Flow Injection Analysis of H2O2 in Natural Waters Using Acridinium Ester Chemiluminescence: Method Development and Optimization Using a Kinetic Model

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• 作者：D. Whitney King ; William J. Cooper ; Steven A. Rusak ; Barrie M. Peake ; James J. Kiddle ; Daniel W. O'Sullivan ; Megan L. Melamed ; Chris R. Morgan ; Stephen M. Theberge
• 刊名：Analytical Chemistry
• 出版年：2007
• 出版时间：June 1, 2007
• 年：2007
• 卷：79
• 期：11
• 页码：4169 - 4176
• 全文大小：413K
• 年卷期：v.79,no.11(June 1, 2007)
• ISSN：1520-6882

文摘

Chemiluminescence (CL) of acridinium esters (AE) hasfound widespread use in analytical chemistry. Using themechanism of the reaction of H₂O₂ with 10-methyl-9-(p-formylphenyl)acridinium carboxylate trifluoromethanesulfonate and a modified flow injection system, thereaction rates of each step in the mechanism wereevaluated and used in a kinetic model to optimize theanalysis of H₂O₂. Operational parameters for a flowinjection analysis system (reagent pH, flow rate, samplevolume, PMT settings) were optimized using the kineticmodel. The system is most sensitive to reaction pH dueto competition between AE hydrolysis and CL. The optimized system was used to determine H₂O₂ concentrationsin natural waters, including rain, freshwater, and seawater. The lower limit of detection varied in natural waters,from 352 pM in open ocean seawater (mean, 779 pM ±15.0%, RSD) to 58.1 nM in rain (mean, 6,340 nM ±0.92%, RSD). The analysis is specific for H₂O₂ and istherefore of potential interest for atmospheric chemistryapplications where organoperoxides have been reportedin the presence of H₂O₂.