Determination of synthetic ferric chelates used as fertilizers by liquid chromatography-electrospray/mass spectrometry in agricultural matrices

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.     

Effect of oxygen content on the 29Si NMR, Raman spectra and oxide ion conductivity of the apatite series, La8+xSr2-x(SiO4)6O2+x/2

29Si NMR data have been recorded for the apatite series La8+xSr2-x(SiO4)6O2+x/2 (0 < or = x < or = 1.0). For x = 0, a single NMR peak is observed at a chemical shift of approximately -77 ppm, while as the La : Sr ratio and hence interstitial oxygen content is increased, a second peak at a chemical shift of approximately -80 ppm is observed, which has been attributed to silicate groups neighbouring interstitial oxide ions. An increase in the intensity of this second peak is observed with increasing x, consistent with an increase in interstitial oxide ion content, and the data are used to estimate the level of interstitial oxide ions, and hence Frenkel-type disorder in these materials. The increase in second 29Si NMR peak intensity/interstitial oxide ion content is also shown to correlate with an increase in conductivity. The effect of interstitial oxygen content can also be studied by means of Raman spectroscopy, with a new mode at 360 cm(-1) appearing for samples with x > 0 in the symmetric bending mode energy region of the SiO4 group. The intensity of this mode increases with increasing oxygen content, yielding results comparable to those from the NMR studies, showing the complementarities of the two techniques.     

Insight into the local structure of barium indate oxide-ion conductors: an X-ray total scattering study

In this paper we presented the X-ray PDF investigation of orthorhombic Ba(2)In(2)O(5) and cubic Ba(2)In(1.7)P(0.3)O(5.3) and Ba(2)In(1.7)S(0.3)O(5.45) samples. Pure Ba(2)In(2)O(5) was found to be properly described-at the local scale-by the orthorhombic average structure. Ba(2)In(1.7)P(0.3)O(5.3) and Ba(2)In(1.7)S(0.3)O(5.45) cannot be described, at the local scale, by a cubic symmetry. The PDFs of these two samples clearly showed a distorted atom arrangement in the short-range which can be described again with the orthorhombic symmetry found in pure barium indate.     

EPR study of the [H−Ca+]0 defect in Tcr CaO

Abstract

A new hydrogen related low-temperature trap for the electrons released during the photoconversion of F→F⁺ centers is studied by EPR. The defects are stable up to 80 K. Below 20 K the spectrum corresponds to the static situation showing tetragonal symmetry. Above this temperature the spectrum is isotropic a consequence of the hopping among the six equivalent orientations. A model for the defect and the study of its reorientational motion are given.     

Electron and hole trapped defects produced by thermoreduction or irradiation in Stabilized Zirconia

Abstract

When undoped Yttrium Stabilized Zirconia is exposed either to reducing atmospheres or to electrical currents it becomes coloured. In this paper we present the results of a systematic study applying optical and EPR techniques to zirconia single crystals stabilized by calcium or yttrium, in which defects were produced by several methods including X-irradiation or reduction at different temperatures. Two EPR signals and three absorption bands have been related with three defects involving holes trapped in oxygen ions and electrons trapped in zirconium ions. The photothermal stability of the defects has been studied. Taking into account their spectroscopical properties and statistical considerations we propose novel models for these defects.     

Near infrared to visible upconversion of Er in CaZrO3/CaSZ eutectic crystals with ordered lamellar microstructure

In this work we report the near infrared to visible upconversion luminescence of Er³⁺ ions in CaZrO₃/CaSZ eutectic crystals with ordered lamellar microstructure. The microstructure consists of alternating 2-μm-thick lamellae of calcia-stabilized zirconia (CaSZ) and calcium zirconate (CaZrO₃) single crystals. Er³⁺ ions enter both phases but at a higher concentration in CaSZ. Wavelength selective excitation along the ⁴I_15/2→⁴I_9/2 absorption band allows to distinguish the upconverted emission from Er³⁺ sites in the two eutectic phases. In the CaZrO₃ phase the upconversion emission spectrum is dominated by an intense green emission characterized by sharp (²H_11/2,⁴S_3/2) levels together with a more weak red emission from ⁴F_9/2 level. In the CaSZ phase, a broad green and red emissions occur with an enhancement of the red emission from level ⁴F_9/2. These upconverted emissions are attributed to a two photon process. The excitation wavelength dependence of the upconverted luminescence together with its time evolution after infrared pulsed excitation suggest that energy transfer upconversion processes are responsible for the upconversion luminescence.     

Ni-GDC microtubular cermets

Ni-GDC cermet tubes (~ 3 mm inside diameter, 0.3–0.4 mm wall thickness and ～ 100 mm in length) with different amounts of porosity have been prepared by sintering of NiO-Ce_0.9Gd_0.1O_1.95 (NiO-GDC) nanopowders and further reduction. The NiO-GDC nanopowders were synthesized by chemical route and the different pore density was obtained by modifying the processing conditions (calcining and adjustment of carbonous remains).Ni-GDC cermets were obtained from the sintered NiO-GDC composites using reduction treatment at 700 °C for 3 h in reducing atmosphere (5 vol.% H₂–95 vol.% Ar). After the reduction process, tubes with 25–32% porosity were obtained. Gas permeability and Hg porosimetry studies were used to evaluate permeability, pore distribution and pore density. Electrical conductivity studies of the cermets were also performed.     

Conductivity anisotropy in directionally solidified CaZrO3---CaSZ and MgO-MgSZ eutectics

The results of the impedance spectroscopy measurements on eutectic samples based on zirconium oxide are presented here. Samples of CaZrO₃---ZrO₂(cubic) and MgO---ZrO₂(cubic) have been grown by a directional solidification procedure such that the different phases appear nearly oriented along the growth direction (lamellae in the system of CaZrO₃-ZrO₂(cubic) and fibers of MgO in a ZrO₂ matrix in the other system). The DC electrical conductivity has been measured by impedance spectroscopy along and across the growth axis. For CaZrO₃---ZrO₂ the coductivity is clearly anisotropic. The following values for σT have been obtained: the conductivity at 600 °C equals 2.0 × 10⁻⁶ Ω⁻¹ cm⁻¹ perpendicular to the fiber axis and 1.4 × 10⁻⁵ Ω⁻¹ cm⁻¹ parallel to it and with an activation energy of 1.3 eV for σT. For MgO---ZrO₂(cubic) the isotropic value of the conductivity at 600 °C is 10⁻⁴ Ω⁻¹ cm⁻¹ with activation energy for σT of 1.5 eV. The anisotropic conductivity in the CaZrO₃---ZrO₂ (cubic) system has been explained by a model of an ordered stacking of oxygen conducting (cubic ZrO₂) and non-conducting (CaZrO₃ or MgO) phases.     

Non-cubic Mn2+-centers in BaF2

The EPR spectra of thermally treated BaF₂: Mn samples is reported. After thermal annealing at 900 K a trigonal Mn²⁺ center with g=2.000±0.005, |D|=2725±40MHz, |A|=265±10MHz, $\text{D}\text{A}\text{>0}$, is observed. Annealing at 1200 K produces an orthorhombic Mn²⁺ center with g=2.00±0.01, |D|=2430±40MHz, |E|=570±20MHz, |A|=265±10MHz, $\text{D}\text{A}\text{<0}$. The superhyperfine (SHF) structures due to interactions with the neighbouring fluorines indicates that the trigonal manganese interacts with four fluorines, three of them equivalent. The orthorhombic Mn²⁺ shows interaction with four equivalent fluorine nuclei.