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Anal. Chem.

2010, 82, 4950–4987

X-ray Spectrometry
Kouichi Tsuji* and Kazuhiko Nakano

Department of Applied Chemistry & Bioengineering, Graduate School of Engineering, Osaka City University,
3-3-138 Sugimoto, Sumiyoshi-ku, Osaka, 558-8585, Japan

Yoshio Takahashi

Department of Earth and Planetary Systems Science, Graduate School of Science, Hiroshima University,
Higashi-Hiroshima, Hiroshima 739-8526, Japan

Kouichi Hayashi

Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577, Japan

Chul-Un Ro

Department of Chemistry, Inha University, 253 Yonghyun-dong, Nam-gu, Inceon, 402-751, Korea

Review Contents (WD-XRF). This review involves only a selected minority of
Overview 4950 published papers and impressive figures. We attempt to look over
Detection 4952 the current trends in this analytical field with a critically selected
Instrumentation and X-ray Optics 4955 citing of papers to support the research activity of the community
Crystal Spectrometer 4955
of X-ray scientists.
X-ray Generator 4955
X-ray Optics 4955 Since the previous review in Analytical Chemistry, an interna-
Quantification and Fundamental Data 4957 tional group of scientists published two overviews on XRS (1, 2)
X-ray Imaging 4960 in the Journal of Analytical Atomic Spectrometry, covering the
Total Reflection X-ray Fluorescence Analysis 4962
Electron Probe Microanalysis 4963 period 2008-2009 in the main field of XRS analytical spectroscopic
Particle-Induced X-ray Emission 4965 methods and instruments. These review articles involve all the
Micro X-ray Fluorescence Analysis 4967 important sections of XRS in nine chapters: reviews, instrumenta-
X-ray Absorption Spectrometry 4968
Applications 4970
tion, spectrum analysis, matrix correction and calibration, X-ray
Sample Preparation 4970 optics and microfluorescence, synchrotron radiation (SR), TXRF,
Standards 4971 portable and mobile X-ray fluorescence (XRF), and online XRF
EDS 4972 and applications. The section of applications is categorized into
µ-XRF 4974
TXRF 4977 geological and industrial minerals, environmental, archeological,
EPMA 4979 cultural heritage, and forensic science, etc. These review articles
PIXE 4981 are useful, especially for identifying the recent trends of applica-
XAS 4982
Literature Cited 4984
tions of XRS.
Two fundamental and practically useful books were published
OVERVIEW by Springer. The book Modern Developments in X-ray and Neutron
In this review, we focus on the most significant and essential Optics in the Springer series on optical sciences (3), edited by A.
progress in X-ray spectrometry (XRS) published during the period Erko, M. Idir, T. Krist, and A. G. Michette, describes theoretical
2008-2009 covering developments and improvements in X-ray approaches for modeling and ray-tracing and the state-of-the-art
optics, X-ray detectors, new quantification models in X-ray spectra in X-ray optics, such as reflection/refraction optics, multilayer
and data evaluation, micro-X-ray fluorescence (µ-XRF) including optics, and diffraction optics in a total of 533 pages. Many figures
3D-X-ray fluorescence (3D-XRF), imaging techniques such as and experimental data, based on research activities under the
tomography and holography methods for 2D or 3D imaging of framework of the European Programme for Cooperation in
microstructures, electron probe microanalysis (EPMA), total Science and Technology (COST, Action P7), will be helpful for
reflection X-ray fluorescence (TXRF), particle-induced X-ray emis- readers. Another book, the Handbook of Sample Preparation for
sion (PIXE) analysis, and X-ray absorption spectrometry (XAS). Scanning Electron Microscopy and X-ray Microanalysis, written by
In addition, different applications in each subfield of XRS are P. Echlin (4) focuses on sample collection, sample preparation,
described including sample preparation, standard materials, and sample cleaning for scanning electron microscope (SEM) and
energy-dispersive XRF (ED-XRF), and wavelength-dispersive XRF EPMA of various samples, such as inorganic, organic, biological,
4950 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 10.1021/ac101069d  2010 American Chemical Society
Published on Web 05/24/2010
From this point of view, the X-ray laser is a very desirable source.
It was reported that the free-electron laser (FEL) facility at the
Stanford Linear Accelerator Center (SLAC) National Accelerator
Laboratory in California in the U.S. achieved a “hard” X-ray laser
with a wavelength of 1.5 × 10-10 m (7). The electrons, traveling
with the energy of 14 GeV, were oscillated by a periodic
permanent magnet, called a wiggler. The wavelength of light
depends on the speed of the electron beam. The author stated
that an X-ray laser with a short wavelength, high power, and
short pulses (<100 fs) would be a powerful tool for studying
the mechanisms of molecular and atomic processes. Suckewer
and Jaegle wrote a review article on the X-ray laser (8). The
historical background, experimental setup for laser-induced
plasma and discharge plasma, characteristics of soft X-ray lasers
(coherence, divergence, and gain), and recent developments
for future soft X-ray laser systems were described. In addition,
important applications of X-ray lasers in microscopy, hologra-
phy, and interferometry were described.
Micro-XRF, which is an important technique for the analysis
of small areas, is one of the significant trends in XRS. A micro
Figure 1. A cover photograph of the book entitled Portable X-ray X-ray beam can be created by various focusing X-ray optics. The
Fluorescence Spectrometry, showing the analysis of the statue of spot size of the X-ray microbeam is an important factor directly
David by Michelangelo. Reproduced by permission of The Royal influencing lateral resolution in micro-XRF analysis. The research
Society of Chemistry (Copyright 2008, ref 5). group of Yamauchi at Osaka University in Japan successfully
produced a nano X-ray beam with a width of 7 nm at 20 keV (9).
and geological samples, metals, polymers, and semiconductors.
This focal spot was achieved by using a laterally graded multilayer
A large number of color figures and photographs are very
mirror and a grazing-incidence deformable mirror. The authors
instructive for understanding these techniques, not only for
described that this nano X-ray beam would enable SR-based X-ray
students but also for professional researchers. The book Portable
analysis with single-nanometer spatial resolution. The research
X-ray Fluorescence Spectrometry, edited by P. J. Potts and M. West,
was published by the Royal Society of Chemistry (5). Figure 1 is activities on nano-XRF given by other research groups are
a cover photograph of this book, showing the portable EDXRF introduced in the section of Applications: Micro-XRF in this review.
analysis of the statue of David by Michelangelo. Development of Camara et al. reported nanosecond X-ray flashes from peeling
portable XRF devices is one of the hot topics and will undoubtedly tape (10). When a common adhesive tape was peeled in a
introduce new application fields of XRF analysis. After a brief moderate vacuum, radio and visible light emission as well as
explanation of analytical instrumentation and quantification, many nanosecond 100 mW X-ray pulses were observed. The authors
applications of portable XRF for samples were introduced, such applied this X-ray triboluminescence phenomenon as a source of
as coating, paints, and art. In chapter 6 of this book, the application X-ray imaging. Hatakeyama et al. developed a portable XRF
of field-portable XRF analyzers to alloy identification was intro- instrument using a commercially available miniature X-ray emitter
duced. The advantages and disadvantages of excitations by X-ray with a pyroelectric crystal, operated by a 9 V battery (11). They
tubes and radioisotopes were discussed. Tables showing analytical reported a spatial resolution of 3.5 mm with this portable system.
performance obtained with commercial isotope-based and X-ray Development of a portable XRF instrument with a small X-ray
tube-based analyzers are very useful for users. In the last chapter, source is important and opens many application fields of XRS, as
in situ XRF analysis and X-ray remote sensing of planetary surfaces shown in the section of Applications: EDS in this review.
are described. Micro-XRF analysis at different positions on a sample gives
von Bohlen at ISAS in Dortmund, Germany, wrote a review elemental distribution. The drawback of this method of sample
article of TXRF and grazing incidence XRS with 76 references scanning is the long acquisition time needed for scanning a large
(6). The historical background, theory, quantification, instrumen- area. Tichy et al. demonstrated XRF imaging with pixel detectors
tation, and applications of both techniques were discussed. Figure (12). A semiconductor hybrid pixel detector, “Medipix2”, consisted
2 shows the numbers of papers containing the “TXRF” technique, of a sensor chip bonded to a read-out chip. This sensor had a
indicating that TXRF has been used in various fields. After a matrix of 256 × 256 square electrodes (pixels). Each pixel (55
fundamental introduction of X-ray standing waves (XSWs), their µm × 55 µm) works as a single channel analyzer. The authors
applications to the analysis of particles and layered materials were simply built an experimental setup with a tungsten X-ray tube and
introduced. In addition, recently developed commercial TXRF a sample holder. The integral fluorescent spectrum was numeri-
spectrometers were reviewed with their characteristics and cally differentiated, and then an energy spectrum was obtained.
approximate prices. A demonstration of XRF imaging of a printed circuit board
The development and improvement of X-ray sources are of consisting of Cu, Sn, and Pb was successfully performed. The
primary importance for XRS because the analytical performance X-ray detector is also a key technology for critically determining
of XRS depends critically on the intensity of the primary X-rays. the analytical performance of X-ray analytical methods. Further
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4951
Figure 2. Publications containing “TXRF”, obtained from ISI Web of Knowledge in January 2009. Numbers of annually published papers are
represented as bars; the sum as a line. Reprinted from (ref 6) Spectrochim. Acta, Part B, 64, von Bohlen, A. Total reflection X-ray fluorescence
and grazing incidence X-ray spectrometry-Tools for micro- and surface analysis. 821-832, Copyright 2009, with permission from Elsevier.

development of the pixel detector is expected for rapid XRF
elemental imaging.
Many papers reported on a combination of analytical tech-
niques. Here, the research progress in the combination of XRS
and scanning tunneling microscopy (STM) is introduced. Okuda
et al. showed nanoscale chemical imaging by STM assisted by
SR (13). Checkerboard patterned Ni and Fe samples were
irradiated by SR X-rays with energy near Ni (or Fe) L absorption
edge. X-ray induced current images were taken with a STM tip.
Differential current images gave elemental specific contrasts on
a spatial resolution of about 10 nm. Rose et al. also studied X-ray
induced photoelectron spectroscopy, which used an STM tip for
detection (14). The STM tip current and the total electron yield
Figure 3. (a) Schematic diagrams of the cantilevered absorbers.
for the Cu/NiFe sample were measured as a function of the energy The square gray outline marks the edge of the absorbers, which are
of the X-rays with different sample bias voltages. The authors supported only at the contact areas shown shaded in black. (b)
proposed different channels contributing to the X-ray enhanced Photograph of TES array with electroplated Au absorbers. Reprinted
STM current. They concluded that the detection of SR enhanced with permission from (ref 15) Iyomoto, N.; Bandler, S. R.; Brekosky,
R. P.; Brown, A.-D.; Chervenak, J. A.; Finkbeiner, F. M.; Kelley, R. L.;
electrons would have possible applications for high-resolution
Kilbourne, C. A.; Porter, F. S.; Sadleir, J. E.; Smith, S. J. Appl. Phys.
microscopy with chemical sensitivity. Lett. 2008, 92, 013508. Copyright 2008, American Institute of
Physics.

