Sample records for hedta
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Senna, André M; Botaro, Vagner R
2017-08-28
To study the behavior of a biodegradable hydrogel derived from cellulose acetate and ethylenediaminetetraacetic dianhydride (EDTAD), as a reduction substrate of NPK fertilizer in soil. The biodegradable hydrogel (HEDTA) was prepared from cellulose acetate (CA) with a degree substitution (DS) 2.5 by esterification crosslinking with EDTAD catalyzed by triethylamine. We systematically investigated the performance of the HEDTA in the reducing NPK (Ammonium, phosphate and potassium) fertilizer leaching. We also compare the percentage of leaching between the HEDTA and commercial fertilizers. To characterize the esterification and crosslinking between CA and EDTAD, FTIR spectroscopy and thermogravimetric analysis (DTG) were employed. The biodegradation experiments were carried out in simulated soil (23% of sand, 23% of cattle manure, 23% of soil and 31% of water) and the HEDTA was tested in the eucalyptus planting during the dry season in the São Paulo state, Brazil. The HEDTA was able to reduce the leaching of fertilizers and improve the performance of eucalyptus seedlings and reduced the mortality of the seedlings. The HEDTA showed to be an excellent substrate for slow release and water-retention in soil, reducer of the fertilizers leaching, in addition being nontoxic, biodegradable in the soil and environmentally-friendly. Copyright © 2017 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Li, Xingliang; Zhang, Zhicheng; Martin, Leigh R
Complexation of Np(V) with N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) was studied in aqueous solution (I = 1.0 mol L -1 NaClO 4, t = 25 °C) by spectrophotometry, microcalorimetry and Extended X-ray absorption fine structure (EXAFS) spectroscopy. Equilibrium constants for the formation of three complexes, NpO 2L 2-, NpO 2(HL) -, and (NpO 2)2(OH)2L26 -, were determined to be (6.91 ± 0.06), (4.28 ± 0.03) and -(4.93 ± 0.03), respectively. The enthalpies of complexation were determined to be -(8.0 ± 2.0) kJ mol -1 for NpO 2L 2 - and -(2.2 ± 2.0) kJ mol-1 for NpO 2(HL) -. Thermodynamic data ofmore » the complexation of Np(V) with HEDTA were compared to those of Np(V) with other aminopolycarboxylic acids, gaining insight into the possible coordination modes of the complexes. The EXAFS studies provided further structural information on those modes. In both NpO 2L 2 - and NpO 2(HL) - complexes, HEDTA coordinates to Np(V) in a tridentate mode through two oxygens of two carboxylic groups and one nitrogen of the amine group. In the (NpO 2) 2(OH) 2L 2 6- complex, two Np(V) atoms are bridged by two hydroxides and each HEDTA maintains the tridentate coordination mode.« less
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Li, Xingliang; Zhang, Zhicheng; Martin, Leigh R; ...
2016-12-02
Complexation of Np(V) with N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) was studied in aqueous solution (I = 1.0 mol L -1 NaClO 4, t = 25 °C) by spectrophotometry, microcalorimetry and Extended X-ray absorption fine structure (EXAFS) spectroscopy. Equilibrium constants for the formation of three complexes, NpO 2L 2-, NpO 2(HL) -, and (NpO 2)2(OH)2L26 -, were determined to be (6.91 ± 0.06), (4.28 ± 0.03) and -(4.93 ± 0.03), respectively. The enthalpies of complexation were determined to be -(8.0 ± 2.0) kJ mol -1 for NpO 2L 2 - and -(2.2 ± 2.0) kJ mol-1 for NpO 2(HL) -. Thermodynamic data ofmore » the complexation of Np(V) with HEDTA were compared to those of Np(V) with other aminopolycarboxylic acids, gaining insight into the possible coordination modes of the complexes. The EXAFS studies provided further structural information on those modes. In both NpO 2L 2 - and NpO 2(HL) - complexes, HEDTA coordinates to Np(V) in a tridentate mode through two oxygens of two carboxylic groups and one nitrogen of the amine group. In the (NpO 2) 2(OH) 2L 2 6- complex, two Np(V) atoms are bridged by two hydroxides and each HEDTA maintains the tridentate coordination mode.« less
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METHOD OF SEPARATING RARE EARTHS BY ION EXCHANGE
Spedding, F.H.; Powell, J.E.
1960-10-18
A process is given for separating yttrium and rare earth values having atomic numbers of from 57 through 60 and 68 through 71 from an aqueous solution whose pH value can range from 1 to 9. All rare earths and yttrium are first adsorbed on a cation exchange resin, and they are then eluted with a solution of N-hydroxyethylethylenediaminetriacetic acid (HEDTA) in the order of decreasing atomic number, yttrium behaving like element 61; the effluents are collected in fractions. The HEDTA is recovered by elution with ammonia solution and the resin is regenerated with sulfuric acid. Rare earths are precipitated from the various effluents with oxalic acid, and each supernatant is passed over cation exchange resin for adsorption of HEDTA and nonprecipitated rare earths: the oxalic acid is not retained by the resin.
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Thermodynamic Studies to Support Actinide/Lanthanide Separations
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rao, Linfeng
2016-09-04
Thermodynamic data on the complexation of Np(V) with HEDTA in a wide pH region were re-modeled by including a dimeric complex species, (NpO 2) 2(OH) 2L 2 6- where L 3- stands for the fully deprotonated HEDTA ligand and better fits were achieved for the spectrophotometric data. The presence of the dimeric complex species in high pH region was verified for the first time by the EXAFS experiments at Stanford Synchrotron Radiation Laboratory (SSRL).
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Investigation of on-line chelant addition to PWR steam generators. Annual report, 1981
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tvedt, T.J.; Wallace, S.L.; Griffin, F. Jr.
