2016.10.26.

Szent Istvn University, Budapest

Department of Food Preservation

Food Additives

How do food products change?

I. Beneficial, positive changes
Ripening of fruits

Additives extending the shelf-life

Preservatives and Antioxidants

Ripening of cheeses
Maturation of wine

26th October 2016.

Lecturer: Dr. Juhsz Rka

II. Physical changes

Mechanical hurts

II. Physical changes what to do?

Drying, moisture loss proper packaging and storage
conditions, water binding

Drying, moisture loss

Moisture uptake

Moisture uptake
moisture

Storage, Packaging, antiagents

Recrystallization

Recrystallization

emulsifiers

Consolidation of fibres

Consolidation of fibres Processing technology,

thickeners

III. Chemical changes

Color loss

III. Chemical changes what to do?

Color loss Stabilizers, proper food matrix,
antioxidants, colorants

Browning
Browning Dark packaging, antioxidants
Vitamin loss, aroma loss
Rancidity of fats and oils

Vitamin loss, aroma loss Storage, antioxidants,

stabilizers
Rancidity of fats and oils Antioxidants

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IV. Enzyme reactions

Enzymatic browning of fruits
Chlorophyll degradation
Starch hydrolysis
Cellulose, pectin hydrolysis
Organic acid decomposition

IV. Microbial changes

2. Yeasts

IV. Microbial changes

1. Bacteria
a) poisoning, acut problems of consumer only
Staphylococcus aureus
Salmonella
Clostridium botulinum botulism
Lysteria monoscytogenes
b) Infection epidemic could occur
Salmonella typhi
Shigella dysenteriae (dysentery, blood-flux)
Vibrio cholerae (cholera)

IV. Microbial changes

3. Moulds

Osmofil yeasts in honey

On the surface of food products and raw

materials
Toxins produced during storage mycotoxins

Deterioration of cheese

aflatoxin, ochratoxin in nuts

Deterioration of pickles

patulin in fruits
fusariotoxins in cereals

What to do against microbial changes?

I. Preservatives

Provide proper hygienic conditions

Food Preservation!
-

Temperature
Low pH
Low water activity (drying, evaporation)
High salt, sugar concentration
Aseptic packaging etc.

preservatives

2016.10.26.

Preservatives (1333/2008/EK)
are substances which prolong the shelf-life of foods
by protecting them against deterioration caused by
micro-organisms
and/or which protect against growth of pathogenic
micro-organisms

Preservative substances
High concentration substances
(Salt: 3-20%, sugar: 30-60%, organic acids: 2-3%)

Materials used at concentration level lower than 1%

Protect against microorganisms

Factors influencing effect of preservatives

I. concentration

Requirements for food preservatives

Not hazard consumers health

Used when neccessary, in least effective dosis
Not used: to hide hygienic, technological problems
Do not affect organoleptic properties of food (ie. taste)
standard composition, meets purity criteria,
specification
Proper analytical method
easy to use
Low cost

Effects and mechanisms of

preservatives
Decrease water activity (salt, sugar)
Influence ion-balance of the matrix (organic acids)
Antimicrobial effect (preservatives)
metabolism: in complete living cells

Structural change of cell membrane, organelle,

Inhibition of synthesis of nucleic acids, proteins

Factors influencing effect of preservatives

II. water activity decreasing agents

Minimum effective dosis

Dose increase = exponentially increased effect
C=concentration of preservative
n=concentration index
t= acting time
a=constant

lg t1 lg t 2
lg C 2 lg C1

glucose

aw

C t a
n

NaCl

sucrose

n=1,
double concentration = half time
gylcerine

concentration

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Factors influencing effect of preservatives

III. pH

Factors influencing effect of preservatives

III. pH

Undissociated part %

Antimicrobial effect: undissociated molecules (lipofil

character)

Acid (HA) in aquaeous solution

dissociate to (H+) and (A-)

(H )(A )
(HA)

