Determination of Cd(II), Zn(II) and Ag(I)in different matrixes after solid phase extraction on sodium dodecyl sulfate(SDS)-coated alumina as their 2,3 Di Hydro 2,3 ParatolylQinazoline (1 H)-4 one (DPTQO) by flameatomic absorption spectrometric

Article abstract of DOI:10.13005/ojc/320165

A sensitive and selective solid phase extraction procedure for the determination of traces of Cd(II), Zn(II) and Ag(I) ions has been developed. An alumina-sodium dodecyl sulfate (SDS) coated on with 2,3 Di Hydro 2,3 paratolylQinazoline (1 H)-4 one (DPTQO)

Full text of DOI:10.13005/ojc/320165

ISSN: 0970-020 X
CODEN: OJCHEG
016, Vol. 32, No. (1):
Pg. 575-584
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
2
www.orientjchem.org
Determination of Cd(II), Zn(II) and Ag(I)in Different Matrixes
After Solid Phase Extraction on Sodium Dodecyl Sulfate(SDS)-
Coated Alumina as their 2,3 Di Hydro 2,3 ParatolylQinazoline
(
1 H)- 4 one (DPTQO) by FlameAtomic Absorption
Spectrometric
1
2,3
2,
4
FARvEH RAOUFI *,SAIDEH BAꢀHERI , PEDRAM NASEHI EBRAHIM NIkNAM ,
kHODA BAkHSH NIkNAM and HAMID REZA FARMANI6
5
1
Chemistry Department, Islamic Azad University, Ilam Branch, Ilam, Iran.
2
Chemistry Department, Islamic Azad University, Dashtestan, Iran.
3
Young Researchers and Elite Club, Shiraz Branch, Islamic Azad University, Shiraz, Iran.
4
Chemistry Department, Islamic Azad University, Kangan Branch, Kangan, Iran.
5
Department of Chemistry, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran.
6
Chemistry Department, Islamic Azad University, Ahram Branch, Ahram, Iran.
*
Corresponding author E-mail: fraoufi@yahoo.com
http://dx.doi.org/10.13005/ojc/320165
(Received: January 18, 2016; Accepted: February 22, 2016)
ABSTRACT
A sensitive and selective solid phase extraction procedure for the determination of traces of
Cd(II), Zn(II) and Ag(I) ions has been developed. An alumina-sodium dodecyl sulfate (SDS) coated
on with 2,3 Di Hydro 2,3 paratolylQinazoline (1 H)- 4 one (DPTQO).The influences of the analytical
parameters including pH and sample volume were investigated.Common coexisting ions did not
interfere on the separation and determination of analytes under study.The adsorbed analytes were
-
1
-1
2+
desorbed by using 6mL of 4 mol L nitric acid.The responses are linear 0.02–0.85 µg mL for Cd
-
1
2+
-1
+
ion0.01–0.90 µg mL for Zn and0.02–0.92µg mL for Ag detection limit for Cd(II), Zn(II) and Ag(I)
ions were found to be 1.4, 1.3 and1.12(ng mL ), respectively.It was found that the recovery for Cd ,
Zn and Ag ions were 97.7, 98.2 and 98.0 with RSD of 1.9, 1.8 and 1.7. It was also observed that
recovery for repeated recovery on the same solid phase not varies more than 3%. The presented
procedurewas successfully applied for determination of analytes in radiology wastewater, amalgam,
natural water and blood samples.
-1
2+
2
+
+
keywords: Surfactant Coated on Alumina, Solid Phase Extraction,
Determination, recovery. Atomic absorptionspectrometry.

