As we all should really be on holiday, I’m taking a long weekend to look at the stories of three green pigments, starting today with the oldest and most elusive of them, the mineral malachite.

Because green is a secondary colour, it might seem better mixed from blue and yellow, as it has been in various recipes such as Prussian green. But the painter always prefers using single pigments for the purity of their chroma, and the fact that the more pigments that get mixed, the closer the colour comes to muddy grey.

Given the shortage of lightfast bright greens, it’s surprising how little-used malachite green is in European painting, despite its rich colour. For a while it rejoiced quietly under traditional names including chrysocolla, green verditer, and even green bice, but it only ever became popular in Japan and China.

As a natural mineral, malachite is not uncommon, and a reliable source of pure pigment, which is chemically basic carbonate of copper. Malachite green was known to the ancient Egyptians, who appear to have used it as eye-paint. Found abundantly in Japanese and Chinese paintings from the seventh century onwards, it wasn’t used much in Europe until the Renaissance. After that, it almost died out in Europe until the nineteenth century, when it enjoyed a brief revival.

Two versions of the painting by Watanabe Kazan 渡辺崋山 of Sato Issai 佐藤一斎（五十歳）像 show malachite green at its finest.

This version from 1824, now in the Freer in Washington, is known to use malachite green with a slightly blue shade and deep in colour.

This smaller and earlier version from 1821, now in Tokyo, is a lighter, more yellow shade. I’m not aware of its pigment having been analysed, but I’d be surprised if it was straight malachite green.

The biggest problem with its adoption in Europe was the popularity there of oil paint. The pigment worked well where it could be ground quite coarsely and used in water-based media like fresco and egg tempera, but the finer you grind it, the paler it becomes. Oil painters like smooth buttery paints with fine pigment particles, which sadly didn’t work for malachite green.

The rich, almost emerald green robes of Spinello Aretino’s Virgin Enthroned with Angels from about 1380 contain malachite green, here in tempera medium.

Among its earliest appearances in oil paint is this spectacular centre panel of the van Eyck brothers’ Ghent Altarpiece, famous in its own right as the Adoration of the Lamb (c 1425-1432).

Continuing use of egg tempera in the Southern Renaissance helped it survive. Piero della Francesca’s famous The Baptism of Christ (after 1437), made in egg tempera on poplar wood, relies on the pigment for its greens. Microscopic examination of the paint layer here shows coarse mineral particles typical of natural malachite.

In Francesco del Cossa’s Saint Vincent Ferrer from about 1473-75, it has been identified in the dark green grass at the foot of the painting. This too was made using egg tempera.

However, microscopy of this paint layer shows that these pigment particles don’t seem to have been fractured as if they have been ground, but are globular, as occurs when the malachite green has been made by a process of precipitation. Such artificial malachite green didn’t appear in European paintings until after about 1430, just in time for Francesco del Cossa.

Although he painted in oils, Tintoretto was an enthusiastic user of malachite green. To obtain the range of greens seen in the rich and varied colours of vegetation in his Saint George and the Dragon from about 1555, he used this pigment with copper resinate glazes, a technique found in other paintings of the period.

Tintoretto’s vast oil painting of The Last Judgment (1560-62) in the Chiesa della Madonna dell’Orto, Venice, has been found to contain malachite green, I suspect in the band of green depicting the Flood just below the centre. The detail below makes this a bit clearer.

When painting the frescoes formerly in the Villa Aldobrandini between 1616-18, Domenichino and his assistants relied heavily on malachite green. It has been formally identified in this section, showing Apollo pursuing Daphne, where it’s the mainstay colour remaining, and is suspected in most of the others.

Although only classed as moderately permanent, these and other examples of very old frescoes show how well malachite green has retained its colour after four centuries or more. But with the rise of oil painting in European art, it fell from favour.

One of those who participated in its revival in the nineteenth century was Pierre-Auguste Renoir, whose painting of Chrysanthemums from 1881-82 shows how it could still be used in oil paint. But by then there was a much wider choice of more modern green pigments; the revival was short-lived, and malachite green has hardly been used since.

Reference

Rutherford J Gettens and Elisabeth West Fitzhugh (1993) Artists’ Pigments, vol 2, edited by Ashok Roy, Archetype. ISBN 978 1 904982 75 3.

Blue pigments used in painting include some of the oldest used by man, and others that led the change to modern synthetic pigments driven by the arrival of chemistry in the eighteenth century. This weekend I look at two examples, today the queen of pigments, ultramarine, and tomorrow the first synthetic chemical, Prussian blue.

Originally made by crushing and grinding the semi-precious stone lapis lazuli, the cost of ultramarine has exceeded that of gold. Seen in paintings, it produces a rich slightly reddish blue which stands the test of time, as distinctive and effective today as when it was first used. And its use has a history of unmasking fakes and forgeries.

