Chemical Papers

https://doi.org/10.1007/s11696-018-0387-9

ORIGINAL PAPER

Synthesis and application of a novel magnetic nanosorbent

for determination of trace Cd(II), Ni(II), Pb(II), and Zn(II)
in environmental samples
Zohreh Dahaghin1 · Hassan Zavvar Mousavi1 · Ehsan Mirparizi2 · Parand Haghighat1

Received: 24 August 2017 / Accepted: 8 January 2018

© Institute of Chemistry, Slovak Academy of Sciences 2018

Abstract
In this work for the first time, F
­ e3O4@SiO2 core–shell nanoparticles functionalized with isatin groups as a magnetic nano-
sorbent was applied for the simultaneous extraction of trace amounts of cadmium(II), nickel(II), lead(II), and zinc(II). The
characterization of this nanosorbent was studied using Fourier transform infrared spectroscopy, scanning electron microscopy,
energy-dispersive X-ray spectrometry, X-ray diffraction, vibrating sample magnetometer and thermogravimetric analysis.
The effect of several factors such as pH, amount of sorbent, extraction time, type and volume of the eluent, sample volume,
sorption capacity, and potentially interfering ions was investigated. In the selected conditions, it was observed that the limits
of detection were 0.11 ng mL−1 for Cd(II), 0.28 ng mL−1 for Ni(II), 0.47 ng mL−1 for Pb(II), and 0.21 ng mL−1 for Zn(II),
and the maximum sorption capacity of this suggested magnetic nanosorbent was 120, 112, 100, and 100 mg g−1 for Cd(II),
Ni(II), Pb(II), and Zn(II), respectively. Also, the precision of the method (RSD%) for ten replicate measurements was found
2.5, 2.5, 2.8, and 3.1%, for Cd(II), Ni(II), Pb(II), and Zn(II) ions, respectively. Finally, the suggested procedure was applied
for determination of cadmium(II), nickel(II), lead(II), and zinc(II) at trace levels in different water and agricultural products
with satisfactory results.

Keywords Magnetic nanosorbent · Isatin · Cadmium(II) · Nickel(II) · Lead(II) · Zinc(II)

Introduction metallic materials in natural source water was enhanced as a

result of growing the application of heavy metals in indus-
One of the main problems in environmental pollutants is tries and causes several environmental problems (Tangjuank
heavy metal ions, which have toxic effects on the human et al. 2009). Recent years, nanoparticle materials, especially
health and life in aquatic systems. Therefore, one of the magnetic nanoparticles have aroused a great deal of atten-
greatest interested subjects by analytical chemists is deter- tion in analytical chemistry as the sorbents (Ghaemi and
mining the trace amounts of heavy metals and this is one Absalan 2014; Faraji et al. 2010; Bagheri et al. 2012a).
of the important subjects in analytical chemistry (Zhang In contrast, iron oxide nanoparticles due to the important
et al. 1999). The trace amounts of heavy metals are the most properties such as the high surface area to volume, nano-
important contaminants in the source water. The presence of size range and super-magnetism are suitable particles and
in water treatments due to these properties are highly desir-
able (Pan et al. 2010; Laurent et al. 2008). Silica is one of
Electronic supplementary material The online version of this
the most ideal compositions to be used as a shell. The silica
article (http​s://doi.org/10.1007​/s116​96-018-0387​-9) contains
supplementary material, which is available to authorized users. shell protects ­Fe3O4 NPs in acidic medium which is neces-
sary for elution of most metal ions. Also, silica surface with
* Hassan Zavvar Mousavi silanol groups can react with silane coupling to conjugate
[email protected]
with a variety of different ligands (Tadjarodi et al. 2015). A
1
Department of Chemistry, Semnan University, number of preconcentration methods for preconcentration
Semnan 35131‑1911, Iran and detection of trace metal amounts have gained attention
2
Young Researchers and Elite Club, Sirjan Branch, Islamic nowadays, including solvent-assisted dispersive solid-phase
Azad University, Sirjan, Iran extraction (Behbahani et al. 2015), solid-phase extraction