576
RAOUFI et al., Orient. J. Chem., Vol. 32(1), 575-584 (2016)
INTRODUCTION use in solid phase extraction works was introduced by
Hiraide et al. . The organic reagent is incorporated
Trace metals are widely spread in the cores of admicelles of sodium dodecyl sulfate
22
in environment and may enter the food chain attached to alumina surfaces.New organic reagents
from the environment. Some trace metals are are immobilized on surfactant coated on alumina for
2
3,24
essential elements and play an important role in separation and enrichment of different metal ions
,
25
human metabolism. On the other hand, at higher and recently polyaromatic hydrocarbon as well .The
concentrations all of the metals are recognized as purpose of this work is to investigate the feasibility of
1,2
potentially toxic . Therefore determination of trace absorption of these ions including Cd(II), Zn(II) and
heavy metals in different environmental samples is of Ag(I) ions on SDS coated on alumina modified with
great interest to analytical chemists. Recently, solid 2,3 Di Hydro 2,3 paratolyl Qinazoline (1 H)- 4 one
phase extraction has been successfully utilized for (DPTQO). The parameters including pH of sample,
the preconcentration and separation of trace metal amount of ligand and solid phase, type of eluting
3
,4
ions . These difficulties and limitations can be agent and time andflow rate were optimized.
overcome with doing a preliminary separation and/or
preconcentration step and subsequent measurement
by FAAS to decrease the matrix interference (by its
simplification) or improve in the detection limit . Instruments
Variousreconcentrationseparationmethodsincluding All the determinations of the analytes were
EXPERIMENTAL
5
,6
solid-phase extraction, membrane filtration, and carried out using a Sens AA GBC double beam
electroanalytical techniques have been used for this atomic absorption spectrometer (AAS) equipped
7-10
purpose .Solid phase extraction (SPE) composed with deuterium background corrector. Hollow
of two distinct stages; a) selective and reversible cathode lamps were used as radiation sources
binding of analytes to a solid support (modified);and and the operational conditions of the equipment
b) their subsequent elution with a small volume of were established according to the manufacturer’s
solvent that make possible simultaneous simplified recommendations for each element. An adjustable
matrices and enhance in sensitivity. Among various capillary nebulizer and supplies of acetylene
sorbents, silica gel chemically bonded with various and air were used for the generation of aerosols
organic compounds has received great attention and atomizations. The UV/V is spectra were
due to its goodmechanical and thermal stability, obtained from a Perkin-Elmer, model Lambda 2
11-15
less susceptibility to swelling and shrinking . The spectrophotometer. A Gen way model 3510 pH/Ion
SPE can easily be adapted for FAAS to improve meter with a combined glass electrode was used for
the detection limit and selectivity of determinations. pH measurements. Laboratory glassware was kept
Inour laboratory using various types of sorbents over night in 10% nitric acid solution.Before use, the
1
6
17
including activatedcarbon , SDS-coated alumina , glassware was rinsed with distilled deionized water
1
8
modified chromosorb ,and modified polyvinyl and dried in a laminar flux cabinet.
1
9
chloride separation and/or preconcentration of
metal ions has been gaining popularity because of Reagents
its high concentrating ability and simple operation.
Doubly distilled deionized water was used
Among the various solid phases, those obtained by through out the experimental work.Stock solutions of
immobilization of chelating agent on support viz. all understudy elements were prepared by dissolving
alumina and silica gel have gained much attention appropriate amount of ultrapure salt obtained from
with high repeatability and large lifetime.The design Merck (Darmstadt, Germany) in 4M HNO . Working
3
of a stable and selective solid phase sorbents for standard solutions were obtained by appropriate
separation and preconcentration of a target metal ion dilution of the stock standard solution. The pH was
-1
depends on different factors such as the nature of adjusted by addition of0.1mol L nitric acid or 0.1mol
20
-1
solid support, its surface area and activity . Among
L
potassium hydroxide. The Al O and sodium
2 3
these adsorbents, alumina is an important place in dodecyl sulfate (SDS) were purchased from Merck.
the solid phase extraction studies of heavy metal The SDS solution was prepared by dissolving 1.0 g
2
1
ions . A new modification mode for the alumina to of surfactantin 100mL volumetric flask while stirring.

RAOUFI et al., Orient. J. Chem., Vol. 32(1), 575-584 (2016)
577
The ligand 2,3 Di Hydro 2,3 paratolyl Qinazoline (1
H)- 4 one (DPTQO) was synthesized according to
literature .
