2478 X-RAY FLUORESCENCE SPECTROSCOPY, APPLICATIONS

X-Ray Fluorescence Spectroscopy, Applications

Christina Streli, P Wobrauschek and
P Kregsamer, Atominstitut of the Austrian
HIGH ENERGY
Universities, Wien, Austria SPECTROSCOPY
Applications
Copyright © 1999 Academic Press

Introduction fluorescence signal depends on the intensity and

energy of exciting photons hitting the sample atoms.
X-ray fluorescence spectrometry (XRF) has been Low-power X-ray tubes operating in the few W
applied during the 1970s to 1990s as a versatile tool range and standard X-ray tubes dissipating up to
to many analytical problems. The analysis of major, 3 kW, as well as X-ray tubes with a rotating anode,
minor and trace elements in various kinds of samples up to 18 kW, are in use. Photons from radioisotopes
can be performed qualitatively as well as quantita- are used for special applications, offering an excita-
tively. The working principle is based on the excita- tion source independent of any power supply. The
tion of the sample atoms by high-energy X-rays, brightest excitation source is synchrotron radiation.
followed by the emission of characteristic photons It is emitted when bunches of electrons or positrons
with a certain energy, well correlated to the atomic with energies in the GeV range are travelling along
number Z of each element (Moseley’s law). The curved sections in a storage ring. An intensive con-
determination of the energy (or wavelength) of the tinuous spectrum with a strong natural collimation
emitted photon allows qualitative analysis and the in the forward direction is emitted. The radiation is
determination of the number of emitted characteris- continuous from the eV region to some hundreds of
tic photons allows quantitative analysis. The funda- keV and linear polarized in the orbital plane.
mental physical principle of X-ray fluorescence is Due to the different working principles of wave-
described in the article about the theory of X-ray flu- length-dispersive (WD) and energy-dispersive (ED)
orescence spectroscopy. One of the features of XRF XRF the applications differ strongly and it is neces-
besides the accurate, rapid, multielement capacity, is sary to work out the special techniques and their
that the analysis can be performed nondestructively. advantages and disadvantages.
In fact, one has to consider that XRF is a surface-
sensitive method, because of the energy of the excit-
ed and emitted radiation which is in the range 1–115
Instrumentation and methodology
keV (Na to U K-radiation). The penetration depth of
the primary radiation is some µm or so for low-Z Wavelength-dispersive spectrometers
elements and some 100 µm or so for heavy elements,
depending also on the matrix or type of sample Two types of WD instruments are in use, the sequen-
(solid, liquid and powder samples are common). In tial spectrometer and the simultaneous spectrometer.
any case the surface of the object of investigation has The sequential spectrometer scans the radiation
to be representative of the entire volume, and thus emitted by the sample by changing the angle sequen-
requires a homogenous sample. Therefore, because tially. For different wavelength regions different ana-
of the sample preparation, the ‘nondestructiveness’ is lyser crystals must be used to fulfil Bragg’s equation.
lost. To perform XRF a spectrometer is required that A set of 6 to 8 crystals with various lattice spacings d
consists of an excitation source, sample and a is properly mounted and can be changed automati-
detection system, which can be either wavelength- cally. The simultaneous spectrometers consist of var-
dispersive or energy-dispersive. ious combinations of analyser crystals and detectors,
The excitation is mostly performed by X-rays pro- arranged around the sample at fixed angle settings.
duced in and emitted by an X-ray tube. The spectral So each ‘channel’ is optimized to detect an individual
distribution of the emitted radiation is partly the wavelength corresponding to an element. Mostly
bremsstrahlung, with a maximum energy corre- these channels use focusing optics at the detector to
sponding to the applied voltage, and is partly super- increase the signal. These spectrometers are called si-
imposed by the characteristic lines of the respective multaneous multielement spectrometers, but the
anode material. The intensity of the emitted radia- number of simultaneously detected elements depends
tion depends on the atomic number of the target and on the number of channels of the spectrometer. LiF,
the applied voltage. The intensity of the measured topaz and other natural crystals are used for the
 X-RAY FLUORESCENCE SPECTROSCOPY, APPLICATIONS 2479

