Spectrochimica Acta Part B 171 (2020) 105947

Contents lists available at ScienceDirect

Spectrochimica Acta Part B

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

Generation of tellurium hydride and its atomization in a dielectric barrier T

discharge for atomic absorption spectrometry
⁎
Kateřina Bufkováa,b, Stanislav Musila, , Jan Kratzera, Pavel Dvořákc, Martina Mrkvičkovác,
Jan Voráčc, Jiří Dědinaa
a
Institute of Analytical Chemistry of the Czech Academy of Sciences, Veveří 97, Brno 60200, Czech Republic
b
Faculty of Science, Department of Analytical Chemistry, Charles University in Prague, Hlavova 8, Prague, 128 43, Czech Republic
c
Faculty of Science, Department of Physical Electronics, Masaryk University, Kotlářská 2, Brno 611 37, Czech Republic

A R T I C LE I N FO A B S T R A C T

Keywords: Atomization of tellurium hydride in a dielectric barrier discharge (DBD) atomizer was investigated for the first
Tellurium time. First, the conditions of hydride generation were optimized with the use of a miniature diffusion flame
Hydride generation atomizer and high-resolution continuum source atomic absorption spectrometry. Generation efficiency of more
Atomic absorption spectrometry than 90% was determined from a comparison of the response to solution nebulization with inductively coupled
Dielectric barrier discharge atomizer
plasma mass spectrometry. Subsequently, atomization of tellurium hydride in a plane-parallel configuration of
Laser-induced fluorescence
the DBD atomizer was optimized. Argon was found as the best carrier gas under a flow rate of 75 mL min−1 while
the peak-to-peak high voltage was 18 kV. A limit of detection of 56 ng L−1 (3σ, n = 15) and repeatability (RSD)
of 2.8% at 5 μg L−1 were reached. The accuracy and applicability of this methodology was verified by analysis of
water Standard Reference Material NIST 1643f and two model samples of tap and stream water. Laser-induced
fluorescence was employed to investigate a spatial distribution of free Te atoms and to estimate atomization
efficiency in the DBD. Significant fractions of free Te atoms were identified all over the length of the optical tube
of the DBD atomizer covered by the electrodes and atomization efficiency of up to 100% was quantified. A
feasibility of tellurium hydride in-situ collection in the DBD atomizer was studied and collection efficiency of
around 50% was found promising for further studies.

1. Introduction
Tellurium belongs to a group of elements recently defined as tech-
nology-critical elements [1] that can be characterized by several
common features - extremely low concentrations in environmental
compartments but since recently increasingly used in modern technol-
ogies, such as those needed for modern communication, computing and
production of clean energy. Increased use of Te also brought the issue of
its impact on its biogeochemical and environmental cycle and potential
human health, which increases demand for analytical methods for its
determination, to provide data for establishing the natural levels and
assessment of any changes [2,3].
Tellurium exists in a variety of oxidation states (VI, IV, 0, –II).
Because of very low concentrations the analysis of Te is a difficult task.
D'Ulivo wrote a comprehensive review on the determination of Te and
their species in environmental samples [4]. Although inductively cou-
pled plasma mass spectrometry (ICP-MS) has become the method of
choice for measuring trace elements concentrations, Te is a difficult
element for ICP-MS because of poor sensitivity given by its high ioni-
zation energy and number of stable isotopes plagued by the inter-
ferences. Alternatively, Te can be determined at trace levels by vol-
tammetry [5], atomic absorption (AAS) and atomic fluorescence
spectrometry (AFS), the latter two usually coupled to hydride genera-
tion (HG) [6–11]. Enrichment procedures prior to HG [3] as well as in-
situ collection of TeH2 in a graphite furnace (GF) for AAS were often
adopted to enable Te determination at natural levels of concentrations
[12,13].
Generally, HG of Te is performed by NaBH4 reduction from rather
high concentrations of HCl or other mineral acids (3–6 M). Fast gas-
liquid separation is recommended due to high solubility of tellurium
hydride in water [14] and its thermal instability [4,14,15]. Te(VI) does
not produce volatile hydride and pre-reduction step to Te(IV) is ne-
cessary [15]. A detailed study on HG of Te including the effect of
various additives was published by D'Ulivo et al. [16,17].
Low power plasma dielectric barrier discharges (DBD) operating at
almost ambient temperature and pressure are nowadays competing

⁎
Corresponding author.
E-mail address: stanomusil@biomed.cas.cz (S. Musil).

https://doi.org/10.1016/j.sab.2020.105947
Received 19 May 2020; Received in revised form 21 July 2020; Accepted 30 July 2020
Available online 03 August 2020
0584-8547/ © 2020 Elsevier B.V. All rights reserved.
K. Bufková, et al.
with quartz tube atomizers (QTA) for atomization of hydrides in AAS
[18,19]. DBD atomizers in a plane-parallel configuration were reported
for atomization of AsH3 [20–22], BiH3 [23,24], PbH4 [25], SbH3
[26,27], SeH2 [27–30] and SnH4 [27,31] with AAS detection. The
achieved analytical performance of on-line atomization was also im-
proved for some elements by employing in-situ collection of their hy-
drides directly in the optical arm of the DBD [20,23,26,30], similarly as
known for GF. Although much analytical work has been done in recent
years including several applications to real samples, still little is known
about the mechanism of atomization, atomization efficiency and fate of
free atoms in the plasmas [24,29,32]. Very interesting approach to
those studies was presented recently at our laboratory for Pb [25] when
a laser-induced fluorescence (LIF) was employed to examine spatial
distribution of free Pb atoms inside the optical arm during discharge
allowing even quantification of atomization efficiency of lead hydride.
No work on atomization of TeH2 in the DBD has been published so
far. The only related work dealing with Te and DBD lies in application
of the DBD for plasma assisted vapor generation of Te, however, the
detection itself was carried out by AFS in a diffusion flame [33]. An-
other work, published recently by our group, is focused on HG of TeH2
with subsequent atomization and excitation in a capillary DBD and
detection by temporally resolved optical emission spectrometry [34].
The aim of this work was to optimize the conditions of HG of Te, to
couple the hydride generator to the DBD atomizer for sensitive detec-
tion by high-resolution continuum source (HR-CS) AAS and to optimize
the conditions of atomization. Moreover, the longitudinal distribution
and fate of free Te atoms in the DBD atomizer was examined using
spatially resolved LIF measurements which enabled the estimate of
atomization efficiency. The feasibility of TeH2 in-situ collection directly
in the optical arm of the DBD is also demonstrated.
