X-ray Fluorescence

PM. Dr. Banjuraizah Johar

• X-ray fluorescence is
a non-destructive
analytical technique
used to determine
the elemental
composition of
materials.
 Electron-matter interaction volume
and various types of signal generated
Basic principles for XRF
• When a material is irradiated with X-rays, it emits secondary
(fluorescent) X-rays characteristic of the elements present.
• X-ray tube: Produces primary X-rays.
• High-energy photons interact with the electrons in the atoms of
the sample.
• Ejection of inner-shell electrons leads to a vacancy. Electrons
from higher energy levels fill the vacancy, releasing energy as X-
rays.
• Characteristic X-rays: Unique to each element, allowing for
identification
 XRF
• The analysis of major and trace elements in
materials by XRF is possible by the behavior
of atoms when they interact with radiation.
 ATOMIC STRUCTURE

• An atom consists of a nucleus (protons and

neutrons) and electrons
• Z is used to represent the atomic
number of an element (the number
of protons and electrons)
• Electrons spin in shells at specific distances from
the nucleus
• Electrons take on discrete (quantized) energy
levels (cannot occupy levels between shells)
• Inner shell electrons are bound more tightly and
are harder to remove from the atom
 ELECTRON SHELLS
Shells have specific names (i.e., K, L, M) and
only hold a certain number of electrons

The shells are labelled from the

nucleus outward

K shell - 2 electrons

L shell - 8 electrons

M shell - 18 electrons
N shell - 32 electrons

X-rays typically affect only inner shell (K, L) electrons

 MOVING ELECTRONS TO/FROM SHELLS
Binding Energy versus Potential Energy

• The K shell has the highest binding energy

and hence it takes more energy to remove an
electron from a K shell (i.e., high energy X-
ray) compared to an L shell (i.e., lower
energy X-ray)

• The N shell has the highest potential energy

and hence an electron falling from the N shell
to the K shell would release more energy (i.e.,
higher energy X-ray) compared to an L shell
(i.e., lower energy X-ray)
Theory
▪ A source X-ray strikes
an inner shell electron.
If at high enough energy
(above absorption edge
of element), it is ejected
it from the atom.

▪ Higher energy electrons

cascade to fill vacancy,
giving off characteristic
fluorescent X-rays.
Bohr atomic model
• According to Bohr's model, atoms consist of a nucleus (containing protons and
neutrons) surrounded by electrons in defined orbits or energy levels. Each orbit
corresponds to a specific energy state.

• Electrons occupy specific energy levels, which are quantized. For example, in a
hydrogen atom, these levels are designated by the principal quantum number 𝑛n
(1, 2, 3, etc.).

• The energy associated with these levels can be calculated using:

𝐸𝑛=−𝑍2 x 13.6 eV /𝑛2 , where Z is the atomic number.
• In XRF, a sample is irradiated with high-energy X-rays (the excitation source). When
these X-rays interact with the atoms in the sample, they can impart enough energy
to eject an inner-shell electron (for instance, from the K-shell).
• When an inner-shell electron is ejected, a vacancy is created. According to the
Bohr model, this vacancy can be filled by an electron from a higher energy level.
For example, an electron from the L-shell may drop down to fill the K-shell
vacancy.
• The transition of electrons from higher to lower energy levels releases energy in
the form of X-rays.
• The energy of the emitted X-ray is equal to the difference between the energy
levels involved:𝐸emitted=𝐸higher−𝐸lower

• Each element has a unique set of energy levels, meaning that the X-rays emitted
will have specific energies characteristic of that element. This is what allows for
the identification of elements in the sample.
• The emitted X-rays are detected by an XRF instrument, which analyzes the
energies of these X-rays. By measuring the energies and intensities of the emitted
X-rays, the elemental composition of the sample can be determined
Bohr Atomic Model
The term fluorescence is applied to phenomena in
which the absorption of higher-energy radiation
results in the re-emission of lower-energy
radiation.
 Characteristic radiation
• Each element has specific
energy levels for its
electrons (characteristic
energy).

• When an inner electron is

knocked out by a high-
energy photon, an outer
electron moves into its
place.
Figure 1: Electronic transitions in a calcium atom.
• There are only a few ways Remember, when electrons are jumping down, one of the
this can happen, as shown electrons in the outer shell is missing!
in the diagram
The main transitions are given names:
an L →K transition is traditionally called Kα,
an M→K transition is called Kβ,
an M→L transition is called Lα, and so on.
• Each of these transitions yields a fluorescent photon with a
characteristic energy equal to the difference in energy of the initial
and final orbital.

• The wavelength of this fluorescent radiation can be calculated

from Planck's Law:
Analysis Lines
• The spectral lines used for chemical analysis are selected on
the basis of intensity, accessibility by the instrument, and lack
of line overlaps. Typical lines used, and their wavelengths, are
as follows:

wavelength Element line wavelength

Element line
(nm) (nm)
Li Kα 22.8 Ni Kα1 0.1658
Be Kα 11.4 Cu Kα1 0.1541
B Kα 6.76 Zn Kα1 0.1435
C Kα 4.47 Ga Kα1 0.1340
N Kα 3.16 Ge Kα1 0.1254
 wavelength wavelength
Element line Element line
nm nm
I Lα1 0.3149 Pt Lα1 0.1313
Xe Lα1 0.3016 Au Lα1 0.1276
Cs Lα1 0.2892 Hg Lα1 0.1241
Ba Lα1 0.2776 Tl Lα1 0.1207
La Lα1 0.2666 Pb Lα1 0.1175
Ce Lα1 0.2562 Bi Lα1 0.1144
Pr Lα1 0.2463 Po Lα1 0.1114
Nd Lα1 0.2370 At Lα1 0.1085
Pm Lα1 0.2282 Rn Lα1 0.1057
Sm Lα1 0.2200 Fr Lα1 0.1031
Eu Lα1 0.2121 Ra Lα1 0.1005
The fluorescent radiation can be analyzed either by sorting the
energies of the photons (energy-dispersive analysis) or by
separating the wavelengths of the radiation (wavelength-
dispersive analysis).

Once sorted, the intensity of each characteristic radiation is

directly related to the amount of each element in the material.
This is the basis of a powerful technique in analytical chemistry.
Typical energy dispersive XRF spectrum
 Elemental range

beryllium (4) to uranium (92) in solids

fluorine (9) to uranium (92) in liquids

range of elements in solid samples
are shown in green (Be to U)
range of elements in liquid samples
are shown in green (Na to U)
 Detection limits (LLD)
Function of atomic number (Z) & the mix
of elements within the sample (sample
matrix)

< 1 ppm for high Z in a light matrix (e.g.

Pb in petrol)

or > 10 ppm for low Z in a heavy matrix

(Na in slag)
 SIMPLE XRF SPECTRUM
~10% As in Chinese supplement400
As K line
10.53 keV

300

Intensity (cps)
200
As K line
11.73 keV

100

0
0 5 10 15 20 25 30 35 40

Energy (keV)

• The presence of As in this sample is confirmed through observation of two peaks

centered at energies very close (within ±0.05 keV) to their tabulated (reference) line
energies
• These same two peaks will appear in XRF spectra of different arsenic-based
materials (i.e., arsenic trioxide, arsenobetaine, etc.)
 SIMPLE XRF SPECTRUM
700
Pb L  line Pb L  line
10.55 keV 12.61 keV
600

500
Intensity (cps)

400 ~10% Pb in imported Mexican tableware

300

200

100

0
0 5 10 15 20 25 30 35 40
Energy (keV)

