1 Milk: Main

Characteristics
Milk is defined as the secretion of the mammary glands of mammals, its primary
natural function being nutrition of the young. Milk of some animals, especially
cows, buffaloes, goats and sheep, is also used for human consumption, either as
such or in the form of a range of dairy products. In this book, the word milk will
be used for the ‘normal’ milk of healthy cows, unless stated otherwise. Occasion-
ally, a com-parison will be made with human milk.
This chapter is meant as a general introduction. Nearly all that is mentioned —
with the exception of parts of Section 1.2 — is discussed in greater detail in other
chapters. However, for readers new to the field it is useful to have some idea of the
formation, composition, structure, and properties of milk, as well as the variation —
including natural variation and changes due to processing — that can occur in
these characteristics, before starting on the main text.

1.1 COMPOSITION AND STRUCTURE

1.1.1 PRINCIPAL COMPONENTS
A classification of the principal constituents of milk is given in Table 1.1. The
principal chemical components or groups of chemical components are those present
in the largest quantities. Of course, the quantity (in grams) is not paramount in all
respects. For example, vitamins are important with respect to nutritive value; en-
zymes are catalysts of reactions; and some minor components contribute markedly
to the taste of milk. More information on milk composition is given in Table 1.3.
Lactose or milk sugar is the distinctive carbohydrate of milk. It is a disac-
charide composed of glucose and galactose. Lactose is a reducing sugar.
The fat is largely made up of triglycerides, constituting a very complicated
mixture. The component fatty acids vary widely in chain length (2 to 20 carbon
atoms) and in saturation (0 to 4 double bonds). Other lipids that are present include
phospholipids, cholesterol, free fatty acids, monoglycerides, and diglycerides.
About four fifths of the protein consists of casein, actually a mixture of four
proteins: αS1-, αS2-, β-, and κ-casein. The caseins are typical for milk and have some
rather specific properties: They are to some extent phosphorylated and have little
or no secondary structure. The remainder consists, for the most part, of the milk
serum proteins, the main one being β-lactoglobulin. Moreover, milk contains nume-
rous minor proteins, including a wide range of enzymes.
The mineral substances — primarily K, Na, Ca, Mg, Cl, and phosphate —
are not equi-valent to the salts. Milk contains numerous other elements in trace

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4 Milk: Main Characteristics

TABLE 1.1
Approximate Composition of Milk
Average Content Rangea Average Content in
Component in Milk (% w/w) (% w/w) Dry Matter (% w/w)

Water 87.1 85.3−88.7 —

Solids-not-fat 8.9 7.9−10.0 —
Fat in dry matter 31 22−38 —
Lactose 4.6 3.8−5.3 36
Fat 4.0 2.5−5.5 31
Proteinb 3.3 2.3−4.4 25
casein 2.6 1.7−3.5 20
Mineral substances 0.7 0.57−0.83 5.4
Organic acids 0.17 0.12−0.21 1.3
Miscellaneous 0.15 — 1.2

Note: Typical for milks of lowland breeds.

a These values will rarely be exceeded, e.g., in 1 to 2% of samples of separate
milkings of healthy individual cows, excluding colostrum and milk drawn shortly
before parturition.
b Nonprotein nitrogen compounds not included.

quantities. The salts are only partly ionized. The organic acids occur largely as
ions or as salts; citrate is the principle one. Furthermore, milk has many miscel-
laneous components, often in trace amounts.
The total content of all substances except water is called the content of dry
matter. Furthermore, one distinguishes solids-not-fat and the content of fat in the
dry matter.
The chemical composition of milk largely determines its nutritional value; the
extent to which microorganisms can grow in it; its flavor; and the chemical
reactions that can occur in milk. The latter include reactions that cause off-flavours.

1.1.2 STRUCTURAL ELEMENTS

Structure can be defined as the geometrical distribution of the (chemical) compo-
nents in a system. It may imply, as it does in milk, that the liquid contains particles.
This can have important consequences for the properties of the system. For
instance, (1) chemical components are present in separate compartments, which
can greatly affect their reactivity; (2) the presence of particles greatly affects some
physical properties, like viscosity and optical appearance; (3) interaction forces
between particles generally determine the physical stability of the system; and (4)
the separation of some components (fat and casein) is relatively easy.
Figure 1.1 shows the main structural elements of milk. Of course, the figure
is schematic and incomplete. Some properties of the structural elements are given

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1.1 Composition and Structure 5

