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The Use of Fungal Biomass Agaricus bisporus Immobilized on Amberlite XAD-4 Resin for the SolidPhase Preconcentration of Thorium a

a

b

Sadin Ozdemir , Veysi Okumuş , Abdurrahman Dündar & Ersin Kılınç a

c

Department of Biology, Faculty of Arts and Science , Siirt University , Siirt , Turkey

b

Medical Promotion and Marketing Program, Vocational Higher School of Health Services , Mardin Artuklu University , Mardin , Turkey c

Medical Laboratory Techniques, Vocational Higher School of Healthcare Studies , Mardin Artuklu University , Mardin , Turkey Published online: 09 Jan 2014.

To cite this article: Sadin Ozdemir , Veysi Okumuş , Abdurrahman Dündar & Ersin Kılınç (2014) The Use of Fungal Biomass Agaricus bisporus Immobilized on Amberlite XAD-4 Resin for the Solid-Phase Preconcentration of Thorium, Bioremediation Journal, 18:1, 38-45, DOI: 10.1080/10889868.2013.834870 To link to this article: http://dx.doi.org/10.1080/10889868.2013.834870

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Downloaded by [Sadin Ozdemir] at 14:06 09 January 2014

The Use of Fungal Biomass Agaricus bisporus Immobilized on Amberlite XAD-4 Resin for the Solid-Phase Preconcentration of Thorium Sadin Ozdemir,1 Veysi Okumus¸,1 2 ¨ Abdurrahman Dundar, 3 and Ersin Kılınc¸ 1 Department of Biology, Faculty of Arts and Science, Siirt University, Siirt, Turkey 2 Medical Promotion and Marketing Program, Vocational Higher School of Health Services, Mardin Artuklu University, Mardin, Turkey 3 Medical Laboratory Techniques, Vocational Higher School of Healthcare Studies, Mardin Artuklu University, Mardin, Turkey

Address correspondence to Dr. Sadin Ozdemir, Faculty of Arts and Science, Siirt University, 56100 Siirt, Turkey. E-mail: [email protected] Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/bbrm.

ABSTRACT Solid-phase extraction method was developed for the preconcentration of thorium (Th). Fungal biomass Agaricus bisporus was immobilized to Amberlite XAD-4 as solid-phase sorbent. The critical parameters such as pH of the sample solution, flow rate of the sample, volume of the sample, and the effect of major ions that affect the preconcentration of thorium in this system were evaluated. The optimum pH for the sorption of Th is 6.0, and quantitative elution occurs with 1.0 mol L−1 HCl. The loading capacity was determined as 0.079 mmol g−1. The optimized method was validated through analysis of the certified reference material of tea leaves (NCS ZC73014) and successfully applied to the determination of Th in a real ore sample with satisfactory results. KEYWORDS Agaricus bisporus, preconcentration, solid-phase extraction, thorium

INTRODUCTION Nowadays, heavy metals are among the most important pollutants in source and treated water, and they are becoming a severe public health problem (Lors et al. 2011; Ozdemir et al. 2012). Heavy metal solutions are widely used in industrial activities such as metal finishing, electroplating, painting, dying, photography, surface treatment, printed circuit board manufacture, etc. (Sergios et al. 2006). The removal of heavy metal contaminants from aqueous solutions is one of the most important environmental concerns because they are biorefractory and are toxic to many life forms (Ngah and Hanafiah 2008). There are several chemical technologies used in the removal of heavy metals. These conventional physicochemical methods include chemical precipitation, oxidation or reduction, filtration, ion exchange, electrochemical treatment, reverse osmosis, membrane technology, and evaporation recovery. Most of these are ineffective or excessively expensive when the metal concentrations are less than 100 mg L−1 (Ozdemir et al. 2009; Ahluwalia and Goyal 2007). The interest in the development of cost-effective methods for the removal and recovery of heavy metals from contaminated waters has greatly 38