• The presence of Pb in this sample is confirmed through observation of two peaks centered
at energies very close (within ±0.05 keV) to their tabulated (reference) line energies
• These same two peaks will appear in XRF spectra of different lead-based materials
(i.e., lead arsenate, tetraethyl lead, etc.)
Instrumentation components
• X-ray source (tube or radioactive source)
• Sample holder
• Detector (e.g., Si-PIN, Ge)
• Multichannel analyzer
BOX DIAGRAM OF XRF INSTRUMENT
X-ray Digital Pulse XRF Results
Source Detector Spectrum (elements
Processor software
(cps vs keV) and conc’s)

Sample
• X-ray tube source
✓ High energy electrons fired at anode (usually made from Ag or Rh)
✓ Can vary excitation energy from 15-50 kV and current from 10-200 A

• Silicon Drift Detector (SDD) and digital pulse processor

✓ Energy-dispersive multi-channel analyzer – no monochromator needed, Peltier-cooled solid state detector
monitors both the energy and number of photons over a preset measurement time
✓ The energy of photon in keV is related to the type of element
✓ The emission rate (cps) is related to the concentration of that element

• Analyzer software converts spectral data to direct readout of results

✓ Concentration of an element determined from factory calibration data, sample thickness as estimated from
source backscatter, and other parameters
 Overview of XRF methodology

Good accuracy requires:

• careful sample preparation

• fused beads for light elements
• accurate standards
• selection of optimum instrument parameters
• collection of enough counts to avoid statistical errors
XRF instrumental parameters
• x-ray tube kv, mA
• primary beam
filters
• collimator masks

• collimator
• crystal
• detector
• path
Schematic diagram XRF instrument
 The Hardware

• Sources
• Optics
• Filters & Targets
• Detectors
Side Window X-Ray Tube
Be Window
Glass Envelope Target (Ti, Ag, HV Lead
Rh, etc.)

Electron beam
Copper Anode
Filament

Silicone Insulation
Soller Collimators

• Soller and similar types of collimators are used to prevent

beam divergence.
• Used in WDXRF to restrict the angles that are allowed to
strike the diffraction device, thus improving the effective
resolution.
 Detector Filters
Filters are positioned between the sample and detector in
some EDXRF systems to filter out unwanted x-ray peaks.

Sample

X-Ray
Source
 Source Filters
Filters perform one of two functions
– Background Reduction
– Improved Fluorescence

Source Filter

Detector

X-Ray
Source
 Filter Fluorescence Method
With Zn Source filter Target peak

ENERGY (keV) Fe
Region

The filter fluorescence method decreases the background and

improves the fluorescence yield without requiring huge amounts of
extra power.
 Wavelength Dispersive XRF
• Wavelength Dispersive XRF relies on a diffractive device such
as crystal or multilayer to isolate a peak, since the diffracted
wavelength is much more intense than other wavelengths.

device. Sample

Detector

Collimators

X-Ray
Source
Diffraction Device
Energy Dispersive Electronics

Fluorescence generates a current in the detector. In a detector

intended for energy dispersive XRF, the height of the pulse
produced is proportional to the energy of the respective incoming
X-ray.

Signal to Electronics
Element A
Element B
DETECTOR
Element C
Element D
 Multi-Channel Analyser
• Detector current pulses are translated into counts (counts per second, “CPS”).
• Pulses are segregated into channels according to
energy via the MCA (Multi-Channel Analyser).

Intensity (# of CPS
per Channel)
Channels, Energy
Signal from Detector
Detector Principles
➢A detector is composed of a non-conducting or semi- conducting material
between two charged electrodes.
➢X-ray radiation ionizes the detector material causing it to become conductive,
momentarily.
➢The newly freed electrons are accelerated toward the detector anode to
produce an output pulse.
➢In ionized semiconductor produces electron-hole pairs, the number of pairs
produced is proportional to the X-ray photon energy

E
n =
e

where : n = n u m b e r o f e l ec t r o n - h o l e p ai r s p r o d u c e d
E = X-ray ph oton ener gy
e = 3 . 8 ev f or S i a t L N 2 t e m p e r a t u r e s
 Detectors
• Si(Li)
• PIN Diode
• Silicon Drift Detectors
• Proportional Counters
• Scintillation Detectors
 Si(Li) Detector
FET
Window

Super-Cooled Cryostat

Dewar
filled with
Si(Li) LN2
Pre-Amplifier
crystal

Cooling: LN2 or Peltier

Window: Beryllium or Polymer
Counts Rates: 3,000 – 50,000 cps
Resolution: 120-170 eV at Mn K-alpha
 PIN Diode Detector

Cooling: Thermoelectrically cooled (Peltier)

Window: Beryllium
Count Rates: 3,000 – 20,000 cps
Resolution: 170-240 eV at Mn k-alpha
 Silicon Drift Detector- SDD

Packaging: Similar to PIN Detector

Cooling: Peltier
Count Rates; 10,000 – 300,000 cps
Resolution: 140-180 eV at Mn K-alpha
Proportional Counter
Window

Anode Filament

Fill Gases: Neon, Argon, Xenon, Krypton

Pressure: 0.5- 2 ATM
Windows: Be or Polymer
Sealed or Gas Flow Versions
Count Rates EDX: 10,000-40,000 cps WDX: 1,000,000+
Resolution: 500-1000+ eV
 Scintillation Detector

Window: Be or Al
Count Rates: 10,000 to 1,000,000+ cps
Resolution: >1000 eV
Spectral Comparison - Au

Si(Li) Detector Si PIN Diode Detector

10 vs. 14 Karat 10 vs. 14 Karat
 Sample Preparation
Powders:
✓ Grinding (<400 mesh if possible) can minimise scatter affects due to particle
size..
✓ Pressing (hydraulically or manually) compacts more of the sample into the
analysis area, and ensures uniform density and better reproducibility.

Solids:
✓ Orient surface patterns in same manner so as minimise scatter affects.
✓ Polishing surfaces will also minimise scatter affects.
✓ Flat samples are optimal for quantitative results.

Liquids:
✓ Samples should be fresh when analysed and analysed with short analysis time –
if sample is evaporative.
✓ Sample should not contain precipitants/solids
 XRF methodology
First determine the following:
• what elements are to be measured
• what are their concentration ranges
• what accuracy is required
• how many samples are to be measured
• are suitable standards available
 XRF methodology
Elements to be measured
• low Z will require careful preparation
• low Z may have lower accuracy
• low Z may require fusion of powders
• semi-quant does not measure the very light
elements (Be to N)
 XRF methodology
concentration ranges
as the concentration range for each element
increased, accuracy generally decreases

large concentration ranges will require

more standards
 XRF methodology
Good accuracy requires
▪ careful sample preparation
▪ fusion of powder samples for Z  13
▪ longer analysis time
▪ accurate calibration standards
▪ careful selection of each variable
instrument parameter
 XRF methodology
Calibration standards
• require the same sample preparation as
unknown samples.
• accurate chemical analysis
• need to cover concentration ranges
• mechanically stable
 XRF SPECTRA: Consecutive elements in periodic table
15

Zn
Ga
Ge
As
Se
10
Intensity
(cps)

0
5 6 7 8 9 10 11 12 13 14 15
Energy (keV)

• Plotting only a portion of the XRF spectra of several different elements

• Note periodicity - energy is proportional to Z2 (Moseley’s law)
PERIODIC TABLE OF XRF FLUORESCENCE DATA
Including K and L line energies & detection limits
XRF ENERGIES FOR VARIOUS ELEMENTS

• ORGANIC ELEMENTS (i.e., H, C, N, O) DO NOT GIVE XRF PEAKS Fluorescence

photons from these elements are too low in energy to be transmitted through air and are not
efficiently detected using conventional Si- based detectors

• LOW Z ELEMENTS (i.e., Cl, Ar, K, Ca) GIVE ONLY K PEAKS

L peaks from these elements are too low in energy (these photons are not
transmitted through air and not detected with conventional Si-based detectors)

• HIGH Z ELEMENTS (i.e., Ba, Hg, Pb, U) GIVE ONLY L LINES

K peaks from these elements are too high in energy (these electrons have high binding
energies and cannot be removed with the limited voltage available in field portable analyzers)

