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Oxygen in beverages

Introduction

In the world of beverage production, manufacturers share a common goal: ensuring top quality in their final packed products. Quality control plays an important part in the operations of beverage producers when it comes to compliance, brand reputation, cost reduction and continuous improvement.

For beverage production the knowledge about the oxygen concentration at several production steps is crucial for quality control. Whether in beer, wine, mineral water or soft drinks, the oxygen content has to be monitored in order to produce and maintain the best possible quality and keep the customers’ confidence high.

Monitoring oxygen means measuring the concentration of O2 in a certain unit, like parts per billion, over time in order to continuously observe changes. By measuring key parameters throughout the production process, it is possible to detect deviations from target values, react at an early stage and take corrective measures. (Rana, et al. 2019)

It is essential to identify the source of the oxygen ingress, in order to be able to attribute the deviation to a specific step in the process chain. Since O2 can either be found as “dissolved oxygen” in the liquid or as gas in the headspace of the final product, the root cause of the ingress can be identified by measuring both. Dissolved oxygen and headspace oxygen concentrations constitute the “total package oxygen” as depicted in Figure 1. (Janßen und Dr. Biebernik 2019)

Figure 1: Schematic of a bottle indicating headspace oxygen, dissolved oxygen and total package oxygen.

Oxygen in liquids and beverages

What is the role of oxygen?

Oxygen is a key quality control parameter because it can negatively affect the final product in many ways. Therefore, it needs to be closely monitored. Oxygen can lead to reduced shelf life, flavor deterioration, alteration of color, and degradation of certain ingredients.

The physical and chemical impact of oxygen has different root causes, depending on the product and package type. In the case of beer, the presence of yeast leads to oxygen consumption, and thus to a reduction in the oxygen concentration. In soft drinks, on the other hand, the decrease in oxygen content over time is caused by the oxidation process of ingredients such as fruit juices, vitamins and flavors. Soft drink producers often aim for the so called “air in can” amount, which is defined as the air content present within the whole package, including nitrogen and oxygen gas.

For products packed in metal cans, dissolved oxygen is the main cause of corrosion, making it an even more important key parameter in quality control. The corrosion process is accelerated with higher oxygen concentrations, significantly affecting the quality of the final product. Monitoring and controlling the oxygen content in the packaging step is crucial for preventing corrosion. (Davis 1999)

Measuring oxygen

Measurement methods

Oxygen concentrations can be measured using different techniques. The most relevant methods are: 

  • Chemical analysis (Winkler titration)
  • Electrochemical method (Electrode)
  • Optochemical method (Optode)

While instruments based on chemical analyses are no longer state-of-the-art, electrochemical and optical methods are precise and accurate measuring techniques used in many different instruments.

However, conditions that contribute to accuracy must be considered, including proper standard operating procedure upon usage, sensor geometry and design, environment, and calibration/adjustment. 

The advantages of the optochemical method are:

  • No consumption of oxygen during measurement
  • No stirring necessary 
  • No use of chemicals

Optochemical measuring method – Luminescence quenching

Sensors based on optochemical methods consist of a luminescent dye on a carrier material. The sensor is in direct contact with samples, either in the liquid or gaseous phase. 

An optochemical oxygen sensor works by using a special dye that fluoresces when exposed to light. When there is oxygen around, it interacts with the dye and reduces the fluorescence through a process called dynamic quenching. The higher the level of oxygen, the less the dye will fluoresce. By measuring the intensity of the fluorescence, it is possible to determine how much oxygen is in the environment.

The correlation between O2 concentration and emission intensity is summarized in Table 1. 

  Oxygen Concentration Emission Conclusion
1 High Low The more O2 molecules are present, the more energy will be transferred and absorbed.
I.e., the more O2 molecules are present, the less light will be emitted.
2 Low High

 

More information can be found here: Optochemical oxygen sensor

Oxygen monitoring points in the production process

The key production steps for oxygen monitoring depend on the industry. Table 2 summarizes the steps where oxygen monitoring is necessary within the production of beer

Table 2: Key steps including oxygen monitoring throughout beer production.

Industry Production step Description Impact
Beer Wort Production Oxygen monitoring after boiling and cooling. Excessive dissolved oxygen at this stage leads to oxidation of wort components, off-flavor and decreased stability.
Fermentation Cooled wort is transferred to fermentation vessels, where yeast is added. Excessive oxygen can lead to reduced yeast performance.
Storage Tank Tanks are purged with inert gas and sanitized. Beer is then transferred from the fermentation tank to the storage tank.  Excessive oxygen levels can impact carbonation levels and also lead to oxidation processes.
Packaging Beer is ready for packaging into bottles, cans and kegs. After filling, the package is sealed and labeled. Excessive oxygen can cause flavor degradation and reduce shelf life.
Storage – Post packaging  Packed beer is stored in warehouses before distribution, during which oxygen ingress needs to be prevented.

