EVISA Print | Glossary on | Contact EVISA | Sitemap | Home   
 Advanced search
The establishment of EVISA is funded by the EU through the Fifth Framework Programme (G7RT- CT- 2002- 05112).

Supporters of EVISA includes:

An easy way to selectively determine organomercury in seafood


Mercury and its species pose a major risk to all organisms within our biosphere. Environmental behaviour, bioavailability, bioaccumulation and toxicity are species specific, with methylmercury showing higher toxicity than inorganic mercury. The general population is exposed to methylmercury through food consumption, mainly via seafood and rice.  In order to address the human health risk through food consumption, methods for speciation analysis distinguishing between inorganic and organic forms have been accordingly developed since decades. Food samples are extracted usually by the aid of HCL or digested enzymatically under conditions preventing species interconversion. Species specific detection is achieved by chromatographic or non-chromatographic separation methods followed by highly sensitive atomic fluorescence spectrometry (AFS) or inductively coupled plasma mass spectrometry (ICP-MS).  The use of such hyphenated systems is relatively costly, both related to purchase and running costs. In case that only two species have to be differentiated (binary speciation), the high separation power of chromatography may exceed the need, as is the case for inorganic mercury and methylmercury. Methylmercury is the only organic mercury species found in food samples.

The new method:
A team of researchers from Italy have now applied the technique of frontal chromatography for the selective separation of methylmercury from seafood extracts. The method is based on the insertion of a low pressure column packed with a strong anionic exchanger in front of the ICP nebulizer, without the need of any chromatographic pump or injection valve (see figure 1).

Figure 1: FC-ICP-MS instrumental configuration for the determination of methylmercury in extracts of seafood samples

Methylmercury is selectively determined in 100 s by in-line blocking inorganic mercury on the column with a detection limit of 7.8 ng/kg in solution or 1.6 µg/Kg in biological tissue.
Eleven samples representing different trophic positions within the marine food web of the Gulf of Tadjoura were analysed using the proposed method: zooplankton, squid, oil-sardinella and different shark species. 

Methylmercury extraction was performed by a fast procedure using 5 M HCl for 15 min assisted by ultrasound irradiation for sample masses between 50 and 250 mg. The resulting suspension was centrifuged at 4000 rpm for 10 min. and the supernatant was collected and diluted with ultrapure water. Sample solutions were spiked with lutetium solution as internal standard to correct for matrix effects. ICP-MS measurements were performed using a He-collision cell in kinetic energy discrimination (KED) mode. The high capacity of the column for retaining inorganic mercury was regenerated after 100 determinations by passing 2% nitric acid for 30 min. In order to reduce memory effects, thiourea was added online to the eluent from the column. Anyhow, samples containing more than 10 µg/kg MeHg should be diluted for avoiding extensive memory effects.  The whole procedure was validated by using different certified reference materials from the marine food web. All analytical results were within the certified range.

The authors concluded that their method compared favourable with other existing methods when considering its simplicity and the high sample throughput.

The original publication

D. Spanu, L. Butti, G. Boldrocchi, R. Bettinetti, S. Recchia, D. Monticelli, Selective organomercury determination by ICP-MS made easy, Anal. Chim. Acta, 1206 (2022) 339553.  DOI: 10.1016/j.aca.2022.339553.

Instrumentation used:

Related studies

T.-H. Kim, M.-J. Cho, Y. Lee, J.H. Kim, J.-Y. Hwang, H.-E. Lee, S.-H. Kim, J.-D. Choi, G.-J. Kang, Methylmercury Determination in Fish by Direct Mercury Analyzer, J. AOAC Int. 103 (2020) 244–249. DOI: 10.5740/jaoacint.18-0254.

Y. He, M. He, K. Nan, R. Cao, B. Chen, B. Hu, Magnetic solid-phase extraction using sulfur-containing functional magnetic polymer for high-performance liquid chromatography-inductively coupled plasma-mass spectrometric speciation of mercury in environmental samples, J. Chromatogr. A. 1595 (2019) 19–27. DOI: 10.1016/j.chroma.2019.02.050.

A. Thongsaw, R. Sananmuang, Y. Udnan, G.M. Ross, W.C. Chaiyasith, Speciation of mercury in water and freshwater fish samples using two-step hollow fiber liquid phase microextraction with electrothermal atomic absorption spectrometry, Spectrochim. Acta - Part B At. Spectrosc. 152 (2019) 102–108. DOI: 10.1016/j.sab.2018.12.012.
A. Londonio, P.E. Hasuoka, P. Pacheco, R.A. Gil, P. Smichowski, Online solid phase extraction-HPLC ICP-MS system for mercury and methylmercury preconcentration using functionalised carbon nanotubes for their determination in dietary supplements, J. Anal. At. Spectrom. 33 (2018) 1737–1744. DOI: 10.1039/C8JA00188J.

T. Narukawa, T. Iwai, K. Chiba, J. Feldmann, A method for methylmercury and inorganic mercury in biological samples using high performance liquid chromatography- inductively coupled plasma mass spectrometry, Anal. Sci. 34 (2018) 1329–1334. DOI: 10.2116/analsci.18P255.

