Title: Flavoring Beverages: Opportunities and Challenges
1Flavoring BeveragesOpportunities and Challenges
October 2005
- Andrew G. Lynch, Ph.D.
- Quest International
- Global Citrus Applications Manager
- andrew.lynch_at_questintl.com
2What is Food Science ?
Food Science deals with the physical, chemical
and biological properties of food. Food
Scientists are concerned with Nutrition and
Safety Stability Processing and Packaging Cost
and Quality There are very few things as
personal as food!
3flavoring beverages
- background
- opportunities
- challenges
- citrus flavor stability
- orange juice processing
- clouds
- milk coffee drinks
4Quest for creative difference
key facts
- creative leader in the industry
- corporate headquarters in Naarden, the
Netherlands - two businesses Flavours and Fragrances
- total sales US 1.1 billion (2003)
- creative and application centres and production
facilities across Europe, the Americas and Asia
Pacific - approx. 3,500 employees
5Quest for creative difference
sales 2003 US 1.1 billion
6flavoring beverages
- background
- opportunities
- challenges
- citrus flavor stability
- orange juice processing
- clouds
- milk coffee drinks
7opportunities - North American beverage market
8opportunities
market trends
- diet (low carbohydrate, low calorie)
- healthy fats (shift from trans and hydrogenated
fats) - shift from fanciful to more exotic natural flavor
- e.g. Blood orange instead of orange
- masking, suppressing smoothing
- innovative beverages
9opportunities
non-alcoholic beverage segment new launch top
flavors 2004
citrus flavors top the list, moving strawberry
from 1 2003 to 3 in 2004. cranberry and
chocolate are new to the list.
- lemon
- orange
- strawberry
- chocolate
- apple
- peach
- mango
- raspberry
- vanilla
- cranberry
Source Global New Products Database (Mintel)
10opportunities
obesity
Obesity in the US is truly an epidemic. In the
last 10 years, obesity rates have increased by
more than 60 among adults.
Source World Health Organization 2003
11opportunities
masking and suppressing
- bitterness
- (soy, grapefruit, protein drinks, coffee)
- sourness
- (coffee, fermented and acid products)
- saltiness
- (iso-tonic applications)
- artificial sweetener
- (low cal products, lingering aftertaste, lack of
body)
12opportunities
enhancement
- sweetness
- sugar flavors
- aromatics beyond drinking
- odor release prior to consumption, instant teas
coffees - visual
- taste modification
13opportunities
innovation in beverages
- dairy-based beverages
- soy and juice combination drinks
- meal replacement (juice/cereal/yogurt)
14flavoring beverages
- background
- opportunities
- challenges
- citrus flavor stability
- orange juice processing
- clouds
- milk coffee drinks
15challenges
- packaging
- regulatory
- consistent quality of natural ingredients
- stability
- processing
- flavor stability
- physico-chemical stability
16challenges
regulatory
- GMO
- natural artificial
- kosher
- nature identical
- global customers
- globalization of flavors
- Halal
- TTB (formerly BATF)
17challenges
consistent quality of natural ingredients
- natural products have natural variation
- focused quality assurance program is critical
- catastrophe in one part of the world? Example
2004 Florida hurricanes significantly damage
grapefruit crop
18challenges
processing
- consistency in scale-up transfer to other
regions - processing impact on flavor/cloud
- hot fill vs. cold fill
- oxygen control
19challenges
flavor degeneration
- fading
- light induced degradation
- acid hydrolysis
- oxidation
20flavoring beverages
- background
- opportunities
- challenges
- citrus flavor stability
- orange juice processing
- clouds
- milk coffee drinks
21challenges
citrus flavor stability
- oxidation of terpenes
- citral in aqueous low pH
- acid catalyzed hydrations
Source Rouseff, R. and Naim, M. 2000. Citrus
Flavor Stability. In Flavor Chemistry, ed. By
Risch, S.J and Ho, C.T. American Chemical
Society. Pages 101-121.
22challenges
citrus stability demonstration
- soda base
- pH 2.7
- Brix 10.6
- Carbonation 7 g/L
- Good oxygen control
- storage conditions
- 2 weeks at 4C and 2 weeks at 45 C
23challenges
typical off flavor formation in acidic aqueous
solution
24challenges
off flavor formation in lemonade stored at high
ambient temperatures
25challenges
sensory analysis of aged lemonades
3.5
3
2.5
2
1.5
1
0.5
0
26challenges
lemon flavors
less off flavors increased shelf life
citrus flavors that deliver traditional citrus
favorites with authentic taste
profiles
27flavoring beverages
- background
- opportunities
- challenges
- citrus flavor stability
- orange juice processing
- clouds
- milk coffee drinks
28Orange Juice Processing
- Oranges are processed to make not from
concentrate (NFC) or frozen concentrated orange
juice (FCOJ) - Quality must be controlled (variety, growing
conditions, etc) - Processing must be closely controlled to
- Deactivate enzymes
- Limit oxygen levels
- Destroy pathogenic and spoilage microorganisms
- Minimize chemical and flavor changes
- Correct packaging and storage conditions must be
used to deliver safe and stable product to
consumers. -
29Cross section of Orange
Juice vesicles
Flavedo
Albedo
Oil glands
30Citrus Materials Basic Processing
31Overview of Production of Orange Juice Concentrate
Main Products
By-Products
Peel Oil
Oil Phase Water-Phase Aroma
Pulp, Limonene, Citrus Pulp Pellets
32Why does juice need to be pasteurized ?
