Trends in Analytical Chemistry 53 (2014) 73–83

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Trends in Analytical Chemistry

journal homepage: www.elsevier.com/locate/trac

Review

Trace and ultratrace analysis of liquid samples by X-ray fluorescence spectrometry

E. Marguí a,⇑, B. Zawisza b, R. Sitko b
a
Department of Chemistry, University of Girona, Campus Montilivi s/n, 17170 Girona, Spain
b
Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland

a r t i c l e i n f o a b s t r a c t

Keywords: This article gives an overview of the state-of-the-art of recent preconcentration strategies published in
Energy-dispersive X-ray fluorescence X-ray fluorescence spectrometry (XRF), including the use of microextraction procedures, nanomaterials,
(EDXRF) spectrometry filters and activated thin layers. We give special attention to current XRF instrumentation and the advan-
High-energy polarized-beam energy- tages and the limitations of each mode (including large-scale instrumentation, bench-top spectrometers
dispersive X-ray fluorescence (HE-P-EDXRF)
and hand-held systems). Also, we comment on and discuss trends and future perspectives of XRF spec-
spectrometry
trometry in trace and ultratrace analysis of liquid samples.
Liquid sample
Preconcentration Ó 2013 Elsevier Ltd. All rights reserved.
Sample treatment
Total-reflection X-ray fluorescence (TXRF)
spectrometry
Trace analysis
Ultratrace analysis
Wavelength-dispersive X-ray fluorescence
(WDXRF) spectrometry
X-ray fluorescence spectrometry (XRF)

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2. Advances in XRF instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3. Recent trends on sample treatment and preconcentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.1. Preconcentration procedures used in combination with EDXRF and WDXRF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.2. Preconcentration procedures used in combination with TXRF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.3. Benefits of preconcentration procedures based on the use of carbon nanotubes, activated thin layers and LPME procedures
in combination with XRF systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
4. Role of XRF spectrometry in liquid analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5. Trends and future outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82

1. Introduction atomic absorption spectrometry (ET-AAS) [2], inductively-coupled

Element determination and quantification in liquid samples is a
topic of great interest in many fields. Usually, environmentally
important elements are present in water samples at the low lg L 1
range, and the analytical procedures used for their determination
are usually based on anodic stripping voltammetry (ASV) [1] and
atomic absorption spectrometry (AAS), including electrothermal
⇑ Corresponding author. Tel.: +34 972419839; Fax: +34 972418150.
E-mail address: eva.margui@udg.edu (E. Marguí).
plasma atomic emission spectrometry (ICP-AES) [3] and induc-
tively-coupled plasma mass spectrometry (ICP-MS) [4]. Despite
AAS continuing to be well established in elemental analysis, its re-
cent use for water-sample analysis has been limited mostly due to
the sequential character of the determination of the elements,
which significantly increases the analysis time. For this reason,
ICP techniques are preferred for most applications, as they allow
simultaneous determination of a variety of elements over a wide
dynamic concentration range. Moreover, when using ICP-MS sys-
tems, limits of detection (LODs) at the ng L 1 level can be achieved

