Chemical identification of spices from the Gribshunden shipwreck

Abstract

The main purpose of this study was to identify an unknown spice collected from an old shipwreck (Gribshunden). This study was demanding as we were dealing with an aged sample being under water for around 500 years. It is quite probable that many components in our sample have undergone changes or washed away by water, and as a consequence decreased in concentration. However, the strongest guess, judging by its shape and orangish color in the water, is that it is saffron. The main research question was if the suggested spice is saffron. The follow-up question is where its geographical origin is.
Crocin-1 and crocetin which are 2 main components in saffron were identified by two methods, using Supercritical Fluid Chromatography-Diode Array Detection connected to Quadrupole Time of Flight Mass Spectrometry (SFC-DAD/QTOF-MS) and Ultra-High Performance Liquid Chromatography-Diode Array Detection coupled with QTOF-MS. The separation by SFC achieved by gradient elution using a 2-picolylamine (2-pic) column and methanol as a co-solvent. UHPLC analysis was performed using a charged surface hybrid (CSH) column and mobile phases based on water containing 0.1% formic acid (solvent A) and acetonitrile containing 0.1% formic acid (solvent B) following an elution gradient from 5 to 95%.
It was determined that these two substances were discovered in both Gribshunden samples and commercial saffron. Chromatograms and mass spectra were similar in all samples. So, it could be concluded that the spice is saffron.

Popular Abstract

Identification of saffron from Gribshunden shipwreck sample
The Gribshunden ship (a Danish ship) sank around 500 years ago in the Baltic Sea. Currently, an archeological research group is working on many aspects of this ship like its wooden hull, gun powder, some unknown resins, and plant residues that could be spices of different types. In this project, spices have been under study, specifically one that is suggested to be saffron. The primary aim was to use chemical analysis methods to support or reject the hypothesis that the samples are saffron. This has been done by investigating Gribshunden samples, commercial saffron and chemical standards. The second question was if it is possible to discover in which country that spice was produced. The strategy was to compare the Gribshunden sample with commercial saffron from several different regions.
Crocin-1 and crocetin belong to carotenoids, and they are considered unique compounds in saffron. Our results show that crocin-1 and crocetin are found in both the Gribshunden sample and in commercial saffron, hence, it is likely that the Gribshunden sample is saffron. The second question is more challenging to answer, as most of the compounds have been either dissolved and by the surrounding water or have been chemically degraded upon exposure to the surrounding water for five centuries. Therefore, lipids (which are not as much as carotenoids water soluble) were analyzed as well as carotenoids (crocin-1 and crocetin). In order to investigate the origin of the Gribshunden saffron by using commercial saffron samples from different countries were explored.

• author: Norouzi, Mahsa
• supervisor: Charlotta Turner; Sofia Essén
• organization: Department of Chemistry
• course: KEMP30 20221
• year: 2022
• type: L3 - Miscellaneous, Projetcs etc.
• subject: Chemistry
• keywords: Crocin-1, crocetin, mass spectrometry, MS, saffron, supercritical fluid chromatography, SFC, Ultra-High Performance Liquid Chromatography, UHPLC, analytical chemistry
• language: English
• id: 9097822
• date added to LUP: 2022-08-23 08:47:47
• date last changed: 2022-08-23 08:47:47