A
×5

Milk

B
Plasma × 500

Fat
globules

Fat Membrane C
Serum
globule × 50000
Casein
micelles

FIGURE 1.1 Milk viewed at different magnifications, showing the relative size of struc-
tural elements (A) Uniform liquid. However, the liquid is turbid and thus cannot be
homogeneous. (B) Spherical droplets, consisting of fat. These globules float in a liquid
(plasma), which is still turbid. (C) The plasma contains proteinaceous particles, which are
casein micelles. The remaining liquid (serum) is still opalescent, so it must contain other
particles. The fat globules have a thin outer layer (membrane) of different constitution.
(From H. Mulder and P. Walstra, The Milk Fat Globule, Pudoc, Wageningen, 1974.)

in Table 1.2, again in a simplified form; the numerical data mentioned are meant
only to define orders of magnitude. The table clearly shows that aspects of colloid
chemistry are essential for understanding the properties of milk and the many
changes that can occur in it. All particles exhibit Brownian motion; they have an
electrostatic charge, which is negative at the pH of milk. Their total surface area
is large.
Fat globules. To a certain extent, milk is an oil-in-water emulsion. But the
fat globules are more complicated than emulsion droplets. In particular, the
surface layer or membrane of the fat globule is not an adsorption layer of one

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6 Milk: Main Characteristics

TABLE 1.2
Properties of the Main Structural Elements of Milk
Milk
Plasma
Serum
Globular Lipoprotein
Fat Globules Casein Micelles Proteins Particles

Main components Fat Casein, water, Serum protein Lipids, proteins

salts
To be considered as Emulsion Fine dispersion Colloidal Colloidal
solution dispersion
Content 4 2.8 0.6 0.01
(% dry matter)
Volume fraction 0.05 0.1 0.006 10−4
Particle diametera 0.1−10 µm 20−400 nm 3−6 nm 10 nm
Number per ml 1010 1014 1017 1014
Surface area 700 40000 50000 100
(cm2/ml milk)
Density 920 1100 1300 1100
(20°C; kg ⋅ m−3)
Visible with Microscope Ultramicroscope Electron
microscope
Separable with Milk separator High-speed Ultrafiltration Ultrafiltration
centrifuge
Diffusion rate 0.0 0.1–0.3 0.6 0.4
(mm in 1h)a
Isoelectric pH ∼3.8 ∼4.6 4−5 ∼4

Note: Numerical values are approximate averages.

a For comparison, most molecules in solution are 0.4 to 1 nm diameter, and diffuse, say, 5 mm
in 1 h. 1 mm = 103 µm = 106 nm = 107 Å.

single substance but consists of many components; its structure is complicated.

The dry mass of the membrane is about 2.5% of that of the fat. A small part of
the lipids of milk is found outside the fat globules. At temperatures below 35°C,
part of the fat in the globules can crystallize. Milk minus fat globules is called
milk plasma, i.e., the liquid in which the fat globules float.
Casein micelles consist of water, protein, and salts. The protein is casein.
Casein is present as a caseinate, which means that it binds cations, primarily
calcium and magnesium. The other salts in the micelles occur as a calcium
phosphate, varying somewhat in composition and also containing a small amount
of citrate. This is often called colloidal phosphate. The whole may be called
calcium-caseinate/calcium-phosphate complex. The casein micelles are not
micelles in the colloid-chemical sense but just ‘small particles.’ The micelles have

© 2006 by Taylor & Francis Group, LLC

1.2 Milk Formation 7

an open structure and, accordingly, contain much water, a few grams per gram
of casein. Milk serum, i.e., the liquid in which the micelles are dispersed, is milk
minus fat globules and casein micelles.
Serum proteins are largely present in milk in molecular form or as very small
aggregates.
Lipoprotein particles, sometimes called milk microsomes, vary in quantity
and shape. Presumably, they consist of remnants of mammary secretory cell
membranes. Few definitive data on lipoprotein particles have been published.
Cells, i.e., leukocytes, are always present in milk. They account for about
0.01% of the volume of milk of healthy cows. Of course, the cells contain all
cytoplasmic components such as enzymes. They are rich in catalase.
Table 1.3 gives a survey of the average composition and structure of milk.

