Simultaneous iron, zinc, sulfur and phosphorus speciation analysis of barley grain tissues using SEC-ICP-MS and IP-ICP-MS (original) (raw)

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Plant and Soil Science Laboratory, Department of Agriculture and Ecology, Faculty of Life Sciences, University of Copenhagen

, Thorvaldsensvej 40, DK-1871 Frederiksberg C,

Denmark

. Fax: +45 35283460; Tel: +45 35283498

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Plant and Soil Science Laboratory, Department of Agriculture and Ecology, Faculty of Life Sciences, University of Copenhagen

, Thorvaldsensvej 40, DK-1871 Frederiksberg C,

Denmark

. Fax: +45 35283460; Tel: +45 35283498

Search for other works by this author on:

,

Plant and Soil Science Laboratory, Department of Agriculture and Ecology, Faculty of Life Sciences, University of Copenhagen

, Thorvaldsensvej 40, DK-1871 Frederiksberg C,

Denmark

. Fax: +45 35283460; Tel: +45 35283498

Search for other works by this author on:

,

Plant and Soil Science Laboratory, Department of Agriculture and Ecology, Faculty of Life Sciences, University of Copenhagen

, Thorvaldsensvej 40, DK-1871 Frederiksberg C,

Denmark

. Fax: +45 35283460; Tel: +45 35283498

Search for other works by this author on:

Plant and Soil Science Laboratory, Department of Agriculture and Ecology, Faculty of Life Sciences, University of Copenhagen

, Thorvaldsensvej 40, DK-1871 Frederiksberg C,

Denmark

. Fax: +45 35283460; Tel: +45 35283498

Search for other works by this author on:

Published:

05 August 2009

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Daniel P Persson, Thomas H Hansen, Kristian H Laursen, Jan K Schjoerring, Søren Husted, Simultaneous iron, zinc, sulfur and phosphorus speciation analysis of barley grain tissues using SEC-ICP-MS and IP-ICP-MS, Metallomics, Volume 1, Issue 5, September 2009, Pages 418–426, https://doi.org/10.1039/b905688b
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Abstract

The increasing prevalence of iron (Fe) and zinc (Zn) deficiencies in human populations worldwide has stressed the need for more information about the distribution and chemical speciation of these elements in cereal products. In order to investigate these aspects, barley grains were fractionated into awns, embryo, bran and endosperm and analysed for Fe and Zn. Simultaneously, phosphorus (P) and sulfur (S) were determined since these elements are major constituents of phytic acid and proteins, respectively, compounds which are potentially involved in Fe and Zn binding. A novel analytical method was developed in which oxygen was added to the octopole reaction cell of the ICP-MS. This approach greatly improved the sensitivity of sulfur, measured as 48SO+. Simultaneously, Fe was measured as 72FeO+, P as 47PO+, and Zn as 66Zn+, enabling sensitive and simultaneous analysis of these four elements. The highest concentrations of Zn, Fe, S and P were found in the bran and embryo fractions. Further analysis of the embryo using SEC-ICP-MS revealed that the speciation of Fe and Zn differed. The majority of Fe co-eluted with P as a species with the apparent mass of 12.3 kDa, whereas the majority of Zn co-eluted with S as a 3 kDa species, devoid of any co-eluting P. Subsequent ion pairing chromatography of the Fe/P peak showed that phytic acid (_myo_-inositol-1,2,3,4,5,6-hexa_kis_phosphate: IP6) was the main Fe binding ligand, with the stoichiometry Fe4(IP6)18. When incubating the embryo tissue with phytase, the enzyme responsible for degradation of phytic acid, the extraction efficiency of both Fe and P was doubled, whereas that of Zn and S was unaffected. Protein degradation on the other hand, using protease XIV, boosted the extraction of Zn and S, but not that of Fe and P. It is concluded that Fe and Zn have a different speciation in cereal grain tissues; Zn appears to be mainly bound to peptides, while Fe is mainly associated with phytic acid.

Graphical Abstract

A novel SEC-ICP-MS based methodology was developed, which allows sensitive and simultaneous analysis of Fe, Zn, P and S in cereal grains. It was shown that Fe and Zn have different speciation, thus challenging the classical scientific dogma on metal binding in cereals.

© The Royal Society of Chemistry 2009

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