0165-9936/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.trac.2013.09.009
74 E. Marguí et al. / Trends in Analytical Chemistry 53 (2014) 73–83
[5], you can perform isotopic analysis of different elements present
in a sample [6] and/or you can get information on element specia-
tion from coupling high-performance liquid chromatography
(HPLC) with ICP-MS [7].
Most X-ray fluorescence (XRF) techniques also comply with the
desired feature of multi-elemental capability but their use has
been restricted mostly to the analysis of solid samples [8]. Direct
XRF analysis of solutions entails technical difficulties and is
characterized by essential errors in results. Usually, to perform
XRF analysis, a few mL of the liquid sample are placed in a cup with
a thin-film bottom in a non-evacuated XRF set-up. Bubbles re-
leased from solutions due to inadequate filling of the sample
holder and heating of the solution give rise to certain reproducibil-
ity problems [9]. Moreover, liquid samples usually provide a high
X-ray scatter background, resulting in poor signal-to-noise ratio.
Typical LODs of conventional direct XRF are in the mg L 1 range,
which is unsatisfactory for most environmental and industrial
requirements. The sensitivity can be improved using total reflec-
tion X-ray fluorescence spectrometry (TXRF), which makes use of
the fact that, at very low glancing angles, the high background that
would generally occur due to scatter from the sample support is
absent. Because the background is so low, concentrations in the
range of several lg L 1 can be measured in aqueous samples with-
out recourse to preconcentration [10]. However, when dealing
with the analysis of complex water samples (i.e. seawater), a spe-
cial preparation method has to be applied to separate the sus-
pended matter and to remove the salt content prior to
measurement [11]. Moreover, these kinds of X-ray spectrometers,
until recently, were often not available to the general user
community.
However, recent improvements in XRF instrumentation and the
development of new sample-treatment/preconcentration proce-
dures in combination with XRF systems expanded the analytical
capabilities and applications of this technique to the analysis of li-
quid samples. For example, the development of digital signal-pro-
cessing-based spectrometers in combination with enlarged X-ray
production using better designs for excitation-detection has added
the advantage of increased instrumental sensitivity, thus improv-
ing both precision and productivity [12]. Besides, the recent devel-
opment and the commercialization of bench-top and portable
instrumentation, which offer extreme simplicity of operation in a
low-cost design, have promoted XRF for a wide range of analytical
problems in many diverse disciplines [13,14].
In sample-treatment and preconcentration strategies, some
new, efficient variations of existing methods and novel methodol-
ogies were proposed in recent years for the analysis of liquid
samples by XRF techniques [15]. In principle, any preconcentration
and separation method developed for any analytical technique
could be used in combination with XRF. Nevertheless, taking into
account that XRF operates best on solid samples and gives optimal
sensitivity and accuracy for thin, homogeneous targets, preconcen-
tration procedures leading to solid thin targets are ideal for use in
combination with XRF. When using such preconcentration proce-
dures in combination with XRF, the resulting solid can be directly
analyzed, so avoiding the elution step, which is required when AAS
techniques are used. This fact leads to a reduction of the time for
sample preparation and a simplification of the whole preconcen-
tration procedure.
This review covers progress in the use of XRF spectrometry for
trace and ultratrace analysis of liquid samples. The first section
focuses on recent advances in XRF instrumentation and basic
designs of commercial XRF systems. The state-of-the-art of
sample-treatment/preconcentration procedures in combination
with XRF systems is then covered. Also discussed is a short over-
view of the possibilities and the drawbacks of XRF spectrometry
in liquid analysis in comparison with other spectroscopic tech-
niques. Finally, we conclude by commenting on and discussing
trends and future perspectives of X-ray spectrometry in trace and
ultratrace analysis of liquid samples.
2. Advances in XRF instrumentation
The basic principle of the XRF technique is the use of excitation
radiation (usually an X-ray beam) to produce ionization in the in-
ner shells of the atoms present in the sample due to photoelectric
absorption. The energies or wavelengths of the emitted X-rays are
then used to identify the elements present in the sample.
Usually, XRF spectrometers are divided into two main catego-
ries depending on the fundamentals of the detection system:
wavelength-dispersive systems (WDXRF) and energy-dispersive
systems (EDXRF). WDXRF employs diffraction by a dispersing sys-
tem to separate the characteristic wavelengths emitted from the
sample. The geometric arrangement of the components in a
WDXRF instrument is shown in Fig. 1A. As shown, the X-ray source
irradiates the sample and a portion of the characteristic fluorescent
radiation from the specimen is passed via a collimator onto the
surface of the diffraction device (analyzing crystal or multilayer),
where individual wavelengths are diffracted to the detector
according to Bragg’s Law. A goniometer is used to maintain the re-
quired angle between the diffraction device and the detector. Due
to the high-resolution power of crystals and multilayered struc-
tures, photons corresponding to characteristic lines with close
energies can be detected without interfering with each other, thus
providing high specificity in the analysis. As spectral interferences
are avoided, the detection can be performed using proportional
counter detectors with great efficiency.
Unlike WDXRF systems, EDXRF spectrometers consist of only
two basic units: the excitation source and the detection system
(see Fig. 1B). For the EDXRF case, as the resolution of the energy-
dispersive system equates directly to the resolution of the detector,
a semiconductor detector of high intrinsic resolution is typically
employed. The use of this type of detector in combination with a
multichannel analyzer allows the determination of all of the X-rays
emitted by the sample at the same time, giving greater speed in
acquisition and display of data. However, in practice, there is a
limit to the maximum count rate that the semiconductor detector
can handle. For this reason, source modifiers, such as filters, are
usually placed between the X-ray source and the sample to reduce
the continuum of the X-ray tube and thereby avoid saturating the
detector. Another option is to introduce a pure element or com-
pound target between the primary source and the sample in such
a way that a selectable energy range of secondary photons is
incident upon the sample, so selectively exciting certain portions
of the energy range. In current commercial instruments, using
secondary excitation, the primary, the secondary and the charac-
teristic radiations from the sample are configured at mutually
orthogonal angles [polarized EDXRF (P-EDXRF)]. The main advan-
tage of this 3D geometry is that scattered tube radiation cannot
reach the detector because of polarization, so the sensitivity is
better than that of 2D systems.
Both configurations, WDXRF and EDXRF (2D and 3D), have been
widely used for the analysis of solid samples or liquid samples after
a preconcentration procedure. The selection of the most suitable
configuration is based on the requirements for a given purpose.
For example, EDXRF systems are preferred if multi-element
information is needed and WDXRF is usually selected if a fast,
accurate determination of only a few elements is required but flex-
ibility is of little importance.
Another variation of EDXRF systems is total reflection X-ray
(TXRF) spectrometry. In these systems, the primary beam strikes
the sample at a glancing angle of less than 0.1° (and not at the typ-
 E. Marguí et al. / Trends in Analytical Chemistry 53 (2014) 73–83 75

(A)-WDXRF (B)-EDXRF (C)-TXRF

Detector

X-raysource Detector Detector

Fluorescence
X-raysource X-raysource radiation
Fluorescence
2θ radiation
Collimators Totallyreflected
Primary beam
beam Primary
beam
Sample support
Diffraction Sample (reflector)
Primary Device
beam withsample

Sample

Fig. 1. Basic designs for (A) wavelength-dispersive XRF (WDXRF), (B) energy-dispersive XRF (EDXRF) and (C) total-reflection XRF (TXRF) systems.

