Spectrochimica Acta Part B 61 (2006) 642 659

www.elsevier.com/locate/sab

Investigation of plasma-related matrix effects in inductively coupled

plasma-atomic emission spectrometry caused by matrices with
low second ionization potentialsidentification of the secondary factor B
George C.-Y. Chan, Gary M. Hieftje *
Department of Chemistry, Indiana University, Bloomington, IN 47405, USA

Received 19 July 2005; accepted 15 September 2005

Available online 17 November 2005

Abstract

Plasma-related matrix effects induced by a comprehensive list of matrix elements (a total of fifty-one matrices) in inductively coupled plasma-
atomic emission spectrometry were investigated and used to confirm that matrix effects caused by elements with a low second ionization potential are
more severe than those from matrix elements having a low first ionization potential. Although the matrix effect is correlated unambiguously with the
second ionization potential of a matrix, the correlation is not monotonic, which suggests that at least one other factor is operative. Through study of a
large pool of matrix elements, it becomes possible to identify another critical parameter that defines the magnitude of the matrix effect; namely the
presence of low-lying energy levels in the doubly charged matrix ion. Penning ionization by Ar excited states is proposed as the dominant mechanism
for both analyte ionization/excitation and matrix effects; matrices with a low second ionization potential can effectively quench the population of Ar
excited states through successive Penning ionization followed by ion-electron recombination and lead to more severe matrix effects.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Matrix effects; Second ionization; Inductively coupled plasma-atomic emission spectrometry; Penning ionization; Energy levels

1. Introduction atomization of the matrix [7 9], increased collisional excita-

Inductively coupled plasma-atomic emission spectrometry
(ICP-AES) is one of the most prevalent analytical techniques
for elemental analysis and is nowadays widely used for routine
qualitative and quantitative elemental analysis [1,2]. However,
there remains an incomplete understanding of the ICP itself.
For example, an important but yet not fully resolved issue is the
understanding and elimination of sample-dependent matrix
interferences [1 5].
Matrix effects in ICP-AES have been widely reported in the
literature [6 27] and have been reviewed recently [3,4].
Several mechanisms have been proposed to explain the origin
of plasma-related matrix effects, including changes in excita-
tion conditions in the plasma [6], energy consumption during
B
This article is published in a special honor issue of Spectrochimica Acta
Part B dedicated to the memory of Prof. Howard V. Malmstadt, in recognition
of his many outstanding contributions to the spectrochemical analysis, in areas
of research, leadership, and teaching.
* Corresponding author. Tel.: +1 812 855 2189; fax: +1 812 855 0985.
E-mail address: hieftje@indiana.edu (G.M. Hieftje).
0584-8547/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2005.09.007
tion [10 12], ambipolar diffusion [10], a shift of analyte-
ionization equilibrium [10 12], ion-electron recombination
[13 15] and lateral diffusion [11,12,16]. However, so far there
is no agreement on the dominant mechanism [1 5].
The fact that the matrix effect induced by Ca is more severe
than those by K and Na in the ICP is well known and has been
independently reported by several researchers [6,7,17 23].
However, the exact mechanism of the matrix effect Ca
generates is still largely unknown. Matrix effects from Ca
and Na are different in nature. The matrix effect caused by Na
can be easily reduced or eliminated by the use of so-called
robust plasma operating conditions [4,24 27], while that by Ca
is only slightly lessened [19 23]. It has been shown that, under
robust plasma conditions, the MgII/MgI ratio (an indication of
plasma robustness) remains constant in the presence of a Na
matrix and the intensity of analyte emission lines is lowered to
the same extent, regardless of the character of the analyte and
the excitation energy of the emission lines [24 27]. In other
words, matrix effects produced by a Na matrix are controllable,
and the major interference mechanism for a Na matrix under
 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659
such situations is non-plasma-related (i.e., it is related to the
sample introduction system) [24 27]. Interestingly, the first
ionization potential of Ca is higher than that of Na [28] and
quite a number of the proposed matrix-effect mechanisms
involves the addition of electrons generated during matrix
ionization (e.g., ambipolar diffusion, increased collisional
excitation, shift of analyte-ionization equilibrium, ion-electron
recombination). Since the ionization potential is one of the key
parameters that governs the degree of ionization (and hence the
concentration of electrons released by matrix ionization), it has
been surmised that the larger matrix effect from Ca is not an
ionization-type interference; it has been suggested that the
higher atomization energy of Ca salts might be responsible for
its larger matrix effect [7 9]. However, only recently, this
proposed mechanism has been excluded as dominant by
studying matrix effects in ICP-AES with laser-ablation
sampling [29].
When the workers ablated calcium carbonate and lithium
carbonate, which have similar standard enthalpies of atomiza-
tion, the matrix influences on plasma excitation conditions (as
reflected by a change in the ZnII/ZnI ratio) were found to be
different. Yet, the matrix effect from calcium carbonate and
calcium fluoride, which have significantly different enthalpies
of atomization, were similar [29]. These results prove that
energy consumption during atomization of the matrix is not the
dominant mechanism for the greater matrix effect induced by
Ca matrices than by Group I matrices [29]. In a follow-up
study, the matrix effects of thirty-one elements on plasma
excitation conditions were studied by using solution nebuliza-
tion for sample introduction [19]. Ten matrix elements were
found to induce significantly more severe matrix effects than
the others; the only common features of these ten matrices were
their relatively low second ionization potentials (2nd IP); their
2nd IPs lie between 10.0 eV and 13.1 eV (i.e., lower than the
1st IP of Ar at 15.7 eV). Moreover, all elements with a low 2nd
IP produced more severe matrix effects. Therefore, it was
suggested that the more severe matrix effect from Ca and other
low 2nd IP matrix elements (e.g., Ba) can be attributed to the
second ionization of the matrix ions [19].
While there is an unambiguous correlation between the
magnitude of the matrix effect and the 2nd IP of the matrix
element (which logically, but not necessarily, is linked to
second ionization or formation of the doubly-charged ion of the
matrix), the mechanism is unknown. At first glance, one might
think that second ionization merely opens up an additional
channel for the production of extra electrons in the plasma.
However, even though the 2nd IP of these matrices is low, the
degree of second ionization is not high and is at most 10%,
calculated theoretically [30] and reported experimentally in
ICP-MS studies [31,32]. Therefore, the number density of any
additional electrons generated from second ionization of the
matrix is only a fraction of that from first ionization. Even in
the hypothetical situation that all matrix ions are doubly
ionized, the additional electrons generated by low 2nd IP
matrices is only twice that for easily ionizable elements (EIEs,
e.g., the Group I elements). In other words, the matrix effect
from an EIE at a doubled concentration is expected to be
643
identical to that from a low 2nd IP matrix in this hypothetical
situation. In reality, since second-ionization efficiency never
approaches 100%, the matrix effect from a doubled-concen-
tration of an EIE should be larger. However, the reverse is
observed; the matrix effects from Na and K are significantly
smaller than that from Ca even if the molar concentration of the
former elements is doubled [20 23].
Moreover, apart from the 2nd IP, there appear to be other
factor(s) that determine the severity of the matrix effect [19].
For example, barium has the lowest 2nd IP among the elements
in the periodic table; however, matrix effects from the rare-
earth elements (REEs) are even stronger than that from Ba [19].
Unfortunately, the number of low 2nd IP matrix elements
included in the previous study [19] is relatively limitedonly
ten, and there were no conclusions on the additional
parameter(s) that explain the greater matrix effects from REEs
[19]. It is the objective of the present study to identify this
additional factor for matrix effects.
2. Research approach and methodology
The approach employed in the present study is straightfor-
ward; the matrix effect from a comprehensive list of low 2nd IP
matrices was studied. Despite the relatively long history of
matrix-effect studies in ICP-AES, the types of matrices that
have been covered are not large. The most widely studied
metallic matrices were Na, K and Ca [3,4], probably partly
because they are the most abundant matrices encountered in
environmental (e.g., sea water and river water) and biological
(e.g., biological fluid) samples and partly due to historical
reasons, as they were widely studied in flame atomic sources. It
is obvious but noteworthy that any deduced matrix effect
mechanism is valid at most only for the group of investigated
matrix elements, and it is possible that the correlation or
conclusion is incomplete or even erroneous if the group is too
small. Moreover, any conclusions about the mechanism of a
matrix effect cannot be complete if not all the major factors that
govern the matrix behavior are known. Undoubtedly, revealing
the presence of any hidden parameter is possible and
conclusive only if the set of matrices under study is sufficiently
large. Therefore, an expanded approach was used herematrix
effects from a comprehensive list of elements were investigat-
ed, and thus the trends of matrix effects and conclusions are
expected to be globally valid.
The periodic table shown in Fig. 1 lists the 2nd IP of each
element; virtually all (with the exception of non-naturally
occurring or radioactive) low 2nd IP matrix elements were
studied. Those matrix elements that were studied are divided
into three categories according to their 2nd IP with reference to
the 1st IP of Ar (15.75 eV); the three categories are (a) low 2nd
IP (below 15 eV), (b) intermediate 2nd IP (between 15 and
16 eV), and (c) high 2nd IP (above 16 eV).
Our interest in matrix effects lies in those processes that
affect the excitation and ionization of the analyte (the so-called
plasma-related matrix effects), because such matrix effects are
difficult to predict and master by a simple method. The ionic-
to-atomic line-intensity ratio was used as an indicator of
644 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659

