or when it is expressed ectopically in mutant plants deficient in nitrate transport. We measured the impact of an ATNRT2.7 mutation and found no difference from the wild type during vegetative development. By contrast, seed nitrate content was affected by overexpression of ATNRT2.7 or a mutation in the gene. Finally, we showed that this nitrate transporter protein was localized to the vacuolar membrane. Our results demonstrate that ATNRT2.7 plays a specific role in nitrate accumulation in the seed.

  20. Organic nitrates and nitrate tolerance--state of the art and future developments.

    Science.gov (United States)

    Daiber, Andreas; Münzel, Thomas; Gori, Tommaso

    2010-01-01

    The hemodynamic and antiischemic effects of nitroglycerin (GTN) are lost upon chronic administration due to the rapid development of nitrate tolerance. The mechanism of this phenomenon has puzzled several generations of scientists, but recent findings have led to novel hypotheses. The formation of reactive oxygen and nitrogen species in the mitochondria and the subsequent inhibition of the nitrate-bioactivating enzyme mitochondrial aldehyde dehydrogenase (ALDH-2) appear to play a central role, at least for GTN, that is, bioactivated by ALDH-2. Importantly, these findings provide the opportunity to reconcile the two "traditional" hypotheses of nitrate tolerance, that is, the one postulating a decreased bioactivation and the concurrent one suggesting a role of oxidative stress. Furthermore, recent animal and human experimental studies suggest that the organic nitrates are not a homogeneous group but demonstrate a broad diversity with regard to induction of vascular dysfunction, oxidative stress, and other side effects. In the past, attempts to avoid nitrate-induced side effects have focused on administration schedules that would allow a "nitrate-free interval"; in the future, the role of co-therapies with antioxidant compounds and of activation of endogeneous protective pathways such as the heme oxygenase 1 (HO-1) will need to be explored. However, the development of new nitrates, for example, tolerance-free aminoalkyl nitrates or combination of nitrate groups with established cardiovascular drugs like ACE inhibitors or AT(1)-receptor blockers (hybrid molecules) may be of great clinical interest.

  1. Biodegradation of Glycidol and Glycidyl Nitrate

    OpenAIRE

    1982-01-01

    When calcium hydroxide is used to desensitize glycerol trinitrate (nitroglycerine)-containing waste streams, the epoxides glycidol and glycidyl nitrate are formed. The epoxide rings of both compounds are unstable to heat in aqueous solutions, and they open to form glycerol 1-mononitrate and presumably glycerol. These transformations were accelerated by microbial activity. Glycerol 1-mononitrate was slowly denitrated to form glycerol. Glycidol and glycidyl nitrate caused base-pair substitution...

  2. Preformed Nitrate in the Glacial North Atlantic

    Science.gov (United States)

    Homola, K.; Spivack, A. J.; D'Hondt, S.; Estes, E. R.; Insua, T. L.; McKinley, C. C.; Murray, R. W.; Pockalny, R. A.; Robinson, R. S.; Sauvage, J.

    2015-12-01

    Atmospheric CO2 abundances are highly correlated with global temperature variations over the past 800,000 years. Consequently, understanding the feedbacks between climate and CO2 is important for predictions of future climate. Leading hypotheses to explain this feedback invoke changes in ocean biology, circulation, chemistry, and/or gas exchange rates to trap CO2 in the deep ocean, thereby reducing the greenhouse effect of CO2 in the atmosphere. To test these hypotheses, we use sediment pore water profiles of dissolved nitrate and oxygen to reconstruct paleo-preformed nitrate concentrations at two deep-water sites in the western North Atlantic (23°N 57°W, 5557 m water depth; 30°N 58°W, 5367 m water depth). Preformed nitrate increases down-core to 22.7 μM (25.6 m core depth) at the northern site, and to 28.5 μM (27.8 m core depth) at the southern site. The large preformed nitrate gradient between these sites reveals a paleo-boundary between a southern water source high in preformed nitrate and a northern water source with lower concentrations, similar to today's ocean. However, the boundary between these water masses occurs north of where their modern counterparts meet, indicating that Antarctic Bottom Water (AABW) extended farther north during the Last Glacial Maximum (LGM). In addition, the southern source had a higher preformed nitrate concentration than today's AABW (25 μM), contradicting hypotheses that nutrient utilization was more efficient in the Southern Ocean deep-water formation regions during the LGM. Comparison to our previous Pacific data reveals that the average preformed nitrate concentration of the deep ocean was slightly higher during the LGM than today. This result implies that the CO2-climate feedback was not principally due to more efficient nitrate utilization.

  3. Is beetroot juice more effective than sodium nitrate? The effects of equimolar nitrate dosages of nitrate-rich beetroot juice and sodium nitrate on oxygen consumption during exercise.

    Science.gov (United States)

    Flueck, Joelle Leonie; Bogdanova, Anna; Mettler, Samuel; Perret, Claudio

    2016-04-01

    Dietary nitrate has been reported to lower oxygen consumption in moderate- and severe-intensity exercise. To date, it is unproven that sodium nitrate (NaNO3(-); NIT) and nitrate-rich beetroot juice (BR) have the same effects on oxygen consumption, blood pressure, and plasma nitrate and nitrite concentrations or not. The aim of this study was to compare the effects of different dosages of NIT and BR on oxygen consumption in male athletes. Twelve healthy, well-trained men (median [minimum; maximum]; peak oxygen consumption: 59.4 mL·min(-1)·kg(-1) [40.5; 67.0]) performed 7 trials on different days, ingesting different nitrate dosages and placebo (PLC). Dosages were 3, 6, and 12 mmol nitrate as concentrated BR or NIT dissolved in plain water. Plasma nitrate and nitrite concentrations were measured before, 3 h after ingestion, and postexercise. Participants cycled for 5 min at moderate intensity and further 8 min at severe intensity. End-exercise oxygen consumption at moderate intensity was not significantly different between the 7 trials (p = 0.08). At severe-intensity exercise, end-exercise oxygen consumption was ~4% lower in the 6-mmol BR trial compared with the 6-mmol NIT (p = 0.003) trial as well as compared with PLC (p = 0.010). Plasma nitrite and nitrate concentrations were significantly increased after the ingestion of BR and NIT with the highest concentrations in the 12-mmol trials. Plasma nitrite concentration between NIT and BR did not significantly differ in the 6-mmol (p = 0.27) and in the 12-mmol (p = 0.75) trials. In conclusion, BR might reduce oxygen consumption to a greater extent compared with NIT.

  4. Synthesis of a new energetic nitrate ester

    Energy Technology Data Exchange (ETDEWEB)

    Chavez, David E [Los Alamos National Laboratory

    2008-01-01

    Nitrate esters have been known as useful energetic materials since the discovery of nitroglycerin by Ascanio Sobrero in 1846. The development of methods to increase the safety and utility of nitroglycerin by Alfred Nobel led to the revolutionary improvement in the utility of nitroglycerin in explosive applications in the form of dynamite. Since then, many nitrate esters have been prepared and incorporated into military applications such as double-based propellants, detonators and as energetic plasticizers. Nitrate esters have also been shown to have vasodilatory effects in humans and thus have been studied and used for treatments of ailments such as angina. The mechanism of the biological response towards nitrate esters has been elucidated recently. Interestingly, many of the nitrate esters used for military purposes are liquids (ethylene glycol dinitrate, propylene glycol dinitrate, etc). Pentaerythritol tetranitrate (PETN) is one of the only solid nitrate esters, besides nitrocellulose, that is used in any application. Unfortunately, PETN melting point is above 100 {sup o}C, and thus must be pressed as a solid for detonator applications. A more practical material would be a melt-castable explosive, for potential simplification of manufacturing processes. Herein we describe the synthesis of a new energetic nitrate ester (1) that is a solid at ambient temperatures, has a melting point of 85-86 {sup o}C and has the highest density of any known nitrate ester composed only of carbon, hydrogen, nitrogen and oxygen. We also describe the chemical, thermal and sensitivity properties of 1 as well as some preliminary explosive performance data.

  5. Stimulating nitrate removal processes of restored wetlands.

    Science.gov (United States)

    Ballantine, Kate A; Groffman, Peter M; Lehmann, Johannes; Schneider, Rebecca L

    2014-07-01

    The environmental and health effects caused by nitrate contamination of aquatic systems are a serious problem throughout the world. A strategy proposed to address nitrate pollution is the restoration of wetlands. However, although natural wetlands often remove nitrate via high rates of denitrification, wetlands restored for water quality functions often fall below expectations. This may be in part because key drivers for denitrification, in particular soil carbon, are slow to develop in restored wetlands. We added organic soil amendments that range along a gradient of carbon lability to four newly restored wetlands in western New York to investigate the effect of carbon additions on denitrification and other processes of the nitrogen cycle. Soil carbon increased by 12.67-63.30% with the use of soil amendments (p ≤ 0.0001). Soil nitrate, the carbon to nitrogen ratio, and microbial biomass nitrogen were the most significant predictors of denitrification potential. Denitrification potential, potential net nitrogen nitrification and mineralization, and soil nitrate and ammonium, were highest in topsoil-amended plots, with increases in denitrification potential of 161.27% over control plots. While amendment with topsoil more than doubled several key nitrogen cycling processes, more research is required to determine what type and level of amendment application are most effective for stimulating removal of exogenous nitrate and meeting functional goals within an acceptable time frame.

  6. Nitrate Adsorption on Clay Kaolin: Batch Tests

    Directory of Open Access Journals (Sweden)

    Morteza Mohsenipour

    2015-01-01

    Full Text Available Soils possessing kaolin, gibbsite, goethite, and hematite particles have been found to have a natural capacity to attenuate pollution in aqueous phase. On the other hand, the hydroxyl group in soil increases anion exchange capacity under a low pH condition. The main objective of this paper was to evaluate effects of kaolin on nitrate reduction under acidic condition. In order to analyze the kaolin adsorption behaviour under various conditions, four different concentrations of nitrate, 45, 112.5, 225, and 450 mgNO3-/L, with a constant pH equal to 2, constant temperature equal to 25°C, and exposure period varying from 0 to 150 minutes were considered. The capacity of nitrate adsorption on kaolin has also been studied involving two well-known adsorption isotherm models, namely, Freundlich and Longmuir. The results revealed that approximately 25% of the nitrate present in the solution was adsorbed on clay kaolin. The laboratory experimental data revealed that Freundlich adsorption isotherm model was more accurate than Longmuir adsorption model in predicting of nitrate adsorption. Furthermore, the retardation factor of nitrate pollution in saturated zone has been found to be approximately 4 in presence of kaolin, which indicated that kaolin can be used for natural scavenger of pollution in the environment.

  7. Radiation-induced nitration of organic compounds in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Ershov, B.G.; Gordeev, A.V.; Bykov, G.L. [Russian Academy of Sciences, Moscow (Russian Federation). Frumkin Inst. of Physical Chemistry and Electrochemistry; Moisy, P. [CEA, Bagnols sur Ceze (France). Nuclear Energy Div.

    2012-07-01

    Radiolysis in aqueous nitrate and acetic acid solutions and nitrate/nitric acid and phenol was studied. The radiolysis of these solutes occurs with {sup circle} NO{sup 2} radical, which is the active nitrating agent. Accumulation of nitromethane and nitrite was determined during {gamma}-irradiation of aqueous solutions containing acetic and nitrate solutions. Irradiation of aqueous phenol-nitrate/nitric acid solutions results in the formation of 2- and 4-nitrophenols.

  8. Nitrate Biogeochemistry and Reactive Transport in California Groundwater: LDRD Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Esser, B K; Beller, H; Carle, S; Cey, B; Hudson, G B; Leif, R; LeTain, T; Moody-Bartel, C; Moore, K; McNab, W; Moran, J; Tompson, A

    2006-02-24

    Nitrate is the number one drinking water contaminant in the United States. It is pervasive in surface and groundwater systems,and its principal anthropogenic sources have increased dramatically in the last 50 years. In California alone, one third of the public drinking-water wells has been lost since 1988 and nitrate contamination is the most common reason for abandonment. Effective nitrate management in groundwater is complicated by uncertainties related to multiple point and non-point sources, hydrogeologic complexity, geochemical reactivity, and quantification of denitrification processes. In this paper, we review an integrated experimental and simulation-based framework being developed to study the fate of nitrate in a 25 km-long groundwater subbasin south of San Jose, California, a historically agricultural area now undergoing rapid urbanization with increasing demands for groundwater. The modeling approach is driven by a need to integrate new and archival data that support the hypothesis that nitrate fate and transport at the basin scale is intricately related to hydrostratigraphic complexity, variability of flow paths and groundwater residence times, microbial activity, and multiple geochemical reaction mechanisms. This study synthesizes these disparate and multi-scale data into a three-dimensional and highly resolved reactive transport modeling framework.

  9. Historical Tracking of Nitrate in Contrasting Vineyard Using Water Isotopes and Nitrate Depth Profiles

    Science.gov (United States)

    Sprenger, M.; Erhardt, M.; Riedel, M.; Weiler, M.

    2015-12-01

    The European Water Framework Directive (EWFD) aims to achieve a good chemical status for the groundwater bodies in Europe by the year 2015. Despite the effort to reduce the nitrate pollution from agriculture within the last two decades, there are still many groundwater aquifers that exceed nitrate concentrations above the EWFD threshold of 50 mg/l. Viticulture is seen as a major contributor of nitrate leaching and sowing of a green cover was shown to have a positive effect on lowering the nitrate loads in the upper 90 cm of the soil. However, the consequences for nitrate leaching into the subsoil were not yet tested. We analyzed the nitrate concentrations and pore water stable isotope composition to a depth of 380 cm in soil profiles under an old vineyard and a young vineyard with either soil tillage or permanent green cover in between the grapevines. The pore water stable isotopes were used to calibrate a soil physical model, which was then used to infer the age of the soil water at different depths. This way, we could relate elevated nitrate concentrations below an old vineyard to tillage processes that took place during the winter two years before the sampling. We further showed that the elevated nitrate concentration in the subsoil of a young vineyard can be related to the soil tillage prior to the planting of the new vineyard. If the soil is kept bare due to tillage, a nitrate concentration of 200 kg NO3--N/ha is found in 290 to 380 cm depth 2.5 years after the installation of the vineyard. The amount of nitrate leaching is considerably reduced due to a seeded green cover between the grapevines that takes up a high share of the mobilized nitrate reducing a potential contamination of the groundwater.

  10. Timescales for nitrate contamination of spring waters, northern Florida, USA

    Science.gov (United States)

    Katz, B.G.; Böhlke, J.K.; Hornsby, H.D.

    2001-01-01

    Residence times of groundwater, discharging from springs in the middle Suwannee River Basin, were estimated using chlorofluorocarbons (CFCs), tritium (3H), and tritium/helium-3 (3H/3He) age-dating methods to assess the chronology of nitrate contamination of spring waters in northern Florida. During base-flow conditions for the Suwannee River in 1997-1999, 17 water samples were collected from 12 first, second, and third magnitude springs discharging groundwater from the Upper Floridan aquifer. Extending age-dating techniques, using transient tracers to spring waters in complex karst systems, required an assessment of several models [piston-flow (PFM), exponential mixing (EMM), and binary-mixing (BMM)] to account for different distributions of groundwater age. Multi-tracer analyses of four springs yielded generally concordant PFM ages of around 20 ?? 2 years from CFC-12, CFC-113, 3H, and 3He, with evidence of partial CFC-11 degradation. The EMM gave a reasonable fit to CFC-113, CFC-12, and 3H data, but did not reproduce the observed 3He concentrations or 3H/3He ratios, nor did a combination PFM-EMM. The BMM could reproduce most of the multi-tracer data set only if both endmembers had 3H concentrations not much different from modern values. CFC analyses of 14 additional springs yielded apparent PFM ages from about 10 to 20 years from CFC-113, with evidence of partial CFC-11 degradation and variable CFC-12 contamination. While it is not conclusive, with respect to the age distribution within each spring, the data indicate that the average residence times were in the order of 10-20 years and were roughly proportional to spring magnitude. Applying similar models to recharge and discharge of nitrate based on historical nitrogen loading data yielded contrasting trends for Suwanee County and Lafayette County. In Suwanee County, spring nitrate trends and nitrogen isotope data were consistent with a peak in fertilizer input in the 1970s and a relatively high overall ratio of

  11. Nitrate in aquifers beneath agricultural systems.

    Science.gov (United States)

    Burkart, M R; Stoner, J D

    2007-01-01

    Research from several regions of the world provides spatially anecdotal evidence to hypothesize which hydrologic and agricultural factors contribute to groundwater vulnerability to nitrate contamination. Analysis of nationally consistent measurements from the U.S. Geological Survey's NAWQA program confirms these hypotheses for a substantial range of agricultural systems. Shallow unconfined aquifers are most susceptible to nitrate contamination associated with agricultural systems. Alluvial and other unconsolidated aquifers are the most vulnerable and also shallow carbonate aquifers that provide a substantial but smaller contamination risk. Where any of these aquifers are overlain by permeable soils the risk of contamination is larger. Irrigated systems can compound this vulnerability by increasing leaching facilitated by additional recharge and additional nutrient applications. The system of corn, soybean, and hogs produced significantly larger concentrations of groundwater nitrate than all other agricultural systems because this system imports the largest amount of N-fertilizer per unit production area. Mean nitrate under dairy, poultry, horticulture, and cattle and grains systems were similar. If trends in the relation between increased fertilizer use and groundwater nitrate in the United States are repeated in other regions of the world, Asia may experience increasing problems because of recent increases in fertilizer use. Groundwater monitoring in Western and Eastern Europe as well as Russia over the next decade may provide data to determine if the trend in increased nitrate contamination can be reversed. If the concentrated livestock trend in the United States is global, it may be accompanied by increasing nitrogen contamination in groundwater. Concentrated livestock provide both point sources in the confinement area and intense non-point sources as fields close to facilities are used for manure disposal. Regions where irrigated cropland is expanding, such as

  12. In vivo nitrate tolerance is not associated with reduced bioconversion of nitroglycerin to nitric oxide

    DEFF Research Database (Denmark)

    Laursen, J B; Mülsch, A; Boesgaard, S;

    1996-01-01

    left untreated (control). Nitrate tolerance was substantiated by a reduced (55% to 85%) hypotensive response to NTG in vivo and a reduced relaxation to NTG in isolated aortic rings. NTG-derived NO formation in aorta, vena cava, heart, and liver was measured as NOFe(DETC)2 and NO-heme complexes formed...

  13. Electron transport to periplasmic nitrate reductase (NapA) of Wolinella succinogenes is independent of a NapC protein.

    Science.gov (United States)

    Simon, Jörg; Sänger, Monica; Schuster, Stephan C; Gross, Roland

    2003-07-01

    The rumen bacterium Wolinella succinogenes grows by respiratory nitrate ammonification with formate as electron donor. Whereas the enzymology and coupling mechanism of nitrite respiration is well known, nitrate reduction to nitrite has not yet been examined. We report here that intact cells and cell fractions catalyse nitrate and chlorate reduction by reduced viologen dyes with high specific activities. A gene cluster encoding components of a putative periplasmic nitrate reductase system (napA, G, H, B, F, L, D) was sequenced. The napA gene was inactivated by inserting a kanamycin resistance gene cassette. The resulting mutant did not grow by nitrate respiration and did not reduce nitrate during growth by fumarate respiration, in contrast to the wild type. An antigen was detected in wild-type cells using an antiserum raised against the periplasmic nitrate reductase (NapA) from Paracoccus pantotrophus. This antigen was absent in the W. succinogenes napA mutant. It is concluded that the periplasmic nitrate reductase NapA is the only respiratory nitrate reductase in W. succinogenes, although a second nitrate-reducing enzyme is apparently induced in the napA mutant. The nap cluster of W. succinogenes lacks a napC gene whose product is thought to function in quinol oxidation and electron transfer to NapA in other bacteria. The W. succinogenes genome encodes two members of the NapC/NirT family, NrfH and FccC. Characterization of corresponding deletion mutants indicates that neither of these two proteins is required for nitrate respiration. A mutant lacking the genes encoding respiratory nitrite reductase (nrfHA) had wild-type properties with respect to nitrate respiration. A model of the electron transport chain of nitrate respiration is proposed in which one or more of the napF, G, H and L gene products mediate electron transport from menaquinol to the periplasmic NapAB complex. Inspection of the W. succinogenes genome sequence suggests that ammonia formation from

  14. Observations of Alkyl Nitrates during ARCTAS: Investigation of the low NOx Chemistry of Isoprene Nitrates

    Science.gov (United States)

    Browne, E. C.; Cohen, R. C.; Wooldridge, P. J.; Min, K.; Apel, E. C.; Blake, D. R.; Brune, W. H.; Fried, A.; Ren, X.; Weinheimer, A. J.; Wisthaler, A.; Team, A. S.

    2009-12-01

    During numerous ground and airborne experiments alkyl and multifunctional nitrates, measured by Thermal Dissociation-Laser Induced Fluorescence, have been shown to represent a significant fraction of oxidized nitrogen. It is postulated that a large fraction of these nitrates, particularly in forested environments, are isoprene-derived nitrates. The formation of these nitrates is important in terminating photochemical ozone production. However, it is still highly uncertain if these nitrates serve as a permanent termination step or only as a temporary sink that upon further oxidation, releases NO2 back into the atmosphere. The summer portion of the NASA ARCTAS experiment allows us to investigate the role of alkyl nitrates in photochemical ozone production in a new regime: the low NOx of the summer boreal forest. This data set also represents the first time that vertical profiles of the isoprene oxidation products methyl vinyl ketone and methacrolein were obtained along with total alkyl nitrates. We use these measurements to investigate and constrain the low NOx chemistry of isoprene nitrates. We compare these measurements to past airborne and laboratory studies.

  15. Nitrate removal from high strength nitrate-bearing wastes in granular sludge sequencing batch reactors.

    Science.gov (United States)

    Krishna Mohan, Tulasi Venkata; Renu, Kadali; Nancharaiah, Yarlagadda Venkata; Satya Sai, Pedapati Murali; Venugopalan, Vayalam Purath

    2016-02-01

    A 6-L sequencing batch reactor (SBR) was operated for development of granular sludge capable of denitrification of high strength nitrates. Complete and stable denitrification of up to 5420 mg L(-1) nitrate-N (2710 mg L(-1) nitrate-N in reactor) was achieved by feeding simulated nitrate waste at a C/N ratio of 3. Compact and dense denitrifying granular sludge with relatively stable microbial community was developed during reactor operation. Accumulation of large amounts of nitrite due to incomplete denitrification occurred when the SBR was fed with 5420 mg L(-1) NO3-N at a C/N ratio of 2. Complete denitrification could not be achieved at this C/N ratio, even after one week of reactor operation as the nitrite levels continued to accumulate. In order to improve denitrification performance, the reactor was fed with nitrate concentrations of 1354 mg L(-1), while keeping C/N ratio at 2. Subsequently, nitrate concentration in the feed was increased in a step-wise manner to establish complete denitrification of 5420 mg L(-1) NO3-N at a C/N ratio of 2. The results show that substrate concentration plays an important role in denitrification of high strength nitrate by influencing nitrite accumulation. Complete denitrification of high strength nitrates can be achieved at lower substrate concentrations, by an appropriate acclimatization strategy.

  16. The δ15N of nitrate in the Southern Ocean: Consumption of nitrate in surface waters

    Science.gov (United States)

    Sigman, D. M.; Altabet, M. A.; McCorkle, D. C.; Francois, R.; Fischer, G.

    1999-12-01

    We report nitrogen isotope data for nitrate from transects of hydrocast and surface samples collected in the eastern Indian and Pacific sectors of the Southern Ocean, focusing here on the data from the upper water column to study the effect of nitrate consumption by phytoplankton. The δ15N of nitrate increases by 1-2‰ from deep water into the Antarctic summertime surface layer, due to kinetic isotopic fractionation during nitrate uptake. Estimation of the nitrate uptake isotope effect from Antarctic depth profiles yields values in the range of 5-6‰ in east Indian sector and 4-5‰ in the east Pacific sector. Surface transect data from the Pacific sector also yield values of 4-5‰. The major uncertainty in the profile-based estimation of the isotope effect involves the δ15N of nitrate from the temperature minimum layer below the summertime Antarctic surface layer, which deviates significantly from the predictions of simple models of isotope fractionation. For the Subantarctic surface, it is possible to distinguish between nitrate supplied laterally from the surface Antarctic and nitrate supplied vertically from the Subantarctic thermocline because of the distinctive relationships between the δ15N and concentration of nitrate in these two potential sources. Our Subantarctic samples, collected during the summer and fall, indicate that nitrate is supplied to the Subantarctic surface largely by northward transport of Antarctic surface water. Isotopic data from the Pacific sector of the Subantarctic suggest an isotope effect of 4.5‰, indistinguishable from the Antarctic estimates in this sector.

  17. Microbial Reduction of Chromate in the presence of Nitrate by Three Nitrate Respiring Organisms.

    Directory of Open Access Journals (Sweden)

    Peter eChovanec

    2012-12-01

    Full Text Available A major challenge for the bioremediation of toxic metals is the co-occurrence of nitrate, as it can inhibit metal transformation. Geobacter metallireducens, Desulfovibrio desulfuricans, and Sulfurospirillum barnesii are three soil bacteria that can reduce chromate (Cr(VI and nitrate, and may be beneficial for developing bioremediation strategies. All three organisms respire through dissimilatory nitrate reduction to ammonia (DNRA, employing different nitrate reductases but similar nitrite reductase (Nrf. G. metallireducens reduces nitrate to nitrite via the membrane bound nitrate reductase (Nar, while S. barnesii and D. desulfuricans strain 27774 have slightly different forms of periplasmic nitrate reductase (Nap. We investigated the effect of DNRA growth in the presence of Cr(VI in these three organisms and the ability of each to reduce Cr(VI to Cr(III, and each organisms responded differently. Growth of G. metallireducens on nitrate was completely inhibited by Cr(VI. Cultures of D. desulfuricans on nitrate media was initially delayed (48 h in the presence of Cr(VI, but ultimately reached comparable cell yields to the non-treated control. This prolonged lag phase accompanied the transformation of Cr(VI to Cr(III. Viable G. metallireducens cells could reduce Cr(VI, whereas Cr(VI reduction by D. desulfuricans during growth, was mediated by a filterable and heat stable extracellular metabolite. S. barnesii growth on nitrate was not affected by Cr(VI, and Cr(VI was reduced to Cr(III. However, Cr(VI reduction activity in S. barnesii, was detected in both the cell free spent medium and cells, indicating both extracellular and cell associated mechanisms. Taken together, these results have demonstrated that Cr(VI affects DNRA in the three organisms differently, and that each have a unique mechanism for Cr(VI reduction.

  18. The influence of Glyceria maxima and nitrate input on the composition and nitrate metabolism of the dissimilatory nitrate-reducing bacterial community

    NARCIS (Netherlands)

    Nijburg, J.W.; Laanbroek, H.J.

    1997-01-01

    The influence of nitrate addition and the presence of Glyceria maxima (reed sweetgrass) on the composition and nitrate metabolism of the dissimilatory nitrate-reducing bacterial community was investigated. Anoxic freshwater sediment was incubated in pots with or without G. maxima and with or without

  19. The influence of Glyceria maxima and nitrate input on the composition and nitrate metabolism of the dissimilatory nitrate-reducing bacterial community

    NARCIS (Netherlands)

    Nijburg, J.W.; Laanbroek, H.J.

    1997-01-01

    The influence of nitrate addition and the presence of Glyceria maxima (reed sweetgrass) on the composition and nitrate metabolism of the dissimilatory nitrate-reducing bacterial community was investigated. Anoxic freshwater sediment was incubated in pots with or without G. maxima and with or without

  20. Exclusion of Nitrate from Frozen Aqueous Solutions

    Science.gov (United States)

    Marrocco, H. A.; Michelsen, R. R.

    2013-12-01

    Reactions occurring at the surface of ice, sea ice, and snow in Earth's cryosphere have an impact on the composition of the overlying atmosphere. In order to elucidate reaction mechanisms and model their contributions to atmospheric processes, the morphology of frozen aqueous surfaces and amounts of reactants contained therein must be determined. To this end, the exclusion of nitrate ions to the surface of frozen aqueous solutions has been studied by attenuated total reflection infrared spectroscopy (ATR-IR). In this technique the near-surface region of the frozen films are interrogated to a depth of a few hundred nanometers from the film-crystal interface. Aqueous solutions (0.001 to 0.01 M) of sodium nitrate (NaNO3), magnesium nitrate (Mg(NO3)2), and nitric acid (HNO3) were quickly frozen on the germanium ATR crystal and observed at a constant temperature of about -18°C. In addition to ice and the solutes, liquid water in varying amounts was observed in the spectra. The amount of nitrate in the surface liquid is three to four orders of magnitude higher than in the unfrozen solution. While all the nitrate salts exhibit exclusion to the unfrozen surface, the dynamics are different for different counter-ions. Results are compared to freezing point depression data and the predictions of equilibrium thermodynamics.

  1. Nitrate transceptor(s) in plants.

    Science.gov (United States)

    Gojon, Alain; Krouk, Gabriel; Perrine-Walker, Francine; Laugier, Edith

    2011-04-01

    The availability of mineral nutrients in the soil dramatically fluctuates in both time and space. In order to optimize their nutrition, plants need efficient sensing systems that rapidly signal the local external concentrations of the individual nutrients. Until recently, the most upstream actors of the nutrient signalling pathways, i.e. the sensors/receptors that perceive the extracellular nutrients, were unknown. In Arabidopsis, increasing evidence suggests that, for nitrate, the main nitrogen source for most plant species, a major sensor is the NRT1.1 nitrate transporter, also contributing to nitrate uptake by the roots. Membrane proteins that fulfil a dual nutrient transport/signalling function have been described in yeast and animals, and are called 'transceptors'. This review aims to illustrate the nutrient transceptor concept in plants by presenting the current evidence indicating that NRT1.1 is a representative of this class of protein. The various facets, as well as the mechanisms of nitrate sensing by NRT1.1 are considered, and the possible occurrence of other nitrate transceptors is discussed.

  2. Ion Pairing in Alkali Nitrate Electrolyte Solutions.

    Science.gov (United States)

    Xie, Wen Jun; Zhang, Zhen; Gao, Yi Qin

    2016-03-10

    In this study, we investigate the thermodynamics of alkali nitrate salt solutions, especially the formation of contact ion pairs between alkali cation and nitrate anion. The ion-pairing propensity shows an order of LiNO3 activity coefficients and suggest that the empirical "law of matching water affinity" is followed by these alkali nitrate salt solutions. The spatial patterns of contact ion pairs are different in the three salt solutions studied here: Li(+) forms the contact ion pair with only one oxygen of the nitrate while Na(+) and K(+) can also be shared by two oxygens of the nitrate. In reproducing the salt activity coefficient using Kirkwood-Buff theory, we find that it is essential to include electronic polarization for Li(+) which has a high charge density. The electronic continuum correction for nonpolarizable force field significantly improves the agreement between the calculated activity coefficients and their experimental values. This approach also improves the performance of the force field on salt solubility. From these two aspects, this study suggests that electronic continuum correction can be a promising approach to force-field development for ions with high charge densities.

  3. Nitrate and nitrite contents in Cuban cheese of the Gouda type.

    Science.gov (United States)

    García Rocaé, M O; del Pozo, E; Izquierdo, L; Fontaine, M

    1983-01-01

    The nitrate and nitrite contents in cheese of the Gouda type, produced by the Milk Complex of Havanna, were investigated and compared with those found in 5 types of imported cheese consumed in Cuba. No significant differences were found in the mean value (mean) of NaNO3, whereas in the mean value (mean) of NaNO2 differences were found when comparing all cheeses against each other. From these results it is inferred that the consumption of Gouda type cheese does not represent an important contribution to the daily intake of nitrates and nitrites, precursors in the synthesis of cancerogenic N-nitroso compounds.

  4. Environmentally Responsible Use of Nanomaterials for the Photocatalytic Reduction of Nitrate in Water

    Science.gov (United States)

    Doudrick, Kyle

    Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts, (2) determine the effect of water quality parameters (e.g., pH), (3) conduct responsible engineering by ensuring detection methods were in place for novel materials, and (4) develop a conceptual framework for designing nitrate-specific photocatalysts. The key issues for implementing photocatalysis for nitrate drinking water treatment were efficient nitrate removal at neutral pH and by-product selectivity toward nitrogen gases, rather than by-products that pose a human health concern (e.g., nitrite). Photocatalytic nitrate reduction was found to follow a series of proton-coupled electron transfers. The nitrate reduction rate was limited by the electron-hole recombination rate, and the addition of an electron donor (e.g., formate) was necessary to reduce the recombination rate and achieve efficient nitrate removal. Nano-sized photocatalysts with high surface areas mitigated the negative effects of competing aqueous anions. The key water quality parameter impacting by-product selectivity was pH. For pH catalysts that form a Schottky barrier, allowing for localization of electrons, were best for nitrate reduction. Silver was optimal in heterogeneous systems because of its ability to improve nitrate reduction activity and N-gas by-product selectivity, and graphene was optimal in two-electrode systems because of its ability to shuttle electrons to the working electrode. "Environmentally responsible use of nanomaterials" is to ensure that detection methods are in place for the nanomaterials tested. While methods exist for the metals and metal oxides examined, there are currently none for carbon nanotubes (CNTs) and graphene

  5. Evaluating the information content of multiple groundwater age tracers in projecting nitrate vulnerability

    Science.gov (United States)

    Alikhani, J.; Massoudieh, A.; Deinhart, A.; Visser, A.; Esser, B.; Moran, J. E.

    2015-12-01

    Nitrate is one of the major sources of contamination of groundwater in the United States and around the world. In this study the applicability of multiple groundwater age tracers including 3H, 3He, 4He, 14C, 13C, and 85Kr in projecting future trends of nitrate concentration in several long-screened, public drinking water wells in Turlock, California, where nitrate concentrations are increasing toward the regulatory limit, is studied. Several lumped parameter models (LPM)s were considered to represent the groundwater age distribution at each well, including binary mixtures between Inverse Gaussian(young) and Dirac(old), generalized inverse Gaussian, and Levy distributions . LPM model parameters and unknown physical parameters (crustal production rate of 4He, dissolved inorganic carbon contribution from rock dissolution) were estimated using a Bayesian inference, resulting in the posterior probability distribution of the parameters and therefore the uncertainty associated with each. The performance of each LPM in reproducing the data while accounting for the level of model complexity is evaluated using deviance information criteria (DIC) and Bayes Factors (BF). Historical nitrate concentration data are also evaluated as an additional tracer to refine the age distribution. We found that historical nitrate levels can reduce the uncertainty about the age distribution. LPMs with a distinct feature to represent the old fraction of groundwater (for example Inverse Gaussian-Dirac) are better at reproducing the tracer data but with the price of a larger number of parameters, which results in a larger uncertainty about the age distribution itself. Although the uncertainty regarding the shape of the age distribution remains relatively high, whether nitrate is included as a tracer or not, different models predict similar future trends in nitrate concentration.

  6. Ammonium and nitrate tolerance in lichens.

    Science.gov (United States)

    Hauck, Markus

    2010-05-01

    Since lichens lack roots and take up water, solutes and gases over the entire thallus surface, these organisms respond more sensitively to changes in atmospheric purity than vascular plants. After centuries where effects of sulphur dioxide and acidity were in the focus of research on atmospheric chemistry and lichens, recently the globally increased levels of ammonia and nitrate increasingly affect lichen vegetation and gave rise to intense research on the tolerance of lichens to nitrogen pollution. The present paper discusses the main findings on the uptake of ammonia and nitrate in the lichen symbiosis and to the tolerance of lichens to eutrophication. Ammonia and nitrate are both efficiently taken up under ambient conditions. The tolerance to high nitrogen levels depends, among others, on the capability of the photobiont to provide sufficient amounts of carbon skeletons for ammonia assimilation. Lowly productive lichens are apparently predisposed to be sensitive to excess nitrogen.

  7. Insights on nitrate respiration by Shewanella

    Directory of Open Access Journals (Sweden)

    Fengping eWang

    2015-01-01

    Full Text Available Shewanellae are well known for their ability to utilize a number of electron acceptors and are therefore considered to have important roles in element cycling in the environment, such as nitrogen cycling through dissimilatory nitrate reduction to ammonia (DNRA and denitrification. Possessing two periplasmic nitrate reductase systems (NAP-α and NAP-β is a special trait of the Shewanella genus, and both enzymes are likely to provide selective advantage to the host. This review relates the current knowledge and aspects of the nitrate respiration system of Shewanella. Specifically, the potential physiological functions and regulation mechanisms of the duo-NAP system are discussed in addition to the evolution of anaerobic respiration systems of Shewanella.

