Membrane optode for mercury(II) determination in aqueous samples

A color changeable optode for Hg(II) was prepared by the immobilization of a dye 4-(2-pyridylazo)resorcinol (PAR) and a liquid ion-exchanger trioctylmethylammonium chloride (Aliquat-336) in the tri-(2-ethylhexyl) phosphate plasticized cellulose triacetate matrix. Hg(II) and CH(3)Hg(+) from aqueous samples could be quantitatively preconcentrated in this transparent optode producing a distinct color change (lambda(max)=520 nm) within 5 min equilibration time in bicarbonate aqueous medium or 30 min in natural water. Whereas optode sample without Aliquat-336 did not change its color corresponding to Hg-PAR complex on equilibrium with the same aqueous solution containing Hg(II) ions. The uptake of Hg(II) was found to be pH dependent with a maximum (>90%) at a pH 7.5. The uptake of ions like Cu(II), Fe(II), Zn(II) and Pb(II) was negligible in the optode where as the uptake of Cd(II) and Zn(II) ions was 10-15% at pH 7.5. The optode developed in the present work was studied for its analytical application for Hg(II) in the aqueous samples by spectrophotometry, radiotracer ((203)Hg), Energy Dispersive X-ray Fluorescence (EDXRF) analyses and Instrumental Neutron Activation Analysis (INAA). The minimum amount of Hg(II) required to produce detectable response by spectrophotometry, INAA and EDXRF were found to be 5.5, 1 and 12 microg, respectively. This optode showed a linear increase in the absorbance at lambda(max)=520 nm over a concentration range of 0.22-1.32 microg/mL of Hg(II) ions in aqueous solution for 5 min. The preconcentration of Hg(II) from large volume of aqueous solution was used to extend the lower limit of concentration range that can be quantified by the spectrophotometry of optode. It was observed that preconcentration of 11 microg Hg(II) in 100mL (0.11 microg/mL) in aqueous samples gives a distinct color change and absorbance above 3 sigma of the blank absorbance. The optode developed in the present work was found to be reusable.