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Multielement speciation analysis


Speciation analysis calls for more complex instrumentation than simple trace element analysis and therefore also for higher costs for analysis. This is further exaggerated by the lower sample throughput in speciation analysis in comparison to trace element analysis. The costs for speciation analysis could be reduced by reducing the analysis time per sample and analysing more than one element per analysis simultaneously. Also the simultaneous speciation of different elements provides more comprehensive information about a definite sample especially on the relationship between different forms of different elements.  

Problems for multielement speciation analysis:
Unfortunately, the requirements for sampling, preserving species, sample pretreatment and separating species are demanding. It is not easy to optimize conditions for multielement speciation in a single run.

HPLC-ICP-MS for multielement speciation analysis:
In general multi-element speciation analysis by LC-ICP-MS is not that straight forward, since separation conditions for more than one group of elemental species are not easy to establish. Even further, sample preparation often requires special attention for different elemental species distribution.  Because of such difficulties LC-ICP-MS multi-element speciation methods most often focus on a limited set of species such as redox couples (As(IIII)As(V), Se(IV)/Se(VI)) and Cr(III)/Cr(VI) in natural water samples for which sample preparation does not require critical extraction.

Apart from such oxidation species some researchers also tried to develop methods for multi-element determination of biomolecules as binding partners of metals in body fluids. Fast protein liquid chromatography was evaluated already in 1999 for such purpose but also size-exclusion chromatography has been used.

GC-ICP-MS for multielement speciation analysis:
While multi-element capabilities are only seldom demanded for LC-ICP-MS, multi-element applications are quite common for GC-ICP-MS. Time-of-flight ICP-MS systems can deliver about 20.000 full range spectra per second. They are ideal instruments for multi-element analysis with GC coupling. The capabilities of GC-ICP-TOFMS were mainly explored in the period 2000-2005. Unfortunately, early commercial instruments could not reach high enough market share. Currently, two manufacturers (GBC and Tofwerk) are still on the market with an ICP-TOFMS instrument. The ICP-TOFMS instrument by Tofwerk was recently introduced.

CE-ICP-MS for multielemental Speciation analysis:
Compared to other chromatographic techniques, CE provides relatively gentle separation conditions and can therefore preserve the integrity of complex molecules. CE also has the advantage of high separation efficiency, making it more suitable to find compromise conditions for multielement speciation analysis.

Related studies

  M. Marcinkowska, W. Lorenc, D. Baralkiewicz, Study of the impact of bottles material and color on the presence of AsIII, AsV, SbIII, SbV and CrVI in matrix-rich mineral water - Multielemental speciation analysis by HPLC/ICP-DRC-MS, Microchem. J., 132  (2017) 1-7. doi: 10.1016/j.microc.2016.11.022

Yong Fang, Yushi Pan, Peng Li, Mei Xue, Fei Pei, Wenjian Yang, Ning Ma, Qiuhui Hu, Simultaneous determination of arsenic and mercury species in rice by ion-pairing reversed phase chromatography with inductively coupled plasma mass spectrometry, Food Chem., 213 (2016) 609–615. doi: 10.1016/j.foodchem.2016.07.003

M. Marcinkowska, D. Baralkiewicz, Multielemental speciation analysis by advanced hyphenated technique - HPLC/ICP-MS: A review, Talanta, 161 (2016) 177-204. doi: 10.1016/j.talanta.2016.08.034

B. Klencsar, E. Bolea-Fernandez, M.R. Florez, L. Balcaen, F. Cuyckens, F. Lynen, F. Vanhaecke, Determination of the total drug-related chlorine and bromine contents in human blood plasma using high performance liquidchromatography.tandem ICP-mass spectrometry (HPLC.ICP-MS/MS), J. Pharm. Biomed. Anal. 124 (2016) 112-119. doi: 10.1016/j.jpba.2016.02.019

