Instrumentation, Fundamentals,

and Application of Laser Ablation- 1

Inductively Coupled Plasma-Mass
Spectrometry

€nther
Mattias B. Fricker and Detlef Gu

Abstract
Laser ablation-inductively coupled plasma-mass spectrometry
(LA-ICP-MS) is becoming a versatile and mature analytical technique
for quantitative major, minor, and trace element analysis and isotope ratio
determinations. A wide variety of solid and liquid samples can be
analyzed. Besides the fast growing application of this method as an
imaging technique, geology still is and has been the major driving force
for the development of LA-ICP-MS. In this review, the method, instru-
mentation, fundamental observations and quantification procedures are
explained. In addition, pros and cons of the technique are discussed and
some trends and new sampling strategies, with special focus on archaeo-
logical applications, are summarized.

1.1 Introduction related aerosol transport, and the ICP-MS

operating conditions. The ablation cell is an air-
Laser Ablation-Inductively Coupled Plasma- tight container, where samples and calibration
Mass Spectrometry (LA-ICP-MS) is currently reference materials are placed. It incorporates a
the technique of choice for trace elemental anal- window made of a material that is transparent at
ysis of solid samples. In the 29 years since the the wavelength of the laser being used, through
introduction of LA-ICP-MS in 1985 (Gray which the laser beam is focused onto the sample
1985), the fundamental principle of the technique surface, typically with diameters of tens to
has not changed. In addition to many other hundreds of μm. Each pulse of the high-energy
parameters, the performance of LA-ICP-MS laser beam ejects particles of the sample and the
depends upon laser parameters (wavelength, resulting laser generated aerosol is transported to
pulse width), the design of the ablation cell and the ICP by a carrier gas flow (commonly He,
although Ar is also used). During the short resi-
dence time (μs-ms) in the plasma at over 6000 K,
M.B. Fricker • D. G€
unther (*)
Department of Chemistry and Applied Biosciences, the solid aerosol is vaporized, converted to
Laboratory of Inorganic Chemistry, ETH Zurich, atoms, and ionized. The ion beam is then
Vladimir-Prelog-Weg 1, 8093 Zurich, Switzerland extracted into the mass spectrometer interface,
e-mail: [email protected]

# Springer-Verlag Berlin Heidelberg 2016 1

L. Dussubieux et al. (eds.), Recent Advances in Laser Ablation ICP-MS for Archaeology, Natural
Science in Archaeology, DOI 10.1007/978-3-662-49894-1_1
2 M.B. Fricker and D. G€
unther

where the pressure is reduced from ambient to a Research and development of LA-ICP-MS
moderately high vacuum in two stages, by pass- during the last decade has produced a large num-
ing through a sampler cone and a skimmer cone. ber of applications, which is largely due to the
In the high-vacuum chamber the ion beam is fact that using this technique, samples are
shaped by ion optics, and photons as well as analyzed under atmospheric pressure, which
negatively-charged and neutral particles are makes LA-ICP-MS easier to apply when com-
separated by a photon stop or similarly function- pared to secondary ion mass spectrometry
ing ion optics. Positive ions pass through various (SIMS), laser microprobe mass analysis
kinds of analyzers, where ions with differing (LAMMA), or electron probe micro-analysis
mass to charge (m/z) ratios are separated and (EPMA). All of these techniques require
then collected on a detector, where the ions are low-pressure vacuum conditions, which limits
either counted or a generated current is their applicability to some samples. However, it
measured. must be mentioned that some of the figures of
The purpose of LA sampling is to generate an merit for these techniques (limits of detection,
aerosol that can be transported, vaporized, spatial resolution) are superior compared to LA-
atomized and ionized within the ICP. The ions ICP-MS. Furthermore, EPMA is often a comple-
thus formed are then extracted into the interface, mentary technique to LA-ICP-MS, as it allows
separated by the analyzer and recorded by the the determination of major elements very accu-
detector and associated electronics. For bulk rately, a prerequisite of trace element
analysis of homogeneous samples the recorded determinations (e.g. Dussubieux et al. 2008).
transient signal can be integrated for quantifica- The ability to obtain quantitative determinations
tion. When performing a line scan along a het- of major and trace element composition in any
erogeneous sample (such as a stalagmite, paint solid sample along with the ability to determine
layers, or bronze objects, for instance), the tran- isotope ratios with high accuracy and high preci-
sient signal can be used to show variations which sion are some of the key reasons for the success
correspond to concentration changes in the sam- of LA-ICP-MS. The technique is widely used in
ple and provide insights into growth or the many areas, but especially in earth sciences,
manufacturing procedure. Parallel line scans gemology, material sciences, and industrial qual-
can be performed across an area of the sample ity control applications (Durrant 1999). Apart
yielding the distribution of elements in two from bulk- and microanalysis of archeological
dimensions, i.e. elemental imaging or mapping, objects, e.g. glass and ceramics (Barca
which is today one of the fastest growing et al. 2007; Dussubieux et al. 2007; Gratuze
applications of LA-ICP-MS. Recording these 1999), and depth profiling (Pisonero et al. 2007;
variations in transient signals requires an ablation Plotnikov et al. 2001), more advanced
cell with a fast washout of the aerosol to mini- applications such as analyses or fingerprinting
mize mixing of aerosol from different positions of gemstones and archeological objects such as
of the sample, allowing higher spatial resolution. pottery and ceramics (Arnold et al. 2012;
Most commercially available ablation cells are Fontaine et al. 2010; Vaughn and Dussubieux
relatively small, requiring cutting large samples 2011), isotope ratio determinations (Cottle
into smaller pieces in order for the sample piece et al. 2009) and elemental imaging and/or line
to fit into the ablation cell. For many samples, scans (Bi et al. 2000; Campbell and Humayun
cutting and resulting destruction is not possible, 1999; Raab et al. 2009; Sinclair et al. 1998; Tre-
thus a large ablation cell able to contain larger ble et al. 2003; Wirth et al. 2009), profiling
samples in their entirety, is required. Analysis (Mattey et al. 2008), and mapping (Becker
without any ablation cell would be most ideal et al. 2005; Treble et al. 2005; Woodhead
for many applications, and some promising et al. 2007) are rapidly growing applications,
approaches are discussed later in this chapter. and provide valuable information for different
fields of research.
1 Instrumentation, Fundamentals, and Application of Laser. . . 3