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(SPE) (Marwani et al. 2015), magnetic solid-phase extrac- 5° and 90° (λ = 1.5). Thermogravimetric analyses (TGA)
tion (MSPE) (Bagheri et al. 2012b; Zhao et al. 2016), elec- were conducted with a LINSEIS model STS PT 16000 ther-
trochemical deposition (El Aroui et al. 2014), and membrane mal analyzer at a heating rate of 10 °C ­min−1 for the thermal
separation (Sanaeepur et al. 2016). Isatin (Isa) is chemically gravimetric analysis of synthesized nanoparticles.
immobilized on different solid supports such as chelating
resin, bentonite, and silica nanoparticles to form various Preparation of ­Fe3O4@ ­SiO2 core–shell nanosorbent
solid absorbents, where it has been shown to greatly enhance
the removal of heavy metal ions from aqueous solutions. Magnetic ­Fe3O4 nanoparticles (MNPs) were obtained based
Isatin is a kind of strong bidentate chelating agent and has on simple chemical coprecipitation of ­Fe2+ and ­Fe3+ ions
active functional groups containing N, and S, which act as as reported elsewhere (Saraji and Boroujeni 2014). Briefly,
the chelation with metal cations. 6.1 g of ­FeCl3·6H2O and 4.2 g of ­Fe2SO4·7H2O [Fe(III)/
In the current research, for the first time, ­Fe3O4@SiO2 Fe(II) molar ratio = 2/1] were dissolved in 100 mL distilled
core–shell nanosorbent was modified with isatin (­ Fe3O4@ water, and heated at 80 °C for 30 min, then add 10 mL of
SiO2@Isa) and used as a novel magnetic solid-phase sorbent ammonia solution (25 w/w%) dropwise until formation of
for removal and preconcentration of cadmium(II), nickel(II), ­Fe3O4 occurred. This system was mixed for 4 h by a mag-
lead(II), and zinc(II) ions, and flame atomic absorption spec- netic stirrer in the nitrogen atmosphere. During the whole
trometry (AAS) was chosen for monitoring the concentra- procedure, the temperature of the solution was held at 80 °C.
tion of these target ions. The modified magnetic nanosorbent The product ­(Fe3O4 NPs) was effectively separated in few
was synthesized by a simple reaction and characterized by seconds by a strong magnet and repeated washing with dis-
FT-IR, SEM, EDS, XRD, VSM and TGA. The sorbent was tilled water thoroughly, and finally, the nanoparticles were
then used to determine Cd(II), Ni(II), Pb(II), and Zn(II) ions vacuum-dried at 40 °C for 4 h. Next, the grafting proce-
in different water and agricultural products and the obtained dure of magnetic particles with silica was accomplished as
results were good. follows:
1 g of the prepared ­Fe3O4 NPs were dispersed via ultra-
sonic in a solution of 100 mL deionized water, 25 mL eth-
Experimental anol and 1.5 mL ­NH4OH (25%). Then, 3 mL TEOS was
added dropwise to the solution under stirring until the pro-
Reagents and materials cess of magnetic particles with silica was accomplished
(Sadeghi and Aboobakri 2012). After 12 h stirring at 40 °C,
All reagents used in this study (NaOH, N ­ H3, HCl, ­HNO3, with help of the external magnet, the formed ­Fe3O4@SiO2
­H2SO4, isatine, 3-aminopropyltriethoxysilane (APTES), NPs were collected and washed with deionized water and
Cd(NO3)2, Ni(NO3)2, Pb(NO3)2, Zn(NO3)2, toluene, etha- ethanol and then dried.
nol) were purchased from Merck (Darmstadt, Germany),
Fluka (Buchs, Switzerland) or Sigma-Aldrich (Steinheim, Functionalization of ­Fe3O4@ ­SiO2 core–shell NPs
Germany) without any further purification. Tetraethoxysi-
lane, ­FeCl3·6H2O, and F­ eSO4·7H2O were used in magnetic The procedure for functionalizing F­ e3O4@SiO2 core–shell
nanoparticles preparation and were purchased from Aldrich. NPs was performed in two steps as follows: In the first step,
The stock solution (1000 mg L−1) was readied by dissolv- 1.0 g of F ­ e3O4@SiO2 core–shell NPs were ultrasonically
ing suitable amounts of Cd(NO3)2, Ni(NO3)2, Pb(NO3)2, and dispersed in 50 mL dried toluene in a three neck round-
Zn(NO3)2 in deionized water. bottom flask. Then, 3-aminopropyltriethoxysilane (2.0 mL)
was added to the solution in one portion after stirring for
Apparatus 1 h. The black solid was produced after refluxing under
nitrogen atmosphere for 12 h. Afterward, ­Fe3O4@SiO2@
Concentrations of target metal ions were performed with an APTMS core–shell NPs were isolated by the strong mag-
Agilent Series AA (model 240 AA) flame atomic absorp- net and washed with water and ethanol several times until
tion spectrometer (FAAS) equipped with the air-acetylene discard any impurities, GO@Fe3O4@APTMS nanoparticles
burner. The FT-IR spectra (400–4000 cm−1) were recorded were dried completely at 50 °C for overnight and were used
by S, 8400 Shimadzu FT-IR spectrophotometer. A scanning in the next step of the experiment. The FT-IR spectrum,
electron microscopy (SEM) (KYKY, EM 3200) and energy- SEM, EDS and TGA analyses were applied to confirm the
dispersive X-ray spectrometry (EDS) (Tescan Mira3, Czech) synthesis of GO@Fe3O4 functionalized with APTMS (Bagh-
were used to analyze the surface morphology. X-ray powder eri et al. 2016).
diffraction (XRD) patterns were performed using a Bruker In the second step, about 1.0 g of the ­Fe3O4@SiO2@
D8 Advance (Germany) with the 2θ angle varying between APTMS core–shell NPs was dispersed in 50 mL toluene

