Electronic Supplementary Material
Ultrasound-assisted dispersive solid phase extraction of cadmium(II) and lead(II) using a
hybrid nanoadsorbent composed of graphene and the zeolite clinoptilolite
Mehri Ghazaghia, Hamid Shirkhanloob, Hassan Zavvar Mousavia,* , Ali Morad Rashidic
a
Department of Chemistry, College of Science, Semnan University, Semnan, Iran, Zip Code:
35131-19111
b
Occupational and Environmental Health Research Center (OEHRC), Iranian Petroleum
Industry Health Research Institute (IPIHRI), Tehran 1485733111, Iran
c
Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), Tehran
1485733111, Iran
*Corresponding author, Tel.: +982313354058, Fax: +982313354110, E-mail: hzmousavi@semnan.ac.ir
Reagent and material
Nitrate salts of interferences were purchased from Merck (Darmstadt, Germany;
http://www.merckgroup.com). The salt of magnesium nitrate (Mg (NO3)2) was used as a
chemical matrix modifier for determination of Pb (II) and Cd (II) by ETAAS.
Apparatus
The aliquots of 20 µL of all sample and calibration solutions were injected by furnace
auto-sampler (PAL3000). The inert argon gas was used with high purity (99.99 %) as the
protective and purge gas. The pH values were measured with a digital pH meter (Metrohm 744,
USA). The pH-meter supplied with a glass-combined electrode. Absorbent were dispersed in
solution using an ultrasonic water bath (KQ2200DE Ultrasonic Cleanser, 100 W, Equipment
Company, Italy).
Table S1 The ETAAS conditions for determination of mentioned metal
ETAAS
Parameter
Cd
Pb
228.8
283.3
0.5
0.5
3 mA
5 mA
0.22-9.5
4-206
20 μL
20 μL
Peak Area
Peak Area
Argon
Argon
Drying
110
120
Pyrolysis
750
900
Atomization
1900
2200
Cleaning
2000
2300
Wavelength
Slit
Lamp current
Working range
Volume Injection
Mode
Gas
Temperature (◦C)
Fig. S1 Effect of amount of sorbent on the recovery of 0.5 µg L-1 of lead and 0.2 µg L-1 of
cadmium. Conditions: pH: 5.0; volume: 2.0 mL; volume of eluent: 100 µL.
Fig. S2 Effect of concentration of acid on the recovery of 0.5 µg L-1 of lead and 0.2 µg L-1 of
cadmium. Conditions: pH: 5.0; volume: 2.0 mL; amount of adsorbent: 5.0 mg; volume of eluent:
100 µL.
Fig. S3 Effect of volume of acid on the recovery of 0.5 µg L-1 of lead and 0.2 µg L-1 of cadmium.
Conditions: pH: 5.0; volume: 2.0 mL; amount of adsorbent: 5.0 mg; concentration of acid: 0.5
mol L-1.
Fig. S4 Effect of Extraction time on the recovery of 0.5 µg L-1 of lead and 0.2 µg L-1 of
cadmium. Conditions: pH: 5.0; volume: 2.0 mL; amount of adsorbent: 5.0 mg; concentration of
acid: 0.5 mol L-1
Table S2 Comparison of US-assisted-DµSPE coupled G-CL with published method for metal ions in different matrixes
Metal ions
Method
Sorbent
Detection
Matrix
LOD
RSD %
Calibration range
PF/EF
Sample
volume
Ref.
Cd, Co, Cr, Ni, Pb,
Zn
SPE
decanoic acid-coated
Fe3O4 NPs
ICP-OES
water
0.2-0.8 µg L-1
3.1 (N=6)
1-400 µg L-1
116150 b
10 mL
][42
0.15, 0.17 µg L-1
2.8, 3.2
0.5-200 µg L-1
250 b
500 mL
][43
µg L-1 0.16, 0.2
4.6-7.4
-
200 b
100 mL
][44
Water and
herbal
samples
Water and
milk powder
Pb and Cd
SPE
modified nano-alumina
FAAS
Cd, Mn and Pb
SPE
Fe3O4@SiO2@IDA
ICP-MS
Pb
SPE
ion-imprinted particles
FAAS
Water
50.2 µg L-1
3.8
0.05-2.5 mg L-1
10 b
100 mL
][45
Cu2+, Co2+, Ni2+, Pb2+
SPE
MWNT
FAAS
Water
1.64–5.68 µg L−1
-
-
40 b
400 mL
][46
Cd(II), Pb(II), Zn(II)
and Ni(II)
SPE
MWNT
FAAS
Food samples
-
-
16.5 b
50 mL
][47
Pb and Cd
SPE
solid sulfur
FAAS
Water
5.1 , 4.7
Pb : 10-300 µg L-1
Cd :1-20 µg L-1
500 b
1000
mL
][10
Cd: 2.8, Pb: 7.2,
Zn:1.1, Ni: 4.3 68
µg L−1
Pb: 3.2 µg L-1
Cd: 02 µg L−1
Cd, Co, Ni and Pb
FI online
microcolumn SPE
black stone (Pierre
noire)
ICP-OES
Human urine
0.3-1.13 µg L−1
2.7-5.9
-
-
3 mL
][48
of Cd(II) and Pb(II)
SM–SPE1
Fe3O4 nano-particle
FAAS
Water and soil
samples
0.15 , 0.74 µg L−1
3.15, 3.82
Pb : 1–10 mg/L
Cd : 0.1–1.0 mg/L