1982-11-01
The thermostability of both ethylenediaminetetraacetic acid (EDTA) and hydroxyethylethylenediamininetriacetic acid (HEDTA) metal chelates in all volatile treatment water chemistry (AVT) was shown to be greater than or equal to thermostability of EDTA metal chelates in phosphate-sulfite water chemistry. HEDTA metal chelates were shown to have a much greater stability than EDTA metal chelates. Using samples taken from the EDTA metal chelate thermostability studies and samples from Commonwealth Research Corporation (CRC) model steam generators (MSG), EDTA decomposition products were determined. Active metal surfaces were shown to become passivated when exposed to EDTA and HEDTA concentrations as high as 0.1% w/w inmore » AVT. Trace amounts of iron in the water were found to increase the rate of passivation. Material balance and visual inspection data from CRC model steam generators showed that metal is being transported through and cleaning from the MSG's. EDTA metal chelates were removed from chelate solutions by passing the solutions over strong anion exchange resins.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Li, Xingliang; Zhang, Zhicheng; Endrizzi, Francesco
2015-06-01
The TALSPEAK process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Komplexes) has been demonstrated in several pilot-scale operations to be effective at separating trivalent actinides (An 3+) from trivalent lanthanides (Ln 3+). However, fundamental studies have revealed undesired aspects of TALSPEAK, such as the significant partitioning of Na +, lactic acid, and water into the organic phase, thermodynamically unpredictable pH dependence, and the slow extraction kinetics. In the modified TALSPEAK process, the combination of the aqueous holdback complexant HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid) with the extractant HEH[EHP] (2-ethyl(hexyl) phosphonic acid mono-2-ethylhexyl ester) in the organic phase has been found tomore » exhibit a nearly flat pH dependence between 2.5 and 4.5 and more rapid phase transfer kinetics for the heavier lanthanides. To help understand the speciation of Ln 3+ and An 3+ in the modified TALSPEAK, systematic studies are underway on the thermodynamics of major reactions in the HEDTA system under conditions relevant to the process (e.g., higher temperatures). Thermodynamics of the protonation and complexation of HEDTA with Ln 3+ were studied at variable temperatures. Equilibrium constants and enthalpies were determined by a combination of techniques including potentiometry and calorimetry. This paper presents the protonation constants of HEDTA at T = (25 to 70) °C. The potentiometric titrations have demonstrated that, stepwise, the first two protonation constants decrease and the third one slightly increases with the increase of temperature. This trend is in good agreement with the enthalpy of protonation directly determined by calorimetry. The results of NMR analysis further confirm that the first two protonation reactions occur on the diamine nitrogen atoms, while the third protonation reaction occurs on the oxygen of a carboxylate group. These data, in conjunction with the thermodynamic parameters of Ln 3+/An 3+ complexes with HEDTA at different temperatures, will help to predict the speciation and temperature-dependent behavior of Ln 3+/An 3+ in the modified TALSPEAK process.« less
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Critical current densities in superconducting Y-Ba-Cu-O prepared by chelating method
NASA Astrophysics Data System (ADS)
Fujisawa, Tadashi; Okuyama, Katsuro; Ohshima, Shigetoshi; Takagi, Akira
1990-10-01
The IDA, NTA, HEDTA, EDTA, TTHA, and DTPA chelating agents have been used to prepare the Y-Ba-Cu-O compounds whose critical current is presently investigated. It is noted that the precursor YBCO prepared from large stability-constant metal complexes (HEDTA, EDTA, DTPA, and TTHA) exhibited very fine and homogeneous particles. The critical current density of a 1 x 4 x 15 mm block of YBCO sintered at 880-910 C for 24 h and subsequently annealed at 500 C in an O2 flow was approximately 500 A/sq cm at 77 K, in zero magnetic field.
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Ion exchange purification of scandium
Herchenroeder, Laurie A.; Burkholder, Harvey R.
1990-10-23
An improvement in purification of scandium through ion exchange chromatography is disclosed in which the oxidation potential of the eluting solution is altered by the addition of potassium chlorate or ammonium chloride so that removal of contaminants is encouraged. The temperature, pH and concentration of the eluent HEDTA are controlled in order to maintain the scandium in the column while minimizing dilution of the scandium band. Recovery of scandium is improved by pumping dilute scandium over the column prior to stripping the scandium and precipitation. This eliminates the HEDTA ion and other monovalent cations contaminating the scandium band. This method maximizes recovery of scandium while maintaining purity.
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Ion exchange purification of scandium
Herchenroeder, L.A.; Burkholder, H.R.
1990-10-23
An improvement in purification of scandium through ion exchange chromatography is disclosed in which the oxidation potential of the eluting solution is altered by the addition of potassium chlorate or ammonium chloride so that removal of contaminants is encouraged. The temperature, pH and concentration of the eluent HEDTA are controlled in order to maintain the scandium in the column while minimizing dilution of the scandium band. Recovery of scandium is improved by pumping dilute scandium over the column prior to stripping the scandium and precipitation. This eliminates the HEDTA ion and other monovalent cations contaminating the scandium band. This method maximizes recovery of scandium while maintaining purity. 2 figs.
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Evaluation of on-line chelant addition to PWR steam generators. Steam generator cleaning project
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tvedt, T.J.; Wallace, S.L.; Griffin, F. Jr.
