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April 2002 67 Property of AIR LIQUIDE – All copying prohibited II.2. Applications for II.2. Applications for each each group of group of products products ! DRY PRODUCTS " Products : dried fruits, powdered milk, coffee, tea, crisps, peanuts, etc. " Preservation problems : oxidation/rancidity development in fats; low Aw # little bacteria growth " Preservation solution : Aligal 1+ metallized packaging (UV protection) at ambient temperature addition of CO 2 for milk powder (pressure regulation during air transport) " Preservation result : several months

2 Application for Each Group of Products

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  • April 2002

    67Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! DRY PRODUCTS

    " Products: dried fruits, powdered milk, coffee, tea, crisps, peanuts, etc." Preservation problems: oxidation/rancidity development in fats;

    low Aw# little bacteria growth" Preservation solution: Aligal 1+ metallized packaging (UV protection) at ambient

    temperatureaddition of CO2 for milk powder (pressure regulation during air transport)

    " Preservation result: several months

  • April 2002

    68Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! INTERMEDIATE MOISTURE PRODUCTS

    PASTRY PRODUCTS" Products: bread, cake, flaky pastry, blinis, pie bases, sponge cake, etc." Preservation problems: * oxidation/rancidity development in fats# N2;

    * development of moulds+bacteria# CO2 compulsory* release of O2 by bread-making products

    " Preservation solution: * Aw< 0.8: Aligal 12 or Aligal 13 at ambient temperature* Aw>0.8: Aligal 15 or Aligal 2 at 4

    * use an O2 absorber or ethanol releaser" Preservation result: several weeks (Aw>0.8) to several months

  • April 2002

    69Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! INTERMEDIATE MOISTURE PRODUCTS

    PIZZAS/QUICHE/FRESH PASTRY" Products: idem, delicatessen pastries, ready-to-eat meals, etc." Preservation problems: microbe development# CO2 compulsory" Preservation solution:* Aw< 0.8: Aligal 12 or Aligal 13 at ambient temperature

    * Aw>0.8: Aligal 15 or Aligal 2 at 4* Sandwiches: less than 30% of CO2 because sauce is present

    " Preservation result: several weeks (Aw

  • April 2002

    70Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! INTERMEDIATE MOISTURE PRODUCTS

    CHEESES" Products: cooked cheeses, veined cheeses, soft cheeses, etc." Preservation problems: compromise between the development of desired moulds and

    undesirable moulds/appearance of the packaging" Preservation solution:* veined cheeses: Aligal 1, no CO2 for moulds

    * cooked cheese portions: Aligal 2 for acidity regulation, packaging, bacteria control* soft cheese portions: no solution (mould on rind but not on slices)

    " Preservation result: one to several months at 4C

  • April 2002

    71Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! INTERMEDIATE MOISTURE PRODUCTS

    SPECIAL CASE: grated cooked pressed cheeses" Products: grated Emmental, etc." Preservation problems: market demands swollen packets" Preservation solution: Aligal 1 to prevent shrinkage of the packaging

    (low microbiological risk due to absence of rind)" Preservation result: about two months at 4C

  • April 2002

    72Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! VERY MOIST PRODUCTS

    PINK OR RED MEAT" Products: lamb, beef, veal, pork, etc." Preservation problems: high microbial risk, preservation of the colour" Preservation solution: * compromise between shelf life and colour preservation for

    cuts of meat: Aligal 27* whole muscle: Aligal 2 or Aligal 15 (colour not very important)

    " Preservation result: 6 to 15 days (retail) to 1 month (muscles) at 2C

    Meat in100% CO2

  • April 2002

    73Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! VERY MOIST PRODUCTS

    SPECIAL CASE: horse meat" Preservation problems: DFD meat (Dark Firm Dry): dark coloration a few hours

    after slaughtering, high pH (6.5), very rapid microbial spoilage" Preservation solution: Air Liquide recommends using Aligal 15 plus an ATCO

    oxygen absorber at 4C (colour recovery after 15 minutes in the open air)" Preservation result: 10 to 14 days

  • April 2002

    74Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! VERY MOIST PRODUCTS

    PROCESSED MEATS" Products: cooked ham, cured ham, pts, sausages, bacon bits, etc." Preservation problems: * high microbial risk

    * sensitivity to oxidation* various methods of preservation: additives, salting, drying, cooking, etc.

