Analytica Chimica Acta 429 (2001) 135143

On the transport of some metals into inductively coupled

plasma during hydride generation process
P. Pohl, W. Zyrnicki

Analytical Chemistry Division, Chemistry Department, Institute of Inorganic Chemistry and Metallurgy of Rare Elements,
Wroclaw University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland
Received 15 May 2000; received in revised form 17 October 2000; accepted 18 October 2000
Abstract
Transport process of Ca, Cd, Co, Cr, Cu, Fe, Mn, Mg, Ni, Zn and Ti during continuous ow hydride generation in the
system with phase separation was investigated using inductively coupled plasma atomic emission spectrometry. The effect of
HCl and HNO
3
(for concentrations from 0.01 to 5.0 mol l
1
) and arsenic on transport efciency of the metals into plasma was
examined. It was observed that not only Cd but also Cu transport in a form of volatile species was signicant. The present
study also indicated the formation of Co, Cr, Fe and Ni volatile species during hydride generation reaction. Possibility of
spectral interferences between Cd, Cu and Fe lines on the one side and As and Bi lines on the other side was analysed and
discussed. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Hydride generation; Transport of metals; Volatile species; Cd; Co; Cr; Cu; Fe; Ni; Atomic emission spectrometry; Inductively
coupled plasma
1. Introduction
Separation of elements, such as As, Bi, Sb, Se
and Sn in the form of volatile hydrides, from a sam-
ple solution performed in a continuous ow hydride
generation, does not eliminate an inuence of matrix
elements owing to chemical interferences occurring
in the solution. In the recent papers devoted to the
HGICPAES method [110], the attention has been
focused on the investigation of interferences in liquid
phase due to transition metals and various methods
of minimisation of such interferences were discussed.
It was surveyed [11] that ions of these elements,
present in the sample solution in the conditions of

Corresponding author. Tel.: +48-71-320-2494;

fax: +48-71-328-4330.
E-mail address: zyrnicki@ichn.ch.pwr.wroc.pl (W. Zyrnicki).
hydride generation reaction, form metals and metal
borides which particles adsorb hydrides and cause
their decomposition. Interfering ions can also com-
pete with the analytes for reduction. Metal ions and
metal species may catalyse decay of reducing agent
as well. These chemical interferences in liquid phase
lead to a signicant signal suppression of hydride
forming elements.
Because of an assumption of complete separation
of the elements forming volatile hydrides from matrix
elements during the reaction of the acidied sample
with the reductant spectral interferences have not been
considered.
In the last years transport of other than hydride
forming elements during hydride generation reac-
tion was also examined. The generation of volatile
species of Cd [1218], Cu [19,20] and Ag, Au, Pd
and Rh [20] was reported. It was found that cadmium
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136 P. Pohl, W. Zyrnicki / Analytica Chimica Acta 429 (2001) 135143
volatile species formation both for continuous ow
[12,13,15,16] and ow injection [14,17,18] modes
of hydride generation was affected by chemical ex-
perimental conditions. In the presence of vesicles
[12,13,1517] or mixture of cobalt and thiourea [14]
in the sample solution, sensitivity of cadmium deter-
mination was considerably enhanced. The reaction
efciency was found to be dependent on the NaBH
4
and HCl concentrations as well. For copper efciency
of volatile compound generation was also observed
to be dependent on experimental conditions [19].
Formation of a ne aerosol of Co, Cr, Fe and Ni
in a U-type phase separator during the hydride gen-
eration achieved by NaBH
4
attack in medium of HCl
was found to be responsible for transport of these el-
ements [21] to the plasma. The amount of transported
elements depended on the type of a gasliquid sepa-
rator used in the experiments.
In this study, inductively coupled plasma atomic
emission spectrometry was used to investigate a trans-
port process of Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni,
Zn and Ti in the continuous ow hydride generation
with the system with phase separation. The effect of
HCl and HNO
3
concentration in the sample solution
on metal signals was examined thoroughly with regard
to the presence and absence of arsenic in the solution.
