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Analytical Letters
ISSN: 0003-2719 (Print) 1532-236X (Online) Journal homepage: https://www.tandfonline.com/loi/lanl20
Determination of Lead, Copper, and Iron
in Cosmetics, Water, Soil, and Food Using
Polyhydroxybutyrate-B-polydimethyl Siloxane
Preconcentration and Flame Atomic Absorption
Spectrometry
Yunus Emre Unsal, Mustafa Soylak, Mustafa Tuzen & Baki Hazer
To cite this article: Yunus Emre Unsal, Mustafa Soylak, Mustafa Tuzen & Baki Hazer (2015) Determination of Lead, Copper, and Iron in Cosmetics, Water, Soil, and Food Using Polyhydroxybutyrate-B-polydimethyl Siloxane Preconcentration and Flame Atomic Absorption Spectrometry, Analytical Letters, 48:7, 1163-1179, DOI: 10.1080/00032719.2014.971365To link to this article: https://doi.org/10.1080/00032719.2014.971365
Accepted author version posted online: 06 Jan 2015.
Published online: 06 Jan 2015. Submit your article to this journal
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Copyright# Taylor & Francis Group, LLC ISSN: 0003-2719 print/1532-236X online
DOI: 10.1080/00032719.2014.971365
Preconcentration Techniques
DETERMINATION OF LEAD, COPPER, AND IRON IN
COSMETICS, WATER, SOIL, AND FOOD USING
POLYHYDROXYBUTYRATE-B-POLYDIMETHYL
SILOXANE PRECONCENTRATION AND FLAME
ATOMIC ABSORPTION SPECTROMETRY
Yunus Emre Unsal,
1Mustafa Soylak,
2Mustafa Tuzen,
1and
Baki Hazer
31
Chemistry Department, Faculty of Science and Arts, Gaziosmanpasa University, Tokat, Turkey
2
Chemistry Department, Faculty of Science, Erciyes University, Kayseri, Turkey
3
Department of Chemistry, Bulent Ecevit University, Zonguldak, Turkey
A separation and preconcentration method has been established based on solid phase extraction of Fe(III), Cu(II) and Pb(II) as their 2-(5-Bromo-2-pyridylazo)-5-diethylamino-phenol(5-Br-PADAP) chelates adsorbed on polyhydroxybutyrate-b-polydimethyl siloxane. Several analytical conditions including pH, amount of (5-Br-PADAP), eluent type and volume, sample volume, and flow rates were investigated. The effects of foreign ions on the recovery of the analytes were also studied. The detection limits for Cu(II), Fe(III), and Pb (II) were 1.9, 2.2, and 2.5 µg per liter, respectively. Enrichment factors for Cu(II), Fe(III), and Pb(II) were 150, 200, and 80, respectively. The adsorption capacity of the polymer for Cu(II) and Pb(II) studied was 10.2 and 17.2 milligrams per gram respectively. Relative standard deviation was 4%. Standard Reference Material (SRM 1577B Bovine liver), International Atomic Energy Agency(IAEA 336 Lichen), and Certified Reference Waters for Trace Elements(TMDA 51.3 Fortified lake water) were used for the validation of the method. Optimized procedure was applied for the determination of analyte elements in various cosmetic products, hair brilliantine and gel, water, soil, and food samples from Turkey. Keywords: 2-(5-bromo-2-pyridylazo)-5-diethylamino-phenol; Atomic absorption spectrometry; Polyhy-droxybutyrate-b-polydimethyl siloxane; Solid phase extraction; Trace element
INTRODUCTION
In recent years, environmental pollution by heavy metals has received consider-able attention. Some trace metals are essential elements and play an important role in human body. The most toxic heavy metals, namely lead, cadmium, and nickel can be
Received 24 July 2014; accepted 25 September 2014.
