Abstract
In recent years, increasing awareness of the environmental impact of heavy metals has prompted a demand for monitoring and decontaminating industrial wastes prior to discharging into natural water bodies. This paper describes the preparation and electrochemical application of carbon paste electrode modified with nanocellulosic fibers for the determination of cadmium and lead in water samples using anodic stripping voltammetry. First, cadmium and lead were adsorbed on the carbon paste electrode surface at open circuit potential, followed by anodic stripping voltammetric scan from -1 to 0 V. Different factors affecting sensitivity and precision of the electrode, including accumulating solvent, pH of the accumulating solvent, accumulation time, supporting electrolyte, and scan rate were investigated. The proposed method was also applied to the determination of Cd (II) and Pb (II) in the presence of other interfering metal ions and cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, and Triton X-100 as a representative of cationic, anionic, and neutral surfactants. Linear calibration curves were obtained in the concentration ranges of 150–650 μg L−1 and 80–300 μg L−1, respectively, for cadmium and lead at an accumulated time of 10 min with limits of detection 88 and 33 μg L−1. Optimized working conditions are defined as acetate buffer of pH 5 as accumulating solvent, hydrochloric acid as supporting electrolyte, and scan rate 50 mV/s. This technique does not use mercury and therefore has a positive environmental benefit. The method is reasonably sensitive and selective and has been successfully applied to the determination of trace amounts of Cd (II) and Pb (II) in water samples.
Similar content being viewed by others
References
Bagheri H, Afkhami A, Saber-Tehrani M, Shirzadmehr A, Husain SW, Khoshsafar H, Tabatabaee M (2012a) Novel sensor fabrication for the determination of nanomolar concentrations of Ce3+ in aqueous solution. Anal Meth. doi:10.1039/C2AY00005A
Bagheri H, Afkhami A, Shirzadmehr A, Khoshsafar H, Khoshsafar H, Ghaedi H (2012b) Novel potentiometric sensor for the determination of Cd2+ based on a new nano-composite. Int J Environ Anal Chem. doi:10.1080/03067319.2011.649741
Bartlett PN, Denuarret G, Souza MFB (2000) A study of the preconcentration and stripping voltammetry of Pb(II) at carbon electrodes. Analyst 125:1135–1138
Brainina KZ, Malakhova NA, Stojko NY (2000) Stripping voltammetry in environmental and food analysis. Fres J Anal Chem 368:307–325
Cesarino I, Cavalheiro ETG, Brett CMA (2010) Simultaneous determination of cadmium, lead, copper and mercury ions using organo functionalized SBA-15 nanostructured silica modified graphite–polyurethane composite electrode. Electroanal 22(1):61–68
Chuparina EV, Aisueva TS (2011) Determination of heavy metal levels in medicinal plant Hemerocallis minor Miller by X-ray fluorescence spectrometry. Environ Chem Lett 9:19–23
Daniele S, Baldo MA, Bragato C (2008) Recent developments in stripping analysis on microelectrodes. Curr Anal Chem 4(3):215–228
Dey MK, Satpati AK, Sahoo S, Kameswaran R, Reddy AVR, Mukherjee T (2011) Bi-Film on a carbon paste electrode modified with nafion film embedded with multiwall carbon nano tubes for the determination of heavy metals. Anal Meth 3:2540–2546
Economou A, Fielden PR (1998) Selective determination of Ni (II) and Co (II) by flow injection analysis and adsorptive cathodic stripping voltammetry on a wall jet mercury film electrode. Talanta 46(5):1137–1146
Economou A (2005) Bismuth-film electrodes: recent developments and potentialities for electroanalysis. Trend Anal Chem 24:334–340
Gholivand MB, Parvin MH (2010) Differential pulse anodic stripping voltammetric simultaneous determination of copper(II) and silver(I) with bis(2-hydroxyacetophenone) butane-2,3-dihydrazone modified carbon paste electrodes. Electroanal 22(19):2291–2296