Possibilities of spectral interferences between Cd, Cu
and Fe lines and lines of hydride forming elements
were analysed and discussed.
2. Experimental
2.1. Instrumentation
A Jobin Yvon ICP sequential atomic emission
spectrometer (model JY 38S) equipped with a Jobin
Yvon CMA system for continuous hydride gener-
ation and pneumatic nebulisation was used for the
experiments. Hydride generation system consisted of
a cyclone spray chamber, a pneumatic nebuliser of
Meinhard type and peristaltic pumps with delivering
tubes. Here, this system was modied to separate gas
and liquid phases. The sample and NaBH
4
solutions
were pumped into the cyclone chamber in two sepa-
rate streams where they merged and reacted. The car-
rier Ar stream was introduced through the nebuliser
gas inlet (sample inlet was clogged) and transported
Table 1
Operating conditions for HGICPAES experiments
Rf generator (MHz) 40.68
Supplied power (W) 1000
Plasma Ar ow rate (l min
1
) 13
Intermediate Ar ow rate (l min
1
) 0.25
Carrier/nebulising Ar ow rate (l min
1
) 0.25
Pressure on nebuliser (bar) 3.0
Observation high (mm, above load coil) 12
Slit width (entrance/exit) (m) 20/50
Integration time (s) 0.10
Background correction (nm) 0.025
Sample ow rate (ml min
1
) 1.0
NaBH
4
ow rate (ml min
1
) 1.0
NaBH
4
concentration in 0.50 mol l
1
NaOH (% (m/v)) 1.0
Drains ow rate (ml min
1
) 6.3
gaseous products of hydride generation reaction into
the plasma. Wastes were removed to drains by the peri-
staltic pump. Detailed operating conditions for plasma
excitation and hydride generation are listed in Table 1.
2.2. Reagents
Single-element 1000 g ml
1
atomic absorp-
tion standard solutions (Johnson Matthey GmbH,
Karlsruhe, Germany) were used for preparation of
10 g ml
1
multi-element solutions of Ca, Co, Cd,
Cr, Cu, Fe, Mg, Mn, Ni, Ti and Zn without and with
addition of 1.0 g ml
1
of As. For sample solution
acidication, HCl and HNO
3
(Merck, Darmstad,
Germany) were used.
NaBH
4
solution of 1.0% (m/v) for hydride gener-
ation was obtained by dissolution of NaBH
4
powder
(Serva Feinbiochemica GmbH & Co., Heidelberg,
Germany) in 0.50 mol l
1
solution of NaOH(Chempur
Chemical Substances Purication Laboratory, Piekary
Slaskie, Poland). It was ltered before measurement.
For dilution and other solution preparations
de-ionised water was used.
3. Results and discussion
The most sensitive analytical lines of As, Ca, Co,
Cd, Cr, Cu, Fe, Mg, Mn, Ni, Ti and Zn were inves-
tigated during hydride generation process at various
experimental conditions. The effect of HCl and HNO
3
in sample solutions on transport of studied elements
was examined for acid concentrations corresponding
P. Pohl, W. Zyrnicki / Analytica Chimica Acta 429 (2001) 135143 137
to 0.010, 0.10, 0.50, 1.0, 2.0, 3.0 and 5.0 mol l
1
,
respectively.
Reaction between sample acidied with HCl or
HNO
3
and reducing agent was instant. For higher acid
concentration, it was faster and more vigorous. Acid
concentration had an inuence on plasma excitation
conditions referred to the intensity of the Ar atomic
line spectrum only in the narrow range from 0.010
to 1.0 mol l
1
. For higher concentrations of HCl and
HNO
3
, Ar intensity uctuations <2% were observed.
In such conditions, the ionic to atomic line intensity
ratio for Mg (279.55/285.21 and 280.27/285.21) was
also nearly constant.
