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Supplementary Course Topic 1:

Nucleons - The Sub-Atomic Particles

Nuclear and Radiation Chemistry


Nucleons, nuclides and isotopes
Nuclear fusion and stellar nucleogenesis
Natural Radioactivity
Which nuclides are stable and why
Where decay mechanisms come from

Particle

Symbol

Charge

proton

+1

Mass (a.m.u.)
1.007276

neutron

1.008665

electron

e-

-1

0.000549

positron

e+

+1

0.000549

How fast does an unstable nucleus decay? Half-lives


Radiocarbon Dating
How does radiation interact with (biological) matter?
How is radiation exposure measured?
What are common sources of radioactivity?

Not present in
stable atoms.

The unit of mass is atomic mass units (a.m.u.), defined by


setting the mass of the isotope 126C to exactly 12.
1 a.m.u. = 1.66 x 10-27 kg.

Medical Imaging

Nuclides and Isotopes

Nuclides and Isotopes

The composition of any nucleus is defined by two numbers.


The atomic number is the number of protons in the nucleus.
This defines the chemical nature of the atom.
It is equal to the total charge on the nucleus.
The mass number is the total number of nucleons (protons
and neutrons) in the nucleus.

Nuclei with the same atomic number but different mass


numbers are called isotopes.

E.g.

E.g. Carbon may exist as a number of isotopes


11
6

12
6

13
6

14
6

15
6

12
6

C has an atomic number of 6 and a mass number of 12.

A nuclide is an atom with a particular mass number and atomic number.


Nuclei with the same atomic number but different mass numbers are
called isotopes.

How Mass Spectrometry Works


In a mass spectrometer, the atoms or molecules
to be studied are vapourised and then ionised,
usually by an electrical discharge.
In the conventional design of a mass
spectrometer, ions follow a curved path and
their deflection depends on the mass-to-charge
ratio, m/z (sometimes denoted m/e). This
deflection was originally recorded as impact on
a strip of photographic film, but now use digital
current or luminescence detectors.

Unstable
nucleus;
prepared by
nuclear
reaction in a
cyclotron.

Stable
nucleus;
accounts for
98.89% of
natural
carbon.

Stable
nucleus;
accounts for
1.11% of
natural
carbon.

Unstable
nucleus; trace
amounts
present in
living matter.

Unstable
nucleus.

Mass Spectrometry
Astons results established the existence of isotopes. (They were already
known for radioactive elements, but never shown for stable elements.)
1920 - Aston measured two isotopes of Ne (20 and 22), three of S (32, 33, 34),
three of Si (28, 29, 30), six of Kr (78, 80, 82, 83, 84, 86), and many others

Nuclides and Isotopes

Nucleogenesis

The atomic mass of an element is the average of the atomic


masses and abundances of each of the naturally-occurring
isotopes.

Where do the elements come from?

E.g. The atomic mass of carbon is 12.01.

All atoms are generated from the simplest element, hydrogen


1
1 H, by nuclear reactions.

How are atoms (nuclei) formed?

That is (12.0000x98.89 + 13.00335x1.11)/100

12
6

Clouds of atomic hydrogen are pulled together by gravity and begin to


heat as they are compressed. Eventually high enough temperatures for
nuclear fusion are achieved and the cloud ignites as a star.

13
6

Mass of nuclide
is the reference
for a.m.u scale.

Mass of nuclide
taken from a
reference table

Nucleogenesis

Nucleogenesis

The fundamental nuclear reaction is


1
1

The fundamental nuclear reaction is

H + H
H+ e
1
1

2
1

0
1

This denotes a
positron of mass 0
and charge 1

1
1

This is rapidly followed by two other nuclear reactions


2
1

In nuclear reactions, where the nuclide


is changed, we must balance both the
charge as well as the mass numbers

and

In a nuclide, the charge is the same as the atomic number the number of
protons.

H + 11H
12 H + 10 e

H + 11H
23 He +

3
2

This denotes high


energy, short
wavelength gamma
radiation, which has
no mass or charge.

He+ 23He24He + 211p

Again note that both mass numbers and charges


(atomic numbers) must balance.

See - http://www.nobel.se/physics/articles/fusion/index.html
See - http://www.nobel.se/physics/articles/fusion/index.html

Nucleogenesis

Life Cycle of Stars


Helium burning

The overall hydrogen burning reaction

4 H
He + 2 e +
1
1

4
2

Hydrogen burning

0
1

T < 2 x 108K

Carbon core

T ~ 107K

releases energy into the surroundings as heat (exothermic)


and radiation (also releases neutrinos ).
As the star exhausts its hydrogen, it begins helium burning to
fuse heavier nuclei to form increasingly larger atoms.
E.g.

3
2

He+ 24He47 Be +
7
4

Be+11p58B +

Hydrogen
burning
T ~ 107K

Heavier nuclei like 13C, 13N, 14N, 15N, 15O... are produced by red giant stars, still
heavier nuclei in supergiants, and true heavy elements form in supernovae.