1.2 Instrumentation The three most common types of mass

analyzers in inorganic mass spectrometry are
1.2.1 Inductively Coupled the quadrupole, the magnetic sector, and the
Plasma-Mass Spectrometry time of flight mass spectrometer (TOF-MS), as
shown in Fig. 1.1. The quadrupole is a low reso-
The most common sample introduction systems lution, fast sequential mass filter consisting of
used with ICP as an ion source are schematically four parallel rods, connected pair-wise to radio
shown in Fig. 1.1. The two basic systems are used frequency (RF) voltage and direct current
for liquid samples or for solid samples or (DC) voltage. Depending on the applied
combinations thereof. The six most common voltages, ions of only one mass to charge ratio
mass analyzers used for ICP are also shown pass through the filter and are focused onto the
schematically, and will be explained in more detail detector. All types of ICP-MS suffer from
in the following sections. Soon after ICP-MS was interferences, as the mass analysers separate
introduced, reports of elemental analysis were ions based on their mass to charge ratios, most
published with solution nebulization remaining often singly charged ions of an isotope of an
the dominant sample introduction device (Jenner element. Several isobaric interferences occur
et al. 1990). The first coupling to laser ablation due to overlapping ions or the formation of poly-
(Gray 1985), and later overviews (Durrant 1999; atomic ions with a similar mass per charge ratio
Hattendorf et al. 2003; Jackson et al. 1992; Russo (Hattendorf and G€unther 2001; Houk et al.
et al. 2002a) gave some indications of the versatil- 1980). A selection of some more common inter-
ity of this ionization source. ICP-MS has several ference types are listed in Table 1.1, which occur
advantages in comparison to the longer established at low mass resolution (m/Δm¼300, quadrupole
method of ICP-Optical Emission Spectrometry ICP-MS). These interferences also occur during
(ICP-OES), including lower limits of detection, a LA, however, oxide formation is significantly
wider linear dynamic range, access to isotopic lower with dry aerosol introduction.
information, and simpler spectra. Due to the sen- If alternative isotopes that do not suffer from
sitivity of this technique, analyte concentrations interference are not available, high resolution
can be diluted in solution ICP-MS (Longerich (HR) ICP-MS can overcome most interferences.
2012), which reduces matrix effects and The most widely used HR-ICP-MS instrumenta-
contributes to the wide range of applications tion is based on various combinations of a mag-
reported in the literature. netic field analyzer (MSA), and an electrostatic
The ion source, an argon plasma, vaporizes analyzer (ESA, a kinetic energy analyzer) with
introduced particles, converts molecules to single, multiple or array detectors as shown in
atoms, and ionizes these atoms, regardless of Fig. 1.1. The sector field ICP-MS with a single
whether sample enters as a gas, liquid, or solid. detector usually uses a magnetic field prior to the
The ion beam is then extracted through an inter- ESA, which is known as reverse Nier-Johnson
face where the sample passes through a sampler geometry. Sector field ICP-MS with several
cone and a skimmer cone in two or three stages, detectors (multi collector or MC) ICP-MS
dropping from atmospheric pressure into a mod- (Nier-Johnson geometry) has also been used for
erate vacuum. A photon stop or equivalent more precise isotope ratio measurements. This
device, removes negatively charged ions, instrument type records isotope signals simulta-
neutrals and photons from the ion beam, which neously with high precision, and has found appli-
is then shaped by the ion optics before entering cation in geochronology and other analyses
the mass analyzer. The mass filter (or analyzer) requiring precise measurement of isotope ratios
separates these ions by their mass to charge (Halliday et al. 1998). Developments have been
ratios, which are then counted by a single detec- made towards simultaneous detection of all
tor or multi collector. elements (from m/z 7 to 250) using a Mattauch-
4 M.B. Fricker and D. G€
unther

