Skip to main content
Log in

A dual-readout paper-based analytical device for the simultaneous determination of hexavalent Cr and total Cr

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

A paper-based analytical device (PAD) is presented with colorimetric/electrochemical dual readouts for the simultaneous sensing of total chromium (Cr) and hexavalent chromium (Cr(VI)). This device consists of a homemade three-electrode system and a patterned paper chip, integrating multiple functions including electrochemical detection, fluid driving, online oxidation, and colorimetric detection. The fiberglass filter paper with a hydrophilic microchannel was used to achieve self-driving fluidics without external equipment. One end of the microchannel was integrated with a homemade three-electrode system to achieve sample loading and electrochemical detection. The middle region on the microchannel was modified with oxidizing reagents to perform online pretreatment, and the yield of Cr(III) oxidation can reach 97.9%, ensuring reliable colorimetric detection of total Cr at another end of the microchannel modified with chromogenic agents. With this device, the signals of Cr(VI) (the signal peak at 0.29 V vs. Ag/AgCl) and total Cr can be obtained in one single injection. After optimization, the limit of detection (LOD) of Cr(VI) and total Cr were 0.01 mg L−1 and 0.06 mg L−1 and the linear ranges were 0.05–3.0 mg L−1 and 0.2–3.0 mg L−1, respectively. The relative standard deviations (RSD) of the electrochemical testing of Cr(VI) results were in a range 1.3%–8.7% (n = 3), and the RSD values of the colorimetric testing of total Cr were between 0.7–9.2% (n = 3). The device’s reliability was demonstrated by performing the practical speciation of Cr in tap water, river water, and electroplating wastewater while the recoveries obtained using the present method were in the range 93.5–106%. Overall, the proposed device provides high application prospect in the on-site rapid Cr speciation.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Guo SY, Xiao CQ, Zhou N, Chi R (2021) Speciation, toxicity, microbial remediation and phytoremediation of soil chromium contamination. Environ Chem Lett 19:1413–1431. https://doi.org/10.1007/s10311-020-01114-6

    Article  CAS  Google Scholar 

  2. Shahid M, Shamshad S, Rafiq M, Khalid S, Bibi I, Niazi NK, Dumat C, Rashid MI (2017) Chromium speciation, bioavailability, uptake, toxicity and detoxification in soil-plant system: a review. Chemosphere 178:513–533. https://doi.org/10.1016/j.chemosphere.2017.03.074

    Article  CAS  Google Scholar 

  3. Sedman RM, Beaumont J, McDonald TA, Reynolds S, Krowech G, Howd R (2006) Review of the evidence regarding the carcinogenicity of hexavalent chromium in drinking water. J Environ Sci Health C 24:155–182. https://doi.org/10.1080/10590500600614337

    Article  CAS  Google Scholar 

  4. Linos A, Petralias A, Christophi CA (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. https://doi.org/10.1186/1476-069X-10-50

    Article  CAS  Google Scholar 

  5. A Pechova L Pavlata 2007 Chromium as an essential nutrient: a review Veterinarni Medicina 52 1 18 https://doi.org/10.17221/2010-VETMED

  6. Anderson RA, Cheng N, Bryden NA, Polansky MM, Cheng N, Chi J, Feng J (1997) Elevated intakes of supplemental chromium improve glucose and insulin variables in individuals with type 2 diabetes. Diabetes 46:1786–1791. https://doi.org/10.2337/diab.46.11.1786

    Article  CAS  Google Scholar 

  7. Hernández-Ruiz E, Alvarado-Flores J, Rubio-Franchini I, Ventura-Juárez J, Rico-Martínez R (2016) Adverse effects and bioconcentration of chromium in two fresh-water rotifer species. Chemosphere 158:107–115. https://doi.org/10.1016/j.chemosphere.2016.05.067

    Article  CAS  Google Scholar 

  8. Chebeir M, Liu HZ (2016) Kinetics and mechanisms of Cr(VI) formation via the oxidation of Cr(III) solid phases by chlorine in drinking water. Environ Sci Technol 50:701–710. https://doi.org/10.1021/acs.est.5b05739

    Article  CAS  Google Scholar 

  9. Zhu XY, Deng Y, Li PC, Yuan DX, Ma J (2019) Automated syringe-pump-based flow-batch analysis for spectrophotometric determination of trace hexavalent chromium in water samples. Microchem J 145:1135–1142. https://doi.org/10.1016/j.microc.2018.12.040