• MIDDLE Z ELEMENTS (i.e., Rh through I) MAY GIVE BOTH K AND L LINES

 XRF – MORE DETAILED DESCRIPTION
Note energy level diagrams are not drawn to scale

∞ As ∞ Pb

N 4s2p3d10f14 N 4s2p3d10f14

L 12.55 keV
M 3s2p3d10 M 3s2p3d10
K 11.73 keV
L 10.61 keV
L 2s2p6
As Pb
L 2s2p6
>15.21 keV
(absorption edge)

K 10.53 keV

K 1s2 K 1s2
>11.86 keV
(absorption edge - minimum amount of energy needed to remove electron)
• Since XRF affects inner shell and not bonding electrons, the XRF spectrum of an
element is independent of its chemical form (i.e., spectra of lead, lead arsenate, and
tetraethyl lead will ALL show peaks at 10.61 and 12.55 keV)
 K LINE SERIES
~10% As in Chinese supplement
400
As K line
10.53 keV

Intensity (cps) 300

200
As K line
11.73 keV

100

0
0 5 10 15 20 25 30 35 40

Energy (keV)

• L lines not observed (1.28 and 1.32 keV - too low in energy to be excited)
• K and K peak energies are often close together (1.2 keV apart for As)
• K lines observed for low to medium Z elements (i.e., Cl, Fe, As)
• K and K peaks have typical ratio of ~ 5 to 1
 L LINE SERIES
~10% Pb in imported Mexican tableware
700
Pb L  line Pb L  line
10.55 keV 12.61 keV
600

500
Intensity (cps)

400

300

200

100 Pb L line

0
0 5 10 15 20 25 30 35 40
Energy (keV)

• K lines not observed (75.0 and 94.9 keV - too high in energy to be excited)
• L and L peak energies are often further apart (2.1 keV apart for Pb)
• L lines observed for high Z elements (i.e., Hg, Pb, Th)
• L and L peaks have typical ratio of ~ 1 to 1
MORE COMPLEX XRF SPECTRUM
Chinese supplement containing 4% As and 2% Hg
120

As K line
10.53 keV
100

80
Intensity (cps)

Overlapping lines
60
As K 11.73 keV
Hg L 11.82 keV
Hg L line
40 9.99 keV

20

0
9 10 11 12 13

Energy (keV)

• Line overlaps are possible and users must evaluate spectrum to confirm the
presence or absence of an element
 EFFECT OF DETECTOR RESOLUTION
Spectra of 900 ppm Pb added into Pepto-Bismol

Older Si(PIN) detector Newer SDD

Bi L line Bi L line
10.84 keV 10.84 keV
Bi L line Bi L line
13.02 keV 13.02 keV

Pb L line Pb L line Pb L line Pb L line

10.55 keV 12.61 keV 10.55 keV 12.61 keV

• Resolution ~0.2 keV (FWHM) • Resolution ~0.15 keV (FWHM)

• Cannot resolve Pb and Bi peaks • Can resolve Pb and Bi peaks
Evaluating Spectra

• In addition to elemental peaks, other peaks appear in the spectra:

✓ K & L Spectral Peaks
✓ Rayleigh Scatter Peaks
✓ Compton Scatter Peaks
✓ Escape Peaks
✓ Sum Peaks
✓ Bremstrahlung
K & L Spectral Lines

❖K - alpha lines: L shell e- transition to fill

alpha
vacancy in K shell. Most frequent
transition, hence most intense peak.
beta

❖K - beta lines: M shell e- transitions to fill

K alph vacancy in K shell.

Shell ❖ L - alpha lines: M shell e- transition to

L Shell fill vacancy in L shell.
M Shell

N Shell ❖L - beta lines: N shell e-transition to fill

vacancy in L shell.
K & L Spectral Peaks

K-Lines

L-lines

Rh X-ray Tube
Scatter

Sample
• Some of the source X-rays
strike the sample and are
scattered back at the detector.
Sometimes called
“backscatter”
Detector Source
Rayleigh Scatter

• X-rays from the X-ray tube or target strike

atom without promoting fluorescence.
• Energy is not lost in collision. (EI= EO)
• They appear as a source peak in spectra.
• AKA - “Elastic” Scatter

EO

EI
RAYLEIGH PEAKS Elastic scattering from metal alloy sample
50

metal sample
45 Cr, Fe, Ni
peaks from
40
metal sample
35

30 Rayleigh Peaks

Intensity (cps)
25
(Rh L and L lines)

20

15

10

0
0 5 10 15 20 25 30 35 40
1 Energy (keV)
E0 = initial energy of X-ray from target element in x-ray tube source.
E1 = energy of X-ray elastically scattered from (typically dense) sample
• Peaks arising from target anode in X-ray tube source (Rh in this case) that may appear in all XRF spectra.
• No energy is lost in this process so peaks show up at characteristic X-ray energies (Rh L and L at
20.22 and 22.72 keV in this case)
• Typically observed in spectra of dense samples as weak peaks (due to increased absorption of X-ray source
photons by sample)
Compton Scatter

• X-rays from the X-ray tube or target strike

atom without promoting fluorescence.
• Energy is lost in collision. (EI >EO)
• Compton scatter appears as a source peak in
spectra, slightly less in energy than
Rayleigh Scatter.
• AKA - “Inelastic” Scatter

EI EO
COMPTON PEAKS: Inelastic scattering from cellulose sample
100

90
cellulose sample Compton Peaks
(E’s < Rh L and L lines )
80

70
PHOTO
ELECTRON 60

Intensity (cps)
50
Rayleigh Peaks
40 (Rh L and L lines)
30

20

E0 = initial energy of X-ray from target 10

element in x-ray tube source 0

E1 = energy of X-ray inelastically scattered 0 5 10 15 20 25 30 35 40

from (typically non-dense) sample

Energy (keV)

• Peaks arising from target element in X ray tube (again, Rh in this case) that may appear in all XRF spectra.
• Some energy is lost in this process so peaks show up at energies slightly less than characteristic X-ray tube
target energies
• Typically observed in spectra of low density samples as fairly intense peaks (note these peaks are wider than
Rayleigh peaks)
Brehmstrahlung

• Brehmstrahlung (or Continuum) Radiation: German

for “breaking radiation”, noise that appears in the
spectra due to deceleration of electrons as they strike
the anode of the X- ray tube.
BREMSSTRAHLUNG Continuum/backscatter from cellulose sample
100

40 kV
E0 > 90
20 kV
10 kV
80

70
Bremsstrahlung

Intensity (cps)
60

50

40

30

20

10

0
0 5 10 15 20 25 30 35 40

E0 = initial energy of electron in X-ray tube source Energy(keV)

E1 , E2 = energy of X-ray

• Very broad peak due to backscattering of X-rays from sample to detector that may appear in all XRF spectra
• Maximum energy of this peak limited by kV applied to X-Ray tube, maximum intensity of this peak is ~
2/3 of the applied keV
• More prominent in XRF spectra of less dense samples which scatter more of X-ray source photons back to the
detector
Interferences

❖ Spectral Interferences

❖ Environmental Interferences

❖ Matrix Interferences
Spectral Interferences
• Spectral interferences are peaks in the
spectrum that overlap the spectral peak
220 eV Resolution (region of interest) of the element to be
analyzed.

• Examples:
– K & L line Overlap - S & Mo,
Cl & Rh, As & Pb
– Adjacent Element Overlap -
Al & Si, S & Cl, K & Ca...

• Resolution of detector
determines extent of overlap.
Environmental Interferences

Air Environment • Light elements (Na - Cl) emit weak X-rays,

easily attenuated by air.

