Video 1

 Elemental Analysis - Introduction and

applications
Advanced Chemical Analysis

Elemental, Chemical and

Structural Analysis

Dr Aleksandar Radu
 Course Outline
Lectures 1-3
 Introduction
 Elemental (‘Chemical’) Analysis
– Atomic Absorption Spectroscopy (AAS)
– Inductively Coupled Plasma (ICP) spectroscopy
– X-ray fluorescence (XRF) spectroscopy
 Applications of Elemental Analysis
 Chemical and Structural Analysis
– X-ray diffraction (XRD)
– Electron microscopy and X-ray micro-spectroscopy (EDAX)
– Combination with other spectroscopic and analytical techniques
Problem Class
 Applications of Elemental Chemical Analysis in the research
literature
Practical
 Analysis of water, soil and vegetation using ICP spectroscopy
 Suggested Reading
 D.C. Harris, Exploring Chemical Analysis, Ch. 20
 R. Levinson, More Modern Chemical Techniques, p. 1-72
 F.W. Fifield and P.J. Haines, Environmental Analytical
Chemistry
 Chapter 7 – Atomic Spectrometry
 Part II – Specific Applications, p. 307-471
 Chapter 13 – Speciation
 Chapter 15 – Trace elements
 Chapter 17 – Contaminated landsites
 Chapter 18 – Analysis of water
 Chapter 20 - Ecotoxicology
 Session outcomes
 Appreciation of techniques for elemental analysis
 Understanding of advantages and limitations of the
techniques
 Understanding of the role of the techniques in analysis of
unknown sample

Exam questions:
 Explain the basic principle of technique X and why can it be
used in elemental analysis
 Describe advantages and limitation of technique X compared
to technique Y
 Describe how techniques X and Y can complement each
other in practice
 Applications of elemental analysis
 Elemental chemical analysis of solids and liquids
 Elemental analysis in:
– Materials
– Pharmaceuticals
– Geochemistry
• Minerals, rocks, soil
– environmental analysis
• Vegetation, soil, minerals
– forensic analysis
• bullets, gun-shot residue, explosives, glass, document
examination, fibres, paint, body
– cultural heritage
• paintings, documents, archaeological samples, antiques,
provenance, historical samples
 Applications of elemental analysis
 Contaminants, impurities and trace elements,
including in organic matter
– Water, oils, inks, fibres
 Water analysis
– For organic impurities and contaminants, e.g. in water and soil,
such as organic pollutants (chemicals, pesticides, industrial and
agricultural effluent) use GC and GC-MS
 Trace analysis of materials
Applications – Environmental Chemistry

Soil analysis
Applications – Environmental Chemistry

Analysis of Vegetation
Applications – Environmental Chemistry

Water analysis –
contaminated water
Applications – Geochemical Analysis

Analysis of minerals
 Applications – Forensic Analysis

Analysis of gunshot
residue
Applications – Cultural Heritage, Art,
Provenance

Analysis of works of art

– authentication and
forgeries
Applications – soil fertility

Gridded output of total nitrogen (TN ha−1yr−1)

export at 4 km2 resolution for the year 2000
for the River Dee WFD RBD (Water Framework
River Basin District)
Greene et al; A geospatial framework to support integrated biogeochemical modelling in the
United Kingdom; Environmental Modelling & Software; Volume 68, June 2015, Pages 219-232
Applications – Agricultural and Food Science
Environmental Analysis
Requirements for
Type of applications analytical technique
 Soil/minerals 

Suitable for analysis of solid material
Suitable for analysis of liquid materials
 Water
Single/multi-element analysis
Vegetation


 Suitable sensitivity (suitably low limit of
detection (LOD))
 Plant nutrients  Suitable selectivity (ability to differentiate target
analyte from other chemical species present in
 Pollution the sample)

 Portability

 Large area  Destructive/Non-destructive

 Analysis time (especially relevant when a large

 Valuable materials/small number of samples need to be analysed)
– Don’t forget time needed for sampling and sample
amount of sample processing

 Price
Video 2

 Atomic Spectroscopy - introduction

Atomic spectroscopy

 Relies on absorption/emission of light(energy)

 Absorbed/emitted light is characteristic for the specific element
(target analyte)
 Specificity originates from distribution of electrons in electronic
shell of atoms

