historical review and state of the art in time temperature...

1

Historical review and state of the art in Historical review and state of the art in Time Temperature Integrator (TTI) technologyTime Temperature Integrator (TTI) technology

for the management of the cold chain of for the management of the cold chain of refrigerated and frozen foodsrefrigerated and frozen foods

P.S.TaoukisP.S.Taoukis, , Th.TsironiTh.Tsironi, , M.GiannoglouM.Giannoglou, , I.MetaxaI.Metaxa, , E.GogouE.Gogou

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

2

FOOD QUALITY ASSURANCE

Current philosophy :

Decrease of focus on end product testing and verification traditional cornerstones of quality and regulatory controlDevelopment 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

3

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

4

Active packaging vs

Intelligent (Smart) packaging

Direct Quality Indicators vs Indirect Quality Indicators

Time Temperature Integrators (TTI)

5

CHARACTERISTICS OF THE ACTUAL CHILL CHAIN

6

Survey for temperature conditions (1)

Electronic dataloggers

Data loggers were sealed in packages of productsand 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

7

02468

101214

0 5000 10000 15000

time (min)

tem

pera

ture 0

2

4

6

8

10

12

0 5000 10000 15000 20000

time (min)

tem

pera

ture

Temperature conditions FROM production TO the retail outlet

-1

0

1

2

3

4

4000 6000 8000 10000 12000

8

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

9Survey 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 shelf2: middle shelf3: lower shelf4: door

10

0

5

10

15

0 1000 2000 3000 4000

UPMIDDLEDOWNDOOR

tem

pera

ture

time (min)

0

5

10

15

1000 1500 2000 2500 3000 3500 4000 4500 5000

time (min)te

mpe

ratu

re

Temperature conditions IN the domestic refrigerator

11%

of d

omes

tic re

frig

erat

ors

26%

28%

23%

15%

8%

< 4°C4°C<T< 6°C6°C<T< 8°C8°C<T< 10°C10°C<T< 12°C

Average temperature of domestic refrigerators(~400 cases)

Temperature variation within domestic refrigerators

05

1015202530

-2.0-0.80.31.52.73.85.06.27.38.59.710.812.0

upper shelf middle shelf

lower shelf door

Temperature (°C)

12

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

13

Temperature variationsin distribution and storage conditions

Justification for continuous monitoringTTI

14

APPLICABILITY OF TTI FOR MONITORING

THECHILL CHAIN

15

TTI PRINCIPLES &

APPLICATION

16

TTI: main principles

Time Temperature Indicators (TTI) are simple, inexpensivedevices that can show an easily measurable, time and temperaturedependent change that cumulatively indicates the time-temperature history of the product from the point of manufacture to theconsumer, allowing the location and the improvement of the criticalpoints of the chill chain

PRINCIPLES OF TTI

TYPES OF TTI

Enzymatic Polymer based

Diffusion based

Microbial

Photochemical

17

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).

18Early TTI

19

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 orange red

Enzymatic TTI colourscale

20

Microbial TTI

Accepted food quality

The food quality is not accepted

eOR Cryolog, Gentilly, France

21

Polymer TTI

Solid state polymerization reaction.

22

TimeTemp TTI

TimeTemp AS, Norway

DIFFUSION REACTION SYSTEM

23

Photochemical TTI

OnVu, Ciba-Freshpoint Switzerland

Reference scaleReference scale

UVUV--Vis filterVis filter

SelfSelf--adhesive labeladhesive labelActive materialActive material

hn

D

Photosensitive compounds are excited and coloured by exposure at UV radiation

24

Photochromism in crystalline stateColor fading and activation energies of spiropyrancrystals correspond to characteristics of food spoilage

ONR

NO2 N+

O

NO2

R

Light, 365 nmActivation

HeatFading

A, colorless B, dark blue

Photochemical TTIIndustrial / High speed chargers

Manual chargers

25

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 Productsand Assurance System for Chilled Meat Products