Helium
burning
T < 2 x 108K

40Ca58Ni

formed

(C and O burning)
T < 3 x 109K

Heavy
elements

Second-generation stars

Nucleogenesis and the periodic table

Supernova explosions inject carbon, oxygen, silicon and other heavy elements up to iron
into interstellar space. They are also the site where most of the elements heavier than
iron are produced. This heavy element enriched gas will be incorporated into future
generations of stars and planets.
We know from the presence of
heavy elements in our sun that it
is (at least) a second-generation
star, currently undergoing
hydrogen burning.

H burning
He burning. Star
expands to red giant

C burning. Core
of red giant
Red supergiant
core.

Without supernovae, the fiery


death of massive stars, there
would be no carbon, oxygen or
other elements that make life
possible.

Supernova (everything heavier)

Natural Radioactivity

Natural Radioactivity
Nucleogenesis produces nuclides that can be stable or
unstable. Unstable nuclei decay through a range of
mechanisms involving the release of particles with high
kinetic energy or of -radiation. These high-energy products
are collectively known as radioactivity.
Henri Becquerel

The four most important radioactive decay mechanisms are


1. decay
212
83

e.g.

4
Bi
208
81Tl + 2

As with all nuclear reactions, both


mass and charge are balanced.

Pierre Curie

"in recognition of the


extraordinary services
he has rendered by his
discovery of
spontaneous
radioactivity"

"in recognition of the


extraordinary services they
have rendered by their joint
researches on the radiation
phenomena discovered by
Professor Henri Becquerel"

2. decay

e.g.

12
5

(or -) is an electron ejected from


the nucleus.

B
126 C + 10 e

One neutron is changed into a


proton in this nuclear reaction to
balance the charge.

Marie Curie

Natural Radioactivity

Natural Radioactivity - worked example

3. Positron (+) emission


12
7

e.g.

0 +
1

N
C+ e
12
6

The particle is simply a helium


nucleus with mass 4 and charge
2+.

When a positron (+) is ejected


from the nucleus is usually collides
with its antiparticle (the electron) in
the surrounding environment very
soon:
+

Balance the following nuclear decay reactions and identify the


emitted particle where appropriate.
1.

e + e

2.

U
230
90Th +

234
92

63
28

4
2

He or 24

Ni
2963Cu + 10 e

4. Electron capture

e.g.

55
26

Fe + 10 e
2555 Mn

Electron capture is followed by emission


of x-rays as electrons fall into lower
energy states to fill the vacancy left by
the captured electron.

3.

36
17

Cl +

0
1

1636 S
e

(x-rays are not generally classified as


radioactivity, although they can cause
radiation damage.)

Natural Radioactivity - and x-rays

Nuclear Reactions - worked example


Nuclear reactions are balanced in the same way, but may
involve more than one reactant. Balance the following
nuclear reactions and identify the missing nuclide or particle.
1.

14
7

2.

239
94

3.

N + 24 He
178 O + 11H or

1
1

x-rays have shorter wavelengths


than visible or ultraviolet light between 0.01nm and 10nm.

1
Pu + 24 He
242
96 Cm + 0 n

28
14

Both x-rays and radiation are high energy (= high frequency


or short wavelength) forms of light.

rays have very short


wavelengths - less than
0.01nm or 0.1

Si + 12 H
1529 P + 01n

Natural Radioactivity

Natural Radioactivity

Unstable heavy nuclei decay spontaneously by a series of


steps through unstable intermediates. Over time, unstable
nuclei give rise to a family of decay products in a decay
series.

A radioactive decay sequence


(e.g. of 238U) can be
represented more concisely as
a graph of atomic number
versus neutron number.

E.g. 238U decays into


decay is shown as a decrease of
two protons (Z) and two neutrons
(N).

4
U
234
90Th + 2

238
92

0
Th
234
91 Pa + 1

234
90

234
91

decay is shown as a decrease of


one neutron and an increase of one
proton.

0
Pa
234
92 U + 1
4
U
230
90Th + 2

234
92

4
Th
226
88 Ra + 2

230
90

etc, etc,...

Natural Radioactivity

Isotopes (same Z, different N) lie


along vertical lines in this graph.

Radioactive Decay Series and the periodic table

A radioactive isotope like 238U


thus generates a family of
daughter isotopes in a decay
series.
Naturally-occurring uranium
contains 238U, and so will also
contain components of the
decay series.
206Pb

238U

Nuclear Stability

Marie Curie
Born Maria Sklodowska in Warsaw, Poland on November 7,
1867.
In 1891 at 24, Sklodowska went to Paris to study mathematics,
physics and chemistry at the Sorbonne.

