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Historical review and state of the art in Historical review and - - PowerPoint PPT Presentation

1 Historical review and state of the art in Historical review and state of the art in Time Temperature Integrator (TTI) technology Time Temperature Integrator (TTI) technology for the management of the cold chain of for the management of the


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Historical review and state of the art in Historical review and state of the art in Time Temperature Integrator (TTI) technology Time Temperature Integrator (TTI) technology for the management of the cold chain of for the management of the cold chain of refrigerated and frozen foods refrigerated and frozen foods

P.S.Taoukis P.S.Taoukis, , Th.Tsironi Th.Tsironi, , M.Giannoglou M.Giannoglou, , I.Metaxa I.Metaxa, , E.Gogou E.Gogou

National Technical University of Athens National Technical University of Athens, , School of Chemical Engineering, School of Chemical Engineering, Laboratory of Food Chemistry & Technology Laboratory of Food Chemistry & Technology

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FOOD QUALITY ASSURANCE

Current philosophy :

Decrease of focus on end product testing and verification traditional

cornerstones of quality and regulatory control

Development and application of structured quality assurance systems

based on prevention by monitoring, controlling and recording of critical parameters through product’s entire life cycle

INTRODUCTION

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Monitoring tools for chill chain Time Temperature Integrators (TTI)

A prerequisite for effective application of a TTI based control system is the determination and kinetic study and modeling of the food quality loss indices and of the response of the TTI.

Need for development of practical systems to monitor, record and translate the effect of temperature from production to consumption.

INTRODUCTION

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Active packaging vs Intelligent (Smart) packaging

Direct Quality Indicators vs Indirect Quality Indicators

Time Temperature Integrators (TTI)

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CHARACTERISTICS OF THE ACTUAL CHILL CHAIN

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Survey for temperature conditions (1)

Electronic dataloggers Data loggers were sealed in packages of products and monitored from processing through distribution to delivery and storage in SuperMarkets all over Greece 1st stage of the survey:

Weak links in the chill chain

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2 4 6 8 10 12 14

5000 10000 15000

time (min) temperature

2 4 6 8 10 12

5000 10000 15000 20000

time (min) temperature Temperature conditions FROM production TO the retail outlet

  • 1

1 2 3 4 4000 6000 8000 10000 12000

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Temperature conditions FROM production TO the retail outlet

Conclusions from chill chain study

  • Sharp (but short) increases of temperature (during transport)
  • Cases of retail storage at temperatures > 7°C
  • Significant temperature fluctuations
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Survey for temperature conditions (2)

Electronic dataloggers 4 data loggers were distributed randomly to potential consumers to monitor variations INSIDE the refrigerator 2st stage of the survey:

Variations WITHIN the domestic refrigerator

1 2 3 4

1: upper shelf 2: middle shelf 3: lower shelf 4: door

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5 10 15 1000 2000 3000 4000

UP MIDDLE DOWN DOOR

temperature time (min)

5 10 15 1000 1500 2000 2500 3000 3500 4000 4500 5000

time (min) temperature

Temperature conditions IN the domestic refrigerator

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% of domestic refrigerators

26% 28% 23% 15% 8% < 4°C 4°C<T< 6°C 6°C<T< 8°C 8°C<T< 10°C 10°C<T< 12°C

Average temperature of domestic refrigerators (~400 cases) Temperature variation within domestic refrigerators

5 10 15 20 25 30

  • 2.0
  • 0.8

0.3 1.5 2.7 3.8 5.0 6.2 7.3 8.5 9.7 10.8 12.0

upper shelf middle shelf lower shelf door

Temperature (°C)

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Food Refrigeration Innovations for Safety, Consumers’ Benefit, Environmental Impact and Energy Optimisation Along the Cold Chain in Europe

EC 7th Framework RTD Project Grant agreement no.: 245288

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Temperature variations in distribution and storage conditions

Justification for continuous monitoring

TTI

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14

APPLICABILITY OF TTI FOR MONITORING THE CHILL CHAIN

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15

TTI PRINCIPLES & APPLICATION

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TTI: main principles

Time Temperature Indicators (TTI) are simple, inexpensive devices that can show an easily measurable, time and temperature dependent change that cumulatively indicates the time-temperature history of the product from the point of manufacture to the consumer, allowing the location and the improvement of the critical points of the chill chain

PRINCIPLES OF TTI

TYPES OF TTI

Enzymatic

Polymer based Diffusion based

Microbial Photochemical

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TTI applications

  • 1. Constant temperature monitoring of the chill chain-elucidation of

the “problematic” distribution phases 2. Correlation to food quality deterioration kinetics-prediction of the remaining shelf life at ANY point of the distribution chain. 3. Improvement of the management and stock rotation system (FIFO) – introduction of Least Shelf life Out (LSFO)/ Shelf Life Decision system (SLDS).

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Early TTI

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Enzymatic TTI

  • Enzymatic TTI is based on a colour change caused by a pH decrease which is

the result of a controlled enzymatic hydrolysis of a lipid substrate

Enzyme and substrate are mixed by mechanically breaking a separating barrier inside the TTI

Hydrolysis of the substrate causes acid release and the pH drop is translated in a color change of a pH indicator from deep green to bright yellow or

  • range red

Enzymatic TTI colourscale

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Microbial TTI

Accepted food quality The food quality is not accepted eOR Cryolog, Gentilly, France

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Polymer TTI

Solid state polymerization reaction.

