Identification and quantification of cannabinol as a biomarker for local hemp retting in an ancient sedimentary record by HPTLC-ESI-MS

Cannabis products have been used in various fields of everyday life for many centuries, and applications in folk medicine and textile production have been well-known for many centuries. For traditional textile production, hemp fibers were extracted from the stems by water retting in stagnant or slow-moving waters. During this procedure, parts of the plant material‚ among them phytocannabinoids‚ are released into the water. Cannabinol (CBN) is an important degradation product of the predominant phytocannabinoids found in Cannabis species. Thus, it is an excellent indicator for present as well as ancient hemp water retting. In this study, we developed and validated a simple and fast method for the determination of CBN in sediment samples using high-performance thin-layer chromatography (HPTLC) combined with electrospray ionization mass spectrometry (ESI-MS), thereby testing different extraction and cleanup procedures‚ as well as various sorbents and solvents for planar chromatography. This method shows a satisfactory overall analytical performance with an average recovery rate of 73%. Our protocol enabled qualitative and quantitative analyses of CBN in samples of a bottom sediment core‚ having been obtained from a small lake in Northern India, where intense local retting of hemp was suggested in the past. The analyses showed a maximum CBN content in pollen zone 4 covering a depth range of 262–209 cm, dating from approximately 480 BCE to 1050 CE. These findings correlate with existing records of Cannabis-type pollen. Thus, the method we propose is a helpful tool to track ancient hemp retting activities

Faser- und Farbstoffanalysen an historischen und prähistorischen Textilien

In der vorliegenden Arbeit wurden Textilien aus verschiedenen Epochen und Regionen hinsichtlich der verwendeten Fasermaterialien und ihrer Farbigkeit untersucht. Die Untersuchungen lieferten einerseits Hinweise zu eingesetzten Rohstoffen und Färbetechniken, andererseits können die Materialanalysen bei der Erarbeitung von Konservierungs- bzw. Restaurierungsstrategien helfen. Ein Schwerpunkt war die erstmalige Anwendung von ambienten MS-Techniken wie ASAP-MS oder Flowprobe-ESI-HRMS für Farbstoffanalysen an historischen Textilien. Diese Techniken ermöglichen eine minimal-invasive Farbmittelcharakterisierung direkt von der Faseroberfläche. Somit können Farbstoffe - weitestgehend unabhängig von der Probenbeschaffenheit und vom Fasermaterial - ohne zeitaufwendige Probenvorbereitung innerhalb von wenigen Minuten bzw. Sekunden identifiziert werden. Zudem wurden ortsaufgelöste Farbstoffanalysen an mehrfarbigen, textilen Geweben mit Hilfe der bildgebenden Massenspektrometrie durchgeführt. Der Fokus lag dabei auf der Erfassung von Anthrachinonen und indigoiden Farbstoffen.In this thesis, textiles from various periods and regions have been investigated to determine the kind of fibers and colorants having been used. The results obtained give some clues concerning the used raw materials and dyeing technologies. Furthermore, the results can help to develop strategies for conservation and restoration of such historical objects. A central issue was the first-time application of ambient MS techniques, such as ASAP-MS or flowprobe-ESI-HRMS, for dyestuff analyses on historical textiles. These techniques enable minimally invasive analyses of dyestuffs directly from the surface of fiber samples. The identification of dyestuffs was largely independent of sample properties and fiber material. These methods require no time-consuming sample preparation and experiments were completed within a few minutes or seconds. In addition, spatially resolved dyestuff analyses of multicolored, textile fabrics were performed by mass spectrometry imaging. The investigations focused on the detection of anthraquinones and indigo-type dyes.vorgelegt von Annemarie Elisabeth Kramel