 Ability to use atomic spectroscopy relies on instrument design to

successfully utilize absorption/emission of specific light thus
distinguishing target element from others in the sample as well
as the ability of instrument to successfully measure (small) light
intensity in order to correlate it with the amount of target
element
– Selectivity and sensitivity
The Electromagnetic Spectrum
 Principles of Spectroscopy – Quantization of energy

ΔE = E2 – E1 = h  = h c  = h c /
2 E2 h = Planck’s Constant
E2 and E1 are the two energy levels
 = frequency of radiation, Hz
 = wavenumber – units, cm-1
c = speed of light, m s-1
 = wavelength of radiation, m
1 E1 In molar units, J/mol

ΔE = NA h  = NA h c / 

Energy ‘units’: J, kJ/mol, Hz, cm-1, eV

 Atomic Spectroscopy
 Expect to have an understanding of:
 Chemical basis and principles of atomic spectroscopy
 Atomic absorption, emission and fluorescence
 Atomic Absorption Spectroscopy
 flame and graphite furnace
 Inductively Coupled Plasma Spectroscopy
 Optical Emission Spectroscopy and Mass spectroscopy
 Major uses and applications in chemical analysis
 Comparison of Atomic Absorption and ICP Spectroscopy
 Strengths and limitations of elemental analysis compared with
other analytical techniques
 Complementary nature of elemental analysis with other analytical
and spectroscopic techniques, including x-ray diffraction,
vibrational spectroscopy (IR, Raman), UV/vis, NMR, electron
microscopy
Video 3

 Atomic Absorption Spectroscopy (AAS) and

sample preparation
 Atomic Absorption spectroscopy
 Can be carried out on species already in solution, as well as
chemically digested solid samples
– Ideally suited for analysis of water samples –
contaminated water analysis, water purity
 Solid samples need to be chemically digested
– Dissolution of sample
– an involved process, frequently involving high temperature
reflux (or microwave) treatment in concentrated acid
(usually nitric or hydrofluoric) and/or hydrogen peroxide
and then atomised in the instrument
 technique is destructive
Chemical Digestion
 1% Nitric Acid
 Aqua Regia(3:1 mixture of hydrochloric (HCl) and nitric (HNO3) acids;
– considered effective for measuring “total” trace element in soils and is usually
used to give an estimate of the maximum element availability to plants;
– considered adequate for dissolving most base element sulphates, sulphides,
oxides and carbonates but only provides a “partial” extraction for most rock
forming elements and elements of a refractory nature. For example, aqua regia
extraction might give complete recovery for Cd, Cu, Pb and Zn while it is known
to provide partial recovery for Cr, Ni and Ba.
– Addition of H2O2 into Aqua Regia assists with destruction of organic matter

 Hydrofluoric Acid (HF) combinations of HNO3-HCl-HF and HNO3-HClO4-HF assists with

dissolution of silicates

 Fractionation:
– Soluble (DI water, HCO3-, etc)
– Labile (1M KCl, 0.1M acetic acid + 0.1M oxalate buffer, etc)
– Moderately labile organic and/or mineral (0.1M NaOH, HCl, etc)
– Occluded (1% Nitric Acid)
– Total dissolution (Aqua Regia only or with the addition of H2O2, HF, etc)
 Chemical digestion of solid materials

Chemical digestion of
soil samples – high
temperature reflux in
concentrated nitric acid
Video 4

 Atomic Spectroscopy principles and GFAAS

Atomic Absorption and Emission spectroscopy

Atomization: process in which

chemical bonds are broken
(for example due to
application of sufficient
amount of energy such as
thermal energy) but atoms are
Excitation: transition of
NOT ionized
electron from lower energy
orbitals to higher energy
orbitals; no change in charge

Ionization: ejection of electron

from the electronic shell thus
producing positively charged
ion
Atomic Absorption and Emission spectroscopy
 Optical spectra are observed (between 150 – 1000 nm) WHY?
 Absorption / emission lines are extremely narrow (0.001 nm)
 Multi-component (multi-element) analysis is possible
 Various detectors can be used
Pb hollow cathode lamp
Graphite Furnace AAS - GFAAS
GFAAS
Advantages of GFAAS
• More sensitive
• Higher residence
time of analyte in
the optical path
• Less sample required
• Composition of flame,
gas flow and oxidant-
fuel ration are NOT
issues as in FAAS

Disadvantages of GFAAS
• Long measuring time
(up to 5 min/sample)
• High matrix interference
• Limited dynamic range
HGAAS