1.2 MILK FORMATION

Milk components are for the most part formed in the mammary gland (the udder)
of a cow, from precursors that are the results of digestion.
Digestion. Mammals digest their food by the use of enzymes to obtain simple,
soluble, low-molar-mass components, especially monosaccharides; small pep-
tides and amino acids; and fatty acids and monoglycerides. These are taken up
in the blood, together with other nutrients, such as various salts, glycerol, organic
acids, etc. The substances are transported to all the organs in the body, including
the mammary gland, to provide energy and building blocks (precursors) for
metabolism, including the synthesis of proteins, lipids, etc.
In ruminants like the cow, considerable predigestion occurs by means of
microbial fermentation, which occurs for the most part in the first stomach or
rumen. The latter may be considered as a large and very complex bio-fermenter.
It contains numerous bacteria that can digest cellulose, thereby breaking down
plant cell walls, providing energy and liberating the cell contents. From cellulose
and other carbohydrates, acetic, propionic, butyric and lactic acid are formed, which
are taken up in the blood. The composition of the organic acid mixture depends
on the composition of the feed. Proteins are broken down into amino acids. The
rumen flora uses these to make proteins but can also synthesize amino acids from
low-molar-mass nitrogenous components. Further on in the digestive tract the
microbes are digested, liberating amino acids. Also, food lipids are hydrolyzed in
the rumen and partly metabolized by the microorganisms. All these precursors can
reach the mammary gland.
Milk Synthesis. The synthesis of milk components occurs for the greater
part in the secretory cells of the mammary gland. Figure 1.2 illustrates such a
cell. At the basal end precursors of milk components are taken up from the blood,
and at the apical end milk components are secreted into the lumen. Proteins are
formed in the endoplasmic reticulum and transported to the Golgi vesicles, in
which most of the soluble milk components are collected. The vesicles grow in
size while being transported through the cell and then open up to release their
contents in the lumen. Triglycerides are synthesized in the cytoplasm, forming

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TABLE 1.3
Composition and Structure of Milka

8
FAT GLOBULE CASEIN MICELLE SERUM
Water 790 g Organic acids Proteins
Protein
citrate 1600 mg casein +
Glycerides casein 26 g
triglycerides 40 g proteose peptone + Carbohydrates formate 40 mg β-lactoglobulin 3.2 g
diglycerides 0.1 g Salts 2g
monoglycerides 10 mg 850 mg
lactose 46 g acetate 30 mg α-lactalbumin 1.2 g
Ca
Fatty acids 60 mg phosphate 1000 mg glucose 70 mg lactate 20 mg serum albumin 0.4 g
Sterols 100 mg citrate 150 mg
Carotenoids 0.3 mg K, Mg, Na others oxalate 20 mg immunoglobulins 0.8 g
Vitamins A, D, E, K Water ~80 g others 10 mg proteose peptone +
Water 60 mg Enzymes
Others Minerals others
lipase
plasmin Ca, bound 300 mg Gases Nonprotein nitrogenous
MEMBRANE Ca, ions 90 mg oxygen 6 mg compounds
water + Mg 70 mg nitrogen 16 mg peptides +
protein 700 mg
LEUKOCYTE phospholipids 250 mg K 1500 mg Lipids amino acids 50 mg
cerebrosides 30 mg LIPOPROTEIN
Na 450 mg glycerides + urea 250 mg
glycerides + PARTICLE
fatty acids 15 mg Cl 1100 mg fatty acids 20 mg ammonia 10 mg
Many enzymes streols 15 mg
other lipids lipids phosphate 1100 mg phospholipids 100 mg others 300 mg
e.g., catalase protein
enzymes sulfate 100 mg cerebrosides 10 mg Enzymes
Nucleic acids alkaline phosphatase enzymes
Water xanthine oxidase water bicarbonate 100 mg sterols 15 mg acid phosphatase

Milk: Main Characteristics

many others
others peroxidase
Cu 4 µg
Fe 100 µg Trace elements many others
Zn 3 mg Vitamins, e.g. Phosphoric esters ~300 mg
Fe 120 µg riboflavin 2 mg Others
Cu 20 µg ascorbic acid 20 mg
many others
a Approximate average quantities in 1 kg milk. Note: The water in the casein micelles contains some small-molecule solutes.

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1.2 Milk Formation 9

LUMEN

Microvillus

Golgi vesicle
with casein
micelles
Junctional
complex

Golgi apparatus

Cytosol
Nascent
fat globule
Lysosome

Mitochondrion
Outer cell
membrane
Nucleus (plasmalemma)

Endoplasmic Ribosomes
reticulum

Basement
membrane

5 µm

FIGURE 1.2 Stylized diagram of a mammary secretory cell. Below is the basal part, on
top the apical part of the cell. The cell is bounded by other secretory cells to form the
glandular epithelium. See text for further details. (From P. Walstra and R. Jenness, Dairy
Chemistry and Physics, Wiley, New York, 1984. With permission.)

small globules, which grow while they are transported to the apical end of the
cell. They become enrobed by the outer cell membrane (or plasmalemma) while
being pinched off into the lumen. This type of secretion is called merocrine,
which means that the cell remains intact.
Table 1.4 gives some information about the synthesis of specific components.
Most are synthesized in the cell. Others are taken up from the blood but, generally,
not in the same proportion as in the blood; see, especially, the salts. This means
that the cell membranes have mechanisms to reject, or allow passage of, specific
components. Some substances, notably water and small lipophilic molecules, can

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TABLE 1.4

10
Synthesis of Important Milk Components
Milk Component Precursor in Blood Plasma Synthesis of Component
Concentration Concentration In the Specific Specific for
Name (% w/w) Name (% w/w) Secretory Cell? for Milk? the Species?

