Analytical and Bioanalytical Chemistry

, Volume 411, Issue 20, pp 5317–5329 | Cite as

Combination of cloud point extraction with single particle inductively coupled plasma mass spectrometry to characterize silver nanoparticles in soil leachates

  • Laura Torrent
  • Francisco Laborda
  • Eva Marguí
  • Manuela Hidalgo
  • Mònica IglesiasEmail author
Research Paper


The expansion of silver nanoparticle (AgNP) applications in industry as antibacterial agents has generated an increment of their presence in the environment. Once there, their behavior is not clear because they can undergo different transformation processes that affect their transport, mobility, bioavailability, and toxicity. Therefore, the characterization and quantification of these emerging contaminants are important to understand their behavior and the toxicity effects that can be exerted on living beings. Single particle inductively coupled plasma mass spectrometry (SP-ICPMS) has demonstrated its ability to characterize and give quantitative information on AgNPs in aqueous samples. However, sometimes, the discrimination of the signal corresponding to AgNPs from the signal of dissolved species (Ag(I)) is a challenge. In the present contribution, it is shown that the presence of high amounts of Ag(I) hamper silver nanoparticle size and nanoparticle concentration determination in aqueous samples by SP-ICPMS. To facilitate signal discrimination of both chemical forms, the combination of cloud point extraction (CPE) with SP-ICPMS was studied. CPE experimental conditions to separate AgNPs from Ag(I) were assessed and adapted taking into account the characteristics of the SP-ICPMS technique. CPE and soil matrix effects on particle size were evaluated, showing that particle size was not modified after being in contact with soil matrix and after being separated by CPE. Additionally, frequently used calculation methods for SP-ICPMS data treatment were assessed. Finally, the potential of the developed methodology CPE-SP-ICPMS was evaluated in aqueous soil leachates contaminated with mixtures of AgNPs/Ag(I).


Silver nanoparticles Dissolved silver species Single particle inductively coupled plasma mass spectrometry Cloud point extraction Soils Aqueous leachates 


Funding information

The Spanish Ministry of Economy and Competitiveness (MINECO) financially supported this work through CGL2013-48802-C3-2-R project (Program 2014) and CTQ2015-68094-C2-1-R project (Program 2015), this last also cofunded by the European Regional Development Fund (FEDER). L. Torrent received a FPI grant from the Spanish Ministry of Economy and Competitiveness (Ref. BES-2014-070625) and a FPI mobility scholarship for her predoctoral stage in the University of Zaragoza (Ref. EEBB-I-17-12391). The authors would like to acknowledge the use of Servicio General de Apoyo a la Investigación-SAI, Universidad de Zaragoza, for ICPMS measurements.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

216_2019_1914_MOESM1_ESM.docx (230 kb)
ESM 1 (DOCX 229 kb)