1983-09-01
The investigation of chelating agents for continuous water treatment of secondary loops of PWR steam generators were conducted in two general areas: the study of the chemistry of chelating agents and the study of materials compatability with chelating agents. The thermostability of both EDTA and HEDTA metal chelates in All Volatile Treatment (AVT) water chemistry were shown to be greater than or equal to the thermostability of EDTA metal chelates in phosphate-sulfite water chemistry. HEDTA metal chelates were shown to have a much greater stability than EDTA metal chelates. Using samples taken from the EDTA metal chelate thermostability study andmore » from the Commonwealth Research Corporation (CRC) model steam generators (MSG), EDTA decomposition products were determined. Active metal surfaces were shown to become passivated when exposed to EDTA and HEDTA concentrations as high as 0.1% w/w in AVT. Trace amounts of iron in the water were found to increase the rate of passivation. Material balance and visual inspection data from CRC model steam generators showed that metal was transported through and cleaned from the MSG's. The Inconel 600 tubes of the salt water fouled model steam generators experienced pitting corrosion. Results of this study demonstrates the feasibility of EDTA as an on-line water treatment additive to maintain nuclear steam generators in a clean condition.« less
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Iron chelates: a challenge to chemists and Mössbauer spectroscopists
NASA Astrophysics Data System (ADS)
Homonnay, Z.; Szilágyi, P. Á.; Vértes, A.; Kuzmann, E.; Sharma, V. K.; Molnár, G.; Bousseksou, A.; Grenèche, J.-M.; Brausam, A.; Meier, R.; van Eldik, R.
2008-02-01
The speciation of iron in aqueous solutions containing Fe3 + and selected chelates such as EDTA, EDDA, CDTA and HEDTA has been studied using transmission 57Fe Mössbauer spectrometry in frozen solutions. The protonation of various complexes as well as binuclear complex formation could be detected as a function of pH. Autoreduction of Fe3 + to Fe2 + was observed in several cases. Reaction with hydrogen peroxide proved to be rather different for the four ligands, while the dihapto complex [XFe( η 2-O2)]3 - had surprisingly identical Mössbauer parameters for X = EDTA, CDTA or HEDTA. Paramagnetic spin relaxation observed in the Mössbauer spectra was found to be strongly influenced by the identity of the chelating ligand, despite the basically spin-spin origin of the phenomenon.
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Beneficial effects of humic acid on micronutrient availability to wheat
NASA Technical Reports Server (NTRS)
Mackowiak, C. L.; Grossl, P. R.; Bugbee, B. G.
2001-01-01
Humic acid (HA) is a relatively stable product of organic matter decomposition and thus accumulates in environmental systems. Humic acid might benefit plant growth by chelating unavailable nutrients and buffering pH. We examined the effect of HA on growth and micronutrient uptake in wheat (Triticum aestivum L.) grown hydroponically. Four root-zone treatments were compared: (i) 25 micromoles synthetic chelate N-(4-hydroxyethyl)ethylenediaminetriacetic acid (C10H18N2O7) (HEDTA at 0.25 mM C); (ii) 25 micromoles synthetic chelate with 4-morpholineethanesulfonic acid (C6H13N4S) (MES at 5 mM C) pH buffer; (iii) HA at 1 mM C without synthetic chelate or buffer; and (iv) no synthetic chelate or buffer. Ample inorganic Fe (35 micromoles Fe3+) was supplied in all treatments. There was no statistically significant difference in total biomass or seed yield among treatments, but HA was effective at ameliorating the leaf interveinal chlorosis that occurred during early growth of the nonchelated treatment. Leaf-tissue Cu and Zn concentrations were lower in the HEDTA treatment relative to no chelate (NC), indicating HEDTA strongly complexed these nutrients, thus reducing their free ion activities and hence, bioavailability. Humic acid did not complex Zn as strongly and chemical equilibrium modeling supported these results. Titration tests indicated that HA was not an effective pH buffer at 1 mM C, and higher levels resulted in HA-Ca and HA-Mg flocculation in the nutrient solution.
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Synthesis and characterization of an N-(2-hydroxyethyl)-ethylenediaminetriacetic acid resin
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lai, Yuet Fan
1977-10-01
A chelating ion-exchange resin with N-(2-hydroxyethyl)ethylene-diaminetriacetic acid (HEDTA) used as the ligand chemically bonded to XAD-4 by an ester linkage, HEDTA-4, was synthesized. It is stable under normal experimental conditions with the liquid chromatograph. The structure of the resin was confirmed by an infrared spectrum, and by potentiometric titrations. The capacity of the resin was also obtained by potentiometric titration and by a nitrogen analysis. The resin was used to pack a column of 5 mm internal diameter and 5 cm long. The effect of pH on the retention of different metal ions on the resin was studied. It wasmore » found that the resin was most selective for chromium(III), copper(II), lead(II), mercury(II), uranium(VI), zirconium(IV) and zinc(II) at a pH of less than 3. Furthermore, the resin proves to be functioning with a chelating mechanism rather than ion-exchange, and it can concentrate trace metal ions in the presence of a large excess of calcium and magnesium. This makes the resin potentially useful for purifying and analyzing drinking water.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Lumetta, Gregg J.; Levitskaia, Tatiana G.; Wilden, Andreas