Preparation of solid phase
A 10mL of sodium dodecyl sulfate (SDS)–
DPT QO solution was added to 30mL of water
solution containing 1 g of the Al O particles.While
2
6
2
3
Preparationof2,3DiHydro 2,3paratolylQinazoline
shaking the suspension with a stirrer, the pH was
-
1
(
1 H)- 4 one (DPTQO)
A mixture of isatoic anhydride (1 mmol),
adjusted to 2 with 2mol L hydrochloric acid to
form DPT QO impregnatedad micelles on alumina
particles. After mixing for15 min, the supernatant
solution was discarded and the remaining was used
as modified solid phase.The solid phase was purified
para methylbenzaldehyde (2mmol), and ammonium
acetate or primary amine (1.1 mmol) in ethanol
(
5 mL) was added silica-bonded N-propylsulfamic
0C
-1
acid (0.1 g) and heated at 80 in an oil bath. After
completion of the reaction, as indicated by TLC, the
reaction mixture was filtered and remaining washed
with warm ethanol (2-5 mL). After cooling, the
corresponding 2,3-dihydroquinazolinone products
were obtained which purified by recrystallization from
hot ethanol. The recovered catalyst was dried and
reused for subsequent runs.The product was purified
by column chromatography on silica gel [eluent:
EtOAc/n-hexane (1:3)] to give pure 2,3 Di Hydro
by passing 4mL of 4 mol L HNO and neutralized
3
-
1
with 0.1mol L KOH. The sorbent in refrigerator is
stable for at leastone month.The SDS concentration
was fixed below the CMC of SDS(8×10 mol L )
to avoid formation of micelles in the aqueous
solution.
"
3
-1
Application to Real Samples
Real samples including blood samples
2
7
were treated as described previously . Then the
Test Procedure described above was applied. For
the application of the present procedure to amalgam
alloy, an accurately weighed 0.4 g portion of each
amalgam alloy sample was digested as described
2
9
,3 paratolyl Qinazoline (1 H)- 4 one (DPTQO) in
0% yield, figure 1, was synthesized according to
2
6
literature .
0
28,29
Mp: 243-245 C
previously . and dissolved in the smallest volume
1
H NMR (DMSO-d , 400 MHz) d: 2.22 (s,
of water, and the solution was transferred to a
100 mL volumetric flask by adjustment of the pH
of the solution to the desired value; then the Test
Procedure described above was carried out. The
waste radiographic samples were prepared for the
measurement of their cadmium, zinc and silver ions
content as follows. To 20 mL sample were added
about 10 mL 4M nitric acid and 10 mL water. The
solution was boiled until its volume was reduced
to20 mL.The resulting solution was neutralized with
NaOH solution to the desired pH value and filtered.
The filtrate and washings were diluted to 50 mL
in a volumetric flask, and then the Test Procedure
described above was applied.
6
3H), 2.26 (s, 3H), 6.18 (d, 1H, J= 2.8 Hz), 6.68-6.75
(
(
m, 2H), 7.09-7.15 (m, 6H), 7.23-7.28 (m, 3H), 7.55
d, 1H, J= 2.5 Hz), 7.72 (dd, 1H, J = 7.8 Hz, J = 1.5
1
2
Hz).
13
C NMR (DMSO-d , 100 MHz):20.6, 72.6,
6
1
1
1
14.7, 115.4, 117.4, 126.0, 126.4, 127.8, 128.9,
29.0, 133.6, 135.2, 137.5, 137.9, 138.3, 146.5,
62.2.
-
1
IR (KBr) (cm ): 3265, 3078, 1640, 1614,
516, 1475, 1383, 1250, 1152, 1112, 1010, 818,
65, 752, 51
1
7
RESULTS AND DISCUSSION
The adsorption of SDS on alumina is highly
dependent on thesolution pH. Negatively charged
SDS was more effectively and nearly quantitatively
”
1
retained (about 99% even in 2mol L nitricacid) on
the positively charged alumina surfaces at pH 1–4.
