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Journal of Taibah University for Science 11 (2017) 540–547

Flame atomic absorption determination of zirconium in glass and

refractory bricks after coprecipitation with aluminium hydroxide
Ardeshir Shokrollahi ∗ , Masoud Gohari
Department of Chemistry, Yasouj University, 75918-74831 Yasouj, Iran
Received 17 August 2015; received in revised form 16 November 2015; accepted 20 November 2015
Available online 21 December 2015

Abstract
A simple preconcentration method for zirconium based on coprecipitation with aluminium hydroxide prior to flame atomic
absorption (FAAS) determination was established. The recovery values of the analyte ions were higher than 95%. Such parameters
as the type of hydroxide ion source for precipitation, type of acid for the dissolution step, amount of Al3+ ion as the collector,
pH, temperature, standing time and centrifuge time were optimized using 50 mL of a solution containing 150 ␮g of zirconium.
The effect of the solution volume and influences of matrix ions on the extraction of the analyte were also examined. Under the
optimum conditions, the calibration curve was linear up to 10 mg L−1 . The relative standard deviation for solutions containing
150 ␮g of zirconium was found to be 3.9%. The limit of detection (LOD) and limit of quantitation (LOQ) were calculated as 0.17
and 0.57 mg L−1 , respectively. The method is capable of extracting the analyte in different samples with volumes of up to 250 mL.
The preconcentration factor for 250 mL and enhancement factor for 50 mL of analyte solution were calculated to be 250 and 40,
respectively. The proposed method was successfully applied for the determination of zirconium in glass and refractory brick samples.
© 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: Coprecipitation; Zirconium; Aluminium hydroxide; Refractory bricks; Glass; Atomic absorption spectrometry