    " Preservation solution: * very variable: N2/CO2 mixture with 0 to 50% of CO2* pts: less than 30% CO2 to prevent sharp taste

    " Preservation result: from 8 days (black pudding) to two months (sausage)

  • April 2002

    75Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! VERY MOIST PRODUCTS

    SPECIAL CASE: hams" Products: * cured hams or dry salted hams: Bayonne Parma (not very fragile)

    * cooked ham: ordinary (Paris) or superior (Baron, Fleuron)" Preservation problems:* the fat becomes rancid in air and light

    * exudate and bacterial growth especially for the superior cooked" Preservation solution: * good hygiene and temperature between 0-4C

    * CO2 for its bacteriostatic effect and separation of the slices* Aligal 1 (cured), Aligal 13 (ordinary), Aligal 15 (superior)* Argon: better protection against oxidation and bacterial growth

    " Preservation result: 21 days at 4C

    Argon teston hams

  • April 2002

    76Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! VERY MOIST PRODUCTS

    PROCESSED MEAT: uncooked sausages" Products: chipolatas, merguez, Toulouse sausage, etc." Preservation problems: * uncooked products very sensitive to all kinds of spoilage

    * use of colorants, nitrites or nitrates to obtain a pink colour* product/gaseous atmosphere/additives interaction

    " Preservation solution: very variable: N2/CO2 mixture with various ratios to achievea compromise between the stability of the initial colour and an acceptable shelf life(occasional use of oxygen in the absence of additives).

    " Preservation result: 15 to 21 days

  • April 2002

    77Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! VERY MOIST PRODUCTS

    Result of packaging Chipolatas (Van Hees)" Use of an oxygen adsorber recommended for packaging with gas flushing" Without nitrites or nitrates: preservation difficult, colour deteriorates, best results

    with Aligal 13+ATCO" With nitrates: Aligal 13 gives the best results" With nitrites: idem

    Conclusions:" Aligal 13: best shelf life/colour compromise" Aligal 15 preferred for health & safety" With colorant (e.g. cochineal): 30% CO2 maximum" Without additives: use a minimum of 60% O2 (high preservation risk!)

    Testdetails

  • April 2002

    78Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! VERY MOIST PRODUCTS

    SEAFOOD PRODUCTS" Products: fresh fish, dried fish, smoked fish, surimi, roes, shellfish, etc." Preservation problems: * high microbial risk (including anaerobic bacteria)

    * sensitivity to oxidation (depending on the fat content of the product)* initial product preparation conditions very important

    " Preservation solution: * 0-2C with O2/N2/CO2 for fresh fish* 4C and N2/CO2 for smoked fish and surimi* ambient temperature with 100% N2 for dried fish

    " Preservation result: from 6 days (fresh fish) to 30 days (dried fish)

  • April 2002

    79Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! VERY MOIST PRODUCTS

    SPECIAL CASE: fresh fish" Products: * low-fat fish: cod, pollack, whiting, ling, etc.

    * fatty fish: mackerel, sardine, salmon, herring, red tuna,etc." Preservation problems : * sensitivity to oxidation (especially fatty fish)

    * high microbial risk especially after processing (filleting, skinning, etc.)* risk of Clostridium Botulinium E growth (anaerobic)

    " Preservation solution: * packaging 3 days after fishing at 0-2C* Aligal 15 or 60%CO2-40%N2 if kept very clean* 60%CO2-10%O2-30%N2 + O2-permeable film if C.B.E risk

    " Preservation result: from 6 days (fillets) to 8-11 days (whole fish)

    ADRIAstudy

  • April 2002

    80Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! VERY MOIST PRODUCTS

    READY-TO-USE VEGETABLES (excluding salads)" Products: potatoes, fruit, sliced fruit, herbs, raw vegetables, etc." Preservation problems : * high rate of respiration and high Aw in some cases

    * very rapid spoilage after slicing or peeling (browning, bacterial attack,softening, etc.)