A European Commission Research and Technology Development ProjecA European Commission Research and Technology Development Projectt

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

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

26

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 tailorand Fish Products by means of tailor--made Time/Temperature Indicatorsmade Time/Temperature Indicators

http://http://www.freshlabelwww.freshlabel/net/net

FRESHLABELFRESHLABEL

27

Project Project IQIQ--FreshlabelFreshlabelDeveloping 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, fothe influence of smart labels application on waste reduction, food quality and safety in od quality and safety in

the European supply chains the European supply chains

IQIQ--FreshlabelFreshlabel

28Instrumental measurement of TTI colour

X-rite Eye1pro Colorimeter

Illumination D50Measurement of visual response with CIE Lab

29Instrumental measurement of Photochemical TTI colour

kt

EE −=

∆∆ exp

0

0

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 9.00t (h)

L

-12

-10

-8

-6

-4

-2

0

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

a

-45

-40

-35

-30

-25

-20

-15

-10

-5

0

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

b

Response function

2max

2min

2max )()aa()( bbLLE −+−+−=∆

30

Instrumental measurement of Enzymatic TTI colour

Response function

M_100U

t(h)

0 50 100 150 200

norm

((a+

b)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

2.5 oC5 oC8 oC10 oC15 oC

( )2

1

1

1

ktk

eXF −

+

=

( ) ( )( ) ( )minmax

min

babababaX+−+

+−+=

31Kinetics of Food Quality Deterioration

• Degradation of quality index Α:

• Temperature dependence of quality function:

( ) ktAf =

( )

−

−=

ref

aA TTR

EkAfref

11exp

FOOD SHELF LIFE MODELLING for TTI MONITORING

Apparentreaction order

Quality functionQ(A)t

0 Ao-At1 ln(Ao-At)2 1/Ao-1/At

m (m≠1)

−−−−

moAm

tAm

111

1

32Kinetics 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

( ) ( )[ ] tdTTR

EexpkdttTkAft

ref

aA

t

t ref ∫∫

−

−==

00

11

( ) tTTR

EexpkAfrefeff

aAt ref

−

−=

11

FOOD SHELF LIFE MODELLING for TTI MONITORING

33ΤΤΙ response kinetics

( ) t 11

−

−==

ref

aI TTR

EexpkktXF I

ref

ΧΧ: measurable change of : measurable change of ΤΤΙΤΤΙ

Response functionResponse function:

•• Using effective temperature:Using effective temperature:

( ) ( )[ ] tdTTR

EexpkdttTkXF

t

ref

aI

t

tI

ref ∫∫

−

−==

00

11

( ) tTTR

EexpkXF

refeff

aIt

I

ref

−

−=

11

•• For variable temperature distribution:For variable temperature distribution:

TTI RESPONSE MODELING

34

Measurement of theΤΤΙ response

F(X)

Teff

Teff

f (A)

AtQuality at time t

Response function:

Quality function

( ) tTTR

EexpkAfrefeff

aAt ref

11

−

−=

( )

I

ref

a

I

t

refeff EkXFlnR

TT

−= −−

11

Iref aI Ek , aA Ekref

,Εa (ΤΤΙ) = Εa (food)

TTI Application scheme

35

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

36

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 tailorChilled Meat and Fish Products by means of tailor--made made

Time/Temperature IndicatorsTime/Temperature Indicators

http://http://www.freshlabelwww.freshlabel/net/net

FRESHLABELFRESHLABEL

37

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

0 2 4 6 8 10 12 14Storage Temperature (°C)

Shel

f lif

e (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 OnVuOnVu HandchargerHandcharger

38

1s0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400


Shel

f lif

e (h

)








39

2s0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400


Shel

f lif

e (h

)








40

3s0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400


Shel

f lif

e (h

)








41

4s0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400


Shel

f lif

e (h

)








42

6s0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400


Shel

f lif

e (h

)








43

10s

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400


Shel

f lif

e (h

)








44

15s

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400


Shel

f lif

e (h

)








45

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

modified atmospheremodified atmosphere

46

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 filletsGilthead seabream fillets ((SparusSparus aurataaurata))

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 15stored at controlled isothermal conditions 0, 5, 10 and 15°°C.C.