A system is being developed to separate trivalent actinides from lanthanide fission product elements that uses 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester to extract the lanthanide ions into an organic phase, while the actinide ions are held in the citrate-buffered aqueous phase by complexation to N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA). Earlier investigations of this system using a 2-cm centrifugal contactor revealed that the relatively slow extraction of Sm3+, Eu3+, and Gd3+ resulted in low separation factors from Am3+. In the work reported here, adjustments to the aqueous phase chemistry were made to improve the extraction rates. The results suggest that increasing the concentration ofmore » the citric acid buffer from 0.2 to 0.6 mol/L, and lowering the pH from 3.1 to 2.6, significantly improved lanthanide extraction rates resulting in an actinide/lanthanide separation system suitable for deployment in centrifugal contactors. Experiments performed to evaluate whether the lanthanide extraction rates can be improved by replacing aqueous HEDTA with nitrilotriacetic acid (NTA) exhibited promising results. However, NTA exhibited an unsatisfactorily high distribution value for Am3+ under the extraction conditions examined.« less
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Yang, Jiali; Liu, Junzhuo; Wu, Chenxi; Kerr, Philip G; Wong, Po-Keung; Wu, Yonghong
2016-12-01
The aim of this work was to study the bioremediation of agricultural solid waste leachates with high-concentrations of Cu (II) and Cd (II) after washing the wastes with water and Na 2 EDTA solution (0.2M). Results indicate that Cu (II) and Cd (II) are mainly comprised of Cu 2 (OH) 2 2+ , Cu 3 (OH) 4 2+ , CuOH + , Cu(H 2 O) 4 (OH) 2 , Cd 2+ and CdOH + in the water-washed leachates and Cu(EDTA) 2- , Cu(HEDTA) - , Cd(EDTA) 2- and Cd(HEDTA) - in the Na 2 EDTA-washed leachates. Cu (II) removal efficiency by selected native periphyton from the water- and Na 2 EDTA-washed leachates were 80.5% and 68.4% respectively, and for Cd (II) it was 57.1% and 64.6%, because the periphyton was able to maintain a stable pH of the leachates and regulate its microbial composition and carbon metabolic capability to acclimate the chemical conditions of the leachates. This study provides a new biomeasure to treat leachates with high-concentration Cu 2+ and Cd 2+ , and contribute valuable insights into the relationships between periphyton characteristics and heavy metals. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Brown, M. Alex; Wardle, Kent E.; Lumetta, Gregg; ...
2016-12-01
Here, the major components of the modified ALSEP process have been demonstrated on a modified 2-cm annular centrifugal contactor with an enhanced mixing zone using stable fission products and radiotracers. The results show that by decreasing the pH of the minor actinide stripping solution, using HEDTA instead of DTPA, and increasing contact time, the process is very effective in separating americium from the lanthanides and the fission products.
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Biogeochemistry of fluoride in a plant-solution system
NASA Technical Reports Server (NTRS)
Mackowiak, C. L.; Grossl, P. R.; Bugbee, B. G.
2003-01-01
Fluoride (F-) pollutants can harm plants and the animals feeding on them. However, it is largely unknown how complexing and chelating agents affect F bioavailability. Two studies were conducted that measured F- bioavailability and uptake by rice (Oryza sativa L.). In the first study, rice was grown in solution culture (pH 5.0) with 0, 2, or 4 mM F- as KF to compare the interaction of F- with humic acid (HA) and with a conventional chelating agent, N-hydroxyethylenthylenediaminetriacetic acid (HEDTA). In the second study, F was supplied at 0, 0.5, 1.0, and 2.0 mM KF with an additional 2 mM F- treatment containing solution Ca at 2x (2 mM Ca) the level used in the first study, to test the effect added Ca had on F- availability and uptake. Total biomass was greatest with HEDTA and F- < 1 mM. Leaf and stem F concentrations increased exponentially as solution F- increased linearly, with nearly no F partitioning into the seed. Results suggest that F was taken up as HF0 while F- uptake was likely restricted. Additionally, F- competed with HA for Ca, thus preventing the formation of Ca-HA flocculents. The addition of soluble Ca resulted in the precipitation of CaF2 solids on the root surface, as determined by tissue analysis and energy dispersive X-ray spectroscopy.
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Calculated and measured [Ca(2+)] in buffers used to calibrate Ca(2+) macroelectrodes.
McGuigan, John A S; Stumpff, Friederike
2013-05-01
The ionized concentration of calcium in physiological buffers ([Ca(2+)]) is normally calculated using either tabulated constants or software programs. To investigate the accuracy of such calculations, the [Ca(2+)] in EGTA [ethylene glycol-bis(β-aminoethylether)-N,N,N|,N|-tetraacetic acid], BAPTA [1,2-bis(o-aminophenoxy) ethane-N,N,N|,N|-tetraacetic acid], HEDTA [N-(2-hydroxyethyl)-ethylenediamine-N,N|,N|-triacetic acid], and NTA [N,N-bis(carboxymethyl)glycine] buffers was estimated using the ligand optimization method, and these measured values were compared with calculated values. All measurements overlapped in the pCa range of 3.51 (NTA) to 8.12 (EGTA). In all four buffer solutions, there was no correlation between measured and calculated values; the calculated values differed among themselves by factors varying from 1.3 (NTA) to 6.9 (EGTA). Independent measurements of EGTA purity and the apparent dissociation constants for HEDTA and NTA were not significantly different from the values estimated by the ligand optimization method, further substantiating the method. Using two calibration solutions of pCa 2.0 and 3.01 and seven buffers in the pCa range of 4.0-7.5, calibration of a Ca(2+) electrode over the pCa range of 2.0-7.5 became a routine procedure. It is proposed that such Ca(2+) calibration/buffer solutions be internationally defined and made commercially available to allow the precise measurement of [Ca(2+)] in biology. Copyright © 2013 Elsevier Inc. All rights reserved.
