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

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1 Historical review and state of the art in Time Temperature Integrator (TTI) technology for the management of the cold chain of refrigerated and frozen foods P.S.Taoukis, Th.Tsironi, M.Giannoglou, I.Metaxa, E.Gogou National Technical University of Athens, School of Chemical Engineering, Laboratory 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 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

3 Monitoring tools for chill chain Need for development of practical systems to monitor, record and translate the effect of temperature from production to consumption. 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. 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

Weak links in the chill chain 6 Electronic dataloggers 1 st stage of the survey: Data loggers were sealed in packages of products and monitored from processing through distribution to delivery and storage in SuperMarkets all over Greece Survey for temperature conditions (1)

Temperature conditions FROM production TO the retail outlet 7 12 temperature 14 12 1 8 6 4 2 5 1 15 time (min) temperature 1 8 6 4 2 5 1 15 2 4 3 2 1-1 time (min) 4 6 8 1 12

8 Conclusions from chill chain study Temperature conditions FROM production TO the retail outlet Sharp (but short) increases of temperature (during transport) Cases of retail storage at temperatures > 7 C Significant temperature fluctuations

Survey for temperature conditions (2) 9 Variations WITHIN the domestic refrigerator 2 st stage of the survey: 4 data loggers were distributed randomly to potential consumers to monitor variations INSIDE the refrigerator Electronic dataloggers 1 2 3 4 1: upper shelf 2: middle shelf 3: lower shelf 4: door

Temperature conditions IN the domestic refrigerator 1 temperature 15 1 5 UP MIDDLE DOWN DOOR temperature 15 1 5 1 2 3 4 time (min) 1 15 2 25 3 35 4 45 5 time (min)

% of domestic refrigerators 3 25 2 15 1 5 upper shelf lower shelf middle shelf door 12. 1.8 9.7 8.5 7.3 6.2 5. 3.8 2.7 1.5.3 -.8-2. Temperature ( C) 15% Temperature variation within domestic refrigerators 8% 26% 11 Average temperature of domestic refrigerators (~4 cases) 23% < 4 C 4 C<T< 6 C 6 C<T< 8 C 8 C<T< 1 C 1 C<T< 12 C 28%

12 Food Refrigeration Innovations for Safety, Consumers Benefit, Environmental Impact and Energy Optimisation Along the Cold Chain in Europe EC 7 th Framework RTD Project Grant agreement no.: 245288

13 Temperature variations in distribution and storage conditions Justification for continuous monitoring TTI

14 APPLICABILITY OF TTI FOR MONITORING THE CHILL CHAIN

15 TTI PRINCIPLES & APPLICATION

TTI: main principles 16 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 TYPES OF TTI Diffusion Photochemical based Microbial Enzymatic Polymer based PRINCIPLES OF TTI

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).

Early TTI 18

Enzymatic TTI 19 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 Enzymatic TTI colourscale 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

Microbial TTI 2 Accepted food quality The food quality is not accepted eo R Cryolog, Gentilly, France

21 Polymer TTI Solid state polymerization reaction.

TimeTemp TTI 22 DIFFUSION REACTION SYSTEM TimeTemp AS, Norway

23 Photochemical TTI UV-Vis Vis filter Photosensitive compounds are excited and coloured by exposure at UV radiation Active material Reference scale Self-adhesive label hn D OnVu, Ciba-Freshpoint Switzerland

24 Photochemical TTI Light, 365 nm Activation O Industrial / High speed chargers N R O NO 2 Heat N + Fading R NO 2 A, colorless B, dark blue Photochromism in crystalline state Color fading and activation energies of spiropyran crystals correspond to characteristics of food spoilage Manual chargers

25 S M A S Development and application of a TTI based Safety Monitoring and Assurance System for Chilled Meat Products A European Commission Research and Technology Development Project Quality of life and management of living resources http://smas.chemeng.ntua.gr