H He
54.42

Li Be B C N O F Ne
75.64 18.21 25.15 24.38 29.60 35.12 34.97 40.96

Na Mg Al Si P S Cl Ar
47.28 15.04 18.83 16.35 19.77 23.34 23.81 27.63

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
31.63 11.87 12.80 13.58 14.66 16.49 15.64 16.19 17.08 18.17 20.29 17.96 20.51 15.93 18.63 21.19 21.80 24.36

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
27.28 11.03 12.24 13.13 14.32 16.16 15.26 16.76 18.08 19.43 21.49 16.91 18.87 14.63 16.53 18.6 19.13 21.21

Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
23.16 10.00 14.9 16 16.1 17 17 17 18.56 20.20 18.76 20.43 15.03 16.69 19 20 21

Fr Ra
22 10.15

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
11.06 10.85 10.55 10.73 10.90 11.07 11.24 12.09 11.52 11.67 11.80 11.93 12.05 12.18 13.9

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
11.75 11.9 10.6 11.2 11.8 12.0

nd
2 IP < 15 eV
nd
15 eV < 2 IP < 16 eV
nd
2 IP > 16 eV
Fig. 1. Periodic table highlighting the studied matrix elements and their 2nd IPs. Matrices marked with a diagonal pattern have a 2nd IP below 15 eV; those with
horizontal stripes have 15 eV < 2nd IP < 16 eV; and those filled completely in gray have a 2nd IP above 16 eV.

plasma-related matrix effects, as it is sensitive only to changes
in plasma excitation conditions and is independent of the
absolute amount of analyte entering the plasma (i.e., any
sample-introduction-related matrix effect will not affect this
ratio). Under the assumption of local thermodynamic equilib-
rium (LTE), this ratio is a function of plasma temperature and
electron number density according to Eq. (1) [33].
 
IIonic 4:83  1015 gq Apq
R 
IAtomic ne kpq Ionic
 E Eq Eq
i 1
 T 3=2 e kT
where R is the ionic-to-atomic spectral-line intensity ratio, I is
the emission intensity, n e is the electron number density, g q and
g p are the statistical weights (degeneracies) of the upper state q
and lower state p involved in the transitions, respectively, A pq
and k pq are the Einstein transition probability and wavelength
of the transition, respectively, k is the Boltzmann constant, T is
the absolute temperature of the plasma and E+i , E q+ , and E q are
the first ionization potential of the test element and the energy
levels of the upper state q for the ionic and atomic emission
lines, respectively.
Theoretically, any element can be used as a test element.
Technically, however, there are appropriate criteria to apply in
selecting the test element. First, the ionic and atomic emission
lines should be of comparable emission intensities so detector
linearity is not a factor. Second, the emission line pair from
the test element must be strong (so a small amount of analyte
is sufficient). Third, the emission spectrum of the test element
should be relatively simple. Finally, the spectral lines should
be close in wavelength, so the spectral response of the system
causes no distortion. It was found that the line pairs MgII
(280.270 nm)/MgI (285.213 nm), ZnII (206.200 nm)/ZnI
(213.86 nm), and CdII (214.438 nm)/CdI (228.802 nm) meet
most of the above requirements. In addition, FeII/FeI, NiII/
  NiI, PbII/PbI, MnII/MnI, and CrII/CrI can be used in various
kpq combinations of their corresponding ionic and atomic

gq Apq Atomic
emission lines without causing any inter-test-element spectral
interference.
3. Experimental
3.1. Experimental setup
A schematic diagram of the experimental setup is shown in
Fig. 2. A commercial ICP-AES spectrometer capable of nearly
full-wavelength coverage (84% from 185 nm to 900 nm) by
means of a charge-injection device (CID) detector was used. The
test-element and matrix solutions were pumped through two
separate channels of a peristaltic pump and mixed via a glass T-
joint before entering an ultrasonic nebulizer (USN). The plasma
was operated under typical conditions for a robust plasma; the
plasma forward power was held at 1350 W, central-channel gas
flow rate was at 0.8 L/min, and the plasma observation height
was 15 mm above the load coil. The MgII/MgI ratio, which
reflects plasma robustness, was measured to be 13.6. Details for
other operating parameters are given in Table 1.
 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659 645

Echelle-grating various matrices were measured in turn. The standard intensity

hv Spectrometer and
ICP (i.e., intensity of the test element in the absence of any matrix)
2-D imaging
was intermittently measured to check for plasma drift, either
array detector
when five to six matrices had been measured or after the whole
Ultrasonic set of experiments. If there was no drift in the sample-
Nebulizer introduction system and the plasma excitation conditions, the
intensity observed during the drift check should be identical to
Matrix the initially measured reference intensity. The purpose of the
Glass
Pump drift test is to monitor the drift of the system during the whole
Test Element T-joint
(Analyte) course of the experiment and to ensure that any observed
matrix effect is not due to artifacts from long-term stability.
Fig. 2. Schematic diagram of the experimental setup.
4. Results and discussion
3.2. Sample preparation
4.1. Primary factor of matrix effectsecond ionization
10,000 Ag/mL stock solutions of the test elements were potential of the matrix
individually prepared from the analytical-grade nitrate salt. The
test-element working solution was then diluted from the Fig. 3a and b show the matrix effects on the relative MgII/
corresponding stock solution with 2% v/v HNO3. A working MgI, ZnII/ZnI, CdII/CdI and FeII/FeI emission-intensity ratios
solution containing multiple test elements (Mg at 10 Ag/mL, as a function of the first and second ionization potentials of the
Cr, Cd, Mn, and Fe at 20 Ag/mL, Ni and Zn at 50 Ag/mL, Cu
and Pb at 100 Ag/mL) was prepared and emission intensities
from these nine test elements were measured simultaneously. Relative Ionic-to-Atomic Intensity Ratio / %
a
All the matrices were at equimolar concentration (0.05M); the 110
matrix solution was prepared from analytical grade salts
(usually, nitrate or chloride) with the exception of Si, Ti, Ge, 100
B, Be, Zr, Mo, V and Ce. The first three matrices (Si, Ti, and
90
Ge) were prepared from their corresponding ammonium
hexafluoro-complexes, B from boric acid, Be from digestion 80
of its metal, Zr from zirconyl chloride, Mo from ammonium
molybdate, V from digestion of vanadium pentaoxide and Ce 70
from ammonium cerium nitrate.
60
MgII/MgI
3.3. Experimental procedures ZnII/ZnI
50 CdII/CdI
FeII/FeI
A complete matrix-effect experiment comprises several 40
ICP-AES measurements. First, spectral interference by the 3 4 5 6 7 8 9 10
st
matrix on the test elements emission lines was checked. This 1 IP of Matrix / eV
was achieved by pumping the matrix solution into one channel b
Relative Ionic-to-Atomic Intensity Ratio / %

and a 2% v/v HNO3 blank solution into the other. Spectral lines 110
of the test elements that overlap with those of the matrix
element were not used for that matrix element. Second, the 100
emission intensity of the test element in the absence of a matrix
90
(referred to as standard intensity) was then measured. Third,
the emission intensities of the test element in the presence of 80

