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Mathematical Modelling on

Non-Thermal Innovative

Food Preservation Processes

(2)

OUTLINE

OUTLINE

 Introduction

- Non-thermal Processes - Mathematical Modelling

- Experimental Design and Data Analysis

Cases Studies

- Ozone, UV-C, Thermosonication - Red bell pepper / ozone

- Courgette / UV-C

(3)

OUTLINE

OUTLINE

 Introduction

- Non-thermal Processes

- Mathematical Modelling

- Experimental Design and Data Analysis

Cases Studies

- Ozone, UV-C, Thermosonication - Red bell pepper / ozone

- Courgette / UV-C

(4)

Product preparation

Product processing (steaming, blanching, cooking)

Minimally processed

Minimally processed

Packaging and Dispatch

Semi-processed

Semi-processed processedHighly Highly processed

Further processing

(freezing, canning, preserving)

NON

(5)

Impact on several quality attributes

The problem is... Heating!

NEW

TE

CHN

OLO

GIE

S

NON

(6)

little loss of:

- colour

- flavour

- texture

- nutrients

NON-THERMAL TECHNOLOGIES

…but still retaining the desired shelf-life and safety!

NON

(7)

Pulsed Electric Fields Exposure of food to an intense electric field by means of controlled pulses of high voltage

Ohmic Heating Generation of heat inside the food as a consequence of Joule effect

Radio Frequency Exposure of food to electromagnetic waves in the radio-frequency range

Microwave Exposure of food to controlled microwaves

High Pressure Short-time exposure to extremely high pressure (up to 5000 bar)

NON

(8)

Super Critical CO2 Contact of food with CO2 at supercritical pressure

Ozone Exposure of food to ozone

Ultrasonication Exposure of foods to ultrasounds (US)

US + mild temperatures (T)  thermosonication

US + pressure (P)  manosonication

US + T + P  manothermosonication

UV-C Exposure of food to controlled pulses of UV rays

NON

(9)

OUTLINE

OUTLINE

 Introduction

- Non-thermal Processes

- Mathematical Modelling

- Experimental Design and Data Analysis

Cases Studies

- Ozone, UV-C, Thermosonication - Red bell pepper / ozone

- Courgette / UV-C

(10)

Model

Model



mathematical expression

i=1,2,...,n (number of experimental runs/observations) j=1,2,...,v (number of independent variables)

k=1,2,...,p (number of model parameters)

y

i

= f(x

ij

,

θ

k

) +

ε

i

MATHEMATICAL MODELLING

MATHEMATICAL MODELLING

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0 1000 2000 3000 4000 5000 x y

(11)

Modeling

Modeling

and

and

Simulation

Simulation

Makes

Makes

it

it

possible

possible

to:

to:

Gain

Gain

more

more

knowledge

knowledge

about

about

the

the

process

process

and

and

the

the

effects

effects

on

on

the

the

product

product

;

;

MATHEMATICAL MODELLING

(12)

Modeling

Modeling

and

and

Simulation

Simulation

Makes

Makes

it

it

possible

possible

to:

to:

Gain

Gain

more knowledge

more

knowledge

about

about

the

the

process

process

and the

and

the

effects

effects

on

on

the

the

product;

product

;

Reduce

Reduce

the

the

number

number

of

of

experiments

experiments

in

in

the

the

development

development

stage

stage

;

;

MATHEMATICAL MODELLING

(13)

Modeling

Modeling

and

and

Simulation

Simulation

Makes

Makes

it

it

possible

possible

to:

to:

Gain

Gain

more knowledge

more

knowledge

about

about

the

the

process

process

and the

and

the

effects

effects

on

on

the

the

product;

product

;

Reduce

Reduce

the

the

number

number

of

of

experiments

experiments

in

in

the

the

development

development

stage

stage;

;

Optimize

Optimize

the

the

process

process

with

with

respect

respect

to

to

different

different

parameters

parameters

,

,

such

such

as

as

quality

quality

;

;

MATHEMATICAL MODELLING

(14)

Modeling

Modeling

and

and

Simulation

Simulation

Makes

Makes

it

it

possible

possible

to:

to:

Gain

Gain

more knowledge

more

knowledge

about

about

the

the

process

process

and the

and

the

effects

effects

on

on

the

the

product;

product

;

Reduce

Reduce

the

the

number

number

of

of

experiments

experiments

in

in

the

the

development

development

stage

stage;

;

Optimize

Optimize the

the

process

process

with

with

respect

respect

to

to

different

different

parameters

parameters,

,

such

such

as quality

as

quality

;

;

Study

Study

the

the

influence

influence

on

on

the

the

product

product

during

during

process

process

disturbances

disturbances

.

