TUGAS MAKALAH MATA KULIAH KIMIA ANALISIS II

REVIEW JURNAL SPEKTROFOTOMETER SERAPAN ATOM

Dosen Pengampu : Adi Yugatama, S.Farm., M.Sc,. Apt

Anggota Kelompok : Annisa Yuwandari (M0618005)

Eka Luthfiana K.N.H (M0618014)

Izzatul Faizah A ()M0618025)

Ryza Aisyah Tsakiila Sayko (M0618047)

Safira Faradhian Putranto (M0618048)

Yuanita Maharani (M0618054)

PROGRAM STUDI S1 FARMASI

FAKULTAS MATEMATIKA DAN ILMU PENGETAHUAN ALAM
UNIVERSITAS SEBELAS MARET
SURAKARTA
2019
 BAB I

PENDAHULUAN

Timbal dapat terdapat dalam makanan dan minuman sebagai cemaran, sehingga

menimbulkan bahaya bagi kesehatan jangka panjang. Penentuan timbal pada suatu sampel dapat

menggunakan teknik analitis yang sensitif dan handal. Hanya beberapa teknik seperti atom

elektrotermal spektrometri serapan es (ET-AAS) atau voltametri pengupasan anoda dengan

microelectroda yang memiliki sensitivitas yang cukup untuk secara langsung menentukan jumlah

timbal yang rendah. Metode prekonsentrasi dan pemisahan, ditambah dengan FAAS menawarkan

sistem deteksi yang sederhana dan murah. Di antara teknik-tekniknya, prosedur SPE (Solid Phase

Extraction), baik off- atau on-line, dianggap lebih unggul daripada prosedur lainnya untuk

kesederhanaannya, ekonomis dalam penggunaan pelarut organik, kemampuan untuk

menghilangkan komponen matriks yang tidak diinginkan dan kemampuan mereka untuk mencapai

faktor pengayaan yang lebih tinggi. Dibandingkan dengan partikel berukuran mikrometer yang

digunakan di SPE, NP(Nano Particles) menawarkan banyak manfaat. NP memiliki rasio

permukaan yang jauh lebih tinggi, area ke volume dan rute difusi pendek, menghasilkan lebih

tinggi kapasitas ekstraksi; dinamika ekstraksi yang cepat dan efisiensi ekstraksi.

Tujuan dari penelitian pada jurnal yang kami acu adalah untuk mengembangkan metode

berbasis NP untuk prakonsentrasi dan penentuan jumlah timah. Metode ini didasarkan pada

ekstraksi timah sebagai kompleks hidrofobik dari timbal-PAN pada cetyltrimethylam-monium

bromida (CTAB) - dilapisi Fe3O4 NPs. Tingkat timbal dalam fase diekstraksi kemudian

ditentukan oleh FAAS

 BAB II

ISI

A. METODE

2.1 Alat

Model spektrometer serapan atom nyala Varian (Mulgrave, Victoria, Australia)

SpectrAA 110, dengan nyala udara asetilena digunakan untuk penentuan timbal. Pengukuran

absorbansi dilakukan pada 217,0 nm menggunakan lampu katoda timbal berongga (dari Varian)

yang dioperasikan pada 4,0 mA dengan koreksi latar belakang deuterium (pada 10 mA). Parameter

instrumental digunakan sesuai dengan rekomendasi pabrikan. Semua pengukuran didasarkan pada

ketinggian puncak. PH larutan diukur dengan pH meter WTW (Inolab, Jerman) yang disuplai

dengan elektroda pH kombinasi. Gambar TEM diperoleh dengan mikroskop elektron transmisi H-

800 (Hitachi, Jepang) dan sifat magnetik dianalisis menggunakan magnetometer sampel bergetar

(VSM, LDJ9600).

2.2. Reagents

Semua bahan kimia yang digunakan adalah kelas reagen analitis.

• Besi klorida (FeCl3Æ6H2O) • Timah nitrat (Pb (NO3) 2)

• Besi klorida (FeCl2Æ4H2O) • CTAB

• Natrium hidroksida • Metanol

• 1- (2-pyridilazo) -2 naphthol (PAN) • Aseton

 Solusi stok timbal (1000 lgmL1) dibuat dengan melarutkan jumlah Pb (NO3) 2 yang sesuai

dalam air suling ganda. Larutan 1 · 103 mol L1 PAN dibuat dengan melarutkan jumlah yang tepat

dari reagen ini dalam methanol.

2.3. Sintesis Fe3O4 NPs

Fe3O4 dibuat dengan metode pengendapan kimia melalui reaktor.

a. 10,4 g FeCl3Æ6H2O, 4.0g FeCl2Æ 4H2O dan 1,7 mL HCl (12 mol L1) dilarutkan dalam

50 mL air deionisasi untuk menyiapkan larutan stok.

b. Prekonsentrasi jumlah jejak timbal dalam sampel air dengan cetyltrimethylam onium

bromide S1541 besi dan besi klorida dalam gelas kimia yang kemudian didegradasi dengan

gas nitrogen selama 20 menit.

c. Secara bersamaan, 500 mL larutan 1,5 mol L1 NaOH didegradasi (selama 15 menit) dan

dipanaskan hingga 80 C dalam reaktor.

d. Kemudian, larutan stok ditambahkan tetes demi tetes menggunakan corong tetes selama

30 menit di bawah perlindungan gas nitrogen dan pengadukan kuat (1000 rpm) oleh

pengaduk gelas.

e. Selama seluruh proses, suhu larutan dipertahankan pada 80 C dan gas nitrogen dibersihkan

untuk menghilangkan oksigen terlarut.

f. Setelah selesai reaksi, NP Fe3O4 yang diperoleh dipisahkan dari media reaksi oleh medan

magnet, dan kemudiandicuci dengan 500 mL air suling ganda sebanyak empat kali.

g. Akhirnya,NP Fe3O4 yang diperoleh disuspensikan kembali dalam 500 mL air deionisasi

yang telah diuraikan.

