1. 1 LONG TERM LEACHING FROM BOTTLES Prepared by Giancarlo Boschi (Calp) Presented by Pietro Stanghellini (Calp) 13 th ICF TECHNICAL EXCHANGE CONFERENCE

2. 2 INDEX MODEL A - AUTOMATIC BOTTLES: 9 YEARS STORAGE MODEL B - AUTOMATIC / HAND MADE BOTTLES: 3 YEARS STORAGE MODEL C - AUTOMATIC BOTTLES: 4 CONTACTS OF DIFFERENT DURATION MODEL D - ORDINARY AND PRETREATED BOTTLES: A 2 nd CONTACT LASTING 4 YEARS MODEL E - LEAD CRYSTAL AND BARIUM GLASS BOTTLES: LEAD AND BARIUM LEACHING 7 YEARS STORAGE

3. 3 AUTOMATIC BOTTLES AFTER 9 YEARS STORAGE WITH BEVERAGES VOLUME BEVERAGES - 700 ml 24 h ISO Test = 96  gr/Litre “new” bottles SA/V = 0.62 cm -1 TYPE BEVERAGES WHISKY pH=3.4WHISKY pH=3.4 BRANDYpH=3.8BRANDYpH=3.8 ACETIC ACID 4%pH=2. 4ACETIC ACID 4%pH=2. 4

4. 4 AUTOMATIC PRODUCTION AFTER 9 YEARS STORAGE (Model A) Lead leaching into HAc 4% is much higher than Whisky and Brandy after 6 years (+43%) Leaching in Whisky after 6 years is over 600% than leaching after ISO (96  gr/L) After 6 years Whisky and HAc were degraded, the test continued with Brandy

5. 5 AUTOMATIC vs HAND MADE PRODUCTION AFTER 3 YEARS STORAGE (Model B) “Automatic” ISO “new” 127  gr/Litre “Hand made” ISO “new” 318  gr/Litre After 3 years, Lead leaching from Hand made product is about 240% of leaching from Automatic pH BEVERAGES WHISKY (A) - 3,36 WHISKY (H) - 3,87

6. 6 REPEATED SHORT CONTACT PERIODS (2 MONTHS) WITH HAND WASHING AFTER EACH CONTACT (Model C1 ) AUTOMATIC PRODUCTION ISO Test = 241  gr/Litre for “aged” Bottles Type beverage = Whisky pH Whisky = 3.9 SA/V = 0.62 cm -1 Hand washing with mild detergent; time 30”

7. 7 REPEATED SHORT CONTACT PERIOD (2 MONTHS) WITH DISHWASHING MACHINE AFTER EACH CONTACT (Model C2) AUTOMATIC PRODUCTION ISO Test = 241  gr/Litre for “aged” Bottles Type beverage = Whisky pH Whisky = 3.9 SA/V = 0.62 cm -1 Dishwashing machine, rinsing with tap water; time 30’

8. 8 COMPARISON BETWEEN HAND WASHING (C 1) AND DISHWASHING MACHINE (C 2) As known, after the 1 st contact, Lead leaching is lower with hand washing than with dishwashing. In both cases, Lead leaching after the 3 rd contact is relatively low ( < 100  gr/L ).

9. 9 4 th CONTACT OF 3 YEARS AFTER 3 SHORT CONTACTS OF 2 MONTHS EACH (Model C3 and C4) In the case C3 (hand washing) Lead leaching after the 3 rd contact was: 33  gr/L In the case C4 (dishwashing) Lead leaching after the 3 rd contact was: 81  gr/L After the 4 th contact of 3 years Lead leaching is : C3 (hand washing) : 217  gr/L C4 (dishwashing) : 244  gr/L

10. 10 COMPARISON BETWEEN A 1 st CONTACT OF 3 YEARS vs 4 th CONTACT OF 3 YEARS AFTER 3 SHORT CONTACTS OF 2 MONTHS (Models B, C3 and C4) AUTOMATIC BOTTLES In a 3 year contact, after 3 short contacts (2 months each), Lead leaching reduces more than 50 % in both cases C3 and C4

11. 11 ORDINARY and PRETREATED (vinegar) BOTTLES: a 2 nd CONTACT LASTING 4 YEARS (Model D) AFTER THE 1 st YEAR OF CONTACT WITH WHISKY, FOR EACH TYPE OF BOTTLE (ORDINARY AND PRETREATED), 2 SAMPLES HAVE BEEN WASHED BY HAND AND 2 SAMPLES BY WASHING MACHINE (STRONG CYCLE LASTING 1h,30’); THE 8 SAMPLES HAVE BEEN RINSED BY WATER AND THEN REFILLED WITH WHISKY (pH 3.9). DURING THIS 2 ND CONTACT, 1 cc HAS BEEN EXTRACTED FOR LEAD LEACHING DETERMINATION AT 1 YEAR TIME INTERVALS.