1. Introduction
Zirconium is the second element of group 4B. This
element’s name is taken from the name of the mineral zir-
con (ZrSiO4 ), the most important source of zirconium.
∗ Corresponding author. Tel.: +98 7433223048;
fax: +98 74133223048.
E-mail address: ashokrollahi@mail.yu.ac.ir (A. Shokrollahi).
Peer review under responsibility of Taibah University.
http://dx.doi.org/10.1016/j.jtusci.2015.11.006
1658-3655 © 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
The word zircon comes from the Persian word zargun
meaning “gold-coloured” [1]. Zirconium is a corrosion
resistant metal, and it is used in high performance pumps
and valves. Because it also does not easily absorb neu-
trons, zirconium is widely used in nuclear reactors.
Zirconium is superconductive at low temperatures and is
used to make superconductive magnets, which offer the
possibility of realizing the direct large-scale generation
of electric power [2].
Zirconium dioxide (ZrO2 ) is one of the most studied
ceramic materials. It can withstand very high temper-
atures and is used to make crucibles, refractory bricks
and to line the walls of high temperature furnaces. Fused
cast AZS (alumina, zirconia, silica) and AZCS (alumina,
 A. Shokrollahi, M. Gohari / Journal of Taibah University for Science 11 (2017) 540–547
zirconia, chromia, silica) refractories, which have excel-
lent chemical stabilities against molten glass, are the
most widely used materials both in the glass contacts
and superstructures of glass melting furnaces.
The action of zirconium on biological systems
presents an enigma. Some research presents a biolog-
ical effect of zirconium, whereas others do not support
this idea. However, the level of toxicity has been found to
be moderately low in both histological and cytological
studies [3]. In analytical chemistry, zirconium is con-
sumed as an absorption modifier in ET-AAS alone [4] or
with other modifiers [5].
Various analytical techniques used for the deter-
mination of zirconium in different matrices include
spectrophotometry [6], fluorescence spectrophotometry
[7], atomic absorption spectrometry [8], inductively
coupled plasma atomic emission spectrometry [9],
inductively coupled plasma mass spectrometry [10], iso-
tope dilution mass spectrometry [11], X-ray fluorescence
[12], neutron activation analysis [13], proton activation
analysis [14], potentiometry [15], kinetic potentiometry
[16], polarography [17], stripping voltammetry [18,19],
impedimetry [20], and liquid chromatography [21].
Due to analyte levels lower than the quantitation lim-
its of instrumental techniques and interference effects,
separation and preconcentration methods such as liq-
uid extraction [22], extraction based on ion exchange
resin [23], solid phase extraction [24,25], and cloud point
extraction [26] have been used prior to zirconium deter-
mination.
The coprecipitation method has been widely used
for the preconcentration of trace amounts of analytes
[27–31] due to some advantages including its simplicity
and rapidity as well as that it obeys green chemistry rules.
This method has been applied for the preconcentration
of trace amounts of zirconium using different collec-
tors [32–38]. Iron (III) hydroxide [33,35], lanthanum
hydroxide [34,37] Cu(OH)2 , and Fe2 O3 (in the pres-
ence of sub stoichiometric amounts of complexon) [32]
have been used as collectors in the coprecipitation of
zirconium.
Aluminium hydroxide has been widely used as a col-
lector for the coprecipitation of various analytes [39–42],
and in this research, the objective was to use aluminium
hydroxide for the collection of zirconium. Because the
Al3+ ion enhances the zirconium signal in atomic absorp-
tion spectrometry [43], it can be an excellent collector
as well as an absorption modifier. The results of this
study support the preconcentration and extraction of
trace amounts of zirconium after coprecipitation with
aluminium hydroxide prior to determination by flame
atomic absorption spectrometry (FAAS).
541
2. Experimental
2.1. Instrument
All determinations were performed by using a Perkin-
Elmer Atomic Absorption Spectrophotometer (Model
460) equipped with a Zr hallow cathode lamp and nitrous
oxide burner head. The lamp current was adjusted to
40 mA. The wavelength and slit were 360.1 nm and
0.2 nm, respectively. The fuel to oxidant ratio was
adjusted to form a reducing (rich red) flame. The pH
value of the solution was measured by an AZ pH meter
(model 86502) equipped with an AZ combined glass
electrode. A TE214S Sartorius microbalance was used
for weighing the chemicals. An Orum Tadjhiz T4.50
centrifuge was used to accelerate the phase separation
process.
2.2. Reagents and solutions
All chemicals used in this work were of analytical-
reagent grade. Double distilled water was used through-
out. A stock solution of 1000 mg L−1 zirconium was
prepared from dissolving 0.3533 g of zirconyl chloride
octahydrate (Merck, Darmstadt, Germany) in double
distilled water, transferring it to a 100 mL polyethy-
lene volumetric flask, adding 5 mL of concentrated HCl
(Merck) and diluting it to volume with double distilled
water. A solution of 1000 mg L−1 Al3+ ion was prepared
by dissolving 8.9492 g of AlCl3 ·6H2 O (Merck) in double
distilled water, followed by dilution to 1000 mL. A solu-
tion of 10% (w/v) KOH, Na2 CO3 or NaOH was prepared
by dissolving 10 g of KOH, Na2 CO3 or NaOH (all from
Merck) in double distilled water, followed by dilution to
100 mL in a polyethylene flask separately. An ammonia
solution 5% (v/v) was prepared by transferring 20 mL of
25% ammonia (Merck) to a 100 mL polyethylene flask
and diluting it to the mark. A lithium metaborate (J.T.
Baker), was used as the flux, for real sample preparation.
2.3. Procedure
For the optimization, in a 50 mL centrifuge tube, the
pH of a solution of 3 mg L−1 zirconium and 40 mg L−1
Al3+ ion as the collector was adjusted to 8 by adding
an appropriate amount of 5% NH3 and diluting to the
mark with double distilled water. Due to the formation
of aluminium hydroxide, the solution becomes turbid. In
order to facilitate phase separation, the tube containing
the solution and precipitate was centrifuged at 4000 rpm
at room temperature for 5 min. The supernatant was
removed, and the precipitate was dissolved by adding a
542 A. Shokrollahi, M. Gohari / Journal of Taibah University for Science 11 (2017) 540–547
few drops of concentrated HCl along with shaking. The
final volume of 1 mL was reached with double distilled
water. The analyte in the final solution was determined
by flame atomic absorption spectrometry.
2.4. Preparation of real samples
AZS brick, AZCS brick, and glass samples were pul-
verized and screened by sieve No. 120. AZS brick and
glass samples were prepared based on the literature [33]
and involved fusing 0.1000 g of them with approximately
0.6 g of lithium metaborate (LiBO2 ) in a platinum cru-
cible at 1000 ◦ C. Then, the melt was dissolved with a hot
dilute HCl solution, transferred to a 250 mL polyethylene
volumetric flask, and diluted to volume with double dis-
tilled water. AZCS brick sample preparation was similar