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Homogeneous and heterogenized iridium water oxidation catalysts
NASA Astrophysics Data System (ADS)
Macchioni, Alceo
2014-10-01
The development of an efficient catalyst for the oxidative splitting of water into molecular oxygen, protons and electrons is of key importance for producing solar fuels through artificial photosynthesis. We are facing the problem by means of a rational approach aimed at understanding how catalytic performance may be optimized by the knowledge of the reaction mechanism of water oxidation and the fate of the catalytic site under the inevitably harsh oxidative conditions. For the purposes of our study we selected iridium water oxidation catalysts, exhibiting remarkable performance (TOF > 5 s-1 and TON > 20000). In particular, we recently focused our attention on [Cp*Ir(N,O)X] (N,O = 2-pyridincarboxylate; X = Cl or NO3) and [IrCl(Hedta)]Na water oxidation catalysts. The former exhibited a remarkable TOF whereas the latter showed a very high TON. Furthermore, [IrCl(Hedta)]Na was heterogenized onto TiO2 taking advantage of the presence of a dandling -COOH functionality. The heterogenized catalyst maintained approximately the same catalytic activity of the homogeneous analogous with the advantage that could be reused many times. Mechanistic studies were performed in order to shed some light on the rate-determining step and the transformation of catalysts when exposed to "oxidative stress". It was found that the last oxidative step, preceding oxygen liberation, is the rate-determining step when a small excess of sacrificial oxidant is used. In addition, several intermediates of the oxidative transformation of the catalyst were intercepted and characterized by NMR, X-Ray diffractometry and ESI-MS.
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Minutes of the Tank Waste Science Panel Meeting March 25--27, 1992. Hanford Tank Safety Project
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schutz, W W; Consultant, Wellington, Delaware; Strachan, D M
Discussions from the seventh meeting of the Tank Waste Science are presented in Colorado. The subject areas included the generation of gases in Tank 241-SY-101, the possible use of sonication as a mitigation method, and analysis for organic constituents in core samples. Results presented and discussed include: Ferrocyanides appear to be rapidly dissolved in 1M NaOH; upon standing in the laboratory at ambient conditions oxalate precipitates from simulated wastes containing HEDTA. This suggests that one of the main components in the solids in Tank 241-SY-101 is oxalate; hydrogen evolved from waste samples from Tank 241-SY-101 is five times that observedmore » in the off gas from the tank; data suggest that mitigation of Tank 241-SY-101 will not cause a high release of dissolved N{sub 2}O; when using a slurry for radiation studies, a portion of the generated gases is very difficult to remove. To totally recover the generated gases, the solids must first be dissolved. This result may have an impact on mitigation by mixing if the gases are not released. Using {sup 13}C-labeled organics in thermal degradation studies has allowed researchers to illucidate much of the kinetic mechanism for the degradation of HEDTA and glycolate. In addition to some of the intermediate, more complex organic species, oxalate, formate, and CO{sub 2} were identified; and analytic methods for organics in radioactive complex solutions such as that found in Tank 241-SY-101 have been developed and others continue to be developed.« less
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Alvarez-Fernández, Ana; Orera, Irene; Abadía, Javier; Abadía, Anunciación
2007-01-01
A high-performance liquid chromatography-electrospray ionization/mass spectrometry (time of flight) method has been developed for the simultaneous determination of synthetic Fe(III)-chelates used as fertilizers. Analytes included the seven major Fe(III)-chelates used in agriculture, Fe(III)-EDTA, Fe(III)-DTPA, Fe(III)-HEDTA, Fe(III)-CDTA, Fe(III)-o,oEDDHA, Fe(III)-o,pEDDHA, and Fe(III)-EDDHMA, and the method was validated using isotope labeled (57)Fe(III)-chelates as internal standards. Calibration curves had R values in the range 0.9962-0.9997. Limits of detection and quantification were in the ranges 3-164 and 14-945 pmol, respectively. Analyte concentrations could be determined between the limits of quantification and 25 muM (racemic and meso Fe(III)-o,oEDDHA and Fe(III)-EDDHMA) or 50 muM (Fe(III)-EDTA, Fe(III)-HEDTA, Fe(III)-DTPA, Fe(III)-CDTA and Fe(III)-o,pEDDHA). The average intraday repeatability values were approximately 0.5 and 5% for retention time and peak area, respectively, whereas the interday repeatability values were approximately 0.7 and 8% for retention time and peak area, respectively. The method was validated using four different agricultural matrices, including nutrient solution, irrigation water, soil solution, and plant xylem exudates, spiked with Fe(III)-chelate standards and their stable isotope-labeled corresponding chelates. Analyte recoveries found were in the ranges 92-101% (nutrient solution), 89-102% (irrigation water), 82-100% (soil solution), and 70-111% (plant xylem exudates). Recoveries depended on the analyte, with Fe(III)-EDTA and Fe(III)-DTPA showing the lowest recoveries (average values of 87 and 88%, respectively, for all agricultural matrices used), whereas for other analytes recoveries were between 91 and 101%. The method was also used to determine the real concentrations of Fe(III)-chelates in commercial fertilizers. Furthermore, the method is also capable of resolving two more synthetic Fe(III)-chelates, Fe(III)-EDDHSA and Fe(III)-EDDCHA, whose exact quantification is not currently possible because of lack of commercial standards.
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Nguyen, Nguyen Cong; Nguyen, Hau Thi; Chen, Shiao-Shing; Ngo, Huu Hao; Guo, Wenshan; Chan, Wen Hao; Ray, Saikat Sinha; Li, Chi-Wang; Hsu, Hung-Te
2016-06-01
A novel approach was designed to simultaneously enhance nutrient removal and reduce membrane fouling for wastewater treatment using an attached growth biofilm (AGB) integrated with an osmosis membrane bioreactor (OsMBR) system for the first time. In this study, a highly charged organic compound (HEDTA(3-)) was employed as a novel draw solution in the AGB-OsMBR system to obtain a low reverse salt flux, maintain a healthy environment for the microorganisms. The AGB-OsMBR system achieved a stable water flux of 3.62L/m(2)h, high nutrient removal of 99% and less fouling during a 60-day operation. Furthermore, the high salinity of diluted draw solution could be effectively recovered by membrane distillation (MD) process with salt rejection of 99.7%. The diluted draw solution was re-concentrated to its initial status (56.1mS/cm) at recovery of 9.8% after 6h. The work demonstrated that novel multi-barrier systems could produce high quality potable water from impaired streams. Copyright © 2016. Published by Elsevier Ltd.