What factors determine whether a nucleus is stable or


unstable?
If we look at the range of stable nuclides that exist in nature, then there
are two main observations

July 25, 1895 married Pierre Curie


1903 Nobel Prize for Physics
1911 Nobel Prize for Chemistry

1. The size of the nucleus.

Discovered Radium and Polonium, coined term Radio-activity.


In 1906, Pierre Curie, was hit by a horse-drawn carriage and
killed.

2. The composition of the nucleus (proton:neutron)

Marie Curie died at the age of 67 in 1934 of leukemia. Her


cremated remains are kept in the Pantheon in Paris
In 1935, the Curie's daughter, Irene Joliot-Curie won a Nobel
Prize for Chemistry in 1935, making them the first mother and
daughter to share this honor.

Nuclear stability 1. Nuclear size


There are no stable nuclei heavier than

Nuclear Stability 2. neutron:proton (N:Z)


209
83

Bi
All known stable nuclides fall
inside the zone of stability.
This zone has a N:Z ratio
near to 1, but bends
towards more neutrons per
proton as the nucleus gets
larger.
These two observations are enough
to give us a rule for nuclear stability
that goes something like
Unstable isotopes must decay
towards the zone of stability, finally
falling below 209Bi.

Nuclear Stability and Decay Mechanisms

Nuclear Stability and Decay Mechanisms


Each nuclide decays towards the zone of stability by
changing its N/Z ratio at constant mass number.

Consider some of the known isotopes of carbon from the last


lecture.

N/Z too low gives + decay.


11
6

12
6

13
6

14
6

15
6

Unstable
nucleus

Stable
nucleus;

Stable
nucleus;

Unstable
nucleus;

Unstable
nucleus;

N/Z = 0.83

N/Z = 1

N/Z = 1.17

N/Z = 1.33

N/Z = 1.5

too high

too high

too low

C
115 B + 10 e+

11
6

N/Z = 0.83 N/Z = 1.2

N/Z too high gives - decay.

C
147 N + 10 e

14
6

N/Z = 1.33 N/Z = 1.0

Or equivalently by electron capture.


55
26

Fe + 10 e
2555 Mn

N/Z = 1.11

N/Z = 1.2

C
157 N + 10 e

15
6

N/Z = 1.5

N/Z = 1.14

Nuclear Stability

Mass too high


decay.

The rule for nuclear stability:


Unstable isotopes must decay
towards the zone of stability, finally
falling below 209Bi.

N/Z too high


- decay.

Heavier nuclides than 209Bi


decay by a combination of
mechanisms, using decay
to reduce mass (with N/Z = 1)
and the other mechanisms to
change N/Z.

Nuclear Stability
E.g. Here is how the 238U
decay sequence looks on our
zone of stability graph.

N/Z too low


+ decay
or electron
capture.

Nuclear Stability - Origin of Decay Mechanisms

Nuclear Stability - Origin of Decay Mechanisms

The nuclear stability rule is empirical, based on the simple


experimental observation of which nuclides are stable and
which are not.

The stability of a nucleus involves the competition between


two forces.

We can apply it like an algorithm to solve some nuclear decay


problems, without understanding the reasons for nuclear
stability.
To understand the reasons, the rule, and the observations,
we need to consider the forces between nucleons within the
nucleus.

Nuclear Stability - Origin of Decay Mechanisms


How does this explain our observations?
1. In nuclides with too few neutrons, the electrostatic
repulsions overwhelm the strong nuclear attractions.
2. As the nucleus gets larger, the long-range electrostatic
repulsion between protons accumulates and eventually
overwhelms the strong nuclear attraction, even if N/Z is
optimised.

1. Coulomb or electrostatic repulsion between protons acts


to push these nucleons apart over a long range.
2. The strong nuclear force is a short range attraction
between all nucleons.
This is the main function of neutrons in the nucleus. They
contribute to the binding of the nucleus without also
contributing to the electrostatic destabilisation.

Rate of Nuclear Decay


Unstable nuclides are present in nature for two reasons.
Some unstable nuclides have long half-lives, so they simply
havent decayed yet.
Some unstable nuclides continue to be formed by nuclear
reactions.
For each parent nuclide that decays, one daughter nuclide is produced
and a particle or is emitted. e.g.
212
83

4
Bi
208
81Tl + 2

12
5

This microscopic model does not explain how nuclides with too many
neutrons can be unstable. To do so will involve quantum mechanics.

Parent nuclide

B
126 C + 10 e

Emitted
Particle

Daughter
nuclide

The decay of an unstable nuclide is characterised by a half-life. This is


the time required for half of the nuclei present to undergo a decay event.

Rate of Nuclear Decay - Half-Life

The Rate of Nuclear Decay

E.g. 32P decays into 32S with


a half-life of 14.7 days.

The disappearance of a radionuclide by radioactive decay is


described by

32
15

N (t ) = N 0 exp( t )

P
1632 S + 10 e

The number of 32P nuclei halves in


14.7 days, and halves again after a
further 14.7 days...