DETECTION for astrophysics applications, microcalorimeters arrayed with a
Microcalorimeters, which are operated at the millikelvin order, high fill factor are required. They designed an X-ray absorber that
are promising energy dispersive type X-ray detectors. With a low is cantilevered over the sensitive part of the thermometer itself,
heat capacity under such a low temperature, thermal power making contact only at normal metal features. With electroplated
fluctuation in conductivity is reduced to the order of 1 eV. Thus, gold absorbers, an energy resolution between 2.4 and 3.1 eV at
the energy resolution of a microcalorimeter is comparable to a 13 separated pixels was achieved by the thermal and electrical
crystal spectrometer, which is an order of magnitude better than parameters of the devices throughout the superconducting transi-
conventional semiconductor-based energy dispersive detectors, tion. A group at the “Commissariat à l’Énergie Atomique” (CEA-
such as Si or Ge detectors. Low heat capacity absorbers, such as LETI) in Grenoble, France, developed an X-ray spectro-imaging
Bi, Sn, and Ta, and sensitive thermometers are necessary. For camera for next-generation space astronomy missions (16). They
the thermometer, a doped semiconductor, a transition edge sensor developed monolithic silicon microcalorimeters based on im-
(TES), and a superconducting quantum interference device planted thermistors in an improved array, which were suitable
(SQUID) sensor have been used. Iyomoto et al. developed closely for future X-ray missions. The 8 × 8 array consists of a grid of 64
packed arrays of TES calorimeters to provide rapid thermalization suspended pixels fabricated on a Si-on-insulator (SOI) wafer. The
of X-ray energy, as shown in Figure 3 (15). The active area of an Ta absorber array was bound to the thermistor array in a collective
individual detector was small to maintain a small heat capacity. process. The use of a single SOI substrate and microtechnological
In order to cover a wide solid angle of X-ray detection, especially techniques offered an advantage of compatibility between the
4952 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
standard metal oxide semiconductor and mechanical system 1340 × 400 array without overcoating, cooled to -45 °C. In
technologies, based on the steps of deposition, photolithography, dynamic mode, a photon-counting CCD enabled obtaining spectra
and plasma etching. In Italy, there is a small space mission, up to 25 keV from a high repetition rate laser-plasma X-ray source
AGILE, devoted to γ-ray and hard X-ray astrophysics. Labanti et with high statistics in a short acquisition time. A cluster recon-
al. designed and constructed a CsI(Tl) mini-calorimeter that struction algorithm was more efficient than a standard summation
detected γ-rays or charged particle energy loss in the range 300 over the pixel cell. PILATUS is a multipurpose silicon hybrid pixel
keV to 100 MeV (17). The mini-calorimeter was composed of 30 detector system for X-rays operated in single-photon-counting
CsI(Tl) scintillator bars with a photodiode readout at both ends, mode, which has been developed for the needs of macromolecular
arranged in two orthogonal layers. Therefore, it had another crystallography at the Swiss Light Source (SLS) at the Paul
function of a tracker of the incoming radiation, determining the Scherrer Institute. Kraft et al. reported performance of a calibrated
direction of the γ-rays. The spectrometer and tracker systems PILATUS module, characterized with monochromatic SR (21). By
were combined to work together. The architecture of the mini- a threshold scan curve of a pixel, overall energy resolution of about
calorimeter has been designed to accomplish its different tasks 1000 eV was estimated for different X-ray energies, for example,
at the same time starting from a single detector system. The 1000 eV resolution for 8 keV X-rays. The average dead time was
maximum count rate of a microcalorimeter was about 1000 cps, about 100 ns at a low gain setting. With the use of these
which was quite low compared with conventional energy disper- characteristics, surface diffraction experiments at the SLS were
sive X-ray detectors. To improve the maximum count rate, Ohno demonstrated whereby the system’s performance regarding
et al. proposed a new TES pixel design that had a new geometry fluorescence suppression and saturation tolerance was evaluated.
of an absorber self-adjusting the operating temperature (18). In The large detector area with its high pixel count, sensitivity toward
their first prototype, they fabricated TES pixels using a Au/Ti/ high-energy photons, and fast frame rate made the amorphous
Au trilayer consisting of small heat sensors and a radiation silicon (a-Si) detector a very attractive complement to the imaging
absorption area and achieved a decay time constant of incident capability of the CCD and IP. A GE revolution 41RT flat-panel
X-rays from an 55Fe source of less than 20 µs. Rodrigues et al. detector (GE 41RT) has been in operation at the Advanced Photon
have been developing metallic magnetic calorimeters for Source for over 2 or 3 years. The detector has an active area of
enhancing the accuracy of atomic and nuclear data determi- 41 cm × 41 cm with a pixel size of 200 µm × 200 µm. Lee et al.
nation, in particular, X-ray and γ-ray emission probabilities (19). examined a number of its operational characteristics and found
They chose a high-Z material of gold for the detector absorber that its fast frame rate and large active area with high pixel count
and realized an Au/Er sensor of 50 µm diameter and an erbium opened up new opportunities for dynamic X-ray diffraction
concentration of 900 ppm. A SQUID was used as a converter measurements (22). Ideally, a large area, low noise, and wide
of magnetic flux of the Au/Er sensor to voltage. To suppress dynamic range digital X-ray detector is required for laboratory-
the noise of the SQUID read-out system, they adopted a two- based X-ray diffraction studies. In order to fulfill all these
stage SQUID setup. SQUID 1 acts as a magnetometer reading requirements, a group at the Department of Medical Physics,
out the sensor; it is inductively coupled to SQUID 2 through a University College London, fabricated a complementary metal-
resistor of a few ohms and an input coil. That is, SQUID 2 acts oxide-semiconductor (CMOS) active pixel sensor system for
as a low-noise preamplifier. The developed a mini-calorimeter laboratory-based X-ray diffraction studies of biological tissue (23).
offered an energy resolution of 40 eV for an 55Fe source and The CMOS active pixel sensor consisted of a CsI/Tl scintillator
200 eV for an 241Am source, respectively. layer, fiber optic plate, a passivation layer, and an active layer.
As typically represented by roentgenograms, X-ray imaging The prototype was a 520 × 520 array of pixels on a 25 µm pitch.
using X-ray film has played an important role in the history of They estimated this value by using materials covering medical
X-ray applications. Recently, owing to the appearance of highly applications of breast cancer diagnosis, kidney stone identification,
coherent X-ray sources, such as the third generation SR and X-ray and bone mineral density calculations. Multiwire proportional
free electron laser (XFEL) facilities, two-dimensional digital chambers have been widely used in high-energy physics experi-
detectors of X-ray charge-coupled devices (CCDs) have attracted ments for particle track measurements. Although the photon
a great deal of attention from many researchers. CCDs have counter mode of operation presents no advantage due to a low
become increasingly utilized in X-ray medical imaging, X-ray maximum count rate, the devices in the continuous-current mode
astronomy, protein crystallography, and two-dimensional XRF are efficient for multichannel imaging diagnostics, with an excel-
analyses. There are two kinds of X-ray CCDs, namely, the direct lent cost-performance relationship. To benefit from these advan-
detection CCDs and phosphor-coupled CCDs. A direct detection tages, a compact 64-channel multiwire proportional X-ray (MPX)
CCD senses low-energy X-rays (30 eV to 10 keV) while a detector was installed on the TCV tokamak (Tokamak à config-
phosphor-coupled CCD is useful for high X-ray energy detection uration variable). The MPX system consisted of 64 vertically
(>20 keV). Fourment et al. proposed a new device using a CCD viewing channels and was designed to complement the TCV soft
as a dispersionless spectrometer dedicated to repetitive X-ray X-ray tomography system by enhancing spatial resolution. The
sources in a multi-kiloelectronvolt domain (20). A CCD in a MPX detector measured the plasma soft X-ray emission in the
photon-counting mode can record spectrally resolved two- 3-30 keV range with a radial resolution of about 5 mm (24). To
dimensional images. However, the electron cloud generated by characterize hard XFEL pulses at the Linac Coherent Light Source
one X-ray generally spreads over several pixels. They tested in the future, Hau-Riege et al. developed a photoluminescence-
several reconstruction algorithms for spreading events using a based pulse-energy detector. They tested a prototype of this
Princeton Instrument 16-bit CCD equipped with a back-illuminated detector in a quasi-steady-state mode of operation at the conven-
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4953
tional synchrotron light source at the Stanford Synchrotron decay times, making them potential candidates where fast
Radiation Laboratory (25). They found that the luminescence imaging is demanded. Arikawa et al. presented experimental
signal was relatively large and easily detectable. In addition, they results on the neutron scintillating properties of custom-
developed a Monte Carlo (MC) model for X-ray interaction with designed Pr3+-doped fluoro-oxide lithium glass in their manu-
nitrogen gas and the resulting ultraviolet signal and obtained good script (30). For ultraviolet and X-ray excitation, about 20 ns
agreement with the experimental data. decay time was observed, while much faster decay times of 6
Recent developments in the methods of photolithography and ns were observed for R particle and neutron excitation. In time-
plasma etching permit the production of two-dimensional Ge of-flight data in a laser fusion experiment at the GEKKO XII
microstrip detectors with a pitch in the order of a few hundred facility of the Institute of Laser Engineering, Osaka University,
micrometers. Beside their application in classical spectroscopy, they could clearly discriminate fusion neutrons from much
such detectors will work as highly efficient Compton polarimeters. stronger X-ray signals and revealed that the Pr3+-doped fluoro-
Spillmann et al. reported performance of a Ge-microstrip imaging oxide lithium glass would be promising in the future as a
detector, which featured the good energy and time resolution of scattered neutron diagnostic.
semiconductor detectors together with submillimeter position Because of their high sensitivity and fast response, avalanche
resolution (26). For the detector, a single crystal of high purity photodiodes (APDs) are frequently used for optical communica-
n-type Ge with a total area of 41 × 70 mm2, whose surface was tion applications. Johnson et al. developed a Geiger-mode APD
boron-implanted for p+ contact, was used. It was divided by array for X-ray photon correlation spectroscopy (XCPS), which
plasma etching into 128 strips 56 mm long and a pitch of 250 provided an opportunity to study the dynamics of systems by
µm. Using the energy and position sensitivity of the detector, measuring the temporal fluctuations in a far-field diffraction pattern
they demonstrated the ability to obtain a complete reconstruc- (31). The X-ray detector system consists of a thin 100 µm
tion of the Compton event. An X-ray photoelectric polarimeter scintillation crystal coupled to a 6 × 6 Geiger-mode APD array
based on a gas pixel detector was proposed for measurement and was capable of investigating fluctuations in the frequency
of polarized X-ray emission. The estimated sensitivity of the range of several hertz to kilohertz. XCPS measurement was
current prototype peaks at an energy of about 3 keV. Muleri performed using this system.
et al. presented the measurement of the gas pixel detector The CdZnTe detector in pulse mode has great potentials for
polarimetric sensitivity at energies of a few kiloelectronvolts high-flux, high-speed energy-selective, or hyperspectral imaging.
using a light, compact, and transportable polarized source Some researchers consider that applications of CdZnTe detectors
based on the Bragg diffraction at 45° (27). This low-energy for medical computer tomography may produce a large potential
polarized source was employed to measure the polarimetric market but require detectors capable of handling a count rate of
sensitivity of the gas pixel detector between 2.6 and 5.2 keV. (20-200) × 106 counts/mm2/s. Bale and Szele theoretically
The measured modulation factor was in good agreement with investigated the mechanism of polarization in wide-bandgap
the MC results. Michel et al. measured polarization asym- semiconductor radiation detectors under a high-flux detector
metries using a hybrid semiconductor photon counting pixel (32). They developed a general mathematical model for the
detector in order to observe the degree of linear polarization defect structure in the bandgap of CdZnTe that was capable of
of X-rays in the energy regime between 27 and 84 keV (28). describing carrier transport and defect transition dynamics in
The TimePix detectors used included a sensor layer, which the presence of a high-flux X-ray source. Through simulation,
was pixilated with a pitch of 55 µm. Each sensor pixel electrode they identified and presented a sequence of dynamics that
was connected to one electronic cell of the readout ASIC via determines a critical flux of photons above which polarization
bump bonding of a tin-lead alloy. The ASIC was developed to effects were dominant. The predicted dependences were
be used in a time-projection chamber and, by being bump- validated for 16 × 16 pixel CdZnTe monolithic detector arrays
bonded to a Si sensor, serves as a tracking detector for charged subjected to a high-flux 120 kVp X-ray source. There is a great
particles. The pixel cells were organized in a quadratic matrix interest in the use of semi-insulating CdTe semiconductors as
of 256 × 256 giving a total side length of about 1.4 cm. The room temperature X-ray and γ-ray detectors because of their
active thickness of the sensor layer could be larger than in high atomic number and large band gap. Nevertheless, CdTe
CCDs, leading to good efficiency for higher X-ray energy. For detectors are subject to charge losses and leakage current,
irradiation with polarized X-ray photons, asymmetry could be causing electrical noise and decreased energy resolution. The
measured between vertical and horizontal double hit events in formation of both rectifying and near-Ohmic contacts by the
neighboring pixels of the hybrid photon counting TimePix deposition of Ni on opposite surfaces of semi-insulating CdTe
detector at room temperature. crystals, which were prepared by special chemical etching and
Recently, there has been an effort to develop new scintillator Ar-ion bombardment with different parameters, helped to
materials characterized by high light output, fast decay time, high improve detector performance (33). The reduced injection of
detection efficiency, and good energy resolution. Valais et al. the minority carriered from the near-Ohmic contact in the
investigated the luminescence emission properties of (Lu0.9,Y0.1)2- neutral part of the diode provides low leakage current even at
SiO5/Ce (LYSO/Ce) and (Lu0.7, Y0.3)AlO3/Ce (LuYAP/Ce) high bias (<50 nm/cm2 at 2000 V and 293 K).
crystals for use in X-ray medical imaging (29). They found that Diamond-based photodetectors have been studied as synchro-
the LYSO/Ce was superior to the LuYAP/Ce in terms of tron beam radiation monitors because their physical and electronic
luminescence efficiency and compatibility with ordinary Si characteristics are well suited for fabricating X-ray detectors. In
photodiodes. Furthermore, both the crystals showed very short general, their photoresponses are compared with a standard
4954 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
ionization chamber in X-ray absorption spectroscopy applications. rise to the emission of hard X-rays. For this purpose, Beyer et
Sio et al. studied time stability and linearity of a photoconductive al. developed a twin spectrometer, which was operated in the
device based on a nitrogen-doped single crystal diamond using focusing compensated asymmetric Laue geometry (38). A
10 keV X-rays at an SR facility (34). Fe K-edge extended X-ray specially designed two-dimensional position-sensitive X-ray
absorption fine structure (EXAFS) data were recorded both by detector was also coupled to the focusing crystal optics for
both the diamond device and the ionization chamber, and their retaining spectral resolution for fast-moving sources. They
spectroscopic results were in good agreement. GaN and its related tested the detector by employing the Lyman radiation of one-
alloys are now widely used in the area of optoelectronics. Very electron Pb81+ ions traveling at a velocity corresponding to β
recently, a detector based on GaN Schottky diodes was proposed ) ν/c = 0.59.
and tested for X-ray irradiation because it is a stable material under X-ray Generator. There are mainly two types of hard X-ray
X-rays (35). Vertically, Schottky diodes were fabricated based on generators: X-ray tubes and synchrotron-based X-ray sources. A
a 20 µm thick undoped GaN layer grown on a conductive GaN group in Russia studied a new type of X-ray generator utilizing
substrate. They observed anomalous photocurrents, characterized Thomson scattering of laser radiation on a bunch of relativistic
by a strong nonlinear response and by large asymmetry in the electrons and considered that it filled the gap that existed between
turn-on and turn-off transient. Furthermore, a very strong quench- these two conventional sources. They reported the Thomson X-ray
ing of the X-ray photoresponse was observed when the detector source or compact laser-electron X-ray generator operated in quasi-
was simultaneously illuminated with visible light. They mentioned continuous and pulsed modes (39). The proposed system con-
that these effects must be greatly reduced in order to develop tained a ∼50 MeV linac and a picosecond laser with an average
the GaN detector into an ideal X-ray detector. power of approximately a few hundred watts. The X-ray flux
achieved was 5 × 1011 photons in a millisecond flash and an
INSTRUMENTATION AND X-RAY OPTICS
average flux of 1012-1013 photons/s. In order to make an “in-
Crystal Spectrometer. In contrast to the energy dispersive
house” X-ray source that offers X-ray beams stronger than those
X-ray spectrometer (EDS), a wavelength dispersive X-ray spec-
generated by a commercially available generator, Sakabe et
trometer (WDS) using crystals or multilayer mirrors is useful for
al. at the Photon Factory of the High Energy Accelerator
quantitative elemental analysis due to its good energy resolution.
Research Organization, Japan, developed a new type of rotating
However, since the process requires scans of an analyzing crystal
anticathode X-ray generator in which the electron beam
and a detector, it has an inherent problem in that the measurement
irradiated the inner surface of a U-shaped Cu anticathode (40).
time is very long. A research group at Tohoku University in
The causes of the power limitation of a conventional rotating
Sendai, Japan, has a unique technique of deforming Si or Ge single
anticathode, where an electron beam irradiated the outer
crystal wafers to arbitrary shapes without loosing the crystal-
lographic orientation with respect to the crystal surface (36). The surface of a rotating anode, were splashing of the melted
wafers were deformed using upper and lower dies at a temperature materials, surface roughness, and irregular discharge. In the
just below their melting points. They prepared a cylindrical Ge new X-ray generator, the melted materials did not splash
wafer with a radius of curvature of 50 mm and acquired fluorescent because of the strong centrifugal force. Thus, when the
X-rays simultaneously from four elements of an alloy sample by irradiated part was melted, a large amount of energy was stored
combining the cylindrical Ge wafer with a position-sensitive as heat fusion, resulting in emission of X-rays 4.3 times more
detector. The energy resolution was as good as that obtained using brilliant than that obtainable by a conventional rotating
a flat single crystal, and its gain was over 100. anticathode.
Inelastic X-ray scattering spectroscopy is a rapidly developing X-ray Optics. X-ray optics is used for the purposes of focusing
tool for studying the electronic structures of materials. To improve and producing micro X-ray beams and monochromatic X-rays, etc.
the efficiency of the signal collection, Verbeni et al. developed a Therefore, the development of X-ray optics is very important,
multiple-element spectrometer for nonresonant inelastic X-ray sometimes dominating the analytical and practical performance
scattering spectroscopy, which was installed at beamline ID16 of of X-ray analytical techniques. In addition, X-ray optics is used in
the European Synchrotron Radiation Facility (37). It was equipped combination with X-ray sources. Therefore, it is also important to
with nine analyzer crystals with a bending radius R ) 1 m, and use adequate X-ray sources for each type of optics.
by combination of it with a two-dimensional detector, the spectra Capillary X-ray optics is a useful device to produce a high flux
given by all analyzers could be treated individually. The spec- micro X-ray beam, especially in the laboratory. The analytical
trometer was based on a Rowland circle design with fixed Bragg performances of four types of X-ray capillary focusing lenses were
angles of about 88°. The energy resolution was chosen between experimentally evaluated (41). The four lenses were (1) a
30 and 2000 meV with typical incident photon energies of 6-13 polycapillary conical collimator, manufactured by IfG-Institute for
keV. Thus, it was capable of studies of valence and core electron Scientific Instruments GmbH in Germany, (2) a single metallic
excitations resolving both energy and momentum transfer. Highly capillary with parabolic inner channel, designed and manufactured
charged ions with only one or a few electrons, such as Au79+, by the authors, (3) a monolithic glass polycapillary, made up of
Pb82+, or U92+, provided a sensitive probe of relativistic and hundreds of individual capillaries, manufactured by XOS in the
quantum electrodynamic effects in the hitherto unexplored U.S., and (4) a single glass capillary with a tapered inner channel,
domain of very strong electromagnetic fields. Quantum elec- produced by COX Analytical Systems in Sweden, as shown in
trodynamic contributions to the ground-state binding energy Figure 4. The test was performed in air in the IAEA laboratory
in one-electron systems was determined from accurate spec- using an X-ray tube (up to 3 kW, 45 kV, Mo anode, electron spot
troscopy of the corresponding K-shell transitions, which gave on the anode was 12 mm × 0.4 mm), a Si(Li) detector (80 mm2),
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4955
sample to reduce the size of the X-ray beam produced by the
polycapillary lens. The original spot size produced by only
the polycapillary lens was 70 µm. In combination with the
additional glass capillary, the spot size was reduced to 25 µm.
However, the gain for the combined system was about 60% of the
gain for the polycapillary lens. The transmission of X-rays of an
X-ray lens was studied for microfocus XRF (45). In the combina-
tion of a polycapillary X-ray lens and a microfocused X-ray tube,
the alignment of the X-ray lens relative to the spot size of the
emission source in the tube is important. When the tube with a
different anode material is changed, the position of the lens must
be adjusted to have strong X-ray intensity and to perform micro-
XRF under the optimized conditions. Therefore, it is important to
know the transmission properties. The transmission function was
determined by measuring two spectra with and without a lens
Figure 4. Four types of X-ray focusing lenses tested: (1) polycapillary
conical collimator, (2) single metallic capillary, (3) monolithic glass and dividing them by the other. The authors developed an
polycapillary, and (4) single glass capillary. Reprinted with permission alternative way to have the scatter spectrum without a lens. They
from (ref 41) Wegrzynek, D.; Mroczka, R.; Markowicz, A.; Chinea- simulated the scatter spectra when the X-ray tube was set to a 20
Cano, E.; Bamford, S. X-Ray Spectrom. 2008, 37, 635-641. and 40 kV anode voltage. Their model was confirmed by using a
Copyright 2008 John Wiley and Sons.
calibrated EDS.
Interest in curved crystal X-ray optics, which enables a
and two silicon drift detectors (SDDs). First, the spatial
monochromatic micro X-ray beam, is increasing. Bingolbali and
resolution, defined as a focal spot size was evaluated by a wire
MacDonald at the University of Albany in the U.S. studied doubly
scanning method using a tungsten wire 4 µm in diameter. The
curved crystal (DCC) X-ray optics and developed a simulation
smallest spot size (13.2 µm) was achieved by a single glass
model to understand the properties (intensity, beam size, resolu-
capillary. Second, the gain, which is the increase of the beam
tion, etc.) of the optics (46). The simulation was based on simple
intensity (per unit area) compared with the intensity obtained
ray tracing for a symmetric DCC optic in Johan geometry. To
with a pinhole, was evaluated as a function of X-ray energy.
confirm the simulated result, the authors made an experimental
The highest gain was obtained for the polycapillary lens. It was
setup, which consisted of an X-ray source (Oxford ultrabright,
about 2500 at 6 keV, but it decreased with X-ray energy to about
100 at 25 keV. The detection limits were also evaluated using Mo anode, 24 kV, 0.5 mA, source diameter 100 µm), DCC optic
a standard reference material (NIST, SRM 610). The lowest (XOS, UAS), and an x-y-z-θ alignment stage. A laser was used
relative detection limits were obtained with the polycapillary to perform rough optical alignment. The authors concluded that
X-ray lens and the cylindrical collimator. The authors concluded the simulations effectively modeled the behavior of the DCC
that the polycapillary X-ray lens was the optimum focusing optics, which enabled assessment of system performance in a
device for an X-ray tube-based scanning spectrometer. variety of applications. Kraemer et al. designed and produced a
Pérez et al. reported the characterization of a homemade DCC optic in order to apply it to micro-XRF of aerosol particles
polycapillary X-ray lens (42). With the use of fiberglass technology, (47). They introduced the basic theory about DCC Johann and
monolithic polycapillary half lenses were made by drawing a Johansson geometries and explained the production processes of
bundle of glass capillaries at high temperature in a heating furnace. DCC optics, such as fixing the crystal and bending the crystal
The measurements were performed at the LNLS SR facility in under high temperature. After the surface of the produced DCC
Argentina. The spot size, transmission efficiency, and gain were was tested by using the interference of laser light with a 3-D
about 77 µm, 5%, and 22, respectively. They intend to improve profilometer, its X-ray focusing property was investigated by a
the transmission efficiency using capillaries with thinner glass special setup that consisted of a commercial microfocus tungsten
walls. Matsuda et al. investigated X-ray-energy dependence of the tube and the EDS in Johann geometry. The knife-edge scan of
characteristics of the X-ray microbeam produced by a polycapillary the best DCC showed a spot size (full width at half-maximum
X-ray lens (43). Polycapillary optics was combined with a micro- (fwhm) values) of 23 µm × 29 µm.
focused X-ray tube (X-ray emission size on a Mo target: 50 µm × The fundamentals of nanoscaled multilayer coating techniques
50 µm). The spot size was evaluated by a wire scanning method for X-ray optics were explained (48). In particular, multilayer
using wire of different materials (W, Mo, and Ni-Cr). It was coating on a parabolically curved substrate with the d-value
shown that the spot size decreased by increasing the energy of gradient is useful for X-ray focusing or collimating. Coating
the X-rays that were monitored. This result indicated that high technology such as dc- or rf-sputtering, characterization techniques
energy X-rays concentrated at the center of the beam, while low such as X-ray reflectometry and applications of X-ray optics in X-ray
energy X-rays showed a wider distribution. The same research diffraction (XRD) and XRF were introduced. A Mo/B4C multilayer
group studied the combination of polycapillary optics and a glass grating was prepared and applied to measure the X-ray spectra
conical capillary to improve the spatial resolution in micro-XRF of C K and Fe L lines in soft X-ray energy (49). The thickness
(44). A polycapillary optics (XOS, UAS) was attached to a of Mo and B4C was 3 nm, and the period of grating was 1.0
microfocused X-ray tube. A glass conical capillary produced by µm. A multilayer grating was useful for improving the energy
Horiba Ltd. was placed between the polycapillary lens and the resolution, leading to distinguishing the Fe LR and Lβ,
4956 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
separated by 13 eV. In addition, high-resolution X-ray spectra composition profile. To obtain more information from the
for the C K line was sensitive to the chemical state of the carbon sample, EXAFS experiment was performed under grazing
atom in B4C and cellulose. Koike et al. also reported soft X-ray incidence condition, leading to depth-resolved EXAFS. As a
multilayer laminar-type plane gratings and varied-line-spacing result, CoSi intermetallic phase growth was successfully
spherical gratings in the energy range of 1-8 keV (50). monitored during the sample preparation and annealing
Fabrication of Mo/SiO2 multilayer grating, ray tracing tech- processes.
nique, and evaluation of multilayer gratings, such as diffraction
efficiency and spectral resolution, were explained. The first QUANTIFICATION AND FUNDAMENTAL DATA
order efficiency of the Mo/SiO2 multilayer grating was 15-20% One prominent field of application for 3D micro-XRF is
in 1.6-1.8 keV. The fwhm value of Si LR1 (1740.0 eV) was 8.0 characterization of stratified material, for example, paint layers
or biological samples that have a light matrix with traces or major
eV.
contents of high-Z elements and structures in the micrometer
Tamura et al. developed a multilevel-type multilayer X-ray lens
regime. With a typical depth resolution of 10-30 µm, 3D micro-