- (1) Enzyme deactivation
- Deactivation of pectin methyl esterase (PME)
- PME cleaves methyl groups from pectin causing
cloud loss and gelation - Calcium (from the juice) interacts with the
demethylated pectin - Calcium pectate is insoluble and settles at the
base of the container - For Florida-grown Valencia oranges, a heat load
of 2-3 D values is generally sufficient for total
enzyme destruction. - Typically pasteurization conditions employed are
95-98C for 10-30 secs. -
33Why does juice need to be pasteurized ?
- (2) Ensure a microbiologically stable product
- Main micro-organisms of interest in OJ are
- Acid-tolerant bacteria, yeasts and moulds
- Acid-tolerant bacteria, e.g., Lactobacillus
plantarum (grow best at 20-37C) - Spoilage characterized by diacetyl (buttery)
off-notes and CO2 - Saccharomyces cerevisiae is the most common
spoilage microorganism - Spoilage characterized by alcoholic fermentation,
off-flavors and CO2 - Spore-forming microorganisms (thermo-resistant
acidophilic bacteria) - In 1992, Alicyclobacillus classified as new genus
- Spoilage characterized by an off-flavor like
disinfectant or guaicol -
34Thermal processing of OJ
- Thermal resistance of microorganisms is
traditionally expressed in terms - of D values and Z values.
- D value is the time at a specified temperature
for the microbial population - to decrease by 90 or one log cycle (also called
the decimal reduction time) - Z value is the change in temperature needed to
alter the D value by - one log cycle
- For example, if an organism has a z 10C and a
D80C 1 min, - then the D90C 0.1 min and the D70C 10 min.
-
35Thermal processing of OJ
- Pasteurization destroys most vegetative
microorganisms but has little effect - on bacterial spores (Most spores do not grow lt
pH 4.5). - long term survival of some pathogens in
unpasteurized refrigerated juice is possible,
therefore pasteurization is recommended - For microorganisms usually found in fruit juices,
z values are typically 5-7. - Typical pasteurization temperatures are 75-95C
for 15 to 30 secs - For a given increase in temperature, the rate of
destruction of microorganisms and enzymes
increases faster than the rate of destruction of
sensory and nutrient components. - SummaryDeactivate enzymes, Ensure
microbiological safety and minimize heat damage
to nutrient and flavor components. -
36Theoretical thermal destruction curves of pectin
methyl esterase, ascospores and vegetative cells
of Saccharomyces cerevisae in orange juice (The
Orange Book, Tetra Pak)
37challenges
packaging
- trend towards less glass and increased use of
polypropylene and PET (polyEthyleneTerephthalate) - scalping (loss of flavor into the
packaging material) - permeation (movement of compounds through
packaging materials) - migration (movement of components of the
packaging material into food product)
Source Risch, S. 2000. Flavor and packaging
interactions. In Flavor Chemistry, ed. By
Risch, S.J and Ho, C.T. American Chemical
Society. Pages 94-100.
38Barrier properties
oxidation
Flavor
Flavor fading (scalping, permeation)
Permeation rate Diffusion x Solubility P D x S
39Vitamin C stability in different package types
(The Orange Book, Tetra Pak)
AA ½ O2 DHA H20 AA ascorbic acid (vitamin
C), DHA dehydroascorbic acid
40Properties of different polymers P D x S
- Polar polymers PET, ethylene vinyl alcohol
(EVOH) and polyamide (PA) show very slow
diffusion coefficients with polar and non-polar
aroma compounds. - Non-polar polymers low density polyethylene
(LDPE), high density polyethylene (HDPE) and
polypropylene (PP) - Limonene (non-polar aroma compound) has a high
solubility in all the non-polar polymers and
diffusion and consequent permeation rates differ
by orders of magnitude in the different polymers
in decreasing order - LDPE gt HDPE gt PP
- Ethyl butyrate (polar aroma compound) has low
solubility in non-polar polymers. Losses of polar
molecules are negligible with this type of
barrier.