ical EDXRF angle of about 40°) and that results in a low penetration
depth. Moreover, due to the grazing incident excitation angle, the
detector can be positioned very close to the sample leading to a
large solid angle for the detection of the fluorescence signal (see
Fig. 1C). This also contributes to an improvement in the sensitivity
of TXRF systems compared to conventional EDXRF spectrometers.
TXRF is a well-established analytical technique for multi-element
determination in various sample types, especially liquids and pow-
dered or micro samples [10]. To perform analysis under total-
reflection conditions, samples must be provided as thin films. For
liquid samples, this is done by depositing 5–50 lL of sample on a
reflective carrier with subsequent drying of the drop.
Formerly, most XRF analyses were performed using large-scale
instruments equipped with high-power X-ray tubes (demanding
water-cooling systems) and liquid-nitrogen-cooled detectors.
Moreover, these kinds of X-ray spectrometer were often not avail-
able to the general user community and their use in the field of ele-
mental analysis was limited. However, recent technological
advances led to the availability of compact, low-power, metal-
ceramic X-ray tubes that can be air cooled. Despite the fact that
low-power X-ray tubes (50 W) are less sensitive than high-power
X-ray tubes (1–4 kW), the use of source modifiers (usually primary
filters) and the new generation of compact, solid-sate detectors
[PIN diodes and silicon-drift detectors (SDD)] based on thermo-
electrical cooling improved signal-to-noise ratio, and the instru-
mental LODs of portable and hand-held XRF are comparable to
those of laboratory-based instruments but at a relatively modest
cost. Today, almost all manufacturers of XRF spectrometers world-
wide provide EDXRF bench-top spectrometers and hand-held units
at a reasonable price. Table 1 gives a summary of bench-top and
hand-held XRF spectrometers currently available in the market.
In Table 1, only instruments used for chemical analysis are consid-
ered. However, other bench-top and portable XRF systems for
layer-thickness analysis are also commercially available. As shown
in Table 1, even in the more sophisticated XRF configurations
(P-EDXRF, WDXRF and TXRF), one can find bench-top prototypes.
Also, some of the bench-top EDXRF equipment currently available
in the market (i.e. Fischerscope systems, Fischer Technology,
Windsor, CT, USA) give the opportunity to perform the measure-
ments using a small spot beam (0.2 mm, 0.6 mm, 1.0 mm and
2.0 mm) similar to large-scale micro-XRF (l-XRF) instrumentation.
Then a hole mirror located in the path of the primary beam allows

Table 1
Bench-top and hand-held XRF spectrometers currently available in the market. (List of manufacturers in alphabetic order)

Instrument Type of XRF system Manufacturer Website

S2 RANGER Bench-top EDXRF Bruker AXS www.bruker-axs.com
S2 PICOFOX Bench-top TXRF
Tracer III-IV Series Hand-held EDXRF
Fischerscope XDAL Bench-top EDXRF Fischer, Ltd www.helmutfischer.com
Fischerscope XDV-SDD Bench-top EDXRF
Fischerscope XUV-773 Bench-top EDXRF
X-MET7000 Hand-held EDXRF Oxford Instruments www.oxford-instruments.com
Lab X-3500 Bench-top EDXRF
X-Supreme8000 Bench-top EDXRF
MiniPal QC Bench-top EDXRF PANalytical www.panalytical.com
Epsilon 3, 3XL Bench-top EDXRF
Supermini2000 Bench-top WDXRF Rigaku Corporation www.rigaku.com
NEX CG Bench-top P-EDXRF
Nanhunter Bench-top TXRF
EDX-GP/LE Bench-top EDXRF Shimadzu Corportation www.shimadzu.com
Spectro XSORT Hand-held EDXRF Spectro Analytical www.spectro.com
Spectro IQ II Bench-top EDXRF Instruments
Spectro Xepos/He Bench-top P-EDXRF
Niton DXL Hand-held EDXRF Thermo Scientific www.thermoscientific.com
Niton FXL Field Hand-held EDXRF Corporation
Niton XL Series Hand-held EDXRF
ARL QUANT’X Bench-top EDXRF

P-EDXRF, Polarised energy-dispersive X-ray fluorescence.

