Simultaneous determination of Cr, Fe, Ni and V in crude oil by emulsion sampling graphite furnace atomic absorption spectrometry

In this work a simple and reliable method for the simultaneous determination of Cr, Fe, Ni and V in crude oil, using emulsion sampling graphite furnace atomic absorption spectrometry is proposed. Under the best conditions, sample masses around 50 mg were weighed in polypropylene tubes and emulsified in a mixture of 0.5% (v v(-1)) hexane + 6% (m v(-1)) Triton X-100 (R). Considering the compromised conditions, the pyrolysis an atomization temperatures for the simultaneous determination of Cr, Fe, Ni and V were 1400 degrees C and 2500 degrees C, respectively. Aliquots of 20 mu L of reference solution and sample emulsion were co-injected into the graphite tube with 10 mu L of 1.0 g L(-1) Mg(NO(3))(2) as chemical modifier. The detection limits (n = 10, 3 sigma) and characteristic masses were, respectively: 0.07 mu g g(-1) and 19 pg for Cr; 2.15 mu g g(-1) and 31 pg for Fe; 1.25 mu g g(-1) and 44 pg for Ni; and 1.15 mu g g(-1) and 149 pg for V. The reliability of the proposed method was checked by fuel oil Standard Reference Material (SRMTriton X-100 (R) 1634c - NIST) analysis. The concentrations found presented no statistical differences compared to the certified values at 95% confidence level.

Preliminary studies of laser-induced breakdown spectrometry for the determination of Ba, Cd, Cr and Pb in toys

The performance of laser-induced breakdown spectrometry (LIBS) for the determination of Ba, Cd, Cr and Pb in toys has been evaluated by using a Nd:YAG laser operating at 1064 nm and an Echelle spectrometer with intensified charge-coupled device detector. Samples were purchased in different cities of Sao Paulo State market and analyzed directly without sample preparation. Laser-induced breakdown spectrometry experimental conditions (number of pulses, delay time. integration time gate and pulse energy) were optimized by using a Doehlert design. Laser-induced breakdown spectrometry signals correlated reasonably well with inductively coupled plasma optical emission spectrometry (ICP OES) concentrations after microwave-assisted acid digestion of selected samples. Thermal analysis was used for polymer identification and scanning electron microscopy to Visualize differences in crater geometry of different polymers employed for toy fabrication. Results indicate that laser-induced breakdown spectrometry can be proposed as a rapid screening method for investigation of potentially toxic elements in toys. The unique application of laser-induced breakdown spectrometry for identification of contaminants in successive layers of ink and polymer is also demonstrated. (C) 2009 Elsevier B.V. All rights reserved.

Determination of Cr, Fe, Co, Ni, Cu, Zn, As and Pb in liquid chemical waste by energy dispersive X-ray fluorescence

A method for simultaneous determination of Cr, Fe, Co, Ni, Cu, Zn, As e Pb in liquid chemical waste using Energy Dispersive X-Ray Fluorescence (EDXRF) technique was evaluated. A small sample amount (200 mu L) was dried on a 6.35 mu m thickness Mylar film at 60 degrees C and the analyses were carried out using an EDXRF spectrometer operated with an X-ray Mo tube (Zr filter) at 30 kV/20 mA. The acquisition time was 300 s and the Ga element was utilized as internal standard at 25 mg/L for quantitative analysis. The method trueness was assessed by spiking and the detection limit for those elements ranged from 0.39 to 1.7 mg/L. This method is notable because it assists the choice of the more appropriated waste treatment procedure, in which inter elemental interference is a matter of importance. In addition, this inexpensive method allows a non-destructive determination of the elements from (19)K to (92)U simultaneously.