increased because of the ecological awareness of the role of metals in the environment. A number of methods for metal ion removal from wastewaters have been used, but most have several disadvantages such as continuous input of chemicals, high cost, toxic sludge generation, or incomplete metal removal (Montanher, Oliveira, and Rollemberg 2005). Biosorption is the uptake of heavy metal ions and radionuclides from aqueous solutions by biological materials. Microorganisms, including algae, bacteria, yeast, fungi, plant leaves, and root tissues, can be used as biosorbents for detoxification and recovery of toxic or valuable metals from industrial discharges (Pavasant et al. 2006). Biosorption has gained importance during recent years because of the better performance and low cost of these biological materials (Iqbal and Edyvean 2004). Biosorptive processes are generally rapid and are in theory suitable for the extraction of metal ions from large volumes of water (Valdman et al. 2001). Development of chelating materials for solid-phase extraction has gained special attention due to the advantages of the use of these substances in metal ion enrichment. These advantages include a high degree of selectivity by controlling the pH, versatility, durability, good metal loading capacity, and enhanced hydrophilicity (Dogru, Gul-Guven, and Erdogan 2007). The biomass immobilized within a suitable matrix is meant to overcome these problems by offering ideal size (Iqbal and Edyvean 2004), mechanical strength, rigidity, and porous characteristics to the biological material (Valdman et al. 2001; Iqbal and Edyvean 2004). Chelating ligands have been functionalized in several support materials, including the commercially available XAD resin series. Amberlite XAD resins are widely used to develop several chelating materials for preconcentration procedures due to its good physical and chemical properties such as porosity, high surface area, durability, and purity. Amberlite XAD-4 has been often used as a solid sorbent to prepare a ligand-loaded resin (Dogru, Gul-Guven, and Erdogan 2007). Recently, Amberlite XAD resins have received increased attention as basic matrices for designing new chelating resins (Ince, Kaya, and Yaman 2010). The removal of radionuclides such as uranium and thorium from aqueous solutions, especially from contaminated sources, is an important topic in environmental control (Tsuruta 2004). The continuous buildup of toxic radionuclides emanating from various up- and downstream operations of the nuclear industry is of 39

paramount environmental concern (Sar and D’Souza 2002). Since the last century, thorium has been extensively used in a variety of applications. Environmental dispersion of actinoids in the hydrosphere is a very important area of radioecological investigation (Xuepin et al. 2004). Thorium in the environment not only originates from the nuclear industry but also from other human activities such as lignite burning in power plants, ore processing, use of phosphate fertilizers, copper metallurgy, and military activities, and it is usually found in effluents from monitoring laboratories (Harmsen and de Haan 1980; Macaskie 1991; Xuepin et al. 2004; Bituh et al. 2009; Picardo, Ferreira, and Costa 2009). Direct chemical toxicity of thorium is low due to its stability at ambient temperature. However, thorium as a fine powder is self-ignitable and can be easily transformed into thorium oxide. When thorium nitrate enters living organisms, it is mainly localized in the liver, spleen, and marrow, and it is precipitated in the form of hydroxide (Xuepin et al. 2004). Therefore, it is very important to identify potential biosorbents for remediation of thorium from the aqueous medium in order to protect the environment from this radioactive element and its daughter products (Kuber and D’Souza 2009). Most studies using microorganisms for removal of thorium have been conducted in batch experiment conditions by utilizing different microorganisms such as Mycobacterium smegmatis (Andres, MacCordick, and Hubert 1993), Rhizopus arrhizus (Tsezos and Volesky 1981), Aspergillus fumigatus (Kuber and D’Souza 2009), Arthrobacter cireus IAM 12341, Bacillus licheniformis IAM 111054, Citrobacter freundii IAM 12471, Corynebacterium glutamicum IAM 12435, Escherichia coli IAM 1268, Micrococcus varians IAM 13594, Nocardia erythropolis IAM 1399, Pseudomonas aeruginosa IAM 1054, Thiobacillus novellus IAM 12110, and Zooglea ramigera IAM 12136 (Nakajima and Tsurata 2004). However, there are not enough studies on preconcentration and determination of thorium for solid-phase extraction by fungal biomass ¨ (Ozdemir, Erdogan, and Kilinc 2010). It is known that fungal biomass holds distinct advantages over other microbial biomasses with respect to industrial exploitation due to the wide range of morphological types available, including unicellular and filamentous forms, large-scale availability, derived products from industrial and fermentation processes, ability to grow in inexpensive media, and ease of harvesting (Kuber and D’Souza 2009). The aim of this study was to investigate the performance of a packed-bed biosorption column for thorium

Th Preconcentration Using A. bisporus Immobilized on Amberlite

by immobilized A. bisporus as a function of pH, flow rate, volume of sample solution, and effect of major ions.


