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CE-ICP-MS for speciation analysis


CE has certain advantages in comparison to chromatographic techniques, such as:
  • simplicity,
  • low running costs,
  • high spead of analysis,
  • unique selectivity and high degree of matrix tolerance (due to high theoretical plate numbers, i.e. normally ranging from 70,000 to 200,000).
The mechanism of separation of metal ions in CE is based on the difference in electrophoretic mobility of the metal ions. Sepatation can be achieved by several modes of CE, namely capillary zone electrophoresis (CZE), micellar electrokinetic capillary electrophoresis (MECE) or micellar electrokinetic capillary electrophoresis (MECC), capillary isotachophoresis (CI), capillary gel electrophoresis (CGE), ion-exchange electrokinetic chromatography (UIEEC), capillary isolectric focusing (CIEF), affinity capillary electrophoresis (IACE), capillary electrochromatography (CEC). While commonly based on the application of a high voltage, their separation principles are quite different, providing completely different mechanisms of characterization and identification for element species. While CE supplements conventional HPLC methods, it shows unique promise for separation purpose because it causes only a minor disturbance to the existing equilibrium between different species. There is no stationary phase, which has a huge surface area and gives various possibilities for undesired interactions. Therefore, species transformations are thought to be less frequent than with HPLC.

To achieve maximum separation by CE, optimization of CE parameters is critical. The independent parameters under the control of the analysts are:
  • selection of the buffer
  • pH of the buffer,
  • ion strength of the buffer,
  • applied voltage,
  • temperature of the capillary,
  • dimensions of the capillary,
  • additives to the background electrolyte.
The coupling of CE as the separation module with ICP-MS as the element-selective detector is much less straightforward in comparison to the coupling with HPLC or GC. The main problems are the low flow rate of CE that limit the choice of a nebulizer and the necessity to apply a high voltage accross the capillary and keeping the electrode grounded. The nebulizer should not create via a venturi-effect an additional flow component to the electroosmotic flow that would disturb the separation. Also any dead-volumes created by the interface would lead to band-broadening that has to be kept as low as possible.

One possible design of an interface is using a make-up flow that both is reducing the influence of the nebulizer (suction effect) on the separation and also allows for easy grounding of the capillary (see figure below).

Fig. 1 CE-ICP-MS interface using a mackup buffer

As can be seen from the development of publications related to CE-ICP-MS shown in Fig.2, the technique is not very often applied and also has surpassed already the highest interest in 2000. Many of the earlier papers deal with the development and optimization of the interface between CE and ICP-MS. Since the ICP-MS is a mass-flow sensitive detector, sensitivity strongly depends on the analyte stream transported into the plasma. However the CE produces very low flow rates in the range of nL/min only.  Also CE allows only very small sample volumes to be injected, while LC can accept orders of magnitude higher sample volumes. Therefore, while the absolute detection power might look very impressive, the realtive detection power given in concentration is less impressive and can often not compete with those provided by HPLC.

Fig. 2: Yearly publication rate for papers dealing with CE-ICP-MS for speciation analysis.

Tutorial web material related to capillary electrophphoresis

Simple diagram and explanation of CE
Capillary Electrophoresis Primer by the Royal Society of Chemistry
Capillary Electrophoresis Primer by ChemSoc
Capillary Electrophoresis: Injection Modes
QuickTime Movie: Capillary Electrophoresis
ShockWave Movie: Capillary Electrophoresis
Quicktime Movie: Modes of Capillary Electrophoresis
ShockWave Movie: Modes of Capillary Electrophoresis
MicroSolv: Capillary Electrophoresis Primer
Dejan Milosavljevic, Die Kapillar-Elektrophorese (in German)
UCDAVIS CHEMWIKI: Capillary electrophoresis

 Tutorial print material related to capillary electrophphoresis

 An informative classroom tutorial on CE (recommended reading for beginners)
Introduction to CE from Beckman
Micellar Electrokinetic Chromatography from Beckman (written by Prof Terabe who invented the technique).
Agilent CE System: A Quick Start Guide to Maintenance and Troubleshooting
Elektrophorese und Kapillarelektrophorese: pdf-Dokument von der Uni Ulm mit einer ausfühlichen Einführung in dasThema (in German)

 Reviews of CE-ICP-MS (newest first)