2.4. Prosedur prakonsentrasi

a. Satu alikuot sampel air (500 mL, pH = 9.0) dipindahkan ke 2000 gelas gelas.

b. Kemudian, 2,0 mL PAN 1 · 103 mol L1, 10 mL suspensi NP Fe3O4 (10 mg mL1) dan 2,5

mL larutan CTAB (10 mg mL1) secara berurutan ditambahkan ke larutan sampel dan

kemudian dicampur.

c. Campuran dikocok dan dibiarkan menyelesaikan proses ekstraksi selama 2 menit.

d. Selanjutnya, magnet NdFe-B yang kuat (10,5-5,4 cm, 1,4 Tesla) ditempatkan di bagian

bawah gelas kimia, dan NP Fe3O4 yang dilapisi CTAB diisolasi dari larutan.

e. Setelah sekitar 10 menit, larutan menjadi jernih dan solusi supernatan didekantasi.

f. Akhirnya, kompleks timah prakonsentrasi dielusi dari partikel yang diisolasi dengan 1,0

mL HCl 0,5% dalam metanol dan larutan ini dimasukkan ke dalam FAAS untuk penentuan

konsentrasi timbaL.
B. HASIL DAN PEMBAHASAN

3.1. Karakterisasi Fe3O4 nanopartikel

Gambar hasil

Gambar 1. Karakterisasi Fe3O4NPs yang dilapisi CTAB. (a) Spektra IR sebelum (i) dan setelah

modifikasi dengan CTAB (ii). (B) Gambar TEM dari Fe3O4NPs. (c) magnet magnetisasi VSM

dari Fe3O4NPs.
 Fe3O4NPs disintesis dilakukan dengan menggunakan instrumen IR, VSM dan TEM (Gbr.

1). Spektrum IR Fe3O4NPs murni (i) dan Fe3O4NPs yang dilapisi CTAB (ii) ditunjukkan dalam

Gambar. 1a. Puncak pada 3455 cm 1 dikaitkan dengan getaran peregangan –OH, yang ditugaskan

ke permukaan gugus OH dari Fe3O4NPs. Puncak pada 571 cm 1 dikaitkan dengan getaran band

Fe-O dari Fe3O4. Juga, puncak pada 1380 cm 1 disalurkan ke pita C – N dan puncak pada 2885

dan 2925 cm 1 dihubungkan dengan dua pita C-H yang berbeda dari getaran CTAB. Spektra IR

menunjukkan bahwa permukaan Fe3O4NP dapat dimodifikasi dengan baik oleh CTAB.

Juga, gambar TEM dari NP yang sudah disiapkan ditunjukkan pada Gambar 1b.

Berdasarkan gambar TEM, analisis morfologi permukaan Fe3O4 menunjukkan agregasi banyak

partikel ultrafine dengan diameter sekitar 20 nm. Di sisi lain, penting bahwa Fe3O4NPs harus

memiliki properti magnet dan superparamagnetik yang memadai untuk aplikasi praktis teknologi

pembawa magnetik (MCT).

Gambar. 1c menunjukkan kurva magnetisasi VSM ofFe3O4NPs pada suhu kamar.

Fe3O4NPs menunjukkan perilaku supparamagnetic khas karena tidak menunjukkan histeresis,

remanen dan koersivitas. Magnetisasi saturasi besar Fe3O4NPs adalah 76 emu / g, yang cukup

untuk magnet penghapusan dengan magnet konvensional

3.2. Pengaruh pH larutan.

Gambar Hasil

Gambar 2. Efek pH sampel pada efisiensi ekstraksi. Kondisi: 500 mL 50 ng mL 1 timbal; 1,0 mL

larutan 0,001 mol L 1351PAN (L / M = 8); 100 mg Fe3O4NPs; 50 mg CTAB; pengadukan 5

menit, elusi dengan 1,0 mL methanol.

Densitas muatan permukaan oksida mineral adalah faktor utama yang melindungi adsorpsi

analit dan sangat bervariasi dengan pH. Dengan demikian, pH adalah parameter yang sangat

penting untuk adsorpsi senyawa target. Di sisi lain, pH memainkan peran penting dalam

kompleksasi timbal dengan PAN. Untuk menguji pengaruh pH pada efisiensi ekstraksi ion timbal,

pH larutan bervariasi dalam kisaran 6,0-12,0 (Gbr. 2). Seperti yang bisa dilihat dari Gambar. 2,

Fe3O4NPs tidak terlihat jelas adsorpsi timbal sebagai kompleks Pb-PAN ketika nilai pH lebih

rendah dari 8,0. Dengan meningkatnya pH, efisiensi adsorpsi meningkat secara dramatis dan

mencapai maksimum ketika pH antara 9.0 dan 10.0. Hal ini terutama disebabkan oleh fakta bahwa

muatan negatif menguntungkan untuk adsorpsi surfaktan cat-ionik. Ketika nilai pH sekitar NP titik

isoelektrik (sekitar 7,0) kepadatan muatan permukaan Fe3O4NPs sangat rendah (Zhao et al.,
2008b). Ketika nilai pH berada di atas titik isoelektriknya, permukaan Fe3O4NP bermuatan negatif

yang memunculkan daya tarik elektrostatik yang kuat antara molekul CTAB dan permukaan

Fe3O4NPs yang bermuatan. Di bawah keadaan ini, kompleks hidrofobik dari Pb-PAN dapat

berinteraksi dengan permukaan FAB3F4OPN yang dilapisi CTAB. Tetapi, pada pH lebih tinggi

dari 10,0, timbal dapat dipra-sipasi sebagai bentuk hidroksida. Di sisi lain, pH antara 9.0 dan 10.0

menguntungkan untuk kompleksasi timbal dan PAN (Marczenko, 1986). Oleh karena itu, pH 9,0

dipilih untuk penelitian lebih lanjut.

3.3 Pengaruh konsentrasi PAN

Gambar hasil

Gambar 3. Pengaruh konsentrasi PAN pada efisiensi ekstraksi. Kondisi: 500 mL dari 50

ng mL 1355 timbal; sample’spH = 9.0, 100 mg Fe3O4NPs; CTAB 50 mg; 5 menit pengadukan,

elusi dengan 1,0 mL metanol.

