In contrast to blue pigments, yellows have been a greater challenge, and remain so even today. The most common traditional natural pigments are ochres derived from local supplies of coloured earths. Although some really do qualify to be termed yellow ochre, many are just too brown. The quest for a reliable primary yellow has been long and toxic much of the way.

One of the first really good yellows was orpiment, which comes straight from the alchemist’s laboratory. It has been widely used since ancient times, despite being arsenic sulphide and a deadly poison. Derived from natural minerals which are found locally in volcanic areas on most continents, orpiment was available and used in East Asian, Indian, Middle Eastern, Ancient Egyptian, Russian, and European art. As a dry pigment it was among those traded on most routes leading into and out of Europe, and elsewhere.

It has also been manufactured at some time in the past, although one of the key ingredients in its synthesis is arsenic trioxide, which is inevitably left as a residue in synthetic orpiment; that’s even more toxic than arsenic sulphide, and more readily absorbed into the body. Several of the mines which were sources of the pigment were manned by criminals, because of their inevitably brief working lives.

Orpiment was quite commonly combined with indigo to make a dark, rich green. A fine example of this is in The Wilton Diptych (c 1395-9), a very early European painting in egg tempera. The green cloak at the left appears to have been painted using orpiment.

Tintoretto’s Portrait of Vincenzo Morosini from about 1575-80 is a well-studied example of the use of orpiment in its details. As shown in the detail below, the orpiment used to form the brights on Morosini’s embroidered stole include small patches of the orange-red which is characteristic of orpiment’s sister pigment realgar (another form of arsenic sulphide).

Another contender as a primary pigment was Naples yellow, originally the highly toxic lead antimonate yellow, and nothing to do with Naples at all.

Naples yellow occurs in nature, in the unusual mineral Bindheimite, which it seems has never been used as a pigment. Instead, ancient civilisations in the eastern Mediterranean, from about 1500 BCE, used it to colour glass and pottery, and it’s one of the oldest synthetic pigments. By about 300 CE, it had been replaced by lead-tin yellow, and fell into disuse until reappearing as a pigment in paintings after 1600.

As its chemical name reveals, Naples yellow is a salt of two highly toxic metals, lead and antimony, and is therefore extremely poisonous, although less well-absorbed through the skin. Despite this, it remained popular during the rise of plein air landscape painting, as in Johann Georg von Dillis’ delightful oil sketch of Triva Castle from 1797.

In case you’re wondering, modern Naples yellow is very different, and contains neither lead nor antimony, being most commonly the result of mixing cadmium yellow with Chinese white.

Lead-tin yellow seems to have originated in glassmaking, and there is some evidence of its use as a pigment in glass made as early as 400 CE. Its earliest use in paintings seems to date back to Giotto in about 1300, following which it became extremely popular.

The centre panel of Rogier van der Weyden’s St Columba Altarpiece, showing the Adoration of the Magi, from about 1455, has been found to contain lead-tin yellow in the rich yellow sleeve of the king in the centre, shown in the detail below.

What happened later is rather strange. During the first half of the eighteenth century, lead-tin yellow declined markedly in popularity, and by 1750 it appears to have been replaced by other, sometimes less stable, pigments, including Naples yellow. Once replaced, the recipes for its manufacture appear to have been lost, and its use forgotten.

During the eighteenth century, there were also changes in the supply of pigments and paints to artists, and by the nineteenth century most were sourced from specialist colourmen, who appear not to have known about lead-tin yellow as a pigment. When commercial manufacture of oil and other paints became widespread in the late nineteenth century, the pigment was long forgotten.

Many yellow pigments in use, even into the twentieth century, have shown a pronounced tendency to fade, which becomes particularly devastating when mixed to make greens which later become blue. So when someone comes along offering you a ball of compressed powder which is an intense yellow, and appears more lightfast than most that you already have, you’ll believe anything that they say. It comes from the urine of cows? No worries – how much, and when can you deliver?

This seems to have been the story behind the introduction of Indian yellow into European painting. It had a long track-record of use in and around the Indian sub-continent, where it had featured in watercolours and gouache, and buyers in Europe were only too happy to pay high prices when it became available.

This exquisite watercolour miniature showing a Mongol Chieftain and Attendants from the Gulshan Album now in the Freer and Sackler Galleries is a good example, from around 1600. Its yellows and greens have lasted those four centuries very well, and careful testing by Elisabeth FitzHugh has shown the unmistakable presence of the chemicals known to be diagnostic of real Indian yellow.

The snag with European paintings is that so few works have been tested, and records are so scant, that we don’t even know when Indian yellow was first used to the west of the Middle East.

Ernst Willers’ Grove Near Ariccia in the Evening Light (1873) is one of the few European paintings known fairly unequivocally to contain Indian yellow, used perhaps in forming its rich greens.

