Tomokazu Hashiguchi

Method for the isolation of citric acid and malic acid in Japanese apricot liqueur for carbon stable isotope analysis.

A method for detecting the undeclared addition of acidic ingredients is required to control the authenticity of Japanese apricot liqueur. We developed an analytical procedure that minimizes carbon isotope discrimination for measurement of the δ(13)C values of citric and malic acid isolated from Japanese apricot liqueur. Our results demonstrated that freeze-drying is preferable to nitrogen spray-drying, because it does not significantly affect the δ(13)C values of citric acid and results in smaller isotope discrimination for malic acid. Both 0.1% formic acid and 0.2% phosphoric acid are acceptable HPLC mobile phases for the isolation of citric and malic acid, although the δ(13)C values of malic acid exhibited relatively large variation compared with citric acid following isolation using either mobile phase. The developed procedure allows precise δ(13)C measurements of citric and malic acid isolated from Japanese apricot liqueur.

Transfer of Cesium and Potassium from Grapes to Wine

The food-processing transfer parameters of radioactive and stable cesium and radioactive potassium were determined from grapes to wine. The concentration of cesium in the pomace was higher than that in juice, as was the case of potassium. During white and rosé wine fermentation, cesium concentration did not change significantly and potassium concentration decreased. These results suggest that the absorbance of cesium by yeast is much lower than that of potassium in the winemaking environment. The food-processing retention factors (Fr, content in wine/content in grape) of radiocesium and stable cesium for red wine were generally higher than those for white wine, reflecting the yields of wine and the extraction of cesium during maceration.

Preliminary detection method for added rice- and sugarcane-derived brewer’s alcohol in bulk samples of sake by measurement of hydrogen, oxygen, and carbon isotopes

The δD and δ18O of sake without ethanol extraction as well as the δ13C of ethanol were determined in order to detect rice-derived brewer’s alcohol. Brewing tests demonstrated that the δD decreases upon addition of brewer’s alcohol (both rice- and sugarcane-derived), while the δ18O has little response to either, and the δ13C increases only for added sugarcane-derived alcohol.

Lignin Is Linked to Ethyl-Carbamate Formation in Ume (Prunus mume) Liqueur

Ethyl carbamate concentrations in oak barrel-aged ume (Prunus mume) liqueurs were measured, and possible explanations for elevated levels were examined. The average concentration was 0.30 mg/L, significantly higher than in ume liqueurs not aged in oak (0.08 mg/L). Oak powder extracts were prepared from both untoasted and toasted oak powder by extraction with aqueous ethanol, and these were used to make ume liqueurs. Relative to a no-oak control, the ethyl carbamate concentrations were 3.8 and 11 times higher in the ume liqueur made with the untoasted and toasted oak powder extracts respectively. The extracts were loaded onto a C18 column, washed with water, and eluted with methanol. The 13C-NMR spectra for the main constituents of the methanol elution fractions were consistent with those for lignin or fragments thereof. The methanol fractions were added to ume liqueur which was stored for 3 months. Relative to a control, the ethyl carbamate concentrations in the 3-month old liqueurs were found to be 1.2 and 4.6 higher for the untoasted oak-powder and the toasted oak-powder respectively. Ethyl carbamate was formed when lignin was added to a 40% aqueous ethanol solution that contained potassium cyanide. These observations suggest that lignin or fragments thereof promote the formation of ethyl carbamate.

Carbon stable isotopic compositions of citric acid and malic acid in Japanese apricot liqueur decrease as the fruit ripens

The carbon stable isotopic composition (δ13C) is often analyzed to quantify the addition of acidulants to Japanese apricot liqueur, but little is known about the variation in the δ13C values of the main organic acids arising from differences in the ripeness of Japanese apricots. We show that in Japanese apricot liqueur prepared using fruits at different stages of ripeness, the δ13C values of citric acid and malic acid ranged from -25.1‰ to -23.7‰ and from -22.3‰ to -19.7‰, respectively, and the δ13C values decreased as the fruit ripened. The average δ13C value of citric acid from liqueurs was 0.7‰ higher than that from fresh fruits, whereas the δ13C values of malic acid showed no isotope discrimination. The variation in δ13C values of the main organic acids in Japanese apricot liqueurs will help detect acidulant addition and control authenticity.

Application of carbon and hydrogen stable isotope analyses to detect exogenous citric acid in Japanese apricot liqueur

Japanese apricot liqueur manufacturers are required to control the quality and authenticity of their liqueur products. Citric acid made from corn is the main acidulant used in commercial liqueurs. In this study, we conducted spiking experiments and carbon and hydrogen stable isotope analyses to detect exogenous citric acid used as an acidulant in Japanese apricot liqueurs. Our results showed that the δ13C values detected exogenous citric acid originating from C4 plants but not from C3 plants. The δ2H values of citric acid decreased as the amount of citric acid added increased, whether the citric acid originated from C3 or C4 plants. Commercial liqueurs with declared added acidulant provided higher δ13C values and lower δ2H values than did authentic liqueurs and commercial liqueurs with no declared added acidulant. Carbon and hydrogen stable isotope analyses are suitable as routine methods for detecting exogenous citric acid in Japanese apricot liqueur.