Learning Objectives

1
Explain the structure of the
atom and Bohr’s model

Differentiate between emission

2
and absorption spectroscopy

3 Explain the chemistry behind EDX and SEM-EDX

4 Explain the chemistry behind NAA

1
What Is It Made Of?

What are the chemical elements present?

Spectroscopy & the structure of atoms

How can we do elemental analysis?

When and why do we want to

carry out elemental analysis?
2
What Is It Made Of?

When and why do we want to

carry out elemental analysis ?

When it gives the required information

3
Examples

1 Poisoning

Suspected arsenic, lead

or chromium poisoning

Analyze body fluids

Poison
4
Examples

1 Poisoning

2 Determining the time of death

Analyze bone chemistry

5
Examples

1 Poisoning

2 Determining the time of death

3 Elemental analysis of bullets

Forensic information about firearms use

6
Cases

River Thames, London, September 2001

7
Cases

How many people

fired at JFK?

John F Kennedy
8
Cases

Death of Napoleon

Napoleon
9
What is an Element?

Ancient Greeks

4 elements

Concept discarded

10
What is an Element?

Robert Boyle (1627 – 1691)

Elements can neither be

created nor destroyed

Robert Boyle
11
What is an Element?

Elements are the basic building blocks

93 naturally occurring

Others created artificially

12
What is an Element?

Common naturally occurring elements

H Fe Zn

O Ag Sn

C
13
What is an Element?

Less common naturally occurring elements

U Sm Kr

Ir Gd Sb

14
Paper

Made of cellulose C, H, O

Burning a piece of paper

C CO2

H H2O

15
Human Body

C, H, O, N, P, S, Ca, Na, K, Fe…

C CO2

H H2O

N N oxides

P P oxides
16
Human Body

Au or Hg in teeth

Au Au

Hg Hg oxides

17
The Periodic Table

18
The Periodic Table

Dmitri Mendeleev

Chemist

Organized the elements

according to chemistry
Dmitri Mendeleev
19
The Periodic Table

Tom Lehrer

Mathematician and musician

Organized elements musically

http://www.youtube.com/
watch?v=AcS3NOQnsQM Tom Lehrer
20
What Is It Made Of?

Bulk composition

What is most of it made of?

Lead in bullets

Bullet
21
What Is It Made Of?

Trace impurities

What is a very small

part of it made of?

Silver and antimony in bullets

Bullet
22
What Is It Made Of?

Analysis of elements

1 Bulk composition

2 Trace impurities More informative for

forensic scientists

23
Chemical Tests

Disadvantages

Large amounts of samples required

Destructive

Subject to interference
24
Chemical Tests

Advantages

Fast

Easy to do

Simple equipment
25
Trace Impurities

How small is small?

S. I. prefixes for units

26
S. I. Prefixes

1 Megagram 1 Mg 1 000 000 g 1 tonne

1 Kilogram 1 Kg 1 000 g
1 milligram 1 mg 0.001 g 1 / 1000th
1 microgram 1 µg 0.000 001 g 1 / 1000 000th
1 nanogram 1 ng 0.000 000 001 g 1 / billionth
1 picogram 1 pg 0.000 000 000 001 g 1/ trillionth

1 picogram 100 000 000 000 atoms

27
Trace Impurities

Trace elements often measured in ppm

Part per million 1 per 1 000 000

1 g of 1 tonne 1 ppm

28
Trace Impurities

5M people in Singapore

1 ppm = 5 people

Singapore map
29
Trace Impurities

Trace elements often measured in ppm

Sometimes measured in ppb

Part per billion 1 per 1 000 000 000

30
Trace Impurities

7B people in the world

7 000 000 000

1 ppb = 7 people
World map

31
The Spectrum

White light separated

into component colours

Rainbows

Pass light through

glass prism

Double rainbow
32
The Spectrum
White light separated
into component colours

Rainbows

Pass light through

glass prism

White light separated

3
3
The Spectrum

Sunlight

Observe resulting
spectrum

34
The Spectrum

Fraunhofer Discontinuous spectrum

35
The Spectrum

Discontinuous spectrum

Discrete
black bands

Light absorbed
by hydrogen Joseph von
Fraunhofer
36
The Spectrum

Other lines?