The sole source of lapis lazuli in Europe and the West were quarries in Badakshan, described by Marco Polo and now in Afghanistan. It appears that wall paintings made around 507-554 CE adjacent to the great Buddahs of Bamiyan were the first to have used the mineral as a pigment. It was then used in early Persian miniatures, and in early Chinese and Indian paintings too. Tragically, these wall paintings in Bamiyan, Afghanistan, were damaged by the Taliban in 2001 when the two statues were destroyed, and their restoration has made little progress since.

The powdered pigment had made its way, first along the Silk Road, then by sea, to traders in Venice by about 1300. By the Renaissance, it was established as one of the most important and precious of all the pigments used in European art.

Because of its beauty and high cost, ultramarine blue was used for the robes of Jesus Christ and the Virgin Mary. Duccio’s panels from the Maestà Predella, including this of The Healing of the Man born Blind, show this tradition in its earliest years, around 1307-11. As a pigment, it proved practical in egg tempera as here, and in oils, watercolour, and fresco.

Ultramarine blue has been found in the van Eyck brothers’ Ghent Altarpiece from about 1432 (above), and particularly in its most famous panel, The Mystic Lamb, below.

Sandro Botticelli’s early tempera on panel painting Adoration of the Kings from about 1470, apparently made with Filippino Lippi, shows two different blue colours and purple. He painted the purple with an opaque underpainting of lead white tinted with a red lake derived from madder, to create pink. That was then glazed with quite coarse particles of ultramarine blue, so the pigment was thinly dispersed.

Peter Paul Rubens used ultramarine blue widely in his magnificent triptych now in Antwerp Cathedral. In its centre panel, Descent from the Cross (1612-14), it has been found combined with indigo and other pigments.

In van Dyck’s Charity from 1627-8, its most obvious use is in the blue cape, where ultramarine blue was painted over indigo, applied as both a tint and as a glaze over the top.

Visit any of the larger galleries with substantial collections of paintings made before 1700, and you will see works with drapery that I can only describe as arresting in the brilliance of their ultramarine blue. One stunning example in the National Gallery in London is Sassoferrato’s The Virgin in Prayer from 1640-50. The Virgin’s cloak looks as if it was painted only yesterday, and that colour makes you stop in your tracks and draws you into the painting, like no other pigment can.

Given its importance, and limited supply, considerable effort was devoted to ensuring that natural ultramarine blue was of the highest quality, and alternative sources were sought. Deposits in the Chilean Andes, and near Lake Baikal in Siberia, weren’t developed until the nineteenth century, and attempts to make synthetic ultramarine proved unsuccessful until 1828, when Jean Baptiste Guimet was awarded a prize of six thousand francs for his discovery. Almost simultaneously, C G Gmelin of Tübingen discovered a slightly different method.

Commercial production had started by 1830, and it became known as French ultramarine, to distinguish it from the natural pigment. Although almost identical in colour and performance, there are significant differences between natural and synthetic ultramarine when tested in the laboratory. This has enabled the examination of paintings to determine the source of their pigment, and has brought some surprises. These most often relate to later overpainting during restoration. For example, two areas of much later painting have been discovered in the van Eycks’ Ghent Altarpiece.

Examination of Édouard Manet’s Corner of a Café-Concert, from 1878-80, has shown that he used synthetic ultramarine in its blue passages, for example.

Pierre-Auguste Renoir’s The Umbrellas, from about 1881-86, uses synthetic ultramarine in a methodical fashion. The first stage in its painting used only cobalt blue, but in its second stage synthetic ultramarine was applied extensively.

Vincent van Gogh’s A Wheatfield, with Cypresses (1889) contains synthetic ultramarine in its deepest blues, and in some areas of green, although it’s unusual to find ultramarine mixed to form green. Before synthetic pigment became available, this would have been far too expensive a way of making any significant amount of green, but once much cheaper pigment came onto the market, that became more feasible, if still unusual.

The ability to distinguish synthetic ultramarine, which didn’t exist before about 1828, and the natural pigment has proved important in detecting some forgeries. Only the most ignorant would attempt to pass off a painting made with synthetic ultramarine as being very old, but a few fakes fell at that hurdle.

Han van Meegeren was far too knowledgeable and cunning to be caught so easily. He used natural ultramarine, for example when he sold The Men at Emmaus (1937) to the Museum Boijmans Van Beuningen as a Vermeer. What no one knew at the time was that his ultramarine looked genuine, but had been contaminated with a small amount of cobalt blue, which wasn’t discovered until 1803-04, and was first used as a pigment in 1806.

In 1960, the modern artist Yves Klein worked with the paint supplier Edouard Adam to ‘invent’ a paint he termed International Klein Blue (IKB). Although its formulation is a secret, it’s almost entirely synthetic ultramarine blue pigment in a polyvinyl acetate binder.

Like all the best queens, ultramarine blue has an unnerving habit of revealing the truth.

Reference

Joyce Plesters (1993) Artists’ Pigments, vol 2, ed Ashok Roy, Archetype. ISBN 978 1 904982 75 3.