220% CO0% CO22 -- 8800% % airair550% CO0% CO22 -- 5500% % airair880% CO0% CO22 -- 2200% % airair

Gilthead seabream filletsGilthead seabream fillets ((SparusSparus aurataaurata))

48Microbiological analysisMicrobiological analysis

Total viable countTotal viable countPseudomonasPseudomonas spp.spp.Lactic acid bacteriaLactic acid bacteria

pH measurementpH measurementSensory evaluationSensory evaluation

Sensory panel of 8Sensory panel of 8Rating on a 1Rating on a 1--9 descriptive hedonic scale9 descriptive hedonic scaleAppearanceAppearanceOdourOdourFreshnessFreshnessTextureTextureTasteTaste

The microbial growth was modeled using the The microbial growth was modeled using the BaranyiBaranyi Growth ModelGrowth Model

49

-- Samples were stored under non isothermal conditionsSamples were stored under non isothermal conditions

ScenarioScenario 1:1:TTeffeff =5.4=5.4°°C C

TTeffeff =9.4=9.4°°C C

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

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

1

3

5

7

9

0 10 20 30 40 50Time (h)

T(°C

)3

5

7

9

11

13

0 10 20 30Time (h)

T(°C

)ScenarioScenario 2:2:

99°°C, 4hC, 4h55°°C, 3hC, 3h

22°°C, 2hC, 2h

99°°C, 2hC, 2h1212°°C, 3hC, 3h

55°°C, 2hC, 2h

50Gas headspace changesGas headspace changes ((COCO22 andand OO22)) in fish fillet packagesin fish fillet packages

50% CO50% CO22--50% 50% airair

02468

1012

0 100 200 300 400 500 600Χρόνος (h)

%O

2

0C5C10C15C

45

50

55

60

65

0 100 200 300 400 500 600Χρόνος (h)

%CO

2

0C5C10C15C

Time (h) Time (h)

51Microbial growth on chilled gilthead seabream fillets packed undMicrobial growth on chilled gilthead seabream fillets packed under er MA 5MA 50% 0% COCO22 atat 0, 5, 10 and 150, 5, 10 and 15°°CC

4

5

6

7

8

9

0 100 200 300 400 500 600Χρόνος (h)

logC

FU/g

0°C5°C10°C15°C

Total viable countTotal viable count PseudomonasPseudomonas sp.sp.

Lactic acid bacteriaLactic acid bacteria

3

4

5

6

7

8

0 100 200 300 400 500 600Χρόνος (h)

logC

FU/g

0°C5°C10°C15°C

3

4

5

6

0 100 200 300 400 500 600Χρόνος (h)

logC

FU/g

0°C5°C10°C15°C

Time (h) Time (h)

Time (h)

52

Specific growth ratesSpecific growth rates k k ((hh--11)) and kinetic parameters of lactic acid and kinetic parameters of lactic acid bacteria in MAP (50% CObacteria in MAP (50% CO22 –– 50% air)50% air)

1515°°CC

1010°°CC

55°°CC

00°°CC

ΤΤ

0.00.028292829

0.00.019251925

0.00.010781078

0.000.00342342

k (hk (h--11))

EEαα= = 9911 kJ/molkJ/mol

kkref(4ref(4ººC)C)=0.0=0.007390739 hh--11

RR22=0.9=0.94747

−+=

T1

T1

RElnklnk

ref

αref

Arrhenius equation

-6

-5

-4

-3

-0.0001 0 0.0001 0.00021/Tref-1/T

lnk

53Predicted (Predicted (SLSLpredpred) and experimental shelf life () and experimental shelf life (SPSPexpexp) of MAP ) of MAP

gilthead seabream fillets under gilthead seabream fillets under nonisothermalnonisothermal conditionsconditions