25 b
10 mL
][49
Cd
FI-SPE2
oxidized carbon
nanotubes
ETAAS
Serum samples
10 ng L−1
4.0
-
40 a
2 mL
][50
3.2-4.02
Cd: 0.05–500 µg L-1
Pb: 0.05–500 µg L-1
Cu: 0.01–100 µg L-1
4539,
5483 b
5 mL
][51
< 3.2
-
100 a
150 mL
][7
Cu: 0.01-0.34 mg L−1
Zn :0.01-0.3 mg L−1
Mn:0.02-0.31 mg L−1
0.01-0.5 mg L-1
0.015-0.6 mg L-1
0.02-0.4 mg L-1
0.02-0.6 mg L-1
35 b
39 b
27 b
1350
mL
[37]
-
250 mL
[38]
20 b
2 mL
Present
work
3
Cd, Cu and Pb
HF-SPME
Pb and Cd
Column SPE
4
MWNT
DPASV
Rice
MnO2-CNT
ETAAS
Water
Column SPE
DCPIMI -Amberlite
FAAS
Water and
fruits
Zn, Ni, Fe and Pb
Dispersive SPE
SDS-coated alumina
FAAS
water and food
Pb and Cd
USA-D-µSPE
GrapheneClinoptilolite hybrid
ETAAS
Water and
human serum
Cu, Zn and Mn
5
a
Preconcentration Factor
b
Enhancement factor
1
Surfactant mediated solid phase extraction
2
Flow injection solid phase extraction
3
Hollow fiber solid phase microextraction
4
Differential pulse anodic stripping voltammetry
5
3-((2,6-Dichlorophenyl)(1H-indol-3-yl)methyl)-1H-indole (DCPIMI)
Cd:0.01 µg L−1
Pb:0.025 µg L−1
Cu:0.0073 µg L−1
Pb: 4.4 µg L−1
Cd: 1.5 µg L−1
Cu: 1.9 µg L−1
Zn :1.5 µg L−1
Mn:2.6 µg L−1
Zn: 1.6 µg L−1
Ni: 2.1 µg L−1
Fe: 2.6 µg L−1
Pb: 2.8 µg L−1
Pb: 0.07 µg L−1
Cd:0.004 µg L−1
≤3.0
-
3.4, 3.9
Pb: 0.24-10.3 µg L-1
Cd: 0.011-0.48 µg L-1
References
[42] Faraji M, Yamini Y, Saleh A, Rezaee M, Ghambarian M, Hassani R (2010) A nanoparticle-based
solid-phase extraction procedure followed by flow injection inductively coupled plasma-optical emission
spectrometry to determine some heavy metal ions in water samples. Anal Chim Acta 659:172-177
[43] Ezoddin M, Shemirani F, Abdi K, Saghezchi MK, Jamali MR (2010) Application of modified nanoalumina as a solid phase extraction sorbent for the preconcentration of Cd and Pb in water and herbal
samples prior to flame atomic absorption spectrometry determination. J Hazard Mater 178:900-905
[44] Zhang N, Peng H, Wang S, Hu B (2011) Fast and selective magnetic solid phase extraction of trace
Cd, Mn and Pb in environmental and biological samples and their determination by ICP-MS. Microchim
Acta 175:121-128
[45] Esen C, Andac M, Bereli N, Say R, Henden E, Denizli A (2009) Highly selective ion-imprinted
particles for solid-phase extraction of Pb2+ ions. Mater Sci Eng C 29:2464-2470
[46] Duran A, Tuzen M, Soylak M (2009) Preconcentration of some trace elements via using multiwalled
carbon nanotubes as solid phase extraction adsorbent. J Hazard Mater 169:466-471
[47] Alothman Z, Habila M, Yilmaz E, Soylak M (2012) Solid phase extraction of Cd(II), Pb(II), Zn(II)
and Ni(II) from food samples using multiwalled carbon nanotubes impregnated with 4-(2thiazolylazo)resorcinol. Microchim Acta 177:397-403
[48] Suleiman JS, Hu B, Huang C, Zhang N (2008) Determination of Cd, Co, Ni and Pb in biological
samples by microcolumn packed with black stone (Pierre noire) online coupled with ICP-OES. J Hazard
Mater 157:410-417
[49] Jalbani N, Soylak M (2014) Ligandless surfactant mediated solid phase extraction combined with
Fe3O4 nano-particle for the preconcentration and determination of cadmium and lead in water and soil
samples followed by flame atomic absorption spectrometry: Multivariate strategy. Ecotox Environ Saf
102:174-178
[50] Acosta M, Savio M, Talio MC, Ferramola ML, Gil RA, Martinez LD (2013) On-line solid phase
extraction of Cd from protein fractions of serum using oxidized carbon nanotubes coupled to
electrothermal atomization atomic absorption spectrometry. Microchem J 110:94-98
[51] Es’haghi Z, Khalili M, Khazaeifar A, Rounaghi GH (2011)Simultaneous extraction and
determination of lead, cadmium and copper in rice samples by a new pre-concentration technique: Hollow
fiber solid phase microextraction combined with differential pulse anodic stripping voltammetry.
Electrochim Acta 56:3139-3146