    " Preservation solution: * good hygiene and temperature between 0 and 4C* limit or stop respiration depending on situation (barrier or O2-permeable film)* Aligal 12 or aligal 15 with percentage of residual O2 kept below 2-3%

    " Preservation result: from 6 to 15 days industrial shelf life

  • April 2002

    81Property of AIR LIQUIDE All copying prohibited

    II.2. Applications for each group of productsII.2. Applications forII.2. Applications for eacheach group ofgroup of productsproducts! VERY MOIST PRODUCTS

    READY-TO-USE VEGETABLES: salads" Products: chicory (escarole), corn salad, lettuce" Preservation problems : * high rate of respiration

    * lettuce more fragile than chicory" Preservation solution: * good hygiene and temperature between 0 and 4C

    * limit respiration depending on the situation (OPP type O2-permeable film)* percentage residual O2 required = 2-3%* Aligal 1 for chicory* Argon: best respiration inhibition and longer shelf life/N2 ( K. Spencer)

    " Preservation result: from 6 to 10 days industrial shelf life

    Argon teston salads

  • Property of AIR LIQUIDE - L. PROST 2001

    STORAGE IN 100%CO2STORAGE IN 100%COSTORAGE IN 100%CO22 Little used in Europe, developed mainly in South Africa and New Zealand for exporting

    beef and veal or sheep meat over long distances. Key factors for obtaining long shelf life:

    temperature: shelf lives of several weeks can be achieved if the storage temperature iskept below 0C.

    microbiological quality of the raw material.

    Claimed shelf lives with the CaptechR processBEEF 5 monthsLAMB 4 monthsPORK 3 months

    Storage temperature = -2 to 0C

    Starting with meat of very high microbiological qualityQuantity of CO2 used = 1.5 l/kg of meatAluminized film, oxygen permeability < 0.05 cc/m2/24h

    viande de buf

  • Property of AIR LIQUIDE - L. PROST 2001

    MEAT IN 100% CO2 - colourMEAT IN 100% COMEAT IN 100% CO22 -- colourcolour Brown colour while remaining in this atmosphere => re-packed in a mixture containing

    oxygen (Aligal 27 or air), where it returns to a red colour in a few minutes. It is very important that the residual oxygen content in the bag stays below 0.5% during

    the whole period of storage. necessary to have a very low oxygen content at To - which requires high performance

    machines with several vacuum/gas injection cycles to be used - or the use of oxygenabsorbers.

    use impermeable bags especially for long-term storage (aluminized).

    Comparison of packaging loins of pork in a vacuum / in gas

    in vacuum in 100% CO2bacteria slows the development of lactic and

    Enterobacteria coloniesprevents the development of Pseudomonasand Bronchotrix

    colour no difference if the oxygen in the bag remains below 0.5%exudate loss of 1% loss of 5 to 6% (because of the use of a blotter)

  • Property of AIR LIQUIDE - L. PROST 2001

    MEAT IN 100% CO2 - example of porkMEAT IN 100% CO2MEAT IN 100% CO2 -- example of porkexample of porkSLIGHTLY CONTAMINATED MEAT shelf life in bags shelf life in UVC

    (stored at -1C) (stored at 5C)

    in vacuum 4 weeks 4 daysin 100% CO2 8 weeks 4 days

    HEAVILY CONTAMINATED MEAT shelf life in bags shelf life in UVC(stored at -1C) (stored at 5C)

    in vacuum < 4 weeks < 3 daysin 100% CO2 < 8 weeks 4 days

    Residual shelf life in Consumer Sales Units (UVC) depends on the bag storage time.A residual bacteriostatic effect of CO2 on meat in trays was observed.

    To limit exudation during packaging in gas, do not use blotter to wrap the meat, but in thatcase the bacteriostatic effect will be weaker.

  • Property of AIR LIQUIDE - L. PROST 2001

    MEAT IN 100% CO2 - beefMEAT IN 100% COMEAT IN 100% CO22 -- beefbeef

    in a vacuum in 100% CO2bacteria slows the development of Lactobacilli and Pseudomonasappearance muscles deformed looks like fresh meatcolour no difference if the oxygen in the bag is less than 0.5%exudate comparable exudation in vacuum/in CO2;

    very little loss when packaging raw muscles (without trimming)

    in industrial tests, no improvement in residual UVC shelf life for muscles packaged in100% CO2.

    absolutely essential to use oxygen absorbers or to pack the muscles on a very high-performance machine to avoid irreversible browning of the meat.

