Identification of anthraquinone dye colourants in red fibres from an Ohio Hopewell mound site by direct analysis in real time mass spectrometry

Abstract

Among prehistoric native groups of North America, the Ohio Hopewell was a particularly notable cultural manifestation that prevailed during the Middle Woodland Period (ca. 2100 -1500 BP). The group is defined by the construction of elaborate burial mounds, evidence of ritual burning and cremation ceremonies, The presence of anthraquinones in these Ohio Hopewell textiles, and the absence of the bloodroot alkaloids, supports previous studies suggesting the prehistoric use of Galium species as dye plants in Eastern North America.Statement of significance Among the prehistoric native groups of North America, the Hopewell cultural manifestation are particularly notable for their elaborate ceremonial mounds, and the intricately decorated objects they made. While few textiles have survived, those fragments which remain provide important evidence for the technological knowledge and craftsmanship of the people of the past. A rapid method that requires a very small sample yields information about the red dye colorants employed in this fabrics. Direct analysis in real time-time-of-flight mass spectrometry (DART-MS) was used to examine fibers from red-and yellow-coloured textiles from the Seip Mound Group in Ohio, USA. The analysis showed that compounds characteristic of bedstraw plants of the Galium genus, rather than those from bloodroot, provide the red colour.This supports previous work suggesting the use of bedstraw for dyeing in prehistoric Eastern North America.

The analysis of the Saltzman Collection of Peruvian dyes by high performance liquid chromatography and ambient ionisation mass spectrometry

“…A form of electrospray ionization, paper spray makes molecules that are not readily ionized with DART accessible in a low-volume format. The Armitage group has pioneered the use of DART-MS for analysis of natural dyes for applications to ancient textiles [9,[19][20][21][22] and other cultural heritage materials [23][24][25]. While paper spray has been used by others for characterizing both natural and artificial colorants in food and beverage [26,27], this is the first instance of which we are aware for its use in heritage science applications.…”

Direct analysis in real time-mass spectroscopy for identification of red dye colourants in Paracas Necropolis Textiles

“…Direct analysis in real time (DART) ionisation coupled to time-of-flight mass spectrometry has been demonstrated as a rapid, simple method for the identification of dye colourants on cotton (Selvius DeRoo and Armitage 2011; Geiger, Armitage and Selvius DeRoo 2012) as well as on wool and silk fibres (Day, Selvius DeRoo and Armitage 2013). Most recently, DART-MS has shown that textile fibres from the Seip Mound group in Ohio were consistent with the use of anthraquinone dyes obtained from Galium species but did not show any evidence of benzoisoquinoline alkaloids from bloodroot (Sanguinaria canadensis) (Armitage, Day and Jakes 2015).…”

Chemical characterization and radiocarbon dating of the rock art of Las Charcas caves, Cuba

“…2013; DeRoo and Armitage 2014; Armitage et al . 2015a, 2015b, 2019; Armitage and Jakes 2015), residues (Hopkins and Armitage 2012; Fraser et al . 2013; Kaktins et al .…”