Spectrochimica Acta Part B 55 2000.

11011108

Determination of zinc, cadium, cobalt and nickel by

flame atomic absorption spectrometry after
preconcentration by poly ethylene terephthalate / fibers
grafted with methacrylic acid
b,U
Huseyin
Bag
, Ramazan Coskuna , Mehmet Sacak c ,

a , A. Rehber Turker

Mustafa Yigitoglu
a
a

Faculty of Science and Arts, Krkkale Uni ersity, TR-71450 Krkkale, Turkey
b
Faculty of Science and Arts, Gazi Uni ersity, TR-06500 Ankara, Turkey
c
Faculty of Science, Ankara Uni ersity, TR-06100 Ankara, Turkey
Received 22 September 1999; accepted 19 January 2000

Abstract
A method for the determination of Zn, Cd, Co and Ni by flame atomic absorption spectrophotometry after
preconcentrating on polyethylene terephthalate . fibers grafted with methacrylic acid has been developed. The batch
adsorption method was used for the preconcentration studies. Effect of pH, amount of adsorbent, concentration and
volume of elution solution, shaking time and interfering ions on the recovery of the analytes have been investigated.
Recoveries of Zn, Cd, Co and Ni were 97.3" 0.4%, 98.3" 0.2%, 94.1" 0.3% and 96.5" 0.6% at 95% confidence
level, respectively, at optimum conditions. Langmuir adsorption isotherm curves were also studied for the analytes.
The adsorption capacity of the adsorbent was found as 298, 412, 325 and 456 mgrg for Zn, Cd, Co and Ni,
respectively. Polyethylene terephthalate . fibers grafted with methacrylic acid are suitable for repeated use without
loss of capacity for more than thirty cycles. The proposed method was applied to the determination of trace metals in
river water and synthetic sea water. Trace metals have been determined with high precision. 2000 Elsevier Science
B.V. All rights reserved.
Keywords: Trace element; Preconcentration; Polymer; Water; Flame atomic absorption spectrometry

This paper was presented at Colloquium Spectroscopicum Internationale XXXI, held in Ankara, Turkey, September 1999, and
is published in the Special Issue of Spectrochimica Acta Part B, dedicated to that conference.
U
Corresponding author. Tel.: q90-312-212-29-00; fax: q90-312-212-22-79.
..
E-mail address: rturker@quark.fef.gazi.edu.tr A.R. Turker

0584-8547r00r$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 5 8 4 - 8 5 4 7 0 0 . 0 0 1 6 2 - 2

1102

H. Bag et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 11011108

1. Introduction
Many preconcentration techniques have been
proposed for the determination of metals in various environmental samples, including solvent
extraction w1,2x, ion exchange w3,4x, coprecipitation w5,6x and sorption w711x. Recently, solid
phase techniques have become increasingly popular in comparison with the more traditional
liquidliquid extraction methods w12x.
The use of chelating polymers for the preconcentration and separation of trace elements is
reasonably well understood and progress today is
mainly in improving the specificity of the resin
and the techniques of application. The functional
group atoms capable of forming chelate rings
usually include oxygen, nitrogen and sulfur. These
groups can be introduced into the polymer by
chemical transformation of the matrix or by the
synthesis of sorbent from monomeric ligands. The
insertion of suitable specific functional groups
into the polymeric matrix makes them capable to
react with metal ions or metal species under
certain favorable conditions, to form chelate rings
w13x. In recent years, grafted fibrous materials
have been widely used for the adsorption w14x and
preconcentration w15x of metal ions. Fibrous reactive agents have shown many advantages. The
large specific surface areas of the fibrous materials leads to the great adsorption capacity. The
fibrous materials grafted with various vinyl
monomers are other potential groups which can
be used to adsorption of heavy metals. Although
grafting is a well-known method for the modification of polymer structure, it has been used for
adsorption only recently w14x.
This paper presents a simple preconcentration
method which yields a sufficient enrichment factor, requires minimum reagent and produces an
aqueous solution. In this work we developed a
new ion exchange chelating fiber by grafting
methacrylic acid on polyethylene terephthalate .
PET. fibers for the preconcentration of zinc,
cadmium, cobalt and nickel from river water and
synthetic sea water. An investigation of the efficiency of the preconcentration and of the subsequent determination of Zn, Cd, Co and Ni by

flame atomic absorption spectrometry FAAS. was

performed.