.

MATHEMATICAL MODELLING

(15)

Models

Models

should

should

:

:

predict

the response variable

accurately

MATHEMATICAL MODELLING

(16)

Models

Models

should

should

:

:

predict

the response variable

accurately

adequacy

adequacy of the model

MATHEMATICAL MODELLING

(17)

Models

Models

should

should

:

:

predict

the response variable

accurately

adequacy

adequacy of the model

parameters

parameters

quality

quality

MATHEMATICAL MODELLING

(18)

Processes

Chemical Physical Food Processes Transport phenomena • heat transfer • mass transfer • momentum transfer Reaction kinetics Properties

MATHEMATICAL MODELLING

MATHEMATICAL MODELLING

(19)

Processes

Chemical Modelling Physical Food Processes Transport phenomena • heat transfer • mass transfer • momentum transfer Reaction kinetics Properties mathematical function variables parameters data points Experimental design Regression schemes

MATHEMATICAL MODELLING

MATHEMATICAL MODELLING

(20)

Processes

Optimisation Chemical Modelling Physical Food Processes Control Design Assessment Transport phenomena • heat transfer • mass transfer • momentum transfer Reaction kinetics Properties Criteria Objectives mathematical function variables parameters data points Experimental design Regression schemes

MATHEMATICAL MODELLING

MATHEMATICAL MODELLING

(21)

Processes

Optimisation Safety Chemical Modelling Physical Food Processes Control Design Assessment Transport phenomena • heat transfer • mass transfer • momentum transfer Reaction kinetics Properties Quality Criteria Objectives mathematical function variables parameters data points Experimental design Regression schemes

MATHEMATICAL MODELLING

MATHEMATICAL MODELLING

(22)



Mechanistic models are more complex, but in

general allow accurate predictions



Empirical models are much simple, but usually

are appropriate to limited practical uses

MATHEMATICAL MODELLING

(23)



Mechanistic models are more complex, but in

general allow accurate predictions



Empirical models are much simple, but usually

are appropriate to limited practical uses

Balance of the advantages and disadvantages,

depending on the final purpose.

MATHEMATICAL MODELLING

(24)

Difficulties

Difficulties

in

in

food

food

processes

processes

modelling

modelling

:

:

MATHEMATICAL MODELLING

(25)

Difficulties

Difficulties

in

in

food

food

processes

processes

modelling

modelling

:

:



Dynamic processes

MATHEMATICAL MODELLING

(26)

Difficulties

Difficulties

in

in

food

food

processes

processes

modelling

modelling

:

:



Dynamic processes



Complexity and heterogeneity of products

MATHEMATICAL MODELLING

(27)

Difficulties

Difficulties

in

in

food

food

processes

processes

modelling

modelling

:

:



Dynamic processes



Complexity and heterogeneity of products



Structural and physicochemical changes

MATHEMATICAL MODELLING

(28)

Kinetic

Kinetic

Studies

Studies

:

:

Allow the quantification of the extension and rate

of production/consumption of any substance

MATHEMATICAL MODELLING

(29)

Kinetic

Kinetic

Studies

Studies

:

:

Allow the quantification of the extension and rate

of production/consumption of any substance

Safety

MATHEMATICAL MODELLING

(30)

Kinetic

Kinetic

Studies

Studies

:

:

Allow the quantification of the extension and rate

of production/consumption of any substance

Safety

Quality

MATHEMATICAL MODELLING

(31)

Safety

Safety

and

Quality

Quality

depend on:

Intrinsic factors

Extrinsic factors

MATHEMATICAL MODELLING

(32)

Safety

Safety

and

Quality

Quality

depend on:

Intrinsic factors

Extrinsic factors

pH

a

w others

MATHEMATICAL MODELLING

MATHEMATICAL MODELLING

(33)

Safety

Safety

and

Quality

Quality

depend on:

Intrinsic factors

Extrinsic factors

pH

a

w others

T

pH

humidity gas concentration others

MATHEMATICAL MODELLING

MATHEMATICAL MODELLING

(34)