70
Table 1
Plasma operating conditions
60
ICP spectrometer TJA IRIS ICP-AES spectrometer MgII/MgI
Forward power 1350 W ZnII/ZnI
50 CdII/CdI
Outer gas flow 15 L/min
FeII/FeI
Intermediate gas flow 1 L/min
40
Central gas flow 0.8 L/min 10 15 20 25 30
Injector-tube inner diameter 1.5 mm nd
Observation height 15 mm ALC 2 IP of Matrix / eV
Solution uptake rate 1.5 mL/min for each channel
Fig. 3. Matrix effect on ionic-to-atomic line-intensity ratio for Mg, Zn. Cd and
MgII/MgI ratio 13.6
Fe versus (a) 1st IP and (b) 2nd IP of the matrix element. The circled group of
Replicates 5
matrices shows out-of-trend behavior.
646 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659

matrices, respectively. The relative ionic-to-atomic line-inten- arranged in order of ascending 2nd IP (from 10.0 to 16.2 eV).
sity ratio used to assess the matrix effect is obtained by The four matrices that show unambiguous out-of-trend behavior
dividing the value of MII/MI in the presence of a matrix to that are Ba, Sr, Ca and Yb. To a lesser extent, Sn (2nd IP= 14.63 eV),
in an absence of a matrix. If the resulting ratio (quotient) is Pb (2nd IP= 15.03 eV), and Ge (2nd IP= 15.93 eV) also exhibit
100%, there is no indication of a plasma-related matrix effect. out-of-trend behavior compared to their neighbors (cf. Fig. 4). It
The experimental uncertainty and long-term drift of the relative has already been reported in the literature that matrix effects
MII/MI ratio is typically within 3%. Other studied test elements from alkaline earth elements (Ba, Sr and Ca) are less severe than
show similar results. those from other low 2nd IP matrices [19]. The experiment
In agreement with previous reports in the literature [19,34], summarized in Fig. 4 suggests that four additional elements
there is no trend between matrix effects and the 1st IP of the (Yb, Sn, Pb and Ge) should be included in the list of low 2nd IP
matrices (Fig. 3a). However, there exists a strong correlation matrices that exhibit comparatively less severe matrix effects.
between the matrix effect and the 2nd IP; matrices with a 2nd Although these seven matrix elements are found in only three
IP lower than 15 eV induce severe matrix effects (Fig. 3b). groups in the periodic table (alkaline earth, Group IVB and rare
At first glance, it might seem that there exists a correlation with earth), there are no obvious similarities in either physical or
the 1st IP of the matrix (Fig. 3a); matrices with a 1st IP chemical properties among these seven elements or among
between 5 and 7 eV cause a more severe effect. However, that these three periodic groups.
apparent correlation is an artifact; it just happens that all the
low 2nd IP matrices (those showing a strong matrix effect in 4.2. Identification of the secondary factor for the matrix effect
Fig. 3b) have a 1st IP in the 5 7 eV range. It should be noted
that there also exists some matrix elements with a 1st IP in this A number of physical properties of these matrices were
5 7 eV range that do not induce a matrix effect (Fig. 3a). compared with the trend observed in Fig. 4; clearly, it is
Undoubtedly, matrices with a low 2nd IP cause a significant impossible to consider all combinations of physical parameters
change in the plasma excitation and ionization conditions; and only those that might be directly related to plasma
moreover, this effect is global, considering that almost all low interactions need be examined. The list of these physical
2nd IP elements were covered in the present study. It is also parameters includes: 1st and 3rd IPs of the matrix, the atomic
evident that at least one other factor is operative, as there are partition function of the singly-charged (M+) and the doubly-
four matrix elements that show unambiguous out-of-trend charged (M2+) matrix ion, the partition function ratio of M2+ to
behavior (see the circled group in Fig. 3b); their effect is M+, and the averaged excitation energy and the metal-oxide
smaller (yet significant) than that of other elements with similar bond energy of the matrix. These seven parameters are
2nd IP. For ease of discussion in the present paper, the 2nd IP considered here because of their possible direct link to
of the matrix will be referred to as the primary factor for the matrix-effect mechanisms that have already been discussed in
matrix effect and the additional unknown factor(s) to be the literature, or because they spring directly from the
investigated are referred to as the secondary factor for the experimental data.
matrix effect. This section is arranged so the identified secondary factor is
To search for the secondary factor, it is important to know the presented first. It turns out that only one of these seven
identity these four out-of-trend low 2nd IP matrices. Fig. 4 is a candidates (the partition function of M2+) showed a strong one-
plot of matrix effect severity against each matrix element, to-one correlation with the observed matrix effects. After
presentation and discussion of the identified secondary factor,
the results of the remaining candidates are considered.
Relative Ionic-to-Atomic Intensity Ratio / %

110 Sn Pb Ge
Before proceeding, it is useful to point out that these seven
100
physical properties of the matrix can be divided into two
categories, depending on whether or not they have a direct link
90 Ca Yb to the primary factor of the matrix effect (i.e., the 2nd IP or its
Sr
physical equivalentthe second ionization process). It should
80 Ba be noted that if the secondary factor for the matrix effect
involves a physical property that is independent of the 2nd IP
70
(e.g., the metal-oxide bond energy of the matrix), its effect
60 should be extendable to all the studied matrices, regardless
MgII/MgI their 2nd IP. In other words, such an effect will operate
ZnII/ZnI
50
CdII/CdI
independent of the 2nd IP (or second ionization) and be
FeII/FeI additive in nature. On the other hand, if the physical property is
40 of a type that is directly connected to the 2nd IP (e.g., the 3rd
Y

V
Ba
Pr
Nd
Ce
Sr
La
Sm
Eu
Tb
Dy
Ho
Ca
Er
Tm
Gd
Yb
Sc
Zr
Ti
Lu
Nb
Sn
Hf
Pb
Mg
Mn
Ge
Mo

IP), then its effect is applicable only to those matrices whose

Increasing 2nd Ionization Potential from 10.00 to 16.16 eV 2nd IP is low. In such a case, the effect of the 2nd IP and the
Fig. 4. Matrix effect on ionic-to-atomic line-intensity ratio from individual candidate physical property operate together, analogous to a
matrix elements sorted in ascending order of the 2nd IP. Ba, Sr, Ca, Yb, Sn, Pb multiplicative effect. In the last example, the 3rd IP (third
and Ge showed out-of-trend behavior compared to their neighbors. ionization) can be considered a factor dependent on the 2nd IP
 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659
(second ionization), because if the 2nd IP is sufficiently high, it
is improbable that third ionization will occur no matter how
low the 3rd IP is. Table 2 classifies the seven secondary factor
candidates in this study.
4.2.1. Atomic partition function of doubly-charged matrix ion
as an identified secondary factor for matrix effects
Our consideration of the partition function of the doubly-
charged matrix ion as a secondary factor is based on a
deduction from the electronic configuration of Ba2+, Sr2+ and
Ca2+. Doubly ionized Ba, Sr and Ca ions have a noble-gas
electronic configuration. Two features of such a configuration
are (1) the high IP for the next successive ionization step (i.e.,
the 3rd IP, which will be discussed in the next section), and (2)
the absence of low-lying energy levels and a high excitation
energy for the first excited state. For instance, the first excited
states of Ba2+, Sr2+ and Ca2+ lie at 16.5 eV [35], 21.9 eV [36]
and 25.2 eV [37], respectively, above the ground state of the
corresponding doubly-charged ion. Such a high energy for the
first excited state implies that Ba2+, Sr2+ and Ca2+ ions are all
in their ground electronic state. In contrast, due to the
incompletely filled f-shell for the REEs, low-lying energy
levels are available for the doubly charged REE ions.
Therefore, the electronic partition function of the doubly-
charged matrix ion is an appropriate candidate for a secondary
factor, as the physical meaning of the partition function can be
regarded as the number of thermally accessible states.
Fig. 5 shows the relation between the matrix effects and the
electronic partition function [30,38 40] of M2+ at an assumed
plasma temperature 7000 K. The matrices are arranged in
ascending order of their 2nd IP, so the 2nd IPs are very similar
between any matrix element and its neighbors. Plots arranged
in this way simplify the identification of the secondary factor;
if the partition function is a secondary factor, its value should
be correlated with the severity of the matrix effect when
arranged in a plot like this. For clarity, the matrix effect from
only one test element is shown; Zn was chosen as a
representative because it is the only element that suffers no
spectral interference from all these thirty low 2nd IP matrices.
Other studied test elements suffer from spectral interference
from some of these matrices and lead to an incomplete trend.
Figs. 3 and 4 already showed that Zn is a valid representative;
results from other test elements support the same conclusion
drawn below from Zn data.
Table 2
Classification of secondary factor candidates for the matrix effect
Physical properties that are independent of 2nd IP or second ionization
1st IP of matrix
Atomic partition function of singly-charged matrix ion
Averaged excitation energy of singly-charged matrix ion
Metal-oxide bond energy of matrix
Physical properties that are dependent of 2nd IP or second ionization
3rd IP of matrix
Atomic partition function of doubly-charged matrix ion
Partition function ratio of M2+ to M+
647
Fig. 5 shows a strong correlation between the matrix effect
and the electronic partition function of M2+; for matrices with
similar 2nd IP, the lower the partition function, the lower the
matrix effect (the higher the ZnII/ZnI ratio). In particular, all
of the seven out-of- trend matrices (Ba, Sr, Ca, Yb, Sn, Pb
and Ge) have the lowest electronic partition function, with a
value virtually equal to one (i.e. there are virtually no
thermally accessible states from the ground state of the
doubly charged ion).
To further investigate the possibility that the electronic
partition function (or its physical equivalentthe presence of
low-lying energy levels) of the doubly-charged matrix ion is
one secondary factor, the matrix effect can be compared with
the energy-level diagram of the matrix elements. Fig. 6 shows
an energy level diagram for M+ and M2+ [37,41 43] of the
thirty studied low 2nd IP matrix elements in ascending order of
their 2nd IP. The identified primary factor for the matrix effect
is the 2nd IP, which corresponds to the ionization energy from
the ground state of the singly charged ion to the ground state of
the doubly-charged ion. Accordingly, the energy levels in Fig. 6
are referenced to the ground state of M+, which is given an
energy equal to zero. As is clear in Fig. 6, six of the out-of-
trend matrix elements presented in Fig. 5 (Ba, Sr, Ca, Yb, Sn,
and Pb) have no energy level between the ground state of their
doubly-charged ion and the first ionization potential of Ar
(15.75 eV); in contrast, other elements (from Pr to Hf) possess
energy levels between their doubly-charged ground state and
the 1st ionization limit of Ar.
The fact that the NIST database [37,41,42] is not complete,
especially for doubly charged rare-earth elements, has also
been considered in this analysis. In cases when there appears a
large gap in energy levels between the M2+ ground-state and its
first excited/low-lying level (e.g., Eu and Yb), other more
recent references [44 51], based mostly on theoretical
calculation of energy levels, have been consulted. In contrast,
no further reference was sought when the NIST database
already listed the presence of close energy gaps above the M2+
ground state. Table 3 lists the energy of the ground-state and
the low-lying energy level or first excited state (whichever is
lower) of the doubly-charged matrix ion. It clearly argues that
the presence of low-lying energy levels in M2+ is a determining
factor for the matrix effect caused by low 2nd IP elements;
matrices with first excited state or low-lying energy levels
below the 1st IP of Ar (15.75 eV) induce stronger matrix
effects in the plasma.
4.2.2. Third ionization potential of the matrix
The third ionization potential of the matrix might be a
secondary factor, as a logical extension of arguments made for
the 2nd IP. Moreover, at first glance, the 3 rd IP of Ba, Sr and
Ca are high, as the ionization M2+YM3+ for these three
elements involves removal of an electron from a rare-gas
electronic configuration. Fig. 7 shows the relationship between
the matrix effect and the 3rd IP [28] of the matrix in ascending
order of 2nd IP. Although the 3rd IP shows good correlation
with the matrix effect caused by Ba, Sr and Ca (higher 3 rd IP,
higher relative ZnII/ZnI ratio, i.e., less severe matrix effect), no
648 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659