Coconut coir as biosorbent for Cr(VI) removal from laboratory wastewater

A high cost-effective treatment of sulphochromic waste is proposed employing a raw coconut coir as biosorbent for Cr(VI) removal. The ideal pH and sorption kinetic, sorption capacities, and sorption sites were the studied biosorbent parameters. After testing five different isotherm models with standard solutions, Redlich-Peterson and Toth best fitted the experimental data, obtaining a theoretical Cr(VI) sorption capacity (SC) of 6.3 mg g(-1). Acid-base potentiometric titration indicated around of 73% of sorption sites were from phenolic compounds, probably lignin. Differences between sorption sites in the coconut coir before and after Cr adsorption identified from Fourier transform infrared spectra suggested a modification of sorption sites after sulphochromic waste treatment, indicating that the sorption mechanism involves organic matter oxidation and chromium uptake. For sulphocromic waste treatment, the SC was improved to 26.8 +/- 0.2 mg g(-1), and no adsorbed Cr(VI) was reduced, remaining only Cr(III) in the final solution. The adsorbed material was calcinated to obtain Cr2O3, with a reduction of more than 60% of the original mass. (c) 2008 Elsevier B.V. All rights reserved.

Microstructural characterization of as-cast Cr-B alloys

Accurate knowledge of several Me-B (Me - Metal) phase diagrams are important to evaluate higher order systems such as Me-Si-B ternaries. This work presents results of microstructural characterization of as-cast Cr-B alloys which are significant to assess the liquid compositions associated to most of the invariant reactions of this system. Alloys of different compositions were prepared by arc melting pure Cr and B pressed powder mixtures under argon atmosphere in a water-cooled copper crucible with non-consumable tungsten electrode and titanium getter. The phases were identified by scanning electron microscopy (SEM), using back-scattered electron (BSE) image mode and X-ray diffraction (XRD). In general, a good agreement was found between our data and those from the currently accepted Cr-B phase diagram. (c) 2006 Elsevier Inc. All rights reserved.

Microstructural characterization of as-cast Cr-Si alloys

This work presents results of microstructural characterization of as-cast Cr-Si alloys. The alloys were prepared by arc melting pure Cr (min. 99.996%) and Si (min. 99.998%) powder mixtures under argon atmosphere in a water-cooled copper crucible with nonconsumable tungsten electrode and titanium getter. The phases were identified by scanning electron microscopy (SEM), using the back-scattered electron (BSE) image mode and X-ray diffraction (XRD). The results confirm the currently accepted Cr-Si phase diagram in terms of the invariant reactions and solid phases present in this system. Small corrections are proposed for the compositions of the liquid phase in the following reactions: (i) L double left right arrow Cr-ss+Cr3Si, from 15 to 16 at.% Si; (ii) L+alpha Cr5Si3 double left right arrow CrSi, from 51 at.% Si to slightly above 53 at.% Si; (iii) L double left right arrow CrSi+CrSi2, from 56 to slightly above 57 at.% Si; (iv) L double left right arrow CrSi2+Si, from 82 to slightly above 85 at.% Si. (c) 2006 Elsevier Inc. All rights reserved.

Adsorption of Cr(VI) from aqueous solution by hydrous zirconium oxide

A type of ZrO(2)center dot nH(2)O Was synthesized and its Cr(VI) removal potential was investigated in this study. The kinetic study, adsorption isotherm, pH effect, thermodynamic study and desorption were examined in batch experiments. The kinetic process was described by a pseudo-second-order rate model very well. The Cr(VI) adsorption tended to increase with a decrease of pH. The adsorption data fitted well to the Langmuir model. The adsorption capacity increased from 61 to 66 mg g(-1) when the temperature was increased from 298 to 338 K. The positive values of both Delta H degrees and Delta S degrees suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption. Delta G degrees values obtained were negative indicating a spontaneous adsorption process. The effective desorption of Cr(VI) on ZrO(2)center dot nH(2)O could be achieved using distilled water at pH 12. (C) 2009 Elsevier B.V. All rights reserved.