26 FRESHLABEL Integrated Approach to enable Traceability of the Cold chain of Fresh Chilled Meat and Fish Products by means of tailor-made Time/Temperature Indicators http://www.freshlabel www.freshlabel/net

27 IQ-Freshlabel Project IQ-Freshlabel Developing novel intelligent labels for chilled and frozen food products and promoting the influence of smart labels application on waste reduction, food od quality and safety in the European supply chains

Instrumental measurement of TTI colour X-rite Eye1pro Colorimeter Measurement of visual response with CIE Lab Illumination D5 28

Instrumental measurement of Photochemical TTI colour 29 L b 8 7 6 5 4 3 2 1. 1. 2. 3. 4. 5. 6. 7. 8. 9. t (h) -5-1 -15-2 -25 a -2-4 -6-8 -1-12. 1. 2. 3. 4. 5. 6. 7. 8. 9. t (h) Response function E E = exp kt -3-35 -4 E = ( L L b 2 2 2 max ) + (a a min) + ( b max) -45. 1. 2. 3. 4. 5. 6. 7. 8. 9. t (h)

3 Instrumental measurement of Enzymatic TTI colour M_1U 1.2 1..8 norm((a+b).6.4.2 2.5 o C 5 o C 8 o C 1 o C 15 o C Response function X = ( a + b) ( a + b) min ( a + b) max ( a + b) min. 5 1 15 2 t(h) F ( X ) = 1+ 1 e k1 t k 2

Kinetics of Food Quality Deterioration 31 Degradation of quality index Α: f ( A) = kt Apparent reaction order Quality function Q(A)t A o -A t 1 ln(a o -A t ) 2 1/A o -1/A t 1 m (m 1) A 1 m A 1 m m 1 t o Temperature dependence of quality function: f ( A) = k A ref exp E R a 1 T T 1 ref FOOD SHELF LIFE MODELLING for TTI MONITORING

Kinetics of Food Quality Deterioration 32 Quality deteriorartion for variable temperature distribution: f t ( A) = k T ( t ) t t [ ] E 1 1 dt = k exp a dt Aref R T T ref Τ eff : constant temperature that results in the same quality change as the variable temperature distribution over the same time period f ( ) E 1 1 A = k exp a t A R T T t ref eff ref FOOD SHELF LIFE MODELLING for TTI MONITORING

ΤΤΙ response kinetics 33 Χ: : measurable change of ΤΤΙ Response function: F F E ( ) 1 1 a X = kt = k exp I t I ref R T Tref For variable temperature distribution: ( X ) = k T ( t ) t Using effective temperature: F t t E [ ] 1 1 a dt = k exp I dt Iref R T T E ( ) 1 1 a X = k exp I t t I ref R T T TTI RESPONSE MODELING eff ref ref

TTI Application scheme 34 Response function: T k 1 1 eff = Tref I ref a I F R ln ki E Measurement of the ΤΤΙ response a ( X ) I ref t F(X) T eff T eff f f (A) A t Quality at time t 1 T a ( A) = k exp t A t ref E R, E A, E a Ε a(ττι) = Ε a (food) k ref Quality function eff 1 T ref

Studies of different types of TTIs for monitoring chilled food shelf life 35

36 FRESHLABEL Integrated Approach to enable Traceability of the Cold chain of Fresh Chilled Meat and Fish Products by means of tailor-made Time/Temperature Indicators http://www.freshlabel www.freshlabel/net

37 34 32 3 28 26 24 22 fresh salmon vacuum packed gilthead seabream fillets stored in MAP (2% CO2) gilthead seabream fillets stored in MAP (8% CO2) red herring salad raw tuna loins vacuum packed cold smoked salmon slices gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (5% CO2) MAP beef fillets marinated salmon trout cuts MAP cooked ham Shelf life (h) 2 18 16 14 12 1 8 6 4 2 2 4 6 8 1 12 14 Ciba OnVu Handcharger Storage Temperature ( C)