2+
ZnII/ZnI Partition function of M
110
Sn Pb Ge 100

Relative ZnII/ZnI Intensity Ratio / %

Partition Function of M2+ at 7000K

100

90 Ca
Sr Yb
80 Ba
10
70

60

50

1
40
Ba
Pr
Nd
Ce
Sr
La
Sm
Eu
Tb
Dy
Ho
Ca
Er
Tm
Gd
Yb
Y
Sc
Zr
Ti
Lu
Nb
Sn
V
Hf
Pb
Mg
Mn
Ge
Mo
Increasing 2nd Ionization Potential from 10.00 to 16.16 eV

Fig. 5. Correlation of matrix effect on relative ZnII/ZnI ratio with the partition function of the doubly-charged matrix ion, Q(M2+), at an assumed plasma temperature
of 7000 K. Matrix elements are sorted in ascending order of the 2nd IP.

significant correlation is observed for Yb, Sn, Pb and Ge. IP is not a significant factor in governing the matrix effect from
Therefore, it is not probable that the secondary factor involves low 2nd IP matrix elements.
the 3rd IP of the matrix.
4.2.4. Partition function ratio of M+ to M2+ of the matrix
4.2.3. First ionization potential of the matrix According to the Saha Equation (cf. Eq. (2)), which governs
There are abundant literature references involving the the ratio of the population density of successive ionization
relationship between a matrix effect and the 1st IP of the stages [52],
matrix [11,13]. Although Fig. 3a clearly shows no correlation     
between the matrix effect and the 1st IP (i.e., 1st IP is not the n
i 1 3=2 2pme k 2Qi T  Ei
Te exp 2
primary factor), Fig. 3a does not preclude the possibility that it ni ne h2 Q
i T kTi
is a secondary factor. Fig. 8 compares the matrix effect on the
ZnII/ZnI ratio with the 1st IP for the low 2nd IP matrix where n i is the number density of the ion, n e is the electron
elements, arranged in ascending order of 2nd IP. Clearly, no number density, Te and Ti are the electron temperature and
correlation is found and it can safely be concluded that the 1st ionization temperature, respectively, m e, k and h are the

20
Energy (from ground state M+) / eV

st
Ar 1 IP
15

10

0
Ba
Pr
Nd
Ce
Sr
La
Sm
Eu
Tb
Dy
Ho
Ca
Er
Tm
Gd
Yb
Y
Sc
Zr
Ti
Lu
Nb
Sn
V
Hf
Pb
Mg
Mn
Ge
Mo

nd
Increasing 2 Ionization Potential from 10.00 to 16.16 eV

Fig. 6. Energy level diagram for the singly-charged and doubly-charged matrix ions. An energy of zero refers to the ground state of the singly charged ion. The
second ionization potential for each element is indicated by a dotted line. There is a correlation between the matrix effect and the presence of low-lying energy levels
in the doubly charged matrix ion.
 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659 649

Table 3
Total excitation potential (E.P.) from ground-state singly charged ion and electronic configuration of ground-state and low-lying or first excited state (whichever is
lower) of doubly-charged matrix ion
Matrix 2nd IP (eV) Configuration of Configuration of M2+ Energy from ground Total Reference
M2+ ground-state first excited state M2+ (eV) E.P. (eV)
Ba* 10.00 5p6-1S0 5p55d-[1/2]0 16.46 26.46 [35]
Pr 10.55 4f 3-4I9/2 4f 3-4I11/2 0.17 10.72 [42]
Nd 10.73 4f 4-5I4 4f 4-5I5 0.14 10.87 [42]
Ce 10.85 4f2-3H4 4f2-3H5 0.19 11.04 [42]
Sr* 11.03 4p6-1S0 4p54d-[1/2]0 21.88 32.91 [36]
La 11.06 5d-2D3/2 5d-2D5/2 0.20 11.26 [42]
Sm 11.07 4f6-7F0 4f6-7F1 0.04 11.11 [42]
Eu 11.24 4f7-8S7/2 4f7-6P7/2 3.50 14.74 [44,45]
Tb 11.52 4f9-6H15/2 4f9-6H13/2 0.35 11.87 [42]
Dy 11.67 4f10-5I8 4f10-5I7 0.52 12.19 [46]
Ho 11.80 4f11-4I15/2 4f11-4I13/2 0.67 12.47 [42]
Ca* 11.87 3p6-1S0 3p53d-[1/2]0 25.22 37.09 [37]
Er 11.93 4f12-3H6 4f12-3H5 0.86 12.79 [42]
Tm 12.05 4f13-2F7/2 4f13-2F5/2 1.09 13.14 [42]
Gd 12.09 4f75d-9D2 4f75d-9D3 0.03 12.12 [42]
Yb* 12.18 4f14-1S0 4f135d-(7/2,3/2)2 4.14 16.32 [42,47]
Y 12.24 4d-2D3/2 4d-2D5/2 0.09 12.33 [48]
Sc 12.80 3d-2D3/2 3d-2D5/2 0.02 12.82 [41]
Zr 13.13 4d2-3F2 4d2-3F3 0.08 13.21 [41,49]
Ti 13.58 3d2-3F2 3d2-3F3 0.02 13.60 [41]
Lu 13.9 4f146s-2S1/2 4f146d-2D3/2 0.71 14.61 [42]
Nb 14.32 4d3-4F3/2 4d3-4F5/2 0.06 14.38 [41,50]
Sn* 14.63 5s2-1S0 5s5p-3P0 6.64 21.27 [41]
V 14.66 3d3-4F3/2 3d3-4F5/2 0.02 14.68 [41]
Hf 14.9 5d2-3F2 5d6s-3D1 0.34 15.24 [40,51]
Pb* 15.03 6s2-1S0 6s6p-3P0 7.49 22.52 [41]
Mg 15.04 2p6-1S0 2p53s-3P2 52.77 67.81 [41]
Mn 15.64 3d5-6S5/2 3d5-4G11/2 3.33 18.97 [41]
Ge* 15.93 4s2-1S0 4s4p-3P0 7.65 23.58 [41]
Mo 16.16 4d4-5D0 4d4-5D1 0.03 16.19 [41]
Matrices marked with asterisks are out-of-trend elements that show comparatively less severe matrix effect than matrices with similar 2nd IP.

