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:

HPLC-ICPMS/MS as a versatile tool for the speciation of non-metals: Sulfur species in wine

(14.11.2019)


Background:
While ICP-MS is capable of detecting nearly all elements of the whole periodic system, non-metals do not belong to those that can be determined easily with adequate detection power. When it comes to sulfur determination, ICP-MS detection power for m/z 32 is greatly reduced by polyatomic interferences resulting from 16O16O+. The most often applied approaches to overcome these interferences are the detection of sulfur with high resolution sector field mass spectrometry or detection in the form of its oxide at m/z 48. Unfortunately, this approach lacks selectivity, since other species with the same m/z might be present, such as 31P16O1H+, 48Ca+, and 36Ar12C+. These species can arise in biological materials due to their high content of phosphorus, calcium and carbon. These problems can be overcome by the use of the triple quadrupole technology, enhancing the selectivity significantly, thereby reducing the background signal leading to greatly improved detection power.

The new study
:
Researchers from the University of Graz have now used this detection technique in combination with HPLC separation to explore the sulfur speciation in wine.


Figure: S detection as SO+ by ICP-MS/MS


Chromatographic separation was performed by using an anion-exchange column with different mobile phases depending on the target species. Different white and red wines were directly injected without sample pretreatment except for simple filtration. In addition to the analysis of native wine, the researchers also performed several chemical treatments including oxidation with hydrogen peroxide, base hydrolysis using sodium hydroxide and enzymatic digestion with proteinase K. For mass balancing, total sulfur was determined after microwave assisted acid digestion.

The major sulfur species in regular red and white wines were found to be sulfite and sulfate, while in "sulfite-free" wines the major species was sulfate. Chromatographic behavior of sulfite was very critically dependent on pH, calling for pH 12. As minor species, methionine could be identified, while several other minor species could not be identified. Overall, the sum of detected species accounted only for 65-77 % of the total sulfur. The amount of unaccounted sulfur was lower in sulfite-free wines. The authors speculated, that the lost sulfur compounds probably show strong retention on the polymer-based stationary phase.       

The detection power of the used triple-quadrupole approach was found to be 0.1 pmol of injected sulfur, which is about 100-fold better than detection with the dynamic reaction cell, which already achieved a 10 to 20-fold improvement against simple quadrupole detection.

The authors conclude that future work may involve closer exploration of the sulfur compounds lost by the anion-exchange chromatographic separation.




The original study:

B. Lajin, W. Goessler, Exploring the sulfur species in wine by HPLC-ICPMS/MS, Analytica Chimica Acta, DOI: 10.1016/j.aca.2019.09.074.



Used techniques and instrumentation:

Agilent Technologies Inc. - 8800 - Triple Quad ICP-MS



Related studies

I. Milovanovic, B. Lajin, S. Braeuer, O. Steiner, F. Lisa, W. Goessler, Simultaneous selenium and sulfur speciation analysis in cultivated Pleurotus pulmonarius mushroom, Food Chem., 279 (2019) 231-236. DOI: 10.1016/j.foodchem.2018.12.009

N. Kroepfl, K.A. Francesconi, T. Schwerdtle, D. Kuehnelt, Selenoneine and ergothioneine in human blood cells determined simultaneously by HPLC/ICP-QQQ-MS, J. Anal. At. Spectrom., 34 (2019) 127-134. DOI: 10.1039/c8ja00276b

B. Lajin, W. Goessler, Sulfur speciation by HPLC-ICPQQQMS in complex human biological samples: taurine and sulfate in human serum and urine, Anal. Bioanal. Chem., 410 (2018) 6787-6793. DOI: 10.1007/s00216-018-1251-z

Andrea Raab, Marilena Ronzan and Joerg Feldmann, Sulphur fertilization influences the sulphur species composition in Allium sativum: sulphomics usingHPLC-ICPMS/MS-ESI-MS/MS, Metallomics, 9/10 (2017) 1429-1438.  DOI: 10.1039/c7mt00098g

Nina Kroepfl, Talke A. Marschall, Kevin A. Francesconi, Tanja Schwerdtle, Doris Kuehnelt, Quantitative determination of the sulfur containing antioxidant ergothioneine by HPLC/ICP-QQQ-MS, J. Anal. At. Spectrom., 32 (2017) 1571-1581. DOI: 10.1039/c7ja00030h

E. Bolea-Fernandez, L. Balcaen, M. Resano, F. Vanhaecke, Overcoming spectral overlap via inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS). A tutorial review, Anal. Chim. Acta, 32 (2017) 1660-1679. DOI: 10.1039/c7ja00010c