Address correspondence to Mustafa Tuzen, Chemistry Department, Gaziosmanpasa University, Faculty of Science and Arts, 60250 Tokat, Turkey. E-mail:mustafa.tuzen@gop.edu.tr
Color versions of one or more of the figures in the article can be found online at www.tandfonline. com/lanl
allocated from other pollutants, because they cannot be demeaned naturally but accumulate in living organisms. Therefore, they bring on various diseases and disor-ders even in lower concentrations(Soylak and Turkoglu1999; D. Chen et al.2010; Kołodyńska2010; Mirzaei et al.2011; Pan et al. 2010; Zhang, Xu, and Yan2010).
Important sources of heavy metal pollution are wastewaters and agricultural sources. Wastewaters arise from industries like chemical, tanneries, dye produce, plating, mining, metal covered, lead- acid battery factory, and petroleum refining (Çekiç, Filik, and Apak 2004; Mohammadi et al. 2011; das Graças et al. 2006; Arora et al.2008; Mishra, Balomajumder, and Agarwal 2010).
Lead is highly toxic element. The World Health Organization (WHO) has released the guidelines for drinking water quality containing the guideline value of 10mg/L for lead (World Health Organization2006; WHO/FAO2007). Iron and
cop-per are essential elements used in a variety of industrial materials and both elements are considered as essential micronutrients for human body and animal. However, high amounts of iron and copper can be harmful, causing irritation of nose and throat, nausea, vomiting, and anemia. Copper at nearly 40 ng/mL is required for nor-mal metabolism of many living organisms. Maximum permissible concentrations of copper in drinking water by WHO, are 1–2, and 1.3 mg/L, respectively APHA (American Public Health Association) 2005; World Health Organization2006; Yu et al. 2006; Şahin, Tokgöz, and Bektaş 2010). Therefore, sensitive, reproducible
and accurate analytical methods are required for the determination of trace amount of copper, iron, and lead in such samples (S. Chen et al.2007; Chwastowska et al.
2007; Chou, Wang, and Huang 2010; Reddy et al.2010). There are several
techni-ques which have been used for determination of metal ions such as inductively coupled plasma-optical emission spectrometry (ICP-OES) (Stripeikis et al. 2001; Zhao et al.2012), inductively coupled plasma mass spectrometry (ICP-MS) (Jiménez,
Velarte, and Castillo 2002; S. Chen et al. 2007), electrothermal atomic absorption
spectrometry (ETAAS) (Baysal, Akman, and Calisir 2008; Čundeva, Stafilov, and Pavlovska 2008), and flame atomic absorption spectrometry (FAAS) (Yamamoto, Nishino, and Ueda 1985; Satyaveni et al. 2007; C. L. Wu et al. 2007; Sadrzadeh et al.2008; Nureddin et al.2010).
In the determination of metal ions at trace levels in the highly saline samples including seawater, mineral waters, urine, table salt samples, and so forth, separation process is necessary due to negative or positive effects of group IA and IIA elements at high concentrations. Also this separation process should include the preconcentra-tion step, because of lower level of analytes than the detecpreconcentra-tion limit of the instrument. Several separation methods have been used for metal ions such as precipitation, liquid–liquid extraction, ion exchange, electrodialysis, membrane fil-tration, and adsorption of metal ions on various solid phases (Saracoglu, Soylak, and Elci 2002; Zhao et al. 2006; Vithlani and Patel 2007; X. H. Wu et al. 2007; Birinci, Gülfen, and Aydın 2009; Gando-Ferreira, Romão, and Quina 2011; Li et al.2012).
Aliphatic polyesters have been extensively investigated because of their biocom-patibility and biodegradability. They have been used for biomedical, drug delivery, tissue engineering, and packaging applications(B. Hazer et al.2012).
Polyhydroxybu-tyrate-b-polydimethyl siloxane is a biodegradable polyester block copolymer(D. B. Hazer, Kilicay, and Hazer 2012). We recently studied separation of some metal
ions on polyhydroxybutyrate-b-polydimethyl siloxane disc(Tuzen et al.2013). In the
present work, newly synthesized polyhydroxybutyrate-b-polydimethyl siloxane was used for the separation and preconcentration of copper, lead, and iron in various samples from Turkey.