(Fresnel zone plate, FZP) by a sputter deposition technique (51).
XRF is currently capable of contributing to nondestructive
The multilayer FZP can achieve a high aspect ratio, which was
investigation of elemental distribution in these samples. A proce-
difficult for the conventional FZP produced by using lithography-
dure for quantitative reconstruction of the composition of stratified
based technology. A multilevel-type multilayer with lens with a
material by means of 3D micro-XRF was proposed and validated
six-step structure consisting of a high-Z layer, composite layer,
by Mantouvalou et al. (56). With this procedure, it is now possible
and a low-Z layer was developed in order to attain high diffraction
to nondestructively determine the chemical composition and the
efficiency. The diffraction efficiency was more than 50%, and the
thickness of layers. As no adequate stratified reference samples
focused beam size was 0.8 µm at 41.3 keV, as evaluated at SPring-8
were available for validation, stratified reference materials (RMs)
in Japan. It was also proved that the produced FZP was structurally
were reported to be developed that are appropriate for 3D micro-
stable for at least 9 months.
XRF or other depth-sensitive X-ray techniques. In comparison to
A multiprism lens, which is one kind of refractive X-ray lens,
classical micro-XRF, quantification is more laborious and the
was developed (52). This lens consists of two rows of prisms
results are less accurate. Nevertheless, 3D micro-XRF as a tool
facing each other at an angle arranged around the optical axis.
for the investigation of stratified materials is an alternative, if
The authors modified the original multiprism lens in a way that
sectioning of the sample has serious disadvantages or nondestruc-
introduced additional small gaps in a special arrangement. The
tive characterization is the only option. Further improvements
optics was combined with a tungsten target X-ray tube and an
concerning instrumentation as well as calibration will contribute
edge-on silicon strip detector. This imaging system was applied
to a wider applicability of this method and the quantification of
for a scanning mammography of an artificial tumor (3.17 mm complex stratified materials.
diameter) in a MEDITEST phantom. Kunimura and Kawai made A new indirect method for the determination of beryllium by
an X-ray refractive lens, which consisted of two sections each 5 XRF was proposed (57). The method is based on the determina-
mm long cut from a phonograph record (53). Tungsten foils (50 tion of beryllium via cobalt in the hexamminecobalt(III) carbon-
µm thick) were used as spacers between the two sections. The atoberyllate complex. Until now, direct determination of beryllium
groove pitch and depth of the record disk were about 120 and 30 by ED-XRF was impossible, and it is very difficult because of the
µm, respectively. In their portable TXRF setup, this refractive lens extremely low fluorescent yield, which is a major limitation of
was attached to the X-ray tube instead of a waveguide. It was sensitivity of wavelength-dispersive XRF (WD-XRF) for elements
confirmed that the spectral background was reduced by applying of low atomic number. This investigation developed a precise,
the refractive lens, leading to an increase in the signal to accurate, and selective procedure for determining beryllium that
background ratio. The detection limits for 3d transition metals can be applied to real samples with minor amounts of beryllium
were subnanograms to a few nanograms. such as, for example, beryllium alloys. A good ratio of beryllium
Dabagov explained X-ray waveguiding in narrow collimators to cobalt (1:3) and a very sensitive Co KR line gave a potential to
for micro- and nanofocusing by using the unified theory of X-ray determine beryllium in low amounts, even 28 ng, taking into
trapped propagation: surface channeling in microguides and bulk account the standard deviation of the X-ray background, but the
channeling in submicrometer (nano) guides (54). After introduc- process of precipitating the complex gave significantly poorer
tion of the basics of X-ray waveguiding, discussions on waveguid- results at the detection and determination limits. The minimum
ing in micro- and nanochannels in addition to tunneling and flux amount of beryllium in the form of this complex that could be
peaking for X-rays were given. This discussion would be useful precipitated was 0.2 mg, which was thereby the actual determi-
for developing waveguide optics and understanding the experi- nation limit of this method. The main advantage of the proposed
mental results obtained by the optics. Experimental results on method is that it enhances XRF capabilities for determination of
grazing incidence XRF (GIXRF) and EXAFS in a waveguide very light elements, undetectable by most commercially available
structure were shown (55). A layered material of SiO2 (substrate)/ XRF spectrometers.
Ta(35 nm)/a-Si(25 nm)/Co(5 nm)/a-Si(20 nm)/Ta(5 nm) was Vasquez (58) presented a quantitative analysis of XRF mea-
prepared by magnetron sputtering. In this material, the Ta surements of transmitting samples with complex chemical com-
layers were waveguide reflectors, Si was the spacer, and the position using a portable instrument for which the excitation
Si/Co/Si layers were the samples under test. An incident angle- source and detector are on opposite sides of a thin transmitting
dependent curve of XRF intensity of Co showed an oscillation sample. The proposed quantitative method is based on the
structure, which was compared the calculated curve with a Co fundamental parameter (FP) method and measured fluorescence
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4957
signal intensities and analytically calculates compositions from using the traditional calibration curve method and the gravimetric
transmitting samples with no measurement of standards and SAM approach. No significant difference was found between the
without being biased by matrix effects. As this work was the first two methods when measuring sulfur in petroleum diesel. How-
step in developing a formalism for X-ray quantitative analysis that ever, sulfur determinations in biodiesel using petroleum diesel
is applicable to transmission geometry measurements, it encoun- as a calibration material were lower by ∼19% relative to the
tered limitations that would be significant in many cases of interest gravimetric SAM at the 3, 7, and 12 µg/g levels. They claimed
and thus should be resolved. Ochi et al. (59) reported a that XRF using gravimetric SAM yields accurate sulfur measure-
quantitative analysis of an irregular shaped sample of lead in tin- ments in biodiesel samples.
plated electronic components. The FP method was used, using The quantification of XRF spectra is, in general, based on the
bulk solders as the standard sample. The scattered X-ray monitor use of appropriate RMs that are as similar as possible to the
method was also used to obtain the measured intensity ratio of sample to be analyzed, as the interplay of many often unknown
fluorescent and scattered X-rays to correct the results, as the instrumental and fundamental atomic parameters determines the
analyzed electronic components do not have a large and smooth measured element-specific fluorescence count-rates in a complex
surface suitable for quantitative analysis. An analytical result of manner. When the appropriate RMs are not available, standardless
6.0 µm film thickness and 1430 ppm lead concentration was (reference-free) XRF quantification is the other option. Beckhoff
obtained for a 5.4 µm thickness and 1388 ppm concentration (63) made an extensive introduction on the requirements for
sample using the scattered X-ray monitor method. standardless quantification in XRS that is based on both instru-
Intensity calculations of XRF mainly used nowadays consider mental and fundamental atomic parameters and on related
only the processes of atom photoionization by primary and instrumentation by the Physikalisch-Technische Bundesanstalt
fluorescence radiation. However, fluorescing atoms can be excited (PTB), Germany’s national metrology institute. The author
in other ways, one of which is atom ionization by photo- and Auger described the monochromatic excitation radiation of well-
electrons arising in the analyzed material. In the long-wave region characterized beamlines, reliable XRS instrumentation, and ab-
of the fluorescence spectrum, the accuracy of the results of solutely calibrated X-ray detectors for the nondestructive inves-
calculations is insufficient without taking into account this process. tigation of bulk and layered samples employed in PTB, claiming
In particular, photo- and Auger electrons make a significant that the overall relative uncertainty of its experimental data is
contribution to the excitation of low-Z elements. Thus, for carbon about 3%. In addition, several applications of standardless XRS
with the primary radiation of X-ray tubes, this contribution can quantification were described for studies in surface contamination,
be as high as 60-80% of the total fluorescence intensity. Pavlinskii depth profiling, bulk and layer analysis, and high-resolution
and Vladimirova (60) performed FP-based XRF analysis of materi- spectrometry. An ancient Chinese ceramic piece was investigated
als containing low-Z elements (fluorine, oxygen, nitrogen, carbon, to further develop and validate FP-based quantification procedures
and boron). It was shown by the examples of carbon and oxygen for standardless XRF analysis (64). XRF measurements of this
that the account of C and O atom ionization by photo- and Auger sample were performed at the four-crystal monochromator beam-
electrons of the irradiated sample was obligatory. If the contribu- line of PTB at the BESSY II SR facility employing different
tions for the test samples differ significantly, the computational excitation energies. The parallel processing of the XRF spectra
modeling of the effect of photo- and Auger electrons in the iterative recorded at different excitation energies provided a means to
process becomes necessary. simultaneously evaluate relevant FP and secondary enhancement
The effects of the absorption edge structure in XRF manifest processes such as those induced by photoelectrons. All experi-
themselves as a very strong attenuation of the analytical line mental parameters involved in XRF employ well-characterized and
radiation when it is in the X-ray absorption near edge structure absolutely calibrated instrumentation and are known for small
(XANES) range. Borkhodoev (61) investigated this effect exempli- relative uncertainties, allowing for completely standardless quan-
fied by an ultrastrong Ba-caused attenuation of the Ce Lβ1 line. tification. Apart from traces of rare earth elements, the analytical
Comparison of measured and calculated relative intensities results of the Chinese ceramic piece achieved by standardless
showed that the actual mass attenuation coefficient of the Ce Lβ1 XRF are in line with target values as given by a proficiency test
line in Ba is 1.6 times greater than known values. This is due to of the International Atomic Energy Agency.
the fact that the Ce Lβ1 line is within the initial range of the L3 Sitko et al. (65) developed an ED-XRF spectrometer for
Ba absorption edge, i.e., the XANES range. An effect like this of standardless analysis of samples of various sizes. In the con-
the absorption edge structure of atoms must be considered using structed spectrometer, the radiation from the Ag target X-ray tube
the FP method in quantitative XRF analysis. excites the secondary target and the characteristic radiation of
Sulfur in petroleum diesel is typically detected by WD-XRF by the second target, which is monochromatized using a LiF(200)
comparing the response of the unknown to a linear calibration crystal, excites elements in the analyzed sample. The X-ray spectra
curve composed of a series of matrix-identical standards. Because are collected by a thermoelectrically cooled Si-PIN detector. The
biodiesel contains about 11% oxygen by mass and petroleum diesel pinhole collimator placed in front of the X-ray detector allows the
is oxygen-free, the determination of sulfur in biodiesel by the size of the analyzed area to be reduced. The described ED-XRF
calibration using petroleum diesel is predicted to be biased ∼-16% system allows for obtaining very low levels of background signals.
due to oxygen absorptive attenuation of the X-ray signal. Barker Because the sample is excited using monochromatized radiation,
et al. (62) reported a gravimetric standard addition method (SAM) FP calculations are much simpler and analysis error resulting from
to overcome this bias as the method should be matrix-indepen- the uncertainty of X-ray tube spectral distribution is completely
dent. RMs both for petroleum diesel and biodiesel were analyzed eliminated. The use of the secondary target and an analyzing
4958 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
crystal in the spectrometer causes a loss of radiation intensity. improved description of the detector response can enable the
Thus, the spectrometer is recommended for the determination detection of minor components of characteristic lines in
of major and minor elements other than trace elements. Sitko (66) fluorescence spectra, which were attributed to the detector
also investigated the influence of X-ray tube spectral distribution earlier.
on the accuracy of the analysis of thin films and bulk samples With the advent of SDD, a range of new geometries has
using theoretical methods of matrix correction, i.e., FP methods become possible in electron optical columns. Because of their
and theoretical influence coefficient algorithms. The Fe-CrsNi compact size, these detectors can potentially achieve high geo-
system was investigated as an example, and the calculations were metrical collection efficiencies; however, with the use of traditional
performed for X-ray tubes commonly applied in XRF, i.e., Cr, Mo, approximations, detector solid angle calculations can rapidly break
Rh, and W. The influence of X-ray tube spectra on the FP analysis down. Zaluzec (69) presented generalized formulas that can be
of bulk samples was evaluated using pure-element and multiele- used to calculate the variation in detection solid angle for Si(Li)
ment bulk standards similar to the analyzed material, whereas and SDD configurations. With the use of this formulation, the
for FP analysis of thin films, the bulk and thin pure element development of new detector configurations, which range from
standards were used. Calculations showed that applying pure- ultrasmall to annular geometries and can achieve collection
element standards resulted in 5% relative error. Better results were efficiencies approaching several steradian, could be feasible. Also,
obtained when multielement standards similar to an unknown the generalized formulas provided an optimum specimen-to-
sample were used. XRF analysis of thin films using bulk standards detector distance for annular configurations that maximizes their
leads to unacceptable errors, especially in the determination of effective solid angle.
sample thickness. The errors resulting purely from X-ray tube Although WDS has been the preferred technique because of
spectral distribution exceeded 10% relative. For the evaluation of its higher spectral resolution and ability to detect trace elements,
the influence of X-ray tube spectra on XRF analysis performed by new-generation EDS with SDD, equipped with thin windows and
theoretical influence coefficient methods, two algorithms for bulk integrated digital processing electronics, are claimed to approach
samples and two algorithms (constant and linear coefficients) for the WDS throughput. Cubukcu et al. (70) compared the analytical
thin films were evaluated. The results showed that the differences capability of a SDD-EDS with respect to WDS using natural silicate
between coefficients calculated using experimental and theoretical minerals. SDD-EDS yielded satisfactory results for major elements
X-ray tube spectra were considerable. (Na, Mg, Al, Si, K, Ca, Ti, Mn, and Fe) compared with the results
For FP-based quantification, detailed knowledge of the char- of the same minerals obtained by various WDS systems. Regard-
acteristics of the detector, including efficiency, energy resolution, ing the fact that WDS needs longer time for analyses (3-7 min
and the precise shape of the response function, is essential. depending on the number of installed spectrometers), SDD-EDS
Trincavelli et al. (67) presented a method for the experimental systems can yield comparable results in 30-35 s thanks to their
determination of the absolute efficiency of WDS, based on the impressive count rates and enhanced signal processing electron-
comparison of spectra measured with a WDS and with an EDS. ics. Considering the cost of purchase and maintenance, SDD-EDS
For WDS spectrometers, the efficiency εWDS is difficult to predict, systems seem to be advantageous as rapid, accurate, and
as it depends on the quantum efficiency of the proportional economical solutions for detecting mineral compositions with
counter, on geometrical factors, and on the reflectivity of the major elements.
analyzing crystal. A simple analytical expression was obtained An FP approach that explicitly incorporates the energy-
for the efficiency curve for three crystals (TAP, PET, and LiF) broadening response of the detector has been reported (71). The
with the spectrometer used, within an energy range from 0.77 ratio between the KR fluorescence peak area and the sum of
to 10.83 keV. Although this expression is specific for the system coherently and incoherently scattered peak areas was used as an
used in their work, the method may be extended to other indicator of trace element concentration. The peak ratio was
spectrometers and crystals for EPMA and XRF. Scholze and theoretically calculated using FPM. The energy-broadening re-
Procop (68) presented an analytical description of the physical sponse curve of the Si(Li) detector was estimated by matching
processes determining the spectral response of an EDS with a the theoretical and experimental values of this ratio. The method
silicon detector (Si(Li) or SDD). The model considered the was implemented for the analysis of the K-shell XRF spectra of
detector statistical noise, the electronic noise, the incomplete six polyester resin samples corresponding to six different arsenic
charge collection that gives rise to the peak tailing, the escape concentrations. A 109Cd radioactive source provided the excita-
effect, the fluorescence of the front contact or the dead layer, tion radiation for spectra acquisition. The predicted detector
and hot photoelectrons that cause the shelf. Only five free energy resolutions, expressed as fwhm, for Fe KR fluorescence
parameters were claimed to be necessary to model the peak (208 ± 5 eV at 6.4 keV) and As KR fluorescence peak
response function: electronic noise, three parameters describ- (222 ± 5 eV at 10.5 keV) were in agreement with the
ing the shape of the charge collection efficiency beneath the experimental measurements. The method was further devel-
front contact, and the thickness of the detector front layer. The oped for the XRF analysis of arsenic depth-dependent concen-
algorithm was implemented in IDL and MATLAB and is tration in polyester resin disks (72). Experimental trials with
available as a MATLAB stand-alone program. The calculated two-disk stacks of various arsenic concentrations validated the
response functions were in agreement with the pulse height model for the case of two homogeneous layers. Future
distributions measured with monochromatic SR in the energy experiments and applications such as the measurement of
range from 0.1 to 10 keV for three spectrometers with detector arsenic in skin could make feasible the model to account for
crystals of different constructions, demonstrating that the more realistic elemental distributions. The authors also re-
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4959
ported a modified analytical method of the traditional FPM,
which assumes the parallel paths both of incident and emerging
photons, in order to account for nonparallel X-ray beams (73).
For a given direction of the excitation photons, the fluorescent
photons can travel in any straight pathway from the point of
origin to the detector if not scattered or absorbed. For each
point of origin of the fluorescence radiation, the average
attenuation factor for fluorescent radiation and the correspond-
ing solid angle were calculated using analytical geometry
techniques. The XRF signal was then computed as an integral Figure 5. Schematic representation of the experimental setup. (A)
over all points of origin on the pathway of the incident photon. The incoming hard X-ray beam is focused on the specimen. A pixel
The derived XRF signal equation explicitly depends on the array detector records a complete oversampled diffraction pattern for
each raster position of the specimen. (B) Example of diffraction
length of the collimator in front of the detector, the detector
patterns. The color scale is logarithmic, and the units are in photon
size, position, and orientation. An algorithm which numerically counts. The focused beam geometry generates a diverging beam past
calculates the XRF signal for any set of parameters was the specimen, thereby removing the need for a beam stop at the
developed and implemented for the KR XRF signal of arsenic detector. From Thibault, P.; Dierolf, M.; Menzel, A.; Bunk, O.; David,
in skin, providing optimal positions and orientations of the C.; Pfeiffer, F. Science 2008, 321, 379-382 (ref 77). Reprinted with
permission from AAAS.
detector and collimator ensemble for the maximum XRF signal.
Silicon diodes have traditionally been the detectors of choice
X-RAY IMAGING
for quantitative X-ray spectroscopy, but they have limited sensitiv-
If X-rays with a well-defined wavefront were generated, they
ity at energies above 30 keV. Recent environmental regulations,
are coherently diffracted by an object even only a micrometer in
such as Europe’s RoHS (Restrictions on Hazardous Substance)/
size. The coherent X-ray diffraction pattern is speckled when the
WEEE directives, require nondestructive measurement of heavy
sample is disordered. The speckled pattern, which is finely
metals such as lead and mercury with K X-ray emissions well
recorded enough to satisfy the oversampling condition, can offer
above 30 keV. Redus et al. (74) investigated a CdTe detector for
a real-space image by retrieving the phase using an iterative
quantitative X-ray spectroscopy which has much higher stopping
method. Nishino et al. visualized a 3D image of an unstained
power, making it an attractive alternative in these applications.
human chromosome using coherent X-ray diffraction (76). The
For a 5 mm × 5 mm × 0.75 mm device, with a Schottky diode
reconstructed 3D electron-density map of the unstrained human
structure and Peltier cooling, electronic noise was around 500 eV,
chromosome showed relatively high density near the central axis
providing adequate energy resolution for distinguishing peaks of of each chromatid. They claimed that the X-ray coherent diffraction
interest. However, the response function of a CdTe detector has would allow noninvasive analysis of thicker biological objects, to
some important differences from that of Si detectors, and these which electron tomography is hardly applicable. Thibault et al.
differences must be understood and quantified to achieve accurate combined coherent X-ray diffractive imaging and scanning trans-
results. Redus et al. discussed several important effects in the mission X-ray microscopy (STXM) (77). Although the resolution
response of CdTe, including hole tailing due to poor charge of the STXM was limited by spot size on the specimen, coherent
transport, escape peaks, spectral background, linearity, and X-ray diffractive imaging reached a resolution below 10 nm. They
stability. measured complete coherent diffraction patterns from the test
A quantitative model that describes confocal micro-PIXE data specimen of a FZP at each point of a scan. In their article, a
for stratified materials was proposed by Sokaras et al. (75). The reconstruction example, from a 61 × 61 subset of the 201 × 201
model incorporates the effect of the finite ion microbeam dimen- diffraction patterns data set, was shown in Figure 5. In the
sions and the restricted spatial resolution of an X-ray lens to reconstruction, the outermost rings of the zone plate (70 nm wide)
generate the sensitivity function of the confocal setup probing a were very well resolved. This method will enable investigation of
microvolume in a closed form. The Gaussian-like dependence of a wide range of complex mesoscopic life and material science
the sensitivity function was validated for the case that the proton specimens with high spatial resolution. The coherent diffractive
microbeam size is much smaller than the lateral size of the lens imaging by Nishino et al. and Thibault et al. employed small angle
field of view in the focal point. Among the experimental param- scattering although coherent diffractive imaging was realized by
eters, the angles that the beam direction forms with the sample using Bragg reflections from the nanocrystalline. Robinson and
surface and the detector, respectively, are critical and may his co-workers investigated this method and explored its possibil-
considerably improve the sensitivity of the confocal micro-PIXE ity for strain at the nanoscale. In their review article in Nature
technique. For various cases of stratified materials, the simulated Materials (78), they explained how they solved the phase problem
intensity profiles and 2D elemental maps demonstrated that even by coherent diffractive imaging and sensitivity to lattice strain.
the raw confocal micro-PIXE data include unique analytical They also showed examples of 3D visualizations of strain inside
information that may provide the first clues of the structure of Pb and Au nanocrystals. In the reconstruction of the strain of the
the analyzed sample. In comparison with differential PIXE, in Pb nanocrystal, the contact strain due to the substrate and the
principle, the confocal micro-PIXE technique seems to exhibit an surface strain were clearly visualized. Such a coherent diffraction
enhanced sensitivity with respect to spatial resolution, which technique, known as coherent diffractive imaging, is ultimately
should be proved in practice by the analysis of the same real expected as atomic resolution 3D imaging. A major difficulty in
sample by both techniques. atomic resolution imaging is loss of weak coherent scattering
4960 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
signals in recorded diffraction patterns. Huang et al. proposed that holography using magnetic circular dichroism. Also, Günther et
this could be resolved by combining the information of both al. investigated the microscopic reversal behavior of magnetic
diffraction and low-resolution imaging (79). The low-resolution domains in Co/Pd multilayer films (83). They measured the
image, which was obtained from different sources, provided the holograms at the Co-L3 edge under the magnetic field and
starting phase, real-space constraint, missing information in the observed propagations of the domains from their reconstruc-
central beam, and essential marks for aligning the diffraction tions. X-ray Fourier-transform holography is a promising
pattern, and the resulting diffraction provides high-resolution technique for nanoscale imaging but, so far, is too inefficient.
information. They demonstrated the phasing of experimental Marchesini et al. proposed massively parallel X-ray holography
electron diffraction patterns of an individual CdS quantum dot and to improve the efficiency significantly by orders of magnitude
the improved image resolution, which enabled determination of (84). They placed a uniformly redundant array next to the
the atomic structure. The above-mentioned coherent diffractive sample and simultaneously illuminated both of them with a
imaging will be greatly improved by an XFEL owing to its high coherent X-ray beam. The Fourier transform of their diffraction
coherency and ultimately strong intensity. For the first time ever, pattern yields an autocorrelation map with a holographic term
the Linac Coherent Light Source (LCLS) at the SLAC in California displaced from the center. They demonstrated this method by
successfully generated the brightest X-ray pulses, jumping almost imaging a nanofabricated object at a synchrotron source at
9 orders of magnitude beyond current synchrotron-based X-ray Berkeley’s Advanced Light Source (ALS) and a bacterial cell
facilities. The Japanese compact XFEL at the Riken Harima with a soft-XFEL at the Free-Electron Laser in Hamburg,
Institute and the 3 km-long European XFEL in Hamburg are FLASH, where illumination by a single 150 fs pulse was
currently under construction. Chapman commented on the successfully used in producing the hologram image.
feasibility of imaging macromolecules, such as a virus, from recent The X-ray holography of refs 83 and 84 is analogous to classical
experiments and simulations (80). optical holography, and neither of their spatial resolutions can
X-ray radiographic absorption imaging has been widely used reach the atomic one. On the contrary, atomic resolution holo-
in medical diagnostics since Röntgen discovered X-rays in 1985. graphy using secondary emission does exist such as XRF. XRF-
However, for biological tissue samples, polymers, or fiber com- holography (XFH) measures the intensity modulation of the XRF
posites, which primarily consist of light elements, conventional as a function of the direction of the incident X-ray beam or the
X-ray radiography is limited due to their weak absorption. This XRF and provides three-dimensional images around specified
problem is resolved by phase-sensitive imaging methods to elements by a simple Fourier transformation-like reconstruction
improve contrast. Pfeiffer et al. have developed phase-sensitive algorithm. Hu et al. measured Fe KR XRF holograms of the
imaging using a grating interferometer (81), and recently they martensitic material of Ti50Ni44Fe6 at 225 and 100 K, which
reported a new approach based on a grating interferometer that corresponded to parent and commensurate phases, respectively
can efficiently yield high-quality dark-field scatter images with hard (85). They found that the first neighbor Ti atoms around Fe,
X-rays. The setup consisted of a source grating close to the X-ray fluctuating in the parent phase, were strongly stabilized in the
source, a phase grating, and an analyzer grating. A specimen was commensurate phase and that a clusterlike structure with a
placed in front of the phase grating. Dark-field images of a Teflon radius of 0.8 nm was formed in this lower temperature phase.
plastic tube and chicken wing were successfully demonstrated. These findings offer an important key to understanding the
In contrast to exiting crystal-analyzer-based methods, their method precursor to the martensitic phase transition of the shape