  8. Plasma nitrate and nitrite are increased by a high-nitrate supplement but not by high-nitrate foods in older adults.

    Science.gov (United States)

    Miller, Gary D; Marsh, Anthony P; Dove, Robin W; Beavers, Daniel; Presley, Tennille; Helms, Christine; Bechtold, Erika; King, S Bruce; Kim-Shapiro, Daniel

    2012-03-01

    Little is known about the effect of dietary nitrate on the nitrate/nitrite/nitric oxide cycle in older adults. We examined the effect of a 3-day control diet vs high-nitrate diet, with and without a high-nitrate supplement (beetroot juice), on plasma nitrate and nitrite kinetics and blood pressure using a randomized 4-period crossover controlled design. We hypothesized that the high-nitrate diet would show higher levels of plasma nitrate/nitrite and lower blood pressure compared with the control diet, which would be potentiated by the supplement. Participants were 8 normotensive older men and women (5 female, 3 male, 72.5 ± 4.7 years old) with no overt disease or medications that affect nitric oxide metabolism. Plasma nitrate and nitrite levels and blood pressure were measured before and hourly for 3 hours after each meal. The mean daily changes in plasma nitrate and nitrite were significantly different from baseline for both control diet + supplement (P < .001 and P = .017 for nitrate and nitrite, respectively) and high-nitrate diet + supplement (P = .001 and P = .002), but not for control diet (P = .713 and P = .741) or high-nitrate diet (P = .852 and P = .500). Blood pressure decreased from the morning baseline measure to the three 2-hour postmeal follow-up time points for all treatments, but there was no main effect for treatment. In healthy older adults, a high-nitrate supplement consumed at breakfast elevated plasma nitrate and nitrite levels throughout the day. This observation may have practical utility for the timing of intake of a nitrate supplement with physical activity for older adults with vascular dysfunction.

  9. Techniques for Measurement of Nitrate Movement in Soils

    Science.gov (United States)

    Broadbent, F. E.

    1971-01-01

    Contamination of surface and ground waters with nitrate usually involves leaching through soil of nitrate produced by mineralization of soil organic matter, decomposition of animal wastes or plant residues, or derived from fertilizers. Nitrate concentrations in the soil solution may be measured by several chemical procedures or by the nitrate electrode. since nitrate is produced throughout the soil mass it is difficult to identify a source of nitrate contamination by conventional means. This problem can be solved by use of N-15-enriched or N-15-depleted materials as tracers. The latter is particularly attractive because of the negligible possibility of the tracer hazardous to health.

  10. Stochastic Controls on Nitrate Transport and Cycling

    Science.gov (United States)

    Botter, G.; Settin, T.; Alessi Celegon, E.; Marani, M.; Rinaldo, A.

    2005-12-01

    In this paper, the impact of nutrient inputs on basin-scale nitrates losses is investigated in a probabilistic framework by means of a continuous, geomorphologically based, Montecarlo approach, which explicitly tackles the random character of the processes controlling nitrates generation, transformation and transport in river basins. This is obtained by coupling the stochastic generation of climatic and rainfall series with simplified hydrologic and biogeochemical models operating at the hillslope scale. Special attention is devoted to the spatial and temporal variability of nitrogen sources of agricultural origin and to the effect of temporally distributed rainfall fields on the ensuing nitrates leaching. The influence of random climatic variables on bio-geochemical processes affecting the nitrogen cycle in the soil-water system (e.g. plant uptake, nitrification and denitrification, mineralization), is also considered. The approach developed has been applied to a catchment located in North-Eastern Italy and is used to provide probabilistic estimates of the NO_3 load transferred downstream, which is received and accumulated in the Venice lagoon. We found that the nitrogen load introduced by fertilizations significantly affects the pdf of the nitrates content in the soil moisture, leading to prolonged risks of increased nitrates leaching from soil. The model allowed the estimation of the impact of different practices on the probabilistic structure of the basin-scale hydrologic and chemical response. As a result, the return period of the water volumes and of the nitrates loads released into the Venice lagoon has been linked directly to the ongoing climatic, pluviometric and agricultural regimes, with relevant implications for environmental planning activities aimed at achieving sustainable management practices.

  11. Parsimonious Hydrologic and Nitrate Response Models For Silver Springs, Florida

    Science.gov (United States)

    Klammler, Harald; Yaquian-Luna, Jose Antonio; Jawitz, James W.; Annable, Michael D.; Hatfield, Kirk

    2014-05-01

    Silver Springs with an approximate discharge of 25 m3/sec is one of Florida's first magnitude springs and among the largest springs worldwide. Its 2500-km2 springshed overlies the mostly unconfined Upper Floridan Aquifer. The aquifer is approximately 100 m thick and predominantly consists of porous, fractured and cavernous limestone, which leads to excellent surface drainage properties (no major stream network other than Silver Springs run) and complex groundwater flow patterns through both rock matrix and fast conduits. Over the past few decades, discharge from Silver Springs has been observed to slowly but continuously decline, while nitrate concentrations in the spring water have enormously increased from a background level of 0.05 mg/l to over 1 mg/l. In combination with concurrent increases in algae growth and turbidity, for example, and despite an otherwise relatively stable water quality, this has given rise to concerns about the ecological equilibrium in and near the spring run as well as possible impacts on tourism. The purpose of the present work is to elaborate parsimonious lumped parameter models that may be used by resource managers for evaluating the springshed's hydrologic and nitrate transport responses. Instead of attempting to explicitly consider the complex hydrogeologic features of the aquifer in a typically numerical and / or stochastic approach, we use a transfer function approach wherein input signals (i.e., time series of groundwater recharge and nitrate loading) are transformed into output signals (i.e., time series of spring discharge and spring nitrate concentrations) by some linear and time-invariant law. The dynamic response types and parameters are inferred from comparing input and output time series in frequency domain (e.g., after Fourier transformation). Results are converted into impulse (or step) response functions, which describe at what time and to what magnitude a unitary change in input manifests at the output. For the

  12. Evaluation of nitrate removal effect on groundwater using artificial neural networks

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Considering the non-linear, complex and multivariable process of biological denitrification, an activated sludge process was introduced to remove nitrate in groundwater with the aid of artificial neural networks(ANN) to evaluate the nitrate removal effect. The parameters such as COD, NH3-N, NO3--N, NO2--N, MLSS,DO, etc. , were used for input nodes, and COD , NH3 -N , NO3--N , NO2--N were selected for output nodes. Experimental ANN training results show that ANN was able to predict the output water quality parameters very well. Most of relative errors of NO3--N and COD were in the range of ± 10% and ±5% respectively. The results predicted by ANN model of nitrate removal in groundwater produced good agreement with the experimental data. Though ANN model can optimize effect of the whole system, it cannot replace the water treatment process.

  13. NITRATE-SELECTIVE ELECTRODES BASED ON THE TRINUCLEAR CHROMIUM(III PIVALATES

    Directory of Open Access Journals (Sweden)

    Mihail Revenco

    2008-06-01

    Full Text Available The paper describes the analytical potentialities of the trinuclear chromium(III complexes as potentiometric ionophores for the construction of electrodes sensitive to the presence of nitrate anion. The electroactive material containing 4,4’-bipyridil was synthesized in situ. The membrane was prepared using dioctylphthalate as a solvent mediator and poly (vinyl chloride as a polymeric matrix. The electrodes presented a slope of 56 mV/decade, a low limit of detection (3,2.10-6 mol/l, an adequate lifetime (4 months, and suitable selectivity characteristics when compared with other nitrate electrodes. The good parameters of this electrode made possible its application to the determination of nitrate in different types of fertilizers.

  14. Estimating water and nitrate leaching in tree crops using inverse modelled plant and soil hydraulic properties

    Science.gov (United States)

    Couvreur, Valentin; Kandelous, Maziar; Mairesse, Harmony; Baram, Shahar; Moradi, Ahmad; Pope, Katrin; Hopmans, Jan

    2015-04-01

    Groundwater quality is specifically vulnerable in irrigated agricultural lands in California and many other (semi-)arid regions of the world. The routine application of nitrogen fertilizers with irrigation water in California is likely responsible for the high nitrate concentrations in groundwater, underlying much of its main agricultural areas. To optimize irrigation/fertigation practices, it is essential that irrigation and fertilizers are applied at the optimal concentration, place, and time to ensure maximum root uptake and minimize leaching losses to the groundwater. The applied irrigation water and dissolved fertilizer, root nitrate and water uptake interact with soil and root properties in a complex manner that cannot easily be resolved. It is therefore that coupled experimental-modelling studies are required to allow for unravelling of the relevant complexities that result from typical variations of crop properties, soil texture and layering across farmer-managed fields. A combined field monitoring and modelling approach was developed to quantify from simple measurements the leaching of water and nitrate below the root zone. The monitored state variables are soil water content within the root zone, soil matric potential below the root zone, and nitrate concentration in the soil solution. Plant and soil properties of incremented complexity are optimized with the software HYDRUS in an inverse modelling scheme, which allows estimating leaching under constraint of hydraulic principles. Questions of optimal irrigation and fertilization timing can then be addressed using predictive results and global optimization algorithms.

  15. Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

    Science.gov (United States)

    Hiatt-Gipson, Glyn D; Mills, Graham P; Reeves, Claire E

    2016-01-01

    Summary Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a ’halide for nitrate’ substitution. Employing readily available starting materials, reagents and Horner–Wadsworth–Emmons chemistry the synthesis of easily separable, synthetically versatile ‘key building blocks’ (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, ’off the shelf’ materials. Exploiting their reactivity we have studied their ability to undergo an ‘allylic halide for allylic nitrate’ substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates (‘isoprene nitrates’) in 66–80% overall yields. Using NOESY experiments the elucidation of the carbon–carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our ‘halide for nitrate’ substitution chemistry we outline the straightforward transformation of (1R,2S)-(−)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(−)-myrtenol nitrate. PMID:27340495

  16. Nitrate removal and denitrification affected by soil characteristics in nitrate treatment wetlands.

    Science.gov (United States)

    Lin, Ying-Feng; Jing, Shuh-Ren; Lee, Der-Yuan; Chang, Yih-Feng; Shih, Kai-Chung

    2007-03-01

    Several small-scale surface flow constructed wetlands unplanted and planted (monoculture) with various macrophytes (Phragmites australis, Typha orientalis, Pennisetum purpureum, Ipomoea aquatica, and Pistia stratiotes) were established to continuously receive nitrate-contaminated groundwater. Soil characteristics and their effects on nitrate removal and soil denitrification were investigated. The results showed that planted wetland cells exhibited significantly higher (P wetland cell (1%, 0.11 microg N2O-N/g/h). However, the unplanted uncovered wetland cell showed a nitrate removal efficiency (55%) lower than but a soil denitrification rate (9.12 microg N2O-N/g/h) comparable to the planted cells. The nitrate removal rate correlated closely and positively with the soil denitrification rate for the planted cells, indicating that soil denitrification is an important process for removing nitrate in constructed wetlands. The results of nitrogen budget revealed that around 68.9-90.7% of the overall nitrogen removal could be attributed to the total denitrification. The soil denitrification rate was found to correlate significantly (P wetland soil, which accordingly were concluded as suitable indicators of soil denitrification rate and nitrate removal rate in nitrate treatment wetlands.

  17. Excess nitrate loads to coastal waters reduces nitrate removal efficiency: mechanism and implications for coastal eutrophication.

    Science.gov (United States)

    Lunau, Mirko; Voss, Maren; Erickson, Matthew; Dziallas, Claudia; Casciotti, Karen; Ducklow, Hugh

    2013-05-01

    Terrestrial ecosystems are becoming increasingly nitrogen-saturated due to anthropogenic activities, such as agricultural loading with artificial fertilizer. Thus, more and more reactive nitrogen is entering streams and rivers, primarily as nitrate, where it is eventually transported towards the coastal zone. The assimilation of nitrate by coastal phytoplankton and its conversion into organic matter is an important feature of the aquatic nitrogen cycle. Dissolved reactive nitrogen is converted into a particulate form, which eventually undergoes nitrogen removal via microbial denitrification. High and unbalanced nitrate loads to the coastal zone may alter planktonic nitrate assimilation efficiency, due to the narrow stochiometric requirements for nutrients typically shown by these organisms. This implies a cascade of changes for the cycling of other elements, such as carbon, with unknown consequences at the ecosystem level. Here, we report that the nitrate removal efficiency (NRE) of a natural phytoplankton community decreased under high, unbalanced nitrate loads, due to the enhanced recycling of organic nitrogen and subsequent production and microbial transformation of excess ammonium. NRE was inversely correlated with the amount of nitrate present, and mechanistically controlled by dissolved organic nitrogen (DON), and organic carbon (Corg) availability. These findings have important implications for the management of nutrient runoff to coastal zones.

  18. Nitrate stimulation of indigenous nitrate-reducing, sulfide-oxidising bacterial community in wastewater anaerobic biofilms.

    Science.gov (United States)

    Garcia-de-Lomas, Juan; Corzo, Alfonso; Carmen Portillo, M; Gonzalez, Juan M; Andrades, Jose A; Saiz-Jimenez, Cesáreo; Garcia-Robledo, Emilio

    2007-07-01

    The role of the nitrate-reducing, sulfide-oxidising bacteria (NR-SOB) in the nitrate-mediated inhibition of sulfide net production by anaerobic wastewater biofilms was analyzed in two experimental bioreactors, continuously fed with the primary effluent of a wastewater treatment plant, one used as control (BRC) and the other one supplemented with nitrate (BRN). This study integrated information from H(2)S and pH microelectrodes, RNA-based molecular techniques, and the time course of biofilm growth and bioreactors water phase. Biofilms were a net source of sulfide for the water phase (2.01 micromol S(2-)(tot)m(-2)s(-1)) in the absence of nitrate dosing. Nitrate addition effectively led to the cessation of sulfide release from biofilms despite which a low rate of net sulfate reduction activity (0.26 micromol S(2-)(tot)m(-2)s(-1)) persisted at a deep layer within the biofilm. Indigenous NR-SOB including Thiomicrospira denitrificans, Arcobacter sp., and Thiobacillus denitrificans were stimulated by nitrate addition resulting in the elimination of most sulfide from the biofilms. Active sulfate reducing bacteria (SRB) represented comparable fractions of total metabolically active bacteria in the libraries obtained from BRN and BRC. However, we detected changes in the taxonomic composition of the SRB community suggesting its adaptation to a higher level of NR-SOB activity in the presence of nitrate.

  19. Biodegradation of Glycidol and Glycidyl Nitrate

    Science.gov (United States)

    Kaplan, David L.; Cornell, John H.; Kaplan, Arthur M.

    1982-01-01

    When calcium hydroxide is used to desensitize glycerol trinitrate (nitroglycerine)-containing waste streams, the epoxides glycidol and glycidyl nitrate are formed. The epoxide rings of both compounds are unstable to heat in aqueous solutions, and they open to form glycerol 1-mononitrate and presumably glycerol. These transformations were accelerated by microbial activity. Glycerol 1-mononitrate was slowly denitrated to form glycerol. Glycidol and glycidyl nitrate caused base-pair substitutions in the Ames test for mutagenicity, whereas glycerol 1-mononitrate tests were negative. PMID:16345917

  20. Biodegradation of glycidol and glycidyl nitrate.

    Science.gov (United States)

    Kaplan, D L; Cornell, J H; Kaplan, A M

    1982-01-01

    When calcium hydroxide is used to desensitize glycerol trinitrate (nitroglycerine)-containing waste streams, the epoxides glycidol and glycidyl nitrate are formed. The epoxide rings of both compounds are unstable to heat in aqueous solutions, and they open to form glycerol 1-mononitrate and presumably glycerol. These transformations were accelerated by microbial activity. Glycerol 1-mononitrate was slowly denitrated to form glycerol. Glycidol and glycidyl nitrate caused base-pair substitutions in the Ames test for mutagenicity, whereas glycerol 1-mononitrate tests were negative.

  1. 9-Amino­acridinium nitrate monohydrate

    OpenAIRE

    Pourayoubi, Mehrdad; Eshtiagh-Hosseini, Hossein; Sanaei Ataabadi, Somayyeh; Mancilla Percino, Teresa; A. Leyva Ramírez, Marco

    2011-01-01

    The pyridine N atom of the cation in the title hydrated salt, C13H11N2 +·NO3 −·H2O, is protonated; the N atom of the NH2 group shows a planar conformation. The former N atom is hydrogen bonded to a water mol­ecule. The amino group is involved in three N—H⋯O hydrogen bonds with two neighboring nitrate anions. The water mol­ecule is hydrogen bonded to two adjacent nitrate anions. In the crystal, this results in a layered network.

  2. 9-Amino­acridinium nitrate monohydrate

    Science.gov (United States)

    Pourayoubi, Mehrdad; Eshtiagh-Hosseini, Hossein; Sanaei Ataabadi, Somayyeh; Mancilla Percino, Teresa; A. Leyva Ramírez, Marco

    2011-01-01

    The pyridine N atom of the cation in the title hydrated salt, C13H11N2 +·NO3 −·H2O, is protonated; the N atom of the NH2 group shows a planar conformation. The former N atom is hydrogen bonded to a water mol­ecule. The amino group is involved in three N—H⋯O hydrogen bonds with two neighboring nitrate anions. The water mol­ecule is hydrogen bonded to two adjacent nitrate anions. In the crystal, this results in a layered network. PMID:21522328

  3. Alkyl nitrate production and persistence in the Mexico City Plume

    Directory of Open Access Journals (Sweden)

    G. Sachse

    2009-11-01

    Full Text Available Alkyl and multifunctional nitrates (ΣANs have been observed to be a significant fraction of NOy in a number of different chemical regimes. Their formation is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. ΣANs also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Numerous studies have investigated the role of nitrate formation from biogenic compounds. Less attention has been paid to the role ΣANs may play in the complex mixtures of hydrocarbons typical of urban settings. Measurements of ΣANs, NO2, total peroxy nitrates (ΣPNs, HNO3 and a wide suite of hydrocarbons were obtained from the NASA DC-8 aircraft during spring of 2006 in and around Mexico City and the Gulf of Mexico. ΣANs were observed to be 10–20% of NOy in the Mexico City plume and to increase in importance with increased photochemical age. We describe three conclusions: 1 Correlations of ΣANs with odd-oxygen (Ox indicate a stronger role for ΣANs in the photochemistry of Mexico City than is expected based on currently accepted photochemical mechanisms, 2 ΣAN formation suppresses peak ozone production rates by as much as 30% in the near-field of Mexico City and 3 ΣANs play a comparable role to ΣPNs in the export of NOy to the Gulf Region.

  4. Highly active Pd-In/mesoporous alumina catalyst for nitrate reduction.

    Science.gov (United States)

    Gao, Zhenwei; Zhang, Yonggang; Li, Deyi; Werth, Charles J; Zhang, Yalei; Zhou, Xuefei

    2015-04-09

    The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd-In/Al2O3 with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO2-buffered water and under continuous H2 as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd-In ratio of 4, with a first-order rate constant (k(obs) = 0.241 L min(-1) g(cata)(-1)) that was 1.3× higher than that of conventional Pd-In/Al2O3 (5 wt% Pd; 0.19 L min(-1) g(cata)(-1)). The Pd-In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate.

  5. The Acid Catalyzed Nitration of Methanol: Formation of Methyl Nitrate via Aerosol Chemistry

    Science.gov (United States)

    Riffel, Brent G.; Michelsen, Rebecca R.; Iraci, Laura T.

    2004-01-01

    The liquid phase acid catalyzed reaction of methanol with nitric acid to yield methyl nitrate under atmospheric conditions has been investigated using gas phase infrared spectroscopy. This nitration reaction is expected to occur in acidic aerosol particles found in the upper troposphere/lower stratosphere as highly soluble methanol and nitric acid diffuse into these aerosols. Gaseous methyl nitrate is released upon formation, suggesting that some fraction of NO(x) may he liberated from nitric acid (methyl nitrate is later photolyzed to NO(x)) before it is removed from the atmosphere by wet deposition. Thus, this reaction may have important implications for the NO(x) budget. Reactions have been initiated in 45-62 wt% H2SO4 solutions at 10.0 C. Methyl nitrate production rates increased exponentially with acidity within the acidity regime studied. Preliminary calculations suggest that the nitronium ion (NO2(+) is the active nitrating agent under these conditions. The reaction order in methanol appears to depend on the water/methanol ratio and varies from first to zeroth order under conditions investigated. The nitration is first order in nitronium at all acidities investigated. A second order rate constant, kappa(sub 2), has been calculated to be 1 x 10(exp 8)/ M s when the reaction is first order in methanol. Calculations suggest the nitration is first order in methanol under tropospheric conditions. The infinitesimal percentage of nitric acid in the nitronium ion form in this acidity regime probably makes this reaction insignificant for the upper troposphere; however, this nitration may become significant in the mid stratosphere where colder temperatures increase nitric acid solubility and higher sulfuric acid content shifts nitric acid speciation toward the nitronium ion.

  6. The Acid Catalyzed Nitration of Methanol: Formation of Methyl Nitrate via Aerosol Chemistry

    Science.gov (United States)

    Riffel, Brent G.; Michelsen, Rebecca R.; Iraci, Laura T.

    2004-01-01

    The liquid phase acid catalyzed reaction of methanol with nitric acid to yield methyl nitrate under atmospheric conditions has been investigated using gas phase infrared spectroscopy. This nitration reaction is expected to occur in acidic aerosol particles found in the upper troposphere/lower stratosphere as highly soluble methanol and nitric acid diffuse into these aerosols. Gaseous methyl nitrate is released upon formation, suggesting that some fraction of NO(x) may he liberated from nitric acid (methyl nitrate is later photolyzed to NO(x)) before it is removed from the atmosphere by wet deposition. Thus, this reaction may have important implications for the NO(x) budget. Reactions have been initiated in 45-62 wt% H2SO4 solutions at 10.0 C. Methyl nitrate production rates increased exponentially with acidity within the acidity regime studied. Preliminary calculations suggest that the nitronium ion (NO2(+) is the active nitrating agent under these conditions. The reaction order in methanol appears to depend on the water/methanol ratio and varies from first to zeroth order under conditions investigated. The nitration is first order in nitronium at all acidities investigated. A second order rate constant, kappa(sub 2), has been calculated to be 1 x 10(exp 8)/ M s when the reaction is first order in methanol. Calculations suggest the nitration is first order in methanol under tropospheric conditions. The infinitesimal percentage of nitric acid in the nitronium ion form in this acidity regime probably makes this reaction insignificant for the upper troposphere; however, this nitration may become significant in the mid stratosphere where colder temperatures increase nitric acid solubility and higher sulfuric acid content shifts nitric acid speciation toward the nitronium ion.

  7. Reactions between water-soluble organic acids and nitrates in atmospheric aerosols: Recycling of nitric acid and formation of organic salts

    Science.gov (United States)

    Wang, Bingbing; Laskin, Alexander

    2014-03-01

    Atmospheric particles often include a complex mixture of nitrate and secondary organic materials accumulated within the same individual particles. Nitrate as an important inorganic component can be chemically formed in the atmosphere. For instance, formation of sodium nitrate (NaNO3) and calcium nitrate (Ca(NO3)2) occurs when nitrogen oxides and nitric acid (HNO3) react with sea salt and calcite, respectively. Organic acids contribute a significant fraction of photochemically formed secondary organics that can condense on the preexisting nitrate-containing particles. Here we present a systematic microanalysis study on chemical composition of laboratory-generated particles composed of water-soluble organic acids and nitrates (i.e., NaNO3 and Ca(NO3)2) using computer-controlled scanning electron microscopy with energy-dispersive X-ray microanalysis and Fourier transform infrared microspectroscopy. The results show that water-soluble organic acids can react with nitrates and release gaseous HNO3 during the dehydration process. These reactions are attributed to acid displacement of nitrate with weak organic acids driven by the evaporation of HNO3 into gas phase because of its relatively high volatility. The reactions result in significant nitrate depletion and formation of organic salts in mixed organic acids/nitrate particles that, in turn, may affect their physical and chemical properties relevant to atmospheric environment and climate. Airborne nitrate concentrations are estimated by thermodynamic calculations corresponding to various nitrate depletions in selected organic acids of atmospheric relevance. The results indicate a potential mechanism of HNO3 recycling that may further affect concentrations of gas and condensed phase species in the atmosphere and the heterogeneous reaction chemistry between them.

  8. Genome-enabled studies of anaerobic, nitrate-dependent iron oxidation in the chemolithoautotrophic bacterium Thiobacillus denitrificans

    Directory of Open Access Journals (Sweden)

    Harry R Beller

    2013-08-01

    Full Text Available Thiobacillus denitrificans is a chemolithoautotrophic bacterium capable of anaerobic, nitrate-dependent U(IV and Fe(II oxidation, both of which can strongly influence the long-term efficacy of in situ reductive immobilization of uranium in contaminated aquifers. We previously identified two c-type cytochromes involved in nitrate-dependent U(IV oxidation in T. denitrificans and hypothesized that c-type cytochromes would also catalyze Fe(II oxidation, as they have been found to play this role in anaerobic phototrophic Fe(II-oxidizing bacteria. Here we report on efforts to identify genes associated with nitrate-dependent Fe(II oxidation, namely (a whole-genome transcriptional studies [using FeCO3, Fe2+, and U(IV oxides as electron donors under denitrifying conditions], (b Fe(II oxidation assays performed with knockout mutants targeting primarily highly expressed or upregulated c-type cytochromes, and (c random transposon-mutagenesis studies with screening for Fe(II oxidation. Assays of mutants for 26 target genes, most of which were c-type cytochromes, indicated that none of the mutants tested were significantly defective in nitrate-dependent Fe(II oxidation. The non-defective mutants included the c1-cytochrome subunit of the cytochrome bc1 complex (complex III, which has relevance to a previously proposed role for this complex in nitrate-dependent Fe(II oxidation and to current concepts of reverse electron transfer. A transposon mutant with a disrupted gene associated with NADH:ubiquinone oxidoreductase (complex I was ~35% defective relative to the wild-type strain; this strain was similarly defective in nitrate reduction with thiosulfate as the electron donor. Overall, our results indicate that nitrate-dependent Fe(II oxidation in T. denitrificans is not catalyzed by the same c-type cytochromes involved in U(IV oxidation, nor have other c-type cytochromes yet been implicated in the process.

  9. A toxicological study of gadolinium nitrate

    Energy Technology Data Exchange (ETDEWEB)

    London, J.E.

    1988-05-01

    The sensitization study in the guinea pig did not show gadolinium nitrate to have potential sensitizing properties. Skin application studies in the rabbit demonstrated that it was cutaneously a severe irritant. This material was considered an irritant in the rabbit eye application studies. 3 refs., 1 tab.

  10. Nitrate Salt Surrogate Blending Scoping Test Plan

    Energy Technology Data Exchange (ETDEWEB)

    Anast, Kurt Roy [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2015-11-13

    Test blending equipment identified in the “Engineering Options Assessment Report: Nitrate Salt Waste Stream Processing”. Determine if the equipment will provide adequate mixing of zeolite and surrogate salt/Swheat stream; optimize equipment type and operational sequencing; impact of baffles and inserts on mixing performance; and means of validating mixing performance

  11. Protein Tyrosine Nitration: Role in Aging.

    Science.gov (United States)

    Chakravarti, Bulbul; Chakravarti, Deb Narayan

    2017-03-15

    Aging is the inevitable fate of all living organisms, but the molecular basis of physiological aging is still poorly understood. Oxidative stress is believed to play a key role in the aging process. In addition to reactive oxygen species (ROS), reactive nitrogen species (RNS) are generated during aerobic metabolism in living organisms. Protein damage and functional modification by ROS have been demonstrated in details by different investigators. However, compared to protein carbonylation by ROS, fewer studies have been reported on the protein damage by RNS and its implication with the aging process. Due to the high chemical reactivity of RNS, they can covalently modify various endogenous macromolecules including proteins and alter their essential biological functions. Tyrosine residues in protein molecules are nitrated following their interaction with RNS under nitrosative stress. Proteins undergoing tyrosine nitration are associated with pathophysiology of several diseases, as well as physiological aging. The purpose of the current review is to provide a brief summary of the biochemical mechanisms of tyrosine nitration, methodologies used for the detection of these modified proteins, effect of this post translational modification on biological functions and the putative role of tyrosine nitrated proteins in the aging process. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  12. Trend Analyses of Nitrate in Danish Groundwater

    DEFF Research Database (Denmark)

    Hansen, B.; Thorling, L.; Dalgaard, Tommy;

    2012-01-01

    This presentation assesses the long-term development in the oxic groundwater nitrate concentration and nitrogen (N) loss due to intensive farming in Denmark. Firstly, up to 20-year time-series from the national groundwater monitoring network enable a statistically systematic analysis of distribut......This presentation assesses the long-term development in the oxic groundwater nitrate concentration and nitrogen (N) loss due to intensive farming in Denmark. Firstly, up to 20-year time-series from the national groundwater monitoring network enable a statistically systematic analysis...... of distribution, trends and trend reversals in the groundwater nitrate concentration. Secondly, knowledge about the N surplus in Danish agriculture since 1950 is used as an indicator of the potential loss of N. Thirdly, groundwater recharge CFC (Chlorofluorocarbon) age determination allows linking of the first...... two dataset. The development in the nitrate concentration of oxic groundwater clearly mirrors the development in the national agricultural N surplus, and a corresponding trend reversal is found in groundwater. Regulation and technical improvements in the intensive farming in Denmark have succeeded...

  13. Denitration of High Nitrate Salts Using Reductants

    Energy Technology Data Exchange (ETDEWEB)

    HD Smith; EO Jones; AJ Schmidt; AH Zacher; MD Brown; MR Elmore; SR Gano

    1999-05-03

    This report describes work conducted by Pacific Northwest National Laboratory (PNNL), in conjunction with Idaho National Engineering and Environmental Laboratory (INEEL), to remove nitrates in simulated low-activity waste (LAW). The major objective of this work was to provide data for identifying and demonstrating a technically viable and cost-effective approach to condition LAW for immobilization (grout).

  14. Assimilatory Nitrate Reduction in Hansenula polymorpha

    Science.gov (United States)

    Rossi, Beatrice; Berardi, Enrico

    In the last decade, the yeast Hansenula polymorpha (syn.: Pichia angusta) has become an excellent experimental model for genetic and molecular investigations of nitrate assimilation, a subject traditionally investigated in plants, filamentous fungi and bacteria. Among other advantages, H. polymorpha offers classical and molecular genetic tools, as well as the availability of genomic sequence data.

  15. Detonation characteristics of ammonium nitrate products

    NARCIS (Netherlands)

    Kersten, R.J.A.; Hengel, E.I.V. van den; Steen, A.C. van der

    2006-01-01

    The detonation properties of ammonium nitrate (AN) products depend on many factors and are therefore, despite the large amount of information on this topic, difficult to assess. In order to further improve the understanding of the safety properties of AN, the European Fertilizer Manufacturers Associ

  16. The Path to Nitrate Salt Disposition

    Energy Technology Data Exchange (ETDEWEB)

    Funk, David John [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-03-16

    The topic is presented in a series of slides arranged according to the following outline: LANL nitrate salt incident as thermal runaway (thermally sensitive surrogates, full-scale tests), temperature control for processing, treatment options and down selection, assessment of engineering options, anticipated control set for treatment, and summary of the overall steps for RNS.

  17. Reinforced Sisal Fiber with Ferric Nitrate Composites

    Directory of Open Access Journals (Sweden)

    Asif Jehan

    2015-06-01

    Full Text Available Ferric oxide synthesized through annealing route. The present research work deals with ferrite composite prepared using chemical reactions. Ferric nitrates and ammonium chloride doped with sisal fiber has been prepared. The structural behavior of aluminum oxide was studied in XRD, SEM, TEM, FTIR & dielectric measurement. This behavior showed ferrite nature of the sample.

  18. NITRATE DESTRUCTION LITERATURE SURVEY AND EVALUATION CRITERIA

    Energy Technology Data Exchange (ETDEWEB)

    Steimke, J.

    2011-02-01

    This report satisfies the initial phase of Task WP-2.3.4 Alternative Sodium Recovery Technology, Subtask 1; Develop Near-Tank Nitrate/Nitrite Destruction Technology. Some of the more common anions in carbon steel waste tanks at SRS and Hanford Site are nitrate which is corrosive, and nitrite and hydroxide which are corrosion inhibitors. At present it is necessary to periodically add large quantities of 50 wt% caustic to waste tanks. There are three primary reasons for this addition. First, when the contents of salt tanks are dissolved, sodium hydroxide preferentially dissolves and is removed. During the dissolution process the concentration of free hydroxide in the tank liquid can decrease from 9 M to less than 0.2 M. As a result, roughly half way through the dissolution process large quantities of sodium hydroxide must be added to the tank to comply with requirements for corrosion control. Second, hydroxide is continuously consumed by reaction with carbon dioxide which occurs naturally in purge air used to prevent buildup of hydrogen gas inside the tanks. The hydrogen is generated by radiolysis of water. Third, increasing the concentration of hydroxide increases solubility of some aluminum compounds, which is desirable in processing waste. A process that converts nitrate and nitrite to hydroxide would reduce certain costs. (1) Less caustic would be purchased. (2) Some of the aluminum solid compounds in the waste tanks would become more soluble so less mass of solids would be sent to High Level Vitrification and therefore it would be not be necessary to make as much expensive high level vitrified product. (3) Less mass of sodium would be fed to Saltstone at SRS or Low Level Vitrification at Hanford Site so it would not be necessary to make as much low level product. (4) At SRS less nitrite and nitrate would be sent to Defense Waste Processing Facility (DWPF) so less formic acid would be consumed there and less hydrogen gas would be generated. This task involves

  19. Impact of Sulfide on Nitrate Conversion in Eutrophic Nitrate-Rich Marine Sludge

    DEFF Research Database (Denmark)

    Schwermer, Carsten U.; Krieger, Bärbel; Lavik, Gaute

    2006-01-01

    IMPACT OF SULFIDE ON NITRATE CONVERSION IN EUTROPHIC NITRATE-RICH MARINE SLUDGE C.U. Schwermer 1, B.U. Krieger 2, G. Lavik 1, A. Schramm 3, J. van Rijn 4, D. de Beer 1, D. Minz 5, E. Cytryn 4, M. Kuypers 1, A. Gieseke 1 1 Max Planck Institute for Marine Microbiology, Bremen, Germany; 2 Dept...... and Environmental Sciences, Volcani Research Center, Bet-Dagan, Israel Multiple anaerobic processes are responsible for carbon mineralization in eutrophic nitrate-rich marine environments (e.g., upwelling areas, estuaries, and aquacultures), involving electron acceptors from both the nitrogen and sulfur cycle....... The interaction of these processes is less understood. Our aim was to investigate the functional interaction of nitrate reduction, denitrification and sulfate reduction in an anaerobic marine sludge. We hypothesize that sulfide (from sulfate reduction) (i) causes incomplete denitrification, and (ii) directs...

  20. Benefits of Safer Drinking Water: The Value of Nitrate Reduction

    OpenAIRE

    Crutchfield, Stephen R.; Cooper, Joseph C.; Hellerstein, Daniel

    1997-01-01

    Nitrates in drinking water, which may come from nitrogen fertilizers applied to crops, are a potential health risk. This report evaluates the potential benefits of reducing human exposure to nitrates in the drinking water supply. In a survey, respondents were asked a series of questions about their willingness to pay for a hypothetical water filter, which would reduce their risk of nitrate exposure. If nitrates in the respondent's drinking water were to exceed the EPA minimum safety standard,...

  1. Identification of nitrate sources and discharge-depending nitrate dynamics in a mesoscale catchment

    Science.gov (United States)

    Mueller, Christin; Strachauer, Ulrike; Brauns, Mario; Musolff, Andreas; Kunz, Julia Vanessa; Brase, Lisa; Tarasova, Larisa; Merz, Ralf; Knöller, Kay

    2017-04-01

    During the last decades, nitrate concentrations in surface and groundwater have increased due to land use change and accompanying application of fertilizer in agriculture as well as increased atmospheric deposition. To mitigate nutrient impacts on downstream aquatic ecosystems, it is important to quantify potential nitrate sources, instream nitrate processing and its controls in a river system. The objective of this project is to characterize and quantify (regional) scale dynamics and trends in water and nitrogen fluxes of the entire Holtemme river catchment in central Germany making use of isotopic fingerprinting methods. Here we compare two key date sampling campaigns in 2014 and 2015, with spatially highly resolved measurements of discharge at 23 sampling locations including 11 major tributaries and 12 locations at the main river. Additionally, we have data from continuous runoff measurements at 10 locations operated by the local water authorities. Two waste water treatment plants contribute nitrogen to the Holtemme stream. This contribution impacts nitrate loads and nitrate isotopic signatures depending on the prevailing hydrological conditions. Nitrogen isotopic signatures in the catchment are mainly controlled by different sources (nitrified soil nitrogen in the headwater and manure/ effluents from WWTPs in the lowlands) and increase with raising nitrate concentrations along the main river. Nitrate loads at the outlet of the catchment are extremely different between both sampling campaigns (2014: NO3- = 97 t a-1, 2015: NO3- = 5 t a-1) which is associated with various runoff (2014: 0.8 m3 s-1, 2015: 0.2 m3 s-1). In 2015, the inflow from WWTP's raises the NO3- loads and enriches δ18O-NO3 values. Generally, oxygen isotope signatures from nitrate are more variable and are controlled by biogeochemical processes in concert with the oxygen isotopic composition of the ambient water. Elevated δ18O-NO3 in 2015 are most likely due to higher temperatures and lower

  2. 76 FR 49449 - Continuation of Antidumping Duty Order on Solid Fertilizer Grade Ammonium Nitrate From the...