2. Experimental
2.1. Standards, reagents and materials
Deionized water (DIW, < 0.2 μS cm−1, Ultrapur, Watrex, Czech
Republic) was employed for preparation of all solutions. For HG,
working Te(IV) standards were prepared by serial dilution of a
1000 mg L−1 stock standard solution (Analytika, Czech Republic) in
3 M HCl (p.a., Merck, Germany) that was also used as a carrier medium
for HG. If explicitly stated, also Te(VI) standards were employed and
prepared from a 1000 mg L−1 stock standard solution (BDH, UK). A
reductant solution containing 2% (m/v) NaBH4 (98%, Sigma-Aldrich,
USA) in 0.4% (m/v) KOH (p.a., Lach-Ner, Czech Republic) was pre-
pared fresh daily. Concentrated H2SO4 (96%, p.a. Carlo Erba, Italy),
NaOH pellets (p.a., Penta, Czech Republic) and solid CaCl2 (Lachema,
Czech Republic) were used for drying of the gas phase in some sets of
experiments. For experiments with ICP-MS, HNO3 (65%, semiconductor
grade, Sigma-Aldrich, USA) was used to prepare a carrier solution for
nebulization and 1000 mg L−1 Ge standard solution (Analytika, Czech
Republic) for an internal standard (IS).
The methodology was verified by an analysis of SRM NIST 1643f
(Trace Elements in Water) and applied to two water samples (tap and
stream).
2.2. Hydride generator
The same generator as described in Refs. [35, 36] with a flow in-
jection (FI) sample introduction was used (Fig. 1). A sample was in-
jected by a six port injection valve with a loop of 0.94 mL volume into
the flow of the carrier liquid (4 mL min−1) before mixing with the re-
ductant (1.2 mL min−1). The outlet of the GLS was connected by 12 cm
long PTFE tube (1.6 mm i.d.) either to a miniature diffusion flame
(MDF) atomizer or to a dielectric barrier discharge (DBD) atomizer (see
Section 2.3) or to ICP-MS (see Section 2.5). If explicitly stated, auxiliary
Ar flow was introduced downstream the GLS. In some experiments,
2
Spectrochimica Acta Part B 171 (2020) 105947
continuous flow (CF) version of the generator was used. In this case, the
six port injection valve was removed and either blank/carrier (3 M HCl)
or standards in carrier were continuously delivered using a three-way
valve for switching between them (not shown in Fig. 1).
2.3. Atomizers
Exactly the same MDF atomizer described for example in Refs. [37,
38] and illustrated in Fig. 2A was employed with AAS to optimize
conditions of HG. It was supplied at the lower end with H2 (flame H2)
that served as a fuel of the diffusion flame. The optical axis of the
spectrometer, i.e. the axis of the radiation beam, intersects the vertical
axis of the atomizer. The lower edge of the radiation beam was set just
above the top of the atomizer. Unless otherwise stated, the flow rates of
gases for atomization of TeH2 in the MDF with HR-CS-AAS were chosen
as 100 mL min−1 flame H2 and 100 mL min−1 carrier Ar.
The design of the quartz T-shaped DBD atomizer, illustrated in
Fig. 2B, was similar to that used in previous studies [20,23–26,28–30].
Its optical arm was 75 mm long with a 7 mm × 3 mm internal rectan-
gular cross-section. Two copper electrodes (50 mm long, 5 mm wide)
were placed on the vertical outer sides of the optical arm and they were
supplied with sinusoidal voltage with a frequency of 28.5 kHz. A quartz
tube (20 mm long, 2 mm i.d., 4 mm o.d.) was sealed to the center of the
optical arm and served as an inlet arm. In a special set of experiments
dealing with in-situ collection of TeH2, an extra T-connector made of
polypropylene (2 mm i.d.) was placed upstream the inlet arm. A deac-
tivated fused silica capillary (Supelco, Germany, 0.53 mm i.d.) was
centered inside the inlet arm with its tip aligned with the junction of the
inlet arm with the optical arm. A low flow of O2 was introduced
through the capillary whereas all the gases from the GLS were in-
troduced into the inlet arm (see Fig. 2C).
If explicitly stated, various dryers (see Supplementary Material for
details) were inserted at the outlet of the GLS to prevent aerosol and
water vapor co-generated with TeH2 from entering the DBD atomizer
(dryers not displayed in Fig. 1). They comprised cartridges packed with
solid NaOH [39] or CaCl2, a glass vial filled with concentrated H2SO4
and a membrane syringe disc filter (0.45 μm).
2.4. Atomic absorption spectrometry
A high-resolution continuum source atomic absorption spectrometer
(HR-CS-AAS) ContrAA 300 (Analytik Jena, Germany) with ASpect CS
2.1.2.0 software was employed for AAS measurements. It is equipped
with a Xe short-arc lamp operating in a hot-spot mode, high-resolution
monochromator and a linear charge coupled device (CCD) array as a
detector. The central pixel was set at 214.281 nm for detection of Te, at
this wavelength the spectral resolution corresponded to approximately
1.5 pm per pixel. Three pixels were used for evaluation - as a sum of a
central pixel and two adjacent pixels because the best signal-to-noise
ratio is obtained under these conditions [40]. However, the entire
spectral range around the analytical line was displayed by 200 pixels
(≈0.3 nm). The iterative background correction (IBC) mode was used
throughout. The recorded spectra were exported to and integrated in
MS Excel.
A standard flame burner was removed and either MDF or DBD
atomizers were situated into the optical path of the spectrometer. The
vertical and horizontal positions of both atomizers were set each day. In
the case of the DBD, the orientation of the optical arm towards the
radiation beam was optimized in order to reach as high energy of the
beam on the detector as possible.
2.5. Determination of generation efficiency
Generation efficiency, i.e. the fraction of the analyte that actually
enters the atomizer/detector, was determined from a comparison of
relative sensitivities obtained with HG and with nebulization of Te
K. Bufková, et al.
Fig. 1. Scheme of the hydride generator with FI sample introduction; PP1 and PP2 – peristaltic pumps.
Fig. 2. Atomizer setups (side view) used in combination with the hydride generator; A) miniature diffusion flame (MDF); B) dielectric barrier discharge (DBD)
atomizer for on-line atomization; C) DBD atomizer for in-situ collection.
standard solutions to the ICP-MS under the same plasma conditions as
described previously [37,38,41,42]. The scheme of the way of coupling
of HG to ICP-MS (Fig. S1) and description of the apparatus are detailed
in Supplementary Material.
Nebulization efficiency, representing here the fraction of the neb-
ulized analyte that enters the plasma, was determined using a modified
waste collection method – see References [42–44] and Supplementary
Material for details.
2.6. Laser-induced fluorescence measurements
The laser beam for the diagnostics was generated by combination of
Nd:YAG laser (Quanta-Ray PRO-270-30), a dye laser (Sirah, PRSC-D-24-
EG, with the dye Rhodamine 101/B) and a frequency conversion unit.
The system produced short laser pulses at the frequency of 30 Hz, with
duration 8 ns and spectral width 0.4 pm. The excitation and fluores-
cence scheme for LIF measurements is shown in Fig. S2. The
225.903 nm excitation to the quintet 5p36s 5S2 state of Te atoms was
used instead of the spin-allowed 214.28 nm excitation to the triplet
5p36s 3S1 state, since the wavelength around 226 nm was easily ac-
cessible in the described experiment and the use of the weaker spin-
forbidden transition reduced the saturation of the fluorescence process.