• Solution:
– Purge instrument with He (less dense than air
= less attenuation).
– Evacuate air from analysis chamber via a
vacuum pump.
• Either of these solutions also eliminate
interference from Ar (spectral overlap to Cl).
Argon (Ar) is a component of air.
 Matrix Interferences
Absorption/Enhancement Effects

• Absorption: Any element can absorb or scatter the fluorescence of

the element of interest.

• Enhancement: Characteristic x-rays of one element excite another

element in the sample,

ence
Absorption-Enhancement Affects

Red = Fe, absorbed

Blue = Ca, enhanced

▪ Incoming source X-ray fluoresces Fe.

▪ Fe fluorescence is sufficient in energy to fluoresce Ca.
▪ Ca is detected, Fe is not. Response is proportional to concentrations of each element.
 ARTIFACT PEAKS

• Arising from detection process.

• The interaction of X-ray fluorescence photons from the sample with the
detector can generate several different types of artifact peaks in an XRF
spectrum which may include the following:

➢Sum peaks

➢Escape peaks
 SUM PEAKS Example from analysis of Fe sample

Detector
Fe K photon Fe K peak
6.40 keV 6.40 keV

Sum peak
12.80 keV
Fe K photon
6.40 keV

Sum Peak = Fe + Fe 12.80

= 6.40 + 6.40 Fe sum peak
12.80 keV

• Artifact peak due to the arrival of 2 photons at the detector at exactly the same
time (i.e.,K + K, K + K )
• More prominent in XRF spectra that have high concentrations of an element
• Can be reduced by keeping count rates low
 Sum Peaks
▪ 2 photons strike the detector at the same time.

▪ The fluorescence is captured by the detector, recognized as 1 photon

twice its normal energy.

▪ A peak appears in spectra, at: 2 X (Element keV).

ESCAPE PEAKS Example from analysis of Pb sample
700
Pb L  line Pb L  line
Detector 10.55 keV 12.61 keV
Si K photon 600
1.74 keV
500

Intensity (cps)
400 Pb escape peak
Escape peak (from L)
8.81 keV 300
Pb L photon
Pb escape peak
10.55 keV 200
(from L)
100
Escape Peak = Pb – Si
8.81 = 10.55 – 1.74 0
0 5 10 15
Adapted from Thermo Scientific Quant’X EDXRF training manual

• Artifact peak due to the absorption of some of the energy of a photon by Si atoms in the detector
(Eobserved = Eincident –Esi where ESi = 1.74 keV)
• More prominent in XRF spectra that have high concentrations of an element and for lower Z
elements
• Can be reduced by keeping count rates low
 ARTIFACT PEAKS DUE TO BLANK MEDIA
20

18 cellulose blank
16

14

12
Intensity

10
Artifact Peaks
(cps)

8 (Fe, Cu, Zn)

0 0 5 10 15 20 25 30 35 40

Energy (keV)

• May observe peaks due to contaminants in XRF cups, Mylar film, and matrix
• In this case, the cellulose matrix is highly pure and the peaks are due to trace elements in
the XRF analyzer window and detector materials
• This can complicate interpretation (false positives)
SUMMARY OF FACTORS THAT COMPLICATE
INTERPRETATION OF XRF SPECTRA
• Elements in the sample may produce 2 or more lines
✓ K, K  L, L  (we use simplified nomenclature and discussed only  and  lines)
✓ L, L, L, L (can also have  and  lines,  and  lines,  lines, etc.)

• Peak overlaps arising from the presence of multiple elements in the sample and
limited detector
 resolution

• Peaks from X-ray source

✓ Bremsstrahlung (more prominent in less dense samples)
✓ Rayleigh peaks from X-ray source target (typically Ag L, L)
✓ Compton peaks from X-ray source target (typically at energies < Ag L , L)
SUMMARY OF FACTORS THAT COMPLICATE
INTERPRETATION OF XRF SPECTRA

• Sum peaks (two X-ray photons arriving at the detector at the same
time)

• Escape peaks (Si in the detector absorbing some of the energy from a
X-ray)

• Other artifact peaks

• Product packaging, XRF cup, Mylar film, (measure what you want to measure)
• Contaminants on XRF window or trace levels of elements in XRF window or detector
materials (analyze blanks to confirm source of these artifacts)
QUALITATIVE ANALYSIS

• What is the GOAL of the analysis and WHAT ELEMENTS do we want

to look for (toxic elements such as As, Cd, Hg, Pb; nutrient elements such
as Ca, Fe)?
• Answer: Define the problem (what to measure, typical concentration
range, required detection limit, accuracy, precision, etc.)

• Are there any potential SPECTRAL OVERLAPS with other elements in

sample?
• Compare line energies of target elements and other elements to identify
any possible interferences
• If we get a “positive” (detection of a toxic element), do we know for
certain that it is IN THE SAMPLE and not in the product packaging or
the background materials used to hold the sample?
• Measure what you want to measure and be sure to do “blanks”

• How do we know that the analyzer software is not giving ERRONEOUS

RESULTS (false positives or false negatives)?
• Answer: Users must evaluate the spectrum to verify the reported
results – positive identification of an element requires observation
of two peaks at energies close to their tabulated values
QUALITATIVE ANALYSIS False positive for Pb in baby food cap
Spectrum Closeup of Pb lines

Fe sum peak
12.80 keV

• User acquired sample spectrum near lid (>10% Fe), which gave Fe sum peak at 6.40 keV * 2
photons = 12.80 keV
• Vendor algorithm incorrectly identified Pb in this sample at over 2000 ppm (detection and
quantitation based on signal at the Pb L line at 12.61 keV, zero intensity of Pb L line at
10.55 keV not considered by algorithm)
• Be wary of analyzer software and be sure to avoid potential false positives such as this by
evaluating the spectrum to confirm the presence of an element
QUALITATIVE ANALYSIS
Spectra for positive, tentative, and negative identifications
6

blank As K line
5 10 ppm As and Hg 10.54 keV
100 ppm As and Hg

Overlapping lines
Intensity

3 As K 10.54 keV
(cps)

Hg L 11.82 keV
2 Hg L line
9.99 keV
1

0
9 10 11 12 1
3
Energy (keV)
• As and Hg clearly present in blue spectrum (see both  and  peaks)
• As and Hg possibly present in purple spectrum ( peaks barely > blank)
• As and Hg not present in black spectrum (no visible peaks)
 CONCLUSIONS ON QUALITATIVE ANALYSIS
• Vendor software in commercial XRF analyzers are usually reliable in identifying which
elements are present in a sample, but are not foolproof and an occasional false positive or
false negative is possible

• FALSE POSITIVES (element detected when not present)

• Due to limitations in the vendor software, which may not take into account line
overlaps, sum peaks, escape peaks.
• Users must confirm positive detection of an element based on the observation of two
peaks centered within ±0.05 keV of the tabulated line energies for that element at the
proper intensity ratio (5:1 for K lines, 1:1 for L lines)

• FALSE NEGATIVES (element not detected when present)

• Due to limitations in the analyzer software, which may not be set up to detect all
possible elements in the periodic table.
• Unlikely occurrence for toxic elements such as As, Hg, Pb, and Se, more common for
rare elements such as U, Th, and Os.
• Users must identify “non-detected” elements through manual interpretation of
Quantitative and semi-quantitative method

• The quantitative method is the most accurate, but

requires calibration standards.

• Semi-quantitative method is less accurate, but does

not require standards.
Quantitative analysis - calibration

• For a single element (a), the concentration C is a function of the

intensity I :
• Ca = f (Ia)

• For multiple elements (a & b) in a sample matrix, the

concentration is related to both a & b:

• Ca = f(Ia, Ib)
Quantitative Analysis
• XRF is a reference method, so
standards are required for
quantitative results.

• Standards are analysed, intensities

obtained, and a calibration plot is
generated (intensities vs.
concentration).