2. Experimental
2.1. Apparatus
A Philips PU 9285 model flame atomic absorption spectrometer equipped with deuterium lamp
background correction, hollow cathode lamps and
air acetylene burner was used for the determination of the metals. The instrumental parameters
were those recommended by the manufacturer
w16x. All pH measurements were performed with a
JENWAY 3010 model digital pH meter. A
ColeParmer microfiltration apparatus with
membrane filter paper, 0.45 m pore size, was
used for filtration of water samples.
2.2. Reagents
All chemicals used for preparation of solutions
were of analytical grade unless otherwise indicated. All metal stock solutions 1000 g mly1 .
were prepared by dissolving the appropriate
amounts of metals or compounds with tripledistilled water. The working solutions were prepared by appropriate dilution of the stock solutions immediately prior to their use.
Methacrylic acid MAA. Merck. was treated
with NaCl, dried over CaCl 2 , and distilled in
vacuum at 40C. Benzoyl peroxide was twice precipitated from chloroform solution in methanol
and dried in a vacuum desiccator for 2 days.
Benzene was crystallized by cooling in the refrigerator at 4C, then the crystallized part was used
to prepare the benzoyl peroxide solution. Middle
oriented polyethylene terephthalate . fibers 100
denier, 28 filaments. were supplied from Sasa Co.
Adana, Turkey..
2.3. Synthesis of the grafted fibers
The fiber samples were washed with distilled
water at 40C, Soxhlet extraction was performed
for 6 h with acetone. The fibers 0.10" 0.01 g

H. Bag et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 11011108

samples. were placed in 45 ml de-ionized water

containing 0.94= 10y4 mol MAA. Then, 5 ml of
benzoxyl peroxide solution prepared in benzene
9.68 g ly1 . was added. The mixture was put in a
water bath Lauda D 40 S. at 80 " 0.1C. The
grafted PET fibers were taken at specific time
intervals 15120 min. in order to obtain different graft yields w17x, and subjected to a prewashing procedure with distilled water at 25C for 2 h
before being washed in boiling water for 1 h. The
grafted fibers were Soxhlet extracted with acetone
for 8 h, dried, and weighed. The percentage graft
yield was calculated from the difference between
the weights of original and grafted samples.
2.4. General procedure
An aliquot of a solution 100 ml. containing
one or several elements Zn, 20 g; Cd, Co and
Ni, 25 g. was placed in a 250-ml beaker. The pH
of the solution was adjusted to the desired value
with hydrochloric acid or ammonia solutions. The
resulting solution was transferred into a 250-ml
Erlenmeyer flask containing 0.1 g of grafted PET
fibers. After shaking the solution at 200 rev. miny1

1103

for 30 min, the grafted PET fibers were removed

by filtration through membrane filter. The grafted
PET fibers were then put in a 50-ml flask, and the
retained metal ions were desorbed by shaking
with a suitable elution solution, typically 5 ml of 1
mol ly1 nitric acid solution. After filtering of the
grafted PET fibers, the elution solution was aspirated into an airacetylene flame and the metals
were determined by FAAS. The grafted PET fibers
have been used repeatedly after washing with 1
mol ly1 nitric acid solution and triply distilled
water, respectively. Using the procedure described above, the recovery of the elements was
calculated from the ratio of the concentration
found by FAAS and the concentration calculated
theoretically.

3. Results and discussion

3.1. Effect of pH
The effect of the pH of the sample solutions
was evaluated by adjusting the pH in a range of
210 with HCl or NH 3 solutions. Fig. 1 shows the

Fig. 1. Effect of pH on the recovery sample volume: 100 ml; trace metal ion concentration: 0.2 g mly1 for Zn and 0.25 g mly1
for Cd, Co and Ni; eluent: 5 ml of 1 mol ly1 HNO3 ..

1104

H. Bag et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 11011108

effect of pH on the recoveries of the studied

metal ions. It is clear that all the metals were
poorly adsorbed at pHF 4. Maximum recoveries
were achieved at pH 6 for all metals. Above pH 6,
quantitative recoveries were obtained for Zn and
Ni, but not for Cd and Co.
3.2. Effect of the amount of adsorbent
The percentage recovery of metal ions on
grafted PET fibers was determined by using different amounts of grafted PET fibers. One hundred millilitres of a metal ion solution was maintained at the optimum pH and was stirred with
different amounts of grafted PET fibers between
0.1 and 0.5 g.. It was seen that no significant
change in recovery was observed with increasing
amount of grafted PET fibers.
3.3. Effect of eluent type, concentration and olume
The elution efficiency of hydrochloric acid and
nitric acid were studied at different concentrations. For this purpose, 0.5 mol ly1 and 1 mol ly1
hydrochloric and nitric acid solutions with the
volumes of 5 and 10 ml have been tested. As can
be seen in Table 1, 5 ml of 1 mol ly1 nitric acid
solution for all metals was found to be satisfactory for complete desorption. Concentrations
lower than 1 mol ly1 are not adequate for the
quantitative elution of metals.