    Science.gov (United States)

    2011-08-10

    ... Nitrate From the Russian Federation AGENCY: Import Administration, International Trade Administration... duty investigation on solid fertilizer grade ammonium nitrate (``ammonium nitrate'') from the Russian... and the ITC instituted a second sunset review of the ammonium nitrate suspended investigation....

  3. 76 FR 23569 - Termination of the Suspension Agreement on Solid Fertilizer Grade Ammonium Nitrate From the...

    Science.gov (United States)

    2011-04-27

    ... Nitrate From the Russian Federation and Notice of Antidumping Duty Order AGENCY: Import Administration... (``AD'') Investigation on Solid Fertilizer Grade Ammonium Nitrate from the Russian Federation (``the... determine whether imports of solid fertilizer grade ammonium nitrate (``ammonium nitrate'') from Russia...

  4. Nitrate ammonification in mangrove soils: A hidden source of nitrite?

    NARCIS (Netherlands)

    Balk, Melike; Laverman, A.M.; Keuskamp, Joost A.; Laanbroek, Hendrikus J.

    2015-01-01

    Nitrate reduction is considered to be a minor microbial pathway in the oxidation of mangrove-derived organic matter due to a limited supply of nitrate in mangrove soils. At a limited availability of this electron acceptor compared to the supply of degradable carbon, nitrate ammonification is thought

  5. Synthesis, Characterization, and Sensitivity Analysis of Urea Nitrate (UN)

    Science.gov (United States)

    2015-04-01

    ARL-TR-7250 ● APR 2015 US Army Research Laboratory Synthesis, Characterization, and Sensitivity Analysis of Urea Nitrate (UN...Characterization, and Sensitivity Analysis of Urea Nitrate (UN) by William M Sherrill Weapons and Materials Research Directorate...Characterization, and Sensitivity Analysis of Urea Nitrate (UN) 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S

  6. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  7. Nitrate to ammonia ceramic (NAC) bench scale stabilization study

    Energy Technology Data Exchange (ETDEWEB)

    Caime, W.J.; Hoeffner, S.L. [RUST - Clemson Technical Center, Anderson, SC (United States)

    1995-10-01

    Department of Energy (DOE) sites such as the Hanford site, Idaho National Engineering Laboratory (INEL), Savannah River site, Oak Ridge National Laboratory (ORNL) have large quantities of sodium-nitrate based liquid wastes. A process to reduce the nitrates to ammonia has been developed at ORNL. This technology creates a sludge lower in nitrates. This report describes stabilization possibilities of the sludge.

  8. A nitrate sensitive planar optode; performance and interferences

    DEFF Research Database (Denmark)

    Pedersen, Lasse; Dechesne, Arnaud; Smets, Barth F.

    2015-01-01

    We present a newly developed nitrate sensitive planar optode. It exhibits a linear response to nitrate from 1 to 50 mM at pH 8.0, a fast response time below 10 s and a good lifetime, allowing for fast two dimensional nitrate measurements over long periods of time. Interference from nitrite...

  9. 78 FR 32690 - Certain Ammonium Nitrate From Ukraine

    Science.gov (United States)

    2013-05-31

    ... COMMISSION Certain Ammonium Nitrate From Ukraine Determination On the basis of the record \\1\\ developed in... antidumping duty order on certain ammonium nitrate from Ukraine would be likely to lead to continuation or... Publication 4396 (May 2013), entitled Certain Ammonium Nitrate from Ukraine: Investigation No....

  10. 40 CFR 721.7500 - Nitrate polyether polyol (generic name).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Nitrate polyether polyol (generic name... Substances § 721.7500 Nitrate polyether polyol (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance nitrate polyether polyol (PMN P88-2540)...

  11. Solid state interaction studies on binary nitrate mixtures of uranyl nitrate hexahydrate and lanthanum nitrate hexahydrate at elevated temperatures

    Science.gov (United States)

    Kalekar, Bhupesh; Raje, Naina; Reddy, A. V. R.

    2017-02-01

    Interaction behavior of uranyl nitrate hexahydrate (UNH) and lanthanum nitrate hexahydrate (LaNH) have been investigated on the mixtures in different molar ratios of the two precursors and monitoring the reactions at elevated temperatures with thermoanalytical and X-ray diffraction measurement techniques. During the decomposition of equimolar mixture of LaNH and UNH, formation of lanthanum uranate (U0.5La0.5)O2, was seen by the temperature of 500 °C along with lanthanum oxide (La2O3) and uranium trioxide (UO3). By the temperature of 700 °C, the formation of uranium sesquioxide (U3O8) was observed along with (U0.5La0.5)O2 as end products in uranium rich mixtures. Lanthanum rich compositions decomposed by the temperature of 700 °C to give (U0.5La0.5)O2 and La2O3 as end products.

  12. Protein Tyrosine Nitration : Selectivity, Physicochemical and Biological Consequences, Denitration, and Proteomics Methods for the Identification of Tyrosine-Nitrated Proteins

    NARCIS (Netherlands)

    Abello, Nicolas; Kerstjens, Huib A. M.; Postma, Dirkje S.; Bischoff, Rainer

    Protein tyrosine nitration (PTN) is a post-translational modification occurring under the action of a nitrating agent. Tyrosine is modified in the 3-position of the phenolic ring through the addition of a nitro group (NO(2)). In the present article, we review the main nitration reactions and

  13. Protein Tyrosine Nitration: Selectivity, physicochemical and biological consequences, denitration and proteomics methods for the identification of tyrosine-nitrated proteins

    NARCIS (Netherlands)

    Abello, N.; Kerstjens, H.A.M.; Postma, D.S; Bischoff, Rainer

    2009-01-01

    Protein tyrosine nitration (PTN) is a post-translational modification occurring under the action of a nitrating agent. Tyrosine is modified in the 3-position of the phenolic ring through the addition of a nitro group (NO2). In the present article, we review the main nitration reactions and elucidate

  14. Effect of Sodium Nitrate and Nitrate Reducing Bacteria on In vitro Methane Production and Fermentation with Buffalo Rumen Liquor.

    Science.gov (United States)

    Sakthivel, Pillanatham Civalingam; Kamra, Devki Nandan; Agarwal, Neeta; Chaudhary, Lal Chandra

    2012-06-01

    Nitrate can serve as a terminal electron acceptor in place of carbon dioxide and inhibit methane emission in the rumen and nitrate reducing bacteria might help enhance the reduction of nitrate/nitrite, which depends on the type of feed offered to animals. In this study the effects of three levels of sodium nitrate (0, 5, 10 mM) on fermentation of three diets varying in their wheat straw to concentrate ratio (700:300, low concentrate, LC; 500:500, medium concentrate, MC and 300:700, high concentrate, HC diet) were investigated in vitro using buffalo rumen liquor as inoculum. Nitrate reducing bacteria, isolated from the rumen of buffalo were tested as a probiotic to study if it could help in enhancing methane inhibition in vitro. Inclusion of sodium nitrate at 5 or 10 mM reduced (pfeed reduced (pfeeding and introduced individually (3 ml containing 1.2 to 2.3×10(6) cfu/ml) into in vitro incubations containing the MC diet with 10 mM sodium nitrate. Addition of live culture of NRBB 57 resulted in complete removal of nitrate and nitrite from the medium with a further reduction in methane and no effect on IVTD compared to the control treatments containing nitrate with autoclaved cultures or nitrate without any culture. The data revealed that nitrate reducing bacteria can be used as probiotic to prevent the accumulation of nitrite when sodium nitrate is used to reduce in vitro methane emissions.

  15. Nitration transforms a sensitive peroxiredoxin 2 into a more active and robust peroxidase.

    Science.gov (United States)

    Randall, Lía M; Manta, Bruno; Hugo, Martín; Gil, Magdalena; Batthyàny, Carlos; Trujillo, Madia; Poole, Leslie B; Denicola, Ana

    2014-05-30

    Peroxiredoxins (Prx) are efficient thiol-dependent peroxidases and key players in the mechanism of H2O2-induced redox signaling. Any structural change that could affect their redox state, oligomeric structure, and/or interaction with other proteins could have a significant impact on the cascade of signaling events. Several post-translational modifications have been reported to modulate Prx activity. One of these, overoxidation of the peroxidatic cysteine to the sulfinic derivative, inactivates the enzyme and has been proposed as a mechanism of H2O2 accumulation in redox signaling (the floodgate hypothesis). Nitration of Prx has been reported in vitro as well as in vivo; in particular, nitrated Prx2 was identified in brains of Alzheimer disease patients. In this work we characterize Prx2 tyrosine nitration, a post-translational modification on a noncatalytic residue that increases its peroxidase activity and its resistance to overoxidation. Mass spectrometry analysis revealed that treatment of disulfide-oxidized Prx2 with excess peroxynitrite renders mainly mononitrated and dinitrated species. Tyrosine 193 of the YF motif at the C terminus, associated with the susceptibility toward overoxidation of eukaryotic Prx, was identified as nitrated and is most likely responsible for the protection of the peroxidatic cysteine against oxidative inactivation. Kinetic analyses suggest that tyrosine nitration facilitates the intermolecular disulfide formation, transforming a sensitive Prx into a robust one. Thus, tyrosine nitration appears as another mechanism to modulate these enzymes in the complex network of redox signaling. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

  16. Highly active Pd–In/mesoporous alumina catalyst for nitrate reduction

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Zhenwei; Zhang, Yonggang; Li, Deyi [State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Werth, Charles J. [Civil, Architectural and Environmental Engineering, University of Texas at Austin, 301 East Dean Keeton St., Stop C1786, Austin, TX 78712 (United States); Zhang, Yalei, E-mail: zhangyalei2003@163.com [State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Zhou, Xuefei, E-mail: zhouxuefei@tongji.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China)

    2015-04-09

    Highlights: • Pd–In nanoparticles (6–7 nm) uniformly form in the mesopores of alumina (4 nm). • Pd–In nanoparticles aggregation is prevented during the synthesis process. • The reduction rate of nitrate is efficient by using the obtained catalyst. • The selectivity toward N{sub 2} is ideal by using the obtained catalyst. - Abstract: The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd–In/Al{sub 2}O{sub 3} with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO{sub 2}-buffered water and under continuous H{sub 2} as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd–In ratio of 4, with a first-order rate constant (k{sub obs} = 0.241 L min{sup −1} g{sub cata}{sup −1}) that was 1.3× higher than that of conventional Pd–In/Al{sub 2}O{sub 3} (5 wt% Pd; 0.19 L min{sup −1} g{sub cata}{sup −1}). The Pd–In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate.

  17. Nitration of soluble proteins in organotypic culture models of Parkinson's disease.

    Science.gov (United States)

    Larsen, Trine R; Söderling, Ann-Sofi; Caidahl, Kenneth; Roepstorff, Peter; Gramsbergen, Jan Bert

    2008-02-01

    Protein nitration due to oxidative and nitrative stress has been linked to the pathogenesis of Parkinson's disease (PD), but its relationship to the loss of dopamine (DA) or tyrosine hydroxylase (TH) activity is not clear. Here we quantified protein-bound 3-nitrotyrosine (3-NT) by a novel gas chromatography/negative chemical ionization tandem mass spectrometry technique and DA and 3,4-dihydroxyphenylalanine (DOPA) by HPLC in tissues or medium of organotypic, mouse mesencephalon cultures after acute or chronic treatments with the peroxynitrite donor 3-morpholino-sydnonimine (SIN-1), the dopaminergic toxin 1-methyl-4-phenylpyridinium (MPP(+)) or the lipophilic complex I inhibitor rotenone. Incubation with SIN-1 (24 h) or MPP(+) treatments (48 h) caused dose-dependent protein nitration reaching a maximum of eightfold increase by 10 mM SIN-1 or twofold by 10 microM MPP(+), but significant DA depletions occurred at much lower concentrations of MPP(+) (1 microM). Chronic MPP(+) or rotenone treatments (3 weeks) caused maximum protein nitration by 1 microM (twofold) or 10nM (fourfold), respectively. Co-treatment with the nitric oxide synthase inhibitor l-NAME (300 microM) prevented protein nitration by MPP(+), but did not protect against MPP(+)-induced DA depletion or inhibition of TH activity. Acute incubation with 100 microM SIN-1 inhibited TH activity, which could be blocked by co-treatment with the tetrahydrobiopterin precursor l-sepiapterin, but tissue DA depletions required higher doses of SIN-1 (>1 mM, 24 h) and longer survival. In conclusion, protein nitration and TH activity or DA depletion are not directly related in these models.

  18. Effect of nitrate on activities and transcript levels of nitrate reductase and glutamine synthetase in rice

    Institute of Scientific and Technical Information of China (English)

    CAO Yun; FAN Xiao-Rong; SUN Shu-Bin; XU Guo-Hua; HU Jiang; SHEN Qi-Rong

    2008-01-01

    Real-time polymerase chain reaction analysis was used to compare the effect of NO-3 on the activities of nitrate reductase (NR) and glutamine synthetase (GS),and the transcript levels of two NR genes,OsNia1 and OsNia2,two cytceolic GS1 genes,OsGln1;1 and OsGln1;2,and one plastid GS2 gene OsGln2,in two rice (Oryza sativa L.) cultivars Nanguang (NG) and Yunjing (YJ).Both cultivars achieved greater biomass and higher total N concentration when grown in a mixed N supply than in sole NH+ nutrition.Supply of NO-3 increased NR activity in both leaves and roots.Expression of both NR genes was also substantially enhanced and transcript levels of OsNia2 were significantly higher than those of OsNia1.NO-3 also caused an increase in GS activity,but had a complex effect on the expression of the three GS genes.In roots,the OsGln1;1 transcript increased,but OsGln1;2 decreased.In leaves,NO-3 had no effect on the GS1 expression,but the transcript for OsGln2 increased both in the leaves and roots of rice with a mixed supply of N.These results suggested that the increase in GS activity might be a result of the complicated regulation of the various GS genes.In addition,the NO-3 induced increase of biomass,NR activity,GS activity,and the transcript levels of NR and GS genes were proportionally higher in NG than in YJ,indicating a stronger response of NG to NO-3 nutrition than YJ.

  19. Open-Source Photometric System for Enzymatic Nitrate Quantification.

    Science.gov (United States)

    Wittbrodt, B T; Squires, D A; Walbeck, J; Campbell, E; Campbell, W H; Pearce, J M

    2015-01-01

    Nitrate, the most oxidized form of nitrogen, is regulated to protect people and animals from harmful levels as there is a large over abundance due to anthropogenic factors. Widespread field testing for nitrate could begin to address the nitrate pollution problem, however, the Cadmium Reduction Method, the leading certified method to detect and quantify nitrate, demands the use of a toxic heavy metal. An alternative, the recently proposed Environmental Protection Agency Nitrate Reductase Nitrate-Nitrogen Analysis Method, eliminates this problem but requires an expensive proprietary spectrophotometer. The development of an inexpensive portable, handheld photometer will greatly expedite field nitrate analysis to combat pollution. To accomplish this goal, a methodology for the design, development, and technical validation of an improved open-source water testing platform capable of performing Nitrate Reductase Nitrate-Nitrogen Analysis Method. This approach is evaluated for its potential to i) eliminate the need for toxic chemicals in water testing for nitrate and nitrite, ii) reduce the cost of equipment to perform this method for measurement for water quality, and iii) make the method easier to carryout in the field. The device is able to perform as well as commercial proprietary systems for less than 15% of the cost for materials. This allows for greater access to the technology and the new, safer nitrate testing technique.

  20. Nitrate removal by microbial enhancement in a riparian wetland.

    Science.gov (United States)

    Pei, Yuansheng; Yang, Zhifeng; Tian, Binghui

    2010-07-01

    A riparian wetland (RW) was constructed in a river bend to study the effect of the addition of Bacillus subtilis FY99-01 on nitrate removal. Nitrate was removed more efficiently in the summer than in the winter owing to integrated hydraulic, microbial and environmental effects. The maximal nitrate removal and the mean nitrate loss rate in the RW were 36.1% and 50.5 g/m(2)/yr, respectively. Statistic analyses indicated that the redox potential was very significant to denitrification while organic matter in the outflow, temperature and nitrate in the inflow significantly affected nitrate removal. These results suggest that an RW can be a cost-effective approach to enhance microbial nitrate removal and can potentially be extended to similar river bends.

  1. Understanding nitrate assimilation and its regulation in microalgae

    Directory of Open Access Journals (Sweden)

    Emanuel eSanz-Luque

    2015-10-01

    Full Text Available Nitrate assimilation is a key process for nitrogen (N acquisition in green microalgae. Among Chlorophyte algae, Chlamydomonas reinhardtii has resulted to be a good model system to unravel important facts of this process, and has provided important insights for agriculturally relevant plants. In this work, the recent findings on nitrate transport, nitrate reduction and the regulation of nitrate assimilation are presented in this and several other algae. Latest data have shown nitric oxide (NO as an important signal molecule in the transcriptional and posttranslational regulation of nitrate reductase and inorganic N transport. Participation of regulatory genes and proteins in positive and negative signaling of the pathway and the mechanisms involved in the regulation of nitrate assimilation, as well as those involved in Molybdenum cofactor synthesis required to nitrate assimilation, are critically reviewed.

  2. Observations on particulate organic nitrates and unidentified components of NOy

    DEFF Research Database (Denmark)

    Nielsen, T.; Egeløv, A.H.; Granby, K.

    1995-01-01

    A method to determine the total content of particulate organic nitrates (PON) has been developed and ambient air measurements of PON, NO, NO2, HNO3, peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), gas NOy and particulate inorganic nitrate have been performed in the spring and early...... = gas NOy + particulate inorganic nitrate). Residual gas NOy was much higher than the particulate fraction of organic nitrates (PON). PON was only 0.25 +/- 0.11% of concentrations of photochemical oxidants in connection with high-pressure systems suggesting atmospheric processes being the major source...... summer al an agricultural site in Denmark and compared with measurements of ozone, H2O2, SO2, formic acid, acetic acid and methane sulphonic acid. The gas NOy detector determines the sum NO + NO2 + HNO2 + HNO3 + PAN + PPN + gas phase organic nitrates + 2 x N2O5 + NO3. The content of residual gas NOy...

  3. Nitrate intake from drinking water on Tenerife island (Spain).

    Science.gov (United States)

    Caballero Mesa, J M; Rubio Armendáriz, C; Hardisson de la Torre, A

    2003-01-20

    Although meat and vegetable products contain higher concentrations of nitrate, drinking water is the fastest and most direct form of nitrate consumption by the population. It becomes contaminated with nitrates when sea water infiltrates fresh water aquifers and when rain and irrigation water wash through soils that have been excessively treated with nitrated fertilizers. Nitrates are of great toxicological interest as they are involved in the origin of nitrites and nitrosamines and the development of metahaemoglobinaemia in infants. The objective of this study was to determine the quantities of NO(3)(-) in the water supply of each of the Island's municipalities and in the leading brands of bottled waters consumed by the population of Tenerife. This parameter is necessary for the determination of Acceptable Daily Intake (A.D.I.) of nitrates from drinking water. With one unremarkable exception, the nitrate levels found in the water analyzed were optimum for human consumption and amply complied with current European Legislation.

  4. Understanding nitrate assimilation and its regulation in microalgae.

    Science.gov (United States)

    Sanz-Luque, Emanuel; Chamizo-Ampudia, Alejandro; Llamas, Angel; Galvan, Aurora; Fernandez, Emilio

    2015-01-01

    Nitrate assimilation is a key process for nitrogen (N) acquisition in green microalgae. Among Chlorophyte algae, Chlamydomonas reinhardtii has resulted to be a good model system to unravel important facts of this process, and has provided important insights for agriculturally relevant plants. In this work, the recent findings on nitrate transport, nitrate reduction and the regulation of nitrate assimilation are presented in this and several other algae. Latest data have shown nitric oxide (NO) as an important signal molecule in the transcriptional and posttranslational regulation of nitrate reductase and inorganic N transport. Participation of regulatory genes and proteins in positive and negative signaling of the pathway and the mechanisms involved in the regulation of nitrate assimilation, as well as those involved in Molybdenum cofactor synthesis required to nitrate assimilation, are critically reviewed.

  5. Silver nanoparticles can attenuate nitrative stress

    Directory of Open Access Journals (Sweden)

    Mariusz Zuberek

    2017-04-01

    Full Text Available We have reported previously that glucose availability can modify toxicity of silver nanoparticles (AgNPs via elevation of antioxidant defence triggered by increased mitochondrial generation of reactive oxygen species. In this study, we examined the effect of glucose availability on the production of reactive nitrogen species in HepG2 cells and modification of nitrative stress by AgNPs. We found that lowering the glucose concentration increased expression of genes coding for inducible nitric oxide syntheas, NOS2 and NOS2A resulting in enhanced production of nitric oxide. Surprisingly, AgNPs decreased the level of nitric oxide accelerated denitration of proteins nitrated by exogenous peroxynitrite in cells grown in the presence of lowered glucose concentration, apparently due to further induction of protective proteins.

  6. Respiratory Ammonification of Nitrate Coupled to Anaerobic Oxidation of Elemental Sulfur in Deep-Sea Autotrophic Thermophilic Bacteria

    Science.gov (United States)

    Slobodkina, Galina B.; Mardanov, Andrey V.; Ravin, Nikolai V.; Frolova, Anastasia A.; Chernyh, Nikolay A.; Bonch-Osmolovskaya, Elizaveta A.; Slobodkin, Alexander I.

    2017-01-01

    Respiratory ammonification of nitrate is the microbial process that determines the retention of nitrogen in an ecosystem. To date, sulfur-dependent dissimilatory nitrate reduction to ammonium has been demonstrated only with sulfide as an electron donor. We detected a novel pathway that couples the sulfur and nitrogen cycles. Thermophilic anaerobic bacteria Thermosulfurimonas dismutans and Dissulfuribacter thermophilus, isolated from deep-sea hydrothermal vents, grew autotrophically with elemental sulfur as an electron donor and nitrate as an electron acceptor producing sulfate and ammonium. The genomes of both bacteria contain a gene cluster that encodes a putative nitrate ammonification enzyme system. Nitrate reduction occurs via a Nap-type complex. The reduction of produced nitrite to ammonium does not proceed via the canonical Nrf system because nitrite reductase NrfA is absent in the genomes of both microorganisms. The genome of D. thermophilus encodes a complete sulfate reduction pathway, while the Sox sulfur oxidation system is missing, as shown previously for T. dismutans. Thus, in high-temperature environments, nitrate ammonification with elemental sulfur may represent an unrecognized route of primary biomass production. Moreover, the anaerobic oxidation of sulfur compounds coupled to growth has not previously been demonstrated for the members of Thermodesulfobacteria or Deltaproteobacteria, which were considered exclusively as participants of the reductive branch of the sulfur cycle. PMID:28194142

  7. Temporal patterns and source apportionment of nitrate-nitrogen leaching in a paddy field at Kelantan, Malaysia.

    Science.gov (United States)

    Hussain, Hazilia; Yusoff, Mohd Kamil; Ramli, Mohd Firuz; Abd Latif, Puziah; Juahir, Hafizan; Zawawi, Mohamed Azwan Mohammed

    2013-11-15

    Nitrate-nitrogen leaching from agricultural areas is a major cause for groundwater pollution. Polluted groundwater with high levels of nitrate is hazardous and cause adverse health effects. Human consumption of water with elevated levels of NO3-N has been linked to the infant disorder methemoglobinemia and also to non-Hodgkin's disease lymphoma in adults. This research aims to study the temporal patterns and source apportionment of nitrate-nitrogen leaching in a paddy soil at Ladang Merdeka Ismail Mulong in Kelantan, Malaysia. The complex data matrix (128 x 16) of nitrate-nitrogen parameters was subjected to multivariate analysis mainly Principal Component Analysis (PCA) and Discriminant Analysis (DA). PCA extracted four principal components from this data set which explained 86.4% of the total variance. The most important contributors were soil physical properties confirmed using Alyuda Forecaster software (R2 = 0.98). Discriminant analysis was used to evaluate the temporal variation in soil nitrate-nitrogen on leaching process. Discriminant analysis gave four parameters (hydraulic head, evapotranspiration, rainfall and temperature) contributing more than 98% correct assignments in temporal analysis. DA allowed reduction in dimensionality of the large data set which defines the four operating parameters most efficient and economical to be monitored for temporal variations. This knowledge is important so as to protect the precious groundwater from contamination with nitrate.

  8. Enzyme catalytic nitration of aromatic compounds.

    Science.gov (United States)

    Kong, Mingming; Wang, Kun; Dong, Runan; Gao, Haijun

    2015-06-01

    Nitroaromatic compounds are important intermediates in organic synthesis. The classic method used to synthesize them is chemical nitration, which involves the use of nitric acid diluted in water or acetic acid, both harmful to the environment. With the development of green chemistry, environmental friendly enzyme catalysis is increasingly employed in chemical processes. In this work, we adopted a non-aqueous horseradish peroxidase (HRP)/NaNO2/H2O2 reaction system to study the structural characteristics of aromatic compounds potentially nitrated by enzyme catalysis, as well as the relationship between the charges on carbon atoms in benzene ring and the nitro product distribution. Investigation of various reaction parameters showed that mild reaction conditions (ambient temperature and neutral pH), plus appropriate use of H2O2 and NaNO2 could prevent inactivation of HRP and polymerization of the substrates. Compared to aqueous-organic co-solvent reaction media, the aqueous-organic two-liquid phase system had great advantages in increasing the dissolved concentration of substrate and alleviating substrate inhibition. Analysis of the aromatic compounds' structural characteristics indicated that substrates containing substituents of NH2 or OH were readily catalyzed. Furthermore, analysis of the relationship between natural bond orbital (NBO) charges on carbon atoms in benzene ring, as calculated by the density functional method, and the nitro product distribution characteristics, demonstrated that the favored nitration sites were the ortho and para positions of substituents in benzene ring, similar to the selectivity of chemical nitration. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. Potential of dietary nitrate in angiogenesis

    Institute of Scientific and Technical Information of China (English)

    Christos; Rammos; Peter; Luedike; Ulrike; Hendgen-Cotta; Tienush; Rassaf

    2015-01-01

    Endothelial dysfunction with impaired bioavailability of nitric oxide(NO) is the hallmark in the development of cardiovascular disease. Endothelial dysfunction leads to atherosclerosis, characterized by chronic inflammation of the arterial wall and stepwise narrowing of the vessel lumen. Atherosclerosis causes deprivation of adequate tissue blood flow with compromised oxygen supply. To overcome this undersupply, remodeling of the vascular network is necessary to reconstitute and sustain tissue viability. This physiological response is often not sufficient and therapeutic angiogenesis remains an unmet medical need in critical limb ischemia or coronary artery disease. Feasible approaches to promote blood vessel formation are sparse. Administration of pro-angiogenic factors, gene therapy, or targeting of micro RNAs has not yet entered the daily practice. Nitric oxide is an important mediator of angiogenesis that becomes limited under ischemic conditions and the maintenance of NO availability might constitute an attractive therapeutic target. Until recently it was unknown how the organism provides NO under ischemia. In recent years it could be demonstrated that NO can be formed independently of its enzymatic synthesis in the endothelium by reduction of inorganic nitrite under hypoxic conditions. Circulating nitrite derives from oxidation of NO or reduction of inorganic nitrate by commensal bacteria in the oral cavity. Intriguingly, nitrate is a common constituent of our everyday diet and particularly high concentrations are found in leafy green vegetables such as spinach, lettuce, or beetroot. Evidence suggests that dietary nitrate supplementation increases the regenerative capacity of ischemic tissue and that this effect may offer an attractive nutrition-based strategy to improve ischemia-induced revascularization. We here summarize and discuss the regenerative capacity of dietary nitrate on the vascular system.

  10. Methemoglobinaemia in Cardiac Patients on Nitrate Therapy

    Directory of Open Access Journals (Sweden)

    Abdel Aziz A. Ghanem

    2010-06-01

    Full Text Available Background: Methaemoglobinaemia refers to the oxidation of ferrous iron to ferric iron within the haemoglobin molecule, which occurs following oxidative stresses. The subsequent impairment in oxygen transport may lead to progressive hypoxia that is highly dangerous condition especially in borderline patients like the cardiac patient.Objectives: In the present work, authors explore the extent of methaemoglobinaemia in cardiac patients receiving nitrate therapy.Methodology: The study included 970 cardiac patients presented in cardiology department, Mansoura Specialised Medical Hospital, Egypt, in the period from February to July 2009. Patients were taking oral, sublingual, dermal preparation or a combination of two preparations.Results: cases of the study had methemoglobin level 1.1782 ± 0.3476 g/dL with insignificant difference between males and females. Methemoglobin showed positive correlation with carboxyhemogloin and negative correlation with O2 content and O2 saturation. It was significantly higher in cardiac patient with chest infection, anaemia and diabetic patients but didn't differ in hepatic or non hepatic cardiac patients. 3.2% of cardiac patients who receive more than one nitrate preparation (either oral and dermal or oral and sublingual therapy have methemoglobin level significantly higher than those who receive single preparation. There is significant difference in methemoglobin level in cardiac patients complaining of myocardial infarction “MI”, unstable Angina, atrial fibrillation “AF” and hypertensive heart disease “HTN”.Conclusions: It is concluded that commonly used dosages of nitrates are capable of causing elevations of methemoglobin ranged from 0.9 – 5.3 g/dl. Although the elevation in methaemoglobin (MetHb levels was not of routine clinical significance, there was statistically significant increase in MetHb levels in cardiac patients with another pathologic condition as anaemia, diabetes mellitus or chest

  11. Potential of dietary nitrate in angiogenesis.

    Science.gov (United States)

    Rammos, Christos; Luedike, Peter; Hendgen-Cotta, Ulrike; Rassaf, Tienush

    2015-10-26

    Endothelial dysfunction with impaired bioavailability of nitric oxide (NO) is the hallmark in the development of cardiovascular disease. Endothelial dysfunction leads to atherosclerosis, characterized by chronic inflammation of the arterial wall and stepwise narrowing of the vessel lumen. Atherosclerosis causes deprivation of adequate tissue blood flow with compromised oxygen supply. To overcome this undersupply, remodeling of the vascular network is necessary to reconstitute and sustain tissue viability. This physiological response is often not sufficient and therapeutic angiogenesis remains an unmet medical need in critical limb ischemia or coronary artery disease. Feasible approaches to promote blood vessel formation are sparse. Administration of pro-angiogenic factors, gene therapy, or targeting of microRNAs has not yet entered the daily practice. Nitric oxide is an important mediator of angiogenesis that becomes limited under ischemic conditions and the maintenance of NO availability might constitute an attractive therapeutic target. Until recently it was unknown how the organism provides NO under ischemia. In recent years it could be demonstrated that NO can be formed independently of its enzymatic synthesis in the endothelium by reduction of inorganic nitrite under hypoxic conditions. Circulating nitrite derives from oxidation of NO or reduction of inorganic nitrate by commensal bacteria in the oral cavity. Intriguingly, nitrate is a common constituent of our everyday diet and particularly high concentrations are found in leafy green vegetables such as spinach, lettuce, or beetroot. Evidence suggests that dietary nitrate supplementation increases the regenerative capacity of ischemic tissue and that this effect may offer an attractive nutrition-based strategy to improve ischemia-induced revascularization. We here summarize and discuss the regenerative capacity of dietary nitrate on the vascular system.

  12. Genetic basis for nitrate resistance in Desulfovibrio strains

    Directory of Open Access Journals (Sweden)

    Hannah eKorte

    2014-04-01

    Full Text Available Nitrate is an inhibitor of sulfate-reducing bacteria (SRB. In petroleum production sites, amendments of nitrate and nitrite are used to prevent SRB production of sulfide that causes souring of oil wells. A better understanding of nitrate stress responses in the model SRB, Desulfovibrio vulgaris Hildenborough and Desulfovibrio alaskensis G20, will strengthen predictions of environmental outcomes. Nitrate inhibition of SRB has historically been considered to result from the generation of small amounts of nitrite, to which SRB are quite sensitive. Here we explored the possibility that nitrate might inhibit SRB by a mechanism other than through nitrite inhibition. We found that nitrate-stressed D. vulgaris cultures grown in lactate-sulfate conditions eventually grew in the presence of high concentrations of nitrate, and their resistance continued through several subcultures. Nitrate consumption was not detected over the course of the experiment, suggesting adaptation to nitrate. With high-throughput genetic approaches employing TnLE-seq for D. vulgaris and a pooled mutant library of D. alaskensis, we determined the fitness of many transposon mutants of both organisms in nitrate stress conditions. We found that several mutants, including homologs present in both strains, had a greatly increased ability to grow in the presence of nitrate but not nitrite. The mutated genes conferring nitrate resistance included the gene encoding the putative Rex transcriptional regulator (DVU0916/Dde_2702, as well as a cluster of genes (DVU0251-DVU0245/Dde_0597-Dde_0605 that is poorly annotated. Follow-up studies with individual D. vulgaris transposon and deletion mutants confirmed high-throughput results. We conclude that, in D. vulgaris and D. alaskensis, nitrate resistance in wild-type cultures is likely conferred by spontaneous mutations. Furthermore, the mechanisms that confer nitrate resistance may be different from those that confer nitrite resistance.

  13. Nitrate dual isotopic composition in the northern South China Sea and neighboring West Philippine Sea

    Science.gov (United States)

    Yang, J.; Xu, M.; Wu, Y.; Dai, M.; Kao, S.

    2013-12-01

    of duel isotopes in nitrate, the complex 3-D mixing among the SCS interior and neighboring WPS likely to be resolved if more profiles can be done.

  14. Bis{2-ethoxy-6-[2-(ethylammonioethyliminomethyl]phenolato}thiocyanatozinc(II nitrate

    Directory of Open Access Journals (Sweden)

    Hui-Rui Guo

    2008-10-01

    Full Text Available The title complex, [Zn(NCS(C13H20N2O22]NO3, consists of a complex mononuclear ZnII cation and a nitrate counter-anion. The ZnII ion is five-coordinate in a trigonal-bipyramidal geometry. The thiocyanate N atom and two O atoms from two Schiff bases define the equatorial plane, and the two imine N atoms from the same two Schiff bases occupy the axial positions, with an N—Zn—N angle of 175.98 (7°. The amine N atoms of the Schiff base ligands are protonated and are not involved in the coordination to the metal. The dihedral angle between the two substituted benzene rings is 87.7 (2°. The nitrate counter-ions are linked to the cations through N—H...O hydrogen bonds.

  15. Synthesis and Structural Study of Tris(-pyrazolylhexakis(pyrazoledicobalt(III Nitrate

    Directory of Open Access Journals (Sweden)

    Yifan Shi

    2013-01-01

    Full Text Available The new (Hpyz3Co(μ2-pyz3Co complex has been isolated as the nitrate salt through a reaction of Co(II nitrate, Hpyz (pyrazole, triethylamine, and oxygen. The salt crystallizes in the monoclinic space group P21/m with a = 12.5977(3 Å, b = 15.3387(4 Å, c = 14.0800(3 Å, β = 93.0868(15°, and = 1.464 g/cm3 at 150(1 K. The complex, with pseudo-octahedral coordination about the equivalent cobalt centers, has shorter Co–N distances for the bridging anionic pyz ligands as compared to the neutral Hpyz ligands, with the averages being 1.918(2 and 1.966(4, respectively. The Co–Co separation is 3.568 Å, reflecting the absence of any significant metal-metal interaction.

  16. Carbonyl Alkyl Nitrates as Trace Constituents in Urban Air

    Science.gov (United States)

    Woidich, S.; Gruenert, A.; Ballschmiter, K.

