Simplifying the measurement of different forms of cu in wines and strategies for efficient removal

Abstract

Copper (Cu) is known to substantially impact wine stability through oxidative, reductive or colloidal phenomena. Recent work has shown that Cu exists predominantly in a sulfide-bound form, which may act as a potential source of sulfidic off-odours in wine and hence contribute to reductive flavours. The quanti-fication of different forms of copper in wine may allow winemakers to target more effective strategies for the removal of Cu and also to better understand the likelihood of reductive characters emerging in wines during aging.

A simple colorimetric method, utilising bicinchonic acid (BCA), was validated for the determination of the different forms of Cu in white wines, as well as the total Cu concentration in red wine. The determination of total Cu in white wines utilises an addition of excess silver(I) in order to effectively release copper from sulfide and allow quantitative complexation by BCA. The non-sulfide bound form of Cu in the white wine was determined by BCA analysis of the white wine without silver addition. In the case of red wines, a simple digestion procedure eliminated colour prior to subsequent analysis as per the white wines. The total Cu measured by the colorimetric method had an accuracy equivalent to ICPOES and a linear range of 0.04 to 1.0 mg/L. The different forms of Cu measured in white wines agreed with the results obtained by a more laborious electrochemical method.

The removal of different forms of Cu from white and red wine was subsequently studied using membrane filters of various media and pore size, depth filters and PVI/PVP. Only PVI/PVP could efficiently remove both forms of Cu, whilst the filtration techniques displayed activity for removing the sulfide bound form of Cu. Of the membrane filters, nylon and polytetrafluoroethylene media could adsorb sulfide-bound Cu, with little dependence on pore size, but their capacity for removal decreased rapidly with wine filtration volume. Similar results were observed with cellulose-based depth filters, but much greater removal efficiency was observed for cellulose depth filters impregnated with diatomaceous earth. This type of filter had active re-moval of sulfide-bound Cu from larger volumes of wine. The results allow rapid determination of the Cu forms in wine along with the assessment of the best strategies for their removal.

Abbreviations: PVI/PVP, polyvinylimidazole/polyvinylpyrrolidone.