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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)
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
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).
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
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
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
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
39
2s0
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
40
3s0
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
41
4s0
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
42
6s0
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
43
10s
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
44
15s
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
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)
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
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
Ciba Ciba OnVuOnVu HandchargerHandcharger
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
chilled chopped MAP beef shelf lifechilled chopped MAP beef shelf life
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
chilled chopped MAP beef shelf lifechilled chopped MAP beef shelf life
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
chilled chopped MAP beef shelf lifechilled chopped MAP beef shelf life
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
chilled chopped MAP beef shelf lifechilled chopped MAP beef shelf life
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
chilled chopped MAP beef shelf lifechilled chopped MAP beef shelf life
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
chilled chopped MAP beef shelf lifechilled chopped MAP beef shelf life
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)
Εκθετική (B1_0.6UV)
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
Εκθετική (B1_0.2UV)
Εκθετική (B1 0.4UV)
Εκθετική (B1_0.6UV)
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
Εκθετική (B1_0.2UV)
Εκθετική (B1 0.4UV)
Εκθετική (B1_0.6UV)
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_0.2UV)
Εκθετική (B1 0.4UV)Εκθετική (B1_0.6UV)
chilled chopped MAP beef shelf lifechilled chopped MAP beef shelf life
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
chilled chopped MAP beef shelf lifechilled chopped MAP beef shelf life
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
chilled chopped MAP beef shelf lifechilled chopped MAP beef shelf life
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
chilled chopped MAP beef shelf lifechilled chopped MAP beef 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
School of Chemical EngineeringNational Technical University of Athens, Greece
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
School of Chemical EngineeringNational Technical University of Athens, Greece
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
School of Chemical EngineeringNational Technical University of Athens, Greece
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
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 5Time to end of shelf life (days)
% o
f pro
duct
s SMASSMAS
REJ
ECTE
D
School of Chemical EngineeringNational Technical University of Athens, Greece
84
FIFOFIFO
05
1015202530354045
<0 0.6 1.3 1.9 2.5 3.1 3.8 4.4 5.0
SMASSMAS
Time to end of shelf life (days)
% o
f pro
duct
s
School of Chemical EngineeringNational Technical University of Athens, Greece
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
chilled chopped MAP beef shelf lifechilled chopped MAP beef shelf life
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
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
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