    2003-04-01

    Organic nitrates, esters of nitric acid, significantly contribute to the entire pool of odd nitrogen (NOY) in the atmosphere. Organic nitrates are formed in NO rich air by degradation of alkanes and alkenes initiated by OH and NO3 radicals during daytime and nighttime, respectively. Bifunctional organonitrates like the alkyl dinitrates and hydroxy alkyl nitrates are formed primarily from alkenes. The two main sources for Alkenes are traffic emissions and naturally occurring terpenes. So far a broad spectrum of alkyl dinitrates and hydroxy alkyl nitrates including six different isoprene nitrates has been identified in urban and marine air (1-3). We report here for the first time about the group of C4 C7 carbonyl alkyl nitrates as trace constituents in urban air collected on the campus of the University of Ulm Germany, and in the downtown area of Salt Lake City, Utah. Air sampling was done by high volume sampling (flow rate 25 m3/h) using a layer of 100 g silica gel (particle diameter 0.2 - 0.5 mm) as adsorbent. The organic nitrates were eluted from the silica gel by pentane/acetone (4:1, w/w) and the extract was concentrated to a volume of 500 µL for a group separation using normal phase HPLC. Final analysis was performed by high resolution capillary gas chromatography with electron capture detection as well as by mass selective detection in the (CH4)NCI mode using NO2- = m/e 46 as the indicator mass. The carbonyl alkyl nitrates were identified by self synthesized reference standards . So far we have identified eight non-branched a-carbonyl alkyl nitrates (vicinal carbonyl alkyl nitrates), two b-carbonyl alkyl nitrates and one g-carbonyl alkyl nitrate with carbon chains ranging from C4 to C7. The mixing ratios are between 0.05 and 0.30 ppt(v) for daytime samples and are two to three times higher for samples taken at night. (1) M. Schneider, O. Luxenhofer, Angela Deißler, K. Ballschmiter: 2C1-C15 Alkyl Nitrates, Benzyl Nitrate, and Bifunctional Nitrates

  17. Atomic structure of nitrate-binding protein crucial for photosynthetic productivity

    Energy Technology Data Exchange (ETDEWEB)

    Koropatkin, Nicole M.; Pakrasi, Himadri B.; Smith, Thomas J.

    2006-06-27

    Cyanobacteria, blue-green algae, are the most abundant autotrophs in aquatic environments and form the base of all aquatic food chains by fixing carbon and nitrogen into cellular biomass. The single most important nutrient for photosynthesis and growth is nitrate, which is severely limiting in many aquatic environments particularly the open ocean (1, 2). It is therefore not surprising that NrtA, the solute-binding component of the high-affinity nitrate ABC transporter, is the single-most abundant protein in the plasma membrane of these bacteria (3). Here we describe the first structure of a nitratespecific receptor, NrtA from Synechocystis sp. PCC 6803, complexed with nitrate and determined to a resolution of 1.5Å. NrtA is significantly larger than other oxyanionbinding proteins, representing a new class of transport proteins. From sequence alignments, the only other solute-binding protein in this class is CmpA, a bicarbonatebinding protein. Therefore, these organisms created a novel solute-binding protein for two of the most important nutrients; inorganic nitrogen and carbon. The electrostatic charge distribution of NrtA appears to force the protein off of the membrane while the flexible tether facilitates the delivery of nitrate to the membrane pore. The structure not only details the determinants for nitrate selectivity in NrtA, but also the bicarbonate specificity in CmpA. Nitrate and bicarbonate transport are regulated by the cytoplasmic proteins NrtC and CmpC, respectively. Interestingly, the residues lining the ligand binding pockets suggest that they both bind nitrate. This implies that the nitrogen and carbon uptake pathways are synchronized by intracellular nitrate and nitrite.3 The nitrate ABC transporter of cyanobacteria is composed of four polypeptides (Figure 1): a high-affinity periplasmic solute-binding lipoprotein (NrtA), an integral membrane permease (NrtB), a cytoplasmic ATPase (NrtD), and a unique ATPase/solute-binding fusion protein (Nrt

  18. [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%.

  19. Nitration of Hsp90 on Tyrosine 33 Regulates Mitochondrial Metabolism.

    Science.gov (United States)

    Franco, Maria C; Ricart, Karina C; Gonzalez, Analía S; Dennys, Cassandra N; Nelson, Pascal A; Janes, Michael S; Mehl, Ryan A; Landar, Aimee; Estévez, Alvaro G

    2015-07-31

    Peroxynitrite production and tyrosine nitration are present in several pathological conditions, including neurodegeneration, stroke, aging, and cancer. Nitration of the pro-survival chaperone heat shock protein 90 (Hsp90) in position 33 and 56 induces motor neuron death through a toxic gain-of-function. Here we show that nitrated Hsp90 regulates mitochondrial metabolism independently of the induction of cell death. In PC12 cells, a small fraction of nitrated Hsp90 was located on the mitochondrial outer membrane and down-regulated mitochondrial membrane potential, oxygen consumption, and ATP production. Neither endogenous Hsp90 present in the homogenate nor unmodified and fully active recombinant Hsp90 was able to compete with the nitrated protein for the binding to mitochondria. Moreover, endogenous or recombinant Hsp90 did not prevent the decrease in mitochondrial activity but supported nitrated Hsp90 mitochondrial gain-of-function. Nitrotyrosine in position 33, but not in any of the other four tyrosine residues prone to nitration in Hsp90, was sufficient to down-regulate mitochondrial activity. Thus, in addition to induction of cell death, nitrated Hsp90 can also regulate mitochondrial metabolism, suggesting that depending on the cell type, distinct Hsp90 nitration states regulate different aspects of cellular metabolism. This regulation of mitochondrial homeostasis by nitrated Hsp90 could be of particular relevance in cancer cells. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  20. Nitrate removal using different carbon substrates in a laboratory model.

    Science.gov (United States)

    Hashemi, Seyyed Ebrahim; Heidarpour, Manouchehr; Mostafazadeh-Fard, Behrouz

    2011-01-01

    Agricultural fields have been frequently identified as major contributors of nitrate leaching into surface and ground waters. Tile drains can act as direct pathways, transferring leached nitrate to surface water. Bioreactor filters are useful for the removal of nitrate from drainage waters; however, these filters require an external carbon supply to sustain denitrification. In this study, four organic carbon sources including wood, barley straw, rice husks, and date palm leaf, were used to enhance denitrification and the effects of water velocity and influent nitrate concentration on the nitrate removal were evaluated. Cumulative nitrate removal was highest for the date palm leaf treatments and was lowest for the wood treatments. The effects were in decreasing order for date palm leaf, barley straw, rice husks, and wood, respectively. The performance of the biofilters improved with increasing influent nitrate concentration and decreasing water velocity, allowing for high nitrate removal rates to be achieved. The results showed that all of the treatments had reduced the effluent nitrate concentrations below the USEPA maximum contaminant level for drinking water of 45 mg L(-1) nitrate at the end of the study.

  1. Nitrate removal using Brevundimonas diminuta MTCC 8486 from ground water.

    Science.gov (United States)

    Kavitha, S; Selvakumar, R; Sathishkumar, M; Swaminathan, K; Lakshmanaperumalsamy, P; Singh, A; Jain, S K

    2009-01-01

    Brevundimonas diminuta MTCC 8486, isolated from marine soil of coastal area of Trivandrum, Kerala, was used for biological removal of nitrate from ground water collected from Kar village of Pali district, Rajasthan. The organism was found to be resistance for nitrate up to 10,000 mg L(-1). The optimum growth conditions for biological removal of nitrate were established in batch culture. The effect of carbon sources on nitrate removal was investigated using mineral salt medium (MSM) containing 500 mg L(-1) of nitrate to select the most effective carbon source. Among glucose and starch as carbon source, glucose at 1% concentration increased the growth (182+/-8.24 x 10(4) CFU mL(-1)) and induced maximum nitrate reduction (86.4%) at 72 h. The ground water collected from Kar village, Pali district of Rajasthan containing 460+/-5.92 mg L(-1) of nitrate was subjected to three different treatment processes in pilot scale (T1 to T3). Higher removal of nitrate was observed in T2 process (88%) supplemented with 1% glucose. The system was scaled up to 10 L pilot scale treatment plant. At 72 h the nitrate removal was observed to be 95% in pilot scale plant. The residual nitrate level (23+/-0.41 mg L(-1)) in pilot scale treatment process was found to be below the permissible limit of WHO.

  2. Reductive denitrification of nitrate by scrap iron filings

    Institute of Scientific and Technical Information of China (English)

    HAO Zhi-wei; XU Xin-hua; WANG Da-hui

    2005-01-01

    Reduction of nitrate by zero-valent iron is a highly exergonic reaction that has long been known to occur. Use of scrap iron filings (SIF) as the PRB (Permeable Reactive Barrier) material can be used to recycle certain by-products, and identify cheaper replacements for expensive conventional PRB materials, especially pure metallic iron. The feasibility of reductive denitrification of nitrate by SIF was studied by batch experiments. Operational parameters such as pH value, SIF dosage and initial concentration of nitrate were investigated. The removal efficiency of nitrate reached 80% under the conditions of pH of 2.5, nitrate initial concentration of 45 mg/L and SIF dosage of 100 g/L within 4 h. Results indicated that nitrate removal is inversely related to pH. Low pH value condition favors for the nitrate transformation. Different from the results of others who studied nitrate reduction using iron powder, we found that there was a lag time before nitrate reduction occurs, even at low pH. Finally, the possible mechanism of nitrate reduction by Fe0 is discussed.

  3. Growing patterns to produce 'nitrate-free' lettuce (Lactuca sativa).

    Science.gov (United States)

    Croitoru, Mircea Dumitru; Muntean, Daniela-Lucia; Fülöp, Ibolya; Modroiu, Adriana

    2015-01-01

    Vegetables can contain significant amounts of nitrate and, therefore, may pose health hazards to consumers by exceeding the accepted daily intake for nitrate. Different hydroponic growing patterns were examined in this work in order to obtain 'nitrate-free lettuces'. Growing lettuces on low nitrate content nutrient solution resulted in a significant decrease in lettuces' nitrate concentrations (1741 versus 39 mg kg(-1)), however the beneficial effect was cancelled out by an increase in the ambient temperature. Nitrate replacement with ammonium was associated with an important decrease of the lettuces' nitrate concentration (from 1896 to 14 mg kg(-1)) and survival rate. An economically feasible method to reduce nitrate concentrations was the removal of all inorganic nitrogen from the nutrient solution before the exponential growth phase. This method led to lettuces almost devoid of nitrate (10 mg kg(-1)). The dried mass and calcinated mass of lettuces, used as markers of lettuces' quality, were not influenced by this treatment, but a small reduction (18%, p lettuces and their modifications are also discussed in the paper. It is possible to obtain 'nitrate-free' lettuces in an economically feasible way.

  4. Selective recognition of uranyl ions from bulk of thorium(iv) and lanthanide(iii) ions by tetraalkyl urea: a combined experimental and quantum chemical study.

    Science.gov (United States)

    Vats, Bal Govind; Das, Debasish; Sadhu, Biswajit; Kannan, S; Pius, I C; Noronha, D M; Sundararajan, Mahesh; Kumar, Mukesh

    2016-06-21

    The selective separation of uranyl ions from an aqueous solution is one of the most important criteria for sustainable nuclear energy production. We report herein a known, but unexplored extractant, tetraalkyl urea, which shows supreme selectivity for uranium in the presence of interfering thorium and other lanthanide ions from a nitric acid medium. The structural characterization of the uranyl complex (UO2X2·2L, where X = NO3(-), Cl(-) and Br(-)) by IR, NMR and single crystal X-ray diffraction provides insight into the strong interaction between the uranyl ion and the ligand. The origin of this supreme selectivity for uranyl ions is further supported by electronic structure calculations. Uranyl binding with the extractant is thermodynamically more favourable when compared to thorium and the selectivity is achieved through a combination of electronic and steric effects.

  5. Microbial community in packed bed bioreactor involved in nitrate remediation from low level radioactive waste.

    Science.gov (United States)

    Mishra, Madhusmita; Jain, Savita; Thakur, Ashoke Ranjan; RayChaudhuri, Shaon

    2014-03-01

    Nitrate is the second largest contaminant of agriculture soil after pesticides. It also is a major pollutant from nuclear and metallurgical operations. Conventional methods for nitrate removal suffers from high cost and complexity leaving bioremediation as a viable alternative strategy. A pilot plant of 2.5 m(3)/day capacity has been functioning since 2005 based on microbial consortia treating actual effluent from nuclear power plant having pH of 7-8.5 (optimum) with N:C ratio of 1:1.7. The maximum biodegradable nitrate concentration of 3000 ppm could be reduced to below permissible limit (44.2 ppm) within 24 h in presence of sodium acetate as carbon source. Culture independent analysis (16S rDNA based) revealed clones having closest identity with uncultured bacterium, Pseudomonas stutzeri and Azoarcus sp. The existence of dissimilatory pathway of nitrate reduction in the community DNA is indicated by presence of nirS and nirK gene. Though the microbial mass was developed using municipal sewage, absence of Mycobacterium sp was confirmed using PCR. The understanding of the molecular identification of the consortium would help in developing the preservation strategy of the microbial mass for replication and perpetuation of the system. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Change in metabolic status of glutathione by palladium nitrate in blood components.

    Science.gov (United States)

    Mukhtiar, Muhammad; Khan, Muhammad Farid; Jan, Syed Umer; Khan, Haroon; Ullah, Naseem; Badshah, Amir

    2013-01-01

    This piece of research work present the toxicological impact of varied concentrations of palladium nitrate [Pd (NO3)2] by changing the chemical status of glutathione and the way how glutathione plays its role in detoxification and conjugation processes of [Pd (NO(3))(2))] in whole blood components (plasma and cytosolic fraction). The impact of different concentration of [Pd (NO3)2] on reduced glutathione level in whole blood component (plasma and cytosolic fraction) were measured spectrophotometrically following Standard Ellman's method. Compared with control sample, significant decrease in the GSH content in whole blood components (plasma and cytosolic fraction) was obtained with various concentrations (100µM-1000µM) of palladium nitrate. Depleted GSH level was more pronounced with time incubation period (0-90) minutes. These finding shows that changes in the GSH status produced by palladium nitrate could either be due to palladium nitrate and glutathione( Pd-SG) complex formation or by conversion of reduce glutathione (2GSH + Pd(+2) - GSSG). This change in the GSH metabolic status provides information regarding the mechanism of palladium, in blood components.

  7. Liquid-liquid extraction kinetics of uranyl nitrate and actinides (III)-lanthanides nitrates by extractants with amide function; Cinetique d`extraction liquide-liquide du nitrate d`uranyle et des nitrates d`actinides (III) et de lanthanides (III) par des extractants a fonction amide

    Energy Technology Data Exchange (ETDEWEB)

    Toulemonde, V.

    1995-12-20

    Nowadays, the most important part of electric power is generated by fission energy. But spent fuels have then to be reprocessed. The production of these reprocessed materials separately and with a high purity level is done according to a liquid-liquid extraction process (Purex process) with the use of tributyl phosphate as solvent. Optimization studies concerning the extracting agent have been undertaken. This work gives the results obtained for the uranyl nitrate and the actinides (III)-lanthanides (III) nitrates extraction by extractants with amide function (monoamide for U(VI) and diamide for actinides (III) and lanthanides (III)). The extraction kinetics have been studied in the case of a metallic specie transfer from the aqueous phase towards the organic phase. The experiments show that the nitrates extraction kinetics is limited by the complexation chemical reaction of the species at the interface between the two liquids. An adsorption-desorption interfacial reactional mechanism (Langmuir theory) is proposed for the uranyl nitrate. (O.M.). 89 refs.

  8. Trace concentration - Huge impact: Nitrate in the calcite/Eu(III) system

    Science.gov (United States)

    Hofmann, Sascha; Voïtchovsky, Kislon; Schmidt, Moritz; Stumpf, Thorsten

    2014-01-01

    The interactions of trivalent lanthanides and actinides with secondary mineral phases such as calcite is of high importance for the safety assessment of deep geological repositories for high level nuclear waste (HLW). Due to similar ionic radii, calcium-bearing mineral phases are suitable host minerals for Ln(III) and An(III) ions. Especially calcite has been proven to retain these metal ions effectively by both surface complexation and bulk incorporation. Since anionic ligands (e.g., nitrate) are omnipresent in the geological environment and due to their coordinating properties, their influence on retentive processes should not be underestimated. Nitrate is a common contaminant in most HLW forms as a result of using nitric acid in fuel reprocessing. It is also formed by microbial activity under aerobic conditions. In this study, atomic force microscopy investigations revealed a major influence of nitrate upon the surface of calcite crystals. NaNO3 causes serious modifications even in trace amounts (surface layer of low crystallinity on top of the calcite crystal. Time-resolved laser fluorescence spectroscopy of Eu(III) showed that, within this layer, Eu(III) ions are incorporated, while losing most of their hydration shell. The results show that solid solution modelling for actinides in calcite must take into account the presence of nitrate in pore and ground waters.

  9. Pollution par les nitrates des eaux souterraines du bassin d'Essaouira (Maroc)

    Science.gov (United States)

    Laftouhi, Nour-Eddine; Vanclooster, Marnik; Jalal, Mohammed; Witam, Omar; Aboufirassi, Mohamed; Bahir, Mohamed; Persoons, Étienne

    2003-03-01

    The Essaouira Basin (Morocco) contains a multi-layered aquifer situated in fractured and karstic materials from the Middle and Upper Cretaceous (the Cenomanian, Turonian and Senonian). Water percolates through the limestone and dolomite formations of the Turonian stage either through the marls and calcareous marls of the Cenomanian or through the calcareous marly materials of the Senonian. The aquifer system may be interconnected since the marl layer separating the Turonian, Cenomanian and Senonian aquifers is thin or intensively fractured. In that case, the water is transported through a network of fractures and stratification joints. This paper describes the extent of the nitrate pollution in the area and its origin. Most of the wells and drillholes located in the Kourimat perimeter are contaminated by nitrates with some concentrations over 400 mg l-1. Nitrate contamination is also observed in the surface water of the Qsob River, which constitutes the natural outlet of the multi-layered complex aquifer system. In this area, agriculture is more developed than in the rest of the Essaouira Basin. Diffuse pollution of the karstic groundwater body by agricultural fertiliser residues may therefore partially explain the observed nitrate pollution. However, point pollution around the wells, springs and drillholes from human wastewater, livestock faeces and the mineralisation of organic debris close to the Muslim cemeteries cannot be excluded.

  10. High-resolution in situ measurement of nitrate in runoff from the Greenland Ice Sheet.

    Science.gov (United States)

    Beaton, Alexander David; Wadham, Jemma L; Hawkings, Jon; Bagshaw, Elizabeth A; Lamarche-Gagnon, Guillaume; Mowlem, Matthew C; Tranter, Martyn

    2017-09-27

    We report the first in situ high-resolution nitrate time series from two proglacial meltwater rivers draining the Greenland Ice Sheet, using a recently developed submersible analyser based on lab-on-chip (LOC) technology. The low sample volume (320 μL) required by the LOC analyser meant that low concentration (few to sub μM), highly turbid subglacial meltwater could be filtered and colourimetrically analysed in situ. These data are linked to an unparalleled, multi-component data set. Nitrate concentrations in rivers draining Leverett Glacier in South-West Greenland and Kiattuut Sermiat in Southern Greenland exhibited a clear diurnal signal and a gradual decline at the commencement of the melt season, displaying trends would not be discernible using traditional daily manual sampling. Nitrate concentrations varied by 4.4 μM (+/- 0.2 μM) over a 10-day period at Kiattuut Sermiat and 3.0 μM (+/- 0.2 μM) over a 14 day period at Leverett Glacier. Marked changes in nitrate concentrations were observed when discharge began to increase. High resolution in situ measurements such as these have the potential to significantly advance the understanding of nutrient cycling in remote systems, where the dynamics of nutrient release are complex but are important for downstream biogeochemical cycles.

  11. Nitrate ammonification in mangrove soils: A hidden source of nitrite?

    Directory of Open Access Journals (Sweden)

    Melike eBalk

    2015-03-01

    Full Text Available Nitrate reduction is considered to be a minor microbial pathway in the oxidation of mangrove-derived organic matter due to a limited supply of nitrate in mangrove soils. At a limited availability of this electron acceptor compared to the supply of degradable carbon, nitrate ammonification is thought to be the preferential pathway of nitrate reduction. Mangrove forest mutually differ in their productivity, which may lead to different available carbon to nitrate ratios in their soil. Hence, nitrate ammonification is expected to be of more importance in high- compared to low-productive forests.The hypothesis was tested in flow-through reactors that contain undisturbed mangrove soils from high-productive Avicennia germinans and Rhizophora mangle forests in Florida and low-productive Avicennia marina forests in Saudi Arabia. Nitrate was undetectable in the soils from both regions. It was assumed that a legacy of nitrate ammonification would be reflected by a higher ammonium production from these soils upon the addition of nitrate. Unexpectedly, the soils from the low-productive forests in Saudi Arabia produced considerably more ammonium than the soils from the high-productive forests in Florida. Hence, other environmental factors than productivity must govern the selection of nitrate ammonification or denitrification. A rather intriguing observation was the 1:1 production of nitrite and ammonium during the consumption of nitrate, more or less independent from sampling region, location, sampling depth, mangrove species and from the absence or presence of additional degradable carbon. This 1:1 ratio points to a coupled production of ammonium and nitrite by one group of nitrate-reducing microorganisms. Such a production of nitrite will be hidden under the nitrate-limited conditions of most mangrove forest soils.

  12. Nitrate ammonification in mangrove soils: a hidden source of nitrite?

    Science.gov (United States)

    Balk, Melike; Laverman, Anniet M; Keuskamp, Joost A; Laanbroek, Hendrikus J

    2015-01-01

    Nitrate reduction is considered to be a minor microbial pathway in the oxidation of mangrove-derived organic matter due to a limited supply of nitrate in mangrove soils. At a limited availability of this electron acceptor compared to the supply of degradable carbon, nitrate ammonification is thought to be the preferential pathway of nitrate reduction. Mangrove forest mutually differ in their productivity, which may lead to different available carbon to nitrate ratios in their soil. Hence, nitrate ammonification is expected to be of more importance in high- compared to low-productive forests. The hypothesis was tested in flow-through reactors that contain undisturbed mangrove soils from high-productive Avicennia germinans and Rhizophora mangle forests in Florida and low-productive Avicennia marina forests in Saudi Arabia. Nitrate was undetectable in the soils from both regions. It was assumed that a legacy of nitrate ammonification would be reflected by a higher ammonium production from these soils upon the addition of nitrate. Unexpectedly, the soils from the low-productive forests in Saudi Arabia produced considerably more ammonium than the soils from the high-productive forests in Florida. Hence, other environmental factors than productivity must govern the selection of nitrate ammonification or denitrification. A rather intriguing observation was the 1:1 production of nitrite and ammonium during the consumption of nitrate, more or less independent from sampling region, location, sampling depth, mangrove species and from the absence or presence of additional degradable carbon. This 1:1 ratio points to a coupled production of ammonium and nitrite by one group of nitrate-reducing microorganisms. Such a production of nitrite will be hidden by the presence of active nitrite-reducing microorganisms under the nitrate-limited conditions of most mangrove forest soils.

  13. Nitrate ammonification in mangrove soils: a hidden source of nitrite?

    KAUST Repository

    Balk, Melike

    2015-03-02

    Nitrate reduction is considered to be a minor microbial pathway in the oxidation of mangrove-derived organic matter due to a limited supply of nitrate in mangrove soils. At a limited availability of this electron acceptor compared to the supply of degradable carbon, nitrate ammonification is thought to be the preferential pathway of nitrate reduction. Mangrove forest mutually differ in their productivity, which may lead to different available carbon to nitrate ratios in their soil. Hence, nitrate ammonification is expected to be of more importance in high- compared to low-productive forests. The hypothesis was tested in flow-through reactors that contain undisturbed mangrove soils from high-productive Avicennia germinans and Rhizophora mangle forests in Florida and low-productive Avicennia marina forests in Saudi Arabia. Nitrate was undetectable in the soils from both regions. It was assumed that a legacy of nitrate ammonification would be reflected by a higher ammonium production from these soils upon the addition of nitrate. Unexpectedly, the soils from the low-productive forests in Saudi Arabia produced considerably more ammonium than the soils from the high-productive forests in Florida. Hence, other environmental factors than productivity must govern the selection of nitrate ammonification or denitrification. A rather intriguing observation was the 1:1 production of nitrite and ammonium during the consumption of nitrate, more or less independent from sampling region, location, sampling depth, mangrove species and from the absence or presence of additional degradable carbon. This 1:1 ratio points to a coupled production of ammonium and nitrite by one group of nitrate-reducing microorganisms. Such a production of nitrite will be hidden by the presence of active nitrite-reducing microorganisms under the nitrate-limited conditions of most mangrove forest soils.

  14. Lanthanum(III) and Lutetium(III) in Nitrate-Based Ionic Liquids: A Theoretical Study of Their Coordination Shell.

    Science.gov (United States)

    Bodo, Enrico

    2015-09-03

    By using ab initio molecular dynamics, we investigate the solvent shell structure of La(3+) and Lu(3+) ions immersed in two ionic liquids, ethylammonium nitrate (EAN) and its hydroxy derivative (2-ethanolammonium nitrate, HOEAN). We provide the first study of the coordination properties of these heavy metal ions in such a highly charged nonacqueous environment. We find, as expected, that the coordination in the liquid is mainly due to nitrate anions and that, due to the bidentate nature of the ligand, the complexation shell of the central ion has a nontrivial geometry and a coordination number in terms of nitrate molecules that apparently violates the decrease of ionic radii along the lanthanides series, since the smaller Lu(3+) ion seems to coordinate six nitrate molecules and the La(3+) ion only five. A closer inspection of the structural features obtained from our calculations shows, instead, that the first shell of oxygen atoms is more compact for Lu(3+) than for La(3+) and that the former coordinates 8 oxygen atoms while the latter 10 in accord with the typical lanthanide's trend along the series and that their first solvation shells have a slight irregular and complex geometrical pattern. When moving to the HOEAN solutions, we have found that the solvation of the central ion is possibly also due to the cation itself through the oxygen atom on the side chain. Also, in this liquid, the coordination numbers in terms of oxygen atoms in both solvents is 10 for La(3+) and 8 for Lu(3+).

  15. Impact of ammonium nitrate and sodium nitrate on tadpoles of Alytes obstetricans.

    Science.gov (United States)

    Garriga, Núria; Montori, A; Llorente, G A

    2017-07-01

    The presence of pesticides, herbicides and fertilisers negatively affect aquatic communities in general, and particularly amphibians in their larval phase, even though sensitivity to pollutants is highly variable among species. The Llobregat Delta (Barcelona, Spain) has experienced a decline of amphibian populations, possibly related to the reduction in water quality due to the high levels of farming activity, but also to habitat loss and alteration. We studied the effects of increasing ammonium nitrate and sodium nitrate levels on the survival and growth rate of Alytes obstetricans tadpoles under experimental conditions. We exposed larvae to increasing concentrations of nitrate and ammonium for 14 days and then exposed them to water without pollutants for a further 14 days. Only the higher concentrations of ammonium (>33.75 mg/L) caused larval mortality. The growth rate of larvae was reduced at ≥22.5 mg/L NH4(+), although individuals recovered and even increased their growth rate once exposure to the pollutant ended. The effect of nitrate on growth rate was detected at ≥80 mg/L concentrations, and the growth rate reduction in tadpoles was even observed during the post-exposure phase. The concentrations of ammonium with adverse effects on larvae are within the range levels found in the study area, while the nitrate concentrations with some adverse effect are close to the upper range limit of current concentrations in the study area. Therefore, only the presence of ammonium in the study area is likely to be considered of concern for the population of this species, even though the presence of nitrate could cause some sublethal effects. These negative effects could have an impact on population dynamics, which in this species is highly sensitive to larval mortality due to its small clutch size and prolonged larval period compared to other anuran amphibians.

  16. Protein nitration in biological aging: proteomic and tandem mass spectrometric characterization of nitrated sites.

    Science.gov (United States)

    Kanski, Jaroslaw; Schöneich, Christian

    2005-01-01

    Proteomic techniques for the identification of 3-nitrotyrosine-containing proteins in various biological systems are described with emphasis on the direct mass spectrometric detection and sequencing of 3-nitrotyrosine-containing peptides. Strengths and weaknesses of various separation and mass spectrometric techniques are discussed. Some examples for the MS/MS analysis of nitrated peptides obtained from aging rat heart and skeletal muscle are provided, such as nitration of Tyr105 of the mitochondrial electron-transfer flavoprotein and Tyr14 of creatine kinase.

  17. Complexation of Nd(III) with tetraborate ion and its effect on actinide (III) solubility in WIPP brine

    Energy Technology Data Exchange (ETDEWEB)

    Borkowski, Marian [Los Alamos National Laboratory; Richmann, Michael K [Los Alamos National Laboratory; Reed, Donald T [Los Alamos National Laboratory; Yongliang, Xiong [SNL

    2010-01-01

    The potential importance of tetraborate complexation on lanthanide(III) and actinide(III) solubility is recognized in the literature but a systematic study of f-element complexation has not been performed. In neodymium solubility studies in WIPP brines, the carbonate complexation effect is not observed since tetraborate ions form a moderately strong complex with neodymium(III). The existence of these tetraborate complexes was established for low and high ionic strength solutions. Changes in neodymium(III) concentrations in undersaturation experiments were used to determine the neodymium with tetraborate stability constants as a function of NaCl ionic strength. As very low Nd(III) concentrations have to be measured, it was necessary to use an extraction pre-concentration step combined with ICP-MS analysis to extend the detection limit by a factor of 50. The determined Nd(III) with borate stability constants at infinite dilution and 25 C are equal to log {beta}{sub 1} = 4.55 {+-} 0.06 using the SIT approach, equal to log {beta}{sub 1} = 4.99 {+-} 0.30 using the Pitzer approach, with an apparent log {beta}{sub 1} = 4.06 {+-} 0.15 (in molal units) at I = 5.6 m NaCl. Pitzer ion-interaction parameters for neodymium with tetraborate and SIT interaction coefficients were also determined and reported.

  18. Complexation of Nd(III) with tetraborate ion and its effect on actinide(III) solubility in WIPP brine

    Energy Technology Data Exchange (ETDEWEB)

    Borkowski, M.; Richmann, M.; Reed, D.T. [Earth and Environmental Sciences Div., Los Alamos National Lab., Carlsbad Operations, NM (United States); Xiong, Y. [Sandia National Labs., Carlsbad Program Group, Carlsbad, NM (United States)

    2010-07-01

    The potential importance of tetraborate complexation on lanthanide(III) and actinide(III) solubility is recognized in the literature but a systematic study of f-element complexation has not been performed. In neodymium solubility studies in WIPP brines, the carbonate complexation effect is not observed since tetraborate ions form a moderately strong complex with neodymium(III). The existence of these tetraborate complexes was established for low and high ionic strength solutions. Changes in neodymium(III) concentrations in undersaturation experiments were used to determine the neodymium with tetraborate stability constants as a function of NaCl ionic strength. As very low Nd(III) concentrations have to be measured, it was necessary to use an extraction pre-concentration step combined with ICP-MS analysis to extend the detection limit by a factor of 50. The determined Nd(III) with borate stability constants at infinite dilution and 25 C are equal to log {beta}{sub 1} = 4.55 {+-} 0.06 using the SIT approach, equal to log {beta}{sub 1} = 4.99 {+-} 0.30 using the Pitzer approach, with an apparent log {beta}{sub 1} = 4.06 {+-} 0.15 (in molal units) at I = 5.6 m NaCl. Pitzer ion-interaction parameters for neodymium with tetraborate and SIT interaction coefficients were also determined and reported. (orig.)

  19. NITRATE DESTRUCTION LITERATURE SURVEY AND EVALUATION CRITERIA

    Energy Technology Data Exchange (ETDEWEB)

    Steimke, J.

    2011-02-01

    This report satisfies the initial phase of Task WP-2.3.4 Alternative Sodium Recovery Technology, Subtask 1; Develop Near-Tank Nitrate/Nitrite Destruction Technology. Some of the more common anions in carbon steel waste tanks at SRS and Hanford Site are nitrate which is corrosive, and nitrite and hydroxide which are corrosion inhibitors. At present it is necessary to periodically add large quantities of 50 wt% caustic to waste tanks. There are three primary reasons for this addition. First, when the contents of salt tanks are dissolved, sodium hydroxide preferentially dissolves and is removed. During the dissolution process the concentration of free hydroxide in the tank liquid can decrease from 9 M to less than 0.2 M. As a result, roughly half way through the dissolution process large quantities of sodium hydroxide must be added to the tank to comply with requirements for corrosion control. Second, hydroxide is continuously consumed by reaction with carbon dioxide which occurs naturally in purge air used to prevent buildup of hydrogen gas inside the tanks. The hydrogen is generated by radiolysis of water. Third, increasing the concentration of hydroxide increases solubility of some aluminum compounds, which is desirable in processing waste. A process that converts nitrate and nitrite to hydroxide would reduce certain costs. (1) Less caustic would be purchased. (2) Some of the aluminum solid compounds in the waste tanks would become more soluble so less mass of solids would be sent to High Level Vitrification and therefore it would be not be necessary to make as much expensive high level vitrified product. (3) Less mass of sodium would be fed to Saltstone at SRS or Low Level Vitrification at Hanford Site so it would not be necessary to make as much low level product. (4) At SRS less nitrite and nitrate would be sent to Defense Waste Processing Facility (DWPF) so less formic acid would be consumed there and less hydrogen gas would be generated. This task involves

  20. Effect of Sodium Nitrate and Nitrate Reducing Bacteria on Methane Production and Fermentation with Buffalo Rumen Liquor

    Directory of Open Access Journals (Sweden)

    Pillanatham Civalingam Sakthivel

    2012-06-01

    Full Text Available Nitrate can serve as a terminal electron acceptor in place of carbon dioxide and inhibit methane emission in the rumen and nitrate reducing bacteria might help enhance the reduction of nitrate/nitrite, which depends on the type of feed offered to animals. In this study the effects of three levels of sodium nitrate (0, 5, 10 mM on fermentation of three diets varying in their wheat straw to concentrate ratio (700:300, low concentrate, LC; 500:500, medium concentrate, MC and 300:700, high concentrate, HC diet were investigated in vitro using buffalo rumen liquor as inoculum. Nitrate reducing bacteria, isolated from the rumen of buffalo were tested as a probiotic to study if it could help in enhancing methane inhibition in vitro. Inclusion of sodium nitrate at 5 or 10 mM reduced (p<0.01 methane production (9.56, 7.93 vs. 21.76 ml/g DM; 12.20, 10.42 vs. 25.76 ml/g DM; 15.49, 12.33 vs. 26.86 ml/g DM in LC, MC and HC diets, respectively. Inclusion of nitrate at both 5 and 10 mM also reduced (p<0.01 gas production in all the diets, but in vitro true digestibility (IVTD of feed reduced (p<0.05 only in LC and MC diets. In the medium at 10 mM sodium nitrate level, there was 0.76 to 1.18 mM of residual nitrate and nitrite (p<0.01 also accumulated. In an attempt to eliminate residual nitrate and nitrite in the medium, the nitrate reducing bacteria were isolated from buffalo adapted to nitrate feeding and introduced individually (3 ml containing 1.2 to 2.3×106 cfu/ml into in vitro incubations containing the MC diet with 10 mM sodium nitrate. Addition of live culture of NRBB 57 resulted in complete removal of nitrate and nitrite from the medium with a further reduction in methane and no effect on IVTD compared to the control treatments containing nitrate with autoclaved cultures or nitrate without any culture. The data revealed that nitrate reducing bacteria can be used as probiotic to prevent the accumulation of nitrite when sodium nitrate is used to reduce

  1. Accumulation of Nitrate in Vegetables and Its Possible Implications to Human Health

    Institute of Scientific and Technical Information of China (English)

    DU Shao-ting; ZHANG Yong-song; LIN Xian-yong

    2007-01-01

    In recent times, there are two kinds of completely opposite viewpoints about the impacts of nitrate on human health. To further objectively understand the effects of nitrate on human health, both of harmfulness and possible benefits of nitrate to human body, it is discussed in this review from the aspects of nitrate accumulation in vegetables, the source of nitrate ingested into human body, and the transformation of nitrate in human body, as well as the pathogenesis and physiological functions of nitrate metabolism.

  2. Evaluating Ecosystem Services for Reducing Groundwater Nitrate Contamination: Nitrate Attenuation in the Unsaturated and Saturated Zones

    Science.gov (United States)

    Wang, J.

    2013-12-01

    Nitrates are the most common type of groundwater contamination in agricultural regions. Environmental policies targeting nitrates have focused on input control (e.g., restricted fertilizer application), intermediate loads control (e.g., reduce nitrate leached from crop fields), and final loads control (e.g., reduce catchment nitrate loads). Nitrate loads can be affected by hydrological processes in both unsaturated and saturated zones. Although many of these processes have been extensively investigated in literature, they are commonly modeled as exogenous to farm management. A couple of recent studies by scientists from the Lawrence Livermore National Laboratory show that in some situations nitrate attenuation processes in the unsaturated/saturated zone, particularly denitrification, can be intensified by certain management practices to mitigate nitrate loads. Therefore, these nitrate attenuation processes can be regarded as a set of ecosystem services that farmers can take advantage of to reduce their cost of complying with environmental policies. In this paper, a representative California dairy farm is used as a case study to show how such ecosystem attenuation services can be framed within the farm owner's decision-making framework as an option for reducing groundwater nitrate contamination. I develop an integrated dynamic model, where the farmer maximizes discounted net farm profit over multiple periods subject to environmental regulations. The model consists of three submodels: animal-waste-crop, hydrologic, and economic model. In addition to common choice variables such as irrigation, fertilization, and waste disposal options, the farmer can also endogenously choose from three water sources: surface water, deep groundwater (old groundwater in the deep aquifer that is not affected by farm effluent in the short term), and shallow groundwater (drainage water that can be recycled via capture wells at the downstream end of the farm). The capture wells not only

  3. Glucose elevates NITRATE TRANSPORTER2.1 protein levels and nitrate transport activity independently of its HEXOKINASE1-mediated stimulation of NITRATE TRANSPORTER2.1 expression.