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TimeTemp TTI

TimeTemp AS, Norway

DIFFUSION REACTION SYSTEM

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Photochemical TTI

OnVu, Ciba-Freshpoint Switzerland

Reference scale Reference scale UV UV-

  • Vis filter

Vis filter Self Self-

  • adhesive label

adhesive label Active material Active material

hn D

Photosensitive compounds are excited and coloured by exposure at UV radiation

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Photochromism in crystalline state Color fading and activation energies of spiropyran

crystals correspond to characteristics of food spoilage

O N R NO2 N

+

O NO2 R Light, 365 nm Activation Heat Fading A, colorless B, dark blue

Photochemical TTI

Industrial / High speed chargers Manual chargers

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S M A S

Development and application of a TTI based Safety Monitoring Development and application of a TTI based Safety Monitoring and Assurance System for Chilled Meat Products and Assurance System for Chilled Meat Products

A European Commission Research and Technology Development Projec A European Commission Research and Technology Development Project t

Quality of life and management of living resources Quality of life and management of living resources

http:// http://smas.chemeng.ntua.gr smas.chemeng.ntua.gr

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Integrated Approach to enable Traceability of the Cold chain of Integrated Approach to enable Traceability of the Cold chain of Fresh Chilled Meat Fresh Chilled Meat and Fish Products by means of tailor and Fish Products by means of tailor-

  • made Time/Temperature Indicators

made Time/Temperature Indicators http:// http://www.freshlabel www.freshlabel/net /net

FRESHLABEL FRESHLABEL

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Project Project IQ IQ-

  • Freshlabel

Freshlabel

Developing novel intelligent labels for chilled and frozen food Developing novel intelligent labels for chilled and frozen food products and promoting products and promoting the influence of smart labels application on waste reduction, fo the influence of smart labels application on waste reduction, food quality and safety in

  • d quality and safety in

the European supply chains the European supply chains

IQ IQ-

  • Freshlabel

Freshlabel

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Instrumental measurement of TTI colour

X-rite Eye1pro Colorimeter Illumination D50 Measurement of visual response with CIE Lab

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Instrumental measurement of Photochemical TTI colour

kt

E E

= ∆ ∆ exp

10 20 30 40 50 60 70 80 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 t (h) L

  • 12
  • 10
  • 8
  • 6
  • 4
  • 2

0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 t (h) a

  • 45
  • 40
  • 35
  • 30
  • 25
  • 20
  • 15
  • 10
  • 5

0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 t (h) b

Response function

2 max 2 min 2 max

) ( ) a a ( ) ( b b L L E − + − + − = ∆

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Instrumental measurement of Enzymatic TTI colour

Response function

M_100U

t(h)

50 100 150 200

norm((a+b)

0.0 0.2 0.4 0.6 0.8 1.0 1.2 2.5 oC 5 oC 8 oC 10 oC 15 oC

( )

2 1

1 1

k t k

e X F

+ =

( ) ( ) ( ) ( )min

max min

b a b a b a b a X + − + + − + =

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Kinetics of Food Quality Deterioration

  • Degradation of quality index Α:
  • Temperature dependence of quality function:

( )

kt A f =

( )

                − − =

ref a A

T T R E k A f

ref

1 1 exp

FOOD SHELF LIFE MODELLING for TTI MONITORING

Apparent reaction order Quality function Q(A)t Ao-A

t

1 ln(A

  • -A

t)

2 1/Ao-1/At m (m≠1)

       

− − − − m

  • A

m t A m 1 1 1 1

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Kinetics of Food Quality Deterioration

  • Quality deteriorartion for variable temperature distribution:

Τeff : constant temperature that results in the same quality change

as the variable temperature distribution over the same time period

( ) ( )

[ ]

t d T T R E exp k dt t T k A f

t ref a A t t

ref ∫

                − − = = 1 1

( )

t T T R E exp k A f

ref eff a A t

ref

                − − = 1 1

FOOD SHELF LIFE MODELLING for TTI MONITORING

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ΤΤΙ response kinetics

( )

t 1 1                 − − = =

ref a I

T T R E exp k kt X F

I ref

Χ Χ: measurable change of : measurable change of ΤΤΙ ΤΤΙ

Response function Response function:

  • Using effective temperature:

Using effective temperature:

( ) ( )

[ ]

t d T T R E exp k dt t T k X F

t ref a I t t

I ref ∫

                − − = = 1 1

( )

t T T R E exp k X F

ref eff a I t

I ref

                − − = 1 1

  • For variable temperature distribution:

For variable temperature distribution:

TTI RESPONSE MODELING

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Measurement of the ΤΤΙ response F(X)

Teff Teff

f (A) At

Quality at time t

Response function: Quality function

( )

t T T R E exp k A f

ref eff a A t

ref

1 1                 − − =

( )

I ref

a I t ref eff

E k X F ln R T T         − =

− − 1 1

I ref

a I

E k ,

a A

E k

ref

,

Εa (ΤΤΙ) = Εa (food)

TTI Application scheme

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Studies of different types of TTIs for monitoring chilled food shelf life

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Integrated Approach to enable Traceability of the Cold chain of Integrated Approach to enable Traceability of the Cold chain of Fresh Fresh Chilled Meat and Fish Products by means of tailor Chilled Meat and Fish Products by means of tailor-

  • made

made Time/Temperature Indicators Time/Temperature Indicators http:// http://www.freshlabel www.freshlabel/net /net

FRESHLABEL FRESHLABEL

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200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 2 4 6 8 10 12 14 Storage Temperature (°C) Shelf life (h)

fresh salmon vacuum packed gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (20% CO2) gilthead seabream fillets stored in MAP (50% CO2) gilthead seabream fillets stored in MAP (80% CO2) MAP beef fillets red herring salad marinated salmon trout cuts raw tuna loins vacuum packed MAP cooked ham cold smoked salmon slices

