On-column capillary suppressor for open tubular ion chromatography.

Background: Suppressors with different dead volumes are required to match different suppressed ion chromatography systems. Especially for suppressed open tubular ion chromatography (SOTIC), the dead volume is a critical parameter. Both connection tubes between open tubular (OT) columns and suppressors and the dead volumes of the suppressors should be as short/small as possible to minimize peak dispersion. Suppressors with different dead volumes are required to match the various suppressed ion chromatography systems that operate at low flow rates 20-200 nL/min.

Results: We describe three designs of on-column capillary suppressors for SOTIC: (A) on-column electrodialytic suppressor prepared by making small cracks on the cycloolefin polymer (COP) capillary at targeted locations, (B) on-column electrodialytic suppressor built on a polyether ether ketone (PEEK) capillary by removing the wall materials at target locations, (C) on-column chemical suppressor based on a single cut on a PEEK capillary at a targeted location a single cut on a PEEK capillary at a targeted location. The on-column electrodialytic suppressors work in two different modes with suppression voltage applied in co-current and counter-current direction to the eluent flow. Because of very narrow column inner diameter (i.d.), up to several hundred volts were required to suppress the hydroxide eluent, but it was found the there was a >90% loss of analytes in the suppressor accompanied with a high noise level after on-column electrodialytic suppression. Theoretical analysis reveals that high suppression voltage significantly affects the retention of specific analytes by electromigration. Further analysis indicated that the electrodialytic on-column suppressor in co-current mode would behave totally different from traditional suppressors. The on-column chemical suppression, with minimum dead volume of 0.27 nL, provides fairly well suppression of low hydroxide eluent without analyte loss in the suppressor. In design C, an efficiency of 47000 ± 1800 plates/m for Cl, corresponding to a peak volume of 17.9 ± 0.7 nL, was obtained when separating five anion mixture (0.5 mM each) in the 25 μm i.d. AS18 latex coated PEEK OT column with an injection of 7.3 nL. Theoretical calculation revealed that a column efficiency loss of ≤3% would result in a cylindrical chemical suppression channel and thus it is taken as the acceptable dispersion contribution originating from the on-column chemical suppressor.

Significance: Different on-column suppressors have been designed on OT columns with i.d.s less than 30 μm. Two electrodialytic on-column suppressor designs with eluent flow parallel to the direction of electric field were proposed and tested. The eluent flow rate, analytes' retention behavior, resistance of suppression channel, current-voltage relationship, and working principles in both co-current and counter-current were experimentally investigated and comprehensively discussed. It was found that although the on-column electrodialytic suppressions (Design A and B) are not feasible in practice, the electrodialytic on-column suppressor on co-current mode has a potential of being used as an enriching capillary column for analyte ions. Design C provides fairly well chemical suppression. Theoretical calculation indicates that the loss of column efficiency can be controlled within 3%.