Vitamin Stabilty Beverage

Application of Vitamins in Beverages
February 5th, 2014

By Hendrik Ruijter
Head Food Application
Technical Marketing
Technical Issues of Fortification
• Clean‘ labelling and traceability of ingredients

• Sensory impact (appearance, flavour, taste)
– By added substance itself
– Due to interaction with food constituents
• Stability (chemical, physical, microbiological)
– Sensitivity of added substance at manufacturing, storage, cooking, …
Guarantee of labelled concentration
– Separation (neck ringing, sedimentation)
– Ca / Mg may enable growth of coliforme bacteria
• Bioavailability
– New requirement for added vitamins and minerals in the EU Regulation
– Provision to get health / risk reduction claims approved (efficacy)
Page 1
Solutions to Technical Issues of Fortification
• Portfolio and documentation of ingredient suppliers

• Know-how of ingredient suppliers
– Application expertise
– Adequate (over)dosing
– Formulation skills (special application forms of pure
nutrients)
• Sensory and technical performance
• Bioavailability
• Packaging innovation
– Sufficient barriers („protects what´s good …“)
– Compartment packs
Page 2
Vitamin stability
Vitamins are ...
Stable Unstable
A simple question,
but no simple answer !
Page 3
Vitamin Stability in Food
Numerous Factors Acting Over Time!
Temperatur
pH-Value Light
rH-Value
Oxygen
Energy
Vitamins
Water activity
(humidity)
Irradiation
Catalysts
Composition (Mass transfers) Time!
Page 4
Vitamin Stability in Food
Determining Factors for Beverages
Temperatur
pH-Value Light
rH-Value
Oxygen
Energy
Vitamins
Water activity
(humidity)
Irradiation
Catalysts
Composition (Mass transfers) Time!
Page 5
Stability of Vitamins
Multivitamin 10-fruit juice
Vit. E Acetate
Vitamin C
Biotin
Folic Acid
0.2 l
Niacinamide
Tetra-brik
Ca-Pantothenate
Vitamin B12
0.7 l
Vitamin B6
brown glass
Vitamin B2
Vitamin B1
β-Carotene
0 10 20 30 40 50 60 70 80 90 100
% Vitamin Retention after 12 months, at 20°C
Page 6
Vitamin stability
Vitamins are ...
Stable Unstable
The decisive questions are:

Which vitamin, which application form, where added, ... ?
Under which conditions, parameters?
Page 7
Application Profiles
for Beverages
Abbreviations used: RDA Recommended daily allowance

in the European Union (EU)
J: Fruit juices RLV proposed new Reference
N: Nectars Labelling Values in the EU
SD: Soft drinks
SP: Sports drinks Conversion factor: x = mg of product form
SO: Soy drinks in order to deliver 1.0 mg active vitamin
EN: Energy drinks
SM: Smoothies RT room temperature
VJ: Vegetable juices
WP: Water Plus products
T: Tea products
IP: Instant products
Page 8
Vitamin Stability: General Overview
Vitamin Heat Oxygen Light pH - Value

acid neutral basic
A U U U U S S
D U U U S S U
E (Acetate) S U (S) U (S) S (U) S S
K S S U U S U
C U U U S U U
B1 U U S S U U
B2 S S U S S U
B6 S S S S S S
B12 S U U S S S
Biotin S S S S S S
Folic Acid S S U U U S
Niacin S S S S S S
Pantothenic Acid U S S U S U
S = stable / U = unstable
Page 9
for Beverages
Vitamin A (Retinol)
• RDA: 800 µg (RE)
• Recommended form: Vitamin A palmitate
• Conversion factor: 1IU = 0.3 µg RE
• Appearance: turbid (emulsion)
• Taste/flavor: neutral
• Solubility (g/100 ml at RT): (emulsion)
• Stability: pasteurization good
storage light very poor
• Suitable for: chilled distribution (short t.)
• Not suitable for: most beverages
• Typical overage (6-9 mo, RT): (60-80%)
• Regulatory aspects: depends national
• Other remarks: not recommended for SD, etc.
Page 11
Vitamin A Stability in Beverages
Orange Drink (10% Fruit), Storage at RT
Product Form: Dry Vitamin A Acetate, Type 325 CWS/A

100
80
Retention [%]
60
40
20
0
Initial 1 2 3 4 5 6
Storage Time [months]
Glas white without CO2 Glas white with CO2 PET without CO2
PET with CO2 Light protected without CO2 Light protected with CO2
Page 12
Vitamin A Stability in Beverages
Orange Drink (10% Fruit), Storage at RT
Product Form: Dry Vitamin A Palmitate, Type 250 CWS/F