Absorption of light
by an unknown
element

Helium
Norman Lockyer
37
The Electromagnetic Spectrum

Different spectroscopic techniques

use different frequencies of light

Light is a small portion of spectrum

38
The Electromagnetic Spectrum

39
Structure of the Atom

1 Plum pudding model

Plum pudding model

40
Structure of the Atom

1 Plum pudding model

Plum pudding
41
Structure of the Atom

1 Plum pudding model

Rutherford’s
2
planetary model

Ernest Rutherford
42
Structure of the Atom

1 Plum pudding model

Rutherford’s
2
planetary model

3 Bohr’s model

Niels Bohr
43
Bohr’s Model
Electrons

1 Restricted to specific energy levels

Energy is quantized

Energy is not continuous

Very small quanta of energy

44
Bohr’s Model
2 Can move from one energy level to another

Jump to higher energy level Absorb energy

Drop to lower energy level Release energy

Electromagnetic radiation / light

Frequency proportional to energy change

de Broglie equation: E = hv
45
Allowed Energy Levels for Absorption

Energy
absorbed

Energy levels = ladder rungs

Energy added matches gap to next rung

46
Elemental Analysis
1 Using electrons

Absorption spectroscopy

47
Allowed Energy Levels for Emission

Energy
emitted

Energy levels = ladder rungs

Energy released matches gap to next rung

48
Elemental Analysis
1 Using electrons

Absorption spectroscopy

Emission spectroscopy

49
Elemental Analysis
Excited
1 Using electrons state

Absorption
spectroscopy

What light is absorbed?

Ground
state

50
Elemental Analysis
Excited
1 Using electrons state

Emission
spectroscopy

What light is emitted?

Ground
state

51
Bohr’s Theory
Multiple energy levels

Multiple emissions
or absorptions

Multiple lines in spectra

Pattern is characteristic
for each element
52
Flame test for Metals

Metal salt added to flame

Characteristic colour produced

Energy of flame excites electrons

Drop back to ground state

Sodium
(orange)
Emit light
53
Elemental Analysis
1 Using electrons

Absorption spectroscopy

Emission spectroscopy

2 Using the nucleus

Neutron Activation Analysis (NAA)

54
Neutron Activation Analysis
1 Irradiate sample with neutrons

55
Neutron Activation Analysis
2 Excited nucleus

56
Neutron Activation Analysis
3 Nucleus decays Gives out gamma ray

57
Neutron Activation Analysis
4 Nucleus becomes radioactive

58
Neutron Activation Analysis
5 Gives out delayed gamma ray

59
Neutron Activation Analysis
6 Product nucleus formed

60
Neutron Activation Analysis

Gamma rays are characteristic

Measure energy of gamma rays

Analyze element

61
Neutron Activation Analysis

Advantage

Non-destructive of sample

Disadvantage

Require nuclear reactor

62
Neutron Activation Analysis

Qualitative &
quantitative
multi-element
analysis

63
Microscopy

Analyze extremely small objects

GSR particle

Diameter of 5 μm

Gunshot residue particle

64
Microscopy

Analyze extremely small objects

Scanning Electron Microscope (SEM)

Uses electron instead of light

65
SEM-EDX

Energy Dispersive X-ray fluorescence (EDX)

SEM-EDX Hyphenated technique

SEM Look at very small objects

EDX Non-destructive analysis

looking at core electrons
66
SEM-EDX

67
N apoleon

68
Napoleon’s Career

Emperor of
General most of Europe

Artillery Dictator 1815

Officer of France
Battle of
Waterloo

Defeated
69
Napoleon’s Career

Emperor of Exiled to
General most of Europe St. Helena

Artillery Dictator 1815 1821

Officer of France
Battle of Died
Waterloo

St. Helena Defeated

70
Napoleon’s death

Died in his fifties Respectable age

Rumors: murdered?