38 34 32 3 28 26 24 22 fresh salmon vacuum packed gilthead seabream fillets stored in MAP (2% CO2) gilthead seabream fillets stored in MAP (8% CO2) red herring salad raw tuna loins vacuum packed cold smoked salmon slices gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (5% CO2) MAP beef fillets marinated salmon trout cuts MAP cooked ham Shelf life (h) 2 18 16 14 12 1 8 6 4 2 2 4 6 8 1 12 14 Storage Temperature ( C) 1s Ciba OnVu Handcharger

39 34 32 3 28 26 24 22 fresh salmon vacuum packed gilthead seabream fillets stored in MAP (2% CO2) gilthead seabream fillets stored in MAP (8% CO2) red herring salad raw tuna loins vacuum packed cold smoked salmon slices gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (5% CO2) MAP beef fillets marinated salmon trout cuts MAP cooked ham Shelf life (h) 2 18 16 14 12 1 8 6 4 2 2 4 6 8 1 12 14 Storage Temperature ( C) 2s Ciba OnVu Handcharger

4 34 32 3 28 26 24 22 fresh salmon vacuum packed gilthead seabream fillets stored in MAP (2% CO2) gilthead seabream fillets stored in MAP (8% CO2) red herring salad raw tuna loins vacuum packed cold smoked salmon slices gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (5% CO2) MAP beef fillets marinated salmon trout cuts MAP cooked ham Shelf life (h) 2 18 16 14 12 1 8 6 4 2 2 4 6 8 1 12 14 Storage Temperature ( C) 3s Ciba OnVu Handcharger

41 34 32 3 28 26 24 22 fresh salmon vacuum packed gilthead seabream fillets stored in MAP (2% CO2) gilthead seabream fillets stored in MAP (8% CO2) red herring salad raw tuna loins vacuum packed cold smoked salmon slices gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (5% CO2) MAP beef fillets marinated salmon trout cuts MAP cooked ham Shelf life (h) 2 18 16 14 12 1 8 6 4 2 2 4 6 8 1 12 14 Storage Temperature ( C) 4s Ciba OnVu Handcharger

42 34 32 3 28 26 24 22 fresh salmon vacuum packed gilthead seabream fillets stored in MAP (2% CO2) gilthead seabream fillets stored in MAP (8% CO2) red herring salad raw tuna loins vacuum packed cold smoked salmon slices gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (5% CO2) MAP beef fillets marinated salmon trout cuts MAP cooked ham Shelf life (h) 2 18 16 14 12 1 8 6 4 2 2 4 6 8 1 12 14 Storage Temperature ( C) 6s Ciba OnVu Handcharger

43 34 32 3 28 26 24 22 fresh salmon vacuum packed gilthead seabream fillets stored in MAP (2% CO2) gilthead seabream fillets stored in MAP (8% CO2) red herring salad raw tuna loins vacuum packed cold smoked salmon slices gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (5% CO2) MAP beef fillets marinated salmon trout cuts MAP cooked ham Shelf life (h) 2 18 16 14 12 1 8 6 4 2 2 4 6 8 1 12 14 Storage Temperature ( C) 1 s Ciba OnVu Handcharger

44 34 32 3 28 26 24 22 fresh salmon vacuum packed gilthead seabream fillets stored in MAP (2% CO2) gilthead seabream fillets stored in MAP (8% CO2) red herring salad raw tuna loins vacuum packed cold smoked salmon slices gilthead seabream fillets stored aerobically gilthead seabream fillets stored in MAP (5% CO2) MAP beef fillets marinated salmon trout cuts MAP cooked ham Shelf life (h) 2 18 16 14 12 1 8 6 4 2 2 4 6 8 1 12 14 Storage Temperature ( C) 15 s Ciba OnVu Handcharger

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

46 Gilthead seabream fillets (Sparus Sparus aurata) The limited and variable shelf life of chilled fish products is a major problem for their quality assurance and commercial viability. Products like chilled fillets from marine cultured Mediterranean fish such as gilthead seabream have high commercial potential if their shelf life can be extended through packaging or minimal processing.

