Development of 2-acetylpyridine-4-phenyl-3-thiosemicarbazone functionalized polymeric resin for the preconcentration of metal ions prior to their ultratrace determinations by MIS-F

2-Acetylpyridine-4-phenyl-3-thiosemicarbazone (APPT) ligand was incorporated onto Amberlite XAD-2 resin through an azo spacer and characterized by FTIR spectroscopy, elemental analysis, TGA, and SEM analysis. The synthesized resin was used for the preconcentration of Pb(II), Zn(II), Co(II), Ni(II), Cu(II), and Cd(II) ions. The sorbed metal ions were eluted with 10 mL of 2.0 mol L−1 HCl and determined by microsample injection coupled flame atomic spectrometry (MIS-FAAS).

⃝ T¨UB˙ITAK

doi:10.3906/kim-1308-51

h t t p : / / j o u r n a l s t u b i t a k g o v t r / c h e m /

Research Article

Development of 2-acetylpyridine-4-phenyl-3-thiosemicarbazone functionalized polymeric resin for the preconcentration of metal ions prior to their ultratrace

determinations by MIS-FAAS

Ali Nawaz SIYAL1,2, Saima Qayoom MEMON2, Aydan ELC ¸ ˙I3, ¨ Umit D˙IVR˙IKL˙I1,

Muhammad Yar KHUHAWAR2, Latif ELC ¸ ˙I1, ∗

1Chemistry Department, Faculty of Science and Arts, University of Pamukkale, Denizli, Turkey

2

Institute of Advance Research Studies in Chemical Science, University of Sindh, Jamshoro, Pakistan

3Department of Chemistry, Faculty of Sciences, University of Ege, Bornova, Turkey

Abstract: 2-Acetylpyridine-4-phenyl-3-thiosemicarbazone (APPT) ligand was incorporated onto Amberlite XAD-2 resin

through an azo spacer and characterized by FTIR spectroscopy, elemental analysis, TGA, and SEM analysis The synthesized resin was used for the preconcentration of Pb(II), Zn(II), Co(II), Ni(II), Cu(II), and Cd(II) ions The sorbed metal ions were eluted with 10 mL of 2.0 mol L−1 HCl and determined by microsample injection coupled flame atomic spectrometry (MIS-FAAS) The recoveries of studied metal ions were ≥ 95.1% with RSD ≥ 4.0% at optimum pH 8;

resin amount, 300 mg; flow rates, 2.0 mL min−1 (of eluent) and 3.0 mL min−1 (sample solution) The limits of detection (LOD) and limits of quantifications (LOQ) of the studied metal ions were 0.11, 0.05, 0.07, 0.08, 0.09, and 0.03; and 0.37,

0.17, 0.21, 0.13, 0.31, and 0.10 µ g L −1, respectively, with a preconcentration factor of 500 for the 6 studied metal ions The total saturation capacity of the resin was 0.36, 1.20, 1.50, 1.61, 1.07, and 0.71 mmol g−1, respectively

Key words: Amberlite XAD-2, chelating resin, 2-acetylpyridine-4-phenyl-3-thiosemicarbazone, preconcentration,

MIS-FAAS

1 Introduction

Some heavy metals are essential for life functioning at trace level but most of them are recognized as

and reduction of various enzymes by substitution of essential metal ions from enzymes and complexation with

absorption spectrometry (FAAS) has been extensively employed for the determination of metal ions because

this problem, a preconcentration procedure is often recommended prior to the trace determination of heavy metal ions.8 Several preconcentration based onco-precipitation,9,10 ion exchange,11,12 solvent extraction,13,14

∗Correspondence: elci@pau.edu.tr

attractive because of its advantages such as ease of operation, recycling of solid phase, higher preconcentration

ma-terials such as activated carbon, silica gel, polyurethane foam, microcrystalline naphthalene, C18 cartridges,

has been increasing in the synthesis of chelating resins for SPE due to their high degree of selectivity,

by these methods exhibit excellent resistance to ligand leaching as compared to the impregnation method

de-signed by choosing a cross-linked polymer matrix and small sized ligand, populated with functional groups

chelat-ing ligands such as Tiron,23o -vanillin thiosemicarbazone,24 1-(2-pyridylazo)-2-naphthol (PAN),25 thiosalicylic