Ciba Ciba OnVu OnVu Handcharger Handcharger

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1s

200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 2 4 6 8 10 12 14 Storage Temperature (°C) Shelf life (h)

fresh salmon vacuum packed gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (20% CO2) gilthead seabream fillets stored in MAP (50% CO2) gilthead seabream fillets stored in MAP (80% CO2) MAP beef fillets red herring salad marinated salmon trout cuts raw tuna loins vacuum packed MAP cooked ham cold smoked salmon slices

Ciba Ciba OnVu OnVu Handcharger Handcharger

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2s

200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 2 4 6 8 10 12 14 Storage Temperature (°C) Shelf life (h)

fresh salmon vacuum packed gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (20% CO2) gilthead seabream fillets stored in MAP (50% CO2) gilthead seabream fillets stored in MAP (80% CO2) MAP beef fillets red herring salad marinated salmon trout cuts raw tuna loins vacuum packed MAP cooked ham cold smoked salmon slices

Ciba Ciba OnVu OnVu Handcharger Handcharger

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3s

200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 2 4 6 8 10 12 14 Storage Temperature (°C) Shelf life (h)

fresh salmon vacuum packed gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (20% CO2) gilthead seabream fillets stored in MAP (50% CO2) gilthead seabream fillets stored in MAP (80% CO2) MAP beef fillets red herring salad marinated salmon trout cuts raw tuna loins vacuum packed MAP cooked ham cold smoked salmon slices

Ciba Ciba OnVu OnVu Handcharger Handcharger

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4s

200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 2 4 6 8 10 12 14 Storage Temperature (°C) Shelf life (h)

fresh salmon vacuum packed gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (20% CO2) gilthead seabream fillets stored in MAP (50% CO2) gilthead seabream fillets stored in MAP (80% CO2) MAP beef fillets red herring salad marinated salmon trout cuts raw tuna loins vacuum packed MAP cooked ham cold smoked salmon slices

Ciba Ciba OnVu OnVu Handcharger Handcharger

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6s

200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 2 4 6 8 10 12 14 Storage Temperature (°C) Shelf life (h)

fresh salmon vacuum packed gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (20% CO2) gilthead seabream fillets stored in MAP (50% CO2) gilthead seabream fillets stored in MAP (80% CO2) MAP beef fillets red herring salad marinated salmon trout cuts raw tuna loins vacuum packed MAP cooked ham cold smoked salmon slices

Ciba Ciba OnVu OnVu Handcharger Handcharger

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43

10 s

200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 2 4 6 8 10 12 14 Storage Temperature (°C) Shelf life (h)

fresh salmon vacuum packed gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (20% CO2) gilthead seabream fillets stored in MAP (50% CO2) gilthead seabream fillets stored in MAP (80% CO2) MAP beef fillets red herring salad marinated salmon trout cuts raw tuna loins vacuum packed MAP cooked ham cold smoked salmon slices

Ciba Ciba OnVu OnVu Handcharger Handcharger

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44

15 s

200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 2 4 6 8 10 12 14 Storage Temperature (°C) Shelf life (h)

fresh salmon vacuum packed gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (20% CO2) gilthead seabream fillets stored in MAP (50% CO2) gilthead seabream fillets stored in MAP (80% CO2) MAP beef fillets red herring salad marinated salmon trout cuts raw tuna loins vacuum packed MAP cooked ham cold smoked salmon slices

Ciba Ciba OnVu OnVu Handcharger Handcharger

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Shelf life study of gilthead Shelf life study of gilthead seabream fillets packed under seabream fillets packed under modified atmosphere modified atmosphere

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  • The limited and variable shelf life of chilled fish

The limited and variable shelf life of chilled fish products is a major problem for their quality products is a major problem for their quality assurance and commercial viability. assurance and commercial viability.

  • Products like chilled fillets from marine cultured

Products like chilled fillets from marine cultured Mediterranean fish such as gilthead seabream Mediterranean fish such as gilthead seabream have high commercial potential if their shelf life have high commercial potential if their shelf life can be extended through packaging or minimal can be extended through packaging or minimal processing. processing.

Gilthead seabream fillets Gilthead seabream fillets ( (Sparus Sparus aurata aurata) )

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47

  • Marine cultured gilthead seabream fillets were MA packed and

Marine cultured gilthead seabream fillets were MA packed and stored at controlled isothermal conditions 0, 5, 10 and 15 stored at controlled isothermal conditions 0, 5, 10 and 15° °C. C.

  • 2

20% CO 0% CO2

2 -

  • 8

80 0% % air air

  • 5

50% CO 0% CO2

2 -

  • 5

50 0% % air air

  • 8

80% CO 0% CO2

2 -

  • 2

20 0% % air air

Gilthead seabream fillets Gilthead seabream fillets ( (Sparus Sparus aurata aurata) )

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48

Microbiological analysis Microbiological analysis

  • Total viable count

Total viable count

  • Pseudomonas

Pseudomonas spp. spp.

