Cathodic preconcentration of f-elements on a mercury film carbon fiber disk microelectrode.

Field detection and quantification of f-elements is an important problem in radioanalytical chemistry requiring small, portable devices. Here, characterization of a 10 µm Hg film carbon fiber disk microelectrode to accumulate f-elements is described. Accumulation was performed by cathodic deposition and evaluated by anodic stripping and subsequent ICPMS analyses. La(3+) was used as the model element, and subsequent studies were conducted on a 17 element mixture (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Th). In the model studies, La(3+) undergoes a sorption phenomenon, and as in other studies and confirmed by ICPMS, a monolayer of atoms on the electrode surface is formed. Dissolved O(2) was found to have no effect on the cathodic accumulation of La(3+). Consideration of electrode reaction conditions is made, and reactions are hypothesized. The limit of detection (LOD) was found to be 10(-7) M with mass detection of 10(9) atoms, approximately 5 orders of magnitude less than at conventionally sized electrodes. To solve a dilution problem in follow-on analyses, a suggestion to use microelectrode chip-based sensors was made.

Preconcentration of f-elements from aqueous solution utilizing a modified carbon paste electrode.

An evaluation using paraffin oil based, Acheson 38 carbon paste electrodes modified with α-hydroxyisobutyric acid (HIBA) to preconcentrate f-elements cathodically is described. The modified paste was made by directly mixing solid HIBA into the carbon paste. A chemically reversible cyclic voltammogram for HIBA was observed on this modified carbon paste, which was found to be a non-Nerstian, single electron transfer process. Lanthanides (less promethium) were found to accumulate onto the electrode surface during a 30 s electrodeposition step at -0.4 V vs Ag/AgCl from 0.1 M LiCl. The elements were then stripped off into a 2% HNO(3) solution by an oxidative step at +0.8 V vs Ag/AgCl; quantitative removal from the electrode was confirmed by ICPMS. Ultratrace solutions with initial concentrations down to 5 parts per quadrillion (ppq) were preconcentrated in 5 min above our instrumental limit of detection (LOD) of around 1 ppt for lanthanides.

Preconcentration of trivalent lanthanide elements on a mercury film from aqueous solution using rotating disk electrode voltammetry.

An approach to concentrate trivalent lanthanide elements into or onto mercury film electrodes supported on rotating disk glassy carbon electrodes in small volumes (