Oxygen and wine
Wes Ward
April 2013
Oxygen and wine
Make
Break
Impacts depend on:
 Period of addition
 Oxygen amount
 pH
 SO2
 Temperature
 Etc…
Measurement application domain
Why measuring?
Assessing winemaking steps
Controling at different oxygen amounts (macro/micro/nano)
Assessing consistency
Degree of Oxygen Exposure
Must Preparation
Maturation (barrel aging,
micro-oxygenation)
Bottling (TPO) & Bottle Aging (OTR)
Objectives
Mapping the process and defining strategies
source Oenomeca
Process Mapping
HACCP
Electrochemical methods
Generated current is proportional
to O2 partial pressure or to mass
of O2 transformed during electrolysis
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Circulation in the cell
Destructive method
Need of inert gas
Portable
Very Accurate
1 point calibration
HS measurement possible
Luminescence Methods
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Immersion
Stirring in the tank
Non-destructive
Non-invasive depending on
device and brand
• Very Accurate
• No calibration
• Portable
Main Measurement Methods
Principle
NomaSense
Oxysense
Ocean Optics
Non-Invasive
Luminescence
Pros
Cons
Accurate
Easy to use
DO, HS, TPO
Orbisphere
Accurate for DO Difficult to use
Electrochemistry
Clark Electrode
Responsive
HS not accurate
Hach Lange
LDO
Oxybaby
Checkmate
Luminescence
Cheap
Easy to use
No HS
Only DO in
tanks
Amperometry
Cheap
Easy to use
O2 and CO2
Only HS, no DO
YSI - Probe
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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
Oxybaby
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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
Orbisphere
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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
Hach Ultra LDO
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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
Oxysense
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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
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
NomaSense
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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
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
Reproducibility in % O2
Elements of validation
1,8
1,5
1,2
0,9
0,6
0,3
0
m-GC
Orbisphere
NomaSense
0
0,1
0,2
0,3
Limit of quantification in % O2
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All technologies are very accurate
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NomaSense showing the best performances
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Broader range of application for NomaSense
0,4
Available tools
Dipping Probe
Sight Glass
Analyzer
Transparent BIB taps
Sensors
Side Glass
Different measurement approaches
Dipping Probe
Sight Glass
Sensors
Measuring in a bottle
Headspace
How much oxygen is in the bottle?
Dissolved
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Oxygen (ppm)
Selected Audit Results
14.00
12.00
HS (ppm)
10.00
DO (ppm)
8.00
6.00
4.00
2.00
0.00
Bottling Consistency
3.50
HS (ppm)
DO (ppm)
DO + HS Oxygen Pickup (ppm)
3.00
O2 difference of 0.90 ppm O2
2.50
2.00
1.50
1.00
0.50
0.00
6
9 29 4
8
5
7 17 24 3
2 20 26 30 18 27 10 14 25 19 22 28 1 21 23 16 15
Filling Head number
42
Typical DO Evolution in Bottles
Inerting before Filling
0.80
0.70
Without Inerting
Oxygen (ppm)
0.60
0.50
DO Nomacorc
DO Screwcap
0.40
0.30
0.20
With inerting
0.10
0.00
0
2
4
6
8
10
12
14
16
Inerting before filling can reduce up to 0.5 ppm
Head Space Management
for Inner Seals
No Vacuum
400.000
Pick-up = 3ppm
300.000
Oxygène dégarni (hPa)
HSO in hPa
350.000
Vacuum:
Pick-up= 1.4 ppm
250.000
Vacuum + CO2
200.000
Pick-up = 0.2 ppm
150.000
100.000
50.000
0.000
The New NomaSense O2 analyzer
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
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The only TPO meter on the market

No need to run separate calculations in
excel files