Fig. 1.1 Schematic representation (Fricker 2012) of the detectors. The quadrupole (E) and the single collector
most common optical emission and mass spectrometer (reverse Nier-Johnson) sector field (F) are sequential
configurations used in combination with ICP as the pho- MS, while G (multi collector, Nier-Johnson geometry)
ton emission or ion source: torch, load coil, plasma, and and H (Mattauch-Herzog geometry) are simultaneous
interface (C). Aerosols generated from solution nebuliza- MS. The time-of-flight (I) is a pulsed MS and while not
tion (A) or from laser ablation (B) are transported (dotted exhibiting simultaneous detection does simultaneously
line) to the ion source (C). The ions (grey solid line) can sample the ions. ICP optical emission spectrometry is
be separated using several types of analyzers (E–I) before represented by D which shows a multichannel system
being converted to a suitable electrical signal by various

Table 1.1 List of selected common interferences and with an array detector (Cromwell and
backgrounds in ICP-MS analysis (Fricker 2012) and Arrowsmith 1996; Felton et al. 2011; Fricker
suggested alternative isotopes
2012; Resano et al. 2012; Schilling et al. 2009).
Interference Interference Isotope of The coupling of TOF-MS to the ICP ion source is
form example interest Alternative
complicated due to the continuous ion beam
An++ 138
Ba+ 69
Ga+ 71
Ga+
delivered to the ICP and the pulsed nature of
AnAr+ 23
Na40Ar+ 63
Cu+ 65
Cu+
the TOF analyzer. However, reports using ICP-
AnO+ 40
Ar16O+ 56 +
Fe 57
Fe+
O2+ 16
O2+ 32 +
S 34 +
S
TOF-MS have been published (Borovinskaya
An+ 50 +
Cr 50 +
Ti 48 +
Ti et al. 2013; Feldmann et al. 2002; Gonzalez
AnCl+ 40
Ar35Cl+ 75
As+ HR-ICP- et al. 2012; Guilhaus 2000; Mahoney
MS et al. 1996; Myers and Hieftje 1993; Tanner and
Ar+, high 40
Ar+, 80Ar+ 40
Ca+, 42
Ca+, G€unther 2006) and commercially available and
80
abundance Se+ 78
Se+ custom built instruments are currently both in
The formation of interferences needs to be evaluated for use. The TOF-MS configuration is potentially
each analysis, as interferences heavily depend on matrix
very interesting for the simultaneous sampling
composition. Analyte (An) can be any element to be
detected of all isotopes and therefore very interesting for
direct solid analysis by laser ablation. However,
Herzog ESA-MSA sector field geometry early TOF-MS instruments had significantly
(Mattauch and Herzog 1934) in combination lower sensitivity when compared to available
1 Instrumentation, Fundamentals, and Application of Laser. . . 5

quadrupole or sector field instruments. Recent Table 1.2 Wavelength of the first harmonic (bold type)
developments in TOF-MS have achieved limits of various available lasers, and frequency multiplied
wavelengths
of detection comparable with quadrupole
ICP-MS (Borovinskaya et al. 2013). IR VIS UV
Ti: 760–820 nm 380–410 nm
sapphire, (2nd), 265 nm
~30–150 fs (3rd)
1.2.2 Laser Ablation Nd:YAG, 1064 nm 532 nm 355 nm (3rd),
<6 ns (2nd) 266 nm (4th),
The availability of ruby lasers first led to studies 213 nm (5th)
which introduced solid aerosols instead of liquid ArF, 193 nm
15–20 ns
droplets into an ICP ion source. The early devel-
opment of laser ablation was carried out by cou-
pling LA to an ICP-Optical Emission
Spectrometer (Carr and Horlick 1982; Ishizuka loss of energy. Despite the lower energy output,
and Uwamino 1983; Thompson et al. 1981), short wavelength lasers are now most often used,
which was soon followed by LA-ICP-MS as it has been shown that shorter wavelength LA
(Arrowsmith 1987; Arrowsmith and Hughes generates aerosols with nm particle sizes favorable
1988; Gray 1985). The laser is commonly used for ICP-MS due to more complete vaporization
as a micro-sampling device, with the laser beam within the plasma (Guillong and G€unther 2002).
focused onto the sample surface using spot sizes Several reports of the superior qualities of UV LA
of between ~ten to a hundred or more μm compared to IR LA have been published (Geertsen
diameters. The high-energy laser pulse ablates a et al. 1994; Jeffries et al. 1995, 1998; Shuttleworth
small amount of sample, which is transported by 1996). The output energy of an ArF excimer laser
a carrier gas as a solid aerosol or gas phase via is sufficiently high (240 mJ) to enable the use of
transport tube into the ICP. In contrast to all other beam homogenizing optics, leading to flat top laser
laser-based techniques, in LA-ICP-MS, sampling beam profiles that result in more controlled, homo-
and aerosol ionization are physically separated geneous ablation, and flat bottomed ablation
from each other. This is one of the major craters. Despite the loss of energy through the
advantages of this technique as 100 % aerosol additional optical components used, fluencies of
transport and 100 % vaporization within the ICP more than 40 J/cm2 can be reached. The use of
allows quantitative analysis without using matrix a homogenized beam improved precision and
matched calibration materials. accuracy in various applications, particularly on
The types of lasers used for LA-ICP-MS are highly transparent samples (G€unther et al. 1997;
categorized (Table 1.2) by lasing source, the Heinrich et al. 2003). Another advantage of the
wavelength of the emitted energy imaging optics is that the beam energy density
(157–1064 nm), and the pulse duration (approxi- is independent of the crater size. The schematic
mately nanosecond to femtosecond range). All optical beam path of a 193 nm ArF laser ablation
lasers used for ablation are pulsed lasers. The system is shown in Fig. 1.2. Performing flat
most common types are solid state lasers (Nd: top ablation leads to improved signal stability
YAG) and gas lasers (ArF excimer) both of over time, whereas a Gaussian profile crater
which have ns pulse widths. More recently quickly reaches a critical depth from which little
IR/UV fs Ti:sapphire solid state lasers have also or no aerosol leaves the crater site. The influence
been applied for various applications. of the aspect ratio (depth/diameter) and its signifi-
Most solid state lasers, such as the Nd:YAG, cant influence on the representative aerosol sam-
emit light in the near infrared (1064 nm) which can pling has been studied in detail by Mank and
be frequency doubled (532 nm), tripled, quadru- Mason (1999).
pled (266 nm), or quintupled (213 nm). However, The influence of carrier gas composition on
each step of frequency multiplication results in the laser-generated aerosol transport has also been
6 M.B. Fricker and D. G€
unther