--1.01.0

233233

235235

5050% CO% CO22

% % errorerror

SLSLexpexp (h)(h)SLSLpredpred (h)(h)

ScenarioScenario 11

--12.812.8

112112

127127

5050% CO% CO22

% % errorerror

SLSLexpexp (h)(h)SLSLpredpred (h)(h)

ScenarioScenario 22

1

3

5

7

9

0 10 20 30 40 50Time (h)

T(°C

)

3

5

7

9

11

13

0 10 20 30Time (h)

T(°C

)

54Shelf life evaluation of gilthead sea bream Shelf life evaluation of gilthead sea bream

stored in MAP (50% COstored in MAP (50% CO22))

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 bymicrobiological growth(lactic acid bacteria <6

logCFU/g)

Storage temperature

EEαα= 85.5 kJ/mol= 85.5 kJ/molEEαα= 90.8 kJ/mol= 90.8 kJ/mol

55Application of the ArrheniusApplication of the Arrhenius--type model for shelf life prediction of type model for shelf life prediction of

chilled gilthead seabream fillets under MAPchilled gilthead seabream fillets under MAP

−

−=

T1

T1

REexp

COCOCOkk

ref

α

2max

22maxref

% CO% CO2 2 concentrationconcentrationTemperatureTemperature ΤΤ Shelf lifeShelf life

Limit:Limit: 101066 for LABfor LAB**

2828 dd1818 dd1313 dd1010 dd99 dd77 dd66 dd55°°CC

6161 dd4040 dd2929 dd2323 dd1919 dd1616 dd1414 dd00°°CC

80%80%70%70%60%60%50%50%40%40%30%30%20%20%TT

COCO22 concentrationconcentration

** Based on Based on organolepticorganoleptic acceptability the end of shelf life coincided with 10acceptability the end of shelf life coincided with 1066 LAB for MAP stored samples.LAB for MAP stored samples.

56Application of the ArrheniusApplication of the Arrhenius--type model for shelf life prediction of type model for shelf life prediction of chilled gilthead seabream fillets under MAPchilled gilthead seabream fillets under MAP

0

200

400

600

800

1000

1200

1400

0 2 4 6 8 10 12 14 16

Temperature (°C)

Shel

f lif

e (h

)aerobically packed

ΜΑΡ (20% CO2)

ΜΑΡ (30% CO2)

ΜΑΡ (40% CO2)

ΜΑΡ (50% CO2)

ΜΑΡ (60% CO2)

ΜΑΡ (70% CO2)

ΜΑΡ (80% CO2)

57

Kinetic Study of the Kinetic Study of the

TTIsTTIs

58

Instrumental measurement of TTI colour

0

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 9.00t (h)

L

-12

-10

-8

-6

-4

-2

0

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

a

-45

-40

-35

-30

-25

-20

-15

-10

-5

0

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

b

59

Response function

kt

EE −=

∆∆ exp

0

2max

2min

2max )()aa()( bbLLE −+−+−=∆

60

TTI Activation: UV lamp exposure for 2 seconds

B1 TTI response modelling

05

101520253035404550

0 50 100 150 200 250 300t (h)

DE

mod

el

327,27327,270,00370,00373.53.5

396,75396,750,00310,00312.52.5

245,82245,820,00490,004955

39,3639,360,03080,03081515

96,7996,790,01250,01251010

139,96139,960,00870,008788

645,98645,980,00190,001900

Shelf lifeShelf life(hours)(hours)

Rate Rate k (hk (h--11))

Storage Storage temperature temperature

((ooCC))

61

B1 TTI response modellingEa=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

62

B1 TTI response modelling

0.00

240.00

480.00

720.00

960.00

1200.00

1440.00

1680.00

1920.00

0 2 4 6 8 10 12 14 16Temperature (°C)

Shel

f 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.

