Use of 2-Hydrazinobenzothiazole-Modified Copolymer(s) as Potential Chelating Agent for Sensitive and Selective...

In this study, a new method was developed for the pre-concentration of trace mercury from seafood samples prior to analysis by spectrophotometry. The method is based on the complexation between 2-hydrazinobenzothiazole (2-HBT)-modified copolymer(s) and Hg(II) in the presence of an ionic surfactant, cetyltrimethylammonium bromide (CTAB), as sensitivity enhancer at pH 4.5 and the extraction of the complex into the surfactant-rich phase of polyethylene glycol tert-octylphenyl ether (Triton X-114) as the extractant. The variables affecting extraction efficiency were evaluated and optimized. Due to the observation that the modified copolymers are 2.5-fold more sensitive and selective to the Hg²⁺ ions than the CH₃Hg⁺, the amounts of free Hg²⁺ and total Hg were determined at 325 nm by spectrophotometric detection of free Hg²⁺ and total Hg in the pre-treated and extracted fish samples using dilute acid mixture containing Triton X-114 and K₂Cr₂O₇, before and after oxidation of CH₃Hg⁺ to Hg²⁺ with mixture of KBr and KBrO₃ in the acidic media. The amount of CH₃Hg⁺ was calculated from the difference between total Hg and free Hg²⁺ amounts. The accuracy was tested by analysis of two certified samples. The results were statistically in good agreement with the certified values, and the precision was lower than 6.4%. The limits of detection were 1.40 (1.58) and 1.91 (2.11) μg L^-1 for Hg²⁺ from the two calibration solutions spiked before the pre-treatment, respectively. It has been observed that there is no significant matrix effect by comparison of slopes of the calibration curves. The method was applied to seafood samples for speciation analysis of free Hg²⁺ and CH₃Hg⁺. In terms of speciation, while total Hg is detected in the range of 12.6-143.8 μg kg^-1, the distribution of mercury in seafood was in the range of 7.4-53.3 μg kg^-1 for CH₃Hg⁺ and in 8.3-90.5 μg kg^-1 for free Hg²⁺.