electron mass, Boltzmanns constant and Plancks constant, ratio of M2+/M+ depends also on the ratio of the partition
respectively, and Q i and E++
i are the partition function and the functions for the two stages of ionization[ Q(M2+)/Q(M+)].
second ionization potential, respectively. The superscripts + Consequently, it is logical to consider the partition function
and ++ refer to the singly charged ion and doubly charged ion, ratio as a candidate for a secondary factor in dictating the
respectively. Therefore, apart from the 2nd IP, the population matrix effect.

rd
90
ZnII/ZnI 3 IP of Matrix
110
Third Ionization Potential of Matrix / eV

Sn Pb Ge 80
Relative ZnII/ZnI Intensity Ratio / %

100
70
90 Ca
60
Sr Yb
80 Ba
50

70
40

60 30

50 20

40 10
Ba
Pr
Nd
Ce
Sr
La
Sm
Eu
Tb
Dy
Ho
Ca
Er
Tm
Gd
Yb
Y
Sc
Zr
Ti
Lu
Nb
Sn
V
Hf
Pb
Mg
Mn
Ge
Mo

nd
Increasing 2 Ionization Potential from 10.00 to 16.16 eV

Fig. 7. Relation of matrix effect on relative ZnII/ZnI ratio with the 3rd IP of the matrix. Matrix elements are sorted in ascending order of the 2nd IP.
650 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659

st 10
ZnII/ZnI 1 IP of Matrix
110
Sn Pb Ge

First Ionization Potential of Matrix / eV

Relative ZnII/ZnI Intensity Ratio / %
100 9

90 Ca
Sr Yb 8
80 Ba

70 7

60
6
50

40 5
Ba
Pr
Nd
Ce
Sr
La
Sm
Eu
Tb
Dy
Ho
Ca
Er
Tm
Gd
Yb
Y
Sc
Zr
Ti
Lu
Nb
Sn
V
Hf
Pb
Mg
Mn
Ge
Mo
nd
Increasing 2 Ionization Potential from 10.00 to 16.16 eV

Fig. 8. Relation of matrix effect on relative ZnII/ZnI ratio with the 1st IP of the matrix. Matrix elements are sorted in ascending order of the 2nd IP.

Fig. 9 shows the relationship between the matrix effect and species MO on the excitation conditions in the plasma is not
the partition function ratio of the matrix [30,38 40,53], well characterized. For example, it is well known that
Q(M2+)/Q(M+), at an assumed plasma temperature of 7000K. quenching of excited states (in this case, the excited states
Clearly, no correlation exists, indicating that the partition of the analyte) is more efficient by molecular species than
function ratio is probably not a secondary factor. atomic species [54,55]. Regrettably, there is no study in the
literature that lists the percentage oxide formation for all
4.2.5. Metal-oxide bond energy of the matrix thirty matrix elements included in Fig. 4, and it is not
From Fig. 4, all other REEs but Yb induce a stronger practical to use the data from different literature reports, as
matrix effect than Ba despite the fact that the 2nd IP of Ba is oxide formation in the ICP is highly dependent on plasma
the lowest. A common feature of REE is the strength of the conditions [31,32,56,57]. Fortunately, several independent
oxide bond; the MO+ ion for REE can be readily observed in studies that were focused on main group and transition
ICP-MS and, under some experimental conditions, the MS- elements [32,57] and the REE [31,56] have shown that the
signal for MO+ can even exceed that of M+. Although the logarithmic ratio of MO+ /M+ is correlated linearly with the
formation of MO would reduce the population of the matrix bond energy of the corresponding metal oxide. Therefore, the
as free atoms/ions (and hence might reduce the matrix effect M O bond energy was considered here as a candidate for a
if it is caused directly by M2+), the influence of the molecular secondary factor.

2+ +
ZnII/ZnI Ratio of Q(M ) / Q(M )
110 2.0
Sn Pb Ge
Relative ZnII/ZnI Intensity Ratio / %

100
Ratio of Q(M 2+) / Q(M + )

90 1.5
Ca
Sr Yb
80 Ba
1.0
70

60
0.5

50

40 0.0
Ba
Pr
Nd
Ce
Sr
La
Sm
Eu
Tb
Dy
Ho
Ca
Er
Tm
Gd
Yb
Y
Sc
Zr
Ti
Lu
Nb
Sn
V
Hf
Pb
Mg
Mn
Ge
Mo

nd
Increasing 2 Ionization Potential from 10.00 to 16.16 eV

Fig. 9. Relation of matrix effect on relative ZnII/ZnI ratio with the partition function ratios of doubly-charged to singly-charged matrix ion, Q(M2+)/Q(M+), at an
assumed plasma temperature of 7000 K. Matrix elements are sorted in ascending order of the 2nd IP.
 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659 651

Fig. 10a shows the relationship between the matrix effect M O bond energy and 2nd IP are considered as two
and the M O bond energy [28] of the matrix, in ascending independent parameters; there is no known correlation or
order of 2nd IP. Six out of the seven out-of-trend elements Ba, mechanism that directly links the formation of doubly
Sr, Ca, Yb, Sr and Pb, with Eu and Tm as additional elements charged ions and metal-oxide species in the plasma. If the
show good correlation with the M O bond energy; a dip in the formation of metal-oxide species is responsible for the more
corresponding M O bond energy correlates with an increase in severe matrix effects caused by the REEs, it is logical to
the ZnII/ZnI ratio (i.e., a reduced matrix effect). However, Ge expect that other species with high M O bond energies
shows the opposite correlation; the M O bond energy of Ge is should also induce stronger matrix effects. Fig. 10b shows
larger than that of both its neighbors (Mn and Mo) in Fig. 10a, the relationship between matrix effects and M O bond
but it shows a smaller matrix effect (higher recovery of the energy [28] for the studied high 2nd IP matrices in
ZnII/ZnI ratio). Overall, the M O bond energy cannot be ruled ascending order of 2nd IP. Both B and Si have high M O
out as a secondary factor based on only one mismatching data bond energies ( 800 kJ/mol), similar to that of many of the
point. REEs shown in Fig. 10a. However, neither B nor Si induces
To further evaluate the possibility of M O bond energy a more severe matrix effect than other high 2nd IP elements.
as a secondary factor, the M O bond energy was correlated Therefore, M O bond energy is probably not an important
with matrix effect for all other studied matrices. That is, the secondary factor. Further, the rather ambiguous correlation of

a
900
ZnII/ZnI Metal-Oxide Bond Energy
110
Sn Pb Ge

Metal-Oxide Bond Energy / kJ mol-1

800
Relative ZnII/ZnI Intensity Ratio / %

100
700
90 Ca
600
Sr Yb
80 Ba
500

70
400

60 300

50 200

40 100
Ba
Pr
Nd
Ce
Sr
La
Sm
Eu
Tb
Dy
Ho
Ca
Er
Tm
Gd
Yb
Y
Sc
Zr
Ti
Lu
Nb
Sn
V
Hf
Pb
Mg
Mn
Ge
Mo

nd
Increasing 2 Ionization Potential from 10.00 to 16.16 eV

b
900
ZnII/ZnI Metal-Oxide Bond Energy
110
Metal-Oxide Bond Energy / kJ mol-1

800
Relative ZnII/ZnI Intensity Ratio / %

100
700
90
600

80
500

70
400

60 300

50 200

40 100
Hf
Pb
Mg
Mn
Ge
Mo
Fe
Si
Cr
Ru
Cd
Co
Zn
Ni
Be
Hg
Al
In
Cu
Tl
Ga
Cs
B
Rb
K
Na
Li