  • Lactic acid bacteria

Lactic acid bacteria

pH measurement pH measurement Sensory evaluation Sensory evaluation

  • Sensory panel of 8

Sensory panel of 8

  • Rating on a 1

Rating on a 1-

  • 9 descriptive hedonic scale

9 descriptive hedonic scale Appearance Appearance Odour Odour Freshness Freshness Texture Texture Taste Taste The microbial growth was modeled using the The microbial growth was modeled using the Baranyi Baranyi Growth Model Growth Model

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49

  • Samples were stored under non isothermal conditions

Samples were stored under non isothermal conditions

  • Scenario

Scenario 1: 1: T Teff

eff =5.4

=5.4° °C C T Teff

eff =9.4

=9.4° °C C

Validation of the developed kinetic models under dynamic Validation of the developed kinetic models under dynamic temperature conditions temperature conditions

Temperature profiles were obtained from electronic data loggers (COX TRACERTM, Belmont, NC)

1 3 5 7 9 10 20 30 40 50 Time (h) T(°C) 3 5 7 9 11 13 10 20 30 Time (h) T(°C)

  • Scenario

Scenario 2: 2:

9 9° °C, 4h C, 4h 5 5° °C, 3h C, 3h 2 2° °C, 2h C, 2h 9 9° °C, 2h C, 2h 12 12° °C, 3h C, 3h 5 5° °C, 2h C, 2h

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50

Gas headspace changes Gas headspace changes ( (CO CO2

2 and

and O O2

2)

) in fish fillet packages in fish fillet packages 50% CO 50% CO2

2-

  • 50%

50% air air

2 4 6 8 10 12 100 200 300 400 500 600 Χρόνος (h) %O2 0C 5C 10C 15C 45 50 55 60 65 100 200 300 400 500 600 Χρόνος (h) %CO2 0C 5C 10C 15C

Time (h) Time (h)

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51

Microbial growth on chilled gilthead seabream fillets packed und Microbial growth on chilled gilthead seabream fillets packed under er MA 5 MA 50% 0% CO CO2

2 at

at 0, 5, 10 and 15 0, 5, 10 and 15° °C C

4 5 6 7 8 9 100 200 300 400 500 600 Χρόνος (h) logCFU/g 0°C 5°C 10°C 15°C

Total viable count Total viable count Pseudomonas Pseudomonas sp. sp.

Lactic acid bacteria Lactic acid bacteria

3 4 5 6 7 8 100 200 300 400 500 600 Χρόνος (h) logCFU/g

0°C 5°C 10°C 15°C

3 4 5 6 100 200 300 400 500 600 Χρόνος (h) logCFU/g 0°C 5°C 10°C 15°C

Time (h) Time (h) Time (h)

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52

Specific growth rates Specific growth rates k k ( (h h-

  • 1

1)

) and kinetic parameters of lactic acid and kinetic parameters of lactic acid bacteria in MAP (50% CO bacteria in MAP (50% CO2

2 –

– 50% air) 50% air)

15 15° °C C 10 10° °C C 5 5° °C C 0° °C C Τ Τ 0.0 0.02829 2829 0.0 0.01925 1925 0.0 0.01078 1078 0.00 0.00342 342 k (h k (h-

  • 1

1)

) E Eα

α=

= 9 91 1 kJ/mol kJ/mol k kref(4

ref(4º ºC) C)=0.0

=0.00739 0739 h h-

  • 1

1

R R2

2=0.9

=0.947 47         − + = T 1 T 1 R E lnk lnk

ref α ref

Arrhenius equation

  • 6
  • 5
  • 4
  • 3
  • 0.0001

0.0001 0.0002 1/Tref-1/T lnk

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53

Predicted ( Predicted (SL SLpred

pred) and experimental shelf life (

) and experimental shelf life (SP SPexp

exp) of MAP

) of MAP gilthead seabream fillets under gilthead seabream fillets under nonisothermal nonisothermal conditions conditions

  • 1.0

1.0 233 233 235 235 50 50% CO % CO2

2

% % error error

SL SLexp

exp (h)

(h) SL SLpred

pred (h)

(h)

Scenario Scenario 1 1

  • 12.8

12.8 112 112 127 127 50 50% CO % CO2

2

% % error error

SL SLexp

exp (h)

(h) SL SLpred

pred (h)

(h)

Scenario Scenario 2 2

1 3 5 7 9 10 20 30 40 50 Time (h) T(°C) 3 5 7 9 11 13 10 20 30 Time (h) T(°C)

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54

Shelf life evaluation of gilthead sea bream Shelf life evaluation of gilthead sea bream stored in MAP (50% CO stored in MAP (50% CO2

2)

)

82 (3 d) 76 (3 d) 15°C 140 (6 d) 129 (5 d) 10°C 301 (12 d) 268 (11 d) 5°C 563 (23 d) 612 (25 d) 0°C Shelf life (h) evaluated by sensory analysis (total impression>5) Shelf life (h) evaluated by microbiological growth (lactic acid bacteria <6 logCFU/g) Storage temperature

E Eα

α= 85.5 kJ/mol

= 85.5 kJ/mol E Eα

α= 90.8 kJ/mol

= 90.8 kJ/mol

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55

Application of the Arrhenius Application of the Arrhenius-

  • type model for shelf life prediction of

type model for shelf life prediction of chilled gilthead seabream fillets under MAP chilled gilthead seabream fillets under MAP

                −         − = T 1 T 1 R E exp CO CO CO k k

ref α 2max 2 2max ref

% CO % CO2

2 concentration

concentration Temperature Temperature Τ Τ Shelf life Shelf life Limit: Limit: 10 106

6 for LAB

for LAB*

*

28 28 d d 18 18 d d 13 13 d d 10 10 d d 9 9 d d 7 7 d d 6 6 d d 5 5° °C C 61 61 d d 40 40 d d 29 29 d d 23 23 d d 19 19 d d 16 16 d d 14 14 d d 0° °C C 80% 80% 70% 70% 60% 60% 50% 50% 40% 40% 30% 30% 20% 20% T T CO CO2

2 concentration

concentration

* * Based on

Based on organoleptic

  • rganoleptic acceptability the end of shelf life coincided with 10

acceptability the end of shelf life coincided with 106

6 LAB for MAP stored samples.

LAB for MAP stored samples.