Francisco Calderón-Celis, Silvia Diez-Fernández, José Manuel Costa-Fernández, Jorge Ruiz Encinar, Juan J. Calvete, Alfredo Sanz-Medel, Elemental Mass Spectrometry for Absolute Intact Protein Quantification without Protein-Specific Standards: Application to Snake Venomics, Anal. Chem., 88 (2016) 9699−9706.  DOI: 10.1021/acs.analchem.6b02585

Laura Hyrup Moller, André Macherius, Thomas Hasselhoj Hansen, Hanne Mřrck Nielsen, Claus Cornett, Jesper Řstergaard, Stefan Stürup, Bente Gammelgaard, Quantification of pharmaceutical peptides in human plasma by LC-ICP-MS sulfur detection, J. Anal. At. Spectrom., 31/9 (2016) 1877-1884. DOI: 10.1039/c6ja00132g

Zhanglin Ni, Fubin Tang, Yihua Liu, Danyu Shen, Runhong Mo, Rapid Determination of Low-level Sulfite in Dry Vegetables and Fruits by LCICP-MS, Food Sci. Technol. Res., 21/1 (2015) 1-6. DOI: 10.3136/fstr.21.1

L. Balcaen, E. Bolea-Fernandez, M. Resano, F. Vanhaecke, Inductively coupled plasma–Tandem mass spectrometry (ICP-MS/MS): A powerful and universal tool for the interference-free determination of (ultra) trace elements–A tutorial review, Anal. Chim. Acta, 894 (2015) 7-19. DOI: 10.1016/j.aca.2015.08.053

J.G. Martínez-Sierra, O.G. San Blas, J.M. Gayón, J.G. Alonso, Sulfur analysis by inductively coupled plasma-mass spectrometry: a review, Spectrochim. Acta B: At. Spectrosc., 108 (2015) 35-52. DOI: 10.1016/j.sab.2015.03.016

Yoshinari Suzuki, Ayumi Nobusawa, Naoki Furuta, Quantification of Protreins by Measuring the Sulfur Content of their Constituent Peptides by Means of nano HPLC-ICPMS, Anal. Sci., 30/5 (2014) 551-559. DOI: 10.2116/analsci.30.551

J. Giner Martínez-Sierra, F. Moreno Sanz, P. Herrero Espílez, J.M. Marchante Gayón, J. Rodríguez Fernández, J.I. García Alonso, Sulphur tracer experiments in laboratory animals using 34S-labelled yeast, Anal. Bioanal. Chem., 405 (2013) 2889-2899. DOI: 10.1007/s00216-012-6420-x

S.D. Fernández, N. Sugishama, J.R. Encinar, A. Sanz-Medel, Triple quad ICPMS (ICPQQQ) as a new tool for absolute quantitative proteomics and phosphoproteomics, Anal. Chem., 84 (2012) 5851-5857. DOI: 10.1021/ac3009516

C. Losada, J.J. Alberti, J. Saurina, S. Sentellas, Determining of S-containing drug metabolitwes from in vitro and in vivo metabolism studies using LC-ICP/MS, Anal. Bioanal. Chem., 404/2 (2012) 539-551. DOI: 10.1007/s00216-012-6145-x

Evelyn Rampler, Thomas Dalik, Gerhard Stingeder, Stephan Hann, Gunda Koellensperger, Sulfur containing amino acids - challenge of accurate quantification, J. Anal. At. Spectrom., 27/6 (2012) 1018-1023. DOI: 10.1039/c2ja10377j

Cathy MacDonald, Christopher Smith, Filippos Michopoulos, Richard Weaver, Ian D. Wilson, Identification and quantification of gluthathione adducts of clozapine using ultra-high-performance liquid chromatogtraphy with orthogonal acceleration time-of-flight mass spectrometry and inductively coupled plasma mass spectrometry, Rapid Commun. Mass Spectrom., 25/13 (2011) 1787-1793. DOI: 10.1002/rcm.5043

T. Konz, M. Montes-Bayón, J. Bettmer, A. Sanz-Medel, Analysis of hepcidin, a key peptide for Fe homeostasis, via sulfur detection by capiollary liquid chromatography-inductively coupled plasma mass spectrometry, J. Anal. At. Spectrom., 26/2 (2011) 334-340. DOI: 10.1039/c0ja00053a

J. Giner Martínez-Sierra, F. Moreno Sanz, P. Herrero Espílez, R. Santamaria-Fernandez, J.M. Marchante Gayón, J.I. García Alonso, Evaluation of different analytical strategies for the quantification of sulfur-containing biomolecules by HPLC-ICP-MS: Application to the characterisation  of 34S-labelled yeast, J. Anal. At. Spectrom., 25/7 (2010) 989-997. DOI: 10.1039/B925366A