PAN bertindak sebagai ligan tridentate dan dapat membentuk kompleks yang sangat stabil

dengan ion logam (seperti ML atau ML2) melalui atom hidroksil oksi-gen, atom nitrogen piridin

dan salah satu atom atom gugus azo (Marczenko, 1986). Kompleks PAN timbal dapat dengan
mudah berinteraksi dengan Fe3O4NPs yang dilapisi CTAB, yang meningkatkan efisiensi ekstraksi

timah. Pada 50 ng mL 1 timbal, efek konsentrasi PAN pada efisiensi ekstraksi dipantau dengan

mengubah rasio molar PAN menjadi timah di sekitar 0-20 (Gbr. 3). Hasil menunjukkan bahwa

dengan meningkatkan rasio PAN untuk memimpin hingga 16 akan menyebabkan peningkatan

pemulihan ekstraksi; setelah itu, tetap konstan. Oleh karena itu, PANto lead ratio 16 digunakan

untuk penelitian selanjutnya.

3.4. Pengaruh jumlah surfaktan

Adsorpsi surfaktan pada permukaan mineral oksida dibagi menjadi tiga wilayah

(hemimicelles, hemimicelles campuran, dan admicelles). Wilayah pertama, potensi zeta mineral

oksida berubah dari negatif menjadi nol karena fakta bahwa hemimikel secara bertahap terbentuk

pada permukaan mineral oksida. Setelah meningkatkan konsentrasi surfaktan kationik, admicelles

terbentuk secara dominan pada permukaan dan zeta-potensial meningkat dari nol menjadi positif.

Sehingga, permukaan luar hemimicelles bersifat hidrofobik sedangkan permukaan dalam adalah

ionik. Pada fase campuran hemimicelles, baik hemimicelles dan admicelles terbentuk di

permukaan mineral oksida dan adsorpsi didorong oleh interaksi hidrofobik dan tarikan

elektrostatik. Efek jumlah CTAB pada efisiensi ekstraksi dipertimbangkan dalam kisaran 0-100

mg. Berdasarkan hasil yang diperoleh, jumlah CTAB meningkat hingga 25 mg diperoleh

peningkatan pemulihan ekstraksi , kemudian menurun karena interaksi yang tidak sesuai. Jadi, 25

mg CTAB dipilih sebagai jumlah optimal untuk mencapai efisiensi ekstraksi yang memungkinkan.

3.5. Pengaruh jumlah adsorben dan waktu ekstraksi

Berdasarkan perbandingan, NP lebih memberikan rasio luas permukaan yang lebih tinggi

dibanding sorben ukuran mikro. Maka, hasil memuaskan dapat dicapai dengan jumlah NP lebih
sedikit. Untuk mempelajari efek adsorben, 10–150 mg NP Fe3O4 ditambahkan ke 500 mL larutan

sampel. Diperoleh hasil bahwa dengan meningkatkan jumlah adsorben dari 25 hingga 100 mg,

efisiensi ekstraksi meningkat perlahan karena peningkatan aksesibilitas situs dan tetap konstan.

Karena difusi yang lebih pendek rute untuk NP ditambah pemisahan yang dibantu secara magnetis

dari NP magnetik larutan sampel, ekstraksi timbal dapat dicapai dalam waktu yang lebih sedikit

bahkan untuk volume sampel yang lebih besar. Pada waktu 1-5 menit digunakan untuk mengukur

waktu pemulihan ekstraksi. Hasilnya diperoleh pemulihan ekstraksi meningkat hingga 2 menit

dan tetap konstan. Oleh karena itu, 2 menit dipilih sebagai yang optimalnilai untuk mendapatkan

waktu analisis yang lebih singkat.

3.6. Kondisi desorpsi

Pelarut organik diketahui mengganggu agregat surfaktan dan digunakan untuk mengelusi

kompleks timbal dari permukaan Fe3O4 NPs yang dilapisi CTAB. Jadi, aseton, etanol, dan

metanol dipilih sebagai eluen. Metanol menunjukkan desorpsi yang lebih baik. Berdasrkan hal

tersebut maka efek keasaman metanol pada efisiensi desorpsi dipertimbangkan. Hasilnya bahwa

kemampuan desorpsi metanol yang mengandung 0,5% HCl ditemukan lebih unggul. Kompleks

timbal dielusi secara kuantitatif dari agregat CTAB dengan menggunakan 1,0 mL HCl 0,5% dalam

metanol. Hal ini dapat dikaitkan dengan fakta bahwa ketika tingkat pH di bawah atau di sekitar

titik isoelektriknya, kepadatan muatan di permukaan NP Fe3O4 lemah dan menguntungkan untuk

gangguan agregat CTAB. Untuk mendapatkan efisiensi desorpsi maksimum, efek waktu desorpsi

diselidiki dalam kisaran 1-5 menit. Hasilnya, waktu 2 menit dipilih untuk studi lebih lanjut. Selain

itu, adsorben dapat digunakan untuk setidaknya lima analisis berturut-turut tanpa perubahan yang

berarti.
3.7. Pengaruh volume sampel

Untuk mendapatkan faktor pengayaan yang lebih tinggi, diperlukan volume larutan

sampel yang lebih besar. Keuntungannya karena pemisahan adsorben (Fe3O4 NPs yang dibantu

secara magnetis), dimungkinkan untuk mengumpulkan adsorben dari volume yang lebih besar dari

larutan sampel. Dengan demikian ekstraksi 25 lg timbal dari volume berbeda dari sampel air mulai

dari 500 hingga 1500 mL diselidiki (Gambar 5). Ditemukan bahwa pemulihan kuantitatif terbaik

(> 90%) diperoleh ketika volume sampel kurang dari 1000 mL. Namun, efisiensi ekstraksi akan

sedikit menurun ketika volume sampel lebih dari 1000 mL. Oleh karena itu, volume sampel 1000

mL dipilih sebagai volume yang ideal untuk analisis jejak timbal dalam sampel air.