76 E. Marguí et al. / Trends in Analytical Chemistry 53 (2014) 73–83
for a precise selection of the measurement spot using a color video
camera and also permits viewing the area on a PC monitor during
the measurement procedure.
Some of the commercially-available table-top and portable XRF
instruments have been designed for particular analytical applica-
tions, including the determination of elements in petroleum prod-
ucts, and bulk analysis for specific industrial applications.
However, recent published papers also indicated the versatility of
these systems for environmental applications. For example, a por-
table TXRF spectrometer was successfully applied for metal deter-
mination in various types of industrial wastewater samples [13].
The fact that the analysis could be performed directly on the raw
wastewaters entailed less sample manipulation and lower
amounts of reagents, so there were savings in cost and time for
the laboratories. Additional advantages of the TXRF method pro-
posed were the multi-elemental information from the sample,
the easy quantitation through internal standardization and also
low operating costs since the bench-top system use did not require
cooling media and gas consumption to function.
Hand-held or bench-top EDXRF systems have also been applied
for the determination of trace-metal concentrations in tap-water
and wastewater samples after preconcentration by solid-phase
extraction (SPE) disks [14]. With hand-held XRF units, direct mea-
surement in the field (in situ) is possible and could be particularly
interesting to provide the near real-time data necessary to guide
critical field decisions about the extent of contamination, removal
and remediation actions. In Section 4 (below), we review recent
contributions based on the use of bench-top, portable and hand-
held units.
Certainly, hand-held and bench-top XRF units have also given a
boost to the XRF technique in liquid analysis.
3. Recent trends on sample treatment and preconcentration
In addition to the recent improvements in XRF instrumentation
above, the development of new, efficient preconcentration strate-
gies in recent years has also extended the possibilities of XRF for
analysis of liquid samples, as highlighted in the annual reviews
‘‘Atomic Spectrometry Update. X-ray Fluorescence Spectrometry’’,
published by the Royal Society of Chemistry.
3.1. Preconcentration procedures used in combination with EDXRF and
WDXRF
As stated in the Introduction (Section 1, above), in principle, any
preconcentration and separation method developed for any analyt-
Evaporation/Freeze drying
Electrodeposition
Precipitation
Liquid-Liquid extraction
Solid-Liquid extraction
14%
.
8%
2%
10%
Fig. 2. Pie chart on preconcentration procedures used in combination with conventional XRF sytems (EDXRF and WDXRF) for the period 2000–12.
ical technique could be used in combination with conventional
XRF. Nevertheless, taking into account that EDXRF and WDXRF
operate best on solid samples and give optimal sensitivity and
accuracy for thin homogeneous targets, preconcentration proce-
dures leading to solid thin targets are ideal for use in combination
with XRF [16]. When using such preconcentration procedures, the
resulting solid can be directly analyzed by XRF, so avoiding the elu-
tion step, required when atomic spectroscopic techniques are used.
However, it is important to keep in mind that there is no ideal, uni-
versal method of preconcentration applicable over an infinite con-
centration range, free of interferences, capable of determining all
elements, and simple, fast and economical.
The preconcentration techniques, developed so far, are based on
physical and/or chemical principles. For this reason, in general,
preconcentration methods used in X-ray spectrometric techniques
are grouped into two main categories:
 physical (evaporation and freeze drying); and,
 chemical (electrodeposition, coprecipitation, liquid-liquid
extraction (LLE) and liquid-solid extraction).
Fig. 2 shows a pie chart on preconcentration procedures used
in combination with conventional XRF systems (EDXRF and
WDXRF) for the period 2000–12. As can be seen, chemical precon-
centration methods are preferred over physical ones (which ac-
count for only 10% of published papers). Among the chemical
preconcentration procedures, electrodeposition has hardly been
used in the past decade compared to other sample-treatment
methodologies [17].
Precipitation was one of the methods of choice for most XRF
users some years ago. The basic principle of the precipitation
method is the addition of a precipitating agent to the solution
and the determination of the target elements in the solid obtained
after a filtration procedure. The thickness of the precipitate formed
(5–10 lg cm 2) can be considered thin film, so it is not necessary
to apply a correction for the matrix effect for further XRF analysis.
For that reason, it is a convenient means of preconcentration to be
applied in combination with XRF spectrometry. However, in recent
years, the use of this preconcentration approach has been signifi-
cantly reduced [15]. In the decade 1996–2005, 33% of the
published works on liquid-sample analysis by XRF were based on
the precipitation method, whereas, in the period 2000–12, it ac-
counted for only 8% of all methods developed (see Fig. 2).
Currently, most of the methodologies developed for metal pre-
concentration by XRF are based on solid-liquid extraction (66%).
This trend can be related to the development of new solid sorbents
66%
Activated
thin layers
31%
Solid
sobrents
59%
Chemofiltration
10%
 E. Marguí et al. / Trends in Analytical Chemistry 53 (2014) 73–83 77

Fig. 3. Preconcentration strategies based on the use of (a) activated thin layers, (b) nanomaterials and (c) liquid-phase microextraction procedures, in combination with
conventional XRF (EDXRF and WDXRF) and TXRF systems.