    Article  CAS  Google Scholar 

  10. N Dawra N Dabas 2022 Advances in spectrophotometric determination of Chromium (III) and Chromium (VI) in water: a review Int J Environ Anal Chem 1–22 https://doi.org/10.1080/03067319.2022.2076224

  11. Rahbar N, Salehnezhad Z, Hatamie A, Babapour A (2018) Graphitic carbon nitride nanosheets as a fluorescent probe for chromium speciation. Microchim Acta 185:1–9. https://doi.org/10.1007/s00604-017-2615-3

    Article  CAS  Google Scholar 

  12. Tahmasebi Z, Davarani SSH (2016) Selective and sensitive speciation analysis of Cr (VI) and Cr (III), at sub-μg L-1 levels in water samples by electrothermal atomic absorption spectrometry after electromembrane extraction. Talanta 161:640–646. https://doi.org/10.1016/j.talanta.2016.09.016

    Article  CAS  Google Scholar 

  13. Islam A, Ahmad H, Zaidi N, Kumar S (2016) A graphene oxide decorated with triethylenetetramine-modified magnetite for separation of chromium species prior to their sequential speciation and determination via FAAS. Microchim Acta 183:289–296. https://doi.org/10.1007/s00604-015-1641-2

    Article  CAS  Google Scholar 

  14. Jia XY, Gong DR, Xu B, Chi QQ, Zhang X (2016) Development of a novel, fast, sensitive method for chromium speciation in wastewater based on an organic polymer as solid phase extraction material combined with HPLC–ICP-MS. Talanta 147:155–161. https://doi.org/10.1016/j.talanta.2015.09.047

    Article  CAS  Google Scholar 

  15. Chen SZ, Zhu L, Lu DB, Cheng XL, Zhou XR (2010) Separation and chromium speciation by single-wall carbon nanotubes microcolumn and inductively coupled plasma mass spectrometry. Microchim Acta 169:123–128. https://doi.org/10.1007/s00604-010-0328-y

    Article  CAS  Google Scholar 

  16. Noviana E, Ozer T, Carrell CS, Link JS, McMahon C, Jang I, Henry CS (2021) Microfluidic paper-based analytical devices: from design to applications. Chem Rev 121:11835–11885. https://doi.org/10.1021/acs.chemrev.0c01335

    Article  CAS  Google Scholar 

  17. Stern CM, Jegede TO, Hulse VA, Elgrishi N (2021) Electrochemical reduction of Cr(VI) in water: lessons learned from fundamental studies and applications. Chem Soc Rev 50:1642–1667. https://doi.org/10.1039/d0cs01165g

    Article  CAS  Google Scholar 

  18. Wang W, Bai H, Li HY, Lv Q, Wang ZJ, Zhang Q (2017) Disposable plastic electrode for electrochemical determination of total chromium and hexavalent chromium. J Electroanal Chem 794:148–155. https://doi.org/10.1016/j.jelechem.2017.04.016

    Article  CAS  Google Scholar 

  19. Hilali N, Mohammadi H, Amine A, Zine N, Errachid A (2020) Recent advances in electrochemical monitoring of chromium. Sensors 20:5153. https://doi.org/10.3390/s20185153

    Article  CAS  Google Scholar 

  20. Metters JP, Kadara RO, Banks CE (2012) Electroanalytical sensing of chromium (III) and (VI) utilising gold screen printed macro electrodes. Analyst 137:896–902. https://doi.org/10.1039/c2an16054d

    Article  CAS  Google Scholar 

  21. Alahmad W, Sahragard A, Varanusupakul P (2021) An overview of the recent developments of microfluidic paper-based analytical devices for the detection of chromium species. Microchem J 170:106699. https://doi.org/10.1016/j.microc.2021.106699

    Article  CAS  Google Scholar 

  22. Rattanarat P, Dungchai W, Cate DM, Siangproh W, Volckens J, Chailapakul O, Henry CS (2013) A microfluidic paper-based analytical device for rapid quantify-cation of particulate chromium. Anal Chim Acta 800:50–55. https://doi.org/10.1016/j.aca.2013.09.008