EXPERIMENTAL
Reagents and Solutions
All reagents used were of the highest available purity and at least analytical reagent grade (Merck, Darmstadt, Germany). The used water in all experiments was purified in a Human model RO 180 as conductivity of 1µS per centimeter. Stock solutions of diverse elements were prepared from compounds with high purity from Pb(NO3)2, Fe(NO3)3, and Cu(NO3)2(Merck, Darmstadt, Germany).
The 2-(5-Bromo-2-pyridylazo)-5-diethylamino-phenol (5-Br-PADAP) was purchased from Sigma–Aldrich Co., USA.
The pH values were adjusted by addition of phosphate buffer solutions (H2PO4/H3PO4), acetate buffer solutions (CH3COO/CH3COOH) and ammonium buffer solutions(NH4þ/NH3).
Instrument
Perkin-Elmer Model 3110 flame atomic absorption spectrometer was used for all absorption measurements. Copper, iron, and lead hollow cathode lamps and air-acetylene flame were used for all measurements. The operating parameters for the investigated analytes were those recommended by the manufacturer(Table 1).
All measurements were carried out without background correction. A pH meter, Nel pH-900 Model glass-electrode was employed for measuring pH values in the aqueous phase.
Synthesis of Polyhydroxybutyrate-b-polydimethyl Siloxane Block Copolymer
PHB is a microbial polyester and received from Biomer (Germany). Poly (dimethyl siloxane) bis (2-aminopropyl ether) with MW 2,000 grams per mole (coded as: PDMSNH2) was received from Aldrich. Block copolymer was prepared according to the procedure described in D. B. Hazer et al.(2012) and B. Hazer et al. (2012).
Briefly, 3.0 grams of PHB, 3.0 grams of PDMSNH2 and 0.02 grams Tinn-2-octanoate, Sn(oct)2 as catalyst were dissolved in 50 mL of chloroform, and the
Table 1. Working conditions of elements in FAAS
Parameters Pb Cu Fe
Wavelength, nanometer 217.0 324.8 248.3
Slit width, nanometer 0.7 0.7 0.2
Lamp current, milliampere 20 30 30
solution was refluxed for 3 h. The solvent was evaporated by using a rotary evapor-ator. The resulting polyhydroxybutyrate-b-polydimethyl siloxane block copolymer was redissolved in 10 mL of chloroform and precipitated in 100 mL of methanol. This purification procedure was repeated once more and the polymer product dried under vacuum overnight at 40°C. FTIR spectrum of polyhydroxybutyrate-b-polydimethyl siloxane are given in Figure1. The multiple signals arising between 1000 and 1100 per centimeter and the single signal at 798 per centimeter are related to Si-O and Si-O-Si stretching vibrations.
Solid-Phase Extraction Procedure
The glass column, having a stopcock and a porous disk, was 100 mm long, and 10 mm in diameter was used during the experiments. The 400 mg of polyhydroxybu-tyrate-b-polydimethyl siloxane was placed into the column. A minimal amount of glass wool was fixed on top to avert disturbance of the polymer.
The 400 mg of the polyhydroxybutyrate-b-polydimethyl siloxane was washed with acetate buffer solution, pH 5.5, and 25 mL of the model solution containing 0.2 mg/L Cu(II), 0.2 mg/mL Fe(III), and 0.4 mg/mL Pb(II) and 200 µL of 0.1% (weight by volume) 2-(5-Bromo-2-pyridylazo)-5-diethylamino-phenol (5-Br-PADAP) was adjusted to pH 5.5 with acetate buffer solution. The column loaded with 400 mg of the polyhydroxybutyrate-b-polydimethyl siloxane was washed with acetate buffer solution, pH 5.5, and water before passing model solution through the column. The flow of sample solution through the column was gravitationally performed at 3.0 mL/ min. After finishing the passage of the model solution, the column was washed with distilled water. Then, the retained Cu(II), Fe(III), and Pb(II) ions were eluted from the
column by 5 mL of 1 mol/L HNO3in acetone at 5 mL/min of flow rate. The eluent was evaporated over a hot plate to near dryness. The residue diluted to 4.0 mL with 1 mol/ L HNO3. Eluent was analyzed for the determination of Cu, Fe, and Pb by flame atomic absorption spectrometer. Blank analyses were performed.