 

Table 3 and Table 4 summarize the steps where oxygen monitoring is necessary within production of soft drinks and wine, respectively. 

 

Table 3: Key steps including oxygen monitoring throughout soft drink production.

Industry Production step Description Impact
Soft drink Process water treatment Water as an ingredient needs to be controlled and checked for quality standards. Excessive oxygen can affect flavor and stability of final product.
Blending and carbonation Various ingredients are mixed together in precise proportions. Carbon dioxide gas is being dissolved into liquid. Excessive oxygen can affect the efficiency of the carbonation process.
Filling and packaging Soft drink mixture is ready for packaging into bottles, cans and kegs. After filling the package is sealed and labeled. Excessive oxygen can cause oxidation of ingredients and reduce shelf life.
Storage Packed products are stored in warehouses before distribution, during which oxygen ingress needs to be prevented.

 

Table 4: Key steps including oxygen monitoring throughout wine production

Industry Production step Description Impact
Wine Fermentation Must, which contains acids, sugars and other compounds, undergoes fermentation. Yeast converts sugar into alcohol and CO2. Excessive oxygen affects activity of yeast, may cause formation of unwanted by-products and leads to oxidation of the ingredients.
Filtration and stabilization Removal of remaining solids, bacteria and yeast. Excessive oxygen impacts the stability of wine and leads to further oxidation.
Maturation and aging Development of complexity and character of wine in aging vessels. Wine interacts with oxygen. Oxygen in aging vessel influences flavor, texture and aroma. Controlling the O2 content ensures the development of desired characteristics.
Bottling Wine is ready to be filled in corked or capped bottles and labeled. Excessive oxygen in final product leads to enhanced (unwanted) oxidation of the wine.

Dissolved oxygen and headspace oxygen – total package oxygen (TPO)

As shown in Figure 1, the total package oxygen is the sum of headspace oxygen and dissolved oxygen. Either the gas molecules are dissolved in the liquid or they are present as part of the overall gas constitution in the headspace, e.g. besides nitrogen gas. 

The solubility of oxygen in liquid phases is highly dependent on temperature, pressure and the composition of the liquid. It is expressed as the gas absorption coefficient ξ in [g/L*bar], a substance-specific quantity that decreases with higher temperatures. (Biebernik 2018)

The absorption coefficient for oxygen in water at 20 °C and a pressure of 1 bar is 0.0433 g/L*bar, while at 
5 °C it is 0.0603 g/L*mol. (Biebernik 2018)

The distribution of oxygen between dissolved oxygen and headspace oxygen can vary depending on the sample (e.g. beer or soft drink), container types (e.g. metal cans or glass bottles) and size. 

Figure 2 and Figure 3 illustrate examples of typical oxygen distribution in beer samples packaged in various types and sizes of containers.  For metal cans, the majority of oxygen is found in the headspace, with 76 % and 82 %, respectively (Figure 2). Similarly, for glass bottles, 75 % and 68 % of the oxygen is found in the headspace. (Figure 3). This results in an average ratio of headspace oxygen to dissolved oxygen of 3:1 for beer samples. 

Figure 2: Oxygen distribution of beer samples filled in metal cans. Column on left showing package size 12 fl. oz. and column on right showing 19.2 fl. oz.

Figure 3: Oxygen distribution of beer samples filled in glass bottles. Column on left showing package size 12. fl. oz. and column on right showing samples filled in aluminum bottles of size 16 fl. oz.

An exemplarily schematic description of oxygen ingress throughout the production process of soft drinks is depicted in Figure 4 and Figure 5 and divided into dissolved oxygen (DO) and headspace oxygen (HSO). The figures show at which manufacturing process step (x-axis) increased oxygen content will be measured (y axis).

Figure 4: Simplified graph visualizing sources of dissolved oxygen (DO) increase due to e.g. process water, raw materials (syrup), and defect filler head gaskets and their impact on the total package oxygen value.

Figure 5: Simplified graph showing sources of increased headspace oxygen (HSO) and its influence on the total package oxygen values.

For example, if there are issues with the syrup mixing, this will result in increased dissolved oxygen readings, whereas problems with package seaming lead to increased headspace oxygen values. 
Moreover, hardware-related issues can also contribute to elevated oxygen levels, such as: 

  • De-aeration systems
  • Insufficient purging of tanks and pipes upon storage 
  • Leaking pumps, valves and pipes
  • Issues with filtration aid dosing systems 
  • Outdated separator systems 

Influences on oxygen measurements

Instruments based on optical oxygen sensors may display different influencing factors compared to other techniques. Some factors which contribute to accuracy and reproducibility are summarized in Table 5.

Table 5: Influencing factors on oxygen measurements and their origin.