The shape of the laser beam was restricted by diaphragms to a rectangle
(5 × 2 mm) which passed through the center of the optical arm of the
atomizer investigated. The energy of the laser pulses was monitored by
a pyroelectric energy meter (Ophir PE9) and was kept low (around
0.3 μJ) in order to reduce the fluorescence saturation. The remaining
weak saturation was quantified and corrected by means of a numerical
model of the fluorescence process. The fluorescence radiation was de-
tected perpendicularly to the laser beam and optical arm axis after
passing through the “upper” quartz wall of the DBD (see Fig. 2B). The
3
Spectrochimica Acta Part B 171 (2020) 105947
detected fluorescence wavelength (253.074 nm) was separated from the
surrounding radiation by an interference filter (AHF 257/12 BrightLine
HC) and detected by an ICCD camera (Princeton Instruments, PI-MAX
1024). The fluorescence signal was temporally integrated over 100 ns,
which safely covered the whole laser pulse and the fluorescence decay.
In order to obtain the absolute concentration of Te atoms, the sensi-
tivity of the method was calibrated by Rayleigh scattering of the laser
beam. In addition, an independent calibration was realized by mea-
surement of laser absorption. The Te concentration values obtained by
these two methods differed by only 8%.
All the LIF measurements performed in this work were carried out
with the hydride generator with continuous flow (CF) sample in-
troduction using a three-way valve instead of the six port injection
valve (see Section 2.2) to switch between suction of either standard or
blank solution into the generator. It necessitated about 15 s to reach the
discharge after switching the three-way valve from blank to the Te
standard solution, hence the LIF measurement started no sooner than
30 s after changing from blank to Te standard solution. The DBD ato-
mizer was thus supplied by a constant flow of TeH2, which enabled
measurement of steady LIF signal.
2.7. Measurement procedure and conventions
Unless otherwise stated, FI was utilized for introduction of the
acidified sample to the generator. With HG in continuous operation
(both peristaltic pumps running), the sample was manually injected
into the carrier 5 s after the recording of the signal had started.
Measurements were almost exclusively carried out in on-line atomiza-
tion mode. A FI peak shaped signal was recorded for 80 s, which was
sufficient for the FI signal to decline to the baseline. Peak area was
employed as a measure of analyte response. If the in-situ collection
K. Bufková, et al.
mode was used, the measurement procedure comprised two stages -
trapping and volatilization. In the trapping stage, O2 was introduced
through the capillary into the DBD (see Fig. 2C) all over the period
(80 s) that would normally cover recording of the FI peak shaped signal
during the on-line atomization mode. Volatilization stage followed and
it was initiated in time 80 s by switching off the O2 supply through the
capillary while HG was still in operation. As a consequence, a sharp
peak shaped signal was recorded. In the experiments with LIF, CF was
utilized for introduction of either acidified sample or blank. The height
of the steady state corrected to the blank was used for evaluation.
Averages of at least 3 replicates are shown in all relevant figures.
Uncertainties are presented as ± standard deviation (SD) or combined
SD where results are relative. If sensitivity is mentioned, it refers to
peak area related to the analyte mass taken for the measurement. Limit
of detection (LOD) is expressed as 3× SD(blank) / sensitivity.
2.8. Sample preparation
Twenty mL of SRM NIST 1643f was evaporated to dryness in a
40 mL quartz vial using a thermoblock (temperature: ≈100 °C). The
residue was dissolved in 5 mL of 6 M HCl and heated to 95 °C for 1 h in
order to reduce Te(VI) to Te(IV). After that the solution was diluted to
10 mL, thus being the sample twice concentrated. A sample preparation
blank (DIW) was prepared as well. Two water samples were also em-
ployed to demonstrate acceptable recovery of Te(IV) analysis. The
samples included a tap water collected in the laboratory and a stream
river water collected from the Počepický potok in Nechvalice (district of
Central Bohemia). Both samples were filtered through a 0.45 μm PTFE
filter, prepared in 3 M HCl and spiked with 1 and 2 μg L−1 Te(IV) for
the analysis with HG-DBD-AAS.
3. Results and discussion
3.1. Conditions of HG
The relevant generation conditions (concentrations of HCl in the
carrier and NaBH4 in the reductant and reaction coil volume) were
optimized in terms of sensitivity in the on-line atomization mode using
the MDF atomizer and HR-CS-AAS detection. Despite a short absorption
path length, which was reflected in a LOD of approximately 0.7 μg L−1,
the MDF atomizer was employed due to its simplicity, operational cost,
excellent robustness [45], repeatability (< 4%) and our previous ex-
perience with atomization of various analytes [36–38,45].
Only Te(IV) standards were employed during optimization of HG
conditions because HG was not observed using Te(VI) without pre-re-
duction, which is in line with earlier works [9–13,46]. Efficient pre-
reduction can be achieved by heating the Te(VI) standard solution at
95 °C in 6 M HCl for 1 h [15], which was also confirmed in this work.
The optimized conditions of HG are summarized in Table 1. The de-
tailed description of the experiments is given in the Supplementary
Material and in Figs. S3-S5. Only those results that are related to other
experiments are briefly discussed below.
Rather high concentrations of HCl (Fig. S3) and NaBH4 (Fig. S4)
were found necessary for efficient HG, which corresponds to the earlier
works [7,10,16]. No significant effect of a reaction coil length on sen-
sitivity was observed so that the shortest reaction coil (10 cm, 0.08 mL)
was selected for further experiments (Fig. S5). The resultant flow rate of
H2 generated from decomposition of NaBH4 at given conditions in
Table 1
Chosen optimal parameters for HG of tellurium.
HCl concentration in carrier 3M
NaBH4 concentration in reductant 2% (m/v)
KOH concentration in reductant 0.4% (m/v)
Reaction coil volume (length, i.d.) 0.08 mL (10 cm, 1 mm)
4
Spectrochimica Acta Part B 171 (2020) 105947
Table 1 was volumetrically measured as 55 mL min−1. This is in line
with a theoretical amount of 61 mL min−1, corresponding to the com-
plete decomposition of NaBH4, taking into account the flow rate and
concentration of NaBH4.
3.2. Generation efficiency
The hydride generator with optimized parameters (Table 1) was
coupled to ICP-MS. The analytical performance of HG-ICP-MS was
found outstanding with excellent repeatability (< 2% at 2 μg L−1) and
LOD of 1.6 ng L−1 (3σ, n = 13). Moreover, the determination of Te in
SRM NIST 1643f after pre-reduction in 6 M HCl (see Section 2.8 for
details) yielded very good agreement of the result
(0.99 ± 0.01 μg L−1) with the certified value of
0.977 ± 0.0084 μg L−1, which suggests well optimized HG step.
Generation efficiency was determined from a comparison of the
sensitivities obtained with HG sample introduction and conventional
solution nebulization, both coupled to ICP-MS. It is supposed that all
the nebulized sample of analyte is vaporized and converted to free
atoms and ions with the same efficiency as the analyte delivered in the
form of TeH2. The crucial factor of this determination lies in the precise
knowledge of nebulization efficiency that was determined in the way as
described in Section 2.5. Nebulization efficiency, determined using
exactly the same plasma settings as used with HG, reached 8.2 ± 0.4%.