3.1. Transport of metals into the plasma
To evaluate the amounts of metals that were trans-
ferred into the plasma during the hydride genera-
tion with phase separation, the approach used by
Wickstrm et al. [21] was followed. The measure-
ments of line intensities were referred to those ob-
served for pneumatic nebulisation in the cyclone spray
chamber with concentric nebuliser. Plasma excitation
conditions and the HCl and HNO
3
concentrations in
the samples were identical for the hydride generation
and for the pneumatic nebulisation. The efciency
of the pneumatic nebulisation in the cyclone cham-
ber/concentric nebuliser system was found out here
to be 4.5%. The amount of element which entered the
plasma during the hydride generation was expressed in
a form of a nebulisation efciency equivalent, which
was estimated as a product of pneumatic nebulisation
efciency and the ratio of line intensity for hydride
generation to line intensity for pneumatic nebulisation.
The variations of the nebulisation efciency equiv-
alent for Cd, Co, Cr, Cu, Fe, Mn, Ni, Zn and Ti in
solutions acidied with HCl and HNO
3
are depicted
in Figs. 1 and 2, respectively. Differences in line in-
tensities of the examined elements in dependence on
the acid type and its concentration were observed.
For elements, such as Ca, Cr, Mg, Mn, Zn and
Ti, the nebulisation efciency equivalent was very
small and varied from 0.001 to 0.03%, both in HCl
and in HNO
3
solutions. It generally increased slightly
with rise of acid concentration or reached a plateau
above acid concentration of 2.0 mol l
1
, although be-
haviour of each element was different for both the ap-
plied acids. Higher magnitudes of the nebulisation ef-
ciency equivalent were obtained for Mn and Zn in
HCl solutions than in HNO
3
solutions. For Cr and Ti,
a reversed situation was observed; responses of these
elements in HNO
3
medium were higher than those in
HCl. The nebulisation efciency equivalent for Co, Fe
and Ni was considerably higher in comparison to Cr,
Mn, Zn and Ti as can be seen from Figs. 1 and 2.
For Co and Ni, it was higher in HNO
3
medium than
in HCl. For Fe, the nebulisation efciency equivalent
was comparable for both the acids.
Behaviour of Cd and Cu was remarkably different
in comparison to other elements investigated here.
Meaningfully, higher nebulisation efciency equiv-
alents were observed for these elements. For Cd at
acid concentration of 0.50 mol l
1
, it reached a max-
imum, corresponding to 0.55% in HCl and 0.80% in
HNO
3
. Then, it fell and attained a plateau (0.14% in
HCl and 0.19% in HNO
3
). For Cu, the nebulisation
efciency equivalent increased with increasing acid
concentration and reached in the range from 2.0 to
3.0 mol l
1
, a plateau for both the acids. It corre-
sponded to the nebulisation efciency equal to 0.38%
in HCl solutions and 1.2% in HNO
3
.
Relative standard deviations for three repeated
intensity measurements changed from 10 to 50%
indicating that transport of metals into the plasma
was not very stable. For higher acid concentrations,
noticeably smaller values of R.S.D were obtained.
In this work, measurements of Cd were made with-
out any optimisation. Relative standard deviations
referred to the maximum of cadmium nebulisation
efciency equivalent for ionic line 226.502 nm were
equal to 4050% both for HCl and HNO
3
and it could
be explained by cadmium hydride decomposition
[13]. For Cu, closeness of results obtained from two
atomic lines 324.754 and 327.396 nm was very good.
Relative standard deviations for three measurements
of 10 g ml
1
of Cu were here from 10 to 20%.
Similarly, the R.S.D. values for replicate intensity
measurements were obtained in [19].
