LC-ICP-MS: The most often used hyphenated system for speciation analysis

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LC-ICP-MS: The most often used hyphenated system for speciation analysis

(21.06.2007)

Coupling of Liquid Chromatography with ICP-MS is straightforward. Nebulizers are available that can accept the effluent from standard, µ-HPLC and even nano-HPLC. With all the different possiblities of ion exchange, reverse-phase, affinity, size-exclusion, ion-pairing and any other of the numerous techniques, liquid chromatography offers a very rich tool-box for separation that can be used to separate many of the species of interest.

Liquid chromatography (LC) is an extremely versatile technique with numerous advantages:

both the stationary phase and the mobile phase may be altered to achieve the desired separation,
separations can be further enhanced by the addition of additives (chiral additives, ion pair reagents, surfactants) to the mobile phase,
separations can be enhanced by changing the mobile phase during the analysis (gradient elution),
an enourmous variety of stationary phases are commercially available based on a rich variety of separation principles such as
- normal phase chromatography (NPC)
- reversed phase chromatography (RPC)
- reversed phase ion pair chromatography (IPC)
- micellar chromatography
- ion exchange chromatography (IEC)
- size exclusion chromatography (SEC).
Usually, minimum sample preparation is required.

Fig. 1 Coupling of HPLC with ICP-MS

Liquid sample introduction is the standard in ICP-MS, therefore coupling of liquid chromatography with ICP-MS in the simplest form is just the connection of the column outlet with the nebulizer of the sample introduction system via a transfer tubing. It is not a surprise that the hyphenated system resulting from the coupling of liquid chromatography and ICP-MS is the most often used system for speciation analysis related to the ICP-MS detection. About 1/3 of all publications on speciation analysis related to ICP-MS describe the use of LC-ICP-MS.

Fig. 2: Development of publications related to LC-ICP-MS for speciation analysis

LC-ICP-MS has important advantages for speciation analysis:

Complex chromatograms are reduced to simple "elementograms"
Quantification of even unknown element species is possible with respect to the detected element due to compound independent sensitivity without the necessity of having standards.

However the hard ionization and atomization power of the plasma source also has some drawbacks:

All molecular information is lost
Species characterization is limited to chromatographic retention times

Looking more closely onto the hyphenated system, some details have to be discussed:

contamination with metallic compounds arising from the chromatographic system (pump, valve, tubing) or the stationary and mobile phase,
dispersion effects, that means the influence on the sample introduction system on the separation power of the chromatographic system,
plasma solvent load effects, that means the influence on the mobile phase on the stability and ionization power of the inductively coupled plasma.

Plasma solvent load effects limit the free choice of the mobile phase, since now the mobile phase has to be selected both with respect to the separation task but also with respect to the degree of tolerance by the ICP. Tolerance by the ICP can be enhanced by reducing the flow-rate, which can be achieved by reducing the size-factor of the HPLC system from standard to micro-HPLC or even nano-HPLC. Tolerance of the ICP with nano-liter flow rates is so high that nearly any solvent can be introduced with total consumption nebulizers.

On the other hand, the negative influence of dead-volumes and other poor design factors on the chromatographic separation power is the more pronounced the smaller the flow rate of the system is. Therefore, especially careful design considerations are necessary for nano-HPLC coupling while standard system are less critical.

With respect to the type of MS detection system, one has to consider the transient character of the chromatogtaphic signals. Depending on the number of simultaneous channels that have to be monitored (only one in the simple case of a single element speciation), systems that can either simultaneously collect data on different channels or can do fast sequential measurements will have advantages.

Tutorial material related to HPLC

Animation of Dual Head HPLC Pump
Animation of sample loop HPLC injections

HPLC Trouble-Shooting
IonSource.com: Introduction to Capillary Chromatography
IUPAC: Chromatography Nomenclature and Definitions
LC-GC Europe: Glossary of Liquid-Phase Separation Terms
Prof. Yuri Kazakevich, Prof. H. M. McNair, On-line Textbook on High Performance Liquid Chromatography (HPLC)
Upchurch Scientific: HPLC Introduction
Waters: High Performance Liquid Chromatography ( HPLC ) Primer

Reviews of LC-ICP-MS (newest first)

Kevin A. Francesconi, Michael Sperling, Speciation analysis with HPLC-mass spectrometry: time to take stock, Analyst (London), 130/7 (2005) 998-1001.
DOI: 10.1039/b504485p

Maria Montes-Bayón, K. DeNicola, Joseph A. Caruso, Liquid chromatography-inductively coupled plasma mass spectrometry, J. Chromatogr. A, 1000 (2003) 457-476. doi:10.1016/S0021-9673(03)00527-2

Joanna Szpunar, Ryszard Lobinski, Liquid Chromatography with ICP MS Detection, in: Hyphenated Techniques in Speciation Analysis, RSC, Cambridge, 2003, pp. 53-64.

