Determination of major to trace level elements in Zircaloys by electrolyte cathode discharge atomic emission spectrometry using formic acid

Abstract

An electrolyte cathode discharge atomic emission spectrometry (ELCAD-AES) method using formic acid is described for the determination of major to trace level of the elements Ni, Co, Fe, Mn, Mg, Cu, Cr, Pb, Ca in Zircaloys. The influence of HCOOH and CH 3 COOH to improve the sensitivity of ELCAD-AES for analyte determination is investigated. Sensitivity of ELCAD-AES was significantly improved with HCOOH for the determination of these elements. 20% (v/v) HCOOH was found to produce a maximum enhancement in the sensitivity of ELCAD-AES for the analytes. With 20% (v/v) HCOOH, improved detection limits were determined for Ni (5 ng mL À1 ), Co (9 ng mL À1 ), Fe (16 ng mL À1 ), Mn (7 ng mL À1 ), Mg (5 ng mL À1 ), Cu (6 ng mL À1 ), Cr (65 ng mL À1 ), Pb (10 ng mL À1 ), and Ca (8 ng mL À1 ). The improvement is 2-fold for most elements, 5-fold for Pb, and essentially unchanged for Cr. The use of HCOOH enabled the direct determination of analytes in Zircaloys by ELCAD-AES. The method has been validated by determining the concentrations of analytes Ni, Co, Fe, Mn, Mg, Cu, Cr, Pb, Ca in a Zircaloy certified reference material (Zircaloy-4 NIST-360b) and also in a Zircaloy sample which was analysed by glow discharge quadrupole mass spectrometer (GD-QMS). The precision expressed as a percentage relative standard deviation of signals of multiple analyses (N ¼ 4) of the ELCAD-AES method was found to be between 2 and 10% for major (>0.1 wt%) and minor level (<0.1 wt% and >100 mg g À1 ) elements and 10-15% for trace level (<100 mg g À1 and >10 ng g À1 ) elements. Depending on the levels of the impurities the relative error in accuracy of the ELCAD-AES method was found to be between 3 and 20%.

Coupling of cold vapor generation with an atmospheric pressure glow microdischarge sustained between a miniature flow helium jet and a flowing liquid cathode for the determination of mercury by optical emission spectrometry

“…9,13,15,16,21,26 In our latest papers, 9,21 physicochemical properties of the liquid cathode solution were modied by addition of non-ionic Triton surfactants. The effect of size and concentration of Triton surfactants on the analytical performance of APGD-OES was investigated.…”

On the coupling of hydride generation with atmospheric pressure glow discharge in contact with the flowing liquid cathode for the determination of arsenic, antimony and selenium with optical emission spectrometry

“…In general, these new excitation sources enable efficient excitation of elements with relatively low excitation potentials, i.e., alkali and alkaline earth elements and some of transition metals. Limits of detection (LODs) of elements usually vary from several to tens micro gram per liter and because of that miniaturized excitation sources are commonly used for their quantification in different samples [4][5][6][7][8][9][10][11][12][13][14][15][16]. On the other hand, mentioned radiation sources are rarely utilized for the determination of elements with high excitation potentials, e.g., As, Sb or Se, with OES.…”

“…They sheared a considerable interest and are the subject of a growing number of works [1][2][3]. Among developed and studied in recent years miniaturized excitation sources there are dielectric barrier discharge (DBD), electrolyte as cathode glow discharge (ELCAD), liquid sampling atmospheric pressure glow discharge (LS-APGD), solution cathode glow discharge (SCGD), capacitively coupled plasma (CCP) and microstrip plasma (MSP) [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. In general, these new excitation sources enable efficient excitation of elements with relatively low excitation potentials, i.e., alkali and alkaline earth elements and some of transition metals.…”

On-line separation and preconcentration of hexavalent chromium on a novel mesoporous silica adsorbent with determination by solution-cathode glow discharge-atomic emission spectrometry

“…34 Additionally, the net intensity of the atomic emission lines of Cr solutions with 0.15% (mass percentage) CTAC improved by 2.6-fold, compared with solutions without CTAC, affording DL of Cr for 42 mg L À1 . 35 However, the DLs were still much higher than those from other detection systems such as ETAAS and ICP-MS, and far from levels normally required.…”