63

B1 TTI response modeling based on charging energy

))T1

T1(

REexp(tkk

ref

aac(4C,1sec)ref −⋅

−⋅⋅= −

)16,277

1T1(

314,8122071exp(t00667,0k 71031,0

c −⋅−

⋅⋅= −

)16,277

11(314,8

122071exp(1074.0 71031,0 −⋅−

⋅⋅= −

TEk UV

(s)t50)/(E c2

UV ⋅=cmmJ

64

0

100

200

300

400

500

600

700

0 5 10 15Storage Temperature (°C)

She

lf li

fe (h

)gi lthead seabream fillets stored in MAP (50% CO2)TTI 2.3s


65

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

66Study of different types of Study of different types of TTIsTTIs for monitoringfor monitoringchilled chopped MAP (80% Ochilled chopped MAP (80% O22, 12% CO, 12% CO22, 8% N, 8% N22) beef shelf life) beef shelf life

Kinetic study of three different types of enzymatic Kinetic study of three different types of enzymatic TTIsTTIs. From each type . From each type three three TTIsTTIs with different concentrations of the enzyme were studied duringwith different concentrations of the enzyme were studied duringstorage at storage at 2.5, 5, 8, 10 2.5, 5, 8, 10 καικαι 1515°°C.C.LP: LPLP: LP--600600UU, , LPLP--800800UU, , LPLP--10001000UUL: L: LL--600600YY, , LL--600600RR, , LL--10001000UUΜΜ: : ΜΜ--5050UU, , MM--100100UU, , MM--200200UUKinetic study of photochemical TTI exposed at the UV radiation fKinetic study of photochemical TTI exposed at the UV radiation for or 0.2, 0.4, 0.2, 0.4, 0.6, 0.8 0.6, 0.8 andand 1 1 secsec during storage at during storage at 2.5, 5, 8, 10 2.5, 5, 8, 10 καικαι 1515°°C.C.OnVuOnVu B1 B1 Kinetic study of the Kinetic study of the TTIsTTIs at a variable timeat a variable time--temperature profile (5temperature profile (5°°C C --> 4 h, > 4 h, 99°°C C --> 4 h, 12> 4 h, 12°°C C --> 4h)> 4h)Kinetic study of the microbial growth of the chopped meatKinetic study of the microbial growth of the chopped meatCorrelation of the kinetic characteristics of the main microbialCorrelation 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 TTIsTTIs and selection of the and selection of the appropriate one appropriate one

chilled chopped MAP beef shelf lifechilled chopped MAP beef shelf life

67

L 6 0 0 - R

t ( h )0 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 C5 C8 C1 0 C1 5 C

L - 6 0 0 Y

t ( h )0 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 C5 o C8 o C1 0 o C1 5 o C

L - 1 0 0 0 U

t ( h )0 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 C5 o C8 o C1 0 o C1 5 o C

L 5 -8 R

t (h )0 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

2 .5 oC5 oC8 oC1 0 oC1 5 oC

Enzymatic TTI response


68

0.9925.3224.61107.2M-200U0.9748.9441.6497.3M-100U

0.98019.0981.7995.8M-50U

0.98117.4455.3145.3L5-8R

0.91549.98132.47179.4L-1000U

0.90942.98107.88194.6L-600Y

0.94333.6874.43192.8L-600R

0.9676.0516.65149.0LP-1000U

0.9749.2427.80181.8LP-800U

0.95611.2439.68185.7LP-600U

R2

k2ref

(h-1)k1ref

(h-1)ΕA (kJ/mol)Enzymatic ΤΤΙ

Kinetic characteristics of the Enzymatic TTIs


69

0 o C

t ( h )0 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 UM - 1 0 0 UL A B

2 .5 o C

t ( h )0 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 UM -1 0 0 UL A B

5 o C

t ( h )0 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 UM - 1 0 0 UL A B

1 0 o C

t ( h )0 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 UM - 1 0 0 UL A B

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


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

TTREC

tTTR

EC

XFX

11exp*27.675

11exp*9.2363

exp1

1)(

9217.0

8663.0

Estimated valueParameter

0.987R2

105.5Eα (KJ/mol)4Τref (οC)