Therefore, retention of organic compounds on SDS-
Fig. 1:The structure of ligand2,3 Di Hydro 2,3
paratolylQinazoline (1 H)- 4 one (DPTQO).
30–32
coated alumina
occurs.This phenomenon greatly

578
RAOUFI et al., Orient. J. Chem., Vol. 32(1), 575-584 (2016)
increases by decreasing the pH due to the higher have attracted increasing attention, generally due
30,31
charge density on the mineraloxide surface . The to their reactivity mainly in the area of binding
anionic surfactant SDS is effectively retained on small molecules. Consequently, we study the
2+
2+
+
positively charged alumina surfaces via formation of complexation of Cd , Zn and Ag ions in methanol.
32
self-aggregates over a wide pH range (1–6), where Typical spectra and moleratio plot were depicted in
+
as very little amount of SDS could be retained on inert Figure2, for Ag ion. As it were observed, significant
surface of alumina. Therefore, alumina is essential apparent changes in the spectrumof ligand, on
for the preparation of surfactant-coated sorbents. It addition of metal ions indicate that, the ligand has
was also confirmed that, while solid phase of alumina strong interaction with metal ions and is an efficient
or alumina coated with SDS show lowtendency for sorbentfor trace metal enrichment.Further analyzing
retention of metal ions, the solid phase of immobilized the absorbance atmaximum wavelength using Kinfit
Schiff base on surfactant-coated alumina was program the stoichiometry and stability constant of
capable ofretaining these metal ions from the sample DPTQO complexes with under study metal ions.The
solution quantitatively.Therefore, it was chosen as stability constant for complexation of this ligand with
the sorbent for subsequent work.
these metal ions is as following. For ML the stability
2+
2+
constant is 4.0±0.01 for Cd ion,5.8±0.04 for Zn ion
+
Inꢁestigation of complexation of ligand with and 5.8±0.01 forAg ion, which lead to following order
metal ions
2+
2+
+
Cd <Zn <Ag ion.He cumulative stability constant
+
2+
The 2,3 Di Hydro 2,3 paratolyl Qinazoline for ML is 9.9±0.04 for Ag ion,7.0±0.04 for Cd ion
2
2
+
(
1- H)- 4 one (DPTQO),with one oxygen, two and 10.7±0.07 for Zn ion. This nature seems to
nitrogen in water at neutral pH. It is known that the be not originated from their back bone structure of
Schiff bases ligands form very stable complexes ligands but mainly from the use of ligand-N-donors
33,34
with transition metal ions. The resulting complexes on the complexation .The unique nature of Schiff
−
5
−1
−3
−1
Fig. 2: Uv–ꢁisible spectra for titration of L (7.41×10 mol L ) with Ag+ (1.00×10 mol L ) in MeOH
0
−1
(
T=25 C and I = 0.05 mol L ). (a) The molar ratio plot in λmax = 545 nm. (b) The corresponding
+
computer-fitted curꢁe of absorbance ꢁs. [Ag /L]

RAOUFI et al., Orient. J. Chem., Vol. 32(1), 575-584 (2016)
579
base-N-donor is enhanced by the existence of
widely spread conjugation system. The extraction
mechanism corresponds to a cation exchange,in
which a complex of stoichiometric formula (ML
low pH is due to the competition of the hydrogen ion
with the metal ions for complexation and binding to
Schiff base. The decrease in absorption at pH >9.5
2+
2+
is probably due to the precipitation of Cd , Zn and
+
+
or/and ML ) isformed and liberating at the same
Ag ions as insoluble M(OH) or M(OH) . To achieve
2
2
+
time 2 mol H ions into solution.The results of the
high efficiency and good selectivity, a pH of 9.5 was
selected for subsequent work.
present investigation show that the reagent H Lcan
2
be successfully used for the quantitative extraction
of heavymetals ions. The authors decided to use
DPTQO as a suitable modifier for the selective
concentration and extraction of some heavy and
transition metal ions on SDS-coated alumina.