CCD camera
Lens

Power meter Petrographic

(alternatively) microscope
N2 in
Excimer laser
(ArF, 193 nm)
Adjustment
diode Optical beam path Mirror
laser Beam splitter
Schwarzschild
objective
Ar Ar
in Out

Ablation cell
with sample

Homo-genizer Field
Prism set up arrays Mask Microscope
lens
aperture Observation through
Raw dielectric 193 nm
laser mirror
beam
Condenser
lens Schwarzschild Secondary
objective Primary mirror mirror
Chamber
window

Image

Fig. 1.2 The ArF excimer laser and details of the beam homogenizer (G€
unther et al. 1997). Reproduced with
permission of the Royal Society of Chemistry

studied (Eggins et al. 1998; G€unther and especially useful for elements with high ioniza-
Heinrich 1999; Mank and Mason 1999). Eggins tion potentials.
et al. (1998) proposed the use of He which allows The quantitative analysis of trace
a more efficient transport of smaller aerosol concentrations of rare earth elements in a variety
particles resulting in a three- to fivefold increase of minerals were reported by Jackson
in sensitivity and a significant reduction in sur- et al. (1992), using a 1064 nm Nd:YAG laser.
face deposition of ablated material around abla- Soon after this study, limitations to the accurate
tion craters. Sensitivity enhancement has also quantitative determination of some analytes were
been observed by the addition of small amounts discovered when analyzing a wide variety of
of H2 to the carrier gas, upstream of the ablation elements, including highly volatile ones. This
cell (Guillong and Heinrich 2007), which is phenomenon was dubbed elemental fractionation
1 Instrumentation, Fundamentals, and Application of Laser. . . 7

