MISSION STATEMENT. The PNRI contributes to the improvement of the quality of Filipino life through the

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1 Our Organization

2 Our Organization MISSION STATEMENT The PNRI contributes to the improvement of the quality of Filipino life through the highest standards of nuclear research and development, specialized nuclear services, nuclear technology transfer, and efficient and effective implementation of nuclear safety practices and regulations

3 VINEGAR Vinegar being one of the oldest chemicals known to man, has been used as as a condiment, and as a natural preservative, salad dressing, pickling solution, etc., in the preparation of food. Acetic acid, CH 3 COOH is the compound in vinegar that gives vinegar its sour taste. Vinegar is 4-5% acetic acid by volume.

4 UNCOVERING THE METHOD OF PRODUCTION AND DETECTION OF SYNTHETIC ACETIC ACID ADULTERATION IN VINEGAR BY TANDEM USE OF 14 C LIQUID SCINTILLATION COUNTING AND 13 C/ 12 C RATIO MASS SPECTROMETRY. Stefan Wechner, 2 AndreyVoropaev 2, Lorenz Eichinger, 2 Flora L Santos 1, Soledad Castaneda 1,Joseph Michael Racho 1, Preciosa Corazon Pabroa 1, Ryan Morco 1 and Raymond J. Sucgang, 1 Philippine Nuclear Research Institute, Diliman,, Quezon City Philippines; rjsucgang@pnri.dost.gov.ph HYDROISOTOP GmbHk Scweitenkirchen, Germany.

5 Fraud in one form or another has accompanied commercial transactions for centuries... EXAMPLE 1: FRAUD IN THE DECLARATION OF BOTANICAL ORIGIN: Corn syrup sold as Dalandan Juice or as Ponkan Juice EXAMPLE 2: SUBSTITUTION WITH CHEAPER SYNTHETIC RAW MATERIALS: Adulteration of Vinegar With Synthetic Acetic Acid Solutions. EXAMPLE 3: MISDECLARATION OF GEOGRAPHICAL ORIGIN: Carabao mangoes planted in Mexico and Sold in the U.S as Guimaras Philippine mangoes

6 DETECTION OF NON BIOGENIC/ SYNTHETIC ACETIC ACID ADULTERATION. The Department of Health Administrative Order 134 s 1970, which defines the quality of vinegar for local consumption, prohibits the sale of vinegar containing synthetic or nonbiogenic acetic acid. The lack of reliable analytical tools however, has hampered the proper implementation of these laws.

7 C-12 C-14 C-12 C-14 SYNTHETIC ACETIC ACID BIOGENIC ACETIC ACID

8 SUCCESS STORIES 14 C ANALYSIS OF VINEGAR PNRI EXPERIENCE Vinegar is an exact molecular match with acetic acid from an industrial supply but not isotopically. Natural acetic acid as well as ethanol has a measurable radioactivity which can be a useful criterion for the differentiation of biogenic from synthetic materials. The method: LOW LEVEL LIQUID SCINTILLATION COUNTING

9 Figure 2. Variation of natural C-14 activity with time C-14 activity (dpm/g C) y = x R 2 = (PNRI) 15.7 Linear (C-14 levels in Acetic Acid ( )) Year Calculated C-14 activity C-14 levels in Acetic Acid ( ) C-14 levels in Acetic Acid (1986 to date)

10 METHODOLOGY for C-14 analysis: 1 Vacuum distillation of vinegar, lower & higher boiling fractions discarded 2 Treatment with CaCO3, excess CaCO3 filtered off. 3 Concentration of filtrate in rotary evaporator, and drying of residue on water bath; final drying of Ca acetate in vacuum oven. 4 Reaction of dried Ca acetate precipitate with pyrophosphoric acid in rotary evaporator and vacuum distillation of glacial acetic acid. 5 Preparation of 5 ml 90% acetic acid solution; addition of 15 ml of scintillant; counting in low-level level LSC.