medium-Z elements. The use of synthetic multilayer techniques have been developed to reduce the scat-
structures (consisting of alternating layers of a high- tered radiation.
Z and a low-Z material with a bilayer thickness of
∼ 1–10 nm) as dispersive elements and measurement Use of monochromatic radiation
in an evacuated environment allows the efficient de- The scattering can be drastically reduced, if monoen-
termination of low-energy characteristic radiation ergetic radiation is used for excitation. Then only
down to even Be–K lines (O = 11 nm) if a flow coun- monoenergetic photons are arriving at the sample
ter with an ultrathin entrance window is used. The and can be scattered and so contribute to spectral
big advantage of the WD spectrometers is their ex- background. Various methods of producing mo-
cellent wavelength-to-energy resolution, especially in noenergetic radiation are in use.
the low-energy region and the high count-rate range
(106 cps) in operation. Filtered radiation The easiest way to reduce the
number of photons not used for sample excitation is
the insertion of a filter. It mainly absorbs the low-
Energy-dispersive spectrometers
energy bremsstrahlung, but also a filter with Z as
An ED detector consists of a semiconductor crystal Zanode−1 can be used to effectively reduce the charac-
(Si, Ge) prepared as p-i-n diode, mounted under vac- teristic Kβ radiation from the anode.
uum, generally operated at 77 K and cooled with
liquid nitrogen (LN) and the necessary connected Secondary target excitation The radiation from an
X-ray tube is used to excite a suitable target and the
electronics. Therefore a large, heavy dewar (7–30 L
of LN) is required for an ED detector. LN consump- fluorescence radiation from the secondary target is
tion is ~1 L a day. The crystal environment has to be used to excite the sample. This method of achieving
quasi-monochromatic radiation suffers from a tre-
a vacuum, and as an entrance window in front of the
crystal generally Be is used. Be is chosen as it is avail- mendous loss of photon flux, but this can be com-
pensated for by using higher current from high-
able with 8–25 µm thickness, vacuum and light-tight
and its absorption of low-energy photons is tolera- power tubes.
ble. If very low energy photons (E < 1 keV) are to be Radioisotope excitation (RIXRF) A few radioiso-
measured, an ultrathin (< 1 µm) entrance window is tope sources (with acceptable half-life) emit radia-
required. Generally, the energy resolution is much tion in the X-ray region, such as Am-241 (59.5 keV),
larger with ED detectors than with WD systems, so Cd-109 (Ag–K lines, 22 and 25 keV) and Fe-55 (Mn
ED is more susceptible to line overlaps. Especially in lines, 5.9 keV), and can be used for excitation. The
the low-energy regions this leads to difficulties in the advantage of radioisotope sources is their independ-
interpretation of the measured spectrum and mathe- ence of a generator and power supply, which makes
matical procedures for spectrum deconvolution are their use interesting for portable instruments, in
required. To overcome the problem of LN cooling, field, on-line and even extraterrestrial applications.
new Peltier cooled detectors are available offering The disadvantage is the low photon flux in compari-
smaller size and lighter weight, but worse resolution. son to tube excitation.
As common practice the value for the energy resolu-
tion is given at 5.9 keV and is in the range 130– Crystal monochromators and multilayer struct-
180 eV for LN-cooled detectors, and 175–200 eV ures Crystal monochromators in the beam path of
for Peltier cooled detectors. an X-ray tube allow the selection of either the charac-
ED spectrometers measure all photons coming teristic line from the anode or the selection of an
from the sample simultaneously. On one hand this is energy from the continuous spectrum. Mono-chro-
an advantage, because many elements can be mators with a high reflectivity as well as a large
detected within a short time, but on the other hand it energy band width are usually preferred, because the
is a disadvantage, because the maximum count-rate product of these two parameters determines the pho-
is limited to 50–80 kcps. The processing of the meas- ton flux on the sample. In comparison to crystal mon-
ured signal from each photon requires a certain ochromators, the multilayer offers high reflectivity as
length of time and during that interval the system is well as larger band width (dE/E = 10−2). Higher pho-
not ready to process the signal from the next arriving ton fluxes could be obtained. They are used with
photon. The result is a deadtime, which has to be either X-ray tubes or synchrotron radiation.
corrected. The reason for the saturation is not the
XRF using a linear polarized beam
number of fluorescence photons from the sample
mainly, but the exciting radiation being scattered by If linear polarized radiation is scattered, in the ideal
the sample and the sample carrier. Therefore special case no scattering radiation is emitted in the
2480 X-RAY FLUORESCENCE SPECTROSCOPY, APPLICATIONS