3.8. Studi gangguan

Mengingat selektivitas tinggi yang disediakan oleh FAAS, satu-satunya gangguan dapat

dikaitkan dengan langkah prakonsentrasi, dimana kation dapat bereaksi dengan PAN yang dapat

menyebabkan penurunan efisiensi ekstraksi. Jadi, gangguan ko-eksistensi ion pada prekonsentrasi

timbal diselidiki. Untuk menyelidiki efek ion asing pada efisiensi ekstraksi, larutan (500 mL) yang

mengandung 50 ng mL ion timbal dan berbagai jumlah ion asing disiapkan dan diekstraksi sesuai

dengan prosedur yang dijelaskan dalam bagian eksperimental. Deviasi ± 10% dari pemulihan

solusi standar dianggap sebagai gangguan. Hasilnya ditunjukkan pada Tabel 1. Dapat dilihat

bahwa selektivitas yang sangat baik telah dicapai.

 Gambar 5. Pengaruh volume sampel pada efisiensi ekstraksi. Kondisi : 500mL dari 50

ng mL-1 pada sampel; pH sampel= 9,0, 2.0 mL dari 0.001 mol L-1 365 PAN (L/M=16); 100 mg;

NP Fe3O4; 25 mg CTAB; diaduk 2 menit, dengan elusi 1,0 mL 0,5% HCl dalam metanol

3.9. Fitur analitik

Fitur analitik dari metode yang diusulkan seperti presisi, rentang linier kurva kalibrasi

dan batas deteksi juga diperiksa. Hasilnya diringkas dalam Tabel 2. Ketepatan metode

diperkirakan dengan menerapkan siklus retensi dan elusi berturut-turut dengan 1000 mL larutan

sampel yang mengandung 10 lg timbal dalam kondisi optimal. Pemulihan timbal adalah kuantitatif

(> 95%) dan ketepatan metode ini sangat baik (RSD = 2,1%). Kisaran kalibrasi linear untuk

pengukuran dalam kondisi optimal adalah 0,05-100 ng mL 1 (R2 = 0,9996) untuk 1000 mL larutan.

3.10. Analisis sampel air lingkungan

Untuk memeriksa penerapan metode yang diusulkan untuk berbagai sampel air, ion timbal

ditentukan secara berbeda sampel air termasuk air keran Teheran, air sumur, air mineral dan

sampel air limbah dikumpulkan di sekitar Kilang Teheran. Volume solusi sampel yang sesuai

disesuaikan dengan pH optimal dan dilakukan prosedur yang direkomendasikan dengan metode

kalibrasi eksternal. Konsentrasi ion timbal yang rendah ditemukan dalam air sumur dan sampel air

limbah

3.11. Perbandingan metode yang diusulkan dengan metode lain

Metode yang diusulkan dibandingkan dengan berbagai metode dilaporkan baru-baru ini

dalam literatur untuk prekonsentrasi dan penentuan timah, terbukti bahwa faktor peningkatan

diperoleh dengan NP3 Fe3O4 yang dilapisi CTAB sangat tinggi dibandingkan dengan metode lain.

Kisaran linear dinamis yang besar, juga, LOD dan RSD yang sangat rendah adalah fitur signifikan
lainnya metode yang sebanding atau bahkan lebih baik daripada offline cloud point ekstraksi (CPE)

diikuti oleh yang sangat sensitive metode deteksi (ET-AAS).

BAB III

PENUTUP

KESIMPULAN

Metode SPE baru berdasarkan Fe3O4 NPs berlapis CTAB adalah dikembangkan untuk

prekonsentrasi ion timbal dalam sampel air lingkungan. Penggunaan NP mengakhiri metode SPE

dengan kapasitas ekstraksi yang tinggi dan faktor prekonsentrasi. Hasil yang diperoleh dalam

karya ini menunjukkan penerapan prosedur yang diusulkan untuk prakonsentrasi dan penentuan

jejak ion timbal. Pemulihan ana lytes hampir kuantitatif (> 95%). Metode yang dikembangkan

sederhana, cepat dan sensitif serta sangat cocok untuk adsorpsi cepat logam berat dari volume

besar larutan sampel.

Arabian Journal of Chemistry (2016) 9, S1540–S1546

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Preconcentration of trace amounts of lead in water

samples with cetyltrimethylammonium bromide
coated magnetite nanoparticles and its
determination by flame atomic absorption
spectrometry
Mohammad Faraji a, Shahab Shariati b,*
, Yadollah Yamini c, Mahnaz Adeli d

a
Young Researchers Club, Rasht Branch, Islamic Azad University, Rasht, Iran
b
Department of Chemistry, Rasht Branch, Islamic Azad University, Rasht, Iran
c
Department of Chemistry, Tarbiat Modares University, Tehran, Iran
d
Knowledge Development & University Relationship Department, Iran Khodro Company, Tehran, Iran

Received 15 September 2011; accepted 6 April 2012

Available online 17 April 2012

KEYWORDS Abstract A sensitive and simple magnetic solid phase extraction procedure was presented for the
Lead; preconcentration of lead ions in environmental water samples. In the present study, lead ions form
Magnetite nanoparticles; complexes with 1-(2-pyridilazo)-2-naphthol reagent (PAN) in basic medium, and then are quantita-
Solid phase extraction; tively extracted to the surface of cetyltrimethylammonium bromide (CTAB)-coated magnetite
Flame atomic absorption nanoparticles (Fe3O4 NPs). After magnetic separation of adsorbent, the adsorbent was eluted with
spectrometry 0.5% (v/v) HCl in methanol prior to its analysis by flame atomic absorption spectrometry (FAAS).
The pH of sample, concentrations of PAN, amounts of CTAB and Fe3O4 NPs, sample volume and
desorption conditions were optimized. Under optimum conditions, the calibration curve was linear
in the range of 0.05–100 ng mL 1 with R2 = 0.9996. Detection and quantification limits of the
proposed method were 0.005 and 0.05 ng mL 1, respectively. Enhancement factor of 1050 was
achieved using this method to extract 1000 mL of different environmental water samples. Com-
pared with conventional solid phase extraction methods, the advantages of this method still include