    Science.gov (United States)

    de Jong, Femke; Thodey, Kate; Lejay, Laurence V; Bevan, Michael W

    2014-01-01

    Mineral nutrient uptake and assimilation is closely coordinated with the production of photosynthate to supply nutrients for growth. In Arabidopsis (Arabidopsis thaliana), nitrate uptake from the soil is mediated by genes encoding high- and low-affinity transporters that are transcriptionally regulated by both nitrate and photosynthate availability. In this study, we have studied the interactions of nitrate and glucose (Glc) on gene expression, nitrate transport, and growth using glucose-insensitive2-1 (gin2-1), which is defective in sugar responses. We confirm and extend previous work by showing that HEXOKINASE1-mediated oxidative pentose phosphate pathway (OPPP) metabolism is required for Glc-mediated NITRATE TRANSPORTER2.1 (NRT2.1) expression. Treatment with pyruvate and shikimate, two products derived from intermediates of the OPPP that are destined for amino acid production, restores wild-type levels of NRT2.1 expression, suggesting that metabolites derived from OPPP metabolism can, together with Glc, directly stimulate high levels of NRT2.1 expression. Nitrate-mediated NRT2.1 expression is not influenced by gin2-1, showing that Glc does not influence NRT2.1 expression through nitrate-mediated mechanisms. We also show that Glc stimulates NRT2.1 protein levels and transport activity independently of its HEXOKINASE1-mediated stimulation of NRT2.1 expression, demonstrating another possible posttranscriptional mechanism influencing nitrate uptake. In gin2-1 plants, nitrate-responsive biomass growth was strongly reduced, showing that the supply of OPPP metabolites is essential for assimilating nitrate for growth.

  4. Laboratory study of nitrate photolysis in Antarctic snow

    DEFF Research Database (Denmark)

    Berhanu, Tesfaye A.; Meusinger, Carl; Erbland, Joseph;

    2014-01-01

    Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. [" Laboratory study of nitrate photolysis...... in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate (15N, 17O, and 18O) provide...... additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters...

  5. Ice core measurements of the isotopic composition of nitrate: new results and interpretation

    Science.gov (United States)

    Steig, E. J.; Hastings, M. G.; Alexander, B.; Jarvis, J. C.; Kunasek, S. C.

    2006-12-01

    Several fundamental questions about the magnitude of natural variability in the global nitrogen cycle, and the impact of human activities in the last century, remain open. For example, lakes around the world show significant declines in organic nitrogen isotope ratios but it remains unclear to what extent this reflects changed nitrate sources or in situ changes in lake biogeochemistry. It also remains unknown whether atmospheric NOx mixing ratios were significantly different during the last glacial period; because atmospheric NOx abundances influence methane oxidation chemistry, this may have implications for closure of the global methane budget. While ice core measurements of nitrate concentration demonstrate that human activity has at least doubled the concentration of nitrogen oxides in the atmosphere in the last century, more quantitative use of such data has proven difficult due to the variety of possible nitrate sources, the complex atmospheric chemistry, and the potential for post-depositional change. The utility of ice cores in elucidating past changes in the global nitrogen cycle may be greatly enhanced through the analysis of nitrate isotope ratios. Our work on ice cores is coupled with direct atmospheric measurements of gas-phase HNO3 and its precursors, and global modeling of isotope variations in reactive nitrogen species, reported elsewhere at this meeting. Here, we report on our ongoing analyses of nitrogen and oxygen isotope ratios from ice cores at South Pole, the WAIS Divide (site of the new US drilling effort in West Antarctica), GISP2, and a new 100-meter core from Summit, Greenland. Snow pit data demonstrate that changes in oxygen isotope ratios (δ18O and Δ17O [= δ17O -0.52*δ18O]) in nitrate can be related directly to changes in the ratio of gas phase ("daytime") vs. aqueous phase ("nighttime") chemistry in the production of nitrate in the atmosphere. Nitrogen isotope ratios (δ15N) are also affected by photochemistry, but variations in

  6. Impact of weather variability on nitrate leaching

    Science.gov (United States)

    Richards, Karl; Premrov, Alina; Hackett, Richard; Coxon, Catherine

    2016-04-01

    The loss of nitrate (NO3 - N) to water via leaching and overland flow contributes to eutrophication of freshwaters, transitional and near coastal waters with agriculture contributing significantly to nitrogen (N) loading to these water. Environmental regulations, such as the Nitrates and Water Framework Directives, have increased constraints on farmers to improve N management in regions at risk of NO3--N loss to water. In addition, farmers also have to manage their systems within a changing climate as the imapcts of climate change begin to impact resulting in more frequent extreme events such as floods and droughts. The objective of this study was to investigate the link between weather volatility and the concentration of leached NO3--N spring barley. Leaching was quantified under spring barley grown on a well-drained, gravelly sandy soil using ceramic cup samplers over 6 drainage years under the same farming practices and treatments. Soil solution NO3--N concentrations under spring barley grown by conventional inversion ploughing and reduced tillage were compared to weather parameters over the period. Weather was recorded at a national Met Eireann weather station on site. Soil solution NO3--N varied significantly between years. Within individual years NO3--N concentrations varied over the drainage season, with peak concentrations generally observed in the autumn time, decreasing thereafter. Under both treatments there was a three-fold difference in mean annual soil solution NO3--N concentration over the 6 years with no change in the agronomic practices (crop type, tillage type and fertiliser input). Soil solution nitrate concentrations were significantly influenced by weather parameters such as rainfall, effective drainage and soil moisture deficit. The impact of climate change in Ireland could lead to increased NO3--N loss to water further exacerbating eutrophication of sensitive estuaries. The increased impact on eutrophication of waters, related to climatic

  7. Endogenously nitrated proteins in mouse brain: links to neurodegenerative disease.

    Science.gov (United States)

    Sacksteder, Colette A; Qian, Wei-Jun; Knyushko, Tatyana V; Wang, Haixing; Chin, Mark H; Lacan, Goran; Melega, William P; Camp, David G; Smith, Richard D; Smith, Desmond J; Squier, Thomas C; Bigelow, Diana J

    2006-07-04

    Increased abundance of nitrotyrosine modifications of proteins have been documented in multiple pathologies in a variety of tissue types and play a role in the redox regulation of normal metabolism. To identify proteins sensitive to nitrating conditions in vivo, a comprehensive proteomic data set identifying 7792 proteins from a whole mouse brain, generated by LC/LC-MS/MS analyses, was used to identify nitrated proteins. This analysis resulted in the identification of 31 unique nitrotyrosine sites within 29 different proteins. More than half of the nitrated proteins that have been identified are involved in Parkinson's disease, Alzheimer's disease, or other neurodegenerative disorders. Similarly, nitrotyrosine immunoblots of whole brain homogenates show that treatment of mice with 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP), an experimental model of Parkinson's disease, induces an increased level of nitration of the same protein bands observed to be nitrated in brains of untreated animals. Comparing sequences and available high-resolution structures around nitrated tyrosines with those of unmodified sites indicates a preference of nitration in vivo for surface accessible tyrosines in loops, a characteristic consistent with peroxynitrite-induced tyrosine modification. In addition, most sequences contain cysteines or methionines proximal to nitrotyrosines, contrary to suggestions that these amino acid side chains prevent tyrosine nitration. More striking is the presence of a positively charged moiety near the sites of nitration, which is not observed for non-nitrated tyrosines. Together, these observations suggest a predictive tool of functionally important sites of nitration and that cellular nitrating conditions play a role in neurodegenerative changes in the brain.

  8. NITRATE REMOVAL FROM WATER USING SURFACE-MODIFIED ULTRAFILTRATION MEMBRANES

    OpenAIRE

    Habuda-Stanić, Mirna; Nujić, Marija; Santo, Vera

    2014-01-01

    Elevated nitrate concentrations in natural water sources are a worldwide concern due to the extensive levels of soil N-fertilization. This study investigates three commercially available polyethersulfone (PES) ultrafiltration (UF) membranes with different molecular weight cut-offs (5, 10, and 30 kDa), which we modified with a cationic surfactant, cetylpyridinium chloride to improve their nitrate removal. The nitrate removal efficiency of these membranes was examinated as functions of initial ...

  9. Peroxidase catalyzed nitration of tryptophan derivatives. Mechanism, products and comparison with chemical nitrating agents.

    Science.gov (United States)

    Sala, Alberto; Nicolis, Stefania; Roncone, Raffaella; Casella, Luigi; Monzani, Enrico

    2004-07-01

    The enzymatic nitration of tryptophan derivatives by oxidation of nitrite has been studied using lactoperoxidase and horseradish peroxidase, and compared with the chemical nitration produced by nitrogen dioxide and peroxynitrite. HPLC, mass spectra and NMR analysis of the mixture of products clearly show that nitration occurs at position 4-, 6-, 7-, and N1 of the indole ring, and nitrosation at position N1. Kinetic studies performed on peroxidase/NO2-/H2O2 systems showed substrate saturation behavior with all the tryptophan derivatives employed. The rate dependence on nitrite concentration was found to be linear with horseradish peroxidase while it exhibited saturation behavior with lactoperoxidase. The composition of the product mixture depends on the nitrating agent. While the production of 4-nitro, 6-nitro, 7-nitro and N1-nitro derivatives follows a similar trend, indicating that they are formed according to a similar mechanism, the ratio between the N1-nitroso derivative and other derivatives depends markedly on the nitrite concentration when tryptophan modification is performed by the peroxidase/H2O2/nitrite systems. Analysis of the data indicates that at low nitrite concentration the enzymatic reaction occurs through the classical peroxidase cycle. At high nitrite concentration the reaction proceeds through a different intermediate that we assume to be a protein bound peroxynitrite species.

  10. Immobilization of nitrate reductase onto epoxy affixed silver nanoparticles for determination of soil nitrates.

    Science.gov (United States)

    Sachdeva, Veena; Hooda, Vinita

    2015-08-01

    Epoxy glued silver nanoparticles were used as immobilization support for nitrate reductase (NR). The resulting epoxy/AgNPs/NR conjugates were characterized at successive stages of fabrication by scanning electron microscopy and fourier transform infrared spectroscopy. The immobilized enzyme system exhibited reasonably high conjugation yield (37.6±0.01 μg/cm(2)), with 93.54±0.88% retention of specific activity. Most favorable working conditions of pH, temperature and substrate concentration were ascertained to optimize the performance of epoxy/AgNPs/NR conjugates for soil nitrate quantification. The analytical results for soil nitrate determination were consistent, reliable and reproducible. Minimum detection limit of the method was 0.05 mM with linearity from 0.1 to 11.0 mM. The % recoveries of added nitrates (0.1 and 0.2 mM) wereEpoxy/AgNPs bound NR had a half-life of 18 days at 4 °C and retained 50% activity after 15 reuses. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. NITRATE REDUCTASE ACTIVITY DURING HEAT SHOCK IN WINTER WHEAT

    Directory of Open Access Journals (Sweden)

    Klimenko S.B.

    2006-03-01

    Full Text Available Nitrates are the basic source of nitrogen for the majority of plants. Absorption and transformation of nitrates in plants are determined by external conditions and, first of all, temperature and light intensity. The influence of the temperature increasing till +40 0С on activity of nitrate reductase was studied. It is shown, that the rise of temperature was accompanied by sharp decrease of activity nitrate reductase in leaves of winter wheat, what, apparently, occurred for the account deactivations of enzyme and due to its dissociation.

  12. Electrochemical Studies of Nitrate-Induced Pitting in Carbon Steel

    Energy Technology Data Exchange (ETDEWEB)

    Zapp, P.E.

    1998-12-07

    The phenomenon of pitting in carbon steel exposed to alkaline solutions of nitrate and chloride was studied with the cyclic potentiodynamic polarization technique. Open-circuit and pitting potentials were measured on specimens of ASTM A537 carbon steel in pH 9.73 salt solutions at 40 degrees Celsius, with and without the inhibiting nitrite ion present. Nitrate is not so aggressive a pitting agent as is chloride. Both nitrate and chloride did induce passive breakdown and pitting in nitrite-free solutions, but the carbon steel retained passivity in solutions with 0.11-M nitrite even at a nitrate concentration of 2.2 M.

  13. Endogenously Nitrated Proteins in Mouse Brain: Links To Neurodegenerative Disease

    Energy Technology Data Exchange (ETDEWEB)

    Sacksteder, Colette A.; Qian, Weijun; Knyushko, Tanya V.; Wang, Haixing H.; Chin, Mark H.; Lacan, Goran; Melega, William P.; Camp, David G.; Smith, Richard D.; Smith, Desmond J.; Squier, Thomas C.; Bigelow, Diana J.

    2006-07-04

    Increased nitrotyrosine modification of proteins has been documented in multiple pathologies in a variety of tissue types; emerging evidence suggests its additional role in redox regulation of normal metabolism. In order to identify proteins sensitive to nitrating conditions in vivo, a comprehensive proteomic dataset identifying 7,792 proteins from whole mouse brain, generated by LC/LC-MS/MS analyses, was used to identify nitrated proteins. This analysis resulted in identification of 31 unique nitrotyrosine sites within 29 different proteins. Over half of the nitrated proteins identified have been reported to be involved in Parkinson's disease, Alzheimer's disease, or other neurodegenerative disorders. Similarly, nitrotyrosine immunoblots of whole brain homogenates show that treatment of mice with 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP), an experimental model of Parkinson's disease, induces increased nitration of the same protein bands observed to be nitrated in brains of untreated animals. Comparing sequences and available high resolution structures around nitrated tyrosines with those of unmodified sites indicates a preference of nitration in vivo for surface accessible tyrosines in loops, characteristics consistent with peroxynitrite-induced tyrosine modification. More striking is the five-fold greater nitration of tyrosines having nearby basic sidechains, suggesting electrostatic attraction of basic groups with the negative charge of peroxynitrite. Together, these results suggest that elevated peroxynitrite generation plays a role in neurodegenerative changes in the brain and provides a predictive tool of functionally important sites of nitration.

  14. Regioselective nitration of aromatic substrates in zeolite cages

    Indian Academy of Sciences (India)

    T Esakkidurai; M Kumarraja; K Pitchumani

    2003-04-01

    Phenol is nitrated regioselectively by fuming nitric acid inside the cages of faujasite zeolites (dependent on the loading level) and a remarkable orthoselectivity is observed in solid state nitration. Toluene and chlorobenzene also containing ortho-/para-orienting substituents, undergo faster nitration, though the regioselectivity is less significant in zeolite media. The results are explained on the basis of diffusion and binding of phenol inside zeolite, which facilitate regioselectivity (and which is absent in toluene and chlorobenzene). Other advantages of employing zeolites as media for mild and selective nitration are also highlighted.

  15. Thioploca spp: filamentous sulfur bacteria with nitrate vacuoles

    DEFF Research Database (Denmark)

    Jørgensen, BB; Gallardo, VA

    1999-01-01

    communities of large Thioploca species live along the Pacific coast of South America and in other upwelling areas of high organic matter sedimentation with bottom waters poor in oxygen and rich in nitrate. Each cell of these thioplocas harbors a large liquid vacuole which is used as a storage for nitrate...... with a concentration of lip to 506 mM. The nitrate is used as an electron acceptor for sulfide oxidation and the bacteria may grow autotrophically or mixotrophically using acetate or other organic molecules as carbon source. The filaments stretch up into the overlying seawater, from which they take up nitrate...

  16. Anoxic Activated Sludge Monitoring with Combined Nitrate and Titrimetric Measurements

    DEFF Research Database (Denmark)

    Petersen, B.; Gernaey, Krist; Vanrolleghem, P.A.

    2002-01-01

    An experimental procedure for anoxic activated sludge monitoring with combined nitrate and titrimetric measurements is proposed and evaluated successfully with two known carbon sources, (-)acetate and dextrose. For nitrate measurements an ion-selective nitrate electrode is applied to allow...... was with the carbon source in excess, since excess nitrate provoked nitrite build-up thereby complicating the data interpretation. A conceptual model could quantitatively describe the experimental observations and thus link the experimentally measured proton production with the consumption of electron acceptor...... and carbon source during denitrification....

  17. Significant accumulation of nitrate in Chinese semi-humid croplands

    Science.gov (United States)

    Zhou, Junyu; Gu, Baojing; Schlesinger, William H.; Ju, Xiaotang

    2016-04-01

    Soil nitrate is important for crop growth, but it can also leach to groundwater causing nitrate contamination, a threat to human health. Here, we report a significant accumulation of soil nitrate in Chinese semi-humid croplands based upon more than 7000 samples from 141 sites collected from 1994 to 2015. In the 0-4 meters depth of soil, total nitrate accumulation reaches 453 ± 39, 749 ± 75, 1191 ± 89, 1269 ± 114, 2155 ± 330 kg N ha-1 on average in wheat, maize, open-field vegetables (OFV), solar plastic-roofed greenhouse vegetables (GHV) and orchard fields, respectively. Surprisingly, there is also a comparable amount of nitrate accumulated in the vadose-zone deeper than 4 meters. Over-use of N fertilizer (and/or manure) and a declining groundwater table are the major causes for this huge nitrate reservoir in the vadose-zone of semi-humid croplands, where the nitrate cannot be denitrified due to the presence of oxygen and lack of carbon sources. Future climatic change with more extreme rainfall events would increase the risk of accumulated nitrate moving downwards and threatening groundwater nitrate contamination.

  18. Theoretical studies on new potential high energy density compounds (HEDCs) adamantyl nitrates from gas to solid

    Institute of Scientific and Technical Information of China (English)

    XU XiaoJuan; ZHU WeiHua; GONG XueDong; XIAO HeMing

    2008-01-01

    A series of adamantyl nitrates have been theoretically studied from gas to solid to search for new po-tential high energy density compounds (HEDCs). The heats of formation (HOFs) for the 26 title com-pounds were calculated by designing isodesmic reactions at the B3LYP/6-31G* level. It was found that the HOFs of the 26 isomers with the same number of -ONO2 groups (n) are not correlated well with the corresponding substituted positions. According to the obtained heats of detonation (Q), detonation velocities (D), and detonation pressures (P) using the Kamlet-Jacobs equations, it was found that when n=7~8, the adamantyl nitrates meet the criterion as an HEDC. The calculations on bond dissociation energies of O-N (EO-N) showed that the adamantyl nitrates with gemi -ONO2always have the worst stability among the isomers, and all the adamantyl nitrates with gemi -ONO2 have similar stability. Due to the complexity of their structures, values of Eo-, do not decrease with the increase of the substituent number n obviously, and the stability of adamantyl nitrates is not determined by only one structural parameter. Considering the stability requirement, only 1,2,4,6,8,9,10-adamantyl heptanitrate is recom-mended as a feasible HEDC. Molecular packing searching for 1,2,4,6,8,9,10-adamantyl heptanitrate among 7 most possible space groups (P21/c, P-1, P212121, P21, Pbca, C2/c, and Pna21) using Compass and Dreiding force fields showed that this compound tends to crystallize in P21/c. Ab initio periodic calculations on the electronic structure of the predicted packing showed that the O-NO2 bond is the trigger bond during thermolysis, which agrees with the result derived from the study of dissociation energies of O-N bonds.

  19. Ground-water discharge and base-flow nitrate loads of nontidal streams, and their relation to a hydrogeomorphic classification of the Chesapeake Bay Watershed, middle Atlantic Coast

    Science.gov (United States)

    Bachman, L. Joseph; Lindsey, Bruce D.; Brakebill, John W.; Powars, David S.

    1998-01-01

    billion gallons of water that reaches the Chesapeake Bay each day, nearly 27 billion gallons is base flow. Generalized lithology (siliciclastic, carbonate, crystalline, and unconsolidated) was combined with physiographic province (the Appalachian Plateau, the Valley and Ridge, the Blue Ridge, the Piedmont, including the Mesozoic Lowland section, and the Coastal Plain) to delineate 11 hydrogeomorphic regions. Areal variation of base flow and base-flow nitrate yield were assessed by means of nonparametric, one-way analysis of variance on basins grouped by the dominant hydrogeomorphic region and by correlation analysis of base flow or base-flow nitrate yield with the percentage of land area of a given hydrogeomorphic region within a basin. Base flow appeared to have a significant relation to the hydrogeomorphic regions. The highest percentages of base flow were found in areas underlain by carbonate rock, crystalline rock with relatively low relief, and unconsolidated sediments. Lower percentages were found in areas underlain by siliclastic rocks and crystalline rocks with relatively high relief. The relation between base-flow nitrate yield and hydrogeomorphic region is less clear. Although there is a relation between low nitrate yields and areas underlain by highrelief siliciclastic rocks, and a relation between high yields and carbonate rocks, much of this relation can be explained by the strong association between the hydrogeomorphic units and land use. In addition, most basins are mixtures of several hydrogeomorphic regions, so the nitrate yield from a basin depends on a large number of complex interacting factors. These unclear results indicate that the sample of available data used here may not be adequate to fully assess the relation between base-flow nitrate yield and the hydrogeomorphic setting of the basin. The results appear to show, however, that ground-water discharge is an important component of the total nontidal streamflow, and that ground

  20. Does the evidence about health risks associated with nitrate ingestion warrant an increase of the nitrate standard for drinking water?

    Directory of Open Access Journals (Sweden)

    Benjamin Nigel

    2006-09-01

    Full Text Available Abstract Several authors have suggested that it is safe to raise the health standard for nitrate in drinking water, and save money on measures associated with nitrate pollution of drinking water resources. The major argument has been that the epidemiologic evidence for acute and chronic health effects related to drinking water nitrate at concentrations near the health standard is inconclusive. With respect to the chronic effects, the argument was motivated by the absence of evidence for adverse health effects related to ingestion of nitrate from dietary sources. An interdisciplinary discussion of these arguments led to three important observations. First, there have been only a few well-designed epidemiologic studies that evaluated ingestion of nitrate in drinking water and risk of specific cancers or adverse reproductive outcomes among potentially susceptible subgroups likely to have elevated endogenous nitrosation. Positive associations have been observed for some but not all health outcomes evaluated. Second, the epidemiologic studies of cancer do not support an association between ingestion of dietary nitrate (vegetables and an increased risk of cancer, because intake of dietary nitrate is associated with intake of antioxidants and other beneficial phytochemicals. Third, 2–3 % of the population in Western Europe and the US could be exposed to nitrate levels in drinking water exceeding the WHO standard of 50 mg/l nitrate, particularly those living in rural areas. The health losses due to this exposure cannot be estimated. Therefore, we conclude that it is not possible to weigh the costs and benefits from changing the nitrate standard for drinking water and groundwater resources by considering the potential consequences for human health and by considering the potential savings due to reduced costs for nitrate removal and prevention of nitrate pollution.

  1. Nitration of pollen aeroallergens by nitrate ion in conditions simulating the liquid water phase of atmospheric particles.

    Science.gov (United States)

    Ghiani, Alessandra; Bruschi, Maurizio; Citterio, Sandra; Bolzacchini, Ezio; Ferrero, Luca; Sangiorgi, Giorgia; Asero, Riccardo; Perrone, Maria Grazia

    2016-12-15

    Pollen aeroallergens are present in atmospheric particulate matter (PM) where they can be found in coarse biological particles such as pollen grains (aerodynamic diameter dae>10μm), as well as fragments in the finest respirable particles (PM2.5; daeNitration of tyrosine residues in pollen allergenic proteins can occur in polluted air, and inhalation and deposition of these nitrated proteins in the human respiratory tract may lead to adverse health effects by enhancing the allergic response in population. Previous studies investigated protein nitration by atmospheric gaseous pollutants such as nitrogen dioxide and ozone. In this work we report, for the first time, a study on protein nitration by nitrate ion in aqueous solution, at nitrate concentrations and pH conditions simulating those occurring in the atmospheric aerosol liquid water phase. Experiments have been carried out on the Bovine serum albumin (BSA) protein and the recombinant Phleum pratense allergen (Phl p 2) both in the dark and under UV-A irradiation (range 4-90Wm(-2)) to take into account thermal and/or photochemical nitration processes. For the latter protein, modifications in the allergic response after treatment with nitrate solutions have been evaluated by immunoblot analyses using sera from grass-allergic patients. Experimental results in bulk solutions showed that protein nitration in the dark occurs only in dilute nitrate solutions and under very acidic conditions (pHnitration is always observed (at pH0.5-5) under UV-A irradiation, both in dilute and concentrated nitrate solutions, being significantly enhanced at the lowest pH values. In some cases, protein nitration resulted in an increase of the allergic response. Copyright © 2016. Published by Elsevier B.V.

  2. Spatialised fate factors for nitrate in catchments: modelling approach and implication for LCA results.

    Science.gov (United States)

    Basset-Mens, Claudine; Anibar, Lamiaa; Durand, Patrick; van der Werf, Hayo M G

    2006-08-15

    The challenge for environmental assessment tools, such as Life Cycle Assessment (LCA) is to provide a holistic picture of the environmental impacts of a given system, while being relevant both at a global scale, i.e., for global impact categories such as climate change, and at a smaller scale, i.e., for regional impact categories such as aquatic eutrophication. To this end, the environmental mechanisms between emission and impact should be taken into account. For eutrophication in particular, which is one of the main impacts of farming systems, the fate factor of eutrophying pollutants in catchments, and particularly of nitrate, reflects one of these important and complex environmental mechanisms. We define this fate factor as: the ratio of the amount of nitrate at the outlet of the catchment over the nitrate emitted from the catchment's soils. In LCA, this fate factor is most often assumed equal to 1, while the observed fate factor is generally less than 1. A generic approach for estimating the range of variation of nitrate fate factors in a region of intensive agriculture was proposed. This approach was based on the analysis of different catchment scenarios combining different catchment types and different effective rainfalls. The evolution over time of the nitrate fate factor as well as the steady state fate factor for each catchment scenario was obtained using the INCA simulation model. In line with the general LCA model, the implications of the steady state fate factors for nitrate were investigated for the eutrophication impact result in the framework of an LCA of pig production. A sensitivity analysis to the fraction of nitrate lost as N(2)O was presented for the climate change impact category. This study highlighted the difference between the observed fate factor at a given time, which aggregates both storage and transformation processes and a "steady state fate factor", specific to the system considered. The range of steady state fate factors obtained for

  3. New infrared spectroscopic database for bromine nitrate

    Science.gov (United States)

    Wagner, Georg; Birk, Manfred

    2016-08-01

    Fourier transform infrared measurements of bromine nitrate have been performed in the spectral region 675-1400 cm-1 at 0.014 cm-1 spectral resolution. Absorption cross sections were derived from 38 spectra covering the temperature range from 203 to 296 K and air pressure range from 0 to 190 mbar. For line-by-line analysis, further spectra were recorded at 0.00094 cm-1 spectral resolution at 223 and 293 K. The sample was synthesized from ClONO2 and Br2. Band strengths of the bands ν3 around 803 cm-1 and ν2 around 1286 cm-1 were determined from three pure BrONO2 measurements at different temperatures and pressures. Number densities in the absorption cell were derived from pressure measurements of the purified sample taking into account small amounts of impurities determined spectroscopically. Resulting band strengths are Sν3 = 2.872(52) × 10-17 cm2 molec-1 cm-1 and Sν2 = 3.63(15) × 10-17 cm2 molec-1 cm-1. Absorption cross sections of all measurements were scaled to these band strengths. Further data reduction was achieved with an interpolation scheme based on two-dimensional polynomials in ln(pressure) and temperature. The database is well-suited for remote-sensing application and should reduce the atmospheric bromine nitrate error budget substantially.

  4. Electrochemical processing of nitrate waste solutions

    Energy Technology Data Exchange (ETDEWEB)

    Genders, D.; Weinberg, N.; Hartsough, D. (Electrosynthesis Co., Inc., Cheektowaga, NY (United States))

    1992-10-07

    The second phase of research performed at The Electrosynthesis Co., Inc. has demonstrated the successful removal of nitrite and nitrate from a synthetic effluent stream via a direct electrochemical reduction at a cathode. It was shown that direct reduction occurs at good current efficiencies in 1,000 hour studies. The membrane separation process is not readily achievable for the removal of nitrites and nitrates due to poor current efficiencies and membrane stability problems. A direct reduction process was studied at various cathode materials in a flow cell using the complete synthetic mix. Lead was found to be the cathode material of choice, displaying good current efficiencies and stability in short and long term tests under conditions of high temperature and high current density. Several anode materials were studied in both undivided and divided cell configurations. A divided cell configuration was preferable because it would prevent re-oxidation of nitrite by the anode. The technical objective of eliminating electrode fouling and solids formation was achieved although anode materials which had demonstrated good stability in short term divided cell tests corroded in 1,000 hour experiments. The cause for corrosion is thought to be F[sup [minus

  5. Thermal decomposition of supported lithium nitrate catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz, Maria Lucia [INTEQUI (CONICET-UNSL), 25 de Mayo 384, V. Mercedes, 5730, San Luis (Argentina); Lick, Ileana Daniela [CINDECA (CONICET-UNLP), Calle 47 No 257, La Plata, 1900, Buenos Aires (Argentina); Ponzi, Marta Isabel [INTEQUI (CONICET-UNSL), 25 de Mayo 384, V. Mercedes, 5730, San Luis (Argentina); Castellon, Enrique Rodriguez; Jimenez-Lopez, Antonio [Departamento de Quimica Inorganica, Cristalografia y Mineralogia. Facultad de Ciencias, Universidad de Malaga, Campus de Teatinos, 29071 Malaga (Spain); Ponzi, Esther Natalia, E-mail: eponzi@quimica.unlp.edu.ar [CINDECA (CONICET-UNLP), Calle 47 No 257, La Plata, 1900, Buenos Aires (Argentina)

    2010-02-20

    New catalysts for soot combustion were prepared by impregnation of different supports (SiO{sub 2}, ZrO{sub 2} and ZrO{sub 2}.nH{sub 2}O) with a LiNO{sub 3} solution and then characterized by means of FTIR, XPS, TGA and UV-vis spectroscopy, whereby the presence of lithium nitrate in the prepared catalysts was identified and quantified. The soot combustion rate using this series of catalysts (LiNO{sub 3}/support) was compared with the activity of a series of impregnated catalysts prepared using LiOH (Li{sub 2}O/supports). Catalysts prepared using LiNO{sub 3} are found to be more active than those prepared using LiOH. The catalytic performance was also studied with a NO/O{sub 2} mixture in the feed, demonstrating that NO increases the combustion rate of soot, probably as a consequence of lithium oxide forming an 'in situ' nitrate ion.

  6. Assessing the Role of Sewers and Atmospheric Deposition as Nitrate Contamination Sources to Urban Surface Waters using Stable Nitrate Isotopes

    Science.gov (United States)

    Sikora, M. T.; Elliott, E. M.

    2009-12-01

    Excess nitrate (NO3-) contributes to the overall degraded quality of streams in many urban areas. These systems are often dominated by impervious surfaces and storm sewers that can route atmospherically deposited nitrogen, from both wet and dry deposition, to waterways. Moreover, in densely populated watersheds there is the potential for interaction between urban waterways and sewer systems. The affects of accumulated nitrate in riverine and estuary systems include low dissolved oxygen, loss of species diversity, increased mortality of aquatic species, and general eutrophication of the waterbody. However, the dynamics of nitrate pollution from each source and it’s affect on urban waterways is poorly constrained. The isotopes of nitrogen and oxygen in nitrate have been proven effective in helping to distinguish contamination sources to ground and surface waters. In order to improve our understanding of urban nitrate pollution sources and dynamics, we examined nitrate isotopes (δ15N and δ18O) in base- and stormflow samples collected over a two-year period from a restored urban stream in Pittsburgh, Pennsylvania (USA). Nine Mile Run drains a 1,600 hectare urban watershed characterized by 38% impervious surface cover. Prior work has documented high nitrate export from the watershed (~19 kg NO3- ha-1 yr-1). Potential nitrate sources to the watershed include observed sewer overflows draining directly to the stream, as well as atmospheric deposition (~23 kg NO3- ha-1 yr-1). In this and other urban systems with high percentages of impervious surfaces, there is likely minimal input from nitrate derived from soil or fertilizer. In this presentation, we examine spatial and temporal patterns in nitrate isotopic composition collected at five locations along Nine Mile Run characterized by both sanitary and combined-sewer cross-connections. Preliminary isotopic analysis of low-flow winter streamwater samples suggest nitrate export from Nine Mile Run is primarily influenced by

  7. A modified procedure for measuring oxygen-18 content of nitrate

    Science.gov (United States)

    Ahmed, M. A.; Aly, A. I. M.; Abdel Monem, N.; Hanafy, M.; Gomaa, H. E.

    2012-11-01

    SummaryMass spectrometric analysis of O-isotopic composition of nitrate has many potential applications in studies of environmental processes. Through this work, rapid, reliable, precise, broadly applicable, catalyst-free, low-priced and less labor intensive procedure for measuring δ18O of nitrate using Isotope Ratio Mass Spectrometer has been developed and implemented. The conditions necessary to effect complete nitrate recovery and complete removal of other oxygen containing anions and dissolved organic carbon (DOC) without scarifying the isotopic signature of nitrate were investigated. The developed procedure consists of two main parts: (1) wet chemistry train for extraction and purification of nitrate from the liquid matrix; (2) off-line pyrolysis of extracted nitrate salt with activated graphite at 550 °C for 30 min. The conditions necessary to effect complete nitrate recovery and complete removal of other oxygen containing compounds were investigated. Dramatic reduction in processing times needed for analysis of δ18O of nitrate at natural abundance level was achieved. Preservation experiments revealed that chloroform (99.8%) is an effective preservative. Isotopic contents of some selected nitrate salts were measured using the modified procedure and some other well established methods at two laboratories in Egypt and Germany. Performance assessment of the whole developed analytical train was made using internationally distributed nitrate isotopes reference materials and real world sample of initial zero-nitrate content. The uncertainty budget was evaluated using the graphical nested hierarchal approach. The obtained results proved the suitability for handling samples of complicated matrices. Reduction of consumables cost by about 80% was achieved.

  8. Nitrate in the Columbia Aquifer, central Delmarva Peninsula, Maryland

    Science.gov (United States)

    Bachman, L.J.

    1984-01-01

    A study of nitrate in water from 604 wells tapping the Columbia aquifer on the Delmarva Peninsula in eastern Maryland describes the factors that affect nitrate variability. Samples were collected from 196 randomly selected wells and analyzed for nitrogen species. Many were also analyzed for major ions. In addition, results of 313 nitrate analyses were randomly selected from county health department files. About 95 analyses of water samples collected from 1945 to 1978 were also evaluated. The frequency distribution of the nitrate analyses is bimodal, with 25 percent of the sample ranging from 0 to about 0.42 milligrams per liter (mg/L) nitrate as nitrogen (N), and the median is about 0.1 mg/L; the rest ranges from 0.42 to 58 mg/L, and the median is about 5.9 mg/L. The overall median nitrate concentration is about 3.5 mg/L as N. Over half of the samples had nitrate concentrations of 3 mg/L as N or higher, indicating that the water in the aquifer has been affected by human activity. Nitrate-nitrogen concentrations exceeded the water-quality standard of 10 mg/L in 15 percent of the samples established by the U.S. Environmental Protection Agency. The major factors affecting nitrate concentration are the presence of a nitrogen source, hydrogeological conditions, and the soil drainage. Sites with poorly drained soils may have a lower nitrate concentration either because the soils block the entrance of nitrate into the aquifer or because the aquifer under a poorly drained soil is associated with a chemical environment that promotes denitrification. (USGS)

  9. Parental brine evolution in the Chilean nitrate deposits (Pedro de Valdivia, II region de Antofagasta) : mineralogical and petrographic data

    OpenAIRE

    M. Vega; Chong, G; Pueyo, J. J.

    1996-01-01

    Les gisements de nitrate du Chili sont formés par des paragenèses complexes de minéraux salins qui remplissent la porosité de roches d'âge très variable (du Paléozoïque au Cénozoïque). Ces minéraux (nitrates, nitrate-sulfates, iodates, iodate-sulfates) sont très rares dans d'autres environnements. Les gisements sont situés dans le désert d'Atacama et suivent une frange irrégulière (N-S) au contact entre la Cordillère côtière et la dépression centrale. La saumure qui remplit la porosité interg...

  10. Synthesis of microspheres of triuranium octaoxide by simultaneous water and nitrate extraction from ascorbate-uranyl sols.