3-(2-nitrophenyl)-1 H -3-(2-nitrophenyl)-1,2,4-triazole-5(4 H) -thione,31 2-(2-benzothiazolylazo)- p -cresol (BTAC),32 pyrocatechol violet,33 and o

thiosemicarbazones and phenyl-3-thiosemicarbazones have been widely used as spectrophotometric and

extractive preconcentration of metal ions

In the present study, we focused on the synthesis and characterization of APPT functionalized Amberlite XAD-2 resin for solid phase extractive preconcentration and ultratrace determination of Pb(II), Zn(II), Co(II),

Ni(II), Cu(II), and Cd(II) ions in water samples by MIS-FAAS using 100 µ L of sample solution per element

determination (for a single run)

2 Results and discussion

2.1 Characterization

2.1.1 FTIR spectroscopy

Figure 1 shows the FTIR spectrum of plain Amberlite XAD-2 (a) and Amberlite XAD-2-N=N-APPT resin (b)

the stretching vibrations of N–H, ArN–H, C–H, C=N, N=N, and C=S, respectively, indicating the successful coupling of APPT with Amberlite XAD-2 through an azo spacer

2.1.2 Elemental analysis

5.79%; N, 18.55%; S, 7.14%, O; 7.23% and theoretical values of elements calculated for a single repeating

7.10% The results showed good correlation between experimental and theoretical values, which indicated the successful coupling of APPT ligand with each of the repeating units of Amberlite XAD-2 through an azo spacer

Figure 1 FTIR spectrum of Amberlite XAD-2 (a) and Amberlite XAD-2-N=N-2-APPT resin (b).

2.1.3 Thermal gravimetric analysis (TGA)

Figure 2 shows a thermogram of Amberlite XAD-2-N=N-APPT resin with 2 distinct mass loss steps Step 1

repeating unit of polymeric chelating resin The theoretical value calculated for mass loss of 2 water molecules

is attributed to the mass loss of the fragment, 1-(1-(pyridin-2-yl)ethylidene)-hydrazinyl per repeating unit of the polymeric chelating resin The theoretical value calculated for loss of the fragment is 29.78% The good correlation between experimental and theoretical mass loss values confirmed the successful coupling of APPT with each of the repeating units of Amberlite XAD-2 through an azo spacer

Figure 2 Thermogram of Amberlite XAD-2-N=N-2-APPT resin.

2.1.4 Scanning electron microscopy (SEM) analysis

Morphological studies of the modified Amberlite XAD-2 surface were carried out by SEM analysis Figure 3 shows the SEM images of ground Amberlite XAD-2 resin (a) and Amberlite XAD-2-N=N-APPT resin (b) A clear difference in morphology between the ground Amberlite XAD-2 resin and the resin can be seen in the images, which confirmed the surface modification of Amberlite XAD-2

Figure 3 SEM images of ground Amberlite XAD-2 (a) and Amberlite XAD-2N=N-2-APPT resin (b).

2.2 Effect of pH

The surface activity of the resin for metal ions is strongly pH dependent Thus, the effect of pH on the retention

of studied metal ions was investigated For this purpose, 50 mL of model solution containing 2.5–20 µ g of

Pb(II), Zn(II), Co(II), Ni(II), Cu(II), and Cd(II) ions was adjusted to pH 2–10 using desired buffer solutions

pH for further experiments

0

10

20

30

40

50

60

70

80

90

100

pH

Pb(II) Zn(II) Co(II) Ni(II) Cu(II) Cd(II)

Figure 4 Effect of pH on the recoveries of studied metal ions (V = 50 mL, n = 3).