Effect of amount of ligand on metal ion
recoꢁery
In order to investigate the optimum amount
of ligand for the quantitative extraction of the metal
ions by the SDS-coated alumina, the extraction was
conducted by varying the amount of ligand from 0 to
60mg. Therefore, solid phase comprises of various
amount of ligand coated on constant amount of
alumina were prepared and enrichment experiment
was carried out, results are shown in Figure 4. As
can be seen, with increasing amount of ligand up
to 30mg an increase in recoveries can be achieved
and further increase does not enhance the efficiency.
The various amount of solid phase has been used
Effect of pH on metal ion recoꢁery
pH is one of the important factors which
affect the efficiency of retention/elution metal ions
35–37
by solid phase extraction
. The effect of pH was
studied by varying pH in the range of 5.5–12. It can
be seen from Figure 3. that the adsorption amounts
of mixed hemimicelles systems decreased obviously
with the increasing of pH. Especially, when pH was
above the potential of zero charge (PZC) of alumina
2
+
2+
(
about 10.0), the adsorption amount of SDS-coated
for the preconcentration of understudy Cd , Zn
+
alumina had a sharp decrease. With increasing the
pH, the positive charge of alumina surface reduced
gradually and became negative charged when the pH
was above its PZC. As a result, the SDS molecules
desorbed from alumina surface gradually and begin
to decrease. On the other hand the progressive
decrease in the retention of these metal ions at a
and Ag ions and results display that up to 1.0 g of
solid phase, the extractions efficiency was increase
and further addition has not significant effect on
recoveries.
Amount of SDS
The influence of SDS amount on the
percentage of complexed ions ad-solubilized
Fig. 3: Effect of pH on recoꢁery of metal
Fig. 4: Effect of amount of DPTQO on recoꢁery
of metal ions (N= 3), Conditions: 250mL of
sample at pH 9.5, eluent, 8mL of 4.0 mol L
ions (N= 3), Conditions: 250 mL of sample at
−
1
−1
ꢁ
arious pH, eluent, 8mL of 4.0 mol L HNO3,
solid phase, 1.0 g Al O , 60mg SDS and
HNO , solid phase, 1.0 g Al O , 60mg SDS and
2
3
3
2
3
30mg ligand.
different amount of ligand.

580
RAOUFI et al., Orient. J. Chem., Vol. 32(1), 575-584 (2016)
was investigated by shaking 250mL of a solution
2+
2+
+
containing 50µg of each Cd , Zn and Ag ions with
solid phase containing various amounts of SDS, 1
gg- Al O and 10 mg DPTQO at pH 9.5 for 90min
2
3
with stirring rate 300 rpm. In the absence of SDS,
metal ions retained on DPTQOalumina with 60%
lower efficiency for all ions. The retention of metal
ions on hemi-micelles, which have a hydrophobic
surface, was clearly dependent on analyte complex
polarity. Therefore, addition of SDS is necessary.
The formation of minute amounts of ad-micelles was
essential to achieve complete ad-solubilization of
chelates of these ions. At surfactant concentrations
higher than about 60 mg/g alumina, a decrease in
the retention percentage of ions was observed, as
a result of the formation of micelles (Figure5). The
adsorption amount began to decrease when the
SDS added exceeded 60mg for 1.0 g of alumina.
It can be explained by the fact that with more SDS
added, its molecules began to form micelles in the
bulk aqueous solution; moreover, the micelles make
the DPTQO distribute into the bulk solution again. In
this region the slope of alumina adsorption curve is
flat, which indicated that the interactions between
DPTQO and SDS-coated alumina were strong. As
a result, it was more difficult for SDS-coated alumina
to desorb DPTQO into aqueous solution.
Fig. 5: Effect of amount of SDS on recoꢁery of
metal ions (N= 3), Conditions: 250mL of sample
at PH=9.5, eluent, 6mL of 4.0 mol L−1 HNO3,
solid phase, 1.0 g Al O , ꢁarious amount of SDS
2
3
and 30mg ligand
Eluent types and eluent ꢁolume
In order to choose the most effective
2+
2+
+
eluent for desorbing the Cd ,Zn and Ag ions from
the sorbent surface, a series of eluents (different
acids) were used in order to find a selective eluent
for desorbing enriched ions from sorbent surfaces.
