Saturday, 21 January 2023

INDIGO: NATURAL DYES

Natural dyes are dyes or colourants derived from plants, invertebrates, or minerals. The majority of natural dyes are vegetable dyes from plant sources — roots, berries, bark, leaves, and wood — and other biological sources such as fungi and lichens.

Archaeologists have found evidence of textile dyeing dating back to the Neolithic period. In China, dyeing with plants, barks and insects has been traced back more than 5,000 years and looks to be our first attempt at the practice of chemistry.

The essential process of dyeing changed little over time. Typically, the dye material is put in a pot of water and then the textiles to be dyed are added to the pot, which is heated and stirred until the colour is transferred. Sometimes, we use workers with stout marching legs to mix this up.

Traditional dye works still operate in many parts of the world. There is a revival of using natural indigo in modern Egypt — although their indigo dye is mostly imported. The same is true further south in Sudan. They've been importing cloth from Upper Egypt as far back as we have written records and continue the practice of the cloth and dye imports today. Clean white cotton is more the style of western Sudan and Chad, but they still like to throw in a bit of colour.

Traditional Dye Vats
So do the folk living in North Africa. Years ago, I was travelling in Marrakesh and saw many men with noticeably orange, blueish or purplish legs. It wasn't one or two but dozens of men and I'd wondered why this was.

My guide took me to the top of a building so I could look down on rows and rows of coloured vats. In every other one was a man marching in place to work the dye into the wool. Their legs took on the colour from their daily march in place in huge tubs of liquid dye and sheared wool. 

This wool would be considered textile fibre dyed before spinning — dyed in the wool — but most textiles are yarn-dyed or piece-dyed after weaving. In either case, the finished product is quite fetching even if the dyer's legs are less so. 

Many natural dyes require the use of chemicals called mordants to bind the dye to the textile fibres; tannin from oak galls, salt, natural alum, vinegar, and ammonia from stale urine were staples of the early dyers.

Many mordants and some dyes themselves produce strong odours. Urine is a bit stinky. Not surprisingly, large-scale dyeworks were often isolated in their own districts.

Woad, Isatis tinctoria
Plant-based dyes such as Woad, Isatis tinctoria, indigo, saffron, and madder were raised commercially and were important trade goods in the economies of Asia and Europe. 

Across Asia and Africa, patterned fabrics were produced using resist dyeing techniques to control the absorption of colour in piece-dyed cloth.

Dyes such as cochineal and logwood, Haematoxylum campechianum, were brought to Europe by the Spanish treasure fleets, and the dyestuffs of Europe were carried by colonists to America.

Throughout history, people have dyed their textiles using common, locally available materials, but scarce dyestuffs that produced brilliant and permanent colours such as the natural invertebrate dyes. Crimson kermes became highly prized luxury items in the ancient and medieval world. Red, yellow and orange shades were fairly easy to procure as they exist as common colourants of plants. It was blue that people sought most of all and purple even more so.

Indigofera tinctoria, a member of the legume or bean family proved just the trick. This lovely plant —  named by the famous Swedish botanist Carl Linneaus, the father of formalized binomial nomenclature — grows in tropical to temperate Asia and subtropical regions, including parts of Africa.

The plants contain the glycoside indican, a molecule that contains a nitrogenous indoxyl molecule with some glucose playing piggyback. 

Indigo dye is a product of the reaction of indoxyl by a mild oxidizing agent, usually just good old oxygen.

To make the lovely blue and purple dyes, we harvest the plants and ferment them in vats with urine and ash. The fermentation splits off the glucose, a wee bit of oxygen mixes in with the air (with those sturdy legs helping) and we get indigotin — the happy luxury dye of royalty, emperors and kings.

While much of our early dye came from plants — now it is mostly synthesized — other critters played a role. Members of the large and varied taxonomic family of predatory sea snails, marine gastropod mollusks, commonly known as murex snails were harvested by the Phoenicians for the vivid dye known as Tyrian purple.

While the extant specimens maintained their royal lineage for quite some time; at least until we were able to manufacture synthetic dyes, it was their fossil brethren that first captured my attention. There are about 1,200 fossil species in the family Muricidae. 

They first appear in the fossil record during the Aptian of the Cretaceous. Their ornate shells fossilize beautifully. I first read about them in Addicott's Miocene Gastropods and Biostratigraphy of the Kern River Area, California. It is a wonderful survey of 182 early and middle Miocene gastropod taxa.

References:

George E. Radwin and Anthony D'Attilio: The Murex shells of the World, Stanford University press, 1976, ISBN 0-8047-0897-5

Pappalardo P., Rodríguez-Serrano E. & Fernández M. (2014). "Correlated Evolution between Mode of Larval Development and Habitat in Muricid Gastropods". PLoS ONE 9(4): e94104. doi:10.1371/journal.pone.0094104

Miocene Gastropods and Biostratigraphy of the Kern River Area, California; United States Geological Survey Professional Paper 642