CSIRO Publishing blank image blank image blank image blank imageBooksblank image blank image blank image blank imageJournalsblank image blank image blank image blank imageAbout Usblank image blank image blank image blank imageShopping Cartblank image blank image blank image You are here: Journals > Environmental Chemistry   
Environmental Chemistry
Journal Banner
  Environmental problems - Chemical approaches
blank image Search
blank image blank image
blank image
  Advanced Search

Journal Home
About the Journal
Editorial Structure
Online Early
Current Issue
Just Accepted
All Issues
Special Issues
Research Fronts
Virtual Issues
Sample Issue
Upcoming Research Front
For Authors
General Information
Submit Article
Author Instructions
Open Access
For Referees
Referee Guidelines
Review an Article
For Subscribers
Subscription Prices
Customer Service
Library Recommendation

blue arrow e-Alerts
blank image
Subscribe to our Email Alert or RSS feeds for the latest journal papers.

red arrow Connect with us
blank image
facebook twitter logo LinkedIn


Open Access Article << Previous     |     Next >>   Contents Vol 11(4)

Separation, detection and characterisation of engineered nanoparticles in natural waters using hydrodynamic chromatography and multi-method detection (light scattering, analytical ultracentrifugation and single particle ICP-MS)

Kim Proulx A and Kevin J. Wilkinson A B

A Department of Chemistry, Biophysical Environmental Chemistry group, University of Montreal, C.P. 6128, succursale Centre-ville, Montreal, QC, H3C 3J7, Canada.
B Corresponding author. Email: kj.wilkinson@umontreal.ca

Environmental Chemistry 11(4) 392-401 http://dx.doi.org/10.1071/EN13232
Submitted: 17 December 2013  Accepted: 2 May 2014   Published: 24 July 2014

 Full Text
 PDF (603 KB)
 Supplementary Material
 Export Citation

Environmental context. The effects of engineered nanoparticles on the environment and on human health are difficult to evaluate largely because nanoparticles are so difficult to measure. The main problems are that concentrations are low and the engineered nanoparticles are often difficult to distinguish from the environmental matrices in which they are found. We report a separation technique that facilitates the detection of engineered nanoparticles in natural waters.

Abstract. Few analytical techniques are presently able to detect and quantify engineered nanoparticles (ENPs) in the environment. The major challenges result from the complex matrices of environmental samples and the low concentrations at which the ENPs are expected to be found. Separation techniques such as asymmetric flow field flow fractionation (AF4) and more recently, hydrodynamic chromatography (HDC) have been used to partly resolve ENPs from their complex environmental matrices. In this paper, HDC was first coupled to light scattering detectors in order to develop a method that would allow the separation and detection of ENPs spiked into a natural water. Size fractionated samples were characterised using off-line detectors including analytical ultracentrifugation (AUC), dynamic light scattering (DLS) and single particle inductively coupled plasma mass spectrometry (SP-ICP-MS). HDC was able to separate a complex mixture of polystyrene, silver and gold nanoparticles (radii of 60, 40, 20 and 10 nm) contained within a river water matrix. Furthermore, the feasibility of using HDC coupled to SP-ICP-MS was demonstrated by detecting 4 µg L–1 of a 20-nm (radius) nAg in a river water sample.


[1]  M. F. Hochella, Nanoscience and technology the next revolution in the Earth sciences. Earth Planet. Sci. Lett. 2002, 203, 593.
CrossRef | CAS |

[2]  M. R. Wiesner, G. V. Lowry, P. Alvarez, D. Dionysiou, P. Biswas, Assessing the risks of manufactured nanomaterials. Environ. Sci. Technol. 2006, 40, 4336.
CrossRef | CAS | PubMed |

[3]  D. P. Rakcheev, A. Philippe, G. E. Schaumann, Hydrodynamic chromatography coupled with single particle-inductively coupled plasma mass spectrometry for investigating nanoparticles agglomerates. Anal. Chem. 2013, 85, 10 643.
CrossRef | CAS |