and activated thin layers, as shown in Fig. 2. A wide variety of solid fied silica gel [20], polyurethane foams [21,22] and natural
sorbents have been used for preconcentration purposes in combi- sorbents, such as activated carbon, due to their extensive surface
nation with XRF analysis including synthetic resins [18,19], modi- area and porosity.
78 E. Marguí et al. / Trends in Analytical Chemistry 53 (2014) 73–83
But perhaps the most novel solid sorbents used for element pre-
concentration in liquid samples by XRF spectrometry are carbon
nanotubes (CNTs). CNTs are relatively new adsorbents that have
more advantages than activated carbon. First, CNTs have a well-de-
fined structure at the atomic scale, so more reproducible results
can be achieved. Also, due to their large surface areas and small
dimensions, CNTs have an excellent sorption capacity for organic
compounds and heavy metal ions [23]. Nevertheless, raw CNTs
are insoluble and difficult to disperse in most solvents, so metal
ions present in hydrated forms or as complexes associated with
simple anions are not adsorbed on raw CNTs. To cope with this
drawback, different strategies can be applied:
 complexation of metal ions using an appropriate chelating
agent;
 functionalization of CNTs; or,
 preparation of CNT-based composites with metal oxides or che-
lating polymers [24].
Fig. 3A shows preconcentration strategies based on the use
CNTs. As can be seen, after the adsorption process, the aqueous
samples are usually filtered, and the loaded CNTs are collected
on a filter that is directly measured on EDXRF or WDXRF systems.
Another interesting, extensively used approach for element
preconcentration in combination with XRF spectrometry involves
activated thin layers. In this category, we can include commer-
cially-available ion-collecting filters or extraction disks [25] and
laboratory-made organic thin layers containing extracting agents
selective for preconcentration of analytes [26]. In the first case,
the functionalized filter or extraction disk is placed between a frit-
ted-glass support base and the sample reservoir of a vacuum filter
assembly and secured with an aluminum clamp. Then, a certain
volume of aqueous sample (containing the elements of interest)
is filtered through. The resulting metal-loaded disks are vacuum
dried and directly analyzed by XRF.
With regards to the preparation of the activated thin layers, two
different strategies have been applied:
 impregnation of a commercial polymeric support by an organic
solution of the extractant; or,
 physical inclusion of the extractant in a polymeric matrix (mix-
ture of a polymer and a plasticizer) [15].
Once the activated thin layers are prepared, the preconcentra-
tion experiments are usually carried out by putting the aqueous
solution into contact with the prepared activated thin layer by
continuous stirring for an optimized period of time (depending
on the metal extracted). At the end of the experiments, the
loaded thin layer is removed from the vessel, washed with deion-
ized water, dried at room temperature and mounted directly in the
spectrometer for XRF analysis. Both approaches have been
successfully applied for the determination of trace elements in
different types of liquid sample by XRF. We discuss a detailed
summary of most relevant applications in the next section of this
review.
Another interesting approach, when extraction disks or acti-
vated thin layers are not available, is the complex formation of
the elements being determined with selective organic reagents in
solution followed by sorption of this complex onto a non-selective
membrane or filter in the course of filtration. Highly-selective pre-
concentration can be attained using this procedure, known as
chemofiltration, by selecting a suitable complexing agent [27,28].
At present, preconcentration methods based on chemofiltration
represent one-tenth of the published works on solid-liquid precon-
centration procedures used in combination with conventional XRF
systems (Fig. 2).
Despite the fact that LLE is certainly one of the most popular
preconcentration methods applied in atomic spectrometry, it has
not commonly been applied in XRF, mainly because subsequent
evaporation of the organic phase is needed and because preconcen-
tration coefficients are usually quite low. However, the recent
development of liquid-phase microextraction (LPME) has solved
these drawbacks. LPME is a solvent-minimized sample-pretreat-
ment procedure of conventional LLE, in which only several lL of
solvent are required to concentrate analytes from the sample
rather than hundreds of mL needed in conventional LLE. As a result,
this methodology entails higher preconcentration coefficients and
is more environmental friendly, since a very small volume of or-
ganic phase is needed. Different LPME modes have been developed
including hollow-fiber liquid-phase microextraction (HF-LPME),
single-drop LPME (SD-LPME) and dispersive liquid-liquid microex-
traction (DLLME) [29]. Despite LPME originally being applied to
preconcentrate organic compounds, in recent years, it has been
also used as a preconcentration strategy for determination of inor-
ganic compounds when using microanalytical atomic spectro-
scopic techniques, such as ET-AAS [30].
The combination of LPME and EDXRF with a small-spot X-ray
beam has also proved to be a good analytical strategy for the
simultaneous determination of trace and ultratrace elements in li-
quid samples [31]. After the LPME procedure, we can deposit the
small drop (using pipetting or spray-on technique) onto a thin-film
substrate (membrane filter of Mylar foil) and, after drying, the
deposited drop can be directly analyzed by EDXRF with a small-
spot X-ray beam. Fig. 3A shows experimental procedures based
on LPME and EDXRF. Certainly, the development of LPME proce-
dures will offer new interesting analytical strategies for element
and speciation analysis when using conventional XRF instrumenta-
tion in the coming years.
Using pipetting or a spray-on technique to obtain thin samples
is one of the alternative methods to sample deposition. Many
authors have demonstrated that the dried-spot sample-
preparation method can be improved by using much smaller
droplet volumes, in the nanoliter (nL) and even picoliter (pL)
ranges. Thus, the automated printing technology (APT) as an alter-
native to manual methods for nL dried-spot sample preparation of
liquid samples was particularly explored. Horntrich et al.
proposed the nanodispensing system consisting of the UltraMicro-
Pump III and a positioning device. This system allows the precise
deposition of volumes in the nL range on the wafer [32]. Fittschen
and Havrilla introduced a Hewlett-Packard prototype pL pipette,
the thermal inkjet picofluidic system (TIPS), for analytical pur-
poses [33]. They showed that the evaporation of solvent from
the TIPS nozzles has a major effect on the elemental amounts jet-
ted and should be treated seriously if pL volumes are to be used
for calibration purposes. In this context, they introduced a conve-
nient strategy to minimize evaporation by jetting droplets with
short quiet times (time between shootings) (130 ms and less)
[34]. The advantage of automated droplet deposition is rapidity
and the minimization of operator skill and human error in the
sample-preparation process. Furthermore, multiple dried spots
could be accurately, reproducibly deposited in the same precise
location on the substrate surface, so allowing increased sample
loadings within the l-XRF and TXRF analysis area for higher ele-
mental sensitivity [35,36].
3.2. Preconcentration procedures used in combination with TXRF
Taking into account the microanalytical capability of TXRF spec-
trometry (see Section 2 for details), LPME procedures are also a
powerful methodology to be combined with TXRF spectrometry
for the determination of low levels of metals and inorganic species
in aqueous samples in a simple, non-time consuming and low-cost
 E. Marguí et al. / Trends in Analytical Chemistry 53 (2014) 73–83