Applications
The 250 mL of spring water samples or 25 mL of TMDA 51.3 fortified water certified reference material was added into a beaker, and then the pH of the sample was adjusted to pH 5.5 with acetate buffer solution. Then, presented method in solid-phase extraction procedure was applied. The concentration of iron, copper, and lead in the final solution was determined by FAAS.
The 1.0 g of cosmetic product, food sample, and 0.5 g SRM 1577B Bovine liver, IAEA 336 Lichen were digested with 12 mL concentrated HNO3(65%) at 95°C. The mixture was evaporated almost to dryness on a hot plate and mixed with 4 mL of concentrated H2O2(30%). The mixture was again evaporated to dryness on a hot plate. After evaporation, 5–10 mL of distilled water was added and the sample was mixed. The resulting mixture was filtered through a blue band filter paper. The pH of the filtrate was adjusted to pH 5.5 by using acetate buffer solution and the aforementioned procedure was performed. The iron, copper, and lead in the final solution were determined with flame AAS.
RESULT AND DISCUSSIONS Effect of pH
The pH plays an important role for quantitative recovery of analytes(Furusho et al.2008; Chowdhury, Pandit, and Mandal2008; Tuzen, Saygi, and Soylak2008; Sari et al.2009; Rahman et al. 2011) in the solid phase extraction procedure. The
effect of pH upon the extraction of iron(III), copper(II), and lead(II) ions on poly-hydroxybutyrate-b-polydimethyl siloxane column was examined in the pH range of 2–8. The resulting data are given in Figure 2. The quantitative recovery (>95) for iron(III), copper(II), and lead(II) ions was found in the range of pH 5–6. Then, pH was adjusted to 5.5 with acetate buffer solution. Active binding sites available on the surface of the polyhydroxybutyrate-b-polydimethyl siloxane are ester, amide, and siloxane etheric repeating units. These groups can be easily protonated. This effect may be associated with increased in the quantitative recovery of analytes in pH values above 5. At pH higher than 7 the extraction decreases, probably due to hydrolysis with formation of metal hydroxides.
Influences of Amount of Ligand
The influences of amount of 2-(5-Bromo-2-pyridylazo)-5-diethylamino-phenol (5-Br-PADAP) on the recoveries of iron(III), copper(II), and lead(II) ions were also examined at pH 5.5. The results were summarized in Figure3. The recoveries of Cu (II), Fe(III), and Pb(II) were not quantitative (50%) without 5-Br-PADAP. The recovery values for copper(II), iron(III), and lead(II) ions increased after addition of 5-Br-PADAP. The quantitative values of analyte ions were found after 150µL
of 0.1% (weight by volume) 5-Br-PADAP. All subsequent experiments were applied with 200µL of 0.1% (weight by volume) 5-Br-PADAP.
Eluent Type and Volume
Various types of eluent solutions were examined for the desorption of iron(III), copper(II), and lead(II) from polyhydroxybutyrate-b-polydimethyl siloxane column.
Figure 2. Influences of pH on the recoveries of Cu(II), Fe(III), and Pb(II) (N ¼ 3).
Figure 3. The influences of amount of 5-Br-PADAP on the recoveries of Cu(II), Fe(III), and Pb(II) (N ¼ 3).