Monika Marcinkowska, Izabela Komorowicz, Danuta Baralkiewicz, New procedure for multielemental speciation analysis of five toxic species: As(III), As(V), Cr(VI), Sb(III) and Sb(V) in drinking water samples by advanced hyphenated technique HPLC/ICP-DRC-MS, Anal. Chim. Acta, 920 (2016) 102-111. doi: 10.1016/j.aca.2016.03.039

  Lihong Liu, Zhaojun Yun, Bin He, and Guibin Jiang, Simultaneous Speciation of Arsenic and Selenium using CE-ICP-MS, Agilent ICP-MS J., 65 (2016) 4-5.

Monika Marcinkowska, Izabela Komorowicz, Danuta Baralkiewicz, Study on multielemental speciation analysis of Cr(VI), As(III) and As(V) in water by advanced hyphenated technique HPLC/ICP-DRC-MS. Fast and reliable procedures, Talanta 144 (2015) 233–240. doi: 10.1016/j.talanta.2015.04.087

C. Wei, Z. Ge, W. Chu, R. Feng, Speciation of antimony and arsenic in the soils and plants in an old antimony mine, Environ. Exp. Bot. 109 (2015) 31-39. doi: 10.1016/j.envexpbot.2014.08.002

R.E. Wolf, S.A. Morman, P.L. Hageman, T.M. Hoefen, G.S. Plumlee, Simultaneus speciation of arsenic, selenium and chromium: species stability, sample preserwation, and analysis of ash and soil leachates, Anal. Bioanal. Chem. 401 (2011) 2733-2745. doi: 10.1007/s00216-011-5275-x

M. Mulugeta, G. Wibetoe, C.J. Engelsen, W. Lund, Optimization of an anion-exchange high-performance liquid chromatography-inductively coupled plasma mass spectrometric method for the speciation analysis of oxyanion-forming metals and metalloids in leachates from cement-based materials, J. Chromatogr. A 1217 (2010) 6186-6194. doi: 10.1016/j.chroma.2010.07.082

M. Mulugeta, G. Wibetoe, C.J. Engelson, W. Lund, Speciation analysis of As, Sb and Se in leachates of cementitious construction materials using selective solid phase extraction and ICP-MS, J. Anal. At. Spectrom. 25 (2010) 169-177. doi: 10.1039/b919994m

Y.-K. Tsoi, K.S.-Y. Leung, Simultaneous determination of seven elemental species in estuarine waters by LC-ICP-DRC-MS, J. Anal. At. Spectrom. 25 (2010) 880-885. doi: 10.1039/B923343A

A.J. Bednar, R.A. Kirgan, W.T. Jones, Comparison of standard and reaction cell inductively coupled plasma mass spectrometry in the determination of chromium and selenium species by HPLC-ICP-MS, Anal. Chim. Acta, 632 (2009) 27-34. doi: 10.1016/j.aca.2008.10.050

A. Castillo, A.F. Roig-Navarro, O.J. Pozo, Capabilities of microbore columns coupled to inductively coupled plasma mass spectrometry in speciation of arsenic and selenium, J. Chromatogr. A, 22 (2008) 132-137. doi: 10.1016/j-chroma.2008.06.031

Y. Morita, T. Kobayashi, T. Kuroiwa, T. Narukawa, Study on simultaneous speciation of arsenic and antimony by HPLC-ICP-MS, Talanta 73 (2007) 81-86. doi: 10.1016/j.talanta.2007.03.005

T. Narukawa, A. Takatsu, K. Chiba, K.W. Riley, D.H. French, Investigation on chemical species of arsenic, selenium and antimony in fly ash from coal fuel thermal powerstations, J. Environ. Monit. 7 (2005) 1342-1348. doi: 10.1039/b509817c

K.R. Neubauer, W.M. Reuter, P.A. Perrone, Z.A. Grosser, Simultaneous Arsenic and Chromium Speciation by HPLC/ICP-MS in Environmental Waters, PerkinElmer application note,USA,2004. Availableat: .www.perkinelemr.com.,

