Review of TXRF Applications for Trace Elemental Analysis

Mike Beauchaine
TXRF Product Manager, Bruker AXS Inc.
Madison, Wisconsin

Principles X-ray fluorescence (XRF)

spectroscopy

1. An X-ray quantum hits an inner

shell electron in a (sample)
atom. The electron is removed
leaving the atom in an excited
state
2. The missing inner shell electron
is replaced by an electron from
an outer shell
3. The energy difference between
the inner and outer shell is
balanced by the emission of a
photon (X-ray fluorescence
radiation)

Principles X-ray fluorescence (XRF)

spectroscopy

The energy, and therefore the wavelength, of the X-ray

fluorescence radiation is characteristic for the different
chemical elements.
QUALITATIVE ANALYSIS

The intensity of the X-ray fluorescence radiation is, in first

approximation, proportional to the element concentration.
QUANTITATIVE ANALYSIS

Low Z

High Z

Principles of X-ray fluorescence (XRF)

spectroscopy

Each element shows a specific line

pattern in a spectrum depending on
the orbitals involved

L
K transition

= K line

M
K transition

= K line

M
L transition

= L line

N
L transition

= L line

Principles of ED X-ray fluorescence (EDXRF) spectroscopy

Principles of ED X-ray fluorescence (EDXRF) spectroscopy

Principles of WD X-ray fluorescence (WDXRF) spectroscopy

Principles of WD X-ray fluorescence (WDXRF) spectroscopy

Principles of total reflection X-ray

fluorescence spectroscopy

Quantification in common X-ray fluorescence spectroscopy

absorption of primary beam

and fluorescence radiation

Ii = f (ci, cj)

secondary fluorescence
enhancement

and

ci = f (Ii, cj)

Principles of total reflection X-ray

fluorescence (TXRF) spectroscopy
Total reflection X-ray fluorescence spectroscopy

detector
monochromator
o
o
Beam angle: 0 / 90

sample disc
X-ray tube

Samples must be prepared on a reflective media

Polished quartz glass or polyacrylic glass disc
Dried to a thin layer, or as a thin film or microparticle

Principles of total reflection X-ray

Quantification

C IS N i S IS
Ci =
N IS S i
Ci: Element concentration
CIS: Internal standard concentration
Ni: Element net countrate
NIS: Internal standard net countrate
Si: Element sensitivity factor
SIS: Internal standard sensitivity factor

Principles of total reflection X-ray

fluorescence spectroscopy
In TXRF the samples are prepared
as thin films or layers
 Matrix effects are negligible
 Quantification is possible

Principles of total reflection X-ray

fluorescence spectroscopy
In TXRF the samples are prepared
as thin films or layers
 Matrix effects are negligible
 Quantification is possible

TXRF detects elements from Na(11)

to U(92)
The element sensitivities depend on
the atomic number

Element sensitivity

K-lines

L-lines

The sensitivity factors are calibrated

ex works
Quantification requires the addition
of one standard element
Atomic number

Principles of total reflection X-ray

fluorescence spectroscopy
Samples for TXRF
Powders: Direct preparation
or as suspension
Liquids:

Direct preparation

Always as a thin film, micro fragment or

suspension of a powder
Necessary sample amount:
Low g respectively l range

Simple quantification
 Matrix effects are negligible
due to thin layer
 Quantification is possible by internal
standardization

Elements measured by the Mo PICOFOX

Elements measured by the W PICOFOX

TXRF Spectrum
Multi-element standard

Typical TXRF Results

Multi-element standard

Element
Ca
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
As
Se
Sr

Conc./(mg/l)
0.991
0.997
0.986
0.994
1.015
0.996
1.006
1.005
1
0.989
1.019
1.1
0.987

LLD/(mg/l)
0.003
0.003
0.002
0.002
0.002
0.001
0.001
0.001
0.001
0.001
0
0
0

The instrument - S2 PICOFOX

Benchtop TXRF Spectrometer

S2 Picofox

Metal ceramic X-ray tube

Mo or W anode

Air cooled

Multilayer Monochromator

Xflash silicon drift detector

Electro-thermally cooled

149 eV @ MnK 100 kcps

Automatic Version

25 sample cassette changer

Review of TXRF Applications

Current research areas

Environmental /
Ecology

Nanoparticles

Clinical Research /
Biology

Forensics

Semiconductor

Food/Beverage

Pharmaceutical/
Nutraceutical

University
Research

Sample preparation
Liquid and digested samples
Youll need just a few steps for the preparation of liquid samples

fill sample in micro tube

add internal standard

homogenize
Note: high matrix samples
may require a dilution step

pipette on carrier

Sample preparation
Final steps

dry by heat / vacuum

load the instrument

start data aquisition

Liquid Samples
Trace Element Analysis in Serum & Blood
Measurements and sample preparation
Blood Serum

Whole Blood

Dilution, Ultrapure water

Digestion, 10%
tetramethylammonium
hydroxide @ 1 hr

Dilute in 2% HCl
solution

Int. Standard, Ga

TXRF

Liquid Samples
Trace Element Analysis in Serum & Blood

Comparison of TXRF to ICP-MS reference values for trace elements in

whole blood
Good concordance of TXRF with reference values for essential elements
Other elements (P, S, Cl, K, Ca, Br, Rb, Sr) could also be determined
during One measurement
Samples analyzed at 600s