to that of AZS brick except for the fusion procedure,
which was performed with a mixture of 0.6 g of lithium
metaborate and 0.2 g of potassium carbonate. Two millil-
itres of prepared refractory samples or 10 mL of glass
sample solutions were analyzed according to the proce-
dure given in Section 2.3.
3. Results and discussion
In order to achieve an acceptable recovery, the effects
of variables that may have a significant influence on the
coprecipitation, dissolution and atomic absorption sig-
nal, such as the hydroxide ion type, type of acid solvent,
pH, amount of collector, standing and centrifuge time,
temperature, volume of sample, and interfering ions,
were examined.
3.1. Effect of the hydroxide ion source
The coagulation step is a very important factor for
achieving a quick coprecipitation and the easy sepa-
ration of the coprecipitate from the supernatant with
a simple separation procedure. A high recovery of the
analyte and good reproducibility are also related to the
coprecipitation conditions; therefore, initial studies were
performed with different bases such as ammonia (NH3 ),
soda ash (Na2 CO3 ), caustic soda (NaOH) and caustic
potash (KOH) with recoveries of 104%, 95%, 97%, and
97%, respectively. Because ammonium ion increases the
signal of Zr [44], it was selected as the hydroxide ion
source in the coprecipitation procedure.
3.2. Effect of the acid type as the solvent
HF, HClO4 , HNO3 , and HCl were used for the disso-
lution of the precipitate. Due to the high concentration
Fig. 1. Effect of the pH on the recovery of the analyte: 150 ␮g of
zirconium, 2 mg of Al3+ ion, pH adjustment with ammonia 5% (v/v)
and dilute HCl, initial volume of 50 mL, at 25 ◦ C.
of Al3+ ions and the formation of slightly soluble AlF6 ,
HF was not acceptable for dissolving the precipitate.
The recoveries of the analyte with HClO4 and HNO3
were 55% and 20%, respectively. An acceptable recovery
(over 95%) was found by using HCl; therefore, all fur-
ther work was performed using HCl for the dissolution
of the precipitate.
3.3. Effect of the pH
The influence of the pH of the sample solution on the
recovery of zirconium was investigated in the pH range
of 5.0–10.0 by adjusting the pH value of the solution with
the addition of different amounts of a 5% ammonia solu-
tion. As shown in Fig. 1, zirconium was quantitatively
coprecipitated in the pH range of 7.0–9.0. The decrease
in the signal at pH values >9.0 is due to the dissolution of
the precipitate as Al(OH)4 − in highly alkaline solutions.
In order to achieve a high efficiency and good selectiv-
ity, a pH of approximately 8 was selected for all of the
subsequent coprecipitation experiments.
3.4. Effect of the amount of Al3+ ion
The amount of collector is very important and must
be optimized. A sufficient amount of collector must
be added to the sample solution to ensure the perfect
coprecipitation of the analyte; in contrast, the amount
of collector must be small to limit the final volume.
Therefore, the influence of the amount of Al3+ ion
as the collector on the recovery of zirconium was
investigated in the range of 0–3.0 mg. The results are
depicted in Fig. 2. Acceptable recovery values were
obtained in the range of 1.0–2.5 mg of Al3+ ion. In
lower amounts, the collection is incomplete, and with
higher amounts of collector, the high concentration of
collector in final solution and high viscosity of the final
 A. Shokrollahi, M. Gohari / Journal of Taibah University for Science 11 (2017) 540–547
Fig. 2. Effect of the amount of Al3+ ion on the recovery of the analyte:
150 ␮g of zirconium, different volumes of Al (1000 mg L−1 ), pH = 8,
initial volume of 50 mL, at 25 ◦ C.
solution limit the absorption signal. Consequently, all
further investigations were performed with 2 mg (2 mL
Al3+ 1000 mg L−1 ) of Al3+ ion. According to the litera-
ture [43], 0.2% of Al3+ ion is needed for increasing the
zirconium signal in atomic spectrometry. In this case, the
selected value for the collector in the final solution con-
forms to this value for the Al3+ ion, which is proposed
for increasing the zirconium absorption signal in flame
atomic absorption spectrometry.
3.5. Effects of the standing time, temperature and
centrifugation time
The standing time, which is important for the quality
of the coprecipitation, was evaluated at different times in
the range of 0–6 h at room temperature. The results are
shown in Fig. 3. Quantitative recovery was found after
the formation of the precipitate, and further contact time
did not lead to better recovery; therefore, no standing
time was considered for the following experiments, and
phase separation was performed after adjustment of the
pH. It must be noted that for standing times above 4 h, the
Fig. 3. Effect of the contact time on the recovery of the analyte: 150 ␮g
of zirconium, 2 mg of Al3+ ion, pH = 8, initial volume of 50 mL, dif-
ferent standing times, at 25 ◦ C.
543
Fig. 4. Effect of the temperature on the recovery of the analyte: 150 ␮g
of zirconium, 2 mg of Al3+ ion, pH = 8, initial volume of 50 mL, at
different temperatures.
solubility of the precipitate in acidic medium decreased,
and a viscous fluid was formed after the addition of acid.
The effect of the temperature on the coprecipitation
was also examined in the range of 25–70 ◦ C. As seen
in Fig. 4, quantitative recovery was obtained at room
temperature. A viscous solution was formed after the
dissolution of the precipitate, which had been formed in
high temperatures similar to the case of a long standing
time. A low aspiration efficiency of the viscous solution
and, consequently, a low atomization efficiency in FAAS
would be the reasons for the decreasing absorption signal
at high temperatures and long standing times. Thus, room
temperature was selected for all of the experiments.
The centrifugation time was also optimized within the
1–15 min time period with centrifugation at 4000 rpm.
The required centrifugation time for the successful
coprecipitation with quantitative recovery of the analyte
was determined to be at least 2 min, but in order to obtain
a more compact precipitate, a time of 5 min was chosen
for all subsequent coprecipitation experiments.
3.6. Effect of the sample volume
In order to examine the capability of the presented
coprecipitation system in a large sample volume, the
effect of the sample volume on the coprecipitation effi-
ciency was examined in solution volumes ranging from
15 to 300 mL with recoveries over 95% considered to be
acceptable. The precipitate was successfully dissolved
in 0.5 mL of concentrated HCl, and the final volume was
completed to 1.0 mL with double distilled water. The
recovery was acceptable up to 250 mL. The preconcen-
tration factor based on the ratio of the highest sample
volume (250 mL) to the final volume (1 mL) obtained as
250.
Although the presented coprecipitated system is capa-
ble of extracting zirconium from solutions with different
volumes up to 250 mL, to save time and materials, we
544 A. Shokrollahi, M. Gohari / Journal of Taibah University for Science 11 (2017) 540–547