[4]  K. Tiede, A. B. A. Boxall, X. Wang, D. Gore, D. Tiede, M. Baxter, H. David, S. P. Tear, J. Lewis, Application of hydrodynamic chromatography-ICP-MS to investigate the fate of silver nanoparticles in activated sludge. J. Anal. At. Spectrom. 2010, 25, 1149.
CrossRef | CAS |

[5]  K. Tiede, A. B. A. Boxall, D. Tiede, S. P. Tear, H. David, J. Lewis, A robust size-characterisation methodology for studying nanoparticle behaviour in ‘real’ environmental samples, using hydrodynamic chromatography coupled to ICP-MS. J. Anal. At. Spectrom. 2009, 24, 964.
CrossRef | CAS |

[6]  R. F. Domingos, M. A. Baalousha, Y. Ju-Nam, M. M. Reid, N. Tufenkji, J. R. Lead, G. G. Leppard, K. J. Wilkinson, Characterizing manufactured nanoparticles in the environment: multimethod determination of particle sizes. Environ. Sci. Technol. 2009, 43, 7277.
CrossRef | CAS | PubMed |

[7]  R. Kaegi, A. Voegelin, C. Ort, B. Sinnet, B. Thalmann, J. Krismer, H. Hagendorfer, M. Elumelu, E. Mueller, Fate and transformation of silver nanoparticles in urban wastewater systems. Water Res. 2013, 47, 3866.
CrossRef | CAS | PubMed |

[8]  H. Weinberg, A. Galyean, M. Leopold, Evaluating engineered nanoparticles in natural waters. TRAC – Trends in Analytical Chemistry. 2011, 30, 72.
CrossRef | CAS |

[9]  S. A. Cumberland, J. R. Lead, Particle size distributions of silver nanoparticles at environmentally relevant conditions. J. Chromatogr. A 2009, 1216, 9099.
CrossRef | CAS | PubMed |

[10]  T. J. Cho, V. A. Hackley, Fractionation and characterization of gold nanoparticles in aqueous solution: asymmetric-flow field flow fractionation with MALS, DLS, and UV-Vis detection. Anal. Bioanal. Chem. 2010, 398, 2003.
CrossRef | CAS | PubMed |

[11]  M. E. Hoque, K. Khosravi, K. Newman, C. D. Metcalfe, Detection and characterization of silver nanoparticles in aqueous matrices using asymmetric-flow field flow fractionation with inductively coupled plasma mass spectrometry. J. Chromatogr. A 2012, 1233, 109.
CrossRef | CAS | PubMed |

[12]  E. P. Gray, T. A. Bruton, C. P. Higgins, R. U. Halden, P. Westerhoff, J. F. Ranville, Analysis of gold nanoparticle mixtures: a comparison of hydrodynamic chromatography (HDC) and asymmetrical flow field-flow fractionation (AF4) coupled to ICP-MS. J. Anal. At. Spectrom. 2012, 27, 1532.
CrossRef | CAS |

[13]  A. M. Striegel, A. K. Brewer, Hydrodynamic chromatography. Annu. Rev. Anal. Chem. 2012, 5, 15.
CrossRef | CAS |

[14]  K. J. Wilkinson, J. R. Lead (Eds), Environmental Colloids and Particles: Behaviour, Structure, and Characterisation 2007 (Wiley: Chichester, UK).

[15]  I. Perevyazko, A. Vollrath, S. Hornig, G. M. Pavlov, U. S. Schubert, Characterization of poly(methyl methacrylate) nanoparticles prepared by nanoprecipitation using analytical ultracentrifugation, dynamic light scattering, and scanning electron microscopy. J. Polym. Sci. A Polym. Chem. 2010, 48, 3924.
CrossRef | CAS |

[16]  K. L. Planken, H. Colfen, Analytical ultracentrifugation of colloids. Nanoscale. 2010, 2, 1849.
CrossRef | CAS | PubMed |

[17]  A. Bootz, V. Vogel, D. Schubert, J. Kreuter, Comparison of scanning electron microscopy, dynamic light scattering and analytical ultracentrifugation for the sizing of poly(butyl cyanoacrylate) nanoparticles. Eur. J. Pharm. Biopharm. 2004, 57, 369.
CrossRef | CAS | PubMed |