direction of the polarization vector. This effect can tube. In combination with a monochromator the ex-
be used to reduce the scattering from the sample it- citing radiation can be tuned to the energy with the
self. Barkla polarizers or Bragg polarizers can be optimum value of the photoelectric cross section for
used. The Barkla polarizer scatters the entire spec- the investigated sample. It is also possible to tune the
trum of the exciting radiation; the Bragg polarizer energy below the absorption edge of a main element
acts additionally as a monochromator. Both polariz- in the sample to excite an element at trace levels with
ers use the scattering of the unpolarized radiation Z < Zmain element. This method is called selective excita-
through an angle of 90°. Using polarized radiation tion and offers several advantages in trace element
the spectral background is drastically reduced in analysis. To perform microanalysis, focusing ele-
comparison to nonpolarized radiation, but again ments are inserted to produce high-intensity mi-
losses in intensity occur. crobeams. Also TXRF can be done using SR as
exciting radiation.
Total reflection X-ray fluorescence analysis (TXRF)
Trace element analysis
TXRF is an EDXRF technique, utilizing the total
external reflection of X-rays on the smooth plane To detect elements at trace levels – µg g−1 (ppm), ng
surface of a reflector material, e.g. polished quartz. If g−1(ppb) or even pg g−1 (ppt) – with XRF, generally
a low divergent beam impinges on the reflector sur- special techniques as well as special sample prepara-
face at an angle smaller than the critical angle for tion methods have to be used. The relevant quantity
total reflection, most of the beam is reflected from for trace element analysis is the limit of detection
the surface; only a small part penetrates into the re- (DL), which is given by the formula
flector, causing scattered radiation. This leads to a
reduced spectral background. The fluorescence sig-
nal is enhanced because the primary and also the
reflected beam excite the sample, which is deposited
on the reflector. Due to the small incidence angle the
detector can be brought very close to the sample, so
the detection efficiency is high. All these features IB is the background intensity, t the measuring time
lead to detection limits in the range of pg. Generally and S the sensitivity (cps ppm−1 or cps ng−1). Either
the samples have to be in liquid form. A droplet of increasing the sensitivity or reducing the background
2–100 µL is pipetted onto the sample reflector and leads to a reduction of detection limits. Therefore,
the liquid matrix is evaporated. Also, thin films or special techniques of XRF, mainly EDXRF tech-
thin layers, as well as atoms implanted in a reflecting niques, are applied, like TXRF, MXRF or SRXRF,
material such as Si-wafers, can be measured and as methods for trace element analysis. Detection lim-
thickness and depths determined. its range from ng to fg or µg g−1 to pg g−1.

Microfluorescence analysis (MXRF)

Microfluorescence analysis indicates the analysed Applications

area to be very small, leading to spatially resolved
information of the sample composition. There are The applicability of XRF is almost unlimited with re-
several methods of obtaining a beam with a small di- spect to type of sample and concentration range, but
depends very much on the chosen technique. It can
ameter, from a simple pinhole to highly sophisticated
X-ray optical elements with focusing characteristics. be used for on-line analysis in production processes
or in-field measurements of geological samples with
One very effective method is the use of capillaries us-
ing the principle of total reflection of X-rays on the portable instruments, or quality control, such as im-
inner walls of a glass capillary. Small diameters purity determination on Si-wafer surfaces at ultra-
down to 1 µm can be obtained with satisfactory trace levels, and environmental investigations. Also
intensity. sample preparation is an important factor influenc-
ing the applicability (see Figure 1). For fine art ob-
Synchrotron radiation induced XRF (SRXRF) ject investigation or precious objects from museums,
absolute nondestructiveness is required, contrary to
Synchrotron radiation, as described above, offers environmental sampling where homogenizing and
several advantages for use as an excitation source for pressing to a pellet is no problem.
XRF, especially the higher intensity, orders of To describe the various fields of application in
magnitude greater than that offered by an X-ray detail they are divided into categories.
 X-RAY FLUORESCENCE SPECTROSCOPY, APPLICATIONS 2481

and brass. Typically, simultaneous WD spectrometers

with an automatic sample changer are used.

Mining and ore processing

In mining and ore processing XRF is used for quality

and process control. The spectrometers used differ
very much depending on their application. Laborato-
ry spectrometers for quality control may be WD or
ED systems whith tube excitation. The on-stream
spectrometers are located at in-plant locations, can
be WD and ED systems, with radioisotope excitation
or X-ray tube excitation and equipped with flow
cells. In-stream instruments can be installed in slurry
streams, mainly equipped with radioisotope excita-
tion and scintillation counters for single-element de-
termination. Field instruments must be portable and
battery operated. The big advantage of XRF over
other analytical tools for that application is its sim-
plicity and speed. The usefulness of X-ray instru-
ments to selective mining is well established, the
information being used for ore–waste sorting.