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containing 1.0 g of isatin and the reaction mixture was the clear solution of eluent. Finally, the amount of analyte in
stirred and refluxed for 24 h in an oil bath at 80 °C in the eluent was determined by its injection into FAAS.
presence of nitrogen. Hereafter, the black solid obtained was It should be noted that the percentage of extraction for
successively collected by a strong magnet and washed sev- the employed samples was obtained using the following
eral times with ethanol to remove excess unreacted materi- equation:
als and dried under vacuum at 40 °C overnight (Fig. 1Sa)
%Extraction = Ca −Cb ∕Ca × 100,
(Electronic Supplementary Material, ESM). Then, FT-IR,
SEM, XRD, VSM and TGA were used for characterizing where Ca and Cb are initial and final concentrations of each
obtained ­Fe3O4@SiO2@Isa nanosorbent. ion in the solution, respectively (Fig. 1Sb).

Real sample pretreatment

Results and discussion
Presence of cadmium(II), nickel(II), lead(II), and zinc(II)
ions in diverse samples such as water and vegetable sam- Sorbent characterization
ples were determined by the ­Fe3O4@SiO2@Isa nanosorb-
ent. Water samples, including, tap water (Tehran, Iran), and FT-IR spectrum of ­Fe3O4 was recorded using the KBr pellet
river water (Zayanderud, Isfahan, Iran) were selected for method. The advent of the absorption peaks at 582 cm−1 is
evaluating the influence of the synthetic nanocomposite on ascribed to Fe–O stretching and the band at 3435 cm−1 is due
the efficiency of the proposed approach, and then were fil- to the intramolecular hydrogen bonding. The presented find-
tered. 50 mL of each sample was adjusted to pH 6, and their ings confirm that the synthesis of ­Fe3O4 NPs was performed
cadmium(II), nickel(II), lead(II), and zinc(II) ions content successfully. For the ­Fe3O4@SiO2 nanoparticles, the peaks
were determined by the suggested extraction and precon- at 1089 cm−1 (Si–O–Si) and 798 cm−1 (Fe–O–Si) attributed
centration method. that ­SiO2 was successfully coated on the surfaces of ­Fe3O4
Five types of vegetables, including lettuce, broccoli, car- nanoparticles.
rot, cucumber and tomato (local supermarket, Tehran) were For ­Fe3O4@SiO2@APTMS, the absorption peak in the
selected and 1 g of each was grounded, homogenized and area of 1398 represents a Si–C group in the magnetic nano-
dried at 80 °C. After fractionating, the homogenized samples composite structure and the adsorption peak at 2900 cm−1
were sieved, the samples were transferred to a beaker and (C–H) confirmed the existence of APTMS on the surface
dissolved in 10 mL of concentrated nitric acid and heated to of ­Fe3O4@SiO2 NPs. In FT-IR spectrum of F ­ e3O4@SiO2@
90 °C until brown fumes ceased. Subsequent that 10 mL of Isa nanocomposites, the absorption bands at 1400 and
30% hydrogen peroxide was added to each sample, heating 1618 cm−1 areas represented the vibrational frequency of
was retained until the sample became clear. The dilution C=C and C=N band in ­Fe3O4@SiO2@Isa, respectively.
of obtained solution with double distilled water to 100 mL These observations indicate the modification of F ­ e 3O 4@
was carried out in a volumetric flask after filtration (Pirouz SiO2 with Isa group.
et al. 2015). The recommended procedure was performed at
optimal conditions. SEM and EDS characterization