Annealing behavior of ferritic-martensitic 9%Cr-ODS-Eurofer steel

Oxide dispersion strengthened ferritic-martensitic steels are potential candidates for applications in future fusion power plants. High creep resistance, good oxidation resistance, reduced neutron activation and microstructural long-term stability at temperatures of about 650-700 degrees C are required in this context. In order to evaluate its thermal stability in the ferritic phase field, samples of the reduced activation ferritic-martensitic 9%Cr-ODS-Eurofer steel were cold rolled to 50% and 80% reductions and further annealed in vacuum from 300 to 800 degrees C for 1 h. The characterization in the annealed state was performed by scanning electron microscopy in the backscattered electron mode, high-resolution electron backscatter diffraction and transmission electron microscopy. Results show that the fine dispersion of Y-based particles (about 10 nm in size) is effective to prevent recrystallization. The low recrystallized volume fraction (<0.1) is associated to the nuclei found at prior grain boundaries and around large M(23)C(6) particles. Static recovery was found to be the predominant softening mechanism of this steel in the investigated temperature range. (c) 2010 Elsevier B.V. All rights reserved.

Thermodynamic self-consistency issues related to the Cluster Variation Method: The case of the BCC Cr-Fe (Chromium-Iron) system

The Cluster Variation Method (CVM), introduced over 50 years ago by Prof. Dr. Ryoichi Kikuchi, is applied to the thermodynamic modeling of the BCC Cr-Fe system in the irregular tetrahedron approximation, using experimental thermochemical data as initial input for accessing the model parameters. The results are checked against independent data on the low-temperature miscibility gap, using increasingly accurate thermodynamic models, first by the inclusion of the magnetic degrees of freedom of iron and then also by the inclusion of the magnetic degrees of freedom of chromium. It is shown that a reasonably accurate description of the phase diagram at the iron-rich side (i.e. the miscibility gap borders and the Curie line) is obtained, but only at expense of the agreement with the above mentioned thermochemical data. Reasons for these inconsistencies are discussed, especially with regard to the need of introducing vibrational degrees of freedom in the CVM model. (C) 2008 Elsevier Ltd. All rights reserved.

Precipitation of Laves phase in a 28%Cr-4%Ni-2%Mo-Nb superferritic stainless steel

The main objective of the present work was to study the precipitation of the Laves phase in the X1 CrNiMoNb 28 4 2 (Werkstoff-Nr. DIN 1.4575) superferritic stainless steel employing several complementary techniques of microstructural analysis. The phase that precipitated in largest quantity in the DIN 1.4575 steel was the sigma (sigma) phase. However, along grain boundaries, after aging at 850 degrees C, a Laves phase of the MgZn2 type, with a hexagonal C14 crystal structure and chemical composition (Fe,Cr,Ni)(2)(Nb,Mo,Si), was also identified. Growth of the Laves phase is curtailed by exhaustion of niobium of the matrix and by the presence of the sigma phase, which also precipitates in the vicinity of the grain boundaries, however in larger amounts. No chi (chi) or austenite phases were detected in the temperature range studied. (C) 2007 Elsevier Inc. All rights reserved.

Ecophysiological responses of water hyacinth exposed to Cr(3+) and Cr(6+)

