Cobalt as chemical modifier to improve chromium sensitivity and minimize matrix effects in tungsten coil atomic emission spectrometry |
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Authors: | Sidnei G Silva George L Donati Luana N Santos Bradley T Jones Joaquim A Nóbrega |
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Institution: | 1. Group of Applied Instrumental Analysis, Department of Chemistry, Federal University of São Carlos, P.O. Box 676, São Carlos, SP 13560-970, Brazil;2. Department of Chemistry, Wake Forest University, Winston-Salem, NC 27109, USA |
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Abstract: | Cobalt is used as chemical modifier to improve sensitivity and minimize matrix effects in Cr determinations by tungsten coil atomic emission spectrometry (WCAES). The atomizer is a tungsten filament extracted from microscope light bulbs. A solid-state power supply and a handheld CCD-based spectrometer are also used in the instrumental setup. In the presence of 1000 mg L−1 Co, WCAES limit of detection for Cr (λ = 425.4 nm) is calculated as 0.070 mg L−1; a 10-fold improvement compared to determinations without Co modifier. The mechanism involved in such signal enhancement is similar to the one observed in ICP OES and ICP-MS determinations of As and Se in the presence of C. Cobalt increases the population of Cr+ by charge transfer reactions. In a second step, Cr+/e− recombination takes place, which results in a larger population of excited-state Cr atoms. This alternative excitation route is energetically more efficient than heat transfer from atomizer and gas phase to analyte atoms. A linear dynamic range of 0.25–10 mg L−1 and repeatability of 3.8% (RSD, n = 10) for a 2.0 mg L−1 Cr solution are obtained with this strategy. The modifier high concentration also contributes to improving accuracy due to a matrix-matching effect. The method was applied to a certified reference material of Dogfish Muscle (DORM-2) and no statistically significant difference was observed between determined and certified Cr values at a 95% confidence level. Spike experiments with bottled water samples resulted in recoveries between 93% and 112%. |
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Keywords: | Chemical modifier Tungsten coil Ionization/excitation mechanism Atomic emission Ionization potential |
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