The number of
nuclei remaining
after time t.

The number of
nuclei present at
the beginning.

The decay
constant.

3H,

E.g. Decay curve for


T1/2 = 12.26 years.

0.75

N/N0

So, after 14.7 days, half of an initial 10g of 32P will have decayed, leaving
5g. At the same time 5g of 32S will have formed.
After a further 14.7 days, only 2.5g of 32P will remain, and 7.5g of
32S will be present

The number if nuclei halves


every 12.26 years.

This also tells us that the rate of decay, the number of nuclei that
disintegrate each second, also halves every 14.7 days.
The rate of decay halves after every half-life.

0.5

0.25

0
0

25

50

75

100

time (years)

The Rate of Nuclear Decay

Activity is the Rate of Nuclear Decay

The half-life is the time required for half of the nuclides to


decay (and for half to be left). So if we let N = N0/2

The activity, A, of a radionuclide is simply the rate of


emission, or minus the rate of disappearance of the nuclide.
i.e.
dN
d
A=
= N 0 exp( t )
dt
dt
= N 0 exp(t )

N0
= N 0 exp( t1 2 )
2
ln(2) 0.693
=
and solve, this gives t1 2 =

So finally we can write the decay in terms of half-life as

N (t ) = N 0 exp( 0.693t / t1 2 )

= N

The activity (rate of decomposition) of a sample is proportional to the


number of nuclei present.
i.e. when the number of nuclei present is halved, the activity is also
halved.

Units of Activity

Activity and Half-Life

Fundamental unit of activity - Disintegrations per second,


also known as the becquerel (Bq)

Activity and Half-Life are related.

Curie (Ci) 1 Ci equals the number of nuclei disintegrating


each second in 1g of 226Ra.
= 3.70 x 1010 counts per second (or Bq).

Low activity (few disintegrations per second) = long half-life.


High activity = short half-life

A = N =

0.693
N
t1 2

0.693
NA
t1 2
N A 0.693 N A
=
Specific Activity = Activity/gram AS =
M
t1 2 M
Molar Activity = Activity/mole

AM = N A =

M = atomic mass
Molar Activity, Specific Activity and Half-Life are both independent
of the amount of radioactive material present in the sample.

Activity and Half-Life - worked example

Rate of Nuclear Decay - Decay Series

What is the molar activity of 13N, which has a half life of 9.96
minutes?

In a decay series, each step in the


mechanism has its own half-life.

Answer.

AM = N A =

0.693
NA
t1 2

9.96 minutes = 598s


AS = 0.693 x 6.022 x 1023/598
= 6.98 x 1020 disintegrations mol-1 s-1 (or Bq mol-1)

Notice that the half-life of 238U is 4.5x109 y, so that


many of the atoms present when the earth was
formed still have not decayed. However the
daughter nuclides decay much more quickly.
Notice also that half lives can be as long as billions
of years or as short as a ms or less.

or 6.98 x 1020/3.70 x 1010 = 1.88 x 1010 Ci mol-1

Radiocarbon Dating
14C

is an example of an isotope that is continuously produced


in our environment.
14C

99.9% of the naturally abundant


is
produced in the upper atmosphere by
neutrons reacting with 14N, which then
enters the carbon cycle.
14
7

N + 01n
146 C + 11 p

The production rate is 2.5 atom cm-2 s-1


with a global inventory of 3 x 1030 14C
atoms (90% oceans, 8% biosphere and
soils, 2% atmosphere). Typical 14C
concentration in sea waters is
1.2 x 109 14C atoms/L (2 x 10-15 M).
www.ansto.gov.au/ansto/environment1/ams/ams_14c.htm

Radiocarbon Dating
Other Sources of 14C:
In-situ (0.1%): 14C is produced by spallation reactions induced by neutrons and
muons incident on the surface of the Earth. The 14C production rate from quartz
(at sea-level) is 20 atoms g-1 yr-1 and varies with elevation and geomagnetic
latitude. A wide range of geophysical problems can be studied by this method
including erosion histories, uplift rates, glacial histories, eruption ages, rates of
movements of sand dunes, accumulation and ablation rates of ice and climatic
change.
Radiogenic: 14C can be produced underground, directly or indirectly, by the decay
of uranium and thorium series. An estimate of this 14C can be useful in the study of
hydrological environments where uranium and thorium contents are high.
Anthropogenic: 14C levels in the atmosphere show a major peak in 1963 (with
about 100% increase in 14C concentration) because of contributions from nuclear
weapons testing and a slow drop since then. This bomb pulse is useful in the
study of environmental problems such as the air enclosure process in ice and the
circulation of groundwaters.
http://www.ansto.gov.au/ansto/environment1/ams/ams_14c.htm

How Radiocarbon Dating Works


All organic living matter contains a
fixed fraction of 14C amongst all its
carbon. This comes mostly (from
atmospherically generated) material
taken up by biochemical paths.