Table 1
Effects of diverse ions on the zirconium recovery under the following conditions: 150 ␮g of zirconium, 2 mg of Al3+ ion, pH = 8, initial volume of
50 mL, at 25 ◦ C.
Ion Recovery (%) Concentration (mgL−1 )

NH4 + , Na+ , K+ , Ca2+ , Ba2+ , B3+ (as H3 BO3 ), OAC− , 105, 101, 97, 95,97, 95, 95, 1000
NO3 − , Cl− , Br− , I− , MoO4 2− 99, 98, 95, 105,97
Mg2+ , Zn2+ , Fe3+ , Al3+ , Cr2 O7 2− , SiO3 2− , SO4 2− , F− 97,96, 95, 99, 96,95, 95, 99 100
Cu2+ , Ni2+ , Mn2+ , Ti4+ (dissolved TiO2 ), PO4 3− 95, 96, 96, 98, 95 10

applied a 50 mL sample volume for all optimizations and
determinations.
3.7. Interference studies
In order to assess the possible analytical applications
of the presented coprecipitation procedure, the effects
of some foreign ions that ordinarily exist in various real
samples were examined under the optimized conditions.
The recovery of the analyte was generally higher than
95%. A tolerable limit was defined as the highest amount
of foreign ions that produce an error not exceeding 5%
in the determination of the analyte by the coprecipitation
method. The tolerable levels of NH4 + , Li+ , Na+ , Ca2+ ,
Mg2+ , Cr2 O7 2− , and B3+ ions are suitable for the sep-
aration and preconcentration of zirconium in glass and
refractory brick samples (Table 1).
3.8. Analytical performance
An Abs vs. concentration calibration graph was
plotted after the coprecipitation of 50 mL of standard
solutions under the optimum experimental conditions.
The graph was linear up to 10 mg L−1 . The equation of
the calibration graph was y = 0.0243x + 0.003 with a cor-
relation coefficient of 0.9991. The detection limit (LOD)
and limit of quantitation (LOQ) under the optimal exper-
imental conditions for ten blank solutions and based on
three times the standard deviation of the blank were
found to be 0.17 and 0.57 mg L−1 , respectively. The pre-
cision of the method was evaluated under the optimum
conditions. For this purpose, the procedure was repeated
ten times with 50 mL of solution containing 3 mg L−1
zirconium. The relative standard deviation was calcu-
lated to be 3.9%. The preconcentration factor, which is
the ratio of the initial volume to the final volume, was

Table 2
Zirconium determination in refractory brick samples (n = 4).
Sample Added (mg L−1 ) Found (mg L−1 ) Recovery (%) Value in sample (ZrO2 %) Accepted
value (ZrO2 %)