• XRF instruments compare the

spectral intensities of unknown
samples to those of known
standards.
 QUANTITATIVE ANALYSIS: Issues To Consider

• Are the element CONCENTRATIONS within the detection range of XRF (% to ppm
levels)?

• What sort of SAMPLE PREP is required (can samples be analyzed as is or do they need
to be ground up)?

• For SCREENING PRODUCTS, are semi-quantitative results good enough? For

example, if percent levels of a toxic element are found in a supplement, is this sufficient
evidence to detain it or to initiate a regulatory action?

• For ACCURATE QUANTITATIVE ANALYSES, what is the most appropriate

calibration model to use for the samples of interest (Compton Normalization,
Fundamental Parameters, empirical calibration, standard additions)?
Semi-quant (standardless analysis)

Accuracy is limited by:

• particle size

• inhomogeneity
 Semi-quant (standardless
analysis)
• Accuracy of the semi-quantitative method
can be as good as 1% relative;

• typically accuracy is between 5% and 10%

 SLFP
Standardless Fundamental Parameters
• With standardless analysis, all parameters are based upon
theoretical equations, precise modeling of the detector, X-
ray tube, and geometry.

• The algorithm computes both the intensity to

concentration relationship and the absorption affects

• Results are typically within 10 - 20 % of actual values.

 FP (with Standards)
• The fundamental parameters are based on the measured
response of the system for each element. The most
accurate analytical results are obtained using a “type”
standard, a standard with composition similar to the
material under measurement. Measured “scatter ratios”
can be used to estimate the fraction of the sample which
consists of low-Z materials that cannot be quantified by
XRF.

▪ The concentration to intensity relationship is

determined with standards, while the FP handles the
absorption affects.

• Results are usually within 5 - 10 % of actual values

 Standards
▪ Standards (such as certified reference materials) are
required for Quantitative Analysis.
▪ Standard concentrations should be known to a better
degree of precision and accuracy than is required for the
analysis.
▪ Standards should be of the same matrix as samples to be
analyzed.
▪ Number of standards required for a purely empirical
method, N=(E+1)2, N=# of standards, E=# of Elements.
▪ Standards should vary independently in concentration
when empirical absorption corrections are used.
 TYPES OF CALIBRATION MODELS
VISUAL OBSERVATION (rough approximation, depends on many variables)
• Peak intensity >100 cps corresponds to concentrations >10,000 ppm (% levels)
• Peak intensity of 10-100 cps corresponds to concentrations of ~100-1000ppm
• Peak intensity of 1-10 cps corresponds to concentrations ~10-100 ppm
• Peak intensity < 1 cps corresponds to concentrations ~1-10 ppm

COMPTON NORMALIZATION (CN)

• Uses “factory” calibration based on pure elements (i.e., Fe, As2O3) and ratioing the
intensity of the peak for the element of interest to the source backscatter peak to
account for differences in sample matrices, orientation, etc.
• Best for samples that are relatively low density and samples containing relatively
low concentrations of elements (i.e., soil)
 Fundamental Parameters (FP)
• XRF analysis with Fundamental Parameters (FP) converts elemental
peak intensities to elemental concentrations or film thicknesses. It
processes the raw X-ray spectra measured using Amptek’s detectors
and signal processors to obtain (1) the elemental peak intensities (i.e.
the intensity of the peaks corresponding to each element) and then (2)
the elemental concentrations or film thicknesses.
• Best for samples containing elements that can be detected by XRF (i.e.,
alloys, well characterized samples, and samples containing relatively
high concent. of elements)
•
 TYPES OF CALIBRATION MODELS
EMPIRICAL CALIBRATION
• Involves preparation of standards of the element of interest in a matrixthat
closely approximates that of the samples
• Provides more accurate results than factory calibration and Compton
Normalization
• Note : XRF analyzer can be configured and used with this type of calibration
to give more accurate results for the elements and matrices of interest
• Usually using a high purity metal salt containing the element of interest, an
appropriate matrix, homogenization via mixing or grinding

STANDARD ADDITIONS
• Involves adding known amounts of element of interest into the sample
• Provides most accurate results as the standards are prepared in thesample
matrix as the sample
• Usually reserved for laboratory analyses by trained analysts, and even then
used only as needed as this is labor intensive and time consuming
 EFFECT OF CONCENTRATION
Spectra of As standards in cellulose
80

1000 ppm
70 100 ppm
10 ppm
blank
60

Intensity (cps) 50

40

30

As K line
20 11.7 keV
As K line
10.5 keV
10

0
9 10 11 12 13
Energy (keV)

• Intensity is proportional to concentration

• Detection limits depend on element, matrix, measurement time, etc.
• Typical detection limits are as low as 1 part per million (ppm)
 Linearity falls off at high
1000 concentrations
Se in yogurt

800

Intensity (cps) 600

400

200

0
0 2000 4000 6000 8000 10000 12000
Concentration (ppm)

• Response becomes nonlinear between 1000-10,000 ppm

• Use of Compton Normalization will partially correct for this
COMPTON NORMALIZED INTENSITY VS CONC.
Linearity improves through use of “internal standard”
50000
Se in yogurt

40000

)
m
p p
3
CN response ( 0000
y = 4.1359x - 847.3
R2 = 0.9973

y = 6E-05x 2 + 3.4574x - 356.83

20000 R2 = 0.9991

10000

0
0 2000 4000 6000 8000 10000 12000
Concentration (ppm)

• Use of Compton Normalization (X-ray tube source backscatter from sample)

partially corrects for self absorption and varying sample density
 QUANTITATIVE ANALYSIS AT HIGH CONC’S
Cr standards in stainless steel for medical instrument analysis
14

FP mode with -2% error

12 empirical calibration
Instrument reading (%Cr) y = 0.9905x - 0.1712
10
-3% error R2 = 0.9996

6
-7% error
4

-11% error
2
-5% error
0
0 2 4 6 8 10 12 14
True %Cr
• Although Fundamental Parameters based quantitation gives fairly accurate
results, it also gives determinate error (consistently negative errors)
• Determination of Cr in surgical grade stainless steel samples using an XRF
analyzer calibrated with these standards gave results that were statistically
equivalent to flame atomic absorption spectrophotometry
• For determining % levels of an element, use Fundamental Parameters mode
 QUANTITATIVE ANALYSIS AT LOW CONC’S
As, Hg, Pb, and Se standards in cellulose for supplement analysis
1800
Hg
y = 1.6371x - 19.023

1600
As
Hg CN mode with R2 = 0.9993

Pb
Se
empirical calibration Se
y = 1.3598x - 5.3975
1400 R2 = 0.9998

As
y = 1.2494x - 1.5008

Instrument reading (ppm)

1200 R2 = 0.9991

Pb
1000 y = 1.091x - 3.0741

9% error R2 = 0.9999

800

600

8% error
400

200
4% error
0
0 200 400 600 800 1000 1200
True concentration (ppm)

• Although Compton Normalization based quantitation gives fairly accurate results,

it can also give significant determinate error (slopes > 1)
• Determination of Pb in supplements using an XRF analyzer calibrated with these
standards gave results that were statistically equivalent to ICP-MS
• For determining ppm levels of an element, use Compton Norm. mode
 STANDARD ADDITIONS METHOD
Determination of As in grapeseed sample
0.025

Normalized Intensity (As/Compton)

0.020

y = 0.0003x + 0.0106
R2 = 0.9928
0.015

0.010

0.005 35 ppm via ICP-MS

42 ppm via XRF (21% RSD from 3 reps )
20% difference
0.000
-50 -40 -30 -20 -10 0 10 20 30 40 50
ppm As

• Typically gives more reliable quantitative results as this method involves matrix
matching (the sample is “converted” into standards by adding known amounts of the
element of interest)
• This process is more time consuming (requires analysis of sample “as is” plus two or
more samples to which known amounts of the element of interest have been added)
 EFFECT OF MEASUREMENT TIME
Longer analysis times give better precision and lower LODs
30