47 Gilthead seabream fillets (Sparus Sparus aurata) Marine cultured gilthead seabream fillets were MA packed and stored at controlled isothermal conditions, 5, 1 and 15 C. 2% CO 2-8% air 5% CO 2-5% air 8% CO 2-2% air

Microbiological analysis Total viable count Pseudomonas spp. Lactic acid bacteria The microbial growth was modeled using the Baranyi Growth Model 48 ph measurement Sensory evaluation Sensory panel of 8 Rating on a 1-91 9 descriptive hedonic scale Appearance Odour Freshness Texture Taste

Validation of the developed kinetic models under dynamic temperature conditions 49 - Samples were stored under non isothermal conditions Scenario 1: 2 C, 2h T( C) 9 7 5 3 T eff =5.4 C 5 C, 3h 9 C, 4h 1 1 2 3 4 5 Time (h) 13 Scenario 2: 5 C, 2h T( C) 11 9 7 T eff =9.4 C 5 12 C, 3h 9 C, 2h 3 1 2 3 Time (h) Temperature profiles were obtained from electronic data loggers (COX TRACER TM, Belmont, NC)

Gas headspace changes (CO and 2 O ) in 2 fish fillet packages 5 5% CO -5% air 2 %O2 12 1 8 6 4 2 C 5C 1C 15C %CO2 65 6 55 5 45 C 5C 1C 15C 1 2 3 4 5 6 Χρόνος (h) Time (h) 1 2 3 4 5 6 Χρόνος (h) Time (h)

Microbial growth on chilled gilthead seabream fillets packed under MA 5% 5 CO at 2, 5, 1 and 15 C 51 logcfu/g 9 8 7 6 5 4 C 5 C 1 C 15 C logcfu/g 6 5 4 3 C 5 C 1 C 15 C 1 2 3 4 5 6 Time Χρόνος (h) (h) Total viable count logcfu/g 8 7 6 5 1 2 3 4 5 6 Χρόνος Time (h) (h) C 5 C 1 C 15 C Pseudomonas sp. Lactic acid bacteria 4 3 1 2 3 4 5 6 Χρόνος (h) Time (h)

Specific growth rates k (h - 1 ) and kinetic parameters of lactic acid bacteria in MAP (5% CO 5% 2 air) 52 Τ k (h - 1 ) Arrhenius equation C 5 C 1 C 15 C.342.178.1925.2829-3 -4 lnk -5-6 -.1.1.2 1/Tref-1/T lnk = lnk E α = 91 kj/mol k ref(4ºc) ref R 2 =.947 + E R 1 T ref C)=.739739 h -1 α 1 T

Predicted (SL( ) pred and experimental shelf life (SP( ) exp of MAP gilthead seabream fillets under nonisothermal conditions 53 5% % CO 2 SL pred (h) SL exp (h) % error 235 233-1. T( C) 9 7 5 3 1 1 2 3 4 5 Time (h) Scenario 1 5% % CO 2 13 SL pred (h) SL exp (h) % error 127 112-12.8 T( C) 11 9 7 5 3 1 2 3 Time (h) Scenario 2

Shelf life evaluation of gilthead sea bream stored in MAP (5% CO ) 2 54 Storage temperature C 5 C 1 C 15 C Shelf life (h) evaluated by microbiological growth (lactic acid bacteria <6 logcfu/g) 612 (25 d) 268 (11 d) 129 (5 d) 76 (3 d) E α = 9.8 kj/mol Shelf life (h) evaluated by sensory analysis (total impression>5) 563 (23 d) 31 (12 d) 14 (6 d) 82 (3 d) E α = 85.5 kj/mol

