Complexation of Hg(II) by humic acid studied by square wave stripping voltammetry at screen-printed gold electrodes

This paper reports the development of a sequential injection (SI) method to study the complexation of Hg(II) by humic acid (HA) using square wave anodic stripping voltammetry at a screen-printed gold electrode (SPGE). The SI system injected samples (in 0.020 mol L(-1) NaNO(3) and pH 6.0) to the flow cell during the deposition step and exchanged the medium to 0.050 mol L(-1) HCl to perform the stripping step under stopped flow conditions. For sample volume=750 μL, flow rate=15 μL s(-1) (deposition step), and square wave frequency=100 Hz, the detection limit was 20 nmol L(-1) and the sampling throughput was 17 analyses per hour. Complexation of Hg(II) was studied using a 25.0 mg L(-1) suspension of HA (72.5 μmol L(-1) of ionizable sites), and total Hg(II) concentrations from 1 to 20 μmol L(-1). The diffusion coefficient of the complex was (1.3±0.2)×10(-7) cm(2) s(-1). A complexing capacity of 537 μmol g(-1) was found. The log of the differential stability constant (logK(DEF)) decreased from 7.0 to 5.3 as the log of the degree of site occupation (logθ) increased from -1.6 to -0.5. The values of logK(DEF) were consistent with complexation of Hg(II) by carboxylic and phenolic groups.