3.2. Inuence of the arsenic presence
The effect of HCl and HNO
3
concentration on the
nebulisation efciency equivalent for Ca, Cd, Co, Cr,
Fe, Mg, Mn, Ni, Zn and Ti was also examined in the
presence of arsenic and it is shown in Figs. 3 and
4, respectively. As can be seen from comparison of
138 P. Pohl, W. Zyrnicki / Analytica Chimica Acta 429 (2001) 135143
Fig. 1. Effect of HCl concentration on nebulisation efciency equivalent of metals.
Figs. 14, the presence of As in the sample solutions
enhanced transport of some transition metals to the
plasma and it was varying with the type of acid.
It was observed that in HCl medium, the presence
of arsenic led to a growth in the nebulisation efciency
equivalents for elements, such as Fe (two to three
times) and Zn (about two times) in comparison with
values obtained for solutions without arsenic. For Ca,
Cr, Mg, Mn and Ti, the inuence of As on the transport
scale was not meaningful and nebulisation efciency
equivalents were very low. In practice, changes in the
Co and Ni response were also not observed, although
their nebulisation efciency equivalents were one or-
der higher than those for Ca, Cr, Mg, Mn and Ti.
In the solutions acidied with HNO
3
, the pres-
ence of arsenic caused a noticeable increase in the
nebulisation efciency equivalent for Cr (four to ve
times), Mn (seven to eight times) and Ni and Ti (two
times). For Ca, Co, Fe, Mg and Zn, no signicant
differences between transport process of individual el-
ements in the presence and in the absence of As were
noticed.
In the presence of As, the amount of Cd transported
to the plasma in conditions corresponding to the max-
imum of the nebulisation efciency equivalent was
increased by about 20% for HCl and almost by 80%
for HNO
3
in comparison to the conditions in which
As was absent in the sample solution. Similar effect
P. Pohl, W. Zyrnicki / Analytica Chimica Acta 429 (2001) 135143 139
Fig. 2. Effect of HNO
3
concentration on nebulisation efciency equivalent of metals.
was observed for the Cu transport. It was enhanced
by about 20% for HCl and over 90% for HNO
3
. The
equivalent of nebulisation efciency for Cu in the pres-
ence of As reached 2.3% in HNO
3
medium and it was
about ve times higher than obtained in HCl solutions.
Effect of the matrix containing 10 g ml
1
of Ca,
Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Ti and Zn on As I line
intensities (1.0 g ml
1
) was also investigated here. It
was observed that the matrix elements seriously sup-
pressed the As I line intensities as it is shown for the
As 193.759 nm line in Fig. 5. Error bars denote the
precision of three intensity measurements given as the
standard deviation. With increasing HCl concentra-
tion, the effect of signal reduction became smaller. For
HCl concentration of 6.0 mol l
1
, arsenic line inten-
sity was depressed by 60% in comparison to the signal
obtained without presence of interfering elements. It
is in an agreement with previous results reported in
[22] where an increase in the HCl concentration from
0.5 to 5 mol l
1
resulted in an increase in the tolerance
limit for Cu(II) and Ni(II) present in the solution.
3.3. Generation of volatile species
Comparison of the nebulisation efciency equi-
valents for various metals investigated in this study
140 P. Pohl, W. Zyrnicki / Analytica Chimica Acta 429 (2001) 135143
Fig. 3. Effect of HCl concentration on nebulisation efciency equivalent of metals in the presence of As.
conrmed formation of cadmium and copper volatile
species with signicant efciency.
The efciency of volatile cadmiumspecies transport
in this investigation was found to show a maximum
at about 0.50 mol l
1
for HCl and similar effect was
observed in [15]. In addition to that, it was observed
that comparable or higher efciency of Cd volatile
species generation can be obtained in the presence of
HNO
3
in the sample solution.