Extraction procedure The morphology of ­Fe3O4@SiO2 and ­Fe3O4@SiO2 nano-

composite functionalized with isatin group was studied using
For the extraction procedure, the pH of 10 mL aqueous solu- SEM for showing the structure of the synthesized nanosorb-
tion including 0.5 mg L−1 of target ions was set at optimal ents. Our literature survey at this stage revealed that accord-
pH (the solution pH was adjusted by dilute NaOH or HCl to ing to SEM patterns shown in Fig. 1a, b reveal the obvious
desired value). Then, 20 mg of the dried magnetic nanosorb- growth of nanocomposite particle size in ­Fe3O4@SiO2@Isa
ent was added into the solution and the prepared mixture was nanocomposite. EDS spectra taken from the F ­ e3O4@SiO2@
stirred for the suitable amount of time for ensuring adequate APTMS nanocomposite are presented in Fig. 2S.
interaction between magnetic sorbent and ions. Afterward,
the magnetic sorbent was collected from the solution with X‑ray characterization
an appropriate magnet and the concentrations of the metal
ions in supernatant were directly determined by FAAS. In Figure 3S shows XRD patterns of ­Fe3O4@SiO2 nanocom-
the elution step, 4 mL of 2 mol L−1 HCl was used to elute posite and ­Fe3O4@SiO2@Isa nanocomposite after reaction
the metal ions adsorbed on the sorbent. For this purpose, the of magnetic ­Fe3O4@SiO2 with isatin group. Different peaks
mixture of sorbent and eluent was stirred for 5 min and then at 2θ = 30.1, 35.5, 43.2, 57.1 and 62.7 and the broad peak at
again exposed on the strong external magnet until obtaining 2θ = 20–30 ­(SiO2 group) in Fig. 3S showed that the structure

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Fig. 1  The SEM image of a ­Fe3O4@SiO2 b ­Fe3O4@SiO2@Isa nanocomposite

of ­Fe3O4@SiO2 nanoparticles remained intact after coating

with Isa groups and any changes and decomposition occur-
ring in the structure of ­Fe3O4@SiO2 after modification. The
low-angle X-ray diffraction pattern of F ­ e3O4@SiO2@Isa
showed decrease in intensity in peaks in comparison with
unfunctionalized ­Fe3O4@SiO2. The average crystallite size
of the ­Fe3O4@SiO2@Isa NPs was estimated from the XRD
pattern using the Scherrer formula:
D = k𝜆∕cos𝜃,
where D is average crystallite size, λ is the X-ray wave-
length, β is the full-width at half maximum (FWHM) and θ
is the diffraction angle. Here, λ = 1.54 Å is chosen for X-ray
wavelength. Thus, the crystallite size of F ­ e3O4@SiO2 NPs
Fig. 2  The TGA curves of ­
Fe3O4@SiO2@APTMS and F
­e3O4@
and ­Fe3O4@SiO2@Isa NPs were computed from the XRD SiO2@Isa nanocomposites
pattern and found to be about 40 and 50 nm.

Thermogravimetric analysis

TGA analysis of F­ e3O4@SiO2@APTMS and F ­ e3O4@SiO2@

Isa nanocomposites are shown in Fig. 2. According to the
TGA analysis, these nanocomposites are stable up to 600 °C.
The weight losses occurred at 250 °C is due to the loss of
residual water and pyrolysis of oxygen-containing groups
in the surface of nanosorbents. Comparing ­Fe3O4@SiO2@
APTMS and ­Fe3O4@SiO2@Isa curves, the difference in
reduction in weight of these nanocomposites (weight loss
about 30 and 60% for ­Fe3O4@SiO2@APTMS and ­Fe3O4@
SiO2@Isa, respectively) indicates the presence of isatin
group in the nanocomposite.