Results from analysis of 100 ppm Pb

y = 12.855x 0.504
R2 = 0.9995
25

20

Long measurement times

give ↑S/N and ↓LODs but provide
S/N 15 diminishing returns in precision
(%RSD can be misleading as
precision unrelated to accuracy)
10

Short measurement times -

poor statistics/precision
0
0 1 2 3 4 5

Measurement time (min)

• S/N = mean signal / standard deviation of instrument response (noise)

• As per theory, S/N is proportional to square root of measurement time
• 1-2 min measurement gives a good compromise between speed and precision
• Longer measurement times give better S/N and lower LODs
 CONCLUSIONS ON QUANTITATIVE ANALYSIS

For field applications, the sample is often analyzed “as is” and some
accuracy is sacrificed in the interest of shorter analysis times and higher
sample throughput, as the more important issue here is sample triage
(identifying potential samples of interest for more detailed lab analysis)

– Use FP mode to analyze samples that contain % levels of elements

– Use CN mode to analyze samples that contain ppm levels of elements
and have varying densities

For lab applications, more accurate quantitative results are obtained by

an empirical calibration process

Grind/homogenize product to ensure a representative sample

Calibrate the analyzer using standards and/or SRMs
Use a calibration curve to compute concentrations in samples
When suitable standards are not available or cannot be readily
prepared, consider using the method of standard additions
 OUTLINE
1. INTRODUCTION
The electromagnetic spectrum and X-rays
Basic theory of XRF and simple XRF spectra
Different types of XRF instruments

2. INTERPRETATION OF XRF SPECTRA

XRF spectra of different elements
Limited resolution and overlapping peaks
Artifact peaks

3. QUALITATIVE AND QUANTITATIVE ANALYSIS

Confirmation of detection of an element
Different calibration models
Example calibration curves

4. APPLICATIONS OF XRF
Screening for toxic elements in large numbers of samples
Accurate quantitative analysis of target elements in various matrices

5. CONCLUSIONS
XRF advantages and limitations
References and additional reading
 FOUR KEY ADVANTAGES OF XRF
FOR MANY APPLICATIONS
SIMPLICITY
• Relatively simple theory, instrument, and spectra (versus IR, MS, NMR)

MINIMAL SAMPLE PREP

• For many screening applications, samples can often be analyzed “as is” with
minimal sample processing
• For accurate quantitative analysis, samples must be ground up and
homogenized (faster and easier than acid digestion required for conventional
atomic spectrometry methods)

TYPICAL ANALYSIS TIMES ON THE ORDER OF 1 MINUTE

• For determining % levels of an element (which typically gives high count rates),
measurement times can be as short as a few seconds
• For ppm-level detection limits, measurement times on the order of 1-10 minutes
are needed

PORTABILITY
• Instrument can be brought to the samples
 ANALYTICAL PROCESS STREAM
More intelligent
• Use XRF for “sample triage” (sort into analysis protocol
“detects” and “non-detects”) Screen
product via
XRF

• Avoid wasting time trying to quantify

X
non-detectable levels of a toxic element detected? NO
Product
OK
with more time consuming methods such Typical
analysis protocol YES
as ICP-MS
Acquire Acquire
samples sample

• Avoid problems trying to quantify %

levels of a toxic element with a very
Homogenize Homogenize
sensitive technique such as ICP-MS samples sample
(contaminating digestion vessels,
glassware, instrument, etc. in low-level Digest &
Digest & [X] >
process stream) filter 10 ppm? NO filter
samples sample
YES

• Perform accurate quantitative Analyze via Analyze via Analyze via

analysis (via XRF or ICP-MS) where ICP-MS XRF ICP-MS

warranted
 TYPICAL APPLICATIONS OF XRF

XRF is currently used in many different disciplines:

Geology
• Major, precious, trace element analysis
• Characterization of rocks, ores, and soils

Environmental Remediation
• Pb in paint
• Heavy metals in soil (EPA method 6200)

Recycling
• Alloy identification
• Waste processing

Miscellaneous
• Art and archeology
• Industrial hygiene
• Forensics
 Pb and other elements are
still causing problems
Pb and U
detected in ceramic material
imported from Mexico

Pb, Co, and other elements

detected in individual pigments
in plate imported from China

• Ceramic plates may contain toxic elements that can leach into food
• XRF can be used to quickly identify elements and their concentrations in
tableware, glazes, and base ceramic material, and food
 Handheld XRF analysis of
Kervorkian-designed biopsy
forceps

• Atomic absorption method gave 12.7% Cr

(difficult prep and digestion, >1-day effort)
• XRF analysis gave 12.8% Cr and correctly identified alloy (no sample prep, FP
mode, empirical calibration with Cr standards, <1 min reading)
• Results used to confirm labeling requirements for Cr content in surgical products
used in medical applications
CHINESE HERBAL MEDICINE - Niuhuang Jiedu Pian

• Product manufactured in China (Cow yellow detoxification tablet),

Intended to treat mouth ulcers, relieve tooth aches, reduce fever, and “release
toxins”, product import document indicated that As in the form of realgar (As4S4)

• ICP-MS showed 6.85% As (note low value here versus XRF may be due to
inability of acid digestion procedures to dissolve realgar)

• Handheld XRF showed 11.7% As in product (Compton Normalization mode,

empirical calibration with As standards, diluted sample into range of standards)

• Recommended max dose of 9 tablets per day is equivalent to consumption of

0.173 g of As (minimum lethal dose ~0.130 g*) *
 IMPORTED AND DOMESTIC SUPPLEMENTS

• Dolan, Capar, et al (FDA/CFSAN) reported on determination of As, Hg, and Pb in

dietary supplements via microwave digestion followed by high resolution ICP-
MS
• A subset of these samples (28) were the focus of a study to compare and evaluate
several different XRF analysis methods

• This represents a very challenging application for XRF due to

➢ Low levels of toxic elements in these samples (highest was 50 ppm)
➢ Tremendous variability of sample matrices and preparation of appropriate
standards for an empirical calibration (cellulose was used to approximate
the predominantly organic content of the samples)
➢ As and Pb spectral overlaps and co-occurrence of both in some samples

• Our goal was to evaluate XRF in two different modes of operation

➢ Screening products “as is” using an empirically calibrated handheld XRF
(results not included in this presentation)
➢ Accurate quantitative analysis of homogenized products using an
empirically calibrated lab-based XRF (completely automated data
acquisition, calibration, quantitative analysis, and report generation)
 XRF VS ICP-MS FOR
50
TOXIC ELEMENTS IN SUPPLEMENTS
40
ppm Pb via XRF

30

y = 0.8176x + 0.0926
20
R2 = 0.9964

10

0
0 5 10 15 20 25 30 35 40 45 50
ppm Pb via ICPMS

• t test indicates no significant differences at the 95% confidence level between lab-
grade XRF and conventional ICP-MS method
• Such data demonstrate that XRF can give accurate quantitative results
(impressive considering most samples contain these elements at concentration
that are very close to the detection limit)
 OUTLINE
1. INTRODUCTION
The electromagnetic spectrum and X-rays
Basic theory of XRF and simple XRF spectra
Different types of XRF instruments

2. INTERPRETATION OF XRF SPECTRA

XRF spectra of different elements
Limited resolution and overlapping peaks
Artifact peaks

3. QUALITATIVE AND QUANTITATIVE ANALYSIS

Confirmation of detection of an element
Different calibration models
Example calibration curves

4. APPLICATIONS OF XRF
Screening for toxic elements in large numbers of samples
Accurate quantitative analysis of target elements in various matrices

5. CONCLUSIONS
XRF advantages and limitations
References and additional reading
 ADVANTAGES OF XRF

Selectivity: True multi-element analysis (from S to U, ~80 different elements)

Measures total element concentration (independent of chemical form)

LODs: 1 to 10 ppm at best (depends on source, element, matrix, etc.)