* Corresponding author. Tel.: +98 131 4224343; fax: +98 131

4224949.
E-mail address: shariaty@iaurasht.ac.ir (S. Shariati).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

http://dx.doi.org/10.1016/j.arabjc.2012.04.005
1878-5352 ª 2012 Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
Preconcentration of trace amounts of lead in water samples with cetyltrimethylammonium bromide
easy preparation of sorbents, short times of sample pre-treatment, high extraction yield, and high
breakthrough volume. It shows great analytical potential in preconcentration of lead from large
volume water samples.
ª 2012 Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
1. Introduction
Lead enters food and drinks, contaminating them and there-
fore, it is a serious health hazard for everybody (Mosquera,
1999). Lead is particularly harmful, but even at high levels it
is considered innocuous in the past (Ladron de Guevara,
1995). Water is one of the main sources of lead contamination
for the general public. Even though the lead quantity in these
samples is low, its introduction in the daily diet may have sig-
nificant physiological effects (Cabrera, 1994). Determination
of lead at trace levels in water samples requires the use of
highly sensitive and reliable analytical techniques (Mena
et al., 1997). Only few techniques such as electrothermal atom-
ic absorption spectrometry (ET-AAS) (Bruno et al., 1994; Jor-
hem and Sundström, 1995), or anodic stripping voltammetry
with microelectrodes (Baldo et al., 1997) have enough sensitiv-
ity to directly determine the low quantities of lead. Flame
atomic absorption spectrometry (FAAS) is available in most
laboratories and is normally less subjected to interferences,
but it requires a preconcentration step in order to increase
the lead concentration because of lead concentrations in envi-
ronmental water samples are typically below the FAAS detec-
tion limit. Preconcentration and separation procedures
coupled with FAAS offer the possibility of using a relatively
simple and cheap detection system (Naghmush et al., 1995;
Ferreira et al., 2001).
Several methods have been proposed for separation and
preconcentration of trace amounts of lead such as dispersive
liquid–liquid microextraction, cloud point extraction, liquid–
liquid extraction, and solid-phase extraction (SPE). Such sys-
tems improve the sensitivity and the selectivity of FAAS allow-
ing the determination of traces of lead in water samples, and
could represent an alternative to ET-AAS (Ferreira et al.,
2001). Among these techniques, the SPE procedures, either
off- or on-line, are considered superior to the other procedures
for their simplicity, consumption of small volumes of organic
solvents, capability to eliminate undesirable matrix compo-
nents, and their ability to achieve a higher enrichment factors
(Fang et al., 1991).
More recently, the use of magnetic NPs for sample extrac-
tion and preconcentration is gaining researchers interest
(Huang and Hu, 2008a,b; Zhao et al., 2008a,b; Suleiman
et al., 2009; Zargar et al., 2009; Sun et al., 2009; Faraji et al.,
2010a). Compared with micrometer-sized particles used in
the SPE, the NPs offer a multitude of benefits that make them
a better choice. They have significantly higher ratio of surface
area-to-volume and a short diffusion route, resulting in higher
extraction capacity; rapid dynamics of extraction and higher
extraction efficiencies (Moeller et al., 2007). Moreover, by
using superparamagnetic NPs such as Fe3O4 a shorter analysis
time can be achieved, due to the magnetically assisted separa-
tion of these particles from the sample solution. These particles
are attracted to a magnetic field but retain no magnetic charge
S1541
after the field removal. This property makes them particularly
suitable for sample preparation because in comparison with
non-magnetic adsorbents no centrifuging or filtration of the
sample is needed after extraction.
The aim of the present study was to develop a NP-based
method for the preconcentration and determination of trace
amounts of lead. The method is based on the extraction of lead
as hydrophobic complexes of lead-PAN on cetyltrimethylam-
monium bromide (CTAB) – coated Fe3O4 NPs. The level of
lead in extracted phase was then determined by FAAS. To
the best of our knowledge, this method has not been employed
previously in the extraction and determination of trace
amounts of lead from aqueous samples.
2. Experimental
2.1. Instrumentation
A Varian (Mulgrave, Victoria, Australia) flame atomic absorp-
tion spectrometer model SpectrAA 110, with an air-acetylene
flame was used for lead determinations. Absorbance measure-
ments were carried out at 217.0 nm using lead hollow cathode
lamp (from Varian) operated at 4.0 mA with deuterium back-
ground correction (at 10 mA). The instrumental parameters
were used according to the manufacturer’s recommendations.
All measurements were based on peak height. The pH of the
solutions were measured with a WTW pH meter (Inolab, Ger-
many) which was supplied with a combined pH electrode.
TEM images were obtained with an H-800 transmission electron
microscope (Hitachi, Japan) and magnetic properties were ana-
lyzed using a vibrating sample magnetometer (VSM, LDJ9600).
2.2. Reagents
All chemicals used were of analytical reagent grade. Ferric
chloride (FeCl3Æ6H2O), ferrous chloride (FeCl2Æ4H2O), sodium
hydroxide, 1-(2-pyridilazo)-2-naphthol (PAN), lead nitrate
(Pb(NO3)2), CTAB, methanol, acetone, and 1-propanol,
hydrochloric acid were all purchased from Merck (Darmstadt,
Germany). The stock solution of lead (1000 lg mL 1) was pre-
pared by dissolving the appropriate amounts of Pb(NO3)2 in
doubly distilled water. A solution of 1 · 10 3 mol L 1 PAN
was prepared by dissolving the appropriate amount of this re-
agent in methanol.
2.3. Synthesis of Fe3O4 NPs
Fe3O4 NPs were prepared by chemical co-precipitation method
via a reactor which was designed in our previous work (Faraji
et al., 2010b). Briefly, 10.4 g of FeCl3Æ6H2O, 4.0 g of FeCl2Æ
4H2O and 1.7 mL of HCl (12 mol L 1) were dissolved in
50 mL of deionized water in order to prepare stock solution
S1542 M. Faraji et al.