41Terpenes the largest single chemical class
within citrus volatiles
- Three month study of orange juice in Tetra-Pak
laminated containers showed - Significant loss of limonene due to
absorption/scalping by polymer barrier - a-terpineol (formed from degradation of limonene)
increased more rapidly at higher storage
temperatures - Duerr et al., Alimenta 1981, 20, 91-93
42Volatile contribution to orange juice aroma
- Contribution to typical aromas Contribution to
off-notes - Important Desirable Precursors Detrimental
- ethyl butyrate linalool linalool a-terpin
eol - neral limonene limonene carvone
- geranial a-pinene valencene t-carveol
- valencene 4-vinyl guaiacol
- acetaldehyde 2,5-demethyl-4- hydro
xy-3-(2H) furanone octanal - nonanal
- a-sinensal
- b-sinensal
43flavoring beverages
- background
- opportunities
- challenges
- citrus flavor stability
- orange juice processing
- clouds
- milk coffee drinks
44challenges
clouds
- provides turbidity to a beverage visual
enhancement that gives finished beverage more
value - many different types of cloud systems
- weighting agents in clouds are regulated
- sucrose acetate isobutyrate (SAIB)
- brominated vegetable oil (BVO)
- ester gum
- blended systems
45challenges
clouds
- Neutral cloud
- Goal cloud with minimal taste impact
- Most made from orange terpenes
- Vegetable oil as an alternative
- typically less stability
- cleaner taste
46challenges
cloud ringing
- emulsion in beverage product breaks down giving
rise to creaming - perform tests to predict stability
- make assumptions for predictions
- microscope, particle size analyzer, shelf-life
studies etc.
47challenges
cloud ringing
- Stokes Law
- V 2gr2 (po-p)
- 9no
- v velocity
- r droplet radius
- g gravity
- po - p difference in density
- no viscosity
v negative creaming v 0 stable cloud v
positive sedimentation
48challenges
cloud ringing
ringing
stable
phase separation, shrinkage of cloud layer
49flavoring beverages
- background
- opportunities
- challenges
- citrus flavor stability
- orange juice processing
- clouds
- milk coffee drinks
50milk-coffee RTD challenges
matrix complexity
- milk-coffee drinks contain coffee, milk,
sweeteners, flavors, salts, hydrocolloids,
proteins, emulsifiers amongst other components - complex mixture of ingredients
- physico-chemical and flavor stability issues
(processing and storage)
51Milk coffee RTD matrix
Milk coffee RTD matrix
Coffee
Specialty proteins
Alternative systems
Black Coffee
Fresh whole milk Fresh skimmed milk Skim/whole
milk powders
Caseinate
Clouds
Whey proteins
Others
Others
Dairy/non-dairy fat with milk flavour
Effect of heating, antioxidants, pH, O2 content,
stabilizing salts, homogenization etc.
Processing
Emulsifiers, Proteins Hydrocolloids
RD
Application, Sensory Flavour expertise
Beverages with improved stability fresher
coffee flavour
52milk-coffee RTD opportunities
consumption
- coffee consumption is growing
- 2.5 billion liters of canned coffee are consumed
annually in Japan alone! - served hot during winter cold in summer
- beverage manufacturers are adopting coffee house
trends into RTDs
53milk-coffee RTD challenges
flavor complexity
- coffee contains over 830 volatile components!
- some of the key flavor components responsible for
freshroast coffee character are - 2-furfurylthiol
- coffee aroma and taste is dependent on the type
of coffee used - species Arabica or Robusta
- origin
- degree of roasting
54milk-coffee RTD challenges
flavor complexity
- at temperatures gt 60C, acidity increases,
sourness increases and volatiles are lost
resulting in an unpleasant drinking experience - milk is added to coffee for
- appearance
- taste
- mouthfeel
55LC Fractionation of Arabica Coffee (filtered brew)
56milk-coffee RTD challenges
flavor complexity
- coffee flavors are needed to compensate for the
damage to the coffee volatiles during the
extraction and beverage processing stages - fruity (eg. acetaldehyde)
- phenolic (eg. guaiacol)
- earthy (eg. 2-ethyl-3,5-dimethylpyrazine)
- roast (eg. 2-furfurylthiol)
- sweet (eg. methylpropanal)
- opportunities for flavored coffees include
- vanilla
- Irish Cream
- chocolate and caramel
- macadamia Nut and Hazelnut
- amaretto and almond
- coconut
- fruit flavors eg.
orange raspberry
57The composition of milk
58Main fatty acids of milk fat
59Distribution of the major constituents of the
casein micellebetween the serum and micellar
phases of bovine milk at pH 6.7 at 20C
60Some physico-chemical characteristics of casein
micelles
61Schematic representation of a sub-micelle (A) and
a casein micelle (B) composed of sub-micelles
(from Schmidt, 1982)
62Possible reactions of side-chain residuesof
proteins at high temperatures 1
1.
-CH2-CONH2 H2O Asparagine
-(CH2)2-CONH2 H2O Glutamine
2.