Application of the Arrhenius-type model for shelf life prediction of chilled gilthead seabream fillets under MAP 55 % CO 2 concentration Temperature Τ k = k ref CO 2max CO CO 2max 2 Eα exp R 1 T Limit: 1 6 for LAB * ref 1 T Shelf life CO 2 concentration T 2% 3% 4% 5% 6% 7% 8% C 14 d 16 d 19 d 23 d 29 d 4 d 61 d 5 C 6 d 7 d 9 d 1 d 13 d 18 d 28 d * Based on organoleptic acceptability the end of shelf life coincided with 1 6 LAB for MAP stored samples.

Application of the Arrhenius-type model for shelf life prediction of chilled gilthead seabream fillets under MAP 56 Shelf life (h) 14 12 1 8 6 4 aerobically packed ΜΑΡ (2% CO2) ΜΑΡ (3% CO2) ΜΑΡ (4% CO2) ΜΑΡ (5% CO2) ΜΑΡ (6% CO2) ΜΑΡ (7% CO2) ΜΑΡ (8% CO2) 2 2 4 6 8 1 12 14 16 Temperature ( C)

57 Kinetic Study of the TTIs

58 Instrumental measurement of TTI colour L 8 7 6 5 4 3 2 1. 1. 2. 3. 4. 5. 6. 7. 8. 9. t (h) a -2-4 -6-8 -1-12. 1. 2. 3. 4. 5. 6. 7. 8. 9. t (h) -5-1 -15-2 b -25-3 -35-4 -45. 1. 2. 3. 4. 5. 6. 7. 8. 9. t (h)

59 Response function E E = exp kt E = ) 2 + (a a ) 2 + ( ) 2 max min max ( L L b b

6 B1 TTI response modelling DE model 5 45 4 35 3 25 2 15 1 5 5 1 15 2 25 3 t (h) Storage temperature ( o C) 2.5 3.5 5 8 1 15 Rate k (h -1 ),19,31,37,49,87,125,38 Shelf life (hours) 645,98 396,75 327,27 245,82 139,96 96,79 39,36 TTI Activation: UV lamp exposure for 2 seconds

61 E a =116KJ/mol B1 TTI response modelling -4, -4,5 lnk -5, -5,5-6, -1,E-4-8,E-5-6,E-5-4,E-5-2,E-5,E+ 2,E-5 1/T-1/Tref TTI Activation: UV lamp exposure for 2s

B1 TTI response modelling 62 192. 168. 144. 12. 1 second ch.t. 2 seconds ch.t. 3 seconds ch.t. 4 seconds ch.t. 6 seconds ch.t. 1 seconds ch.t. 15 seconds ch.t. Shelf life (h) 96. 72. 48. 24.. 2 4 6 8 1 12 14 16 Temperature ( C)

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 = ) 277,16 1 T 1 ( 8,314 12271 exp( t,667 k,7131 c = ) 277,16 1 1 ( 8,314 12271 exp(.174,7131 = T E k UV (s) t 5 ) / ( E c 2 UV = cm mj

64 7 6 gilthead seabream fillets stored in MAP (5% CO2) TTI 2.3s Shelf life (h) 5 4 3 2 1 5 1 15 Storage Temperature ( C) Ciba OnVu Handcharger

Studies of different types of TTIs for monitoring chilled food shelf life 65

Study of different types of TTIs for monitoring chilled chopped MAP (8% O 2, 12% CO 2, 8% N 2 ) beef shelf life 66 Kinetic study of three different types of enzymatic TTIs.. From each type three TTIs with different concentrations of the enzyme were studied during storage at 2.5, 5, 8, 1 και 15 C. LP: LP-6 6U, LP-8 8U, LP-1 1U L: L-6Y, L-6R, L-1U Μ: Μ-5U, M-1U, M-2U Kinetic study of photochemical TTI exposed at the UV radiation for f.2,.4,.6,.8 and 1 sec during storage at 2.5, 5, 8, 1 και 15 C. OnVu B1 Kinetic study of the TTIs at a variable time-temperature temperature profile (5 C -> > 4 h, 9 C -> > 4 h, 12 C -> > 4h) Kinetic study of the microbial growth of the chopped meat Correlation of the kinetic characteristics of the main microbial growth of the chopped meat with the kinetic characteristics of the TTIs and selection of the appropriate one chilled chopped MAP beef shelf life

