Microchimica Acta

, 186:734 | Cite as

Gold nanostar-based voltammetric sensor for chromium(VI)

  • Susom Dutta
  • Guinevere Strack
  • Pradeep KurupEmail author
Original Paper


This paper presents an electrochemical sensor for Cr(VI) (chromate ion) in water. A disposable screen-printed electrode was modified with gold nanostars (AuNSs) that were synthesized by Good’s buffer method. Linear sweep voltammetry (LSV) was employed for the detection of Cr(VI) in 0.1 M sulfuric acid solution. The AuNSs are shown to provide higher current response to Cr(VI) than spherically shaped gold nanoparticles. The sensor gives the strongest response at a scan rate of 0.05 V (vs Ag/AgCl) and exhibits minimal interference from other electroactive species. The linear range extends from 10 to 75,000 ppb, and the limit of detection is 3.5 ppb. This is well below the provisional guideline value given by the World Health Organization. Excellent recoveries (ranging between 95 and 97%) were found when analyzing contaminated ground water samples obtained from a site situated in Wellesley, MA.

Graphical abstract

Schematic presentation of preparation of gold nanostars (AuNS) on carbon paste screen printed electrode (CPSPE) by drop casting and electrochemical detection of chromium (VI) using linear sweep voltammetry (LSV).


Heavy metals Ground water analysis Linear sweep voltammetry Carbon paste screen-printed electrode Nanoparticle Monitoring wells Star-shaped nanoparticle 



This work was supported by the National Science Foundation award # 1543042. Any opinions, findings, and conclusions or recommendations expressed in this paper are those of the researchers and do not necessarily reflect the views of the funding agency. The authors would like to thank Dr. Earl Ada for performing the TEM imaging. The authors acknowledge Mr. John Fitzgerald (MassDEP), and two graduate students Connor Sullivan and Michaela Fitzgerald for sampling water from groundwater monitoring wells located in Wellesley, MA.

Compliance with ethical standards

Competing interests

The author(s) declare that they have no competing interests.

Supplementary material

604_2019_3847_MOESM1_ESM.docx (694 kb)
ESM 1 (DOCX 693 kb)