Goyal N, Gupta VK, Bachheti N (2007a) Voltammetric determination of adenosine and guanosine using fullerene-C60-modified glassy carbon electrode. Talanta 71(3):1110–1117
Goyal N, Gupta VK, Oyama M, Bachheti N (2007b) Gold nanoparticles modified indium tin oxide electrode for the simultaneous determination of dopamine and serotonin: application in pharmaceutical formulations and biological fluids. Talanta 72(3):976–983
Goyal RN, Gupta VK, Chatterjee S (2009) Fullerene—C60—modified edge plane pyrolytic graphite electrode for the determination of dexamethasone in pharmaceutical formulations and human biological fluids. Biosens Bioelectron 24:1649–1654
Grzes IM (2010) Ants and heavy metal pollution—a review. Eur J Soil Bio 46:350–355
Gupta VK, Jain AK, Singh LP, Khurana U (1997a) Porphyrins as carrier in PVC based membrane potentiometric sensors for nickel(II). Anal Chim Acta 355:33
Gupta VK, Jain S, Khurana U (1997b) A PVC-based pentathia-15-crown-5 membrane potentiometric sensor for mercury(II). Electroanalysis 9(6):478–480
Gupta VK, Kumar P (1999) Cadmium (II) selective sensors based on dibenzo-24-crown-8 in PVC matrix. Anal Chim Acta 389(1–3):205–212
Gupta VK, Mangla R, Khurana U, Kumar P (1999) Determination of uranyl ions using poly (vinyl chloride) based 4-tert-butylcalix [6] arene membrane sensor. Electroanalysis 11(8):573–576
Gupta VK, Mangla R, Agarwal S (2002) Pb (II) selective potentiometric sensor based on 4-tert-butylcalix [4] arene in PVC matrix. Electroanal 14:1127–1132
Gupta VK, Jain S, Chandra S (2003) Chemical sensor for lanthanum(III) determination using aza-crown as ionophore in poly(vinyl chloride) matrix. Anal Chim Acta 486(2):199–207
Gupta VK, Singh AK, Gupta B (2007) Schiff bases as cadmium (II) selective ionophores in polymeric membrane electrodes. Anal Chim Acta 583(2):340–348
Gupta VK, Goyal RN, Sharma RA (2009a) Comparative studies on neodymium (III)-selective membrane sensors. Anal Chim Acta 647:66–71
Gupta VK, Goyal RN, Sharma RA (2009b) Novel alizarin sensor for determination of vanadium, zirconium and molybdenum. Int J Electrochem Sci 4:156–172
Gupta VK, Khayat MA, Singh AK, Pal MK (2009c) Nano level detection of Cd (II) using poly (vinyl chloride) based membranes of Schiff bases. Anal Chim Acta 634(1):36–43
Gupta VK, Jain R, Pal MK (2010a) Mn2+ selective electrode based on 3-(6-aminopyridin-2-ylimino)-1, 3-diphenylpropylidene) pyridine-2, 6-diamine. Int J Electrochem Sci 5:1164–1178
Gupta VK, Rastogi A, Nayak A (2010b) Adsorption studies on the removal of hexavalent chromium from aqueous solution using a low cost fertilizer industry waste material. J Colloid Interface Sci 342:135–141
Jain AK, Gupta VK, Sahoo BB, Singh LP (1995a) Copper (II)-selective electrodes based on macrocyclic compounds. Anal Proc, (RSC) 32:99–101
Jain AK, Gupta VK, Singh LP (1995b) Neutral carrier and organic resin based membranes as sensors for uranyl ions. Anal Proc (RSC) 32:263–265
Jain AK, Gupta VK, Singh LP, Khurana U (1997a) Macrocycle based membrane sensors for the determination of cobalt (II) ions. Analyst 122:583–586
Jain AK, Gupta VK, Khurana U, Singh LP (1997b) A new membrane sensor for UO2+, based on 2-hydroxyacetophenoneoxime-thioureatrioxane resin. Electroanalysis 9:857–860
Jain AK, Gupta VK, Radi S, Singh LP, Raisoni JR (2006) A comparative study of Pb2+ sensors based on derivatized tetrapyrazole and calix[4]arene receptors. Electrochim Acta 51(12):2547–2553
Jia G, Wang H, Yan L, Wang X, Pei R, Yan T, Zhao Y, Guo X (2005) Cytotoxicity of carbon nanomaterials: singlewall nanotube, multi-wall nanotube, and fullerene. Env Sci & Tech 39(5):1378–1383
John AC, Ibironke LO, Adedeji V, Oladunni O (2011) Equilibrium and kinetic studies of the biosorption of heavy metal (cadmium) on Cassia siamea Bark. American-Eurasian Journal of Scientific Research 6(3):123–130