of ferrous and ferric chloride in a beaker which was then de-
gassed with nitrogen gas for 20 min. Simultaneously, 500 mL
of 1.5 mol L 1 NaOH solution was degassed (for 15 min)
and heated to 80 C in a reactor. Then, the stock solution
was added dropwise using the dropping funnel during 30 min
under nitrogen gas protection and vigorous stirring
(1000 rpm) by a glassware stirrer. During the whole process,
the solution temperature was maintained at 80 C and nitrogen
gas was purged to remove the dissolved oxygen. After comple-
tion of the reaction, the obtained Fe3O4 NPs were separated
from the reaction medium by the magnetic field, and then
(a)
washed with 500 mL doubly distilled water four times. Finally,
the obtained Fe3O4 NPs were resuspended in 500 mL of de-
gassed deionized water.
2.4. Preconcentration procedure
An aliquot of water sample (500 mL, pH = 9.0) was trans-
ferred to 2000 mL glassware beakers. Then, 2.0 mL of
1 · 10 3 mol L 1 PAN, 10 mL of the suspension of Fe3O4
NPs (10 mg mL 1) and 2.5 mL of the CTAB solution
(10 mg mL 1) were sequentially added to the sample solution
and then mixed. The mixture was shaken and allowed to com-
plete the extraction process for 2 min. Subsequently, an Nd-
Fe-B strong magnet (10 · 5 · 4 cm, 1.4 Tesla) was placed at
the bottom of the beaker, and the CTAB-coated Fe3O4 NPs
were isolated from the solution. After about 10 min, the solu-
tions became limpid and supernatant solutions were decanted.
Finally, the preconcentrated lead complex was eluted from the
isolated particles with 1.0 mL of 0.5% HCl in methanol and
this solution was introduced into FAAS for determination of
lead concentration.

3. Results and discussion

3.1. Characterization of Fe3O4 nanoparticles

(b)
Characterization of synthesized Fe3O4 NPs was done using IR,
VSM and TEM instruments (Fig. 1). IR spectra of pure Fe3O4
NPs (i) and CTAB-coated Fe3O4 NPs (ii) are shown in Fig. 1a.
The peak at 3455 cm 1 is attributed to the stretching vibra-
tions of –OH, which is assigned to surface OH groups of
Fe3O4 NPs. The peak at 571 cm 1 is attributed to the Fe–
O band vibration of Fe3O4. Also, the peak at 1380 cm 1 is
attributed to C–N band and the peaks at 2885 and
2925 cm 1 are attributed to two different C–H bands vibration
of CTAB. The IR spectra show that the surface of Fe3O4 NPs
was well modified by CTAB. Also, the TEM image of the pre-
pared NPs is shown in Fig. 1b. Based on the TEM image, the
Fe3O4 surface morphology analysis demonstrated the agglom-
eration of many ultrafine particles with a diameter of about
20 nm. On the other hand, it is important that Fe3O4 NPs
should possess sufficient magnetic and superparamagnetic
(c) property for magnetic carrier technology (MCT) practical
80 application. Fig. 1c shows VSM magnetization curves of
60 Fe3O4 NPs at room temperature. Fe3O4 NPs exhibited typical
Magnetization (emu/g)

40
superparamagnetic behavior due to not exhibiting hysteresis,
remanence and coercivity. The large saturation magnetization
20
of Fe3O4 NPs was 76 emu/g, which is sufficient for magnetic
0
-10000 -5000 0 5000 10000 separation with a conventional magnet.
-20

-40 3.2. Effect of solution’s pH

-60

-80 The charge density of mineral oxide surface is a main factor

Applied magnetic field (Oe)
Fe3O4
Figure 1 Characterization of the CTAB-coated Fe3O4 NPs. (a)
The IR spectra before (i) and after the modification with CTAB
(ii). (b) The TEM image of the Fe3O4 NPs. (c) VSM magnetization
curves of Fe3O4 NPs.
affecting the adsorption of analytes and it varies strongly with
pH. Thus, pH is a very important parameter for the adsorption
of target compounds. On the other hand, pH plays an impor-
tant role in the complexation of lead with PAN. To examine
the effect of pH on extraction efficiency of lead ions, pH of
the solution varied in the range of 6.0–12.0 (Fig. 2). As can
be seen from Fig. 2, the Fe3O4 NPs do not exhibit obvious
Preconcentration of trace amounts of lead in water samples with cetyltrimethylammonium bromide S1543

adsorption of lead as Pb–PAN complex when the pH value

was lower than 8.0. With increasing pH, the adsorption effi-
ciency increased dramatically and reached maximum when
the pH was between 9.0 and 10.0. This is mainly due to the fact
that negative charges were favorable for the adsorption of cat-
ionic surfactants. When pH value was around NPs isoelectric
point (about 7.0) the charge density of Fe3O4 NPs surface
was very low (Zhao et al., 2008b). When the pH value was
above their isoelectric point, the Fe3O4 NPs surface became
negatively charged which gave rise to the strong electrostatic
attraction between the CTAB molecules and the charged
Fe3O4 NPs surface. Under this circumstance, hydrophobic
complexes of Pb–PAN can be interacted with CTAB-coated
Figure 3 Effect of PAN concentration on extraction efficiency.
Fe3O4 NPs surface. But, at pH higher than 10.0, lead can pre-
Conditions: 500 mL of 50 ng mL 1 355 of lead; sample’s
cipitate as hydroxide form. On the other hand, pH between 9.0
pH = 9.0, 100 mg Fe3O4 NPs; 50 mg CTAB; 5 min stirring,
and 10.0 is favorable for complexation of lead and PAN
elution with 1.0 mL methanol.
(Marczenko, 1986). Therefore, pH of 9.0 was selected for
further studies.
tion, admicelles were formed dominatingly on the surface
3.3. Effect of PAN concentration and the zeta-potential increases from zero to positive (Zhao
et al., 2008a). Therefore, the outer surface of hemimicelles is
PAN acts as a tridentate ligand and can form very stable com- hydrophobic whereas that of admicelles is ionic, which pro-
plexes with metal ions (as ML or ML2) through hydroxyl oxy- vides different mechanisms for retention of compounds and
gen atom, nitrogen atom of pyridine and one of the azo group are both suitable for the SPE method. In the mixed hemimi-
nitrogen atoms (Marczenko, 1986). PAN complexes of lead celles phase, both hemimicelles and admicelles are formed in
can be easily interacted with CTAB-coated Fe3O4 NPs, which the surface of mineral oxides and the adsorption is driven by
increases extraction efficiency of lead. At 50 ng mL 1 of lead, both hydrophobic interaction and electrostatic attraction.
the effect of PAN concentration on extraction efficiency was The effect of CTAB amounts on the extraction efficiency was
studied by changing the molar ratio of PAN to lead in the considered in the ranges of 0–100 mg. Based on the obtained
range of 0–20 (Fig. 3). Results showed that by increasing the results (Fig. 4), increasing the amount of CTAB up to 25 mg
PAN to lead ratio up to 16 will cause an increase in the extrac- resulted an increase in the extraction recovery; after that, it de-
tion recovery; after that, it remained constant. Therefore, PAN creased due to unsuitable interactions. So, 25 mg of CTAB was
to lead ratio of 16 was used for the subsequent studies. chosen as optimum amount in order to achieve the highest
possible extraction efficiency.
3.4. Effect of the amount of surfactant
3.5. Effect of the adsorbent amount and extraction time
The adsorption of surfactant on the surface of mineral oxides
can be divided into three regions (hemimicelles, mixed hemim- In comparison with the traditional sorbents (micro size sor-
icelles, and admicelles). In the first region, the zeta potential of bents), NPs offer a significantly higher surface area-to-volume
mineral oxides changed from negative to zero due to the fact ratio. Therefore, satisfactory results can be achieved with fewer
that hemimicelles were gradually formed on the mineral oxide amounts of NPs. In order to study the effect of the adsorbent,
surfaces. Upon increasing the cationic surfactant concentra-