  1. 1.
    Goswami L, Kim KH, Deep A, Das P, Bhattacharya SS, Kumar S, et al. Engineered nano particles: nature, behavior, and effect on the environment. J Environ Manag. 2017;196:297–315. Scholar
  2. 2.
    Bundschuh M, Filser J, Lüderwald S, McKee MS, Metreveli G, Schaumann GE, et al. Nanoparticles in the environment: where do we come from, where do we go to? Environ Sci Eur. 2018;30:1–17. Scholar
  3. 3.
    Dwivedi AD, Dubey SP, Sillanpää M, Kwon Y-N, Lee C, Varma RS. Fate of engineered nanoparticles: implications in the environment. Coord Chem Rev. 2015;287:64–78. Scholar
  4. 4.
    McGillicuddy E, Murray I, Kavanagh S, Morrison L, Fogarty A, Cormican M, et al. Silver nanoparticles in the environment: sources, detection and ecotoxicology. Sci Total Environ. 2017;575:231–46. Scholar
  5. 5.
    Yu S, Yin Y, Liu J. Silver nanoparticles in the environment. Environ Sci Process. 2013;15:78–92. Scholar
  6. 6.
    Lead JR, Batley GE, Alvarez PJJ, Croteau MN, Handy RD, McLaughlin MJ, et al. Nanomaterials in the environment: behavior, fate, bioavailability, and effects—an updated review. Environ Toxicol Chem. 2018;37:2029–63. Scholar
  7. 7.
    Pace HE, Rogers NJ, Jarolimek C, Coleman VA, Higgins CP, Ranville JF. Determining transport efficiency for the purpose of counting and sizing nanoparticles via single particle inductively coupled plasma mass spectrometry. Anal Chem. 2011;83:9361–9. Scholar
  8. 8.
    Hagendorfer H, Lorenz C, Kaegi R, Sinnet B, Gehrig R, Goetz NV, et al. Size-fractionated characterization and quantification of nanoparticle release rates from a consumer spray product containing engineered nanoparticles. J Nanopart Res. 2010;12:2481–94. Scholar
  9. 9.
    Farkas J, Peter H, Christian P, Gallego Urrea JA, Hassellöv M, Tuoriniemi J, et al. Characterization of the effluent from a nanosilver producing washing machine. Environ Int. 2011;37:1057–62. Scholar
  10. 10.
    Kent RD, Vikesland PJ. Controlled evaluation of silver nanoparticle dissolution using atomic force microscopy. Environ Sci Technol. 2012;46:6977–84. Scholar
  11. 11.
    Akaighe N, MacCuspie RI, Navarro DA, Aga DS, Banerjee S, Sohn M, et al. Humic acid-induced silver nanoparticle formation under environmentally relevant conditions. Environ Sci Technol. 2011;45:3895–901. Scholar
  12. 12.
    Li X, Lenhart JJ. Aggregation and dissolution of silver nanoparticles in natural surface water. Environ Sci Technol. 2012;46:5378–86. Scholar
  13. 13.
    Kaegi R, Voegelin A, Ort C, Sinnet B, Thalmann B, Krismer J, et al. Fate and transformation of silver nanoparticles in urban wastewater systems. Water Res. 2013;47:3866–77. Scholar
  14. 14.
    Kaegi R, Voegelin A, Sinnet B, Zuleeg S, Hagendorfer H, Burkhardt M, et al. Behavior of metallic silver nanoparticles in a pilot wastewater treatment plant. Environ Sci Technol. 2011;45:3902–8. Scholar
  15. 15.
    Lombi E, Donner E, Taheri S, Tavakkoli E, Jämting ÅK, McClure S, et al. Transformation of four silver/silver chloride nanoparticles during anaerobic treatment of wastewater and post-processing of sewage sludge. Environ Pollut. 2013;176:193–7. Scholar
  16. 16.
    Elzey S, Grassian VH. Agglomeration, isolation and dissolution of commercially manufactured silver nanoparticles in aqueous environments. J Nanopart Res. 2010;12:1945–58. Scholar
  17. 17.
    El Badawy AM, Luxton TP, Silva RG, Scheckel KG, Suidan MT, Tolaymat TM. Impact of environmental conditions (pH, ionic strength, and electrolyte type) on the surface charge and aggregation of silver nanoparticle suspensions. Environ Sci Technol. 2010;44:1260–6. Scholar
  18. 18.
    Lau BLT, Hockaday WC, Ikuma K, Furman O, Decho AW. A preliminary assessment of the interactions between the capping agents of silver nanoparticles and environmental organics. Colloids Surf A Physicochem Eng Asp. 2013;435:22–7. Scholar
  19. 19.
    Ma R, Levard C, Marinakos SM, Cheng Y, Liu J, Michel FM, et al. Size-controlled dissolution of organic-coated silver nanoparticles. Environ Sci Technol. 2012;46:752–9. Scholar
  20. 20.
    Laborda F, Bolea E, Cepriá G, Gómez MT, Jiménez MS, Pérez-Arantegui J, et al. Detection, characterization and quantification of inorganic engineered nanomaterials: a review of techniques and methodological approaches for the analysis of complex samples. Anal Chim Acta. 2016;904:10–32. Scholar
  21. 21.