    Article  CAS  Google Scholar 

  23. Zhai HM, Zhou T, Fang F, Wu ZY (2020) Colorimetric speciation of Cr on paper-based analytical devices based on field amplified stacking. Talanta 210:120635. https://doi.org/10.1016/j.talanta.2019.120635

    Article  CAS  Google Scholar 

  24. Alahmad W, Varanusupakul P, Kaneta T, Varanusupakul P (2019) Chromium speciation using paper-based analytical devices by direct determination and with electromembrane microextraction. Anal Chim Acta 1085:98–106. https://doi.org/10.1016/j.aca.2019.08.002

    Article  CAS  Google Scholar 

  25. Muhammed A, Hussen A, Kaneta T (2021) Speciation of chromium in water sam-ples using microfluidic paper-based analytical devices with online oxidation of tri-valent chromium. Anal Bioanal Chem 413:3339–3347. https://doi.org/10.1007/s00216-021-03274-y

    Article  CAS  Google Scholar 

  26. Wang W, Ding SN, Wang ZJ, Lv Q, Zhang Q (2021) Electrochemical paper-based microfluidic device for on-line isolation of proteins and direct detection of lead in urine. Biosens Bioelectron 187:113310. https://doi.org/10.1016/j.bios.2021.113310

    Article  CAS  Google Scholar 

  27. Danilov FI, Protsenko VS (1998) Electroreduction of hexavalent chromium compounds. Russ J Electrochem 34:276–281

    CAS  Google Scholar 

  28. Jin W, Wu GS, Chen AC (2014) Sensitive and selective electrochemical detection of chromium (VI) based on gold nanoparticle-decorated titania nanotube arrays. Analyst 139:235–241. https://doi.org/10.1039/c3an01614e

    Article  CAS  Google Scholar 

  29. Wang W, Bai H, Li HY, Lv Q, Zhang Q, Bao N (2016) Carbon tape coated with gold film as stickers for bulk fabrication of disposable gold electrodes to detect Cr (VI). Sens Actuators, B Chem 236:218–225. https://doi.org/10.1016/j.snb.2016.05.155

    Article  CAS  Google Scholar 

  30. Kachoosangi RT, Compton RG (2013) Voltammetric determination of Chromium(VI) using a gold film modified carbon composite electrode. Sens Actuators, B Chem 178:555–562. https://doi.org/10.1016/j.snb.2012.12.122

    Article  CAS  Google Scholar 

  31. Welch CM, Nekrassova O, Compton RG (2005) Reduction of hexavalent chromium at solid electrodes in acidic media: reaction mechanism and analytical applications. Talanta 65:74–80. https://doi.org/10.1016/j.talanta.2004.05.017

    Article  CAS  Google Scholar 

  32. Nair V, Deepthi A (2007) Cerium (IV) ammonium nitrate a versatile single-electron oxidant. Chem Rev 107:1862–1891. https://doi.org/10.1021/cr068408n

    Article  CAS  Google Scholar 

Download references

Funding

This work was supported by the Beijing Outstanding Young Scientist Program (BJJWZYJH01201910005017) and the National Natural Science Foundation of China (No. 21936001).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Qing Zhang or Xiayan Wang.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher's note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Additional file 1: Fig. S1 Reaction of Cr (VI) with DPC to form Cr(III)-DPCO complex [7]. Fig. S2 (a) Effect of Ce (IV) oxidizerconcentration on the colorimetric intensity of the Cr-DPCO complex (n=3). (b) Effect of DPC concentration on the colorimetric intensity of the resulting complex (n=3). Sample: 2.0 mg L-1 Cr (III) in 0.01 M HCl. Insets display the corresponding photos. Fig. S3 Storage stability of the gold-coated PET electrodes (n = 3) for detection of the 1.0 mg L-1 Cr(VI). Table S1 Analytical performance of electrochemical and colorimetric methods for chromium speciation. Table S2 Determination of Cr (VI) and total Cr in real samples (n=3)

Supplementary file1 (DOCX 188 kb)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

An, Y., Wang, W., Lv, Q. et al. A dual-readout paper-based analytical device for the simultaneous determination of hexavalent Cr and total Cr. Microchim Acta 189, 445 (2022). https://doi.org/10.1007/s00604-022-05532-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-022-05532-x

Keywords

Navigation