VSM characterization

Figure 3 shows the magnetization curve of the F ­ e 3O 4@

SiO2@Isa nanocomposites. The saturation magnetization Fig. 3  Magnetization curves of F
­ e3O4@SiO2@Isa nanocomposites at
of the nanocomposite was found to be equal to 15 emu g−1. 300 K

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Optimization of extraction conditions Isa nanocomposite and extraction procedure was performed.
The obtained result indicated that the better eluent for Cd(II),
Effect of pH Ni(II), Pb(II), and Zn(II) ions from the sorbent was 3 mL of
2 mol L−1 HCl solution (Fig. 7S). Then, the effect of elution
To investigate the effect of pH on the extraction recovery, time on recovery of Cd(II), Ni(II), Pb(II), and Zn(II) ions
10 mL of different aqueous sample solutions containing was studied in the range of 2–20 min. The results indicated
specified amount of analytes (0.5 mg L−1 of Cd(II), Ni(II), the suitability of 10 min for a better recovery.
Pb(II), and Zn(II) ions) was studied in the pH range from 2
to 9. The pH of solutions was set using hydrochloric acid or Effect of sample volume
sodium hydroxide solutions. As can be observed in Fig. 4S,
the suitable recoveries of target metal ions occurred at pH The volume of sample plays an important role in analyzing
6. At alkaline pH, analyte ions convert to M ­ n+(OH)n and real samples and it is effective on the preconcentration factor.
produce hydroxide forms. Thus, they lose their tendency to In a condition in which all solutions were adjusted according
form complexes with amine and oxygen groups of magnetic to the optimum condition obtained for the suggested tech-
nanosorbent and the efficiency decreases. nique, examination of the effect of sample volume param-
eter on quantitative sorption of Cd(II), Ni(II), Pb(II), and
Effect of nanosorbent amounts Zn(II) ions was performed using 20 mg of ­Fe3O4@SiO2@Isa
sorbent in various volumes of the sample within the range
For achieving the highest quantitative efficiency for extract- of 25–1000 mL containing 1 mg of target ions. According
ing Cd(II), Ni(II), Pb(II), and Zn(II) ions, the optimal to the results given in Fig. 4, the recovery of all ions on
amount of F ­ e3O4@SiO2@Isa nanocomposites was obtained. the ­Fe3O4@SiO2@Isa nanocomposite was obtained more
Thus, varying amounts of nanocomposite ranging from 5 than 98% for the sample volumes up to 800 mL, but it was
to 30 mg were tested. The illustrated outcomes in Fig. 5S reduced when dilution was raised up at higher volume. Thus,
indicated by increasing amounts of F ­ e 3O 4@SiO 2@Isa 800 mL of the sample volume was chosen for the proposed
nanocomposite up to 20 mg and the extraction efficiency extraction method and the preconcentration factor (PF) for
increased in response to the increase of surface area. There- synthetic magnetic nanocomposite was calculated to be 266
fore, the subsequent studies were performed using 20 mg of when 3 mL of elution was used.
nanocomposite to get a satisfactory result. The extraction
recovery was nearly constant with using higher amounts of Effect of potentially interfering ions
the sorbent.
To assess the effect of potentially interfering ions,
Effect of sorption time several common anions and cations with different

Different time periods (2, 4, 5, 8 and 10 min) for Cd(II),

Ni(II), Pb(II), and Zn(II) ions sorption on the magnetic
­Fe3O4@SiO2@Isa nanocomposite were tested. For this step,
20 mg ­Fe3O4@SiO2@Isa was added to 10 mL of sample
solutions (0.5 mg L−1 of target ions) at optimal pH, and
the mixture was shaken for various ranges of time periods.
Based on obtaining outcomes in Fig. 6S, for obtaining the
maximum yield, 5 min is enough for extracting the analytes
from solution quantitatively, and this time was selected as
the optimum sorption time.

Elution condition

In the current study, several types of eluents (HCl, H

­ NO3, Fig. 4  Effect of sample volume on recovery of Cd(II), Ni(II), Pb(II),
­H2SO4, NaOH, and ­NH3) were selected for elution of Cd(II), and Zn(II) ions on F­ e3O4@SiO2@Isa nanocomposite
Ni(II), Pb(II), and Zn(II) ions from magnetic ­Fe3O4@SiO2@