nd
Increasing 2 Ionization Potential from 14.9 to 75.6 eV

Fig. 10. Relation of matrix effect on relative ZnII/ZnI ratio with the metal-oxide bond energy of the matrix for (a) low to intermediate 2nd IP matrices from Ba to Mo
and (b) intermediate to high 2nd IP matrices from Hf to Li. Matrices with intermediate 2nd IP are presented in both figures for continuity. Matrix elements are sorted
in ascending order of the 2nd IP.
652 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659
M O energy to matrix effects clearly shows the necessity of
a comprehensive study of matrix elements.
4.2.6. Atomic partition function of the singly-charged matrix
ion
Apart from high oxide bond energies, another distinct
difference between Group II elements and the REEs is the
distribution of energy levels in their atomic structure. It is well
known that the emission spectra of the REEs (and to a slightly
lesser extent, those of transition metals) in the ICP are complex
and line rich, in contrast to those of the Group II which are
comparatively much simpler. The underlying reason for the
richness in emission spectra for the transition metals and the
REEs is their incompletely filled d-shells and f-shells, opening
up many possible combinations of energy levels with different
terms and energies. To investigate the effect of richness in
energy levels on the matrix effect, two parameters can be
studied. The first parameter is the electronic partition function
of the various matrix ions and the second one, which will be
discussed in the next section, is the averaged excitation energy
of the matrix.
The first-ionization efficiencies for most elements (the
possible exceptions in our present list of matrices are Be, B,
Si, Zn, Cd and Hg) in an ICP are high (> 90%), whereas the
second ionization efficiency, even for the most easily doubly
ionizable element (i.e., Ba) is low (< 10%). Even for the six
highest 1st IP matrix elements in the present study, the first
ionization efficiency is not low and was estimated to be >80%
for Si and Cd, > 70% for Be and Zn, > 50% for B and >30% for
Hg [58]. Therefore, with the possible exceptions of B and Hg,
the singly charged matrix ion is the dominant atomic matrix
species. It is thus sufficient to consider the partition function of
only the singly charged matrix ion (the underlying reason to
consider the partition function of the doubly charged matrix ion
that was discussed in Section 4.2.1 is different and is not based
on population density).
Fig. 11a shows the relationship between the severity of
matrix effects and the atomic partition function [30,39,53] of M+
at an assumed plasma temperature of 7000 K, in ascending order
of 2nd IP of the matrix. All seven of the out-of-trend elements
Ba, Sr, Ca, Yb, Sn, Pb and Ge, with Eu and Tm as additional
elements show good correlation with the partition function of
the singly-charged matrix ion; a dip in the corresponding M+
partition function correlates with an increase in the ZnII/ZnI
ratio (i.e., a reduced matrix effect). Fig. 11a also shows that the
partition function of Lu+ has a sharp dip compared to its
neighbors and with a value very similar to those of the seven out-
of-trend elements; however, there was no significant rise in the
corresponding ZnII/ZnI ratio for Lu as a matrix element.
This rather ambiguous situation is similar to the case of the
M O bond energy presented above. Therefore, to further
evaluate the possibility that the partition function of the singly-
charge matrix ion is a secondary factor, the partition function
was correlated with all other studied matrices. Just as with the
M O bond energy, the partition functions of the singly charged
matrix ion are independent from the 2nd IPs and, therefore, can
be extended to all studied matrices regardless their 2nd IPs.
Fig. 11b shows the relationship between matrix effects and
partition function of the singly charged matrix ion [30,39] for
other studied high 2nd IP matrices, arranged in order of
increasing 2nd IP. The M+ partition function values of Fe, Ru
and Co are similar to those of many of the transition metals or
even REEs shown in Fig. 11a (about 30 60). However, none
of Fe, Ru and Co induces a more severe matrix effect than
other high 2nd IP elements. In addition to the uncorrelated
matrix effects and the M+ partition function of the matrices Lu,
Fe, Ru and Co, the following consideration led us to conclude
that the partition function of the singly charged matrix ion is
probably not an independent secondary factor.
With some exceptions (one such exception is when the next
ionization stage involves the removal of electrons from a fully
or a half-filled sub-shell), the values of the partition function
between successive ionization stages are correlated because
atomic structures for successive ionization stages are connected
by the fact that they differ by only one electron. This is
reflected by the relatively flat partition function ratios, Q(M+)/
Q(M2+), as shown in Fig. 9; such ratios for most studied low
2nd IP matrices are in the range of 0.2 0.5, with the exceptions
of Lu, Hf and Mo (the ionization from singly charged to doubly
charged for these three matrix elements involves the removal of
an electron from either a fully or a half-filled sub-shell:
Lu+(4f 146s 2)YLu2+(4f 146s 1), Hf+(5d6s 2)YHf2+(5d 2) and
Mo+(4d 5)YMo2+(4d 4) [59], linking them to the exceptional
group of elements described earlier). Therefore, the pattern
with respect to partition function for the singly-charged ions,
Q(M+), is similar to that for the doubly-charged ion, Q(M2+)
(cf. Figs. 5 and 11a). As already discussed in Section 4.2.1,
Q(M2+) offers a good (and better when compare to Q(M+))
correlation with the observed matrix effect, so it is possible that
the apparent correlation of the matrix effect with Q(M+) shown
in Fig. 11a is an artifact caused by the close relationship
between Q(M+) and Q(M2+). Of course, because of this close
relationship, it is impossible to conclude whether the atomic
partition function of M+ is a secondary factor or not. However,
even if it is a secondary factor, it will belong to the type that
couple with the 2nd IP (i.e., not independent of the 2nd IP, cf.
Fig. 11a and b). It should be noted that apart from the ratio of
partition functions, Q(M2+)/Q(M+), there is no known rela-
tionship between the partition function of the singly-charge ion,
Q(M+) and the 2nd IP or the second ionization. Nevertheless,
the possibility that the partition function of M+ is a 2nd IP-
dependent secondary factor is also taken into account in the
proposed matrix effect mechanism that will be discussed in
Section 4.4.
4.2.7. Averaged excitation energy of the singly-charged matrix
ion
Another way in which energy-level rich matrices might
induce more severe matrix effects is through excitation. Just as
atomization and ionization, excitation of the matrix species
consumes energy in the plasma that would otherwise be
available for excitation of the analyte. There have been reports
that discussed the correlation of matrix effects or changes in
plasma fundamental characteristics (e.g., plasma temperature
 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659 653

a
+
ZnII/ZnI Partition function of M
110
Sn Pb Ge

Relative ZnII/ZnI Intensity Ratio / %

Partition Function of M+ at 7000K

100
100
90 Ca
Sr Yb
80 Ba

70
10

60

50

40 1
Ba
Pr
Nd
Ce
Sr
La
Sm
Eu
Tb
Dy
Ho
Ca
Er
Tm
Gd
Yb
Y
Sc
Zr
Ti
Lu
Nb
Sn
V
Hf
Pb
Mg
Mn
Ge
Mo
nd
Increasing 2 Ionization Potential from 10.00 to 16.16 eV

b
+
ZnII/ZnI Partition function of M
110
Relative ZnII/ZnI Intensity Ratio / %

Partition Function of M+ at 7000K

100
100
90

80

70
10

60

50

40 1
V
Hf
Pb
Mg
Mn
Ge
Mo
Fe
Si
Cr
Ru
Cd
Co
Zn
Ni
Be
Hg
Al
In
Cu
Tl
Ga
Cs
B
Rb
K
Na
Li

nd
Increasing 2 Ionization Potential from 14.9 to 75.6 eV

Fig. 11. Relation of matrix effect on relative ZnII/ZnI ratio with the partition function of the singly-charged matrix ion, Q(M+), at an assumed plasma temperature of
7000 K for (a) low to intermediate 2nd IP matrices from Ba to Mo, and (b) intermediate to high 2nd IP matrices from Hf to Li. Matrices with intermediate 2nd IP are
presented in both figures for continuity. Matrix elements are sorted in ascending order of the 2nd IP.