Table 1: Effect of type and concentration of
eluting agent on recoꢁery of analytes
Eluent
Recoꢁery (%)
Table 2: Specification of Method at
Optimum Conditions for Each element
According
Cd
Zn
Ag
−
1
8
8
8
8
8
8
8
8
4
6
9
1
mL 4mol L H PO4
mL 4mol L H SO4
mL 4mol L HCL
mL 4mol L CH COOH
mL 2mol L HNO3
mL 3mol L HNO3
mL 4mol L HNO3
mL 5mol L HNO3
mL 4mol L HNO3
mL 4mol L HNO3
mL 4mol L HNO3
0mL 4mol L HNO3
28.7
12.4
53.6
29.6
64.5
70.6
98.0
84.0
90.0
98.0
98.0
98.0
31.8
16.2
58.6
32.4
68.0
73.2
98.5
86.1
92.1
98.5
98.5
98.5
26.4
14.5
54.2
30.1
66.7
71.2
98.1
81.2
89.2
98.1
98.1
98.1
3
−
1
2
Parameters
value for each ions
−
1
Cd
Zn
Ag
−
1
3
−
1
Linear Range
(µg mL )
0.02
-0.85
1.4
0.01
-0.90
1.3
0.02
-0.92
1.2
−
1
-1
−
1
Detection Limit
−
1
-1
(ng mL )
−
1
Loading Capacity
(mg g )
0.45
0.46
0.61
−
1
-1
−
1
RSD %
1.9
1.8
1.7
−
1
Recovery %
97.7
98.2
98.0

RAOUFI et al., Orient. J. Chem., Vol. 32(1), 575-584 (2016)
581
A total of 6ml of 4.0 M of the above-mentioned
eluents were used for desorbing the adsorbed ions.
The results (Table 1) showed that the recovery
is best when nitric acid solution was used as the
eluent. The influence of the concentration of nitric
acid on the desorption of these ions was studied.
For desorbing 40 µg of ions, already adsorbed on
increasing of temperature the adsorbate–adsorbent
bonds were weakened and DPTQO had desorption
trend from the solid phase to solution phase. It can
also be proved by the changes of SDS adsorption
amounts.With the temperature increasing, the bond
between alumina and SDS became weak and partial
SDS molecules began to desorb from alumina
surface.
1.0 g of adsorbent, different concentrations of the
eluent (nitric acid) have been used.At concentrations
more than 4 M the extraction efficiency reached
maximum.
Inꢁestigation of method performances
Added 250 mL of solution of metal ions in
-1
the range of 0.01–1.00 gmL with coated adsorbents
at the optimum conditions, to obtain the calibration
curves, repeatability and reproducibility. The
Effect of time and rate of shaꢂing
The efficiencies of the analyte deposition
-
1
2+
depend on the contact time and stirring rate of
sample with the solid phase. It is necessary to
require the preconcentrate of metal ions in short
time. In this regard, a replicate six set of analyte and
adsorbents were prepared and stirring at different
time intervals (20–120 min) with stirring rate of
responses are linear 0.02–0.85µg mL for Cd ion,
-
1
2+
-1
0.01–0.90 µg mL for Zn ion, 0.02–0.92 µg mL
+
for Ag ion. The sensitivity of developed method
was reproduced by detecting the limit of detection
(LOD), defined as the lowest concentration of metal
ions below which quantitative sorption of the metal
ion by basic alumina is not perceptibly seen. The
limits of detection (LOD) of the present work were
calculated under optimal experimental conditions
after application of the preconcentration procedure
to blank solutions (without samples or standards).
The limits of detections based on three times the
1
3
00–400 rpm. It was observed that 90 minmixing at
2+
00rpm stirring rate to optimum recoveries of Cd ,
2+
+
Zn and Ag ions.On the other hand, a set of similar
solid phase extraction were carried out at 300rpm
%C
while keeping the temperature at 25–60 for 90min.