was implemented efficiently with a standard X-ray tube. Combining memory alloy TiNi series. Kopecky et al. proposed and put in
a grating with a FZP, Yashiro et al. developed hard X-ray phase- practice the method of X-ray diffuse scattering holography
difference microscopy (82). This method, which uses an objective using anomalous scattering from the atoms of the selected
and a transmission grating, was devised based on the Talbot effect. element measured on a spherical surface in the reciprocal
The microscope generated twin features of a sample image space. Extending this idea, they developed multienergy anoma-
(polystyrene spheres and a micrometer-thick Ta Siemens star lous diffuse scattering for local atomic structures, which can
pattern were used as samples), which were processed to generate map a three-dimensional region of the reciprocal space by
an image mapping the X-ray phase shift through a simple measuring X-ray diffuse scattering patterns at different sample
algorithm. Sensitivity in the phase-difference image was about 2 orientations (86). The phase problem was solved by means of
orders of magnitude greater than that of the absorption-contrast anomalous scattering at X-ray energies near the absorption
X-ray microscopy that was attained by simply removing the edge. They demonstrated multienergy anomalous diffuse scat-
grating. Furthermore, the grating did not degrade the spatial tering by a real-space reconstruction of the average short-range
resolution of the images. order atomic arrangement around strontium in a SrTiO3 single
Although coherent diffractive imaging offers a real-space image crystal.
of a specimen from a diffraction pattern alone, it requires a Combining XRF with the computed tomography technique
complex iterative phase retrieval algorithm. X-ray holography, enables establishing a low-invasive or nondestructive cross-
which records an interference of a reference simple spherical or sectional imaging method for biological use at high sensitivity and
plane wave and diffracted wave from an object, can reconstruct high spatial resolution. Huo et al. developed a fluorescence
an unambiguous image of the object using a simple Fourier computed tomography imaging system using thin incident beams.
transformation. On the basis of Fourier transform holography, a However, the system required a very long time to obtain a whole
group at Berliner Electronen-Speicherring Gesellschaft Gesell- set of projections. Thus, they proposed a novel imaging geometry
schaft für Synchrotronstrahlung (BESSY) has developed spectro- using sheet incident beams and detector array and performed a
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4961
proof of concept experiment at beamline BLNE-5A, KEK, Japan module, modified from the previous version, had a Peltier cooled
(87). The efficacy of the system was demonstrated by reconstruct- SDD (active area, 10 mm2; energy resolution, 140 eV at 5.9 keV;
ing images of a physical phantom containing various concentra- 8 µm-Be window). An X-ray CCD camera was also attached
tions of an iodine solution and a mouse brain that was extracted for beam adjustment. A monochromator (Mo/Si multilayers)
after intravenous injection of 127I-IMP. De Nolf et al. developed was used for monochromatic excitation with Mo KR emitted
micro X-ray tomography combined of XRD and XRF, which from a Mo (3 kW) fine focus tube. The standard 30 mm round
enabled visualization of the distribution of chemical elements quartz, Si wafer, and Plexiglas reflectors were used for sample
and associated crystalline phases inside complex, heteroge- carriers. A low-background intensity was detected in TXRF
neous materials in a nondestructive fashion (88). A paint layer spectra in vacuum. The detection limits were evaluated by using
system of eight layers with thicknesses of around 100 µm was a standard reference material, NIST 1640. A sensitivity of 70
investigated using this tomography technique. In the XRF cps/ng for Rb and a detection limit of 2 pg were reported.
tomograms, significant self-absorption distorted the element- The same group at the Vienna University of Technology
specific tomograms corresponding to the low energy (<7 keV) presented a review article on SR-induced TXRF (93). SR is an
characteristic radiation, limiting their usefulness. While, in the optimal excitation source for TXRF because energy-selective
XRD tomograms, all paint layers could be easily distinguished. monochromatic brilliant X-rays can be used. They explained how
They concluded that quantitative determinations of the elemen- the detection limit could be improved in TXRF. To reduce the
tal and crystal-phase content of each layer is possible by means background intensity, the total reflection geometry is, of course,
of a combination of microbeam-based XRF and XRD tomography. useful as well as linearly polarized primary radiation. Effective
Saito et al. have attempted to develop a new method of STM excitation of XRF can be achieved with the use of optimal energy
combined with SR for elemental analysis of solid surfaces at the excitation. Although the adjustment of X-ray energy for excitation
nanometer scale (89). They demonstrated this SR-STM system is difficult, SR enables adjustment of the energy of the X-rays to
by elemental imaging of a Cu nanodomain. A lock-in amplifier just above the absorption edge of the element of interest with
was used for extracting differential tip current between under brilliant intensity. Detection limits in the femtogram range could
irradiated and nonirradiated conditions. The differential tip current be achieved. XAS under total reflection conditions was additionally
was changed depending on whether the X-ray energy was above possible at SR facilities for chemical characterization at trace levels.
the X-ray absorption edge. In the experiment using a Cu nan- SR-induced TXRF and grazing incidence XAS measurements
odomain, the Cu island in the SR-STM image was darker than were performed at the Stanford Synchrotron Radiation Facility
the surrounding area at an X-ray energy above the Cu K (SSRF) by a European group (94). They measured mineral dust
absorption edge. At an X-ray energy below the Cu K absorption particles extracted on a Si wafer from the Antarctic and from an
edge, such a contrast could not be seen. Most recent advances
Alpine deep ice core. A high precision micropositioner was
have been performed with SR. However, in-house X-ray imaging
installed in a high vacuum chamber (10-7 Torr). The manipulator
is also important because of its accessibility. Hoshino and Aoki
had six degrees of freedom with high precision (<1 µm
developed a laboratory-scale soft X-ray imaging microtomography
accuracy for three directions), while it had a large translation
system with Wolter mirror optics (90). Quasi-monochromatic
range of 25 mm (x, y directions) and 50 mm (z direction). Fe
X-rays with a wavelength of 3.2 nm were generated using laser
inclusion of the 1-10 µg range was detected. XANES measure-
plasma from a tantalum target. To improve spatial resolution, a
ment gave information of Fe oxidation and the coordination
relayered tandem configuration with three mirrors was adopted.
state, while XAS gave local and species-selective information.
With measurement of some test patterns, it was known that a
A portable waveguide TXRF spectrometer (9 cm × 23 cm × 30
spatial resolution of 250 nm was achieved. Some naturally dried
cm) was developed by Kunimura and Kawai (95). They were able
biological cells were observed, and images of their 3D volume
to simultaneously conduct trace elemental analyses with a compact
were obtained with good resolution.
instrument. To be made more compact, the X-ray path between
the X-ray tube and the sample was reduced, leading to primary
TOTAL REFLECTION X-RAY FLUORESCENCE
ANALYSIS X-ray excitation with sufficient intensity. They also used strong
TXRF is a well-established analytical technique. In the initial white X-rays emitted from a compact X-ray tube (9.5 kV in the
stage of TXRF research, a TXRF instrument was developed for present paper) with waveguide optics, which produced a sheet-
contamination control of Si wafers. The instrument has been type X-ray beam for TXRF excitation. As a result, detection of
routinely applied in Si semiconductor companies. The 12th nanograms of rare earth elements was achieved. They optimized
Conference on TXRF and Related Methods was held in Trento in the incident angle of the X-ray beam produced by the waveguide
Italy in 2007. The conference proceedings were published in a optic (96). The critical angle for total reflection of 9.5 keV X-rays
special issue of Spectrochimica Acta, Part B (91). The reader can was 0.2° on quartz. They concluded that the optimal incident angle
learn of the research trends of TXRF from these proceedings. The was 0.13°. The detection limits were subnanograms to 10 nano-
applications of TXRF for trace analysis of various types of samples grams for Ca, Sc, Ti, V, Cr, Mn, Fe, and Ni.
have been increasing, especially in the laboratory. Trace analysis Yang et al. developed a laboratory TXRF instrument by using
of light elements was one of the remaining problems of TXRF. a polycapillary X-ray lens for excitation (97). They have studied
European researchers leading on TXRF analysis, Wobrauschek the development of various polycapillary optics and their applica-
et al. developed a TXRF attachment module for analysis in a tions. A polycapillary half lens was used to have a parallel X-ray
vacuum (92). They developed a low-cost TXRF attachment that beam collecting the strong X-rays emitted from a point source in
could be installed in the X-ray tube. The newly developed TXRF the X-ray tube. The X-ray emission source (0.3 mm × 0.3 mm)
4962 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
was a rotating anode target X-ray tube operated at 35 kV and 50 excitation with a micro X-ray beam can be combined in GE-XRF.
mA. The polycapillary half lens (focal distance, 70 mm; length, Yang et al. produced an X-ray microbeam using polycapillary X-ray
47 mm) collected the X-rays from the Mo target and produced a optics (104). This X-ray microbeam irradiated a sample surface
parallel beam with a Zr filter (70 µm) instead of a monochromator. at a right angle. The X-ray fluorescence was measured through
A microparallel beam was produced by a pinhole of 0.02 mm × an exit slit by a Si-PIN detector at a small exit angle, which was
0.05 mm. The divergence of this beam was 0.6 mrad. They showed controlled by a rotating stage. The authors applied GE-micro-XRF
clear angle-dependent curves for an Fe thin layer (10 nm) on a Si for the analysis of thin films on a GaAs substrate. Two-dimensional
substrate. It was confirmed that a polycapillary X-ray lens was scans for Fe KR and Ti KR in the double-layered films were
useful as a collimator in a TXRF instrument. obtained and the uniformity of the film was discussed. A Japanese
When the X-rays are totally reflected on a flat substrate, an group also applied the GE-micro-XRF technique for elemental
interference phenomenon between the incident primary X-ray analysis of hazardous metals attached to a plant leaf surface (105).
beam and the reflected X-ray beam occurs, leading to an XSW on Similar to the previous work (104), they applied an X-ray
the substrate. The period of the standing wave changes drastically microbeam produced by polycapillary X-ray optics. XRF was
with the incident angle. Therefore, the intensity of the XRF emitted detected by SDD at a small exit angle, which was controlled by
from the sample on the substrate also depends on the incident moving the SDD and the exit slit using a z-axis translation stage.
angle. This X-ray standing analysis is useful for the structural They proposed the use of an X-ray absorber to improve surface
analysis of layered material on a flat substrate. This technique sensitivity in GE-micro-XRF.
was applied for the study of the self-assembling process in a
ELECTRON PROBE MICROANALYSIS
protein-lipid film on a water subphase (98). The authors proposed
A quantitative single-particle analytical EPMA technique using
a four-layered model of the protein-lipid film; the thickness of
SEM equipped with thin-window EDX, called low-Z particle EPMA,
each layer was evaluated by XSW measurement. von Bohlen et
where elemental concentrations of individual particles are deter-
al. applied the XSW technique to Au nanoparticles (99). They
mined from their X-ray intensities by the application of a MC
considered the influence of X-ray coherence length, particle size,
calculation combined with reverse successive approximations, has
particle shape, and distribution in the intensity in the XSW
been widely used for the characterization of atmospheric aerosol
measurement. They pointed out that the coherent length under
samples for a decade. In the quantitative single particle analysis,
the normal SR-TXRF condition was 350 nm, i.e., XSW is observed
number concentration data for chemical species encountered in
in a small volume above the reflector. The simulated XSW-scan
aerosol samples are provided. However, it will be more useful if
curve fitted well with the experimental plots.
mass concentration data can be obtained from single particle
Wellenreuther et al. investigated the influence of heterogeneity
analysis; i.e., the single particle analysis data for weight fractions
of the dried residues and the separation of the internal standard of chemical species can be complementarily used in combination
and the analyte (protein) on TXRF analysis (100). The shape of with bulk analysis data for a more clear understanding of the
the dried residue critically depends on the chemical properties behavior of airborne aerosols. In order to investigate how reliably
of the surface of the sample carrier. They concluded that mass concentration data can be obtained from quantitative single
siliconized quartz is the best material for a sample carrier of TXRF particle analysis, a potassium feldspar powdered RM, of which
analysis to obtain the homogeneous residue from the sample elemental weight fractions are well-defined by various bulk
solution and to obtain the most reliable TXRF result. Researchers analytical techniques, was analyzed using the low-Z particle EPMA
in Greece developed a new sampling technique for TXRF (101). technique (106). That work demonstrated that weight fractions
They produced an anion-selective membrane on a quartz reflector. of major elements in the powdered RM sample obtained by the
This membrane contains a few micrograms of different complex- low-Z particle EPMA were within 8% of the certified values
ing reagents in polyvinyl chloride (PVC) matrix. The reflector with obtained by bulk analytical techniques, although the single particle
the membrane was immersed in the sample solution, and then and bulk analyses employ different approaches. Further, it was
the dried reflector was analyzed by TXRF. Detection limits of 1 shown that the quantitative single particle analysis can provide
ng/mL level were obtained for several elements. The same molecular mass concentration data for chemical species, which
research group developed a selective membrane for Cr(III) and is not easy to obtain using bulk analysis.
Cr(VI) and applied it for chromium speciation by TXRF analysis SEM/EDS can provide morphological and elemental chemical
(102). compositional data of individual particles. However, if molecular
Uncertainty in quantification by TXRF was studied theoretically speciation of the individual particles in addition to elemental
(103). The contributions of the internal standard concentration, concentrations can be performed, greater insight on the nature
net intensity, and relative sensitivity to the uncertainty were of atmospheric particles can be obtained. One approach includes
considered. The author proposed two theoretical models and a technique that employs the combined application of SEM/EDS
compared the results with experimental data. It was emphasized and µ-Raman spectrometry for the same atmospheric particle.
that the roughness and small geometrical variations of the sample During the review period, another analytical methodology was
setup would be more important uncertain sources in TXRF reported (107), which combined SEM/EDS and attenuated total
measurements. reflection FT-IR (ATR-FT-IR) imaging techniques for the analysis
At the end of this subsection, the technique related to TXRF, of the same individual particles. The authors claimed that these
a grazing exit XRF (GE-XRF), is introduced. In GE-XRF, XRF is two single-particle analytical techniques provided complementary
detected at a small exit angle. As a result, surface-sensitive analysis information on the physicochemical characteristics of the same
is achieved. One of the unique advantages over TXRF is that individual particles, that is, the low-Z particle EPMA giving
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4963
information on the morphology and elemental concentration and processing of experimental results. The results of the MC
the ATR-FT-IR imaging showing functional group, molecular calculation of the depth distribution of X-ray radiation generated
species, and crystal structure. The ATR-FT-IR imaging technique in the sample were used in the processing. The technique allowed
was reported to provide sufficient FT-IR absorption signals to for the estimation of the parameters of the depth distribution of
perform molecular speciation of individual particles of micrometer elements in the sample under study. The results obtained were
size when applied to artificially generated aerosol particles such in good agreement with the data of other analytical methods
as ascorbic acid and NaNO3 aerosols. An exemplary indoor (SIMS, TEM). The possibility of determining the sought distribu-
atmospheric aerosol sample was investigated to demonstrate tions rather rapidly without sample destruction allowed control
the practical feasibility of the combined application of the ATR- of technological processes of complex semiconductor structures.
FT-IR imaging and low-Z particle EPMA techniques for the Scott and Ritchie (111) demonstrated that NISTMonte for the MC
characterization of individual airborne particles. simulations can be a useful tool for 3D elemental analysis of
With the advent of fast computers and affordable memory biological samples using the focused ion beam (FIB) based X-ray
storage, the utilization of MC simulations in quantitative EPMA microanalysis technique. NISTMonte provides a framework to
becomes a practical tool. MC-based quantification methods can define complex sample geometry into a hierarchy of overlapping
provide the most versatile approach for quantification, especially regions and specify the material properties for each region. For
for samples with complex geometries or for unconventional a marine diatom Thalassiosira pseudonana used as a model
measurement conditions. Ritchie (108) introduced software for organism, X-ray mapping performed using the 5 keV beam energy
EPMA, called DTSA-II, that provides both easy-to-use and flexible resulted in 3D elemental distributions that closely reflect the
tools for simulating common and more complex sample geom- elemental distributions in the original model. At 5 keV, the depth
etries and materials. Analytical models based on φ(Fz) curves resolution of the X-ray maps was about 250 nm for the model
provide quick simulations of simple samples. MC models based organism. It was shown that nanoparticles that are 50 nm or
on electron and X-ray transport using the NISTMonte algorithms greater in diameter were easily located. Much work is still needed
provide more sophisticated models of arbitrarily complex samples. in generating more accurate biological models and simulating
The examples demonstrated that DTSA-II MC is capable of experimental conditions relevant to these samples.
modeling gross features and is more than sufficient for answering EPMA of stratified specimens has been intensively developed
many of the questions for which one might turn to simulation. during the last few decades. The homogeneous bulk assumption
DTSA-II was developed in Java for a high level of platform used in traditional EPMA can be applied for thin-layered systems
independence and available free from the NIST Web site. Ar- with individual layers as thick as 50 nm if the penetration depth
migliato and Rosa (109) applied their MC computer model and of the lowest accelerating voltage exceeds the total film thickness.
so-called “2-tilt-angle” method for X-ray microanalysis of plain In cases where the same element is present in multiple layers
sections consisting of bilayers and triple layers using transmission or in the substrate as well as the film, the homogeneous
electron microscope (TEM). To test the validity of the method assumption in EPMA alone is not sufficient to determine composi-
for quantification purposes, a commercially available NiOx tion. Phung et al. (112) developed an approach to the problem of
(x ∼ 1) thin film, deposited on a carbon layer, was analyzed. multiple layers containing the same element for the case of
The composition and thickness of the NiO film and the ultrathin films by using both X-ray reflectivity (XRR) and EPMA
thickness of the C support layer were obtained by fitting to in tandem. XRR is an accurate technique for the determination of
the three X-ray intensity ratios, i.e., I(Ni K)/I(O K), I(Ni K)/ film thickness, and if the composition is known, the critical angle
I(C K), and I(O K)/I(C K). The extent to which the resulting of the reflectivity scan can determine the density. EPMA, on the
film composition is affected by the presence of a contaminating other hand, gives accurate compositional information if the thin
carbon film at the sample surface was also investigated. For film thickness and density are known. This technique was utilized
reliable analysis, a carbon contaminating film of a few tens of to determine the composition of Ni-Si ultrathin films grown on
nanometers as well as the C support film must be considered. silicon. The Ni-Si composition determined using this multi-
By assuming the proper C/NiOx/C stack in the simulations, instrumental technique matched that of Ni-Si films simulta-
the MC method yielded the correct oxygen concentration and neously deposited on GaAs.
thickness of the NiOx film. The ultralight element Li has attracted attention as an important
When various technological processes of semiconductor struc- element for various industrial fields. However, Li is also well-known
tures are developed, such as implantation, diffusion, and epitaxy, as one of the most difficult elements for X-ray chemical state analysis.
depth profiling analysis, i.e., the determination of concentration Ogiwara et al. (113) reported a general-purpose electron beam
profiles of components in the surface layer 0.1-1.0 µm deep, is excitation ultrasoft X-ray analyzer with a newly designed high-
required. One of the most promising nondestructive methods for resolution flat-field VLS grating spectrometer for the analysis of the
solving this problem is EPMA. In this method, the thickness of ultralight elements, such as Li and Be. To obtain the practical yield
the analyzed layer depends on the electron probe energy and can of ultrasoft X-rays (<100 eV), electron beam excitation using a field-
vary from 50 nm to several micrometers. The penetration depth emission type electron gun was utilized in this system. They
of electrons increases with their energy, which makes it possible demonstrated that the spectrometer has a sufficiently high energy
to analyze increasingly deeper layers, hence, to determine resolution and a high sensitivity using metallic Li and worked well
concentration depth profiles of elements. Bakaleinikov et al. (110) for the chemical state analysis with Al-LR.
proposed a depth profiling technique of structures based on The importance of electron bremsstrahlung has continuously
varying the energy of primary electrons followed by mathematical grown and has being increasingly involved in different scientific
4964 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
areas. Trincavelli and Castellano (114) have a review on the SEMs, and atomic force microscopes (AFM) were able to image
prediction of thick target electron bremsstrahlung spectra in the the ROI without requiring special chemical processes or conduc-
0.25-50 keV energy range. Developments carried out from tive coatings.
theoretical bases were considered, as well as the role played by
MC simulations. They claimed that only empirical models have PARTICLE-INDUCED X-RAY EMISSION
Particle-induced X-ray emission (PIXE) is well-known as a trace
succeeded to provide analytical expressions for prediction of the
analytical method. This is because the continuous background
continuum spectrum in a wide range of experimental situations
intensity in the PIXE spectrum is originally low. Continuous X-ray
as a function of atomic number, incident energy, and photon
produced in light-ion atom collisions was experimentally and
energy. Further developments based on theoretical considerations
theoretically studied (117). The authors measured continuous
will need to include a reliable study on the generated bremsstrahl-
X-ray spectra from Ag and Au targets with 1.5 MeV protons. It
ung spectrum, i.e., avoiding inaccuracies inherent to backscatter-
was found that the experimental production cross section of
ing, absorption, and efficiency corrections. Recent advances in
continuous X-rays were much smaller than the theoretical predic-
MC methodology appear as a promising tool to perform “con- tion based on the plane wave Born approximation. By application
trolled experiments,” allowing an appropriate description of the of the binary encounter approximation, experimental cross sec-
different corrections applied. tions could clearly be theoretically explained.
In WD-EPMA, quantitative analysis is traditionally based on Alberti et al. developed a new detection module based on an
the measurement of X-ray intensities from RMs. Unfortunately, SDD (sensitive area, 10 mm2; thickness, 450 µm) and an X-ray
in some situations, RMs are not easily available for measure- polycapillary lens (IFG GmbH, Berlin) for PIXE analysis (118).
ment. In such cases, standardless methods of analysis would The polycapillary X-ray lens was attached to an SDD to collect
be a suitable alternative but since these methods require X-rays. The performance of the detector module was investi-
accurate knowledge of the proper instrumental and physical gated at the external collimated beamlines of a 3 MV Tandetron
parameters to begin with, the accuracy of such methods is accelerator. PIXE spectra were collected with and without the
generally poor. One possibility to overcome this difficulty is to polycapillary optics. It was found that the continuous back-
perform reference measurements in one laboratory and transfer ground intensity was reduced by using the polycapillary optics.
them to other instruments. To do that, X-ray intensities have The focal spot sizes on the sample were 1.6 mm at 1 keV (Zn
to be converted into absolute units. Merlet et al. (115) tested L line) and 0.7 mm at 8.6 keV (Zn K line). A paint layer was
a calibration method aimed at converting X-ray intensities into measured with a high-quality PIXE spectrum in the low energy
absolute units in different electron microprobes. The calibration region including Na.
requires measurement of the X-ray peak profile and measure- Žitnik et al. developed an elemental selective 3D imaging
ment and calculation of the bremsstrahlung intensity emitted technique with confocal micro-PIXE (119). They used a 3 MeV
from a reference sample at the energy of the X-ray line of microproton beam with a size of 1.6 µm × 2.4 µm. A polycapillary
interest. Specifically, measurements of the U MR and Mβ lines X-ray lens was attached to a Si(Li) detector. This polycapillary
emitted from UO2 and bremsstrahlung intensities emitted X-ray lens showed a lens focus of 26 µm at 8 keV. Aerosol samples
from an Al reference sample were performed on five different were collected in a filter by using a pumping system, and the size
instruments. The absolute intensities of the U MR and Mβ was selected by using an impactor. Elemental maps for Fe, Ca,
X-ray lines emitted from reference samples of UO2 can be and Si were obtained at different depths for the collected aerosol
samples. Researchers in the U.K. obtained 3D quantitative
transferable with an uncertainty of 7% among different
elemental maps of a section of a strand of hair by PIXE
electron microprobes using WDS of the other kind. They
tomography (120). The strand of hair was inserted in a thin glass
claimed that the uncertainty, which is over three times
capillary and set on a sample holder. A 3 MeV proton beam with
higher than that expected for an analysis with standards,
a beam size of 4.3 µm was used. A total of 22 projections of 12
could be reduced to values closer to 3% by optimization of
slices were taken over 360° with a Si(Li) detector (sensitive area,
the spectrometer parameters for standardless operation.
80 mm2). They used a PIXE-tomographic reconstruction pack-
With increasing interest in nanometer-scale studies, a common
age (Discrete Image Space Reconstruction Algorithm). Recon-
research issue is the need to use different analytical systems with
structed elemental maps of the slice of hair were obtained for
a universal substrate to relocate objects on the nanometer scale, K, Ca, Fe, and Zn.
where determination of the regions of interest (ROIs) from one Tada et al. developed wavelength-dispersive PIXE (WD-PIXE)
analytical tool to another is nearly impossible without a reference and applied it to chemical speciation of sulfur in activated carbon
map. Suspending small particles on commercial TEM grids offer (121). In the WD-PIXE setup, as shown in Figure 6, a von Hamos-
the ability to study the particles; however, the smallest standard type spectrometer with a bent crystal (PET, size, 15 mm × 50
openings available are on the order of ∼100 µm. To find a sample mm) and a CCD detector (size, 27 mm × 2 mm) were used. A 2
position on the order of 100 nm can still take a long time. Nowak MeV proton beam was focused on a 3 mm diameter sample. MoS2,
et al. (116) reported a method of fabrication of a versatile substrate S, Na2SO3, and (NH4)2SO4 were used as RMs in addition to
for finding samples on the nanometer scale. With the use of the activated carbon. During the WD-PIXE measurement, the S
delicate milling capability of a FIB system, a ROI on a sample is X-ray yield was monitored by a Si-PIN detector to check
labeled by means of a milled reference grid. FIB technology allows whether the sulfur evaporates. This WD-PIXE spectrometer
for milling and deposition of material at the sub 20 nm level. With enabled an energy resolution of 0.6 eV for sulfur KR X-ray
a grid on the order of a few micrometers, optical, FIBs, TEMs, energy. The chemical shift of sulfur in activated carbon clearly
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4965
Figure 6. Schematic diagram of a high-resolution WD-PIXE setup. Reprinted with permission from (ref 121) Tada, T.; Fukuda, H.; Hasegawa,
J.; Oguri, Y.; Tsuji, M. X-Ray Spectrom. 2009, 38, 239-243. Copyright 2009 John Wiley and Sons.