2.3 Effect of type and concentration of eluent

The effect of type, concentration, and volume of eluents on the recoveries of the studied metal ions was

recoveries of Pb(II), Zn(II), Co(II), Ni(II), Cu(II), and Cd(II) ions were 96.7 ± 3.2%, 97.9 ± 3.6%, 97.9 ±

Table 1 Effect of type, concentration, and volume of the eluent on the recoveries of metal ions (V = 50 mL, n = 3).

HNO3 1.0 10 51.0± 1.5 46.7 ± 1.6 54.6 ± 2.7 48.0 ± 1.5 55.5 ± 3.1 65.5 ± 1.4

HNO3 1.0 20 53.0± 3.4 55.5 ± 3.1 60.0 ± 2.5 56.5 ± 3.8 67.0 ± 3.0 76.6 ± 2.7

HNO3 2.0 10 47.8± 3.6 65.1 ± 2.5 65.2 ± 3.4 60.5 ± 2.9 76.0 ± 2.4 74.3 ± 1.8

HNO3 2.0 20 67.7± 4.1 70.5 ± 2.5 71.1 ± 1.3 76.3 ± 1.7 85.4 ± 2.3 80.8 ± 2.6

HNO3 3.0 10 51.7± 2.3 76.9 ± 3.0 78.2 ± 3.2 80.5 ± 3.1 88.9 ± 2.5 84.9 ± 1.6

HNO3 3.0 20 74.8± 2.5 88.9 ± 1.7 85.9 ± 4.1 85.9 ± 2.5 90.5 ± 1.7 89.2 ± 3.1

HCl 1.0 10 71.5± 4.1 60.3 ± 3.1 70.9 ± 3.7 80.5 ± 2.9 75.2 ± 3.6 71.8 ± 2.5

HCl 1.0 20 80.5± 3.7 73.7 ± 3.7 83.1 ± 1.9 88.3 ± 1.5 87.1 ± 2.9 88.9 ± 3.1

HCl 2.0 5.0 90.7± 3.2 87.9 ± 3.6 91.9 ± 2.9 86.3 ± 2.9 90.6 ± 3.5 82.1 ± 2.9

HCl 2.0 10 96.7± 3.2 97.9 ± 3.6 97.9 ± 2.9 97.3 ± 2.9 96.6 ± 3.5 98.1 ± 2.9

HCl 3.0 5.0 85.4± 2.2 88.7 ± 1.7 83.2 ± 1.5 90.1 ± 1.6 92.1 ± 2.7 90.5 ± 2.1

HCl 3.0 10 96.8± 2.4 97.1 ± 2.5 97.8 ± 2.3 97.9 ± 2.3 97.2 ± 3.1 98.4 ± 3.2

HCl 3.0 20 96.8± 1.3 97.3 ± 3.1 97.6 ± 2.2 92.5 ± 2.5 97.1 ± 2.3 98.8 ± 3.4

Conc.: Concentration of eluent (mol L−1) , V: Volume of eluent (mL), R: Recoveries (%), RSD: Relative standard deviation

2.4 Effect of flow rate

The effect of flow rate of eluent and sample solution on the recoveries of the studied metal ions was investigated

eluent and sample solution, respectively

Table 2 Effect of flow rates of eluent and sample solutions on the recoveries of metal ions (V = 50 mL, n = 3).