Liquid Samples
Trace Element Analysis in Serum & Blood

Comparison of TXRF and AAS reference values in blood serum

TXRF has better standard deviations compared to AAS

No Digestion procedure was applied
Samples analyzed at 600s

Application studies
Sample preparation for solids

Sample preparation of
plants, tissues, grains

Solid materials are ground to fine particle size

and resuspended for direct analysis without
digestion

fill powder in mortar

grind carefully

weigh about 20-50 mg

transfer to tube

Application studies
Sample preparation for solids

suspend in detergent solution

add standard

homogenize

pipette on carrier

Application studies
Sample preparation for solids

dry by heat / vacuum

load the instrument

start data aquisition

Application Studies
Wheat Flour
Source
Announcement of the
Federal Reserve Bank Of
Minneapolis

Sales price for Se-poor wheat: < 3 US$/bushel

Sales price for Se-rich wheat: < 10 15 US$/bushel

Application studies
Wheat Flour

Demand for on-site analysis

of Se in wheat

Requirements

Fast and easy sample

preparation

Rugged equipment with

no need for external
media

High sensitivity/accuracy

Application studies
Wheat Flour

10000

Results

element
concentrations

1000

Reference Values (mg/kg)

P
Cl
Ca
100

Fe

Zn
Mn

10

Se

Cu
Ba

Br
Rb

Ni
0
0

10

100

TXRF Values (mg/kg)

1000

10000

Application studies
Wheat Flour

Results

10000

element
concentrations

TXRF-value:
Reference:
3 LLD:

S
1000

Reference Values (mg/kg)

Cl
Ca

100

1.40 0.03 mg/kg

1.23 0.90 mg/kg
60 g/kg
10

Fe

Zn
Mn

Se

Cu
Ba

Br
Rb

Ni
0
0

10

100

TXRF Values (mg/kg)

1000

10000

Application studies
Palladium Analysis
Introduction:

Palladium is extensively used in pharmaceutical small molecule drug

processes as a catalyst

It must be removed prior to release of the API

Looking for an easy to use technique with fast sample prep and little to no
consumables that can be implemented on the manufacturing floor

Study:

6 separate pharmaceutical drugs

Standards

Determine linearity, sensitivity, accuracy, and precision for Pd plus Cr, Fe,
Cu, Rh, and Pt

Compare TXRF vs. ICP-MS instrumentation

14.02.2012

Application studies
Palladium Analysis

TXRF Solid Samples Preparation

Diluent Choice

Detector

Sample

5 10 mg
of Sample

14.02.2012

Internal
Standard(s)

Sample Prepared in
Organic Solvent /
Dilute Acid Diluent

Sample Solution
Spotted
and Dried
on Substrate

TXRF
Sample Spot
Analysis

Application studies
Palladium Analysis

Conclusion
o The choice of the X-ray target is very important for Pd
analysis because of the Pd-L line interferes with Ar-K line
o TXRF can accept organic solvent-based diluents
o Instrument is easy enough for a technician to be able to run
samples at or near the plant floor
o Also allows for fast analysis of impurities with small sample
size requirements

Acknowledgments: Bradley Shaw, David Semin, et.al Analytical and Research Development, Amgen Inc.
Thousand Oaks, CA Comparison of Total Reflection X-Ray Fluorescence (TXRF) to Inductively-Coupled
Plasma Spectrometry (ICP-MS): Applicability of TXRF for Open-access

14.02.2012

Sample preparation
Microparticles
Microparticles are measured semi-quantitatively and
non-destructively

dab vacuum grease on carrier

pick-up some particles with a (glass) rod

drop particles on grease

Particles
Characterization of nanoparticles

Analytical question

element ratios in CdSe nanoparticles
coated with ZnS
Analytical issues

extremely small sample amount (R&D)

non-destructive method preferred
TXRF measurement

transfer of nanoparticles to quartz carrier
by cotton bud

standardless quantification
Results

even smallest sample amounts allow the
determination of element ratios in
nanoparticles

Particles
Characterization of nanoparticles

Results

S2 PICOFOX
Standardless
analysis applied

12
Sample 1

10

Sample 2

10
Ratio (wt.-%)

even smallest sample

amounts allow the
determination of
element ratios in
nanoparticles

Element ratios of nanoparticles

Sample 3

8
6
4
4
2

0
Zn/S

Cd/Se

Measured ratios of 3 samples

versus target value ()

Zn/Cd

Application Examples
Conclusion
Accuracies and Sensitivities comparable to AAS or ICP without the need for
complex and time-consuming sample preparation and instrument calibration

Ability to analyze minute

samples
Allows for analysis of toxic
and nutritious elements at
very low levels
Virtually any sample is
possible with limited
sample prep (powders,
nanoparticles, liquids, thin
films, etc.)

Elements Na to U within one

measurement

Detection limits of 1 to 100 ppb

for most elements

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