Cement analysis

Finishing cements and raw mixes typically contain

Ca, Si, Al and O at high concentrations, plus Fe, K,
Mg and Na at low concentrations. One of the major
problems in accurate cement analysis is homogenei-
ty, particularly in the case of raw mixes, where the
source of raw material may be variable. Most of the
elements to be determined are of low atomic
number, hence the penetration of their characteristic
lines will be of the order of a few micrometres only.
Careful grinding and pelletizing will suffice, but the
fusion bead technique with Li3BO4 is strongly rec-
ommended. Simultaneous multichannel WD systems
are ideally suited for this kind of application.
Figure 1 Overview of sample preparation techniques typical
for XRF.
Lubricating oil analysis

Raw or used oils are usually analysed for additive-

Metals and alloys element content including Ba, Zn, Mn, Ca, P and Cl,
plus naturally occurring elements including S, N, Ni
Process control in today’s highly automated produc-
and Na. In blended stocks the concentration of these
tion facilities is strongly dependent upon fast, precise
elements would typically lie in the range 0.01–2.5%.
and accurate chemical analysis, and XRF has been
In a standard case the analysis will be performed in
found to be widely applicable in the metal industries.
the liquid phase and under a He atmosphere. Large
XRF of metallic samples includes several solvable
matrix effects are likely because of the variable con-
problems, especially in the areas of sample prepara-
centration levels of relatively heavy elements in a
tion and modelling calculations to convert intensities
very low average atomic number matrix.
into concentration data. In general, metallic samples
do not need complicated sample preparation, but the Geology
analytical information is derived from a volume close
to the surface which must be polished. XRF is applied XRF offers a rapid, accurate, low-cost method of
to various kinds of alloys, such as Na–Mg alloys, and analysis. Fully automated XRF spectrometers,
Al, Ti, ferrous, Ni, Cu, Zr, W and Au alloys, bronzes sequential as well as simultaneous WD instruments,
2482 X-RAY FLUORESCENCE SPECTROSCOPY, APPLICATIONS

and ED instruments are in use. The analysis of geo-

chemical samples often involves the analysis of sam-
ples having concentrations ranging from 0.0001 to
80%. Elements from Na to U are routinely deter-
mined. Detection limits depend very much on sample
preparation and are in the range 20–1000 µg g−1 for
low-Z elements, 5–10 µg g−1 for medium-Z elements
and 1–20 µg g−1 for high-Z elements.
One spectacular application of EDXRF was the
Mars Pathfinder which was designed to inspect the
rocks on the surface of Mars. Radioisotope excita-
tion was used and one of the new electrically cooled
ED detectors mounted on a small vehicle. Surface
analysis of rocks could be performed quickly and the
data could be transferred to Earth.
Figure 2 Spectrum of lichen sample. Pressed pellet, meas-
Fine art and archaeological objects ured with a standard EDXRF spectrometer, Rh tube 30 kV, 0.2
mA, 500 s, Pd filter, Si(Li) detector; concentration values of re-
In principle, with EDXRF, nondestructive analysis spective elements given in µg g−1.
can be performed, which opens up the wide field of
art and museum objects. Coins, bronzes, paintings, maps of bone cross-sections, superconductor films,
pottery, ceramics and ancient glasses can all be ana- human hair, pig heart muscles, metal alloys, leaves,
lysed. Paintings can be analysed pixel by pixel. With chinaware, environmental particles, tree rings and
a spectrometer mounted on an x–y stage, a selected glass fragments.
area can be analysed and the whole painting can be
scanned. In particular, MXRF techniques are very Medicine
well adapted to analysing specific points on figures
or vessels, as well as lines on ancient documents. In vivo measurements as well as in situ measure-
ments and analysis of malignant cells, as well as tis-
Environmental analysis sue sampling have been performed. In vivo
measurements started with the determination of io-
This is probably the most versatile and important dine in the thyroid and range from Cd in liver and
application as all kinds of biological material such as kidney and Pt in kidneys and tumours, to Hg in the
plants, roots, needles, food-stuff, algae and lichens as wrists and skulls of dentists, Pb in various near-sur-
biomonitors can be analysed with XRF. Lichens of- face bones, Cu in the eye and Fe in the skin. For the
fer the advantage of a natural sampler collecting in vivo measurements, the use of polarized radiation
aerosols without exchange with the substrate. See offers big advantages. Hg and Pb can be analysed by
Figure 2 as example of a sample lichen measured their K-radiation thus giving information from even
with an EDXRF spectrometer. Soil, river sediments, deeper tissues. Also, the analysis of biopsy samples,
sewage sludge, dust, coal fly ash, car exhaust and fog whole blood and blood serum (Se) can be performed
condensate or the aerosols, sampled in impactor using EDXRF. Trace element content in malignant
stages, are well suited for XRF. All kinds of liquids and benign tissues was investigated, as well as lung
can be analysed: river water, sea water, snow, ice. tissue from different factory workers, showing dif-
However, special techniques for sample preparation ferent elements at higher concentrations correspond-
should be applied especially when trace element ing to their profession. Various body fluids were
analysis is required. analysed, and correlation between trace element con-
tent and diseases found. EDXRF, TXRF and SRXRF
Microfluorescence analysis were used, depending on the task.
MXRF allows spatial resolution of analysis. To per- TXRF applications
form it with sufficient intensity in the laboratory
with X-ray tubes, special optics should be applied TXRF extends EDXRF to a method for trace and ul-
such as capillaries. Using capillaries, X-ray tube exci- tratrace element analysis. A special feature is the
tation with SR allows much higher intensities, and so small sample amount required, which is in the range
lower detection limits can be obtained. Applications µg–ng of a solid material and less than 100–10 µL of
range from microelectronics and plating thickness, a liquid. Therefore, TXRF is a microanalysis method
 X-RAY FLUORESCENCE SPECTROSCOPY, APPLICATIONS 2483

