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Application of MnO2Resin and Dowex 1X8 manganese dioxide impregnated resin for the separation of chromium from biological samples

  • Iga ZubaEmail author
  • Halina Polkowska-Motrenko
Open Access
Article

Abstract

MnO2Resin and Dowex 1X8 manganese dioxide impregnated resin was used for chromium separation from biological samples. We examined sorption of chromium from acid solutions: hydrochloric, nitric and sulphuric in concentration range from 0.01 to 2 mol/dm3. The sorption process was evaluated by batch and column experiments. We also examined sorption of other elements in the developed systems, to check the selectivity of the process. Determination of chromium by radiochemical neutron activation analysis after separation with MnO2Resin was described.

Keywords

MnO2Resin Dowex 1X8 manganese dioxide impregnated resin Chromium sorption Radiochemical neutron activation analysis Chromium determination 

Introduction

Chromium is one of the elements widely distributed in the environment [1]. The large amounts of this metal come from industrial activities like electroplating, pigment production, leather tanning, and wood processing [2, 3]. The properties of chromium depend upon oxidation states and are very different. Chromium(III) is an important microelement, which is necessary to glucose, lipid and protein metabolism. Chromium(VI) has strong oxidizing potential and can easily penetrate biological membranes. The consequences of excessive exposure to this form may be skin damage, respiratory problems or in the same case cancer of kidneys, lungs or liver [4, 5, 6, 7]. For these reasons amounts of this metal in biological and geological samples should be constantly monitored. Institutions like EPA, FAO/WHO and EU recommend the permissible content of chromium in water, food and soil [8, 9, 10, 11, 12].

Determination of chromium is often realized after separation process with the use of exchange resin. Ion exchange method gives the possibility to recover and concentrate elements of interest from samples with different matrices. This method has many advantages such as: easy recovery of the element, low operation cost, selectivity, concentration of the element of interest, removal of interfering ions and possible regeneration of the resin after processing [13, 14]. Many adsorbents are used for chromium preconcentration, e.g. Amberlite IRA-910 [15], Dowex 1X8 [16], Amberlite IRA-96 [16], activated carbon [17], functionalized Amberlite XAD-7 [18] and nanoparticles (TiO2) [19].

MnO2Resin is an inorganic, amphoteric resin dedicated for sorption of radium from water samples [20]. This resin is characterized by high surface area, oxidizing properties and stability under acidic conditions. MnO2Resin was used primarily to extract radium from liquid waste by the uranium industry and to monitor marine waters for the presence of radioisotopes released from a nuclear reactor. The use of this sorbent is also mentioned in the literature for the preconcentration of lead, cadmium and chromium [21, 22, 23]. In natural systems (soils, water) manganese dioxide (MnO2) is a strong oxidizing agent which oxidizes Cr(III) to Cr(VI). The oxidation process depends upon concentration of soluble Cr, pH, surface area and the form of MnO2 [24]. Chromium(III) oxidation by MnO2 has fast initial stage and then proceeds to the slower rate [25]. Chung et al. studied the oxidation process of Cr(III) by three different Mn oxides: hausmanite, binessite and pyrolusite. Generally hausmanite, which has the highest Mn content, is a better oxidizing agent than binessite or pyrolusite [26]. Moreover Cr(VI) is also sorbed on the MnO2 surface. Bhutani et al. [27] reported that the chromate ions have a strong affinity for the surface of manganese dioxide and suggested the sorption process takes place by a mechanism of ligand exchange. Gheju et al. reported that the sorption process of Cr(VI) on MnO2 can occur through two mechanisms: physical (non-specific adsorption, electrostatic interactions) and chemical (specific adsorption, chemical interactions). Non-specific adsorption by electrostatic interactions comes from the charge of the MnO2 surface. The charge of the MnO2 surface depends on the pH of the solutions, in acidic medium it is positively charged and in basic medium—negatively. Generally, the sorption of chromates or dichromates occurs rapidly from acidic solutions. Specific adsorption in the case of Cr(VI) takes places as a result of ionic sphere complexation [28].