showed that sulfur resided as elemental sulfur. The same Paris. A 3 MeV proton beam with a diameter of 100 µm was used
research group applied the same WD-PIXE spectrometer to for Micro-PIXE. Micro-SR-XRF measurement was performed at
investigate the chemical shift of the chlorine K X-ray spectra the BESSY SR facility in Berlin. An X-ray beam with excitation
(122). They measured the chlorine K X-ray spectra for NaCl, energy of 34 keV and a beam size of 100 µm × 200 µm was used
NH4Cl, and PVC. The energy resolution was 1.1 eV at the for micro-SR-XRF. Native gold on five Dacian bracelets, exhibited
energy of the chlorine K X-ray. Unfortunately, the authors could at the National Museum of Romanian History, was measured. The
not find any chemical effects in the measured Cl KR X-ray authors summarized that both techniques were useful tools in
spectra. However, they could successfully observe satellite establishing the authenticity and the provenance of ancient gold
structures of the Kβ spectra, which reflected the chemical artifacts. However, in cases where it is difficult to take the artifacts
environments of chlorine atoms. out of a museum, the authors suggested that in situ XRF
Preoteasa et al. investigated normal enamel and the in vitro measurement might be a good alternative technique. An Italian
formation of precarious lesions in lactic acid solution by using research group analyzed samples of particulate matter by PIXE
broad-beam PIXE and µ-PIXE (123). The broad-beam PIXE and XRF methods (126). Both PIXE and XRF are very effective
measurement was performed with 3 MeV protons. The proton techniques in an atmospheric aerosol study. The PIXE measure-
beam with a diameter of 2 mm hit the target at 45°. Micro-PIXE ment was performed at the 3 MeV Tandetron accelerator of the
was performed with 3.1 MeV protons focused to an approximately INFN-LABEC Laboratory in Italy, while XRF measurement was
3 µm spot at a current of 300 pA. Micro-PIXE gave elemental maps performed by an Oxford Instruments ED-2000 spectrometer with
of Ca, Fe, and Zn at a resolution of 3-4 µm, while broad-beam a Ag anode (15-30 keV and 0.1-0.5 mA) at the University of
PIXE gave the information of the thickness of the analyzed layer. Genoa and Milan. Fourteen samples of PM10 and PM2.5 particulate
They obtained spectrochemical evidence of demineralization- matters were collected by standard low-volume sequential
induced changes in the surface layer of dental enamel. samplers at an urban sampling site. Experimental data obtained
There are many articles reporting combinations of PIXE and by both techniques were compared. The comparison showed
other instrumental techniques. Salomon et al. performed ion beam a good agreement. The difference in the elemental sensitivity
analysis of works of art at the Louvre Museum’s laboratory in (minimum detection limits) for XRF and PIXE was obtained,
Paris (124). A microbeam setup permitting simultaneous or mainly caused by different ionization cross sections for photons
sequential PIXE/RBS (Rutherford backscattering) combination and protons.
with an external proton beam was developed. The simultaneous A feasibility of PIXE analysis of trace elemental profiling of
application of PIXE and RBS with a 3 MeV proton beam provided gunshot residues (GSRs) was studied (127). The results obtained
a fast analysis of the same position, with a large analyzing depth by PIXE were compared with the experimental data obtained by
for RBS measurement. This combined setup was applied for the a conventional technique, SEM-EDS. GSR samples were collected
analysis of a Russian icon, a bronze chandelier of the Hildesheim from four different firearms loaded with different types of am-
Cathedral, and Renaissance glazed plates. munition. PIXE spectra were obtained using a 2.5 MeV proton
Micro-SR-XRF is a strong competitor of micro-PIXE. Constan- beam, focused to about 4 µm, and a Si(Li) detector. SEM-EDS
tinescu et al. used both techniques to study identification of spectra were taken by using a Philips XL30 SEM with an EDAX
archeological gold (125). Micro-PIXE measurement was per- EDS system at an electron beam energy of 30 keV with a Si(Li)
formed at the AGLAE accelerator, Louvre Museum laboratory in UTW (ultrathin window) detector. SEM-EDS spectra have large
4966 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
continuous X-rays, while PIXE spectra showed a low background.
The authors concluded that PIXE revealed trace or minor
elements, which could not be detected by SEM-EDS, leading to
the discrimination between different types of GSRs. However, the
authors remarked that due to the relatively high cost and large
footprint of PIXE equipment and lack of availability, it is unlikely
that PIXE would be used as a primary technique for the analysis
of gunshot residues in forensic science. However, PIXE would
be highly complementary to SEM-EDS in high-profile casework.
Demortier et al. studied the combination of PIXE and accelera-
tor mass spectrometry (AMS) to determine the composition of
ancient objects and radiocarbon dating (128). The experiment was
performed at CEDAD, a multidisciplinary research facility at the
University of Salento in Italy. A 3 MeV Tandetron accelerator was Figure 7. Three-dimensional image of the unexposed Daphnia
used for micro-PIXE measurement. The AMS spectrometer magna sample. The grayscale data set gives a full 3D absorption
consisted of a Cs sputtering ion source, a low energy sequential reconstruction of the daphnid (3 µm resolution) obtained by the UGCT
injector, and a high-energy mass spectrometer. 12C3+ and 13C3+ micro/nano CT setup at Ghent University. Two RGB composed micro-
XRF data sets obtained at HASYLAB are also incorporated in the
beam currents were measured by two Faraday cups, while the
14 3+
image: a micro-XRF 2D dynamic scan and a micro-XRF computed
C ions were measured by another analysis system. The tomography cross section through the gill tissue, eggs, and gut. From
reproducible precision levels were 0.3-0.4% and 0.05-0.1% on (ref 130) De Samber, B.; Silversmit, G.; Evans, R.; De Scham-
the 14C/12C and 13C/12C determinations, respectively. The phelaere, K.; Janssen, C.; Masschaele, B.; Van Hoorebeke, L.;
combination of PIXE and AMS was applied to various ancient Balcaen, L.; Vanhaecke, F.; Falkenberg, G.; Vincze, L. Anal. Bioanal.
Chem. 2008, 390, 267-271, Figure 3, Copyright 2008. With kind
objects. This system was used for the provenance study of
permission of Springer Science + Business Media.
obsidian tools excavated in Turkey. AMS radiocarbon dating
was successfully applied for calibrating calendar ages. As a performed on polished thin sections of the lower and middle levels
result, elemental distributions of Sr, Zr, F, and Si, obtained by with different compositions. Confocal Raman spectroscopy indi-
micro-PIXE, suggested two geochemical groups for the ana- cated that the matrix of the lower level is mainly composed of
lyzed samples. anorthoclase ((Na, K)AlSi3O8), which was supported by the
results of the µ-XRF analysis. The authors concluded that the
MICRO X-RAY FLUORESCENCE ANALYSIS different compositions of the lower and middle levels were
µ-XRF analysis enables the two-dimensional imaging of el- because of the compositional changes of K and slightly Fe
emental distribution in inhomogeneous samples with the great elements. Ramos et al. (132) studied the data analysis for
advantage of nondestructive elemental analysis at an ambient combined micro-Raman spectroscopy and µ-XRF experiments.
pressure. Currently, new approaches of µ-XRF have been proposed They attempted to classify ochre pigments investigated in the
by combination with other spectroscopic methods, e.g., X-ray field of cultural heritage using partial least-squares-discriminant
tomography and µ-Raman spectroscopy. De Samber et al. (129, 130) analysis. The results showed that the combination of signal
demonstrated 2D and 3D elemental distributions (Zn, Fe, and Ca) features was the most suitable for a rapid and unique process-
in a Daphnia magna samples by combination with SR-µ-XRF and ing of both types of spectra. Castro et al. (133) performed
X-ray microcomputed tomography (CT). Their experiments were micro-Raman and µ-XRF analysis of the Spanish 15 cent stamp
carried out at Beamline L of the DORIS II storage ring, HASYLAB from the King Alfonso XIII (1889-1901) issue with color error
in Germany. The primary X-ray beam monochromatized by a Ni/C in order to confirm the authenticity of these 15 cents stamps.
monochromator at 20.7 keV was focused to 15 µm by single They aimed to clarify the reason of difference in color and the
capillary optics. Fast dynamic 2D µ-XRF scanning and dynamic nature and cause of this printing error by using atomic and
XRF micro-CT experiments gave the quantitative information of molecular techniques. µ-XRF analysis was carried out by a
the accumulation of metals within specific organs. The X-ray compact µ-XRF spectrometer (ArtTAX; Röntec) with a Mo
micro-CT was used to generate a full 3D model on a resolution anode and SDD. The primary X-rays were collimated by a
level of 3 µm. By combination of SR-XRF and micro-CT data sets tantalum collimator with a diameter of 0.65 mm. Raman
using appropriate software packages, it was possible to show the spectroscopy was performed with a Renishaw RA-100 system,
2D/3D distribution of metals at the 3-15 µm resolution level, as and results suggested the presence of a red iron oxide
shown in Figure 7. (hematite, Fe2O3) with a black amorphous carbon pigment. As
µ-XRF provides quantitative information on elemental distribu- a result of the detailed scientific analysis, it was concluded that
tion, while Raman spectroscopy provides chemical structure the differences of the color were caused by the use of different
information of the surface of samples. The combination of µ-XRF kinds of inks.
and µ-Raman technique is very useful for understanding the Polycapillary X-ray optics can provide a highly concentrated
samples such as geological and art samples. Koralay and Kadioglu X-ray beam in a small area by using a laboratory X-ray source
(131) investigated color changes of ignimbrite rock samples by because hundreds of thousands of individual capillaries can
using µ-XRF and confocal Raman spectroscopy. The µ-XRF capture the X-ray irradiation with a large collection angle. The
analysis was carried out with a 30 W X-ray tube and SDD at a micro X-ray beam sizes focused by the polycapillary X-ray optics
spot size of 0.7 mm. µ-XRF and Raman spectroscopy studies were are dependent on the X-ray energy: usually the beam size in the
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4967
low-energy region is larger than that in the high-energy region. The species in the paint were determined to be chalk (CaCO3),
Nakano et al. (134) studied an improvement of spatial resolution red lead (Pb3O4), yellow arsenic (As2S3), and red arsenic
of the micro X-ray beam using a laboratory X-ray source. To make (As2S3).
the X-ray beam size small, Ti-Cu thin foil was placed between Kanngiesser et al. (138) performed confocal 3D µ-XRF analysis
the output of the lens and the focal point as a metal filter to re- for the investigation of reverse-glass paintings. Their experiment
duce the continuous X-rays. As a result, the size of the X-ray beam was carried out at the µ-Spot-beamline at BESSY II. The primary
was reduced to 30 µm, and the spatial resolution of the µ-XRF X-ray beam was monochromatized by a Si(111) double mono-
was improved. The proposed method is a simple and useful chromator. The confocal arrangement consisted of two polycap-
method for decreasing the size of X-ray microbeams of laboratory illary X-ray half lenses having a spot size of 24 µm at 18 keV for
X-ray sources. the one exciting the sample and a spot size of 12 µm for the one
Czyzycki et al. (135) proposed a MC method with a µ-XRF in front of the Si(Li) detector. They focused on the analysis of
technique for determination of the chemical composition of heavier elements such as Rb and Sr in the material. The authors
individual particles. Glass microsphere standard materials (NIST found that Pb and Hg ions migrated into the glass matrix from
K3089 and NIST SRM 1833) with diameters in the range of 25-45 the paint layer in which they were in the form of Pb-white and
µm were investigated by using a micro-XRF spectrometer with a Hg-cinnabar. The nondestructive depth profiling technique using
3 kW Mo X-ray tube. The micro X-ray beam was collimated with a confocal 3D-XRF will be very useful for understanding the
single straight capillary optics with a diameter of 15 µm. It was chemical processes in glass corrosion and others. Nakano and
suggested that the MC calculated concentrations of low-Z elements Tsuji (139) performed the nondestructive depth profiling of
(Si and Ca) were overestimated in the case of the larger particles, Japanese lacquerware, “Tamamushi-nuri”, using confocal 3D-XRF
probably due to the absorption of X-rays and the geomaterial in comparison with the micro-GEXRF. Two independent polycap-
model, indicating that the MC results obtained for low-Z elements illary X-ray lenses and two X-ray sources (Cr and Mo targets) were
were highly dependent on particle size. More accurate results used for the confocal 3D XRF spectrometer to achieve highly
were obtained for high-Z elements such as Fe-Pb. The elemental effective excitation of light elements by applying a Cr target. Two
uncertainty did not exceed 14% for any particular sample and 6% polycapillary full lenses for X-ray irradiation were attached to each
for the average of the whole group of the measured microsphere. X-ray tube, and another half lens was attached to an SDD. The
The authors expect the next development stage of the MC method focal spots of the three lenses were adjusted exactly to a common
in confocal 3D X-ray imaging. point. The depth resolution of the 3D-XRF setup evaluated from
A recent topic in µ-XRF analysis is three-dimensional (3D) XRF the fwhm value of the X-ray intensity profile obtained by scanning
microscale analysis. In particular, confocal 3D-XRF combined with a Au thin-foil was approximately 80 µm. 2D-XRF images of
Japanese lacquerware showed specific distributions of elements
polycapillary optics is an interesting method because it provides
at different depths, indicating that Tamamushi-nuri lacquerware
nondestructive 3D elemental mapping in a microvolume of the
had a layered structure.
sample. In the confocal 3D-XRF configuration, at first, a micro
Sokaras and Karydas (140) studied the influence of secondary
X-ray beam irradiates the sample. In addition, polycapillary
fluorescence enhancement in confocal XRF analysis, especially
monolithic optics is equipped in front of the X-ray detector. The
for the stratified materials. They proposed a global model that
focusing spots for excitation and detection are adjusted to be at
precisely described the secondary fluorescence enhancement
the same location, which is called the “confocal point.” Under the
effect. With the use of an ab initio mathematical formulation for
configuration, it is possible to obtain XRF intensity of the analyte
all the involved experimental parameters (excitation/detection
in a spatially small region, leading to 3D elemental mapping
channel, sample structure, etc.), a proper multidimensional
images. Sun et al. (136) has designed and characterized a confocal
integral expression was deduced. They evaluated the contributions
3D-XRF facility based on polycapillary optics and Kirkpatrick-Baez
of primary and secondary emissions in the depth profile for the
(K-B) mirrors. Their study was carried out at 4W1B-XRF
specific layered models such as the Fe layer on a Cu substrate. It
beamline of Beijing Synchrotron Radiation Facility in China. The
was shown that the secondary fluorescence effect in confocal X-ray
SR beam with a 250 × 250 µm2 area was focused into a microfocal
microscopy was strongly dependent on the sample and the
spot with a 20 × 50 µm2 area by using K-B mirrors at 15.3
geometry of the experimental setup as well as on the experimental
keV. A polycapillary X-ray half lens was attached with a Si(Li)
conditions. The proposed mathematical formalism within the
detector. The lateral resolution of their confocal configuration
quantification analysis procedure is expected to improve the
was 76.3 × 53.4 µm2, and the depth resolution was 77.1 µm.
analytical accuracy of confocal XRF and X-ray elemental depth
The authors applied the confocal XRF system to a plant sample
profiling.
(twig of B. microphylla) and airborne particles. The same
research group (137) also demonstrated elemental depth X-RAY ABSORPTION SPECTROMETRY
analysis of faux bamboo paint in Emperor Qianlong’s Lodge XAS or X-ray absorption fine structure (XAFS) is a method
of Retirement in the Forbidden City using this confocal setup. with various advantages such as element selectivity and applicabil-
The Qianlong Emperor was the sixth emperor of the Qing ity to various sample states (crystalline, amorphous, solution,
Dynasty of China. Faux bamboo paint was made by stratifying colloids, etc.), and it is informative because XAS includes two
the paint and covering it with some kind of lucid glazing oil. theoretically independent methods, namely, XANES and EXAFS.
The elemental depth profile for Ca, Fe, As, and Pb, analyzed These two methods provide local structural information concern-
by the confocal 3D-XRF setup, showed that the paint had a ing the oxidation state and coordination environment, respectively.
multilayered structure consisting of different pigment layers. On the basis of these unique features, applications of XAS have
4968 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
extended into many scientific fields such as physics, chemistry, environments, and oxidation states inherent in XANES spectra
materials science, biology, and earth and environmental sciences. were revealed by comparing the spectra with the results of DFT
Over the last 10 years, more than 1000 papers per year have calculations as described in Yano and Yachandra (143).
been published that are related to EXAFS, XANES, and NEXAFS A more empirical approach was used by Chalmin et al. (144)
(near-edge X-ray absorption fine structure; the term often used to determine the oxidation state and symmetry environment of
for XANES in the soft X-ray region for lighter elements such as Mn in minerals. In this study, high-resolution manganese K-edge
C and N). During this review period, the number of papers XANES spectra focusing on pre-edge structures were collected
concerning XANES (and NEXAFS) has steadily increased, whereas for 40 Mn-bearing minerals. The pre-edge feature information
the number concerning EXAFS has been almost constant. (position, area) was extracted by multiple scattering and multiplet
Although EXAFS can give direct local structural information about calculations for the model compounds. As a result, it was
targeted atoms, recent advances in computational chemistry suggested that this method provides a quantitative estimate of
enable us to extract similar structural information using only the average valence of Mn in complex minerals and silicate
XANES (and NEXAFS) in some cases. If we compare XANES and glasses. The method can be widely applied to various natural
EXAFS, XANES spectra can be measured for more samples, minerals. Similar methods were successfully applied to Fe by the
including more dilute elements in samples. Thus, advances in same group to estimate the average valence of Fe in various
computational chemistry have increased the chance of obtaining samples.
structural data using XAS. In addition, considering that it is Yamamoto (145) summarized the characteristics of pre-edge
practically impossible to obtain EXAFS spectra for the lighter peaks in K-edge XANES spectra of 3d transition metals in terms
elements (e.g., C and N), the development of theory toward of the selection rule, coordination number, number of d-electrons,
understanding XANES (and NEXAFS) spectra has made XAS and symmetry of the coordination sphere. The intensity of the
more powerful as an analytical technique suitable for lighter pre-edge peak was enhanced by hybridization of 3d orbitals with
elements in various scientific fields.
p orbitals. It was shown that the intense pre-edge peak for
Advances can be seen in a variety of studies. Ching and Rulis
tetrahedral species of 3d transition metals was not due to the
(141) calculated XANES spectra of anions and cations at various
1s-3d transition but that the transition was caused by the p
edges in 12 crystals of the Y-SisON system using an ab initio
component in d-p hybridized orbitals. The intensity, which is
supercell method based on density functional theory (DFT). The
related to the number of 3d electrons regardless of the type of
calculations took into account the coreshole effect and included
element, is maximized for d0 species and decreases to zero for
explicit evaluation of the transition elements. On the basis of the
d10. The d-p hybridization did not occur in octahedral
extensive calculated data, it was shown that there is no clear
compounds, where only a weak pre-edge peak was observed
evidence of trends in the XANES spectra that can be established
arising from the 1s-3d electric quadrupole transition. The clear
to justify the “fingerprint method” of fitting XANES spectra. For
trends observed in this study are useful as a first step to
example, very different Si-K edge XANES spectra were obtained
interpret XANES spectra of various elements.
in various crystals having similar well-defined Si-O4 units. It was
The increasing use of XAS studies in the soft X-ray region also
indicated that structural modeling is needed to understand
depends on developments in experimental methods such as
XANES spectra properly. Evidently, the use of RMs similar to
microbeam technology and other devices for measuring samples
the examined samples is recommended if one can use only
under atmospheric pressure. In particular, STXM has become one
the “fingerprint method” for spectral interpretation.
Risberg et al. (142) analyzed experimental sulfur K-edge of the most powerful techniques, as indicated by Yoon (146),
XANES spectra of the amino acids cysteine, homocysteine, etc. because the method can give nanometer scale chemical informa-
by using transition potential DFT calculations. They computed tion under in situ conditions for light elements such as C and N,
absolute energies and intensities of the main pre-edge sulfur 1s which has not been possible using other methods. This method
electron transitions, by which it was possible to determine the can be applied to various studies including hydrated materials such
character of the unoccupied molecular orbitals (MO) and to as environmental and biological samples. Because dehydration
investigate the influence of interactions with other atoms on the can cause serious changes in some chemical species, the method
XANES spectra. For example, pKa values of thiol and protonated applicable under atmospheric pressure enables us to determine
amine groups can be estimated by considering the molecular the original speciation of elements in samples.
charge distribution obtained by coupling XANES spectra and Various types of time-resolved XAS have been developed over
DFT calculation. It was also found that externally induced more than 10 years. In particular, femtosecond X-ray pulses
changes in the intramolecular bonding, e.g., by coordination, obtained by plasma emission from metal targets irradiated by
conformation geometry, or hydrogen bonding, can significantly intense ultrashort laser pulses have been readily available and
influence the S K-edge XANES spectra. These results also applied to various types of studies. Such applications include
showed the importance of choosing RMs having a similar chemical and biological systems that may be disordered and
chemical environment to sample in order to explain and diluted samples, for which XAS is a very suitable probe. For
deconvolute experimental spectra. example, Bressler et al. (147) successfully applied the femtosec-
Another example of a biological study using XANES is the ond XANES technique to spin crossover phenomena of Fe(II)
study of the role of Mn4Cu clusters in photosynthetic systems. complexes induced by light. The study solved a long-standing
Among various studies in this field where EXAFS spectra problem concerning the electronic states, especially the quintet
cannot always be obtained, coordination numbers, ligand state of Fe(II) complexes.
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4969
Energy-dispersive XAFS or simply dispersive XAFS (DXAFS) interference in the measurement of U LIII-edge XANES spectra
employs an energy dispersive spectrometer using a bent crystal because of the presence of the Rb KR line in the vicinity of the
to focus and disperse a polychromatic X-ray beam onto the sample. U LR1 line. By separation of the U LR1 line from the Rb KR
The X-ray beam passing through the sample then diverges toward line, it was possible to obtain U LIII-edge XANES spectra for
a position sensitive detector, where beam position is related to less than 1 ppm of U in granitic rocks. Determination of the
the incident X-ray energy. The main advantages of DXAFS are oxidation state of U based on the XANES spectrum is important
the short acquisition time and the great stability during the in understanding the migration of U, an important element in
measurements due to the absence of any mechanical movement. environmental sciences because of the higher mobility of U(VI)
In particular, its time-resolved characteristics are highlighted in than U(IV) in natural systems.
the article by Newton (148), particularly for its application in Advanced X-ray sources have often given breakthroughs in
catalysis. Moreover, this article indicated that the combination of X-ray spectroscopy. Development of a compact, high-sensitivity,
time-resolved XAFS with other time-resolved techniques such as low-power, and low-cost tabletop instrument for measuring XANES
X-ray diffraction and scattering is important for understanding spectra for transition metals was described by Wei et al. (153).
dynamic reactions related to the structural change of supported The system could measure Cr at 100 ppm concentration levels
metal nanoparticles in heterogeneous catalysis. and improvements in the system could allow the measurement
Another type of time-resolved XAS method is the quick- of Cr at <10 ppm levels. Very short (<1 s) measurement times
scanning XAS technique, often called QXAFS or QEXAFS. QXAFS were possible for a large variety of elements.
is performed by a continuously scanning monochromator during Many new methodologies such as ultrafast X-ray sources for
measurement of XAFS, which can be used both in transmission time-resolved analyses have been developed to study transient
and fluorescence modes. The time resolution of QXAFS is limited structures of any material. Among the various methods, Guo (154)
by the maximum scanning speed of the Bragg angle of the pointed out that the FEL, which has been built or will be built in
monochromator. Stötzel et al. (149) established a QEXAFS various facilities, will contribute to better understanding of
method that has a time resolution of ∼50 ms, which is faster than dynamics in chemistry, physics, materials science, and more
previous QXAFS methods. Since QXAFS can be applied to any importantly in biology. For example, this method will enable us
energy region and can also be measured in fluorescence yield to control synthesis in chemical and material sciences by
(FY) mode, wider application of QXAFS in various fields as a time- manipulating the reaction dynamics using in situ methods such
resolved method is strongly anticipated. For example, QXAFS was as photons or heat. The first FEL experiment began in September
used to determine reaction rates of metal ions at the mineral-water 2009 in the Linac Coherent Light Source (LCLS) using the 2 mile-
interface (150). The reaction rate at the interface has been long linear accelerator in SLAC, Stanford, U.S. Currently, two other
FELs operating in the X-ray region are being built, one in Europe
estimated traditionally by batch methods coupled with extraction
(FLASH) and another in Japan (XFEL in SPring-8). It is expected
of adsorbed species into the aqueous phase or by flow techniques.
that these new sources will open various new scientific fields.
The QXAFS method is in situ analysis of metal ions at the
solid-water interface, which can give more reliable information
APPLICATIONS
about the reactions at the interface such as oxidation of As(III) Sample Preparation. XRF has great beneficial advantages
to As(V) at the MnO2-water interface. Understanding of these over other analytical methods in that it enables nondestructive
reactions is critical for predicting the fate of contaminants in measurement and does not damage the sample. However,
aquatic environments. quantitative determinations for the geochemical samples (rock,
FY-XAS analysis is usually more sensitive than that in the clay, sediment, and soil) by XRF often require the suitable sample
transmission mode. In particular, an energy-dispersive detector preparation because elemental distributions in these samples are
such as a Ge detector is very useful for recording FY-XAS spectra, most of the time inhomogeneous. The fused glass bead technique
but wavelength-dispersive methods using a crystal spectrometer is the best promised method to determinate major and minor
are often used to obtain more detailed information from XAS. For elements in the geochemical samples by XRF. Nakayama and
example, Hayashi et al. (151) employed a multicrystal and Nakamura (155) reviewed calibration standards using chemical
multidetector spectrometer consisting of five pairs of a spherically reagents for the glass bead method of the geochemical samples.
bent Si(444) crystal and a scintillation counter for high-sensitivity Although rock references issued by geological organizations have
detection of weak Lγ4 emissions of Eu. In their study, they found often been applied to glass bead XRF, several problems remain,
that the emission exhibited a large chemical shift (= 5 eV) that i.e., limited varieties and numbers and uncertainty related to
depended on the valence state of the Eu compounds. Application uncertified (recommended or preferred) values. The authors
of this emission to valence-selective XANES by partial FY concluded that synthesized calibration standards with chemical
measurements was conducted for a 1:1 mixture of EuS and Eu2O3 reagents had constitutive properties that were superior to those
and for the valence-fluctuating compound Eu3Pd20Ge6. of the rock RMs. Synthesized standards can ensure the traceability
Lower resolution wavelength-dispersive methods can be used of the analytical procedure and the accuracy of calibration curves,
to measure FY-XAS spectra of trace elements in a matrix that can although they must be prepared by fitting elemental compositions
cause interference in the measurement of FY of targeted elements. to each geological sample. Reliable calibration curves were
Yamamoto et al. (152) employed a commercial bent crystal Laue obtainable by designing parameters such as the number of plots,
analyzer (BCLA) to obtain uranium LIII-edge XANES spectra for plotting arrangements, and calibrating ranges. Gazulla et al. (156)
trace amounts of uranium in natural rocks. In natural rocks, investigated the bead-releasing agents (NaI, LiBr, NH4I, and LiI)
more abundant elements such as Rb and Sr cause serious in the preparation of fused bead specimens for WD-XRF
4970 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
analysis. They reported that the best bead-releasing agent was complexation of As3+ with sodium dibenzyldithiocarbamate
LiI in terms of sample reproducibility of WD-XRF analysis when (Na-DBDTC) and solid phase extraction (silica gel). The
a relatively small quantity (LiI, 0.11 g/bead) was used. The detection limit for arsenic was 10 ng L-1.
same research group investigated a sample preparation method The small-volume droplet technique is a recent trend for the
for sulfur analysis in geological samples by WD-XRF (157). preparation of liquid sampling. Fittschen et al. (163) investigated
Various sulfur compounds (CuS, CuSO4, BaSO4, CaSO4 · 2H2O, a picodroplet technique as a reference for microbeam analysis,
FeS, and Na2SO4) were used for calibration. These sulfur e.g., laser ablation-inductively coupled plasma-time-of-flight-mass
compounds were individually mixed with a sulfur-free kaoline spectrometry (LA-ICP-TOF-MS) and µ-XRF analysis. A modified
and prepared as powder pellets and glass beads. Calibration inkjet printer was used for picodroplet generation. The dried
curves obtained from sulfur compounds in powder pellets residues of picodroplets were characterized by µ-XRF and TXRF
showed different slopes due to their different mineralogical for the quantification and the precision of dosing, optical micro-
structures and matrixes of the compounds, whereas those scope for the residue size, and AFM for the morphology. A dosing
obtained from glass bead samples showed similar slopes. precision calculated by TXRF determination was 4-15%. The sizes
However, very largely scattered data were obtained for all the of the dried residues were 5-20 µm. The diameter of the dried
sulfur compounds, except BaSO4, as sulfur loss occurred in residues depended on the concentration of sample and substrate
the fusion process. The proper amount of BaO was added in material. The elemental distribution of the dried residues was
the sample to minimize the sulfur loss during the fusion measured by SR-µ-XRF and showed high uniformity for element
process, resulting in the calibration curves with a good linearity. deposition of every single droplet with an RSD of 4-6%. The shape
Shibata et al. (158) studied in-house soil standard materials and height profiles of the dried residues obtained by AFM were
containing As, Cr, Se, Cd, Hg, and Cd, prepared by pressed powder symmetrical spherical segments with maximum heights of 1.7 µm.
pellet and loose powder methods for WD-XRF analysis. XRF intensi- Finally, the potential of this technique for the direct LA-ICP-TOF-
ties of analytes obtained by the pressed powder pellet method agreed MS analysis was studied. The calibration curves of 48Ti, 69Ga, and
138
well with those of the loose powder method without the matrix Ba showed good linearity, and the limits of detection (LOD)
correction. They also reported that the intensity ratio of Pb LR to Pb were 24 pg for 48Ti, 3 pg for 69Ga, and 1 pg for 138Ba,
Lβ was dependent on the tube voltage. In addition, they confirmed respectively.
that corrections with Compton scattering for As KR, Se KR, Cd KR, Standards. Quantification of trace metals in plastic materials
Hg LR, and Pb Lβ were effective and produced identical inclinations is of great importance for quality control and for monitoring
of calibration curve. These results were useful for determining the hazardous metals. Currently, hazardous elements in industrial
elements of actual soil samples. Ohbuchi (159) studied the standard plastic materials have been restricted internationally since the
fly ash samples using the powder pellet method. The standard European Union (EU) enforced the RoHS directive as set out in
samples were prepared by mixing chemical reagents of 10 major Directive 2002/95/EC. In particular, IEC 62321:2008, which is an
components (Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, international standard for the determination of Pb, Hg, Cd, Cr(VI),
MnO, and Fe2O3) and 5 minor components (Cr, Ni, Cu, Zn, and polybrominated biphenyls (PBB), and polybrominated diphenyl
Pb) to match the chemical components of the real fly ash samples. ethers (PBDE) in electrotechnical products, defined screening of
The prepared standard samples were successfully used for these compounds with XRF analysis. The RMs for XRF analysis
quantitative WD-XRF analysis of 13 major and 5 minor elements are essential tools for determining the analytical results of toxic
in fly ash samples. elements for the RoHS directive. Mans et al. (164) developed a
Gonzalez-Fernandez et al. (160) evaluated the instrumental set of 10 candidate RMs, named as BAM H001-BAM H010, based
sensitivity and detection limits for determination of elemental on the acrylonitrile-butadiene-styrene terpolymer (ABS) con-
composition of dried residues from liquid samples by WD-XRF. taining Br, Pb, Cd, Cr, and Hg for the calibration of XRF and LA-
The preconcentration of elements from liquid samples (1-6 mL) ICPMS, supported by the Federal Institute of Materials Research
was performed by means of a simple dried residue process using and Testing (BAM), Germany. The mass fractions of all elements
a special liquid sample holder attached with a 4.0 µm-thick prolene range from 0 (blank)-1500 mg/kg, and the candidate RMs were
film attached. Elemental sensitivities were determined with atomic produced as granulates and solid disks with a diameter of 40 mm.
number after measuring multielemental standard solutions. The The candidate RMs were already produced in 2006 and reported
calculated detection limits with the proposed methodology were in a previous paper published in 2007. In this paper (164), they
from 0.005 to 0.1 mg L-1 depending on the element. Nakano et investigated the influence of XRF signals with sample thickness
al. (161) studied the convenient preconcentration procedure and the microscopic homogeneity of samples using SR-µ-XRF. XRF
of the XRF analysis of environmental waters by using a natural and LA-ICPMS were successfully calibrated by using the devel-
polymer (agar). A thin agar film was prepared by drying a oped RMs, showing LOD in the range of 0.4-22 mg/kg for XRF
homogeneous agar gel after mixing the aqueous sample and 2.3-26.8 mg/kg for LA-ICPMS. The Japan Society for Analyti-
solution (10 mL) with the agar powder. With the formation of cal Chemistry (JSAC; Japan) have developed a set of five certified
the thin film, the S/N (signal-to-noise) ratios of the XRF reference materials based on polyester resin, named JSAC 0651-
intensity of analytes were drastically improved. Staniszewski 0655, for XRF analysis of Br (165). The 300 candidate RMs were
and Freimann (162) investigated a liquid sampling procedure prepared by filling Al-cylindrical molds with polyester resin liquid
for TXRF determinations of arsenic in seawater by solid phase that was mixed with hardener and organometallic compounds.
extraction. Their sample preparation consisted of an arsenate The disks prepared after 12 h of hardening at room temperature
reduction process using an L-cysteine solution followed by a were ground to a thickness of 4.00 ± 0.05 mm and their surface
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4971
was polished. The homogeneity of the prepared disks was
investigated by WD-XRF. The certified values were evaluated to
be about 100, 300, 600, and 1000 mg/kg by statistical analyses of
the results from an interlaboratory comparison study.
Adriaens et al. (166) proposed new (in-house) RMs consisting
of thin cobalt films on gold for the µ-XRF quantification of cobalt
phthalocyanine and cobalt porphyrin films on gold. The RMs were
prepared by magnetron sputter deposition in various thicknesses
ranging from 10 to 100 nm on a gold substrate. The thicknesses
and homogeneity of the prepared film were determined by SR-
µ-XRF. The surface concentrations calculated by the FP method
showed very good correlation with the detected cobalt signal. The
heterogeneity of all samples was below 1.5%.
Schaumann et al. (167) prepared and characterized in-house
polymer layered RMs for the validation of confocal 3D-XRF Figure 8. The vacuum chamber of the µ-XRF instrument. Reprinted
analysis. An ethylene-propylene-diene rubber (EPDM) was with permission from (ref 169) Uhlir, K.; Griesser, M.; Buzanich, G.;
Wobrauschek, P.; Streli, C.; Wegrzynek, D.; Markowicz, A.; Chinea-
chosen as a polymer matrix for the RMs because the matrix effects Cano, E. X-Ray Spectrom. 2008, 37, 450-457. Copyright 2008 John
in the light matrix were minimized. Polymer layered RMs were Wiley and Sons.
prepared by assembling single layers of EPDM rubber filled with
of pigments was successfully determined by micro-XRF. One of
different concentrations of silica and zinc oxide as inorganic
the technical problems encountered was the short working
additives. Layer thicknesses were in the range of 30-150 µm.
distance between the measuring head of the ARTAX and the
Prepared RMs were characterized by conventional scanning µ-XRF
sample. It was difficult to measure curved surfaces of sculptures
with regard to filler dispersion, by infrared microscopy and light
or paintings close to frames.
microscopy to determine layer thicknesses, and by ICP-OES to
New applications obtained by using previously developed
verify the concentrations of the analytes in the layers. The confocal
portable µ-XRF instruments were reported by Uhlir et al.,
3D-XRF analysis was performed at the SR facility (BESSYII) and
researchers in Austria and Poland (169). The XRF instrument was
in the laboratory with a Mo X-ray tube. The depth resolution of
specially designed with a vacuum chamber housing (about 0.1
SR-3D-XRF analysis was determined to be about 30 µm, while it
mbar) for the X-ray optics and the X-ray detector in order to
was about 80 µm at the laboratory 3D-XRF setup. With the results
analyze low-Z elements with high efficiency. A 50 W low power
obtained for stacked polymer systems, the validity of the analytical Pd anode X-ray tube was operated up to 50 kV and 1 mA. As shown
quantification model for the determination of stratified materials in Figure 8, a polycapillary lens, producing a spot size of about
by confocal 3D µ-XRF was demonstrated. 40 µm, was attached to the X-ray tube. The X-rays were focused
EDS. Compared with conventional Si(Li) EDS, which is on the sample through a Kapton window (thickness, 7.5 µm) at a
operated with liquid nitrogen, recently developed EDS, such as distance of about 1-2 mm outside the chamber. The detection
Si-PIN detector and SDD, can be operated with a Peltier cooled limits of Al, Si, P, K, Ca, and Ti were evaluated to be 623, 352,
device. Therefore, the total size of the EDS is quite small. This 179, 107, 64, and 26 ppm, respectively. The analytical performance
downsizing of the EDS enables development of mobile EDXRS. of this instrument was investigated at the Conservation Science
Actually, the number of articles on mobile EDS is increasing. One Department of the Kunsthistorisches Museum Vienna (KHM).
of the most important applications of such mobile EDS will be Quantitative analysis of alloys and identification of pigments were
the in situ analysis of art, archeology, and cultural heritage successfully performed. The authors commented that one problem
samples, because it is usually difficult to transport these samples was the large size of the vacuum chamber, limiting accessibility
to the laboratory. In addition, µ-XRF analysis is useful in order to to certain parts of objects. In addition, semiquantitative analysis
obtain detailed information of the elemental distribution of the of light elements in glass and enamel was possible. Standard RMs
samples. A review article on mobile µ-XRF for medieval paintings for glass were required for more precise quantitative XRF analysis.
was published (168). Recent developments on X-ray sources, X-ray Tantrakarn et al. analyzed Roman glass excavated from Zadar
optics, and X-ray detectors, which are used for mobile EDS, and in Croatia by using a newly developed portable EDXRF spectrom-
commercially available mobile µ-XRF systems were briefly ex- eter (170). The instrument (100FA-IIL, OURSTEX) was composed
plained in this article. Besides commercial products, laboratory- of four separate parts: an X-ray spectrometer, a compact digital
developed instruments were also introduced. Some applications processing unit controlled by a notebook PC, a compact power
obtained by a commercially available setup (ARTAX) were shown. unit, and a vacuum sampling chamber. The X-ray spectrometer
In this article, three case studies were reported in which the consisted of an X-ray tube with a Pd target and an SDD with a
ARTAX spectrometer was applied for the analysis of medieval polymer window (AP3.3, MOXTEK). The total weight of this
paintings. The ARTAX spectrometer consisted of an air-cooled instrument was approximately 25 kg. The authors analyzed a
X-ray tube, a CCD camera with laser pointer for sample visualiza- standard glass sample (containing Na2O and MgO) to check the
tion, and remote motorized positioning. The diameters of the capability of the quantitative analysis of Na and Mg. The result
measuring areas of 80 or 650 µm matched well with the require- confirmed that the detection limit of Na was 1.2 wt %. The
ments of the detailed surface analysis of paintings. The ARTAX instrument was carried to the Republic of Croatia and used
spectrometer was mounted on a camera stand. The composition for XRF analysis at the research institute of the Archaeological
4972 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
Museum. The XRF results showed that all the glass excavated ingredients were successfully determined in good agreement
from Zadar was typical Roman natron-soda lime-silica glass with with the results obtained by ICP-AES.
low Mg and K content. In addition, quantitative analysis of Nakanishi et al. applied SR high-energy XRF analysis in
major and trace elements in the glass samples showed the forensic science (174). SR-XRF was performed using 75.5 keV
possibility of using Mg oxide and Sb oxide as a decolorizer. X-ray radiation at SPring-8, Japan. Glass standard reference
Cesareo and Brunetti analyzed 19th century stamps by using material (NIST, SRM612) was measured, and the K-lines of 31
a portable EDXRF (171). The portable EDXRF consists of an elements (from Ca to Hf) including rare earth elements were
X-ray tube (Eclipse II, Oxford-Amptek) with a Ag anode and a successfully measured without any interference. The RSDs were
Si-PIN detector (Amptek) with a brass cylinder collimator. A less than 9.7% except for Ca and the lower limits of detection
polycapillary conical capillary collimator (poly-CCC, produced were on the picogram level for Ba, Ce, and Sm and 10 pg for Sr,
by IfG) was attached to the detector to measure small areas Zr, Sn, and Hf. Fragments of collected sheet glass were measured
and to obtain a line elemental scan. A large number of stamps as forensic samples. Several trace elements such as Pb, Rb, Sr,
from the period from 1850 to 1900 were analyzed. The Zr, La, Ce, and Hf could be used as indexes to characterize the
relationship between the inorganic pigments determined by different types of glass samples. The same research group
EDXRF and the year of production was presented. In particular, reported trace elemental analyses of TiO2 pigments and automo-
the data obtained by XRF could be very useful for detecting tive white paint fragments by SR-XRF for the purpose of
forgeries, which are common in the case of rare stamps. forensic investigation (175). In this case, high energy X-rays
Palmer et al. applied a field portable (hand-held type) XRF (116 keV) were used for SR-XRF at SPring-8. TiO2 (rutile type)
analyzer for the rapid screening of toxic elements in products in nature tends to contain heavy elements such as Zr, Nb, Mo,
regulated by the FDA (U. S. Food and Drug Administration) and Sn, Sb, Ta, Hf, and W. The authors concluded that these
discussed the prospects of hand-held XRF devices (172). In this elements could be used as effective indexes for the discrimina-
article, the fundamentals of XRF analysis and its analytical tion and classification of pigments and paint fragments.
advantages and drawbacks, especially in comparison with ICPMS, Similarly, trace elements in the surface coating layers detected
were carefully explained for actual users. Previous applications by SR-XRF were effective for identifying samples.
of XRF in the analysis of foods and beverages were listed in tables. Issue 1 of volume 37 (2008) of X-ray Spectrometry is a special
The authors showed several applications of XRF analysis per- issue on XRS in Medicine, edited by Chettle at McMaster
formed by using two commercially available hand-held XRF University in Canada. Many important articles were included in
analyzers (Niton XLi and Innov-X R 2000). These devices were this issue. In vivo XRF studies of Pb, Cd, and Hg, mainly
battery powered. The X-ray source was either a radioisotope or performed at Lund University in Sweden in 1970-2005 were
an X-ray tube. XRF spectra obtained from an antique Fiestaware reviewed (176). Pb, Cd, and Hg are toxic elements, which are
plate showed high levels of both Pb and U. The authors also capable of causing damage to the human body. In vivo XRF
measured red-pigmented portions of the enamel coating on steel techniques provide noninvasive estimations of the concentrations
cups, indicating the presence of Cd and Se. EDXRF was applied of these elements. After a brief historical introduction on in vivo
to the elemental analysis of various supplements. It was found XRF analysis, some experimental setups developed at Lund
that imported Ayurvedic medicine contained 8% Pb and 7% Hg, University were shown along with the obtained results. EDXRF
which were also nearly the same as the data obtained by FAAS. results showed the high levels of toxic elements in the bones and
A total of 11.7% As was found in another medicine. The authors kidneys of workers who were occupationally exposed to Pb and
emphasized that the most important features of XRF were its Cd, respectively. Retired Pb workers showed a clear association
simplicity and speed, leading to the ideal technique for rapid between bone Pb and blood Pb and biological half-lives for bone
screening of a large number of samples. Pb of several years. Besides these toxic elements (Pb, Cd, and
High -energy polarized beam EDS (HE-P-EDXRF) was Hg), in vivo XRF results showed some other interesting elements
applied for the determination of Pd-catalyst residues in active such as Pt, In, Au, U, Zn, and As. The in vivo XRF technique was
pharmaceutical ingredients (173). This instrument consists of applied to the analysis of As and Ag in human skin (177). Three
a high voltage Gd X-ray tube and a high energy Ge EDS, which different configuration setups developed at McMaster University
enabled analysis of K lines of high atomic number elements were used for XRF analysis. 109Cd, 125I, and a normal X-ray tube
such as Pd. In the HE-P-EDXRF setup, the primary X-ray beam were used as X-ray sources. XRF was measured by a Si(Li)
was scattered by a secondary target. The use of suitable detector (EG&G Ortec) with an active diameter of 16 mm and
secondary targets in a three-dimensional polarizing geometry a sensitive thickness of 5.8 mm. A Si(Li) detector was employed
for excitation allowed a reduction in the intensity of continuum rather than a Ge detector because escape peaks from Ge are
radiation, leading to an increasing S/B ratio and the realization a problem for the detection of As. The detection limits for Ag
of highly sensitive XRF analysis. The authors used a com- and As with the developed XRF system were low enough (<10
mercial HE-P-EDXRF instrument (Epsilon-5, PANalytical), ppm) to allow the study of humans.
equipped with a 600 W Gd anode, 13 secondary targets, primary A review article of the application of EDXRF and dual-photon
beam filters, and a high-purity Ge detector. Since there were absorptiometry (DPA) in γ-ray spectrometry to in vivo Sr
no suitable pharmaceutical RMs for Pd determination, the measurement was published (178). More than 50 articles were
calibration standards were prepared in their laboratory. The reviewed. Sr is a natural constituent of the human skeleton.
LOD for Pd under the best conditions was 0.11 mg kg-1. Recently, the beneficial effects on bone of pharmacological
Finally, Pd concentrations in three active pharmaceutical dosages of Sr have been pointed out. The advantage of the DPA
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4973
Figure 9. (a) Tritonal color reconstruction of Sb (yellowish white) and Hg (red) representing the flesh color of the hidden face. (b) Detail from
Vincent van Gogh, Head of a Woman, Nuenen, winter 1884-1885, oil on canvas, 42 cm × 33 cm, Kröller-Müller Museum, Otterlo (KM 105.591;
F154/JH608). (c) Detail from Vincent van Gogh, Head of a Woman, Nuenen, winter 1884-1885, oil on canvas, 42 cm × 34 cm, Van Gogh
Museum, Amsterdam (F156/JH569). Reprinted from ref 182, Figure 7. 2008 American Chemical Society.

