On-line electrodialytic matrix isolation for chromatographic determination of organic acids in wine

Chromatographic determination of organic acids is widely performed, but the matrix often calls for lengthy and elaborate sample preparation prior to actual analysis. Matrix components, e.g., proteins, non-ionics, lipids etc. are typically removed by a combination of centrifugation/filtration and solid phase extraction (SPE) that may include the use of ion-exchange media. Here we report the quantitative electrodialytic transfer of organic acids from complex samples to ultrapure water in seconds using cellulose membranes modified with N,N-dimethylaminoethyl methacrylate, which essentially eliminates the negative ζ-potential of a regenerated cellulose membrane surface. The transfer characteristics of the ion transfer device (ITD) were evaluated with linear carboxylic acids. While the ion transfer efficiencies may be affected by the acid dissociation constants, in most cases it is possible to achieve quantitative transfer under optimized device residence time (solution flow rate) and the applied voltage. In addition, the transfer efficiency was unaffected by the wide natural variation of pH represented in real samples. The approach was applied to organic acids in various samples, including red wine, considered to represent an especially difficult matrix. While quantitative transfer of the organic acids (as judged by agreement with standard pretreatment procedures involving SPE) was achieved, transfer of other matrix components was <5%. The processed samples could then be chromatographically analyzed in a straightforward manner. We used ion exclusion chromatography with direct UV detection; in treated samples; there was a dramatic reduction of the large early peaks observed compared to only 0.45μm membrane filtered samples.