Selenium (Se) in Food

By

Elis Cen
Dr. Darryl M. Small

The Element Se

One of the rarest elements

Once known only for its toxicity
Plays a key role in all animal life
Essential component of the human diet (minute
amount required)

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Se Chemistry

Atomic weight: 78.96

Atomic number: 34
Group 16/VIA (with oxygen, sulfur and Tellurium)
A metalloid (neither fully metallic nor nonmetallic,
shares chemical and physical properties of both)
Boils at 684C
Very stable and highly insoluble
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Common inorganic Se compounds

Ferro- (FeSe) and nickel-selenide (NiSe)
Selenium dioxide (SeO2)
Cadmium sulfoselenide
O
Cd++

Se
S

O
S

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Common inorganic Se compounds

Selenium diethyldithiocarbamate

S-

SeH2++

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Common inorganic Se compounds

Sodium selenite (Na2O3Se)
Na+
-

O
Se
ONa

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Common inorganic Se compounds

Selenate (SeO42)
OO

Se

O-

Selenide sulfide (SeS and SeS2)

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Common organic Se compounds

Selenomethionine
O
Se
HO
NH2
O
S
HO
NH2

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Common organic Se compounds

Selenocysteine
HO

SeH

NH2

HO

SH

NH2
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Isotopes of Se
74Se, 76Se, 77Se, 78Se, 80Se, and 82Se
Relative abundance:
80Se (49.8%) > 78Se (23.5%) >
76Se (9.4%) > 82Se (8.7%) > 77Se (7.6%) >
74Se (0.87%)

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Other applications of Se
Glass industry: to decolorise and to color glass
Component of lubrication oils and greases used
at high temperatures
Metallurgy: added to improve the machinability
of wrought iron and steel castings
Used in photocopier and laser printers (when
light strikes Se, it becomes charged electrically)

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Applications of Se (cont)
Agricultural and horticultural: sodium selenite
and selenate as
Additives and dietary supplements in animal feeds
Fertilizers
Top dressings for soil deficiency

Pharmaceutical industry: sodium selenite and

selenate, selenomethionine and seleniumenriched yeast are used as over-the-counter
dietary supplements
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Se analysis
Challenges:
Low levels in biological materials
Very volatile and easily lost during sample
preparation

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Se analysis
Sample preparation:
Removal of organic matter
Brings the element into the mineralized state in
solution
Involves some forms of oxidation

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Se analysis
Various approaches:
Dry procedure: sample is incinerated at high
temperature in a furnace or other type of heating
apparatus
Wet digestion: sample is heated with various
acids or mixtures of them

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Se analysis (comparison)
Factors

Dry procedure/ Wet digestion/

dry ashing
wet ashing

Risk of loss
Sample size

Higher
Wide range

Lower
Small

Amount of
digestion fluid

Minimum

Relatively large
volume

Practicality

More
convenient

Relatively more
complex

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Wet ashing
Using open vessels
on a temperature controlled heating block
plate heater
under reflux

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Wet ashing
Using closed digestion systems
an oxygen bomb or
microwave-heated sealed polytetrafluoroethylene
(PTFE) tubes

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End-determination methods for Se

analysis
1. Spectrofluorimetry

Can measure down to nanogram quantities in

many different biological matrices

2. Atomic Absorption Spectrophotometry (AAS)

Can measure down to microgram per gram range

with ease in biological samples
Commonly used: Hydride Generation AAS
(HGAAS)
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End-Determination Methods for Se

Analysis
3. Inductively Coupled Plasma Atomic Emission
Spectrophotometry (ICP-AES)

Can measure down to microgram per gram

4. Inductively Coupled Plasma Mass

Spectrometry (ICP-MS)

Capable of determining Se down to 10 pg/g

(where p indicates pico which is 10-12)

Both allow simultaneous multi-element analysis

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ICP-MS

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Speciation analysis
To detect the different Se compounds
Among the separation techniques found to be
effective for selenium speciation are:
High Performance Liquid Chromatography (HPLC),
including
Ion Exchange (IE)
Size Exclusion Chromatography (SEC)
Capillary Electrophoresis (CE)

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Speciation analysis
Detectors used include:

Mass Spectrometry (MS)

ICP-MS
Neutron Activation Analysis (NAA)
Atomic Fluorescence Spectrometry (AFS)

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Se in health
A constituent of the antioxidant enzyme
glutathione peroxidase (GPX):
has diverse roles in the animal body in addition to
its antioxidant function.
involved in thyroid hormone homeostasis,
immunity and fertility, has anticancer properties,
acts as a growth factor, plays important roles in
metabolism.