and samples can seldom be analysed as-received. Pre- It is obvious that the sample preparation technique
treatment is generally required to prepare the samples used influences the detection limits. Table 1 shows
as solutions, suspensions, fine powders or thin sec- this influence on various samples from different fields
tions. For a determination of ultratraces, the matrix of application. Table 2 gives an overview of applica-
of the sample should be separated and removed. All tions of TXRF already analysed. Figure 3 shows a
preparation techniques can be applied that have been spectrum of a water standard reference sample (NIST
tested with other methods of atomic spectrometry, 1643c) obtained with a TXRF vacuum chamber, con-
e.g. AAS, inductively coupled plasma mass spectrom- structed at Atominstitut, Vienna. Generally, an excel-
etry. The quantification is generally very simple, be- lent field of application of TXRF in trace element
cause the sample forms a thin layer, so the thin-film analysis can be seen in liquid samples. All kinds of liq-
approximation is valid. One element of known con- uids, ranging from different kinds of water to acids
centration has to be added as internal standard. and oils, as well as body fluids, can be analysed. Envi-
Quantification can be performed after the determina- ronmental samples, like airborne particles, plant
tion of the sensitivity factors of all elements relative to material or medical and biological samples such as
the internal standard. Also, surface and thin-layer tissue can be analysed directly on a reflector.
analysis, as well as analysis of atoms below a reflect- The main industrial application of TXRF is the
ing surface, can be performed by varying the angle of surface quality control of Si-wafer material. Wafers
incidence in the region of total reflection. This angle- offer the required flatness and are polished, so that
dependent intensity profile allows a qualitative differ- they can be directly analysed by TXRF. Several com-
entiation between contaminations on the surface, in mercial instruments have been developed as wafer
the layers, in implantations or in so-called residues af- analysers and some 100 instruments are utilized in
ter evaporation of liquid samples. Quantitative deter- the semiconductor industry. TXRF is capable of
minations can be made by applying an algorithm checking the contaminations brought in by different
deduced from theory in combination with an external steps during the production process. The required
standard. sensitivity is now 109 atoms cm−2 for transition

Table 1 Influence of sample preparation on detection limits in TXRF (after Klockenkämper R (1997))
Freeze- Chemical matrix Open Pressure Freeze
Sample Drying drying separation digestion Ashing Suspension Solution digestion cutting
Rain, river 0.1–3 ng 20–100 pg 3–20 pg mL1 1–3 ng
water mL1 mL1 mL1
Blood, serum Digest: 2–30 20–80 40–220 ng mL1
ng mL1 ng mL1
Air dust, ash, 5–200 10–100 µg g1 0.1–3
aerosols µg g1 µg g1
Air dust on 0.6–20 ng cm 0.2–6
filter ng cm
Suspended 3–25 10–100 µg g1
matter µg g1
Sediment 10–100 µg g1 15–300
µg g1
Powdered 1–10 µg g1 0.2–2
biomaterial µg g1
Fine roots 1–10 Digest: 0.1–1
µg g1 µg g1
High-purity 5–50 pg
acids mL1
Tissue, food- 0.5–5
stuff, biomate- µg g1
rial
Mineral oil 1–15
µg g−1
Mussel, fish 0.1–1
µg g−1
High purity 1 pg mL1
water
2484 X-RAY FLUORESCENCE SPECTROSCOPY, APPLICATIONS