Christina Hein, Jonas M Sander and Ralf Kautenburger, Speciation via Hyphenation–Metal Speciation in Geological and Environmental Samples by CE-ICP-MS, J. Anal. Bioanal. Tech., 5/6 (2014) 225. doi: 10.4172/2155-9872.1000225

Andrei R.Timerbaev, Katarzyna Pawlak, Svetlana S.Aleksenko, Lidia S.Foteeva, Magdalena Matczuk, Maciej Jarosz, Advances of CE-ICP-MS in speciation analysis related to metalloproteomics of anticancer drugs, Talanta, 102 (2012) 164-170. doi: 10.1016/j.talanta.2012.07.031

Petr Kuban, Pavlina Houserova, Pavel Kuban, Peter C. Hauser, Vlastimil Kuban, Mercury speciation by CE: a review, Electrophoresis, 28/1-2 (2007) 58-68. doi: 10.1002/elps.200600457

Andreas Prange, Daniel Pröfrock, Application of CE-ICP-MS and CE-ESI-MS in metalloproteomics: challenges, developments, and limitations, Anal. Bioanal. Chem., 383/3 (2005) 372-389. DOI: 10.1007/s00216-005-3420-0

Bernhard Michalke, Capillary electrophoresis-inductively coupled plasma-mass spectrometry: A report on technical principles and problem solutions, potential, and limitations of this technology as well as on examples of application, Electrophoresis, 26/7-8 (2005) 1584-1597. DOI: 10.1002/elps.200410314

Gloria Alvarez-Llamas, María del Rosario Fernández de la Campa, Alfredo
, ICP-MS for specific detection in capillary electrophoresis, Trends Anal. Chem. (Pers. Ed.), 24/1 (2005) 28-36. doi:10.1016/j.trac.2004.09.007

 S.S. Kannamkumarath, K. Wrobel, K. Wrobel, C. B'Hymer, Joseph A. Caruso, Capillary electrophoresis-inductively coupled plasma-mass spectrometry: an attractive complementary technique for elemental speciation analysis, J. Chromatogr. A, 975/2 (2002) 245-266. doi:10.1016/S0021-9673(02)01218-9

J.W. Olesik, J.A. Kinzer, E.J. Grunwald, K.K. Thaxton, S.V. Olesik, The potential and challenges of elemental speciation by capillary electrophoresis - inductively coupled plasma mass spectrometry and electrospray or ionspray mass spectrometry, Spectrochim. Acta, Part B, 53/2 (1998) 239-251. doi: 10.1016/S0584-8547(97)00145-6

Studies on the instrumentation and instrumental parameters of CE-ICP-MS

Vahid Majidi, Nancy Miller-Ihli, Potential sources of error in capillary electrophoresis-inductively coupled plasma mass spectrometry for chemical speciation, Analyst (London), 123/5 (1998) 809-813.

Dirk Schaumlöffel, Andreas Prange, A new interface for combining capillary electrophoresis with inductively coupled plasma mass spectrometry, Fresenius J. Anal. Chem., 364/5 (1999) 452-456. doi: 10.1007/s002160051366

Anders Tangen, Walter Lund, Capillary electrophoresis-inductively coupled plasma mass spectrometry interface with minimised dead volume for high separation efficiency, J. Chromatogr. A, 891/1 (2000) 129-138. doi: 10.1016/S0021-9673(00)00617-8

Zhi-xin Wang, Andreas Prange, Use of Surface-Modified Capillaries in the Separation and Characterization of Metallothionein Isoforms by Capillary Electrophoresis Inductively Coupled Plasma Mass Spectrometry, Anal. Chem., 74/3 (2002) 626-631. doi: 10.1021/ac010862y

Gloria Alvarez-Llamas, María del Rosario Fernández de la Campa, Alfredo Sanz-Medel, Sample stacking capillary electrophoresis with ICP-(Q)MS detection for Cd, Cu and Zn speciation in fish liver metallothioneins, J. Anal. At. Spectrom.,  18/5 (2003) 460-466.  DOI: 10.1039/b300709j

J.E. Sonke, D.J. Furbish, V.J.M. Salters, Dispersion effects of laminar flow and spray chamber volume in capillary electrophoresis-inductively coupled plasma-mass spectrometry: a numerical and experimental approach, J. Chromatogr. A, 1015    (2003) 205-218. doi:10.1016/S0021-9673(03)01210-X

