Direct Measurement of Aqueous Mercury(II): Combining DNA-Based Sensing with Diffusive Gradients in Thin Films

A highly specific DNA-functionalized hydrogel sensing layer was integrated with the diffusive gradients in thin films (DGT) technique for the direct determination of aqueous mercury(II). The DNA-functionalized layer in the DGT unit exhibited both high affinity (complexation constant K-c = 10(19.8) at 25 degrees C) and high binding capacity (9.5 mg Hg disk(-1)) toward Hg2+. The diffusion coefficient for Hg2+ complexed with common inorganic ligands was an order of magnitude higher than that for Hg2+ complexed with natural dissolved organic matter: 9.0 x 10(-6) versus 9.8 x 10(-7) cm(2) s(-1) at 25 degrees C. The performance of the DNA-DGT sensor was further assessed under variable pH (3-10) and temperature (5-40 degrees C) conditions, as well as across a range of hydrochemically diverse artificial and natural freshwaters. The observed effects of the environmental and solution compositional variables on Hg2+ binding to the DNA in the sensing layer were successfully accounted for by equilibrium speciation calculations and temperature-corrected, multicomponent diffusion coefficients for aqueous Hg(II). The results therefore support the use of the DNA-DGT sensor as an alternative to traditional sampling and analysis methods for measuring aqueous Hg(II) concentrations down to the nanomolar level in freshwater environments.