  1. 1.
    Oze C, Bird DK, Fendorf S (2007) Genesis of hexavalent chromium from natural sources in soil and groundwater. Proc Natl Acad Sci 104(16):6544–6549CrossRefGoogle Scholar
  2. 2.
    Moffat I, Martinova N, Seidel C, Thompson CM (2018) Hexavalent chromium in drinking water. Journal-American Water Works Association 110(5):E22–E35CrossRefGoogle Scholar
  3. 3.
    Costa M (2003) Potential hazards of hexavalent chromate in our drinking water. Toxicol Appl Pharmacol 188(1):1–5CrossRefGoogle Scholar
  4. 4.
    Smith AH, Steinmaus CM (2009) Health effects of arsenic and chromium in drinking water: recent human findings. Annu Rev Public Health 30:107–122CrossRefGoogle Scholar
  5. 5.
    Paustenbach D, Rinehart W, Sheehan P (1991) The health hazards posed by chromium-contaminated soils in residential and industrial areas: conclusions of an expert panel. Regul Toxicol Pharmacol 13(2):195–222CrossRefGoogle Scholar
  6. 6.
    Sharma P, Bihari V, Agarwal SK, Verma V, Kesavachandran CN, Pangtey BS, Mathur N, Singh KP, Srivastava M, Goel SK (2012) Groundwater contaminated with hexavalent chromium [Cr (VI)]: a health survey and clinical examination of community inhabitants (Kanpur, India). PLoS One 7(10):e47877CrossRefGoogle Scholar
  7. 7.
    EPA U (2013) The third unregulated contaminant monitoring rule (UCMR 3): data summary. EPA, Washington DCGoogle Scholar
  8. 8.
    Jacobs JA, Testa SM (2005) Overview of chromium (VI) in the environment: background and history. Chromium (VI) handbook. CRC Press, New York, pp 1–21Google Scholar
  9. 9.
    Grabarczyk M (2008) Speciation analysis of chromium by adsorptive stripping voltammetry in tap and river water samples. Electroanalysis: An International Journal Devoted to Fundamental and Practical Aspects of Electroanalysis 20(20):2217–2222CrossRefGoogle Scholar
  10. 10.
    Baś B, Bugajna A, Jakubowska M, Niewiara E (2012) Normal pulse voltammetric determination of subnanomolar concentrations of chromium (VI) with continuous wavelet transformation. Electroanalysis 24(11):2157–2164CrossRefGoogle Scholar
  11. 11.
    Grabarczyk M, Baś B, Korolczuk M (2009) Application of a renewable silver based mercury film electrode to the determination of Cr (VI) in soil samples. Microchim Acta 164(3–4):465–470CrossRefGoogle Scholar
  12. 12.
    Ouyang R, Zhang W, Zhou S, Xue Z-L, Xu L, Gu Y, Miao Y (2013) Improved bi film wrapped single walled carbon nanotubes for ultrasensitive electrochemical detection of trace Cr (VI). Electrochim Acta 113:686–693CrossRefGoogle Scholar
  13. 13.
    Jorge E, Rocha M, Fonseca I, Neto M (2010) Studies on the stripping voltammetric determination and speciation of chromium at a rotating-disc bismuth film electrode. Talanta 81(1–2):556–564CrossRefGoogle Scholar
  14. 14.
    Cox JA, Kulesza PJ (1983) Stripping voltammetry of chromium (VI) at a poly (4-vinvlpyridine)-coated platium electrode. Anal Chim Acta 154:71–78CrossRefGoogle Scholar
  15. 15.
    Hallam PM, Kampouris DK, Kadara RO, Banks CE (2010) Graphite screen printed electrodes for the electrochemical sensing of chromium (VI). Analyst 135(8):1947–1952CrossRefGoogle Scholar
  16. 16.
    Miscoria SA, Jacq C, Maeder T, Negri RM (2014) Screen-printed electrodes for electroanalytical sensing, of chromium VI in strong acid media. Sensors Actuators B Chem 195:294–302CrossRefGoogle Scholar
  17. 17.
    Sánchez-Moreno RA, Gismera MJ, Sevilla MT, Procopio JR (2011) Potentiometric screen-printed Bisensor for simultaneous determination of chromium (III) and chromium (VI). Electroanalysis 23(1):287–294CrossRefGoogle Scholar
  18. 18.
    Tsai M-C, Chen P-Y (2008) Voltammetric study and electrochemical detection of hexavalent chromium at gold nanoparticle-electrodeposited indium tinoxide (ITO) electrodes in acidic media. Talanta 76(3):533–539CrossRefGoogle Scholar
  19. 19.
    Ouyang R, Bragg SA, Chambers JQ, Xue Z-L (2012) Flower-like self-assembly of gold nanoparticles for highly sensitive electrochemical detection of chromium (VI). Anal Chim Acta 722:1–7CrossRefGoogle Scholar
  20. 20.
    Dutta S, Strack G, Kurup P (2019) Gold nanostar electrodes for heavy metal detection. Sensors Actuators B Chem 281:383–391CrossRefGoogle Scholar
  21. 21.
    de Puig H, Tam JO, Yen C-W, Gehrke L, Hamad-Schifferli K (2015) Extinction coefficient of gold nanostars. J Phys Chem C 119(30):17408–17415CrossRefGoogle Scholar
  22. 22.
    Haiss W, Thanh NT, Aveyard J, Fernig DG (2007) Determination of size and concentration of gold nanoparticles from UV− Vis spectra. Anal Chem 79(11):4215–4221CrossRefGoogle Scholar
  23. 23.
    Jena BK, Raj CR (2008) Highly sensitive and selective electrochemical detection of sub-ppb level chromium (VI) using nano-sized gold particle. Talanta 76(1):161–165CrossRefGoogle Scholar
  24. 24.
    Svancara I, Foret P, Vytras K (2004) A study on the determination of chromium as chromate at a carbon paste electrode modified with surfactants. Talanta 64(4):844–852CrossRefGoogle Scholar
  25. 25.
    Bergamini MF, dos Santos DP, Zanoni MVB (2007) Development of a voltammetric sensor for chromium (VI) determination in wastewater sample. Sensors Actuators B Chem 123(2):902–908CrossRefGoogle Scholar
  26. 26.
    Calvo-Pérez A, Domínguez-Renedo O, Alonso-Lomillo M, Arcos-Martínez M (2014) Speciation of chromium using chronoamperometric biosensors based on screen-printed electrodes. Anal Chim Acta 833:15–21CrossRefGoogle Scholar
  27. 27.
    Domínguez-Renedo O, Ruiz-Espelt L, García-Astorgano N, Arcos-Martínez MJ (2008) Electrochemical determination of chromium (VI) using metallic nanoparticle-modified carbon screen-printed electrodes. Talanta 76(4):854–858CrossRefGoogle Scholar
  28. 28.
    Metters JP, Kadara RO, Banks CE (2011) New directions in screen printed electroanalytical sensors: an overview of recent developments. Analyst 136(6):1067–1076CrossRefGoogle Scholar
  29. 29.
    Kachoosangi RT, Compton RG (2013) Voltammetric determination of chromium (VI) using a gold film modified carbon composite electrode. Sensors Actuators B Chem 178:555–562CrossRefGoogle Scholar
  30. 30.
    Jin W, Wu G, Chen A (2014) Sensitive and selective electrochemical detection of chromium (VI) based on gold nanoparticle-decorated titania nanotube arrays. Analyst 139(1):235–241CrossRefGoogle Scholar
  31. 31.
    Wang Y, Laborda E, Crossley A, Compton RG (2013) Surface oxidation of gold nanoparticles supported on a glassy carbon electrode in sulphuric acid medium: contrasts with the behaviour of ‘macro’gold. Phys Chem Chem Phys 15(9):3133–3136CrossRefGoogle Scholar
  32. 32.
    Purwidyantri A, Chen C-H, Chen L-Y, Chen C-C, Luo J-D, Chiou C-C, Tian Y-C, Lin C-Y, Yang C-M, Lai H-C (2017) Speckled zno nanograss electrochemical sensor for staphylococcus epidermidis detection. J Electrochem Soc 164(6):B205–B211CrossRefGoogle Scholar
  33. 33.
    Khairy M, Choudry NA, Ouasti M, Kampouris DK, Kadara RO, Banks CE (2010) Gold nanoparticle ensembles allow mechanistic insights into electrochemical processes. ChemPhysChem 11(4):875–879CrossRefGoogle Scholar
  34. 34.
    Seo M, Chung TD (2019) Nanoconfinement effects in electrochemical reactions. Current Opinion in Electrochemistry 13:47–54CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Civil and Environmental EngineeringUniversity of Massachusetts LowellLowellUSA
  2. 2.Department of Electrical and Computer EngineeringUniversity of Massachusetts LowellLowellUSA

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