Direct determination of cyclohexyltin derivatives by atomic absorption spectrophotometry with a graphite furnace atomizer (GFAA) was developed and this method was applied to residue analysis of tricyclohexyltin hydroxide in green tea and orange sprayed PLICTRAN miticide. Hitachi 170-70 type FGAA using the ZEEMAN EFFECT for the back ground correction was used. Analytical line was 286.3nm and Argon as sheath gas was used at flow rate of 3 liter/min. Ten μl of sample solution was introduced into the graphite furnace by Eppendorf pipette. Four cyclohexyltin derivatives, tetracyclohexyltin (Cy
4Sn), tricyclohexyltin hydroxide (Cy
3SnOH), dicyclohexyltin oxide (Cy
2SnO), monocyclohexylstannoic acid (CySnOOH) and inorganic tin were investigated on their operating conditions in the graphite furnace. The ashing condition by which the organotin was completely decomposed to inorganic form was seemed to be affected by its chemical and physical properties. Calibration curves were linear up to 3ng tin and relative standard deviation at ten times determinations were below 5% for all compounds. Lower limit of detection which gave 0.005 absorbance were 0.5ng tin for monocyclohexylstannoic acid and 0.2ng tin for the others. Tricyclohexyltin hydroxide in green tea or orange was extracted with
n-hexane and acetic acid. The residue was purified by following column chromatography. Basic alumina (3.5g, activity grade I) was packed into column (300×15mm I·D). After the sample had passed through, the column was developed with 50ml of
n-hexane, 50ml of ether (tetracyclohexyltin was eluted in these fractions) and 20ml of ethanol containing 2% benzene. Tricyclohexyltin hydroxide was eluted in the last fraction and monocyclohexylstannoic acid and dicyclohexyltin oxide still remained on the alumina. The solution was evaporated and the residue was dissolved in
n-hexane, then determined by GFAA. The operating conditions were as follows, Drying: 100°C, 20sec; Ashing: 900°C, 60sec; Atomization: 2, 800°C, 5sec. The lower limits of detection were 0.05ppm in 5g of green tea, 0.01ppm in 20g of orange peel and 0.006ppm in 50g of orange flesh and orange juice. Recoveries from green tea (fortified at the 2.0ppm level), orange flesh (0.1ppm), orange peel (0.3ppm) and orange juice (0.1ppm) were 91, 94, 82 and 109%, respectively. No acid digestion and a series of solvent extraction step were required for this analysis.
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