Determination of a total mathematic model of the Enzymatic ΤΤΙs


71

For the selection of the appropriate enzymatic TTI for monitoring chopped meat shelf life the total mathematic model was used…

0

100

200

300

400

500

600

0 5 10 15T (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)

Cho

pped

mea

t she

lf lif

e (h

)

M- 45U


72

Photochemical TTI response∆Εtot

0

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 C5 C8 C10 C15 C

∆Εtot

0

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

0

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

0

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


73Correlation of the response of the Photochemical TTI with lactic acid bacteria growth

0oC

0

5

10

1520

25

30

35

40

0 100 200 300 400 500 600

t (h)

∆Ε

0

1

2

34

5

6

7

8

log

cfu/

g

LAB

Εκθετική (B1_0.2UV)

Εκθετική (B1 0.4UV)


2.5oC

0

5

10

15

20

25

30

35

40

0 100 200 300 400 500 600

t (h)

∆Ε

0

1

2

3

4

5

6

7

8

log

cfu/

g

LAB




5oC

0

5

10

15

20

25

30

35

40

0 50 100 150 200 250 300

t (h)

∆Ε

0

1

2

3

4

5

6

7

8

log

cfu/

g

LAB




10oC

0

5

10

15

20

25

30

35

40

0 20 40 60 80

t (h)

∆Ε

0

1

2

3

4

5

6

7

8

log

cfu/

g

LAB


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


74

Kinetic characteristics of the Photochemical TTI

0.9940.0035166.2OnVu B1-1UV

0.9920.0037178.0OnVu B1-0.8UV

0.9650.0041188.9OnVu B1-0.6UV

0.9670.0061179.4OnVu B1-0.4UV

0.9740.1296165.6OnVu B1-0.2UV

R2kΑ(h-1)ΕA (kJ/mol)PhotochemicalΤΤΙ


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):

))11(exp()6.0,(ref

aCstTrefref TTR

Eatkkc

−−

= −=

199.9Ea (KJ/mol)

0.815α

0.002kref (h-1)

Estimated valueParameter


76

0.00

240.00

480.00

720.00

960.00

1200.00

1440.00

1680.00

1920.00

0 2 4 6 8 10 12 14 16Temperature (°C)

Shel

f 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.

77

0

100

200

300

400

500

600

700

0 5 10 15Τ (oC)

Χρόν

ος ζωής

(h)

Εκθετική (Κιµάς 1/2 kg)

Εκθετική (ΟnVu B1-0.4UV)

Chopped meat shelf life (h)

Shel

f 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


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 Productsand Assurance System for Chilled Meat Products

A European Commission Research and Technology Development ProjecA European Commission Research and Technology Development Projectt

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

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

79

Current practice: First In- First Out (FIFO)Disadvantages:

ignores variations of product characteristicsignores the REAL time-temperature history of the

product

Proposed practice: SMASMain Advantages:

variations of product characteristics are consideredthe REAL time-temperature history of the product is

taken into account based on TTI response

School of Chemical EngineeringNational Technical University of Athens, Greece

80

TThhee ccoonnttrriibbuuttiioonn ooff SSMMAASS iinn tthhee cchhiillll cchhaaiinn mmaannaaggeemmeenntt ccaann bbee vviissuuaalliizzeedd aass aa mmiinniimmiizzaattiioonn ooff rriisskk ffoorr iillllnneessss aanndd ooppttiimmiissaattiioonn ooff tthhee pprroodduucctt qquuaalliittyy aatt tthhee ttiimmee ooff ccoonnssuummppttiioonn