MATERIALS AND METHODS Instrumentation Inductively coupled plasma optical emission spectrometry (ICP-OES; PerkinElmer Optima 2100 DV; Shelton, CT, USA) was used for determination of Th. The pH of the solutions was adjusted using a Mettler Toledo MPC 227 (Columbus, OH, USA) digital pH meter. For solid-phase extraction (SPE), 1.0 × 10.0cm filtration columns equipped with polypropylene frites were used. The solutions were passed through the column with a Waters Marlow 323 (Milford, MA, USA) peristaltic pump. Infrared spectra of magnetic nanoparticle in KBr pellet were recorded in the range 4000–400 cm−1 on a Mattson model 1000 Fourier transform infrared (FT-IR) spectrophotometer. The operating conditions of the ICP-OES are given in Table 1.

Reagents and Solutions All chemicals were analytical reagent grade. All solutions were prepared in distilled-deionized water. Standard Th solution was prepared by diluting a correspondTABLE 1 Operating Conditions of the ICP-OES RF power (W) Plasma gas flow rate (L min−1) Auxiliary gas flow rate (L min−1) Nebulizer gas flow rate (L min−1) Sample flow rate (L min−1) View mode Read Source equilibration time (s) Read delay (s) Replicates Background correction Spray chamber Nebulizer

Detector Purge gas Shear gas Gas Analytical wavelength (nm)

S. Ozdemir et al.

1450 15 0.2 0.8 1.5 Axial Peak area 15 50 3 2-Point (manual point correction) Scott type spray chamber Cross-flow GemTip nebulizer (HF resistant) CCD Nitrogen Air Argon Th 283.730

ing 1000 μg ml−1 solution (Merck, Darmstadt, Germany). Certified reference tea leave samples were purchased from China National Analysis Center for Iron and Steel (Tuebingen, Germany). The solutions were centrifuged on a Sigma 2K15 (St. Louis, MO, USA). All laboratory glassware was rigorously cleaned and kept in 1.0 mol L−1 nitric acid for at least 24 h. The materials were then rinsed three times with distilled-deionized water. Adsorber resin (polystyrene divinyl benzene) Amberlite XAD-4 (surface area 725 m2 g−1, pore diameter 4 nm, and bead size 20–60 mesh) was purchased from Sigma. The XAD-4 resin obtained from the supplier contained organic and inorganic impurities. To remove the contaminants, it was treated with 4.0 mol L−1 HCl. The resin was firstly rinsed with distilled water until its pH was neutral, secondly with an ethanol-water (1:1) solution, and finally with distilled water again. It was then stored in a polyethylene bottle.

Growth and Preparation of Fungal Biomass The biomass used in the present work was Agaricus bisporus, collected from southeastern Turkey. The fungal sample was extensively washed twice with distilled water in order to remove sand and impurities from its surface, followed by sun drying. To obtain a fine powder, dried cells were ground in a porcelain mortar, and fungal biomass of A. bisporus was oven-dried at 80◦ C for 24 h to assess complete death of the dried cells. Then, the cells were inoculated to malt agar 25◦ C for 168 h, and the absence of any mycelia of A. bisporus indicated positive results (complete death of the fungus).

Column Preparation The immobilization of biomass on the substrate was performed as follows: 250 mg of dry biomass powder was mixed with 1.0 g of Amberlite XAD-4. The mixture was wetted with 15 ml of doubly distilled water and thoroughly mixed. The amount of biomass taken up by the resin was determined by measuring the increase in the weight of the resin after mixing the paste, which was heated in an oven at about 105◦ C for 1 h to dry the mixture. The wetting and drying steps were repeated to maximize the contact between A. bisporus and the Amberlite XAD-4, thereby improving the immobilization efficiency. Then, the product obtained was ground 40

General Sorption Studies


The biosorption of Th with the solid-phase extraction system was tested with model solutions. A 100-ml aliquot of 1.0 μg ml−1 solution of Th was taken and the pH adjusted with HCl and NH3 . The resulting solution was passed through the column with a peristaltic pump. The retained Th was then eluted from the solid phase with 5.0 ml of 1.0 mol L−1 HCl. The concentration of Th in the eluate was determined with ICP-OES. A. bisporus immobilized on Amberlite XAD-4 was used repeatedly (up to 10 times) after washing with 1.0 mol L−1 HNO3 solution and distilled water.

