Oxygen and wine

Wes WardApril 2013

Oxygen and wine

Make Break

Color stabilityReduction of astringency

BrowningOrganoleptic

defaults

Micro-organism growth

Aroma profile evolution

Impacts depend on:

Period of additionOxygen amountpHSO2TemperatureEtc…

Must Preparation

Maturation (barrel aging, micro-oxygenation)

Bottling (TPO) & Bottle Aging (OTR)

Deg

ree

of

Oxy

gen

Exp

osu

re

Measurement application domain

Why measuring?

Assessing winemaking stepsControling at different oxygen amounts (macro/micro/nano)Assessing consistency

ObjectivesMapping the process and defining strategies

Process MappingHACCP

source Oenomeca

Electrochemical methods

Generated current is proportional to O2 partial pressure or to massof O2 transformed during electrolysis

• Circulation in the cell• Destructive method• Need of inert gas• Portable• Very Accurate• 1 point calibration• HS measurement possible

Luminescence Methods

• Immersion• Stirring in the tank• Non-destructive• Non-invasive depending on

device and brand• Very Accurate• No calibration• Portable

Main Measurement Methods

Principle Pros Cons

NomaSenseOxysense

Ocean Optics

Non-InvasiveLuminescence

AccurateEasy to useDO, HS, TPO

OrbisphereClark Electrode

Electrochemistry

Accurate for DOResponsive

Difficult to useHS not accurate

Hach Lange LDO

LuminescenceCheapEasy to use

No HSOnly DO in tanks

OxybabyCheckmate

AmperometryCheapEasy to useO2 and CO2

Only HS, no DO

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

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

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

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

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

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

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

Elements of validation

0

0,3

0,6

0,9

1,2

1,5

1,8

0 0,1 0,2 0,3 0,4Limit of quantification in % O2

Rep

rod

uci

bil

ity

in %

O2

-GC

NomaSense Orbisphere

All technologies are very accurate NomaSense showing the best performances Broader range of application for NomaSense

Available tools

Analyzer

Dipping Probe

Sensors

Sight Glass

Side GlassTransparent BIB taps

Different measurement approaches

Dipping Probe Sight Glass Sensors

Measuring in a bottle

Headspace

DissolvedHow much oxygen is in the bottle?

Selected Audit Results

0.00

2.00

4.00

6.00

8.00

10.00

12.00

14.00

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59

Oxy

ge

n

(pp

m)

HS (ppm)

DO (ppm)

Bottling Consistency

0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

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

DO

+ H

S O

xyg

en P

icku

p (

pp

m)

HS (ppm)DO (ppm)

O2 difference of 0.90 ppm O2

42

Typical DO Evolution in Bottles

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0 2 4 6 8 10 12 14 16

Oxy

gen

(p

pm

)

DO Nomacorc

DO Screwcap

Inerting before Filling

With inerting

Without Inerting

Inerting before filling can reduce up to 0.5 ppm

Head Space Management for Inner Seals

0.000

50.000

100.000

150.000

200.000

250.000

300.000

350.000

400.000

Oxy

gèn

e d

égar

ni

(hP

a)

No Vacuum

Pick-up = 3ppm

Vacuum + CO2

Pick-up = 0.2 ppm

Vacuum:

Pick-up= 1.4 ppm

HS

O i

n h

Pa

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

The only TPO meter on the market No need to run separate calculations in excel files