Linearity: Linear response over 3 orders of magnitude (1-1000 ppm)

Accuracy: Relative errors ~ 50% with factory calibrated instrument

Relative errors < 10% using authentic standards for calibration

Precision: RSDs < 5% (must have homogeneous sample)

Speed: Minimal sample prep (analyze “as is” or homogenize and transfer to cup)
Fast analysis times (typically seconds to minutes)

Cost: $25,000-$50,000 for field portable instrument

Far less expensive per sample than FAAS, GFAAS, ICP-AES, and ICP-MS

Miscellaneous: Simple (can be used by non-experts in the field)

Nondestructive (sample can be preserved for follow up analysis)
Field-portable instruments can operate under battery power for several hours
 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
 Multiply wt% ELEMENT by numerical value
• Ag2O 1.0741 • below for equivalent
CuO 1.2518 • MnO 1.2912 • RhO 1.5555 • Tm2O3 1.1421
• Dy2O3 1.1477 • MnO2 1.5825 • RuO 1.1583

expressed as OXIDE
• Al2O3 1.8895 • UO2 1.1344
• As2O3 1.3203 • Er2O3 1.1435 • MoO3 1.5003 • SO3 2.4972 • UO3 1.2017
• As2O5 1.5339 • Eu2O3 1.1579 • N2O5 3.8551 • Sb2O5 1.3284 • U3O8 1.1792
• Au2O 1.0406 • FeO 1.2865 • Na2O 1.3480 • Sc2O3 1.5338 • V2O5 1.7852
• B2O3 3.2202 • Fe2O3 1.4297 • Nb2O5 1.4305 • SeO3 1.6079 • WO3 1.2610
• BaO 1.1165 • Ga2O3 1.3442 • Nd2O3 1.1664 • SiO2 2.1392 • Y2O3 1.2699
• BeO 2.7758 • Gd2O3 1.1526 • NiO 1.2725 • Sm2O3 1.1596 • Yb2O3 1.1387
• Bi2O5 1.1914 • GeO2 1.4408 • OsO 1.0841 • SnO2 1.2696 • ZnO 1.2448
• CO2 3.6644 • HfO2 1.1793 • P2O5 2.2916 • SrO 1.1826 • ZrO2 1.3508
• CaO 1.3992 • HgO 1.0798 • PbO 1.0772 • Ta2O5 1.2211

• CdO 1.1423 • Ho2O3 1.1455 • PbO2 1.1544 • Tb2O3 1.1510

• Ce2O3 1.1713 • In2O3 1.2091 • PdO 1.1504 • Tb4O7 1.1762

• CeO2 1.2284 • IrO 1.0832 • Pr2O3 1.1703 • TeO3 1.3762

• CoO 1.2715 • K2O 1.2046 • Pr6O11 1.2082 • ThO2 1.1379

• Cr2O3 1.4615 • Li2O 2.1527 • PtO 1.0820 • TiO2 1.6681

• Cs2O 1.0602 • Lu2O3 1.1371 • Rb2O 1.0936 • Tl2O3 1.1174

• MgO 1.6582 • ReO 1.0859 • Tm2O3 1.1421
Types of XRF
• Energy Dispersive X-ray Fluorescence (EDXRF)

• Wavelength Dispersive X-ray Fluorescence (WDXRF

 WD-XRF

1.Single crystal of fixed 2θ acts as a spectrum analyzer.

2.Scanning 2θ range allows the complete spectrum to be
acquired.
3.Selection of single wavelength is achieved by selection of
equivalent 2θ value.
Wavelength Dispersive XRF (WD-XRF)

 The generated X-ray spectrum consists of a number of spectral

lines, which must be separated and identified by wavelength
or energy.

 Wavelength dispersive system uses a diffraction crystal to focus

specific wavelengths onto a detector.
 WD-XRF

Schematic illustration of the major components

of an X-ray fluorescence analyzer
WD-XRF

Figure 6: Schematic arrangement of wavelength

dispersive spectrometer
WD-XRF

• A wavelength range is scanned by changing the

angle in which the X- rays strike the crystal.

• The polychromatic secondary X-rays originating from

the sample are diffracted by an analyzing crystal in all
directions.
 WD-XRF

• Therefore the X-rays are diffracted by a diffraction

crystal with known spacing d under a specified angle
and counted by an X-ray detector.
 WD-XRF
• Diffracting crystal and detector is placed in positions complying
with Bragg's Law.

where d is the spacing of atomic

layers parallel to the crystal surface
WD-XRF
• The wavelength dispersive spectrometer may be a
single channel instrument in which a single crystal
and a single detector are used for the sequential
measurement of a series of wavelengths.

• In a multi-channel spectrometer, many crystal /

detector sets are used to measure many elements
simultaneously.
Figure : Schematic of the WDXRF instrument
WD-XRF

• By selecting the relevant Bragg angle, each individual

wavelength (spectral line of an element) is measured
by the detection system.
 WD-XRF

• The wavelength is specific to the elements responsible for

their production.

• Since the wavelength, λ of the emitted fluorescence is

characteristic of the element being excited, measurement
of this wavelength enables us to identify the element.
• For qualitative studies, the angle of diffraction
θ is measured.
• From this measurement, the wavelength λ of
fluorescence can be calculated by using the Bragg
equation
nλ = 2d sin θ
• Knowing λ of the fluorescence, we can identify
the element from a chart of the known elements.
 WD-XRF

• The intensity of the fluorescence depends on how

much of that element is in the X-ray beam.

• Hence, measurement of the fluorescence

intensity makes possible the quantitative
determination of an element.
Energy-Dispersive XRF (ED-XRF)

• When a sample is exposed to X-rays in an ED-XRF system, atoms in the

sample emit secondary (fluorescent) X-rays with characteristic
energies.
• These X-rays correspond to the elements present in the sample. The
detector’s job is to capture these emitted X-rays and measure their
energy.
• Different elements emit X-rays at specific energy levels (characteristic
peaks). The detector must accurately resolve these energy levels to
identify which elements are present in the sample. For instance, X-rays
emitted from iron will have a different energy than those from copper or
lead. The detector must distinguish these small differences to
accurately identify elements.
• ED-XRF systems use energy-dispersive detectors, which means
they separate the X-rays based on their energy.

• High energy resolution is critical because it allows the detector to

differentiate between X-rays that have very similar energies,
avoiding peak overlap.
• If the detector has poor resolution, the energy peaks may blend
together, making it difficult to identify elements accurately.
Quantitative Analysis
• After identifying the elements, the detector also quantifies them.

• It does this by counting how many X-rays of a particular energy

(associated with a specific element) are detected.

• The number of X-rays counted is proportional to the concentration

of the element in the sample.

• High precision and sensitivity of the detector are essential for

accurate quantification
Detector Electronics
• The electronics of the detector process the signals generated
when X-rays are absorbed by the detector material.

• The electronics are crucial in converting the absorbed X-ray

energy into a measurable signal and interpreting it correctly.

• Well-designed electronics ensure minimal noise, reducing errors

and improving the precision of the analysis.
• Energy dispersive X-ray spectroscopy (EDS, EDX or EDXRF)
is an analytical technique used for the elemental analysis or
chemical characterization of a sample.

• As a type of spectroscopy, it relies on the investigation

of a sample through interactions between
electromagnetic radiation and matter.
ED-XRF
• The number and energy of the X-rays emitted from a specimen
can be measured by an energy dispersive spectrometer.

• As the energy of the X-rays are characteristic of the difference in

energy between the two shells, and of the atomic structure of the
element from which they were emitted, this allows the elemental
composition of the specimen to be measured.
ED-XRF
 An energy dispersive (ED) system focuses all the emitted X-rays
onto an energy analyzing detector.