(Fryer et al. 1995), and later shown to originate sizes (sizes >150 nm) are not completely
not only from non-stoichiometric sampling, but vaporized within the ICP. This effect was
also processes taking place during aerosol trans- visualized by Aeschliman et al. (2003), who
port (Koch et al. 2004), and incomplete vapori- observed incompletely vaporized particles pass-
zation in the plasma (Guillong and G€unther ing through the plasma. As a result of these issues
2002). Different types of fractionation are mainly with fractionation, today most of the laser
caused by the ablation process, and it has been systems applied for non-conducting samples in
shown that a reduction in laser wavelength geology, medicine, and archaeology are excimer
towards vacuum ultraviolet (VUV) improves lasers (193 nm) or solid state Nd:YAG lasers
the absorption of laser energy, leading to an operated at 213 nm.
aerosol size which can be better transported and Further developments in laser technology
vaporized within the ICP. For non-conducting have led to the introduction of femtosecond
samples, the use of an 193 nm wavelength ArF (fs) lasers as a sampling tool. Studies utilizing
Excimer laser was shown to reduce elemental fs lasers for LA of metallic samples were first
fractionation due to improved absorption of the published using Laser-Induced Breakdown Spec-
laser by the sample. troscopy (LIBS) (Margetic et al. 2000). The first
This resulted in a more controlled ablation, application using LA-ICP-MS was Fe isotope
where controlled means that the rate of ablation ratio determinations performed using a
was slower and the resulting craters showed 196 nm fs LA system coupled to a Multi-
reduced amounts of surrounding debris. More Collector (MC)-ICP-MS instrument (Horn
homogeneous energy distribution also produced et al. 2006). The advantages of using fs lasers,
fewer molten particles and flat bottomed craters. in particular when ablating conducting samples,
Improved ablation behavior was demonstrated has been demonstrated by analyzing the stoichio-
on quartz samples when analyzing fluid metric composition of the aerosols formed during
inclusions in mineral thin sections (G€unther ablation (Garcia et al. 2008, see also a review by
et al. 1997, 1998) and many other applications Koch and G€ unther 2011). It has been shown that
(see Heinrich et al. 2003). Furthermore, the use the elemental composition of the various
of He as carrier gas for transporting laser- particles sizes is not equal, which was already
generated aerosols, first reported by Eggins known from nanosecond (ns) LA experiments.
et al. (1998), led to improved transportation of However, the overall composition of all particle
nm-sized particles and thus to more complete sizes, when combined, represented the stoichi-
vaporization in the plasma. Other laser systems ometry of the ablated sample. Given the stoichi-
in the UV range (213 nm and 266 nm, ometry and knowing that the transport efficiency
e.g. Jeffries et al. 1998) also became available. is comparably high (determined between 78 and
The fundamental differences in particle size dis- 92 %) (Garcia et al. 2008; Wälle et al. 2009) and
tribution produced by the three (266, 213, and the fact that fs-LA produces particles small
193 nm) UV laser wavelengths are reported by enough to be completely vaporized, it becomes
Guillong et al. (2003), who showed the clear that fs-LA is advantageous. Studies on the
advantages of the VUV wavelengths, particularly differences between ns and fs lasers, the expan-
improved particle size distribution. The impor- sion of the laser plume and aerosol formation
tance of particle size distribution has led to stud- (Koch et al. 2007, 2008a, 2010), transport and
ies investigating ICP-induced fractionation on transport efficiency of laser-generated aerosols
generated aerosol using various laser (Garcia et al. 2007, 2008), visualization of the
wavelengths (Guillong and G€unther 2002). It expansion of laser aerosols within the ablation
has been shown that incomplete vaporization of cell (Koch et al. 2008b) and within the transport
large particles in the plasma can take place. For tubes (Koch et al. 2008a) have been extensively
example, Guillong et al. (2003) and Kuhn and reported. All studies revealed that the expansion
G€unther (2003) demonstrated that larger particle of the aerosols is significantly different between
8 M.B. Fricker and D. G€
unther

ns and fs lasers. However, the original particle Further studies have focused on other aspects
size formed during ablation is not so different of laser ablation, for instance the impact of dif-
between ns (193 nm) and fs lasers (265 nm, ferent transport tube materials (Kovacs and
780 nm), which indicates that the improved stoi- G€unther 2008) and the use of rectangular rather
chiometry of the generated aerosol must be the than circular craters (Eggins et al. 1998). A more
major improvement when applying fs lasers for recent fundamental study investigated the forma-
sampling. tion of gas phases during the ablation of carbon
In the last 20 years it has been shown that containing materials (Frick and G€unther 2012),
UV-ns laser ablation is not suitable for stoichio- as carbon is one of the most frequently used
metric sampling of conducting samples and/or internal standards for the analysis of tissue,
volatile elements. For example, Chen (1999), paints, and carbonates (Becker et al. 2008;
Figg et al. (1998), and Outridge et al. (1996) Feldmann et al. 2002).
reported temporal changes of element ratios.
Fryer et al. (1995) introduced the term elemental
fractionation (EF) for these temporal changes in 1.2.3 Ablation Cells
elemental ratios. Later, EF indices were revised
(G€unther et al. 1999) with several other studies The ablation cell is amongst the most important
investigating fractionation effects using ns and fs parts influencing the performance of LA-ICP-MS
LA (Horn et al. 2006; Jackson and G€unther 2003; and several requirements are indispensable for a
Košler et al. 2005; Kroslakova and G€unther routinely used ablation cell. An ablation cell
2007; Kuhn and G€unther 2003; Longerich must be airtight, preventing atmospheric gases
et al. 1996a) at different wavelengths (Russo from entering and extinguishing the ICP, as
et al. 2000). It has been shown that EF can be well as preventing loss of carrier gas and aerosol.
significantly reduced for non-conducting Secondly, the carrier gas flowing through the cell
samples by using 193 nm lasers when compared must transport as much of the laser-generated
to 266 nm Nd:YAG lasers. aerosol as possible (ideally 100 %) to the ICP.
The comparatively long pulse width of ns Finally, containment and mounting of at least
lasers leads to partial heating of conducting one sample and one external standard must be
samples, which results in non-representative possible.
sampling of volatile elements. Therefore, femto- However, generally a number of samples and
second lasers with pulse durations smaller than standards are mounted simultaneously, and it
1 picosecond have been reported to be more must therefore be possible to position the abla-
suitable for LA-ICP-MS (Bian et al. 2005, tion cell while observing sample positioning.
2006; Horn et al. 2006; Koch et al. 2007). Most commercially available ablations cells
Major advantages of fs LA have been reported meet these requirements, and a wide variety of
for the analysis of metallic samples (Mozna ablation cells have been developed. However, for
et al. 2006; Wiltsche and G€unther 2010). This more demanding applications than bulk analysis,
improvement is attributed to the short pulse such as elemental depth profiling (Pisonero
width of fs lasers, on the order of femtoseconds, et al. 2007; Plotnikov et al. 2001) and/or imaging
being sufficiently short to reduce heat effects in (Woodhead et al. 2007) or the analysis of fluid
the ablation zone (Koch and G€unther 2011; inclusions (Heinrich et al. 2003; Pettke
Russo et al. 2002b), thereby decreasing elemen- et al. 2012), these requirements, particularly for
tal fractionation. However, the use of fs-LA for aerosol washout, are more stringent.
the analysis of non-conducting materials did not The spatial resolution of transient signals
result in superior results as reported by Birbaum generated from line scans is determined by crater
(2011) and Glaus et al. (2010). More studies are diameter, scan speed, and aerosol washout time.
currently being performed to provide conclusive For bulk analysis of homogeneous samples the
information. washout time is less critical, as the entire signal
1 Instrumentation, Fundamentals, and Application of Laser. . . 9