    Sportelli MC, Picca RA, Cioffi N. Recent advances in the synthesis and characterization of nano-antimicrobials. Trends Anal Chem. 2016;84:131–8. Scholar
  22. 22.
    Tulve NS, Stefaniak AB, Vance ME, Rogers K, Mwilu S, LeBouf RF, et al. Characterization of silver nanoparticles in selected consumer products and its relevance for predicting children’s potential exposures. Int J Hyg Environ Health. 2015;218:345–57. Scholar
  23. 23.
    Koopmans GF, Hiemstra T, Regelink IC, Molleman B, Comans RNJ. Asymmetric flow field-flow fractionation of manufactured silver nanoparticles spiked into soil solution. J Chromatogr A. 2015;1392:100–9. Scholar
  24. 24.
    Laborda F, Bolea E, Jiménez-Lamana J. Single particle inductively coupled plasma mass spectrometry for the analysis of inorganic engineered nanoparticles in environmental samples. Trends Environ Anal Chem. 2016;9:15–23. Scholar
  25. 25.
    Meermann B, Nischwitz V. ICP-MS for the analysis at the nanoscale-a tutorial review. J Anal At Spectrom. 2018;33:1432–68. Scholar
  26. 26.
    Laborda F, Jiménez-Lamana J, Bolea E, Castillo JR. Selective identification, characterization and determination of dissolved silver(I) and silver nanoparticles based on single particle detection by inductively coupled plasma mass spectrometry. J Anal At Spectrom. 2011;26:1362. Scholar
  27. 27.
    Peters R, Herrera-Rivera Z, Undas A, Van Der Lee M, Marvin H, Bouwmeester H, et al. Single particle ICP-MS combined with a data evaluation tool as a routine technique for the analysis of nanoparticles in complex matrices. J Anal At Spectrom. 2015;30:1274–85. Scholar
  28. 28.
    Gomez-Gonzalez MA, Bolea E, O’Day PA, Garcia-Guinea J, Garrido F, Laborda F. Combining single-particle inductively coupled plasma mass spectrometry and X-ray absorption spectroscopy to evaluate the release of colloidal arsenic from environmental samples. Anal Bioanal Chem. 2016;408:5125–35. Scholar
  29. 29.
    Linsinger TPJ, Peters R, Weigel S. International interlaboratory study for sizing and quantification of Ag nanoparticles in food simulants by single-particle ICPMS. Anal Bioanal Chem. 2014;406:3835–43. Scholar
  30. 30.
    Liu J, Murphy KE, Winchester MR, Hackley VA. Overcoming challenges in single particle inductively coupled plasma mass spectrometry measurement of silver nanoparticles. Anal Bioanal Chem. 2017;409:6027–39. Scholar
  31. 31.
    Laborda F, Jiménez-Lamana J, Bolea E, Castillo JR. Critical considerations for the determination of nanoparticle number concentrations, size and number size distributions by single particle ICP-MS. J Anal At Spectrom. 2013;28:1220. Scholar
  32. 32.
    Hadioui M, Peyrot C, Wilkinson KJ. Improvements to single particle ICPMS by the online coupling of ion exchange resins. Anal Chem. 2014;86:4668–74. Scholar
  33. 33.
    Pace HE, Rogers NJ, Jarolimek C, Coleman VA, Gray EP, Higgins CP, et al. Single particle inductively coupled plasma-mass spectrometry: a performance evaluation and method comparison in the determination of nanoparticle size. Environ Sci Technol. 2012;46:12272–80. Scholar
  34. 34.
    Mitrano DM, Lesher EK, Bednar A, Monserud J, Higgins CP, Ranville JF. Detecting nanoparticulate silver using single-particle inductively coupled plasma-mass spectrometry. Environ Toxicol Chem. 2012;31:115–21. Scholar
  35. 35.
    Lee S, Bi X, Reed RB, Ranville JF, Herckes P, Westerhoff P. Nanoparticle size detection limits by single particle ICP-MS for 40 elements. Environ Sci Technol. 2014;48:10291–300. Scholar
  36. 36.
    Tuoriniemi J, Cornelis G, Hassellöv M. Size discrimination and detection capabilities of single-particle ICPMS for environmental analysis of silver nanoparticles. Anal Chem. 2012;84:3965–72. Scholar
  37. 37.
    Cornelis G, Hassellöv M. A signal deconvolution method to discriminate smaller nanoparticles in single particle ICP-MS. J Anal At Spectrom. 2014;29:134–44. Scholar
  38. 38.
    Mudalige TK, Qu H, Linder SW. Asymmetric flow-field flow fractionation hyphenated ICP-MS as an alternative to cloud point extraction for quantification of silver nanoparticles and silver speciation: application for nanoparticles with a protein corona. Anal Chem. 2015;87:7395–401. Scholar
  39. 39.
    Franze B, Engelhard C. Fast separation, characterization, and speciation of gold and silver nanoparticles and their ionic counterparts with micellar electrokinetic chromatography coupled to ICP-MS. Anal Chem. 2014;86:5713–20. Scholar