Enrique G. Yanes, Nancy J. Miller-Ihli, Use of a parallel path nebulizer for capillary-based microseparation techniques coupled with an inductively coupled plasma mass spectrometer for speciation measurements, Spectrochim. Acta, Part B, 59/6 (2004) 883-890. doi:10.1016/j.sab.2004.03.005

Qi Jun Song, Gillian M. Greenway, Tom McCreedy, Interfacing a microfluidic electrophoresis chip with inductively coupled plasma mass spectrometry for rapid elemental speciation, J. Anal. At. Spectrom., 19/7 (2004) 883-887. DOI: 10.1039/b401657b

Douglas D. Richardson, Sasi S. Kannamkumarath, Rodolfo G. Wuilloud, Joseph A. Caruso, Hydride Generation Interface for Speciation Analysis Coupling Capillary Electrophoresis to Inductively Coupled Plasma Mass Spectrometry, Anal. Chem., 76/23 (2004) 7137-7142. DOI: 10.1021/ac049066t

Jean Chamoun, Agnès Hagège, Sensitivity enhancement in capillary electrophoresis-inductively coupled plasma-mass spectrometry for metal/protein interactions analysis by using large volume stacking with polarity switching, J. Anal. At. Spectrom., 20/10 (2005) 1030-1034. DOI: 10.1039/b502838h

EVISA Database system

Journals related to Electrophoresis
Organizations (Societies, Associations) related to Electrophoresis
Companies: Manufacturers of CE Systems
Instruments: Commercially available CE Systems
Instruments: Commercially availabe CE-ICP-MS Interface kits
Scientists working with capillary electrophoresis

EVISA link pages

Resources related to analytical sciences
Resources related to mass spectrometry

Resources related to quality assurance/quality control

 Instrument manufacturer's application notes

Agilent Technologies: #5988-4332EN: Technical Features of the ICP-MS Plasma Chromatographic Software
Agilent Technologies: #5989-6160EN: Handbook of Hyphenated ICP-MS Applications (First edition)
Agilent Technologies: #5990-9473EN: Handbook of Hyphenated ICP-MS Applications (Second edition)

 Other web resources:

Email listings of journal literature on CE
Agilent web site on Capillary Electrophoresis Instruments and Application Notes
 Agilent Technologies: Handbook of Hyphenated ICP-MS Applications (1st edition, 2007)
Agilent Technologies: Handbook of Hyphenated ICP-MS Applications (2nd edition, 2012)
SeparationsNow.com with electrophoresis news and articles
CE Trouble-Shooting
Analytical Methods Committee, Report of the Instrumental Criteria Subcommittee: Part XII (2000): Instrumentation for Capillary Electrophoresis

News related to CE-ICP-MS for speciation analysis (newest first)

EVISA  News, January 24, 2007: Agilent Technologies joins University of Cincinnati to study impact of metal species in biology and the environment
EVISA News, October 20, 2004: Thermo Electron and Pau University Establish New Center of Excellence for Elemental Speciation Analysis

Further chapters on techniques and methodology for speciation analysis:

Chapter 1: Tools for elemental speciation
Chapter 2: ICP-MS - A versatile detection system for speciation analysis
Chapter 3: LC-ICP-MS - The most often used hyphenated system for speciation analysis
Chapter 4: GC-ICP-MS- A very sensitive hyphenated system for speciation analysis
Chapter 5: CE-ICP-MS for speciation analysis
Chapter 6: ESI-MS: The tool for the identification of species
Chapter 7: Speciation Analysis - Striving for Quality
Chapter 8: Atomic Fluorescence Spectrometry as a Detection System for Speciation Analysis
Chapter 9: Gas chromatography for the separation of elemental species
Chapter 10: Plasma source detection techniques for gas chromatography
Chapter 11: Fractionation as a first step towards speciation analysis
Chapter 12: Flow-injection inductively coupled plasma mass spectrometry for speciation analysis
Chapter 13: Gel electrophoresis combined with laser ablation inductively coupled plasma mass spectrometry for speciation analysis
Chapter 14: Non-chromatographic separation techniques for speciation analysis

last time modified: December 14, 2016


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