H. Goenaga Infante, K. Van Campenhout, D. Schaumlöffel, R. Blust, F.C. Adams, Multi-element speciation of metalloproteins in fish tissue using size-exclusion chromatography coupled "on-line" with ICP-isotope dilution-time-of-flight-mass spectrometry, Analyst 128, 651-657 (2003).  doi: 10.1039/b212889f

C.N. Ferrarello, M.R. Fernández de la Campa, A. Sanz-Medel, Multielement trace-element speciation in metal-biomolecules by chromatography coupled with ICP-MS, Anal. Bioanal. Chem.  373, 412-421 (2002). doi: 10.1007/s00216-002-1278-y

Imran Ali, Hassan Y. Aboul-Enein, Speciation of arsenic and chromium metalions by reversed phase high performance liquid chromatography, Chemosphere, 48 (2002) 275-278. doi: 10.1016/S0045-6535(02)00085-1

Andreas Prange, Dirk Schaumlöffel, Peter Brätter, Andrea-Nicole Richarz, Christian Wolf, Species analysis of metallothionein isoforms in human brain cytosols by use of capillary electrophoresis hyphenated to inductively coupled plasma–sector field mass spectrometry, Fresenius J. Anal. Chem., 371 (2001) 764–774. doi: 10.1007/s002160101019

A.F. Roig-Navarro, Y. Martinez-Bravo, F.J. Lopez ,F. Hermandez, Simultaneus determination of arsenic species and chromium(VI) by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry, J. Chromatogr. A912 (2001) 319-327. doi: 10.1016/S0021-9673(01)00572-6

Y. Martinez-Bravo, A.F. Roig-Navarro, F.J. Lopez, F. Hernandez, Multielemental determination of arsenic, selenium and chromium(VI) species in water by high-performance liquid chromatography-inductively coupled plasma mass spectrometry, J. Chromatogr. A 926 (2001)265-274. doi: 10.1016/j.aca.2008.10.050

U.M. Grüter, J. Kresimon, A.V. Hirner, A new HG/LT-GC/ICP-MS multi-element speciation technique for real samples in different matrices, Fresenius J. Anal. Chem., 368 (2000) 67–72. doi: 10.1007/s002160000443

T. Lindemann, A. Prange, W. Dannecker, B. Neidhart, Simultaneus determination of arsenic, selenium and antimony species using HPLC/ICP-MS, Fresenius J. Anal. Chem. 364 (1999) 462-466. doi: 10.1007/s002160051368

B.P. Jackson, W.P. Miller, Arsenic and selenium speciation in coal fly ash extracts by ion chromatography-inductively coupled plasma mass spectrometry, J. Anal. At. Spectrom., 13 (1998) 1107-1112. doi:  10.1039/A806159I

T. Guerin, M. Astruc, A. Batel, M. Borsier, Multielemental speciation of As, Se, Sb and Te by HPLC-ICP-MS, Talanta, 44 (1997) 2201-2208. doi: 10.1016/S0039-9140(97)00036-2

M. Pantsar-Kallio, P.K.G. Manninen, Simultaneus determination of toxic arsenic and chromium species in water samples by ion chromarography-inductively coupled plasma mass spectrometry, J. Chromatogr. A, 779 (1997) 139-146. doi: 10.1016/S0021-9673(97)00402-0

Canny Haraldsson, Benny Lyven, Marianne Pollak and Annelie Skoog, Multi-element speciation of trace metals in fresh water adapted to plasma source mass spectrometry, Anal. Chim. Acta, 284 (1993) 327-335. doi: 10.1016/0003-2670(93)85317-D

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
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
Chapter 15: Mercury 'speciation analysis' by using thermal desorption analysis
Chapter 16: Multielement speciation analysis

last time modified: May 14, 2017


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