    Science.gov (United States)

    Brykala, M; Deptula, A; Rogowski, M; Lada, W; Olczak, T; Wawszczak, D; Smolinski, T; Wojtowicz, P; Modolo, G

    A new method for synthesis of uranium oxide microspheres (diameter Sol-Gel Process, which has been used to synthesize high-quality powders of a wide variety of complex oxides. Starting uranyl-nitrate-ascorbate sols were prepared by addition of ascorbic acid to uranyl nitrate hexahydrate solution and alkalizing by aqueous ammonium hydroxide and then emulsified in 2-ethylhexanol-1 containing 1v/o SPAN-80. Drops of emulsion were firstly gelled by extraction of water by the solvent. Destruction of the microspheres during thermal treatment, owing to highly reactive components in the gels, requires modification of the gelation step by Double Extraction Process-simultaneously extraction of water and nitrates using Primene JMT, which completely eliminates these problem. Final step was calcination in air of obtained microspheres of gels to triuranium octaoxide.

  11. Bis(ethylenediamine-κ2N,N′(nitrato-κ2O,O′cobalt(III hydroxide nitrate

    Directory of Open Access Journals (Sweden)

    Ji-Bo Zhang

    2009-09-01

    Full Text Available The Co ion in the title salt, [Co(NO3(H2NCH2CH2NH22](OH(NO3, has oxidation state + III and is coordinated by four N atoms from two ethylenediamine molecules and two O atoms from a nitrate anion in a distorted octahedral geometry. The charge of the complex cation is balanced by a hydroxide anion and a nitrate anion. The cations and anions are connected by N—H...O and O—H...O hydrogen bonds, resulting in a three-dimensional supramolecular framework. There are two independent ion pairs with similar configurations in the unit cell. Both uncoordinated nitrate counter-anions are disordered.

  12. Evaluation of nitrate source in groundwater of southern part of North China Plain based on multi-isotope

    Institute of Scientific and Technical Information of China (English)

    方晶晶; 周爱国; 马传明; 刘存富; 蔡鹤生; 甘义群; 刘运德

    2015-01-01

    Nitrate pollution in groundwater is a serious water quality problem that increases the risk of developing various cancers. Groundwater is the most important water resource and supports a population of 5 million in Anyang area of the southern part of the North China Plain. Determining the source of nitrate pollution is the challenge in hydrology area due to the complex processes of migration and transformation. A new method is presented to determine the source of nitrogen pollution by combining the composition characteristics of stable carbon isotope in dissolved organic carbon in groundwater. The source of groundwater nitrate is dominated by agricultural fertilizers, as well as manure and wastewater. Mineralization, nitrification and mixing processes occur in the groundwater recharge area, whereas the confined groundwater area is dominated by denitrification processes.

  13. Solvent extraction of uranium(VI) and thorium(IV) from nitrate media by Cyanex 923

    Energy Technology Data Exchange (ETDEWEB)

    Sahu, S.K.; Chakravortty, V. [Utkal Univ., Bhubaneswar (India). Dept. of Chemistry; Reddy, M.L.P.; Ramamohan, T.R. [Regional Research Lab. (CSIR), Trivandum (India)

    2000-07-01

    The extraction behaviour of uranium(VI) and thorium(IV) from nitrate solutions has been investigated using Cyanex 923 (TRPO) in xylene as an extractant. The extraction data have been analyzed by both graphical and theoretical methods by taking into account complexation of the metal ion in the aqueous phase with inorganic ligands and all plausible complexes extracted into the organic phase. The results demonstrate that these metal ions are extracted into xylene as Th(NO{sub 3}){sub 4} . 2 TRPO and UO{sub 2}(NO{sub 3}){sub 2} . 2 TRPO. The equilibrium constants of the extracted complexes have been deduced by non-linear regression analysis. Infrared spectral data of the extracted complexes have been used to further clarify the nature of the complexes. The selectivities between these metal ions were evaluated and compared with commercially important extractants like tri-n-butylphosphate (TBP). (orig.)

  14. The Role of Organic Nitrates in the Chemistry of the Continents: An Assessment Using WRF-CHEM

    Science.gov (United States)

    Zare, A.; Cohen, R. C.; Romer, P.

    2015-12-01

    Nitrogen oxides (NOx) play a fundamental role in the chemistry of atmospheric oxidation and affect air quality and climate. Recent experiments have shown that formation of organic nitrates is a more important immediate sink of NOx than nitric acid in the rural continental locations. In particular, in regions with high emissions of biogenic volatile organic compounds (BVOCs), isoprene and monoterpene derived organic nitrates can be expected to control the fate of nitrogen oxides, and consequently the ozone production efficiency. Thus understanding of the complex production and loss processes of organic nitrates are required for determining the lifetime of NOx in the present day and in preindustrial times. Using the chemical transport model WRF-Chem, we investigate impacts of organic nitrate chemistry on the NOx and ozone budgets of the southeastern United States. We evaluate changes to the NOx budget in response to decreases in anthropogenic NOx emissions. The model has been updated with recent advances in representation of BVOC oxidation chemistry and deposition rates, including a detailed representation of organic nitrates. We compared simulations to measurements from the Southern Oxidant and Aerosol Study (SOAS) campaign in central Alabama in summer 2013 and examine the sensitivity to emission rates.

  15. Treatment Study Plan for Nitrate Salt Waste Remediation Revision 1.0

    Energy Technology Data Exchange (ETDEWEB)

    Juarez, Catherine L. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Funk, David John [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Vigil-Holterman, Luciana R. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Naranjo, Felicia Danielle [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-03-07

    The two stabilization treatment methods that are to be examined for their effectiveness in the treatment of both the unremediated and remediated nitrate salt wastes include (1) the addition of zeolite and (2) cementation. Zeolite addition is proposed based on the results of several studies and analyses that specifically examined the effectiveness of this process for deactivating nitrate salts. Cementation is also being assessed because of its prevalence as an immobilization method used for similar wastes at numerous facilities around the DOE complex, including at Los Alamos. The results of this Treatment Study Plan will be used to provide the basis for a Resource Conservation and Recovery Act (RCRA) permit modification request of the LANL Hazardous Waste Facility Permit for approval by the New Mexico Environment Department-Hazardous Waste Bureau (NMED-HWB) of the proposed treatment process and the associated facilities.

  16. Chemical synthesis of nanocrystalline magnesium aluminate spinel via nitrate-citrate combustion route

    Energy Technology Data Exchange (ETDEWEB)

    Saberi, Ali [Ceramic Division, Iran University of Science and Technology, Tehran (Iran, Islamic Republic of)], E-mail: ASaberi@IUST.ac.ir; Golestani-Fard, Farhad; Sarpoolaky, Hosein [Ceramic Division, Iran University of Science and Technology, Tehran (Iran, Islamic Republic of); Willert-Porada, Monika; Gerdes, Thorsten [Chair of Materials Processing, University of Bayreuth, Bayreuth (Germany); Simon, Reinhard [Chair of Ceramic Materials Engineering, University of Bayreuth, Bayreuth (Germany)

    2008-08-25

    Nanocrystalline magnesium aluminate spinel (MgAl{sub 2}O{sub 4}) was synthesized using metal nitrates, citric acid and ammonium solutions. The precursor and the calcined powders at different temperatures were characterized by X-ray diffraction (XRD), simultaneous thermal analysis (STA), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The combustion mechanism was also studied by a quadrupole mass spectrometer (QMS) which coupled to STA. The generated heat through the combustion of the mixture of ammonium nitrate and citrate based complexes decreased the synthesis temperature of MgAl{sub 2}O{sub 4} spinel. The synthesized MgAl{sub 2}O{sub 4} spinel at 900 deg. C has faced shape with crystallite size in the range of 18-24 nm.

  17. Trends in concentrations of nitrate and total dissolved solids in public supply wells of the Bunker Hill, Lytle, Rialto, and Colton groundwater subbasins, San Bernardino County, California: Influence of legacy land use

    Science.gov (United States)

    Kent, Robert; Landon, Matthew K.

    2013-01-01

    Concentrations and temporal changes in concentrations of nitrate and total dissolved solids (TDS) in groundwater of the Bunker Hill, Lytle, Rialto, and Colton groundwater subbasins of the Upper Santa Ana Valley Groundwater Basin were evaluated to identify trends and factors that may be affecting trends. One hundred, thirty-one public-supply wells were selected for analysis based on the availability of data spanning at least 11 years between the late 1980s and the 2000s. Forty-one of the 131 wells (31%) had a significant (p < 0.10) increase in nitrate and 14 wells (11%) had a significant decrease in nitrate. For TDS, 46 wells (35%) had a significant increase and 8 wells (6%) had a significant decrease. Slopes for the observed significant trends ranged from − 0.44 to 0.91 mg/L/yr for nitrate (as N) and − 8 to 13 mg/L/yr for TDS. Increasing nitrate trends were associated with greater well depth, higher percentage of agricultural land use, and being closer to the distal end of the flow system. Decreasing nitrate trends were associated with the occurrence of volatile organic compounds (VOCs); VOC occurrence decreases with increasing depth. The relations of nitrate trends to depth, lateral position, and VOCs imply that increasing nitrate concentrations are associated with nitrate loading from historical agricultural land use and that more recent urban land use is generally associated with lower nitrate concentrations and greater VOC occurrence. Increasing TDS trends were associated with relatively greater current nitrate concentrations and relatively greater amounts of urban land. Decreasing TDS trends were associated with relatively greater amounts of natural land use. Trends in TDS concentrations were not related to depth, lateral position, or VOC occurrence, reflecting more complex factors affecting TDS than nitrate in the study area.

  18. Closure of the condensed-phase organic-nitrate reaction USQ at hanford

    Energy Technology Data Exchange (ETDEWEB)

    COWLEY, W.L.

    1999-06-24

    A discovery Unreviewed Safety Question (USQ) was declared on the underground waste storage tanks at the Hanford Site in May 1996. The USQ was for condensed-phase organic-nitrate reactions (sometimes called organic complexant reactions) in the tanks. This paper outlines the steps taken to close the USQ, and resolve the related safety issue. Several processes were used at the Hanford Site to extract and/or process plutonium. These processes resulted in organic complexants (for chelating multivalent cations) and organic extraction solvents being sent to the underground waste storage tanks. This paper addresses the organic complexant hazard. The organic complexants are in waste matrices that include inert material, diluents, and potential oxidizers. In the presence of oxidizing material, the complexant salts can be made to react exothermically by heating to high temperatures or by applying an external ignition source of sufficient energy. The first organic complexant hazard assessments focused on determining whether a hulk runaway reaction could occur, similar to the 1957 accident at Kyshtm (a reprocessing plant in the former U.S.S.R.). Early analyses (1977 through 1994) examined organic-nitrate reaction onset temperatures and concluded that a bulk runaway reaction could not occur at the Hanford Site because tank temperatures were well below that necessary for bulk runaway. Therefore, it was believed that organic-nitrate reactions were adequately described in the then current Authorization Basis (AB). Subsequent studies examined a different accident scenario, propagation resulting from an external ignition source (e.g., lightning or welding slag) that initiates a combustion front that propagates through the organic waste. A USQ evaluation determined that localized high energy ignition sources were credible, and that point source ignition of organic complexant waste was not adequately addressed i n the then existing AB. Consequently, the USQ was declared on the

  19. Is nitrate an endocrine active compound in fish?

    DEFF Research Database (Denmark)

    Mose, M. P.; Kinnberg, Karin Lund; Bjerregaard, Poul;

    concentrations around or below the limits for drinking water). Nitrate concentrations in streams may be elevated due to releases from agricultural practices. The effects of nitrate and nitrite on endocrine relevant endpoints were investigated in zebrafish (Danio rerio) and brown trout (Salmo trutta). Zebrafish...

  20. Distribution and Sources of Nitrate-Nitrogen in Kansas Groundwater

    Directory of Open Access Journals (Sweden)

    Margaret A. Townsend

    2001-01-01

    Full Text Available Kansas is primarily an agricultural state. Irrigation water and fertilizer use data show long- term increasing trends. Similarly, nitrate-N concentrations in groundwater show long-term increases and exceed the drinking-water standard of 10 mg/l in many areas. A statistical analysis of nitrate-N data collected for local and regional studies in Kansas from 1990 to 1998 (747 samples found significant relationships between nitrate-N concentration with depth, age, and geographic location of wells. Sources of nitrate-N have been identified for 297 water samples by using nitrogen stable isotopes. Of these samples, 48% showed fertilizer sources (+2 to +8 and 34% showed either animal waste sources (+10 to +15 with nitrate-N greater than 10 mg/l or indication that enrichment processes had occurred (+10 or above with variable nitrate-N or both. Ultimate sources for nitrate include nonpoint sources associated with past farming and fertilization practices, and point sources such as animal feed lots, septic systems, and commercial fertilizer storage units. Detection of nitrate from various sources in aquifers of different depths in geographically varied areas of the state indicates that nonpoint and point sources currently impact and will continue to impact groundwater under current land uses.

  1. determination of nitrate concentrations in dutsin-ma fadama land ...

    African Journals Online (AJOL)

    DR. AMINU

    2014-06-01

    Jun 1, 2014 ... (January to October) using Spectrophotometric measurement, to determine the level of nitrate in the water. ... treatment practices, such as sedimentation or pH adjustment with ... nitrate in the surface water of Tunga – Kawo irrigation scheme and ... colour of the skin, particularly around the eyes and mouth.

  2. Aromatic nitrations by mixed acid. Fast liquid-liquid regime

    NARCIS (Netherlands)

    Zaldivar, J.M.; Zaldivar, J.M.; Molga, E.J.; Alos, M.A.; Hernandez, H.; Westerterp, K.R.

    1996-01-01

    Aromatic nitration by mixed acid was selected as a specific case of heterogeneous liquid-liquid reaction. An extensive experimental programme was followed using adiabatic and heat flow calorimetry and pilot reactor experiments, supported by chemical analysis. A series of nitration experiments was

  3. Nitrate leaching and pesticide use in energy crops

    DEFF Research Database (Denmark)

    Jørgensen, Uffe

    2006-01-01

    Nitrate leaching measured below willow and miscanthus is very low from the established crops. Pesticide use in energy crops is low as well.......Nitrate leaching measured below willow and miscanthus is very low from the established crops. Pesticide use in energy crops is low as well....

  4. Spatial assessment of animal manure spreading and groundwater nitrate pollution

    Directory of Open Access Journals (Sweden)

    Roberta Infascelli

    2009-11-01

    Full Text Available Nitrate concentration in groundwater has frequently been linked to non-point pollution. At the same time the existence of intensive agriculture and extremely intensive livestock activity increases the potential for nitrate pollution in shallow groundwater. Nitrate used in agriculture could cause adverse effects on human and animal health. In order to evaluate the groundwater nitrate pollution, and how it might evolve in time, it is essential to develop control systems and to improve policies and incentives aimed at controlling the amount of nitrate entering downstream water systems. The province of Caserta in southern Italy is characterized by high levels of animal manure loading. A comparison between manure nitrogen production and nitrate concentration in groundwater was carried out in this area, using geostatistical tools and spatial statistics. The results show a discrepancy between modelling of nitrate leaching and monitoring of the groundwater and, moreover, no spatial correlation between nitrogen production in livestock farms and nitrate concentration in groundwater, suggesting that producers are not following the regulatory procedures for the agronomic use of manure. The methodology developed in this paper could be applied also in other regions in which European Union fertilization plans are not adequately followed.

  5. Evaluation of nitrate and nitrite destruction/separation technologies

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, D.T.

    1997-08-29

    This report describes and evaluates four types of nitrate and nitrite destruction and separation technologies that could be used to treat the aqueous, alkaline, nitrate-bearing mixed waste that is generated by the In-Tank Precipitation (ITP) process at the Savannah River Site (SRS). The technologies considered in this report include thermal, hydrothermal, chemical, and electrochemical technologies.

  6. INVESTIGATION OF SENSITIVITY OF FERTILIZER GRADE AMMONIUM NITRATE TO EXPLOSION

    Science.gov (United States)

    In order to determine the probable cause and mechanism of the explosion of cargoes of fertilizer grade ammonium nitrate on shipboard at Texas City...undergo explosion and in turn initiate the explosion of unconsumed nitrate fertilizer . A hypothesis of the mechanism of the Texas City disaster was established on this basis. (Author)

  7. Nitrate and nitrite in biology, nutrition and therapeutics

    NARCIS (Netherlands)

    Lundberg, J.O.; van Faassen, E.E.H.; Gladwin, M.T.; Ahluwalia, A.; Benjamin, N.

    2009-01-01

    Inorganic nitrate and nitrite from endogenous or dietary sources are metabolized in vivo to nitric oxide (NO) and other bioactive nitrogen oxides. The nitrate-nitrite-NO pathway is emerging as an important mediator of blood flow regulation, cell signaling, energetics and tissue responses to hypoxia.

  8. Removal of Nitrate From Aqueous Solution Using Rice Chaff

    Directory of Open Access Journals (Sweden)

    Dehghani

    2015-09-01

    Full Text Available Background Nitrate is largely dissolved in the surface and ground water, due to its high solubility. Continual uptake of nitrite through drinking water can lead to problems and diseases (such as blue baby for humans, especially children. Objectives The aim of this study was to develop a new and inexpensive method for the removal of nitrate from water. In this regard, the possibility of using chaff for removal of nitrate from aqueous solutions was studied and the optimum operating conditions of nitrate removal was determined. Materials and Methods This is a cross-sectional study conducted in laboratory scale. The UV spectrophotometer at a wavelength of maximum absorbance (220 nm was used to determine the nitrate concentration. The effect of pH, amount of chaff, temperature, and contact time were investigated. Results The result of this study revealed that chaff as an absorbent could remove nitrate from solutions, and the efficiency of adsorption increased as contact time increased from 5 to 30 minutes, amount of chaff increased from 1 to 3 g, temperature increased in a range of 300 - 400°C and the amount of pH decreased from 10 to 3. The maximum adsorption rate was around pH 3 (53.14%. Conclusions It was shown that the removal efficiency of nitrate was directly proportional to the amount of chaff, temperature, and contact time but inversely to the pH. This study showed that nitrate removal by chaff is a promising technique.

  9. [Accumulation of nitrates in carrot root--agronomical consequences].

    Science.gov (United States)

    Blanc, D; Otto, C; Mars, S

    1980-01-01

    This paper deals with the effects of various parameters involved in plant nitrogen metabolism, on the nitrate content in carrot roots. Level of mineral nitrogen supply, activity of leaves and light intensity have been taken into account in factorial experiments. Results are discussed with a view to the improvement of the quality of root production with respect to their nitrate content.

  10. Robust options to remove nitrate and phosphate from tile drainage

    NARCIS (Netherlands)

    Jansen, Stefan; Gerritse, Jan; Stuurman, Roelof; Chardon, W.J.; Talens, René

    2016-01-01

    Diffuse emission from agricultural land is a major, persistent source of nitrogen and phosphorus in surface waters. In this contribution, we present field experiments of a series of robust options to remove nitrate and phosphorus at
    field drainage level. Nitrate removal was enhanced by stimulati

  11. Assessment of nitrate concentration in groundwater in Saudi Arabia.

    Science.gov (United States)

    Alabdula'aly, Abdulrahman I; Al-Rehaili, Abdullah M; Al-Zarah, Abdullah I; Khan, Mujahid A

    2010-02-01

    Contamination of groundwater by nitrate is considered a global problem. Nitrates are introduced in the groundwater from a variety of sources like agricultural activities, poor sewer system, wastewaters, and industrial activities. In the present research, a survey of wells (n = 1,060) was undertaken in all 13 regions of the Kingdom of Saudi Arabia to assess the contained nitrate (NO(3)) levels. The results indicated variation in nitrate levels from 1.1 to 884.0 mg/L as NO(3) throughout the Kingdom. The average nitrate levels in milligrams per liter as NO(3) were as follows in descending order: 65.7 (Jizan), 60.3 (Asir), 60.0 (Qassim), 51.3 (Hail), 41.8 (Makkah Al Mukaramma), 41.3 (Madina Al Munnawara), 38.0 (Al Baha), 37.0 (Najran), 30.7, (Tabouk), 25.2 (Eastern Province), 18.8 (Riyadh), 15.8 (Al Jouf), and 9.1 (Hadwed Shamalyah). The results indicated that nitrate levels exceeded the maximum contaminant limits for drinking water (45 mg/L as NO(3)) in a number of wells (n = 213) in different regions of the Kingdom. The maximum and minimum wells exceeding the maximum contaminant limits for nitrate in drinking water were in Jizan (52.6%) and Hadwed Shamalyah (4.9%), respectively. Most of the wells which exceeded the maximum allowed limits for nitrate were in the areas which were used for agricultural and residential purposes.

  12. Iron-mediated effects on nitrate reductase in marine phytoplankton

    NARCIS (Netherlands)

    Timmermans, K.R.; Stolte, W.; Baar, H.J.W. de

    1994-01-01

    The potential activity of nitrate reductase was determined in uni-algal cultures in the laboratory and in natural marine phytoplankton assemblages. In the laboratory bioassays, distinct differences in nitrate reductase activity were observed in iron replete versus depleted cultures for Emiliania hux

  13. Nitrate, Nitrite, and Ammonium Variability in Drinking Water Distribution Systems.

    Science.gov (United States)

    Schullehner, Jörg; Stayner, Leslie; Hansen, Birgitte

    2017-03-09

    Accurate assessments of exposure to nitrate in drinking water is a crucial part of epidemiological studies investigating long-term adverse human health effects. However, since drinking water nitrate measurements are usually collected for regulatory purposes, assumptions on (1) the intra-distribution system variability and (2) short-term (seasonal) concentration variability have to be made. We assess concentration variability in the distribution system of nitrate, nitrite, and ammonium, and seasonal variability in all Danish public waterworks from 2007 to 2016. Nitrate concentrations at the exit of the waterworks are highly correlated with nitrate concentrations within the distribution net or at the consumers' taps, while nitrite and ammonium concentrations are generally lower within the net compared with the exit of the waterworks due to nitrification. However, nitrification of nitrite and ammonium in the distribution systems only results in a relatively small increase in nitrate concentrations. No seasonal variation for nitrate, nitrite, or ammonium was observed. We conclude that nitrate measurements taken at the exit of the waterworks are suitable to calculate exposures for all consumers connected to that waterworks and that sampling frequencies in the national monitoring programme are sufficient to describe temporal variations in longitudinal studies.

  14. Nitrate Water Activities, Science Study Aid No. 4.

    Science.gov (United States)

    Agricultural Research Service (USDA), Washington, DC.

    Intended to supplement a regular program, this pamphlet provides background information, related activities, and suggestions for other activities on the subject of nitrate as a water pollutant. Two activities related to plant nutrient pollution, nitrate filtration and measuring mitrate used by plants, are explained in detail, outlining objectives,…

  15. More answers to the still unresolved question of nitrate tolerance.

    Science.gov (United States)

    Münzel, Thomas; Daiber, Andreas; Gori, Tommaso

    2013-09-01

    Organic nitrates are traditionally felt to be a safe adjuvant in the chronic therapy of patients with coronary artery disease. Despite their long use, progress in the understanding of the pharmacology and mechanism of action of these drugs has been achieved only in the last two decades, with the identification of the role of oxidative stress in the pathophysiology of nitrate tolerance, with, the discovery of the ancillary effects of nitrates, and with the demonstration that nitrate therapy has important chronic side effects that might modify patients' prognosis. These advances are however mostly confined to the molecular level or to studies in healthy volunteers, and the true impact of organic nitrates on clinical outcome remains unknown. Complicating this issue, evidence supports the existence of important differences among the different drugs belonging to the group, and there are reasons to believe that the nitrates should not be treated as a homogeneous class. As well, the understanding of the effects of alternative nitric oxide (NO) donors is currently being developed, and future studies will need to test whether the properties of these new medications may compensate and prevent the abnormalities imposed by chronic nitrate therapy. Intermittent therapy with nitroglycerin and isosorbide mononitrate is now established in clinical practice, but they should neither be considered a definitive solution to the problem of nitrate tolerance. Both these strategies are not deprived of complications, and should currently be seen as a compromise rather than a way fully to exploit the benefits of NO donor therapy.

  16. Heat transfer behavior of molten nitrate salt

    Science.gov (United States)

    Das, Apurba K.; Clark, Michael M.; Teigen, Bard C.; Fiveland, Woodrow A.; Anderson, Mark H.

    2016-05-01

    The usage of molten nitrate salt as heat transfer fluid and thermal storage medium decouples the generation of electricity from the variable nature of the solar resource, allowing CSP plants to avoid curtailment and match production with demand. This however brings some unique challenges for the design of the molten salt central receiver (MSCR). An aspect critical to the use of molten nitrate (60wt%/40wt% - NaNO3/KNO3) salt as heat transfer fluid in the MSCR is to understand its heat transfer behavior. Alstom collaborated with the University of Wisconsin to conduct a series of experiments and experimentally determined the heat transfer coefficients of molten nitrate salt up to high Reynolds number (Re > 2.0E5) and heat flux (q″ > 1000 kW/m2), conditions heretofore not reported in the literature. A cartridge heater instrumented with thermocouples was installed inside a stainless steel pipe to form an annular test section. The test section was installed in the molten salt flow loop at the University of Wisconsin facility, and operated over a range of test conditions to determine heat transfer data that covered the expected operating regime of a practical molten salt receiver. Heat transfer data were compared to widely accepted correlations found in heat transfer literature, including that of Gnielinski. At lower Reynolds number conditions, the results from this work concurred with the molten salt heat transfer data reported in literature and followed the aforementioned correlations. However, in the region of interest for practical receiver design, the correlations did not accurately model the experimentally determined heat transfer data. Two major effects were observed: (i) all other factors remaining constant, the Nusselt numbers gradually plateaued at higher Reynolds number; and (ii) at higher Reynolds number a positive interaction of heat flux on Nusselt number was noted. These effects are definitely not modeled by the existing correlations. In this paper a new

  17. Green and controllable metal-free nitrification and nitration of arylboronic acids

    Institute of Scientific and Technical Information of China (English)

    Shuai Wang; Chun Chun Shu; Tao Wang; Jian Yu; Guo Bing Yan

    2012-01-01

    A novel and green nitrating reagent has been developed for the nitrification and nitration of arylboronic acids,which can be controlled by the reaction conditions.The process provides an attractive alternative to the traditional nitration protocols.

  18. The dependence of nitrate reductase activity on the level of soluble sugars in wheat and cucumber roots growing in the presence of simazine, in light or in darkness

    Directory of Open Access Journals (Sweden)

    Józef Buczek

    2014-01-01

    Full Text Available At concentrations of 25 and 5 µM, simazine inhibited nitrate reductase activity in wheat and cucumber roots, respectively. It also lowered the content of soluble sugars and decreased the activities of NADH malate dehydrogenase and NADP+ glucose-6-phosphate dehydrogenase. The inclusion of 50 mM glucose into the medium partially reversed the inhibitory effect of simazine on the activity of nitrate reductase in cucumber roots and slightly increased the activity of this enzyme in wheat roots These results suggest a complex influence of the herbicide on the activity of nitrate reductase: simazine lowers the level of soluble sugars in roots and decreases the activity of the dehydrogenases supplying the reduced nucleotides indispensable for reduction of nitrates.

  19. Transcriptional networks in the nitrate response of Arabidopsis thaliana.

    Science.gov (United States)

    Vidal, Elena A; Álvarez, José M; Moyano, Tomás C; Gutiérrez, Rodrigo A

    2015-10-01

    Nitrogen is an essential macronutrient for plants and its availability is a key determinant of plant growth and development and crop yield. Besides their nutritional role, N nutrients and metabolites are signals that activate signaling pathways that modulate many plant processes. Because the most abundant inorganic N source for plants in agronomic soils is nitrate, much of the work to understand plant N-signaling has focused on this nutrient. Over the last years, several studies defined a comprehensive catalog of nitrate-responsive genes, involved in nitrate transport, metabolism and a variety of other processes. Despite significant progress in recent years, primarily using Arabidopsis thaliana as a model system, the molecular mechanisms by which nitrate elicits changes in transcript abundance are still not fully understood. Here we highlight recent advancements in identifying key transcription factors and transcriptional mechanisms that orchestrate the gene expression response to changes in nitrate availability in A. thaliana.

  20. Photooxidation of cellulose nitrate: new insights into degradation mechanisms.

    Science.gov (United States)

    Berthumeyrie, Sebastien; Collin, Steeve; Bussiere, Pierre-Olivier; Therias, Sandrine

    2014-05-15

    Cellulose nitrate (or nitrocellulose) has received considerable interest due to its uses in various applications, such as paints, photographic films and propellants. However, it is considered as one of the primary pollutants in the energetic material industries because it can be degraded to form polluting chemical species. In this work, the UV light degradation of cellulose nitrate films was studied under conditions of artificially accelerated photooxidation. To eliminate the reactivity of nitro groups, the degradation of ethylcellulose was also investigated. Infrared spectroscopy analyses of the chemical modifications caused by the photooxidation of cellulose nitrate films and the resulting formation of volatile products revealed the occurrence of de-nitration and the formation of oxidation photoproducts exhibiting lactone and anhydride functions. The impact of these chemical modifications on the mechanical and thermal properties of cellulose nitrate films includes embrittlement and lower temperatures of ignition when used as a propellant.

  1. RIXS of Ammonium Nitrate using OCEAN

    Science.gov (United States)

    Vinson, John; Jach, Terrence; Mueller, Matthias; Unterumsberger, Rainer; Beckhoff, Burkhard

    The ocean code allows for calculations of near-edge x-ray spectroscopies using a GW/Bethe-Salpeter equation (BSE) approach. Here we present an extension of the code for calculating resonant inelastic x-ray scattering (RIXS). Recent work has shown that peak-specific broadening of nitrogen K α emission in nitrates is due to a valence-band lifetime that is an order of magnitude shorter than that of the nitrogen 1s hole, an inversion of the usual assumption that valence holes have longer lifetimes than core-level holes. Using the BSE, including GW corrections to the DFT energies, as implemented in ocean we are able to compare calculations of RIXS with measured spectra of the same. By utilizing an approach free from fitting parameters we are able to identify the origins of various broadening effects observed in experiment.

  2. Removal of gadolinium nitrate from heavy water

    Energy Technology Data Exchange (ETDEWEB)

    Wilde, E.W.

    2000-03-22

    Work was conducted to develop a cost-effective process to purify 181 55-gallon drums containing spent heavy water moderator (D2O) contaminated with high concentrations of gadolinium nitrate, a chemical used as a neutron poison during former nuclear reactor operations at the Savannah River Site (SRS). These drums also contain low level radioactive contamination, including tritium, which complicates treatment options. Presently, the drums of degraded moderator are being stored on site. It was suggested that a process utilizing biological mechanisms could potentially lower the total cost of heavy water purification by allowing the use of smaller equipment with less product loss and a reduction in the quantity of secondary waste materials produced by the current baseline process (ion exchange).

  3. Thermal Decomposition of Nitrated Tributyl Phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Paddleford, D.F. [Westinghouse Savannah River Company, Aiken, SC (United States); Hou, Y.; Barefield, E.K.; Tedder, D.W.; Abdel-Khalik, S.I. [Georgia Institute of Technology, GA (United States)

    1995-01-01

    Contact between tributyl phosphate and aqueous solutions of nitric acid and/or heavy metal nitrate salts at elevated temperatures can lead to exothermic reactions of explosive violence. Even though such operations have been routinely performed safely for decades as an intrinsic part of the Purex separation processes, several so-called ``red oil`` explosions are known to have occurred in the United States, Canada, and the former Soviet Union. The most recent red oil explosion occurred at the Tomsk-7 separations facility in Siberia, in April 1993. That explosion destroyed part of the unreinforced masonry walls of the canyon-type building in which the process was housed, and allowed the release of a significant quantity of radioactive material.

  4. Hydrogels made from chitosan and silver nitrate.

    Science.gov (United States)

    Kozicki, Marek; Kołodziejczyk, Marek; Szynkowska, Małgorzata; Pawlaczyk, Aleksandra; Leśniewska, Ewa; Matusiak, Aleksandra; Adamus, Agnieszka; Karolczak, Aleksandra

    2016-04-20

    This work describes a gelation of chitosan solution with silver nitrate. Above the critical concentration of chitosan (c*), continuous hydrogels of chitosan-silver can be formed. At lower concentrations, the formation of nano- and micro-hydrogels is discussed. The sol-gel analysis was performed to characterise the hydrogels' swelling properties. Moreover, the following were employed: (i) mechanical testing of hydrogels, (ii) inductively coupled plasma-optical emission spectroscopy (ICP-OES) for the measurement of silver concentration, (iii) scanning electron microscopy (SEM) to examine the morphology of products obtained, and (iv) dynamic light scattering (DLS) and UV-vis spectrophotometry to examine products formed at low concentration of chitosan (chydrogels were used for modification of cotton fabric in order to give it antimicrobial properties. The products obtained acted against Escherichia coli and Bacillus subtilis apart from the chitosan used that showed no such activity.

  5. Characterization of the lanthanum(III) and europium(III) trichloroacetate complexes extracted with 18-crown-6

    Energy Technology Data Exchange (ETDEWEB)

    Imura, H.; Saito, Y.; Ohashi, K. [Ibaraki Univ., Mito (Japan); Meguro, Y.; Yoshida, Z. [Japan Atomic Energy Research Inst., Tokai (Japan); Choppin, G.R. [Florida State Univ., Tallahassee, FL (United States)

    1996-08-01

    Extraction of lanthanide(III) ions with 18-crown-6 (18C6) and trichloroacetate (tca) has been studied. The composition, hydration, and structure of the La(III) and Eu(III) complexes extracted into 1,2-dichloroethane were investigated by using several methods such as the liquid-liquid distribution technique, conductimetry, Karl Fisher titration, laser luminescence spectroscopy, and {sup 1}H NMR. The La(III) complex was found to be a monohydrate, La(tca){sub 3}(18C6)(H{sub 2}O), while that of Eu(III) was a mixture of a monohydrate and a dihydrate, i.e., Eu(tca){sub 3}(18C6)(H{sub 2}O) and Eu(tca){sub 3}(18C6)(H{sub 2}O){sub 2}. The origin of the selectivity by 18C6 which gives much higher extractability of La(III) than of Eu(III) is explained by considering the hydration and probable structure of their complexes. 12 refs., 5 figs., 4 tabs.

  6. Nitrate removal by nitrate-dependent Fe(II) oxidation in an upflow denitrifying biofilm reactor.

    Science.gov (United States)

    Zhou, Jun; Wang, Hongyu; Yang, Kai; Sun, Yuchong; Tian, Jun

    2015-01-01

    A continuous upflow biofilm reactor packed with ceramsite was constructed for nitrate removal under an anaerobic atmosphere without an organic carbon source. Denitrifying bacteria, Pseudomonas sp. W1, Pseudomonas sp. W2 and Microbacterium sp. W5, were added to the bioreactor as inocula. Nitrate concentration, nitrite accumulation and nitrogen removal efficiency in the effluent were investigated under various conditions set by several parameters including pH, hydraulic retention time (HRT), ratios of carbon to nitrogen (C/N) and temperature. The results illustrated that the maximum removal efficiency of nitrogen was 85.39%, under optimum reaction parameters, approximately pH 6.5-7, HRT = 48 hours and C/N = 13.1:1 at temperature of 30 °C, which were determined by experiment.

  7. Tyrosine-Nitrated Proteins: Proteomic and Bioanalytical Aspects.

    Science.gov (United States)

    Batthyány, Carlos; Bartesaghi, Silvina; Mastrogiovanni, Mauricio; Lima, Analía; Demicheli, Verónica; Radi, Rafael

    2017-03-01

    "Nitroproteomic" is under active development, as 3-nitrotyrosine in proteins constitutes a footprint left by the reactions of nitric oxide-derived oxidants that are usually associated to oxidative stress conditions. Moreover, protein tyrosine nitration can cause structural and functional changes, which may be of pathophysiological relevance for human disease conditions. Biological protein tyrosine nitration is a free radical process involving the intermediacy of tyrosyl radicals; in spite of being a nonenzymatic process, nitration is selectively directed toward a limited subset of tyrosine residues. Precise identification and quantitation of 3-nitrotyrosine in proteins has represented a "tour de force" for researchers. Recent Advances: A small number of proteins are preferential targets of nitration (usually less than 100 proteins per proteome), contrasting with the large number of proteins modified by other post-translational modifications such as phosphorylation, acetylation, and, notably, S-nitrosation. Proteomic approaches have revealed key features of tyrosine nitration both in vivo and in vitro, including selectivity, site specificity, and effects in protein structure and function. Identification of 3-nitrotyrosine-containing proteins and mapping nitrated residues is challenging, due to low abundance of this oxidative modification in biological samples and its unfriendly behavior in mass spectrometry (MS)-based technologies, that is, MALDI, electrospray ionization, and collision-induced dissociation. The use of (i) classical two-dimensional electrophoresis with immunochemical detection of nitrated proteins followed by protein ID by regular MS/MS in combination with (ii) immuno-enrichment of tyrosine-nitrated peptides and (iii) identification of nitrated peptides by a MIDAS™ experiment is arising as a potent methodology to unambiguously map and quantitate tyrosine-nitrated proteins in vivo. Antioxid. Redox Signal. 26, 313-328.