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concentrations were added to 100 mL of the solution con- ions. The LOD was calculated based on three times of
taining 0.003 mg L−1 of cadmium(II), nickel(II), lead(II), blank signal (six replicate blank measurements) divided by
and, zinc(II) (Table 1S). The reported tolerance limit was the slope of the calibration curve ­(3Sb/m) and it was 0.11,
herein defined as the ion concentration producing a relative 0.28, 0.47, and 0.21 ng mL −1 for Cd(II), Ni(II), Pb(II),
error ≤ ± 5%. The results showed (Table 1S) this technique and Zn(II), respectively. The relative standard deviation
could be suggested for determination of these heavy metal (RSD%) was measured for a standard solution containing
ions in samples with a complicated matrix with excellent specific amount of these ions (n = 10). This value was 2.5,
selectivity. 2.5, 2.8, and 3.1%, for Cd(II), Ni(II), Pb(II), and Zn(II)
ions, respectively.
Maximum adsorption capacity study
Determination of Cd(II), Ni(II), Pb(II), and Zn(II) ions
The total amount of every analyte sorbed per gram of in various real samples
the magnetic sorbent is specified as the highest sorption
capacity of the sorbent. To determine this parameter, the To evaluate the performance of the synthetic ­F e 3O 4@
batch MSPE procedure was investigated using an aqueous SiO2@Isa nanocomposites, the suggested technique was
solution containing 50 mg L−1 of Cd(II), Ni(II), Pb(II), used to determine Cd(II), Ni(II), Pb(II), and Zn(II) in the
and Zn(II) ions, and it was calculated by determining the real samples such as water and vegetable samples (let-
difference between the concentration of analyte in the tuce, broccoli, carrot, cucumber and tomato), under the
solution before and after extraction using FAAS. This optimum conditions. The recovery percentages relating to
parameter was calculated using the following equation: extract analytes from real samples were given in Table 1.
[ ] Table 1 show that higher yields are obtained using this
Q = (C0 − CA ) × V ∕m,
novel nanosorbent.
where Q, C0, CA, V and m are the amount of metal ions
sorbed onto the unit, amount of the composites (mg g−1), ini- Comparison of developed method with other
tial concentration (mg L−1) of each ion, final concentrations published methods
(mg L−1) of each ion, the volume of the aqueous phase (L),
and the weight of the magnetic nanosorbent (g), respectively. Table 2 presents the results of comparing the characteris-
The sorption capacity of magnetic ­Fe3O4@SiO2@Isa nano- tic data of mentioned method with other previous methods
composite was calculated 120, 112,100, and 100 mg g−1 (Kumar et al. 2000; Pourreza et al. 2014; Silva and dos San-
for Cd(II), Ni(II), Pb(II), and Zn(II) ions, respectively. The tos Roldan 2009; Ghodsbin et al. 2014; ALOthman et al.
sorption capacity of magnetic ­Fe3O4@SiO2 nanocompos- 2012). According to the table, the obtained detection limit
ite was calculated 50, 80, 37, and 44 mg g−1 for Cd(II), using ­Fe3O4@SiO2@Isa nanocomposite is significantly
Ni(II), Pb(II), and Zn(II) ions, respectively, that depicts bet- lower than other approaches. As can be seen, this magnetic
ter absorption by ­Fe3O4@SiO2@Isa nanocomposite. Also, nanocomposite has good preconcentration factor comparing
under the chosen conditions, it was observed that ­Fe3O4@ to other techniques.
SiO2@Isa nanosorbent can be applied six times without sig-
nificant considerable loss in their sorption capacity.
Conclusion
Analytical performance of method
Heavy metal pollutants are considered to be a criti-
For this ­F e 3 O 4 @SiO 2 @Isa nanocomposite linearity cal contaminant as they pose harmful health risks and
was within the range of 0.2–50 ng mL−1 for cadmium, extraction of heavy metal ions from water solutions is
0.5–120 ng mL−1 for nickel, 1–200 ng mL−1 for lead, and done using different methods and adsorption processes
0.1–90 ng mL−1 for zinc in the initial solution. The cor- (Dahaghin et al. 2017a, b, c). In the current research for
relation of determination (r2) was 0.9966 for Cd(II) and the first time, we introduce a novel magnetic nanosorbent
0.9985 for Ni(II), 0.9985 for Pb(II), and 0.9987 for Zn(II)

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Table 1  Analysis of cadmium, nickel, lead and zinc ions in different water and agricultural products
Solid sample Analyte Real sample Added Found Recovery (%) RSD%
(ng mL−1) (ng mL−1) (ng mL−1)