[18]  F. Laborda, J. Jimenez-Lamana, E. Bolea, J. R. Castillo, 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.
CrossRef | CAS |

[19]  C. Degueldre, P. Y. Favarger, Colloid analysis by single particle inductively coupled plasma-mass spectroscopy: a feasibility study. Colloids Surf. A Physicochem. Eng. Asp. 2003, 217, 137.
CrossRef | CAS |

[20]  M. Hadioui, C. Peyrot, K. J. Wilkinson, Improvements to single particle ICP-MS by the on-line coupling of ion exchange resins. Anal. Chem. 2014, 86, 4668.
CrossRef | CAS | PubMed |

[21]  H. E. Pace, N. J. Rogers, C. Jarolimek, V. A. Coleman, E. P. Gray, C. P. Higgins, J. F. Ranville, Single particle inductively coupled plasma-mass spectrometry: a performance evaluation and method comparison in the determination of nanoparticle size. Environ. Sci. Technol. 2012, 46, 12 272.
CrossRef | CAS |

[22]  H. E. Pace, N. J. Rogers, C. Jarolimek, V. A. Coleman, C. P. Higgins, J. F. Ranville, Determining transport efficiency for the purpose of counting and sizing nanoparticles via single particle inductively coupled plasma mass spectrometry. Anal. Chem. 2011, 83, 9361.
CrossRef | CAS | PubMed |

[23]  D. M. Mitrano, E. K. Lesher, A. Bednar, J. Monserud, C. P. Higgins, J. F. Ranville, Detecting nanoparticulate silver using single-particle inductively coupled plasma-mass spectrometry. Environ. Toxicol. Chem. 2012, 31, 115.
CrossRef | CAS | PubMed |

[24]  B. Franze, I. Strenge, C. Engelhard, Single particle inductively coupled plasma mass spectrometry: evaluation of three different pneumatic and piezo-based sample introduction systems for the characterization of silver nanoparticles. J. Anal. At. Spectrom. 2012, 27, 1074.
CrossRef | CAS |

[25]  D. Mahl, J. Diendorf, W. Meyer-Zaika, M. Epple, Possibilities and limitations of different analytical methods for the size determination of a bimodal dispersion of metallic nanoparticles. Colloids Surf. A Physicochem. Eng. Asp. 2011, 377, 386.
CrossRef | CAS |

[26]  J. W. Dolan, Why do Peaks Tail? 2003 (BASi Northwest Laboratory: McMinnville, OR, USA). Available at http://www.chromatographyonline.com/lcgc/data/articlestandard/lcgceurope/382003/69793/article.pdf [Verified 6 June 2014].

[27]  L. R. Snyder, J. J. Kirkland, J. L. Glajch, Practical HPLC Method Development 1997 (Wiley: New York).

[28]  H. Small, M. A. Langhorst, Hydrodynamic chromatography. Anal. Chem. 1982, 54, 892A.
CrossRef | CAS |

[29]  J. R. Lead, K. J. Wilkinson, S. Balnois, B. J. Cutak, C. K. Larive, S. Assemi, R. Beckett, Diffusion coefficients and polydispersities of the Suwannee River fulvic acid: comparison of fluorescence correlation spectroscopy, pulsed-field gradient nuclear magnetic resonance, and flow field-flow fractionation. Environ. Sci. Technol. 2000, 34, 3508.
CrossRef | CAS |

[30]  J. R. Lead, K. J. Wilkinson, Aquatic colloids and nanoparticles: current knowledge and future trends. Environ. Chem. 2006, 3, 159.
CrossRef | CAS |

[31]  M. Hadioui, S. Leclerc, K. J. Wilkinson, Multimethod quantification of Ag+ release from nanosilver. Talanta 2013, 105, 15.
CrossRef | CAS | PubMed |

[32]  J. Tuoriniemi, G. Cornelis, M. Hassellov, Size discrimination and detection capabilities of single-particle ICPMS for environmental analysis of silver nanoparticles. Anal. Chem. 2012, 84, 3965.
CrossRef | CAS | PubMed |

Legal & Privacy | Contact Us | Help


© CSIRO 1996-2016