In our previous paper we have developed a procedure based on radiochemical neutron activation analysis where the separation process of chromium was carried out using MnO2Resin. Application of radiochemical version of neutron activation analysis for chromium determination in biological samples has allowed for the elimination of the interferences and has resulted in the lower limit of detection [29]. In this work we used Dowex 1X8 impregnated with saturated potassium permanganate solution for chromium separation and preconcentration. We examined resins with batch and column experiments. The results obtained for MnO2Resin and potassium permanganate impregnated Dowex 1X8 were compared. The results allowed to develop a procedure for the radiochemical determination of chromium in biological samples.

Experimental

Chromium standards for irradiation were prepared by weighing aliquots of the standard solution in polyethylene capsules (Type “V’’ Vrije Universiteit, Biologisch Laboratorium, Netherlands) and evaporating to dryness before encapsulation. The following radioactive tracers were used: 134Cs (T1/2 = 2.06 y), 60Co (T1/2 = 5.27 years), 51Cr (T1/2 = 27.7 days), 46Sc (T1/2 = 83.8 days), 65Zn (T1/2 = 244 days). All tracers were prepared by neutron irradiation of spectrally pure oxides or salts (mostly nitrates) in a Polish nuclear reactor MARIA (neutron flux of 1014 cm−2 s−1). All reagents were of analytical grade. MnO2 Resin 100–200 mesh (Eichrom Technologies LLC) was used as received. High purity water, 18 MΩ cm from Milli QRG Ultra Pure Water System, Millipore Co., was used for the preparation of all solutions.

Preparation of manganese dioxide impregnated resin

A mass of 40 g of Dowex 1X8 [Cl] resin (100–200 mesh), was washed twice with water from the Millipore system (reverse osmosis). The anion exchanger was then flooded with 40 mL of previously prepared saturated KMnO4 solution and stirred vigorously for 15 min. After that time the sample was centrifuged and the liquid from the sediment was poured off. The ionite impregnated with manganese groups was washed with 80 mL of distilled water of high purity, which was then centrifuged and washed away from the surface of the exchanger. This action was repeated three times. The resins prepared in this way were filtered and quantitatively transferred to a beaker. The exchanger was dried at 70 °C overnight and then gently mixed. The prepared resins were used in studies allowing for the determination of weight distribution coefficients.

Apparatus

Micro-analytical and analytical balances, Sartorius MC5 and Sartorius BP221S calibrated by the Central Office of Measures, were used to prepare standards, CRMs and samples for irradiation.

A high-pressure microwave system Anton Paar 3000 was applied to digest the samples.

Gamma-ray spectroscopic measurements were performed with the aid of a 255 cm3 HPGe well-type (Canberra) detector with associated electronics (resolution 2.15 keV for 1332 keV 60Co line, efficiency approximately 40% of a NaI (Tl) detector), coupled to the multichannel analyser and Genie-2000 spectroscopy software (Canberra).

Glass columns of I.D. 0.50 cm were used in column experiments.

Determination of distribution coefficient

Mass distribution coefficients of 51Cr and selected elements were determined in the system: MnO2Resin or manganese dioxide impregnated Dowex 1X8 resin—in hydrochloric, nitric and sulphuric acids by a batch equilibrium method at room temperature. Radioactive tracers of 134Cs, 51Cr, 65Zn, 46Sc, 60Co were used. A 0.2 g amount of the MnO2Resin or manganese dioxide impregnated Dowex 1X8 resin was weighed into a plastic flask, and 10 mL of hydrochloric, nitric or sulphuric acids solution and radioactive tracers of the elements examined were added. After 24 h shaking at room temperature, the resin was separated by filtration and the content of the radionuclide in the solution was measured by gamma spectrometry. The distribution coefficients were calculated from the equation:
$$ K_{\text{d}} = \frac{{A_{0} - A_{\text{S}} }}{{A_{\text{S}} }} \times \frac{V}{{m_{j} }} $$
(1)
where A0: the count rate of individual tracer in the standard solution; AS: is the count rate of individual tracer in an aliquot of the solution, after equilibration with the resin, loaded with a given reagent, V: volume of the solution (mL); and mj: mass of dry resin (g).