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56

Application of the Arrhenius Application of the Arrhenius-

  • type model for shelf life prediction of

type model for shelf life prediction of chilled gilthead seabream fillets under MAP chilled gilthead seabream fillets under MAP

200 400 600 800 1000 1200 1400 2 4 6 8 10 12 14 16 Temperature (°C) Shelf life (h) aerobically packed ΜΑΡ (20% CO2) ΜΑΡ (30% CO2) ΜΑΡ (40% CO2) ΜΑΡ (50% CO2) ΜΑΡ (60% CO2) ΜΑΡ (70% CO2) ΜΑΡ (80% CO2)

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57

Kinetic Study of the Kinetic Study of the TTIs TTIs

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58

Instrumental measurement of TTI colour

10 20 30 40 50 60 70 80 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 t (h) L

  • 12
  • 10
  • 8
  • 6
  • 4
  • 2

0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 t (h) a

  • 45
  • 40
  • 35
  • 30
  • 25
  • 20
  • 15
  • 10
  • 5

0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 t (h) b

slide-59
SLIDE 59

59

Response function

kt

E E

= ∆ ∆ exp

2 max 2 min 2 max

) ( ) a a ( ) ( b b L L E − + − + − = ∆

slide-60
SLIDE 60

60

TTI Activation: UV lamp exposure for 2 seconds

B1 TTI response modelling

5 10 15 20 25 30 35 40 45 50 50 100 150 200 250 300 t (h) DE model

327,27 327,27 0,0037 0,0037 3.5 3.5 396,75 396,75 0,0031 0,0031 2.5 2.5 245,82 245,82 0,0049 0,0049 5 5 39,36 39,36 0,0308 0,0308 15 15 96,79 96,79 0,0125 0,0125 10 10 139,96 139,96 0,0087 0,0087 8 8 645,98 645,98 0,0019 0,0019 Shelf life Shelf life (hours) (hours) Rate Rate k (h k (h-

  • 1

1)

) Storage Storage temperature temperature ( (o

  • C

C) )

slide-61
SLIDE 61

61

B1 TTI response modelling

Ea=116KJ/mol

TTI Activation: UV lamp exposure for 2s

  • 6,000
  • 5,500
  • 5,000
  • 4,500
  • 4,000
  • 1,0E-04
  • 8,0E-05
  • 6,0E-05
  • 4,0E-05
  • 2,0E-05

0,0E+00 2,0E-05 1/T-1/Tref lnk

slide-62
SLIDE 62

62

B1 TTI response modelling

0.00 240.00 480.00 720.00 960.00 1200.00 1440.00 1680.00 1920.00 2 4 6 8 10 12 14 16 Temperature (°C) Shelf life (h)

1 second ch.t. 2 seconds ch.t. 3 seconds ch.t. 4 seconds ch.t. 6 seconds ch.t. 10 seconds ch.t. 15 seconds ch.t.

slide-63
SLIDE 63

63

B1 TTI response modeling based on charging energy

)) T 1 T 1 ( R E exp( t k k

ref a a c (4C,1sec) ref

− ⋅ − ⋅ ⋅ =

) 16 , 277 1 T 1 ( 314 , 8 122071 exp( t 00667 , k

71031 , c

− ⋅ − ⋅ ⋅ =

) 16 , 277 1 1 ( 314 , 8 122071 exp( 1074 .

71031 ,

− ⋅ − ⋅ ⋅ =

T E k

UV

(s) t 50 ) / ( E

c 2 UV

⋅ = cm mJ

slide-64
SLIDE 64

64

100 200 300 400 500 600 700 5 10 15 Storage Temperature (°C) Shelf life (h) gilthead seabream fillets stored in MAP (50% CO2) TTI 2.3s

Ciba Ciba OnVu OnVu Handcharger Handcharger

slide-65
SLIDE 65

65

Studies of different types of TTIs for monitoring chilled food shelf life

slide-66
SLIDE 66

66

Study of different types of Study of different types of TTIs TTIs for monitoring for monitoring chilled chopped MAP (80% O chilled chopped MAP (80% O2

2, 12% CO

, 12% CO2

2, 8% N

, 8% N2

2) beef shelf life

) beef shelf life

  • Kinetic study of three different types of enzymatic

Kinetic study of three different types of enzymatic TTIs

  • TTIs. From each type

. From each type three three TTIs TTIs with different concentrations of the enzyme were studied during with different concentrations of the enzyme were studied during storage at storage at 2.5, 5, 8, 10 2.5, 5, 8, 10 και και 15 15° °C. C. LP: LP LP: LP-

  • 600

600U U, , LP LP-

  • 800

800U U, , LP LP-

  • 1000

1000U U L: L: L L-

  • 600

600Y Y, , L L-

  • 600

600R R, , L L-

  • 1000

1000U U Μ Μ: : Μ Μ-

  • 50

50U U, , M M-

  • 100

100U U, , M M-

  • 200

200U U

  • Kinetic study of photochemical TTI exposed at the UV radiation f

Kinetic study of photochemical TTI exposed at the UV radiation for

  • r 0.2, 0.4,

0.2, 0.4, 0.6, 0.8 0.6, 0.8 and and 1 1 sec sec during storage at during storage at 2.5, 5, 8, 10 2.5, 5, 8, 10 και και 15 15° °C. C.

