1. Oxygen and wine
Wes Ward
April 2013

2. Make Break Oxygen and wine Impacts depend on: Micro-organism growth
Period of addition
Oxygen amount pH
SO2
Temperature
Etc…
Color stability
Reduction of astringency
Browning
Organoleptic defaults
Micro-organism growth
Aroma profile evolution

3. Measurement application domain
Why measuring?
Assessing winemaking steps
Controling at different oxygen amounts (macro/micro/nano)
Assessing consistency
Must Preparation
Maturation (barrel aging, micro-oxygenation)
Bottling (TPO) & Bottle Aging (OTR)
Degree of Oxygen Exposure

4. Mapping the process and defining strategies
Objectives
Mapping the process and defining strategies
source Oenomeca
Process Mapping
HACCP

5. Electrochemical methods
Generated current is proportional to O2 partial pressure or to mass of O2 transformed during electrolysis
Circulation in the cell
Destructive method
Need of inert gas
Portable
Very Accurate
1 point calibration
HS measurement possible

6. Luminescence Methods Immersion Stirring in the tank Non-destructive
Non-invasive depending on device and brand
Very Accurate
No calibration
Portable

7. Main Measurement Methods
Principle
Pros
Cons
NomaSense
Oxysense
Ocean Optics
Non-Invasive
Luminescence
Accurate
Easy to use
DO, HS, TPO
Orbisphere
Clark Electrode
Electrochemistry
Accurate for DO
Responsive
Difficult to use
HS not accurate
Hach Lange
LDO
Cheap
No HS
Only DO in tanks
Oxybaby
Checkmate
Amperometry
O2 and CO2
Only HS, no DO

8. YSI - Probe Method – Electro-chemistry Evasive Somewhat Portable
Can measure both Dissolved O2 Only
Detection Limit of .001 ppm (1ppb)
Detection Limit - 0–20ppm
Accuracy +/- .01ppm
No cross sensitivity to C02 or SO2
Food Certified
Primary Industry – Water

9. Oxybaby Method – amperometry – probe only Invasive – probe only
Portable
Cannot measure Dissolved O2
Can measure Headspace O2 only
No In-line measurement
Detection Limit of .1% O2
Detection Limit – 0-100% O2
Accuracy .10%
No cross sensitivity to C02 or SO2
Headspace only with Bag-in-Box applications
Not food certified, probe only
Primary Industry – Food Packaging

10. Orbisphere Method – Electro-chemistry – no dipping probe Invasive
Portable, but usually fixed (lab application)
Can measure Dissolved O2
Extremely difficult to measure headspace O2
In-line only
Detection Limit of .001 ppm (1ppb)
Detection Limit – 0-20ppm
Accuracy <= 1% of reading
No cross sensitivity to C02 or SO2
Ability to measure Bag-in-Box applications
Not food certified, it is a destructive test
Primary Industry - Beverage

11. Hach Ultra LDO Method – Luminescence – dipping probe only Invasive
Portable
Can measure Dissolved O2 – No HS
In-line not possible
Detection Limit of .001 ppm (1ppb)
Detection Limit – 0-20ppm
Accuracy <= .2ppm
Low sensitivity to C02 or SO2
Not able to measure with Bag-in-Box applications
Not food certified, it is a destructive test
Primary Industry – Waste Water

12. Oxysense Method - Luminescence – sensor spots, Non-invasive
Not truly portable
Can measure Dissolved O2 & Headspace O2
Can measure In-line
Detection Limit of .015 ppm (15ppb)
Detection Limit – 0-15ppm
Accuracy <= 5% of reading
Cross sensitive to C02 or SO2
Light interferences
Bag-in-Box applications possible
Not food certified
Primary Industry – Food Packaging

13. Ocean Optics – Neofox
Method – Luminescence – sensor spots & dipping probe
Non-Invasive
Portable, but requires a PC to read
Can measure Dissolved O2 & Headspace O2
In-line ability
Detection Limit of .04 ppm (40ppb)
Detection Limit – 0-40ppm
Accuracy <= 5% of reading
Cross sensitivity to C02 or SO2 is unknown
Sensors susceptible to ethanol
Bag-in-Box applications possible
Not food certified
Primary Industry – Waste Water

14. NomaSense Method – Luminescence (sensor spots & dipping probe)
Non-destructive & Non – Invasive
Very Portable
Can measure both Dissolved O2 & Head Space O2
Can measure in-line
Detection Limit of .001 ppm (1ppb)
Detection Limit - 0–40ppm
Accuracy <= .01ppm
No cross sensitivity to C02 or SO2
Ability to measure Bag-in-Box applications
Food Certified
CIP possible
Primary Industry – Wine
Fully validated for wine applications

15. Validation procedure Certified gases (GEC) ranging from 0 to 21% O2
Experimental set-up for both
Head space and dissolved oxygen
Procedure MA-F-AS1-06-PROVAL
recommended by the OIV
 Linearity, repeatability, reproducibility
LOD, LOQ, selectivity and accuracy

16. Elements of validation
m-GC
NomaSense
Orbisphere
All technologies are very accurate
NomaSense showing the best performances
Broader range of application for NomaSense

17. Available tools Sight Glass Dipping Probe Analyzer Side Glass Sensors
Transparent BIB taps

18. Different measurement approaches
Dipping Probe
Sight Glass
Sensors

19. How much oxygen is in the bottle?
Measuring in a bottle
Headspace
How much oxygen is in the bottle?
Dissolved 19

20. Selected Audit Results

21. Bottling Consistency
O2 difference of 0.90 ppm O2 42

22. Typical DO Evolution in Bottles

23. Inerting before Filling
Without Inerting
With inerting
Inerting before filling can reduce up to 0.5 ppm

24. Head Space Management for Inner Seals
No Vacuum
Pick-up = 3ppm
Vacuum:
Pick-up= 1.4 ppm
Vacuum + CO2
Pick-up = 0.2 ppm
HSO in hPa

25. The New NomaSense O2 analyzer

26. The New NomaSense O2 analyzer
2nd Generation NomaSense
Overall reduction in size & weight
More intuitive user interface
New calibration management through bar code reading
New sensor management via new file structure
Compatible with existing sensors and accessories
The only TPO meter on the market
No need to run separate calculations in excel files