Forensic Science International 2008-01-30

Selective colorimetric determination of TNT partitioned between an alkaline solution and a strongly basic Dowex 1-X8 anion exchanger.

Ayşem Uzer, Erol Erçağ, Reşat Apak

Index: Forensic Sci. Int. 174(2-3) , 239-43, (2008)

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Abstract

The Meisenheimer anions formed from TNT in KOH solutions in alcohol or acetone were used in screening tests for TNT among possible nitro-explosives. The same reaction was used for the spectrophotometric assay of TNT in soil by CRREL (Cold Regions Research & Engineering Laboratory of the U.S. Army) method, also known as Jenkins' method, but the color stability was too dependent on the solution composition and the water tolerance was low, necessitating complete drying of soil samples (which may cause partial analyte decomposition) prior to analysis. This study reports the development of a colorimetric method based on the solid phase extraction (SPE) of the Meisenheimer anion formed from TNT and aqueous NaOH into a strongly basic anion exchange resin Dowex 1-X8 (OH(-) form). The orange-red color that developed both in the solid resin and solution phases was persistent for at least 1h. The resin was let to swell in alcohol, washed first with 1M aqueous NaOH, and then with H(2)O before use. To 5 mL of 4-400 ppm TNT solutions in 1:1 (v/v) acetone-water, 0.5 mL of 5% NaOH was added, diluted to 50 mL with 1:1 acetone-water, and the resulting solutions (containing the orange-red Meisenheimer anion of TNT) were agitated at room temperature with 0.9 g resin for < or =50 min. TNT exhibited a reasonably constant distribution coefficient between the resin and aqueous phases. The absorbance of the filtered solutions was measured against a reagent blank at 500nm. The TNT-loaded resins were regenerated with 1M HCl containing sodium sulfite. The calibration line of filtrate absorbance versus analytical concentration was linear over two orders of magnitude between 0.4 and 40 ppm TNT in final solution. Unlike Jenkins' method, the method was tolerant to 100-fold (by mass) of common soil anions like sulfate, nitrate, and chloride. The basic advantages of the developed colorimetric method over the similar CRREL/Jenkins' method may be summarized as color stability, water and common ion tolerance, lowering of the LOD, and widening of the linear range. As opposed to Jenkins' method, the charge-transfer bands characteristic to colorimetric detection were not obscured by the presence of water. The method is suitable for on-site applications, because the color developed in heterogenous solution was stabilized, and the method can be easily practiced with a portable colorimeter to large numbers of samples.