was that the Sr and Ca concentrations could be measured used to deduce a strong association between several parts of
simultaneously, while it was difficult with XRF due to strong signal bones. The concentrations of Sr and Zn did not change after burial.
attenuation. It was concluded that XRF and DPA had the potential Therefore, they were not affected by diagenesis and reflected in
to obtain unique information on Sr concentration in bone. In vivo conditions. In contrast, it was found that K, Ti, Mn, Fe, and
addition, there was another review article of the use of EDXRS in Pb from the soil easily penetrated into the bones, and they were
the study of human lead metabolism (179). In total, 22 papers enriched in all the bone structures.
were reviewed concerning the relationship between bone Pb and µ-XRF. µ-XRF analysis is powerful tool for obtaining 2D
cumulative blood Pb concentration, the half-life of Pb in bone, and mapping images of elemental distribution in samples. The µ-XRF
the kinetic parameters in models of Pb metabolism. Although the technique has been established in producing micro X-ray beams
technical description of EDXRS was short, 109Cd K XRF was one by the recent development of X-ray focusing optics. Numerous
of the measurement methods used. investigations of µ-XRF measurements were performed for various
Da Silva et al. applied EDXRF for in vivo and ex vivo sample types such as biological cells, plants, airborne particles,
quantification of Sr in human teeth (180). Mass attenuation of paintings, and archeological objects.
the Sr and Cr X-rays enabled probing depths of 1.8 and 0.15 mm, Dik et al. presented the application of SR-XRF mapping for
respectively. The EDXRF instrument consisted of a Si(Li) detector
visualization of a woman’s head hidden under a work by Vincent
and an 125I excitation source. The Sr concentrations determined
van Gogh (182). His small painting in oil, Patch of Grass (Kröller-
in fresh enamel by EDXRF showed good agreement with those
Müller Museum, Otterlo, The Netherlands), was painted on canvas
determined by graphite furnace AAS. The Sr concentrations
(30 cm × 40 cm) during his 1886-1887 Paris period. The authors
from the measured samples of fresh enamel ranged from 42
analyzed this painting by µ-XRF and XANES to visualize a hidden
to 301 ppm with a mean Sr concentration of 169 ppm. The
painting beneath the surface. The µ-XRF and XANES measure-
author’s further interest is whether factors such as diet, age,
ments were carried out at beamline L at DORIS-III and beamline
gender, or ethnicity may be responsible for differences in Sr
C of HASYLAB at DESY. For the µ-XRF measurement, a pencil
content in teeth.
The elemental concentration in buried human bones was beam (0.5 × 0.5 mm2) of quasi-monochromatic SR-X-rays with
studied by EDXRF for the purpose of an assessment of elemental an energy of 38.5 keV was used for primary excitation. With
concentrations in several different bones of the same population this beam, they scanned a square of approximately 17.5 × 17.5
of the Middle Ages (181). The authors considered that this mm2 for about 2 days. The obtained XRF intensity imaging
research would be important in determining the relationship reflected the distribution of specific elements in the paint layers,
between elemental concentrations in bones and dietary habits as resulting in the successful visualization of the hidden face. They
well as environmental living conditions of the populations. The succeeded in visualizing the hidden face. In particular, the
bone samples were collected from the same archeological site in distribution of Hg and Sb in the red and light tones, respec-
southern Portugal, where it was identified as being from the tively, enabled an approximate color reconstruction of the flesh
Middle Ages, dating from the 13th century. From each bone, a tones. This reconstruction proved to be the missing link for
few grams were taken, powdered, and pressed into pellets 2.0 cm comparing the hidden face with van Gogh’s known paintings,
in diameter. The EDXRF instrument consisted of an X-ray tube as shown in Figure 9. This approach can be applied for the
with a W anode, equipped with a secondary target of Mo, and a nondestructive study of hidden paint layers in other paints of van
Si(Li) detector. The concentrations of Ca, Zn, and Sr could be Gogh in particular.
4974 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
Figure 10. High-resolution elemental maps. The elliptical object indicated by arrows in the Au distribution map shows a single mitochondrion
and the dense region at the lower left represents the piles of mitochondria. Color bars indicate the elemental contents (femtograms) in an
irradiation area. Reprinted with permission from (ref 183) Matsuyama, S.; Shimura, M.; Mimura, H.; Fujii, M.; Yumoto, H.; Sano, Y.; Yabashi, M.;
Nishio, Y.; Tamasaku, K.; Ishikawa, T.; Yamauchi, K. X-Ray Spectrom. 2009, 38, 89-94. Copyright 2009 John Wiley and Sons.