Sampling The certified reference sample of tea leaves (NCS ZC-73014) was digested with a temperature and pressure controlled analytical microwave oven. A 5.0-g portion of tea leaves was weighed and inserted into a beaker. Then, 5 ml of concentrated HNO3 :HCl (1:1) was added and stirred carefully with a clean glass bar until dry. Then, 6.0 ml of concentrated HNO3 :HCl:H2 O2 (1:1:0.2) was added, and the solution was transferred to a microwave vessel. The vessel was then applied with the recommended program in a microwave pressure digestion system (Speedwave MWS-3; Berghof, Beijing, China). The volume was brought up to 100 ml, and the developed biosorption method was applied to the sample. The ore sample containing the rare earth element was sampled in Sivrihisar-Eskis¸ehir (Turkey). The sample was homogenized and ground to size 100 mesh. It was digested with a microwave oven by using the recommended method of the procedure. The volume was then completed to 250 ml, and the developed biosorption method was applied to the sample. The results were obtained from the ICP-OES.

of the biosorbent for heavy metal ions (Krishnani et al. 2008; Hu et al. 2010; Munagapati et al. 2010). It not only influences the speciation of metal ions but also the charges on the sorption sites of biomass type. Therefore, it is very important to consider the ionic states of the functional groups of the biosorbent as well as the metal solution chemistry at different pH values (Farooq et al. 2010). The study of solution pH on uptake of Th ions onto Agaricus bisporus biomass was carried out in the range of pH 2.0–8.0 at 10 mg L−1 of Th(II) ions concentration with a flow rate of 1 ml min−1. The pH value of the sample solutions was adjusted to a range of 2.0–8.0 with HCl and NH3 . It is clearly seen in Figure 1 that maximum Th biosorption was obtained at pH 6.0. The recovery of immobilized cells of A. bisporus was low at pH 2.0 but increased significantly from 35.4% to 93.6% as the pH of the solution increased to 5.0. On further increase in pH to 7.0 and 8.0, the recovery of thorium obtained was 94.9% and 91.1%, respectively. At a pH lower than 4.0, little biosorption occurred. This could be due to a competition between Th ions and hydrogen ions, thus resulting in lower metals uptake onto immobilized cells of A. bisporus (Yahaya, Don, and Bhatia 2009). In acidic conditions, the functional groups of the cell walls are protonated, which means that the majority of the binding sites are occupied by protons, thereby decreasing the fungal metal biosorbent capacity (Areco and Afonso 2010). In general, pH 3.0–6.0 has been found to be favorable for the biosorption of metal ions by microbial biomass (Ozdemir et al. 2009). Subsequent experiments were carried out at an initial pH of 6.0.

120 100

Recovery (%)

to get the original size (20–60 mesh) and used as a biosorbent. All the analyses were performed three times and average values were given.

80 60 40 20 0

RESULTS AND DISCUSSION Effect of pH on the Recovery of Th

2

4

5

6

7

8

pH

The pH value of the aqueous solution is the most important variable governing the biosorption capacity 41

3

FIGURE 1 Effect of pH on the recovery of Th. Experimental conditions: Th concentration: 1.0 μg ml−1, volume: 50 ml, eluent: 1.0 mol L−1 HCl, flow rate of sorption: 1.0 ml min−1.


102

120

100 98 Recovery (%)

Recovery (%)

100 80 60

96 94 92 90 88

40

86

20

84 50

0

100

250

500

1000

Volume of the sample solution (mL)

1

2

3

4

5

FIGURE 3 Effect of the volume of the solution on the biosorp-

Flow rate (m L/m in)

FIGURE 2 Effect of flow rate on biosorption. Experimental con-

ditions: Th concentration: 1.0 μg ml−1, volume: 50 ml, pH 6, eluent: 1.0 mol L−1 HCl.

tion of Th. Experimental conditions: Th concentration: 1.0 μg ml−1, pH 6, eluent: 1.0 mol L−1 HCl, flow rate of solution: 2.0 ml min−1.