Column experiments

In column experiments we used a previously calibrated column (h = 10 cm, r = 0.25 cm) filled with MnO2Resin or Dowex 1X8 resin impregnated with potassium permanganate. For the column experiment, we used the radioactive tracers 134Cs, 51Cr, 65Zn, 46Sc, 60Co. We prepared test and standard samples which contained the same radioactive tracers. Test samples were placed onto the column, and after the separation process measured with gamma spectrometry and compared with standard.

Results and discusion

MnO2Resin (Eichrom) and potassium permanganate impregnated Dowex 1X8 resin were tested for chromium sorption. In Figs. 1, 2 and 3 we show results from batch experiments for commercially available resin MnO2Resin (Eichrom) for chromium and other elements (Cs, Sc, Zn, Co). Figures 1, 2 and 3 shows mass distribution coefficients in different concentrations of inorganic acids in range 0.01–2 mol/dm3.
Fig. 1

Mass distribution coefficients of 51Cr (Cr(VI)) and 134Cs, 46Sc, 65Zn and 60Co on MnO2Resin in sulphuric acid (concentration range 0.01–2 mol/dm3)

Fig. 2

Mass distribution coefficients of 51Cr (Cr(VI)) and 134Cs, 46Sc, 65Zn and 60Co on MnO2Resin in hydrochloric acid (concentration range 0.01–2 mol/dm3)

Fig. 3

Mass distribution coefficients of 51Cr (Cr(VI)) and 134Cs, 46Sc, 65Zn and 60Co on MnO2Resin in nitric acid (concentration range 0.01–2 mol/dm3)

As it can be seen in the Figs. 1, 2 and 3 sorption of chromium(VI) ions on MnO2Resin occurs preferably from dilute solutions of hydrochloric, nitric and sulphuric acids (0.01 mol/dm3). The highest mass distribution coefficient is observed in 0.01 mol/dm3 sulphuric acid. The sorption of chromium decreases when the concentration of acids increases. The mass distribution coefficient for other elements (Cs, Sc, Zn) in applied conditions were not high (excluding Co in 0.01 mol/dm3 HCl).

In Figs. 4, 5 and 6 we show the results from batch experiments for potassium permanganate impregnated Dowex 1X8 resin.
Fig. 4

Mass distribution coefficients of 51Cr (Cr(VI)) and 134Cs, 46Sc, 65Zn and 60Co on impregnated Dowex 1X8 resin in sulphuric acid (concentration range 0.01–2 mol/dm3)

Fig. 5

Mass distribution coefficients of 51Cr (Cr(VI)) and 134Cs, 46Sc, 65Zn and 60Co on impregnated Dowex 1X8 resin in hydrochloric acid (concentration range 0.01– mol/dm3)

Fig. 6

Mass distribution coefficients of 51Cr (Cr(VI)) and 134Cs, 46Sc, 65Zn and 60Co on impregnated Dowex 1X8 resin in nitric acid (concentration range 0.01–2 mol/dm3)

As it can be seen from Figs. 4, 5 and 6, sorption of chromium(VI) ions on impregnated Dowex 1X8 resin also occurs from diluted solutions of inorganic acids. The highest mass distribution coefficient for chromium was observed in 0.01 mol/dm3 HNO3. The sorption of chromium ions (similarly for MnO2Resin) decreases with increase of acids concentrations. The mass distribution coefficient for Cr(VI) on impregnated Dowex 1X8 resin is much smaller than for commercially available MnO2Resin. Probably the reason for this was heterogeneous planting of impregnated resin with manganese groups. The mass distribution coefficients for other examined elements were very small (Cs, Sc), but we observed sorption of cobalt in 0.01 mol/dm3 nitric acid. For Zn, the highest mass distribution coefficient was obtained in 2 mol/dm3 hydrochloric acid.