  • OnVu

OnVu B1 B1

  • Kinetic study of the

Kinetic study of the TTIs TTIs at a variable time at a variable time-

  • temperature profile (5

temperature profile (5° °C C -

  • > 4 h,

> 4 h, 9 9° °C C -

  • > 4 h, 12

> 4 h, 12° °C C -

  • > 4h)

> 4h)

  • Kinetic study of the microbial growth of the chopped meat

Kinetic study of the microbial growth of the chopped meat

  • Correlation of the kinetic characteristics of the main microbial

Correlation of the kinetic characteristics of the main microbial growth of the growth of the chopped meat with the kinetic characteristics of the chopped meat with the kinetic characteristics of the TTIs TTIs and selection of the and selection of the appropriate one appropriate one

chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-67
SLIDE 67

67

L 6 0 0 - R

t ( h )

2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0

norm(a+b)

0 , 0 0 , 2 0 , 4 0 , 6 0 , 8 1 , 0 1 , 2 2 . 5 C 5 C 8 C 1 0 C 1 5 C

L - 6 0 0 Y

t ( h )

2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0 1 2 0 0

norm(a+b)

0 ,0 0 ,2 0 ,4 0 ,6 0 ,8 1 ,0 1 ,2 2 .5 o C 5 o C 8 o C 1 0 o C 1 5 o C

L - 1 0 0 0 U

t ( h )

2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0

norm(a+b)

0 ,0 0 ,2 0 ,4 0 ,6 0 ,8 1 ,0 1 ,2 2 .5 o C 5 o C 8 o C 1 0 o C 1 5 o C

L 5-8R

t (h )

100 200 300 400 500

norm(a+b)

0,0 0,2 0,4 0,6 0,8 1,0 1,2 2.5 oC 5 oC 8 oC 10 oC 15 oC

Enzymatic TTI response

chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-68
SLIDE 68

68

0.992 5.32 24.61 107.2 M-200U 0.974 8.94 41.64 97.3 M-100U 0.980 19.09 81.79 95.8 M-50U 0.981 17.44 55.3 145.3 L5-8R 0.915 49.98 132.47 179.4 L-1000U 0.909 42.98 107.88 194.6 L-600Y 0.943 33.68 74.43 192.8 L-600R 0.967 6.05 16.65 149.0 LP-1000U 0.974 9.24 27.80 181.8 LP-800U 0.956 11.24 39.68 185.7 LP-600U

R2 k2ref (h-1) k1ref (h-1) ΕA (kJ/mol) Enzymatic ΤΤΙ

Kinetic characteristics of the Enzymatic TTIs

chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-69
SLIDE 69

69

0 o C

t(h )

1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0

norm(a+b)

0 ,0 0 ,2 0 ,4 0 ,6 0 ,8 1 ,0 1 ,2

log cfu/g

2 3 4 5 6 7 8 M -2 0 0 U M -1 0 0 U L A B

2 .5 o C

t(h )

1 0 0 2 0 0 3 0 0 4 0 0 5 0 0

norm(a+b)

0 ,0 0 ,2 0 ,4 0 ,6 0 ,8 1 ,0 1 ,2

log cfu/g

2 3 4 5 6 7 8 M -2 0 0 U M -1 0 0 U L A B

5 o C

t(h )

5 0 1 0 0 1 5 0 2 0 0 2 5 0

norm(a+b)

0 ,0 0 ,2 0 ,4 0 ,6 0 ,8 1 ,0 1 ,2

log cfu/g

2 3 4 5 6 7 8 M -2 0 0 U M -1 0 0 U L A B

1 0 o C

t(h )

2 0 4 0 6 0 8 0

norm(a+b)

0 ,0 0 ,2 0 ,4 0 ,6 0 ,8 1 ,0 1 ,2

log cfu/g

2 3 4 5 6 7 8 M -2 0 0 U M -1 0 0 U L A B

Correlation of the response of the Enzymatic TTIs with lactic acid bacteria growth

chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-70
SLIDE 70

70

Τhe following mathematic model describes the effect of the time, temperature and the concentration of the enzyme of the TTI on the response of the TTI:

                                − −                 − + = =

− − ref A ref A C

T T R E C t T T R E C X F X 1 1 exp * 27 . 675 1 1 exp * 9 . 2363 exp 1 1 ) (

9217 . 8663 .

E stima te d va lue Pa ra me te r

0.987 R2 105.5 E

α (K

J/ mo l) 4

Τre f (οC)

Determination of a total mathematic model of the Enzymatic ΤΤΙs

chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-71
SLIDE 71

71

For the selection of the appropriate enzymatic TTI for monitoring chopped

meat shelf life the total mathematic model was used…

100 200 300 400 500 600 5 10 15 T (oC) Χρόνος ζωής (h) Εκθετική (M-45U) Εκθετική (Κιµάς 1 kg) Εκθετική (Κιµάς 1/2 kg)

Correlation of the response of the Enzymatic TTI M-45U with the chopped beef shelf life

Chopped meat shelf life (h) Chopped meat shelf life (h) M- 45U

chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-72
SLIDE 72

72

Photochemical TTI response

∆Εtot

2 4 6 8 10 12 14 16 18 20 0.0 20.0 40.0 60.0 80.0

t (h) ∆Ε 2.5 C 5 C 8 C 10 C 15 C

∆Εtot

5 10 15 20 25 30 35 0.0 50.0 100.0 150.0 200.0 250.0 300.0 350.0

t (h) ∆Ε

2.5 C 5 C 8 C 10 C 15 C

∆Εtot

5 10 15 20 25 30 35 40 0.0 50.0 100.0 150.0 200.0 250.0 300.0 350.0 400.0 450.0

t (h) ∆Ε

2.5 C 5 C 8 C 10 C 15 C

∆Ε tot

5 10 15 20 25 30 35 40 0.0 100.0 200.0 300.0 400.0 500.0 600.0

t (h) ∆Ε

2.5 C 5 C 8 C 10 C 15 C

OnVu B1-0.2UV OnVu B1-0.4UV

OnVu B1-0.6UV OnVu B1-0.8UV

chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-73
SLIDE 73

73

Correlation of the response of the Photochemical TTI with lactic acid bacteria growth