way. When using such approach, after the extraction procedure,
the few lL of organic solvent (containing the extracted analytes)
are directly deposited and dried on the sample carrier for
subsequent TXRF analysis (see Fig. 3B). Recent results on the use
of two-phase HF-LPLME-TXRF and DLLME-TXRF systems
demonstrated that the DLLME mode is more suitable for use in
combination with TXRF than the two-phase HF-LPME method.
Chlorine-containing organic solvents used in DLLME mode (i.e. car-
bon tetrachloride) are better solvents to measure with TXRF due to
their high volatility that permits high deposition volumes on the
reflective carrier and facilitates the drying step of the organic drop
for subsequent analysis [37]. This analytical strategy was success-
fully applied to the quantification of Cd in the low lg L 1 range in
different types of spiked environmental water samples [38] and to
Se determination in more complex liquid samples, such as soil di-
gests [39].
Another preconcentration procedure used in the past decade in
combination with TXRF involved selective membranes containing
a few lg of complexing reagents in a polymeric matrix. These
membranes are created on the center of the sample carrier (quartz
reflector) and they are used to collect trace elements from various
water solutions in volumes of 5–500 mL [40]. The cleaning proce-
dure after TXRF analysis is simple and the membranes can be easily
removed from the quartz surface. Additional advantages of the
combination of these membranes with TXRF include the small
quantities of the reagents needed to create the membranes (lg
or lL), unlike the amounts of reagents used when they are applied
in combination with conventional XRF systems (EDXRF and
WDXRF) (see Fig. 3B).
Finally, taking into account the micro-analytical capability of
TXRF and the possibility of analyzing suspensions, the use of
nanomaterials (i.e. CNTs) as solid sorbents is also an interesting,
emerging preconcentration strategy to improve the analytical per-
formance of trace-metal analysis when using, above all, bench-top
TXRF systems. As stated above, CNTs have desirable characteristics
as SPE sorbents mainly because of their large specific surface area
and their well-defined structure at the atomic scale, but also the
very small particle size of CNTs make these solid sorbents suitable
for preparing a representative suspension to be later analyzed by
TXRF. Usually, the analytical procedures involving the use of
nanomaterials as preconcentration solids are based on dispersive
microSPE (DMSPE) since only lg or mg of solid sorbent are dis-
persed in the analyzed solution. Application of CNTs in DMSPE pro-
vides a large contact area between the sorbent and the analytes of
interest, so the equilibrium state is achieved immediately and the
extraction process is almost independent of time. Besides, the use
of TXRF as the detection system eliminates the need for an elution
step after the adsorption of the analytes on the CNTs, simplifying
the procedure and reducing the total analysis time (see Fig. 3B). A
recent study demonstrated the suitability of a DMSPE (using mul-
ti-walled CNTs)-TXRF system for the determination of Cd and Pb
in the low ng mL 1 range in different types of water sample [41].
3.3. Benefits of preconcentration procedures based on the use of
carbon nanotubes, activated thin layers and LPME procedures in
combination with XRF systems
As mentioned in the previous sub-section, current trends in
preconcentration procedures used in combination with XRF
spectrometry focus on the use of LPME, the use of activated thin
layers and the employment of nanomaterials (i.e. CNTs) in DMSPE.
The use of these preconcentration procedures leads to solid thin
targets loaded with the analytes (Fig. 3), which are ideal samples
to analyze by conventional XRF systems and TXRF spectrometers.
When analyzing solid thin targets in XRF spectrometry, adsorp-
tion-enhancement effects and spectral background, usually related
79
to the analysis of intermediate-thick and thick solid samples, are
significantly reduced. Matrix and thickness-effect corrections can
therefore be avoided and the XRF signal can be directly related to
the element concentration. This property facilitates quantification
and decreases the overall time for data treatment compared to
other preconcentration methods.
Another advantage of these analytical strategies is the great
improvement in the sensitivity compared with the direct analysis
of the liquid sample by XRF spectrometry. Fig. 4 shows selected
examples. As shown, in addition to the increase in sensitivity, a
reduction of the XRF spectrum is also achieved, leading to a signif-
icant improvement of LODs. For instance, the calculated LOD for Cd
in seawater samples by HE-P-EDXRF after preconcentration using a
selective activated thin layer (0.1 lg L 1 of Cd) is significantly
enhanced compared to that associated with the direct analysis of
the same type of water (600 lg L 1 of Cd) (Fig. 4A) [42]. This
characteristic is also significant when using bench-top and porta-
ble TXRF systems that offer extreme simplicity of operation in a
low-cost compact design (no cooling media or gas consumption
are required for operation) but they also have limited sensitivity
compared with top-scale instrumentation. These systems are also
useful to increase analytical performance of XRF systems equipped
with Mo and W-target X-ray tubes for the determination of trace
amounts of high-Z elements (i.e. Cd and Sb) that have limited
excitation when using this kind of X-ray tube. In a recent study,
an LOD for Cd as low as 0.04 lg L 1 was obtained for aqueous
samples using LPME in combination with a bench-top W X-ray
tube TXRF spectrometer [38].
It is also important to remark on the versatility of this kind of
preconcentration strategy. Depending on the complexing agent
or the extractant used in the LPME method, the activated thin layer
or the DMSPE procedure using CNTs, we can obtain single-element
(Fig. 4A, Fig. 4C) or multi-element information (Fig. 4B). The user
can therefore design a suitable preconcentration method depend-
ing on the purpose of the analysis.
Last, but not least, is the low consumption of reagents in these
preconcentration procedures. For this reason, they are included
within the framework of so-called ‘‘green analytical chemistry’’
that is an unquestionable trend in analytical chemistry [43].
4. Role of XRF spectrometry in liquid analysis
Usually, atomic spectrometry techniques, including FAAS, ET-
AAS, ICP-AES and ICP-MS, are the techniques of choice for trace
and ultratrace element determination in liquid samples, mainly be-
cause the basic instrumentation is designed for analysis of liquid
samples. At present, ICP-MS is usually preferred among the atomic
spectroscopic techniques due to its multi-elemental capability and
the extremely low LODs for most elements. However, the complex-
ity of most environmental matrices (e.g., seawater) hampers the
analysis and sample treatment of the liquid sample is usually
needed before ICP-MS analysis [44,45].
Taking into account the basic principles and the analytical capa-
bilities of TXRF (see Section 2, above), since its development in the
early 1970s, it has been primarily used for chemical micro and
trace analysis of small quantities of solutions and suspensions.
However, the use of these systems in analytical chemistry
laboratories was limited in comparison to atomic spectrometry
techniques due to high capital and running costs of large-scale
instruments equipped with high-power X-ray tubes demanding
water-cooling systems and liquid-nitrogen-cooled detectors. Re-
cent technological advances have led to the availability of bench-
top and portable TXRF that present instrumental LODs comparable
to those of large-scale systems but at relatively modest cost. This
factor has promoted the approach of TXRF in analytical chemistry
laboratories worldwide.
80 E. Marguí et al. / Trends in Analytical Chemistry 53 (2014) 73–83