Sample

3 95.0± 2.4 98.5 ± 2.1 95.0± 2.2 96.0 ± 2.0 97.5 ± 3.9 96.8 ± 4.1

4 88.1± 2.9 98.7 ± 1.9 82.6± 3.5 92.1 ± 3.1 87.3 ± 2.1 88.1 ± 1.2

5 85.1± 2.1 98.9 ± 3.1 70.1± 3.5 90.1 ± 3.1 81.4 ± 2.2 80.0 ± 2.8

Eluent

1 97.0± 2.4 98.0 ± 2.1 98.4± 3.1 97.0 ± 2.1 99.0 ± 2.1 98.9 ± 1.3

2 96.5± 3.2 97.4 ± 2.1 97.3± 1.9 96.0 ± 2.0 98.1 ± 1.1 97.4 ± 2.1

3 91.5± 2.2 88.5 ± 3.5 92.1± 2.5 90.9 ± 3.2 87.8 ± 3.6 90.0 ± 1.3

4 89.9± 2.2 81.4 ± 3.0 84.6± 2.0 85.6 ± 2.5 77.4 ± 3.8 86.1 ± 2.5

5 80.3± 3.5 73.0 ± 2.5 72.5± 3.5 70.3 ± 3.0 63.7 ± 2.0 81.3 ± 3.3

FR: Flow rate (mL min−1) , R: Recoveries (%), RSD: Relative standard deviation

2.5 Effect of resin amount

The effect of resin amount on the recoveries of the studied metal ions was investigated For this, 50 mL of model solution was adjusted to pH 8 and passed through the column packed with 100–500 mg of the chelating

with 300–500 mg of the resin as shown in Figure 5 Therefore, 300 mg was chosen as the optimum resin amount for further experiments

2.6 Effect of sample volume

The effect of sample volume on the recoveries of the studied metal ions was investigated For this, model solution

containing 50, 10, 40, 25, 15, and 5.0 µ g of Pb(II), Zn(II), Co(II), Ni(II), Cu(II), and Cd(II) ions, respectively,

was diluted to 25–1200 mL and passed through the column at optimum conditions The retained metal ions

preconcentration factor calculated was 500 for all 6 studied metal ions as 2.0 mL of final solution was subjected

to MIS-FAAS

0

10

20

30

40

50

60

70

80

90

100

Resin amount (mg)

Pb(II) Zn(II) Co(II) Ni(II) Cu(II) Cd(II)

10

20

30

40

50

60

70

80

90

100

0 200 400 600 800 1000 1200

Sample volume (mL)

Pb(II) Zn(II) Co(II) Ni(II) Cu(II) Cd(II)

Figure 5 Effect of resin amount on recoveries of studied

metal ions (V = 50 mL, n = 3).

Figure 6 Effect of sample volume on the recoveries of

studied metal ions ( n = 3).

2.7 Effect of matrix ions

The effect of possible matrix ions present in natural water samples on the recoveries of the studied metal ions was investigated For this, 50 mL of model solution containing matrix ions was passed through the column at

high tolerance limits of the chelating resin for the studied matrix ions as shown in Table 3

2.8 Sorption capacity

The capacity of Amberlite XAD-2-N=N-APPT resin for the studied metal ions was examined by determining by

The resin amount, initial concentration of studied metal ions, and flow rate of sample solution were fixed as 500

mg, 10 mg L−1, and 3.0 mL min−1, respectively, for the column experiment Therefore, the total saturation

and breakthrough capacities of chelating resin for Pb(II), Zn(II), Co(II), Ni(II), Cu(II), and Cd(II) ions were 0.36, 1.20, 1.50, 1.61, 1.07, and 0.71; and 0.29, 1.07, 1.38, 1.44, 0.98, and 0.65 mmol g−1, respectively.

Table 3 Tolerance limits of the resin for the matrix ions (V = 50 mL, n = 3).