Table 2 Applications of TXRF The implantation depth as well as the depth profile
Environment can be determined.
Water Rain, river, sea, drinking water,
TXRF can also be applied to fine art and museum
waste water. objects. The sampling technique – a dry cotton bud
Air Aerosols, airborne particles, can be used to rub off a small amount of paint – can
dust, fly ash. only be applied during restoration, because the
Soil Sediments, sewage sludge. varnish has to be removed. For analysis the bud is
Plant material Algae, hay, leaves, lichen, dipped onto a sample carrier by a single tip. An
moss, needles, roots, wood.
amount of less than 100 ng is transmitted and can be
Foodstuffs Fish, flour, fruits, crab, mussel,
mushrooms, nuts, vegetables,
analysed.
wine, tea.
Various Coal, peat. Application of SRXRF
Medicine/biology/pharmacology
Body fluids Blood, serum, urine, amniotic The rapid development of the SR X-ray sources since
fluid. about 1975 is starting to have an impact on X-ray
Tissue Hair, kidney, liver, lung, nails,
analysis. Due to the features of SR, especially the
stomach, colon.
Various Enzymes, polysaccharides,
small source size and therefore the high brilliance,
glucose, proteins, cosmetics, the use of microprobes is obvious. There are several
biofilms. approaches to producing a microbeam; the simplest
Industrial/technical applications is to use a pinhole collimator, but more sophisticated
Surface analysis Si-wafer surfaces, GaAs-wafer systems use focusing optics. Monochromatic as well
surfaces. as continuous radiation is used. Because SR is linear-
Implanted ions Depth and profile variations.
ly polarized in the orbital plane, scattering from the
Thin films Single layers, multilayers.
sample is reduced, leading to low detection limits.
Oil Crude oil, fuel oil, grease.
Chemicals Acids, bases, salts, solvents.
SRXRF is a trace element analytical method as well
Fusion/fission research Transmutational elements in Al
as an MXRF method. SRXRF is performed at sever-
Cu, iodine in water. al SR facilities, most prominently NSLS Brookhaven,
Mineralogy HASYLAB Hamburg, SSRL Stanford, SLS Dares-
Ores, rocks, minerals, rare bury, Photon Factory Tsukuba, DCI Lure and ESRF
earth elements. Grenoble. The available spot sizes are in the region
Fine arts/archaeological/forensic of 10 µm and the detection limits in the low pg to fg
Pigments, paintings, varnish.
range. Interesting applications were found in the
Bronzes, pottery, jewellery.
fields of geology (mineral inclusions can be ana-
Textile fibres, glass, cognac,
dollar bills, gunshot residue, drugs, tapes,
lysed), as well as in biology and medicine (distribu-
sperm, fingerprints. tion of trace elements in bone, tooth, brain, hair or
algae strands, tree rings and aerosol particles), giving
interesting information. Also, application in archae-
elements like Cr, Fe, Co, Ni, Cu and Zn. TXRF has ology is found, letters in different ancient papers be-
an ‘up-time’ of 90% and is nondestructive. Surface ing analysed to allow the differentiation of the ink
mapping can be performed and differentiation used to help identify the workshop. Even extraterres-
between film type or particle type is possible. The trial minerals and rocks have been analysed.
detection limits can be improved by more than two TXRF can also be done using SR as the excitation
orders of magnitude, if the impurities of the entire source (SR-TXRF) offering the advantage of higher
surface of the wafer are collected and preconcen- photon flux and improved detection limits. Experi-
trated prior to TXRF analysis. The native oxide ments are performed at SSRL, HASYLAB, Photon
layer is dissolved by HF vapour and the impurities Factory and ESRF. The main application is the
remaining on the surface are collected by scanning surface quality control of Si wafers. With SR-TXRF,
the wafer with a drop of a suitable liquid. This detection limits on wafer surfaces of 107 atoms cm−2
method has the advantage of higher sensitivity, but have been obtained. At SSRL there is a beamline
nondestructiveness is lost. dedicated for routine wafer analysis. SR is the ideal
It is also possible to measure the thickness of near- source for the excitation of low-Z elements. It offers
surface layers in the range 1–500 nm on reflecting high intensity also in the low-energy region, in com-
substrates with TXRF. Single layers as well as multi- parison to standard X-ray tubes. They do not emit
layer samples can be analysed. Also, atoms enough intensity in the low-energy region; therefore
implanted in the reflecting surface can be detected. the analysis of low-Z elements always lacks intensity
 X-RAY FLUORESCENCE SPECTROSCOPY, APPLICATIONS 2485