OUTLINE

OUTLINE

 Introduction

- Non-thermal Processes - Mathematical Modelling

- Experimental Design and Data Analysis

Cases Studies

- Ozone, UV-C, Thermosonication - Red bell pepper / ozone

- Courgette / UV-C

(35)

Model

Model

Validation

Validation

:

:

Heuristic sampling

Experimental design

Minimize variance of:

predicted response

parameter estimates

EXPERIMENTAL DESIGN AND

EXPERIMENTAL DESIGN AND

DATA ANALYSIS

(36)

Data

Data

Analysis

Analysis

:

:

Regression schemes

Analysis of residuals

(

)

[

]

2 n 1 i k ij i n 1 i 2 i

y

f

x

,

e

SSR

= =

θ

=

=

Least-squares method

EXPERIMENTAL DESIGN AND

EXPERIMENTAL DESIGN AND

DATA ANALYSIS

(37)

OUTLINE

OUTLINE

 Introduction

- Non-thermal Processes - Mathematical Modelling

- Experimental Design and Data Analysis

Cases Studies

- Ozone, UV-C, Thermosonication

- Red bell pepper / ozone - Courgette / UV-C

(38)

Ozone Exposure of food to ozone

Ultrasonication Exposure of foods to ultrasounds (US)

US + mild temperatures (T)  thermosonication

US + pressure (P)  manosonication

US + T + P  manothermosonication

UV-C Exposure of food to controlled pulses of UV rays

CASE STUDIES

(39)

OZONE

-Gas formed by 3 oxygen atoms -Highly instable

-In nature it is formed by the action of sun UV light (185 nm)

CASE STUDIES

(40)

OZONE

-Commercially:

Ozone generated by

Electrical Discharge

CASE STUDIES

CASE STUDIES

(41)

OZONE

-Powerful antimicrobial agent  strong oxidant

-Lethal or inhibitory effect on microorganisms due to its reaction with: - intracellular enzymes

- nucleic material

- membrane components  destruction of coating of spores and viral

capsules

CASE STUDIES

(42)

ULTRASOUNDS

- Vibrations similar to sound waves

- Very high frequencies: 18 kHz – 500 MHz  greater than upper limit of

human hearing!

- Some animals, such as dogs, dolphins, and bats, have an upper limit

that is greater than that of the human ear and thus can hear ultrasound.

CASE STUDIES

(43)

ULTRASOUNDS

- In a biological medium: production of compression and expansion cycles

 CAVITATION phenomenon

- The implosion of gas bubbles  high temperature

and high pressure spots

 Cell disruption  cellular death

CASE STUDIES

(44)

ULTRAVIOLET RADIATION

- Ultraviolet light in the non-ionizing region of the electromagnetic

spectrum, between X-rays (200 nm) and visible light (400 nm)

CASE STUDIES

(45)

UV light can be divided into three regions:

- UVA: 320-400 nm – therapeutic effects (dermatological);

- UVB: 280-320 nm – sun burn and plant damage

- UVC: 100-280 nm – dangerous to life – maximum lethal effect at 254 nm

ULTRAVIOLET RADIATION

CASE STUDIES

(46)

ULTRAVIOLET RADIATION - UVC

Lethal effect (254 nm) due to its destroying action on DNA chains 

decreasing or inactivation of vital functions of cells

CASE STUDIES

(47)

Products

Strawberry Red bell pepper Watercress

(48)

Technologies

(49)

SAFETY

water ozone US + 65ºC

-+ QU AL ITY UV-C ultrasounds

QUALITY

UV-C water ozone US + 65ºC

-+ S A F E T Y ultrasounds combined

Compromise: safety + quality

Colour pH Antocianins Vitamin C Texture Microstructure Sensorial analysis

However, the impact depends on: Microorganism / Product

(50)

OUTLINE

OUTLINE

 Introduction

- Non-thermal Processes - Mathematical Modelling

- Experimental Design and Data Analysis

Cases Studies

- Ozone, UV-C, Thermosonication

- Red bell pepper / ozone

- Courgette / UV-C

(51)

0 1 2 3 4 5 6 0 10 20 30 40 50 60 70

Tempo de tratamento (min)

L o g ( N 0 /N )

Red pepper ozonated Red pepper washed Red bell pepper / Listeria innocua

Ozone

red bell pepper

Kinetc

Kinetc behaviourbehaviour

Ozone

Water

Water / Listeria innocua

-3,5 -3,0 -2,5 -2,0 -1,5 -1,0 -0,5 0,0 0 2 4 6 8 10 12 14 16

Tempo de tratamento (min)

