1. 1 From Grape To Bottle: Avoiding Haloanisole Taint Napa Valley Wine Technical Group 26 February 2008 Eric Hervé, Ph.D. E T S Laboratories, St. Helena, CA

2. 2 1.Origins of Haloanisoles 2.Prevention at the Winery 3.Prevention of Cork Taint

3. 3

4. 4 Phenols Microorganisms Halogens Haloanisoles Halophenols The Haloanisoles Triangle

5. 5 Phenol + Chlorine => Trichlorophenol Cl OH

6. 6 “Hidden Phenols” - Wood - Water - Grape / wine - Synthetic polymers (phenolic resin)

7. 7 Halogens - Chlorine (bleach, hypochlorite)  Trichlorophenol (TCP) - Bromine (tablets)  Tribromophenol (TBP) - Iodine ?

8. 8 Microorganisms - Detoxification of halophenols  Haloanisoles

9. 9 Microorganisms - Molds/Fungi Trichoderma, Fusarium, Penicillium… (Alvarez-Rodriguez et al., 2003) - Soil bacteria Streptomyces (Mara et al., 2005)

10. 10 Phenols Microorganisms Halogens Haloanisoles Halophenols Pesticides, Flame Retardants

11. 11 Chloroanisoles in the Press France, 1998: “La maladie cachee du Vin” Wines “corked” by TeCA

12. 12 2,3,4,6- Tetrachlorophenol (TeCP) Present in pentachlorophenol - based wood preservatives Cl OH Cl

13. 13 February 2007: “Chile's Viña Errázuriz Confronts Contaminated Cellar - Problem with TBA may be widespread in Chile and Argentina“ James Molesworth

14. 14 2,4,6-Tribromophenol (TBP) Wood preservative and flame retardant Widely used in South America Beware of pallets!!! Br OH

15. 15 Vineyards Dichloran (Botran ® ) Traces of TCP, TeCP and PCP found in one sample Haloanisoles in treated moldy grapes (TCA > 20 ppt) Cl NO 2 NH 2

16. 16 1.Origins of Haloanisoles 2.Prevention at the Winery 3.Prevention of Cork Taint

17. 17 - Phenols:. few options… - Halogens:. no chlorine or bromine - Microorganisms:. humidity <70%

18. 18 - Halophenols:. Replacing bleach-sanitized items (hoses…). Checking wood materials

19. 19 Risk Assessment Visit Main Control Points: - Water - Air - Wood

20. 20 After “shock” chlorination (well, storage tanks) Water stored in wooden tanks Epoxy linings Contact with hoses Water Supply

21. 21 Concentrate airborne haloanisoles Drip pan sanitized with bromine tablets Where does the drip line go? A/C Unit Condensates

22. 22 Drains Wine and bleach mix TCP  TCA TCA volatilized and distributed by drain system

23. 23 Haloanisoles are airborne contaminants get in wine via contaminated air or materials minute amounts (ppt) needed

24. 24 Trap for Atmospheric Haloanisoles Early detection < 0.1ppbbest 0.1 - 0.3 ppb“trace amounts” (common) ~ 1.0 ppbdanger! > 1.0 ppb wine contamination probable Monitoring (efficiency of corrective actions) “Snapshots”

25. 25 Barrel runners and chocks, wood tanks, wall paneling, posts stairs, catwalks, beams and rafters, plywood ceiling … Inventory, Sampling, Analysis (haloanisoles AND halophenols)

26. 26 Barrels and Winemaking Supplies. Hot issue: TBA. Ask barrel suppliers about QA program. Citric, tartaric, bentonite, DE, filter pads… Use your nose, beware of pallets,! In doubt… test (traps, soaks, analysis)

27. 27 “moldy”, “corked” “wet concrete” “muted” 0 ~ 2 ~ 6 TCA ng/L DifferenceRecognition The Threshold Fallacy: Gradation of Sensory Effects Sub-recognition levels are of concern

28. 28 Sensory Training

29. 29 Last Line of Defense Analysis right before bottling

30. 30 Remediation Options - Whole milk (0.2 to 0.6%) - Half and half (0.2 to 0.6%) - Yeast hulls (3 to 7 pounds / 1000 Gal) - Food-grade polyethylene sheets (~ 2 sq. feet / gal) - Commercial “TCA-Removal” offerings

31. 31 1.Origins of Haloanisoles 2.Prevention at the Winery 3.Prevention of Cork Taint

32. 32 Releasable TCA (RTCA) For a cork, or group of corks, the concentration of TCA reached at equilibrium in a wine soak. Expressed in ng/L (or ppt). (Hervé E., Price S. and Burns G. - ASEV 1999) Bulk vs. Individual

33. 33 Bale G: 3.8 ng/L No clear-cut line “good cork” / “bad cork”

34. 34 Individual soaks Bulk (group) soaks

35. 35 Bottle TCA after 9 months

36. 36 www.etslabs.com Thank You!