HGAAS
• For metaloids (As, Sb,
Se, Te and Hg)
• Cheaper then ICP
 Atomic Absorption spectroscopy
 Atomisation of species in solution occurs in either a flame
or a graphite furnace at temperatures in range ~ 2100 –
2800°C
 Technique of Atomic Absorption Spectroscopy (AAS)
– Flame AAS (FAAS)
– Graphite furnace AAS (GFAAS)
– Hydride generation AAS (HGAAS)
 Single element analysis
 Highly sensitive method of elemental analysis
– Flame AAS – ppm
– Graphite furnace - ppb
Video 5

 ICP AES and ICP MS

 Interferences
 Summary
 Atomic emission spectroscopy
 Atomisation occurs using a flame or plasma

Plasma
• More uniform temperature
• Longer sample residence time
• Hotter (~6000-8000 oC)more
complete atomization)
• Formation of oxides and
hydroxides almost negligible

Nebulizer
Inductively-coupled Plasma (ICP) spectroscopy
(Atomic emission spectroscopy)
 Atomisation occurs using a plasma – plasma temperature ~
6000 - 8000°C
 Detect emission either optically or using mass
spectrometer
 Technique of Inductively-coupled Plasma (ICP)
spectroscopy
– ICP-OES (ICP-Optical emission spectroscopy)
– ICP-MS (ICP-mass spectroscopy)
 Multi-element analysis is possible in single experiment
 Highly sensitive method of elemental analysis
– ICP-OES  ppb
– ICP-MS  ppt
ICP spectroscopy

Plasma and nebulizer

Plasma
ICP spectroscopy – multiple samples

Autosampler

Sample rack
 Atomic Spectroscopy – Detection Limits
 Most (but not all) elements can be analysed
 Detection limits can be as low as parts per trillion (ppt) –
generally parts per billion (ppb)
 Atomic Spectroscopy - Interferences
 Spectral
– Overlap of analyte signal with signals originating from other
elements/molecules
 Background

•Absorption of IR
or scattering
A
from sample
matrix
I0 IT=I0-
IR
Deuterium lamp


A
Rotating chopper


Mirror Atomizer Monochromator Analyser
 Atomic Spectroscopy - Interferences
 Chemical
– Caused by a component in the sample that decreases
atomization of the analyte (e.g. SO42- and PO43- hinder
atomization of Ca2+ by forming nonvolatile salts)

 Ionization
– Forming ions instead of excited atoms
Na(g) – Na+(g) + e-

 Price
– ICPMS = 3-4 ICP OES=5-10 GFAAS=10-20AAS (~$10-
15k base)
 Atomic Spectroscopy - Summary
 AAS and ICP are carried on liquid samples
– Species in solution can be studied as well as digested solid
samples
– Destructive techniques
 Qualitative and quantitative elemental analysis
 ICP gives multi-element analysis, whereas AAS only gives
single-element analysis
 High sensitivity (generally ppm and ppb, can be as high as ppt
for ICP-MS and GF-AAS)
 Data acquisition is very quick in all cases and analysis is relatively
straightforward, once instrument has been calibrated
 Accurate calibration is essential
 Minimal chemical interference in spectra in ICP
Video 5

 XRF
X-ray Fluorescence (XRF)
spectroscopy
 Principles of XRF
 Basis of XRF is that different elements in a sample emit
characteristic x-rays when excited by x-ray or high energy
electron source