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Mercury removal in utility wet scrubber using a chelating agent
Amrhein, Gerald T.
2001-01-01
A method for capturing and reducing the mercury content of an industrial flue gas such as that produced in the combustion of a fossil fuel or solid waste adds a chelating agent, such as ethylenediaminetetraacetic acid (EDTA) or other similar compounds like HEDTA, DTPA and/or NTA, to the flue gas being scrubbed in a wet scrubber used in the industrial process. The chelating agent prevents the reduction of oxidized mercury to elemental mercury, thereby increasing the mercury removal efficiency of the wet scrubber. Exemplary tests on inlet and outlet mercury concentration in an industrial flue gas were performed without and with EDTA addition. Without EDTA, mercury removal totaled 42%. With EDTA, mercury removal increased to 71%. The invention may be readily adapted to known wet scrubber systems and it specifically provides for the removal of unwanted mercury both by supplying S.sup.2- ions to convert Hg.sup.2+ ions into mercuric sulfide (HgS) and by supplying a chelating agent to sequester other ions, including but not limited to Fe.sup.2+ ions, which could otherwise induce the unwanted reduction of Hg.sup.2+ to the form, Hg.sup.0.
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Mixed monofunctional extractants for trivalent actinide/lanthanide separations: TALSPEAK-MME
DOE Office of Scientific and Technical Information (OSTI.GOV)
Johnson, Aaron T.; Nash, Kenneth L.
The basic features of an f-element extraction process based on a solvent composed of equimolar mixtures of Cyanex-923 (a mixed trialkyl phosphine oxide) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) extractants in n-dodecane are investigated in this report. This system, which combines features of the TRPO and TALSPEAK processes, is based on co-extraction of trivalent lanthanides and actinides from 0.1 to 1.0 M HNO 3 followed by application of a buffered aminopolycarboxylate solution strip to accomplish a Reverse TALSPEAK selective removal of actinides. This mixed-extractant medium could enable a simplified approach to selective trivalent f-element extraction and actinide partitioning in amore » single process. As compared with other combined process applications in development for more compact actinide partitioning processes (DIAMEX-SANEX, GANEX, TRUSPEAK, ALSEP), this combination features only monofunctional extractants with high solubility limits and comparatively low molar mass. Selective actinide stripping from the loaded extractant phase is done using a glycine-buffered solution containing N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) or triethylenetetramine-N,N,N',N'',N''',N'''-hexaacetic acid (TTHA). Lastly, the results reported provide evidence for simplified interactions between the two extractants and demonstrate a pathway toward using mixed monofunctional extractants to separate trivalent actinides (An) from fission product lanthanides (Ln).« less
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Immobilization of Fe chelators on sepharose gel and its effect on their chemical properties.
Yehuda, Zehava; Hadar, Yitzhak; Chen, Yona
2003-09-24
Iron chelates are usually costly and easily leached beyond the root zone. This creates a need to frequently replenish the rhizosphere with chelated Fe and might contaminate groundwater with organic compounds and metals. The development of a slow-release Fe fertilizer that will efficiently supply Fe to plants while exhibiting high resistance toward leaching and/or degradation in the rhizosphere has been the focus of this study. Desferrioxamine B (DFOB) and ethylenediaminebis(o-hydroxyphenylacetic acid) (EDDHA) were immobilized on Sepharose. (13)C NMR and FTIR measurements confirmed that coupling of DFOB to the gel did not appear to influence its ability to chelate Fe(3+) or its binding nature. Isotherms for the immobilized ligands were determined in the presence of 1 mM HEDTA, at 25 degrees C and at an ionic strength of 0.1 M. The isotherms showed a high affinity of Fe(3+) to the ligands and binding up to saturation level throughout the pH range examined (4.0-9.0). The K(app) values for the immobilized Fe chelates were determined using a modified Scatchard model and found to be lower than the soluble ones. This decrease in K(app) might facilitate Fe uptake from these chelates by plants.
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Mixed monofunctional extractants for trivalent actinide/lanthanide separations: TALSPEAK-MME
Johnson, Aaron T.; Nash, Kenneth L.