Radiocarbon Dating
How is the amount of 14C determined?
As noted before, 14C undergoes decay.

C
147 N + 10 e

14
6

Radiocarbon dating can be achieved either


After death, 14C no longer
accumulates, and decays into

C
147 N + 10 e

14
6

with a half-life of 5730 y.


Thus comparing the concentration of
14C in dead and comparable living
matter can tell us how long since the
sample died.

by measuring the concentration of 14C present in a sample, or


by measuring the activity due to emission. (Recall that activity is
proportional to the number of decaying nuclei: A = N =

0.693
N )
t1 2

http://www.c14dating.com/

Radiocarbon Dating - Activity Ratio

Scintillation is the emission of light when exposed to ionizing radiation.


Scintillation counters simply measure the intensity of light emitted as a
result of exposure to a radiation source. By calibration against a standard,
this can read activity directly.

Measuring 14C - accelerator mass spectrometry (AMS)


AMS is a high precision mass spectrometry technique that can measure
small amounts of sample and resolve isotopic composition. In 14C dating,
AMS is used to measure the ratio of 14C/13C and 14C/12C. As 13C and 12C
are stable, these ratios can be used directly to obtain radiocarbon age. As
carbon from different sources can have slightly different isotopic ratios due
to various chemical processes, the ratio of 13C/12C is measured directly in
AMS as an additional calibration correction.

The activity is proportional to the number of nuclei present.

A dN dN 0 N
N
=
=
= exp( t )

=
A0 dt dt N 0 N 0
To determine the age of a sample we compare the activity A with the activity of a
still-living (or recently dead) sample, A0, and use the half-life or decay constant.
1

0.75

0.75

0.5

0.25

0.5

0.25

25

50

75

100

time (years)

Radiocarbon Dating

A = N

Thus the ratio of the activity after death to activity while alive is equal to
the ratio of the number of 14C nuclides.

A/A0

Measuring Activity - scintillation counter.

N/N0

Radiocarbon Dating

25

50

75

100

time (years)

Calibration of Radiocarbon Dating

This method assumes that the concentration of 14C in living


matter has been constant over the dating period.
This assumption is known not to be exactly true, so a number of
qualifications and corrections are applied to 14C dates, and a standard
method is always used to report radiocarbon age.

Willard Libby, who invented 14C dating in 1946 (Nobel Prize, 1960), prepared a
primary calibration graph, shown below, using samples with independentlydetermined ages.
The curve shows the Libby half-life of 5568y, which is used to determine the
radiocarbon age of materials and effectively assumes a constant rate of 14C
production.

1. The age of a sample is reported as its radiocarbon age. This may be reported
as years BP (before present, where present = AD1950 when radiocarbon dating
was invented).
2. An uncertainty or error range is often reported based on known changes in
levels as well as on experimental uncertainty.

14C

3. The radiocarbon age may be corrected using a calibration graph obtained from
independent data.

Note that all the independent


data is <5000 years old.

4. Variations in natural isotopic ratios between sources are also corrected.

Radiocarbon Dating - worked example

Radiocarbon Dating by AMS

E.g. A one gram sample of carbon from peat moss has an


activity of 0.350mCi. A reference or modern standard sample
yields 0.446mCi. What is the radiocarbon age of the sample?

AMS has two major advantages over activity measurements.

This pre-factor is
obtained from the Libby
half-life and is equal to
5568/ln(2)

This is a ratio. The units


A
of activity must be the
t = 8033ln 0
same in the numerator &
A
denominator.
0.446

= 8033ln

0.350
= 1950 Years BP (rounded up from 1947)
The units of time are determined by the units
of the pre-factor or half-life.

1. Sensitivity. AMS can measure samples as small as a few mg of carbon, or


much older samples in which the fraction of the original 14C remaining is very small.
AMS has an effective limit of around 26,000 years, whereas activity ages are limited
to about 10,000y.
2. Internal Calibration. AMS can measure the ratios between all carbon isotopes
directly. This means that local variations in isotopic composition (fractionation) for
stable (12C and 13C) and unstable 14C isotopes are determined in situ.
In AMS, ratios are often expressed as deviations from a standard. For the
stable isotopes the National Institute of Standards and Technology (NIST)
gives the value Rstd=13C/12C = 0.011237. Deviation from this value for
different materials is expressed in parts per thousand (per mille, or )

R Rstd
1000
Rstd

Radiocarbon Dating by AMS - The Shroud of Turin

The Bomb Pulse

Read the original scientific article at http://www.shroud.com/nature.htm

AMS was used to determine the age of the Shroud of Turin by radiocarbon dating in
1989. Each sample investigated consisted of 50mg of cloth, which was analysed
independently by three different laboratories.
13C was measured directly, and gave results around -25, consistent with
calibration standards for such fibres (independent of age).
Radiocarbon age (corrected for 13C) was
determined from the 14C/13C ratio to be 69030
years BP. Three similar references samples were
also dated:
11-12th century linen dated at 940y BP
Linen from the mummy of Cleopatra dated at
1960y BP
Threads independently dated to 1300AD, 14C
dated at 724y BP.