Very recently, Sturgeon et al. [19,20] reported the
fact of volatile copper species formation in continuous
ow hydride generation. This work is the next one
that delivers that fact. A maximum relative intensity
of copper in [19] was obtained at 1.0 mol l
1
of HCl,
while in this study, it was observed at 2.0 mol l
1
of HCl. However, both results are in much better
agreement taking into account the sample and NaBH
4
ow rates and NaOH amount used for stabilisation
of reducing agent and calculating the available HCl
concentration in the reaction cells. In the system used
in this work response due to generation of copper
volatile species in the HNO
3
medium was about three
times higher than this in HCl solution.
The arsenic and HNO
3
presence in the sample
solution led to the enhancement of the nebulisation
efciency equivalents for Cd and Cu. It was well
comparable with results obtained during pneumatic
nebulisation.
P. Pohl, W. Zyrnicki / Analytica Chimica Acta 429 (2001) 135143 141
Fig. 4. Effect of HNO
3
concentration on nebulisation efciency equivalent of metals in the presence of As.
Wickstrm et al. [21] considered that Co, Cr, Fe
and Ni were transported into ICP as a ne aerosol.
However, enhanced nebulisation efciency equivalents
for Co, Fe and Ni (and at some conditions also for
Cr) in comparison to metals, such as Ca, Mg, Mn, Ti
and Zn, indicate that transport of these elements into
plasma can at least partly occurs in the form of volatile
species as it takes place for Cd and Cu.
3.4. Spectral interferences
Relatively high line intensities of elements, such as
Cd, Cu and also Co, Fe and Ni, observed despite of
gasliquid phase separation in the hydride generation
technique can cause spectral interferences.
For example, for pneumatic nebulisation, the As I
228.812 nm line can be seriously disturbed by the Cd
I 228.802 nm line if the Cd to As concentration ratio
is higher than 1000. It was found here that for hydride
generation systemwith phase separation spectral inter-
ferences of the As I 228.812 nm and Cd I 228.802 nm
lines could be ignored in arsenic determination if the
Cd to As concentration ratio was below 100. Such in-
terferences could be a reason for a high recovery of
As(V) in the presence of Cd observed in [10]. The
next often used As I line at 193.759 nm suffered from
142 P. Pohl, W. Zyrnicki / Analytica Chimica Acta 429 (2001) 135143
Fig. 5. Effect of HCl concentration on intensity of the As I 193.76 nm line.
overlapping by Fe I 193.727 nm line at high concen-
tration ratio of Fe to As.
Transport of Cu due to volatile species formation in
conditions of hydride generation reaction can bring a
potential danger for the determinations of Bi. At some
conditions, spectral interferences between Bi 222.825
and Bi 223.061 nm lines and the Cu I 222.778 nm, Cu
II 222.886 and Cu II 223.008 nm cannot be ignored.
These two cases (dealing with spectral interferences
of CdAs and CuBi) show that the sample composi-
tion can affect the results of arsenic and bismuth de-
termination by the HGICPAES method.
4. Conclusions
Meaningful transport of Cd and Cu in a form of
volatile species into inductively coupled plasma was
observed during hydride generation. The transport ef-
ciency of the volatile species elements (1.4% for Cd
and 2.3%for Cu) was well comparable with pneumatic
nebulisation efciency (4.5%) and strongly dependent
on experimental conditions.
Comparison of transport efciency of various met-
als (Ca, Cd, Co, Cr, Cu, Fe, Mn, Mg, Ni, Zn and Ti)
at conditions of hydride generation reaction indicates
that transport of Co, Cr, Fe and Ni is also due to the
formation of any volatile compounds.
It can lead to serious spectral interferences between
metals, such as Cd, Cu or Fe and elements forming
volatile hydrides, such as As or Bi during reaction with
NaBH
4
in acid medium in gasliquid phase separation
system.
It was found that not only conditions, such as type
of acid and its concentration but also presence of ar-
senic in the sample inuences the metal transport ef-
ciencies into the plasma. Study on effect of other
hydride forming elements, such as Sn, Sb, Bi and Se
on transport of metals into plasma during the hydride
generation is undertaken.
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