Due to its wide industrial use, chromium (Cr) is considered a serious environmental pollutant of aquatic bodies. in order to investigate the ecophysiological responses of water hyacinth [Eichhornia crassipes (Mart.) Solms] to Cr treatment, plants were exposed to 1 and 10 mM Cr(2)O(3) (Cr(3+)) and K(2)Cr(2)O(7) (Cr(6+)) concentrations for two or 4 days in a hydroponic system. Plants exposed to the higher concentration of Cr(6+) for 4 days did not survive, whereas a 2 days treatment with 1 mM Cr(3+) apparently stimulated growth. Analysis of Cr uptake indicated that most of the Cr accumulated in the roots, but some was also translocated and accumulated in the leaves. However, in plants exposed to Cr(6+) (1 mM), a higher translocation of Cr from roots to shoots was observed. it is possible that the conversion from Cr(6+) to Cr(3+), which immobilizes Cr in roots, was not total due to the presence of Cr(6+), causing deleterious effects on gas exchange, chlorophyll a fluorescence and photosynthetic pigment contents. Chlorophyll a was more sensitive to Cr than chlorophyll b. Cr(3+) was shown to be less toxic than Cr(6+) and, in some cases even increased photosynthesis and chlorophyll content. This result indicated that the F(v)/F(0) ratio was more effective than the F(v)/F(m) ratio in monitoring the development of stress by Cr(6+). There was a linear relationship between qP and F(v)/F(m). No statistical differences were observed in NPQ and chlorophyll a/b ratio, but there was a tendency to decrease these values with Cr exposure. This suggests that there were alterations in thylakoid stacking, which might explain the data obtained for gas exchanges and other chlorophyll a fluorescence parameters. (C) 2008 Elsevier B.V. All rights reserved.

Photochemical cleavage of nitrate ion coordinated to a Cr(III) porphyrin#

Photolysis of the nitrato chromium(III) tetraphenylporphyrinato compound Cr(TPP)(NO(3)) (TPP, tetraphenylporphyrin) in toluene solution clearly leads to the formation of the Cr(IV) oxo complex Cr(TPP)(O) with a quantum yield of 0.011. The other product, NO(2), was detected quantitatively by its reaction with the spin trapping agent 2,2,6,6-tetramethyl-piperidine-1-oxyl.

Synthesis, structure and magnetism of the oxalato-bridged chromium(III) complex [NBu4n](4)[Cr-2(ox)(5)]center dot 2CHCl(3)

The binuclear complex [NBu4n](4)[Cr-2(ox)(5)]. 2CHCl(3) has been prepared by an ion-exchange procedure employing Dowex 50WX2 cation-exchange resin in the n-butylammonium form and potassium tris(oxalato)chromate(III). The dimeric complex was characterised by a crystal structure determination: monoclinic, space group C2/c, a = 29.241(7), b = 15.192(2), c = 22.026(5) Angstrom, beta = 94.07(1)degrees, Z = 4. The magnetic susceptibility (300-4.2 K) indicated that the chromium(III) sites were antiferromagnetically coupled (J = -3.1 cm(-1)).

Nickel complexes with tris(2-aminoethyl)amine (tren): [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2)center dot 6H(2)O (ox = oxalate), {[Ni-2(tren)(3)][ClO4](4)center dot H2O}(n), and [Ni-2(tren)(2)(aepd)][ClO4](4)center dot 2H(2)O (aepd = N-(2-aminoethyl)pyrrolidi

Reaction of K-3[Cr(ox)(3)] (ox = oxalate) with nickel(II) and tris(2-aminoethyl)amine (tren) in aqueous solution resulted in isolation of the bimetallic assembly [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2). 6H(2)O. The polymeric complex {[Ni-2(tren)(3)][ClO4](4). H2O}(n) has been prepared by reaction of nickel(II) perchlorate and tren in aqueous solution. From the same reaction mixture the complex [Ni-2(tren)(2)(aepd)][ClO4](4). 2H(2)O (aepd = N-(2-aminoethyl)pyrrolidine-3,4-diamine), in which a bridging tren ligand contains a carbon-carbon bond between two arms forming a substituted pyrrolidine, has been isolated. The complexes have been characterized by X-ray crystallography. The magnetic susceptibility (300-4.2 K) and magnetization data (2, 4 K, H = 0-5 T) for {[Ni-2(tren)(3)][ClO4](4). H2O}(n) (300 K , 4.23 mu(B)) exhibit evidence of weak antiferromagnetic coupling and zero field splitting (2J = -1.8 cm(-1); \ D\ = 2 cm(-1)) at low temperature. For [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2). 6H(2)O the susceptibility data at 300 K are indicative of uncoupled nickel(II) and chromium(III) sites with zero-field splitting and intramolecular antiferromagnetic coupling predicted at low temperature.