Preconcentration using DLLME

Without preconcentration
Pulses
40
Cd-K

30

20

Cd-Kβ
10

0
20 25 30
- keV -

Fig. 4. XRF spectra showing the benefits of preconcentration using activated thin layers and liquid-phase microextraction strategies: (A) activated thin layers for Cd
determination at trace levels in seawater samples by HE-P-EDXRF; (B) dispersive liquid–liquid microextraction for determination of trace elements in water samples by
EDXRF; and, (C) dispersive liquid-liquid microextraction for determination of trace Cd by TXRF.
 E. Marguí et al. / Trends in Analytical Chemistry 53 (2014) 73–83 81

Table 2
Recent published methods (2004–13) on preconcentration procedures based on the use of activated thin layers, carbon nanotubes and liquid-phase microextraction procedures
for cation and anion determination in water samples by XRF techniques

Preconcentration XRF system Elements Sample LOD Ref.

procedure (lg/L)
Activated thin layers Hand-held EDXRF Ni, Cu, Zn, Pb, Cd Tap/waste water 0.1 –45 [14]
(commercially available Bench-top EDXRF
and/or prepared in HE-P-EDXRF
the laboratory) Bench-top EDXRF Cr(VI), Cd(II), Pd(II), Pt(IV) Aqueous solutions 14–300 [46]
WDXRF
WDXRF Cd Aqueous solutions 100 [47]
HE-P-EDXRF Cd Saline solutions 0.08 [48]
HE-P-EDXRF Cd Sea water 0.7 [42]
Bench-top EDXRF Cr(VI) Electroplating waters [49]
WDXRF Cr(III), Cr (VI) Tap water, river water 0.17 [50]
TXRF U Saline solutions 0.8 [51]
TXRF Hg Drinking water 0.8 [52]
TXRF Hg Sea water 0.4 [53]
TXRF Pb Aqueous solutions 1 [54]
TXRF Cu, Co, Ni, Zn Sea water 1 [40]
TXRF Ni, Cu, Mn, V Aqueous solutions 1 [55]
TXRF Cr(III), Cr(VI) Drinking water 0.6 [56]
TXRF Bromate Drinking water 1 [57]
TXRF Perclorate Drinking water 0.8 [58]
Carbon nanotubes WDXRF Se(IV), total Se, Se (VI) Spiked water samples 0.06–0.13 [59]
as solid sorbents Bench-top EDXRF
Bencthop EDXRF Co, Ni, Cu, Pb Tap/waste water 0.1–0.8 [60]
WDXRF V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Se, Pb, Cd Water samples 0.6–1.9 [61]
WDXRF Cr(VI) Drinking water 0.5 [62]
WDXRF Cr(VI) Drinking water 1 [63]
Bench-top TXRF Cd, Pb Sea/river/waste water 1–2 [41]
Liquid-phase EDXRF Fe, Co, Zn, Ga, Se, Pb River water 1–4 [31]
microextraction procedures EDXRF Fe, Co, Ni, Cu, Zn, Se, Pb River water 1.5–4 [64]
Bench-top TXRF Cd Estuarine/river/sea water 0.04 [38]
Bench-top TXRF Sb(III), Sb (total), Sb (V) Bottled/river/sea water 0.09 [37]