2015-08-20
The basic features of an f-element extraction process based on a solvent composed of equimolar mixtures of Cyanex-923 (a mixed trialkyl phosphine oxide) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) extractants in n-dodecane are investigated in this report. This system, which combines features of the TRPO and TALSPEAK processes, is based on co-extraction of trivalent lanthanides and actinides from 0.1 to 1.0 M HNO 3 followed by application of a buffered aminopolycarboxylate solution strip to accomplish a Reverse TALSPEAK selective removal of actinides. This mixed-extractant medium could enable a simplified approach to selective trivalent f-element extraction and actinide partitioning in amore » single process. As compared with other combined process applications in development for more compact actinide partitioning processes (DIAMEX-SANEX, GANEX, TRUSPEAK, ALSEP), this combination features only monofunctional extractants with high solubility limits and comparatively low molar mass. Selective actinide stripping from the loaded extractant phase is done using a glycine-buffered solution containing N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) or triethylenetetramine-N,N,N',N'',N''',N'''-hexaacetic acid (TTHA). Lastly, the results reported provide evidence for simplified interactions between the two extractants and demonstrate a pathway toward using mixed monofunctional extractants to separate trivalent actinides (An) from fission product lanthanides (Ln).« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa
Potentiometric and spectroscopic techniques were combined with DFT calculations to probe the coordination environment and determine thermodynamic features of trivalent f-element complexation by N-hydroxyethyl-diethylenetriamine-N,N',N",N"-tetraacetic acid, HEDTTA. Ligand protonation constants and lanthanide stability constants were determined using potentiometry. Five protonation constants were accessible in I = 2.0 M (H +/Na +)ClO 4. UV–vis spectroscopy was used to determine stability constants for Nd 3+ and Am 3+ complexation with HEDTTA. Luminescence spectroscopy indicates two water molecules in the inner coordination sphere of the Eu/HEDTTA complex, suggesting HEDTTA is heptadentate. Luminescence data was supported by DFT calculations, which demonstrate that substitution of themore » acetate pendant arm by a N-hydroxyethyl group weakens the metal–nitrogen bond. This bond elongation is reflected in HEDTTA’s ability to differentiate trivalent actinides from trivalent lanthanides. The trans-lanthanide Ln/HEDTTA complex stability trend is analogous to Ln/DTPA complexation; however, the loss of one chelate ring resulting from structural substitution weakens the complexation by ~3 orders of magnitude. Successful separation of trivalent americium from trivalent lanthanides was demonstrated when HEDTTA was utilized as aqueous holdback complexant in a liquid–liquid system. Time-dependent extraction studies for HEDTTA were compared to diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA) and N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid (HEDTA). The results presented here indicate substantially enhanced phase-transfer kinetic rates for mixtures containing HEDTTA.« less
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Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa; ...
2017-01-24
Potentiometric and spectroscopic techniques were combined with DFT calculations to probe the coordination environment and determine thermodynamic features of trivalent f-element complexation by N-hydroxyethyl-diethylenetriamine-N,N',N",N"-tetraacetic acid, HEDTTA. Ligand protonation constants and lanthanide stability constants were determined using potentiometry. Five protonation constants were accessible in I = 2.0 M (H +/Na +)ClO 4. UV–vis spectroscopy was used to determine stability constants for Nd 3+ and Am 3+ complexation with HEDTTA. Luminescence spectroscopy indicates two water molecules in the inner coordination sphere of the Eu/HEDTTA complex, suggesting HEDTTA is heptadentate. Luminescence data was supported by DFT calculations, which demonstrate that substitution of themore » acetate pendant arm by a N-hydroxyethyl group weakens the metal–nitrogen bond. This bond elongation is reflected in HEDTTA’s ability to differentiate trivalent actinides from trivalent lanthanides. The trans-lanthanide Ln/HEDTTA complex stability trend is analogous to Ln/DTPA complexation; however, the loss of one chelate ring resulting from structural substitution weakens the complexation by ~3 orders of magnitude. Successful separation of trivalent americium from trivalent lanthanides was demonstrated when HEDTTA was utilized as aqueous holdback complexant in a liquid–liquid system. Time-dependent extraction studies for HEDTTA were compared to diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA) and N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid (HEDTA). The results presented here indicate substantially enhanced phase-transfer kinetic rates for mixtures containing HEDTTA.« less
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Aihara, Eitaro; Hentz, Courtney L.; Korman, Abraham M.; Perry, Nicholas P. J.; Prasad, Vikram; Shull, Gary E.; Montrose, Marshall H.
2013-01-01
We report that a localized intracellular and extracellular Ca2+ mobilization occurs at the site of microscopic epithelial damage in vivo and is required to mediate tissue repair. Intravital confocal/two-photon microscopy continuously imaged the surgically exposed stomach mucosa of anesthetized mice while photodamage of gastric epithelial surface cells created a microscopic lesion that healed within 15 min. Transgenic mice with an intracellular Ca2+-sensitive protein (yellow cameleon 3.0) report that intracellular Ca2+ selectively increases in restituting gastric epithelial cells adjacent to the damaged cells. Pretreatment with U-73122, indomethacin, 2-aminoethoxydiphenylborane, or verapamil inhibits repair of the damage and also inhibits the intracellular Ca2+ increase. Confocal imaging of Fura-Red dye in luminal superfusate shows a localized extracellular Ca2+ increase at the gastric surface adjacent to the damage that temporally follows intracellular Ca2+ mobilization. Indomethacin and verapamil also inhibit the luminal Ca2+ increase. Intracellular Ca2+ chelation (1,2-bis(o-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid/acetoxymethyl ester, BAPTA/AM) fully inhibits intracellular and luminal Ca2+ increases, whereas luminal calcium chelation (N-(2-hydroxyetheyl)-ethylendiamin-N,N,N′-triacetic acid trisodium, HEDTA) blocks the increase of luminal Ca2+ and unevenly inhibits late-phase intracellular Ca2+ mobilization. Both modes of Ca2+ chelation slow gastric repair. In plasma membrane Ca-ATPase 1+/− mice, but not plasma membrane Ca-ATPase 4−/− mice, there is slowed epithelial repair and a diminished gastric surface Ca2+ increase. We conclude that endogenous Ca2+, mobilized by signaling pathways and transmembrane Ca2+ transport, causes increased Ca2+ levels at the epithelial damage site that are essential to gastric epithelial cell restitution in vivo. PMID:24121509
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Aihara, Eitaro; Hentz, Courtney L; Korman, Abraham M; Perry, Nicholas P J; Prasad, Vikram; Shull, Gary E; Montrose, Marshall H
2013-11-22
We report that a localized intracellular and extracellular Ca(2+) mobilization occurs at the site of microscopic epithelial damage in vivo and is required to mediate tissue repair. Intravital confocal/two-photon microscopy continuously imaged the surgically exposed stomach mucosa of anesthetized mice while photodamage of gastric epithelial surface cells created a microscopic lesion that healed within 15 min. Transgenic mice with an intracellular Ca(2+)-sensitive protein (yellow cameleon 3.0) report that intracellular Ca(2+) selectively increases in restituting gastric epithelial cells adjacent to the damaged cells. Pretreatment with U-73122, indomethacin, 2-aminoethoxydiphenylborane, or verapamil inhibits repair of the damage and also inhibits the intracellular Ca(2+) increase. Confocal imaging of Fura-Red dye in luminal superfusate shows a localized extracellular Ca(2+) increase at the gastric surface adjacent to the damage that temporally follows intracellular Ca(2+) mobilization. Indomethacin and verapamil also inhibit the luminal Ca(2+) increase. Intracellular Ca(2+) chelation (1,2-bis(o-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid/acetoxymethyl ester, BAPTA/AM) fully inhibits intracellular and luminal Ca(2+) increases, whereas luminal calcium chelation (N-(2-hydroxyetheyl)-ethylendiamin-N,N,N'-triacetic acid trisodium, HEDTA) blocks the increase of luminal Ca(2+) and unevenly inhibits late-phase intracellular Ca(2+) mobilization. Both modes of Ca(2+) chelation slow gastric repair. In plasma membrane Ca-ATPase 1(+/-) mice, but not plasma membrane Ca-ATPase 4(-/-) mice, there is slowed epithelial repair and a diminished gastric surface Ca(2+) increase. We conclude that endogenous Ca(2+), mobilized by signaling pathways and transmembrane Ca(2+) transport, causes increased Ca(2+) levels at the epithelial damage site that are essential to gastric epithelial cell restitution in vivo.