Later on, the residual concentration was determined
where the metal ion uptake was estimated. The
DPTQO adsorption amounts of SDS-coated alumina
systems decreased with increasing temperature.The
decreased adsorption amounts suggested that the
two-adsorption systems were exothermic. With the
Table 4: Recoꢁery of trace elements from
radiology wastewater and amalgam samples
after application of presented flotation
procedure(N=3)
Table 3: Effects of the matrix ions on the
recoꢁeries of the examined metal ions (N=3).
Ion
Added, Found,
RSD Recoꢁery
-
1
-1
µg L
µg L
%
%
Ion
Added
As
Tolerance Limit
Radiology wastewater
-
1
Ion mg mL
Zn
Cd
0
0.5
0
0.17
0.66
6.6
8.6
1.6
1.6
1.2
1.5
1
1.4
1
---
98.4
---
102.3
---
Cd
Ag
Zn
+
Na
K
NaCl,
KCl
CaCl2
NaCl
3000
2500
2500
2500
5000
2500
2500
2500
2500
1000
1000
2500
600
3000
2500
2500
2500
2500
800
800
2500
500
0.5
0
+
Ag
2
+
Ca
0.5
2.1
101.1
-
Cl
Amalgam
Cd
2
-
SO4
(NH4) SO4 2500
2
2
+
Mg
MgCl2
NaHCO3
750
800
2500
500
0
0.5
0
0.06
0.51
1.3
1.9
0.4
1.4
1.1
1.3
1.2
1.2
0.9
---
103.6
---
101.6
---
3
-
HCO
PO4
3
-
Na PO4
Zn
3
2
+
2+
Cu , Co ,
Nitrate
salt
0.5
0
2
+
2+
Hg , Ni ,
Ag
3
+
3+
2+
Al , Cr ,Ba ,
0.5
0.9
102.1

582
RAOUFI et al., Orient. J. Chem., Vol. 32(1), 575-584 (2016)
standard deviations of the blank (N= 5, LOD= Xb+3s, Effect of foreign ions
where LOD is the limits of detection and Xb is the
To assess the possible applications of the
blank value) for Cd , Zn and Ag ions to be 1.4, 1.3 procedure, the effect of foreign ions or/and often
2+
2+
+
-
1
and1.2 (ng mL ), respectively. were found that the accompany analyte ions in various real samples,
2
+
2+
+
2+
recovery for Cd , Zn and Ag ions were 97.7, 98.2, which are interfere with the determination of Cd ,
9
2
2
+
+
8.0 and 95.0 with RSD of 1.9, 1.8 and 1.7.( Table Zn and Ag ions, was examined at optimized
). It was also observed that recovery for repeated conditions. The results are given in Table 3. A fixed
recovery on the same solid phase not varies more amount of understudy analytes were taken with
than 3%. Therefore, understudy solid phase can be different amounts of foreign ions and proposed
repeatedly use without considerable loss of uptake procedure was followed. The recoveries of analytes
3
8
capacity .
were higher than 95%.Tolerable limit was defined as
the highest amount of foreign ions that produced an
error which is not exceeding 5%, in the determination
of investigated analyte ions by the combination of
the SDS-coated alumina solid phase extraction
procedure followed by the flame atomic absorption
spectrometry. It was observed that, most of the ion
tested, have no significant effect on the recoveries
of analyte ion. Cd , Zn and Ag ions were
quantitatively recovered in the presence of optimum
mount of alkaline, earth alkaline, transition and heavy
metal ions as well as some anions.