Table 3 Overview of various applications (from Török S and Van Grieken R (1994) X-ray spectrometry. Analytical Chemistry 66:
186R–206R; Török S, Labar J, Injuk J and Van Grieken R (1996) Analytical Chemistry 68: 467R–485R)
Field Method Field Method
Archaeology Se in soil SR-TXRF
General MXRF Soil, marine sediments WDXRF
Paintings TXRF Impurities in ice TXRF
Obsidian EDXRF V, Ni, in oil, asphaltene EDXRF
Medals WDXRF Bitumen solutions EDXRF
Pottery WDXRF Geology
Pigments TXRF Rocks WDXRF
Biomedical MXRF Mineral grains SRXRF
General SR-TXRF Soils, sediments MXRF
Single-cell analysis EDXRF, TXRF Fossilized bone WDXRF
Biopsy samples EDXRF, RIXRF Crysolite EDXRF
Blood EDXRF Geological samples WDXRF
Skin in vivo RIXRF Phosphate in rocks EDXRF
Bone EDXRF Oxides, silicates, carbonates WDXRF
Bone in vivo RIXRF Liquid petroleum products EDXRF
Leaves TXRF, WDXRF Microlayer of Fe–Mn nodules SRXRF
Hair EDXRF Au in micas SRXRF
Vegetables TXRF Materials science
Plants WDXRF Thin-film characterization XRF, EDXRF
Lichens WDXRF Impurities on Si-wafers TXRF, SRXRF
Moss RIXRF Multilayers EDXRF
Cd in kidney RIXRF Superconductors WDXRF
Mussel shells WDXRF Zirconium oxide WDXRF
Cu, Se, Zn in kidney SR-TXRF Alumina WDXRF
Marine bivalve shells SRCXRF Cu corrosions EDXRF
Pt in tumour tissues EDXRF Ultrapure reagents TXRF
Cu in human serum EDXRF Glasses WDXRF, EDXRF
Pb in bones, serum, blood RIXRF Ferroalloys EDXRF
Fe in vivo RIXRF High-purity Cu EDXRF
Hg in vivo RIXRF GaAs-wafers TXRF
Amniotic fluids TXRF Electrolytic solutions RIXRF
Plankton in polluted lakes EDXRF Al2O3 thin films WDXRF
Meadow moths SRXRF Plastic materials EDXRF, WDXRF
Environmental Ceramic materials WDXRF
Aerosols WDXRF, EDXRF, Hf in Zr matrix EDXRF
TXRF, SRXRF Ga in polyurethane foam WDXRF
Fly ash SRXRF P in PbO films EDXRF
Rain water TXRF Cu, Sr, Bi film on MgO RIXRF
River water TXRF Molybdate crystals EDXRF
Sea water TXRF Ferrous alloy WDXRF
Sediments, suspensions EDXRF, TXRF Ta in Ti–Ta alloys WDXRF
Waste EDXRF Pb in houseware RIXRF
Coal EDXRF, WDXRF Textile fibres TXRF
Dust EDXRF W analysis TXRF
Pb in dust WDXRF HTSC films SRXRF
HTSC = High-temperature semiconductor.
2486 X-RAY FLUORESCENCE SPECTROSCOPY, APPLICATIONS

Figure 3 Spectrum of water sample, NIST 1643c standard reference material, 10 µL, dried on a quartz reflector, measured with the
TXRF vacuum chamber of Atominstitut, Mo monochromatic excitation, 40 kV, 50 mA, 1000 s; concentration values of respective ele-
ments given in µg L−1.

of the fluorescence lines. TXRF is also applied to the List of symbols

determination of low-Z elements using a special
detector. Detection limits of 60 fg for Mg have been d = lattice spacing; DL = detection limit; IB = back-
achieved using SR and have to be compared to 7 pg ground intensity; S = sensitivity; t = measuring time;
with windowless Si-anode tube (prototype) Z = atomic number; λ = wavelength.
excitation.
SR-TXRF generally is a very fast growing field and See also: Environmental and Agricultural Applica-
the problem of reduced access to SR sources for tions of Atomic Spectroscopy; Environmental Appli-
routine analytical applications is becoming less cations of Electronic Spectroscopy; Geology and
severe due to the large number of dedicated facilities. Mineralogy, Applications of Atomic Spectroscopy;
Table 3 gives an overview of applications and Inorganic Compounds and Minerals Studied Using X-
techniques published from 1994 to 1998. Ray Diffraction; IR and Raman Spectroscopy Studies
of Works of Art; IR Spectroscopy Sample Preparation
Methods; MRI of Oil/Water in Rocks; X-Ray Fluores-
Conclusions cence Spectrometers.

