Uncovering the method of production and detection of synthetic acetic acid adulteration in vinegar by tandem use of {sup 1}4C liquid scintillation counting and {sup 1}3C/{sup 1}2C ratio mass spectrometry

Fraudulent adulteration and or misrepresentation had been a problem for commercial vinegar in the Philippines. Solutions of synthetic acetic acid mixed with colorants and flavour enhancers have been marketed as {sup v}inegar{sup .} Philippine regulations prohibit the sale of these vinegars produced by non-biogenic means as well as misrepresentation of the fine natural vinegars with cheaper version produced using lower value raw materials. The lack of reliable analytical tools however, has hampered the proper implementation of these laws. In this study, authentic vinegar samples were acquired, which were prepared by natural fermentation of : sugar cane, pineapple juice, and mango juice. Another type of cane vinegar was prepared by fermentation of cane sugar using acetator. Commercial vinegar samples, purchased from major supermarkets in the Philippines, were likewise obtained. Calcium acetate was produced by reaction of distilled vinegar samples with calcium carbonate, and subsequent drying of the resulting solution. Portions of the calcium acetate derived from the samples,were reacted with pyrophosphoric acid in a reflux and the glacial acetic acid was recovered by distillation under reduced pressure. The recovered glacial acetic acid were reconstituted to 90 % v/v. The acetic solutions were mixed with an Optiphase Hisafe Scintillant in vials. The C14 activities of the samples were measured in a 1414 Wallac Scintillation Counter and expressed as disintegrations per gram carbon or dpm/g C. Biogenic samples exhibit 12-15 dpm/g C activities, while synthetic samples show 0-2 dpm/g C activities. The remaining portions of the calcium acetate powder were placed in evacuated glass ampoules containing potassium peroxidisulfate and silver (1) permanganate. The samples inside the ampoules were oxidized to Carbon Dioxide, CO{sub 2} gas, in a furnace. The CO{sub 2} were then purified and bled to an Isotope Ratio mass spectrometer. {sup 1}3C/{sup 1}2C ratios were determined and compared against a standard CO{sub 2} gas (standardized against the International Pee Dee Belemnite Standard). Delta values of acetic acid obtained from C4 plants including sugar cane, and pineapple were between (-12.2) to (-15.9) per mil respectively. The vinegar obtained from mango, a C3 plant, gave (-20.1) per mil. The acetic acid produced from sugar cane using an acetator presented a fractionation (-10.2 per mil.) which allows for it to be differentiated from cane vinegar produced via the conventional fermentation production, not using an acetator. Possible synthetic/petroleum derived vinegars exhibit delta values beyond (-30) per mil. Five out of seven of the commercial vinegar brands were suspected to be made of synthetic acetic acid. Isotope ratio mass spectrometry and liquid scintillation counting are promising tools for revealing the botanical origin and method of production, and detection of synthetic acid adulteration in vinegar samples.