The results from batch experiments were verified with a series of column experiments. For MnO2Resin we have chosen 0.01 mol/dm3 sulphuric acid, for impregnated Dowex 1X8 resin, 0.01 mol/dm3nitric acid, because the sorption of chromium in these media was the highest. The results obtained for MnO2Resin are shown in Fig. 7, and for impregnated Dowex 1X8 resin in Fig. 8.
Fig. 7

Separation of chromium from selected elements on MnO2Resin in 0.01 mol/dm3 H2SO4 (column experiment)

Fig. 8

Separation of chromium from selected elements on impregnated with potassium permanganate Dowex 1X8 resin in 0.01 mol/dm3 HNO3 (column experiment)

In Figs. 7 and 8 we show the separation process of chromium on MnO2Resin and impregnated Dowex 1X8 resin. As can be seen chromium is completely separated from other elements in both cases studied. However in the case of manganese dioxide impregnated resin the shape of the chromium elution curve suggests the possibility of the presence of two forms of chromium. This also confirms the recovery of chromium after the separation process onto the column. The process is quantitative only in the case of MnO2Resin and we have chosen this resin for further research on chromium determination in biological samples.

Chromium determination in biological samples after the separation with MnO2Resin

In our work, we determined chromium in biological samples with radiochemical neutron activation analysis. Chromium is determined via 51Cr formed after reaction 50Cr (n,γ) 51Cr, with half-life (T1/2 = 27.7 days) and 320 keV line in gamma spectrum. Radiochemical neutron activation analysis is an analytical method, where the test samples are irradiated in neutron flux (usually in nuclear reactor) and after that, the separation process of selected element is carried out. Separation process can be carried out with different methods, for example: extraction, distillation, precipitation or ion chromatography. As a result, for the separation process, we minimized the influence from other elements which occur in biological matrix (40K, 24Na, 32P). For quantitative and selective separation of chromium from biological matrix we used previously checked by batch and column experiments MnO2Resin. The separation process was carried out in the same way like the column experiments on MnO2Resin. The irradiated samples were digested using a microwave system and the resulting solution was evaporated and dissolved in 0.01 mol/dm3 H2SO4. The obtained solution was introduced onto the top of a column filled with resin and the elution process started. Impurities were eluted by washing with first 0.1 mol/dm3 HNO3, and then with 4 mol/dm3 HCl. Chromium was quantitatively eluting with 8 mol/dm3 H2SO4. The procedure was checked by analysis of several certified references materials. The results are presented in Table 1.
Table 1

Determination of Cr in certified reference materials after separation with MnO2Resin

CRM

Cr certified value and its confidence limit (95%)

Cr Obtained result

X ± U (k = 2)

IAEA-392 algae

4.57 ± 0.18 mg kg−1

4.58 ± 0.18 mg kg−1

IAEA-336 lichen

1.06 ± 0.34 mg kg−1

1.05 ± 0.04 mg kg−1

NIST SRM 1566a oyster tissue

1.43 ± 0.46 mg kg−1

1.41 ± 0.04 mg kg−1

MODAS M-3 herring tissue

919 ± 105 ng g−1

1030 ± 30 ng g−1

As it can be seen from Table 1, the results obtained for chromium after separation process using MnO2Resin, agree very well with certified values. The analysis of several certified references materials confirms the high accuracy of the developed procedure. The detection limit calculated with the Curie equation is 4.9 ng g−1 (20,000 s counting time) [30].

Conclusion

MnO2Resin and Dowex 1X8 impreganted with potassium permanganate resin was used for chromium preconcentration and separation from other elements. Chromium has a high affinity to both resins. However, the Kd values for chromium were higher in MnO2Resin than for Dowex 1X8 impregnated resin. The column experiments show that the separation process of chromium from other elements is selective but only in the case of MnO2Resin was quantitative and selective. The procedure of quantitative separation of chromium on MnO2Resin was checked by analysis of several certified references materials. The results show agreement with certified values, which confirms the accuracy of the developed procedure.