Water 86 Identical 91 No No No
Lactose 4.7 Glucosea 0.05 Yes Yes No
Protein
Caseins 2.6 ⎫ Yes Yes Yesb
β-lactoglobulin 0.32 ⎪⎪ Amino acids 0.04 Yes Yes Yes
α-lactalbumin 0.12 ⎬⎪ Yes Yes Yes
Lactoferrin 0.01 ⎪⎭ Yes No Yes
Serum albumin 0.04 Identical 3.2 No No Yes
Immunoglobulins 0.07 Most are identical 1.5 No No Yes
Enzymes Trace Various — Yesc Noc Yes
Lipids
⎧Acetic acid 0.01⎫
⎪ ⎪
Triglycerides 4 ⎨β -Hydroxy butyric acid 0.006 ⎬ Partly Partly
⎪Acylglycerols ⎪
⎩ ⎭
Phospholipids 0.03 Some lipids 0.3
Citric Acid 0.17 Glucosea 0.05 Yes No No

Milk: Main Characteristics

Minerals Identical No No No
Ca 0.13 0.01
Pd 0.09 0.01
Na 0.04 0.34
K 0.15 0.03
Cl 0.11 0.35
a Glucose can also be formed in the secretory cells from some amino acids.
b All proteins are species specific, but comparable proteins occur in the milk of all ruminants.
c Is not true for all enzymes.
d In various phosphates.

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1.2 Milk Formation 11

pass the cell more or less unhindered. Some other components, such as serum
albumin and chlorides, can ‘leak’ from the blood into the milk by passing through
the spaces between secretory cells. Also, some leukocytes somehow reach the
lumen. Finally, cell remnants, such as part of the microvilli depicted in Figure 1.2
and tiny fragments of cytoplasm that occasionally adhere to a fat globule, are
secreted and form the lipoprotein particles of Table 1.2.
Excretion. The glandular epithelium, consisting of layers of secretory cells,
form spherical bodies called alveoli. Each of these has a central lumen into which
the freshly formed milk is secreted. From there, the milk can flow through small
ducts into larger and still larger ones until it reaches a cavity called the cistern.
From the cistern, the milk can be released via the teat. A cow has four teats and
hence four separate mammary glands, commonly called (udder) quarters.
Excretion of the milk does not happen spontaneously. The alveoli have to
contract, which can be achieved by the contraction of muscle tissue around the
alveoli. Contraction is induced by the hormone oxytocin. This is released into
the blood by stimulation of the teats of the animal, be it by the suckling young
or by the milker. The udder is not fully emptied.
Lactation. When a calf is born, lactation — i.e., the formation and secretion
of milk — starts. The first secretion greatly differs in composition from milk (see
Subsection 2.7.1.5). Within a few days the milk has become normal and milk yield
increases for some months, after which it declines. The yield greatly varies among
cows and with the amount and the quality of the feed taken by the cow. For milch
cows, milking is generally stopped after about 10 months, when yield has become
quite low. The duration from parturition to leaving the cow dry is called the
lactation period, and the time elapsed after parturition is the stage of lactation.

1.3 SOME PROPERTIES OF MILK

Milk as a Solution. Milk is a dilute aqueous solution and behaves accord-
ingly. Because the dielectric constant is almost as high as that of pure water, polar
substances dissolve well in milk and salts tend to dissociate (although this dis-
sociation is not complete). The ionic strength of the solution is about 0.073 M. The
pH of milk is about 6.7 at room temperature. The viscosity is low, about twice that
of water, which means that milk can readily be mixed, even by convection currents
resulting from small temperature fluctuations. The dissolved substances give milk
an osmotic pressure of about 700 kPa (7 bar) and a freezing-point depression
close to 0.53 K. The water activity is high, about 0.995. Milk density ( ρ 20) equals
about 1029 kg⋅m−3 at 20°C; it varies especially with fat content.
Milk as a Dispersion. Milk is also a dispersion; the particles involved are
summarized in Table 1.2. This has several consequences, such as milk being
white. The fat globules have a membrane, which acts as a kind of barrier between
the plasma and the core lipids. The membrane also protects the globules against
coalescence. The various particles can be separated from the rest.
The fat globules can be concentrated in a simple way by creaming, which
either occurs due to gravity or — more efficiently — is induced by centrifugation.

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