or electron number density) with the atomization energies and decay; the energy released from the de-excitation process is
first ionization potentials of the matrix elements [8,9,11,13]. then in the form of a photon which will be lost since the ICP
In comparison to atomization and ionization, which are is optically thin and the probability of re-absorption is
generally assumed to occur irreversibly in the plasma (i.e., consequently low. In addition, since the rate of dipole-allowed
each process happens only once for an individual atom), the radiative decay (Einstein transition probability) is typically
process of excitation can repeatedly occur through cycles of high (on the order of 108 s1), the effect of energy con-
excitation and de-excitation. (Of course, it might happen that sumption by cyclic, continuous excitation of the matrix atom
ionization also occurs repeatedly due to three-body ion- or ion should be considered. Accordingly, the averaged ex-
electron recombination, the exact reverse of electron-impact citation energy of the singly-charged matrix ion is considered
ionization, with three-body ion-electron recombination per- here as a candidate for a secondary factor of the matrix effect.
fectly balancing the energy flow for this pair of ionization/de- The energy required to excite an atom/ion depends on its
ionization routes.) The most important distinction for the energy levels and degeneracy. The averaged excitation energy
excitation process is that the routes for excitation and de- for each atom/ion is equal to
Ej
excitation can be different (i.e., not simply the reverse of each Xi
Ej gj e kT
other). For example, it is plausible that excitation is achieved Averaged excitation energy 3
j0
Q T
by electron impact while de-excitation is through radiative
654 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659

where all variables have the same meaning as in Eqs. (1) and charge transfer, (III) Penning ionization, and (IV) ion-electron
(2). The values of energy levels and their degeneracies were recombination. Although direct experimental evidence for
obtained from [43]. some of these mechanisms has been given in the literature
Fig. 12 shows the relationship between the matrix effect and and although it is also generally accepted that some mechan-
the averaged excitation energy of the singly charged matrix ion isms (e.g., charge transfer and ion-electron recombination) are
at an assumed plasma temperature of 7000 K. The reason that dominant over the others in specific situations, the dominant
only the singly charged matrix ions are considered here is mechanism is not conclusive and is debatable for some classes
because they are by far the most abundant matrix species, of energy levels.
based on arguments presented in the last section. Although the In electron-impact excitation/ionization, the analyte is
matrix effects from Group II matrices show some correlation ionized and/or excited by electron collision according to the
with the averaged excitation energy (the lower the averaged reactions:
excitation energy, the higher the ZnII/ZnI ratio, which indicates
Mp e YMq e
a less severe matrix effect), the overall correlation is poor. In
particular, the averaged excitation energy of Dy ( 1.24 eV) is Mp e YMp e e
much higher than that of Ho ( 0.52 eV) which in turn is
similar to that of Ca ( 0.44 eV); yet the matrix effect of this Mp e YMq e
neighboring group follows the order Dy Ho >> Ca. Moreover,
the averaged excitation energies decline monotonically for the In the above reactions, M represents a generic analyte atom
matrix group Er, Tm, Gd, Yb, Y and Sc, whereas the matrix and the subscripts p and q pertain to lower and upper energy
effect does not follow such a trend. Further, Yb clearly shows levels, respectively. Although these reactions can all occur in
exceptional behavior which cannot be explained by the both directions, only the forward direction will be considered
averaged excitation energy. Therefore, it is not likely that the here, as these are the reactions responsible for excitation; the
secondary factor for the matrix effect involves excitation reverse are responsible for de-excitation. Such an arrangement
energies of the matrix ions. allows the classification of excitation mechanisms according to
the energetic species involved. For example, three-body ion-
4.3. Brief review of excitation mechanisms in the ICP electron recombination (listed as category IV above) is the
exact reverse of electron-impact ionization. Clearly, electron-
To investigate plausible mechanisms for the matrix effect, it impact depends on the electron number density and the electron
is necessary to consider analyte excitation mechanisms in energy distribution (electron temperature) and is a rather non-
parallel, since a plasma-related matrix effect can be viewed as a selective mechanism. Undoubtedly, excitation by electron
change in the analyte excitation efficiency. Therefore, com- impact occurs and should be important in the ICP; however,
monly considered excitation mechanisms in the ICP are briefly for some classes of energy levels, it might not be the dominant
reviewed below. mechanism.
Analyte excitation mechanisms in the ICP can be classified Charge transfer is an important excitation mechanism for
into four main categories, involving the species responsible, specific high-energy ionic levels of some elements in the ICP
namely: (I) electron-impact excitation and ionization, (II) [60 65]. Charge transfer from argon ions, which are abundant

1.4
ZnII/ZnI Averaged Excitation Energy
110
Sn Pb Ge
1.2
Relative ZnII/ZnI Intensity Ratio / %

Averaged Excitation Energy of M+ / eV

100
1.0
90 Ca
Sr Yb
0.8
80 Ba

0.6
70

60 0.4

50 0.2

40 0.0
Ba
Pr
Nd
Ce
Sr
La
Sm
Eu
Tb
Dy
Ho
Ca
Er
Tm
Gd
Yb
Y
Sc
Zr
Ti
Lu
Nb
Sn
V
Hf
Pb
Mg
Mn
Ge
Mo

nd
Increasing 2 Ionization Potential from 10.00 to 16.16 eV

Fig. 12. Relationship of the matrix effect on the relative ZnII/ZnI ratio with the averaged excitation energy of the singly charged matrix ion at an assumed plasma
temperature of 7000 K. Matrix elements are sorted in ascending order of the 2nd IP.
 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659
in the ICP, provides a direct link between the ground state of a
neutral metal atom and selected excited states of its singly
charged ion, as shown by the equation
Ar MYAr M 4 DE:
For appreciable charge transfer reaction to occur, DE needs
to be small. In other words, the energy level of the excited
analyte ion and the Ar ionization potential need to be quasi-
resonant. Literature values of possible DE usually range from
2 eV down to  1.6 eV [60 65]. Due to the strict energy
requirement, charge transfer is important only for high-energy
ionic levels above 14 eV [60 65].
Penning ionization involves energy transfer from an
energetic neutral Ar species (e.g., Ar metastable) to the analyte.
Because the excited levels of neutral Ar species have high
energies ( 11.5 to 15 eV), most analytes can be ionized and
even excited.
Ar4 MYAr M e
Ar4 MYAr M 4 e
The importance of Penning ionization in the ICP has been
suggested by different researchers [66 69]; however, direct
experimental evidence for its existence in the ICP has not yet
been reported. Penning ionization has been experimentally
confirmed in other types of analytical plasmas (e.g., micro-
wave-induced plasmas [70] and glow discharges [71]) as being
significant for excitation of ionic species. In contrast to charge
transfer, the energy-matching requirement for Penning ioniza-
tion is relaxed because the liberated electron can efficiently
carry the excess energy away due to its small mass [72,73].
Ion-electron recombination, further classified as radiative or
three-body, are the following:
M e YM4 hvcont radiative
M e e YM4 e three-body:
The importance of ion-electron recombination as a popu-
lating route for high-level atomic-neutral states has been
experimentally confirmed in the ICP [74]. Moreover, radiative
recombination of Ar ions is the dominant process responsible
for the bright continuum emission of an ICP [75].
4.4. Proposed matrix-effect mechanism
Any realistic mechanism should follow the behavior
observed in matrix effects, namely: it should show a correlation
with the 2nd IP of the matrix and the electronic partition
function of M2+, and possibly a coupled correlation between
the 2nd IP and the electronic partition function of M+, but not
with the 1st IP or the theoretical second-ionization efficiency of
the matrix, nor any other parameters investigated but rejected
in the present study.
The data presented above show that matrix effects lower the
MII/MI ratios. A drop in this ratio could be caused by a relative
decrease in MII or/and a relative increase in MI intensity in the
655
presence of a matrix. Therefore, it is necessary to know the
direction and magnitude of the change in ion (MII) and atom
(MI) emission intensity when a matrix is present. By using two
nebulizers connected in parallel, the matrix and the test element
can be independently introduced into the plasma. This dual-
nebulizer setup completely eliminates the possibility of a
sample-introduction-related matrix effect and any change in the
test-element emission intensities must be due solely to plasma-
related matrix effects. We have previously reported the matrix
effects caused by Na, Ca and Ba on a variety of test elements
using dual-nebulizers setup [64]. A representative example for
Fe is given in Fig. 13. The observed general trend is that for
neutral-atomic emission lines, the relative intensities in the
presence of a matrix are generally closer to 100% than for their
ionic counterparts. Also, the relative intensities of low-energy
ionic emission lines are similar to those of neutral-atomic lines
in Na matrices but are significantly lower in Ca and Ba
matrices (Fig. 13). As the excitation potential approaches 16 eV,
the relative intensities of the ionic emission lines of most
elements begin to rise and approach the value of their neutral-
atomic counterparts due to a charge-transfer (CT) reaction.
[64]. Therefore, it can be concluded that non-CT-excited ionic-
emission lines suffer more from matrix effects than CT-excited
lines, and the major cause for the lower MII/MI ratio reported
above is due to a decline in emission intensities of the ionic
lines.
Electron-impact ionization/excitation and ion-electron re-
combination are probably not related to the matrix-effect
mechanism. As was mentioned in the introduction, second
ionization should contribute only a fraction of additional
electrons compared with those from first ionization. In addition,
a change in electron number density should be correlated with
the degree of second ionization of a matrix element, but the
matrix effects do not show such a correlation, either from
experimentally determined second ionization efficiencies by
ICP-MS, or from theoretical calculations based on the Saha
equation or thermodynamic simulation [30]. Moreover, there is
no clear link between the electron properties (e.g., n e and Te) and
110
Neutral-atom Ionic
emission lines emission lines
Fe Relative Intensity / %
100
90
80
Na matrix
Ca matrix
Ba matrix
70
3 4 5 6 7 12 13 14 15 16 17 18
Total Excitation Potential / eV
Fig. 13. Relative intensities of various Fe emission lines in the presence of Na,
Ca and Ba matrices with a dual-nebulizer setup.
656 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659