  Factor What is causing the error? Why?
1. Calibration/Adjustment Wrong adjustment  Faultily-adjusted sensors give wrong absolute readings of oxygen partial pressure.
2. Interference Carrier gas If the carrier gas used to operate the instrument contains O2, the results will be inaccurately high.
3. Humidity High humidity  High levels of humidity, due to insufficient drying, can cause compromised results and increase uncertainties in data.
4. Sample preparation Oxygen distribution  Some techniques require certain sample preparation in order to measure accurately. E.g., to measure dissolved oxygen, it might be necessary to shake the container for 3 minutes in order to equilibrate the sample 
5. Cleaning  Residues  Optical measuring techniques require cleaning procedures in order to keep the accuracy of the measurement high.

 

Influencing factor: Sample preparation

The overall total package oxygen within a package always stays constant. Depending on how the package was handled and whether/how the package (=sample) was prepared, different levels of dissolved oxygen and headspace oxygen can be expected. So, to conclude, there can be a transfer of oxygen between dissolved oxygen (DO) and headspace oxygen (HSO). However, the total packaged oxygen (TPO) value always remains the same.

Once the package is filled with product (e.g. beer, soft drink, etc..) the gas and liquid phase start to equilibrate. (Biebernik 2018) The distribution between gas and liquid phase can change significantly. It changes over time and is influenced by e.g. agitation. 

Figure 6 and Figure 7 show the distribution of a soft drink sample before and after shaking the sample for 3 minutes and 1 minute respectively. 

Figure 6: Oxygen distribution between gas phase (headspace) and dissolved (liquid). Left column showing the distribution directly after filling into 33 cl metal cans. Right column shows distribution after shaking samples for 3 min.

Figure 7: Oxygen distribution between gas phase (headspace) and dissolved (liquid). Left column showing the distribution directly after filling into 33 cl metal cans. Right column shows distribution after shaking samples for 1 min.

After filling the soft drink into the package, the ratio between headspace oxygen and dissolved oxygen is approximately 0.9:1. After sample preparation, the oxygen molecules will migrate from the liquid into the headspace. However, the overall total package oxygen concentration will remain constant

Applications

In addition to the typical applications that mainly measure dissolved oxygen concentration in-line, at-line or in the laboratory environment within industries such as soft drink, beer and wine production, there is a constant need for oxygen measurement in various other applications. 

Headspace and total package oxygen concentrations are becoming increasingly significant. Monitoring these parameters, in addition to dissolved oxygen, provides insights and information on which manufacturing process needs to be verified for proper functioning.

The demand for oxygen monitoring in the food industry is increasing, since the presence of oxygen may contribute to microbial growth and cause oxidation of e.g. fats and proteins. 
Examples of possible applications include: 

  • Tetra-Pak packages 
  • Plant-based drinks 
  • Milk 

Further industries where dissolved oxygen measurement is relevant are:

  • Power plants
  • Pharmaceutical industry
  • Medical research industry

Conclusion

In quality control within the beverage industry, the measurement of dissolved oxygen is a fundamental requirement. This critical parameter holds significant importance due to the substantial impact on the final products. Maintaining low levels of oxygen throughout the manufacturing process is the goal, meaning continuous monitoring is necessary. 
Through effective control of this variable, beverage producers can uphold superior quality standards, reduce costs and consistently meet customers’ expectations. Filling and packaging processes, particularly, can be optimized and errors can be detected immediately at the production line by continuous monitoring of dissolved oxygen, headspace O2 and total package oxygen. 

Manufactures are investing in instruments that enable accurate and precise measurements to meet the requirements and demands. State-of-the-art technologies like luminescence quenching in optochemical sensors are indispensable for achieving the necessary accuracy and precision. 

Such sensors can be used either in-line, at-line or in the laboratory environment, providing a comprehensive overview across the entire production line. 

For more information about carbon dioxide in beverages, see the corresponding Anton Paar Wiki Article: Carbon Dioxide in beverages.

References

Biebernik, Karin. "TPO: Getting the Whole Picture." Brauwelt International, 2018: 38-41.
Davis, J. R. Corrosion of Aluminum and Aluminum Alloys. ASM International, 1999.
Howard, G. A., and J. D. R Mawer. "The determination of dissolved oxygen in beer." J. Inst. Bew. , October 4, 1976: 144-152.
Janßen, Georg, und Karin Dr. Biebernik. "Oxygen the importance of measurement in soft drinks." Soft Drinks International, Oktober/November 2019: 74-77.
Merima Cajlakovic, Alessandro Bizzarri, Christian Konrad, Hannes Voraberger. "Optochemical Sensors Based on Luminescence." (American Scientific Publishers) 7, 2006.
Rana, Muhammad Aadil, Muhammad Madni Ghulam, Roobab Ume, ur Rahman Ubaid, and Zeng Xin-An. Quality Control in the Beverage Industry. Academic Press, 2019.