3.4. Effect of contact (shaking) time

The effect of contact time on the adsorption of
the metals was also evaluated. For this purpose,
an aliquot of a solution 50 ml. of one or several
elements concentration of 4 g mly1 for Zn and
5 g mly1 for Cd, Co and Ni. was placed in a
100-ml Erlenmeyer flask. The pH of the solution
was adjusted to pH 6 with hydrochloric acid.
While shaking the solution at 200 rev. miny1 , 5
ml of solution was taken at 10-min intervals. It
was found that the adsorption of metals by grafted
PET fibers reached to equilibrium within 30 min.
3.5. Effect of olume of sample solution
In order to determine the maximum applicable
sample solution i.e. dealing with real samples
containing very low concentration of the metal
ions., the effect of changes in the volume of
sample solution on the retention of Zn, Cd, Co
and Ni was investigated. By varying the volume of
sample solution for the fixed amount of adsorbent
and metal, no change in the recovery of metals
was observed up to a volume of 750 ml. The
sample solution and elution volume were 750 ml
and 5 ml, respectively. So, a preconcentration
factor of 150 was obtained for all elements studied. These results show that Zn could be determined at a concentration of 0.027 g mly1 ;
Cd, Co and Ni could be determined at a concentration of 0.033 g mly1 .

Table 1
Effect of type, concentration and volume of elution solution on the recovery of elements sample volume: 100 ml; trace metal ion
concentration: 0.2 g mly1 for Zn and 0.25 g mly1 for Cd, Co and Ni.
Type of the
elution solution

Volume
ml.

Concentration
mol ly1 .

HCl

5
10
5
10
5
10
5
10

0.5

HCl
HNO3
HNO3
a

Mean of three replicates.

1.0
0.5
1.0

Recovery %.a
Zn

Cd

Co

Ni

44
47
63
68
75
79
97
97

52
58
69
74
81
88
98
98

49
55
64
70
73
82
94
94

46
51
66
72
77
84
96
96

H. Bag et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 11011108

3.6. Precision of the method

The precision of the method was investigated
at optimum conditions mentioned above pH 6;
eluent, 5 ml 1 mol ly1 HNO3 ; shaking time, 30
min; volume of sample, 100 ml. by performing
successive retention and elution cycles and followed the determination by FAAS. As can be
seen in Table 2, the recoveries of all metals are
approximately 95% which is sufficient for preconcentration purposes. Relative standard deviations
were approximately 2%.
3.7. Adsorption isotherms and adsorption capacity

1105

was determined by studying the amount of adsorbed metal as a function of metal concentration.
One hundred millilitres of solutions containing
metal ion concentrations in the range 101000
g mly1 were maintained at the optimum conditions determined before. The metal ions in the
supernatant were determined by FAAS and the
adsorption capacities of grafted PET fibers for
the metals studied were calculated from Langmuir plots w18x. Fig. 2 shows the adsorption
isotherms of the metals studied. The adsorption
capacity of the adsorbent was found as 298, 412,
325 and 456 mgrg for Zn, Cd, Co and Ni, respectively.

The adsorption behavior of grafted PET fibers

3.8. Effect of foreign ions
Table 2
Precision of the method
Element

Zn
Cd
Co
Ni
a

Recovery a %.

R " tsr'N

Relative standard
deviation %.

97.3" 0.4
98.3" 0.2
94.1" 0.3
96.5" 0.6

1.9
1.6
2.2
2.1

7
7
7
7

Average of N determinations with 95% confidence level.

The effect of the interfering elements and matrix ions of sea water on the recovery of the
analytes were examined. For this purpose, 100 ml
of synthetic solutions containing 10010 000 g
mly1 Ca, Mg, Na and K as their chlorides and
containing 150 g mly1 Cu, Fe, Zn, Cd, Co, Ni,
Mg and Pb have been prepared. The recoveries of
the analytes have been determined at optimum

Fig. 2. Adsorption isotherms of metals on grafted PET fibers sample volume: 100 ml; pH 6..

1106

H. Bag et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 11011108

Table 3
Effect of other ions on recovery
Recoverya %.

Interfering
ions

Concentration of
each interfering
iond g mly1 .

Znb

Cdc

Coc

Nic

Cu2q, Zn2q
Ni2q, Cd2q
Co2q, Mn2q
Pb2q, Fe3q

1
5
20
50

97
97
97
95
93

98
98
96
94
91

94
94
94
93
92

96
96
95
94
91

Mean of three replicates.