67 Enzymatic TTI response L6-R L-6Y 1,2 1,2 1, 1, norm(a+b),8,6,4,2, 2 4 6 8 1 t(h ) 2.5 C 5 C 8 C 1 C 15 C norm(a+b),8,6,4,2, 2 4 6 8 1 12 t(h ) 2.5 o C 5 o C 8 o C 1 o C 15 o C L-1U L5-8R 1,2 1,2 1, 1, norm(a+b),8,6 norm(a+b),8,6,4,2 2.5 o C 5 o C 8 o C 1 o C 15 o C,4,2 2.5 o C 5 o C 8 o C 1 o C 15 o C, 2 4 6 8 1 t(h), 1 2 3 4 5 t (h) chilled chopped MAP beef shelf life

Kinetic characteristics of the Enzymatic TTIs 68 Enzymatic ΤΤΙ Ε A (kj/mol) k 1ref (h -1 ) k 2ref (h -1 ) R 2 LP-6U 185.7 39.68 11.24.956 LP-8U 181.8 27.8 9.24.974 LP-1U 149. 16.65 6.5.967 L-6R 192.8 74.43 33.68.943 L-6Y 194.6 17.88 42.98.99 L-1U 179.4 132.47 49.98.915 L5-8R 145.3 55.3 17.44.981 M-5U 95.8 81.79 19.9.98 M-1U 97.3 41.64 8.94.974 M-2U 17.2 24.61 5.32.992 chilled chopped MAP beef shelf life

Correlation of the response of the Enzymatic TTIs with lactic acid bacteria growth 69 o C 2.5 o C 1,2 8 1,2 8 1, 7 1, 7,8 6,8 6 norm(a+b),6 5 log cfu/g norm(a+b),6 5 log cfu/g,4 4,4 4,2 M-2U M-1U LAB 3,2 M -2U M -1U LAB 3, 2 1 2 3 4 5 6, 2 1 2 3 4 5 t(h) t(h) 5 o C 1 o C 1,2 8 1,2 8 1, 7 1, 7,8 6,8 6 norm(a+b),6 5 log cfu/g norm(a+b),6 5 log cfu/g,4 4,4 4,2 M-2U M-1U LAB 3,2 M -2U M -1U LAB 3, 2 5 1 15 2 25, 2 4 6 8 2 t(h) chilled chopped MAP beef shelf life t(h)

Determination of a total mathematic model of the Enzymatic ΤΤΙs 7 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: X = F( X C ) = 1+ exp 2363.9* C 675.27* C.8663 1.9217 E A 1 1 exp t R T Tref E A 1 1 exp R T Tref Parameter Estimated value Τ ref ( ο C) chilled chopped MAP beef shelf life Eα (KJ/mol) 15.5 R 2.987 4

Correlation of the response of the Enzymatic TTI M-45U with the chopped beef shelf life 71 For the selection of the appropriate enzymatic TTI for monitoring chopped meat shelf life the total mathematic model was used 6 5 Εκθετική (M-45U) M- 45U Εκθετική Chopped meat (Κιµάς shelf 1 life kg) (h) Εκθετική (Κιµάς 1/2 kg) Chopped meat shelf life (h) Χρόνος ζωής (h) 4 3 2 1 chilled chopped MAP beef shelf life 5 1 15 T ( o C)