of the sample is integrated to calculate elemental introduced the use of a rotating nozzle reducing
concentrations. On the other hand, when the dead volume in a large ablation cell, with the
performing line scans on heterogeneous samples, inlet gas sweeping the entire cell volume. A
the transient signal should reflect the variation of cyclonic flux cell, sweeping the carrier gas from
element concentration within the sample. There- the ablation cell walls to the centre, has been
fore, a long washout (high dispersion) leads to proposed (Monticelli et al. 2009). Tangential or
mixing of aerosol originating from different laser circular gas flows have also been reported by
pulses at different locations along the line scan, Pisonero et al. (2006) using a High Efficiency
resulting in distorted signals. As a consequence, Aerosol Dispersion (HEAD) cell. This principle
spatial information is lost and can only be made was based on two volumes, in combination with
available by using complex deconvolution a Venturi-effect extraction. Some approaches to
algorithms (Plotnikov et al. 2008). In addition, ablation cell design are based on the geometry of
long washout and mixing of the aerosol may lead an enlarged transport tube resulting in a fast
to cross contamination, which has a significant washout for relatively large samples (Gurevich
influence on the accuracy of the analysis. and Hergenröder 2007). Small ablation cells
Early ablation cells were developed for based on the same principle have also been
LA-Graphite Furnace-Atomic Absorption Spec- reported, providing shorter washout times
trometry (GF-AAS) (Schrön et al. 1983) and LA- (Bi et al. 2000; Horstwood et al. 2003; Wang
ICP-Atomic Emission Spectrometry (AES) (Carr et al. 2013).
and Horlick 1982; Ishizuka and Uwamino 1983; Ultimately, the fast aerosol washout of in-tube
Thompson et al. 1981) but are in principle similar ablation can only be made shorter by using an
to those used for LA-ICP-MS. An early study by in-torch ablation such as reported by Tanner and
Arrowsmith and Hughes (1988) reported a “cell G€unther (2005, 2006; Tanner 2007), which had
in the cell” approach in order to entrain and severe limitations in sample handling,
transport laser-generated aerosol. This approach prohibiting many applications in routine analy-
was further developed by several groups (Garcia sis. It must be mentioned that such fast washout
et al. 2007; M€ uller et al. 2009). M€uller and cells are only applicable when simultaneous
colleagues suggested the use of an aerosol detection of the signals becomes possible,
mixing device, placed between the ablation cell e.g. using an ICP-TOF-MS.
and the ICP for smoothing signal. The use of a In addition to attempts to reduce washout
Volume-Optional Low Memory (VOLM) abla- times using in-torch ablation, further work has
tion cell, which uses two cell volumes, has been focused on ablation cell development for both
reported (Liu et al. 2007). These approaches are routine analysis and specialized applications.
based on a sample holder and an insert of a small Analysis of large samples is usually done by
volume cylinder, which is moved together with cutting the sample, in order to fit it into the
the laser beam to the location where LA is small volume ablation cells that are currently
performed. These cells can host a large number available. As the most common applications of
of samples, show less surface contamination LA-ICP-MS have been analyses of geological
between different samples and have reduced sig- samples, e.g. minerals in rock thick or thin
nal dispersion. sections; the volume of ablation cells has not
Fundamental studies on aerosol transport in been very critical. These samples are in most
the ablation cell and transport tubing using pow- cases small enough (a few cm) to be hosted in
der deposition have been reported (Bleiner and traditional ablation cells that have a volume of a
G€unther 2001), and reproduced using gas flow few hundred cm3, which includes the sample
modelling studies. The authors report that when holder and the effective aerosol transport
using extremely small ablation cells, transport volume.
efficiency was limited due to particle-wall However, for many types of samples it is
interactions. Bleiner and Altorfer (2005) simply impractical or impossible to employ
10 M.B. Fricker and D. G€
unther