Effect of Volume of the Solution on the Recoveries Effect of Elution Parameters on Recovery The interaction of Th in solution with a sorbent is affected by the flow rate of the sample solution; thus, an optimization is required. It was investigated at 1.0–5.0 ml min−1, and it was decided to apply the sample flow as 2.0 ml min−1. Variation of recoveries with changes in flow rate of the sample solution is given in Figure 2. After the optimization of flow rate, other parameters such as type and volume of the eluent were considered. According to our experience, HCl and HNO3 were tried in different volumes and at different concentrations. The results given in Table 2 clearly indicate that quantitative elution was achieved when 5.0 ml of 1.0 mol L−1 HCl was used. The recovery value in this condition was 98.4 ± 0.3.

TABLE 2 Effect of the Type and Volume of Elution Solutions on the Recovery of Th

Type of elution solution HCI

HNO3

S. Ozdemir et al.

Volume (ml)

Concentration (mol L−1)

Recovery (%)

3 5 3 5 3 5 3 5

0.5 0.5 1 1 0.5 0.5 1 1

92.1 ± 0.2 97.3 ± 0.5 95.5 ± 0.4 98.4 ± 0.3 90.3 ± 0.5 95.1 ± 0.2 94.9 ± 0.5 97.7 ± 0.1

The effect of sample volume on the recovery of Th was investigated for 50, 100, 250, 500, and 1000 ml of solution containing 0.2, 0.1, 0.04, 0.02, and 0.01 μg ml−1. It was observed that higher recovery was obtained for lower volumes. Recovery values for 250 and 500 ml volumes were 98.5 and 97.6, respectively (Figure 3).

Effect of Electrolytes and Features of Column Effect of major ions such as K(I), Mg(II), Ca(II), Na(I), and Fe(II) were investigated, and tolerance values were obtained higher than 500 without a loss in recovery of more than 3.6%. Detailed results are illustrated in Table 3. From an analytical point of view, it is desirable to use the same column many times. This feature provides an economical value. For the biomass originating from bacteria or fungus, the number of times for reuse should be high. In our study, reuse of the column was tested for 50 ml of initial volume, and it was determined that the same column could be used 35 times (Figure 4). It was then observed that there was a decrease of more than 6% in recovery.

FT-IR Studies on Th Biosorption FT-IR spectra of Amberlite XAD-4, Agaricus bisporus, A. bisporus immobilized on Amberlite XAD-4, and Th adsorbed on A. bisporus–immobilized Amberlite XAD4 are given in Figure 5. Additional peaks in the FT-IR spectrum of the A. bisporus–functionalized Amberlite XAD-4 resin that do not appear in the spectrum of the free Amberlite XAD-4 are at 3500, 1640, 1700, 1200, 42

TABLE 3 Effect of the Major Components on the Recovery of Th

Ion

Concentration (μg ml−1)

Recovery (%)

0 50 500 0 50 500 0 50 500 0 50 500 0 50 500

100 ± 0.3 100 ± 0.1 97.4 ± 0.5 100 ± 0.4 99.6 ± 0.2 98.2 ± 0.3 100 ± 0.2 100 ± 0.2 98.8 ± 0.6 100 ± 0.4 99.8 ± 0.3 98.4 ± 0.1 100 ± 0.1 100 ± 0.5 99.6 ± .0.3

KCl

MgCl2

CaCl2

NaCl

and 650 cm−1, which appear to originate due to modification of the resin by the A. bisporus. The wide absorption band at about 3500 cm−1 is assigned to the O–H stretching vibration. Additionally, the peaks at about 1460 and 1700 cm−1 are attributed to C=O and C–C vibrations. However, no significantly different peaks were observed after complexation except for shifting of peaks at 1460 and 1720 cm−1.

Analytical Features of the Method One of the important parameters of a column is loading capacity. A high loading capacity is necessary for practical application. However, the column should be effective from low concentration of analyte to high

110 100 90 80 Recovery (%)

70 60 50 40 30 20 10

32

34

30

26

28

24

22

20

16

18

14

12

9

10

7

3

5

0

1


FeCl2

Number of Times Column Reused

FIGURE 4 Reusing the column. Experimental conditions: Th concentration: 1.0 μg ml−1, pH 6.0, eluent: 1.0 mol L−1 HCl, volume: 50 ml, flow rate of solution: 2.0 ml min−1.