The results are depicted in Table2. Quantitative recoveries of iron(III), copper(II), and lead(II) were obtained by using 1 mol/L HNO3in acetone(100%). The volume of eluent is important for the high enrichment factor. The effects of volume of 1 mol/ L HNO3 in acetone as eluent were also examined in the range of 2.0–10.0 mL. Quantitative recovery values (>95%) for iron(III), copper(II), and lead(II) found by using 5.0 mL of 1 mol/L HNO3 in acetone. In all subsequent works, 5.0 mL of 1 mol/L HNO3in acetone was applied as eluent.
Influences of Amount of Polyhydroxybutyrate-b-polydimethyl Siloxane
The effect of amount of polyhydroxybutyrate-b-polydimethyl siloxane on the recoveries of iron(III), copper(II), and lead(II) ions were also examined at the range of 200–750 mg. The results were demonstrated in Figure4. The recovery values for copper, iron, and lead ions increased with the remaining amount of polyhydroxybuty-rate-b-polydimethyl siloxane. The quantitative values of analyte ions were found after 400 mg of polyhydroxybutyrate-b-polydimethyl siloxane. All further experiments were applied with 400 mg of polyhydroxybutyrate-b-polydimethyl siloxane.
Effect of Sample Volume
In order to obtain high enrichment factor(Soylak, Erdogan, and Elci2004; Elçi
et al.2000; A. Khan2007; Pedro et al.2008; Tuzen et al.2009), the maximum sample
volume for quantitative recoveries, different volumes in the ranges of 25–1000 mL of model solutions containing 0.2µg/L Cu(II), 0.2 µg/L Fe(III), and 0.4 µg/L Pb(II) were passed through the column packed with 400 mg of polyhydroxybutyrate-b-polydimethyl siloxane. Elution was applied with 5.0 mL of 1 mol/L HNO3in acetone.
Table 2. Effects of eluent type and volume on the recoveries of the Cu(II), Fe(III), and Pb(II)
Eluent type Recovery, percentage
Pb Cu Fe
1 mole per liter HNO3(10 milliliters) 35 2* 61 3 69 1 2 moles per liter HNO3(10 milliliters) 71 1 74 2 74 1 3 moles per liter HNO3(10 milliliters) 75 1 94 1 85 1 3 moles per liter HNO3(15 milliliters) 80 2 95 1 84 1
1 mole per liter HCl(10 milliliters) 39 1 78 2 69 2
2 moles per liter HCl(10 milliliters) 67 2 81 1 78 2 3 moles per liter HCl(10 milliliters) 65 2 84 2 84 2 3 moles per liter HCl(15 milliliters) 79 1 86 2 88 3
1 mole per liter NH3(10 milliliters) 24 2 30 3 6 2
2 moles per liter NH3(10 milliliters) 30 2 39 1 41 2 1 mole per liter HCl in acetone(10 milliliters) 92 1 95 2 98 2 1 mole per liter HNO3in acetone(10 milliliters) 99 1 96 2 97 1 1 mole per liter HNO3in acetone(5 milliliters) 96 2 98 1 100 1 1 mole per liter CH3COOH(10 milliliters) 31 1 23 2 26 2 2 moles per liter CH3COOH(10 milliliters) 44 2 39 1 27 2 2 moles per liter CH3COOH(15 milliliters) 54 2 61 1 63 1
As it can be seen in Figure 5, the recovery values for Cu(II), Fe(III), and Pb(II) were found to be in the range of 95–100% in the sample volume 750, 1000, and 400 mL, respectively. The enrichment factor was 150 for Cu(II), 200 for Fe(III), and 80 for Pb(II).