72 Photochemical TTI response Ε tot Ε tot 2 35 Ε 18 16 14 12 1 8 OnVu B1-.2UV 2.5 C 5 C 8 C 1 C 15 C Ε 3 25 2 15 OnVu B1-.4UV 2.5 C 5 C 8 C 1 C 15 C 6 1 4 2 5. 2. 4. 6. 8. t (h). 5. 1. 15. 2. 25. 3. 35. t (h) Ε tot Ε tot 4 4 Ε 35 3 25 2 15 OnVu B1-.6UV 2.5 C 5 C 8 C 1 C 15 C Ε 35 3 25 2 15 OnVu B1-.8UV 2.5 C 5 C 8 C 1 C 15 C 1 1 5 5. 5. 1. 15. 2. 25. 3. 35. 4. 45. t (h). 1. 2. 3. 4. 5. 6. t (h) chilled chopped MAP beef shelf life

Correlation of the response of the Photochemical TTI 73 Ε 4 35 3 25 2 15 1 5 with lactic acid bacteria growth o C 6 5 4 3 2 1 1 2 3 4 5 6 t (h) 8 7 log cfu/g LAB Εκθετική (B1_.2UV) Εκθετική (B1.4UV) Εκθετική (B1_.6UV) Ε 4 35 3 25 2 15 1 5 2.5 o C 6 5 4 3 2 1 1 2 3 4 5 6 t (h) 8 7 log cfu/g LAB Εκθετική (B1_.2UV) Εκθετική (B1.4UV) Εκθετική (B1_.6UV) 4 35 5 o C 8 7 4 35 1 o C 8 7 3 6 3 6 Ε 25 2 15 5 4 3 log cfu/g Ε 25 2 15 5 4 3 log cfu/g 1 2 1 2 5 5 1 15 2 25 3 t (h) chilled chopped MAP beef shelf life LAB 1 Εκθετική (B1_.2UV) Εκθετική (B1.4UV) Εκθετική (B1_.6UV) 5 1 2 4 6 8 t (h) LAB Εκθετική (B1_.2UV) Εκθετική (B1.4UV) Εκθετική (B1_.6UV)

74 Kinetic characteristics of the Photochemical TTI Photochemical ΤΤΙ Ε A (kj/mol) k Α (h -1 ) R 2 OnVu B1-.2UV 165.6.1296.974 OnVu B1-.4UV 179.4.61.967 OnVu B1-.6UV 188.9.41.965 OnVu B1-.8UV 178..37.992 OnVu B1-1UV 166.2.35.994 chilled 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): Ea 1 k = k t a exp( ( ref ( Tref, tc =.6s) C R T T 1 ref )) Parameter k ref (h -1 ) α Ea (KJ/mol) Estimated value.2.815 199.9 chilled chopped MAP beef shelf life

76 192. 168. 144. 12. 1 second ch.t. 2 seconds ch.t. 3 seconds ch.t. 4 seconds ch.t. 6 seconds ch.t. 1 seconds ch.t. 15 seconds ch.t. Shelf life (h) 96. 72. 48. 24.. 2 4 6 8 1 12 14 16 Temperature ( C)

77 Correlation of the response of the Photochemical TTI B1-.4 s UV with the chopped meat shelf life 7 6 Chopped meat shelf life (h) Εκθετική (Κιµάς 1/2 kg) OnVu B1-.4UV Εκθετική (ΟnVu B1-.4UV) Χρόνος ζωής (h) Shelf life (h) 5 4 3 2 1 5 Τ ( o C) 1 15 chilled chopped MAP beef shelf life

78 S M A S Development and application of a TTI based Safety Monitoring and Assurance System for Chilled Meat Products A European Commission Research and Technology Development Project Quality of life and management of living resources http://smas.chemeng.ntua.gr

School of Chemical Engineering National Technical University of Athens, Greece 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 8 The contribution of SMAS in the chill chain management can be visualized as a minimization of risk for illness and optimisation of the product quality at the time of consumption