 The wavelength (or energy) of the emitted x-rays are

measured
 Measurement of the wavelength (or energy) of emitted x-rays
gives the identities of the elements present
 Measurement of the intensity of each peak can give the amount
of each element present
Principles of XRF
 Principles of XRF spectroscopy
 When x-rays (or high energy electrons) with energies above a
certain threshold interact with atoms the following changes occur:
 An electron is ejected from one of the inner (core) shells
(energy levels) of the sample, leaving a hole (excitation
process) – i.e. atom is ionised
 This is immediately followed by an internal rearrangement
(relaxation process) within the atom, whereby an electron
from a higher energy level drops down to fill the hole.
 The resulting energy is released as an x-ray which is
simultaneously emitted
 The wavelength (and energy) of the emitted x-ray is
characteristic of the element from which it is emitted
 Hence measuring the wavelengths (or energies) of the
emitted x-rays gives rise to elemental chemical analysis of
the sample
 The emitted x-rays are lower in energy (have longer wavelengths)
than the energy (wavelength) of the incident x-radiation
 The Competing Auger process
 When x-rays interact with atoms two different electronic processes can
occur:
– The first is the XRF process
– A second, competing process, Auger electron emission, can also
occur:
The Auger process
 The first two stages are the same as XRF – the atom is excited by an x-
ray or high energy electron, an electron is ejected from a core shell,
leaving a hole which is filled by an electron from a higher energy
level, and an x-ray is emitted
 However, in the Auger process the escaping x-ray photon is
absorbed when it interacts with an outer electron of the atom
 The outer electron is emitted instead of the photon
 Thus, two electrons are lost – the atom becomes doubly ionised
 Auger emission is particularly common in elements with low atomic
numbers because the relatively small nuclear charge making it
comparatively easy to eject a second electron
 XRF is less sensitive for elements with low atomic numbers and
cannot be used for Z < 4 because the competing Auger process dominates
 XRF Instrumentation
 Two main types of XRF spectrometer:
 wavelength dispersive (WD) XRF spectrometer
 energy dispersive (ED) XRF spectrometer

 Wavelength dispersive XRF spectrometer is the traditionally

most commonly used XRF instrument
– X-rays emitted by sample are diffracted and dispersed by
crystal monochromator
– By rotating the crystal different wavelengths are diffracted
and reach the detector
– Detector converts x-ray photons into visual signal (voltage
pulses)

 Energy dispersive XRF spectrometers have no

monochromator and separate the characteristic x-rays emitted by
sample according to their energies
XRF Instrumentation
 Energy dispersive XRF (EDXRF)
 Energy dispersive XRF spectrometers separate the characteristic x-
rays emitted by fluorescing sample according to their energies
 There is NO crystal monochromator – the detector receives
all the emitted x-rays simultaneously
 For each x-ray photon incident on the detector, a pulse of
electric current is produced which is proportional to the energy
of the x-ray
 A multi-channel detector separates the pulses on the basis
of the energy of x-ray from which pulse originated
Comparison between wavelength dispersive and
energy dispersive XRF techniques
 EDXRF instrument is much more compact and cheaper than
WDXRF – no crystal monochromator and associated drive
mechanism, smaller x-ray source
 portable  on-site applications and in field
 EDXRF requires less intense x-ray source than WDXRF because of
proximity of sample to detector  cheap, low power x-ray tubes
can be used. WDXRF requires more expensive x-ray tubes which
need replacing more often, and thicker (more expensive) windows
for higher intensity x-rays
 Relative advantages of wavelength dispersive
and energy dispersive XRF instruments
EDXRF
particularly suited to
– portable, on-site and field-based applications
– Rapid qualitative (and quantitative) elemental analysis
of samples
–  Can very quickly analyse/screen large number of
samples
–  Elemental mapping/scanning of (non-uniform)
samples and fragments (at high spatial resolution using
micro-XRF)

WDXRF
particularly suited to
– Identifying elements present in very low concentrations
– Accurate quantitative elemental analysis of samples
XRF Spectroscopy – from mobile spectrometers
for measurements in the field

Mobile energy-dispersive XRF

spectrometer for rapid
measurements and analysis on-site

Portable hand-held energy-dispersive

XRF spectrometer for rapid in situ
measurements on-site
XRF Spectroscopy – to international synchrotron
facilities

Diamond – the UK’s

new synchrotron,
near Oxford

Electrons accelerated to near light

speeds and directed towards different
laboratories.