Bernhard Michalke, The coupling of LC to ICP-MS in element speciation - Part II: Recent trends in application, Trends Anal. Chem. (Pers. Ed.), 21/3 (2002) 154-165. doi:10.1016/S0165-9936(02)00303-5

Bernhard Michalke, The coupling of LC to ICP-MS in element speciation: I. General aspects, Trends Anal. Chem. (Pers. Ed.), 21/2 (2002) 142-153. doi:10.1016/S0165-9936(01)00146-7

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

Lothar Rottmann, Klaus G. Heumann, Development of an on-line isotope dilution technique with HPLC/ICP-MS for the accurate determination of elemental species, Fresenius J. Anal. Chem., 350/4-5 (1994) 221-227. doi: 10.1007/BF00322473

Cristina Rivas, Les Ebdon, Steve J. Hill, Effect of different spray chambers on the determination of organotin compounds by high-performance liquid chromatography - inductively coupled plasma mass spectrometry, J. Anal. At. Spectrom., 11/12 (1996) 1147-1150. DOI: 10.1039/JA9961101147

Warren R.L. Cairns, Les Ebdon, Steve J. Hill, A high performance liquid chromatography - inductively coupled plasma-mass spectrometry interface employing desolvation for speciation studies of platinum in chemotherapy drugs, Fresenius J. Anal. Chem., 355/3-4 (1996) 202-208. doi: 10.1007/s0021663550202

Anders Tangen, Roger Trones, Tyge Greibrokk, Walter Lund, Microconcentric Nebulizer for the Coupling Of Micro Liquid Chromatography and Capillary Zone Electrophoresis With Inductively Coupled Plasma Mass Spectrometry, J. Anal. At. Spectrom., 12/6 (1997) 667-670. doi: 10.1039/a607623h

Mary Kate Donais, How to Interface a Liquid Chromatograph to an Inductively Coupled Plasma Mass Spectrometer for Elemental Speciation Studies, Spectroscopy (Eugene, Oreg.), 13/9 (1998) 30-35.

Clayton B'Hymer, Karen L. Sutton, Joseph A. Caruso, Comparison of four nebulizer-spray chamber interfaces for the high-performance liquid chromatographic separation of arsenic compounds using inductively coupled plasma mass spectrometric detection, J. Anal. At. Spectrom., 13/9 (1998) 855-858. doi: 10.1039/a801645c

Erik H. Larsen, Method optimization and quality assurance in speciation analysis using high-performance liquid chromatography with detection by inductively coupled plasma mass spectrometry, Spectrochim. Acta, Part B, 53/2 (1998) 253-265.
doi: 10.1016/S0584-8547(97)00137-7

B. Do, S. Robinet, D. Pradeau, F. Guyon, Application of central composite designs for optimisation of the chromatographic separation of monomethylarsonate and dimethylarsinate and of selenomethionine and selenite by ion-pair chromatography coupled with plasma mass spectrometric detection, Analyst (London), 126/5 (2001) 594. DOI: 10.1039/b008169h

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

Lars Bendahl, Bente Gammelgaard, Sample introduction systems for reversed phase LC-ICP-MS of selenium using large amounts of methanol - Comparison of systems based on membrane desolvation, a spray chamber and direct injection, J. Anal. At. Spectrom., 20/5 (2005) 410-416. DOI: 10.1039/b415717f

Lars Bendahl, Stefan Stürup, Bente Gammelgaard, Steen Honoré Hansen, Ultra-Performance LC-ICP-MS - a fast technique for speciation analysis, J. Anal. At. Spectrom., 20/11 (2005) 1287-1289. DOI: 10.1039/b508653a

Zs. Stefánka, Gunda Koellensperger, Gerhard Stingeder, Stephan Hann, Down-scaling narrowbore LC-ICP-MS to capillary LC-ICP-MS: a comparative study of different introduction systems, J. Anal. At. Spectrom., 21/1 (2006) 86-89. DOI: 10.1039/b511629e

Kirk E. Lokits, Patrick A. Limbach, Joseph A. Caruso, Interfaces for capillary LC with ICPMS detection: A comparison of nebulizers/spray chamber configurations, J. Anal. At. Spectrom., 24/4 (2009) 528-534. DOI: 10.1039/b820121h

Standard operating procedures and methods for LC-ICP-MS

EPA Method 321.8 - Determination of Bromate in Drinking Waters by Ion Chromatography Inductively Coupled Plasma - Mass Spectrometry

Instrument manufacturer's application notes

Agilent Technologies: Handbook of Hyphenated ICP-MS Applications
Agilent Technologies: #5989-7073EN: Determination of Organic and Inorganic Selenium Species Using HPLC-ICP-MS