destructive analysis, e.g. precious objects or developed—one example is shown in Fig. 1.3
museum artefacts (see Chap. 4 for instance). (Fricker 2012), which allows the analysis of
Therefore, ablation cell development has focused laminated sediments of stalagmite samples with
on various so-called “open configurations.” An reduced sample destruction. Further examples
early approach allowing high flexibility with can be found in (Feldmann et al. 2002; Gonzalez
respect to object size was an open ablation cell et al. 2012; M€uller et al. 2009, 2011; Reinhardt
with a plasticine seal to prevent carrier gas et al. 2001, 2003).
containing the laser-generated aerosol from The size and shape of archaeological samples
being lost (G€ unther and Gäckle 1988) and would benefit from a sampling approach without
applied for LA-ICP-OES. This type of cell has any ablation cell. A first possible strategy has
also been applied by Devos et al. (1999) for been demonstrated using a Gas Exchange Device
analysing silver objects. Some limitations of (GED) (Dorta et al. 2013; Kovacs et al. 2010)
this general idea were later improved upon by and was further optimized by Tabersky
Wagner and Je˛dral (2011), using an ablation cell et al. (2013). In these devices, the laser aerosol
without a bottom and applying adhesive is sampled in air and sucked into a gas exchange
materials to attach the cell to a sample. Both of device that exchanges atmospheric gases (air,
these designs are not truly open, as they form an He) for Ar without affecting the laser-generated
airtight configuration using the sample as part of aerosol. The exchange process allows flow rates
the cell. The only open and so called “non-con- of 0.8 L/min, which is a commonly used flow rate
tact” ablation cell has been reported by Asogan in LA-ICP-MS. This approach allows removing
et al. (2009). This ablation cell uses several con- the ablation cell completely (see Fig. 1.4). Pre-
centric gas curtains to exclude atmospheric gases liminary studies showed a 20–30 % reduction in
from entering the carrier gas flow. The set-up sensitivity when using such a device. The use of a
requires close proximity of the cell to the sample plume entrainment device, introduced by
surface and more importantly, it requires a very Tabersky et al. (2013), significantly improves
flat and even sample surface so that the gas aerosol sampling in combination with a GED.
curtain seals the inner cell completely. There- This open ablation GED configuration is most
fore, a wider application of this cell to different valuable for archaeological objects, since no
archaeological artifacts is partially restricted to sample preparation, cutting or contact with a
very flat objects. sample is required. Quantitative results have
The literature on ablation cells is extensive, been reported for various gold objects and steel
and some very specialized cell designs have been samples and the results indicated that a closed

Fig. 1.3 Perspective view

of a low dispersion high
capacity laser ablation cell
as described in Fricker
(2012)
1 Instrumentation, Fundamentals, and Application of Laser. . . 11

Fig. 1.4 Laser ablation-GED-ICP-MS setup for direct described in Kovacs et al. (2010) and further advanced
laser sampling in air followed by online ICP-MS and reported by Tabersky et al. (2013). Reproduced with
measurements of the laser-generated aerosols as permission of the Royal Society of Chemistry

Fig. 1.5 Portable laser ablation system (Glaus generated aerosols are pumped via a diaphragm pump to a
et al. 2013). The figure shows the sampling head filter collector (Figure is reproduced with permission of
connected to the diode pumped solid laser (not shown) the Royal Society of Chemistry)
via fiber optics, which can be placed on any object. The

cell configuration and the “in air” ablation proce- strategy is based on a diode pumped laser abla-
dure using the GED provide very similar results. tion system coupled to a sampling device (see
Another more recently introduced approach of Fig. 1.5). The aerosol generated by the laser is
interest for archeometrical studies is the concept sucked from the ablation site via a diaphragm
of a portable laser ablation system (pLA), as pump onto a filter. A rotating filter plate can
introduced by Glaus et al. (2012, 2013). The host up to 12 filters, which can be stored and
system weighs 16 kg and can be transported to finally analyzed in the laboratory. The samples
samples outside the laboratory. The sampling can be processed by complete digestion of the
12 M.B. Fricker and D. G€
unther