Conclusion:
...the linen of the shroud of Turin is
mediaeval.

The ambient 14C level increased due to atmospheric nuclear testing,


peaking in 1962 - known as the Bomb Pulse.
This has been accurately tracked over time as the deviation from the prebomb isotope ratio, 14C, and can be used to accurately determine the
(recent) age of carbon-containing materials.
E.g.
wine dating & detecting false labels or blends.
dating drug crops.

U.S. Department of Energy photograph http://www.nv.doe.gov/news&pubs/photos&films/atm.htm

Biological Effects of Radiation

Biological Effects of Radiation

How do various forms of radiation interact with (biological)


matter?

Ionization produces free radicals. These are highly reactive


chemical species.

The basic characteristic of radiation produced by radioactivity is


that it is high energy, and causes the ionization of matter by
ejecting an electron from an atom. (Its generally called
ionizing radiation.)

E.g. Gamma irradiation of water ejects an electron creating a radical ion

When radiation is stopped my matter, it has interacted with it and


therefore caused ionization.

Highly penetrating radiation passes through matter without ionizing it.


Radiation protection and biological effects are the concern of Health
Physicists. Nuclear facilities employ health physicists to train staff,
monitor activites, and develop safety protocols.

+ H2O H2O+. + eBoth products lead to the production of more free radicals

H2O+ + H2O H3O+ + OH.

e- + H2O H . + OH-

Free radicals attack biomolecules such as DNA strands or membrane


lipids. This can (infrequently) lead to genetic damage, cancers,
disruption of cell membranes, or malfunctions in enzymes that
regulate biological processes.

Biological Effects of Radiation

Radiation Exposure

Penetrating power of , and radiation:


are heavy, highly charged particles.

Biological exposure arises through a variety of mechanisms.

When an particle strikes matter, it is stopped by as little as a single


sheet of paper.

E.g. Direct exposure to a radioactive source (external)

particles ionize the surfaces of matter effectively. Surface damage.

Gas or vapour: Diffuse source. May diffuse around shielding.

- are lighter, and more penetrating.

A - particle can be stopped by a few sheets of paper or plastic.


They ionize to a greater depth than particles.

are highly penetrating.

It takes several cm of water to gradually attenuate and stop


radiation.
radiation is less efficient, but causes internal damage.

are highly ionizing and penetrating.

A + particle reacts with an electron causing ionization and the


release of two gamma photons in opposite directions.

Solid or liquid: Localised source. Radiation can be shielded.

E.g. Contamination (external and internal)


External: Picking up radioactive material on hands, shoes, etc
Internal: Ingestion or inhalation.

The risk of damage from particles through internal contamination is


much higher than external, where they are quite well shielded by your
skin.
For more details, you can install and run the U.S. National Centre for Neutron Research safety training programme
available on the First Year Chemistry web site. This is the same programme used to train visitors, temporary and
permanent workers in the nuclear reactor at the National Institute of Standards and Technology.

10

Biological Effects of Radiation

Units of Radiation Dosage

Half-Life and Radiation damage

(Human) Radiation dosage is measured in rems (or millirems)


or in Sieverts (Sv).

Nuclides with longer half-lives disintegrate at lower frequency.

0.693
A = N =
N
t1 2
That is, longer half lives equals lower (molar) activity, so lower
potential for ionization and radiation damage.

From this point of view 238U, with a half-life of 4.5 billion years, or
230Th (T = 83,000 y) is less damaging than 3H (T = 12 y) or
1/2
1/2
234Th (T = 24.5 days).
1/2

Dosage attempts to include all the factors that can affect a living organism activity, energy, penetration, and the mass of living matter irradiated.
Source
Activity

,
Bq or Ci

Energy of
Radiation

Joule

The total expected dosage for an average person is about 360 mrem/year.
What are the short-term effects of radiation dosage?
25,000 mrem in 24h
50,000 mrem in 24h
100,000 mrem in 24h
200,000 mrem in 24h
500,000 mrem in 24h

No detectable effects
Slight temporary blood change
Nausea & fatigue
First death (no medical intervention)
LD50 (50% of humans exposed die.)

N.B. The probability of longer-term effects increases with dose. Most health
physicists use a linear no-threshold model. That is, they assume that there
is no level of exposure that is free from effects. However the time-scale and
statistical nature of the effects make low-dose response hard to determine.

Other Common Sources of Radioactivity

Other common sources of radiation include cosmic rays in the upper


atmosphere. Average annual exposure from this source at ground level
is ~26mrem.
A 4h plane flight increases dosage by a few mrem.

