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), Tehran1485733111, Iran
c Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), Tehran1485733111, Iran
*Corresponding author, Tel.:+982313354058, Fax: +982313354110, E-mail:
Reagent and material
Nitrate salts of interferences werepurchased from Merck (Darmstadt, Germany; 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).
ETAAS / ParameterPb / Cd
283.3 / 228.8 / Wavelength
0.5 / 0.5 / Slit
5 mA / 3 mA / Lamp current
4-206 / 0.22-9.5 / Working range
20 μL / 20 μL / Volume Injection
Peak Area / Peak Area / Mode
Argon / Argon / Gas
120 / 110 / Drying / Temperature (◦C)
900 / 750 / Pyrolysis
2200 / 1900 / Atomization
2300 / 2000 / Cleaning
Table S1 The ETAAS conditions for determination of mentioned metal
Fig. S1Effect 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: 100µL.
Fig. S2Effect 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: 100µL.
Fig. S3Effect 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. S4Effect 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
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 / 116-150 b / 10 mL / [42]
Pb and Cd / SPE / modified nano-alumina / FAAS / Water and herbal samples / 0.15, 0.17 µg L-1 / 2.8, 3.2 / 0.5-200 µg L-1 / 250 b / 500 mL / [43]
Cd, Mn and Pb / SPE / Fe3O4@SiO2@IDA / ICP-MS / Water and milk powder / 0.16, 0.2 µg L-1 / 4.6-7.4 / - / 200 b / 100 mL / [44]
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 / Cd: 2.8, Pb: 7.2, Zn:1.1, Ni: 4.3 68 µg L−1 / - / - / 16.5 b / 50 mL / [47]
Pb and Cd / SPE / solid sulfur / FAAS / Water / Pb: 3.2 µg L-1
Cd: 02 µg L−1 / 5.1 , 4.7 / Pb : 10-300 µg L-1
Cd :1-20 µg L-1 / 500 b / 1000 mL / [10]
Table S2Comparison of US-assisted-DµSPE coupled G-CL with published method for metal ions in different matrixes
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–SPE[1] / 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-SPE[2] / oxidized carbon nanotubes / ETAAS / Serum samples / 10 ng L−1 / 4.0 / - / 40 a / 2 mL / [50]
Cd, Cu and Pb / HF-SPME[3] / MWNT / DPASV[4] / Rice / Cd:0.01 µg L−1
Pb:0.025 µg L−1
Cu:0.0073 µg L−1 / 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]
Pb and Cd / Column SPE / MnO2-CNT / ETAAS / Water / Pb: 4.4 µg L−1
Cd: 1.5 µg L−1 / < 3.2 / - / 100 a / 150 mL / [7]
Cu,Zn and Mn / Column SPE / DCPIMI5-Amberlite / FAAS / Water and fruits / Cu: 1.9 µg L−1
Zn :1.5 µg L−1
Mn:2.6 µg L−1 / ≤3.0 / Cu: 0.01-0.34 mg L−1
Zn :0.01-0.3 mg L−1
Mn:0.02-0.31 mg L−1 / 35 b
39 b
27 b / 1350 mL / [37]
Ni, Fe and Pb,Zn / Dispersive SPE / SDS-coated alumina / FAAS / water and food / Zn: 1.6 µg L−1
Ni: 2.1 µg L−1
Fe: 2.6 µg L−1
Pb: 2.8 µg 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 / - / 250 mL / [38]
Pb and Cd / USA-D-µSPE / Graphene-Clinoptilolite hybrid / ETAAS / Water and human serum / Pb: 0.07 µg L−1
Cd:0.004 µg L−1 / 3.4, 3.9 / Pb: 0.24-10.3 µg L-1
Cd: 0.011-0.48 µg L-1 / 20 b / 2 mL / Present work
References
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aPreconcentration 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
53-((2,6-Dichlorophenyl)(1H-indol-3-yl)methyl)-1H-indole (DCPIMI)