0.20 g mly1 .
c
0.25 g mly1 .
d
Concentration of interfering elements not including the analytes.
b

conditions in the presence of interfering ions. The

results are presented in Tables 3 and 4. As can be
seen, the presence of large amounts of alkali and
alkaline earth elements in the sample have no
significant effect on the recovery of analytes. The
effects of other ions at given concentrations are
also negligible. This shows that the metals studied
Table 4
Effect of matrix ions on recovery
Matrix ions

Recoverya %.
Znb

Cdc

Coc

Nic

97

98

94

96

Ca 10 g mly1 .
Mg 50 g mly1 .
Na 100 g mly1 .
K 10 g mly1 .

97

98

94

96

Ca 100 g mly1 .
Mg 400 g mly1 .
Na 1000 g mly1 .
K 100 g mly1 .

96

97

93

95

Ca 200 g mly1 .
Mg 800 g mly1 .
Na 5000 g mly1 .
K 200 g mly1 .

96

96

93

95

Ca 400 g mly1 .d
Mg 1300 g mly1 . d
Na 10 000 g mly1 . d
K 400 g mly1 . d

95

96

93

94

3.9. The effect of repeated use of adsorbent

To test the long-term stability of the adsorbent,
it was subjected to successive adsorption and elution cycles. The procedure was carried out five
times per day and the next five runs were made 1
day later, and so on up to 5 days 25 adsorptionelution cycles.. The adsorbent was stored in
triple-distilled water during the night. The stability and potential recyclability of the adsorbent
were assessed by monitoring the change in the
recoveries of the metals studied. At the end of 25
adsorption-elution cycles, the recoveries of the
analytes were almost constant within the uncertainty limits. The adsorbent seems to be relatively
stable over the 25 runs.
3.10. Application

Mean of three replicates.

0.20 g mly1 .
c
0.25 g mly1 .
d
Synthetic sea water composition.
b

can be determined quantitatively in river and sea

waters.

For the application of the proposed method,

the determination Zn, Cd, Co and Ni in Kzlrmak
River water located in Krkkale, Turkey. and
sea water was attempted. The river water samples
were filtered through a membrane filter pore size
0.45 m.. The river water samples were spiked
with the analytes to test the accuracy of the
method and analyzed as soon as possible after
sampling. As shown in Table 5, the accuracy and
precision for the determination of zinc, cadmium,
cobalt and nickel were quite satisfactory.

H. Bag et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 11011108

1107

Table 5
Determination of Zn, Cd, Co and Ni in river water sample volume: 250 ml; shaking time: 30 min; eluent volume: 5 ml; pH 6.
Element

Added g.

Founda g.

Recoveryb %.

Zn

10
20

4.28
13.66
23.43

95.6" 0.2
96.5" 0.3

Cd

10
20

3.79
13.11
22.97

95.1" 0.2
96.6" 0.1

Co

10
20

5.16
14.17
23.94

93.5" 0.3
95.2" 0.4

Ni

10
20

4.85
14.10
23.89

94.9" 0.2
96.1 " 0.5

a
b

Mean of five determinations.

Mean of five determinations with 95% confidence level.

For the trace determination in sea water, synthetic sea water was prepared by adding appropriate amounts of Na, K, Mg and Ca w19x and spiked
with Zn, Cd, Co and Ni. The obtained results are
shown in Table 6. The proposed method was
applied successfully for the preconcentration and
determination of trace amounts of Zn, Cd, Co
and Ni in synthetic sea water.

4. Conclusion
The proposed method to use of PET fibers
grafted with MAA for the preconcentration of
Zn, Cd, Co and Ni is simple, precise and accurate.
Zn, Cd, Co and Ni were quantitatively recovered
from the adsorbent with a high precision. The

Table 6
Determination of Zn, Cd, Co and Ni in spiked synthetic sea water a sample volume: 250 ml; shaking time: 30 min; eluent volume: 5
ml; pH 6.
Element

Added g.

Foundb g.

Recoveryc %.

Zn

5
10
20

4.71
9.51
19.15

94.2" 0.4
95.1" 0.2
95.8" 0.3

Cd

5
10
20

4.77
9.63
19.34

95.4" 0.5
96.3" 0.2
96.7" 0.4

Co

5
10
20

4.68
9.43
19.92

93.6" 0.1
94.3" 0.4
94.6" 0.2

Ni

5
10
20

4.70
9.46
18.80

94.1" 0.3
94.6" 0.5
94.0" 0.1

Synthetic sea water element concentrations were too low.