  • Preservation of Boiled HamUsing Argon

    Property of AIR LIQUIDE - Communication to partiesnot member of AIR LIQUIDE Group is prohibited

  • Boiled Ham Deteroration Factors

    Microbial spoilage Color change / loss (oxidation)

  • IntroductionAIR LIQUIDEs Systems Analysis

    AL Gas Mixtures MICROBIAL

    MICROBESFROM

    FOOD PRODUCT

    ENZYMATIC

    ENZYMESFROM

    FOOD PRODUCT

    CHEMICAL

    CHEMICALDEGRADATIVE

    REACTIONS

    MICROBESFROM

    COMMERCIALSOURCES

    ENZYMESFROM

    COMMERCIALSOURCES

    ENZYMESFROMFOOD

    MICROBES

    ENZYMESFROM

    COMMERCIALMICROBES

  • Introduction (cont.)Inhibition of Oxidative Enzymatic Activity

  • Physical Properties of Gases

    Higher specific gravity of argon:Ar 1.38 N2 0.968 (32F, 1 atm, Air=1)

    Higher solubility of argon:

    Source: Wilhelm et.al., 1977. Chemical Reviews , Vol. 77(2).

    G A S S O L U B I L I T Y I NW A T E R @ 2 0 C

    M o l e F r a c t i o n( x 1 0 4 )

    O 2 0 .2 5 0 5N 2 0 .1 2 6 5A r 0 .2 7 4 6

  • Lab-scale test results

    ANAEROBES(N/N0)

    0.01000.02000.03000.04000.05000.06000.0

    0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0TIME(NO. OFDAYS)

    N

    /

    N

    0

    ArAr + 10%O2Ar + 20%CO2N2N2+ 10%O2N2+ 20%CO2

  • Lab-scale test results (cont.)

    AEROBES(N/N0)

    0.0

    1000.02000.0

    3000.0

    4000.05000.0

    6000.0

    0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0TIME (NO. OF DAYS)

    N

    /

    N

    0

    ArAr + 10%O2Ar + 20%CO2N2N2 + 10%O2N2 + 20%CO2

  • Lab-scale test results (cont.)

    COLORREADINGS:L

    50.0

    55.0

    60.0

    65.0

    70.0

    0 5 10 15 20 25 30 35TIME (NO. OF DAYS)

    ArAr + 10%O2Ar + 20%CO2N2N2 + 10%O2N2 + 20%CO2

  • Lab-scale test results (cont.)

    YEASTS/MOLDS(N/N0)

    0.01000.02000.03000.04000.05000.06000.0

    0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0TIME(NO. OFDAYS)

    N

    /

    N

    0

    ArAr +10%O2Ar +20%CO2N2N2+10%O2N2+20%CO2

  • Conclusion

    Packaging with Argon preserves ham againstoxidative degradation much better than doesnitrogen, and reduces microbial spoilage