filter and solution nebulization ICP-MS or unit concentration) in the external calibration
MC-ICP-MS. Alternatively, the filter can also material and the sample is corrected using a
be analyzed by LA-ICP-MS. This sampling strat- “naturally” occurring internal standard
egy allows access to elemental composition of (e.g. Ca), which must be known in both the
the ablated sample and/or isotope sample of interest and the calibration material.
determinations. One requirement is that filter The concentration of the internal standard in the
blanks are also collected. To do so, environmen- unknown sample can be determined using an
tal air at the sampling site is sampled for a similar alternative analytical technique, most commonly
period as the aerosol collection. This strategy has Electron Probe Micro-Analysis (EPMA). In
been tested and validated on pigments and on some cases it is also possible to estimate the
copper objects. The limits of detection are an internal standard concentration from the stoichi-
order of magnitude above those commonly ometry of the sample. A variant internal
obtained using a normal LA-ICP-MS setup. standardization procedure uses normalization to
However, limits of detection below 1 mg/kg 100 % oxide weight. Background-subtracted
were achieved for most elements, and are there- intensities are used to calculate concentrations
fore still below the detection limits of other direct using Eq. (1.1).
sampling techniques such as X-ray Fluorescence
(XRF) and Laser-Induced Breakdown Spectros- I SMP I ES CES
CSMP
X ¼ CSMP
IS  X
SMP
 IS  XES ð1:1Þ
copy (LIBS). This portable instrument configura- I IS I ES
X CIS
tion can also be used in the lab in combination
with the GED, does not require the filter collec- Where:
tion step, and allows the direct measurement of CXSMP Concentration of analyte x in sample
samples of all sizes and geometries. A thorough CISSMP Concentration of internal standard in
validation of the pLA-GED-ICPMS technique sample (obtained from independent
demonstrated that this approach allows trace ele- measurements)
ment determinations within 10–20 % of accepted IXSMP Signal of analyte x in sample
values when using reference materials (Glaus (BG-subtracted, abundance-normalized)
SMP
et al. 2012; Tabersky et al. 2013). IIS Signal of internal standard in sample
(BG-subtracted, abundance-normalized)
IISES Signal of internal standard in external
standard (BG-subtracted, abundance-
1.3 Quantification
normalized, linearly interpolated)
IXES Signal of analyte x in external standard
Quantification in LA-ICP-MS is most often
(BG-subtracted, abundance-
based on the calculation scheme proposed by
normalized, linearly interpolated)
Longerich et al. (1996b). Element concentrations
CXES Concentration of analyte x in external
are calculated using external and internal
standard (certificate of ES)
standardization (see Eq. 1.1). To correct for
CISES Concentration of internal standard in
instrumental drift, the external standard signal
external standard (certificate of ES).
intensities are interpolated between two external
standards analyzed before and after the analyses
For bulk quantification the background-
of the unknown samples. All intensities are back-
subtracted mean signals (SG) are used in
ground corrected using a “gas background”
Eq. (1.1), whereas for imaging quantification or
acquired with the laser not firing on the sample.
depth profiling each data point, or integration
This “gas background” is commonly acquired for
over a few data values, of the SG interval
a period of 30 s prior to the acquisition of the
(background-subtracted) is quantified individu-
analyte signal. Matrix effects and aerosol trans-
ally to obtain a concentration profile. In cases
port, that is the ratio of the sensitivity (signal per
1 Instrumentation, Fundamentals, and Application of Laser. . . 13

Fig. 1.6 Calculation

schemes for the limits of
detection estimation. DT
refers to dwell time

where the presence of spikes (related to the sam- calculation schemes for LOD estimation are
ple) limits data quality, it is also possible to use listed in Fig. 1.6.
the median instead of average signals, which is The quantification scheme shown above is
more robust against outliers than the mean. based on one single external standard and signif-
Ongoing discussions on estimating limits of icantly different from the procedure from solu-
detection (LOD) using either the normal distri- tion nebulization ICP-MS, where many standard
bution (ND) or Poisson distribution (PD) have solutions, including matrix matched ones, can be
led to the use of different formulas. The LOD in prepared to establish the calibration function.
LA-ICP-MS, and in any elemental analysis tech- The lack of suitable calibration materials for
nique, is a function of the uncertainty (standard LA-ICP-MS is one of the major limitations of
deviation) of the background (blank) measure- this technique since the material has to fulfill
ment, the estimated uncertainty in a theoretical certain requirements. The ablation behavior of
sample with zero concentration of the analyte, the sample of interest and the calibration material
and the instrument sensitivity along with its should be similar, which means that similar
estimated uncertainty. Due to the very low amounts of aerosol should enter the ICP for com-
backgrounds (a few counts) for many analytes plete vaporization (Kroslakova and G€unther
in ICP-MS, a large portion of the uncertainty in 2007). Furthermore it is required that the calibra-
the background is from Poisson counting statis- tion material should be homogeneous on the
tics. Thus in some analytical situations an esti- scale of ablation, which is between 5 and
mate of background uncertainty derived from 200 μm. This is rather difficult to achieve by
Poisson statistics alone can be a good approach. mixing powders or adding solutions to powder
As it is common in LA-ICP-MS to have close to samples. Therefore, various approaches to pro-
or zero background signal for heavy isotopes, it duction of in-house prepared calibration
is important to employ suitable statistics to esti- materials have been reported based on fusion
mate the standard deviation of the background. (Jochum et al. 2011). Due to problems with
This is important for several reasons, including homogeneity when using alternative preparation
the non-Gaussian distribution obtained when techniques, glasses of the NIST series 61 are
considering a small number of events. For zero currently the most frequently applied calibration
or close to zero counts the standard deviation of materials in LA-ICP-MS when analyzing
the background follows, to a large extent, non-conducting samples, due to the large number
counting statistics, i.e. a Poisson distribution. of elements present in various concentrations and
The two major ablation schemes are considered the spatial homogeneity of those elements.
(bulk and bore). “Bore” considers each data point Exceptions have been reported by Eggins and
during drilling into a sample or during scanning Shelley (2002). However, a variety of other
on a surface, which means n is equal to one. The glass standards (e.g. MPDING, USGS
14 M.B. Fricker and D. G€
unther

GSA-GSE) are also available. For conducting system provides access to samples which are
samples more calibration materials (e.g. brass, difficult to move (e.g. museums objects) and
bronze, copper) are available and need to be can be used directly in the field.
more closely matrix matched for quantification,
as the ablation process using ns lasers can cause Acknowledgements The authors would like to thank
severe fractionation effects hampering Henry Longerich for fruitful discussion and comments
on this manuscript.
quantification.

1.4 Summary and Outlook References

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