This efficiency is almost the same as determined in our previous study
on photochemical vapor generation (PVG) of Cd (8.3 ± 0.1% was
reached) [47].
The comparison of the sensitivities obtained with HG sample in-
troduction and conventional solution nebulization was carried out with
Te(IV) standards that were introduced either with the injection valve
directing sample to hydride generator (standards 0, 1, 5, 20 μg L−1 in
3 M HCl) or with the chemifold used for sample delivery to the nebu-
lizer (0, 20, 80, 250 μg L−1 in 1% HNO3). When an injected standard
was nebulized, HG was concurrently in operation such that the condi-
tions in the plasma were unchanged, and vice versa. An enhancement
factor (compared to nebulization) and derived generation efficiency
reached 11.3 ± 0.1 and 92.5 ± 4.8%, respectively, which is a value
that highlights well optimized HG. Additional experiments (see
Supplementary Material and Fig. S6) showed that the carrier Ar flow
rate in the range from 25 to 200 mL min−1 did not influence generation
efficiency.
3.3. Atomization in DBD
3.3.1. Drying of the gas phase
The performance of a low-power and low-temperature plasma of the
DBD may be susceptible to the presence of water vapor and fine aerosol
droplets that are co-generated during vigorous reaction in the generator
(2% NaBH4 and 3 M HCl) and transported by the carrier gas to the
plasma. Hence, a possibility of removing the moisture from the gas
phase with TeH2 was investigated using a variety of dryers (see Section
2.3 and Supplementary Material). Using the dryer based on con-
centrated H2SO4 was accompanied with around 70% loss of TeH2 while
even more than 80% of TeH2 was lost in the membrane dryer (0.45 μm).
Using the NaOH dryer caused complete loss of TeH2 and the same re-
tention was also found with the dryer cartridge packed with solid CaCl2.
In conclusion, no suitable dryer was found, which should be accounted
for the high acidity and solubility of tellurium hydride in water [14]. As
a consequence, no drying was employed in further experiments.
3.3.2. Atomization conditions
The electrodes of the DBD atomizer are coupled to the power source
generating a sinusoidal waveform function at a frequency of 28.5 kHz.
The effect of a peak-to-peak high voltage on sensitivity was studied
using Ar as a carrier gas. The minimum value of the peak-to-peak high
voltage to ignite and sustain the discharge was 12 kV. The maximum
K. Bufková, et al.
Fig. 3. Effect of carrier Ar flow rate on peak area from 5 μg L−1 Te(IV); 18 kV
applied high voltage. Uncertainties are presented as ± SD (n ≥ 3).
sensitivity was obtained at 18–19 kV, nevertheless, the sensitivity did
not change much with varied high voltage (see Fig. S7 in
Supplementary Material). The value of 18 kV was selected as optimum
for further experiments. Higher values of peak-to-peak voltage than
35 kV were not tested because of risk of overheating and damage of the
DBD atomizer when operating several hours.
The effect of carrier Ar flow rate was studied at chosen optimum
peak-to-peak voltage of 18 kV (Fig. 3). Since the generation efficiency is
not changing in the studied range of carrier Ar flow rate, as stated in
Section 3.2, the character of the dependence in Fig. 3 is controlled
solely by processes in the atomizer. It should be taken into account that
the fraction of H2 in the gas phase changes dramatically in the studied
range of the carrier flow rate because of the (constant) flow rate of
55 mL min−1 H2 generated during HG. Namely, the fraction of H2 at the
lowest carrier Ar flow rate investigated (25 mL min−1) was 69% while
at 200 mL min−1 it was 22%. In principle, the carrier Ar flow rate can
influence only (i) cross-sectional density of free atoms in the atomizer
and (ii) atomic absorption coefficient of Te free atoms. The cross-sec-
tional density of free atoms in the atomizer is controlled: (a) by ato-
mization efficiency that is influenced by fraction of H2 in the gas phase,
atomization efficiency is lower in H2 than in argon as discussed below;
and (b) by the total gas flow rate which controls dilution of free atoms.
Atomic absorption coefficient of Te free atoms can depend on fraction
of H2 in the atomizer atmosphere - the higher fraction of H2 the lower
atomic absorption coefficient as demonstrated for Se [15,48]. The
character of the dependence in Fig. 3 can be thus interpreted in terms of
negative influence of increasing gas flow rate, resulting in increasing
dilution, and its positive influence causing decrease in fraction of H2 in
the atomizer. The highest sensitivity was found at 75 mL min−1 carrier
Ar (corresponding to 42% fraction of H2) which was chosen as op-
timum. The sensitivity gradually decreased at flow rates higher than
75 mL min−1, as a result of a greater dilution of free atoms. The de-
crease is not inversely proportional to the flow rate since it is partially
offset by the positive influence of decreasing H2 fraction. The formation
of discharge was also visibly impaired at lower flow rates when the
discharge was sometimes not distributed uniformly on both sides of the
DBD covered by the electrodes.
Apart from Ar, also H2, He and N2 were tested as carrier gases. The
atomization conditions (carrier gas flow rate, high voltage) were not
optimized for each carrier gas tested but optimum conditions found for
Ar were adopted (18 kV peak-to-peak high voltage, 75 mL min−1 carrier
gas). In addition, there is always an additional flow rate of 55 mL min−1
H2 originating from HG. The relative sensitivity (related to Ar) was
44 ± 3% for H2 while it reached 65 ± 4% for He. No signal was ob-
tained for N2, however, increasing the peak-to-peak high voltage from
5
Spectrochimica Acta Part B 171 (2020) 105947
18 kV to 25 kV and 35 kV resulted in 76 ± 6% and 75 ± 5% relative
sensitivity, respectively. The lower sensitivity observed for other carrier
gases than Ar indicates lower atomization efficiency due to less “effi-
cient” discharge characteristic in these gases but negative influence of
these gases on atomic absorption coefficient can play a role as well. It is
evident from the above results that the far best performance regarding
sensitivity, but also repeatability, was achieved with Ar as the carrier
gas.
3.3.3. Analytical characteristics and application
Under optimum conditions of HG (Table 1) and atomization in the
DBD (18 kV peak-to-peak high voltage, 75 mL min−1 carrier Ar), the
analytical characteristics of the HG-DBD with HR-CS-AAS were de-
termined. The results are presented for evaluation from 3 pixels (central
pixel set to 214.281 nm) because it provided the best LODs. The cali-
bration function constructed with 0, 0.25, 0.5, 1.0, 2.5, 5.0 and
10 μg L−1 Te(IV) standards was linear (R2 = 0.996) and sensitivity
equaled to 0.43 s ng−1. The relative and absolute LODs (3σ, n = 15)
reached 56 ng L−1 and 52 pg, respectively. A comparison of the relative
LOD to the methods based on various vapor generation techniques –
HG, PVG, electrochemical hydride generation (EcHG) or plasma as-
sisted vapor generation (PAVG) in direct transfer mode (without any
preconcentration step), and coupled to various detectors – AAS, AFS or
ICP-MS published recently, is demonstrated in Table 2. It is evident that
our methodology offers far best LODs when compared to other atomi-
zers used in AAS and even competes with HG or PVG-AFS approaches.