Jones S, Compton RG (2008) Stripping analysis using boron-doped diamond electrodes. Curr Anal Chem 4(3):170–176
Karadjova I, Izgi B, Gucer S (2002) Fractionation and speciation of Cu, Zn and Fe in wine samples by atomic absorption spectrometry. Spectroc Acta Pt B 57:581–590
Kardam A, Rohit Raj K, Arora JK, Srivastava S (2012) Artificial neural network modeling for biosorption of Pb (II) ions on nano cellulose fibers. Bionanoscience. doi:10.1007/s12668-012-0045-6, Springer, USA
Lam C, James JT, McCluskey R, Hunter RL (2004) Pulmonary toxicity of carbon nanotubes in mice 7 and 90 days after intratracheal instillation. Toxicology Science 77:126–134
Ma H, Burger C, Hsiao BS, Chu B (2011) Ultra-fine cellulose nanofibers: new nano-scale materials for water purification. J Mat Chem 21:7507–7510
Oberdorster G, Oberdorster E, Oberdorster J (2005) Nanotoxicology: an emerging discipline evolving from studies of ultrafine particles. Environ Health Persp 113:823–839
Rezaei B, Damiri S (2008) Multiwalled carbon nanotubes modified electrode as a sensor for adsorptive stripping voltammetric determination of hydrochlorothiazide. Sensors 8(9):1523–1529
Sain M, Oksman K (eds) (2006) Cellulose nanocomposites: processing, characterization, and properties, Volume 938 of ACS symposium series. American Chemical Society, Washington, DC
Samir MA, Alloin F, Dufresne A (2005) Review of recent research into cellulosic whiskers, their properties and their application in nanocomposites field. Biomacromolecules 6:612–626
Srivastava SK, Gupta VK, Dwivedi MK, Jain S (1995) Caesium PVC-crown (dibenzo-24-crown-8) based membrane sensor. Anal Proc (RSC) 32:21–23
Srivastava SK, Gupta VK, Jain S (1996a) A PVC-based benzo-15-crown-5 membrane sensor for cadmium. Electroanalysis 8:938–940
Srivastava SK, Gupta VK, Jain S (1996b) PVC-based 2,2,2-crypt and sensor for zinc ions. Anal Chem 68:1272–1275
Srivastava S, Kardam A, Raj KR (2012) Nanotech reinforcement onto cellulosic fibers: green remediation of toxic metals. International Journal of Green Nanotechnology 4:1–8
Svancara I, Vytras K, Kalcher K, Walcarius A, Wang J (2009) Carbon paste electrodes in facts, numbers, and notes: a review on the occasion of the 50-years jubilee of carbon paste in electrochemistry and electroanalysis. Electroanal 21(1):7–28
Visakh PM, Thomas S (2010) Preparation of bionanomaterials and their polymer nanocomposites from waste and biomass. Waste Biomass Valor 1:121–134
Wang J (2005) Stripping analysis at bismuth electrodes: a review. Electroanal 17(15–16):1341–1346
Wu KB, Hu SS, Fei JJ, Bai W (2003) Mercury-free simultaneous determination of Cd2+ and Pb2+ at a glassy carbon electrode modified with multi-wall carbon nanotubes. Anal Chim Acta 489:215–221
Xu H, Zeng LP, Xing SJ, Xian YZ, Shi GY, Jin LT (2008) Ultrasensitive voltammetric detection of trace lead, and cadmium using MWCNTs-Nafion-bismuth composite electrodes. Electroanal 20:2644
Acknowledgments
The authors gratefully acknowledge Prof. V.G. Das, Director, and Prof. L.D. Khemani, Head, Department of Chemistry, Dayalbagh Educational Institute, Dayalbagh, Agra, for providing necessary research facilities. The authors also gratefully acknowledge the Ministry of Human Resource and Development, New Delhi, for rendering financial assistance.
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible editor: Vinod Kumar Gupta
Rights and permissions
About this article
Cite this article
Rajawat, D.S., Kardam, A., Srivastava, S. et al. Nanocellulosic fiber-modified carbon paste electrode for ultra trace determination of Cd (II) and Pb (II) in aqueous solution. Environ Sci Pollut Res 20, 3068–3076 (2013). https://doi.org/10.1007/s11356-012-1194-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-012-1194-4