Karolin Kroening, Douglas Richardson, Scott Afton, Joseph Caruso, Screening hydrolysis products of sulfur mustard agents by high-performance liquid chromatography with inductively coupled plasma mass spectrometry detection, Anal. Bioanal. Chem., 393/8 (2009) 1949-1956. DOI: 10.1007/s00216-009-2642-y

Helen G. Gika, A. Theodoridou, F. Michopoulos, G. Theodoridis, E. Diza, L. Settas, P. Nikolaidis, C. Smith, I.D. Wilson, Determination of two COX-2 inhibitors in serum and synovial fluid of patients with infalammatory arthritis by ultra performance liquid chromatography-ICP-MS and quadrupole time-of-flight mass spectrometry, J. Pharm. Biomed. Anal., 49/3 (2009) 579-586. DOI: 10.1016/j.jpba.2008.12.006

Nico Zinn, Ralf Krüger, Peter Leonhard, Jörg Bettmer, µLC coupled to ICP-SFMS with post-column isotopüe dilution analysis of sulfur for absolute protein quantification, Anal. Bioanal. Chem., 391/2 (2008) 537-543. DOI: 10.1007/s00216-008-2025-9

Meng Wang, Weiyue Feng, Wenwei Lu, Bai Li, Bing Wang, Motao Zhu, Yun Wang, Hui Yuan, Yuliang Zhao, Zhifang Cai, Quantitative Analysis of Proteins via Sulfur Determination by HPLC Coupled to Isotope Dilution ICPMS with a Hexapole Collision Cell, Anal. Chem., 79/23 (2007) 9128-9134. DOI: 10.1021/ac071483t

Dirk Schaumlöffel, Pierre Giusti, Hugues Preud'Homme, Joanna Szpunar, Ryszard Lobinski, Precolumn Isotope Dilution Analysis in nanoHPLC-ICPMS for Absolute Quantification of Sulfur-containing Peptides, Anal. Chem., 79/7 (2007) 2859-2868. DOI: 10.1021/ac061864r

Berit Packert Jensen, Christopher Smith, Ian D. Wilson, Lars Weidolf, Sensitive sulphur-specific detection of omeprazole metabolites in rat urine by high-performance liquid chromatography/innductively coupled plasma mass spectrometry, Rapid. Commun. Mass Spectrom., 18/2 (2004) 181-183. DOI: 10.1002/rcm.1312

Stephan Hann, Gunda Koellensperger, Christian Obinger, Paul Georg Furtmüller, Gerhard Stingeder, SEC-ICP-DRCMS and SEC-ICP-SFMS for determination of metal-sulfur ratios in metalloproteins, J. Anal. At. Spectrom., 19/1 (2004) 74-79. DOI: 10.1039/b310650k

M. Wind, A. Wegener, A. Eisenmenger, R. Kellner, W.D. Lehmann, Sulfur as the key element for quantitative protein analysis by capillary liquid chromatography coupled to element mass spectrometry, Angew. Chem., Int. Ed., 42 (2003) 3425-3427. DOI: 10.1002/anie.200250547

D.R. Bandura, V.I. Baranov, S.D. Tanner, Detection of ultratrace phosphorus and sulfur by quadrupole ICPMS with dynamic reaction cell, Anal. Chem., 74 (2002) 1497-1502. DOI: 10.1021/ac011031v

E. Hywel Evans, Jean-Claude Wolff, Christine Eckers, Sulfur-Specific detection of Impuritiesd in Cimetidine Drug Substance Using Liquid Chromatzography Coupled to High Resolution Inductively Coupled Plasma Mass Spectrometry and Electrospray Mass Spectrometry, Anal. Chem. 73/19 (2001) 4722-4728. DOI: 10.1021/ac0103017

B. Divjak, W. Goessler, Ion chromatographic separation of sulfur-containing inorganic anions with an ICP–MS as element-specific detector, J. Chromatogr. A, 844 (1999) 161-169. DOI: 10.1016/S0021-9673(99)00409-4

Kikuo Takatera, Tadashi Watanabe, Determination of Sulfhydryl Groups in Ovalbumin by High-Performance Liquid Chromatography with Inductively Coupled Plasma Mass Spectrometric Detection, Anal. Chem., 65/24 (1993) 3644-3648. DOI: 10.1021/ac00072a018


 Related EVISA Resources






Comments






Imprint     Disclaimer

© 2003 - 2024 by European Virtual Institute for Speciation Analysis ( EVISA )