12. 12 2 nd CONTACT LASTING 4 YEARS AFTER 1 st CONTACT OF 1 YEAR (Model D) ORDINARY BOTTLES 1 YEAR WHISKY - 426  gr/Litre D1 : HAND WASHING Pb WHISKY 1 st year - 112  gr/Litre 2 nd year - 198  gr/Litre 3 rd year - 238  gr/Litre 4 th year - 258  gr/Litre D2 :WASHING MACHINE Pb WHISKY 1 st year - 362  gr/Litre 2 nd year - 496  gr/Litre 3 rd year - 521  gr/Litre 4 th year - 548  gr/Litre PRETREATED BOTTLES 1 YEAR WHISKY - 7  gr/Litre D3 : HAND WASHING Pb WHISKY 1 st year - 8  gr/Litre 2 nd year - 8  gr/Litre 3 rd year - 8  gr/Litre 4 th year - 9  gr/Litre D4 : WASHING MACHINE Pb WHISKY 1 st year - 16  gr/Litre 2 nd year - 17  gr/Litre 3 rd year - 19  gr/Litre 4 th year - 21  gr/Litre

13. 13 HAND WASHING BOTTLES (D1) ORDINARY BOTTLES (O) 1 st YEAR - 112  gr/Litre Pb 2 nd YEAR - 198  gr/Litre Pb 3 rd YEAR - 238  gr/Litre Pb 4 th YEAR - 258  gr/Litre Pb (D3) PRETREATED BOTTLES (P) 1 st YEAR - 8  gr/Litre Pb 2 nd YEAR - 8  gr/Litre Pb 3 rd YEAR - 8  gr/Litre Pb 4 th YEAR - 9  gr/Litre Pb

14. 14 DISHWASHING MACHINE BOTTLES (D2) ORDINARY BOTTLES (O) 1 st YEAR - 362  gr/Litre Pb 2 nd YEAR - 496  gr/Litre Pb 3 rd YEAR - 521  gr/Litre Pb 4 th YEAR - 548  gr/Litre Pb (D4) PRETREATED BOTTLES (P) 1 st YEAR - 16  gr/Litre Pb 2 nd YEAR - 17  gr/Litre Pb 3 rd YEAR - 19  gr/Litre Pb 4 th YEAR - 21  gr/Litre Pb

15. 15 COMMENTS The benefits of hand washing is confirmed after the 2 nd contact, Lead leaching is : Hand washing D1 = 258  gr/L D3 = 9  gr/L Dishwashing D2 = 548  gr/L D4 = 21  gr/L D1 and D3 = about 50 % of D2 and D4 (respectively) Pre-treated Bottles show an extremely low leaching also during the 2 nd contact; probably a pre-treatment lasting less than 24 hours can be sufficiently effective and more easy to be applied; this approach can be investigated with further tests.

16. 16 LEAD AND BARIUM LEACHING FROM BOTTLES (Model E) Bottles in Barium Glass have been filled with whisky and stored for 7 years; sampling and analysis for Barium leaching determination have been carried out at 1 year time interval. The protocol is similar to Model A. Lead and Barium leaching are compared during the 7 years of test.

17. 17 BARIUM LEACHING from BARIUM GLASS BOTTLES AUTOMATIC BOTTLES ISO Ba = <10  gr/L pH Whisky Model (E) = 4,2 BaO in Barium Glass = 19%

18. 18 COMPARISON BETWEEN LEAD and BARIUM LEACHING ISO Pb Lead Crystal - 96  gr/L ISO Ba Barium Glass - <10  gr/L pH Whisky Model (A) - 3,4 pH Whisky Model (E) - 4,2 PbO Lead Crystal - 25% BaO Barium Glass - 19%

19. 19 COMMENTS Although the Barium Glass has not been specifically designed with the purpose of limiting Barium leaching, it is surprising to observe the very high increase with time of Barium leaching. Barium leaching appears to be extremely low during the ISO test (<10  gr/L), but it becomes very high in whisky after 7 years (2600  gr/L).

20. 20