Table 5: Recoꢁery of trace elements
from natural water and blood samples
after application of presented flotation
procedure(N=3)
Ion
Added, Found,
RSD Recoꢁery
-
1
-1
2+
2+
+
µg L
µg L
%
%
Blood
Cd
0
0.7
1.8
2
1.5
1.2
1.4
1.0
1.2
0.9
---
103
---
103.2
---
10
Zn
Ag
0
Real samples – eꢁaluation of method
10
3.5
The proposed method was applied for
2+
2+
+
0
0.02
13
the determination of Cd , Zn and Ag ions by the
standard addition technique in radiology wastewater,
amalgam, natural water and blood samples.including
well radiology wastewater and amalgam samples
(Table 4). The results of in natural water and
blood samples.as mentioned in the Experimental
section are summarized in (Table 5). Notably, the
10
100.6
Natural water
Cd
0
0.5
1.4
1.2
1.1
1.4
1.2
1.5
1.2
---
101.2
---
100.3
---
10
Zn
Ag
0
3.4
10
6.8
2+
2+
+
0
0.04
0.07
determination of Cd , Zn and Ag ions in radiology
wastewater, amalgam, natural water and blood
10
99
Table 6: Comparatiꢁe data from recent papers on preconcentration studies a
Bytes
Method and
apparatus
EF
DL (µg/L) R.S.D. (%)
5
Cu, Cd, Pb, Zn, Ni,
Co
SPE/FAAS
80.0
0.16–0.60
1–17
[39]
Cd(II), Pb(II)
Cd(II)
Cd(II), Zn(II), Ni(II)
Cd(II), Zn(II), Ag(I)
SPE/FAAS
SPE/FAAS
SPE/FAAS
SPE/FAAS
288.0
75.0
80.0
80.0
0.07–0.09
0.6
2.1–2.3
1.2 – 2.1
<3.7
1.23–1.31
<3.6
[40]
[41]
[42]
Present
work
1.4, 1.3, 1.2
a
EF:enrichment factor,DL: detection limit,R.S.D.:relative standard deviation; SPE: solid
phaseextraction

583
RAOUFI et al., Orient. J. Chem., Vol. 32(1), 575-584 (2016)
samples. is remarkably accurate by the proposed applicability of the separation and preconcentration
2
+
method. The results of the determination of Cd , of metals. This method is simple and there is no
2
+
+
Zn and Ag ions in the in radiology wastewater, necessity for elaborating a cleanup procedure, but
amalgam, natural water and blood samples. as the retained metals were simply eluted with 6mL of 4
”1
mentioned in the experimental section are listed in mol L HNO and were analyzed by FAAS.Each solid
3
Table 5.
phase can be usedfor at least 10 successive analyses
without considerable change in Cd , Zn and Ag
ions recovery.As a result it can be concluded that the
2+
2+
+
Comparison with literature
A comparison of the proposed system with proposed procedure can be satisfactorily considered
other preconcentration procedures using several as an alternative application for preconcentration and
3
9–42
2+
2+
+
sorbents is given in Table 6
, the proposed separation of traces of Cd , Zn and Ag ions from
method shows comparable capacity level, lower aqueous solute. The performance characteristics of
detection limit, and wider linear range and is a the proposed method and other selected SPE/FAAS
convenient, safe, simple, rapid and inexpensive systems for comparative purposes in the literature
method for the determination of trace quantities of are given inTable 5.The proposed procedure shows
these cations in radiology wastewater, amalgam, good detection limits and precision with reasonable
natural water and blood samples with satisfactory eluent volume, flow rate and preconcentration factor
46–51
results. The proposed preconcentration system over other SPE off-line preconcentrationmethods
.
shows goodpreconcentration factors with reasonable The method is simple, accurate can be applied for the
2+
2+
+
preconcentration time over other preconcentration determination of Cd , Zn and Ag ions inradiology
4
3–45
methods
. As seen from Table 6, the detection wastewater, amalgam, natural water and blood
52
limit for the proposed method was comparable to samples .
those given by the many methods.
ACkNOWLEDꢀMENT
CONCLUSION
The authors express their appreciation to
TheDPTQOloadedonSDS-coatedalumina the Graduate School and Research Council of the
is sensitive and accurate adsorbent for determination Ilam Azad University for the financial support of this
2
+
2+
+
of trace amounts of Cd , Zn and Ag ions. The work.
results presented in this paper have confirmed the
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