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A simple method for the rapid extraction and determination of ultra-trace amounts of Ag+ions using octadecyl-bonded silica membrane disks modified with a recently synthesized fulvalen (tetramethyltetrathiafulvalen) (TMTTF) and graphite furnace atomic absorption spectrometry is presented. The extraction efficiency and influence of the flow rate, pH, nature of the counter ion and type and the least amount of eluent for the stripping of Ag+from disks and breakthrough volume were evaluated. The maximum capacity of the membrane disks modified by 5 mg of TMTTF used was found to be 482 ± 6 µg Ag+. The detection limit of the proposed method is 1.0 ng/dm3. The method was applied to the recovery of Ag+ions from different synthetic and water samples.