The repeatability, expressed as an RSD, was determined by con-
secutive measurement of 5 μg L−1 Te(IV) standard followed by a mea-
surement of blank (3 M HCl). It reached 2.8% for 15 replicates of peak
area evaluated from 3 pixels. The inter-day repeatability was also quite
satisfactory – better than 6.8% (n = 7). The interesting feature of the
DBD was found in a little bit longer time necessary to stabilize sensi-
tivity at the beginning of the measurement day. It typically lasted 5–6
measurement cycles with 5 μg L−1 Te(IV) standard and it may be re-
lated to saturation of the inner surface of the DBD with permanent Te
deposits.
Accuracy of HG-DBD-AAS methodology was verified by analysis of
SRM NIST 1643 f. Due to the presence of nitric acid (0.32 mol L−1), low
concentration of total Te (certified concentration
0.977 ± 0.0084 μg L−1) and the fact that all Te was found to be pre-
sent as Te(VI), the material had to be evaporated to dryness and Te(VI)
pre-reduced to Te(IV) in 6 M HCl at 95 °C. Tellurium concentration
determined against an external calibration was 1.14 ± 0.06 μg L−1,
which corresponds to fair recovery of 117% in comparison to the cer-
tified value.
HG-DBD-AAS was further applied to two water samples (tap and
stream water) to determine only Te(IV) species. The concentration of Te
(IV) in the tap water was found below LOD while the concentration in
the stream water was between LOD and LOQ. The practical feasibility
determining of Te(IV) was thus examined by Te(IV) standard addition
to 1 and 2 μg L−1 Te(IV) in those samples. The additions yielded
Table 2
Comparison of LODs for tellurium determination by methods based on vapor
generation and direct transfer (no preconcentration) to the detectors.
Method LOD (μg L−1) Reference
HG-MDF-AAS 0.7 This work
HG-QTA-AAS 0.26; 1.8 [6]; [49]
HG-DBD-AAS 0.056 This work
HG-AFS 0.023; 0.1; 0.21 [8]; [11]; [10]
PVG-AFS 0.06; 0.08 [50]; [51]
EcHG-AFS 0.14; 2.2 [52]; [53]
PAVG-AFS 50 [33]
HG-ICP-MS 0.0016 This work
PVG-ICP-MS 0.001 [54]
K. Bufková, et al.
Fig. 4. Longitudinal distribution of free Te atoms in the DBD atomizer;
50 μg L−1 Te(IV) taken for HG, 18 kV applied high voltage, 75 mL min−1 carrier
Ar. Continuous flow HG mode was used.
acceptable recoveries of 105 ± 3% and 102 ± 2%, respectively, for
the tap water and 95 ± 3% and 89 ± 3%, respectively, for the stream
water.
3.3.4. Spatial distribution and atomization efficiency
Longitudinal distribution of free Te atoms inside the DBD was
measured by LIF under optimum conditions of atomization (18 kV peak-
to-peak high voltage, 75 mL min−1 carrier Ar). CF was employed for
sample introduction to HG so that a constant supply of TeH2 into the
DBD was assured (see Section 2.6 for details). A blank corrected
fluorescence signal of 50 μg L−1 Te(IV) recorded by the ICCD camera
from a top view through the quartz wall is displayed in Fig. 4.
The distribution was constant over the whole 35 μs period of the
driving AC voltage. The apparent peaks in the right atomizer half were
caused by the uneven surface of the quartz wall in this region, which led
to irregular refraction of the fluorescence radiation. Nevertheless, it is
evident that most of free atoms are present in the side parts of the DBD
optical arm at 10–20 mm distance from the junction of the inlet arm
and optical arm (X coordinate = 0 mm). The concentration of free Te
atoms in these two regions reaches average concentration of
(3.65 ± 0.19) × 1018 Te m−3. The concentration of free Te atoms
decreases in the direction to the junction with the inlet arm and also
beyond 20 mm from this junction because these parts are not covered
by the Cu electrodes forming discharge. The distribution of free Te
atoms correlates reasonably well with the distribution of H atoms we
recently determined in a DBD atomizer of the same design [55]. It in-
dicates that the mechanism of hydride atomization in DBDs is similar to
that in quartz tube atomizers - via an interaction with H radicals. In
addition, the observation that free atom concentration steeply de-
creases in atomizer regions uncovered by electrodes, where H radical
concentration should be reduced substantially, suggests a very fast
decay of free Te atoms once they leave area characterized by a high
density of H radicals. Taking into account Te standard concentration of
50 μg L−1 delivered at a flow rate of 4 mL min−1, generation efficiency
of 92.5 ± 4.8% quantified in Section 3.2 and total gas flow rate of
130 mL min−1, Te concentration in the gas phase at the outlet from the
GLS should reach (6.72 ± 0.35) × 1018 Te m−3. Since a gas phase
temperature of 550 K was estimated in the DBD by LIF of OH radicals
[55], a concentration of up to (3.65 ± 0.19) × 1018 Te m−3 can be
theoretically expected inside the DBD atomizer due to gas expansion.
Finally, atomization efficiency in the DBD parts with maximum con-
centration of free Te atoms was estimated as the ratio of blank corrected
number Te atom concentration and the theoretically expected value as
100 ± 7%. This suggests highly efficient atomization of TeH2 in almost
6
Spectrochimica Acta Part B 171 (2020) 105947
whole inner volume of the DBD atomizer.
3.4. In-situ collection in DBD
Recently, efficient preconcentration via hydride trapping and sub-
sequent analyte volatilization and atomization directly in the DBD
atomizer with AAS detection was found feasible. The trapping and
volatilization processes are controlled only by a presence and absence
of O2 in the discharge gas, respectively. This makes the procedure
simple and operator friendly. A successful in-situ collection of As [20]
and Sb [26] hydrides in the same DBD atomizer in the presence of O2
was reported recently with collection efficiency close to 100%. On the
contrary, the collection efficiency of Bi and Se was lower reaching only
60–70% [23,30]. Making use of the same approach, successful pre-
concentration of As [56,57] and Se [58] in a tubular DBD with AFS
detection has been also reported. To test the feasibility of in-situ col-
lection of Te, a capillary for O2 delivery was inserted into the inlet arm
and its tip was aligned with the junction of the inlet arm with the op-
tical tube (see Fig. 2C). Even O2 flow rate to the capillary as low as
2 mL min−1 resulted in 70% sensitivity decrease and in significantly
impaired repeatability. In the range from 4 to 10 mL min−1 of O2 the
sensitivity decreased to almost zero (see Fig. S8 for details), which in-
dicates no atomization and suggests efficient trapping inside the optical
arm of the DBD. This correlates with our previous findings [55,59] that
oxygen supplied to the DBD atomizer reduces H radical concentration
in the optical arm. At small O2 flow rates, even 10-fold smaller than that
of H2, H radicals are removed at the center of the optical arm [55,59].