Notes

References

  1. 1.
    Nayak D, Ghosh K, Lahiri S (2009) Studies on bio-acumulation of Cr-51 in by piper nigrum. J Radioanal Nucl Chem 280(3):503–506CrossRefGoogle Scholar
  2. 2.
    Bampaiti A, Noli F, Misaelides P (2013) Investigation of the Cr(VI) removal from aqueous solutions by stabilized iron-nanoparticles using 51Cr tracer. J Radioanal Nucl Chem 298:909–914CrossRefGoogle Scholar
  3. 3.
    Aber S, Amani-Ghadim AR, Mirzajami V (2009) Removal of Cr(VI) from polluted solutions by electrocoagulation: modeling of experimental results using artificial neural network. J Hazard Mater 171:484–490CrossRefGoogle Scholar
  4. 4.
    Chen S, Zhu L, Lu D, Cheng X, Zhan X (2010) Separation and chromium speciation by single-wall carbon nanotubes microcolumn and inductively coupled plasma mass spectrometry. Mirochem Acta 169:123–128Google Scholar
  5. 5.
    Pazos-Capeáns P, Barciela-Alons MC, Bermejo-Barrera A, Bermejo-Barrera P, Fisher A, Hill SJ (2006) On-line sequential determination of Cr(III) and Cr(VI) with selective elution of solid extracts using an alumina column. At. Spectr. 27(4):107–116Google Scholar
  6. 6.
    Shadid M, Shamshad S, Rafid M, Khalid S, Bibi I, Niazi NK, Dumat C, Rashid MI (2017) Chromium speciation, bioavailability, uptake, toxicity and detoxication in soil-plant system: review A. Chemosphere 178:513–533CrossRefGoogle Scholar
  7. 7.
    Linos A, Petralias A, Christophi CA, Chrisotoforidou E, Kourouton P, Stodilis M, Veloudaki A, Tzala E, Makris KC, Karagas MR (2011) Oral ingestion of hexavalent chromium through drinking water and cancer mortality in an industrial area of Greece–an ecological study. Environ Health 10:50–58CrossRefGoogle Scholar
  8. 8.
    US EPA (United States Environmental Protection Agency) (2004) Edition of the drinking water standards and health advisories, EPA 882-R-04-005, Office of Water U.S. Environmental Protection Agency, Washington, DC, WinterGoogle Scholar
  9. 9.
    EPA’s (2008) Report on the environment. http://www.epa.gov/roe
  10. 10.
    (2008) Guidelines for drinking water quality, 3rd edn, vol 1, Recommendations, WHO, GenevaGoogle Scholar
  11. 11.
    (2003) Chromium in drinking water, background document for development of WHO, guidelines for drinking water quality, WHO/SDE/WSH/03.04/4, WHO, GenevaGoogle Scholar
  12. 12.
    Council directive of 3 November 1998 on the quality of water intended for human consumption, OJEU, L 330/32,5.12/98Google Scholar
  13. 13.
    Galan B, Calzada M, Ortiz I (2006) Separation and concentration of Cr(VI)from ground waters by anion exchange using Lewatit MP-64: mathematical modelling at acidic pH. Solvent Extr Ion Exch 24:621–637CrossRefGoogle Scholar
  14. 14.
    Rengaraj S, Yeon KH, Moon SH (2001) Removal of chromium from water and wastewater by ion exchange resins. J Hazard Mater B87:273–287CrossRefGoogle Scholar
  15. 15.
    Lopez-Guerro MM, Verreda AE, Cano Pavon JM, Siles Coredo MT, Garcia de Torres A (2012) On-line preconcentration using chelating and ion-exchange minicolumns for the speciation of chromium(III) and chromium(VI) and their quantitative determination in natural waters by inductively coupled plasma mass spectrometry. JAAS 27:682–688Google Scholar