L o g ( N /N 0 )

(52)

UV Water Chemicals Ozone US + 65 ºC

-+ Blanching (50 – 85 ºC) 0.5 – 0.8 0.5 – 1.5 0.5 – 2.0 2.5 – 3.0 0.5 – 4.5 4.0 – 5.0

SAFETY (total mesophyls)

No synergetic effects of

ozone with temperature

(53)

OUTLINE

OUTLINE

 Introduction

- Non-thermal Processes - Mathematical Modelling

- Experimental Design and Data Analysis

Cases Studies

- Ozone, UV-C, Thermosonication - Red bell pepper / ozone

- Courgette / UV-C

(54)
(55)
(56)

0,001 0,01 0,1 1 10 0 20 40 60 80 100 Tim e(s) N /N0 ( (◊◊) ) — 11 J/m11 J/m22 ( () ) ---- 8 J/m8 J/m22 ( () ) ······ 5 J/m5 J/m22 total mesophyls at 30 º30 ºCC

(57)

0 0.2 0.4 0.6 0.8 1 1.2 0 50 100 150 200 Time (s) C /C 0 0 0.2 0.4 0.6 0.8 1 1.2 0 50 100 150 200 Time (s) C /C 0 0 0.2 0.4 0.6 0.8 1 1.2 0 50 100 150 200 Time (s) C /C 0 0 0.2 0.4 0.6 0.8 1 1.2 0 50 100 150 200 Time (s) C /C 0 0 0.2 0.4 0.6 0.8 1 1.2 0 50 100 150 200 Time (s) C /C 0 0 0.2 0.4 0.6 0.8 1 1.2 0 50 100 150 200 Time (s) C /C 0 0 0.2 0.4 0.6 0.8 1 1.2 0 1000 2000 3000 4000 Time (s) C /C 0

() heat () heat and UV-C

Effect on Peroxidase ….

Temp. and UV-C

(11 J/m

2

)

(58)

OUTLINE

OUTLINE

 Introduction

- Non-thermal Processes - Mathematical Modelling

- Experimental Design and Data Analysis

Cases Studies

- Ozone, UV-C, Thermosonication - Red bell pepper / ozone

- Courgette / UV-C

(59)

Effect on Peroxidase ….

Synergetic effect of

(60)

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

+

=

t e k t e k R T Tref Ea ref ref T T R Ea ref

e

C

e

C

C

1 1 2 2 1 1 1 1 02 01

(61)

0 0.2 0.4 0.6 0.8 1 1.2 1.4 0 0.5 1 1.5 2 Time (min) C /C o 0 0.2 0.4 0.6 0.8 1 1.2 1.4 0 0.5 1 1.5 2 Time (min) C /C o 0 0.2 0.4 0.6 0.8 1 1.2 1.4 0 0.5 1 1.5 2 Time (min) C /C o 0 0.2 0.4 0.6 0.8 1 1.2 1.4 0 0.5 1 1.5 2 Time (min) C /C o 0 0.2 0.4 0.6 0.8 1 1.2 1.4 0 0.5 1 1.5 2 Time (min) C /C o 82.5 ºC 85 ºC 87.5 ºC 90 ºC 92.5 ºC Vitamina C             −                 − −

=

t e k R T T a E

e

C

C

ref 1 1 ref 0

(62)

          −             − −

=

k e t T T R E

e

C

C

C

C

ref 1 1 a ref e 0 e 0.8 0.9 1.0 1.1 1.2 0 20 40 60 80 100 120 Time (s) a n 0.8 0.9 1.0 1.1 1.2 0 20 40 60 80 100 120 Time (s) a n 0.8 0.9 1.0 1.1 1.2 0 20 40 60 80 100 120 Time (s) a n 0.8 0.9 1.0 1.1 1.2 0 20 40 60 80 100 120 Time (s) a n 0.8 0.9 1.0 1.1 1.2 0 20 40 60 80 100 120 Time (s) a n Colour a*

(63)
(64)
(65)

CBQF CBQF CBQF

CBQF ---- INTERFACE AINTERFACE AINTERFACE AINTERFACE A4444

State Associated Laboratory State Associated LaboratoryState Associated Laboratory State Associated Laboratory

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