  8. Proteome responses to nitrate in bioethanol production contaminant Dekkera bruxellensis.

    Science.gov (United States)

    Neto, Adauto Gomes Barbosa; Pestana-Calsa, Maria Clara; de Morais, Marcos Antonio; Calsa, Tercilio

    2014-06-02

    Dekkera bruxellensis is an industrially relevant yeast, especially in bioethanol production. The capacity of D. bruxellensis to assimilate nitrate can confer advantages of this yeast over Saccharomyces cerevisiae at industrial conditions. In the present work we present the consequences of nitrate assimilation, using ammonium as reference, to the proteomics of D. bruxellensis. Thirty-four protein spots were overproduced in nitrate medium and were identified by MS-TOF/TOF analysis and were putatively identified by using local Mascot software. Apart from the overexpression of genes of nitrate metabolism, ATP synthesis and PPP and TCA pathways previously reported, cultivation on nitrate induced overproduction of glycolytic enzymes, which corroborate the high energy demand and NADH availability for nitrate assimilation. Overproduction of alcohol dehydrogenase (Adh) protein was also observed. Proteomic profile of D. bruxellensis cultivated in nitrate and described in the present work agrees with the hypothesis of metabolic flux regulation, making available the energy in the form of NADH to support nitrate assimilation. This work contributes with an initial picture of proteins presenting differential accumulation in industrial contaminant yeast, in strict association with possible metabolic responses to nitrate as sole nitrogen source in cultivation medium. The present study investigated the gene expression at translational level of yeast D. bruxellensis for nitrate assimilation. This study corroborated with biological models that consider the ability to assimilate this nitrogen source confers advantages on this yeast during the fermentation process industry. However, larger studies are needed in this way as our group is investigating new proteins under LC-MS/MS approach. Together, these studies will help in understanding the operation of networks and cellular regulation of the process of assimilation of nitrogen sources for the D. bruxellensis, unravelling new aspects of

  9. The effect of nitrate on ethylene biofiltration

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sang-Hun, E-mail: lee323@alumni.purdue.edu [Department of Agricultural and Biological Engineering, Purdue University, 225 South University St., West Lafayette, 47907-2093 IN (United States); Li, Congna; Heber, Albert J. [Department of Agricultural and Biological Engineering, Purdue University, 225 South University St., West Lafayette, 47907-2093 IN (United States)

    2012-11-30

    Highlights: Black-Right-Pointing-Pointer Ethylene biofiltration strongly depends on nitrate concentrations and media types. Black-Right-Pointing-Pointer We examine reduced N supply can increase ethylene removals in biofilters. Black-Right-Pointing-Pointer Perlite medium is better for ethylene biofiltration than activated carbon medium. - Abstract: This study investigated the effects of filter media types and nitrate (NO{sub 3}{sup -}) concentrations in nutrient solutions on C{sub 2}H{sub 4} biofiltration. A new nutrient solution with zero NO{sub 3}{sup -} concentration was supplied to two perlite-bed biotrickling filters, two perlite-bed biofilters, and two GAC (Granular Activated Carbon)-bed biofilters, while the other with 2 g L{sup -1} of NO{sub 3}{sup -} was used for the other two GAC biofilters. All reactors underwent a total test duration of over 175 days with an EBRT (Empty Bed Residence Time) of 30 s, inlet gas flow rate of 7 L min{sup -1}, and inlet C{sub 2}H{sub 4} concentrations of 20-30 mg m{sup -3}. NO{sub 3}{sup -} concentration and media type significantly affected the C{sub 2}H{sub 4} removal efficiencies in all types of biofiltration. The perlite media with no NO{sub 3}{sup -} achieved C{sub 2}H{sub 4} removal efficiencies 10-50% higher than the others. A NO{sub 3}{sup -} concentration as high as 2 g L{sup -1} in the original nutrient solution may act as an inhibitor that suppresses the growth or activity of C{sub 2}H{sub 4} degraders. In addition, the perlite media resulted in higher C{sub 2}H{sub 4} removal efficiencies than GAC media, because the hydrophilic surface of the perlite leads to a higher moisture content and thus to favorable microbial growth.

  10. ARRAYS OF BOTTLES OF PLUTONIUM NITRATE SOLUTION

    Energy Technology Data Exchange (ETDEWEB)

    Margaret A. Marshall

    2012-09-01

    In October and November of 1981 thirteen approaches-to-critical were performed on a remote split table machine (RSTM) in the Critical Mass Laboratory of Pacific Northwest Laboratory (PNL) in Richland, Washington using planar arrays of polyethylene bottles filled with plutonium (Pu) nitrate solution. Arrays of up to sixteen bottles were used to measure the critical number of bottles and critical array spacing with a tight fitting Plexiglas® reflector on all sides of the arrays except the top. Some experiments used Plexiglas shells fitted around each bottles to determine the effect of moderation on criticality. Each bottle contained approximately 2.4 L of Pu(NO3)4 solution with a Pu content of 105 g Pu/L and a free acid molarity H+ of 5.1. The plutonium was of low 240Pu (2.9 wt.%) content. These experiments were sponsored by Rockwell Hanford Operations because of the lack of experimental data on the criticality of arrays of bottles of Pu solution such as might be found in storage and handling at the Purex Facility at Hanford. The results of these experiments were used “to provide benchmark data to validate calculational codes used in criticality safety assessments of [the] plant configurations” (Ref. 1). Data for this evaluation were collected from the published report (Ref. 1), the approach to critical logbook, the experimenter’s logbook, and communication with the primary experimenter, B. Michael Durst. Of the 13 experiments preformed 10 were evaluated. One of the experiments was not evaluated because it had been thrown out by the experimenter, one was not evaluated because it was a repeat of another experiment and the third was not evaluated because it reported the critical number of bottles as being greater than 25. Seven of the thirteen evaluated experiments were determined to be acceptable benchmark experiments. A similar experiment using uranyl nitrate was benchmarked as U233-SOL-THERM-014.

  11. REMOVAL OF ADDED NITRATE IN COTTON BURR COMPOST, MULCH COMPOST, AND PEAT: MECHANISMS AND POTENTIAL USE FOR GROUNDWATER NITRATE REMEDIATION

    Science.gov (United States)

    We conducted batch tests on the nature and kinetics of removal of added nitrate in cotton burr compost, mulch compost, and sphagnum peat that may be potentially used in a permeable reactive barrier (PRB) for groundwater nitrate remediation. A rigorous steam autoclaving protocol (...

  12. REMOVAL OF ADDED NITRATE IN COTTON BURR COMPOST, MULCH COMPOST, AND PEAT: MECHANISMS AND POTENTIAL USE FOR GROUNDWATER NITRATE REMEDIATION

    Science.gov (United States)

    We conducted batch tests on the nature and kinetics of removal of added nitrate in cotton burr compost, mulch compost, and sphagnum peat that may be potentially used in a permeable reactive barrier (PRB) for groundwater nitrate remediation. A rigorous steam autoclaving protocol (...

  13. Synthesis, spectroscopic, thermal and antimicrobial studies of neodymium(III) and samarium(III) complexes derived from tetradentate ligands containing N and S donor atoms.

    Science.gov (United States)

    Ain, Qurratul; Pandey, S K; Pandey, O P; Sengupta, S K

    2015-04-05

    Trivalent lanthanide complexes of the type [Ln(L)Cl(H2O)2] (where Ln=Nd(III) or Sm(III) and LH2=Schiff bases derived by the condensation of 3-(phenyl/substitutedphenyl)-4-amino-5-mercapto-1,2,4-triazole with diacetyl/benzil) have been synthesized by the reactions of anhydrous lanthanide(III) chloride with Schiff bases in methanol. The structures of the complexes have been proposed on the basis of elemental analysis, electrical conductance, magnetic moment, spectroscopic measurements (IR, 1H, 13C NMR and UV-vis spectra) and X-ray diffraction studies. The spectral data reveal that the Schiff base ligands behave as dibasic tetradentate chelating agents having coordination sites at two thiol sulfur atoms and two azomethine nitrogen atoms. The presence of coordinated water in metal complexes was confirmed by thermal and IR data of the complexes. All the Schiff bases and their metal complexes have also been screened for their antibacterial activity against Bacillus subtilis, Staphylococcus aureus and antifungal activities against Aspergillus niger, Curvularia pallescens and Colletotrichum capsici.

  14. Conductometric nitrate biosensor based on methyl viologen/Nafion/nitrate reductase interdigitated electrodes.

    Science.gov (United States)

    Xuejiang, Wang; Dzyadevych, Sergei V; Chovelon, Jean-Marc; Renault, Nicole Jaffrezic; Ling, Chen; Siqing, Xia; Jianfu, Zhao

    2006-04-15

    A highly sensitive, fast and stable conductometric enzyme biosensor for determination of nitrate in water is reported for the first time. The biosensor electrodes were modified by methyl viologen mediator mixed with nitrate reductase (NR) from Aspergillus niger by cross-linking with glutaraldehyde in the presence of bovine serum albumin and Nafion((R)) cation-exchange polymer. The process parameters for the fabrication of the enzyme electrode and various experimental variables such as pH, the enzyme loading and time of immobilization in glutaralaldehyde vapor were investigated with regard to their influence on sensitivity, limit of detection, dynamic range and operational and storage stability. The biosensor can reach 95% of steady-state conductance value in about 15s. Linear calibration in the range of 0.02 and 0.25 mM with detection limits of 0.005 mM nitrate was obtained with a signal-to-noise ratio of 3. When stored in 5 mM phosphate buffer (pH 7.5) at 4 degrees C, the sensor showed good stability over 2 weeks.

  15. Fractionation of Nitrogen and Oxygen Isotopes During Microbial Nitrate Reduction

    Science.gov (United States)

    Lehmann, M. F.; Bernasconi, S. M.; Reichert, P.; Barbieri, A.; McKenzie, J. A.

    2001-12-01

    Lakes represent an important continental sink of fixed nitrogen. Besides the burial of particulate nitrogen, fixed nitrogen is eliminated from lakes by emission of N2 and N2O to the atmosphere during dissimilative nitrate reduction within suboxic and anoxic waters or sediments. The understanding and quantification of this efficient nitrogen removal process in eutrophic lakes is crucial for nitrogen budget modelling and the application and evaluation of lake restoration measures. In order to use natural abundance N and O isotope ratios as tracers for microbial nitrate reduction and to obtain quantitative estimates on its intensity, it is crucial to constrain the associated isotope fractionation. This is the first report of nitrogen and oxygen isotope effects associated with microbial nitrate reduction in lacustrine environments. Nitrate reduction in suboxic and anoxic waters of the southern basin of Lake Lugano (Switzerland) is demonstrated by a progressive nitrate depletion coupled to increasing δ 15N and δ 18O values for residual nitrate. 15N and 18O enrichment factors (ɛ ) were estimated using a closed-system (Rayleigh-distillation) model and a dynamic reaction-diffusion model. Calculated enrichment factors ɛ ranged between -11.2 and -22‰ for 15N and between -6.6 and -11.3‰ for 18O with both nitrogen and oxygen isotope fractionation being greatest during times with the highest nitrate reduction rates. The closed-system model neglects vertical diffusive mixing and does not distinguish between sedimentary and water-column nitrate reduction. Therefore, it tends to underestimate the intrinsic isotope effect of microbial nitrate reduction. Based upon results from earlier studies that indicate that nitrate reduction in sediments displays a highly reduced N-isotope effect (Brandes and Devol, 1997), model-derived enrichment factors could be used to discern the relative importance of nitrate reduction in the water column and in the sediment. Sedimentary nitrate

  16. Effects of Amino Acids Replacing Nitrate on Growth, Nitrate Accumulation, and Macroelement Concentrations in Pak-choi (Brassica chinensis L.)

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A hydroponic experiment was carried out to determine the influence of replacing 20% of nitrate-N in nutrient solutions with 20 individual amino acids on growth, nitrate accumulation, and concentrations of nitrogen (N), phosphorus (P), and potassium (K) in pak-choi (Brassica chinensis L.) shoots. When 20% of nitrate-N was replaced with arginine (Arg)compared to the full nitrate treatment, pak-choi shoot fresh and dry weights increased significantly (P ≤ 0.05), but when 20% of nitrate-N was replaced with alanine (Ala), valine (Val), leucine (Leu), isoleucine (Ile), proline (Pro), phenylalanine (Phe), methionine (Met), aspartic acid (Asp), glutamic acid (Glu), lysine (Lys), glycine (Gly), serine (Ser), threonine(Thr), cysteine (Cys), and tyrosine (Tyr), shoot fresh and dry weights decreased significantly (P ≤ 0.05). After replacing 20% of nitrate-N with asparagine (Asn) and glutamine (Gln), shoot fresh and dry weights were unaffected. Compared to the full nitrate treatment, amino acid replacement treatments, except for Cys, Gly, histidine (His), and Arg, significantly reduced (P ≤ 0.05) nitrate concentrations in plant shoots. Except for Cys, Leu, Pro, and Met, total N concentrations in plant tissues of the other amino acid treatments significantly increased (P ≤ 0.05). Amino acids also affected total P and K concentrations, but the effects differed depending on individual amino acids. To improve pak-choi shoot quality, Gln and Asn, due to their insignificant effects on pak-choi growth, their significant reduction in nitrate concentrations, and their increase in macroelement content in plants, may be used to partially replace nitrate-N.

  17. Plasma nitrate clearance in mice: modeling of the systemic production of nitrate following the induction of nitric oxide synthesis.

    Science.gov (United States)

    Veszelovsky, E; Holford, N H; Thomsen, L L; Knowles, R G; Baguley, B C

    1995-01-01

    Nitric oxide (NO) is produced in mammals by the enzyme NO synthase (NOS) in response to a number of agents, including the experimental antitumour agent flavone acetic acid (FAA) and the cytokine tumour necrosis factor-alpha (TNF). NO is converted rapidly in the presence of oxygen, water and haemoglobin to oxidation products, largely nitrate. To quantitate the production of nitric oxide it is necessary to know the clearance of nitrate. The concentration of nitrite and nitrate ion in the plasma of C3H and BDF1 (C57BL6 x DBA2) mice was assessed before and after injection of sodium nitrate and sodium nitrite. Nitrite was covered rapidly to nitrate and the kinetics of elimination of nitrate were determined. There was no significant difference between results obtained with different mouse strains, between levels of nitrite and nitrate, or between i.p. and i.v. administration, and the observations were therefore combined. The volume of distribution of nitrate was 0.71 +/- 0.04 l/kg and the clearance was 0.32 +/- 0.02 l/h-1/kg-1 (plasma half-life, 1.54 h). Using previously published data, we developed a pharmacokinetic-pharmacodynamic model that relates the production of TNF in response to administration of FAA, the enhancement of NOS activity in response to TNF, and the elevation of plasma nitrate in response to NO production. This information permits the prediction from observed plasma nitrate values of the amount of NOS induced in vivo.

  18. The Nitrate App: Enhancing nutrient best management practice adoption and targeting via instantaneous, on-farm nitrate data

    Science.gov (United States)

    Rozemeijer, J.; De Geus, D.; Ekkelenkamp, R.

    2016-12-01

    Sociological surveys suggest that farmers understand that agriculture contributes to nutrient pollution but the same surveys also indicate that in the absence of on-farm nitrate data, farmers assume someone else is causing the problem. This tendency to overestimate our own abilities is common to all of us and often described as "Lake Wobegon Syndrome" after the mythical town where "where all the women are strong, all the men are good-looking, and all the children are above average." We developed the Nitrate App for smartphones to enable farmers and citizens to collect and share nitrate concentration measurements. The app accurately reads and interprets nitrate test strips, directly displays the measured concentration, and gives the option to share the result. The shared results are immediately visualised in the online Delta Data Viewer. Within this viewer, user group specific combinations of background maps, monitoring data, and study area characteristics can be configured. Through the Nitrate App's mapping function project managers can more accurately target conservation practices to areas with the highest nitrate concentrations and loads. Furthermore, we expect that the actual on-farm data helps to overcome the "Lake Wobegon Effect" and will encourage farmers to talk to specialists about the right nutrient best management practices (BMP's) for their farm. After implementing these BMP's, the farmers can keep monitoring to evaluate the reduction in nitrate losses. In this presentation, we explain the Nitrate App technology and present the results of the first field applications in The Netherlands. We expect this free to download app to have wide transferability across watershed projects worldwide focusing on nitrate contamination of groundwater or surface water. Its simple design requires no special equipment outside of the nitrate test strips, a reference card, and a smartphone. The technology is also transferable to other relevant solutes for which test strips

  19. Atmospheric peroxyacetyl nitrate (PAN): a global budget and source attribution

    Science.gov (United States)

    Fischer, E. V.; Jacob, D. J.; Yantosca, R. M.; Sulprizio, M. P.; Millet, D. B.; Mao, J.; Paulot, F.; Singh, H. B.; Roiger, A.; Ries, L.; Talbot, R. W.; Dzepina, K.; Pandey Deolal, S.

    2014-03-01

    Peroxyacetyl nitrate (PAN) formed in the atmospheric oxidation of non-methane volatile organic compounds (NMVOCs) is the principal tropospheric reservoir for nitrogen oxide radicals (NOx = NO + NO2). PAN enables the transport and release of NOx to the remote troposphere with major implications for the global distributions of ozone and OH, the main tropospheric oxidants. Simulation of PAN is a challenge for global models because of the dependence of PAN on vertical transport as well as complex and uncertain NMVOC sources and chemistry. Here we use an improved representation of NMVOCs in a global 3-D chemical transport model (GEOS-Chem) and show that it can simulate PAN observations from aircraft campaigns worldwide. The immediate carbonyl precursors for PAN formation include acetaldehyde (44% of the global source), methylglyoxal (30%), acetone (7%), and a suite of other isoprene and terpene oxidation products (19%). A diversity of NMVOC emissions is responsible for PAN formation globally including isoprene (37%) and alkanes (14%). Anthropogenic sources are dominant in the extratropical Northern Hemisphere outside the growing season. Open fires appear to play little role except at high northern latitudes in spring, although results are very sensitive to plume chemistry and plume rise. Lightning NOx is the dominant contributor to the observed PAN maximum in the free troposphere over the South Atlantic.

  20. Ultrastructural and metabolic changes in osteoblasts exposed to uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Tasat, D.R. [Universidad Nacional de San Martin, Escuela de Ciencia y Tecnologia, Pcia de Bs.As. (Argentina); Universidad de Buenos Aires, Catedra de Histologia y Embriologia, Facultad de Odontologia, Buenos Aires (Argentina); Orona, N.S. [Universidad Nacional de San Martin, Escuela de Ciencia y Tecnologia, Pcia de Bs.As. (Argentina); Mandalunis, P.M. [Universidad de Buenos Aires, Catedra de Histologia y Embriologia, Facultad de Odontologia, Buenos Aires (Argentina); Cabrini, R.L. [Comision Nacional de Energia Atomica, Departamento de Radiobiologia, Buenos Aires (Argentina); Ubios, A.M. [Comision Nacional de Energia Atomica, Departamento de Radiobiologia, Buenos Aires (Argentina); Universidad de Buenos Aires, Catedra de Histologia y Embriologia, Facultad de Odontologia, Buenos Aires (Argentina)

    2007-05-15

    Exposure to uranium is an occupational hazard to workers who continually handle uranium and an environmental risk to the population at large. Since the cellular and molecular pathways of uranium toxicity in osteoblast cells are still unknown, the aim of the present work was to evaluate the adverse effects of uranyl nitrate (UN) on osteoblasts both in vivo and in vitro. Herein we studied the osteoblastic ultrastructural changes induced by UN in vivo and analyzed cell proliferation, generation of reactive oxygen species (ROS), apoptosis, and alkaline phosphatase (APh) activity in osteoblasts exposed to various UN concentrations (0.1, 1, 10, and 100 {mu}M) in vitro. Cell proliferation was quantified by means of the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, ROS was determined using the nitro blue tetrazolium test, apoptosis was morphologically determined using Hoechst 3332 and APh activity was assayed spectrophotometrically. Electron microscopy revealed that the ultrastructure of active and inactive osteoblasts exposed to uranium presented cytoplasmic and nuclear alterations. In vitro, 1-100 {mu}M UN failed to modify cell proliferation ratio and to induce apoptosis. ROS generation increased in a dose-dependent manner in all tested doses. APh activity was found to decrease in 1-100 {mu}M UN-treated cells vs. controls. Our results show that UN modifies osteoblast cell metabolism by increasing ROS generation and reducing APh activity, suggesting that ROS may play a more complex role in cell physiology than simply causing oxidative damage. (orig.)

  1. Multiobjective optimization for Groundwater Nitrate Pollution Control. Application to El Salobral-Los Llanos aquifer (Spain).

    Science.gov (United States)

    Llopis-Albert, C.; Peña-Haro, S.; Pulido-Velazquez, M.; Molina, J.

    2012-04-01

    Water quality management is complex due to the inter-relations between socio-political, environmental and economic constraints and objectives. In order to choose an appropriate policy to reduce nitrate pollution in groundwater it is necessary to consider different objectives, often in conflict. In this paper, a hydro-economic modeling framework, based on a non-linear optimization(CONOPT) technique, which embeds simulation of groundwater mass transport through concentration response matrices, is used to study optimal policies for groundwater nitrate pollution control under different objectives and constraints. Three objectives were considered: recovery time (for meeting the environmental standards, as required by the EU Water Framework Directive and Groundwater Directive), maximum nitrate concentration in groundwater, and net benefits in agriculture. Another criterion was added: the reliability of meeting the nitrate concentration standards. The approach allows deriving the trade-offs between the reliability of meeting the standard, the net benefits from agricultural production and the recovery time. Two different policies were considered: spatially distributed fertilizer standards or quotas (obtained through multi-objective optimization) and fertilizer prices. The multi-objective analysis allows to compare the achievement of the different policies, Pareto fronts (or efficiency frontiers) and tradeoffs for the set of mutually conflicting objectives. The constraint method is applied to generate the set of non-dominated solutions. The multi-objective framework can be used to design groundwater management policies taking into consideration different stakeholders' interests (e.g., policy makers, agricultures or environmental groups). The methodology was applied to the El Salobral-Los Llanos aquifer in Spain. Over the past 30 years the area has undertaken a significant socioeconomic development, mainly due to the intensive groundwater use for irrigated crops, which has

  2. Hyporheic nutrient transformation - A panacea for river restoration that solves the "Nitrate Time Bomb" ?

    Science.gov (United States)

    Krause, S.; Heathwaite, L.; Binley, A.; Kaeser, D.

    2009-04-01

    some areas as well as nitrification in others. The spatial patterns of nitrate attenuation or release areas were controlled by the hyporheic connectivity, described by the spatial and temporal coincidence of flow pattern and residence times within areas of variable redox conditions. The hyporheic nitrate contributions were furthermore found to have a seasonally variable impact on the in stream concentrations. The results of this study proof, that hyporheic impacts on in stream nutrient concentrations can be far more complex, even on a small scale, than it has been acknowledged so far.

  3. Using Bayesian hierarchical models to better understand nitrate sources and sinks in agricultural watersheds.

    Science.gov (United States)

    Xia, Yongqiu; Weller, Donald E; Williams, Meghan N; Jordan, Thomas E; Yan, Xiaoyuan

    2016-11-15

    Export coefficient models (ECMs) are often used to predict nutrient sources and sinks in watersheds because ECMs can flexibly incorporate processes and have minimal data requirements. However, ECMs do not quantify uncertainties in model structure, parameters, or predictions; nor do they account for spatial and temporal variability in land characteristics, weather, and management practices. We applied Bayesian hierarchical methods to address these problems in ECMs used to predict nitrate concentration in streams. We compared four model formulations, a basic ECM and three models with additional terms to represent competing hypotheses about the sources of error in ECMs and about spatial and temporal variability of coefficients: an ADditive Error Model (ADEM), a SpatioTemporal Parameter Model (STPM), and a Dynamic Parameter Model (DPM). The DPM incorporates a first-order random walk to represent spatial correlation among parameters and a dynamic linear model to accommodate temporal correlation. We tested the modeling approach in a proof of concept using watershed characteristics and nitrate export measurements from watersheds in the Coastal Plain physiographic province of the Chesapeake Bay drainage. Among the four models, the DPM was the best--it had the lowest mean error, explained the most variability (R(2) = 0.99), had the narrowest prediction intervals, and provided the most effective tradeoff between fit complexity (its deviance information criterion, DIC, was 45.6 units lower than any other model, indicating overwhelming support for the DPM). The superiority of the DPM supports its underlying hypothesis that the main source of error in ECMs is their failure to account for parameter variability rather than structural error. Analysis of the fitted DPM coefficients for cropland export and instream retention revealed some of the factors controlling nitrate concentration: cropland nitrate exports were positively related to stream flow and watershed average slope

  4. Protein tyrosine nitration in pea roots during development and senescence

    Science.gov (United States)

    Corpas, Francisco J.

    2013-01-01

    Protein tyrosine nitration is a post-translational modification mediated by reactive nitrogen species (RNS) that is associated with nitro-oxidative damage. No information about this process is available in relation to higher plants during development and senescence. Using pea plants at different developmental stages (ranging from 8 to 71 days), tyrosine nitration in the main organs (roots, stems, leaves, flowers, and fruits) was analysed using immunological and proteomic approaches. In the roots of 71-day-old senescent plants, nitroproteome analysis enabled the identification a total of 16 nitrotyrosine-immunopositive proteins. Among the proteins identified, NADP-isocitrate dehydrogenase (ICDH), an enzyme involved in the carbon and nitrogen metabolism, redox regulation, and responses to oxidative stress, was selected to evaluate the effect of nitration. NADP-ICDH activity fell by 75% during senescence. Analysis showed that peroxynitrite inhibits recombinant cytosolic NADP-ICDH activity through a process of nitration. Of the 12 tyrosines present in this enzyme, mass spectrometric analysis of nitrated recombinant cytosolic NADP-ICDH enabled this study to identify the Tyr392 as exclusively nitrated by peroxynitrite. The data as a whole reveal that protein tyrosine nitration is a nitric oxide-derived PTM prevalent throughout root development and intensifies during senescence. PMID:23362300

  5. Treatment of nitrate contaminated water using an electrochemical method.

    Science.gov (United States)

    Li, Miao; Feng, Chuanping; Zhang, Zhenya; Yang, Shengjiong; Sugiura, Norio

    2010-08-01

    Treatment of nitrate contaminated water which is unsuitable for biological removal using an electrochemical method with Fe as a cathode and Ti/IrO(2)-Pt as an anode in an undivided cell was studied. In the absence and presence of 0.50 g/L NaCl, the nitrate-N decreased from 100.0 to 7.2 and 12.9 mg/L in 180 min, respectively, and no ammonia and nitrite by-products were detected in the presence of NaCl. The nitrate reduction rate increased with increasing current density, with the nitrate reduction rate constant k(1) increasing from 0.008 min(-1) (10 mA/cm(2)) to 0.016 min(-1) (60 mA/cm(2)) but decreasing slightly with increasing NaCl concentration. High temperature favoured nitrate reduction and the reaction followed first order kinetics. The combination of the Fe cathode and Ti/IrO(2)-Pt anode was suitable for nitrate reduction between initial pH values 3.0 and 11.0. e.g. k(1)=0.010 min(-1) (initial pH 3.0) and k(1)=0.013 min(-1) (initial pH 11.0). Moreover, the surface of all used cathodes appeared rougher than unused electrodes, which may have increased the nitrate reduction rate (4-6%). Copyright 2010 Elsevier Ltd. All rights reserved.

  6. Nitrate pollution study in the aquifer of Dakar (Senegal).

    Science.gov (United States)

    Tandia, A A; Diop, E S; Gaye, C B; Travi, Y

    2000-01-01

    Dakar is a peninsula inhabited by a population of about 2 million people in 1996. In some dug wells and piezometers, the nitrate content (NO3.) in the groundwater is above the World Health Organization (WHO) limit of 50 mg/l. In the unconfined part of the aquifer of the peninsula, all the samples from wells are contaminated by high nitrate contents which increased over time from 100 mg/l in 1987 to more than 250 mg/l in 1996. Only a limited area is affected by nitrate pollution in the confined layer. The results indicate anthropogenic pollution, a fact which indicates the increasing risk of pollution of drinking-water resources. Studies in the unsaturated zone and familiarity with the sanitation practices in the area indicate that the horizontal and vertical flux are linked mainly to defective septic tanks and direct organic waste elimination into the soil by more than 40% of the inhabitants. The correlation between tritium values (3H) and nitrate shows that the source of nitrate is recent. The relation of oxygen 18 (18O) to deuterium (2H) in water with high nitrate levels indicates that the concentrations of nitrate have been identified in evaporated points.

  7. Reduction of nitrate by bimetallic Fe/Ni nanoparticles.

    Science.gov (United States)

    Kang, Haiyan; Xiu, Zongming; Chen, Jiawei; Cao, Wenping; Guo, Yifei; Li, Tielong; Jin, Zhaohui

    2012-09-01

    Bimetallic Fe/Ni nanoparticles were synthesized and their nitrate reduction capacity was studied. Nitrate (354 mg L(-1), equal to 5.71 mmol L(-1)) reduction was performed using Fe/Ni nanoparticles with various Ni contents (1.0, 5.0, 10 and 20%) in an unbuffered condition. Optimum nitrate reduction rate (1.03 +/- 0.087 x 10(-4) mol x min(-1) x greduc(-1)) was obtained with 5.0% nano-scale Fe/Ni, while only 25% nitrate (1.05 +/- 0.091 x 10(-5) mol x min(-1) x greduc(-1)) was transformed by nano-scale Fe(0) within the same reaction time, which means that these bimetallic nanoparticles are obviously more reactive than monometallic nano-scale Fe(0). For this bimetallic system a near-neutral initial pH (6.5) is more favourable than an acidic condition (2.0 and 4.0). Relatively air-stable nano-scale Fe/Ni particles were developed by slowly aging them for 22 h and exhibited similar reactivity to freshly synthesized nano-scale Fe(0). Although undesirable transformation of nitrate (91.0 +/- 0.37%) to ammonium was observed in this study, Fe/Ni particles showed a much higher nitrate reduction rate and an optimum reduction rate at near-neutral pH, which may have important implications for nitrate-contaminated site remediation.

  8. Nitrate in groundwater of the United States, 1991-2003

    Science.gov (United States)

    Burow, Karen R.; Nolan, Bernard T.; Rupert, Michael G.; Dubrovsky, Neil M.

    2010-01-01

    An assessment of nitrate concentrations in groundwater in the United States indicates that concentrations are highest in shallow, oxic groundwater beneath areas with high N inputs. During 1991-2003, 5101 wells were sampled in 51 study areas throughout the U.S. as part of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) program. The well networks reflect the existing used resource represented by domestic wells in major aquifers (major aquifer studies), and recently recharged groundwater beneath dominant land-surface activities (land-use studies). Nitrate concentrations were highest in shallow groundwater beneath agricultural land use in areas with well-drained soils and oxic geochemical conditions. Nitrate concentrations were lowest in deep groundwater where groundwater is reduced, or where groundwater is older and hence concentrations reflect historically low N application rates. Classification and regression tree analysis was used to identify the relative importance of N inputs, biogeochemical processes, and physical aquifer properties in explaining nitrate concentrations in groundwater. Factors ranked by reduction in sum of squares indicate that dissolved iron concentrations explained most of the variation in groundwater nitrate concentration, followed by manganese, calcium, farm N fertilizer inputs, percent well-drained soils, and dissolved oxygen. Overall, nitrate concentrations in groundwater are most significantly affected by redox conditions, followed by nonpoint-source N inputs. Other water-quality indicators and physical variables had a secondary influence on nitrate concentrations.

  9. Modeling groundwater nitrate concentrations in private wells in Iowa

    Science.gov (United States)

    Wheeler, David C.; Nolan, Bernard T.; Flory, Abigail R.; DellaValle, Curt T.; Ward, Mary H.

    2015-01-01

    Contamination of drinking water by nitrate is a growing problem in many agricultural areas of the country. Ingested nitrate can lead to the endogenous formation of N-nitroso compounds, potent carcinogens. We developed a predictive model for nitrate concentrations in private wells in Iowa. Using 34,084 measurements of nitrate in private wells, we trained and tested random forest models to predict log nitrate levels by systematically assessing the predictive performance of 179 variables in 36 thematic groups (well depth, distance to sinkholes, location, land use, soil characteristics, nitrogen inputs, meteorology, and other factors). The final model contained 66 variables in 17 groups. Some of the most important variables were well depth, slope length within 1 km of the well, year of sample, and distance to nearest animal feeding operation. The correlation between observed and estimated nitrate concentrations was excellent in the training set (r-square = 0.77) and was acceptable in the testing set (r-square = 0.38). The random forest model had substantially better predictive performance than a traditional linear regression model or a regression tree. Our model will be used to investigate the association between nitrate levels in drinking water and cancer risk in the Iowa participants of the Agricultural Health Study cohort.

  10. Circuit Design for Sensor Detection Signal Conditioner Nitrate Content

    Directory of Open Access Journals (Sweden)

    Robeth Manurung

    2011-09-01

    Full Text Available Nitrate is one of macro nutrients very important for agriculture. The availability of nitrate in soil is limited because it is very easy to leaching by rain, therefore nitrate could be contaminated ground water by  over-process of fertilizer. This process could also produce inefficiency in agriculture if it happened continuesly without pre-analysis of farm field. The answer those problems, it is need to develop the ion sensor system to measure concentrations of nitrat in soil. The system is consist of nitrate ion sensor device, signal conditioning and data acquisition circuit. The design and fabrications of signal conditioning circuit which integrated into ion nitrate sensor system and will apply for agriculture. This sensor has been used amperometric with three electrodes configuration: working, reference  and auxiliarry; the ion senstive membrane has use conductive polymer. The screen printing technique has been choosen to fabricate electrodes and deposition technique for ion sensitive membrane is electropolymerization. The characterization of sensor has been conducted using nitrate standard solution with range of concentration between 1 µM–1 mM. The characterization has shown that sensor has a good response with cureent output between 2.8–4.71 µA, liniearity factor is 99.65% and time response 250 second.

  11. Isoprene nitrates: preparation, separation, identification, yields, and atmospheric chemistry

    Directory of Open Access Journals (Sweden)

    A. L. Lockwood

    2010-07-01

    Full Text Available Isoprene is an important atmospheric volatile organic compound involved in ozone production and NOx (NO+NO2 sequestration and transport. Isoprene reaction with OH in the presence of NO can form either isoprene hydroxy nitrates ("isoprene nitrates" or convert NO to NO2 which can photolyze to form ozone. While it has been shown that isoprene nitrate production can represent an important sink for NOx in forest impacted environments, there is little experimental knowledge of the relative importance of the individual isoprene nitrate isomers, each of which has a different fate and reactivity. In this work, we have identified the 8 individual isomers and determined their total and individual production yields. The overall yield of isoprene nitrates at atmospheric pressure and 295 K was found to be 0.070(+0.025/−0.015. Three isomers, representing nitrates resulting from OH addition to a terminal carbon, represent 90% of the total IN yield. We also determined the ozone rate constants for three of the isomers, and have calculated their atmospheric lifetimes, which range from ~1–2 h, making their oxidation products likely more important as atmospheric organic nitrates and sinks for nitrogen.