The light is used to study a vast

range of subject matter, from new
medicines and treatments for
disease to innovative engineering
and cutting-edge technology.
 XRF – Issues
 Matrix effect particle size, uniformity, homogeneity, and condition of the surface.
Every effort should be made to homogenize soil samples thoroughly before analysis.
 Moisture content above 20% can interfere with the analysis, since moisture alters
the soil matrix for which the field-portable XRF has been calibrated. This problem can
be minimized by drying
 Inconsistent positioning of samples in front of the probe window is a potential
source of error because the X-ray signal decreases as the distance from the
radioactive source increases. Maintaining a consistent distance between the window
and the sample minimizes this problem.
 Chemical matrix effects also can occur as X-ray absorption and enhancement
phenomena. The presence of certain metals can interfere with the analysis of certain
other metals. For example, iron tends to absorb copper X-rays, whereas chromium
levels will be enhanced in the presence of iron. These effects can be corrected
mathematically through the field-portable XRF instrument’s software. Vendors can
typically provide the necessary information during the planning stage to anticipate
these interferences.
 Instrument resolution limitations may cause problems in analyzing some elements.
If the energy difference between the characteristic X-rays of two elements (as
measured in eV) is less than the resolution of the detector in eVs, then the detector
will not be able to resolve the peaks. In other words, if two peaks are 240 eVs apart,
but the resolution of the detector is 270 eV, the detector will have difficulty in
differentiating those peaks. A common example is the overlap of the arsenic K peak
with the lead L peak. With the use of mathematical corrections that subtract the lead
interference, lead can be measured from the lead L peak and arsenic can be measured
from the arsenic K peak. However, concentrations of arsenic cannot be calculated
efficiently for samples that have lead-to-arsenic ratios of 10 to 1 or more, because the
lead peak will overwhelm the arsenic peak completely.
 LIMITATIONS OF XRF

Selectivity: Interferences between some elements (high levels of one

element may give a false positive for another due to overlapping emission lines and
limited resolution of ~0.2 keV FWHM)

No info on chemical form of element (alternate technique

required for speciation)

Detection Must use alternate technique to measure sub-ppm levels

Limits: (TXRF, GFAAS, ICP-AES, ICP-MS)

Accuracy: XRF is predominantly a surface analysis technique (X-rays

penetrate few mm into sample)

To get more accurate results, one must homogenize the

samples and calibrate instrument response using authentic standards
 X-ray Fluorescence - Summary
 Non-destructive
 Qualitative and quantitative multi-elemental analysis
 High sensitivity (ppm)
 Can analyse any solid samples in situ
 Sample preparation is minimal - no requirement for chemical
digestion and specially prepared solutions
 Cannot be used to analyse species in solution
 Data acquisition is very quick and analysis is relatively
straightforward (once full calibration has been done)
 Minimal chemical interference in spectra
 Advances in technology have led to portable XRF spectrometers
– use for on-site analysis in the field and in remote locations
– screen large number of samples quickly (on site)
 Comparison of XRF with ICP and AAS
 XRF is non-destructive – AAS and ICP are destructive - sample has
to be chemically digested (usually by refluxing in concentrated nitric acid
or HF) and atomised
 XRF much more versatile for analysis of solid materials - can
analyse any solid samples in situ – no requirement for time-
consuming chemical digestion and specially prepared
solutions, unlike ICP and AAS
 Sample preparation is minimal in XRF
 AAS and ICP can be carried on liquid samples, i.e. species in solution,
as well as (digested) solid samples, XRF cannot
 XRF and ICP both give multi-element analysis, whereas AAS only gives
single-element analysis – hence AAS used more for applications involving
element-specific analysis
 ICP has higher sensitivity than AAS and XRF – ppb or even ppt compared
to ppm
 Minimal chemical interference in spectra in XRF and ICP, unlike in AAS

 None of the three techniques provide info on chemical form –

need alternative technique for chemical speciation
Elemental Analysis of materials - Summary
 X-ray Fluorescence (XRF) Spectroscopy
– wavelength (WD) or energy dispersive (ED) XRF
 Inductively Coupled Plasma (ICP) Spectroscopy
– Detection by Optical Emission (ICP-OES) or by mass
spectroscopy (ICP-MS)
 Atomic Absorption Spectroscopy (AAS)
– Detection by flame (FAAS) or graphite furnace (GFAAS)

 Elemental Analysis of materials – any type of solid sample can

be analysed
 Species in solution by ICP and AAS

 None provide information of chemical form

Electron microscopy and
Micro-spectroscopy
Electron microscopy and
Micro-spectroscopy
Resolution: in
nanometer
Magnification: 10x
to 300000x
 Electron Microscopy
 Can use beams of electrons rather than light as the source
 The much shorter wavelengths of electrons compared to visible
light results in electron microscopy having much higher
resolution than with standard optical microscope
 Electron microscopy can be carried out in:
– transmission mode - electrons pass through sample, or
– scanning mode - electrons back-scattered from the sample
surface
 Scanning and Transmission electron microscopy result in
different types of image being formed
 Transmission Electron Microscopy (TEM)
 Electrons pass through the sample
 Scattering of electrons by sample produces an image
 Extremely thin samples required (<0.2 m) to produce a good
image
 Sample preparation requires considerable expertise and can be
extremely time consuming
 Image has no depth profile
 Image observed is very dependent on how sample is prepared
 TEM gives extremely high resolution – 1-100 nm
Inorganic sample/physical science specimen
preparation for TEM

http://www.ammrf.org.au/myscope/tem/practice/prep/inorganic/
 Electron
microscope images
of (a) BEA-CDM1
and (b) MTW-CDM1
(left column: SEM,
right column: TEM)