Concentration of Hydrogen ions

(pH) depends on dissociation level
of acids

pK lg K
pH pK lg

(A )
(HA)

K= dissociation constant
pK= dissociation exponent

Factors influencing effect of preservatives

III. pH

(H )(A )
(HA)

The higher K value = lower pK =

lower concentration of active form

Antimicrobial effect depends on dissociation

constant (K) and pH
The higher K value requires lower pH
(A )
pH pK lg
Low K value: effective at pH 5-6
(HA)
High K value: effective at pH 3-4

Factors influencing effect of preservatives

III. pH
Dissociation

Dissociation

Acid

constant

Undissociated acid %

Preservative

constant

Undissociated acid %

exponent

exponent

Acetic acid
Lactic acid
Citric acid
Tartaric acid

Low K value: effective even at pH 5-6

High K value: effective at pH 3-4, not effective at pH 5-6

Factors influencing effect of preservatives

IV. Partition coefficient

Partition coeffcient = preservative in aquaeous phase

/ preservative in oily phase
Reproduction of microorganisms: in aquaeous phase
The lower PC, the better utilization in fatty food
products

Sulphur-dioxide
Salicic acid
Formic acid
Benzoic acid
P-hydroxy
benzoic acid
Sorbic acid
Propionic acid

Preservatives
1. Inorganic
2. Organic
3. Special

2016.10.26.

Inorganic preservatives
1. Sulphur-dioxide E220 and Sulphites E221- E228

Inorganic preservatives
1. Sulphur-dioxide E220 and Sulphites E221- E228

Sulphur-dioxide E220

Sodium-metabisulphite E223
Sulphites are the salts and esthers of the sulfurous
acid (H2SO4).

antioxidant and antiseptic

Biocide, enzyme inhibitor, discolouring effect
Affect proteins, and enzymes with thiol groups SH
against yeast, bacteria, and moulds
Maximum effectivity: at pH 3-4 (high dissociation constant)

Limited utilization: corrosive, unhealthy effect

Destroy B1 vitamine, irritative, allergenic.
Utilization: wine, beer, crabs, horse radish cream, mustard,
dried fruit

Inorganic preservatives
1. Sulphur-dioxide E220 and Sulphites E221- E228
Sun dried apricots
without any treatment

Sun dried apricots

with sulphur treatment

Inorganic preservatives
2. Nitrites E249, E250 and nitrates E251, E252
Nitrates (KNO3, NaNO3)
Occurs in green leave vegetables, cheese, meat
products
ADI: 3,7 mg/bwkg.
No health risk, but: forms nitrites!

Pealed potatoes
without sulphur treatment

Pealed potatoes
with sulphur treatment

Nitrites (KNO2, NaNO2)

Intensive antimicrobial effect, precaution for
Clostridium botulinum
Colouring and aromatizing effect
Used in combination with nitrates and NaCl
In pickle salt of meat products
(98,5% NaCl, 1% NaNO3, 0,5% NaNO2)

Inorganic preservatives
2. Nitrites E249, E250 and nitrates E251, E252

Inorganic preservatives
2. Nitrites E249, E250 and nitrates E251, E252

utilization in meat products for:

precaution for Clostridium Botulinum
prevent discolouration
Extend shelf life

Caution!!!
Nitrites bind irreversible to hemoglobin
Inhibit oxygene carrier function
React with amino acids producing
nitroze amines - carcinogenes
Potential mutagenes
Prohibited for infants and children

mioglobin

Nitrozomioglobin (red)

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Preservatives

Organic preservatives
1. Formic acid (E 236)
HCOOH
Unpleasant spicy taste
Characteristic odour

1. Inorganic
2. Organic

Against yeast, mould, bacteria

Utilization in acidic products (pH<3)

3. Special

Fruit juices, tobacco, fish processing

Organic preservatives
2. Propionic acid (E 280) and propionates (E281-283)

Organic preservatives
3. Sorbic acid (E 200) and salts (E 202-203)