Current X-ray focusing technology using a specific beamline Figure 10. Carmona et al. (184) performed nanoimaging of trace
from a SR facility combined with K-B mirror optics has enable- metals by SR-XRF into dopaminergic single cells and neurite-like
done to focus X-rays at submicrometer to several tens of nano- processes. The author studied how chemical element imaging was
meters spatial resolutions. Matsuyama et al. (183) performed performed in subcellular compartments of dopaminergic cells at
visualization of the distributions of trace elements in biological high spatial resolution, using the XRF nanoprobe developed at
samples such as tissues and cells at high spatial resolution by the European SR Facility (the nanoimaging facility ID22NI). A
using “a hard X-ray nanobeam”. The authors developed a scanning high-spatial resolution X-ray beam focused to a 90 nm probe by
X-ray fluorescence microscope (SXFM) at SPring-8 using K-B multilayer mirrors bent in K-B geometry was obtained. Their
mirror optics that enable achromatic and highly efficient focusing. setup was applied for trace metal mapping of single dopaminergic
One of the merits of K-B mirror focusing optics is its long cells involved in Parkinson’s disease. The authors concluded that
working distance (about 100 mm). Available minimum beam size (i) Fe was distributed in a granular form into dopamine vesicles,
was 29 × 48 nm2. As a result, a higher resolution better than found mainly in primary neurite outgrowths and distal ends, and
100 nm was achieved in the magnified elemental maps. To (ii) thin neurite-like processes, produced by differentiated cells,
evaluate its performance for biological samples, the SXFM was accumulated Cu, Zn, and to a minor extent Pb. Bohic et al. (185)
used at an X-ray energy of 15 keV to observe NIH/3T3 (mouse characterized the microchemical environment of neuromelanin
embryonic fibroblast cell line) cells in which adenosine triph- (NM) using SR-µ-XRF and micro-XANES measurements. NM is
osphate (ATP) synthase β (specifically localized at the mito- a dark colored pigment synthesized within specific catecholamine-
chondria) were labeled with gold colloidal particles. Various producing neurons in the human brain. Formalin-fixed, paraffin-
elemental distributions were visualized at the single-cell level, embedded transverse midbrain tissue blocks at the level of the
including those for P, S, Cl, Ca, Fe, Cu, Zn, and Au, and high- exiting third nerve fibers were prepared from the brains of each
resolution elemental distribution maps were obtained by subject for a period of 2 weeks prior to examination, so that each
magnifying the labeled single mitochondrion, as shown in brain had comparable fixation-induced changes, including effects
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4975
on metal concentrations. Their first experiments were carried out rats (4 months old) from the femoral head. The authors concluded
at the high-energy undulator beamline (ID22) of the ESRF that both the concentration and distribution of the minerals
(Grenoble, France). A microprobe focused to a 1 × 3 µm2 spot significantly varied among the groups depending on the location
(vertical × horizontal) with a K-B mirror system was used. A and bone site.
second experimental setup installed 65 m from the source of Fukuda et al. (189) investigated the mechanism of a Cd
the ID22 beamline, called nanoimaging facility ID22NI, was also hyperaccumulating plant, Arabidopsis halleri ssp. gemmifera, by
employed. Synchrotron undulator radiation was efficiently using SR-µ-XRF and SR-µ-XANES analyses. A monochromatic
focused using dynamically bent graded multilayers set in the high-energy X-ray (37 keV) was focused into a micro X-ray beam
K-B geometry. The spatial resolution of the nanoprobe was (3.8 × 1.3 µm2) with a K-B mirror on BL37XU at Spring8 in
80 nm. The authors represented the first visualization of a Japan. µ-XRF and micro-XANES measurements were used for
structure regulating the metal-binding properties of NM and the nondestructive analysis of the Cd distribution and chemical
supported a physiological role for NM in the regulation of form of Cd at the cellular level in the plant. The µ-XRF image
functionally important elements in pigmented neurons. Their clearly indicated that Cd was highly accumulated in a part of
results demonstrated that the local chemical environment of the trichomes, epidermal hairs on the surfaces of the leaves.
iron in NM was similar to that found in ferritin and pointed Micro-XANES analysis revealed that the majority of the Cd
out a possible role of iron in NM biosynthesis. Corezzi et al. existed in the divalent state and is bound to the O and/or N
(186) also explored the possibility of SR-chemical nano-XRF ligands. The authors also studied the process of an As
imaging with a spatial resolution of about 100 nm for human hyperaccumulating fern (Pteris vittata L.) using a similar SR-
cells by the use of functionalized CdSe/ZnS QDs. The sample µ-XRF setup (190). In this case, they used the micro X-ray beam
was a commercially available QD-secondary antibody conju- with an energy of 12.8 keV. 2D-XRF elemental images indicated
gate to label the cancer marker HER2 (human epidermal that As transformed from the root to the marginal part of the
growth factor receptor 2) on the surface of SKOV3 cancer cells leaf within 1 h after feeding. Using SR-µ-XRF measurement on
and β-tubulin, a protein associated with cytoskeleton microtu- BL37XU at SPring-8, Kodera et al. (191) investigated the
bules. These samples were prepared with epoxy inclusion and distribution of Pb accumulated in the pteridophyte Blechnum
intracellular labeling as well as without epoxy inclusion and niponicum, a Pb-hyperaccumulator. A quasi-monochromatic
with surface labeling. Nano-XRF measurement was performed beam was monochromatized to 16.5 keV using a Si(111)
at the nanoimaging end station ID22NI of the ESRF. Dynami- monochromator. The monochromatized X-ray beam was fo-
cally bent graded multilayers set in the K-B geometry were cused by a K-B mirror system into a 2.8 (horizontal) × 1.8
used to focus the X-ray beam to a spot size of approximately (vertical) µm2 microbeam at the sample position. From 2D
80 (horizontal) × 130 (vertical) nm2. Excellent nano-XRF maps imaging of Pb at the root, petiole, leaf vein, pinna epidermis,
were obtained for human SKOV3 cells. They claimed that nano- and sorus in the sample, the authors claimed that Pb, first
XRF using QD-based makers is very effective for the colocation transported to the upper parts of the plant, ultimately remained
of a specific intercellular target. at the terminal points of the transpiration stream, including the
Zoeger et al. (187) studied various SR-µ-XRF geometries to stomatal apparatus and water pores.
determine the distributions of Pb, Ca, Zn, and Sr at the One of the great advantages of the µ-XRF method is that it
cartilage-bone interface in human femoral heads and patellae. enables nondestructive elemental analysis at ambient pressure.
Experiments were carried out at beamline L at HASYLAB and at Therefore, µ-XRF analysis can be successfully applied for the
the Fluo-Topo beamline at ANKA. In conventional SR-µ-XRF, the historically-important samples. In addition, the result of elemental
primary X-rays chosen by the Ni/C multilayer around 17.5 keV imaging by µ-XRF can provide useful insights into the possible
were focused by means of a polycapillary half lens to a spot size origins of archeological samples. Powers et al. (192) examined
of 13 µm fwhm. The SR-µ-XRF results matched with backscattered an inscription of uncertain provenance by using XRF, SR-µ-XRF,
electron BE images of the tissue. Conventional SR-µ-XRF at EPMA, and XRD analysis. A stone tablet from New York
HASYLAB beamline L showed that Pb mostly accumulated in a University (NYU) was thought to be a modern copy of an
zone of some micrometers around the transition between calcified inscription from Teanum Sidicinum in central Italy. XRF measure-
and noncalcified cartilage. 3D-confocal SR-µ-XRF and SR-microf- ment of the stone tablet was performed at the Cornell High-Energy
luorescence tomography were performed at the ANKA Fluo-Topo Synchrotron Source (CHESS). A quasi-monochromatic X-ray beam
beamline and HASYLAB beamline L in order to obtain more using a W/B4C multilayer was collimated by mechanical slits
accurate information. It was found that the Pb and Zn coincidedly into 0.5 × 0.5 mm2. A strong Ca and weak Fe, Zn, and Pb were
accumulated at the tidemark. The authors concluded that Pb was detected from the ancient Roman inscriptions on marble. On
associated with this joint disease because the tidemark plays an the other hand, XRF spectra of the NYU tablet showed many
important role in osteoarthritis. Lima et al. (188) characterized of the same elements seen in the ancient Roman inscriptions;
the bone structures of the femoral head and the cortical and however, the XRF intensity of Ca was much weaker and that
trabecular regions by SR-µ-XRF measurement. Their measure- of other elements was much stronger. Therefore, it was
ments were performed in the standard geometry with 45° assumed that the NYU tablet was unlikely made of marble.
incidence and excitation with a white beam and capillary optics Elemental mapping images showed specific distributions in
with a 20 µm diameter collimation on the XRF beamline at the trace elements for the ancient Roman inscriptions, while
Synchrotron Light National Laboratory (Campinas, Brazil). Three elemental distributions of the NYU tablet were almost constant.
groups of bone specimens were obtained from 15 Wistar female On the basis of the results of XRF, EPMA, and XRD measure-
4976 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
ments, the authors concluded that the NYU tablet was not an particles using a laboratory µ-XRF spectrometer based on poly-
authentic Roman tablet. Constantinescu et al. (193) composi- capillary X-ray optics. A Mo rotating anode X-ray generator
tionally characterized several minute fragments of natural (Rigaku Ru-200, 60 kV, 200 mA) with a 300 × 300 µm2 spot size
Transylvanian gold by using SR-µ-XRF at the ANKA SR facility was used for the µ-XRF measurement. A quasi-monochromatic
and µ-PIXE in Dresden, Germany. The SR-X-ray beams mono- X-ray beam with a Nb filter (thickness, 77.4 µm) was focused
chromatized to 32.5 keV by a double-multilayer-monochromator by polycapillary X-ray optics into about 30 µm at the focal point.
were collimated to 93 × 116 µm2. The µ-PIXE analysis indicated The minimum detection limits measured with thin-film RMs
that the gold archeological metallic artifacts contained a high were in the range of 0.7-13.3 ng cm-2. In order to reduce the
amount of Ag (8 to 35%), low amount of Cu (several hundreds effects of the inhomogeneous distributions of X-ray intensity
ppm to 1.5%), and trace amount of Sn, Sb, and Te. To identify in the focal spot on the analysis results, the sensitivities were
the provenance of gold archeological metallic artifacts, trace corrected using a Gaussian function for the quantitative analysis
elements provided more important information than major of single aerosol particles. The accuracy of the analysis of single
components. In particular, the most promising elements were standard solution droplets was 25% on average depending on
platinum group elements (Sn, Sb, Hg, Pb, Te, and Cu). A the element and concentration. The precision of the analysis
spectacular application of these measurements to the authen- was better than 5%.
tication of nine Dacian gold bracelets was presented. Zhang TXRF. TXRF has been applied in many fields. Control of
and Sakurai (194) characterized bloodstone (a cryptocrystalline surface contaminants on Si wafers is one of the most important
variety of quartz) by using SR-XRF and XRD. The SR-XRF applications. Budri in the U.S. described in-line TXRF monitoring,
experiment was performed at BL-4A of the Photon Factory in which provides analytical information on Al, Ti, and Mo with high
Tsukuba, Japan. Highly brilliant SR X-ray beams from a throughput and a large sampling area (197). During implantation,
multipole wiggler source were monochromatized to 19.5 keV which is an important semiconductor process, coimplanting of
by a Si(111) double crystal, and a homogeneous beam of 0.5 × metallic contaminants occurs. Parts of the TXRF results were
0.5 mm2, restricted by an entrance slit, was used to irradiate validated by SIMS. In-line TXRF was applied for continuous routine
the bloodstone sample. Quantification of trace elements (Fe, monitoring of implanters and contaminants. The author pointed
Cu, Zn, Rb, and Sr) in rocks was performed by employing the out the benefits of TXRF, that is, a fast technique of less than 1 h
Lachance-Traill algorithm. XRD measurement was performed per wafer, a fully automated technique in a clean-room environ-
by using a RINT Ultima III plane X-ray diffractometer (Rigaku) ment, and having a large analysis spot size of 10 mm. To improve
operated at 40 kV and 40 mA. 2D-elemental maps of major these positive qualities of TXRF, sweeping TXRF (SP-TXRF) has
components (Fe and Si) in the bloodstone showed heteroge- been developed. In SP-TXRF, the sample is not fixed but rather
neous distributions. In addition, it was found that Ti and Mn is continuously scanned. Therefore, analytical information of any
were correlated to Fe, whereas Cu, Rb, and Sr were correlated surface contaminants on a large Si water is obtained within a short
with the major element Si. The authors suggested that bottle measuring time. Borde et al. studied the optimization of this
green was related to a Fe2+ or Cu compound, yellow and red technique to monitor the presence of metallic contaminants (198).
were from the contribution of Fe2O3 or another Fe3+ compound, The authors investigated SP-TXRF in comparison with normal
and black was from the contribution of Fe3O4. direct TXRF (D-TXRF) in relation to throughput, detection limits,
All the above µ-XRF measurements were performed at SR- surface coverage, accuracy, quantification, etc. The TXRF mapping
facilities. SR is the most desirable source for micro X-ray beams results obtained with different experimental parameters in SP-
because of high brilliance. However, the only drawback of the TXRF were shown in comparison with the D-TXRF map in Figure
SR facilities for conducting such experiments is limited machine 11. The authors concluded that sweeping TXRF was a compromise
time and availability. In addition, in the case of measuring precious between surface coverage, limits on quantification, and through-
or large artifacts, it might be difficult to transport the samples put. Denel et al. studied D-TXRF, SP-TXRF, and vapor phase
into the SR-facility. In contrast, by combining a polycapillary lens decomposition TXRF (VPD-TXRF) for the analysis of metallic
with a finely focused micro X-ray tube, a micro X-ray beam on contaminants on Si wafers (199). The performance of different
the order of several tens of micrometers in diameter is available TXRF modes was investigated. The authors suggested applications
with sufficient intensity for XRF analysis in the laboratory. of these TXRF techniques to various integrated circuit manufac-
Bontempi et al. (195) investigated the contamination of an turing processes, taking into account the advantages and draw-
industrial metallurgical site in the urban area of Brescia (northern backs of each TXRF mode, as follows. VPD-TXRF is an extremely
Italy) measured using a benchtop µ-XRF instrument for measure- sensitive technique. Therefore, VPD-TXRF would be useful for
ments. The authors chose plant samples of the foliose lichen contamination control in the wet clean process and thermal
Xanthoria parietina as biosensors because they are excellent treatment. D-TXRF would be useful for local and distributed
bioaccumulators of trace elements (Fe, Cr, Zn, Ca, Mg, and Mn). particle-like contaminants on the fronts and backs of wafers in
The XRF experiments were performed by means of a Unisantis the process of deposition, etching, and implantation, while SP-
XMF-104 µ-XRF spectrometer equipped with a polycapillary X-ray TXRF might be chosen for contamination analysis on the backs
lens focused to approximately 100 µm. The excitation settings of wafers during the process of lithography and maintenance.
were 30 kV and 300 µA. The authors concluded that the analytical Another application of TXRF to trace metal analysis was
results of the trace elements in the lichens enabled continuous suggested by Takahara et al. (200). Hafnium silicate, which is a
monitoring of the air quality in the surrounding area. Sun et al. high-k material, is a key material in the semiconductor field.
(196) performed quantitative XRF analysis of single aerosol However, when a conventional X-ray tube with a W anode is used,
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4977
Figure 11. TXRF mapping of a wafer contaminated with 10 Mn spots: (a) 10 points D-TXRF centered above spots and (b) various SP-TXRF.
Reprinted from (ref 198) Spectrochim. Acta, Part B, 63, Borde, Y.; Danel, A.; Roche, A.; Veillerot, M. Sweeping total reflection X-ray fluorescence
optimisation to monitor the metallic contamination into IC manufacturing, 1370-1374, Copyright 2008, with permission from Elsevier.