Na et al; Cyclic diquaternary ammoniums for nanocrystalline BEA, MTW and MFI zeolites with intercrystalline mesoporosity;
J. Mater. Chem., 2009, (19), 6713
 Scanning Electron Microscopy (SEM)
 SEM uses electrons reflected (back-scattered) from the surface of
a sample
 Thickness of sample is not important
 Sample preparation much simpler than for TEM
 Practical samples can be examined, often in their native state
 High-intensity focused electron beam is back-scattered from the
surface, and continuously measured as beam is scanned over the
surface
 Scanning Electron Microscopy (SEM)
 Magnification of image can be greater than 1 million
compared to few hundred in conventional optical microscopy
 Resolution of SEM is not as high as TEM
 Very large magnification range of image can be obtained with SEM
from 10 nm - 100 m (0.1 mm)
 Gives insight into sample topography
 Particle/sample shape and morphology
 Particle size
 Surface texture
 Surface details and defects in surfaces, e.g. cavities,
impressions (depth of field)
 Very powerful analytical technique
Can offer chemical composition
Chrystalographic, magnetic and electrical characteristics
 Scanning Electron Microscopy (SEM)

 Drawbacks:
– Operates under high vacuum
– Samples need to be conductive (coating with thin layer of carbon, gold,
platinum…)
 What SEM can do
– Image morphology of samples (bulk material, coatings, fols etc)
– Image compositional and some bonding differences (through contrast and
backscattered electrones)
– Image molecular probes (metal and fluorescent)
– Micro- and nano-litography (remove material sfrom sample, cut pieces (using
focused beam)
– View frozen material (SEM with cryostage)
– Generate X-rays from samples for microanalysis
– Electron difraction using electron backscattered diffraction
 What SEM can not do
– No color images (unless it has specific detector (cathodoluminescence)
– Can not image through water
– Not good for quantifying surface roughness at small scale (need AFM)
– No liquids, chemical reactions, air-gas systems
– Individual atoms (need TEM)
– Elemental analysis below micron scale
 Biological Materials
Geo Science
Science Science

Investigation of soils and Large objects such as In materials science SEM

geological samples is insects and animal is a key tool used for basic
common place in scanning tissues and small research, quality control
electron microscopy. objects such as and failure analysis.
Analysis of morpology can bacteria and viruses SEM plays a key role in
inform about weathering are studied by SEM. many topics of current
processes. Compositional interest including
differences can be seen nanotubes and nanofibres,
with backscattered high temperature
electron imaging superconductors,
mesaporous architectures,
alloy strength and so on.