When increasing the O2 inlet, the H atom deficient central region is
gradually extended [55]. Oxygen flow rate of 6 mL min−1 was selected
as optimum for further experiments.
The fast release and atomization of the trapped analyte was
achieved by switching off the O2 supply because the gas phase leaving
the GLS contains high fraction of H2 (42%). The typical signal obtained
with the in-situ collection procedure is displayed in Fig. 5. Note, the
first interval (0–80 s) corresponds to the stage of trapping of TeH2 at
6 mL min−1 O2 when no Te free atoms can be detected. After the
trapping had been completed, the release of the trapped analyte was
carried by switching off the O2 supply at time 80 s. The typical FI signal
measured in the on-line atomization mode (without applied O2) of the
same Te(IV) concentration is also shown for comparison in Fig. 5. The
difference in full width at half maximum (FWHM) was significant,
namely, it corresponded to 0.8 s for in-situ collection mode and 16 s for
the on-line atomization mode.
Fig. 5. Comparison of the peak signal obtained in in-situ collection mode using
O2 for trapping and H2 rich atmosphere for volatilization (solid line) and with
on-line atomization mode (dotted line); 1 μg L−1 Te(IV), 18 kV applied high
voltage, 75 mL min−1 carrier Ar; trapping conditions: 6 mL min−1 O2 (0–80 s),
volatilization conditions: 0 mL min−1 O2 (80–120 s).
K. Bufková, et al.
Collection efficiency was estimated by comparison of the peak areas
from 1 μg L−1 Te(IV) obtained in the on-line atomization mode (in the
absence of O2) and in the in-situ collection mode (trapping with
6 mL min−1 O2 with subsequent volatilization by H2 contained in the
gas phase). Thus, the signals measured in those two modes were mea-
sured under strictly the same conditions (flow rates of gases and peak-
to-peak high voltage applied). Collection efficiency of 51 ± 6%
(n = 4) was achieved. Such efficiency as well as improvement in FWHM
seems highly promising. However, this approach could not be opti-
mized further since after 15–20 replicates of in-situ collection proce-
dure, sensitivity impaired in both modes contrasting to excellent intra-
day and satisfactory inter-day repeatability achieved in the on-line
atomization mode (check Section 3.3.3). Simultaneously, deposits
started to be visible in the place close to the outlet of the capillary in the
optical arm. These residues could be removed by washing the DBD
inner surface with a mixture of HNO3 and DIW (1:2) which restored
sensitivity. Such a behavior indicates that a fraction of analyte trapped
in the first stage of the collection mode is not volatilized in the second
stage. With increasing number of in-situ collection cycles it inevitably
leads to the enrichment and spreading of analyte deposit layer that, at
some point, starts to reduce the collection efficiency even more. In
principle, this could be due to deterioration of either trapping or vo-
latilization or atomization. Anyway, a perspective way to optimize the
collection mode is to achieve a complete volatilization in the second
stage of the procedure. This would lead to 100% collection efficiency
and it could also prevent formation of deposits and subsequent dete-
rioration of sensitivity. Higher H2 fraction in the atomizer during vo-
latilization, higher applied peak-to-peak voltage and/or different shape
of a waveform function of the high voltage modulation (square wave
instead of sinusoidal) [31] could be a solution to increase the volatili-
zation efficiency.
4. Conclusion
To our best knowledge, this paper describes atomization of Te hy-
dride in the DBD atomizer for the first time. The conditions of HG were
optimized and high generation efficiency (> 90%) was confirmed.
Argon comprising a considerable fraction of H2 originating from HG
was found suitable for atomization in the DBD. The mechanistic study
performed by LIF has clearly revealed that atomization efficiency of
TeH2 is high (≈100%) along almost the entire length of the DBD ato-
mizer. The analytical performance of HG coupled to HR-CS-AAS is
perspective in terms of sensitivity and repeatability. It could be even
further improved because feasibility of in-situ collection in the DBD has
been demonstrated, yielding the collection efficiency of around 50%.
Further optimization and establishing the method of in-situ collection
for routine measurements and development of speciation analysis sce-
nario for distinguishing between Te(IV) and Te(VI) is required for ap-
plications to the samples with natural levels of Te in the environment
[2].
Declaration of Competing Interest
The authors declare the following financial interests/personal re-
lationships which may be considered as potential competing interests:
Acknowledgements
Financial support by the Czech Science Foundation (17-04329S), by
the Institute of Analytical Chemistry of the CAS (Institutional research
plan RVO: 68081715) and by the Ministry of Education, Youth and
Sports of the Czech Republic (LM2018097) is highly acknowledged.
7
Spectrochimica Acta Part B 171 (2020) 105947
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.sab.2020.105947.
References
[1] M. Filella, J.C. Rodriguez-Murillo, Less-studied TCE: are their environmental con-
centrations increasing due to their use in new technologies? Chemosphere 182
(2017) 605–616.
[2] M. Filella, C. Reimann, M. Biver, I. Rodushkin, K. Rodushkina, Tellurium in the
environment: current knowledge and identification of gaps, Environ. Chem. 16
(2019) 215–228.
[3] N. Belzile, Y.W. Chen, Tellurium in the environment: a critical review focused on
natural waters, soils, sediments and airborne particles, Appl. Geochem. 63 (2015)
83–92.
[4] A. D'´Ulivo, Critical review. Determination of selenium and tellurium in environ-
mental samples, Analyst 122 (1997) 117R–144R.
[5] M. Biver, F. Quentel, M. Filella, Direct determination of tellurium and its redox
speciation at the low nanogram level in natural waters by catalytic cathodic
stripping voltammetry, Talanta 144 (2015) 1007–1013.
[6] J. Ha, H.W. Sun, J.M. Sun, D.Q. Zhang, L.L. Yang, Determination of tellurium in
urine by hydride generation atomic absorption spectrometry with derivative signal
processing, Anal. Chim. Acta 448 (2001) 145–149.
[7] H. Matusiewicz, M. Krawczyk, Determination of tellurium by hydride generation
with in situ trapping flame atomic absorption spectrometry, Spectrochim. Acta, Part
B 62 (2007) 309–316.
[8] A. D'Ulivo, I. Paolicchi, M. Onor, R. Zamboni, L. Lampugnani, Flame-in-gas-shield
miniature flame hydride atomizers for ultra trace element determination by che-
mical vapor generation atomic fluorescence spectrometry, Spectrochim. Acta, Part
B 64 (2009) 48–55.
[9] P. Cava-Montesinos, A. de la Guardia, C. Teutsch, M.L. Cervera, M. de la Guardia,
Speciation of selenium and tellurium in milk by hydride generation atomic fluor-
escence spectrometry, J. Anal. At. Spectrom. 19 (2004) 696–699.