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Se in health
The selenoproteins found in mammals include:
several different GPXs
3 thyroid hormone deiodinases
3 thioredoxin reductases (TRs)

Each has selenocysteine (Sec) at the active site

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Se toxicity (selenosis)
Selenosis in farm animals

Characterized by general dullness, lack of vitality,

emaciation, stiffness, lameness, loss of hair, hoofs
to drop off, and reduction in reproductive
performance.
Acute selenosis can be caused by an intake of 400
mg/kg; a lower dose between 5 to 40 mg/kg over a
period of several weeks or months can result in
chronic poisoning.

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Se Toxicity (cont)
Selenosis in humans

Characterised by dermatitis, loose hair, damaged

nails, accompanied by elevated serum and urine Se
levels. More seriously may lead to abnormalities of
the nervous system.

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Se deficiency
In farm animals
White muscle disease (WMD) > affects heart muscle
leading to heart failure and death.
Exudative Diathesis > growth rate is slowed, lose
condition, develop leg weakness and eventually die.
Liver necrosis
Pancreatic degeneration > poor growth and feathering
Ill thrift > loss of weight and death, poor wool quality
and quantity in sheep
Impaired reproduction
Impaired immune response
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Se deficiency (cont)
In humans Se deficiency is one of the contributing
factors to various conditions:

Keshan disease > a sudden onset of precardial

oppression and pain, nausea and vomiting, in some
cases ending in death.
Kashin-Beck disease > an osteoarthropathy,
characterized by chronic disabling degeneration and
necrosis of the joints and the epiphysial-plate
cartilages of the arms and legs.
Goiter or Derbyshire neck
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Se supplementation
Supplementation strategies for animals:
Application of the element directly to pastures
Free choice supplementation, i.e. incorporated into
salt blocks
Direct administration to animals

Combined Se and vitamin E and other

micronutrients >> improve the symptoms due to
Se deficiency in many cases
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Se levels (g/kg) in foods from different

countries

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Enhancing Se content of foods

Adding selenium to fertilizers, used effectively to
increase the Se content of a variety of food
crops, including rice, wheat, broccoli, onion, tea.
Examples of food enrichment:
Se-enriched milk (Korea)
the Mega egg which has added vitamin E as well as
Se (Ireland),
Se-enriched bread and flour (UK),
Se-fortified breakfast cereals, table salt, margarine
and sports drink (various countries)
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Enhancing Se content of foods (cont)

Chemical forms of Se used to fortify foods
Inorganic compounds
sodium selenite, sodium hydrogenselenite, sodium
selenate
Organic forms
selenomethionine, selenocysteine and Se-enriched
yeast

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Dietary Reference Values for Se

EAR Estimated Average Requirement; RDI Recommended Dietary Intake

LRNI Lower Reference Nutrient Intake; RNI Reference Nutrient Intake
RDA Recommended Dietary Allowance; UL Upper Limit
Sources:
1
Department of Health and Aging (2005) Nutrient Reference Values for Australia and New Zealand.
http://www.nhmrc.gov.au
2
Department of Health (1991) Dietary Reference Value for Food Energy and Nutrients for the UK,
COMA, HMSO, London
3
Food and Nutrition Board National Academy of Sciences (2002) US Dietary Reference Intakes:
Elements. http://www.nationalacademies.org

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Additional references
Reilly, C. (2006). Selenium in Food and Health, 2nd ed.
USA
CEM Corporation (2006) MarsXtraction.
http://www.cem.com/analytical/extraction.asp
Reilly, C. (1998). Selenium: A new entrant into the
functional food arena. Trends in Food Science and
Technology, 9, 114-118.

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