0oC

5 10 15 20 25 30 35 40 100 200 300 400 500 600 t (h) ∆Ε 1 2 3 4 5 6 7 8

log cfu/g

LAB Εκθετική (B1_0.2UV) Εκθετική (B1 0.4UV) Εκθετική (B1_0.6UV)

2.5oC

5 10 15 20 25 30 35 40 100 200 300 400 500 600 t (h) ∆Ε 1 2 3 4 5 6 7 8

log cfu/g

LAB Εκθετική (B1_0.2UV) Εκθετική (B1 0.4UV) Εκθετική (B1_0.6UV)

5oC

5 10 15 20 25 30 35 40 50 100 150 200 250 300 t (h) ∆Ε 1 2 3 4 5 6 7 8

log cfu/g

LAB Εκθετική (B1_0.2UV) Εκθετική (B1 0.4UV) Εκθετική (B1_0.6UV)

10oC

5 10 15 20 25 30 35 40 20 40 60 80 t (h) ∆Ε 1 2 3 4 5 6 7 8

log cfu/g

LAB Εκθετική (B1_0.2UV) Εκθετική (B1 0.4UV) Εκθετική (B1_0.6UV)

chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-74
SLIDE 74

74

Kinetic characteristics of the Photochemical TTI

0.994 0.0035 166.2 OnVu B1-1UV 0.992 0.0037 178.0 OnVu B1-0.8UV 0.965 0.0041 188.9 OnVu B1-0.6UV 0.967 0.0061 179.4 OnVu B1-0.4UV 0.974 0.1296 165.6 OnVu B1-0.2UV

R2 kΑ(h-1) ΕA (kJ/mol) Photochemical ΤΤΙ

chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-75
SLIDE 75

75

Determination of a total mathematic model of the Photochemical ΤΤΙ OnVu B1

Τhe following mathematic model describes the effect of the temperature and the charging time on the TTI rate constant (k):

)) 1 1 ( exp(

) 6 . , ( ref a C s t Tref ref

T T R Ea t k k

c

− − =

− =

199.9 Ea (KJ/mol) 0.815 α 0.002 kref (h-1)

Estimated value Parameter

chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-76
SLIDE 76

76

0.00 240.00 480.00 720.00 960.00 1200.00 1440.00 1680.00 1920.00 2 4 6 8 10 12 14 16 Temperature (°C) Shelf life (h)

1 second ch.t. 2 seconds ch.t. 3 seconds ch.t. 4 seconds ch.t. 6 seconds ch.t. 10 seconds ch.t. 15 seconds ch.t.

slide-77
SLIDE 77

77

100 200 300 400 500 600 700 5 10 15 Τ (oC) Χρόνος ζω ής (h) Εκθετική (Κιµάς 1/2 kg) Εκθετική (ΟnVu B1-0.4UV)

Chopped meat shelf life (h) Shelf life (h) OnVu B1-0.4UV

Correlation of the response of the Photochemical TTI B1-0.4 s UV with the chopped meat shelf life

chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-78
SLIDE 78

78

S M A S

Development and application of a TTI based Safety Monitoring Development and application of a TTI based Safety Monitoring and Assurance System for Chilled Meat Products and Assurance System for Chilled Meat Products

A European Commission Research and Technology Development Projec A European Commission Research and Technology Development Project t

Quality of life and management of living resources Quality of life and management of living resources

http:// http://smas.chemeng.ntua.gr smas.chemeng.ntua.gr

slide-79
SLIDE 79

79

Current practice: First In- First Out (FIFO) Disadvantages: ignores variations of product characteristics ignores the REAL time-temperature history of the product Proposed practice: SMAS Main Advantages: variations of product characteristics are considered the REAL time-temperature history of the product is taken into account based on TTI response

School of Chemical Engineering National Technical University of Athens, Greece

slide-80
SLIDE 80

80

T Th he e c co

  • n

nt tr ri ib bu ut ti io

  • n

n

  • f

f S SM MA AS S i in n t th he e c ch hi il ll l c ch ha ai in n m ma an na ag ge em me en nt t c ca an n b be e v vi is su ua al li iz ze ed d a as s a a m mi in ni im mi iz za at ti io

  • n

n

  • f

f r ri is sk k f fo

  • r

r i il ll ln ne es ss s a an nd d

  • p

pt ti im mi is sa at ti io

  • n

n

  • f

f t th he e p pr ro

  • d

du uc ct t q qu ua al li it ty y a at t t th he e t ti im me e

  • f

f c co

  • n

ns su um mp pt ti io

  • n

n

School of Chemical Engineering National Technical University of Athens, Greece

slide-81
SLIDE 81

81

5 10 15 20 25 30 35 40

FIFO FIFO

One out of a trillion One out of 10 billions One out of 100millions One out of a million One out of 10.000 One out of 100

% of products 10 20 30 40

One out of a trillion One out of 10 billions One out of 100millions One out of a million One out of 10.000 One out of 100

SMAS SMAS

School of Chemical Engineering National Technical University of Athens, Greece

slide-82
SLIDE 82

82

One out of a trillion One out of 10 billions One out of 100millions One out of a million One out of 10.000 One out of 100