Mean of six determinations.
c
Mean of six determinations with 95% confidence level.
b

1108

H. Bag et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 11011108

preconcentration technique used in this work is

very simple and the duration of a preconcentration step is approximately 60 min including regeneration of adsorbent for 100 ml of sample solution. This technique is very cheap and only 0.1 g
of adsorbent is needed and repeated use is possible. In conclusion, the proposed method is excellent with respect to simplicity, sensitivity, selectivity, precision, accuracy and stability of adsorbent.

w9x

w10x

w11x

References
w1x P.L. Malvankar, V.M. Shinde, Ion-pair extraction and
determination of copperII. and zincII. in environmental and pharmaceutical samples, Analyst 116 1991. 1081.
w2x K.K. Namboothiri, N. Balasubramanian, T.V. Ramakrishna, Spectrophotometric determination of thallium after its extraction as an ion-pair of the chloro-complex
and pyronine g, Talanta 8 1991. 945.
w3x T. Kiriyama, R. Kuroda, Ion-exchange separation and
spectrophotometric determination of vanadium, cobalt
and titanium in environmental standard reference materials, Fresenius Z. Anal. Chem. 332 1988. 338.
w4x J. Kubova, V. Nevoral, V. Stresko, Determination of
beryllium trace contents in mineral waters after preconcentration on a chelating ion-exchanger, J. Anal. At.
Spectrom. 9 1994. 241.
w5x C.R. Lan, C.L. Tseng, M.H. Yang, Z.B. Alfassi, Two-step
coprecipitation method for differentiating chromium
species in water followed by determination of chromium
by neutron activation analysis, Analyst 116 1991. 35.
w6x C. Frigge, E. Jackwerth, Systematic investigations of the
multi-element preconcentration from copper by precipitation of the matrix as copperI. oxide and copperI.
thiocyanate, Anal. Chim. Acta 242 1991. 99.
w7x N. Ark, A.R. Turker,
Investigation on the preconcentra
tion of trace elements on polyacrylonitrile, Fresenius J.
Anal. Chem. 339 1991. 874.
w8x A.R. Turker,
A. Tunceli, Preconcentration of copper,

w12x
w13x

w14x

w15x

w16x
w17x
w18x
w19x

nickel and zinc with Amberlite XAD-16 resin, Fresenius

J. Anal. Chem. 345 1993. 755.
M.L. Lee, G. Tolg,
Preconcen E. Beinrohr, P. Tschopel,

tration of palladium, platinum and rhodium by on-line

sorbent extraction for graphite furnace atomic absorption spectrometry and inductively coupled plasma atomic
emission spectrometry, Anal. Chim. Acta 272 1993. 193.
M. Soylak, L. Elci, M. Dogan,
Physical and chemical
properties of mineral spring waters from the central
region of Anatolia, Turkey, Fresenius J. Anal. Chem.
351 1995. 308.
Determination of gold in geoA. Tunceli, A.R. Turker,

logical samples and anode slimes by atomic absorption

spectrometry after preconcentration with Amberlite
XAD-16 resin, Analyst 122 1997. 239.
R.A. Nickson, S.J. Hill, P.J. Worsfold, Solid phase techniques for the preconcentration of trace metals from
natural waters, Anal. Proc. Sep. 32 1995. 387.
C. Kantipuly, S. Katragadda, A. Chow, H.D. Gesser,
Chelating polymers and related supports for separation
and preconcentration of trace metals, Talanta 37 1990.
491.
R. Coskun, M. Yigitoglu,
M. Sacak, Adsorption behaviour of copperII. ion from aqueous solution on
methacrylic acid grafted polyethylene terephthalate .
fibers, J. Appl. Polym. Sci. 1999. in press.
B. Wen, X.-Q. Shan, R.-X. Liu, H.-X. Tang, Preconcentration of trace elements in sea water with
polyacrylamino phosphonic-dithiocarbamate. chelating
fiber for their determination by inductively coupled
plasma mass spectrometry, Fresenius J. Anal. Chem. 363
1999. 251.
P.J. Whiteside, B.A. Milner, Atomic Absorption Data
Book, Pye Unicam, Cambridge, 1984.
M. C
elik, M. Sacak, Grafting of methacrylic acid onto
polyethylene terephthalate . fibers using azobisisobutyronitrile, JMS-Pure Appl. Chem. A33 2. 1996. 191.
A.W. Adamson, Physical Chemistry of Surface, 4th ed,
Wiley-Interscience, New York, 1982.
J.E. Cantle, Atomic Absorption Spectrometry, Elsevier
Scientific Publishing Company, New York, 1986.