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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



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