  • PACKAGING OF CHIPOLATAS IN A PROTECTIVE ATMOSPHERE

    12/01/2000 "VACUUM / INJECTION" TESTS

    CHIPOLATAS WITHOUT NITRITES AND WITHOUT NITRATES

    1 2 3 4 5

    Days 100 % N2 100 % CO2 Aligal1550%N2/50%CO2Aligal13

    70%N2/30%CO2 Aligal 13 + ATCO

    0 0.6% O2 0% CO2 1.3% O2 88.2% CO2 0.6% O2 51.4% CO2 0.6% O2 29.8% CO2

    1 sunken

    3

    11 very good taste

    17No colour problem

    when opened0.1% O2 9.2% CO2

    2.3% O2 26% CO2 1% O2 19.4% CO2 0.7% O2 17.6% CO2

    CONCLUSIONS: * Colour problems

  • PACKAGING OF CHIPOLATAS IN A PROTECTIVE ATMOSPHERE

    12/01/2000 "VACUUM / INJECTION" TESTS

    CHIPOLATAS WITH NITRITES

    Days 100 % N2 100 % CO2 Aligal1550%N2/50%CO2Aligal13

    70%N2/30%CO2 Aligal 13 + ATCO

    0

    1 sunken

    3 slightly mauve slightly mauve

    11 slightly swollen more sunken

    17 liquid0.1% O2 7.8% CO2liquid

    9.5% O2 16.6% CO2 0.2% O2 20.8% CO2

    CONCLUSIONS: * Very good results with Aligal 13* Colour slightly mauve + exudate due to lowering of the pH (why with Aligal 13 + ATCO???)* According to VAN HEES, chipolatas with nitrites packed without O2 inevitably turn grey forabout 24 hours before turning pink again. The less O2 there is, the shorter the grey period.

  • PACKAGING OF CHIPOLATAS IN A PROTECTIVE ATMOSPHERE

    12/01/2000 "VACUUM / INJECTION" TESTS

    CHIPOLATAS WITH NITRATES

    Days 100 % N2 100 % CO2 Aligal1550%N2/50%CO2Aligal13

    70%N2/30%CO2 Aligal 13 + ATCO

    0 0.2% O2 0% CO2 1.9% O2 86.2% CO2 0.1% O2 53% CO2 0.2% O2 30.4% CO2

    1 sunken

    3

    11 slightly swollen slightly sunken

    17liquid

    slightly lighter1.4% O2 26.2% CO2

    liquid 4.5% O2 14.2% CO2

    CONCLUSIONS: * Very good results with Aligal 13 + ATCO* Exudate due to lowering of the pH (why with Aligal 13???)

  • PACKAGING OF CHIPOLATAS IN A PROTECTIVE ATMOSPHERE

    12/01/2000 "BDF" TESTS

    CHIPOLATAS WITHOUT NITRITES AND WITHOUT NITRATES

    1 2 3 4 5

    Days 100 % N2 100 % CO2 Aligal1550%N2/50%CO2Aligal13

    70%N2/30%CO2 Aligal 13 + ATCO

    0 0.7% O2 2.2% CO2 3% O2 90.8% CO2 0.6% O2 42% CO2 0.7% O2 31% CO2

    1

    3

    11

    17 0% O2 24% CO2 0.5% O2 9% CO2

    CONCLUSIONS: * Colour deteriorates with time and colour not restored without O2

  • PACKAGING OF CHIPOLATAS IN A PROTECTIVE ATMOSPHERE

    12/01/2000 "BDF" TESTS

    CHIPOLATAS WITH NITRITES

    Days 100 % N2 100 % CO2 Aligal1550%N2/50%CO2Aligal13

    70%N2/30%CO2 Aligal 13 + ATCO

    0

    1

    3

    11 sunken

    17 0.2% O2 12.6% CO2 2.1% O2 56.6% CO2 0.4% O2 30.2% CO2 0.4% O2 22.8% CO2

    CONCLUSIONS: * Very good results with Aligal 13 + ATCO* There is more O2 with BDF so the grey colour lasts longer, except with ATCO

  • PACKAGING OF CHIPOLATAS IN A PROTECTIVE ATMOSPHERE

    12/01/2000 "BDF" TESTS

    CHIPOLATAS WITH NITRATES

    Days 100 % N2 100 % CO2 Aligal1550%N2/50%CO2Aligal13

    70%N2/30%CO2 Aligal 13 + ATCO

    0 0.7% O2 1.4% CO2 2.4% O2 92.6% CO2 1% O2 41.8% CO2 1% O2 29% CO2

    1

    3

    11

    17 0.1% O2 24% CO2

    CONCLUSIONS: * Good results with Aligal 13* With Aligal 13 + ATCO, colour restoration takes a long time

  • Preservation of fresh fish. Comparative study of modified atmosphere and vacuum packaging.