[10] M. Chen, L.C. Wu, X. Yi, K.Z. Yang, H.G. Xie, Tellurium speciation in a bioleaching
solution by hydride generation atomic fluorescence spectrometry, Anal. Methods 9
(2017) 3061–3066.
[11] Y.W. Chen, A. Alzahrani, T.L. Deng, N. Belzile, Valence properties of tellurium in
different chemical systems and its determination in refractory environmental
samples using hydride generation – atomic fluorescence spectroscopy, Anal. Chim.
Acta 905 (2016) 42–50.
[12] E. Yildirim, P. Akay, Y. Arslan, S. Bakirdere, O.Y. Ataman, Tellurium speciation
analysis using hydride generation in situ trapping electrothermal atomic absorption
spectrometry and ruthenium or palladium modified graphite tubes, Talanta 102
(2012) 59–67.
[13] B.M. Yoon, S.C. Shim, H.C. Pyun, D.S. Lee, Hydride generation atomic absorption
determination of tellurium species in environmental samples with in situ con-
centration in a graphite furnace, Anal. Sci. 6 (1990) 561–566.
[14] N.N. Greenwood, A. Earnshaw, Chemistry of the Elements, Pergamon Press Plc,
1984.
[15] J. Dědina, D.L. Tsalev, Hydride Generation Atomic Absorption Spectrometry, John
Wiley & Sons, Chichester, 1995.
[16] A. D’Ulivo, K. Marcucci, E. Bramanti, L. Lampugnani, R. Zamboni, Studies in hy-
dride generation atomic fluorescence determination of selenium and tellurium. Part
1 – self interference effect in hydrogen telluride generation and the effect of KI,
Spectrochim. Acta, Part B 55 (2000) 1325–1336.
[17] K. Marcucci, R. Zamboni, A. D'Ulivo, Studies in hydride generation atomic fluor-
escence determination of selenium and tellurium. Part 2 – effect of thiourea and
thiols, Spectrochim. Acta, Part B 56 (2001) 393–407.
[18] S. Brandt, A. Schutz, F.D. Klute, J. Kratzer, J. Franzke, Dielectric barrier discharges
applied for optical spectrometry, Spectrochim. Acta, Part B 123 (2016) 6–32.
[19] S. Liu, Y.L. Yu, J.H. Wang, Advances in discharge-based microplasmas for the
analysis of trace species by atomic spectrometry, J. Anal. At. Spectrom. 32 (2017)
2118–2126.
[20] P. Novák, J. Dědina, J. Kratzer, Preconcentration and atomization of Arsane in a
dielectric barrier discharge with detection by atomic absorption spectrometry, Anal.
Chem. 88 (2016) 6064–6070.
[21] M. Straka, S. Burhenn, K. Marschner, S. Brandt, U. Marggraf, J. Dědina, J. Franzke,
J. Kratzer, Novel designs of dielectric barrier discharge hydride atomizers for
atomic spectrometry, Spectrochim. Acta, Part B 146 (2018) 69–76.
[22] Z.L. Zhu, S.C. Zhang, Y. Lv, X.R. Zhang, Atomization of hydride with a low-tem-
perature, atmospheric pressure dielectric barrier discharge and its application to
arsenic speciation with atomic absorption spectrometry, Anal. Chem. 78 (2006)
865–872.
[23] J. Kratzer, J. Boušek, R.E. Sturgeon, Z. Mester, J. Dědina, Determination of bismuth
by dielectric barrier discharge atomic absorption spectrometry coupled with hy-
dride generation: method optimization and evaluation of analytical performance,
Anal. Chem. 86 (2014) 9620–9625.
[24] J. Kratzer, O. Zelina, M. Svoboda, R.E. Sturgeon, Z. Mester, J. Dědina, Atomization
of Bismuthane in a dielectric barrier discharge: a mechanistic study, Anal. Chem. 88
(2016) 1804–1811.
[25] M. Albrecht, M. Mrkvičková, M. Svoboda, J. Hraníček, J. Voráč, P. Dvořák,
J. Dědina, J. Kratzer, Atomization of lead hydride in a dielectric barrier discharge
atomizer: optimized for atomic absorption spectrometry and studied by laser-
K. Bufková, et al.
induced fluorescence, Spectrochim. Acta, Part B 166 (2020) 105819.
[26] P. Zurynková, J. Dědina, J. Kratzer, Trace determination of antimony by hydride
generation atomic absorption spectrometry with analyte preconcentration/atomi-
zation in a dielectric barrier discharge atomizer, Anal. Chim. Acta 1010 (2018)
11–19.
[27] Z.L. Zhu, S.C. Zhang, J.H. Xue, X.R. Zhang, Application of atmospheric pressure
dielectric barrier discharge plasma for the determination of Se, Sb and Sn with
atomic absorption spectrometry, Spectrochim. Acta, Part B 61 (2006) 916–921.
[28] O. Duben, J. Boušek, J. Dědina, J. Kratzer, Dielectric barrier discharge plasma
atomizer for hydride generation atomic absorption spectrometry-performance
evaluation for selenium, Spectrochim. Acta, Part B 111 (2015) 57–63.
[29] J. Kratzer, S. Musil, K. Marschner, M. Svoboda, T. Matoušek, Z. Mester,
R.E. Sturgeon, J. Dědina, Behavior of selenium hydride in heated quartz tube and
dielectric barrier discharge atomizers, Anal. Chim. Acta 1028 (2018) 11–21.
[30] J. Kratzer, S. Musil, J. Dědina, Feasibility of in situ trapping of selenium hydride in a
DBD atomizer for ultrasensitive Se determination by atomic absorption spectro-
metry studied with a 75Se radioactive indicator, J. Anal. At. Spectrom. 34 (2019)
193–202.
[31] L. Juhászová, S. Burhenn, L. Sagapova, J. Franzke, J. Dědina, J. Kratzer, Hydride
generation atomic absorption spectrometry with a dielectric barrier discharge
atomizer: method optimization and evaluation of analytical performance for tin,
Spectrochim. Acta, Part B 158 (2019) 105630.
[32] S. Burhenn, J. Kratzer, F.D. Klute, J. Dědina, J. Franzke, Atomization of arsenic
hydride in a planar dielectric barrier discharge: behavior of As atoms studied by
temporally and spatially resolved optical emission spectrometry, Spectrochim. Acta,
Part B 152 (2019) 68–73.
[33] M. Yang, J. Xue, M. Li, G.J. Han, Z. Xing, S.C. Zhang, X.R. Zhang, Low temperature
hydrogen plasma assisted chemical vapor generation for atomic fluorescence
spectrometry, Talanta 126 (2014) 1–7.
[34] S. Burhenn, J. Kratzer, J. Franzke, Temporal evolution of tellurium emission lines in
a capillary dielectric barrier discharge after hydride generation, Spectrochim. Acta,
Part B 171 (2020) 105936.
[35] S. Musil, J. Dědina, A sapphire tube atomizer for on-line atomization and in situ
collection of bismuthine for atomic absorption spectrometry, J. Anal. At. Spectrom.