  16. 16.
    Edebali S, Pehlivan E (2010) Evaluation of Amberlite IRA96 and Dowex 1 × 8 ion-exchange resins for the removal of Cr(VI) from aqueous solution. Chem Eng J 161:161–166CrossRefGoogle Scholar
  17. 17.
    Gil RA, Cerutii S, Gasquez JA, Olsina RA, Martinez LD (2006) Preconcentration and speciation of chromium in drinking water samples by coupling of on-line sorption on activated carbon to ETAAS determination. Talanta 68(4):1065–1070CrossRefGoogle Scholar
  18. 18.
    Sadia M (2017) Indirect speciation of Cr(VI) and Cr(III) in water and food samples using newly synthesized Amberlite XAD-7 functionalized resin. J Biodivers Environ Sci 10(1):36–48Google Scholar
  19. 19.
    Mohamed A, Nasser WS, Osman TA, Toprak MS, Muhammed M, Uheida A (2017) Removal of chromium (VI) from aqueous solutions using surface modified composite nanofibres. J Colloid Interface Sci 505:682–691CrossRefGoogle Scholar
  20. 20.
    Moon DS, Burnett WC, Nour S, Horwitz P, Bond A (2003) Preconcentration of radium isotopes from natural waters using MnO2Resin. Appl Radiat Isotopes 59(4):255–262CrossRefGoogle Scholar
  21. 21.
    Burnett JL, Croudace IW, Warwick PE (2012) Lead pre-concentration using a novel manganese dioxide resin. Environ Earth Sci 67:637–640CrossRefGoogle Scholar
  22. 22.
    Huang X, Chen T, Zou X, Zhu M, Chen D, Pan M (2017) The adsorption of Cd(II) on manganese oxide investigated by batch and modeling techniques. Int J Environ Res Public Health 14(10):1145–1153CrossRefGoogle Scholar
  23. 23.
    Dai R, Liu J, Yu Ch, Sun R, Lan Y, Mao JD (2009) A comparative study of oxidation of Cr(III) in aqueous ions, complex ions and insoluble compounds by manganese-bearing mineral (birnessite). Chemosphere 76:536–541CrossRefGoogle Scholar
  24. 24.
    Zayed AM, Terry N (2003) Chromium in the environment factors affecting biological remediation. Plant Soil 249:139–156CrossRefGoogle Scholar
  25. 25.
    Schroeder DC, Lee GF (1975) Potential transformations of chromium in natural waters. Water Air Soil Pollut 4:355CrossRefGoogle Scholar
  26. 26.
    Chung JB, Zasoski RJ, Lim SU (1994) Kinetics of chromium (III) oxidation by various manganese oxides. Agric Chem Biotechnol 37:414–420Google Scholar
  27. 27.
    Bhutani MM, Mitra AK, Kumari R (1992) Kinetic study of Cr(VI) sorption on MnO2. J Radioanal Nucl Chem 157(1):75–86CrossRefGoogle Scholar
  28. 28.
    Gheju M, Balcu I, Mosoarca G (2016) Removal of Cr(VI) from aqueous solutions by adsorption on MnO2. J Hazard Mater 310:270–277CrossRefGoogle Scholar
  29. 29.
    Kuzelewska I, Polkowska-Motrenko H, Danko B (2016) Determination of chromium in biological materials by radiochemical neutron activation analysis (RNAA) using manganese dioxide. J Radioanal Nucl Chem 310:559–564CrossRefGoogle Scholar
  30. 30.
    Currie LA (1968) Limits for qualitative detection and quantitative determination. Application to radiochemistry. Anal Chem 40:586–593CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.Laboratory of Nuclear Analytical MethodsInstitute of Nuclear Chemistry and TechnologyWarsawPoland
  2. 2.Frank Laboratory of Neutron PhysicsJoint Institute for Nuclear ResearchDubnaRussia

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