43

FIGURE 5 Comparison of FT-IR spectra of (a) Amberlite XAD-4, (b ) A. Bisporus, (c ) A. bisporus immobilized on Amberlite XAD4, and (d ) Th adsorbed on A. bisporus–immobilized Amberlite XAD-4.

ranges. The loading capacity of A. bisporus immobilized on Amberlite XAD-4 was evaluated from the breakthrough curve plot from a method given by Bag, Lale, and Turker (1998). The loading capacity of Th on the resin was also calculated from the curve mentioned above. The sorption capacity was found to be 0.079 mmol g−1 (18280 μg g−1). The limit of detection (LOD) of the present work was calculated under optimum experimental conditions after application of the preconcentration method to blank solutions. The limit of detection for Th was based on the ratio of 3 times the standard deviations of the blank to slope of the calibration curve, and the limit of quantification (LOQ) was defined as the ratio of 10 times the standard deviations of the blank to slope of the calibration curve. The precision of the determination of Th was evaluated by the model solutions containing 10 ng ml−1 of Th under the optimum conditions mentioned above. For this purpose, the procedure was repeated 10 times. The mean concentration of Th was 8.9 ± 0.45 ng ml−1 at 95% confidence interval. The relative standard deviation (RSD) of the measurement was lower than 2%. The LOD and LOQ for Th were found to be 0.1 and 0.4 ng ml−1, respectively, whereas the LOD and LOQ of ICP-OES for Th were 9 and 30 ng


TABLE 4 Preconcentration Factor and Concentration Limit of Enrichment Using Column Technique

Volume of Concentration Preconcentration Recovery factor (%) solution (ml) (ng ml−1) 500 500

25 50

100 100

100 99.7


Note. Final volume was 5 ml.

ml−1. A linear calibration equation was obtained in the concentration range of 0.5–250 ng ml−1 for 500 ml of initial volume and 2.0–1000 ng ml−1 for 100 ml of initial volume. The slope of the calibration curve for direct measurement of Th by ICP-OES was improved 92-fold for 500 ml of initial volume and 45-fold for 100 ml of initial volume. The preconcentration factor was obtained as 100 for an initial volume of 500 ml. For this purpose, 25 and 50 ng ml−1 of Th in initial volumes were subjected to the preconcentration procedure. High recovery values were obtained from the experiments (Table 4). The interfering effects of foreign ions on the recovery of Th were investigated for 0.1 μg ml−1 of Th when the concentration of the possible ions (Cu, Co, Cr, Pb, Ni, Cd) was 10 μg ml−1. The results showed that the recovery of Th was not affected significantly when the ions were considered one by one (recoveries were higher than 96%). The co-effect of ions was investigated in a solution that contained the ions at a concentration of 10.0 μg ml−1. The results showed that when the abovementioned ions were in solution of 0.1 μg ml−1 of Th, the recovery value was 85.4 ± 0.4%.

Determination of Th in Real Samples and Accuracy of the Method The applicability of the method was validated through the analysis of a certified reference material of tea leaves (NCS ZC73014). It was digested in a microwave oven by using a mixture of HNO3 :HCl:H2 O2 TABLE 5 The Results for Th in Certified Reference Sample and Ore

Sample NCS ZC73014

Ore

S. Ozdemir et al.

Added (μg g−1)

Certified (μg g−1)

Found (μg g−1)

— 0.2 0.4 —

0.038 ± 0.012 — — —

0.035 ± 0.005 0.236 ± 0.003 0.437 ± 0.002 742 ± 3.9

(1:1:0.2). The digested sample was diluted with distilled water, and it was subjected to the preconcentration procedure. The results are similar to the certified values for Th. The presented method was used to determine the Th levels in the real ore sample from Sivrihisar-Eskis¸ehir (Turkey) by SPE. The standard addition method was used to assure accuracy of the method. The results are seen in Table 5.

CONCLUSIONS An alternative and low-cost method was developed and optimized for preconcentration of Th by using Agaricus bisporus as a solid-phase extractant and following determination by ICP-OES. It is well known that the sensitivity of atomic spectroscopic methods such as Atomic absorption spectroscopy (AAS) and ICPOES are not sufficient for low-level determination of Th. This disadvantage can be overcome by using inductively coupled plasma mass spectrometry (ICP-MS). However, the total cost of analysis is high. Therefore, the developed method has advantages over the others, including simplicity, a short time required for the analysis, low risk of contamination, and a low analytical cost based on the reduction of reagent consumed.

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