11 Analysis of isolated acetic acid using a Wallac Guardian Low level LSC

12 LIQUID SCINTILLATION SPECTROMETRY (LSC) Analytical Measurements Research Philippine Nuclear Research Institute

13 Figure 1. Correlation between mean C-14 activity and synthetic acetic acid concentration Mean C-14 activity (dpm/g C) y = x R 2 = Percent synthetic acetic acid

14 Figure 11. Range of C-14 Activity in Commercial Vinegar Samples C-14 Activ vity (dpm/g C) Brand Code

15 Figure 11. Summary of C-14 data grouped by brands (A to G) (Metro Manila, Daet, Baguio City, Lucena, Isabela, and Iloilo) A A A A A A0 A1 B B B B B B B0 B1 C C C1 D D D D D D D D D1 DO E E E E E E E1 EO F F F F F1 FO G G G G

16 Figure 12. Summary of C-14 data grouped by brands (G1 to Z) (Metro Manila, Daet, Baguio City, Lucena, Isabela, and Iloilo) G1 H H H H H1 I I I1 J1 K K L L L L M N N O P Q Q Q Q R S S T T U V W Z

17 Tuba_a Tuba_b Tuba_a Tuba_a Tuba_a C-14 content of Vinegar of known origin Cane_a Cane_b Cane_b Cane_b Mango Mango_a Pineapple Pineapple Rice_a Rice_b Tuba_a Cane_a Cane_a Cane_a Cane_a

18 SUCCESS STORIES 14 C ANALYSIS OF VINEGAR PNRI EXPERIENCE 14C RADIOASSAY OF VINEGAR SAMPLES FROM MAJOR CITIES THROUGHOUT THE PHILIPPINES REVEALED THAT 7 OUT OF 10 BRANDS, WHICH HAS PASSED THE LOCAL STANDARDS FOR NATURAL VINEGAR ARE ACTUALLY ADULTERATED WITH SYNTHETIC ACETIC ACID. The method: LOW LEVEL LIQUID SCINTILLATION COUNTING

19 Radiocarbon assay of acetic acid isolated from vinegar is an alternative analytical technique which is based on lower C-14 levels in petroleum- derived synthetic acetic acid.

20 13 C/ 12 C Ratio Determination by Isotope Ratio Mass Spectrometry. DETECTION OF GEOGRAPHICAL ORIGIN, BOTANICAL ORIGIN AND PRODUCTION PRACTICES. Isotope ratio analysis

22 Mass number Atomic C H 16 O C 2 1H 17 O H C O 6 number

23 Molecular Species of Water of Practical Interest Species Mass 1 H 1 H 16 O : 18 1 H 2 H 16 O : 19 1 H 1 H 18 O : 20 1 H 3 H 16 O : 20

25 Examples of this phenomenon are: 1) 1 H 2 18 O and 1 H 2 H 16 O have lower vapour pressures than 1 H 2 16 O; they also evaporate less easily and 2) In most chemical reactions the light isotopic species reacts faster than the heavy, e.g. Ca 12 CO 3 dissolves faster in an acid solution than does Ca 13 CO 3. In an isotope equilibrium between two chemical compounds the heavy isotope is generally more concentrated in the compound having larger molecular weight. At high temperatures the differences between binding energies of isotopic molecules becomes smaller, resulting in smaller and ultimately disappearing- isotope effects.

26 Isotopes in rain get more negative further inland and at higher altitude d 18 O = 12 d 2 H = 86 d 18 O = 21 d 2 H = 158 d 18 O = 11 d 18 O = 3 d 2 H = 14 d 2 H = 78 Continent Ocean d 18 O=0 SOURCE: PRESENTATION OF DR. A. HERCZERG d 2 H=0

28 Ranges for δ 13 C values in selected natural compounds. Especially noteworthy is the spread in 13 C seen in different plant groups and resulting soil CO 2

29 Commonly used feeds in the acetous fermentation manufacture of vinegar include sugar cane, rice wine, pineapple or mango shavings, and coconut juice or sap, etc. The quality and taste are characteristic of the alcoholic liquor from which the condiment is made. Fraud may also be in the form of misrepresentation of the fine vinegars, with the cheaper and lower quality products, i.e. substitution of apple cider and balsamic vinegar with cane or other cheaper vinegars.