    ADRIA, 1988 Experimental conditions * Raw Materials: whole mackerel (fatty fish) and whole whiting (low-fat fish) caught fresh (1-3 days) and gutted in ice. * Temperature conditions: kept at +2C after packaging * Packaging:

    In air (EPS tray with PVC clingfilm) In a vacuum: Vacuum Skin Packaging (VSP) and conventional

    vacuum packaging In a modified atmosphere: 40% N2 / 60% CO2 mixture (among

    others) with O2-tight film (15 cm3 O2/m2/24h OPP-PVDC-PE) and possibly 30% N2 / 60% CO2 / 10% O2

    * Assessment between 1 and 11 days after packing:

    Total Volatile Basic Nitrogen (ABVT) Mesophilic Aerobic Bacteria (FAM) Organoleptic Test (before and after cooking)

    Results: ! IN ALL CASES, packaging in a modified atmosphere was shown to perform better than vacuum-packaging which is itself better than packaging in air (ABVT, FAM and organoleptic tests). ! The best results were obtained with the 60% CO2 / 40% N2 mixture + barrier film. ! However, the 60% CO2 / 30% N2 / 10% O2 mixture may be preferred for low-fat fish, to preserve colour and cut down the clostridium risk. Comparison of shelf lives with various types of packaging PRODUCT

    In Modified Atmosphere

    Vacuum Skin

    Packaging

    Conventional vacuum-packed

    In Air (PVC

    clingfilm) Whole fish 8-11 days 6-9 days 6-9 days 6-9 days Fillets 6 days 5 days 4 days -

  • Preservation of Fresh-CutVegetables Using Noble Gases

    Property of AIR LIQUIDE - Communication toparties not member of AIR LIQUIDE Group is

    prohibited

  • ARGON/SALADS

    Customer benefits:

    ! Production flexibility (35h, w/e, re-stocking shops)! DLC for long cycle distribution networks! + 2 days for the consumer vs N2

  • ARGON/SALADS

    Optimum mixtures: Argon: 77% 75% 82%CO2: 15% 15% 10%O2: 8% 10% 8%

    Machine: Sandiacre TG 320 LD (VFFS) Films: standard OPP antimist, PVDC Temperature: 8C (simulating reality) Results for each product: organoleptic assessment in-house

    Coffee shop salad: 9 daysShredded iceberg : 7-8 days

    Mixed saladMicrobial activity is not the limiting factor for salad storage.No improvement over N2.

  • ARGON/SALADS

    PVDC/PP (impermeable) > OPP (permeable)PVDC: + 1 to 2 days vs OPP with argon mixtureThere is a risk of anaerobic activity with PVDC if the cold chain breaks down

    Argon reduces the respiration coefficient compared with N2; CO2 emissions are20% lower at 4 days vs packaging under N2.

    Consequence: maintenance of water and sugar levels and therefore of goodappearance, texture and taste.

    The greater the respiration coefficient of the vegetable, the more pronounced theeffect of argon.

  • Vegetables Deterioration Vectors

    BiologicalBiological factors: respiration, ethylene production,transpiration.

    PhysiologicalPhysiological factors: chilling / heat injury. MechanicalMechanical factors: bruises and damages caused

    during harvesting, handling, storage, andtransportation.

    MicrobialMicrobial contaminants.

  • Environmental Factors InfluencingDeterioration of Vegetables

    Temperature Relative humidity Oxygen (O2) concentration Carbon dioxide (CO2) concentration

  • Vegetables Preservation Factors

    Strict temperaturetemperature managementmanagement immediately afterharvest: the single most important operation inpreserving quality.

    Modified AtmosphereModified Atmosphere (MA)(MA) as a supplement torefrigeration.

    Good initialinitial qualityquality of product (e.g. low initialmicrobial load).

  • Functions of Modified Atmosphere

    Slow down metabolic processes (e.g. respiration) Reduce oxidative browning (e.g. polyphenol oxidase) Inhibit growth of microorganisms Reduce moisture loss

  • Most Commonly Used MA Gases

    O2/CO2/N2

    Preservation of fresh-cut vegetables usuallyinvolves packaging under reducedreduced OO22, or elevatedelevated

    COCO22, or combination of both, with a nitrogennitrogenbalancebalance.

  • Respiration of Fresh-Cut Vegetables

    RESPIRATIONRESPIRATION+ O+ O22

    Sugars CO2 H2O Heat

    Respiration rates vary with horticultural commodity(e.g. type, cultivar, maturity, physiological condition).

    Respiration rates increase with increasing temperature. Respiration rates increase with processing (e.g. peeling,

    cutting).