We know with rather greater certainty when Indian yellow came off the market, as by the end of the nineteenth century supplies had essentially dried up. The claim is that, between the late 1500s and then, Indian herdsmen fed their cows with mango leaves, collected the cows’ urine, and dried it to generate the pigment as balls of compressed powder, some of which still exist. In the nineteenth century, this was increasingly viewed as being cruel to the cows, and the practice was eliminated.

Whether this story is accurate, or indeed the pigment ever saw much use, remains open to doubt. Certain claims, for example of a ban on the production of the pigment from 1908, have not been verified and appear legendary. But there is evidence that some artists in both India and Europe used the pigment in their paintings.

Chrome yellow, a family of pigments ranging from pale lemon to deep orange-red, is based on lead chromate, which had been ‘discovered’ as a mineral in the middle of the eighteenth century. Its use as a pigment wasn’t recognised until the early nineteenth century, when it became increasingly popular and versatile.

Initially, its supply was limited, and it was expensive as a result. As general commercial demand for the mineral increased, new sources of supply were found, and its price fell accordingly. During the latter half of the nineteenth century it was probably the mainstay yellow and orange in the palette of most painters.

The first evidence of the use of chrome yellow as a pigment in painting dates from just before 1810. Johann Friedrich Overbeck’s painting of Italia and Germania (or possibly Sulamith and Maria) was made in 1828, and is thus from the early adoption phase, when the pigment was expensive and encountered infrequently. Although Overbeck was restrained in his use of colours from orange through to yellow and green, he has achieved a subtle chromatic effect in the green fabric.

Carl Blechen used chrome yellow more extensively in his imposing View of Assisi, painted a few years later in 1832-35. By this time, the mixture of chrome yellow with Prussian blue had become known as green cinnabar or chrome green, although the chromium salt used was not itself green, of course.

Chrome yellow was widely used by the Impressionists and shown at the Salon, and is demonstrated well in Paul Cézanne’s famous painting of The Railway Cutting (c 1870). I believe that most if not all of the greens seen here rely on chrome yellow mixed with blue.

As some of the Impressionists, like Claude Monet, generated more income, they could afford to start using the newer, and far more expensive, cadmium-based pigments which were coming onto the market. Cadmium yellow is considerably more lightfast and durable than chrome yellow, so during the late nineteenth and early twentieth centuries, many painters switched away from chrome yellow.

However, both are potentially environmentally damaging, and in this century more modern, less toxic synthetic organic pigments have been introduced as substitutes. Thankfully, as both cadmium and chrome pigments trap their toxic salts in insoluble particles, neither presents any danger to the careful painter when used in paint. For the pastellist, though, inhalation of pigment in dust is a more significant risk.

Cadmium hadn’t been discovered until recently – 1817 – and then only by a chance observation of abnormal yellow colouration of a sample of what should have been zinc carbonate. The brilliant yellow colour of its salt cadmium sulphide was noticed the following year, but it wasn’t exploited as a pigment until the 1840s, when it became possible to manufacture in quantity.

Nevertheless, it has been claimed that it was used as a pigment for oil paints as early as 1829, and by 1851 it was shown by Winsor & Newton at the Great Exhibition at Crystal Palace in London, but remained extremely costly.

Few artists could afford to use cadmium yellow until its price fell late in the nineteenth century. Claude Monet was among its early users, in this painting of The Artist’s House at Argenteuil from 1873.

In summary, we’ve tried:

• yellow ochre, too dull and brown,
• orpiment, too poisonous,
• Naples yellow, too poisonous,
• lead-tin yellow, also toxic,
• Indian yellow, too cruel to cows, if it even existed,
• chrome yellow, not environmentally friendly,
• cadmium yellow, not environmentally friendly,

and quite a few other synthetic pigments more recently.

References

NS Baer, A Joel, RL Feller & N Indictor (1986) Artists’ Pigments, vol 1, ed Robert L Feller, Archetype. ISBN 978 1 904982 74 6. (Indian yellow)
Inge Fiedler and Michael Bayard (1986) Artists’ Pigments, vol 1, ed Robert L Feller, Archetype. ISBN 978 1 904982 74 6. (Cadmium yellow)
Elisabeth West Fitzhugh (1997) Artists’ Pigments, vol 3, ed Elisabeth West Fitzhugh, Archetype. ISBN 978 1 904982 76 0. (Orpiment)
Hermann Kühn, Mary Curran (1986) Artists’ Pigments, vol 1, ed Robert L Feller, Archetype. ISBN 978 1 904982 74 6. (Chrome yellow)
Hermann Kühn (1993) Artists’ Pigments, vol 2, ed Ashok Roy, Archetype. ISBN 978 1 904982 75 3. (Lead-tin yellow)
Ian NM Wainwright, John M Taylor and Rosamond D Harley (1986) Artists’ Pigments, vol 1, ed Robert L Feller, Archetype. ISBN 978 1 904982 74 6. (Naples yellow)