http://www.ammrf.org.au/myscope/sem/background/practical/practical/
 Micro X-ray spectroscopy
 The X-rays emitted from the sample in both SEM and TEM can
be energy analysed to give elemental analysis as in XRF, i.e.
combining electron microscopy with x-ray fluorescence to
give micro X-ray fluorescence
 Elemental mapping (imaging) of sample at a microscopic
level
 Can superimpose elemental mapping (imaging) onto
sample topography
 Generally SEM is combined with energy dispersive XRF
 Often called Energy Dispersive Analysis of X-rays (EDAX or
EDX)
Schematic of micro XRF
 Micro X-ray spectroscopy
 Enables very small amounts of sample to be analysed non-
destructively
 Combination of topography and elemental composition is very
powerful
 Spectrometer is an integrated component of instrument
 Scan sample with precision motorised computer-controlled sample
stage
 Allows automated mapping of samples
 Limitation is the intensity of x-ray source of microscope
 Recent technological advances in detector technology have helped
overcome this
 Micro X-ray spectroscopy
 These huge advances in recent years in micro x-ray spectroscopy
have revolutionised the ability to study a huge and very diverse
range of samples
– Trace elements, contaminants and impurities in soil, wood and
other vegetable and animal matter, and in water
– Geological materials
– archaeological fragments
– Famous works of art, antiques, historical documents, ancient
fibres
– individual fibres, fragments of explosives, gunshot residue,
paint chips, glass fragments, bullets
– space dust
X-ray Diffraction (XRD)
 X-ray Diffraction (XRD)
 X-ray diffraction (XRD) is the major technique for identification
and characterisation of crystalline inorganic materials
 Most widely used and least ambiguous method for determination
of structure of crystalline solids
 XRF, ICP and AAS give elemental composition of material, BUT
give limited chemical insight - chemical speciation – can only
be inferred without employing additional analytical techniques
 Spectroscopic techniques, such as infrared spectroscopy, although
useful for study of inorganic samples, do not give complete picture
 Huge structural diversity of inorganic materials and minerals in
terms of elements involved, coordination numbers, geometries and
bond lengths, means that each crystalline inorganic material
has a unique diffraction pattern
 Principles of XRD
 X-rays interact with electrons in matter
 When x-ray beam impinges on material it is scattered by the
electron clouds of the atoms
 If the wavelength of x-rays is comparable to the separation
between atoms in compounds interference of scattered x-rays
occurs
– Use x-rays of wavelengths typically 60 –190 pm
 A crystalline solid (ordered array of scattering centres) 
interference maxima and minima
 Principles of XRD
 X-rays interact with planes of atoms
(different lattice planes) in the 3D
crystalline solid
 Each lattice plane is member of set of
equally spaced planes
 Each atom (lattice point) must lie on
one of the planes
 Planes are labelled using Miller
indices, designated h, k, l
 The XRD experiment
 Generate a collimated x-ray beam of single wavelength (60 -190
pm) (monochromatic), typically using copper K x-ray source,
and
 Sometimes use a crystal monochromator to improve resolution
of diffraction pattern
– More monochromatic x-rays, but reduced intensity, so lower
sensitivity
 X-ray beam interacts with solid powder sample (or crystal) loaded
onto sample stage
 X-rays are scattered from the sample
 Detect scattered x-rays with a moving detector
The XRD experiment – sample geometries
 Fixed x-ray source and sample stage and detector move through
angles of  and 2 respectively (-2 geometry)
 Stationary sample and both x-ray source and detector move
through angle of  (- geometry)

Schematic of -2
geometry
 Scattering of x-rays from crystalline solids

Scattering of X-rays from a set of lattice planes defined by Miller

indices h, k, l
 Scattering from crystalline solids – Bragg equation
 Scattering of x-rays from points A and D in neighbouring planes
results in diffracted x-rays which are in phase (constructive
interference) IF the extra distance travelled by x-ray scattered
from D is a whole number of wavelengths more than that
scattered from A
 Extra distance travelled = distance BD + distance DC
 This distance depends on lattice spacing (dhkl) and angle of
incidence of x-ray beam, 
 Extra difference travelled = BD + DC = 2 x dhkl x sin 
 Thus, for a whole number of wavelengths, , extra travelled
(the condition for diffraction):
2 dhkl sin  = n  The Bragg Equation
 n normally considered to be unity
 Each set of planes, h, k, l, has particular separation, dhkl,
 Thus, for each set of planes there will be a diffraction peak
at a particular angle, 
Scattering from crystalline solids – Bragg equation
 The relationship between the d-spacing and lattice parameters
of the crystalline solid (i.e. the structure) can be determined
geometrically
 By combining the equation relating d-spacing to the lattice
parameters for a particular crystal system, with the Bragg
equation, and eliminating dhkl
 Direct relationship between diffraction angle and lattice
parameters (structure) of the material
 Scattering of an x-ray beam by a crystalline solid  large
number of diffraction peaks, the positions of which are
related to the lattice parameters of the material , i.e. the
chemical structure of the material
 X-ray diffraction gives structural information about
crystalline solids
Typical XRD pattern
 Powder X-ray diffraction
 Consequence of the huge range of different structures which
inorganic materials adopt (coordination numbers, geometries and
bond lengths) means that each crystalline inorganic material
or mineral has a unique powder x-ray diffraction pattern in
terms of the positions of the observed reflections (peaks)

