Ozone Technology for Foods

Valente B. Alvarez Food Industries Center Department of Food Science and technology

Ozone Technology for Foods

Contents Ozone O3 generation methods Applications Advantages and disadvantages

V.B. Alvarez/Ozone Tech/10-2007

Ozone
Ozone is an unstable form of consisting of 3 oxygen atoms (O3). oxygen

It reacts with other gases changing their chemical structure. As ozone oxidizes/disinfects, it destroys odorcausing and toxic gases, and then reverts to normal oxygen.

Where can ozone be found?

(Mustafa, 1990)

In the Stratosphere In photochemical smog

Ozone can be produced in UV sterilization lamps High voltage electric arcs Gamma radiation plants

V.B. Alvarez/Ozone Tech/10-2007

Ozone generation
Diatomic oxygen molecule splits Resulting free radical oxygen reacts freely with another diatomic oxygen to form triatomic ozone molecule

Properties of ozone

Nearly colorless gas at room temperature Has a pungent, charateristic odor (similar to fresh air after thunderstorm) Readily detectable at 0.01-0.05ppm Has a longer half-life in the gaseous state than in aqueous solution Ozone solubility in water is 13 times that of oxygen at 030C (Rice, 1986) Ozone cannot be stored since ozone spontaneously degrades back to oxygen atoms

V.B. Alvarez/Ozone Tech/10-2007

Corona discharge method to initiate free radical

High tension and low tension (ground) electrode separated by a ceramic dielectric medium and narrow discharge gap When the electrons have sufficient kinetic energy (@ 6-7eV), oxygen molecule dissociates Molecules of ozone are formed with new oxygen atom Ozone production rate:

1-3% if air is the feed gas 6% if pure oxygen is the feed gas Commercial method

Methods to initiate free radical oxygen formation

Corona discharge (CD) method
Heat Electrode (high tension)

O2

Discharge gap

Ceramic Ceramicdielectric medium Dielectric O3

Heat

Electrode (low tension)

V.B. Alvarez/Ozone Tech/10-2007

Advantages of CD ozone generation

Corona discharge ozone generators can use oxygen preparation thereby doubling the ozone output per given volume vs. dry air Small construction allowing generator to be installed in virtually any area Creates a more pure form of ozone without creating other harmful or irritating gases Corona cell life can exceed ten years Can create high quantities of ozone (up to 100-lbs/day) Can be more cost-effective than UV-ozone generation

UV/Ozone: How does it work?

Organic contaminant molecules are excited or dissociated by the absorption of UV (188 or 254 nm). The excited contaminants react with the atomic oxygen to form volatile products, such as CO2, H2O, etc. The whole process takes place in one to several minutes at room temperature.

V.B. Alvarez/Ozone Tech/10-2007

Comparison of UV Vs CD
Maximum ozone production rate is two grams/hr per UV bulb depending on size Highest concentration of ozone that can be produced by 185-nm UV lamp is 0.2 percent by weight, approximately 10% of the average concentration available by corona discharge Considerably more electrical energy is required to produce a given quantity of ozone by UV radiation than by corona discharge Lower gas phase concentrations of ozone generated by UV radiation translate into the handling of much higher gas volumes than with CD-generated ozone UV lamps require periodic replacement

Ozone Vs Oxygen
Property
Molecular formula Molecular weight Color Smell Solubility in water (@ 0C) Density (g/l) Electrochemical potential, V

Ozone
O3 48 Light blue Smell after lightning storms 0.64 2.144 2.07

Oxygen
O2 32 Colorless Odorless 0.049 1.429 1.23

V.B. Alvarez/Ozone Tech/10-2007

Status of ozone in the food industry

1982 - O3 declared GRAS for treatment of bottled water (Federal Register, Vol. 47, No. 113, November 5, 1982) 1997 - Expert panel report : Evaluation of the history and safety of ozone in processing foods for human consumption. Vol. 2 : Abstracts. Electric Power Research Institute,
Palo Alto, CA. R & D Enterprise, Inc. / GRAS self declaration (Federal Register, v. 62 #74, April 19, 1997)

2000 - FDA and USDA approval granted.

Potential applications in the food industry

Microbial destruction Food surface hygiene Sanitation in food plant equipment Reuse of waste water Lowering BOD and COD of food plant waste Germicide in cold storage plants Shelf life extension of fruits and vegetables

V.B. Alvarez/Ozone Tech/10-2007

Antimicrobial mechanism of ozone

(Victorin, 1992)

Destroys microorganisms by progressive oxidation of vital cellular components First, ozone oxidizes sulfhydryl groups and amino acids of enzymes, peptides and proteins to shorter peptides. Second, ozone oxidizes polyunsaturated fatty acids to acid peroxides Ozone degradation of the cell envelope unsaturated lipids results in cell disruption and subsequent leakage of cellular contents

Ozone effectiveness
As a comparison based on 99.99% of bacterial concentration being killed and time taken: Ozone is 25 times of that of HOCl (Hypochlorous Acid) 2,500 times of that of OCl (Hypochlorite) 5,000 times of that of NH2Cl (Chloramine). Further more, ozone is at least 10 times stronger than chlorine as a disinfectant. Ozone does not leave any trace of residual product upon its oxidative reaction.