  40. 40.
    Zhou XX, Liu R, Liu J-F. Rapid chromatographic separation of dissoluble Ag(I) and silver-containing nanoparticles of 1−100 nanometer in antibacterial products and environmental waters. Environ Sci Technol. 2014:14516–24.
  41. 41.
    Hagarová I. Separation and quantification of metallic nanoparticles using cloud point extraction and spectrometric methods: a brief review of latest applications. Anal Methods. 2017;9:3594–601. Scholar
  42. 42.
    Torrent L, Iglesias M, Hidalgo M, Marguí E. Determination of silver nanoparticles in complex aqueous matrices by total reflection X-ray fluorescence spectrometry combined with cloud point extraction. J Anal At Spectrom. 2018;33:383–94. Scholar
  43. 43.
    Li L, Stoiber M, Wimmer A, Xu Z, Lindenblatt C, Helmreich B, et al. To what extent can full-scale wastewater treatment plant effluent influence the occurrence of silver-based nanoparticles in surface waters? Environ Sci Technol. 2016;50:6327–33. Scholar
  44. 44.
    Wimmer A, Kalinnik A, Schuster M. New insights into the formation of silver-based nanoparticles under natural and semi-natural conditions. Water Res. 2018;141:227–34. Scholar
  45. 45.
    Wimmer A, Ritsema R, Schuster M, Krystek P. Sampling and pre-treatment effects on the quantification of (nano) silver and selected trace elements in surface water - application in a Dutch case study. Sci Total Environ. 2019;663:154–61. Scholar
  46. 46.
    El Hadri H, Hackley VA. Investigation of cloud point extraction for the analysis of metallic nanoparticles in a soil matrix. Environ Sci Nano. 2017;4:105–16. Scholar
  47. 47.
    German Standard legislation (1984) DIN 38414-S4: German standards methods for examination of water, waste water and sludge; group S (sludge and sediments); determination of leachability by water (S4). Berlin: Deutsches Institut für Noemung E.V. (DIN).Google Scholar
  48. 48.
    Bolea E, Laborda F, Castillo JR. Metal associations to microparticles, nanocolloids and macromolecules in compost leachates: size characterization by asymmetrical flow field-flow fractionation coupled to ICP-MS. Anal Chim Acta. 2010;661:206–14. Scholar
  49. 49.
    Abad-Álvaro I, Peña-Vázquez E, Bolea E, Bermejo-Barrera P, Castillo JR, Laborda F. Evaluation of number concentration quantification by single-particle inductively coupled plasma mass spectrometry: microsecond vs. millisecond dwell times. Anal Bioanal Chem. 2016;408:5089–97. Scholar
  50. 50.
    Montaño MD, Olesik JW, Barber AG, Challis K, Ranville JF. Single particle ICP-MS: advances toward routine analysis of nanomaterials. Anal Bioanal Chem. 2016;408:5053–74. Scholar
  51. 51.
    Van Der Zande M, Vandebriel RJ, Van Doren E, Kramer E, Rivera ZH, Serrano-Rojero CS, et al. Distribution, elimination, and toxicity of silver nanoparticles and silver ions in rats after 28-day oral exposure. ACS Nano. 2012;6:7427–42. Scholar
  52. 52.
    Liu J, Chao J, Liu R, Tan Z, Yin Y, Wu Y, et al. Cloud point extraction as an advantageous preconcentration approach for analysis of trace silver nanoparticles in environmental waters. Anal Chem. 2009;81:6496–502. Scholar
  53. 53.
    Torrent L, Iglesias M, Hidalgo M, Marguí E. Analytical capabilities of total reflection X-ray fluorescence spectrometry for silver nanoparticles determination in soil adsorption studies. Spectrochim Acta B At Spectrosc. 2016;126:71–8. Scholar
  54. 54.
    Tourinho PS, van Gestel CAM, Lofts S, Svendsen C, Soares AMVM, Loureiro S. Metal-based nanoparticles in soil: fate, behavior, and effects on soil invertebrates. Environ Toxicol Chem. 2012;31:1679–92. Scholar
  55. 55.
    Anjum NA, Gill SS, Duarte AC, Pereira E, Ahmad I. Silver nanoparticles in soil–plant systems. J Nanopart Res. 2013;15:1896. Scholar
  56. 56.
    Hartmann G, Schuster M. Species selective preconcentration and quantification of gold nanoparticles using cloud point extraction and electrothermal atomic absorption spectrometry. Anal Chim Acta. 2013;761:27–33. Scholar
  57. 57.
    Hartmann G, Hutterer C, Schuster M. Ultra-trace determination of silver nanoparticles in water samples using cloud point extraction and ETAAS. J Anal At Spectrom. 2013;28:567–72. Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of GironaGironaSpain
  2. 2.Group of Analytical Spectroscopy and Sensors (GEAS), Institute of Environmental Sciences (IUCA)University of ZaragozaZaragozaSpain

Personalised recommendations