Generally used, degraded completely

White, sour crystalls
Poor solubility sorbic acid: (0,16 g/100 g water)

Strong, pungent odour

Degradated to water and CO2
Competitive inhibition
Low dissociation constant: effective at pH 5-6

Against moulds and glutionusness (caused by

Bacillus subtilis) in bakery products
Utilization level:
packed, sliced bread: : 3000 mg/kg
bread, cake: 2000 mg/kg

Organic preservatives
4. Benzoic acid (E 210) and salts (E 211-213)
Generally used, exhausted from organism
White crystalline powder
Poor solubility (0,34 g/100g)
Na-benzoate: 63 g/100g

Affects enzyme system of microorganisms (citric acid

cycle)
Against yeast and moulds
Not effective against bacteria
High dissociation constant : effective at pH 3-4
Utilization: widespread
Drinks, fillings, sauces, fruits, vegetables, margarine, meat, fish,
salads, liquid egg, tobacco etc.

Na-sorbate: 32 g/100g water

K-sorbate: 138 g/100g water

Against yeast and moulds

Used in combination because off-taste
Low dissociation constant: effective at pH 5-6
Low partition coefficient (margarine, mayonnaise,
cheese, sausages)

drinks, pastry fillings, fruit and vegetable products, meat and fish
products, bakery products, fermented products (lactic acid)

Organic preservatives
5. p-hidroxy-benzoic acid (E215) and residues (E216-219)
Against moulds (fungstatic)
Bacteristatic effect because of phenolic hydroxyl
Estherized by alcohols: the longer chain the stronger
antimicrobial effect
methyl: 3-4x
ethyl: 5-8x
propyl 25x effect compared to phenol

Do not dissociate: independent from pH

Health issues: discussed
Utilization:
preserved and dried meat products , snacks, sweets, cold buffets

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Summary: Inorganic and organic preservatives

Bacteria

Yeasts

Moulds

Nitrite

++

Sulphites

++

Propionic acid

++

Sorbic acid

+++

+++

Benzoic acid

++

+++

+++

P-hydroxy-benzoic
acid

++

+++

+++

Preservatives
1. Inorganic

2. Organic
3. Special

Special preservatives
1. Nisin (E234)

polypeptide
Produced by Lactobacillus lactis from milk
Antibiotic, bacteriocin
Against Gram negative spoilage bacteria

inhibition of cell wall synthesis

forming pores in the cytoplasmic membrane

Special preservatives
1. Nisin (E234)
soluble in water
most stable in acid conditions,
Utilization:
in heat processed and low pH foods
ADI = 02 mg/kg bw
For cheeses: 12,5 mg/kg
Mascarpone 10mg/kg

often used in combination with other synergistic preservation

methods such as low pH and high salt concentrations.

Special preservatives
2. Natamycin (E235)

Special preservatives
2. Natamycin (E235)

Produced by submerged aerobic fermentation

by Streptomyces natalensis and related species
Effective against yeasts and moulds

Has no effect on bacteria, making

it useful for food products
produced by bacterial cultures

Soluble in water - 20-50 mg/L

Effective over a wide range of pH values (3-9)
low dosage rate

surface treatment of rind of semihard and semi-soft cheese and

of dried, cured sausages
Secures desired food flavor

Can cause nausea, vomitting, diarrhoea, skin

irritation

As a medicine: eye drops, fungicid

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Special preservatives
3. Boric acid (E284) and borax (E285)

Special preservatives
3. Boric acid (E284) and borax (E285)

Boric acid is industrially synthesised by treating borax with

strong acid.

Utilization:
buffer to control acidity in products

Antiseptic
Boric acid

in multi-vitamin/mineral products as a
mineral source

may cause reproductive disorders.

add a firm rubbery texture ie. Chinese
foods like hand-pulled noodles: la mian

risk of liver cancer with high consumption over a period of

510 years
banned in the US.