the overlapping of W L lines and Hf L lines pose a serious problem. lines. Actually, different ratios of 5.98 and 8.44 were obtained
Thus, the authors used a 1.2 kW Ir anode fine focus diffraction for slowly growing HCA-7 (human colon adenocarcinoma) and
tube for TXRF analysis. They pointed out that X-ray resonant rapidly proliferating HT-29 (human Caucasian colon adenocar-
Raman scattering and the escape peak of Ir LR overlapped with cinoma) cells, respectively. A research group from Portugal
Ni KR. By taking these effects into account, detection limits from and Germany also studied breast cancer tissues by TXRF (205).
9 × 109 to 2 × 1010 atoms/cm2 were achieved for Ti, Cr, Fe, Ni, P, S, L, Ca, Fe, Ni, Zn, Cu, and Br of normal and cancerous
and Cu on a hafnium silicate film deposited on a Si water. tissues were measured. A thin section between 5 and 10 µm
Sekowski et al. applied TXRF for the investigation of sputtering of each tissue was prepared by a microtome. TXRF analysis
processes (201). They studied an Ar ion beam sputtering process was performed by a laboratory TXRF (Atomika, Extra II) with
for a Ge target with angles of incidence of 75° and 80° and with a Mo X-ray tube. Concentrations of almost all elements
an ion energy of 20 keV. The sputtered particles were deposited including Br measured from cancerous tissues were larger than
on a silicon wafer and then analyzed by TXRF. The sputtering those for normal breast tissue, although a previous study
yield was measured as a function of the incident angle of the Ar showed decreased Br concentrations for different carcinoma
ions. The experimental results were compared to Monte Carlo tissues.
simulations. The comparison showed strong differences due to Archaeological ceramics were measured by a Spanish research
the influence of primary knock-on atoms. The authors concluded group (206). The ceramic samples were digested in HNO3 and
that this influence should be included in the Monte Carlo HCl acids in a microwave oven. The authors optimized the acid
simulations. digestion procedure. A volume of 5 µL of the leached solution
Hönicke et al. developed micro- and nanostructured materials with a standard Se solution (10 ppm) was deposited on a quartz
on a Si wafer for investigation of depth profiling by GIXRF at reflector. The five leaching protocols for the ORC-2 reference
BESSY II (202). 3-D test structures, which were Si bars with material were analyzed by INAA (Instrumental Neutron Activa-
widths and spacing in the micrometer or nanometer range, were tion Analysis) and TXRF (EXTRA-II with a Mo X-ray tube). The
prepared by IMEC in Belgium. These structures had thin layers correlation between the quantitative data obtained by INAA and
oxidized on the sidewall. Depth-dependent sidewall contamination, TXRF was shown with a squared correlation coefficient of 0.998.
layer thickness, and composition could be obtained by applying The authors attempted Fe liquid-liquid extraction with MIBK
GIXRF. A group from France and Rigaku reported thin-film solution to improve the accuracy of the quantitative TXRF
analysis by TXRF (203). The thickness of the thin films was analysis because the high signal of Fe was a serious problem
evaluated by TXRF at a fixed incident angle less than the critical in the TXRF analysis of microwave acid leaching. As a result,
angle using calibration standards. A good linearity of the TXRF the squared correlation coefficient in the relationship between
calibration relationship for Al2O3 films was obtained in a limited the INAA and TXRF quantitative data was improved to 0.9992.
range of less than 1.5 nm. The authors described that TXRF Vázquez et al. analyzed Argentinean cultural objects by TXRF
signal saturation occurred rapidly for dense films such as HfO2, (207). A small amount of pigment was taken from a painting by
depending on the incident angle of the primary X-rays. rubbing it with a piece of cotton. TXRF analysis was performed
Another growing field of TXRF application is the analysis of by a laboratory-made TXRF module with a Mo X-ray tube. Five
biological samples. A Hungarian research group studied the TXRF identified pigments were detected. Pigments in rock painting in
analysis of human adenocarcinoma cancer cell lines (204). Cancer Argentina were also successfully analyzed by TXRF. The TXRF
cells were sedimented to a quartz plate after centrifugation. Then, spectra suggested that a Hg2Cl2 compound was used as a
3 mL of HNO3 solution was added for microwave-assisted bactericide for underwater archeology. Groma et al. analyzed
digestion. The sample preparation conditions (centrifugation aerosols in an airport by SR-TXRF (208). Fine particulate
and digestion parameters) were optimized. Precision, recovery, matters (PM2.5) originating from emissions of aircraft, ground
and dynamic range were evaluated for Zn, Fe, and Cu by using handling vehicles, etc. were critical pollutants in the airport.
a laboratory TXRF instrument (Atomika Extra IIA). The Zn/ Size fractionated aerosol samples were collected on Si wafers
Cu ratio was found to be a characteristic index for cancer cell by using a seven-stage May cascade impactor at Budapest’s
4978 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
Ferihegy airport. TXRF analysis was performed at the HASY- investigated the Athabasca granulite terrane of continental lower
LAB facility. Typical elements coming from combustion pro- crust exposed in the hanging wall of the thrust-sense Legs Lake
cesses (Zn and Pb), aircraft related emissions (Cu), and road shear zone in the western Canadian Shield, where the terrane
salting processes (Cl) were detected. The authors concluded and the thrust zone are cut by the Grease River shear zone. The
that the combination of May impactor sampling and TXRF structure hosts a syn-tectonic granite dike, and detailed textural
analysis had potential for environmental monitoring in industrial analysis and in situ EPMA of monazite in the dike indicated three
and traffic processes. Óvári et al. determined the presence of discrete episodes of strain accumulation, each corresponding to
carbon in natural freshwater biofilms by TXRF (209). They syn-kinematic growth of monazite. The results provided evidence
used a laboratory TXRF instrument (ATI low-Z spectrometer) for a previously unrecognized episodic record of subhorizontal
made at Atominstitut, Vienna, Austria. A Cr anode X-ray tube NW-SE shortening and dextral shear strain along the Grease
was operated at 30 kV and 12 mA. The internal standard was River shear zone. Two gneiss and one granulite cobble from the
the natural Ti content of the biofilm. The inside of the TXRF Silesian Unit flysch rocks (Western Outer Carpathians, southern
spectrometer was evacuated by a rotating pump. The carbon Poland) were studied using EPMA (214). The pebble to cobble
in the biofilm was successfully determined. size clastic material present in the Carpathian flysch rocks turned
Stas et al. in Syria measured uranium by TXRF (210). They out to provide the only opportunity to improve knowledge
used a laboratory TXRF instrument with a Si(Li) detector. The concerning the evolution of the Silesian Ridge. Th-U-total-Pb
uranium measured was contained in the organic phase, which monazite chronology was used to constrain the timing of meta-
resulted from the first and second cycles of uranium extraction morphism and magmatic protolith of gneiss cobbles derived from
from wet-process phosphoric acid. The uranium LR (13.6 keV) the Silesian Ridge. On the basis of microtextural observations and
was measured with an internal standard of Ga. The detection limit chronological results, four monazite populations were identified.
of uranium was 0.15 µg mL-1. The authors concluded that the Results obtained using improved EPMA techniques were consis-
result obtained by TXRF was in very good agreement with that tent with existing data but much more tightly constrained,
obtained by fluorometry (stripping analysis) method. highlighting the potential role of EPMA for monazite analysis in
EPMA. EPMA is a powerful technique for nondestructive provenance studies.
chemical analysis of ancient artifacts. Cagno et al. (211) examined During the review period, a substantial amount of applications
91 samples of vessel glass originating from a number of sites of quantitative light element analysis of atmospheric individual
throughout Tuscany, Italy, and compared their SEM/EDX data particles using thin-window EPMA (TW-EPMA) were reported.
with those of Venetian glass in order to evaluate differences in This technique can identify chemical species of individual airborne
glassmaking materials. Two kinds of ash used as a fluxing agent particles without a special treatment of the sample. Kang et al.
were identified, one of which is of east Mediterranean origin while (215) demonstrated its capacity to obtain detailed information on
the other is likely to be Spanish. Two types of silica sources were individual particles collected in a city by the combined use of
also found. One of these was recognized as being quartziferous quantitative X-ray spectral and morphological data. Many different
river pebbles, while the other is proposed to be local sand. In particle types were identified and their emission source, transport,
their application, the quantitative EPMA was demonstrated to and reactivity in the air elucidated. In the aerosol samples, particles
clearly identify the different fluxing agents and silica sources used in the “soil-derived particles” group were the most common,
in Tuscan glassmaking during the Middle Ages to Renaissance followed by “reacted sea-salts”, “reacted CaCO3-containing par-
period. Window glass fragments (5th- to 7th-century) from the ticles”, “genuine sea-salts”, “reacted sea-salts + others”, “Fe-
Petra Church in Jordan were analyzed by EPMA and spectropho- containing particles”, “anthropogenic organics”, (NH4)2SO4, “K-
tometry in order to determine the provenance of the raw glass containing particles”, and “fly ash”. The application of this
and the secondary production procedures of the window-panes single-particle analysis clearly revealed the different charac-
(212). The chemical composition and manufacturing techniques teristics and sources of six aerosol samples investigated. Six
of the window glass recovered from the Petra Church as well as sets of aerosol samples collected in the Marine Boundary Layer
glass groups prevalent in Late Antiquity were investigated. The (MBL) of the Bohai Sea and the Yellow Sea were analyzed
chemical data showed that the assemblage forms a homogeneous using TW-EPMA by Geng et al. (216). Samples D1, D2, and
group of soda-lime-silica glass of the Levantine I type and green D3 were collected during an Asian dust storm event, whereas
glass has higher silica and lower soda contents than aqua-blue samples N1, N2, and N3 were collected on non-Asian dust days.
fragments. The composition of one sample suggested the recycling On the basis of the X-ray spectral and SEI data, 15 types of
of Roman glass. Overall, their results confirmed the trade of glass particles were characterized. For all the samples, soil-derived
between the Levantine coast and Petra during Late Antiquity. particles (aluminosilicates, SiO2, and CaCO3) were the most
U-Th-Pb geochronological dating of monazite using EPMA, abundantly encountered, followed by (C, N, O)-rich droplet
a method developed in the past decade, has attracted wide particles, marine particles, and then carbonaceous, Fe-rich, fly
attention for its speed, low cost, and relatively high reliability. In ash, and (C, N, O, S)-rich droplet particles. During the Asian
addition, it has a very high spatial resolution, superior to other in dust storm event, primary soil-derived particles decreased and
situ techniques for analyzing compositions of zoned monazite secondary particles, especially those containing nitrates, in-
crystals of less than 50 µm in size. Therefore, the method has creased. Moreover, the relative abundance of the (C, N, O)-
been widely applied to determine the timing of multistage tectono- rich droplet particles was elevated in both PM2.5-10 and PM1.0-2.5
metamorphism, which is demonstrated by many reported applica- fractions, and the abundances of carbonaceous and (C, N, O,
tions during the review period. For example, Dumond et al. (213) S)-rich droplet particles were reduced. The results imply that
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4979
Asian dust aerosols were an important carrier of gaseous of the shooting person. The experiments were designed in such
inorganic nitrogen-containing species (within 1.0-10 µm), a manner that the substrates for collecting GSR were reminiscent
especially NOx (or HNO3) and NH3, in the MBL of the Bohai of those usually obtained for examinations in criminal cases. The
Sea and the Yellow Sea. Kang et al. (217) performed an results of the performed examinations in the form of parameters
extensive study on seasonal subway samples collected at an describing GSR particles showed that the number of GSR, and
underground subway station in Seoul, Korea. For all 8 samples proportions of their chemical classes as well as their sizes,
collected twice in each season, 4 major types of subway revealed a dependence on the shooting distance, in both the
particles, based on their chemical compositions, are signifi- direction of shooting and backward, i.e., on the shooting person.
cantly encountered: Fe-containing, soil-derived, carbonaceous, The analysis of the distribution of particles in the vicinity of the
and secondary nitrate and/or sulfate particles. Fe-containing shooting gun may be utilized in description of the general rules
particles are generated indoors from wear processes at of the dispersion of GSR as well as in the reconstruction of a real
rail-wheel-brake interfaces, while the others may be intro- shooting case.
duced mostly from the outdoor urban atmosphere. Fe-contain- The study of the hygroscopic properties of airborne particles
ing subway particles almost always exist either as partially or is important, as solid or aqueous particles play different roles in
fully oxidized forms in underground subway microenviron- climate change. Aqueous particles are larger and scatter solar
ments. The relative abundances of the particles of outdoor radiation back to space more efficiently than solid particles. They
origin vary somewhat among seasonal samples to a lesser can also modify atmospheric chemistry through reactions such
degree, reflecting the fact that indoor emission sources as N2O5 hydrolysis and secondary organic aerosol production.
predominate. For several years, environmental SEM (ESEM) has been used
Li et al. (218) reported the characterization of suspended to determine water uptake by individual airborne particles as
particulate matter (SPM) collected in the urban area of Tokyo a function of relative humidity (RH). However, most previous
using a TES microcalorimeter X-ray detector mounted on a FE- reports in this area have been on the hygroscopic behavior of
SEM system. This prototype microcalorimeter spectrometer with standard particles with known chemical compositions. Comple-
an energy resolution of 19 eV identified some severe peak overlaps mentary determination of the elemental composition of single
in the spectra measured by the traditional Si(Li) solid state particles can be performed using EDS, and thus the ESEM/
detector, especially in the low region of X-ray energy. In addition, EDS technique has a potential to provide hygroscopic, mor-
the TES microcalorimeter showed good spatial resolution for the phological, and chemical properties of ambient aerosols and
microanalysis of SPM. The FIB was successfully applied to to identify possible correlations between these properties.
fabricate a cross section of a single SPM particle. The chemical Hiranuma et al. (221) reported measurements of the hygro-
compositional difference between the surface and inner parts, and scopicity of size-selected agricultural aerosols collected from
among different surface parts of the SPM, was also determined. a ground site at the nominal downwind and upwind edges of a
However, new modeling for the quantitative analysis of SPM using feedlot in the Texas Panhandle. They claimed that most of the
this system is still needed. agricultural particles do not take up significant amounts of
As a forensic application, the analysis of gunshot residues water when exposed to up to 96% RH. However, a small fraction
(GSR) has been routinely performed in order to solve particular of particles in the coarse mode deliquesced at approximately
problems such as differentiation of entry and exit wounds, 75% RH and reached twice their original sizes by 96% RH. The
estimation of the shooting distance, establishing the kind of observed changes in particle size with increased RH signifi-
ammunition used, tracing the trajectory of a projectile, and relating cantly impact total aerosol extinction, visibility, and human
an individual to a shooting incident. Fulfilling any of these tasks health. Asian dust particles of diameter (>1 µm) collected in
may contribute to a shooting incidence reconstruction. A profi- southwestern Japan were also analyzed with ESEM (222). The
ciency test on the detection and identification of GSR by SEM/ hygroscopic behavior of sea-salt-free dust particles were
EDS was carried out over a 2 year term (219). The latest test investigated with respect to their contents of sulfate and nitrate.
was performed in 2005/2006. A total of 75 laboratories from 28 Sulfate- and nitrate-free dust particles (not containing sulfur
countries participated in this proficiency test and submitted a total and nitrogen), as well as sulfate-containing ones, did not change
of 83 independent data sets. The participating laboratories were in their crystalline morphology as the RH was increased from
requested to determine the total number of PbSbBa-containing 15% to 90%. In contrast, calcium nitrate-containing dust particles
particles on a synthetic test sample, following their own laboratory appeared in the aqueous phase, even at 15% RH. These results
specific methods of automated GSR particle search and detection indicate that nitrate formation on coarse dust particles could
by SEM/EDS. Size and position of the detected particles had to substantially enhance the hydrophilicity of the particles and
be reported by the laboratories and were evaluated statistically. possibly vice versa, whereas sulfate formation could not.
The results were compiled by means of z-scores to assess EPMA is a powerful tool for quantitative elemental analysis.
individual laboratory achievements (interlaboratory) as well as However, if molecular speciation of the specimen in addition to
intralaboratory performance, and the comparison to the results elemental concentrations can be performed, rich information on
of the previous proficiency test run showed that there was a the specimen can be obtained. The combined use of SEM/EDS
noticeable improvement in the method’s detection capability. and µ-Raman techniques can be very promising, as the combined
Brozek-Mucha (220) examined various features of GSR collected system permits in situ characterization of a sample based on both
from targets in a function of the shooting distance as well as from its molecular and elemental makeup. Falcone et al. (223) exam-
hands and the forearm, front, and back parts of the upper clothing ined crystalline inclusions, commonly called stones, which are
4980 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
Figure 12. Elemental maps of K (a), Ca (b), and Ni (c) taken on a hand-sectioned cryo-fixed freeze-dried Hybanthus floribundus subsp.
floribundus leaf. Reprinted with permission from (ref 230) Siegele, R.; Kachenko, A. G.; Bhatia, N. P.; Wang, Y. D.; Ionescu, M.; Singh, B.;
Baker, A. J. M.; Cohen, D. D. X-Ray Spectrom. 2008, 37, 133-136. Copyright 2008 John Wiley and Sons.
dangerous defects present in industrial glass products. The Šmit et al. in Slovenia obtained elemental depth profiles in paint
reactions occurring between refractory stone materials and molten layers by PIXE (227). They varied the proton energy to probe
glass were studied by the combined use of SEM/EDS and the concentration depth profile of metal-based pigments in the
µ-Raman spectroscopy. The Raman spectra of pure crystalline paint layers. The energy scans were performed by varying the
compounds were compared with those of the unknown phases. beam exit energy of the accelerator. Algorithms previously
This technique allowed the identification of the nature of the developed for depth profiling were improved to include light
recrystallized phases, clearly revealing the origin and character- elements. A test fresco painted with known metal pigments was
istics of stones in glass. Samples of the secondary uranium analyzed. The deconvoluted profiles measured at different colors
minerals collected in the abandoned uranium mine at Pecs were successful and reproduced the profiles as confirmed by SEM
(Hungary) were investigated by the combined use of SEM/EDS observation. This technique was applied to several historical
and µ-Raman spectroscopy (224). They were applied to locate samples, such as the portrait of an archbishop of Prague, the
U-rich particles and identify the chemical form and oxidation state painting of Matej Sternen, etc.
of the uranium compounds. The most abundant mineral was a K Several elementals in the leaves of Cd/Zn hyperaccumulator,
and/or Na uranyl sulfate (zippeite group). U(VI) was also present Thlaspi praecox, were measured by micro-PIXE (228). The plants
in a form showing intensive Raman scattering at 860 cm-1, which were collected in the highly Cd, Zn, and Pb polluted area of
can be attributed to uranium trioxide. In that work, the Slovenia. It was found that the most of the accumulated Zn was
successful application of µ-Raman spectroscopy for the identi- located in the epidermis, while most of the Cd and Pb was
fication of uranyl mineral species on the level of individual distributed within the mesophyll. The authors concluded that the
particles was demonstrated. main Zn detoxification mechanism was Zn sequestration in the
PIXE. PIXE, especially with an external proton beam, has been symplast of large vacuolated epidermal cells and that S and Ca
applied in many fields, such as archeology, paintings, environ- played a role in Cd detoxification and tolerance. Yamazaki et al.
mental samples (e.g., air dusts), and biological samples. Calligaro at Tohoku University in Japan studied an As hyperaccumulator
at CNRS in Paris reported applications of PIXE as well as particle- plant (Pteris vittata) for phytoremediation research by a submilli-
induced γ-ray emission (PIGE) and RBS to archeological and PIXE imaging system (229). The developed submilli-PIXE setup
historical glasses (225). An external microbeamline of the AGLAE provided spatial distribution images of elements in a region of 3
facility was used with two X-ray detectors for PIXE, one HPGe × 3 cm2 with a resolution of about 0.5 mm. A 3 MeV proton
detector for PIGE, and a surface barrier detector for RBS. The beam was used in air. Elemental images of laminas were
first Si(Li) for PIXE was operated in a helium steam to measure obtained in vivo without sample preparation, showing that As
light elements from O to Fe, which were the principal constituents accumulated in the edges of the Pteris vittata fronds. Siegele
of the glass. The second detector for PIXE was used with a 50 et al. at ANSTO in Australia also measured trace metals in
µm Al foil to absorb the strong Si characteristic line emitted from metal-accumulating plants by micro-PIXE at 5 µm resolution
the glass. This setup was applied to the analysis of a 12th century (230). The sample was prepared by freeze-substitution and
stained glass window to determine the various medieval glasses freeze-drying techniques. Elemental maps of K, Ca, Ni, and
employed in this panel. With the combination of PIGE and RBS, Cu were obtained for the plant leaf as shown in Figure 12. For
alternate makers of the glass surface were revealed. This informa- the sample prepared using freeze-substitution with THF, cellular
tion was useful for conservation science. or subcellular resolution could be achieved. However, the redis-
de Viguerie et al. in CNRS in Paris studied the composition of tribution of metals might be a drawback. In the case of freeze-
Renaissance paint layers by simultaneous PIXE and backscattering dried leaf sections, cellular metal concentration was preserved;
spectrometry (BS) (226). They used 3 MeV-PIXE for the analysis however, only cellular resolution was achieved.
of the elemental composition from major elements to traces, while The concentrations of some elements were measured on pine
BS was used as a complementary technique to determine the tree rings from forests located at 6 km from a volcano’s crater in
proportion of pigments and organic binder. BS spectra of C and Mexico by PIXE-RBS with an external proton beam (231). The
O clearly showed the difference for pigments with and without composition of the tree rings exhibited an increased tendency for
oil. Finally, an elemental profile was taken for the painting cross P, S, and K concentrations since 1991, while metallic elements
section with 5 µm steps as well as profiles of the pigments and (Mn, Fe, and Cu) did not show any special distribution. This result
organic binder. was probably related to the fact that the Popocatepetl volcano
Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4981
increased its activity starting in 1991. In addition, the result 1940s that transmission of X-ray beams through a perfect crystal
suggested that the changes in the pines’ elemental compositions dramatically increases when X-rays satisfying Bragg’s law are
were more related to gaseous volcanic exhalation than ash applied, even if normal X-ray transmission is much less. This
emissions. Asian yellow sand dust particles were analyzed by PIXE phenomenon is called the Borrmann effect and was revisited by
(232). The yellow dust particles were collected on a thin poly- Pettifer et al. (237). They observed that XANES at Gd L-edges
carbonate film by a single stage impactor in the Kyushu area of (including LI, LII, and LIII edges) of Gd3Ga5O12 (Gd-Ga garnet)
Japan. Besides the principal elements such as Si, Ca, O, C, and exhibits intense pre-edge absorption in the Borrmann case,
H, the particles contained S and heavier elements, which origi- which is usually not observed in conventional spectra. They
nated from mixing with anthropogenic aerosols. Marine aerosols showed that this effect could be seen when the electric field
(Na, Mg, and Cl) were also observed, indicating that the particles of the X-ray beam approached zero amplitude at the crystal
were transported from the Asian continent. The authors concluded planes. In this case, the electric field gradient reached its
that single-particle analysis of yellow sand dust is useful for maximum, which enhanced the usually weak quadrupole
understanding their formation process during transportation. absorption, such as the pre-edge peak in Gd L-edge XANES.
Lunderberg et al. studied PIXE analysis of trace metals of These results are related to discussions about resonant X-ray
sediments in comparison with ICP-OES (233). A standard soil diffraction, the nature of pre-edge lines being identified by
sample (NIST SRM 2586) was analyzed by both techniques. For inelastic X-ray scattering, and applications to photonic crystals.
PIXE analysis, the sediments were pressed into a pellet, which Ruffoni et al. (238) directly measured magnetostriction at the
was placed in a vacuum and irradiated with a 2.3 MeV proton intrinsic atomic scale. For this purpose, differential XAS was
beam. For ICP-OES, the sediment samples were digested with employed using dispersive XAS apparatus for Fe81Ga19 alloys. This
microwave-assisted acid. The eluents were analyzed by ICP-OES. method is a new approach to dichroism studies and it exploits
The total sample preparation time for PIXE analysis was roughly high-stability, low-noise conditions to measure tiny perturba-
one-third that of acid digestion ICP-OES. PIXE measurement tions to atomic structures induced by modulating some external
enabled nondestructive total metal analysis, while the acid diges- sample properties. By combination of this technique with
tion did not elute all the metal. However, a drawback of PIXE is conventional EXAFS to obtain average local structures, it was
its high limits of detection for many environmental metals in soils. found that the enhanced magnetostriction induced by the
Nakazato et al. studied subcellular changes of essential metals addition of Ga to Fe originated from the Ga environment. These
by micro-PIXE for Cd-exposed mice (234). Four mice were dosed results revealed the atomic origins of strain enhancement,
orally with 100 mg/L of Cd in drinking water for 1.5 or 2 years. which allows true comparison with the results of theoretical
Frozen liver and kidney specimens were cut by a cryostat into 15 studies.
µm sections and then measured by micro-PIXE with a 1 µm beam Bimetallic nanomaterials have been used in various technolo-
spot size. It was found that Cd and Zn accumulated in the renal gies because of their unique catalytic, electronic, and magnetic
cortex. An elemental map showed that a large amount of Cd was properties. Teng et al. (239) demonstrated the formation of Pd/
spatially combined with Zn. This result suggested that Zn might Au nanostructures from Pd nanowires via galvanic replacement
contribute to protect against orally administered Cd toxicity. Simon reactions using EXAFS coupled with high-resolution transmission
et al. studied the skin barrier function by micro-PIXE (235). Skin electron microscopy. They found progressive changes in chemical
was exposed to various stresses, such as sun and urban or composition and crystalline structure from pure Pd nanowires to
industrial pollution. The authors measured pig ear skin, which Pd68Au32, subsequently to Pd45Au55, and finally to Au nanopar-
was shock-frozen in liquid nitrogen and sectioned by cryomicro- ticles. The results obtained mainly by EXAFS showed that a
tome. A 16 µm thick tissue section was measured by scanning nonrandom Pd68Au32 alloy with an Au-rich core and a Pd-rich
with micro-PIXE with a beam diameter of about 2 µm. The authors shell is formed at an early stage but, following diffusion of Au
confirmed that the elemental distributions obtained were altered atoms into the core region, the random alloy Pd45Au55 is
after exposure to a chemical compound (sodium dodecyl sulfate). formed. The performance of bimetallic nanomaterials is closely
In addition, no penetration of aluminum oxides, which originated related to the structure of the alloys and whether they are
from cosmetics, was found in their experiments. intermetallic alloys, random alloys, or nonrandom alloys. Thus,
Strontium is naturally present in human bone; however, its the findings in their study revealed that the galvanic replace-
influence on human health is not well-known. XRF analysis has ment technique introduced in that study is novel in terms of
been recently applied to the analysis of Sr in bone. In this case, preparing nonrandom alloys. Nonrandom Pd/Au alloys could
however, depth distribution of Sr in bone must be taken into be particularly relevant to several important catalytic applica-
account. Thus, Zamburlini et al. measured Sr-depth distribution tions such as the water gas shift reaction, CO oxidation, and
by micro-PIXE (236). Five intact cadaver index fingers from five oxidation of alcohols to aldehydes.
male subjects were prepared. Five bone slices were embedded It appears that NEXAFS is a powerful tool in polymer sciences.
in resin, and different depths were measured by micro-PIXE with Even for copolymers having the simplest structures, polymers
a beam energy of 3 MeV and a spot size of about 5 µm × 5 µm. produce a wide range of intricate structures and morphologies,
The result showed that Sr was uniformly distributed inside the which leads to various phenomena and technological applications
bone at least on a 100 µm scale, indicating that there is no need of polymers. To understand these phenomena and applications,
for the correction of XRF data of Sr in bone. structural characterization of these polymers by spectroscopies
XAS. XAS has been studied in various scientific fields of is essential. Since polymers usually consist of light elements such
fundamental and applied interests. It has been known since the as C and N, XAS in the soft X-ray region (NEXAFS) has been
4982 Analytical Chemistry, Vol. 82, No. 12, June 15, 2010
used as a characterization tool. Ade and Hitchcock (240) sum- the formation of Cu nanoparticles were also discussed in the
marized the application of NEXAFS to this field with their unique manuscript.
aspects. In particular, STXM is a powerful tool for investigating Speciation of elements in aerosols, or atmospheric dusts, can
heterogeneous materials formed within polymers. An example be important when considering their influence on the environ-
concerning precipitates in polyurethane analyzed by STXM was ment, such as on climate change, transportation of pollutants, and
given. The analyses revealed quantitative compositions of the health effects. Takahashi et al. (244) studied speciation of Ca in
matrix and precipitates consisting of urea, urethane, and polyol Asian dusts transported from western China to the North Pacific
functionalities. In such soft X-ray region, wet cells, such as Ocean. Calcium K-edge XANES spectra of dusts collected in
sandwich-type cells using two thin Si3N4 membranes, have been western China, eastern China, and Japan showed that the calcite
used to measure NEXAFS spectra for microgels and wet and gypsum contents in the dust decreased and increased,
polymers. Comparison with other methods and technical respectively, as the dust was transported to the east. These results
information about radiation damage to polymers caused by showed that acidic sulfur species such as sulfuric acid were
neutralized by calcite contained in such Asian dusts. In particular,
incident X-rays and about spatial resolution attained by various
successful application of conversion electron yield detection in
methods were also discussed. They also pointed out that
the XANES measurement, which is a surface sensitive method,
coupling with resonant soft X-ray scattering is effective because
showed that the neutralization reaction occurred at the surface
of its smaller nanometer-scale spatial resolution.
of the dust particles, suggesting that the neutralization reaction
Metallocenes having a sandwich structure consisting of a
proceeded during the long-range transportation of Asian dust in
transition metal and two cyclopentadienyl ligands have been used
the atmosphere.
as catalysts in coordination polymerization processes. Among
In earth sciences, it has become clear that the ratios of stable
these, metallocenes of group 4, especially Zr, are active in catalytic
isotopes of heavy elements can change through various chemical
olefin polymerization. Since the coordination sphere around the reactions in natural systems, which is linked to precise determi-
metal center is responsible for the structural and electronic effects, nation of atomic weight, a very fundamental value in science. Juillot
which in turn affect the activity and selectivity of the catalyst, et al. (245) focused on the variation of isotopic ratios of Zn (e.g.,
Silveira et al. (241) analyzed the structure of various Zr metal- 66
Zn/64Zn, 67Zn/64Zn, and 68Zn/64Zn) during sorption on goethite
locenes using EXAFS and X-ray photoelectron spectroscopy. They and iron hydroxide. According to EXAFS analyses, hydrated
found that electronic effects are important for the catalytic activity Zn2+ ion and Zn2+ sorbed on goethite are in 6-fold coordination,
of unbridged metallocenes, but structural factors represented by whereas a tetrahedral surface complex was observed for Zn2+
Zr-C interatomic distance do not play a key role. In contrast, the on iron hydroxide. It is well-known that heavier isotopes are
Zn-C distance affects catalytic activity for bridged metallocenes. enriched in the species with shorter bond lengths in the
EXFAS is a powerful tool for obtaining local structure around the equilibrium isotope fractionation system. This is consistent with
center atom, as will also be shown below for protein-metal ion the fact that the 66Zn/64Zn isotopic ratio relative to the hydrated
interactions. Zn2+ ion is larger for Zn2+ sorbed on iron hydroxide than that
Peroza et al. (242) studied binding of Zn2+ ions with metal- sorbed on goethite by considering the structures of their
lothionein Ec-1, small cysteine-rich proteins considered impor- surface complexes. The ability to determine local structures
tant in the homeostasis of essential metal ions such as Zn2+ of such sorbed species by EXAFS is quite important in
and Cu+. Multiple methods such as 113Cd NMR spectroscopy understanding isotope fractionation in natural and laboratory
and mass spectroscopy were employed. Among these, EXAFS systems.
was effective in identifying binding sites of Zn2+ in the Kouichi Tsuji graduated in 1992 at Tohoku University, Japan, and
metallothionein, in particular providing clear evidence that the received his Ph.D. in metallurgy. After that, he became research associate
in the Analytical Science Division of the Institute for Materials Research
two conserved histidine residues in the C-terminal part of the (IMR), Tohoku University, Japan. Since 2002, he has studied at Osaka
protein are participating in the coordination of Zn2+. Finally, City University, Japan. At present, he is a Full Professor in the Department
the possible relevance of these findings for the proposed of Applied Chemistry & Bioengineering. His research activities involve
the development and improvement of analytical X-ray methods, such as
biological functions of wheat Ec-1 was discussed. TXRF, Micro(3D)-XRF, EDXRF, PIXE, EPMA, and their applications.
Manceau et al. (243) reported an interesting formation of Cu Kazuhiko Nakano graduated in the field of industrial chemistry from
nanoparticles at the soil-root interface based on careful examina- Meiji University in Tokyo, Japan, in 2000. He received his Ph.D. from
Meiji University in 2005. At present, he is a Visiting Researcher at the
tion of EXAFS spectra recorded at bulk and micrometer scales. Department of Applied Chemistry & Bioengineering at Osaka City
Copper as a free ion can catalyze the production of damaging University, Osaka. His research interests include the development of a
radicals. Thus, it is considered that plants diminish excess Cu novel 3D microregion XRF spectrometer, quantitative analysis of trace
elements in environmental samples, and development of environmental
strategically. On the basis of the EXAFS spectra of Cu in the reference materials.
root-soil system, it was revealed that the common wetland plants Yoshio Takahashi graduated in 1997 from The University of Tokyo,
Phragmites australis and Iris pseudoacorus can transform Cu into Japan, and received his Ph.D. in environmental radiochemistry. After
that, he became research associate in Department of Earth and Planetary
metallic nanoparticles in and near the roots, assisted by endomy-
Systems Science, Hiroshima University, Japan. At present, he is a Full
corrhizal fungi when grown in contaminated soil in the natural Professor in the same department in Hiroshima University. His research
environment. The mechanism of Cu nanoparticle formation was interest is primarily in the speciation studies in environmental chemistry
and geochemistry to understand fates of contaminants, geochemical cycles,
discussed in terms of the complexation of Cu with organic and evolution of the earth.
molecules as templates controlling the shape and size of the Kouichi Hayashi graduated in 1996 at Kyoto University, Japan, and
metallic nanoparticles. General and environmental implications of received his Ph.D. in electronics science. After that, he became Assistant

Analytical Chemistry, Vol. 82, No. 12, June 15, 2010 4983
Professor at Kyoto University. Since 2003, he has been Associate Professor (27) Muleri, F.; Soffitta, P.; Baldini, L.; Bellazzini, R.; Bregeon, J.; Brez, A.;
at the Institute for Materials Research, Tohoku University, Japan. His Costa, E.; Frutti, M.; Latronico, L.; Minuti, M.; Negri, M. B.; Omodei, N.;
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out his Ph.D. work at the University of North Carolina at Chapel Hill, 55, 785–789.
NC, dealing with surface analysis using XPS and SIMS. At present, he is (30) Arikawa, Y.; Yamanoi, K.; Nakazato, T.; Estacio, E. S.; Shimizu, T.;
a Full Professor in the Department of Chemistry at Inha University in Sarukuwa, N.; Makai, M.; Norimatsu, T.; Azechi, H.; Murata, T.; Fujino,
Korea. His research interest is primarily in the application of quantitative S.; Yoshida, H.; Kamada, K.; Usuki, Y.; Suyama, T.; Yoshikawa, A.; Sato,
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