Applications range from on-line analysis and in-field

inspections to ultratrace analysis of semiconductor Further reading
surfaces. There is almost no sample that cannot be
analysed by XRF as long as elemental analysis is re- Bertin EP (1978) Introduction to X-ray Spectrometric An-
quired. The achievable detection limits depend on alyis. New York: Plenum Press.
Carpenter DA (ed) (1997) Special Issue on Micro X-ray
the method used and range from µg g−1 (ppm) to pg
Fluorescence Analysis. X-ray Spectrometry 26(6):
g−1 (ppt). Nondestructive analysis can be performed
Ellis A, Potts Ph, Holmes M, Oliver GL, Streli C and Wo-
but sometimes sophisticated sample preparation brauschek P (1996) Atomic spectrometry update: X-ray
techniques are required. The elemental range (Be to fluorescence spectrometry. Journal of Analytical Atom-
U) depends on the excitation source as well as the ic Spectrometry 11: 409R–442R.
detection system. Generally XRF can be seen as a Ellis A, Potts Ph, Holmes M, Oliver GL, Streli C and Wo-
work-horse for elemental analysis and is easy to use. brauschek P (1997) Atomic spectrometry update: X-ray
 X-RAY SPECTROSCOPY, THEORY 2487

fluorescence spectrometry. Journal of Analytical Atom- Sparks CJ (1982) X-ray fluorescence microprobe for chem-
ic Spectrometry 12: 461R–490R. ical analysis. In: Winick H and Doniach S (eds) Syn-
Herglotz HK and Birks LS (eds) (1978) X-ray Spectrome- chrotron Radiation Research, pp 459–509. New York:
try. New York: Marcel Dekker. Plenum Press.
Holynska B (1993) Sampling and sample preparation in Török S and Van Grieken R (1994) X-ray spectrometry.
EDXRS. X-ray Spectrometry 22: 192–198. Analytical Chemistry 66: 186R–206R.
Iida A and Gohshi Y (1991) Trace element analysis by X- Török S, Labar J, Injuk J and Van Grieken R (1996) X-ray
ray fluorescence. In: Ebashi S, Koch M and Rubenstein spectrometry. Analytical Chemistry 68: 467R–485R.
R (eds) Handbook on Synchrotron Radiation, Vol. 4, Van Grieken R and Markowicz A (eds) (1993) Handbook
pp 307–349. Amsterdam: North Holland, Elsevier. of X-ray Spectrometry. New York: Marcel Dekker.
Jenkins R, Gould RW and Gedcke D (1981) Quantitative Wielopolski L and Ryon RW (eds) (1995) Workshop at
X-ray Spectrometry. New York: Marcel Dekker. the Denver X-ray conference on in vivo XRF measure-
Klockenkämper R (1997) Total-Reflection X-ray Fluores- ment of heavy metals. Advances in X-ray Analysis 38:
cence Analysis. New York: Wiley. 641.

X-Ray Spectroscopy, Theory

Prasad A Naik, Centre for Advanced Technology,
HIGH ENERGY
Indore, India
SPECTROSCOPY
Copyright © 1999 Academic Press Theory

X-ray is the region of the electromagnetic spectrum X-rays from inner shell transitions in
lying between gamma rays and extreme ultraviolet atoms
(XUV / EUV) corresponding to a wavelength range of
about 0.1 to 100 Å. The radiation on the lower end X-rays are produced when an electron in an outer
of the XUV region, up to about 300 Å, is also some- shell of an atom jumps to an inner shell to fill an
times referred to as X-ray. On the lower wavelength electron vacancy. The difference in energy is emitted
side, radiation of shorter wavelengths is termed X-ray as an X-ray photon. The vacancy giving rise to such
if it is nonnuclear in origin. The wavelength of the ra- a transition can be produced by an energetic photon,
diation is related to the photon energy by the stand- bombardment of charged particles (e –, p, α ..), or by
ard relation E (keV) = 12.4/λ(Å). In terms of energy, nuclear processes such as internal conversion, K-cap-
the X-ray region is roughly between 125 eV and ture, etc. If a charged particle collision or a nuclear
125 keV. Being electromagnetic radiation, X-rays process produces the vacancy, the resulting X-ray
can be reflected, refracted, scattered, absorbed, polar- emission is called primary. If the vacancy is pro-
ized etc. They also show interference and diffraction duced by an X-ray photon, the subsequent emission
effects. is called secondary or fluorescence radiation.
There are several sources of X-rays such as a In all these cases the singly ionized atom lowers its
Coolidge tube, vacuum sparks, hot-dense fusion energy by emission of a photon of definite wave-
plasmas, synchrotron, pinch devices, muonic atoms, length which is characteristic of the emitting atom.
beam-foil interaction, stellar X-ray emitters, solar Hence, these X-rays are also called characteristic X-
flares, etc. The X-rays originating from all these rays.
sources can be broadly categorized into main types:
(1) atomic inner shell transitions, (2) emission by Characteristic X-rays
free electrons, (3) X-rays from few electron systems.
The most energetic X-ray emission comes when a va-
The basic spectroscopic aspects of the various types
cancy in a K shell (n = 1) is filled by an outer
of X-rays are discussed in this article.
electron. Removal of a 1s electron from a neutral
atom raises it to the highest energy state represented
by lsls–1 or 1 2S1/2 or KI. Removal of a 2s electron