% of products Probability of illness

5 10 15 20 25 30 35 40

FIFO FIFO % of products

School of Chemical Engineering National Technical University of Athens, Greece

SMAS SMAS

slide-83
SLIDE 83

83

5 10 15 20 25 30 35 40 45 <0 0.6 1.3 1.9 2.5 3.1 3.8 4.4 5

FIFO FIFO

REJECTED

Time to end of shelf life (days) % of products 5 10 15 20 25 30 35 40 45 <0 0.6 1.3 1.9 2.5 3.1 3.8 4.4 5

FIFO FIFO

REJECTED

Time to end of shelf life (days) % of products

5 10 15 20 25 30 35 40 45 <0 0.6 1.3 1.9 2.5 3.1 3.8 4.4 5

Time to end of shelf life (days) % of products

SMAS SMAS

REJECTED

School of Chemical Engineering National Technical University of Athens, Greece

slide-84
SLIDE 84

84

FIFO FIFO

5 10 15 20 25 30 35 40 45 <0 0.6 1.3 1.9 2.5 3.1 3.8 4.4 5.0

SMAS SMAS

Time to end of shelf life (days) % of products

School of Chemical Engineering National Technical University of Athens, Greece

REJECTED

slide-85
SLIDE 85

85

Field Test Design Field Test Design

120 samples of MAP minced beef

Laboratory Laboratory simulated simulated conditions conditions

Distribution center Distribution center (decision point) (decision point) Local market Local market Export market Export market consumers consumers chilled chopped MAP beef shelf life chilled chopped MAP beef shelf life

slide-86
SLIDE 86

86

2nd step 24 h at various T conditions TTI based split

Decision point TTIs reading

Microbiological analysis 4th step

Field test Design

120 packages 1st step 60 Packages TTI tag attached on each package 60 packages without TTIs 3rd step Local market 4oC 8oC 12, 24, 36 hours Export market 4oC 8oC 48, 72, 96 hours

3 6 9 12 15 12 24 36 48 60 72 Time (hours) Storage temperature (oC)

t-T profil1 t-T profil2 t-T profil4

3 6 9 12 15 12 24 36 48 60 72 Time (hours) Storage temperature (oC)

t-T profil3 t-T profil5

slide-87
SLIDE 87

87

Distribution of Lactic acid bacteria growth for all samples at time of microbiological analysis

  • time of ‘consumption’.

FIELD TEST RESULTS

Spoiled products

The distribution of microbiological growth moves to the left, to lower values, for the TTI bearing products

5 10 15 20 25 30 35 40 45 > 1 5 1 5

  • 1

1

  • 5

5

  • (
  • 5

)

  • 5
  • (
  • 1

) Remaining shelf life at 4°C (hours) % of samples FIFO samples SMAS samples

10 20 30 40 50 <log4 log4-log5 log5-log6 log6-log7 log7-log8 Microbial growth (logN) % of samples

FIFO samples SMAS samples

slide-88
SLIDE 88

88

FROZEN FOODS

slide-89
SLIDE 89

89

FROZEN FOOD QUALITY ASSURANCE Quality of optimally processed frozen food products depends on the

temperature conditions of storage, handling and distribution. Monitoring and control of these conditions would allow chill chain optimization and reliable product shelf life prediction.

INTRODUCTION

slide-90
SLIDE 90

90

It has been reported that a substantial portion of frozen produc It has been reported that a substantial portion of frozen products are exposed, ts are exposed, throughout the distribution, including retail and domestic stora throughout the distribution, including retail and domestic storage, to effective ge, to effective temperatures that deviated significantly from the recommended ra temperatures that deviated significantly from the recommended range. nge.

Average storage temperatures measured in different types of reta Average storage temperatures measured in different types of retail freezers in several il freezers in several stores of a large supermarket chain. stores of a large supermarket chain. ( (Temperature data from recent surveys conducted by NTUA in collab Temperature data from recent surveys conducted by NTUA in collaboration with a

  • ration with a

leading supermarket chain). leading supermarket chain).

20% 20% 10% 30% 20% 10 20 30 40

  • 20 to -18 -18 to -16 -16 to -14 -14 to -12 -12 to -10

T (°C) % samples

slide-91
SLIDE 91

91

Optimization of shelf life distribution Optimization of shelf life distribution

  • f frozen products
  • f frozen products

based on modelling and TTI monitoring based on modelling and TTI monitoring

slide-92
SLIDE 92

92

Project Project IQ IQ-

  • Freshlabel

Freshlabel

Developing novel intelligent labels for chilled and frozen food Developing novel intelligent labels for chilled and frozen food products and promoting products and promoting the influence of smart labels application on waste reduction, fo the influence of smart labels application on waste reduction, food quality and safety in

  • d quality and safety in

the European supply chains the European supply chains

IQ IQ-

  • Freshlabel

Freshlabel

slide-93
SLIDE 93

93

Thank you for your attention Thank you for your attention! !

National Technical University of Athens National Technical University of Athens, , School of Chemical Engineering, School of Chemical Engineering, Laboratory of Food Chemistry & Technology Laboratory of Food Chemistry & Technology

slide-94
SLIDE 94

94

ICEF11 welcomes you in 2011 in Athens ICEF11 welcomes you in 2011 in Athens

http://www.icef11.org http://www.icef11.org

slide-95
SLIDE 95

95

Abstract submission is now open Abstract submission is now open Login and submit your abstract! Login and submit your abstract!

http:/ / www.icef11.org http:/ / www.icef11.org

Abstract Submission Deadline Abstract Submission Deadline

15 October 2010 15 October 2010