  • Impact of Modified Atmosphereon Respiration

    Lower temperature Reduced O2 Elevated CO2 Combination of above

    parameters

    REDUCEDREDUCEDRESPIRATION RATE:RESPIRATION RATE:

    Reduced loss ofcarbohydrates(i.e. sweetness is retained,better taste, betternutritional value).

    Reduced moisture loss.

  • AIR LIQUIDE New MAP TechnologyNoble Gases

    Gas Volume (%)N2 78.08O2 20.95Ar 0.93CO2 0.03Ne 0.0018H2 0.00005He 0.0005Kr 0.0001Xe 0.000009

    Altogether, noble gasesmake up about 1% ofthe earths atmosphere.

    Merck Index, 1983.

  • Role of Noble Gases in MAPof Fresh-Cut Vegetables

    Improve qualityImprove quality andand extend shelfextend shelf--life oflife of freshfresh--cutcutvegetables throughvegetables through::

    Better control of respiration and surface distributionof water.

    Inhibition of oxidative enzyme activity(e.g. enzymatic browning).

    Inhibition of chemical oxidation reactions(e.g. pigments, aroma/flavour compounds).

  • Role of Noble Gases in MAPof Fresh-Cut Vegetables (cont.)

    BenefitsBenefits ofof extended shelfextended shelf--life:life: Added production flexibility for food processors Reduced product losses for retailers

  • Cost Issues Associated with Noble Gases

    Noble gases are moremore expensiveexpensive than classical gases:

    e.g. Argon vs. Nitrogen

    However, lower argon volumes are needed due tohigher densityhigher density of argon (e.g. better flush efficiency 2.2(Ar) vs. 2.5 (N2) vol.gas/vol.bag - Geest/Oct. 1996).

    Lower volumes needed may partially offset the costdifference.

  • Regulatory Status of Noble Gases

    European Parliament and Council DirectiveNo. 95/2/EC of 20 February 1995 on food additivesother than colours and sweeteners: Argon = E938;Helium = E939.

    U.S. Food and Drug Administration: He, Ne, Ar, Krand Xe are Generally Recognized as Safe (GRAS).

  • Control of Respiration(CRC Laboratory Results)

  • Control of Respiration(CRC Laboratory Results)

  • Inhibition of Oxidative Enzymatic Activity(CRC Laboratory Results)

  • AIR LIQUIDE Case Studies

    GreenGreen SaladsSalads:: Commercial References:

    Arneberga (Sweden) - gas contract Geest (U.K.) - licence (signed Oct. 1, 1996)

    Other Customer Tests (no commercial results): Soleco (France)

    Raw Peeled PotatoesRaw Peeled Potatoes (commercial references): Skal-Man (Sweden) - gas contract Nature Frais (France) - gas contract

  • Case Study No. 1 - Arneberga (Sweden)

    Product: shredded Iceberg lettuce (2 kg/bag) Wash: water Packaging film: polypropylene/polyethylene laminate

    (OTR = 1,500 cc/m2/24h) Storage temperature: 6C

  • Case Study No. 1 (cont.)

    Switch:From To[N2:CO2:O2] bag 65:15:10 [Ar:CO2:O2] feed 77:15:8

    [CO2] bag 12-14[O2] bag 8-11

    Shelf-life: 7 days Benefit to customer: better quality of product

    (especially towards end of shelf-life)

  • Case Study No. 2 - Geest (U.K.)(March 1996 Trial)

    Products: - shredded Iceberg lettuce (250 g/bag)- Mixed Salad (250 g/bag)

    Wash: standard hypochlorite (100 ppm) Packaging films:

    Standard Antimist (Lawson Mardon): polypropylene(OTR = 1,100 cc/m2/24h)

    PVDC Standard (Lawson Mardon): polyvinylidenechloride/polypropylene laminate (OTR = 25 cc/m2/24h)

    Storage temperature: 5C

  • Case Study No. 2 - Results

  • Case Study No. 2 - Results (cont.)

  • Case Study No. 2 - Conclusions

    PVDCPVDC film performed better than standardstandard antimistantimistfilm, but has potential anaerobiosis risk, shouldtemperaturetemperature abuseabuse occur.