28 (2013) 593–600.
[36] B. Štádlerová, M. Kolrosová, J. Dědina, S. Musil, Ultrasensitive determination of
bismuth by hydride generation atomic fluorescence spectrometry, J. Anal. At.
Spectrom. 35 (2020) 993–1002.
[37] J. Šoukal, O. Benada, T. Matoušek, J. Dědina, S. Musil, Chemical generation of
volatile species of copper - optimization, efficiency and investigation of volatile
species nature, Anal. Chim. Acta 977 (2017) 10–19.
[38] J. Vyhnanovský, J. Kratzer, O. Benada, T. Matoušek, Z. Mester, R.E. Sturgeon,
J. Dědina, S. Musil, Diethyldithiocarbamate enhanced chemical generation of vo-
latile palladium species, their characterization by AAS, ICP-MS, TEM and DART-MS
and proposed mechanism of action, Anal. Chim. Acta 1005 (2018) 16–26.
[39] P. Taurková, M. Svoboda, S. Musil, T. Matoušek, Loss of di- and trimethylarsine on
Nafion membrane dryers following hydride generation, J. Anal. At. Spectrom. 26
(2011) 220–223.
[40] U. Heitmann, B. Welz, D.L.G. Borges, F. Lepri, Feasibility of peak volume, side pixel
and multiple peak registration in high-resolution continuum source atomic ab-
sorption spectrometry, Spectrochim. Acta, Part B 62 (2007) 1222–1230.
[41] J. Šoukal, R.E. Sturgeon, S. Musil, Efficient photochemical vapor generation of
molybdenum for ICPMS detection, Anal. Chem. 90 (2018) 11688–11695.
[42] J. Vyhnanovský, R.E. Sturgeon, S. Musil, Cadmium assisted photochemical vapor
generation of tungsten for ICPMS detection, Anal. Chem. 91 (2019) 13306–13312.
[43] S. Cuello-Nunez, I. Abad-Álvaro, D. Bartczak, M.E. del Castillo Busto, D.A. Ramsay,
Spectrochimica Acta Part B 171 (2020) 105947
F. Pellegrino, H. Goenaga-Infante, The accurate determination of number con-
centration of inorganic nanoparticles using spICP-MS with the dynamic mass flow
approach, J. Anal. At. Spectrom. (2020), https://doi.org/10.1039/C9JA00415G
accepted.
[44] H.E. Pace, N.J. Rogers, C. Jarolimek, V.A. Coleman, C.P. Higgins, J.F. Ranville,
Determining transport efficiency for the purpose of counting and sizing nano-
particles via single particle inductively coupled plasma mass spectrometry, Anal.
Chem. 83 (2011) 9361–9369.
[45] K. Marschner, S. Musil, J. Dědina, Flame-in-gas-shield and miniature diffusion
flame hydride atomizers for atomic fluorescence spectrometry: optimization and
comparison, Spectrochim. Acta, Part B 109 (2015) 16–23.
[46] P. Vinas, I. López-García, B. Merino-Merono, M. Hernández-Córdoba, Ion chroma-
tography–hydride generation-atomic fluorescence spectrometry speciation of tell-
urium, Appl. Organometal. Chem. 19 (2005) 930–934.
[47] E. Nováková, K. Horová, V. Červený, J. Hraníček, S. Musil, UV photochemical vapor
generation of Cd from a formic acid based medium: optimization, efficiency and
interferences, J. Anal. At. Spectrom. 35 (2020) 1380–1388.
[48] J. Dědina, Atomic absorption coefficient of the Se 196 nm line–theoretical calcu-
lation and experimental evaluation, Spectrochim. Acta, Part B 46B (1991) 379–391.
[49] Q. Tan, Y. Pan, L. Liu, S.B. Shu, Y. Liu, Determination of ultratrace tellurium in
water by hydride generation atomic absorption spectrometry using online separa-
tion and pre-concentration with nano-TiO2 microcolumn, Microchem. J. 144
(2019) 495–499.
[50] W. Zeng, J. Hu, H.J. Chen, Z.R. Zou, X.D. Hou, X.M. Jiang, Cobalt ion-enhanced
photochemical vapor generation in a mixed acid medium for sensitive detection of
tellurium(iv) by atomic fluorescence spectrometry, J. Anal. At. Spectrom. 35 (2020)
1405–1411.
[51] C.B. Zheng, Q. Ma, L. Wu, X.D. Hou, R.E. Sturgeon, UV photochemical vapor gen-
eration-atomic fluorescence spectrometric determination of conventional hydride
generation elements, Microchem. J. 95 (2010) 32–37.
[52] E. Nováková, J. Smolejová, T. Položijová-Resslerová, J. Hraníček, Increasing the
sensitivity of electrochemical generation of volatile Te species, Spectrochim. Acta,
Part B 149 (2018) 294–299.
[53] X.J. Jiang, W.E. Gan, S.P. Han, Y.Z. He, Determination of Te in soldering tin using
continuous flowing electrochemical hydride generation atomic fluorescence spec-
trometry, Spectrochim. Acta, Part B 63 (2008) 710–713.
[54] H.Y. He, X.H. Peng, Y. Yu, Z.M. Shi, M. Xu, S.J. No, Y. Gao, Photochemical vapor
generation of tellurium: synergistic effect from ferric ion and nano-TiO2, Anal.
Chem. 90 (2018) 5737–5743.
[55] P. Dvořák, M. Talába, A. Obrusník, J. Kratzer, J. Dědina, Concentration of atomic
hydrogen in a dielectric barrier discharge measured by two-photon absorption
fluorescence, Plasma Sources Sci. Technol. 26 (2017) 085002.
[56] X.F. Mao, Y.H. Qi, J.W. Huang, J.X. Liu, G.Y. Chen, X. Na, M. Wang, Y.Z. Qian,
Ambient-temperature trap/release of arsenic by dielectric barrier discharge and its
application to ultratrace arsenic determination in surface water followed by atomic
fluorescence spectrometry, Anal. Chem. 88 (2016) 4147–4152.
[57] Y.H. Qi, X.F. Mao, J.X. Liu, X. Na, G.Y. Chen, M.T. Liu, C.G. Zheng, Y.Z. Qian, In situ
dielectric barrier discharge trap for ultrasensitive arsenic determination by atomic
fluorescence spectrometry, Anal. Chem. 90 (2018) 6332–6338.
[58] M.T. Liu, J.X. Liu, X.F. Mao, X. Na, L. Ding, Y.Z. Qian, High sensitivity analysis of
selenium by ultraviolet vapor generation combined with microplasma gas phase
enrichment and the mechanism study, Anal. Chem. 92 (2020) 7257–7264.
[59] P. Dvořák, M. Mrkvičková, A. Obrusník, J. Kratzer, J. Dědina, V. Procházka,
Fluorescence measurement of atomic oxygen concentration in a dielectric barrier
discharge, Plasma Sources Sci. Technol. 26 (2017) 065020.