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%.

An electrolyte cathode discharge atomic emission spectrometric (ELCAD-AES) method has been reported for the determination of cadmium in Zircaloys. Formic and acetic acids are examined to improve the sensitivity of ELCAD-AES for cadmium determination. The sensitivity of ELCAD-AES is improved 2-fold with 20% (v/v) formic acid. With 20% (v/v) formic acid, the improved detection limit of ELCAD-AES for cadmium is found to be 2 ng mL À1 . A previously reported matrix separation procedure using ammonium pyrrolidine dithiocarbamate (APDC) and methylisobutylketone (MIBK) for the extraction of Cd from Zirconium matrices has been optimised for ELCAD-AES analysis of cadmium. This procedure is found to be useful for the quantitative determination of cadmium in Zircaloys by ELCAD-AES. The precision expressed as a percentage relative standard deviation of the signals of multiple analyses (N ¼ 5) of ELCAD-AES method using the above matrix separation procedure has been found to be 10-15% for trace Cd. This ELCAD-AES method is validated with the certified values of Zircaloy CRM and the glow discharge quadrupole mass spectrometry (GD-QMS) values of Zircaloy samples.

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