As a primary colour, red is essential to most palettes, but it has also proved technically challenging to find pigments that are both intense and lasting. This weekend I look at the history of two contenders, in vermilion and crimson, names also steeped in history.

There’s one red that looks as brilliant today as when it was first brushed out five hundred or even two thousand years ago. It’s a pigment known to, and used by, the Romans, and in ancient China was not only used extensively in art, but was scattered in graves. Vermilion is one of the most toxic pigments, and over the last century has been displaced by cadmium red and more novel organic pigments. Look at many paintings made before 1870, and their reds are likely to be dominated by vermilion.

For a long time, vermilion paint was made using powdered cinnabar, naturally-occurring mercuric sulphide, and is then technically known as cinnabar rather than vermilion. Its manufacture from liquid mercury was probably brought from China to Europe, since when much of the vermilion pigment used in Europe has been synthetic.

The main source of cinnabar, and of the metal mercury, in Europe were the mines at Almadén in Spain. These were used by the Romans, and until their closure in 2000 had produced more cinnabar and mercury than any other location. In 1563, deposits were discovered in Huancavelica in Peru, and they were the second largest source over the following three hundred years. Other important sources have been located in China, Slovenia, Italy, Mexico, and the USA.

The mining of cinnabar has long been recognised as hazardous due to its great toxicity, something known as far back as the Romans. Locked in pigment particles in oil paint it’s less hazardous than in water-based paints such as egg tempera; it’s wisest not to use cinnabar or vermilion in dry form, as in pastels, even with good respiratory and skin protection. Even with careful handling, pigment residues pose a serious threat to the environment.

The brightest of the reds in Duccio’s Transfiguration, from the Maestà Predella Panels painted in 1307-11, have the distinctive colour of vermilion. It is often associated with holy people, and holy objects, and contrasts with the other brilliant pigment of ultramarine, which is conventionally used in the clothing of the Virgin Mary.

Its one unfortunate habit is a tendency to blacken, by forming the black version of cinnabar known as metacinnabar. This tends to happen more often in the thinner, less protective paint films of aqueous media, particularly egg tempera, as shown in Nardo di Cione’s Saint John the Baptist, Saint John the Evangelist and Saint James from 1363-65. The lining of the clothing of the saint at the right uses vermilion, and has darkened in patches as a result.

Masaccio’s panel of Saints Jerome and John the Baptist from the Santa Maria Maggiore Altarpiece, from 1428-29, is another fine example of the use of a lot of vermilion (as cinnabar). The robes of Saint Jerome, on the left, may also show a little darkening in patches, but contrast well with the paler and pinker red of Saint John the Baptist at the right.

Cinnabar saw extensive and highly effective use by the van Eycks in The Ghent Altarpiece (c 1432). Because this was painted in oils, the chances of discolouration are much lower.

Botticelli used cinnabar in several passages in his Mystic Nativity (1500), where its persistent colour contrasts with his use of other red pigments, which haven’t retained their colour as well.

All the Masters and most other significant artists of the past used cinnabar, or vermilion when it was being manufactured in Europe by the early seventeenth century. Tintoretto was no exception, as shown in these two examples: Jupiter and Semele (1545) above, and The Origin of the Milky Way (c 1575), below.

Peter Paul Rubens’ centre panel of the Descent from the Cross (1612-14) in the huge triptych in Onze-Lieve-Vrouwekathedraal, in Antwerp, is one of the most spectacular demonstrations of the use of vermilion, and its lasting chromatic brilliance.

Rembrandt is another Master who used vermilion to great effect, here in the dress of the woman at the right, in his Belshazzar’s Feast (c 1635-38). The colour draws attention to her as she is so shocked as to empty the goblet she is holding in her right hand. A duller colour might have allowed this dramatic action to pass unnoticed by the viewer.

Aelbert Cuyp’s Hilly River Landscape with a Horseman talking to a Shepherdess from about 1655-60 is one of the few oil paintings in which darkening of cinnabar has become obvious. The pigment serves well in the huntsman’s coat, but has darkened in patches.

William Hogarth played on another common association of the colour red in the third painting, The Inspection, from his series Marriage A-la-Mode (c 1743). Although in English we usually refer to a scarlet woman, rather than a vermilion one, his use of vermilion here is effective in portraying the woman as a prostitute.

Vermilion remained popular well into the latter half of the nineteenth century, long enough for it to grace the paintings of the Pre-Raphaelite movement and the French Impressionists.

Although Claude Monet used just a few dabs and strokes of vermilion in his landmark painting Bathers at la Grenouillère (1869), he continued to use it well into the latter years of his career. By that time, though, the new cadmium reds were replacing vermilion, a process that is almost complete today, with cadmiums now being superceded by modern organic pigments.

Reference

RJ Gettens, RL Feller & WT Chase (1993) Artists’ Pigments, vol 2, ed Ashok Roy, Archetype. ISBN 978 1 904982 75 3.