100
An overage of 30 – 40 % is
80 recommended to guaranty
the claimed vitamin A
Retention [%]
content on the end of the

60 6 months shelf life
40
20
0
Initial 1 2 3 4 5 6
Storage Time [months]
Glas white without CO2 Glas white with CO2 PET without CO2
PET with CO2 Light protected without CO2 Light protected with CO2
Page 13
for Beverages
Provitamin A (ß-Carotene)
• Recommended forms: ß-Carotene 10% CWS or CWS/S or Emulsions
or 3% CWS/M
• RDA: 4.8 mg
• Conversion factor: 1 mg RE = 6 mg ß-Car
• Appearance: strong yellow-orange red
• Solubility (g/100 ml at RT): n.a. (emulsion)
storage (light, pH) good,
when protected by sufficient asc. acid
• Suitable for: all (< 50% RDA/100)
• Not suitable for: WP or when no fit to flavor
• Typical overage (12 mo, RT): 0-10%
• Regulatory aspects: ok
• Other remarks: check our special information on our wide portfolio of carotene forms.
Page 14
Stability of ß-Carotene in Beverages
ß-Carotene 10 % CWS / influence of ascorbic acid
110
100
90
80
Retention in %
With ASC
70
Without ASC
60
50
40
30
20
10
0
0 2 4 6 8 10 12 14
Storage Time in Weeks
Roche Basle, VFP, 19 July 94 / Re:20.13.93.47
Page 15
Vitamin Stability in Beverages
Storage: 12 months at RT
Tetra (0,25 l)
Vitamin E Tetra (0,2 l)
Tetra (1,0 l)
PKL (0,2 l) 98
PKL (1,0 l)
88
PKL (1,5 l) 99
Glas white (0,75 l)
beta-Carotene 92
Glas brown (0,75 l) 86
98
98
64
48
75
Ascorbic Acid 69
73
69
77
76
0 20 40 60 80 100
Retention in %
Samples from ECKES GRANINI 1998
BACK
Page 16
for Beverages
Vitamin D (Cholecalciferol)
• Recommended form: D3 100 CWS/A
• RDA: 5 µg
• Conversion factor: 1 IU = 0.025 µg
• Appearance: pale, turbid (emulsion)
storage low pH satisfactory
storage light sensitive
• Suitable for: J, N, SM
• Not suitable for: clear WP, SP, EN, SD
• Typical overage (6-9 mo, RT): (40-50%)
• Regulatory aspects: depends national
• Other remarks: Necessary to add to calcium fortified products (bone health concepts).
Page 18
Vitamin D3 in Aviva® Orange drink (20 % juice)
Declared 800
Initial 733 5 °C
1 month
ambient
2 months
250 ml
3 months
glass bottles
6 months protected
from day
9 months light by
original
12 months wrapping
0 100 200 300 400 500 600 700 800 900

Vitamin D3 found (IU per liter)
Manufacturer: Novartis, analysed by VFP (S. König-Grillo), 2001

BACK
Page 19
for Beverages
Vitamin E (Tocopherol)
• Recommende form: Tocopherol Acetate 50% CWS/S
• RDA/RLV: 12 mg (TE)
• Conversion factor: 1.49 TE (2.98 of 50%)
• Appearance: turbid (emulsion)
storage low pH good
storage light good
• Not suitable for: clear products; for this application
Vitamin E 15% CC is recommended.
• Other remarks: T. acetate is inactive as an antioxidant in
vitro, but active in vivo.
As food antioxidant in vivo alpha-Tocopherol
(E307) is available for fat stabilization.
Page 21
Vitamin stability in Near Water Beverage
PET w Zn
PET w/o Zn
Vitamin E
glass w Zn
glass w/o Zn
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Retention % after 6 months

Storage Condition: 6 months in white glass (0.2 l), and PET bottle (0.33 l),
RT, ambient light
BACK
Page 22
for Beverages
Vitamin K
• Recommended form: Dry Vitamin K1 5% SD
• RDA: 75 µg
• Conversion factor: 1.0 (20)
• Appearance: slightly turbid
• Solubility (g/100 ml at RT): n.a. (emulsion)
storage low pH satisfactory
storage light sensitive
• Suitable for: J, N, VJ (< 50% RDA/100)
• Not suitable for: WP, SP, EN
• Typical overage (12 mo, RT): tbd
• Regulatory aspects: implemented in new EU legislation
• Other remarks:
Page 24
Vitamin Stability in Orange Nectar
Vitamin A Palmitate
Vitamin K1
Vitamin D3
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Retention [%] after 9 months of storage
Storage condition: white glass bottles (0.2l), RT, dark