90

70 80
Extraction efficiency (%)

60 70
Extraction efficiency (%)

60
50
50
40
40
30 30

20 20

10
10
0
0 0 10 25 50 75 100
6 7 8 9 10 11 12 Amount of CTAB (mg)
pH of sam ple
Figure 4 Effect of CTAB amount on extraction efficiency.
Figure 2 Effect of sample pH on extraction efficiency. Condi- Conditions: 500 mL of 50 ng mL 1 of lead; sample’s pH = 9.0,
tions: 500 mL of 50 ng mL 1 of lead; 1.0 mL of 0.001 mol L 1 351 2.0 mL of 0.001 mol L 1 359 PAN solution (L/M = 16); 100 mg
PAN solution (L/M = 8); 100 mg Fe3O4 NPs; 50 mg CTAB; Fe3O4 NPs; 50 mg CTAB; 5 min stirring, elution with 1.0 mL
5 min stirring, elution with 1.0 mL methanol. methanol.
S1544 M. Faraji et al.

10–150 mg of the Fe3O4 NPs was added to 500 mL of the sam- 90

ple solution. The obtained results showed that by increasing

Extraction efficiency (%)

80
the adsorbent amounts from 25 up to 100 mg; extraction effi- 70
ciency was increased slowly due to the increasing of accessible 60
sites, and remained constant. So, a 100 mg of the Fe3O4 NPs 50
was selected for all subsequent experiments.
40
Also, the effect of the extraction time on the extraction
30
recovery of lead was investigated. Due to the shorter diffusion
route for NPs plus the magnetically assisted separation of the 20

magnetic NPs from the sample solutions, extraction of lead 10

can be achieved in less time even for larger volumes of samples. 0

500 750 1000 1250 1500
The effect of the extraction time on the extraction recovery was
Sam ple volum e (m L)
investigated in the range of 1–5 min. Based on the obtained re-
sults, extraction recovery increased up to 2 min and then re- Figure 5 Effect of sample volume on extraction efficiency.
mained constant. Therefore, 2 min was chosen as optimum Conditions: 500 mL of 50 ng mL 1 of lead; sample’s pH = 9.0,
value in order to obtain a shorter analysis time. 2.0 mL of 0.001 mol L 1 364 PAN solution (L/M = 16); 100 mg
Fe3O4 NPs; 25 mg CTAB; 2 min stirring, elution with 1.0 mL of
3.6. Desorption conditions 0.5% HCl in methanol.

Organic solvents are known to disrupt surfactant aggregates

and were used to elute lead complex from the CTAB-coated in which the cations may react with PAN which may lead to
Fe3O4 NPs surface (Zhao et al., 2008a,b; Sun et al., 2009). a decrease in extraction efficiency. So, interference of co-exist-
So, acetone, ethanol and methanol were selected as eluent. ing ions on the preconcentration of lead was investigated. In
Among these eluents, methanol showed better desorption abil- order to investigate the effect of foreign ions on the extraction
ity. In continue, effect of methanol’s acidity on desorption effi- efficiency, solutions (500 mL) containing 50 ng mL 1 of lead
ciency was considered. Results showed that desorption ability ions and various amounts of foreign ions were prepared and
of methanol containing 0.5% HCl was found to be superior to were extracted according to the procedure described in the
that without adding HCl. Lead complex was quantitatively experimental section. The deviation of ±10% from the recov-
eluted from CTAB aggregates by using 1.0 mL of 0.5% HCl ery of the standard solution was taken as interference. The re-
in methanol. This can be attributed to the fact that when the sults are shown in the Table 1. It can be seen that a very good
pH level was below or around its isoelectric point, charge den- selectivity was achieved.
sity in Fe3O4 NPs surface was weak and favorable for the dis-
ruption of CTAB aggregates. Thus, 1.0 mL of 0.5% HCl in 3.9. Analytical features
methanol was selected for desorption. On the other hand, in
order to obtain maximum desorption efficiency, effect of the The analytical features of the proposed method such as preci-
desorption time was investigated in the range of 1–5 min. sion, linear range of calibration curve and limit of detection
Based on the obtained results, a time of 2 min was chosen were also examined. The results are summarized in Table 2.
for further studies. Moreover, further studies showed that Precision of the method was estimated by applying successive
the adsorbent can be used for at least five successive analyses retention and elution cycles with 1000 mL of a sample solution
without a considerable change. containing 10 lg of lead under the optimum conditions. The
recovery of lead was quantitative (>95%) and the precision
3.7. Effect of sample volume of the method was very good (RSD = 2.1%). The linear cali-
bration range for measurements under the optimum conditions
In order to obtain a higher enrichment factor, a larger volume was 0.05–100 ng mL 1 (R2 = 0.9996) for 1000 mL of solution.
of sample solution is required. Fortunately, due to the magnet-
ically assisted separation of the adsorbent (Fe3O4 NPs), it is
possible to collect the adsorbent from larger volumes of the
Table 1 Tolerance limit of interfering ions.
sample solution. Thus the extraction of 25 lg of lead from dif-
ferent volumes of the water samples ranging from 500 to Interference Interference to metal ion ratio Recovery (%)
1500 mL was investigated (Fig. 5). It was found that the best Na +
10,000 100
quantitative recovery (>90%) was obtained when the sample K+ 10,000 90
volumes were less than 1000 mL. However, the extraction effi- Ba2+ 250 95
ciency would slightly decrease when the sample volumes were Ca2+ 100 91
more than 1000 mL. Hence, a sample volume of 1000 mL Mg2+ 750 96
Mn2+ 1000 108
was selected as the ideal volume for trace analysis of lead in
Hg2+ Saturated solution 107
water samples.
Al3+ Saturated solution 94
Cu2+ 20 100
3.8. Interference studies Cd2+ 50 95
Co2+ 50 91
In view of the high selectivity provided by FAAS, the only Ni2+ 20 94
interference may be attributed to the preconcentration step, Zn2+ 20 97
Preconcentration of trace amounts of lead in water samples with cetyltrimethylammonium bromide S1545