V.B. Alvarez/Ozone Tech/10-2007

Oxidation mechanism of ozone

Use of ozone for food hygiene

Acc. To the Code of Federal Regulations (USDA, 1997), there must be at least 60% reduction in total microorganisms and similar reduction in coliforms, E.Coli, and Salmonella spp. Direct application of ozone to poultry carcasses destroyed more than 2 log-units of all carcass microorganisms with no significant lipid oxidation, offflavor development or loss in carcass skin color (Sheldon and Brown, 1986) Shelf life of fruits and vegetables increased due to oxidation of ethylene (Rice, et.al.,1982)

V.B. Alvarez/Ozone Tech/10-2007

Treatment of beverage waters

Ozone as a replacement for the prechlorinating step Sanitizing the granular activated carbon (GAC) filters Sanitization of bottles prior to filling with the soft drink Sanitization of fill lines and vessels

Oxidizing agents and their oxidizing potential

(Manley and Niegowski, 1967)

Oxidizing agent Fluorine Ozone Permanganate Chlorine oxide Hypochlorous acid Chlorine gas

Oxidizing potential (mV) 3.06 2.07 1.67 1.50 1.49 1.36

V.B. Alvarez/Ozone Tech/10-2007

10

Food plant equipment sanitation methods

Thermal sanitation very expensive Radiation methods not practical Chlorine has many disadvantages:
Harmful and irritating in high conc. Prone to forming carcinogenic compounds Toxic to the environment

When to apply ozone?

At pre-processing stage, during processing, or on the finished product while at storage Advantageous to apply ozone on the raw than the processed product e.g., Whole grains require less ozone to disinfect than the powder product

V.B. Alvarez/Ozone Tech/10-2007

11

Advantages
More powerful oxidizer available Instantly destroys microbes eliminates chemical storage environmentally friendly stops mold spores does not affect product taste no harmful by-products can be used in air and water

Drawbacks

No residual antimicrobial effect during storage of treated food. Cannot be stored and therefore, should be produced on site.

V.B. Alvarez/Ozone Tech/10-2007

12

Safety on exposure to ozone

In the US, current exposure level-time weighted average (PEF-TWA) in the work environment is 0.1 ppm (8-h day/40-h working week) Short term exposure limit is 0.3 ppm for an exposure less than 15 min and four times per day Recommended by American Conference of Governmental Industrial Hygienists (ACGIH, 1986) and adopted by the United States Occupational Safety and Health Administration (OSHA)

Ozone technology for foods

Summary
Ozone Generation methods Advantages and disadvantages Applications

V.B. Alvarez/Ozone Tech/10-2007

13

References
Kim, J.-G., Yousef, A.E., and Khadre, M. H. 2003. Ozone and its current and future application in the food industry, p. 167-218. In S. Taylor (ed.). Advances in food science and nutrition, Vol 45. Elsevier Sci. Ltd., London, UK Manley,T.C and Niegowski, S.J. 1967. Ozone. In Encyclopedia of chemical technology (Vol.14, 2nd ed., pp410-432). Wiley: New York, NY. Sheldon,B.W., and Brown,A.L. 1986. Efficacy of ozone as a disinfectant for poultry carcasses and chill water. Journal of Food Science, 51(2), 305-309 USDA. Code of Federal Regulations, Title 9, Part 381.66-poultry products; temperatures and chilling and freezing procedures. 1997. Office of the Federal Registrar National Archives and Records Administration,Washington,DC. Victorin,K. 1992. Review of the genotoxicity of ozone. Mutation Research, 277, 221-238. Zepnep, B.G., Annel, K.G., and Seydim,A.C. 2004. Use of ozone in the food industry. Lebensm.-Wiss.u.-Technol. 37, 453-460.