K+ 3000 98.0± 1.3 97.2 ± 2.3 98.6 ± 2.1 97.5 ± 3.0 95.5 ± 3.0 97.3 ± 2.4

Ca2+ 5000 97.6± 3.5 95.0 ± 2.9 96.0 ± 3.0 96.1 ± 2.9 95.5 ± 2.5 95.5 ± 3.1

Mg2+ 5000 98.0± 1.3 96.0 ± 3.7 96.2 ± 2.1 97.4 ± 2.3 97.0 ± 2.2 96.9 ± 2.5

Ba2+ 1100 97.9± 3.5 95.2 ± 1.9 97.8 ± 1.9 96.0 ± 3.1 96.5 ± 1.9 95.3 ± 3.1

SO2−

4 1000 95.4± 2.7 95.6 ± 3.5 95.5 ± 2.1 96.5 ± 1.8 95.0 ± 2.9 97.9 ± 2.4

PO3−

4 4000 98.1± 2.2 96.0 ± 2.9 97.1 ± 1.3 95.9 ± 2.4 95.0 ± 3.1 95.9 ± 3.0

CO2−

3 2700 96.3± 3.5 95.0 ±3.5 97.3± 2.0 96.0 ± 2.6 94.5 ± 3.1 95.9 ± 2.9

3 3000 97.2± 3.5 98.0 ± 2.1 97.7 ± 1.1 95.7 ± 1.9 95.0 ± 2.6 96.0 ± 3.5

3 8000 96.1± 1.4 94.6 ± 2.1 96.4 ± 2.9 95.7 ± 2.0 95.2 ± 3.6 96.1 ± 2.0

Cl− 2200 97.5± 2.3 96.0 ± 3.9 97.1 ± 2.1 96.0 ± 3.5 96.9 ± 3.1 95.1 ± 3.1

F− 3500 95.3± 1.9 97.5 ± 3.0 95.6 ± 3.0 97.0 ± 2.6 95.6 ± 3.0 97.0 ± 2.6 TLC: Tolerance limits concentration ( µ g mL −1) of matrix ions, R: Recoveries (%), RSD: Relative standard deviation

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

0 200 400 600 800 1000 1200 1400 1600 1800 2000

Volume (mL)

Pb(II) Zn(II) Co(II) Ni(II) Cu(II) Cd(II)

Figure 7 Breakthrough curve for capacity of the resin for the studied metals ions.

2.9 Sorption mechanism

Incorporation of the polydentate ligand APPT onto Amberlite XAD-2 resin played a vital role in metal ion adsorption The N and S of Amberlite XAD-2-N=N-APPT resin participated in the metal chelate formation The formation of APPT-metal (II) complex increased to its maximum at pH 8.0 due to the formation of enolate-like ions These 2 enolate-enolate-like ions interacted with divalent metal ions through S and N to form 5-membered chelate rings (Figure 8)

2.10 Analytical performance of the method

Validation and accuracy of the proposed method were evaluated by analysis of CRMs The recoveries of studied metal ions were achieved in good agreement with certified values as shown in Table 4 The validation and

N N S

C

N M

N

C C

N=N

M = Pb(II), Zn(II), Co(II), Ni(II), Cu(II) and Cd(II)

Figure 8 The sorption mechanism for the retention of metal ions onto Amberlite XAD-2-N=N-2-APPT resin.

high accuracy of the proposed method were confirmed by t-test at a confidence level of 95.0% The linear

The experimental enhancement factors (EFs) and theoretical preconcentration factors (PFs) were calculated from the ratio of the slopes of the calibration equations and from the ratio of the sample solution volumes (1000 mL) to 2.0 mL of final effluent volume, respectively The relative errors of the experimental enhancement factors

were smaller than 7.6% The limits of detection (LOD) (blank + 3 σ , where σ is the standard deviation of

parameters of the method are summarized in Table 5 The resin was recycled more than 100 times ( n = 3) in

different intervals of time without significant loss in recoveries and capacities for the studied metal ions

Table 4 Determination of the studied metal ions in CRMs (V = 100 mL, n = 3).

Metals

CV: Certified value, FV: Found value, R: Recoveries (%), RSD: Relative standard deviation

2.11 Applications of the method

The optimized method was successfully applied for preconcentration and ultratrace determination of Pb(II), Zn(II), Co(II), Ni(II), Cu(II), and Cd(II) ions in wastewater, river water, canal water, and lake water samples

The samples were analyzed with and without the standard addition method The recoveries of the studied

Table 5 Method’s parameters for the preconcentration of metal ions.

LOD: Limit of detection, LOQ: Limit of quantification, PF: Preconcentration factor, EF: Enhancement factor

Table 6 Determination of the studied metal ions in spiked water samples (V = 100 mL, n = 3).

Metals

Pb(II)

Zn(II)

Co(II)

Ni(II)

Cu(II)

20 19.9 99.5± 3.1 19.7 98.5± 3.5 19.5 97.5± 3.5 19.8 99.0± 3.0

Cd(II)

FV: Found value ( µ g), R: Recoveries (%), RSD: Relative standard deviation, nd: Not detected.