3.
-CH2-O-PO32- H2O Phosphoserine
4.
-CH2-O-PO32- Phosphoserine
-CH2-SH OH- Cysteine
5.
R1-CH2-S-S-CH2-R2 R3-CH2-S-
6.
63Possible reactions of side-chain residuesof
proteins at high temperatures 2
7.
-CH-S- -S-CH2- Cysteine
-CH2-S- Cysteine
8.
9.
CH2 HS-CH2-
10.
-(CH2)4-NH3 H2C OH- Lysine
-(CH2)4-NH3 -O2C-CH2 Lysine Aspartic acid
11.
-(CH2)4-NH3 -O2C-(CH2)2- Lysine Glutamic acid
12.
64Browning (Maillard) reactions in milk
- in milk the main Maillard reactants are lactose
and lysine - the rate of Maillard reaction in milk is
dependent on pH, time, temperature and water
activity - some of the compounds identified from dry
extracts of milk systsems incubated at pH 6 or 7
and water activity 0.75 to 0.80 included
5-hydroxymethyl-furfural, furfuryl alcohol,
furfural, maltol, acetol, 2-oxo-proponal,
acetaldehyde, and formic, acetic, propionic,
butyric and lactic acids
65Heat stability versus pH curvesfor normal skim
milk heated at 140C
HEAT COAGULATION TIME (HCT) (min.)
50
40
maximum
30
milk B
milk A
20
minimum
10
0
6.2
6.4
6.6
6.8
7
7.2
pH
66Changes which can occur to milk constituents on
heating 1
- calcium and phosphate are converted from soluble
to colloidal state - formic acid and lactulose are formed from lactose
at temperatures gt 100C - hydrolysis of the phosphoserine residues at high
temperatures - the titratable acidity of the milk increases and
pH decreases - solubility of the whey proteins decreases
significantly at temperatures gt 75C
67Changes which can occur to milk constituents on
heating 2
- enzymes are inactivated by heating at gt 50C, but
varies with enzyme - there is a decrease in redox potential probably
due to the formation of free sulphydryl groups
and hydrogen sulphide formation at temperatures gt
60C - Maillard reactions increase as temperature of
heating increases - casein micelles may start to aggregate above
110C - lactones and methyl ketones are formed from the
fat
68Alkaline urea-PAGE of solutions of sodium
caseinate heated at different pH values and
temperatures.
as1-casein
as2-caseins
Alkaline urea-PAGE of unheated sodium caseinate
(1) sodium caseinate, pH 7, heated at 110C (2),
120C (4), of 130C (6) for 5 min. and sodium
caseinate, pH 10.0, heated at 110C (3), 120C
(5) or 130C (7) for 5 min. Lynch, Andrew, Ph.D
thesis, NUI, Cork, Ireland, 1995.
b-casein
k-casein
g-casein
69milk-coffee RTD challenges
preparation of milk-coffee beverages
- Coffee-milk mixtures usually have near neutral pH
values and careful processing is required to
ensure a stable product with good organoleptic
properties - controlled temperature duration of heating
during coffee extraction - homogenization is required if milk fat or other
fat is used - sufficient amount of surface active material
must be present - check coffee-milk/ingredient and flavor
compatibility - pH of the mixture needs careful control
- sterilization/UHT processing is required for
long shelf-life products
70milk-coffee RTD challenges
why homogenize?
under homogenization
optimum homogenization
71milk-coffee RTD challenges
emulsion stability
OIL
Creaming
Coalescence separation
Aggregation creaming
Reversible
Irreversible
STABLE
UNSTABLE
72milk-coffee RTD challenges
droplet stabilitly
73Emulsifiers
- Surface active molecules
- Contain water-loving hydrophilic part and
oil-loving lipophilic part - Reduce surface tension
- Orientate at oil / water or air / water interface
- Interact with other ingredients (e.g. protein,
starch)
74Emulsifiers Chemical Characteristics
- Iodine value unsaturated fatty acids
- gram iodine absorbed per 100 g emulsifier
- Peroxidase value oxidation level
- meq. oxygen bound as peroxide per kg emulsifier
- Acid value free fatty acids
- mg KOH needed to neutralise 1 g emulsifier
- Saponification value free bound fatty acids
- mg KOH needed to saponify 1 g emulsifier
75Composition of emulsifiers
76Hydrophilic / Lipophilic Balance of Emulsifiers
77E
-o-
-OH
-OH
GMP (glyceromonopalmitate)
78- Sodium stearoyl-2-Lactylate
79milk-coffee RTD challenges
effect of homogenization pressure on particle
size distribution
volume
80flavoring beverages
- background
- opportunities
- challenges
- citrus flavor stability
- orange juice processing
- clouds
- milk coffee drinks
81Flavoring BeveragesOpportunities and Challenges