Break

V.B. Alvarez/Ozone Tech/10-2007

14

Modified Atmosphere Packaging

Valente B. Alvarez Food Industries Center Department of Food Science and technology

Modified Atmosphere Packaging (MAP)

Modified atmosphere packaging (MAP)
Enclosure of food in a package in which the atmosphere inside the package is modified with respect to CO2, O2, N2, water vapor and trace gases Generally achieved by removing air and replacing it with a controlled mixture of gases

V.B. Alvarez/Ozone Tech/10-2007

15

Background
Known for over 100 years that the preservative effect of chilling can be greatly enhanced when it is combined with control or modification of the gas atmosphere surrounding the food. Air composition: 78% nitrogen, 21%, oxygen, 0.9% argon, 0.3% carbon dioxide, and traces of nine other gases Atmosphere is changed by increasing or decreasing the concentration of O2, and/or by increasing the concentration of CO2

Important Factors of MAP

1. Temperature 2. Choice of gas 3. Choice of packaging material 4. Choice of packaging machinery

V.B. Alvarez/Ozone Tech/10-2007

16

Temperature
Holding food at low temperatures Biostatic effects of CO2 are temperature dependent O2 present in the package
Growth of aerobic spoilage organisms Absence of O2 will favor the growth of anaerobic microorganisms Aerobic and anaerobic pathogens can grow at temperatures as low as 4C and produce toxins

Choice of gas
Depends largely on the nature of the food and its principal mode(s) of deterioration Carbon dioxide is highly soluble in water and oils. It is absorbed by the food until equilibrium is attained The internal atmosphere will be modified by the food during storage Dissolution of CO2 in water lowers the pH and consequently slows reaction rates.

V.B. Alvarez/Ozone Tech/10-2007

17

Choice of packaging material

A low water vapor transmission rate and a high gas barrier MAP packages are based on thermoplastic polymers. Such materials allow some gas transmission, even at low temperatures Mechanical strength to withstand machine handling and subsequent storage, distribution and retailing Materials in use are Laminations or co extrusions of polyethylene with:
Polyester or nylon, with or without the addition of a high barrier layer of vinylidene chloride/vinyl chloride copolymer or ethylene/vinyl alcohol copolymer, depending on the barrier required

Choice of packaging machinery

Related to the two methods of packaging employed:
Thermoforming
use of a rigid or semi-rigid base material which is thermoformed into a tray

Pillow packaging
Horizontal form-fill-seal machine employs a single reel of flexible packaging material

V.B. Alvarez/Ozone Tech/10-2007

18

Modified Atmosphere Packaging (MAP)

Modified Atmosphere Packaging
Flushing of food packaging with antimicrobial gases just before sealing 40 - 1100 ppm

Shelf-life Extension of Cottage Cheese With CO2 Injection

Control
70

CO2 Injection

Shelf life (days)

60 50 40 30 20 10 0

Plant A Plant B

Plant C

Commercial Dairy Plants

V.B. Alvarez/Ozone Tech/10-2007

19

MAP
The gas enters microbial cells, lowering the pH so that microbes can no longer grow. Disadvantage: Gas dissipates quickly during modern processing

Modified Atmosphere Packaging

Extends shelf-life of solid dairy foods Shredded cheese Increased the shelf life by 2-3 times Had no effect on the product's flavor.

V.B. Alvarez/Ozone Tech/10-2007

20

Modified Atmosphere Processing

Cottage cheese Fluid Milk Yogurt Sour cream Ice cream Requirement
packaging the product in high-barrier materials

Fresh meat
Atmospheres of about 30% CO2 and up to 70% O2
Extend the color stability and delay microbial spoilage of display-packaged meat

100% nitrogen
As effective as vacuum for storing fresh meat joints

100% carbon dioxide around fresh meat

V.B. Alvarez/Ozone Tech/10-2007

21

Fish
Fillets of fresh fish in MAPs stored continuously at temperatures below 4 oC are available in Europe Effective gas compositions vary according to fish species
Low O2 concentrations are used with fatty fish which are susceptible to oxidative rancidity For non/fatty fish would be 30% O2, 40% CO2 and 30%N2, For smoked fatty fish 40% CO2 and 60% N2.

Real-time Oxygen Monitoring for MAP

Real-time oxygen monitoring for MAP in both batch process and form, fill and seal MAP machines. No sample atmosphere extraction Can take and log measurements every second

V.B. Alvarez/Ozone Tech/10-2007

22

References
Brody, A.L. (ed.) (1989). ControIledlModified AtmospherelVacuuln Packaging of Foods, Food & Nutrition Press, Inc., Trumball, Connecticut, USA. Farber, J .M. (1991). Microbiological aspects of modifiedatmosphere packaging technology -a review. J. Food Protect. 54: 58-70. Gill, c.a. (1990), Controlled atmosphere packaging of chilled meat. Food Control 2, 74-78. Inns, R. (1987). Modified atmosphere packaging. ln Modern Processing, Packaging and Distribution Systems for Food, F.A. Paine (ed.), Blackie and Son Limited, Glasgow, Great Britain, chap. 3.

V.B. Alvarez/Ozone Tech/10-2007

23