30 RESULTS SAMPLE DESCRIPTION C-14 Delta values CODE (dpm/g C) VI-0044 commercial cane vinegar VI-0109 commercial cane vinegar ,8 VI-0116 commercial vinegar VI-0140 commercial vinegar ,9 VI-0142 commercial vinegar ,6 VI-0152 commercial vinegar ,5 VI-0158 commercial vinegar 2,83-32,7 VI-0130 Sugar Cane Acetator ,2 VI-0131 Natural Sugar Cane ,2 VI-0135 Fresh Pineapple Juice ,9 VI-0136 Fresh Mango Natural ,1

31 ISOTOPIC RATIOS CAN GIVE INDICATIONS ABOUT THE BOTANIC AND GEOGRAPHIC ORIGIN OF PRIME MATTERS AND, IN CERTAIN CASES, ON THE TECHNOLOGICAL PROCESSES USED IN FOOD PRODUCTION.

32 Ranges in the δ 34 S content of sulphur and sulphur compounds in different materials and environments.

33 Ranges in the δ 15 N in natural materials

34 What may be analyzed: PRODUCT COMMON ADULTERATION DETECTION METHOD Fruit Juice Addition of /Dilution with Water 18 O IRMS Fruit Juice Addition of Sugar 13 C IRMS Honey Addition of Corn or Cane Sugar 13 C IRMS Vanilla Spirit Addition of Artificial Vanillin or p-hydroxybenzaldehyde Mislabelling of Botanical Origin 13 C IRMS 13 C IRMS Vegetable Addition of Cheaper Seed Oil Mass Spectrometry Oil

35 Wine Dilution with Water (D/H) and 18 O IRMS Wine Chaptalization 13 C IRMS Wine Mislabeling of Age 14 C Scintillation Counting Vinegar Vinegar Addition of or Substitution with Synthetic Acetic Acid Mislabeling of Botanical Origin 14 C Scintillation Counting 13 C IRMS Milk & Misdeclaration of Products Geographical Origin 13 C IRMS, (D/H), 18 O, 34 S, 85 Sr IRMS

36 Wine Dilution with Water (D/H) and 18 O IRMS Wine Chaptalization 13 C IRMS Wine Mislabeling of Age 14 C Scintillation Counting Vinegar Vinegar Addition of or Substitution with Synthetic Acetic Acid Mislabeling of Botanical Origin 14 C Scintillation Counting 13 C IRMS Milk & Misdeclaration of Products Geographical Origin 13 C IRMS, (D/H), 18 O, 34 S, 85 Sr IRMS

37 What may be analyzed: PRODUCT COMMON ADULTERATION DETECTION METHOD Fruit Juice Addition of /Dilution with Water 18 O IRMS Fruit Juice Addition of Sugar 13 C IRMS Honey Addition of Corn or Cane Sugar 13 C IRMS Vanilla Spirit Addition of Artificial Vanillin or p-hydroxybenzaldehyde Mislabelling of Botanical Origin 13 C IRMS 13 C IRMS Vegetable Addition of Cheaper Seed Oil Mass Spectrometry Oil

38 Wine Dilution with Water (D/H) and 18 O IRMS Wine Chaptalization 13 C IRMS Wine Mislabeling of Age 14 C Scintillation Counting Vinegar Vinegar Addition of or Substitution with Synthetic Acetic Acid Mislabeling of Botanical Origin 14 C Scintillation Counting 13 C IRMS Milk & Misdeclaration of Products Geographical Origin 13 C IRMS, (D/H), 18 O, 34 S, 85 Sr IRMS

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