No evidence Buried

No exhumation allowed
71
Napoleon’s death

Artefacts Hair samples

19th century

After the death of famous people

Some of their hair was kept as souvenir

72
Napoleon’s hair

NAA carried out in 1952

Presence of arsenic

Murdered?

Motive?

British? Napoleon
73
Napoleon’s hair

NAA carried out in 1952

Presence of arsenic

Murdered?

Motive?

Or French? Napoleon
74
Newcastle, 1980

Dr. David Jones

“What colour was

Napoleon’s wallpaper?”

Someone knew what color the wallpaper was

Also had a sample of the wallpaper

75
St. Helena

Port of call

Napoleon’s house is a tourist attraction

Tourists tore off a piece of wallpaper

Souvenir
St. Helena
76
Arsenic from Wallpaper?

Historic sample Cannot destroy it

SEM-EDX Non-destructive

Analyze specific
microscopic objects

77
Arsenic from Wallpaper?

Green pigments

Copper arsenite
(Scheele’s Green)

How did it get from

the wallpaper to
Napoleon? Napoleon’s wallpaper
78
Arsenic from Wallpaper?

Green pigments

St. Helena’s climate breeds mold

Mold
CuAsHO3 AsH3 (arsine gas)

Arsine gas breathed in by Napoleon

79
Who Killed Napoleon?

Autopsy results

Stomach cancer

80
Who Killed Napoleon?

Autopsy results

Eyewitnesses

Attendants recorded what they saw

81
Who Killed Napoleon?

Autopsy results

Eyewitnesses

Doctors?

Treated him with mercury chloride

82
 Kennedy
Assassination

83
Kennedy just before
his assassination

84
Lee Harvey
Oswald

85
Questions

1 Did Lee Harvey Oswald act alone?

2 Was there a second gunman?

If there was a second gunman,

how many bullets would there be?

86
Questions

How many bullets fired by Lee Harvey Oswald?

One missed

Two hit

87
Bullet Analysis

Bullets can fragment

How to put fragments together?

How to determine the

total number of bullets?

88
Bullet Analysis

Trace element
composition

Silver (Ag)

Antimony (Sb)
 Bullet Analysis

Neutron Activation Analysis (NAA) results

Fragment Ag / ppm Sb / ppm Sample description

1 8.8 ± 0.5 833 ± 9 Connally stretcher bullet
2 9.8 ± 0.5 797 ± 7 Connally’s wrist (fragment)
3 8.1 ± 0.6 602 ± 4 Car (large fragment)
4 7.9 ± 0.3 621 ± 4 Kennedy’s brain (fragments)
5 8.2 ± 0.4 642 ± 6 Car (fragment)

90
NAA Analysis

Bullet fragments divided into two groups

Two bullets

Most likely a single gunman

91
“Adam”

92
Thames, 2001

Torso found

Missing head

Missing arms

Professional cuts

Blood drained
93
Evidence

1 A torso

2 A pair of shorts

94
Shorts

Made in China

Manufacturer found

Batch identified

Sold in West Germany

95
Torso

Stomach contents examined

1 Food

2 Pollen

Identify plant

Identify origin Northern Europe

96
Torso

Stomach contents examined

1 Food 4 Calabar beans

2 Pollen Toxic
3 Clay From Africa

97
Torso

Stomach contents examined

1 Food 4 Calabar beans

2 Pollen 5 Gold particles

3 Clay

Items 3, 4, 5 associated with African black magic

98
From Evidence

Murder?

Human sacrifice

How to continue with the investigation?

Where did Adam come from?

99
You Are What You Eat

Bones

Calcium phosphate
in protein matrix

Calcium derived from diet

Other metals
incorporated into bones
100
Traditional Societies

Eat home-grown food

Minerals from local soil

Incorporated into bones

101
You Are What You Eat

Relative abundance of trace elements in bones

Indicate geographical origin

Strontium, copper, lead

Analyze Adam’s bones

102
You Are What You Eat

Strontium
Copper
Lead

103
Summary

1 How spectroscopic methods work

Emission spectroscopy

Absorption spectroscopy

2 EDX & SEM-EDX

3 Neutron Activation Analysis

104