Medical exposure (x-rays and nuclear medicine) is around 40mrem/year

Consumer products ~10mrem/y

Nuclear fallout <1mrem/y

Nuclear power ~.05mrem/y

Relative
Biological
Effectiveness

Gray (J/kg)
or Rad

10
1
Q-factor

Effective Dosage
Equivalent

rem = rad x Q
Sievert =Gy x Q
1Sv = 100 rem
1Gy = 100 rad

Energy per particle x


activity x exposure
time

Dosages and Their Effects

Energy
Absorbed per
unit mass
(dose)

Radiation distributed
or localised?

Less penetrating
radiation does
more damage.

Common Sources of Radioactivity


We are exposed to several common natural sources of radioactivity. These
account for about 300mrem/year. The most common is radon, which is part
of the decay series of 238U and other heavy elements, and decays into
polonium with a half-life of 3.82 days.
222
86

4
Rn
218
84 Po + 2 He

decay of radon gas causes damage to lungs and is thought


to be responsible for up to 10% of lung cancers.
Other ambient isotopes include
40
K
18
Ar + 10 e

40
19

as dissolved potassium ions, and

C
147 N + 10 e

14
6

in CO2 and organic compounds.

Medical Imaging
Basic principles of medical imaging.
Use a radioisotope to specifically target a chemical agent, organ or process
in the body with high selectivity.
Isotope should emit low-energy, highly-penetrating radiation to minimise
effective dosage equivalent to patient. In practice this usually means .
Image distribution of radioisotope (by its activity) using scintillation counting
gamma camera (planar image like an x-ray) or
computer-assisted tomography (CAT or CT scan - cross section or
three-dimensional reconstruction)
Images may be a simple gray scale density or pseudo-colour signal.
Pseudo colour is especially common in computer-reconstructed imaging.

11

Gamma camera

CT scanner

Medical Imaging - 99mTc


Technetium-99m (99mTc) is used in about 85% of radionuclear
chemistry. It is formed by the decay of 99Mo by
99
42

Mo
9943mTc + 10 e

N/Z = 1.36 N/Z = 1.30

Tc is a wholly synthetic element and is


unknown in nature. It has no stable isotopes.

E.g. -camera image of 131I (from NaI


solution) uptake in a normal and
diseased thyroid gland, showing
localisation of iodine.

E.g. tomographic
image of a single
anatomical level of
the brain using 18Flabelled glucose.

Medical Imaging - 99mTc

The first isotope prepared was 98Tc


obtained in 1937 by the nuclear reaction
98
42

1
Mo + 12 H
98
43Tc + 2 0 n

Chemical Generation of 99mTc from 99Mo

Technetium-99m a metastable isomer that decays into 99Tc by


emission with a half-life of 6h.

Tc
99
43Tc +

99 m
43

Highly penetrating
radiation.

Then decays into ruthenium by emission, but with a half-life


of 2.1 x 105 years.

Tc
4499 Ru + 10 e

99
43

Long half-life = low activity.

N.B. As a gamma emitter, 99mTc remains the same element during its
residence in the body so it doesnt change its chemistry when it decays.

99Mo

has a half-life of 67h. It can be used for ~1 week as a continuous


source of 99mTc, which it replenishes after extraction. (Commonly
referred to as a Molly cow periodically milked for Tc.)
Extraction is based on the differential solubility of molybdate (MoO42-,
insoluble) and pertechnetate ions (TcO4-, soluble) in NaCl solution.
99MoO 2- is supplied in a cartridge, precipitated or adsorbed onto the
4
surface of a support like alumina (Al2O3). This is flushed with saline
solution to extract the daughter isotope 99mTc for use.
Pertechnetate ion may be used directly for imaging, e.g. thyroid or blood
circulation, or it may be chemically transformed to target other sites.
Several other generators are also used, exploiting chemical changes
accompanying radioactive decay to form and separate short half-life
nuclides for imaging. E.g.
82
38

Sr
3782 Rb + 10 e +

t1/2(82Rb) = 76 s

Medical Imaging

Medical Imaging - Positron Emission Tomography

How is 99mTc used?

Unlike 99mTc and other direct gamma emitters, positron emitters undergo
a nuclear transformation when they decay.

99mTc

e.g.

is incorporated into a wide variety


of compounds that are used to
specifically target sites in the body.

E.g.1. Technetium pyrophosphate is used to


target bones and identify bone cancer, as in
this gamma camera image.
E.g.2. Real-time imaging of technetium
penetrate is used to monitor kidney function.