 It is faster and less expensive.

 wavelength dispersive spectrometers are more sensitive and have

higher resolution.
 ED-XRF
There are four primary components of the EDS setup: the beam
source; the X-ray detector; the pulse processor; and the analyzer.

Schematic arrangement of EDX spectrometer

 ED-XRF
• An energy dispersive X-ray fluorescence (ED-XRF) makes use of the fact that the
pulse height of the detector signal is proportional to the X-ray photon energy,
which is correlated with the wavelength.

• Therefore the optical path is simpler than for WDXRF spectrometers because no
crystals or goniometers are needed and the fluorescence photons from the
sample hit the detector directly.

• The ED-XRF only consists of two basic units, the excitation source and the
spectrometer / detection system.
 ED-XRF

• The samples are normally irradiated by X-rays from a tube with lower
power than that used with the WD-XRF spectrometers.

• The elements and their concentration are identified by counting the

pulses at the different energy levels.
Fig. 8. Spectrum of the standard sample D846 of composition: 69.1%Fe,
18.35%Cr, 9.11%Ni, 0.53%Mn, 0.19%Cu, 0.43%Mo, 0.60%Nb, 1.19%Si,
0.34%Ti, 0.04%W. Measurement conditions: voltage 30 kV, current 200 μA,
measurement time 600 s, collimator 1000 μm.
 ED-XRF

• Usually a multi-channel analyzer is used for display and

providing the data.

• Here each channel counts the number of photons with a

certain energy level simultaneously.
 ED-XRF

• The resolution of an ED-XRF spectrometer depends strongly

upon the detector used. The resolution improves at higher
energy levels in contrast to the resolution of WD-XRF set-
ups.
Si (Li) Detectors

• These consist essentially of a 3-5 mm thick silicon junction type p-i-n

diode. The Li-drifted centre part forms the non-conducting i-layer.

• When an X-ray photon passes through, it causes a swarm of electron-

hole pairs to form, and this causes a voltage pulse.

• To obtain sufficiently low conductivity, the detector must be maintained at

low temperature, and liquid-nitrogen must be used for the best
resolution.
Figure 5: Schematic form of a Si(Li) detector
ED-XRF

• EDX spectrometers compare favorably with WDX spectrometers in

that they can be smaller, simpler in design and have fewer
engineered parts.

• They can also use miniature X-ray tubes or gamma sources. This
makes them cheaper and allows miniaturization and portability.
 ED-XRF
• This type of instrument is commonly used for portable quality control
screening applications, such as testing toys for Lead (Pb) content, sorting
scrap metals, and measuring the lead content of residential paint.

• On the other hand, the low resolution and problems with low count rate
and long dead- time makes them inferior for high-precision and high-speed
analysis.
 Feature WD-XRF ED-XRF

Uses a crystal to disperse X-rays by wavelength, Uses a semiconductor detector to measure X-ray
Principle
allowing for high-resolution detection. energies directly.

Generally provides better energy resolution due to Lower energy resolution compared to WD-XRF,
Resolution
wavelength dispersion. but faster analysis.

Quantitative Highly accurate quantitative analysis; well-suited Good quantitative capabilities, but less precise
Analysis for trace element detection. than WD-XRF for trace elements.

Element Effective for heavier elements (higher atomic Suitable for a broader range of elements,
Range number); less effective for lighter elements. including lighter elements.

Typically requires solid samples; can analyze Can analyze solids, liquids, and powders;
Sample Type
powders, thin films, and some liquids. versatile sample types.

Speed of Slower due to the complexity of the wavelength Faster analysis time; ideal for routine testing and
Analysis selection process. high-throughput applications.

Cost and More complex and generally more expensive due to Simpler and typically less expensive; easier to
Complexity the required optics and components. maintain.
Used in applications requiring high precision, such Commonly used in industries for quality control,
Applications as mineralogy, metallurgy, and environmental environmental monitoring, and material
analysis. characterization.
 Energy-Dispersive XRF

(ED-XRF)

Energy dispersive X-ray fluorescence (ED-XRF) relies on the detector and

detector electronics to resolve spectral peaks due to different energy X-
rays.
 ED-XRF
b) Energy Dispersive

1. Proportional Si(Li) detector gives a distribution of voltage pulses proportional to the

spectrum of X-ray photons.
2. A multi-channel analyzer is used to isolate the voltage pulses into discrete intervals.
Consecutive output of the multi-channel analyzer (MCA) intervals allows complete spectrum
to be displayed.
3. Selection of a single energy interval is obtained by selection of appropriate voltage window.
(i.e., range of the channels) on the MCA.
 Amplifiers
• The pulses generated by the detector are processed by pulse-
shaping amplifiers.
• It takes time for the amplifier to shape the pulse for optimum
resolution, and therefore a trade-off between resolution and count-rate:
long processing time for good resolution results in "pulse pile-up" in
which the pulses from successive photons overlap.
• So, pile-up correction should be built into the software in applications
that require trace analysis.
Sample Preparation
• Form: Solid, liquid, or powder
• Ensure uniformity for accurate results
• Require optimal sample thickness for effective excitation
General Sample Preparation Steps
• Ensure that the sample is uniform in composition. This is
especially important for solid samples and powders
(homogeneity)
• Techniques include grinding, mixing, or using a blender to achieve
a homogeneous material.
• For powders, reducing particle size can improve X-ray penetration
and excitation.
• Typically, a particle size of less than 100 micrometers is ideal for
most XRF applications.
Sample preparation : XRF testing
• Pelletization (for powders)
• Powders may be pressed into pellets to create a flat, uniform surface.This
helps in obtaining consistent results and reduces the effects of surface
irregularities.
• Binding Agents may be needed for pelletizing, binding agents (like wax or
cellulose) can be added to improve cohesion. The choice of binding agent
should not interfere with the XRF analysis
• Film Preparation (For liquid samples)
• Liquid samples can be analyzed by placing them in thin, transparent films
(like Mylar or Kapton) that do not interfere with XRF measurements.
Ensures that the sample is held securely while allowing X-rays to
penetrate.
Specific Sample Preparation Techniques
• Fusion:
• For some samples, especially minerals, fusion involves mixing the sample with a
flux (often lithium borate) and heating it until molten. The molten sample is then
cooled to form a glass disk, providing a homogenous, smooth surface for
analysis.
• Coating:
• Some samples may require a conductive coating to reduce charging effects,
especially in non-conductive materials. Common coatings include carbon or
gold.
• Thin Films:
• For certain applications, creating thin films from samples (using techniques like
spin coating) can provide better results. Thin films should be uniform and have a
known thickness for accurate analysis.
Figure: Elements that can be determined by WDXRF.
Data Analysis
• Spectrum Interpretation: Peaks corresponding to specific
elements
• Quantitative analysis using calibration curves
• Calibration: Use of standards to convert peak areas to
concentrations.
XRF
SPECTRUM
Applications of XRF
• Material Science: Composition analysis of metals, alloys, and
ceramics.
• Environmental Studies: Soil and water contamination analysis.
• Cultural Heritage: Analysis of art and archaeological artifacts.
• Industrial Applications: Quality control in manufacturing
processes
Advantages and Limitations
• Advantages: Non-destructive analysis, minimal sample
preparation, quick results.

• Limitations: Limited to elements with atomic number > 11

(sodium), Detection limits vary by element and matrix
Interferences from overlapping peaks.
 Important Questions to enhance your understanding!!

1. Explain theory of XRF by using Bohr atomic model.

2. The wavelength of this fluorescent radiation can be calculated from

Planck's Law. Give the equation.

3. Sketch and explain in detail the XRF examination technique to

determine the chemical composition in materials.

4. Distinguish in between wdxrf and edxrf in XRF examination technique

5. Discuss the advantages each of wdxrf and edxrf techniques in material

characterization.