 Fingerprint  identify what compounds and phases are

present (provided crystalline)
 In mixtures, each crystalline compound present will have
its own unique set of reflections
 Relative intensities of one set of reflections compared with another
depends on the amount of each compound present (as well as
ability of given structure to scatter x-rays)
 quantitative technique (once calibration experiments have
been carried out)
 Application of X-ray Diffraction in
Environmental Science and Geoscience
Identification of crystalline materials and minerals
 Over 500,000 unique powder XRD patterns have been
collected and complied onto a database – JCPDS (Joint
Committee on Powder Diffraction Standards
 Database can be used to rapidly identify a crystalline material
from its powder XRD pattern – cross-match by on-line search
 Much quicker identification of unknown materials compared
with other methods, especially wet methods
 In mixtures, each different crystalline phase present
will contribute separately to the overall powder XRD
pattern
 Example of Analysis of mixture by XRD

Reaction of
MgO + Al2O3
 Limitations of X-ray Diffraction
 Phase must be crystalline – XRD will not detect
amorphous (non-crystalline) materials however much
of the material is present
 Phase must be present at level of > ~3%
 Analysis of complex mixtures with several different phases
present at different levels can be quite complicated
 Chemical insight often necessary
 combine with XRF or ICP which give overall elemental
composition
 As x-rays are scattered by electrons, light elements
scatter x-rays poorly in comparison with heavy
elements
 Identification of minority compounds can be quite difficult,
especially if these contain light elements, in the presence of
other compounds
 X-ray Diffraction - Summary
 Non-destructive
 Routine identification of crystalline materials
 Highly complementary to X-ray fluorescence (or ICP) -
gives additional chemical insight, as well as other
spectroscopic and microscopic techniques
 Much quicker identification of unknown materials compared with other
methods, especially wet methods
 Quantitative analysis of (crystalline materials within) mixtures, though
calibration can be time-consuming
 Can analyse any solid samples in situ
 Sample preparation is minimal
 Data acquisition is quick
 Data analysis is straightforward for single materials and simple mixtures.
Can be difficult for more complex mixtures or if only small amount of
particular compound present
 New advances in terms of x-ray intensity (synchrotron radiation) and
detector technology have increased sensitivity and data acquisition times,
and mean that XRD can be used:
– Can examine very small amounts of sample
– To image and establish maps of crystalline phases present in
heterogeneous practical samples
 Correlation
Is there relationship between two variables?

Correlation = Direction and strength of (linear) relationship

between two variables

Relationship between hours studying (X) Relationship between water hardness

and exam marks (Y) determined by titration (Y) and ICPAES
7 0.05
(X)
6
5 0.04
Y (score)

4
titration 0.03
3
2
0.02
1
0 0.01
0 2 4 6 8
X (hours of studying)
0
0 0.01 0.02 0.03 0.04 0.05
ICP
Pearson coefficient
degree to which X & Y vary together
r=
degree to which X & Y vary separately
σ 𝑋−𝑋 𝑌−𝑌
r=
2 2
𝑋−𝑋 𝑌−𝑌

r = .90 r = -.40

r = -1.0 r = .00
 Words of caution
 Restricted range
 Outliers
 Correlation vs.
causality
Group work

 Groups of 4 (four)
 Discuss the task and write brief conclusions
(bullet points; line of thoughts) (10 min)
– Sensitivity, cost, simplicity/reliability, dynamic
range of concentration, speed, accuracy,
precision, utility, waste generation, field
portability, ruggedness, and compatibility with
existing EPA methods.
 Student with the highest student number in
the group presents
 Class discussion (5 min)
Quality control of foundry products
(Aluminium bronze)
 The aluminium bronzes are a range of copper based
alloys in which aluminium up to 14% is the primary
alloying element. Their combination of strength and
corrosion resistance makes them one of today's most
important engineering materials for highly stressed
components in corrosive environments.

 You need to suggest to CEO of the newly formed

foundry an instrument that will enable routine
monitoring of Al in bronze samples. You are on a
VERY limited budget. Suggest a technique of choice
and justify (also give important issues to be aware
of)
Heavy metal soil pollution

 Tailing site from an abandoned silver mine

was deemed to be a source of serious heavy
metal pollution (As, Pb, Cd, Cu and Zn) or soil
in nearby farming community. Explain what
technique (combination of techniques?)
would you use to quantify the pollution and
monitor the site

 Justify your choice and give important issues

to be aware of
Analysis of Martian rocks

 Phoenix Mars Mission brought a rock sample

from Martian soil.
 Identify a technique (or combination of two
techniques) that posses the optimal
characteristics for analysis of such sample.
Fully justify your answer
Technique principles

 Atomic emission and XRF are fundamentally

very similar techniques.
 Note the similarity and differences and
explain why both of these techniques can be
used in elemental analysis.