    Compared to nitrogen control, argon based mixtureprovided 11 to 22 extra days of shelf life.

    COCO22/O/O22 ratio is also critical; the best result wasachieved at 15:815:8--1010.

  • Case Study No. 3 - Geest (U.K.)(October 1996 Trial)

    Products: mixed salad (200 g/bag) green herb salad (60 g/bag)

    Wash: standard chlorine (100 ppm) Packaging film: Standard Antimist (Lawson

    Mardon); polypropylene (OTR = 1,100 cc/m2/24h) Storage temperature: 8C

  • Case Study No. 3 - Gas Mixtures

    Gas M ix Code Gas M ix Com positionGas mix 1 Factory N2 Control 85:10:5

    Gas mix 2 Ar:CO 2:O 2 77:15:8

    Gas mix 3 Ar:CO 2:O 2 75:15:10

    Gas mix 4 Ar:CO 2:O 2 82:10:8

    Gas mix 5 Ar:CO 2:O 2 85:10:5

  • Case Study No. 3 - ResultsHeadspace Analysis

  • Case Study No. 3 - Results (cont.)Headspace Analysis

  • Case Study No. 3 - Results (cont.)Sensory Evaluation

  • Case Study No. 3 - Results (cont.)Shelf-Life Determination

  • Case Study No. 3 - Results (cont.)Microbial Analysis

  • Case Study No. 3 - Results (cont.)Headspace Analysis

  • Case Study No. 3 - Results (cont.)Headspace Analysis

  • Case Study No. 3 - Results (cont.)Sensory Evaluation

  • Case Study No. 3 - Results (cont.)Shelf-Life Determination

  • Case Study No. 3 - Conclusions

    Study confirmed inhibitory effect of argon on respirationvs. nitrogen.

    The higher the respiration rate of the product (e.g.Mixed Salad), the more pronounced the argon effect.

    Extended shelf-life was achieved for both test productsusing argon based mixtures (1-2 days).

    No comparison between March and October trials due tothe different storage temperatures.

  • Case Study No. 4 - Soleco (France)

    Fresh-cut Products: Lettuce Frise

    Wash: standard chlorine Packaging film: Propafilm MG35 (ICI) - oriented

    polypropylene (OTR 1,800 cc/m2/24h) Storage temperature: 5C

  • Case Study No. 4 - Results(Trial No. 2)

  • Case Study No. 4 - Results (cont.)(Trial No. 2)

  • Case Study No. 4 - Results (cont.)(Trial No. 2)

  • Case Study No. 4 - Results(Trial No. 3)

  • Case Study No. 4 - Results (cont.)(Trial No. 3)

  • Case Study No. 4 - Results (cont.)(Trial No. 3)

  • Case Study No. 4 - Results (cont.)(Trial No. 3)

  • Case Study No. 4 - Conclusions

    Inhibitory effect of argon on respiration of fresh-cutvegetables.

    The higher the respiration rate of the product (e.g.Frise), the more pronounced the argon effect.

    Better preservation of the product organolepticquality under an argon atmosphere vs. nitrogen.

    No differentiation between argon and N2 from amicrobiological standpoint.

  • Case Study No. 5 - Skal-Man (Sweden)

    Product: fresh raw peeled potatoes (7 kg/bag) Wash: water w/ citric acid Packaging film: impermeable (low OTR) Storage under refrigerated conditions Switch:

    From To[N2:CO2] 60:40 [Ar:CO2] 80:20

    Shelf-life: 10 days Benefit to customer: higher consistency of shelf-life attained.

  • Case study No. 6 - Nature Frais

    Product: fresh raw peeled potatoes var. Charlotte(500 g/tray)

    Wash: standard chlorine Packaging materials: impermeable (low OTR) Storage temperature: 3-6C MAP: 100% argon Shelf-life: 10 days

  • Benefits to customer: improved product appeal (i.e. drier appearance) using

    argon vs. N2. higher sensory score for argon vs. N2.Note: no differentiation between argon and N2regarding microbiological quality of product.

    Case study No. 6 (cont.)

  • Q & A

    II.2. Applications for each product groupMore detailMeat in 100% CO2Argon test on hamsPackaging of chipolatas in a protective atmosphereAdria studyArgon test on salads