H. Cheng, W. Zhang, Y. Wang, J. Liu, Graphene oxide as a stationary phase for speciation of inorganic and organic species of mercury, arsenic and selenium using HPLC with ICP-MS detection, Microchim. Acta. 185 (2018) 2–9. DOI: 10.1007/s00604-018-2960-x.

B. Chen, Y. Wu, X. Guo, M. He, B. Hu, Speciation of mercury in various samples from the microecosystem of East Lake by hollow fiber-liquid-liquid-liquid microextraction-HPLC-ICP-MS, J. Anal. At. Spectrom. 30 (2015) 875–881. DOI: 10.1039/c4ja00312h.

D. Deng, S. Zhang, H. Chen, L. Yang, H. Yin, X. Hou, C. Zheng, Online solid sampling platform using multi-wall carbon nanotube assisted matrix solid phase dispersion for mercury speciation in fish by HPLC-ICP-MS, J. Anal. At. Spectrom. 30 (2015) 882–887. DOI: 10.1039/c4ja00436a

I. Sánchez Trujillo, E. Vereda Alonso, J.M. Cano Pavón, A. García de Torres, Use of a new enrichment nanosorbent for speciation of mercury by FI-CV-ICP-MS, J. Anal. At. Spectrom. 30 (2015) 2429–2440. DOI: 10.1039/C5JA00335K.

A. V. Zmozinski, S. Carneado, C. Ibáñez-Palomino, À. Sahuquillo, J.F. López-Sánchez, M.M. da Silva, Method development for the simultaneous determination of methylmercury and inorganic mercury in seafood, Food Control. 46 (2014) 351–359. DOI: 10.1016/j.foodcont.2014.05.054.

X. Chen, C. Han, H. Cheng, Y. Wang, J. Liu, Z. Xu, L. Hu, Rapid speciation analysis of mercury in seawater and marine fish by cation exchange chromatography hyphenated with inductively coupled plasma mass spectrometry, J. Chromatogr. A. 1314 (2013) 86–93. DOI: 10.1016/j.chroma.2013.08.104

J. Masbou, D. Point, J.E. Sonke, Application of a selective extraction method for methylmercury compound specific stable isotope analysis (MeHg-CSIA) in biological materials, J. Anal. At. Spectrom. 28 (2013) 1620. DOI: 10.1039/c3ja50185j.

R. Jagtap, F. Krikowa, W. Maher, S. Foster, M. Ellwood, Measurement of methyl mercury (I) and mercury (II) in fish tissues and sediments by HPLC-ICPMS and HPLC-HGAAS, Talanta. 85 (2011) 49–55. DOI: 10.1016/j.talanta.2011.03.022

M. Popp, S. Hann, G. Koellensperger, Environmental application of elemental speciation analysis based on liquid or gas chromatography hyphenated to inductively coupled plasma mass spectrometry-A review, Anal. Chim. Acta. 668 (2010) 114–129. DOI: 10.1016/j.aca.2010.04.036.

Y.-W. Chen, N. Belzile, High performance liquid chromatography coupled to atomic fluorescence spectrometry for the speciation of the hydride and chemical vapour-forming elements As, Se, Sb and Hg: A critical review, Anal. Chim. Acta. 671 (2010) 9–26. DOI: 10.1016/j.aca.2010.05.011

L.H. Reyes, G.M.M. Rahman, H.M.S. Kingston, Robust microwave-assisted extraction protocol for determination of total mercury and methylmercury in fish tissues, Anal. Chim. Acta. 631 (2009) 121–128. DOI: 10.1016/j.aca.2008.10.044.

E. Vereda Alonso, M.T. Siles Cordero, A. García de Torres, P. Cañada Rudner, J.M. Cano Pavón, Mercury speciation in sea food by flow injection cold vapor atomic absorption spectrometry using selective solid phase extraction, Talanta. 77 (2008) 53–59. DOI: 10.1016/j.talanta.2008.05.053.

L. Perna, A. LaCroix-Fralish, S. Stürup, Determination of inorganic mercury and methylmercury in zooplankton and fish samples by speciated isotopic dilution GC-ICP-MS after alkaline digestion, J. Anal. At. Spectrom. 20 (2005) 236–238. DOI: 10.1039/B410545A.

W.C. Davis, S.S. Vander Pol, M.M. Schantz, S.E. Long, R.D. Day, S.J. Christopher, An accurate and sensitive method for the determination of methylmercury in biological specimens using GC-ICP-MS with solid phase microextraction, J. Anal. At. Spectrom. 19 (2004) 1546. DOI: 10.1039/b412668h.

J. Sanz, J.C. Raposo, J. Larreta, I. Martinez-Arkarazo, A. de Diego, J.M. Madariaga, On-line separation for the speciation of mercury in natural waters by flow injection-cold vapour-atomic absorption spectrometry, J. Sep. Sci. 27 (2004) 1202–1210. DOI: 10.1002/jssc.200301701.

L. Ebdon, M.E. Foulkes, S. Le Roux, R. Muñoz-Olivas, Cold vapour atomic fluorescence spectrometry and gas chromatography-pyrolysis-atomic fluorescence spectrometry for routine determination of total and organometallic mercury in food samples, Analyst. 127 (2002) 1108–1114. DOI: 10.1039/B202927H.

Related EVISA Resources


Imprint     Disclaimer

© 2003 - 2010 by European Virtual Institute for Speciation Analysis ( EVISA )