Table 2 Figures of merit of the proposed method for the extraction and determination of the lead.
Enhancement factor Limit of detection RSD % Dynamic linear range Calibration equation R2
(ng mL 1) (n = 6) (10 ng mL 1) (ng mL 1)
1050 0.005 2.1 0.05–100 I = 516 c + 761 0.9996

Table 3 Determination of lead in different water samples by applying the proposed method.
Sample Added (ng mL 1) Found (ng mL 1)a Relative recovery (%)
Tap water 0.00 – –
2.00 1.93 ± 0.09 95
10.00 9.78 ± 0.35 97
Well water 0.00 0.21 ± 0.01 –
2.00 2.01 ± 0.05 91
10.00 10.34 ± 0.45 101
Mineral water 0.00 – –
2.00 2.13 ± 0.21 105
10.00 9.92 ± 0.15 99
Wastewater sample 0.00 4.80 ± 0.08 –
2.00 6.40 ± 0.35 94
10.00 14.10 ± 0.62 95
a
Mean ± SD (n = 3).

Table 4 Comparison of the proposed method with some of the methods reported in the literature for extraction and determination of
lead.
Metal ions System Technique EF DLRa DLb RSD % Detection References
c c
Pb, Cu, Ni, Co, Cd Modified silica gel with Batch SPE 0.95–22.5 <9 FAAS Tuzen and Soylak, 2009
aminothioamidoanthraquinone
c
Cd, Co, Ni, Pb Black stone (Pierre noire) On-line SPE 20 0.3–1.1 1.1–5.9 ICP-OES Suleiman et al., 2008
c
Cd, Cr, Ni, Mn, Pb Cu(II)-dibenzyldithiocarbamate Coprecipitation 50 0.3–0.87 <10 FAAS Tuzen et al., 2005
Cd, Co, Cr, Cu, TTA/TritonX-114 On-line CPE 42–97 0.5–100 0.1–2.2 2.2–4.6 ICP-OES Yamini et al., 2008
Fe, Mn
Pb 5-Br-PADAP/ Triton X-1 14 Off-line CPE 50 0.1–30 0.08 2.8 ET-AAS Chen et al., 2005
Pb CTAB-coated Fe3O4 Batch SPE 1050 0.05–100 0.005 2.1 FAAS This work
nanoparticles
a
Dynamic linear range (ng mL 1).
b
Detection limit (ng mL 1).
c
Data not reported.

The detection limit based on three-times of the standard devi-
ation of the blank solution (3Sb/m) was found to be
0.005 ng mL 1. Also, an enhancement factor of 1050 was cal-
culated as the ratio between the slopes of the calibration curve
submitted by the SPE procedure (for V = 1000 mL) and the
direct calibration curve (without preconcentration).
3.10. Analysis of environmental water samples
wastewater samples. Reliability was checked by spiking sam-
ples. 1000 mL of the water samples spiked with 2.0 and
10.0 ng mL 1 of lead ions was extracted by the proposed
SPE procedure. Table 3 lists the recoveries and concentrations
found for lead, expressed as the mean value (n = 3). Recover-
ies of lead ranged between 91% and 105% for the all four
water samples. The results demonstrate the applicability of
the proposed method to water analysis.

In order to check the applicability of the proposed method for
various water samples, lead ions were determined in different
water samples including Tehran tap water, well water (Jaber
Ebne Hayyan Pharmaceutical Company), mineral water
(Damavand Brand) and wastewater sample collected around
Tehran Refinery. An appropriate volume of sample solutions
was adjusted to the optimum pH and subjected to the recom-
mended procedure with external calibration method. Low con-
centrations of lead ions were found in the well water and
3.11. Comparison of the proposed method with other methods
The proposed method was compared with a variety of methods
reported recently in the literature for the preconcentration and
determination of lead. The distinct features of the proposed
method are summarized in Table 4. As can be seen from
Table 4, it is evident that the enhancement factor obtained
with the CTAB-coated Fe3O4 NPs is very high in comparison
with other methods. Large dynamic linear range, also, very
S1546
low LOD and RSD are the other significant features of the
method which are comparable to or even better than off-line
cloud point extraction (CPE) followed by the very sensitive
detection method (ET-AAS) (Chen et al., 2005).
4. Conclusion
A new SPE method based on CTAB-coated Fe3O4 NPs was
developed for the preconcentration of lead ions in environmen-
tal water samples. The use of NPs endued the SPE method with
high extraction capacity and preconcentration factors. The
magnetic separation greatly improved the separation rate while
avoided the time-consuming column passing or filtration
operation. The results obtained in this work demonstrate the
applicability of the proposed procedure for preconcentration
and determination of traces of lead ions. The recoveries of ana-
lytes were nearly quantitative (>95%). The developed method
is simple, rapid and sensitive and very suitable for rapid adsorp-
tion of heavy metals from large volume of sample solution.
Acknowledgment
This work was financially supported by the Young Research-
ers Club of Islamic Azad University of Rasht Branch and
the authors thank for their valuable assistance.
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