AZS bricka 0.0 3.46 ± 0.10 – 36.1 ± 0.4 36.4

1.0 4.53 ± 0.11 98.5
2.0 5.38 ± 0.13 101.4
3.0 6.45 ± 0.19 100.1
4.0 7.48 ± 0.20 99.8

AZCS brickb 0 1.73 ± 0.10 – 18.2 ± 0.2 18

1.0 2.74 ± 0.10 100.2
2.0 3.68 ± 0.12 98.5
3.0 4.62 ± 0.14 97.6
4.0 5.73 ± 0.14 99.9
Glassc 0.0 Ndd – – –
1.0 1.03 ± 0.10 102.5
2.0 1.97 ± 0.10 98.3
3.0 3.03 ± 0.11 101.1
4.0 4.10 ± 0.13 102.5
a Type RT-36 from the Ruitai Company [45].
b Type Zichrom 30 from the Sefpro Corporation [46].
c C glass, produced at the Iran Glass Wool Co.
d Not detected.
 A. Shokrollahi, M. Gohari / Journal of Taibah University for Science 11 (2017) 540–547 545

Table 3
Comparison of the characteristics of the presented method for zirconium determination with those of some previous methods.
Method LOD (mg L−1 ) RSD (%) Dynamic range (mg L−1 ) Enhancement factor Ref

Stripping voltammetry 2 × 10−5 1.7 0.001–0.01 60 19

ICP-AES (liquid extraction) 5 × 10−3 0.11 0.02–0.4 NR 22
Spectrophotometry (SPE) 1 × 10−3 3.7 0.005–0.3 80 25
ICP-OES (cloud point) 3 × 10−4 2.9 5 × 10−4 –1.0 38.9 26
Isotope dilution (coprecipitation) NR 8.3 1–100 NR 32
ICP-AES (coprecipitation) 0.02 1.0 1–50 25 37
Presented method 1.7 × 10−1 3.9 up to 10 40 –

NR, not reported.

calculated as 250 for 250 mL of analyte solution.
Because the equation of calibration graph for the direct
signal of zirconium was y = 0.0006x + 0.003 with a cor-
relation coefficient of 0.9992, the enhancement factor,
which is calculated by dividing the slope of the cali-
bration curve with coprecipitation by the slope of the
calibration curve without coprecipitation, was calculated
to be 40 for 50 mL of analyte solution. Sample through-
put was also found to be 12 samples h−1 .
3.9. Application to real samples
The proposed method was applied for the determina-
tion of zirconium in AZS and AZCS refractory bricks
as well as glass samples produced in a furnace with
AZS and AZCS refractory bricks in its paving and walls.
As shown in Table 2, the recoveries of spiked sam-
ples are acceptable, and there is satisfactory agreement
between the results obtained by the presented method
and accepted values, suggesting that the coprecipitation
procedure is suitable for analysing the zirconium content
in refractory bricks, glass, and related materials.
4. Conclusions
Due to the low sensitivity for the determination of
zirconium by flame atomic absorption spectrometry,
a preconcentration step prior to the determination is
needed for most samples, such as silicate glass. Copre-
cipitation is one of the most efficient methods for the
preconcentration of zirconium. The coprecipitation of
zirconium with different collectors has been reported
in the literature [32–38], but using the Al3+ ion (as a
collector which increases the sensitivity of zirconium
in FAAS) has not been reported previously. The pro-
posed coprecipitation method, which is performed at
room temperature, is simple, fast, efficient and inexpen-
sive for the determination of zirconium. Additionally,
ammonia (as the hydroxide ion source) similar to the
Al3+ ion, increases the zirconium sensitivity in flame
atomic absorption spectrometry. This method can be
recommended for the routine analysis of zirconium in
geological and industrial samples, especially refractory
bricks as well as water and biological samples. Under the
optimum experimental conditions, quantitative recovery
was achieved with a preconcentration factor of 250.
Merit numbers of the presented method have been
compared with those of some previous methods for
the determination of zirconium. As shown in Table 3,
although the limit of detection of the proposed method is
higher than those of all of the reported methods, the RSD
of the presented method is better than those of some of
the other methods [32] and is comparable to that of spec-
trophotometry [25]. Additionally, the dynamic range of
the proposed method is broader than that of stripping
voltammetry [19] and is comparable to that of ICP-AES
(liquid extraction) [22]. This method also has a good pre-
concentration factor compared with all of the methods
reported in Table 3.
Acknowledgements
We gratefully acknowledge the support of Yasouj
University for this study. We also acknowledge the Iran
Glass Wool Company for assistance with this research,
especially for preparing the zirconia-containing bricks
and glass samples.
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