Cucumber Cadmium – 10.00 9.00 90.00 1.00

Nickel 6.73 10.00 16.50 97.70 1.35
Lead 3.11 10.00 13.53 104.20 1.65
Zinc 10.43 10.00 20.22 97.90 1.86
Tomato Cadmium – 10.00 8.87 88.70 1.85
Nickel 8.35 10.00 18.16 98.10 1.81
Lead 6.54 10.00 16.04 95.00 1.30
Zinc 8.76 10.00 18.54 97.80 1.76
Carrot Cadmium 2.12 10.00 11.51 93.90 1.56
Nickel 5.41 10.00 15.24 98.30 2.11
Lead – 10.00 9.90 99.00 1.20
Zinc 10.31 10.00 20.10 97.90 2.10
Lettuce Cadmium – 10.00 9.70 97.00 2.23
Nickel 4.51 10.00 14.32 98.10 2.15
Lead – 10.00 8.72 87.20 1.57
Zinc 9.50 10.00 19.40 99.00 2.32
Broccoli Cadmium – 10.00 10.82 108.2 1.68
Nickel 8.27 10.00 18.18 99.10 2.20
Lead 5.89 10.00 15.45 95.60 1.55
Zinc 8.98 10.00 18.70 97.20 1.56
Sample Analyte Real sample Added Found Recovery (%) RSD%
(ng mL−1) (ng mL−1) (ng mL−1)

Tap (Tehran, Iran) Cadmium – 10.00 9.85 98.50 1.83

Nickel – 10.00 9.90 99.00 1.87
Lead – 10.00 11.65 116.5 2.31
Zinc 4.59 10.00 14.20 96.10 1.38
River water (Zayanderud, Cadmium 2.47 10.00 12.24 97.70 1.72
Isfahan, Iran) Nickel 8.49 10.00 18.10 96.10 1.45
Lead 4.23 10.00 13.58 93.50 2.10
Zinc 9.82 10.00 19.69 98.70 2.13

consisted of ­SiO2, ­Fe3O4 nanoparticles, and isatin group the high preconcentration factors of this new developed
and applied for rapid and facile separation of trace quanti- method, trace amounts of heavy metals in high-volume
ties of cadmium(II), nickel(II), lead(II), and zinc(II) ions samples can be quantified using this magnetic nanocom-
from various matrices. The characterization of this novel posite. In conclusion, considering the obtained outcomes,
sorbent was performed using FT-IR, SEM, EDS, XRD, the suggested new nanocomposite is facile, easy and fast,
VSM, and TGA. Low LOD and RSD, and excellent yields and can be used in complex matrices.
with short extraction times are the main advantages of
this magnetic nanocomposite. Another advantage, due to

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Table 2  Comparison between proposed methods with previous works

Instrument Analytical technique Elements LOD PFa MACb Refs.

(ng mg−1) (mg g−1)

FAAS XAD-2 functionalized with o-aminophenol Cadmium 2.0 50 3.42 Pirouz et al. (2015)
Nickel 7.5 65 3.24
Lead 25.0 40 3.32
Zinc – – –
FAAS Nano-TiO2-MBT-FAAS Cadmium 0.12 106 – Pourreza et al. (2014)
Nickel – – –
Lead 1.38 83 –
Zinc – – –
FAAS Cloud point extraction Cadmium 0.74 43 – Sadeghi and Aboobakri (2012)
Nickel – – –
Lead 4.6 43 –
Zinc – – –
FAAS SPE on soft husk of Pistachio Cadmium 0.13 133 – Sanaeepur et al. (2016)
Nickel 0.98 133 –
Lead 2.58 133 –
Zinc – – –
FAAS Multiwalled carbon nanotubes impregnated Cadmium 2.8 – 3.9 Saraji and Boroujeni (2014)
with 4-(2-thiazolylazo)resorcinol Nickel 4.3 – 4.6
Lead 7.2 – 1
Zinc 1.1 – 6.2
FAAS Fe3O4@SiO2@Isatin Cadmium 0.11 266 120 This work
Nickel 0.28 266 112
Lead 0.47 266 100
Zinc 0.21 266 100
a
Preconcentration factor
b
Maximum adsorption capacity

Acknowledgements Due to the support of this work, the author thanks Behbahani M, Hassanlou PG, Amini MM, Omidi F, Esrafili A, Far-
the Semnan University Research Council. zadkia M et al (2015) Application of solvent-assisted dispersive
solid phase extraction as a new, fast, simple and reliable precon-
centration and trace detection of lead and cadmium ions in fruit
and water samples. Food Chem 187:82–88
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