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Evaluate the role of organic acids in the protection of ligands from radiolytic degradation
DOE Office of Scientific and Technical Information (OSTI.GOV)
Miller, Anneka; Mezyk, Stehpen; Peterman, Dean
In the Advanced TALSPEAK process, the bis(2-ethylhexyl)phosphoric acid (HDEHP) extractant used in the traditional TALSPEAK process is replaced by the extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). In addition, the aqueous phase complexant and buffer used in traditional TALSPEAK is replaced with the combination of N-(2-hydroxyethyl)ethylenediamine-N,N’,N’-triacetic acid (HEDTA) and citric acid. In order to evaluate the possible impacts of gamma radiolysis upon the efficacy of the Advanced TALSPEAK flowsheet, aqueous and organic phases corresponding to the extraction section of the proposed flowsheet were irradiated in the INL test loop under an ambient atmosphere. The results of these studies conducted at INL,more » led INL researchers to conclude that the scarcity of values of rate constants for the reaction of hydroxyl radical with the components of the Advanced TALSPEAK process chemistry was severely limiting the interpretation of the results of radiolysis studies performed at the INL. In this work, the rate of reaction of hydroxyl radical with citric acid at several pH values was measured using a competitive pulse radiolysis technique. This report describes those results and is written in completion of milestone M3FT-16IN030102028, the goal of which was to evaluate the role of organic acids in the protection of ligands from radiolytic degradation. The results reported here demonstrate the importance of obtaining hydroxyl radical reaction rate data for the conditions that closely resemble actual solution conditions expected to be used in an actual solvent extraction process. This report describes those results and is written in completion of milestone M3FT-16IN030102028, the goal of which was to evaluate the role of organic acids in the protection of ligands from radiolytic degradation.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Shepherd, R.E.; Myser, T.K.; Elliott, M.G.
The kinetics of the reaction of O/sub 2/ and Fe/sub 2/(ttha)/sup 2/minus// (ttha/sup 6/minus// = triethylenetetraminehexaacetate) are reported. The mechanism of oxidation is discussed in terms of the equilibrium binding of O/sub 2/ forming an ((Fe/sup III/O/sub 2//sup /minus//)ttha(Fe/sup II/)) intermediate in an open-chain configuration. When Fe/sub 2/(ttha)/sup 2/minus// is oxidized by H/sub 2/O/sub 2/, the HODMPO/sup /center dot// (DMPO = 5,5-dimethyl-1-pyrrolis-N-oxide) adduct is readily detected by its characteristic four-line 1:2:2:1 pattern (a/sub N/ = a/sub H/ = 15.0 G) in its ESR spectrum. The bound O/sub 2//sup /minus// intermediate in the Fe/sub 2/(ttha)/sup 2/minus// autoxidation scheme will extract anmore » H atom from C/sub 2/H/sub 5/OH in its solvent cage; the DMPO adduct of CH/sub 3/CHOH is trapped, giving a pattern of six equal lines (a/sub N/ = 16.0 G, a/sub H/ = 22.8 G). A maximum of 6% of the pathway results in a carbon-centered radial; the remainder of the reduction events produce Fe/sub 2/O(ttha)/sup 2/minus// by rapid reduction of the (Fe/sup III//sub 2/(O/sub 2//sup 2/minus//)(ttha))/sup 2/minus// intermediate. The Fe/sub 2/O(ttha)/sup 2/minus// ion was precipitated as its Me/sub 2/Dabco/sup 2+/ salt. This compound was shown to have ferric ions in an /sup 6/A/sub 1/ state; the Moessbauer spectrum yielded 0.63 mm/s for the isomer shift and 1.56 mm/s for the quadrupole splitting parameter vs sodium nitroprusside. The solid exhibited an Fe-O-Fe asymmetric stretch at 833 cm/sup /minus/1/ for /sup 16/O and 846 cm/sup /minus/1/ for the /sup 18/O-labeled complex. The uv-visible spectrum is very similar to that of the Fe/sub 2/(hedta)/sub 2//sup 2/minus// complex. 62 references, 7 figures, 3 tables.« less