Effect of Flow Rates
The flow rates of sample and eluent solutions on the recoveries of Cu(II), Fe (III), and Pb(II) ions on column packed with polyhydroxybutyrate-b-polydimethyl siloxane were examined in the range of 0.5–8 mL per minute. The resulting data are illustrated in Figure 6 for sample solution. Cu(II), Fe(III), and Pb(II) were
Figure 4. The influences of amount of polyhydroxybutyrate-b-polydimethyl siloxane on the recoveries of Cu(II), Fe(III), and Pb(II) (N ¼ 3).
obtained quantitative for both sample and eluent solution in the range of 0.5–5 mL/ min. Therefore, 5 mL/min flow rates were applied to both sample and eluent solutions.
Matrix Effects
The positive and negative effects of the matrix components of highly saline sam-ples are known as“matrix effects” in the instrumental detection of traces analytes (Soylak, Elci, and Dogan 2000; Krishna et al. 2004; Dutta and Das 2007; Jamali et al. 2009; S. Khan et al.2011; Ghaedi et al. 2013a, 2013b, 2013c,2013d, 2013e).
To evaluate the possibility of analytical practice for the developed solid phase extrac-tion procedure, the influences of some matrix ions, which interfere with the determi-nation of Cu(II), Fe(III), and Pb(II) and these Cu(II), Fe(III), and Pb(II) ions in various real samples were investigated under the optimum parameters. The results are given in Table3. Investigated cations and anions in Table 3 had no influence on the recoveries and the determination of Cu(II), Fe(III), and Pb(II) ions. It was obtained that recoveries of Cu(II), Fe(III), and Pb(II) were almost quantitative in the presence of high concentrations of diverse ions.
Sorption Capacity of the Polymer
The adsorption isotherm of the resin for Cu(II), Fe(III), and Pb(II) were studied by the column method. The amount of metal ions adsorbed (adsorption capacity) at equilibrium were calculated using Eq. (1) (Atia 2005; Yirikoglu and Gulfen2008):
C=n
ð Þ ¼ 1=nð mKÞ þ 1=nð mÞ C ð1Þ
Figure 6. The influences of flow rate of sample solution on the recoveries of Cu(II), Fe(III), and Pb(II) (N ¼ 3).
where C(mg/L) is the concentration of metal ions in solution at equilibrium and n (mg/g) is the amount of adsorbed Cu(II), Fe(III), and Pb(II) per gram of the resin at equilibrium (mg/g). A breakthrough curve was gained by plotting the Cu(II), Fe (III), and Pb(II) concentration (mg/L) vs. the mg of Cu(II), Fe(III), and Pb(II) adsorbed per gram of the resin. The adsorption capacity(nm) and the binding equi-librium constant(K) were obtained from the slope and the intercept of the regression plot obtained by the least squares method. In order to determine the adsorption capacity, the model solutions of 25 mL containing 10.0–700 µg/mL of Cu(II) and 20.0–1000 µg/mL of Pb(II) were passed through column packed with 400 mg of poly-hydroxybutyrate-b-polydimethyl siloxane. The adsorption capacity polymer for Cu (II) and Pb(II) was 10.2 and 17.2 mg/g, respectively, and binding equilibrium con-stants were found to be 0.94 for Cu(II) and 0.002 for Pb(II). The adsorption isotherm for Fe(III) could not perform owing to precipitation of 50 µg/mL of Fe(III) at pH 5.5.
Analytical Performance
Analytical performance of the present study was examined under optimized parameters on the polyhydroxybutyrate-b-polydimethyl siloxane column. The limit of detection, described as the concentration equivalent to three times the standard deviation (n ¼ 10) of a reagent blank were found 1.9 µg/L for Cu(II), 2.2 µg/L for Fe(III) and 2.5 µg/L for Pb(II). The recoveries (n ¼ 10) of the analytes were found to be 99 2 for Cu(II), 97 2 for Fe(III), and 99 3 for Pb(II). A regression equa-tion for the calibraequa-tion curve was linear in the range of 3–33 µg/L, A ¼ 0,0102C 0,00005 (A: absorbance, C: concentration), r2¼ 0.9996 for Cu(II), 2–25 µg/L, A ¼ 0,0121C 0,0002, r2¼ 0.9994 for Fe(III) and 12–125 µg/L, A ¼ 0,0161C 0,0003, r2¼ 0.9997 for Pb(II).