  12. In vivo protein tyrosine nitration in Arabidopsis thaliana

    Science.gov (United States)

    Lozano-Juste, Jorge; Colom-Moreno, Rosa; León, José

    2011-01-01

    Nitration of tyrosine (Y) residues of proteins is a low abundant post-translational modification that modulates protein function or fate in animal systems. However, very little is known about the in vivo prevalence of this modification and its corresponding targets in plants. Immunoprecipitation, based on an anti-3-nitroY antibody, was performed to pull-down potential in vivo targets of Y nitration in the Arabidopsis thaliana proteome. Further shotgun liquid chromatography–mass spectrometry (LC-MS/MS) proteomic analysis of the immunoprecipitated proteins allowed the identification of 127 proteins. Around 35% of them corresponded to homologues of proteins that have been previously reported to be Y nitrated in other non-plant organisms. Some of the putative in vivo Y-nitrated proteins were further confirmed by western blot with specific antibodies. Furthermore, MALDI-TOF (matrix-assisted laser desorption ionization-time of flight) analysis of protein spots, separated by two-dimensional electrophoresis from immunoprecipitated proteins, led to the identification of seven nitrated peptides corresponding to six different proteins. However, in vivo nitration sites among putative targets could not be identified by MS/MS. Nevertheless, an MS/MS spectrum with 3-aminoY318 instead of the expected 3-nitroY was found for cytosolic glyceraldehyde-3-phosphate dehydrogenase. Reduction of nitroY to aminoY during MS-based proteomic analysis together with the in vivo low abundance of these modifications made the identification of nitration sites difficult. In turn, in vitro nitration of methionine synthase, which was also found in the shotgun proteomic screening, allowed unequivocal identification of a nitration site at Y287. PMID:21378116

  13. Metal-catalyzed protein tyrosine nitration in biological systems.

    Science.gov (United States)

    Campolo, Nicolás; Bartesaghi, Silvina; Radi, Rafael

    2014-11-01

    Protein tyrosine nitration is an oxidative postranslational modification that can affect protein structure and function. It is mediated in vivo by the production of nitric oxide-derived reactive nitrogen species (RNS), including peroxynitrite (ONOO(-)) and nitrogen dioxide ((•)NO₂). Redox-active transition metals such as iron (Fe), copper (Cu), and manganese (Mn) can actively participate in the processes of tyrosine nitration in biological systems, as they catalyze the production of both reactive oxygen species and RNS, enhance nitration yields and provide site-specificity to this process. Early after the discovery that protein tyrosine nitration can occur under biologically relevant conditions, it was shown that some low molecular weight transition-metal centers and metalloproteins could promote peroxynitrite-dependent nitration. Later studies showed that nitration could be achieved by peroxynitrite-independent routes as well, depending on the transition metal-catalyzed oxidation of nitrite (NO₂(-)) to (•)NO₂ in the presence of hydrogen peroxide. Processes like these can be achieved either by hemeperoxidase-dependent reactions or by ferrous and cuprous ions through Fenton-type chemistry. Besides the in vitro evidence, there are now several in vivo studies that support the close relationship between transition metal levels and protein tyrosine nitration. So, the contribution of transition metals to the levels of tyrosine nitrated proteins observed under basal conditions and, specially, in disease states related with high levels of these metal ions, seems to be quite clear. Altogether, current evidence unambiguously supports a central role of transition metals in determining the extent and selectivity of protein tyrosine nitration mediated both by peroxynitrite-dependent and independent mechanisms.

  14. Magnesium nitrate attenuates blood pressure rise in SHR rats.

    Science.gov (United States)

    Vilskersts, Reinis; Kuka, Janis; Liepinsh, Edgars; Cirule, Helena; Gulbe, Anita; Kalvinsh, Ivars; Dambrova, Maija

    2014-01-01

    The administration of magnesium supplements and nitrates/nitrites decreases arterial blood pressure and attenuates the development of hypertension-induced complications. This study was performed to examine the effects of treatment with magnesium nitrate on the development of hypertension and its complications in spontaneously hypertensive (SHR) rats. Male SHR rats with persistent hypertension at the age of 12-13 weeks were allocated to two groups according to their arterial blood pressure. Rats from the control group received purified water, while the experimental animals from the second group received magnesium nitrate dissolved in purified water at a dose of 50 mg/kg. After four weeks of treatment, blood pressure was measured, the anatomical and functional parameters of the heart were recorded using an ultrasonograph, vascular reactivity was assayed in organ bath experiments and the cardioprotective effects of magnesium nitrate administration was assayed in an ex vivo experimental heart infarction model. Treatment with magnesium nitrate significantly increased the nitrate concentration in the plasma (from 62 ± 8 μmol/l to 111 ± 8 μmol/L), and attenuated the increase in the arterial blood pressure. In the control and magnesium nitrate groups, the blood pressure rose by 21 ± 3 mmHg and 6 ± 4 mmHg, respectively. The administration of magnesium nitrate had no effect on the altered vasoreactivity, heart function or the size of the heart infarction. In conclusion, our results demonstrate that magnesium nitrate effectively attenuates the rise in arterial blood pressure. However, a longer period of administration or earlier onset of treatment might be needed to delay the development of complications due to hypertension.

  15. Glyphosate detection with ammonium nitrate and humic acids as potential interfering substances by pulsed voltammetry technique.

    Science.gov (United States)

    Martínez Gil, Pablo; Laguarda-Miro, Nicolas; Camino, Juan Soto; Peris, Rafael Masot

    2013-10-15

    Pulsed voltammetry has been used to detect and quantify glyphosate on buffered water in presence of ammonium nitrate and humic substances. Glyphosate is the most widely used herbicide active ingredient in the world. It is a non-selective broad spectrum herbicide but some of its health and environmental effects are still being discussed. Nowadays, glyphosate pollution in water is being monitored but quantification techniques are slow and expensive. Glyphosate wastes are often detected in countryside water bodies where organic substances and fertilizers (commonly based on ammonium nitrate) may also be present. Glyphosate also forms complexes with humic acids so these compounds have also been taken into consideration. The objective of this research is to study the interference of these common pollutants in glyphosate measurements by pulsed voltammetry. The statistical treatment of the voltammetric data obtained lets us discriminate glyphosate from the other studied compounds and a mathematical model has been built to quantify glyphosate concentrations in a buffer despite the presence of humic substances and ammonium nitrate. In this model, the coefficient of determination (R(2)) is 0.977 and the RMSEP value is 2.96 × 10(-5) so the model is considered statistically valid.

  16. Quantum mechanics and molecular dynamics simulations of complexation of alkaline-earth and lanthanide cations by poly-amino-carboxylate ligands; Simulations par mecanique quantique et dynamique moleculaire de la complexation de cations alcalino-terreux et lanthanides par des ligands polyaminocarboxylates

    Energy Technology Data Exchange (ETDEWEB)

    Durand, S

    1999-07-01

    Molecular dynamics (MD) simulations on lanthanide(III) and alkaline-earth(II) complexes with poly-amino-carboxylates (ethylene-diamino-tetra-acetate EDTA{sup 4-}, ethylene-diamino-tri-acetate-acetic acid EDTA(H){sup 3-}, tetra-aza-cyclo-dodecane-tetra-acetate DOTA{sup 4-}, methylene-imidine-acetate MIDA{sup 2-}) are reported. First, a consistent set of Lennard-Jones parameters for La{sup 3+}, Eu{sup 3+} and Lu{sup 3+} cations has been derived from free energy calculations in aqueous solution. Observed differences in hydration free energies, coordination distances and hydration numbers are reproduced. Then, the solution structures of 1:1 complexes of alkaline-earth and/or lanthanide cations with EDTA{sup 4-}, EDTA(H){sup 3-}, DOTA{sup 4-} and 1:2 complexes of lanthanide cations with MIDA{sup 2-} were studied by MD in water. In addition, free energy calculations were performed to study, for each ligand, the relative thermodynamic stabilities of complexes with Ca{sup 2+} vs Sr{sup 2+} and vs Ba{sup 2+} on the one hand, and with La{sup 3+} vs Eu{sup 3+} and vs Lu{sup 3+} on the other hand. Model does not take into account explicitly polarization and charge transfer. However, the results qualitatively agree with experimental complexation data (structure and selectivities). (author)

  17. Protein tyrosine nitration in cellular signal transduction pathways

    Science.gov (United States)

    Yakovlev, Vasily A.; Mikkelsen, Ross B.

    2015-01-01

    How specificity and reversibility in tyrosine nitration are defined biologically in cellular systems is poorly understood. As more investigations identify proteins involved in cell regulatory pathways in which only a small fraction of that protein pool is modified by nitration to affect cell function, the mechanisms of biological specificity and reversal should come into focus. In this review experimental evidence has been summarized to suggest that tyrosine nitration is a highly selective modification and under certain physiological conditions fulfills the criteria of a physiologically relevant signal. It can be specific, reversible, occurs on a physiological time scale, and, depending on a target, can result in either activation or inhibition. PMID:20843272

  18. Electrolytic Removal of Nitrate From CELSS Crop Residues

    Science.gov (United States)

    Colon, Guillermo; Sager, John

    1996-01-01

    The controlled ecological life support system (CELSS) resource recovery system is a waste processing system using aerobic and anaerobic bioreactors to recover plant nutrients and secondary foods from inedible biomass. Crop residues contain significant amounts of nitrate which presents two problems: (1) both CELSS biomass production and resource recovery consume large quantities of nitric acid, (2) nitrate causes a variety of problems in both aerobic and anaerobic bioreactors. A technique was proposed to remove the nitrate from potato inedible biomass leachate and to satisfy the nitric acid demand using a four compartment electrolytic cell.

  19. Soybean nitrate reductase activity influenced by manganese nutrition

    OpenAIRE

    Damien P., Heenan; Lindsay C., Campbell; Department of Agronomy and Horticultural Science, University of Sydney

    1980-01-01

    Nitrate assimilation by soybeans [Glycine max (L.) Merrill cvv. Lee and Bragg] was investigated in plants grown in solution culture at manganese concentrations of 0, 1.8 and 275 μM and at day-night temperatures of 33-28℃ and 22-17℃. Manganese deficiency occurred in plants of both cultivars grown at 0 μM Mn; under these conditions, leaf nitrate concentration increased in both cultivars and nitrate reductase activity in vivo but not in vitro was reduced. High solution Mn (275 μM) produced sympt...

  20. Nitrogen cycling in the Southern Ocean Kerguelen Plateau area: evidence for significant surface nitrification from nitrate isotopic compositions

    Science.gov (United States)

    Dehairs, F.; Fripiat, F.; Cavagna, A.-J.; Trull, T. W.; Fernandez, C.; Davies, D.; Roukaerts, A.; Fonseca Batista, D.; Planchon, F.; Elskens, M.

    2015-03-01

    This paper presents whole water column data for nitrate N, O isotopic composition for the Kerguelen Plateau area and the basin extending east of Heard Island, aiming at understanding the N-cycling in this naturally iron fertilized area that is characterized by large re-current phytoplankton blooms. The KEOPS 2 expedition (October-November 2011) took place in spring season and complements knowledge gathered during an earlier summer expedition to the same area (KEOPS 1, February-March 2005). As noted by others a remarkable condition of the system is the moderate consumption of nitrate over the season (nitrate remains >20 μM) while silicic acid becomes depleted, suggesting significant recycling of nitrogen. Nitrate isotopic signatures in the upper water column do mimic this condition, with surprising overlap of spring and summer regressions of δ18ONO3 vs. δ15NNO3 isotopic compositions. These regressions obey rather closely the 18ϵ/15ϵ discrimination expected for nitrate uptake (18ϵ/15ϵ = 1), but regression slopes as large as 1.6 were observed for the mixed layer above the Kerguelen Plateau. A preliminarily mass balance calculation for the early bloom period points toward significant nitrification occurring in the mixed layer and which may be equivalent to up to 47% of nitrate uptake above the Kerguelen Plateau. A further finding concerns deep ocean low δ18ONO3 values (Polar Front Zone and which cannot be explained by remineralization and nitrification of the local particulate nitrogen flux, which is too small in magnitude. However, the studied area is characterized by a complex recirculation pattern that would keep deep waters in the area and could impose a seasonally integrated signature of surface water processes on the deep waters.

  1. Fine structure characterization of zero-valent iron nanoparticles for decontamination of nitrites and nitrates in wastewater and groundwater

    Directory of Open Access Journals (Sweden)

    Kuen-Song Lin et al

    2008-01-01

    Full Text Available The main objectives of the present study were to investigate the chemical reduction of nitrate or nitrite species by zero-valent iron nanoparticle (ZVIN in aqueous solution and related reaction kinetics or mechanisms using fine structure characterization. This work also exemplifies the utilization of field emission-scanning electron microscope (FE–SEM, transmission electron microscopy (TEM, and x-ray diffraction (XRD to reveal the speciation and possible reaction pathway in a very complex adsorption and redox reaction process. Experimentally, ZVIN of this study was prepared by sodium borohydride reduction method at room temperature and ambient pressure. The morphology of as-synthesized ZVIN shows that the nearly ball and ultrafine particles ranged of 20–50 nm were observed with FE–SEM or TEM analysis. The kinetic model of nitrites or nitrates reductive reaction by ZVIN is proposed as a pseudo first-order kinetic equation. The nitrite and nitrate removal efficiencies using ZVIN were found 65–83% and 51–68%, respectively, based on three different initial concentrations. Based on the XRD pattern analyses, it is found that the quantitative relationship between nitrite and Fe(III or Fe(II is similar to the one between nitrate and Fe(III in the ZVIN study. The possible reason is due to the faster nitrite reduction by ZVIN. In fact, the occurrence of the relative faster nitrite reductive reaction suggested that the passivation of the ZVIN have a significant contribution to iron corrosion. The extended x-ray absorption fine structure (EXAFS or x-ray absorption near edge structure (XANES spectra show that the nitrites or nitrates reduce to N2 or NH3 while oxidizing the ZVIN to Fe2O3 or Fe3O4 electrochemically. It is also very clear that decontamination of nitrate or nitrite species in groundwater via the in-situ remediation with a ZVIN permeable reactive barrier would be environmentally attractive.

  2. Nitrogen cycling in the Southern Ocean Kerguelen Plateau area: evidence for significant surface nitrification from nitrate isotopic compositions

    Directory of Open Access Journals (Sweden)

    F. Dehairs

    2014-09-01

    Full Text Available This paper presents whole water column data for nitrate N, O isotopic composition for the Kerguelen Plateau area and the basin extending east of the island, aiming at understanding the N-cycling in this naturally iron fertilized area that is characterized by large re-current phytoplankton blooms. The KEOPS 2 expedition (October–November 2011 took place in spring season and complements knowledge gathered during an earlier summer expedition to the same area (KEOPS 1, February–March 2005. As noted by others a remarkable condition of the system is the moderate consumption of nitrate over the season (nitrate remains > 20 μM while silicic acid becomes depleted, suggesting significant recycling of nitrogen. Nitrate isotopic signatures in the upper water column do mimic this condition, with surprising overlap of spring and summer regressions of δ18ONO3 vs. δ15NNO3 isotopic compositions. These regressions obey rather closely the 18ϵ/15ϵ discrimination expected for nitrate uptake (18ϵ/15ϵ = 1, but regression slopes as large as 1.6 were observed for the mixed layer above the Kerguelen Plateau. A preliminary mass balance calculation for the early bloom period points toward significant nitrification occurring in the mixed layer and which could account for up to 80 % of nitrate uptake above the Kerguelen Plateau. A further finding concerns deep ocean low δ18ONO3 values (< 2‰ underlying high chlorophyll waters at the Polar Front Zone and which cannot be explained by remineralisation and nitrification of the local particulate nitrogen flux, which is too small in magnitude. However, the studied area is characterised by a complex recirculation pattern that would keep deep waters in the area and could impose a seasonally integrated signature of surface water processes on the deep waters.

  3. Trends in concentrations of nitrate and total dissolved solids in public supply wells of the Bunker Hill, Lytle, Rialto, and Colton groundwater subbasins, San Bernardino County, California: influence of legacy land use.

    Science.gov (United States)

    Kent, Robert; Landon, Matthew K

    2013-05-01

    Concentrations and temporal changes in concentrations of nitrate and total dissolved solids (TDS) in groundwater of the Bunker Hill, Lytle, Rialto, and Colton groundwater subbasins of the Upper Santa Ana Valley Groundwater Basin were evaluated to identify trends and factors that may be affecting trends. One hundred, thirty-one public-supply wells were selected for analysis based on the availability of data spanning at least 11 years between the late 1980s and the 2000s. Forty-one of the 131 wells (31%) had a significant (pwells (11%) had a significant decrease in nitrate. For TDS, 46 wells (35%) had a significant increase and 8 wells (6%) had a significant decrease. Slopes for the observed significant trends ranged from -0.44 to 0.91 mg/L/yr for nitrate (as N) and -8 to 13 mg/L/yr for TDS. Increasing nitrate trends were associated with greater well depth, higher percentage of agricultural land use, and being closer to the distal end of the flow system. Decreasing nitrate trends were associated with the occurrence of volatile organic compounds (VOCs); VOC occurrence decreases with increasing depth. The relations of nitrate trends to depth, lateral position, and VOCs imply that increasing nitrate concentrations are associated with nitrate loading from historical agricultural land use and that more recent urban land use is generally associated with lower nitrate concentrations and greater VOC occurrence. Increasing TDS trends were associated with relatively greater current nitrate concentrations and relatively greater amounts of urban land. Decreasing TDS trends were associated with relatively greater amounts of natural land use. Trends in TDS concentrations were not related to depth, lateral position, or VOC occurrence, reflecting more complex factors affecting TDS than nitrate in the study area.

  4. Luminescent properties of heterotrinuclear 3d-4f complexes constructed from a naphthalenediol-based acyclic bis(salamo)-type ligand

    Science.gov (United States)

    Dong, Wen-Kui; Zheng, Shan-Shan; Zhang, Jin-Tong; Zhang, Yang; Sun, Yin-Xia

    2017-09-01

    Heterotrinuclear 3d-4f complexes with a naphthalenediol-based acyclic bis(salamo)-type ligand have been synthesized and structurally characterized. Spectral titrations clearly show that the heterotrinuclear complexes [Zn2(L)La(OAc)3] (1), [Zn2(L)Ce(OAc)3] (2) and [Zn2(L)Dy(OAc)3(CH3OH)]·CH2Cl2 (3) are acquired by the substitution reaction of the obtained homotrinuclear Zn(II) complex with 1 equiv. of Ln(NO3)3 (Ln3 + = La3 +, Ce3 + and Dy3 +). Two Zn(II) ions are penta- and hexa-coordinated with geometries of distorted tetragonal pyramid and octahedron. La(III) ion is deca-coordinated, adopting a distorted bicapped square antiprism geometry. Ce(III) ion is nona-coordinated with geometry of distorted capped square antiprism as well as Dy(III) ion. The different coordination modes of acetate ions in complexes 1, 2 and 3 lead to different coordination numbers of the lanthanide(III) ions. Furthermore, the structures and fluorescence properties have been discussed.

  5. Impact of Vitamin B12 and Nitrate on Transcript and Metabolite Abundances in Marine Diatoms.

    Science.gov (United States)

    Pound, H. L.; Schanke, N. L.; Penta, W. B.; Zavala, J.; Casu, F.; Bearden, D. W.; Lee, P. A.

    2016-02-01

    Phytoplankton play countless roles in the support and regulation of marine ecosystems, as well as in global biogeochemical cycling processes. They are also, to varying extents, reliant on other physical and biological processes to supply their nutrient demands, such as the production of vitamin B12 by bacteria and archaea or the regeneration and upwelling of nitrate. One such process in the global biogeochemical sulfur cycle is the pathway that begins with the production of dimethylsulfoniopropionate (DMSP) by marine phytoplankton and leads to the atmospheric formation of sulfate-based cloud condensation nuclei, which contribute to the Earth's albedo. Nutrient limitation is thought to play a major role in the amount of DMSP produced by phytoplankton. Vitamin B12 and nitrate are of particular interest due to their involvement as a co-factor and nitrogen source, respectively, in the synthesis of methionine, the precursor for DMSP. Laboratory-based nutrient limitation experiments have been performed on cultures of the diatom Phaeodactylum tricornutum. In addition to the B12-dependent methionine synthase (MetH) P. tricornutum has a unique B12-independent methionine synthase gene (MetE). Based on classic techniques, B12 limitation had little impact on cell growth, whereas nitrate limitation had a significant effect on both culture health and DMSP concentration. Yet, targeted transcriptomic analysis (using Nanostring nCounter technology) and metabolomics analysis (using Nuclear Magnetic Resonance (NMR)) revealed complex changes in transcript abundance towards upregulated gene expression associated with the MetE gene in B12 limited cultures, and shifts away from nitrogen-based metabolites towards DMSP in nitrate-limited cultures. These experiments help verify the role of B12 in DMSP production and link the underlying metabolic pathways that drive the cellular portion of the sulfur cycle to ecosystem and global scale processes.

  6. Investigating nitrate dynamics in a fine-textured soil affected by feedlot effluents

    Science.gov (United States)

    Veizaga, E. A.; Rodríguez, L.; Ocampo, C. J.

    2016-10-01

    Feedlots concentrate large volumes of manure and effluents that contain high concentrations of nitrate, among other constituents. If not managed properly, pen surfaces run-off and lagoons overflows may spread those effluents to surrounding land, infiltrating into the soil. Soil nitrate mobilization and distribution are of great concern due to its potential migration towards groundwater resources. This work aimed at evaluating the migration of nitrate originated on feedlots effluents in a fine-textured soil under field conditions. Soil water constituents were measured during a three-year period at three distinct locations adjacent to feedlot retention lagoons representing different degrees of exposure to water flow and manure accumulation. A simple statistical analysis was undertaken to identify patterns of observed nitrate and chloride concentrations and electrical conductivity and their differences with depth. HYDRUS-1D was used to simulate water flow and solute transport of Cl-, NO4+sbnd N, NO3-sbnd N and electrical conductivity to complement field data interpretation. Results indicated that patterns of NO3-sbnd N concentrations were not only notoriously different from electrical conductivity and Cl- but also ranges and distribution with depth differed among locations. A combination of dilution, transport, reactions such as nitrification/denitrification and vegetation water and solute uptake took place at each plots denoting the complexity of soil-solution behavior under extreme polluting conditions. Simulations using the concept of single porosity-mobile/immobile water (SP-MIM) managed structural controls and correctly simulated -all species concentrations under field data constrains. The opposite was true for the other two locations experiencing near-saturation conditions, absence of vegetation and frequent manure accumulation and runoff from feedlot lagoons. Although the results are site specific, findings are relevant to advance the understanding of NO3-sbnd

  7. Inorganic nitrate promotes the browning of white adipose tissue through the nitrate-nitrite-nitric oxide pathway.

    Science.gov (United States)

    Roberts, Lee D; Ashmore, Tom; Kotwica, Aleksandra O; Murfitt, Steven A; Fernandez, Bernadette O; Feelisch, Martin; Murray, Andrew J; Griffin, Julian L

    2015-02-01

    Inorganic nitrate was once considered an oxidation end product of nitric oxide metabolism with little biological activity. However, recent studies have demonstrated that dietary nitrate can modulate mitochondrial function in man and is effective in reversing features of the metabolic syndrome in mice. Using a combined histological, metabolomics, and transcriptional and protein analysis approach, we mechanistically defined that nitrate not only increases the expression of thermogenic genes in brown adipose tissue but also induces the expression of brown adipocyte-specific genes and proteins in white adipose tissue, substantially increasing oxygen consumption and fatty acid β-oxidation in adipocytes. Nitrate induces these phenotypic changes through a mechanism distinct from known physiological small molecule activators of browning, the recently identified nitrate-nitrite-nitric oxide pathway. The nitrate-induced browning effect was enhanced in hypoxia, a serious comorbidity affecting white adipose tissue in obese individuals, and corrected impaired brown adipocyte-specific gene expression in white adipose tissue in a murine model of obesity. Because resulting beige/brite cells exhibit antiobesity and antidiabetic effects, nitrate may be an effective means of inducing the browning response in adipose tissue to treat the metabolic syndrome.

  8. The effect of peroxynitrite decomposition catalyst MnTBAP on aldehyde dehydrogenase-2 nitration by organic nitrates: role in nitrate tolerance.

    Science.gov (United States)

    Mollace, Vincenzo; Muscoli, Carolina; Dagostino, Concetta; Giancotti, Luigino Antonio; Gliozzi, Micaela; Sacco, Iolanda; Visalli, Valeria; Gratteri, Santo; Palma, Ernesto; Malara, Natalia; Musolino, Vincenzo; Carresi, Cristina; Muscoli, Saverio; Vitale, Cristiana; Salvemini, Daniela; Romeo, Francesco

    2014-11-01

    Bioconversion of glyceryl trinitrate (GTN) into nitric oxide (NO) by aldehyde dehydrogenase-2 (ALDH-2) is a crucial mechanism which drives vasodilatory and antiplatelet effect of organic nitrates in vitro and in vivo. Oxidative stress generated by overproduction of free radical species, mostly superoxide anions and NO-derived peroxynitrite, has been suggested to play a pivotal role in the development of nitrate tolerance, though the mechanism still remains unclear. Here we studied the free radical-dependent impairment of ALDH-2 in platelets as well as vascular tissues undergoing organic nitrate ester tolerance and potential benefit when using the selective peroxynitrite decomposition catalyst Mn(III) tetrakis (4-Benzoic acid) porphyrin (MnTBAP). Washed human platelets were made tolerant to nitrates via incubation with GTN for 4h. This was expressed by attenuation of platelet aggregation induced by thrombin (40U/mL), an effect accompanied by GTN-related induction of cGMP levels in platelets undergoing thrombin-induced aggregation. Both effects were associated to attenuated GTN-induced nitrite formation in platelets supernatants and to prominent nitration of ALDH-2, the GTN to NO metabolizing enzyme, suggesting that GTN tolerance was associated to reduced NO formation via impairment of ALDH-2. These effects were all antagonized by co-incubation of platelets with MnTBAP, which restored GTN-induced responses in tolerant platelets. Comparable effect was found under in in vivo settings. Indeed, MnTBAP (10mg/kg, i.p.) significantly restored the hypotensive effect of bolus injection of GTN in rats made tolerants to organic nitrates via chronic administration of isosorbide-5-mononitrate (IS-5-MN), thus confirming the role of peroxynitrite overproduction in the development of tolerance to vascular responses induced by organic nitrates. In conclusion, oxidative stress subsequent to prolonged use of organic nitrates, which occurs via nitration of ALDH-2, represents a key event

  9. Ammonium nitrate: a promising rocket propellant oxidizer

    Science.gov (United States)

    Oommen; Jain

    1999-06-30

    Ammonium nitrate (AN) is extensively used in the area of fertilizers and explosives. It is present as the major component in most industrial explosives. Its use as an oxidizer in the area of propellants, however, is not as extensive as in explosive compositions or gas generators. With the growing demand for environmental friendly chlorine free propellants, many attempts have been made of late to investigate oxidizers producing innocuous combustion products. AN, unlike the widely used ammonium perchlorate, produces completely ecofriendly smokeless products. Besides, it is one of the cheapest and easily available compounds. However, its use in large rocket motors is restricted due to some of its adverse characteristics like hygroscopicity, near room temperature phase transformation involving a volume change, and low burning rate (BR) and energetics. The review is an attempt to consolidate the information available on the various issues pertaining to its use as a solid propellant oxidizer. Detailed discussions on the aspects relating to phase modifications, decomposition chemistry, and BR and energetics of AN-based propellants, are presented. To make the review more comprehensive brief descriptions of the history, manufacture, safety, physical and chemical properties and various other applications of the salt are also included. Copyright 1999 Elsevier Science B.V.

  10. Nitration of Polystyrene Part-I Effect of Molecular Weight of Polymer on Nitration

    Directory of Open Access Journals (Sweden)

    I. Bajaj

    1967-01-01

    Full Text Available Polystyrene in the molecular weight range, 3.67*10/Sup4 to 47.86*10/Sup10 has been nitrated in fuming nitric acid at 50 Degree C and degree of substitution of nitro group per monomeric unit in the polymer chains varying from 1.03 to 1.11 has been obtained. Molecular weight of the initial polymers have been found no appreciable effect on the degree of substitution. Degradation of the polymer chain is, however, found to be more pronounced in high molecular weight polymers.

  11. Mechanisms of peroxynitrite-mediated nitration of tyrosine.

    Science.gov (United States)

    Gunaydin, Hakan; Houk, K N

    2009-05-01

    The mechanisms of tyrosine nitration by peroxynitrous acid or nitrosoperoxycarbonate were investigated with the CBS-QB3 method. Either the protonation of peroxynitrite or a reaction with carbon dioxide gives a reactive peroxide intermediate. Peroxynitrous acid-mediated nitration of phenol occurs via unimolecular decomposition to give nitrogen dioxide and hydroxyl radicals. Nitrosoperoxycarbonate also undergoes unimolecular decomposition to give carbonate and nitrogen dioxide radicals. The reactions of tyrosine with the hydroxyl or carbonate radicals give a phenoxy radical intermediate. The reaction of the nitrogen dioxide with this radical intermediate followed by tautomerization gives nitrated tyrosine in both cases. According to CBS-QB3 calculations, the rate-limiting step for the nitration of phenol is the decomposition of peroxynitrous acid or nitrosoperoxycarbonate.

  12. Biological nitrate removal using wheat straw and PLA as substrate.

    Science.gov (United States)

    Fan, Zhenxing; Hu, Jun; Wang, Jianlong

    2012-01-01

    Biological nitrate removal using wheat straw and polylactic acid (PLA) as both carbon source and biofilm support was investigated. The results showed that biofilm could develop on the surface of wheat straw within 15 d, the denitrification rate was 0.067 mg-N/(g-wheat straw x h) and nitrate removal efficiency was about 100%. For PLA, the time required for biofilm development was 40 d, the denitrification rate was 0.0026 mg-N/(g-PLA x h) and nitrate removal efficiency could also reach 100%. Temperature had a substantial influence on the denitrification performance of both wheat straw and PLA. The FTIR analysis and SEM observation confirmed that wheat straw and PLA were used for denitrification, and explained some reasons for the differences between the two substrates. The wheat straw was superior to PLA when used as carbon source for nitrate removal, in terms of the denitrification rate.

  13. Cyclic Voltammetric Responses of Nitrate Reductase on Chemical Modified Electrodes

    Institute of Scientific and Technical Information of China (English)

    YaRuSONG; HuiBoSHAO; 等

    2002-01-01

    Electrochemistry of nitrate reductases (NR) incorporated into 2-aminoethanethiol self-assembled on the gold electrode and polyacrylamide cast on the pyrolytic graphite electrode was examined. NR on chemical modified electrode showed electrochemical cyclic voltammetric responses in phosphate buffers.

  14. The optical properties of alkali nitrate single crystals

    Science.gov (United States)

    Anan'ev, Vladimir; Miklin, Mikhail

    2000-08-01

    Absorption of non-polarized light by a uniaxial crystal has been studied. The degree of absorption polarization has been calculated as a function of the ratio of optical densities in the region of low and high absorbances. This function is proposed for analysis of the qualitative and quantitative characteristics of uniaxial crystal absorption spectra. Non-polarized light spectra of alkali nitrate single crystals, both pure and doped with thallium, have been studied. It is shown that the absorption band at 300 nm is due to two transitions, whose intensities depend on temperature in various ways. There is a weak band in a short wavelength range of the absorption spectrum of potassium nitrate crystal, whose intensity increases with thallium doping. The band parameters of alkali nitrate single crystals have been calculated. Low-energy transitions in the nitrate ion have been located.

  15. Nitrate reducing activity pervades surface waters during upwelling.

    Digital Repository Service at National Institute of Oceanography (India)

    Fernandes, S.O.; Halarnekar, R.; Malik, A.; Vijayan, V.; Varik, S.; RituKumari; Jineesh V.K.; Gauns, M.U.; Nair, S.; LokaBharathi, P.A.

    Nitrate reducing activity (NRA) is known to be mediated by microaerophilic to anaerobic bacteria and generally occurs in the sub-surface waters. However, we hypothesize that NRA could become prominent in the surface waters during upwelling. Hence...

  16. Deprotection of oximes using urea nitrate under microwave irradiation

    Indian Academy of Sciences (India)

    P T Perumal; M Anniyappan; D Muralidharan

    2004-08-01

    A new mild and efficient method for the cleavage of oximes to carbonyl compounds using readily available urea nitrate in acetonitrile-water (95 : 5), under microwave irradiation within 2 min, in good yields is reported.

  17. Bis[4-chloro-N′-(2-pyridylmethylidenebenzohydrazidato]cobalt(III nitrate sesquihydrate

    Directory of Open Access Journals (Sweden)

    Genhua Wu

    2010-12-01

    Full Text Available In the title compound, [Co(C13H9ClN3O2]NO3·1.5H2O, the central Co3+ atom in the cation is coordinated by four N and two O atoms from the two tridentate ligands in a distorted octahedral fashion. In the crystal, the cobalt complex cations are linked to the half-occupied and the fully occupied water molecules, and the nitrate anion via classical intermolecular O—H...O and O—H...N hydrogen bonds and weak C—H...O contacts.

  18. Construction of Polynuclear Lanthanide (Ln = Dy(III), Tb(III), and Nd(III)) Cage Complexes Using Pyridine-Pyrazole-Based Ligands: Versatile Molecular Topologies and SMM Behavior.

    Science.gov (United States)

    Bala, Sukhen; Sen Bishwas, Mousumi; Pramanik, Bhaskar; Khanra, Sumit; Fromm, Katharina M; Poddar, Pankaj; Mondal, Raju

    2015-09-08

    Employment of two different pyridyl-pyrazolyl-based ligands afforded three octanuclear lanthanide(III) (Ln = Dy, Tb) cage compounds and one hexanuclear neodymium(III) coordination cage, exhibiting versatile molecular architectures including a butterfly core. Relatively less common semirigid pyridyl-pyrazolyl-based asymmetric ligand systems show an interesting trend of forming polynuclear lanthanide cage complexes with different coordination environments around the metal centers. It is noteworthy here that construction of lanthanide complex itself is a challenging task in a ligand system as soft N-donor rich as pyridyl-pyrazol. We report herein some lanthanide complexes using ligand containing only one or two O-donors compare to five N-coordinating sites. The resultant multinuclear lanthanide complexes show interesting magnetic and spectroscopic features originating from different spatial arrangements of the metal ions. Alternating current (ac) susceptibility measurements of the two dysprosium complexes display frequency- and temperature-dependent out-of-phase signals in zero and 0.5 T direct current field, a typical characteristic feature of single-molecule magnet (SMM) behavior, indicating different energy reversal barriers due to different molecular topologies. Another aspect of this work is the occurrence of the not-so-common SMM behavior of the terbium complex, further confirmed by ac susceptibility measurement.

  19. Nitrate leaching from short-hydroperiod floodplain soils

    Directory of Open Access Journals (Sweden)

    B. Huber

    2012-05-01

    Full Text Available Numerous studies have shown the importance of riparian zones to reduce nitrate (NO3 contamination coming from adjacent agricultural land. Much less is known about nitrogen (N transformations and nitrate fluxes in riparian soils with short hydroperiods (1–3 days of inundation and there is no study that could show whether these soils are a N sink or source.

    Within a restored section of the Thur River in NE Switzerland, we measured nitrate concentrations in soil solutions as an indicator of the net nitrate production. Samples were collected along a quasi-successional gradient from frequently inundated gravel bars to an alluvial forest, at three different depths (10, 50 and 100 cm over a one-year period. Along this gradient we quantified N input (atmospheric deposition and sedimentation and N output (leaching to create a nitrogen balance and assess the risk of nitrate leaching from the unsaturated soil to the groundwater.

    Overall, the main factor explaining the differences in nitrate concentrations was the variability in soil texture and volumetric water content (VWC at field capacity (FC. In subsoils with high VWC at FC and VWC near 100 % FC, high nitrate concentrations were observed, often exceeding the Swiss and EU groundwater quality criterions of 400 and 800 μmol l−1, respectively. High sedimentation rates of river-derived nitrogen led to apparent N retention up to 200 kg N ha−1 yr−1 in the frequently inundated zones. By contrast, in the mature alluvial forest, nitrate leaching exceeded total N input most of the time. As a result of the large soil N pools, high amounts of nitrate were produced by nitrification and up to 94 kg N-NO3 ha−1 yr−1 were leached into the groundwater. Thus, during flooding when water fluxes are high, nitrate from soils can contribute up to 11 % to the total nitrate load in groundwater.

  20. Nitrate leaching from short-hydroperiod floodplain soils

    Directory of Open Access Journals (Sweden)

    B. Huber

    2012-11-01

    Full Text Available Numerous studies have shown the importance of riparian zones to reduce nitrate (NO3 contamination coming from adjacent agricultural land. Much less is known about nitrogen (N transformations and nitrate fluxes in riparian soils with short hydroperiods (1–3 days of inundation and there is no study that could show whether these soils are a N sink or source. Within a restored section of the Thur River in NE Switzerland, we measured nitrate concentrations in soil solutions as an indicator of the net nitrate production. Samples were collected along a quasi-successional gradient from frequently inundated gravel bars to an alluvial forest, at three different depths (10, 50 and 100 cm over a one-year period. Along this gradient we quantified N input (atmospheric deposition and sedimentation and N output (leaching to create a nitrogen balance and assess the risk of nitrate leaching from the unsaturated soil to the groundwater. Overall, the main factor explaining the differences in nitrate concentrations was the field capacity (FC. In subsoils with high FCs and VWC near FC, high nitrate concentrations were observed, often exceeding the Swiss and EU groundwater quality criterions of 400 and 800 μmol L−1, respectively. High sedimentation rates of river-derived nitrogen led to apparent N retention up to 200 kg N ha−1 yr−1 in the frequently inundated zones. By contrast, in the mature alluvial forest, nitrate leaching exceeded total N input most of the time. As a result of the large soil N pools, high amounts of nitrate were produced by nitrification and up to 94 kg N-NO3 ha−1 yr−1 were leached into the groundwater. Thus, during flooding when water fluxes are high, nitrate from soils can contribute up to 11% to the total nitrate load in groundwater.