C
115 B + 10 e +

11
6

18
9

F
188 O + 10 e +

This means that chemical reactions may ensue from both the nuclear
change and the reaction with an electron that produces the two s for
tomographic scanning.

e + + e
2
The annihilation of the positron by its
antiparticle produces energy in the form
of two s. Conservation of momentum
ensures that they travel in exactly
opposite directions, so the tomographic
detector gets two signals from each
decay event.

http://www.nuclearonline.org/PIbyGeneric2.htm

12

Medical Imaging - Positron Emission Tomography

Medical Imaging - Positron Emission Tomography

Positron Emitting Isotopes are generally formed in a cyclotron, which


bombards a stable sample with protons or deuterons.
Charged protons or deuterons are generated and accelerated in electric
field and magnetic fields along a spiral path until they strike their target
(stable) nuclide.

The nuclear reactions that generate PET radioisotopes transform atoms


within stable molecules. The desired products then need to be
chemically isolated from the product mixture.

14
7

N + 11H
116 C + 24 He

t1/2 = 20.3 min

O + 11H
137 N + 24 He

16
8

C + H
N+ n

13
6

1
1

13
7

14
7

1
0

E.g 14N in target N2 is transformed by 1H into 11C, producing CN.


14
1
116 C + 24 He
7 N + 1 H
Target N2 mixed with H2 leads to H11CN formation, which is
an important reagent used to produce many radiolabelled
organic molecules.

t1/2 = 9.97 min

N + 12 H
158 O + 01n t1/2 = 2.07 min
20
10

Ne + 12 H
189 F + 24 He t1/2 = 109.7 min

The short half-life of these radionuclides means that cyclotrons need to


be on-site at hospitals. E.g. The Australian Medical Cyclotron is located
next door to RPAH.

Medical Imaging - Positron Emission Tomography


These radiolabelled molecules must be purified, and can then be used
directly for imaging purposes, or used to synthesise more complex
molecules for research or diagnostic use at specific chemical sites. Fast
synthetic procedures are needed to keep the isotope active for use, often
using automated procedures or robots.
E.g. fluorodeoxyglucose (FDG) is synthesised in 35 minutes with 50%
radiochemical yield in a two-step process.
20
10

Ne + 12 H
189 F + 24 He

1. 18F- salt added in CH3CN solution


and heated to evaporate (10 min)
2. HCl added and heated (10 min)

FDG
Precursor glucose
derivative reagent

Target N2 mixed with O2 yields a mixture of products


including 11CO2 and 11CO.

Medical Imaging - Positron Emission Tomography


Fast synthesis of radiolabelled molecules allows them to be used to study
specific biochemical processes and responses.
E.g.1. FDG is absorbed by the brain like glucose, but the fluorine
substitution stops it from being completely metabolised. 18FDG It can be
used to examine the reaction mechanism, and changes in uptake &
metabolism accompanying various diseases.
These PET scans of a single
anatomical level in the brain
show changes in the brain
chemistry and glucose
metabolism by 18FDG with the
progress of AIDS Dementia
Complex.
Colour scale increases:
black-blue-yellow-red-white

Recognising organic molecules and synthetic


techniques will come up later in this course.

Medical Imaging - Summary


Nuclear imaging is useful because it allows us to radiolabel molecules
that specifically target organs, molecules or chemical processes for
diagnosis or biochemical research.
The synthetic chemistry to design these target molecules differs widely: Cyclotron-produced PET isotopes (11C, 18F) are often exploited
in the synthesis of organic molecules (drugs, peptides,
carbohydrates, steroids, vitamins)
Metals (99mTc, 82Rb,) may be used as soluble or insoluble salts,
or as co-ordination compounds, to mimic biological molecules,
toxins, as heavy heavy metal tracers,
Footnote: Magnetic Resonance Imaging (MRI) is not a radiochemical technique.
Although based on the technique of nuclear magnetic resonance (NMR), MRI uses the
quantum mechanical properties of 1H and other stable nuclei (e.g. 13C) to measure and map
the concentration of chemical species at different positions in an organ or whole body.

Summary I
You should now be able to
Recognise nuclear reactions, including the major
spontaneous decay mechanisms.
Define and distinguish between nucleons, nuclides &
isotopes, x-rays & gamma rays, decay series and
daughter isotopes.
Explain stellar nucleogenesis.
Calculate the average atomic mass from isotope
information.
Balance nuclear reactions.

There are no nuclear reactions or decay processes involved.

13

Summary II

Summary III

You should now be able to

You should now be able to


Explain the main factors that contributes to effective
radiation dose, including penetrating power, activity,
energy.
Explain the main mechanism of biological damage by
ionizing radiation.
Explain the use of radioactive isotopes in medical
imaging, and distinguish the information obtained from xrays.
Explain how isotope generators produce e.g. 99mTc for
medical imaging, and give some examples of its use.
Explain PET, the generation of radioisotopes by a
cyclotron, and the know the kinds of isotopes produced.

Recognise stable and unstable nuclides.


Predict the decay mechanism for an unstable isotope.
Calculate the activity or half-life of an unstable nuclide
from appropriate data.
Calculate the age of a sample using the carbon-14
method, and know the underlying assumptions and
appropriate timescale for its application.

14

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