Table 3. Influences of matrix ions on the recoveries of the Cu(II), Fe(III), and Pb(II) (N ¼ 3) Ion
Added as
Concentrations (milligrams per liter)
Recovery, percentage Pb Cu Fe Naþ NaCl 9000 99 1* 98 2 100 1 SO4 2-Na2SO4 1500 96 3 100 1 98 1 Kþ KCl 2500 94 2 96 3 96 2 Mg2þ Mg(NO3)2 2500 95 2 95 2 97 2 Cl- NH4Cl 12500 95 2 95 2 99 2 F- NaF 750 97 2 97 2 95 2 Ca2þ CaCl2 2000 95 2 98 2 96 1 NO3- NaNO3 3000 100 1 97 2 99 2 Cu2þ Cu(NO3)2.·3H2O 20 100 2 100 1 Mn2þ MnSO4 10 96 1 96 1 94 2 Fe3þ Fe(NO3)3· 9H2O 10 99 2 94 2 Pb2þ Pb(NO3)2 20 98 1 95 2 Zn2þ Zn(NO3)2· 6H2O 10 96 1 99 1 99 1 Cr3þ Cr(NO3)3· 9H2O 20 96 1 100 2 100 1 Ni2þ Ni(NO3)2· 6H2O 20 96 2 96 2 99 2 Cd2þ Cd(NO3)2· 4H2O 20 93 2 96 1 95 1
The relative standard deviation(RSD) was found 4%. Different amounts of Cu (II), Fe(III), and Pb(II) were added in Yahyalı tap water, hair brilliantine and Develi apricot samples. The results are in Table4. The recovery values for the Cu(II), Fe
(III), and Pb(II) were in the range of 94%–101%. These values are quantitative. Optimized procedure can be used for the separation and preconcentration of analyte ions from real samples.
Application to Real Samples
The accuracy of developed method was investigated by the analysis of TMDA 51.3 fortified lake water, SRM 1577B Bovine liver and IAEA 336 Lichen certified
Table 4. Test of addition/recovery for the application of presented method (N ¼ 6) Hair brilliantine Develi apricot Yahyalı tap water Added (micrograms) Found (micrograms) Recovery (percent) Found (micrograms) Recovery (percent) Found (micrograms) Recovery (percent) Fe 0.0 26.1 1.4* 10.1 1.1 26.8 1.1 5.0 30.7 1.9 92 14.8 1.2 94 31.8 1.6 100 10.0 35.4 2.1 93 19.7 1.4 96 36.7 1.8 99 Pb 0.0 BDL – BDL – BDL 5.0 5.0 0.1 100 4.9 0.2 98 4.7 0.1 94 10.0 9.7 0.3 97 9.8 0.4 98 9.9 0.2 99 Cu 0.0 9.1 0.6 9.6 0.7 15.1 0.6 5.0 13.8 1.1 94 14.5 1.1 98 20.0 0.8 98 10.0 27.5 1.4 92 19.2 1.4 96 24.7 1.0 96
BDL: Below detection limit;*mean standard deviation.
