Oxygen and wine Wes Ward April 2013

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

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

Mapping the process and defining strategies 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 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 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

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

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

Different measurement approaches Dipping Probe Sight Glass Sensors

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

Selected Audit Results

Bottling Consistency O2 difference of 0.90 ppm O2 42

Typical DO Evolution in Bottles

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

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

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