81

05

10152025303540

FIFOFIFO

One

out

of

a tri

llion

One

out

of

10 b

illio

ns

One

out

of

100m

illio

ns

One

out

of

a m

illio

n

One

out

of

10.0

00

One

out

of

100

% o

f pro

duct

s

0

10

20

30

40

One

out

of

a tri

llion

One

out

of

10 b

illio

ns

One

out

of

100m

illio

ns

One

out

of

a m

illio

n

One

out

of

10.0

00

One

out

of

100

SMASSMAS


82

One

out

of

a tri

llion

One

out

of

10 b

illio

ns

One

out

of

100m

illio

ns

One

out

of

a m

illio

n

One

out

of

10.0

00

One

out

of

100

% o

f pro

duct

s

Probability of illness

05

10152025303540

FIFOFIFO

% o

f pro

duct

s


SMASSMAS

83

05

1015202530354045

<0 0.6 1.3 1.9 2.5 3.1 3.8 4.4 5

FIFOFIFO

REJ

ECTE

D

Time to end of shelf life (days)

% o

f pro

duct

s

05

1015202530354045

<0 0.6 1.3 1.9 2.5 3.1 3.8 4.4 5

FIFOFIFO

REJ

ECTE

D


% o

f pro

duct

s

05

1015202530354045

<0 0.6 1.3 1.9 2.5 3.1 3.8 4.4 5Time to end of shelf life (days)

% o

f pro

duct

s SMASSMAS

REJ

ECTE

D


84

FIFOFIFO

05

1015202530354045

<0 0.6 1.3 1.9 2.5 3.1 3.8 4.4 5.0

SMASSMAS


% o

f pro

duct

s


RE

JEC

TE

D

85Field Test DesignField Test Design

120 samples of MAP minced beef

LaboratoryLaboratorysimulatedsimulatedconditionsconditions

Distribution centerDistribution center(decision point)(decision point)

Local marketLocal market

Export marketExport marketconsumersconsumers


86

2nd step24 h at various T conditions

TTIbased split

Decision point

TTIs reading

Microbiological analysis4th step

Field test Design

120 packages

1st step

60 PackagesTTI tag

attached on each package

60 packages without TTIs

3rdst

ep

Local market

4oC

8oC12, 24, 36 hours

Export market

4oC

8oC48, 72, 96 hours

0

3

6

9

12

15

0 12 24 36 48 60 72Time (hours)

Stor

age

tem

pera

ture

(oC

)

t-T profil1

t-T profil2

t-T profil4

0

3

6

9

12

15

0 12 24 36 48 60 72Time (hours)

Stor

age

tem

pera

ture

(oC

)

t-T profil3

t-T profil5

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 microbiologicalgrowth moves to the left, to lower

values, for the TTI bearing products

05

1015202530354045

>150

150-100

100-50 50-0

0-(-50)

- 50-(-1

00)

Remaining shelf life at 4°C (hours)%

of s

ampl

es

FIFO samplesSMAS samples

0

10

20

30

40

50

<log4 log4-log5 log5-log6 log6-log7 log7-log8

Microbial growth (logN)

% o

f sam

ples

FIFO samplesSMAS samples

88

FROZEN FOODS

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

90

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

Average storage temperatures measured in different types of retaAverage 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 collabTemperature data from recent surveys conducted by NTUA in collaboration with a oration with a leading supermarket chain).leading supermarket chain).

20%20%

10%

30%

20%

0

10

20

30

40

-20 to -18 -18 to -16 -16 to -14 -14 to -12 -12 to -10T (°C)

% s

ampl

es

91

Optimization of shelf life distribution Optimization of shelf life distribution

of frozen products of frozen products

based on modelling and TTI monitoringbased on modelling and TTI monitoring

92

Project Project IQIQ--FreshlabelFreshlabelDeveloping 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, fothe influence of smart labels application on waste reduction, food quality and safety in od quality and safety in

the European supply chains the European supply chains

IQIQ--FreshlabelFreshlabel

93

Thank you for your attentionThank you for your attention!!

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

94

ICEF11 welcomes you in 2011 in AthensICEF11 welcomes you in 2011 in Athens

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

95

Abstract submission is now openAbstract submission is now open

Login and submit your abstract!Login and submit your abstract!

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

Abstract Submission DeadlineAbstract Submission Deadline

15 October 201015 October 2010

historical review and state of the art in time temperature...

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