4 35 3 25 2 15 1 5 FIFO 81 % of products One out of a trillion One out of 1 billions One out of 1millions One out of a million One out of 1. One out of 1 One out of a trillion One out of 1 billions One out of 1millions One out of a million One out of 1. One out of 1 4 3 2 1 School of Chemical Engineering National Technical University of Athens, Greece SMAS

Probability of illness 82 % of % products of products One out of a trillion One out of 1 billions One out of 1millions One out of a million One out of 1. One out of 1 4 35 3 25 2 15 1 5 School of Chemical Engineering National Technical University of Athens, Greece SMAS FIFO

School of Chemical Engineering National Technical University of Athens, Greece 83 % of products 45 4 35 3 25 2 15 1 5 REJECTED FIFO % of products 45 4 35 3 25 2 15 1 5 REJECTED SMAS <.6 1.3 1.9 2.5 3.1 3.8 4.4 5 Time to end of shelf life (days) <.6 1.3 1.9 2.5 3.1 3.8 4.4 5 Time to end of shelf life (days)

School of Chemical Engineering National Technical University of Athens, Greece 84 % of products 45 4 35 3 25 2 15 1 5 REJECTED FIFO SMAS <.6 1.3 1.9 2.5 3.1 3.8 4.4 5. Time to end of shelf life (days)

Field Test Design 85 12 samples of MAP minced beef Distribution center (decision point) Local market Laboratory simulated conditions consumers Export market chilled chopped MAP beef shelf life

Field test Design 86 12 packages 6 packages without TTIs 6 Packages TTI tag attached on each package 1 st step Storage temperature (oc) Storage temperature (oc) 15 12 9 6 3 15 12 9 6 3 t-t profil4 t-t profil2 t-t profil1 12 24 36 48 6 72 Time (hours) t-t profil5 t-t profil3 12 24 36 48 6 72 Time (hours) 2 nd step 24 h at various T conditions TTI based split Decision point TTIs reading 3 rd step Local market 12, 24, 36 hours Export market 48, 72, 96 hours 4 o C 8 o C Microbiological analysis 4 th step 4 o C 8 o C

FIELD TEST RESULTS 87 Distribution of Lactic acid bacteria growth for all samples at time of microbiological analysis - time of consumption. 45 FIFO samples % of samples 5 4 3 2 1 FIFO samples SMAS samples Spoiled products % of samples 4 35 3 25 2 15 1 5 SMAS samples <log4 log4-log5 log5-log6 log6-log7 log7-log8 Microbial growth (logn) >15 15-1 1-5 5- Remaining shelf life at 4 C (hours) -(-5) - 5-(-1) The distribution of microbiological growth moves to the left, to lower values, for the TTI bearing products

FROZEN FOODS 88

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

9 It has been reported that a substantial portion of frozen products are exposed, throughout the distribution, including retail and domestic storage, to effective temperatures that deviated significantly from the recommended range. 4 % samples 3 2 1 2% 3% 1% 2% 2% -2 to -18-18 to -16-16 to -14-14 to -12-12 to -1 Average storage temperatures measured in different types of retail freezers in several stores of a large supermarket chain. (Temperature data from recent surveys conducted by NTUA in collaboration oration with a leading supermarket chain). T ( C)

91 Optimization of shelf life distribution of frozen products based on modelling and TTI monitoring

92 IQ-Freshlabel Project IQ-Freshlabel Developing novel intelligent labels for chilled and frozen food products and promoting the influence of smart labels application on waste reduction, food od quality and safety in the European supply chains

93 Thank you for your attention! National Technical University of Athens, School of Chemical Engineering, Laboratory of Food Chemistry & Technology

94 ICEF11 welcomes you in 211 in Athens http://www.icef11.org

95 Abstract submission is now open Login and submit your abstract! http://www.icef11.org Abstract Submission Deadline 15 October 21