BACK
Page 25
for Beverages
Vitamin C
• Recommended form: Ascorbic acid
• RDA: 80 mg
• Conversion factor: 1.0
• Appearance: neutral
• Taste/flavor: acid/neutral
• Solubility (g/100 ml at RT): 28
air/oxygen very sensitive
storage/light good
• Suitable for: all <50% RDA/100
• Not suitable for: nutritional labeling in low-barrier PET
(O2 migration!)
• Typical overage (12 mo, RT): 100 – 300 mg per liter, depending on
packaging).
• Other remarks: The classical antioxidant (E300) to protect color and flavor of beverages.
Prevents enzymatic browning, but may cause slight discoloration in WP products.
Page 27
Vitamin C Losses in Beverages
Effect of oxygen and filling technologies
Different filling technologies Oxygen content Loss of vitamin C
before filling
0,7 l glass bottle mg/l mg/l
1) without any dearation 10 85
2) dearation by heat, open system 4 30
3) 2) + dearation of water 2 28
4) vacuum dearation with aroma recovery1 14
5) vacuum dear. + partial dear. of water 1 14
0,2 l TETRA-BRIK
6) same as 4) 1 15
Storage losses of vitamin C mean values over

filled in 1 year at 20 °C
0,7 l glass bottle 70 - 100 mg/l
0,2 l carton 160 - 220 mg/l
Source: Wiesenberger et al. (1990)
Page 28
Reaction of Vitamin C with Oxygen
Vitamin C is also called ASCORBIC ACID

Ascorbic acid is involved in many RED-OX-REACTIONS
Oxidation
1/ O2 H 2O
2
GSSG 2 GSH
Glutathione- Glutathione
disulphide
Reduction
Page 29
Removal of oxygen by ascorbic acid
6
Asc Acid solution
Oxygen content [mg/l]
pH=6
5
Expon. (Asc Acid
solution pH=6)
4
3
y = 7.4558e-1.7697x
2 R2 = 0.9958
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
time [days]
BACK
Page 30
for Beverages
Vitamin B1 (Thiamin)
• Recommended form: Thiamine mononitrate
• RDA: 1.1 mg
• Taste/flavor: typical
• Solubility (g/100 ml at RT): 2.7
• Stability: pasteurisation good
• storage good
• Suitable for: all products with more intense
flavors (<50% RDA/100)
• Not suitable for: WP (low flavored)
• Other remarks:
Page 32
Stability of Vitamin B1
Examples: milk and cookies
Thiamine loss Increase of baking

20 – 40 % time by 2 min. 
decrease of
thiamine retention
from 60 to 40 %
Excess soda 5 or
10 g/kg flour 
decrease of
Thiamine loss < 5 % thiamine retention
from 80 % to 60 or
40 %
BACK
Page 33
for Beverages
Vitamin B2 (Riboflavin)
• Recommended form: Riboflavin
• RDA/RLV: 1.4 mg
• Appearance: yellow color
• Taste/flavor: slightly bitter
• Stability: pasteurization: good
storage dark: good
storage light: poor
• Suitable for: all, except products with significant light
exposure
• Not suitable for: WP in glass or PET
• Typical overage (12 mo, RT): 30%
Page 35
Multivitamin Juice - Light Stability
Brand product (A) in 0,7 L white bottles; light box: 900
Lux intensity
91
Riboflavin 85
76
97
beta-Carotene 96
92
100
Ascorbic Acid 97
95
0 20 40 60 80 100
Retention in % (dark)
2 days 6 days 13 days
300 Lux: Min. light intensity according to DIN 5035 Working Place Reg. (Shops)
BACK
BACK
Page 36
for Beverages
Vitamin B6 (Pyridoxine)
• Recommended form: Pyridoxine hydrochloride
• RDA/RLV: 1.4 mg
• Taste/flavor: rather neutral
• Stability: pasteurization: good
storage: good
storage light: good
• Suitable for: all (<50% RDA/100)
• Not suitable for: -
• Other remarks:
Page 38
88
89
91
Vitamin B1 Tetra (0,25 l) 88
92
87
Tetra (0,2 l) 92
Tetra (1,0 l) 91
PKL (0,2 l)
Vitamin B2 PKL (1,0 l)
PKL (1,5 l)
Glas white (0,75 l)
Glas brown (0,75 l)
Vitamin B6
Vitamin B12 93
90
88
90
0 20 40 60 80 100
Retention in %
BACK
Page 39
for Beverages
Vitamin B12 (Cyanocobalamin)
• Recommended form: Vitamin B12 0.1% WS (/N)
• RDA/RLV: 2.5 µg
• Conversion factor: 1.0 (1‘000)
storage good
storage intense light sensitive
• Other remarks:
Page 41
Vitamin Stability in Beverage
Multi Vitamin Juice
– Storage Conditions:
5 months in 0.5 PET bottles.
80
Vitamin B1 98
Vitamin B12 88
81
2 Months
Pantothenic Acid 89
72 5 Months
Folic Acid 65
46
Biotin 100
0 20 40 60 80 100
Retention [%]
BACK
Page 42
for Beverages
Biotin (Vitamin B8 or H)
• Recommended form: Biotin
• RDA/RLV: 50 µg
storage good
storage light good
• Other remarks:
Page 44
Multivitamin juice in 0.5 l PET bottles
Vitamin E Acetate
ß-Carotene
Ascorbic Acid
Vitamin B1
Vitamin B6
Vitamin B12
Biotin
Folic Acid
Ca-Pantothenate
Niacinamide
0 10 20 30 40 50 60 70 80 90 100
% Vitamin Retention after 6 months, at RT
Roche Basle Assay, 1998
BACK
Page 45
for Beverages
Folic acid (Vitamin B9)
• Recommended form: Folic acid
• RDA: 200 µg
storage (low pH) poor
• Not suitable for: red juices, berries
• Other remarks: Not compatible with polyphenols from red fruits/berries!
Page 47
Niacin Tetra (0,25 l)