120
1011 1012 cm 3 [76,77]) and a moderate matrix concentration
Rel. Ionic-to-atomic Intensity Ratio / %

110 can approach or even exceed this number density in the plasma.
For example, a 0.05M matrix solution pumped at 2 mL/min
100 and nebulized by an USN with a typical nebulization efficiency
of 10%, entrained in 1 L/min carrier gas would result in
90
3  1013 matrix species/cm3 in the central channel of the
80 plasma. This value is very likely overestimated, as it assumes
all the matrix species are concentrated in the central channel
70 without diffusion. Olesik et al. found that such an estimate for
number density is about an order of magnitude high [78].
60
However, even if the number density of matrix species is an
50 CuII/CuI
order of magnitude lower than the above estimated value, it is
ZnII/ZnI still substantial and comparable to that of the Ar metastables.
40 For matrices with a low 2nd IP, the energy of the excited Ar
Ba
Pr
Nd
Ce
Sr
La
Sm
Eu
Tb
Dy
Ho
Ca
Er
Tm
Gd
Yb
Y
Sc
Zr
Ti
Lu
Nb
Sn
V
Hf
Pb
Mg
Mn
Ge
Mo
species is sufficient to promote second ionization from the
nd
Increasing 2 Ionization Potential from 10.00 to 16.16 eV singly-charged matrix ion via Penning ionization [Ar* + M+Y
Fig. 14. Matrix effect on ZnII/ZnI and CuII (224.700 nm)/CuI intensity ratios Ar + M2+ + e], which would further lower the Ar* population.
from individual matrix elements sorted in ascending order of the 2nd IP. The Moreover, the combined effect of the two stepwise Penning
CuII 224.700 nm emission line is excited mainly by charge transfer from Ar+. ionization events for a low 2nd IP matrix is more substantial
than simply doubling the concentration of the matrix. Once the
the partition function (or its equivalentthe presence of low- doubly-charged matrix ions are formed, they would tend to
lying energy levels) of the doubly-charged matrix ion. recombine with the abundant electrons, due to their high
A change in analyte excitation efficiency by ion-electron potential energy.
recombination can also be neglected, because this populating The rate of ion-electron recombination follows a Z 2 [79,80]
mechanism is applicable only to high-energy neutral-atom and Z 3 [81] dependency (where Z is the charge of the ion) for
levels, and it has been shown that the change in the MII/MI radiative and three-body recombination, respectively. There-
ratio results predominately from a decline in MII intensity fore, it would be expected that the ion-electron recombination
without a corresponding increase in MI intensity (cf. Fig. 13). rate for these doubly charged matrix ions will be about 4 to
Charge transfer can also be eliminated from further consid- 8 times higher than that for singly-charged ions. As the doubly
eration. If, for any reason (e.g., charge transfer between Ar ions charged matrix ions recombine, the singly charged ion will be
and the low 2nd IP matrix), there were a significant reduction in available again for further quenching of Ar excited species. A
the Ar+ population, it is the ionic energy levels that can be schematic diagram for this proposed cyclic mechanism
directly excited via charge transfer that will suffer the most involving Penning ionization followed by ion-electron recom-
severe matrix effect. CuII 224.700 nm is one of the emission bination is shown in Fig. 15. The net effect is a significant
lines that is known to be significantly populated by charge quenching of Ar excited states the key reactant in Penning
transfer [61,64,65]. Fig. 14 shows the CuII (224.700 nm)/CuI ionization and a corresponding drop in excitation efficiency of
ratio in the presence of various low 2nd IP matrices. (The two the analyte ionic energy levels and hence of the ionic emission
well known MgII CT lines at 279.806 nm and 279.079 nm are intensities.
weak and suffer strong spectral interference from the REEs so This proposed mechanism is further supported by the fact
were not used here.). The behavior of the CuII(CT)/CuI ratio is that the matrix effect is correlated with the partition function
significantly different from that of other MII/MI ratios presented and the presence of low-lying energy levels of the doubly
earlier (cf. Fig. 4). The CuII/CuI ratio remains close to 100% for charged matrix ion. From Fig. 6, it can be realized that the
almost all matrices, indicating that the CT CuII level is relatively seven out-of-trend matrices (Ba, Sr, Ca, Yb, Sn, Pb and Ge)
free of a matrix effect. that show less severe matrix effects than other matrices with
In contrast, Penning ionization is a suitable candidate for the
explanation of matrix effects caused by these low 2nd IP
matrices. Unlike charge transfer, Penning ionization does not Ar* + Analyte Analyte+* + Ar + e-
have a strict requirement on energy matching because the
liberated electron can effectively carry away any energy Ar* + Matrix Matrix+* + e- + Ar
surplus. Also, the energy range of Ar excited states is broad decay
(from 11.5 eV to 15 eV). Therefore, it is reasonable to expect
that, under the hypothesis that Penning ionization is an Ar* + Matrix+ Matrix 2+ + e- + Ar
important mechanism for the ionization/excitation of an ionic
level, similar reaction routes would occur also for the matrix. In Significantly quenched Z 2 and Z 3 for radiative and
by low 2 nd IP matrix three-body recombination
other words, the analyte and the matrix are competitors for Ar
excited states in Penning ionization. Moreover, the population Fig. 15. Schematic diagram showing the proposed matrix-effect mechanism
density of Ar excited states is relatively low (n Ar-metastable through cyclic Penning ionization and ion-electron recombination.
 G.C.-Y. Chan, G.M. Hieftje / Spectrochimica Acta Part B 61 (2006) 642 659
similar 2nd IP, can have only the ground-state of their doubly
charged ion populated by Penning ionization, since all of them
possess no low-lying M2+ energy levels and their first M2+
excited state is too high to become populated by Penning
ionization. In contrast, all other low 2nd IP elements have M2+
excited states lying below the first ionization potential of Ar
(15.75 eV); these levels can possibly be populated by Penning
ionization from the ground state of their singly-ionized
counterparts and would therefore cause a greater depletion of
Ar excited species and a correspondingly greater matrix effect.
There are two possible ways that matrices with low-lying
M2+ energy levels induce more severe matrix effects. First,
matrices rich with low-lying energy levels offer more possible
reaction routes (degeneracy) for Penning ionization and hence
will raise the overall quenching rate. Second, since the
quenching cross section for an individual route depends on
the crossing of the potential energy curves of the pseudo-
molecules (Ar* M and M+* Ar), having more possible
reaction routes would increase the likelihood of a particular
route existing that has a very favorable quenching cross-
section, which in turn will increase the overall quenching rate.
It should be noted that the above explanation for the
correlation between matrix effects and the partition function of
the doubly-charged matrix ion is also applicable to the partition
function of the singly-charged matrix ion, Q(M+). Although the
present study cannot confirm unambiguously any correlation
between the matrix effect and Q(M+) (Section 4.2.6), if a
correlation exists, Q(M+) is a secondary factor that couples
with the 2nd IP or second ionization of the matrix and the
above argument on numbers of feasible Penning ionization
reaction routes is a plausible explanation for such a correlation.
5. Conclusions
Plasma-related interference effects in ICP-AES by a
comprehensive list of matrices were investigated. The second
ionization potential of the matrix is confirmed to be a
determining primary factor for the matrix effect. In addition,
the availability of low-lying energy levels in the doubly-
charged matrix ion contributes to the matrix effect. Penning
ionization followed by ion-electron recombination, which leads
to effective quenching of Ar excited states, is proposed as the
matrix-effect mechanism for most ionic emission lines (i.e.,
those not excited by charge transfer).
Acknowledgement
George Chan acknowledges the Croucher Foundation for
the award of a scholarship. This research was supported by the
U.S. Department of Energy through Grant DE-FG02-
98ER14890.
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