Table 5. Levels of analytes in TMDA-51.3 fortified water, IAEA 336 Lichen, and SRM 1577B Bovine liver certified reference material after application of presented method(N ¼ 4)
SRM 1577B Bovine liver certified reference material Analyte Certified value,
micrograms per gram
Found value, micrograms per gram
Recovery, percentage Paired t-test T-criticala Cu 160 155.2 4.1* 97 2.3 Pb 0.129 BDL – Fe 184 176.6 4.5 96 3.2
IAEA 336 Lichen certified reference material Analyte Certified value,
micrograms per gram
Found value,
micrograms per gram
Recovery, percent
Cu 3.55 3.52 0.2 99 0.3
Pb 4.9 4.65 0.3 95 1.7
Fe 425 399.1 7.8 94 6.7
TMDA 51.3 fortified water certified reference material Analyte Certified value,
micrograms per liter
Found value, micrograms per liter
Recovery, percent
Cu 89.2 82.1 2.9 92 4.9
Pb 73.3 70.4 2.2 96 2.6
Fe 109 105.7 3.1 97 2.2
reference materials. The resulting data are given in Table5. The results of our study and certified values for Cu(II), Fe(III), and Pb(II) ions are in good agreement. The developed method was applied to various water (tap water, natural spring water), cosmetic product, hair brilliantine and gel, soil, and food samples including apple (Malus domestica), apricot (Prunus armeniaca), and walnut (Juglans regia). The results are provided in Table 6.
CONCLUSION
A solid phase extraction with polyhydroxybutyrate-b-polydimethyl siloxane is an effective enrichment method for Cu(II), Fe(III), and Pb(II). The polyhydroxybu-tyrate-b-polydimethyl siloxane has a good stability and selectivity. Matrix effects are tolerable. The polymer could be used at least 450 cycles without any loss in the recov-eries of the metal ions. The enhanced hydrophobicity of the block copolymer coming from the PDMS blocks could be responsible for reusing of this material so many times. The developed solid phase extraction technique is better for having lower rela-tive standard deviation, a higher sorption capacity, lower detection limits, and higher
Table 6. Levels of analyte ions in all analyzed samples(N ¼ 5)
Samples Concentration(micrograms per gram)
Pb Cu Fe Lipstick 1 BDL 8.8 0.8* 11.2 1.2 Lipstick 2 BDL 10.3 1.1 9.8 0.9 Nail polish 1 BDL 10.5 0.9 14.1 1.2 Nail polish 2 BDL 6.2 0.5 7.3 0.5 Shampoo 1 BDL 16.9 1.5 29.4 1.8 Shampoo 2 BDL 15.2 1.4 14.2 1.2
Perfume 1 BDL 6.5 0.5 (micrograms per liter) 5.4 0.6 Perfume 2 BDL 4.2 0.4 (micrograms per liter) 7.1 0.5
Hair gel 1 BDL 6.7 0.5 32.1 2.1
Hair gel 2 BDL 5.9 0.4 18.7 1.4
Hair brilliantine BDL 9.1 0.6 36.1 2.2
Yahyalı tap water (micrograms per liter)
BDL 15.1 0.6 26.8 1.1
Develi tap water (micrograms per liter)
BDL 22.5 0.8 41.6 1.5
Yahyalı spring water (micrograms per liter)
6.2 0.4 29.7 1.2 229.9 9.2
Develi spring water (micrograms per liter)
BDL 18.4 1.0 162.5 5.9
Yahyalı soil 49.9 1.9 61.5 2.1 12.7 0.3 milligrams per gram Develi soil 24.8 1.0 49.9 1.7 10.9 0.2 milligrams per gram
Yahyalı Walnut 11.3 0.2 12.8 0.3 25.5 1.0 Develi walnut BDL 7.9 0.2 15.1 0.6 Yahyalı apricot 18.3 0.4 10.8 0.4 21.9 1.1 Develi apricot BDL 9.6 0.7 10.1 0.6 Yahyalı apple 9.2 0.1 10.1 1.1 29.1 1.3 Develi apple BDL 10.6 0.8 18.4 1.2
enrichment factor when compared to literature values(Dutta and Das2007; A. Khan
2007; Pan et al.2010;Şahin et al.2010; Zhang et al.2010; Mohammadi et al.2011).
FUNDING
The authors are fully grateful for the financial support of the Unit of the Scientific Research Projects of Gaziosmanpasa University, Erciyes University and Bulent Ecevit University. Dr. Mustafa Tuzen thanks Turkish Academy of Sciences for financial support. This work was also partially supported by TUBITAK [Grant Number 211T016 for the preparation of the polyester].
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