Tetra (0,2 l)
Tetra (1,0 l)
52
PKL (0,2 l) 52
50
PKL (1,0 l) 50
Pantothenic Acid 58
PKL (1,5 l) 52
46
Glas white (0,75 l) 52
Glas brown (0,75 l) 40
38
91
Folic acid 37
37
43
50
Biotin
0 20 40 60 80 100
Content in %
BACK
Page 48
for Beverages
Niacin (Vitamin B3)
• RDA/RLV: 16 mg
• Recommended form: Niacinamide
storage good
storage light good
• Other remarks:
Page 50
Vitamin Stability in Diet Nectar *
Storage: 9 months at RT in 1 L COMBIBLOC (PKL)
Vitamin E 87
beta-Carotene 99
Ascorbic Acid 70
Vitamin B1 100
Vitamin B2 97
Vitamin B6 100
Vitamin B12 94
Biotin 89
Folic Acid 56
Pantothenate 55
Niacin 96
0 20 40 60 80 100
Retention in % of conc. after production
* Brand product with artificial sweetener, 1 RDA per serving (300 ml)
BACK
Page 51
for Beverages
Pantothenic acid (Vitamin B5)
• Recommended form: Calcium-pantothenate
• RDA: 6 mg
• Stability: pasteurisation good
storage (low pH) poor
• Other remarks:
Page 53
Hot isotonic sports beverage
Vitamin B1
Vitamin B2
Vitamin B6
Vitamin B12
Ca-Pantothenate
Folic Acid
Niacinamide
Vitamin C
Vitamin A Acetate
Vitamin E Acetate
0 10 20 30 40 50 60 70 80 90 100
% Vitamin Retention after: 4 hours 8 hours
Enrichment level: 1 RDA / litre
Powder dissolved in boiling water, kept in a thermos-flask. Temperature of beverage after 8 hours: 53 °C
Source: Roche Basle Assay L 85.64 PS (1985)

BACK
Page 54
Generic Information about Micronutrients
Please visit www.nutri-facts.org
Page 56

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Application of Vitamins in Beverages

February 5th, 2014

• Clean‘ labelling and traceability of ingredients

• Portfolio and documentation of ingredient suppliers

The decisive questions are:

Abbreviations used: RDA Recommended daily allowance

Vitamin Heat Oxygen Light pH - Value

Product Form: Dry Vitamin A Acetate, Type 325 CWS/A

Product Form: Dry Vitamin A Palmitate, Type 250 CWS/F

content on the end of the

0 100 200 300 400 500 600 700 800 900

Manufacturer: Novartis, analysed by VFP (S. König-Grillo), 2001

Retention % after 6 months

Retention [%] after 9 months of storage

Storage condition: white glass bottles (0.2l), RT, dark

Storage losses of vitamin C mean values over

Vitamin C is also called ASCORBIC ACID

Thiamine loss Increase of baking

Niacin Tetra (0,25 l)

Source: Roche Basle Assay L 85.64 PS (1985)

Please visit www.nutri-facts.org

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