Sodium-borate

II. Antioxidants

In EU: preservatives of sturgeon eggs

(caviar) up to a maximum concentration
of 4 g boric acid/kg.

II. Antioxidants
substances which prolong the shelf-life of foods
by protecting them against deterioration
caused by oxidation,
such as fat rancidity and colour changes

Antioxidants: grouping
Mechanism

examples

Oxygene binder

ascorbic acid and salts E 300 303

Antioxidants
1. Ascorbic acid (E300) and residues
Sodium-ascorbate (E301), Calcium-ascorbate (E302)

Complex forming citric acid E 330,

ascorbic acid E 300,

sulphur compounds E 220 228

Radical catcher

BHA E 320; BHT, E 321,

tocopherols E 306 309,
gallates E 310 312

synergents

tartaric acid E 334,

citric acid E 330,
phosphoric acid E 338,
lactic acid E 270,
sodium-lactate E 325

Ascorbic acid + fatty acids (palmitate, stearate)

BHA

Eritro-ascorbates (E315-E316)

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Antioxidants
1. Ascorbic acid (E300) and residues
To prevent: browning of fruits and vegetables and seafood
Browning: polyphenols to chinons by polyphenol oxidase (PPO) enzyme
resulting brown pigments
may be responsible for up to 50% of all losses during fruit and vegetables
production

As a flour treatment agent to increase loaf volume

Antioxidants
2. Tocopherols (E306-309)
Fat soluble
Vitamin E
Naturally occurs in: sunflower seed
oil, nuts
Synergent effect with ascorbic acid
Radical catcher

In presence of gluthation reduction of disulfide-bonds in wheat proteins

As a stabilizer agent in gels and fillings

to control pH of food products

Antioxidants
3. Buthyl-hydroxy-toluol BHT (E321)
Buthyl-hydroxy-anizol BHA (E322)
Rancidity Unpleasant odour and flavor in food because of
deterioration of fats and oils
May caused by: oxidation, microbial effects, hydrolysis
Hazards of rancidity:
Toxic compounds: poisoning, cancer,
Destroy: fat soluble vitamins, essential fatty acids
Inedible food products economic loss

Utilization:
Meats, soft drinks, deep forzen
products, icecreams, ready-to-eat
meals

Antioxidants
3. Buthyl-hydroxy-toluol BHT (E321)
Buthyl-hydroxy-anizol BHA (E322)

synthetic antioxidants
Used in combination
white or yellowish crystalline or waxy solid

Prevent fats and oils from becoming rancid

Oxygen reacts preferentially with BHA rather than
oxidizing fats or oils
fat-soluble > added to foods with fat

Permitted level: 200-400mg/kg

ADI =1.0 mg/kg bw/day

Growth retardation, increased mortality and

behavioral effects

Oils, Cereal based food (cakes, snaks, pre-cook cereals),

Dehydrated soups, meat and potatos, Processed nuts, Sauces,
Butter, Cereals, Chewing gum

Antioxidants
4. Gallates (E310-312)

BHA

BHT

References

synthetic antioxidants

1.

1333/2008/EK

2.

1129/2011/EK

Prevent fats and oils from becoming rancid

3.

Horvth D.n: A gymlcsfeldolgozs adalkanyagai 205-208. In.: Barta

J. (szerk.), 2007, Budapest: A gymlcsfeldolgozs technolgii

Used in fatty foods

4.

Sohr P.n-Domoki J. (szerk), 2005, Budapest: Mit kell tudni az

lelmiszeripari adalkanyagokrl?

5.

Sohr P.n-Rcz E.(2008): szintn s rtheten az adalkanyagokrl

1. rsz, lelmezsi Ipar, LXII.,4., 108-110.

6.

Szenes E.n-Olh Mikls (szerk.) 1991, Konzervipari kziknyv

Utilization: Oils, Cereal based food (cakes, snaks, precook cereals), Dehydrated soups, meat and potatos,
Processed nuts, Sauces, Butter, Cereals, Chewing gum