Some advantages of these systems compared with most atomic
spectrometry techniques are the possibility to analyze mass-lim-
ited samples (volume  few lL) and complex liquid samples with-
out previous sample treatment. For example, a recent contribution
demonstrated that, for routine and screening analysis of industrial
inlet and outlet effluents, TXRF wastewater-sample analysis could
be directly performed by depositing 20 lL of the internal standard-
ized sample on a quartz-glass reflector [13]. A further enhance-
ment of analytical quality of TXRF results can be achieved using
more sophisticated sample-treatment and preconcentration
procedures described in detail in Section 3, above. Table 2 summa-
rizes recent published methods on preconcentration procedures
based on the use of activated thin layers, carbon nanotubes and
liquid phase microextraction procedures for element determina-
tion in water samples by TXRF and other XRF systems. As shown,
LODs obtained (in the low lg L 1 range) are adequate for most
environmental applications. Moreover, using these preconcentra-
tion strategies and TXRF analysis, it is possible to determine anions
(i.e. bromate and perchlorate) or element speciation [i.e. Cr(VI) and
Cr(III)] that were impossible using direct analysis of the water
sample by TXRF systems.
As stated in the Introduction (Section 1, above), the use of con-
ventional XRF spectrometry (EDXRF and WDXRF) in liquid analysis
has been restricted due to the limited sensitivity and poor repro-
ducibility inherent in the direct analysis of liquid samples. How-
ever, recent preconcentration strategies, based on the use of
activated thin layers, nanomaterials and LPME, led to considerable
improvement in the analytical capabilities of XRF instrumentation
for the analysis of liquid samples. Table 2 summarizes the most rel-
evant contributions. As shown, LODs for the methodologies devel-
oped using conventional XRF systems are in the low lg L 1 range,
even when using bench-top or hand-held systems. Usually, these
LODs are adequate for most environmental and industrial applica-
tions, and they are competitive with those obtained using other
popular spectrometric techniques, such as FAAS and ICP-AES.
Although the minimum element concentration that can be de-
tected using XRF methods is higher than those usually associated
with ET-AAS and ICP-MS techniques, the low costs of most XRF sys-
tems combined the simplicity of the aforementioned preconcen-
tration procedures makes the use of conventional XRF systems a
promising complementary analytical tool for element determina-
tion at trace levels in liquid samples. It is important to remark that,
for the analysis of complex liquid samples when using atomic
spectroscopic techniques, a preconcentration procedure is also
usually needed, and, after the preconcentration step, an additional
elution step is necessary to recover the species in an appropriate
medium to be analyzed. By contrast, when using conventional
XRF systems, direct quantification of elements held in solid mate-
rials (usually used for preconcentration purposes) is possible, so,
apart from reducing sample handling, an elution step can be
avoided.
On the whole, atomic spectrometry techniques are still the
techniques of choice for the analysis of liquid samples. However,
recent studies highlighted the potential of XRF spectrometry in this
field, so XRF can be considered a complementary analytical tool to
other atomic spectrometry techniques. XRF methods are especially
interesting if capital and running costs are a restriction or if in-situ
analysis is needed (hand-held and portable XRF units are commer-
cially available). In addition, since conventional XRF systems are
specially designed for the analysis of solid samples, using the com-
bination of SPE plus XRF analysis, for some applications, an
analytical laboratory can use the same instrument for the analysis
of solid and liquid samples. This approach is of significance in
avoiding additional costs in instrumentation.
82 E. Marguí et al. / Trends in Analytical Chemistry 53 (2014) 73–83
5. Trends and future outlook
In the past decade, the significant technological advances in XRF
instrumentation in combination with the development of new pre-
concentration strategies based mostly on the use of nanomaterials,
LPME procedures and activated thin layers have shown the poten-
tial use of XRF spectrometry in liquid analysis. We expect that
future improvements in both instrumentation and preconcentra-
tion procedures will focus on miniaturization, one of the clear
trends in science and technology for the future. In previous years,
the micro-total analysis system (lTAS), also named ‘‘lab-on-a-
chip’’, has revolutionized and facilitated the automation of routine
works so that the consumption of expensive reagents and samples
can be readily reduced to the nL scale. Various chemical processes,
such as mixing, chemical reactions and separation, are performed
inside the microchannels on a microchip several tens of mm2.
The small size of the chemical microchip is also one of the major
advantages when considering in-situ analysis in environmental
monitoring. In this respect, miniaturized chip systems have been
developed and used for preconcentration for subsequent XRF
analysis.
Tsuji and co-workers designed a chemical microchip, which has
a flat region on the surface, to determine Zn by TXRF [65]. A sample
solution was introduced from an inlet by a microsyringe and
flowed into a microchannel. Finally, it overflowed from the
well-type microchannel on the flat region, which was dried and
analyzed by TXRF. A similar approach was also used in combina-
tion with l-XRF [66]. Despite further improvement of the move-
ment and the drying of the solutions being required for
quantitative XRF analysis, these systems will be a promising ana-
lytical tool in the future.
In miniaturization, it is also important to remark on the possible
use of smaller spots and thinner substrates in dried-spot technol-
ogy. Recently, pL and fL droplets were generated by vibration,
extrusion and solvent elimination [67] and may be applicable for
preconcentration in the near future in combination with l-XRF
and TXRF systems.
To sum up, we expect that, with future improvements in
both instrumentation and preconcentration procedures, XRF
spectrometry could offer new possibilities in the determination
of trace elements in liquid samples.
Acknowledgment
This work was supported by the Spanish National Research Pro-
gram (Project Ref. CGL2010-22168-C03-01).
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