Table 7 Comparison of analytical parameters for the trace determination studied metal ions by FAAS using different

chelating resins

milk &

mvt

Pb(II) Zn(II) Co(II) Ni(II) Cu(II) Cd(II)

0.15 0.18 0.09 0.12 0.41 0.07

300 250

150 250

250 200

13.9 3.88 0.30 8.72 1.24 4.71

milk

& mvt

Pb(II) Zn(II) Co(II) Ni(II) Cu(II) Cd(II)

0.13 0.20 0.22 0.27 0.47 0.10

250 300

167 100

300 250

0.67 1.12 1.08 1.76 2.52 0.77

& mvt

Pb(II) Zn(II) Co(II) Ni(II) Cu(II) Cd(II)

0.11 0.17 0.24 0.22 0.42 0.56

200 200

250 300

250 150

2.10 1.72 3.23 2.56 2.93 0.44

Co(II) Ni(II) Cu(II) Cd(II)

0.02 0.04 0.06 0.06 0.05 0.03

40 40

100 65

50 50

25.0 2.50 5.00 7.50 4.00 2.00

Ni(II) Cu(II) Cd(II)

-0.23 0.12 0.12 0.50 0.14

-50 -50

50 60

40

-4.30 1.20 1.10 0.90 1.00

Ni(II) Cu(II) Cd(II)

-0.03 0.02 0.05 0.09 0.04

-200 -200

200 100

200

-2.85 0.06 0.24 3.76 0.39

Ni(II) Cu(II) Cd(II)

-0.02 0.08 0.08 0.08 0.04

-200 -200

200 200

200

-0.12 0.07 0.16 0.08 0.06

Ni(II) Cu(II) Cd(II)

-0.15 0.07 0.12 0.24 0.14

-320 200

280 360

300

-0.63 1.41 0.96 0.42 0.77

Co(II) Ni(II) Cu(II)

-0.38 1.13 1.24 1.24 1.16

-50 -50

50 50

50

-0.15 0.19 0.21 0.18 0.18

Co(II) Ni(II) Cd(II)

-0.06 0.12 0.08 0.12 0.08

-400 -400

150 200

400

-2.50 -2.50 6.50 5.00 2.50

Ni(II) Cu(II) Cd(II)

-0.15 0.06 0.22 0.18 0.12

-180 160

190 190

180

-0.75 0.85 0.62 0.65 0.72

Co(II) Ni(II) Cu(II) Cd(II)

0.36 1.20 1.50 1.61 1.07 0.71

500 500

500 500

500 500

0.11 0.05 0.07 0.08 0.09 0.03

≤ 4.0 This work

X: Amberlite XAD resin, CP: Capacity (mmol g−1 ) , LOD: PF: Preconcentration factor Limit of detection ( µ g L −1) , mvt: Multivitamin tablet, mvc: Multivitamin capsule, DHP: 2,3-Dihydroxypyridine, San: Salicylanilide, HIMB:

4-{[(2–Hydroxyphenyl) imino] methyl} -1,2-benzenediol, DMABA: 2-{[1-(3,4-Dihydroxyphenyl)methylidene]amino} ben-zoic acid, o AP: o -Aminophenol, PC: Pyrocatechol, PAN: 1-(2-pyridylazo)-2-naphthol, SA: salicylic acid, SAS: Salicyl aspartide, o ABA: o -Aminobenzoic acid, PTA: Phthalic acid, APPT: 2-Acetylpyridine-4-phenyl-3-thiosemicarbazone

2.12 Comparison with other methods

Various methods have been reported for preconcentration of metal ions on different chelating resins as an adsorbent In our method, Amberlite XAD-2-N=N-APPT resin was used for preconcentration of Pb(II), Zn(II), Co(II), Ni(II), Cu(II), and Cd(II) ions in water samples The analytical parameters such as preconcentration